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
  • 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
  • B01J19/2485—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
  • 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
• • 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
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00796—Details of the reactor or of the particulate material
  • B01J2208/00823—Mixing elements
  • B01J2208/00831—Stationary elements
  • B01J2208/00849—Stationary elements outside the bed, e.g. baffles
• • 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
  • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1005—Arrangement or shape of catalyst

Definitions

• Catalytic reactor comprising a catalytic alveolar structure and at least one structural element
• the present invention relates to a catalytic reactor comprising a catalytic cellular structure, in particular a catalytic ceramic or metal foam, and at least one structural element reducing the preferential flows of gas along the walls of the reactor and promoting the transfer of heat.
• 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 Permitted by this method covers a range of 30% to 95% for a pore size ranging 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.
• microstructure of the material itself, ie its chemical formulation, the micro and / or meso-porosity, the size, the dispersion and the metallic surface of the active phase (s), thickness of deposit (s), ...
• the architecture of the catalyst that is to say its geometric shape (granules, barrels, honeycomb monoliths, foam-type foam structures, spheres, pills, sticks, ...),
• the structure of the bed within the reactor (stack of catalytic materials), that is to say the arrangement of catalytic materials architecture / microstructure controlled (s) within the catalytic reactor. It can be envisaged, for example, as catalytic bed structure (s) of successive stacks with or without non-catalytic elements of various functionalities.
• structure of catalytic reactors is meant successive stacks of various architectures and varied (foams, barrels, spheres, ...) of ceramic and / or metal covered with ceramics and microstructures controlled.
• monolithic structure of catalytic reactors is meant successive stacks of ceramic and / or metal honeycomb architectures (foams) covered with ceramics and controlled microstructures.
• a solution of the present invention is a catalytic reactor comprising:
• the reactor according to the invention may have one or more of the following characteristics:
• the catalytic alveolar architecture is a catalytic ceramic foam
• the catalytic alveolar architecture is a metal foam covered with a protective oxide layer on which a catalyst is deposited;
• the catalytic reactor comprises a structural element in the form of a ring, arches, disc or perforated grid, or at least two structural elements in the form of a ring, a disk, a pierced grid or a combination of these forms ;
• the structural element is a disc having at least one opening, for example with 4 openings, with the opening or openings representing between 85% and 95% of the surface of the disc; ( Figure 5)
• the structural element is metallic in nature; it preferably comprises an alloy rich in nickel and chromium;
• the metallic structural element is machined in the same alloy as the catalytic reactor casing.
• the envelope of the catalytic reactor is generally composed of an alloy comprising nickel and chromium;
• the structural element is ceramic in nature.
• 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 ceramic type typically comprises inorganic particles selected from alumina (Al 2 03) and / or doped-alumina (La (1 to 20% by weight) - A1 2 0 3, This (1 to 20 wt.% By weight) - Al 2 O 3 , Zr (1 to 20 wt.%) -Al 2 O 3 ), magnesia (MgO), spinel (MgAl 2 O 4 ), hydrotalcites CaO, silicocalcary, silicoaluminous, zinc oxide, cordierite, mullite, aluminum titanate, and zircon (ZrSiC ⁇ ); or ceramic particles selected from ceria (Ce0 2 ), zirconium (Zr0 2 ), stabilized ceria (Gd 2 0 3 between 3 and 10 mol% cerine) and stabilized zirconium (Y 2 0 3 between 3 and 10 mol% zirconium) and the mixed oxides of formula (I):
• 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.
• FIGS. 1 to 5 Each figure represents an example of a structural element.
• Figure 1 shows:
• one or more architectures (a) of ceramic and / or metal cells with controlled catalytic micro-structures
• the bed is entirely structured in ceramic foam, in order to benefit from a volume catalytic activity and optimum heat transfer along the entire tube.
• the static mixer at the inlet makes it possible to avoid possible preferential flows to the walls.
• the static mixer is in contact with the inner wall of the reactor.
• the foam may also be metallic in nature.
• Figure 2 shows: ceramic and / or metal and controlled catalytic microstructure architectures (these architectures are, for example, stacked ceramic catalytic foam bars), and
• non-catalytic structural elements preferably metallic or ceramic, in the form of rings (c) between the cellular architectures.
• inorganic non-oxide type materials having intrinsic properties of high thermal conductivity (silicon carbide, silicon nitride, etc.) will be chosen.
• any flow to the walls are avoided by the rings.
• the rings are in contact with the inner wall of the reactor.
• ceramic and / or metal and controlled catalytic microstructure architectures are, for example, stacked ceramic catalytic foam bars
• non-catalytic structural elements preferably metallic, in the form of rings (c) and central discs (d) arranged between the cellular architectures.
• ceramic and / or metal and controlled catalytic microstructure architectures are, for example, stacked ceramic catalytic foam bars
• non-catalytic structural elements preferably metal or ceramic, in the form of arches (e) arranged between the cellular architectures.
• FIG. 5 represents an example of a structural element to be inserted between the cellular architectures.
• This element has the shape of a ring of diameter corresponding to internal diameter of the reaction chamber, with a cross centered on the middle of the diameter of the honeycomb architecture.
• This element if it is metallic, must be strongly open to generate the lowest possible pressure drop and will preferably be machined in the same alloy as the reactor so that the expansion is identical to that of the reaction chamber so as to stick well. at the wall.
• the structural element according to FIG. 5 is in contact with the internal wall of the reactor. This element interposed between the cellular architectures allows:
• 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, carbon dioxide or water vapor mixed with methane.
• these catalytic bed structures can be deployed on all the catalytic reactors of the hydrogen production process by steam forming, 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Inorganic Chemistry (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Hydrogen, Water And Hydrids (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=42124329

Family Applications (1)

Country Status (6)

Families Citing this family (3)

Family Cites Families (8)

• 2009
  • 2009-12-01 FR FR0958553A patent/FR2953150B1/fr not_active Expired - Fee Related
• 2010
  • 2010-11-24 CN CN2010800540758A patent/CN102639436A/zh active Pending
  • 2010-11-24 BR BR112012013313A patent/BR112012013313A2/pt not_active Application Discontinuation
  • 2010-11-24 US US13/513,364 patent/US20120248377A1/en not_active Abandoned
  • 2010-11-24 EP EP10803605A patent/EP2507163A1/de not_active Withdrawn
  • 2010-11-24 WO PCT/FR2010/052501 patent/WO2011067506A1/fr active Application Filing

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events