WO2015181472A1 - Catalyst in the form of a cylinder perforated from one side to the other - Google Patents

Catalyst in the form of a cylinder perforated from one side to the other Download PDF

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Publication number
WO2015181472A1
WO2015181472A1 PCT/FR2015/051324 FR2015051324W WO2015181472A1 WO 2015181472 A1 WO2015181472 A1 WO 2015181472A1 FR 2015051324 W FR2015051324 W FR 2015051324W WO 2015181472 A1 WO2015181472 A1 WO 2015181472A1
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WIPO (PCT)
Prior art keywords
catalyst
cylinder
catalyst according
barrel
hole
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PCT/FR2015/051324
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French (fr)
Inventor
Marie BASIN
Caroline Bertail
Pascal Del-Gallo
Daniel Gary
Amara FEZOUA
Nik LYGEROS
Clémence NIKITINE
Isabelle PITAULT
Original Assignee
L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Centre National De La Recherche Scientifique
L'ecole Superieure De Chimie-Physique-Electronique De Lyon
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Application filed by L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude, Centre National De La Recherche Scientifique, L'ecole Superieure De Chimie-Physique-Electronique De Lyon filed Critical L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Publication of WO2015181472A1 publication Critical patent/WO2015181472A1/en

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    • 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
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical 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
    • B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J35/40—
    • B01J35/50—
    • B01J35/56—
    • B01J35/60—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
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    • 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
    • C01B3/323—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 catalyst
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • B01J2208/00008—Controlling the process
    • B01J2208/00539—Pressure
    • 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
    • B01J2208/00008—Controlling the process
    • B01J2208/00548—Flow
    • 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
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30215—Toroid or ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30223—Cylinder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30242—Star
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/304—Composition or microstructure of the elements
    • B01J2219/30416—Ceramic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/304—Composition or microstructure of the elements
    • B01J2219/30475—Composition or microstructure of the elements comprising catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/31—Size details
    • B01J2219/312—Sizes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
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    • 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
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    • 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]
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    • 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
    • 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

  • the present invention relates to novel catalyst structures.
  • a catalyst is a material that converts reagents into product through repeated and uninterrupted cycles of elemental phases. The catalyst participates in the conversion by returning to its original state at the end of each cycle throughout its lifetime.
  • Hollow forms (cylinders or multi-lobes) is perforated with several convex holes of different shapes (circle, angular sector, lobe) or holes with several non-convex holes such as the inner quadrilobe.
  • PFV Vacuum Fraction
  • the percentage of vacuum fraction of the stack (PFVE) catalytic structures is directly related to the pressure drop of the catalytic bed.
  • the PFVE is defined as follows: ⁇ -, ⁇ ⁇ Total volume of full cylinders
  • the S / M ratio is defined as follows:
  • miniliths or small monoliths that is to say cylinders of centimeter dimensions having a network of square, triangular or hexagonal channels.
  • Monoliths are used in the clearance of gases in the form of a single block that takes the entire volume of the reactor (Ex: monolith used in the car catalytic converters of the order of D20xL40 cm).
  • Miniliths are centimetric blocks (such as barrels) with, for example, a diameter that can range from 5 to 20 mm and a height that can range from 5 to 20 mm, which are stacked loose in a reactor.
  • the channels are the same, it is the size and use of the set that change.
  • the thin film systems are not the optimal solution to allow stable catalytic bed performance over time and ensure a long service life. adequate life of the catalytic bed.
  • the geometry of the substrate and the current coating techniques limit the maximum thickness that can be deposited to have an adherent deposit and not cracked.
  • the present invention proposes (i) improving the energy efficiency of gas / solid, liquid / solid or gas / liquid / solid catalytic processes by reducing the pressure drop within the catalytic reactors, (ii) increasing the catalytic efficiency of gas / solid, liquid / solid or gas / liquid / solid reactions limited by intraparticle and extraparticle material and heat transfers, (iii) increase the transfer of heat and material in the gas phase.
  • a solution of the present invention is a catalyst for catalytic reactors in the form of a centimetric barrel and whose geometry defines at least one hole opening on either side of the barrel and such as the percentage of vacuum fraction (PFV) of the barrel is between 20% and 50%, the Percentage of Internal Surface (PSI) of the barrel is between 60% and
  • PFV percentage of vacuum fraction
  • PSI Percentage of Internal Surface
  • the surface / volume (S / V) ratio of the barrel is greater than 1000 m 2 / m 3 .
  • PSI Internal Surface Percentage
  • the catalyst according to the invention may have one or more of the following characteristics:
  • the barrel has a diameter ranging from 5 to 20 mm and a height ranging from 5 to 20 mm, with a diameter / height ratio of between 0.5 and 2, preferably between 0.8 and 1.5.
  • the surface / volume ratio (S / V) is greater than 2000 m 2 / m 3 .
  • the barrel has an external shape chosen from the hexagonal prism, the cylinder, the cylinder with elliptical section, the Vauban prism and the ellipsoid.
  • the hole has a non-convex shape chosen from the von Koch flake, the Star of David, the Greek cross, and the serrated side square.
  • the hole has an axis of symmetry not parallel to the axis of symmetry of the barrel (we speak of oblique or helical holes); note that if the geometry of the barrel defines several holes, the axes of symmetry of these holes are preferably non-parallel.
  • said catalyst consists of a support and an active phase deposited on the support;
  • the catalyst support is of the oxide type or of a mixture of inorganic oxides.
  • the inorganic oxides are chosen from Al 2 O 3 , MgO, CaO, ZrO 2 , TiO 2 , Ce 2 O 3 , and CeO 2
  • the active phase deposited in and / or on the support by all types of techniques consists of metal particles chosen from Ni, Rh, Pt, Pd, Co, Mo,
  • the active phase can be deposited in and / or on the support by all types of techniques (impregnation, coprecipitation, ...)
  • the barrel may also have on its outer wall one or more grooves.
  • the losses in catalytic reactors are a paramount parameter influencing the performance of certain gas / solid, liquid / solid or gas / liquid / solid processes.
  • the pressure drop in a reactor is related to the geometry of the catalyst and the compactness of its stack and / or the formation of fines during filling due to its low mechanical strength.
  • Some catalytic gas / solid, liquid / solid or gas / liquid / solid processes involve several catalytic reactors which may have recycles (eg the flow leaving a secondary reactor is returned to the top of a primary reactor). In these cases, compression steps may be necessary and adversely affect the overall efficiency of the process if the pressure drops in the reactors are too great.
  • other processes may involve, downstream of the catalytic reactors, units whose performance can be reduced by a too low inlet pressure (eg purification units).
  • the invention proposes new geometries with high PFV (greater than 20%) in order to reduce the pressure drops.
  • the catalytic reactions gas / solid, liquid / solid or gas / liquid / solid having a fast intrinsic kinetics are then limited by the transfer of material (transfer of reagents) or gas or liquid phases to the catalyst surface (extraparticular transfer), or from the surface of the catalyst to the active sites within the pores of the catalyst (intraparticular transfer).
  • transfer of material transfer of reagents
  • extraparticular transfer transfer of material
  • intraparticular transfer the transfer of material
  • the step limiting the catalytic efficiency is the transport of the reagents to the active site where the reaction takes place.
  • a key catalyst parameter influencing intraparticle and extraparticular transfers is the S / V ratio.
  • the extraparticular material transfer is, in turn, also related to the turbulence generated in the gas phase by the shape of the catalyst.
  • the invention described here proposes new catalyst geometries to reduce these limitations. An analogy between the transfers of matter and heat can be made.
  • the improvement of heat transfer can extend the life of tubular reactors exposed to endothermic reactions, type SMR (ex-situ heating by any type of heat source: flame, electric).
  • This invention proposes, on the one hand, new external forms for the barrel that have not been proposed before; on the other hand, new geometries of holes that have never been considered.
  • the external shape of the barrel can be in the following forms:
  • the internal structure is composed of holes having a non-convex shape:
  • Figures la) and lb) show examples of catalyst according to the invention in the form of barrel comprising a single hole of non-convex shape;
  • Figures 2a) and 2b) show examples of the catalyst according to the invention in the form of a barrel comprising a plurality of non-convex shaped holes.
  • the proposed new catalyst geometries are of barrel type with a diameter ranging from 5 to 20 mm and a height ranging from 5 to 20 mm, with a ratio of diameter / height (D / H) for example between 0.5 and 2 but preferably between 0.8 and 1.5.
  • This ratio D / H is important because it will also condition the arrangement / stacking of the bed.
  • the stacking density is important because it will reflect the amount of active material present in the reactor, the stack will be defined by the position of the object (horizontal, vertical, oblique). These parameters will also influence the pressure drop in the bed.
  • the oblique position will be preferentially sought because it will promote turbulent flows within the reactor.
  • An object with a ratio ⁇ 0.8 will tend to stack horizontally, while a ratio object between 0.8 and 1.5 will tend to stack obliquely due to the height of its center of gravity.
  • the external forms of barrel according to the invention make it possible to obtain a robust mechanical strength because the thickness of the walls is adapted to the geometry of the holes.
  • the order of magnitude for the wall thickness is about 2 mm.
  • the barrels according to the invention have a high PFV: from 20% to 50%.
  • a single barrel with a diameter of 10 mm and a height of 15 mm and a hole diameter of 5 mm has a PFV of 25%.
  • a barrel of diameter 10 mm and height 15 mm pierced with 7 holes of diameter 2 mm has a PFV of 28%.
  • Both forms above have PFVEs between 35% and 40%.
  • these forms have been designed to reduce the number of symmetries.
  • These shapes were designed via a fractal approach by exploiting a self-similar form based on a single pattern generator, and the number of holes at the periphery will preferably be odd or the central pattern will be shifted.
  • the hole has an axis of symmetry not parallel to the axis of symmetry of the cylinder (oblique or helical holes) and if the geometry of the barrel defines several holes, the axes of symmetry of these holes are preferably non-parallel.
  • the catalyst according to the invention can be used in any type of reaction (oxidation, hydrogenation, etc.).
  • the main targeted reactions of the gas / solid type will be the reforming reactions of a hydrocarbon (natural gas, naphtha, biogas, off-gas refinery ...), an alcohol (MeOH, EtOH), glycerol, by a oxidant such as water vapor, C0 2 , oxygen or their mixture, transformation reactions of a synthesis mixture rich in H 2 / CO such as the reaction of water gas shift, the reverse water reaction gas shift, the synthesis reaction of an alcohol (MeOH, ..), the methanation reaction.
  • a hydrocarbon natural gas, naphtha, biogas, off-gas refinery
  • an alcohol MeOH, EtOH
  • glycerol glycerol
  • transformation reactions of a synthesis mixture rich in H 2 / CO such as the reaction of water gas shift, the reverse water reaction gas shift, the synthesis reaction of an alcohol (MeOH, ..), the methan
  • the use of the catalyst according to the invention is not limited to the gas / solid type reactions but is applicable to liquid / solid and gas / liquid / solid reactions.
  • the catalyst according to the invention can operate under pressure (1 to 60 atm) and temperature (150 - 1000 ° C).
  • the subject of the present invention is also a catalytic reactor comprising a stack of catalysts according to the invention.
  • Example 1 The advantages of the subject of the invention have been illustrated by the example below.
  • Example 1 The advantages of the subject of the invention have been illustrated by the example below.
  • the pressure drop and tracing experiments were carried out in a reactor 15 cm in diameter and 2.5 m high (bed volume 46.9 L). This pilot has 5 taps for the pressure drop and 2 taps measurements for the radial dispersion of the gas.
  • the gas phase used is air with a flow rate ranging from 0 to 185 m / n (ie 0 to 2.9 m / s) and the tracer is methane. For tracer measurements, methane is injected through the top and center of the bed section ( Figure 3).
  • Samples are taken over the entire diameter of the reactor using canes passing through the reactor taps ( Figure 3).
  • Axial dispersions make it possible to obtain information on reactor performance (ideal piston, dispersion piston, etc.) by measuring the number of
  • v interstitial velocity
  • m bed height
  • Dax axial dispersion
  • the information on the fluid distribution through the bed is obtained by the radial dispersion data.
  • the object according to the invention tested in this example is the Von Koch Vauban drum 7 holes 19 mm in diameter and 15 mm in height. It is compared to commercial objects which are 5 mm diameter glass beads and barrels with 10 holes 19 mm in diameter and 15 mm in height with a 5 mm central hole and 9 3 mm peripheral holes.
  • a 10-hole cylinder is shown in FIG.
  • the porosity for the 7-hole Von Koch Vauban drills is 0.63, for the 10-hole drums of 0.53 and for the 0.37-glass drums.
  • Table 1 shows the pressure drop of the 10-hole cylinders as a function of volume flow or empty drum speed.
  • Table 2 shows the pressure drop of the glass beads as a function of volume flow or empty drum speed.
  • Table 3 shows the pressure drops of the Von Koch barrels as a function of volume flow or empty drum speed.
  • Figure 5 allows a comparison of the results given in Tables 1, 2 and 3.
  • Table 4 shows the axial dispersion of the 10-hole drums as a function of the empty drum speed.
  • Table 5 shows the axial dispersion of Von Koch barrels as a function of the empty drum speed.
  • FIG. 6 allows a comparison of the results given in Tables 4 and 5.
  • the triangles correspond to the axial dispersion for the Von Koch barrels and the squares correspond to the axial dispersion for the 10-hole barrels.
  • Table 6 shows the number of Peclets determined with a flow rate of 80 m / n for 10-hole cylinders and Von Koch barrels.
  • the pressure drops are of the same order of magnitude for Von Koch Vauban barrels and 10-hole barrels, but much better than those of 5 mm balls.
  • the Von Koch Vauban barrels have a higher bedlet than the 10-hole barrels (400 and 280 respectively). Therefore, a reactor with von Koch Vauban barrels will operate closer to that of a perfectly piston reactor. This result is supported by the calculations of the axial dispersions as a function of the empty drum speeds. In fact, as shown in FIG. 6, the axial dispersions (Dax) of von Koch Vauban barrels are smaller than that of 10-hole barrels, in other words the deviations from a perfectly piston flow are lower with the von barrels. Koch Vauban.
  • Example 2 Radial dispersion measurements were made in a tube 15 cm in diameter and 80 cm high. The tube was filled on 40cm of the different particles and the measurements were carried out with an air flow of 40m3 / h. The experiment consisted of injecting methane taps 28 cm high with respect to the holding grid, the injector being located in the stack. The samples were taken using a cane under the particle holding grid at 9 points per axis (distances from the center: -7.5 cm, -5.5 cm, -3.5 cm; -1.5 cm, 0 cm, 1.5 cm, 3.5 cm, 5.5 cm, 7.5 cm) and 6 axes spaced 30 degrees apart (ie at 0, 30, 60, 90, 120 and 150 degrees).
  • the object according to the invention tested in this example is the von Koch Vauban 7-hole drum with a diameter of 19 mm and a height of 15 mm. It is compared to commercial objects which are 5 mm diameter glass beads and barrels with 10 holes 19 mm in diameter and 15 mm in height with a 5 mm central hole and 9 3 mm peripheral holes.
  • a 10-hole cylinder is shown in Figure 5. It is compared to wooden cylinders with a diameter of 19 mm and a height of 15 mm and a Vauban cylinder with a diameter of 19 mm and a height of 15 mm (von Koch Vauban barrel, 7 holes in diameter). 19 mm and height 15 mm whose holes were obstructed).
  • the cylindrical type shapes greatly improve the radial dispersion of the stacks compared to the stacks of balls.
  • the radial dispersions for the 19mmx15mm cylinders and for the Vauban are equivalent. Between the Vauban and the von Koch Vauban, the presence of the holes and their characteristics improve the radial dispersion of 130%, whereas, for the barrels, the presence of the holes and their characteristics, improve the radial dispersion than of 95% (comparison Barrels and Cylinders 19mmx15mm). In summary, the von Koch Vauban forms improve radial dispersions by 40% compared with commercial barrel-type shapes.
  • Example 3 Measurements of liquid flow dispersions were made in a tube 30 cm in diameter and 50 cm high. The tube was filled on 30cm of different particles. The experiment consisted of injecting 100 ml of water at the top center of the stack and collecting under the holding grid the liquid flowing in 96 receptacles of size 30mmx30mmx28mm. The receptacles are positioned in such a way as to form a grid of 10x10 receptacles (there is no receptacle in the corners). For each experiment, the receptacles are then weighed and the impacted surface is measured by the liquid flow. Stacks were previously saturated with water to fill the porosities of the constituent constituents 10-hole barrels and von Koch Vauban.
  • the object according to the invention tested in this example is the von Koch Vauban 7-hole drum with a diameter of 19 mm and a height of 15 mm. It is compared to commercial objects which are 5 mm diameter glass beads and barrels with 10 holes 19 mm in diameter and 15 mm in height with a 5 mm central hole and 9 3 mm peripheral holes.
  • a 10-hole cylinder is shown in FIG.
  • the table below shows the number of wet receptacles and the percentage of impacted area relative to the section of the tube obtained at the end of pouring 100 mL of water.
  • von Koch Vauban exhibits better dispersions in liquid flow than 10-hole and 10-hole barrels.

Abstract

The invention relates to a catalyst for catalytic reactors in the form of a centimetric cylinder of which the geometry defines at least one hole which opens on both sides of the cylinder, such that the void fraction percentage (VFP) of the cylinder is between 20 % and 50 %, the internal surface area percentage (ISP) of the cylinder is between 60 % and 220 % and the surface area / volume ratio (S/V) of the cylinder is greater than 1000 m2 / m3.

Description

CATALYSEUR SOUS LA FORME D'UN BARILLET PERFORE DE  CATALYST IN THE FORM OF A PERFORATED BARREL
PART EN PART  SHARE
La présente invention concerne des nouvelles structures de catalyseurs. The present invention relates to novel catalyst structures.
Un catalyseur est un matériau qui convertit des réactifs en produit à travers des cycles répétés et ininterrompus de phases élémentaires. Le catalyseur participe à la conversion en retournant à son état d'origine à la fin de chaque cycle durant toute sa durée de vie. A catalyst is a material that converts reagents into product through repeated and uninterrupted cycles of elemental phases. The catalyst participates in the conversion by returning to its original state at the end of each cycle throughout its lifetime.
Actuellement les catalyseurs commerciaux pour les procédés gaz/solide, liquide/solide ou gaz/liquide/solide se présentent sous différentes formes :  Currently commercial catalysts for the gas / solid, liquid / solid or gas / liquid / solid processes come in different forms:
- des formes pleines (sphère, cylindre, trilobé, quadrilobe, tétraèdre, cube, octaèdre, dodécaèdre, icosaèdre) - solid shapes (sphere, cylinder, trilobe, quadrilobe, tetrahedron, cube, octahedron, dodecahedron, icosahedron)
- des formes creuses (cylindres ou multi-lobes) soit trouées de plusieurs trous convexes de différentes formes (cercle, secteur angulaire, lobe), soit trouées de plusieurs trous non convexes comme le quadrilobe interne.  - Hollow forms (cylinders or multi-lobes) is perforated with several convex holes of different shapes (circle, angular sector, lobe) or holes with several non-convex holes such as the inner quadrilobe.
Toutes ces formes pleines ou faiblement percées présentent l'inconvénient de générer une perte de charge importante car leur Pourcentage de Fraction de Vide (PFV) et le Pourcentage de Fraction de Vide de leur Empilement (PFVE) sont faibles. De plus, ces géométries ont un rapport Surface/Volume (S/V) faible; ce qui implique que les transferts de matière (transfert des réactifs) intraparticulaire (i.e. de la surface du catalyseur vers les sites actifs au sein des pores du catalyseur) et extraparticulaire (i.e. des phases gazeuse ou liquide vers la surface du catalyseur) sont faibles et limitants dans le cas d'une réaction à cinétique intrinsèque rapide (cas des réactions catalytiques gaz/solide, liquide/solide ou gaz/liquide/solide). Ainsi, dans le cas des réactions limitées par le transfert de matière, ces géométries mettent en jeu des quantités importantes de matière catalytique dont seulement une partie est utile à la réaction. All these solid or slightly pierced forms have the disadvantage of generating a significant pressure drop because their percentage of vacuum fraction (PFV) and the percentage of vacuum fraction of their stack (PFVE) are low. In addition, these geometries have a low Surface / Volume (S / V) ratio; which implies that transfers of material (transfer of reagents) intraparticular (ie from the surface of the catalyst towards the active sites within the pores of the catalyst) and extraparticular (ie from the gaseous or liquid phases towards the surface of the catalyst) are weak and limiting in the case of a fast intrinsic kinetics reaction (case of catalytic reactions gas / solid, liquid / solid or gas / liquid / solid). Thus, in the case of reactions limited by the transfer of material, these geometries involve large amounts of catalytic material of which only a part is useful for the reaction.
Le pourcentage de Fraction de Vide (PFV) des structures catalytiques est directement lié à la perte de charge du lit catalytique. Le PFV est défini comme suit : The percentage of Vacuum Fraction (PFV) catalytic structures is directly related to the pressure drop of the catalytic bed. The PFV is defined as follows:
„„T, Volume de vide du barillet . nr. "" T , Vacuum volume of the barrel. nr .
PFV— x lOO  PFV-x 100
Volume total du même barillet plein  Total volume of the same full barrel
Le pourcentage de Fraction de Vide de l'Empilement (PFVE) des structures catalytiques est directement lié à la perte de charge du lit catalytique. Le PFVE est défini comme suit : ηΊ-,τ^ Volume total des barillets pleins The percentage of vacuum fraction of the stack (PFVE) catalytic structures is directly related to the pressure drop of the catalytic bed. The PFVE is defined as follows: ηΊ -, τ ^ Total volume of full cylinders
PFVE= 100-—— —— — x 100  PFVE = 100 --- - - x 100
Volume total de l empilement  Total volume of the stack
Le rapport S/M est défini comme suit :  The S / M ratio is defined as follows:
S _ Surface géométrique du catalyseur  S _ Geometric surface of the catalyst
V Volume géométrique du catalyseur  V Geometric volume of the catalyst
Il est aussi possible de trouver des catalyseurs non-commerciaux actuellement tels que:  It is also possible to find non-commercial catalysts currently such as:
- des formes cylindriques ou sphériques où la phase catalytique est supportée sur un substrat de type mousse (céramique voire métallique). Ces substrats permettent de diminuer notablement la perte de charge et d'augmenter le ratio S/M. Ce type de catalyseur est décrit par exemple dans les documents EP2009057386, EP2009057451 et EP2009055783. cylindrical or spherical shapes in which the catalytic phase is supported on a foam-type substrate (ceramic or even metallic). These substrates can significantly reduce the pressure drop and increase the S / M ratio. This type of catalyst is described for example in the documents EP2009057386, EP2009057451 and EP2009055783.
- minilithes ou petits monolithes, c'est-à-dire des cylindres de dimensions centimétriques présentant un réseau de canaux carrés, triangulaires ou hexagonaux. Les monolithes sont utilisés dans la dépollution des gaz sous la forme d'un bloc unique qui prend tout le volume du réacteur (Ex : monolithe utilisé dans les pots catalytiques de voiture de dimensions de l'ordre de D20xL40 cm). Les minilithes (mot encore peu employé) sont des blocs centimétriques (comme des barillets) ayant, par exemple, un diamètre pouvant aller de 5 à 20 mm et une hauteur pouvant aller de 5 à 20 mm, que l'on empile en vrac dans un réacteur.  miniliths or small monoliths, that is to say cylinders of centimeter dimensions having a network of square, triangular or hexagonal channels. Monoliths are used in the clearance of gases in the form of a single block that takes the entire volume of the reactor (Ex: monolith used in the car catalytic converters of the order of D20xL40 cm). Miniliths (a word that is still little used) are centimetric blocks (such as barrels) with, for example, a diameter that can range from 5 to 20 mm and a height that can range from 5 to 20 mm, which are stacked loose in a reactor.
Les canaux sont les mêmes, c'est la dimension et l'utilisation de l'ensemble qui changent.  The channels are the same, it is the size and use of the set that change.
Ces formes sont très poreuses, présentent un PFV supérieur à 50% et génèrent donc moins de pertes de charge. Toutefois, les minilithes basés sur un réseau de canaux présentant des symétries conduisent à un empilement ayant, statistiquement, de nombreux chemins préférentiels. Cela induit une faible dispersion radiale, peu de turbulence et donc de mauvais transferts de matière extraparticulaire. These forms are very porous, have a PFV greater than 50% and therefore generate less pressure drop. However, the miniliths based on a network of channels with symmetries lead to a stack having, statistically, many preferential paths. This induces a low radial dispersion, little turbulence and therefore poor extraparticular material transfers.
Dans le cas de certaines réactions gaz/solide, liquide/solide ou gaz/liquide/solide, les systèmes sous forme de couches minces ne sont pas la solution optimale pour permettre des performances du lit catalytique stables au cours du temps et assurer une durée de vie adéquate du lit catalytique. D'autre part, la géométrie du substrat et les techniques d'enduction actuelles limitent l'épaisseur maximale qu'il est possible de déposer permettant d'avoir un dépôt adhérent et non fissuré. La présente invention se propose (i) d'améliorer l'efficacité énergétique des procédés catalytiques gaz/solide, liquide/solide ou gaz/liquide/solide en diminuant la perte de charge au sein des réacteurs catalytiques, (ii) d'augmenter l'efficacité catalytique des réactions gaz/solide, liquide/solide ou gaz/liquide/solide limitées par les transferts de matière et de chaleur intraparticulaires et extraparticulaires, (iii) d'augmenter le transfert de chaleur et de matière dans la phase gazeuse. In the case of certain gas / solid, liquid / solid or gas / liquid / solid reactions, the thin film systems are not the optimal solution to allow stable catalytic bed performance over time and ensure a long service life. adequate life of the catalytic bed. On the other hand, the geometry of the substrate and the current coating techniques limit the maximum thickness that can be deposited to have an adherent deposit and not cracked. The present invention proposes (i) improving the energy efficiency of gas / solid, liquid / solid or gas / liquid / solid catalytic processes by reducing the pressure drop within the catalytic reactors, (ii) increasing the catalytic efficiency of gas / solid, liquid / solid or gas / liquid / solid reactions limited by intraparticle and extraparticle material and heat transfers, (iii) increase the transfer of heat and material in the gas phase.
Une solution de la présente invention est un catalyseur pour réacteurs catalytiques sous la forme d'un barillet centimétrique et dont la géométrie définit au moins un trou débouchant de part et d'autre du barillet et tel que le pourcentage de fraction de vide (PFV) du barillet est compris entre 20% et 50%, le Pourcentage de Surface Interne (PSI) du barillet est compris entre 60% et A solution of the present invention is a catalyst for catalytic reactors in the form of a centimetric barrel and whose geometry defines at least one hole opening on either side of the barrel and such as the percentage of vacuum fraction (PFV) of the barrel is between 20% and 50%, the Percentage of Internal Surface (PSI) of the barrel is between 60% and
220% et le rapport surface / volume (S/V) du barillet est supérieur à 1000 m2/m3. 220% and the surface / volume (S / V) ratio of the barrel is greater than 1000 m 2 / m 3 .
Le Pourcentage de Surface Interne (PSI) des structures catalytiques est directement lié au transfert extraparticulaire. Le PSI est défini comme suit :  The Internal Surface Percentage (PSI) of catalytic structures is directly related to extraparticular transfer. The PSI is defined as follows:
p£ = Surface des trous du barillet 100 p £ = Drill hole area 100
Surface totale du barillet - Surface des trous du barillet  Total barrel area - barrel hole area
Selon le cas, le catalyseur selon l'invention peut présenter une ou plusieurs des caractéristiques suivantes : Depending on the case, the catalyst according to the invention may have one or more of the following characteristics:
- le barillet présente un diamètre pouvant aller de 5 à 20 mm et une hauteur pouvant aller de 5 à 20 mm, avec un rapport diamètre / hauteur compris entre 0,5 et 2, de préférence compris entre 0,8 et 1,5.  - The barrel has a diameter ranging from 5 to 20 mm and a height ranging from 5 to 20 mm, with a diameter / height ratio of between 0.5 and 2, preferably between 0.8 and 1.5.
- le rapport surface / volume (S/V) est supérieur à 2000 m2/m3. the surface / volume ratio (S / V) is greater than 2000 m 2 / m 3 .
- le barillet présente une forme externe choisie parmi le prisme hexagonal, le cylindre, le cylindre à section elliptique, le prisme de Vauban et l'ellipsoïde.  the barrel has an external shape chosen from the hexagonal prism, the cylinder, the cylinder with elliptical section, the Vauban prism and the ellipsoid.
- le trou présente une forme non convexe choisie parmi le flocon de Von Koch, l'étoile de David, la croix grecque, et le carré à côté dentelé.  - the hole has a non-convex shape chosen from the von Koch flake, the Star of David, the Greek cross, and the serrated side square.
- le trou présente un axe de symétrie non parallèle à l'axe de symétrie du barillet (on parlera de trous obliques ou hélicoïdaux); notons que si la géométrie du barillet définit plusieurs trous, les axes de symétrie de ces trous sont de préférence non parallèles. - ledit catalyseur est constitué d'un support et d'une phase active déposée sur le support ; - The hole has an axis of symmetry not parallel to the axis of symmetry of the barrel (we speak of oblique or helical holes); note that if the geometry of the barrel defines several holes, the axes of symmetry of these holes are preferably non-parallel. said catalyst consists of a support and an active phase deposited on the support;
- le support du catalyseur est de type oxyde ou d'un mélange d'oxydes inorganiques.  the catalyst support is of the oxide type or of a mixture of inorganic oxides.
- les oxydes inorganiques sont choisis parmi Al203, MgO, CaO, Zr02, Ti02, Ce203, et Ce02 the inorganic oxides are chosen from Al 2 O 3 , MgO, CaO, ZrO 2 , TiO 2 , Ce 2 O 3 , and CeO 2
- la phase active déposée dans et /ou sur le support par tous types de techniques (imprégnation, coprécipitation,...) est constituée de particules métalliques choisies parmi Ni, Rh, Pt, Pd, Co, Mo, the active phase deposited in and / or on the support by all types of techniques (impregnation, coprecipitation, etc.) consists of metal particles chosen from Ni, Rh, Pt, Pd, Co, Mo,
Cu, Fe et/ou leur mélange ; la phase active peut être déposée dans et /ou sur le support par tous types de techniques (imprégnation, coprécipitation,...) Cu, Fe and / or their mixture; the active phase can be deposited in and / or on the support by all types of techniques (impregnation, coprecipitation, ...)
- le barillet peut aussi présenter sur sa paroi externe une ou plusieurs saignées.  - The barrel may also have on its outer wall one or more grooves.
Les pertes de charges dans les réacteurs catalytiques sont un paramètre primordial influençant les performances de certains procédés gaz/solide, liquide/solide ou gaz/liquide/solide. La perte de charge dans un réacteur est liée à la géométrie du catalyseur et à la compacité de son empilement et/ou à la formation de fines lors du remplissage en raison de sa faible tenue mécanique. Certains procédés catalytiques gaz/solide, liquide/solide ou gaz/liquide/solide mettent en jeu plusieurs réacteurs catalytiques pouvant présenter des recycles (ex. le flux sortant d'un réacteur secondaire est renvoyé en tête d'un réacteur primaire). Dans ces cas, des étapes de compression peuvent être nécessaires et nuire à l'efficacité globale du procédé si les pertes de charge dans les réacteurs sont trop importantes. De plus, d'autres procédés peuvent mettre en jeu, en aval des réacteurs catalytiques, des unités dont les performances peuvent être diminuées par une pression d'entrée trop basse (ex. unités de purification).  The losses in catalytic reactors are a paramount parameter influencing the performance of certain gas / solid, liquid / solid or gas / liquid / solid processes. The pressure drop in a reactor is related to the geometry of the catalyst and the compactness of its stack and / or the formation of fines during filling due to its low mechanical strength. Some catalytic gas / solid, liquid / solid or gas / liquid / solid processes involve several catalytic reactors which may have recycles (eg the flow leaving a secondary reactor is returned to the top of a primary reactor). In these cases, compression steps may be necessary and adversely affect the overall efficiency of the process if the pressure drops in the reactors are too great. In addition, other processes may involve, downstream of the catalytic reactors, units whose performance can be reduced by a too low inlet pressure (eg purification units).
L'invention propose de nouvelles géométries à fort PFV (supérieur à 20%) afin de diminuer les pertes de charge. The invention proposes new geometries with high PFV (greater than 20%) in order to reduce the pressure drops.
D'autre part, les réactions catalytiques gaz/solide, liquide/solide ou gaz/liquide/solide présentant une cinétique intrinsèque rapide sont alors limitées par le transfert de matière (transfert des réactifs) soit des phases gazeuse ou liquide vers la surface du catalyseur (transfert extraparticulaire), soit de la surface du catalyseur vers les sites actifs au sein des pores du catalyseur (transfert intraparticulaire). Ces transferts de matière sont, dans ces cas, plus lents que la réaction et l'étape limitant l'efficacité catalytique est le transport des réactifs vers le site actif où a lieu la réaction. Un paramètre clé du catalyseur influençant les transferts intraparticulaires et extraparticulaires est le rapport S/V. On the other hand, the catalytic reactions gas / solid, liquid / solid or gas / liquid / solid having a fast intrinsic kinetics are then limited by the transfer of material (transfer of reagents) or gas or liquid phases to the catalyst surface (extraparticular transfer), or from the surface of the catalyst to the active sites within the pores of the catalyst (intraparticular transfer). These transfers of material are, in these cases, slower than the reaction and the step limiting the catalytic efficiency is the transport of the reagents to the active site where the reaction takes place. A key catalyst parameter influencing intraparticle and extraparticular transfers is the S / V ratio.
Le transfert de matière extraparticulaire est, quant à lui, également lié à la turbulence générée dans la phase gazeuse par la forme du catalyseur.  The extraparticular material transfer is, in turn, also related to the turbulence generated in the gas phase by the shape of the catalyst.
L'invention décrite ici propose de nouvelles géométries de catalyseur permettant de diminuer ces limitations. Une analogie entre les transferts de matière et de chaleur peut être faite. The invention described here proposes new catalyst geometries to reduce these limitations. An analogy between the transfers of matter and heat can be made.
L'amélioration notamment du transfert de chaleur peut permettre de rallonger la durée de vie des réacteurs tubulaires exposés à des réactions endothermiques, type SMR (chauffage ex-situ par tout type de source de chaleur : flamme, électrique). In particular, the improvement of heat transfer can extend the life of tubular reactors exposed to endothermic reactions, type SMR (ex-situ heating by any type of heat source: flame, electric).
Cette invention propose d'une part, de nouvelles formes externes pour le barillet qui n'ont pas été proposées auparavant ; d'autre part, de nouvelles géométries de trous qui n'ont jamais été envisagées. This invention proposes, on the one hand, new external forms for the barrel that have not been proposed before; on the other hand, new geometries of holes that have never been considered.
La forme externe du barillet peut se présenter sous les formes suivantes :  The external shape of the barrel can be in the following forms:
- prisme hexagonal,  - hexagonal prism,
- cylindre, - cylinder,
- cylindre à section elliptique,  - cylinder with elliptical section,
- prisme de Vauban,  - Vauban prism,
- ellipsoïde.  - ellipsoid.
La structure interne est composée de trous présentant une forme non convexe :  The internal structure is composed of holes having a non-convex shape:
- flocon de Von Koch, - Von Koch flake,
- étoile de David,  - David's star,
- croix grecque,  - Greek cross,
- carré à côté dentelé,  - square with serrated side,
Les figures la) et lb) montrent des exemples de catalyseur selon l'invention sous la forme de barillet comprenant un seul trou de forme non convexe ; les figures 2a) et 2b) montrent des exemples de catalyseur selon l'invention sous la forme de barillet comprenant plusieurs trous de forme non convexe.  Figures la) and lb) show examples of catalyst according to the invention in the form of barrel comprising a single hole of non-convex shape; Figures 2a) and 2b) show examples of the catalyst according to the invention in the form of a barrel comprising a plurality of non-convex shaped holes.
Les nouvelles géométries de catalyseur proposées sont de type barillet avec un diamètre pouvant aller de 5 à 20 mm et une hauteur pouvant aller de 5 à 20 mm, avec un rapport diamètre / hauteur (D/H) compris par exemple entre 0.5 et 2 mais préférablement compris entre 0,8 et 1,5. Ce ratio D/H est important car il va également conditionner l'arrangement / empilement du lit. La densité d'empilement est importante car elle va refléter la quantité de matière active présente dans le réacteur, l'empilement va être défini par la position de l'objet (horizontale, verticale, oblique). Ces paramètres vont également influencer la perte de charge dans le lit. La position oblique sera préférentiellement recherchée car elle va favoriser les écoulements turbulents au sein du réacteur. Un objet de ratio < 0.8 aura tendance à s'empiler horizontalement, alors qu'un objet de ratio compris entre 0.8 et 1.5 aura plus tendance à s'empiler en oblique dû à la hauteur de son centre de gravité. The proposed new catalyst geometries are of barrel type with a diameter ranging from 5 to 20 mm and a height ranging from 5 to 20 mm, with a ratio of diameter / height (D / H) for example between 0.5 and 2 but preferably between 0.8 and 1.5. This ratio D / H is important because it will also condition the arrangement / stacking of the bed. The stacking density is important because it will reflect the amount of active material present in the reactor, the stack will be defined by the position of the object (horizontal, vertical, oblique). These parameters will also influence the pressure drop in the bed. The oblique position will be preferentially sought because it will promote turbulent flows within the reactor. An object with a ratio <0.8 will tend to stack horizontally, while a ratio object between 0.8 and 1.5 will tend to stack obliquely due to the height of its center of gravity.
Les formes externes de barillet selon l'invention permettent d'obtenir une tenue mécanique robuste car l'épaisseur des parois est adaptée à la géométrie des trous. L'ordre de grandeur pour l'épaisseur des parois est d'environ 2 mm. Les barillets selon l'invention présentent un PFV important : de 20% à 50%. Un barillet simple de diamètre 10 mm et hauteur 15 mm percé d'un trou de diamètre 5 mm présente un PFV de 25%. Un barillet de diamètre 10 mm et hauteur 15 mm percé de 7 trous de diamètre 2 mm a un PFV de 28%. Les deux formes ci-dessus ont des PFVE compris entre 35% et 40%. Ces nouvelles géométries devraient donc permettre de diminuer les pertes de charge des lits catalytiques. De plus, plus le PFV est important, moins l'encours de matière catalytique est important. The external forms of barrel according to the invention make it possible to obtain a robust mechanical strength because the thickness of the walls is adapted to the geometry of the holes. The order of magnitude for the wall thickness is about 2 mm. The barrels according to the invention have a high PFV: from 20% to 50%. A single barrel with a diameter of 10 mm and a height of 15 mm and a hole diameter of 5 mm has a PFV of 25%. A barrel of diameter 10 mm and height 15 mm pierced with 7 holes of diameter 2 mm has a PFV of 28%. Both forms above have PFVEs between 35% and 40%. These new geometries should therefore make it possible to reduce the losses of load of the catalytic beds. In addition, the larger the PFV, the less the outstanding amount of catalytic material is important.
D'autre part, afin d'améliorer les transferts de matière et de chaleur intraparticulaires et extraparticulaires, ces formes ont été conçues pour développer un rapport S/V important : supérieur à 1000, préférentiellement supérieur à 2000 m2/m3 et un PSI supérieur à 100 %. Par comparaison, les structures mentionnées plus haut (barillet simple de diamètre 10 mm et hauteur 15 mm percé d'un trou de diamètre 5 mm et un barillet de diamètre 10 mm et hauteur 15 mm percé de 7 trous de diamètre 2 mm) présentent, respectivement, un S/V de 933 ηΊ /Ίη3 et 1467 m2/m3 et des PSI de 40% et 113%. On the other hand, in order to improve intraparticle and extraparticle transfer of material and heat, these forms have been designed to develop a significant S / V ratio: greater than 1000, preferably greater than 2000 m 2 / m 3 and a PSI greater than 100%. By comparison, the structures mentioned above (single barrel diameter 10 mm and height 15 mm with a hole diameter of 5 mm and a barrel diameter 10 mm and height 15 mm with 7 holes of diameter 2 mm) have, respectively, an S / V of 933 ηΊ / Ίη 3 and 1467 m 2 / m 3 and PSI of 40% and 113%.
Enfin, afin de limiter les écoulements préférentiels, ces formes ont été pensées pour réduire le nombre de symétrie. Ces formes ont été conçues via une approche fractale en exploitant une forme autosimilaire basée sur un générateur à motif unique, et le nombre de trous en périphérie sera préférentiellement impair ou le motif central sera décalé. Notons que de préférence le trou présente un axe de symétrie non parallèle à l'axe de symétrie du barillet (trous obliques ou hélicoïdaux) et si la géométrie du barillet définit plusieurs trous, les axes de symétrie de ces trous sont de préférence non parallèles. Finally, in order to limit preferential flows, these forms have been designed to reduce the number of symmetries. These shapes were designed via a fractal approach by exploiting a self-similar form based on a single pattern generator, and the number of holes at the periphery will preferably be odd or the central pattern will be shifted. Note that preferably the hole has an axis of symmetry not parallel to the axis of symmetry of the cylinder (oblique or helical holes) and if the geometry of the barrel defines several holes, the axes of symmetry of these holes are preferably non-parallel.
Le catalyseur selon l'invention peut être utilisé dans tout type de réactions (oxydation, hydrogénation...). Les principales réactions visées de type gaz/solide seront les réactions de reformage d'un hydrocarbure (gaz naturel, naphta, biogaz, off gas de raffinerie...), d'un alcool (MeOH, EtOH), de glycérol, par un oxydant tels que la vapeur d'eau, le C02, l'oxygène ou leur mélange, les réactions de transformation d'un mélange de synthèse riche en H2/CO telles que la réaction de water gas shift, la réaction de reverse water gas shift, la réaction de synthèse d'un alcool (MeOH,..), la réaction de méthanation. The catalyst according to the invention can be used in any type of reaction (oxidation, hydrogenation, etc.). The main targeted reactions of the gas / solid type will be the reforming reactions of a hydrocarbon (natural gas, naphtha, biogas, off-gas refinery ...), an alcohol (MeOH, EtOH), glycerol, by a oxidant such as water vapor, C0 2 , oxygen or their mixture, transformation reactions of a synthesis mixture rich in H 2 / CO such as the reaction of water gas shift, the reverse water reaction gas shift, the synthesis reaction of an alcohol (MeOH, ..), the methanation reaction.
L'utilisation du catalyseur selon l'invention ne se limite pas aux réactions type gaz/solide mais est applicable aux réactions liquide/solide et gaz/liquide/solide.  The use of the catalyst according to the invention is not limited to the gas / solid type reactions but is applicable to liquid / solid and gas / liquid / solid reactions.
Le catalyseur selon l'invention peut opérer sous pression (1 à 60 atm) et température (150 - 1000°C).  The catalyst according to the invention can operate under pressure (1 to 60 atm) and temperature (150 - 1000 ° C).
Enfin, la présente invention a également pour objet un réacteur catalytique comprenant un empilement de catalyseurs selon l'invention. Finally, the subject of the present invention is also a catalytic reactor comprising a stack of catalysts according to the invention.
Les avantages de l'objet de l'invention ont été illustrés par l'exemple ci-dessous. Exemple 1 The advantages of the subject of the invention have been illustrated by the example below. Example 1
Les expériences de perte de charge et de traçage (dispersions axiales et radiales) ont été effectuées dans un réacteur de 15 cm de diamètre et 2,5 m de haut (volume du lit 46,9 L). Ce pilote dispose de 5 piquages pour les mesures de perte de charge et de 2 piquages pour la dispersion radiale du gaz. La phase gaz utilisée est de l'air avec un débit pouvant varier de 0 à 185 m /n (i.e 0 à 2,9 m/s) et le traceur est du méthane. Pour les mesures de traçage, le méthane est injecté par puise en haut et au centre de la section du lit (Figure 3). Concernant les dispersions axiales, la concentration de méthane est mesurée par un FID (Flamme lonization Detector = détecteur à ionisation de flamme en langue française) dans un cône en sortie du réacteur avec une fréquence d'acquisition de 100Hz. Pour les dispersions radiales, les prélèvements sont faits sur tout le diamètre du réacteur à l'aide de cannes passant par les piquages du réacteur (Figure 3). Les dispersions axiales permettent d'avoir des informations sur les performances du réacteur (piston idéal, piston à dispersion,...) par la mesure du nombre deThe pressure drop and tracing experiments (axial and radial dispersions) were carried out in a reactor 15 cm in diameter and 2.5 m high (bed volume 46.9 L). This pilot has 5 taps for the pressure drop and 2 taps measurements for the radial dispersion of the gas. The gas phase used is air with a flow rate ranging from 0 to 185 m / n (ie 0 to 2.9 m / s) and the tracer is methane. For tracer measurements, methane is injected through the top and center of the bed section (Figure 3). Concerning the axial dispersions, the concentration of methane is measured by an FID (Flame lonization Detector = flame ionisation detector in French language) in a cone at the outlet of the reactor with an acquisition frequency of 100 Hz. For radial dispersions, Samples are taken over the entire diameter of the reactor using canes passing through the reactor taps (Figure 3). Axial dispersions make it possible to obtain information on reactor performance (ideal piston, dispersion piston, etc.) by measuring the number of
Péclet (Pe=vL/Dax) avec v, la vitesse interstitielle (m/s), L, la hauteur du lit (m) et Dax la dispersion axiale (m2/s). Plus le nombre de Péclet est élevé, plus le réacteur tend vers le réacteur parfaitement piston. Les informations sur la distribution du fluide à travers le lit sont obtenues par les données de dispersion radiale. Peclet (Pe = vL / D ax) with v, interstitial velocity (m / s), L, bed height (m) and axial dispersion Dax (m 2 / s). The higher the number of Peclet, the more the reactor tends to the reactor perfectly piston. The information on the fluid distribution through the bed is obtained by the radial dispersion data.
Par la suite, on désignera par :  Then, we will designate by:
DP : pertes de charge (mbar ou Pa)  DP: pressure drop (mbar or Pa)
L : longueur du lit (m) L: length of the bed (m)
Q : Débit volumique d'air (m /n)  Q: Volume flow rate of air (m / n)
u : vitesse en fût vide (m/s) u: empty drum speed (m / s)
v : vitesse interstitielle (m/s) v: interstitial velocity (m / s)
ε : porosité du lit ε: porosity of the bed
Dax : dispersion axiale (m2/s) Dax: axial dispersion (m 2 / s)
avec u = ε v with u = ε v
L'objet selon l'invention testé dans cet exemple est le barillet Von Koch Vauban 7 trous de diamètre 19 mm et de hauteur 15 mm. Il est comparé aux objets commerciaux qui sont des billes de verre de 5 mm de diamètre et des barillets à 10 trous de diamètre 19 mm et de hauteur 15 mm avec un trou central de 5 mm et 9 trous périphériques de 3 mm. Un barillet à 10 trous est représenté figure 4.  The object according to the invention tested in this example is the Von Koch Vauban drum 7 holes 19 mm in diameter and 15 mm in height. It is compared to commercial objects which are 5 mm diameter glass beads and barrels with 10 holes 19 mm in diameter and 15 mm in height with a 5 mm central hole and 9 3 mm peripheral holes. A 10-hole cylinder is shown in FIG.
La porosité pour les barillets Von Koch Vauban 7 trous est de 0,63, pour les barillets à 10 trous de 0,53 et pour les billes de verre de 0,37.  The porosity for the 7-hole Von Koch Vauban drills is 0.63, for the 10-hole drums of 0.53 and for the 0.37-glass drums.
Le tableau 1 indique les pertes de charge des barillets à 10 trous en fonction du débit volumique ou de la vitesse en fût vide.  Table 1 shows the pressure drop of the 10-hole cylinders as a function of volume flow or empty drum speed.
Le tableau 2 indique les pertes de charge des billes en verre en fonction du débit volumique ou de la vitesse en fût vide.  Table 2 shows the pressure drop of the glass beads as a function of volume flow or empty drum speed.
Le tableau 3 indique les pertes de charge des barillets Von Koch en fonction du débit volumique ou de la vitesse en fût vide. La figure 5 permet une comparaison des résultats donnés dans les tableaux \, 2 et 3. Table 3 shows the pressure drops of the Von Koch barrels as a function of volume flow or empty drum speed. Figure 5 allows a comparison of the results given in Tables 1, 2 and 3.
Le tableau 4 indique la dispersion axiale des barillets à 10 trous en fonction de la vitesse en fût vide.  Table 4 shows the axial dispersion of the 10-hole drums as a function of the empty drum speed.
Le tableau 5 indique la dispersion axiale des barillets Von Koch en fonction de la vitesse en fût vide.  Table 5 shows the axial dispersion of Von Koch barrels as a function of the empty drum speed.
La figure 6 permet une com paraison des résultats donnés dans les tableaux 4 et 5. Les triangles correspondent à la dispersion axiale pour les barillets Von Koch et les carrés correspondent à la dispersion axiale pour les barillets 10 trous.  FIG. 6 allows a comparison of the results given in Tables 4 and 5. The triangles correspond to the axial dispersion for the Von Koch barrels and the squares correspond to the axial dispersion for the 10-hole barrels.
Le tableau 6 indique le nombre de Péclet déterminé avec un débit de 80 m /n pour les barillets 10 trous et les barillets Von Koch.  Table 6 shows the number of Peclets determined with a flow rate of 80 m / n for 10-hole cylinders and Von Koch barrels.
Figure imgf000011_0001
Figure imgf000011_0001
Tableau 1 Table 1
Figure imgf000012_0001
Figure imgf000012_0001
Tableau 2
Figure imgf000012_0002
Table 2
Figure imgf000012_0002
Tableau 3 v(m/s) u(m/s) Dax(m2/s) Table 3 v (m / s) u (m / s) D max (m 2 / s)
1 ,97 0,97 1.93E-002  1, 97 0.97 1.93E-002
2,49 1 ,22 2.15E-002  2.49 1, 22 2.15E-002
3,44 1 ,69 2.73E-002  3.44 1, 69 2.73E-002
Tableau 4  Table 4
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0002
Tableau 6  Table 6
En résumé, les pertes de charges sont du même ordre de grandeur pour les barillets Von Koch Vauban et les barillets 10 trous, mais bien meilleures que celles des billes de 5 mm. In summary, the pressure drops are of the same order of magnitude for Von Koch Vauban barrels and 10-hole barrels, but much better than those of 5 mm balls.
En revanche, concernant la dispersion axiale, les barillets Von Koch Vauban présentent un Péclet de lit plus élevé que celui des barillets 10 trous (400 et 280 respectivement). Par conséquent, un réacteur avec des barillets von Koch Vauban aura un fonctionnement plus proche de celui d'un réacteur parfaitement piston. Ce résultat est conforté par les calculs des dispersions axiales en fonction des vitesses en fût vide. En effet, comme le montre la figure 6 les dispersions axiales (Dax) des barillets von Koch Vauban sont inférieures à celle des barillets 10 trous, en d'autres terme les écarts par rapport à un écoulement parfaitement piston sont plus faibles avec les barillets von Koch Vauban. On the other hand, with regard to the axial dispersion, the Von Koch Vauban barrels have a higher bedlet than the 10-hole barrels (400 and 280 respectively). Therefore, a reactor with von Koch Vauban barrels will operate closer to that of a perfectly piston reactor. This result is supported by the calculations of the axial dispersions as a function of the empty drum speeds. In fact, as shown in FIG. 6, the axial dispersions (Dax) of von Koch Vauban barrels are smaller than that of 10-hole barrels, in other words the deviations from a perfectly piston flow are lower with the von barrels. Koch Vauban.
Exemple 2 Des mesures de dispersions radiales ont été réalisées dans un tube de 15cm de diamètre et de 80cm de haut. Le tube était rempli sur 40cm des différentes particules et les mesures ont été réalisées avec un débit d'air de 40m3/h. L'expérience a consisté à injecter des puises de méthane à 28cm de haut par rapport à la grille de maintien, l'injecteur étant localisé dans l'empilement. Les prélèvements ont été réalisés à l'aide d'une canne sous la grille de maintien des particules sur 9 points par axe (distances par rapport au centre : -7,5 cm ; -5,5 cm ; -3,5 cm ; -1,5 cm ; 0 cm ; 1,5 cm ; 3,5 cm ; 5,5 cm ; 7,5 cm) et sur 6 axes espacés de 30 degrés (soit à 0, 30, 60, 90, 120 et 150 degrés). Example 2 Radial dispersion measurements were made in a tube 15 cm in diameter and 80 cm high. The tube was filled on 40cm of the different particles and the measurements were carried out with an air flow of 40m3 / h. The experiment consisted of injecting methane taps 28 cm high with respect to the holding grid, the injector being located in the stack. The samples were taken using a cane under the particle holding grid at 9 points per axis (distances from the center: -7.5 cm, -5.5 cm, -3.5 cm; -1.5 cm, 0 cm, 1.5 cm, 3.5 cm, 5.5 cm, 7.5 cm) and 6 axes spaced 30 degrees apart (ie at 0, 30, 60, 90, 120 and 150 degrees).
L'objet selon l'invention testé dans cet exemple est le barillet von Koch Vauban 7 trous de diamètre 19 mm et de hauteur 15 mm. Il est comparé aux objets commerciaux qui sont des billes de verre de 5 mm de diamètre et des barillets à 10 trous de diamètre 19 mm et de hauteur 15 mm avec un trou central de 5 mm et 9 trous périphériques de 3 mm. Un barillet à 10 trous est représenté figure 5. Il est comparé à des cylindres en bois de diamètre 19 mm et de hauteur 15 mm et à un barillet Vauban de diamètre 19 mm et de hauteur 15 mm (barillet von Koch Vauban 7 trous de diamètre 19 mm et de hauteur 15 mm dont les trous ont été obstrués).  The object according to the invention tested in this example is the von Koch Vauban 7-hole drum with a diameter of 19 mm and a height of 15 mm. It is compared to commercial objects which are 5 mm diameter glass beads and barrels with 10 holes 19 mm in diameter and 15 mm in height with a 5 mm central hole and 9 3 mm peripheral holes. A 10-hole cylinder is shown in Figure 5. It is compared to wooden cylinders with a diameter of 19 mm and a height of 15 mm and a Vauban cylinder with a diameter of 19 mm and a height of 15 mm (von Koch Vauban barrel, 7 holes in diameter). 19 mm and height 15 mm whose holes were obstructed).
Les profils de concentration de méthane sont donnés sur les figures 7 a) à 7 e). The methane concentration profiles are given in Figures 7 (a) to 7 (e).
Les formes de type cylindriques améliorent fortement la dispersion radiale des empilements comparativement aux empilements de billes. The cylindrical type shapes greatly improve the radial dispersion of the stacks compared to the stacks of balls.
Les dispersions radiales pour les cylindres 19mmxl5mm et pour les Vauban sont équivalentes. Entre les Vauban et les von Koch Vauban, la présence des trous et leurs caractéristiques améliorent la dispersion radiale de 130 %, alors que, pour les barillets, la présence des trous et leurs caractéristiques, améliorent la dispersion radiale que de 95 % (comparaison Barillets et Cylindres 19mmxl5mm). En résumé, les formes von Koch Vauban améliorent de 40 % les dispersions radiales par rapport aux formes commerciales de type barillets. The radial dispersions for the 19mmx15mm cylinders and for the Vauban are equivalent. Between the Vauban and the von Koch Vauban, the presence of the holes and their characteristics improve the radial dispersion of 130%, whereas, for the barrels, the presence of the holes and their characteristics, improve the radial dispersion than of 95% (comparison Barrels and Cylinders 19mmx15mm). In summary, the von Koch Vauban forms improve radial dispersions by 40% compared with commercial barrel-type shapes.
Exemple 3 Des mesures de dispersions d'écoulement de liquide ont été réalisées dans un tube de 30cm de diamètre et de 50cm de haut. Le tube était rempli sur 30cm des différentes particules. L'expérience a consisté à injecter 100 ml d'eau en haut au centre de l'empilement et à collecter sous la grille de maintien le liquide écoulé dans 96 réceptacles de dimension 30mmx30mmx28mm. Les réceptacles sont positionnés de telles sortes à former un quadrillage de 10x10 réceptacles (il n'y a pas de réceptacle dans les coins). Pour chaque expérience, les réceptacles sont ensuite pesés et la surface impactée est mesurée par l'écoulement de liquide. Les empilements ont été au préalable saturés d'eau pour permettre de remplir les porosités des solides constituants les Barillets 10 trous et les von Koch Vauban. Example 3 Measurements of liquid flow dispersions were made in a tube 30 cm in diameter and 50 cm high. The tube was filled on 30cm of different particles. The experiment consisted of injecting 100 ml of water at the top center of the stack and collecting under the holding grid the liquid flowing in 96 receptacles of size 30mmx30mmx28mm. The receptacles are positioned in such a way as to form a grid of 10x10 receptacles (there is no receptacle in the corners). For each experiment, the receptacles are then weighed and the impacted surface is measured by the liquid flow. Stacks were previously saturated with water to fill the porosities of the constituent constituents 10-hole barrels and von Koch Vauban.
L'objet selon l'invention testé dans cet exemple est le barillet von Koch Vauban 7 trous de diamètre 19 mm et de hauteur 15 mm. Il est comparé aux objets commerciaux qui sont des billes de verre de 5 mm de diamètre et des barillets à 10 trous de diamètre 19 mm et de hauteur 15 mm avec un trou central de 5 mm et 9 trous périphériques de 3 mm. Un barillet à 10 trous est représenté figure 5. The object according to the invention tested in this example is the von Koch Vauban 7-hole drum with a diameter of 19 mm and a height of 15 mm. It is compared to commercial objects which are 5 mm diameter glass beads and barrels with 10 holes 19 mm in diameter and 15 mm in height with a 5 mm central hole and 9 3 mm peripheral holes. A 10-hole cylinder is shown in FIG.
Le tableau ci-dessous indique le nombre de réceptacles mouillés et le pourcentage de surface impactée par rapport à la section du tube obtenus en fin de coulée de 100 mL d'eau. The table below shows the number of wet receptacles and the percentage of impacted area relative to the section of the tube obtained at the end of pouring 100 mL of water.
Figure imgf000015_0001
Figure imgf000015_0001
Tableau 7  Table 7
En résumé, les von Koch Vauban présentent de meilleures dispersions à l'écoulement de liquide que les Barillets 10 trous et les Billes. In summary, von Koch Vauban exhibits better dispersions in liquid flow than 10-hole and 10-hole barrels.

Claims

Revendications claims
1. Catalyseur pour réacteurs catalytiques sous la forme d'un barillet centimétrique et dont la géométrie définit au moins un trou débouchant de part et d'autre du barillet et tel que le pourcentage de fraction de vide (PFV) du barillet est compris entre 20% et 50%, le Pourcentage de Surface Interne (PSI) du barillet est compris entre 60% et 220% et le rapport surface / volume (S/V) du barillet est supérieur à 1000 m2/m3, avec : 1. Catalyst for catalytic reactors in the form of a centimetric cylinder and whose geometry defines at least one hole opening on either side of the cylinder and such that the void fraction percentage (PFV) of the cylinder is between 20 % and 50%, the Percentage Internal Surface (PSI) of the barrel is between 60% and 220% and the surface / volume (S / V) ratio of the barrel is greater than 1000 m 2 / m 3 , with:
- le barillet présentant une forme externe choisie parmi le prisme hexagonal, le cylindre, le cylindre à section elliptique, le prisme de Vauban et l'ellipsoïde ; et  the barrel having an external shape chosen from the hexagonal prism, the cylinder, the cylinder with elliptical section, the Vauban prism and the ellipsoid; and
- le trou présentant une forme non convexe choisie parmi le flocon de Von Koch, l'étoile de David, la croix grecque, et le carré à côté dentelé. - the hole with a non-convex shape chosen from the von Koch flake, the Star of David, the Greek cross, and the serrated side square.
2. Catalyseur selon la revendication 1, caractérisé en ce que le barillet présente un diamètre pouvant aller de 5 à 20 mm et une hauteur pouvant aller de 5 à 20 mm, avec un rapport diamètre / hauteur compris entre 0,5 et 2, de préférence compris entre 0,8 et 1,5. 2. Catalyst according to claim 1, characterized in that the barrel has a diameter ranging from 5 to 20 mm and a height ranging from 5 to 20 mm, with a diameter / height ratio of between 0.5 and 2, of preferably between 0.8 and 1.5.
3. Catalyseur selon l'une des revendications 1 ou 2, caractérisé en ce que le rapport surface / volume (S/V) est supérieur à 2000 m2/m3. 3. Catalyst according to one of claims 1 or 2, characterized in that the surface / volume ratio (S / V) is greater than 2000 m 2 / m 3 .
4. Catalyseur selon l'une des revendications 1 à 3, caractérisé en ce que le trou présente un axe de symétrie non parallèle à l'axe de symétrie du barillet (trous obliques ou hélicoïdaux). 4. Catalyst according to one of claims 1 to 3, characterized in that the hole has an axis of symmetry not parallel to the axis of symmetry of the cylinder (oblique or helical holes).
5. Catalyseur selon l'une des revendications 1 à 4, caractérisé en ce que ledit catalyseur est constitué d'un support et d'une phase active déposée sur le support. 5. Catalyst according to one of claims 1 to 4, characterized in that said catalyst consists of a support and an active phase deposited on the support.
6. Catalyseur selon la revendication 5, caractérisé en ce que le support est de type oxyde ou d'un mélange d'oxydes inorganiques. 6. Catalyst according to claim 5, characterized in that the support is of the oxide type or a mixture of inorganic oxides.
7. Catalyseur selon la revendication 6, caractérisé en ce que les oxydes inorganiques sont choisis parmi Al203, MgO, Cad, Zr02, Ti02, Ce02 et Ce203 7. Catalyst according to claim 6, characterized in that the inorganic oxides are chosen from Al 2 0 3, MgO, Cad, Zr0 2, Ti0 2, Ce0 2 and Ce 2 0 3
8. Catalyseur selon l'une des revendications 5 à 7, caractérisé en ce que la phase active est constituée de particules métalliques choisies parmi Ni, Rh, Pt, Pd, Co, Mo, Cu, Fe et/ou leur mélange. 8. Catalyst according to one of claims 5 to 7, characterized in that the active phase consists of metal particles selected from Ni, Rh, Pt, Pd, Co, Mo, Cu, Fe and / or their mixture.
9. Catalyseur selon l'une des revendications 1 à 8, caractérisé en ce que le barillet peut présenter sur sa paroi externe une ou plusieurs saignées. 9. Catalyst according to one of claims 1 to 8, characterized in that the barrel may have on its outer wall one or more grooves.
10. Utilisation d'un catalyseur selon l'une des revendications 1 à 8 pour les réactions gaz/solide de type reformage d'un hydrocarbure, d'un alcool et de glycérol et les réactions de transformation d'un mélange de synthèse riche en H2/CO. 10. Use of a catalyst according to one of claims 1 to 8 for the gas / solid reactions of the reforming type of a hydrocarbon, an alcohol and glycerol and the reaction reactions of a synthesis mixture rich in H 2 / CO.
11. Utilisation d'un catalyseur selon l'une des revendications 1 à 8 pour les réactions liquide/solide et gaz/liquide/solide. 11. Use of a catalyst according to one of claims 1 to 8 for the liquid / solid and gas / liquid / solid reactions.
12. Réacteur catalytique comprenant un empilement de catalyseurs selon l'une des revendications 1 à 7. 12. Catalytic reactor comprising a catalyst stack according to one of claims 1 to 7.
PCT/FR2015/051324 2014-05-30 2015-05-20 Catalyst in the form of a cylinder perforated from one side to the other WO2015181472A1 (en)

Applications Claiming Priority (2)

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FR1454904 2014-05-30
FR1454904A FR3021555B1 (en) 2014-05-30 2014-05-30 CATALYST IN THE FORM OF A BARREL WITH A GEOMETRY DEFINING A HOLE

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FR3021555A1 (en) 2015-12-04

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