EP2164630A2

EP2164630A2 - Pd/Au SHELL CATALYST CONTAINING HfO2, METHOD FOR PRODUCING THE SAME AND USE THEREOF

Info

Publication number: EP2164630A2
Application number: EP08773355A
Authority: EP
Inventors: Alfred Hagemeyer; Gerhard Mestl; Peter Scheck
Original assignee: Sued Chemie AG
Current assignee: Sued Chemie IP GmbH and Co KG
Priority date: 2007-05-31
Filing date: 2008-05-30
Publication date: 2010-03-24
Also published as: CN101687175A; US20110166010A1; KR20100027185A; CN101687175B; WO2008145392A3; JP2010527779A; WO2008145392A2; DE102007025443A1; US8466082B2

Abstract

The invention relates to a shell catalyst for producing vinyl acetate monomer. Said shell catalyst comprises an oxidic porous catalyst support having an outer shell that contains metallic Pd and Au, the framework of the porous catalyst support containing hafnium oxide moieties. The shell catalyst according to the invention is suitable for the production of VAM and is characterized by a relatively high activity and VAM selectivity and preserves this activity and selectivity over a relatively long service life. The invention also relates to a method for producing the shell catalyst.

Description

Pd / Au coated catalyst containing HfO ₂ , process for its preparation and its use

The present invention relates to a coated catalyst for the production of vinyl acetate monomer (VAM) comprising an oxidic porous catalyst support of Hafniumoxidein- units containing an outer shell containing metallic Pd and Au, and its preparation.

VAM is an important monomer building block in the production of plastic polymers. The main application areas of VAM are i.a. the preparation of polyvinyl acetate, polyvinyl alcohol and polyvinyl acetal and the co- and terpolymerization with other monomers such as ethylene, vinyl chloride, acrylate, maleate, fumarate and vinyl laurate.

VAM is predominantly produced in the gas phase from acetic acid and ethylene by reaction with oxygen, wherein the catalysts used for this synthesis preferably contain Pd and Au as the catalytically active metals and an alkali metal component as a promoter, preferably potassium in the form of its acetate. The catalytically active metals Pd and Au are presumably not present in the form of metal particles of the respective pure metal, but rather in the form of Pd / Au alloy particles of possibly different composition, although non-alloyed particles can not be excluded.

At present, VAM is predominantly produced by means of so-called shell catalysts in which the catalytically active Metals of the catalyst formed as a Formkorper Katrzationstrager not completely in the entire mold body are present, but rather only in a more or less wide outer region, the so-called shell of the catalyst transformer Formkorpers are contained (see, for this purpose EP 565 952 Al , EP 634 214 Al, EP 634 209 Al and EP 634 208 Al). The further inner areas of the carrier are virtually free of the catalytically active metals. With the help of coated catalysts, a more selective reaction is possible in many cases than with catalysts in which the carriers impregnated into the carrier core with the catalytically active components ("durchimpragniert") are.

The shell catalysts known from the prior art for the preparation of VAM have, for example, catalyst supports based on silica, alumina, aluminosilicates, titanium oxide or zirconium oxide (cf., for this, EP 839 793 A1, WO 98/018553 A1, WO 2000 / 058008 Al and WO 2005/061107 Al). However, catalyst supports based on titanium oxide or zirconium oxide are currently scarcely used, since these catalyst carriers are not long-term stable or relatively expensive with respect to acetic acid.

The predominant fraction of catalysts currently used for the preparation of VAM are coated catalysts with a Pd / Au shell on an oxide porous catalyst support designed as a shaped body, for example a porous, amorphous aluminosilicate support in the form of a sphere based on natural, acid-treated, calcined bentonitrile. The catalyst support is usually impregnated with potassium acetate as a so-called promoter.

Such VAM shell catalysts are usually prepared by a wet-chemical process, in which the catalyst carrier with corresponding solutions of metal precursor compounds, for example by immersing the carrier in the solutions or by means of the incipient wetness method (pore filling method), in which the carrier is loaded with a solution volume corresponding to its pore volume by impregnation.

The Pd / Au shell of the catalyst can be produced, for example, by first treating the catalyst support in a first step with a solution of a Pd salt, e.g. B. a Na ₂ PdCl ₄ - solution, soaked and then in a second step, the Pd component is fixed by applying a NaOH solution to the catalyst support in the form of their Pd hydroxide compound. In a subsequent, separate third step, the catalyst support with a solution of a gold salt, eg. As a NaAuCl ₄ solution, and then the Au component are also fixed by means of NaOH. After fixing the noble metal components in an outer shell of the catalyst support, the loaded catalyst support is then washed substantially free of chloride and Na ions, subsequently dried and finally reduced at 150 ^° C. with ethylene. The generated Pd / Au shell usually has a thickness of about 100 to 500 microns.

After the fixation and / or reduction step, the catalyst support loaded with the noble metals is usually used with

Loaded with potassium acetate (the promoter), the loading with

Potassium acetate is not only in the outer shell loaded with precious metals, but rather the catalyst support is completely thoroughly impregnated with the promoter. The catalyst carrier used can be, for example, a spherical carrier with the name "KA-160" from Süd-Chemie AG on the basis of naturally occurring acid-treated calcined benzene. tonites are used, which has a BET surface area of about 160 m ² / g.

The selectivities in the preparation of VAM using the known from the prior art Pd / Au shell catalysts are about 90 mol .-% based on the ethylene used, the remaining 10 mol .-% of the reaction products consisting essentially of CO ₂ exist, which is formed by total oxidation of the organic starting materials / products.

To increase the activity of such coated catalysts, various possibilities have been proposed, in particular the doping of the catalyst support or of the shell with further promoter metals.

Thus, US Pat. No. 6,849,243 B1 describes, in addition to the use of TiO ₂ as constituent of the catalyst support, the use of barium and cadmium as additional promoter metal components. In particular, neodymium, titanium, magnesium, zirconium, yttrium, praseodymium, lanthanides and rubidium and their binary combinations are disclosed as additional promoters in the shell of the shell catalyst in US 2006/0135809 A1.

Furthermore, it is known from US Pat. No. 6,605,739 to use MoVNbX catalysts for the production of VAM, wherein X is selected from phosphorus, boron, hafnium, tellurium, arsenic or mixtures thereof.

Likewise, EP 1 102 635 Bl teaches the use of one or more hafnium compounds which are arranged on the support, in particular in the shell of the shell catalyst, so that the catalytically active component of the formula Pd / Au / HfO ₂ obeys. In particular, the concepts of the three aforementioned publications, hafnium in addition to palladium and gold in the shell of the coated catalyst, proved to be unsuccessful, in particular due to the insufficient solubility of hafnium compounds.

Furthermore, it was found that these catalysts have an increased activity with respect to the VAM reaction compared to the previously known catalysts with a pure Pd / Au shell, however, their activity is increased only over a relatively short period of time and rapidly decreases again after a maximum.

The object of the present invention was therefore to provide a novel coated catalyst, in particular for the production of VAM, which is characterized by a high activity and VAM selectivity and continues to retain the increased activity and selectivity over a long period of time.

This object is achieved by the provision of a shell catalyst, in particular for the production of vinyl acetate monomer (VAM) comprising an oxidic porous catalyst support having an outer shell, the outer shell containing metallic Pd and Au and wherein the framework structure of the porous catalyst support hafnium oxide units (HfO _2).

The term "hafnium oxide units (HfO ₂ )" is understood here to mean either discrete hafnium oxide in particle form, which firmly adheres, for example by sintering, to the framework structure of the catalyst support and thus forms an integral part of the framework structure of the support For example, silica, alumina or ZrO ₂ units of the corresponding support materials by HfO ₂ - units in the backbone, for example in the form of HfO ₄ tetrahedra in place of the SiO ₄ - can contact ₄ tetrahedra or ZrO, and thus have a chemical bond to the backbone structure -, AlO ₄ and thus also an integral part of the framework structure. In short, it is important in the invention that HfO _2, in one form or another, is an integral part of the framework structure.

The replacement of the scaffolding constituents can be achieved by the person skilled in the art by methods known per se, for example even in the direct synthesis of such support materials or by solid-state ion exchange or liquid ion exchange, for example in aluminosilicates.

By integrating the hafnium oxide units in the framework structure of the carrier or in the carrier, instead of the prior art as on the carrier, the disadvantages of the previously known hafnium oxide additions are avoided. As a result, the catalyst according to the invention is distinguished by a higher activity and higher VAM selectivity than the hafnium oxide-containing VAM catalysts known from the prior art. This activity and selectivity he keeps over long periods of time.

The activity and selectivity were related to the conditions of the conventional VAM preparation: Typically, the reaction to produce VAM is performed in plants at 45% oxygen conversion and then the space-time yield of VAM (kg VAM per liter of catalyst per hour) is determined ,

A hafnium doping according to the invention leads to an increase of the RZA by> 5%, preferably even> 10%. Through a targeted adaptation of the surface and porosity of the wearer (Lower surface and larger pores), the activity advantage can be further transformed into a selectivity improvement of the catalyst of the invention of> 1%. As a rule, the higher the Hf0 ₂ doping the lower the carrier surface has to be. Typical values are 20-40 m ² / g (BET) for pure HfO ₂ , and about 60-120 m ² / g (BET) for calcined acid-treated phyllosilicates with an HfO ₂ content (scaffold doping) of 0.01 to 50 % By weight, preferably from 0.01 to 25% by weight.

According to the invention, the oxidic porous catalyst support either per se already formed as a homogeneous molded body, or is on a porous or non-porous shaped body of z. As steatite, bentonite, alumina, etc. or other suitable material such as ZrO ₂ or mixtures of these ma- materials applied.

Hereinafter, the terms "catalyst" and "shell catalyst" are used interchangeably.

The hafnium oxide units are preferably evenly distributed in the framework structure of the catalyst support, but also an uneven distribution in the framework structure is provided according to the invention.

The term "uniformly distributed" used above is understood to mean that the hafnium oxide units in a corresponding form are either homogeneously distributed as individual or groups of hafnium oxide units in the framework of the porous catalyst support or that the hafnium oxide is present in the framework of the catalyst support is present in the form of hafnium oxide particles which are uniformly distributed in the framework structure of the catalyst support, in other words, the framework structure of the catalyst support. gers of a solid structure of zusammengesinterten together particles of porous oxidic catalyst support and hafnium oxide is formed. In the case of HfO ₂ - scaffold-doped ZrO ₂ often arise HfO ₂ -ZrO ₂ mixed oxides, which are preferred according to the invention.

Accordingly, the term "uniformly distributed" used according to the invention excludes those catalyst supports of which only the inner or the inner and outer surface of the porous catalyst support is coated or coated with the doping oxide or the HfO ₂ is enriched only in an outer shell Such catalyst supports are obtained, for example, by impregnating the surface of a porous oxidic catalyst carrier shaped body with a solution of a corresponding compound and then converting the compound into the corresponding oxide.

The hafnium oxide unit-containing catalyst carrier (in other words, the hafnium oxide-doped catalyst carrier) can be obtained, for example, by the following method comprising the steps of

a) mixing a powdery oxidic porous carrier material with a powdered hafnium compound and / or a solution or slurry of a hafnium salt;

b) shaping a shaped body from the mixture obtained according to step a);

c) calcination of the molded article obtained in step b). Preferably during calcination, the hafnium compound, if it is not already hafnium oxide, is converted into the oxide. Suitable hafnium compounds include, but are not limited to (NH ₄ J ₂ [HfF _6], HfCl _4, HfO _2, HfI _3, HfCl _3, HfCl _2, HfOCl _2, HfO (NOA) _2, HfO (OAc) _2, HfB ₅ , K ₅ [Hf (CN) ₅ ], [Hf (bipy) ₃ ], Hf (SO ₄ J ₂ , Na ₂ HfO ₃ , Na ₄ HfO ₄ .

According to a preferred embodiment of the coated catalyst according to the invention, it is provided that the porous oxidic catalyst support is a silicon oxide, aluminum oxide, aluminosilicate (eg zeolites), zirconium oxide, titanium oxide, a calcined acid-treated bentonite, more generally sheet silicates or a mixture of two or more comprising or being composed of the aforementioned oxides. Particular preference is given to pure zirconium dioxide and calcined bentonite / sheet silicates which contain up to 20% by weight of ZrO ₂ .

It is very particularly preferred if the hafnium oxide units in the framework structure of the catalyst support are contained in a proportion of 0.03 to 20 wt .-%, based on the weight of the pure catalyst support. If the hafnium oxide units are present in a proportion of less than 0.03% by weight in the framework structure of the catalyst support, the properties of the hafnium oxide which increase the activity of the shell catalyst according to the invention have only a slight effect, while above a fraction of 25% by weight. the increase in the activity of the catalyst is accompanied by a significant decrease in VAM selectivity.

It has been found that the smaller the surface area of the catalyst support, the higher the VAM selectivity of the coated catalyst according to the invention. In addition, the thickness of the Pd / Au shell can be chosen to be larger, depending smaller the surface of the catalyst support is, without significant losses of VAM selectivity.

According to a preferred embodiment of the catalyst according to the invention, the specific surface area of the catalyst support has a value of less than or equal to 160 m ² / g, preferably one of less than 140 m ² / g, preferably less than 135 TVi ² Zq preferably less than 120 m ² / g, more preferably less than 100 m ² / g, even more preferably less than 80 m ² / g and most preferably less than 65 m ² / g.

In the context of the present invention, the term "specific surface area" of the catalyst support is understood to mean the BET surface area of the support which is determined by adsorption of nitrogen in accordance with DIN 66132.

According to a particularly advantageous development of the coated catalyst of the invention, it may be provided that the catalyst support has a specific surface area in the range of 160 to 40 m ² / g, preferably one of between 140 and 50 m ² / g, preferably one of between 135 and 50 m ² / g, more preferably one of between 120 and 50 m ² / g, most preferably one of between 100 and 50 m ² / g.

The term "catalyst support" according to the invention refers either to a molding of the aforementioned materials or their mixtures, or a layer, the z. B. in the form of a washcoat, ie an aqueous slurry of the aforementioned materials or mixtures thereof, was applied to a porous or non-porous shaped body and thus also forms a "shell". Functionally according to the invention, "catalyst support" thus means the part of the shell catalyst according to the invention which absorbs the metallic damage. Ie carrying the Pd / Au catalyst. From the context, it results in the present casually, if moldings are meant consisting of the porous catalyst support material. Otherwise, the term "catalyst support" refers both to a shell containing or consisting of the catalyst carrier material and to a shaped body of the materials.

The porous catalyst support molding of the catalyst according to the invention can be prepared, for example, based on an iron oxide-doped, calcined acid-treated bentonite by a powdered (uncalcined) acid-treated bentonite with a powdered iron compound and / or an iron solution and ground water and then intimately to is mixed to homogeneity. Likewise, there are naturally occurring bentonites which already contain iron as an impurity from which more or less iron can be washed out with acid to produce an iron-doped carrier without having to add additional iron. The resulting mixture is compacted into a shaped article by means known to those skilled in the art per se devices such as extruders or tablet presses and then the uncured molded body is calcined to form a stable shaped body. The calcination is preferably carried out at temperatures at which a solid structure results and optionally the iron compound is converted into iron (III) oxide. The size of the specific surface of the doped catalyst support depends in particular on the quality of the (bent) bentonite used, the acid treatment process of the bentonite used, ie, for example, the nature and relative to bentonite and the concentration of the inorganic acid used, the acid treatment time and the temperature, from the compression pressure as well as the calcination time and temperature as well as the calcination atmosphere.

Acid-treated bentonites can be obtained by treatment of bentonites with strong (Brønsted) acids, such as, for example, sulfuric acid, phosphoric acid or hydrochloric acid. The definition of the term "bentonite" used in the context of the present invention is given in: Römpp, Lexikon Chemie, 10th Edition, Georg Thieme Verlag Bentonites which are particularly preferred for the purposes of the present invention are natural aluminum-containing sheet silicates which contain montmorillonite (US Pat. In the form of smectite, the bentonite is usually washed with water, dried and ground to a powder.

The shell catalyst according to the invention is usually prepared by subjecting a large number of shaped bodies to a batch process in whose individual process steps the shaped bodies are mediated, for example, by stirring and mixing tools, subject to relatively high mechanical loads. In addition, the catalyst according to the invention can be mechanically stressed during the filling of a reactor, which can lead to an undesirable development of dust and damage to the catalyst support, in particular its located in an outer region, catalytically active shell.

In particular, in order to keep the abrasion of the catalyst according to the invention within reasonable limits, the catalyst support therefore preferably has a hardness greater than or equal to 20 N, preferably greater than or equal to 25 N, most preferably greater than or equal to 35 N and most preferably one of greater than or equal to 40 N. The determination of the hardness in the present case by means of a tablet hardness tester 8M Fa. Schleuniger Pharmatron AG determined as an average of 99 pieces coated catalysts after drying the catalyst at 130 ⁰ C for 2 h, where the machine settings are as follows:

Hardness: N

Distance to the molded body: 5.00 mm

Time delay: 0.80 s

Feed type: 6 D

Speed: 0.60 mm / s

The hardness of the catalyst support can also be influenced, for example, by the variation of the process parameters during its production, for example by selecting the support material and the type of hafnium starting material and its amount, the calcination time and / or the calcination temperature of an uncured molded part formed from a corresponding support mixture. or by certain optional additives, such as methyl cellulose or magnesium stearate.

The catalyst according to the invention therefore comprises a shaped body as the actual catalyst support, preferably based on a correspondingly doped, calcined acid-treated bentonite or a mixed oxide based on zirconium dioxide or mixtures thereof.

The term "on the basis" means that the catalyst according to the invention in this case comprises a doped calcined acid-treated bentonite It is preferred that the proportion of calcined acid-treated bentonite is greater than or equal to 50% by weight, preferably greater than or equal to 60% by weight, preferably greater than or equal to 70% by weight, more preferably greater than or equal to 80% by weight, based on the weight of the catalyst support containing hafnium dioxide units.

It was found that the VAM selectivity of the catalyst according to the invention was increased as the integral pore volume of the catalyst support increases. According to a further preferred embodiment of the catalyst according to the invention, therefore, the catalyst support has an integral BJH pore volume of greater than 0.25 ml / g, preferably greater than 0.30 ml / g, and most preferably greater than 0.35 ml / g. In the case of pure ZrO ₂ , for comparison, the pore volume is in the range of 0.2-0.4 ml / g.

The integral pore volume of the catalyst support is determined by the method of BJH by means of nitrogen adsorption. The surface of the catalyst support and its integral pore volume are determined by the BET or by the BJH method. The BET surface area is determined by the BET method according to DIN 66131; a publication of the BET method can also be found in J. Am. Chem. Soc. 60, 309 (1938). To determine the surface area and the integral pore volume of the catalyst support or of the catalyst, the sample can be measured, for example, with a fully automatic nitrogen porosimeter from the company Mikromeritics, type ASAP 2010, by means of which an adsorption and a desorption isotherm are recorded.

To determine the surface area and the porosity of the catalyst carrier or of the catalyst by the BET method, the data are evaluated in accordance with DIN 66131. The pore volume is determined from the measurement data using the BJH method (EP Barret, LG Joiner, PP Haienda, J. Am. Chem. Soc. 73 (1951, 373)). This procedure also takes into account effects of capillary condensation. Pore volumes of certain pore size ranges are determined by summing up incremental pore volumes, which are obtained from the evaluation of the adsorption isotherm according to BJH. The integral pore volume according to the BJH method refers to pores with a diameter of 1.7 to 300 nm.

According to a further preferred embodiment of the coated catalyst according to the invention, it is also advantageous if the water absorbency of the catalyst support is 40 to 75%, preferably 50 to 70% calculated as weight increase by water absorption. The absorbency is determined by soaking 10 g of the carrier sample with deionized water for 30 minutes until gas bubbles no longer escape from the carrier sample. Then, the excess water is decanted and the soaked sample is blotted with a cotton cloth to free the sample from adhering moisture. Then the water-loaded carrier is weighed and the absorbency calculated according to:

(Weight (g) - weight (g)) x 10 = water absorbency (%)

It is advantageous if the catalyst support has an integral pore volume according to BJH in the range of 0.25 and 0.7 ml / g, preferably in a range of 0.3 and 0.55 ml / g and very particularly preferably in the range from 0.35 to 0.5 ml / g.

According to a further preferred embodiment of the catalyst according to the invention, it is preferred that at least 80% of the integral pore volume of the catalyst carrier according to BJH are formed by mesopores and macropores, preferably at least 85% and preferably at least 90%. Thereby, decreased activity caused by diffusion limitation counteracted the catalyst of the invention, in particular for Pd / Au shells with relatively large thicknesses. In this context, the terms micropores, mesopores and macropores are understood to mean pores having a diameter of less than 1 nm, a diameter of 1 to 50 nm and a diameter of greater than 50 nm.

Also in view of a low pore diffusion limitation, it is preferred according to a further embodiment of the catalyst according to the invention that the catalyst carrier has an average pore diameter of 8 to 50 nm, preferably one of 9 to 20 nm and preferably one of 10 to 15 nm ,

The catalyst according to the invention should preferably have a bulk density of more than 0.4 g / ml, preferably one of more than 0.45 g / ml and more preferably a bulk density of between 0.45 and 0.75 g / ml.

In order to ensure a sufficient chemical resistance of the catalyst according to the invention, has in the case that the

Contains carrier calcined acid-treated bentonite, a

SiO ₂ content of at least 65 mass%, preferably at least 80 mass%, and preferably from 95 to 99.5

Mass .-% based on the mass of the undoped calcined acid-treated bentonite.

In the gas phase synthesis of VAM from acetic acid and ethene, a relatively low Al ₂ θ ₃ content in the calcined acid-treated bentonite has little adverse effect, while at high Al ₂ O ₃ levels must be expected with a significant decrease in the pressure hardness. According to a preferred embodiment of the catalyst according to the invention, the acid-treated bentonite therefore contains less than 10% by mass of Al ₂ O ₃ , preferably 0.1 to 3% by mass and preferably 0.3 to 1.0% by mass, based on the mass of the calcined acid-treated bentonite.

The acidity of the catalyst support advantageously influences the activity of the catalyst according to the invention in the gas-phase synthesis of VAM from acetic acid and ethene. According to a further preferred embodiment of the catalyst according to the invention, the catalyst support has a Bayer acidity of between 1 and 150 μval / g, preferably between 5 and 130 μval / g and more preferably between 10 and 100 μval / g.

As already mentioned, the catalyst support of the catalyst according to the invention is preferably present as a so-called "shaped body." In this case, the catalyst support can basically take the form of any geometric body on which a shell, which contains catalytically active metals described below, can be applied. However, it is preferred if the catalyst support as a ball, cylinder (even with rounded end faces), perforated cylinder (also with rounded faces), trilobus, "capped tablet", tetralobus, ring, donut, star, cartwheel, "inverse" cartwheel , or is formed as a strand, preferably as a rib strand or star strand, is very particularly preferred since it can also be provided with a "shell" simply.

The diameter or the length and thickness of the catalyst support of the catalyst according to the invention is preferably 2 to 9 mm, depending on the geometry of the reactor tube in which the catalyst is to be used. If the catalyst support is designed as a sphere, the catalyst support preferably has a diameter of greater than 2 mm, preferably a diameter. greater than 3 mm and preferably 4 mm to 9 mm in diameter.

In general, the smaller the thickness of the Pd / Au shell of the catalyst, the higher the VAM selectivity of the catalyst according to the invention. According to a further preferred embodiment of the catalyst according to the invention, therefore, the shell of the catalyst has a thickness of less than 300 microns, preferably one of less than 200 microns, preferably one of less than 150 microns, more preferably one of less than 100 microns and even more preferably one of less than 80 microns.

The thickness of the shell can be optically measured by means of a microscope. Namely, the area where the noble metals Pd / Au are deposited appears black, while the non-precious areas appear white. The borderline between precious metal-containing and -free areas is usually very sharp and visually clearly visible. If the abovementioned boundary line is not sharp and can not be visually clearly identified, the thickness of the shell corresponds to the thickness of a shell, measured from the outer surface of the catalyst support, in which 95% of the noble metal deposited on the support is contained.

However, it has also been found that in the catalyst according to the invention, in particular the surface arms, the Pd / Au shell can be formed with a relatively high thickness causing a high activity of the catalyst without a significant reduction in the VAM selectivity of the catalyst according to the invention to effect. According to another, likewise preferred embodiment of the catalyst according to the invention, the shell of the catalyst therefore has a thickness in the range of 200 and 2000 μm to, preferably in the range of 250 and 1800 microns, most preferably in the range of 300 and 1500 microns and more preferably in the range of between 400 and 1200 microns.

In order to ensure a sufficient activity of the catalyst according to the invention, the proportion of the catalyst in Pd is 0.5 to 2.5% by weight, preferably 0.6 to 2.3% by weight and preferably 0.7 to 2 Wt .-% based on the weight of the loaded with noble metal catalyst support.

Furthermore, it may be preferred for the catalyst according to the invention to have a Pd content of from 1 to 20 g / l, preferably from 2 to 15 g / l and preferably from 3 to 10 g / l.

Also, to ensure sufficient activity and selectivity of the catalyst of the invention, the Au / Pd atomic ratio of the catalyst is preferably between 0 and 1.2, preferably between 0.1 and 1, preferably between 0.3 and 0.9, and more preferably between 0.4 and 0.8.

Moreover, it may be preferable if the Au content of the catalyst of the present invention is from 1 to 20 g / L, preferably from 1.5 to 15 g / L, and preferably from 2 to 10 g / L.

In order to ensure a largely uniform activity of the catalyst according to the invention across the thickness of the Pd / Au shell, the noble metal concentration should vary only relatively little over the shell thickness. That is, the profile of the noble metal concentration of the catalyst over a range of 90% of the shell thickness, with the outer and inner shell boundary regions each being spaced 5% of the shell thickness, decreases by a maximum of +/- 20% from the mean noble metal concentration of that region , in front- preferably by a maximum of +/- 15% and preferably by a maximum of +/- 10

In further preferred embodiments, hafnium oxide units are additionally present in the shell of the catalyst according to the invention, preferably in an amount of from 0.1 to 20% by weight, based on the weight of the total catalyst.

Further, the shell may also contain zirconia, the content of zirconia being in the range of 10 to 20% by weight, based on the weight of the total catalyst.

Chloride poisoned the catalyst of the invention and leads to a deactivation of the same. According to a further preferred embodiment of the catalyst according to the invention, therefore, its content of chloride is less than 250 ppm, preferably less than 150 ppm.

In addition to the hafnium oxide, the catalyst according to the invention preferably contains at least one alkali metal compound as further promoter, preferably a potassium, a sodium, a cesium or a rubidium compound, preferably a potassium compound. Suitable and particularly preferred potassium compounds include potassium acetate KOAc, potassium carbonate K ₂ CO ₃ , potassium hydrogen carbonate KHCO ₃ and potassium hydroxide KOH, as well as all potassium compounds which convert to potassium acetate (KOAc) under the particular reaction conditions of VAM synthesis. The potassium compound can be applied both before and after the reduction of the metal components to the metals Pd and Au on the catalyst support. According to a further preferred embodiment of the catalyst according to the invention, the catalyst comprises an alkali metal acetate, preferably potassium acetate. To ensure a sufficient promoter activity, it is particularly preferable that the content of the catalyst of alkali metal acetate is 0.1 to 0.7 mol / 1, preferably 0.3 to 0.5 mol / 1.

According to a further preferred embodiment of the catalyst according to the invention, the alkali metal / Pd atomic ratio is between 1 and 12, preferably between 2 and 10 and more preferably between 4 and 9. In this case, the smaller the surface area of the alkali metal / Pd atomic ratio Catalyst carrier is.

The present invention further relates to a process for the preparation of a coated catalyst according to the invention, comprising the steps of

a) Preparing an oxide porous catalyst support whose framework structure contains hafnium oxide (HfO ₂ ) units.

b) applying a solution of a Pd precursor compound to the catalyst support;

c) applying a solution of an Au precursor compound to the catalyst support whose framework structure contains hafnium oxide units (HfO ₂ );

d) converting the Pd component of the Pd precursor compound into the metallic form;

e) converting the Au component of the Au precursor compound into the metallic form.

In principle, any Pd or Au compound can be used as Pd and Au precursor compounds, by means of which a high The degree of dispersion of the metals can be achieved. In this case, the term "degree of dispersion" is understood to mean the ratio of the number of all surface metal atoms of all metal / alloy particles of a supported metal catalyst to the total number of all metal atoms of the metal / alloy particles In general, it is preferred if the degree of dispersion corresponds to a relatively high numerical value since in this case as many metal atoms as possible are freely accessible for a catalytic reaction.

That is, with a relatively high degree of dispersion of a supported metal catalyst, a certain catalytic activity thereof can be achieved with a relatively small amount of metal used. According to a further preferred embodiment of the catalyst according to the invention, the degree of dispersion of the metal particles is 1 to 20%. The values of the degree of dispersion are determined by CO adsorption.

It is preferred that the Pd and Au precursor compounds are selected from the halides, in particular chlorides, oxides, nitrates, nitrites, formates, propionates, oxalates, acetates, hydroxides, bicarbonates, amine complexes or organic complexes, for example triphenylphosphine complexes or acetylacetonate complexes , these metals.

Examples of particularly preferred Pd precursor compounds are water-soluble Pd salts. According to particularly preferred embodiments of the process according to the invention, the Pd precursor compounds are selected from the group consisting of Pd (NH ₃ J ₄ (OH) ₂ , Pd (NO ₃ ) ₂ , K ₂ Pd (OAc) ₂ (OH) ₂ , Pd ( NH ₃ MNO ₂ ), Pd (NH ₃ ) ₄ (NO ₃ ) ₂ , K ₂ Pd (NO ₂ ) ₄ , Na ₂ Pd (NO ₂ J ₄ , Pd (OAc) ₂ , PdCl ₂ and Na ₂ PdCl ₄ and H ₂ PdCl ₄ and K ₂ PdCl ₄ and (NH ₄ ) ₂ PdCl ₄ and Pd (NH ₃ ) ₄ Cl ₂ and Pd (NH ₃ ) ₄ (HPO ₄ ) and ammonium Pd oxalate and Pd oxalate and K ₂ Pd (C ₂ O ₄ ) ₂ and Pd (II) trifluoroacetate. In addition to Pd (OAc) ₂ , it is also possible to use other carboxylates of palladium, preferably the salts of the aliphatic monocarboxylic acids having 3 to 5 carbon atoms, for example the propionate or the butyrate salt.

According to a further preferred embodiment of the method according to the invention, Pd nitrite precursor compounds may also be preferred. Preferred Pd nitrite precursor compounds are, for example, those obtained by dissolving Pd (OAc) ₂ in a NaNO ₂ solution.

Examples of preferred Au precursor compounds are water-soluble Au salts. According to a particularly preferred embodiment of the method according to the invention, the Au precursor compound is selected from the group consisting of

KAuO ₂ , HAuCl ₄ , NaAuO ₂ , KAu (NO ₂ ) ₄ , AuCl ₃ , NaAuCl ₄ , KAuCl ₄ ,

(NH4) AuCl _4, KAu (OAc) ₃ (OH), NaAu (OAc) ₃ (OH), HAu _(NO3 J ₄ and

Au (OAc) ₃ . It may be advisable to do this

Au (OAc) ₃ or the KAuO ₂ by precipitation of the oxide / hydroxide from a solution of gold acid, washing and isolation of the precipitate and recording the same in acetic acid or KOH fresh each time.

Suitable solvents for the precursor compounds are all solvents in which the selected precursor compounds are soluble and which, after application to the catalyst support, can easily be removed therefrom by drying. Preferred solvent examples of the metal acetates as precursor compounds are, in particular, unsubstituted carboxylic acids, in particular acetic acid, and, for the metal chlorides, especially water or dilute hydrochloric acid. If the precursor compounds are not sufficiently soluble in acetic acid, water or dilute hydrochloric acid or mixtures thereof, alternatively or in addition to the solvents mentioned, other solvents may also be used. Other solvents which may be considered here are preferably those solvents which are inert and which are miscible with acetic acid or water. Preferred solvents which are suitable as an additive to acetic acid are ketones, for example acetone or acetylacetone, furthermore ethers, for example tetrahydrofuran or dioxane, acetonitrile, dimethylformamide and solvents based on hydrocarbons such as benzene, but also in others Embodiments can be used as the sole solvent.

Preferred solvents which are suitable as additives to water are ketones, for example acetone, or alcohols, for example ethanol or isopropanol or methoxyethanol, lyes, such as aqueous KOH or NaOH, or organic acids, such as acetic acid, formic acid, citric acid, tartaric acid, apples - Acid, glyoxylic acid, glycolic acid, oxalic acid, pyruvic acid or lactic acid, called, but which can also be used in other embodiments as the sole solvent.

If chloride compounds are used as precursor compounds, it must be ensured that the chloride ions are reduced to a tolerable residual amount before use of the catalyst prepared by the process according to the invention, since chloride is a catalyst poison. For this purpose, the catalyst carrier is usually washed extensively with water after fixing the Pd and Au components of the Pd or Au precursor compound on the catalyst support. This is generally done either immediately after fixation by Hydroxide precipitation of the Pd and Au components by means of lye or after the reduction of the noble metal components to the respective metal / alloy.

According to a preferred embodiment of the method according to the invention, however, chloride-free Pd and Au precursor compounds are used and chloride-free solvents in order to keep the content of the catalyst of chloride as low as possible and to avoid a complex chloride-free washing. In this case, the corresponding acetate compounds are preferably used as precursor compounds, since they contaminate the catalyst support only to a very limited extent with chloride.

The deposition of the Pd and Au precursor compounds onto the catalyst support in the region of an outer shell of the catalyst support can be achieved by processes known per se. So the order of the precursor solutions can be made by impregnation by immersing the carrier in the precursor solutions or impregnated according to the Incipient-wetness method. Subsequently, a base, for example sodium hydroxide solution or potassium hydroxide solution, is applied to the catalyst support, whereby the noble metal components in the form of hydroxides are precipitated onto the support. For example, it is also possible first to impregnate the carrier with caustic and then to apply the precursor compounds to the carrier pretreated in this way. The same applies if in addition hafnium oxide is present in the shell, wherein likewise preferably water-soluble hafnium compounds are used.

According to a further preferred embodiment of the method according to the invention, it is therefore provided that the Pd and the Au precursor compound is applied to the catalyst support by the catalyst support with the solution of Pd- Precursor compound and with the solution of the Au precursor compound or with a solution containing both the Pd and the Au precursor compound is soaked.

According to the state of the art, the active metals Pd and Au and, if appropriate, Hf are applied starting from chloride compounds in the region of a shell of the support on the same by means of impregnation. However, this technique has reached its limits in terms of minimum shell thicknesses and maximum Au loading and maximum Hf loading. The shell thickness of the corresponding known VAM catalysts is about 100 μm and it is not foreseeable that still thinner shells can be obtained by means of impregnation. In addition, higher Au loadings within the desired shell by impregnation are difficult to realize because the Au precursor compounds tend to diffuse from the shell to inner zones of the catalyst support body, resulting in wide Au shells that are scarcely in regions mixed with Pd.

The active metals, or rather their precursor compounds, can for example also be applied to the carrier by means of so-called physical methods. For this purpose, according to the invention, the support can preferably be sprayed, for example, with a solution of the precursor compounds, the catalyst support being moved in a coating drum in which warm air is blown in so that the solvent evaporates rapidly.

According to a further preferred embodiment of the process according to the invention, it is provided that the solution of the Pd precursor compound and the solution of the Au precursor compound is applied to the catalyst support by spraying the solutions onto a fluidized bed or a fluidized bed of the catalyst support, preferably way by means of an aerosol of the solutions. As a result, the shell thickness can be adjusted continuously and optimized, for example up to a thickness of 2 mm. But even very thin shells with a thickness of less than 100 microns are possible.

The abovementioned embodiment of the method according to the invention can be carried out by means of a fluidized bed system or fluidized bed system. It is particularly preferred if there is a so-called controlled air sliding layer in the system. On the one hand, the catalyst carrier shaped bodies are thoroughly mixed by the controlled air sliding layer, while they rotate about their own axis, whereby they are dried uniformly by the process air. On the other hand, due to the consequent orbital movement of the shaped bodies caused by the controlled air sliding layer, the catalyst carrier shaped bodies pass the spraying process (application of the precursor compounds) in almost constant frequency.

As a result, a substantially uniform shell thickness of a treated batch of moldings is achieved. Furthermore, it is achieved that the noble metal concentration varies only relatively small over a relatively large range of shell thickness, ie that the noble metal concentration over a large range of shell thickness describes approximately a rectangular function, whereby a substantially uniform activity of the resulting catalyst on the thickness of the Pd / Au shell is ensured. Suitable drageeing drums, fluidized bed systems or fluidized bed systems for carrying out the method according to the invention in accordance with preferred embodiments are known in the art and are described, for example, in US Pat. From the companies Heinrich Brucks GmbH (Alfeld, Germany) ERWEK GmbH (Heusenstamm, Germany), Stechel (Germany), DRIAM Anlagenbau GmbH (Eriskirch, Germany) smooth GmbH (Binzen, Germany), GS Divisione Verniciatura (Osteria, Italy), HOFER-Pharma Maschinen GmbH (Weil am Rhein, Germany), LB Bohle Maschinen + Verfahren GmbH (Enningerloh, Germany), Lödige Maschinenbau GmbH (Paderborn, Germany), Manesty (Merseysid, Great Britain), Vector Corporation (Marion, IA, USA), Aeromatic-Fielder AG (Bubendorf, Switzerland), GEA Process Engineering (Hampshire, UK), Fluid Air Inc. (Aurora, Ill., USA), Heinen Systems GmbH (Varel, Germany), Hüttlin GmbH (Steinen, Germany), Umang Pharmatech Pct. (Marharashtra, India) and Innojet Technologies (Lörrach, Germany).

According to a further preferred embodiment of the method according to the invention, the catalyst support is heated during the application of the solutions, for example by means of heated process air. The degree of heating of the catalyst supports can be used to determine the drying rate of the applied solutions of the noble metal precursor compounds. At relatively low temperatures, for example, the rate of desiccation is relatively slow, so that, given appropriate quantitative coverage, the formation of larger shell thicknesses may occur due to the high diffusion of precursor compounds due to the presence of solvent. For example, at relatively high temperatures, the rate of desiccation is relatively high, so that solution of the precursor compounds coming into contact with the shaped body dries almost instantaneously, so solution applied to the catalyst support can not penetrate deeply into it. At relatively high temperatures so relatively small shell thickness can be obtained with high precious metal loading. Commercially available solutions of the precursor compounds, such as Na ₂ PdCl ₄ , NaAuCl ₄ or HAuCl ₄ solutions, are usually used in the processes described for the preparation of VAM shell catalysts based on Pd and Au. , Pd (NH) ₂ (NO ₂ J ₂ and KAuO ₂ are performed, such as loading already above, and chloride-free Pd or Au precursor compounds such as Pd (NH3) ₄ (OH) ₂ in the recent literature, are used. These precursor compounds react basic in solution while the classical chloride, nitrate and acetate precursors in solution all react acidically.

For the application of the precursor compounds to the catalyst support, preference is usually given to using aqueous Na ₂ PdCl ₄ and NaAuCl ₃ solutions. These metal salt solutions are normally applied to the support at room temperature and then the metal components are fixed with NaOH as insoluble Pd or Au hydroxides. Thereafter, the loaded carrier is usually washed free of chloride with water. In particular, the Au fixation is associated with disadvantages such as long exposure times of the base to induce the precipitation of the stable Au-Tetrachlorokomplexes, incomplete precipitation and associated poor Au retention.

According to a further preferred embodiment of the method according to the invention, the method comprises the steps of

a) a first solution of a Pd and / or an Au precursor compound is provided;

b) a second solution of a Pd and / or an Au precursor compound is provided, wherein the first solution precipitates the noble metal component (s) of the precursor compound. ferverbindung / en the second solution causes and vice versa;

c) the first solution and the second solution is applied to the catalyst support.

This embodiment of the method according to the invention uses two mutually different precursor solutions, one of which, for example, contains one Pd and the other an Au precursor compound.

In this case, preferably one of the solutions has a basic and the other an acidic pH, as a rule. The application of the solutions to the catalyst support is usually carried out by first impregnating the support with the first and then in a subsequent step with the second solution as described above by impregnation. When applying the second solution, the two solutions are then combined on the support, whereby the pH of the solutions changes and the Pd or Au component of the respective precursor compound is precipitated onto the support, without having a as in the state of Technik usual auxiliary base such as NaOH or KOH must be applied to the carrier.

The abovementioned embodiment of the method according to the invention is therefore based on an impregnation of the catalyst support with the first solution of a Pd and / or Au precursor compound and the second solution of a Pd and / or Au precursor compound, the two solutions being incompatible with one another, ie that the first solution causes a precipitation of the noble metal component (s) of the precursor compound (s) of the second solution, and vice versa, so that in the contact zone of both solutions both the preimpregnated Pd / Au component (s) and the postimpregnated Pd - / Au Component / n precipitate almost simultaneously and thus lead to an intimate Pd / Au mixing. Between the two impregnation steps can be optionally dried.

Suitable aqueous solutions of Pd precursor compounds for impregnation with incompatible solutions are listed by way of example in Table 1.

Table 1:

If NH ₃ should be too strongly reducing with respect to premature Au reduction, instead of the palladium amine complexes, the corresponding diamine complexes with ethylenediamine as ligand or the complexes with ethanolamine as ligand can also be used.

Suitable aqueous solutions of Au precursor compounds for impregnation with incompatible solutions are listed by way of example in Table 2. Table 2:

Suitable combinations of incompatible solutions for base-free precipitation of the noble metal components are, for example, a PdCl ₂ and a KAuO ₂ solution; a Pd (NOs) ₂ and a KAuO ₂ solution; a Pd (NH ₃ ) ₄ (OH) ₂ and an AuCl ₃ or HAuCl ₄ solution.

According to a further preferred embodiment of the process according to the invention, Pd can also be precipitated with incompatible Pd solutions and analogously to Au with incompatible Au solutions, for example by contacting a PdCl ₂ solution with a Pd (NH ₃ ) ₄ (OH) ₂ - Solution or a HAuCl ₄ - with a KAuO ₂ solution. In this way, high Pd and / or Au contents can be deposited in the shell without having to use highly concentrated solutions.

According to a further embodiment of the method according to the invention, it is also possible to use mutually compatible mixed solutions which are brought into contact with the noble metal precipitate with a solution which is incompatible with the mixed solution. An example of a mixed solution is a solution containing PdCl ₂ and AuCl ₃ , whose noble metal components have a KAuO ₂ solution can be precipitated, or a solution containing Pd (NH ₃ ) ₄ (OH) ₂ and KAuO ₂ whose noble metal components can be precipitated with a solution containing PdCl ₂ and HAuCl ₄ . Another example of a mixed solution is the pair HAuCl ₄ and KAuO ₂ .

The impregnation with the incompatible solutions is preferably carried out by impregnation or by spray impregnations, the incompatible solutions being sprayed simultaneously, for example, by one or more double nozzles or simultaneously by two nozzles or nozzle groups or sequentially by one or more nozzles.

Impregnation with the incompatible solutions may result in thinner shells due to the rapid immobilization (fixation) of the metallic components of the precursor compounds in the shell, and the concomitant shortened Pd and Au diffusion, than the conventional use of mutually compatible solutions. By means of the incompatible solutions, high precious metal contents in thin shells, improved metal retention, faster and more complete precipitation of the noble metals, the reduction of the interfering Na residual content of the carrier, the simultaneous fixation of Pd and Au in only one fixing step and the omission of the NaOH costs and the NaOH handling and avoidance of a mechanical weakening of the carrier by contact with excess NaOH can be achieved.

By means of impregnation with incompatible solutions, a single fixing step, which involves only the application of two incompatible solutions, allows larger noble metal contents to be deposited on the catalyst support than is possible with classical bases (NaOH) fixation. By acid fixation of chloride-free precious metal precursors, damage is Catalysts with particularly low Cl and Na residual contents available.

In particular, by means of the principle of incompatible solutions, high Au contents can be easily achieved with an Au / Pd atomic ratio of 0, 6 and more, which is highly desirable in terms of increasing VAM selectivity.

According to a further preferred embodiment of the method according to the invention, it is provided that after the Pd and / or the Au precursor compound has been applied to the catalyst support, the catalyst support is subjected to a fixing step for fixing the noble metal component (s) Precursor compound (s) on the catalyst support. The fixation step may, as already stated above, include the treatment of the support with caustic or a calcination of the support for transferring the noble metal component (s) into a hydroxide compound (s) or into an oxide. The fixing step may also be omitted and reduced directly, e.g. in the gas phase.

It is likewise possible to introduce the doped catalyst support as a powder and to impregnate it with the precursor compounds of the active metals. The pretreated powder can then be applied in the form of a washcoat to a suitable shaped body, for example a sphere made of steatite or a KA-160 support, and then further processed by calcination and reduction to give the catalyst.

Accordingly, the invention relates to a second process for preparing a coated catalyst according to the invention, comprising the steps of a) providing a powdery oxidic porous catalyst support containing hafnium oxide (HfO ₂ ) units in its framework structure and wherein the catalyst support is loaded with a Pd and an Au precursor compound or with Pd and Au particles;

b) applying the loaded catalyst support to a shaped body in the form of a shell;

c) calcining the loaded shaped body according to step b);

d) optionally, converting the Pd and the Au component of the Pd or Au precursor compound into the metallic form.

Alternatively, the said method can also be carried out by first applying the powder-shaped catalyst support not loaded with noble metal to a shaped body and only then applying the noble metals.

After loading with the precursor compounds or after the fixation of the noble metal components, the support can be calcined to convert the noble metal components into the corresponding oxides. The calcination is preferably carried out at temperatures of less than 700 ⁰ C. Particularly preferably between 300-450 ⁰ C with access of air. The calcination time depends on the calcination temperature and is preferably chosen in the range of 0.5-6 hours. At a calcination temperature of about 400 ^° C., the calcination time is preferably 1-2 hours. At a calcination temperature of 300 ^° C., the calcination time is preferably up to 6 hours. The noble metal components are typically reduced before the use of the catalyst, wherein the reduction in situ, ie in the process reactor, or ex situ, ie in a special reduction reactor, can be performed. The reduction in situ is preferably carried out with ethylene (5% by volume) in nitrogen at a temperature of about 150 ^° C. over a period of, for example, 5 hours. The reduction can situ ex, for example, 5 vol .-% hydrogen in nitrogen, for example by forming gas, are carried out at temperatures in the range of preferably 150-500 ⁰ C over a period of 5 hours.

Gaseous or vaporizable reducing agents such as CO, NH ₃ , formaldehyde, methanol and hydrocarbons may also be used, which gaseous reducing agents may also be diluted with inert gas such as carbon dioxide, nitrogen or argon. Preferably, an inert gas diluted reducing agent is used. Preference is given to mixtures of hydrogen with nitrogen or argon, preferably with a hydrogen content of between 1% by volume and 15% by volume.

The reduction of the noble metals can also be carried out in the liquid phase, preferably by means of the reducing agents hydrazine, K-formate, H ₂ O ₂ or Na-hypophosphite, K-hypophosphite, hypophosphorous acid.

The amount of reducing agent is preferably chosen so that during the treatment time at least the necessary for the complete reduction of the noble metal components equivalent is passed over the catalyst. Preferably, however, an excess of reducing agent is passed over the catalyst to ensure rapid and complete reduction. Preferably, it is depressurized, ie at an absolute pressure of about 1 bar, reduced. For the production of technical amounts of inventive catalyst, a rotary kiln or fluidized bed reactor is preferably used to ensure a uniform reduction of the catalyst.

The invention furthermore relates to the use of the catalyst according to the invention as oxidation catalyst, as hydrogenation / dehydrogenation catalyst, as catalyst in hydrodesulfurization, as hydrodenitrification catalyst, as hydrodeoxigenation catalyst or as catalyst in the synthesis of alkenylalkanoates, in particular in the synthesis of vinyl acetate monomer, in particular in the gas phase oxidation of ethylene and acetic acid to vinyl acetate monomer.

The catalyst according to the invention is preferably used for the production of VAM. This is generally carried out by passing acetic acid, ethylene and oxygen or oxygen-containing gases at temperatures of 100-200 ⁰ C, preferably 120-200 ° C, and at pressures of 1-25 bar, preferably 1-20 bar, over the catalyst of the invention, wherein unreacted starting materials can be recycled. The oxygen concentration is expediently kept below 10% by volume. Under certain circumstances, however, a dilution with inert gases such as nitrogen or carbon dioxide is advantageous. In particular, carbon dioxide is suitable for dilution since it is formed in small amounts in the course of VAM synthesis. The resulting vinyl acetate is isolated by suitable methods described, for example, in US 5,066,365 A.

The following exemplary embodiments serve to explain the invention without it being to be understood as limiting: Example 1:

500 g of various acid-treated dried pulverulent ger Bentonitgemische as layered silicate component based on natural bentonites with skin component montmorillonite commercial ZrO ₂ and 10 g of HfO2, and 13 g of methyl cellulose were ground to an intimate mixture by a ball mill for up to 100 g.

The resulting mixture was taken up in water and made into a dough by means of a mixer from which spherical shaped bodies were prepared under pressure by means of a tablet press. For curing, the balls were calcined at a temperature of 640 ⁰ C over a period of 4 h. The shaped bodies thus obtained have the characteristics listed in Table 3:

Table 3: Properties of molded articles according to the invention

225 g of the above-prepared spheres with a surface area of 122m2 / g were charged into a commercially available fluid bed apparatus and by means of temperature-controlled at 80 ⁰ C compressed air (6 bar) placed in a fluidized bed state.

After the moldings had been heated to a temperature of about 75 ^° C., 300 ml of an aqueous noble metal mixed solution containing 7.5 g of commercially available Na ₂ PdCl ₄ (sodium tetrachloropalladate) and 4.6 g of commercially available NaAuCl ₄ (sodium tetrachloroaurate) were placed on the fluidized bed of the moldings. sprayed over a period of 40 min.

After impregnation of the catalyst supports with the mixed noble metal solution, the carrier beads were fluidized under the above conditions over a period of 30 minutes with a 0.05 molar NaOH solution. The NaOH was allowed to act on the moldings for 16 hours.

After NaOH exposure, the supports were washed extensively with water in the fluidized bed apparatus to free the support as much as possible from alkali metal and chloride introduced into the support via the noble metal compounds and NaOH.

After washing, the molded bodies were dried in the fluidized bed apparatus at a temperature of 200 to 250 ^° C.

After drying the moldings, they were reduced to a Pd / Au coated catalyst with a gas mixture of ethylene (5% by volume) in nitrogen at a temperature of about 150 ° C in the fluidized bed apparatus.

The resulting coated catalyst contained about 1.2% by weight of Pd and had an Au / Pd atomic ratio of about 0.5, a shell thickness of about 170 μm and a hardness of 37 N. The noble metal concentration of the Pd / Au coated catalyst thus produced deviated over a range of 90% of the shell thickness, with the outer and inner shell boundary areas each spaced 5% of the shell thickness, from the average noble metal concentration of this region by a maximum of +/- 10 % off.

Example 2:

50 g of ZrO ₂ powder having a specific surface area of 39 m ₂ / g was mixed with 8 g of powdery HfO ₂ and ground to a intimate mixture by means of a ball mill. The resulting average particle size was about 2 μm.

The HfO ₂ / ZrO ₂ powder thus obtained has the characteristics listed in Table 4:

Table 4: Properties of the HfO ₂ / ZrO ₂ powder

Geometric shape sphere

D50 2μm

Moisture content <2.0% by weight

Waste weight 620 gl ^'1

Water suction specific. Surface area (BET) 39 m ² / g

HfO ₂ content 11.1%

ZrO ₂ content 88, 8% by weight

Loss on ignition 1000 ⁰ C <1 wt .-%

BJH pore volume N ₂ 0 _f 28 cm ³ g ^"1

The HfO ₂ / ZrO ₂ powder was mixed with 30 g of a 20% zirconate ZrO (OAc) ₂ solution as a binder, stirred for Ih and then sprayed onto 75 g KA-O (Süd-Chemie). The held balls were calcined at 600 ⁰ C for 5h. The result was a Hfθ ₂ / Zrθ ₂ shell of 261μm.

225 g of the above-prepared spheres with a surface area of 97m2 / g were filled in the direction of a standard Fließbettvor- and by means of temperature-controlled at 80 ⁰ C compressed air (6 bar) placed in a fluidized bed state.

After drying the moldings, they were reduced to a Pd / Au coated catalyst with a gas mixture of ethylene (5% by volume) in nitrogen at a temperature of about 150 ^° C. in the fluidized bed apparatus. The resulting coated catalyst contained about 1.2 mass% Pd and had an Au / Pd atomic ratio of about 0.5, a shell thickness of about 210 microns and a hardness of 43 N.

The noble metal concentration of the Pd / Au coated catalyst thus produced deviated over a range of 90% of the shell thickness, with the outer and inner shell boundary areas each spaced 5% of the shell thickness, from the average noble metal concentration of this region by a maximum of +/- 10 % off.

Claims

claims

A coated catalyst for the production of vinyl acetate monomer (VAM) comprising an oxidic porous catalyst support having an outer shell containing metallic Pd and Au, characterized in that the framework structure of the porous catalyst support contains hafnium oxide units (HfO ₂ ).

2. coated catalyst according to claim 1, characterized in that the catalyst support is selected from the group consisting of silicon oxides, aluminum oxides, Alumosilika- th, zirconium oxide, titanium oxide, calcined acid-treated bentonites or mixtures thereof.

3. coated catalyst according to claim 2, characterized in that the Hafniumoxideinheiten in the framework structure of the catalyst support have a proportion of 0.01 to 50 wt .-% based on the weight of the catalyst support.

4. coated catalyst according to claim 3, characterized in that the catalyst support has a specific surface area (BET) of less than / equal to 160 m ² / g.

5. coated catalyst according to claim 4, characterized in that the specific surface area (BET) of the catalyst support in the range of 160 to 40 m ² / g.

6. coated catalyst according to claim 5, characterized in that the catalyst support has a hardness of greater than or equal to 20 N.

7. coated catalyst according to claim 6, characterized in that the catalyst carrier has an integral BJH pore volume of more than 0.25 ml / g.

8. coated catalyst according to claim 7, characterized in that the catalyst support has an integral BJH pore volume in the range of 0.25 to 0.7 ml / g.

9. coated catalyst according to claim 8, characterized in that the catalyst support has an average pore diameter of 8 to 50 nm.

10. coated catalyst according to claim 9, characterized in that the catalyst support has a Bayer acidity in the range of 1 and 150 microval / g.

11. coated catalyst according to one of the preceding claims, characterized in that the catalyst support comprises a calcined acid-treated bentonite, preferably with a proportion of greater than or equal to 50 wt .-%, based on the weight of the catalyst support.

12. coated catalyst according to claim 11, characterized in that the catalyst carrier contained in the calcined acid-treated bentonite has a SiO ₂ content of at least 65 wt .-%.

13. coated catalyst according to claim 12, characterized in that the catalyst carrier contained in the calcined acid-treated bentonite contains less than 10 wt .-% Al ₂ O ₃ .

14. coated catalyst according to one of claims 1 to 10, characterized in that the catalyst support consists of ZrO ₂ .

15. A coated catalyst according to one of the preceding claims, characterized in that the catalyst support is applied to a porous or non-porous shaped body which is different from the catalyst support.

16. coated catalyst according to one of the preceding claims, characterized in that the catalyst has a bulk density of more than 0.4 g / ml.

17. A coated catalyst according to claim 16, characterized marked, that the outer shell of the shell catalyst a

Thickness of less than 300 microns has.

18. coated catalyst according to one of claims 1 to 16, characterized in that the outer shell of the shell catalyst has a thickness in the range of 200 and 2000 microns.

19. A coated catalyst according to claim 17 or 18, characterized in that the content of Pd is 0.5 to 2.5 wt .-% is based on the weight of the loaded with precious metal catalyst.

20. coated catalyst according to claim 19, characterized in that the Au / Pd atomic ratio of the catalyst see between 0 and 1.2.

21. coated catalyst according to claim 20, characterized in that in the outer shell further HfO ₂ and / or ZrO _{2 is} included.

22. coated catalyst according to one of claims 17 to 21, characterized in that the noble metal concentration of the catalyst over a range of 90% of the shell thickness , wherein the area to the outer and inner shell boundary each spaced by 5% of the shell thickness deviates from the mean noble metal concentration of this range by a maximum of +/- 20%.

23. A coated catalyst according to claim 22, characterized in that the shell catalyst has a content of chloride of less than 250 ppm.

24. A coated catalyst according to claim 23, characterized in that the coated catalyst further contains an alkali metal acetate.

25. A coated catalyst according to claim 24, characterized in that the content of the catalyst of alkali metal acetate is 0.1 to 0.7 mol / 1.

26. A coated catalyst according to claim 25, characterized in that the alkali metal / Pd atomic ratio is between 1 and 12.

27. A process for the preparation of a coated catalyst, according to one of the preceding claims, comprising the steps of

b) applying a solution of a Pd precursor compound to the catalyst support; c) applying a solution of an Au precursor compound to the catalyst support whose framework structure contains hafnium oxide units (HfO ₂ );

28. The method according to claim 27, characterized in that the Pd and Au precursor compounds are selected from the halides, in particular chlorides, oxides, nitrates, nitrites, formates, propionates, oxalates, acetates, hydroxides, bicarbonates, amine complexes or organic complexes, for example triphenylphosphone complexes or acetylacetonate complexes, these metals.

29. The method according to claim 28, characterized in that the Pd precursor compound is selected from the group consisting of Pd (NH ₃ ) ₄ (OH) ₂ , Pd (NO ₃ ) ₂ , K ₂ Pd (OAc) ₂ (OH) ₂ , Pd (NH ₃ ) ₂ (NO ₂ ) ₂ , K ₂ Pd (NO ₂ ) _{4 /} Na ₂ Pd (NO ₂ ) ₄ , Pd (OAc) ₂ , PdCl ₂ , Na ₂ PdCl ₄ , and Pd (NH ₃ ) ₄ (NO ₃ ) ₂ .

30. The method according to claim 28, characterized in that the Au precursor compound is selected from the group consisting of KAuO ₂ , HAuCl ₄ , KAu (NO ₂ J ₄ , AuCl ₃ , NaAuCl ₄ , KAu (OAc) ₃ (OH), HAu (NO ₃ ) ₄ and Au (OAc) ₃ .

31. The method according to any one of the preceding claims, characterized in that the Pd and the Au precursor compound are applied to the catalyst support by the catalyst support with the solution of the Pd precursor compound and with the solution of the Au precursor compound or with a a solution containing both the Pd and the Au precursor compound is soaked.

32. The method according to any one of claims 27 to 30, characterized in that the solution of the Pd precursor compound and the solution of the Au precursor compound is applied to the catalyst support by the solutions are sprayed onto a fluidized bed or fluidized bed of the catalyst support, preferably by means an aerosol of solutions.

33. The method according to any one of the preceding claims, characterized in that the catalyst support is heated during the application of the solutions.

34. The method according to any one of the preceding claims, characterized in that

a) a first solution of a Pd and / or an Au precursor compound is provided;

b) providing a second solution of a Pd and / or an Au precursor compound, wherein the first solution causes precipitation of the noble metal component (s) of the precursor compound (s) of the second solution, and vice versa;

c) the first and the second solution are applied to the catalyst support.

35. The method according to claim 34, characterized in that the precursor compounds of the first solution are acidic and those of the second solution are basic.

36. The method according to any one of the preceding claims, characterized in that the catalyst support, after the Pd and / or the Au precursor compound has been applied to the catalyst support / is subjected to a fixing step.

37. A process for the preparation of a coated catalyst, in particular a coated catalyst according to one of the preceding claims, comprising the steps of

a) providing a powdery oxidic porous catalyst support containing units in its framework hafnium oxide (HfO ₂ ) units and wherein the catalyst support is loaded with a Pd and an Au precursor compound or with Pd and Au particles;

c) calcining the loaded shaped body according to step b);