WO2019109999A1 - 用于汽油机废气处理的新型多区twc催化剂 - Google Patents

用于汽油机废气处理的新型多区twc催化剂 Download PDF

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WO2019109999A1
WO2019109999A1 PCT/CN2018/119728 CN2018119728W WO2019109999A1 WO 2019109999 A1 WO2019109999 A1 WO 2019109999A1 CN 2018119728 W CN2018119728 W CN 2018119728W WO 2019109999 A1 WO2019109999 A1 WO 2019109999A1
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oxide
catalyst article
cerium
article according
catalytic
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PCT/CN2018/119728
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English (en)
French (fr)
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吉红宇
乔东升
郑翔
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庄信万丰(上海)化工有限公司
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Priority to EP18885243.8A priority Critical patent/EP3721990A4/en
Priority to JP2020530583A priority patent/JP7451402B2/ja
Priority to BR112020009899-0A priority patent/BR112020009899A2/pt
Priority to RU2020116416A priority patent/RU2776996C2/ru
Priority to US15/733,193 priority patent/US11439987B2/en
Publication of WO2019109999A1 publication Critical patent/WO2019109999A1/zh
Priority to JP2023188364A priority patent/JP2024016163A/ja

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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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    • 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
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    • 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
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    • 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
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
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    • B01J37/02—Impregnation, coating or precipitation
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    • B01J37/0244—Coatings comprising several layers
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/101—Three-way catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2839—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
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    • B01D2255/00—Catalysts
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2258/01—Engine exhaust gases
    • B01D2258/014—Stoichiometric gasoline engines
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    • F01N2370/00—Selection of materials for exhaust purification
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    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction

Definitions

  • the present invention relates to a catalytic article for treating exhaust emissions from a gasoline engine.
  • the internal combustion engine produces exhaust gases containing a variety of pollutants including hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides ("NO x ").
  • Emission control systems including exhaust gas catalytic conversion catalysts are widely used to reduce the amount of these pollutants emitted to the atmosphere.
  • a common catalyst for gasoline engine tail gas treatment is TWC (three-way catalyst). TWC performs three main functions: (1) oxidation of CO; (2) the oxidation of unburned HC; and (3) reduction of NO x.
  • TWC is coated on a high surface area support that can withstand high temperatures, such as a flow-through honeycomb support.
  • the large surface area of these supports facilitates the efficiency of the heterogeneous reaction, but increases the exhaust back pressure, i.e., limits the flow of exhaust gases from the engine to the exhaust pipe.
  • U.S. Patent No. 6,022,825, U.S. Patent No. 9,352,279, U.S. Patent No. 9,040,003, and U.S. Patent Publication No. 2016/02288108 there is still a need for an improved catalytic converter for certain engine platforms that simultaneously improves Performance during the cold start phase and / or provide better light-off performance.
  • the present invention addresses these problems in particular.
  • One aspect of the invention relates to a catalyst for treating gasoline engine exhaust comprising: a carrier including an inlet end, an outlet end and having an axial length L; a first catalytic region starting at the inlet end and extending less than the axial length L Wherein the first catalytic region comprises a first palladium component; a second catalytic region starting at the outlet end and extending less than the axial length L, wherein the second catalytic region comprises a second palladium component; starting at the outlet And extending a third catalytic region that is less than the axial length L, wherein the third catalytic region comprises a third antimony component; and wherein the third catalytic region is superposed over the second catalytic region.
  • the present invention also includes an exhaust system for an internal combustion engine comprising the three-way catalyst component of the present invention.
  • the invention also includes treating exhaust gases from internal combustion engines, particularly exhaust gases from gasoline engines.
  • the method includes contacting an exhaust gas with a three-way catalyst component of the present invention.
  • Figure 1 shows that the total length of the second catalytic zone and the first catalytic zone is equal to the axial length L of the carrier, in accordance with an embodiment of the present invention.
  • Figures 2a and 2b show a second catalytic region overlapping a first catalytic region in accordance with two embodiments of the present invention.
  • Figure 3 shows that the total length of the second catalytic zone and the first catalytic zone is less than the axial length L of the carrier, in accordance with an embodiment of the present invention.
  • Figures 4a, 4b and 4c show, respectively from the catalyst A, diluted bags accumulated THC mining Comparative Catalyst C and Comparative Catalyst B testing vehicle, CO and NO x emissions.
  • This invention relates to the catalytic treatment of combustion exhaust gases such as those produced by gasoline engines and other engines, and to related catalysts and systems. More particularly, the present invention relates to simultaneously process NO x, CO and HC in the exhaust system of the vehicle.
  • the present inventors have found that a synergistic relationship between certain catalytically active metal and a coating method thereof, which is unexpectedly high conversion of NO x production, CO and HC; improved performance in the cold start phase; and better Light-off performance.
  • the process of the invention also reduces catalyst costs.
  • One aspect of the invention relates to a catalyst article for treating exhaust gas comprising: a carrier comprising an inlet end, an outlet end and having an axial length L; a first catalytic region starting at the inlet end and extending less than the axial length L Wherein the first catalytic region comprises a first palladium component; a second catalytic region starting at the outlet end and extending less than the axial length L, wherein the second catalytic region comprises a second palladium component; starting at the outlet And extending a third catalytic region that is less than the axial length L, wherein the third catalytic region comprises a third antimony component; and wherein the third catalytic region is superposed over the second catalytic region.
  • a catalyst employing this coating mode exhibits superior catalyst performance which cannot be achieved using a catalyst of a separate or conventional coating method.
  • An unexpected benefit of the present invention is that it has superior catalyst light-off performance compared to conventional TWC catalysts of similar concentrations (e.g., washcoat loading), which can significantly reduce the row during the cold start phase of the vehicle. Emissions of gaseous pollutants make it easier to meet emission targets. These benefits are achieved by reducing the amount of precious metals in the catalyst and thereby reducing costs.
  • the first catalytic zone may extend 30-70% of the axial length L.
  • the first catalytic zone may extend from 40 to 60%, more preferably from 45 to 55% of the axial length L.
  • the second catalytic region may extend 30-70% of the axial length L.
  • the second catalytic zone may extend from 40 to 60%, more preferably from 45 to 55% of the axial length L.
  • the second catalytic region may overlap the first catalytic region by 0.1-15% of the axial length L (see, for example, Figures 2a and 2b, the first catalytic region may be stacked above the second catalytic region, or the second catalytic region may be stacked Above the first catalytic zone).
  • the total length of the second catalytic zone and the first catalytic zone may be equal to the axial length L (see, for example, Figure 1).
  • the total length of the second catalytic zone and the first catalytic zone may be less than the axial length L, such as no more than 95%, 90%, 80%, or 70% of the axial length L (see, for example, Figure 3). .
  • the third catalytic region may extend 50-99% of the axial length L.
  • the third catalytic zone may extend from 50 to 95%, more preferably from 60 to 95% of the axial length L.
  • the first catalytic region may be substantially free of PGM metal other than the first palladium component.
  • the first catalyst layer may contain a PGM metal other than the first palladium component, for example, platinum and/or rhodium.
  • the first catalytic region may comprise from 0.1 to 300 g/ft 3 of the first palladium or platinum palladium component.
  • the first catalytic region may comprise from 50 to 250 g/ft 3 of a first palladium or platinum palladium component, more preferably from 100 to 220 g/ft 3 of a first palladium or platinum palladium component, wherein the weight ratio of platinum palladium It may be from 60:1 to 1:60, preferably from 30:1 to 1:30, more preferably from 10:1 to 1:10.
  • the total washcoat loading of the first catalytic zone may be less than 3.5 g/in 3 , preferably less than 3.0 g/in 3 , 2.5 g/in 3 or 1.5 g/in 3 .
  • the first catalytic region may further comprise a first oxygen storage (OSC) material, a first alkali metal or alkaline earth metal component, and/or a first inorganic oxide.
  • OSC oxygen storage
  • the first OSC material is preferably selected from the group consisting of cerium oxide, zirconium oxide, cerium oxide-zirconia mixed oxide, and aluminum oxide-yttria-zirconia mixed oxide. More preferably, the first OSC material comprises a cerium oxide-zirconia mixed oxide.
  • the cerium oxide-zirconia mixed oxide may further contain some doping elements such as lanthanum, cerium, lanthanum, cerium oxide and the like. Additionally, the first OSC material can serve as a carrier material for the first palladium component.
  • the first palladium component can be supported on the first inorganic oxide and the first OSC material.
  • the cerium oxide-zirconia mixed oxide has a molar ratio of at least 50:50, preferably greater than 60:40, more preferably greater than 75:25.
  • the first OSC material (e.g., yttria-zirconia mixed oxide) may be from 10 to 90 wt%, preferably from 25 to 75 wt%, more preferably from 30 to 60 wt%, based on the total washcoat loading of the first catalytic zone.
  • the first OSC material loading in the first catalytic zone may be less than 1.5 g/in 3 . In some embodiments, the first OSC material loading in the first catalytic zone is no greater than 1.2 g/in 3 , 1.0 g/in 3 , 0.9 g/in 3 , 0.8 g/in 3 or 0.7 g/in 3 .
  • a first alkali metal or alkaline earth metal can be deposited on the first OSC material.
  • a first alkali metal or alkaline earth metal may be deposited on the first inorganic oxide. That is, in some embodiments, the first alkali metal or alkaline earth metal may be deposited, i.e., present on both the first OSC material and the first inorganic oxide.
  • the first alkali metal or alkaline earth metal is generally in contact with the first inorganic oxide.
  • the first alkali metal or alkaline earth metal is supported on the first inorganic oxide.
  • the first alkali metal or alkaline earth metal may also be in contact with the first OSC material.
  • the first alkali metal or alkaline earth metal is preferably ruthenium or osmium, and a mixed oxide or composite oxide thereof.
  • the loading of rhodium or ruthenium is from 0.1 to 15% by weight, more preferably from 3 to 10% by weight, based on the total weight of the first catalytic zone, of ruthenium or osmium.
  • the first alkali metal or alkaline earth metal is cerium.
  • the loading of rhodium is preferably from 0.1 to 15% by weight, more preferably from 3 to 10% by weight, based on the total weight of the first catalytic zone.
  • the first alkali metal or alkaline earth metal is a mixed oxide or composite oxide of cerium and lanthanum.
  • the mixed oxide or composite oxide of cerium and lanthanum is present in an amount of from 0.1 to 15% by weight, based on the total weight of the first catalytic zone, more preferably from 3 to 10% by weight. More preferably, the first alkali metal or alkaline earth metal is a composite oxide of cerium and lanthanum.
  • ruthenium or osmium is present as BaCO 3 or SrCO 3 .
  • Such materials can be obtained by any method known in the art, such as incipient wetness impregnation or spray drying.
  • the first inorganic oxide is preferably an oxide of the Group 2, 3, 4, 5, 13 and 14 elements.
  • the first inorganic oxide is preferably selected from the group consisting of alumina, magnesia, silica, cerium oxide, cerium oxide, and mixed oxides or composite oxides thereof.
  • the first inorganic oxide is alumina, cerium-alumina, cerium oxide or magnesia/alumina composite oxide.
  • a particularly preferred first inorganic oxide is alumina or cerium-alumina composite oxide.
  • the first OSC material and the first inorganic oxide may have a weight of no greater than 10:1, preferably no greater than 8:1 or 5:1, more preferably no greater than 4:1 or 3:1, and most preferably no greater than 2:1 ratio.
  • the first OSC material and the first inorganic oxide may have from 10:1 to 1:10, preferably from 8:1 to 1:8 or from 5:1 to 1:5, more preferably from 4:1 to 1:4 or 3:1-1:3, most preferably a weight ratio of 2:1-1:2.
  • the second catalytic region may be substantially free of PGM metal other than the second palladium component.
  • the second catalyst layer may contain a PGM metal other than the second palladium component, for example, platinum and/or rhodium.
  • the second catalytic region may comprise from 0.1 to 100 g/ft 3 of a second palladium or platinum palladium component.
  • the second catalytic region may comprise from 5 to 60 g/ft 3 , more preferably from 10 to 50 g/ft 3 of the second palladium or platinum palladium component, wherein the weight ratio of platinum palladium may be from 60:1 to 1:60.
  • it is from 30:1 to 1:30, more preferably from 10:1 to 1:10.
  • the second catalytic region may further comprise a second oxygen storage (OSC) material, a second alkali metal or alkaline earth metal component, and/or a second inorganic oxide.
  • OSC second oxygen storage
  • the second OSC material is preferably selected from the group consisting of cerium oxide, zirconium oxide, cerium oxide-zirconia mixed oxide, and aluminum oxide-yttria-zirconia mixed oxide. More preferably, the second OSC material comprises a cerium oxide-zirconia mixed oxide. Additionally, the second OSC material may further comprise one or more of doping elements such as ruthenium, osmium, iridium, osmium, and the like. Also, the second OSC material can serve as a carrier material for the second palladium component.
  • the second palladium or platinum palladium component can be supported on the second inorganic oxide and the second OSC material.
  • the cerium oxide-zirconia mixed oxide may have a molar ratio of zirconia to cerium oxide of at least 50:50, preferably greater than 60:40, more preferably greater than 75:25.
  • the second OSC material (eg, yttria-zirconia mixed oxide) may be from 10 to 90 wt%, preferably from 25 to 75 wt%, more preferably from 30 to 60 wt%, based on the total washcoat loading of the second catalytic zone.
  • the second OSC material loading in the second catalytic zone may be less than 1.5 g/in 3 . In some embodiments, the second OSC material loading in the second catalytic zone is no greater than 1.2 g/in 3 , 1.0 g/in 3 , 0.9 g/in 3 , 0.8 g/in 3 or 0.7 g/in 3 .
  • the total carrier coating loading of the second catalytic zone may be less than 3.5 g/in 3 , preferably less than 3.0 g/in 3 , 2.5 g/in 3 , or 1.5 g/in 3 .
  • a second alkali or alkaline earth metal can be deposited on the second OSC material.
  • a second alkali metal or alkaline earth metal may be deposited on the second inorganic oxide. That is, in some embodiments, a second alkali metal or alkaline earth metal can be deposited, ie, present on both the second OSC material and the second inorganic oxide.
  • the second alkali metal or alkaline earth metal is generally in contact with the second inorganic oxide.
  • the second alkali metal or alkaline earth metal is supported on the second inorganic oxide.
  • the second alkali metal or alkaline earth metal may be in contact with the second OSC material.
  • the second alkali metal or alkaline earth metal is preferably cerium, lanthanum, a mixed oxide thereof or a composite oxide.
  • the cerium or lanthanum content is from 0.1 to 15% by weight, more preferably from 3 to 10% by weight, based on the total weight of the second catalytic zone, of cerium or lanthanum.
  • the second alkali metal or alkaline earth metal is cerium.
  • rhenium is preferably present in an amount of from 0.1 to 15% by weight, more preferably from 3 to 10% by weight, based on the total weight of the second catalytic zone.
  • the second alkali metal or alkaline earth metal is a mixed oxide or composite oxide of cerium and lanthanum.
  • the mixed oxide or composite oxide of cerium and lanthanum is present in an amount of from 0.1 to 15% by weight, based on the total weight of the second catalytic region, more preferably from 3 to 10% by weight. More preferably, the second alkali metal or alkaline earth metal is a composite oxide of cerium and lanthanum.
  • ruthenium or osmium is present as BaCO 3 or SrCO 3 .
  • Such materials can be obtained by any method known in the art, such as incipient wetness impregnation or spray drying.
  • the second inorganic oxide is preferably an oxide of the Group 2, 3, 4, 5, 13 and 14 elements.
  • the second inorganic oxide is preferably selected from the group consisting of alumina, magnesia, silica, cerium oxide, cerium oxide, and mixed oxides or composite oxides thereof.
  • the second inorganic oxide is alumina, cerium-alumina, cerium oxide or magnesia/alumina composite oxide.
  • a particularly preferred second inorganic oxide is alumina or cerium-alumina composite oxide.
  • the second OSC material and the second inorganic oxide may have no more than no more than 10:1, preferably no more than 8:1 or 5:1, more preferably no more than 4:1 or 3:1, and most preferably no more than 2:1 Weight ratio.
  • the second OSC material and the second inorganic oxide may have from 10:1 to 1:10, preferably from 8:1 to 1:8 or from 5:1 to 1:5, more preferably from 4:1 to 1:4 or 3:1-1:3, most preferably a weight ratio of 2:1-1:2.
  • the third catalytic region may be substantially free of PGM metal other than the third ruthenium component.
  • the third catalytic region may comprise from 0.1 to 20 g/ft 3 of a third ruthenium or platinum rhodium component.
  • the third catalytic region may comprise 3-15 g/ft 3 , more preferably 5-13 g/ft 3 of the third ruthenium or platinum rhodium component, wherein the platinum rhodium may have a weight ratio of 20:1-1:20 Preferably, it is from 15:1 to 1:15, more preferably from 10:1 to 1:10.
  • the total carrier coating loading of the third catalytic zone may be less than 3.5 g/in 3 ; preferably less than 3.0 g/in 3 or 2 g/in 3 ; more preferably less than 1.5 g/in 3 or 1.0 g/in 3 .
  • the third catalytic region may further comprise a third oxygen storage (OSC) material, a third alkali metal or alkaline earth metal component, and/or a third inorganic oxide.
  • OSC oxygen storage
  • the third OSC material is preferably selected from the group consisting of cerium oxide, zirconium oxide, cerium oxide-zirconia mixed oxide, and aluminum oxide-yttria-zirconia mixed oxide.
  • the third OSC material comprises a cerium oxide-zirconia mixed oxide and has one or more of doping elements such as lanthanum, cerium, lanthanum, cerium and the like. Additionally, the third OSC material can serve as a carrier material for the third bismuth component.
  • the cerium oxide-zirconia mixed oxide may have a molar ratio of zirconia to cerium oxide of at least 50:50, preferably greater than 60:40, more preferably greater than 80:20.
  • the third OSC material may be from 10 to 90% by weight, preferably from 25 to 75% by weight, more preferably from 35 to 65% by weight, based on the total carrier coating loading of the third catalytic zone.
  • the third OSC material loading in the third catalytic zone may be less than 2 g/in 3 . In some embodiments, the third OSC material loading in the third catalytic zone is no greater than 1.5 g/in 3 , 1.2 g/in 3 , 1.0 g/in 3 or 0.5 g/in 3 .
  • the third catalytic zone is substantially free of a third alkali metal or alkaline earth metal, more preferably substantially free of a third alkali metal or alkaline earth metal.
  • the third inorganic oxide is preferably an oxide of the Group 2, 3, 4, 5, 13 and 14 elements.
  • the third inorganic oxide is preferably selected from the group consisting of alumina, cerium oxide, magnesium oxide, silicon dioxide, cerium, zirconium, hafnium, cerium oxide and mixed oxides or composite oxides thereof.
  • the third inorganic oxide is alumina, cerium/alumina composite oxide or zirconium/alumina composite oxide.
  • a particularly preferred third inorganic oxide is a cerium/alumina composite oxide or a zirconium/aluminum oxide composite oxide.
  • the third inorganic oxide may be a carrier material of the third bismuth component and/or the third OSC material.
  • the preferred third inorganic oxide preferably has a fresh surface area greater than 80 m 2 /g, a pore volume of from 0.1 to 4 mL/g. Particularly preferably having a surface area greater than 100m 2 / g, high surface area inorganic oxide, such as high surface area alumina.
  • Other preferred third inorganic oxides include a cerium/alumina composite oxide, optionally further comprising a zirconium component such as zirconia. In such a case, zirconium may be present on the surface of the cerium/alumina composite oxide, for example as a coating.
  • the third OSC material and the third inorganic oxide may have a weight ratio of at least 1:1, preferably at least 2:1, more preferably at least 3:1.
  • the third OSC material and the third inorganic oxide may have from 10:1 to 1:10, preferably from 8:1 to 1:8 or from 5:1 to 1:5, more preferably from 4:1 to 1:4 or 3:1-1:3 weight ratio.
  • the first palladium component and the second palladium component have a weight ratio of from 50:1 to 1:50. In a further embodiment, the first palladium component and the second palladium component have a weight ratio of from 30:1 to 1:30. In another embodiment, the first palladium component and the second palladium component have a weight ratio of from 10:1 to 1:10. In yet another embodiment, the first palladium component and the second palladium component have a weight ratio of from 5:1 to 1:5.
  • the first palladium component and the second palladium component have a weight ratio of greater than 1:1, more preferably at least 3:1 or 4:1, even more preferably at least 5:1.
  • the third rhodium component and the first palladium component have a weight ratio of from 60:1 to 1:60.
  • the third rhodium component and the first palladium component have a weight ratio of 40:1 to 1:40. More preferably, the third rhodium component and the first palladium component have a weight ratio of from 30:1 to 1:30. Most preferably, the third rhodium component and the first palladium component have a weight ratio of from 10:1 to 1:10.
  • the catalyst articles of the present invention may comprise other components known to those skilled in the art.
  • the compositions of the present invention may further comprise at least one binder and/or at least one surfactant.
  • a binder is present, a dispersible alumina binder is preferred.
  • the carrier is a flow-through monolith.
  • the carrier length can be greater than 90 mm.
  • the flow-through monolith carrier has a first side and a second side defining a longitudinal direction therebetween.
  • the flow-through monolith carrier has a plurality of channels extending between the first side and the second side.
  • the plurality of channels extend longitudinally to provide a plurality of inner surfaces (e.g., surfaces defining walls of the respective channels).
  • the plurality of channels each have an opening in the first face and an opening in the second face.
  • the flow-through monolithic carrier is not a wall flow filter.
  • the first side is typically at the inlet end of the carrier and the second side is at the outlet end of the carrier.
  • the channels can be of constant width and each of the plurality of channels can have a uniform channel width.
  • the monolithic carrier has from 300 to 900 channels per square inch, preferably from 400 to 800, in a plane perpendicular to the longitudinal direction.
  • the open first channel and the closed second channel have a density of 600-700 channels per square inch.
  • the channels may have a cross section of a rectangle, a square, a circle, an ellipse, a triangle, a hexagon, or other geometric shapes.
  • the monolithic carrier acts as a support for supporting the catalytic material.
  • Suitable materials for forming the support include ceramic-like materials such as cordierite, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica, magnesia or zirconium silicate or porous Refractory metal. Such materials and their use in making porous monolithic carriers are well known in the art.
  • the flow-through monolithic carrier described herein is a single component (ie, a monolithic carrier).
  • the carrier used can be formed by bonding a plurality of channels together or by bonding a plurality of smaller carriers as described herein.
  • Such techniques, as well as suitable housings and configurations of the exhaust treatment system, are well known in the art.
  • the ceramic support can be made of any suitable refractory material such as alumina, silica, yttria, zirconia, magnesia, zeolite. , silicon nitride, silicon carbide, zirconium silicate, magnesium silicate, aluminosilicate and metal aluminosilicate (such as cordierite and spodumene) or a mixture or mixture of any two or more thereof Oxide. Cordierite, magnesium aluminosilicate and silicon carbide are particularly preferred.
  • the metal support can be made of any suitable metal, particularly a heat resistant metal and a metal alloy, such as titanium and stainless steel, and containing iron, Nickel, chromium and/or aluminum and other ferritic alloys of trace metals.
  • the first catalytic region can be directly loaded/deposited on the support.
  • the second catalytic region can be directly supported/deposited on the support.
  • the catalyst is treated contains NO x, CO and HC methods vehicle emissions.
  • a catalytic converter equipped with a TWC made according to the method of the present invention shows an improvement over conventional TWC (having the same PGM loading), and in particular shows improved performance and better THC light-off performance in the cold start phase. (See, for example, Examples 1 and 2 and Tables 1 and 2).
  • Another aspect of the invention relates to a system for treating vehicle exhaust, comprising a catalyst article as described herein, along with an exhaust pipe for conveying the exhaust gas through the system.
  • region refers to a range on a support, typically obtained by drying and/or calcining a washcoat.
  • a “region” can be located as a “layer” or “zone” or loaded on a carrier.
  • the range or arrangement on the support is generally controlled during the process of applying the washcoat to the support.
  • “Zones” usually have sharp boundaries or edges (that is, one area can be distinguished from another by conventional analytical techniques).
  • the "region" has a substantially uniform length.
  • substantially uniform length refers to a deviation from its mean value (eg, the difference between the maximum and minimum lengths) of no more than 10%, preferably a deviation of no more than 5%, more preferably a deviation of no more than 1%. .
  • each "region" has a substantially uniform composition (i.e., there is no substantial difference in the composition of the washcoat when a portion of the region is compared to another portion of the region).
  • a substantially uniform composition means that when a portion of a region is compared to another portion of the region, the difference in composition is 5% or less, often 2.5% or less, most typically 1 % or less material (eg area).
  • zone refers to a region having a length less than the total length of the carrier, such as ⁇ 75% of the total length of the carrier.
  • a “zone” typically has a length (i.e., a substantially uniform length) of at least 5% (e.g., > 5%) of the total length of the carrier.
  • the total length of the carrier is the distance between its inlet end and its outlet end (e.g., the opposite end of the carrier).
  • area at the inlet end of the carrier refers to a zone that is or is supported on the carrier, wherein the zone is closer to the carrier inlet end than the zone and the carrier outlet end. Therefore, the midpoint is closer to the carrier inlet end than the midpoint of the zone (i.e., half of its length) and the exit end of the carrier.
  • area at the outlet end of the carrier refers to a zone that is or is supported on the carrier, wherein the zone is closer to the outlet end of the carrier than the inlet end of the zone and the carrier. Therefore, the midpoint is closer to the carrier exit end than the midpoint of the zone (i.e., half of its length) and the carrier inlet end.
  • the midpoint of the zone i.e., half of its length
  • (a) is closer to the inlet end of the inlet passage than the closed end of the inlet passage of the carrier, and/or (b) The midpoint is closer to the closed end of the outlet passage of the outlet passage of the carrier.
  • the term "area at the outlet end of the carrier" as used generally refers to the zone located or supported on the carrier, which:
  • (b) is closer to the closed end of the inlet passage (e.g., the occluded or blocked end) than the inlet end (e.g., the open end) of the inlet passage of the carrier.
  • the midpoint of the zone i.e., half of its length
  • (a) is closer to the outlet end of the outlet passage than the closed end of the outlet passage of the carrier, and/or (b) The midpoint is closer to the closed end of the inlet passage of the inlet of the carrier.
  • the zone can satisfy both (a) and (b).
  • carrier coating is well known in the art and refers to a bond coat that is typically applied to a carrier during the production of a catalyst.
  • platinum group metal generally refers to a metal selected from the group consisting of Ru, Rh, Pd, Os, Ir, and Pt, preferably a metal selected from the group consisting of Ru, Rh, Pd, Ir, and Pt.
  • PGM preferably refers to a metal selected from the group consisting of Rh, Pt and Pd.
  • mixture oxide generally refers to a mixture of oxides of a single phase, as is conventionally known in the art.
  • composite oxide as used herein generally refers to a composition having more than one phase of oxide, as is conventionally known in the art.
  • the expression “consisting essentially of” defines a range of features to include a specified material or step and any other material or step that does not materially affect the essential characteristics of the feature, such as a small amount of impurities.
  • the expression “consisting mainly of” encompasses the expression “consisting of.”
  • the expression “substantially free” as used herein means that the material is in small amounts, such as ⁇ 5 wt%, preferably ⁇ 2 wt%, more preferably ⁇ 1 wt%.
  • the expression “substantially free” encompasses the expression “not included”.
  • the expression “substantially free” as used herein means that the material is in trace amounts, such as ⁇ 1 wt%, preferably ⁇ 0.5 wt%, more preferably ⁇ 0.1 wt. %.
  • the expression “substantially free” encompasses the expression “not included”.
  • the amount of any of the doping elements mentioned herein, particularly the total amount, expressed in wt%, refers to the weight of the support material or its refractory metal oxide.
  • loading amount refers to a measurement based on the weight of a metal in g/ft 3 .
  • the first catalytic region is supported by Pd in a coating consisting of a first CeZr mixed oxide, La stabilized alumina, and a Ba promoter.
  • the coating loading of the first catalytic zone was about 1.7 g/in 3 with a Pd loading of 200 g/ft 3 .
  • washcoat was then coated from the entrance face of a ceramic support (750 pore density, 2.5 mil wall thickness) using a standard coating procedure with a target coating depth of 50% of the length of the support and dried at 90 °C.
  • the second catalytic region is supported by Pd in a coating consisting of a second CeZr mixed oxide, La stabilized alumina, and Ba promoter.
  • the coating loading of the second catalytic zone was about 1.7 g/in 3 with a Pd loading of 34 g/ft 3 .
  • the second washcoat is applied from the exit face of the ceramic support containing the first catalytic zone, the target coating depth is 50% of the length of the support, dried at 90 ° C and at 500 Calcined at ° C for 45 minutes.
  • the third catalytic region is composed of Rh supported on alumina stabilized by a third CeZr mixed oxide and La.
  • the third catalyst zone had a coating loading of about 1.3 g/in 3 with a Rh loading of 8 g/ft 3 .
  • the third washcoat is then coated from the exit face of the ceramic support containing the first and second catalytic zones using a standard coating procedure with a target coating depth of 90% of the length of the support and dried at 90 °C. It was calcined at 500 ° C for 45 minutes.
  • Comparative Catalyst B was prepared according to a procedure similar to Catalyst A except that the third catalytic zone in Comparative Catalyst B was coated with the entire length of the support (i.e., 100%).
  • the total Pd loading was 117 g/ft 3 and the total Rh loading was 8 g/ft 3 .
  • Comparative Catalyst C is a commercial three-way (Pd-Rh) catalyst having a two-layer structure.
  • the bottom layer is supported by Pd in a coating consisting of a first CeZr mixed oxide, La stabilized alumina, and Ba promoter.
  • the undercoat had a coating loading of about 1.7 g/in 3 with a Pd loading of 117 g/ft 3 .
  • the upper layer consists of Rh supported on a second CeZr mixed oxide and La stabilized alumina.
  • the upper layer had a coating loading of about 1.3 g/in 3 with a Rh loading of 8 g/ft 3 .
  • the total coating loading of Catalyst C was about 3.0 g/in 3 .
  • Catalyst D was prepared according to a procedure similar to Catalyst A except that 50% of the Ba promoter was replaced with Sr in the first catalytic zone.
  • Catalyst E was prepared according to a procedure similar to Catalyst A except that 100% of the Ba adjuvant was replaced with Sr in the first catalytic zone.
  • Catalyst A and Comparative Catalyst B and Comparative Catalyst C were tested on a 1.5 liter engine vehicle using the New European Test Cycle (NEDC).
  • the bag data from the exhaust pipe is shown in Table 1.
  • Catalyst A as compared with the comparative catalysts B and C of the present invention there is provided a significantly lower THC, CO and NO x emissions (see, eg, when Catalyst A and Comparative Catalyst B were compared to THC, CO and NO x Emissions related performance improvements of approximately 20%, 10% and 24%).
  • Catalyst A of the present invention provides significantly improved emission control performance during the cold start phase as compared to Comparative Catalysts B and C.
  • Table 2 shows a summary of cumulative emissions data for the first 30 seconds, 50 seconds, and 100 seconds of the driving cycle.
  • Catalyst A and Comparative Catalyst B were tested separately on a gasoline engine.
  • the light-off test was a typical condition, the exhaust flow rate was 80 kg/hr, the heating rate was 30 ° C/min, and the air-fuel ratio (AFR) ⁇ was 14.55. From the concentration of the feed gas and outlet gas of the catalyst calculated by comparing the conversion of THC, CO and NO x.
  • Catalyst A and Comparative Catalyst B were subjected to a 100-hour engine bench aging test under a 6.1 L engine under a 6.1 L engine under a 6.1 L engine. The peak bed temperature of the catalyst was approximately 980. °C.
  • Table 3 shows the comparative catalyst A and catalyst B of THC, CO and NO x T 50 off temperature. Surprisingly, the data indicates that when compared to comparative example bilayer Catalyst B, Catalyst A multizone present invention provide significantly improved light-off performance, a low of about 20 °C T 50 (T 50 to a conversion of The temperature reached 50%).

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Abstract

公开了一种三效催化剂制品，及其在用于内燃机的排气系统中的用途。用于处理废气的催化剂制品包含：包括入口端、出口端并具有轴向长度L的载体；开始于该入口端并延伸小于该轴向长度L的第一催化区域，其中该第一催化区域包含第一钯组分；开始于该出口端并延伸小于该轴向长度L的第二催化区域，其中该第二催化区域包含第二钯组分；开始于该出口端并延伸小于该轴向长度L的第三催化区域，其中该第三催化区域包含第三铑组分；和其中该第三催化区域叠在该第二催化区域之上。

Description

用于汽油机废气处理的新型多区TWC催化剂 技术领域
本发明涉及用于处理汽油机的废气排放的催化制品。
背景技术
内燃机产生含有多种污染物的废气，污染物包括烃(HC)、一氧化碳(CO)和氮氧化物(“NO x”)。广泛地使用包含废气催化转化催化剂的排放控制系统来减少这些污染物排放到大气的量。用于汽油机尾气处理的常用催化剂是TWC(三效催化剂)。TWC执行三个主要功能：(1)CO的氧化；(2)未燃烧的HC的氧化；和(3)NO x的还原。
在多数催化转化器中，TWC被涂覆在可以承受高温的高表面积载体如流通式蜂窝体载体上。这些载体的大表面积有利于提高非均相反应的效率，但会增加排气背压，即限制废气从发动机流到尾气管。尽管TWC技术取得了进步，如美国专利6,022,825、美国专利9,352,279、美国专利9,040,003和美国专利公布2016/0228818中描述的那些，但是仍需要用于某些发动机平台的改进的催化转化器，其同时改进冷起动阶段的性能和/或提供更好的起燃性能。本发明尤其解决了这些问题。
发明内容
本发明的一个方面涉及用于处理汽油机废气的催化剂，其包含：包括入口端、出口端并具有轴向长度L的载体；开始于该入口端并延伸小于该轴向长度L的第一催化区域，其中该第一催化区域包含第一钯组分；开始于该出口端并延伸小于该轴向长度L的第二催化区域，其中该第二催化区域包含第二钯组分；开始于该出口端并延伸小于该轴向长度L的第三催化区域，其中该第三催化区域包含第三铑组分；和其中该第三催化区域叠在该第二催化区域之上。
本发明还包括用于内燃机的排气系统，其包含本发明的三效催化剂部件。
本发明还包括处理内燃机的废气，特别是处理汽油机的废气。该方法包括使废气与本发明的三效催化剂部件接触。
附图说明
图1显示了根据本发明的一个实施方案，第二催化区域和第一催化区域的总长度 等于载体的轴向长度L。
图2a和图2b显示了根据本发明的两个实施方案，第二催化区域与第一催化区域重叠。
图3显示了根据本发明的一个实施方案，第二催化区域和第一催化区域的总长度小于载体的轴向长度L。
图4a、4b和4c显示了分别来自催化剂A、对比催化剂B和对比催化剂C的车辆测试的累计稀释袋采的THC、CO和NO x排放。
具体实施方式
本发明涉及燃烧废气如由汽油机和其他发动机产生的废气的催化处理，并涉及相关的催化剂和系统。更具体地，本发明涉及在车辆排气系统中NO x、CO和HC的同时处理。本发明人发现某些具有催化活性的金属和它们的涂覆方式之间的协同关系，其出人意料地产生NO x、CO和HC的高转化率；改进冷起动阶段中的性能；并提供更好的起燃性能。本发明的方法还可降低催化剂成本。
本发明的一个方面涉及用于处理废气的催化剂制品，其包含：包括入口端、出口端并具有轴向长度L的载体；开始于该入口端并延伸小于该轴向长度L的第一催化区域，其中该第一催化区域包含第一钯组分；开始于该出口端并延伸小于该轴向长度L的第二催化区域，其中该第二催化区域包含第二钯组分；开始于该出口端并延伸小于该轴向长度L的第三催化区域，其中该第三催化区域包含第三铑组分；和其中该第三催化区域叠在该第二催化区域之上。
本发明人发现，采用这种涂覆方式的催化剂表现出更优异的催化剂性能，这是使用单独的或常规涂覆方式的催化剂所不能实现的。本发明的预料不到的益处是，与类似浓度(例如载体涂层(washcoat)负载量)的常规TWC催化剂相比，具有优异的催化剂起燃性能，在整车冷起动阶段，可显著降低排气污染物的排放，从而更容易达到排放目标。这些益处的获得，可降低催化剂中贵金属的用量，从而降低成本。
第一催化区域可以延伸轴向长度L的30-70％。优选地，第一催化区域可以延伸轴向长度L的40-60％，更优选45-55％。
第二催化区域可以延伸轴向长度L的30-70％。优选地，第二催化区域可以延伸轴向长度L的40-60％，更优选45-55％。
第二催化区域可以与第一催化区域重叠轴向长度L的0.1-15％(例如参见图2a和 图2b，第一催化区域可以叠在第二催化区域之上，或者第二催化区域可以叠在第一催化区域之上)。可选地，第二催化区域和第一催化区域的总长度可以等于轴向长度L(例如参见图1)。在又一选项中，第二催化区域和第一催化区域的总长度可以小于轴向长度L，例如不大于轴向长度L的95％、90％、80％或70％(例如参见图3)。
第三催化区域可以延伸轴向长度L的50-99％。优选地，第三催化区域可以延伸轴向长度L的50-95％，更优选60-95％。
第一催化区域可以基本上不含第一钯组分之外的PGM金属。
第一催化剂层可以含第一钯组分之外的PGM金属，例如，铂和/或铑。第一催化区域可以包含0.1-300g/ft 3的第一钯或铂钯组分。优选地，第一催化区域可以包含50-250g/ft 3的第一钯或铂钯组分，更优选100-220g/ft 3的第一钯或铂钯组分，其中，铂钯的重量比例可以为60:1-1:60，优选地为30:1-1:30，更优选地为10:1-1:10。
第一催化区域的总载体涂层负载量可以小于3.5g/in 3，优选小于3.0g/in 3，2.5g/in 3或1.5g/in 3。
第一催化区域可以进一步包含第一储氧(OSC)材料、第一碱金属或碱土金属组分和/或第一无机氧化物。
第一OSC材料优选选自氧化铈、氧化锆、氧化铈-氧化锆混合氧化物和氧化铝-氧化铈-氧化锆混合氧化物。更优选地，第一OSC材料包含氧化铈-氧化锆混合氧化物。氧化铈-氧化锆混合氧化物可以进一步包含一些掺杂元素，如镧、钕、镨、钇氧化物等。另外，第一OSC材料可充当第一钯组分的载体材料。
第一钯组分可以负载在第一无机氧化物和第一OSC材料上。
氧化铈-氧化锆混合氧化物至少50:50，优选大于60:40，更优选大于75:25的摩尔比。
第一OSC材料(例如氧化铈-氧化锆混合氧化物)可以为基于第一催化区域的总载体涂层负载量的10-90wt％，优选25-75wt％，更优选30-60wt％。
第一催化区域中的第一OSC材料负载量可以小于1.5g/in 3。在一些实施方案中，第一催化区域中的第一OSC材料负载量不大于1.2g/in 3，1.0g/in 3，0.9g/in 3，0.8g/in 3或0.7g/in 3。
在一些实施方案中，第一碱金属或碱土金属可以沉积在第一OSC材料上。替代地或另外地，第一碱金属或碱土金属可以沉积在第一无机氧化物上。即在一些实施方案中，第一碱金属或碱土金属可以沉积在，即存在于第一OSC材料和第一无机氧化物二 者上。
第一碱金属或碱土金属总体上与第一无机氧化物接触。优选地，第一碱金属或碱土金属负载在第一无机氧化物上。或者第一碱金属或碱土金属也可与第一OSC材料接触。
第一碱金属或碱土金属优选为钡或锶，及其混合氧化物或复合氧化物。优选地，当存在时，钡或锶的负载量为基于第一催化区域的总重量计0.1-15wt％，更优选3-10wt％的钡或锶。
甚至更优选地，第一碱金属或碱土金属为锶。当存在时，锶的负载量优选为基于第一催化区域的总重量计0.1-15wt％，更优选3-10wt％。
还优选的是，第一碱金属或碱土金属为钡和锶的混合氧化物或复合氧化物。优选地，钡和锶的混合氧化物或复合氧化物的存在量为基于第一催化区域的总重量计0.1-15wt％，更优选3-10wt％。更优选的是，第一碱金属或碱土金属为钡和锶的复合氧化物。
优选地，钡或锶作为BaCO 3或SrCO 3形式存在。这样的材料可以以本领域已知的任何方法，例如初湿浸渍或喷雾干燥来获得。
第一无机氧化物优选为第2、3、4、5、13和14族元素的氧化物。第一无机氧化物优选选自氧化铝、氧化镁、二氧化硅、氧化铈、钡氧化物及其混合氧化物或复合氧化物。特别优选地，第一无机氧化物为氧化铝、镧-氧化铝、氧化铈或氧化镁/氧化铝复合氧化物。一种尤其优选的第一无机氧化物为氧化铝或镧-氧化铝复合氧化物。
第一OSC材料和第一无机氧化物可以具有不大于10:1，优选不大于8:1或5:1，更优选不大于4:1或3:1，最优选不大于2:1的重量比。
替代地，第一OSC材料和第一无机氧化物可以具有10:1-1:10，优选8:1-1:8或5:1-1:5，更优选4:1-1:4或3:1-1:3，最优选2:1-1:2的重量比。
第二催化区域可以基本上不含第二钯组分之外的PGM金属。
第二催化剂层可以含第二钯组分之外的PGM金属，例如，铂和/或铑。第二催化区域可以包含0.1-100g/ft 3的第二钯或铂钯组分。优选地，第二催化区域可以包含5-60g/ft 3，更优选10-50g/ft 3的第二钯或铂钯组分，其中，铂钯的重量比例可以为60:1-1:60，优选地为30:1-1:30，更优选地为10:1-1:10。
第二催化区域可以进一步包含第二储氧(OSC)材料、第二碱金属或碱土金属组分和/或第二无机氧化物。
第二OSC材料优选选自氧化铈、氧化锆、氧化铈-氧化锆混合氧化物和氧化铝-氧化铈-氧化锆混合氧化物。更优选地，第二OSC材料包含氧化铈-氧化锆混合氧化物。另外，第二OSC材料可以进一步包含掺杂元素如镧、钕、镨、钇等中的一种或几种。并且，第二OSC材料可以充当第二钯组分的载体材料。
第二钯或铂钯组分可以负载在第二无机氧化物和第二OSC材料上。
氧化铈-氧化锆混合氧化物可以具有氧化锆与氧化铈至少50:50，优选大于60:40，更优选大于75:25的摩尔比。
第二OSC材料(例如氧化铈-氧化锆混合氧化物)可以为基于第二催化区域的总载体涂层负载量计10-90wt％，优选25-75wt％，更优选30-60wt％。
第二催化区域中的第二OSC材料负载量可以小于1.5g/in 3。在一些实施方案中，第二催化区域中的第二OSC材料负载量不大于1.2g/in 3，1.0g/in 3，0.9g/in 3，0.8g/in 3或0.7g/in 3。
第二催化区域的总载体涂层负载量可以小于3.5g/in 3，优选小于3.0g/in 3，2.5g/in 3，或1.5g/in 3。
在一些实施方案中，第二碱金属或碱土金属可以沉积在第二OSC材料上。替代地或另外地，第二碱金属或碱土金属可以沉积在第二无机氧化物上。即在一些实施方案中，第二碱金属或碱土金属可以沉积在，即存在于第二OSC材料和第二无机氧化物二者上。
第二碱金属或碱土金属总体上与第二无机氧化物接触。优选地，第二碱金属或碱土金属负载在第二无机氧化物上。对于与第二无机氧化物接触而言另外地或替代地，第二碱金属或碱土金属可以与第二OSC材料接触。
第二碱金属或碱土金属优选为钡、锶、其混合氧化物或复合氧化物。优选地，当存在时，钡或锶的含量为基于第二催化区域的总重量计0.1-15wt％，更优选3-10wt％的钡或锶。
甚至更优选地，第二碱金属或碱土金属为锶。当存在时，锶的存在量优选为基于第二催化区域的总重量计0.1-15wt％，更优选3-10wt％。
还优选的是，第二碱金属或碱土金属为钡和锶的混合氧化物或复合氧化物。优选地，钡和锶的混合氧化物或复合氧化物的存在量为基于第二催化区域的总重量计0.1-15wt％，更优选3-10wt％。更优选的是，第二碱金属或碱土金属为钡和锶的复合氧化物。
优选地，钡或锶作为BaCO 3或SrCO 3形式存在。这样的材料可以本领域已知的任何方法，例如初湿浸渍或喷雾干燥来获得。
第二无机氧化物优选为第2、3、4、5、13和14族元素的氧化物。第二无机氧化物优选选自氧化铝、氧化镁、二氧化硅、氧化铈、钡氧化物及其混合氧化物或复合氧化物。特别优选地，第二无机氧化物为氧化铝、镧-氧化铝、氧化铈或氧化镁/氧化铝复合氧化物。一种尤其优选的第二无机氧化物为氧化铝或镧-氧化铝复合氧化物。
第二OSC材料和第二无机氧化物可以具有不大于不大于10:1，优选不大于8:1或5:1，更优选不大于4:1或3:1，最优选不大于2:1的重量比。
替代地，第二OSC材料和第二无机氧化物可以具有10:1-1:10，优选8:1-1:8或5:1-1:5，更优选4:1-1:4或3:1-1:3，最优选2:1-1:2的重量比。
第三催化区域可基本上不含第三铑组分之外的PGM金属。
第三催化区域可包含0.1-20g/ft 3的第三铑或铂铑组分。优选地，第三催化区域可以包含3-15g/ft 3，更优选5-13g/ft 3的第三铑或铂铑组分，其中，铂铑的重量比例可以为20:1-1:20，优选地为15:1-1:15，更优选地为10:1-1:10。
第三催化区域的总载体涂层负载量可以小于3.5g/in 3；优选地，小于3.0g/in 3或2g/in 3；更优选地，小于1.5g/in 3或1.0g/in 3。
第三催化区域可进一步包含第三储氧(OSC)材料、第三碱金属或碱土金属组分和/或第三无机氧化物。
第三OSC材料优选选自氧化铈、氧化锆、氧化铈-氧化锆混合氧化物和氧化铝-氧化铈-氧化锆混合氧化物。优选地，第三OSC材料包含氧化铈-氧化锆混合氧化物，并具有镧、钕、钇、镨等掺杂元素的一种或几种。另外，第三OSC材料可充当第三铑组分的载体材料。
氧化铈-氧化锆混合氧化物可具有氧化锆与氧化铈至少为50:50，优选大于60:40，更优选大于80:20的摩尔比。
第三OSC材料可以为基于第三催化区域的总载体涂层负载量计10-90wt％，优选25-75wt％，更优选35-65wt％。
第三催化区域中的第三OSC材料负载量可小于2g/in 3。在一些实施方案中，第三催化区域中的第三OSC材料负载量不大于1.5g/in 3，1.2g/in 3，1.0g/in 3或0.5g/in 3。
优选地，第三催化区域大体上不含第三碱金属或碱土金属，更优选基本上不含第三碱金属或碱土金属。
第三无机氧化物优选为第2、3、4、5、13和14族元素的氧化物。第三无机氧化物优选选自氧化铝，氧化铈，氧化镁，二氧化硅，镧、锆、钕、镨氧化物及其混合氧化物或复合氧化物。特别优选地，第三无机氧化物为氧化铝、镧/氧化铝复合氧化物或锆/氧化铝复合氧化物。一种尤其优选的第三无机氧化物为镧/氧化铝复合氧化物或锆/氧化铝复合氧化物。第三无机氧化物可为第三铑组分和/或第三OSC材料的载体材料。
优选的第三无机氧化物优选具有大于80m 2/g的新鲜表面积，0.1-4mL/g的孔体积。特别优选具有大于100m 2/g的表面积的高表面积无机氧化物，例如高表面积氧化铝。其他优选的第三无机氧化物包括镧/氧化铝复合氧化物，任选地进一步包含锆组分例如氧化锆。在这样的情况中，锆可以存在于该镧/氧化铝复合氧化物的表面上，例如作为涂层。
第三OSC材料和第三无机氧化物可以具有至少1:1，优选至少2:1，更优选至少3:1的重量比。
替代地，第三OSC材料和第三无机氧化物可以具有10:1-1:10，优选8:1-1:8或5:1-1:5，更优选4:1-1:4或3:1-1:3的重量比。
在一些实施方案中，第一钯组分和第二钯组分具有50:1-1:50的重量比。在另外的实施方案中，第一钯组分和第二钯组分具有30:1-1:30的重量比。在另一实施方案中，第一钯组分和第二钯组分具有10:1-1:10的重量比。在又一实施方案中，第一钯组分和第二钯组分具有5:1-1:5的重量比。
优选的是，第一钯组分和第二钯组分具有大于1:1，更优选至少3:1或4:1，甚至更优选至少5:1的重量比。
在一些实施方案中，第三铑组分和第一钯组分具有60:1-1:60的重量比。优选地，第三铑组分和第一钯组分具有40:1-1:40的重量比。更优选地，第三铑组分和第一钯组分具有30:1-1:30的重量比。最优选地，第三铑组分和第一钯组分具有10:1-1:10的重量比。
本发明的催化剂制品可以包含本领域技术人员已知的其他组分。例如，本发明的组合物可以进一步包含至少一种粘结剂和/或至少一种表面活性剂。当存在粘结剂时，优选可分散的氧化铝粘结剂。
优选地，载体是流通式整料。
载体长度可以大于90mm。
流通式整料载体具有其间限定了纵向的第一面和第二面。流通式整料载体具有多个在第一面和第二面之间延伸的通道。多个通道在纵向上延伸，提供多个内表面(例如限定各个通道的壁的表面)。多个通道每个具有在第一面的开口和在第二面的开口。为避免疑义，流通式整料载体不是壁流式过滤器。
第一面通常在载体的入口端，第二面在载体的出口端。
通道可以为恒定的宽度，并且多个通道每个可以具有均匀的通道宽度。
优选地，在与纵向垂直的平面内，整料载体具有每平方英寸300-900个通道，优选400-800个。例如，在第一面上，开放的第一通道和封闭的第二通道的密度为每平方英寸600-700个通道。通道可以具有矩形、正方形、圆形、椭圆形、三角形、六边形或其他几何形状的横截面。
整体式的载体充当用于支撑催化材料的载体。用于形成载体的适合材料包括陶瓷样材料，如堇青石、碳化硅、氮化硅、氧化锆、莫来石、锂辉石、氧化铝-二氧化硅、氧化镁或硅酸锆或者多孔的难熔金属。这样的材料和它们在制造多孔整体式载体中的应用是本领域中公知的。
应当注意，本文所述的流通式整体式载体是单个部件(即单块载体)。不过，当形成排放处理系统时，所用的载体可以通过将多个通道粘在一起或者通过将多个较小的本文所述的载体粘在一起来形成。这样的技术，以及排放处理系统的适合的外壳和构造是本领域中公知的。
在本发明的催化剂制品包含陶瓷载体的实施方案中，该陶瓷载体可以由任何适合的难熔材料制成，该难熔材料例如氧化铝、二氧化硅、氧化铈、氧化锆、氧化镁、沸石、氮化硅、碳化硅、锆硅酸盐、镁硅酸盐、铝硅酸盐和金属铝硅酸盐(如堇青石和锂辉石)或者其任意两种或更多种的混合物或混合氧化物。特别优选堇青石、铝硅酸镁和碳化硅。
在本发明的催化剂制品包含金属载体的实施方案中，该金属载体可以由任何适合的金属，特别是耐热金属和金属合金制成，该耐热金属和金属合金例如钛和不锈钢以及含有铁、镍、铬和/或铝还有其他痕量金属的铁素体合金。
在一些实施方案中，第一催化区域可以直接负载/沉积在载体上。在某些实施方案中，第二催化区域可以直接负载/沉积在载体上。
本发明的另一方面涉及使用本文所述的催化剂制品来处理含有NO x、CO和HC的车辆废气的方法。装备有根据本发明方法制造的TWC的催化转化器显示了与常规TWC(具 有相同的PGM负载量)相比的改进，而且尤其显示了冷起动阶段中改进的性能和更好的THC起燃性能(例如参见实施例1和2以及表1和2)。
本发明的另一方面涉及用于处理车辆废气的系统，该系统包含本文所述的催化剂制品，连同用于将该废气输送过该系统的排气管。
定义
本文使用的术语“区域”指的是载体上的一个范围，通常通过干燥和/或煅烧载体涂层来获得。例如，“区域”可以作为“层”或“区”位于或负载在载体上。在将载体涂层施用到载体的工艺过程中，载体上的范围或布置总体上受到控制。“区域”通常具有清晰的边界或边缘(即可以使用常规分析技术将一个区域与另一个区域区分开)。
通常，“区域”具有大体上均匀的长度。在本文语境中提及的“大体上均匀的长度”指的是与其平均值偏离(例如最大和最小长度之差)不大于10％，优选偏离不大于5％，更优选偏离不大于1％。
优选的是，各个“区域”具有大体上均匀的组成(即当将区域的一部分与该区域的另一部分进行比较时，载体涂层的组成上没有实质的差别)。在本文语境中，大体上均匀的组成指的是当将区域的一部分与该区域的另一部分进行比较时，组成上的差别为5％或更小，经常2.5％或更小，最通常1％或更小的材料(例如区域)。
本文使用的术语“区”指的是长度小于载体总长度，如≤载体总长度的75％的区域。“区”通常具有载体总长度的至少5％(例如≥5％)的长度(即大体上均匀的长度)。
载体总长度为其入口端与其出口端(例如载体的相对端)之间的距离。
本文使用中提到的“位于载体入口端的区”指的是位于或负载在该载体上的区，其中比起该区与载体出口端，该区更接近于载体入口端。所以，比起该区的中点(即其长度的一半)与载体出口端，该中点更接近于载体入口端。类似地，本文使用中提到的“位于载体出口端的区”指的是位于或负载在该载体上的区，其中比起该区与载体入口端，该区更接近于载体出口端。所以，比起该区的中点(即其长度的一半)与载体入口端，该中点更接近于载体出口端。
当载体为壁流式过滤器时，则总体上提到的“位于载体入口端的区”指的是位于或负载在该载体上的区，其：
(a)比起该区与该载体的入口通道的封闭端(例如闭塞的或堵塞的端)，更接近于 该入口通道的入口端(例如开口端)，和/或
(b)比起该区与该载体的出口通道的出口端(例如开口端)，更接近于该出口通道的封闭端(例如闭塞的或堵塞的端)。
所以，该区的中点(即其长度的一半)(a)比起该中点与该载体的入口通道的封闭端，更接近于该入口通道的入口端，和/或(b)比起该中点与该载体的出口通道的出口端，更接近于该出口通道的封闭端。
类似地，当载体为壁流式过滤器时，则总体上提到的“位于载体出口端的区”指的是位于或负载在该载体上的区，其：
(a)比起该区与该载体的出口通道的封闭端(例如闭塞的或堵塞的)，更接近于该出口通道的出口端(例如开口端)，和/或
(b)比起它与该载体的入口通道的入口端(例如开口端)，更接近于该入口通道的封闭端(例如闭塞的或堵塞的端)。
所以，该区的中点(即其长度的一半)(a)比起该中点与该载体的出口通道的封闭端，更接近于该出口通道的出口端，和/或(b)比起该中点与该载体的入口通道的入口端，更接近于该入口通道的封闭端。
当载体涂层存在于壁流式过滤器的壁中(即区在壁中)时，该区可以满足(a)和(b)二者。
术语“载体涂层”是本领域中公知的，指的是通常在生产催化剂过程中施用到载体的粘合涂层。
本文使用的缩写“PGM”指的是“铂族金属”。术语“铂族金属”总体上指的是选自Ru、Rh、Pd、Os、Ir和Pt的金属，优选为选自Ru、Rh、Pd、Ir和Pt的金属。总的来说，术语“PGM”优选指的是选自Rh、Pt和Pd的金属。
本文使用的术语“混合氧化物”总体上指的是单一相的氧化物的混合物，如本领域中常规上已知的。本文使用的术语“复合氧化物”总体上指的是具有多于一相的氧化物的组合物，如本领域中常规上已知的。
本文使用的表达“主要由……组成”将特征范围限定为包括指定的材料或步骤和不实质影响该特征的基本特性的任何其他材料或步骤，例如少量杂质。表达“主要由……组成”囊括表达“由……组成”。
通常在区域、层或区的含量的语境中，本文针对材料使用的表达“大体上不含”意思是该材料为少量，如≤5wt％，优选≤2wt％，更优选≤1wt％。表达“大体上不含” 囊括表达“不包含”。
通常在区域、层或区的含量的语境中，本文针对材料使用的表达“基本上不含”意思是该材料为痕量，如≤1wt％，优选≤0.5wt％，更优选≤0.1wt％。表达“基本上不含”囊括表达“不包含”。
本文使用中任何提及的掺杂元素的量，特别是总量，用wt％表示，指的是载体材料或其难熔金属氧化物的重量。
本文使用的术语“负载量”指的是基于金属重量的测量，单位为g/ft 3。
以下实施例仅例示本发明。本领域技术人员将认识到本发明主旨和权利要求书范围内的许多变化。
实施例
材料
全部材料是可商购的和从已知供应商处获得，除非另外指出。
催化剂A：
第一催化区域：
第一催化区域由Pd负载在由第一CeZr混合氧化物、La稳定化的氧化铝和Ba助剂组成的涂层中。第一催化区域的涂层上载量为约1.7g/in 3，其中Pd负载量为200g/ft 3。
然后，使用标准涂覆程序，将该载体涂层从陶瓷载体(750孔密度，2.5mil壁厚)的入口面涂覆，目标涂覆深度为载体长度的50％，在90℃干燥。
第二催化区域：
第二催化区域由Pd负载在由第二CeZr混合氧化物、La稳定化的氧化铝和Ba助剂组成的涂层中。第二催化区域的涂层上载量为约1.7g/in 3，其中Pd负载量为34g/ft 3。
然后，使用标准涂覆程序，将第二载体涂层从含有第一催化区域的该陶瓷载体的出口面从上涂覆，目标涂覆深度为载体长度的50％，在90℃干燥并在500℃煅烧45分钟。
第三催化区域：
第三催化区域由Rh负载在由第三CeZr混合氧化物和La稳定化的氧化铝组成。第三催化区域的涂层上载量为约1.3g/in 3，其中Rh负载量为8g/ft 3。
然后，使用标准涂覆程序，将第三载体涂层从含有第一和第二催化区域的该陶瓷载体的出口面从上涂覆，目标涂覆深度为载体长度的90％，在90℃干燥并在500℃煅烧45分钟。
对比催化剂B：
根据与催化剂A类似的程序制备对比催化剂B，除了将对比催化剂B中的第三催化区域涂覆载体的整个长度(即100％)。总Pd负载量为117g/ft 3，和总Rh负载量为8g/ft 3。
对比催化剂C：
对比催化剂C是具有双层结构的商业三效(Pd-Rh)催化剂。底层由Pd负载在由第一CeZr混合氧化物、La稳定化的氧化铝和Ba助剂组成的涂层中。底层的涂层负载量为约1.7g/in 3，其中Pd负载量为117g/ft 3。上层由Rh负载在第二CeZr混合氧化物和La稳定化的氧化铝组成。上层的涂层上载量为约1.3g/in 3，其中Rh负载量为8g/ft 3。催化剂C的总涂层上载量为约3.0g/in 3。
催化剂D
根据与催化剂A类似的程序制备催化剂D，除了在第一催化区域中用Sr替换50％的Ba助剂。
催化剂E
根据与催化剂A类似的程序制备催化剂E，除了在第一催化区域中用Sr替换100％的Ba助剂。
实施例1：车辆测试程序和结果
用新欧洲测试循环(NEDC)，在1.5升发动机的车辆上测试催化剂A和对比催化剂B和对比催化剂C的新鲜性能。表1中显示了来自尾气管的袋采数据。本发明的催化 剂A与对比催化剂B和C相比，提供了显著更低的THC、CO和NO x排放(例如，参见与当催化剂A与对比催化剂B进行比较时分别对THC、CO和NO x排放大约20％、10％和24％的相关性能改进)。
表1 整车稀释袋采尾气排放数据
Figure PCTCN2018119728-appb-000001
另外，如图4a、4b和4c中所示，本发明的催化剂A与对比催化剂B和C相比，提供了在冷起动阶段显著改进的排放控制性能。表2中显示了驾驶周期最初30秒、50秒、100秒的累计排放数据总结。
表2 在冷起动阶段的累计尾气排放结果
Figure PCTCN2018119728-appb-000002
实施例2：发动机测试中的起燃性能测试
在汽油机上分别测试催化剂A和对比催化剂B。起燃测试为典型条件，排气流量为80kg/小时，升温速率为30℃/分钟，空燃比(AFR)的λ为14.55。从对进料气体和催化剂出口气体的浓度进行比较来计算THC、CO和NO x的转化率。在发动机起燃测试之前，将催化剂A和对比催化剂B在相同运转中，在6.1L发动机下，用四工况标准老化循环进行100小时的发动机台架老化实验，催化剂的峰值床温约为980℃。
表3中显示了催化剂A和对比催化剂B的THC、CO和NO x T 50起燃温度。数据令人惊讶地指出，当与对比催化剂B的双层实例相比时，本发明的多区催化剂A提供了显著改进的起燃性能，低约20℃的T 50(T 50为当转化率达到50％时的温度)。
表3 发动机实验台起燃测试结果
Figure PCTCN2018119728-appb-000003
实施例3：车辆测试程序和结果
用新欧洲测试循环(NEDC)，在1.5升发动机的车辆上测试催化剂A、催化剂D和催化剂E的经台架老化的样件。台架老化在相同运转中，在6.1L发动机下，用四工况标准老化循环进行150小时的发动机台架老化实验，催化剂的峰值床温约为980℃。表4中显示了来自整车的排气管稀释袋采数据结果。本发明的催化剂D和催化剂E与催化剂A相比，提供了甚至更低的THC、CO和NO x排放(例如，参见与当催化剂E与催化剂A进行比较时分别对THC、CO和NO x排放大约26％、18％和14％的相关性能改进)。
表4 通过整车稀释袋采排放结果
Figure PCTCN2018119728-appb-000004

Claims (40)

  1. 用于处理废气的催化剂制品，其包含：
    包括入口端、出口端并具有轴向长度L的载体；
    开始于该入口端并延伸小于该轴向长度L的第一催化区域，其中该第一催化区域包含第一钯组分；
    开始于该出口端并延伸小于该轴向长度L的第二催化区域，其中该第二催化区域包含第二钯组分；
    开始于该出口端并延伸小于该轴向长度L的第三催化区域，其中该第三催化区域包含第三铑组分；和
    其中该第三催化区域叠在该第二催化区域之上。
  2. 根据权利要求1所述的催化剂制品，其中该第一催化区域延伸该轴向长度L的30-70％。
  3. 根据权利要求1或2所述的催化剂制品，其中该第二催化区域延伸该轴向长度L的30-70％。
  4. 根据前述权利要求中任一项所述的催化剂制品，其中该第二催化区域与该第一催化区域重叠该轴向长度L的1-15％。
  5. 根据权利要求1-3中任一项所述的催化剂制品，其中该第二催化区域和该第一催化区域的总长度等于该轴向长度L。
  6. 根据权利要求1-3中任一项所述的催化剂制品，其中该第二催化区域和该第一催化区域的总长度小于该轴向长度L。
  7. 根据前述权利要求中任一项所述的催化剂制品，其中该第三催化区域延伸该轴向长度L的50-95％。
  8. 根据前述权利要求中任一项所述的催化剂制品，其中该第一催化区域基本上不含 该第一钯组分之外的PGM金属。
  9. 根据前述权利要求中任一项所述的催化剂制品，其中该第一催化区域包含0.1-300g/ft 3的该第一钯组分。
  10. 根据前述权利要求中任一项所述的催化剂制品，其中该第一催化区域进一步包含第一储氧(OSC)材料、第一碱金属或碱土金属组分和/或第一无机氧化物。
  11. 根据权利要求10所述的催化剂制品，其中该第一OSC材料选自氧化铈、氧化锆、氧化铈-氧化锆混合氧化物和氧化铝-氧化铈-氧化锆混合氧化物。
  12. 根据权利要求11所述的催化剂制品，其中该第一OSC材料包括氧化铈-氧化锆混合氧化物。
  13. 根据权利要求10-12中任一项所述的催化剂制品，其中该第一碱金属或碱土金属为钡、锶或者钡和锶的混合氧化物或复合氧化物。
  14. 根据权利要求13所述的催化剂制品，其中该第一碱金属或碱土金属的负载量为基于该第一催化区域的涂层总重量计0.1-15wt％。
  15. 根据权利要求10-14中任一项所述的催化剂制品，其中该第一钯组分负载在该第一无机氧化物和该第一OSC材料上。
  16. 根据权利要求10-15中任一项所述的催化剂制品，其中该第一无机氧化物选自氧化铝，氧化铈，氧化镁，二氧化硅，镧、钕、镨、钇氧化物，及其混合氧化物或复合氧化物。
  17. 根据权利要求16所述的催化剂制品，其中该第一无机氧化物为氧化铝、氧化镧/氧化铝复合氧化物或氧化镁/氧化铝复合氧化物。
  18. 根据前述权利要求中任一项所述的催化剂制品，其中该第二催化区域基本上不含该第二钯组分之外的PGM金属。
  19. 根据前述权利要求中任一项所述的催化剂制品，其中该第二催化区域包含0.1-50g/ft 3的该第二钯组分。
  20. 根据前述权利要求中任一项所述的催化剂制品，其中该第二催化区域进一步包含第二储氧(OSC)材料、第二碱金属或碱土金属组分和/或第二无机氧化物。
  21. 根据权利要求20所述的催化剂制品，其中该第二OSC材料选自氧化铈、氧化锆、氧化铈-氧化锆混合氧化物和氧化铝-氧化铈-氧化锆混合氧化物。
  22. 根据权利要求21所述的催化剂制品，其中该第二OSC材料包括氧化铈-氧化锆混合氧化物。
  23. 根据权利要求20-22所述的催化剂制品，其中该第二碱金属或碱土金属为钡、锶或者钡和锶的混合氧化物或复合氧化物。
  24. 根据权利要求23所述的催化剂制品，其中该第二碱金属或碱土金属的负载量为基于该第二催化区域的总重量计0.1-15wt％。
  25. 根据权利要求20-24中任一项所述的催化剂制品，其中该第二无机氧化物选自氧化铝，氧化铈，氧化镁，二氧化硅，镧、钕、镨、钇氧化物，及其混合氧化物或复合氧化物。
  26. 根据权利要求25所述的催化剂制品，其中该第二无机氧化物为氧化铝、氧化镧/氧化铝复合氧化物或氧化镁/氧化铝复合氧化物。
  27. 根据前述权利要求中任一项所述的催化剂制品，其中该第三催化区域包含0.1-20g/ft 3的该第三铑组分。
  28. 根据前述权利要求中任一项所述的催化剂制品，其中该第三催化区域进一步包含第三储氧(OSC)材料、第三碱金属或碱土金属组分和/或第三无机氧化物。
  29. 根据权利要求28所述的催化剂制品，其中该第三OSC材料选自氧化铈、氧化锆、氧化铈-氧化锆混合氧化物和氧化铝-氧化铈-氧化锆混合氧化物。
  30. 根据权利要求29所述的催化剂制品，其中该第三OSC材料包括氧化铈-氧化锆混合氧化物。
  31. 根据权利要求28-30中任一项所述的催化剂制品，其中该第三铑组分负载在该第三OSC材料上。
  32. 根据权利要求28-31中任一项所述的催化剂制品，其中该第三无机氧化物选自氧化铝，氧化铈，氧化镁，二氧化硅，镧、钕、镨、钇氧化物，及其混合氧化物或复合氧化物。
  33. 根据权利要求28-32中任一项所述的催化剂制品，其中该第三无机氧化物为氧化铝、氧化镧/氧化铝复合氧化物或氧化镁/氧化铝复合氧化物。
  34. 根据权利要求28-33中任一项所述的催化剂制品，其中该第三催化区域基本上不含该第三碱金属或碱土金属。
  35. 根据前述权利要求中任一项所述的催化剂制品，其中该载体为流通式整料。
  36. 根据前述权利要求中任一项所述的催化剂制品，其中该载体长度大于90mm。
  37. 根据前述权利要求中任一项所述的催化剂制品，其中该第一催化区域直接负载/沉积在该载体上。
  38. 根据前述权利要求中任一项所述的催化剂制品，其中该第二催化区域直接负载/ 沉积在该载体上。
  39. 用于处理燃烧废气流的排放处理系统，其包含根据权利要求1-38中任一项所述的催化剂制品。
  40. 处理内燃机废气的方法，其包括使该废气与根据权利要求1-39中任一项所述的催化剂制品接触。
PCT/CN2018/119728 2017-12-08 2018-12-07 用于汽油机废气处理的新型多区twc催化剂 WO2019109999A1 (zh)

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EP18885243.8A EP3721990A4 (en) 2017-12-08 2018-12-07 NEW MULTI-REGION TWC FOR TREATMENT OF EXHAUST GAS FROM A PETROL ENGINE
JP2020530583A JP7451402B2 (ja) 2017-12-08 2018-12-07 ガソリンエンジンからの排気ガス処理のための新規多領域ｔｗｃ
BR112020009899-0A BR112020009899A2 (pt) 2017-12-08 2018-12-07 artigo catalisador para o tratamento de gás de escape, sistema de tratamento de emissão para tratar um fluxo de um gás de escape de combustão, e, método de tratamento de um gás de escape de um motor de combustão interna.
RU2020116416A RU2776996C2 (ru) 2017-12-08 2018-12-07 Новый многослойный катализатор twc для очистки отработавшего газа из бензинового двигателя
US15/733,193 US11439987B2 (en) 2017-12-08 2018-12-07 Multi-region TWC for treatment of exhaust gas from gasoline engine
JP2023188364A JP2024016163A (ja) 2017-12-08 2023-11-02 ガソリンエンジンからの排気ガス処理のための新規多領域ｔｗｃ

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