catalyst article, method to reduce emissions from an exhaust stream, and exhaust purification system

专利摘要:
a catalyst article including a substrate with an inlet and outlet end, a first zone and a second zone, the first zone comprising: a) a lower layer of ammonia slip catalyst (asc) comprising a metal the platinum group on a support; and b) a scr layer comprising a second scr catalyst, the scr layer being located on the bottom asc layer; wherein the second zone comprises a catalyst (second zone catalyst) selected from the group consisting of a diesel oxidation catalyst (doc) and an exothermic diesel catalyst (dec); wherein the bottom layer of asc extends to the second zone; and where the first zone is located upstream of the second zone. the bottom asc layer may include a mixture of: (1) the platinum group metal on a support and (2) a first scr catalyst.
公开号:BR112019020350A2
申请号:R112019020350
申请日:2018-03-29
公开日:2020-04-28
发明作者:Newman Andrew；Micallef David；Chen Hai-Ying；Lu Jing；Fedeyko Joseph；Larsson Mikael；Greenham Neil；Marsh Per
申请人:Johnson Matthey Plc；
IPC主号:

专利说明:

CATALYST ARTICLE, METHOD TO REDUCE EMISSIONS FROM AN EXHAUST CHAIN, AND EXHAUST PURIFICATION SYSTEM
BACKGROUND OF THE INVENTION [001] Hydrocarbon combustion in diesel engines, stationary gas turbines and other systems generates exhaust gas that must be treated to remove nitrogen oxides (NOx), which comprise NO (nitric oxide) and NO2 (carbon dioxide) nitrogen), with NO being the majority of NOx formed. NOx is known to cause numerous health problems in people as well as numerous harmful environmental effects that include the formation of smoke and acid rain. To mitigate both human and environmental impact from NO _X in exhaust gas, it is desired to eliminate these undesirable components, preferably, by a process that does not generate other harmful or toxic substances.
[002] The exhaust gas generated in low-burn and diesel engines is generally oxidative. NOx needs to be selectively reduced with a catalyst and a reducer in a process known as selective catalytic reduction (SCR) that converts NOx to elemental nitrogen (N2) and water. An SCR process, a gaseous reducer, typically anhydrous ammonia, aqueous ammonia or urea, is added to an exhaust gas stream before the exhaust gas comes in contact with the catalyst. The reducer is absorbed into the catalyst and NO _X is reduced as gases pass through or over the catalyzed substrate. In order to maximize NOx conversion, it is usually necessary to add more than a stoichiometric amount of ammonia to the gas stream. However, the release of excess ammonia into the atmosphere could be harmful to people's health and the environment. In addition, ammonia is caustic, especially in its aqueous form. Condensation of ammonia and water in areas of the exhaust line downstream of the exhaust catalysts can result in a corrosive mixture
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2/41 that can damage the exhaust system. Therefore, the release of ammonia in the exhaust gas should be eliminated. In many conventional exhaust systems, an ammonia oxidation catalyst (also known as an ammonia leak catalyst or “ASC”) is installed downstream of the SCR catalyst to remove ammonia from the exhaust gas by converting it to nitrogen. The use of ammonia leak catalysts can allow conversions of NO _X greater than 90% over a typical diesel drive cycle.
[003] It would be desirable to have a catalyst and a system that includes a catalyst that provides both removal of NO _X by SCR and conversion of selective ammonia to nitrogen, where the conversion of ammonia occurs over a wide range of temperatures in a drive cycle of the vehicle and minimal nitrogen oxide and nitrous oxide by-products are formed.
SUMMARY OF THE INVENTION [004] According to some embodiments of the present invention, a catalyst article includes a substrate with an inlet and outlet end, a first zone and a second zone, wherein the first zone comprises: a) a lower layer of ammonia catalyst (ASC) comprising a metal of the platinum group on a support; and b) an SCR layer comprising a second SCR catalyst, the SCR layer located on the lower ASC layer; wherein the second zone comprises a catalyst ("second zone catalyst") selected from the group consisting of a diesel oxidation catalyst (DOC) and an exothermic diesel catalyst (DEC); wherein the lower ASC layer extends to the second zone; and where the first zone is located upstream of the second zone. The lower ASC layer may include a combination of: (1) the platinum group metal in a support and (2) a first SCR catalyst. In some modalities, the first SCR and / or the second
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3/41 SCR catalyst includes Fe, Mn, Cu or combinations thereof.
[005] In certain embodiments, the bottom layer of ASC extends from the outlet end to less than a total length of the substrate; the SCR layer extends from the inlet end to less than a total length of the substrate and which at least partially overlaps the lower ASC layer; and the catalyst of the second zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, where the second layer is located on top of the bottom layer of ASC and is shorter than the layer bottom of ASC.
[006] In some embodiments, the bottom layer of ASC extends from the entry end to less than a total length of the substrate; the SCR layer extends from the inlet end to less than a total length of the substrate, where the SCR layer is located on top of the bottom ASC layer and does not extend further to the outlet end than the bottom layer of ASC; and the catalyst of the second zone is included in a second layer extending from the outlet end to less than a total length of the substrate, the second layer at least partially overlapping the lower ASC layer.
[007] In some embodiments, the bottom layer of ASC extends from the entry end to less than a total length of the substrate; the SCR layer extends from the inlet end to less than a total length of the substrate, where the SCR layer is located on top of the bottom ASC layer and extends further to the outlet end than the bottom ASC layer ; and the catalyst of the second zone is included in a layer that extends from the outlet end to less than a total length of the substrate.
[008] In some embodiments, the bottom layer of ASC covers a
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4/41 total length of the substrate; the SCR layer extends from the input end to less than a total length of the substrate, where the SCR layer is located on top of the bottom ASC layer; and the catalyst of the second zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, where the second layer is located on top of the lower ASC layer.
[009] In some embodiments, the catalyst for the second zone is located within the substrate. The support may include a siliceous material, such as, for example, a material selected from the group consisting of: (1) silica; (2) a zeolite with a silica to alumina ratio greater than 200; and (3) alumina doped with amorphous silica with an SIO2 content <40%. In some embodiments, the platinum group metal is present in the support in an amount of about 0.1% by weight to about 10% by weight; about 0.5% by weight to about 10% by weight, about 1% by weight to about 6% by weight, or about 1.5% by weight to about 4% by weight of the total weight of the platinum group metal and support. In some embodiments, the platinum group metal comprises platinum, palladium or a combination of platinum and palladium. In some embodiments, the metal of the platinum group comprises platinum.
[0010] Within the combination, a weight ratio of the first SCR catalyst to the platinum group metal on a support can be from about 3: 1 to about 300: 1; about 5: 1 to about 100: 1; or about 10: 1 to about 50: 1. In some embodiments, the first SCR catalyst is a base metal, a base metal oxide, a molecular sieve, a metal-substituted molecular sieve or a mixture thereof. In some embodiments, the first SCR catalyst includes copper. In some embodiments, the second SCR catalyst is a base metal, a base metal oxide, a molecular sieve, a molecular sieve replaced by
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5/41 metal or a mixture thereof.
[0011] In some aspects of the invention, the first zone and the second zone are located on a single substrate and the first zone is located on the substrate inlet side and the second zone is located on the substrate outlet side. In some embodiments, the substrate comprises a first substrate and a second substrate, where the first zone is located on a first substrate and the second zone is located on the second substrate and the first substrate is located upstream of the second substrate.
[0012] According to some embodiments of the present invention, a method of reducing exhaust stream emissions includes contacting the exhaust stream with a catalytic article comprising a substrate with an inlet end and an outlet end, a first zone and a second zone, wherein the first zone comprises: (a) a lower layer of ammonia catalyst (ASC) comprising a platinum group metal on a support; and b) an SCR layer comprising a second SCR catalyst, the SCR layer located on the lower ASC layer; wherein the second zone comprises a catalyst ("second zone catalyst") selected from the group consisting of a diesel oxidation catalyst (DOC) and an exothermic diesel catalyst (DEC); wherein the lower ASC layer extends to the second zone; and where the first zone is located upstream of the second zone. In some embodiments, the ASC bottom layer comprises a combination of: (1) the platinum group metal on a support and (2) a first SCR catalyst. The first SCR catalyst and / or the second SCR catalyst can include Fe, Mn, Cu or combinations thereof.
[0013] In accordance with some embodiments of the present invention, an exhaust purification system for reducing exhaust stream emissions includes: (a) a turbocharger; (b) a third catalyst
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SCR; and (c) a catalyst article which includes a substrate with an inlet and outlet end, a first zone and a second zone, wherein the first zone comprises: (i) a lower layer of ammonia catalyst (ASC) comprising a metal of the platinum group on a support; and (ii) an SCR layer comprising a second SCR catalyst, the SCR layer located on the lower ASC layer; wherein the second zone comprises a catalyst ("second zone catalyst") selected from the group consisting of a diesel oxidation catalyst (DOC) and an exothermic diesel catalyst (DEC); wherein the lower ASC layer extends to the second zone; and where the first zone is located upstream of the second zone. In some embodiments, the third SCR catalytic converter is located upstream of the turbocharger. In some embodiments, the third SCR catalyst is located downstream from the turbocharger. In some embodiments, the ASC bottom layer comprises a combination of: (1) the platinum group metal on a support and (2) a first SCR catalyst. The first SCR catalyst and / or the second SCR catalyst can comprise, for example, Fe, Mn, Cu or combinations thereof.
[0014] In some embodiments, the third SCR catalyst and the catalyst article are located on a single substrate, with the third SCR catalyst located upstream of the first zone and the second zone. In some embodiments, the third SCR catalyst is located on a substrate upstream of the catalyst article substrate. In some embodiments, the third SCR catalyst is coupled to the catalyst article.
[0015] In some embodiments, the system may also include a filter, an SCR catalyst downstream located downstream of the catalyst article, a pre-turbo SCR catalyst located upstream of the turbocharger, a reducing injector located upstream of the third SCR catalyst, a reducing injector located upstream of the SCR catalyst downstream and / or an injector
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7/41 reducer located upstream of the pre-turbo SCR catalyst.
[0016] In some respects, the bottom layer of ASC extends from the outlet end to less than a total length of the substrate; the SCR layer extends from the inlet end to less than a total length of the substrate and which at least partially overlaps the lower ASC layer; and the catalyst of the second zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, where the second layer is located on top of the bottom layer of ASC and is shorter than the layer bottom of ASC.
[0017] In some embodiments, the bottom layer of ASC extends from the entry end to less than a total length of the substrate; the SCR layer extends from the inlet end to less than a total length of the substrate, where the SCR layer is located on top of the bottom ASC layer and does not extend further to the outlet end than the bottom layer of ASC; and the catalyst of the second zone is included in a second layer extending from the outlet end to less than a total length of the substrate, the second layer at least partially overlapping the lower ASC layer.
[0018] In some embodiments, the bottom layer of ASC extends from the entrance end to less than a total length of the substrate; the SCR layer extends from the inlet end to less than a total length of the substrate, where the SCR layer is located on top of the bottom ASC layer and extends further to the outlet end than the bottom ASC layer ; and the catalyst of the second zone is included in a layer that extends from the outlet end to less than a total length of the substrate.
[0019] In some embodiments, the bottom layer of ASC covers a
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8/41 total length of the substrate; the SCR layer extends from the input end to less than a total length of the substrate, where the SCR layer is located on top of the bottom ASC layer; and the catalyst of the second zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, where the second layer is located on top of the lower ASC layer.
[0020] In some embodiments, the catalyst for the second zone is located inside the substrate. In some embodiments, the support comprises a siliceous material, such as, for example, a material selected from the group consisting of: (1) silica; (2) a zeolite with a silica to alumina ratio greater than 200; and (3) alumina doped with amorphous silica with an SIO2 content <40%.
[0021] In some embodiments, the metal of the platinum group is present in the support in an amount of about 0.1% by weight to about 10% by weight; about 0.5% by weight to about 10% by weight, about 1% by weight to about 6% by weight, or about 1.5% by weight to about 4% by weight of the total weight of the platinum group metal and support. In some embodiments, the platinum group metal comprises platinum, palladium or a combination of platinum and palladium. In some embodiments, the metal of the platinum group comprises platinum.
[0022] Within the combination, a weight ratio of the first SCR catalyst to the platinum group metal on a support can be from about 3: 1 to about 300: 1; about 5: 1 to about 100: 1; or about 10: 1 to about 50: 1. In some embodiments, the first SCR catalyst is a base metal, a base metal oxide, a molecular sieve, a metal-substituted molecular sieve or a mixture thereof. In some embodiments, the first SCR catalyst includes copper. In some embodiments, the second SCR catalyst is a base metal, an oxide of a
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9/41 base metal, a molecular sieve, a molecular sieve replaced by metal or a mixture thereof.
[0023] In some aspects of the invention, the first zone and the second zone are located on a single substrate and the first zone is located on the substrate inlet side and the second zone is located on the substrate outlet side. In some embodiments, the substrate comprises a first substrate and a second substrate, where the first zone is located on a first substrate and the second zone is located on the second substrate and the first substrate is located upstream of the second substrate.
[0024] In accordance with some embodiments of the present invention, an exhaust purification system for reducing exhaust stream emissions includes: (a) a turbocharger; (b) a third SCR catalyst; and (c) a catalyst article comprising a substrate comprising an inlet and outlet end, a first zone and a second zone, the first zone comprising an ammonia slip catalyst (ASC) comprising a metal platinum group on a support and a first SCR catalyst; wherein the second zone comprises a catalyst selected from the group consisting of a diesel oxidation catalyst (DOC) and an exothermic diesel catalyst (DEC); and where the first zone is located upstream of the second zone. In some embodiments, the third SCR catalytic converter is located upstream of the turbocharger. In some embodiments, the third SCR catalyst is located downstream from the turbocharger. The third SCR catalyst can include, for example, V, Fe, Mn, Cu or combinations thereof. In some embodiments, the third SCR catalyst and the catalyst article are located on a single substrate, with the third SCR catalyst located upstream of the first zone and the second zone. In some embodiments, the third SCR catalyst is located in a
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10/41 substrate upstream of the catalyst article substrate. In some embodiments, the third SCR catalyst is coupled to the catalyst article.
[0025] In some embodiments, the system may also include a filter, an SCR catalyst downstream located downstream of the catalyst article, a pre-turbo SCR catalyst located upstream of the turbocharger, a reducing injector located upstream of the third SCR catalyst, a reducing injector located upstream of the downstream SCR catalyst and / or a reducing injector located upstream of the pre-turbo SCR catalyst.
[0026] In some embodiments, the first zone comprises: (a) a lower layer comprising a combination of: (1) the platinum group metal on a support and (2) the first SCR catalyst; and (b) an upper layer comprising a second SCR catalyst, the upper layer located on the lower layer.
[0027] In some embodiments, the support comprises a siliceous material, such as, for example, a material selected from the group consisting of: (1) silica; (2) a zeolite with a silica to alumina ratio greater than 200; and (3) alumina doped with amorphous silica with an SIO2 content <40%.
[0028] In some embodiments, the metal of the platinum group is present in the support in an amount of about 0.1% by weight to about 10% by weight; about 0.5% by weight to about 10% by weight, about 1% by weight to about 6% by weight, or about 1.5% by weight to about 4% by weight of the total weight of the platinum group metal and support. In some embodiments, the platinum group metal comprises platinum, palladium or a combination of platinum and palladium. In some embodiments, the metal of the platinum group comprises platinum.
[0029] Within the combination, a weight ratio of the first SCR catalyst to the platinum group metal on a support can be from about 3: 1 to about 300: 1; about 5: 1 to about 100: 1; or about 10: 1 to about 50: 1. In some embodiments, the first SCR catalyst is a
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11/41 base metal, an oxide of a base metal, a molecular sieve, a molecular sieve substituted by metal or a mixture thereof. In some embodiments, the first SCR catalyst includes copper. In some embodiments, the second SCR catalyst is a base metal, a base metal oxide, a molecular sieve, a metal-substituted molecular sieve or a mixture thereof.
[0030] In some aspects of the invention, the first zone and the second zone are located on a single substrate and the first zone is located on the substrate inlet side and the second zone is located on the substrate outlet side. In some embodiments, the substrate comprises a first substrate and a second substrate, where the first zone is located on a first substrate and the second zone is located on the second substrate and the first substrate is located upstream of the second substrate.
[0031] In accordance with some embodiments of the present invention, an exhaust purification system for reducing exhaust stream emissions includes: (a) a turbocharger; (b) a third SCR catalyst; and (c) a catalyst article comprising a substrate comprising an inlet and outlet end, a first zone, a second zone and a third zone, the first zone comprising a second SCR catalyst; wherein the second zone comprises a sliding ammonia catalyst (ASC) comprising a combination of: (1) a platinum group metal on a support and (2) a first SCR catalyst; wherein the third zone comprises a catalyst ("third zone catalyst") selected from the group consisting of a diesel oxidation catalyst (DOC) and an exothermic diesel catalyst (DEC); and wherein the first zone is located upstream of the second zone and the second zone is located upstream of the third zone. In some embodiments, the third SCR catalyst is located upstream
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12/41 of the turbocharger. In some embodiments, the third SCR catalyst is located downstream from the turbocharger. The third SCR catalyst can include, for example, V, Fe, Mn, Cu or combinations thereof. In some embodiments, the third SCR catalyst and the catalyst article are located on a single substrate, with the third SCR catalyst located upstream of the first zone and the second zone. In some embodiments, the third SCR catalyst is located on a substrate upstream of the catalyst article substrate. In some embodiments, the third SCR catalyst is coupled to the catalyst article.
[0032] In some embodiments, the system may also include a filter, an SCR catalyst downstream located downstream of the catalyst article, a pre-turbo SCR catalyst located upstream of the turbocharger, a reducing injector located upstream of the third SCR catalyst, a reducing injector located upstream of the downstream SCR catalyst and / or a reducing injector located upstream of the pre-turbo SCR catalyst.
[0033] In some modalities, the ASC is included in a first layer; the catalyst of the third zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, where the second layer is located on top of the first layer and is shorter in length than the first layer; and the second SCR catalyst is included in a layer that extends from the inlet end to less than a total length of the substrate and that at least partially overlaps the first layer. In some embodiments, the first layer extends from the outlet end to less than a total length of the substrate. In some embodiments, the first layer extends from the entry end to less than a total length of the substrate.
[0034] In some embodiments, the support comprises a siliceous material, such as, for example, a material selected from the group consisting of
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13/41 in: (1) silica; (2) a zeolite with a silica to alumina ratio greater than 200; and (3) alumina doped with amorphous silica with an SIO2 content <40%. [0035] In some embodiments, the metal of the platinum group is present in the support in an amount of about 0.1% by weight to about 10% by weight; about 0.5% by weight to about 10% by weight, about 1% by weight to about 6% by weight, or about 1.5% by weight to about 4% by weight of the total weight of the platinum group metal and support. In some embodiments, the platinum group metal comprises platinum, palladium or a combination of platinum and palladium. In some embodiments, the metal of the platinum group comprises platinum.
[0036] Within the combination, a weight ratio of the first SCR catalyst to the platinum group metal on a support can be from about 3: 1 to about 300: 1; about 5: 1 to about 100: 1; or about 10: 1 to about 50: 1. In some embodiments, the first SCR catalyst is a base metal, a base metal oxide, a molecular sieve, a metal-substituted molecular sieve or a mixture thereof. In some embodiments, the first SCR catalyst includes copper. In some embodiments, the second SCR catalyst is a base metal, a base metal oxide, a molecular sieve, a metal-substituted molecular sieve or a mixture thereof.
[0037] In some embodiments of the invention, the first zone, the second zone and the third zone are located on a single substrate and the first zone is located on the substrate inlet side and the second zone is located on the substrate outlet side . In some embodiments, the substrate comprises a first substrate and a second substrate, where the first zone and the second zone are located on a first substrate and the third zone is located on the second substrate and the first substrate is located upstream of the second substrate . In some embodiments, the substrate comprises a first substrate, a second
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14/41 substrate and a third substrate, where the first zone is located on the first substrate, the second zone is located on the second substrate and the third zone is located on the third substrate, and the first substrate is located upstream of the second substrate and the second substrate is located upstream of the third substrate.
BRIEF DESCRIPTION OF THE DRAWINGS [0038] Figure 1 represents system configurations of modalities of the present invention, which includes a pre-turbo and post-turbo close coupling catalyst.
[0039] Figure 2 represents a configuration of the modalities system of the present invention, which includes a post-turbo close coupling SCR / ASC / DOC catalyst.
[0040] Figure 3 represents a modal system configuration of the present invention, which includes a close coupled post-turbo SCR catalyst followed by an ASC / DOC catalyst.
[0041] Figure 4 represents a modal system configuration of the present invention, which includes a close coupled pre-turbo SCR catalyst followed by a post-turbo ASC / DOC catalyst.
[0042] Figure 5 shows the catalyst configurations tested in simulated engine output conditions with systematically varied functionalities: (1) SCR only, (2) SCR / DOC, (3) ASC / DOC and (4) SCR / ASC / DOC.
[0043] Figure 6 shows the conversion of NH3 from inventive and reference catalysts.
[0044] Figure 7 shows NH3 slip of the inventive and reference catalysts.
[0045] Figure 8 shows the NO conversion of the inventive and reference catalysts.
[0046] Figure 9 shows the CO conversion of the catalysts
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[0047] Figure 10 shows the HC conversion of inventive and reference catalysts.
[0048] Figure 11 shows the N2O formation of inventive and reference catalysts.
[0049] Figure 12 shows N2 yield of inventive and reference catalysts.
[0050] Figure 13 shows the outlet temperature of the catalysts of the invention and reference.
DETAILED DESCRIPTION OF THE INVENTION [0051] The catalysts of the present invention refer to catalyst articles, which include various catalyst configurations (or catalysts) of SCR, ASC and DOC or DEC. Specific catalysts and configurations are described in more detail below. The systems of the present invention refer to these SCR / ASC / DOC or DEC catalysts in various system configurations with a turbocharger. Specific systems and configurations are described in more detail below.
TWO-ZONE CONFIGURATIONS [0052] Modalities of the present invention refer to a catalyst article comprising a substrate with an inlet and outlet end, a first zone and a second zone, where the first zone is located upstream of the second zone. The first zone can include a lower layer of ammonia slip catalyst (ASC) with a platinum group metal on a support; and an SCR layer with an SCR catalyst, wherein the SCR layer is located on the lower ASC layer. The second zone can include a diesel oxidation catalyst (DOC) or an exothermic diesel catalyst (DEC). In such catalyst articles, the bottom layer of ASC can extend into the second zone. In some embodiments, the bottom ASC layer includes a mixture
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16/41 of (1) the metal of the platinum group on a support and (2) a first SCR catalyst.
[0053] In some embodiments, the bottom layer of ASC extends from the outlet end to less than a total length of the substrate; the SCR layer extends from the inlet end to less than a total length of the substrate and which at least partially overlaps the lower ASC layer; and the second zone catalyst (DOC or DEC) is included in a second layer that extends from the outlet end to less than a total length of the substrate, where the second layer is located on top of the bottom ASC layer and is shorter than the bottom ASC layer.
[0054] In some embodiments, the bottom ASC layer extends from the input end to less than a total length of the substrate, and the SCR layer extends from the input end to less than a total length of the substrate. In some embodiments, the SCR layer may be located on top of the bottom ASC layer and does not extend further to the outlet end than the bottom ASC layer. The second zone catalyst (DOC or DEC) can be included in a second layer that extends from the outlet end to less than a total length of the substrate, where the second layer at least partially overlaps the lower ASC layer.
[0055] In some embodiments, the lower ASC layer extends from the input end to less than a total length of the substrate, and the SCR layer extends from the input end to less than a total length of the substrate. In some embodiments, the SCR layer may be located on top of the bottom ASC layer and extends further to the outlet end than the bottom ASC layer. The second zone catalyst (DOC or DEC) can be included in a layer that extends from the outlet end to less than one
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17/41 total length of the substrate.
[0056] In some embodiments, the bottom ASC layer covers a total length of the substrate, and the SCR layer extends from the input end to less than a total length of the substrate. The SCR layer can be located on top of the bottom ASC layer, and the second zone catalyst (DOC or DEC) can be included in a second layer that extends from the outlet end to less than a total substrate length, wherein the second layer is located on top of the bottom ASC layer.
[0057] In some embodiments, the catalyst for the second zone is located inside the substrate.
[0058] In some embodiments, the first and second zones are located on a single substrate with the first zone located on the substrate inlet side and the second zone located on the substrate outlet side. In another embodiment, the first zone is located on a first substrate and the second zone is located on a second substrate in which the first substrate is located upstream of the second substrate. The first and second substrates can be close coupled. When the first and second substrates are coupled close together, the second substrate can be placed near and / or directly downstream of the first substrate.
[0059] Modalities of the present invention refer to catalyst articles with a first zone and a second zone, the first zone which includes an ammonia catalyst (ASC) comprising a platinum group metal in a support and a first SCR catalyst; and the second zone, which includes a diesel oxidation catalyst (DOC) or diesel exothermic catalyst (DEC). The first zone can be configured to include a lower layer, which includes a mixture of (1) the platinum group metal in a support and (2) the first SCR catalyst; and an upper layer that
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18/41 includes a second SCR catalyst, in which the upper layer is located on the lower layer. In some embodiments, the first and second zones are located on a single substrate with the first zone located on the substrate inlet side and the second zone located on the substrate outlet side. In another embodiment, the first zone is located on a first substrate and the second zone is located on a second substrate in which the first substrate is located upstream of the second substrate. The first and second substrates can be close coupled. When the first and second substrates are coupled close together, the second substrate can be placed near and / or directly downstream of the first substrate.
[0060] A method of reducing exhaust chain emissions may include contacting the exhaust chain with a catalyst article, as described in this document.
CONFIGURATION OF THREE ZONES [0061] Modalities of the present invention refer to catalyst articles that have a first zone, a second zone and a third zone. The first zone can include an SCR catalyst. The second zone can include an ASC that has a mixture of a platinum group metal on a support with a first SCR catalyst. The third zone can include a catalyst ("third zone catalyst") such as a DOC or DEC. The first zone is located upstream of the second zone and the second zone is located upstream of the third zone.
[0062] In some modalities, the ASC is included in a first layer. The catalyst of the third zone can be located in a second layer that extends from the outlet end to less than a total length of the substrate, and the second layer is located on top of the first layer and is less than the first layer. The second SCR catalyst can be included in a layer that extends from the
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19/41 inlet end to less than a total length of the substrate and which at least partially overlaps the first layer. In some embodiments, the first layer extends from the outlet end to less than a total length of the substrate. In some embodiments, the first layer extends from the entry end to less than a total length of the substrate.
[0063] In some embodiments of the invention, the first zone, the second zone and the third zone are located on a single substrate and the first zone is located on the substrate inlet side and the second zone is located on the substrate outlet side . In some embodiments, the first zone and the second zone are located on a first substrate and the third zone is located on a second substrate and the first substrate is located upstream of the second substrate. The first and second substrates can be close coupled. When the first and second substrates are coupled close together, the second substrate can be placed near and / or directly downstream of the first substrate.
[0064] In some embodiments, the first zone is located on a first substrate, the second zone is located on a second substrate and the third zone is located on a third substrate, where the first substrate is located upstream of the second substrate and the second substrate is located upstream of the third substrate. The first, second and / or third substrate can be close coupled. When the first, second and / or third substrate are coupled close together, the second substrate can be placed close and / or directly downstream of the first substrate and the third substrate can be placed close and / or directly downstream of the second substrate.
[0065] A method of reducing exhaust chain emissions may include contacting the exhaust chain with a catalyst article, as described in this document.
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SYSTEM CONFIGURATIONS [0066] The system configurations of the present invention can include a turbocharger, an upstream SCR catalyst and a catalytic article with a two or three zone configuration, as described in the previous sections. The upstream SCR catalyst can be located upstream of the catalytic article which has a two or three zone configuration, as described in the previous sections; in some embodiments, the upstream SCR catalyst and the catalytic article can be closely coupled. In some embodiments, the upstream SCR catalyst and the catalytic article are located on a single substrate, with the upstream SCR catalyst located upstream of the first and second (and third, if any) zones of the catalytic article. In some embodiments, the upstream SCR catalyst is located upstream of the turbocharger. When the upstream SCR catalyst is located upstream of the turbocharger, the upstream SCR catalyst is combined with an ASC. In some embodiments, the upstream SCR catalyst is located downstream from the turbocharger.
[0067] The catalytic article that has a configuration of two or three zones, as described above, can be located downstream of the turbocharger. In some embodiments, the system includes an SCR catalyst located downstream of the catalytic article which has a two or three zone configuration, as described above. In some embodiments, a system may also include a filter.
[0068] The system can include one or more reducing injectors, for example, upstream of any SCR catalyst in the system. In some embodiments, the system includes a reducing injector upstream of the SCR catalyst and / or the catalytic article which has a two or three zone configuration, as described above. In a system that has an SCR catalyst downstream, a reducing injector can be included upstream of the SCR catalyst downstream. [0069] With reference to Figure 1, the systems of the present invention
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21/41 may include a number of combinations of catalyst components. In general, the system can include a pre-turbo and post-turbo close coupling catalyst that can include any combination of the catalysts shown in Figure 1. As shown in Figure 1, a system can include a pre-turbo catalyst that can include an SCR catalyst , an ASC or a SCR / ASC of various configurations. The SCR / ASC pre-turbo catalyst configurations can include a lower layer that includes an ASC and an upper layer that includes an SCR catalyst. The bottom layer of ASC can extend the entire length of the substrate, or it can extend from the outlet end to the inlet end and cover less than the entire length of the substrate. The top layer SCR catalyst can extend from the inlet end of the substrate towards the outlet end and can at least partially overlap the bottom ASC layer. The SCR catalyst of the upper layer can extend the entire length of the substrate or it can extend from the inlet end and cover less than the entire length of the substrate.
[0070] As shown in Figure 1, the system can include a urea injector upstream of the pre-turbo catalyst. The post-turbo catalyst can include an SCR catalyst, an ASC and / or a DOC, as described in this document and as shown in Figure 1. The post-turbo catalyst can be configured to include: 1) only a DOC, 2) an ASC and DOC or 3) a combination of SCR, ASC and DOC. The post-turbo catalyst can include a lower layer that includes an ASC and an upper layer that includes an SCR catalyst. The bottom layer of ASC can extend the entire length of the substrate, or it can extend from the outlet end to the inlet end and cover less than the entire length of the substrate. The top layer SCR catalyst can extend from the inlet end of the substrate towards the end of
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22/41 exit and can at least partially overlap the lower ASC layer. The SCR catalyst of the upper layer can extend the entire length of the substrate or it can extend from the inlet end and cover less than the entire length of the substrate. DOC can be included in an upper layer that extends from the substrate's outlet end towards an inlet end, which covers less than an entire length of the substrate and can be located on top of the bottom ASC layer. DOC can be impregnated with a solution of platinum nitrate or palladium nitrate or a mixture of platinum nitrate and palladium.
[0071] The ASC sections shown in Figure 1 may comprise a combination as described in this document. The downstream catalyst can include a filter and / or an SCR / ASC with another injection of urea / NHs before SCR / ASC.
[0072] With reference to Figure 2, a system of the present invention can include a urea turbocharger and injector, a closely coupled SCR / ASC / DOC catalyst, a filter, another urea injector and an SCR / ASC catalyst. As shown in Figure 2, the SCR / ASC / DOC catalyst can include a lower layer of ASC that extends from the outlet end of the substrate towards the inlet end and covers less than the entire length of the substrate, a layer of DOC extends from the outlet end of the substrate towards the inlet end and which covers less than the entire length of the substrate and located on top of the bottom ASC layer, and a layer of SCR catalyst that extends from the inlet end towards to the outlet end of the substrate and at least partially the bottom ASC layer. The ASC sections shown in Figure 2 can comprise a combination as described in this document.
[0073] Referring to Figure 3, a modalities system configuration of the present invention can include a post-turbo SCR catalyst
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23/41 close coupling followed by an ASC / DOC catalyst. A system can include a turbocharger, a urea injector, an SCR catalyst and ASC / DOC catalyst, a filter, another urea injector and an SCR / ASC catalyst. The ASC / DOC catalyst may include a lower ASC layer that extends from the inlet end to the outlet end of the substrate. In one configuration, the bottom ASC layer extends the entire length of the substrate, with an upper layer of SCR that extends from the end of the inlet towards the end of the outlet and covers less than the entire length of the substrate, and a top DOC layer extends from the outlet end towards the inlet end and covers less than the entire length of the substrate, where the top SCR layer and the top DOC layer are located on top of the bottom ASC layer . In another configuration, the lower ASC layer extends from the end of the inlet towards the end of the outlet and covers less than the entire length of the substrate, with an upper layer of SCR located on top of the lower layer of ASC and extending from the end of the inlet towards the outlet end and cover less than the entire length of the substrate, and a layer of DOC that extends from the outlet end towards the inlet end and covers less than an entire length of the substrate. The DOC layer can partially overlap the lower ASC layer. The ASC sections shown in Figure 3 can comprise a combination as described in this document.
[0074] Figure 4 represents a modal system configuration of the present invention, which includes a close coupled pre-turbo SCR catalyst followed by a post-turbo ASC / DOC catalyst. A system can include a urea injector upstream of the SCR catalyst, followed by the turbocharger, an ASC / DOC catalyst, a filter, another urea injector and an SCR / ASC catalyst. The ASC / DOC catalyst can
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24/41 include a lower layer of ASC extending from the inlet end to the outlet end of the substrate. In one configuration, the bottom ASC layer extends the entire length of the substrate, with an upper layer of SCR that extends from the end of the inlet towards the end of the outlet and covers less than the entire length of the substrate, and a top DOC layer extends from the outlet end towards the inlet end and covers less than the entire length of the substrate, where the top SCR layer and the top DOC layer are located on top of the bottom ASC layer . In another configuration, the lower ASC layer extends from the end of the inlet towards the end of the outlet and covers less than the entire length of the substrate, with an upper layer of SCR located on top of the lower layer of ASC and extending from the end of the inlet towards the outlet end and cover less than the entire length of the substrate, and a layer of DOC that extends from the outlet end towards the inlet end and covers less than an entire length of the substrate. The DOC layer can partially overlap the lower ASC layer. The ASC sections shown in Figure 4 can comprise a combination as described in this document.
AMMONIA OXIDATION CATALYST [0075] The catalyst articles of the present invention may include one or more ammonia oxidation catalysts, also called ammonia catalyst ("ASC"). One or more ASCs can be included or downstream from an SCR catalyst, to oxidize excess ammonia and prevent it from being released into the atmosphere. In some embodiments, ASC can be included on the same substrate as an SCR catalyst or combined with an SCR catalyst. In certain embodiments, the ammonia oxidation catalyst material can be selected to favor ammonia oxidation rather than the formation of NO _X or N2O. Catalyst materials
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Preferred 25/41 include platinum, palladium or a combination thereof. The ammonia oxidation catalyst may comprise platinum and / or palladium supported on a metal oxide. In some embodiments, the catalyst is arranged on a high surface area support, which includes, but is not limited to, alumina.
[0076] In some embodiments, the ammonia oxidation catalyst comprises a metal of the platinum group on a siliceous support. A siliceous material can include a material such as: (1) silica; (2) a zeolite with a silica to alumina ratio of at least 200; and (3) alumina doped with amorphous silica with a SiO2 content <40%. In some embodiments, a siliceous material may include a material such as a zeolite with a silica to alumina ratio of at least 200; at least 250; at least 300; at least 400; at least 500; at least 600; at least 750; at least 800; or at least 1,000. In some embodiments, a platinum group metal is present in the support in an amount of about 0.1% by weight to about 10% by weight of the total weight of the platinum group metal and the support; about 0.5% by weight to about 10% by weight of the total weight of the platinum group metal and the support; about 1% by weight to about 6% by weight of the total weight of the platinum group metal and the support; about 1.5% by weight to 4% by weight of the total weight of the platinum group metal 10% by weight 0.1% by weight 0.5% by weight 1% about about about about weight about 2% by weight about 3% by weight about 4% by weight about 5% by weight about 6% by weight weight weight weight weight weight weight weight weight weight weight total weight metal group total platinum group metal total group platinum group metal total platinum group metal total platinum group metal total platinum group metal total platinum group metal total platinum group metal the platinum group of the support;
support;
support;
support;
support;
do do do do support;
Support;
Support;
Support;
Support;
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26/41 about 7% by weight of the total weight of the platinum group metal and the support; about 8% by weight of the total weight of the platinum group metal and the support; about 9% by weight of the total weight of the platinum group metal and the support; or about 10% by weight of the total weight of the platinum group metal and the support.
[0077] In some embodiments, the silicon support may comprise a molecular sieve that has a Frame Type of BEA, CDO, CON, FAU, MEL, MFI or MWW.
SCR CATALYST [0078] The systems of the present invention can include one or more SCR catalysts. In some embodiments, a catalyst article may include a first SCR catalyst and a second SCR catalyst. In some embodiments, the first SCR catalyst and the second SCR catalyst can comprise the same formulation as each other. In some embodiments, the first SCR catalyst and the second SCR catalyst may comprise different formulations from each other.
[0079] The exhaust system of the invention may include an SCR catalyst that is positioned downstream of an injector to introduce ammonia or an ammonia-decomposable compound into the exhaust gas. The SCR catalyst can be positioned directly downstream of the injector to inject ammonia or a compound decomposed into ammonia (for example, there is no intermediate catalyst between the injector and the SCR catalyst).
[0080] The SCR catalyst includes a substrate and a catalyst composition. The substrate can be a through-flow substrate or a filtering substrate. When the SCR catalyst has a through-flow substrate, then the substrate may comprise the SCR catalyst composition (that is, the SCR catalyst is obtained by extrusion) or the SCR catalyst composition may be arranged or supported on the substrate (that is, the SCR catalyst composition is applied to the substrate by a coating method).
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27/41 [0081] When the SCR catalyst has a filtering substrate, it is a selective catalytic reduction filter catalyst, which is mentioned in the present document by the abbreviation “SCRF”. SCRF comprises a filtering substrate and the selective catalytic reduction (SCR) composition. References to the use of SCR catalysts throughout this application should include the use of SCRF catalysts, where applicable.
[0082] The selective catalytic reduction composition may comprise or consist essentially of a metal oxide based SCR catalyst formulation, a molecular sieve SCR catalyst formulation or a mixture thereof. Such SCR catalyst formulations are known in the art.
[0083] The selective catalytic reduction composition may comprise or consist essentially of a metal oxide-based SCR catalyst formulation. The metal oxide-based SCR catalyst formulation comprises vanadium or tungsten or a mixture thereof supported in a refractory oxide. Refractory oxide can be selected from the group consisting of alumina, silica, titania, zirconia, ceria and combinations thereof.
[0084] The metal oxide-based SCR catalyst formulation can comprise, or consist essentially of, a vanadium oxide (eg V2O5) and / or a tungsten oxide (eg WO3) supported on a selected refractory oxide from the group consisting of titania (for example, T1O2), ceria (for example, CeO2) and a mixed oxide or compound of cerium and zirconium (for example, Ce _x Zr (i _X ) O2, where x = 0 , 1 to 0.9, preferably x = 0.2 to 0.5).
[0085] When the refractory oxide is titania (for example, T1O2), preferably the concentration of the vanadium oxide is 0.5 to 6% by weight (for example, of the SCR formulation based on metal oxide) and / or the concentration of tungsten oxide (eg WO3) is 5 to 20% in
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28/41 weight. Most preferably, vanadium oxide (for example, V2O5) and tungsten oxide (for example, WO3) are supported on titanium oxide (for example, T1O2).
[0086] When the refractory oxide is ceria (eg CeCE), then preferably the concentration of vanadium oxide is 0.1 to 9% by weight (eg metal oxide based on the SCR formulation) ) and / or the tungsten oxide concentration (for example, WO3) is 0.1 to 9% by weight.
[0087] The metal oxide-based SCR catalyst formulation can comprise or consist essentially of a vanadium oxide (eg V2O5) and optionally a tungsten oxide (eg WO3), supported on titania (eg , T1O2).
[0088] The selective catalytic reduction composition may comprise or consist essentially of an SCR catalyst formulation based on molecular sieve. The SCR catalyst formulation based on molecular sieve comprises a molecular sieve, which is optionally a molecular sieve substituted by transition metal. It is preferred that the SCR catalyst formulation comprises a transition metal-substituted molecular sieve.
[0089] In general, the SCR catalyst formulation based on molecular sieve may comprise a molecular sieve with an aluminosilicate structure (eg zeolite), an aluminophosphate structure (eg AIPO), a silicoaluminophosphate structure (eg example, SAPO), an aluminosilicate structure that contains heteroatom, a structure that contains aluminophosphate structure (for example, MeAlPO, where Me is a metal) or a silicoaluminophosphate structure that contains heteroatom (for example, MeAPSO, where Me is a metal). The heteroatom (that is, in a structure that contains heteroatom) can be selected from the group consisting of boron (B), gallium
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29/41 (Ga), titanium (Ti), zirconium (Zr), zinc (Zn), iron (Fe), vanadium (V) and combinations of any two or more. It is preferred that the heteroatom is a metal (for example, each of the structures that contain heteroatom above can be a structure that contains metals).
[0090] It is preferred that the SCR catalyst formulation based on molecular sieve comprises, or consists essentially of a molecular sieve that has an aluminosilicate structure (for example, zeolite) or a silicoaluminophosphate structure (for example, SAPO).
[0091] When the molecular sieve has an aluminosilicate structure (for example, the molecular sieve is a zeolite), then normally the molecular sieve has a molar ratio of silica to alumina (SAR) from 5 to 200 (eg 10 to 200), 10 to 100 (for example, 10 to 30 or 20 to 80), such as 12 to 40 or 15 to 30. In some embodiments, a suitable molecular sieve has a SAR of> 200; > 600; or> 1,200. In some embodiments, the molecular sieve has a SAR of about 1,500 to about 2,100.
[0092] Normally, the molecular sieve is microporous. A microporous molecular sieve has pores with a diameter of less than 2 nm (for example, according to the IUPAC definition of “microporous” [see Pure & Appl. Chem. 66 (8), (1994), 1,739 to 1,758))).
[0093] The molecular sieve SCR catalyst formulation may comprise a small pore molecular sieve (eg, a molecular sieve with a maximum ring size of eight tetrahedral atoms), a medium pore molecular sieve (eg, a molecular sieve with a maximum ring size of ten tetrahedral atoms) or a large pore molecular sieve (for example, a molecular sieve with a maximum ring size of twelve tetrahedral atoms) or a combination of two or more of the same.
[0094] When a molecular sieve is a molecular sieve of
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30/41 small pore, then the small pore molecular sieve may have a frame structure represented by the Frame Type Code (FTC) selected from the group consisting of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, LTA, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SFW, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON or a mixture and / or intergrowth of two or more of them. Preferably, the small pore molecular sieve has a structural structure represented by an FTC selected from the group consisting of CHA, LEV, AEI, AFX, ERI, LRI, SFW, KFI, DDR and ITE. More preferably, the small pore molecular sieve has a structural structure represented by an FTC selected from the group consisting of CHA and ΑΕΙ. The small pore molecular sieve may have a structure organization represented by the FTC CHA. The small pore molecular sieve may have a structure organization represented by the FTC AEI. When the small pore molecular sieve is a zeolite and has a structure represented by the FTC CHA, then the zeolite can be chabazite.
[0095] When a molecular sieve is a medium-pore molecular sieve, then the medium-pore molecular sieve may have a frame structure represented by the Frame Type Code (FTC) selected from the group consisting of AEL, AFO , AHT, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, ITR, JRY, JSR, JST, LAU, LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW , NAB, NAT, NES, OBW, PAR, PCR, PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT, STW, SVR, SZR, TER, TON, TUN, UOS, VSV, WEI and WEN or a mixture and / or intergrowth of two or more of them. Preferably, the medium-pore molecular sieve has a structural structure represented by an FTC selected from the group consisting of FER, MEL, MFI and STT. More preferably, the medium-pore molecular sieve has a structure
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Structural 31/41 represented by an FTC selected from the group consisting of FER and MFI, particularly MFI. When the medium-pore molecular sieve is a zeolite and has a structure represented by the FTC FER or MFI, then the zeolite can be ferrierite, silicalite or ZSM-5.
[0096] When a molecular sieve is a large pore molecular sieve, then the large pore molecular sieve may have a frame structure represented by the Frame Type Code (FTC) selected from the group consisting of AFI, AFR , AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP, DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS , IWV, IWW, JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, ΟΚΟ, OSI, RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO , SFS, SFV, SOF, SOS, STO, SSF, SSY, USI, UWY and VET or a mixture and / or intergrowth of two or more of them. Preferably, the large pore molecular sieve has a structure organization represented by an FTC selected from the group consisting of AFI, BEA, MAZ, MOR and OFF. Most preferably, the large pore molecular sieve has a structural structure represented by an FTC selected from the group consisting of BEA, MOR and MFI. When the large pore molecular sieve is a zeolite and has a structure represented by FTC BEA, FAU or MOR, then the zeolite can be a beta, faujasite, zeolite Y, zeolite X or mordenite.
[0097] In general, it is preferable that the molecular sieve is a small pore molecular sieve.
[0098] The SCR catalyst formulation based on molecular sieve preferably comprises a molecular sieve substituted by transition metal. The transition metal can be selected from the group consisting of cobalt, copper, iron, manganese, nickel, palladium, platinum, ruthenium and rhenium.
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32/41 [0099] The transition metal can be copper. An advantage of SCR catalyst formulations that contain a substituted copper molecular sieve is that such formulations have an excellent NO _X reduction activity at low temperature (for example, it may be superior to the NO _X reduction activity at low temperature of a molecular sieve of substituted iron). The systems and method of the present invention can include any type of SCR catalyst, however, SCR catalysts that include copper (“Cu-SCR catalysts”) can experience more notable benefits from the systems of the present invention, as they are particularly vulnerable to the effects sulfation. Cu-SCR catalyst formulations may include, for example, Cu-substituted SAPO-34, Cu-substituted CHA zeolite, Cu-substituted AEI zeolites or combinations thereof.
[00100] The transition metal may be present in an extra-structural location on the outer surface of the molecular sieve or within a channel, cavity or cage of the molecular sieve.
[00101] Typically, the transition metal-substituted molecular sieve comprises an amount of 0.10 to 10% by weight of the transition metal-replaced molecular sieve, preferably an amount of 0.2 to 5% by weight.
[00102] In general, the selective catalytic reduction catalyst comprises the selective catalytic reduction composition in a total concentration of 0.5 to 4.0 g in ³ , preferably 1.0 to 3.0 4.0 g in ³ .
[00103] The SCR catalyst composition can comprise a mixture of a metal oxide based SCR catalyst formulation and a molecular sieve SCR catalyst formulation. The (a) SCR catalyst formulation based on metal oxide may comprise, or consist essentially of, a vanadium oxide (eg V2O5) and, optionally, a tungsten oxide (eg WO3), supported on
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33/41 titania (for example, T1O2) and (b) the SCR catalyst formulation based on molecular sieve can comprise a molecular sieve replaced by transition metal.
[00104] When the SCR catalyst is an SCRF, then the filter substrate may preferably be a wall flow filter substrate monolith. The wall flow filter substrate monolith (for example, SCR-DPF) typically has a cell density of 60 to 400 cells per square inch (cpsi) (from 0.04 m ² to 0.26 m ² ). It is preferred that the wall flow filter substrate monolith has a cell density of 100 to 350 cpsi (0.06 m ² to 0.23 m ² ), more preferably 200 to 300 cpsi (0.13 m ² to 0.19 m ² ).
[00105] The substrate monolith of the wall flow filter may have a wall thickness (for example, average inner wall thickness) of 0.20 to 0.50 mm, preferably 0.25 to 0.35 mm ( for example, about 0.30 mm).
[00106] Generally, the substrate monolith of the uncoated wall flow filter has a porosity of 50 to 80%, preferably 55 to 75%, and more preferably 60 to 70%.
[00107] The substrate monolith of the uncoated wall flow filter normally has an average pore size of at least 5 μηι. It is preferable that the average pore size is 10 to 40 μηι, like 15 to 35 μηι, more preferably 20 to 30 μηι.
[00108] The wall flow filter substrate can have a symmetric cell design or an asymmetric cell design.
[00109] In general, for an SCRF, the selective catalytic reduction composition is disposed within the monolith wall of the wall flow filter substrate. In addition, the selective catalytic reduction composition may be arranged on the walls of the input channels and / or on the walls of the output channels.
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34/41
COMBINATION [00110] Modalities of the present invention may include a mixture of (1) a platinum group metal on a support and (2) an SCR catalyst. In some embodiments, within the mixture, a weight ratio of the SCR catalyst to the platinum group metal on a support is from about 3: 1 to about 300: 1; about 3: 1 to about 250: 1; about 3: 1 to about 200: 1; about 4: 1 to about 150: 1; about 5: 1 to about 100: 1; about 6: 1a about 90: 1; about 7: 1 to about 80: 1; about 8: 1 to about 70: 1; about 9: 1 to about 60: 1; about 10: 1 to about 50: 1; about 3: 1; about 4: 1; about 5: 1; about 6: 1; about 7: 1; about 8: 1; about 9: 1; about 10: 1; about 15: 1; about 20: 1; about 25: 1; about 30: 1; about 40: 1; about 50: 1; about 75: 1; about 100: 1; about 125: 1; about 150: 1; about 175: 1; about 200: 1; about 225: 1; about 250: 1; about 275: 1; or about 300: 1.
DQC [00111] The catalyst articles and systems of the present invention can include one or more diesel oxidation catalysts. Oxidation catalysts, and in particular diesel oxidation catalysts (DOCs), are well known in the art. The oxidation catalysts are designed to oxidize CO to CO2 and gas phase hydrocarbons (HC) and an organic fraction of diesel particulates (organic fraction soluble) in CO2 and H2O. Typical oxidation catalysts include platinum and, optionally, also palladium on a high surface area inorganic oxide support, such as alumina, silica-alumina and a zeolite.
SUBSTRATE [00112] The catalysts of the present invention can each further comprise a through-flow substrate or filter substrate. In one embodiment, the catalyst can be coated on the through-flow or filter substrate and preferably deposited on the flow substrate
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35/41 through or through filter using a covering layer procedure.
[00113] The combination of an SCR catalyst and a filter is known as a selective catalytic reduction filter (SCRF catalyst). An SCRF catalyst is a single substrate device that combines the functionality of an SCR and particle filter and is suitable for embodiments of the present invention, as desired. Description and references to the SCR catalyst throughout this application must also include the SCRF catalyst, where applicable.
[00114] The through-flow or filter substrate is a substrate that has the ability to contain catalyst / absorbent components. The substrate is preferably a ceramic substrate or a metallic substrate. The ceramic substrate can be produced from any suitable refractory material, for example, alumina, silica, titania, cerium, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates, metalaluminosilicates (such as cordierite and espudomeno), or a mixture or mixed oxide of any two or more of them. Cordierite, a magnesium aluminum silicate, and silicon carbide are particularly preferred.
[00115] Metal substrates can be made of any suitable metal and, in particular, heat-resistant metals and metal alloys, such as titanium and stainless steel, as well as ferritic alloys containing iron, nickel, chromium and / or aluminum in addition to other metals -trace.
[00116] The through-flow substrate is preferably a through-flow monolith that has a honeycomb structure with many small thin-walled parallel channels that run axially through the substrate and that extend along an entrance or substrate exit. The channel cross section of the substrate can be of any shape, but is preferably square, sinusoidal, triangular, rectangular,
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36/41 hexagonal, trapezoidal, circular or oval. The through-flow substrate can also be of high porosity, which allows the catalyst to penetrate the substrate walls.
[00117] The filter substrate is preferably a thin-walled monolith filter. The channels of a wall flow filter are blocked alternately, which allows the exhaust gas stream to enter a channel from the inlet, then flow through the channel walls and exit the filter from a different channel that leads to the output. Particles in the exhaust gas stream are thus trapped in the filter.
[00118] The catalyst / absorber can be added to the through-flow substrate or filter by any known means, such as a coating layer procedure.
UREA INJECTOR / REDUCER [00119] The system may include a means for introducing a nitrogen reducer into the exhaust system upstream of the SCR and / or SCRF catalyst. It may be preferred that the means for introducing a nitrogen reducer into the exhaust system are directly upstream of the SCR or SCRF catalyst (for example, there is no intervening catalyst between the means for introducing a nitrogen reducer and the SCR or SCRF catalyst).
[00120] The reducer is added to the exhaust gases that flow by any suitable means to introduce the reducer into the exhaust gases. Suitable means include an injector, sprayer or feeder. Such means are well known in the art.
[00121] The nitrogen reducer for use in the system can be ammonia alone, hydrazine or an ammonia precursor selected from the group consisting of urea, ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate and ammonium formate. Urea is particularly preferred.
[00122] The exhaust system can also comprise a means for
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37/41 to control the introduction of a reducer in the exhaust gas in order to reduce NOx. Preferred control means may include an electronic control unit, optionally an engine control unit, and may additionally comprise a NOx sensor located downstream of the NO reduction catalyst.
BENEFITS [00123] The catalyst articles of the present invention can provide greater catalytic activity and selectivity. In addition, in some embodiments, HC oxidation and exothermic generation can be concentrated in the rear zone, thus protecting the frontal ASC zone from hydrothermal degradation.
[00124] In some embodiments, the catalyst articles of the present invention may have equivalent or enhanced conversion of NOx compared to a catalyst article that is equivalent, except that it does not include the SCR in the lower layer. In some embodiments, the catalyst articles of the present invention may have an improved conversion of NOx compared to an equivalent catalyst article, except that it does not include the first SCR catalyst, the inventive catalyst article that shows an improvement in NOx conversion of about 40 % to about 50%.
[00125] In some embodiments, catalyst articles of the present invention may have reduced activity for N2O formation at temperatures below about 350 ° C, compared to a catalyst article that is equivalent, except does not include the SCR in the lower layer of ASC. In some embodiments, the catalyst articles of the present invention may have reduced activity for the formation of N2O at temperatures below about 350 ° C compared to a catalyst article that is equivalent, except that it does not include the first SCR catalyst, the article inventive catalyst showing a reduction in the formation of N2O greater than about 60%.
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38/41 [00126] As used in this specification and the appended claims, the singular forms "one", "one" and "a / o" include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to "a catalyst" includes a mixture of two or more catalysts and the like.
[00127] The term "ammonia leak" means the amount of unreacted ammonia that passes through the SCR catalyst.
[00128] The term "support" means the material to which a catalyst is attached.
[00129] The term "calcining" or "calcining" means the heating of the material in air or oxygen. This definition is consistent with the IUPAC definition of calcination. ..... (IUPAC Compendium of Chemical Terminology, 2nd ed (the "Gold Book") Compiled by AD McNaught and A. Wilkinson Blackwell Scientific Publications, Oxford (1997) corrected version online XML: http: //goldbook.iupac .org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi: 10.1351 / goldbook.) Calcination is performed to decompose a metal salt and promote the exchange of metal ions within the catalyst and also to adhere the catalyst to a substrate. The temperatures used in calcination depend on the components in the material to be calcined and, in general, are between about 400 ° C and about 900 ° C, for approximately 1 to 8 hours. In some cases, calcination can be carried out up to a temperature of around 1,200 ° C. In applications involving the processes described in this document, calcinations are generally carried out at temperatures of about 400 ° C to about 700 ° C for approximately 1 to 8 hours, preferably at temperatures of about 400 ° At about 650 ° C for approximately 1 to 4 hours.
[00130] When a range, or ranges, is provided for several numerical elements, the range or ranges may include the values, unless
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39/41 is specified otherwise.
[00131] The term "selectivity of N2" means the conversion of percent ammonia to nitrogen.
[00132] The terms “diesel oxidation catalyst” (DOC), “diesel exothermic catalyst” (DEC), “NOx absorber”, “SCR / PNA” (reduction catalyst / selective catalytic passive NOx), “ cold start catalyst ”(CSC) and“ three-way catalyst ”(TWC) are terms well known in the art used to describe the various types of catalysts used to treat exhaust gases from combustion processes.
[00133] The term "platinum group metal" or "PGM" refers to platinum, palladium, ruthenium, rhodium, osmium and iridium. Platinum group metals are preferably platinum, palladium, ruthenium or rhodium.
[00134] The terms "downstream" and "upstream" describe the orientation of a catalyst or substrate in which the flow of exhaust gas is from the inlet end to the outlet end of the substrate or article.
[00135] The following examples merely illustrate the invention; the knowledgeable person will recognize many variations that are within the spirit of the invention and the scope of the claims.
EXAMPLE [00136] In this example, three nearby catalyst configurations were tested under simulated engine output conditions with systematically varied functionality: (1) SCR only, (2) SCR / DOC, (3) ASC / DOC and (4) SCR / ASC / DOC. In addition, tests were performed with ANR <1 and ANR> 1 to understand the impact of NH ₃ slip and ASC functionality on the overall system performance.
[00137] The tested configurations shown in Figure 5. Test conditions: 600 / 1,200 ppm NH ₃ , 1,000 ppm NO, 500 ppm (based on Cl) C10H22, 200 ppm CO, 10% O ₂ , 4,5% CO ₂ , 4,5% H ₂ O, total SV = 30,000 h-1, 40,000 h-1 and 50,000 h-1 for SCR / DOC catalyst,
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40/41
SCR / ASC / DOC and SCR respectively. The results are shown in Figures 6 to 13.
[00138] In configuration (1) with only one SCR catalyst, the system has the highest NOx conversion and the lowest N2O formation, but it has a very low HC / CO conversion and has no NH3 slip control, especially when ANR > 1. As shown in configuration (2), the NH3 slid from the SCR catalyst is oxidized in the rear area of DOC with very high N2O selectivity at low temperatures (T> 350 ° C); in addition, at higher temperatures (t <350 ° C), the oxidation of NH3 to DOC has a high selectivity for the formation of NOx, which reduces the total NOx conversion of the system.
[00139] To minimize the slip from NH3 to DOC downstream, the configuration (3) with ASC / DOC was evaluated either with the combination ASC or a traditional Pt / alumina type ASC both at 3 g / ft ³ point loading. As shown in Figure 11, configuration (3) with traditional ASC in the front zone, the system produces an even greater amount of N2O than in configuration (2) due to insufficient SCR functionality and the non-selective reaction of NO + NH3 in ASC pt. On the other hand, when configuration (3) is tested with the combination of ASC, the formation of N2O is reduced by> 60% at temperatures below 350 ° C. In fact, the maximum relevant temperatures between 250 ° C and 350 ° C, N2O from that system is still 30 to 50% lower than in the configuration (2). Similarly, the configuration (3) with combination ASC also showed high selectivity at higher temperatures compared to traditional ASC, resulting in a 40 to 50% increase in total NOx conversion. (See Figure 8 ). These results suggest that the ASC of the invention preferably promotes the selective reaction of NO + NH3 catalyzed by the Cu-SCR catalyst, minimizing the non-selective reaction of NO + NH3 and the oxidation of NH3 catalyzed by Pt, making it highly suitable
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41/41 for the coupled application.
[00140] To further improve the system's performance, a three-zone configuration (configuration (4)) with an additional front SCR zone was evaluated. As shown in Figures 8 and 12, the three-zone configuration with combination ASC in the middle zone showed improved NO conversion and N2 selectivity compared to the two-zone configuration with the combination ASC in the front. The overall performance of configuration (4) has NOx conversion and N2O formation similar to configuration (1) (SCR only) and similar NH3, HC and CO conversions of configurations (2) and (3) (SCR / DOC and ASC / DOC). (See Figures 8, 11, 6, 10 and 9).
[00141] In the configurations mentioned above, each zone / functionality can be coated on a single substrate or on separate substrates; and in an engine system equipped with a turbocharger, these features can be divided into pre- and post-turbo catalysts.

权利要求:
Claims (20)
[1]
1. Catalyst article, characterized by the fact that it comprises a substrate comprising an inlet and outlet end, a first zone and a second zone, the first zone comprising:
The. a lower layer of ammonia slip catalyst (ASC) comprising a platinum group metal on a support; and
B. an SCR layer comprising a second SCR catalyst, the SCR layer being located on the lower ASC layer;
wherein the second zone comprises a catalyst ("second zone catalyst") selected from the group consisting of a diesel oxidation catalyst (DOC) and an exothermic diesel catalyst (DEC);
wherein the lower ASC layer extends to the second zone; and where the first zone is located upstream of the second zone.
[2]
2. Catalyst article according to claim 1, characterized in that the bottom layer of ASC comprises a mixture of: (1) platinum group metal on a support with (2) a first SCR catalyst.
[3]
Catalyst article according to claim 1, characterized in that the lower layer of ASC extends from the outlet end to less than a total length of the substrate;
the SCR layer extends from the inlet end to less than a full length of the substrate and which overlaps at least partially with the bottom ASC layer; and
Petition 870190109533, of 10/28/2019, p. 7/11
2/5 the catalyst of the second zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, the second layer being located on top of the lower ASC layer and is shorter than the bottom ASC layer.
[4]
4. Catalyst article according to claim 1, characterized in that the lower layer of ASC extends from the inlet end to less than a total length of the substrate;
the SCR layer extends from the inlet end to less than a full length of the substrate, the SCR layer is located on top of the bottom ASC layer and does not extend further to the outlet end than the bottom layer of ASC; and the catalyst of the second zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, the second layer at least partially overlapping the lower ASC layer.
[5]
Catalyst article according to claim 1, characterized in that the lower layer of ASC extends from the inlet end to less than a total length of the substrate;
the SCR layer extends from the inlet end to less than a full length of the substrate, the SCR layer is located on top of the bottom ASC layer and extends further to the outlet end than the bottom ASC layer ; and the catalyst of the second zone is included in a layer that extends from the outlet end to less than a total length
Petition 870190109533, of 10/28/2019, p. 11/11
3/5 of the substrate.
[6]
6. Catalyst article according to claim 1, characterized by the fact that the bottom layer of ASC covers a total length of the substrate;
the SCR layer extends from the input end to less than a total length of the substrate, where the SCR layer is located on top of the bottom ASC layer; and the catalyst of the second zone is included in a second layer that extends from the outlet end to less than a total length of the substrate, the second layer being located on top of the bottom layer of ASC.
[7]
7. Catalyst article according to claim 1, characterized by the fact that the catalyst of the second zone is located within the substrate.
[8]
8. Catalyst article according to claim 1, characterized by the fact that the support comprises a siliceous material selected from the group consisting of: (1) silica; (2) a zeolite with a silica to alumina ratio greater than 200; and (3) alumina doped with amorphous silica with an S1O2 content of 40%.
[9]
Catalyst article according to claim 1, characterized in that the metal of the platinum group is present in the support in an amount of about 0.1% by weight to about 10% by weight of the total weight of the metal of the platinum and support group.
[10]
10. Catalyst article according to claim 2, characterized in that, within the mixture, a weight ratio between the first SCR catalyst and the platinum group metal in a support is about 10: 1 to about 50: 1.
[11]
Catalyst article according to claim 1,
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4/5 characterized by the fact that the first zone and the second zone are located on a single substrate and the first zone is located on the inlet side of the substrate and the second zone is located on the outlet side of the substrate.
[12]
12. Catalyst article according to claim 1, characterized in that the substrate comprises a first substrate and a second substrate, wherein the first zone is located on the first substrate and the second zone is located on the second substrate and the first substrate is located upstream of the second substrate.
[13]
13. Method for reducing emissions from an exhaust stream, characterized by the fact that it comprises placing the exhaust stream in contact with the catalyst article as defined in claim 1.
[14]
14. Exhaust purification system to reduce emissions from an exhaust stream, characterized by the fact that it comprises:
The. a turbocharger;
B. a third SCR catalyst; and,
ç. the catalyst article as defined in claim 1.
[15]
15. System according to claim 14, characterized by the fact that the third SCR catalyst is located upstream of the turbocharger.
[16]
16. System according to claim 14, characterized by the fact that the third SCR catalyst is located downstream of the turbocharger.
[17]
17. System according to claim 14, characterized by the fact that the third SCR catalyst and the catalyst article are located on a single substrate, with the third SCR catalyst located upstream of the first zone and the second zone.
[18]
18. System according to claim 14, characterized by the fact that the third SCR catalyst is located on a substrate to
Petition 870190109533, of 10/28/2019, p. 11/10
5/5 amount of the catalyst article substrate.
[19]
19. System according to claim 14, characterized by the fact that the third SCR catalyst is in tight coupling with the catalyst article.
[20]
20. System according to claim 14, characterized by the fact that it additionally comprises a pre-turbo SCR catalyst, located upstream of the turbocharger.

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法律状态:
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