WO1999041005A1

WO1999041005A1 - Method for the combinatorial production and testing of heterogeneous catalysts

Info

Publication number: WO1999041005A1
Application number: PCT/EP1999/000902
Authority: WO
Inventors: Hartmut Hibst; Andreas Tenten; Dirk Demuth; Ferdi Schueth; Stephan A. Schunk
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-02-12
Filing date: 1999-02-11
Publication date: 1999-08-19
Also published as: AU2725099A; EP1054727A1; JP2002502697A

Abstract

The invention relates to an array of heterogeneous catalysts and/or their precursors constituted by a body presenting continuous, preferably parallel, channels, in which at least n channels contain n different heterogeneous catalysts and/or their precursors, and where n has a value of 2, preferably a value of 10, more preferably a value of 100, especially a value of 1,000 and specifically a value of 10,000.

Description

- 1 -

Process for combinatorial production and testing of heterogeneous catalysts

The invention relates to a process for the combinatorial production and testing of heterogeneous catalysts and catalysts obtained by this process.

In addition to classic chemistry, which is aimed at the synthesis and investigation of individual substances, so-called combinatorial chemistry has developed for the production and investigation of new chemical compounds. Here, a large number of reactants were first implemented in a one-pot synthesis and it was examined whether the resulting reaction mixture had the desired properties, for example a pharmacological activity. If an efficacy for such a reaction mixture was found, it had to be determined in a further step which specific substance in the reaction mixture was responsible for the efficacy. In addition to the great effort involved in determining the actually active compound, it was also difficult to rule out undesirable side reactions in the case of a large number of reactants.

Another approach to combinatorial synthesis involves the synthesis of a large number of compounds by targeted metering and implementation of a number of reactants in a large number of different reaction vessels. In this process, a reaction product is preferably present in each reaction vessel, so that, for example, given the pharmacological activity of a mixture, the starting materials used for its preparation are immediately known. In addition to the first applications of this more specific combinatorial synthesis in the search for new pharmacologically active substances, the synthetic process has recently also been expanded to include low molecular weight organic compounds and organic and inorganic catalysts.

F.M. Menger et al, "Phosphatase Catalysis Developed via Combinatorial Organic Chemistry", J. Org. Chem. 1995, 60, pages 6666 to 6667 describes the preparation of organic catalysts using combinatorial processes. 8 functionalized different carboxylic acids were bound to a polyallylamine via amide bonds. In addition, different metal ions were bound to the polymer via complex formation. The polymers obtained were then examined for their phosphatase activity. It is not described whether the catalysts were obtained by an automated manufacturing process. Only the production of individual catalysts is described.

In CL Hill, RD Gall, "The first combinatorially prepared and evaluated inorganic catalysts. Polyoxometalates for the aerobic oxidation of the mustard analog tetrahydrothiophene (THT)", J. Mol. Catalysis A: Chemical 114 (1996), pages 103 to 111 describes the combinatorial production and testing of polyoxometalates for the aerobic oxidation of tetrahydrothiophene. The polyoxometalates were prepared by mixing different proportions of metal salt solutions of the desired metals. For this purpose, tungsten, molybdate and vanadate solutions as well as a sodium hydrogen phosphate solution were produced. After the corresponding solutions had been metered in, the pH was adjusted to a predetermined value and a reaction was brought about. The catalysts obtained were used in dissolved form for the reaction. It is not described whether the catalyst production was automated. - 3 -

Methods for the targeted metering of different amounts of different liquid reactants into an array of reaction vessels, which can for example resemble a spotting plate, are described in US Pat. No. 5,449,754. To do this, the print head of an inkjet printer, which is connected to supply solutions of the reactants, is moved over the array with the aid of an XY positioner and the dispensing of the liquids is controlled by a computer.

In F.C. Moathes et al, "Infrared Thermographic Screening of Combinatorial Libraries of Heterogeneous Catalysts", Ind. Eng. Chem. Res. 1996, 35, 4801 to 4803 describes the investigation of combinatorially produced libraries of heterogeneous catalysts by IR analysis. The catalysts consisted of different element metals that were applied to aluminum oxide. They were examined for the catalytic activity of hydrogen oxidation. The individual catalysts were produced by soaking aluminum oxide pellets in corresponding metal salt solutions, drying and calcining. It is not specified whether the production was automated.

The different pellets were placed on predetermined supports on a support and contacted with hydrogen under reaction conditions. In the event of catalytic activity, the catalyst warmed up and the warming was measured with the aid of an infrared camera, whereby the active catalysts could be determined.

In BE Baker et al, "Solution-Based Assembly of Metal Surfaces by Combinatorial Methods", J. Am. Chem.-Soc. 1996, 118, pages 8721 to 8722 describes the production of differently composed metal surfaces by combinatorial processes. For this purpose, a silane-coated glass plate is immersed in a colloidal gold solution at a predetermined speed, so that there is a gradient in the gold distribution on the substrate. After removal and - 4 -

Drying the plate is rotated 90 ° and immersed in a silver ion solution, so that there is a further concentration gradient on the plate. There is a continuous change in the composition of the surface.

X.-D. Xiang et al., "A Cominatorial Approach for Materials Discovery", Science 268 (1995), pages 1738 to 1740 describe the production of BiSrCaCuO and YBaCuO superconductor films on substrates, using physical masking processes and vapor deposition techniques in the deposition of the corresponding metals combinatorial array of different metal compositions is obtained. After calcination, different compositions are present at different positions in the array and can be examined for their conductivity, for example, with microsensors.

In addition to the production of such superconductor arrays, WO 96/11878 also describes the production of zeolites, the amounts required in each case being metered from a plurality of metal salt solutions using an ink jet without prior mixing on a type of spotting plate, with addition of the last solution starts a precipitation. BSCCO superconductors can also be produced by metering the individual nitrate solutions of the required metals separately by spraying onto a type of spotting plate and then heating them up.

Different heterogeneous catalysts can be produced using the known processes. However, the testing of the catalysts is complex and often cannot be carried out under realistic conditions, for example with the required residence times of the reactants on the catalyst, since the catalysts are, for example, on a larger, generally flat support and this is charged, for example, with a gas mixture to be reacted got to. - 5 -

The object of the present invention is to provide a process for producing arrays from inorganic heterogeneous catalysts or their precursors, in which the catalysts obtained can be tested with less effort and under conditions which are similar to an industrial process. The disadvantages of the existing systems should also be avoided. Corresponding arrays should also be provided.

The object is achieved according to the invention by providing an array of, preferably inorganic, heterogeneous catalysts and / or their precursors, constructed from a body which, preferably has parallel, continuous channels, in which at least n channels n different, preferably inorganic, heterogeneous catalysts and / or contain their precursors, where n has the value 2, preferably 10, particularly preferably 100, in particular 1000, especially 10,000.

According to one embodiment of the invention, the body is a tube bundle reactor or heat exchanger, and the channels are tubes.

According to a further embodiment of the invention, the body is a block made of a solid material, which has the channels, for example in the form of bores.

The heterogeneous catalysts and / or their precursors are preferably full contacts or supported catalysts and / or their precursors and are present as catalyst bed, tube wall coating or auxiliary support coating.

The term "array of inorganic heterogeneous catalysts or their

Forerunners "denotes an arrangement of different inorganic

Heterogeneous catalysts or their precursors on predetermined, spatially separated areas of a body, preferably a body with parallel continuous channels, preferably a tube bundle reactor or heat exchanger. The geometric arrangement of the individual areas can be chosen freely. For example, the areas can be arranged in the manner of a row (quasi one-dimensional) or a checkerboard pattern (quasi two-dimensional). In the case of a body with parallel, continuous channels, preferably a tube bundle reactor or heat exchanger with a large number of tubes which are parallel to one another, the arrangement becomes clear when one considers a cross-sectional area perpendicular to the longitudinal axis of the tubes: there is a tach in which the individual tube cross sections represent the different, spaced apart areas . The areas or tubes can also be present in a tight packing, for example for tubes with a circular cross section, so that different rows of areas are arranged offset from one another.

The term "body" describes a three-dimensional object that has a multiplicity (at least n) of continuous channels. The channels thus connect two surface areas of the body and run through the body.

The channels are preferably essentially, preferably completely parallel to one another. The body can be constructed from one or more materials and can be solid or hollow. It can have any suitable geometric shape. It preferably has two mutually parallel surfaces, in each of which there is an opening of the channels. The channels preferably run perpendicular to these surfaces. An example of one

Body is a cuboid or cylinder in which the channels are parallel between two

Surfaces run. However, a large number of similar geometries are also conceivable.

The term "channel" describes a connection running through the body between two openings present on the body surface, for example the

Allows fluid to pass through the body. The channel can have any geometry. It can be one along the length of the channel variable cross-sectional area or preferably have a constant channel cross-sectional area. The channel cross section can, for example, have an oval, round or polygonal outline with straight or curved connections between the corner points of the polygon. A round or equilateral polygonal cross section is preferred. All channels in the body preferably have the same geometry (cross section and length) and run parallel to one another.

The terms “tube bundle reactor” and “heat exchanger” describe combined parallel arrangements of a multiplicity of channels in the form of tubes, the tubes being able to have any cross section. The tubes are arranged in a fixed spatial relationship to one another, are preferably spaced apart from one another and are preferably surrounded by a jacket which comprises all the tubes. In this way, for example, a heating or cooling medium can be passed through the jacket, so that all tubes are kept at an even temperature.

The term "block made of a solid material" describes a body made of a solid material (which in turn can be constructed from one or more starting materials), which has the channels, for example in the form of bores. The geometry of the channels (bores) can be freely selected as described above for the channels. The channels (bores) do not have to be made by drilling, but can also be left free, for example, when molding the solid body / block, for example by extruding an organic and / or inorganic molding compound (for example by means of a corresponding nozzle geometry during the extrusion). In contrast to the tube bundle reactors or heat exchangers, the space in the body between the channels in the block is always filled with the solid material. The block is preferably constructed from one or more metals. - 8th -

The term “predetermined” means that, for example, a number of different catalysts or catalyst precursors are introduced into a tube bundle reactor or heat exchanger in such a way that the assignment of the different catalysts or catalyst precursors to the individual tubes is recorded and later, for example, when determining the activity, selectivity and / or long-term stability of the individual catalysts can be called up in order to enable an unambiguous assignment for specific measured values to specific catalyst compositions. The production and distribution of the catalysts or their precursors to the different tubes of the tube bundle reactor are preferably computer-controlled, the respective composition of a catalyst and the position of the tube in the tube bundle reactor into which the catalyst or catalyst precursor is introduced being stored in the computer and later can be accessed. The term "predetermined" thus serves to differentiate between a random or statistical distribution of the generally different catalysts or catalyst precursors on the tubes of a tube bundle reactor.

The arrays according to the invention can be produced from, preferably inorganic, heterogeneous catalysts and / or their precursors by different processes:

Method a comprises the following steps:

al) preparation of solutions, emulsions and / or dispersions of elements and / or element compounds of the elements present in the catalyst and / or catalyst precursor, and optionally of dispersions of inorganic support materials,

a2) if necessary, adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic Carriers in the solutions, emulsions and / or dispersions,

a3) simultaneous or successive coating of the channels of the

Body with the solutions, emulsions, and / or dispersions, wherein in each channel a predetermined amount of the solutions,

Emulsions and / or dispersions is introduced to obtain a predetermined composition, and

a4) optionally heating the coated body, if appropriate in the presence of inert or reactive gases, to a temperature in the

Range from 20 to 1500 ° C for drying and optionally sintering or calcining the catalysts and / or catalyst precursors.

Method b comprises the following steps:

bl) producing solutions, emulsions and / or dispersions of

Elements and / or element compounds of the elements present in the catalyst and / or catalyst precursor, and optionally of dispersions of inorganic support materials,

b2) optionally adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic carriers into the solutions, emulsions and / or dispersions,

b3) simultaneous or successive coating of in the

Channels of the body present catalyst carriers with the solutions, emulsions and / or dispersions, with a predetermined amount of the solutions, emulsions and / or dispersions being introduced into each channel in order to have a predetermined composition - 10 -

to obtain the catalyst supports, and

b4) optionally heating the body with the coated catalyst supports in the channels, optionally in the presence of inert or reactive gases, to a temperature in the range from 20 to 1500 ° C. for drying and optionally sintering or calcining the catalysts and / or catalyst precursors.

The method c) comprises the following steps:

cl) producing solutions, emulsions and / or dispersions of

Elements and / or element compounds of the chemical elements present in the catalyst and / or catalyst precursor and optionally of dispersions of inorganic support materials,

c2) mixing predetermined amounts of the solutions, emulsions and / or dispersions and optionally of precipitation aids in one or more reaction vessels operated in parallel,

c3) optionally adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic carriers into the mixture (s) obtained,

c4) coating one or more predetermined channels of the body with the mixture or several mixtures,

c5) repetition of steps c2) to c4) for other channels of the

Body until the channels are coated with the respectively predetermined catalyst and / or catalyst precursor compositions, - 11 -

c6) optionally heating the coated body, optionally in the presence of inert or reactive gases, to a temperature in the range from 20 to 1500 ° C. for drying and optionally sintering or calcining the catalysts and / or catalyst precursors.

It preferably comprises the following steps:

cl) Preparation of solutions of element compounds of the chemical elements present in the catalyst except oxygen, and optionally of dispersions of inorganic support materials

c2) mixing predetermined amounts of the solutions or dispersions and, if appropriate, of precipitation aids in one or more reaction vessels operated in parallel with precipitation of the chemical elements present in the catalyst,

c3) if appropriate, adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic

Carriers in the suspension obtained,

c4) coating one or more predetermined tubes of the tube bundle reactor or heat exchanger with the suspension,

c5) repetition of steps c2) to c4) for different pipes of the

Tube bundle reactor or heat exchanger until the tubes are coated with the respectively predetermined catalyst compositions, - 12 -

c6) heating the coated tube bundle reactor or heat exchanger, optionally in the presence of inert or reactive gases, to a temperature in the range from 20 to 1500 ° C. for drying and optionally sintering or calcining the catalysts.

The method d) comprises the following steps:

dl) preparing solutions, emulsions and / or dispersions of

d2) mixing predetermined amounts of the solutions, emulsions and / or dispersions and optionally of precipitation aids in one or more reaction vessels operated in parallel,

d3) optionally adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic carriers into the mixture (s) obtained,

d4) coating catalyst supports present in one or more predetermined channels of the body with the mixture or one or more of the mixtures,

d5) repetition of steps d2) to d4) for others (ie in the

Rule the as yet uncoated catalyst carriers in the channels of the body until the (preferably all) catalyst carriers present in the channels of the body with the respectively predetermined (usually different) catalyst and / or catalyst - 13-

precursor compositions are coated,

d6) optionally heating the body with the coated catalyst supports in the channels, optionally in the presence of inert or reactive gases, to a temperature in the range from 20 to

1500 ° C for drying and optionally sintering or calcining the catalysts and / or catalyst precursors.

The adhesion of the channels (e.g. the inner surface of the tubes) of the body or the catalyst carrier before coating can be increased by chemical, physical or mechanical pretreatment of the inner walls of the channels (e.g. inner tubes) or the catalyst carrier or by applying an adhesive layer, this is particularly true to processes a) and c) or b) and d).

The method e comprises the following steps:

el) manufacture of different heterogeneous catalysts and / or their precursors in the form of full contacts with a predetermined composition,

e2) loading one or more predetermined channels of the

Bodies that are secured against falling out of the heterogeneous catalysts, each with one or more of the heterogeneous catalysts and / or their precursors with a predetermined composition.

e3) optionally heating the body with the heterogeneous catalysts and / or their precursors in the channels, optionally in the presence of inert or reactive gases, to a temperature - 14-

in the range from 20 to 1500 ° C. for drying and optionally sintering or calcining the catalysts and / or catalyst precursors.

The procedure f) comprises the following steps:

fl) coating and optionally heating predetermined ones

Catalyst supports for the production of predetermined supported catalysts in the manner defined above in process b) or d) outside the body,

f2) introduction of the supported catalysts into predetermined channels of the

Body,

f3) optionally heating the filled body, optionally in

^~ Presence of inert or reactive gases, to a temperature in the

Range from 20 to 1500 ° C for drying and optionally sintering or calcining the catalysts.

The outer shape of the supported catalysts preferably corresponds at least substantially, preferably approximately or completely, to the shape of the channel interior in the body.

The invention also relates to inorganic heterogeneous catalyst arrays which can be obtained by one of the above processes. The arrays can also be made by any combination of the above methods.

The processes are suitable for producing a large number of catalyst systems, as described, for example, in G. Ertl, H. Knözinger, J. Weitkamp, editor, - 15 -

"Handbook of Heterogeneous Catalysis", Wiley-VCH, Weinheim, 1997.

In addition, the invention relates to a method g) for determining catalytic properties, in particular the activity, selectivity and / or long-term stability of the catalysts described above and below in an array described, comprising the following steps:

gl) optionally activating the catalysts in the body,

g2) tempering the body to a desired reaction temperature,

g3) passing a fluid reactant or a fluid reaction mixture through (one, several or all of the) channels of the body,

g4) (preferably separate) discharge of the converted fluids from individual or several combined channels of the body,

g5) (preferably separate) analysis of the carried out implemented

Fluids,

g6) if necessary comparative evaluation of the analysis results of several analyzes.

A preferred process variant is characterized in that, after the body has been brought to a first reaction temperature in step g2), steps g3) to g6 are carried out in succession for several different fluid reactants or fluid reaction mixtures, it being possible in each case to insert a flushing step with a flushing gas, and then the body for a second - 16 -

The reaction temperature can be controlled and the above reactions can be repeated at this temperature.

At the beginning of the analysis, the gas flow collected from the entire array can be analyzed in order to detect any implementation. Afterwards, if there is a conversion, the discharges of the individual pipes or several pipes can be analyzed in order to determine an optimal catalyst with a minimal number of analysis processes.

Individual tubes or several or all tubes can be flowed through together.

The fluid reactant or fluid reaction mixture is preferably a gas or gas mixture.

The invention allows automated production and catalytic testing for the purpose of mass screening heterogeneous catalysts for chemical reactions, in particular for reactions in the gas phase, very particularly for partial oxidations of hydrocarbons in the gas phase with molecular oxygen (gas phase oxidations).

Reactions or conversions suitable for the investigation are described in G. Ertl, H. Knözinger, J. Weitkamp, editor, "Handbook of Heterogeneous Catalysis", Wiley-VCH, Weinheim, 1997. Examples of suitable reactions are listed primarily in this literature in volumes 4 and 5 under numbers 1, 2, 3 and 4.

Examples of suitable reactions are the decomposition of nitrogen oxides

Ammonia synthesis, the ammonia oxidation, oxidation of hydrogen sulfide to sulfur, oxidation of sulfur dioxide, direct synthesis of methyl - 17-

chlorosilanes, oil refining, oxidative coupling of methane, methanol synthesis, hydrogenation of carbon monoxide and carbon dioxide, conversion of methanol into hydrocarbons, catalytic reforming, catalytic cracking and hydrocracking, coal gasification and liquefaction, fuel cells, heterogeneous photocatalysis, synthesis of MTBE and TAME, isomerizations, alkylations , Aromatizations, dehydrogenations, hydrogenations, hydroformylations, selective or partial oxidations, aminations, halogenations, nucleophilic aromatic substitutions, addition and elimination reactions, oligomerizations and metathesis, polymerizations, enantioselective catalysis and biocatalytic reactions.

The invention is explained in more detail below on the basis of preferred embodiments.

Manufacture of the inorganic heterogeneous catalyst arrays

First, two or more, preferably 10 or more, very particularly preferably 100 or more, in particular 1000 or more, especially 10,000 or more liquid starting mixtures (hereinafter referred to as mixtures), which contain selected chemical elements of the periodic table, are prepared in Form of solutions, emulsions and / or preferably suspensions (dispersions), the mixtures prepared generally differing in their chemical composition or concentration. Several mixtures of the same composition can also be used to check the reproducibility.

The liquid mixtures generally contain a liquid chemical component which is used as a solvent, emulsifying aid or dispersing aid for the other components of the mixture. Organic solvents and emulsifying aids are used as solvents or dispersing aids - 18 -

and / or water, preferably water.

In addition to the chemical elements of the solvent or dispersing aid, the liquid mixtures contain one or more, preferably 2 or more, particularly preferably 3 or more chemical elements, i.a. but it does not contain more than 50 different chemical elements, each containing more than 1% by weight. The chemical elements in the mixtures are preferably present in very intimate mixing, e.g. in the form of a mixture of various miscible solutions, intimate emulsions with small droplet size and / or preferably as a suspension (dispersion), which the chemical elements in question generally in the form of a fine-particle precipitation, e.g. contains in the form of a chemical mixture. The use of sols and gels has also proven particularly useful, in particular those which contain the chemical elements in question in a largely homogeneous distribution and preferably those which have an adhesive and flow behavior which is favorable for the subsequent coating. The starting compounds for the selected chemical elements are in principle the elements themselves, preferably in finely divided form, and in addition all compounds which contain the selected chemical elements in a suitable manner, such as oxides, hydroxides, oxide hydroxides, inorganic salts, preferably nitrates, Carbonates, acetates and oxalates, organometallic compounds, alkoxides, etc. The respective starting compounds can be used in solid form, in the form of solutions, emulsions and / or in the form of suspensions.

Preferred element compounds, in particular catalytically active metals, are water-soluble oxides, hydroxides or salts with organic or inorganic acids. Active metals are preferably found in the subgroups of the Periodic Table of the Elements, for example in the 5th and 6th subgroups for oxidation catalysts and in the platinum group for hydrogenation catalysts. The method according to the invention also does not allow the screening of as yet - 19 -

(atypical) elements deemed to be catalytically active, in particular metals or metal oxides.

In addition, the liquid mixture can contain further compounds which influence the adhesive properties and the flow behavior of the liquid mixture on the inside of the channel or the inside of the pipe or catalyst support to be coated, and thus the coating properties of the liquid mixture. Organic compounds such as ethylene glycol or glycerin as described in DE-A 4 442 346 or maleic acid copolymers, for example, and inorganic compounds such as SiO ₂ , organic silicon compounds or siloxanes are to be mentioned here.

Furthermore, the mixtures can contain known inorganic carrier materials such as Al ₂ O ₃ , ZrO ₂ , SiO ₂ , Y ₂ O ₃ , TiO ₂ , activated carbon, MgO, SiC or Si ₃ N ₄ , which generally have the surface of the mixture accessible to catalysis Increase contained catalytically active chemical elements, which can also influence the catalytic properties of the active compositions obtained and which can also affect the adhesive and flow properties of the mixture obtained. As a rule, coatings are obtained which contain the preferably oxidic, nitridic or carbidic support material in addition to the actual catalytic material. When the components are mixed or when the coating is subsequently heated, the support material mentioned can also react with the chemical elements used above to form a new solid material.

Furthermore, the mixtures used can additionally contain an inorganic and / or organic binder or a binder system which stabilizes the mixture used. For this purpose, for example, binders or binder systems are suitable, the metal salts, metal oxides, metal oxide hydroxides, metal oxide hydroxide phosphates and / or euteküsche melting at the operating temperature of the catalyst - 20 -

Connections included.

The mixture can also be adjusted in a defined pH range by adding acids and / or bases. In many cases pH-neutral suspensions are used. For this purpose, the mixture can advantageously be adjusted to a pH between 5 and 9, preferably between 6 and 8. Special results can be achieved with the process according to the invention if the mixture has a high solids content of up to 95% by weight, preferably 50 to 80% by weight, with a low viscosity. If the precipitation is insufficient, precipitation aids such as ammonia can be added.

In a preferred embodiment of the invention, the mixture is stirred after and generally also during production and its flowability is measured continuously, but at least at the end of production. This can e.g. by measuring the current consumption of the stirrer. With the help of this measurement, the viscosity of the suspension can e.g. can be adjusted by adding further solvents or thickeners in such a way that optimum adhesion, layer thickness and layer thickness uniformity result on the inner tube wall to be coated or on the auxiliary support (catalyst support) to be coated.

In principle, the invention is not restricted to certain catalyst materials and catalyst compositions. The mixture can be prepared in parallel or in succession and is usually carried out in an automated form, e.g. with the aid of an automatic pipetting device or pipetting robot or also an inkjet method, as described, for example, in US Pat. No. 5,449,754.

For coating the tubes of the tube bundle reactor or heat exchanger

Process variant a), solutions, emulsions or suspensions of individual elements or element compounds can be separated from one another simultaneously or on top of one another. - 21 -

are subsequently introduced into the pipes. The simultaneous introduction can take place, for example, with the aid of a modified ink jet (ink jet printer printhead) which contains separate feed lines for the individual solutions, emulsions or suspensions and which allows simultaneous spraying. Compared to this process variant a, process variant b is preferred, which is carried out in particular as follows:

To produce the catalysts or their precursors, solutions, emulsions and / or suspensions of the required elements are first prepared in separate vessels. These are often metal salt solutions, such as nitrates. From the separate solutions, the amounts required for the production of a catalyst or catalyst precursor are transferred in the desired proportions to a small separate reaction container in which the components are mixed intensively. The dosing can be carried out, for example, with the aid of automatic pipetting devices or ink-jet. When the components are mixed, the components may react or precipitate. With the aid of precipitating agents such as ammonia, precipitation is optionally brought about or completed, so that a suspension of the mixed catalyst precursor material is often present.

Since the suspension should have a suitable viscosity in order to be able to be introduced and distributed into a tube of the tube bundle reactor, so that the catalyst or catalyst precursor is distributed as uniformly and largely as possible on the inner wall of the tube, the suitable one can, if necessary Viscosity of the suspension as described above can be set to the desired value with additional additives. The suspension can be removed from the reaction container using pipettes, for example, and the distribution in the tube, as described below, by spraying or spraying. The reaction vessel can be completely or partially emptied. Several reaction vessels can be operated in parallel, or one - 22 -

After partial emptying, the reaction container can be filled with other components in order to achieve a changed composition.

Coating with the mixtures produced is carried out, preferably by means of a spraying process, on various parts of, in particular, a metallic tube reactor or heat exchanger, in particular on the tube inner walls of (preferably metallic) reaction tubes of a tube bundle reactor with a layer of 10 to 2000 μm thick, with each tube in general a mixture of different compositions is coated (to check the reproducibility, several mixtures of the same composition can be used in several tubes).

To check layer thickness effects (such as transport effects), the same catalyst compositions with different layer thicknesses can also be applied in different tubes.

In a further variant of the invention, auxiliary supports (preferably metallic or ceramic tubes) are used which have been coated with the liquid mixture after or, preferably, before being inserted into the reaction tubes of a tube bundle reactor.

Tubes with any cross-section can be used as auxiliary supports. These are preferably circular. The material of the auxiliary carrier can be chosen freely, for example it can be auxiliary carrier made of glass, metal, ceramic such as glass ceramic, activated carbon, graphite or sintered quartz. The material can be densely sintered or porous. The tubes can also be segmented in such a way that a plurality of channels, preferably parallel to one another, extend parallel to the longitudinal axis of the tube. The cross section of such tubes can, for example, be similar to a spoked wheel. An outer tube and an inner tube can also be connected by a plurality of continuous spokes. - 23 -

The number of spokes can be chosen freely.

The auxiliary supports can also be solid as porous materials, provided that they preferably have a high porosity. For example, they can be constructed from foams of the materials mentioned above. The solid bodies can have any suitable shape. Suitable shapes are, for example, cylinders, cones, disks, blades, etc.

Suitable auxiliary carriers are, for example, from ROBU Glasfϊlter-Geräte GmbH, D-57644 Hattert, offered as a sinter filter, from PoroCer Keramikmembranen GmbH, D-07629 Hermsdorf, offered as tubular membranes for crossflow filtration, from Tami Deutschland GmbH, D -07629 Hermsdorf / Thür. , offered as Ceramic Tube Membranes for Crossflow Filtration and Hi-Tech Ceramics, a Vesuvius Group Company, Alfred, NY 14802, USA, offered as RETICEL ceramics. Products from other providers can of course also be used.

Examples of porous metal auxiliary carriers are sintered metals, metal woven fabrics, knitted fabrics, felts or nets. Metals in particular offer great advantages in terms of reaction technology with regard to their thermal conductivity, in particular when large amounts of heat have to be dissipated or exact temperature control is necessary.

Suitable porous activated carbon and graphite auxiliary carriers are known.

The arrays according to the invention are preferably produced with the aid of such auxiliary carriers by the method f), as described above. The auxiliary carriers are preferably coated outside the body and, if necessary, heated. After the support catalysts thus produced have been introduced into predetermined channels of the body, the filled body becomes - 24 -

optionally heated to dry the catalysts and optionally to sinter or calcine. The supported catalysts described above can have the auxiliary supports as catalyst supports.

The coating of the body or of the preferred heat exchanger is explained in more detail below.

The parts of the, preferably metallic, heat exchanger coated with the previously prepared liquid mixture are preferably the inner walls of the tube, preferably, metallic tube bundle reactors. The reaction tubes of the tube bundle reactor can have any cross section, but generally have a round and in particular circular cross section. The inside diameter is preferably 0.2 to 70 mm, preferably 1 to 25 mm, particularly preferably 3 to 10 mm. The tube bundle reactor can contain up to 30,000 reaction tubes or more, preferably 10 to 20,000, particularly preferably 100 to 10,000 reaction tubes, which are generally each provided with a differently composed coating.

The coating with liquid mixtures can be applied by sponging, slurrying, brushing, spinning, spraying and / or dipping. Furthermore, the mixture can be poured into the individual tubes and at speeds between

200 and 1000 rpm, preferably at speeds between 300 and 800 rpm, are thrown. In a preferred embodiment, the

Coatings are made on the inside of the reaction tubes by spraying the above-mentioned liquid mixture. The sprayed-on mixture material presses itself into the roughness of the surface, preventing air bubbles under the coating. The mixture used can adhere completely to the sprayed inside. However, a portion of the mixture can also be discharged again by dripping, particularly if the mixture has less adhesion and / or the viscosity is low. The ones to be coated - 25 -

Subcarriers, e.g. in the form of inner tubes can be coated completely or only partially. In particular, the respective reactor tube inlet and reactor tube outlet can be left out of the coating by a suitable device in order to prevent later sealing problems with the fluid supply and discharge devices to be connected. A coating in which the mixture is sprayed into the preheated tube or this mixture is introduced into the preheated tube by immersion has also proven useful. For this purpose, the metallic base body is preheated to 60 to 500.degree. C., preferably 200 to 400.degree. C. and particularly preferably 200 to 300.degree. C. before the suspension is sprayed on, and coated with the mixture described at the outset at this temperature. A large part of the volatile constituents of the mixture is evaporated and a preferably 10 to 2000 μm, particularly preferably 20 to 500 μm thick layer of the catalytically active metal oxides is formed on the preferably metallic base body. This type of manufacture can e.g. as described in DE-A-2 510 994 take place with the variant that the mixture is not applied to a preheated carrier, but to a preheated, preferably metallic, base body.

In order to achieve particularly thick layers or particularly homogeneous coatings, the reaction tubes can also be coated several times in succession. Separate drying and / or calcining and / or sintering steps can be interposed between the individual coatings of a reaction tube. In the case of spraying, the inner wall coating is advantageously carried out with the aid of one or more spray lances, preferably with one or more movable spray lances. The spray lance is used during the spraying process e.g. drawn through the pipe to be coated with the aid of an automatic device at a defined constant or varying speed.

The thickness of the applied layer after drying and if necessary - 26 -

Calcination or sintering is preferably 10 to 2000 μm, particularly preferably 20 to 500 μm.

In addition, before the coating on the inner tube, an adhesion promoter can be applied and then a cover layer containing and catalytic material containing catalyst material can be applied to this adhesion promoter. The adhesion promoter can increase the adhesion of the catalytically active cover layer on the inner tube. In addition, the service life can be extended if an adhesion promoter is used. Suitable adhesion promoters have been described above.

In addition, the adhesion of the catalytic layer can be increased by chemical, physical or mechanical pretreatment of the inner tube before coating. In the case of chemical pretreatment, the inner tubes can e.g. be pickled with bases or preferably with acids. Furthermore e.g. the inner tube is roughened by blasting with a dry blasting medium, in particular corundum or quartz sand, in order to support the adhesion. In addition, detergents which have a suspension of hard particles, e.g. Corundum, in a dispersion liquid.

In addition, the coating on the preferably metallic inner tube can comprise the components auxiliary carrier and a catalytic top layer containing catalyst material, as described, for example, in DE-A-19 600 685. The auxiliary carrier preferably has an external shape which at least essentially corresponds to the geometry of the surface to be coated. Metallic or ceramic bodies, for example braids made of wire or pipes made of metal or ceramic, can be used as auxiliary carriers. At least the auxiliary carrier and preferably only the auxiliary carrier is coated with the catalytically active cover layer and the coated auxiliary carrier as a whole -27-

Reaction inner tube or preferably arranged in a part of the inner reaction tube. In this tube-in-tube arrangement, the outer tube can have a taper at one end, for example, in order to prevent the inner tube from falling out; at the other end, the projecting inner tubes can be pressed into the outer tube, for example by springs or a resilient material.

What is special about the process according to the invention is that each auxiliary support in the tube bundle reactor used generally has a different composition or also a different layer thickness of the catalytic coating. In addition, the coated subcarriers can easily be exchanged for other subcarriers with other coatings. For example, a suitable reactor design (provision of shut-off valves, etc.) can make it possible to change individual auxiliary carriers while the reactor is in operation.

When the coated tube bundle reactor is heated under vacuum or under a defined gas atmosphere to temperatures of 20 to 1500 ° C., preferably 60 to 1000 ° C., particularly preferably 200 to 600 ° C., very particularly preferably 250 to 500 ° C., the coating applied beforehand is passed through Drying freed from the preferably aqueous solvent. At elevated temperature, sintering or calcination of the particles forming the coating can also take place. The actual catalytically active coating is generally obtained in this process.

To regulate the temperature, the reaction tubes are preferably surrounded by a heat transfer medium, for example by a molten salt or by liquid metal such as Ga or Na. The liquid heat transfer medium is preferably fed in and discharged at mutually opposite points of the tube bundle reactor, for example by means of a pump, in order to then conduct it via an (for example air-cooled) heat exchanger for heat dissipation or heat absorption. On the one hand, the heat transfer medium ensures that the temperature for drying, - 28 -

for the subsequent sintering of the coating and for the subsequent fluid phase test reaction in the reaction tubes. On the other hand, the heat transfer medium dissipates the heat generated during the subsequent test reaction and thus suppresses the formation of so-called hot spots along the catalyst coating, in which locally a higher temperature than in the rest of the catalyst coating is suppressed.

This type of reaction ensures that the heat occurring during the reaction is dissipated excellently, so that practically no hot spot occurs.

In a further embodiment of the invention, the space located between the reaction tubes is filled with a solid material, preferably a metal or with a solid metal alloy. In this case, the tube bundle tractor merges into a material block as described above, in particular a metal block with channels or bores. The inside diameter of the bores corresponds to the inside diameter of the reaction tubes of the tube bundle reactor.

It is also possible to produce different heterogeneous catalysts in the form of full contacts or supported catalysts using known, for example combinatorial processes, with a predetermined composition and to feed each of these prefabricated heterogeneous catalysts to one or more predetermined tubes of the tube bundle reactor or heat exchanger or tubes or auxiliary carriers to be inserted into them. The known types of molded bodies can be used. For each individual pipe it is possible to vary the height of the bed or the inert content of a bed or to set other bed parameters. Tubes filled with the supported catalysts and secured against falling out can thus be introduced into the actual tube bundle reactor. This leaves the simple one - 29 -

Exchange of individual catalyst fillings too.

The catalysts are tested by reacting fluid reactants or reaction mixtures which are generally in liquid or preferably gaseous form. Oxidation catalysts are preferably tested by subjecting individual, several or all tubes of the coated tube-bundle reactor to a gas mixture of one or more saturated, unsaturated or polyunsaturated organic starting materials (for example hydrocarbons, alcohols, aldehydes etc.) and oxygen-containing gases in parallel or in succession Gas (for example air, O ₂ , N ₂ O, NO, NO ₂ , O ₃ ) and / or for example H ₂ , and optionally an inert gas, for example nitrogen or an inert gas, at temperatures from 20 to 1200 ° C., preferably at 50 up to 800 ° C, particularly preferably at 80 to 600 ° C, with a suitable device ensuring that the respective gas streams of the individual, several or all reaction tubes of the tube bundle reactor are discharged separately or in parallel.

The reaction tubes of the tube bundle reactor, which are usually coated differently, for example, a gas mixture of, for example, an oxygen-containing gas (for example air, O ₂ , N ₂ O, NO, NO ₂ , O ₃ ) and / or H ₂ and the organic starting material to be reacted ( for example propene or o-xylene). In addition to the gaseous substances mentioned, other gaseous substances, such as Cl or P-containing substances, can also be present. The gas mixture can be passed through the individual reactor tubes one after the other. In the preferred embodiment, the gas mixture is passed through the reaction tubes in such a way that the gas mixture flows through all tubes simultaneously. During the start-up of the reaction, ie during the activation time of the catalytic coatings, the composition of the feed, the temperature of the heat exchange medium or the reaction tube, the residence time of the feed and / or the pressure of the total gas in the tube bundle reactor can be changed. The respective one - 30 -

Product gases leaving the reaction tube, which are formed by reaction of the reaction gases used, are generally discharged separately, but if appropriate also in a combined manner, and, e.g. with regard to their composition, analyzed using various probes or analysis methods.

The application of the gas mixture to the coated tube-bundle reactor can also take place directly after the suspension coating (with the omission of drying and sintering or calcining), in which case the drying and possibly subsequent sintering process takes place under the gas mixture mentioned. The composition of the inner tube coating can change. In particular, oxidic coatings can release part or all of their oxygen under strongly reducing conditions or absorb oxygen into their structure under strongly oxidizing conditions.

The supply of a constant gas mixture to the individual, differently coated reaction tubes of the tube bundle reactor can e.g. via a gas supply hood which can be placed essentially gas-tight on the tube bundle reactor.

The mixing of the gases used can take place in the gas supply hood or only in this, e.g. using a static mixer.

The individual reaction gases can be discharged via a device placed essentially gas-tight on the tube bundle reactor, the individual reaction gases of the individual several or all reaction tubes being derived separately and then analyzed separately via a valve circuit.

Another way of separately deriving the individual exhaust gases of the respective generally differently coated reaction tubes consists in a - 31 -

computer-controlled mechanically moved "sniffing device" with a sniffer line for the gas to be withdrawn, which is positioned essentially automatically on, in or above the outlet of the respective reaction tube and then takes a reaction gas sample. The positioning and removal of the respective reaction gas is preferably carried out in such a way that only the actual reaction gas to be analyzed later and no additional foreign gas gets into the sniffer line from the outside. If the sniffing device is positioned on the end of the reaction tube, then an essentially gas-tight attachment of the sniffing line to the end of the reaction tube, for example by pressing the sniffing device onto the end face of the tubular reactor, is advantageous. If the sniffing device is positioned in or above the outlet of the respective reaction tube, it is advantageous to draw the reaction gases into the sniffing devices via a negative pressure set in the sniffing line in such a way that the amount of the reacted gases is so limited that none additional foreign gases are sucked into the sniffer line. In the case of positioning the sniffer line in the outlet of the respective reaction tube, it has proven to be particularly advantageous if the end of the sniffer line is tapered in such a way that an essentially gas-tight seal is provided by inserting the sniffer line into the end of the respective reaction tube the reaction gas escaping the reaction tube in question is guaranteed against the outside. After reaction gas has been withdrawn from the reaction tube of the tube bundle reactor under consideration, the sniffing device is - preferably automatically - positioned on, in or over another, usually the nearest exit of another reaction tube, in order to accomplish the next gas withdrawal there. In this way, all exhaust gases from the reaction tubes for sampling can be started up separately and then analyzed. It is not only possible that the positioning is moved on, in or above the reaction tube outlet and the tube bundle reactor is fixed, but the sniffer line can be fixed during the positioning and the - 32 -

Tube reactor are moved accordingly. Both the sniffing device and the tube bundle reactor can experience a movement during the positioning. In a preferred process variant, the tube bundle reactor remains unchanged and only the sniffer device is moved over or onto the respective reaction tube ends during the positioning. In another preferred process variant, the tube bundle reactor undergoes a rotational movement about its axis during the positioning, while the sniffer line performs a linear movement in the direction of the axis of rotation of the tube bundle reactor when positioned over the respective reaction tube ends, while the sniffer device carries out an additional movement when positioned on the respective reaction tube ends Performs movement parallel to the reactor axis. Several sniffing devices can also be used simultaneously for sampling the different reaction gases. In addition, several combined tubes can also be sampled.

In an analogous manner to how the gas is discharged via so-called sniffer lines, as an alternative to the gas supply hood, the gas supply can also be carried out using such a principle, with the individual tubes being tested sequentially. Of course, the exhaust sniffer line must be positioned synchronously with the fresh gas supply line.

The catalytic performance of the individual catalytic coatings of the individual reaction tubes can be screened by chemical analysis of the respective gas streams using suitable methods known per se. The gas streams individually derived from the individual reaction tubes of the tube bundle reactor are individually analyzed for their composition, for example by means of suitable devices, for example using gas chromatography with HD and / or TCD as a detector, or for example by means of mass spectrometry. The gas composition obtained is particularly important with regard to its relative content of the desired product or of various desired products - 33 -

analyzed and the concentrations obtained in relation to the reacted reactant, resulting in values for the respective conversions (activity) and product selectivities. In many cases it is useful to select the product selectivities of the individual catalysts. longer period of generally hours to several weeks. When selecting the most suitable catalyst coating for the respective reaction, in order to limit the number of gas analyzes, it can be useful to determine the repeat measurements only on gas compositions of selected reactor tubes that exceed a desired limit concentration or limit selectivity for certain products.

After the catalytic test, the applied catalytic inner coatings can be removed so that the tube bundle reactor obtained is again accessible for a new catalytic coating.

The catalyst coatings can be renewed in that the old catalytically active top layer of the coating is at least substantially removed and a new catalytically active coating is applied by means of sponges, brushes, spinning, spraying and / or dipping. Appropriately, one will choose the same coating method with which the previously removed catalytic coating has been applied. The old catalytically active top layer of the coating can be removed in particular by blasting with a blasting medium, e.g. Corundum, silicon carbide, fine sand or the like can be done in a simple manner. As an alternative, treatment with steam or the use of chemical removal methods has also proven itself.

An efficient method for removing the inner coatings - for example after the catalyst test - is usually the use of brush devices, for example analogous to a bottle brush, in conjunction with the described - 34 -

Cleaning agents is preferred. The removal of the inner coatings is at least largely automated.

The method according to the invention can easily be carried out in automated form by robots. A coating of tubes with the catalyst ensures an optimal flow of the fluid, causes only little pressure loss and prevents blockages in the individual reaction tubes of the tube bundle reactor.

The spatial separation and unambiguous assignment of the tested coatings offers the advantage of being able to use one apparatus (tube bundle) to simultaneously test a number of materials that generally corresponds to the number of tubes at the same time, with reduced costs and time.

Furthermore, the tube bundle reactor offers compared to other systems, e.g. Perforated plates, CVD arrays, etc. have the advantage of testing as close as possible to a technical process (scale-up capability is retained). A technically relevant optimization can be carried out very quickly and inexpensively, in particular also because a large number of catalysts can be tested in parallel / simultaneously under the same conditions.

Claims

- 35 patent claims

1. Array of heterogeneous catalysts and / or their precursors, composed of a body which preferably has parallel, continuous channels and in which at least n channels contain n different heterogeneous catalysts and / or their precursors, n being the value 2, preferably 10, particularly preferably 100, in particular 1000, especially 10000.

2. Array according to claim 1, characterized in that the heterogeneous catalysts are inorganic heterogeneous catalysts.

3. Array according to claim 1 or 2, characterized in that the body is a tube reactor or heat exchanger and the channels are tubes, or the body is a block made of a solid material which has the channels.

4. Array according to one of claims 1 to 3, characterized in that the heterogeneous catalysts and / or their precursors are full contacts or supported catalysts and / or their precursors and are present as a catalyst bed, tube wall coating or auxiliary support coating.

5. A method for producing arrays according to one of claims 1 to 4, comprising the following steps:

al) producing solutions, emulsions and / or dispersions of

Elements and / or element compounds of the elements present in the catalyst and / or catalyst precursor, and optionally of dispersions of inorganic support materials, - 36 -

a2) optionally adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic carriers into the solutions, emulsions and / or dispersions,

a3) simultaneous or successive coating of the channels of the

Bodies with the solutions, emulsions and / or dispersions, a predetermined amount of the solutions, emulsions and / or dispersions being introduced into each channel in order to obtain a predetermined composition, and

a4) optionally heating the coated body, optionally in the presence of inert or reactive gases, to a temperature in the

Range from 20 to 1500 ° C for drying and optionally

Sintering or calcining the catalysts and / or catalyst precursors.

6. A method for producing arrays according to one of claims 1 to 4, comprising the following steps:

bl) producing solutions, emulsions and / or dispersions of

b3) simultaneous or successive coating of catalyst supports present in the channels of the body with the solutions - 37 -

gen, emulsions and / or dispersions, a predetermined amount of the solutions, emulsions and / or dispersions being introduced into each channel in order to obtain a predetermined composition on the catalyst supports, and

7. A method for producing arrays according to one of claims 1 to 4, comprising the following steps:

cl) producing solutions, emulsions and / or dispersions of

c2) mixing predetermined amounts of the solutions, emulsions and / or dispersions and, if appropriate, of precipitation aids in one or more reaction vessels operated in parallel,

c4) coating one or more predetermined channels of the body with the mixture or several mixtures, - 38 -

c5) repetition of steps c2) to c4) for other channels of the

Body until the channels are coated with the respectively predetermined catalyst and / or catalyst precursor compositions,

c6) optionally heating the coated body, if appropriate in the presence of inert or reactive gases, to a temperature in the

Range from 20 to 1500 ° C for drying and optionally

Sintering or calcining the catalysts and / or catalyst precursors.

8. A method for producing arrays according to one of claims 1 to 4, comprising the following steps:

dl) preparing solutions, emulsions and / or dispersions of

^~ Elements and / or compounds of elements present in the catalyst and / or catalyst precursor chemical elements and optionally of dispersions of inorganic support materials,

d2) mixing predetermined amounts of the solutions, emulsions and / or dispersions and, if appropriate, of precipitation aids in one or more reaction vessels operated in parallel,

d4) coating catalyst carriers present in one or more predetermined channels of the body with the mixture or - 39 -

one or more of the mixtures,

d5) repeating steps d2) to d4) for other channels of the

Body until the catalyst carrier present in the channels of the body with the respectively predetermined catalyst and / or

Catalyst precursor compositions are coated,

9. The method according spoke 5 or 7, characterized in that the adhesiveness of the channels of the body before coating by chemical, physical or mechanical pretreatment of the inner walls of the channels or by applying an adhesive layer is increased.

10. A method for producing arrays according to one of claims 1 to 4, comprising the following steps:

el) production of different heterogeneous catalysts and / or their precursors in the form of full contacts with a predetermined composition,

e2) loading one or more predetermined channels of the

Bodies that are secured against falling out of the heterogeneous catalysts, each with one or more of the heterogeneous catalysts and / or their precursors with a predetermined composition. - 40 -

e3) optionally heating the body with the heterogeneous catalysts and / or their precursors in the channels, optionally in the presence of inert or reactive gases, to a temperature in the range from 20 to 1500 ° C. for drying and optionally

Sintering or calcining the catalysts and / or catalyst precursors.

11. A method for producing arrays according to one of claims 1 to 4, comprising the following steps:

fl) coating and optionally heating predetermined ones

Catalyst supports for the production of predetermined supported catalysts in the manner defined in claim 6 or 8 outside the body,

2) Introducing the supported catalysts into predetermined channels of the

Body,

O) optionally heating the filled body, optionally in

Presence of inert or reactive gases, to a temperature in the range from 20 to 1500 ° C. for drying and, if appropriate, sintering or calcining the catalysts.

12. The method according to claim 11, characterized in that the outer shape of the supported catalysts corresponds at least substantially to the shape of the channel interior in the body.

13. Array, obtainable by a method according to one of claims 5 to 12. - 41 -

14. A method for determining the activity, selectivity and / or long-term stability of the catalysts in an array according to one of claims 1 to 4 or 13, comprising the following steps:

gl) optionally activating the catalysts in the body,

g2) tempering the body to a desired reaction temperature,

g3) passing a fluid reactant or a fluid reaction mixture through channels in the body,

g4) discharge of the converted fluids from individual or several combined channels of the body,

g5) analysis of the discharged converted fluids,

15. The method according to claim 14, characterized in that after tempering the body to a first reaction temperature in step g2), steps g3) to g6) are carried out in succession for several different fluid reactants or fluid reaction mixtures, each with a flushing step with a flushing gas can be inserted, and then the

Body can be tempered to a second reaction temperature and the above reactions can be repeated at this temperature.

16. The method according spoke 14 or 15, characterized in that it is a gas or in the fluid reactant or fluid reaction mixture - 42 -

Gas mixture acts.

17. The method according to any one of claims 14 to 16, characterized in that the reaction is a gas phase oxidation.

18. The method according spoke 17, characterized in that a molecular oxygen-containing reaction mixture is used.

19. The method according spoke 6 or 8, characterized in that the adhesiveness of the catalyst carrier in the body before coating is increased by chemical, physical or mechanical pretreatment of the catalyst carrier or by applying an adhesive layer.

20. The method according to any one of claims 5 to 12 and 14 to 19, characterized in that the method is automated.