[go: up one dir, main page]

CN1816379B - 废气净化蜂窝状过滤器及其制造方法 - Google Patents

废气净化蜂窝状过滤器及其制造方法 Download PDF

Info

Publication number
CN1816379B
CN1816379B CN200480018961XA CN200480018961A CN1816379B CN 1816379 B CN1816379 B CN 1816379B CN 200480018961X A CN200480018961X A CN 200480018961XA CN 200480018961 A CN200480018961 A CN 200480018961A CN 1816379 B CN1816379 B CN 1816379B
Authority
CN
China
Prior art keywords
containing compound
mixture
honeycomb filter
exhaust gas
aluminum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN200480018961XA
Other languages
English (en)
Other versions
CN1816379A (zh
Inventor
福田勉
福田匡洋
福田匡晃
横尾俊信
高桥雅英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ohcera Co Ltd
Original Assignee
Ohcera Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ohcera Co Ltd filed Critical Ohcera Co Ltd
Publication of CN1816379A publication Critical patent/CN1816379A/zh
Application granted granted Critical
Publication of CN1816379B publication Critical patent/CN1816379B/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24491—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24494—Thermal expansion coefficient, heat capacity or thermal conductivity
    • 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
    • B01D46/247—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—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
    • B01D46/2482—Thickness, height, width, length or diameter
    • 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
    • B01D46/2484—Cell density, area or aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/478—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on aluminium titanates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/30—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
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • 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
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • 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
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • 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
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/30—Honeycomb supports characterised by their structural details
    • F01N2330/48—Honeycomb supports characterised by their structural details characterised by the number of flow passages, e.g. cell density
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24149—Honeycomb-like

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Filtering Materials (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)

Abstract

本发明提供由于耐热性和耐热冲击性良好、而且具有高抗热分解性和高机械强度，因而在变化的高温条件下可稳定地使用的废气净化蜂窝状过滤器及其制造方法。本发明的蜂窝状过滤器是用于从废气除去以碳为主要成分的固体微粒的蜂窝状过滤器，该蜂窝状过滤器的材料为将混合物的成形体在1000～1700℃下烧结得到的钛酸铝镁烧结体，所述混合物是以与化学式：MgXAl2(1-X)Ti(1+X)O5(式中，0＜X＜1)所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的金属成分比例含有含镁化合物、含铝化合物和含钛化合物的混合物，或含有换算成氧化物的量为100质量份的所述混合物和1～10质量份化学式：(NayK1-y)AlSi3O8(式中，0≤y≤1)所表示的碱性长石的混合物。

Description

废气净化蜂窝状过滤器及其制造方法
技术领域
本发明涉及用于捕获、除去柴油发动机等的废气中所含的以碳为主要成分的固体微粒(颗粒物)的废气净化蜂窝状过滤器及其制造方法。
背景技术
汽车等的柴油发动机等的废气中含有较高浓度(150～250mg/Nm3)的以碳为主要成分的颗粒物，与氮氧化物等一起成为环境问题的原因之一，所以急需将其高效、经济地除去。以往，提出有被称作DPF(柴油发动机颗粒物过滤器)等的用于捕获、除去这样的废气中的固体微粒的各种过滤器。
例如，在日本专利特开昭57-35918号公报和日本专利特开平5-214922号公报中，揭示了使蜂窝状过滤器的两端在多条流路的上游侧或下游侧端部交替闭塞的废气过滤器。这种蜂窝状过滤器所具有的结构为，将要净化的燃烧废气供给过滤器的上游侧的开口，使其通过过滤器的隔壁，通过隔壁捕获、除去废气中的颗粒物后，从过滤器的下游侧的开口排出净化后的废气。
另一方面，由于上述蜂窝状过滤器的材质要求高耐热性，同时由于处于骤热和骤冷的环境下，所以要求热膨胀系数小且具有强耐热冲击性，因此提出并使用碳化硅或堇青石材料等。然而，这些材料不具有足以作为废气过滤器的特性。
即，在废气过滤器中，捕获的未燃烧的碳质固体微粒异常堆积时，所堆积的碳起火燃烧，在局部引发达到1400～1500℃的急剧的温度上升。这样的情况下，碳化硅材料的过滤器中，因为过滤器的各个部分产生温度分布，热膨胀系数为4.2×10-6K-1，不足够小，所以由于材质受到热应力和热冲击，发生裂缝，引起局部破损。另一方面，堇青石材料的过滤器的情况下，由于热膨胀系数小，只有0.6～1.2×10-6K-1，所以相较由热冲击引起裂缝的问题而言，下述问题更为严重，即由于熔点仅为1400～1450℃，不足够高，所以因上述碳的异常燃烧引起部分熔损。
如果由于如上所述的破损和熔损引起废气过滤器内部产生缺陷，则不仅过滤器中的碳的捕集效率下降，而且废气对过滤器的压力成为对缺陷部位过度的负荷，会进一步引发新的破损，最终废气过滤器整体失去作用。
作为上述蜂窝状过滤器的材料，在WO 01/037971号公报中与碳化硅和堇青石一起提出了钛酸铝。钛酸铝具有超过1700℃的高温下的耐热性、较小的热膨胀系数和良好的耐热冲击性。但是，另一方面，由于钛酸铝通常在800～1280℃的温度范围内存在分解区域，所以存在无法在包括这样的温度范围的变化的温度区域中稳定地使用的巨大问题。另外，由于晶体结构的各向异性强，因而在晶界容易出现因热应力产生的位错，所以存在机械强度不够大的缺点，在壁厚薄且孔密度大的蜂窝体的制造和作为搭载在汽车等上且在高温下承受机械振动等负荷的废气过滤器的使用上留有疑问。
本发明提供耐热性良好、热膨胀系数小、耐热冲击性良好的，而且即使在变化的高温条件下也不发生热分解等的，由于机械强度大而可以长期稳定地使用的，能够高效地捕获、除去柴油发动机等的废气中所含的微粒碳等颗粒物的废气净化蜂窝状过滤器及其制造方法。
发明的揭示
本发明是在为了解决上述课题而认真研究后，基于以下的新发现而完成的：使用将以特定比例含有含镁化合物、含铝化合物和含钛化合物的混合物、或者较好是在该混合物中添加特定量特定的碱性长石所得的混合物烧结得到的钛酸铝镁烧结体的废气净化蜂窝状过滤器不仅具有以往的钛酸铝类陶瓷原有的良好的耐热性、较小的热膨胀系数和较强的耐热冲击性，而且抗热分解性提高，机械强度也改善。
所述本发明主要具有以下的主要内容。
(1)废气净化蜂窝状过滤器，它是用于从燃烧废气除去以碳为主要成分的固体微粒的蜂窝状过滤器，其特征在于，该蜂窝状过滤器为将混合物在1000～1700℃下烧结得到的钛酸铝镁烧结体，所述混合物以与化学式：MgXAl2(1-X)Ti(1+X)O5(式中，0＜X＜1)所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的金属成分比例含有含镁化合物、含铝化合物和含钛化合物。
(2)废气净化蜂窝状过滤器，其特征在于，该蜂窝状过滤器的材料为将混合物在1000～1700℃下烧结得到的钛酸铝镁烧结体，所述混合物含有换算成氧化物的量为100质量份的以与化学式：MgXAl2(1-X)Ti(1+X)O5(式中，0＜X＜1)所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的金属成分比例含有含镁化合物、含铝化合物和含钛化合物的混合物，以及1～10质量份化学式：(NayK1-y)AlSi3O8(式中，0≤y≤1)所表示的碱性长石。
(3)上述(1)或(2)所述的废气净化蜂窝状过滤器，蜂窝状过滤器具有0.2～0.6mm的壁厚、15～47孔/cm2的孔密度，而且隔壁的气孔率为40～60％，热膨胀系数在3.0×10-6K-1以下。
(4)废气净化蜂窝状过滤器的制造方法，其特征在于，制备混合物，在该混合物中加入助成形剂混炼，进行可塑化使其可以挤出成形，挤出成形为蜂窝体后，在1000～1700℃下烧结，所述混合物是以与化学式：MgXAl2(1-X)Ti(1+X)O5(式中，0＜X＜1)所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的金属成分比例含有含镁化合物、含铝化合物和含钛化合物的混合物，或含有换算成氧化物的量为100质量份的所述混合物和1～10质量份化学式：(NayK1-y)AlSi3O8(0≤y≤1)所表示的碱性长石的混合物。
(5)上述(4)所述的废气净化蜂窝状过滤器的制造方法，所述混合物所含的各成分的平均粒径在30μm以下。
(6)废气净化装置，其特征在于，在缸体内装备上述(1)～(3)中的任一项所述的废气净化蜂窝状过滤器。
(7)上述(6)所述的废气净化装置，用于净化来自搭载柴油发动机的汽车的废气。
对于如上所述，本发明的钛酸铝镁烧结体的蜂窝状过滤器在具备原有的耐热性和较小的热膨胀系数，且耐热冲击性良好的同时，还具有高抗热分解性、以及较高的机械强度的原因并不清楚，但是大致推测是因为下述的原因。
即，钛酸铝镁具有其生成温度比钛酸铝更低的特性，由于其生成温度低，钛酸铝镁的热分解反应速度变小，抗热分解性提高。事实上，热分解反应速度与分解相的核的生成速度和生长速度的乘积成正比，而分解相的核的生成速度随过冷却度(与平衡状态的温度的差)增大而增加，另一方面，由于核的生长速度依赖于阳离子的扩散系数，所以随温度上升(过冷却度变小)而增加。因为它们互为相反的因子，所以意味着热分解反应速度在某一个过冷却度下达到极大值。这时，如果假定构成钛酸铝镁和钛酸铝的阳离子的同一温度下的扩散系数大致相同，则平衡分解温度越高，或过冷却度越大，热分解反应速度的极大值越大。钛酸铝镁的生成温度比钛酸铝低约100℃，所以达到热分解反应速度的极大值的过冷却度与钛酸铝的相比小很多。结果，钛酸铝镁的热分解反应被抑制，表现出良好的抗热分解性。
此外，在形成钛酸铝镁的混合物中添加碱性长石时，由于在生成钛酸铝镁的温度附近碱性长石呈液相存在，所以钛酸铝镁的生成反应在液相中进行，形成致密的结晶，机械强度提高。而且，碱性长石所含的Si成分固溶到钛酸铝镁的晶格中，但相比钛酸镁晶系更优先地固溶到钛酸铝晶系中。这是因为由于在假板钛矿型晶体结构中，钛酸铝构成晶体结构的八面体的畸变大，结晶学的各向异性显著，所以晶体结构不如钛酸镁稳定。
即，Si优先地固溶到钛酸铝的晶格中，主要占据Al的位置。这时，相比4价的Si单独置换本来3价的保持电荷平衡的Al的位置，更多地是与位于晶系内的2价的Mg形成一对，Si和Mg两者总共6价，置换相邻的2个Al(总共6价)。对于这一点，也可以从各阳离子的离子半径方面进行说明。
另一方面，由于Si4+和Mg2+的离子半径分别为0.54
Figure 200480018961X10000210003_0
和0.86，两者的平均离子半径为0.70，近似Al3+的离子半径0.68，Si和Mg的对替换Al比Si单独的置换在能量上是更合理的固溶状态。因此，由于同时存在Si和Mg，在高温下也可以抑制各阳离子之间的离子扩散，形成稳定的晶体结构，所以得到了更好的抗热分解性。
附图的简单说明
图1本发明的废气净化蜂窝状过滤器的一例的切去一部分后的立体示意图。
图2表示图1的蜂窝状过滤器的端面的模式图。
图3表示图2的蜂窝状过滤器的A-A线所在截面的模式图。
图4表示关于本发明的实施例1、2的各烧结体的钛酸铝镁的残存率α和关于比较例3的烧结体的钛酸铝的残存率β随时间的变化。
符号的说明
1：蜂窝状过滤器                    2：隔壁
3：通孔                            4、5：闭塞材料
实施发明的最佳方式
本发明中，蜂窝状过滤器的材质使用将混合物在1000～1700℃下烧结得到的钛酸铝镁烧结体，所述混合物含有换算成氧化物的量为100质量份的以与化学式：MgXAl2(1-X)Ti(1+X)O5(式中，0＜X＜1)所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的金属成分比例含有含镁化合物、含铝化合物和含钛化合物的混合物，以及1～10质量份化学式：(NayK1-y)AlSi3O8(式中，0≤y≤1)所表示的碱性长石。
作为原料使用的上述含镁化合物、含铝化合物和含钛化合物，只要是可以通过烧结合成钛酸铝镁的成分都可以使用，没有特别限定。含镁化合物、含铝化合物和含钛化合物可以不是分别不同的化合物，也可以是含有两种以上金属成分的化合物。这些原料化合物从通常用作为氧化铝陶瓷、二氧化钛陶瓷、氧化镁陶瓷、钛酸铝陶瓷、钛酸镁陶瓷、尖晶石陶瓷、钛酸铝镁陶瓷等各种陶瓷的原料的化合物中适当选择即可。这样的化合物的具体例子可以例举Al2O3、TiO2、MgO等氧化物，MgAl2O4、Al2TiO5、MgTi2O5、含Mg和Ti的各尖晶石型结构体等含2种以上金属成分的复合氧化物，含有选自Al、Ti和Mg的1种或2种以上的金属成分的化合物(碳酸盐、硝酸盐、硫酸盐等)。
含镁化合物、含铝化合物和含钛化合物的混合比例是使这些化合物所含的金属成分的比例为与上述化学式：MgXAl2(1-X)Ti(1+X)O5(式中，0＜X＜1，较好是0.2≤X≤0.8)所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的比例，较好实质上是同一比例。通过以这样的比例混合上述各化合物使用，可以得到具有与用作原料的混合物中金属成分比相同的金属成分比的钛酸铝镁。
要获得本发明的蜂窝状过滤器，较好是在上述含有含镁化合物、含铝化合物和含钛化合物的混合物中加入碱性长石作为添加剂。碱性长石是钛酸铝镁的烧结助剂，同时也兼具向钛酸铝镁中添加Si成分的作用，以化学式：(NayK1-y)AlSi3O8表示。式中，y满足0≤y≤1，较好是0.1≤y≤1，特别好是0.15≤y≤0.85。具有该范围内的y值的碱性长石熔点低，对促进钛酸铝镁的烧结特别有效。
碱性长石的使用量相对将各化合物换算成氧化物总计100质量份的作为原料使用的含镁化合物、含铝化合物和含钛化合物，为1～10质量份左右，较好是3～5质量份左右。这里的将混合物换算成氧化物的总量是指进行用于除去上述混合物中所含的水分和有机物的加热处理后，再进行预烧结的情况下，预烧结后、正式烧结前的质量。
本发明中，在含有含镁化合物、含铝化合物和含钛化合物的混合物、或者在该混合物中添加了碱性长石的混合物中，可以根据需要加入其它添加剂来改善得到的烧结体的性质。其它的添加剂可以例举例如SiO2、ZrO2、Fe2O3、MgO、Al2O3、TiO2、CaO、Y2O3等氧化物和含Mg的尖晶石型结构的氧化物等。其中一种或两种以上的添加剂相对100质量份上述混合物较好是添加15质量份以下。
上述混合物充分混合、粉碎。混合物的混合、粉碎没有特别限定，可以通过已知的方法进行。可以使用例如球磨机、介质搅拌机等进行。上述混合物的粉碎程度没有特别限定，平均粒径较好是在30μm以下，特别好为8～15μm以下。混合物只要是在不形成次级粒子的范围内，粒径越小越好。
较好是在上述混合物中加入助成形剂。助成形剂可以使用粘合剂、造孔剂、脱模剂、消泡剂和散凝剂等已知的助剂。粘合剂较好是聚乙烯醇、微晶蜡乳胶、甲基纤维素、羧甲基纤维素等。造孔剂较好是活性炭、焦炭、聚乙烯树脂、淀粉、石墨等。脱模剂较好是硬脂酸乳胶等，消泡剂较好是正辛醇、辛基苯氧基乙醇等，散凝剂较好是二乙胺、三乙胺等。
助成形剂的使用量没有特别限定，在本发明中，相对将各化合物换算成氧化物总计100质量份的用作原料的含镁化合物、含铝化合物和含钛化合物，全部以固体成分换算较好是分别在以下的范围内。即，粘合剂较好是使用0.2～0.6质量份左右，造孔剂较好是使用40～60质量份左右，脱模剂较好是使用0.2～0.7质量份左右，消泡剂较好是使用0.5～1.5质量份左右，散凝剂较好是使用0.5～1.5质量份左右。
加入上述助成形剂的混合物混合、混炼，将进行可塑化使其可以挤出成形的混合物通过挤出成形形成蜂窝体。挤出成形的方法可以使用已知的方法，蜂窝体的孔的截面形状可以是圆形、椭圆形、四边形、三角形中的任一种。此外，蜂窝体的整体形态可以是圆筒形、多边筒形。成形得到的蜂窝体较好是进行干燥，接着在1000～1700℃、较好是1250～1500℃下烧结。烧结的气氛没有特别限定，较好是通常采用的空气等含氧气氛。烧结时间进行到烧结充分为止，通常采用1～20小时左右。
进行上述烧结时的升温速度和降温速度也没有特别限定，适当设定使得到的烧结体上不出现裂缝等的条件即可。较好是例如，为了充分除去上述混合物中所含的水分、粘合剂等助成形剂，不是急剧地升温，而是缓缓地升温。此外，在加热至上述的烧结温度前，根据需要较好是在500～1000℃左右的温度范围内，通过10～30小时左右缓和的升温进行预烧结，从而可以缓解钛酸铝镁形成时引起裂缝产生的烧结体内的应力，能够抑制烧结体中裂缝的产生，从而得到均一的烧结体。
这样得到的烧结体是以化学式：MgXAl2(1-X)Ti(1+X)O5(式中，0＜X＜1)所表示的钛酸铝镁，或者是将其为基本成分、碱性长石所含的Si成分固溶在钛酸铝镁的晶格中的钛酸铝镁。如上所述，这样的烧结体成为兼具良好的耐热性和低膨胀系数，而且通过使晶体结构稳定化，具有良好的抗热分解性和高机械强度的烧结体。
其结果，由该烧结体构成的蜂窝状过滤器具有壁厚为例如0.2～0.6mm、较好是0.3～0.48mm，孔密度为例如15～47孔/cm2的薄壁蜂窝结构。而且，隔壁的气孔率为例如30～70％、较好是40～60％，热膨胀系数例如在3.0×10-6K-1以下、较好是在1.5×10-6K-1以下。该蜂窝状过滤器在从室温到1600℃左右的高温下，都可以抑制钛酸铝镁的热分解反应，稳定地使用。
图1是本发明的废气净化蜂窝状过滤器的一例的立体示意图。图2是表示图1的蜂窝状过滤器的端面的模式图，图3是表示图2的蜂窝状过滤器的A-A线所在截面的模式图。这些图中，废气净化蜂窝状过滤器1中，通过闭塞材料4、5交替地闭塞由以多个隔壁2构成的通孔3形成的蜂窝状过滤器的上游侧和下游侧的两端。即，如图2所示，在上游侧或下游侧的端部，闭塞材料4、5呈格子状地闭塞通孔3，而从通孔3的角度看是上游侧或下游侧的某一端部被闭塞材料4、5闭塞。对于这样的蜂窝体，将要净化的废气供给蜂窝体的上游侧的通孔3，通过其隔壁2，废气中的颗粒物被隔壁2捕获、除去后，净化后的废气从下游侧的通孔3排出。
废气净化蜂窝状过滤器较好是使用适当的保持材料装备在缸体中，用于捕获、除去废气中所含的以碳为主要成分的固体微粒(颗粒物)。关于废气的种类，可以将来自固定体和移动体的任一种的燃烧源等排出的气体作为对象，其中，如上所述，非常适用于净化来自搭载了对特性要求最严格的柴油发动机的汽车的废气。
实施例
以下，根据实施例对本发明进行具体说明，但是本发明当然并不限定于这些解释。
实施例1
对应于100质量份由26.7质量％(20摩尔％)易烧结性α型氧化铝、62.8质量％(60摩尔％)锐钛矿型氧化钛和10.5质量％(20摩尔％)作为天然矿物存在的方镁石(periclase)型氧化镁构成的混合物，加入0.25质量份作为粘合剂的聚乙烯醇、1质量份作为散凝剂的二乙胺、0.5质量份作为消泡剂的聚丙二醇和50质量份作为造孔剂的粒径50～80μm的活性炭，用球磨机混合3小时后，用干燥机在120℃下干燥12小时以上，得到原料粉末。
将得到的原料粉末粉碎到平均粒径10μm以下，用真空挤出成形机(宫崎铁工公司制)成形，得到蜂窝状成形体。将该成形体干燥后，于1500℃在大气中烧结2小时，然后通过放置冷却得到图1～图3所示的具有截面为四边形的孔的、整体为圆筒形的蜂窝状过滤器。该蜂窝状过滤器具有0.38mm的壁厚、31孔/cm2的孔密度，圆筒的外径为144mm、长为152mm。
实施例2
对应于100质量份由26.7质量％(20摩尔％)易烧结性α型氧化铝、62.8质量％(60摩尔％)锐钛矿型氧化钛和10.5质量％(20摩尔％)作为天然矿物存在的方镁石(periclase)型氧化镁构成的混合物，加入4质量份(Na0.6K0.4)AlSi3O8所表示的碱性长石、0.25质量份作为粘合剂的聚乙烯醇、1质量份作为散凝剂的二乙胺、0.5质量份作为消泡剂的聚丙二醇和50质量份作为造孔剂的粒径50～80μm的活性炭，用球磨机混合3小时后，用干燥机在120℃下干燥12小时以上，得到原料粉末。
使用得到的原料粉末，通过与实施例1同样地进行粉碎、成形、干燥和烧结得到与实施例1同样形状的蜂窝状过滤器。
比较例
分别使用市场上销售的碳化硅粉末(昭和电工公司制，商品名：ショゥセラム)、堇青石粉末(2MgO·2Al2O3·5SiO2)和钛酸铝粉末(Al2O3·TiO2)作为蜂窝状过滤器的材料，由这些材料通过用已知的方法操作，得到与实施例1相同形状的蜂窝状烧结体。其中，将碳化硅制蜂窝体作为比较例1，堇青石制蜂窝体作为比较例2，钛酸铝制蜂窝体作为比较例3。
[关于蜂窝状烧结体的特性试验]
对上述的实施例1、2和比较例1、2的蜂窝状烧结体测定气孔率(％)、从室温到800℃的热膨胀系数(×10-6K-1)、投入水中法得到的耐热冲击温度(℃)、软化温度(℃)和压缩强度(MPa)，其结果如表1所示。气孔率、热膨胀系数、耐热冲击温度、软化温度、压缩强度分别根据JISR1634、JISR1618、JISR1648、JISR2209、JISR1608的方法进行测定。测定压缩强度时，从各蜂窝状烧结体切取筒截面纵、横的孔数都为5个的、长度方向为15mm的方筒状检测样品，对其从(A)长度方向(axial)、(B)垂直方向(tangential)、(C)与长轴呈45度倾斜的方向(diagonal)3个方向进行测定。
表1
Figure G04818961X20060124D000091
由表1可知，实施例1、2和比较例1、2的蜂窝体实际使用中都保持了40～60％的范围内的充分的气孔率和压缩强度。但是实施例1、2的蜂窝体都具有比比较例1小得多的热膨胀系数，此外还具有比比较例2高得多的软化温度。另外，关于耐热冲击温度，实施例1、2都具有比比较例1、2高得多的特性。
[抗热分解性试验]
从实施例1、2的蜂窝状过滤器上切取全部是纵10mm×横10mm×长10mm的试验片，放置在1100℃的高温气氛中，通过考察钛酸铝镁的残存率α(％)随时间的变化进行抗热分解性试验。
钛酸铝镁的残存率从X射线衍射测定(XRD)的图谱通过以下方法求得。
首先，由于钛酸铝镁热分解时产生MgAl2O4(尖晶石)和TiO2(金红石)，用金红石的(110)面的衍射峰的积分强度(ITiO2(110))和钛酸铝镁的(023)面的衍射峰的积分强度(IMAT(023))通过下式求得钛酸铝镁对金红石的强度比R。
R＝IMAT(023)/(IMAT(023)+ITiO2(110))
另外，对在进行1100℃下的进行热处理前的烧结体也用同样的方法求得钛酸铝镁对金红石的强度比R0。接着，用上述方法求得的R和R0通过下式求得钛酸铝镁的残存率α(％)。
α＝(R/R0)×100
此外，从比较例3的蜂窝状过滤器上切取全部是纵10mm×横10mm×长10mm的试验片，放置在1100℃的高温气氛中，通过考察钛酸铝的残存率β(％)随时间的变化，进行与实施例1、2的比较。
钛酸铝的残存率从X射线衍射测定(XRD)的图谱通过以下方法求得。
首先，由于钛酸铝热分解时产生Al2O3(刚玉)和TiO2(金红石)，用金红石的(110)面的衍射峰的积分强度(ITiO2(110))和钛酸铝的(023)面的衍射峰的积分强度(IAT(023))通过下式求得钛酸铝对金红石的强度比r。
r＝IAT(023)/(IAT(023)+ITiO2(110))
另外，对在进行1100℃下的热处理前的烧结体也用同样的方法求得钛酸铝对金红石的强度比r0。接着，用上述方法求得的r和r0通过下式求得钛酸铝的残存率β(％)。
β＝(r/r0)×100
对于实施例1、2和比较例3的各烧结体，各结晶(实施例1、2为钛酸铝镁，比较例3为钛酸铝)的残存率α和β随时间的变化在图4中制成图表表示。由图4可知，实施例1、2与比较例3相比，残存率经过长时间仍维持较高，抗热分解性良好。另外，图4的经过200小时后的实施例1的残存率稍稍降低，但实施例2的烧结体依然维持较高的残存率，与实施例1相比抗热分解性更好。
实施例3～8
将易烧结性α型氧化铝、锐钛矿型氧化钛和方镁石型氧化镁以表2所示的各个比例混合，得到原料混合物。
表2
Figure G04818961X20060124D000101
对应于100质量份所得的混合物，加入4质量份化学式：(Na0.6K0.4)AlSi3O8所表示的碱性长石、0.25质量份作为粘合剂的聚乙烯醇、1质量份作为散凝剂的二乙胺、0.5质量份作为消泡剂的聚丙二醇和50质量份作为造孔剂的粒径50～80μm的活性炭，用球磨机混合3小时后，用干燥机在120℃下干燥12小时以上，得到原料粉末。
使用得到的原料粉末，通过与实施例1同样地进行粉碎、成形、干燥和烧结得到与实施例1同样形状的蜂窝状过滤器。
对实施例3～8中得到的蜂窝状烧结体与实施例1同样地试验其特性。其结果如表3所示。表3中也记载了化学式：MgXAl2(1-X)Ti(1+X)O5中X的值。
表3
Figure G04818961X20060124D000112
由表3可知，实施例3～8的烧结体实际使用中都保持了40～60％的范围内的充分的气孔率和压缩强度，具有低热膨胀系数、高耐热冲击性、高软化温度。
另外，对各蜂窝状过滤器通过与实施例1、2同样的方法求得保持在1100℃的大气中的状态下的钛酸铝镁的残存率α(％)随时间的变化。对于各烧结体，经过150小时后和经过200小时后的钛酸铝镁的残存率α(％)如表4所示。表4中也一并记载了对实施例1、2和比较例3的烧结体的测定结果。
表4
由表4可知，各实施例的烧结体具有良好的抗热分解性。
产业上利用的可能性
由本发明得到的钛酸铝镁烧结体构成的蜂窝状过滤器材料耐热性良好，维持低热膨胀系数、耐热冲击性，而且具有高抗热分解性和高机械强度，与以往的过滤器材料相比明显具有更优异的特性。因此，本发明的废气蜂窝状过滤器适合用作用于除去来自固定体和移动体的任一种的燃烧源的废气中的固体微粒。其中，如上所述，最适合用于净化来自搭载了对特性要求最严格的柴油发动机的汽车的废气。

Claims (6)

1.废气净化蜂窝状过滤器，其特征在于，该蜂窝状过滤器的材料为将混合物在1000～1700℃下烧结得到的钛酸铝镁烧结体，所述混合物含有：
1)换算成氧化物的量为100质量份的含镁化合物、含铝化合物和含钛化合物的混合物，所述含镁化合物、含铝化合物和含钛化合物的混合物以与化学式：MgXAl2(1-X)Ti(1+X)O5所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的金属成分比例含有含镁化合物、含铝化合物和含钛化合物，式中，0＜X＜1，以及
2)1～10质量份化学式：(NayK1-y)AlSi3O8所表示的碱性长石，式中，0≤y≤1。
2.如权利要求1所述的废气净化蜂窝状过滤器，其特征还在于，蜂窝状过滤器具有0.2～0.6mm的壁厚、15～47孔/cm2的孔密度，而且隔壁的气孔率为30～70％，热膨胀系数在3.0×10-6K-1以下。
3.废气净化蜂窝状过滤器的制造方法，其特征在于，制备混合物，在该混合物中加入助成形剂混炼，进行可塑化使其可以挤出成形，挤出成形为蜂窝体后，在1000～1700℃下烧结，所述混合物含有：
1)换算成氧化物的量为100质量份的含镁化合物、含铝化合物和含钛化合物的混合物，所述含镁化合物、含铝化合物和含钛化合物的混合物以与化学式：MgXAl2(1-X)Ti(1+X)O5所表示的钛酸铝镁中的Mg、Al和Ti的金属成分比同样的金属成分比例含有含镁化合物、含铝化合物和含钛化合物，式中，0＜X＜1，以及
2)1～10质量份化学式：(NayK1-y)AlSi3O8所表示的碱性长石，式中，0≤y≤1。
4.如权利要求3所述的废气净化蜂窝状过滤器的制造方法，其特征还在于，所述混合物所含的各成分的平均粒径在30μm以下。
5.废气净化装置，其特征在于，在缸体内装备权利要求1或2所述的废气净化蜂窝状过滤器。
6.如权利要求5所述的废气净化装置，其特征还在于，用于净化来自搭载柴油发动机的汽车的废气。
CN200480018961XA 2003-07-11 2004-07-09 废气净化蜂窝状过滤器及其制造方法 Expired - Fee Related CN1816379B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP196119/2003 2003-07-11
JP2003196119 2003-07-11
PCT/JP2004/010147 WO2005005019A1 (ja) 2003-07-11 2004-07-09 排ガス浄化ハニカムフィルタ及びその製造方法

Publications (2)

Publication Number Publication Date
CN1816379A CN1816379A (zh) 2006-08-09
CN1816379B true CN1816379B (zh) 2010-11-24

Family

ID=34055770

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200480018961XA Expired - Fee Related CN1816379B (zh) 2003-07-11 2004-07-09 废气净化蜂窝状过滤器及其制造方法

Country Status (9)

Country Link
US (1) US7575792B2 (zh)
EP (1) EP1645319B1 (zh)
JP (1) JP4950492B2 (zh)
KR (1) KR101093467B1 (zh)
CN (1) CN1816379B (zh)
CA (1) CA2528921A1 (zh)
PL (1) PL1645319T3 (zh)
TW (1) TW200502481A (zh)
WO (1) WO2005005019A1 (zh)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2533387A1 (en) 2003-07-29 2005-02-03 Ohcera Co., Ltd. Honeycomb carrier for exhaust gas-cleaning catalyst and process for its production
JP4609831B2 (ja) * 2003-07-29 2011-01-12 オーセラ株式会社 排ガス浄化触媒用ハニカム担体及びその製造方法
JP5123483B2 (ja) * 2003-08-22 2013-01-23 オーセラ株式会社 排ガス浄化ハニカムフィルタの製造方法
JP5230935B2 (ja) 2004-04-28 2013-07-10 オーセラ株式会社 チタン酸アルミニウムマグネシウム結晶構造物及びその製造方法
JP2007105622A (ja) * 2005-10-13 2007-04-26 Ohcera Co Ltd 排ガス浄化ハニカムフィルタ及びその製造方法
US10501375B2 (en) 2006-06-30 2019-12-10 Corning Incorporated Cordierite aluminum magnesium titanate compositions and ceramic articles comprising same
US8956436B2 (en) 2006-06-30 2015-02-17 Corning Incorporated Cordierite aluminum magnesium titanate compositions and ceramic articles comprising same
WO2008005249A2 (en) 2006-06-30 2008-01-10 Corning Incorporated Cordierite aluminum magnesium titanate compositions and ceramic articles comprising same
US7744669B2 (en) * 2006-07-14 2010-06-29 Corning Incorporated Plugging material for aluminum titanate ceramic wall flow filter manufacture
CN101484288A (zh) * 2006-09-28 2009-07-15 日立金属株式会社 陶瓷蜂窝结构体的制造方法及制造装置
US20100257829A1 (en) * 2007-09-28 2010-10-14 Kyocera Corporation Honeycomb Structure and Purifying Apparatus Using the Same
US20100300053A1 (en) * 2007-12-17 2010-12-02 Alary Jean-Andre Ceramic honeycomb structures
KR20100118976A (ko) * 2008-01-21 2010-11-08 스미또모 가가꾸 가부시끼가이샤 티탄산알루미늄마그네슘의 제조 방법
EP2202211A4 (en) * 2008-03-31 2011-09-28 Ibiden Co Ltd HONEYCOMB STRUCTURE
FR2931698B1 (fr) * 2008-05-29 2011-01-07 Saint Gobain Ct Recherches Structure en nid d'abeille a base de titanate d'aluminium.
JP2011523616A (ja) * 2008-05-29 2011-08-18 サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン チタン酸アルミニウムを含有する多孔質構造体
FR2933399B1 (fr) * 2008-07-04 2011-02-18 Saint Gobain Ct Recherches Melange de grains pour la synthese d'une structure poreuse du type titanate d'alumine
FR2933401B1 (fr) * 2008-07-04 2010-07-30 Saint Gobain Ct Recherches Structure poreuse du type titanate d'alumine
US8187353B2 (en) * 2009-01-21 2012-05-29 Corning Incorporated Filtration structures for improved particulate filter performance
BR112012022551A2 (pt) * 2010-03-08 2016-08-30 Sumitomo Chemical Co método para a produção de titanato de alumínio e magnésio poroso e titanato de alumínio e magnésio poroso
US20130043624A1 (en) * 2010-03-08 2013-02-21 Sumitomo Chemical Company, Limited Green compact and method for producing aluminum titanate sintered body
US9079799B2 (en) 2012-11-30 2015-07-14 Corning Incorporated Cordierite aluminum magnesium titanate compositions and ceramic articles comprising same
US10526249B2 (en) 2012-11-30 2020-01-07 Corning Incorporated Cordierite aluminum magnesium titanate compositions and ceramic articles comprising same
WO2022026236A1 (en) * 2020-07-30 2022-02-03 Corning Incorporated Aluminum titanate-feldspar ceramic bodies, batch mixtures, and methods of manufacture

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3366498A (en) * 1965-03-10 1968-01-30 Raymond G Osborne Lab Inc Ceramic bodies and preparation thereof
US3531307A (en) * 1967-02-23 1970-09-29 Intern Pipe & Ceramics Corp Ceramic article and method for producing same
US3930522A (en) * 1973-05-02 1976-01-06 General Refractories Company Structural ceramic article and method of making same
JPS5689844A (en) * 1979-12-25 1981-07-21 Asahi Glass Co Ltd Ceramic honeycomb and its production
JPS605545B2 (ja) 1980-03-19 1985-02-12 日本碍子株式会社 低膨脹セラミックスおよびその製法
JPS573767A (en) * 1980-06-04 1982-01-09 Nippon Toki Kk High temperature-stable high strength aluminium titanate sintered body
US4329162A (en) 1980-07-03 1982-05-11 Corning Glass Works Diesel particulate trap
US4483940A (en) * 1981-11-24 1984-11-20 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for manufacture of honeycomb catalyst
US4483944A (en) * 1983-07-27 1984-11-20 Corning Glass Works Aluminum titanate-mullite ceramic articles
JPS6030656A (ja) * 1983-07-29 1985-02-16 Soda Koryo Kk 香味入り豆腐
US4625511A (en) * 1984-08-13 1986-12-02 Arvin Industries, Inc. Exhaust processor
JPS6221756A (ja) * 1985-07-22 1987-01-30 日本碍子株式会社 チタン酸アルミニウム―ムライト系セラミック体の製造方法
JPH01296023A (ja) * 1988-05-24 1989-11-29 Nissin Kogyo Kk 輻射暖房を伴う強制通風空気調和方法並びにその装置
US5137789A (en) 1990-12-03 1992-08-11 Caterpillar Inc. Composite ceramic and metal article
JPH05115721A (ja) 1991-10-24 1993-05-14 Matsushita Electric Ind Co Ltd 排ガスフイルタおよびその製造方法
JPH05214922A (ja) 1992-02-05 1993-08-24 Asahi Glass Co Ltd ディーゼル機関用パティキュレートトラップ
JPH05306614A (ja) * 1992-04-28 1993-11-19 Matsushita Electric Ind Co Ltd 排気ガスフィルタとその製造方法
US5565245A (en) * 1993-07-28 1996-10-15 Virginia Tech Intellectual Properties, Inc. Magnesium doped β-aluminum titanate thin film coating
JPH08290963A (ja) 1995-04-21 1996-11-05 Matsushita Electric Ind Co Ltd 低熱膨張材料及びそれを用いた排ガスフィルター
JP3336157B2 (ja) * 1995-07-03 2002-10-21 京セラ株式会社 集塵用セラミックフィルタ
JPH0929024A (ja) * 1995-07-21 1997-02-04 Matsushita Electric Ind Co Ltd 排ガスフィルター
US6171373B1 (en) * 1996-04-23 2001-01-09 Applied Ceramics, Inc. Adsorptive monolith including activated carbon, method for making said monolith, and method for adsorbing chemical agents from fluid streams
JP3712785B2 (ja) * 1996-06-03 2005-11-02 松下電器産業株式会社 排ガスフィルタ及び排ガス浄化装置
JP3555382B2 (ja) * 1997-04-22 2004-08-18 松下電器産業株式会社 排ガスフィルターとその製造方法及びこの排ガスフィルターを備えたディーゼルエンジン
DE69817945D1 (de) * 1997-07-28 2003-10-16 Corning Inc Verfahren zur Herstellung von Cordierit-Körpern mittels Schnellbrand
US6206944B1 (en) * 1999-10-15 2001-03-27 Corning Incorporated Low aspect ratio diesel exhaust filter
JP2001037971A (ja) 2000-01-01 2001-02-13 Sankyo Kk 弾球遊技機の遊技盤用ゲージプレス
JP3600933B2 (ja) * 2000-11-08 2004-12-15 オーセラ株式会社 チタン酸アルミニウム系焼結体の製造方法
US6620751B1 (en) * 2002-03-14 2003-09-16 Corning Incorporated Strontium feldspar aluminum titanate for high temperature applications
CN101117286A (zh) 2002-11-01 2008-02-06 王世来股份有限公司 钛酸铝镁烧结体
CA2533387A1 (en) * 2003-07-29 2005-02-03 Ohcera Co., Ltd. Honeycomb carrier for exhaust gas-cleaning catalyst and process for its production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开平8-290963A 1996.11.05

Also Published As

Publication number Publication date
TW200502481A (en) 2005-01-16
PL1645319T3 (pl) 2013-12-31
US7575792B2 (en) 2009-08-18
EP1645319B1 (en) 2013-05-29
KR101093467B1 (ko) 2011-12-13
CA2528921A1 (en) 2005-01-20
EP1645319A4 (en) 2007-08-22
JPWO2005005019A1 (ja) 2006-08-24
CN1816379A (zh) 2006-08-09
EP1645319A1 (en) 2006-04-12
JP4950492B2 (ja) 2012-06-13
WO2005005019A1 (ja) 2005-01-20
US20070059484A1 (en) 2007-03-15
KR20060030855A (ko) 2006-04-11

Similar Documents

Publication Publication Date Title
CN1816379B (zh) 废气净化蜂窝状过滤器及其制造方法
CN100402127C (zh) 排气净化蜂窝状过滤器及其制造方法
US7923093B2 (en) High porosity filters for 4-way exhaust gas treatment
EP1911732B1 (en) Process for producing ceramic honeycomb structure
KR100931755B1 (ko) 고온에서 사용할 수 있는 스트론튬 펠드스파 알루미늄티타네이트
US7071135B2 (en) Ceramic body based on aluminum titanate and including a glass phase
US7001861B2 (en) Aluminum titanate-based ceramic article
CN101091925B (zh) 废气净化催化剂用蜂窝状载体及其制造方法
DE60318062T2 (de) Mullit-aluminium titanat dieselabgasfilter
JP3393554B2 (ja) 低熱膨脹で高気孔率のコージエライトボディおよびその製造方法
KR101971331B1 (ko) 알루미늄 티타네이트 조성물, 이를 포함하는 세라믹 제품, 및 이의 제조방법
US20120096821A1 (en) Process for producing aluminum titanate ceramics body
US20130269303A1 (en) Green formed body, and process for production of honeycomb structure
US20190177232A1 (en) Aluminum titanate compositions, aluminum titanate articles, and methods of making same
JP2011005417A (ja) ハニカムフィルタ及びその製造方法
WO2010150609A1 (ja) ハニカムフィルタ

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20101124

Termination date: 20190709

CF01 Termination of patent right due to non-payment of annual fee