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    • 专利摘要:
    COMPOSITION, METHODS TO SYNTHESIZE A ZEOLITE AND TO TREAT AN EXHAUST GAS, AND, CATALYST ARTICLE. A transition metal-AEl / ITE molecular sieve catalyst and the mixed model synthesis procedure are described.
    公开号:BR112016012397B1
    申请号:R112016012397-2
    申请日:2014-12-02
    公开日:2020-11-24
    发明作者:Joseph Michael Fedeyko；Alejandra RIVAS-CARDONA；Hai-Ying Chen
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    [0001] [001] The present invention relates to the transition metal zeolite having an AEI backbone. The invention also relates to a method for preparing such zeolites and their use as a catalyst. FUNDAMENTALS
    [0002] [002] The zeolites are crystalline or quasi-crystalline aluminosilicates constructed from repetitive SiO4 and AlO4 tetrahedral units. These units are linked to form main chains having regular molecular dimensions cavities and intra-crystalline channels. Numerous types of synthetic zeolites have been synthesized and each had a unique backbone based on the specific arrangement of its tetrahedral units. By convention, each type of main chain is indicated by a unique three-letter code (for example, “AEI”) by the International Zeolite Association (IZA).
    [0003] [003] Synthetic zeolites are typically produced using a structure targeting agent (SDA), also referred to as a "model" or "modeling agent". SDAs are typically complex organic molecules that guide or direct the molecular shape or pattern of the zeolite backbone. In general, the SDA serves to position hydrated silica and alumina and / or as a mold around which zeolite crystals are formed. After the crystals are formed, the SDA is removed from the interior structure of the crystals, leaving a molecularly porous aluminosilicate cage.
    [0004] [004] Zeolites have numerous industrial applications including internal combustion engines, gas turbines, coal-fired power plants and the like. In one example, nitrogen oxides (NOx) in the exhaust gas can be controlled through a so-called selective catalytic reduction (SCR) process, whereby NOx compounds in the exhaust gas are brought into contact with an agent reduction in the presence of a zeolite catalyst.
    [0005] [005] ZSM-5 and Beta zeolites have been studied as catalysts for SCR due to their relatively wide temperature activity window. However, the relatively large porous structures of these zeolites have several disadvantages. First, they are susceptible to high temperature hydrothermal degradation that results in a loss of activity. Also, medium and large pore sizes tend to absorb hydrocarbons that are oxidized when the temperature of the catalyst increases, thereby generating a significant exotherm that can thermally damage the catalyst. This problem is particularly acute in deficient flaring systems, such as diesel vehicle engines, where significant amounts of hydrocarbon can be absorbed during cold starting. Hydrocarbon coking represents another significant disadvantage of these medium and large pore molecular sieve catalysts. In contrast, small pore molecular sieve materials, such as those having an AEI backbone, offer an improvement in which less hydrocarbons are able to permeate in the backbone.
    [0006] [006] To promote the catalytic reaction, transition metals may be included in the zeolite material, as a substituted main chain metal (commonly referred to as “metal-substituted zeolite”) or as a metal with ion exchanged or post-impregnated synthesis (commonly referred to as “zeolite with exchanged metal”). As used here, the term "post-synthesis" means subsequent to the crystallization of the zeolite. The typical process for incorporating a transition metal into a zeolite occurs by cationic exchange or impregnation of metals or precursors after the molecular sieve is formed. However, these exchange and impregnation processes for the incorporation of metals often lead to deficient uniformity in the distribution of the metal, particularly when exchanged in molecular sieve with small pore. SUMMARY
    [0007] [007] A unique family of zeolites containing transition metal has been developed which are referred to here as “JMZ-2 zeolite” or “JMZ-2”. This zeolite material contains AEI backbones and optionally ITE backbones as a mixed phase material and / or as an inter-development and transition metal of the non-backbone. Preferably, the transition metal, such as copper, is an ionic species located in the cavities and channels of the zeolite crystal. The transition metal is incorporated into the zeolite material as zeolite crystals are formed.
    [0008] [008] According to certain aspects of the invention, JMZ-2 can be prepared by mixing a pot synthesis by incorporating a transition metal-amine complex that serves as a first SDA and a second different SDA. As used here, the terms "first" and "second" with respect to SDA are used to clarify that the two SDAs are distinct compounds, but the terms do not suggest or represent the order or sequence of operation or addition to the synthesis reaction mixture . The combination of two SDAs in a simple reaction mixture is referred to here as a mixed model and the incorporation of a transition metal in the zeolite during crystallization is referred to as the synthesis of a pot. Preferably, Cu versions of JMZ-2 are synthesized using Cu-tetraethylenepentamine (Cu-TEPA) as the first SDA and N, N-Dimethyl-3,5-dimethylpiperidinium or 1,1-diethyl-2,6-dimethylpiperidinium as the second SDA.
    [0009] [009] In a certain embodiment of the invention, a catalyst composition is provided comprising a synthetic zeolite having an AEI backbone and optionally an ITE backbone and a transition metal in situ uniformly dispersed within the zeolite cavities and channels .
    [0010] [0010] In another embodiment of the invention, a catalyst composition is provided which comprises a synthetic zeolite having an AEI backbone and optionally an ITE backbone, containing about 0.1 to about 7 weight percent of non-main chain copper based on the total weight of the zeolite, and containing less than 5 weight percent CuO based on the total weight of the zeolite.
    [0011] [0011] In other embodiments of the invention, a method is provided for synthesizing a zeolite comprising the steps of (1) preparing a reaction mixture comprising (a) at least one source of alumina, (b) at least one source of silica, (c) an organic transition metal-amine modeling agent, (d) seed crystals and (e) a second distinct organic modeling agent, each of which the first and second modeling agents is suitable for forming structures AEI main chain and (2) heat the reaction mixture under crystallization conditions for a time sufficient to form zeolite crystals having an AEI main chain and containing the transition metal. In certain embodiments, these steps are performed sequentially as described.
    [0012] [0012] In another embodiment of the invention, a catalyst article is provided for treating the exhaust gas comprising a catalyst composition described herein, wherein the catalyst composition is arranged in and / or within the honeycomb monolith substrate.
    [0013] [0013] In yet another embodiment of the invention, a method is provided for treating an exhaust gas comprising contacting a combustion exhaust gas containing NOx and / or NH3 with a catalyst article described here to selectively reduce at least a portion of NOx to N2 and H2O and / or oxidize at least a portion of NH3. DETAILED DESCRIPTION
    [0014] [0014] In general, JMZ-2 zeolites are prepared from the synthesis mixture of a pot containing a source of silica, a source of alumina, a first main chain organic modeling agent in the form of a transition metal- amine and a second organic modeling agent. The transition-amine metal is used to incorporate an ionic species of the transition metal, such as copper, into the zeolite channels and / or cavities during crystallization. The non-main chain transition metal incorporated in the zeolite during its synthesis is referred to here as in situ metal. In certain embodiments, silica, alumina, modeling agents and seed crystals are mixed to form a reaction mixture, for example, a gel, which is then heated to facilitate crystallization. The zeolite crystals containing metal precipitate from the reaction mixture. The crystals are collected, washed and dried.
    [0015] [0015] As used here, the term "AEI" refers to an AEI type main chain and the term "ΠΈ" refers to an ITE type main chain as recognized by the International Zeolite Association (IZA) Structure Commission. The new synthesis method described here is capable of producing a zeolite material having about 1 to 99% by weight of aluminosilicates having an AEI backbone and about 99 to 1% by weight of aluminosilicates having an ITE backbone, provided that the zeolite material comprises at least 70% by weight of, preferably at least about 80% by weight of, at least about 90% by weight of, at least about 95% by weight of or at least about 99% by weight of a combination of AEI and ITE main chains, based on the total weight of aluminosilicate in the zeolite material. Other secondary phases, such as FAU and / or MOR, may also be present. Preferably, these secondary phases comprise less than about 10 weight percent of the zeolite material, more preferably less than about 5 weight percent and even more preferably less than about 2 weight percent.
    [0016] [0016] Certain zeolite materials comprise an AEI backbone majority over the ITE backbone. For example, JMZ-2 zeolite may contain aluminosilicates having an AEI backbone and aluminosilicates having an ITE backbone in an AEEITE ratio of about 1.05: 1, about 1.5: 1, about 2: 1 , about 3: 1, about 4: 1, about 5: 1, about 10: 1, about 20: 1 or about 100: 1.
    [0017] [0017] In other embodiments, the zeolite material comprises a majority of the ITE main chain over the AEI main chain. For example, the JMZ-2 zeolite may contain aluminosilicates having an ITE backbone and aluminosilicates having an AEI backbone in an ITE: AEI ratio of about 1.05: 1, about 1.5: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 10: 1, about 20: 1 or about 100: 1.
    [0018] [0018] As used here, the term "zeolite" means a synthetic aluminosilicate molecular sieve having a structure constructed of alumina and silica (ie, tetrahedral units of repeat SiO4 and AlO4) and preferably having a molar ratio of silica to alumina (SAR) of at least 10, for example about 20 to about 50.
    [0019] [0019] The zeolites of the present invention are not silica-aluminophosphates (SAPOs) and, therefore, do not have an estimated amount of phosphorus in their main chain. That is, the zeolite backbones do not have phosphorus as a regular repeat unit and / or do not have an amount of phosphorus that should affect the material's basic physical and / or chemical properties, particularly with respect to the material's ability to selectively reduce NOx over a wide temperature range. In certain embodiments, the amount of phosphorus in the main chain is less than 0.1 weight percent, preferably less than 0.01 or less than 0.001 weight percent, based on the total weight of the zeolite.
    [0020] [0020] Zeolites, as used here, are free or substantially free of other main chain metals other than aluminum. In this way, a "zeolite" is distinct from a "metal-substituted zeolite" (also referred to as "isomorph-substituted zeolite"), in which the latter comprises a main chain containing one or more metals other than aluminum substituted in the main chain of zeolite.
    [0021] [0021] Suitable silica sources include, without limitation, fumigated silicas, silicates, precipitated silica, colloidal silica, silica gels, dealuminated zeolites, such as dealuminated Y zeolite and silicon hydroxides and alkoxides. Silica sources that result in a high relative yield are preferred. Typical sources of alumina are also generally known and include aluminates, alumina, other zeolites, aluminum colloids, bohemites, pseudoboemites, aluminum hydroxides, aluminum salts, such as aluminum sulfate and alumina chloride, aluminum hydroxides and alkoxides, alumina gels.
    [0022] [0022] When a first SDA, a transition metal-amine complex is used. Suitable transition metals include those that are known for use in promoting SCR of compostosx compounds in exhaust gases, with Cu and Fe being preferred and Cu being particularly preferred. Amine components suitable for the metal-amine complex include organic amines and polyamines that are capable of directing the formation of AEI backbone. A preferred amine component is tetraethylenepentamine (ΤΕΡΑ). The metal-amine complex (i.e., Cu-TEPA) can be preformed or formed in situ in the synthesis mixture from the individual metal and the amine components.
    [0023] [0023] A second main chain modeling agent, other than the copper-amine complex noted above, is selected to target the synthesis of AEI. Examples of suitable second modeling agents include cation of N, N-Diethyl-2,6-dimethylpiperidinium; N, N-Dimethyl-9-azoniabicycle 3.3.1nonane; N, N-Dimethyl-2,6-dimethylpiperidinium cation; cation of N-Ethyl-N-methyl-2,6-dimethylpiperidinium; N, N-Diethyl-2-ethylpiperidinium cation; cation of N, N-Dimethyl-2- (2-hydroxyethyl) piperidinium; N, N-Dimethyl-2-ethylpiperidinium cation; N, N-Dimethyl-3,5-dimethylpiperidinium cation; cation of N-Ethyl-N-methyl-2-ethylpiperidinium; 2,6-Dimethyl-1-Azonium cation 5.4 decane; cation of N-Ethyl-N-propyl-2,6-dimethylpiperidinium; 2,2,4,6,6-Pentamethyl-2-azoniabicycle cation 3.2.1 octane and N, N-Diethyl-2,5-dimethyl-2,5-dihydropyrrole cation, with N, N-Dimethyl -3,5-dimethylpiperidinium or 1,1-Diethyl-2,6-dimethylpiperidinium being particularly preferred. The anion associated with the cation can be any anion that is not harmful to the formation of the zeolite. Representative anions include halogens, for example, fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate and the like. Hydroxide is the most preferred anion. In certain embodiments, the reaction mixture and the subsequent zeolite are free or essentially free of fluorine.
    [0024] [0024] The synthesis of a pot is conducted by the predetermined combination of relative quantities of a source of silica, source of alumina, transition metal-amine complex, the second organic modeling agent and optionally a source of hydroxide ions, such such as NaOH and seed crystals, such as AEI zeolite, under various mixing and heating regimes as will be readily apparent to those skilled in the art. JMZ-2 can be prepared from a reaction mixture having the composition shown in Table 1 (shown as weight ratios). The reaction mixture can be in the form of a solution, gel or paste, with a gel being preferred. Reagents containing silicon and aluminum are expressed as SiO2 and Al2O3, respectively.
    [0025] [0025] The reaction temperatures, mixing times and speeds and other pressure parameters that are suitable for conventional AEI synthesis techniques are also generally suitable for the present invention. Without limitation, the following synthesis steps can be followed to synthesize JMZ-2. A source of alumina (eg, de-aluminated Y zeolite) is mixed in water with sodium hydroxide to promote the dissolution of alumina. The mixture is combined with an organic modeling agent (for example, 1,1-Diethyl-2,6-dimethylpiperidinium) and mixed by stirring for several minutes (for example, about 5 to 30). A source of silica (for example, TEOS) is added and mixed for several minutes (for example, about 30 to 120 minutes) until a homogeneous mixture is formed. Then, a source of copper (for example, copper sulphate) and ΤΕΡΑ are added to the mixture and mixed by stirring for several minutes (for example, about 15 to 60 minutes). Hydrothermal crystallization is usually conducted under autogenous pressure, at a temperature of about 100 to 200 ° C for a duration of several days, such as about 1 to 20 days, preferably around 1 to 3 days.
    [0026] [0026] At the conclusion of the crystallization period, the resulting solids are separated from the remaining reaction liquid by mechanical separation techniques, such as vacuum filtration. The recovered solids are then rinsed with deionized water and dried at an elevated temperature (for example, 75 to 150 ° C) for several hours (for example, about 4 to 24 hours). The drying step can be carried out under vacuum or at atmospheric pressure.
    [0027] [0027] The dried JMZ-2 crystals are preferably calcined, but can also be used without calcination.
    [0028] [0028] It will be estimated that the preceding sequence of steps, as well as each of the periods mentioned above, of time and temperature values are merely exemplary and can be varied.
    [0029] [0029] In certain embodiments, an alkali metal source, such as sodium, is not added to the synthesis mixture. The phrases "essentially alkali free" or "alkali free" as used here mean that alkali metal is not added to the synthesis mixture as an intentional ingredient. A "essentially alkali free" or "alkali free" catalyst as referred to here generally means that the catalyst material contains an irrelevant level of alkali metal with respect to the desired catalytic cavity. In certain embodiments, the JMZ-2 zeolite contains less than about 0.1 weight percent and preferably less than about 0.01 weight percent, alkali metal such as sodium or potassium.
    [0030] [0030] It has also been found that the pot synthesis procedure allows to adjust the transition metal content of the crystals based on the composition of the starting synthesis mixture. For example, a desired Cu or Fe content can be driven by providing a predetermined relative amount of Cu or Fe source in the synthesis mixture, without requiring post-synthesis impregnation to increase or decrease the copper charge in the material. In certain embodiments, the synthesized zeolite contains about 0.1 to about 5 weight percent copper, iron or a combination thereof, for example about 0.5 weight% to about 5 weight%, of about from 1 to about 3% by weight, from about 0.5 to about 1.5% by weight and about 3.5% by weight to about 5% by weight. For example, a controlled Cu load of 0.5 to 5% by weight, 0.1 to 1.5% by weight or 2.5 to 3.5% by weight, for example, can be achieved without post-processing additional synthesis. In certain embodiments, zeolite is free of post-synthesized exchanged metal, including copper and iron.
    [0031] [0031] The transition metal is catalytically active and substantially uniformly dispersed within the main chains of AEI and optionally ITE. Here, a substantially uniformly dispersed transition metal means that the zeolite substance contains no more than about 5 weight percent transition metal in the form of a transition metal oxide (eg CuO, FeO, Fe2O3 , Fe3O4), also referred to here as a free transition metal oxide or a soluble transition metal oxide, with respect to the total amount of that transition metal in the JMZ-2 zeolite. For example, the JMZ-2 zeolite contains no more than about 5 weight percent, no more than about 3 weight percent, no more than about 1 weight percent and no more than about 0.1 percent by weight, from the example, about 0.01 to about 5 percent by weight, about 0.01 to about 1 percent by weight, or about 0.01 to 3 percent weight percent CuO based on the total weight of copper in the zeolite material. It was observed that the minimization of the CuO concentration improves the hydrothermal durability and the performance of the exhaust gas treatment of the JMZ-2 zeolite.
    [0032] [0032] Preferably, the JMZ-2 zeolite contains a majority of transition metal in situ compared to the metal free of transition oxides. In certain embodiments, the JMZ-2 zeolite contains a weight ratio of free transition metal oxides (eg, CuO) to transition metal (eg, ionic Cu) less than about 1, less than about 0.5, less than about 0.1 or less than about 0.01, for example about 1 to about 0.001, about 0.5 to about 0.001, about 0.1 to about 0.001 or about 0.01 to about 0.001.
    [0033] [0033] Preferably, the JMZ-2 zeolite does not contain major chain transition metals in an estimated amount. Instead, copper and iron are present as an ionic species within the inner channels and cavities of the zeolite main chain. Consequently, the metal-containing zeolite JMZ-2 is not a metal-substituted zeolite (for example, a zeolite having a metal substituted in a backbone structure) and not necessarily a zeolite with exchanged metal (for example, a zeolite that has passed through a post-synthesis ion exchange). In certain embodiments, the JMZ-2 zeolite is free or essentially free of metals other than copper and aluminum or is essentially free of metals other than iron and aluminum. For example, in certain embodiments, JMZ-2 zeolite is free or essentially free of nickel, zinc, tin, tungsten, molybdenum, cobalt, bismuth, titanium, zirconium, antimony, manganese, magnesium, chromium, vanadium, niobium, ruthenium, rhodium, palladium, gold, silver, Indian, platinum, iridium and / or rhenium. In certain embodiments, the JMZ-2 zeolite is free or essentially free of iron. In certain embodiments, the JMZ-2 zeolite is free or essentially free of calcium. In certain embodiments, the JMZ-2 zeolite is free or essentially cerium free.
    [0034] [0034] JMZ-2 zeolite is useful as a catalyst in certain applications. The JMZ-2 catalyst can be used without a post-synthesis metal exchange. However, in certain modalities, the JMZ-2 may undergo a post-synthesis metal exchange. Thus, in certain embodiments, a catalyst is provided which comprises a JMZ-2 zeolite containing one or more catalytic metals exchanged in the zeolite channels and / or cavities after zeolite synthesis in addition to copper in situ or iron in situ. Examples of metals that can be exchanged or impregnated post-zeolite include transition metals, including copper, nickel, zinc, iron, tungsten, molybdenum, cobalt, titanium, zirconium, manganese, chromium, vanadium, niobium, as well as tin, bismuth and antimony; noble metals including platinum group metals (PGMs), such as ruthenium, rhodium, palladium, indium, platinum and precious metals, such as gold and silver; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium and rare earth metals such as marsh, cerium, praseodymium, neodymium, europium, terbium, erbium, ytterbium and yttrium. The preferred transition metals for post-synthesis exchange are base metals and preferred base metals include those selected from the group consisting of manganese, iron, cobalt, nickel and mixtures thereof. Post-synthesis embedded metals
    [0035] [0035] In certain embodiments, the zeolite containing metal contains alkaline earth metal exchanged post-synthesis, particularly calcium and / or magnesium, disposed within the channels and / or cavities of the zeolite main chain. In this way, the metal-containing zeolite of the present invention may have transition metals (Tm), such as copper or iron, incorporated in the zeolite channels and / or cavities and have one or more alkaline earth metals (Am), such as calcium or potassium, incorporated post-synthesis. The alkaline earth metal may be present in an amount with respect to the transition metal that is present. For example, in certain embodiments, TM and AM are present, respectively, in a molar ratio of about 15: 1 to about 1: 1, for example, about 10: 1 to about 2: 1, about 10 : 1 to about 3: 1 or about 6: 1 to about 4: 1, particularly where Tm is copper and Am is calcium. In certain embodiments, the relative cumulative amount of transition metal (Tm) and alkaline and / or alkaline earth metal (Am) is present in the zeolite material in an amount relative to the amount of aluminum in the zeolite, that is, the chain aluminum main. As used here, the ratio (Tm + Am): A1 is based on the relative molar quantities of TM + AM for the molar main chain Al in the corresponding zeolite. In certain embodiments, the catalyst material has a ratio (Tm + Am): A1 of no more than about 0.6. In certain embodiments, the ratio (Tm + Am): A1 is no more than 0.5, for example about 0.05 to about 0.5, about 0.1 to about 0.4 or about from 0.1 to about 0.2.
    [0036] [0036] In certain modalities, Ce is impregnated after synthesis in JMZ-2, for example by adding Ce nitrate to a zeolite promoted with copper by means of a conventional incipient humidity technique. Preferably, the concentration of cerium in the catalyst material is present in a concentration of at least about 1 weight percent, based on the total weight of the zeolite. Examples of preferred concentrations include at least about 2.5 weight percent, at least about 5 weight percent, at least about 8 weight percent, at least about 10 weight percent, about 1.35 to about 13.5 weight percent, about 2.7 to about 13.5 weight percent, about 2.7 to about 8.1 weight percent, about 2 to about 4 weight percent, about 2 to about 9.5 weight percent and about 5 to about 9.5 weight percent, based on the total weight of the zeolite. In certain embodiments, the concentration of cerium in the catalyst material is about 50 to about 550 g / ft3. Other Ce ranges include: over 100 g / ft3, over 200 g / ft3, over 300 g / ft3, over 400 g / ft3, over 500 g / ft3, from about 75 to about 350 g / ft3, from about 100 to about 300 g / ft3 and from about 100 to about 250 g / ft3.
    [0037] [0037] For embodiments in which the catalyst is part of a coating composition, the coating may additionally comprise a binder containing Ce or ceria. For such modalities, the Ce containing particles in the binder are significantly larger than the particles containing Ce in the catalyst.
    [0038] [0038] It was further verified that the pot synthesis procedure allows to adjust the catalyst SAR based on the composition of the starting synthesis mixture. SARs of 10 - 50, 20 - 40, 30 - 40, 10 - 15 and 25 - 35 for example, can be selectively achieved based on the composition of the starting synthesis mixture and / or adjustment of other process variables. The SAR of zeolites can be determined by conventional analysis. This reason is understood to represent, as closely as possible, the reason in the rigid atomic main chain of the zeolite crystal and to exclude silicon or aluminum in the binder or, in cationic or other form, within the channels. It will be estimated that it can be extremely difficult to directly measure the zeolite SAR after being combined with a binder material. Consequently, the SAR was previously expressed in the SAR term of the precursor zeolite, i.e., the zeolite used to prepare the catalyst, as measured before combining this zeolite with the other catalyst components.
    [0039] [0039] The process of synthesizing a previous pot can result in zeolite crystals of uniform size and shape with relatively low amounts of agglomeration. In addition, the synthesis procedure can result in zeolite crystals having an average crystalline size of about 0.1 to about 10 μm, for example about 0.5 to about 5 μm, about 0.1 to about 1 μm, about 1 to about 5 μm, about 3 to about 7 μm and others. In certain embodiments, large crystals are crushed using a jet mill or another technique of grinding particle into particle at an average size of about 1.0 to about 1.5 microns to facilitate the coating of a paste containing the catalyst to a substrate, such as a monolith through flow.
    [0040] [0040] The crystal size is the length of one edge of a face of the crystal. Direct measurement of the crystal size can be performed using microscopy methods, such as SEM and TEM. Other techniques for determining the average particle size, such as laser diffraction and dispersion, can also be used. In addition to the average crystal size, the catalyst compositions preferably have a majority of the crystal sizes are greater than about 0.1 μm, preferably between about 0.5 and about 5 μm, such as about 0.5 about 5 μm, about 0.7 to about 5 μm, about 1 to about 5 μm, about 1.5 to about 5.0 μm, about 1.5 to about 4.0 μm, about 2 to about 5 μm or about 1 μm to about 10 μm.
    [0041] [0041] The catalysts of the present invention are particularly applicable to heterogeneous catalytic reaction systems (ie, sodium catalysts in contact with a gas reagent). To improve the contact surface area, mechanical stability and / or fluid flow characteristics, the catalysts can be arranged on and / or within a substrate, preferably a porous substrate. In certain embodiments, a coating containing the catalyst is applied to an inert substrate, such as corrugated metal plate or an alveolar cordierite block. Alternatively, the catalyst is kneaded along with other components, such as fillers, binders and reinforcing agents, into an extrudable paste that is then extruded through a die to form a honeycomb block. Consequently, in certain embodiments, a catalyst article is provided which comprises a JMZ-2 catalyst described herein coated in and / or incorporated into a substrate.
    [0042] [0042] Certain aspects of the invention provide a catalytic coating. The coating comprising the JMZ-2 catalyst described here is preferably a solution, suspension or paste. Suitable coatings include surface coatings, coatings that penetrate a portion of the substrate, coatings that permeate the substrate or some combination thereof.
    [0043] [0043] A coating can also include non-catalytic components, such as fillers, binders, stabilizers, rheology modifiers and other additives, including one or more alumina, silica, silica alumina other than zeolite, titania, zirconia, ceria. In certain embodiments, the catalyst composition may comprise pore-forming agents, such as graphite, cellulose, starch, polyacrylate and polyethylene and the like. These additional components do not necessarily catalyze the desired reaction, but instead improve the effectiveness of the catalytic material, for example, by increasing its temperature range, increasing the catalyst's contact surface area, increasing the catalyst's adherence to a substrate, etc. in preferred embodiments, the coating load is> 0.3 g / in3, such as> 1.2 g / in3,> 1.5 g / in3,> 1.7 g / in3 or> 2.00 g / in3 and preferably <3.5 g / in3, such as <2.5 g / in3, In certain embodiments, the coating is applied to a substrate in a loading of about 0.8 to 1.0 g / in3, 1, 0 to 1.5 g / in3 or 1.5 to 2.5 g / in3.
    [0044] [0044] Two of the most common substrate designs are plate and honeycomb. Preferred substrates, particularly for mobile applications, include flow monoliths having a so-called honeycomb geometry that comprises multiple adjacent parallel channels that are open at both ends and, in general, extend from the inlet face of the substrate and result in a ratio of surface area to high volume. For certain applications, the monolith through the honeycomb flow preferably has a high cell density, for example, about 600 to 800 cells per square inch and / or an average wall thickness of about 0.18 - 0, 35 mm, preferably about 0.20 to 0.25 mm. For other certain applications, the monolith through the honeycomb flow preferably has a low cell density of about 150 to 600 cells per square inch, more preferably about 200 to 400 cells per square inch. Preferably, the honeycomb monoliths are porous. In addition to cordierite, silicon carbide, silicon nitride, ceramics and metal, other materials that can be used for the substrate include aluminum nitride, silicon nitride, aluminum titanate, α-alumina, mullite, for example, acite mullite, polucite, a thermet such as Al2OsZFe, Al2O3 / Ni or B4CZFe or composites comprising segments of either one or more of these. Preferred materials include cordierite, silicon carbide and alumina titanate.
    [0045] [0045] Plate type catalysts have smaller pressure drops and are less susceptible to clogging or dirt than hollow types, which is advantageous in high efficiency stationary applications, but plate configurations can be much larger and more expensive. A honeycomb configuration is typically smaller than a plate type, which is an advantage in mobile applications, but has higher pressure drops and therefore more easily. In certain embodiments, the plate substrate is constructed of metal, preferably corrugated metal.
    [0046] [0046] In certain embodiments, the invention is a catalyst article made by a process described here. In a particular embodiment, the catalyst article is produced by a process that includes the steps of applying a JMZ-2 catalyst composition, preferably as a coating, to a substrate such as a layer before or after at least one additional layer of a another composition to treat the exhaust gas was applied to the substrate. The one or more layers of catalyst on the substrate, including the JMZ-2 catalyst layer, are arranged in consecutive layers. As used here, the term "consecutive" with respect to the catalyst layers on a substrate means that each layer is in contact with its adjacent layers and that the catalyst layers as a whole are arranged on top of each other on the substrate.
    [0047] [0047] In certain embodiments, the JMZ-2 catalyst is arranged on the substrate as a first layer and another composition, such as an oxidation catalyst, reduction catalyst, decontaminating component or NOx storage component, is arranged on the substrate as a second layer. In other embodiments, the JMZ-2 catalyst is disposed on the substrate as a second layer and another composition, such as an oxidation catalyst, reduction catalyst, decontaminating component or NOx storage component, is disposed on the substrate as a first layer. As used here, the terms "first layer" and "second layer" are used to describe the relative positions of catalyst layers in the catalyst article with respect to the normal direction of direct flow of exhaust gas, past and / or over the catalyst article . Under normal exhaust gas flow conditions, the exhaust gas contacts the first layer before contacting the second layer. In certain embodiments, the second layer is applied to an inert substrate as a bottom layer and the first layer is the top layer which is applied over the second layer as a consecutive series of sublayers. In such embodiments, the exhaust gas penetrates (and consequently brings into contact) the first layer before contacting the second layer and subsequently takes up through the first layer to leave the catalyst component. In other embodiments, the first layer is a first zone arranged in an upstream portion of the substrate and the second layer is arranged on the substrate as a second zone, the second zone being downstream of the first.
    [0048] [0048] In another embodiment, the catalyst article is produced by a process that includes the steps of applying a JMZ-2 catalyst composition, preferably as a coating, to a substrate as a first zone and subsequently applying at least one composition additional for treating an exhaust gas to the substrate as a second zone, where at least a portion of the first zone is downstream of the second zone. Alternatively, the JMZ-2 catalyst composition can be applied to the substrate in a second zone that is downstream of the first zone containing the additional composition. Examples of the additional compositions include oxidation catalysts, reduction catalysts, decontaminating components (e.g., sulfur, water, etc.), or NOx storage components.
    [0049] [0049] To reduce the amount of space required by an exhaust system, individual exhaust components in certain modes are indicated to perform more than one function. For example, applying an SCR catalyst to a wall flow filter substrate instead of a substrate through the flow serves to reduce the total size of an exhaust treatment system to allow a substrate to serve two functions, that is ie, catalytically reducing the NOx concentration in the exhaust gas and mechanically removing soot from the exhaust gas. Consequently, in certain embodiments, the substrate is an alveolar wall flow filter or partial filter. Wall flow filters are similar to honeycomb substrates in that they contain a plurality of parallel, adjacent channels. However, the channels of alveolar substrates through the flow are opened at both ends, whereas the channels of wall flow substrates have a capped end, where the covering occurs at opposite ends of adjacent channels in an alternating pattern. Covering the alternating ends of the channels prevents the entry of gas into the substrate inlet face from the direct flow through the channel and existing. Instead of the exhaust gas, it enters in front of the substrate and travels around half the channels where it is forced through the channel walls before the second half of the channels enters and exits the back side of the substrate.
    [0050] [0050] The substrate wall has a porosity and pore size that is permeable to gas, but it traps a larger portion of the particulate substance, such as soot, from the gas as the gas passes through the wall. The preferred wall flow substrates are high efficiency filters. Wall flow filters for use as the present invention preferably have an efficiency of at least 70%, at least about 75%, at least about 80%, or at least about 90%. In certain embodiments, the efficiency will be about 75 to about 99%, about 75 to about 90%, about 80 to about 90%, or about 85 to about 95%. Here, efficiency occurs with respect to soot and other similarly sized particles and for particulate concentrations typically seen in conventional diesel exhaust gas. For example, particulates in the diesel exhaust can vary in size from 0.05 microns to 2.5 microns. Thus, efficiency can be based on this range or a sub-range, such as 0.1 to 0.25 microns, 0.25 to 1.25 microns, or 1.25 to 2.5 microns.
    [0051] [0051] Porosity is a measure of the percentage of empty space in a porous substrate and is related to back pressure in an exhaust system: generally, the lower the porosity, the greater the back pressure. Preferably, the porous substrate has a porosity of about 30 to about 80%, for example, about 40 to about 75%, about 40 to about 65%, or about 50 to about 60%.
    [0052] [0052] The pore interconnectivity, measured as a percentage of the total empty volume of substrate is the degree to which the pores, voids and / or channels, are joined to form continuous paths through a porous substrate, that is, the face of the exit face enters. In contrast, the pore interconnectivity is the sum of the closed pore volume and the pore volume that has a conduit to only one of the substrate surfaces. Preferably, the porous substrate has a volume of pore interconnectivity of at least about 30%, more preferably at least about 40%.
    [0053] [0053] The average pore size of the porous substrate is also important for filtration. The average pore size can be determined by any acceptable means, including mercury porosimetry. The average pore size of the porous substrate should be high enough to promote low backpressure, while providing adequate efficiency by the substrate itself, by promoting a layer of soot pie on the surface of the substrate, or a combination of both. Preferred porous substrates have an average pore size of about 10 to about 40 μm, for example, about 20 to about 30 μm, about 10 to about 25 μm, about 10 to about 20 μm, about 20 to about 25 μm, about 10 to about 15 μm and about 15 to about 20 μm.
    [0054] [0054] In general, the production of an extruded solid body containing the JMZ-2 catalyst involves the combination of the JMZ-2 catalyst, a binder, a compound that enhances the optional organic viscosity in a homogeneous paste that is then added to a component binder / matrix or a precursor thereof and optionally one or more of stabilized ceria and inorganic fibers. The combination is compacted in a mixture or mechanism or an extruder. The mixtures have organic additives, such as binders, pore builders, plasticizers, surfactants, lubricants, dispersants as processing aids to intensify wetting and therefore provide a uniform batch. The resulting plastic material is then molded, in particular using an extrusion press or an extruder including an extrusion die and the resulting moldings are dried and calcined. Organic additives are "burned" during the calcination of the extruded solid body. A JMZ-2 catalyst can also be coated or otherwise applied to the extruded solid body as one or more sublayers that reside on the surface or fully or partially penetrate the extruded solid body.
    [0055] [0055] Extruded solid bodies containing JMZ-2 catalysts according to the present invention generally comprise a unitary structure in the form of an alveolus having uniform and parallel sized channels extending from the first end to a second end thereof. The channel walls defining the channels are porous. Typically, an external "skin" surrounds a plurality of extruded solid body channels. The extruded solid body can be formed from any desired cross section, such as circular, square or oval. The individual channels in the plurality of channels can be triangular, hexagonal, circular squares, etc. The channels at a first upstream end can be blocked, for example, with a suitable ceramic cement and unblocked channels at the first upstream end can also be blocked as a second downstream end to form a wall flow filter. Typically, the arrangement of the blocked channels at the first upstream end looks like a checkerboard with a similar arrangement of the blocked and downstream channel ends.
    [0056] [0056] The binder / matrix component is preferably selected from the group consisting of cordierite, nitrides, carbides, borides, intermetallic, lithium aluminum silicate, a spinel, an optionally contaminated alumina, a source of silica, titania, zirconia, titania-zirconia, zirconia and mixtures of any two or more of these. The paste can optionally contain the reinforcement of the inorganic fibers selected from the group consisting of carbon fibers, glass fibers, metallic fibers, boron fibers, alumina fibers, silica fibers, silica-alumina fibers, carbide fibers silicon, potassium titanate fibers, aluminum borate fibers and ceramic fibers.
    [0057] [0057] The aluminum binder / matrix component is preferably gamma alumina, but it can be any other transition alumina, i.e., alpha alumina, beta alumina, chi alumina, eta alumina, rho alumina, alumina cover, theta alumina, delta alumina, beta lanthanum alumina and mixtures of any two or more such transition aluminas. It is preferred that the alumina is contaminated with at least one non-aluminum element to increase the thermal stability of the alumina. Suitable alumina contaminants include silicon, zirconium, barium, lanthanides and mixtures of any two or more of these. Suitable lanthanide contaminants include La, Ce, Nd, Pr, Gd and mixtures of any two or more of these.
    [0058] [0058] Silica sources may include a silica sol, quartz, fused or amorphous silica, sodium silicate, an amorphous aluminosilicate, an alkoxysilane, a silicone resin binder such as silicone methylphenyl resin, a clay, talc or a mixture of any two or more of these. From this list, silica can be SiO2 such as feldspar, mullite, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium, silica-biliary, silica-titanium dioxide, silica-alumina-ternary zirconia, silica- ternary alumina-magnesia, ternary silica-magnesia-zirconia, ternary silica-alumina-thorium and mixtures of any two or more of these.
    [0059] [0059] Preferably, the JMZ-2 catalyst is dispersed everywhere and preferably exactly everywhere, the total extruded catalyst body.
    [0060] [0060] When any of the above extruded solid bodies are made in a wall flow filter, the porosity of the wall flow filter can be 30-80%, such as 40-70%. Porosity and pore volume and pore radius can be measured, for example, using mercury intrusion porosity.
    [0061] [0061] The JMZ-2 catalyst described here can promote the reaction of a reducer, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N2) and water (H2O). In this way, in one embodiment, the catalyst can be formulated to favor the reduction of nitrogen oxides with a reducer (that is, an SCR catalyst). Examples of such reducers include hydrocarbons (for example, C3 - C6 hydrocarbons) and nitrogenous reducers such as ammonia and hydrazine ammonia or any suitable ammonia precursor, such as urea ((NH2) 2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.
    [0062] [0062] The JMZ-2 catalyst described here can also promote ammonia oxidation. Thus, in another embodiment, the catalyst can be formulated to favor oxidation of ammonia with oxygen, particularly at ammonia concentrations typically found downstream of an SCR catalyst (eg, ammonia oxidation catalyst (AMOX), such as a ammonia slip catalyst (ASC)). In certain embodiments, the JMZ-2 catalyst is arranged in an upper layer in an oxidative sublayer, where the sublayer comprises a platinum group metal catalyst (PGM) or a non-PGM catalyst. Preferably, the catalyst component in the sublayer is arranged on a surface area support including, but not limited to, alumina.
    [0063] [0063] In yet another modality, the SCR and AMOX operations are carried out in series, in which both processes use a catalyst that comprises the JMZ-2 catalyst described here and in which an SCR process occurs upstream of the AMOX process. For example, an SCR formulation of the catalyst can be arranged on the inlet side of a filter and an AMOX formulation of the catalyst can be arranged on the outlet side of the filter.
    [0064] [0064] Consequently, a method is provided for reducing NOx Compounds or oxidizing NH3 to a gas, which comprises contacting the gas with a catalyst composition described here for the catalytic reduction of NOx compounds for a period sufficient to reduce the level of NOx and / or NH3 compounds in the gas. In certain embodiments, a catalyst article is provided having an ammonia slip catalyst disposed downstream of a selective catalytic reduction (SCR) catalyst. In such embodiments, the ammonia slip catalyst oxidizes at least a portion of any nitrogen reducer that is not consumed by the selective catalytic reduction process. For example, in certain embodiments, the sliding ammonia catalyst is arranged on the outlet side of a wall flow filter and an SCR catalyst is arranged on the upstream side of a filter. Still in certain embodiments, the ammonia slip catalyst is disposed at the downstream end of a substrate through the flow and an SCR catalyst is disposed at the upstream end of the substrate through the flow. In other embodiments, the ammonia slip catalyst and SCR catalyst are arranged in separate blocks within an exhaust system. These separate blocks can be adjacent and in contact with each other or separated by a specific distance, as long as they are in fluid communication with each other and as long as the SCR catalyst block is arranged upstream of the sliding catalyst block of ammonia.
    [0065] [0065] In certain modalities, the SCR and / or AMOX process is carried out at a temperature of at least 100 ° C. In another embodiment, the processes take place at a temperature of about 150 ° C to about 750 ° C. In a particular embodiment, the temperature range is about 175 to about 550 ° C. In another mode, the temperature range is 175 to 400 ° C. In yet another embodiment, the temperature range is 450 to 900 ° C, preferably 500 to 750 ° C, 500 to 650 ° C, 450 to 550 ° C, or 650 to 850 ° C. Modes using temperatures higher than 450 ° C are particularly useful for treating exhaust gases from a heavy and light diesel engine that is equipped with an exhaust system comprising particulate diesel filters (optionally catalyzed) which are actively regenerated, for example, by injecting hydrocarbon into the exhaust system upstream of the filter, where the zeolite catalyst for use in the present invention is located downstream of the filter.
    [0066] [0066] According to another aspect of the invention, a method is provided for reducing Compounds ΝΟχ and / or oxidizing NH3 in a gas, which comprises contacting the gas with a catalyst described here for a period sufficient to reduce the level of compounds ΝΟx in the gas. The methods of the present invention can comprise one or more of the following steps: (a) soot accumulation and / or burning which is in contact with the entry of a catalyst filter; (b) introducing a nitrogen reducing agent in the exhaust gas stream before putting the catalytic filter in contact, preferably with no intervention of the catalytic steps involving the NOx treatment and the reducer; (c) generating NH3 in a NOx-absorbing catalyst or deficient NOx siphon and preferably using such NH3 as a reducer in a downstream SCR reaction; (d) contacting the exhaust gas stream with a DOC to oxidize hydrocarbon based on the soluble organic fraction (SOF) and / or carbon monoxide to CO2, and / or to oxidize NO to NO2, which in turn can be used to oxidize particulate matter in the particulate filter; and / or reduce the particulate matter (PM) in the exhaust gas; (e) contacting an exhaust gas with one or more SCR catalyst devices through the flow in the presence of a reducing agent to reduce the NOx concentration in the exhaust gas; and (f) contacting an exhaust gas with an ammonia slip 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 passing the exhaust gas exhaust through a recirculation arc before the exhaust gas enters / re-enters the engine.
    [0067] [0067] In another modality, all or at least a portion of the nitrogen-based reducer, particularly NH3, for consumption in the SCR process can be provided by a NOx absorber catalyst (NAC), a deficient ΝΟx siphon (LNT), a ΝΟx 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 a base material (such as alkali metal, alkaline earth metal or rare earth metal, including alkali metal oxide, alkaline earth metal oxides and combinations thereof) and a precious metal (such as platinum) and optionally a reduction catalyst component, such as rhodium. Specific types of basic material useful in NAC 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 / ft3, such as 20 to 60 g / ft3. Alternatively, the precious metal of the catalyst is characterized by the average concentration which can be from about 40 to about 100 g / ft3.
    [0068] [0068] Under certain conditions, during periodically rich regeneration events, NH3 can be generated in a NOx-absorbing catalyst. The SCR catalyst downstream of the ΝΟx-absorbing catalyst can improve the efficiency of the NOx reduction of the total system. In the combined system, the SCR catalyst is able to store ο NH3 released from the NAC catalyst during rich regeneration events and uses ο stored NH3 to selectively reduce some or all of NOx whether it slides through the NAC catalyst during poor operating conditions normal.
    [0069] [0069] The method for treating the exhaust gas as described here can be carried out on an exhaust gas derived from a combustion process, such as an internal combustion engine (whether mobile or fixed), a gas turbine a plant of energy powered by coal or oil. The method can also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, furnaces, the chemical processing industry, coke mills, municipal waste plants and incinerators, etc. In a particular embodiment, the method is used to treat the exhaust gas from a vehicular flaring combustion engine, such as a diesel engine, a flaring gasoline engine or an engine powered by petroleum gas liquid or natural gas.
    [0070] [0070] In certain aspects, the invention is a system for treating the exhaust gas generated by the combustion process, such as an internal combustion engine (whether mobile or fixed), a gas turbine, coal-fired power plants or oil and others. Such systems include a catalytic article comprising the JMZ-2 catalyst described herein and at least one additional component for treating the exhaust gas, wherein the catalytic article and at least one additional component are indicated to function as a coherent unit.
    [0071] [0071] In certain embodiments, the system comprises a catalytic article comprising a JMZ-2 catalyst described here, a conduit for directing an exhaust gas flow, a source of nitrogen reducer arranged upstream of the catalytic article. The system may include a controller to measure the nitrogen reducer in the exhaust gas flow only when it is determined that the zeolite catalyst is able to catalyze the NOx reduction at or above a desired efficiency, such as above 100 ° C , above 150 ° C or above 175 ° C. The measurement of the nitrogen reducer can be arranged such that 60% to 200% of the theoretical ammonia is present in the exhaust gas that enters the SCR catalyst calculated in 1: 1 NH3 / NO and 4: 3 NH3 / NO2.
    [0072] [0072] In another embodiment, the system comprises an oxidation catalyst (for example, a diesel oxidation catalyst (DOC)) to oxidize nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a point of mediation of the nitrogen reducer in the exhaust gas. In one embodiment, the oxidation catalyst is adapted to produce a tender gas stream in the SCR zeolite catalyst having a NO to NO2 ratio of about 4: 1 to about 1: 3 by volume, for example, in a exhaust gas temperature at the oxidation catalyst inlet from 250 ° C to 450 ° C. The oxidation catalyst may include at least one platinum group metal (or some combinations thereof), such as platinum, palladium or rhodium, coated on a monolith substrate through the flow. In one embodiment, the at least one metal in the platinum group 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, silica alumina other than zeolite, ceria, zirconia, titanium dioxide or an oxide mixed or composite containing both ceria and zirconia.
    [0073] [0073] In an additional embodiment, a suitable filter substrate is located between the oxidation catalyst and the SCR catalyst. The filter substrates can be selected from any of those mentioned above, for example, wall flow filters. Where the filter is catalyzed, for example, with an oxidation catalyst from the group discussed above, preferably the measurement point of the nitrogen reducer is located between the filter and the zeolite catalyst. Alternatively, if the filter is not catalyzed, the means for measuring the nitrogen reducer can be located between the oxidation catalyst and the filter.
    权利要求:
    Claims (8)
    [0001]
    Method for synthesizing a zeolite, characterized by the fact that it comprises: preparing a reaction mixture comprising (a) at least one source of alumina, (b) at least one source of silica, (c) an organic transition metal-amine modeling agent that is Cu-TEPA, (d) an alkali metal hydroxide and (e) second distinct organic modeling agent which is N, N-Dimethyl-3,5-dimethylpiperidinium or 1,1-Diethyl-2,6-dimethylpiperidinium, wherein each of the modeling agent organic transition metal-amine and the second organic modeling agent is suitable for the formation of an AEI backbone structure and in which the reaction mixture is essentially fluorine free; heat the reaction mixture under crystallization conditions for a time sufficient to form zeolite crystals having an AEI backbone and an ITE backbone and containing the transition metal.
    [0002]
    Method according to claim 1, characterized in that the majority of the transition metal is ionic metal dispersed in the crystalline zeolite.
    [0003]
    Method according to claim 1, characterized in that the organic transition metal-amine modeling agent is formed in situ in the reaction mixture from the individual metal and the amine components.
    [0004]
    Method according to claim 1, characterized in that the zeolite has a SAR of 10 to 50 and contains 0.5 to 5 weight percent copper ion.
    [0005]
    Method according to claim 1, characterized in that the zeolite is washed, dried and calcined to form a Cu-AEI / ITE catalyst.
    [0006]
    Composition of zeolite, characterized by the fact that it is prepared by preparing a reaction mixture comprising (a) at least one source of alumina, (b) at least one source of silica, (c) Cu-TEPA, (d) an alkali metal hydroxide and (e) one of N, N-Dimethyl-3,5-dimethylpiperidinium or 1,1-Diethyl-2,6-dimethylpiperidinium; heat the reaction mixture under crystallization conditions long enough to form zeolite.
    [0007]
    Exhaust gas catalyst article, characterized by the fact that it comprises a zeolite composition as defined in claim 6 arranged in and / or within an alveolar monolith substrate.
    [0008]
    Method for treating an exhaust gas, characterized in that it comprises contacting a combustion exhaust gas containing NOx and / or NH3 with a catalyst article as defined in claim 7 to selectively reduce at least a portion of NOx in N2 and H2O and / or oxidize at least a portion of the NH3.
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    同族专利:
    公开号 | 公开日
    DE102014117671A1|2015-06-03|
    RU2744763C2|2021-03-15|
    EP3077107A1|2016-10-12|
    GB201421334D0|2015-01-14|
    JP6920390B2|2021-08-18|
    GB2522753A|2015-08-05|
    GB2537023A|2016-10-05|
    KR102288100B1|2021-08-11|
    JP2020033256A|2020-03-05|
    GB201602660D0|2016-03-30|
    US9480976B2|2016-11-01|
    CN104801338B|2020-07-31|
    KR20160093681A|2016-08-08|
    JP2016538237A|2016-12-08|
    CN104801338A|2015-07-29|
    JP2021167270A|2021-10-21|
    US20150151285A1|2015-06-04|
    WO2015084834A1|2015-06-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    KR19980702947A|1995-03-17|1998-09-05|터너 더블유. 케이쓰|Process for preparing zeolite using organic template and amine|
    US5958370A|1997-12-11|1999-09-28|Chevron U.S.A. Inc.|Zeolite SSZ-39|
    WO2004070025A2|2003-02-05|2004-08-19|Juan Saus|Novel goodpasture antigen-binding protein isoforms and protein misfolded-mediated disorders|
    CA2548315C|2003-12-23|2009-07-14|Exxonmobil Chemical Patents Inc.|Chabazite-containing molecular sieve, its synthesis and its use in the conversion of oxygenates to olefins|
    CN100475699C|2003-12-23|2009-04-08|埃克森美孚化学专利公司|Aei-type zeolite, synthesis and use in the conversion of oxygenates to olefins|
    US8057782B2|2006-12-27|2011-11-15|Chevron U.S.A. Inc.|Preparation of small pore molecular sieves|
    US7645718B2|2007-03-26|2010-01-12|Pq Corporation|Microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same|
    EP3300791B1|2007-04-26|2019-03-27|Johnson Matthey Public Limited Company|Transition metal/zeolite scr catalysts|
    US8715618B2|2008-05-21|2014-05-06|Basf Se|Process for the direct synthesis of Cu containing zeolites having CHA structure|
    GB2482094B|2009-04-17|2014-05-14|Johnson Matthey Plc|Small pore molecular sieve supported copper catalysts durable against lean/rich ageing for the reduction of nitrogen oxides|
    EP2718010A1|2011-06-05|2014-04-16|Johnson Matthey Public Limited Company|Platinum group metal catalyst for treating exhaust gas|
    JP5831367B2|2011-06-27|2015-12-09|三菱樹脂株式会社|Process for producing transition metal-containing zeolite|
    US9409787B2|2011-06-27|2016-08-09|Mitsubishi Plastics, Inc.|Transition-metal-containing zeolite|
    EP2995790A1|2012-04-27|2016-03-16|Haldor Topsøe A/S|System for the purification of exhaust gas from an internal combustion engine|
    CN109590018A|2013-03-15|2019-04-09|庄信万丰股份有限公司|For handling the catalyst of exhaust gas|
    JP6278561B2|2013-07-10|2018-02-14|国立大学法人広島大学|Crystalline aluminosilicate and method for producing the same|
    BR112016004021B1|2013-08-30|2021-01-12|Johnson Matthey Public Limited Company|exhaust gas treatment catalyst, exhaust gas treatment catalyst article, and exhaust gas treatment method|CN110540215A|2014-11-21|2019-12-06|三菱化学株式会社|AEI-type aluminosilicate zeolite, catalyst and exhaust gas treatment method|
    ES2586770B1|2015-04-16|2017-08-14|Consejo Superior De Investigaciones Científicas |DIRECT SYNTHESIS METHOD OF CU-SILICOALUMINATE MATERIAL WITH AEI ZEOLITHIC STRUCTURE, AND ITS CATALYTIC APPLICATIONS|
    US10556802B2|2015-09-01|2020-02-11|Tosoh Corporation|Method for producing AEI zeolite|
    CN108136380B|2015-10-12|2021-07-30|优美科股份公司及两合公司|One-pot synthesis of copper-containing small pore zeolites|
    WO2017134005A1|2016-02-01|2017-08-10|Haldor Topsøe A/S|Method for the removal of nitrogen oxides from exhaust gas by selective catalytic reduction in presence of an scr catalyst comprising a fe-aei zeolithic material essentially free of alkali metal|
    WO2017134007A1|2016-02-01|2017-08-10|Haldor Topsøe A/S|Method for the removal of nitrous oxide from off gas in presence of catalyst comprising an fe-aei zeolite material essentially free of alkali metal|
    WO2017134006A1|2016-02-01|2017-08-10|Haldor Topsøe A/S|Method for the direct synthesis of iron-containing aei-zeolite catalyst|
    WO2017134001A1|2016-02-01|2017-08-10|Haldor Topsøe A/S|Hydrothermally stable iron containing aei zeolite scr catalyst|
    CN109982969A|2016-09-30|2019-07-05|庄信万丰股份有限公司|The new synthesis of the zeolite catalyst of metal promoted|
    GB2569754A|2016-09-30|2019-06-26|Johnson Matthey Plc|Synthesis of AEI and Cu-AEI zeolites|
    CN110300730A|2016-09-30|2019-10-01|庄信万丰股份有限公司|High silicon dioxide AEI zeolite|
    CA3041422A1|2016-10-24|2018-05-03|Basf Corporation|Integrated scr catalyst and lnt for nox abatement|
    KR101879695B1|2016-12-02|2018-07-18|희성촉매 주식회사|Zeolite structures with specific Cu2+ / Cu2+ratio in NO DRIFTS spectrum, a method for preparing zeolite structures, and a catalyst composition comprising the zeolite structures|
    CN110171835A|2017-03-16|2019-08-27|天津触净科技有限公司|A kind of cupric zeolite, its Manufacturing approach and use|
    EP3388392B1|2017-04-12|2021-01-20|Umicore Ag & Co. Kg|Copper-containing zeolites having a low alkali metal content, method of making thereof, and their use as scr catalysts|
    WO2018224651A2|2017-06-09|2018-12-13|Basf Se|Catalytic article and exhaust gas treatment systems|
    US11154847B2|2017-06-09|2021-10-26|Basf Corporation|Catalytic article and exhaust gas treatment systems|
    US20220032277A1|2018-10-30|2022-02-03|Basf Corporation|In-situ copper ion-exchange on pre-exchanged copper zeolitic material|
    CN109336131B|2018-11-01|2022-02-22|山东国瓷功能材料股份有限公司|Method for quickly synthesizing AEI type molecular sieve|
    TW202110740A|2019-07-09|2021-03-16|大陸商中國石油化工科技開發有限公司|Silicon- and germanium-based scm-25 molecular sieve, preparation method therefor, and use thereof|
    法律状态:
    2020-02-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-24| 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 02/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361910629P| true| 2013-12-02|2013-12-02|
    US61/910,629|2013-12-02|
    PCT/US2014/068134|WO2015084834A1|2013-12-02|2014-12-02|Synthesis of aei zeolite|
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