WO2019008053A1 - Système constitué d'un support pourvu de canaux d'écoulement et d'un revêtement dit « wash coat » - Google Patents

Système constitué d'un support pourvu de canaux d'écoulement et d'un revêtement dit « wash coat » Download PDF

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Publication number
WO2019008053A1
WO2019008053A1 PCT/EP2018/068120 EP2018068120W WO2019008053A1 WO 2019008053 A1 WO2019008053 A1 WO 2019008053A1 EP 2018068120 W EP2018068120 W EP 2018068120W WO 2019008053 A1 WO2019008053 A1 WO 2019008053A1
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Prior art keywords
carrier
coating
catalyst
catalytically active
porosity
Prior art date
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PCT/EP2018/068120
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German (de)
English (en)
Inventor
David L. DECK
Original Assignee
Exentis Knowledge Gmbh
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Publication date
Application filed by Exentis Knowledge Gmbh filed Critical Exentis Knowledge Gmbh
Priority to EP18740147.6A priority Critical patent/EP3648883A1/fr
Publication of WO2019008053A1 publication Critical patent/WO2019008053A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/42—Platinum
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/20—Carbon compounds
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    • B01J27/228—Silicon carbide with phosphorus, arsenic, antimony or bismuth
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    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/657—Pore diameter larger than 1000 nm
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/0201—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
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • 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
    • B01J37/0217—Pretreatment of the substrate before coating
    • 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
    • B01J37/0225—Coating of metal substrates
    • 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
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
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    • B01J37/08—Heat treatment
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9431—Processes characterised by a specific device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • B01J37/32—Freeze drying, i.e. lyophilisation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2807—Metal other than sintered metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs

Definitions

  • the invention relates to a system consisting of a support with flow channels and at least one catalytically active substance according to the preamble of patent claim 1.
  • the third partners in the product and application chain are the coaters, who in large-scale production-suitable coating systems provide the carriers with surface-increasing carrier layers and incorporate the catalytic substances in them.
  • a large number of small and medium-sized businesses are filling the small to medium series and single piece production gap by combining known supports with known catalysts using known techniques such as wash-coat, sputtering and plasma coating and soaking for short application times.
  • a further significant deficit of classical coating technology is the development of supported catalysts, in which the catalyst is introduced into the composition during molding and is fired. In this case, more than 90% of the catalyst material is lost for the catalytic reaction, since this ratio of catalytic substance by inclusion and fusion in the support structure of the exhaust gas for the catalytic reaction is not achievable.
  • the plasma coating is known as wash-coattransport coating, but this is more suitable for two-dimensional catalyst support such as films, since the penetration depth of the plasma in the channels of the support structures is only a few millimeters and hardly, or not in the random still existing material porosity.
  • the plasma coating is possible only as an additional coating in the inlet and outlet regions of a catalyst, filter or reactor, or in the case of very small monoliths, such as, for example, in the bulk material catalyst.
  • FIG. 1 shows a catalyst according to the prior art.
  • a carrier 1 is provided on both sides with a washcoat layer 2, the outer layer 3 is penetrated by a catalyst material.
  • This object is achieved by a system consisting of a carrier with flow channels and at least one catalytically active substance having the features of patent claim 1.
  • the present invention consists of a combination of a system of catalytically active substances based on rare earths and / or classical catalyst materials as catalyst, and ceramic or metallic and plastic porous carriers with capillary interconfective pore systems based on extruded, cast, sprayed or additive manufactured straps.
  • the catalytically active substance is in solution in the preparation process or dispersed in fine-grained low-viscosity suspension or distributed as a vapor or mist component.
  • the catalyst adheres by means of thermal, chemical or physical method to the individual grains of the support material not only in the outer wall region, but also within the material walls of the carrier webs, which process-related high catalyst material surface achievable for the exhaust gases is present both on the channel walls and within the material of the channel wall webs.
  • the support structure of the catalyst, the filter or the reactor is constructed of materials which consist of the group of metals.
  • these are low or high alloy steels, aluminum, copper, titanium.
  • the group of ceramics as support material ie silicate ceramics and oxide ceramics, materials such as corundum, cordierite, cordierite silicon carbide, silicon carbide and oxide ceramics of titanium oxide, aluminum oxide, magnesium oxide as material are preferred, but not exclusively.
  • FIG. 3 shows a detail of a coated, capillary interconnecting porous material web
  • Fig. 4 shows schematically the flow behavior of an exhaust gas in adjacent
  • a capillary interconnecting porous support 4 is provided, which is impregnated with a catalyst 5 in dissolved or suspended low-viscosity form and leads to a catalytic filter system 6.
  • the support structure of the catalyst, the filter or the reactor is composed of materials which consist of the group of metals. Preferably, but not exclusively, these are low or high alloy steels, aluminum, copper, titanium.
  • the group of ceramics as support material i. Silicate ceramics and oxide ceramics, above all, but not exclusively, materials such as corundum, cordierite, cordierite silicon carbide, silicon carbide and oxide ceramics of titanium oxide, aluminum oxide, magnesium oxide are preferred as the material.
  • FIG. 3 shows schematically a section of a coated, capillary interconnecting porous material web 7, which has grains 8 with capillary pores 9.
  • the material porosity be designed in such a way that the pores communicate with one another and permit a transverse flow within the material web in their arrangement. It has been shown that the addition of temporary porosifying agents is helpful.
  • the proportion of porosity agent, the grain size of which corresponds at least to that of the solid, is at most three times the solids. It has been shown that the porosity medium particle size between 0.5 ⁇ and 35 ⁇ is most suitable.
  • porosity agent in the mass is between 0 and 25 percent by volume of the carrier material.
  • the mixture of solvent, plasticizer and binder used is available, which can make up to 80 percent by volume of the carrier material.
  • the porosity agent is also removed thermally. This results in a material matrix which contains a capillary action within the pore system. This porosity and capillarity relates to the material matrix and not to the spatial porosity and capillarity of the channels of the support caused by the support structure.
  • the material used in the matrix can have grain sizes with an average value, which is referred to as the D50 value, of up to 150 ⁇ , but preferably not exclusively a particle size with a D50 value of 5 to 25 ⁇ , best of all of 8 ⁇ , most suitable.
  • the resulting average pore size, at 5 volume percent porosity with a maximum particle size of 25 ⁇ , is 7.5 ⁇ average pore size and can be up to 150 ⁇ .
  • the pore system is suitable for channel widths of 0.1 mm to 10 mm, preferably between 1 mm and 3 mm.
  • Deviating channel widths require a change in the material proportions which can easily be determined by a person skilled in the art, in particular because of the increasing overall porosity, material porosity plus structural porosity, decreasing body strength.
  • catalysts such as platinum, rhodium in question.
  • these are used to save material in dissolved and diluted form.
  • the granular catalyst composition has a high mass fraction, but has only a limited reaction surface due to the grain size of the catalyst, it is advantageous in the case of the granular catalyst composition to have a particle size below the ⁇ range down to single-digit nm ranges and smaller.
  • nanoparticulate catalyst preferably below 25 nm, is advantageous here.
  • FIG. 4 shows schematically the flow behavior of the fluid to be cleaned in adjacent material channels and in the material.
  • the capillary interconnecting porous material 1 1 is with flow channels. 12 interspersed.
  • the indicated with arrow 13 longitudinal flow of the fluid in the channel 12 has a velocity V1 and temperature T1
  • indicated by arrow 14 longitudinal flow of the fluid in the adjacent channel 12 has a speed V2 and T2 temperature.
  • Turbulence elements 16 can optionally be provided on the duct walls.
  • the high efficiency is caused by the occurring dual flow of the fluid to be purified in the catalyst, filter or reactor.
  • the fluid flows along the carrier channels in the longitudinal direction of the carrier structure. Surface roughness on the channel wall, flow velocities and thermal turbulence close to the wall result in intensive wall contact and thus contact between the fluid and the catalyst.
  • This is not sufficient because the effective residence time of the fluid in the catalyst, filter or reactor is still too short for reliable complete fluid conversion, especially because of the small available catalyst surface area.
  • the fluid is subjected to a second flow which takes place within the material matrix transverse to the longitudinal axis of the channels.
  • the flow of the fluid in the capillary interconnecting porosity of the carrier material is supported by temperature differences and different local flow differences in the channels, so that the effect of a type of jet pump to increased cross-flow of the fluid in the capillary porous material an increased contact of catalytically active substance with Fluid causes.
  • the generated cross-flows in turn increase the turbulence of the fluid flow in the channel longitudinal direction through their entry and exit from the material wall what within the Channel in turn leads to a contact increase between fluid and catalyst surface on the channel wall.
  • the channel of the carrier can be supported with turbulence-generating structural elements such as projections, increasing the surface roughness of the channels, constrictions, preferably as a flow aperture, or structural cross-connections between the longitudinally oriented channels.
  • the, in particular in the constellation of the wall penetration filtration with catalytic treatment of the fluid through an alternating channel closure at the inlet and outlet side, Wand be Spotifyung to the main flow direction and the fluid catalyst contact in the web material is maximally enforced. If the material porosity is high enough, the resulting low back pressure generated, the filtration system can certainly be used as a pure catalyst with low back pressure in the fluid flow without filtration of the fluid must be made.
  • the present invention differentiates the porosity of the catalyst support into two regions.
  • the first porosity range is for the use of the porosity for coating in the manufacture
  • the second porosity range is the effect of the porosity in the flow behavior in the application.
  • the lanthanum for the petroleum cracking with deoxidizer tion and desulfurization, cerium as oxide, nitrate, sulfate, carbonate, chloride or fluoride as catalyst scandium especially in the hydrogen chloride catalysis and samarium in the catalytic hydrogenation and dehydrogenation of ethanol currently the preferred rare earths.
  • rare earths and rare earth oxides or combinations and mixtures thereof are scandium, yttrium, lanthanum, cerium, praseodymium, neodynium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, the oxides for Y2O3, SC2O3, La2O3, Ce2O3 , Pr 2 O 3 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tu 2 O 3 , Yb 2 O 3 and Lu 2 O 3 .
  • the rare earth metal chlorides are introduced into the coating of the capillary porous materials, then it is metal Cl 3 , as a rare earth metal fluoride to metal F 3 . Since, with a few exceptions, the rare earth metals have low melting temperatures, these are contrary to the catalysts platinum and rhodium not for direct coating before sintering of the carrier and must be introduced after its preparation and subjected to a renewed annealing process to enter into a bond with the carrier crystals, or to be transformed from the dissolved constellation into the oxide form. As a rule, the tempering temperatures are below 800 ° C.
  • the maximum production temperatures are also significantly lower - at Y- 700 ° C, at Sc-960 ° C, at La-852 ° C, at Ce-802 ° C, at Pr -776 ° C, at Nd- 760 ° C, at Sm-728 ° C, at Eu-731 ° C, at Gd-609 ° C, at Tb-588 ° C, at Dy-654 ° C, at Tb-588 ° C, at Dy-654 ° C, at -718 ° C, at -774 ° C, at Tu-821 ° C, at Yb-854 ° C, and at Lu-892 ° C.
  • the maximum production temperatures are between 977 ° C and 1552 ° C. It is also possible to introduce the rare earth metals from the degradation products themselves in the manufacturing process and to use as a mass component of the structure matrix.
  • the mineral monazite (Ce (PO)) usually in conjunction with the zirconium mineral (Zr [PO 4 ]) comes as a raw material component in the carrier production with capillary porosity in question.
  • the aim of which is the application of a support layer on the structural support for increasing the surface area and absorption of the catalyst, in which capillary forces due to the channel shape can also act in the longitudinal direction of the monolith
  • the aiming direction is to bring about an inner coating of the carrier structure materials.
  • the porosity used is intended for dipping, gassing or misting with catalyst-containing solutions or low-viscosity suspensions, drawing them into the wall of the support through the capillary interconnecting porosity, or sucking it through or pumping it, preferably but not exclusively in one direction, but according to the invention alternately or oscillatingly in the direction of flow in order to obtain as intimate contact as possible between catalyst carrier material crystals and catalyst-containing solution, suspension, mist or gas.
  • the capillary porosity also serves to prevent the catalyst-containing solution, suspension, mist or gas from being withdrawn from the support structure when the loaded support is removed from the coating medium, but rather, except for the excess suspension present in the channels , Solution, mist or vapor, to be kept in the material porosity and fed to the subsequent adhesion-improving process step.
  • the catalyst is dried by reducing the solvent or suspending agent, not only by thermal treatment, also vacuum-assisted, but also by alternative methods such as freeze-drying. It is also advantageous to temporarily seal the channels after impregnation, misting or fumigation, for example, but not exclusively by a wax layer on the channel surface or at the inlet or outlet of the flow channels, especially to prevent the evaporation of effective catalyst substance during drying prior to its connection to the crystal surfaces.
  • the amount of catalyst substance remaining is determined by the specific concentration of the catalyst in the solution, suspension, vapor or mist, the crystals forming the capillary interconnecting pores and their accessible surfaces. Since there is capillarity, the degree of filling of the pores and contact with the crystal surfaces with catalyst-containing solution, suspension, vapor or mist is almost completely within a short time and uniformly over the entire inner and outer surface of the structure-forming support material. To ensure absolute completeness of the coating, the coating can optionally be carried out under vacuum.
  • a further catalyst material coating with a further catalyst having an exemplary attachment temperature of 930 ° C, followed by one or more Coatings with attachment temperatures of, for example, 803 ° C, 750 ° C and other temperatures. Since the catalysts behave quite differently in the sintering or calcination is the use of vacuum sintering, calcination, protective gas sintering or Schutzgaskalzination, vacuum or pressure sintering or calcination both in a single-layer coating with a catalyst or catalyst mixture, as well as a multiple coating provide according to the invention.
  • a coating of the inner and outer surface of the carrier within the manufacturing process of the carrier.
  • the only requirement is that the completion temperature of the support is not higher than the maximum production temperature of the catalyst, which is related to the maximum applicable temperature of the catalyst before its destruction or adverse change.
  • a low-melting ceramic glass base material with production temperatures of around 600 ° C. is suitable for taking up catalysts with maximum use temperatures above 600 ° C., the bonding temperatures being less than or equal to 600 ° C.
  • this may be, for example, cordierite - a classic support material for catalysts whose manufacturing temperature is usually between 1230 ° C and 1425 ° C, or silicon carbide with production temperatures above 1800 ° C.
  • the coating can take place after the carrier preparation, for example with steel, copper, aluminum, molybdenum, titanium and other carrier metals or alloys, but also during the production of the carrier.
  • the in-process coating is that the catalyst is introduced into the carrier mass before its shaping.
  • the disadvantage here is the relatively high proportion of catalyst material by shaping losses and the coating of the catalyst in the melt constituents of the support material.
  • the second possibility according to the invention is the coating of the carrier after its debindering in question.
  • the carrier is already freed from the shaping additives without the solidifying sintering - in the sinter metallurgical or ceramic production of the material has taken place.
  • the version is possible, in which the carrier has already taken its solidifying and final crystal structure formation.
  • This variant is also the most mechanically stable form for a coating and the easiest to automate compared to the two previous variants.
  • the structure-forming support material has to be oxygen-containing, but that only a high surface-forming fraction of oxygen-containing support material should be present in order to effect a rare earth catalyst coating.
  • An exemplary example of this is the combination of cordierite with silicon carbide which strengthens during oxidative sintering, the grains of which already have a silicon coating in the cordierite sintering, which is advantageous not only for the attachment of the catalyst, but also for the bonding of the cordierite to the silicon carbide. With the degree of fineness of the silicon carbide and its proportion in the mass in the support structure production, the reactive accessible crystal surface for binding the rare earth catalysts is determined.
  • Other oxygen-containing ceramics are known to those skilled in the art.
  • the coating has a thin oxide layer on the outer and inner metal surfaces, such as aluminum with aluminum oxide, copper with copper oxide, titanium with titanium oxide, magnesium with magnesium oxide and others Expert known metals and metal oxides advantageous.
  • a capillary interconnectingly porous catalyst support composed of a mixture of 50 percent by volume of cordierite and 50 percent by volume silicon carbide with a geometric outer diameter of 2 1/2 inches with quadrangular Strömungskanä- the clear width len of 1, 5 mm with a wall thickness of 350 ⁇ with a material porosity of 57% and average interconnecting pore size of 7.5 ⁇ , oxidatively oxidized in the production sintering process below 1400 ° C, is applied to a solution containing a content of 2.5% cerium.
  • the carrier is withdrawn from the catalyst solution at a constant rate, so that the excess contained in the channels of the catalyst structure, not insubstantially altered in their catalyst content, or for further impregnation mixture, unhindered on the contained in the material porosity Catalyst solution, pulled out. Due to the separation of the impregnated support from the catalyst solution, any solution that drips off because of possible concentration differences separately from the work-up - concentration adjustment - is fed in order to achieve the highest possible yield through the re-introduction To ensure coating process.
  • the impregnated and leaked now containing dissolved catalyst from rare earth is subjected to a gentle drying process to remove the solvent of the catalyst wherein the final phase of the drying, which serves exclusively to protect the subsequent kiln, vacuum-assisted can take place.
  • a temperature treatment with heating-holding and cooling phase in which a temperature of 800 ° C is not exceeded.
  • the nitrate, sulphate, carbonate, chloride and fluoride form can also be produced here.
  • this technology of the carrier with capillary interconnecting porosity and catalytically active coating can be used within the carrier-forming material are mainly the automotive industry in the mobile application as a catalyst or as a particle filter with catalytically active ingredient in to call the indoor and outdoor application. Further areas of application are the catalysis and filtration of industrial stationary exhaust and exhaust air treatment, the use as a reactor in chemical process processes as well as further applications in the environmental industry in water and wastewater treatment as well as air and exhaust air treatment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
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Abstract

L'invention concerne un système constitué d'un support pourvu de canaux d'écoulement et d'au moins une substance catalytiquement active, de préférence Pt, Rh ou de composés de terres rares, le matériau formant support ayant une porosité d'interconnexion capillaire et le revêtement catalytiquement actif étant appliqué au moins à l'intérieur des pores du matériau sur les cristaux formant les pores, de manière que la liaison de la substance catalytiquement active s'effectue par voie thermique et que le revêtement des cristaux du matériau support s'effectue sans revêtement auxiliaire dit « wash-coat ».
PCT/EP2018/068120 2017-07-07 2018-07-04 Système constitué d'un support pourvu de canaux d'écoulement et d'un revêtement dit « wash coat » WO2019008053A1 (fr)

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EP18740147.6A EP3648883A1 (fr) 2017-07-07 2018-07-04 Système constitué d'un support pourvu de canaux d'écoulement et d'un revêtement dit « wash coat »

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CH00882/17A CH713958A1 (de) 2017-07-07 2017-07-07 System bestehend aus einem Träger mit Strömungskanälen und mindestens einer katalystisch wirksamen Substanz.
CH00882/17 2017-07-07

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CN114477979B (zh) * 2021-12-24 2023-04-14 广州蓝日生物科技有限公司 一种具有连续微孔隙结构的实体聚合硅酸盐的制备方法

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