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• • 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
  • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
  • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
• • 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
  • B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
  • B01J15/005—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
• • 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
  • B01J19/2495—Net-type 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
  • 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
• • 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
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
  • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
  • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, 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
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
  • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
• • 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
  • 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
  • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• • 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
  • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
  • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1005—Arrangement or shape of catalyst
  • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1005—Arrangement or shape of catalyst
  • C01B2203/1029—Catalysts in the form of a foam
• • 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
  • C01B2203/1052—Nickel or cobalt catalysts
  • C01B2203/1058—Nickel catalysts
• • 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
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1205—Composition of the feed
  • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
  • C01B2203/1235—Hydrocarbons
  • C01B2203/1241—Natural gas or methane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/141—Feedstock
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• Catalytic reactor comprising a honeycomb structure and elements by optimizing the contact with the internal wall of the reactor
• the subject of the present invention is a catalytic reactor comprising a catalytic alveolar structure, in particular a catalytic ceramic or metal foam, and elements that optimize contact with the internal wall of the reactor.
• Ceramic foams or metal alloy foams are known to be used as a catalyst support for chemical reactions, in particular heterogeneous catalysis reactions. These foams are particularly interesting for highly exo- or endothermic reactions (ex: Fischer-Tropsch exothermic reaction, gas-water shift reaction, partial oxidation reaction, reaction of water-gas-shift reaction). methanation ...), and / or for catalytic reactors where one seeks to obtain high space velocities (steam reforming reaction of natural gas, naphtha, LPG ).
• the method of producing open-porosity macro-porous ceramic foams is the impregnation of a polymeric foam (most often polyurethane or polyester), cut to the desired geometry, by a suspension of ceramic particles in an aqueous solvent or organic.
• the excess suspension is removed from the polymer foam by repeated application of compression or centrifugation, in order to keep only a thin layer of suspension on the strands of the polymer.
• After one or more impregnations of the polymeric foam by this method it is dried so as to remove the solvent while maintaining the mechanical integrity of the deposited ceramic powder layer.
• the foam is then heated at high temperature in two stages.
• the first step called debinding is to degrade the polymer and other organic substances possibly present in the suspension, by a slow and controlled temperature rise until complete elimination of the organic volatile substances (typically 500-900 ° C.).
• the second step called sintering consists in consolidating the residual mineral structure by a high temperature heat treatment.
• the final porosity allowed by this method covers a range of 30% to 95% for a pore size ranging from from 0.2mm to 5mm.
• the final pore size (or open macroporosity) is derived from the macrostructure of the initial organic template (polymer foam, usually polyurethane). That varies generally from 60 to 5 ppi (ppi: pore per inch, 50 ⁇ to 5 mm).
• the foam may also be metallic in nature with a chemical formulation that makes it possible to ensure the chemical stability of the architecture under operating conditions (temperature, pressure, gas composition, etc.).
• the metal honeycomb architecture will consist of surface-oxidized NiFeCrAl-based chemical formulations, this surface oxidation allowing the formation of a layer of micrometric alumina protecting the surface. metal alloy of any corrosion phenomenon.
• Ceramic and / or metal honeycomb architectures covered with ceramic are good catalyst supports in several respects:
• Axial means along the axis of the catalytic reactor, and by radial of the inner or outer wall of the catalytic reactor at the center of the catalyst bed,
• thermomechanical and / or thermochemical stresses supported by the bed
• a filling control to improve the homogeneity of the filling of a tube to another.
• a solution of the present invention is a catalytic reactor comprising:
• At least one catalytic structure consisting of at least one catalytic alveolar architecture of external dimensions less than 10% less than the internal dimensions of the reaction chamber;
• At least one second structure positioned in the annular space chosen from:
• a structure comprising at least one metal collar enclosing at least a portion of the cellular architectures and supporting metal fins or
• the fibrous structure may optionally be covered with an active catalytic phase.
• internal dimensions of the reaction chamber is generally meant the internal diameter and the length because the reaction chamber is generally a tube but it may be other dimensions if the reaction chamber has a different shape.
• the catalytic structure comprises several cellular architectures, it will then be constituted by the successive stacking of alveolar architectures.
• the second structure will preferably have characteristics close to that of the reaction chamber (composition, coefficient of thermal expansion, thermal conductivity, etc.) and flexibility characteristics.
• fibrous structure is meant a structure of ceramic fiber type based on silicocalcary, silicoaluminous, ... or a fibrous structure of a metallic nature (iron straw for example, ).
• the constraint concerning the chemical nature (formulation) of the fibrous structure is, with respect to the reaction mixtures, a chemical stability of the constituent material (s) and a chemical inertness. This point is also valid for structures b) and c).
• the fins (structure b) also have the function of increasing the heat transfer.
• the transfer between the inner wall of the reactor, the fin and the catalytic structure is carried out mainly by conduction.
• the powder or the mixture of metallic and / or ceramic powders also serves to improve the heat transfer.
• the transfer between the inner wall of the reactor, the fin and the catalytic structure is carried out mainly by conduction.
• the powder or powder mixture has grain sizes of between 1 and 5,000 ⁇ .
• FIG. 1 represents the peripheral wrapping of the catalytic ceramic or metallic foams stacked successively and surrounded by a fibrous structure.
• FIG. 2 represents a catalytic ceramic or metallic foam sandwiched in a "collar or finned ring" structure.
• FIG. 3 represents a catalytic ceramic or metal foam sandwiched in a bed structure of ceramic and / or metallic powder (s)
• the scale is not representative. Indeed, the annular space is generally smaller than 20 mm, preferably less than 10 mm.
• the reactor according to the invention may have one or more of the following characteristics:
• the cellular architectures are either a ceramic foam or a surface-coated metal foam for high temperature applications, that is to say greater than 500 ° C., of a protective layer of a ceramic nature;
• the second structure is a fibrous structure made of ceramic (alumina, silicate, silicoaluminous fibers, etc.) or metal;
• the metallic fibrous structure may consist of an alloy comprising nickel and chromium, or any alloy compatible with the conditions of the reaction envisaged, for example alloys of Inconel type;
• the fibrous ceramic structure comprises at least one element selected from (i) the following oxides: alumina, silico-aluminous (SiO 2 -Al 2 O 3 ), silico-calcareous (CaO-SiO 2 ), s ilico -magnets (MgO-SiO2), or a combination of these elements or (ii) the following non-oxides: carbides, nitrides;
• the fibrous structure of a metallic nature comprises nickel, preferably an alloy based on NiCrO, NiCrAlO or NiFeCrAlO;
• the second structure is a structure consisting of at least one collar consisting of an alloy comprising predominantly nickel and chromium and enclosing at least a portion of the cellular architectures, and supporting fins consisting of an alloy comprising predominantly nickel and chromium.
• the metal collar and the fins are in inconel;
• the second structure is a structure consisting of a powder or mixture of ceramic and / or metal powders comprising at least 50% of inorganic oxides or non-oxide materials comprising at least one element chosen from (i) the following oxides : alumina, silico-aluminous (S1O2-Al2O3), silico-calcareous (CaO-SiC), silico-magnesium (MgO-SiC), or a combination of these elements or (ii) the following non-oxides carbides, nitrides; and / or metallic materials comprising nickel, preferably an NiCrO, NiCrAlO or NiFeCrAlO-based alloy;
• the second structure is stable and chemically inert vis-à-vis gaseous atmospheres present in the reaction chamber.
• the catalytic alveolar architectures are manufactured from a matrix of polymeric material chosen from polyurethane (PU), polyvinyl chloride (PVC), polystyrene (PS), cellulose and latex, but the ideal choice of foam is limited by stringent requirements.
• the polymeric material must not release toxic compounds, for example PVC is avoided because it can lead to the release of hydrogen chloride.
• the catalytic alveolar architecture when it is ceramic in nature typically comprises inorganic particles chosen from alumina (Al 2 O 3 ) and / or doped alumina (La (1 to 20% by weight) -Al 2 O 3 , Ce ( 1 to 20 wt.% By weight) -Al 2 O 3 , Zr (1 to 20% by weight) -Al 2 O 3 ), magnesia (MgO), spinel (MgAl 2 O 4), hydrotalcites, CaO, silico-calcic, silicoaluminous, zinc oxide, cordierite, mullite, aluminum titanate, and zircon (ZrSiO 2) or ceramic particles selected from ceria (CeO 2 ) and zirconium (ZrO 2 ) ceria stabilized (Gd 2 0 3 between 3 and 10 mol% cerine) and stabilized zirconium (Y 2
• D is selected from magnesium (Mg), yttrium (Y), strontium (Sr), lanthanum (La), presidium (Pr), samarium (Sm), gadolinium (Gd), Erbium (Er) or Ytterbium (Yb); where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0; 5 and ⁇ ensures the electrical neutrality of the oxide.
• the catalytic reactor according to the invention can be used to produce gaseous products, in particular a synthesis gas
• the feed gas preferably comprises oxygen and / or carbon dioxide and / or water vapor mixed with methane.
• these catalytic bed structures can be deployed on all catalytic reactors of the process for producing hydrogen by steam reforming, namely in particular the pre-reforming, reforming and water-gas-shift beds.
• reaction temperatures employed are high and range from 200 to 1000 ° C, preferably from 400 ° C to 1000 ° C.
• the pressure of the reagents can be between 10 and 50 bar, preferably between 15 and 35 bar.
• the present invention also relates to the use, within a catalytic reactor comprising a reaction chamber and a catalytic alveolar structure: - a fibrous structure; and or - A structure comprising at least one metal collar enclosing at least a portion of the honeycomb structure and supporting metal fins to prevent the formation of an annular space between the inner wall of the reaction chamber and the catalytic alveolar structure; and or
• a fibrous structure and / or a structure comprising at least one metal collar, enclosing at least a portion of the cellular architectures and supporting metal fins and / or a powder or a mixture of powder metallic and / or ceramic, in the annular space between the inner wall of the reaction chamber and the catalytic alveolar structure allows both to improve the radial heat transfer, and to limit the flow along the walls.

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