WO2011061836A1 - ハニカム構造体及び排ガス浄化装置 - Google Patents

ハニカム構造体及び排ガス浄化装置 Download PDF

Info

Publication number
WO2011061836A1
WO2011061836A1 PCT/JP2009/069656 JP2009069656W WO2011061836A1 WO 2011061836 A1 WO2011061836 A1 WO 2011061836A1 JP 2009069656 W JP2009069656 W JP 2009069656W WO 2011061836 A1 WO2011061836 A1 WO 2011061836A1
Authority
WO
WIPO (PCT)
Prior art keywords
honeycomb structure
honeycomb
structure according
phosphate
zeolite
Prior art date
Application number
PCT/JP2009/069656
Other languages
English (en)
French (fr)
Inventor
陽介 松川
真之助 後藤
Original Assignee
イビデン株式会社
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 イビデン株式会社 filed Critical イビデン株式会社
Priority to CN200980162507.4A priority Critical patent/CN102666430B/zh
Priority to PCT/JP2009/069656 priority patent/WO2011061836A1/ja
Priority to EP10175407.5A priority patent/EP2324920B1/en
Priority to US12/910,876 priority patent/US8658104B2/en
Publication of WO2011061836A1 publication Critical patent/WO2011061836A1/ja

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006Honeycomb structures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447Shaped 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 phosphates, e.g. hydroxyapatite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
    • C04B35/6303Inorganic additives
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
    • C04B35/6303Inorganic additives
    • C04B35/6316Binders based on silicon compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • C04B35/82Asbestos; Glass; Fused silica
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003Joining 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
    • C04B37/005Joining 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201Alkali metal oxides or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3218Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232Titanium oxides or titanates, e.g. rutile or anatase
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427Silicates other than clay, e.g. water glass
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427Silicates other than clay, e.g. water glass
    • C04B2235/3436Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445Magnesium silicates, e.g. forsterite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427Silicates other than clay, e.g. water glass
    • C04B2235/3463Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3472Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36Glass starting materials for making ceramics, e.g. silica glass
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447Phosphates or phosphites, e.g. orthophosphate or hypophosphite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/522Oxidic
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/522Oxidic
    • C04B2235/5224Alumina or aluminates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/522Oxidic
    • C04B2235/5228Silica and alumina, including aluminosilicates, e.g. mullite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/522Oxidic
    • C04B2235/5232Silica or silicates other than aluminosilicates, e.g. quartz
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/524Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5244Silicon carbide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/526Fibers characterised by the length of the fibers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5264Fibers characterised by the diameter of the fibers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5292Flakes, platelets or plates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04Ceramic interlayers
    • C04B2237/09Ceramic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/10Glass interlayers, e.g. frit or flux
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32Ceramic
    • C04B2237/34Oxidic
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32Ceramic
    • C04B2237/38Fiber or whisker reinforced
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00Adding substances to exhaust gases
    • F01N2610/02Adding substances to exhaust gases the substance being ammonia or urea
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066Selective catalytic reduction [SCR]
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2803Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825Ceramics
    • F01N3/2828Ceramic multi-channel monoliths, e.g. honeycombs

Definitions

  • the present invention relates to a honeycomb structure and an exhaust gas purification apparatus having the honeycomb structure.
  • an SCR Selective Catalytic Reduction system that uses ammonia to reduce NOx to nitrogen and water has been known as one of systems for purifying automobile exhaust gas.
  • zeolite is known as a material that adsorbs ammonia in the SCR system.
  • the honeycomb unit includes inorganic particles and inorganic fibers and / or whiskers, and the inorganic particles are one or more selected from the group consisting of alumina, silica, zirconia, titania, ceria, mullite, and zeolite.
  • a honeycomb structure is disclosed.
  • the present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a honeycomb structure and an exhaust gas purification device that are excellent in NOx purification performance.
  • a honeycomb structure of the present invention includes a honeycomb unit including a phosphate-based zeolite and an inorganic binder, and a plurality of through holes arranged in parallel in a longitudinal direction with a partition wall therebetween.
  • the average pore diameter is 0.1 ⁇ m or more and 0.3 ⁇ m or less, and the porosity is 30% or more and 40% or less.
  • the phosphate zeolite is preferably at least one selected from the group consisting of SAPO, MeAPO, and MeAPSO. *
  • the SAPO is preferably one or more selected from the group consisting of SAPO-5, SAPO-11, and SAPO-34. *
  • the phosphate-based zeolite preferably includes zeolite ion-exchanged with Cu and / or Fe.
  • the inorganic binder is preferably a solid content contained in one or more selected from the group consisting of alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite and boehmite. *
  • the honeycomb unit preferably further includes inorganic fibers and / or scaly substances.
  • the inorganic fiber is at least one selected from the group consisting of alumina, silica, silicon carbide, silica alumina, glass, potassium titanate and aluminum borate, and the scaly substance includes glass, muscovite, alumina, silica and It is desirable to be at least one selected from the group consisting of zinc oxide.
  • the honeycomb structure of the present invention preferably includes a plurality of the honeycomb units.
  • the exhaust gas purification apparatus of the present invention has the honeycomb structure of the present invention.
  • FIG. Fig. 4 is a perspective view showing a honeycomb unit constituting the honeycomb structure of Fig. 3.
  • FIG. 1 shows an example of the honeycomb structure of the present invention.
  • the honeycomb structure 10 includes a phosphate-based zeolite as inorganic particles and an inorganic binder, and an outer peripheral surface of a single honeycomb unit 11 in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b interposed therebetween.
  • An outer peripheral coat layer 12 is formed on the outer periphery.
  • the average pore diameter of the macropores in the honeycomb unit 11 is 0.1 to 0.3 ⁇ m.
  • the average pore diameter of the macropores is less than 0.1 ⁇ m, the exhaust gas does not easily penetrate into the partition walls 11b, and thus the phosphate zeolite is not effectively used for the purification of NOx.
  • the average pore diameter of the macropores exceeds 0.3 ⁇ m, the number of pores in the honeycomb unit 11 is small, so that the exhaust gas hardly penetrates into the partition walls 11b, and the phosphate-based zeolite is used for purification of NOx. It will not be used effectively.
  • the pore size distribution of the honeycomb unit 11 includes a peak of micropores derived from phosphoric acid-based zeolite and a peak of macropores inside the partition walls 11b.
  • the porosity of the honeycomb unit 11 is 30 to 40%.
  • the porosity of the honeycomb unit 11 is less than 30%, the exhaust gas does not easily penetrate into the partition walls 11b, and thus the phosphate zeolite is not effectively used for purifying NOx.
  • the porosity of the honeycomb unit 11 exceeds 40%, the content of phosphate-based zeolite in the honeycomb unit 11 decreases, and the NOx purification rate decreases.
  • the average pore diameter and porosity of the honeycomb unit 11 can be measured using a mercury intrusion method.
  • phosphate zeolite examples include SAPO such as SAPO-5, SAPO-11, and SAPO-34; MeAPO; MeAPSO and the like.
  • the phosphate-based zeolite includes a phosphate-based zeolite ion-exchanged with Cu and / or Fe in consideration of NOx purification ability.
  • the phosphate-based zeolite may further include a phosphate-based zeolite that has not been ion-exchanged and a phosphate-based zeolite that has been ion-exchanged with a metal other than the above.
  • the phosphate zeolite ion-exchanged with Cu and / or Fe preferably has an ion exchange amount of 1.0 to 5.0% by mass.
  • the ion exchange amount of the phosphate zeolite is less than 1.0% by mass, the purification performance of NOx may be insufficient.
  • the ion exchange amount of the phosphate-based zeolite exceeds 5.0% by mass, the metal to be ion-exchanged may exist as an oxide and may not be ion-exchanged.
  • the average particle size of primary particles or secondary particles of phosphate zeolite is preferably 0.5 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • the average particle size of the primary particles or secondary particles of the phosphate zeolite is less than 0.5 ⁇ m, the exhaust gas hardly penetrates into the partition wall 11b, and the phosphate zeolite is effective for purifying NOx. May not be used.
  • the average particle size of the primary particles or secondary particles of the phosphate-based zeolite exceeds 10 ⁇ m, the number of pores in the honeycomb unit 11 is reduced, so that the exhaust gas is less likely to penetrate into the partition walls 11b. In some cases, acid-based zeolites may not be effectively used for NOx purification.
  • the honeycomb unit 11 may further include zeolite other than phosphate zeolite such as ⁇ -type zeolite and ZSM-5-type zeolite.
  • zeolite other than phosphate zeolite such as ⁇ -type zeolite and ZSM-5-type zeolite.
  • the honeycomb unit 11 preferably has a zeolite content of 230 to 360 g / L per apparent volume. If the zeolite content per apparent volume is less than 230 g / L, the apparent volume of the honeycomb unit 11 may have to be increased in order to improve the NOx purification rate. On the other hand, if the zeolite content per apparent volume exceeds 360 g / L, the strength of the honeycomb unit 11 may be insufficient, or the aperture ratio of the honeycomb unit 11 may be reduced.
  • the inorganic binder contained in the honeycomb unit 11 is not particularly limited, and examples thereof include solids contained in alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite and the like, and two or more kinds may be used in combination.
  • the content of the inorganic binder in the honeycomb unit 11 is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass. When the content of the inorganic binder is less than 5% by mass, the strength of the honeycomb unit 11 may be reduced. On the other hand, when the content of the inorganic binder exceeds 30% by mass, extrusion of the honeycomb unit 11 may be difficult.
  • the honeycomb unit 11 preferably further includes inorganic fibers and / or scaly substances in order to improve the strength.
  • the inorganic fibers contained in the honeycomb unit 11 are not particularly limited as long as the strength of the honeycomb unit 11 can be improved, but alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate Etc., and two or more of them may be used in combination.
  • the aspect ratio of the inorganic fiber is preferably 2 to 1000, more preferably 5 to 800, and particularly preferably 10 to 500.
  • the aspect ratio of the inorganic fiber is less than 2, the effect of improving the strength of the honeycomb unit 11 may be reduced.
  • the aspect ratio of the inorganic fiber exceeds 1000, the mold is clogged when the honeycomb unit 11 is extruded, or the inorganic fiber breaks and the effect of improving the strength of the honeycomb unit 11 is small. There are times when it becomes.
  • the scaly substance contained in the honeycomb unit 11 is not particularly limited as long as the strength of the honeycomb unit 11 can be improved, and examples thereof include glass, muscovite, alumina, silica, zinc oxide, and the like. You may use together.
  • the content of inorganic fibers and scaly substances in the honeycomb unit 11 is preferably 3 to 50% by mass, more preferably 3 to 30% by mass, and particularly preferably 5 to 20% by mass.
  • the content of the inorganic fibers and the scaly substance is less than 3% by mass, the effect of improving the strength of the honeycomb unit 11 may be reduced.
  • the content of inorganic fibers and scaly substances exceeds 50% by mass, the content of phosphate zeolite in the honeycomb unit 11 may decrease, and the NOx purification rate may decrease.
  • the honeycomb unit 11 preferably has an opening ratio of a cross section perpendicular to the longitudinal direction of 50 to 75%. If the opening ratio of the cross section perpendicular to the longitudinal direction is less than 50%, the phosphate zeolite may not be effectively used for NOx purification. On the other hand, when the opening ratio of the cross section perpendicular to the longitudinal direction exceeds 75%, the strength of the honeycomb unit 11 may be insufficient.
  • the density of the through holes 11a having a cross section perpendicular to the longitudinal direction is preferably 31 to 124 / cm 2 . If the density of the through holes 11a of the cross section perpendicular to the longitudinal direction is less than 31 / cm 2, less likely to contact exhaust gas and phosphate-based zeolite, the purification rate of NOx may decrease. On the other hand, when the density of the through holes 11a having a cross section perpendicular to the longitudinal direction exceeds 124 holes / cm 2 , the pressure loss of the honeycomb structure 10 may increase.
  • the thickness of the partition wall 11b of the honeycomb unit 11 is preferably 0.10 to 0.50 mm, and more preferably 0.15 to 0.35 mm. If the thickness of the partition wall 11b is less than 0.10 mm, the strength of the honeycomb unit 11 may be reduced. On the other hand, when the thickness of the partition wall 11b exceeds 0.50 mm, the exhaust gas hardly penetrates into the partition wall 11b, and the phosphate zeolite may not be effectively used for NOx purification.
  • the outer peripheral coat layer 12 preferably has a thickness of 0.1 to 2 mm. If the thickness of the outer peripheral coat layer 12 is less than 0.1 mm, the effect of improving the strength of the honeycomb structure 10 may be insufficient. On the other hand, if the thickness of the outer peripheral coat layer 12 exceeds 2 mm, the content of phosphate-based zeolite per unit volume of the honeycomb structure 10 may decrease, and the NOx purification rate may decrease.
  • the honeycomb structure 10 has a cylindrical shape, but is not particularly limited, and may have a prismatic shape, an elliptical column shape, or the like. Moreover, although the shape of the through-hole 11a is a quadrangular prism shape, it is not specifically limited, A triangular prism shape, a hexagonal column shape, etc. may be sufficient.
  • Extrusion molding is performed using a paste to produce a raw cylindrical honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween. Thereby, even if the firing temperature is lowered, the cylindrical honeycomb unit 11 having sufficient strength can be obtained.
  • the inorganic binder contained in the raw material paste is added as alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite, etc., and two or more kinds may be used in combination.
  • an organic binder, a dispersion medium, a molding aid and the like may be appropriately added to the raw material paste as necessary.
  • the organic binder is not particularly limited, and examples thereof include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, phenol resin, and epoxy resin, and two or more kinds may be used in combination.
  • the addition amount of the organic binder is preferably 1 to 10% with respect to the total mass of the zeolite other than the phosphate zeolite, the inorganic binder, the inorganic fiber, the scaly substance, and the phosphate zeolite.
  • the dispersion medium is not particularly limited, and examples thereof include water, organic solvents such as benzene, alcohols such as methanol, and the like.
  • the molding aid is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol and the like, and two or more kinds may be used in combination.
  • the raw material paste it is preferable to mix and knead, and it may be mixed using a mixer, an attritor or the like, or may be kneaded using a kneader or the like.
  • the obtained honeycomb formed body is dried using a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, or a freeze dryer.
  • a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, or a freeze dryer.
  • the obtained honeycomb formed body is degreased.
  • the degreasing conditions are not particularly limited and can be appropriately selected depending on the type and amount of the organic substance contained in the molded body, but it is preferably 400 ° C. for 2 hours.
  • the firing temperature is preferably 600 to 1200 ° C, more preferably 600 to 1000 ° C.
  • the firing temperature is less than 600 ° C.
  • the sintering does not proceed and the strength of the honeycomb unit 11 may be lowered.
  • the firing temperature exceeds 1200 ° C., sintering proceeds too much, and the reaction sites of the phosphate zeolite may decrease.
  • the outer peripheral coat layer paste is applied to the outer peripheral surface of the columnar honeycomb unit 11.
  • the outer periphery coating layer paste may further contain an organic binder.
  • an organic binder Polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose, etc. are mentioned, You may use 2 or more types together.
  • the outer peripheral coat layer paste contains an organic binder, it is preferably degreased.
  • the degreasing conditions can be appropriately selected depending on the kind and amount of the organic matter, but it is preferably 20 minutes at 700 ° C.
  • the phosphate zeolite can be ion-exchanged by immersing the honeycomb unit 11 in an aqueous solution containing Cu ions or Fe ions. Moreover, you may use the raw material paste containing the phosphate type zeolite ion-exchanged with Cu and / or Fe.
  • FIG. 2 shows an example of the exhaust gas purifying apparatus of the present invention.
  • the exhaust gas purification apparatus 100 is obtained by canning the metal tube 30 in a state where the holding sealing material 20 is disposed on the outer peripheral portion of the honeycomb structure 10.
  • the exhaust gas purification apparatus 100 is provided with injection means (not shown) such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • injection means such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • injection means such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • injection means such as an injection nozzle for injecting ammonia or a precursor thereof upstream of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows.
  • ammonia is added to the exhaust gas.
  • FIG. 3 shows a modification of the honeycomb structure 10.
  • the honeycomb structure 10 ′ has a configuration in which a plurality of honeycomb units 11 (see FIG. 4) in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b therebetween are bonded via an adhesive layer 13. This is the same as the honeycomb structure 10.
  • the honeycomb unit 11 preferably has a cross-sectional area of a cross section perpendicular to the longitudinal direction of 5 to 50 cm 2 .
  • the cross-sectional area of the cross section perpendicular to the longitudinal direction is less than 5 cm 2 , the pressure loss of the honeycomb structure 10 ′ may increase.
  • the cross-sectional area of the cross section perpendicular to the longitudinal direction exceeds 50 cm 2 , the strength against thermal stress generated in the honeycomb unit 11 may be insufficient.
  • the adhesive layer 13 preferably has a thickness of 0.5 to 2 mm. If the thickness of the adhesive layer 13 is less than 0.5 mm, the adhesive strength may be insufficient. On the other hand, when the thickness of the adhesive layer 13 exceeds 2 mm, the pressure loss of the honeycomb structure 10 ′ may increase.
  • the shape of the honeycomb unit 11 excluding the honeycomb unit 11 located on the outer peripheral portion of the honeycomb structure 10 ′ is a quadrangular column shape, but is not particularly limited, and may be, for example, a hexagonal column shape.
  • honeycomb structure 10 Next, an example of a method for manufacturing the honeycomb structure 10 'will be described. First, in the same manner as the honeycomb structure 10, a quadrangular columnar honeycomb unit 11 is manufactured. Next, an adhesive layer paste is applied to the outer peripheral surface of the honeycomb unit 11, the honeycomb units 11 are sequentially bonded, and dried and solidified, whereby an aggregate of the honeycomb units 11 is manufactured.
  • a honeycomb unit 11 having a columnar shape may be manufactured by bonding the honeycomb units 11 having a cross-section formed in a fan shape or a square shape.
  • the adhesive layer paste is not particularly limited, and examples thereof include a mixture of inorganic binder and inorganic particles, a mixture of inorganic binder and inorganic fibers, a mixture of inorganic binder, inorganic particles, and inorganic fibers.
  • the adhesive layer paste may contain an organic binder. Although it does not specifically limit as an organic binder, Polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose, etc. are mentioned, You may use 2 or more types together.
  • the outer peripheral coat layer paste is applied to the outer peripheral surface of the aggregate of the cylindrical honeycomb units 11.
  • the outer periphery coating layer paste is not particularly limited, it may contain the same material as the adhesive layer paste or may contain a different material. Further, the outer peripheral coat layer paste may have the same composition as the adhesive layer paste.
  • a cylindrical honeycomb structure 10 ′ is obtained.
  • an organic binder is contained in the adhesive layer paste and / or the outer peripheral coat layer paste, it is preferable to degrease.
  • the degreasing conditions can be appropriately selected depending on the kind and amount of the organic matter, but it is preferably 20 minutes at 700 ° C.
  • outer peripheral coat layer 12 may not be formed in the honeycomb structures 10 and 10 ′.
  • Example 1 First, SAPO 3100 g having an average particle diameter of 3.3 ⁇ m, 875 g boehmite, 485 g alumina fiber having an average fiber diameter of 100 ⁇ m, 380 g methylcellulose, 280 g oleic acid, ion-exchanged with 2.7% by mass with Cu And 2425 g of ion-exchanged water was mixed and kneaded to prepare a raw material paste 1.
  • the raw material paste 1 was extrusion-molded using an extruder, and a raw regular quadrangular prism-shaped honeycomb formed body was produced. Then, the honeycomb formed body was dried at 110 ° C. for 10 minutes using a microwave dryer and a hot air dryer, and then degreased at 400 ° C. for 5 hours. Next, the honeycomb unit 11 was fired at 700 ° C. for 2 hours to form a square prism-shaped honeycomb unit 11 having a side of 34.3 mm and a length of 150 mm.
  • the honeycomb unit 11 had a density of through-holes 11a of 93 / cm 2 , a partition wall 11b thickness of 0.23 mm, an average pore diameter of macropores of 0.20 ⁇ m, and a porosity of 35%.
  • the average pore diameter and porosity of the macropores were measured using a mercury porosimeter.
  • alumina fibers having an average fiber diameter of 0.5 ⁇ m and an average fiber length of 15 ⁇ m, 2500 g of silica glass, 17 g of carboxymethylcellulose, 600 g of silica sol having a solid content of 30% by mass, 167 g of polyvinyl alcohol, 167 g of surfactant, and 17 g of alumina balloon Were mixed and kneaded to prepare a heat-resistant adhesive layer paste.
  • the adhesive layer paste was applied so that the thickness of the adhesive layer was 2 mm, the 16 honeycomb units 11 were adhered, the adhesive layer paste was dried and solidified at 150 ° C. for 10 minutes, and then using a diamond cutter, The honeycomb unit 11 was assembled by cutting into a cylindrical shape so that the cross section perpendicular to the longitudinal direction was substantially point-symmetric.
  • the adhesive layer paste is used by using a microwave dryer and a hot air dryer.
  • a microwave dryer and a hot air dryer was dried and solidified at 150 ° C. for 10 minutes and degreased at 400 ° C. for 2 hours to produce a cylindrical honeycomb structure 10 ′ having a diameter of 143.8 mm and a height of 150 mm.
  • the honeycomb structure 10 ′ is canned to the metal pipe (shell) 30 to produce an exhaust gas purification device (see FIG. 2). .
  • Example 2 SAPO 3100 g having an average particle diameter of 1.3 ⁇ m, 895 g of boehmite, 485 g of alumina fibers having an average fiber length of 100 ⁇ m, 420 g of methyl cellulose, 280 g of oleic acid, and ions ion-exchanged with Cu by 2.7% by mass
  • the raw material paste 2 was prepared by mixing and kneading 2600 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 2 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.10 ⁇ m and a porosity of 35%.
  • SAPO 3100 g having an average particle diameter of 5.0 ⁇ m, boehmite 895 g, average fiber diameter 6 ⁇ m, average fiber length 100 ⁇ m alumina fiber 485 g, methylcellulose 350 g, oleic acid 280 g, and ions
  • the raw material paste 3 was prepared by mixing and kneading 2250 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 3 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.30 ⁇ m and a porosity of 35%.
  • Example 4 SAPO 3100 g having an average particle size of 3.3 ⁇ m, 895 g boehmite, 485 g alumina fiber having an average fiber length of 100 ⁇ m, 350 g of methyl cellulose, 280 g of oleic acid and ions ionic exchanged with Cu by 2.7% by mass
  • the raw material paste 4 was produced by mixing and kneading 2250 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 4 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.20 ⁇ m and a porosity of 30%.
  • Example 5 SAPO 3100 g having an average particle size of 3.3 ⁇ m, 895 g boehmite, 485 g of alumina fibers having an average fiber length of 100 ⁇ m, 420 g of methyl cellulose, 280 g of oleic acid and ions ion-exchanged with Cu by 2.7% by mass
  • the raw material paste 5 was prepared by mixing and kneading 2600 g of exchange water.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 5 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.20 ⁇ m and a porosity of 40%.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 6 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macro pores of 0.08 ⁇ m and a porosity of 32%.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were produced in the same manner as in Example 1 except that the raw material paste 7 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.35 ⁇ m and a porosity of 38%.
  • a honeycomb structure 10 ′ and an exhaust gas purification device were manufactured in the same manner as in Example 1 except that the raw material paste 8 was used instead of the raw material paste 1.
  • the honeycomb unit 11 had an average pore diameter of macropores of 0.20 ⁇ m and a porosity of 43%.
  • the NOx purification rate [%] represented by The constituent components of the simulated gas are 175 ppm of nitric oxide, 175 ppm of nitrogen dioxide, 350 ppm of ammonia, 14% by volume of oxygen, 5% by volume of carbon dioxide, 10% by volume of water, and nitrogen (balance). The measurement results are shown in Table 1.
  • the honeycomb unit 11 has an average pore diameter of 0.1 to 0.3 ⁇ m and a porosity of 30 to 40%. It is considered that the NOx purification performance is excellent.
  • honeycomb structure 10 ′ is shown, but it is considered that the same effect can be obtained with the honeycomb structure 10.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

 本発明のハニカム構造体は、リン酸塩系ゼオライトと、無機バインダとを含み、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカムユニットを有し、前記ハニカムユニットは、マクロ気孔の平均気孔径が0.1μm以上0.3μm以下であり、気孔率が30%以上40%以下である。

Description

ハニカム構造体及び排ガス浄化装置
 本発明は、ハニカム構造体及びハニカム構造体を有する排ガス浄化装置に関する。
 従来、自動車の排ガスを浄化するシステムの一つとして、アンモニアを用いて、NOxを窒素と水に還元するSCR(Selective Catalytic Reduction)システムが知られている。
 また、SCRシステムにおいて、アンモニアを吸着する材料として、ゼオライトが知られている。
 特許文献1には、ハニカムユニットが無機粒子と、無機繊維及び/又はウィスカを含んでなり、無機粒子は、アルミナ、シリカ、ジルコニア、チタニア、セリア、ムライト及びゼオライトからなる群より選択される一種以上であるハニカム構造体が開示されている。
国際公開第06/137149号パンフレット
 しかしながら、特許文献1のハニカム構造体において、無機粒子がゼオライトである場合よりも高いNOxの浄化性能が求められている。
 本発明は、上記の従来技術が有する問題に鑑み、NOxの浄化性能に優れるハニカム構造体及び排ガス浄化装置を提供することを目的とする。
 本発明のハニカム構造体は、リン酸塩系ゼオライトと、無機バインダとを含み、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカムユニットを有し、前記ハニカムユニットは、マクロ気孔の平均気孔径が0.1μm以上0.3μm以下であり、気孔率が30%以上40%以下である。
前記リン酸塩系ゼオライトは、SAPO、MeAPO及びMeAPSOからなる群より選択される一種以上であることが望ましい。 
前記SAPOは、SAPO-5、SAPO-11及びSAPO-34からなる群より選択される一種以上であることを特徴とすることが望ましい。 
前記リン酸塩系ゼオライトは、Cu及び/又はFeでイオン交換されているゼオライトを含むことが望ましい。 
前記無機バインダは、アルミナゾル、シリカゾル、チタニアゾル、水ガラス、セピオライト、アタパルジャイト及びベーマイトからなる群より選択される一種以上に含まれる固形分であることが望ましい。 
前記ハニカムユニットは、無機繊維及び/又は鱗片状物質をさらに含むことが望ましい。 
前記無機繊維は、アルミナ、シリカ、炭化ケイ素、シリカアルミナ、ガラス、チタン酸カリウム及びホウ酸アルミニウムからなる群より選択される一種以上であり、鱗片状物質は、ガラス、白雲母、アルミナ、シリカ及び酸化亜鉛からなる群より選択される一種以上であることが望ましい。
 本発明のハニカム構造体は、前記ハニカムユニットを複数有することが望ましい。
本発明の排ガス浄化装置は、本発明のハニカム構造体を有する。
 本発明によれば、NOxの浄化性能に優れるハニカム構造体及び排ガス浄化装置を提供することができる。
本発明のハニカム構造体の一例を示す斜視図である。 本発明の排ガス浄化装置の一例を示す断面図である。 図1のハニカム構造体の変形例を示す斜視図である。 図3のハニカム構造体を構成するハニカムユニットを示す斜視図である。
 次に、本発明を実施するための形態を図面と共に説明する。
 図1に、本発明のハニカム構造体の一例を示す。ハニカム構造体10は、無機粒子としてのリン酸塩系ゼオライトと、無機バインダとを含み、複数の貫通孔11aが隔壁11bを隔てて長手方向に並設された単一のハニカムユニット11の外周面に外周コート層12が形成されている。
 ハニカムユニット11のマクロ気孔の平均気孔径は、0.1~0.3μmである。マクロ気孔の平均気孔径が0.1μm未満であると、排ガスが隔壁11bの内部まで浸透しにくいため、リン酸塩系ゼオライトがNOxの浄化に有効に利用されなくなる。一方、マクロ気孔の平均気孔径が0.3μmを超えると、ハニカムユニット11中の気孔の数が少ないため、排ガスが隔壁11bの内部まで浸透しにくくなり、リン酸塩系ゼオライトがNOxの浄化に有効に利用されなくなる。
 このとき、ハニカムユニット11の気孔径分布には、リン酸系ゼオライト由来のミクロ気孔のピークと隔壁11bの内部のマクロ気孔のピークが存在する。
 ハニカムユニット11の気孔率は、30~40%である。ハニカムユニット11の気孔率が30%未満であると、排ガスが隔壁11bの内部まで浸透しにくいため、リン酸塩系ゼオライトがNOxの浄化に有効に利用されなくなる。一方、ハニカムユニット11の気孔率が40%を超えると、ハニカムユニット11中のリン酸塩系ゼオライトの含有量が少なくなるため、NOxの浄化率が低下する。
 なお、ハニカムユニット11の平均気孔径及び気孔率は、水銀圧入法を用いて測定することができる。
リン酸塩系ゼオライトとしては、SAPO-5、SAPO-11、SAPO-34等のSAPO;MeAPO;MeAPSO等が挙げられる。
 リン酸塩系ゼオライトは、NOx浄化能を考慮すると、Cu及び/又はFeでイオン交換されているリン酸塩系ゼオライトを含むことが好ましい。なお、リン酸塩系ゼオライトは、イオン交換されていないリン酸塩系ゼオライト、上記以外の金属でイオン交換されたリン酸塩系ゼオライトをさらに含んでもよい。
 Cu及び/又はFeでイオン交換されたリン酸塩系ゼオライトは、イオン交換量が1.0~5.0質量%であることが好ましい。リン酸塩系ゼオライトのイオン交換量が1.0質量%未満であると、NOxの浄化性能が不十分となることがある。一方、リン酸塩系ゼオライトのイオン交換量が5.0質量%を超えると、イオン交換されるべき金属が酸化物として存在して、イオン交換されないことがある。
 リン酸塩系ゼオライトの一次粒子又は二次粒子の平均粒径は、0.5~10μmであることが好ましく、1~5μmがさらに好ましい。リン酸塩系ゼオライトの一次粒子又は二次粒子の平均粒径が0.5μm未満であると、排ガスが隔壁11bの内部まで浸透しにくくなって、リン酸塩系ゼオライトがNOxの浄化に有効に利用されなくなることがある。一方、リン酸塩系ゼオライトの一次粒子又は二次粒子の平均粒径が10μmを超えると、ハニカムユニット11中の気孔の数が少なくなるため、排ガスが隔壁11bの内部まで浸透しにくくなり、リン酸塩系ゼオライトがNOxの浄化に有効に利用されなくなることがある。
 ハニカムユニット11は、β型ゼオライト、ZSM-5型ゼオライト等のリン酸塩系ゼオライト以外のゼオライトをさらに含んでもよい。
 ハニカムユニット11は、見掛けの体積当たりのゼオライトの含有量が230~360g/Lであることが好ましい。見掛けの体積当たりのゼオライトの含有量が230g/L未満であると、NOxの浄化率を向上させるためにハニカムユニット11の見掛けの体積を大きくしなければならないことがある。一方、見掛けの体積当たりのゼオライトの含有量が360g/Lを超えると、ハニカムユニット11の強度が不十分になること又はハニカムユニット11の開口率が小さくなることがある。
 ハニカムユニット11に含まれる無機バインダとしては、特に限定されないが、アルミナゾル、シリカゾル、チタニアゾル、水ガラス、セピオライト、アタパルジャイト、ベーマイト等に含まれる固形分が挙げられ、二種以上併用してもよい。
 ハニカムユニット11の無機バインダの含有量は、5~30質量%であることが好ましく、10~20質量%がさらに好ましい。無機バインダの含有量が5質量%未満であると、ハニカムユニット11の強度が低下することがある。一方、無機バインダの含有量が30質量%を超えると、ハニカムユニット11の押出成形が困難になることがある。
 ハニカムユニット11は、強度を向上させるために、無機繊維及び/又は鱗片状物質をさらに含むことが好ましい。
 ハニカムユニット11に含まれる無機繊維としては、ハニカムユニット11の強度を向上させることが可能であれば、特に限定されないが、アルミナ、シリカ、炭化ケイ素、シリカアルミナ、ガラス、チタン酸カリウム、ホウ酸アルミニウム等が挙げられ、二種以上併用してもよい。
 無機繊維のアスペクト比は、2~1000であることが好ましく、5~800がさらに好ましく、10~500が特に好ましい。無機繊維のアスペクト比が2未満であると、ハニカムユニット11の強度を向上させる効果が小さくなることがある。一方、無機繊維のアスペクト比が1000を超えると、ハニカムユニット11を押出成形する際に金型に目詰まり等が発生したり、無機繊維が折れて、ハニカムユニット11の強度を向上させる効果が小さくなったりすることがある。
 ハニカムユニット11に含まれる鱗片状物質としては、ハニカムユニット11の強度を向上させることが可能であれば、特に限定されないが、ガラス、白雲母、アルミナ、シリカ、酸化亜鉛等が挙げられ、二種以上併用してもよい。
 ハニカムユニット11の無機繊維及び鱗片状物質の含有量は、3~50質量%であることが好ましく、3~30質量%がさらに好ましく、5~20質量%が特に好ましい。無機繊維及び鱗片状物質の含有量が3質量%未満であると、ハニカムユニット11の強度を向上させる効果が小さくなることがある。一方、無機繊維及び鱗片状物質の含有量が50質量%を超えると、ハニカムユニット11中のリン酸塩系ゼオライトの含有量が低下して、NOxの浄化率が低下することがある。
 ハニカムユニット11は、長手方向に垂直な断面の開口率が50~75%であることが好ましい。長手方向に垂直な断面の開口率が50%未満であると、リン酸塩系ゼオライトがNOxの浄化に有効に利用されなくなることがある。一方、長手方向に垂直な断面の開口率が75%を超えると、ハニカムユニット11の強度が不十分となることがある。
 ハニカムユニット11は、長手方向に垂直な断面の貫通孔11aの密度が31~124個/cmであることが好ましい。長手方向に垂直な断面の貫通孔11aの密度が31個/cm未満であると、排ガスとリン酸塩系ゼオライトが接触しにくくなって、NOxの浄化率が低下することがある。一方、長手方向に垂直な断面の貫通孔11aの密度が124個/cmを超えると、ハニカム構造体10の圧力損失が増大することがある。
 ハニカムユニット11の隔壁11bの厚さは、0.10~0.50mmであることが好ましく、0.15~0.35mmがさらに好ましい。隔壁11bの厚さが0.10mm未満であると、ハニカムユニット11の強度が低下することがある。一方、隔壁11bの厚さが0.50mmを超えると、排ガスが隔壁11bの内部まで浸透しにくくなって、リン酸塩系ゼオライトがNOxの浄化に有効に利用されなくなることがある。
 外周コート層12は、厚さが0.1~2mmであることが好ましい。外周コート層12の厚さが0.1mm未満であると、ハニカム構造体10の強度を向上させる効果が不十分になることがある。一方、外周コート層12の厚さが2mmを超えると、ハニカム構造体10の単位体積当たりのリン酸塩系ゼオライトの含有量が低下して、NOxの浄化率が低下することがある。
 ハニカム構造体10は、円柱状であるが、特に限定されず、角柱状、楕円柱状等であってもよい。また、貫通孔11aの形状は、四角柱状であるが、特に限定されず、三角柱状、六角柱状等であってもよい。
 次に、ハニカム構造体10の製造方法の一例について説明する。まず、リン酸塩系ゼオライト及び無機バインダを含み、必要に応じて、無機繊維及び/又は鱗片状物質、β型ゼオライト、ZSM-5型ゼオライト等のリン酸塩系ゼオライト以外のゼオライトをさらに含む原料ペーストを用いて押出成形し、複数の貫通孔が隔壁を隔てて長手方向に並設された生の円柱状のハニカム成形体を作製する。これにより、焼成温度を低くしても、十分な強度を有する円柱状のハニカムユニット11が得られる。
 なお、原料ペーストに含まれる無機バインダは、アルミナゾル、シリカゾル、チタニアゾル、水ガラス、セピオライト、アタパルジャイト、ベーマイト等として添加されており、二種以上併用されていてもよい。
 また、原料ペーストには、有機バインダ、分散媒、成形助剤等を、必要に応じて、適宜添加してもよい。
 有機バインダとしては、特に限定されないが、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリエチレングリコール、フェノール樹脂、エポキシ樹脂等が挙げられ、二種以上併用してもよい。なお、有機バインダの添加量は、リン酸塩系ゼオライト、無機バインダ、無機繊維、鱗片状物質及びリン酸塩系ゼオライト以外のゼオライトの総質量に対して、1~10%であることが好ましい。
 分散媒としては、特に限定されないが、水、ベンゼン等の有機溶媒、メタノール等のアルコール等が挙げられ、二種以上併用してもよい。
 成形助剤としては、特に限定されないが、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、二種以上併用してもよい。
 原料ペーストを調製する際には、混合混練することが好ましく、ミキサー、アトライタ等を用いて混合してもよく、ニーダー等を用いて混練してもよい。
 次に、マイクロ波乾燥機、熱風乾燥機、誘電乾燥機、減圧乾燥機、真空乾燥機、凍結乾燥機等の乾燥機を用いて、得られたハニカム成形体を乾燥する。
 さらに、得られたハニカム成形体を脱脂する。脱脂条件は、特に限定されず、成形体に含まれる有機物の種類や量によって適宜選択することができるが、400℃で2時間であることが好ましい。
 次に、得られたハニカム成形体を焼成することにより、円柱状のハニカムユニット11が得られる。焼成温度は、600~1200℃であることが好ましく、600~1000℃がさらに好ましい。焼成温度が600℃未満であると、焼結が進行せず、ハニカムユニット11の強度が低くなることがある。一方、焼成温度が1200℃を超えると、焼結が進行しすぎて、リン酸塩系ゼオライトの反応サイトが減少することがある。
 次に、円柱状のハニカムユニット11の外周面に外周コート層用ペーストを塗布する。
 外周コート層用ペーストとしては、特に限定されないが、無機バインダ及び無機粒子の混合物、無機バインダ及び無機繊維の混合物、無機バインダ、無機粒子及び無機繊維の混合物等が挙げられる。
 また、外周コート層用ペーストは、有機バインダをさらに含有してもよい。有機バインダとしては、特に限定されないが、ポリビニルアルコール、メチルセルロース、エチルセルロース、カルボキシメチルセルロース等が挙げられ、二種以上併用してもよい。
 次に、外周コート層用ペーストが塗布されたハニカムユニット11を乾燥固化することにより、円柱状のハニカム構造体10が得られる。このとき、外周コート層用ペーストに有機バインダが含まれている場合は、脱脂することが好ましい。脱脂条件は、有機物の種類や量によって適宜選択することができるが、700℃で20分間であることが好ましい。
 なお、ハニカムユニット11をCuイオン又はFeイオンを含有する水溶液中に浸漬することにより、リン酸塩系ゼオライトをイオン交換することができる。また、Cu及び/又はFeでイオン交換されたリン酸塩系ゼオライトを含む原料ペーストを用いてもよい。
 図2に、本発明の排ガス浄化装置の一例を示す。排ガス浄化装置100は、ハニカム構造体10の外周部に保持シール材20を配置した状態で、金属管30にキャニングすることにより得られる。また、排ガス浄化装置100には、排ガスの流れる方向に対して、ハニカム構造体10の上流側に、アンモニア又はその前駆体を噴射する噴射ノズル等の噴射手段(不図示)が設けられている。これにより、排ガスにアンモニアが添加され、その結果、ハニカムユニット11に含まれるリン酸塩系ゼオライト上で、排ガス中に含まれるNOxが還元される。このとき、アンモニア又はその前駆体の貯蔵安定性を考慮すると、アンモニアの前駆体として、尿素水を用いることが好ましい。なお、尿素水は、排ガス中で加熱されることにより、加水分解し、アンモニアが発生する。
 図3に、ハニカム構造体10の変形例を示す。なお、ハニカム構造体10’は、複数の貫通孔11aが隔壁11bを隔てて長手方向に並設されたハニカムユニット11(図4参照)が接着層13を介して複数個接着されている以外は、ハニカム構造体10と同様である。
 ハニカムユニット11は、長手方向に垂直な断面の断面積が5~50cmであることが好ましい。長手方向に垂直な断面の断面積が5cm未満であると、ハニカム構造体10’の圧力損失が増大することがある。一方、長手方向に垂直な断面の断面積が50cmを超えると、ハニカムユニット11に発生する熱応力に対する強度が不十分になることがある。
 接着層13は、厚さが0.5~2mmであることが好ましい。接着層13の厚さが0.5mm未満であると、接着強度が不十分になることがある。一方、接着層13の厚さが2mmを超えると、ハニカム構造体10’の圧力損失が増大することがある。
 また、ハニカム構造体10’の外周部に位置するハニカムユニット11を除くハニカムユニット11の形状は、四角柱状であるが、特に限定されず、例えば、六角柱状等であってもよい。
 次に、ハニカム構造体10’の製造方法の一例について説明する。まず、ハニカム構造体10と同様にして、四角柱状のハニカムユニット11を作製する。次に、ハニカムユニット11の外周面に接着層用ペーストを塗布して、ハニカムユニット11を順次接着させ、乾燥固化することにより、ハニカムユニット11の集合体を作製する。
 このとき、ハニカムユニット11の集合体を作製した後に、円柱状に切削加工し、研磨してもよい。また、断面が扇形状や正方形状に成形されたハニカムユニット11を接着させて円柱状のハニカムユニット11の集合体を作製してもよい。
 接着層用ペーストとしては、特に限定されないが、無機バインダ及び無機粒子の混合物、無機バインダ及び無機繊維の混合物、無機バインダ、無機粒子及び無機繊維の混合物等が挙げられる。
 また、接着層用ペーストは、有機バインダを含有してもよい。有機バインダとしては、特に限定されないが、ポリビニルアルコール、メチルセルロース、エチルセルロース、カルボキシメチルセルロース等が挙げられ、二種以上併用してもよい。
 次に、円柱状のハニカムユニット11の集合体の外周面に外周コート層用ペーストを塗布する。外周コート層用ペーストは、特に限定されないが、接着層用ペーストと同じ材料を含有してもよいし、異なる材料を含有してもよい。また、外周コート層用ペーストは、接着層用ペーストと同一の組成であってもよい。
 次に、外周コート層用ペーストが塗布されたハニカムユニット11の集合体を乾燥固化することにより、円柱状のハニカム構造体10’が得られる。このとき、接着層用ペースト及び/又は外周コート層用ペーストに有機バインダが含まれている場合は、脱脂することが好ましい。脱脂条件は、有機物の種類や量によって適宜選択することができるが、700℃で20分間であることが好ましい。
 なお、ハニカム構造体10及び10’は、外周コート層12が形成されていなくてもよい。
 [実施例1]
 まず、Cuで2.7質量%イオン交換された、平均粒径が3.3μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース380g、オレイン酸280g及びイオン交換水2425gを混合混練して、原料ペースト1を作製した。
 次に、押出成形機を用いて、原料ペースト1を押出成形し、生の正四角柱状のハニカム成形体を作製した。そして、マイクロ波乾燥機及び熱風乾燥機を用いて、ハニカム成形体を110℃で10分間乾燥させた後、400℃で5時間脱脂した。次に、700℃で2時間焼成し、一辺が34.3mm、長さが150mmの正四角柱状のハニカムユニット11を作製した。
 ハニカムユニット11は、貫通孔11aの密度が93個/cm、隔壁11bの厚さが0.23mm、マクロ気孔の平均気孔径が0.20μm、気孔率が35%であった。ここで、マクロ気孔の平均気孔径及び気孔率は、水銀ポロシメーターを用いて測定した。
 次に、平均繊維径が0.5μm、平均繊維長が15μmのアルミナ繊維767g、シリカガラス2500g、カルボキシメチルセルロース17g、固形分30質量%のシリカゾル600g、ポリビニルアルコール167g、界面活性剤167g及びアルミナバルーン17gを混合混練して、耐熱性の接着層用ペーストを作製した。
 接着層の厚さが2mmになるように接着層用ペーストを塗布して、ハニカムユニット11を16個接着させ、接着層用ペーストを150℃で10分間乾燥固化した後、ダイヤモンドカッターを用いて、長手方向に垂直な断面が略点対称になるように円柱状に切削加工し、ハニカムユニット11の集合体を作製した。
 さらに、ハニカムユニット11の集合体の外周面に、外周コート層の厚さが1mmになるように接着層用ペーストを塗布した後、マイクロ波乾燥機及び熱風乾燥機を用いて、接着層用ペーストを150℃で10分間乾燥固化し、400℃で2時間脱脂して、直径143.8mm、高さ150mmの円柱状のハニカム構造体10’を作製した。
 次に、ハニカム構造体10’の外周部に保持シール材(無機繊維からなるマット)20を配置した状態で、金属管(シェル)30にキャニングし、排ガス浄化装置を作製した(図2参照)。
 [実施例2]
 Cuで2.7質量%イオン交換された、平均粒径が1.3μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース420g、オレイン酸280g及びイオン交換水2600gを混合混練して、原料ペースト2を作製した。
 原料ペースト1の代わりに、原料ペースト2を用いた以外は、実施例1と同様にして、ハニカム構造体10’及び排ガス浄化装置を作製した。
 なお、ハニカムユニット11は、マクロ気孔の平均気孔径が0.10μm、気孔率が35%であった。
 [実施例3]
 Cuで2.7質量%イオン交換された、平均粒径が5.0μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース350g、オレイン酸280g及びイオン交換水2250gを混合混練して、原料ペースト3を作製した。
 原料ペースト1の代わりに、原料ペースト3を用いた以外は、実施例1と同様にして、ハニカム構造体10’及び排ガス浄化装置を作製した。
 なお、ハニカムユニット11は、マクロ気孔の平均気孔径が0.30μm、気孔率が35%であった。
 [実施例4]
 Cuで2.7質量%イオン交換された、平均粒径が3.3μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース350g、オレイン酸280g及びイオン交換水2250gを混合混練して、原料ペースト4を作製した。
 原料ペースト1の代わりに、原料ペースト4を用いた以外は、実施例1と同様にして、ハニカム構造体10’及び排ガス浄化装置を作製した。
 なお、ハニカムユニット11は、マクロ気孔の平均気孔径が0.20μm、気孔率が30%であった。
 [実施例5]
 Cuで2.7質量%イオン交換された、平均粒径が3.3μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース420g、オレイン酸280g及びイオン交換水2600gを混合混練して、原料ペースト5を作製した。
 原料ペースト1の代わりに、原料ペースト5を用いた以外は、実施例1と同様にして、ハニカム構造体10’及び排ガス浄化装置を作製した。
 なお、ハニカムユニット11は、マクロ気孔の平均気孔径が0.20μm、気孔率が40%であった。
 [比較例1]
 Cuで2.7質量%イオン交換された、平均粒径が1.3μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース380g、オレイン酸280g及びイオン交換水2425gを混合混練して、原料ペースト6を作製した。
 原料ペースト1の代わりに、原料ペースト6を用いた以外は、実施例1と同様にして、ハニカム構造体10’及び排ガス浄化装置を作製した。
 なお、ハニカムユニット11は、マクロ気孔の平均気孔径が0.08μm、気孔率が32%であった。
 [比較例2]
 Cuで2.7質量%イオン交換された、平均粒径が5.5μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース350g、オレイン酸280g及びイオン交換水2250gを混合混練して、原料ペースト7を作製した。
 原料ペースト1の代わりに、原料ペースト7を用いた以外は、実施例1と同様にして、ハニカム構造体10’及び排ガス浄化装置を作製した。
 なお、ハニカムユニット11は、マクロ気孔の平均気孔径が0.35μm、気孔率が38%であった。
 [比較例3]
 Cuで2.7質量%イオン交換された、平均粒径が3.3μmであるSAPO3100g、ベーマイト895g、平均繊維径が6μm、平均繊維長が100μmのアルミナ繊維485g、メチルセルロース450g、オレイン酸280g及びイオン交換水2740gを混合混練して、原料ペースト8を作製した。
 原料ペースト1の代わりに、原料ペースト8を用いた以外は、実施例1と同様にして、ハニカム構造体10’及び排ガス浄化装置を作製した。
 なお、ハニカムユニット11は、マクロ気孔の平均気孔径が0.20μm、気孔率が43%であった。
 [NOxの浄化率の測定]
 実施例1~5及び比較例1~3で作製したハニカム構造体10’から、一辺が34.3mm、長さが40mmの正四角柱状のハニカムユニット11の一部を切り出し、評価用の試料とした。
 各評価用の試料に、150℃の模擬ガスを空間速度(SV)35000/hrで流しながら、触媒評価装置SIGU(堀場製作所社製)を用いて、評価用の試料から流出する一酸化窒素(NO)の流出量を測定し、式
 (NOの流入量-NOの流出量)/(NOの流入量)×100
で表されるNOxの浄化率[%]を測定した。なお、模擬ガスの構成成分は、一酸化窒素175ppm、二酸化窒素175ppm、アンモニア350ppm、酸素14体積%、二酸化炭素5体積%、水10体積%、窒素(balance)である。測定結果を表1に示す。
Figure JPOXMLDOC01-appb-T000001
 
表1より、実施例1~5で作製したハニカム構造体10’から切り出した評価用の試料は、NOxの浄化率が高いことがわかる。
 以上のことから、ハニカムユニット11は、マクロ気孔の平均気孔径が0.1~0.3μmであり、気孔率が30~40%であることにより、ハニカム構造体10’及び排ガス浄化装置は、NOxの浄化性能に優れると考えられる。
 なお、本実施例では、ハニカム構造体10’について示したが、ハニカム構造体10についても同様の効果が得られると考えられる。
 10、10’  ハニカム構造体
 11  ハニカムユニット
 11a  貫通孔
 11b  隔壁
 12  外周コート層
 13  接着層
 20  保持シール材
 30  金属管
 100  排ガス浄化装置

Claims (9)

  1.  リン酸塩系ゼオライトと、無機バインダとを含み、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカムユニットを有するハニカム構造体であって、
     前記ハニカムユニットは、マクロ気孔の平均気孔径が0.1μm以上0.3μm以下であり、気孔率が30%以上40%以下であることを特徴とするハニカム構造体。
  2. 前記リン酸塩系ゼオライトは、SAPO、MeAPO及びMeAPSOからなる群より選択される一種以上であることを特徴とする請求項1に記載のハニカム構造体。
  3. 前記SAPOは、SAPO-5、SAPO-11及びSAPO-34からなる群より選択される一種以上であることを特徴とすることを特徴とする請求項2に記載のハニカム構造体。
  4. 前記リン酸塩系ゼオライトは、Cu及び/又はFeでイオン交換されているゼオライトを含むことを特徴とする請求項1乃至3のいずれか一項に記載のハニカム構造体。
  5.  前記無機バインダは、アルミナゾル、シリカゾル、チタニアゾル、水ガラス、セピオライト、アタパルジャイト及びベーマイトからなる群より選択される一種以上に含まれる固形分であることを特徴とする請求項1乃至4のいずれか一項に記載のハニカム構造体。
  6.  前記ハニカムユニットは、無機繊維及び/又は鱗片状物質をさらに含むことを特徴とする請求項1乃至5のいずれか一項に記載のハニカム構造体。
  7. 前記無機繊維は、アルミナ、シリカ、炭化ケイ素、シリカアルミナ、ガラス、チタン酸カリウム及びホウ酸アルミニウムからなる群より選択される一種以上であり、 鱗片状物質は、ガラス、白雲母、アルミナ、シリカ及び酸化亜鉛からなる群より選択される一種以上であることを特徴とする請求項6に記載のハニカム構造体。
  8. 前記ハニカムユニットを複数有することを特徴とする請求項1乃至7のいずれか一項に記載のハニカム構造体。
  9. 請求項1乃至8のいずれか一項に記載のハニカム構造体を有することを特徴とする排ガス浄化装置。
PCT/JP2009/069656 2009-11-19 2009-11-19 ハニカム構造体及び排ガス浄化装置 WO2011061836A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN200980162507.4A CN102666430B (zh) 2009-11-19 2009-11-19 蜂窝结构体以及尾气净化装置
PCT/JP2009/069656 WO2011061836A1 (ja) 2009-11-19 2009-11-19 ハニカム構造体及び排ガス浄化装置
EP10175407.5A EP2324920B1 (en) 2009-11-19 2010-09-06 Honeycomb structural body and exhaust gas conversion apparatus
US12/910,876 US8658104B2 (en) 2009-11-19 2010-10-25 Honeycomb structural body and exhaust gas conversion apparatus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2009/069656 WO2011061836A1 (ja) 2009-11-19 2009-11-19 ハニカム構造体及び排ガス浄化装置

Publications (1)

Publication Number Publication Date
WO2011061836A1 true WO2011061836A1 (ja) 2011-05-26

Family

ID=43827287

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/069656 WO2011061836A1 (ja) 2009-11-19 2009-11-19 ハニカム構造体及び排ガス浄化装置

Country Status (4)

Country Link
US (1) US8658104B2 (ja)
EP (1) EP2324920B1 (ja)
CN (1) CN102666430B (ja)
WO (1) WO2011061836A1 (ja)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014054143A1 (ja) 2012-10-03 2014-04-10 イビデン株式会社 ハニカム構造体
EP2845648A2 (en) 2013-08-27 2015-03-11 Ibiden Co., Ltd. Honeycomb catalyst and exhaust gas purifying apparatus
JP5732169B1 (ja) * 2013-12-27 2015-06-10 イビデン株式会社 ゼオライトの製造方法及びハニカム触媒
JP5740040B1 (ja) * 2014-07-07 2015-06-24 イビデン株式会社 ゼオライト、ハニカム触媒及び排ガス浄化装置
US9878315B2 (en) 2014-07-07 2018-01-30 Ibiden Co., Ltd. Zeolite, method for manufacturing zeolite, honeycomb catalyst, and exhaust gas purifying apparatus

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012029159A1 (ja) * 2010-09-02 2012-03-08 イビデン株式会社 シリコアルミナリン酸塩、ハニカム構造体及び排ガス浄化装置
CN102877920B (zh) * 2012-10-09 2014-09-17 浙江达峰汽车技术有限公司 机动车尾气催化净化器用载体
JP6245895B2 (ja) * 2013-08-27 2017-12-13 イビデン株式会社 ハニカム触媒及び排ガス浄化装置
GB2522435B (en) * 2014-01-23 2018-10-03 Johnson Matthey Plc Catalytic extruded solid honeycomb body
JP6231908B2 (ja) * 2014-03-14 2017-11-15 日本碍子株式会社 目封止ハニカム構造体
JP6081951B2 (ja) * 2014-03-26 2017-02-15 日本碍子株式会社 ハニカム構造体の製造方法
JP6764451B2 (ja) * 2018-09-12 2020-09-30 イビデン株式会社 ハニカム構造体の製造方法
JP6771005B2 (ja) * 2018-09-12 2020-10-21 イビデン株式会社 ハニカム構造体の製造方法
CN110711489A (zh) * 2019-11-12 2020-01-21 庆泓技术(上海)有限公司 一种生活垃圾恶臭与生活污水臭气的去除方法
CN110721579A (zh) * 2019-11-12 2020-01-24 庆泓技术(上海)有限公司 一种用于冰箱除臭杀菌的方法
CN115417669A (zh) * 2022-09-30 2022-12-02 武汉科技大学 高硅氧玻璃纤维增强焦磷酸锆基复合材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003033664A (ja) * 2001-07-25 2003-02-04 Ngk Insulators Ltd 排ガス浄化用ハニカム構造体及び排ガス浄化用ハニカム触媒体
WO2006137149A1 (ja) * 2005-06-24 2006-12-28 Ibiden Co., Ltd. ハニカム構造体
JP2007296514A (ja) * 2006-04-07 2007-11-15 Ngk Insulators Ltd 触媒体とその製造方法
JP2007296521A (ja) * 2006-05-02 2007-11-15 Argillon Gmbh 押出し成形された固体触媒及びその製造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4867954A (en) * 1988-04-07 1989-09-19 Uop Catalytic reduction of nitrogen oxides
US5589147A (en) * 1994-07-07 1996-12-31 Mobil Oil Corporation Catalytic system for the reducton of nitrogen oxides
WO2001012961A1 (en) * 1999-08-13 2001-02-22 Corning Incorporated Compact catalyst/adsorber for exhaust gas treatment
DE60034027T2 (de) * 1999-12-24 2007-12-13 Asahi Glass Co., Ltd. Siliziumnitridfilter und verfahren zu dessen herstellung
JP4776151B2 (ja) * 2003-05-27 2011-09-21 日産自動車株式会社 排気ガス浄化システム
JP4295279B2 (ja) * 2003-06-23 2009-07-15 イビデン株式会社 ハニカム構造体
US7481983B2 (en) * 2004-08-23 2009-01-27 Basf Catalysts Llc Zone coated catalyst to simultaneously reduce NOx and unreacted ammonia
EP1968730A1 (en) * 2005-12-01 2008-09-17 Basf Catalysts Llc Hydrothermally stable ag-zeolite traps for for small olefin hydrocarbon molecules
JPWO2008059576A1 (ja) * 2006-11-16 2010-02-25 イビデン株式会社 ハニカム構造体及びその製造方法
EP3626329B1 (en) * 2007-04-26 2021-10-27 Johnson Matthey Public Limited Company Exhaust system comprising copper/zsm-34 zeolite scr catalyst and method of converting nitrogen oxides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003033664A (ja) * 2001-07-25 2003-02-04 Ngk Insulators Ltd 排ガス浄化用ハニカム構造体及び排ガス浄化用ハニカム触媒体
WO2006137149A1 (ja) * 2005-06-24 2006-12-28 Ibiden Co., Ltd. ハニカム構造体
JP2007296514A (ja) * 2006-04-07 2007-11-15 Ngk Insulators Ltd 触媒体とその製造方法
JP2007296521A (ja) * 2006-05-02 2007-11-15 Argillon Gmbh 押出し成形された固体触媒及びその製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014054143A1 (ja) 2012-10-03 2014-04-10 イビデン株式会社 ハニカム構造体
EP2845648A2 (en) 2013-08-27 2015-03-11 Ibiden Co., Ltd. Honeycomb catalyst and exhaust gas purifying apparatus
JP5732169B1 (ja) * 2013-12-27 2015-06-10 イビデン株式会社 ゼオライトの製造方法及びハニカム触媒
EP2889269A2 (en) 2013-12-27 2015-07-01 Ibiden Co., Ltd. Method for manufacturing cha-zeolite and honeycomb catalyst
JP5740040B1 (ja) * 2014-07-07 2015-06-24 イビデン株式会社 ゼオライト、ハニカム触媒及び排ガス浄化装置
US9656253B2 (en) 2014-07-07 2017-05-23 Ibiden Co., Ltd. Zeolite, method for manufacturing zeolite, honeycomb catalyst, and exhaust gas purifying apparatus
US9878315B2 (en) 2014-07-07 2018-01-30 Ibiden Co., Ltd. Zeolite, method for manufacturing zeolite, honeycomb catalyst, and exhaust gas purifying apparatus

Also Published As

Publication number Publication date
CN102666430A (zh) 2012-09-12
EP2324920A1 (en) 2011-05-25
EP2324920B1 (en) 2014-11-19
US8658104B2 (en) 2014-02-25
CN102666430B (zh) 2015-04-29
US20110116989A1 (en) 2011-05-19

Similar Documents

Publication Publication Date Title
WO2011061836A1 (ja) ハニカム構造体及び排ガス浄化装置
JP5560158B2 (ja) ハニカム構造体及び排ガス浄化装置
WO2009141895A1 (ja) 排ガス浄化装置
WO2011061841A1 (ja) ハニカム構造体及び排ガス浄化装置
WO2011061835A1 (ja) ハニカム構造体及び排ガス浄化装置
JP5317959B2 (ja) ハニカム構造体
JP2011125849A (ja) ハニカム構造体及び排ガス浄化装置
WO2009141886A1 (ja) ハニカム構造体
JP5837408B2 (ja) ハニカム構造体及び排ガス浄化装置
JP5815220B2 (ja) ハニカム構造体及び排ガス浄化装置
WO2009141898A1 (ja) ハニカム構造体
WO2011061839A1 (ja) ハニカム構造体及び排ガス浄化装置
JP6204751B2 (ja) ハニカム触媒及び排ガス浄化装置
JP5746061B2 (ja) ハニカム構造体及びハニカム構造体の製造方法
JP6245896B2 (ja) ハニカム触媒及び排ガス浄化装置
WO2014054143A1 (ja) ハニカム構造体
JP2010000499A (ja) ハニカム構造体
WO2013024548A1 (ja) ハニカム構造体及びその製造方法、排ガス浄化装置並びにシリコアルミノホスフェート粒子
JP5563952B2 (ja) ハニカム構造体及び排ガス浄化装置
WO2013024545A1 (ja) 複合粒子、ハニカム構造体及びその製造方法並びに排ガス浄化装置
JP2012215166A (ja) 排ガス浄化システム及び排ガス浄化方法
WO2012131913A1 (ja) 排ガス浄化システム及び排ガス浄化方法
WO2012131914A1 (ja) ハニカム構造体及び排ガス浄化装置
WO2011061837A1 (ja) ハニカム構造体の製造方法及び排ガス浄化装置の製造方法
WO2012131915A1 (ja) 排ガス浄化システム及び排ガス浄化方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980162507.4

Country of ref document: CN

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

Ref document number: 09851458

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09851458

Country of ref document: EP

Kind code of ref document: A1