[go: up one dir, main page]

WO2018164069A1 - ハニカムフィルタ - Google Patents

ハニカムフィルタ Download PDF

Info

Publication number
WO2018164069A1
WO2018164069A1 PCT/JP2018/008387 JP2018008387W WO2018164069A1 WO 2018164069 A1 WO2018164069 A1 WO 2018164069A1 JP 2018008387 W JP2018008387 W JP 2018008387W WO 2018164069 A1 WO2018164069 A1 WO 2018164069A1
Authority
WO
WIPO (PCT)
Prior art keywords
honeycomb filter
cell
wall
honeycomb
base material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/008387
Other languages
English (en)
French (fr)
Inventor
真之助 後藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ibiden Co Ltd
Original Assignee
Ibiden Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ibiden Co Ltd filed Critical Ibiden Co Ltd
Priority to EP18764791.2A priority Critical patent/EP3593885A4/en
Priority to CN201880015092.7A priority patent/CN110382080B/zh
Priority to US16/491,147 priority patent/US10821420B2/en
Publication of WO2018164069A1 publication Critical patent/WO2018164069A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2027—Metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24492—Pore diameter
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J35/651—50-500 nm
    • 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
    • B01J35/64—Pore diameter
    • B01J35/653—500-1000 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—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
    • B01J37/0215—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
    • B01J37/08—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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C04B35/4885—Composites with aluminium oxide
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • C04B35/6365—Cellulose or derivatives thereof
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • 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
    • C04B38/0006—Honeycomb structures
    • 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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • 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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors
    • 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
    • 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
    • F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/915—Catalyst supported on particulate filters
    • B01D2255/9155—Wall flow filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9202—Linear dimensions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2279/00—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses
    • B01D2279/30—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses for treatment of exhaust gases from IC Engines
    • 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
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • 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
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/322—Transition aluminas, e.g. delta or gamma aluminas
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5212—Organic
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/522—Oxidic
    • C04B2235/5224—Alumina or aluminates
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/526—Fibers characterised by the length of the fibers
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5264—Fibers characterised by the diameter of the fibers
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron

Definitions

  • the present invention relates to a honeycomb filter used for collecting fine particles.
  • Patent Document 1 discloses a honeycomb filter made of silicon carbide as a honeycomb filter used for collecting fine particles.
  • Patent Document 2 discloses an exhaust gas purification catalyst in which a noble metal is supported on a monolith substrate containing ceria-zirconia composite oxide particles. It is described that the base material is composed of ceria-zirconia composite oxide particles to reduce the heat capacity, to easily raise the temperature of the monolith base material, and to improve the warm-up performance of the catalyst.
  • a substrate containing ceria-zirconia composite oxide particles disclosed in Patent Document 2 is adopted as the wall portion of the honeycomb filter.
  • the base material containing the ceria-zirconia composite oxide particles disclosed in Patent Document 2 hardly allows gas containing fine particles to pass therethrough, as the wall portion of the honeycomb filter that collects fine particles, Is unsuitable.
  • the silicon carbide particles are recrystallized to form pores between the particles, but the ceria-zirconia composite oxide particles are bonded with an inorganic binder. This is because no pores are formed.
  • a configuration in which a wall portion made of a substrate such as silicon carbide is covered with a ceria-zirconia composite oxide is also conceivable, but the supported amount of the ceria-zirconia composite oxide is limited to a range in which the wall portion can be covered.
  • the effect of improving exhaust gas purification performance is small.
  • the weight of the honeycomb filter also increases, so that the warm-up performance decreases.
  • the present invention has been made in view of these circumstances, and an object thereof is to provide a honeycomb filter having excellent warm-up performance.
  • a honeycomb filter of the present invention for solving the above problems is a honeycomb filter used for collecting fine particles, and includes a wall portion made of a base material containing ceria-zirconia composite oxide and an inorganic binder as constituent components,
  • the wall has a peak in the pore diameter range of 0.01 ⁇ m or more and less than 1 ⁇ m in the pore diameter distribution with the pore diameter and log differential pore volume measured by the mercury intrusion method as the horizontal axis and the vertical axis, respectively.
  • the gist is to have a peak in the pore diameter range of 1 ⁇ m to 50 ⁇ m.
  • the honeycomb filter has the wall portion made of the base material containing the ceria-zirconia composite oxide as a constituent component so that the wall portion made of the base material such as silicon carbide is covered with the ceria-zirconia composite oxide.
  • the heat capacity of the wall can be reduced if the content of the same ceria-zirconia composite oxide is the same.
  • the gas to be treated can be efficiently diffused into the wall through the pores having a peak in the pore diameter range of 0.01 ⁇ m or more and less than 1 ⁇ m. As a result, the purification performance of the gas diffused inside the wall is improved.
  • the presence of pores having a peak in the pore diameter range of 1 ⁇ m or more and 50 ⁇ m or less improves the gas permeability of the wall, so that the pressure loss is kept low while providing a function as a filter for collecting fine particles. be able to.
  • “warm-up performance” means the ease with which the honeycomb filter can be raised to a temperature at which sufficient gas purification performance can be obtained. That is, when the weight per unit volume is small and the purification performance is high like the honeycomb filter of the present invention, the “warm-up performance” is good.
  • the wall portion preferably has linear pores having a diameter of 1 ⁇ m or more and 50 ⁇ m or less penetrating the wall portion. According to this configuration, gas easily passes through the wall portion through the pores penetrating the wall portion, so that the gas permeability of the wall portion is preferably improved.
  • the base material of the honeycomb filter of the present invention preferably contains alumina as a constituent component. According to this configuration, by including alumina as a constituent component of the base material, the catalyst can be highly dispersed when the base material is supported on the base material, and the purification performance of the gas to be processed can be improved. Moreover, the mechanical strength of the wall part in a high temperature state can be improved.
  • the honeycomb filter of the present invention it is preferable that a catalyst is supported on the substrate. According to this configuration, the honeycomb filter can exhibit not only a function of collecting fine particles but also a function based on a catalyst such as a purification action of a gas to be processed.
  • the catalyst is preferably a noble metal.
  • the ceria-zirconia composite oxide has a function as a co-catalyst that promotes the catalytic action of a catalyst made of a noble metal. Therefore, the honeycomb filter of the present invention can exhibit a high catalytic action when combined with a catalyst made of a noble metal.
  • the honeycomb filter of the present invention preferably includes a plurality of cells which are partitioned by the wall portion and extend from a first end portion which is one end side of the honeycomb filter to a second end portion which is the other end side.
  • the cell includes a first cell in which an end on the first end side is opened and an end on the second end side is sealed, and the first end adjacent to the first cell.
  • a second cell whose end on the side is sealed and whose end on the second end side is open, and adjacent to at least one of the first cell and the second cell, the first end side It is preferable to provide the 3rd cell by which both the edge part of this and the edge part of the said 2nd edge part side were open
  • fine particles can be collected at the wall portion between the first cell and the second cell.
  • the pressure loss of a honey-comb filter can be reduced by providing the 3rd cell by which both the edge part by the side of a 1st edge part and the edge part by the side of a 2nd edge part were open
  • a honeycomb filter having excellent warm-up performance can be provided.
  • FIG. 2 is a sectional view taken along line 2-2 of FIG.
  • the graph which shows the pore diameter distribution of the wall part of an Example.
  • the graph which shows the pore diameter distribution of the wall part of a comparative example.
  • the honeycomb filter 10 of the present embodiment includes a cylindrical peripheral wall 11 and a partition wall 12 having a honeycomb shape in section that partitions the inside of the peripheral wall 11 into a plurality of cells S.
  • Each cell S extends from one end side in the axial direction of the peripheral wall 11 to the other end side, that is, from a first end portion that is one end side of the honeycomb filter 10 to a second end portion that is the other end side.
  • a wall portion 13 is constituted by the peripheral wall 11 and the partition wall 12.
  • the cell structure of the honeycomb filter 10 is not particularly limited.
  • the wall portion 13 is formed of a base material containing ceria-zirconia composite oxide (hereinafter also referred to as “CZ composite oxide”), an inorganic binder, and alumina as constituent components. That is, the base material constituting the wall portion 13 contains a CZ composite oxide, an inorganic binder, and alumina. And the catalyst is carry
  • CZ composite oxide ceria-zirconia composite oxide
  • the CZ composite oxide constituting the base material of the honeycomb filter of the present invention preferably contains 10% by mass or more, more preferably 20% by mass or more of ceria. Moreover, it is preferable to contain 70 mass% or less of ceria, and it is more preferable to contain 60 mass% or less. By containing 10% by mass or more of ceria, the ability to occlude and release oxygen in the exhaust gas is increased, and by setting it to 70% by mass or less, thermal durability is increased.
  • the CZ composite oxide may further contain an element selected from rare earth elements other than cerium.
  • rare earth elements other than cerium include scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium ( Dy), ytterbium (Yb), lutetium (Lu) and the like.
  • the content of the CZ composite oxide in the substrate is preferably 15 to 60% by mass.
  • the inorganic binder include alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgyro, bentonite, and boehmite.
  • the content of the inorganic binder in the substrate is not particularly limited, but it is preferably 10 to 30% by mass with respect to the substrate.
  • alumina particles are included as the alumina.
  • a noble metal used as the catalyst is easily dispersed and supported, and the mechanical strength of the wall portion 13 can be improved.
  • the type of alumina particles is not particularly limited, but it is preferable to use ⁇ -phase alumina (hereinafter also referred to as “ ⁇ -alumina”) or ⁇ -phase alumina (hereinafter also referred to as “ ⁇ -alumina”). . Since ⁇ -alumina suppresses phase transition even when exposed to a high temperature of about 1000 ° C., the mechanical strength of the honeycomb filter 10 at a high temperature is improved by using ⁇ -alumina as a constituent component of the substrate. . Since ⁇ -alumina has a large specific surface area, the precious metal used as a catalyst can be highly dispersed.
  • the content of alumina particles in the substrate is not particularly limited, but it is preferably 15 to 60% by mass based on the substrate.
  • the base material may contain other components other than CZ composite oxide, inorganic binder, and alumina.
  • other components include other inorganic particles such as particles having a smaller coefficient of thermal expansion than CZ composite oxide and alumina (hereinafter also referred to as “low thermal expansion coefficient particles”).
  • the thermal expansion coefficient of the substrate can be reduced, so that the thermal shock resistance of the honeycomb filter 10 is improved.
  • the low thermal expansion coefficient particles include cordierite, aluminum titanate, and lithium aluminosilicate material particles.
  • lithium aluminosilicate materials include ⁇ -spodumene and ⁇ -eucryptite.
  • the content of the low thermal expansion coefficient particles is not particularly limited, but is preferably 5 to 30% by mass with respect to the base material.
  • the catalyst supported on the base material examples include noble metals, alkali metals (element periodic table group 1), alkaline earth metals (element periodic table group 2), rare earth elements (element periodic table group 3), and transition metal elements. Is preferably a noble metal.
  • the noble metal include platinum group metals such as platinum, palladium, and rhodium.
  • the amount of the noble metal supported is not particularly limited, but is preferably 0.1 to 20 g / L, more preferably 0.5 to 15 g / L with respect to the apparent volume (L) of the honeycomb filter 10. .
  • the honeycomb filter 10 includes the first cell S1 in which the end on the first end side (one end side) of the honeycomb filter 10 is opened and the end on the second end side (other end side) is sealed.
  • the second cell S2 is adjacent to the first cell S1, and the end on the first end side is sealed and the end on the second end side is open. Since the ends of the first cell S1 and the second cell S2 are different from each other, the gas flowing into the first cell S1 on one end side of the honeycomb filter 10 as shown by an arrow in FIG.
  • the honeycomb filter 10 is adjacent to at least one of the first cell S1 and the second cell S2, and the third cell S3 in which both the end on one end side and the end on the other end side of the honeycomb filter 10 are opened. May be further provided. That is, some of the plurality of cells S may not be sealed at both ends.
  • the gas that has flowed into the third cell S3 on one end side of the honeycomb filter 10 can pass through the same third cell S3 as it is and flow out of the honeycomb filter 10 on the other end side of the honeycomb filter 10.
  • the third cell S3 is adjacent to the first cell S1
  • the gas that has flowed into the first cell S1 on one end side of the honeycomb filter 10 flows into the wall portion 13 between the first cell S1 and the third cell S3. It can also flow into the third cell S3 through the inside, and then flow out of the honeycomb filter 10 on the other end side of the honeycomb filter 10.
  • the arrangement position of the third cell S3 is appropriately selected in a range adjacent to at least one of the first cell S1 and the second cell S2.
  • a cell S having a small cross-sectional area on the outer peripheral side of the honeycomb filter 10 can be set as the third cell S3.
  • the ratio of the third cells S3 to all the cells S is not particularly limited, but is preferably 1/3 or less.
  • the length T of the sealing part 14 shown in FIG. 2 is not particularly limited, it is preferably thicker than the wall thickness of the partition wall 12.
  • the length T of the sealing portion 14 is preferably 1 to 10 mm.
  • the honeycomb filter 10 of the present embodiment is used for collecting fine particles contained in a gas discharged from an internal combustion engine such as a vehicle or a construction machine. For this reason, the partition wall 12 of the honeycomb filter 10 has pores for allowing the gas to be processed to pass therethrough.
  • the partition wall 12 is a wall portion having a specific pore size distribution. As shown in FIG. 3, the specific pore size distribution transverses the pore size and log differential pore volume measured by the mercury intrusion method.
  • the pore diameter range of 0.01 ⁇ m or more and less than 1 ⁇ m and in the pore diameter range of 1 ⁇ m or more and 50 ⁇ m or less there are peaks in the pore diameter range of 0.01 ⁇ m or more and less than 1 ⁇ m and in the pore diameter range of 1 ⁇ m or more and 50 ⁇ m or less.
  • the peak existing in the pore diameter range of 0.01 ⁇ m or more and less than 1 ⁇ m is derived from pores formed in the gaps between particles of the CZ composite oxide used as the raw material.
  • the number of peaks present in the pore diameter range of 0.01 ⁇ m or more and less than 1 ⁇ m may be only one or plural.
  • the peak existing in the pore diameter range of 1 ⁇ m or more and 50 ⁇ m or less is derived from pores formed by the manufacturing method of the honeycomb filter 10 described later.
  • the pores derived from this manufacturing method are, for example, formed in a linear shape having a diameter of 1 ⁇ m or more and 50 ⁇ m or less that penetrates the partition wall 12.
  • the number of peaks present in the pore diameter range of 1 ⁇ m or more and 50 ⁇ m or less may be only one or plural.
  • the ratio of the pores present in the pore diameter range of 0.01 ⁇ m to less than 1 ⁇ m and the pores present in the pore diameter range of 1 ⁇ m to 50 ⁇ m is not particularly limited, but is 10: 1 to 1.5: 1 by volume. Preferably there is.
  • the linear pores penetrating the partition wall 12 can be confirmed by observing the fracture surface of the partition wall 12 using an electron microscope.
  • the pores having a diameter of 1 ⁇ m or more and 50 ⁇ m or less observed using an electron microscope 80% or more of the pores are preferably linear pores penetrating the partition wall 12.
  • the shape of the linear pores may be any of a linear shape, a curved shape, and a broken line shape.
  • the porosity of the partition wall 12 is not particularly limited, but is preferably 40 to 80%, and more preferably 55 to 75%.
  • the porosity of the sealing portion 14 is not particularly limited, but is preferably 40 to 80%, and more preferably 55 to 75%.
  • the pore diameter distribution and the porosity of the partition wall 12 can be measured by a mercury intrusion method under the conditions of a contact angle of 130 ° and a surface tension of 485 mN / m.
  • the honeycomb filter 10 is manufactured by sequentially performing a mixing process, a forming process, a sealing process, a degreasing process, a firing process, and a supporting process described below.
  • the mixing step is a step of preparing a raw material mixture by mixing raw materials such as CZ composite oxide particles, inorganic binder, alumina particles, and organic fibers.
  • the CZ composite oxide particles it is preferable to use a solid solution of ceria and zirconia.
  • the solid solution of ceria and zirconia is, for example, by adding ammonia water to an aqueous solution in which a cerium salt such as cerium nitrate and a zirconium salt such as zirconium oxynitrate is dissolved to form a coprecipitate, and the resulting precipitate is dried. And then calcining at 400 to 500 ° C. for about 5 hours.
  • the average particle size of the CZ composite oxide particles that are one of the raw materials is not particularly limited, but is preferably 1 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • the average particle diameter can be measured with a laser diffraction particle size distribution analyzer.
  • the inorganic binder any of the specific examples of the inorganic binder described above can be used.
  • the proportion of the inorganic binder in the raw material mixture is not particularly limited, but is preferably 10 to 30% by mass as the solid content.
  • ⁇ -alumina particles and ⁇ -alumina particles can be used as the alumina particles.
  • the proportion of the alumina particles in the raw material mixture is not particularly limited, but is preferably 10 to 50% by mass as the solid content.
  • the average particle diameter of the alumina particles is not particularly limited, but the secondary particles are preferably 1 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • organic fibers examples include acrylic fibers and polyester fibers.
  • the size of the organic fiber is not particularly limited, but the diameter is preferably 1 to 50 ⁇ m, and more preferably 3 to 40 ⁇ m.
  • the length is preferably 0.1 to 30 mm, and more preferably 0.1 to 10 mm.
  • the ratio of the organic fiber in the raw material mixture is not particularly limited, but is preferably 10 to 50% by mass as a solid content.
  • the raw material mixture may contain low thermal expansion coefficient particles as described above, or inorganic fibers, organic binders, pore formers, molding aids, and dispersion media.
  • the average particle diameter of the low thermal expansion coefficient particles is not particularly limited, but is preferably 1 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • Examples of the material constituting the inorganic fiber include alumina, silica, silica alumina, and glass.
  • Examples of the organic binder include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, phenol resin, and epoxy resin.
  • the pore former may be in the form of particles, and examples of such pore former include acrylic resin, coke, and starch.
  • examples of the molding aid include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol, and surfactant.
  • dispersion medium examples include water, organic solvents such as benzene, and alcohols such as methanol. These raw materials may be mixed using a known mixer or attritor, and further kneaded with a kneader.
  • the forming step is a step of forming a honeycomb formed body by forming the raw material mixture obtained in the mixing step.
  • the honeycomb formed body is produced by, for example, extruding a raw material mixture using an extrusion die and cutting it to a predetermined length so as to have the same shape as the honeycomb filter 10 through firing shrinkage in a subsequent firing step. . That is, the wall part 13 which comprises the surrounding wall 11 and the partition wall 12 of the honey-comb filter 10 is produced by extruding at once.
  • the sealing step is a step of forming the sealing portion 14 by filling the end portion of the cell S of the honeycomb formed body obtained by the forming step with a sealing material paste.
  • a sealing material paste the same paste as the above raw material mixture can be used, but it is preferable that no organic fiber is contained. By not using the organic fiber, the porosity of the sealing portion 14 can be reduced.
  • the honeycomb formed body in which the sealing portion 14 is formed by the sealing process is dried as necessary. Note that the sealing step may be performed after a degreasing step or a firing step described later.
  • the degreasing step is a step of producing a degreased body by degreasing the honeycomb formed body on which the sealing portion 14 is formed, in other words, a step of heating the honeycomb formed body to remove organic components contained in the honeycomb formed body. .
  • a degreasing process can be performed using a well-known single furnace, what is called a batch furnace, and a continuous furnace.
  • the degreasing temperature is not particularly limited, but is preferably 300 to 800 ° C, more preferably 400 to 750 ° C.
  • the degreasing time is not particularly limited, but the degreasing temperature is preferably maintained for 1 to 10 hours, more preferably 2 to 5 hours.
  • the degreasing atmosphere is not particularly limited, but the oxygen concentration is preferably 0.1 to 20%.
  • the firing process is a process for producing the honeycomb filter 10 by firing the degreased body obtained in the degreasing process.
  • the mechanical strength of the honeycomb filter 10 is improved by bonding particles such as CZ composite oxide with an inorganic binder by firing.
  • the firing step can be performed using a known single furnace, a so-called batch furnace, or a continuous furnace.
  • the firing temperature is not particularly limited, but is preferably 800 to 1300 ° C, more preferably 900 to 1200 ° C.
  • the firing time is not particularly limited, but it is preferably held for 1 to 20 hours, more preferably 1 to 15 hours, at the above firing temperature.
  • the firing atmosphere is not particularly limited, but the oxygen concentration is preferably 1 to 20%.
  • the firing process may be performed separately using a furnace different from the degreasing process, or may be performed continuously using the same furnace as the degreasing process.
  • the honeycomb filter 10 of the present embodiment having the wall portion 13 made of a CZ composite oxide and having the above-described specific pore size distribution through the mixing step, the forming step, the sealing step, the degreasing step, and the firing step. Can be manufactured.
  • the supporting step is a step of supporting the catalyst on the honeycomb filter 10 obtained by the firing step.
  • the method for supporting the catalyst include a method in which the honeycomb filter 10 is immersed in a solution containing catalyst particles and a complex, and then the honeycomb filter 10 is pulled up and heated.
  • the wall portion 13 of the honeycomb filter 10 includes a base material containing a CZ composite oxide as a constituent component and a catalyst supported on the base material.
  • the honeycomb filter is provided with a wall portion made of a base material containing CZ composite oxide and an inorganic binder as constituents, so that the wall portion made of a base material such as silicon carbide is coated with the CZ composite oxide.
  • the heat capacity of the wall portion can be reduced.
  • the gas to be treated can be efficiently diffused into the wall through the pores having a peak in the pore diameter range of 0.01 ⁇ m or more and less than 1 ⁇ m. As a result, the purification performance of the gas diffused inside the wall is improved.
  • the presence of pores having a peak in the pore diameter range of 1 ⁇ m or more and 50 ⁇ m or less improves the gas permeability of the wall, so that the pressure loss is kept low while providing a function as a filter for collecting fine particles. be able to.
  • the wall portion has linear pores having a diameter of 1 ⁇ m or more and 50 ⁇ m or less penetrating the wall portion. Accordingly, gas easily passes through the wall through the pores penetrating the wall, and thus the gas permeability of the wall is preferably improved.
  • the base material of the wall portion contains alumina as a constituent component. Therefore, since the supported catalyst can be highly dispersed, the purification performance of the gas to be processed can be improved. Moreover, the mechanical strength of the wall part in a high temperature state can be improved.
  • the base material of the wall is provided with a supported catalyst. Therefore, the honeycomb filter can exhibit not only a function of collecting fine particles but also a function based on a catalyst such as a purification action of a gas to be processed.
  • the honeycomb filter can exhibit high catalytic action.
  • the honeycomb filter has a plurality of cells which are partitioned by the wall portion and extend from the first end portion which is one end side of the honeycomb filter to the second end portion which is the other end side.
  • the cell has an end on the first end side opened, a first cell on which the end on the second end side is sealed, and an end on the first end side adjacent to the first cell.
  • the pressure loss of a honey-comb filter can be reduced by providing the 3rd cell by which both the edge part by the side of a 1st edge part and the edge part by the side of a 2nd edge part were open
  • the present embodiment can be implemented with the following modifications. Moreover, it is also possible to implement combining the structure of the said embodiment and the structure shown in the following modified examples suitably.
  • the wall part was comprised with the surrounding wall and the partition wall, you may be comprised only with the partition wall.
  • the honeycomb filter may be formed by forming an outer peripheral coat layer on the outer periphery of the partition wall.
  • the base material which comprises a wall part does not necessarily need to contain an alumina as a structural component.
  • the raw material for the honeycomb filter does not necessarily include alumina particles.
  • the honeycomb filter does not necessarily have to include the third cell. That is, all the cells may have a configuration in which either one of both end portions is sealed. With this configuration, the collection efficiency of the honeycomb filter can be improved.
  • Example 1 The following raw materials were mixed to prepare a raw material mixture.
  • CZ composite oxide particles having an average particle diameter of 2 ⁇ m: 24.0% by mass ⁇ -alumina particles with an average particle diameter of 2 ⁇ m: 12.0% by mass ⁇ -alumina fiber (inorganic fiber) having an average fiber diameter of 3 ⁇ m and an average fiber length of 60 ⁇ m: 5.0% by mass Acrylic fiber (organic fiber) having an average fiber diameter of 30 ⁇ m and an average fiber length of 1 mm: 13.0% by mass Boehmite (inorganic binder): 10.0% by mass Methyl cellulose (organic binder): 7.0% by mass Polyoxyethylene oleyl ether (molding aid): 4.0% by mass Ion exchange water (dispersion medium): 25.0% by mass Using this raw material mixture, a cylindrical molded body was formed by an extruder.
  • this molded body is cut to a predetermined length to produce a honeycomb molded body, and then the end of a predetermined cell is sealed with a sealing agent to form a sealed portion as shown in FIG. did.
  • the composition of the sealing agent is the same as that of the raw material mixture except that it does not contain organic fibers. Moreover, the length of the sealing part was about 3 mm.
  • the honeycomb formed body was dried, degreased at 700 ° C. for 3 hours, and fired at 1100 ° C. for 10 hours to produce a honeycomb filter.
  • the obtained honeycomb filter had a cylindrical shape with a diameter of 117 mm and a length of 80 mm, a cell density of 46 cells / cm 2 (300 cpsi), and a wall thickness of 0.254 mm (10 mil).
  • dinitrodiammine palladium nitrate solution [Pd (NH 3 ) 2 (NO 2 ) 2 ] HNO 3 , palladium concentration 100 g / L
  • rhodium nitrate solution [Rd (NO 3 ) 3 ], rhodium concentration 50 g / L)
  • the honeycomb filter manufactured by the above process was immersed in this mixed solution and held for 15 minutes. Then, it dried at 110 degreeC for 2 hours, and baked at 500 degreeC in nitrogen atmosphere for 1 hour, and carried the palladium catalyst and the rhodium catalyst on the honeycomb filter.
  • the amount of catalyst supported was 0.14 g / L per apparent volume of the honeycomb filter in total of palladium and rhodium.
  • Comparative Example 1 A honeycomb filter of Comparative Example 1 was produced by omitting organic fibers from the raw material of Example 1 and following the same procedure as in Example 1 with the other raw material blend ratios unchanged.
  • the cells were alternately plugged with a plugging agent having the same composition as that of the raw material mixture.
  • the cut end of the honeycomb molded body is used as a support material, and the honeycomb molded body is heated at 450 ° C. for 5 hours in a state where the honeycomb molded body is placed on the support material.
  • a degreased body from which was removed was obtained.
  • the honeycomb fired body was obtained by holding at 2000 ° C. for 4.5 hours in an argon atmosphere. Next, the honeycomb fired body is held at 800 ° C.
  • a honeycomb structure mainly composed of silicon carbide having a thickness of 46.5 pieces / cm 2 (300 cpsi) and a wall thickness of 0.254 mm was manufactured. This honeycomb structure had an average pore diameter of 20 ⁇ m and a porosity of 60%. This honeycomb structure was bonded with an inorganic adhesive and subjected to outer peripheral processing to produce a cylindrical honeycomb structure having a diameter of 117 mm and a length of 80 mm.
  • FIGS. 3 and 4 The results of measuring the pore size distribution of the wall portions of the honeycomb filters of Example 1 and Comparative Example 1 are shown in FIGS. 3 and 4, respectively.
  • the pore size distribution of the wall part was measured by a mercury intrusion method under the conditions of a contact angle of 130 ° and a surface tension of 485 mN / m, and the pore size and log differential pore volume were represented on the horizontal axis and the vertical axis, respectively. .
  • Example 1 As shown in FIG. 3, in Example 1, one peak was confirmed in the pore diameter range of 0.01 ⁇ m to less than 1 ⁇ m, and one peak was confirmed in the pore diameter range of 1 ⁇ m to 50 ⁇ m. On the other hand, as shown in FIG. 4, in Comparative Example 1, although one peak could be confirmed in the pore size range of 0.01 ⁇ m to less than 1 ⁇ m, no peak was confirmed in the pore size range of 1 ⁇ m to 50 ⁇ m.
  • the metal pipe in which the honeycomb filters of Example 1 and Comparative Examples 1 and 2 are arranged in an airtight state is connected to the exhaust pipe of a V-type 6-cylinder 3.5L engine, and the HC concentration ((HC inflow) from the stoichiometric engine start.
  • the time required for -HC outflow amount / (HC inflow amount) ⁇ 100) to be 50% or less was measured to evaluate the warm-up performance.
  • FIG. 5 is a cross-sectional view schematically showing a pressure loss measuring method.
  • the honeycomb filter 10 is disposed in an airtight state in the metal tube 21.
  • a metal tube 23 connected to the blower 22 is connected to the metal tube 21.
  • air having a flow rate of 10 m / s was passed through the honeycomb filter 10 from the blower 22, and the differential pressure (pressure loss) before and after the honeycomb filter 10 was measured with the pressure gauge 24.
  • Table 1 shows the results of warm-up performance measurement and pressure loss measurement.
  • the honeycomb filter of Example 1 has a shorter time until the hydrocarbon (HC) purification rate reaches 50% than the honeycomb filters of Comparative Examples 1 and 2, and warm-up performance. It was confirmed to be excellent.
  • the honeycomb filter of Example 1 had a lower pressure loss than the honeycomb filter of Comparative Example 1, and it was confirmed that the honeycomb filter functions as a filter that collects fine particles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Toxicology (AREA)
  • Geometry (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Filtering Materials (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)

Abstract

ハニカムフィルタは、微粒子の捕集に用いられ、セリア－ジルコニア複合酸化物と無機バインダを構成成分とする基材からなる壁部（１３）を備える。壁部（１３）は、水銀圧入法で測定される気孔径及びｌｏｇ微分細孔容積をそれぞれ横軸及び縦軸とする気孔径分布において、気孔径０．０１μｍ以上１μｍ未満の範囲にピークを有するとともに、気孔径１μｍ以上５０μｍ以下の範囲にピークを有する。

Description

ハニカムフィルタ
　本発明は、微粒子の捕集に用いられるハニカムフィルタに関する。
　特許文献１には、微粒子の捕集に用いられるハニカムフィルタとして、炭化ケイ素からなるハニカムフィルタが開示されている。特許文献２には、セリア－ジルコニア複合酸化物粒子を含むモノリス基材に貴金属が担持された排ガス浄化触媒が開示されている。セリア－ジルコニア複合酸化物粒子で基材を構成することで熱容量を小さくし、モノリス基材の温度を上げやすくして、触媒の暖機性能を向上させることが記載されている。
国際公開第２００６／０４１１７４号 特開２０１５－８５２４１号公報
　ところで、特許文献１に開示されるハニカムフィルタの暖機性能を向上させるために、ハニカムフィルタの壁部として、特許文献２に開示されるセリア－ジルコニア複合酸化物粒子を含む基材を採用することが考えられる。しかしながら、特許文献２に開示されるセリア－ジルコニア複合酸化物粒子を含む基材は、壁部が微粒子を含むガスをほとんど通過させることができないために、微粒子を捕集するハニカムフィルタの壁部としては不適である。炭化ケイ素粒子は再結晶することで、粒子間に気孔（pore）が形成されるが、セリア－ジルコニア複合酸化物粒子は無機バインダで結合しているため、粒子間にガスが通過する適当なサイズの気孔が形成されないためである。また、炭化ケイ素等の基材からなる壁部をセリア－ジルコニア複合酸化物により被覆する構成も考えられるが、セリア－ジルコニア複合酸化物の担持量が壁部に被覆可能な範囲に限定されるため、排ガスの浄化性能の向上効果は小さい。加えて、基材に被覆する構造とすることでは、ハニカムフィルタの重量も増加するため、暖機性能が低下する。この発明は、こうした実情に鑑みてなされたものであり、その目的は、暖機性能に優れるハニカムフィルタを提供することにある。
　上記課題を解決するための本発明のハニカムフィルタは、微粒子の捕集に用いられるハニカムフィルタであって、セリア－ジルコニア複合酸化物と無機バインダを構成成分とする基材からなる壁部を備え、上記壁部は、水銀圧入法で測定される気孔径及びｌｏｇ微分細孔容積をそれぞれ横軸及び縦軸とする気孔径分布において、気孔径０．０１μｍ以上１μｍ未満の範囲にピークを有するとともに、気孔径１μｍ以上５０μｍ以下の範囲にピークを有することを要旨とする。
　この構成によれば、セリア－ジルコニア複合酸化物を構成成分とする基材からなる壁部をハニカムフィルタが備えることにより、炭化ケイ素等の基材からなる壁部にセリア－ジルコニア複合酸化物が被覆された構成に比べて、同じセリア－ジルコニア複合酸化物の含有量であれば、壁部の熱容量を小さくすることができる。また、気孔径０．０１μｍ以上１μｍ未満の範囲にピークを有する気孔を通じて、処理対象となるガスを壁部の内部に効率良く拡散させることができる。これらにより、壁部の内部に拡散したガスの浄化性能が向上する。また、気孔径１μｍ以上５０μｍ以下の範囲にピークを有する気孔が存在することにより、壁部のガス透過性が向上するため、微粒子を捕集するフィルタとしての機能を持たせつつ圧力損失を低く抑えることができる。ここで、「暖機性能」とは、ハニカムフィルタの十分なガス浄化性能が得られる温度までの上がりやすさを意味するものである。すなわち本発明のハニカムフィルタのように単位体積当たりの重量が小さく、浄化性能が高いと「暖機性能」がよい。
　本発明のハニカムフィルタについて、上記壁部は、当該壁部を貫通する直径１μｍ以上５０μｍ以下の線状の気孔を有することが好ましい。この構成によれば、壁部を貫通する気孔を通じてガスが壁部を通過しやすくなるため、壁部のガス透過性が好適に向上する。
　本発明のハニカムフィルタの基材は、構成成分としてアルミナを含むことが好ましい。この構成によれば、基材の構成成分としてアルミナを含むことにより、触媒を基材に担持させたときに高分散させることができ、処理対象となるガスの浄化性能を向上させることができる。また、高温状態における壁部の機械的強度を向上させることができる。
　本発明のハニカムフィルタについて、上記基材に触媒が担持されていることが好ましい。この構成によれば、ハニカムフィルタは、微粒子を捕集する機能だけでなく、処理対象となるガスの浄化作用等の触媒に基づく機能も発揮することができる。
　本発明のハニカムフィルタについて、上記触媒は、貴金属であることが好ましい。セリア－ジルコニア複合酸化物は、貴金属からなる触媒の触媒作用を促進させる助触媒としての機能を有する。そのため、本発明のハニカムフィルタは、貴金属からなる触媒と組み合わせることにより、高い触媒作用を発揮することができる。
　本発明のハニカムフィルタは、上記壁部によって区画されるとともに、上記ハニカムフィルタの一端側である第１端部から他端側である第２端部に延びる複数のセルを有することが好ましい。上記セルは、上記第１端部側の端部が開放され、上記第２端部側の端部が封止された第１セルと、上記第１セルに隣接して、上記第１端部側の端部が封止され、上記第２端部側の端部が開放された第２セルと、上記第１セル及び上記第２セルの少なくとも一方に隣接して、上記第１端部側の端部及び上記第２端部側の端部の両方が開放された第３セルとを備えることが好ましい。この構成によれば、第１セルと第２セルの間の壁部で微粒子を捕集することができる。また、第１端部側の端部と第２端部側の端部の両方が開放された第３セルを備えることにより、ハニカムフィルタの圧力損失を低下させることができる。
　本発明によれば、暖機性能に優れるハニカムフィルタを提供することができる。
ハニカムフィルタの斜視図。 図１の２－２線断面図。 実施例の壁部の気孔径分布を示すグラフ。 比較例の壁部の気孔径分布を示すグラフ。 圧力損失測定装置の模式図。
　以下、本発明の一実施形態を説明する。
　図１に示すように、本実施形態のハニカムフィルタ１０は、筒状の周壁１１と、周壁１１の内部を複数のセルＳに区画する断面ハニカム形状の区画壁１２とを備えている。各セルＳは、周壁１１の軸方向の一端側から他端側、すなわち、ハニカムフィルタ１０の一端側である第１端部から他端側である第２端部に延びている。周壁１１と区画壁１２とによって壁部１３が構成されている。ハニカムフィルタ１０のセル構造は特に限定されるものではないが、例えば、区画壁１２の壁厚が０．１～０．７ｍｍであり、セル密度が１ｃｍ２あたり１５．５～１２４セルであるセル構造とすることができる。なお、上記「０．１～０．７ｍｍ」は、「０．１ｍｍ以上０．７ｍｍ以下」を意味し、上記「１５．５～１２４セル」は、「１５．５セル以上１２４セル以下」を意味する。すなわち、本明細書中、「Ａ～Ｂ」とは「Ａ以上Ｂ以下」を意味するものとする。
　壁部１３は、セリア－ジルコニア複合酸化物（以下、「ＣＺ複合酸化物」ともいう。）と無機バインダとアルミナを構成成分とする基材によって形成されている。すなわち、壁部１３を構成する基材には、ＣＺ複合酸化物と無機バインダとアルミナが含まれている。そして、基材を構成する粒子の表面には触媒が担持されている。
　本発明のハニカムフィルタの基材を構成するＣＺ複合酸化物は、セリアを１０質量％以上含むことが好ましく、２０質量％以上含むことがより好ましい。また、セリアを７０質量％以下含むことが好ましく、６０質量％以下含むことがより好ましい。セリアを１０質量％以上含むことで、排ガス中の酸素の吸蔵放出能が高くなり、７０質量％以下とすることで熱耐久性が高くなる。
　ＣＺ複合酸化物は、セリウム以外の希土類元素から選択される元素をさらに含んでいてもよい。セリウム以外の希土類元素としては、スカンジウム（Ｓｃ）、イットリウム（Ｙ）、ランタン（Ｌａ）、プラセオジム（Ｐｒ）、ネオジム（Ｎｄ）、サマリウム（Ｓｍ）、ガドリニウム（Ｇｄ）、テルビウム（Ｔｂ）、ジスプロシウム（Ｄｙ）、イッテルビウム（Ｙｂ）、ルテチウム（Ｌｕ）などが挙げられる。
　基材におけるＣＺ複合酸化物の含有率は１５～６０質量％であることが好ましい。
　上記無機バインダとしては、例えば、アルミナゾル、シリカゾル、チタニアゾル、水ガラス、セピオライト、アタパルジャイロ、ベントナイト、ベーマイトを用いることができる。基材における無機バインダの含有量は特に限定されないが、基材に対して、１０～３０質量％含有していることが好ましい。
　上記アルミナとして、アルミナ粒子が含まれていることが好ましい。アルミナ粒子が含まれていると、上記触媒として用いられる例えば貴金属が分散担持されやすく、また、壁部１３の機械的強度を向上させることができる。アルミナ粒子の種類としては、特に限定されないが、θ相のアルミナ（以下、「θ－アルミナ」ともいう。）や、γ相のアルミナ（以下、「γ－アルミナ」ともいう）を用いることが好ましい。θ－アルミナは、１０００℃程度の高温に曝されても相転移が抑制されるため、θ－アルミナを基材の構成成分に用いることにより、高温状態におけるハニカムフィルタ１０の機械的強度が向上する。γ－アルミナは比表面積が大きいため、触媒として用いる貴金属を高分散させることができる。基材におけるアルミナ粒子の含有量は特に限定されないが、基材に対して、１５～６０質量％含有していることが好ましい。
　基材には、ＣＺ複合酸化物、無機バインダ、アルミナ以外のその他の成分が含まれていてもよい。その他の成分としては、例えば、ＣＺ複合酸化物やアルミナよりも熱膨張係数が小さい粒子（以下、「低熱膨張係数粒子」ともいう。）等のその他の無機粒子が挙げられる。
　その他の成分として、低熱膨張係数粒子を含有させた場合には、基材の熱膨張係数を小さくすることができるため、ハニカムフィルタ１０の耐熱衝撃性が向上する。低熱膨張係数粒子としては、例えば、コージェライト、チタン酸アルミニウム、リチウムアルミノケイ酸塩系材料の粒子が挙げられる。リチウムアルミノケイ酸塩系材料としては、例えば、βスポジュメンやβユークリプタイトが挙げられる。低熱膨張係数粒子の含有量は特に限定されるものではないが、基材に対して、５～３０質量％含有していることが好ましい。
　基材に担持される触媒としては、貴金属、アルカリ金属（元素周期表１族）、アルカリ土類金属（元素周期表２族）、希土類元素（元素周期表３族）、遷移金属元素が挙げられるが、貴金属であることが好ましい。貴金属としては、例えば、白金、パラジウム、ロジウム等の白金族金属が挙げられる。貴金属の担持量は特に限定されないが、ハニカムフィルタ１０の見掛けの体積（Ｌ）に対して、０．１～２０ｇ／Ｌであることが好ましく、０．５～１５ｇ／Ｌであることがより好ましい。
　図２に示すように、複数のセルＳのうち所定のいくつかのセルＳは、端部が封止部１４により封止されている。すなわち、ハニカムフィルタ１０は、ハニカムフィルタ１０の第１端部側（一端側）の端部が開放され、第２端部側（他端側）の端部が封止された第１セルＳ１と、第１セルＳ１に隣接して第１端部側の端部が封止され、第２端部側の端部が開放された第２セルＳ２とを備えている。第１セルＳ１と第２セルＳ２は互いに異なる側の端部が封止されているため、図２中の矢印で示すように、ハニカムフィルタ１０の一端側において第１セルＳ１内に流入したガスは、第１セルＳ１と第２セルＳ２の間の壁部１３の内部を通過して第２セルＳ２内に流入し、その後、ハニカムフィルタ１０の他端側でハニカムフィルタ１０の外に流出する。この際、壁部１３における第１セルＳ１側の表面に、ガス中に含まれる微粒子が捕集される。
　また、ハニカムフィルタ１０は、第１セルＳ１及び第２セルＳ２の少なくとも一方に隣接して、ハニカムフィルタ１０の一端側の端部と他端側の端部の両方が開放された第３セルＳ３を更に備えてもよい。すなわち、複数のセルＳのうちのいくつかは、両端部がともに封止されていなくてもよい。ハニカムフィルタ１０の一端側において第３セルＳ３内に流入したガスは、そのまま同じ第３セルＳ３内を通過してハニカムフィルタ１０の他端側でハニカムフィルタ１０の外に流出することができる。第３セルＳ３が第１セルＳ１に隣接している場合、ハニカムフィルタ１０の一端側において第１セルＳ１内に流入したガスは、第１セルＳ１と第３セルＳ３の間の壁部１３の内部を通過して第３セルＳ３内に流入し、その後、ハニカムフィルタ１０の他端側でハニカムフィルタ１０の外に流出することもできる。
　第３セルＳ３の配置位置は、第１セルＳ１及び第２セルＳ２の少なくとも一方に隣接している範囲において適宜選択される。例えば、図２に示すように、ハニカムフィルタ１０の外周側における断面積が小さいセルＳを第３セルＳ３とすることができる。また、全てのセルＳに占める第３セルＳ３の割合は特に限定されるものではないが、１／３以下であることが好ましい。
　図２に示す封止部１４の長さＴは特に限定されるものではないが、区画壁１２の壁厚よりも厚いことが好ましい。区画壁１２の壁厚が０．１～０．７ｍｍである場合、封止部１４の長さＴは、１～１０ｍｍであることが好ましい。
　次に、ハニカムフィルタ１０の壁部１３の気孔径分布について説明する。
　本実施形態のハニカムフィルタ１０は、車両や建設機械等の内燃機関から排出されるガスに含まれる微粒子の捕集に用いられる。そのため、ハニカムフィルタ１０の区画壁１２は、処理対象のガスを通過させるための気孔（pore）を有している。区画壁１２は、特定の気孔径分布を有する壁部であり、図３に示すように、上記特定の気孔径分布は、水銀圧入法で測定される気孔径及びｌｏｇ微分細孔容積をそれぞれ横軸及び縦軸としたときに、気孔径０．０１μｍ以上１μｍ未満の範囲と、気孔径１μｍ以上５０μｍ以下の範囲とに、それぞれピークを有する。気孔径０．０１μｍ以上１μｍ未満の範囲に存在するピークは、原料に用いたＣＺ複合酸化物等の粒子間の隙間に形成された気孔に由来する。気孔径０．０１μｍ以上１μｍ未満の範囲に存在するピークの数は、１つのみであってもよいし、複数であってもよい。
　気孔径１μｍ以上５０μｍ以下の範囲に存在するピークは、後述のハニカムフィルタ１０の製造方法によって形成された気孔に由来する。この製造方法に由来する気孔は、例えば、区画壁１２を貫通する直径１μｍ以上５０μｍ以下の線状に形成されている。気孔径１μｍ以上５０μｍ以下の範囲に存在するピークの数は、１つのみであってもよいし、複数であってもよい。気孔径０．０１μｍ以上１μｍ未満の範囲に存在する気孔と、気孔径１μｍ以上５０μｍ以下の範囲に存在する気孔の割合は、特に限定されないが、体積比で１０：１～１．５：１であることが好ましい。
　なお、区画壁１２を貫通する線状の気孔は、区画壁１２の破断面を電子顕微鏡を用いて観察することによって確認することができる。電子顕微鏡を用いて観察される直径１μｍ以上５０μｍ以下の気孔のうち、８０％以上の気孔が、区画壁１２を貫通する線状の気孔であることが好ましい。また、線状の気孔の形状は、直線状、曲線状、折れ線状のいずれであってもよい。
　区画壁１２の気孔率は特に限定されないが、４０～８０％であることが好ましく、５５～７５％であることがより好ましい。封止部１４の気孔率は特に限定されないが、４０～８０％であることが好ましく、５５～７５％であることがより好ましい。区画壁１２の気孔径分布及び気孔率は、水銀圧入法にて、接触角を１３０°、表面張力を４８５ｍＮ／ｍの条件で測定することができる。
　次に、本実施形態のハニカムフィルタ１０の製造方法について説明する。ハニカムフィルタ１０は、以下に記載する混合工程、成形工程、封止工程、脱脂工程、焼成工程、担持工程を順に経ることにより製造される。
　（混合工程）
　混合工程は、ＣＺ複合酸化物粒子、無機バインダ、アルミナ粒子、有機繊維などの原料を混合して原料混合物を作製する工程である。ＣＺ複合酸化物粒子としては、セリアとジルコニアの固溶体を用いることが好ましい。セリアとジルコニアの固溶体は、例えば、硝酸セリウムなどのセリウム塩と、オキシ硝酸ジルコニウムなどのジルコニウム塩を溶解させた水溶液に、アンモニア水を加えて共沈殿を生成させ、得られた沈殿物を乾燥させた後に４００～５００℃で５時間程度焼成することにより調製することができる。
　原料の１つであるＣＺ複合酸化物粒子の平均粒子径は特に限定されるものではないが、１～１０μｍであることが好ましく、１～５μｍであることがより好ましい。平均粒子径は、レーザー回折式粒度分布測定装置にて測定することができる。
　無機バインダとしては、上記した無機バインダの具体例のうちいずれかを用いることができる。原料混合物中の無機バインダの割合は特に限定されないが、固形分として１０～３０質量％であることが好ましい。
　アルミナ粒子としては、上記したようにθ－アルミナ粒子やγ－アルミナ粒子を用いることができる。原料混合物中のアルミナ粒子の割合は特に限定されないが、固形分として１０～５０質量％であることが好ましい。アルミナ粒子の平均粒子径は特に限定されないが、二次粒子として１～１０μｍであることが好ましく、１～５μｍであることがより好ましい。
　有機繊維としては、例えば、アクリル繊維、ポリエステル繊維などを用いることができる。有機繊維の寸法は特に限定されるものではないが、直径が１～５０μｍであることが好ましく、３～４０μｍであることがより好ましい。また、長さが０．１～３０ｍｍであることが好ましく、０．１～１０ｍｍであることがより好ましい。原料混合物中の有機繊維の割合は特に限定されないが、固形分として１０～５０質量％であることが好ましい。
　上記原料混合物には、必要に応じて、上記したような低熱膨張係数粒子、あるいは、無機繊維、有機バインダ、造孔剤、成形助剤、分散媒を加えてもよい。
　低熱膨張係数粒子の平均粒子径は特に限定されるものではないが、１～１０μｍであることが好ましく、１～５μｍであることがより好ましい。
　無機繊維を構成する材料としては、例えば、アルミナ、シリカ、シリカアルミナ、ガラスが挙げられる。
　有機バインダとしては、例えば、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリエチレングリコール、フェノール樹脂、エポキシ樹脂が挙げられる。
　造孔剤は、有機繊維とは異なり粒子状であってもよく、そのような造孔剤としては、アクリル樹脂、コークス、デンプンが挙げられる。
　成形助剤としては、エチレングリコール、デキストリン、脂肪酸、脂肪酸石鹸、ポリアルコール、界面活性剤が挙げられる。
　分散媒としては、水、ベンゼン等の有機溶媒、メタノール等のアルコールが挙げられる。
　これらの原料は、公知のミキサーやアトライタなどを用いて混合してもよく、さらにニーダーなどで混練してもよい。
　（成形工程）
　成形工程は、混合工程により得られた原料混合物を成形してハニカム成形体を作製する工程である。ハニカム成形体は、後の焼成工程における焼成収縮を経てハニカムフィルタ１０と同一形状となるよう、例えば、原料混合物を押出金型を用いて押出成形し、所定の長さに切断することにより作製する。すなわち、ハニカムフィルタ１０の周壁１１と区画壁１２とを構成する壁部１３を一度に押出成形することにより作製する。
　（封止工程）
　封止工程は、成形工程により得られたハニカム成形体のセルＳの端部に封止材ペーストを充填して、封止部１４を形成する工程である。封止材ペーストとしては、上記の原料混合物と同様のものを用いることができるが、有機繊維を含まないことが好ましい。有機繊維を用いないことにより、封止部１４の気孔率を小さくすることができる。封止工程によって封止部１４を形成したハニカム成形体は、必要に応じて乾燥を行う。なお、封止工程は後述する脱脂工程又は焼成工程の後で行われてもよい。
　（脱脂工程）
　脱脂工程は、封止部１４を形成したハニカム成形体を脱脂して脱脂体を作製する工程、換言すれば、ハニカム成形体を加熱してハニカム成形体に含まれる有機分を除去する工程である。脱脂工程において長尺状の有機繊維が消失することにより、壁部１３に線状の気孔を形成することができる。脱脂工程は、公知の単独炉、いわゆるバッチ炉や、連続炉を用いて行うことができる。脱脂温度は特に限定されないが、３００～８００℃が好ましく、４００～７５０℃であることがより好ましい。脱脂時間は特に限定されないが、上記の脱脂温度において１～１０時間保持することが好ましく、２～５時間保持することがより好ましい。脱脂雰囲気は特に限定されないが、酸素濃度が０．１～２０％であることが好ましい。
　（焼成工程）
　焼成工程は、脱脂工程により得られた脱脂体を焼成してハニカムフィルタ１０を作製する工程である。焼成によって、ＣＺ複合酸化物等の粒子間が無機バインダで結合されることにより、ハニカムフィルタ１０の機械的強度が向上する。焼成工程は、公知の単独炉、いわゆるバッチ炉や、連続炉を用いて行うことができる。焼成温度は特に限定されないが、８００～１３００℃が好ましく、９００～１２００℃であることがより好ましい。焼成時間は特に限定されないが、上記の焼成温度において１～２０時間保持することが好ましく、１～１５時間保持することがより好ましい。焼成雰囲気は特に限定されないが、酸素濃度が１～２０％であることが好ましい。焼成工程は、脱脂工程とは別の炉を用いて別途行ってもよいし、脱脂工程と同じ炉を用いて連続的に行ってもよい。上記の混合工程、成形工程、封止工程、脱脂工程、焼成工程を経ることにより、ＣＺ複合酸化物からなり上記した特定の気孔径分布を示す壁部１３を有する本実施形態のハニカムフィルタ１０を製造することができる。
　（担持工程）
　担持工程は、焼成工程により得られたハニカムフィルタ１０に触媒を担持する工程である。触媒を担持する方法としては、例えば、触媒の粒子や錯体を含む溶液にハニカムフィルタ１０を浸漬した後、ハニカムフィルタ１０を引き上げて、加熱する方法が挙げられる。触媒を担持することによって、ハニカムフィルタ１０の壁部１３は、ＣＺ複合酸化物を構成成分とする基材と、この基材に担持された触媒とを備えるものとなる。
　本実施形態の作用及び効果を説明する。
　（１）ＣＺ複合酸化物と無機バインダを構成成分とする基材からなる壁部をハニカムフィルタが備えることにより、炭化ケイ素等の基材からなる壁部にＣＺ複合酸化物が被覆された構成に比べて、同じＣＺ複合酸化物の含有量であれば、壁部の熱容量を小さくすることができる。また、気孔径０．０１μｍ以上１μｍ未満の範囲にピークを有する気孔を通じて、処理対象となるガスを壁部の内部に効率良く拡散させることができる。これらにより、壁部の内部に拡散したガスの浄化性能が向上する。また、気孔径１μｍ以上５０μｍ以下の範囲にピークを有する気孔が存在することにより、壁部のガス透過性が向上するため、微粒子を捕集するフィルタとしての機能を持たせつつ圧力損失を低く抑えることができる。
　（２）壁部は、壁部を貫通する直径１μｍ以上５０μｍ以下の線状の気孔を有する。したがって、壁部を貫通する気孔を通じてガスが壁部を通過しやすくなるため、壁部のガス透過性が好適に向上する。
　（３）壁部の基材が、構成成分としてアルミナを含む。したがって、担持した触媒を高分散させることができるため、処理対象となるガスの浄化性能を向上させることができる。また、高温状態における壁部の機械的強度を向上させることができる。
　（４）壁部の基材は担持された触媒を備える。したがって、ハニカムフィルタは、微粒子を捕集する機能だけでなく、処理対象となるガスの浄化作用等の触媒に基づく機能も発揮することができる。
　（５）触媒が貴金属である場合、貴金属からなる触媒の触媒作用を促進させる助触媒としての機能をセリア－ジルコニア複合酸化物が有することから、ハニカムフィルタは高い触媒作用を発揮することができる。
　（６）ハニカムフィルタは、壁部によって区画されるとともに、ハニカムフィルタの一端側である第１端部から他端側である第２端部に延びる複数のセルを有する。セルは、第１端部側の端部が開放され、第２端部側の端部が封止された第１セルと、第１セルに隣接して、第１端部側の端部が封止され、第２端部側の端部が開放された第２セルと、第１セル及び第２セルの少なくとも一方に隣接して、第１端部側の端部及び第２端部側の端部の両方が開放された第３セルとを備える。したがって、第１セルと第２セルの間の壁部で微粒子を捕集することができる。また、第１端部側の端部と第２端部側の端部の両方が開放された第３セルを備えることにより、ハニカムフィルタの圧力損失を低減させることができる。
　本実施形態は、次のように変更して実施することも可能である。また、上記実施形態の構成や以下の変更例に示す構成を適宜組み合わせて実施することも可能である。
　・本実施形態では、壁部は周壁と区画壁とで構成されていたが、区画壁のみで構成されていてもよい。この場合、区画壁の外周に外周コート層を形成することによりハニカムフィルタが形成されていてもよい。
　・壁部を構成する基材は、必ずしもアルミナを構成成分として含まなくてもよい。また、ハニカムフィルタの原料には、必ずしもアルミナ粒子が含まれなくてもよい。
　・ハニカムフィルタは必ずしも第３セルを備えていなくてもよい。すなわち、全てのセルがその両端部のいずれか一方を封止された構成であってもよい。この構成により、ハニカムフィルタの捕集効率を向上させることができる。
　以下、上記実施形態をさらに具体化した実施例について説明する。
　（実施例１）
　下記原料を混合して原料混合物を調製した。
　平均粒子径２μｍのＣＺ複合酸化物粒子：２４．０質量％
　平均粒子径２μｍのθ－アルミナ粒子：１２．０質量％
　平均繊維径３μｍ、平均繊維長６０μｍのαアルミナ繊維（無機繊維）：５．０質量％
　平均繊維径３０μｍ、平均繊維長１ｍｍのアクリル繊維（有機繊維）：１３．０質量％
　ベーマイト（無機バインダ）：１０．０質量％
　メチルセルロース（有機バインダ）：７．０質量％
　ポリオキシエチレンオレイルエーテル（成形助剤）：４．０質量％
　イオン交換水（分散媒）：２５．０質量％
　この原料混合物を用いて、押出成形機によって円柱状の成形体を成形した。次に、この成形体を所定の長さに切断してハニカム成形体を作製した後、図２に示すように所定のセルの端部を封止剤にて封止して封止部を形成した。封止剤の組成は、有機繊維を含まないこと以外は上記の原料混合物と同じ組成である。また、封止部の長さは約３ｍｍとした。次に、ハニカム成形体を乾燥させた後、７００℃で３時間脱脂し、１１００℃で１０時間焼成することにより、ハニカムフィルタを作製した。得られたハニカムフィルタは、直径が１１７ｍｍ、長さが８０ｍｍの円柱状であり、セルの密度が４６個／ｃｍ２（３００ｃｐｓｉ）、壁部の厚さが０．２５４ｍｍ（１０ｍｉｌ）であった。
　次に、ジニトロジアンミンパラジウム硝酸溶液（［Ｐｄ（ＮＨ３）２（ＮＯ２）２］ＨＮＯ３、パラジウム濃度１００ｇ／Ｌ）と硝酸ロジウム溶液（［Ｒｄ（ＮＯ３）３］、ロジウム濃度５０ｇ／Ｌ）を３：１の体積割合で混合して、混合溶液を調製した。この混合溶液中に、上記工程により製造されたハニカムフィルタを浸漬し、１５分間保持した。その後、１１０℃で２時間乾燥し、窒素雰囲気中５００℃で１時間焼成することによって、ハニカムフィルタにパラジウム触媒とロジウム触媒を担持した。触媒の担持量は、パラジウムとロジウムの合計でハニカムフィルタの見掛けの体積当たり０．１４ｇ／Ｌとした。
　（比較例１）
　実施例１の原料から有機繊維を省き、それ以外の原料の配合比はそのままで実施例１と同様の手順を踏むことにより、比較例１のハニカムフィルタを作製した。
　（比較例２）
　まず、下記原料物を混合して原料混合物を調製した。
　平均粒子径１５μｍの炭化ケイ素粒子：２８質量％
　平均粒子径０．９５μｍの炭化ケイ素粒子：１９質量％
　平均粒子径３４μｍのシラスバルーン（造孔剤）：９質量％
　平均粒子径２８μｍのデンプン（造孔剤）：１６質量％
　メチルセルロース（有機バインダ）：５質量％
　ソルビタン脂肪酸エステル（分散剤）：３質量％
　ポリオキシアルキレン系化合物（可塑剤）：２質量％
　水（分散媒）：１８質量％
　この原料混合物を用いて、押出成形機によって角柱状の成形体を成形した。次に、この成形体を切断してハニカム成形体を作製した後、セルを互い違いに上記原料混合物と同じ組成の目封止剤にて目封止した。次に、ハニカム成形体を切断した際の切れ端を支持材として用い、この支持材の上にハニカム成形体を載置した状態で、ハニカム成形体を４５０℃で５時間加熱することにより、有機分が除去された脱脂体を得た。さらに、脱脂体を支持材の上に載置したままの状態で、アルゴン雰囲気下２０００℃で４．５時間保持してハニカム焼成体を得た。次に、ハニカム焼成体を窒素分圧１０ｋＰａの窒素雰囲気下８００℃で４．５時間保持して窒化工程を行うことにより、縦３４．４ｍｍ×横３４．３ｍｍ×長さ８０ｍｍでセルの密度が４６．５個／ｃｍ２（３００ｃｐｓｉ）、壁部の厚さが０．２５４ｍｍの炭化ケイ素を主成分とするハニカム構造体を作製した。このハニカム構造体の平均気孔径は２０μｍ、気孔率は６０％であった。このハニカム構造体を、無機接着材で接着し、外周加工を施すことで、直径が１１７ｍｍ、長さが８０ｍｍの円柱状のハニカム構造体を作製した。
　次に、γ－アルミナ粒子にパラジウムを担持した粒子とＣＺ複合酸化物にロジウムを担持した粒子を１：２で混合して、上記円柱状のハニカム構造体にウォッシュコートして、ハニカムフィルタを作製した。この時の触媒の担持量は、パラジウムとロジウムの合計でハニカムフィルタの見掛けの体積当たり０．１４ｇ／Ｌとした。
　（評価試験）
　実施例及び比較例のハニカムフィルタについて、以下の方法により、気孔径分布、暖機性能及び圧力損失を測定した。
　（気孔径分布測定）
　実施例１及び比較例１のハニカムフィルタの壁部の気孔径分布を測定した結果を図３及び図４にそれぞれ示す。壁部の気孔径分布は、水銀圧入法にて接触角を１３０°、表面張力を４８５ｍＮ／ｍの条件で測定し、気孔径及びｌｏｇ微分細孔容積をそれぞれ横軸及び縦軸にして表した。
　図３に示すとおり、実施例１では、気孔径０．０１μｍ以上１μｍ未満の範囲に１つのピークが確認されるとともに、気孔径１μｍ以上５０μｍ以下の範囲に１つのピークが確認された。これに対し、図４に示すとおり、比較例１では、気孔径０．０１μｍ以上１μｍ未満の範囲に１つのピークが確認できるものの、気孔径１μｍ以上５０μｍ以下の範囲にピークは確認されなかった。
　（暖機性能測定）
　実施例１及び比較例１，２の各ハニカムフィルタが気密状態で配置された金属管をＶ型６気筒３．５Ｌエンジンの排気管に接続し、ストイキエンジン始動からＨＣ濃度（（ＨＣの流入量－ＨＣの流出量）／（ＨＣの流入量）×１００）が５０％以下となるまでに要する時間を測定し、暖気性能を評価した。
　（圧力損失測定）
　図５に示したような圧力損失測定装置２０を用いて実施例１及び比較例１，２のハニカムフィルタの圧力損失を測定した。図５は、圧力損失測定方法を模式的に示す断面図である。まず、ハニカムフィルタ１０を金属管２１の中に気密状態に配置する。この金属管２１に、送風機２２に接続された金属管２３を接続する。そして、送風機２２から流速が１０ｍ／ｓの空気をハニカムフィルタ１０に流通させ、ハニカムフィルタ１０の前後における差圧（圧力損失）を圧力計２４で測定した。
　暖機性能測定と圧力損失測定の結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
 　表１に示すとおり、実施例１のハニカムフィルタは、比較例１、２のハニカムフィルタと比較して、炭化水素（ＨＣ）の浄化率が５０％に到達するまでの時間が短く、暖機性能に優れることが確認された。また、実施例１のハニカムフィルタは、比較例１のハニカムフィルタよりも圧力損失が低くなっており、微粒子を捕集するフィルタとして機能することが確認された。
　１０…ハニカムフィルタ、１１…周壁、１２…区画壁、１３…壁部、１４…封止部、Ｓ…セル。

Claims (6)

  1. 　微粒子の捕集に用いられるハニカムフィルタであって、
    　セリア－ジルコニア複合酸化物と無機バインダを構成成分とする基材からなる壁部を備え、
    　前記壁部は、水銀圧入法で測定される気孔径及びｌｏｇ微分細孔容積をそれぞれ横軸及び縦軸とする気孔径分布において、気孔径０．０１μｍ以上１μｍ未満の範囲にピークを有するとともに、気孔径１μｍ以上５０μｍ以下の範囲にピークを有することを特徴とするハニカムフィルタ。
  2. 　前記壁部は、当該壁部を貫通する直径１μｍ以上５０μｍ以下の線状の気孔を有する請求項１に記載のハニカムフィルタ。
  3. 　前記基材は、構成成分としてアルミナを含む請求項１又は２に記載のハニカムフィルタ。
  4. 　前記基材に触媒が担持されている請求項１～３のいずれか一項に記載のハニカムフィルタ。
  5. 　前記触媒は、貴金属である請求項４に記載のハニカムフィルタ。
  6. 　前記壁部によって区画されるとともに、前記ハニカムフィルタの一端側である第１端部から他端側である第２端部に延びる複数のセルを有し、
    　前記セルは、前記第１端部側の端部が開放され、前記第２端部側の端部が封止された第１セルと、
    　前記第１セルに隣接して、前記第１端部側の端部が封止され、前記第２端部側の端部が開放された第２セルと、
    　前記第１セル及び前記第２セルの少なくとも一方に隣接して、前記第１端部側の端部及び前記第２端部側の端部の両方が開放された第３セルとを備える請求項１～５のいずれか一項に記載のハニカムフィルタ。
PCT/JP2018/008387 2017-03-06 2018-03-05 ハニカムフィルタ Ceased WO2018164069A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP18764791.2A EP3593885A4 (en) 2017-03-06 2018-03-05 Honeycomb filter
CN201880015092.7A CN110382080B (zh) 2017-03-06 2018-03-05 蜂窝过滤器
US16/491,147 US10821420B2 (en) 2017-03-06 2018-03-05 Honeycomb filter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-041790 2017-03-06
JP2017041790A JP2018143955A (ja) 2017-03-06 2017-03-06 ハニカムフィルタ

Publications (1)

Publication Number Publication Date
WO2018164069A1 true WO2018164069A1 (ja) 2018-09-13

Family

ID=63448571

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/008387 Ceased WO2018164069A1 (ja) 2017-03-06 2018-03-05 ハニカムフィルタ

Country Status (5)

Country Link
US (1) US10821420B2 (ja)
EP (1) EP3593885A4 (ja)
JP (1) JP2018143955A (ja)
CN (1) CN110382080B (ja)
WO (1) WO2018164069A1 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020025899A (ja) * 2018-08-09 2020-02-20 エヌ・イーケムキャット株式会社 排ガス浄化触媒
WO2021044874A1 (ja) * 2019-09-04 2021-03-11 イビデン株式会社 ハニカムフィルタ及びハニカムフィルタの製造方法
US11433382B2 (en) * 2018-03-13 2022-09-06 Ibiden Co., Ltd. Honeycomb filter and method for manufacturing honeycomb filters

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021145326A1 (ja) * 2020-01-14 2021-07-22 三井金属鉱業株式会社 排ガス浄化システム
JP7449720B2 (ja) * 2020-03-02 2024-03-14 日本碍子株式会社 ハニカムフィルタ
JP2022152985A (ja) * 2021-03-29 2022-10-12 日本碍子株式会社 ハニカムフィルタ

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006041174A (ja) 2004-07-27 2006-02-09 Toshiba Corp 不揮発性半導体記憶装置
JP2011183360A (ja) * 2010-03-11 2011-09-22 Ngk Insulators Ltd ハニカム触媒体
JP2013517934A (ja) * 2010-02-01 2013-05-20 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 押出しソリッド本体を含む三元触媒
JP2014024058A (ja) * 2012-06-20 2014-02-06 Toyota Central R&D Labs Inc 排ガス浄化用触媒担体、それを用いた排ガス浄化用触媒、及び排ガス浄化用触媒担体の製造方法
JP2015085241A (ja) 2013-10-29 2015-05-07 トヨタ自動車株式会社 排ガス浄化触媒
JP2016169127A (ja) * 2015-03-13 2016-09-23 日野自動車株式会社 ハニカム構造体の製造方法
JP2017006827A (ja) * 2015-06-18 2017-01-12 株式会社デンソー ハニカム構造体及び自動車用触媒コンバータ
WO2017110313A1 (ja) * 2015-12-25 2017-06-29 株式会社デンソー 排ガスフィルタ
WO2018012565A1 (ja) * 2016-07-14 2018-01-18 イビデン株式会社 ハニカム構造体及び該ハニカム構造体の製造方法

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5139992A (en) * 1989-11-08 1992-08-18 Engelhard Corporation Three-way conversion catalyst including a ceria-containing zirconia support
ATE190240T1 (de) * 1991-11-26 2000-03-15 Engelhard Corp Oxidationskatalysator und verfahren zur anwendung
US5266548A (en) * 1992-08-31 1993-11-30 Norton Chemical Process Products Corp. Catalyst carrier
DE19533486A1 (de) * 1995-09-12 1997-03-13 Basf Ag Monomodale und polymodale Katalysatorträger und Katalysatoren mit engen Porengrößenverteilungen und deren Herstellverfahren
DE19533484A1 (de) * 1995-09-12 1997-03-13 Basf Ag Monomodale und polymodale Katalysatorträger und Katalysatoren mit engen Porengrößenverteilungen und deren Herstellverfahren
US20010026838A1 (en) * 1996-06-21 2001-10-04 Engelhard Corporation Monolithic catalysts and related process for manufacture
EP1243335B1 (en) * 1999-11-16 2014-03-05 Ibiden Co., Ltd. Catalyst and method for preparation thereof
US6827754B2 (en) * 2001-09-13 2004-12-07 Hitachi Metals, Ltd. Ceramic honeycomb filter
US7276212B2 (en) * 2001-10-01 2007-10-02 Engelhard Corporation Exhaust articles for internal combustion engines
US7041622B2 (en) * 2002-02-06 2006-05-09 Delphi Technologies, Inc. Catalyst, an exhaust emission control device and a method of using the same
US7214643B2 (en) * 2002-03-22 2007-05-08 Kabushiki Kaisha Toyota Chuo Kenkyusho Metal oxide and method for producing the same, and catalyst
JP4200430B2 (ja) * 2003-02-18 2008-12-24 トヨタ自動車株式会社 排ガス浄化フィルタ触媒用基材の良否判別方法
US7875250B2 (en) * 2003-12-11 2011-01-25 Umicore Ag & Co. Kg Exhaust treatment device, and methods of making the same
US7722829B2 (en) * 2004-09-14 2010-05-25 Basf Catalysts Llc Pressure-balanced, catalyzed soot filter
DE602005019182D1 (de) * 2004-09-30 2010-03-18 Ibiden Co Ltd Wabenstruktur
DE602005015610D1 (de) * 2004-10-12 2009-09-03 Ibiden Co Ltd Keramische wabenstruktur
KR20080042902A (ko) * 2004-12-27 2008-05-15 이비덴 가부시키가이샤 세라믹 허니컴 구조체
CN104529422B (zh) * 2006-03-07 2018-11-16 日本碍子株式会社 陶瓷结构体的制造方法
RU2009132612A (ru) * 2007-01-31 2011-03-10 Басф Каталистс Ллк (Us) Газовые катализаторы, включающие пористую сотовидную стенку
JP4845795B2 (ja) * 2007-04-09 2011-12-28 トヨタ自動車株式会社 排ガス浄化フィルタとその製造方法
JP5150132B2 (ja) * 2007-04-27 2013-02-20 日本碍子株式会社 ハニカムフィルタシステム
US8038951B2 (en) * 2007-08-09 2011-10-18 Basf Corporation Catalyst compositions
WO2009073099A1 (en) * 2007-11-30 2009-06-11 Corning Incorporated Zeolite-based honeycomb body
WO2009118816A1 (ja) * 2008-03-24 2009-10-01 イビデン株式会社 ハニカム構造体
JP5273446B2 (ja) * 2008-05-12 2013-08-28 日産自動車株式会社 排ガス浄化用触媒及びその製造方法
WO2009141874A1 (ja) * 2008-05-20 2009-11-26 イビデン株式会社 ハニカム構造体
EP2127729A1 (en) * 2008-05-30 2009-12-02 Mazda Motor Corporation Exhaust gas purification catalyst
WO2010077843A2 (en) * 2008-12-29 2010-07-08 Basf Catalysts Llc Oxidation catalyst with low co and hc light-off and systems and methods
FR2948116B1 (fr) * 2009-07-17 2012-05-04 Rhodia Operations Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse
US8833064B2 (en) * 2009-11-06 2014-09-16 Basf Corporation Small engine layered catalyst article and method of making
WO2011067823A1 (ja) * 2009-12-01 2011-06-09 イビデン株式会社 ハニカムフィルタ及び排ガス浄化装置
FR2959735B1 (fr) * 2010-05-06 2012-06-22 Rhodia Operations Composition a base d'oxydes de zirconium, de cerium d'au moins une autre terre rare, a porosite specifique, procede de preparation et utilisation en catalyse.
CN102553653B (zh) * 2010-12-22 2016-09-14 太平洋工业发展公司 具有储氧能力的催化剂载体材料及其制造方法
US10232348B2 (en) * 2010-12-22 2019-03-19 Pacific Industrial Development Corporation Doped catalyst support materials having oxygen storage capacity (OSC) and method of making thereof
GB2513364B (en) * 2013-04-24 2019-06-19 Johnson Matthey Plc Positive ignition engine and exhaust system comprising catalysed zone-coated filter substrate
SG11201408381QA (en) * 2012-06-15 2015-01-29 Basf Corp Composites of mixed metal oxides for oxygen storage
GB201220912D0 (en) * 2012-11-21 2013-01-02 Johnson Matthey Plc Oxidation catalyst for treating the exhaust gas of a compression ignition engine
GB201302686D0 (en) * 2013-02-15 2013-04-03 Johnson Matthey Plc Filter comprising three-way catalyst
GB2512648B (en) * 2013-04-05 2018-06-20 Johnson Matthey Plc Filter substrate comprising three-way catalyst
US20140369912A1 (en) * 2013-06-13 2014-12-18 Basf Corporation Integrated Supports for Emission Control Catalysts
US10258978B2 (en) * 2013-08-14 2019-04-16 Dinex A/S Multilayer coated particle filter
JP6380249B2 (ja) * 2015-06-18 2018-08-29 株式会社デンソー ハニカム構造体の製造方法
JP6431823B2 (ja) * 2015-07-13 2018-11-28 株式会社Ｓｏｋｅｎ 排ガス浄化フィルタ
JP2019506289A (ja) * 2015-12-09 2019-03-07 コーニング インコーポレイテッド 多孔質セラミック材料、フィルタ、および物品
CN109070000A (zh) * 2016-04-29 2018-12-21 庄信万丰股份有限公司 排气系统
JP2018143956A (ja) * 2017-03-06 2018-09-20 イビデン株式会社 ハニカムフィルタ
JP6637008B2 (ja) * 2017-09-29 2020-01-29 株式会社キャタラー 排ガス浄化用触媒

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006041174A (ja) 2004-07-27 2006-02-09 Toshiba Corp 不揮発性半導体記憶装置
JP2013517934A (ja) * 2010-02-01 2013-05-20 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 押出しソリッド本体を含む三元触媒
JP2011183360A (ja) * 2010-03-11 2011-09-22 Ngk Insulators Ltd ハニカム触媒体
JP2014024058A (ja) * 2012-06-20 2014-02-06 Toyota Central R&D Labs Inc 排ガス浄化用触媒担体、それを用いた排ガス浄化用触媒、及び排ガス浄化用触媒担体の製造方法
JP2015085241A (ja) 2013-10-29 2015-05-07 トヨタ自動車株式会社 排ガス浄化触媒
JP2016169127A (ja) * 2015-03-13 2016-09-23 日野自動車株式会社 ハニカム構造体の製造方法
JP2017006827A (ja) * 2015-06-18 2017-01-12 株式会社デンソー ハニカム構造体及び自動車用触媒コンバータ
WO2017110313A1 (ja) * 2015-12-25 2017-06-29 株式会社デンソー 排ガスフィルタ
WO2018012565A1 (ja) * 2016-07-14 2018-01-18 イビデン株式会社 ハニカム構造体及び該ハニカム構造体の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3593885A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11433382B2 (en) * 2018-03-13 2022-09-06 Ibiden Co., Ltd. Honeycomb filter and method for manufacturing honeycomb filters
JP2020025899A (ja) * 2018-08-09 2020-02-20 エヌ・イーケムキャット株式会社 排ガス浄化触媒
WO2021044874A1 (ja) * 2019-09-04 2021-03-11 イビデン株式会社 ハニカムフィルタ及びハニカムフィルタの製造方法

Also Published As

Publication number Publication date
JP2018143955A (ja) 2018-09-20
EP3593885A4 (en) 2021-01-13
US20190388873A1 (en) 2019-12-26
US10821420B2 (en) 2020-11-03
CN110382080B (zh) 2021-09-17
CN110382080A (zh) 2019-10-25
EP3593885A1 (en) 2020-01-15

Similar Documents

Publication Publication Date Title
WO2018164069A1 (ja) ハニカムフィルタ
JP6998870B2 (ja) ハニカム構造体及び該ハニカム構造体の製造方法
WO2018012562A1 (ja) ハニカム構造体及び該ハニカム構造体の製造方法
US11298687B2 (en) Honeycomb catalytic converter
JP6965289B2 (ja) ハニカム構造体及びハニカム構造体の製造方法
WO2018164070A1 (ja) ハニカムフィルタ
WO2019176868A1 (ja) ハニカムフィルタ及びハニカムフィルタの製造方法
JP6949019B2 (ja) ハニカム構造体及び該ハニカム構造体の製造方法
JP6782571B2 (ja) ハニカム構造体
CN111450816A (zh) 蜂窝结构体
JP2019026547A (ja) ハニカム構造体の製造方法
JP6845777B2 (ja) ハニカム触媒の製造方法
JP6781080B2 (ja) ハニカムフィルタ
JP6811121B2 (ja) ハニカムフィルタの製造方法
JP2018143959A (ja) ハニカム構造体
WO2019026645A1 (ja) ハニカム構造体の製造方法及びハニカム構造体
WO2020105666A1 (ja) ハニカム構造体
JP2021037485A (ja) ハニカムフィルタ及びハニカムフィルタの製造方法
JP2020083695A (ja) ハニカム構造体

Legal Events

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

Ref document number: 18764791

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018764791

Country of ref document: EP

Effective date: 20191007