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    • 专利摘要:
    catalyst composition for the treatment of exhaust gases, catalytic coating, catalytic article, system for treatment of exhaust gases, and, method for the treatment of an exhaust gas, a composition of catalyst for the treatment of exhaust gases is provided which comprises a mixture of a first component and the second component, where the first component is an aluminum silicate or a ferrous silicate molecular sieve component, where the molecular sieve is either in the h + form or is the ion exchange with one or more transition metals, and the second component is a vanadium oxide supported on a metal oxide support selected from alumina, titania, zirconia, ceria, silica, and combinations thereof. also provided are methods, systems and catalytic articles which incorporate or use such a catalyst mixture.
    公开号:BR112015002829B1
    申请号:R112015002829-2
    申请日:2013-08-16
    公开日:2020-03-31
    发明作者:Juergen Bauer；Ralf Dotzel；Joerg Jodlauk；Rainer Leppelt；Jorg Muench；Irene Piras；Gudmund Smedler
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    “CATALYST COMPOSITION, SYSTEM AND METHOD FOR TREATING EXHAUST GAS, COATING AND CATALYTIC ARTICLE”
    BACKGROUND
    A.) Field of Use:
    [001] The present invention relates to catalysts, systems and methods that are useful for the treatment of an exhaust gas resulting from the combustion of a hydrocarbon fuel, and in particular, exhaust gas containing nitrogen oxides, such as a nitrogen gas. exhaust produced by diesel engines.
    B.) Description of Related Art:
    [002] Most of the flue exhaust gases contain relatively benign nitrogen (N2), water vapor (H2O), and carbon dioxide (CO2); but the exhaust gas also contains in a relatively small part, harmful and / or toxic substances, such as incomplete combustion carbon monoxide (CO), unburned fuel hydrocarbons (HC), combustion temperature nitrogen oxides (NOx) particles and particulate matter (mainly soot). To minimize the environmental impact of the exhaust gases released into the atmosphere, it is desirable to eliminate or reduce the amount of these undesirable components, preferably by a process that, in turn, does not generate other harmful or toxic substances.
    [003] One of the heaviest components to remove from a vehicle exhaust gas is NO X , which includes nitric oxide (NO), nitrogen dioxide (NO2), and / or nitrous oxide (N2O). The reduction of NOx to N2, in a poorly burned exhaust gas, such as that created by diesel engines, is particularly problematic because the exhaust gas contains enough oxygen to favor oxidative reactions instead of reduction. NOx can be reduced in an exhaust gas from diesel engines, in the
    Petition 870190099502, of 10/04/2019, p. 12/37 / 23 however, by a process commonly known as Selective Catalytic Reduction (SCR). An SCR process involves the conversion of NOx, in the presence of a catalyst and with the aid of a reducing agent, into elementary nitrogen (N2) and water. In an SCR process, a gaseous reducer, such as ammonia, is added to an exhaust gas stream, before contacting the exhaust gas with the SCR catalyst. The reducer is absorbed over the catalyst and the NOx reduction reaction occurs as the gases pass through or over the catalyzed substrate.
    [004] Several chemical reactions occur in a selective catalytic reduction (SCR) system using NH3 as a reducer, all of which represent desirable reactions that reduce NOx in elementary nitrogen. The dominant reaction mechanism is represented by equation (1).
    NO + 4 NH3 + O2 4 N2 + 6 H2O (1) [005] Non-selective competitive reactions with oxygen can produce secondary emissions or can consume NH3 unproductively. One such non-selective reaction is the complete oxidation of NH3, represented in equation (2).
    NH3 + 5 O2 4 NO + 6 H2O (2) [006] In addition, the reaction of NO2 present in NOx with NH3 is considered to proceed according to reaction (3).
    NO2 + 4 NH3 (7/2) N2 + 6 H2O (3) [007] In addition, the reaction between NH3 and NO and NO2 is represented by reaction (4):
    NO + NO2 + 2 NH3 2 N2 + 3 H2O (4) [008] Although the reaction rates of reactions (1), (3) and (4) vary greatly, depending on the reaction temperature and the type of catalyst used, that the reaction of (4) is, in general, 2 to 10 times higher than that of reactions (1) and (3).
    [009] The application of SCR technology to treat NOx emissions
    Petition 870190099502, of 10/04/2019, p. 13/37 / 23 of vehicle internal combustion engines, particularly low-burn internal combustion engines, is well known. The typical prior art SCR catalyst disclosed for that purpose includes TiO2-supported V2O5 / WO3 (see WO 99/39809). However, in some applications, the durability and thermal performance of the vanadium-based catalyst may not be acceptable.
    [0010] A class of SCR catalysts that has been investigated for the treatment of NOx of exhaust gases from the internal combustion engine is transition metal switched zeolites (see WO 99/39809 and US 4,961,917). However, in use, certain aluminosilicate zeolites, such as ZSM-5 and beta zeolites, have a number of drawbacks. They are susceptible to de-alumination during hydrothermal aging at high temperature, resulting in a loss of acidity, especially with Cu / beta and Cu / ZSM-5 catalysts; both beta-based and ZSM-5 catalysts are also affected by hydrocarbons that start to be adsorbed on the catalysts at relatively low temperatures and are oxidized as the temperature of the catalytic system is increased, generating a significant exothermic reaction, which can thermally damage the catalyst. This problem is particularly serious in vehicle diesel applications where significant amounts of hydrocarbons can be absorbed into the catalyst during cold start. And beta zeolites and ZSM5 are also prone to depositing coke by hydrocarbons, which reduces the performance of the catalyst. Therefore, there remains a need for an improved catalyst for selective catalytic reduction processes.
    SUMMARY OF THE INVENTION [0011] The Applicant has found that the mixture of vanadium-based SCR or ASC catalysts with certain molecular sieves improves the catalytic performance that is not observed when each of these
    Petition 870190099502, of 10/04/2019, p. 14/37 / 23 components is considered by itself. In particular, the catalyst of the present invention achieves improved high temperature performance, improved hydrothermal stability, high sulfur tolerance, and improved NO2 tolerance compared to the SCR catalyst known ASC catalysts. Such mixtures preferably contain aluminosilicate or ferrosilicate molecular sieves, preferably in H + form or an ion exchanged with a transition metal, such as Fe. Preferably, the molecular sieves have a selected structure of MFI, BEA, or FER .
    [0012] Thus, a catalyst composition for the treatment of exhaust gases is provided which comprises a mixture of a first component and the second component, wherein the first component is an aluminum silicate or a ferrous silicate molecular sieve component, in that the molecular sieve is either in H + form or is exchanged for ions with one or more transition metals, and the second component is a vanadium oxide supported on a metal oxide support selected from alumina, titania, zirconia, ceria, silica, and combinations thereof.
    [0013] According to another aspect of the invention, a catalytic coating is provided comprising a catalyst mixture, as described herein.
    [0014] According to another aspect of the invention, a catalytic article, preferably an extruded through-flow honeycomb, comprising a catalyst mixture, as described herein, is provided.
    [0015] In accordance with yet another aspect of the invention, a method is provided for the treatment of NOx or NH3 in an exhaust gas, such as an exhaust gas generated by an internal combustion diesel engine, wherein the method involves the contact of the exhaust gas with
    Petition 870190099502, of 10/04/2019, p. 15/37 / 23 a catalyst mixture, as described here that the concentration of NO X or NH3 in an exhaust gas is reduced.
    BRIEF DESCRIPTION OF THE DRAWING [0016] Figure 1 is a graph showing the conversion data from NOx to a fresh catalyst according to an embodiment of the present invention and the comparative data for a catalyst known in the prior art.
    [0017] Figure 2 is a graph showing NOx conversion data for a fresh catalyst according to an embodiment of the present invention and comparative data for a catalyst known in the prior art.
    [0018] Figure 3 is a graph showing the NOx conversion data for a fresh catalyst according to an embodiment of the present invention and the comparative data for a catalyst known in the prior art.
    [0019] Figure 4 is a graph showing NOx conversion data for aged catalysts according to an embodiment of the present invention and comparative data for aged catalysts known in the prior art.
    [0020] Figure 5 is a graph showing NOx conversion data for two different catalysts according to an embodiment of the present invention and comparative data for a catalyst known in the prior art.
    DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION [0021] In a preferred embodiment, the invention is directed to a catalyst to improve ambient air quality, in particular to improve exhaust gas emissions generated by diesel engines and other poor-burning engines. Exhaust gas emissions are
    Petition 870190099502, of 10/04/2019, p. 16/37 / 23 improved, at least in part, by the reduction of NO X and / or slip concentrations of NH3 in the exhaust gases of poor combustion over a wide operating temperature range. Useful catalysts are those that selectively reduce NOx and / or oxidize ammonia (ammonia slip) in an oxidizing environment (for example, an SCR catalyst and / or an ASC catalyst).
    [0022] According to a preferred embodiment, a catalyst composition is provided comprising a mixture of (a) a molecular sieve component comprising an iron-promoted aluminosilicate molecular sieve or a ferrosilicate molecular sieve (also known as a molecular sieve of amorphous iron) which has a structure selected from the group consisting of MFI, BEA and FER; and (b) a vanadium component comprising one or more vanadium oxides supported on a metal oxide support comprising titanium oxide.
    [0023] As used herein, the term mixture means an essentially uniform combination of two or more catalytic components, any of which can be used alone for the same purpose as the mixture. When combined in a mixture, the individual non-catalytic components are easily separable. And due, at least in part, to the nature of the synergistic combination, the catalytic effects of the constituent parts are indistinguishable from each other.
    [0024] In a preferred embodiment, the catalyst composition comprises a majority of the vanadium component (including the metal oxide support) over the molecular sieve component (including iron), based on weight. In certain embodiments, the catalyst composition comprises a vanadium component and a molecular sieve component in a weight ratio of about 1: 1 to about 99: 1. Preferably, the vanadium component and the sieve component
    Petition 870190099502, of 10/04/2019, p. 17/37 / 23 molecular are present in a weight ratio of about 2: 1 to about 4: 1, about 5: 1 to about 10: 1, or about 10: 1 to about 50: 1 Here, the vanadium component is calculated for the weight ratio based on the amount of titanium oxide (s), vanadium oxide (s), and, optionally, tungsten oxide (s) that are present in the mixture and does not include other non-catalytic metal oxides that are present, if any. Non-limiting examples of non-catalytic metal oxides that may be present in the composition include binders and other types of additives, such as alumina, zirconia, ceria, gel, mixtures of alumina with zirconia or ceria, alumina-coated ceria and mixed oxides, such as such as (not zeolite) silicaalumina, alumina-zirconia, chromium alumina, alumina and ceria. The binders are distinct from catalytic metal oxides in the composition because the binders are not promoted with a metal that is catalytically active for SCR processes and / or has a much larger particle size compared to catalytic metal oxides. A person skilled in the art will also appreciate that the reasons describe the relative proportions of the catalytically active components in the mixture and do not take into account other components such as fillers, fibrous reinforcing agents, processing aids, water, and the like that may be present in various forms of the catalyst composition, such as suspensions, coatings and extrusable pastes.
    [0025] In another embodiment, the catalyst composition comprises about 60 to about 99% by weight of the vanadium component and from about 1 to about 40% by weight of the molecular sieve component, based on the weight total of the catalytically active components in the mixture. In certain embodiments, the catalyst composition comprises about 60 to about 70, about 75 to about 85, or about 90 to about 97% by weight of the vanadium component and from about 30 to about 40, about 15 to about 25, or about 3 to about 10% by weight of the
    Petition 870190099502, of 10/04/2019, p. 18/37 / 23 molecular sieve.
    Preferred vanadium components include vanadium oxides on a support comprising titanium oxides and, optionally, tungsten oxides. In certain embodiments, titanium oxides and vanadium oxides are present in a weight ratio of about 30: 1 to about 2: 1, more preferably about 20: 1 to about 5: 1 , and even more preferably from about 15: 1 to about 7: 1. In certain embodiments, the catalyst composition comprises up to about 25% by weight of tungsten oxides, preferably from about 1 to about 25% by weight, more preferably from about 5 to about 20 % by weight, and even more preferably from about 7 to about 15% by weight, based on the total weight of the vanadium component.
    [0027] A titanium oxide is preferably titanium dioxide (TiO2), which is also known as titania or titanium (IV) oxide, and is preferably in the form of anatase. In certain embodiments, TiO2 is at least 90% by weight, and more preferably at least 95% by weight, in anatase form over the rutile form. In certain embodiments, TiO2 is chemically stabilized and / or pre-calcined, for example, as a final product from sulphate processing. Such a chemically stabilized TiO2 shows the X-ray reflections that are specific to the TiO2 structure in X-ray diffractometry.
    [0028] Typically, TiO2 serves as a high surface area support for vanadium oxide (s), which in a preferred embodiment is vanadium pentoxide (V2O5), also known as vanadium oxide (V) or vanádia. In certain embodiments, the vanadium oxide (s) are one or more of vanadium pentoxide, vanadium trioxide, vanadium dioxide, or a transition metal or rare earth metal vanadate, such as iron vanadate. The support may also include tungsten oxide (s), preferably tungsten trioxide (WO3), also
    Petition 870190099502, of 10/04/2019, p. 19/37 / 23 known as tungsten oxide (VI). Thus, V2O5-T1O2 or V2O5T1O2 / WO3 is in the form of self-supporting catalyst particles. In various embodiments, the catalytic metal oxide will have a surface area (BET) of about 10 to about 300 m 2 / g or more. In certain embodiments, TiO2 or TiO2 / WO3 will have an average particle size of about 10 to about 250 nanometers (nm), preferably about 10 to about 100 nm.
    [0029] Preferably, the molecular sieve is an aluminum silicate, preferably without substituted metals in the structure, or a ferrosilicate. Preferred structures include FER, MFI, and BEA. In certain embodiments, the molecular sieve is not a small pore molecular sieve. The molecular sieves, in particular, are aluminosilicates in the H + form or are exchanged for ions with a transition metal. Preferably, the aluminosilicate is substantially free of alkali and alkaline earth metals. Molecular sieves of form + H are preferably free of non-structural metals. Examples of useful transition metals include Fe, Cu, Ni, Co, Zn and Ni, Fe and Cu as being preferred, and Fe being particularly preferred. In certain embodiments, the molecular sieve is essentially free of any non-structural metal other than Fe. Preferably, the ion exchange occurs after synthesis of the molecular sieve.
    [0030] Preferred mixtures comprise an iron-promoted molecular sieve or ferrosilicate molecular sieve having at least one structure selected from MFI, BEA, and FER. Molecular sieves can be selected from zeolites and non-zeolite materials. A zeolite is generally considered to be an aluminosilicate, whereas a non-zeolite molecular sieve is a molecular sieve with a specific zeolite crystalline structure (for example, type IZA structure), but instead of being an aluminum silicate, the sieve molecular of not
    Petition 870190099502, of 10/04/2019, p. 20/37 / 23 zeolite has one or more non-aluminum / non-silicon cations present in its crystal lattice, for example, phosphorus, iron, etc. Useful types of non-zeolite molecular sieve include silicoaluminophosphates (SAPOs) and ferrosilicates. Particularly preferred are iron-containing aluminosilicate zeolites, such as MFI, BEA, and Fe-containing FER, with MFI being preferred.
    [0031] Useful MFI isotypes include ZSM-5, [Fe-Si-O] -MFI, AMS1B, AZ-1, Bor-C, boralite, encilite, FZ-1, LZ-105, nutinaite, NU-4, NU-5, silicalite, TS-1, ZST, ZST-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, and ZMQ-TB, with ZSM-5 being particularly preferred. Useful FER isotypes include ferrierite, [Si-O] -FER, FU-9, ISI-6, monoclinic ferrierite, NU-23, Sr-D, and ZSM-35. Useful BEA isotypes include Beta, [Ti-Si-O] - * BEA, CIT-6, and Tschernichite. Typical SiO2 / Al2O3 molar ratios for such materials are 30 to 100 and typical SiO2 / Fe2O3 in molar ratios are 20 to 300, such as 20 to 100.
    [0032] Preferably, the BEA structure contains exchanged iron or is an iron isomorphic BEA molecular structure (also referred to as the BEA type ferrosilicate), with the iron isomorphic BEA molecular structure being particularly preferred. In certain preferred embodiments, the BEA-type ferrosilicate molecular structure is a crystalline silicate which has (1) an iron-containing BEA structure, which has a SiO2 / Fe2O3 molar ratio of about 20 to about 300, and / or (2) less than 80% of the iron contained as fresh Fe 3+ isolated iron ions. Preferred BEA-type ferrosilicates useful in the present invention have a composition represented by the following formula:
    (x + y) M (2 / n) x O • x Fe2O3 * y AÍ2Ü3 • z SiO2 • w H2O where n is an atomic cation value M; x, y, and z represent the molar fractions of Fe2O3, AÍ2Ü3 and SiO2, respectively; x + y + z = l; w is a number of at least 0; z / x is 20 to 300, y can be 0, and,
    Petition 870190099502, of 10/04/2019, p. 21/37 / 23 optionally, z / y is at least 100.
    [0033] Preferably, iron-containing BEA structure has a SiO2 / Fe2O3 molar ratio of about 25 to about 300, about 20 to about 150, about 24 to about 150, about 25 to about 100, or about 50 to about 80. The upper limit of log (SiO2 / AhO3) per mole is not particularly limited, as long as the log (SiO2 / Al2O3) per mole is at least two (ie that is, the SiO2 / Al2O3 to mol ratio is at least 100). The log (SiO2 / Al2O3) per mole is preferably at least 2.5 (that is, the SiO2 / Al2O3 ratio per mole is at least 310), more preferably at least 3 (i.e., the SiO2 ratio / Al2O3 per mol is at least 1000). When the log (SiO2 / Al2O3) per mole exceeds 4 (that is, the SiO2 / Al2O3 per mole ratio becomes at least 10,000).
    [0034] In certain embodiments, the Fe-BEA aluminosilicate molecular sieve is pre-aged. Pre-aged Fe-BEA aluminosilicate can produce substantially better results than conventional Fe-BEA. Therefore, instead of the more conventional aging treatment at 500 ° C for 1 hour, Fe-BEA aluminosilicate is preferably aged from 600 to 900 ° C, preferably from 650 to 850 ° C, more preferably from 700 at 800 ° C, and even more preferably from 725 to 775 ° C, for 3 to 8 hours, preferably 4 to 6 hours, more preferably 4.5 to 5.5 hours, and even more preferably from 4.75 to 5.25 hours. Embodiments using pre-aged Fe-BEA aluminosilicate are advantageous in applications in which the formation of N2O is undesirable.
    [0035] In certain embodiments, iron is present in the molecular sieve material at a concentration of about 0.1 to about 10% by weight based on the total weight of the molecular sieve, for example, about 0 , 5% by weight to about 5% by weight, from about 0.5 to about 1% by weight, from about1 to about 5% by weight, about 2% by weight to
    Petition 870190099502, of 10/04/2019, p. 22/37 / 23 about 4% by weight, and about 2% by weight to about 3% by weight. Iron can be incorporated into molecular sieves for use in the present invention using techniques well known in the art, including liquid or solid ion exchange phase or by an incipient impregnation process. Such materials are referred to herein as molecular sieves promoted from iron containing or iron. For the manufacture of iron-containing aluminosilicate zeolites see Journal of Catalysis 232 (2) 318-334 (2005); EP2072128; and WO2009 / 023.202 which are incorporated herein by reference.
    [0036] The catalytic composition of the present invention can be prepared by mixing the vanadium component and the molecular sieve component. The type of mixing technique is not particularly limited. In certain embodiments, a TiO2 / WO3 suspension is prepared so that V2O5 powder and iron-promoted molecular sieve powder are added. The resulting suspension can be formulated as a coating or it can be dried and calcined in a powder form, which is then used to prepare a coating or an extrudable material.
    [0037] The catalytic zeolites described here can promote the reaction of a reducer, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N2) and water (H2O), vis-à-vis the competition reaction of oxygen and ammonia. In one embodiment, the catalyst can be formulated to favor the reduction of nitrogen oxides, with ammonia (ie, SCR catalyst). In another embodiment, the catalyst can be formulated to treat ammonia that is not consumed in the SCR catalyst reaction (i.e., ammonia slip). Here, the ammonia slip catalyst (ASC) was formulated to favor the oxidation of ammonia with oxygen. In yet another embodiment, an SCR catalyst and an ASC catalyst are used in series, wherein both catalysts comprise the catalyst mixture described herein, and
    Petition 870190099502, of 10/04/2019, p. 23/37 / 23 where the SCR catalyst is upstream of the ASC catalyst.
    [0038] In certain embodiments, the ASC catalyst is arranged as a top layer over an oxidative sub-layer, the sub-layer comprising a platinum group metal (PGM) catalyst or a non-PGM catalyst. In certain embodiments, the ASC catalyst is a honeycomb brick extruded or applied to a substrate, preferably substrates that are designed to provide a large contact surface with minimal back pressure, such as cordierite or metal honeycombs. flow through. For example, a preferred substrate has between about 25 and about 300 cells per square inch (6.45 cm 2 ) (CPSI) to guarantee low back pressure. Obtaining low back pressure is particularly important to minimize the effect of the ASC catalyst on the performance of low pressure EGR. The ASC catalyst can be applied to the substrate as a coating, preferably to achieve a loading of about 0.3 to 3.5 g / in 3 (16.39 cm 3 ). To further provide the conversion of NOx, the front part of the substrate can be coated with SCR-only coating, and the rear part coated with SCR and ASC catalyst, which can also include Pt or Pt / Pd on an alumina support .
    [0039] In accordance with another aspect of the invention, a method is provided for the selective catalytic reduction of NOx compounds or the oxidation of NH3 in an exhaust gas, which comprises contacting the exhaust gas with a catalyst mixture described herein. long enough to reduce the level of NOx and / or NH3 compounds in the exhaust gases. In certain embodiments, nitrogen oxides are reduced in the presence of a mixture of catalyst and the reducing agent at a temperature of at least about 100 ° C. In certain embodiments, NO X compounds are reduced at a temperature of about 200 ° C to about 650 ° C. Embodiments using higher temperatures
    Petition 870190099502, of 10/04/2019, p. 24/37 / 23 at about 450 ° C are particularly useful for the treatment of exhaust gases from heavy duty and light diesel engines, which are equipped with an exhaust system comprising diesel particulate filters (optionally catalyzed) which are actively regenerated, for example, by hydrocarbon injection into the exhaust system upstream of the filter, where the zeolite catalyst for use in the first invention is located downstream of the filter. In other embodiments, the SCR catalyst molecular sieve is incorporated into a filter substrate. The methods of the present invention can comprise one or more of the following steps: (a) the accumulation and / or combustion of soot that is in contact with the entry of a catalytic filter; (b) the introduction of a nitrogen reducing agent in the exhaust gas flow, before contacting the catalytic filter, preferably without intermediate catalytic steps involving the NOx treatment and the reducer; (c) the generation of NH3 over a NOx adsorbent catalyst, and preferably using NH3 such as a reducer in a reaction downstream of the SCR; (d) contact of the exhaust gas stream with a DOC to oxidize the soluble organic fraction based on hydrocarbon (SOF) and / or carbon monoxide in CO2, and / or oxidize NO to NO2, which, in turn, , can be used to oxidize particulate matter in a particle filter; and / or reduce particulate matter (PM) in the exhaust gases; (e) contacting the exhaust gas with one or more flow through SCR catalyst device (s) in the presence of a reducing agent to reduce the NOx concentration in the exhaust gases; and (f) contact of the exhaust gas with an ASC catalyst, preferably downstream of the SCR catalyst to oxidize most, if not all, of the ammonia before emitting the exhaust gas into the atmosphere or the passage of exhaust gases through a recirculation circuit, before the exhaust gas enters / re-enters the engine.
    [0040] The reducer (also known as a reducing agent) for
    Petition 870190099502, of 10/04/2019, p. 25/37 / 23 SCR processes means widely any compound that promotes the reduction of NOx in an exhaust gas. Examples of reducers useful in the present invention include ammonia, hydrazine or any suitable ammonia precursor, such as urea ((NH2) 2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate, and hydrocarbons, such as diesel fuel, and the like. Particularly preferred reducers are nitrogen-based, with ammonia being particularly preferred. In certain embodiments, the reducing agent may be a hydrocarbon, such as methane, diesel fuel, or the like.
    [0041] In certain embodiments, all or at least a portion of the nitrogen-based reducing agent, especially NH3, can be supplied by a NOx adsorbent catalyst (NAC), a poor NOx trap (LNT), or a NOx storage / reduction catalyst (NSRC), arranged upstream of the SCR catalyst, for example, an SCR catalyst of the present invention arranged in a wall flow filter. The NAC components useful in the present invention include a combination of catalysts of a base material (such as alkali metal, alkaline earth metal or a rare earth metal, including alkali metal oxides, alkaline earth metal oxides, and combinations thereof) of them), and a precious metal (such as platinum) and, optionally, a reducing catalyst component, such as rhodium. Specific types of base materials useful in CNS include cesium oxide, potassium oxide, magnesium oxide, sodium oxide, calcium oxide, strontium oxide, barium oxide, and combinations thereof. The precious metal is preferably present at about 10 to about 200 g / ft 3 (0.03 m 3 ), such as 20 to 60 g / ft 3 (0.03 m 3 ). Alternatively, the precious metal of the catalyst is characterized by the average concentration, which can be from about 40 to about 100 grams / ft 3 (0.03 m 3 ).
    Petition 870190099502, of 10/04/2019, p. 26/37 / 23 [0042] Under certain conditions, during periodically rich regeneration events, NH3 can be generated on a NOx adsorbent catalyst. The catalyst downstream of the NOx adsorbent SCR catalyst can improve the overall efficiency of the NOx reduction. In the combined system, the SCR catalyst is able to store the NH3 released from the NAC catalyst during rich regeneration events and uses the stored NH3 to selectively reduce some or all of the NOx that slides through the NAC catalyst during conditions normal poor operating conditions. [0043] In other embodiments, a nitrogen reducing agent, or precursor thereof, is introduced into the exhaust gas flow stream, preferably upstream of an SCR catalyst and downstream of a diesel oxidation catalyst . The introduction of this reducing agent can be carried out by an injector, spray nozzle, or other similar device.
    [0044] The methods of the present invention can be carried out on an exhaust gas from a combustion process, such as from an internal combustion engine (either mobile or stationary), an energy installation powered by oil or coal and gas turbine. The method can also be used to treat gases from industrial processes, such as refining, from heaters in refineries and boilers, ovens, the chemical processing industry, coke ovens, municipal waste facilities and incinerators, etc. . In a particular embodiment, the method is used to treat exhaust gas from an internal combustion engine for a low-burn vehicle, such as a diesel engine, a low-burn gasoline engine or an engine powered by liquefied petroleum gas or natural gas.
    [0045] According to another aspect, the invention provides a discharge system for an internal combustion engine for poor vehicle burning, which system comprises a duct to carry a flow of
    Petition 870190099502, of 10/04/2019, p. 27/37 / 23 exhaust gas, a source of nitrogen reducer, and a mixture of catalyst described here. The system may include a controller for the measurement of the nitrogen reducer, for the exhaust gas in circulation only when it is determined that the catalyst mixture is capable of catalyzing the reduction of NOx at or above a desired efficiency, such as above 100 ° C, above 150 ° C or above 175 ° C. The determination by the control means can be assisted by one or more appropriate sensor inputs indicating an engine condition selected from the group consisting of: exhaust gas, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, collector vacuum, ignition point, engine speed, lambda value of the exhaust gases, the amount of fuel injected into the engine, the position of the exhaust gas recirculation (EGR) of the valve and thus the amount of EGR and the thrust pressure.
    [0046] In a particular embodiment, the measurement is controlled in response to the amount of nitrogen oxides in the exhaust gases determined either directly (using a suitable NOx sensor) or indirectly, such as by means of consultation tables or maps pre-correlated - stored in the control means - correlating any one or more of the indicative inputs of an engine condition with the predicted NOx content of the above-mentioned exhaust gas. The measurement of the nitrogen reducer can be arranged in such a way that 60% to 200% of theoretical ammonia is present in the exhaust gas that enters the SCR catalyst calculated in 1: 1 NH3 / NO and 4: 3 NH3 / NO2. The control means can comprise a pre-programmed processor, such as an electronic control unit (ECU).
    [0047] In another embodiment, a diesel oxidation catalyst for the oxidation of nitrogen monoxide in the exhaust gases to nitrogen dioxide may be located upstream of a
    Petition 870190099502, of 10/04/2019, p. 28/37 / 23 measurement of the nitrogen reducer, for the exhaust gas. In one embodiment, the diesel oxidation catalyst is adapted to produce a gas flow that enters the SCR zeolite catalyst having a NO to NO2 ratio from about 4: 1 to about 1: 3 by volume, for example, at an exhaust gas temperature at the catalyst inlet oxidation of 250 ° C to 450 ° C. In another embodiment, the ratio of NO to NO2 is maintained at about 1: 2 to about 1: 5 by volume. The diesel oxidation catalyst can include at least one platinum group metal (or any combination thereof), such as platinum, palladium, or rhodium, coated on a flow monolith substrate. In one embodiment, the at least one platinum group metal is platinum, palladium, or a combination of both platinum and palladium. The platinum group metal can be supported on a high surface area coating component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, non-zeolite silica alumina, ceria, zirconia, titania or a mixed oxide or composition that contains both ceria and zirconia.
    [0048] In another embodiment, a suitable filter substrate is located between the diesel oxidation catalyst and the SCR catalyst. Filter substrates can be selected from any of the above, for example, wall flow filters. When the filter is catalyzed, for example, with an oxidation catalyst of the type discussed above, preferably the measuring point of the nitrogen reducer is located between the filter and the SCR catalyst mixture. Alternatively, if the filter is not catalyzed, the means for metering the nitrogen reducer can be located between the diesel oxidation catalyst and the filter.
    [0049] In another embodiment, the catalyst mixture for use in the present invention is coated on a filter located downstream of the oxidation catalyst. When the filter includes the catalyst mixture, the measuring point of the nitrogen reducer is preferably
    Petition 870190099502, of 10/04/2019, p. 29/37 / 23 located between the oxidation catalyst and the filter.
    [0050] In another aspect, a poor vehicle combustion engine is provided which comprises an exhaust system in accordance with the present invention. The internal combustion engine for low-burning vehicles can be a diesel engine, a low-burning gasoline engine or an engine powered by liquefied petroleum gas or natural gas.
    [0051] As used herein, the term essentially consisting of with respect to a catalytic composition means that the composition contains the named catalytic components, but does not contain additional components that materially affect the basic and novel features of the claimed invention. That is, the composition of the catalyst does not include additional components that would otherwise function as a catalyst for the intended reaction or serve to improve the catalytic base character of the claimed catalyst.
    EXAMPLES
    Example 1: Preparation of the Catalyst [0052] A catalyst composition was prepared by mixing iron-exchanged MFI aluminosilicate with a suspension of V2O5 TiO2 / WO3. The resulting composition contained about 20% by weight of iron-exchanged MFI aluminum silicate based on the combined weight of iron-exchanged MFI aluminum silicate and V2O5 - TiO2 / WO3 solids. A similar process was followed to prepare a catalyst containing 5 wt% iron-exchanged MFI aluminum silicate; a catalyst containing 20% by weight of iron-exchanged FER aluminosilicate; a catalyst containing 5 wt% iron-exchanged FER aluminosilicate; a catalyst containing 20% by weight of a BEA ferrosilicate; and a catalyst containing 10% by weight of a BEA ferrosilicate.
    [0053] These catalyst mixtures were formed into an extrudable mass, kneaded, stretched, and then extruded to form
    Petition 870190099502, of 10/04/2019, p. 30/37 / 23 honeycomb bricks 1 inch (2.54 cm) in diameter x 140 mm.
    [0054] In addition, the catalyst material containing 20% by weight of iron-exchanged MFI aluminum silicate was formed into an extruded, kneaded, stretched mass, and then extruded to form honeycomb bricks 400/11 of 10, 5 inches (26.67 cm) in diameter x 5.0 inches (12.7 cm) and also 400/11 honeycomb bricks of 10.5 inches (26.67 cm) in diameter x 7.0 inches (17.78 cm).
    Example 2: Catalyst Performance (varying NO2 levels) [0055] A 1 inch (2.54 cm) diameter x 140 mm extruded honeycomb brick containing a mixture of iron-exchanged MFI aluminosilicate and V2O5 - TiO2 / WO3 (20% by weight of Fe-MFI), was exposed to a simulated diesel engine exhaust gas at a spatial speed of around 60,000 / hour. The simulated exhaust gases contained about 9.3% by weight of O2, about 7.0% by weight of H2O, about 100 ppm of NOx (NO only) about 100 ppm of NH3, and the equilibrium N2 . The catalyst capacity for NOx conversion was determined at temperatures of 180, 215, 250, 300, 400, and 500 ° C.
    [0056] For comparison, a similar catalytic brick was prepared using only V2O5 - TiO2 / WO3. The comparative sample was also tested for the conversion of NO X under similar conditions.
    [0057] NO X conversion data for these fresh samples (ie, not aged) are provided in Figure 1. Here, the data shows that at 0% NO2, a catalyst based on a mixture of Fe-MFI and TiO2 / WO3 V2O5 resulted in better conversion of NOx at elevated temperatures, compared to a catalyst containing only V2O5 - TiO2 / WO3.
    [0058] This test was repeated with the exception that the NO X flow was adjusted to contain 35% by weight of NO2. The NOx conversion data for these fresh samples is provided in Figure 2. Here, the data
    Petition 870190099502, of 10/04/2019, p. 31/37 / 23 show that at 35% NO2, a catalyst based on a mixture of Fe-MFI and V2O5 - TO2 / WO3 resulted in better conversion of NOx compared to a catalyst containing only V2O5 - TiO2 / WO3 through a wide range of temperatures.
    [0059] This test was repeated again except that the NOx flow was adjusted to contain 65% by weight of NO2. Conversion data for NOx for these fresh samples is provided in Figure 3. Here, the data shows that 65% NO2, a catalyst based on a mixture of Fe-MFI and V2O5 - TiO2 / WO3 resulted in better conversion of NOx compared to a catalyst containing only V2O5 - TiO2 / WO3 across a wide temperature range.
    Example 3: Catalyst performance (post-hydrothermal aging) [0060] A 1 inch (2.54 cm) diameter x 140 mm extruded honeycomb brick containing a mixture of iron-exchanged MFI aluminosilicate and V2O5 - TiO2 / WO3 (20% by weight of Fe-MFI), was aged for 100 hours at 580 C. Three additional fresh bricks were also aged, under each of the following conditions: 100 hours at 580 C and 10% H2O; 100 hours at 650 ° C; and 100 hours at 650 C and 10% H2O.
    [0061] For comparison, two similar catalytic bricks were prepared using only V2O5 - TiO2 / WO3. Each of the comparative examples was aged under one of the following conditions: 100 hours at 580 C and 100 hours at 650 C.
    [0062] All the bricks were exposed to an exhaust gas from the simulated diesel engine at a spatial speed of about 60,000 / hour. The simulated exhaust gases contained about 9.3 wt.% O2, about 7.0 wt.% H2O, about 100 ppm NOx (NO only) about 100 ppm NH3, and the equilibrium N2 . The capacity of the catalyst for the conversion of NOx was determined at temperatures of 180, 215, 250, 300, 400, and 500 ° C.
    Petition 870190099502, of 10/04/2019, p. 32/37 / 23 [0063] NO X conversion data for these aged samples are provided in Figure 4. Here, the data shows that the catalyst based on a mixture of Fe-MFI and V2O5 - TiO2 / WO3 was very more hydrothermally stable compared to the catalyst containing only V2O5 - TiO2 / WO3, namely under harsh aging conditions. Example 4: Comparative Catalyst Performance [0064] An extruded honeycomb brick 1 inch (2.54 cm) in diameter x 140 mm containing a mixture of iron-exchanged MFI aluminosilicate and V2O5 - TiO2 / WO3 (20% by weight of Fe-MFI), it was exposed to a simulated diesel engine exhaust gas at a spatial speed of about 60,000 / hour. The simulated exhaust gas contained about 9.3% by weight of O2, about 7.0% by weight of H2O, about 100 ppm NOx (65% by weight NO2), about 100 ppm of NH3, and the Balance N2. The capacity of the catalyst for the conversion of NOx was determined at temperatures of 180, 215, 250, 300, 400, and 500 ° C.
    [0065] Another extruded honeycomb brick 1 inch (2.54 cm) in diameter x 140 mm, but which contains a mixture of iron-exchanged FER aluminosilicate and V2O5 - TiO2 / WO3 (20% by weight of Fe- FER), was exposed to a simulated diesel engine exhaust gas at a space speed of around 60,000 / hour. The simulated exhaust gas contained about 9.3% by weight of O2, about 7.0% by weight of H2O, about 100 ppm of NOx (65% by weight of NO2), about 100 ppm of NH3, and the equilibrium N2. Catalyst's ability to convert NOx was determined at temperatures of 180, 215, 250, 300, 400, and 500 ° C.
    [0066] For comparison, a similar catalytic brick was prepared using only V2O5 - TiO2 / WO3. The comparative sample was also tested for NOx conversion under similar conditions.
    [0067] Those NOx conversion data for these samples are shown in Figure 5. Here, the said data shows that at 65% NO2,
    Petition 870190099502, of 10/04/2019, p. 33/37 / 23 a catalyst based on a mixture of Fe-MFI and V2O5 - from T1O2 / WO3 resulted in better conversion of NOx at elevated temperatures compared to a catalyst containing a mixture of Fe-FER and V2O5 TO2 / WO3, and that a catalyst based on a mixture of Fe-MFI and V2O5 TiO2 / WO3 resulted in better conversion of NOx at elevated temperatures compared to a catalyst containing only V2O5 - TiO2 / WO3.
    权利要求:
    Claims (11)
    [1]
    1. Catalyst composition for the treatment of exhaust gas, characterized by the fact that it comprises a mixture of (a) 25 to 15% by weight of an aluminosilicate zeolite molecular sieve promoted by iron having a structure selected from the group consisting of MFI, BEA and FER; and (b) 75 to 85% by weight of one or more vanadium oxides supported on titanium oxide and tungsten oxides, based on the total weight of (a) and (b) in the mixture.
    [2]
    2. Catalyst composition according to claim 1, characterized by the fact that the aluminosilicate zeolite molecular sieve is exchanged for ion with iron.
    [3]
    Catalyst composition according to claim 1, characterized by the fact that iron is present in the aluminosilicate zeolite molecular sieve in a concentration of 0.1 to 10% by weight based on the total weight of the molecular sieve.
    [4]
    Catalyst composition according to claim 1, characterized in that the titanium oxide in (b) is titanium dioxide (TiO2).
    [5]
    Catalyst composition according to claim 1, characterized in that it comprises an extruded flow honeycomb as a catalytic article, comprising a catalyst mixture.
    [6]
    6. Exhaust gas treatment system, characterized by the fact that it comprises a selective catalytic reduction (SCR) catalyst upstream of an ammonia sliding catalyst (ASC), in which at least one of said SCR and ASC catalysts comprises the catalyst composition as defined in claim 1.
    [7]
    7. Exhaust gas treatment method, characterized by the fact that it comprises the steps of:
    The. contacting an exhaust gas stream containing NOx and / or NH3 in the presence of the catalyst composition as defined in the claim
    Petition 870190099502, of 10/04/2019, p. 35/37
    2/2
    1; and
    B. convert at least a portion of said NO X to N2 and / or convert at least a portion of NH3 to at least one of N2 and NO2.
    [8]
    Method according to claim 7, characterized in that said exhaust gas comprises a NO to NO2 ratio of 4: 1 to 1: 3 by volume.
    [9]
    9. Catalytic coating comprising the catalyst composition as defined in claim 1, characterized by the fact that it further comprises one or more fillers, binders, processing aids, water and contaminants.
    [10]
    10. Catalytic article comprising a substrate coated with or incorporating the catalyst composition as defined in claim 1, characterized in that the substrate is selected from a metal through-flow substrate, a ceramic through-flow substrate, a filter wall flow, a sintered metal filter, a partial filter, and an extruded honeycomb catalyst.
    [11]
    11. Catalytic article according to claim 10, characterized in that the substrate comprises a first layer containing a platinum group metal for the oxidation of ammonia and a second layer comprising the catalyst composition as defined in claim 1 , wherein the first layer is arranged directly on or inside the substrate and the second layer covers the first layer.
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    同族专利:
    公开号 | 公开日
    RU2670760C9|2018-12-17|
    JP2019048295A|2019-03-28|
    DK2755764T3|2016-11-28|
    GB201406893D0|2014-05-28|
    GB2510284B|2016-01-06|
    CN107335425B|2020-12-01|
    US20150224486A1|2015-08-13|
    RU2015109149A|2016-10-10|
    JP6742382B2|2020-08-19|
    RU2018136362A|2018-12-03|
    EP2755764B1|2016-07-27|
    PL2755764T3|2017-06-30|
    EP2755764A1|2014-07-23|
    JP2015530921A|2015-10-29|
    DE112013000477T5|2014-10-30|
    CN107335425A|2017-11-10|
    EP3088082A1|2016-11-02|
    US20190299198A1|2019-10-03|
    GB2510284A|2014-07-30|
    KR20200032259A|2020-03-25|
    WO2014027207A1|2014-02-20|
    RU2670760C2|2018-10-25|
    KR20150044911A|2015-04-27|
    US10252252B2|2019-04-09|
    BR112015002829A2|2017-08-08|
    CN104582845A|2015-04-29|
    KR102245483B1|2021-04-29|
    CN104582845B|2018-08-14|
    JP6476115B2|2019-02-27|
    KR102143811B1|2020-08-12|
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    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-09| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-03-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-03-31| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261684352P| true| 2012-08-17|2012-08-17|
    US61/684,352|2012-08-17|
    PCT/GB2013/052181|WO2014027207A1|2012-08-17|2013-08-16|Zeolite promoted v/ti/w catalysts|
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