catalyst system for selective catalytic reduction

专利摘要:
Summary catalytic selective reduction catalyst system scr catalyst systems are described comprising a first scr catalyst composition and a second scr catalyst composition arranged in the system, the first scr catalyst composition promoting higher n2 formation and lower formation. than the second scr catalyst composition, and the second scr catalyst composition having a different composition from the first scr catalyst composition, the second scr catalyst composition promoting lower n2 formation and higher n2o formation. that the first scr. scr catalyst systems are useful in methods and systems for catalyzing the reduction of nitrogen oxides in the presence of a reducer. 1/1
公开号:BR112015022048A2
申请号:R112015022048
申请日:2014-03-13
公开日:2019-09-10
发明作者:Tang Weiyong
申请人:Basf Corp；
IPC主号:

专利说明:

CATALYST SYSTEM FOR SELECTIVE CATALYTIC REDUCTION TECHNICAL FIELD [0001] The present invention relates to the field of selective catalytic reduction catalysts. More particularly, the modalities of the invention relate to selective catalytic reduction catalyst systems which comprise a first SCR catalyst composition and a second SCR catalyst composition, a poorly combustion engine exhaust system, and methods of using these. catalyst systems in a variety of processes such as mitigating pollutants in exhaust gases.
BACKGROUND OF THE INVENTION [0002] The operation of lean mix engines, for example, diesel engines and lean mix gasoline engines, provide the user with excellent fuel economy and have relatively low gaseous hydrocarbon and carbon monoxide emissions due to its operation at high air / fuel rates in poor fuel conditions. Diesel engines, in particular, also offer significant advantages over gasoline engines in terms of durability and their ability to generate high torque at low speed.
[0003] From an emissions point of view, however, diesel engines have more serious problems than their spark ignition counterparts. Emission problems concern particulate matter (PM), nitrogen oxides (NO _X ), unburned hydrocarbons (HC) and carbon monoxide (CO). NO _X is a term used to describe several chemical species of nitrogen oxides, nitrogen monoxide (NO), and nitrogen dioxide (NO ₂ ), among others. NO is a concern because it is believed to participate under a process known as photochemical smog formation, through a series of reactions in the presence of sunlight and hydrocarbons, and NO is a significant contributor to acid rain NO ₂ , for other side,
2/39 has a high potential as an oxidizer and an oxidizer and is a strong irritant to the lung. Particulate matter (PM) is also linked to respiratory problems. As engine operation changes are made to reduce particulates and unburned hydrocarbons in diesel engines, NO and NO ₂ emissions tend to increase.
[0004] The effective reduction of NO _X in lean mix engines is difficult to achieve, because high conversion rates of NO _X typically convert rates requiring conditions rich in reducers. The conversion of the NO _X component from exhaust streams into harmless components generally requires specialized NO _X reduction strategies for operation in poor fuel conditions.
[0005] Selective catalytic reduction (SCR), which uses ammonia or ammonia precursor as a reducing agent, is believed to be the most viable technique for removing nitrogen oxides from the exhaust of diesel vehicles. In typical exhaust, nitrogen oxides are mainly composed of NO (> 90%), so that the SCR catalyst favors the conversion of NO and NH ₃ into nitrogen and water. The two main challenges in the development of catalysts for the automotive application of the ammonia SCR process are to provide a wide operating window for SCR activity, including low temperatures from 200Ό and higher and improving the hydrothermal stability of the catalyst for temperatures above 500Ό. As used in this document, hydrothermal stability refers to the retention of a material's ability to catalyze the NO _X SCR, with a preference that the retention is at least 85% of the material's NO _X conversion ability before hydrothermal aging .
[0006] Metal-promoted zeolite catalysts including, but not limited to, iron-promoted and promoted zeolite catalysts
3/39 by copper, in which, for example, the metal is introduced through ion exchange, for the selective catalytic reduction of nitrogen oxides with ammonia are known. Iron-promoted beta zeolite has been an effective catalyst for the selective reduction of nitrogen oxides with ammonia. Unfortunately, it was found that the same under harsh hydrothermal conditions, such as, for example, the reduction of NO _X from gas exhaustion at temperatures exceeding 500 ° C, the activity of many zeolites promoted by metal, such as, for example, Cu and Fe versions of ZSM-5 and Beta, begins to decline. This decline in activity is believed to be due to the destabilization of the zeolite, for example, through dealumination and the consequent loss of catalytic sites containing metal within the zeolite.
[0007] In order to maintain the overall NO _X reduction activity, marked levels of washcoat loading of the iron-promoted zeolite catalyst need to be provided. As zeolite catalyst levels are increased to provide adequate NO _X removal, there is an obvious reduction in the cost efficiency of the process for removing NO _X as the catalyst costs increase.
[0008] In some SCR systems, in particular, heavy duty diesel engine (HDD), which control the secondary N ₂ O pollutant emitted from the SCR system has become more important. In addition, certain existing catalysts, such as promoted copper zeolites (for example, Cu-SSZ-13), tend to produce an unacceptably high level of N ₂ O emissions. Due to the fact that N ₂ O is a greenhouse effect and emissions regulations are becoming increasingly strict, there is a need for systems that reduce the amount of N ₂ O emitted from SCR systems.
SUMMARY [0009] One aspect of the invention concerns a selective catalytic reduction (SCR) catalyst system. In a first modality, the system comprises a first composition of
4/39 SCR catalyst and a second SCR catalyst composition positioned in the system, the first SCR catalyst composition promoting greater N ₂ formation and less N ₂ O formation than the second SCR catalyst composition, and the second SCR catalyst composition having a different composition than the first SCR catalyst composition, the second SCR catalyst composition promoting less N ₂ formation and greater N ₂ O formation than the first SCR catalyst composition.
[0010] In a second embodiment, the first SCR catalyst composition is modified so that the first SCR catalyst composition and the second SCR catalyst composition are positioned on a common substrate.
[0011] In a third embodiment, the SCR catalyst system, the first or second embodiment is modified so that the first SCR catalyst composition is located upstream of the second SCR catalyst composition.
[0012] In a fourth embodiment, the SCR catalyst system from the first to the third embodiment is modified so that the first SCR catalyst composition and the second SCR catalyst composition are positioned on different substrates.
[0013] In a fifth embodiment, the system from the first to the fourth embodiment is modified so that the first SCR catalyst composition is located upstream of the second SCR catalyst composition.
[00l4] In a sixth embodiment, the first or second embodiment is modified in which the first SCR catalyst composition and the second SCR catalyst composition are in a layered relationship, with the first layered SCR catalyst composition in above the second SCR catalyst composition.
[0015] In the seventh modality, any one of the first to the sixth modality, the SCR catalyst system of the claim, the
5/39 The first SCR catalyst composition comprises a mixed oxide.
[0016] In an eighth modality, the seventh modality can be modified so that the mixed oxide is selected from Fe / titania, Fe / alumina, Mg / titania, Cu / titania, Ce / Zr, vanádia / titania, and their mixtures.
[0017] In a ninth modality, the eighth modality is modified so that the mixed oxide comprises vanádia / titania.
[0018] In a tenth modality, the ninth modality is modified so that vanádia / titania is stabilized with tungsten.
[0019] In an eleventh embodiment, any one from the first to the eleventh modality can be modified in which the second SCR catalyst comprises a metal-exchanged small 8-ring molecular sieve.
[0020] In an twelfth modality, the eleventh modality can be modified in which the molecular sieve has a type of structure selected from the group consisting of AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT , DDR, and SAV.
[002l] In a thirteenth modality, the twelfth modality is modified in which the molecular sieve is an aluminosilicate zeolite and has the structure of the CHA type.
[0022] In a fourteenth modality, the thirteenth modality is modified in which the zeolite is selected from SSZ13 and SSZ-62.
[0023] In a fifteenth modality, any one from the eleventh to the fourteenth modality can be modified in which the metal is selected from the group consisting of Cu, Fe, Co, Ce and Ni.
[0024] In a sixteenth modality, the fifteenth modality is modified, in which the metal is selected from Cu.
[0025] In a seventeenth modality, the sixteenth modality is modified, in which the zeolite is exchanged with Cu in the range
6/39 from 2% to 8% by weight.
[0026] An eighteenth modality relates to a selective catalytic reduction (SCR) catalyst system comprising a first SCR catalyst composition comprising vanadium / titania positioned on a substrate and a second SCR catalyst composition comprising a molecular sieve metal-exchanged small pore ring positioned on a substrate.
[0027] In a nineteenth modality, the eighteenth modality is modified, in which the molecular sieve has a type of structure selected from the group consisting of AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT , DDR, and SAV.
[0028] In a twentieth modality, the nineteenth modality is modified in which the molecular sieve is an aluminosilicate zeolite and has the structure of the CHA type.
[0029] In a twenty-first modality, the twenty modality is modified in which the zeolite is selected from SSZ-13 and SSZ62.
[0030] In a twenty-second modality, the eighteenth to the twenty-first modality is modified, in which the metal is selected from the group consisting of Cu, Fe, Co, Ce and Ni.
[0031] In a twenty-third modality, the twenty-second modality is modified, in which the metal is selected from Cu.
[0032] In a twenty-fourth modality to the eighteenth to the twenty-third modality are modified, in which the zeolite is exchanged with Cu in the range of 2% to 8% by weight.
[0033] In a twenty-fifth modality, the eighteenth to the twenty-fourth modalities are modified, vanádia / titania is stabilized with tungsten.
[0034] In a twenty-sixth modality, the eighteenth to the twenty-fifth modalities are modified, in which the first
7/39 SCR catalyst composition and second SCR catalyst composition are positioned on a common substrate.
[0035] In a twenty-seventh modality, the eighteenth to the twenty-sixth modalities are modified, wherein the first SCR catalyst composition is located upstream of the second SCR catalyst composition.
[0036] In a twenty-eighth modality, the eighteenth to the twenty-seventh modalities are modified, in which vanádia / titania promotes greater formation of N ₂ and less formation of N2O than the molecular sieve of the small metal-exchanged 8-ring pore and wherein the small pore molecular sieve 8-exchanged with metal ring formation promotes N ₂ formation , and lower N ₂ to the upper vanadia / titania.
[0037] In a twenty-ninth modality, the eighteenth to twenty-fifth modalities are modified, in which the first SCR catalyst composition and second SCR catalyst composition are positioned on the separate substrates.
[0038] In a thirty modality, the twenty-ninth modality is modified, in which the first SCR catalyst composition is located upstream of the second SCR catalyst composition.
[0039] In a thirty-first embodiment, the twenty-sixth embodiment is modified in which the first SCR catalyst composition and the second SCR catalyst composition are in a layered relationship, with the first SCR catalyst composition positioned in layers by above the second SCR catalyst composition.
[0040] In a thirty-second modality, the thirty-fifth modality is modified, in which the molecular sieve has a type of structure selected from the group consisting of AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT , DDR, and SAV.
[0041] In a thirty-third modality, the thirty-second
8/39 modality is modified, in which the molecular sieve is an aluminosilicate zeolite and has the CHA type structure.
[0042] In a thirty-fourth modality, the thirty-third modality is modified, in which the zeolite is selected from SSZ-13 and SSZ-62.
[0043] In a thirty-fifth modality, the thirty-first to the thirty-fourth modalities are modified, in which the metal is selected from the group consisting of Cu, Fe, Co, Ce and Ni.
[0044] In a thirty-sixth modality, the thirty-fifth modality is modified, in which the metal is selected from Cu.
[0045] In a thirty-seventh modality, the thirty-third modality is modified, in which the zeolite is exchanged with Cu.
[0046] In a thirty-eighth modality, the thirty-first to the thirty-seventh modalities are modified, in which vanádia / titania is stabilized with tungsten.
[0047] Another aspect of the invention relates to an exhaust gas treatment system for a poorly-mixed engine. In a thirty-ninth embodiment, an exhaust gas treatment system for the lean mix engine comprises the catalyst system from any one of the first to the thirty-seventh mode, a lean mix engine, and an exhaust gas conduit in fluid communication with the lean mix engine, where the catalyst system is downstream of the engine.
[0048] In a fortieth modality, the thirty-ninth modality is modified, in which the engine is a heavy duty diesel engine.
[0049] Another aspect of the invention concerns a method of removing nitrogen oxides from the exhaust gases of a lean mix engine. In a forty-first modality, a method of removing nitrogen oxides from the exhaust gases of a lean mix engine, the method comprising contacting a
9/39 exhaust gas stream with selective catalytic reduction of the catalyst system (SCR) which includes a first SCR catalyst composition comprising vanadium / titania positioned on a substrate and a second SCR catalyst composition comprising a molecular sieve small pore size of the metal-exchanged ring-8 positioned on a substrate.
[0050] In a forty-second modality, the forty-first modality is modified, in which the exhaust gas comprises NO _X.
[0051] In a fortieth modality, the forty-first and fortieth second modalities are modified, in which the lean mixture engine is a heavy duty diesel engine.
[0052] In a forty-fourth modality, an exhaust gas treatment system for the lean mix engine comprises the catalyst system of the nineteenth modality, a poor mix engine, and an exhaust gas conduit in fluid communication with the lean mix engine, where the catalyst system is downstream of the engine.
[0053] In a forty-fifth modality, the forty-fourth modality is modified, in which the engine is a heavy-duty diesel engine.
[0054] A forty-sixth modality refers to a method of removing nitrogen oxides from the exhaust gases of a lean mix engine, the method comprising contacting the exhaust gas with the selective catalytic reduction catalyst (SCR) system ) which includes a first SCR catalyst composition and a second SCR catalyst composition positioned in the system, the first SCR catalyst composition promoting greater N ₂ formation and less N ₂ O formation than the second catalyst composition, and the second catalyst composition that has a different composition than the first SCR catalyst composition, the
10/39 second catalyst composition promoting less N ₂ formation and greater N ₂ O formation than the first SCR catalyst composition.
[0055] In a forty-seventh modality, the first to the thirty-seventh modalities are modified, in which the second catalyst composition has a greater NH ₃ storage capacity than the first catalyst composition.
[0056] In a forty-eighth modality, a selective catalytic reduction (SCR) of the hybrid catalyst system for removing NOx from the engine exhaust gases, the system comprises a first SCR catalyst composition and a second SCR catalyst composition positioned in the system, the first SCR catalyst composition having a faster DeNOx response time when exposed to ammonia than the second catalyst composition and the second SCR catalyst composition has a higher DeNOx performance at steady state. that the first catalyst composition and the first SCR catalyst composition provides a target percentage of DeNOx at a lower ammonia storage level than the second SCR catalyst composition to provide the same percentage of DeNOx, and in which the system provides a higher steady-state DeNOx performance than the first c composition heater.
[0057] In a forty-ninth modality, the forty-eighth modality is modified, in which under conditions of acceleration in which sudden increases in the exhaust temperature are produced, the ammonia dissolved from the hybrid system due to the increase in temperature is less than the ammonia dissolved from a system that has only the second catalyst composition.
[0058] In a fiftieth modality, the forty-eighth or forty-ninth modalities are modified, in which the first
11/39 catalyst composition comprises vanadium / titania stabilized with tungsten.
[0059] In a fifty-first embodiment, the fifty-fifth embodiment is modified, wherein the second catalyst composition comprises a metal-exchanged 8-ring small pore molecular sieve.
[0060] In a fifty-second modality, the fifty-first modality is modified, in which the molecular sieve has a type of structure selected from the group consisting of AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT , DDR, and SAV.
[0061] In a fifty-third modality, the fifty-second modality is modified, in which the molecular sieve is an aluminosilicate zeolite and has the CHA type structure.
[0062] In a fifty-fourth modality, the forty-eighth to fifty-third modalities are modified, in which the zeolite is selected from SSZ-13 and SSZ-62 and the metal comprises Cu.
[0063] In a fifty-fifth modality, the system of the first to thirty-eighth modalities are modified in which the first SCR catalyst composition promotes greater N ₂ formation and less N ₂ O formation than the second SCR catalyst composition , and the second SCR catalyst composition promotes less N ₂ formation and more N ₂ O formation in a temperature range from 2000 to 6000.
[0064] In a fifty-sixth modality, the forty-eighth to fifty-fourth modalities are modified, in which the first SCR catalyst composition has a faster DeNOx response time when exposed to ammonia than the second catalyst composition and the second SCR catalyst composition has a higher steady-state DeNOx performance than the first catalyst composition and the first
12/39 SCR catalyst composition provides a target percentage of DeNOx at a lower ammonia storage level than the second SCR catalyst composition to provide the same percentage of DeNOx, and where the system provides a higher performance of Steady DeNOx than the formation for the first catalyst composition in a temperature range from 2000 to 6000.
BRIEF DESCRIPTION OF THE FIGURES [0065] FIG. 1 shows a cross-sectional view of an SCR catalyst system according to one or more embodiments;
[0066] FIG. 2 shows a partial cross-sectional view of an SCR catalyst system according to one or more embodiments;
[0067] FIG. 3 shows a cross-sectional view of an SCR catalyst system according to one or more embodiments;
[0068] FIG. 4 is a graph comparing N ₂ O emissions for an SCR catalyst system according to one or more modalities and a comparative system;
[0069] FIG. 5 is a graph comparing N ₂ O emissions for an SCR catalyst system according to one or more modalities and a comparative system;
[0070] FIG. 6 is a graph comparing N ₂ O emissions for an SCR catalyst system according to one or more modalities and a comparative system, both systems with an oxidation catalyst upstream of the diesel;
[0071] FIG. 8 is a graph comparing the NO _x conversions of an SCR catalyst system according to one or more modalities and a comparative system, both systems with an oxidation catalyst upstream of the diesel;
13/39 [0072] FIG. 9 is a graph comparing NO _X conversions after sulfation of an SCR catalyst system according to one or more modalities and a comparative system, both systems with an oxidation catalyst upstream of the diesel;
[0073] FIG. 10 is a graph generated by a computer model, as described in Example 6, which shows a Response Curve of the DeNO _x vs. vs. Analysis. 225Ό time and 10% NO ₂ ; θ [0074] FIG. 11 is a graph generated by a computer model, as described in Example 6, which shows a Response Curve of the DeNO _x vs. vs. Analysis. Total Absorbed NH ₃ at 225Ό and 10% NO ₂ .
DETAILED DESCRIPTION [0075] Before describing several exemplary embodiments of the invention, it should be understood that the invention is not limited to the details of construction or process steps set out in the following description. The invention is capable of other modalities and can be practiced or performed in different ways.
[0076] Government regulations mandate the use of NO _X reduction technologies for light and heavy duty poor-mix engine vehicles. The selective catalytic reduction (SCR) of NO _x using urea is an effective and dominant emission control technology for NO _X control. To meet future government regulations, an SCR catalyst system that has improved performance compared to current Cu-SSZ-13 based systems. The modalities of the invention relate to an SCR catalyst system that has lower N ₂ O emissions and also better conversion efficiency of NO _X at low levels of NH ₃ storage than simple SCR catalyst systems and other systems of dual SCR catalyst. Without the intention of being linked to the theory, it is believed that the dynamic response of the SCR catalyst system according to one or more modalities is provided
14/39 through the improved NH ₃ storage capacity. The characteristics of the invention described here must be provided over the entire SCR temperature range of interest, that is, 200Ό to 600Ό. According to one or more embodiments, the first and second SCR catalyst compositions exclude metals from the platinum group, such as Pt, Pd and Rh.
[0077] The modalities of the invention are directed to SCR catalyst systems, methods for their preparation, exhaust gas purification systems and exhaust gas nitrogen oxide reduction methods with the use of such SCR catalyst systems .
[0078] The modalities are directed to the use of SCR catalyst systems that provide the improved NO _X performance for poor mix engines. While SCR catalyst systems can be used in any lean mix engine, in specific embodiments, catalyst systems must be used in heavy duty diesel engine applications. Heavy duty diesel engine applications include diesel powered vehicles that have a gross vehicle weight (GVWR) rating of over 8,500 Ibs by the federal government and over 14,000 Ibs in California (1995 model year and later). SCR catalyst systems according to the modalities can be used in other engines as well, including, but not limited to, non-road diesel engines, locomotives, marine engines, and stationary diesel engines. The invention may have applicability to other types of lean mix engines as well, for example, light duty diesel engines, compressed natural gas engines and lean mix gasoline direct injection engines.
[0079] With regard to the terms used in the disclosure, the following definitions are provided.
[0080] As used in this document, the term catalyst or
15/39 catalyst composition refers to a material that promotes a reaction. As used herein, the phrase catalyst system refers to a combination of two or more catalysts, for example, a combination of a first SCR catalyst and a second SCR catalyst. The catalyst system can be in the form of a washcoat in which the two SCR catalysts are mixed.
[0081] As used in this document, the terms upstream and downstream refer to relative directions according to the flow of an engine exhaust gas stream from an engine towards an exhaust, with the engine in one upstream and exhaust and any pollution reduction items such as filters and catalysts are downstream of the engine.
[0082] As used in this document, the term current refers broadly to any combination of flowing gas that may contain matter in solid or liquid particle. The term gaseous stream or exhaust gas stream means a stream of gaseous constituents such as exhaust from a lean mix engine, which may contain entrained non-gaseous components such as liquid droplets, solid particles, and the like. The exhaust gas flow of a lean mix engine also typically comprises combustion products, incomplete combustion products, nitrogen oxides, particulate matter in fuel and / or carbonaceous (soot), and unreacted oxygen and nitrogen.
[0083] As used in this document, the term substrate refers to monolithic material, in which the catalyst composition is placed, typically in the form of a washcoat that contains a plurality of particles containing a catalytic composition therein. A washcoat is formed by preparing a paste that contains a specified solids content (for example, 30-90% by weight) of particles in a liquid vehicle, which is then coated in a
16/39 substrate and dried to provide a washcoat layer.
[0084] As used in this document, the term washcoat has its common meaning in the technique of a thin and adherent coating of a catalytic material or other material applied to a substrate material, such as a honeycomb carrier member, which is sufficiently porous to allow passage of the gas stream being treated.
[0085] Catalytic article refers to an element that is used to promote a desired reaction. For example, a catalytic article can include a washcoat that contains catalytic compositions on a substrate.
[0086] In one or more modalities, the substrate is a ceramic or metal that has a honeycomb structure. Any suitable substrate can be employed, such as a monolithic substrate of the type that has parallel slender gas flow passages that extend through it from an entrance face or an exit face of the substrate, so that the passages are open to the fluid flow through them. The passages, which are essentially straight paths from the fluid inlet to the fluid outlet, are defined by walls on which the catalyst material is coated like a washcoat so that gases flowing through the passages come into contact with the material catalytic. The flow passages of the monolithic substrate are thin-walled channels, which can have any suitable cross-sectional shape and size, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures can contain from about 60 to about 900 or more gas inlet openings (i.e., cells) per square inch of cross-section.
[0087] The ceramic substrate can be made of any suitable refractory material, for example, cordierite, cordierite-α alumina, silicon nitrite, zirconium mullite, spodumene, silica-magnesia alumina,
17/39 zirconium silicate, sillimanite, a magnesium silicate, zirconium, petalite, α-alumina, an aluminosilicate and the like.
[0088] The substrates useful for the catalyst compositions of the embodiments of the present invention can also be of a metallic nature and are composed of one or more metals or metal alloys. Metal substrates can be used in various formats, for example, in pellets, corrugated sheet or monolithic form. Specific examples of metallic substrates include heat-resistant base metal alloys, especially those in which iron is a substantial or major component. Such alloys may contain one or more of nickel, chromium, and aluminum, and the total of these metals may advantageously comprise at least about 15% by weight of the alloy, for example, about 10 to 25% by weight of chromium, about 1 to 8% by weight of aluminum, and about 0 to 20% by weight of nickel.
[0089] According to a first aspect of the invention, a selective catalytic reduction (SCR) catalyst system comprises a first SCR catalyst composition and a second SCR catalyst composition positioned in the system. In one or more embodiments, the second SCR catalyst composition has a different composition than the first SCR catalyst composition. The first SCR catalyst composition promotes greater N ₂ formation and less N ₂ O formation than the second SCR catalyst composition, while the second catalyst composition promotes less N ₂ formation and greater formation of N ₂ O than the first SCR catalyst composition. To reduce NH ₃ emissions, in one or more modalities, the first SCR catalyst must have a lower NH ₃ desorption temperature / adsorption capacity than the second SCR catalyst composition.
[0090] In one or more embodiments, the first SCR catalyst composition and the second SCR catalyst composition
18/39 are on the same or on a common substrate. In other embodiments, the first SCR catalyst composition and the second SCR catalyst composition are on separate substrates.
[0091] In one embodiment, the first SCR catalyst and the second SCR catalyst are positioned in a laterally zoned configuration, with the first catalyst upstream of the second catalyst. The upstream and downstream catalysts can be positioned on the same substrate or on different substrates separated from each other. In another specific embodiment, the first SCR catalyst and the second SCR catalyst are in a layered arrangement, with the second SCR catalyst being positioned on a substrate and the first SCR catalyst in a layer that covers the second SCR catalyst. Each of these modalities will be described in more detail below.
[0092] In specific embodiments, each of the first SCR catalyst composition and the second SCR catalyst composition is used as a molded catalyst, even more specifically as a molded catalyst in which the SCR catalyst composition is deposited in a suitable refractory substrate, even more specifically in a honeycomb type substrate, for the selective reduction of NO _X nitrogen oxides, that is, for the selective catalytic reduction of nitrogen oxides. According to the embodiments of the invention, the SCR catalyst composition can be in the form of self-sustaining catalyst particles, or as a honeycomb monolith formed from the SCR catalyst composition.
[0093] According to one or more embodiments, the first SCR catalyst composition comprises a mixed oxide. As used in this document, the term mixed oxide refers to an oxide that contains cations from more than one chemical element or cations from a single element in various states of oxidation. In one or more
19/39 modalities, the mixed oxide is selected from Fe / titania (eg FeTiO ₃ ), Fe / alumina (eg FeAI ₂ O ₃ ), Mg / titania (eg MgTiO ₃ ), Mg / alumina ( for example, MgAI ₂ O ₃ ), Mn / alumina, Mn / titania (for example, MnO _x / TiO ₂ ) (for example, MnO _x / AI ₂ O ₃ ), Cu / titania (for example, CuTiO ₃ ), Ce / Zr (for example, CeZrO ₂ ), Ti / Zr (for example, TiZrO ₂ ), vanádia / titania (for example, V ₂ O ₅ / TiO ₂ ), and mixtures thereof. In specific modalities, the mixed oxide comprises vanádia / titania. Vanadium / titania can be activated or stabilized with tungsten (eg WO ₃ ) to provide V ₂ O ₅ / TiO ₂ / WO ₃ .
[0094] According to one or more embodiments, a first SCR catalyst composition comprising vanadium / titania that generates significantly less N ₂ O than SCR catalyst zeolites, especially under rich NO ₂ conditions. In one or more embodiments, the first SCR catalyst composition comprises titania over which vanádia has been dispersed. Vanádia can be dispersed in concentrations ranging from 1 to 10% by weight, including 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight. In the specific modalities vanádia is activated or stabilized by tungsten (WO ₃ ). Tungsten can be dispersed in concentrations ranging from 0.5 to 10% by weight, including 1, 2, 3, 3. 4, 5, 6, 7, 8, 9 and 10% by weight. All percentages are on an oxide basis.
[0095] According to one or more embodiments, the second SCR catalyst comprises a metal-exchanged molecular sieve. The metal is selected from Cu, Fe, Co, Ni, Ce and Pt. In the specific modalities, the metal is Cu.
[0096] As used herein, the term molecular sieves refers to materials based on an extensive three-dimensional network of oxygen ions containing sites of generally tetrahedral type and having a pore distribution. Molecular sieves such as zeolites have been widely used to catalyze a series of chemical reactions in refinery and petrochemical reactions, and catalysis, adsorption, separation and
Chromatography. For example, with respect to zeolites, both natural and synthetic zeolites and their use in promoting certain reactions, including converting methanol to olefins (MTO reactions) and selective catalytic reduction (SCR) of nitrogen oxides with a reducer such as ammonia, urea or a hydrocarbon in the presence of oxygen, are well known in the art. Zeolites are crystalline materials, having very uniform pore sizes that, depending on the type of zeolite and the type and quantity of cations included in the zeolite structure, vary from about 3 to 10 Angstroms in diameter.
[0097] The compositions of the catalysts employed in the SCR process should ideally be able to maintain good catalytic activity over the wide range of temperature conditions of use, for example, 2000 to 6000 or higher, under hydrothermal conditions. Hydrothermal conditions are often encountered in practice, such as during the regeneration of a soot filter, a component of the exhaust gas treatment system used to remove particles.
[0098] According to the modalities, the molecular sieves of the second SCR catalyst composition have 8-ring pore openings and double six-ring secondary construction units, for example, those having the following types of structure: AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT, DDR, and SAV. According to one or more modalities, it will be appreciated that when defining molecular sieves by their type of structure, it is intended to include the type of structure and any and all isotypic frame material such as SAPO, AIPO and MeAPO materials, having the same type of structure.
[0099] Zeolites having 8-ring pore openings and secondary double-six ring construction units, particularly those having cage-like structures have recently found interest in use as SCR catalysts. A specific type of zeolite with these properties is chabazite (CHA), which is a zeolite of
21/39 small pore with eight ring member pore openings (having a pore size of at least a maximum dimension of less than 4.3 Angstroms, for example, about 3.8 Angstrom) accessible through its three-dimensional porosity. A cage-like structure results from the connection of double six-ring building units by 4 rings.
[00100] Aluminosilicate zeolites promoted by metal, especially promoted by copper, having the type of structure CHA (for example, SSZ-13 and SSZ-62) and a molar ratio of silica to alumina greater than 1, specifically those having a ratio molar silica to alumina greater than or equal to 5, 10, or 15 and less than about 1000, 500, 250, 100 and 50 have recently aroused a high degree of interest as catalysts for the SCR of nitrogen oxides in mixing engines poor using nitrogen reducers. This is due to the wide temperature window together with the excellent hydrothermal durability of these materials, as described in United States Patent No. ^Q 7,601,662. Prior to the discovery of the metal-promoted zeolites described in United States Patent No. ^Q 7,601,662, while the literature had indicated that a large number of metal-promoted zeolites had been proposed in the scientific and patent literature for use as SCR catalysts , each of the proposed materials suffered from one or both of the following defects: (1) poor conversion of nitrogen oxides at low temperatures, for example 350Ό and below; and (2) poor hydrothermal stability, marked by a significant decline in catalytic activity in the conversion of nitrogen oxides by SCR. Thus, the invention described in United States Patent No. ^Q 7,601,662 addressed an imperative, unresolved need to provide a material that would provide the conversion of nitrogen oxides at low temperatures and retention of SCR catalytic activity after hydrothermal aging at temperatures above 650Ό.
[00101]
Zeolitic chabazite includes a mineral tectosilicate of
22/39 natural occurrence of a zeolite group with approximate formula: (Ca, Na ₂ , K ₂ , Mg) AI ₂ Si ₄ 0i ₂ · 6H ₂ O (for example, hydrated calcium aluminum silicate). Three synthetic forms of zeolitic chabazite are described in Zeolite Molecular Sieves, by DW Breck, published in 1973 by John Wiley & Sons, incorporated herein by reference. The three synthetic forms reported by Breck are Zeolite KG, described in J. Chem. Soc., P. 2822 (1956), Barrer et al; Zeolite D, described in British Patent No. ^Q 868,846 (1961); and Zeolite R, described in US Patent No. ^Q 3,030,181, which are incorporated herein by reference. The synthesis of another synthetic form of the zeolitic chabazite, SSZ-13, is described in Pat. N ^Q US 4,544,538, which is incorporated herein by reference. The synthesis of a synthetic form of a molecular sieve having the chabazite crystal structure, silicoaluminophosphate 34 (SAPO34), is described in US Patent No. ^Q 4,440,871 and ^Q 7,264,789, which are incorporated herein by reference. One method of making yet another molecular sieve having chabazite structure, SAPO-44, is described in US Patent No. ^Q 6,162,415, which is incorporated herein by reference.
[00102] In the most specific modalities, reference to a type of aluminosilicate zeolite structure limits the material to molecular sieves that do not include phosphorus or other substituted metals in the frame. Obviously, aluminosilicate zeolites can subsequently have an ion exchange with one or more promoter metals such as platinum metals. However, to make it clear, as used in this document, aluminosilicate zeolite excludes aluminophosphate materials such as SAPO, AIPO and MeAPO materials, and the broader term zeolite is intended to include aluminosilicate and aluminophosphate. In one or more embodiments, the molecular sieve can include all compositions of aluminosilicate, borosilicate, galossilicate, MeAPSO, and MeAPO. These include, but are not limited to, SSZ-13, SSZ-62, natural chabazite, K-G zeolite, Linde
23/39
D, Linde R, LZ-218, LZ-235. LZ-236, ZK-14, SAPO-34, SAPO-44, SAPO47, ZYT-6, CuSAPO-34, CuSAPO-44, and CuSAPO-47.
[00103] In one or more embodiments, the molecular sieve of the second SCR catalyst composition has a type of structure selected from the group consisting of AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT, DDR , and SAV. In a specific embodiment, the molecular sieve is an aluminosilicate zeolite and has the type of CHA structure, for example, SSZ-13 or SSZ-62. In another specific embodiment, the molecular sieve is an aluminosilicate zeolite and has the structure type AEI, for example SSZ-39.
[00104] In the specific embodiments, the small 8-ring pore molecular sieve promoted by copper has a molar ratio of silica to alumina greater than about 15, even more specifically greater than about 20. In the specific embodiments, the molecular sieve Small 8-ring pores promoted by copper have a molar ratio of silica to alumina in the range of about 20 to about 256, more specifically in the range of about 25 to about 40.
[00105] In specific modalities, the atomic ratio of copper to aluminum exceeds about 0.25. In more specific embodiments, the copper to aluminum ratio is about 0.25 to about 1, even more specifically about 0.25 to about 0.5. In even more specific embodiments, the copper to aluminum ratio is about 0.3 to about 0.4.
[00106] In general, the SCR catalyst system according to one or more modalities should exhibit both good low temperature conversion activity NO _X (NO _X conversion> 50% at 200Ό) and good high temperature conversion activity NO _X (NO _X conversion> 70% at 4500). NO _X activity is measured under stable conditions at maximum NH ₃ -slip conditions in a gas mixture of 500 ppm NO, 500 ppm NH ₃ , 10% O ₂ , 5% H ₂ O, equilibrate N ₂ at a space speed based on a volume of 80,000
24/39 h ' ¹ .
[00107] According to one or more modalities, to reduce NH ₃ emissions, the first SCR catalyst composition must have a lower NH ₃ adsorption / desorption temperature than the second SCR catalyst composition.
[00108] According to one or more embodiments, the second SCR catalyst composition comprises a metal-exchanged small 8-ring molecular pore sieve. In other words, the second SCR catalyst composition is a small 8-ring pore molecular sieve that is promoted with metal. In one or more modalities, the metal can be selected from the group consisting of Cu, Fe, Co, Ce, and Ni. In a specific modality, the metal is selected from Cu.
Metal promoter% by weight:
[00109] The promoter metal content (e.g. Cu) of the metal-exchanged 8-ring small pore molecular sieve, calculated as metal oxide, in specific embodiments, is at least about 2% by weight , even more specifically, at least about 2.5% by weight and in even the most specific modalities, at least about 3% by weight, reported on a non-volatile basis. In even more specific embodiments, the metal content (for example, Cu) of the molecular sieve of the small metal-exchanged 8-ring pore, calculated as metal oxide, is in the range of up to about 8% by weight, based on total weight of the calcined molecular sieve reported on a non-volatile basis. Therefore, in the specific modalities, the range of the 8-ring small pore molecular sieve promoted with a metal selected from Cu, Fe, Co, Ce, and Ni, calculated as the metal oxide, is about 2 to about 8% by weight, more specifically from about 2 to about 5% by weight, and even more specifically from about 2.5 to about 3.5% by weight, in each case reported on a of oxide.
25/39 [00110] In one or more embodiments, the first SCR catalyst and the second SCR catalyst are arranged in a laterally zoned configuration, with the first catalyst upstream of the second catalyst. As used herein, the term laterally zoned refers to the location of the two SCR catalysts relative to each other. Lateral means side-by-side so that the first SCR catalyst composition and the second SCR catalyst composition are located side by side with the first SCR catalyst composition upstream of the second SCR catalyst composition . According to one or more embodiments, the first and second laterally zoned SCR catalysts can be arranged on the same or on a common substrate or on different substrates separated from each other.
[00111] According to one or more modalities, vanádia / titania and the metal-exchanged 8-ring small pore molecular sieve are positioned on a common substrate or on it. In other embodiments, vanádia / titania and the metal-exchanged 8-ring small pore molecular sieve are positioned on separate substrates. Whether on the same substrate or on different substrates, according to one or more modalities, vanádia / titania is located in the metal-exchanged 8-ring small pore molecular sieve.
[00112] In one or more modalities, vanádia / titania promotes greater N ₂ formation and less N ₂ O formation than the metal-exchanged 8-ring small pore molecular sieve and the small pore molecular sieve of 8-ring exchanged with metal promotes less formation of N ₂ and greater formation of N ₂ O than the formation of vanádia / titania.
[00113] Compositions used commercially, especially in mobile applications, comprise TiO ₂ in which WO ₃ and V ₂ O ₅ were dispersed in concentrations ranging from 5 to 20%
26/39 by weight and 0.5 to 6% by weight, respectively. These catalysts can contain other inorganic materials such as SiO ₂ and ZrO ₂ as binding and promoting agents.
[00114] With reference to FIG. 1, an exemplary embodiment of a laterally spaced system is shown. The SCR catalyst system 10 is shown in a laterally zoned arrangement where the first SCR catalyst composition 18 is located upstream of the second SCR catalyst composition 20 on a common substrate 12. Substrate 12 has an inlet end 22 and an outlet end 24 defining an axial length L. In one or more embodiments, substrate 12 generally comprises a plurality of channels 14 of a honeycomb substrate, of which only one is shown in the transverse channel for clarity. The first SCR catalyst composition 18 extends from the inlet end 22 of the substrate 12 to less than the entire axial length L of the substrate 12. The length of the first SCR catalyst composition 18 is designated as the first zone 18a in the FIG. 1. The first SCR 18 catalyst composition may, in the specific embodiments, comprise vanádia / titania. The second SCR 20 catalyst composition may, in specific embodiments, comprise a metal-exchanged, small 8-ring molecular sieve. The second SCR catalyst composition 20 extends from the outlet end 24 of substrate 12 less than the entire axial length L of substrate 12. The length of the second catalyst composition is denoted as the second zone 20b in Figure 1. The SCR 10 catalyst system is effective for the selective catalytic reduction of NO _X.
[00115] It will be appreciated that the length of the first zone and the second zone can be varied. In one or more embodiments, the first zone and the second zone can be equal in length. In other modalities, the first zone can be 20%, 25%, 35% or 40%,
27/39
60%, 65%, 75% or 80% of the L length of the substrate, with the second zone, respectively, covering the rest of the L length of the substrate.
[00116] With reference to FIG. 2, another embodiment of a laterally zoned SCR catalyst system 110 is shown. The SCR 110 catalyst system is shown in a laterally zoned arrangement in which the first SCR catalyst composition 118 is located upstream of the second SCR catalyst composition 120 on separate substrates 112 and 113. The first SCR 118 catalyst composition it is positioned on a substrate 112, and the second SCR catalyst composition is positioned on a separate substrate 113. Substrates 112 and 113 can be made of the same or a different material. The substrate 112 has an input end 122a and an output end 124a defining an axial length L1. The substrate 113 has an input end 122b and an output end 124b defining an axial length L2. In one or more embodiments, substrates 112 and 113 generally comprise a plurality of channels 114 of a honeycomb substrate, of which only one channel is shown in cross section, for clarity. The first SCR catalyst composition 118 extends from the inlet end 122a of the substrate 112 through the entire axial length L1 of the substrate 112 to the outlet end 124a. The length of the first SCR catalyst composition 118 is designated as the first zone 118a in FIG. 2. The first SCR 118 catalyst composition may, in the specific embodiments, comprise vanádia / titania. The second SCR 120 catalyst composition may, in specific embodiments, comprise a metal-exchanged 8-ring small pore molecular sieve. The second SCR catalyst composition 120 extends from the outlet end 124b of the substrate 113 through the entire axial length L2 of the
Substrate 113 for the inlet end 122b. The second catalyst composition 120 defines a second zone 120a. The SCR 110 catalyst system is effective for the selective catalytic reduction of NO _X. The length of zones 118a and 120a can be varied as described in relation to Figure 1.
[00117] One or more embodiments of the present invention are directed to a selective catalytic reduction (SCR) of the catalyst system comprising a first SCR catalyst composition comprising vanadium / titania positioned on a substrate and a second SCR catalyst composition comprising a metal-exchanged 8-ring small pore molecular sieve positioned on a substrate, wherein the first SCR catalyst composition and the second SCR catalyst composition are in a layered relationship or arrangement. In one or more embodiments, the first SCR catalyst composition is layered on top of the second SCR catalyst composition.
[00118] According to one or more modalities, the second SCR catalyst composition is washed by a substrate, and then the first SCR catalyst composition is washed by a layer that overlaps the second catalyst composition. of SCR. In one or more embodiments, the layering has been designed to optimize the first catalyst composition / second dry gain catalyst composition for a desirable balance between the benefits of acting as a protective shield and the potential disadvantages of increasing the barrier of diffusion. Under low temperatures for prolonged operations, sulfur is a major concern for Cu-CHA catalysts. In comparison, vanadium / titania (V ₂ O ₅ / TiO ₂ ) SCR catalysts are known to have superior sulfur tolerance.
[00119] The first and second SCR catalyst composition can include the compositions as described above.
29/39 [00120] With reference to FIG. 3, an exemplary embodiment of a layered SCR catalyst system 210 is shown. The SCR catalyst system can be in a layered arrangement where the first SCR catalyst composition 218 is layered on top of the second SCR catalyst composition 220 on a common substrate 212. Substrate 212 has an inlet end 222 and an outlet end 224 that defines an axial length L3. In one or more embodiments, substrate 212 generally comprises a plurality of channels 214 of a honeycomb substrate, of which only one channel is shown in cross section, for clarity. The first SCR catalyst composition 218 extends from the inlet end 222 of the substrate 212 through the entire axial length L3 of the substrate 212 to the outlet end 224. The length of the first SCR catalyst composition 218 is denoted as 218a in FIG. 3. The first SCR 218 catalyst composition may, in the specific embodiments, comprise vanádia / titania. The second SCR 220 catalyst composition may, in the specific embodiments, comprise a metal-exchanged 8-ring small pore molecular sieve. The first SCR catalyst composition 220 extends from the inlet end 224 of substrate 212 through the entire axial length L3 of substrate 212 to the outlet end 224. The SCR catalyst system 210 is effective for catalytic reduction selective NO _X.
[00121] It will be appreciated that the thickness of layer 218 can be relatively thin compared to the thickness of layer 220. The thickness of layer 218 can be thick enough to form a protective coating on layer 220 to protect the catalyst composition from sulfation layer 220. In one embodiment, the thickness of the composition layer of the first catalyst 218 is 5-10% of the total thickness of the compound layer
30/39
218 and 220. In other embodiments, the thickness of the first catalyst composition layer is 20-30% of the total thickness of the compound layer 218 and 220. In some embodiments, the thickness of the first catalyst composition layer is 30 -40% of the total layer thickness of compound 218 and 220.
Exhaust Gas Treatment System:
[00122] In one aspect of the invention, the exhaust gas treatment system comprises a lean mix engine, and the exhaust gas conduit in fluid communication with the lean mix engine, and a selective catalytic reduction catalyst system including a first SCR catalyst composition and a second SCR catalyst composition positioned in the system according to one or more embodiments. In the specific embodiments, the lean mix engine is a heavy-duty diesel engine.
[00123] In one or more modalities, the exhaust gas treatment system includes an exhaust gas flow containing a reducer such as ammonia, urea and / or hydrocarbon, and in specific modalities, ammonia and / or urea. In the specific embodiments, the exhaust gas treatment system further comprises a second exhaust gas treatment component, for example, a particulate filter or a diesel oxidation catalyst.
[00124] The soot filter, catalyzed or not catalyzed, can be upstream or downstream of the SCR catalyst system, according to one or more modalities. The diesel oxidation catalyst in specific embodiments is located upstream of the SCR catalyst system, according to one or more embodiments. In specific embodiments, the diesel oxidation catalyst and the catalyzed soot filter are upstream of the SCR catalyst system.
[00125] In specific modalities, the exhaust is transported from the lean mixture engine to a downstream position in the
31/39 exhaust system, and, in more specific modalities, containing NO _X , in which a reducer is added and the exhaust gas stream with the reducer added is transported to the SCR catalyst system, according to one or more more modalities.
[00126] In specific embodiments, the soot filter comprises a wall flow filter substrate, in which the channels are blocked alternately, allowing a gas stream entering the channels in one direction (direction of entry) to flow through the walls the channel and exit the channels from the other direction (exit direction).
[00127] An ammonia oxidation catalyst can be provided downstream of the SCR catalyst system to remove any unreacted or excess ammonia from the system. In specific embodiments, the AMOX catalyst can comprise a platinum metal such as platinum, palladium, rhodium or combinations thereof. In more specific embodiments, the AMOX catalyst may include a washcoat containing an SCR catalyst system that includes a first SCR catalyst composition positioned on a substrate and a second SCR catalyst composition positioned on a substrate.
[00128] AMOX and / or the SCR catalyst composition can be coated on the flow filter or on the wall filter. If a wall-flow substrate is used, the resulting system will be able to remove particulate matter together with polluting gases. The wall flow filter substrate can be made of materials known in the art, such as cordierite, aluminum titanate or silicon carbide. It will be understood that the loading of the catalytic composition onto a flow substrate by walls will depend on substrate properties, such as porosity and wall thickness and will normally be less than the load on a flow through the substrate.
32/39
SCR activity:
[00129] The invention is now described with reference to the following examples. Before describing several exemplary embodiments of the invention, it should be understood that the invention is not limited to the details of construction or process steps set out in the following description. The invention is capable of other modalities and can be practiced or performed in different ways.
EXAMPLES [00130] EXAMPLE 1 - PREPARATION OF CATALYST MATERIALS [00131] Vanádia-Titania Catalyst [00132] A standard vanadium / titania / tungsten catalyst (V ₂ O ₅ (2.5%) / WO ₃ (10%) / TiO ₂ ) was prepared and a paste was made in about 30-40% solids by grinding to provide a wash coat paste.
[00133] Cu-Zeolite [00134] A Cu-CHA powder (SSZ-13) was prepared by mixing 100 g of CHA in the form of Na, having an alumina / silica molar ratio of 30, with 400 ml of a copper (II) acetate solution of about 1.0 Μ. The pH was adjusted to about 3.5 with nitric acid. An ion exchange reaction was carried out between CHA in the form of Na and copper ions by stirring the paste at about 80 ° C for about 1 hour. The resulting mixture was then filtered to provide a filter mass, and the filter mass was washed with deionized water in three portions until the filtrate was clear and colorless, and the washed sample was dried.
[00135] The CuCHA catalyst obtained comprises CuO in a range of about 2.5 to 3.5% by weight, as determined by the ICP analysis. A CuCHA slurry was prepared for 40% target solids. The paste was ground and a binder of zirconium acetate in dilute acetic acid (containing 30% ZrO ₂ ) was added to the paste with
33/39 agitation.
[00136] EXAMPLE 2- LATERALLY ZONE CATALYST SYSTEM [00137] The pastes described above were coated separately on the 12Dx6L cell ceramic substrate having a cell density of 400 cpsi (cells per square inch) and a wall thickness of 4 mil. The coated substrates were dried at 110 ° C for 3 hours and calcined at about 400 ° C for 1 hour. The coating process was repeated once to obtain a target washcoat load in the range of 3 g / ³ in the vanadium-titania coated core, and 2.1 g / ³ in the CuCHA-coated core. Samples were aged for 200 hours at 550 ⁰ C in an engine test cell of heavy duty diesel.
[00138] COMPARATIVE EXAMPLE 3- LATERALLY ZONE CATALYST SYSTEM [00139] Example 2 was repeated with the exception of both substrates that were coated with CuCHA at the same loading.
[00140] EXAMPLE 4- SIDE SYSTEMS LATERALLY ENGINE TESTS [00141] The catalyst systems in Example 3 and 4 were tested on a 9L heavy duty engine together with an electric motor dynamometer. The bench is able to run both in steady state and transient test cycles. In the current work, a heavy duty transient test cycle (HDTP) and a non-road transient test cycle (NRTC) were performed. Catalyst samples were in full size with diameters of 12 in parts (400/4), which spent 200h at 550Ό of aging per engine before evaluations. To demonstrate the advantage of the side zone system of a 12x6 Cu-CHA brick upstream of a 12x 6 Cu-CHA brick, a sequential reference of 12x6 Cu + 12x6 Cu of the SCR system was also evaluated. In a comparative study,
34/39 only the first SCR catalyst brick was switched between V-SCR and-Cu-SCR, other systems, such as the second SCR brick, the urea injection system, drill sample locations were kept the same .
[00142] During the evaluation tests, two MKS FTIR samplers were positioned in the SCR upstream and downstream, respectively, for gaseous emissions measurements, including, but not limited to, NO, NO2, N2O and etc. The exhaust sampling lines were heated to constant 1900. All evaluation tests in this example were performed with ULSD fuel (ultra low diesel sulfur), where the sulfur concentration is less than 15 ppm (% by weight).
[00143] In one configuration, a diesel oxidation catalyst and catalyzed soot filter were placed upstream of the SCR catalyst system to simulate a heavy duty engine transient cycle. In another configuration, the SCR catalyst system was tested without catalysts or filters upstream.
[00144] Figure 4 shows the results of the HDTP cycle and Figure 5 shows the results of the NRTC cycle. Both tests showed a significant reduction in the emission of N ₂ O for the samples in which the vanádia-titania catalyst was placed upstream of the Cu-zeolite sample.
[00145] The tests were repeated with a diesel oxidation catalyst and soot catalyst filter, upstream. Figure 6 shows the results for the HDTP cycle, and Figure 7 shows the results of the NRTC. Once again, the system with the vanádia-titania catalyst upstream of the Cu Zeolite system showed much lower N ₂ O emissions.
EXAMPLE 5 - PREPARATION OF THE LAYER CATALYST SYSTEM [00146] The washcoats of Example 1 were used and
35/39 coated on a single substrate in a layered configuration as described in relation to Figure 3. Stratification was varied as follows for the following samples.
Comparative Sample 5A of 2.1 g / in ³ single-coated CuCHA
Comparative Sample 5B of CuCHA lower coating of 2.1 g / in ³ ; Top coat of 0.2 g / in titania ³
Sample 5C of lower coating of CuCHA - CuCHA of 2.1 g / in ³ ; Top coat of 0.1 g / in ³ from Vanádia Titânia
5D sample of CuCHA lower coating of 2.1 g / in ³ ; Top coat of 0.2 g / in ³ of Vanádia Titânia
Sample 5E of CuCHA lower coating of 2.1 g / in ³ ; Top coating of 0,5 g / in ³ of Vanádia-Titânia
Sample 5F of CuCHA lower coating of 2.1 g / em3; Top coating of 1 g / in ³ from Vanádia Titânia [00147] EXAMPLE 6 - LAYER SYSTEM TEST [00148] The efficiency of selective catalytic reduction (SCR) of nitrogen oxides and selectivity of a fresh catalyst core was measured by addition of a feed gas mixture of 500 ppm NO, 500 ppm NH ₃ , 10% O ₂ , 5% H ₂ O, equilibrated with N ₂ to a steady-state reactor containing the 1D catalyst core x 3. The reaction was carried out at a spatial speed of 80,000 h ' ¹ over a temperature range of 150 ° C to 460 ° C.
[00149] The samples were hydrothermally aged in the presence of 10% H ₂ O at 550 ° C for 4 hours, followed by measuring the efficiency and selectivity of SCR of nitrogen oxides by the same process as described above for the evaluation of SCR in a fresh catalyst core.
[00150] The efficiency of selective catalytic reduction (SCR) of nitrogen oxides and selectivity of a fresh catalyst core was measured by adding a feed gas mixture of 500
36/39 ppm NO, 500 ppm NH ₃ , 10% O ₂ , 5% H ₂ O, equilibrated with N ₂ to a steady state reactor containing the 1D x 3 catalyst core. The reaction was carried out at a spatial speed of 80,000 ^{l 1} across a temperature range of 150 ° C to 460 ° C.
[00151] The samples prepared as described above were tested for SCR performance. In addition, all samples except 5F were exposed to sulfur (sulfation) at 300 ⁰ C at 20 ppm SO ₂ and 5% H ₂ O and 10% O ₂ in a feed gas upstream of a DOC core with SCR catalysts downstream for 6 hours.
[00152] FIG. 8 shows the conversion of NO _X as a function of temperature, for samples 5A-F before sulfation and Figure 9 shows the conversion of NOx as a function of temperature, after sulfation. Fresh conversions were comparable for all samples, except sample 5F. For the sulfated sample, Figure 9 shows that sample 5E had a significantly better conversion of NO _x .
[00153] EXAMPLE 9 - RESPONSE MODELING
DYNAMICS [00154] Figures 10 and 11 illustrate the improvements in the dynamic response behavior of a system according to one or more modalities. Figures 10 and 11 were prepared using a computer model. The performance measurements of the DeNO _x laboratory reactor and laboratory engine to describe the performance of the individual components within the system are the inputs for the computer model used. The example in Figure 10 shows the performance of DeNO _x as a function of the time obtained with fresh systems without stored ammonia before the start of the urea simulation / measurement. A Cu-SSZ13 system and a vanádia-based SCR system are compared with the Vanádia / Cu-SSZ-13 hybrid system. The SCR catalyst based on Vanádia was placed in front of the Cu-SSZ13 catalyst with a 50/50 ratio
37/39 in size within the modeled hybrid system. Low temperature operation at 225Ό of escape temperature and 5000 0 for 1 / h of the space speed at 500ppm at the NO _X input concentration at a NO ₂ / NO _X ratio of 10% was used for the comparison. These SCR entry conditions can be seen as being typical for systems operated in engine applications with a low precious metal load from an oxidation system in front of the SCR or in SCR only systems. The NSR was chosen in 1.1 in order to achieve the maximum DeNO _x performance of the studied systems relatively quickly. Although the Cu-SSZ13 system achieves greater DeNO _x performance after 700 seconds of dosing, the response behavior of DeNO _x after the start of application of the doses in 0 seconds has a different classification. The response of the Vanádia-based SCR system is faster in relation to the increase in DeNO _x after starting dosing compared to the Cu-SSZ13 system (for example, up to 350 seconds). The SCR based on the Vanádia hybrid system in combination with the Cu-SSZ13 has the advantage of being close to the behavior of the SCR dynamic response based on Vanádia and, in addition, offering greater steady state to the performance of DeNO _x , as shown in Figure 10, after, for example, 1000 seconds.
[00155] Figure 11 was generated by retracing Figure 10 using the total NH ₃ adsorbed on the catalysts, in grams, according to the results for the x-axis. The practical advantage of the hybrid system can be seen when comparing the necessary ammonia stored in the catalysts to achieve, for example, 70% DeNO _x . The Cu-SSZ13 system needs approximately 4.5 g of NH ₃ , while the Vanádia-based system would need about 2.5 g, and the proposed hybrid system of approximately 3 g of stored ammonia. The hybrid system, therefore, would deliver DeNOx performance faster and with lower NH ₃ storage levels in
38/39 compared to the Cu-SSZ13 SCR system. In addition, the hybrid system would deliver steady-state performance of greater DeNO _x compared to the Vanadian-based SCR system. The higher DeNO _x performance achieved at lower NH ₃ storage levels has an additional advantage when the engine accelerates with sudden increases in exhaust temperature. In this case, the amount of ammonia desorbed from the catalysts as a function of the temperature increase is less for the hybrid system compared to the Cu-SSZ13 system and, therefore, would result in lower slip values of NH ₃ behind the part the SCR of the after-treatment system. Even when using an ammonia oxidation catalyst, it is used to control the slip of NH ₃ from the SCR, very high ammonia peaks from acceleration events are often problems for the ammonia oxidation catalyst, due to the volumes typical installed in combination with ammonia light-off characteristics.
[00156] References throughout this specification to a modality, certain modalities, one or more modalities or modality mean that a specific characteristic, structure, material or resource described in relation to the modality is included in at least one modality of the invention. Thus, the appearances of the phrases as in one or more modalities, in certain modalities, in one modality, or in the modality in several places throughout this specification are not necessarily referring to the same modality of the invention. Furthermore, specific resources, structures, materials or characteristics can be combined in any suitable way in one or more modalities.
[00157] Although the invention of this document has been described with reference to specific modalities, it should be understood that these modalities are merely illustrative of the principles and applications of the present invention. It will be evident to
39/39 those skilled in the art that various modifications and variations can be made in the methods and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention includes modifications and variations that are within the scope of the appended claims and their equivalents.

权利要求:
Claims (17)
[1]
1. Selective catalytic reduction (SCR) catalyst system, characterized by the fact that it comprises a first SCR catalyst composition and a second SCR catalyst composition arranged in the system, the first SCR catalyst composition promoting greater N formation ₂ and less N ₂ O formation than the second SCR catalyst composition, and the second SCR catalyst composition having a different composition than the first SCR catalyst composition, the second SCR catalyst composition promoting less N formation ₂ and greater N ₂ O formation than the first SCR catalyst composition, wherein the first SCR catalyst composition and the second SCR catalyst composition are in a layered relationship with the first SCR catalyst composition layered on top of the second SCR catalyst composition.
[2]
2. SCR catalyst system according to claim 1, characterized in that the first SCR catalyst composition and the second SCR catalyst composition are positioned on a common substrate.
[3]
3. SCR catalyst system according to claim 1, characterized by the fact that the first SCR catalyst composition and the second SCR catalyst composition are positioned on different substrates.
[4]
SCR catalyst system according to any one of claims 1 to 3, characterized in that the first SCR catalyst composition comprises a mixed oxide.
[5]
5. SCR catalyst system according to claim 4, characterized by the fact that the mixed oxide is selected from Fe / titania, Fe / alumina, Mg / titania, Cu / titania, Ce / Zr, vanádia / titania, and their mixtures.
[6]
6. SCR catalyst system, according to
2/3 claims 4 or 5, characterized by the fact that the mixed oxide comprises vanádia / titania.
[7]
7. SCR catalyst system according to claims 5 or 6, characterized by the fact that vanádia / titania is stabilized with tungsten.
[8]
SCR catalyst system according to any one of claims 1 to 7, characterized in that the second SCR catalyst comprises a metal-exchanged small ring-8 molecular pore sieve.
[9]
9. Selective catalytic reduction (SCR) catalyst system, characterized by the fact that it comprises a first SCR catalyst composition comprising vanadium / titania positioned on a substrate and a second SCR catalyst composition comprising a small pore molecular sieve of Metal-exchanged 8-rings positioned on a substrate, where the first catalyst composition is located laterally upstream of the second catalyst composition.
[10]
10. SCR catalyst system according to claims 8 or 9, characterized by the fact that the molecular sieve has a type of structure selected from the group consisting of AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV , SAS, SAT, DDR and SAV.
[11]
11. SCR catalyst system according to any one of claims 8 to 10, characterized by the fact that the molecular sieve is an aluminosilicate zeolite and has the structure of the CHA type.
[12]
12. Catalyst according to claim 11, characterized by the fact that the zeolite is selected from SSZ13eSSZ-62.
[13]
13. Catalyst system according to any one of claims 8 to 12, characterized by the fact that the metal is selected from the group consisting of Cu, Fe, Co, Ce and Ni.
[14]
14. Catalyst system, according to any of the
3/3 claims 8 to 13, characterized by the fact that the metal is selected from Cu and is exchanged in the range of 2% to 8% by weight.
[15]
15. Exhaust gas treatment system for lean mix engine, characterized in that it comprises the catalyst system according to any one of claims 1 to 14, a lean mix engine, and an exhaust gas conduit in fluid communication with the lean mix engine, where the catalyst system is downstream of the engine.
[16]
16. Method for removing nitrogen oxides from the exhaust gases of a lean-mix engine, the method characterized by the fact that it comprises the contact of an exhaust gas stream from the catalyst system according to any one of claims 1 to 14.
[17]
17. Catalyst system according to claim 9, characterized by the fact that vanádia / titania promotes greater N ₂ formation and less N ₂ O formation than the metal-exchanged 8-ring small pore molecular sieve , and where the metal-exchanged 8-ring small pore molecular sieve promotes less N ₂ formation and greater N ₂ O formation than vanádia / titania, and the 8-ring small pore molecular sieve has a ammonia storage capacity greater than that of vanádia / titania.

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同族专利:

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公开号 | 公开日

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法律状态:
2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-17| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US14/208,904, DE 13/03/2014, REIVINDICADA NO PCT/US2014/026253, DE 13/03/2014, TENDO EM VISTA O PRAZO DEFINIDO NO ART. 4O DA CONVENCAO DA UNIAO DE PARIS. |

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2020-07-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-20| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-10-05| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-12-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-03-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361781760P| true| 2013-03-14|2013-03-14|

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PCT/US2014/026253|WO2014160292A1|2013-03-14|2014-03-13|Selective catalytic reduction catalyst system|

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