WO1999041005A1 - Procede de production et d'essai combinatoires de catalyseurs heterogenes - Google Patents

Procede de production et d'essai combinatoires de catalyseurs heterogenes Download PDF

Info

Publication number
WO1999041005A1
WO1999041005A1 PCT/EP1999/000902 EP9900902W WO9941005A1 WO 1999041005 A1 WO1999041005 A1 WO 1999041005A1 EP 9900902 W EP9900902 W EP 9900902W WO 9941005 A1 WO9941005 A1 WO 9941005A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
channels
optionally
catalysts
dispersions
Prior art date
Application number
PCT/EP1999/000902
Other languages
German (de)
English (en)
Inventor
Hartmut Hibst
Andreas Tenten
Dirk Demuth
Ferdi Schueth
Stephan A. Schunk
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19805719A external-priority patent/DE19805719A1/de
Priority claimed from DE19855894A external-priority patent/DE19855894A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP99907540A priority Critical patent/EP1054727A1/fr
Priority to JP2000531246A priority patent/JP2002502697A/ja
Priority to AU27250/99A priority patent/AU2725099A/en
Publication of WO1999041005A1 publication Critical patent/WO1999041005A1/fr
Priority to US11/336,843 priority patent/US20060127287A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00281—Individual reactor vessels
    • B01J2219/00286—Reactor vessels with top and bottom openings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00306—Reactor vessels in a multiple arrangement
    • B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00511—Walls of reactor vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00513—Essentially linear supports
    • B01J2219/0052—Essentially linear supports in the shape of elongated tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00612—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports the surface being inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00614—Delimitation of the attachment areas
    • B01J2219/00621—Delimitation of the attachment areas by physical means, e.g. trenches, raised areas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00632—Introduction of reactive groups to the surface
    • B01J2219/00637—Introduction of reactive groups to the surface by coating it with another layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00639—Making arrays on substantially continuous surfaces the compounds being trapped in or bound to a porous medium
    • B01J2219/00644—Making arrays on substantially continuous surfaces the compounds being trapped in or bound to a porous medium the porous medium being present in discrete locations, e.g. gel pads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B01J2219/00747—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B30/00—Methods of screening libraries
    • C40B30/08—Methods of screening libraries by measuring catalytic activity
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/18—Libraries containing only inorganic compounds or inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

  • the invention relates to a process for the combinatorial production and testing of heterogeneous catalysts and catalysts obtained by this process.
  • 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.
  • 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.
  • the synthetic process has recently also been expanded to include low molecular weight organic compounds and organic and inorganic catalysts.
  • the different pellets were placed on predetermined supports on a support and contacted with hydrogen under reaction conditions.
  • the catalyst warmed up and the warming was measured with the aid of an infrared camera, whereby the active catalysts could be determined.
  • 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.
  • 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.
  • 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.
  • the body is a tube bundle reactor or heat exchanger, and the channels are tubes.
  • 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.
  • 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.
  • the areas can be arranged in the manner of a row (quasi one-dimensional) or a checkerboard pattern (quasi two-dimensional).
  • 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.
  • 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.
  • Body is a cuboid or cylinder in which the channels are parallel between two
  • channel describes a connection running through the body between two openings present on the body surface, for example the
  • 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.
  • 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.
  • 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).
  • 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 -
  • 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.
  • 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:
  • adhesion promoters if necessary, adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic Carriers in the solutions, emulsions and / or dispersions,
  • Emulsions and / or dispersions is introduced to obtain a predetermined composition
  • Method b comprises the following steps:
  • adhesion promoters optionally adding adhesion promoters, binders, viscosity regulators, pH regulators and / or solid inorganic carriers into the solutions, emulsions and / or dispersions,
  • 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 -
  • the method c) comprises the following steps:
  • the method d) comprises the following steps:
  • coating catalyst supports present in one or more predetermined channels of the body with the mixture or one or more of the mixtures
  • 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:
  • 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.
  • the procedure f) comprises the following steps:
  • Catalyst supports for the production of predetermined supported catalysts in the manner defined above in process b) or d) outside the body,
  • 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 -
  • 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:
  • 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.
  • 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.
  • 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).
  • 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.
  • mixtures 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 -
  • 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.
  • 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 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 -
  • 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.
  • 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.
  • 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.
  • the mixtures used can additionally contain an inorganic and / or organic binder or a binder system which stabilizes the mixture used.
  • 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 -
  • 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.
  • 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.
  • 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.
  • solutions, emulsions or suspensions of individual elements or element compounds can be separated from one another simultaneously or on top of one another. - 21 -
  • process variant b is preferred, which is carried out in particular as follows:
  • 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.
  • 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.
  • 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 -
  • reaction container 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 ⁇ m 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).
  • the same catalyst compositions with different layer thicknesses can also be applied in different tubes.
  • auxiliary supports preferably metallic or ceramic tubes
  • auxiliary supports 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.
  • 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 Glasf ⁇ lter-Gedorfe 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 Germany 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.
  • 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 -
  • the supported catalysts described above can have the auxiliary supports as catalyst supports.
  • 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
  • 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.
  • Subcarriers e.g. in the form of inner tubes can be coated completely or only partially.
  • 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.
  • 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 ⁇ m, particularly preferably 20 to 500 ⁇ m 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.
  • 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.
  • 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.
  • Calcination or sintering is preferably 10 to 2000 ⁇ m, particularly preferably 20 to 500 ⁇ m.
  • an adhesion promoter can be applied before the coating on the inner tube 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.
  • the service life can be extended if an adhesion promoter is used. Suitable adhesion promoters have been described above.
  • the adhesion of the catalytic layer can be increased by chemical, physical or mechanical pretreatment of the inner tube before coating.
  • the inner tubes can e.g. be pickled with bases or preferably with acids.
  • the inner tube is roughened by blasting with a dry blasting medium, in particular corundum or quartz sand, in order to support the adhesion.
  • detergents which have a suspension of hard particles, e.g. Corundum, in a dispersion liquid.
  • 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.
  • 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.
  • each auxiliary support in the tube bundle reactor used generally has a different composition or also a different layer thickness of the catalytic coating.
  • the coated subcarriers can easily be exchanged for other subcarriers with other coatings.
  • a suitable reactor design provision of shut-off valves, etc.
  • the coated tube bundle reactor 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.
  • 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.
  • the heat transfer medium ensures that the temperature for drying, - 28 -
  • 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.
  • the space located between the reaction tubes is filled with a solid material, preferably a metal or with a solid metal alloy.
  • 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.
  • 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).
  • 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).
  • an oxygen-containing gas for example air, O 2 , N 2 O, NO, NO 2 , O 3
  • H 2 organic starting material to be reacted
  • other gaseous substances such as Cl or P-containing substances
  • 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.
  • 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.
  • 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 -
  • 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.
  • 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.
  • 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.
  • 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.
  • the gas supply can also be carried out using such a principle, with the individual tubes being tested sequentially.
  • 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 -
  • 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.
  • a new catalytically active coating is applied by means of sponges, brushes, spinning, spraying and / or dipping.
  • 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.
  • a blasting medium e.g. Corundum, silicon carbide, fine sand or the like can be done in a simple manner.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un groupement de catalyseurs hétérogènes et/ou de leurs précurseurs, constitués d'un corps qui présente des canaux traversants, de préférence parallèles, et dans lequel n canaux contiennent n catalyseurs hétérogènes différents et/ou leurs précurseurs, n ayant la valeur 2, de préférence la valeur 10, idéalement la valeur 100, en particulier la valeur 1000 et spécialement la valeur 10.000.
PCT/EP1999/000902 1998-02-12 1999-02-11 Procede de production et d'essai combinatoires de catalyseurs heterogenes WO1999041005A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99907540A EP1054727A1 (fr) 1998-02-12 1999-02-11 Procede de production et d'essai combinatoires de catalyseurs heterogenes
JP2000531246A JP2002502697A (ja) 1998-02-12 1999-02-11 不均一系触媒のコンビナトリアル製造法および評価法
AU27250/99A AU2725099A (en) 1998-02-12 1999-02-11 Method for the combinatorial production and testing of heterogeneous catalysts
US11/336,843 US20060127287A1 (en) 1998-02-12 2006-01-23 Combinatorial preparation and testing of heterogeneous catalysts

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19805719.9 1998-02-12
DE19805719A DE19805719A1 (de) 1998-02-12 1998-02-12 Verfahren zur kombinatorischen Herstellung und Testung von Heterogenkatalysatoren
DE19855894.5 1998-12-03
DE19855894A DE19855894A1 (de) 1998-12-03 1998-12-03 Verfahren zur kombinatorischen Herstellung und Testung von Heterogenkatalysatoren

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/336,843 Division US20060127287A1 (en) 1998-02-12 2006-01-23 Combinatorial preparation and testing of heterogeneous catalysts

Publications (1)

Publication Number Publication Date
WO1999041005A1 true WO1999041005A1 (fr) 1999-08-19

Family

ID=26043821

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/000902 WO1999041005A1 (fr) 1998-02-12 1999-02-11 Procede de production et d'essai combinatoires de catalyseurs heterogenes

Country Status (4)

Country Link
EP (1) EP1054727A1 (fr)
JP (1) JP2002502697A (fr)
AU (1) AU2725099A (fr)
WO (1) WO1999041005A1 (fr)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1108466A2 (fr) * 1999-12-13 2001-06-20 Basf Aktiengesellschaft Procédé de préparation et d'essais combinatoires de catalyseurs hétérogènes
WO2001043866A1 (fr) * 1999-12-13 2001-06-21 Hte Ag Procede pour la production de bibliotheques de materiaux par deposition electrochimique
WO2001057498A1 (fr) * 2000-02-04 2001-08-09 Hte Ag Procede et appareil pour la preparation combinatoire et l'analyse de bibliotheques de materiaux au moyen de procedes analytiques photoacoustiques
WO2001068236A2 (fr) * 2000-03-16 2001-09-20 Basf Aktiengesellschaft Procede et appareil pour la production et le test combines de bibliotheques de materiaux a l'aide d'au moins deux methodes analytiques
DE10019976A1 (de) * 2000-04-24 2001-10-31 Gwp Ges Fuer Werkstoffpruefung Vorrichtung und Verfahren zur iterativen Präparation und Testung von katalytisch oder chemisch aktiven Festkörpern
DE10038495A1 (de) * 2000-08-08 2002-02-21 Abb Research Ltd Einrichtung zum Prüfen von Werkstoffen
WO2002018040A1 (fr) * 2000-08-31 2002-03-07 Hte Ag Bibliotheque de matieres tridimensionnelle et procede de production d'une bibliotheque de matieres tridimensionnelle
DE10101118A1 (de) * 2001-01-05 2002-07-18 Inst Angewandte Chemie Berlin Verfahren zur Bewertung der Leistungsfähigkeit von Feststoffkatalysatoren für ein Reaktionsnetzwerk
WO2002087751A1 (fr) * 2001-04-27 2002-11-07 Bayer Aktiengesellschaft Reacteur pour reactions en parallele comportant une cartouche a gaz conçu pour analyser des catalyseurs heterogenes
US6602714B1 (en) 1999-11-09 2003-08-05 Sri International Viscosity and mass sensor for the high-throughput synthesis, screening and characterization of combinatorial libraries
US6627571B1 (en) 2000-03-01 2003-09-30 Symyx Technologies, Inc. Method and system for the situ synthesis of a combinatorial library of supported catalyst materials
US6749814B1 (en) 1999-03-03 2004-06-15 Symyx Technologies, Inc. Chemical processing microsystems comprising parallel flow microreactors and methods for using same
DE10117275B4 (de) * 2001-04-06 2005-02-24 Hte Ag The High Throughput Experimentation Company Vorrichtung zur Archivierung und Analyse von Materialien
US6862533B2 (en) 2000-06-10 2005-03-01 Hte Aktiengesellschaft The High Throughput Experimentation Company Computer-aided optimization of substance libraries
DE10036633B4 (de) * 2000-07-27 2005-03-10 Hte Ag The High Throughput Exp Anordnung in modularer Bauweise und Verfahren zur paralellen Testung einer Mehrzahl von Bausteinen einer Materialbibliothek
US7118917B2 (en) 2001-03-07 2006-10-10 Symyx Technologies, Inc. Parallel flow reactor having improved thermal control
US7122156B2 (en) 2000-03-07 2006-10-17 Symyx Technologies, Inc. Parallel flow reactor having variable composition
US7150994B2 (en) 1999-03-03 2006-12-19 Symyx Technologies, Inc. Parallel flow process optimization reactor
US7867937B2 (en) 2006-12-15 2011-01-11 Exxonmobil Research And Engineering Company Drying device for producing small quantities of controlled particle size catalysts which are appropriate for use in fluidized bed operations such as fluid catalytic cracking
US8563325B1 (en) 2009-09-29 2013-10-22 Sandia Corporation Coaxial microreactor for particle synthesis

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10357339A1 (de) * 2003-12-09 2005-07-14 Degussa Ag Verfahren und Vorrichtung zur Herstellung von anorganischen Materialien
JP2007183266A (ja) * 2006-12-25 2007-07-19 Seiko Epson Corp 組成探査方法および燃料電池用電極触媒の組成探査方法
PL2878369T3 (pl) * 2013-11-27 2016-09-30 Sposób powlekania

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0570842A1 (fr) * 1992-05-21 1993-11-24 BASF Aktiengesellschaft Procédé pour fixer de grands cristaux d'une zéolithe ou d'un tamis moléculaire analogue sur un support
EP0682982A2 (fr) * 1994-05-18 1995-11-22 William C. Pfefferle Méthode catalytique
EP0704241A1 (fr) * 1994-09-29 1996-04-03 Corning Incorporated Structure catalytique comprenant un substrat cellulaire et une couche de matériau catalytiquement actif
WO1997032208A1 (fr) * 1996-02-28 1997-09-04 Technology Licensing Co. L.L.C. Appareil et procede d'essai de catalyseurs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0570842A1 (fr) * 1992-05-21 1993-11-24 BASF Aktiengesellschaft Procédé pour fixer de grands cristaux d'une zéolithe ou d'un tamis moléculaire analogue sur un support
EP0682982A2 (fr) * 1994-05-18 1995-11-22 William C. Pfefferle Méthode catalytique
EP0704241A1 (fr) * 1994-09-29 1996-04-03 Corning Incorporated Structure catalytique comprenant un substrat cellulaire et une couche de matériau catalytiquement actif
WO1997032208A1 (fr) * 1996-02-28 1997-09-04 Technology Licensing Co. L.L.C. Appareil et procede d'essai de catalyseurs

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7150994B2 (en) 1999-03-03 2006-12-19 Symyx Technologies, Inc. Parallel flow process optimization reactor
US6902934B1 (en) 1999-03-03 2005-06-07 Symyx Technologies, Inc. Methods for identifying optimizing catalysts in parallel-flow microreactors
US6890493B1 (en) 1999-03-03 2005-05-10 Symyx Technologies, Inc. Methods and apparatus for fluid distribution in microfluidic systems
US6749814B1 (en) 1999-03-03 2004-06-15 Symyx Technologies, Inc. Chemical processing microsystems comprising parallel flow microreactors and methods for using same
US6602714B1 (en) 1999-11-09 2003-08-05 Sri International Viscosity and mass sensor for the high-throughput synthesis, screening and characterization of combinatorial libraries
US6896783B2 (en) 1999-12-13 2005-05-24 Hte Aktiengesellschaft The High Throughput Experimentation Company Method for producing material libraries by means of electrochemical deposition
WO2001043866A1 (fr) * 1999-12-13 2001-06-21 Hte Ag Procede pour la production de bibliotheques de materiaux par deposition electrochimique
EP1108466A2 (fr) * 1999-12-13 2001-06-20 Basf Aktiengesellschaft Procédé de préparation et d'essais combinatoires de catalyseurs hétérogènes
US6720171B2 (en) * 1999-12-13 2004-04-13 Basf Aktiengesellschaft Combinatorial preparation and testing of heterogeneous catalysts
EP1108466A3 (fr) * 1999-12-13 2002-10-09 Basf Aktiengesellschaft Procédé de préparation et d'essais combinatoires de catalyseurs hétérogènes
WO2001057498A1 (fr) * 2000-02-04 2001-08-09 Hte Ag Procede et appareil pour la preparation combinatoire et l'analyse de bibliotheques de materiaux au moyen de procedes analytiques photoacoustiques
US6875717B2 (en) 2000-03-01 2005-04-05 Symyx Technologies, Inc. Method and system for the in situ synthesis of a combinatorial library of supported catalyst materials
US6627571B1 (en) 2000-03-01 2003-09-30 Symyx Technologies, Inc. Method and system for the situ synthesis of a combinatorial library of supported catalyst materials
US7122156B2 (en) 2000-03-07 2006-10-17 Symyx Technologies, Inc. Parallel flow reactor having variable composition
US7374942B2 (en) 2000-03-16 2008-05-20 Basf Aktiengesellschaft Process and apparatus for the combinatorial production and testing of catalyst material libraries by using at least two analytical methods
WO2001068236A3 (fr) * 2000-03-16 2002-03-28 Hte Ag Procede et appareil pour la production et le test combines de bibliotheques de materiaux a l'aide d'au moins deux methodes analytiques
WO2001068236A2 (fr) * 2000-03-16 2001-09-20 Basf Aktiengesellschaft Procede et appareil pour la production et le test combines de bibliotheques de materiaux a l'aide d'au moins deux methodes analytiques
DE10019976A1 (de) * 2000-04-24 2001-10-31 Gwp Ges Fuer Werkstoffpruefung Vorrichtung und Verfahren zur iterativen Präparation und Testung von katalytisch oder chemisch aktiven Festkörpern
US6862533B2 (en) 2000-06-10 2005-03-01 Hte Aktiengesellschaft The High Throughput Experimentation Company Computer-aided optimization of substance libraries
DE10036633B4 (de) * 2000-07-27 2005-03-10 Hte Ag The High Throughput Exp Anordnung in modularer Bauweise und Verfahren zur paralellen Testung einer Mehrzahl von Bausteinen einer Materialbibliothek
DE10038495A1 (de) * 2000-08-08 2002-02-21 Abb Research Ltd Einrichtung zum Prüfen von Werkstoffen
WO2002018040A1 (fr) * 2000-08-31 2002-03-07 Hte Ag Bibliotheque de matieres tridimensionnelle et procede de production d'une bibliotheque de matieres tridimensionnelle
DE10101118C2 (de) * 2001-01-05 2002-12-19 Inst Angewandte Chemie Berlin Verfahren zur Bewertung der Leistungsfähigkeit von Feststoffkatalysatoren für ein Reaktionsnetzwerk
DE10101118A1 (de) * 2001-01-05 2002-07-18 Inst Angewandte Chemie Berlin Verfahren zur Bewertung der Leistungsfähigkeit von Feststoffkatalysatoren für ein Reaktionsnetzwerk
US7118917B2 (en) 2001-03-07 2006-10-10 Symyx Technologies, Inc. Parallel flow reactor having improved thermal control
DE10117275B4 (de) * 2001-04-06 2005-02-24 Hte Ag The High Throughput Experimentation Company Vorrichtung zur Archivierung und Analyse von Materialien
US7384603B2 (en) 2001-04-06 2008-06-10 Hte Aktiengesellschaft The High Throughput Experimentation Company Device for archiving and analyzing of materials
WO2002087751A1 (fr) * 2001-04-27 2002-11-07 Bayer Aktiengesellschaft Reacteur pour reactions en parallele comportant une cartouche a gaz conçu pour analyser des catalyseurs heterogenes
US7867937B2 (en) 2006-12-15 2011-01-11 Exxonmobil Research And Engineering Company Drying device for producing small quantities of controlled particle size catalysts which are appropriate for use in fluidized bed operations such as fluid catalytic cracking
US8563325B1 (en) 2009-09-29 2013-10-22 Sandia Corporation Coaxial microreactor for particle synthesis

Also Published As

Publication number Publication date
AU2725099A (en) 1999-08-30
EP1054727A1 (fr) 2000-11-29
JP2002502697A (ja) 2002-01-29

Similar Documents

Publication Publication Date Title
WO1999041005A1 (fr) Procede de production et d'essai combinatoires de catalyseurs heterogenes
DE3731688C2 (fr)
DE19959973A1 (de) Verfahren zur kombinatorischen Herstellung und Testung von Heterogenkatalysatoren
DE60024462T2 (de) Katalysatorstruktur und Verfahren zur Fischer-Tropsch-Synthese
DE69603982T2 (de) Methode und apparat zur verwendung für katalytische reaktionen
DE19805719A1 (de) Verfahren zur kombinatorischen Herstellung und Testung von Heterogenkatalysatoren
DE2045488A1 (de) Verfahren und Katalysator zur Reinigung von Gasen
EP1278600A1 (fr) Catalyseurs a coque, leur procede de production et leur utilisation
DE19653991A1 (de) Reaktor zur Durchführung endothermer katalytischer Reaktionen
EP1232004A1 (fr) Procede d'oxydation catalytique en phase gazeuse permettant d'obtenir de l'acide (meth)acroleine et/ou (meth)acrylique
DE10012847A1 (de) Verfahren und Vorrichtung zur kombinatorischen Herstellung und Testung von Materialbibliotheken durch Anwendung mindestens zweier Analysemethoden
EP1858629B1 (fr) Procede pour produire une membrane polymere, et membrane polymere
DE19855894A1 (de) Verfahren zur kombinatorischen Herstellung und Testung von Heterogenkatalysatoren
DE19806848A1 (de) Verfahren zur kombinatorischen Herstellung und Testung von Heterogenkatalysatoren
US20060127287A1 (en) Combinatorial preparation and testing of heterogeneous catalysts
KR20040002892A (ko) 3-상 화학 공정용 미니-구조 촉매 베드
DE60016525T2 (de) Reaktor zur katalytischen selektiven Oxidation eines Wasserkohlenstoffes
DE69924995T2 (de) Herstellungsverfahren für katalytische funktionalisierte metallische faserplatten
WO1999044736A1 (fr) Procede pour la realisation de transformations chimiques dans un microreacteur, et un tel microreacteur
EP1243334A1 (fr) Préparation d'une couche hydrofuge de catalyseur sur un support céramique ou métallique
CH651481A5 (de) Verfahren und vorrichtung zum innenbeschichten von kontaktrohren.
DE10335968A1 (de) Verfahren zur sequentiellen Herstellung einer Heterogenkatalysator-Bibliothek
DE69813882T2 (de) Verfahren zur hydrierung von makromolekularen organischen substraten
DE102021127105A1 (de) Katalysatorherstellung mittels Mehreinheitenoperationen in einem Mischerreaktor
DE102004002477A1 (de) Vorrichtung zur Erzeugung von Wasserstoff

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): 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

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: KR

WWE Wipo information: entry into national phase

Ref document number: 09622173

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1999907540

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1999907540

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)