CN1479648A - 一种用于废气净化的催化剂 - Google Patents

一种用于废气净化的催化剂 Download PDF

Info

Publication number
CN1479648A
CN1479648A CNA018202721A CN01820272A CN1479648A CN 1479648 A CN1479648 A CN 1479648A CN A018202721 A CNA018202721 A CN A018202721A CN 01820272 A CN01820272 A CN 01820272A CN 1479648 A CN1479648 A CN 1479648A
Authority
CN
China
Prior art keywords
catalyst
nox storage
base material
storage component
component
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.)
Pending
Application number
CNA018202721A
Other languages
English (en)
Inventor
W・A・卡特勒
W·A·卡特勒
戴
J·P·戴
拉赫瓦尼
S·G·拉赫瓦尼
奥冈伍米
S·B·奥冈伍米
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.)
Corning Inc
Original Assignee
Corning Inc
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 Corning Inc filed Critical Corning Inc
Publication of CN1479648A publication Critical patent/CN1479648A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—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
    • C04B35/44—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 aluminates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8646—Simultaneous elimination of the components
    • B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—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
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
    • F01N3/0842—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B01D2255/2022—Potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2042—Barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2045—Calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2047—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/91—NOx-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • 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
    • C04B2235/3234—Titanates, not containing zirconia
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—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
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—Alkaline earth 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
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction

Abstract

一种净化废气的催化剂，包含：(1)负载于载体材料上的催化促进涂层，包含贵金属催化剂和NOx存储组分组分，其中，NOx存储组分包含碱金属，以及(2)支撑催化促进涂层的陶瓷基材，所述陶瓷基材在1000℃以下可以阻止碱金属迁移，其热膨胀系数约小于25×10－7/℃(25－800℃)。本发明还提供了净化稀燃发动机废气的方法，包括：使稀燃发动机产生的废气与本发明废气净化催化剂接触，同时除去一氧化碳、烃类和氮氧化物，该方法中，在氧浓度大于氧化废气中被氧化组分所需的化学计量值的稀燃气氛中，废气中大多数NOx被多孔性支撑体的NOx存储组分所吸附，废气暂时由稀燃状态转变为富燃料状态时，被吸附的氮氧化物释放出来，在化学计量气氛或氧浓度低于化学计量值的富燃料气氛中与废气中的烃类和一氧化碳发生反应而被化学还原。

Description

一种用于废气净化的催化剂
本发明申请要求Cutler等人于2000年11月6日提出的题为“一种用于废气净化的催化剂”的美国(U.S.)临时申请号60/246,483的权益。
发明背景
本发明涉及一种用于净化废气的催化剂及相应的净化方法。具体地说，本发明涉及一种能够高效净化废气中氮氧化物的催化剂及相应的方法，被处理的废气中氧浓度大于或等于使废气中一氧化碳和烃类发生氧化所需的化学计量值。
在汽车排气系统中，使用催化剂将发动机运转过程中产生的一氧化碳(CO)，烃类及氮氧化物(NOx)转化为更理想的气体。当发动机以等于或稍大于理想的空气/燃油(A/F)比运转时，即氧气浓度较低，A/F比小于14.6时，含有钯或铂的催化剂可高效地将上述三种气体同时有效地转化，即一氧化碳和烃类被氧化成二氧化碳和水，而NOx则还原成氧。因此，这类催化剂被称为“三用(three-way)”催化剂。众所周知的一种“三用”催化剂包括由耐热的堇青石或类似的基材与负载如铂、铑等贵金属的多孔性γ-氧化铝载体层组成。
由于CO2大量排放，以及可开采石油储量的快速消耗，使得内燃机的燃油经济正成为一个被关注的问题。这些导致了对燃油经济及减少排放的更严格的要求。解决这些问题的一种方式是采用将汽油直接注入(GDI)发动机，从而使发动机的大部分工作循环在稀燃状态下运转。在上述“稀燃”条件下，A/F比大于14.6，导致高的氧含量。当空气/燃料混合物处于等于化学计量值的空气/燃料比时，前述传统的三用催化剂可以使CO、烃类和NOx发生氧化或还原从而使废气得到净化。然而，在“稀燃”条件下，由于含有过量的氧，这些催化剂显示出对氮氧化物的净化能力不足。这些情况下，要求开发能够在包含过量氧气的气氛中高效净化NOx的催化剂及净化系统。
US No.5,948,376(Miyoshi)公开了一种在富氧气氛中净化废气的催化剂/净化系统。其中，催化剂包括载体如γ-氧化铝和一种负载于该载体上的NOx存储组分(storage component)。这种NOx存储组分至少包括碱土金属、碱金属和稀土金属元素中的一种。另外，载体中还含有负载于多孔性支撑物质上的贵金属催化剂组分。这种催化剂以下述方式发挥作用：(1)在稀燃气氛中，氧浓度高于氧化废气中需氧化组分所需的化学计量值，废气中的大多数氮氧化物被载体上的NOx存储组分吸附；(2)当废气暂时从稀燃变为富燃状态，即氧含量低于化学计量值时，被吸附的氮氧化物释放出来，然后与废气中的烃类和一氧化碳发生反应而被化学还原。
具体地说，Miyoshi揭示了一些较好的实施方案，即利用蜂窝状堇青石基材，其上载有含CeO2的铝载体，含Ba、La、Li、K和Na的NOx存储组分，以及Pt或Pd贵金属催化剂。
根据涂层中的碱金属和/或碱土金属，NOx在稀燃条件下通常以形成硝酸盐方式进行吸附，这种吸附可以在-200℃至550℃的较低温度范围进行。在同一温度范围内发生NOx解吸并还原成N2，不同的是该过程是在前面所述的富燃料状态下发生的。该系统90％以上的使用时间处于这一温度范围。由于燃料中含有硫，而硫酸盐的形成比硝酸盐的形成更容易，因此也需要周期性地再生硫。此外，硫酸盐也比硝酸盐更稳定。硫的吸附还减少了可用于形成硝酸盐的部位。硫的再生通常在富燃料状态下，在较高的温度范围约600℃-800℃内进行，同样与涂层中的碱金属和/或碱土金属有关。该系统在这一高温范围内使用的时间不到其寿命的10％。一般认为NOx捕集系统在较低温度下的性能十分稳定，而在800℃以上，NOx吸附组分的性能会降低。
本发明人发现了现有催化剂/净化系统的一个缺点，即在有利于NOx吸附组分使用的温度范围内，大多数碱金属很容易与堇青石发生反应。例如，钾是理想的用作吸附剂的碱金属，由于系统运转的温度范围较宽，它很容易与堇青石发生反应，吸引钾离开表面积很高的洗涤涂层(washcoat)，从而阻止钾发挥其吸附剂的作用。而且，钾与堇青石反应形成了热膨胀系数(CTE)相当高的相态，使基材进而使催化剂系统的抗热冲击性极低。本发明是针对上述情况而开发的。与此相应，本发明的目的是提供一种用于废气净化的催化剂，当发动机在稀燃状态下运行时，即废气中氧含量等于或大于化学计量值时，这种催化剂的性能在发动机如此运行时的较高温度下不会退化。
发明概要
根据本发明的第一种实施方案，揭示的废气净化催化剂包括：(1)负载于载体之上的催化促进涂层，包含贵金属催化剂和NOx存储组分，其中NOx存储组分包含碱金属，(2)用于支撑催化促进涂层的陶瓷基材，这种陶瓷基材在1000℃以下可以阻止碱金属迁移，且其热膨胀系数小于25×10-7/℃(25-800℃)。
另一方面，本发明提供净化稀燃发动机产生的废气的方法，该方法涉及使稀燃发动机产生的废气与本发明揭示的废气净化催化剂接触，同时除去一氧化碳、烃类和氮氧化物。在该方法中，废气中的大多数氮氧化物在稀燃气氛中被多孔性支撑涂层上的NOx存储组分吸附，此时氧浓度高于氧化废气中各组分所需的化学计量值。进一步地，当废气暂时从稀燃状态转变为富燃料状态时，被吸附的氮氧化物释放出来，并与废气中的烃类和一氧化碳在等化学计量状态或氧含量低于化学计量值的富燃料状态下发生反应而被还原。
更有利的是，我们发现本发明提出的废气净化催化剂改善了在高达约1000℃的高温时的高温耐久性，与含传统堇青石基材的催化系统相比，吸附效率得到了提高，而后者由于碱金属、碱土金属和稀土金属的迁移使其耐热性能和机械寿命降低，并且吸附能力也降低。
附图简述
图1a和1b分别为铝酸钙支撑基材在洗涤涂布了载体材料和钾的NOx存储组分后，在900℃老化16小时前、后的显微探针元素图，放大倍数为225X。
图2a和2b分别为堇青石支撑基材在洗涤涂布了载体材料和钾的NOx存储组分后，在900℃下老化16小时前、后的显微探针元素图，放大倍数为56X。
发明详述
本发明的一个方面，涉及一种用于在富氧气氛中净化废气的催化剂，特别是用于废气中氧浓度等于或大于使其中如烃类和一氧化碳的组分发生氧化所需的化学计量值的稀燃气氛，对废气进行净化。该催化剂系统包括：(1)负载于载体材料上的催化剂促进涂层，包含贵金属催化剂和NOx存储组分，其中NOx存储组分包含碱金属，和(2)用于支撑催化促进涂层的陶瓷基材，该陶瓷基材在1000℃以下可阻止碱金属的迁移，且其热膨胀系数小于25×10-7/℃(25-800℃)，较好的小于15×10-7/℃(25-800℃)。
合适的陶瓷基材材料包括但不限于硅酸盐和不含磷酸盐的材料，如铝酸钙，一缩二亚钛酸镁，钛酸铁，钛酸锆以及它们的各种混合物和固溶体。由于这些材料在使用条件下与碱金属几乎或完全不发生反应，因此这一体系可以避免在传统的堇青石基材催化系统中存在的碱金属的迁移。
研究已证明碱金属具有很强的反应性，可与大多数材料发生反应，特别是在接近1000℃高温的条件下，可与堇青石发生反应。碱金属这种易迁移性及与支撑基材如堇青石的反应性，导致形成对催化剂系统有害的第二相。特别是形成的这些第二相会导致NOx存储组分从洗涤涂层上流失，从而降低系统的催化能力。进一步地，NOx存储组分与基材材料反应生成高热膨胀系数的相，使得系统的机械强度降低。与之相反，本发明的基材不会因在高温下使用而使碱金属的存储NOx组分从洗涤涂层上流失。NOx存储组分得以保留在洗涤涂层上，从而实现其催化/吸附剂的功能。
宜用作支撑基材的材料包括具有选自下列组成的材料：按摩尔比计，1∶1的铝酸钙(CaO)∶氧化铝(Al2O3)，1∶2的CaO∶Al2O3，以及它们的各种组合。此外，支撑基材也可包含具有上述之一的基本体系配合以固溶体或第二相组成的材料，所述固溶体或第二相选自下列各种组分：K2Al2O4，Li2Al2O4，MgAl2O4，ZnO，SrO和Y2O3，其中，这些替代组分的含量应在1～15重量％之间。另外，支撑基材可包含由50％MgTi2O5和50％ZrTiO4组成的混合物或50％Fe2TiO5和50％ZrTiO4组成的混合物。
正如本领域技术人员所了解的，通用的形成支撑基材结构的方法为，将合适的材料混合，较好的将各批材料制成粉末状原料，平均粒径小于150μm，最好小于50μm。然后该混合物混匀，再通过诸如挤压等使之形成蜂窝状坯体。随后将挤压成形的蜂窝状坯体进行烧结，得到刚性的多孔性结构。按制备支撑基材的方法，混和时需向所述批料中加入各种润滑剂和有机粘结剂如甲基纤维素，用以控制烧结前的粘度和强度以及提供烧结后结构孔隙率。孔隙率也与原料和烧结温度有关，温度越高，烧结后所得的结构就越致密。
至于用来负载NOx存储组分和贵金属催化剂的载体材料，一般为一层洗涤涂层，且包含表面积为10～300m2/g的高表面积材料。这类合适的材料包括但不限于：沸石，氧化锆，α-或γ-氧化铝及氧化铈。本领域的技术人员皆知这类用来负载NOx吸附组分和贵金属催化剂的洗涤涂层材料。然而，对本发明而言，选择特定的载体材料并不是关键，但最好选用γ-氧化铝作为洗涤涂层材料。
NOx存储组分包括选自下列的碱金属：锂(Li)，钠(Na)，钾(K)，铷(Rb)，铯(Cs)，钫(Fr)。最好用钾作为NOx存储组分，因为在较宽的温度范围内及升高温度下，其NOx的吸附能力高于其它NOx存储组分。此外，NOx存储组分也可以包含碱土金属和稀土金属。
合适的碱土金属包括：钡(Ba)，铍(Be)，镁(Mg)，钙(Ca)和锶(Sr)。合适的稀土金属包括：钪(Sc)，钇(Y)，镧(La)，铈(Ce)，镨(Pr)和钕(Nd)。贵金属催化剂组分选自Pt，Rh和Pd。
以1升多孔性支撑材料计，贵金属催化剂组分的负载量宜为0.1～20克，而以0.5～10克最好。
通常将NOx存储组分和贵金属催化剂与载体材料的料浆混合在一起，形成洗涤涂料，然后将该涂料施涂于支撑基材上。或者，首先将载体材料洗涤涂布在支撑基材上，然后将NOx存储组分和贵金属催化剂混合后涂布于支撑基材上，或将两者相继涂布于有载体材料的支撑基材上。实际采用的洗涤涂布多孔支撑材料以及NOx和贵金属催化剂材料的方法对在此公开的本发明并不重要，对本领域技术人员而言为合适的任何方法都能采用。不管采用以上哪种洗涤涂布技术，当各涂层洗涤涂布于支撑基材后，一般都要在高温下干燥和焙烧。
本发明内燃机催化剂系统中，除了在此所描述的系统外，还可以包括含有诸如钯、铂和铑，或钯和铑的三用催化剂装置。三用催化剂装置可置于NOx捕集系统的上游，因而靠近发动机。按这种排列，三用催化剂安装位置距发动机较近，因此会迅速升温，从而保证有效地控制发动机冷启动时的废气排放。一旦发动机温度上升，三用催化剂将在等化学计量运转期间除去废气中的烃类、一氧化碳和氮氧化物，而在稀燃运转期间除去烃类和一氧化碳。本发明催化剂系统可位于三用催化剂的下游，此处废气的温度能使催化剂的效率达到最高。在发动机稀燃运转期间，当NOx通过三用催化剂时，废气中大多数氮氧化物被多孔性支撑材料上的NOx存储组分所吸附。本发明催化剂可通过短时期的发动机富燃运转来定时地再生。在这段从稀燃转变为富燃料期间，吸附的氮氧化物释放出来，与废气中的烃类和一氧化碳在等化学计量或富燃料状态下反应而被化学还原。将本发明催化剂置于三用催化剂的下游，距发动机相对较远，可避免催化剂受废气高温的影响，因为高温对NOx捕集系统不利。为保证再生期间脱附的NOx能被高效还原，也需要在本发明催化剂的捕集系统的下游放置第二个三用催化剂系统。
实施例
混合下列组分，制备本发明组合物的混合物，获得的组成为24.8重量％CaO和75.2重量％Al2O3。
    371g  CaCO3(3～4μm APS)
    629g  Al2O3(～4μm APS)
    50g   甲基纤维素
    10g   润滑剂
    200g  水
*APS：平均粒径
按上表所列的量将甲基纤维素粘结剂组分加入干燥的氧化钙和氧化铝的粉末混合物中，所得混合物进一步与去离子水混合，形成增塑的陶瓷混合物。
将该增塑陶瓷混合物通过挤出机挤出，形成长约3英寸，直径约1.5～1.75英寸，孔隙率为400孔/英寸2的蜂窝状基材。由上述组合物形成的蜂窝状坯体充分干燥以除去水分或可能存在的各种液相物质，然后经过循环加热和焙烧，充分除去挤出的条状物和蜂窝中的有机粘结剂，从而烧结该挤出条和蜂窝。具体地说，上述坯体在1500～1600℃下焙烧8～96小时，这是适宜生成具有硬质多孔结构的陶瓷体的烧结条件。
将200克γ-AL2O3和67克K2CO3与400克蒸馏水混合，形成载体材料-NOx存储组分的洗涤涂布浆料，用来涂布于蜂窝状基材。将上述组合物构成的蜂窝状支撑基材和用作对比的堇青石基材分别完全浸没在以上制备的浆料中。一旦生成一个稳定的涂层，即将洗涤涂布后的样品从浆料中取出，然后将蜂窝状物稍稍振摇从中吹去多余的浆料。除去多余的浆料后，所得浸涂好的蜂窝状支撑基材于90℃下干燥15～30分钟，再于550℃煅烧4小时。
将上述各个样品进行老化处理，即将上述浸涂好的支撑基材在900℃的空气中放置16小时。对这三个样品分别在老化前后进行WDS显微探针分析，得到放大倍数为30,000X的老化前后的钾(K)元素图，以测定富钾区域。以判断在老化过程中NOx钾存储组分是否向支撑基材内部发生了迁移。
图1a和图1b所示分别为本发明实施例的洗涤涂布后的铝酸钙支撑基材在老化前后的钾元素图。比较图1a和图1b可见，钾含量较高的区域，即图中呈灰色或较明亮的区域没有发生任何变化，图中黑色或较暗的区域为基材。因此在老化处理后钾基本上保留在原位(洗涤涂层上)。这证实了钾的NOx存储组分没有从洗涤涂层迁移至基材。而若发生这种迁移可能会使基材的耐热性能和机械强度下降，或导致催化剂效率下降。
图2a和2b分别为对照实施例的洗涤涂布后的堇青石基材，在老化前后的钾(K)元素图。比较图2a和图2b可见，与洗涤涂布铝酸钙的支撑基材相反，对照样品中几乎所有的钾(K)的NOx存储组分都从涂层中迁移到了支撑基材。具体地说，图2a中，像元素图上基材部分为较暗或黑色区域，而在图2b中，基材部分变成了灰色或明亮的区域，这证实钾发生了迁移。
应理解，在参考一些说明性非具体实施方案对本发明进行详细阐述时，但不仅限于此，在不偏离权利要求定义的本发明的精神和范围内，可以进行各种各种修改。

Claims (23)

1.一种用于在富氧气氛中净化废气的催化剂，所述富氧气氛中，废气的氧浓度等于或大于氧化其中各需氧化组分所需的化学计量值，所述催化剂主要由下列组分组成：
(1)负载于载体材料上的催化促进涂层，包含贵金属催化剂和NOx存储组分组分，其中，NOx存储组分包含碱金属，以及
(2)支撑催化促进涂层的陶瓷基材，所述陶瓷基材在1000℃以下可以阻止碱金属迁移，其热膨胀系数约小于25×10-7/℃(25-800℃)。
2.如权利要求1所述的催化剂，其特征在于所述基材包含硅酸盐和不含磷酸盐的材料。
3.如权利要求2所述的催化剂，其特征在于所述材料选自下列物质：铝酸钙，一缩二亚钛酸镁，钛酸铁，钛酸锆，以及它们的混合物和固溶体。
4.如权利要求2所述的催化剂，其特征在于所述基材包含选自下列的材料：1∶1的CaO∶Al2O3，1∶2的CaO∶Al2O3，以及它们的混合物。
5.如权利要求3所述的催化剂，其特征在于所述材料还包含由选自下列物质形成的第二相：K2Al2O4，Li2Al2O4，MgAl2O4，ZnO，SrO及Y2O3。
6.如权利要求2所述的催化剂，其特征在于所述基材包含由50％Fe2TiO5和50％ZrTiO4组成的混合物。
7.如权利要求2所述的催化剂，其特征在于所述基材包含由50％MgTi2O5和50％ZrTiO4组成的混合物。
8.如权利要求1所述的催化剂，其特征在于所述基材的热膨胀系数小于15×10-7/℃(25-800℃)。
9.如权利要求2所述的催化剂，其特征在于所述材料包含选自下列的材料：氧化铝，沸石，氧化锆或它们的混合物。
10.如权利要求1所述的催化剂，其特征在于所述NOx存储组分的碱金属选自：锂(Li)，钠(Na)，钾(K)，铷(Rb)，铯(Cs)，钫(Fr)。
11.如权利要求8所述的催化剂，其特征在于所述NOx存储组分的碱金属是钾(K)。
12.如权利要求10所述的催化剂，其特征在于所述NOx存储组分还包括选自碱土金属、稀土金属以及它们的混合物的组分。
13.如根据权利要求12所述的催化剂，其特征在于所述碱土金属选自：钡(Ba)，铍(Be)，镁(Mg)，钙(Ca)和锶(Sr)。
14.如权利要求13所述的催化剂，其特征在于所述NOx存储组分是钡(Ba)，镁(Mg)或钙(Ca)。
15.如权利要求12所述的催化剂，其特征在于稀土金属选自：钪(Sc)，钇(Y)，镧(La)，铈(Ce)，镨(Pr)和钕(Nd)。
16.如权利要求1所述的催化剂，其特征在于所述NOx存储组分的负载量为能有效存储其中的氧含量等于或大于使一氧化碳和烃类(HC)氧化所需的化学计量值的废气中的NOx。
17.如权利要求1所述的催化剂，其特征在于所述NOx存储组分的负载量为每升多孔性支撑基材上负载0.025～0.5摩尔该组分。
18.如权利要求1所述的催化剂，其特征在于所述贵金属催化剂是至少一种选自下列的元素：铂(Pt)，铑(Rh)和钯(Pd)。
19.如权利要求1所述的催化剂，其特征在于所述中贵金属催化剂的负载量为能有效净化其中氧含量等于或大于使一氧化碳(CO)和烃类(HC)氧化所需的化学计量值的废气中的NOx，CO和HC。
20.如权利要求1所述的催化剂，其特征在于所述贵金属催化剂的负载量为每升多孔性支撑基材上负载0.1～20克。
21.如权利要求1所述的催化剂，其特征在于所述催化剂包括铝酸钙支撑基材、γ-氧化铝载体材料、钾(K)的NOx存储组分和铂(Pt)贵金属催化剂。
22.一种净化稀燃发动机废气的方法，该方法包括：
(a)使稀燃发动机产生的废气与废气净化催化剂接触，同时除去废气中的一氧化碳、烃类和氮氧化物，所述催化剂主要由下列组分组成：
(1)负载于载体材料上的催化促进涂层，包含贵金属催化剂和NOx存储组分，所述NOx存储组分包含碱金属，以及
(2)支撑催化促进涂层的陶瓷基材，所述陶瓷基材在1000℃以下可以阻止碱金属的迁移，且热膨胀系数小于25×10-7/℃(25-800℃)，
其中，在氧浓度大于氧化废气中被氧化组分所需的化学计量值的稀燃气氛中，废气中大多数NOx被多孔性支撑体的NOx存储组分所吸附，废气暂时由稀燃状态转变为富燃料状态时，被吸附的氮氧化物释放出来，在化学计量气氛或氧浓度低于化学计量值的富燃料气氛中与废气中的烃类和一氧化碳发生反应而被化学还原。
23.如权利要求22所述的方法，其特征在于所述催化剂包括铝酸钙支撑基材、γ-氧化铝载体材料、钾(K)的NOx存储组分和铂(Pt)贵金属催化剂。
CNA018202721A 2000-11-06 2001-10-15 一种用于废气净化的催化剂 Pending CN1479648A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24648300P 2000-11-06 2000-11-06
US60/246,483 2000-11-06

Publications (1)

Publication Number Publication Date
CN1479648A true CN1479648A (zh) 2004-03-03

Family

ID=22930869

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA018202721A Pending CN1479648A (zh) 2000-11-06 2001-10-15 一种用于废气净化的催化剂

Country Status (7)

Country Link
US (1) US6897182B2 (zh)
EP (1) EP1341599B1 (zh)
JP (1) JP2004515338A (zh)
KR (1) KR20030061393A (zh)
CN (1) CN1479648A (zh)
DE (1) DE60139569D1 (zh)
WO (1) WO2002036254A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105214238A (zh) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 一种防治雾霾的口罩
CN105268126A (zh) * 2015-11-13 2016-01-27 无锡桥阳机械制造有限公司 一种防毒面具用滤毒罐
CN105327469A (zh) * 2015-11-13 2016-02-17 无锡桥阳机械制造有限公司 一种防毒面具用滤毒罐
CN107405606A (zh) * 2015-02-09 2017-11-28 巴斯夫公司 柴油机氧化催化剂
CN109477410A (zh) * 2016-08-04 2019-03-15 恩亿凯嘉股份有限公司 适应冷起动的尿素scr系统

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020082164A1 (en) * 2000-01-14 2002-06-27 Danan Dou Methods to reduce alkali material migration from NOx adsorber washcoat to cordierite
GB0022786D0 (en) 2000-09-16 2000-11-01 Johnson Matthey Plc NOx-Trap composition
GB0028198D0 (en) * 2000-11-20 2001-01-03 Johnson Matthey Plc High temperature nox-trap component
JP2002282702A (ja) * 2001-01-19 2002-10-02 Ngk Insulators Ltd 触媒体
US6756338B2 (en) * 2001-09-19 2004-06-29 Johnson Matthey Public Limited Company Lean NOx trap/conversion catalyst
FR2833253B1 (fr) * 2001-12-12 2004-10-08 Rhodia Elect & Catalysis Procede de preparation d'un oxyde a base de zirconium et de titane, oxydes ainsi obtenus et utilisation de ces oxydes comme catalyseurs
JP3912294B2 (ja) * 2003-02-19 2007-05-09 トヨタ自動車株式会社 内燃機関の排気浄化方法および排気浄化装置
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
US7238640B2 (en) * 2003-12-30 2007-07-03 Ford Global Technologies, Llc Minimization of purge NOx release from NOx traps by optimizing the oxygen storage capacity
KR100577837B1 (ko) * 2005-01-27 2006-05-12 (주)이엔디솔루션 디젤엔진 배출가스 저감 촉매 및 장치
JP4778724B2 (ja) * 2005-05-02 2011-09-21 株式会社キャタラー 硫化水素発生抑制触媒
JP4714568B2 (ja) * 2005-11-22 2011-06-29 マツダ株式会社 排気ガス浄化用触媒及びその製造方法
JP2007136420A (ja) * 2005-11-22 2007-06-07 Mazda Motor Corp 排気ガス浄化用触媒及びその製造方法
JP4851190B2 (ja) * 2006-01-13 2012-01-11 戸田工業株式会社 排気ガス浄化用触媒
US10501375B2 (en) 2006-06-30 2019-12-10 Corning Incorporated Cordierite aluminum magnesium titanate compositions and ceramic articles comprising same
JP5178715B2 (ja) 2006-06-30 2013-04-10 コーニング インコーポレイテッド コージェライトチタン酸アルミニウムマグネシウム組成物及びこの組成物を含むセラミック製品
US8956436B2 (en) 2006-06-30 2015-02-17 Corning Incorporated Cordierite aluminum magnesium titanate compositions and ceramic articles comprising same
JP5459927B2 (ja) * 2006-07-07 2014-04-02 株式会社キャタラー 排ガス浄化用触媒
NO327431B1 (no) * 2006-09-08 2009-06-29 Yara Int Asa Fremgangsmate og anordning for fangst av platinagruppeelementer
CA2671051C (en) 2006-11-30 2015-11-24 Purafil, Inc. Dry-scrubbing media compositions and methods of production and use
US7713897B2 (en) * 2007-02-27 2010-05-11 Corning Incorporated Ceramic materials for 4-way and NOx adsorber and method for making same
WO2009120744A1 (en) * 2008-03-25 2009-10-01 Purafil, Inc. Dry-scrubbing media compositions and methods of production and use
US20110195007A1 (en) * 2008-05-16 2011-08-11 Postech Academy-Industry Foundation CATALYST FOR REMOVING NOx FROM EXHAUST GAS OF LEAN-BURNING AUTOMOBILES OR INCINERATORS
US8920759B2 (en) * 2009-03-02 2014-12-30 GM Global Technology Operations LLC Method and apparatus for reducing NOx emissions from a lean burning hydrocarbon fueled power source
US8815763B2 (en) * 2010-05-28 2014-08-26 Corning Incorporated Method of manufacturing a transition metal catalyzed zeolite 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
KR101438953B1 (ko) * 2012-12-18 2014-09-11 현대자동차주식회사 저온에서의 NOx 흡장성능이 개선된 LNT촉매
KR101524054B1 (ko) * 2013-12-24 2015-05-29 희성촉매 주식회사 압축천연가스 연소시스템 배기가스 산화촉매
CN103736511B (zh) * 2013-12-25 2016-05-25 上海纳米技术及应用国家工程研究中心有限公司 用于一氧化碳常温催化氧化的催化剂及制备方法和应用
KR101825469B1 (ko) 2015-12-23 2018-02-05 희성촉매 주식회사 압축천연가스 연소시스템 배기가스 산화촉매

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3922235A (en) * 1974-07-31 1975-11-25 Exxon Research Engineering Co Stabilized ruthenium catalysts for selective reduction of oxides of nitrogen
JPS5479191A (en) * 1977-12-08 1979-06-23 Matsushita Electric Ind Co Ltd Carbon monoxide purging catalyst element
JPS5689844A (en) 1979-12-25 1981-07-21 Asahi Glass Co Ltd Ceramic honeycomb and its production
US4350613A (en) * 1980-03-11 1982-09-21 Matsushita Electric Industrial Company, Limited Catalyst for purifying exhaust gases and method for manufacturing same
JPS6154238A (ja) * 1984-08-22 1986-03-18 Matsushita Electric Ind Co Ltd 排ガス浄化用触媒体
JPH084749B2 (ja) * 1985-01-21 1996-01-24 日本碍子株式会社 セラミツクハニカム構造体
US4915887A (en) 1988-04-04 1990-04-10 Corning Incorporated Method of preparing high temperature low thermal expansion ceramic
JPH0724774B2 (ja) * 1988-11-25 1995-03-22 株式会社日本触媒 排ガス処理触媒用担体、その製造方法ならびに該担体を含有してなる排ガス処理用触媒
JP3113662B2 (ja) 1990-02-26 2000-12-04 株式会社日本触媒 ディーゼルエンジン排ガス浄化用触媒体
JPH0487625A (ja) 1990-07-31 1992-03-19 Mazda Motor Corp エンジンの排ガス浄化装置
JP3363564B2 (ja) * 1994-02-04 2003-01-08 トヨタ自動車株式会社 排ガス浄化用触媒
US6245307B1 (en) 1994-06-17 2001-06-12 Ict Co., Ltd. Catalyst for purifying exhaust gas from lean burn engine and method for purification
JPH10165817A (ja) 1996-12-10 1998-06-23 Toyota Central Res & Dev Lab Inc 排ガス浄化用触媒

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107405606A (zh) * 2015-02-09 2017-11-28 巴斯夫公司 柴油机氧化催化剂
CN107405606B (zh) * 2015-02-09 2021-09-10 巴斯夫公司 柴油机氧化催化剂
CN105214238A (zh) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 一种防治雾霾的口罩
CN105268126A (zh) * 2015-11-13 2016-01-27 无锡桥阳机械制造有限公司 一种防毒面具用滤毒罐
CN105327469A (zh) * 2015-11-13 2016-02-17 无锡桥阳机械制造有限公司 一种防毒面具用滤毒罐
CN109477410A (zh) * 2016-08-04 2019-03-15 恩亿凯嘉股份有限公司 适应冷起动的尿素scr系统

Also Published As

Publication number Publication date
EP1341599B1 (en) 2009-08-12
DE60139569D1 (de) 2009-09-24
JP2004515338A (ja) 2004-05-27
US6897182B2 (en) 2005-05-24
EP1341599A1 (en) 2003-09-10
EP1341599A4 (en) 2006-07-19
US20020081255A1 (en) 2002-06-27
WO2002036254A1 (en) 2002-05-10
KR20030061393A (ko) 2003-07-18

Similar Documents

Publication Publication Date Title
CN1479648A (zh) 一种用于废气净化的催化剂
JP3907884B2 (ja) 窒素酸化物貯蔵触媒、その製造方法およびその使用
JP3786954B2 (ja) 層状触媒複合体
KR100361417B1 (ko) 적층촉매복합물
US5981427A (en) Catalyst composition
US8454917B2 (en) Nitrogen oxide storage catalytic converter for use in a motor vehicle in a close-coupled position
JP3291086B2 (ja) 排ガス浄化用触媒及び排ガス浄化方法
EP0931590A1 (en) Catalyst for purifying exhaust gas and manufacturing method thereof
JP3494147B2 (ja) 排ガス浄化用触媒とその製造方法及び排ガス浄化方法
KR20030090728A (ko) ＳＯｘ에 내성이 있는 ＮＯｘ 트랩 촉매 및 이의 제조방법 및 사용 방법
JPH0899034A (ja) 排気ガス浄化用触媒
JP4172272B2 (ja) 排ガス浄化触媒及び該触媒を備えた内燃機関
JP2000079327A (ja) リ―ンバ―ン・エンジン用ＮＯｘトラップ触媒
JPH11207190A (ja) 排気ガス浄化用触媒及びその製造方法
JP3378096B2 (ja) 排ガス浄化用触媒
KR100665606B1 (ko) 내연기관 배기가스 정화용 촉매조성물 제조용 400ｐｐｍ 이상 이리듐 성분이 불순물로 포함된 로듐용액
JP2013072334A (ja) 排ガス浄化装置および排ガス浄化触媒ユニット
JP3154620B2 (ja) 排ガス浄化用触媒及び排ガス浄化方法
JP2008229546A (ja) 排ガス浄化用触媒及びその製造方法
JP4019351B2 (ja) ＮＯｘ浄化触媒及びＮＯｘ浄化システム
JP3786666B2 (ja) 排気ガス浄化用触媒及びその製造方法
JP7228451B2 (ja) 自動車用排ガス浄化触媒
JPH0857314A (ja) 排気ガス浄化用触媒
JP4172370B2 (ja) 排ガス浄化用触媒の製造方法
JPH11253758A (ja) 排気ガス浄化用触媒及び排気ガス浄化方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
AD01 Patent right deemed abandoned
C20 Patent right or utility model deemed to be abandoned or is abandoned