WO2010013574A1 - 排気ガス浄化触媒 - Google Patents
排気ガス浄化触媒 Download PDFInfo
- Publication number
- WO2010013574A1 WO2010013574A1 PCT/JP2009/061995 JP2009061995W WO2010013574A1 WO 2010013574 A1 WO2010013574 A1 WO 2010013574A1 JP 2009061995 W JP2009061995 W JP 2009061995W WO 2010013574 A1 WO2010013574 A1 WO 2010013574A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- exhaust gas
- gas purification
- powder
- catalyst
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 213
- 238000000746 purification Methods 0.000 title claims abstract description 118
- 150000001875 compounds Chemical class 0.000 claims abstract description 196
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 91
- 239000002923 metal particle Substances 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims description 156
- 239000007789 gas Substances 0.000 claims description 139
- 239000011148 porous material Substances 0.000 claims description 59
- 239000010410 layer Substances 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000010948 rhodium Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 17
- 229910052878 cordierite Inorganic materials 0.000 description 13
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 13
- 229940125782 compound 2 Drugs 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910001593 boehmite Inorganic materials 0.000 description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 230000004931 aggregating effect Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01D2255/1021—Platinum
-
- 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
- B01D2255/1023—Palladium
-
- 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
- B01D2255/1025—Rhodium
-
- 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
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20746—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20753—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/908—O2-storage component incorporated in the catalyst
-
- 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
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9202—Linear dimensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9205—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/014—Stoichiometric gasoline engines
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous 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
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to an exhaust gas purification catalyst suitable for application to a process for purifying exhaust gas discharged from an internal combustion engine.
- alumina Al 2 Exhaust gas purification catalysts in which noble metal particles such as platinum (Pt) and rhodium (Rh) are supported on a metal oxide carrier such as O 3 ) are widely used.
- a large amount of noble metal particles is used in order to improve the durability of the noble metal particles against ambient fluctuations.
- using a large amount of noble metal particles is not desirable from the viewpoint of protecting earth resources.
- One measure for reducing the amount of noble metal used while maintaining a certain level of exhaust gas purification performance is to reduce the particle size of the noble metal particles. If the particle diameter of the noble metal particles is reduced, the specific surface area increases, so that the amount of noble metal used for obtaining the desired catalyst purification performance can be reduced. However, if the particle diameter of the noble metal particles is small, the heat aggregation (sintering) may occur due to use at a high temperature or use for a long time, which may reduce durability.
- noble metal particles are supported on the first compound, the first compound supporting the noble metal particles is encapsulated in the second compound, and the first compounds supporting the noble metal are supported by the second compound.
- An exhaust gas purification catalyst having a separated structure has been developed (Patent Document 1).
- the noble metal particles are supported on the first compound, and the noble metal particles are chemically fixed to the first compound.
- the first compound supporting the noble metal particles is physically separated from each other by the second compound, thereby preventing the first compounds supporting the noble metal from contacting and aggregating with each other. .
- the exhaust gas purification catalyst described in the above-mentioned Patent Document 1 needs to reduce the amount of the noble metal particles supported on the first compound in order to keep the particle diameter of the noble metal particles small. Therefore, the exhaust gas purification catalyst has a small particle size of the first compound. However, if the particle diameter of the first compound is small, the pore volume, which is an index of the pore size of the exhaust gas purification catalyst, becomes small, and the gas diffusibility sometimes decreases. Therefore, although the exhaust gas purification catalyst has a structure that keeps the particle diameter of the noble metal particles small, the exhaust gas purification performance may not be sufficiently improved by reducing the particle diameter of the noble metal particles.
- an exhaust gas purification catalyst includes a noble metal particle, a first compound supporting the noble metal particle, a second compound of a type different from the first compound, These noble metal particles, an oxide covering the first compound and the second compound, and the median diameter of the first compound and the median diameter of the second compound are the following inequalities: It is summarized that the relationship of the median diameter of ⁇ the median diameter of the second compound is satisfied.
- gas diffusivity can be improved by the presence of the second compound having a large particle diameter in the structure capable of keeping the noble metal particles small, and thereby the exhaust gas purification. Capability can be improved.
- FIG. 1 is a schematic diagram of an exhaust gas purification catalyst according to an embodiment of the present invention.
- FIG. 2 is a micrograph of the exhaust gas purification catalyst of the present invention.
- FIG. 3 is a sketch diagram of FIG.
- FIG. 4 is a schematic view of a conventional exhaust gas purification catalyst.
- FIG. 5 is a micrograph of a conventional exhaust gas purification catalyst.
- FIG. 6 is a sketch diagram of FIG.
- FIG. 7 is a graph showing an example of pore distribution by the N 2 adsorption method in the exhaust gas purification catalyst of the present invention and the conventional exhaust gas purification catalyst.
- FIG. 1 is a schematic diagram of an exhaust gas purification catalyst according to an embodiment of the present invention.
- FIG. 2 is a micrograph of the exhaust gas purification catalyst of the present invention.
- FIG. 3 is a sketch diagram of FIG.
- FIG. 4 is a schematic view of a conventional exhaust gas purification catalyst.
- FIG. 5 is a micrograph of a conventional exhaust gas
- FIG. 8 is a graph showing the relationship between the pore volume of the exhaust gas purification catalyst having a pore diameter in the range of 0 to 200 [nm] and the NOx conversion rate as an example of the exhaust gas purification performance.
- FIG. 9 is a schematic perspective view of an example of a refractory inorganic carrier coated with the exhaust gas purification catalyst of the present invention.
- FIG. 10 is an enlarged cross-sectional view of one pore of the refractory inorganic carrier in a cross section perpendicular to the penetration direction.
- FIG. 1 is a schematic diagram of an exhaust gas purification catalyst according to an embodiment of the present invention.
- the exhaust gas purification catalyst shown in FIG. 1 includes a noble metal particle 1 having catalytic activity, a first compound 2 carrying the noble metal particle 1, a second compound 3 of a type different from the first compound, The noble metal particles 1, the first compound 2, and the oxide 4 covering the second compound 3 are included.
- the noble metal particle 1 carries the first compound 2.
- the first compound acts as an anchor material for chemical bonding with the noble metal particles 1 and chemically suppresses the movement of the noble metal particles 1.
- the oxide 4 is interposed between the first compound 2 and the second compound 3 that carry the noble metal particles 1, the plurality of first compounds, the plurality of second compounds, or the first compound
- the compound 2 is separated from the second compound by the oxide 4. Therefore, the first compounds 2 supporting the noble metal particles 1, the plurality of second compounds, or the first compound 2 and the second compound are prevented from contacting and aggregating with each other.
- the aggregation of the first compound 2 carrying the noble metal particles 1 the aggregation of the noble metal particles 1 carried thereon is also suppressed.
- the exhaust gas purification catalyst of the present embodiment has such a catalyst structure, the movement of the noble metal particles 1 is suppressed, so that the aggregation of the noble metal particles 1 is suppressed.
- the particle size can be kept small.
- FIG. 2 shows a micrograph of the exhaust gas purification catalyst of the present invention.
- FIG. 3 shows a sketch diagram of FIG. In FIG. 2, the part shown in black is the first compound 2 or the second compound 3, the part shown in white is the pore P, and the part shown in gray is the oxide 4. is there.
- an exhaust gas purification catalyst comprising the first compound 2, the second compound 3, and the oxide 4 configured according to the present invention and having the pores P is actually obtained. It has been.
- the noble metal particles 1 cannot be discriminated in FIG. 2 because the particle diameter of the noble metal particles 1 is much smaller than that of the first compound 2 or the like.
- FIG. 4 is a schematic diagram of a conventional exhaust gas purification catalyst for comparison.
- the same elements as those in FIG. the noble metal particles 1 carry the first compound 2 and the oxide 4 is formed covering the first compound.
- the conventional exhaust gas purification catalyst shown in FIG. 4 is different in that it does not include the second compound 3 in the exhaust gas purification catalyst of the present invention shown in FIG. In this case, the conventional exhaust gas purification catalyst shown in FIG. 4 has a smaller pore P than the exhaust gas purification catalyst of the present invention shown in FIG.
- FIG. 5 is a micrograph of the conventional exhaust gas purification catalyst shown in FIG.
- the micrograph shown in FIG. 5 has the same magnification as the exhaust gas purification catalyst of the present invention shown in FIG.
- the part shown in black is the first compound 2
- the part shown in white is the pore P
- the part shown in gray is the oxide 4.
- FIG. 6 shows a sketch diagram of FIG.
- one of the features of the exhaust gas purification catalyst of the present embodiment shown in FIGS. 1, 2, and 3 is the first And having a second compound having a particle size larger than that of the compound.
- the size of the pores can be made larger than that of the conventional exhaust gas purification catalyst, so that the gas diffusibility can be improved and, consequently, the catalyst performance can be improved.
- the above effect of the second compound will be described more specifically.
- the catalyst performance is determined by (1) the surface area of the noble metal particles, (2) the contact of the gas with the noble metal particles, and (3) the effective utilization of the contacted gas.
- the conventional exhaust gas purification catalyst shown in FIG. 4 and FIG. 5 in order to maintain a predetermined good noble metal particle surface area even after use (durable use) of the catalyst at a high temperature for a long time.
- the structure as described above that is, a structure in which noble metal particles are supported on the first compound as the anchor material, and the first compound supporting the noble metal particles is included in the oxide (anchor-inclusion). I took it. This has succeeded in increasing the surface area of the noble metal particles by keeping the particle diameter of the noble metal at about 10 [nm] after durability.
- the exhaust gas purification catalyst having such an anchor-cladding structure has a structure in which the noble metal / anchor that is the active point is covered with the oxide that is the clathrating material, so that it is difficult for the gas to reach the active point. There was a problem of becoming. For this reason, in order to improve gas diffusibility, it is necessary to enlarge the pore diameter (pore capacity) formed by the oxide as the inclusion material.
- the present invention is compatible with the two contradictory matters, namely, reducing the particle diameter of the noble metal after durability and increasing the pore volume of the clathrate.
- the anchor material on which the noble metal particles are supported has a small particle diameter, and is provided with another particle having a particle diameter larger than that of the anchor material. It was found that it is effective to include in. Therefore, the present invention has one of the requirements to satisfy the following inequality: median diameter of the first compound ⁇ median diameter of the second compound. This requirement makes it possible to simultaneously reduce the particle diameter of the noble metal after durability and increase the pore volume of the inclusion material. Therefore, it is possible to improve the gas diffusibility of the exhaust gas purification catalyst while maintaining good suppression of the aggregation of the noble metal particles, thereby improving the performance of the exhaust gas purification catalyst.
- the point is that the first compound and the second compound are simultaneously included in the oxide.
- separate inclusion that is, in the case of an exhaust gas purification catalyst in which the first compound is clad with an oxide, and the second compound is clad with an oxide separately, and the clad clathrate is mixed,
- the pore volume is large, the pore volume in the vicinity where the precious metal particles are present cannot be expanded, so that the performance is not high.
- the median diameter of the first compound and the second compound was measured using LA920 manufactured by HORIBA, and the pore volume measured by the N 2 adsorption method was measured using ASAP2010 manufactured by Shimadzu. Also refers to a D 50 is the median diameter.
- the precious metals effective for exhaust gas purification include Pt (platinum), Pd (palladium), and Rh (rhodium), and there is a preferable combination of the first compounds corresponding to these precious metals.
- the first compound can be an oxide containing Ce or an oxide containing Zr, and in this case, it can also be a complex oxide.
- the second compound is preferably a compound having a cocatalyst action.
- At least one of the first compound and the second compound includes a plurality of types of compounds.
- first compounds anchor materials carrying noble metal particles and / or having a plurality of second compound particles having a particle diameter larger than the first compound, noble metal particles,
- the interaction between the noble metal particles and the second compound as the promoter is enhanced, and among the elements that determine the catalyst performance described above, the function of (3) effective utilization of the contacted gas is enhanced. .
- the second compound is an oxide having an oxygen absorption / release function.
- a cocatalyst is an oxygen release material. Therefore, when the second compound is an oxide having an oxygen absorption / release function, the second compound functions effectively as a promoter. Therefore, the catalyst performance can be improved.
- the oxide having an oxygen absorption / release function include an oxide containing Ce (cerium).
- the median diameter of the first compound is 300 [nm] or less
- the median diameter of the second compound is 1000 [nm] or less.
- the median diameter of the first compound exceeds 300 [nm]
- the function of keeping the noble metal particles small rapidly decreases.
- the median diameter of the second compound is larger than 1000 [nm]
- the minimum of the median diameter of a 1st compound is not specifically limited, It can be set as the median diameter in the range which can be manufactured industrially.
- the median diameter of the first compound is 200 [nm] or less and the median diameter of the second compound is 1000 [nm] or less.
- the median diameter of the first compound is 200 [nm] or less, the amount of noble metal supported on one first compound particle can be reduced, and thus the exhaust gas purification performance is reduced due to aggregation of the noble metal particles. Can be effectively suppressed.
- the median diameter of the first compound and the median diameter of the second compound are expressed by the following formula (median diameter of the second compound) / (median diameter of the first compound) ⁇ 1.2. It is more preferable to satisfy the relationship. For example, if the median diameter of the first compound is 150 [nm], the median diameter of the second compound is 180 [nm] or more. The ratio of the median diameter of the second compound to the median diameter of the first compound is 1.2 or more, so that the median diameter of the second compound is larger than the median diameter of the first compound. The gas diffusibility can be improved more reliably.
- the pore volume within the pore diameter range of 0 to 200 [nm] by the N 2 adsorption method is 0.3 [cc / g] or more.
- the effective pore diameter for contact between the noble metal particles and the gas is in the range of 200 [nm] or less.
- the pore diameters in this numerical range indicate those in the catalyst powder.
- the pores in the region larger than 200 [nm] are the inner walls separating the through-holes of the refractory inorganic carrier such as the honeycomb carrier. The pores of the catalyst coat layer applied and formed on the substrate.
- the exhaust gas purification performance can be improved when the pore volume in the pore diameter range of 0 to 200 [nm] by the N 2 adsorption method is 0.3 [cc / g] or more.
- the pore volume in the pore diameter range of 0 to 200 [nm] by the N 2 adsorption method is less than 0.3 [cc / g] (per 1 g of catalyst), the performance rapidly decreases.
- Such pore volume can be easily realized by appropriately including the second compound in the exhaust gas purification catalyst.
- FIG. 7 is a graph showing an example of pore distribution by the N 2 adsorption method for the exhaust gas purification catalyst of the present invention containing the second compound and the prior art exhaust gas purification catalyst not containing the second compound. is there. It can be seen that the exhaust gas purification catalyst of the present invention has a pore distribution peak on the larger pore diameter side and an increased pore volume, as compared with the exhaust gas purification catalyst of the prior art.
- FIG. 8 is a graph showing the relationship between the pore volume of the exhaust gas purification catalyst having a pore diameter in the range of 0 to 200 [nm] and the NOx conversion rate as an example of the exhaust gas purification performance. As can be seen from FIG. 8, the NOx conversion increases as the pore volume of the catalyst increases.
- the pore volume in the pore diameter range of 0 to 200 [nm] by the N 2 adsorption method is 0.4 [cc / g] or more.
- the combination of the noble metal particles and the first compound in the exhaust gas purification catalyst of the present invention can be an oxide in which the noble metal is Pt and the first compound contains at least Ce.
- the oxide containing Ce may be not only a Ce oxide but also a composite oxide of Ce and another transition metal (for example, Zr).
- Another combination of the noble metal and the first compound in the exhaust gas purification catalyst of the present invention can be an oxide in which the noble metal is Pd and the first compound contains at least Zr.
- the oxide containing Zr may be not only a Zr oxide but also a composite oxide of Zr and another transition metal (for example, Ce or La).
- the noble metal may be Rh
- the first compound may be an oxide containing at least Zr.
- the oxide containing Zr may be not only a Zr oxide but also a composite oxide of Zr and another transition metal (for example, La).
- the second compound can be an oxide containing at least Ce.
- the oxide containing Ce is an oxygen storage / release material, so that it effectively functions as a co-catalyst and can improve the catalyst performance.
- This oxide containing Ce is not limited to Ce oxide, but may be a composite oxide containing other transition metals other than Ce, for example, Zr (zirconium), Pr (praseodymium), and Y (yttrium).
- the second compound is an oxide containing at least Ce
- no noble metal particles are present on the second compound. Therefore, the second compound does not deteriorate when impregnating the noble metal particles in the catalyst production process.
- the noble metal particles are higher than the measured exhaust gas temperature when the noble metal particles purify the exhaust gas. Is less susceptible to degradation due to this high temperature.
- the second compound may be an oxide containing at least one element selected from ⁇ Fe, Mn, Co, and Ni ⁇ .
- An oxide containing at least one transition element selected from ⁇ Fe, Mn, Co, and Ni ⁇ functions effectively as a co-catalyst, and improves the function of effectively using the contact gas, thereby improving the catalyst performance. Because you can.
- One kind of oxide of these transition elements may be used, an oxide containing two or more kinds may be used, and a composite oxide may be used.
- the second compound may be a compound containing at least one selected from ⁇ Ba, Mg and Ca ⁇ .
- the compound containing at least one alkaline earth metal element or Mg selected from ⁇ Ba, Mg, and Ca ⁇ is a NOx adsorbent, so that it functions effectively as a co-catalyst and effectively uses the gas in contact with it. This is because the catalyst performance can be improved. Therefore, an exhaust gas purification catalyst containing at least one selected from ⁇ Ba, Mg and Ca ⁇ in the second compound is particularly effective as a NOx adsorption catalyst. This is because the NOx adsorption reaction is very sensitive to gas contact. Therefore, the exhaust gas purification catalyst that improves the gas contact by including the second compound according to the present invention enhances the NOx adsorption reaction. Because you can.
- the exhaust gas purification catalyst of the present invention is supplied to an actual machine by coating the powder of the exhaust gas purification catalyst having the above-described requirements on a refractory inorganic carrier such as a honeycomb carrier.
- FIG. 9 is a schematic perspective view of an example of a refractory inorganic carrier coated with the exhaust gas purification catalyst of the present invention.
- the refractory inorganic carrier 100 shown in FIG. 9 is made of a refractory inorganic material, has a substantially cylindrical shape, and has a large number of through holes 100a extending from one end face to the other end face.
- the through-hole 100a is typically drawn so that an understanding of invention may be made easy. Therefore, the shape, size, number of through-holes 100a and the thickness of the inner wall of the refractory inorganic carrier separating the adjacent through-holes are different from the actual through-holes of the carrier.
- the exhaust gas purification catalyst powder is coated on the inner wall surface of the through-hole of the refractory inorganic carrier.
- a catalyst slurry containing powder of an exhaust gas purification catalyst is prepared, and after the catalyst slurry is attached to the inner wall surface of the refractory inorganic carrier, the excess slurry is removed, and then dried and fired.
- the coating amount may be an appropriate amount corresponding to the amount of noble metal contained in the exhaust gas purification catalyst.
- the refractory inorganic carrier on which the catalyst coat layer is formed is connected to the exhaust side of an automobile engine and used for purification of exhaust gas. This catalyst coat layer has the constituent requirements of the exhaust gas purification catalyst of the present invention.
- the catalyst coat layer formed by coating on a refractory inorganic carrier is preferably composed of a plurality of layers.
- FIG. 10 shows an enlarged cross-sectional view of one through hole 100a in the refractory inorganic carrier 100 of FIG. 9 in a cross section perpendicular to the penetrating direction. As shown in the enlarged sectional view of FIG. 10, the catalyst coat layer 10 is formed on the inner wall surface of the refractory inorganic carrier 100. In this catalyst coat layer, a total of two catalyst layers of a first catalyst layer 11 and a second catalyst layer 12 having different types of exhaust gas purification catalysts are laminated.
- the functions of the exhaust gas purification catalyst can be divided for each layer. Therefore, a plurality of functions can be optimized by each layer, and the performance of the exhaust gas purification catalyst as the entire catalyst coat layer can be improved.
- FIG. 10 shows a total of two catalyst coat layers.
- the exhaust gas purification catalyst of the present invention is not limited to the two-layer example, and has three or more layers. May be.
- Test 1 is an examination of the exhaust gas purification performance after endurance by the conversion rate.
- the exhaust gas purification catalysts of Examples 1 to 23 and Comparative Examples 1 and 2 below were prepared. These exhaust gas purification catalysts are composed of a catalyst layer coated on the inner wall surface of a cordierite monolith support as a refractory inorganic support.
- the cordierite-type monolith carrier on which the catalyst of each example and each comparative example was formed was mounted on an exhaust system of a gasoline engine having a displacement of 3500 [cc], the catalyst inlet temperature was set to 800 [° C.], and the system was operated for 50 hours. .
- Example 1 La-containing ZrO 2 powder having a specific surface area of 70 [m 2 / g] was impregnated with a Rh nitrate solution, and supported so that the supported concentration was 1.0 [wt%] as Rh. This was dried at 150 [° C.] for a whole day and night, and then calcined at 400 [° C.] for 1 hour to obtain Rh (1.0 [wt%]) / La-containing ZrO 2 powder (hereinafter referred to as “powder A”). This was pulverized, and powder A became Rh / La—ZrO 2 powder having a median diameter (D 50 ) of 148 [nm].
- a Zr-containing CeO 2 powder having a specific surface area of 80 [m 2 / g] was pulverized to obtain a median diameter (D 50 ) 231 [nm] (hereinafter referred to as “powder B”).
- boehmite, nitric acid and water were mixed and stirred for 1 [hr].
- the powder A and the powder B were slowly put into this liquid and further stirred for 2 [hr]. This was dried for 3 [hr] at 80 [° C.] under reduced pressure.
- powder C was obtained by calcination in air at 550 [° C.] for 3 [hr].
- the ratio of the total amount of powder A and powder B (powder A + powder B) to Al 2 O 3 is 70:30 by weight.
- the ratio of powder A to powder B is 80:20 by weight.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed by air flow and dried at 130 [° C], and then 400 [° C] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Example 2 The production process of the catalyst of Example 2 is the same as the production process of the catalyst of Example 1 described above, with the Rh support concentration in the powder A being 1.4 [wt%], and the total amount of the powder A and the powder B (powder A + powder B ) And Al 2 O 3 is the same as Example 1 except that the ratio is 50:50.
- Comparative Example 1 is an example that does not have the second compound.
- Rh nitrate solution was supported on La-containing ZrO 2 powder having a specific surface area of 70 [m 2 / g] so that the supported concentration was 0.8 [wt%] as Rh.
- powder D became Rh / La-ZrO 2 powder having a median diameter (D 50 ) of 148 [nm].
- boehmite, nitric acid and water were mixed and stirred for 1 [hr].
- the powder D was slowly put into this liquid and further stirred for 2 [hr]. This was dried for 3 [hr] at 80 [° C.] under reduced pressure.
- powder E After drying, calcination was performed at 550 [° C.] for 3 [hr] in air to obtain powder E.
- the ratio of the powder D to Al 2 O 3 is 70:30 by weight.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed by air flow and dried at 130 [° C], and then 400 [° C] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Comparative Example 2 is an example in which the first compound and the second compound are separately included in the oxide.
- Rh nitrate solution was supported on La-containing ZrO 2 powder having a specific surface area of 70 [m 2 / g] so that the supported concentration was 1.0 [wt%] as Rh.
- This was pulverized, and the powder F became Rh / La-ZrO 2 powder having a median diameter (D 50 ) of 148 [nm].
- boehmite, nitric acid and water were mixed and stirred for 1 [hr].
- the powder F was slowly put into this liquid and further stirred for 2 [hr]. This was dried for 3 [hr] at 80 [° C.] under reduced pressure.
- powder G After drying, calcination was performed at 550 [° C.] for 3 [hr] in air to obtain powder G.
- the ratio of powder F to Al 2 O 3 in powder G is 70:30.
- a Zr-containing CeO 2 powder having a specific surface area of 80 [m 2 / g] is pulverized to obtain a powder having a median diameter (D 50 ) of 231 [nm] (hereinafter referred to as “powder H”). Obtained.
- powder I was obtained by firing in air at 550 [° C.] for 3 [hr].
- the ratio of powder H to Al 2 O 3 is 70:30.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed by air flow and dried at 130 [° C], and then 400 [° C] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Comparative Example 3 is an example in which the median diameter of the second compound is smaller than the median diameter of the first compound.
- Rh nitrate solution was immersed in La-containing ZrO 2 powder having a specific surface area of 70 [m 2 / g], and supported so that the supported concentration was 1.0 [wt%] as Rh. This was dried at 150 [° C.] for a whole day and night and then calcined at 400 [° C.] for 1 hour to obtain Rh (1.0 [wt%]) / La-containing ZrO 2 powder (powder A). This was pulverized, and powder A became Rh / La-ZrO 2 powder having a median diameter (D 50 ) of 148 [nm].
- a Zr-containing CeO 2 powder having a specific surface area of 80 [m 2 / g] was pulverized to obtain a powder having a median diameter (D 50 ) of 117 nm (hereinafter referred to as “powder BB”). Obtained.
- boehmite, nitric acid and water were mixed and stirred for 1 [hr].
- the powder A and the powder BB were slowly put into this liquid, and further stirred for 2 [hr]. This was dried for 3 [hr] at 80 [° C.] under reduced pressure.
- powder CC After drying, it was fired in air at 550 [° C.] for 3 [hr] to obtain powder CC.
- the ratio of the total amount of powder A and powder BB (powder A + powder BB) to Al 2 O 3 is 70:30 by weight.
- the ratio of powder A to powder BB is 80:20 by weight.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed by air flow, and the slurry was dried at 130 [° C.].
- the catalyst was fired for a time to obtain a catalyst layer having a coat layer of 200 [g / L].
- Table 1 shows the characteristics and catalyst performance of the catalysts of Example 1, Example 2, Comparative Example 1, Comparative Example 2, and Comparative Example 3 described above.
- Example 1 and Example 2 have the second compound having a median diameter larger than that of the first compound, Comparative Example 1 without the second compound or Compared with Comparative Example 2 in which the first compound and the second compound were separately included in the oxide, the NOx conversion rate after durability was high.
- Comparative Example 2 has the second compound, but is included in the oxide separately from the first compound, so the pore volume is higher than Comparative Example 1, but the conversion rate is It was worse than Example 1 and Example 2. This is considered to mean that the pore volume in the vicinity of the first compound cannot be obtained and the gas diffusibility around the noble metal particles is poor. It is considered that the performance of Comparative Example 2 is higher than that of Comparative Example 1 because the second compound works as a promoter.
- Comparative Example 3 the first compound has the same median diameter as in Example 1, but the second compound has a median diameter smaller than the median diameter of the first compound. Therefore, the expansion effect of the pore volume of the catalyst powder due to the presence of the second compound was poor, and thus the powder pore volume and the NOx conversion rate were comparable to those of Comparative Example 1.
- a comparison between Comparative Example 3 and Example 1 shows that the second compound having a median diameter larger than that of the first compound according to the present invention increases the pore volume of the catalyst powder, and thus NOx. It is clear that the conversion is improved.
- Example 3 is an example having a plurality of first compounds.
- a dinitrodiamine Pt salt was supported on a Zr-containing CeO 2 powder having a specific surface area of 80 [m 2 / g] so that the supported concentration was 1.0 [wt%]. This was dried at 150 [° C.] for a whole day and night, and then calcined at 400 [° C.] for 1 hour to obtain Pt (1.0 [wt%]) / Zr-containing CeO 2 powder (hereinafter referred to as “powder J”). This was pulverized, and the powder J became a Pt / Zr—CeO 2 powder having a median diameter (D 50 ) of 131 [nm].
- powder K After drying, calcination was performed at 550 [° C.] for 3 [hr] in the air to obtain powder K.
- powder K the ratio of the total amount of powder A, powder B and powder J (powder A + powder B + powder J) to Al 2 O 3 is 70:30 by weight.
- powder A: powder B: powder J 40: 20: 40 by weight ratio.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cells was removed by air flow and dried at 130 [° C.], and then 400 [° C.] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Example 4 is an example having a plurality of first compounds and a plurality of second compounds.
- Pr-containing CeO 2 having a specific surface area of 80 [m 2 / g] was pulverized to obtain a powder having a median diameter (D 50 ) of 228 [nm] (powder L).
- powder M was obtained by baking in air at 550 [° C.] for 3 [hr].
- the powder M was 225 [g]
- the alumina sol was 25 [g]
- water was 230 [g]
- acetic acid was 20 [g].
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed with an air flow, and dried at 130 [° C.], then 400 [ °C]] for 1 hour to obtain a catalyst layer having a coating layer of 200 [g / L].
- Example 5 is an example having a plurality of first compounds. Further, Ce and Y-containing ZrO 2 powder (hereinafter referred to as “powder N”) was used as the second compound instead of the Zr-containing CeO 2 powder (powder B) in Example 3.
- a Ce and La-containing ZrO 2 powder having a specific surface area of 70 [m 2 / g] was supported with a Pd nitrate salt so that the supported concentration was 1.0 [wt%].
- powder P After drying, calcination was performed at 550 [° C.] for 3 [hr] in the air to obtain powder P.
- the weight ratio of the total amount of powder J, powder O and powder N (powder J + powder O + powder N) to Al 2 O 3 in the powder P is 70:30.
- powder J: powder N: powder O 40: 20: 40 by weight ratio.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed by air flow and dried at 130 [° C], and then 400 [° C] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Example 6 is an example having a plurality of first compounds.
- Boehmite, nitric acid and water were mixed and stirred for 1 [hr]. Powder A, powder O, and powder B were slowly added to this liquid, and further stirred for 2 [hr]. This was dried for 3 [hr] at 80 [° C.] under reduced pressure.
- powder Q After drying, it was calcined in air at 550 [° C.] for 3 [hr] to obtain powder Q.
- powder Q the ratio of the total amount of powder A, powder O and powder B (powder A + powder O + powder B) to Al 2 O 3 is 70:30.
- Powder A: Powder B: Powder M 40: 20: 40.
- Powder 225 [g], alumina sol 25 [g], water 230 [g], and acetic acid 20 [g] were prepared, and these were put into a magnetic ball mill, mixed and ground to obtain a catalyst slurry.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed by air flow and dried at 130 [° C], and then 400 [° C] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Table 2 shows the characteristics and catalyst performance of the catalysts of Examples 3 to 6 described above.
- the weight ratio of the total amount of the first compound and the second compound to the oxide (Al 2 O 3 ) was 70:30.
- the catalyst of the present invention is not limited to such a weight ratio.
- the performance could be further improved by having multiple types of the first compound and / or the second compound.
- Examples 7 to 19 are examples in which the median diameter of the first compound, the median diameter of the second compound, and the pore volume of the catalyst powder were various values. These median diameters were adjusted by pulverizing the first compound and the second compound.
- the types of the noble metal particles, the first compound, and the second compound in the catalysts of Examples 7 to 19 are the same as in Example 1.
- Example 1 for comparison of the noble metal species, first compound type and median diameter, second compound type and median diameter, catalyst powder pore volume, and purification performance of the catalysts of Examples 7 to 19 Table 3 also shows them.
- the median diameter of the first compound is 300 [nm] or less and the median diameter of the second compound is 1000 [nm] or less. Improved. Furthermore, when the median diameter of the first compound is 200 [nm] or less and the median diameter of the second compound is 1000 [nm] or less, the catalyst performance after durability is further improved.
- the catalyst performance after endurance was improved because the pore volume in the pore diameter range of 0 to 200 [nm] in the catalyst was 0.3 [cc / g] or more. Furthermore, when the pore volume is 0.4 [cc / g] or more, the catalyst performance after durability is further improved.
- Examples 20 to 23 are examples in which the second compound is an oxide containing at least one element selected from ⁇ Fe, Mn, Co, and Ni ⁇ . Examples 20 to 23 are the same as Example 1 except for the type of the second compound and the median diameter adjusted by grinding.
- Example 1 The values of Example 1 for comparison of the noble metal species, first compound type and median diameter, second compound type and median diameter, catalyst powder pore volume, and purification performance of the catalysts of Examples 20 to 23 In addition, it is shown in Table 4.
- Test 1 is an examination of the exhaust gas purification performance after endurance by the conversion rate when the air-fuel ratio is changed from the lean side to the rich side.
- the exhaust gas purification catalysts of Examples 24 to 29 below were prepared. These exhaust gas purification catalysts are composed of a catalyst layer coated on the inner wall surface of a cordierite monolith support as a refractory inorganic support.
- the cordierite-type monolith carrier on which the catalyst of each Example and each Comparative Example was formed was mounted on an exhaust system of a gasoline engine having a displacement of 3500 [cc], the catalyst inlet temperature was set to 700 [° C.], and the system was operated for 50 hours. .
- Example gas purification test The test temperature was 300 [° C.] to 350 [° C.].
- the exhaust gas purification rate in the section was obtained.
- Example 24 to 27 the second compound is an oxide containing Ce or an oxide containing at least one element selected from ⁇ Ba, Mg and Ca ⁇ .
- powder J was used instead of powder A in Example 1.
- the second compound was an oxide containing Ce or an oxide containing at least one element selected from ⁇ Ba, Mg, and Ca ⁇ , and a median diameter adjusted by pulverization. The rest is the same as in Example 1.
- Table 5 shows the noble metal species, the first compound type and median diameter, the second compound type and median diameter, the pore volume of the catalyst powder, and the NOx conversion rate after endurance of the catalysts of Examples 24-27.
- the second compound is an oxide containing at least one element selected from ⁇ Fe, Mn, Co and Ni ⁇ as compared with the case where the second compound is an oxide containing Ce. Had excellent characteristics as a NOx adsorption catalyst.
- Example 28 is an example in which the catalyst coat layer formed by coating on a refractory inorganic support is composed of a plurality of layers.
- a catalyst slurry in which the powder A of Example 1 was replaced with the powder J was obtained.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cells was removed by air flow and dried at 130 [° C.], and then 400 [° C.] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Example 1 the catalyst slurry of Example 1 was attached onto the catalyst layer, and after removing excess slurry in the cell with an air stream and drying at 130 [° C.], it was calcined at 400 [° C.] for 1 hour, A catalyst layer having a coating layer of 100 [g / L] was obtained.
- Example 29 is an example in which a catalyst coat layer formed by coating on a refractory inorganic support is composed of a plurality of layers in the same manner as in Example 28. The type of the coating layer is different from that in Example 28.
- a catalyst slurry in which the powder A of Example 1 was replaced with the powder O was obtained.
- the obtained catalyst slurry was attached to a cordierite monolith support (0.12 [L], 400 cells), excess slurry in the cell was removed by air flow and dried at 130 [° C], and then 400 [° C] Was fired for 1 hour to obtain a catalyst layer having a coat layer of 200 [g / L].
- Example 1 the slurry of Example 1 was deposited on the catalyst layer, and the excess slurry in the cell was removed with an air stream and dried at 130 [° C.], followed by firing at 400 [° C.] for 1 hour, A catalyst layer having a layer of 100 [g / L] was obtained.
- Table 6 shows the type of each coating layer and the purification performance of the catalyst in Example 28 and Example 29.
- Example 28 and Example 29 have a plurality of catalyst layers, so that the NOx conversion rate is improved as compared with Example 1 having a single layer, and excellent after durability. Had exhaust gas purification performance.
- the exhaust gas purifying catalyst of the present invention is superior in exhaust gas purifying performance than the conventional one, the amount of noble metal used can be reduced while maintaining the performance of purifying exhaust gas more than a certain level, and the exhaust gas system of an automobile Can be suitably used.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
第1の化合物のメジアン径<第2の化合物のメジアン径
の関係を満たすことを要旨とする。
第1の化合物のメジアン径<第2の化合物のメジアン径
を満たすことを要件の一つとしている。この要件により、耐久後の貴金属の粒子径を小さくすること、及び、包接材の細孔容量を大きくすることを両立させることができる。よって、貴金属粒子の凝集抑制を良好に維持しつつ、排気ガス浄化触媒のガス拡散性を向上させることができ、ひいては排気ガス浄化触媒の性能向上が図られる。
(第2の化合物のメジアン径)/(第1の化合物のメジアン径)≧1.2
の関係を満たすことが、より好ましい。例えば、第1の化合物のメジアン径が150[nm]であれば、第2の化合物のメジアン径は180[nm]以上である。第1の化合物のメジアン径に対する第2の化合物のメジアン径の比が1.2以上であることにより、第2の化合物のメジアン径が第1の化合物のメジアン径よりも大きいことによる、排気ガス浄化触媒のガス拡散性の向上をより確実に実現することができる。
試験1は、耐久後の排気ガス浄化性能を、転化率で調べたものである。
各実施例及び各比較例の触媒が形成されたコージェライト質モノリス担体を、排気量3500[cc]のガソリンエンジンの排気系に装着し、触媒入口温度を800[℃]とし、50時間運転した。
上記耐久を施した後のコージェライト質モノリス担体を、排気量3500[cc]のガソリンエンジンの排気系に装着し、触媒入口温度を150℃から500℃まで10℃/分で昇温し、そのときの触媒入口及び触媒出口におけるそれぞれの排気ガス中のHC、CO及びNOxの濃度を測定し、次式に従いHC転化率、CO転化率及びNOx転化率及び転化率を算出した。
CO転化率(%)=[(触媒入口CO濃度)-(触媒出口CO濃度)] /(触媒入口CO濃度)×100
NOx転化率(%)=[(触媒入口NOx濃度)-(触媒出口NOx濃度)] /(触媒入口NOx濃度)×100
また、50%転化率温度として、上記計算による転化率が50%となる温度についても求めた。この50%転化率温度が低いほうが低温活性が良い触媒といえる。
比表面積70[m2/g]のLa含有ZrO2粉末に硝酸Rh溶液を含浸し、担持濃度がRhとして1.0[wt%]となるように担持した。これを150[℃]で一昼夜乾燥後、400[℃]で1時間焼成して、Rh(1.0[wt%])/La含有ZrO2粉末(以下、「粉末A」という)を得た。これを粉砕し、粉末Aはメジアン径(D50)148[nm]のRh/La-ZrO2粉末となった。
実施例2の触媒の製造工程は、上述した実施例1の触媒の製造工程において、粉末A中のRh担持濃度を1.4[wt%]とし、粉末A及び粉末Bの合計量(粉末A+粉末B)とAl2O3との比を50:50にした以外は実施例1と同じである。
比較例1は、第2の化合物を有していない例である。
比較例2は、第1の化合物と第2の化合物とを別々に酸化物で包接した例である。
比較例3は、第1の化合物のメジアン径よりも第2の化合物のメジアン径が小さい例である。
実施例3は、第1の化合物を複数種で有する例である。
実施例3は、第1の化合物を複数種で有し、かつ、第2の化合物を複数種で有する例である。
実施例5は、第1の化合物を複数種で有する例である。また、第2の化合物として実施例3におけるZr含有CeO2粉末(粉末B)ではなく、Ce及びY含有ZrO2粉末(以下、「粉末N」という。)を用いた。
実施例6は、第1の化合物を複数種で有する例である。
実施例7~19は、第1の化合物のメジアン径、第2の化合物のメジアン径、触媒粉末の細孔容積を種々の値にした例である。これらのメジアン径の調整は、第1の化合物及び第2の化合物の粉砕により行った。なお、実施例7~19の触媒における貴金属粒子、第1の化合物及び第2の化合物の種類は、実施例1と同じである。
実施例20~23は、第2の化合物が、少なくとも{Fe、Mn、Co及びNi}から選ばれる少なくとも一種の元素を含む酸化物である例である。なお、実施例20~23は、第2の化合物の種類及びそれを粉砕により調整したメジアン径以外は実施例1と同じである。
試験1は、耐久後の排気ガス浄化性能を、空燃比をリーン側からリッチ側へと変化させたときの転化率で調べたものである。
各実施例及び各比較例の触媒が形成されたコージェライト質モノリス担体を、排気量3500[cc]のガソリンエンジンの排気系に装着し、触媒入口温度を700[℃]とし、50時間運転した。
試験温度は300[℃]~350[℃]とした。排気量2000[cc]のガソリンエンジンの排気系に触媒を装着して、リーン(A/F=25)40[sec]→リッチ(A/F=11)2[sec]の運転を行い、この区間における排気浄化率を求めた。
実施例24~27は、第2の化合物がCeを含む酸化物又は少なくとも{Ba、Mg及びCa}から選ばれる少なくとも一種の元素を含む酸化物である例である。なお、実施例24~27は、実施例1における粉末Aの代わりに粉末Jを用いた。また、第2の化合物を、Ceを含む酸化物又は少なくとも{Ba、Mg及びCa}から選ばれる少なくとも一種の元素を含む酸化物とし、かつ、それを粉砕により調整したメジアン径とした。それ以外は実施例1に同じである。
実施例28は、耐火性無機担体にコーティングされることにより形成された触媒コート層が複数層からなる例である。
実施例29は、実施例28と同様に耐火性無機担体にコーティングされることにより形成された触媒コート層が複数層からなる例である。なお、実施例28とコート層の種類が異なる。
Claims (16)
- 貴金属粒子と、
この貴金属粒子を担持した第1の化合物と、
この第1の化合物とは異なる種類の第2の化合物と、
これらの貴金属粒子、第1の化合物及び第2の化合物を覆った酸化物と
からなり、
前記第1の化合物のメジアン径と前記第2の化合物のメジアン径とが、次の不等式
第1の化合物のメジアン径<第2の化合物のメジアン径
の関係を満たすことを特徴とする排気ガス浄化触媒。 - 前記第1の化合物及び前記第2の化合物の少なくとも一方は、複数種の化合物を含むことを特徴とする請求項1に記載の排気ガス浄化触媒。
- 前記第2の化合物が、酸素吸放出機能を有する酸化物であることを特徴とする請求項1又は2に記載の排気ガス浄化触媒。
- 前記第1の化合物のメジアン径が300[nm]以下であり、かつ、前記第2の化合物のメジアン径が1000[nm]以下であることを特徴とする請求項1~3のいずれか1項に記載の排気ガス浄化触媒。
- 前記第1の化合物のメジアン径が200[nm]以下であり、かつ、前記第2の化合物のメジアン径が1000[nm]以下であることを特徴とする請求項1~3のいずれか1項に記載の排気ガス浄化触媒。
- 前記第1の化合物のメジアン径と第2の化合物のメジアン径とが、次式
(第2の化合物のメジアン径)/(第1の化合物のメジアン径)≧1.2
の関係を満たすことを特徴とする請求項1~3のいずれか1項に記載の排気ガス浄化触媒。 - 前記排気ガス浄化触媒は、N2吸着法による細孔径0~200[nm]の範囲の細孔容積が、0.3[cc/g]以上であることを特徴とする請求項1~6のいずれか1項に記載の排気ガス浄化触媒。
- 前記排気ガス浄化触媒は、N2吸着法による細孔径0~200[nm]の範囲の細孔容積が、0.4[cc/g]以上であることを特徴とする請求項1~6のいずれか1項に記載の排気ガス浄化触媒。
- 前記貴金属粒子がPtであり、前記第1の化合物が少なくともCeを含む酸化物であることを特徴とする請求項1~8のいずれか1項に記載の排気ガス浄化触媒。
- 前記貴金属粒子がPdであり、前記第1の化合物が少なくともZrを含む酸化物であることを特徴とする請求項1~8のいずれか1項に記載の排気ガス浄化触媒。
- 前記貴金属粒子がRhであり、前記第1の化合物が少なくともZrを含む酸化物であることを特徴とする請求項1~8のいずれか1項に記載の排気ガス浄化触媒。
- 前記第2の化合物が少なくともCeを含む酸化物であることを特徴とする請求項1~11のいずれか1項に記載の排気ガス浄化触媒。
- 前記第2の化合物が少なくとも{Fe、Mn、Co及びNi}から選ばれる少なくとも一種の元素を含む酸化物であることを特徴とする請求項1~11のいずれか1項に記載の排気ガス浄化触媒。
- 前記第2の化合物が少なくとも{Ba、Mg及びCa}から選ばれる少なくとも一種の元素を含む化合物であることを特徴とする請求項1~11のいずれか1項に記載の排気ガス浄化触媒。
- 前記排気ガス浄化触媒の粉末が耐火性無機担体にコーティングされてなることを特徴とする請求項1~14のいずれか1項に記載の排気ガス浄化触媒。
- 前記耐火性無機担体にコーティングされることにより形成された触媒コート層が複数層からなることを特徴とする請求項15に記載の排気ガス浄化触媒。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09802819.4A EP2308593B1 (en) | 2008-07-31 | 2009-06-30 | Catalyst for purification of exhaust gas |
US13/056,438 US8609578B2 (en) | 2008-07-31 | 2009-06-30 | Exhaust gas purifying catalyst |
JP2010522665A JP5447377B2 (ja) | 2008-07-31 | 2009-06-30 | 排気ガス浄化触媒 |
CN2009801303418A CN102112225B (zh) | 2008-07-31 | 2009-06-30 | 废气净化催化剂 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-198263 | 2008-07-31 | ||
JP2008198263 | 2008-07-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010013574A1 true WO2010013574A1 (ja) | 2010-02-04 |
Family
ID=41610274
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/061995 WO2010013574A1 (ja) | 2008-07-31 | 2009-06-30 | 排気ガス浄化触媒 |
Country Status (5)
Country | Link |
---|---|
US (1) | US8609578B2 (ja) |
EP (1) | EP2308593B1 (ja) |
JP (1) | JP5447377B2 (ja) |
CN (1) | CN102112225B (ja) |
WO (1) | WO2010013574A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011245416A (ja) * | 2010-05-26 | 2011-12-08 | Daihatsu Motor Co Ltd | 排ガス浄化用触媒およびその製造方法 |
JP2013180235A (ja) * | 2012-03-01 | 2013-09-12 | Nissan Motor Co Ltd | 排ガス浄化触媒及びその製造方法 |
JP2016505380A (ja) * | 2013-01-24 | 2016-02-25 | ビーエーエスエフ コーポレーション | 二金属層を有する自動車用触媒複合体 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102112225B (zh) | 2008-07-31 | 2013-10-23 | 日产自动车株式会社 | 废气净化催化剂 |
JP4956801B2 (ja) * | 2009-03-04 | 2012-06-20 | 日産自動車株式会社 | 排気ガス浄化触媒及びその製造方法 |
JP5041103B2 (ja) | 2009-11-17 | 2012-10-03 | 日産自動車株式会社 | 排ガス浄化用触媒及びその製造方法 |
JP5768474B2 (ja) * | 2011-04-28 | 2015-08-26 | 日産自動車株式会社 | 排気ガス浄化システム |
JP5942894B2 (ja) * | 2013-02-21 | 2016-06-29 | マツダ株式会社 | 排気ガス浄化用触媒の製造方法 |
RU2015143689A (ru) | 2013-03-14 | 2017-04-17 | Басф Корпорейшн | Каталитическое изделие с разъединенным тонкослойным покрытием и способы его изготовления |
ES2924391T3 (es) * | 2013-10-30 | 2022-10-06 | Basf Corp | Recubrimientos de catalizador para el control de la contaminación |
EP3144062B1 (en) * | 2014-05-13 | 2020-08-05 | Nissan Motor Co., Ltd | Exhaust gas purification catalyst |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10249198A (ja) * | 1997-03-10 | 1998-09-22 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒及びその製造方法 |
WO2007052627A1 (ja) | 2005-11-01 | 2007-05-10 | Nissan Motor Co., Ltd. | 排気ガス浄化用触媒及びその製造方法 |
JP2007229653A (ja) * | 2006-03-02 | 2007-09-13 | Nissan Motor Co Ltd | 排気ガス浄化触媒 |
JP2007229654A (ja) * | 2006-03-02 | 2007-09-13 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
JP2008168192A (ja) * | 2007-01-10 | 2008-07-24 | Nissan Motor Co Ltd | 排気ガス浄化触媒及びその製造方法 |
JP2008198263A (ja) | 2007-02-09 | 2008-08-28 | Konica Minolta Opto Inc | 近接場光発生器、光アシスト式磁気記録ヘッド、光アシスト式磁気記録装置 |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2005538C1 (ru) | 1992-02-05 | 1994-01-15 | Елена Алексеевна Дробаха | Способ приготовления катализатора для очистки выхлопных газов двигателей внутреннего сгорания |
US5948377A (en) * | 1996-09-04 | 1999-09-07 | Engelhard Corporation | Catalyst composition |
US6025297A (en) * | 1996-11-14 | 2000-02-15 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gas and process for producing the same |
US6107239A (en) * | 1998-01-19 | 2000-08-22 | Luchuang Environment Protection Science Co. Ltd. | Heat resistant metallic oxide catalyst for reducing pollution emission |
US20020128151A1 (en) * | 1998-05-01 | 2002-09-12 | Michael P. Galligan | Catalyst members having electric arc sprayed substrates and methods of making the same |
US20050163677A1 (en) * | 1998-05-01 | 2005-07-28 | Engelhard Corporation | Catalyst members having electric arc sprayed substrates and methods of making the same |
EP1046423B8 (en) | 1999-04-23 | 2007-11-21 | Umicore AG & Co. KG | Layered noble metal-containing exhaust gas catalyst and its preparation |
JP3688974B2 (ja) | 1999-05-24 | 2005-08-31 | ダイハツ工業株式会社 | 排ガス浄化用触媒 |
DE10024994A1 (de) | 1999-05-24 | 2001-01-04 | Daihatsu Motor Co Ltd | Katalytischer Umwandler zum Reinigen von Abgasen |
US6528029B1 (en) * | 1999-10-13 | 2003-03-04 | Engelhard Corporation | Catalyst compositions employing sol gel particles and methods of using the same |
US6458741B1 (en) | 1999-12-20 | 2002-10-01 | Eltron Research, Inc. | Catalysts for low-temperature destruction of volatile organic compounds in air |
MXPA03007403A (es) * | 2001-02-19 | 2004-07-30 | Toyota Motor Co Ltd | Catalizador para purificar gases de escape. |
US6528451B2 (en) | 2001-03-13 | 2003-03-04 | W.R. Grace & Co.-Conn. | Catalyst support material having high oxygen storage capacity and method of preparation thereof |
EP1287886A1 (de) * | 2001-08-09 | 2003-03-05 | OMG AG & Co. KG | Katalysator für die Reinigung der Abgase eines Verbrennungsmotors |
US7022644B2 (en) | 2002-02-20 | 2006-04-04 | Engelhard Corporation | Hydrogen sulfide-suppressing catalyst compositions |
US20040074230A1 (en) | 2002-10-16 | 2004-04-22 | Guinther Gregory H. | Method of oxidizing soot and reducing soot accumulation in a diesel fuel combustion after treatment system |
JP4175186B2 (ja) | 2003-06-12 | 2008-11-05 | トヨタ自動車株式会社 | 排ガス浄化用触媒とその製造方法 |
DE10335785A1 (de) * | 2003-08-05 | 2005-03-10 | Umicore Ag & Co Kg | Katalysatoranordnung und Verfahren zur Reinigung des Abgases von mager betriebenen Verbrennungsmotoren |
JP4236543B2 (ja) * | 2003-09-08 | 2009-03-11 | 本田技研工業株式会社 | 窒素酸化物の接触分解のための触媒と方法 |
JP4959129B2 (ja) * | 2004-02-16 | 2012-06-20 | 株式会社キャタラー | 排ガス浄化用触媒 |
JP4547930B2 (ja) * | 2004-02-17 | 2010-09-22 | 日産自動車株式会社 | 触媒、触媒の調製方法及び排ガス浄化用触媒 |
JP4547935B2 (ja) * | 2004-02-24 | 2010-09-22 | 日産自動車株式会社 | 排ガス浄化用触媒、排ガス浄化触媒、及び触媒の製造方法 |
JP4465352B2 (ja) * | 2004-03-11 | 2010-05-19 | 株式会社キャタラー | 排ガス浄化触媒 |
JP4513372B2 (ja) * | 2004-03-23 | 2010-07-28 | 日産自動車株式会社 | 排ガス浄化用触媒及び排ガス浄化触媒 |
JP4513384B2 (ja) * | 2004-03-31 | 2010-07-28 | 日産自動車株式会社 | 高耐熱性排ガス浄化用触媒及びその製造方法 |
EP1755778A1 (en) * | 2004-04-26 | 2007-02-28 | HTE Aktiengesellschaft The High Throughput Experimentation Company | Catalysts for the simultaneous removal of carbon monoxide and hydrocarbons from oxygen-rich exhaust gases and processes for the manufacture thereof |
EP1786562A2 (en) * | 2004-07-08 | 2007-05-23 | Nissan Motor Co., Ltd. | Catalyst, exhaust gas purification catalyst, and method for manufacturing same |
JP4513453B2 (ja) | 2004-08-02 | 2010-07-28 | マツダ株式会社 | 排気ガス浄化用触媒 |
US7566424B2 (en) | 2004-07-23 | 2009-07-28 | Mazda Motor Corporation | Exhaust gas purification catalyst |
US7713908B2 (en) * | 2004-08-30 | 2010-05-11 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Porous composite metal oxide and method of producing the same |
JP4277771B2 (ja) | 2004-09-09 | 2009-06-10 | トヨタ自動車株式会社 | 排ガス浄化用触媒、排ガス浄化装置および内燃機関を備えるシステム |
CN101080275B (zh) * | 2004-12-14 | 2010-05-05 | 日产自动车株式会社 | 催化剂、排气净化催化剂以及催化剂的制造方法 |
JP5200315B2 (ja) * | 2004-12-22 | 2013-06-05 | 日産自動車株式会社 | 排気ガス浄化触媒、及び排気ガス浄化触媒の製造方法 |
JP4999331B2 (ja) | 2005-03-24 | 2012-08-15 | 東京濾器株式会社 | 排気ガス浄化用触媒 |
EP1704910B1 (en) | 2005-03-24 | 2018-09-19 | Tokyo Roki Co., Ltd. | Exhaust gas purification catalyst |
US20080233039A1 (en) * | 2005-06-02 | 2008-09-25 | Symyx Technologies, Inc. | Catalysts For Co Oxidation,Voc Combustion And Nox Reduction And Methods Of Making And Using The Same |
JP2007050382A (ja) | 2005-08-19 | 2007-03-01 | Nissan Motor Co Ltd | 排ガス浄化触媒 |
JP2007105632A (ja) | 2005-10-13 | 2007-04-26 | Nissan Motor Co Ltd | 排ガス浄化触媒 |
US8119075B2 (en) | 2005-11-10 | 2012-02-21 | Basf Corporation | Diesel particulate filters having ultra-thin catalyzed oxidation coatings |
JP2007144290A (ja) | 2005-11-25 | 2007-06-14 | Nissan Motor Co Ltd | 排ガス浄化触媒及び排ガス浄化触媒の製造方法 |
KR101010070B1 (ko) | 2006-04-03 | 2011-01-24 | 르노 에스.아.에스. | 배기 가스 정화 촉매 및 그의 제조 방법 |
JP4881758B2 (ja) * | 2006-04-28 | 2012-02-22 | 日産自動車株式会社 | 排気ガス浄化用触媒及びその製造方法 |
JP2007313493A (ja) | 2006-04-28 | 2007-12-06 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
JP2007301526A (ja) * | 2006-05-15 | 2007-11-22 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒及びその製造方法 |
US20080044330A1 (en) * | 2006-08-21 | 2008-02-21 | Shau-Lin Franklin Chen | Layered catalyst composite |
US7550124B2 (en) * | 2006-08-21 | 2009-06-23 | Basf Catalysts Llc | Layered catalyst composite |
US7517510B2 (en) * | 2006-08-21 | 2009-04-14 | Basf Catalysts Llc | Layered catalyst composite |
JP4760625B2 (ja) | 2006-09-06 | 2011-08-31 | マツダ株式会社 | 排ガス浄化用触媒装置 |
JP4956130B2 (ja) | 2006-10-05 | 2012-06-20 | 日産自動車株式会社 | 排ガス浄化用触媒 |
JP5551329B2 (ja) * | 2006-11-14 | 2014-07-16 | 日産自動車株式会社 | 排気ガス浄化触媒及びその製造方法 |
RU2322296C1 (ru) | 2006-12-04 | 2008-04-20 | Институт физико-химических проблем керамических материалов Российской академии наук (ИПК РАН) | Способ приготовления катализатора очистки отработавших газов двигателей внутреннего сгорания и катализатор, полученный этим способом |
JP2008168278A (ja) * | 2006-12-15 | 2008-07-24 | Nissan Motor Co Ltd | 排ガス浄化用触媒及びその製造方法 |
EP2055367A3 (en) * | 2007-01-25 | 2009-05-27 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and manufacturing method thereof |
US7754171B2 (en) * | 2007-02-02 | 2010-07-13 | Basf Corporation | Multilayered catalyst compositions |
JP4998350B2 (ja) | 2007-04-05 | 2012-08-15 | 日産自動車株式会社 | 排ガス浄化用触媒 |
CN102112225B (zh) | 2008-07-31 | 2013-10-23 | 日产自动车株式会社 | 废气净化催化剂 |
JP4956801B2 (ja) | 2009-03-04 | 2012-06-20 | 日産自動車株式会社 | 排気ガス浄化触媒及びその製造方法 |
JP5041103B2 (ja) | 2009-11-17 | 2012-10-03 | 日産自動車株式会社 | 排ガス浄化用触媒及びその製造方法 |
-
2009
- 2009-06-30 CN CN2009801303418A patent/CN102112225B/zh active Active
- 2009-06-30 JP JP2010522665A patent/JP5447377B2/ja active Active
- 2009-06-30 US US13/056,438 patent/US8609578B2/en active Active
- 2009-06-30 EP EP09802819.4A patent/EP2308593B1/en active Active
- 2009-06-30 WO PCT/JP2009/061995 patent/WO2010013574A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10249198A (ja) * | 1997-03-10 | 1998-09-22 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒及びその製造方法 |
WO2007052627A1 (ja) | 2005-11-01 | 2007-05-10 | Nissan Motor Co., Ltd. | 排気ガス浄化用触媒及びその製造方法 |
JP2007229653A (ja) * | 2006-03-02 | 2007-09-13 | Nissan Motor Co Ltd | 排気ガス浄化触媒 |
JP2007229654A (ja) * | 2006-03-02 | 2007-09-13 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
JP2008168192A (ja) * | 2007-01-10 | 2008-07-24 | Nissan Motor Co Ltd | 排気ガス浄化触媒及びその製造方法 |
JP2008198263A (ja) | 2007-02-09 | 2008-08-28 | Konica Minolta Opto Inc | 近接場光発生器、光アシスト式磁気記録ヘッド、光アシスト式磁気記録装置 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011245416A (ja) * | 2010-05-26 | 2011-12-08 | Daihatsu Motor Co Ltd | 排ガス浄化用触媒およびその製造方法 |
JP2013180235A (ja) * | 2012-03-01 | 2013-09-12 | Nissan Motor Co Ltd | 排ガス浄化触媒及びその製造方法 |
JP2016505380A (ja) * | 2013-01-24 | 2016-02-25 | ビーエーエスエフ コーポレーション | 二金属層を有する自動車用触媒複合体 |
Also Published As
Publication number | Publication date |
---|---|
JP5447377B2 (ja) | 2014-03-19 |
US8609578B2 (en) | 2013-12-17 |
US20110177939A1 (en) | 2011-07-21 |
JPWO2010013574A1 (ja) | 2012-01-12 |
CN102112225A (zh) | 2011-06-29 |
EP2308593A4 (en) | 2017-02-22 |
CN102112225B (zh) | 2013-10-23 |
EP2308593B1 (en) | 2018-08-22 |
EP2308593A1 (en) | 2011-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5447377B2 (ja) | 排気ガス浄化触媒 | |
JP4853291B2 (ja) | 排気ガス浄化触媒及びその製造方法 | |
KR101051418B1 (ko) | 배기가스 정화용 촉매, 그 제조방법 및 이러한 촉매를이용한 배기가스의 정화방법 | |
JP6999555B2 (ja) | 希薄ガソリン直接噴射エンジン用触媒システム | |
US20080254978A1 (en) | Exhaust gas purifying catalyst and method of producing the same | |
KR20110129381A (ko) | 배기가스 정화용 촉매 | |
KR100993975B1 (ko) | 배기 가스 정화용 촉매 및 그 제조 방법 | |
JP2008168278A (ja) | 排ガス浄化用触媒及びその製造方法 | |
JP5014845B2 (ja) | 排ガス浄化用触媒、その製造方法、およびかかる触媒を用いた排ガスの浄化方法 | |
JP5589321B2 (ja) | 排気ガス浄化用触媒およびその製造方法 | |
JPWO2007145152A1 (ja) | 排ガス浄化用触媒 | |
JP5578369B2 (ja) | 排ガス浄化用触媒 | |
JP6748590B2 (ja) | 排ガス浄化用触媒 | |
EP2611536A1 (en) | Catalyst for gasoline lean burn engines with improved nh3-formation activity | |
JP2006523530A (ja) | 触媒支持体 | |
JP5987519B2 (ja) | 排ガス浄化触媒構造体 | |
WO2020195778A1 (ja) | 排ガス浄化用触媒 | |
JP4797838B2 (ja) | ガス浄化触媒 | |
JP2022534180A (ja) | 触媒化ガソリン微粒子フィルタ | |
JP5094049B2 (ja) | 排ガス浄化用触媒 | |
JP3876731B2 (ja) | 触媒担体構造体と排気ガス浄化用触媒 | |
JP4371600B2 (ja) | 排気ガス浄化用触媒及びその製造方法 | |
JP5328133B2 (ja) | 排ガス浄化用触媒 | |
JP2005279437A (ja) | 排ガス浄化用触媒 | |
JP5987518B2 (ja) | 排ガス浄化触媒 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980130341.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09802819 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010522665 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009802819 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13056438 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |