WO2013114876A1 - 排ガス成分浄化触媒材及びそれを備えた触媒材付きパティキュレートフィルタ - Google Patents
排ガス成分浄化触媒材及びそれを備えた触媒材付きパティキュレートフィルタ Download PDFInfo
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- WO2013114876A1 WO2013114876A1 PCT/JP2013/000506 JP2013000506W WO2013114876A1 WO 2013114876 A1 WO2013114876 A1 WO 2013114876A1 JP 2013000506 W JP2013000506 W JP 2013000506W WO 2013114876 A1 WO2013114876 A1 WO 2013114876A1
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- Prior art keywords
- exhaust gas
- composite oxide
- oxide particles
- catalyst material
- purification catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000002245 particle Substances 0.000 claims abstract description 142
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 37
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 34
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 23
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 110
- 239000002131 composite material Substances 0.000 claims description 97
- 238000000746 purification Methods 0.000 claims description 49
- 229910052760 oxygen Inorganic materials 0.000 claims description 47
- 239000001301 oxygen Substances 0.000 claims description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 3
- 238000002485 combustion reaction Methods 0.000 description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 34
- 229910052799 carbon Inorganic materials 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910002830 PrOx Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 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 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UYXRCZUOJAYSQR-UHFFFAOYSA-N nitric acid;platinum Chemical compound [Pt].O[N+]([O-])=O UYXRCZUOJAYSQR-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
-
- 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
- B01D2255/2063—Lanthanum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2066—Praseodymium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/2068—Neodymium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/40—Mixed oxides
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- 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
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- 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
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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
Definitions
- the present invention relates to a catalyst material used for burning and removing particulates discharged from an engine, and a particulate filter with a catalyst material provided with the catalyst material.
- a filter for collecting particulates (PM: Particulate matter such as carbonaceous fine particles) in the exhaust gas is provided.
- PM particulates
- the PM accumulation amount is estimated based on the pressure difference of the pressure sensors provided before and after the filter, and when the accumulation amount reaches a predetermined value, engine fuel injection control (fuel increase, post-injection, etc.)
- the unburned HC is contained in the exhaust gas and supplied to the oxidation catalyst, and the unburned HC is burned by the oxidation catalyst, thereby increasing the temperature of the exhaust gas reaching the filter and burning off PM.
- a catalyst material is generally carried on the exhaust gas passage wall of the filter.
- Patent Document 1 discloses a catalyst in which an exhaust gas passage wall of a filter is mixed with a composite oxide of Zr and a rare earth metal other than Ce and a composite oxide containing Ce and a rare earth metal or an alkaline earth metal. It is described that a layer is provided.
- Patent Document 2 describes that a catalyst layer in which a noble metal-doped CePr-based composite oxide and a composite oxide of Zr and a rare earth metal are mixed is provided on the passage wall of the filter.
- Patent Document 3 includes a catalyst layer containing a Zr-based composite oxide containing Zr, Nd, and a rare earth metal other than Nd and Ce, such as La or Pr, on the exhaust gas passage wall of the filter.
- a catalyst layer containing a Zr-based composite oxide containing Zr, Nd, and a rare earth metal other than Nd and Ce, such as La or Pr, on the exhaust gas passage wall of the filter.
- a filter is described.
- the mixture of the Zr-based composite oxide and the Ce-based composite oxide in the catalyst layer increases the PM combustion speed and shortens the regeneration time of the filter. It can be improved.
- the graph of FIG. 1 schematically shows a change with time of the PM remaining ratio when PM deposited on the catalyst layer burns. Initially, the combustion of PM proceeds rapidly, but after passing through the rapid combustion region (for example, the first combustion period until the PM remaining ratio becomes 100% to 50%), the combustion of PM becomes slow (PM It shifts to the combustion late stage until the remaining ratio becomes 50% to 0%. This point will be described in detail below.
- the catalyst layer is formed to be porous with large internal voids so that PM can easily enter the catalyst layer.
- PM is dispersed and deposited not only on the surface of the catalyst layer but also inside the catalyst layer, so that most of the PM comes into contact with the catalyst and is easily combusted.
- the catalyst layer becomes bulky, and there is a problem that the flow resistance of the exhaust gas passing through the filter increases.
- the present invention has been made in view of the above problems, and an object thereof is to allow the combustion to proceed efficiently in both the rapid combustion region and the slow combustion region of PM deposited on the filter.
- the present invention provides an exhaust gas component purification catalyst material comprising praseodymium oxide (Pr 2 O 3 , Pr 6 O 11 : hereinafter referred to as PrO x ) particles and zirconium (Zr) -based composite oxide. It was set as the structure which particle
- PrO x praseodymium oxide
- Zr zirconium
- the exhaust gas component purification catalyst material according to the present invention is used to burn and remove particulates in exhaust gas, and includes composite oxide particles containing zirconium and neodymium and not containing cerium, and the composite oxide particles. And praseodymium oxide particles in contact with.
- the ZrNd-based composite oxide containing Zr and neodymium (Nd) has high ionic conductivity, and oxygen is taken into the inside by an oxygen exchange reaction to release active oxygen.
- PrO x has a high oxygen storage capacity (OSC ability) like cerium oxide (CeO 2 ) that has been conventionally used as a co-catalyst, and moreover than CeO 2. Large amount of oxygen exchange between gas phase oxygen and oxide surface. That is, PrO x becomes an excellent oxygen supply source for the ZrNd-based composite oxide.
- the complex oxide particles containing Zr and Nd and not containing Ce and the PrO x particles are brought into contact with each other so that oxygen released in a large amount from the PrO x particles is close to the complex oxide particles.
- the combustion of PM proceeds efficiently by the active oxygen released from the surface of the composite oxide particles.
- the composite oxide particles and the praseodymium oxide particles may be mixed and in contact with each other.
- the composite oxide particles and the praseodymium oxide particles may be mixed together and aggregated.
- one of the composite oxide particles and the praseodymium oxide particles forms a core and the other is supported on the surface of the core.
- the core may be formed by aggregation of one of the composite oxide particles and the praseodymium oxide particles.
- the composite oxide particles are located on the surface of the catalyst material.
- the active oxygen released from the can be efficiently supplied to the PM, and the combustion rate of the PM can be improved.
- the composite oxide particles containing Zr and Nd and not containing Ce serve as the core and the praseodymium oxide particles are supported on the surface of the core, the composite oxide particles are partially covered with the oxidized praseodymium particles. Become. For this reason, compared with the above-mentioned case, the efficiency with which the active oxygen released from the composite oxide particles is supplied to the PM is slightly reduced. However, since many praseodymium oxide particles are in contact with the composite oxide particles, a large amount of oxygen activated by the composite oxide particles is supplied to the praseodymium oxide particles. Release amount increases. As a result, the PM combustion rate can be improved.
- the composite oxide particles containing Zr and Nd and not containing Ce are ZrNd composite oxide particles composed of Zr, Nd and oxygen, Zr, Nd, Pr and oxygen. At least one composite oxide selected from ZrNdPr composite oxide particles comprising Zr, Nd, La and oxygen, and ZrNdY composite oxide particles comprising Zr, Nd, Y, and oxygen Physical particles may be used.
- the average particle diameter of the core (“number average particle diameter”; hereinafter the same) is 100 nm or more and 300 nm or less, and the average of the particles supported on the surface of the core
- the particle diameter is preferably 20 nm or more and 100 nm or less.
- the composite oxide particles and the praseodymium oxide particles are preferably contained in a mass ratio of 10:90 to 90:10, 10:90 to 50: More preferably, it is contained in the range of 50.
- the above exhaust gas component purification catalyst material may be carried on the exhaust gas passage wall of a particulate filter that collects particulates in the exhaust gas, or on the cell wall surface of a straight flow honeycomb carrier used in a three-way catalyst or the like. You may contain in the catalyst layer provided.
- the composite oxide particles containing Zr and Nd and not containing Ce, and the praseodymium oxide particles in contact with the composite oxide particles are provided. Therefore, the composite oxide particles and the praseodymium oxide particles combine with each other, and the effect that the combustion of PM proceeds efficiently is obtained.
- (A) is a diagram schematically illustrating an exhaust gas component purifying catalyst material obtained by mixing a composite oxide particles PrO x particles
- (b) is a composite oxide particles of the surface support material as the core of PrO x particles an exhaust gas component purifying catalyst material is a diagram schematically showing
- (c) is a diagram showing an exhaust gas component purifying catalyst material in which a composite oxide PrO x particles surface support material particles as the core schematically. It is a figure which shows the state which has arrange
- the mass ratio of the composite oxide and PrO x in exhaust gas components purification catalytic material is a graph showing the relationship between the carbon burning rate. It is a graph which shows the relationship between the structure of an exhaust gas component purification catalyst material, and a carbon combustion rate. It is a graph which shows the relationship between the structure of an exhaust gas component purification catalyst material, and a carbon combustion rate.
- ⁇ About catalyst material> 6 (a) to 6 (c) are diagrams each schematically showing the structure of the exhaust gas component purification catalyst material.
- the exhaust gas component purification catalyst material 1 includes a composite oxide particle 2 containing zirconium (Zr) and neodymium (Nd) supporting a noble metal (not shown) and not containing cerium (Ce), and a noble metal (not shown). Supported praseodymium oxide (PrO x ) particles 3 are provided.
- the noble metal is, for example, platinum (Pt).
- the exhaust gas component purification catalyst material 1 has a structure in which the composite oxide particles 2 and the PrO x particles 3 are mixed and in contact with each other and are arranged irregularly. .
- the composite oxide particle 2 contains a Zr oxide as a main component, and Nd is added and dissolved therein.
- the composite oxide particle 2 has high ionic conductivity and is active by taking oxygen into the inside by an oxygen exchange reaction. Release oxygen.
- the PrO x particles 3 have a high oxygen storage capacity (OSC capacity) and become an excellent oxygen supply source for the composite oxide.
- OSC capacity oxygen storage capacity
- the composite oxide particles 2 and the PrO x particles 3 are mixed and in contact with each other, their functions are efficiently exhibited, which is advantageous for PM combustion removal.
- the exhaust gas component purification catalyst material 1 includes a composite oxide particle 2 on the surface of a core 4 formed of PrO x particles 3 and a surface support material 5. It may be supported as.
- the core 4 is formed by agglomerating PrO x particles 3, for example.
- PrO x particles 3 may be supported as a surface support material 5 on the surface of the core 4 formed of the composite oxide particles 2.
- the core 4 is formed by, for example, agglomeration of the composite oxide particles 2.
- many praseodymium oxide particles are in contact with the composite oxide particles, and oxygen activated by the composite oxide particles is supplied to the praseodymium particles in a large amount, and the amount of active oxygen released from the surface of the praseodymium oxide particles is large. Therefore, the combustion rate of PM can be improved.
- the average particles of the composite oxide particles 2 and the PrO x particles 3 are used.
- the diameter is preferably 20 nm or more and 100 nm or less, and the average particle diameter of the core 4 is preferably 100 nm or more and 300 nm or less.
- the particles 2 and the PrO x particles 3 are preferably included in a mass ratio in the range of 10:90 to 90:10, and more preferably in a mass ratio of 10:90 to 50:50. .
- a composite oxide powder containing Zr and Nd and PrO x powder pulverized until the average particle size becomes about 20 nm to 100 nm are mixed with a predetermined amount. Mix uniformly at a mass ratio to make a slurry.
- Pt is used as the catalyst metal
- a solution obtained by diluting a dinitrodiamine platinum nitric acid solution with ion-exchanged water is added to the above slurry so that a predetermined amount of Pt is supported, followed by evaporation to dryness.
- the dried product is dried at 150 ° C. in the air, pulverized, and calcined at 500 ° C. for 2 hours in the air to obtain a catalyst material.
- a mixed oxide powder containing Zr and Nd pulverized to an average particle size of about 20 nm to 100 nm and an aqueous nitrate solution of Pr are mixed.
- the slurry is mixed with an aqueous ammonia solution and coprecipitated.
- the obtained coprecipitate is dried at 150 ° C., calcined at 500 ° C., and then loaded with Pt by the same method as described above, whereby a catalyst material having a core having an average particle diameter of about 100 nm to 300 nm. Is obtained.
- the exhaust gas component purification catalyst material shown in FIG. 6 (c) When the exhaust gas component purification catalyst material shown in FIG. 6 (c) is prepared, first, a powder of Pr oxide pulverized until the average particle diameter is about 20 nm to 100 nm and a predetermined amount of nitrate aqueous solution of Zr and Nd. The slurry is mixed to form a slurry, and this slurry is mixed with an aqueous ammonia solution and coprecipitated. Thereafter, the obtained coprecipitate is dried at 150 ° C., calcined at 500 ° C., and then loaded with Pt by the same method as described above, whereby a catalyst material having a core having an average particle diameter of about 100 nm to 300 nm. Is obtained.
- the exhaust gas component purification catalyst material obtained as described above is carried on the exhaust gas passage wall of a particulate filter for collecting, for example, PM.
- FIG. 7 shows a particulate filter (hereinafter simply referred to as “filter”) 10 disposed in the exhaust gas passage 11 of the diesel engine.
- filter a particulate filter
- an oxidation catalyst (not shown) in which a catalytic metal typified by Pt, Pd or the like is supported on a support material such as activated alumina can be disposed.
- the exhaust gas component purification catalyst material according to the present embodiment can be used for the oxidation catalyst to be disposed.
- the filter 10 has a honeycomb structure and includes a large number of exhaust gas passages 12 and 13 extending in parallel with each other. That is, in the filter 10, the exhaust gas inflow path 12 whose downstream end is blocked by the plug 14 and the exhaust gas outflow path 13 whose upstream end is blocked by the plug 14 are alternately provided. Is separated by a thin wall 15. In FIG. 8, hatched portions indicate the plugs 14 at the upstream end of the exhaust gas outflow passage 13.
- the filter body including the partition wall 15 is formed of an inorganic porous material such as cordierite, SiC, Si 3 N 4 , or sialon.
- the exhaust gas flowing into the exhaust gas inflow passage 12 flows out into the adjacent exhaust gas outflow passage 13 through the surrounding partition wall 15 as indicated by an arrow in FIG. That is, as shown in FIG. 10, the partition wall 15 has minute pores (exhaust gas passages) 16 that connect the exhaust gas inflow passage 12 and the exhaust gas outflow passage 13, and the exhaust gas passes through the pores 16.
- PM is trapped and accumulated mainly in the exhaust gas inlet 12 and the walls of the pores 16.
- a catalyst layer 17 is formed on the wall surface forming the exhaust gas passage (exhaust gas inflow passage 12, exhaust gas outflow passage 13 and pore 16) of the filter body. It is not always necessary to form a catalyst layer on the wall surface on the exhaust gas outflow passage 13 side.
- ZrNd composite oxide ZN: Examples 1 to 5, 9 and 11 to 15
- Zr, Nd and Pr with a molar ratio of ZrO 2 : Nd 2 O 3 : Pr 2 O 3 65: 15: 20 ZrNdPr composite oxide (ZNP: Examples 6, 10 and 16)
- Zr, Nd, and La in a molar ratio of ZrO 2 : Nd 2 O 3 : La 2 O 3 65: 15: 20 ZrNdLa composite oxide comprising oxygen (ZNL: Examples 7 and 17)
- ZrO 2 : Nd 2 O 3 : Y 2 O 3 65: 15: 20 in molar ratio Zr, Nd, Y, oxygen, ZrNdY complex acid consisting of By: was used (ZnY Examples
- Comparative Example 12 is a particle that does not contain the above complex oxide.
- Table 1 shows the composition of the prepared exhaust gas component purification catalyst material of each Example and each Comparative Example.
- the catalyst materials of Examples 1 to 8 and Comparative Examples 1 to 12 were formed by the catalyst material preparation method (physical mixing) shown in FIG. 6 (a), and the catalyst materials of Examples 9 and 10 were A catalyst material preparation method (PrO x is a surface-supporting material) shown in FIG. 6 (c), and the catalyst materials of Examples 11 to 18 were prepared as the catalyst material preparation method (PrOx) shown in FIG. 6 (b).
- x is a core).
- a sample filter (particulate filter with catalyst) was obtained by coating the filter with the exhaust gas component purification catalyst material of each Example and Comparative Example. Carbon (carbon black) was deposited on each sample filter after aging, and the carbon burning rate was measured. Aging is a heat treatment in which the sample filter is kept at a temperature of 800 ° C. in the atmosphere for 24 hours.
- FIG. 11 shows an apparatus for carbon deposition.
- reference numeral 21 denotes a container for containing carbon powder, to which an air supply pipe 22 and a carbon powder pressure feed pipe 23 are connected.
- Carbon powder is put into the container 21, a sample filter 24 is fitted to the tip of the pressure feeding pipe 23, and air is blown into the container 21 from the air supply pipe 22.
- the carbon powder rolls up and diffuses in the container 21 and flows along with the air through the pressure feeding tube 23 and accumulates on the sample filter 24.
- Each of the obtained sample filters was attached to a simulated gas flow reactor, and the gas temperature was raised while flowing N 2 gas. After the filter inlet temperature was stabilized at 580 ° C., the simulated exhaust gas was switched from N 2 gas to simulated exhaust gas (O 2 ; 7.5%, remaining N 2 ), and flowed at a space velocity of 40000 / h. Then, the CO and CO 2 gas concentrations produced by the combustion of carbon are measured in real time at the filter outlet, and from these concentrations, the carbon combustion rate (unit time) is determined at predetermined intervals using the following formula. Per PM combustion amount) was calculated.
- Carbon burning rate (g / h) ⁇ Gas flow rate (L / h) x [(CO + CO 2 ) concentration (ppm) / (1 x 10 6 )] ⁇ x 12 (g / mol) /22.4 (L / mol)
- the time-dependent change in the integrated value of the carbon combustion amount is obtained based on the carbon combustion rate for each predetermined time, and the time required for the carbon combustion rate to reach from 0% to 90% and the integrated value of the carbon combustion amount during that time are calculated.
- the combustion rate (PM combustion amount per minute (1 mg / min-L) in the filter 1 L) was determined. The results are shown in the rightmost column of Table 1 and FIGS.
- FIG. 12 shows the relationship between the mass ratio of the Zr-based composite oxide containing Zr and Nd and not containing Ce and PrO x or CeO 2 and the carbon burning rate.
- Examples 1 to 5 physical mixing of ZN and PrO x
- Comparative Examples 2 to 6 physical mixing of ZN and CeO 2
- Examples 1 to 5 using PrO x have a higher carbon burning rate.
- Examples 1-5 and Examples 11 ⁇ 15 are compared, and were each oxide cores PrO x even mass ratio in either case the Examples 11 to 15 have a higher carbon burning rate.
- the mass ratio of ZN: PrO x is 10:90 to 50:50, the carbon combustion rate can be further improved.
- FIG. 13 is a graph comparing the cases where the mass ratio of the Zr-based composite oxide and PrO x or CeO 2 is 70:30. As shown in Table 1 and FIG. 13, Examples 4, 9 and 10 using PrO x have a higher carbon combustion rate than Comparative Example 5 using CeO 2 , and Zr-based composite oxide is used as a core. Examples 9 and 10 used have a higher carbon burning rate.
- FIG. 14 is a graph comparing the cases where the mass ratio of the Zr-based composite oxide to PrO x or CeO 2 is 30:70.
- any of ZN, ZNP, ZNL, and ZNY is used as the Zr-based composite oxide, compared with the case of mixing these with CeO 2 (Comparative Examples 3 and 8 to 10).
- the carbon burning rate is higher.
- PrO x is used as the core (Examples 12 and 16 to 18)
- the carbon burning rate becomes higher.
- CZN and PrO x were mixed (Comparative Example 11)
- a carbon burning rate comparable to that of Comparative Examples 3 and 8 to 10 was shown.
- the carbon combustion rate can be improved by mixing PrO x in place of CeO 2 in the Zr-based composite oxide. Furthermore, by using either Zr-based composite oxide or PrO x as a core and the other as a surface support material, the carbon combustion rate can be further improved.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
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- Exhaust Gas After Treatment (AREA)
- Processes For Solid Components From Exhaust (AREA)
Abstract
Description
図6(a)~(c)は、それぞれ排ガス成分浄化触媒材の構造を模式的に示す図である。
以下、PMを捕集するためのパティキュレートフィルタの構造について説明する。
={ガス流速(L/h)×[(CO+CO2)濃度(ppm)/(1×106)]}×12(g/mol)/22.4(L/mol)
上記所定時間毎のカーボン燃焼速度に基づいてカーボン燃焼量積算値の経時変化を求め、カーボン燃焼率が0%から90%に達するまでに要した時間とその間のカーボン燃焼量の積算値とからカーボン燃焼速度(フィルタ1Lでの1分間当たりのPM燃焼量(mg/min-L))を求めた。結果を表1の最右欄及び図12~図14に示す。
2 複合酸化物粒子
3 酸化プラセオジム(PrOx)粒子
4 コア
5 表面担持材
10 フィルタ
11 排ガス通路
12 排ガス流入路(排ガス通路)
13 排ガス流出路(排ガス通路)
14 栓
15 隔壁
16 細孔(排ガス通路)
17 触媒層
Claims (12)
- 排ガス中のパティキュレートを燃焼除去するために用いられる排ガス成分浄化触媒材において、
ジルコニウム及びネオジムを含み且つセリウムを含まない複合酸化物粒子と、
前記複合酸化物粒子に接触する酸化プラセオジム粒子とを備えていることを特徴とする排ガス成分浄化触媒材。 - 前記複合酸化物粒子と前記酸化プラセオジム粒子とは、互いに混ざり合って接触していることを特徴とする請求項1に記載の排ガス成分浄化触媒材。
- 前記複合酸化物粒子及び前記酸化プラセオジム粒子のうちの一方はコアを形成し、他方は前記コアの表面に担持されていることを特徴とする請求項1に記載の排ガス成分浄化触媒材。
- 前記複合酸化物粒子は、ジルコニウムとネオジムと酸素とからなるZrNd複合酸化物粒子、ジルコニウムとネオジムとプラセオジムと酸素とからなるZrNdPr複合酸化物粒子、ジルコニウムとネオジムとランタンと酸素とからなるZrNdLa複合酸化物粒子、及びジルコニウムとネオジムとイットリウムと酸素とからなるZrNdY複合酸化物粒子から選択される少なくとも1つの複合酸化物粒子であることを特徴とする請求項1に記載の排ガス成分浄化触媒材。
- 前記複合酸化物粒子は、ジルコニウムとネオジムと酸素とからなるZrNd複合酸化物粒子、ジルコニウムとネオジムとプラセオジムと酸素とからなるZrNdPr複合酸化物粒子、ジルコニウムとネオジムとランタンと酸素とからなるZrNdLa複合酸化物粒子、及びジルコニウムとネオジムとイットリウムと酸素とからなるZrNdY複合酸化物粒子から選択される少なくとも1つの複合酸化物粒子であることを特徴とする請求項2に記載の排ガス成分浄化触媒材。
- 前記複合酸化物粒子は、ジルコニウムとネオジムと酸素とからなるZrNd複合酸化物粒子、ジルコニウムとネオジムとプラセオジムと酸素とからなるZrNdPr複合酸化物粒子、ジルコニウムとネオジムとランタンと酸素とからなるZrNdLa複合酸化物粒子、及びジルコニウムとネオジムとイットリウムと酸素とからなるZrNdY複合酸化物粒子から選択される少なくとも1つの複合酸化物粒子であることを特徴とする請求項3に記載の排ガス成分浄化触媒材。
- 前記コアの平均粒子径は、100nm以上300nm以下であり、
前記コアの表面に担持された粒子の平均粒子径は、20nm以上100nm以下であることを特徴とする請求項3に記載の排ガス成分浄化触媒材。 - 前記複合酸化物粒子と前記酸化プラセオジム粒子とが質量比で10:90から90:10の範囲で含まれていることを特徴とする請求項1~7のいずれか1項に記載の排ガス成分浄化触媒材。
- 前記複合酸化物粒子と前記酸化プラセオジム粒子とが質量比で10:90から50:50の範囲で含まれていることを特徴とする請求項8に記載の排ガス成分浄化触媒材。
- 排ガス中のパティキュレートを捕集するパティキュレートフィルタであって、
排ガス通路壁に、請求項1~7のいずれか1項に記載の排ガス成分浄化触媒材が担持されていることを特徴とするパティキュレートフィルタ。 - 排ガス中のパティキュレートを捕集するパティキュレートフィルタであって、
排ガス通路壁に、請求項8に記載の排ガス成分浄化触媒材が担持されていることを特徴とするパティキュレートフィルタ。 - 排ガス中のパティキュレートを捕集するパティキュレートフィルタであって、
排ガス通路壁に、請求項9に記載の排ガス成分浄化触媒材が担持されていることを特徴とするパティキュレートフィルタ。
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DE112013000781.9T DE112013000781T5 (de) | 2012-01-31 | 2013-01-30 | Katalytisches Material zur Abgaskomponentenreinigung und katalysierter Partikelfilter mitdem katalytischen Material |
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