Oxidation catalysts containing platinum group metals and base metal oxides

Abstract

This disclosure relates to oxidation catalyst compositions comprising a platinum group metal (PGM) component comprising palladium, platinum, or a combination thereof; a manganese component; and a first refractory metal oxide support material comprising zirconium oxide; a catalyst article; and an exhaust gas treatment system, as well as methods for preparing and using such oxidation catalyst compositions, for example, for reducing formaldehyde levels in engine exhaust emissions.

Description

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 071,584, filed August 28, 2020, the contents of which are incorporated herein by reference in their entirety.

[0002] This disclosure relates to catalyst compositions suitable for treating exhaust gases from internal combustion engines, such as diesel engines, as well as catalytic articles and systems comprising such compositions and methods of using them.

[0003] Environmental regulations governing emissions from internal combustion engines are becoming increasingly stringent worldwide. Lean-burn engines, such as diesel engines, offer excellent fuel economy due to their operation under lean-fuel conditions with a high air / fuel ratio. However, diesel engines also emit particulate matter (PM), unburned hydrocarbons (HC) and oxygenated hydrocarbon derivatives (e.g., formaldehyde), carbon monoxide (CO), and nitrogen oxides (NOx). x The exhaust emissions of NO x This describes various chemical substances of nitrogen oxides, including nitric oxide and nitrogen dioxide. The two main components of particulate matter in exhaust gases are the soluble organic fraction (SOF) and the insoluble carbonaceous soot fraction. SOF condenses on the soot in the form of a layer and typically originates from unburned diesel fuel and lubricating oil. SOF can exist in diesel exhaust gases as vapor or aerosols (i.e., fine droplets of liquid condensate), depending on the exhaust gas temperature. The soot is primarily composed of carbon particles.

[0004] Oxidation catalysts comprising one or more platinum group metals (PGMs) dispersed on a refractory metal oxide support such as alumina are known for treating diesel engine exhaust gases to convert pollutants by catalytically oxidizing hydrocarbons, oxygenated hydrocarbon derivatives, and carbon monoxide gaseous pollutants to carbon dioxide and water. Such catalysts are typically contained in a unit called a diesel oxidation catalyst (D°C), which is placed in the exhaust gas flow path from the diesel engine to treat the exhaust gases before they are released into the atmosphere. Typically, diesel oxidation catalysts are formed on a ceramic or metal substrate on which one or more catalyst coating compositions are deposited. In addition to converting gaseous HC and CO emissions and particulate matter (SOF portion), oxidation catalysts containing one or more PGMs also promote the oxidation of NO to NO2. Catalysts are typically categorized by their ignition temperature or the temperature at which 50% conversion is achieved (also known as T). 50 Defined by ).

[0005] As regulations concerning vehicle emissions become more stringent, emissions control during cold starts is becoming increasingly important. While a variety of harmful exhaust components need to be considered, given the increasingly stringent regulations, NO... xIt has received particular attention. For the 2024 model year, NO... x Heavy-duty diesel vehicle emission regulations require tailpipe NO x Less than or equal to 0.1 g / HP-Hr. Furthermore, the 2024 model year emissions regulations further require vehicles to meet formaldehyde emission standards.

[0006] Various treatment methods have been used to treat NO-containing substances. x The waste gas mixture is treated to reduce air pollution. One type of treatment involves a selective catalytic reduction (SCR) process, in which ammonia or ammonia precursors are used as a reducing agent. In the selective reduction process, a high degree of nitrogen oxide removal can be achieved by using a stoichiometric amount of reducing agent, resulting in the formation of nitrogen gas and vapor.

[0007] Furthermore, stricter regulations are being implemented regarding formaldehyde emissions from bus and commercial vehicle engine exhaust. Manganese dioxide (MnO2) is known to be reactive against formaldehyde under ambient conditions, but it does not exhibit the thermal stability required in typical engine exhaust environments. Phase transitions at high temperatures (e.g., 800°C) cause structural collapse in MnO2, resulting in such low surface area and pore volume that catalytic ineffectiveness. The high-temperature stability of manganese oxides (and other catalytically useful base metal oxides such as copper oxides, cerium dioxide, and iron oxides) can be improved by loading them onto refractory oxide materials that are themselves highly stable when exposed to high temperatures in engine exhaust. Materials such as alumina and zirconium oxide are useful in this regard.

[0008] Furthermore, catalysts used to treat internal combustion engine exhaust gases perform poorly during relatively low-temperature operation, such as the initial cold start of engine operation, because the exhaust gas temperature is not high enough for effective catalytic conversion of harmful components in the exhaust gas (i.e., below 200°C). At these low temperatures, exhaust gas treatment systems typically do not demonstrate sufficient effectiveness in treating hydrocarbons (HC), oxygenated hydrocarbon derivatives (e.g., HCHO), and nitrogen oxides (NOx). x Catalytic activity for NO and / or carbon monoxide (CO) emissions. Typically, catalytic components such as SCR catalyst components are very effective at temperatures above 200°C in removing NO. x It is converted to N2, but does not exhibit sufficient activity in the lower temperature range (<200°C), such as the activity found during cold starts or prolonged low-speed city driving. During initial engine start-up, i.e., the first 400 seconds of operation, the exhaust gas temperature at the SCR inlet is below 170°C, at which temperature the SCR has not yet fully functioned. Therefore, nearly 70% of the system output NO... x Emissions occur during the first 500 seconds of engine operation.

[0009] Currently, there is a disconnect between D℃ and SCR performance during cold start (i.e., NO before SCR takes effect). x (Conversion performance), because D℃ operates at temperatures lower than SCR. One way to address this disconnect is by enhancing the NO2 / NO ratio of D℃ at temperatures below 250°C. x To improve SCR performance at the low-temperature end of the spectrum, this study explored methods to address these issues by using Mn-doped alumina to stabilize Pt, thereby generating a favorable NO2 / NO2 / NO2 ratio. x Performance. See, for example, U.S. Patent Application Publications US2015 / 0165422 and US2015 / 0165423 granted to BASF, both of which are incorporated herein by reference. However, while the Mn-doped alumina / Pt catalysts disclosed therein provide stable NO2 / NO x Performance, but it does not provide the enhanced low-temperature NO2 / NO2 / NO2 ratio required for downstream SCR catalysts. x Performance. Therefore, there is a need in the art for catalyst compositions that enhance the performance of D℃+SCR systems during low-temperature operation and effectively oxidize formaldehyde during low-temperature operation.

[0010] This disclosure provides, in general, oxidation catalyst compositions with enhanced hydrocarbon conversion and NO2 formation compared to conventional oxidation catalysts. Surprisingly, it has been found that, in certain embodiments of this disclosure, oxidation catalyst compositions comprising platinum group metals (including palladium) (PGM), certain base metal oxides, and refractory metal oxides (including zirconium oxide) support materials promote NO2 formation, exhibit enhanced hydrocarbon conversion (HC), and oxidize oxygen-containing hydrocarbon derivatives (such as formaldehyde) at temperatures comparable to those at which carbon monoxide (CO) is oxidized. In particular, it has been found that adding manganese to a lanthanum oxide-doped zirconium oxide support is beneficial for HC conversion and NO2 yield. Additionally and surprisingly, while the addition of copper to a Mn / La-Zr support leads to increased CO conversion, HC conversion, and NO2 yield, this is influenced by the amount of copper added.

[0011] Therefore, in a first aspect, an oxidation catalyst composition is provided for use in an exhaust gas treatment system comprising a compression ignition internal combustion engine, the composition comprising a platinum group metal (PGM) component comprising palladium, platinum, or a combination thereof; a manganese component; and a first refractory metal oxide support material comprising zirconium oxide.

[0012] In some embodiments, the oxidation catalyst composition comprises manganese in an amount of about 1% to about 40% by weight of the oxide based on the weight of the first refractory metal oxide support material.

[0013] In some embodiments, the first refractory metal oxide support material comprises about 5% to about 99% by weight of zirconium oxide based on the weight of the first refractory metal oxide support material. In some embodiments, the first refractory metal oxide support material comprises about 20% to about 99% by weight of zirconium oxide based on the weight of the first refractory metal oxide support material.

[0014] In some embodiments, the zirconium oxide is doped with lanthanum in an amount of about 1% to about 40% by weight of the oxide, based on the weight of the zirconium oxide.

[0015] In some embodiments, the oxidation catalyst composition further comprises a base metal oxide, wherein the base metal of the base metal oxide is selected from (e.g., selected from the group consisting of) cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, copper, and combinations thereof. In some embodiments, the base metal is selected from (e.g., selected from the group consisting of) cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, and combinations thereof. In some embodiments, the base metal oxide is cerium dioxide, wherein the cerium dioxide is present in an amount of up to about 50% by weight based on the weight of the first refractory metal oxide support material.

[0016] In some embodiments, the oxidation catalyst composition comprises manganese in an amount of about 1 wt% to about 30 wt%, or about 5 wt% to about 20 wt% based on the weight of the first refractory metal oxide support material; and cerium dioxide in an amount of about 1 wt% to about 30 wt%, about 1 wt% to about 20 wt%, or about 1 wt% to about 10 wt% based on the weight of the first refractory metal oxide support material.

[0017] In some embodiments, palladium is loaded on the first refractory metal oxide support in an amount of 0% to 10% by weight based on the weight of the first refractory metal oxide support; platinum is loaded on the first refractory metal oxide support in an amount of 0% to 10% by weight based on the weight of the first refractory metal oxide support; and at least one of the platinum or the palladium is present in an amount of about 0.1% by weight or more based on the weight of the first refractory metal oxide support.

[0018] In some embodiments, the PGM component comprises palladium and platinum. In some embodiments, the weight ratio of palladium to platinum is from about 100 to about 0.01 (e.g., from about 100 to about 0.05). In some embodiments, the weight ratio of palladium to platinum is from about 1 to about 0.01, from about 1 to about 0.05, or from about 0.5 to about 0.1.

[0019] In some implementations, the PGM component is essentially composed of palladium.

[0020] In some implementations, the PGM component is essentially composed of platinum.

[0021] In some embodiments, the oxidation catalyst composition further comprises a second refractory metal oxide support material. In some embodiments, the second refractory metal oxide support material comprises alumina, silica, zirconium oxide, titanium dioxide, cerium dioxide, or combinations thereof. In some embodiments, the second refractory metal oxide support material comprises alumina. In some embodiments, the second refractory metal oxide support material comprises zirconium oxide. In some embodiments, the zirconium oxide is doped with lanthanum in an amount of about 1% to about 40% by weight of the oxide, based on the weight of the zirconium oxide.

[0022] In some embodiments, the manganese component is loaded on the first refractory metal oxide support material, and the PGM component is loaded on the second refractory metal oxide support material.

[0023] In some embodiments, the PGM component is loaded onto the second refractory metal oxide support material in an amount of about 0.5% to about 10% by weight based on the weight of the second refractory metal oxide support material.

[0024] In some embodiments, the manganese component is a manganese oxide supported on the first refractory metal oxide carrier material, the amount of which is from about 1 wt% to about 40 wt% based on the weight of the first refractory metal oxide, wherein the first refractory metal oxide carrier material comprises zirconium oxide; and the PGM component is supported on a second refractory metal oxide carrier material, wherein the second refractory metal oxide carrier material is selected from (e.g., selected from the group consisting of) alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and lanthanum oxide-doped zirconium oxide, the amount of which is from about 1 wt% to about 40 wt% based on the weight of the zirconium oxide.

[0025] In some embodiments, the zirconium oxide is doped with about 1% to about 40% lanthanum oxide based on the weight of the zirconium oxide.

[0026] In some embodiments, the first refractory metal oxide support material further comprises about 1% to about 50% by weight of cerium dioxide based on the weight of the first refractory metal oxide support material.

[0027] In some embodiments, the oxidation catalyst composition is essentially copper-free.

[0028] In another aspect, a catalytic article is provided, the catalytic article comprising an inlet end and an outlet end having a defined total length, and a catalytic coating disposed on at least a portion of the substrate, the catalytic coating comprising a first carrier coating and a second carrier coating, wherein the first carrier coating comprises a manganese component and a first refractory metal oxide carrier material, the first refractory metal oxide carrier material comprising zirconium oxide, wherein the manganese component is supported on the first refractory metal oxide carrier material as a manganese oxide or a mixed oxide; and the second carrier coating comprises a platinum group metal (PGM) component and a second refractory metal oxide carrier material, the platinum group metal component comprising palladium, platinum, or a combination thereof, wherein the PGM component is supported on the second refractory metal oxide carrier material.

[0029] In some embodiments, the catalyst comprises manganese in an amount of about 1% to about 40% by weight of the oxide based on the weight of the first refractory metal oxide support material.

[0030] In some embodiments, the catalyst further comprises a base metal oxide supported on the first refractory metal oxide support material, said base metal being selected (e.g., from the group consisting of) cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, copper, and combinations thereof. In some embodiments, the base metal is selected (e.g., from the group consisting of) cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, and combinations thereof.

[0031] In some embodiments, the base metal oxide is cerium dioxide, wherein the cerium dioxide is present in an amount of up to about 30% by weight based on the weight of the first refractory metal oxide carrier material.

[0032] In some embodiments, the catalyst comprises manganese in an amount of about 1% to about 30% by weight, or about 5% to about 20% by weight, based on the weight of the first refractory metal oxide support material; and cerium dioxide in an amount of about 1% to about 30% by weight, about 1% to about 20% by weight, or about 1% to about 10% by weight, based on the weight of the first refractory metal oxide support material.

[0033] In some embodiments, the zirconium oxide is doped with about 1% to about 40% lanthanum oxide based on the total weight of the zirconium oxide.

[0034] In some embodiments, the second refractory metal oxide support material comprises alumina, silica, zirconium oxide, titanium dioxide, cerium dioxide, or combinations thereof. In some embodiments, the second refractory metal oxide support material comprises alumina. In some embodiments, the second refractory metal oxide support material comprises zirconium oxide. In some embodiments, the zirconium oxide is doped with about 1% to about 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide. In some embodiments, the second refractory metal oxide support material is selected from (e.g., selected from the group consisting of) alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and zirconium oxide doped with lanthanum oxide, wherein the amount of lanthanum oxide is about 1% to about 40% by weight based on the weight of the zirconium oxide.

[0035] In some embodiments, the PGM component comprises a combination of platinum and palladium. In some embodiments, the weight ratio of palladium to platinum is from about 100 to about 0.01 (e.g., from about 100 to about 0.05). In some embodiments, the weight ratio of palladium to platinum is from about 1 to about 0.01, from about 1 to about 0.05, or from about 0.5 to about 0.1.

[0036] In some implementations, the PGM component is essentially composed of palladium.

[0037] In some implementations, the PGM component is essentially composed of platinum.

[0038] In some embodiments, the total PGM component supported on the catalyst is about 5 g / ft. 3 Approximately 200g / ft 3 .

[0039] In some embodiments, PGM is loaded onto the second refractory metal oxide support material in an amount of about 0.5% to about 5% by weight based on the weight of the second refractory metal oxide support material.

[0040] In some embodiments, the manganese component is a manganese oxide supported on the first refractory metal oxide carrier material, the amount of which is from about 1 wt% to about 30 wt% based on the weight of the first refractory metal oxide, wherein the first refractory metal oxide carrier material comprises alumina or zirconium oxide doped with lanthanum oxide, the amount of which is from about 1 wt% to about 40% based on the weight of the zirconium oxide; the first refractory metal oxide carrier material further comprises cerium dioxide, the amount of which is from about 1 wt% to about 50 wt% based on the weight of the first refractory metal oxide carrier material; and the PGM component is supported on the second refractory metal oxide carrier material, wherein the second refractory metal oxide carrier material is selected (e.g., selected from the group consisting of) alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and lanthanum oxide doped zirconium oxide, the amount of which is from about 1 wt% to about 40 wt% based on the weight of the zirconium oxide.

[0041] In some implementations, the first carrier coating and the second carrier coating are substantially copper-free.

[0042] In some embodiments, a first carrier coating is disposed directly on the substrate, and a second carrier coating is disposed on at least a portion of the first carrier coating. In some embodiments, a second carrier coating is disposed directly on the substrate, and a first carrier coating is disposed on at least a portion of the second carrier coating. In some embodiments, the catalyst article has a partitioned configuration, wherein the first carrier coating is disposed directly on the substrate from the outlet end to a length of approximately 20% to approximately 100% of the total length; and the second carrier coating is disposed on the substrate from the inlet end to a length of approximately 20% to approximately 100% of the total length. In some embodiments, the catalyst article has a partitioned configuration, wherein the second carrier coating is disposed directly on the substrate from the outlet end to a length of approximately 20% to approximately 100% of the total length; and the first carrier coating is disposed on the substrate from the inlet end to a length of approximately 20% to approximately 100% of the total length.

[0043] In another aspect, an exhaust gas treatment system is provided, the exhaust gas treatment system including a catalyst as disclosed herein, wherein the catalyst is downstream of and in fluid communication with a compression ignition internal combustion engine.

[0044] In another aspect, a method for treating an exhaust gas stream containing hydrocarbons and / or carbon monoxide and / or NO is provided. xThe method includes contacting the waste gas stream with the catalyst or the waste gas treatment system, each as disclosed herein.

[0045] These and other features, aspects, and advantages of this disclosure will become apparent from the following detailed description and the accompanying drawings, which are briefly described below. This disclosure includes any combination of two, three, four, or more of the above embodiments, and any combination of two, three, four, or more features or elements set forth in this disclosure, regardless of whether such features or elements are expressly combined in the specific embodiments described herein. This disclosure is intended to be understood holistically such that, unless the context clearly indicates otherwise, any separable features or elements of the disclosed subject matter in any aspect and embodiment of this disclosure shall be considered composable. Other aspects and advantages of this disclosure will become apparent from the following description. Attached Figure Description

[0046] To provide an understanding of certain embodiments of this disclosure, reference is made to the accompanying drawings, wherein reference numerals indicate components of exemplary embodiments of this disclosure. The drawings are exemplary only and should not be construed as limiting the scope of this disclosure. The disclosure described herein is illustrated in the drawings by way of example, not limitation. For simplicity and clarity of illustration, features shown in the drawings are not necessarily drawn to scale. For example, the dimensions of some features may be enlarged relative to other features for clarity. Furthermore, reference numerals have been repeated in the drawings where deemed appropriate to indicate corresponding or similar elements.

[0047] Figure 1A It may include a perspective view of a honeycomb substrate comprising an oxidation catalyst composition according to the present disclosure.

[0048] Figure 1B It is relative to Figure 1A Magnify and along parallel Figure 1A A partial cross-sectional view of the end face of the substrate, showing an embodiment in which the substrate is a flow-through substrate. Figure 1A An enlarged view of the multiple airflow channels shown.

[0049] Figure 2 This is a cross-sectional view of a representative wall-flow filter.

[0050] Figure 3A , 3B The diagrams for 3C are non-limiting illustrations of possible coating configurations.

[0051] Figure 4 This is a schematic diagram of an embodiment of an emission treatment system using the D℃ catalyst product disclosed herein.

[0052] Figure 5 This is a depiction of the compositional load of a test article according to certain embodiments of the present disclosure.

[0053] Figure 6 This describes the % NO2 / NO2 ratio for Pt / Pd catalysts containing 5% Mn supported on various supports. x A graph showing the relationship between temperature and inlet temperature.

[0054] Figure 7 This describes the % NO2 / NO2 ratio for Pt / Pd catalysts containing 25% Mn supported on various supports. x A graph showing the relationship between temperature and inlet temperature.

[0055] Figure 8 This describes the NO2 / NO2 ratio of aged Pt / Pd(2 / 1) powder samples (9% La, loaded on Zr (reference); 10% Y, loaded on Zr) at 300 °C and 250 °C. x A graph of yield.

[0056] Figure 9 This describes the NO2 / NO2 ratio of aged Pt / Pd(2 / 1) powder samples (9% La, loaded on Zr (reference); 10% Si / ZrO2) at 300 °C and 250 °C. x A graph of yield.

[0057] Figure 10 This describes the NO2 / NO2 ratio of an aged Pt / Pd(2 / 1) powder sample (9% La, loaded on Zr (reference); Zr75 / Mn24) at 300°C and 250°C. x A graph of yield.

[0058] Figure 11 This describes the NO2 / NO2 ratio of aged Pt / Pd(2 / 1) powder samples (9% La, supported on Zr (reference); 10% Si, supported on Ti) at 300 °C and 250 °C. x A graph of yield.

[0059] Figure 12 This describes the NO2 / NO2 ratio of aged Pt / Pd(2 / 1) powder samples (9% La, supported on Zr (reference); 5% Si, supported on Al) at 300 °C and 250 °C. x A graph of yield.

[0060] In some embodiments, this disclosure provides an oxidation catalyst composition for use in an exhaust gas treatment system comprising a compression-ignition internal combustion engine. The composition comprises a platinum group metal (PGM) component including palladium; a manganese component; and a first refractory metal oxide support material comprising zirconium oxide. Surprisingly, it has been found that adding manganese to a lanthanum oxide-doped zirconium oxide support is beneficial for HC conversion and NO2 yield. Surprisingly, while further addition of copper to the Mn / La-Zr support leads to increased CO conversion, this addition negatively impacts HC conversion and NO2 yield.

[0061] The subject matter disclosed herein will now be described more fully below. However, the disclosed subject matter may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art.

[0062] definition

[0063] As used herein, the articles “a” and “an” refer to one or more grammatical objects (e.g., at least one). Any ranges listed herein include end values. The term “about” as used throughout the text is used to describe and explain small fluctuations. For example, “about” may indicate that a value can be modified by ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%, ±0.3%, ±0.2%, ±0.1%, or ±0.05%. All numerical values ​​are modified by the term “about”, whether explicitly stated or not. Numerical values ​​modified by the term “about” include specific identifying values. For example, “about 5.0” includes 5.0.

[0064] As used in this article, the term “mitigation” means a reduction in quantity caused by any means.

[0065] As used herein, the term "associated" means, for example, "equipped with," "connected to," or "in communication with," such as "electrically connected" or "fluidly connected" or connected in a manner that performs a function. As used herein, the term "associated" can mean, for example, directly or indirectly associated with, for example, through one or more other articles or elements.

[0066] As used in this article, "average grain size" and D 50 Synonymous, this means that half of the particle size in a particle group is above this point, and the other half is below this point. Particle size refers to the primary particle size. Particle size can be measured using laser scattering techniques, with dispersions or dry powders, for example, according to ASTM method D4464.90 Particle size distribution indicates that 90% of the particles (by number) have a Feret diameter smaller than that of submicron particles, as measured by scanning electron microscopy (SEM) or transmission electron microscopy (TEM); and that particles containing carriers (micron-sized) have a size measured by a particle size analyzer.

[0067] As used herein, the term "catalyst" refers to a material that facilitates a chemical reaction. Catalysts include the "catalytically active material" and the "support" that carries or loads the active material.

[0068] As used herein, the term “functional article” means an article comprising a substrate having a functional coating composition disposed thereon, specifically a catalyst and / or adsorbent coating composition.

[0069] As used herein, the term "catalytic article" means an article comprising a substrate having a catalyst-coated composition.

[0070] As used herein, "CSF" refers to a catalytic flue gas filter, which is a wall-flow filter. A wall-flow filter consists of alternating inlet and outlet channels, with the inlet channel clogging at the outlet end and the outlet channel clogging at the inlet end. Flue gas carrying particulate matter entering the inlet channel is forced through the filter wall before exiting the outlet channel. In addition to flue gas filtration and regeneration, the CSF can carry an oxidation catalyst to oxidize CO and HC to CO2 and H2O, or oxidize NO to NO2, thereby accelerating downstream SCR catalysis or promoting the oxidation of particulate matter at lower temperatures. When positioned downstream of an LNT catalyst, the CSF can also function to suppress the oxidation of H2S emissions during the LNT desulfurization process. In some embodiments, the SCR catalyst can also be directly coated onto a wall-flow filter called an SCRofer (SCRoF).

[0071] As used herein, “D℃” refers to a diesel oxidation catalyst that converts hydrocarbons and carbon monoxide in the exhaust gases of a diesel engine. In some embodiments, D℃ comprises one or more platinum group metals (such as palladium and / or platinum) and a refractory metal oxide support material.

[0072] As used in this article, "LNT" refers to rare NO. x The trap, which contains platinum group metals, cerium dioxide, and alkaline earth trapping materials, is suitable for adsorbing NO under lean-burn conditions. x Catalysts (e.g., BaO or MgO). Under enrichment conditions, NO is released. x And then reduce it to nitrogen gas.

[0073] As used herein, the phrase "catalyst system" refers to a combination of two or more catalysts, for example, an existing oxidation catalyst and another catalyst (e.g., dilute NO). x A combination of a lump-filled nitrogen (LNT), a catalytic flue filter (CSF), or a selective catalytic reduction (SCR) catalyst. The catalyst system may alternatively be in the form of a support coating, wherein the two or more catalysts are mixed together or coated in separate layers.

[0074] The term "configured" as used in the specification and claims is intended to be an open-ended term such as "comprising" or "containing". The term "configured" does not imply the exclusion of other possible articles of manufacture or elements. The term "configured" may be equivalent to "adapted".

[0075] Typically, the term "effective" means, for example, about 35% to 100% by weight or molar, relative to the defined catalytic activity or storage / release activity, such as about 40%, about 45%, about 50%, or about 55% to about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95%.

[0076] As used herein, “substantially free” means “rare or none” or “no intentional addition”, and also only in trace and / or unintentional amounts. For example, in some embodiments, “substantially free” means less than 2% by weight (wt%), less than 1.5% by weight, less than 1.0% by weight, less than 0.5% by weight, less than 0.25% by weight, or less than 0.01% by weight based on the indicated total composition.

[0077] As used herein, the term "exhaust stream" or "exhaust gas stream" refers to any combination of flowing gases that may contain solid or liquid particulate matter. A stream contains gaseous components and, for example, the exhaust gas from a lean-burn engine, may contain certain non-gaseous components such as droplets, solid particles, etc. The exhaust stream from an internal combustion engine typically also contains combustion products (CO2 and H2O), incomplete combustion products (carbon monoxide (CO) and hydrocarbons (HC)), and nitrogen oxides (NOx). xCombustible materials and / or carbonaceous particulate matter (smoke), as well as unreacted oxygen and nitrogen. As used herein, the terms “upstream” and “downstream” refer to the relative directions of flow of engine exhaust gas from the engine to the tailpipe, where the engine is located upstream and the tailpipe and any contaminant mitigation products such as filters and catalysts are located downstream of the engine. The inlet end of the substrate is synonymous with the “upstream” end or “front” end. The outlet end is synonymous with the “downstream” end or “rear” end. The upstream zone is upstream of the downstream zone. The upstream zone can be closer to the engine or manifold, while the downstream zone can be further away from the engine or manifold.

[0078] The term "fluidly connected" is used to refer to articles located on the same exhaust line, that is, articles through which a common exhaust gas flows. Fluidly connected articles may be adjacent to each other in the exhaust line. Alternatively, fluidly connected articles may be separated by one or more articles, also referred to as "carrier-coated monolithic materials".

[0079] As used herein, the term "nitrogen oxides" or "NO" refers to... x "Refers to oxides of nitrogen, such as NO or NO2."

[0080] As used in this article, "impregnated" or "impregnated" refers to the catalytic material penetrating into the porous structure of the carrier material.

[0081] As used herein, the term “support” or “support material” refers to any high surface area material, typically a metal oxide material, on which a catalytic noble metal is applied. The term “on a support” means “dispersed on,” “bonded into,” “impregnated into,” “on,” “in,” “deposited on,” or otherwise associated with it.

[0082] As used herein, the term “selective catalytic reduction” (SCR) refers to a catalytic process that uses a nitrogen-containing reducing agent to reduce nitrogen oxides to nitrogen ions (N2).

[0083] As used herein, the term "substrate" refers to an integral material on which a catalyst composition (i.e., a catalyst coating) is typically disposed in the form of a carrier coating. In some embodiments, the substrate is a flow-through monolithic filter and a monolithic wall-flow filter. For example, flow-through substrates and wall-flow substrates are taught in International Application Publication No. WO2016 / 070090, which is incorporated herein by reference. The carrier coating is formed by preparing a slurry containing a specific solids content (e.g., 30-90% by weight) of catalyst in a liquid, then coating the slurry onto the substrate and drying it to provide a carrier coating layer. The reference to "monolithic substrate" refers to a uniform and continuous monolithic structure from inlet to outlet. The carrier coating is formed by preparing a slurry containing a certain solids content (e.g., 20%-90% by weight) of particles in a liquid medium, then coating the slurry onto the substrate and drying it to provide a carrier coating layer.

[0084] The terms “on” and “on top of” regarding coatings are used synonymously herein. The term “directly on” means direct contact. In some embodiments, the disclosed article of manufacture is referred to as being contained “on” a second coating, and such language is intended to cover embodiments with an intermediate layer where direct contact between coatings is not required (i.e., “on” is not equivalent to “directly on”).

[0085] As used herein, the term "vehicle" means, for example, any vehicle having an internal combustion engine, and includes, but is not limited to, passenger cars, sports utility vehicles, minivans, vans, trucks, buses, garbage trucks, freight trucks, engineering vehicles, heavy equipment, military vehicles, agricultural vehicles, etc.

[0086] As used herein, the term "carrier coating" generally means in the art a thin, adhesive coating of catalytic material or other material applied to a substrate material (such as a honeycomb carrier component) that is sufficiently porous to allow the flow of the treated gas stream. The carrier coating may optionally include a binder selected from silica, alumina, titanium dioxide, zirconium oxide, cerium dioxide, or combinations thereof. The binder loading is approximately 0.1% to 10% by weight of the carrier coating. As used herein and as described in Heck, Ronald, and Farrauto, Robert, Catalytic Air Pollution Control (New York: Wiley-Interscience, 2002, pp. 18-19), a carrier coating layer comprises layers of materials with different compositions disposed on a monolithic substrate or an underlying carrier coating layer. The substrate may contain one or more carrier coating layers, and each carrier coating layer may differ in some way (e.g., in its physical properties, such as particle size or microcrystalline phase) and / or in its chemocatalytic function.

[0087] Unless otherwise indicated, all parts and percentages are by weight. Unless otherwise stated, “weight percentage (wt%)” is based on the whole composition excluding any volatiles, that is, on the dry solids content.

[0088] Unless otherwise stated herein or clearly contradicted by the context, all methods described herein may be performed in any suitable order. The use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better illustrate the materials and methods and does not limit the scope unless otherwise claimed. The language in this specification should not be construed as indicating that any unclaimed element is necessary for the practice of the materials and methods of this disclosure.

[0089] All U.S. patent applications, published patent applications, and patents cited in this article are incorporated herein by reference.

[0090] Non-restrictive example implementation scheme 1 :

[0091] In a non-limiting manner, some non-limiting embodiments of this disclosure include:

[0092] 1. An oxidation catalyst composition, said oxidation catalyst composition comprising:

[0093] Platinum group metals (PGM) composition, which includes palladium, platinum, or combinations thereof;

[0094] Manganese component; and

[0095] The first refractory metal oxide carrier material contains zirconium oxide.

[0096] 2. The oxidation catalyst composition as described in Embodiment 1 comprises manganese in an amount of about 0.1 wt% to about 90 wt% (e.g., about 1 wt% to about 90 wt%; about 1 wt% to about 40 wt%) based on the weight of the first refractory metal oxide support material.

[0097] 3. The oxidation catalyst composition as described in Embodiment 1 or Embodiment 2, wherein the manganese component is deposited on the first refractory metal oxide support material.

[0098] 4. The oxidation catalyst composition of any one of embodiments 1 to 3, wherein the first refractory metal oxide support material comprises about 1% to about 99% by weight (e.g., about 5% to about 99% by weight) of zirconium oxide.

[0099] 5. The oxidation catalyst composition as described in any one of embodiments 1 to 4, wherein the first refractory metal oxide support material further comprises alumina, silicon dioxide, cerium dioxide, titanium oxide, silicon dioxide-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina oxide, and combinations thereof.

[0100] 6. The oxidation catalyst composition of any one of embodiments 1 to 5, wherein the zirconium oxide in the first refractory metal oxide support material is doped with lanthanum in an amount of about 1% to about 40% by weight of the oxide based on the weight of the zirconium oxide.

[0101] 7. The oxidation catalyst composition of any one of embodiments 1 to 6 further comprises a base metal oxide selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, copper, magnesium, antimony, tin, lead, yttrium, and combinations thereof.

[0102] 8. The oxidation catalyst composition as described in Embodiment 7, wherein the base metal oxide is supported on the first refractory metal oxide support material.

[0103] 9. The oxidation catalyst composition as described in embodiment 7 or embodiment 8, wherein:

[0104] The base metal oxide is cerium dioxide oxide, and

[0105] The cerium dioxide is present in an amount of up to about 99% by weight (e.g., up to about 50% by weight) based on the weight of the first refractory metal oxide carrier material.

[0106] 10. The oxidation catalyst composition as described in any one of embodiments 1 to 9, comprising:

[0107] Based on the weight of the first refractory metal oxide support material, manganese in amounts of about 1 wt% to about 60 wt% (e.g., about 1 wt% to about 30 wt%; about 5 wt% to about 20 wt%; about 5 wt% to about 40 wt%) of oxide; and

[0108] The amount of cerium dioxide is about 1% to about 99% by weight (e.g., about 1% to about 30% by weight; about 1% to about 20% by weight; about 1% to about 10% by weight) based on the weight of the first refractory metal oxide support material.

[0109] 11. The oxidation catalyst composition as described in any one of embodiments 1 to 10, wherein:

[0110] The palladium is loaded onto the first refractory metal oxide support in an amount of about 0% to about 10% by weight based on the weight of the first refractory metal oxide support;

[0111] The platinum is loaded onto the first refractory metal oxide support in an amount of about 0% to about 10% by weight based on the weight of the first refractory metal oxide support; and

[0112] The platinum or palladium is present in an amount of about 0.1% by weight or more based on the weight of the first refractory metal oxide support material.

[0113] 12. The oxidation catalyst composition as described in any one of embodiments 1 to 11, wherein the PGM component comprises a combination of platinum and palladium.

[0114] 13. The oxidation catalyst composition as described in embodiment 12, wherein the weight ratio of palladium to platinum is about 100 to about 0.01.

[0115] 14. The oxidation catalyst composition as described in embodiment 12, wherein the weight ratio of palladium to platinum is from about 1 to about 0.01.

[0116] 15. The oxidation catalyst composition as described in any one of embodiments 1 to 14 further comprises a second refractory metal oxide support material.

[0117] 16. The oxidation catalyst composition of embodiment 15, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, silicon dioxide-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina oxide, or combinations thereof.

[0118] 17. The oxidation catalyst composition of embodiment 15 or embodiment 16, wherein the second refractory metal oxide support material comprises a base metal oxide selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, copper, magnesium, antimony, tin, lead, yttrium, and combinations thereof.

[0119] 18. The oxidation catalyst composition of any one of embodiments 15 to 17, wherein the PGM component is loaded on the second refractory metal oxide support material in an amount of about 0.1% to about 10% by weight (e.g., about 0.5% to about 10% by weight) based on the weight of the second refractory metal oxide support material.

[0120] 19. The oxidation catalyst composition of any one of embodiments 15 to 18, wherein the second refractory metal oxide support material comprises alumina or zirconium oxide.

[0121] 20. The oxidation catalyst composition of embodiment 19, wherein the zirconium oxide in the second refractory metal oxide support material is doped with lanthanum in an amount of about 0.1 wt% to about 40 wt% (e.g., about 1 wt% to about 40 wt%) based on the weight of the zirconium oxide.

[0122] 21. The oxidation catalyst composition of any one of embodiments 15 to 19, wherein the second refractory metal oxide support material is substantially free of lanthanum.

[0123] 22. The oxidation catalyst composition of any one of embodiments 15 to 21, wherein the second refractory metal oxide support material comprises manganese.

[0124] 23. The oxidation catalyst composition of any one of embodiments 15 to 22, wherein the manganese component is supported on the first refractory metal oxide support material and the PGM component is supported on the second refractory metal oxide support material.

[0125] 24. The oxidation catalyst composition of embodiment 23, wherein the component PGM is loaded on the second refractory metal oxide support material in an amount of about 0.1% to about 10% by weight (e.g., about 0.5% to about 5% by weight) based on the weight of the second refractory metal oxide support material.

[0126] 25. The oxidation catalyst composition as described in embodiment 15, wherein:

[0127] The manganese component is manganese oxide, which is loaded onto the first refractory metal oxide support material in an amount of about 0.1 wt% to about 40 wt% (e.g., about 1 wt% to about 40 wt%) based on the weight of the first refractory metal oxide support material; and

[0128] The PGM component is loaded onto the second refractory metal oxide support material, wherein the second refractory metal oxide support material is selected from alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and zirconium oxide doped with lanthanum oxide, wherein the amount of lanthanum oxide is from about 1% by weight to about 40% by weight based on the weight of the zirconium oxide.

[0129] 26. The oxidation catalyst composition of embodiment 25, wherein the first refractory metal oxide support material further comprises cerium dioxide in an amount of about 1% to about 50% by weight based on the weight of the first refractory metal oxide support material.

[0130] 27. The oxidation catalyst composition as described in any one of embodiments 1 to 25, wherein the oxidation catalyst composition is substantially free of copper.

[0131] 28. A catalytic article comprising an inlet end and an outlet end having a defined total length, and a catalytic coating disposed on at least a portion of the substrate, the catalytic coating comprising a first carrier coating and a second carrier coating, wherein:

[0132] The first carrier coating comprises a manganese component and a first refractory metal oxide carrier material, the first refractory metal oxide carrier material comprising zirconium oxide, wherein the manganese component is loaded onto the first refractory metal oxide carrier material in the form of manganese oxide or a mixed oxide; and

[0133] The second carrier coating comprises a platinum group metal (PGM) component and a second refractory metal oxide carrier material, wherein the platinum group metal component comprises palladium, platinum, or a combination thereof, and wherein the PGM component is loaded onto the second refractory metal oxide carrier material.

[0134] 29. The catalyst article of embodiment 28 comprises manganese in an amount of about 0.1 wt% to about 40 wt% (e.g., about 1 wt% to about 40 wt%) of oxide based on the weight of the first refractory metal oxide support material.

[0135] 30. The catalyst article as described in embodiment 28 or embodiment 29 further comprises a base metal oxide supported on the first refractory metal oxide support material, wherein the base metal oxide is selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, copper, and combinations thereof.

[0136] 31. The catalytic article as described in embodiment 28 or embodiment 29 further comprises a base metal oxide supported on the first refractory metal oxide support material, wherein the base metal oxide is selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, magnesium, antimony, tin, lead, yttrium, and combinations thereof.

[0137] 32. The catalyst article of embodiment 30, wherein the base metal oxide is cerium dioxide oxide, and wherein the cerium dioxide is present in an amount of up to about 30% by weight based on the weight of the first refractory metal oxide support material.

[0138] 33. The catalyst article as described in embodiment 32, comprising:

[0139] Based on the weight of the first refractory metal oxide support material, manganese in an amount of approximately 1% to approximately 30% by weight of the oxide; and

[0140] The amount of cerium dioxide is approximately 1% to approximately 30% by weight of the first refractory metal oxide carrier material.

[0141] 34. The catalyst article of any one of embodiments 28 to 33, wherein the zirconium oxide in the first refractory metal oxide support material is doped with about 1% by weight to about 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide.

[0142] 35. The catalyst article of any one of embodiments 28 to 34, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, or a combination thereof.

[0143] 36. The catalytic article of any one of embodiments 28 to 34, wherein the second refractory metal oxide support material comprises alumina.

[0144] 37. The catalyst article of any one of embodiments 28 to 34, wherein the second refractory metal oxide support material comprises zirconium oxide.

[0145] 38. The catalyst article of embodiment 37, wherein the zirconium oxide in the second refractory metal oxide support material is doped with about 1% to about 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide.

[0146] 39. The catalyst article of any one of embodiments 28 to 34, wherein the second refractory metal oxide support material is selected from alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and zirconium oxide doped with lanthanum oxide, wherein the amount of lanthanum oxide is from about 1% by weight to about 40% by weight based on the weight of the zirconium oxide.

[0147] 40. The catalyst article as described in any one of embodiments 28 to 39, wherein the PGM component comprises a combination of platinum and palladium.

[0148] 41. The catalyst article as described in embodiment 40, wherein the weight ratio of palladium to platinum is about 100 to about 0.01.

[0149] 42. The catalyst article as described in embodiment 40, wherein the weight ratio of palladium to platinum is from about 1 to about 0.01.

[0150] 43. The catalyst article as described in any one of embodiments 28 to 42, wherein the total PGM component supported on the catalyst article is about 5 g / ft. 3 Approximately 200g / ft 3 .

[0151] 44. The catalyst article of any one of embodiments 28 to 42, wherein the PGM is loaded on the second refractory metal oxide support material in an amount of about 0.5% to about 10% by weight (e.g., about 0.5% to about 5% by weight) based on the weight of the second refractory metal oxide support material.

[0152] 45. The catalyst article as described in embodiment 28, wherein:

[0153] The manganese component is manganese oxide, which is loaded on the first refractory metal oxide support material in an amount of about 1% to about 30% by weight of oxide based on the weight of the first refractory metal oxide support material, wherein the first refractory metal oxide support material comprises alumina or zirconium oxide, wherein the zirconium oxide is doped with about 1% to about 40% by weight of lanthanum oxide based on the weight of the zirconium oxide.

[0154] The first refractory metal oxide support material further comprises cerium dioxide in an amount of about 1% to about 50% by weight based on the weight of the first refractory metal oxide support material; and

[0155] The PGM component is loaded onto the second refractory metal oxide support material, wherein the second refractory metal oxide support material is selected from alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and zirconium oxide doped with lanthanum oxide, wherein the amount of lanthanum oxide is from about 1% by weight to about 40% by weight based on the weight of the zirconium oxide.

[0156] 46. ​​The catalyst article of any one of embodiments 28 to 45, wherein the first carrier coating and the second carrier coating are substantially free of copper.

[0157] 47. The catalyst article of any one of embodiments 28 to 46, wherein the first carrier coating is disposed directly on the substrate, and the second carrier coating is disposed on at least a portion of the first carrier coating.

[0158] 48. The catalyst article of any one of embodiments 28 to 46, wherein the second carrier coating is disposed directly on the substrate, and the first carrier coating is disposed on at least a portion of the second carrier coating.

[0159] 49. The catalyst article of any one of embodiments 28 to 46, wherein the catalyst article has a partitioned configuration, wherein the first carrier coating is directly disposed on the substrate from the outlet end to a length of about 20% to about 100% of the total length; and the second carrier coating is disposed on the substrate from the inlet end to a length of about 20% to about 100% of the total length.

[0160] 50. The catalyst article of any one of embodiments 28 to 46, wherein the catalyst article has a partitioned configuration, wherein the second carrier coating is directly disposed on the substrate from the outlet end to a length of about 20% to about 100% of the total length; and the first carrier coating is disposed on the substrate from the inlet end to a length of about 20% to about 100% of the total length.

[0161] 51. A catalytic article comprising an inlet end and an outlet end having a defined total length, and a catalytic coating disposed on at least a portion of the substrate, the catalytic coating comprising a first carrier coating, a second carrier coating, and a third carrier coating, wherein:

[0162] The first carrier coating comprises a manganese component and a first refractory metal oxide carrier material, wherein the first refractory metal oxide carrier material comprises zirconium oxide, and wherein the manganese component is loaded on the first refractory metal oxide carrier material in the form of manganese oxide or mixed oxide.

[0163] The second carrier coating comprises a base metal oxide component and a second refractory metal oxide carrier material, wherein the base metal oxide component includes cerium dioxide, manganese oxide, zirconium oxide, lanthanum oxide, copper oxide, or combinations thereof, and wherein the base metal oxide component is loaded onto the second refractory metal oxide carrier material; and

[0164] The third carrier coating comprises a platinum group metal (PGM) component and a third refractory metal oxide carrier material, wherein the platinum group metal component comprises palladium, platinum, or a combination thereof, and wherein the PGM component is loaded onto the third refractory metal oxide carrier material.

[0165] 52. The catalyst article of embodiment 51, wherein the zirconium oxide in the first refractory metal oxide support material is doped with lanthanum oxide at about 1% to about 40% by weight based on the total weight of the zirconium oxide.

[0166] 53. The catalyst article as described in embodiment 51 or embodiment 52, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, silicon dioxide-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina oxide, or combinations thereof.

[0167] 54. The catalytic article of any one of embodiments 51 to 53, wherein the second refractory metal oxide support material comprises alumina.

[0168] 55. The catalytic article of any one of embodiments 51 to 54, wherein the second refractory metal oxide support material comprises silicon dioxide-doped alumina.

[0169] 56. The catalytic article of any one of embodiments 51 to 53, wherein the second refractory metal oxide support material comprises zirconium oxide.

[0170] 57. The catalyst article of embodiment 56, wherein the zirconium oxide in the second refractory metal oxide support material is doped with lanthanum oxide at about 0.1% to about 40% by weight based on the total weight of the zirconium oxide.

[0171] 58. The catalyst article of any one of embodiments 51 to 57, wherein the third refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, silicon dioxide-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, silicon dioxide-titanium dioxide, silicon dioxide-zirconia, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, lanthanum-zirconia, lanthanum-zirconia-alumina, magnesium-alumina oxide, or combinations thereof.

[0172] 59. The catalytic article of any one of embodiments 51 to 58, wherein the PGM component comprises a combination of platinum and palladium.

[0173] 60. The catalyst article of any one of embodiments 51 to 59, wherein the first carrier coating is disposed directly on the substrate, and the second carrier coating is disposed on at least a portion of the first carrier coating.

[0174] 61. The catalyst article of any one of embodiments 51 to 59, wherein the second carrier coating is disposed directly on the substrate, and the first carrier coating is disposed on at least a portion of the second carrier coating.

[0175] 62. The catalyst article of any one of embodiments 51 to 59, wherein the first carrier coating is disposed directly on the substrate, the second carrier coating is disposed on at least a portion of the first carrier coating, and the third carrier coating is disposed on at least a portion of the second carrier coating.

[0176] 63. The catalyst article of any one of embodiments 51 to 59, wherein the third carrier coating is directly disposed on the substrate, the second carrier coating is disposed on at least a portion of the third carrier coating, and the first carrier coating is disposed on at least a portion of the second carrier coating.

[0177] 64. The catalyst article of any one of embodiments 51 to 59, wherein the first carrier coating is disposed directly on the substrate, the third carrier coating is disposed on at least a portion of the first carrier coating, and the second carrier coating is disposed on at least a portion of the third carrier coating.

[0178] 65. The catalyst article of any one of embodiments 51 to 59, wherein the second carrier coating is directly disposed on the substrate, the third carrier coating is disposed on at least a portion of the second carrier coating, and the first carrier coating is disposed on at least a portion of the third carrier coating.

[0179] 66. The catalyst article of any one of embodiments 51 to 59, wherein the second carrier coating is disposed directly on the substrate, the first carrier coating is disposed on at least a portion of the second carrier coating, and the third carrier coating is disposed on at least a portion of the first carrier coating.

[0180] 67. The catalyst article as described in any one of embodiments 51 to 59, wherein the catalyst article has a partitioned configuration, wherein:

[0181] The first carrier coating is applied directly to the substrate over a length of approximately 20% to approximately 100% of the total length from the outlet end;

[0182] The second carrier coating is applied to the substrate over a length of approximately 20% to approximately 100% of its total length from the inlet end; and

[0183] The third carrier coating is applied to the substrate over a length of approximately 20% to approximately 100% of the total length from the inlet end.

[0184] 68. An exhaust gas treatment system comprising a catalytic article as described in any one of embodiments 28 to 67, wherein the catalytic article is downstream of and in fluid communication with a compression ignition internal combustion engine.

[0185] 69. A method for treating an exhaust gas stream, the exhaust gas stream comprising hydrocarbons and / or carbon monoxide and / or NO. x The method includes contacting the waste gas stream with a catalyst as described in any one of embodiments 28 to 67 or a waste gas treatment system as described in embodiment 68.

[0186] 70. A formaldehyde oxidation catalyst composition, said formaldehyde oxidation catalyst composition comprising:

[0187] Refractory metal oxide carrier materials, including zirconium oxide;

[0188] Based on the weight of the refractory metal oxide support material, manganese in amounts from about 1% to about 30% by weight of the oxide; and

[0189] Based on a weight of approximately 0% to approximately 30% cerium dioxide from the refractory metal oxide support material,

[0190] The formaldehyde oxidation catalyst composition described herein is substantially free of copper.

[0191] 71. The formaldehyde oxidation catalyst composition of embodiment 70, wherein the manganese is disposed on the refractory metal oxide support material.

[0192] 72. The formaldehyde oxidation catalyst composition of embodiment 70, wherein the cerium dioxide is disposed on the refractory metal oxide support material.

[0193] 73. The catalyst article of embodiment 70, wherein the zirconium oxide in the refractory metal oxide support material is doped with lanthanum oxide at about 0.1% to about 40% by weight based on the total weight of the zirconium oxide.

[0194] Non-restrictive example implementation scheme 2 :

[0195] In a non-restrictive manner, some non-restrictive embodiments / clauses of this disclosure include:

[0196] 1. An oxidation catalyst composition for use in an exhaust gas treatment system comprising a compression-ignition internal combustion engine, the composition comprising:

[0197] Platinum group metals (PGM) composition, which includes palladium, platinum, or combinations thereof;

[0198] Manganese component; and

[0199] The first refractory metal oxide support material includes zirconium oxide.

[0200] Optional second refractory metal oxide carrier material

[0201] 2. The oxidation catalyst composition as described in Clause 1, comprising manganese in an amount of about 1% to about 40% by weight of the oxide based on the weight of the first refractory metal oxide support material.

[0202] 3. The oxidation catalyst composition as described in Clause 1, wherein the first refractory metal oxide support material comprises about 5% by weight to about 99% by weight of zirconium oxide.

[0203] 4. The oxidation catalyst composition as described in paragraph 1, wherein the zirconium oxide is doped with lanthanum in an amount of about 1% to about 40% by weight of oxide based on the weight of the zirconium oxide.

[0204] 5. The oxidation catalyst composition as described in clause 1 further comprises a base metal oxide, said base metal being selected from the group consisting of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, copper, and combinations thereof.

[0205] 6. The oxidation catalyst composition as described in paragraph 5, wherein the base metal is selected from the group consisting of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, and combinations thereof.

[0206] 7. The oxidation catalyst composition as described in paragraph 5, wherein the base metal oxide is cerium dioxide, and wherein the cerium dioxide is present in an amount of up to about 50% by weight based on the weight of the first refractory metal oxide support material.

[0207] 8. The oxidation catalyst composition as described in clause 1, comprising:

[0208] Based on the weight of the first refractory metal oxide support material, manganese in amounts of about 1% to about 30% by weight of the oxide, or about 5% to about 20% by weight; and

[0209] Cerium dioxide in an amount of about 1% to about 30% by weight, about 1% to about 20% by weight, or about 1% to about 10% by weight, based on the weight of the first refractory metal oxide support material.

[0210] 9. The oxidation catalyst composition as described in clause 1, wherein:

[0211] The palladium is loaded onto the first refractory metal oxide support in an amount of 0% to 10% by weight based on the weight of the first refractory metal oxide support;

[0212] The platinum is loaded onto the first refractory metal oxide support in an amount of 0% to 10% by weight, based on the weight of the first refractory metal oxide support; and

[0213] The platinum or palladium is present in an amount of about 0.1% by weight or more based on the weight of the first refractory metal oxide support.

[0214] 10. The oxidation catalyst composition as described in paragraph 1, wherein the PGM component comprises a combination of platinum and palladium.

[0215] 11. The oxidation catalyst composition as described in paragraph 9, wherein the weight ratio of palladium to platinum is about 100 to about 0.05.

[0216] 12. The oxidation catalyst composition as described in paragraph 9, wherein the weight ratio of palladium to platinum is from about 1 to about 0.05, or from about 0.5 to about 0.1.

[0217] 13. The oxidation catalyst composition as described in clause 1 further comprises a second refractory metal oxide support material.

[0218] 14. The oxidation catalyst composition as described in clause 13, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, or a combination thereof.

[0219] 15. The oxidation catalyst composition as described in clause 13, wherein the second refractory metal oxide support material comprises alumina.

[0220] 16. The oxidation catalyst composition as described in clause 13, wherein the PGM component is loaded on the second refractory metal oxide support material in an amount of about 0.5% to about 10% by weight based on the weight of the second refractory metal oxide support material.

[0221] 17. The oxidation catalyst composition as described in clause 13, wherein the second refractory metal oxide support material comprises zirconium oxide.

[0222] 18. The oxidation catalyst composition of claim 17, wherein the zirconium oxide is doped with lanthanum in an amount of about 1% to about 40% by weight of oxide based on the weight of the zirconium oxide.

[0223] 19. The oxidation catalyst composition of claim 13, wherein the manganese component is supported on the first refractory metal oxide support material and the PGM component is supported on the second refractory metal oxide support material.

[0224] 20. The oxidation catalyst composition as described in clause 19, wherein the PGM component is loaded on the second refractory metal oxide support material in an amount of about 0.5% to about 5% by weight based on the weight of the second refractory metal oxide support material.

[0225] 21. The oxidation catalyst composition as described in clause 1, wherein:

[0226] The manganese component is manganese oxide, which is loaded onto the first refractory metal oxide support material in an amount of about 1% to about 40% by weight of the oxide, based on the weight of the first refractory metal oxide support material, wherein the first refractory metal oxide support material comprises zirconium oxide; and

[0227] The PGM component is loaded onto the second refractory metal oxide support material, wherein the second refractory metal oxide support material is selected from the group consisting of: alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and lanthanum oxide-doped zirconium oxide, wherein the amount of lanthanum oxide is from about 1% by weight to about 40% by weight based on the weight of the zirconium oxide.

[0228] 22. The oxidation catalyst composition as described in paragraph 21, wherein the zirconium oxide is doped with about 1% to about 40% lanthanum oxide based on the weight of the zirconium oxide.

[0229] 23. The oxidation catalyst composition as described in clause 21, wherein the first refractory metal oxide support material further comprises about 1% to about 50% by weight of cerium dioxide based on the weight of the first refractory metal oxide support material.

[0230] 24. The oxidation catalyst composition of any one of clauses 1 to 23, wherein the oxidation catalyst composition is substantially free of copper.

[0231] 25. A catalytic article comprising an inlet end and an outlet end having a defined total length, and a catalytic coating disposed on at least a portion of the substrate, the catalytic coating comprising a first carrier coating and a second carrier coating, wherein:

[0232] The first carrier coating comprises a manganese component and a first refractory metal oxide carrier material, the first refractory metal oxide carrier material comprising zirconium oxide, wherein the manganese component is loaded onto the first refractory metal oxide carrier material in the form of manganese oxide or a mixed oxide; and

[0233] The second carrier coating comprises a platinum group metal (PGM) component and a second refractory metal oxide carrier material, wherein the platinum group metal component comprises palladium, platinum, or a combination thereof, and wherein the PGM component is loaded onto the second refractory metal oxide carrier material.

[0234] 26. The catalyst article as described in paragraph 25 comprises manganese in an amount of about 1% to about 40% by weight of the oxide based on the weight of the first refractory metal oxide support material.

[0235] 27. The catalyst article as described in paragraph 25 further comprises a base metal oxide supported on the first refractory metal oxide carrier material, said base metal being selected from the group consisting of: cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, copper, and combinations thereof.

[0236] 28. The catalyst article as described in paragraph 27, wherein the base metal is selected from the group consisting of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, and combinations thereof.

[0237] 29. The catalyst article as described in paragraph 27, wherein the base metal oxide is cerium dioxide, and wherein the cerium dioxide is present in an amount of up to about 30% by weight based on the weight of the first refractory metal oxide support material.

[0238] 30. The catalyst article as described in clause 25, comprising:

[0239] Based on the weight of the first refractory metal oxide support material, manganese in amounts of about 1% to about 30% by weight of the oxide, or about 5% to about 20% by weight; and

[0240] Cerium dioxide in an amount of about 1% to about 30% by weight, about 1% to about 20% by weight, or about 1% to about 10% by weight, based on the weight of the first refractory metal oxide support material.

[0241] 31. The catalyst article as described in paragraph 25, wherein the zirconium oxide is doped with about 1% to about 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide.

[0242] 32. The catalyst article as described in clause 25, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, or a combination thereof.

[0243] 33. The catalyst article as described in clause 32, wherein the second refractory metal oxide support material comprises alumina.

[0244] 34. The catalyst article as described in clause 32, wherein the second refractory metal oxide support material comprises zirconium oxide.

[0245] 35. The catalyst article as described in paragraph 34, wherein the zirconium oxide is doped with about 1% to about 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide.

[0246] 36. The catalyst article as described in clause 32, wherein the second refractory metal oxide support material is selected from the group consisting of: alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and lanthanum oxide-doped zirconium oxide, wherein the amount of lanthanum oxide is from about 1% by weight to about 40% by weight based on the weight of the zirconium oxide.

[0247] 37. The catalyst article as described in paragraph 25, wherein the PGM component comprises a combination of platinum and palladium.

[0248] 38. The catalyst article as described in paragraph 37, wherein the weight ratio of palladium to platinum is about 100 to about 0.05.

[0249] 39. The catalyst article as described in paragraph 37, wherein the weight ratio of palladium to platinum is from about 1 to about 0.05, or from about 0.5 to about 0.1.

[0250] 40. The catalyst article as described in clause 37, wherein the total PGM component supported on the catalyst article is about 5 g / ft. 3 Approximately 200g / ft 3 .

[0251] 41. The catalyst article as described in paragraph 25, wherein the PGM is loaded on the second refractory metal oxide support material in an amount of about 0.5% to about 5% by weight based on the weight of the second refractory metal oxide support material.

[0252] 42. The catalyst article as described in clause 25, wherein:

[0253] The manganese component is manganese oxide, which is loaded on the first refractory metal oxide carrier material in an amount of about 1% to about 30% by weight of oxide based on the weight of the first refractory metal oxide carrier material, wherein the first refractory metal oxide carrier material comprises alumina or comprises zirconium oxide doped with lanthanum oxide, wherein the amount of lanthanum oxide is about 1% to about 40% by weight based on the weight of the zirconium oxide.

[0254] The first refractory metal oxide support material further comprises cerium dioxide in an amount of about 1% to about 50% by weight based on the weight of the first refractory metal oxide support material; and

[0255] The PGM component is loaded onto the second refractory metal oxide support material, wherein the second refractory metal oxide support material is selected from the group consisting of: alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and lanthanum oxide-doped zirconium oxide, wherein the amount of lanthanum oxide is from about 1% by weight to about 40% by weight based on the weight of the zirconium oxide.

[0256] 43. The catalytic article as described in any one of paragraphs 25 to 42, wherein the first carrier coating and the second carrier coating are substantially free of copper.

[0257] 44. The catalytic article of any one of clauses 25 to 42, wherein the first carrier coating is disposed directly on the substrate, and the second carrier coating is disposed on at least a portion of the first carrier coating.

[0258] 45. The catalytic article of any one of clauses 25 to 42, wherein the second carrier coating is disposed directly on the substrate, and the first carrier coating is on at least a portion of the second carrier coating.

[0259] 46. ​​The catalyst article of any one of paragraphs 25 to 42, having a partitioned configuration, wherein the first carrier coating is directly disposed on the substrate from the outlet end to a length of about 20% to about 100% of the total length; and the second carrier coating is disposed on the substrate from the inlet end to a length of about 20% to about 100% of the total length.

[0260] 47. The catalyst article of any one of clauses 25 to 42, having a partitioned configuration, wherein the second carrier coating is directly disposed on the substrate from the outlet end to a length of about 20% to about 100% of the total length; and the first carrier coating is disposed on the substrate from the inlet end to a length of about 20% to about 100% of the total length.

[0261] 48. An exhaust gas treatment system comprising a catalytic article as described in any one of claims 25 to 47, wherein the catalytic article is downstream of and in fluid communication with a compression-ignition internal combustion engine.

[0262] 49. A method for treating an exhaust gas stream, the exhaust gas stream comprising hydrocarbons and / or carbon monoxide and / or NO. x The method includes contacting the waste gas stream with a catalyst as described in any one of paragraphs 25 to 47 or a waste gas treatment system as described in paragraph 48.

[0263] Oxidation catalyst composition

[0264] As described above, this disclosure provides an oxidation catalyst composition comprising a refractory metal oxide support material, a platinum group metal (PGM) component, and a manganese component. Each of the individual components of the composition is further described below.

[0265] Refractory metal oxide carrier

[0266] The oxidation catalyst compositions disclosed herein comprise refractory metal oxide support materials. As used herein, "refractory metal oxide" refers to porous metal oxide materials that exhibit chemical and physical stability at high temperatures, such as those associated with diesel engine exhaust gases. Exemplary refractory metal oxides include, but are not limited to, alumina, silica, zirconium oxide, titanium dioxide, cerium dioxide, and physical mixtures or chemical combinations thereof, including atomically doped combinations and including high surface area or active compounds, such as activated alumina. In some embodiments, the refractory metal oxide support comprises alumina, silica, cerium dioxide, titanium oxide, silica-doped alumina, silica-titanium dioxide, silica-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina oxide, and combinations thereof. Exemplary alumina comprises macroporous boehmite, γ-alumina, and δ / θ alumina. Useful commercially available alumina includes active alumina, such as high-density gamma-alumina, low or medium-density macroporous gamma-alumina, and low-density macroporous boehmite and gamma-alumina.

[0267] High-surface-area refractory oxide supports, such as alumina support materials, also known as "gamma alumina" or "active alumina," typically exhibit surface areas exceeding 60 μm. 2 / g, typically up to about 200m 2 / g or higher BET surface area. Such activated alumina is typically a mixture of the γ and δ phases of alumina, but may also contain significant amounts of η, κ, and θ alumina phases. As used herein, “BET surface area” has its general meaning: referring to the Brunol, Emmett, and Taylor methods used to determine surface area by N2 adsorption. In some embodiments, the refractory metal oxide support material (e.g., activated alumina) has a specific surface area of ​​60 m² / g or higher. 2 / g to 350m 2 / g, for example, about 90m 2 / g to approximately 250m 2 / g.

[0268] In some embodiments, the refractory metal oxide support material comprises alumina (Al₂O₃), silicon dioxide (SiO₂), zirconium oxide (ZrO₂), titanium dioxide (TiO₂), cerium dioxide (CeO₂), or physical mixtures or chemical combinations thereof. In some embodiments, the refractory metal oxide support that can be used in the oxidation catalyst compositions disclosed herein is doped with another metal oxide, said other metal oxide including, but not limited to, silicon dioxide (SiO₂), cerium dioxide (CeO₂), titanium dioxide (TiO₂), or lanthanum oxide (La₂O₃). In some embodiments, the refractory metal oxide support is selected from doped materials such as Si-doped alumina materials (including, but not limited to, 1%-10% SiO₂-Al₂O₃), doped titanium dioxide materials such as Si-doped titanium dioxide materials (including, but not limited to, 1%-10% SiO₂-TiO₂), or doped zirconium oxide materials such as Si-doped ZrO₂ (including, but not limited to, 5%-30% SiO₂-ZrO₂). Therefore, in some embodiments, the refractory metal oxide support material comprises SiO2-doped Al2O3, SiO2-doped TiO2, or SiO2-doped ZrO2 (including but not limited to 5%-30% SiO2-ZrO2).

[0269] In some embodiments, the refractory metal oxide support material comprises zirconium oxide. In some embodiments, the zirconium oxide is doped with one or more dopants. In some embodiments, the refractory metal oxide support material comprises about 5% to about 99% zirconium oxide (i.e., the total amount of dopants present is about 1% to about 95%). In some embodiments, the refractory metal oxide support material comprises about 20% to about 99% zirconium oxide (i.e., the total amount of dopants present is about 1% to about 80%). In some embodiments, the zirconium oxide is doped with lanthanum oxide. In some embodiments, the refractory metal oxide support material comprises zirconium oxide doped with about 1% to about 40% La2O3. In some embodiments, the zirconium oxide is doped with about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% to about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, or about 40 wt% of lanthanum oxide based on the weight of the zirconium oxide. In some embodiments, the zirconium oxide is doped with about 1% to about 10% of lanthanum oxide. In some embodiments, the zirconium oxide is doped with about 9% of lanthanum oxide.

[0270] One or more dopant metal oxides can be introduced using techniques such as initial wet impregnation. In some embodiments, the metal oxides may exist in the doped refractory metal oxide support material as a mixed oxide, meaning that the metal oxides are covalently bonded to each other through shared oxygen atoms.

[0271] The oxidation catalyst composition may contain any and any amount of the refractory metal oxides described above. For example, the refractory metal oxides in the catalyst composition may comprise, on a total dry weight basis, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, or about 50% by weight to about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, about 80% by weight, about 85% by weight, about 90% by weight, about 95% by weight, or about 99% by weight.

[0272] The terms "first" and "second" in this document, referring to the refractory metal oxide support material, are used to distinguish between the two materials. The first and second refractory metal oxide support materials may be the same or different. In some embodiments, the first and second refractory metal oxide support materials are the same. In other embodiments, they are different.

[0273] In some embodiments, the first refractory metal oxide support material comprises zirconium oxide. In some embodiments, the first refractory metal oxide support comprises zirconium oxide doped with lanthanum oxide. In some embodiments, the first refractory metal oxide support material comprises zirconium oxide doped with 1%-40% lanthanum oxide. In some embodiments, the first refractory metal oxide support material comprises zirconium oxide doped with 1%-10% lanthanum oxide. In some embodiments, the first refractory metal oxide support material comprises zirconium oxide doped with about 9% lanthanum oxide.

[0274] In some implementations, the first refractory metal oxide support material is essentially lanthanum-free.

[0275] In some implementations, the second refractory metal oxide carrier material comprises manganese.

[0276] In some embodiments, the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, silicon dioxide-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina oxide, or combinations thereof. In some embodiments, the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, or combinations thereof. In one or more embodiments, the second refractory metal oxide support is selected from (e.g., selected from the group consisting of) γ-alumina, silicon dioxide-doped alumina, cerium dioxide-doped alumina, and titanium dioxide-doped alumina. In some embodiments, the second refractory metal oxide support material is selected from (e.g., selected from the group consisting of) alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and zirconium oxide doped with lanthanum oxide, wherein the amount of lanthanum oxide is from about 1 wt% to about 40 wt% based on the weight of the zirconium oxide. In some embodiments, the second refractory metal oxide support material is selected from (e.g., selected from the group consisting of) γ-alumina and alumina doped with about 1 wt% to about 10 wt% SiO2. In some embodiments, the second refractory metal oxide support material is alumina doped with about 1 wt% to about 10 wt% SiO2, for example, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% SiO2. In some embodiments, the second refractory metal oxide support material is alumina.

[0277] In some embodiments, the second refractory metal oxide support material comprises zirconium oxide. In some embodiments, the second refractory metal oxide support material is selected from (e.g., selected from the group consisting of) alumina, silica-doped alumina, zirconium oxide, and lanthanum oxide-doped zirconium oxide, wherein the amount of lanthanum oxide is from about 1% to about 40% by weight based on the weight of the zirconium oxide. In some embodiments, the second refractory metal oxide support is lanthanum oxide-doped zirconium oxide. In some embodiments, the second refractory metal oxide support material is zirconium oxide doped with 1% to 40% lanthanum oxide. In some embodiments, the second refractory metal oxide support material is zirconium oxide doped with 1% to 10% lanthanum oxide. In some embodiments, the second refractory metal oxide support material is zirconium oxide doped with about 9% lanthanum oxide. In some embodiments, both the first and second refractory metal oxide support materials comprise zirconium oxide doped with about 1% to 10% lanthanum oxide. In some embodiments, the first refractory metal oxide support material comprises zirconium oxide doped with about 1%-10% lanthanum oxide, and the second refractory metal oxide support material is alumina.

[0278] In some implementations, the second refractory metal oxide support material is essentially lanthanum-free.

[0279] Platinum group metals (PGM) composition

[0280] The oxidation catalyst compositions described herein comprise a platinum group metal (PGM) component. PGMs include platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), osmium (Os), iridium (Ir), gold (Au), and mixtures thereof. The PGM component can comprise PGMs in any valence state. As used herein, the term "PGM component" refers both to the catalytically active form of the individual PGM and the corresponding PGM compound, complex, etc., which decomposes or otherwise transforms into its catalytically active form upon calcination or use with the catalyst, typically a metal or metal oxide. PGMs can be in metallic form with a zero valence ("PGM(0)"), or PGMs can be in oxide form (e.g., including but not limited to platinum or oxides thereof). The amount of PGM(0) can be determined by ultrafiltration followed by inductively coupled plasma / optical emission spectrometry (ICP-OES) or by X-ray photoelectron spectroscopy (XPS).

[0281] In some embodiments, the PGM component includes platinum, palladium, or a combination thereof. In some embodiments, the PGM component is palladium. In some embodiments, the PGM component is platinum. In some embodiments, the PGM component is a combination of palladium and platinum. Exemplary weight ratios of such Pd / Pt combinations include, but are not limited to, from about 100 to about 0.01 Pd:Pt, such as about 100:1, about 50:1, about 40:1, 30:1, about 25:1, about 20:1, about 15:1, about 10:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:5, about 1:10, or about 1:20 Pd / Pt weight ratios. In some embodiments, the Pd / Pt weight ratio is about 100. In some embodiments, the palladium to platinum weight ratio is from about 1 to about 0.01, from about 1 to about 0.05, or from about 0.5 to about 0.1. In each case, the weight ratio is based on the element (metal).

[0282] The PGM component is loaded (e.g., impregnated) onto a refractory metal oxide support material as described above. The PGM component may be present in an amount ranging from about 0.01% to about 20% (e.g., about 0.1% to about 10%; about 0.5% to about 5%) based on the total weight of the refractory metal oxide support material (including the loaded PGM) and the weight of the metal. The oxidation catalyst composition may comprise about 0.1 wt%, about 0.5 wt%, about 1.0 wt%, about 1.5 wt%, or about 2.0 wt% to about 3 wt%, about 5 wt%, about 7 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, or about 20 wt% of PGM, such as Pd or Pt / Pd, based on the total weight of the refractory metal oxide support material (including the loaded PGM).

[0283] In some embodiments, the platinum group metal component is loaded onto the second refractory metal oxide support material. In some embodiments, the PGM component is platinum, palladium, or a combination thereof, and the PGM is loaded onto the second refractory metal oxide support material in an amount of about 0.5% to about 5% by weight based on the weight of the second refractory metal oxide support material. In some embodiments, the PGM is loaded onto the second refractory metal oxide support material in an amount of about 2% by weight based on the weight of the second refractory metal oxide support material.

[0284] In some embodiments, the total PGM component supported on the catalyst is about 5 g / ft. 3 Approximately 200g / ft 3 .

[0285] manganese components

[0286] In some embodiments, the oxidation catalyst composition as described herein comprises a manganese component. As used herein, reference to “manganese component” is intended to include various oxidation states, salts, and physical forms of Mn, typically in oxide form. Reference herein to “supported” manganese component means that the manganese component is disposed in or on a refractory metal oxide support material by association, dispersion, impregnation, or other suitable methods, and may reside on a surface or be distributed throughout the refractory metal oxide support material. In some embodiments, the manganese component is derived from soluble Mn substances, including but not limited to Mn salts such as acetates, nitrates, sulfates, or combinations thereof. Those skilled in the art will understand that upon calcination, the Mn substance (e.g., Mn salt) will be converted into one or more forms of manganese oxide (MnxO). y ,in x (It is 1 or 2, and y is 1, 2 or 3). In some embodiments, the manganese component is MnO2, Mn2O3, Mn3O4 or a combination thereof.

[0287] According to some embodiments, refractory metal oxide supports are impregnated with Mn salts. As used herein, the term "impregnation" refers to placing a solution containing Mn into the pores of a material such as a refractory metal oxide support. In some embodiments, Mn impregnation is achieved by incipient wetness, wherein the volume of the diluted solution containing Mn is approximately equal to the pore volume of the support. Incipient wetness typically results in a substantially uniform distribution of the precursor solution throughout the pore system of the material. Alternative methods of adding metals such as Mn are known in the art and can be used.

[0288] Therefore, according to some embodiments, the refractory metal oxide support is treated dropwise in a planetary mixer with a Mn source (e.g., a solution of Mn salt) to impregnate the support with the Mn component. In some embodiments, the refractory metal oxide support containing the Mn component is available from commercial sources.

[0289] In some embodiments, manganese can be co-precipitated with a Mn substance (e.g., Mn salt) and a refractory metal oxide support precursor, followed by calcination of the co-precipitated material, such that the refractory oxide support material and manganese are in a solid solution, thereby being loaded onto the refractory oxide support. Therefore, according to some embodiments, mixed oxides containing oxides of manganese, aluminum, cerium, silicon, zirconium, or titanium can be formed.

[0290] The manganese component can be present in the refractory metal oxide support material in a certain concentration range. In some embodiments, the Mn content, based on the weight of the refractory metal oxide support and calculated in terms of metal oxides, ranges from about 1% to about 40% (including 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%). In some embodiments, the Mn content, based on the weight of the refractory metal oxide support, ranges from about 5% to about 15% by weight or from about 8% to about 12% by weight. In some embodiments, the composition comprises manganese in amounts from about 1% to about 30% by weight, about 5% to about 20% by weight, or about 1% to about 10% by weight based on oxides, based on the weight of the refractory metal oxide support material. In some embodiments, the manganese component is loaded onto a first refractory metal oxide support material.

[0291] Base metal oxides

[0292] In some embodiments, such as the oxidation catalyst compositions disclosed herein, base metal oxides are also included. As used herein, "base metal oxide" refers to an oxide compound containing a transition metal or lanthanide metal that is catalytically active for the oxidation of one or more waste gas components. For ease of reference herein, the concentration of base metal oxide material is reported according to the elemental metal concentration rather than the oxide form. Typically, at least a portion of the base metal oxide is disposed on or within a refractory metal oxide support. Depending on the valence of the particular metal, these oxides may comprise various oxidation states of the metal, such as monooxides, dioxides, trioxides, tetroxides, etc.

[0293] Suitable base metals include, but are not limited to, cerium, iron, cobalt, zinc, chromium, nickel, tungsten, copper, molybdenum, or combinations thereof. In some embodiments, the base metal is selected from (e.g., from the group consisting of) cerium, copper, iron, cobalt, zinc, chromium, nickel, tungsten, molybdenum, and combinations thereof. In some embodiments, the base metal is selected from (e.g., from the group consisting of) cerium, iron, cobalt, zinc, chromium, nickel, tungsten, molybdenum, and combinations thereof. In some embodiments, the base metal is selected from (e.g., from the group consisting of) cerium, copper, and combinations thereof. In some embodiments, the base metal is selected from cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, magnesium, antimony, tin, lead, yttrium, manganese, and combinations thereof.

[0294] In some embodiments, the oxidation catalyst composition is substantially free of copper. "Substantially free" means that no copper has been intentionally added and may be present only in trace amounts as an impurity, such as less than 0.1% by weight, less than 0.01% by weight, less than 0.001% by weight, or even 0% by weight.

[0295] The concentration of any single base metal oxide can vary, but will typically be from about 1% to about 50% by weight relative to the weight of the refractory metal oxide support material on which it is loaded (e.g., from about 1% to about 50%, from about 1% to about 30%, or from about 5% to about 20% by weight relative to the weight of the refractory metal oxide support material). In some embodiments, the concentration of any single base metal oxide is from about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, or about 10% by weight to about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, or about 50% by weight, based on the weight of the refractory oxide support material.

[0296] In some embodiments, a base metal oxide is supported on a first refractory metal oxide carrier material. In some embodiments, the base metal oxide is cerium dioxide. In some embodiments, cerium dioxide is present in an amount of up to about 50% by weight based on the weight of the first refractory metal oxide carrier material. In some embodiments, cerium dioxide is present in an amount of about 1% to about 10% by weight, about 5% to about 20% by weight, about 10% to about 30% by weight, or about 20% to about 50% by weight based on the weight of the first refractory metal oxide carrier material.

[0297] Preparation of oxidation catalyst composition

[0298] In some embodiments, the disclosed oxidation catalyst composition can be prepared via an incipient wetness impregnation method. Incipient wetness impregnation, also known as capillary impregnation or dry impregnation, is commonly used to synthesize heterogeneous materials, i.e., catalysts. Typically, a metal precursor (e.g., PGM, manganese, or base metal oxide precursor) is dissolved in an aqueous or organic solution, and then the metal-containing solution is added to a refractory metal oxide support containing a pore volume equal to the volume of the added solution. Capillary action draws the solution into the pores of the support. Adding a solution exceeding the pore volume of the support causes the transport of the solution to shift from a capillary process to a much slower diffusion process. The catalyst can then be dried and calcined to remove volatile components from the solution, thereby depositing the metal onto the surface of the catalyst support. The maximum loading is limited by the solubility of the precursor in the solution. The concentration distribution of the impregnated material depends on the mass transfer conditions within the pores during impregnation and drying. Those skilled in the art will recognize other methods for loading various components (e.g., PGM, manganese, or base metals) into the carriers of the compositions of the present invention, such as adsorption, precipitation, etc.

[0299] During a subsequent calcination step, or at least during the initial stage of using the composition, the metal precursor compound is converted into a catalytically active form of the metal or its compound. Non-limiting examples of suitable PGM precursors include palladium nitrate, tetraamine palladium nitrate, tetraamine platinum acetate, and platinum nitrate. Non-limiting examples of suitable base metal oxide precursors are nitrates, acetates, or other soluble salts of, for example, cerium, manganese, copper, etc. A suitable method for preparing the oxidation catalyst composition is to prepare a mixture of the desired PGM compound (e.g., platinum and / or palladium compounds) and a solution of at least one support, such as a finely divided high-surface-area refractory metal oxide support, such as lanthanum oxide-doped zirconium oxide, said support being sufficiently dry to absorb substantially all of the solution to form a wet solid that subsequently combines with water to form a coatable slurry. In some embodiments, the slurry is acidic, with a pH, for example, from about 2 to less than about 7. The pH of the slurry can be lowered by adding an appropriate amount of inorganic or organic acid to the slurry. A combination of both can be used when compatibility with the acidic material and the raw material is taken into account. Examples of inorganic acids include, but are not limited to, nitric acid. Examples of organic acids include, but are not limited to, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, tartaric acid, citric acid, etc. The impregnated refractory metal oxide carrier material is then dried and calcined as described above.

[0300] The aforementioned wet impregnation method can be similarly used to introduce manganese components, base metals, or both into refractory metal oxide carrier materials. Impregnation can be carried out stepwise (in sequence) or in various combinations thereof.

[0301] Formaldehyde oxidation catalyst composition

[0302] Some embodiments of this disclosure relate to formaldehyde oxidation catalyst compositions, said formaldehyde oxidation catalyst compositions comprising:

[0303] Refractory metal oxide carrier materials, including zirconium oxide;

[0304] Based on the weight of the refractory metal oxide support material, manganese in an amount of about 1% to about 30% by weight (e.g., about 10% by weight) of the oxide; and

[0305] Based on an amount of cerium dioxide of about 0% to about 30% (e.g., 0%; 10%) by weight of the refractory metal oxide support material,

[0306] The formaldehyde oxidation catalyst composition described herein is substantially free of copper.

[0307] In some embodiments, the refractory metal oxide support material further comprises alumina, silicon dioxide, cerium dioxide, titanium oxide, silicon dioxide-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina oxide, and combinations thereof.

[0308] In some embodiments, manganese is disposed on a refractory metal oxide support material. In some embodiments, cerium dioxide is disposed on a refractory metal oxide support material. In some embodiments, both manganese and cerium dioxide are disposed on a refractory metal oxide support material.

[0309] In some embodiments, the refractory metal oxide support material is doped with about 1% to about 40% (e.g., about 9% by weight) of lanthanum oxide based on the total weight of the zirconia.

[0310] Catalysts

[0311] In one aspect, an oxidation catalyst article comprising an oxidation catalyst composition as disclosed herein is provided. The article comprises a substrate on which at least a portion thereof is disposed the oxidation catalyst composition as disclosed herein. Suitable substrates are described below.

[0312] substrate

[0313] In some embodiments, the oxidation catalyst composition of the present invention is disposed on a substrate to form a catalytic article. Catalytic articles comprising a substrate are typically used as part of an exhaust gas treatment system (e.g., catalyst articles, including but not limited to articles comprising the oxidation catalyst composition disclosed herein). A useful substrate is three-dimensional, having a length, diameter, and volume similar to a cylinder. The shape need not conform to a cylinder. The length is the axial length defined by the inlet end and the outlet end.

[0314] In some embodiments, the substrate for one or more of the disclosed compositions may be made of any material commonly used in the preparation of automotive catalysts and will typically include a metallic or ceramic honeycomb structure. The substrate typically provides multiple wall surfaces on which a carrier coating composition is applied and adhered, thereby serving as the substrate for the catalyst composition.

[0315] The ceramic substrate can be made of any suitable refractory material, such as cordierite, cordierite-α-alumina, aluminum titanate, silicon titanate, silicon carbide, silicon nitride, zircon mullite, spodumene, alumina-silica-magnesium oxide, zirconium silicate, sillimanite, magnesium silicate, zircon, selenite, α-alumina, aluminosilicate, etc.

[0316] The substrate can also be metallic, comprising one or more metals or metal alloys. Metallic substrates can include any metallic substrate, such as those with openings or "punch-outs" in the channel walls. Metallic substrates can be used in various shapes (e.g., granules, corrugated sheets, or integral foam). Specific examples of metallic substrates include, but are not limited to, heat-resistant base metal alloys, particularly those in which iron is a basic or major component. Such alloys may contain one or more of nickel, chromium, and aluminum, and the total amount of these metals may advantageously account for at least about 15% by weight (weight percentage) of the alloy, for example, about 10% to about 25% by weight of chromium, about 1% to about 8% by weight of aluminum, and 0% to about 20% by weight of nickel, based on the weight of the substrate in each case. Examples of metallic substrates include, but are not limited to, substrates having straight channels; substrates having blades projecting along the axial channel to interrupt airflow and open communication between channels; and substrates with blades and holes to enhance gas transport between channels, allowing radial gas transport in the bulk. Specifically, in some embodiments, a metal substrate is advantageously used in a tightly coupled position, thereby allowing the substrate to be heated rapidly, and correspondingly, the catalyst composition coated therein (e.g., an oxidation catalyst composition) is heated rapidly.

[0317] Any suitable substrate for the catalytic articles disclosed herein can be used, such as a monolithic substrate having fine, parallel airflow channels extending through the substrate from an inlet or outlet face, such that the channels are open to fluid flowing through the substrate (“flow-through substrate”). Another suitable substrate is of the type having a plurality of fine, substantially parallel airflow channels extending along the longitudinal axis of the substrate, wherein typically each channel is blocked at one end of the substrate body, with alternating channels blocked at opposite end faces (“wall-flow filter”). Flow-through and wall-flow substrates are also taught, for example, in International Application Publication No. WO2016 / 070090, which is incorporated herein by reference in its entirety.

[0318] In some embodiments, the catalyst substrate includes a honeycomb substrate in the form of a wall-flow filter or a flow-through substrate. In some embodiments, the substrate is a wall-flow filter. Flow-through substrates and wall-flow filters will be discussed further below.

[0319] Flow-through substrate

[0320] In some embodiments, the substrate is a flow-through substrate (e.g., a monolithic substrate, comprising a flow-through honeycomb monolithic substrate). The flow-through substrate has narrow, parallel airflow channels extending from an inlet end to an outlet end of the substrate, such that the channels are open to fluid flow. The channels, following a substantially straight path from their fluid inlet to their fluid outlet, are defined by walls on which a catalytic coating is disposed, allowing the gas flowing through the channels to contact the catalytic material. The flow channels of the flow-through substrate are thin-walled channels that can have any suitable cross-sectional shape and size, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, elliptical, circular, etc. As described above, the flow-through substrate can be ceramic or metallic.

[0321] Flow-through substrates can, for example, have approximately 50 inches. 3 Approximately 1200 inches 3 The volume, approximately 60 cells / square inch (cpsi) to approximately 500 cpsi or up to approximately 900 cpsi (inlet opening), such as approximately 200 to approximately 400 cpsi and a wall thickness of approximately 50 to approximately 200 micrometers or approximately 400 micrometers. Figure 1A and 1B An exemplary substrate 2 is shown in the form of a flowable substrate coated with a catalyst composition as described herein. Reference Figure 1A The exemplary substrate 2 has a cylindrical shape and a cylindrical outer surface 4, an upstream end face 6, and a corresponding downstream end face 8, the downstream end face being identical to end face 6. The substrate 2 has a plurality of parallel fine gas flow channels 10 formed therein. Figure 1B As shown, the flow channel 10 is formed by the wall 12 and extends from the upstream end face 6 through the carrier 2 to the downstream end face 8. The channel 10 is unobstructed, thus allowing fluid, such as airflow, to flow longitudinally through its airflow channel 10 across the carrier 2. As in Figure 1B As can be more readily seen, the dimensions of the wall 12 are set and configured such that the airflow channel 10 has a substantially regular polygonal shape. As shown, the catalyst composition can be applied in multiple different layers if desired. In the illustrated embodiment, the catalyst composition consists of both a discrete underlayer 14 adhered to the wall 12 of the carrier member and a second discrete top layer 16 coated on the underlayer 14. This disclosure can be practiced with one or more (e.g., two, three, or four or more) catalyst composition layers and is not limited thereto. Figure 1B The two-layer implementation is shown. Further coating configurations are disclosed below.

[0322] Wall-flow filter substrate

[0323] In some implementations, the substrate is a wall-flow filter, which typically has multiple thin, substantially parallel airflow channels extending along the longitudinal axis of the substrate. Typically, each channel is blocked at one end of the substrate body, with alternating channels blocked at opposite end faces. Such integral wall-flow filter substrates can contain up to about 900 channels (or “pores”) per square inch of cross-section, although much fewer channels can be used. For example, the substrate can have about 7 to 600 pores per square inch, more typically about 100 to 400 pores per square inch (“cpsi”). The pores can have rectangular, square, circular, elliptical, triangular, hexagonal, or other polygonal cross-sections.

[0324] Figure 2 The image shows a cross-sectional view of a substrate section of a monolithic wall-flow filter, illustrating alternating blocked and open channels (cells). Blocked or shut-off ends 100 alternate with open channels 101, each opposite end being open and blocked respectively. The filter has an inlet end 102 and an outlet end 103. Arrows passing through porous cell walls 104 indicate exhaust gas flow entering the open cell end, diffusing through the porous cell walls 104, and exiting the open outlet cell end. The shut-off end 100 prevents gas flow and promotes diffusion through the cell walls. Each cell wall will have an inlet side 104a and an outlet side 104b. The channels are surrounded by the cell walls.

[0325] The substrate of wall-flow filter products can have, for example, about 50 cm. 3 Approximately 100cm 3 Approximately 200cm 3 Approximately 300cm 3 Approximately 400cm 3 Approximately 500cm 3 Approximately 600cm 3 Approximately 700cm 3 Approximately 800cm 3 Approximately 900cm 3 or about 1000cm 3 Approximately 1500cm 3 Approximately 2000cm 3 Approximately 2500cm 3 Approximately 3000cm 3 Approximately 3500cm 3 Approximately 4000cm 3 Approximately 4500cm 3 or about 5000cm 3 The volume. The wall thickness of the substrate for wall flow filters is typically from about 50 micrometers to about 2000 micrometers, for example, from about 50 micrometers to about 450 micrometers or from about 150 micrometers to about 400 micrometers.

[0326] The walls of wall-flow filters are porous and typically have a wall porosity of at least about 50% or at least about 60% before the application of the functional coating, with an average pore size of at least about 5 micrometers. For example, in some embodiments, the wall-flow filter article substrate will have a porosity of ≥50%, ≥60%, ≥65%, or ≥70%. For example, before the application of the catalytic coating, the wall-flow filter article substrate will have a wall porosity of about 50%, about 60%, about 65%, or about 70% to about 75%, about 80%, or about 85%, and an average pore size of about 5 micrometers, about 10 micrometers, about 20 micrometers, about 30 micrometers, about 40 micrometers, or about 50 micrometers to about 60 micrometers, about 70 micrometers, about 80 micrometers, about 90 micrometers, or about 100 micrometers.

[0327] As used herein, the terms "wall porosity" and "substrate porosity" mean the same thing and are interchangeable. Porosity is the ratio of pore volume to the total volume of the substrate. Pore size can be determined according to the ISO 15901-2 (static volume) procedure for nitrogen pore size analysis. Nitrogen pore size can be determined on a Micromeritics TRISTAR 3000 series instrument. Nitrogen pore size can be determined using BJH (Barrett-Joyner-Halenda) calculations and 33 desorption points. In some embodiments, useful wall-flow filters have high porosity, allowing for high loadings of the catalyst composition during operation without generating excessive back pressure.

[0328] Coating composition and formulation

[0329] In order to produce the catalytic articles of this disclosure, a substrate as described herein is contacted with an oxidation catalyst composition as disclosed herein to provide a coating (i.e., a slurry comprising particles of the catalyst composition is disposed on the substrate). The coating of the oxidation catalyst composition on the substrate is referred to herein, for example, as a “catalytic coating composition” or “catalytic coating.” As used herein, the terms “catalytic composition” and “catalytic coating composition” are synonymous.

[0330] The oxidation catalyst compositions disclosed herein can be prepared using binders, such as ZrO2 binders derived from suitable precursors like zirconium oxyacetate or any other suitable zirconium precursor like zirconium oxynitrate. Zirconium acetate binders provide a uniform and intact coating after thermal aging, such as when the catalyst is exposed to high temperatures of at least about 600°C, for example about 800°C, and an environment with about 5% or more of water vapor. Other potentially suitable binders include, but are not limited to, alumina and silica. Alumina binders include alumina, aluminum hydroxide, and alumina hydroxyaluminate. Colloidal forms of aluminum salts and alumina can also be used. Silica binders include various forms of SiO2, including silicates and colloidal silica. Binder compositions can include any combination of zirconium oxide, alumina, and silica. Other exemplary binders include, but are not limited to, boehmite, γ-alumina, or δ / θ alumina, and silica sol. When present, the binder is typically used in an amount of about 1% to 5% by weight of the total carrier coating loading. Alternatively, the binder can be zirconia-based or silica-based, such as zirconium acetate, zirconia sol, or silica sol. When present, alumina binders are typically used at approximately 0.05 g / in. 3 Approximately 1g / in 3 The amount used. In some implementations, the binder is aluminum oxide.

[0331] The catalytic coating of the present invention may include one or more coatings, wherein at least one layer comprises the (oxidation) catalyst composition of the present invention. The catalytic coating of the present invention may include a single layer or multiple coatings. The catalytic coating may include one or more thin adhesive coatings disposed on and adhered to at least a portion of a substrate. The entire coating comprises a single “coating”.

[0332] In some embodiments, the catalytic article of the present invention may comprise the use of one or more catalyst layers and combinations thereof. The catalytic material may be present only on the inlet side of the substrate wall, only on the outlet side, on both the inlet and outlet sides, or the wall itself may be wholly or partially composed of the catalytic material. The catalytic coating may be on the surface of the substrate wall and / or in the pores of the substrate wall, i.e., in the substrate wall and / or on the substrate wall. Therefore, the phrase "catalytic coating disposed on a substrate" refers to any surface, such as on the wall surface and / or on the pore surface.

[0333] The catalyst compositions of the present invention can generally be applied in the form of a carrier coating containing a carrier material having a catalytically active substance thereon. The carrier coating is formed by preparing a slurry containing a specified solid content (e.g., about 10% to about 60% by weight) of a carrier in a liquid medium, then applying the slurry to a substrate and drying and calcining it to provide a coating. If multiple coatings are applied, the substrate is dried and calcined after each layer is applied and / or after applying a large number of desired layers. In one or more embodiments, one or more catalytic materials are applied as a carrier coating to the substrate. A binder may also be used as described above.

[0334] For the purpose of coating catalyst substrates such as honeycomb substrates, the above-described catalyst compositions are typically mixed independently with water to form a slurry. In addition to catalyst particles, the slurry may optionally contain binders (e.g., alumina, silica), water-soluble or water-dispersible stabilizers, accelerators, associative thickeners, and / or surfactants (including anionic, cationic, nonionic, or amphoteric surfactants). The typical pH range of the slurry is from about 3 to about 6. Acidic or alkaline substances may be added to the slurry to adjust the pH accordingly. For example, in some embodiments, the pH of the slurry is adjusted by adding an aqueous solution of ammonium hydroxide or nitric acid.

[0335] The slurry can be ground to enhance particle mixing and the formation of homogeneous materials. Grinding can be performed in a ball mill, continuous mill, or other similar equipment, and the solids content of the slurry can be, for example, about 20-60% by weight, more specifically about 20-40% by weight. In one embodiment, the ground slurry is characterized by D... 90 The particle size is from about 10 micrometers to about 40 micrometers, for example from about 10 micrometers to about 30 micrometers, for example from about 10 micrometers to about 15 micrometers.

[0336] The slurry is then coated onto the catalyst substrate using any carrier coating technique known in the art. In some embodiments, the substrate is dipped into the slurry once or multiple times, or otherwise coated with the slurry. The coated substrate is then dried at an elevated temperature (e.g., 100-150°C) for a period of time (e.g., 10 minutes to 3 hours), and then calcined, for example, at 400-600°C, typically for about 10 minutes to about 3 hours. After drying and calcination, the final carrier coating can be considered substantially solvent-free.

[0337] After calcination, the catalyst loading obtained by the above-described carrier coating technology can be determined by calculating the difference in weight between the coated and uncoated substrates. As will be apparent to those skilled in the art, the catalyst loading can be modified by altering the rheological properties of the slurry. Furthermore, the coating / drying / calcination process for producing the carrier coating can be repeated as needed to construct the coating to the desired loading level or thickness, meaning that more than one carrier coating may be applied.

[0338] In some embodiments, the catalytic article includes a catalytic coating disposed on at least a portion of a substrate, the catalytic coating comprising a first carrier coating and a second carrier coating. In some embodiments, the first carrier coating comprises a manganese component and a first refractory metal oxide carrier material, each as described herein. In some embodiments, the manganese component is supported on the first refractory metal oxide carrier material in the form of manganese oxide or a mixed oxide.

[0339] In some embodiments, the second carrier coating comprises a platinum group metal (PGM) component (including palladium) and a second refractory metal oxide carrier material, each as described herein. In some embodiments, the PGM component is loaded onto the second refractory metal oxide carrier material.

[0340] A carrier coating can be applied so that different coatings can directly contact the substrate. Alternatively, one or more "undercoating layers" may be present such that at least a portion of the catalyst or adsorbent coating or multiple coatings does not directly contact the substrate (but rather contacts the undercoating layer). One or more "outer coating layers" may also be present such that at least a portion of the coating or multiple coatings is not directly exposed to the gas stream or atmosphere (but rather contacts the outer coating layer). The catalyst composition of the present invention may be in a base layer above the substrate.

[0341] Alternatively, the catalyst composition of the present invention can be in a top coating layer above a base coating layer. The catalyst composition can be present in both a top layer and a bottom layer. Either layer can extend the entire axial length of the substrate; for example, the bottom layer can extend the entire axial length of the substrate, and the top layer can extend the entire axial length of the substrate over the bottom layer. Each of the top and bottom layers can extend from either an inlet end or an outlet end.

[0342] For example, both the base coat and the top coat can extend from the same end of the substrate, wherein the top coat partially or completely covers the base coat, and wherein the base coat extends part or all of the length of the substrate, and wherein the top coat extends part or all of the length of the substrate. Alternatively, the top coat can cover a portion of the base coat. For example, the base coat can extend the entire length of the substrate, and the top coat can extend from the inlet or outlet end by about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, or about 90% of the substrate length.

[0343] Alternatively, the bottom layer may extend from the inlet or outlet end to approximately 10%, 15%, 25%, 30%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 95% of the substrate length, and the top layer may extend from the inlet or outlet end to approximately 10%, 15%, 25%, 30%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 95% of the substrate length, wherein at least a portion of the top layer covers the bottom layer. This "covered" area may, for example, extend from approximately 5% of the substrate length to approximately 80%, such as approximately 5%, 10%, 20%, 30%, 40%, 50%, 60%, 60%, or 70% of the substrate length.

[0344] The topcoat and / or basecoat may be in direct contact with the substrate. Alternatively, one or more "basecoats" may be present such that at least a portion of the topcoat and / or basecoat is not in direct contact with the substrate (but is in direct contact with the basecoat). One or more "outer coatings" may also be present such that at least a portion of the topcoat and / or basecoat is not directly exposed to a gas stream or atmosphere (but is in contact with the outer coating). The basecoat is a layer "below" the coating, the outer coating is a layer "above" the coating, and the intermediate layer is a layer "between" the two coatings.

[0345] The top and bottom coatings can be in direct contact with each other without any intermediate layer. Alternatively, the different coatings may not be in direct contact, with a "gap" between the two zones. An intermediate layer (if present) can prevent direct contact between the top and bottom layers. An intermediate layer can partially prevent direct contact between the top and bottom layers, thereby allowing partial direct contact between the top and bottom layers. The intermediate layer, bottom coating, and outer coating may contain one or more catalysts or may not contain a catalyst. The catalytic coating of the present invention may comprise more than one identical layer, for example, more than one layer containing the same catalyst composition.

[0346] The catalytic coating can advantageously be “partitioned,” comprising partitioned catalytic layers, i.e., wherein the catalytic coating contains different compositions along the axial length of the substrate. This can also be described as “lateral partitioning.” For example, a layer may extend from the inlet end to the outlet end, extending approximately 10%, approximately 20%, approximately 30%, approximately 40%, approximately 50%, approximately 60%, approximately 70%, approximately 80%, or approximately 90% of the substrate length. Another layer may extend from the outlet end to the inlet end, extending approximately 10%, approximately 20%, approximately 30%, approximately 40%, approximately 50%, approximately 60%, approximately 70%, approximately 80%, or approximately 90% of the substrate length. Different coatings may be adjacent to each other and not overlap. Alternatively, different layers may partially overlap each other, thereby providing a third “intermediate” zone. The intermediate zone can extend from approximately 5% of the substrate length to approximately 80%, for example, approximately 5%, approximately 10%, approximately 20%, approximately 30%, approximately 40%, approximately 50%, approximately 60%, or approximately 70% of the substrate length.

[0347] Different layers may each extend the entire length of the substrate, or may each extend a portion of the substrate length, and may partially or completely cover or pad each other. Each different layer may extend from either the inlet or outlet end. Different catalytic compositions may be present in each individual coating. The catalytic coating of the present invention may comprise more than one identical layer.

[0348] The regions disclosed herein are defined by the relationship between the coatings. For different coatings, there are many possible partitioning configurations. For example, there may be upstream and downstream regions, upstream, intermediate, and downstream regions, or four distinct regions, etc. When two layers are adjacent and do not overlap, there are upstream and downstream regions. When two layers overlap to some extent, there are upstream, downstream, and intermediate regions. For example, when the coating extends the entire length of the substrate and different coatings extend a certain length from the exit end and cover a portion of the first coating, upstream and downstream regions exist.

[0349] In some embodiments, the first and second coatings may overlap, with the first coating on top of the second coating or vice versa (i.e., top / bottom coating), for example, where the first coating extends from the inlet to the outlet and the second coating extends from the outlet to the inlet. In this case, the catalytic coating will include an upstream region, an intermediate (cover) region, and a downstream region. The first and / or second coatings may be synonymous with the aforementioned top and / or bottom layers.

[0350] In some implementations, the first coating may extend from the inlet end to the outlet end and the second coating may extend from the outlet end to the inlet end, wherein the layers do not overlap each other, for example, they may be adjacent to each other.

[0351] Figure 3A , 3BFigures 3C and 3C show some possible coating configurations with two coatings, at least one of which contains a catalyst composition as disclosed herein. A substrate wall 200 is shown with coatings 201 (top coating) and 202 (bottom coating) disposed thereon. This is a simplified illustration; in the case of a porous wall flow substrate, the pores and the coatings adhered to the pore walls are not shown, and the blocked ends are not shown. Figure 3A In the middle, coatings 201 and 202 each extend the entire length of the substrate, with the top layer 201 covering the bottom layer 202. Figure 3A The substrate does not have a partitioned coating configuration. Figure 3B In the middle layer, the base coating 202 extends approximately 50% of the substrate length from the outlet, and the top coating 201 extends more than 50% of the length from the inlet and covers a portion of the layer 202, thereby providing an upstream region 203, an intermediate cover region 205, and a downstream region 204. Figure 3C In the middle, coating 202 extends from the outlet for about 50% of the length of the substrate, and coating 201 extends from the inlet for more than 50% of the length and covers a portion of coating 202, thereby providing an upstream region 203, an intermediate coverage region 205 and a downstream region 204. Figure 3A , 3B 3C can be used to demonstrate coating compositions on wall-flow or flow-through substrates.

[0352] In some implementations, the first carrier coating and the second carrier coating are substantially copper-free.

[0353] In some embodiments, the first carrier coating is directly applied to the substrate, and the second carrier coating is applied to at least a portion of the first carrier coating.

[0354] In some embodiments, the catalyst article has a partitioned configuration, wherein a first support coating is directly applied to a substrate extending from the outlet end to approximately 20% to approximately 100% of the total length; and a second support coating is applied to a substrate extending from the inlet end to approximately 20% to approximately 100% of the total length. In some embodiments, the catalyst article has a partitioned configuration, wherein a second support coating is directly applied to a substrate extending from the outlet end to approximately 20% to approximately 100% of the total length; and a first support coating is applied to a substrate extending from the inlet end to approximately 20% to approximately 100% of the total length.

[0355] The (oxidative) catalytic coating of the present invention, and any area, layer, or portion thereof, is, for example, about 0.3 g / in based on the volume of the substrate. 3 Approximately 6.0 g / in 3Or approximately 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 g / in 3 Approximately 1.5 g / in 3 Approximately 2.0g / in 3 Approximately 2.5g / in 3 Approximately 3.0g / in 3 Approximately 3.5g / in 3 Approximately 4.0g / in 3 Approximately 4.5g / in 3 Approximately 5.0g / in 3 or approximately 5.5g / in 3 The loading (concentration) of the coating is present on the substrate. This refers to the dry solids weight per unit volume of the substrate, such as per unit volume of a single honeycomb cell. The concentration is based on the cross-section of the substrate or on the entire substrate. In some embodiments, the top coating is present with a lower loading than the bottom coating.

[0356] The loading of the PGM component (e.g., palladium and optionally platinum) of the disclosed oxidation catalyst composition onto the substrate can be approximately 2 g / ft based on the substrate volume. 3 Approximately 5g / ft 3 or about 10g / ft 3 Approximately 250g / ft 3 For example, about 20g / ft 3 Approximately 30g / ft 3 Approximately 40g / ft 3 Approximately 50g / ft 3 or about 60g / ft 3 Approximately 100g / ft 3 Approximately 150g / ft 3 or about 200g / ft 3 Approximately 210g / ft 3 Approximately 220g / ft 3 Approximately 230g / ft 3 Approximately 240g / ft 3 or approximately 250g / ft 3 Within the range. PGM is present in the catalyst layer, for example, in amounts of about 0.1 wt%, about 0.5 wt%, about 1.0 wt%, about 1.5 wt%, or about 2.0 wt%, to about 3 wt%, about 5 wt%, about 7 wt%, about 9 wt%, about 10 wt%, about 12 wt%, or about 15 wt%, based on the weight of the layer.

[0357] Catalyst activity

[0358] In some embodiments, the levels of hydrocarbons (e.g., methane) or CO in the exhaust gas are reduced compared to the levels of hydrocarbons or CO present in the exhaust gas prior to contact with the catalyst article. In some embodiments, the efficiency of the reduction in HC and / or CO levels is measured as conversion efficiency. In some embodiments, conversion efficiency is expressed as the ignition temperature (i.e., T0). 50 or T 70 It is measured using a function of ). T 50 or T 70 Ignition temperature is the temperature at which a catalyst composition can convert 50% or 70% of hydrocarbons or carbon monoxide into carbon dioxide and water, respectively. Generally, for any given catalyst composition, the lower the measured ignition temperature, the more efficient the catalyst composition is in catalytic reactions such as hydrocarbon conversion.

[0359] In some implementations, the NO2 level in the exhaust gas is increased compared to the nitrogen dioxide (NO2) level present in the exhaust gas prior to contact with the catalyst product. This increase in NO2 content generally benefits the catalytic activity of downstream SCR catalysts.

[0360] Exhaust gas treatment system

[0361] In another aspect, a system is provided for treating exhaust gas from an internal combustion engine, the exhaust gas containing hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). x The system includes a diesel oxidation catalyst (D°C) article positioned downstream of an internal combustion engine as described herein. The engine may be, for example, a diesel engine operating under combustion conditions where air exceeds the air required for stoichiometric combustion, i.e., lean-burn conditions. In other embodiments, the engine may be a gasoline engine (e.g., a lean-burn gasoline engine) or an engine associated with a stationary source (e.g., a generator or pumping station).

[0362] Exhaust gas treatment systems typically contain more than one catalyst, located downstream of the engine and in fluid communication with the exhaust gas flow. The system may include, for example, oxidation catalysts (e.g., D°C) disclosed herein, selective catalytic reduction (SCR) catalysts, and one or more components including a reductant injector, a particulate filter, an ammonia oxidation catalyst (AMOx), or a dilute NO₂. xArticles containing a reducing agent (LNT). Articles containing a reducing agent syringe are reducing articles. Reduction systems include reducing agent syringes and / or pumps and / or reservoirs, etc. The processing system of the present invention may further include a dust filter and / or an ammonia oxidation catalyst. The dust filter may be uncatalyzed or may be catalyzed (CSF), such as the CSF disclosed herein. For example, from upstream to downstream, the processing system of the present invention may include: articles containing D°C, CSF, urea syringes, SCR articles, and articles containing AMOx. Dilute NO may also be included. x LNT (Low-Nutrient Toxin)

[0363] The relative positions of the various catalytic components present in the emission treatment system can vary. In the exhaust gas treatment system and method of the present invention, the exhaust gas stream is contained into the product or treatment system by entering at an upstream end and exiting at a downstream end. The inlet end of the substrate or product is synonymous with the "upstream" end or "front" end. The outlet end is synonymous with the "downstream" end or "rear" end. The treatment system is typically located downstream of the internal combustion engine and is in fluid communication with the internal combustion engine.

[0364] exist Figure 4 An exemplary emission treatment system is illustrated, depicting a schematic diagram of emission treatment system 20. As shown, the emission treatment system may include multiple catalyst components connected in series downstream of engine 22 (e.g., a lean-burn engine). At least one catalyst component may include an oxidation catalyst composition as described herein (e.g., D°C, CSF, or both). The oxidation catalyst composition of this disclosure may be combined with a number of other catalyst materials and may be placed in different locations compared to other catalyst materials. Figure 4 Five catalyst components 24, 26, 28, 30, and 32 are shown in series; however, the total number of catalyst components can vary, and the five components are just one example.

[0365] Non-limiting, Table 1 shows various exhaust gas treatment system configurations of one or more embodiments of this disclosure. Note that each catalyst is connected to the next catalyst via an exhaust gas conduit, such that the engine is upstream of catalyst A, catalyst A is upstream of catalyst B, catalyst B is upstream of catalyst C, catalyst C is upstream of catalyst D, and catalyst D is upstream of catalyst E (if present). References to component AE in the table may be related to... Figure 5 Cross-referencing of the same name in the same file.

[0366] The D℃ catalysts listed in Table 1 can be any catalyst commonly used as a diesel oxidation catalyst, which effectively converts CO and HC into CO2 and H2O.

[0367] The ccD℃ catalysts listed in Table 1 can be any catalyst conventionally used as a diesel oxidation catalyst. They are positioned in a close coupling location near the engine block to convert CO and HC into CO2 and H2O, and generate heat through exothermic reaction, thereby effectively heating the downstream catalyst.

[0368] The D℃ (BMO) catalysts listed in Table 1 can be any catalyst conventionally used as a diesel oxidation catalyst, which converts CO and HC to CO2 and H2O and does not contain platinum group metals (PGMs). BMO stands for base metal oxide as defined herein. The combination of component A (D℃) + component B (D℃ (BMO)) indicates an arrangement of component A located upstream of component B, either in the same tank or in two separate tanks.

[0369] The D℃+BMO catalyst listed in Table 1 is a diesel oxidation catalyst that contains PGM and BMO components on the same substrate.

[0370] The LNT catalysts listed in Table 1 can be conventionally used for NO production. x Any catalyst that acts as a trap, and typically contains NO. x The adsorbent composition comprises base metal oxides (BaO, MgO, CeO2, etc.) and platinum group metals (e.g., Pt and Rh) for catalyzing the oxidation and reduction of NO.

[0371] The LT-NA catalysts listed in Table 1 can be those capable of adsorbing NO at low temperatures (<250℃). x (e.g., NO or NO2) and any catalyst that releases it into the gas stream at high temperatures (>250°C). The released NO x Typically, N2 and H2O are converted via downstream SCR or SCRoF catalysts. LT-NA catalysts typically comprise Pd-promoted zeolites or Pd-promoted refractory metal oxides.

[0372] The reference to SCR in the table refers to the SCR catalyst. Mentions of SCRof (or SCR on a filter) refer to particulate or dust filters (e.g., wall-flow filters) that may contain an SCR catalyst composition.

[0373] The reference to AMOx in the table refers to an ammonia oxidation catalyst, which may be provided downstream of the catalyst in one or more embodiments of this disclosure to remove any slipping ammonia from an exhaust gas treatment system. In some embodiments, the AMOx catalyst may contain a PGM component. In some embodiments, the AMOx catalyst may comprise a base coating and a top coating, wherein the base coating contains PGM and the top coating has SCR functionality.

[0374] As those skilled in the art will recognize, in the configurations listed in Table 1, any one or more of components A, B, C, D, or E can be disposed on a particulate filter (such as a wall-flow filter) or on a flow-through honeycomb substrate. In some embodiments, the engine exhaust system includes one or more catalyst compositions mounted near the engine (in an immediately coupled location, CC) and additional catalyst compositions mounted under the vehicle body (in an underfloor location, UF). In some embodiments, the exhaust treatment system may also include a urea injection unit.

[0375] Table 1. Possible exhaust gas treatment system configurations

[0376]

[0377] Methods for treating waste gas flow

[0378] The present disclosure relates to a method for treating engine exhaust gas containing hydrocarbons and / or carbon monoxide and / or NO. x The method includes contacting the exhaust gas stream with the catalyst of this disclosure or the emission treatment system of this disclosure.

[0379] Typically, hydrocarbons (HC) and carbon monoxide (CO) present in the exhaust gas of any engine can be converted into carbon dioxide and water. Hydrocarbons typically present in engine exhaust gas include C1-C6 hydrocarbons (i.e., lower hydrocarbons) such as methane, but higher hydrocarbons (greater than C6) can also be detected. In some embodiments, the method includes contacting the gas stream with the catalyst or exhaust gas treatment system of this disclosure at a temperature sufficient to reduce the CO and / or HC levels in the gas stream for a time sufficient to reduce the CO and / or HC levels in the gas stream.

[0380] Typically, any NO, such as NO, present in engine exhaust gas... x The substance can be converted (oxidized) into NO2. In some embodiments, the method includes contacting the gas stream with the catalyst or exhaust gas treatment system of this disclosure at a temperature sufficient to oxidize at least a portion of the NO present in the gas stream to NO2 for a time sufficient to oxidize at least a portion of the NO present in the gas stream to NO2.

[0381] The articles, systems, and methods of the present invention are suitable for treating exhaust gas streams from mobile emission sources (e.g., trucks and automobiles). The articles, systems, and methods of the present invention are also suitable for treating exhaust gas streams from stationary sources (e.g., power plants).

[0382] It will be apparent to those skilled in the art that suitable modifications and adaptations can be made to the compositions, methods, and applications described herein without departing from the scope of any embodiments or aspects thereof. The compositions and methods provided are exemplary and are not intended to limit the scope of the claimed embodiments. All the various embodiments, aspects, and options disclosed herein can be combined in all variations. The scope of the compositions, formulations, methods, and processes described herein includes all actual or potential combinations of the embodiments, aspects, options, examples, and preferences herein. All patents and publications referenced herein are incorporated herein by reference for their specific teachings as mentioned, unless otherwise specifically stated as incorporated herein. Example

[0383] This disclosure is further illustrated by the following examples, which are provided to illustrate the subject matter and should not be construed as limiting it. Unless otherwise indicated, all parts and percentages are by weight, and all weight percentages are expressed on a dry weight basis, meaning excluding water content, unless otherwise specified.

[0384] Example 1A: Pd supported on a lanthanum-containing zirconium oxide support

[0385] A sample containing 2% palladium loaded on lanthanum-containing zirconium oxide was prepared. A certain amount of palladium nitrate solution was impregnated onto a lanthanum-containing zirconium oxide support (containing approximately 9 wt% lanthanum oxide) to obtain a coated powder with 2 wt% Pd based on the total weight of the impregnated support. The Pd-impregnated support powder was added to deionized water (the solid content of the slurry was 30 wt%). The slurry was milled using a ball mill to a D0.05 level. 90 Particle size less than 15 μm. The ground slurry was dried at 120 °C with stirring and calcined in air at 590 °C for 2 hours. The calcined sample was cooled in air until it reached room temperature. The calcined powder was pulverized and sieved to a particle size range of 250-500 μm. The sieved powder was divided into two parts. The first part was evaluated as a fresh sample. The second part was aged in air at 800 °C with 10% steam for 16 hours to obtain an aged sample.

[0386] Example 1B: Pt and Pd supported on an alumina substrate

[0387] Platinum and palladium samples (2% of the total PGM weight) were prepared and loaded onto an alumina support. Platinum nitrate and palladium nitrate (Pt and Pd weight ratio of 2:1) were impregnated onto high-surface-area alumina (approximately 150 m²) according to a standard procedure. 2 / g). Add 2% PGM-impregnated alumina carrier powder to deionized water (slurry solids content 30% by weight). Grind the slurry to D using a ball mill. 90Particle size less than 15 μm. The ground slurry was dried at 120 °C with stirring and calcined in air at 590 °C for 2 hours. The calcined sample was cooled in air until it reached room temperature. The calcined powder was pulverized and sieved to a particle size range of 250-500 μm. The sieved powder was divided into two parts. The first part was evaluated as a fresh sample. The second part was aged in air at 800 °C with 10% steam for 16 hours to obtain an aged sample.

[0388] Example 2: Ce / Mn-doped alumina support

[0389] Base metal oxide materials are prepared by impregnating an alumina support with cerium nitrate and then drying it. As described in Examples 1A and 1B, the cerium-impregnated alumina support is then impregnated with manganese nitrate, dried, calcined, crushed, and sieved to provide Ce / Mn-doped alumina support material (particle size in the range of 250-500 μm) containing 10% cerium dioxide and 10% manganese oxide based on the weight of alumina, according to the total weight of the doped alumina support material. The sieved powder is divided into two fractions. The first fraction is evaluated as a fresh sample. The second fraction is aged in air at 800°C with 10% vapor for 16 hours to obtain an aged sample.

[0390] Example 3: Mn-doped lanthanum-containing zirconium oxide support

[0391] The base metal oxide material was prepared using the procedure of Example 2 by impregnating a lanthanum-containing zirconium oxide support (containing approximately 9 wt% lanthanum oxide), but replacing the alumina with lanthanum-zirconium oxide and removing the cerium nitrate. The powder obtained after calcination, calculated by oxide content and based on the total weight of the impregnated support, had a Mn content of approximately 10 wt%.

[0392] Example 4: Ce / Mn-doped lanthanum-containing zirconium oxide support

[0393] The base metal oxide material was prepared using the procedure of Example 3 by sequentially impregnating cerium nitrate and manganese nitrate onto a lanthanum-containing zirconium oxide support (containing approximately 9 wt% lanthanum oxide). The powder obtained after calcination, calculated by oxide content and based on the total weight of the impregnated support, had approximately 10 wt% Ce and 10 wt% Mn content.

[0394] Example 5: Cu / Mn-doped lanthanum-containing zirconium oxide support

[0395] The base metal oxide material was prepared using the procedure of Example 4 by sequentially impregnating copper nitrate and manganese nitrate onto a lanthanum-containing zirconium oxide support (containing approximately 9 wt% lanthanum oxide), but with copper nitrate instead of cerium nitrate. The powder obtained after calcination, calculated by oxide content and based on the total weight of the impregnated support, had approximately 10 wt% Cu and 10 wt% Mn content.

[0396] Example 6: Ce / Cu / Mn-doped lanthanum-containing zirconium oxide support

[0397] The base metal oxide material was prepared using the procedure of Example 5 by sequentially impregnating cerium nitrate, copper nitrate, and manganese nitrate onto a lanthanum-containing zirconium oxide support (containing approximately 9 wt% lanthanum oxide), but first impregnated with cerium nitrate. The powder obtained after calcination, calculated by oxide content and based on the total weight of the impregnated support, had approximately 10 wt% Ce, 10 wt% Cu, and 10 wt% Mn content.

[0398] Examples 7-12. Pd catalyst products

[0399] The catalyst products were prepared from the powders of Examples 1A and 2-6. To prepare the products, appropriate powder samples (fresh and aged) were loaded into separate test beds. The total volume of the test bed was 1 ml, with two equal sections: a bottom and a top, as shown. Figure 5 As shown. In each case, the top was filled with 2% Pd powder loaded on a La / Zr support as in Example 1A, and the bottom of the test stage was filled with a reference lanthanum-containing zirconium oxide support (Example 7), or a support from one of Examples 2-6 (Examples 8-12), mixed with an equal amount of corundum. The composition of the articles is summarized in Table 2.

[0400] Example 13. Reference Pt / Pd catalyst product

[0401] The catalyst product was prepared from the powder of Example 1B. To prepare the product, a suitable powder sample (fresh) was loaded into a test bed. The total volume of the test bed was 1 ml, with two equal parts: a bottom and a top, as shown. Figure 5 As shown. The top layer is filled with 2% Pt / Pd (2:1Pt / Pd) loaded on alumina as in Example 1B, and the bottom of the test stage is filled with a reference lanthanum-containing zirconium oxide support without additional dopants. The composition of the product is summarized in Table 2.

[0402] Example 14. Pt / Pd catalyst products

[0403] The catalyst product was prepared from the powder of Example 1B. To prepare the product, a suitable powder sample (fresh) was loaded into a test bed. The total volume of the test bed was 1 ml, with two equal parts: a bottom and a top, as shown. Figure 5 As shown. The top layer is filled with 2% Pt / Pd (2:1 Pt / Pd) loaded on alumina as in Example 1B, and the bottom of the test stage is filled with the Ce / Mn / La / ZrO2 support of Example 4. The composition of the product is summarized in Table 2.

[0404] Table 2. Layer composition of the articles in Examples 7-14

[0405]

[0406] Example 15: Reactor Ignition Test

[0407] Under steady-state conditions, hydrocarbon (HC) and carbon monoxide (CO) ignition of the products from Examples 7-12 (fresh and aged) and 13 and 14 (fresh) were evaluated in a reactor. The gas feed consisted of 1250 ppm CO, 100 ppm ethylene (as C1), 300 ppm a 2:1 decane-toluene mixture (as C1), 180 ppm nitric oxide, 10% carbon dioxide, 10% water vapor, and 10% oxygen (O2). A 3-minute gradual equilibration time was used for steady-state ignition, and a 30-second sampling time was used for temperatures ranging from 135 to 400°C. The first ignition test was considered as degreening of the sample, and then the second ignition test was recorded.

[0408] As a performance indicator for both fresh and aged catalysts, CO(T) is determined. 50 _CO) and HC(T) 70 _HC) ignition temperature and NO2 yield. CO(T) 50 _CO) and HC(T) 70 The ignition temperatures of HC are provided in Table 3, which shows that all articles of the present invention exhibit improved HC conversion for both fresh and aged samples.

[0409] While Ce-Mn impregnation on an alumina support (Example 8) provided improved HC performance compared to Example 7 (reference article), the use of a lanthanum-containing zirconium oxide support (Examples 9-12) instead of an alumina support, whether fresh or aged, further improved HC performance. Unwilling to be bound by theory, this demonstrates a Mn-Zr synergistic effect that favors improved HC performance. Surprisingly, the presence of cerium and copper (Example 12) increased the HC ignition temperature compared to samples with Cu and Mn, samples with Mn alone, or samples with Ce and Mn (Examples 11, 9, and 10, respectively).

[0410] Although the reference catalyst with a Pt / Pd impregnated alumina support (Example 13) provided improved HC / CO performance compared to Example 7 (reference product), the addition of cerium dioxide and manganese supported on a lanthanum-containing zirconium oxide support (Example 14) further unexpectedly improved the HC performance (Table 3).

[0411] Table 3. HC / CO ignition (L / O) temperature

[0412]

[0413] As a further performance measurement standard, NO2 yield was evaluated at an inlet temperature of 300°C. Data provided in Table 4 show that all products of the present invention, whether fresh or aged, provided significantly higher NO2 yields compared to the reference product (Example 7). The listed synergistic effect of Mn-Zr on HC ignition also contributes to improved NO2 yield. This increased NO2 yield is expected to have beneficial effects on downstream SCR catalysts, as shown in Table 4. Furthermore, this synergistic effect improves NO2 performance stability for aging, while Ce-Mn supported on alumina does not improve performance stability. Additionally, the addition of Cu to the Mn / La-Zr support (Examples 11 and 12) resulted in increased CO conversion, both fresh and aged. However, unexpectedly, the addition of Cu affected both HC conversion and NO2 yield compared to Examples 9 and 10.

[0414] Table 4. NO2 yield at 300℃

[0415]

[0416] As a further performance measurement standard for Examples 13 and 14, NO2 yield was evaluated at an inlet temperature of 225°C. Data provided in Table 5 show that the product of the present invention in Example 14, even with Pt / Pd supported on an alumina top layer, provides a significantly higher NO2 yield compared to the reference product (Example 13).

[0417] Table 5. NO2 yield at 225℃

[0418]

[0419] Example 16: Reactor ignition test using formaldehyde

[0420] Formaldehyde emissions from automobile exhaust are currently regulated in the United States. Therefore, the performance of the products of Examples 7-12 was evaluated according to the protocol of Example 15, but with formaldehyde (150 ppm) added to the feed gas. Shortly before the ignition test, the sample from Example 15 was cooled from a second L / O run under a N2 atmosphere. The data are provided in Table 6.

[0421] Table 6. HC / CO ignition (L / O) temperature and NO2 yield at 300℃

[0422]

[0423]

[0424] As shown in Table 6, a similar trend to that observed in Example 15 was observed; that is, all articles of the present invention, whether fresh or aged, showed improved HC conversion compared to the reference article (Example 7), and provided significantly higher NO2 yields. Adding Mn to the lanthanum-containing zirconium oxide support was beneficial to both HC conversion and NO2 yield.

[0425] Examples 16-17: Formaldehyde Oxidation Function Evaluation

[0426] The examples using powdered catalysts described above were also tested in a configuration where the feed gas passed through the catalyst from top to bottom, similar to the front and back zone configurations in a honeycomb-structured waste gas treatment system, with a carrier coating flowing around the perimeter of the channels. Since the back zone catalyst did not contain PGM, as shown in Examples 7-14, another set of experiments was conducted by blending PGM with the carrier, as shown in Tables 7, 8, and 9. The procedure for preparing this carrier is as follows: the obtained commercially available zirconia had a surface area of ​​approximately 100 m². 2 / g, zirconia was impregnated with palladium nitrate solution to obtain a carrier coating with a Pd concentration of approximately 0.67% on the carrier. After drying in an oven at 120°C for one hour, the Pd-impregnated powder was further impregnated with platinum-amine solution to obtain a 1% Pt / Pd carrier coating powder with a Pt / Pd ratio of 2 / 1. For La / ZrO2 (Example 16), the pre-prepared La / ZrO2 was commercially available and contained approximately 9% La loaded on ZrO2. The addition of Pt / Pd followed the same procedure as in Example 15. For Zr / Al2O3 (Example 17), a similar procedure to that in Example 15 was used, except that the carrier was aluminum oxide (alumina) with a surface area of ​​approximately 150 m². 2 / g. Zr was impregnated onto alumina in the form of a zirconium acetate solution to obtain a 30% Zr support. Throughout this set of experiments, 1% Pt / Pd (2 / 1) was consistently used because the Pt / Pd-containing catalyst provided a higher NO2 yield compared to the Pd-only catalyst (Table 5). Since ZrO2 was the dominant element in the support used in the previous set of experiments (Examples 7-14, powder form), this new set of experiments used zirconium oxide as a reference support in a 1”Dx3”L honeycomb structure (400 cpsi – cells / square inch). Formaldehyde conversion was the focus of this evaluation.

[0427] Table 7. Catalyst products: Pt / Pd supported on various supports

[0428]

[0429] Examples 18-22: Assessment of Mn content

[0430] Since Mn is the major element responsible for the observed improvement in HC conversion (see Examples 9 and 7), the effect of adding different amounts of Mn to the support was investigated, as shown in Tables 8 and 9. The addition of Mn was similar to that of Zr to an alumina support (Example 17), except that a manganese acetate solution was used instead of zirconium acetate (Examples 18-22). Five different supports, containing 5% Mn loaded on them, were investigated, as shown in Table 8.

[0431] Table 8. Catalyst product: 1% Pt / Pd, containing 5% Mn supported on various supports.

[0432]

[0433] To investigate whether increasing the amount of Mn loaded on the support affects the HC / CO and HCHO conversion rates, 25% Mn loaded on various supports was tested under the same L / O scheme as the 5% Mn sample, as shown in Table 9.

[0434] Table 9. Catalyst product: 1% Pt / Pd, containing 25% Mn supported on various supports.

[0435] 18 (Refer to E) <![CDATA[1% 2:1 Pt / Pd, containing 25% Mn, supported on ZrO2]]> 19 (Refer to F) <![CDATA[1% 2:1 Pt / Pd, containing 25% Mn, supported on La / ZrO2]]> 20 <![CDATA[1% 2:1 Pt / Pd, containing 25% Mn, supported on Zr / Al2O3]]> 21 <![CDATA[1% 2:1 Pt / Pd, containing 25% Mn, supported on La / Zr / Al2O3]]> 22 <![CDATA[1% 2:1 Pt / Pd, containing 25% Mn, supported on Zr / CeO2]]>

[0436] Steady-state ignition (L / O) tests in the core reactor test unit were conducted according to the following protocol: CO: 1000 ppm, HCHO: 25 ppm, C2H4 (as C1): 100 ppm, C 10 H 22 / C7H8 (2.5:1 ratio, based on C1): 190ppm, NO: 180ppm, O2: 10%, CO2: 10%, H2O: 10%; Heating rate: 20°C / min, space velocity: 50,000 1 / h. All core samples were aged in a tube furnace for 16 hours at 800°C with 10% H2O vapor in the air.

[0437] For the samples listed in Table 7 (Examples 15-17), the ignition results of HCHO, CO, and HC (excluding HCHO) at 200°C and the NO2 / NOx performance are listed in Table 10. Since the focus of this evaluation is on HCHO conversion, the conversion of the remaining HC (excluding HCHO) is listed here to show the effect of HCHO on the L / O of other HC components.

[0438] Table 10. Catalyst products: Pt / Pd supported on various supports

[0439]

[0440] Example 17 (1% Pt / Pd, supported on Zr / Al2O3) provides better CO / HC and HCHO L / O, as well as higher NO2 / NO at 200°C. x The performance values ​​indicate that Zr itself may not be the optimal support, and Zr deposited on a high surface area alumina support provides better overall performance. It can also be noted that the Zr support provides HC... T80 The L / O temperature cannot be lower than 300℃, which is the upper limit of the L / O scheme.

[0441] The L / O results after adding 5% Mn to various supports, as shown in Table 11, indicate that Mn is indeed an enhancer of overall performance compared to supports without Mn (except for the NO2 / NO2 ratio at 200°C). x Beyond performance (Table 10). However, 图6 A comparison of the NO2 / NOx L / O performance of these supports shows that the sample containing 1% 2:1 Pt / Pd and 5% Mn loaded on Zr / Al2O3 provides the best NO2 / NOx L / O performance at T>210℃. x Performance. Furthermore, all samples with non-zirconium supports (Examples 20, 21, and 22) provided better HC L / O performance. Except for La / Zr (Reference D), all supports of the present invention outperformed zirconium-only supports in HCHO L / O conversion. While for Zr / Al2O 3 5% Mn HC L / O The improvement exceeded 20°C, but it could not increase the HC value of the zirconia-based support. T80 L / O is less than 300℃, as shown in Table 11.

[0442] Table 11. Catalyst products: Pt / Pd supported on various supports containing 5% Mn

[0443]

[0444]

[0445] As shown in Table 12, at higher Mn loadings (25% Mn loaded on the support), the HCHO L / O ratio improved for all supports, while the improvement in CO L / O was smaller. An improvement in HC L / O was observed for Pt / Pd supported on Zr / CeO2 containing 25% Mn. Compared to the 5% Mn samples (Table 11), a greater improvement in HC L / O was observed for the Zr / CeO2 support than 25%, while the additional 20% Mn loaded on the La / Zr / Al2O3 support did not improve HC L / O. T80L / O indicates that the Mn / La ratio may have different optimal values ​​for HCHO and HC conversion. However, the greatest benefit of using the support in Example 21 is the increased NO2 / NO ratio at low temperatures. x Value, such as Figure 7 As shown in Table 12. Therefore, the Mn loaded on the Zr / CeO2 support of the present invention exhibits good HC / CO L / O and NO2 / NOx performance at low temperatures, as well as HCHO L / O performance comparable to that of the La / Zr / Al2O3 support.

[0446] Table 12. Catalyst products: Pt / Pd supported on various supports containing 25% Mn

[0447]

[0448]

[0449] In addition to the supports listed above (Examples 15-22), several different supports in powder form, other than Reference B (Example 16), were evaluated. The sample preparation process was similar to that of Example 2, except for the dopants and supports. Table 13 lists detailed descriptions of the various powder samples used in this new set of experiments; all supports were prefabricated (commercially available).

[0450] Table 13. Catalyst product: 1% Pt / Pd (Pt / Pd = 2 / 1), supported on various supports.

[0451]

[0452] The powder sample preparation and testing procedures were the same as those described in Example 15. The results are listed in Tables 14 to 17.

[0453] Table 14. HC / CO ignition (L / O) temperature and NO2 yield at 300℃ and 250℃ (fresh and aged samples)

[0454]

[0455]

[0456] From Table 14 and Figure 8 It can be seen that Y loaded on the ZrO2 support (Example 24 of the present invention) is superior to La / ZrO2 in terms of CO / HC L / O and NO2 yields, whether for fresh or aged samples.

[0457] Table 15HC / CO ignition (L / O) temperature and NO2 yield at 300℃ and 250℃ (fresh and aged samples)

[0458]

[0459] From Table 15 and Figure 9 It can be seen that Si supported on ZrO2 (Example 25 of the present invention) also outperforms La / ZrO2 in terms of CO / HC L / O and NO2 yields, whether for fresh or aged samples.

[0460] Table 16. HC / CO ignition (L / O) temperature and NO2 yield at 300℃ and 250℃ (fresh and aged samples)

[0461]

[0462] From Table 16 and Figure 10 It can be seen that Mn loaded on the ZrO2 support (Example 26 of the present invention) outperforms La / ZrO2 in terms of CO / HC L / O and NO2 yields, especially in terms of NO2 yield, regardless of whether the sample is fresh or aged. The sample of Example 26 of the present invention also provides very good NO2 performance stability between fresh and aged samples.

[0463] Table 17. HC / CO ignition (L / O) temperature and NO2 yield at 300℃ and 250℃ (fresh and aged samples)

[0464]

[0465] From Table 17 and Figure 11 It can be seen that Si supported on TiO2 (Example 27 of the present invention) is superior to La / ZrO2 in terms of CO / HC L / O and NO2 yields, especially in terms of NO2 yield, whether it is a fresh or aged sample.

[0466] Table 18. HC / CO ignition (L / O) temperature and NO2 yield at 300℃ and 250℃ (fresh and aged samples)

[0467]

[0468] Similarly, from Table 18 and Figure 12 It can be seen that Si supported on Al2O3 (Example 28 of the present invention) is superior to La / ZrO2 in terms of CO / HC L / O and NO2 yields, whether it is a fresh or aged sample.

Claims

1. An oxidation catalyst composition, said oxidation catalyst composition comprising: Platinum group metals, comprising palladium, platinum, or combinations thereof; Manganese component; and A first refractory metal oxide support material comprising 20% ​​to 99% by weight of zirconium oxide, wherein the zirconium oxide is doped with 1% to 40% by weight of lanthanum based on the weight of the oxide. in, Based on the weight of the first refractory metal oxide carrier material, the amount of manganese in the oxide is 5% to 30% by weight, and The oxidation catalyst composition contains less than 0.1% by weight of copper.

2. The oxidation catalyst composition of claim 1, wherein the manganese component is supported on the first refractory metal oxide support material.

3. The oxidation catalyst composition of claim 1, wherein the first refractory metal oxide support material further comprises alumina, silicon dioxide, cerium dioxide, titanium oxide, silicon dioxide-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina, and combinations thereof.

4. The oxidation catalyst composition of claim 1 further comprises a metal oxide selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, magnesium, antimony, tin, lead, yttrium, and combinations thereof.

5. The oxidation catalyst composition of claim 4, wherein the metal oxide is supported on the first refractory metal oxide support material.

6. The oxidation catalyst composition of claim 4, wherein: The metal oxide is cerium dioxide oxide, and The cerium dioxide is present in an amount of up to 99% by weight based on the weight of the first refractory metal oxide carrier material.

7. The oxidation catalyst composition of claim 1, comprising: The amount of cerium dioxide is from 1% to 99% by weight based on the weight of the first refractory metal oxide carrier material.

8. The oxidation catalyst composition of claim 1, wherein: The palladium, when present, is loaded onto the first refractory metal oxide support in an amount of 0.1% to 10% by weight based on the weight of the first refractory metal oxide support; The platinum, when present, is loaded onto the first refractory metal oxide support in an amount of 0.1% to 10% by weight based on the weight of the first refractory metal oxide support.

9. The oxidation catalyst composition of claim 1, wherein the platinum group metal component comprises a combination of platinum and palladium.

10. The oxidation catalyst composition of claim 9, wherein the weight ratio of palladium to platinum is 100 to 0.

01.

11. The oxidation catalyst composition of claim 9, wherein the weight ratio of palladium to platinum is 1 to 0.

01.

12. The oxidation catalyst composition of claim 1 further comprises a second refractory metal oxide support material.

13. The oxidation catalyst composition of claim 12, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, silicon dioxide-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina, or combinations thereof.

14. The oxidation catalyst composition of claim 12, wherein the second refractory metal oxide support material comprises a metal oxide selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, magnesium, antimony, tin, lead, yttrium, and combinations thereof.

15. The oxidation catalyst composition of claim 12, wherein the platinum group metal component is loaded on the second refractory metal oxide support material in an amount of 0.1% to 10% by weight based on the weight of the second refractory metal oxide support material.

16. The oxidation catalyst composition of claim 12, wherein the second refractory metal oxide support material comprises alumina or zirconium oxide.

17. The oxidation catalyst composition of claim 16, wherein the zirconium oxide in the second refractory metal oxide support material is doped with lanthanum in an amount of 0.1 wt% to 40 wt% based on the oxide, according to the weight of the zirconium oxide.

18. The oxidation catalyst composition of claim 12, wherein the second refractory metal oxide support material comprises less than 1.0% by weight of lanthanum.

19. The oxidation catalyst composition of claim 12, wherein the second refractory metal oxide support material comprises manganese.

20. The oxidation catalyst composition of claim 12, wherein the manganese component is supported on the first refractory metal oxide support material, and the platinum group metal component is supported on the second refractory metal oxide support material.

21. The oxidation catalyst composition of claim 20, wherein the platinum group metal component is loaded on the second refractory metal oxide support material in an amount of 0.1% to 10% by weight based on the weight of the second refractory metal oxide support material.

22. The oxidation catalyst composition of claim 12, wherein: The manganese component is manganese oxide, which is loaded onto the first refractory metal oxide support material in an amount of 5% to 30% by weight of the oxide, based on the weight of the first refractory metal oxide support material; and The platinum group metal component is loaded on the second refractory metal oxide carrier material, wherein the second refractory metal oxide carrier material is selected from alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and lanthanum oxide-doped zirconium oxide, wherein the amount of lanthanum oxide is from 1% to 40% by weight based on the weight of the zirconium oxide.

23. The oxidation catalyst composition of claim 22, wherein the first refractory metal oxide support material further comprises cerium dioxide in an amount of 1% to 50% by weight based on the weight of the first refractory metal oxide support material.

24. A catalytic article comprising an inlet end and an outlet end having a defined total length, and a catalytic coating disposed on at least a portion of the substrate, the catalytic coating comprising a first support coating and a second support coating, wherein: The first carrier coating comprises a manganese component and a first refractory metal oxide carrier material, the first refractory metal oxide carrier material comprising 20% ​​to 99% by weight of zirconium oxide, the zirconium oxide being doped with 1% to 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide, and wherein the manganese component is loaded on the first refractory metal oxide carrier material as manganese oxide or a mixed oxide, and the amount of manganese in the oxide is 5% to 30% by weight based on the weight of the first refractory metal oxide carrier material. The second carrier coating comprises a platinum group metal component and a second refractory metal oxide carrier material, wherein the platinum group metal component comprises palladium, platinum, or a combination thereof, and wherein the platinum group metal component is loaded on the second refractory metal oxide carrier material. The first carrier coating and the second carrier coating contain less than 0.1% by weight of copper.

25. The catalyst article of claim 24 further comprises a metal oxide supported on the first refractory metal oxide support material, wherein the metal oxide is selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, and combinations thereof.

26. The catalyst article of claim 24 further comprises a metal oxide supported on the first refractory metal oxide support material, wherein the metal oxide is selected from oxides of cerium, iron, cobalt, zinc, chromium, molybdenum, nickel, tungsten, magnesium, antimony, tin, lead, yttrium, and combinations thereof.

27. The catalyst article of claim 25, wherein the metal oxide is cerium dioxide oxide, and wherein the cerium dioxide is present in an amount of up to 30% by weight based on the weight of the first refractory metal oxide support material.

28. The catalyst article of claim 27, comprising: The amount of cerium dioxide is 1% to 30% by weight of the first refractory metal oxide carrier material.

29. The catalyst article of claim 24, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, or a combination thereof.

30. The catalyst article of claim 24, wherein the second refractory metal oxide support material comprises alumina.

31. The catalyst article of claim 24, wherein the second refractory metal oxide support material comprises zirconium oxide.

32. The catalyst article of claim 31, wherein the zirconium oxide in the second refractory metal oxide support material is doped with 1% to 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide.

33. The catalyst article of claim 24, wherein the second refractory metal oxide support material is selected from alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and lanthanum oxide-doped zirconium oxide, wherein the amount of lanthanum oxide is from 1% to 40% by weight based on the weight of the zirconium oxide.

34. The catalyst article of claim 24, wherein the platinum group metal component comprises a combination of platinum and palladium.

35. The catalyst article of claim 34, wherein the weight ratio of palladium to platinum is 100 to 0.

01.

36. The catalyst article of claim 34, wherein the weight ratio of palladium to platinum is 1 to 0.

01.

37. The catalyst article of claim 24, wherein the total platinum group metal composition supported on the catalyst article is 5 g / ft. 3 Up to 200 g / ft 3 .

38. The catalyst article of claim 24, wherein the platinum group metal is loaded on the second refractory metal oxide support material in an amount of 0.5% to 10% by weight based on the weight of the second refractory metal oxide support material.

39. The catalyst article of claim 24, wherein: The manganese component is a manganese oxide, wherein the first refractory metal oxide carrier material comprises aluminum oxide; The first refractory metal oxide support material further comprises cerium dioxide in an amount of 1% to 50% by weight based on the weight of the first refractory metal oxide support material; and The second refractory metal oxide carrier material is selected from alumina, silica-doped alumina, titanium dioxide, titanium dioxide-doped alumina, zirconium-doped alumina, zirconium oxide, and zirconium oxide doped with lanthanum oxide, wherein the amount of lanthanum oxide is from 1% to 40% by weight based on the weight of the zirconium oxide.

40. The catalyst article according to any one of claims 24 to 39, wherein the first carrier coating is disposed directly on the substrate, and the second carrier coating is disposed on at least a portion of the first carrier coating.

41. The catalyst article according to any one of claims 24 to 39, wherein the second carrier coating is disposed directly on the substrate, and the first carrier coating is disposed on at least a portion of the second carrier coating.

42. The catalyst article of any one of claims 24 to 39, wherein the catalyst article has a partitioned configuration, wherein the first carrier coating is directly disposed on the substrate for a length of 20% to 100% of the total length from the outlet end; and the second carrier coating is disposed on the substrate for a length of 20% to 100% of the total length from the inlet end.

43. The catalyst article of any one of claims 24 to 39, wherein the catalyst article has a partitioned configuration, wherein the second carrier coating is directly disposed on the substrate for a length of 20% to 100% of the total length from the outlet end; and the first carrier coating is disposed on the substrate for a length of 20% to 100% of the total length from the inlet end.

44. A catalytic article comprising an inlet end and an outlet end having a defined total length, and a catalytic coating disposed on at least a portion of the substrate, the catalytic coating comprising a first support coating, a second support coating, and a third support coating, wherein: The first carrier coating comprises a manganese component and a first refractory metal oxide carrier material, the first refractory metal oxide carrier material comprising 20% ​​to 99% by weight of zirconium oxide, wherein the zirconium oxide in the first refractory metal oxide carrier material is doped with 1% to 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide, wherein the manganese component is loaded on the first refractory metal oxide carrier material as manganese oxide or a mixed oxide, and the amount of manganese based on the oxide is 5% to 30% by weight based on the weight of the first refractory metal oxide carrier material. The second carrier coating comprises a metal oxide component and a second refractory metal oxide carrier material, wherein the metal oxide component includes cerium dioxide, manganese oxide, zirconium oxide, lanthanum oxide, or combinations thereof, and wherein the metal oxide component is loaded onto the second refractory metal oxide carrier material; and The third carrier coating comprises a platinum group metal component and a third refractory metal oxide carrier material, wherein the platinum group metal component comprises palladium, platinum, or combinations thereof, and wherein the platinum group metal component is loaded onto the third refractory metal oxide carrier material. The first carrier coating and the second carrier coating contain less than 0.1% by weight of copper.

45. The catalyst article of claim 44, wherein the second refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, silicon dioxide-doped alumina, titanium dioxide-doped alumina, zirconium-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, yttrium-zirconium, manganese-zirconium, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, manganese-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina, or combinations thereof.

46. ​​The catalyst article of claim 44, wherein the second refractory metal oxide support material comprises alumina.

47. The catalyst article of claim 44, wherein the second refractory metal oxide support material comprises silicon dioxide-doped alumina.

48. The catalyst article of claim 44, wherein the second refractory metal oxide support material comprises zirconium oxide.

49. The catalyst article of claim 48, wherein the zirconium oxide in the second refractory metal oxide support material is doped with 0.1% to 40% by weight of lanthanum oxide based on the total weight of the zirconium oxide.

50. The catalyst article of claim 44, wherein the third refractory metal oxide support material comprises alumina, silicon dioxide, zirconium oxide, titanium dioxide, cerium dioxide, silicon dioxide-doped alumina, titanium dioxide-doped alumina, zirconium-doped alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconium oxide, tungsten-titanium dioxide, zirconium oxide-titanium dioxide, zirconium oxide-cerium dioxide, zirconium oxide-alumina, lanthanum-zirconium oxide, lanthanum-zirconium oxide-alumina, magnesium-alumina, or combinations thereof.

51. The catalyst article of claim 44, wherein the platinum group metal component comprises a combination of platinum and palladium.

52. The catalyst article according to any one of claims 44 to 51, wherein the first carrier coating is disposed directly on the substrate, and the second carrier coating is disposed on at least a portion of the first carrier coating.

53. The catalyst article according to any one of claims 44 to 51, wherein the second carrier coating is disposed directly on the substrate, and the first carrier coating is disposed on at least a portion of the second carrier coating.

54. The catalyst article according to any one of claims 44 to 51, wherein the first carrier coating is disposed directly on the substrate, the second carrier coating is disposed on at least a portion of the first carrier coating, and the third carrier coating is disposed on at least a portion of the second carrier coating.

55. The catalyst article according to any one of claims 44 to 51, wherein the third carrier coating is directly disposed on the substrate, the second carrier coating is disposed on at least a portion of the third carrier coating, and the first carrier coating is disposed on at least a portion of the second carrier coating.

56. The catalyst article according to any one of claims 44 to 51, wherein the first carrier coating is directly disposed on the substrate, the third carrier coating is disposed on at least a portion of the first carrier coating, and the second carrier coating is disposed on at least a portion of the third carrier coating.

57. The catalyst article according to any one of claims 44 to 51, wherein the second carrier coating is directly disposed on the substrate, the third carrier coating is disposed on at least a portion of the second carrier coating, and the first carrier coating is disposed on at least a portion of the third carrier coating.

58. The catalyst article according to any one of claims 44 to 51, wherein the second carrier coating is directly disposed on the substrate, the first carrier coating is disposed on at least a portion of the second carrier coating, and the third carrier coating is disposed on at least a portion of the first carrier coating.

59. The catalyst article of any one of claims 44 to 51, wherein the catalyst article has a partitioned configuration, wherein: The first carrier coating is directly applied to the substrate at a length of 20% to 100% of the total length from the outlet end; The second carrier coating is applied to the substrate over a length of 20% to 100% of the total length from the inlet end; and The third carrier coating is applied to the substrate over a length of 20% to 100% of the total length from the inlet end.

60. An exhaust gas treatment system comprising a catalytic article as claimed in any one of claims 24 to 59, wherein the catalytic article is downstream of and in fluid communication with a compression-ignition internal combustion engine.

61. A method for treating an exhaust gas stream, the exhaust gas stream comprising hydrocarbons and / or carbon monoxide and / or NO. x The method includes contacting the waste gas stream with a catalyst as described in any one of claims 24 to 59 or a waste gas treatment system as described in claim 60.

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