Integrated scr and amox catalyst systems.
Abstract
Catalysts and catalytic articles for treating exhaust gas streams are described. In one or more embodiments, a catalyst system includes a first zone to abate nitrogen oxides by selective catalytic reduction, a second zone to oxidize ammonia and a third zone to oxidize carbon monoxide and hydrocarbons. Methods and systems for treating the exhaust gas stream are also provided. Methods of making and using such catalysts and catalytic articles are also described,.
Term
4.6 yearsleft in the term
Expires 4 May 2031.
- Priority
- Filed
- Granted
- Today
- Expires
16 claims: 10 independent, 6 dependent
- 1REIVINDICACIONES 1. Un artículo catalítico para tratar una corriente de gas de descarga que contiene material particulado, hidrocarburos, CO y amoníaco, el artículo comprende:un sustrato que tiene un extremo de entrada y un extremo de salida que definen una longitud axial;un primer recubrimiento catalítico que Incluye un metal del grupo del platino, el primer recubrimiento catalítico se extiende desde el extremo de salida hacia el extremo de entrada sobre menos que la longitud axial total del sustrato;y un segundo recubrimiento catalítico que Incluye un catalizador para la reducción catalítica selectiva (SCR) de óxidos de nitrógeno, el segundo recubrimiento catalítico se extiende desde el extremo de entrada hacia el extremo de salida sobre menos que la longitud axial total del sustrato y solapa una porción del primer recubrimiento catalítico.
- 2El artículo catalítico de la reivindicación 1, en donde el sustrato es un sustrato de flujo pasante tiene una pluralidad de pasajes extendidos longitudinalmente formados por paredes extendidas longitudinalmente que limitan y definen dichos pasajes.
- 3El artículo catalítico de la reivindicación 1, en donde el sustrato es una filtro de flujo de pared tiene paredes permeables al gas formadas en una pluralidad de canales que se extienden axialmente, cada canal tiene un extremo taponado con cualquier par de canales adyacentes taponados en los extremos opuestos de estos.
- 4El artículo catalítico de cualquiera de las reivindicaciones 1-3, en donde al menos una porción del metal del grupo del platino está en un soporte de óxido metálico refractario particulado.
- 5El artículo catalítico de cualquiera de las reivindicaciones 1-4, en donde el metal del grupo del platino es platino.
- 6El artículo catalítico de cualquiera de las reivindicaciones 1-5, en donde el primer recubrimiento catalítico y el segundo recubrimiento catalítico se solapan para formar tres zonas, una primera zona para eliminar el NOx por reducción catalítica selectiva, una segunda zona para oxidar amoníaco y una tercera zona para oxidar monóxldo de carbono e hidrocarburos.
- 7El artículo catalítico de cualquiera de las reivindicaciones 1-6, en donde el metal del grupo del platino se soporta directamente sobre las paredes del sustrato.
- 8El artículo catalítico de cualquiera de las reivindicaciones 1-7, en donde cada una de las tres zona ocupa individualmente en el intervalo de aproximadamente 10 a aproximadamente 80% de la longitud axial del sustrato.
- 9Un sistema de tratamiento de emisiones que comprende:un motor diesel que emite una corriente de descarga que incluye materia particulada, NOx y monóxldo de carbono;y un artículo catalítico de acuerdo con cualquiera de las reivindicaciones 1-8.
- 10El sistema de tratamiento de emisiones de la reivindicación 9, en donde hay un sustrato corriente arriba recubierto con un catalizador para la reducción catalítica selectiva de óxidos de nitrógeno dispuesto en comunicación continua con la corriente de descarga y entre el motor de diesel y el primer sustrato.
- 11El sistema de tratamiento de emisiones de la reivindicación 10, en donde el sustrato corriente comprende un sustrato de flujo pasante de estructura tipo panal de abeja.
- 12El sistema de tratamiento de emisiones de la reivindicación 10, en donde el sustrato corriente arriba comprende un sustrato de filtro de flujo de pared que tiene paredes permeables al gas formadas en una pluralidad de canales que se extienden axialmente, cada canal tiene un extremo taponado con cualquier par de canales adyacentes taponados en los extremos opuestos de estos.
- 13El sistema de tratamiento de emisiones de cualquiera de las reivindicaciones 9-11, en donde hay un sustrato de filtro de flujo de pared que tiene paredes permeables al gas formadas en una pluralidad de canales que se extienden axialmente, cada canal tiene un extremo taponado con cualquier par de canales adyacentes taponados en los extremos opuestos de estos recubiertos con un catalizador de oxidación de hidrocarburos o CO dispuesto en comunicación continua con la corriente de descarga y entre el motor de diesel y el primer sustrato.
- 14Un método para preparar un artículo catalítico de acuerdo con cualquiera de las reivindicaciones 1-8, el método comprende:recubrir directamente un primer metal del grupo del platino sustancialmente no soportado sobre las paredes porosas de un sustrato con estructura tipo panal de abeja;secar y calcinar el sustrato recubierto para fijar el primer metal del grupo del platino sustancialmente no soportado en el sustrato;recubrir con la suspensión una porción de las paredes porosas con una capa de recubrimiento sellador que contiene un catalizador para la reducción catalítica selectiva (SCR) de óxidos de nitrógeno;y secar y calcinar el sustrato recubierto para fijar la capa de recubrimiento sellador sobre el sustrato.
- 15Un método para preparar un artículo catalítico que tiene un extremo de entrada y un extremo de salida de acuerdo con cualquiera de las reivindicaciones 1-8, el método comprende:recubrir con la suspensión una primera capa de recubrimiento sellador que contiene un metal del grupo del platino adyacente a las paredes porosas del extremo de salida de un sustrato con estructura tipo panal de abeja;recubrir con la suspensión las paredes porosas con una segunda capa de recubrimiento sellador que contiene un catalizador para la reducción catalítica selectiva (SCR) de óxidos de nitrógeno, la segunda capa de recubrimiento sellador se extiende desde el extremo de entrada y al menos parcialmente solapa la primera capa de recubrimiento sellador;y secar y calcinar el sustrato recubierto para fijar las capas de recubrimiento sellador sobre el sustrato para proporcionar una primera zona para disminuir la reducción catalítica selectiva de amoniaco, una segunda zona para oxidar el amoniaco y una tercera zona para oxidar el monóxido de carbono e hidrocarburos.
- 16Un método para preparar un artículo catalítico de acuerdo con cualquiera de las reivindicaciones 1-8, el sustrato Incluye un extremo de entrada y extremo de salida que definen un longitud axial, el método comprende:recubrir una porción de salida del sustrato con un primer recubrimiento catalítico que contiene un metal del grupo del platino efectivo para catalizar la oxidación del monóxido de carbono en la corriente de descarga, la primera capa de recubrimiento catalítico se extiende desde el extremo de salida del sustrato hacia el extremo de entrada sobre menos que la longitud axial total;secar y calcinar el sustrato recubierto para fijar el primer recubrimiento catalítico sobre la porción de salida del sustrato;recubrir una porción de entrada del sustrato con un segundo recubrimiento catalítico que contiene un catalizador de reducción catalítica selectiva (SCR) efectivo para 5 reducir el NOx en la corriente de descarga, el segundo recubrimiento catalítico se extiende desde el extremo de entrada del sustrato hacia el extremo de salida sobre menos que la longitud axial total y solapa una porción de la primera capa de recubrimiento catalítico;y secar y calcinar el sustrato recubierto para fijar el segundo recubrimiento catalítico 10 sobre la porción de entrada del sustrato.
Independent claims16
92 paragraphs in 6 sections, as filed
(54) Title: INTEGRATED SCR AND AMOX CATALYTIC SYSTEMS. (54) Title: INTEGRATED SCR AND AMOX CATALYST SYSTEMS.
(57) Summary
Catalysts and catalytic articles for treating exhaust gas streams are described. In one or more embodiments, a catalyst system includes a first zone for scavenging nitrogen oxides by selective catalytic reduction, a second zone for oxidizing ammonia, and a third zone for oxidizing carbon monoxide and hydrocarbons. Methods and systems for treating the exhaust gas stream are also provided. Methods of manufacturing and using catalysts and catalytic articles are also described.
(57) Abstract
Catalysts and catalytic articles for treating exhaust gas streams are described. In one or more implementations, a catalyst system ineludes a first zone to abate nitrogen oxides by selective catalytic reduction, a second zone to oxidize ammonia and a third zone to oxidize carbon monoxide and hydrocarbons. Methods and systems for treating the exhaust gas stream are also provided. Methods of making and using such catalysts and catalytic articles are also described ,.
INTEGRATED SCR AND AMOX CATALYTIC SYSTEMS
TECHNICAL FIELD
The invention pertains to catalysts, methods for their manufacture, and methods for treating emissions in a discharge stream.
BACKGROUND
Diesel engine discharge is a heterogeneous mixture containing particulate emissions such as soot and gaseous emissions such as carbon monoxide, burned or partially burned hydrocarbons, and nitrogen oxides (collectively referred to as NO<sub>X</sub>), but also condensed phase materials (liquids and solids) which constitute the so-called particulate or particulate material. The catalyst compositions, often arranged on one or more monolithic substrates, are placed in the engine discharge systems to convert some or all of these discharge components to harmless compounds. For example, diesel discharge systems may contain one or more of a diesel oxidation catalyst, a soot filter, and a NO reduction catalyst.<sub>X</sub>.
Oxidation catalysts containing platinum group metals, base metals and combinations of these are known to facilitate the treatment of diesel engine discharge by activating the conversion of gaseous pollutants HC and CO and some proportion of the particulate material through the oxidation of these pollutants to carbon dioxide and water. Such catalysts are generally contained in units called diesel oxidation catalysts (DOC), which are placed in the discharge of diesel engines to treat the discharge before it is released into the atmosphere. Such catalysts are also contained in units called catalytic soot filters which simultaneously cover the particulate material and oxidize the HC, CO and the particulate material. In addition to the conversions of HC, gaseous CO, and particulate matter, these platinum group metal-containing oxidation catalysts (which are typically dispersed on support of refractory oxides) activate the oxidation of nitric oxide (NO) to NO<sub>2</sub>.
Selective catalytic reduction of ammonia (SCR) is a NO reduction technology<sub>X</sub> to be used to meet the strict targets of NO emissions<sub>X</sub> in diesel and poor burn engines. In the SCR ammonia process, NO<sub>X </sub>(normally consists of NO + NO<sub>2</sub>) reacts with ammonia (or a precursor to ammonia like urea) to form dinitrogen (NO<sub>2</sub>) on a catalyst typically composed of base metals. This technology is capable of NO conversions<sub>X </sub>greater than 90% in a typical diesel drive cycle, and thus represents one of the best approaches to achieve the severe NO reduction goals<sub>X</sub>.
A characteristic feature of some ammonia SCR catalyst materials is the propensity to retain considerable amounts of ammonia at the Lewis and Bronsted acid sites on the catalyst surface during the low temperature portions of a typical drive cycle. Subsequent increases in the discharge temperature can cause ammonia to desorb from the surface of the SCR ammonia catalyst and flow out of the vehicle's discharge line. An overdose of ammonia with the aim of increasing the NO conversion rate<sub>X</sub> It is another potential scenario where ammonia can exit the ammonia SCR catalyst.
The release of ammonia from the ammonia SCR catalyst presents several problems. The odor threshold for NH<sub>3</sub> it is 20 ppm in the air. Eye or throat irritation is noticeable above 100 ppm, skin irritation occurs at approximately 400 ppm, and IDLH is 500 ppm in air. NH<sub>3</sub> it is caustic, especially in its aqueous form, the condensation of NH<sub>3</sub> and water in the colder regions of the discharge line downstream of the discharge catalysts will give a corrosive mixture.
Therefore, it is desirable to remove the ammonia before it can pass into the exhaust pipe. A selective ammonia oxidation catalyst (AMOx) is used for this purpose, with the aim of converting excess ammonia to N<sub>2</sub>. It would be desirable to provide a selective ammonia oxidation catalyst that is capable of converting ammonia over a wide temperature range where ammonia release occurs in the motor cycle of vehicles, and can produce minimal nitrogen oxide by-products. The AMOx catalyst must also produce N<sub>2</sub>Or minimum, which is a powerful greenhouse gas.
SUMMARY
Aspects of the invention employ catalytic articles, catalyst systems, and methods for treating discharge gas streams, and methods for preparing catalytic articles for treating such gas. A first aspect pertains to a catalytic article for treating a discharge gas stream containing particulate matter, hydrocarbons, CO, and ammonia. In a first embodiment, the article comprises a substrate having an inlet end and an outlet end that define an axial length, a first catalytic coating including a platinum group metal, the first catalytic coating extending from the end of outlet to the inlet end over less than the total axial length of the substrate; and a second catalytic coating including a catalyst for selective catalytic reduction (SCR) of nitrogen oxides, the second catalytic coating extends from the inlet end to the outlet end over less than the total axial length of the substrate and overlaps one portion of the first catalytic coating. In a second embodiment, the substrate is a through-flow substrate having a plurality of longitudinally extending passages formed by longitudinally extending walls that limit and define said passages. In a third embodiment, the substrate is a wall flow filter having gas permeable walls formed in a plurality of axially extending channels, each channel having one end plugged with any pair of adjacent channels plugged at the opposite ends of these. .
In a fourth embodiment, the first to third embodiments can be modified such that at least a portion of the platinum group metal is on a particulate refractory metal oxide support. In a fifth embodiment, the first through fourth modalities can be modified such that the platinum group metal is platinum. In a sixth mode, the first to fifth modes can be modified so that the first catalytic coating and the second catalytic coating overlap to form three zones, a first zone to remove NOx by selective catalytic reduction, a second zone to oxidize ammonia and a third zone to oxidize carbon monoxide and hydrocarbons. In a seventh embodiment, the first to sixth modalities can be modified so that each of the three zones individually occupies a range of about 10 to 80% of the axial length of the substrate. In an eighth embodiment, the first through seventh modalities can be modified so that the platinum group metal is supported directly on the walls of the substrate.
Another aspect of the invention belongs to an emission treatment system. In a ninth embodiment, the system comprises a diesel engine that emits a discharge current that includes particulate matter, NOx and carbon monoxide; and a catalytic article according to the modalities from the first to the eighth. For example, the catalytic article may include a first substrate that has an inlet end and an outlet end that define an axial length positioned downstream and in continuous communication with the diesel engine, the substrate that has a first catalytic coating that includes a platinum group metal, the first catalytic coating that extends from the outlet end to the inlet end over less than the total axial length of the substrate, and a second catalytic coating including a catalyst for selective catalytic reduction (SCR) of nitrogen oxides, the second catalytic coating extends from the inlet end to the outlet end over less than the total axial length of the substrate and overlaps a portion of the first catalytic coating layer. In one or more system embodiments, the first substrate is selected from the group consisting of a wall-flow substrate and a through-flow substrate.
In a tenth embodiment, the ninth embodiment can be modified so that there is an upstream substrate coated with a catalyst for selective catalytic reduction of nitrogen oxides arranged in continuous communication with the discharge stream and between the diesel engine and the first substratum. In an eleventh embodiment, the tenth embodiment is modified so that the upstream substrate comprises a through-flow honeycomb structure substrate. In a twelfth embodiment, the tenth embodiment is modified so that the upstream substrate comprises a wall flow filter substrate having gas permeable walls formed in a plurality of axially extending channels, each channel having one end plugged with any pair of adjacent channels plugged at opposite ends of these.
In a thirteenth embodiment, the tenth embodiment is modified such that there is a wall flow filter substrate having gas permeable walls formed in a plurality of axially extending channels, each channel has one end plugged with any pair of adjacent channels plugged at opposite ends of these coated with a hydrocarbon or CO oxidation catalyst arranged in continuous communication with the discharge stream and between the diesel engine and the porous substrate.
Another aspect of the invention pertains to a method of preparing a catalytic article. In the fourteenth embodiment according to the first to eighth modalities, a catalytic article is prepared according to a method comprising directly coating a first platinum group metal substantially unsupported on the porous walls of a honeycomb structure substrate from bee; drying and calcining the coated substrate to fix the first platinum group metal substantially unsupported on the substrate; coating a portion of the porous walls with the suspension with a sealant coating layer containing a catalyst for selective catalytic reduction (SCR) of nitrogen oxides; dry and calcine the coated substrate to fix the sealant coating layer on the substrate.
In a fifteenth embodiment, a method is provided for preparing a catalytic article having an inlet end and an outlet end for treating a discharge stream containing NOx. In the fifteenth embodiment, a catalytic article according to the first to eighth modalities is prepared according to a method using a method comprising coating the suspension with a first layer of sealant coating containing a platinum group metal adjacent to the outlet end of the porous walls of a honeycomb structure substrate; coat the porous walls with the suspension with a second layer of sealing coating containing a catalyst for selective catalytic reduction (SCR) of nitrogen oxides, the second layer of sealing coating extends from the inlet end and at least partially overlaps the first layer of sealant coating; and drying and calcining the coated substrate to affix the sealant coating layers onto the substrate to provide a first zone to decrease selective catalytic reduction of ammonia, a second zone to oxidize ammonia, and a third zone to oxidize carbon monoxide and hydrocarbons.
In a sixteenth embodiment, a method is provided for preparing a catalytic article having an inlet end and an outlet end for treating a discharge stream containing NOx. In the fifteenth embodiment, a catalytic article according to the first to eighth modalities is prepared according to a method comprising coating an outlet portion of the substrate with a first catalytic coating containing a platinum group metal effective for catalyze the oxidation of carbon monoxide in the discharge stream, the first catalytic coating layer extends from the outlet end of the substrate to the inlet end over less than the total axial length; drying and calcining the coated substrate to fix the first catalytic coating on the outlet portion of the substrate; coating a portion of the substrate inlet with a second catalytic coating containing an effective selective catalytic reduction (SCR) catalyst to reduce NOx in the discharge stream, the second catalytic coating extends from the inlet end of the substrate to the end outlet over less than total axial length and overlapping a portion of the first catalytic coating layer; and drying and calcining the coated substrate to fix the second catalytic coating on the inlet portion of the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings illustrate the embodiments of the invention. It will be understood that the Figures are not to scale and that some features such as monolith channels can be increased in size to show the features according to the embodiments of the invention.
Figure 1 shows a schematic of a monolith of the catalyst and the geometry of the sealant coating on a single channel of the monolith after coating with both a first and second catalyst;
Figure 2 is a schematic view illustrating NH conversion<sub>3</sub> a N<sub>2</sub>and CO, HC to CO<sub>2</sub> in a catalytic system according to one or more modalities;
Figure 3 shows a schematic of a catalyst monolith and the geometry of the sealant coating on a single channel of the monolith after coating the entire substrate of Figure 1; and
Figure 4 is a schematic of an engine emission treatment system, in accordance with an embodiment of the present invention;
DETAILED DESCRIPTION
Before describing various illustrative embodiments of the invention, it will be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The invention is capable of other embodiments and of being carried out or practiced in various ways.
As used in this description and the appended claims, the singular forms one, one and the include plural referents unless the context clearly indicates otherwise. Thus, for example, the reference to a catalyst includes a mixture of two or more catalysts, and the like. As used herein, the term decrease means decrease in quantity and decrease means a decrease in quantity, caused by any means. Where they appear in the present description, the terms engine discharge current and discharge current refer to the engine output effluent as well as the downstream effluent of one or more catalyst system components including but not limited to an oxidation catalyst diesel and / or soot filter.
One aspect of the invention pertains to a catalyst. According to one or more embodiments, the catalyst can be disposed on a monolithic substrate as a sealer coating layer. As used herein and as described in Heck, Ronald, and Robert Farrauto, Catalytic Air Pollution Control, New York: Wiley-lnterscience, 2002, pgs. 18-19, a sealant coating layer includes a layer of material of different composition disposed on the surface of the monolithic substrate or an underlying sealant coating layer. A catalyst can contain one or more layers of sealing coating, and each layer of sealing coating can have unique catalytic chemical functions.
In one or more embodiments, bifunctional catalysts are provided. In accordance with one aspect of the invention, a bifunctional catalyst is provided comprising a modular catalyst system with physically separate compositions for the SCR function and the NH oxidation function<sub>3</sub>. According to one or more modalities, such modular catalytic systems allow greater flexibility to adjust the kinetics of the two functions independently. By doing this, the physical structure of the catalyst can be used to control the sequence of chemical-catalytic events, to increase NO conversion<sub>X</sub> and NH<sub>3</sub>, and to increase the selectivity to N<sub>2</sub>. Catalyst Compositions for SCR Function and NH Oxidation Function<sub>3 </sub>they may reside in discrete layers of coating on the substrate or, alternatively, the compositions for the SCR and NH oxidation functions<sub>3</sub> they may reside in discrete longitudinal zones on the substrate.
The term SCR function will be used in the present description to refer to a chemical process described by stoichiometric Eq. 1.
NOT<sub>X</sub> + 4 NH<sub>3</sub> + (3-2x) O<sub>2</sub> - ♦ 4 N<sub>2</sub> + 6 H<sub>2</sub>O Ec. 1
More generally it will refer to any chemical process in which NO<sub>X</sub> and NH<sub>3</sub> combine to produce preferably N<sub>2</sub>. The term SCR composition refers to a material composition effective in catalyzing SCR function. The term NH oxidation function<sub>3</sub> will be used to refer to a chemical process herein described by Eq 2.
NH<sub>3</sub> + 5 O<sub>2</sub> - 4 NO + 6 H<sub>2</sub>O Ec. 2
More generally, this will refer to a process in which NH<sub>3</sub> reacts with oxygen to produce NO, NO<sub>2</sub>, N<sub>2</sub>O, or preferably N<sub>2</sub>. The term NH oxidation composition<sub>3</sub> refers to a material composition effective to catalyze the oxidation function of NH<sub>3</sub>
Referring to Figure 1, one or more embodiments of the invention are directed to catalytic articles 10 for treatment of a discharge gas stream containing particulate matter, hydrocarbons, CO, and ammonia. The catalytic articles comprise a substrate 12, often referred to as a carrier or carrier substrate. Substrate 12 has an inlet end 22 and an outlet end 24 that generally define an axial length L. Substrate 12 generally has a plurality of channels 14 of which only one is shown for clarity. A first catalytic coating 16 on the substrate includes a platinum group metal. The first catalytic coating extends from the outlet end 24 of the substrate 12 to the inlet end 22 over less than the total axial length L of the substrate 12. A second catalytic coating 18 includes a catalyst for selective catalytic reduction (SCR) of nitrogen oxides. The second catalytic coating 18 extends from the inlet end 22 of the substrate 12 to the outlet end 24 over less than the total axial length L of the substrate 12. The second catalytic coating 18 overlaps a portion 20 of the first catalytic coating 16.
The metal of the platinum group of some modalities is one or more of platinum, palladium, radius, ruthenium, osmium and iridium. In the disclosed embodiments, the platinum group metal is one or more of palladium, platinum, and combinations thereof. In specific embodiments, the platinum group metal includes platinum, or alone or in combination with other platinum group metals.
In accordance with disclosed embodiments, a portion of the platinum group metal is supported on a particulate refractory oxide support. In some specific embodiments, the platinum group metal is supported directly on the walls of the substrate. As used in this description and the appended claims, the term "directly supported on the substrate wall" means that the metal is not on a particulate support, such as by impregnating the solution. Additionally, the term "substantially unsupported" means that the metal is supported directly on the wall of the substrate. For example, metal is deposited on the substrate without involving a particulate refractory oxide support,
In exposed embodiments, the first catalytic coating and the second catalytic coating overlap to form three zones 16, 18, and 20. As shown in Figure 2, the first zone 18 removes NOx by selective catalytic reduction. The second zone 20 oxidizes ammonia and the third zone 16 oxidizes carbon monoxide and hydrocarbons. To allow oxidation of CO and HC, the third zone must be accessible to CO and HC to allow activation and oxidation.
In exposed modalities, each of the three zones individually occupies in the range of approximately 10 to 80% of the axial length of the substrate. In specific modalities, each of the three zones occupies 1/3 of the axial length of the substrate.
The substrate
According to one or more embodiments, the catalyst substrate can be any of those materials typically used to prepare automotive catalysts and will typically comprise a metal or ceramic honeycomb structure. Any suitable substrate can be employed, such as a monolithic through-flow substrate and having a plurality of parallel thin gas flow ducts that extend from an inlet to an outlet face of the substrate, such that the ducts are open to the fluid flow. Ducts that are essentially straight pathways from its fluid inlet to fluid outlet are defined by the walls over which the catalytic material is coated as a "sealing coating" so that gases flowing through the ducts contact the material Catalytic Monolithic substrate flow ducts are thin walled channels that can be of any suitable cross-sectional shape such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures can contain from about 60 to about 1,200 or more gas inlet openings (i.e. cells) per square inch of cross section (cpsi). A representative and commercially available through-flow substrate is Corning 400/6 cordierite material that is constructed of cordierite and has 400 cpsi and a wall thickness of 6 mil. However, it will be understood that the invention is not limited to a particular type of substrate, material, or geometry.
Ceramic substrates can be made from any suitable refractory material, for example, cordierite, cordierite-α-alumina, silicon nitride, zllcon mulllta, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicates, zircon, petalite, a-alumina, aluminosilicates and the like.
Useful substrates for catalysts according to one or more embodiments of the present invention may also be metallic in nature and be composed of one or more metals or metallic alloys. Illustrative metal supports include heat resistant metals and metal alloys such as titanium and stainless steel as well as other alloys in which iron is a substantial or majority component. Such alloys may contain one or more nickel, chromium, and / or aluminum, and the total amount of those metals may comprise at least 15% by weight of the alloy, eg, 10-25% by weight of chromium, 3-8 % by weight of aluminum and up to 20% by weight of nickel. The alloys can also contain small amounts or traces of one or more other metals such as manganese, copper, vanadium, titanium, and the like. Metal substrates can be used in various forms such as corrugated sheets or monolithic form. A representative commercially available metal substrate is manufactured by Emitec. However, it will be understood that the invention is not limited to a particular type of substrate, material, or geometry. The surface of the metal substrates can be oxidized at high temperatures, for example 1000 ° and higher, to form an oxide layer on the surface of the substrate, and thus improves the corrosion resistance of the alloy. Such high temperature-induced oxidation can further improve the adhesion of the refractory metal oxide support and metal catalytic promoter components to the substrate.
Wall flow substrates useful for supporting SCR catalyst compositions in accordance with embodiments of the invention have a plurality of thin, substantially parallel gas flow passages that extend along the longitudinal axis of the substrate. Typically, each passage is blocked at one end of the body of the substrate, with alternate passages blocked at opposite ends of the faces. Such monolithic carriers can contain up to about 700 or more flow passages (or cells) per square inch of cross section, although much less can be used. For example, the carrier may have from about 7 to 600, more typically from about 100 to 400, cells per square inch (cpsi). Cells can have cross sections that are rectangular, square, round, oval, triangular, hexagonal, or are of other polygonal shapes. Wall flow substrates have a wall thickness typically between 0.002 and 0.1 inches. Suitable wall flow substrates have wall thicknesses between 0.002 and 0.015 inches.
Suitable wall flow filter substrates are composed of ceramic-like materials such as cordierite, alpha alumina, silicon carbide, silicon nitride, zirconia, mulite, spoumene, alumina-silica-magnesia, or zirconium silicate, or made of a porous, refractory metal. Wall flow substrates can also be formed from ceramic fiber composites. Suitable wall flow substrates are formed from cordierite and silicon carbide. Such materials are capable of resisting the environment, particularly the high temperatures, encountered in the treatment of discharge currents. The wall flow filter can be coated with the SCR catalyst over its entire axial length, or a portion of the total axial length of the filter in a coated configuration zone.
Wall flow substrates suitable for use in the system of the invention employ thin, porous-walled, monoliths of the honeycomb type (monoliths) through which the fluid stream passes without causing too great an increase in back pressure or pressure through the Article. Typically, the presence of a clean wall flow article will create a reprint of a 1-inch water column at 10 psig. In one embodiment, the ceramic wall flow substrates used in the system are formed of a material having a porosity of at least 40% or 45% (eg, 40% to 80%) having an average size of pores of at least 5 microns (for example, 5 to 30 microns). In specific embodiments, such materials have a porosity of at least 50% (eg, 50% to 80%). The porosity of the material that forms the walls can be defined by the density of the wall versus the theoretical density of the material. In specific embodiments, the substrates have a porosity of at least 55% and have an average pore size of at least 10 microns. When substrates with these porosities and these average pore sizes are coated with the techniques described below, suitable levels of SCR catalyst compositions can be loaded onto the substrates to achieve excellent NO conversion efficiency<sub>X</sub>. These substrates are still capable of retaining the proper characteristics of the discharge flow, that is, an acceptable back pressure, despite the SCR catalyst charge. United States Patent No. 4,329,162 is incorporated herein by reference with respect to the description of suitable wall flow substrates. Substrates 12 can also be a high efficiency filter that removes at least about 70% of the particulate matter in the gas stream.
Typical commercial use wall flow filters are typically formed with lower wall porosities, eg, about 35% to 50%, than the wall flow filters used in the invention. In general, the pore size distribution of commercial wall flow filters is typically very wide with an average pore size of less than 17 microns.
SCR Composition
In accordance with one or more embodiments of the invention, an effective component for catalyzing SCR function (referred to herein as a SCR component) is used in a coating as part of a NO-lowering catalyst composition.<sub>X</sub>. Typically, the SCR component is part of a composition that includes other components in a sealant coating. However, in one or more modalities the NO lowering catalyst composition<sub>X</sub> it can include only the SCR component.
In some embodiments, the invention utilizes an SCR component that includes a ml-porous Inorganic framework or molecular sieve on which a metal from one of the VB, VIB, VIIB, VIIIB, IB, or IIB groups of the periodic table is deposited at extra-framework sites on the outer surface or within the channels, cavities, or cages of the molecular sieve. The metals can be in one of several forms, which include, but are not limited to, zero-valent or clustered metal atoms, isolated cations, mononuclear or polynuclear oxyl tolons, or as extended metal oxides. In specific embodiments, metals include iron, copper, and mixtures or combinations thereof.
In certain embodiments, the SCR component contains in the range of approximately
0.10% and approximately 10% by weight of a group VB, VIB, VIIB, VIIIB, IB, or IIB metal located at the extra-entangled sites on the external surface or within the channels, cavities, or cages of the molecular sieve. In preferred embodiments, the metal of the extra framework is present in an amount in the range of about 0.2% and about 5% by weight.
The microporous Inorganic framework may consist of a microporous zeolite or aluminosilicate or have any of the framework structures listed in the Zeolite Structures Database published by the International Zeolite Association (IZA). Lattice structures include, but are not limited to those of the CHA, FAU, BEA, MFI, MOR types. Non-limiting examples of zeolites with these structures include chabasite, faujasite, zeolite Y, ultrastable zeolite Y, zeolite beta, mordenite, silicalite, zeolite X, and ZSM-5. Some modalities use aluminosilicate zeolites that have a silica / alumina molar ratio (defined as SiO<sub>2</sub>/AI<sub>2</sub>OR<sub>3</sub> and abbreviated as SAR) of at least about 5, preferably at least about 20, with useful ranges of about 10 to 200.
In specific embodiments, the SCR component includes an aluminosilicate molecular sieve having a CHA crystal lattice type, a SAR greater than about 15, and a copper content exceeding about 0.2 wt%. In a more specific embodiment, the SAR is at least about 10, and copper content from about 0.2% by weight to about 5% by weight. Zeolites having the CHA structure include, but are not limited to, natural chabasite, SSZ-13, LZ-218, Linde D, Linde R, Phi, ZK-14, and ZYT-6. Other suitable zeolites are further described in US Patent No. 7,601,662 entitled Copper CHA Zeolite Catalysts, the entire content of which is incorporated herein by reference.
In accordance with one or more embodiments of the invention, SCR compositions are provided that include non-zeolitic molecular sieves. As used herein, the term non-zeolitic molecular sieve refers to corner-sharing tetrahedral webs where at least a portion of the tetrahedral sites are occupied by an element other than silicon or aluminum. Non-limiting examples of such molecular sieves include aluminophosphates and metal-aluminophosphates, where the metal can include silicon, copper, zinc, or other suitable metals. Such modalities may include a non-zeolitic molecular sieve having a type of glass lattice selected from CHA, FAU, MFI, MOR, and BEA.
The non-zeolitic compositions can be used in the SCR component in accordance with the embodiments of the present invention. Specific non-limiting examples include the silicoaluminophosphates SAPO-34, SAPO-37, SAPO-44. Synthesis of the synthetic form of SAPO-34 is described in US Patent No. 7,264,789, which is hereby incorporated by reference. A method for preparing another synthetic non-zeolitic molecular sieve having a chabasite structure, SAPO-44, is described in US Patent No. 6,162,415, which is hereby incorporated by reference.
SCR compositions consisting of vanadium supported on a refractory metal oxide such as alumina, silica, zirconia, titania, ceria, and combinations thereof are well known and widely used commercially in mobile applications. Typical compositions are described in US Patent Nos. 4,010,238 and 4,085,193, the entire contents of which are incorporated herein by reference. Commercially used compositions, especially in mobile applications, comprise TIO<sub>2</sub> about which WO<sub>3</sub> and V<sub>2</sub>OR<sub>5</sub> they disperse at concentrations in the Range of 5 to 20% by weight and 0.5 to 6% by weight, respectively. These catalysts may contain other Inorganic materials such as SIO<sub>2</sub> and ZrO<sub>2</sub> they act as binders and promoters.
Composition for NH oxidation<sub>3</sub>
According to one or more embodiments of the invention, an effective composition to catalyze the oxidation function of NH<sub>3</sub> (herein referred to as NH oxidation component<sub>3</sub>) is used in a NO decrease catalyst<sub>X</sub>. Ammonia contained in a discharge gas stream reacts with oxygen on the NH oxidation component<sub>3</sub> to form N<sub>2</sub> according to Eq 1.
According to one or more modalities, the oxidation component of NH<sub>3 </sub>it can be a supported precious metal component which is effective in removing ammonia from the discharge gas stream. In one or more embodiments, the precious metal component includes ruthenium, rhodium, iridium, palladium, platinum, silver, or gold. In specific embodiments, the precious metal component includes physical and chemical mixtures and atomically doped combinations of ruthenium, radium, iridium, palladium, platinum, silver, and gold. In a more specific embodiment, the precious metal component includes platinum, in an even more specific embodiment, platinum is present in an amount in the Range of about 0.008% to 2% by weight (metal), based on the bearing load of Pt.
According to one or more embodiments, the precious metal component is deposited on a large surface area refractory metal oxide support. Examples of suitable large surface area refractory metal oxides employ, but are not limited to, alumina, silica, titania, ceria, and zirconia, as well as the physical mixtures, chemical combinations, and / or atomically doped combinations thereof. In specific embodiments, the refractory metal oxide may contain a mixed oxide such as silica-alumina, amorphous or crystalline aluminosilicates, alumina-zirconia, alumina-lanthanum, alumina-chromia, alumina-baria, alumina-ceria, and the like. An example of a refractory metal oxide comprises γ-alumina with a large surface area having a specific surface area of approximately 50 to 300 m.<sup>2</sup> / g.
Furthermore as mentioned herein, the oxidation component of NH<sub>3</sub> It can include a zeolitic or non-zeolitic molecular sieve which can have any of the lattice structures listed in the Zeolite Structures Database published by the International Association of Zeolites (IZA). Lattice structures include, but are not limited to those of the CHA, FAU, BEA, MFI, and MOR types. In one embodiment, a component of the molecular sieve can be physically mixed with an oxide that supports the platinum component. In an alternative embodiment, platinum can be distributed on the outer surface or in the channels, cavities, or cages of the molecular sieve.
The oxidation composition of NH<sub>3</sub> It may contain an active component for the SCR function of ammonia. The SCR component can consist of any of the SCR components described in the previous section. In one embodiment, the oxidation component of NH<sub>3</sub> It includes a physical mixture of an oxide supported platinum component and an SCR component. In an alternative embodiment, platinum can be distributed on the external surface or in the channels, cavities, or cages of the SCR component. In one or more embodiments, the catalyst article includes two layers for NH oxidation<sub>3</sub>, a first layer that includes a platinum group metal component, for example, Pt, and a second layer that includes a molecular sieve, for example, a zeolite.
Sealant Coating Layers
According to one or more modalities, the SCR component and the NH oxidation component<sub>3</sub> They can be applied in sealer coating layers which are coated and adhered to the substrate.
For example, a sealer coating layer containing a composition of the NH oxidation component<sub>3</sub> It can be formed by preparing a mixture or a solution of a platinum precursor in a suitable solvent, for example, water. Generally, from an economic and environmental point of view, aqueous solutions of soluble platinum compounds or complexes are preferred. Typically, the platinum precursor is used in the form of a compound or complex to achieve dispersion of the platinum precursor in the support. For the purposes of the present invention, the term platinum precursor means any compound, complex, or the like, which, during calcination or Initial phase of use, decomposes or otherwise converts to a catalytically active form. Suitable platinum complexes and compounds, include but are not limited to platinum chlorides (eg, salts of [PtCI<sub>4</sub>]<sup>2</sup>', [PtCI6]<sup>2</sup>'), platinum hydroxides (for example the salts of [Pt (OH) 6]<sup>2</sup>'), platinum amines (for example the salts of [Pt (NH3) 4]<sup>2+</sup>, [Pt (NH3)<sub>6</sub>]<sup>4+</sup>), platinum hydrates (for example the salts of [Pt (OH2) 4]<sup>2</sup>*), bls (acetyllacetonates) of platinum, and mixed or complex compounds (for example, [Pt (NH3)<sub>2</sub>(CI)<sub>2</sub>]). A representative and commercially available source of platinum is 99% ammonium hexachloroplatinate from Strem Chemicals, Inc. which may contain traces of other precious metals. However, it will be understood that this invention is not restricted to platinum precursors of a particular type, composition, or purity. A mixture or solution of the platinum precursor is added to the support by one of several chemical means. These include impregnation of a platinum precursor solution onto the support which is followed by a fixing step that incorporates an acid component (eg acetic acid) or a basic component (eg ammonium hydroxide). This wet solid can be chemically reduced or calcined or used as is. Alternatively, the support can be suspended in a suitable vehicle (for example water) and reacted with the platinum precursor in solution. The latter method is more typical when the support is a zeolite, and it is desired to attach the platinum precursor to the ion exchange sites in the zeolite framework. Additional process steps may include fixation by an acidic component (eg acetic acid) or a basic component (eg ammonium hydroxide), chemical reduction, or calcination,
In one or more embodiments using sealant coating layers of an SCR composition, the layer may contain a zeolitic or non-zeolitic molecular sieve into which a metal of one of the VB, VIB, VIIB, VIIIB, IB groups is distributed, or IIB of the periodic table. An example of metal in this series is copper. An illustrative metal in these series is copper. Examples of molecular sieves include, but are not limited to, zeolites having one of the following crystal structures CHA, BEA, FAU, MOR, and MFI. A suitable method of distributing the metal in the zeolite is first to prepare a mixture or solution of the metal precursor in a suitable solvent, for example water. Generally, from an economic and environmental point of view, aqueous solutions of soluble metal compounds or complexes are preferred. For the purposes of the present invention, the term metal precursor means any compound, complex, or the like that can be dispersed on the zeolite support to give a catalytically active metal component. For copper, example metal from group IB, suitable complexes, or compounds include, but are not limited to anhydrous or hydrated copper sulfate, copper nitrate, copper acetate, copper acetylacetonate, copper oxide, copper hydroxide, and copper amine salts (for example [Cu (NH<sub>3</sub>)<sub>4</sub>]<sup>2+</sup>). A representative commercially available source of copper is 97% copper acetate from Strem Chemicals, Inc., which may contain traces of other metals, particularly iron and nickel. However, it will be understood that this invention is not restricted to metal precursors of a particular type, composition, or purity. The molecular sieve can be added to the metal component solution to form a suspension. This suspension can be allowed to react so that the copper component is distributed in the zeolite. This can result in the copper being distributed in the pore channels as well as on the outer surface of the molecular sieve. Copper can be distributed as copper (II) ions, copper (I) ions, or as copper oxide. After the copper is distributed on the molecular sieve, the solids can be separated from the liquid phase of the suspension, washed, and dried. The resulting copper-containing molecular sieve can also be calcined to fix the copper.
To apply a sealant coating layer according to one or more embodiments of the invention, the finely divided particles of a catalyst, which may consist of the SCR component, the NH oxidation component<sub>3</sub>, or a mixture of these, is suspended in an appropriate vehicle, for example water, to form a suspension. Other promoters and / or stabilizers and / or surfactants may be added to the suspension as mixtures or solutions in water or a more flexible vehicle with Water. In one or more embodiments, the suspension is sprayed to result in substantially all solids having particle sizes of less than about 10 microns, i.e., in the Range of about 0.1-8 microns, at an average diameter. Spraying can be done in a ball mill, Eiger continuous mill, or other similar equipment. In one or more modalities, the suspension has a pH of about 2 to 7. The pFI of the suspension can be adjusted if necessary by adding a suitable amount of an inorganic or organic acid to the suspension. The solids content of the suspension can be, for example, about 20-60% by weight, and more particularly about 35-45% by weight. The substrates can then be dipped into the suspension, or else the suspension can be coated with the substrate, so that a desired charge of the catalyst layer will be deposited on the substrate. Thereafter, the coated substrate is dried at about 100 ° C and calcined by heating, for example, at 300-650 ° C for about 1 to 3 hours. Drying and calcination are typically carried out in air. The coating, drying, and calcination processes can be repeated if necessary to achieve the desired final gravimetric amount of the catalyst sealant coating layer on the support. In some cases, complete removal of the liquid and other volatile components may not occur until the catalyst is put into use and subjected to the high temperatures encountered during operation.
After calcination, the charge of the catalyst coating can be determined by calculating the difference between the weights of the coated and uncoated substrate. As will be apparent to those skilled in the art, the catalyst load can be modified by altering the solids content of the coating suspension and the viscosity of the suspension. Alternatively, repeated dips of the substrate can be conducted in the coating suspension, followed by removal of excess suspension as described above.
Method for preparing a catalyst
As shown in Figure 3, a catalyst or catalytic article according to one or more embodiments of the present invention can be prepared in a two step process. In the first stage, a carrier substrate 12, which, in specific embodiments, is a honeycomb structure substrate with porous walls and containing channels 14 of dimensions in the range of about 100 channels / in.<sup>2</sup> and 1000 channels / in<sup>2</sup>, is directly coated with a metal from the platinum group. To facilitate illustration, a single channel 14 is shown. In exposed embodiments, the platinum group metal is coated without intervening a particulate refractory oxide support. To facilitate illustration, this is shown as the first catalytic coating 16. The coated substrate 12 is dried and calcined to fix the substantially unsupported platinum group metal on the substrate 12. A portion of the porous walls of substrate 12 is then coated with the suspension with a sealant coating layer of second catalyst coating 18 containing a catalyst for selective catalytic reduction of nitrogen oxides. The substrate 12 is dried and calcined to fix the coating layer of the second catalytic coating 18 on the substrate 12.
In exposed embodiments the second catalytic coating 18 is formed over a zone between inlet end 22 and outlet end 24 of substrate 12, to provide three zones, a first zone to decrease selective catalytic reduction of ammonia, a second zone to oxidize ammonia and a third zone to oxidize carbon monoxide. In specific embodiments, substrate 12 comprises a wall flow filter having gas permeable walls formed in a plurality of axially extending channels, each channel having one end plugged with any pair of adjacent channels plugged at the opposite ends of these .
Further embodiments of the invention are directed to methods of preparing a catalytic article having an inlet end 22 and an outlet end 24 for treating a NOx-containing discharge stream. A first sealing coating layer 16 is coated by the suspension on the walls of the honeycomb structure substrate 12 adjacent to the outlet end 24 of the substrate 12. In the disclosed embodiments, the first sealer coating layer 16 comprises a platinum group metal. The porous walls of substrate 12 are then coated with the suspension with a second layer of sealant coating 18 containing a catalyst for selective catalytic reduction (SCR) of nitrogen oxides. The second sealing coating layer 18 extends from inlet end 22 and at least partially overlaps the first sealing coating layer 16. The coated substrate 12 is dried and calcined to fix the sealant coating layers 16, 18 on the substrate 12. This provides a first zone to decrease ammonia through selective catalytic reduction, a second zone to oxidize ammonia and a third zone to oxidize carbon monoxide and hydrocarbons. In exposed embodiments, substrate 12 comprises a through-flow substrate.
In one or more specific embodiments, substrate 12 comprises a wall flow filter substrate having gas permeable walls, formed into a plurality of axially extending channels, each channel having one end plugged with any pair of adjacent plugged channels at opposite ends of these.
Additional embodiments of the invention are directed to methods of preparing a catalyst for treating a discharge stream containing particulate matter, NOx, and carbon monoxide. Substrate 12 includes an inlet end 22 and an outlet end 24 that define an axial length L. A portion of the outlet end of the substrate 12 is coated with a first catalytic coating 16 containing a platinum group metal effective to catalyze the oxidation of carbon monoxide in the discharge stream. The first catalytic coating layer 16 extends from the exit end 24 of the substrate 12 towards the entry end 22 over at least the total axial length L. The coated substrate 12 is dried and calcined to fix the first catalytic coating 16 on an outlet portion of the substrate 12. An inlet portion of the substrate 12 is coated with a second catalytic coating 18 containing an effective catalyst for catalytic reduction. Selective (SCR) to reduce NOx in the discharge stream. The second catalytic coating 18 extends from the inlet end 22 of the substrate 12 to the outlet end 24 over at least the total axial length L and overlaps a portion of the first catalytic coating layer 16. The coated substrate 12 is dried and calcine to fix the second catalytic coating 18 on the inlet portion of the substrate
12.
Method of dealing with emissions
Another aspect of the present invention includes a method of treating emissions produced in the discharge gas stream from an engine. The discharge gas stream may include one or more NO<sub>X</sub>, CO, hydrocarbons, and ammonia. In one or more embodiments, the method includes injecting ammonia or an ammonia precursor into a discharge gas stream and then first passing the discharge gas stream through an upstream SCR zone described herein for remove NO<sub>X</sub> by the SCR function. In such embodiments, the discharge gas stream is then passed through an AMOx zone in the middle stream to remove ammonia by the NH oxidation function<sub>3</sub>. The catalyst zone in the middle stream can also be followed by a downstream zone which oxidizes one or more CO and hydrocarbons.
In one embodiment, the upstream SCR zone, the midstream AMOx zone, and the downstream DOC zone are arranged on a single catalytic substrate. The SCR zone can be present in a range of about 50% to 90% of the length of the substrate or in a range of about 20% to 90% of the length of the substrate, and consists of only the SCR component. The AMOx zone is in the range of about 5% to 50% of the length of the substrate, and includes a bottom coating layer containing the NH oxidation component<sub>3</sub> and a top coat layer containing the SCR component. The downstream DOC zone is in the range of about 5% to 50% of the length of the substrate, and includes an oxidation component.
In an alternative embodiment of the method, the upstream SCR zone is arranged on a carrier substrate, and the downstream AMOx zone is arranged on a separate carrier substrate. In this embodiment, the AMOx zone is prepared as an AMOx support as described above. The volume of the downstream AMOx catalyst support is in the range of about 10% to 100% of the volume of the upstream SCR catalyst, and consists of a bottom coating layer containing the NH oxidation component<sub>3</sub> and a top coat layer containing the SCR component.
In both previous modalities, the AMOx zone includes two different composition and function layers. The bottom coating layer Includes a supported precious metal component and works to oxidize ammonia according to Eq 2. Ammonia molecules that are desorbed from the SCR catalyst under conditions where it cannot be rapidly consumed by a NO molecule<sub>X</sub> (eg, under a thermal desorption event) they move down channel 14 although they collide with the sealant coating layer 18 in the upstream zone comprising an SCR catalyst. The molecule can diffuse in and out of the sealant coating layer 18, but on the other hand it is not converted by the catalyst until it enters the comment zone below and contacts the undercoat layer 16 which contains a composition which Includes NH oxidation component<sub>3</sub>. In the lower coating layer 16, ammonia is converted to NO, which can subsequently diffuse into the upper coating layer 18. In the upper coating layer containing an SCR catalyst composition, NO can react with NH<sub>3</sub> to form N<sub>2</sub>, Therefore increasing the net selectivity for N<sub>2</sub>.
The placement of the supported precious metal at the bottom of the sealer coat layer below the SCR component in the top coat layer restricts the generation of NO only in the bottom coat layer. This has the effect of increasing the residence half-life of NO within the catalyst sealant coating layers. As the residence time of NO increases, NO has a higher probability of colliding with an ammonia molecule in the SCR sealant coating layer and producing N<sub>2</sub> which is finally released from the catalyst.
In use, the upstream SCR 18 catalyst zone is primarily responsible for eliminating NO emissions<sub>X</sub> of the discharge by the selective catalytic reduction reaction of ammonia. The comment AMOx zone below is primarily responsible for the oxidation function of ammonia. As discussed in any other way herein, the downstream zone 20, which has an overlay of the SCR composition will have SCR activity and may further function in NO decrease.<sub>X</sub>. In this way, the AMOx zone can contribute to the net elimination of NO<sub>X</sub>. Furthermore, at elevated temperatures, some SCR compositions, particularly copper-based SCR catalysts, can also have appreciable ammonia oxidation activity even in the absence of a precious metal component. Additionally, copper-based SCR catalyst compositions can convert NH<sub>3</sub> a N<sub>2</sub> with high selectivity at temperatures above 350 ° C. In one or more modalities, the SCR zone can therefore contribute to the decrease of excess ammonia.
Emission treatment system
One aspect of the invention is directed to emission treatment systems for treating exhaust gases emitted by a diesel engine. Figure 4 shows one or more modalities of the emission treatment system 40 that includes a diesel engine 41 that emits a discharge current that includes particulate matter, NOx and carbon monoxide. A first substrate 45 has an inlet end and an outlet end that define an axial length. The first substrate 45 is placed downstream and in continuous communication with the diesel engine 41. The first substrate 45 has a first catalytic coating that includes a platinum group metal, the first catalytic coating extends from the outlet end to the input end over less than the total axial length of the substrate, and a second catalytic coating that includes a catalyst for selective catalytic reduction (SCR) of nitrogen oxides, the second catalytic coating extends from the inlet end to the outlet end over less than the total axial length of the substrate and overlaps a portion of the layer of the first catalytic coating. In disclosed embodiments, the first substrate 45 is selected from the group consisting of a wall flow substrate and a through flow substrate. In specific embodiments, at least a portion of the platinum group metal is on a refractory metal oxide support. In additional specific embodiments, the platinum group metal is platinum.
In one or more embodiments, there is an upstream substrate 43 coated with a catalyst for selective catalytic reduction of nitrogen oxides. The upstream substrate 43 is in continuous communication with the discharge current of the diesel engine 41 and disposed between the diesel engine 41 and the first substrate 45. In disclosed embodiments, the upstream substrate 43 comprises a honeycomb structure substrate. through flow. In specific embodiments, the upstream substrate 43 comprises a wall flow filter substrate having gas permeable walls formed in a plurality of axially extending channels, each channel having one end plugged with any pair of adjacent channels plugged in the opposite ends of these.
In some specific embodiments, the first catalyst and the second catalyst overlap to form three zones. A first zone decreases nitrogen oxides by selective catalytic reduction, a second zone oxidizes ammonia and a third zone oxidizes carbon monoxide and hydrocarbons, and the platinum group metal is supported directly on the substrate walls in the first zone. and the third zone.
In accordance with one or more disclosed embodiments, the first substrate comprises a through-flow honeycomb structure substrate and the first catalyst and the second catalyst overlap to form three zones. The first zone reduces nitrogen oxides by selective catalytic reduction, the second zone oxidizes ammonia, and the third zone oxidizes carbon monoxide and hydrocarbons. At least a portion of the platinum group metal is on a particulate refractory oxide support.
In some specific embodiments, the first substrate is a wall flow filter substrate having gas permeable walls formed in a plurality of axially extending channels. Each channel has one end plugged with any pair of adjacent channels plugged at opposite ends of these.
In one or more embodiments, there is a wall flow filter substrate having gas permeable walls formed in a plurality of axially extending channels in continuous communication with and disposed between the diesel engine 41 and the first substrate 45. Each channel of the substrate Wall flow filter 43 has one end plugged with any pair of adjacent channels plugged at the opposite ends of these coated with a hydrocarbon or CO oxidation catalyst.
Reference throughout this description to a modality, certain modalities, one or more modalities or modality means that a particular characteristic, structure, material, or characteristic described with respect to the modality is included in at least one modality of the invention. Thus, the occurrences of the phrases such as in one or more modalities, in certain modalities, in one modality or in the modality in various places throughout this description do not necessarily refer to the same modality of the invention. Furthermore, the particular elements, structures, materials or characteristics can be combined in any suitable way in one or more modalities.
Although the invention in the present description has been described with reference to particular embodiments, it will be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations of the method and apparatus of the present invention can be made without departing from the spirit and scope of the invention. Thus, the present invention is intended to include modifications and variations that are within the scope of the appended claims and their equivalents.
Contents6
26 members in 13 offices
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 77446910 | United States of America | A | |
| 2011035234 | United States of America | W |
Members26
| Document | Office | Kind | |
|---|---|---|---|
| CA2798332A1 | Canada | A1 | |
| US2011271664A1 | United States of America | A1 | |
| WO2011140251A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2011140251A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US8293182B2 | United States of America | B2 | |
| MX2012012829AThis record | Mexico | A | |
| EP2567081A2 | European Patent Office (EPO) | A2 | |
| CN102985655A | China | A | |
| JP2013525109A | Japan | A | |
| KR20130098880A | Republic of Korea | A | |
| ZA201209014B | South Africa | B | |
| EP2567081A4 | European Patent Office (EPO) | A4 | |
| CN102985655B | China | B | |
| JP2016193429A | Japan | A | |
| BR112012028320A2 | Brazil | A2 | |
| JP6254844B2 | Japan | B2 | |
| JP6259484B2 | Japan | B2 | |
| KR20180016638A | Republic of Korea | A | |
| CA2798332C | Canada | C | |
| KR101867259B1 | Republic of Korea | B1 | |
| EP3674524A1 | European Patent Office (EPO) | A1 | |
| EP2567081B1 | European Patent Office (EPO) | B1 | |
| MY179455A | Malaysia | A | |
| PL2567081T3 | Poland | T3 | |
| ES2820459T3 | Spain | T3 | |
| BR112012028320B1 | Brazil | B1 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 2012012829
- Application
- 2012012829
Titles2
- English
- INTEGRATED SCR AND AMOX CATALYST SYSTEMS.
- Spanish
- SISTEMAS CATALÍTICOS SCR Y AMOX INTEGRADOS.
Classification
- CPC, 33
- B01D53/9468
- F01N3/28
- H10W42/20
- B01D53/9472
- B01D2255/1021
- B01D2255/9022
- B01D2255/9035
- B01D2255/9155
- B01D2257/404
- B01D2257/502
- B01D2257/702
- B01J23/42
- B01J29/061
- B01J29/072
- B01J29/763
- B01J37/024
- B01J37/0244
- B01J37/0246
- F01N3/035
- F01N3/103
- F01N3/106
- F01N3/2066
- F01N2510/0682
- F01N2510/0684
- F01N2570/18
- F01N13/0097
- B01J23/40
- Y02T10/12
- Y02A50/20
- B01J35/19
- B01J35/56
- B01D53/94
- F01N3/20
- IPC, 3
- F01N3 28
- B01J35 56
- F01N3 08