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    • 专利摘要:
    COMPOSITION, METHODS TO SYNTHETIZE A ZEOLITH AND TO TREAT AN EXHAUST GAS, AND, ARTICLE OF CATALISA DOR. A CHA-transition metal molecular sieve and mixed template synthesis procedure is described.
    公开号:BR112016012390B1
    申请号:R112016012390-5
    申请日:2014-12-02
    公开日:2021-05-04
    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:

    FIELD OF THE INVENTION
    [001] The present invention relates to transition metal containing zeolite having a main chain of CHA. The invention also relates to a method for preparing such transition metal containing zeolites and their use as a catalyst. FUNDAMENTALS
    [002] Zeolites are crystalline or quasi-crystalline aluminosilicates constructed of repeating SiO4 and AlO4 tetrahedral units. These units are linked to form main chains having regular intra-crystalline channels and cavities of molecular size. Numerous types of synthetic zeolites were synthesized and each had a unique main chain based on the specific arrangement of their tetrahedral units. By convention, each main-chain type is denoted by a unique three-letter code (eg, “CHA”) by the INTERNATIONAL ZEOLITE ASSOCIATION (IZA).
    [003] Synthetic CHA zeolites are 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, SDA serves to position hydrated silica and alumina and/or as a mold around which zeolite crystals form. After the crystals are formed, the SDA is removed from the inner structure of the crystals, leading to the molecularly porous aluminosilicate cage
    [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. of reduction in the presence of a zeolite catalyst.
    [005] Zeolites ZSM-5 and Beta were studied as SCR catalysts 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 as the catalyst temperature increases, thereby generating a significant exotherm that can thermally damage the catalyst. This problem is particularly acute in a deficient burner system, such as vehicular diesel engines, where significant amounts of hydrocarbon can be absorbed during a cold start. 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 a CHA backbone type code (as defined by the International Zeolite Association), offer an improvement in that less hydrocarbons are able to permeate into the backbone.
    [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 an ion-exchanged or post-impregnated metal. synthesis (commonly referred to as “metal-exchanged zeolite”). As used herein, the term "post-synthesis" means subsequent to the crystallization of the zeolite. The typical process for incorporating a transition metal into a zeolite is by cation 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 poor uniformity of metal distribution, and the smaller pores of CHA-type molecular sieve materials exacerbate that problem.
    [007] So-called "single pot" synthesis procedures in which a transition metal compound is present vis-à-vis molecular sieve backbone synthesis present as a post-synthesis ion exchanged metal. However, known single pot processes need sufficient control over metal loading, produce main chain structures with inadequate silicon to aluminum (SAR) ratios, and/or necessarily include alkali metal in the synthesis mixture which can contaminate acidic and have a detrimental effect on hydrothermal stability. In addition, reported single pot synthesis procedures to form metal-containing molecular sieves have been observed to produce significant amounts, in some instances as much as 20%, of amorphous phase, copper oxides and other impurities, which negatively impact stability and catalyst activity. SUMMARY
    [008] A unique family of CHA-type aluminosilicate molecular sieves containing copper and/or iron has been developed having a molecular ratio of silica to alumina (SAR) of about 25 to about 250, which are referred to herein as "zeolite JMZ-3 ” or “JMZ-3”. These metal-containing zeolites have an unexpectedly high SAR, are unexpectedly high in purity, and contain a high uniformity of distribution of transition metal species maintained within the main chain cavities and channels. Here, "high purity" means that the zeolite has at least one, at least two, or all three of (a) a high crystalline phase purity, (b) low amorphous zeolite and low amorphous silica-alumina content, and (c) ) low concentration of free or soluble transition metal (eg transition metal oxides). Like the catalyst, these materials exhibit improved SCR activity, thermal durability and resistance to hydrothermal aging. Furthermore, JMZ-3 zeolite shows surprisingly high catalytic activity at relatively low copper concentrations.
    [009] According to certain aspects of the invention, JMZ-3 can be prepared via a one-pot synthesis mixture by incorporating a metal-amine complex that serves as a first SDA with a CHA backbone and a second SDA with distinct CHA main chain. As used herein, 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 single reaction mixture is referred to here as a mixed model and the incorporation of a transition metal into the zeolite during crystallization is referred to as a pot synthesis. Preferably, Cu versions of JMZ-3 are synthesized using Cu-tetraethylenepentamine (Cu-TEPA) and N,N,N-dimethylethylcyclohexylammonium (DMECHA) as the first and second SDAs, respectively. Surprisingly, it has been found that the addition of very low amounts of zeolite seed crystals to the reaction mixture, particularly a reaction mixture that is free or substantially free of fluorine, results in zeolite CHA with a high silica to alumina (SAR) ratio. ).
    [0010] In a certain embodiment of the invention, there is provided a catalyst composition comprising a synthetic zeolite having a CHA backbone structure, a silica to alumina SAR molar ratio of about 25 to about 150, and a metal IN SITU transition layers evenly dispersed within the zeolite cavities and channels.
    [0011] In another embodiment of the invention, there is provided a composition comprising copper-containing synthetic zeolite having a CHA backbone structure, having a SAR of about 25 to about 150 and a unit cell volume of about 2355 to about 2375 Â3.
    [0012] In another embodiment of the invention, there is provided a catalyst composition comprising a synthetic zeolite having a CHA backbone structure, a SAR of about 25 to about 150 and containing about 0.1 to about 7 weight percent copper off the main chain based on the total weight of the zeolite, wherein the zeolite has a phase purity of at least 95% by weight and contains less than 5 weight percent CuO based on the total weight of the zeolite.
    [0013] 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 amine-transition metal organic shaping agent, (d) seed crystals, and (e) separate second organic shaping agent, wherein each of the first and second shaping agents is suitable to form a CHA backbone structure and in which the reaction mixture is essentially fluorine-free and (2) heat the reaction mixture under crystallization conditions for a time sufficient to form zeolite crystals having the CHA framework having a SAR of at least 25 and containing the transition metal. In certain embodiments, these steps are performed sequentially as described.
    [0014] In another embodiment of the invention, a catalyst article is provided for treating exhaust gas which comprises a catalyst composition described herein, wherein the catalyst composition is disposed in and/or within the alveolar monolith substrate.
    [0015] In yet another embodiment of the invention, there is provided a method for treating an exhaust gas which comprises contacting a combustion exhaust gas containing NOx and/or NH3 with a catalyst article described herein to selectively reduce at least a portion of the NOx to N2 and H2O and/or oxidize at least a portion of the NH3. BRIEF DESCRIPTION OF THE DRAWING
    [0016] Figure 1 shows comparative NOx conversion data for catalyst according to certain embodiments of the invention. DETAILED DESCRIPTION
    [0017] In general, JMZ-3 zeolites are prepared from the synthesis mixture of a pot containing a silica source, a source of alumina, a first organic shaping agent of CHA main chain in the form of a metal of amine-transition, a second organic CHA shaping agent, and seed crystals. The amine-transition metal is used to incorporate an ionic transition metal species, such as copper, into the channels and/or cavities of the zeolite during crystallization. The non-main chain transition metal incorporated into the zeolite during its synthesis is referred to herein as IN SITU metal. In certain embodiments, silica, alumina, molding agents and seed crystals are mixed to form a reaction mixture, eg, a gel, which is then heated to facilitate crystallization. Metal-containing zeolite crystals precipitate from the reaction mixture. Crystals are collected, washed and dried.
    [0018] As used herein, the term "CHA" refers to a CHA-type main chain as recognized by the INTERNATIONAL ZEOLITE ASSOCIATION (IZA) STRUCTURE COMMISSION and the term "CHA zeolite" means an aluminosilicate in which the primary crystalline phase is TEA.
    [0019] The novel synthesis method described here has been found to be capable of producing a high phase purity CHA zeolite, i.e., phase purities of 95% to greater than 99% (as determined by Rietveld analysis (XRD), for example). As used herein, the term phase purity with respect to a zeolite means the amount of a single crystalline phase of the zeolite (eg, based on weight) relative to the total weight of all phases (crystalline and amorphous) in the substance of zeolite. In this way, while other crystalline phases are present in the CHA zeolite, the JMZ-3 zeolite comprises at least about 95 weight percent CHA as a primary crystalline phase, preferably at least about 98 weight percent CHA and further more preferably at least about 99 or at least about 99.9 weight percent CHA, wherein the weight percent CHA is provided with respect to the total weight of the zeolite crystalline phases in the composition. Existing procedures for synthesizing Cu-containing CHA materials typically contain at least 10 percent by weight and still 20 percent by weight of impurities.
    [0020] It was also observed that the JMZ-3 zeolite has a smaller cell volume compared to the other copper-containing CHA zeolites. For example, the JMZ-3 zeolite has a unit cell volume of about 2355 to about 2375 Â3, for example about 2360 to about 2370 Â3, about 2363 to about 2365 Â3 or about 2363.5 to about of 2364.5 Â3 compared to other copper zeolites having a unit cell volume of about 2380 Â3 or to aluminosilicate CHA having a unit cell volume of about 2391.6 Â3. These unit cell volumes are applicable to each of the SAR ranges and transition metal concentration ranges described herein for JMZ-3. The property is believed to improve the catalytic performance and/or thermal durability of the material.
    [0021] Preferably, the CHA zeolite is substantially free of other crystalline phases and is not an intergrowth of two or more main chain types. By "substantially free" with respect to other crystalline phases, it is meant that zeolite JMZ-3 contains at least 99 percent by weight of CHA.
    [0022] As used herein the term "zeolite" means a synthetic aluminosilicate molecular sieve having a backbone constructed of alumina and silica (i.e. tetrahedral units of SiO4 and AlO4 repeating) and preferably having a silica to alumina molar ratio (SAR) of at least 25, for example about 25 to about 150. This high SAR is achieved without the need for post-synthesis delumination or main chain and defect curing processes. Consequently, in certain embodiments, the JMZ-3 catalyst is free from delumination and main-chain defect healing treatments, particularly post-synthesis and such treatment with acid (e.g., acetic acid), leaching with chelating agents or steaming (eg steaming at 400 to 650°C for 8 to 170 hours).
    [0023] The zeolites of the present invention are not silica-aluminophosphates (SAPOs) and, therefore, have no estimable amount of phosphorus in its main chain. That is, the zeolite scaffolds do not have phosphorus as a regular repeating unit and/or do not have an amount of phosphorus that should affect the basic physical and/or chemical properties of the material, particularly with respect to the material's ability to selectively reduce NOx over a wide temperature range. In certain embodiments, the amount of backbone phosphorus is less than 0.1 percent by weight, preferably less than 0.01 or less than 0.001 percent by weight, based on the total weight of the zeolite.
    [0024] Zeolites, as used herein, are free or substantially free of other main chain metals other than aluminum. In this way, a "zeolite" is distinguished from a "metal substituted zeolite" (also referred to as an "isomorph substituted zeolite"), in which the latter comprises a backbone that contains one or more non-aluminum substituted metals in the backbone of zeolite.
    Suitable silica sources include, without limitation, fumigated silicas, silicates, precipitated silica, colloidal silica, silica gels, de-aluminated zeolites such as de-aluminated zeolite Y, and silicon hydroxides and alkoxides. Silica sources that result in a high relative yield are preferred. Typical alumina sources are also generally known and include aluminates, alumina, other zeolites, aluminum colloids, boehmites, pseudoboehmites, aluminum hydroxides, aluminum salts such as aluminum sulfate and alumina chloride, aluminum hydroxides and alkoxides, alumina gels.
    [0026] When a first CHA SDA, a transition metal-amine complex is used. Suitable transition metals include those that are known for use in the SCR promotion of NOx compounds in exhaust gases, with Cu and Fe being preferred and Cu being particularly preferred. Suitable amine components for the metal-amine complex include organic amines and polyamines which are capable of directing CHA backbone formation. A preferred amine component is tetraethylenepentamine (TEPA). The metal-amine complex (ie Cu-TEPA) can be preformed or formed IN SITU in the synthetic mixture from the individual metal and amine components.
    [0027] A second CHA backbone shaping agent, other than the copper-amine complex noted above, is selected to drive CHA synthesis. Suitable second organic molding agents include those having the general formula: [R1R2R3N—R4]+Q- wherein R1 and R2 are independently selected from alkyl hydrocarbyl groups and hydroxy substituted hydrocarbyl groups having 1 to 3 carbon atoms, provided that R1 and R2 can be joined to form a nitrogen-containing heterocyclic structure, R3 is an alkyl group having 2 to 4 carbon atoms and R4 is selected from a 4 to 8 membered cycloalkyl group, optionally substituted by 1 to 3 groups alkyl, each having 1 to 3 carbon atoms and a 4- to 8-membered heterocycle group having 1 to 3 heteroatoms, said heterocycle group being optionally substituted by 1 to 3 alkyl groups, each having 1 to 3 atoms of carbon and the or each heteroatom in said heterocyclic group being selected from the group consisting of O, N and S or R3 and R4 are hydrocarbyl groups having 1 to 3 carbon atoms joined to form a containing heterocycle structure. of nitrogen and Q- is an anion. Suitable structure targeting agents include N,N,N-dimethylethylcyclohexylammonium (DMECHA), N,N,N-methyldiethylcyclohexylammonium and N,N,N-triethylcyclohexylammonium cations. Other suitable SDAs include benzyltrimethylammonium, tetramethylammonium and 1-adamantyltrimethylammonium (TMAda) and N,N,N-triethylcyclohexylammonium cations. In certain modalities, the second SDA is DMECHA.
    [0028] The second organic model is in the form of a cation and preferably is associated with an anion that is not harmful to the formation of the zeolite. Representative anions include halogen, for example, fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate and others. Hydroxide is the most preferred ion, particularly with respect to DMECHA. In certain embodiments, the reaction mixture and subsequent zeolite are free or essentially free of fluorine.
    [0029] The synthesis of a pot is conducted by the predetermined combination of relative amounts of a silica source, alumina source, transition metal-amine complex, the second organic shaping agent and optionally a source of hydroxide ions, such as such as NaOH and seed crystals, such as CHA zeolite, under various mixing and heating regimes as will be readily apparent to those skilled in the art. JMZ-3 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. TABLE 1

    [0030] Reaction temperatures, mixing times and rates, and other pressure parameters that are suitable for conventional CHA synthesis techniques are also generally suitable for the present invention. Without limitation, the following synthesis steps can be followed to synthesize JMZ-3. An alumina source (eg Al(OEt)3) is combined with an organic shaping agent (eg DMECHA) in water and optionally an alkali hydroxide and mixed by stirring for several minutes (eg approx. 5 to 30). A source of silica (eg SiO2) is added and mixed for several minutes (eg about 30 to 120 minutes) until a homogeneous mixture is formed. Then seed crystals (eg chabazite), a copper source (eg copper sulphate) and TEPA are added to the mixture and mixed by stirring for several minutes (eg 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.
    [0031] In the preferred synthesis methods, CHA seed crystals are added to the reaction mixture. It has been unexpectedly found that adding a small amount of seed crystals, for example, less than about 1 percent by weight, such as about 0.01 to about 1, about 0.05 to about 0.5 or about 0.01 to about 0.1 percent by weight, based on the total weight of the silica in the reaction mixture.
    [0032] 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 (eg 75 to 150°C) for several hours (eg about 4 to 24 hours). The drying step can be carried out under vacuum or at atmospheric pressure.
    The dried JMZ-2 crystals are preferably calcined, but can also be used without calcining.
    [0034] It will be estimated that the preceding sequence of steps, as well as each of the aforementioned periods of time and temperature values are merely exemplary and may be varied.
    [0035] 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 herein mean that the alkali metal is not added to the synthesis mixture as an intended ingredient. An "essentially alkali free" or "alkali free" catalyst as referred to herein generally means that the catalyst material contains an irrelevant level of alkali metal with respect to the intended catalytic cavity. In certain embodiments, the JMZ-2 zeolite contains less than about 0.1 percent by weight, and preferably less than about 0.01 percent by weight, alkali metal such as sodium or potassium.
    [0036] It has also been found that the one 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 addressed 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 load on the material. In certain embodiments, the synthesized zeolite contains from about 0.01 to about 5 percent by weight of copper, iron or a combination thereof, for example about 0.1% by weight to about 5% by weight, from about from 0.1 to about 3% by weight, from about 0.5 to about 1.5% by weight, about 0.1% by weight to about 1% by weight and about 1% by weight to about 3% by weight, For example, a Cu charge controlled from 0.3 to 5% by weight, from 0.5 to 1.5% by weight or from 0.5 to 1.0% by weight, for example, they can be achieved without additional post-synthesis process. In certain embodiments, the zeolite is free of post-synthesis exchanged metal, including copper and iron.
    [0037] The transition metal is catalytically active and substantially uniformly dispersed within the CHA backbone. 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 herein 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-3 zeolite. For example, JMZ-3 zeolite contains no more than about 5 percent by weight, no more than about 3 percent by weight, no more than about 1 percent by weight, 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. Preferably, transition metals are not introduced into the reaction mixture as a metal oxide and are not present in the synthesized zeolite crystal as a metal oxide. Minimizing the CuO concentration has been observed to improve the hydrothermal durability and exhaust gas treatment performance of the JMZ-3 zeolite.
    [0038] Preferably, the JMZ-3 zeolite contains a majority of transition metal IN SITU compared to the metal free of transition oxides. In certain embodiments, the JMZ-3 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.
    [0039] Preferably, the JMZ-3 zeolite does not contain main chain transition metals in an estimable amount. Instead, copper and iron are present as an ionic species within the channels and interior cavities of the zeolite main chain. Consequently, the metal-containing JMZ-3 zeolite is not a metal-substituted zeolite (eg, a zeolite having a substituted metal in a main-chain structure) and not necessarily a metal-exchanged zeolite (eg, a zeolite that has gone through a post-synthesis ion exchange). In certain embodiments, the JMZ-3 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, the JMZ-3 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, indium, platinum, iridium and/or rhenium. In certain embodiments, the JMZ-3 zeolite is free or essentially free of iron. In certain embodiments, the JMZ-3 zeolite is free or essentially free of calcium. In certain embodiments, the JMZ-3 zeolite is free or essentially free of cerium.
    [0040] The JMZ-3 zeolite is useful as a catalyst in certain applications. The JMZ-3 catalyst can be used without a post-synthesis metal exchange. However, in certain modalities, the JMZ-3 may undergo post-synthesis metal exchange. Thus, in certain embodiments, a catalyst is provided which comprises a JMZ-3 zeolite containing one or more catalytic metals exchanged in the channels and/or cavities of the zeolite post-synthesis zeolite in addition to copper IN SITU or iron IN SITU. Examples of metals that can be exchanged or impregnated with 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 lanthanum, cerium, praseodymium, neodymium, europium, terbium, erbium, ytterbium and yttrium. 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 incorporated metals can be added to the molecular sieve by any known technique, such as ion exchange, impregnation, isomorphic substitution, etc. The amount of post-synthesis metal exchanged can be from about 0.1 to about 3 percent by weight, for example about 0.1 to about 1 percent by weight, based on the total weight of the zeolite.
    [0041] In certain embodiments, the metal-containing zeolite contains post-synthesis exchanged alkaline earth metal, particularly calcium and/or magnesium, disposed within the channels and/or cavities of the zeolite backbone. In this way, the metal-containing zeolite of the present invention may have transition metals (TM), such as copper or iron, incorporated into the zeolite channels and/or cavities and have one or more exchanged alkaline earth metals (AM), such as calcium or potassium, incorporated post-synthesis. The alkaline earth metal can be present in an amount relative 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 alkali and/or alkaline earth (AM) metal is present in the zeolite material in an amount relative to the amount of aluminum in the zeolite, i.e. the aluminum in the chain. main. As used herein, the ratio (TM+AM):A1 is based on the relative molar amounts of TM + AM to the molar backbone Al in the corresponding zeolite. In certain embodiments, the catalyst material has a (TM+AM):A1 ratio 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.
    [0042] In certain embodiments, Ce is impregnated post-synthesis in JMZ-3, for example by adding Ce nitrate to a copper-promoted zeolite through a conventional incipient moisture technique. Preferably, the concentration of cerium in the catalyst material is present at a concentration of at least about 1 percent by weight, based on the total weight of the zeolite. Examples of preferred concentrations include at least about 2.5 percent by weight, at least about 5 percent by weight, at least about 8 percent by weight, at least about 10 percent by weight, about 1.35 to about 13.5 percent by weight, about 2.7 to about 13.5 percent by weight, about 2.7 to about 8.1 percent by weight, about 2 to about 4 percent by weight, about 2 to about 9.5 percent by weight, and about 5 to about 9.5 percent by weight, based on the total weight of the zeolite. In certain embodiments, the concentration of cerium in the catalyst material is from about 50 to about 550 g/ft3 . Other ranges of Ce include: above 100 g/ft3, above 200 g/ft3, above 300 T/A-3 rno³/100 T/A-3 QPirno z~1 rz* rr/A-3/4Í g/ft, above 400 g/ft, above 500 g/ft, from about /5 to about 350 g/ft3, from about 100 to about 300 g/ft3 and from about 100 to about 250 g/ft3.
    [0043] For embodiments where the catalyst is part of a coating composition, the coating may additionally comprise binder containing Ce or ceria. For such embodiments, the Ce containing particles in the binder are significantly larger than the Ce containing particles in the catalyst.
    [0044] It was further observed that the one pot synthesis procedure allows to adjust the SAR of the catalyst based on the composition of the starting synthesis mixture. SARs of 25 - 150, 25 - 50, 50 - 100, 30 - 50, 30 - 40, and 25 - 35, for example, can be selectively achieved based on the composition of the starting synthesis mixture and/or adjustment of others 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 appreciated that it can be extremely difficult to directly measure the SAR of the zeolite after it is combined with a binding material. Consequently, SAR was expressed earlier in the term of the SAR of the precursor zeolite, that is, the zeolite used to prepare the catalyst, as measured prior to combining this zeolite with the other catalyst components.
    [0045] The process of synthesizing a preceding pot can result in zeolite crystals of uniform size and shape with relatively low amounts of agglomeration. Furthermore, the synthesis procedure can result in zeolite crystals having an average crystalline size of from 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 ground using a jet mill or other particle-to-particle grinding technique to an average size of about 1.0 to about 1.5 microns to facilitate coating of a paste containing the catalyst to a substrate, such as a monolith through the flow.
    [0046] The crystal size is the length of an edge of a face of the crystal. Direct measurement of crystal size can be performed using microscopy methods such as SEM and TEM. Other techniques for determining average particle size such as laser diffraction and scattering can also be used. In addition to the average crystal size, catalyst compositions preferably have a majority of crystal sizes that are greater than about 0.1 µm, preferably between about 0.5 and about 5 µm, such as about 0.5 to 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.
    [0047] The catalysts of the present invention are particularly applicable for heterogeneous catalytic reaction systems (ie, sodium catalysts in contact with a gas reagent). To improve contact surface area, mechanical stability and/or fluid flow characteristics, catalysts can be disposed 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 a block of alveolar cordierite. Alternatively, the catalyst is kneaded together with other components, such as fillers, binders and reinforcing agents, into an extrudable paste which is then extruded through a die to form a honeycomb block. Accordingly, in certain embodiments, a catalyst article is provided which comprises a JMZ-3 catalyst described herein coated on and/or incorporated into a substrate.
    [0048] Certain aspects of the invention provide a catalytic coating. The coating comprising the JMZ-3 catalyst described herein 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 of these.
    [0049] A coating can also include non-catalytic components such as fillers, binders, stabilizers, rheology modifiers and other additives including one or more of alumina, silica, silica alumina other than zeolite, titania, zirconia, ceria. In certain embodiments, the catalyst composition can comprise pore forming agents such as graphite, cellulose, starch, polyacrylate and polyethylene and others. These additional components do not necessarily catalyze the desired reaction, but rather improve the effectiveness of the catalytic material, for example, by increasing its temperature range, increasing catalyst contact surface area, increasing catalyst adhesion to a substrate, etc. in preferred embodiments, the coating loading 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 at 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.
    [0050] Two of the most common substrate designs are board and honeycomb. Preferred substrates, particularly for mobile applications include through-flow monoliths having a so-called honeycomb geometry comprising multiple adjacent parallel channels that are open at both ends and generally extend from the input face of the substrate and result in a high surface area to volume ratio. For certain applications, the monolith through alveolar 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 certain other applications, the monolith through 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 alveolar monoliths are porous. In addition to cordierite, silicon carbide, silicon nitride, ceramic and metal, other materials that can be used for the substrate include aluminum nitride, silicon nitride, aluminum titanate, α-alumina, mullite, eg acicular mullite, polucite, a thermet such as AFOsZFe, AFCF/Ni or B4CZFe or composites comprising segments of any two or more of these. Preferred materials include cordierite, silicon carbide and alumina titanate.
    [0051] Plate type catalysts have lower pressure drops and are less susceptible to clogging or fouling than honeycomb 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 clogs more easily. In certain embodiments the plate substrate is constructed of metal, preferably corrugated metal.
    [0052] In certain embodiments, the invention is a catalyst article made by a process described herein. In a particular embodiment, the catalyst article is produced by a process that includes the steps of applying a JMZ-3 catalyst composition, preferably as a coating, to a substrate 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 catalyst layers on the substrate, including the JMZ-3 catalyst layer, are arranged in consecutive layers. As used herein, 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 disposed one on top of the other on the substrate.
    [0053] In certain embodiments, the JMZ-3 catalyst is disposed on the substrate as a first layer and another composition, such as an oxidation catalyst, reduction catalyst, decontaminant component or NOx storage component, is disposed on the substrate as a second layer. In other embodiments, the JMZ-3 catalyst is disposed on the substrate as a second layer and another composition, such as an oxidation catalyst, reduction catalyst, decontaminant component, or NOx storage component, is disposed on the substrate as a first layer. As used herein 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, exhaust gas penetrates (and therefore contacts) the first layer before contacting the second layer and subsequently returns through the first layer to exit the catalyst component. In other embodiments, the first layer is a first region disposed in an upstream portion of the substrate and the second layer is disposed on the substrate as a second region, wherein the second region is downstream of the first.
    [0054] In another embodiment, the catalyst article is produced by a process that includes the steps of applying a JMZ-3 catalyst composition, preferably as a coating, to a substrate as a first zone and subsequently applying at least one composition further for treating an exhaust gas to the substrate as a second zone, wherein at least a portion of the first zone is downstream of the second zone. Alternatively, the JMZ-3 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 additional compositions include oxidation catalysts, reduction catalysts, decontaminant components (eg, sulfur, water, etc.), or NOx storage components.
    [0055] To reduce the amount of space required by an exhaust system, individual exhaust components in certain embodiments are indicated to perform more than one function. For example, applying an SCR catalyst to a substrate wall flow filter rather than a substrate through the flow serves to reduce the overall size of an exhaust treatment system that allows one substrate to serve two functions, i.e., catalytically reducing the NOx concentration in the exhaust gas and mechanically removing the soot from the exhaust gas. Consequently, in certain embodiments, the substrate is a honeycomb wall flow filter or partial filter. Wall flow filters are similar to alveolar substrates through flow in that they contain a plurality of adjacent, parallel channels. However, the alveolar substrate channels through the flow are open at both ends, whereas the wall flow substrate channels have a capped end, where capping occurs at opposite ends of adjacent channels in an alternating pattern. Covering the alternating ends of the channels prevents gas from entering the substrate inlet face from direct flow through the channel and existing. Instead the exhaust gas enters the front of the substrate and travels around the half of the channels where it is forced through the channel walls before the entry of the second half of the channels and exits on the rear face of the substrate.
    [0056] The substrate wall has a porosity and pore size that is permeable to gas, but traps a larger portion of the particulate substance, such as soot, from the gas as the gas passes through the wall. Preferred wall flux substrates are high efficiency filters. Wall flow filters for use with 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 is relative to soot and other similarly sized particles and to particulate concentrations typically seen in conventional diesel exhaust gas. For example, particulates in diesel exhaust can range 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.
    [0057] Porosity is a measure of the percentage of empty space in a porous substrate and is related to the backpressure in an exhaust system: generally, the smaller the porosity, the greater the backpressure. 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%.
    [0058] Pore interconnectivity, measured as a percentage of the total substrate void volume is the degree to which pores, voids and/or channels are joined to form continuous paths through a porous substrate, i.e., the face of enter the exit face. In contrast, pore interconnectivity is the sum of closed pore volume and pore volume that has a conduit on only one surface of the substrate. Preferably, the porous substrate has a pore volume interconnectivity of at least about 30%, more preferably at least about 40%.
    [0059] The average pore size of the porous substrate is also important for filtration. Average pore size can be determined by any acceptable means, including mercury porosimetry. The average pore size of the porous substrate must be of a sufficiently large value to promote low back pressure, while providing adequate efficiency by the substrate itself, by promoting a soot cake layer on the substrate surface, 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.
    [0060] In general, the production of an extruded solid body containing the JMZ-3 catalyst involves the combination of the JMZ-3 catalyst, a binder, a compound that enhances the optional organic viscosity into a homogeneous paste which is then added to a binder/matrix component or a precursor thereof and optionally one or more of stabilized ceria and inorganic fibers. The blend is compacted in a mixture or mechanism or an extruder. The blends have organic additives such as binders, pore builders, plasticizers, surfactants, lubricants, dispersants as processing aids to enhance 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 calcinations of the extruded solid body. A JMZ-3 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.
    [0061] Extruded solid bodies containing the JMZ-3 catalysts according to the present invention generally comprise a unitary structure in the form of a honeycomb 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 outer "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 square, triangular, hexagonal, circular, etc. 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 blocked channels at the first upstream end resembles a checkerboard with a similar arrangement of the ends of blocked channels and downstream.
    [0062] The binder/matrix component is preferably selected from the group consisting of cordierite, nitrides, carbides, borides, intermetallics, lithium aluminum silicate, a spinel, an optionally contaminated alumina, a source of silica, titania, zirconia, titania- zirconia, zirconium and mixtures of any two or more of these. The slurry may optionally contain inorganic fiber reinforcement 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.
    The aluminum matrix/binder component is preferably gamma alumina, but can be any other transitional alumina, i.e. alpha alumina, beta alumina, chi alumina, eta alumina, rho alumina, cap alumina, theta alumina, delta alumina, lanthanum beta alumina and mixtures of any two or more such transitional aluminas. It is preferred that the alumina is contaminated with at least one non-aluminium 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.
    [0064] 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 methylphenyl silicone resin, a clay, talc or a mixture of any two or more of these. From this list, the silica can be SiO2 such as, feldspar, mullite, silica-alumina, silica-magnesia, silica-zirconia, silica-toria, silica-beryl, silica-titanium dioxide, silica-alumina-ternary zirconia, silica- ternary alumina-magnesia, ternary silica-magnesia-zirconia, ternary alumina-silica, and mixtures of any two or more of these.
    [0065] Preferably, the JMZ-3 catalyst is dispersed everywhere, and preferably exactly everywhere, the entire extruded catalyst body.
    [0066] Where any of the above extruded solids are made into a wall flow filter, the wall flow filter porosity may be 30-80%, such as 40-70%. Porosity and pore volume and pore radius can be measured, for example, using mercury intrusion porosity.
    [0067] The JMZ-3 catalyst described here can promote the reaction of a reductant, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N2) and water (H2O). Thus, in one embodiment, the catalyst can be formulated to favor the reduction of nitrogen oxides with a reducer (ie, an SCR catalyst). Examples of such reductants include hydrocarbons (eg C3 - C6 hydrocarbons) and nitrogen reductants such as ammonia and ammonia hydrazine or any suitable ammonia precursor such as urea ((NH2)2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.
    [0068] The JMZ-3 catalyst described here can also promote the oxidation of ammonia. Thus, in another embodiment, the catalyst can be formulated to favor the oxidation of ammonia with oxygen, particularly at the ammonia concentrations typically found downstream of an SCR catalyst (eg, ammonia oxidation catalyst (AMOX) such as an ammonia slip catalyst (ASC)). In certain embodiments, the JMZ-3 catalyst is disposed on an upper layer in an oxidative sublayer, wherein the sublayer comprises a platinum group metal (PGM) catalyst or a non-PGM catalyst. Preferably, the catalyst component in the sublayer is disposed on a surface area support including, but not limited to, alumina.
    [0069] In yet another modality, the SCR and AMOX operations are performed in series, in which both processes use a catalyst comprising the JMZ-3 catalyst described herein and in which an SCR process occurs upstream of the AMOX process. For example, an SCR catalyst formulation may be disposed on the inlet side of a filter and an AMOX catalyst formulation may be disposed on the exit side of the filter.
    [0070] Consequently, there is provided a method for the reduction of NOx compounds or oxidation of NH3 in a gas, which comprises contacting the gas with a catalyst composition described herein for the catalytic reduction of NOx compounds for a sufficient period 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 nitrogenous reductant that is not consumed by the selective catalytic reduction process. For example, in certain embodiments, an ammonia slip catalyst is disposed on the outlet side of a wall flow filter and an SCR catalyst is disposed 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 stream and an SCR catalyst is disposed at the upstream end of the substrate through the stream. 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 as long as the SCR catalyst block is disposed upstream of the sliding catalyst block. ammonia.
    [0071] In certain embodiments, 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 from 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. Modalities using temperatures greater than 450°C are particularly useful for treating exhaust gases from a heavy and light duty 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, wherein the zeolite catalyst for use in the present invention is located downstream of the filter.
    [0072] According to another aspect of the invention, there is provided a method for the reduction of NOX Compounds and/or oxidation of NH3 in a gas, which comprises contacting the gas with a catalyst described herein for a period sufficient to reduce the level of NOX compounds in the gas. The methods of the present invention may comprise one or more of the following steps: (a) accumulation and/or burning of soot that is in contact with the inlet of a catalyst filter; (b) introducing a nitrogen reducing agent into the exhaust gas stream prior to contacting the catalytic filter, preferably with no intervention from the catalytic steps involving the NOx treatment and the reducer; (c) generating NH3 in a deficient NOx scavenger or NOx siphon catalyst and preferably using such NH3 as a reductant 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 oxidize NO to NO2, which in turn can be used to oxidize particulate substance in the particulate filter; and/or reduce the particulate substance (PM) in the exhaust gas; (e) contacting an exhaust gas with one or more SCR catalyst devices by flowing in the presence of a reducing agent to reduce the NOx concentration in the exhaust gas; and (f) contacting an exhaust gas with an exhaust catalyst. ammonia slip, 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 through a recirculation arc prior to the exhaust gas inlet/reentry. exhaust in the engine.
    [0073] 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 absorbing catalyst (NAC), a NOX deficient siphon (LNT) , a NOx storage/reduction (NSRC) catalyst disposed upstream of the SCR catalyst, e.g., an SCR catalyst of the present invention disposed in a wall flow filter. NAC components useful in the present invention include a combination of a base material (such as an alkali metal, alkaline earth metal or rare earth metal, including alkali metal oxides, alkaline earth metal oxides and combinations thereof) and a precious metal (such as platinum) and optionally a component of the reduction catalyst such as rhodium. Specific types of base 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 an average concentration which can be from about 40 to about 100 grams/ft 3 .
    [0074] Under certain conditions, during the periodically rich regeneration events, NH3 can be generated in a NOx-absorbing catalyst. The SCR catalyst downstream of the NOx-absorbing catalyst can improve the NOx reduction efficiency of the total system. In the combined system, the SCR catalyst is capable of storing the NH3 released from the NAC catalyst during rich regeneration events and utilizes the stored NH3 to selectively reduce some or all of the NOx that slips through the NAC catalyst during poor operating conditions normal.
    [0075] The method for treating exhaust gas as described here can be performed on an exhaust gas derived from a combustion process, such as from an internal combustion engine (whether mobile or stationary), 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, chemical processing industry, coke ovens, municipal waste plants and incinerators, etc. In a particular embodiment, the method is used to treat exhaust gas from a poorly burning vehicular internal combustion engine, such as a diesel engine, a poorly burning gasoline engine or an engine powered by petroleum gas. liquid or natural gas.
    [0076] In certain aspects, the invention is a system for treating exhaust gas generated by the combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine, coal-fired power plants or oil and others. Such systems include a catalytic article comprising the JMZ-3 catalyst described herein and at least one additional component for treating exhaust gas, wherein the catalytic article and at least one additional component are designed to function as a coherent unit.
    [0077] In certain embodiments, the system comprises a catalytic article comprising a JMZ-3 catalyst described herein, a conduit for directing a flow of exhaust gas, a source of nitrogenous reducer disposed upstream of the catalytic article. The system may include a controller to measure nitrogen reductant in the exhaust gas flow only when it is determined that the zeolite catalyst is capable of catalyzing the NOx reduction at or above a desired efficiency, such as above 100°C , above 150°C or above 175°C. The nitrogen reductant measurement can be arranged such that 60% to 200% of the theoretical ammonia is present in the exhaust gas entering the SCR catalyst calculated at 1:1 NH3/NO and 4:3 NH3/NO2.
    [0078] In another embodiment, the system comprises an oxidation catalyst (e.g., 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 nitrogenous reducer in the exhaust gas. In one embodiment, the oxidation catalyst is adapted to produce a gas stream that has an SCR zeolite catalyst having a NO to NO2 ratio of from about 4:1 to about 1:3 by volume, for example, in a exhaust gas temperature at the inlet of the oxidation catalyst from 250°C to 450°C. The oxidation catalyst can include at least one platinum group metal (or some combinations thereof), such as platinum, palladium or rhodium, coated onto a monolith substrate through the flow. 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, silica alumina other than zeolite, ceria, zirconia, titanium dioxide or an oxide mixed or composite containing both ceria and zirconia.
    [0079] In a further embodiment, a suitable filter substrate is located between the oxidation catalyst and the SCR catalyst. 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 measuring point of the nitrogen reductant is located between the filter and the zeolite catalyst. Alternatively, if the filter is not catalyzed, the means for measuring the nitrogen reductant can be located between the oxidation catalyst and the filter. EXAMPLES Example 1: Synthesis of JMZ-3 Zeolite Using the One Pot Mixed Model Process
    [0080] The catalysts obtained by the model mixed pot synthesis procedure described here demonstrate the significantly improved attributes compared to those obtained by the simple model synthesis.
    [0081] Here, the alkali hydroxide (NaOH) is combined with an organic styling agent (DMECHA) in water and mixed for approximately 5 minutes. An aluminum source (Al(OEt)3) is added to the mixture and mixed for approximately 5 minutes. A source of silica (SiO2) is added to the mixture and mixed until a homogeneous mixture is formed. Then seeds (eg CHA zeolite), a Cu source and TEPA are added to the mixture and blended for approximately 30 minutes. The resulting mixture is heated at 160°C for about two days. At the conclusion of the heating period, solids are collected by vacuum filtration, rinsed with deionized water, and dried at approximately 100°C overnight. The resulting molecular sieve catalyst material is calcined at around 560°C for approximately 8 hours. Example 2: Synthesis of Sodium Free JMZ-3 Zeolite Using the One Pot Mixed Model Process
    [0082] A sodium-free synthesis pathway can be achieved by modifying the model ratios and the model ratio for total silica. Sodium free JMZ-3 was prepared using the general steps in Example 1, but using the synthesis mixture shown in Table 2. Table 1. Molar composition of starting synthesis mixture.

    [0083] Sodium-free JMZ-3 showed better total NOx conversion after hydrothermal aging comparing JMZ-3 with sodium (see Figure 1).
    [0084] While the present invention has been described in connection with various illustrative embodiments thereof, it is to be understood that those embodiments are not to be used as a pretext to limit the scope of protection afforded by the true scope and spirit of the appended claims.
    权利要求:
    Claims (17)
    [0001]
    1. Catalyst composition, characterized in that it comprises a synthetic copper-containing JMZ-3 zeolite having a CHA backbone structure, a silica to alumina SAR molar ratio of 25 to 150, and a unit cell volume in the range from 2355 to 2375 Â3.
    [0002]
    2. Composition according to claim 1, characterized in that it further comprises iron.
    [0003]
    3. Composition according to any one of claims 1 or 2, characterized in that the zeolite has a phase purity of at least 95% by weight as determined by Rietveld analysis (XRD).
    [0004]
    4. Composition according to any one of claims 1 to 3, characterized in that the zeolite contains at most 5 percent by weight of copper in the form of copper oxide in relation to the total amount of copper in the zeolite.
    [0005]
    5. Composition according to any one of claims 1 to 4, characterized in that the zeolite contains from 0.05 to 5 percent by weight of copper.
    [0006]
    6. Composition according to any one of claims 1 to 5, characterized in that the zeolite contains uniformly distributed ionic copper.
    [0007]
    7. Composition according to any one of claims 1 to 6, characterized in that the zeolite contains less than 5 percent by weight of CuO based on the total weight of the zeolite.
    [0008]
    8. Composition according to claim 1, characterized in that the catalyst is sodium free.
    [0009]
    9. Composition according to any one of claims 1 to 8, characterized in that the zeolite comprises from 0.1 to 5 percent by weight of copper off the main chain based on the total weight of the zeolite, the zeolite has a phase purity of at least 95% by weight and contains less than 5 weight percent CuO based on the total weight of the zeolite.
    [0010]
    10. Composition according to claim 9, characterized in that the zeolite is free of copper exchanged in the post-synthesis.
    [0011]
    11. Method for synthesizing a catalyst composition defined according to any one of claims 1 to 10, characterized in that it comprises: preparing a reaction mixture comprising (a) at least one source of alumina, (b) at least a silica source, (c) first organic shaping agent comprising a copper-amine, (d) seed crystals, and (e) second organic shaping agent, wherein the second organic shaping agent is distinct from the first organic shaping agent. organic modeling, where each of the first and second molding agents is suitable to form a CHA backbone structure and where the reaction mixture is essentially fluorine-free; and heating the reaction mixture under crystallization conditions for a time sufficient to form zeolite crystals having a CHA backbone having a SAR of at least 25 and containing copper.
    [0012]
    12. The method of claim 11, characterized in that the second shaping agent has a general formula: [R1R2R3N—R4]Q- where: R1 and R2 are independently selected from hydrocarbyl alkyl groups and substituted hydrocarbyl groups by hydroxy having 1 to 3 carbon atoms, provided that R1 and R2 can be joined to form a nitrogen-containing heterocyclic structure, R3 is an alkyl group having 2 to 4 carbon atoms, and R4 is selected from a 4-cycloalkyl group to 8-membered, optionally substituted by 1 to 3 alkyl groups, each having 1 to 3 carbon atoms and a 4 to 8-membered heterocycle group having 1 to 3 heteroatoms, the heterocycle group being optionally substituted by 1 to 3 groups alkyl, each having 1 to 3 carbon atoms and the or each heteroatom in the heterocyclic group being selected from the group consisting of O, N and S, or R3and R4 are hydrocarbyl groups having 1 to 3 carbon atoms joined to form one is breakdown of nitrogen-containing heterocycle, and Q- is an anion.
    [0013]
    13. Method according to claim 11, characterized in that the second organic shaping agent is formed IN SITU in the reaction mixture from individual metal and amine components.
    [0014]
    14. Method according to claim 11, characterized in that the first organic shaping agent is Cu-TEPA.
    [0015]
    15. Method according to claim 13, characterized in that the second organic modeling agent is DMECHA.
    [0016]
    16. Catalyst article for treating exhaust gas, characterized in that it comprises a catalyst composition as defined in any one of claims 1 to 10 disposed in and/or within an alveolar monolith substrate.
    [0017]
    17. A 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 16 to selectively reduce at least a portion of the 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
    CN109317190B|2022-01-07|
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    CN109317190A|2019-02-12|
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    KR20160093680A|2016-08-08|
    US11207666B2|2021-12-28|
    GB201421362D0|2015-01-14|
    GB201421333D0|2015-01-14|
    RU2703462C1|2019-10-17|
    EP3077108A1|2016-10-12|
    JP2017504558A|2017-02-09|
    EP3077108B1|2020-09-02|
    CN105980052B|2019-12-06|
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    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| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| 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
    US201361910621P| true| 2013-12-02|2013-12-02|
    US61/910,621|2013-12-02|
    PCT/US2014/068110|WO2015084817A1|2013-12-02|2014-12-02|Mixed template synthesis of high silica cu-cha|
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