WO2025242537A1 - Corps de catalyseur façonnés électriquement conducteurs destinés à être utilisés dans un réacteur chimique - Google Patents

Corps de catalyseur façonnés électriquement conducteurs destinés à être utilisés dans un réacteur chimique

Info

Publication number
WO2025242537A1
WO2025242537A1 PCT/EP2025/063407 EP2025063407W WO2025242537A1 WO 2025242537 A1 WO2025242537 A1 WO 2025242537A1 EP 2025063407 W EP2025063407 W EP 2025063407W WO 2025242537 A1 WO2025242537 A1 WO 2025242537A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrically conductive
shaped catalyst
catalyst bodies
materials
bed
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/EP2025/063407
Other languages
English (en)
Inventor
Michael Bender
Frank Rosowski
Frederik SCHEIFF
Michael Kraemer
Elias Christopher FREI
Dina Zakgeym
Benjamin Frank
Claus Hofmann
Michael Geske
Robert DIECKMANN
Emre Turan
Johannes BODE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Technische Universitaet Berlin
Original Assignee
BASF SE
Technische Universitaet Berlin
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
Application filed by BASF SE, Technische Universitaet Berlin filed Critical BASF SE
Publication of WO2025242537A1 publication Critical patent/WO2025242537A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/12—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/02—Preparation, separation or purification of hydrogen cyanide
    • C01C3/0208—Preparation in gaseous phase
    • C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
    • C01C3/0216—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/02—Preparation, separation or purification of hydrogen cyanide
    • C01C3/0208—Preparation in gaseous phase
    • C01C3/0241—Preparation in gaseous phase from alcohols or aldehydes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina

Definitions

  • the present invention relates to electrically conductive shaped catalyst bodies for use in a chemical reactor comprising a mixture of at least two different solid materials, wherein the mixture comprises i) at least one catalytically active or activatable material, and ii) at least one electrically conductive material, wherein the sum of the volume fractions of all electrically conductive materials of the shaped catalyst bodies is in the range of from 0.2 to 0.35, and wherein the shaped catalyst bodies have a characteristic diameter in the range of from 1 mm to 50 mm, and wherein the sum of the mass fractions of all catalytically active or activatable materials and of the mass fractions of all electrically conductive materials of the shaped catalyst bodies is in the range of from 0.9 to 1..
  • the present invention further relates to a process for preparing the electrically conductive shaped catalyst bodies, to the use of the electrically conductive shaped catalyst bodies as part of a directly electrically heatable catalyst bed or as directly electrically heatable catalyst bed in a chemical reactor and to a chemical reactor for conducting a chemical reaction containing a catalyst bed comprising or consisting of the electrically conductive shaped catalyst bodies.
  • the present invention further relates to a process for conducting a chemical reaction, which is catalyzed by the electrically conductive shaped catalyst bodies.
  • U.S. Pat. No. 2,982,622 describes a heat-integrated pyrolysis of hydrocarbons in a moving bed composed of inert materials. The temperatures of 1200 °C that are required for the pyrolysis are attained with the aid of electrical heating. The heat is generated by ohmic losses of an electrical current that is passed through a bed of carbon particles, which are heated in the process. A catalyst is not needed in the described pyrolysis.
  • WO 02/45837 describes an electrically heated fixed bed reactor which contains at least one pair of electrodes in a reactor housing and a fluid-permeable fixed bed of a particulate material having suitable electrical conductivity and being suitable for resistance heating.
  • the electrically directly heatable fixed bed contains a bed of electrically conductive shaped bodies which contain at least one conductive component and optionally one or more non-conductive portions, wherein both the conductive and the non-conductive components can have a catalytic effect.
  • WO 02/45837 does not disclose any explicit example of electrically conductive shaped bodies suitable for the heatable fixed bed.
  • DE 102 36 019 A1 describes a reactor for performance of endothermic reactions which is equipped with one or more heating blocks that completely fill the reactor cross section and are electrically insulated from the reactor inner wall and optionally from one another, wherein the heating blocks are formed from open-cell foam.
  • the presence of an alkali metal comprising compound as a catalyst is not described.
  • DE 10 2013 226 126 describes a method and an arrangement for allothermal methane reforming with physical energy recovery, wherein synthesis gas consisting of molecular hydrogen and carbon monoxide is produced from methane and steam and/or carbon dioxide with high efficiency and low energy costs.
  • synthesis gas consisting of molecular hydrogen and carbon monoxide is produced from methane and steam and/or carbon dioxide with high efficiency and low energy costs.
  • the starting materials methane and carbon dioxide are fed into a fixed bed reactor consisting of electrically conductive and catalytic particles, which are electrically heated to temperatures of approx. 1000 K.
  • the reactant gases are converted in the fixed bed and the formed synthesis gas is heated and expended.
  • the average size of the electrically conductive particles is from 2 to 10 times, preferably 4 times, the average size of the catalyst particles, while the catalytically active particles have an average size of from 1 mm to 50 mm, preferably from 5 mm to 10 mm.
  • WO2017/072057 A1 discloses a reactor system for dehydrogenation of alkanes.
  • the reactor system comprises a reactor unit arranged to accommodate a catalytic mixture, wherein the catalytic mixture comprises catalyst particles and a ferromagnetic material.
  • the reactor system moreover comprises an induction coil arranged to be powered by a power source supplying alternating current and being positioned so as to generate an alternating magnetic field within the reactor unit upon energization by the power source. By this arrangement, the catalytic mixture is heated to the required reaction temperature by means of the alternating magnetic field.
  • WO2022/023355 A1 discloses a process to perform an endothermic steam reforming of hydrocarbons, said process comprising the steps of providing a fluidized bed reactor comprising at least two electrodes and a bed comprising particles, wherein the particles are put in a fluidized state to obtain a fluidized bed; heating the fluidized bed to a temperature ranging from 500 °C to 1200 °C by passing an electric current through the fluidized bed to conduct the endothermic reaction.
  • the fluidized bed comprises electrically conductive particles and particles of a catalytic composition.
  • the fluidized bed is heated by passing an electric current through the fluidized bed.
  • the particles of the fluidized bed have an average particle size preferably ranging from 30 pm to 150 pm as determined by sieving according to ASTM D4513-11.
  • M. Greuel et al., Chem. Ing. Tech. 2024, 96, No. 5, 671-678, DOI: 10.1002/cite.202300207 discloses the preparation of conductive pellets comprising a catalytic active material (saponite) and electrically conductive material without disclosing the composition of the electrically conductive pellets.
  • the conductive pellets are used in an ohmic reactor for the conversion of ethanol to 1 ,3-butadiene.
  • AU2021318837 A1 which corresponds to WO2022/023368 A1 , discloses a process to perform an endothermic methane pyrolysis reaction, said process comprising the steps of providing at least one fluidized bed reactor comprising at least two electrodes; and a bed comprising particles, wherein the particles are put in a fluidized state by passing upwardly through the said bed a fluid stream, to obtain a fluidized bed; heating the fluidized bed to a temperature ranging from 500°C to I2OO°C to conduct the endothermic methane pyrolysis reaction; wherein the particles of the bed comprise electrically conductive particles and particles of a catalytic composition; wherein at least 10 wt.% of the particles are electrically conductive particles and have a resistivity ranging from 0.001 Ohm.
  • the electrically conductive particles and the particles of a catalytic composition have an average particles size ranging from 5 to 300 pm as determined by sieving according to ASTM D4513-11.
  • US 5,480,622 discloses an electrically heatable automotive catalyst system comprising an electrically insulating substrate, such as monolithic honeycomb structure made of cordierite, carrying a layer of an electrically conductive material; such as tin oxide doped indium oxide, applied over a surface of the substrate, a washcoat, such as titanium dioxide, carried on a surface of the electrically conductive material, and a catalyst, such as platinum, rhodium and/or palladium, carried on a surface of the washcoat.
  • an electrically insulating substrate such as monolithic honeycomb structure made of cordierite, carrying a layer of an electrically conductive material; such as tin oxide doped indium oxide, applied over a surface of the substrate, a washcoat, such as titanium dioxide, carried on a surface of the electrically conductive material, and a catalyst, such as platinum, rhodium and/or palladium, carried on a surface of the washcoat.
  • shaped catalyst bodies are available for a wide variety of reaction types. For reactions taking place in the gas phase, shaped catalyst bodies are used in fixed bed reactors or moving bed reactors. The shaped catalyst bodies are usually not used in fluidized bed reactors due to their size and the associated weight. In case of commercially available shaped catalyst bodies the largest dimension of said shaped catalyst bodies is usually in the range of from 1 mm to 100 mm.
  • an object of the invention was to provide electrically conductive shaped catalyst bodies, which comprise a catalytically active or activatable material and electrically conductive material, wherein a catalyst bed comprising said shaped catalyst bodies can be realized which is electrically heatable to temperatures well above 500 °C, preferably electrically heatable at a high voltage and low amperage, and wherein the shaped catalyst bodies show a high catalytic activity and allow to carry out more economical procedures with lower capital expenditures.
  • electrically conductive shaped catalyst bodies for use in a chemical reactor comprising a mixture of at least two different solid materials, wherein the mixture comprises i) at least one catalytically active or activatable material, and ii) at least one electrically conductive material, wherein the sum of the volume fractions of all electrically conductive materials of the shaped catalyst bodies is in the range of from 0.2 to 0.35, and wherein the shaped catalyst bodies have a characteristic diameter in the range of from 1 mm to 50 mm, and wherein the sum of the mass fractions of all catalytically active or activatable materials and of the mass fractions of all electrically conductive materials of the shaped catalyst bodies is in the range of from 0.9 to 1 .
  • bodies refers to three-dimensional geometric objects, wherein the smallest dimension of these object is in the mm range, and which can be viewed with the naked eye.
  • the smallest dimension starts preferably at about 0.2 mm, more preferably at about 0.5 mm, even more preferably at about 1 mm, in particular at about 2 mm.
  • shaped bodies refers to bodies, which are produced through a shaping process or form giving process.
  • the geometry of the shaped bodies is very similar or identical in view of at least two dimensions.
  • Geometric objects formed by extrusion are very similar or almost identical in view of two dimensions, the cross-sectional area, but variable in view of their lengths.
  • Geometric objects formed by tableting, casting, or 3D-pri nting are very similar or almost identical in view of all three dimensions.
  • the inventive electrically conductive shaped catalyst bodies are applied in a chemical reactor meaning they are designed for the use in a chemical reactor. Chemical reactors for different chemical reactions, in particular for the above-mentioned endothermic reactions are known to the person skilled in the art.
  • the inventive electrically conductive shaped catalyst bodies are preferably suitable for their use in a moving bed reactor or a fixed bed reactor, more preferably for their use in a fixed bed reactor.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the chemical reactor is a moving bed reactor or a fixed bed reactor, preferably a fixed bed reactor.
  • fresh solids can be fed from the top, while a gas stream is fed from the bottom. These solid particles slowly move down the reactor and are withdrawn from the bottom of the bed.
  • Fixed bed reactors are the main type of catalytic reactors for large-scale chemical synthesis. The process is characterized by different gaseous chemical species reacting on the catalyst surface placed in a fixed position inside the reactor.
  • the inventive electrically conductive shaped catalyst bodies comprise a mixture of at least two different solid materials, wherein the mixture comprises as a first component (I) at least one catalytically active or activatable material, and as a second component (II) at least one electrically conductive material.
  • catalytically active or activatable material means a material, that is already catalytically active before it is contacted with the starting materials of an envisioned chemical reaction, or a material, that is converted into a catalytically active material either before its first contacted with the starting materials of said envisioned chemical reaction or during the first contact with any of the starting materials of said envisioned chemical reaction.
  • the inventive electrically conductive shaped catalyst bodies are built up by a mixture of at least two different solid materials which are usually in the form of powders consisting of powder particles before converted into shaped bodies by compacting said powder by known methods like extrusion, tableting, or 3D-printing.
  • the powder particles themselves might have been formed by grinding a pre-compacted material or a pre-compacted mixture of materials.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the mixture of the at least two different solid materials is in the form of compacted powder particles.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the mixture of the at least two different solid materials is used as a powder before converted into the shaped catalyst bodies.
  • the mixture of the at least two different solid materials building up the inventive electrically conductive shaped catalyst bodies might comprise beside the at least one catalytically active or activatable material (component (I)) and the at least one electrically conductive material (component (II)) additional materials, which are neither catalytically active or activatable nor electrically conductive, but which might improve another desirable characteristic of the mixture such as its mechanical or chemical stability, in particular its ability to be compacted.
  • the additional material is an auxiliary material for compacting powder particles.
  • the auxiliary material might for example act as lubricant or binder during or after the formation of the shaped bodies.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the mixture of the at least two different solid materials additionally comprises ill) at least one auxiliary material for compacting powder particles.
  • auxiliary materials for compacting powder particles are known to the person skilled in the art for the different compacting processes such as extrusion, tableting, or 3D-printing.
  • Typical but non-limiting examples of auxiliary materials are water, colloidal silica, stearic acid, methyl cellulose or boehmite. Further examples are listed in US7651968B2 and in the references cited therein.
  • the shaped catalyst bodies consist of as few components as possible.
  • the bodies consist preferably by at least 90% by weight, preferably by at least 95% by weight, in particular by at least 98% by weight only of the catalytically active or activatable materials (component (I)) and the electrically conductive materials.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the sum of the mass fractions of all catalytically active or activatable materials and of the mass fractions of all electrically conductive materials of the shaped catalyst bodies is in the range of from 0.9 to 1, more preferably in the range of from 0.95 to 1 , in particular in the range of from 0.98 to 1 .
  • the inventive electrically conductive shaped catalyst bodies comprise not more than two different, preferably only one catalytically active or activatable material and not more than two different, preferably only one electrically conductive material.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the at least one catalytically active or activatable material is one catalytically active or activatable material. In another embodiment of the present invention, the inventive electrically conductive shaped catalyst bodies are characterized in that the at least one electrically conductive material is one electrically conductive material.
  • the mixture of the at least two different solid materials is used as a powder before converted into the shaped catalyst bodies
  • the at least one catalytically active or activatable material and the at least one electrically conductive material are also used as powders before converted into the shaped catalyst bodies.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the at least one catalytically active or activatable material and the at least one electrically conductive material are used as powders before converted into the shaped catalyst bodies.
  • the term powder describes a dispersed system of the solid-gaseous category, in which the particles of the inner phase touch each other.
  • the powder particles can differ in mass, shape, size and in their physicochemical properties. They can be present individually in a crystalline or amorphous structure or as a composite of particles.
  • the particles of fine powders usually have a particle size below 100 pm.
  • the particles of the at least one catalytically active or activatable material and of the at least one electrically conductive material usually show an average particle size below 1 mm.
  • the particles have an average particle size in the range of from 0.1 pm to 1000 pm before converted into the inventive shaped catalyst bodies.
  • the particles of the at least one electrically conductive material have preferably an average particle size in the range of from 1 pm to 300 pm, more preferably in the range of from 10 pm to 100 pm before converted into the inventive shaped catalyst bodies.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the particles of at least one catalytically active or activatable material and of the at least one electrically conductive material have an average particle size in the range of from 0.1 pm to 1000 pm before converted into the shaped catalyst bodies.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the particles of the at least one electrically conductive material have an average particle size preferably in the range of from 1 pm to 300 pm, more preferably in the range of from 10 pm to 100 pm before converted into the shaped catalyst bodies.
  • the average particle size can be determined by sieving according to ASTM D4513-11 .
  • the inventive electrically conductive shaped catalyst bodies can show a wide variety of geometric shapes, preferably geometric shapes with a characteristic diameter ranging from 1 mm to 50 mm, preferably ranging from 2 mm to 30 mm, more preferably ranging from 3 mm to 15 mm with preference being given to extrudates, pellets, rings, cylinders, stars, wagon wheels, spheres, extrudates, trilobes, or quadrilobes, preferably pellets, spheres or extrudates.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the bodies have a shape selected from the group consisting of pellets, rings, cylinders, stars, wagon wheels, spheres, extrudates, trilobes and quadrilobes, preferably pellets, spheres and extrudates.
  • the aspect ratio of the inventive electrically conductive shaped catalyst bodies can be varied in a wide range, wherein the aspect ratio is defined as the ratio between the largest dimension of the body and the smallest dimension of the body.
  • the inventive electrically conductive shaped catalyst bodies have an aspect ratio in the range of from 1 to 20, preferably in the range of from 1 to 10, more preferably in the range of from 1 to 5, even more preferably in the range of from 1 to 4, preferably in the range of from 1 to 3, in particular in the range of from 1 to 2.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the bodies have an aspect ratio in the range of from 1 to 20, preferably in the range of from 1 to 10, more preferably in the range of from 1 to 5, even more preferably in the range of from 1 to 4, preferably in the range of from 1 to 3, in particular in the range of from 1 to 2.
  • the inventive electrically conductive shaped catalyst bodies can be characterized by a characteristic diameter.
  • characteristic diameter of shaped bodies is defined by the product of the diameter of a circumscribed sphere d css surrounding the shaped body and the sphericity TT of the convex hull of said shaped body.
  • the characteristic diameter of the inventive electrically conductive shaped catalyst bodies is determined by methods known to the person skill in the art.
  • the characteristic diameter of shaped bodies can be determined by simple measuring the dimensions of said body with calipers or a microscope and some calculations. In case of extrudates as shaped bodies with a certain distribution in length, the mass-based average length should be used in calculations.
  • the characteristic diameter d is equal the product of the diameter of a circumscribed sphere d css surrounding the shaped body and the sphericity T C h of the convex hull of the shaped body: d d css ⁇ Vg ] with ch being a function of the volume V C h of the convex hull of the shaped body and the surface Ach of the convex hull of the shaped body.
  • the characteristic diameter of inventive electrically conductive shaped catalyst bodies d can be varied in a wide range.
  • the shaped catalyst bodies have a characteristic diameter d in the range of from 1 mm to 50 mm, preferably in the range of from 2 mm to 30 mm, more preferably in the range of from 3 mm to 15 mm.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the bodies have a characteristic diameter d in the range of from 1 mm to 50 mm, preferably in the range of from 2 mm to 30 mm, more preferably in the range of from 3 mm to 15 mm.
  • the specific surface area of the inventive electrically conductive shaped catalyst bodies can be varied in a wide range depending on the production methods and the employed materials and auxiliaries.
  • the specific surface area of the shaped catalyst bodies is in the range of from 0.1 m 2 /g to 500 m 2 /g, more preferably in the range of from 10 m 2 /g to 300 m 2 /g determined by using the Brunauer-Emmett-Teller (N2-BET) adsorption method.
  • the electrically conductive shaped catalyst bodies are characterized in that the bodies have a specific surface area in the range from 0.1 m 2 /g to 500 m 2 /g (N2-BET), more preferably in the range of from 10 m 2 /g to 300 m 2 /g (N2-BET).
  • the at least one catalytically active or activatable material (component (I)) and the at least one electrically conductive material (component (II)) of the mixture building up the inventive electrically conductive shaped catalyst bodies are different solid materials meaning that they have different chemical compositions.
  • the optionally present at least one auxiliary material for compacting powder particles differs in its chemical composition from the catalytically active or activatable materials and from the electrically conductive materials.
  • the structure and the chemical composition of the inventive electrically conductive shaped catalyst bodies can be varied in a wide range depending on the chemical reaction, preferably an endothermic or a highly endothermic reaction, which can be catalyzed by the shaped catalyst body and depending on the temperature range that must be reached for running the desired chemical reaction, preferably one of the above-mentioned endothermic reactions.
  • the at least one catalytically active or activatable material (component (I)) and the at least one electrically conductive material (component (II)) do not only differ in their chemical composition but also in different material characteristics, in particular different electrical resistivities.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the catalytically active or activatable materials and the electrically conductive materials have different chemical compositions.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the auxiliary material for compacting powder particles differs in its chemical composition from the catalytically active or activatable materials and from the electrically conductive materials.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the catalytically active or activatable materials and the electrically conductive materials have different electrical resistivities.
  • the bulk electrical resistivity at 20 °C of the at least one catalytically active or activatable material is by a factor of at least 5 higher than the bulk electrical resistivity at 20 °C of the at least one electrically conductive material, preferably higher by a factor of at least 10 1 , more preferably higher by a factor of at least 10 2 , in particular higher by a factor of at least 10 3 . That means, that any significant contribution of the catalytically active or activatable materials in view of the needed current flow for heat generation can be neglected.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the bulk electrical resistivity at 20 °C of the at least one catalytically active or activatable material is by a factor of at least 5 higher than the bulk electrical resistivity at 20 °C of the at least one electrically conductive material, preferably higher by a factor of at least 10 1 , more preferably higher by a factor of at least 10 2 , in particular higher by a factor of at least 10 3 .
  • the bulk electrical resistivity at 20 °C is determined by methods known to the person skilled in the art.
  • the electrical resistivity of materials consisting of electrical conductors is determined by ASTM B193-20.
  • the electrical resistivity is preferably determined by ASTM C611-21 .
  • the electrical resistivity is preferably determined by ASTM D1829-90.
  • inventive electrically conductive shaped catalyst bodies comprising a mixture of at least one catalytically active or activatable material (component (i)) and at least one electrically conductive material (component (ii)) generate heat by ohmic losses, when an electrical current is passed through said bodies.
  • electric currents flow internally via contact points between the electrically conductive materials and externally between neighbored bodies through contact points which are sufficiently electrically conductive.
  • the inventive electrically conductive shaped catalyst bodies have a fixed bed electrical resistivity at 20 °C, which can be varied in a broad range depending among others on the amount and on the bulk electrical resistivity of the electrically conductive materials present in the bodies.
  • the bed electrical resistivity at 20 °C of the inventive electrically conductive shaped catalyst bodies is in the range of from 10 4 Qm to 10 2 Qm, preferably 10 3 Qm to 10 2 Qm, even more preferably 10- 3 Qm to 10 1 Qm.
  • the fixed bed electrical resistivity at 20 °C of the inventive electrically conductive shaped catalyst bodies can be determined as described in EP-application No. 23208352.7 or as described in ISO 10143:2019.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the electrically conductive shaped catalyst bodies have a fixed bed electrical resistivity at 20 °C in the range of from 10 4 Qm to 10 2 Qm, preferably 10 3 Qm to 10 2 Qm, even more preferably 10 3 Qm to 10 1 Qm.
  • the bulk electrical resistivity at 20 °C of the one or more electrically conductive materials present in the inventive electrically conductive shaped catalyst bodies can be varied in a wide range depending on the nature of the chosen electrically conductive material or mixture of electrically conductive materials.
  • the value of the bulk electrical resistivity at 20 °C of the one or more electrically conductive materials present in the inventive electrically conductive shaped catalyst bodies is lower than the above-mentioned value of the fixed bed electrical resistivity at 20 °C of the inventive electrically conductive shaped catalyst bodies due to the pathway of an electrical current through the mixture of at least two different solid materials in each body and between the bodies via contact points as described above.
  • the at least one electrically conductive material or a mixture of said electrically conductive materials have preferably a bulk electrical resistivity at 20 °C in the range of from 10 8 Qm to 10 2 Qm, more preferably 10 7 Qm to 10’ 3 Qm, even more preferably 10 7 Qm to 10’ 4 Qm.
  • the electrically conductive shaped catalyst bodies are characterized in that the at least one electrically conductive material has a bulk electrical resistivity at 20 °C in the range of from 10’ 8 Qm to 10’ 2 Qm, more preferably 10 7 Qm to 10’ 3 Qm, even more preferably 10 7 Qm to 10’ 4 Qm.
  • Catalytically active or activatable materials which are part of the inventive electrically conductive shaped catalyst bodies, are known to the person skilled in the art for all chemical reactions of industrial relevance.
  • the catalytically active or activatable materials comprise a compound selected from the group consisting of transition metals, transition metal oxides, main group metal oxides, rare earth metal oxides, and mixtures thereof.
  • An electrically conductive material is preferably selected from the group consisting of metals, metallic alloys, non-metallic resistors, metallic carbides, transition metal nitrides, metallic borides, metallic silicides, metallic phosphides, carbon in a polymorph comprising at least 60% sp 2 -hy bridized carbon atoms, superionic conductors, phosphate electrolytes, mixed oxides doped with lower- valent cations, mixed sulfides doped with lower-valent cations, composite materials comprising at least 30% by weight of any of the previously mentioned electrically conductive materials and any mixtures thereof.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the at least one electrically conductive material is selected from the group consisting of metals, metallic alloys, non-metallic resistors, metallic carbides, transition metal nitrides, metallic borides, metallic silicides, metallic phosphides, carbon in a polymorph comprising at least 60% sp 2 -hybridized carbon atoms, superionic conductors, phosphate electrolytes, mixed oxides doped with lower-valent cations, mixed sulfides doped with lower-valent cations, composite materials comprising at least 30% by weight of any of the previously mentioned electrically conductive materials and any mixtures thereof.
  • the at least one electrically conductive material is selected from the group consisting of metals, metallic alloys, non-metallic resistors, metallic carbides, transition metal nitrides, metallic borides, metallic silicides, metallic phosphides, carbon in a polymorph comprising at least 60% sp 2 -
  • Metallic alloys Ni-Cr, Fe-Ni-Cr, Fe-Ni-AI or a mixture thereof
  • Non-metallic resistors SIC or Si doped SIC
  • Metallic carbides Fe2C, MoC or M02C
  • Transition metal nitrides ZrN, W2N, WN, WN2, VN, TaN or NbN
  • Metallic borides TIB2, HfB2, TaBa, W2B5, Fe2B or LaBe
  • Metallic silicides MoSia, NISI, NaaSi, MgaSi, PtSi, TISI or WSi2
  • Metallic phosphides CU3P, InP, GaP, NaaP, AIP, ZnaPa or CaaPa
  • Carbon in a polymorph comprising at least 60% sp 2 -hybridized carbon atoms: activated carbon such as carbon black, graphite, graphene, petroleum coke, coke or a mixture thereof
  • garnet-type structures such as LizLaaZraOia or substituted ABOa-per- ovskite-type structures
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the at least one electrically conductive material is selected from the group consisting of carbon in a polymorph comprising from 75% to 100% sp 2 - hybridized carbon atoms, such as carbon black, graphite, graphene, petroleum coke, coke or a mixture thereof, metals such as Cu or Ni, metallic alloys, non-metallic resistors such as SiC or Si doped SiC, and any mixtures thereof.
  • the inventive electrically conductive shaped catalyst bodies which comprise at least one catalytically active or activatable material and at least one electrically conductive material, are characterized in that in the sum of the volume fractions of all electrically conductive materials of the shaped catalyst bodies is in the range of from 0.1 to 0.5, preferably in the range of from 0.15 to 0.4, more preferably in the range of from 0.2 to 0.35.
  • volume fraction is defined as the volume of a constituent divided by the sum of the volumes of all constituents of the mixture prior to mixing.
  • the sum of the volume fractions of all different electrically conductive materials of the shaped catalyst bodies can be easily calculated when the volume fractions of all components present in the final electrically conductive shaped catalyst bodies have been determined before forming and converting the mixture of the at least two different materials into said shaped bodies by a compacting method as described above.
  • the volume of each single component of the catalyst bodies is determine by methods known to the person skilled in the art before forming the mixture. It goes without saying that the volumes of the individual components of a mixture are all determined using the same method. Since the individual components forming the mixture are preferably used as powders as described above, the directly measured bulk volume of the respective component in powder form or the calculated bulk volume of said component determined from measuring its mass and its bulk density can be used.
  • tapped volume and mass divided by tapped density or compressed volume and mass divided by compressed density can be used instead of using the measured bulk volume or measured mass divided by measured bulk density.
  • tapped volume and mass divided by tapped density or compressed volume and mass divided by compressed density it is necessary to ensure equal conditions for the measurements. Determining the tapped density is described in DIN EN ISO 787-11 for tapped density. If compressed density and compressed volume are used, the applied pressure to all used powders must be the same.
  • the sum of the volume fractions of all different electrically conductive materials of the shaped catalyst bodies can be also determined from the shaped catalyst bodies themselves in an optical detection of thin sections.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the volume of each solid material of the shaped catalyst bodies is measured or determined by the same method before forming the mixture of the at least two different solid materials.
  • the inventive electrically conductive shaped catalyst bodies are characterized in that the volume fractions of each solid material of the shaped catalyst bodies are measured or determined by using the compressed volume, or mass divided by compressed density, wherein the applied pressure for each solid material is the same value chosen from the range of from 1 MPa to 1000 MPa, preferably from the range of from 10 MPa to 100 MPa, more preferably from the range of from 50 MPa to 70 MPa.
  • the present invention further also provides a process for preparing the inventive electrically conductive shaped catalyst bodies as described in detail above, comprising the process steps of
  • a mixture preferably a homogeneous mixture, comprising at least two different materials, at least one catalytically active or activatable material and at least one electrically conductive material, in particular wherein the materials are in the form of powder particles, are known to the person skilled in the art.
  • mixing processes can be performed by using mortar and pestle, using ball mills, jet mills or other mills, and using mixers or blenders. In most cases the mixing is accompanied by a reduction in the size of the particles of the materials.
  • the inventive process for preparing the electrically conductive shaped catalyst bodies is characterized in that in process step (a) defined amounts of the at least one catalytically active or activatable material and the at least one electrically conductive material are determined by measuring the volumes or the masses of the respective materials before combining them to form the mixture.
  • the inventive electrically conductive shaped catalyst bodies are manufactured by a compaction process as described above. Preferably, a mixture of powdered materials is converted into shaped bodies by a compaction method, which are known to the person skilled in the art.
  • the preferred methods for producing the inventive electrically conductive shaped catalyst bodies are extrusion and tableting.
  • the inventive process for preparing the electrically conductive shaped catalyst bodies is characterized in that in process step (c) the mixture obtained in process step (a) or (b) is converted into shaped bodies by a compaction step selected from the group consisting of extrusion and tableting.
  • the inventive electrically conductive shaped catalyst bodies are preferably used in an electrically heatable catalyst bed in a chemical reactor.
  • the electrically heatable catalyst bed of a chemical reactor which is preferably a moving bed reactor or a fixed bed reactor, in particular a fixed bed reactor, comprises said electrically conductive shaped catalyst bodies or preferably consists of electrically conductive shaped catalyst bodies.
  • the electrically heatable catalyst bed of a moving bed reactor is usually almost identical in all parts of the catalyst bed from top to bottom
  • the electrically heatable catalyst bed of a fix bed reactor might comprise regions (layers) of different electrically conductive shaped catalyst bodies in order to generated different amounts of heat in different parts of the catalyst bed or to vary the number or nature of catalytic reaction centers for example from bottom to top to optimize the desired reaction (zoned catalyst bed).
  • the present invention further provides the use of the above described inventive electrically conductive shaped catalyst bodies as part of a directly electrically heatable catalyst bed or as directly electrically heatable catalyst bed in a chemical reactor, preferably in a moving bed reactor or a fixed bed reactor, in particular in a fixed bed reactor.
  • the present invention further also provides a process for conducting a chemical reaction, which is catalyzed by the electrically conductive shaped catalyst bodies as described in detail above, comprising the process steps of
  • Examples of chemical reactions, which need permanent input of energy in form of heat, and which can be performed in the presence of the inventive electrically conductive shaped catalyst bodies, are endothermic or highly endothermic reactions as mentioned at the beginning.
  • Highly endothermic reactions encompass pyrolysis reactions, dehydrogenation reactions, reforming reactions inter alia.
  • Highly endothermic reactions can also be described by their volume-specific energy consumption in the heated zone, which is preferably greater than 0.5 MW/m 3 , more preferably greater than 1 MW/m 3 , especially greater than
  • the energy consumption may be between 0.5 and 10 MW/m 3 in the heated zone.
  • Preferred chemical reactions according to the above-described inventive process are endothermic gas phase reactions selected from the group of reactions consisting of steam methane reforming (SMR), dry reforming of methane (DRM), alkane dehydrogenation such as propane dehydrogenation, HCN from methane and ammonia (BMA), methanol to (dry) formaldehyde, acetaldehyde from ethanol, methanol to syngas, cyclohexanol dehydrogenation, butadiene from acetaldehyde plus ethanol, alcohol dehydration to olefins, acetic acid dehydration to ketene, HCN from formamide (BMA), acrolein from glycerol, and reverse water-gas shift (RWGS).
  • SMR steam methane reforming
  • DRM dry reforming of methane
  • alkane dehydrogenation such as propane dehydrogenation
  • HCN from methane and ammonia
  • the inventive process for conducting a chemical reaction which is catalyzed by the electrically conductive shaped catalyst bodies as described in detail above is characterized in that the chemical reaction is selected from the group of reactions consisting of steam methane reforming (SMR), dry reforming of methane, alkane dehydrogenation such as propane dehydrogenation, HCN from methane and ammonia (BMA), methanol to (dry) formaldehyde, acetaldehyde from ethanol, methanol to syngas, cyclohexanol dehydrogenation, butadiene from acetaldehyde plus ethanol, alcohol dehydration to olefins, acetic acid dehydration to ketene, HCN from formamide (BMA), acrolein from glycerol and reverse water-gas shift (RWGS).
  • SMR steam methane reforming
  • BMA dry reforming of methane
  • alkane dehydrogenation such as propane dehydrogenation
  • HCN from
  • the present invention further also provides a chemical reactor for conducting a chemical reaction, preferably an endothermic or a highly endothermic reaction, containing a catalyst bed comprising or consisting of the electrically conductive shaped catalyst bodies as described in detail above.
  • the chemical reactor comprising the above disclosed inventive electrically conductive shaped catalyst bodies as part of a directly electrically heatable catalyst bed or as directly electrically heatable catalyst bed is a moving bed reactor or a fixed bed reactor, preferably a fixed bed reactor.
  • the inventive chemical reactor is characterized in that the chemical reactor is a fixed bed reactor.
  • Suitable chemical reactors comprising a directly electrically heatable catalyst bed have been described in the past. Examples of these reactors are for example described in WO 2019/145279 (Title: Device packed with solid material for performing endothermic reactions with direct electrical heating), WO 2020/200522 (Title: Reactor for endothermic high-temperature reactions), WO 2022/194775 (Title: Reactor and method for the pyrolysis of hydrocarbon-contain- ing fluids) or the documents cited in the introduction of the present description.
  • the electrically heatable solid beds inside of the chemical reactors are usually contacted with at least one pair of electrodes for conducting an electric current through a reactor bed.
  • the inventive chemical reactor is characterized in that the chemical reactor is electrically heatable via at least one pair of electrodes conducting an electric current through a reactor bed comprising or consisting of said electrically conductive shaped catalyst bodies.
  • the fixed bed electrical resistivity at 20 °C of the inventive electrically conductive shaped catalyst bodies can be determined as described in EP-application No. 23208352.7 or as described in ISO 10143:2019.
  • a small-scale set-up was used for rapid screening of small volumes of samples (few milliliters).
  • resistivity measurements were performed in a quartz glass tube reactor with an inner diameter (di) of 8.9 mm and outer diameter (d 0 ) of 12.0 mm.
  • the electrodes are constructed out of 1/8” stainless steel tubes and drilled through to ensure gas flow as well as positioning of quartz glass capillary with an inner diameter of 400 pm and outer diameter of 650 pm for surrounding of thermocouples (Type K) with an outer diameter of 0.25 mm.
  • the material under investigation was crushed and sieved into the particle size fraction of 0.5 mm to 1 .0 mm and filled for a bed height hbed between 3 cm to 5 cm (hbed/dj > 3).
  • Figure 1 depicts the resistivity measurement setup and the design of the stainless-steel electrodes.
  • the setup can realize investigations under inert and reactive atmosphere at temperatures up to 900 °C.
  • Argon was dosed with a volume flow of 50 ml/min.
  • the resistivity measurement was conducted by applying direct voltage with a Voltcraft PPS-11815 power supplier, while the voltage was set to 1.1 V to avoid additional heating.
  • the bed resistivity p was determined according to with the electrical resistance R of the catalyst bed and cross section of the catalyst bed Abed.
  • Starting materials for this investigation comprised electrode graphite (1 mm to 5 mm particles) and an industrial AI2O3 catalyst (3 mm extrudates). Both materials were ground and sieved to a powder ( ⁇ 100 pm).
  • the compressed density of pure component powders was determined.
  • the compressed densities after compression at 446 MPa for 1 min were used as a reference.
  • This pressure corresponds to a pressing weight of 7 1 when using a circular stamp with 14 mm in diameter.
  • the amount of powder in the pressing tool is adjusted in a way that the thickness of the resulting tablet is in the range of 3 mm to 5 mm.
  • Table 1 shows the composition and resistivity of particles comprising a compressed powder mixture.
  • Particle size of powder precursors is 100 m to 315 pm.
  • Coupling the resistive heating of a fixed bed with an endothermic catalytic reaction was realized in a -5 ml scale double walled vacuum insulated lab reactor.
  • the reactor is designed to minimize heat losses in radial direction.
  • the catalyst bed is fixed in axial position between two electrodes.
  • Results of directly heated catalytic experiments are compared with reference experiments in a conventional lab reactor with external heating through the reactor wall.
  • the endothermic gas phase dehydration of ethanol to ethylene over Y-AI2O3 as the heterogeneous catalyst was used as a probe reaction.
  • the conductive catalyst particles comprised of 50/50 vol% AI2O3 and graphite powder, respectively, prepared as described in Examples 1 (tablets) and 2 (extrudates).
  • the reaction temperature was varied between 250 °C and 375 °C. Details of test conditions are listed in Table 2 together with the results of catalytic studies.
  • WHSV weight hourly space velocity
  • Ni x Mgi. x Al2O4 catalysts according to WC2018/219992 with considerably increased Ni content were synthesized.
  • the Ni content was increased by the addition of NiO powder (325 mesh).
  • the resulting precursors were transformed into 2.5 mm extrudates, dried, and calcined. Extrudates were crushed and sieved to a defined particle size fraction. Particles were reduced in 10% H2 at 950°C for 1 h. Electric resistivity of the samples was determined as described above. These samples providing nominal Ni contents of 43, 56, and 67 wt% showed no electric conductivity. It is seen that this synthesis route does not lead to electrically conductive particles although the nominal Ni content is similar to the sample of Example 6.
  • Figure 1 Resistivity measurement setup (left) and design of electrodes as side view and top view (right)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne des corps de catalyseur façonnés électriquement conducteurs destinés à être utilisés dans un réacteur chimique comprenant un mélange d'au moins deux matériaux solides différents, le mélange comprenant i) au moins un matériau catalytiquement actif ou activable, et ii) au moins un matériau électriquement conducteur, la somme des fractions volumiques de tous les matériaux électriquement conducteurs des corps de catalyseur façonnés étant dans la plage de 0,2 à 0,35, et les corps de catalyseur façonnés ayant un diamètre caractéristique dans la plage de 1 mm à 50 mm, et la somme des fractions massiques de tous les matériaux catalytiquement actifs ou activables et des fractions massiques de tous les matériaux électriquement conducteurs des corps de catalyseur façonnés étant comprise entre 0,9 et 1. La présente invention concerne en outre un procédé de préparation des corps de catalyseur façonnés électriquement conducteurs, l'utilisation des corps de catalyseur façonnés électriquement conducteurs en tant que partie d'un lit de catalyseur pouvant être directement chauffé électriquement ou en tant que lit de catalyseur pouvant être directement chauffé électriquement dans un réacteur chimique et un réacteur chimique pour conduire une réaction chimique contenant un lit de catalyseur comprenant ou constitué des corps de catalyseur façonnés électriquement conducteurs. La présente invention concerne en outre un procédé de réalisation d'une réaction chimique, qui est catalysée par les corps de catalyseur façonnés électriquement conducteurs.
PCT/EP2025/063407 2024-05-23 2025-05-15 Corps de catalyseur façonnés électriquement conducteurs destinés à être utilisés dans un réacteur chimique Pending WO2025242537A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP24177679 2024-05-23
EP24177679.8 2024-05-23

Publications (1)

Publication Number Publication Date
WO2025242537A1 true WO2025242537A1 (fr) 2025-11-27

Family

ID=91274546

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2025/063407 Pending WO2025242537A1 (fr) 2024-05-23 2025-05-15 Corps de catalyseur façonnés électriquement conducteurs destinés à être utilisés dans un réacteur chimique

Country Status (1)

Country Link
WO (1) WO2025242537A1 (fr)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2982622A (en) 1958-09-02 1961-05-02 Exxon Research Engineering Co Hydrocarbon conversion process
US5480622A (en) 1994-07-05 1996-01-02 Ford Motor Company Electrically heatable catalyst device using electrically conductive non-metallic materials
WO2002045837A2 (fr) 2000-12-09 2002-06-13 Degussa Ag Reacteur a lit fixe chauffe electriquement et son utilisation
DE10236019A1 (de) 2002-08-06 2004-02-19 Basf Ag Reaktor zur Durchführung einer endothermen Reaktion
US7651968B2 (en) 2005-12-12 2010-01-26 Basf Se Shaped body comprising a microporous material and at least one silicon-containing binding agent method for production and use thereof as catalyst in particular in a method for continuous synthesis of methylamines
DE102013226126A1 (de) 2013-12-16 2015-06-18 Technische Universität Bergakademie Freiberg Allotherme Methan-Reformierung mit physikalischer Energierückgewinnung
WO2017072057A1 (fr) 2015-10-28 2017-05-04 Haldor Topsøe A/S Déshydrogénation d'alcanes
WO2018219992A1 (fr) 2017-06-02 2018-12-06 Basf Se Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant du nickel et des spinelles de magnésium
WO2019145279A1 (fr) 2018-01-26 2019-08-01 Basf Se Dispositif garni d'une substance solide pour la mise en œuvre de réactions endothermiques, à chauffage électrique direct
WO2020200522A1 (fr) 2019-04-05 2020-10-08 Linde Gmbh Réacteur pour réactions endothermiques à hautes températures
WO2022023368A1 (fr) 2020-07-28 2022-02-03 Totalenergies Se Processus de pyrolyse directe endothermique de méthane dans un réacteur à lit fluidisé
WO2022023355A1 (fr) 2020-07-28 2022-02-03 Totalenergies Se Processus pour réaliser une réaction de déshydrogénation et/ou d'aromatisation endothermique dans un réacteur à lit fluidisé
WO2022194775A1 (fr) 2021-03-15 2022-09-22 Thyssenkrupp Industrial Solutions Ag Réacteur et procédé de pyrolyse de fluides contenant des hydrocarbures

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2982622A (en) 1958-09-02 1961-05-02 Exxon Research Engineering Co Hydrocarbon conversion process
US5480622A (en) 1994-07-05 1996-01-02 Ford Motor Company Electrically heatable catalyst device using electrically conductive non-metallic materials
WO2002045837A2 (fr) 2000-12-09 2002-06-13 Degussa Ag Reacteur a lit fixe chauffe electriquement et son utilisation
DE10236019A1 (de) 2002-08-06 2004-02-19 Basf Ag Reaktor zur Durchführung einer endothermen Reaktion
US7651968B2 (en) 2005-12-12 2010-01-26 Basf Se Shaped body comprising a microporous material and at least one silicon-containing binding agent method for production and use thereof as catalyst in particular in a method for continuous synthesis of methylamines
DE102013226126A1 (de) 2013-12-16 2015-06-18 Technische Universität Bergakademie Freiberg Allotherme Methan-Reformierung mit physikalischer Energierückgewinnung
WO2017072057A1 (fr) 2015-10-28 2017-05-04 Haldor Topsøe A/S Déshydrogénation d'alcanes
WO2018219992A1 (fr) 2017-06-02 2018-12-06 Basf Se Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant du nickel et des spinelles de magnésium
WO2019145279A1 (fr) 2018-01-26 2019-08-01 Basf Se Dispositif garni d'une substance solide pour la mise en œuvre de réactions endothermiques, à chauffage électrique direct
WO2020200522A1 (fr) 2019-04-05 2020-10-08 Linde Gmbh Réacteur pour réactions endothermiques à hautes températures
WO2022023368A1 (fr) 2020-07-28 2022-02-03 Totalenergies Se Processus de pyrolyse directe endothermique de méthane dans un réacteur à lit fluidisé
WO2022023355A1 (fr) 2020-07-28 2022-02-03 Totalenergies Se Processus pour réaliser une réaction de déshydrogénation et/ou d'aromatisation endothermique dans un réacteur à lit fluidisé
AU2021318837A1 (en) 2020-07-28 2023-02-16 Totalenergies Onetech Process to conduct endothermic direct pyrolysis of methane in a fluidized bed reactor
WO2022194775A1 (fr) 2021-03-15 2022-09-22 Thyssenkrupp Industrial Solutions Ag Réacteur et procédé de pyrolyse de fluides contenant des hydrocarbures

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DIMOV S. V. ET AL: "Thermal conductivity of composite catalysts containing metallic copper as a reinforcing component", THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING, vol. 41, no. 2, 1 April 2007 (2007-04-01), Moscow, pages 184 - 192, XP093305080, ISSN: 0040-5795, Retrieved from the Internet <URL:http://link.springer.com/article/10.1134/S0040579507020121/fulltext.html> DOI: 10.1134/S0040579507020121 *
M. GREUEL ET AL., CHEM. ING. TECH., vol. 96, no. 5, 2024, pages 671 - 678

Similar Documents

Publication Publication Date Title
Vafaeian et al. Ultrasound assisted dispersion of different amount of Ni over ZSM-5 used as nanostructured catalyst for hydrogen production via CO2 reforming of methane
Wang et al. Engineering Ni-Co bimetallic interfaces for ambient plasma-catalytic CO2 hydrogenation to methanol
Danaci et al. Innovative 3D-manufacture of structured copper supports post-coated with catalytic material for CO2 methanation
Chen et al. Catalytic dehydration of bioethanol to ethylene over TiO2/γ-Al2O3 catalysts in microchannel reactors
Bepari et al. Selective production of hydrogen by steam reforming of glycerol over Ni/Fly ash catalyst
Jafarbegloo et al. NiO–MgO solid solution prepared by sol–gel method as precursor for Ni/MgO methane dry reforming catalyst: effect of calcination temperature on catalytic performance
Düdder et al. The role of carbonaceous deposits in the activity and stability of Ni-based catalysts applied in the dry reforming of methane
Wang et al. Boosting CO2 hydrogenation of Fe-based monolithic catalysts via 3D printing technology-induced heat/mass-transfer enhancements
Asalieva et al. Exfoliated graphite as a heat-conductive frame for a new pelletized Fischer–Tropsch synthesis catalyst
Lindström et al. Steam reforming of methanol over copper-based monoliths: the effects of zirconia doping
Pudi et al. Selective hydrogenolysis of glycerol to 1, 2‐propanediol over highly active copper–magnesia catalysts: reaction parameter, catalyst stability and mechanism study
Lu et al. Direct syngas conversion to liquefied petroleum gas: Importance of a multifunctional metal-zeolite interface
CN105107515B (zh) 一种甲烷干重整制合成气的镍‑碳化钼复合催化剂
Tapah et al. Processing of glycerol under sub and supercritical water conditions
Sun et al. Tunable synthesis of ethanol or methyl acetate via dimethyl oxalate hydrogenation on confined iron catalysts
Pegios et al. Ni nanoparticles and the Kirkendall effect in dry reforming of methane
Dai et al. Pt nanoparticles encapsulated in a hollow zeolite microreactor as a highly active and stable catalyst for low-temperature ethanol steam reforming
Zafarnak et al. Co-Ni bimetallic supported on mullite as a promising catalyst for biogas dry reforming toward hydrogen production
Zhang et al. Highly efficient steam reforming of biomass tar model compound using a high-entropy alloy-based structured catalyst
Yahi et al. Dry reforming of methane over Ni/CeO2 catalysts prepared by three different methods
Boahene et al. Higher alcohol synthesis using K-doped CoRhMoS2/MWCNT catalysts: influence of pelletization, particle size and incorporation of binders
Liu et al. Highly efficient selective hydrogenation of levulinic acid to γ-valerolactone over Cu–Re/TiO 2 bimetallic catalysts
Tikhov et al. Preparation of porous ceramometal composites through the stages of mechanical activation and hydrothermal partial oxidation of Me–Al powders
Du et al. The short-channel function of hollow carbon nanoparticles as support in the dehydrogenation of cyclohexane
Zeng et al. Impact of Pd single-site coordination structure on catalytic performance for semihydrogenation of acetylene

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25724783

Country of ref document: EP

Kind code of ref document: A1