WO2016075197A1 - Doped molded catalyst body - Google Patents

Doped molded catalyst body Download PDF

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Publication number
WO2016075197A1
WO2016075197A1 PCT/EP2015/076343 EP2015076343W WO2016075197A1 WO 2016075197 A1 WO2016075197 A1 WO 2016075197A1 EP 2015076343 W EP2015076343 W EP 2015076343W WO 2016075197 A1 WO2016075197 A1 WO 2016075197A1
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Prior art keywords
catalyst
oxide
metal oxides
shaped body
dopants
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PCT/EP2015/076343
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German (de)
French (fr)
Inventor
Anja Roscher
Hans-Jürgen EBERLE
Christoph RÜDINGER
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Wacker Chemie Ag
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Publication of WO2016075197A1 publication Critical patent/WO2016075197A1/en

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    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/66—Silver or 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
    • 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
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • 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
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/06—Washing
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to a doped shaped catalyst body and its use in processes for the preparation of vinyl acetate by means of gas phase oxidation of acetic acid and ethylene.
  • Suitable catalysts may contain as catalytically active components palladium and / or its compounds and alkali compounds, as well as additionally gold and / or its compounds (system Pd / alkali / Au).
  • the catalytically active components are applied to shaped bodies as catalyst supports.
  • Suitable support materials are metal oxides such as silicon dioxides, in particular pyrogenically prepared metal oxides such as fumed silicas.
  • the production of the shaped bodies from the metal-oxide powders is generally carried out by pressing or extrusion, if appropriate using binders and lubricants, in order to obtain stable shaped bodies.
  • Several types of catalyst are known in the prior art, for example, balls, (hole) cylinders or rings.
  • the catalyst molding is doped with other metals in addition to the equipment with the active components palladium, gold and alkali metal (potassium).
  • WO 2008/145395 A2 describes doped palladium-gold shell catalysts. It is described that the activity and
  • WO 2010/060649 A2 relates to a coated catalyst comprising a zirconium oxide-containing catalyst support which contains palladium, gold and potassium. It is claimed that the shell catalyst is additionally doped with at least one oxide of a metal selected from the group consisting of hafnium, titanium, niobium, tantalum, tungsten, magnesium, rhenium, yttrium and iron.
  • the object of the present invention was to increase the activity of catalysts for the production of vinyl acetate by means of gas phase oxidation of acetic acid and ethylene.
  • the invention relates to shaped catalyst bodies of metal oxides, which are equipped with palladium and gold and an alkali compound and dopants, characterized in that the catalyst shaped body having at least two dopants from the group consisting of the oxides of tungsten, titanium, zirconium, aluminum , Boron, iron and niobium are equipped.
  • Suitable metal oxides for the catalyst moldings are Silizi ⁇ oxide (Si x O y), aluminum oxide (Al x O y), titanium oxide (Ti x O y), zirconium ⁇ oxide (ZrxOy), cerium oxide (CexOy) or mixtures of these metal oxides.
  • Fumed silica is preferably used, particularly preferably silicon dioxide (Si02), such as WACKER HDK ® T40 from Wacker Chemie AG.
  • the dopants are used as ⁇ based in each case in an amount of 0.001 to 3.0 wt .-% each based on the total weight of metal oxide and dopants.
  • the amount of dopant is in each case 1.0 to 3.0 wt .-%, each based on the total weight of metal oxide and dopants.
  • the method can be used from DE 10 2006 058 800 AI, the relevant information is part of the application (incorporated by reference).
  • the metal oxide and the dopants are suspended in water, for example by means of a dissolver or planetary dissolver.
  • the solids content of the aqueous metal oxide / dopant suspension is preferably adjusted to values of 15 to 30% by weight.
  • the aqueous suspension of the metal oxide and the dopants is coagulated.
  • the mass thus obtained is then shaped into shaped articles, for example spheres, cylinders, perforated cylinders or rings.
  • the shaped catalyst bodies have a diameter of 1 to 20 mm, preferably 2 to 10 mm.
  • their length is preferably 1 to 10 mm.
  • rings with a length of 1 mm to 2 mm, an outer diameter of 3 mm to 5 mm, an inner diameter of 2 mm to 3 mm and a wall thickness of 0.5 mm to 1.5 mm.
  • the shaping is preferably carried out by means of extrusion, wherein the length of the extrudates is adjusted by cutting the extrudates accordingly with a cutting device.
  • the moldings thus obtained are then dried, preferably at a temperature of 25 ° C to 100 ° C.
  • the drying step is followed by the calcination of the moldings.
  • the calcination can be carried out in an oven under an air atmosphere, if appropriate under protective gas. Generally this is done to a temperature of Heated to 500 ° C to 1000 ° C.
  • the sintering time is generally between 2 and 10 hours.
  • the conversion of the catalyst molding in an active catalyst is done by applying one or more catalytically active compounds such as palladium and gold or their precursor compounds and the alkali compound.
  • the shaped catalyst bodies can be impregnated with a solution containing palladium salt and gold salt.
  • the support materials used can be impregnated with a basic solution.
  • the latter serves to transfer the palladium compound and gold compound into their hydroxides.
  • Suitable palladium salts are, for example, palladium chloride, sodium or potassium palladium chloride, palladium acetate or palladium nitrate.
  • Suitable gold salts are gold (III) chloride and tetrachloroauric (III) acid.
  • the compounds in the basic solution are preferably potassium hydroxide, sodium hydroxide or sodium metasilicate.
  • the reaction of the noble metal salt solution with the basic solution to form insoluble noble metal compounds can be slow and, depending on the preparation method, is generally completed after 1 to 24 hours. Thereafter, the water-insoluble noble metal compounds are treated with reducing agents. It can be made a gas phase reduction, for example with hydrogen, ethene or forming gas.
  • the chloride which may be present on the support can be removed by a thorough washing with water. After the wash, the catalyst preferably contains less than 500 ppm of chloride.
  • the catalyst precursor obtained after the reduction can be dried and finally treated with alkali metal acetates or alkali compounds which are under the reaction conditions in the production of vinyl acetate monomer completely or partially in alkali metal acetates, impregnated. Preferably, it can be impregnated with potassium acetate.
  • the finished catalyst can then be dried to a residual moisture of less than 5%. The drying can be carried out in air, optionally under nitrogen, as an inert gas.
  • the palladium content of the Pd / alkali / Au catalysts is 0.2 to 5.0 wt .-%, preferably 0.3 to 3.0 wt .-%, each based on the total weight of the shaped catalyst body.
  • the gold content of the Pd / alkali / Au catalysts is 0.2 to 5.0 wt .-%, preferably 0.3 to 3.0 wt .-%, each based on the total weight of the shaped catalyst body.
  • the alkali content of the Pd / alkali / Au catalysts is 0.5 to 15 wt .-%, preferably 1.0 to 12 wt .-%, each based on the total weight of the shaped catalyst body.
  • potassium is used as the alkali metal.
  • Another object of the invention is the use of the catalyst moldings of the invention in the production of vinyl acetate by gas phase oxidation of acetic acid and ethylene.
  • the catalyst moldings doped with the combination according to the invention show, in comparison to non-doped or only with a dopant doped catalyst moldings higher yield with high selectivity.
  • Comparative Example 1 4 kilograms of fumed silica (WACKER HDK ® T40) were stirred into 35 kilograms of deionized water. By addition of hydrochloric acid, a pH of 2.8 was set and kept constant. With constant stirring, an additional 4.5 kilograms of fumed silica (WACKER HDK® T40) were stirred in. After complete addition of the metal oxide powder was homogenized for a further 10 minutes before the suspension for a period of 45 minutes in a stirred ball mill with grinding beads of silicon nitride (diameter of the grinding beads 2.0 mm, degree of filling 70 vol .-%) under pH consistency at a pH of 2.8 was milled by the addition of further hydrochloric acid.
  • the angular velocity during the milling step was 11 meters per second.
  • an aqueous ammonia solution was added to the suspension with constant stirring until a pH of 6.2 was obtained and at this point gelation of the mass took place.
  • the resulting mass was extruded and cut in a ram extruder by a suitable tool.
  • the resulting molded articles - in this case rings of 1 mm in length, 4 mm in outer diameter and 2.5 mm in bore - were dried for 24 hours at a temperature of 85 ° C. and a relative humidity of 70% and then for calcined at 900 ° C for a period of 2 hours.
  • the rings had a surface area (BET surface area) of 212 m 2 / g and a pore volume of 0.99 ml / g. Bulk density was 202 grams per liter.
  • the catalyst was dried at a temperature of 80 ° C for a period of 5 hours in vacuo. Subsequently, the catalyst was treated with an aqueous ammonia solution containing 0.25% by weight of ammonia for a period washed for 45 hours. The catalyst was reduced at a temperature of 200 ° C for 5 hours with forming gas (95% N 2 /5% H 2 ). Subsequently, the catalyst was impregnated with acetic acid-containing Kaiiumacetat solution (71.65 grams of potassium acetate in 375 milliliters of acetic acid) and finally dried at a temperature of 80 ° C for a period of 5 hours in vacuo. The final catalyst had a concentration of 2.0 wt% palladium (7.4 g / l), 2.0 wt% gold (7.4 g / l) and 6.5 wt% potassium ( 24.1 g / l).
  • Example 2 Example 2:
  • the impregnation of the catalyst moldings with palladium, gold and potassium was likewise carried out analogously to Comparative Example 1.
  • the finished catalyst likewise had a concentration of 2.0% by weight of palladium, 2.0% by weight of gold and 6.5% by weight. -% potassium, and additionally 2.5 wt .-% tungsten, 2.5 wt .-% titanium, 2.5 wt .-% zirconium, 2.5 wt .-% aluminum, 0.003 wt .-% boron.
  • Activity and selectivity of the catalysts of Comparative Example 1 and Example 2 were measured over a period of 200 hours.
  • the catalysts were tested in an oil tempered flow reactor (reactor length 1200 mm, inner diameter 19 mm) at an absolute pressure of 9.5 bar and a space velocity (GHSV) of 3500 Nm3 / (m3 * h) with the following gas composition: 60 vol. % Ethene, 19.5% by volume of carbon dioxide, 13% by volume of acetic acid and 7.5% by volume of oxygen.
  • the catalysts were investigated in the temperature range from 130 ° C to 180 ° C, measured in the catalyst bed.
  • the reaction products were in the outlet of the reactor by means of online

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to molded catalyst bodies made of metal oxides, which are equipped with palladium and gold as well as an alkali compound and dopants, characterized in that the molded catalyst bodies are equipped with at least two dopants from the group consisting of the oxides of tungsten, titanium, zirconium, aluminum, boron, iron and niobium. Another object of the invention is the use of the molded catalyst bodies in processes for the production of vinyl acetate by means of gas phase oxidation of acetic acid and ethylene.

Description

Dotierter Katalysator-Formkörper  Doped catalyst shaped body
Die Erfindung betrifft einen dotierten Katalysator-Formkörper und dessen Verwendung in Verfahren zur Herstellung von Vinylacetat mit- tels Gasphasenoxidation von Essigsäure und Ethylen. The invention relates to a doped shaped catalyst body and its use in processes for the preparation of vinyl acetate by means of gas phase oxidation of acetic acid and ethylene.
Es ist bekannt, dass man Ethylen in der Gasphase mit Essigsäure und Sauerstoff an Festbettkatalysatoren zu Vinylacetat umsetzen kann. Geeignete Katalysatoren können als katalytisch aktive Komponenten Pal- ladium und/oder dessen Verbindungen und Alkaliverbindungen, sowie zusätzlich Gold und/oder dessen Verbindungen (System Pd/Alkali/Au) enthalten. Die katalytisch aktiven Komponenten sind auf Formkörpern als Katalysatorträger aufgetragen. Als Trägermaterialien eignen sich Metalloxide wie Siliziumdioxide, insbesondere pyrogen hergestellte Metalloxide wie pyrogene Siliziumdioxide. Die Herstellung der Formkörper aus den metalloxydischen Pulvern erfolgt in der Regel durch Pressen, oder Extrusion, gegebenenfalls unter Verwendung von Bindern und Gleitmitteln, um stabile Form- körper zu erhalten. Aus dem Stand der Technik sind mehrere Katalysatorformen bekannt, beispielsweise Kugeln, (Loch) Zylinder oder Ringe. It is known that one can implement ethylene in the gas phase with acetic acid and oxygen on fixed bed catalysts to vinyl acetate. Suitable catalysts may contain as catalytically active components palladium and / or its compounds and alkali compounds, as well as additionally gold and / or its compounds (system Pd / alkali / Au). The catalytically active components are applied to shaped bodies as catalyst supports. Suitable support materials are metal oxides such as silicon dioxides, in particular pyrogenically prepared metal oxides such as fumed silicas. The production of the shaped bodies from the metal-oxide powders is generally carried out by pressing or extrusion, if appropriate using binders and lubricants, in order to obtain stable shaped bodies. Several types of catalyst are known in the prior art, for example, balls, (hole) cylinders or rings.
Zur Steigerung der Aktivität von solchen Katalysatoren wird der Katalysator-Formkörper zusätzlich zur Ausrüstung mit den Aktivkomponenten Palladium, Gold und Alkalimetall (Kalium) mit weiteren Metallen dotiert. In der WO 2008/145392 A2 wird beispielsweise die Dotierung mit Hafniumoxid Hf02 beansprucht . To increase the activity of such catalysts, the catalyst molding is doped with other metals in addition to the equipment with the active components palladium, gold and alkali metal (potassium). In WO 2008/145392 A2, for example, the doping with hafnium oxide Hf0 2 claimed.
In der WO 2008/145395 A2 werden dotierte Palladium-Gold-Schalenkata- lysatoren beschrieben. Es wird beschrieben, dass die Aktivität undWO 2008/145395 A2 describes doped palladium-gold shell catalysts. It is described that the activity and
Selektivität bei der Vinylacetat-Herstellung unter Verwendung solcher Schalenkatalystoren gesteigert werden kann, wenn der Katalysatorträger mit zumindest einem Oxid eines Elements ausgewählt aus der Gruppe bestehend aus Lithium, Phosphor, Calcium, Vanadium, Chrom, Mangan, Eisen, Strontium, Niob, Tantal, Wolfram, Lanthan und den Seltenerdmetallen dotiert wird. Die WO 2010/060649 A2 betrifft einen Schalenkatalysator umfassend einen Zirkonoxid enthaltenden Katalysatorträger, welcher Palladium, Gold und Kalium enthält. Es wird beansprucht, dass der Schalenkataly- sator zusätzlich noch mit zumindest einem Oxid eines Metalls ausgewählt aus der Gruppe bestehend aus Hafnium, Titan, Niob, Tantal, Wolfram, Magnesium, Rhenium, Yttrium und Eisn dotiert ist. Selectivity in vinyl acetate production using such shell catalysts can be increased if the catalyst support with at least one oxide of an element selected from the group consisting of lithium, phosphorus, calcium, vanadium, chromium, manganese, iron, strontium, niobium, tantalum, tungsten , Lanthanum and the rare earth metals is doped. WO 2010/060649 A2 relates to a coated catalyst comprising a zirconium oxide-containing catalyst support which contains palladium, gold and potassium. It is claimed that the shell catalyst is additionally doped with at least one oxide of a metal selected from the group consisting of hafnium, titanium, niobium, tantalum, tungsten, magnesium, rhenium, yttrium and iron.
Der vorliegenden Erfindung lag die Aufgabe zugrunde die Aktivität von Katalysatoren für die Herstellung von Vinylacetat mittels Gaspha- senoxidation von Essigsäure und Ethylen zu erhöhen. The object of the present invention was to increase the activity of catalysts for the production of vinyl acetate by means of gas phase oxidation of acetic acid and ethylene.
Gegenstand der Erfindung sind Katalysator-Formkörper aus Metalloxiden, welche mit Palladium und Gold sowie einer AlkaliVerbindung und Dotierstoffen ausgerüstet sind, dadurch gekennzeichnet, dass die Katalysator-Formkörper mit mindestens zwei Dotierstoffen aus der Gruppe bestehend aus den Oxiden von Wolfram, Titan, Zirkonium, Aluminium, Bor, Eisen und Niob ausgerüstet sind. Als Metalloxide für den Katalysator-Formkörper geeignet sind Silizi¬ umoxid (SixOy) , Aluminiumoxid (AlxOy) , Titanoxid (TixOy) , Zirkonium¬ oxid (ZrxOy) , Ceroxid (CexOy) oder Mischungen dieser Metalloxide. Bevorzugt wird pyrogen hergestelltes Siliziumoxid verwendet, besonders bevorzugt Siliziumdioxid (Si02), beispielsweise WACKER HDK® T40 von der Wacker Chemie AG. The invention relates to shaped catalyst bodies of metal oxides, which are equipped with palladium and gold and an alkali compound and dopants, characterized in that the catalyst shaped body having at least two dopants from the group consisting of the oxides of tungsten, titanium, zirconium, aluminum , Boron, iron and niobium are equipped. Suitable metal oxides for the catalyst moldings are Silizi ¬ oxide (Si x O y), aluminum oxide (Al x O y), titanium oxide (Ti x O y), zirconium ¬ oxide (ZrxOy), cerium oxide (CexOy) or mixtures of these metal oxides. Fumed silica is preferably used, particularly preferably silicon dioxide (Si02), such as WACKER HDK ® T40 from Wacker Chemie AG.
Bevorzugt wird mit einem Blend aus Wolframoxid, Titanoxid, Zirkonium¬ oxid, Aluminiumoxid und Boroxid dotiert. Die Dotierstoffe werden da¬ bei jeweils in einer Menge von 0,001 bis 3,0 Gew.-% jeweils bezogen auf das Gesamtgewicht aus Metalloxid und Dotierstoffe eingesetzt. Vorzugsweise beträgt die Menge an Dotierstoff jeweils 1,0 bis 3,0 Gew.-%, jeweils bezogen auf das Gesamtgewicht aus Metalloxid und Dotierstoffe . Zur Herstellung der Katalysator-Formkörper kann das Verfahren aus der DE 10 2006 058 800 AI eingesetzt werden, deren diesbezügliche Angaben Teil der Anmeldung sind ( incorporated by reference) . Dazu werden das Metalloxid und die Dotierstoffe in Wasser suspendiert, bei- spielsweise mittels eines Dissolvers oder Planetendissolvers . Preferably is doped with a blend of tungsten oxide, titanium oxide, zirconium oxide ¬, aluminum oxide and boron oxide. The dopants are used as ¬ based in each case in an amount of 0.001 to 3.0 wt .-% each based on the total weight of metal oxide and dopants. Preferably, the amount of dopant is in each case 1.0 to 3.0 wt .-%, each based on the total weight of metal oxide and dopants. For the preparation of the shaped catalyst body, the method can be used from DE 10 2006 058 800 AI, the relevant information is part of the application (incorporated by reference). For this purpose, the metal oxide and the dopants are suspended in water, for example by means of a dissolver or planetary dissolver.
Der Feststoffgehalt der wässerigen Metalloxid/Dotierstoff -Suspension wird vorzugsweise auf Werte von 15 bis 30 Gew.-% eingestellt. Der pH- Wert der Metalloxid/Dotierstoff-Suspension wird während deren Her- Stellung in einem Bereich von pH = 2,0 bis 4,0 gehalten. Dies kann durch Zugabe einer Säure, beispielsweise Phosphorsäure, oder durch Zugabe von Base, beispielsweise wässerige Ammoniaklösung, erfolgen. The solids content of the aqueous metal oxide / dopant suspension is preferably adjusted to values of 15 to 30% by weight. The pH of the metal oxide / dopant suspension is maintained in the range of pH = 2.0 to 4.0 during its production. This can be done by adding an acid, for example phosphoric acid, or by adding base, for example aqueous ammonia solution.
Im nächsten Schritt wird die wässerige Suspension des Metalloxids und der Dotierstoffe zur Koagulation gebracht. Im Falle von Siliziumdioxid kann das beispielsweise durch Verschiebung des pH-Wertes der Suspension in einen Bereich von pH = 5 bis 10 erfolgen. In the next step, the aqueous suspension of the metal oxide and the dopants is coagulated. In the case of silicon dioxide, this can be done, for example, by shifting the pH of the suspension to a range of pH = 5 to 10.
Die damit erhaltene Masse wird dann zu den Formkörpern geformt, bei- spielsweise zu Kugeln, Zylindern, Lochzylindern oder Ringen. Im Allgemeinen haben die Katalysator-Formkörper einen Durchmesser von 1 bis 20 mm, bevorzugt von 2 bis 10 mm. Im Falle von Zylindern, Lochzylindern und Ringen beträgt deren Länge vorzugsweise 1 bis 10 mm. Am meisten bevorzugt werden Ringe mit einer Länge von 1 mm bis 2 mm, ei- nem Außendurchmesser von 3 mm bis 5 mm, einem Innendurchmesser von 2 mm bis 3 mm und einer Wandstärke von 0,5 mm bis 1,5 mm. Die Formgebung erfolgt vorzugsweise mittels Extrusion, wobei die Länge der Extrudaten dadurch eingestellt wird, dass die Extrudate mit einer Schneidvorrichtung entsprechend geschnitten werden. The mass thus obtained is then shaped into shaped articles, for example spheres, cylinders, perforated cylinders or rings. In general, the shaped catalyst bodies have a diameter of 1 to 20 mm, preferably 2 to 10 mm. In the case of cylinders, perforated cylinders and rings, their length is preferably 1 to 10 mm. Most preferred are rings with a length of 1 mm to 2 mm, an outer diameter of 3 mm to 5 mm, an inner diameter of 2 mm to 3 mm and a wall thickness of 0.5 mm to 1.5 mm. The shaping is preferably carried out by means of extrusion, wherein the length of the extrudates is adjusted by cutting the extrudates accordingly with a cutting device.
Die damit erhaltenen Formkörper werden anschließend getrocknet, vorzugsweise bei einer Temperatur von 25°C bis 100°C. Dem Trocknungsschritt schließt sich die Kalzinierung der Formkörper an. Die Kalzinierung kann in einem Ofen unter Luftatmosphäre, gegebenenfalls unter Schutzgas, erfolgen. Im Allgemeinen wird dazu auf eine Temperatur von 500°C bis 1000°C erhitzt. Die Sinterzeit beträgt im Allgemeinen zwischen 2 und 10 Stunden. The moldings thus obtained are then dried, preferably at a temperature of 25 ° C to 100 ° C. The drying step is followed by the calcination of the moldings. The calcination can be carried out in an oven under an air atmosphere, if appropriate under protective gas. Generally this is done to a temperature of Heated to 500 ° C to 1000 ° C. The sintering time is generally between 2 and 10 hours.
Die Überführung des Katalysator-Formkörpers in einen aktiven Kataly- sator geschieht durch Aufbringen einer oder mehrerer katalytisch aktiver Verbindungen wie Palladium und Gold oder deren Precursor- Verbindungen und der Alkaliverbindung. The conversion of the catalyst molding in an active catalyst is done by applying one or more catalytically active compounds such as palladium and gold or their precursor compounds and the alkali compound.
Zur Beladung mit Palladium und Gold können die Katalysator-Formkörper mit einer Palladiumsalz und Goldsalz enthaltenden Lösung imprägniert werden. Gleichzeitig mit der edelmetallhaltigen Lösung können die eingesetzten Trägermaterialien mit einer basischen Lösung imprägniert werden. Letztere dient zur Überführung der Palladiumverbindung und Goldverbindung in ihre Hydroxide. Geeignete Palladiumsalze sind bei- spielsweise Palladiumchlorid, Natrium- oder Kaliumpalladiumchlorid, Palladiumacetat oder Palladiumnitrat. Als Goldsalze eignen sich Gold (III) -Chlorid und Tetrachlorogold (III) -säure . Die Verbindungen in der basischen Lösung sind vorzugsweise Kaliumhydroxid, Natriumhydroxid oder Natriummetasilikat verwendet. For loading with palladium and gold, the shaped catalyst bodies can be impregnated with a solution containing palladium salt and gold salt. Simultaneously with the noble metal-containing solution, the support materials used can be impregnated with a basic solution. The latter serves to transfer the palladium compound and gold compound into their hydroxides. Suitable palladium salts are, for example, palladium chloride, sodium or potassium palladium chloride, palladium acetate or palladium nitrate. Suitable gold salts are gold (III) chloride and tetrachloroauric (III) acid. The compounds in the basic solution are preferably potassium hydroxide, sodium hydroxide or sodium metasilicate.
Die Umsetzung der Edelmetallsalzlösung mit der basischen Lösung zu unlöslichen Edelmetallverbindungen kann langsam erfolgen und ist je nach Präparationsmethode im Allgemeinen erst nach 1 bis 24 Stunden abgeschlossen. Danach werden die wasserunlöslichen Edelmetallverbin- düngen mit Reduktionsmitteln behandelt. Es kann eine Gasphasenreduktion beispielsweise mit Wasserstoff, Ethen oder Formiergas vorgenommen werden. The reaction of the noble metal salt solution with the basic solution to form insoluble noble metal compounds can be slow and, depending on the preparation method, is generally completed after 1 to 24 hours. Thereafter, the water-insoluble noble metal compounds are treated with reducing agents. It can be made a gas phase reduction, for example with hydrogen, ethene or forming gas.
Vor und/oder nach der Reduktion der Edelmetallverbindungen kann das auf dem Träger gegebenenfalls vorhandene Chlorid durch eine gründliche Waschung mit Wasser entfernt werden. Nach der Waschung enthält der Katalysator bevorzugt weniger als 500 ppm Chlorid. Before and / or after the reduction of the noble metal compounds, the chloride which may be present on the support can be removed by a thorough washing with water. After the wash, the catalyst preferably contains less than 500 ppm of chloride.
Die nach der Reduktion erhaltene Katalysatorvorstufe kann getrocknet und abschließend mit Alkaliacetaten oder AlkaliVerbindungen, die sich unter den Reaktionsbedingungen bei der Produktion von Vinylacetatmo- nomer ganz oder teilweise in Alkaliacetate umwandeln, imprägniert werden. Vorzugsweise kann mit Kaliumacetat imprägniert werden. Der fertige Katalysator kann anschließend bis auf eine Restfeuchte von weniger als 5 % getrocknet werden. Die Trocknung kann an Luft, gegebenenfalls unter Stickstoff, als Inertgas erfolgen. The catalyst precursor obtained after the reduction can be dried and finally treated with alkali metal acetates or alkali compounds which are under the reaction conditions in the production of vinyl acetate monomer completely or partially in alkali metal acetates, impregnated. Preferably, it can be impregnated with potassium acetate. The finished catalyst can then be dried to a residual moisture of less than 5%. The drying can be carried out in air, optionally under nitrogen, as an inert gas.
Der Palladium-Gehalt der Pd/Alkali/Au-Katalysatoren beträgt 0,2 bis 5,0 Gew.-%, bevorzugt 0,3 bis 3,0 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Katalysator-Formkörper. The palladium content of the Pd / alkali / Au catalysts is 0.2 to 5.0 wt .-%, preferably 0.3 to 3.0 wt .-%, each based on the total weight of the shaped catalyst body.
Der Gold-Gehalt der Pd/Alkali/Au-Katalysatoren beträgt 0,2 bis 5,0 Gew.-%, bevorzugt 0,3 bis 3,0 Gew.-% , jeweils bezogen auf das Gesamtgewicht der Katalysator-Formkörper.  The gold content of the Pd / alkali / Au catalysts is 0.2 to 5.0 wt .-%, preferably 0.3 to 3.0 wt .-%, each based on the total weight of the shaped catalyst body.
Der Alkali-Gehalt der Pd/Alkali/Au-Katalysatoren beträgt 0,5 bis 15 Gew.-%, vorzugsweise 1,0 bis 12 Gew.-% , jeweils bezogen auf das Gesamtgewicht der Katalysator-Formkörper. Vorzugsweise wird Kalium als Alkalimetall verwendet. Ein weiterer Gegenstand der Erfindung ist die Verwendung der erfindungsgemäßen Katalysator-Formkörper bei der Herstellung von Vinyl- acetat mittels Gasphasenoxidation von Essigsäure und Ethylen. The alkali content of the Pd / alkali / Au catalysts is 0.5 to 15 wt .-%, preferably 1.0 to 12 wt .-%, each based on the total weight of the shaped catalyst body. Preferably, potassium is used as the alkali metal. Another object of the invention is the use of the catalyst moldings of the invention in the production of vinyl acetate by gas phase oxidation of acetic acid and ethylene.
Die mit der erfindungsgemäßen Kombination dotierten Katalysator- Formkörper zeigen im Vergleich zu nicht dotierten oder nur mit einem Dotierstoff dotierten Katalysator-Formkörpern höhere Ausbeute mit hoher Selektivität. The catalyst moldings doped with the combination according to the invention show, in comparison to non-doped or only with a dopant doped catalyst moldings higher yield with high selectivity.
In den folgenden Beispielen wird die Leistungsfähigkeit der erfin- dungsgemäßen dotierten Katalysator-Formkörper mit der von herkömmlichen Katalysator-Formkörpern ohne Dotierung verglichen. In the following examples, the performance of the inventive doped catalyst moldings is compared with that of conventional catalyst moldings without doping.
Beispiele : Vergleichsbeispiel 1: 4 Kilogramm pyrogene Kieselsäure (WACKER HDK® T40) wurden in 35 Kilogramm entionisiertem Wasser eingerührt. Durch Zugabe von Salzsäure wurde ein pH-Wert von 2,8 eingestellt und konstant gehalten. Unter ständigem Rühren wurden weitere 4,5 Kilogramm pyrogener Kieselsäure (WACKER HDK® T40) eingerührt. Nach abgeschlossener Zugabe des Metalloxid-Pulvers wurde für eine Dauer von weiteren 10 Minuten homogenisiert, bevor die Suspension für eine Dauer von 45 Minuten in einer Rührwerkskugelmühle mit Mahlperlen aus Siliciumnitrid (Durchmesser der Mahlperlen 2,0 mm, Füllgrad 70 Vol.-%) unter pH-Konstanz bei einem pH-Wert von 2,8 durch Zugabe weiterer Salzsäure vermählen wurde. Die Winkelgeschwindigkeit während des Mahlschrittes betrug 11 Meter pro Sekunde. Nach Abschluss der Mahlung wurde der Suspension unter ständigem Rühren eine wässrige Ammoniaklösung zugegeben, bis sich ein pH-Wert von 6,2 ergab und an diesem Punkt eine Vergelung der Masse erfolgte. Die erhaltene Masse wurde in einer Kolbenstrangpresse durch ein geeignetes Werkzeug verstrangt und geschnitten. Die erhaltenen Formkörper - in diesem Fall Ringe mit einer Länge von 1 mm, einem Außendurchmesser von 4 mm und einer Bohrung von 2,5 mm - wurden 24 Stunden lang getrocknet bei einer Temperatur von 85°C und einer Luftfeuchtigkeit von 70 % und anschließend für eine Dauer von 2 Stunden bei 900°C kalziniert. Die Ringe wiesen eine Oberfläche (BET- Oberfläche) von 212 m2/g und ein Porenvolumen von 0,99 ml/g auf. Die Schüttdichte betrug 202 Gramm pro Liter. Examples: Comparative Example 1 4 kilograms of fumed silica (WACKER HDK ® T40) were stirred into 35 kilograms of deionized water. By addition of hydrochloric acid, a pH of 2.8 was set and kept constant. With constant stirring, an additional 4.5 kilograms of fumed silica (WACKER HDK® T40) were stirred in. After complete addition of the metal oxide powder was homogenized for a further 10 minutes before the suspension for a period of 45 minutes in a stirred ball mill with grinding beads of silicon nitride (diameter of the grinding beads 2.0 mm, degree of filling 70 vol .-%) under pH consistency at a pH of 2.8 was milled by the addition of further hydrochloric acid. The angular velocity during the milling step was 11 meters per second. After completion of the grinding, an aqueous ammonia solution was added to the suspension with constant stirring until a pH of 6.2 was obtained and at this point gelation of the mass took place. The resulting mass was extruded and cut in a ram extruder by a suitable tool. The resulting molded articles - in this case rings of 1 mm in length, 4 mm in outer diameter and 2.5 mm in bore - were dried for 24 hours at a temperature of 85 ° C. and a relative humidity of 70% and then for calcined at 900 ° C for a period of 2 hours. The rings had a surface area (BET surface area) of 212 m 2 / g and a pore volume of 0.99 ml / g. Bulk density was 202 grams per liter.
500 Gramm des Trägermaterials wurden mit 375 Millilitern einer wäss- rigen Lösung imprägniert, die 27,60 Gramm einer 41,8 %igen (Gew.-%) Lösung von Tetrachlorogoldsäure und 42,20 Gramm einer 20,8 %igen (Gew.-%) Lösung von Tetrachloropalladiumsäure enthielt. Nach einer Dauer von 2 Stunden wurde in einem nächsten Schritt der Katalysator bei einer Temperatur von 80°C für eine Dauer von 5 Stunden im Vakuum getrocknet. Anschließend wurden 236 Milliliter einer 1 molaren Natri- umcarbonatlösung zusammen mit 139 Millilitern destilliertem Wasser aufgebracht. Nach einer Dauer von 2 Stunden wurde der Katalysator bei einer Temperatur von 80°C für eine Dauer von 5 Stunden im Vakuum getrocknet. Anschließend wurde der Katalysator mit einer wässrigen Ammoniaklösung mit einem Anteil von 0,25 Gew.-% Ammoniak für eine Dauer von 45 Stunden gewaschen. Der Katalysator wurde bei einer Temperatur von 200 °C für eine Dauer von 5 Stunden mit Formiergas (95 % N2 / 5 % H2) reduziert. Anschließend wurde der Katalysator mit einer Essigsäure-haltigen Kaiiumacetat-Lösung imprägniert (71,65 Gramm Kaliumacetat in 375 Millilitern Essigsäure) und abschließend bei einer Temperatur von 80°C für eine Dauer von 5 Stunden im Vakuum getrocknet. Der fertige Katalysator hatte eine Konzentration von 2,0 Gew.-% Palladium (7,4 g/1) , 2,0 Gew.-% Gold (7,4 g/l)und 6,5 Gew.-% Kalium (24,1 g/1) . Beispiel 2: 500 grams of the carrier material was impregnated with 375 milliliters of an aqueous solution containing 27.60 grams of a 41.8% (wt%) solution of tetrachloroauric acid and 42.20 grams of a 20.8% (w / w) weight of the solution. %) Solution of tetrachloropalladic acid. After a period of 2 hours, in a next step, the catalyst was dried in vacuo at a temperature of 80 ° C for a period of 5 hours. Subsequently, 236 milliliters of a 1 molar sodium carbonate solution was applied along with 139 milliliters of distilled water. After a period of 2 hours, the catalyst was dried at a temperature of 80 ° C for a period of 5 hours in vacuo. Subsequently, the catalyst was treated with an aqueous ammonia solution containing 0.25% by weight of ammonia for a period washed for 45 hours. The catalyst was reduced at a temperature of 200 ° C for 5 hours with forming gas (95% N 2 /5% H 2 ). Subsequently, the catalyst was impregnated with acetic acid-containing Kaiiumacetat solution (71.65 grams of potassium acetate in 375 milliliters of acetic acid) and finally dried at a temperature of 80 ° C for a period of 5 hours in vacuo. The final catalyst had a concentration of 2.0 wt% palladium (7.4 g / l), 2.0 wt% gold (7.4 g / l) and 6.5 wt% potassium ( 24.1 g / l). Example 2:
Es wurde analog Vergleichsbeispiel 1 vorgegangen mit dem Unterschied, dass zusammen mit 4 Kilogramm pyrogener Kieselsäure (WACKER HDK® T40) noch 128 g Wolframoxid W203( 173 g Titanoxid Ti02, 139 g Zirkoniumoxid Zr02, 197 g Aluminiumoxid A1203 und 0,39 g Boroxid B203 in 35 Kilogramm entionisiertem Wasser eingerührt wurden. The procedure was analogous to Comparative Example 1 with the difference that together with 4 kilograms of fumed silica (WACKER HDK ® T40) still 128 g of tungsten oxide W 2 0 3 ( 173 g titanium oxide Ti0 2 , 139 g zirconium oxide Zr0 2 , 197 g alumina A1 2 0 3 and 0.39 g boron oxide B 2 0 3 were stirred into 35 kilograms of deionized water.
Die Imprägnierung der Katalysator-Formkörper mit Palladium, Gold und Kalium erfolgte ebenfalls analog zu Vergleichsbeispiel 1. Der fertige Katalysator hatte ebenfalls eine Konzentration von 2,0 Gew.-% Palladium, 2,0 Gew.-% Gold und 6,5 Gew.-% Kalium, und zusätzlich noch 2,5 Gew.-% Wolfram, 2,5 Gew.-% Titan, 2,5 Gew.-% Zirkonium, 2,5 Gew.-% Aluminium, 0,003 Gew.-% Bor. Aktivität und Selektivität der Katalysatoren aus dem Vergleichsbeispiel 1 und dem Beispiel 2 wurden über die Dauer von 200 Stunden gemessen. Die Katalysatoren wurden in einem Öl temperierten Strömungsreaktor (Reaktorlänge 1200 mm, Innendurchmesser 19 mm) bei einem absoluten Druck von 9,5 bar und einer Raumgeschwindigkeit (GHSV) von 3500 Nm3/(m3*h) mit folgender Gaszusammensetzung geprüft: 60 Vol.-% Ethen, 19,5 Vol.-% Kohlendioxid, 13 Vol.-% Essigsäure und 7,5 Vol.-% Sauerstoff. Die Katalysatoren wurden im Temperaturbereich von 130°C bis 180°C, gemessen im Katalysatorbett, untersucht. Die Reaktionsprodukte wurden im Ausgang des Reaktors mittels onlineThe impregnation of the catalyst moldings with palladium, gold and potassium was likewise carried out analogously to Comparative Example 1. The finished catalyst likewise had a concentration of 2.0% by weight of palladium, 2.0% by weight of gold and 6.5% by weight. -% potassium, and additionally 2.5 wt .-% tungsten, 2.5 wt .-% titanium, 2.5 wt .-% zirconium, 2.5 wt .-% aluminum, 0.003 wt .-% boron. Activity and selectivity of the catalysts of Comparative Example 1 and Example 2 were measured over a period of 200 hours. The catalysts were tested in an oil tempered flow reactor (reactor length 1200 mm, inner diameter 19 mm) at an absolute pressure of 9.5 bar and a space velocity (GHSV) of 3500 Nm3 / (m3 * h) with the following gas composition: 60 vol. % Ethene, 19.5% by volume of carbon dioxide, 13% by volume of acetic acid and 7.5% by volume of oxygen. The catalysts were investigated in the temperature range from 130 ° C to 180 ° C, measured in the catalyst bed. The reaction products were in the outlet of the reactor by means of online
Gaschromatographie analysiert. Als Maß für die Katalysatoraktivität wurde die Raum- Zeit-Ausbeute des Katalysators in Gramm Vinylacetatmo- nomer pro Stunde und Liter Katalysator (g (VAM) /lKat*h) bestimmt. Kon lendioxid, das insbesondere durch die Verbrennung von Ethen gebildet wird, wurde ebenfalls bestimmt und zur Beurteilung der Katalysatorse lektivität herangezogen. Gas chromatography analyzed. As a measure of the catalyst activity, the space-time yield of the catalyst in grams of vinyl acetate moiety nomer per hour and liter of catalyst (g (VAM) / lKat * h). Con lendioxid, which is formed in particular by the combustion of ethene, was also determined and used to assess the catalyst selectivity.
Tabelle 1 Table 1
Figure imgf000009_0001
Figure imgf000009_0001
* = 2,5 Gew.-% Wolfram, 2,5 Gew.-% Titan, 2,5 Gew.-% Zirkonium, 2,5 Gew.-% Aluminium, 0,003 Gew.-% Bor  * = 2.5 wt% tungsten, 2.5 wt% titanium, 2.5 wt% zirconium, 2.5 wt% aluminum, 0.003 wt% boron

Claims

Patentansprüche : Claims:
1. Katalysator-Formkörper aus Metalloxiden, welche mit Palladium und Gold sowie einer AlkaliVerbindung und Dotierstoffen ausgerüstet sind, dadurch gekennzeichnet, dass die Katalysator- Formkörper mit mindestens zwei Dotierstoffen aus der Gruppe bestehend aus den Oxiden von Wolfram, Titan, Zirkonium, Aluminium, Bor, Eisen und Niob ausgerüstet sind. 1. Catalyst shaped body of metal oxides, which are equipped with palladium and gold and an alkali compound and dopants, characterized in that the catalyst molded body with at least two dopants from the group consisting of the oxides of tungsten, titanium, zirconium, aluminum, boron , Iron and niobium are equipped.
2. Katalysator-Formkörper aus Metalloxiden nach Anspruch 1, dadurch gekennzeichnet, dass mit einem Dotierstoff-Blend aus Wolfram- oxid, Titanoxid, Zirkoniumoxid, Aluminiumoxid und Boroxid dotiert wird. 2. Catalyst shaped body of metal oxides according to claim 1, characterized in that doped with a dopant blend of tungsten oxide, titanium oxide, zirconium oxide, aluminum oxide and boron oxide.
3. Katalysator-Formkörper aus Metalloxiden nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Dotierstoffe jeweils in einer Menge von 0,001 bis 3,0 Gew.-% jeweils bezogen auf das Gesamtgewicht aus Metalloxid und Dotierstoffe eingesetzt werden. 3. Catalyst shaped body of metal oxides according to claim 1 or 2, characterized in that the dopants are used in each case in an amount of 0.001 to 3.0 wt .-% in each case based on the total weight of metal oxide and dopants.
4. Katalysator-Formkörper aus Metalloxiden nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass als Metalloxid Siliziumoxid, Aluminiumoxid, Titanoxid, Zirkoniumoxid, Ceroxid oder Mischungen dieser Metalloxide eingesetzt werden. 4. Catalyst shaped body of metal oxides according to claim 1 to 3, characterized in that are used as the metal oxide silica, alumina, titania, zirconia, ceria or mixtures of these metal oxides.
5. Katalysator-Formkörper aus Metalloxiden nach Anspruch 1 bis 4, dadurch gekennzeichnet, dass der Palladium-Gehalt 0,2 bis 3,5 Gew. -% beträgt . 5. Catalyst shaped body of metal oxides according to claim 1 to 4, characterized in that the palladium content is 0.2 to 3.5 wt -.%.
6. Katalysator-Formkörper aus Metalloxiden nach Anspruch 1 bis 5, dadurch gekennzeichnet, dass der Gold-Gehalt 0,2 bis 3,5 Gew.-%, beträgt . 6. Catalyst shaped body of metal oxides according to claim 1 to 5, characterized in that the gold content is 0.2 to 3.5 wt .-%, is.
7. Katalysator-Formkörper aus Metalloxiden nach Anspruch 1 bis 6, dadurch gekennzeichnet, dass der als AlkaliVerbindung Kalium eingesetzt wird, wobei der Kalium-Gehalt 0,5 bis 15 Gew.-% beträgt . Katalysator-Formkörper aus Metalloxiden nach Anspruch 1 bis 7, dadurch gekennzeichnet, dass diese Ringe mit einer Länge von 1 mm bis 2 mm, einem Außendurchmesser von 3 mm bis 5 mm, einem Innendurchmesser von 2 mm bis 3 mm und einer Wandstärke von 0,5 mm bis 1,5 mm sind . 7. Catalyst shaped body of metal oxides according to claim 1 to 6, characterized in that the alkali compound used is potassium, wherein the potassium content is 0.5 to 15 wt .-%. Catalyst shaped body of metal oxides according to claim 1 to 7, characterized in that these rings with a length of 1 mm to 2 mm, an outer diameter of 3 mm to 5 mm, an inner diameter of 2 mm to 3 mm and a wall thickness of 0, 5 mm to 1.5 mm.
Verwendung der Katalysator-Formkörper aus Metalloxiden nach Anspruch 1 bis 8 bei der Herstellung von Vinylacetat mittels Gas- phasenoxidation von Essigsäure und Ethylen. Use of the metal oxide shaped catalyst bodies according to claims 1 to 8 in the production of vinyl acetate by gas phase oxidation of acetic acid and ethylene.
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WO2019072655A1 (en) 2017-10-13 2019-04-18 Wacker Chemie Ag Catalyst for producing vinyl acetate

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