WO2015076403A1 - 排気ガス浄化用触媒 - Google Patents
排気ガス浄化用触媒 Download PDFInfo
- Publication number
- WO2015076403A1 WO2015076403A1 PCT/JP2014/081034 JP2014081034W WO2015076403A1 WO 2015076403 A1 WO2015076403 A1 WO 2015076403A1 JP 2014081034 W JP2014081034 W JP 2014081034W WO 2015076403 A1 WO2015076403 A1 WO 2015076403A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- exhaust gas
- layer
- osc
- catalyst layer
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 167
- 238000000746 purification Methods 0.000 title abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 109
- 239000007789 gas Substances 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 19
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000002002 slurry Substances 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
- B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
-
- 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
- B01J35/19—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
- B01J35/50—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
-
- 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
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
-
- 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
- B01J37/0248—Coatings comprising impregnated particles
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
-
- 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
Definitions
- the present invention relates to an exhaust gas purification catalyst.
- Exhaust gas discharged from an internal combustion engine such as an engine contains harmful substances such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). Since these substances cause air pollution, it is necessary to purify the exhaust gas.
- harmful substances such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). Since these substances cause air pollution, it is necessary to purify the exhaust gas.
- Exhaust gas can be purified using an exhaust gas purification catalyst.
- the exhaust gas purifying catalyst is usually composed of a base material and a catalyst layer disposed on the base material, and the catalyst layer includes a support and a catalyst metal supported on the support.
- noble metals such as platinum, palladium and rhodium are used as the catalyst metal.
- OSC material oxygen storage / release capacity
- cerium-zirconium composite oxide is used as a carrier
- the cerium-zirconium composite oxide occludes oxygen by oxidizing cerium from trivalent to tetravalent under oxygen-excess conditions.
- oxygen is released by reducing cerium from tetravalent to trivalent under oxygen-deficient conditions. Thereby, it is possible to suppress the atmospheric fluctuation in the vicinity of the catalytic metal and efficiently purify the exhaust gas.
- the exhaust gas temperature varies in a wide range from the low temperature range to the high temperature range.
- the temperature of the exhaust gas is low, and the exhaust gas purification catalyst is not sufficiently activated. Therefore, it is difficult to sufficiently purify the exhaust gas. Therefore, the conventional exhaust gas purification catalyst is designed so that OSC is exhibited in a state where the temperature of the exhaust gas is low. However, if the OSC is exhibited when the temperature of the exhaust gas is low, the OSC is no longer exhibited even if the temperature of the exhaust gas is increased thereafter. As a result, it becomes difficult to sufficiently purify the exhaust gas in a high temperature region.
- an object of the present invention is to provide an exhaust gas purifying catalyst capable of efficiently purifying exhaust gas in a wide temperature range from a low temperature region to a high temperature region.
- exhaust gas can be efficiently purified over a wide temperature range by arranging a plurality of layers that exhibit OSC in different temperature ranges on a substrate. Further, it has been found that the OSC material on which the catalyst metal is supported exhibits OSC in the low temperature range, and the OSC material on which the catalyst is not supported exhibits OSC in the high temperature range.
- the present invention includes the following.
- An exhaust gas purifying catalyst comprising a base material, a lower layer disposed on the base material, and an upper layer disposed on the lower layer, A lower catalyst layer including a first material having an oxygen storage / release capability and a first catalyst metal supported on the first material, wherein the lower layer is laminated in an arbitrary order; and an oxygen storage / release capability A non-catalytic layer that includes a second material having An exhaust gas purifying catalyst, wherein the upper layer includes an upper catalyst layer containing a second catalytic metal.
- an exhaust gas purification catalyst that efficiently purifies exhaust gas in a wide temperature range from a low temperature region to a high temperature region.
- An example of the exhaust gas purifying catalyst is shown. A part of sectional drawing of the catalyst for exhaust gas purification is shown. A part of sectional drawing of the catalyst for exhaust gas purification is shown. The relationship between the weight ratio of the first OSC material and the second OSC material and the HC purification rate is shown. The relationship between temperature and OSC is shown.
- the present invention is an exhaust gas purification catalyst including a base material, a lower layer disposed on the base material, and an upper layer disposed on the lower layer, wherein the lower layers are laminated in an arbitrary order.
- a lower catalyst layer comprising a first material having oxygen storage / release capability (hereinafter referred to as “first OSC material”) and a first catalyst metal supported on the first OSC material; and oxygen storage / release
- first OSC material a first material having oxygen storage / release capability
- second OSC material non-catalytic layer that includes a second material having a function
- the upper layer includes an upper catalytic layer that includes a second catalytic metal
- the present invention relates to an exhaust gas purification catalyst.
- the exhaust gas purifying catalyst according to the present invention includes the first OSC material on which the first catalyst metal is supported and the second OSC material on which the catalyst metal is not supported.
- the OSC material on which the catalyst metal is supported exhibits OSC in a low temperature region.
- an OSC material on which no catalytic metal is supported exhibits OSC in a high temperature region. Therefore, the exhaust gas purifying catalyst according to the present invention exhibits OSC in a low temperature region and a high temperature region.
- the second OSC material on which the catalyst metal is not supported and the first OSC material on which the first catalyst metal is supported are present in different layers. Yes.
- the catalyst metal is not contained in the layer containing the second OSC material.
- the low temperature region means less than 500 ° C.
- the high temperature region means 500 ° C. or more.
- Examples of the base material of the exhaust gas purification catalyst according to the present invention include those generally used in exhaust gas purification catalysts.
- a straight flow type or wall flow type monolith substrate may be used.
- the material of the base material is not particularly limited, and examples thereof include base materials such as ceramic, silicon carbide, and metal.
- the lower layer disposed on the substrate includes a lower catalyst layer and a non-catalyst layer.
- the lower catalyst layer includes a first OSC material and a first catalyst metal supported on the first OSC material.
- the non-catalytic layer includes the second OSC material and does not include the catalytic metal. Since the lower catalyst layer includes the first OSC material on which the first catalyst metal is supported, the lower catalyst layer exhibits OSC in a low temperature region. On the other hand, since the non-catalytic layer includes the second OSC material on which no catalytic metal is supported, the non-catalytic layer exhibits OSC in a high temperature region.
- the lower catalyst layer and the non-catalyst layer can be laminated on the substrate in any order.
- the layer disposed above is easy to come into contact with the exhaust gas, it reacts with the exhaust gas and easily generates reaction heat. As a result, the layer disposed on the upper side has excellent warmth and is easily activated. Therefore, when it is desired to further improve the purification performance in the high temperature region, it is preferable to dispose the non-catalytic layer 4 exhibiting OSC in the high temperature region on the lower catalyst layer 3 as shown in FIG.
- the lower catalyst layer 3 that exhibits OSC in the low temperature region on the non-catalyst layer 4 for example, as shown in FIG.
- the thickness of the non-catalytic layer is not particularly limited, but is preferably 10 to 50 ⁇ m, particularly preferably 20 to 40 ⁇ m.
- the thickness of the non-catalyst layer is not particularly limited, but is preferably 10 to 50 ⁇ m, particularly preferably 20 to 40 ⁇ m.
- the upper layer disposed on the lower layer includes an upper catalyst layer containing a second catalyst metal. Since the upper layer is likely to come into contact with the exhaust gas, the upper catalyst layer containing the second catalyst metal is arranged above the non-catalyst layer, so that the exhaust gas does not contain the catalyst metal. Passing through the layer and being discharged can be suppressed.
- the thickness of the upper catalyst layer is not particularly limited, but is preferably 10 to 50 ⁇ m, and particularly preferably 20 to 40 ⁇ m.
- the thickness of the upper catalyst layer is 10 ⁇ m, particularly 20 ⁇ m or more, the second catalyst metal contained in the upper catalyst layer can be sufficiently brought into contact with the exhaust gas.
- the thickness of the upper catalyst layer is 50 ⁇ m, particularly 40 ⁇ m or less, an increase in pressure loss can be suppressed, and furthermore, exhaust gas can be sufficiently diffused into the non-catalyst layer and the lower catalyst layer.
- the exhaust gas can be purified.
- these catalytic metals include noble metals, more specifically rhodium, palladium, platinum and the like.
- the first catalyst metal and the second catalyst metal may be the same type of metal or different types of metals. Although it does not specifically limit, it is preferable that one catalyst metal is rhodium, the other catalyst metal is palladium and / or platinum, one catalyst metal is rhodium, and the other catalyst metal is palladium. It is more preferable. Further, it is preferable that the first catalyst metal is rhodium, the second catalyst metal is palladium and / or platinum, the first catalyst metal is rhodium, and the second catalyst metal is palladium. More preferred.
- the lower catalyst layer and the non-catalyst layer include the first OSC material supporting the first catalyst metal and the second OSC material not supporting the catalyst metal, respectively, from the low temperature region to the high temperature region OSC can be exhibited in a wide temperature range.
- These OSC materials are not particularly limited, and known materials having the ability to occlude and release oxygen can be used.
- these OSC materials include ceria; cerium-zirconium composite oxide; composite oxide of cerium, zirconium, and at least one selected from the group consisting of hafnium, neodymium, yttrium, lanthanum, praseodymium, and nickel. Etc.
- the first OSC material and the second OSC material are preferably materials having a pyrochlore structure.
- oxygen is easily released from the OSC material, so that it is possible to quickly cope with atmospheric changes.
- the first OSC material and the second OSC material may be the same type of material or different types of materials.
- the first OSC material and the second OSC material are preferably the same type of material, more preferably a material having a pyrochlore structure, and cerium-zirconium having a pyrochlore structure.
- a composite oxide is particularly preferable.
- the weight ratio of cerium and zirconium in such a cerium-zirconium composite oxide is not particularly limited as long as it is a ratio capable of forming a pyrochlore structure, and examples thereof include 45:55 to 55:45, 50:50, and the like. Can do.
- the weight ratio between the first OSC material and the second OSC material is not particularly limited, but is preferably 1: 2 to 2: 1. By adjusting to this range, exhaust gas can be purified in a balanced manner from the low temperature region to the high temperature region.
- the total content of the first OSC material and the second OSC material is not particularly limited, but is preferably 10 to 100 g, more preferably 20 to 80 g, and more preferably 30 to 30 g per 0.635 L of the base material. Particularly preferred is 60 g.
- the exhaust gas purifying catalyst according to the present invention is mainly composed of a base material, a lower catalyst layer, a non-catalyst layer, and an upper catalyst layer, but any layer can be arbitrarily selected as long as the effects of the present invention are not impaired. It may be included at the position.
- the further catalyst layer containing a catalyst metal may be arrange
- a further non-catalytic layer containing an OSC material and not containing a catalytic metal may be disposed at an arbitrary position.
- the lower catalyst layer, the non-catalyst layer, and the upper catalyst layer may contain arbitrary components as long as the effects of the present invention are not impaired.
- additional OSC materials may be included.
- OSC materials include cerium-zirconium composite oxides that do not have a pyrochlore structure.
- Examples of the weight ratio of cerium to zirconium in such a cerium-zirconium composite oxide include 20 to 40:80 to 60, 30 to 40:70 to 60, and the like.
- a base material a base material; a lower catalyst layer including a first OSC material having a pyrochlore structure and rhodium supported on the first OSC material, disposed on the base material; A non-catalytic layer that includes a second OSC material having a pyrochlore structure and does not include a catalytic metal disposed on the lower catalyst layer; and palladium and / or platinum (particularly palladium) disposed on the non-catalytic layer. ) Containing an upper catalyst layer.
- Another embodiment of the present invention includes: a substrate; a second OSC material having a pyrochlore structure disposed on the substrate; and a non-catalytic layer not including a catalytic metal; disposed on the non-catalytic layer A lower catalyst layer comprising a first OSC material having a pyrochlore structure and rhodium supported on the first OSC material; and palladium and / or platinum (in particular, disposed on the lower catalyst layer) And an exhaust gas purification catalyst containing an upper catalyst layer containing palladium).
- the slurry for the lower catalyst layer [1-1] was coated on the monolith substrate (0.635 L) and dried at 250 ° C. for 1 hour. Next, it was calcined at 500 ° C. for 1 hour to form a lower catalyst layer.
- the non-catalyst layer slurry [1-2] was coated on the lower catalyst layer and dried at 250 ° C. for 1 hour. Next, it baked at 500 degreeC for 1 hour, and formed the non-catalyst layer.
- the upper catalyst layer slurry [1-3] was coated on the non-catalyst layer and dried at 250 ° C. for 1 hour. Next, it baked at 500 degreeC for 1 hour, and formed the upper catalyst layer.
- an exhaust gas purification catalyst was manufactured.
- Example 2 An exhaust gas purification catalyst was produced in the same manner as in Example 1 except that 30 g of the first OSC material in Example 1 and 10 g of the second OSC material were used.
- Example 3 An exhaust gas purifying catalyst was produced in the same manner as in Example 1 except that 26 g of the first OSC material in Example 1 and 13 g of the second OSC material were used.
- Example 4 An exhaust gas purifying catalyst was produced in the same manner as in Example 1 except that 10 g of the first OSC material in Example 1 and 30 g of the second OSC material were used.
- Example 5 An exhaust gas purification catalyst was produced in the same manner as in Example 1 except that 13 g of the first OSC material in Example 1 and 26 g of the second OSC material were used.
- Example 6 Exhaust gas purifying catalyst was prepared in the same manner as in Example 1, except that the coating order of the slurry for the lower catalyst layer [1-1] and the slurry for the non-catalyst layer [1-2] in Example 1 was reversed. Manufactured.
- Example 7 An exhaust gas purification catalyst was produced in the same manner as in Example 1 except that a cerium-zirconium composite oxide having no pyrochlore structure was used as the first OSC material in Example 1.
- Example 8 An exhaust gas purification catalyst was produced in the same manner as in Example 1 except that a cerium-zirconium composite oxide having no pyrochlore structure was used as the second OSC material in Example 1.
- Example 9 A cerium-zirconium composite oxide having no pyrochlore structure was used as the first OSC material in Example 1, and a cerium-zirconium composite oxide having no pyrochlore structure was used as the second OSC material. Except this, an exhaust gas purification catalyst was produced in the same manner as in Example 1.
- ⁇ OSC evaluation test> The exhaust gas purification catalyst produced in Example 1 was subjected to an endurance test at 1000 ° C. for 10 hours using a mixed gas containing carbon monoxide and oxygen. Thereafter, the catalyst was measured by a temperature programmed reduction method (TPR). The results are shown in FIG.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (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)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
前記下層が、任意の順番で積層された、酸素吸蔵放出能を有する第1の材料と当該第1の材料上に担持された第1の触媒金属とを含む下層触媒層;及び酸素吸蔵放出能を有する第2の材料を含み、触媒金属を含まない非触媒層;を含み、
前記上層が、第2の触媒金属を含む上層触媒層を含む、排気ガス浄化用触媒。
[実施例1]
(1)硝酸ロジウム溶液(Rh:0.3g)を、パイロクロア構造を有するセリウム-ジルコニウム複合酸化物(第1のOSC材料)[Ce:Zr=50:50(重量比)](20g)に担持させ、Rh担持OSC材料を得た。Rh担持OSC材料、アルミナ(50g)、及びパイロクロア構造を有さないセリウム-ジルコニウム複合酸化物[Ce:Zr=30:70(重量比)](50g)を混合及びミリングして、下層触媒層用スラリー[1-1]を得た。
実施例1における第1のOSC材料を30g使用し、第2のOSC材料を10g使用したこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における第1のOSC材料を26g使用し、第2のOSC材料を13g使用したこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における第1のOSC材料を10g使用し、第2のOSC材料を30g使用したこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における第1のOSC材料を13g使用し、第2のOSC材料を26g使用したこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における下層触媒層用スラリー[1-1]、及び非触媒層用スラリー[1-2]のコートの順番を逆にしたこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における第1のOSC材料として、パイロクロア構造を有さないセリウム-ジルコニウム複合酸化物を使用したこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における第2のOSC材料として、パイロクロア構造を有さないセリウム-ジルコニウム複合酸化物を使用したこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における第1のOSC材料として、パイロクロア構造を有さないセリウム-ジルコニウム複合酸化物を使用し、且つ第2のOSC材料として、パイロクロア構造を有さないセリウム-ジルコニウム複合酸化物を使用したこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における非触媒層用スラリー[1-2]に第2のOSC材料を加えなかったこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
実施例1における下層触媒層用スラリー[1-1]に第1のOSC材料を加えなかったこと以外は、実施例1と同様に排気ガス浄化用触媒を製造した。
各実施例及び比較例で製造した排気ガス浄化用触媒(Φ103×120L、600セル/3ミル)に対して、15万マイル走行相当の耐久試験を行った。その後、当該触媒を排気量2.0Lのエンジンを有する車両に搭載し、LA#4モードで走行して、Bag.1、2山目のHC浄化率を測定した。結果を表1に示す。また、実施例1~5の結果を図4に示す。
実施例1で製造した排気ガス浄化用触媒に対して、一酸化炭素と酸素とを含む混合ガスを用いて1000℃で10時間耐久試験を行った。その後、当該触媒を昇温還元法(TPR)により測定した。結果を図5に示す。
本明細書で引用した全ての刊行物をそのまま参考として本明細書にとり入れるものとする。
Claims (6)
- 基材と、当該基材上に配置された下層と、当該下層上に配置された上層とを含む排気ガス浄化用触媒であって、
前記下層が、任意の順番で積層された、酸素吸蔵放出能を有する第1の材料と当該第1の材料上に担持された第1の触媒金属とを含む下層触媒層;及び酸素吸蔵放出能を有する第2の材料を含み、触媒金属を含まない非触媒層;を含み、
前記上層が、第2の触媒金属を含む上層触媒層を含む、排気ガス浄化用触媒。 - 非触媒層が下層触媒層上に配置されている、請求項1に記載の排気ガス浄化用触媒。
- 下層触媒層が非触媒層上に配置されている、請求項1に記載の排気ガス浄化用触媒。
- 酸素吸蔵放出能を有する第1の材料及び酸素吸蔵放出能を有する第2の材料が、パイロクロア構造を有する材料である、請求項1~3のいずれかに記載の排気ガス浄化用触媒。
- パイロクロア構造を有する材料がセリウム-ジルコニウム複合酸化物である、請求項4に記載の排気ガス浄化用触媒。
- 第1の触媒金属がロジウムであり、第2の触媒金属がパラジウム及び/又は白金である、請求項1~5のいずれかに記載の排気ガス浄化用触媒。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480063256.5A CN105745015A (zh) | 2013-11-22 | 2014-11-25 | 排气净化用催化剂 |
US15/037,829 US20160288100A1 (en) | 2013-11-22 | 2014-11-25 | Catalyst for exhaust gas purification |
JP2015549220A JPWO2015076403A1 (ja) | 2013-11-22 | 2014-11-25 | 排気ガス浄化用触媒 |
EP14863486.8A EP3072587A4 (en) | 2013-11-22 | 2014-11-25 | Catalyst for exhaust gas purification |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013241959 | 2013-11-22 | ||
JP2013-241959 | 2013-11-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015076403A1 true WO2015076403A1 (ja) | 2015-05-28 |
Family
ID=53179662
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/081034 WO2015076403A1 (ja) | 2013-11-22 | 2014-11-25 | 排気ガス浄化用触媒 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20160288100A1 (ja) |
EP (1) | EP3072587A4 (ja) |
JP (1) | JPWO2015076403A1 (ja) |
CN (1) | CN105745015A (ja) |
WO (1) | WO2015076403A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019221212A1 (ja) * | 2018-05-17 | 2019-11-21 | エヌ・イーケムキャット株式会社 | 排ガス浄化触媒及びその製造方法 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10618034B2 (en) * | 2016-01-21 | 2020-04-14 | Cataler Corporation | Exhaust gas purification device |
US10058846B2 (en) * | 2016-09-05 | 2018-08-28 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gas |
JP7195995B2 (ja) * | 2019-03-27 | 2022-12-26 | 株式会社キャタラー | 排ガス浄化用触媒 |
JP7288331B2 (ja) * | 2019-03-29 | 2023-06-07 | 株式会社キャタラー | 排ガス浄化触媒装置 |
US11618008B2 (en) * | 2020-10-05 | 2023-04-04 | Ford Global Technologies, Llc | Precious group metal on pyrochlore-phase ceria zirconia with superior oxygen storage capacity and TWC performance |
US11788450B2 (en) * | 2020-10-30 | 2023-10-17 | Johnson Matthey Public Limited Company | TWC catalysts for gasoline engine exhaust gas treatments |
CN115585039B (zh) * | 2022-11-02 | 2023-12-22 | 四川大学 | 含烧绿石结构的铈锆氧化物载体材料在柴油车中的应用 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08215569A (ja) | 1995-02-10 | 1996-08-27 | Toyota Motor Corp | 排気ガス浄化用触媒及び排気ガス浄化用触媒を備えた排気ガス浄化装置 |
JPH11165067A (ja) | 1997-12-03 | 1999-06-22 | Kinya Adachi | 排ガス浄化用助触媒のためのセリア−ジルコニア複合酸化物の製造方法 |
EP0935055A2 (en) * | 1998-02-05 | 1999-08-11 | Nissan Motor Company, Limited | Device for purifying oxygen rich exhaust gas |
JP2003265958A (ja) | 2002-03-18 | 2003-09-24 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒 |
JP2007530277A (ja) * | 2004-03-30 | 2007-11-01 | エンゲルハード・コーポレーシヨン | 排気ガス処理用触媒 |
US20080045404A1 (en) * | 2006-08-16 | 2008-02-21 | Heesung Catalyst Corporation | Catalyst containing little or no rhodium for purifying exhaust gases of internal combustion engine |
JP2008080196A (ja) * | 2006-09-26 | 2008-04-10 | Cataler Corp | 排ガス浄化用触媒 |
JP2008100152A (ja) * | 2006-10-18 | 2008-05-01 | Cataler Corp | 排ガス浄化用触媒 |
WO2010140780A2 (ko) * | 2009-06-01 | 2010-12-09 | 희성촉매 주식회사 | 3중층 코팅구조의 삼원촉매 |
WO2012105454A1 (ja) * | 2011-02-01 | 2012-08-09 | 株式会社アイシーティー | 排ガス浄化用触媒 |
JP2012152702A (ja) * | 2011-01-27 | 2012-08-16 | Toyota Motor Corp | 排ガス浄化用触媒 |
JP2013241959A (ja) | 2012-05-18 | 2013-12-05 | Jtekt Corp | 転がり軸受用の分割保持器 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020132730A1 (en) * | 2001-01-16 | 2002-09-19 | Engelhard Corporation | Catalytic metal plate |
JP4501166B2 (ja) * | 1998-10-30 | 2010-07-14 | 日産自動車株式会社 | 排ガス浄化システム |
JP2005170774A (ja) * | 2003-12-15 | 2005-06-30 | Tosoh Corp | 複合酸化物及びその製造方法並びに排ガス浄化用触媒 |
JP4240011B2 (ja) * | 2005-06-20 | 2009-03-18 | トヨタ自動車株式会社 | 排ガス浄化触媒 |
CN101568381B (zh) * | 2007-02-01 | 2012-05-09 | 第一稀元素化学工业株式会社 | 用于机动车废气净化装置中的催化剂体系、使用该催化剂体系的废气净化装置及废气净化方法 |
EP2368630A4 (en) * | 2008-12-19 | 2013-07-31 | Cataler Corp | CATALYST FOR THE PURIFICATION OF EXHAUST GASES |
US7981390B2 (en) * | 2008-12-23 | 2011-07-19 | Basf Corporation | Small engine palladium catalyst article and method of making |
US8568675B2 (en) * | 2009-02-20 | 2013-10-29 | Basf Corporation | Palladium-supported catalyst composites |
-
2014
- 2014-11-25 CN CN201480063256.5A patent/CN105745015A/zh active Pending
- 2014-11-25 US US15/037,829 patent/US20160288100A1/en not_active Abandoned
- 2014-11-25 WO PCT/JP2014/081034 patent/WO2015076403A1/ja active Application Filing
- 2014-11-25 JP JP2015549220A patent/JPWO2015076403A1/ja active Pending
- 2014-11-25 EP EP14863486.8A patent/EP3072587A4/en not_active Withdrawn
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08215569A (ja) | 1995-02-10 | 1996-08-27 | Toyota Motor Corp | 排気ガス浄化用触媒及び排気ガス浄化用触媒を備えた排気ガス浄化装置 |
JPH11165067A (ja) | 1997-12-03 | 1999-06-22 | Kinya Adachi | 排ガス浄化用助触媒のためのセリア−ジルコニア複合酸化物の製造方法 |
EP0935055A2 (en) * | 1998-02-05 | 1999-08-11 | Nissan Motor Company, Limited | Device for purifying oxygen rich exhaust gas |
JP2003265958A (ja) | 2002-03-18 | 2003-09-24 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒 |
JP2007530277A (ja) * | 2004-03-30 | 2007-11-01 | エンゲルハード・コーポレーシヨン | 排気ガス処理用触媒 |
US20080045404A1 (en) * | 2006-08-16 | 2008-02-21 | Heesung Catalyst Corporation | Catalyst containing little or no rhodium for purifying exhaust gases of internal combustion engine |
JP2008080196A (ja) * | 2006-09-26 | 2008-04-10 | Cataler Corp | 排ガス浄化用触媒 |
JP2008100152A (ja) * | 2006-10-18 | 2008-05-01 | Cataler Corp | 排ガス浄化用触媒 |
WO2010140780A2 (ko) * | 2009-06-01 | 2010-12-09 | 희성촉매 주식회사 | 3중층 코팅구조의 삼원촉매 |
JP2012152702A (ja) * | 2011-01-27 | 2012-08-16 | Toyota Motor Corp | 排ガス浄化用触媒 |
WO2012105454A1 (ja) * | 2011-02-01 | 2012-08-09 | 株式会社アイシーティー | 排ガス浄化用触媒 |
JP2013241959A (ja) | 2012-05-18 | 2013-12-05 | Jtekt Corp | 転がり軸受用の分割保持器 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3072587A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019221212A1 (ja) * | 2018-05-17 | 2019-11-21 | エヌ・イーケムキャット株式会社 | 排ガス浄化触媒及びその製造方法 |
JPWO2019221212A1 (ja) * | 2018-05-17 | 2021-04-08 | エヌ・イーケムキャット株式会社 | 排ガス浄化触媒及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2015076403A1 (ja) | 2017-03-16 |
EP3072587A4 (en) | 2017-07-19 |
US20160288100A1 (en) | 2016-10-06 |
EP3072587A1 (en) | 2016-09-28 |
CN105745015A (zh) | 2016-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2015076403A1 (ja) | 排気ガス浄化用触媒 | |
JP6133836B2 (ja) | 排ガス浄化触媒 | |
JP5567923B2 (ja) | 排ガス浄化用触媒 | |
JP6855445B2 (ja) | 排ガス浄化用触媒 | |
JP5240275B2 (ja) | 排ガス浄化用触媒 | |
JP6133835B2 (ja) | 排ガス浄化触媒 | |
JP5910833B2 (ja) | 排ガス浄化触媒 | |
JP6034356B2 (ja) | 排ガス浄化触媒 | |
JP6907890B2 (ja) | 排ガス浄化用触媒 | |
US9833771B2 (en) | Exhaust gas purifying catalyst | |
WO2013099251A1 (en) | Exhaust gas purification catalyst | |
WO2017213105A1 (ja) | 排ガス浄化用触媒 | |
WO2016125617A1 (ja) | 排ガス浄化用触媒 | |
WO2015005423A1 (ja) | 排気ガス浄化用触媒 | |
US11141713B2 (en) | Exhaust gas purification catalyst and exhaust gas purification method using the same | |
WO2014171443A1 (ja) | 排気ガス浄化用触媒 | |
WO2022097498A1 (ja) | 排ガス浄化触媒装置 | |
JP2014097459A (ja) | 排気ガス浄化用触媒 | |
JP5413279B2 (ja) | 排ガス浄化用触媒 | |
JP2009255084A (ja) | 排ガス浄化用触媒 | |
JP6571570B2 (ja) | 自動車排ガス浄化用触媒 | |
JP2014100631A (ja) | 排気ガス浄化用連続触媒 | |
JP2015112555A (ja) | 排気ガス浄化用触媒 | |
JP2000237589A (ja) | 排気ガス浄化用触媒 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14863486 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015549220 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15037829 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: IDP00201603376 Country of ref document: ID |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112016010501 Country of ref document: BR |
|
REEP | Request for entry into the european phase |
Ref document number: 2014863486 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014863486 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 112016010501 Country of ref document: BR Kind code of ref document: A2 Effective date: 20160510 |