WO2013175552A1 - ハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法 - Google Patents
ハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法 Download PDFInfo
- Publication number
- WO2013175552A1 WO2013175552A1 PCT/JP2012/062947 JP2012062947W WO2013175552A1 WO 2013175552 A1 WO2013175552 A1 WO 2013175552A1 JP 2012062947 W JP2012062947 W JP 2012062947W WO 2013175552 A1 WO2013175552 A1 WO 2013175552A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- honeycomb filter
- honeycomb
- exhaust gas
- fired body
- thickness
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- B01D46/2422—Mounting of the body within a housing
-
- 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
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2462—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure the outer peripheral sealing
-
- 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
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2474—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the walls along the length of the honeycomb
-
- 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
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2478—Structures comprising honeycomb segments
-
- 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
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2482—Thickness, height, width, length or 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
- B01D53/92—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
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- 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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6264—Mixing media, e.g. organic solvents
-
- 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
- C04B35/6316—Binders based on silicon compounds
-
- 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
- C04B35/6346—Polyesters
-
- 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
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
- C04B37/005—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of glass or ceramic material
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/5089—Silica sols, alkyl, ammonium or alkali metal silicate cements
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- 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
-
- 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
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- 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
- C04B2235/5216—Inorganic
- C04B2235/522—Oxidic
- C04B2235/5228—Silica and alumina, including aluminosilicates, e.g. mullite
-
- 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
-
- 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
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- 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
- C04B2235/5463—Particle size distributions
- C04B2235/5472—Bimodal, multi-modal or multi-fraction
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
- C04B2235/663—Oxidative annealing
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/04—Ceramic interlayers
- C04B2237/08—Non-oxidic interlayers
- C04B2237/083—Carbide interlayers, e.g. silicon carbide interlayers
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/04—Ceramic interlayers
- C04B2237/09—Ceramic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/36—Non-oxidic
- C04B2237/365—Silicon carbide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to a honeycomb filter, an exhaust gas purification device, and an exhaust gas purification method.
- Gasoline engines have the advantage of lower PM emissions than diesel engines. Therefore, normally, a filter for removing PM is not necessary. On the other hand, gasoline engines have the drawback of inferior fuel consumption compared to diesel engines.
- Patent Documents 1 to 4 disclose a honeycomb structure having thin partition walls as a filter for collecting PM contained in exhaust gas.
- An important characteristic of a honeycomb filter for collecting PM contained in exhaust gas is pressure loss.
- a high pressure loss leads to a deterioration in fuel consumption, so a low pressure loss is desirable.
- an increase in pressure loss is suppressed by reducing the cell wall thickness.
- the present invention has been made to solve the above problems, and an object thereof is to provide a honeycomb filter for a gasoline engine having sufficient mechanical strength while suppressing an increase in pressure loss. Moreover, this invention aims at providing the exhaust gas purification apparatus provided with the said honey-comb filter, and the exhaust gas purification method using the said exhaust gas purification apparatus.
- the honeycomb filter according to claim 1 Including a silicon carbide honeycomb fired body in which a large number of cells are arranged in parallel in the longitudinal direction across the cell wall, and an outer peripheral wall is formed on the outer periphery; Either one end of the cell is sealed, The thickness of the cell wall is 0.2 mm or less, The outer peripheral wall is thicker than the cell wall, An oxide layer containing silicon is formed on the surface of the silicon carbide particles constituting the honeycomb fired body, It is used for collecting particulates contained in exhaust gas discharged from a gasoline engine.
- the aperture ratio of the honeycomb filter can be increased by reducing the thickness of the cell wall to 0.2 mm or less. As a result, an increase in pressure loss can be suppressed.
- the honeycomb filter having a thin cell wall has a problem that the mechanical strength is not sufficient. Therefore, in the honeycomb filter according to the first aspect, the mechanical strength in the vicinity of the outer peripheral portion of the honeycomb fired body can be improved by making the thickness of the outer peripheral wall larger than the thickness of the cell wall. Note that exhaust gas does not flow into the outer peripheral wall of the honeycomb fired body. Therefore, even if the thickness of the outer peripheral wall is increased, the pressure loss is not adversely affected.
- an oxide layer containing silicon hereinafter also simply referred to as an oxide layer
- the internal mechanical strength can be improved. The reason is considered as follows.
- the silicon carbide particles constituting the honeycomb fired body there is a constricted portion that is generated when two particles called “neck” are connected. Silicon carbide particles are bonded to each other through a neck.
- the coupling angle of the neck is small, and the coupling end of the neck is sharp. Therefore, when an external force or thermal shock is applied to the honeycomb fired body composed of such silicon carbide particles, stress concentrates on the joint end portion of the neck.
- the neck coupling angle becomes large and the neck coupling end becomes smooth. Therefore, the stress concentration on the coupling end of the neck is alleviated. As a result, it is considered that the mechanical strength of the honeycomb fired body is improved.
- the honeycomb filter according to claim 1 is a filter for collecting particulates contained in exhaust gas discharged from a gasoline engine.
- the exhaust temperature from the gasoline engine is higher than the exhaust temperature from the diesel engine.
- the honeycomb filter according to claim 1 since the outer peripheral wall is thicker than the cell wall and the thickness of the cell wall is adjusted to 0.2 mm or less, the heat capacity between the outer peripheral wall of the honeycomb fired body and the cell wall is adjusted. The difference becomes larger. Therefore, in the honeycomb filter according to claim 1, when a high exhaust temperature from the gasoline engine is received, the thermal stress between the outer peripheral wall and the cell wall of the honeycomb fired body is larger than that of the honeycomb filter for a diesel engine. Thus, cracks are likely to occur in the honeycomb fired body.
- the oxide layer is formed on the surface of the silicon carbide particles, the silicon carbide particles in which the thermal stress between the outer peripheral wall and the cell wall of the honeycomb fired body is most concentrated. Stress concentration can be relaxed in the sintered neck portion.
- the mechanical strength against external force or thermal shock can be improved while suppressing an increase in pressure loss.
- the cell wall has a thickness of 0.2 mm or less, and the outer peripheral wall has a thickness larger than the cell wall. The problem is solved by forming an oxide layer on the surface of silicon carbide particles constituting the honeycomb fired body. Therefore, the above-described effects cannot be expected from the respective configurations alone. Further, the honeycomb filter according to claim 1 solves a specific problem that occurs in a honeycomb filter for a gasoline engine having an exhaust temperature higher than that of a diesel engine. Therefore, the above-described effect cannot be expected from a honeycomb filter for a diesel engine.
- the honeycomb filter when the cell wall is thin, the strength of the cell wall is weakened. Therefore, if PM is burned with a large amount of PM deposited on the cell wall, the strength of the cell wall cannot withstand thermal stress. Cracks occur. Therefore, when the cell wall is thin, the amount of PM that can be deposited on the cell wall is reduced. However, since the exhaust temperature by the gasoline engine is higher than the exhaust temperature by the diesel engine, PM is burned continuously. Further, the amount of PM discharged from the gasoline engine is smaller than the amount of PM discharged from the diesel engine. Therefore, in a filter that collects PM discharged from a gasoline engine, a phenomenon that a large amount of PM is burned at a time does not occur in the first place. Therefore, the honeycomb filter according to claim 1 has sufficient PM collecting ability as a honeycomb filter for a gasoline engine.
- the oxide layer has a thickness of 200 to 400 nm.
- the silicon carbide particles constituting the honeycomb fired body have an average particle diameter of about 11 to 20 ⁇ m. Therefore, when the thickness of the oxide layer is 200 to 400 nm, it is very thin as compared with the silicon carbide particles, so that the pressure loss is not adversely affected. When the thickness of the oxide layer is less than 200 nm, the thickness of the oxide layer is too thin, so that it is not possible to sufficiently obtain the effect of relaxing the stress concentration at the neck coupling end. On the other hand, when the thickness of the oxide layer exceeds 400 nm, the stress due to the difference in thermal expansion coefficient between the silicon carbide particles and the oxide layer increases, and it is assumed that cracks are likely to occur in the honeycomb fired body. .
- the thickness of the cell wall is 0.1 to 0.125 mm.
- the cell wall thickness is 0.1 to 0.125 mm, it is possible to maintain the mechanical strength while effectively suppressing an increase in pressure loss. If the cell wall thickness is less than 0.1 mm, the cell wall becomes too thin, and it becomes difficult to obtain sufficient mechanical strength. On the other hand, when the thickness of the cell wall exceeds 0.125 mm, it is difficult to obtain the effect of suppressing an increase in pressure loss.
- the thickness of the outer peripheral wall is 150 to 300% of the thickness of the cell wall. If the thickness of the outer peripheral wall is less than 150% of the cell wall thickness, the effect of improving the mechanical strength in the vicinity of the outer peripheral portion of the honeycomb fired body cannot be sufficiently obtained. On the other hand, when the thickness of the outer peripheral wall exceeds 300% of the cell wall thickness, the mechanical strength can be improved, but the aperture ratio of the honeycomb filter becomes small, and the pressure loss tends to increase.
- the thickness of the outer peripheral wall is 0.25 to 0.4 mm. If the thickness of the outer peripheral wall is less than 0.25 mm, the effect of improving the mechanical strength in the vicinity of the outer peripheral portion of the honeycomb fired body cannot be sufficiently obtained. On the other hand, when the thickness of the outer peripheral wall exceeds 0.4 mm, the mechanical strength can be improved, but the aperture ratio of the honeycomb filter becomes small and the pressure loss tends to increase.
- a catalyst is supported on the cell wall of the honeycomb fired body.
- the gasoline engine is a gasoline direct injection engine.
- the honeycomb filter according to an eighth aspect includes the one honeycomb fired body.
- a honeycomb filter according to a ninth aspect is formed by binding a plurality of the honeycomb fired bodies through an adhesive layer.
- the exhaust gas purifying apparatus comprises: A metal container having a gas inlet side and a gas outlet side; A honeycomb filter housed in the metal container; An exhaust gas purification apparatus comprising a holding sealing material wound around the honeycomb filter and disposed between the metal container and the honeycomb filter,
- the honeycomb filter is a honeycomb filter of the present invention.
- the exhaust gas purification method comprises: An exhaust gas purification method for purifying exhaust gas discharged from a gasoline engine using an exhaust gas purification device,
- the exhaust gas purification apparatus includes a metal container having a gas inlet side and a gas outlet side, A honeycomb filter housed in the metal container; A holding sealing material wound around the honeycomb filter and disposed between the metal container and the honeycomb filter;
- the honeycomb filter is a honeycomb filter of the present invention, The exhaust gas discharged from the gasoline engine is caused to flow into the exhaust gas purification device from the gas inlet side of the metal container and to flow out from the gas outlet side of the metal container.
- the honeycomb filter of the present invention has low pressure loss and excellent mechanical strength. Therefore, the exhaust gas purifying apparatus according to claim 10 and the exhaust gas purifying method according to claim 11 can suitably purify exhaust gas discharged from a gasoline engine, particularly a gasoline direct injection engine.
- FIG. 1 is a perspective view schematically showing an example of the honeycomb filter according to the first embodiment of the present invention.
- Fig.2 (a) is a perspective view which shows typically an example of the honeycomb fired body which comprises the honeycomb filter shown in FIG.
- FIG. 2B is a cross-sectional view taken along the line AA of the honeycomb fired body shown in FIG.
- Fig.3 (a) is explanatory drawing which shows typically the coupling
- FIG.3 (b) is the elements on larger scale of the silicon carbide particle shown to Fig.3 (a).
- FIG. 4 is a cross-sectional view schematically showing an example of the exhaust gas purifying apparatus according to the first embodiment of the present invention.
- FIG. 4 is a cross-sectional view schematically showing an example of the exhaust gas purifying apparatus according to the first embodiment of the present invention.
- FIG. 5 is an explanatory view schematically showing a method of a three-point bending strength test.
- Fig.6 (a) is a perspective view which shows typically an example of the honey-comb filter which concerns on other embodiment of this invention.
- FIG. 6B is a cross-sectional view of the honeycomb filter shown in FIG. 6A taken along line BB.
- FIG. 1 is a perspective view schematically showing an example of the honeycomb filter according to the first embodiment of the present invention.
- Fig.2 (a) is a perspective view which shows typically an example of the honeycomb fired body which comprises the honeycomb filter shown in FIG.
- FIG. 2B is a cross-sectional view taken along the line AA of the honeycomb fired body shown in FIG.
- honeycomb filter 10 a plurality of silicon carbide honeycomb fired bodies 20 are bound through an adhesive layer 11 to form a ceramic block 13.
- An outer peripheral coat layer 12 for preventing leakage of exhaust gas is formed around the ceramic block 13.
- the outer periphery coating layer should just be formed as needed.
- Such a honeycomb filter formed by binding a plurality of honeycomb fired bodies is also referred to as a collective honeycomb filter.
- the honeycomb fired body 20 has a shape shown in FIGS. 2 (a) and 2 (b).
- a large number of cells 21 are arranged in parallel in the longitudinal direction (in the direction of arrow a in FIG. 2 (a)) with the cell walls 22 therebetween.
- an outer peripheral wall 23 is formed around the periphery. The outer peripheral wall 23 is thicker than the cell wall 22.
- any end portion of the cell 21 is sealed with a sealing material 24. Therefore, the exhaust gas G (in FIG. 2B, the exhaust gas is indicated by G and the flow of the exhaust gas is indicated by an arrow in FIG. 2B) always passes through the cell wall 22 separating the cells 21. After that, the other end face 26 flows out from the open cell 21. Therefore, the cell wall 22 functions as a filter for collecting PM and the like.
- a surface in which cells are open is referred to as an end surface
- a surface other than the end surface is referred to as a side surface.
- the honeycomb filter according to the first embodiment of the present invention is a filter for collecting particulates contained in exhaust gas discharged from a gasoline engine.
- the gasoline engine is preferably a gasoline direct injection engine.
- the silicon carbide honeycomb fired body refers to a honeycomb fired body containing 60% by weight or more of silicon carbide.
- the honeycomb fired body constituting the honeycomb filter according to the first embodiment of the present invention is configured by bonding a large number of silicon carbide particles as an aggregate while maintaining a large number of pores therebetween.
- the honeycomb fired body constituting the honeycomb filter according to the first embodiment of the present invention may contain components other than silicon carbide as long as silicon carbide is contained in an amount of 60% by weight or more.
- the honeycomb fired body may contain 40% by weight or less of silicon.
- the main component of the constituent material of the honeycomb fired body may be silicon-containing silicon carbide in which metal silicon is mixed with silicon carbide, or silicon carbide bonded with silicon or a silicate compound.
- the honeycomb fired body contains silicon such as metal silicon, an oxide layer is also formed on the surface of these silicon.
- the honeycomb fired body preferably contains 98% by weight or more of silicon carbide or 98% by weight or more of silicon carbide and metal silicon.
- the thickness of the cell wall of the honeycomb fired body is 0.2 mm or less, preferably 0.1 to 0.2 mm, more preferably 0.1 to 0.2 mm. 0.125 mm.
- the thickness of the cell wall exceeds 0.2 mm, the pressure loss becomes high.
- the thickness of the cell wall is less than 0.1 mm, the cell wall becomes too thin, and it becomes difficult to obtain sufficient mechanical strength.
- the cell wall thickness is 0.1 to 0.125 mm, it is possible to maintain the mechanical strength while effectively suppressing an increase in pressure loss.
- the thickness of the outer peripheral wall of the honeycomb fired body is thicker than the thickness of the cell wall.
- the thickness of the outer peripheral wall is preferably 150 to 300% of the thickness of the cell wall, and more preferably 200 to 300%. If the thickness of the outer peripheral wall is less than 150% of the cell wall thickness, the effect of improving the mechanical strength in the vicinity of the outer peripheral portion of the honeycomb fired body cannot be sufficiently obtained. On the other hand, when the thickness of the outer peripheral wall exceeds 300% of the cell wall thickness, the mechanical strength can be improved, but the aperture ratio of the honeycomb filter becomes small, and the pressure loss tends to increase.
- the thickness of the outer peripheral wall of the honeycomb fired body is not particularly limited, but is preferably 0.25 to 0.4 mm, preferably 0.25 to 0.00 mm. More preferably, it is 3 mm. If the thickness of the outer peripheral wall is less than 0.25 mm, the effect of improving the mechanical strength in the vicinity of the outer peripheral portion of the honeycomb fired body cannot be sufficiently obtained. On the other hand, when the thickness of the outer peripheral wall exceeds 0.4 mm, the mechanical strength can be improved, but the aperture ratio of the honeycomb filter becomes small and the pressure loss tends to increase.
- the cell wall of the honeycomb fired body refers to a portion that exists between two adjacent cells and separates the two cells.
- the outer peripheral wall of the honeycomb fired body refers to a portion that exists on the outer periphery of the honeycomb fired body and constitutes the outer periphery of the honeycomb fired body.
- an oxide layer (silica film) containing silicon is formed on the surface of silicon carbide particles constituting the honeycomb fired body.
- Fig.3 (a) is explanatory drawing which shows typically the coupling
- FIG.3 (b) is the elements on larger scale of the silicon carbide particle shown to Fig.3 (a).
- the silicon carbide particles 31 constituting the honeycomb fired body are bonded to each other via a neck 31a.
- An oxide layer 32 containing silicon is formed on the surface of the silicon carbide particles 31.
- the coupling angle of the neck 31a is increased, and the coupling end portion of the neck 31a is smooth. Therefore, the stress concentration on the coupling end of the neck 31a is alleviated. As a result, it is considered that the mechanical strength of the honeycomb fired body is improved.
- the thickness of the oxide layer is not particularly limited, but is preferably 200 to 400 nm, and more preferably 250 to 320 nm.
- the silicon carbide particles constituting the honeycomb fired body have an average particle diameter of about 11 to 20 ⁇ m. Therefore, when the thickness of the oxide layer is 200 to 400 nm, it is very thin as compared with the silicon carbide particles, so that the pressure loss is not adversely affected. When the thickness of the oxide layer is less than 200 nm, the thickness of the oxide layer is too thin, so that it is not possible to sufficiently obtain the effect of relaxing the stress concentration at the neck coupling end. On the other hand, when the thickness of the oxide layer exceeds 400 nm, the stress due to the difference in thermal expansion coefficient between the silicon carbide particles and the oxide layer increases, and it is assumed that cracks are likely to occur in the honeycomb fired body. .
- the thickness of the oxide layer can be measured using X-ray photoelectron spectroscopy (XPS).
- XPS is an analysis method that irradiates a sample surface with X-rays and measures the energy of the generated photoelectrons with a device called an energy analyzer.
- the constituent elements of the sample and their electronic states can be analyzed by XPS.
- XPS X-ray photoelectron spectroscopy
- the depth (thickness) of the oxide layer is determined by analyzing the composition by XPS while scraping the surface of the sample at a constant speed by ion sputtering. be able to. Based on the measurement results using such a measuring method, it is preferable that an oxide layer having a thickness of 200 to 400 nm is formed on the surface of the silicon carbide particles.
- the thickness of the oxide layer refers to the thickness of the oxide layer before the honeycomb filter is mounted on a car or the like.
- the weight increase rate is preferably 1.5 to 3.0% by weight.
- the thickness of the oxide layer can be controlled to be a constant value.
- the weight increase rate is the weight increase rate obtained by measuring the weight of the honeycomb fired body or the honeycomb filter before and after forming the oxide layer.
- the oxide layer is formed on the surface of the silicon carbide particles, so that the wettability of the catalyst or the like is excellent.
- the contact angle meter Kelowa Interface Science Co., Ltd., Drop Master 300, measurement system: CCD camera
- the contact angle change time is 14 to 18 seconds in the honeycomb filter according to the first embodiment of the present invention. It is considered that the shorter the contact angle change time, the better the wettability of the catalyst etc., and the easier it is to carry the catalyst etc. on the honeycomb fired body.
- a surfactant manufactured by San Nopco, SN980, viscosity: 3700 cP, surface tension: 30.6 mN / m
- the contact angle change time is about 20 to 22 seconds.
- a method for manufacturing a honeycomb filter according to the first embodiment of the present invention will be described.
- a method for manufacturing a honeycomb filter including the honeycomb fired body illustrated in FIGS. 2A and 2B will be described in the order of steps.
- a forming process for forming a honeycomb formed body in which a large number of cells are arranged side by side in the longitudinal direction with a cell wall therebetween is performed by forming a ceramic raw material.
- a ceramic raw material for producing a honeycomb formed body (wet) is prepared by mixing silicon carbide powder having a different average particle size as an ceramic powder, an organic binder, a liquid plasticizer, a lubricant, and water.
- a mixture is prepared.
- the wet mixture is charged into an extruder.
- a honeycomb formed body having a predetermined shape is produced by extruding the wet mixture.
- the honeycomb formed body is cut into a predetermined length and dried using a microwave dryer, hot air dryer, dielectric dryer, vacuum dryer, vacuum dryer, freeze dryer, or the like.
- the sealing process which fills the edge part of a predetermined cell with the sealing material paste used as a sealing material, and seals the said cell is performed.
- a sealing material paste it can produce by mixing a silicon carbide powder, a binder, a solvent, a dispersing agent, and a lubricant, for example.
- a degreasing step of heating the organic matter in the honeycomb formed body in a degreasing furnace is performed.
- the honeycomb formed body is heated at 300 to 650 ° C. in an oxygen-containing atmosphere.
- the honeycomb formed body that has been subjected to the degreasing treatment is transported to a firing furnace, and heated at 2000 to 2200 ° C. in a non-oxidizing atmosphere to thereby sinter the silicon carbide particles in the honeycomb formed body.
- a honeycomb fired body as shown in FIGS. 2A and 2B is manufactured.
- the sealing material paste with which the edge part of the cell was filled is baked by heating and becomes a sealing material.
- the conditions currently used when manufacturing a honeycomb fired body can be applied to the conditions of a cutting process, a drying process, a sealing process, a degreasing process, and a firing process.
- an oxidation process is performed in which the honeycomb fired body is oxidized by heat treatment at 1200 to 1400 ° C. for 0.5 to 35 hours in an oxidizing atmosphere.
- an oxide layer can be formed on the surface of the silicon carbide particles constituting the honeycomb fired body.
- the oxidation step is performed in an atmosphere containing oxygen, and is preferably performed in an air atmosphere from the viewpoint of cost.
- the oxygen concentration (content converted to oxygen) in the oxidizing atmosphere is not particularly limited, but is preferably 5 to 21% by volume. In view of cost, it is preferable to use air.
- the oxygen concentration in the oxidizing atmosphere is less than 5% by volume, oxidation of the surface of the silicon carbide particles of the honeycomb fired body becomes unstable, and it becomes difficult to form an oxide layer having a desired thickness. Further, if the oxygen concentration in the oxidizing atmosphere is less than 5% by volume, it is necessary to perform heat treatment for a long time, and the production efficiency tends to decrease.
- the oxygen concentration in the oxidizing atmosphere exceeds 21% by volume, a process for generating the oxidizing atmosphere, such as preparing oxygen gas, is required, and the manufacturing efficiency tends to be reduced.
- the heat treatment temperature in the oxidation step is preferably 1200 to 1400 ° C.
- the heat treatment temperature is less than 1200 ° C., it is difficult to form an oxide layer having a desired thickness.
- the heat treatment temperature exceeds 1400 ° C., it is difficult to adjust the thickness of the oxide layer.
- the heat treatment time in the oxidation step is preferably 0.5 to 35 hours, but is appropriately determined according to the heat treatment temperature, the thickness of the target oxide layer, and the like. Specifically, when the heat treatment temperature is 1200 ° C. or more and less than 1300 ° C., the heat treatment time is preferably 5 to 35 hours, and when the heat treatment temperature is 1300 ° C. or more and 1400 ° C. or less, the heat treatment time is 0.5 Preferably it is ⁇ 5 hours. When the heat treatment time is shorter than the lower limit value, it is difficult to form an oxide layer having a target thickness. On the other hand, when the heat treatment time exceeds the upper limit value, an oxide layer thicker than the target thickness is formed.
- the heat treatment time means a time for maintaining the heat treatment temperature after the temperature is raised to the target heat treatment temperature. Therefore, the time during which the honeycomb fired body is heated in the entire oxidation process includes the time required for temperature increase and decrease in addition to the heat treatment time.
- an oxide layer having a desired thickness (preferably 200 to 400 nm) can be formed on the surface of the silicon carbide particles constituting the honeycomb fired body.
- an adhesion step for producing a ceramic block is performed by adhering the plurality of honeycomb fired bodies through an adhesive layer.
- the adhesive paste is applied to each predetermined side surface of the honeycomb fired body to form an adhesive paste layer.
- the process of sequentially stacking other honeycomb fired bodies on the adhesive paste layer is repeated.
- an aggregate of honeycomb fired bodies in which an adhesive paste is applied to the side surfaces of the honeycomb fired bodies is manufactured.
- the aggregate of the honeycomb fired bodies is heated using a dryer or the like to dry and solidify the adhesive paste, thereby producing a ceramic block in which a plurality of honeycomb fired bodies are bonded via the adhesive layer.
- an adhesive paste what consists of an inorganic binder, an organic binder, and an inorganic particle is used, for example.
- the adhesive paste may further contain inorganic fibers and / or whiskers.
- the outer periphery process process which cuts a ceramic block is performed. Specifically, a ceramic block whose outer periphery is processed into a columnar shape is manufactured by cutting the ceramic block using a diamond cutter.
- the outer periphery coating material paste is apply
- the said adhesive paste can be used as an outer periphery coating material paste.
- a paste having a composition different from that of the adhesive paste may be used as the outer periphery coating material paste.
- the outer peripheral coat layer is not necessarily provided, and may be provided as necessary.
- the honeycomb filter according to the first embodiment of the present invention can be manufactured.
- the oxidation process is performed after the honeycomb fired body is manufactured (that is, between the firing process and the bonding process).
- the method for manufacturing a honeycomb filter according to the first embodiment of the present invention between the bonding step and the outer periphery processing step, between the outer periphery processing step and the outer periphery coat layer forming step, or after the outer periphery coat layer forming step.
- An oxidation step may be performed.
- FIG. 4 is a cross-sectional view schematically showing an example of the exhaust gas purifying apparatus according to the first embodiment of the present invention.
- the exhaust gas purification apparatus 100 shown in FIG. 4 includes a metal container 120 having a gas inlet side 121 and a gas outlet side 122, and a honeycomb filter 110 accommodated in the metal container 120.
- the honeycomb filter 10 shown in FIG. 1 is used as the honeycomb filter 110. As shown in FIGS. 2A and 2B, any end portion of the cell 21 of the honeycomb fired body 20 constituting the honeycomb filter 10 is sealed with a sealing material 24.
- a holding sealing material 130 is disposed between the honeycomb filter 110 and the metal container 120, and the honeycomb filter 110 is held by the holding sealing material 130.
- the holding sealing material 130 is wound around the honeycomb filter 110.
- the holding sealing material is a mat-like member having a substantially rectangular shape in plan view mainly made of inorganic fibers such as alumina.
- an inlet pipe for introducing exhaust gas discharged from an internal combustion engine such as a gasoline engine (preferably a gasoline direct injection engine) into the exhaust gas purification apparatus 100 is connected to the gas inlet side 121 of the metal container 120.
- a discharge pipe for discharging the exhaust gas that has passed through the exhaust gas purification apparatus 100 to the outside is connected to the gas outlet side 122 of the metal container 120.
- the exhaust gas discharged from the internal combustion engine (in FIG. 4, the exhaust gas is indicated by G and the flow of the exhaust gas is indicated by an arrow) is sent from the gas inlet side 121 of the metal container 120 to the exhaust gas purification device 100. Inflow. Thereafter, the exhaust gas G flows into the honeycomb filter 110 from the one end face 25 side of the honeycomb fired body 20. Specifically, the exhaust gas G flows into the cell 21 in which one end face 25 of the honeycomb fired body 20 is opened. The exhaust gas G passes through the cell wall 22 separating the cells 21. At this time, PM in the exhaust gas G is collected by the cell wall 22 and the exhaust gas G is purified.
- the purified exhaust gas G flows into the cell 21 in which the other end face 26 of the honeycomb fired body 20 is opened, and is discharged out of the honeycomb filter 110. Then, the exhaust gas G is discharged out of the exhaust gas purification apparatus 100 from the gas outlet side 122 of the metal container 120.
- exhaust gas from a gasoline engine is purified.
- the exhaust gas purification apparatus according to the first embodiment of the present invention can be suitably used as a gasoline particulate filter (GPF).
- GPF gasoline particulate filter
- one honeycomb filter according to the first embodiment of the present invention may be accommodated in a metal container, or a honeycomb structure used as another catalyst carrier It may be arranged with the body.
- the honeycomb filter according to the first embodiment of the present invention manufactured by the above method is placed in a metal container.
- a mat having a substantially rectangular shape in plan view mainly made of inorganic fibers is prepared as a holding sealing material, and the mat is wound around the honeycomb filter.
- An exhaust gas purification apparatus can be obtained by press-fitting a honeycomb filter in which a mat is wound around a substantially cylindrical metal container.
- the metal container is formed in a shape that can be separated into two parts, a first metal container and a second metal container, and a honeycomb filter around which a mat made of inorganic fibers is wound is placed on the first metal container. It can also be set as an exhaust gas purification apparatus by sealing with a second metal container later.
- the aperture ratio of the honeycomb filter can be increased by reducing the thickness of the cell wall to 0.2 mm or less. As a result, an increase in pressure loss can be suppressed.
- the mechanical strength in the vicinity of the outer peripheral portion of the honeycomb fired body can be improved by making the outer peripheral wall thicker than the cell wall. Note that exhaust gas does not flow into the outer peripheral wall of the honeycomb fired body. Therefore, even if the thickness of the outer peripheral wall is increased, the pressure loss is not adversely affected.
- the mechanical strength inside the honeycomb fired body can be improved by forming an oxide layer containing silicon on the surface of the silicon carbide particles constituting the honeycomb fired body.
- the oxide layer is formed on the surface of the silicon carbide particles, the neck bonding angle becomes large and the neck coupling end becomes smooth. Therefore, the stress concentration on the coupling end of the neck is alleviated. As a result, it is considered that the mechanical strength of the honeycomb fired body is improved.
- the honeycomb filter of the present embodiment is a filter for collecting particulates contained in exhaust gas discharged from a gasoline engine.
- the exhaust temperature from the gasoline engine is higher than the exhaust temperature from the diesel engine.
- the outer peripheral wall is thicker than the cell wall, and the thickness of the cell wall is adjusted to 0.2 mm or less. Becomes larger. Therefore, in the honeycomb filter of the present embodiment, when receiving a high exhaust temperature from the gasoline engine, the thermal stress between the outer peripheral wall of the honeycomb fired body and the cell wall becomes larger than that of the honeycomb filter for a diesel engine. Cracks are likely to occur in the honeycomb fired body.
- the thermal stress between the outer peripheral wall and the cell wall of the honeycomb fired body is most concentrated between the silicon carbide particles. In the sintered neck portion, stress concentration can be relaxed.
- the honeycomb filter of the present embodiment it is possible to improve the mechanical strength against external force or thermal shock while suppressing an increase in pressure loss. Further, the honeycomb filter of the present embodiment has sufficient PM trapping ability as a honeycomb filter for a gasoline engine.
- the honeycomb filter of the present embodiment has low pressure loss and excellent mechanical strength. Therefore, in the exhaust gas purification apparatus of this embodiment and the exhaust gas purification method of this embodiment, exhaust gas discharged from a gasoline engine, particularly a gasoline direct injection engine, can be suitably purified.
- Example 1 Production of honeycomb fired body Obtained by mixing 52.8% by weight of silicon carbide coarse powder having an average particle size of 22 ⁇ m and 22.6% by weight of fine powder of silicon carbide having an average particle size of 0.5 ⁇ m 2.1% by weight of acrylic resin, 4.6% by weight of organic binder (methyl cellulose), 2.8% by weight of lubricant (Unilube manufactured by NOF Corporation), 1.3% by weight of glycerin, and water 13% .8 wt% was added and kneaded to obtain a wet mixture. Then, after extruding the wet mixture, it is cut to form a raw honeycomb molded body having the same shape as that shown in FIGS. 2 (a) and 2 (b) and having no cells sealed. Was made.
- the raw honeycomb formed body was dried using a microwave dryer.
- a predetermined cell of the dried honeycomb formed body was filled with a sealing material paste and again dried using a dryer.
- the sealing material paste was composed of 63.3% by weight of silicon carbide coarse powder having an average particle diameter of 11 ⁇ m, 15.8% by weight of fine powder of silicon carbide having an average particle diameter of 0.65 ⁇ m, and a solvent (diethylene glycol mono-2-ethylhexyl ether).
- binder mixture of methacrylic acid ester copolymer and diethylene glycol mono-2-ethylhexyl ether
- dispersant Pricesurf manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- a lubricant unilube 50MB-26 manufactured by NOF Corporation
- the dried honeycomb formed body was degreased at 400 ° C., and further fired under a normal pressure argon atmosphere at 2200 ° C. for 3 hours to prepare a honeycomb fired body made of a silicon carbide sintered body.
- the honeycomb fired body has a porosity of 45%, an average pore diameter of 15 ⁇ m, a size of 34.3 mm ⁇ 34.3 mm ⁇ 150 mm, and the number of cells (cell density) of 46.5 cells / cm 2 (300 cells / inch 2). ),
- the thickness of the cell wall was 0.10 mm (4 mil), and the thickness of the outer shadow was 0.30 mm (12 mil).
- honeycomb fired body The following oxidation process was performed on the obtained honeycomb fired body.
- the temperature is increased from room temperature to 1370 ° C. at a temperature increase rate of 300 ° C./hour in an air atmosphere, held at 1370 ° C. for 3 hours, and then decreased to 300 ° C. at a temperature decrease rate of 100 ° C./hour. (25 ° C.).
- the surface of the honeycomb fired body is oxidized by the oxidation step. Specifically, an oxide layer is formed on the surface of the silicon carbide particles of the honeycomb fired body.
- the honeycomb fired body after the oxidation process is referred to as “honeycomb fired body of Example 1”.
- the measurement conditions were voltage: 15 kV, output: 25 W, measurement area: 100 ⁇ m ⁇ .
- the ion sputtering conditions were ion species: Ar + , voltage: 1 kV, and sputtering rate (SiO 2 conversion): 1.5 nm / min.
- qualitative analysis wide scan
- depth direction analysis C, O, and Si were performed. From the result of depth direction analysis, the thickness of the oxide layer was calculated from the time of the strength intermediate between the highest strength and the lowest strength of the SiO 2 profile and the sputter rate (converted to SiO 2 ) of the sample for XPS measurement.
- the thickness of the oxide layer in Example 1 was 310 nm.
- FIG. 5 is an explanatory view schematically showing a method of a three-point bending strength test. First, 10 silicon carbide portions having a size of 2 cells ⁇ 4 cells ⁇ 40 mm excluding the outer peripheral wall and the sealing portion were cut out from the honeycomb fired body of Example 1 as a sample for measuring three-point bending strength. Then, as shown in FIG.
- a load is applied in a direction perpendicular to the main surface of the three-point bending strength measurement sample 60 (the wider one of the outer peripheral surfaces of the sample), and the breaking load (the sample breaks). Load) was measured.
- the breaking load was measured for ten three-point bending strength measurement samples, and the average value was taken as the bending strength.
- the three-point bending strength test was performed using an Instron 5582 with reference to JIS R 1601, a span distance of 30 mm, and a speed of 1 mm / min.
- the bending strength in Example 1 was 27.9 MPa.
- Example 2 (2-3) Evaluation of wettability
- the honeycomb fired body of Example 1 was evaluated for wettability by the following method. Time for changing the contact angle with a hanging drop from 40 ° to 20 ° using a contact angle meter (Drop Master 300, measurement system: CCD camera, manufactured by Kyowa Interface Science Co., Ltd.) Time). Note that a surfactant (manufactured by San Nopco, SN980, viscosity: 3700 cP, surface tension: 30.6 mN / m) was used as the hanging drop.
- the contact angle change time in Example 1 was 15.0 seconds.
- Example 2 (2-4) Measurement of rate of weight increase
- the honeycomb fired body manufactured in Example 1 was subjected to an oxidation process under the same conditions as in Example 1, and the weight A before the oxidation process and the weight B after the oxidation process were measured. .
- the aggregate of honeycomb fired bodies was heated at 120 ° C. to dry and solidify the adhesive paste, thereby producing a quadrangular columnar ceramic block with an adhesive layer having a thickness of 1.0 mm.
- the outer periphery of the ceramic block was cut using a diamond cutter to produce a ceramic block whose outer periphery was processed into a cylindrical shape having a diameter of 142 mm.
- the outer periphery coating material paste was applied to the outer peripheral surface of the ceramic block whose outer periphery was processed into a columnar shape to form an outer periphery coating material paste layer.
- the outer peripheral coating material paste layer is dried and solidified at 120 ° C. to form an outer peripheral coating layer, thereby manufacturing a cylindrical honeycomb filter having a diameter of 143.8 mm and a length of 150 mm with the outer peripheral coating layer formed on the outer periphery. did.
- the adhesive paste was used as the coating material paste.
- Example 1 A honeycomb fired body was produced in the same manner as in Example 1 except that the oxidation step was not performed.
- the honeycomb fired body of Comparative Example 1 is referred to.
- a honeycomb filter was manufactured in the same manner as in Example 1.
- Example 1 Each characteristic of the fired honeycomb body of Comparative Example 1 was evaluated in the same manner as in Example 1. As a result, the thickness of the oxide layer in Comparative Example 1 was less than 4 nm, the bending strength was 14.4 MPa, and the contact angle change time was 20.0 seconds. In Comparative Example 1, since the oxidation process was not performed, the weight increase rate was set to 0% by weight.
- Table 1 summarizes the thickness, bending strength, contact angle change time, and weight increase rate of the oxide layers in Example 1 and Comparative Example 1.
- Example 1 it can be seen that the thickness of the oxide layer is 310 nm, and the oxide layer is formed on the surface of the silicon carbide particles constituting the honeycomb fired body. On the other hand, in Comparative Example 1 in which the oxidation process was not performed, the thickness of the oxide layer was less than 4 nm, and it is considered that an effective oxide layer was not formed on the surface of the silicon carbide particles.
- honeycomb fired body of Example 1 has higher bending strength than the honeycomb fired body of Comparative Example 1. From this result, it is considered that the mechanical strength of the honeycomb fired body is improved by forming an oxide on the surface of the silicon carbide particles constituting the honeycomb fired body.
- the bending strength can be used as an index for evaluating the resistance to thermal shock as well as the index for evaluating the mechanical strength of the honeycomb fired body.
- the thermal shock fracture resistance coefficient R ′ is expressed by the following mathematical formula (1).
- Equation (1) ⁇ is bending strength, ⁇ is Poisson's ratio, k is thermal conductivity, ⁇ is thermal expansion coefficient, and E is Young's modulus.
- the larger the thermal shock breakdown resistance coefficient R ′ is, the more resistant to thermal shock for example, K. Ohno et al., “Further Durability Enhancement of Re-crystallized SiC-DPF”). , SAE technical paper: 2004-01-0954, etc.).
- the Poisson's ratio ⁇ , the thermal conductivity k, the thermal expansion coefficient ⁇ , and the Young's modulus E do not change depending on the presence or absence of the oxide layer.
- Example 1 in which the oxide layer is formed, the bending strength is higher than that in Comparative Example 1 in which the oxide layer is not formed. Therefore, it is presumed that the honeycomb fired body of Example 1 has higher resistance to thermal shock than the honeycomb fired body of Comparative Example 1.
- the honeycomb fired body of Example 1 has a shorter contact angle change time than the honeycomb fired body of Comparative Example 1. From this result, it is considered that by forming an oxide on the surface of the silicon carbide particles constituting the honeycomb fired body, the surface of the honeycomb fired body becomes smooth, so that the catalyst or the like can be easily carried on the honeycomb fired body.
- the honeycomb filter according to the embodiment of the present invention may be composed of a single silicon carbide honeycomb fired body. Such a honeycomb filter made of one honeycomb fired body is also referred to as an integral honeycomb filter. Even an integrated honeycomb filter has the same effect as the honeycomb filter according to the first embodiment of the present invention.
- FIG. 6 (a) is a perspective view which shows typically an example of the honey-comb filter which concerns on other embodiment of this invention.
- FIG. 6B is a cross-sectional view of the honeycomb filter shown in FIG. 6A taken along line BB.
- a honeycomb filter 40 shown in FIGS. 6A and 6B has a ceramic block 43 made of a single columnar honeycomb fired body, and an outer peripheral coat layer 42 is formed around the ceramic block 43. .
- the outer periphery coating layer should just be formed as needed.
- a large number of cells 51 are separated from each other by a cell wall 52 in the longitudinal direction (the direction of arrow b in FIG. 6 (a)). ) And an outer peripheral wall 53 around the periphery.
- the outer peripheral wall 53 is thicker than the cell wall 52.
- the honeycomb filter 40 shown in FIG. 6A and FIG. 6B either end of the cell 51 is sealed with a sealing material 54. Accordingly, the exhaust gas G (in FIG. 6B, the exhaust gas is indicated by G and the flow of the exhaust gas is indicated by an arrow in FIG. 6B) always passes through the cell wall 52 separating the cells 51. After that, the other end face 56 flows out from the open cell 51. Therefore, the cell wall 52 functions as a filter for collecting PM and the like.
- the size of the honeycomb formed body formed by extrusion molding is larger than the size of the honeycomb formed body described in the first embodiment of the present invention, and the outer shape is different. Is a honeycomb formed body as in the first embodiment of the present invention.
- the oxidation step described in the first embodiment of the present invention may be performed before the outer peripheral coat layer forming step (that is, between the firing step and the outer peripheral coat layer forming step).
- Step of forming an oxide layer on the surface of the silicon carbide particles of the honeycomb fired body may be performed.
- an oxidation process when not performing an outer periphery process process, you may perform an oxidation process between a baking process and an outer periphery coating layer formation process. Furthermore, an oxidation process may be performed on the honeycomb filter on which the outer peripheral coat layer is not formed.
- the shape of the honeycomb filter according to the embodiment of the present invention is not limited to a columnar shape, and may be any columnar shape such as an elliptical column shape or a polygonal column shape.
- the honeycomb fired body constituting the honeycomb filter according to the embodiment of the present invention, it is sufficient that either one end of the cell is sealed, but the end of the cell is alternately sealed. preferable.
- the porosity of the honeycomb fired body constituting the honeycomb filter according to the embodiment of the present invention is not particularly limited, but is preferably 30 to 50%.
- the porosity of the honeycomb fired body is 30 to 50%, the strength of the honeycomb fired body can be maintained and the resistance when the exhaust gas passes through the cell walls can be kept low.
- the porosity of the honeycomb fired body is less than 30%, the honeycomb fired body is likely to be clogged with particulates (PM).
- the porosity of the honeycomb fired body exceeds 50%, the strength of the honeycomb fired body is lowered and easily broken.
- the average pore diameter of the honeycomb fired body constituting the honeycomb filter according to the embodiment of the present invention is preferably 5 to 30 ⁇ m.
- the average pore diameter of the honeycomb fired body is less than 5 ⁇ m, the particulates are easily clogged.
- the average pore diameter of the honeycomb fired body exceeds 30 ⁇ m, the particulates pass through the pores of the cell walls, and the particulates cannot be collected, and the function as a filter becomes insufficient.
- the said porosity and pore diameter can be measured by the mercury intrusion method which is a conventionally well-known method, for example.
- the cell density in the cross section perpendicular to the longitudinal direction of the honeycomb fired body constituting the honeycomb filter according to the embodiment of the present invention is not particularly limited, but a preferable lower limit is 31.0 / cm 2 (200 / inch 2 ).
- the preferable upper limit is 93.0 / cm 2 (600 / inch 2 ), the more preferable lower limit is 38.8 / cm 2 (250 / inch 2 ), and the more preferable upper limit is 77.5 / cm 2. cm 2 (500 pieces / inch 2 ).
- the shape of the cross section perpendicular to the longitudinal direction of the honeycomb fired body of each cell is not limited to a square, for example, a circle, an ellipse, a pentagon, a hexagon, a trapezoid Or any shape such as an octagon. Various shapes may be mixed.
- the bonding process when manufacturing the aggregated honeycomb filter is substantially the same as the shape of the ceramic block to be manufactured (or the aggregate of honeycomb fired bodies), for example, in addition to the method of applying the adhesive paste to the side surfaces of each honeycomb fired body.
- the honeycomb fired bodies may be temporarily fixed in a shape mold, and an adhesive paste may be injected between the honeycomb fired bodies.
- honeycomb fired bodies having different cross-sectional shapes are produced, and a plurality of types of honeycomb fired bodies are combined, and a plurality of honeycomb fired bodies are bundled through an adhesive layer.
- the outer peripheral machining step may be omitted by producing a ceramic block.
- the following three types of honeycomb fired bodies having different cross-sectional shapes may be manufactured.
- the first honeycomb fired body has a cross-sectional shape surrounded by two straight lines and one arc.
- the second honeycomb fired body has a cross-sectional shape surrounded by three straight lines and one arc.
- the third honeycomb fired body has a cross-sectional shape (quadrangle) surrounded by four straight lines.
- honeycomb fired bodies having different cross-sectional shapes can be produced by changing the shape of a mold used in extrusion molding.
- a columnar honeycomb filter can be manufactured by combining eight first honeycomb fired bodies and four second honeycomb fired bodies and four third honeycomb fired bodies.
- an oxide layer can be formed on the surface of the silicon carbide particles by performing an oxidation step after the adhesion step.
- the heat treatment temperature in the oxidation process must be a temperature at which the inorganic fibers contained in the adhesive do not melt.
- the organic binder contained in the wet mixture used when producing the honeycomb fired body constituting the honeycomb filter is not particularly limited, and examples thereof include methyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose. And polyethylene glycol. Of these, methylcellulose is preferred.
- the amount of the organic binder is usually preferably 1 to 10 parts by weight with respect to 100 parts by weight of the ceramic powder.
- a plasticizer contained in a wet mixture For example, glycerol etc. are mentioned.
- the lubricant contained in the wet mixture is not particularly limited, and examples thereof include polyoxyalkylene compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether. Specific examples of the lubricant include polyoxyethylene monobutyl ether and polyoxypropylene monobutyl ether. In some cases, the plasticizer and the lubricant may not be contained in the wet mixture.
- a dispersion medium liquid may be used.
- the dispersion medium liquid include water, an organic solvent such as benzene, and an alcohol such as methanol.
- a molding aid may be added to the wet mixture.
- the molding aid is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol and the like.
- a pore-forming agent such as balloons that are fine hollow spheres containing oxide ceramics, spherical acrylic particles, and graphite may be added to the wet mixture as necessary.
- the balloon is not particularly limited, and examples thereof include an alumina balloon, a glass micro balloon, a shirasu balloon, a fly ash balloon (FA balloon), and a mullite balloon. Of these, alumina balloons are preferred.
- Examples of the inorganic binder contained in the adhesive paste and the coating material paste include silica sol and alumina sol. These may be used alone or in combination of two or more. Among inorganic binders, silica sol is preferable.
- organic binder contained in the adhesive paste and the coating material paste examples include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and the like. These may be used alone or in combination of two or more. Of the organic binders, carboxymethylcellulose is preferred.
- inorganic fibers contained in the adhesive paste and the coating material paste examples include ceramic fibers such as silica-alumina, mullite, alumina, and silica. These may be used alone or in combination of two or more. Among inorganic fibers, alumina fibers are preferable.
- Examples of the inorganic particles contained in the adhesive paste and the coating material paste include carbide particles and nitride particles. Specific examples include silicon carbide particles, silicon nitride particles, and boron nitride particles. These may be used alone or in combination of two or more. Among the inorganic particles, silicon carbide particles having excellent thermal conductivity are preferable.
- a pore-forming agent such as balloons that are fine hollow spheres containing oxide-based ceramics, spherical acrylic particles, and graphite may be added to the adhesive paste and the coating material paste as necessary.
- the balloon is not particularly limited, and examples thereof include an alumina balloon, a glass micro balloon, a shirasu balloon, a fly ash balloon (FA balloon), and a mullite balloon. Of these, alumina balloons are preferred.
- a catalyst may be supported on the cell wall of the honeycomb fired body. Sufficient purification of harmful gas components in exhaust gas by catalytic reaction is carried by supporting a catalyst that can purify harmful gas components in exhaust gas such as CO, HC and NOx on the cell wall of the honeycomb fired body. It becomes possible to do. In addition, by supporting a catalyst that helps combustion of PM, it becomes possible to burn and remove PM more easily.
- a noble metal such as platinum, palladium, or rhodium is desirable.
- a catalyst support layer may be formed on the cell wall of the honeycomb fired body for the purpose of highly dispersing the catalyst.
- the material for forming the catalyst supporting layer is preferably a material having a high specific surface area and capable of supporting the catalyst in a highly dispersed state.
- oxide ceramics such as alumina, titania, zirconia, ceria, and silica are used. Can be mentioned. These materials may be used alone or in combination of two or more.
- the thickness of the cell wall is 0.2 mm or less, and the thickness of the outer peripheral wall is larger than the thickness of the cell wall.
- the silicon oxide particles are formed on the surface of the silicon carbide particles constituting the honeycomb fired body. It must be used as an essential component.
- the use of the honeycomb filter of the present invention is an essential component.
- the essential components include the various configurations detailed in the first embodiment of the present invention and the other embodiments (for example, the configuration of the honeycomb fired body, the configuration of the oxide layer, the conditions of the oxidation step, etc.). Desired effects can be obtained by appropriately combining them.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Filtering Materials (AREA)
- Exhaust Gas After Treatment (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Of Dispersed Particles In Gases (AREA)
- Ceramic Products (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
Description
ディーゼルエンジンには、ガソリンエンジンに比べて燃費に優れるという長所がある。一方、スス等のパティキュレート(以下、PMともいう)が発生するため、排ガスに含まれるPMを除去するためのフィルタが必要である。
特許文献1~4に記載されたハニカム構造体では、セル壁の厚さを薄くすることによって、圧力損失の増大を抑制させている。
また、本発明は、上記ハニカムフィルタを備えた排ガス浄化装置、及び、上記排ガス浄化装置を用いた排ガス浄化方法を提供することを目的とする。
多数のセルがセル壁を隔てて長手方向に並設され、外周に外周壁が形成された炭化ケイ素質のハニカム焼成体を含み、
上記セルのいずれか一方の端部が封止されており、
上記セル壁の厚さは、0.2mm以下であり、
上記外周壁の厚さは、上記セル壁の厚さよりも厚く、
上記ハニカム焼成体を構成する炭化ケイ素粒子の表面には、ケイ素を含む酸化物層が形成されており、
ガソリンエンジンから排出される排ガス中に含有されるパティキュレートを捕集するために用いられることを特徴とする。
そこで、請求項1に記載のハニカムフィルタでは、外周壁の厚さをセル壁の厚さよりも厚くすることにより、ハニカム焼成体の外周部付近における機械的強度を向上させることができる。
なお、ハニカム焼成体の外周壁には排ガスが流入しない。従って、外周壁の厚さを厚くしても、圧力損失に悪影響を及ぼすことがない。
その理由については、以下のように考えられる。
炭化ケイ素粒子の表面に酸化物層が形成されていない場合、ネックの結合角度は小さく、ネックの結合端部は先鋭状になっている。従って、このような炭化ケイ素粒子から構成されたハニカム焼成体に外力又は熱衝撃が加わると、ネックの結合端部に応力が集中する。
一方、炭化ケイ素粒子の表面に酸化物層が形成されている場合、ネックの結合角度が大きくなり、ネックの結合端部が滑らかになる。従って、ネックの結合端部への応力集中が緩和される。その結果、ハニカム焼成体の機械的強度が向上すると考えられる。
ガソリンエンジンによる排気温度は、ディーゼルエンジンによる排気温度よりも高い。また、請求項1に記載のハニカムフィルタでは、外周壁をセル壁よりも厚く、セル壁の厚さを0.2mm以下に調整しているため、ハニカム焼成体の外周壁とセル壁との熱容量の差が大きくなる。
従って、請求項1に記載のハニカムフィルタにおいては、ガソリンエンジンからの高い排気温度を受けると、ディーゼルエンジン用のハニカムフィルタに比べてハニカム焼成体の外周壁とセル壁との間の熱応力が大きくなり、ハニカム焼成体にクラックが発生しやすい状況になっている。
しかし、請求項1に記載のハニカムフィルタでは、炭化ケイ素粒子の表面に酸化物層が形成されているため、ハニカム焼成体の外周壁とセル壁との間の熱応力が最も集中する炭化ケイ素粒子間の焼結ネック部において、応力の集中を緩和することもできる。
請求項1に記載のハニカムフィルタでは、ガソリンエンジン用のハニカムフィルタにおいて、セル壁の厚さを0.2mm以下と薄くすること、外周壁の厚さをセル壁の厚さよりも厚くすることにより生じる課題を、ハニカム焼成体を構成する炭化ケイ素粒子の表面に酸化物層を形成することによって解決している。従って、上述した効果は、それぞれの構成単独からは予期し得ないものである。
また、請求項1に記載のハニカムフィルタでは、ディーゼルエンジンよりも排気温度が高いガソリンエンジン用のハニカムフィルタにおいて生じる特有の課題を解決している。従って、上述した効果は、ディーゼルエンジン用のハニカムフィルタからは予期し得ないものである。
ハニカム焼成体を構成する炭化ケイ素粒子は、11~20μm程度の平均粒子径を有する。そのため、酸化物層の厚さが200~400nmであると、炭化ケイ素粒子に比べて非常に薄いため、圧力損失に悪影響を及ぼすことがない。
酸化物層の厚さが200nm未満であると、酸化物層の厚さが薄すぎるため、ネックの結合端部への応力集中を緩和する効果を充分に得ることができない。一方、酸化物層の厚さが400nmを超えると、炭化ケイ素粒子と酸化物層との熱膨張率の差に起因する応力が大きくなるため、ハニカム焼成体にクラックが発生しやすくなると推察される。
セル壁の厚さが0.1~0.125mmであると、圧力損失の増大を効果的に抑制しつつ、機械的強度を維持することができる。
セル壁の厚さが0.1mm未満であると、セル壁が薄くなりすぎるため、充分な機械的強度が得られにくくなる。一方、セル壁の厚さが0.125mmを超えると、圧力損失の増大を抑制する効果が得られにくくなる。
外周壁の厚さがセル壁の厚さの150%未満であると、ハニカム焼成体の外周部付近における機械的強度を向上させる効果を充分に得ることができない。一方、外周壁の厚さがセル壁の厚さの300%を超えると、機械的強度を向上させることはできるが、ハニカムフィルタの開口率が小さくなり、圧力損失が上昇しやすくなる。
外周壁の厚さが0.25mm未満であると、ハニカム焼成体の外周部付近における機械的強度を向上させる効果を充分に得ることができない。一方、外周壁の厚さが0.4mmを超えると、機械的強度を向上させることはできるが、ハニカムフィルタの開口率が小さくなり、圧力損失が上昇しやすくなる。
ハニカム焼成体のセル壁に触媒を担持することにより、排ガス中の含まれるCO、HC又はNOx等の有害成分を浄化することができる。
また、請求項9に記載のハニカムフィルタは、複数個の上記ハニカム焼成体が接着材層を介して結束されてなる。
ガス入口側及びガス出口側を備えた金属容器と、
上記金属容器に収容されたハニカムフィルタと、
上記ハニカムフィルタの周囲に巻き付けられ、上記金属容器及び上記ハニカムフィルタの間に配設された保持シール材とを備えた排ガス浄化装置であって、
上記ハニカムフィルタは、本発明のハニカムフィルタであることを特徴とする。
排ガス浄化装置を用いてガソリンエンジンから排出される排ガスを浄化する排ガス浄化方法であって、
上記排ガス浄化装置は、ガス入口側及びガス出口側を備えた金属容器と、
上記金属容器内に収容されたハニカムフィルタと、
上記ハニカムフィルタの周囲に巻き付けられ、上記金属容器及び上記ハニカムフィルタの間に配設された保持シール材とを備え、
上記ハニカムフィルタは、本発明のハニカムフィルタであり、
ガソリンエンジンから排出される排ガスを、上記金属容器の上記ガス入口側から上記排ガス浄化装置に流入させ、上記金属容器の上記ガス出口側から流出させることを特徴とする。
そのため、請求項10に記載の排ガス浄化装置、及び、請求項11に記載の排ガス浄化方法では、ガソリンエンジン、特に、ガソリン直噴エンジンから排出される排ガスを好適に浄化することができる。
以下、本発明のハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法の一実施形態である第一実施形態について説明する。
図1は、本発明の第一実施形態に係るハニカムフィルタの一例を模式的に示す斜視図である。
図2(a)は、図1に示すハニカムフィルタを構成するハニカム焼成体の一例を模式的に示す斜視図である。図2(b)は、図2(a)に示すハニカム焼成体のA-A線断面図である。
このような、ハニカム焼成体が複数個結束されてなるハニカムフィルタは、集合型ハニカムフィルタともいう。
また、ハニカム焼成体20は、図2(a)及び図2(b)に示す形状を有している。
従って、一方の端面25が開口したセル21に流入した排ガスG(図2(b)中、排ガスをGで表し、排ガスの流れを矢印で示す)は、必ずセル21を隔てるセル壁22を通過した後、他方の端面26が開口したセル21から流出するようになっている。従って、セル壁22がPM等を捕集するためのフィルタとして機能する。
なお、ハニカム焼成体及びハニカムフィルタの表面のうち、セルが開口している面を端面といい、端面以外の面を側面という。
ガソリンエンジンは、ガソリン直噴エンジンであることが好ましい。
本発明の第一実施形態に係るハニカムフィルタを構成するハニカム焼成体は、骨材としての多数の炭化ケイ素粒子が相互間に多数の細孔を保持した状態で結合することによって構成されている。
また、本発明の第一実施形態に係るハニカムフィルタを構成するハニカム焼成体は、炭化ケイ素を60重量%以上含む限り、炭化ケイ素以外の他の成分を含んでいてもよい。例えば、ハニカム焼成体は、40重量%以下のケイ素を含んでいてもよい。ハニカム焼成体の構成材料の主成分は、炭化ケイ素に金属ケイ素が配合されたケイ素含有炭化ケイ素であってもよいし、ケイ素又はケイ酸塩化合物で結合された炭化ケイ素であってもよい。なお、ハニカム焼成体が金属ケイ素等のケイ素を含む場合には、これらのケイ素の表面にも、酸化物層が形成されていることになる。
これらの中でも、ハニカム焼成体は、炭化ケイ素を98重量%以上含んでいるか、又は、炭化ケイ素と金属ケイ素とを98重量%以上含んでいることが好ましい。
セル壁の厚さが0.2mmを超えると、圧力損失が高くなってしまう。一方、セル壁の厚さが0.1mm未満であると、セル壁が薄くなりすぎるため、充分な機械的強度が得られにくくなる。
また、セル壁の厚さが0.1~0.125mmであると、圧力損失の増大を効果的に抑制しつつ、機械的強度を維持することができる。
具体的には、外周壁の厚さは、セル壁の厚さの150~300%であることが好ましく、200~300%であることがより好ましい。
外周壁の厚さがセル壁の厚さの150%未満であると、ハニカム焼成体の外周部付近における機械的強度を向上させる効果を充分に得ることができない。一方、外周壁の厚さがセル壁の厚さの300%を超えると、機械的強度を向上させることはできるが、ハニカムフィルタの開口率が小さくなり、圧力損失が上昇しやすくなる。
外周壁の厚さが0.25mm未満であると、ハニカム焼成体の外周部付近における機械的強度を向上させる効果を充分に得ることができない。一方、外周壁の厚さが0.4mmを超えると、機械的強度を向上させることはできるが、ハニカムフィルタの開口率が小さくなり、圧力損失が上昇しやすくなる。
図3(a)は、ハニカム焼成体を構成する炭化ケイ素粒子同士の結合状態を模式的に示す説明図である。図3(b)は、図3(a)に示す炭化ケイ素粒子の部分拡大図である。
図3(a)及び図3(b)に示すように、ハニカム焼成体を構成する炭化ケイ素粒子31は、互いにネック31aを介して結合されている。また、炭化ケイ素粒子31の表面には、ケイ素を含む酸化物層32が形成されている。
ハニカム焼成体を構成する炭化ケイ素粒子は、11~20μm程度の平均粒子径を有する。そのため、酸化物層の厚さが200~400nmであると、炭化ケイ素粒子に比べて非常に薄いため、圧力損失に悪影響を及ぼすことがない。
酸化物層の厚さが200nm未満であると、酸化物層の厚さが薄すぎるため、ネックの結合端部への応力集中を緩和する効果を充分に得ることができない。一方、酸化物層の厚さが400nmを超えると、炭化ケイ素粒子と酸化物層との熱膨張率の差に起因する応力が大きくなるため、ハニカム焼成体にクラックが発生しやすくなると推察される。
なお、上記重量増加率は、酸化物層を形成する前後のハニカム焼成体又はハニカムフィルタの重量を測定することにより得られる重量増加率のことである。
例えば、懸滴法により、接触角計(協和界面科学株式会社製、Drop Master 300、計測システム:CCDカメラ)を用いて、懸滴との接触角が40°から20°にまで変化する時間(以下、接触角変化時間という)を測定した場合、本発明の第一実施形態に係るハニカムフィルタでは、接触角変化時間が14~18秒である。
上記の接触角変化時間が短いほど、触媒等の濡れ性に優れており、ハニカム焼成体に触媒等を容易に担持することができると考えられる。
なお、懸滴としては、界面活性剤(サンノプコ社製、SN980、粘度:3700cP、表面張力:30.6mN/m)を用いる。
一方、炭化ケイ素粒子の表面に酸化物層が形成されていない場合、接触角変化時間は、20~22秒程度である。
以下、図2(a)及び図2(b)に示したハニカム焼成体を含むハニカムフィルタを製造する方法について工程順に説明する。
具体的には、まず、セラミック粉末としての平均粒子径の異なる炭化ケイ素粉末、有機バインダ、液状の可塑剤、潤滑剤、及び、水を混合することにより、ハニカム成形体製造用のセラミック原料(湿潤混合物)を調製する。
続いて、上記湿潤混合物を押出成形機に投入する。上記湿潤混合物を押出成形することにより所定の形状のハニカム成形体を作製する。
ここで、封止材ペーストとしては、例えば、炭化ケイ素粉末、バインダ、溶媒、分散剤、及び、潤滑剤を混合することにより作製することができる。また、上記セラミック原料(湿潤混合物)を封止材ペーストとして用いてもよい。
脱脂工程では、ハニカム成形体を、酸素含有雰囲気下において、300~650℃で加熱する。
なお、セルの端部に充填された封止材ペーストは、加熱により焼成され、封止材となる。
また、切断工程、乾燥工程、封止工程、脱脂工程及び焼成工程の条件は、従来からハニカム焼成体を作製する際に用いられている条件を適用することができる。
酸化工程により、ハニカム焼成体を構成する炭化ケイ素粒子の表面に酸化物層を形成することができる。
酸化雰囲気中の酸素濃度(酸素に換算した含有量)は特に限定されないが、5~21容量%であることが好ましい。コスト面から考えると、空気を用いることが好ましい。
酸化雰囲気中の酸素濃度が5容量%未満であると、ハニカム焼成体の炭化ケイ素粒子の表面の酸化が不安定となり、所望の厚さの酸化物層を形成することが困難となる。また、酸化雰囲気中の酸素濃度が5容量%未満であると、長時間熱処理を行う必要があり、製造効率が低下しやすくなる。一方、酸化雰囲気中の酸素濃度が21容量%を超えると、酸素ガスを準備する等、酸化雰囲気を生成する工程が必要となり、製造効率が低下しやすくなる。
熱処理温度が1200℃未満であると、所望の厚さの酸化物層を形成することが難しくなる。また、目的の厚さの酸化物層を形成するために長時間熱処理を行う必要がある。一方、熱処理温度が1400℃を超えると、酸化物層の厚さを調整することが難しい。
具体的には、熱処理温度が1200℃以上1300℃未満である場合、熱処理時間は5~35時間であることが好ましく、熱処理温度が1300℃以上1400℃以下である場合、熱処理時間は0.5~5時間であることが好ましい。
熱処理時間が下限値よりも短いと、目的の厚さの酸化物層を形成することが困難となる。一方、熱処理時間が上限値を超えると、目的の厚さよりも厚い酸化物層が形成されてしまう。
本明細書において、熱処理時間とは、目的の熱処理温度まで昇温した後、その熱処理温度を保持する時間のことをいう。従って、酸化工程全体においてハニカム焼成体を加熱している時間は、上記熱処理時間の他に、昇温及び降温のために必要な時間が含まれる。
まず、ハニカム焼成体のそれぞれの所定の側面に、接着材ペーストを塗布して接着材ペースト層を形成する。そして、この接着材ペースト層の上に、順次他のハニカム焼成体を積層する工程を繰り返す。このような方法により、ハニカム焼成体の側面に接着材ペーストが塗布されてなるハニカム焼成体の集合体を作製する。
続いて、ハニカム焼成体の集合体を乾燥機等を用いて加熱して、接着材ペーストを乾燥固化させることによって、複数のハニカム焼成体が接着材層を介して接着されてなるセラミックブロックを作製する。
なお、接着材ペーストとしては、例えば、無機バインダと有機バインダと無機粒子とからなるものを使用する。また、上記接着材ペーストは、さらに無機繊維及び/又はウィスカを含んでいてもよい。
具体的には、セラミックブロックに対して、ダイヤモンドカッターを用いて切削加工を施すことにより、外周が円柱状に加工されたセラミックブロックを作製する。
ここで、外周コート材ペーストとしては、上記接着材ペーストを使用することができる。
なお、外周コート材ペーストして、上記接着材ペーストと異なる組成のペーストを使用してもよい。
また、外周コート層は必ずしも設ける必要はなく、必要に応じて設ければよい。
しかしながら、本発明の第一実施形態に係るハニカムフィルタの製造方法では、接着工程と外周加工工程との間、外周加工工程と外周コート層形成工程との間、又は、外周コート層形成工程の後に酸化工程を行ってもよい。また、外周コート層が形成されていないセラミックブロックに対して酸化工程を行ってもよい。
本発明の第一実施形態に係る排ガス浄化装置には、上述した本発明の第一実施形態に係るハニカムフィルタが用いられている。
図4に示す排ガス浄化装置100は、ガス入口側121及びガス出口側122を備えた金属容器120と、金属容器120内に収容されたハニカムフィルタ110とを備えている。
図2(a)及び図2(b)に示したように、ハニカムフィルタ10を構成するハニカム焼成体20のセル21のいずれかの端部は、封止材24で封止されている。
保持シール材130は、ハニカムフィルタ110の周囲に巻き付けられている。
保持シール材は、主にアルミナ等の無機繊維からなる平面視略矩形状のマット状の部材である。
そして、排ガスGは、セル21を隔てるセル壁22を通過する。この際、排ガスG中のPMはセル壁22で捕集され、排ガスGが浄化される。
浄化された排ガスGは、ハニカム焼成体20の他方の端面26が開口したセル21に流入し、ハニカムフィルタ110の外に排出される。そして、排ガスGは、金属容器120のガス出口側122から排ガス浄化装置100の外に排出される。
すなわち、本発明の第一実施形態に係る排ガス浄化装置は、ガソリンパティキュレートフィルタ(GPF)として好適に用いることができる。
上記の方法で製造した本発明の第一実施形態に係るハニカムフィルタを金属容器内に配置する。具体的には、保持シール材として、主に無機繊維からなる平面視略矩形状のマットを準備し、このマットをハニカムフィルタに巻き付ける。そして、略円筒状の金属容器にマットが巻き付けられたハニカムフィルタを圧入することによって排ガス浄化装置とすることができる。
また、金属容器を、第一の金属容器及び第二の金属容器の2つの部品に分離可能な形状としておき、無機繊維からなるマットを巻き付けたハニカムフィルタを第一の金属容器上に載置した後に第二の金属容器を被せて密封することによって排ガス浄化装置とすることもできる。
(1)本実施形態のハニカムフィルタでは、セル壁の厚さを0.2mm以下と薄くすることにより、ハニカムフィルタの開口率を大きくすることができる。その結果、圧力損失の増大を抑制させることができる。
なお、ハニカム焼成体の外周壁には排ガスが流入しない。従って、外周壁の厚さを厚くしても、圧力損失に悪影響を及ぼすことがない。
炭化ケイ素粒子の表面に酸化物層が形成されている場合、ネックの結合角度が大きくなり、ネックの結合端部が滑らかになる。従って、ネックの結合端部への応力集中が緩和される。その結果、ハニカム焼成体の機械的強度が向上すると考えられる。
ガソリンエンジンによる排気温度は、ディーゼルエンジンによる排気温度よりも高い。また、本実施形態のハニカムフィルタでは、外周壁をセル壁よりも厚く、セル壁の厚さを0.2mm以下に調整しているため、ハニカム焼成体の外周壁とセル壁との熱容量の差が大きくなる。
従って、本実施形態のハニカムフィルタにおいては、ガソリンエンジンからの高い排気温度を受けると、ディーゼルエンジン用のハニカムフィルタに比べてハニカム焼成体の外周壁とセル壁との間の熱応力が大きくなり、ハニカム焼成体にクラックが発生しやすい状況になっている。
しかし、本実施形態のハニカムフィルタでは、炭化ケイ素粒子の表面に酸化物層が形成されているため、ハニカム焼成体の外周壁とセル壁との間の熱応力が最も集中する炭化ケイ素粒子間の焼結ネック部において、応力の集中を緩和することもできる。
また、本実施形態のハニカムフィルタは、ガソリンエンジン用のハニカムフィルタとして充分なPM捕集能を有している。
そのため、本実施形態の排ガス浄化装置、及び、本実施形態の排ガス浄化方法では、ガソリンエンジン、特に、ガソリン直噴エンジンから排出される排ガスを好適に浄化することができる。
(1)ハニカム焼成体の作製
平均粒子径22μmの炭化ケイ素の粗粉末52.8重量%と、平均粒子径0.5μmの炭化ケイ素の微粉末22.6重量%とを混合し、得られた混合物に対して、アクリル樹脂2.1重量%、有機バインダ(メチルセルロース)4.6重量%、潤滑剤(日油社製 ユニルーブ)2.8重量%、グリセリン1.3重量%、及び、水13.8重量%を加えて混練して湿潤混合物を得た。そして、湿潤混合物を押出成形した後、切断することにより、図2(a)及び図2(b)に示した形状と同様の形状であって、セルを封止していない生のハニカム成形体を作製した。
乾燥後のハニカム成形体の所定のセルに、封止材ペーストを充填し、再び乾燥機を用いて乾燥させた。
封止材ペーストは、平均粒子径11μmの炭化ケイ素の粗粉末63.3重量%、平均粒子径0.65μmの炭化ケイ素の微粉末15.8重量%、溶媒(ジエチレングリコールモノ-2-エチルヘキシルエーテル)11.1重量%、バインダ(メタクリル酸エステル共重合物とジエチレングリコールモノ-2-エチルヘキシルエーテルとの混合物)4.7重量%、分散剤(第一工業製薬社製 プライサーフ)1.6重量%、及び、潤滑剤(日油社製 ユニルーブ50MB-26)3.4重量%を混合することにより調製した。
ハニカム焼成体の気孔率は45%、平均気孔径は15μm、大きさは34.3mm×34.3mm×150mm、セルの数(セル密度)は46.5個/cm2(300個/inch2)、セル壁の厚さは0.10mm(4mil)、外周影の厚さは0.30mm(12mil)であった。
酸化工程では、空気雰囲気下において、室温から昇温速度300℃/時間で1370℃まで昇温し、1370℃で3時間保持した後、降温速度100℃/時間で300℃まで降温した後、室温(25℃)に取り出した。
酸化工程により、ハニカム焼成体の表面が酸化される。具体的には、ハニカム焼成体の炭化ケイ素粒子の表面に酸化物層が形成される。
以下、酸化工程を行った後のハニカム焼成体を「実施例1のハニカム焼成体」という。
実施例1のハニカム焼成体について、以下の特性を評価した。
XPSにより、ハニカム焼成体の酸化物層の厚さ(nm)を測定した。
XPS測定用サンプルとして、実施例1のハニカム焼成体から、2cm×2cm×0.25mmの大きさの炭化ケイ素部分を切り出した。そして、XPS測定用サンプルの破断面ではない表面を観察した。
XPS装置としては、ULVAC-PHI社製のQuantera SXMを用い、X線源としては、モノクロ化されたAl-Kα線(Monochromated Al-Kα)を用いた。測定条件は、電圧:15kV、出力:25W、測定領域:100μmφとした。イオンスパッタ条件は、イオン種:Ar+、電圧:1kV、スパッタレート(SiO2換算):1.5nm/minとした。
上記XPS装置を用いて、XPS測定用サンプルの定性分析(ワイドスキャン)、及び、C、O、Siについての深さ方向分析を行った。深さ方向分析の結果より、SiO2プロファイルの最高強度と最低強度の中間となる強度の時間と、XPS測定用サンプルのスパッタレート(SiO2換算)から酸化物層の厚さを算出した。
実施例1における酸化物層の厚さは、310nmであった。
実施例1のハニカム焼成体について、3点曲げ強度試験を行い、ハニカム焼成体の曲げ強度(MPa)を測定した。
図5は、3点曲げ強度試験の方法を模式的に示す説明図である。
まず、3点曲げ強度測定用サンプルとして、実施例1のハニカム焼成体から、外周壁及び封止部を除く2セル×4セル×40mmの大きさの炭化ケイ素部分を10本切り出した。
そして、図5に示すように、3点曲げ強度測定用サンプル60の主面(サンプルの外周面のうち広い方の面)に対して垂直な方向に荷重を印加し、破壊荷重(サンプルが破壊した荷重)を測定した。10本の3点曲げ強度測定用サンプルについて破壊荷重を測定し、その平均値を曲げ強度とした。
3点曲げ強度試験は、JIS R 1601を参考に、インストロン5582を用い、スパン間距離:30mm、スピード1mm/minで行った。
実施例1における曲げ強度は、27.9MPaであった。
実施例1のハニカム焼成体について、下記の方法により濡れ性を評価した。
懸滴法により、接触角計(協和界面科学社製、Drop Master 300、計測システム:CCDカメラ)を用いて、懸滴との接触角が40°から20°にまで変化する時間(接触角変化時間)を測定した。
なお、懸滴としては、界面活性剤(サンノプコ社製、SN980、粘度:3700cP、表面張力:30.6mN/m)を用いた。
実施例1における接触角変化時間は、15.0秒であった。
実施例1で作製したハニカム焼成体について、実施例1と同様の条件で酸化工程を行い、酸化工程前の重量A及び酸化工程後の重量Bを測定した。以下の式より、重量増加率を求めた。
重量増加率(重量%)=[(B-A)/A]×100
実施例1における重量増加率は、2.3重量%であった。
実施例1のハニカム焼成体を16個用いて、ハニカム焼成体の側面に接着材ペーストを塗布し、この接着材ペーストを介してハニカム焼成体を縦4個、横4個の計16個接着させることにより、ハニカム焼成体の集合体を作製した。
なお、接着材ペーストとして、平均繊維長20μm、平均繊維径2μmのアルミナファイバ30重量%、平均粒子径0.6μmの炭化ケイ素粒子21重量%、シリカゾル(固形分30重量%)15重量%、カルボキシメチルセルロース5.6重量%、及び、水28.4重量%を含むペーストを使用した。
次に、外周が円柱状に加工されたセラミックブロックの外周面に外周コート材ペーストを塗布し、外周コート材ペースト層を形成した。そして、この外周コート材ペースト層を120℃で乾燥固化させて外周コート層を形成することにより、外周に外周コート層が形成された直径143.8mm×長さ150mmの円柱状のハニカムフィルタを製造した。
この際、コート材ペーストとしては、上記接着材ペーストを使用した。
酸化工程を行わなかったこと以外は、実施例1と同様にしてハニカム焼成体を作製した。以下、「比較例1のハニカム焼成体」という。
また、比較例1のハニカム焼成体を用いて、実施例1と同様にして、ハニカムフィルタを製造した。
その結果、比較例1における酸化物層の厚さは4nm未満、曲げ強度は14.4MPa、接触角変化時間は20.0秒であった。また、比較例1では、酸化工程を行っていないため、重量増加率を0重量%とした。
一方、酸化工程を行わなかった比較例1においては、酸化物層の厚さが4nm未満であり、炭化ケイ素粒子の表面に有効な酸化物層が形成されていないと考えられる。
ここで、熱衝撃破壊抵抗係数R’が大きいほど、熱衝撃に対して耐性があることが知られている(例えば、K. Ohno et al.,“Further Durability Enhancement of Re-crystallized SiC-DPF”,SAE technical paper:2004-01-0954等を参照のこと)。
また、酸化物層の有無によっては、ポアソン比γ、熱伝導率k、熱膨張係数α、ヤング率Eが変化しないことが確認されている。
従って、ポアソン比γ、熱伝導率k、熱膨張係数α、ヤング率Eが同じであれば、曲げ強度σが大きいほど、熱衝撃破壊抵抗係数R’は大きくなり、熱衝撃に対する耐性が高いと言える。
そのため、実施例1のハニカム焼成体は、比較例1のハニカム焼成体に比べて熱衝撃に対する耐性が高いと推測される。
この結果から、ハニカム焼成体を構成する炭化ケイ素粒子の表面に酸化物を形成することにより、ハニカム焼成体の表面が平滑になる結果、ハニカム焼成体に触媒等を担持させやすくなると考えられる。
本発明の実施形態に係るハニカムフィルタは、1個の炭化ケイ素質のハニカム焼成体からなるものであってもよい。このような、1つのハニカム焼成体からなるハニカムフィルタは、一体型ハニカムフィルタともいう。
一体型ハニカムフィルタであっても、本発明の第一実施形態に係るハニカムフィルタと同様の効果を奏する。
図6(a)及び図6(b)に示すハニカムフィルタ40は、円柱状の1つのハニカム焼成体からなるセラミックブロック43を有し、セラミックブロック43の周囲に外周コート層42が形成されてなる。なお、外周コート層は、必要に応じて形成されていればよい。
従って、一方の端面55が開口したセル51に流入した排ガスG(図6(b)中、排ガスをGで表し、排ガスの流れを矢印で示す)は、必ずセル51を隔てるセル壁52を通過した後、他方の端面56が開口したセル51から流出するようになっている。従って、セル壁52がPM等を捕集するためのフィルタとして機能する。
なお、外周コート層形成工程の後に酸化工程を行ってもよい。また、外周加工工程を行う場合には、焼成工程と外周加工工程との間、又は、外周加工工程と外周コート層形成工程との間に酸化工程を行ってもよい。また、外周加工工程を行わない場合には、焼成工程と外周コート層形成工程との間に酸化工程を行ってもよい。さらに、外周コート層が形成されていないハニカムフィルタに対して酸化工程を行ってもよい。
ハニカム焼成体の気孔率が30~50%であると、ハニカム焼成体の強度を維持することができるとともに、排ガスがセル壁を通過する際の抵抗を低く保つことができる。
これに対し、ハニカム焼成体の気孔率が30%未満であると、ハニカム焼成体がパティキュレート(PM)の目詰まりを起こしやすくなる。一方、ハニカム焼成体の気孔率が50%を超えると、ハニカム焼成体の強度が低下して容易に破壊されやすくなる。
ハニカム焼成体の平均気孔径が5μm未満であると、パティキュレートが容易に目詰まりを起こしやすくなる。一方、ハニカム焼成体の平均気孔径が30μmを超えると、パティキュレートがセル壁の気孔を通り抜けてしまい、パティキュレートを捕集することができず、フィルタとしての機能が不充分となる。
例えば、以下のような断面形状が異なる3種類のハニカム焼成体を作製してもよい。第1のハニカム焼成体は、断面形状が2本の直線と1本の円弧とで囲まれた形状である。第2のハニカム焼成体は、断面形状が3本の直線と1本の円弧とで囲まれた形状である。第3のハニカム焼成体は、断面形状が4本の直線で囲まれた形状(四角形)である。断面形状の異なるこれら3種類のハニカム焼成体は、押出成形において用いる金型の形状を変更することにより作製することができる。そして、第1のハニカム焼成体を8個、第2のハニカム焼成体及び第3のハニカム焼成体をそれぞれ4個ずつ組み合わせることにより、円柱状のハニカムフィルタを作製することができる。
また、湿潤混合物に含まれる潤滑剤としては、特に限定されず、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシプロピレンアルキルエーテル等のポリオキシアルキレン系化合物等が挙げられる。
潤滑剤の具体例としては、例えば、ポリオキシエチレンモノブチルエーテル、ポリオキシプロピレンモノブチルエーテル等が挙げられる。
なお、可塑剤、潤滑剤は、場合によっては、湿潤混合物に含まれていなくてもよい。
さらに、湿潤混合物中には、成形助剤が添加されていてもよい。
成形助剤としては特に限定されず、例えば、エチレングリコール、デキストリン、脂肪酸、脂肪酸石鹸、ポリアルコール等が挙げられる。
バルーンとしては特に限定されず、例えば、アルミナバルーン、ガラスマイクロバルーン、シラスバルーン、フライアッシュバルーン(FAバルーン)、ムライトバルーン等が挙げられる。これらの中では、アルミナバルーンが好ましい。
ハニカム焼成体のセル壁にCO、HC及びNOx等の排ガス中の有害なガス成分を浄化することが可能となる触媒を担持させることにより、触媒反応により排ガス中の有害なガス成分を充分に浄化することが可能となる。また、PMの燃焼を助ける触媒を担持させることにより、PMをより容易に燃焼除去することが可能となる。
これらの材料は、単独で使用してもよいし、2種以上併用してもよい。
係る必須の構成要素に、本発明の第一実施形態、及び、その他の実施形態で詳述した種々の構成(例えば、ハニカム焼成体の構成、酸化物層の構成、酸化工程の条件等)を適宜組み合わせることにより所望の効果を得ることができる。
11 接着材層
12、42 外周コート層
13、43 セラミックブロック
20 ハニカム焼成体
21、51 セル
22、52 セル壁
23、53 外周壁
24、54 封止材
25 ハニカム焼成体の一方の端面
26 ハニカム焼成体の他方の端面
31 炭化ケイ素粒子
31a ネック
32 ケイ素を含む酸化物層
55 ハニカムフィルタの一方の端面
56 ハニカムフィルタの他方の端面
60 3点曲げ強度測定用サンプル
100 排ガス浄化装置
120 金属容器
121 金属容器のガス入口側
122 金属容器のガス出口側
130 保持シール材
G 排ガス
Claims (11)
- 多数のセルがセル壁を隔てて長手方向に並設され、外周に外周壁が形成された炭化ケイ素質のハニカム焼成体を含み、
前記セルのいずれか一方の端部が封止されており、
前記セル壁の厚さは、0.2mm以下であり、
前記外周壁の厚さは、前記セル壁の厚さよりも厚く、
前記ハニカム焼成体を構成する炭化ケイ素粒子の表面には、ケイ素を含む酸化物層が形成されており、
ガソリンエンジンから排出される排ガス中に含有されるパティキュレートを捕集するために用いられることを特徴とするハニカムフィルタ。 - 前記酸化物層の厚さは、200~400nmである請求項1に記載のハニカムフィルタ。
- 前記セル壁の厚さは、0.1~0.125mmである請求項1又は2に記載のハニカムフィルタ。
- 前記外周壁の厚さは、前記セル壁の厚さの150~300%である請求項1~3のいずれかに記載のハニカムフィルタ。
- 前記外周壁の厚さは、0.25~0.4mmである請求項1~4のいずれかに記載のハニカムフィルタ。
- 前記ハニカム焼成体の前記セル壁には、触媒が担持されている請求項1~5のいずれかに記載のハニカムフィルタ。
- 前記ガソリンエンジンは、ガソリン直噴エンジンである請求項1~6のいずれかに記載のハニカムフィルタ。
- 1個の前記ハニカム焼成体からなる請求項1~7のいずれかに記載のハニカムフィルタ。
- 複数個の前記ハニカム焼成体が接着材層を介して結束されてなる請求項1~7のいずれかに記載のハニカムフィルタ。
- ガス入口側及びガス出口側を備えた金属容器と、
前記金属容器に収容されたハニカムフィルタと、
前記ハニカムフィルタの周囲に巻き付けられ、前記金属容器及び前記ハニカムフィルタの間に配設された保持シール材とを備えた排ガス浄化装置であって、
前記ハニカムフィルタは、請求項1~9のいずれかに記載のハニカムフィルタであることを特徴とする排ガス浄化装置。 - 排ガス浄化装置を用いてガソリンエンジンから排出される排ガスを浄化する排ガス浄化方法であって、
前記排ガス浄化装置は、ガス入口側及びガス出口側を備えた金属容器と、
前記金属容器内に収容されたハニカムフィルタと、
前記ハニカムフィルタの周囲に巻き付けられ、前記金属容器及び前記ハニカムフィルタの間に配設された保持シール材とを備え、
前記ハニカムフィルタは、請求項1~9のいずれかに記載のハニカムフィルタであり、
ガソリンエンジンから排出される排ガスを、前記金属容器の前記ガス入口側から前記排ガス浄化装置に流入させ、前記金属容器の前記ガス出口側から流出させることを特徴とする排ガス浄化方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12877477.5A EP2853303A4 (en) | 2012-05-21 | 2012-05-21 | WAVE FILTER, EXHAUST GAS CLEANING DEVICE AND EXHAUST GAS CLEANING PROCEDURE |
PCT/JP2012/062947 WO2013175552A1 (ja) | 2012-05-21 | 2012-05-21 | ハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法 |
JP2014516537A JPWO2013175552A1 (ja) | 2012-05-21 | 2012-05-21 | ハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法 |
US14/541,025 US20150071829A1 (en) | 2012-05-21 | 2014-11-13 | Honeycomb filter, exhaust gas purifying apparatus, and method for purifying exhaust gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2012/062947 WO2013175552A1 (ja) | 2012-05-21 | 2012-05-21 | ハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/541,025 Continuation US20150071829A1 (en) | 2012-05-21 | 2014-11-13 | Honeycomb filter, exhaust gas purifying apparatus, and method for purifying exhaust gas |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013175552A1 true WO2013175552A1 (ja) | 2013-11-28 |
Family
ID=49623285
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/062947 WO2013175552A1 (ja) | 2012-05-21 | 2012-05-21 | ハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20150071829A1 (ja) |
EP (1) | EP2853303A4 (ja) |
JP (1) | JPWO2013175552A1 (ja) |
WO (1) | WO2013175552A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016148966A1 (en) * | 2015-03-13 | 2016-09-22 | Corning Incorporated | Honeycomb assembly and packaging system |
US20170197170A1 (en) * | 2014-07-25 | 2017-07-13 | Corning Incorporation | Defect tolerant honeycomb structures |
JP2019167278A (ja) * | 2018-03-26 | 2019-10-03 | 日本碍子株式会社 | 多孔質材料、セル構造体および多孔質材料の製造方法 |
JP2021154274A (ja) * | 2020-03-26 | 2021-10-07 | 日本碍子株式会社 | 柱状ハニカム構造フィルタの製造方法 |
US11745384B2 (en) | 2017-12-22 | 2023-09-05 | Corning, Incorporated | Multi-wall thickness, thin-walled honeycomb bodies, and extrusion dies and methods therefor |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016013516A1 (ja) * | 2014-07-23 | 2016-01-28 | イビデン株式会社 | ハニカムフィルタ |
EP3173139B1 (en) * | 2014-07-23 | 2024-04-03 | Ibiden Co., Ltd. | Honeycomb filter |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000218165A (ja) * | 1999-01-29 | 2000-08-08 | Ibiden Co Ltd | ハニカムフィルタ及びその製造方法 |
JP2002172304A (ja) * | 2000-09-26 | 2002-06-18 | Ngk Insulators Ltd | 複層構造ハニカムフィルタ及びその製造方法 |
JP2008238158A (ja) * | 2007-02-28 | 2008-10-09 | Ibiden Co Ltd | ハニカムフィルタ |
JP2010221154A (ja) | 2009-03-24 | 2010-10-07 | Ngk Insulators Ltd | ハニカム触媒体 |
JP2010221153A (ja) | 2009-03-24 | 2010-10-07 | Ngk Insulators Ltd | ハニカム構造体 |
JP2010221155A (ja) | 2009-03-24 | 2010-10-07 | Ngk Insulators Ltd | ハニカム構造体の製造方法及びハニカム触媒体の製造方法 |
JP2011139975A (ja) | 2010-01-05 | 2011-07-21 | Ngk Insulators Ltd | ハニカム構造体 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2545257B2 (ja) * | 1988-01-14 | 1996-10-16 | 東芝セラミックス株式会社 | フイルター |
JP2002530175A (ja) * | 1998-11-20 | 2002-09-17 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | コードレス走査ヘッドの充電器を備える超音波診断イメージングシステム |
JP2001261428A (ja) * | 2000-03-14 | 2001-09-26 | Ngk Insulators Ltd | セラミックハニカム構造体 |
CN100560180C (zh) * | 2005-11-18 | 2009-11-18 | 揖斐电株式会社 | 蜂窝结构体 |
EP2349950B1 (en) * | 2008-09-30 | 2017-12-06 | Pirelli & C. Ambiente S.r.l. | Honeycomb structural body for exhaust gas purification |
JP2011224538A (ja) * | 2009-12-01 | 2011-11-10 | Ibiden Co Ltd | ハニカムフィルタ及び排ガス浄化装置 |
JP5563844B2 (ja) * | 2010-02-16 | 2014-07-30 | 日本碍子株式会社 | 排気ガス浄化装置 |
EP2441741A1 (en) * | 2010-10-13 | 2012-04-18 | Ibiden Co., Ltd. | Honeycomb structured body and exhaust gas purifying apparatus |
-
2012
- 2012-05-21 EP EP12877477.5A patent/EP2853303A4/en not_active Withdrawn
- 2012-05-21 WO PCT/JP2012/062947 patent/WO2013175552A1/ja active Application Filing
- 2012-05-21 JP JP2014516537A patent/JPWO2013175552A1/ja active Pending
-
2014
- 2014-11-13 US US14/541,025 patent/US20150071829A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000218165A (ja) * | 1999-01-29 | 2000-08-08 | Ibiden Co Ltd | ハニカムフィルタ及びその製造方法 |
JP2002172304A (ja) * | 2000-09-26 | 2002-06-18 | Ngk Insulators Ltd | 複層構造ハニカムフィルタ及びその製造方法 |
JP2008238158A (ja) * | 2007-02-28 | 2008-10-09 | Ibiden Co Ltd | ハニカムフィルタ |
JP2010221154A (ja) | 2009-03-24 | 2010-10-07 | Ngk Insulators Ltd | ハニカム触媒体 |
JP2010221153A (ja) | 2009-03-24 | 2010-10-07 | Ngk Insulators Ltd | ハニカム構造体 |
JP2010221155A (ja) | 2009-03-24 | 2010-10-07 | Ngk Insulators Ltd | ハニカム構造体の製造方法及びハニカム触媒体の製造方法 |
JP2011139975A (ja) | 2010-01-05 | 2011-07-21 | Ngk Insulators Ltd | ハニカム構造体 |
Non-Patent Citations (2)
Title |
---|
K. OHNO ET AL.: "Further Durability Enhancement of Re-crystallized SiC-DPF", SAE TECHNICAL PAPER: 2004-01-0954 |
See also references of EP2853303A4 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170197170A1 (en) * | 2014-07-25 | 2017-07-13 | Corning Incorporation | Defect tolerant honeycomb structures |
WO2016148966A1 (en) * | 2015-03-13 | 2016-09-22 | Corning Incorporated | Honeycomb assembly and packaging system |
US11745384B2 (en) | 2017-12-22 | 2023-09-05 | Corning, Incorporated | Multi-wall thickness, thin-walled honeycomb bodies, and extrusion dies and methods therefor |
JP2019167278A (ja) * | 2018-03-26 | 2019-10-03 | 日本碍子株式会社 | 多孔質材料、セル構造体および多孔質材料の製造方法 |
JP7051524B2 (ja) | 2018-03-26 | 2022-04-11 | 日本碍子株式会社 | 多孔質材料、セル構造体および多孔質材料の製造方法 |
JP2021154274A (ja) * | 2020-03-26 | 2021-10-07 | 日本碍子株式会社 | 柱状ハニカム構造フィルタの製造方法 |
JP7366075B2 (ja) | 2020-03-26 | 2023-10-20 | 日本碍子株式会社 | 柱状ハニカム構造フィルタの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2853303A1 (en) | 2015-04-01 |
EP2853303A4 (en) | 2016-03-02 |
JPWO2013175552A1 (ja) | 2016-01-12 |
US20150071829A1 (en) | 2015-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4812316B2 (ja) | ハニカム構造体 | |
KR100855167B1 (ko) | 벌집형 구조체 | |
JP4516017B2 (ja) | セラミックハニカム構造体 | |
JP5142529B2 (ja) | ハニカム構造体 | |
US7862781B2 (en) | Honeycomb structure and method for manufacturing honeycomb structure | |
JP4932256B2 (ja) | セラミック焼結体およびセラミックフィルタ | |
JP5990572B2 (ja) | ハニカム構造体、排ガス浄化用ハニカムフィルタ及び排ガス浄化装置 | |
JP5063604B2 (ja) | ハニカムフィルタ | |
US7981370B2 (en) | Honeycomb filter and exhaust gas purifying apparatus | |
WO2013175552A1 (ja) | ハニカムフィルタ、排ガス浄化装置、及び、排ガス浄化方法 | |
US7947231B2 (en) | Honeycomb structure, method for manufacturing honeycomb structure, and exhaust gas purifying apparatus | |
WO2011042976A1 (ja) | 排ガス浄化装置及び排ガス浄化方法 | |
JP2006289237A (ja) | ハニカム構造体 | |
WO2006070504A1 (ja) | フィルタ及びフィルタ集合体 | |
JP5260982B2 (ja) | ハニカムフィルタ | |
JP2011098335A (ja) | 排ガス浄化装置及び排ガス浄化方法 | |
JP2009255037A (ja) | ハニカム構造体 | |
JP2012102004A (ja) | ハニカム構造体及び排ガス浄化装置 | |
WO2009118810A1 (ja) | ハニカム構造体 | |
JP5227617B2 (ja) | ハニカムフィルタ | |
WO2009101691A1 (ja) | ハニカム構造体 | |
WO2011067823A1 (ja) | ハニカムフィルタ及び排ガス浄化装置 | |
JP2011224538A (ja) | ハニカムフィルタ及び排ガス浄化装置 | |
EP1787702A1 (en) | Honeycomb structured body | |
JP4873326B2 (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: 12877477 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014516537 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2012877477 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012877477 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |