WO2019109998A1 - 用于汽油废气应用的新型三区两层twc催化剂 - Google Patents

用于汽油废气应用的新型三区两层twc催化剂 Download PDF

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WO2019109998A1
WO2019109998A1 PCT/CN2018/119727 CN2018119727W WO2019109998A1 WO 2019109998 A1 WO2019109998 A1 WO 2019109998A1 CN 2018119727 W CN2018119727 W CN 2018119727W WO 2019109998 A1 WO2019109998 A1 WO 2019109998A1
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inlet
outlet
catalyst
oxide
catalyst layer
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PCT/CN2018/119727
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English (en)
French (fr)
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董文杰
吉红宇
乔东升
万亚平
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庄信万丰(上海)化工有限公司
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Priority to BR112020009925-2A priority Critical patent/BR112020009925A2/pt
Priority to JP2020530381A priority patent/JP2021505367A/ja
Priority to EP18886838.4A priority patent/EP3722571B1/en
Priority to RU2020116420A priority patent/RU2780479C2/ru
Priority to US15/733,192 priority patent/US11110447B2/en
Publication of WO2019109998A1 publication Critical patent/WO2019109998A1/zh
Priority to US17/305,899 priority patent/US11577234B2/en
Priority to JP2023149397A priority patent/JP2024001034A/ja

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    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to 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 containing exhaust gas catalysts are widely used to reduce the amount of these pollutants released into the atmosphere.
  • a common catalyst for gasoline engine applications is TWC.
  • the TWC performs three main functions: (1) oxidation of CO; (2) oxidation of unburned HC; and (3) reduction of NO x to N 2 .
  • TWC is coated on high surface area supports that can withstand high temperatures, such as flow-through honeycomb monoliths.
  • the large surface area of these supports promotes the desired heterogeneous reaction, but also causes an increase in exhaust back pressure, i.e., limits the flow of exhaust gases from the engine to the exhaust.
  • High back pressure in the exhaust system reduces engine fuel economy and power output.
  • TWC technology such as those described in U.S. Patent 6,022,825, U.S. Patent No. 9,352,279, U.S. Patent No. 9,040,003, and U.S. Patent Publication No. 2016/0228818, there is still a need for an improved catalytic converter for certain engine platforms that simultaneously produces High conversion rate and low back pressure.
  • the present invention addresses these needs in particular.
  • 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; an inlet catalyst layer starting at the inlet end and extending less than the axial length L, Wherein the inlet catalyst layer comprises an inlet palladium component; an outlet catalyst layer starting at the outlet end and extending less than the axial length L, wherein the outlet catalyst layer comprises an outlet ruthenium component; and wherein the outlet catalyst layer and the inlet catalyst The layers overlap.
  • the 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 a catalyst article having an inlet catalyst layer and an outlet catalyst layer.
  • the inlet catalyst layer is completely directly loaded/deposited on the support.
  • the outlet catalyst layer is partially directly loaded/deposited on the support and partially supported/deposited on top of the inlet catalyst layer.
  • Figure 2 shows a catalyst article having an inlet catalyst layer and an outlet catalyst layer.
  • the outlet catalyst layer is completely directly loaded/deposited on the support.
  • the inlet catalyst layer is partially directly supported/deposited on the support and partially supported/deposited on top of the outlet catalyst layer.
  • Figure 3 shows a comparative commercial catalyst article having two catalyst layers on a support in the same region.
  • This invention relates to the catalytic conversion of combustion exhaust gases such as those produced by gasoline engines or other engines, and to related catalytic articles and systems. More particularly, the present invention relates to purification of NO x, CO and HC while the vehicle exhaust system.
  • the present inventors have discovered a synergistic relationship between some of the catalytically active metals and their orientation, which is unexpectedly high conversion of NO x production, CO and HC, while reducing the exhaust back pressure.
  • the process of the present invention also reduces processing time and 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; an inlet catalyst layer starting at the inlet end and extending less than the axial length L, Wherein the inlet catalyst layer comprises an inlet palladium component; an outlet catalyst layer starting at the outlet end and extending less than the axial length L, wherein the outlet catalyst layer comprises an outlet ruthenium component; and wherein the outlet catalyst layer and the inlet catalyst The layers overlap.
  • the catalyst article of the present invention can be divided into three catalyst zones along the axis of the support: an upstream zone coated only with an inlet catalyst layer, an intermediate zone coated with an inlet and outlet catalyst layer, and a downstream zone coated only with an outlet catalyst layer.
  • An unexpected benefit of the present invention is a lower back pressure compared to conventional TWC catalysts of similar concentration (washcoat loading), as compared to conventional TWC catalysts (even when the conventional TWC has more Improved catalyst performance at high concentrations.
  • the inlet catalyst layer of the catalyst article can extend from 50 to 99% of the axial length L.
  • the inlet catalyst layer may extend from 55 to 95%, 60 to 90%, more preferably from 65 to 85% of the axial length L. (See, for example, Figures 1 and 2)
  • the exit catalyst layer of the catalyst article can extend from 50 to 99% of the axial length L.
  • the outlet catalyst layer may extend from 55 to 95%, 60 to 90%, more preferably from 65 to 85% of the axial length L. (See, for example, Figures 1 and 2)
  • the inlet catalyst layer can be substantially free of PGM metal other than the inlet palladium component.
  • the inlet catalyst layer may contain PGM metal other than the inlet palladium component, for example, platinum and or rhodium.
  • the inlet catalyst layer may comprise up to 300 g/ft 3 of inlet palladium or platinum palladium component.
  • the inlet catalyst layer may comprise from 10 to 200 g/ft 3 , more preferably from 20 to 150 g/ft 3 of the inlet palladium or palladium platinum component, wherein the weight ratio of platinum palladium may be from 60:1 to 1:60, preferably The ground is 30:1-1:30, more preferably 10:1-1:10.
  • the inlet catalyst layer may further comprise an inlet inorganic oxide material, an oxygen storage (OSC) material, an inlet alkali metal or alkaline earth metal component, and/or an inlet inorganic oxide.
  • OSC oxygen storage
  • the total carrier coating loading of the inlet catalyst layer can range from 0.1 to 5 g/in 3 .
  • the total loading of the inlet of the catalyst carrier coating layer is 0.5-3.5g / in 3, and most preferably, the total loading of the inlet of the catalyst carrier coating layer is 1-2.5g / in 3.
  • the inlet OSC material is 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 inlet OSC material comprises a cerium oxide-zirconia mixed oxide.
  • the cerium oxide-zirconia mixed oxide may further contain some dopants such as La, Nd, Y, Pr, and the like.
  • 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 inlet OSC material can act as a carrier material for the inlet palladium component.
  • the inlet OSC material e.g., yttria-zirconia mixed oxide
  • the inlet OSC material may be from 10 to 90% by weight, preferably from 25 to 75% by weight, based on the total carrier coating loading of the inlet catalyst layer. More preferably, it is 35 to 65 wt%.
  • the inlet OSC material loading in the inlet catalyst layer can be less than 1.5 g/in 3 . In some embodiments, the inlet OSC material loading in the inlet catalyst layer is no greater than 1.2 g/in 3 , 1.0 g/in 3 , 0.9 g/in 3 , 0.8 g/in 3 , 0.7 g/in 3 or 0.6 g. /in 3 .
  • an inlet alkali or alkaline earth metal can be deposited on the inlet OSC material.
  • an inlet alkali metal or alkaline earth metal may be deposited on the inlet inorganic oxide. That is, in some embodiments, an inlet alkali or alkaline earth metal can be deposited, ie, present on both the inlet OSC material and the inlet inorganic oxide.
  • the inlet alkali metal or alkaline earth metal is supported/deposited on the inlet inorganic oxide (e.g., alumina). Additionally or alternatively, the inlet alkali metal or alkaline earth metal may be in contact with the inlet OSC material and the inlet palladium component for contact with the inlet inorganic oxide.
  • the inlet inorganic oxide e.g., alumina
  • the inlet alkali metal or alkaline earth metal may be in contact with the inlet OSC material and the inlet palladium component for contact with the inlet inorganic oxide.
  • the inlet alkali metal or alkaline earth metal is preferably ruthenium or osmium.
  • rhenium or rhodium is 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 inlet catalyst layer.
  • hydrazine is present as a BaCO 3 form.
  • Such materials can be obtained by any method known in the art, such as incipient wetness impregnation or spray drying.
  • the inlet inorganic oxide is preferably an oxide of the Group 2, 3, 4, 5, 13 and 14 elements.
  • the inlet inorganic oxide is preferably selected from the group consisting of alumina, cerium oxide, magnesium oxide, silicon dioxide, cerium oxide, cerium, zirconium, hafnium, cerium oxide and mixed oxides or composite oxides thereof.
  • the inlet inorganic oxide is alumina, cerium/alumina composite oxide or magnesia/alumina composite oxide.
  • a particularly preferred inlet inorganic oxide is a cerium/alumina composite oxide or a magnesium oxide/alumina.
  • the inlet inorganic oxide may be a support material for the inlet palladium component and/or for the inlet alkali metal or alkaline earth metal.
  • the preferred inorganic oxide is preferably greater than the inlet 2 / g fresh surface area of 80m, a pore volume 0.1-4mL / g of. Particularly preferably having a surface area greater than 100m 2 / g, high surface area inorganic oxide, such as high surface area alumina.
  • Other preferred inlet inorganic oxides include cerium/alumina composite oxides, optionally further comprising a cerium component such as cerium oxide. In such a case, cerium oxide may be present on the surface of the cerium/alumina composite oxide, for example as a coating.
  • the inlet OSC material and the inlet inorganic oxide may have a weight ratio 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.
  • the inlet OSC material and the inlet 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 to 1:2.
  • the exit catalyst layer may be substantially free of PGM metal other than the outlet rhodium component.
  • the outlet catalyst layer may comprise from 1 to 20 g/ft 3 of an outlet rhodium or platinum rhodium component.
  • the outlet catalyst layer may comprise from 2 to 15 g/ft 3 , more preferably from 3 to 10 g/ft 3 of the outlet rhodium or platinum rhodium component, wherein the platinum rhodium may have a weight ratio of from 20:1 to 1:20, preferably The ground is 15:1-1:15, more preferably 10:1-1:10.
  • the total carrier coating loading of the outlet catalyst layer may range from 0.1 to 3.5 g/in 3 .
  • the total carrier coating loading of the outlet catalyst layer is from 0.5 to 3 g/in 3 , and most preferably, the total carrier coating loading of the outlet catalyst layer is from 0.6 to 2 g/in 3 .
  • the outlet catalyst layer may further comprise an outlet oxygen storage (OSC) material, an outlet alkali metal or alkaline earth metal component, and/or an outlet inorganic oxide.
  • OSC outlet oxygen storage
  • the outlet 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 outlet OSC material comprises a cerium oxide-zirconia mixed oxide.
  • the cerium oxide-zirconia mixed oxide may further contain some doping elements such as ruthenium, osmium, iridium, osmium or the like.
  • 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. Additionally, the exit OSC material can act as a carrier material for the export rhodium component.
  • the outlet OSC material (e.g., loose yttria) may be from 10 to 90 wt%, preferably from 25 to 75 wt%, more preferably from 35 to 65 wt%, based on the total washcoat loading of the outlet catalyst layer.
  • the outlet OSC material loading in the outlet catalyst layer can be less than 1.5 g/in 3 . In some embodiments, the outlet OSC material loading in the outlet catalyst layer is no greater than 1.2 g/in 3 , 1.1 g/in 3 or 1.0 g/in 3 .
  • the alkali metal or alkaline earth metal to be exported is preferably ruthenium or osmium.
  • rhenium or rhodium is 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 outlet catalyst layer.
  • hydrazine is present as a BaCO 3 form.
  • Such materials can be obtained by any method known in the art, such as incipient wetness impregnation or spray drying.
  • the outlet catalyst layer is preferably substantially free of an outlet alkali metal or alkaline earth metal. More preferably, the outlet catalyst layer is substantially free of the outlet alkali metal or alkaline earth metal.
  • the outlet inorganic oxide is preferably an oxide of the Group 2, 3, 4, 5, 13 and 14 elements.
  • the outlet inorganic oxide is preferably selected from the group consisting of alumina, zirconia, magnesia, silica, yttria, cerium, zirconium, hafnium, cerium oxide and mixed oxides or composite oxides thereof.
  • the outlet inorganic oxide is alumina, cerium/alumina composite oxide or magnesia/alumina composite oxide.
  • a particularly preferred outlet inorganic oxide is a cerium/alumina composite oxide or a magnesia/alumina or zirconium/alumina composite oxide.
  • the outlet inorganic oxide may be a carrier material for the export of the rhodium component.
  • the outlet OSC material and the outlet inorganic oxide may have a weight ratio of no greater than 10:1, preferably no greater than 8:1 or 5:1, more preferably no greater than 4:1, and most preferably no greater than 3:1.
  • the outlet OSC material and the outlet 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, most preferably 3:1-1:3 weight ratio.
  • the outlet rhodium component and the inlet palladium component have a weight ratio of from 60:1 to 1:60.
  • the outlet rhodium component and the inlet palladium component have a weight ratio of from 30:1 to 1:30. More preferably, the outlet rhodium component and the inlet palladium component have a weight ratio of from 20:1 to 1:20. Most preferably, the outlet rhodium component and the inlet palladium component have a weight ratio of from 15:1 to 1:15.
  • 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 or a wall-flow gasoline particulate filter. More preferably, the carrier is a flow-through monolith.
  • the carrier length can be less than 100 mm, preferably 50-90 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 unitary carrier has from 100 to 900 channels per square inch, preferably from 300 to 750, in a plane perpendicular to the longitudinal direction.
  • the open first channel and the closed second channel have a density of 300-750 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 carrier material for supporting the catalytic material.
  • Suitable materials for forming the monolithic 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 the manufacture of porous monolith supports 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 together.
  • 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 high temperature resistant material such as alumina, silica, titania, yttria, zirconia, magnesia. , zeolite, silicon nitride, silicon carbide, zirconium silicate, magnesium silicate, aluminosilicate and metal aluminosilicates (such as cordierite and spodumene) or a mixture of any two or more thereof Or mixed oxides. 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 inlet catalyst layer is completely loaded/deposited onto the support.
  • the outlet catalyst layer is partially directly loaded/deposited on the support and partially supported/deposited on top of the inlet catalyst layer. Therefore, the intermediate zone contains both the inlet catalyst layer and the outlet catalyst layer.
  • the outlet catalyst layer is completely directly loaded/deposited on the support.
  • the inlet catalyst layer is partially directly supported/deposited on the support and partially supported/deposited on top of the outlet catalyst layer. Therefore, the intermediate zone contains both the outlet catalyst layer and the inlet catalyst layer.
  • the catalyst is treated contains NO x, CO and HC methods vehicle emissions.
  • a catalytic converter equipped with a TWC made in accordance with the present invention not only exhibits improved or comparable catalyst performance compared to conventional TWC, but also exhibits significant improvements in back pressure (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.
  • 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 a small amount, 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”.
  • loading amount refers to a measurement based on the weight of a metal in g/ft 3 .
  • Catalyst 1 is a commercial ternary (Pd-Rh) catalyst having a two-layer structure (for example as shown in Figure 3).
  • the bottom layer is supported by Pd in a coating consisting of a first CeZr mixed oxide, La stabilized alumina, and Ba promoter.
  • the underlying coating loading was about 2.2 g/in 3 with a Pd loading of 75 g/ft 3 .
  • the upper layer is supported by Rh in a coating composed of a second CeZr mixed oxide, La stabilized alumina.
  • the upper carrier coating loading was about 1.6 g/in 3 with a Rh loading of 5 g/ft 3 .
  • the total washcoat loading of the catalyst is from about 1 3.8g / in 3.
  • Catalyst 2 was prepared in accordance with the present invention.
  • the bottom layer is supported by Pd in a coating consisting of an inlet CeZr mixed oxide, La stabilized alumina, and Ba promoter.
  • the underlying carrier coating loading was about 2.2 g/in 3 with a Pd loading of 75 g/ft 3 .
  • the upper layer is supported by Rh on a coating consisting of an outlet CeZr mixed oxide, La stabilized alumina.
  • the upper carrier coating loading was about 1.6 g/in 3 with a Rh loading of 5 g/ft 3 .
  • the total washcoat loading of catalyst 2 (intermediate region) of about 3.8g / in 3.
  • the final underlayer slurry containing Pd was coated from the inlet face of the same support as Comparative Catalyst 1 using a standard coating procedure with a target coating depth of 80% of the length of the support and dried at 90 °C. Then, using Rh using a standard coating procedure, the upper slurry containing Rh is coated from the exit surface of the support containing the dried underlayer at a target coating depth of 80% of the length of the support, followed by drying at 90 ° C and calcination at 500 ° C for 45 minutes. .
  • Catalyst 3 was prepared in accordance with the present invention.
  • the bottom layer is supported by Pd in a coating consisting of an inlet CeZr mixed oxide, La stabilized alumina, and Ba promoter.
  • the underlying carrier coating loading was about 1.9 g/in 3 with a Pd loading of 75 g/ft 3 .
  • the upper layer is composed of Rh supported on alumina which is stabilized by the outlet CeZr mixed oxide and La.
  • the upper carrier coating loading was about 1.5 g/in 3 with a Rh loading of 5 g/ft 3 .
  • the total carrier coating loading (intermediate zone) of Catalyst 3 was about 3.4 g/in 3 .
  • the final underlayer slurry containing Pd was coated from the inlet face of the same support as Comparative Catalyst 1 using a standard coating procedure with a target coating depth of 80% of the length of the support and dried at 90 °C. Then, using Rh using a standard coating procedure, the upper slurry containing Rh is coated from the exit surface of the support containing the dried underlayer at a target coating depth of 80% of the length of the support, followed by drying at 90 ° C and calcination at 500 ° C for 45 minutes. .
  • Catalyst 4 was prepared in accordance with the present invention.
  • the bottom layer is supported by Pd in a coating consisting of an inlet CeZr mixed oxide, La stabilized alumina, and a Ba adjuvant.
  • the underlying carrier coating loading was about 1.7 g/in 3 with a Pd loading of 75 g/ft 3 .
  • the upper layer is supported by Rh in a coating consisting of an outlet CeZr mixed oxide, La stabilized alumina.
  • the upper carrier coating loading was about 1.3 g/in 3 with a Rh loading of 5 g/ft 3 .
  • the total washcoat loading of catalyst (intermediate region) 4 is about 3.0g / in 3.
  • the final underlayer slurry containing Pd was coated from the inlet face of the same support as Comparative Catalyst 1 using a standard coating procedure with a target coating depth of 80% of the length of the support and dried at 90 °C. Then, using Rh using a standard coating procedure, the upper slurry containing Rh is coated from the exit surface of the support containing the dried underlayer at a target coating depth of 80% of the length of the support, followed by drying at 90 ° C and calcination at 500 ° C for 45 minutes. .
  • Comparative Catalyst 1 and Catalyst 2-4 were subjected to a 200-hour engine bench aging test using a four-case standard aging cycle gantry with a peak temperature of approximately 980 °C. Vehicle emissions are performed on commercial vehicles with a 1.4-liter engine. Emissions were measured before and after the catalyst.
  • Catalyst 4 exhibited comparable or even improved catalyst performance even at a lower total carrier coating loading of about 80% in Comparative Catalyst 1 (see, for example, THC/NMHC emissions related)
  • Comparative Catalyst 1, Catalyst 2 and Catalyst 4 were coated with the same carrier type, number of holes and size, and then their cold flow back pressure was evaluated at air flows of 200, 300, 400 and 600 m 3 /h.
  • Table 2 shows that the percentage of back pressure of Catalyst 1, Catalyst 2 and Catalyst 4 relative to the uncoated support increased.
  • the data indicates that the multi-zone catalyst 4 has a significantly lower contribution to back pressure than the standard two-layer embodiment of Catalyst 1.

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Abstract

一种用于处理废气的催化剂制品及其在用于内燃机的排气系统中的用途。该催化剂制品，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的入口催化剂层，其中该入口催化剂层包含入口钯组分；开始于该出口端并延伸小于该轴向长度L的出口催化剂层，其中该出口催化剂层包含出口铑组分；和其中该出口催化剂层与该入口催化剂层重叠。

Description

用于汽油废气应用的新型三区两层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。用于汽油机应用的常用催化剂是TWC。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还原为N 2。
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整料上。这些载体的大表面积促进所需的非均相反应，但是也会造成排气背压的增高，即限制废气从发动机流到排气管。排气系统中的高背压会降低发动机的燃料经济性和功率输出。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，其同时产生高转化速率和低背压。本发明尤其解决了这些需要。
发明内容
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的入口催化剂层，其中该入口催化剂层包含入口钯组分；开始于该出口端并延伸小于该轴向长度L的出口催化剂层，其中该出口催化剂层包含出口铑组分；和其中该出口催化剂层与该入口催化剂层重叠。
本发明还包括用于内燃机的排气系统，其包含本发明的三元催化剂部件。
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元催化剂部件接触。
附图说明
图1显示了具有入口催化剂层和出口催化剂层的催化剂制品。入口催化剂层完全地直接负载/沉积在载体上。出口催化剂层部分地直接负载/沉积在载体上，并部分地负载/沉积在入口催化剂层的上面。
图2显示了具有入口催化剂层和出口催化剂层的催化剂制品。出口催化剂层完全地直接负载/沉积在载体上。入口催化剂层部分地直接负载/沉积在载体上，并部分地负载/沉积在出口催化剂层的上面。
图3显示了对比的商业催化剂制品，其在同一个区域的载体上具有两个催化剂层。
具体实施方式
本发明涉及燃烧废气如由汽油机或其他发动机产生的废气的催化转化，并涉及相关的催化制品和系统。更具体地，本发明涉及在车辆排气系统中NO x、CO和HC的同时净化。本发明人发现了某些催化活性金属和它们的取向之间的协同关系，其出人意料地产生NO x、CO和HC的高转化率，同时降低排气背压。本发明的方法还减少了处理时间，和降低了催化剂成本。
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的入口催化剂层，其中该入口催化剂层包含入口钯组分；开始于该出口端并延伸小于该轴向长度L的出口催化剂层，其中该出口催化剂层包含出口铑组分；和其中该出口催化剂层与该入口催化剂层重叠。
本发明的催化剂制品可以沿着载体的轴划分为三个催化剂区：仅涂有入口催化剂层的上游区，涂有入口和出口催化剂层的中间区，和仅涂有出口催化剂层的下游区。
本发明人发现，这种包含多种取向的催化剂在提高催化性能和降 低背压方面产生协同效应，这是使用单独的或常规取向的催化剂不能实现。本发明的预料不到的益处是，与类似浓度(载体涂层(washcoat)负载量)的常规TWC催化剂相比更低的背压，和与常规TWC催化剂相比(甚至当该常规TWC具有更高浓度时)改进的催化剂性能。这些益处获得改进的发动机性能，改进的燃料经济性和更低的成本。
催化剂制品的入口催化剂层可以延伸轴向长度L的50-99％。优选地，入口催化剂层可以延伸轴向长度L的55-95％，60-90％，更优选65-85％。(例如参见图1和2)
催化剂制品的出口催化剂层可以延伸轴向长度L的50-99％。优选地，出口催化剂层可以延伸轴向长度L的55-95％，60-90％，更优选65-85％。(例如参见图1和2)
入口催化剂层可以基本上不含入口钯组分之外的PGM金属。
入口催化剂层可以含入口钯组分之外的PGM金属，例如，铂和或铑。入口催化剂层可以包含至多300g/ft 3的入口钯或铂钯组分。优选地，入口催化剂层可以包含10-200g/ft 3，更优选20-150g/ft 3的入口钯或钯铂组分，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。
入口催化剂层可以进一步包含入口无机氧化物材料、储氧(OSC)材料、入口碱金属或碱土金属组分和/或入口无机氧化物。
入口催化剂层的总载体涂层负载量可以为0.1-5g/in 3。优选地，入口催化剂层的总载体涂层负载量是0.5-3.5g/in 3，最优选地，入口催化剂层的总载体涂层负载量是1-2.5g/in 3。
入口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。更优选地，入口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剂，如La、Nd、Y、Pr等。
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。另外，入口OSC材料可以充当入口钯组分的载体材料。
入口OSC材料(例如氧化铈-氧化锆混合氧化物)可以为基于入口 催化剂层的总载体涂层负载量计10-90wt％，优选25-75wt％。更优选35-65wt％。
入口催化剂层中的入口OSC材料负载量可以小于1.5g/in 3。在一些实施方案中，入口催化剂层中的入口OSC材料负载量不大于1.2g/in 3，1.0g/in 3，0.9g/in 3，0.8g/in 3，0.7g/in 3或0.6g/in 3。
在一些实施方案中，入口碱金属或碱土金属可以沉积在入口OSC材料上。替代地或另外地，入口碱金属或碱土金属可以沉积在入口无机氧化物上。即在一些实施方案中，入口碱金属或碱土金属可以沉积在，即存在于入口OSC材料和入口无机氧化物二者上。
优选地，入口碱金属或碱土金属负载/沉积在入口无机氧化物(例如氧化铝)上。对于与入口无机氧化物接触而言另外地或替代地，入口碱金属或碱土金属可以与入口OSC材料还有入口钯组分接触。
入口碱金属或碱土金属优选为钡或锶。优选地，当存在时，钡或锶的存在量为基于入口催化剂层的总重量计0.1-15wt％，更优选3-10wt％的钡含量。
优选地，钡作为BaCO 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。
入口无机氧化物优选为第2、3、4、5、13和14族元素的氧化物。入口无机氧化物优选选自氧化铝、氧化铈、氧化镁、二氧化硅、氧化铌、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，入口无机氧化物为氧化铝、镧/氧化铝复合氧化物或氧化镁/氧化铝复合氧化物。一种尤其优选的入口无机氧化物为镧/氧化铝复合氧化物或氧化镁/氧化铝。入口无机氧化物可以是用于入口钯组分和/或用于入口碱金属或碱土金属的载体材料。
优选的入口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。其他优选的入口无机氧化物包括镧/氧化铝复合氧化物，任选地进一步包含铈组分例如氧化铈。在这样的情况中，氧化铈可以存在于该镧/氧化铝复合氧化物的表面上，例如作为涂层。
入口OSC材料和入口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，入口OSC材料和入口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。
出口催化剂层可以基本上不含出口铑组分之外的PGM金属。
出口催化剂层可以包含1-20g/ft 3的出口铑或铂铑组分。优选地，出口催化剂层可以包含2-15g/ft 3，更优选3-10g/ft 3的出口铑或铂铑组分，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。
出口催化剂层的总载体涂层负载量可以为0.1-3.5g/in 3。优选地，出口催化剂层的总载体涂层负载量为0.5-3g/in 3，最优选地，出口催化剂层的总载体涂层负载量为0.6-2g/in 3。
出口催化剂层可以进一步包含出口储氧(OSC)材料、出口碱金属或碱土金属组分和/或出口无机氧化物。
出口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，出口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、钇等。
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80:20的摩尔比。另外，出口OSC材料可以充当出口铑组分的载体材料。
出口OSC材料(例如松散氧化铈)可以为基于出口催化剂层的总载体涂层负载量计10-90wt％，优选25-75wt％，更优选35-65wt％。
出口催化剂层中的出口OSC材料负载量可以小于1.5g/in 3。在一些实施方案中，出口催化剂层中的出口OSC材料负载量不大于1.2g/in 3，1.1g/in 3或1.0g/in 3。
出口碱金属或碱土金属优选为钡或锶。优选地，当存在时，钡或锶的存在量为基于出口催化剂层的总重量计0.1-15wt％，更优选 3-10wt％的钡含量。
优选地，钡作为BaCO 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。
出口催化剂层优选大体上不含出口碱金属或碱土金属。更优选地，出口催化剂层基本上不含出口碱金属或碱土金属。
出口无机氧化物优选为第2、3、4、5、13和14族元素的氧化物。出口无机氧化物优选选自氧化铝、氧化锆、氧化镁、二氧化硅、氧化铌、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，出口无机氧化物是氧化铝、镧/氧化铝复合氧化物或氧化镁/氧化铝复合氧化物。一种尤其优选的出口无机氧化物是镧/氧化铝复合氧化物或氧化镁/氧化铝或锆/氧化铝复合氧化物。出口无机氧化物可以是用于出口铑组分的载体材料。
出口OSC材料和出口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，最优选不大于3:1的重量比。
替代地，出口OSC材料和出口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，最优选3:1-1:3的重量比。
在一些实施方案中，出口铑组分和入口钯组分具有60:1-1:60的重量比。优选地，出口铑组分和入口钯组分具有30:1-1:30的重量比。更优选地，出口铑组分和入口钯组分具有20:1-1:20的重量比。最优选地，出口铑组分和入口钯组分具有15:1-1:15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，载体是流通式整料或壁流式汽油微粒过滤器。更优选地，载体是流通式整料。
载体长度可以小于100mm，优选为50-90mm。
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，整体式载体具有每平方英寸100-900个通道，优选300-750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300-750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。
整体式载体充当用于支撑催化材料的载体材料。用于形成整体式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料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合在一起或者通过将多个较小的本文所述的载体粘合在一起来形成。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耐高温材料制成，该耐高温材料例如氧化铝、二氧化硅、二氧化钛、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。
如图1中所示，入口催化剂层完全地直接负载/沉积载体上。出口 催化剂层部分地直接负载/沉积在载体上，并部分地负载/沉积在入口催化剂层上面。所以，中间区包含入口催化剂层和出口催化剂层二者。
如图2中所示，出口催化剂层完全地直接负载/沉积在载体上。入口催化剂层部分地直接负载/沉积在载体上，并部分地负载/沉积在出口催化剂层上面。所以，中间区包含出口催化剂层和入口催化剂层二者。
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。装备有根据本发明制造的TWC的催化转化器不仅显示了与常规TWC相比改进的或相当的催化剂性能，而且显示了背压方面显著的改进(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
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剂的量，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1(对比)
催化剂1是具有双层结构(例如如图3中所示)的商业三元(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2.2g/in 3，其中Pd负载量为75g/ft 3。上层由Rh负载在由第二CeZr混合氧化物、La稳定化的氧化铝组成的涂层中。上层的载体涂层负载量为约1.6g/in 3，其中Rh负载量为5g/ft 3。催化剂1的总载体涂层负载量为约3.8g/in 3。
催化剂2
根据本发明来制备催化剂2。底层由Pd负载在由入口CeZr混合氧化物、La稳定化的氧化铝、Ba助剂组成的涂层中。底层的载体涂层负载量为约2.2g/in 3，其中Pd负载量为75g/ft 3。上层由Rh负载在由出口CeZr混合氧化物、La稳定化的氧化铝组成的涂层上。上层的载体涂层负载量为约1.6g/in 3，其中Rh负载量为5g/ft 3。催化剂2的总载体涂层负载量(中间区)为约3.8g/in 3。
使用标准涂覆程序，将含Pd的最终底层浆料从与对比催化剂1相同的载体的入口面涂覆，目标涂覆深度为载体长度的80％，在90℃干燥。然后，使用标准涂覆程序，将含Rh的上层浆料从含有干燥底层的载体的出口面涂覆，目标涂覆深度为载体长度的80％，之后在90℃干燥，在500℃煅烧45分钟。
催化剂3
根据本发明来制备催化剂3。底层由Pd负载在由入口CeZr混合氧化物、La稳定化的氧化铝、Ba助剂组成的涂层中。底层的载体涂层负载量为约1.9g/in 3，其中Pd负载量为75g/ft 3。上层由Rh负载在由出口CeZr混合氧化物、La稳定化的氧化铝组成。上层的载体涂层负载量为约1.5g/in 3，其中Rh负载量为5g/ft 3。催化剂3的总载体涂层负载量(中间区)为约3.4g/in 3。
使用标准涂覆程序，将含Pd的最终底层浆料从与对比催化剂1相同的载体的入口面涂覆，目标涂覆深度为载体长度的80％，在90℃干燥。然后，使用标准涂覆程序，将含Rh的上层浆料从含有干燥底层的载体的出口面涂覆，目标涂覆深度为载体长度的80％，之后在90℃干燥，在500℃煅烧45分钟。
催化剂4
根据本发明来制备催化剂4。底层由Pd负载在由入口CeZr混合氧化物、La稳定化的氧化铝、Ba助剂剂组成的涂层中。底层的载体涂层负载量为约1.7g/in 3，其中Pd负载量为75g/ft 3。上层由Rh负载在由出口CeZr混合氧化物、La稳定化的氧化铝组成的涂层中。上层的载体涂层负载量为约1.3g/in 3，其中Rh负载量为5g/ft 3。催化剂4的总载体涂层负载量(中间区)为约3.0g/in 3。
使用标准涂覆程序，将含Pd的最终底层浆料从与对比催化剂1相同的载体的入口面涂覆，目标涂覆深度为载体长度的80％，在90℃干燥。然后，使用标准涂覆程序，将含Rh的上层浆料从含有干燥底层的载体的出口面涂覆，目标涂覆深度为载体长度的80％，之后在 90℃干燥，在500℃煅烧45分钟。
实验结果
实施例1
将对比催化剂1和催化剂2-4用四工况标准老化循环台架进行200小时的发动机台架老化试验，峰值温度约为980℃。在具有1.4升发动机的商业车辆上进行车辆排放。在催化剂前和后测量排放。
表1 整车稀释袋采尾气排放结果
Figure PCTCN2018119727-appb-000001
如表1中所示，催化剂4甚至以相当于对比催化剂1中的约80％的更低总载体涂层负载量，表现出相当的或者甚至改进的催化剂性能(例如参见与THC/NMHC排放相关的改进性能，当催化剂4与对比催化剂1比较时，从0.047/0.031g/km到0.042/0.026g/km，分别改进11％和16％)。
实施例2
将对比催化剂1、催化剂2和催化剂4以相同的载体类型、孔目数和尺寸进行涂覆，然后在200、300、400和600m 3/h的空气流量评价它们的冷流背压。
表2中显示，催化剂1、催化剂2和催化剂4，相对于未涂覆载体的背压百分比增大。数据指出，多区催化剂4与催化剂1的标准双层实施例相比，对背压具有显著更低的贡献。
表2 催化剂冷流背压测试结果
Figure PCTCN2018119727-appb-000002

Claims (28)

  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的入口催化剂层，其中该入口催化剂层包含入口钯组分；
    开始于该出口端并延伸小于该轴向长度L的出口催化剂层，其中该出口催化剂层包含出口铑组分；和
    其中该出口催化剂层与该入口催化剂层重叠。
  2. 根据权利要求1所述的催化剂制品，其中该入口催化剂层延伸该轴向长度L的50-99％。
  3. 根据权利要求1或2所述的催化剂制品，其中该出口催化剂层延伸该轴向长度L的50-99％。
  4. 根据前述权利要求中任一项所述的催化剂制品，其中该出口催化剂层与该入口催化剂层重叠该轴向长度L的5-90％。
  5. 根据前述权利要求中任一项所述的催化剂制品，其中该出口催化剂层与该入口催化剂层重叠该轴向长度L的40-80％。
  6. 根据前述权利要求中任一项所述的催化剂制品，其中该入口催化剂层基本上不含该入口钯组分之外的PGM金属。
  7. 根据前述权利要求中任一项所述的催化剂制品，其中该入口层包含至多300g/ft 3的该入口钯组分。
  8. 根据前述权利要求中任一项所述的催化剂制品，其中该出口催化剂层基本上不含该出口铑组分之外的PGM金属。
  9. 根据前述权利要求中任一项所述的催化剂制品，其中该出口层包含1-20g/ft 3的该出口铑组分。
  10. 根据前述权利要求中任一项所述的催化剂制品，其中该入口催化剂层进一步包含入口储氧(OSC)材料、入口碱金属或碱土金属组分和/或入口无机氧化物。
  11. 根据权利要求10所述的催化剂制品，其中该入口OSC材料选自氧化铈、氧化锆、氧化铈-氧化锆混合氧化物或氧化铝-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，其中该入口OSC材料包含氧化铈-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，其中该入口钯组分负载在该入口无机氧化物上。
  14. 根据权利要求10-13中任一项所述的催化剂制品，其中该入口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。
  15. 根据权利要求14所述的催化剂制品，其中该入口无机氧化物为氧化铝、镧/氧化铝复合氧化物或氧化镁/氧化铝复合氧化物。
  16. 根据权利要求10-15中任一项所述的催化剂制品，其中该入口碱金属或碱土金属为钡或锶。
  17. 根据权利要求16所述的催化剂制品，其中该入口催化剂层中钡或锶的存在量为基于该入口催化剂层的总重量计0.1-15wt％。
  18. 根据前述权利要求中任一项所述的催化剂制品，其中该出口催化剂层进一步包含出口储氧(OSC)材料和/或出口无机氧化物。
  19. 根据权利要求18所述的催化剂制品，其中该出口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。
  20. 根据权利要求19所述的催化剂制品，其中该出口OSC材料包括氧化铈-氧化锆混合氧化物。
  21. 根据权利要求18-20中任一项所述的催化剂制品，其中该出口无机氧化物选自氧化铝，氧化锆，氧化镁，二氧化硅，镧、钇、钕、镨氧化物及其混合氧化物或复合氧化物。
  22. 根据权利要求21所述的催化剂制品，其中该出口无机氧化物为氧化铝、镧/氧化铝复合氧化物或氧化镁/氧化铝复合氧化物。
  23. 根据前述权利要求中任一项所述的催化剂制品，其中该载体是流通式整料或壁流式过滤器。
  24. 根据前述权利要求中任一项所述的催化剂制品，其中该载体长度小于100mm。
  25. 根据前述权利要求中任一项所述的催化剂制品，其中该入口催化剂层直接负载/沉积在该载体上。
  26. 根据权利要求1-25中任一项所述的催化剂制品，其中该出口催化剂层直接负载/沉积在该载体上。
  27. 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 1-26中任一项所述的催化剂制品。
  28. 处理内燃机废气的方法，其包括使该废气与根据权利要求1-26中任一项所述的催化剂制品接触。
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