WO2005087373A1 - 排ガス浄化触媒 - Google Patents
排ガス浄化触媒 Download PDFInfo
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- WO2005087373A1 WO2005087373A1 PCT/JP2004/003213 JP2004003213W WO2005087373A1 WO 2005087373 A1 WO2005087373 A1 WO 2005087373A1 JP 2004003213 W JP2004003213 W JP 2004003213W WO 2005087373 A1 WO2005087373 A1 WO 2005087373A1
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- WIPO (PCT)
- Prior art keywords
- surface layer
- noble metal
- core
- catalyst
- carrier
- Prior art date
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Classifications
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- 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
- B01J23/58—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
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- 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
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- 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 purifying catalyst, and more particularly to an automobile exhaust gas purifying catalyst provided with a support containing a zirconium-based composite oxide.
- supported catalysts in which a noble metal (a catalytically active component) such as an orifice (R h) is supported on a porous carrier have been widely used as an exhaust gas purifying catalyst for automobiles.
- a supported catalyst is called a three-way catalyst because it can simultaneously oxidize CO and HC in exhaust gas and reduce NO x .
- ⁇ -alumina is used as the carrier.
- ⁇ -alumina undergoes a phase transition to ⁇ -alumina, resulting in a decrease in the specific surface area of the alumina.
- rhodium dissolves in alumina during use at a high temperature and catalyst performance is deteriorated (see Japanese Patent Application Laid-Open No. 2001-34771).
- Japanese Unexamined Patent Publication No. 2000-15001 discloses that rhodium is supported on the surface of a zirconia carrier stabilized with an alkaline earth metal.
- special table 2 0 0 2-5 1 8 1 7 1 Publication International publication wo 9.9 / 6 7 0
- No. 20 discloses a catalyst in which rhodium is supported on the surface of a zirconium carrier stabilized with a rare earth element.
- the stabilizing ginore cone supporting ⁇ -dicum is used, and 1; a daffili mussel is used, and the rhodime is highly dispersed and supported on the surface thereof.
- the rhodium supported on the stabilized dinorecon carrier having such a high specific surface area has a tendency for particles to grow during use at a high temperature, resulting in sintering of the orifice. Activity decreases due to burial of mouth rubber in carrier particles
- the present invention provides a method for using a stabilized dinolenium-based composite oxide such as a stabilized zirconia as a carrier material, while reducing the catalytic activity even during use at high temperatures.
- An object of the present invention is to provide a suppressed exhaust gas purifying catalyst.
- the present inventors have conducted intensive studies to achieve the above object, and as a result,
- Stabilized body with relatively low specific area heat-resistant with relatively high specific surface mussels on the surface of the core part.
- the cycle was repeated, and the catalyst performance was not significantly reduced even after long-term use at high temperatures. Since the surface layer where the noble metal is dissolved is very thin, it can sufficiently follow the fluctuation of the atmosphere during the short IdEI period between the solid solution and the precipitation under noble metal.
- the noble metal supported on the surface of the surface layer which does not form a solid solution in the surface layer, exhibits catalytic activity in the initial process, even though the dissolved metal does not function. The present invention is based on such knowledge.
- the carrier comprises a carrier and an active component comprising a noble metal carried by the carrier, and the carrier is selected from the group consisting of rare earth elements and alkaline earth elements.
- the specific surface area of the surface portion of the IJ is larger than that of the specific surface mussels of the core, and a part of the metal is part of the surface portion of the metal.
- An exhaust gas purifying catalyst is provided, which is dissolved in a zirconium-based multi-portion oxide and the remainder is supported on the surface of the surface layer.
- Figure 1A shows the S particles at 50,000 times magnification of the particles used in Example 1.
- Figure 1B is a SEM photograph of the carrier prepared in Example 1 at a magnification of 50,000 times.
- Figure 2A shows the magnification of the particles used in Example 1 at 200,000 times. It is a SEM photograph
- FIG. 2B is a SEM photograph of the carrier prepared in Example 1 at a magnification of 200,000.
- the carrier of the exhaust gas purifying catalyst of the present invention has a core containing a stabilized zirconium-based composite oxide having a low specific surface area, and a surface layer (coating layer) covering the surface of the core.
- the surface layer contains a heat-resistant zirconium-based composite oxide having a high specific surface area.
- a carrier having a core portion and a surface portion supports a catalytically active component made of a noble metal. Part of the noble metal is dissolved in the surface layer of the carrier, and the rest is supported on the surface of the carrier.
- the specific surface area of the surface layer is larger than that of the core.
- the ratio SSA sur / SSA cor of the specific surface area SSA sur of the surface layer portion to the specific surface area SSA cor of the core portion is 2 to 20.
- the stabilized zirconium-based composite oxide constituting the core of the carrier of the exhaust gas purifying catalyst of the present invention is at least one type of stabilizing material selected from the group consisting of rare earth elements and alkaline earth elements. Includes zirconia stabilized by containing elements.
- Rare earth elements as stabilizing elements include scandium and itt Includes realm and lanthanide, among which are yttrium, lanthanum (La), cerium (Ce), neodymium (Nd), and praseodymium (Pm). Preferred, especially lanterns.
- alkaline earth elements as stabilizing elements include calcium (Ca), strontium (Sr), norium (Ba) and radium (Ra). Of these, Norium is preferred. These stabilizing elements can be used alone or in combination of two or more.
- the stabilized zirconium-based composite oxide preferably contains a stabilizing element in a proportion of 3 to 20 atoms per 100 atoms of zirconium in the zirconia. If the ratio of the stabilizing element is less than 3 atomic%, the stabilizing effect on zirconia is not sufficient, and on the other hand, the ratio of the stabilizing element is 20 atoms. When the ratio exceeds / 0 , a composite oxide having low heat resistance is generated in the zirconia.
- the crystal structure of zirconia stabilized by the stabilizing element is cubic or tetragonal.
- the stabilized zirconia-based composite oxide particles constituting the core have a specific surface area of 50 m 2 Zg or less.
- the specific surface area is usually greater than 15 m 2 / g.
- the stabilized zirconium-based composite oxide particles more preferably have a specific surface area of 15 m 2 Z g to 30 m 2 / g .
- the stabilized zirconia-based composite oxide particles in the core are 5! It preferably has an average particle size of up to 30 ⁇ . Such stabilized zirconia is commercially available.
- the composite oxide is a stabilized zirconium-based composite oxide similar to the stabilized zirconium-based composite oxide contained in the core, except that the specific surface area is higher than that of the core as described above. I prefer being there.
- the surface layer preferably has a specific surface area of 60 m 2 Zg to 300 m 2 / g. Also, the surface layer is preferably provided at a rate of 0 • 1 to 10% of the weight of the core. If the amount of the surface layer portion is less than 0.1% by weight, the coverage of the core portion by the surface layer portion is reduced, and the initial catalyst function cannot be sufficiently exhibited.
- the surface layer becomes thicker, the surface layer peels off from the core, and the solid solution / precipitation of M metal causes a short-period atmosphere between lean and rich at high temperatures. They tend to follow fluctuations and become inextricable.
- the surface layer portion is present in a proportion of 0.1 to 1 0% by weight of ⁇ portion, stabilizing Jirukonia based composite oxide of the surface layer portion, a particle ⁇ s 5 nm ⁇ 1 5 nm particles
- the solid solution Z precipitation of the noble metal can be repeated more rapidly.
- the surface layer portion is present in a proportion of 1 to 5% by weight of the core portion.o The coverage of the core portion surface by the surface layer portion is 5%.
- Preferred examples of the noble metal as the catalytically active component include, but are not limited to, platinum, palladium, alloys of rhodium and platinum, and alloys of palladium and platinum. More preferred.
- a part of the noble metal supported on the surface layer of the carrier is dissolved in the heat-resistant zirconium-based composite oxide on the surface layer of the carrier, and the remainder is supported on the surface of the surface layer of the carrier. .
- the total amount of the noble metal supported is usually 0 .0 of the total weight of the catalyst (support + noble metal).
- the precious metal solid solution rate (the ratio of the precious metal dissolved in the total weight of the supported precious metal) is usually preferably 50% or more.
- the catalyst of the present invention In order to produce the catalyst of the present invention, first, stabilized zirconium-based composite oxide particles serving as a core portion are coated with a heat-resistant zirconia-based composite oxide. Next, a noble metal is carried on the obtained composite carrier, and a part thereof is dissolved in the surface layer of the carrier.
- a method known per se in the art can be employed.
- a water-soluble zirconium salt eg, zirconium oxynitrate (ZrO (NO 3 ) 2)
- ZrO (NO 3 ) 2 zirconium oxynitrate
- Rukoniumu (zr (SO 4) 2), etc.) an aqueous solution with a neutralizing agent (for example, the bicarbonate a Nmoniumu, by adding ammonia, etc.), depositing a Jirukoyua precursor on the core particles.
- the washed particles are then dried, preferably at a temperature of 50 to 200 ° C for 1 to 48 hours, and then preferably at a temperature of 65 to 100 ° C for 1 to 12 hours. Firing, preferably for 2 to 4 hours, in an oxidizing atmosphere (eg, air). In this way, core particles coated with zirconia are obtained.
- an oxidizing atmosphere eg, air
- the zirconia-coated core particles are immersed in an aqueous solution containing a stabilizing element in the form of a water-soluble salt to include the stabilizing element in the zirconia coating layer.
- a stabilized zirconia (a heat-resistant zirconia) containing the stabilizing element in a proportion substantially equal to the proportion of the water-soluble salt of the stabilizing element to the zirconia can be obtained.
- water-soluble salt of the stabilizing element examples include inorganic acid salts such as sulfates, nitrates, hydrochlorides, and phosphates, and organic acids such as acetates and oxalates. it can. Of these, nitrates are preferred.
- the coating layer can also be formed using a mixed salt of a zirconium salt and a salt of a stabilizing element.
- a dispersion of core particles in an organic solvent for example, isopropanol, ethanol, etc.
- a dispersion of zirconium alkoxide for example, tetraethanol
- Rumarupu doo Kishijiruko two Kum Z r (OC 4 H 9 ) 4 the aqueous solution and the stabilizing element or the like) added, including zirconyl two ⁇ beam and stabilizing element by hydrolyze the zirconia Umuaruko sulfoxide
- a dispersion in which the precursor has precipitated is obtained.
- the dispersion is evaporated to dryness, and the evaporated and dried product is dried under the same drying conditions as above, and then fired under the same firing conditions as above.
- a stabilized zirconium surface layer is formed on the core particle surface.
- stabilized zirconium (heat-resistant zirconia) containing the stabilizing element at substantially the same ratio as the proportion of the water-soluble salt of the stabilizing element to the zirconium alkoxide can be obtained.
- Noble metal is added to the carrier of the present invention obtained in this manner.
- the carrier particles are put into an aqueous solution containing a required amount of a noble metal in the form of a water-soluble salt, and the noble metal salt is adsorbed and carried on the surface of the carrier, followed by filtration and drying.
- the noble metal used at this time can be adsorbed and supported on the carrier in its entirety.
- the obtained dried particles can be fired in the air under conditions of a temperature and a time sufficient to cause the noble metal to form a solid solution into the stabilized zirconia powder.
- the sintering temperature for solid solution is preferably from 700 ° C. to 100 ° C.
- the firing temperature is more preferably between 700 ° C and 900 ° C.
- the calcination time varies depending on the calcination temperature, but is usually 2 to 4 hours.
- the solid solution rate of the noble metal can be adjusted by the firing time.
- the water-soluble noble metal salt include inorganic acid salts such as nitrates and hydrochlorides. Of these, nitrates are preferred. In this solid solution, 30% to 90% by weight of the noble metal initially supported on the surface of the stabilized zirconia carrier can be dissolved in the stabilized zirconia.
- the catalyst obtained as described above can be used after being sized, for example, into pellets.
- the amount of the noble metal dissolved in the stabilized zirconium can be analyzed using ICP emission spectroscopy. More specifically, a stabilizing zirconia (including a solid solution of noble metal), which is a force that does not dissolve noble metal oxide fine particles that may be present on the surface of the carrier, is dissolved.
- the catalyst can be immersed in the dissolving agent to be dissolved, and sufficiently stirred to dissolve the stabilized zirconia.
- the solution can be analyzed for noble metals by ICP emission spectroscopy. Use a solution of hydrogen fluoride and water in a volume ratio of 1/15 to 1Z4 as the dissolving agent, and perform the dissolution operation at room temperature (20 ° C to 30 ° C) for 12 hours. be able to.
- the solid solution of the noble metal is deposited on the surface of the carrier. Precipitated as fine particles of nanometer order, and precipitated in a high-temperature lean (oxidizing) atmosphere with a high fuel-air ratio, that is, a low fuel concentration and excess oxygen.
- the precious metal dissolves in the carrier again, the cycle is repeated, and the particle growth of the precious metal is suppressed even if the precious metal is used for a long period of time under a short-period, high-temperature atmosphere between the rinsing and the cleaning. In addition, the high catalytic activity is maintained, and the catalytic performance is not significantly reduced. Precious metal dissolved
- the noble metal supported on the surface of the carrier surface layer exhibits catalytic activity from the beginning of use when the solid solution of the noble metal does not function as a catalyst.
- the exhaust gas purifying catalyst of the present invention sufficiently exhibits the activity of a hornworm for a long period of time from the initial use.o
- the amount of the surface layer in the carrier is small. Since the noble metal is supported on the surface layer with a small amount of metal, the amount of metal used can be reduced.
- Commercially available zirconia particles manufactured by Daiichi Rare Element Co., specific surface area: 24 m 2 g N tetragonal, average particle diameter 13 ⁇
- 20 g of the core particles are put into 100 mL of ion-exchanged water, and the homogenizer is used to rotate the core particles at a rotation speed of 100 to 200 rPm.
- the mixture was stirred for 30 minutes to sufficiently disperse the nanoparticle. Then, the stirring by the homogenizer is changed to the stirring by the stirrer, and the core particle dispersion contains zirconium oxynitrate in an amount corresponding to 5% by weight of the core particles to generate ginole: ⁇ di.
- Aqueous solution contains zirconium oxynitrate in an amount corresponding to 5% by weight of the core particles to generate ginole: ⁇ di.
- the mixture was calcined at 600 ° C. for 3 hours to obtain desired dino-recovered core particles.
- the zirconia-coated core particles obtained in (A) should be added in an amount corresponding to 10 mol% of the coated zirconia amount. Impregnated with an aqueous solution containing lanthanum nitrate at 80 ° C.
- part of the supported rhodium was dissolved in the surface layer.
- a part of the stabilized zirconium in which this rhodium was dissolved was immersed in a solution of hydrogen fluoride and water at a volume ratio of 1/15 at room temperature for 12 hours to dissolve the zirconia, and the resulting solution was obtained.
- the amount of rhodium in the solution was analyzed by ICP emission spectroscopy. 70% of the solid solution was stabilized
- FIG. 1A shows an SEM photograph of the carrier particles used in Example 1 at a magnification of 5 J
- FIG. 1A shows a SEM photograph of the carrier prepared in Example 1 at a magnification of 50,000
- FIG. 2A shows a SEM photograph of the carrier particles used in Example 1 at a magnification of 200,000 times
- FIG. 2B shows a SEM photograph of the carrier prepared in Example 1 at a magnification of 200,000 times.
- Example 2 A procedure was performed in the same manner as in Example 1 except that an aqueous solution containing zirconium oxynitrate in an amount producing dinolecone equivalent to 1% by weight of the core particles in (A) was used. The solid dissolution rate of the dimmed medium from which the B-shaped angle B medium was obtained was 55% by weight.
- the solvent was removed by evaporating under reduced pressure of Hg to dryness.
- the obtained evaporated to dryness was dried at 100 ° C for 2 hours, and then dried at 60 ° C.
- Example 1 the procedure was the same as in Example 1 except that zirconium oxynitrate was used in such an amount as to produce dinorecone in an amount equivalent to 10% by weight of the core particles.
- a catalyst was obtained.
- the catalyst had a supported amount of dime of 0.3% by weight, and a solid solution ratio of the distillate was 80%.
- Comparative Example 1 A pellet-shaped catalyst was obtained by the same procedure as in Example 1 except that no layer was formed on the core material. ⁇ -dime supported on this catalyst
- the village is 0.3 weight 0 /. And the solid solution rate of rhodium was 10%.
- a pellet-shaped catalyst was obtained by the same procedure as in Example 1 except that the step of Example 1 (B) was not performed.
- Each of the pellet-shaped catalysts obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was filled in a flow-type aging apparatus, and then 30 parts by volume of carbon monoxide gas was added to 300 parts by volume of silicon gas.
- the catalyst sample was charged into a fixed-bed flow reactor at normal pressure, and while flowing a model gas equivalent to the stoichiometric pressure, the catalyst sample was heated at a temperature of 100 ° C to 500 ° C at a temperature of 12 Heating is performed at a heating rate of 1 minute, and the purification rates of CO 2, NO x and HC during the heating are continuously measured.
- Table 1 shows the results
- the catalyst of the present invention has a lower 50% purification temperature than the catalyst of the comparative example. This indicates that the exhaust gas purifying catalyst of the present invention does not show a significant decrease in catalytic performance even when used at a high temperature for a long period of time from the beginning.
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- 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)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2004/003213 WO2005087373A1 (ja) | 2004-03-11 | 2004-03-11 | 排ガス浄化触媒 |
EP04719627A EP1736241B1 (en) | 2004-03-11 | 2004-03-11 | Exhaust gas-purifying catalyst |
CNB2004800423852A CN100479920C (zh) | 2004-03-11 | 2004-03-11 | 排气净化催化剂 |
JP2006510841A JP4465352B2 (ja) | 2004-03-11 | 2004-03-11 | 排ガス浄化触媒 |
US11/517,852 US7297654B2 (en) | 2004-03-11 | 2006-09-07 | Exhaust gas-purifying catalyst |
Applications Claiming Priority (1)
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PCT/JP2004/003213 WO2005087373A1 (ja) | 2004-03-11 | 2004-03-11 | 排ガス浄化触媒 |
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Application Number | Title | Priority Date | Filing Date |
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US11/517,852 Continuation US7297654B2 (en) | 2004-03-11 | 2006-09-07 | Exhaust gas-purifying catalyst |
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WO2005087373A1 true WO2005087373A1 (ja) | 2005-09-22 |
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US (1) | US7297654B2 (ja) |
EP (1) | EP1736241B1 (ja) |
JP (1) | JP4465352B2 (ja) |
CN (1) | CN100479920C (ja) |
WO (1) | WO2005087373A1 (ja) |
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JP2007105571A (ja) * | 2005-10-11 | 2007-04-26 | Cataler Corp | 排ガス浄化用触媒及びその製造方法 |
JP2008100202A (ja) * | 2006-10-20 | 2008-05-01 | Cataler Corp | 排ガス浄化用触媒 |
JP2009279544A (ja) * | 2008-05-23 | 2009-12-03 | Toyota Motor Corp | コアシェル構造体及び当該コアシェル構造体を含む排ガス浄化用触媒 |
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EP2789820A4 (en) * | 2011-12-07 | 2015-08-26 | Toyota Motor Co Ltd | EXHAUST GAS PURIFYING DEVICE FOR INTERNAL COMBUSTION ENGINE |
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CN109153009A (zh) * | 2016-05-26 | 2019-01-04 | 巴斯夫公司 | 核/壳催化剂粒子及制造方法 |
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ATE179907T1 (de) * | 1994-11-02 | 1999-05-15 | Anglo American Res Lab Pty Ltd | Katalysator mit zirkonoxid/ceroxid träger |
US6107239A (en) * | 1998-01-19 | 2000-08-22 | Luchuang Environment Protection Science Co. Ltd. | Heat resistant metallic oxide catalyst for reducing pollution emission |
GB9813367D0 (en) | 1998-06-22 | 1998-08-19 | Johnson Matthey Plc | Catalyst |
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JP2001347167A (ja) | 2000-06-09 | 2001-12-18 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒 |
WO2002066155A1 (fr) * | 2001-02-19 | 2002-08-29 | Toyota Jidosha Kabushiki Kaisha | Catalyseur de clarification de gaz d'échappement |
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2004
- 2004-03-11 CN CNB2004800423852A patent/CN100479920C/zh not_active Expired - Fee Related
- 2004-03-11 JP JP2006510841A patent/JP4465352B2/ja not_active Expired - Fee Related
- 2004-03-11 EP EP04719627A patent/EP1736241B1/en not_active Expired - Lifetime
- 2004-03-11 WO PCT/JP2004/003213 patent/WO2005087373A1/ja not_active Application Discontinuation
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2006
- 2006-09-07 US US11/517,852 patent/US7297654B2/en not_active Expired - Fee Related
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JPH1128359A (ja) * | 1997-07-10 | 1999-02-02 | N E Chemcat Corp | 排気ガス浄化用触媒構造体 |
EP1166855A1 (en) * | 2000-06-27 | 2002-01-02 | ICT Co., Ltd. | Exhaust gas purifying catalyst |
JP2003117393A (ja) * | 2001-10-09 | 2003-04-22 | Toyota Motor Corp | 排ガス浄化用触媒 |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007105571A (ja) * | 2005-10-11 | 2007-04-26 | Cataler Corp | 排ガス浄化用触媒及びその製造方法 |
US9073048B2 (en) | 2006-07-05 | 2015-07-07 | Cataler Corporation | Exhaust gas-purifying catalyst and method of manufacturing the same |
JP2008100202A (ja) * | 2006-10-20 | 2008-05-01 | Cataler Corp | 排ガス浄化用触媒 |
KR101432331B1 (ko) | 2006-10-20 | 2014-08-20 | 가부시키가이샤 캬타라 | 배출 가스 정화용 촉매 |
JP2009279544A (ja) * | 2008-05-23 | 2009-12-03 | Toyota Motor Corp | コアシェル構造体及び当該コアシェル構造体を含む排ガス浄化用触媒 |
JP2009279546A (ja) * | 2008-05-23 | 2009-12-03 | Toyota Motor Corp | コアシェル構造体の製造方法及びそれにより製造されたコアシェル構造体を含む排ガス浄化用触媒 |
JP2011183316A (ja) * | 2010-03-09 | 2011-09-22 | Mazda Motor Corp | 排気ガス浄化用触媒 |
JP2015098007A (ja) * | 2013-11-20 | 2015-05-28 | マツダ株式会社 | 排気ガス浄化用触媒材及びその製造方法 |
WO2015075875A1 (ja) * | 2013-11-20 | 2015-05-28 | マツダ株式会社 | 排気ガス浄化用触媒材及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1736241A1 (en) | 2006-12-27 |
JP4465352B2 (ja) | 2010-05-19 |
JPWO2005087373A1 (ja) | 2008-01-24 |
US7297654B2 (en) | 2007-11-20 |
US20070004589A1 (en) | 2007-01-04 |
EP1736241A4 (en) | 2008-11-05 |
CN1925913A (zh) | 2007-03-07 |
EP1736241B1 (en) | 2012-10-03 |
CN100479920C (zh) | 2009-04-22 |
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