JP2002502697A - Combinatorial production and evaluation of heterogeneous catalysts - Google Patents

Abstract

  (57) [Summary] Heterogeneous catalyst comprising a body and / or said catalyst preferably having parallel through passages, wherein at least n said passages comprise n different heterogeneous catalysts and / or precursors of said catalyst A heterogeneous catalyst and / or a precursor of said catalyst, characterized in that n is 2, preferably 10, more preferably 100, particularly preferably 1000, very preferably 10,000. The method of producing the sequence comprises: a1) preparing a solution, an emulsion and / or a dispersion of the element and / or element compound corresponding to the component contained in the catalyst and / or the catalyst precursor; And, if necessary, a step of preparing a dispersion of the inorganic carrier material; a2) optionally, an adhesion promoter, a binder, a viscosity modifier, a pH adjuster in the solution, emulsion and / or dispersion. Adding a stabilizer and / or an inorganic carrier solid; a3) feeding a predetermined amount of said solution, emulsion and / or dispersion into each of the passages to obtain a predetermined composition; Simultaneously or successively coating said passages with said solution, emulsion and / or dispersion, and a4) optionally drying the catalyst and / or catalyst precursor and optionally sintering Or heating the coated body at a temperature in the range of 20 ° C. to 1500 ° C., optionally in the presence of an inert gas or a reactive gas, for firing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a method for combinatorial production and evaluation of heterogeneous catalysts and to the catalysts obtained by this method.

[0002]

[Prior art]

In addition to classical chemistry for the synthesis and study of individual substances, combinatorial chemistry for the synthesis and study of new chemicals has evolved. In this method, a large number of reactants are reacted by a one-pot synthesis, and it is analyzed whether or not the obtained reaction mixture exhibits desired properties, for example, pharmacological activity. If an activity was observed for a reaction mixture as described above, it was necessary in the next step to determine which particular substance in the reaction mixture was responsible for the activity. Determining the actual active compound is costly and it has been difficult to avoid adverse reactions on many reactants.

In another combinatorial synthesis method, a number of compounds were synthesized by performing a particular reaction with a number of reactants in a number of different reactions in a number of different reaction vessels. In this method, only one reaction product is present in each reaction vessel, for example, if pharmacological activity is observed for a mixture, so that the starting material used in the synthesis of the mixture is immediately known. Is preferred.

In addition to the relatively specific first application of combinatorial synthesis to the search for new pharmacologically active substances, recently, combinatorial synthesis has been applied to low molecular weight organic compounds and organic catalysts and inorganic compounds. It has been extended to the field of catalysts.

[0005] FM Menger et al. [Phosphatase Catalyst D
developed via Combinatorial Organic C
chemistry], J.M. Org. Chem. 60 (1995), 6666-6
667 discloses the synthesis of an organic catalyst by a combinatorial method. They conjugated carboxylic acids with eight different functional groups onto polyallylamine via amide bonds. In addition, different metal ions were attached to the polymer via complexation. The resulting polymer was studied for phosphatase activity. However, there is no description as to whether or not the catalyst was obtained by a production method based on automatic control. Only the preparation of the individual catalysts is described.

C. L. Hill and R.A. D. Gall [The first comb
inially prepared and evaluated i
organic catalysts. Polyoxometalates
for the aerobic oxidation of the mu
star analog tetrahydrothiophene (THT
)], J. et al. Mol. Catalysis A: Chemical 114 (1
996), 103-111, discloses a combinatorial production method and evaluation method of a polyoxometalate synthesized by mixing solutions of a desired metal salt at different ratios. They synthesized tungstate, molybdate and vanadate solutions in this way, as well as sodium hydrogen phosphate solutions. After preparing an appropriate solution, p
H was adjusted to a predetermined value to elicit a response. The resulting catalyst was used in dissolved form for the reaction. There is no description as to whether the catalyst production method is based on automatic control.

A special method is described in US Pat. No. 5,449,754 for introducing different amounts of various liquid reactants into an array of reaction vessels, for example similar to a dropping plate. In this method, a printer head of an ink jet printer connected to a storage solution of a reactant is moved on the above-mentioned arrangement by an XY positioner, and discharge of the liquid is controlled by a computer.

F. C. Moathes et al. [Infrared Thermographi
c Screening of Combinatorial Library
es of Heterogeneous Catalysts], Ind. E
ng. Chem. Res. 35 (1996) 4801-4803, discloses a series of heterogeneous catalysts containing substances obtained by applying different metal elements to aluminum oxide.
Discloses a method of screening. They studied the catalytic activity of the catalyst on the oxidation of hydrogen. Each catalyst was prepared by impregnating a solution of the appropriate metal salt with aluminum oxide pellets, drying and calcining. There is no description as to whether or not production was performed by automatic control.

[0009] They placed the different pellets in place on the support and contacted them with hydrogen under the reaction conditions. Since the catalyst generates heat when there is catalytic activity, it was possible to determine the active catalyst by measuring the heat generation using an infrared camera.

B. E. FIG. Baker et al. [Solution-Based Assembly.
of Metal Surfaces by Combinatorial
Methods], J. et al. Am. Chem. Soc. 118 (1996), 872
No. 1-8722 discloses a method for producing metal surfaces having different compositions by a combinatorial method. To this end, they dipped a silane-coated glass plate at a predetermined rate in a colloidal solution of gold to form a gold distribution gradient on the substrate. After the glass plate was pulled out and dried, the glass plate was rotated 90 ° and further immersed in a silver ion solution to form a silver concentration gradient on the plate. As a result, the composition on the surface changes continuously.

X. D. Xiang et al. [A Combinatorial Approac
h for Materials Discovery], Science 2 68 (1995), at 1738-1740, using physical shielding method and an evaporation method as a suitable metal deposition technique, BiSrCaCuO and YBaCuO superconductor on the substrate as a combinatorial array of different metal composition A method for forming a thin film is disclosed. After firing, different compositions of material appear at different locations in the array and can be studied, for example, by microprobes for conductivity.

[0012] WO 96/11878 provides, in addition to the method for producing an array of superconducting materials as described above,
Although it discloses a method for producing zeolites, here, a plurality of metal salt solutions,
Instead of pre-mixing, use the required amount of ink in each case and use an inkjet to introduce only the required amount on each type of dropping plate, and precipitate formation starts when the last solution is added I am trying to do it. BSCCO superconductors can also be synthesized by separately feeding by spraying the individual metal nitrate solutions required for synthesis onto a type of drip plate and further heating.

[0013] Various types of heterogeneous catalysts can be synthesized by known methods. However, methods for evaluating catalysts are complex and often cannot be performed under practical conditions, such as placing the reactants on the catalyst for the required residence time. This is because the catalyst is present on a relatively bulky and generally flat carrier, for example the reactants must be supplied as a gaseous mixture.

[0014]

[Problems to be solved by the invention]

An object of the present invention is to provide a method for producing an inorganic heterogeneous catalyst and an array of precursors of the catalyst, which can evaluate the obtained catalyst at low cost and under conditions similar to industrial methods. It is to be. In addition, it is to avoid the disadvantages of conventional methods. Also provided are sequences obtained corresponding to the method of the invention.

[0015]

[Means for Solving the Problems]

The object is that the object is to have preferably parallel through passages, wherein at least n of the passages comprise n different, preferably inorganic, heterogeneous catalysts and / or precursors of said catalysts. An array of heterogeneous catalysts and / or precursors of said catalysts, preferably composed of a body, preferably inorganic, wherein n is 2, preferably 10, more preferably 100, particularly preferably 1000, very preferably Has been found to be achieved by providing an arrangement of heterogeneous catalysts and / or precursors of said catalysts, which is characterized in that it is 10,000.

In one aspect of the invention, the body is a tube reactor or a heat exchanger and the passage is a tube.

In yet another form of the invention, the body is a block of solid material having a passage, for example in the form of a perforation.

The heterogeneous catalyst and / or catalyst precursor is preferably an unsupported catalyst or a supported catalyst and / or a precursor thereof, and is present as a catalyst layer, a tube wall coating layer or an auxiliary carrier coating layer. I do.

The phrase “arrangement of inorganic heterogeneous catalysts or precursors of said catalysts” is used herein to refer to the heterogeneous heterogeneous inorganic catalysts or precursors of said catalyst being spatially separated from one another in the body. Means a sequence that exists on a given area. The body preferably has parallel through passages, and is preferably a tube reactor or a heat exchanger. The geometry of the individual areas may be freely selected in this case. For example, the respective regions may be arranged in a line (quasi-one-dimensional) or may be arranged like a chessboard (quasi-two-dimensional). In the case of tube nest reactors or heat exchangers having a body with parallel through passages, preferably a number of tubes parallel to each other, the arrangement becomes clear when considering the cross-section perpendicular to the longitudinal axis of the tubes. . That is, in this case, the cross section of each tube is
This will form separate and distinct areas that are separated from each other. The above areas or tubes,
For example, a tightly packed arrangement of tubes having a circular cross section may be used. In this case, different columns will be arranged shifted from each other.

The phrase “body” refers to a three-dimensional object having a large number (at least n) of passages. The passage then connects the two surfaces of the body and passes through the interior of the body. The passages are preferably substantially, preferably completely, parallel to one another. In this case, the main body is made of a single material or a plurality of materials. The body may be of any suitable geometric shape. Preferably, it has two surfaces parallel to each other, each surface having one of the passage openings. The passage preferably runs perpendicular to these surfaces. Examples of this type of body include a parallelepiped or cylinder with a passage passing between two parallel surfaces. However, many similar geometries are possible.

The phrase “passage” refers to a portion passing through the interior of the body, connecting between two openings located on the surface of the body, through which fluid flows, eg, through the body. pass. Here, the passage may be of any desired geometric shape. The cross-sectional area may vary depending on the length of the passage, but preferably has a constant cross-sectional area. The cross-section of the passage may be, for example, an ellipse, a circle, and a polygon in which the line connecting the corners of the polygon is a straight or rounded line. Those having a circular or equilateral polygonal cross section are preferred. Preferably, all the passages contained in the body have the same geometric shape (cross section and length) and are arranged parallel to one another.

The terms “tube reactor” and “heat exchanger” refer to an arrangement of multiple tube-shaped passages collected in parallel. Here, the tube may have any desired cross section. The arrangement of the tubes is in a fixed spatial relationship with respect to each other, preferably the tubes are spatially separated from one another, and are preferably surrounded by a shell covering the entire tube. In this way, for example, a heating or cooling medium conducts heat through the interior of the shell,
The entire tube can be heated or cooled uniformly.

The phrase “block of solid material” means the body of solid material (which may be composed of single or multiple starting materials) with passages in the form of, for example, perforations.
The geometry of the passage (perforation) can be freely selected, as generally described above for the passage. The passages (perforations) do not need to be provided by drilling holes later, and can be used, for example, when forming a solid body / block by extruding an organic and / or inorganic compact (for example, suitable during extrusion). (Using a suitable mold shape). In the case of blocks, as opposed to tube reactors or heat exchangers, the body space between the passages is always filled with solid material. Preferably, the block is composed of one or more metals.

The phrase “predetermined” records the assignment of different catalysts or catalyst precursors to individual tubes, for example, to ensure that particular measurements are assigned to particular catalyst compositions; Later, many different catalysts or catalyst precursors are introduced into the tube reactor or heat exchanger in such a way that they can be searched later, for example, when confirming the activity, selectivity and / or long-term stability of the individual catalysts. Means to do. Preferably, the catalyst or precursor of the catalyst is synthesized by computer control and placed in different tubes of the tube reactor, the composition of each catalyst and the tubes in the tube reactor into which the catalyst or catalyst precursor is introduced. It is preferable to store the position of the file on a computer so that it can be searched later. Thus, the phrase "predetermined" is helpful in distinguishing the accidental or random assignment of generally different catalysts or catalyst precursors to tubes in a tube nest reactor.

The arrangement of the preferably inorganic heterogeneous catalysts or precursors of the catalysts of the present invention is synthesized by various methods.

The production method a) comprises the steps of: a1) preparing a solution, an emulsion and / or a dispersion of an element and / or element compound corresponding to the components contained in the catalyst and / or the catalyst precursor, and Optionally, preparing a dispersion of the inorganic carrier material, a2) if necessary, an adhesion promoter, a binder, a viscosity modifier, a pH modifier and / or the like in the solution, emulsion and / or dispersion. Or adding an inorganic carrier solid; a3) feeding a predetermined amount of said solution, emulsion and / or dispersion into each of said passages to obtain a predetermined composition, whereby said passage of said body is Simultaneously or successively coating with a solution, emulsion and / or dispersion, and a4) optionally drying the catalyst and / or catalyst precursor and optionally sintering or calcining To Optionally in the presence of an inert gas or reactive gas, at temperatures ranging from 20 ° C. to 1500 ° C., comprising, heating the body after coating.

The production method b) comprises the steps of: b1) preparing a solution, an emulsion and / or a dispersion of an element and / or element compound corresponding to the components contained in the catalyst and / or the catalyst precursor, and Optionally preparing a dispersion of the inorganic carrier material; b2) optionally an adhesion promoter, a binder, a viscosity modifier, a pH modifier and / or in said solution, emulsion and / or dispersion. Adding an inorganic support solid; b3) supplying a predetermined amount of said solution, emulsion and / or dispersion into each of the passages to form a predetermined composition on the catalyst support, Simultaneously or successively coating the catalyst support present in the passage of the above with the solution, emulsion and / or dispersion, and b4) optionally drying the catalyst and / or catalyst precursor; Must The body containing the coated catalyst carrier in the passage is heated at a temperature in the range of 20 ° C. to 1500 ° C. in the presence of an inert gas or a reactive gas as required to sinter or calcine according to Heating.

The production method c) comprises: c1) preparing a solution, an emulsion and / or a dispersion of an element and / or element compound corresponding to a chemical component contained in a catalyst and / or a catalyst precursor, and Preparing a dispersion of an inorganic carrier material according to: c2) a predetermined amount of said solution in one or more parallel operated reaction vessels;
Mixing the emulsion and / or dispersion and, if necessary, a precipitating aid; c3) optionally, an adhesion promoter, a binder, a viscosity modifier in the resulting mixture,
adding a pH adjuster and / or an inorganic carrier solid; c4) coating one or more predetermined passages of the body with one or more of said mixture; c5) predetermined catalysts and / or catalyst precursors. Repeating steps c2) to c4) for the other passages of the body until the passages containing the respective body composition are completed; c6) optionally drying the catalyst and / or catalyst precursor Heating the coated body at a temperature in the range of 20C to 1500C, optionally in the presence of an inert gas or a reactive gas, for sintering or firing, including.

The production method c) comprises the steps of: c1) preparing a solution of an elemental compound corresponding to a chemical component present in the catalyst other than oxygen, and, if necessary, preparing a dispersion of an inorganic carrier material; c2 Mixing) a predetermined amount of solution or dispersion and, optionally, a precipitating aid in a single or a plurality of parallel operated reaction vessels, while precipitating the chemicals present in the catalyst; c3) If necessary, an adhesion promoter, a binder, a viscosity modifier, and the like in the obtained suspension.
adding a pH adjusting agent and / or an inorganic carrier solid; c4) coating one or more predetermined tubes of a tube reactor or heat exchanger with the suspension; c5) respectively a predetermined catalyst composition Repeating steps c2) to c4) on different tubes of the tube nest reactor or heat exchanger until the tubes containing the material are coated, c6) optionally drying the catalyst and / or catalyst precursor In order to sinter or calcine as required, an inert gas or a reactive gas is optionally present at a temperature in the range of 20 ° C. to 1500 ° C., and the coated tube reactor or thermal Heating the exchanger.

The production method d) comprises the steps of: d1) preparing a solution, an emulsion and / or a dispersion of an element and / or element compound corresponding to a chemical component contained in a catalyst and / or a catalyst precursor, and Preparing a dispersion of an inorganic carrier material according to: d2) a predetermined amount of said solution in one or more parallel operated reaction vessels;
Mixing the emulsion and / or dispersion and, if necessary, a precipitating aid, d3) optionally, an adhesion promoter, a binder, a viscosity modifier in the resulting mixture,
adding a pH adjuster and / or an inorganic carrier solid; d4) coating the catalyst carrier present in one or more predetermined passages of the body with one or more of said mixture; d5) body (Preferably all) of the catalyst carriers present in the passages of the above, until the coating with the respective predetermined (generally different) composition of the catalyst and / or the composition of the catalyst precursor is completed, Repeating steps d2) to d4) on the catalyst carrier (generally not yet coated); d6) drying the catalyst and / or catalyst precursor, if necessary, Heating the body containing the coated catalyst support in a passage at a temperature in the range of 20 ° C. to 1500 ° C., optionally in the presence of an inert gas or a reactive gas, for sintering or firing; including .

In this process, the adhesion of the body passages (for example the inner surface of the tube) or the catalyst carrier is determined by applying a chemical, physical or mechanical pretreatment to the inner walls of the passages (for example the inner tube) before coating. It can be increased by applying or by providing an adhesive coating.
This step applies in particular to processes a) and c), and b) and d), respectively.

The process e) comprises: e1) producing different heterogeneous catalysts and / or precursors of said catalysts in the form of unsupported catalysts having a predetermined composition; e2) preventing the heterogeneous catalysts from falling off In each of the single or multiple predetermined passages of the body, a heterogeneous catalyst having a single or multiple predetermined compositions and / or
Or filling the respective precursors of the catalyst, e3) optionally drying the catalyst and / or catalyst precursor and optionally sintering or calcining, if necessary with an inert gas or Heating the body containing the heterogeneous catalyst and / or a precursor of the catalyst in a passage at a temperature in the range of 20C to 1500C in the presence of a reactive gas.

The production method f) includes the steps of: f1) coating a predetermined catalyst support and heating as necessary to produce a predetermined supported catalyst by the above-mentioned method outside the main body; f2) Supported catalyst Into a predetermined passage of the body, f3) optionally drying the catalyst and optionally sintering or calcining the presence of an inert gas or a reactive gas as required. And 20 ℃ ~ 1500 ℃
Heating the filled body at a temperature in the range of.

Here, it is preferred that the external shape of the supported catalyst corresponds at least substantially, preferably almost or completely, to the internal shape of the passage in the body.

The present invention also relates to an arrangement of the inorganic heterogeneous catalyst obtained by any of the above methods. This sequence can also be synthesized by a combination of the methods described above.

The above method is described, for example, in G. Ertl, H .; Knoezinger and J.M. W
Edited by Eitkamp [Handbook of Heterogeneo
us Catalysis], Wiley-VCH, Weinheim, 199
7 are suitable for the synthesis of a number of catalysts.

In addition, the present invention provides: g1) activating the catalyst in the body as required; g2) heating or cooling the body to a desired reaction temperature; g3) a fluid reactant or fluidity Passing the reaction mixture through (one, multiple, or all) passages in the body; g4) collecting the reacted fluids individually from the passages in the body or from a plurality of passages, preferably Separately) discharging; g5) analyzing (preferably separately) the discharged reaction fluid; g6) comparing and evaluating the analysis results of a plurality of analyzes as necessary. It relates to a method g) for determining the catalytic properties of the catalysts described above or below in the arrangement, in particular the activity, selectivity and / or long-term stability of the catalyst.

As a preferred variant of the production method, after heating or cooling the body to the first reaction temperature in step g2), steps g3) to g6) are carried out for a plurality of different flowable reactants or flowable reaction mixtures. A continuous method is exemplified. At this time, after each purging step with a purge gas, the main body may be heated or cooled to a second reaction temperature and the reaction may be repeated at this temperature.

At the beginning of the analysis, gas flows from the entire array can be collected and the collected gas analyzed to see if any reaction has taken place overall. Thereafter, if a reaction has occurred, the harvest from individual tubes or from multiple tubes can be analyzed to determine the best catalyst with a minimum number of analytical steps.

The fluid may be passed through individual tubes, or multiple tubes or all tubes may be combined and passed through the fluid.

Preferably, the flowable reactant or flowable reaction mixture is a gas or a mixture of gases.

The present invention provides an automated process for screening a large number of heterogeneous catalysts for chemical reactions, especially gas phase reactions, especially partial oxidation of hydrocarbons in the gas phase with oxygen molecules (gas phase oxidation). And catalyst evaluation.

Reactions suitable for study are described in Ertl, H .; Knoezinger and J.M. W
Edited by Eitkamp [Handbook of Heterogeneo
us Catalysis], Wiley-VCH, Weinheim, 199
7. Examples of suitable reactions are mainly described in volumes 4 and 5 of this document,
Nos. 2, 3 and 4.

Examples of suitable reactions include decomposition of nitrogen oxides, synthesis of ammonia, oxidation of ammonia, oxidation of hydrogen sulfide to sulfur, oxidation of sulfur dioxide, direct synthesis of methylchlorosilane, petroleum refining, oxidation of methane Coupling, methanol synthesis, hydrogenation of carbon monoxide and carbon dioxide, conversion of methanol to hydrocarbons, catalytic reforming, catalytic cracking and hydrocracking, coal gasification and liquefaction, fuel cells, heterogeneous photocatalysts, M
Synthesis, Isomerization, Alkylation, Aromatization, Dehydrogenation, Hydrogenation, Hydroformylation, Selective or Partial Oxidation, Amination, Halogenation, Aromatic Nucleophilic Substitution, Addition and Deprotection of TBE and TAME Elimination reactions, oligomerization and metathesis, polymerization, enantiodiscriminating catalysis and biocatalysis.

The present invention is described in more detail below with reference to preferred embodiments.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION

Preparation of an array of inorganic heterogeneous catalysts First, two or more, preferably ten or more, more preferably 100 or more, particularly preferably 1000 or more, very preferably 10,000 or more selected periodic table of elements. Is prepared in the form of a solution, an emulsion and / or preferably a suspension (dispersion). At this time, a mixed solution is generally prepared by changing the chemical composition or concentration. In order to evaluate reproducibility, a plurality of liquid mixtures having the same composition can be used.

The mixture generally contains a liquid chemical component that is used as a solvent, emulsifier or dispersant with respect to the other components in the mixture. As a solvent or a dispersant, an organic solvent, an emulsifier and / or water is used, and water is preferably used.

In addition to the chemical components which are solvents or dispersants, the mixture may comprise one or more, preferably 2
It generally contains more than one, especially preferably three or more chemical components, but does not contain each of the fifty or more chemical components in an amount of 1% by weight or more. The chemical components are preferably present in a very well-mixed mixture, for example, a mixture of various miscible solutions,
It is preferably present in the form of an emulsion with a small droplet size and / or a suspension containing said chemical components, generally in the form of a fine precipitate (eg a chemical precipitate). The use of sols and gels, especially sols and gels containing the above-mentioned chemical components which are almost homogeneously dispersed, is effective, and sols and gels which exhibit favorable adhesion and flow properties for coating are preferred. Suitable starting compounds for the selected chemical element include in principle preferably the finely divided element itself, as well as converting the selected chemical element into a suitable form, for example, oxides, hydroxides, hydroperoxides, inorganic salts , Preferably nitrates, carbonates, acetates and oxalates, organometallic compounds,
All compounds included in the form of alkoxide and the like can be mentioned. The respective starting compounds can be used in solid form and in the form of solutions, emulsions and / or suspensions.

In particular, the metal compound having catalytic activity is preferably a water-soluble oxide, hydroxide or a salt of an organic or inorganic acid. Active metals belong to the subgroups of the Periodic Table of the Elements, for example, metals active as oxidation catalysts belong to the fifth and sixth subgroups, and metals active as hydrogenation catalysts belong to the platinum group. The method according to the invention allows the screening of (irregular) components, in particular metals or metal oxides, which are not considered to be catalytically active in advance.

In addition, the mixture separately affects compounds that affect the adhesion and flowability of the mixture on the inner surface of the passages and tubes to be coated or on the catalyst carrier, and thus affect the coatability of the mixture. May be included. Here, as an organic compound, for example, DE
-Ethylene glycol or glycerol as disclosed in A 442 346,
Alternatively, a maleic acid copolymer can be used, and examples of the inorganic compound include SiO ₂ , an organic silicon compound, and siloxane.

Further, the mixed solution contains a known inorganic carrier 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. These generally increase the surface area that is correlated with the catalysis of the catalytically active chemical component present in the mixture, and may also affect the catalytic properties of the active composition present, It may also affect the adhesiveness and fluidity of the resulting mixture. In general, in this case, a coating is obtained which contains the preferred oxide, nitride and carbide support materials in addition to the actual catalytic material. However,
While mixing these components, or subsequently heating the coating, the carrier material may react with the chemical components used on the carrier to form new solid materials.

In addition, the mixture used may be an inorganic substance that stabilizes the mixture used and / or
Or it may contain an organic binder or a mixed binder. Suitable binders in this case include, for example, binders or mixed binders comprising metal salts, metal oxides, metal hydroperoxides, metal hydroperoxide-phosphates and / or eutectic compounds which melt at the operating temperature of the catalyst. Can be

Further, the mixture can be adjusted to a predetermined pH range by adding an acid and / or a base. In many cases, a suspension exhibiting a neutral pH is used. For this purpose, it is effective to adjust the mixture to a pH between 5 and 9;
It is preferred to prepare during. In the process according to the invention, special results are obtained with low-viscosity mixtures having a solids content of up to 95% by weight, preferably 50-80% by weight. If the precipitation is insufficient, a precipitation aid such as, for example, ammonia may be added.

In a preferred form of the invention, the mixture is stirred after and generally during the preparation of the mixture and its flow properties are measured continuously, at least at the end of the preparation. This is done, for example, by measuring the power consumption of the stirrer. With this assay, the adhesion is best and the inner wall of the tube to be coated or the auxiliary carrier to be coated (
The viscosity of the suspension can be adjusted, for example by adding further solvents or diluents, in order to optimize and uniform the layer thickness on the catalyst support).

[0055] In principle, the invention is not limited to a certain catalyst substance or catalyst composition. The preparation of the mixture can be carried out in parallel or in succession, generally by automatic control, for example by an automatic pipette or an automatic pipetting device or else for example US 544
This is performed using an ink jet system as described in US Pat.

When coating the tubes of a tube reactor or a heat exchanger according to variant a), it is also possible to simultaneously supply a solution, an emulsion or a suspension containing the element or the elemental compound into the tubes. They can also be supplied separately and continuously. Simultaneous feeding can be effected, for example, using an ink jet printer head, which is provided separately and connected to the solution, emulsion or suspension, and which is modified to allow simultaneous spraying. Compared to this deformation method a), the deformation method b) is particularly preferably carried out as follows.

To produce the catalyst or a precursor of the catalyst, solutions, emulsions and / or suspensions of the required elements are first prepared in separate vessels. These liquors are often metal salt solutions, for example nitrates. The required amount of each solution to produce the catalyst or catalyst precursor is transferred at a predetermined ratio to another small reaction vessel and the components are mixed vigorously.
The liquid can be transferred using, for example, an automatic pipette or an inkjet device. When the components are mixed, the components react or precipitate. The use of a precipitation aid, such as ammonia, can often induce precipitation and, if necessary, complete the precipitation, such that a suspension of the mixed catalyst precursor is obtained.

The suspension has such a viscosity that it is easy to feed into the tubes of the tube reactor and that the distribution of the catalyst or catalyst precursor on the inner wall of the tubes is as uniform as possible and easy to adhere. It is preferable to adjust the viscosity of the suspension to a desired value as described above by adding further additives as necessary. In this case, the suspension can be removed from the reaction vessel, for example using a pipette, and distributed in the tube by the injection or spray method described below. In this case, the reaction vessel may be completely or partially emptied. Multiple reaction vessels may be operated in parallel, and one reaction vessel may be partially emptied to change composition before being filled with other components.

The prepared mixture is preferably injected by injection, in particular at various sites in a metal tube reactor or heat exchanger, in particular on the inner wall of a (preferably metal) reaction tube of a tube nest reactor. Coating is performed with a layer thickness of 10 to 2000 μm. At this time, each tube is generally coated with a mixed solution having a different composition. use).

To evaluate the effect of layer thickness (such as transport effect), the same catalyst composition can be applied to different tubes at different layer thicknesses.

In a further variant of the invention, after or preferably before insertion into the reaction tube of the tube nest reactor, the auxiliary carrier coated with the mixture (preferably a metal or ceramic tube) ).

Auxiliary carriers which can be used here are tubes having the desired cross section, preferably a circular cross section. The auxiliary carrier material can be freely selected, for example, the auxiliary carrier may be glass,
It may be made of metal, ceramics such as pyroceram, activated carbon, graphite or sintered quartz. The material in this case may be sintered densely or may be porous. The tube in this case may be divided into a plurality of passages extending in a direction parallel to the longitudinal axis of the tube, preferably a plurality of passages parallel to one another. The cross section of such a tube is
For example, it may resemble a spoke wheel. The outer tube and the inner tube may be connected by a large number of through spokes.

The number of spokes can be freely selected here.

As a porous material, the auxiliary carrier may preferably consist of a solid with a high porosity. For example, it may be composed of a foam of the above material. The solid body may be of any suitable shape desired. Suitable shapes include, for example, a column, a cone, a disk, and a plate.

A preferred auxiliary carrier is, for example, ROB at D-57644 Hattart
As a sintered filter from U Glassfilter-Geraete, D-
PoroCer Keramikmem, 07629 Hermsdorf
D-07629 Herms as a tubular membrane for cross-flow filtration from Braen
Alfred NY 1480 as a ceramic tubular membrane for cross-flow filtration from Tami Deutschland, Dorf / Thuringingen.
2 Hi-Tech Ceramics, a Vesuvius, USA
It is provided as RETICEL ceramics by Group.

Examples of the porous auxiliary metal carrier include sintered metal, metal gauze, metal woven fabric, metal felt or wire mesh. From a reaction point of view, metals are very effective in terms of thermal conductivity, especially when large amounts of heat must be removed or when precise temperature control is required.

Suitable porous activated carbon and graphite auxiliary carriers are known.

The sequences according to the invention are preferably produced using this type of auxiliary carrier according to method f) described above. In this method, the auxiliary carrier is preferably coated outside the body,
Heat as needed. After the thus-produced supported catalyst is inserted into the predetermined passage of the main body, the inserted main body is heated to dry the catalyst and, if necessary, to sinter or calcine it. The above-mentioned supported catalysts may here have auxiliary carriers as catalyst carriers.

The method of coating the body or a suitable heat exchanger is described in more detail below.

The part coated with the previously prepared mixture in the preferably metallic heat exchanger is preferably the inner tube wall of a metallic tube nest reactor. The reaction tubes of the tube reactor can have any desired cross-section, but generally have a generally circular, especially circular, cross-section. The inner diameter is preferably in the range from 0.2 to 70 mm, preferably in the range from 1 to 25 mm, particularly preferably in the range from 3 to 10 mm. 300 tube reactors
Up to about 00, preferably 10 to 20,000, particularly preferably 100 to 10
It can contain 000 reaction tubes, which are generally provided with coatings of different composition.

The coating with the mixed solution can be applied by a wiping method, a slurry method, a brush application method, a centrifugal separation method, a spraying method and / or a dipping method. In addition, the mixture is poured into individual tubes and rotated at a speed of 200-1000 rpm, preferably 300-800 rpm.
Centrifugation may be performed at rpm. In a preferred form, the coating on the inside of the reaction tube is
It is manufactured by spraying the above mixture. In this process, the sprayed mixture is pushed into the irregularities on the surface of the substrate, which prevents air bubbles from remaining under the coating layer. Therefore, the used liquid mixture can be sufficiently adhered to the inner surface of the sprayed tube. However, especially when the adhesion and / or viscosity of the mixture is low,
Part of the mixture can be dripped and drained again. For example, the auxiliary carrier in the form of an inner tube may be completely covered or partially covered. In this case, it is possible to ensure that the inlets and outlets of the respective reaction tubes are not covered, in particular by means of suitable devices, in order to avoid later a problem of airtightness in the connection with the supply and discharge devices of the fluid. It has been found that spraying the mixture into a pre-heated tube or feeding the mixture by dipping into a pre-heated tube can provide useful coatings. For this purpose, before spraying the suspension, the metal body is heated to 60-500 ° C.
, Preferably in the range from 200 to 400 ° C., particularly preferably in the range from 200 to 300 ° C., and coating at this temperature with the first-mentioned mixture. In this case, most of the volatile components in the mixed solution evaporate, and a thin layer of the catalytically active metal oxide having a layer thickness of preferably 10 to 2000 μm, particularly preferably 20 to 500 μm, is formed on a metal body preferably. Is done. This type of manufacturing process applies, for example, the part of the method disclosed in DE-A-2510994 in which the mixture is not applied to a pre-heated carrier, but to a pre-heated, preferably metal body. To be performed.

To form a particularly thick layer or a particularly uniform coating layer, the reaction tube can be continuously and repeatedly coated. In this case, during the coating stage of each reaction tube,
A drying stage and / or a firing stage and / or a sintering stage can be provided. In the case of the spraying method, it is advantageous if the inner wall is coated using a single or multiple spray sprays, preferably single or multiple mobile spray sprays. In this case, during the spraying process, the spray spray is moved through the tube to be coated at a fixed or variable speed, for example using an automatic device.

After drying and, if necessary, sintering or calcining, the thickness of the applied layer is 10-
The range of 2000 μm is preferred, and the range of 20 to 500 μm is particularly preferred.

In addition, before coating the inner tube, an adhesion promoter can be applied, and subsequently a catalytically active coating layer containing a catalytic substance may be provided over the adhesion promoter. The adhesion promoter increases the adhesion of the catalytically active coating on the inner tube. In addition, the use of an adhesion promoter increases the service life. Suitable adhesion promoters are described above.

Furthermore, the adhesion of the catalyst layer can be increased by pretreating the inner tube chemically, physically or mechanically before coating. As a chemical pretreatment method, for example, the inner tube can be treated with an alkali solution or preferably an acid. Moreover, the inner tube can be roughened by blowing off a drying fluid, in particular corundum or quartz sand, to enhance the adhesion. Moreover, polishing liquids, which are suspensions of hard particles, for example liquids in which corundum is dispersed in a dispersion medium, have also proven useful.

Furthermore, the coating layer on the inner tube, preferably made of metal, is for example DE-A-19600
And a catalytically active coating layer comprising an auxiliary carrier and a catalytic material as disclosed in US Pat. In this case, the auxiliary carrier preferably has an external shape which at least approximately corresponds to the geometry of the surface to be coated. Suitable auxiliary carriers here are, for example, those made of metal or ceramic, such as wire mesh or metal or ceramic tubes. In this case, at least the auxiliary carrier, preferably only the auxiliary element, is covered with a catalytically active coating layer, and the auxiliary carrier covered with the coating layer is disposed in the entire reaction inner tube or preferably in a part of the reaction inner tube. . In the arrangement in which the tube is arranged in this tube, the outer tube is tapered at one end, for example, to prevent the inner tube from falling off, and at the other end, the intended inner tube is, for example, a spring or elastic material. It may be pushed into the outer tube.

A feature of the process of the invention is that each auxiliary carrier in the tube reactor used generally has a different composition or a different thickness of the catalyst coating layer. Moreover, the coated auxiliary carrier can be easily exchanged for another auxiliary carrier having a different coating layer. For example, by employing a suitable reactor configuration (e.g., equipped with a shut-off valve), it is possible to exchange individual auxiliary carriers during the operation of the reactor.

The coated tube reactor is placed in a temperature range of 20 to 1500 ° C., preferably 60 to 1000 ° C., particularly preferably 200 to 600 ° C., particularly preferably 250 to 500 ° C. in a vacuum or a predetermined atmosphere. Upon heating, the previously applied coating dries and preferably loses the aqueous solvent. Moreover, at elevated temperatures, sintering or firing of the particles forming the coating layer may occur. At this stage, the actual catalytically active coating is generally obtained.

To adjust the temperature, it is preferable to surround the reaction tube with a heat transfer medium such as a molten metal or molten salt of Ga or Na. In this case, the melt is preferably pumped from the opposite side of the tube reactor to pass the molten heat transfer medium through a heat exchanger (eg, air cooled) for the purpose of transferring or removing heat. Supply and remove the heat transfer medium. The heat transfer medium firstly maintains the inside of the reaction tube at the drying temperature of the coating layer, the sintering temperature of the coating layer following the drying, and the subsequent reaction test temperature of the fluidized bed. Second, the heat transfer medium removes the heat generated in subsequent reaction tests, thus suppressing the formation of hot spots on the catalyst coating that would be locally hotter than the rest of the catalyst coating. .

According to this type of reaction process, the heat generated in the reaction is removed very well and virtually no hot spots are generated anymore.

In yet another form of the invention, the space between the reaction tubes is filled with a solid material, preferably a metal or a solid metal alloy. In this case, the tube reactor is turned into a block of material as described above, in particular a metal block with passages or perforations.
In this case, the inner diameter of the perforation corresponds to the inner diameter of the functional tube of the tube nest reactor.

The different heterogeneous catalysts having a given composition are prepared in the form of unsupported or supported catalysts using known methods, for example the combinatorial method, and are used in tube reactors or heat exchangers. It is also possible to supply the previously prepared heterogeneous catalyst to each of the single or plurality of predetermined tubes, or to each of the tubes or auxiliary carriers disposed therein. In this case, a known shape can be used. For each individual tube, the height of the catalyst layer or the content of inert components of the layer can be varied, and the parameters of the layer can be set separately. After this,
The tube filled with the supported catalyst which has been subjected to the drop-prevention measures is placed in an actual tube nest reactor.
This simplifies the replacement of individual catalyst fillers.

The catalyst is evaluated by reacting a flowable reactant or reaction mixture, which is generally liquid and preferably gaseous. The oxidation catalyst is a polymer of one or more saturated organic, unsaturated organic, or unsaturated compounds, in parallel, or sequentially, in individual, multiple or all tubes of the tube reactor after coating. Organic starting materials (eg, hydrocarbons, alcohols, aldehydes, etc.), oxygen-containing gases (eg, air, O ₂ , N ₂ O, NO, NO ₂ , O ₃ ) and / or, for example, H ₂ Correspondingly with an inert gas (e.g. nitrogen or a noble gas) at a temperature in the range from 20 to 1200C, preferably from 50 to 800C, particularly preferably from 80 to 600C,
It is preferred to evaluate the individual gas streams from individual, several or all tubes of the tube nest reactor, separately or in parallel, by means of a suitable device.

For example, from oxygen-containing gases (eg, air, O ₂ , N ₂ O, NO, NO ₂ , O ₃ ) and / or H ₂ and organic starting materials that react therewith (eg, propene or o-xylene) The resulting gas mixture is passed, for example, through a reaction tube having a generally different coating layer of a tube reactor. In addition to the above gaseous substances, other gaseous substances such as substances containing Cl or P may be present. At this time, the gas mixture may be continuously passed through individual reaction tubes. In a preferred form, the gas mixture is passed through the reaction tube such that the gas mixture flows through all tubes simultaneously. In this case, at the beginning of the reaction, i.e. while the coating of the catalyst is active, the composition of the feed, the temperature of the heat transfer medium or the reaction tube, the residence time of the feed in the tube reactor and / or the total gas The pressure can be changed. The product gas discharged from each reaction tube generated by the reaction of the used reaction gas is generally collected separately, but may be collected as a whole.For example, the composition of the collected gas may be measured using various probes or analytical methods. Analyze with.

After coating with the suspension directly (omitting the drying and sintering or firing steps), the gas mixture may be fed to the coated tube reactor, in which case the drying step and the The subsequent sintering step takes place in the presence of the above-mentioned gas mixture. In this case, the composition of the coating layer of the inner tube can be changed. In particular, oxygen can be partially or completely released to the oxidizing coating layer under highly reducing conditions, and oxygen can be incorporated into the structure of the coating layer under highly oxidizing conditions. .

The reaction tubes provided with the different coating layers of the drying reactor are supplied with a gas mixture via a gas feed hood, which can be fitted, for example, in such a way that the tube reactor can be kept substantially airtight. Can be supplied.

The gas used may be mixed before it is introduced into the gas supply hood, for example using a static mixer, or may not be mixed until it is introduced.

The gas after the individual reaction can be collected via a device which is substantially airtightly mounted on the tube reactor, wherein individual, several or all reaction tubes are provided. Can be separately collected by opening and closing the valve and separately analyzed.

Other methods of separately extracting individual exhaust gases from each of the reaction tubes, which typically have different coating layers, include, for example, mechanically operated under computer control.
A suction device ". The device has a suction tube for sampling the gas, which is positioned just above, in or above the outlet of each reaction tube, essentially by automatic control, the reaction The subsequent adjustment of the position of the suction tubes and the sampling of each post-reaction gas means that only the actual post-reaction gas to be analyzed later enters the suction tube and is taken from the outside. When the suction device is adjusted just above the end of the reaction tube, for example, by pressing the suction device against the end face of the reactor, it is preferable to carry out the reaction. It is effective to essentially maintain the gas tightness between the end and the suction tube.If the suction device is positioned in or above the outlet of each reaction tube, other external gas may flow into the suction tube. Amount of gas after reaction sucked so as not to be drawn It is effective to restrict the pressure of the suction tube to a reduced pressure, and to suck the gas after the reaction into the suction device.If the suction tube is positioned in the outlet of each reaction tube, the end of each reaction tube is effective. It has been found to be particularly effective to taper the end of the suction tube so that the gas after reaction discharged from the reaction tube is hermetically shut off from the outside by inserting the suction tube into the reaction tube. After the subsequent gas has been withdrawn from said reaction tube of the tube reactor, the suction device is preferably automatically controlled by means of another reaction tube, generally just above, in or above the outlet of the next reaction tube. The position is adjusted so as to collect the next gas.In this way, the exhaust gas from all the reaction tubes can be separately sampled and analyzed. Place the suction device directly above, inside, or In addition to being able to adjust the position of the suction tube, the suction tube can be fixed during the position adjustment and the tube nest reactor can be moved correspondingly. In a preferred variant, the tube nest reactor is fixed and only the suction device is moved in the direction of or towards the end of each reaction tube during the alignment. Rotating the nest reactor around the axis of the reactor during position adjustment, and linearly moving the suction tube in the direction toward the rotation axis of the tube nest reactor when adjusting the position above the end of each reaction tube, When adjusting the position just above the end of the reaction tube, the suction device is moved in a direction parallel to the axis of the reactor, and a plurality of suction devices may be used simultaneously to collect various post-reaction gases. Collect and collect gas from multiple tubes .

In a similar manner to collecting gas via a tube named suction tube, instead of a gas supply hood, the individual tubes to be evaluated can be continuously supplied with gas on the same principle. . Obviously, the exhaust gas suction pipe must be aligned with the fresh gas supply pipe.

The catalytic properties of the individual catalyst coating layers of the individual reaction tubes can be screened by chemical analysis of each gas stream using suitable methods known per se. The gas streams taken individually from the individual reaction tubes of the tube nest reactor are individually separated in this case by a suitable device such as, for example, gas chromatography using a flame ionization detector and / or a thermal conductivity detector. Alternatively, the gas composition is analyzed using mass spectrometry. The resulting gas composition is in particular here the relative content of one or more desired products,
Analyzes are made in terms of the concentrations of the starting materials and the associated products before the reaction, the respective conversions (activity) and the selectivity of the products formed. In this case, it is often effective to measure the selectivity of the products of the individual catalysts over a relatively long period of time, generally from hours to weeks. To select the most suitable catalyst coating for each reaction while limiting the number of gas analyses, select a reaction tube that exceeds the desired critical concentration or selectivity for certain products. It is effective to repeatedly measure the gas composition of the reaction tube.

After catalyst evaluation, the catalyst coating in the applied tube can be removed in order to replace the fresh catalyst coating and use the remaining tube nest reactor again.

The catalytic coating is obtained by removing at least most of the old catalytically active coating and forming a new catalytically active coating by wiping, brushing, centrifuging, spraying and / or dipping. Can be updated. For convenience, the same coating method used to produce the previously removed catalyst coating can be selected. Old catalytically active coatings can be removed in a particularly simple manner, for example by blowing them off with corundum, silicon carbide, fine sand and similar fluids.
Alternatively, the use of steaming and chemical cleaning methods has been found to be effective.

For example, as a method of removing the inner coating layer after the evaluation of the catalyst, a brush tool similar to a bottle washing brush can be generally used in combination with the above polishing liquid. It is preferred to remove the inner coating layer at least almost automatically by a controlled method.

[0095] The method of the present invention can be easily performed by automation control by automation control. The tubes coated with catalyst ensure that the fluid flows optimally so that only low pressure drops occur and clogging in the individual reactor tubes of the tube reactor is prevented.

If the coating layers to be evaluated are spatially separated and clearly assigned, a large number of substances, generally corresponding to the number of tubes, can be obtained using one device (tube nest). There is an advantage that evaluation can be performed simultaneously in parallel, at low cost and in a short time.

In addition, compared to other systems, such as, for example, perforated plates and CVD arrays, tube reactors have the advantage that they can be evaluated in a manner as close as possible to the industrial process (the capacity can also be scaled up). ). In particular, industrially relevant optimizations can be carried out very quickly and economically, since a large number of catalysts can be evaluated in parallel / simultaneously under the same conditions.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] February 3, 2000 (200.2.3)

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[Correction target item name] Claim 1

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──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AU, BG, BR, BY, CA, CN, CZ, GE, HU, ID, IL, IN, JP , KR, KZ, LT, LV, MX, NO, NZ, PL, RO, RU, SG, SI, SK, TR, UA, US (72) Inventor Demut, Dirk Germany, D-68161, Mannheim, Free Drichling, 14 (72) Inventor Chute, Ferdy Germany, D-61440, Oberursel, Darbigsbergstrahl S, 24 (72) Inventors Schunk, Stephan, A Germany, D-69115, Heidelberg, Kaiserstrasse, 59 F-term (reference) 4G069 AA02 AA03 AA08 BA01A BA02A BA04A BA05A BA06A BA08A BB04A BB11A BB15A BC40 EA05 FA02 FA03 FB05 FB06 FB14 FB16 FB17 FB18 FB30 FB57 FB77 FB78 FB80 FC07 FC09 4G075 AA02 BA05 BA10 BD15 BD16 CA02 CA54 CA66 EB21 EB50 EC07 FB03 FB04 FB06 4H006 AA05 AC90

Claims (20)

[Claims] 1. A heterogeneous system comprising a body, preferably having parallel through passages, wherein at least n of said passages comprise n different heterogeneous catalysts and / or precursors of said catalysts. An array of catalysts and / or precursors of said catalysts,
An arrangement of heterogeneous catalysts and / or precursors of said catalysts, characterized in that n is 2, preferably 10, more preferably 100, particularly preferably 1000, very particularly preferably 10,000. 2. The arrangement according to claim 1, wherein the heterogeneous catalyst is an inorganic heterogeneous catalyst. 3. The method according to claim 1, wherein the body is a tube nest reactor or a heat exchanger, and the passage is a tube, or the body is a block made of a solid material having a passage. The sequence according to claim 1 or 2. 4. The heterogeneous catalyst and / or a precursor of the catalyst is an unsupported catalyst or a supported catalyst and / or a precursor thereof, and these are a catalyst layer,
4. The coating composition according to claim 1, wherein said coating is present as a tube wall coating or an auxiliary carrier coating.
3. The sequence according to any of 3. 5. A solution, an emulsion and / or a dispersion of an element and / or an elemental compound corresponding to the components contained in the catalyst and / or the catalyst precursor are prepared, and if necessary, Preparing a dispersion of an inorganic carrier material, a2) optionally, an adhesion promoter, a binder, a viscosity modifier, a pH modifier and / or an inorganic carrier in the solution, emulsion and / or dispersion. Adding a solid; a3) introducing a predetermined amount of said solution, emulsion and / or dispersion into each of the passages to obtain a predetermined composition, thereby allowing the passage of the body, said solution, milk, Simultaneously or sequentially coating with the suspension and / or dispersion, and a4) if necessary, drying the catalyst and / or catalyst precursor and, if necessary, sintering or calcining In response to the Heating the coated body at a temperature in the range of 20 ° C. to 1500 ° C. in the presence of an active gas or a reactive gas. How to make the array. B1) preparing a solution, emulsion and / or dispersion of an element and / or elemental compound corresponding to the components contained in the catalyst and / or the catalyst precursor, and Preparing a dispersion of the carrier material; b2) optionally, an adhesion promoter, binder, viscosity modifier, pH modifier and / or inorganic carrier solid in said solution, emulsion and / or dispersion. B3) feeding a predetermined amount of said solution, emulsion and / or dispersion into each of the passages to form a predetermined composition on the catalyst support, thereby providing Simultaneously or successively coating the catalyst support present in the solution, emulsion and / or dispersion, and b4) optionally drying the catalyst and / or catalyst precursor, Sintering Heating the body containing the coated catalyst support in the passage at a temperature in the range of 20 ° C. to 1500 ° C., optionally in the presence of an inert gas or a reactive gas, for calcination; The method for producing an array according to any one of claims 1 to 4, wherein the method comprises: 7. c1) preparing a solution, an emulsion and / or a dispersion of an element and / or an elemental compound corresponding to the chemical component contained in the catalyst and / or the catalyst precursor, and if necessary, Preparing a dispersion of an inorganic carrier material; c2) in a single or a plurality of parallel operated reaction vessels an amount of said solution;
Mixing the emulsion and / or dispersion and, if necessary, a precipitating aid; c3) optionally, an adhesion promoter, a binder, a viscosity modifier, a pH modifier in the resulting mixture. And / or adding an inorganic carrier solid; c4) coating one or more predetermined passages of the body with one or more of said mixture; c5) composition of a predetermined catalyst and / or catalyst precursor. Repeating steps c2) to c4) for the other passages of the body, until the passage of the respective passage containing the material is finished; c6) drying the catalyst and / or catalyst precursor, if necessary, Heating the coated body at a temperature in the range of 20 ° C. to 1500 ° C., optionally in the presence of an inert gas or a reactive gas, for sintering or firing according to 2. The method according to claim 1, wherein Preparation of sequence of any one of the 4. 8. d1) preparing a solution, an emulsion and / or a dispersion of an element and / or an elemental compound corresponding to the chemical component contained in the catalyst and / or the catalyst precursor, and if necessary, Preparing a dispersion of an inorganic carrier material; d2) in a single or a plurality of parallel operated reaction vessels, an amount of said solution;
Mixing the emulsion and / or dispersion and, if necessary, a precipitating aid, d3) optionally, an adhesion promoter, a binder, a viscosity modifier in the resulting mixture,
adding a pH adjuster and / or an inorganic carrier solid; d4) coating the catalyst carrier present in one or more predetermined passages of the body with one or more of said mixture; d5) body Steps d2) to d4) are repeated with respect to another passage of the main body until the coating of the catalyst carrier present in the passage with the predetermined catalyst composition and / or the catalyst precursor composition is completed. Step, d6) optionally drying the catalyst and / or catalyst precursor and optionally sintering or calcining, optionally in the presence of an inert or reactive gas, at 20 ° C Heating the body containing the coated catalyst support in the passage at a temperature in the range of ~ 1500 [deg.] C. 9. Enhancing the adhesion of the body passages by applying a chemical, physical or mechanical pretreatment to the inner walls of the passages or providing an adhesive coating layer prior to coating. The method according to any one of claims 5 to 7, which is characterized in that: 10. The step of: e1) producing a different heterogeneous catalyst and / or a precursor of said catalyst in the form of an unsupported catalyst having a predetermined composition; e2) taking measures to prevent the heterogeneous catalyst from falling off. In each of one or more predetermined passages of the body, a heterogeneous catalyst having one or more predetermined compositions and / or
Or filling the respective precursors of the catalyst, e3) optionally drying the catalyst and / or catalyst precursor and optionally sintering or calcining, if necessary with an inert gas or Heating the body containing the heterogeneous catalyst and / or a precursor of the catalyst in a passage at a temperature in the range of 20C to 1500C in the presence of a reactive gas. Item 5. The method for producing the sequence according to any one of Items 1 to 4. F1) A predetermined catalyst carrier is coated outside the main body to produce a predetermined supported catalyst by the method according to any one of claims 6 to 8, and heated if necessary. F2) filling the supported catalyst into a predetermined passage of the main body; f3) optionally drying the catalyst and optionally sintering or calcining, if necessary, an inert gas. Or, in the presence of a reactive gas, 20 ° C to 1500 ° C
Heating the filled body at a temperature in the range of. 12. The method according to claim 11, wherein the external shape of the supported catalyst at least substantially corresponds to the internal shape of the passage of the main body. 13. A sequence obtained by the method according to any one of claims 5 to 12. 14. g1) activating the catalyst in the body as required; g2) heating or cooling the body to a desired reaction temperature; g3) adding the body to the flowable reactant or the flowable reaction mixture. G4) collecting and discharging the reacted fluids individually or from a plurality of passages from the main body passages; g5) analyzing the discharged reacted fluids; g6). Optionally comparing and evaluating the results of the analysis in the plurality of analyzes, the activity of the catalyst in the sequence according to any one of claims 1 to 4 or 13,
A method for evaluating selectivity and / or long-term stability. 15. After heating or cooling the body to the first reaction temperature in step g2), steps g3) to g6) are carried out continuously on a plurality of different flowable reactants or flowable reaction mixtures, wherein 15. The method of claim 14, wherein after each purge step with a purge gas, the body can be heated or cooled to a second reaction temperature and the reaction can be repeated at this temperature. 16. The method according to claim 14, wherein the flowable reactant or the flowable reaction mixture is a gas or a mixture of gases. 17. The method according to claim 14, wherein the reaction is a gas phase oxidation reaction.
The method according to any one of claims 16 to 16. 18. Use of a reaction mixture containing molecular oxygen,
The method according to claim 17. 19. A method of increasing the adhesion of the catalyst carrier in the main body by subjecting the catalyst carrier to a chemical, physical or mechanical pretreatment before coating, or by providing an adhesive layer. The production method according to claim 6 or 8, wherein 20. The method according to claim 5, wherein each step is performed by an automatic operation.
20. The method according to any one of to 12 and 14 to 19.