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    • 专利摘要:
    catalyst composition, catalytically active reactive coating, and method for reducing nox in an exhaust gas is provided a catalyst comprising (a) a zeolitic material having an average crystal size of at least about 0.5 micro m, having a silicon and aluminum containing tea matrix having a silica to alumina (sar) molar ratio of from about 10 to about 25; and (b) an extra-matrix promoter metal (m) disposed in the zeolitic material as free and / or exchanged metal, wherein the extra-matrix promoter metal is copper, iron, and mixtures thereof, and is present in an atomic ratio. from promoter metal to aluminum (m: al) from about 0.10 to about 0.24 based on matrix aluminum; and optionally comprising (c) at least about 1 weight percent cerium in the zeolitic material, based on the total weight of the zeolite, wherein cerium is present in a selected form of exchanged cerium ions, monomeric ceria, oligomeric ceria, and combinations thereof as long as the oligomeric aria has a particle size of less than 5 micro m.
    公开号:BR112013013711B1
    申请号:R112013013711-8
    申请日:2011-12-02
    公开日:2019-04-24
    发明作者:Todd Howard Ballinger；Philip Gerald Blakeman；Guy Richard Chandler；Hai-Ying Chen；Julian P. Cóx；Joseph M. Fedeyko；Alexander Nicholas Michael Green；Paul Richard Philips；Erich C. Weigert；James Alexander Wylie；Stuart David Reid
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    “CATALYST COMPOSITION, CATALYTICALLY ACTIVE REACTIVE COATING, AND, METHOD TO REDUCE NOx IN AN EXHAUST GAS”
    FUNDAMENTALS
    A) Field of Use [0001] The present invention relates to catalysts, systems, and methods that are useful for treating an exhaust gas that occurs as a result of the combustion of hydrocarbon fuel, and particularly an exhaust gas containing oxides of nitrogen, such as an exhaust gas produced by diesel engines.
    B) Description of Related Art [0002] The larger portions of most combustion exhaust gases contain relatively benign nitrogen (N2), water vapor (H2O), and carbon dioxide (CO2); but the exhaust gas also contains in relatively small parts, harmful and / or toxic substances, such as incomplete combustion carbon monoxide (CO), unburned fuel hydrocarbons (HC), combustion temperature nitrogen oxides (NOx) excessive, and particulate matter (mainly soot). To mitigate the environmental impact of the exhaust gas released to the atmosphere, it is desirable to eliminate or reduce the amount of these undesirable components, preferably by a process that, in turn, does not generate other harmful or toxic substances.
    [0003] One of the most difficult components to remove from a vehicle exhaust gas is NOx, which includes nitric oxide (NO), nitrogen dioxide (NO2), and nitrous oxide (N2O). The reduction of NOx to N2 in a low-burning exhaust gas, such as that created by diesel engines, is particularly problematic because the exhaust gas contains enough oxygen to favor oxidative reactions rather than reduction. NOx can be reduced in a diesel exhaust gas, however, by a process
    Petition 870190008230, of 01/25/2019, p. 9/48 / 27 commonly known as Selective Catalytic Reduction (SCR). An SCR process involves the conversion of NOx, in the presence of a catalyst and with the aid of a reducing agent, to elemental nitrogen (N2) and water. In an SCR process, a gaseous reducer such as ammonia is added to an exhaust gas stream before contacting the exhaust gas with the SCR catalyst. The reducer is absorbed into the catalyst and the NO,. · Reduction reaction occurs as gases pass through or over the catalyzed substrate. The chemical equation for stoichiometric SCR reactions using ammonia is:
    2NO + 4NH + 2O2 3N2 + 6H2O 2NO2 + 4NH3 + O2 3N2 + 6H2O NO + NO2 + 2NH3 2N2 + 3H2O.
    [0004] Known SCR catalysts include zeolites and other molecular sieves. Molecular sieves are microporous crystalline solids with well-defined structures and generally contain silicon, aluminum and oxygen in their structure and can also contain cations within their pores. A descriptive feature of a molecular sieve is its crystalline or pseudocrystalline structure, which is formed by tetrahedral molecular cells interconnected in a regular and / or repeated manner to form a structure. The unique molecular sieve structures recognized by the International Zeolite Association (IZA) Structure Commission are named with a three letter code to indicate the type of structure. Examples of molecular sieve structures that are known SCR catalysts include the Structure Type Codes CHA (chabazite), BEA (beta), and MOR (mordenite).
    [0005] Some molecular sieves have a three-dimensional molecular structure that originates from the orientation of their interconnected cells. The cells of these molecular sieves typically have volumes in the order of a few cubic nanometers and cell openings (also referred to as “pores” or “openings”) in the order of a few
    Petition 870190008230, of 01/25/2019, p. 10/48 / 27 angstroms in diameter. The cells can be defined by the size of the ring of their pores, where, for example, the term “8-ring” refers to a closed loop that is formed from 8 silicon atoms coordinated in a tetrahedral manner (or aluminum) and 8 atoms of oxygen. In some zeolites, cell pores are aligned within the structure to create one or more channels that extend through the structure, thereby creating a mechanism to restrict the entry or passage of different molecular or ionic species through the molecular sieve, based on relative channel sizes and molecular or ionic species. The size and shape of the molecular sieves affect their catalytic activity, partly because they exert a steric influence on the reagents, controlling the access of reagents and products. For example, small molecules, such as NOx, can typically pass in and out of cells and / or can diffuse through the channels of a small-pore molecular sieve (i.e., those having a structure with a maximum ring size of eight tetrahedral atoms), whereas larger molecules, such as long-chain hydrocarbons, cannot. In addition, partial or total dehydration of a molecular sieve can result in a crystalline structure interlaced with channels of molecular dimensions.
    [0006] Molecular sieves having a small pore structure, i.e., containing a maximum ring size of 8, have been found to be particularly useful in SCR applications. Small pore molecular sieves include those having the following types of crystalline structure: CHA, LEV, ERI and AEI. Examples of aluminosilicates and silicoaluminophosphates specific to molecular sieves having the CHA structure include SAPO-34, AlPO-34, and SSZ-13.
    [0007] Zeolites are molecular sieves of aluminosilicate having a crystalline structure of interconnected alumina and silica, in particular, alumina and silica cross-linked through the sharing of atoms
    Petition 870190008230, of 01/25/2019, p. 11/48 / 27 of oxygen, and thus can be characterized by their ratio of silica to alumina (SAR). In general, as a zeolite SAR increases, the zeolite acquires more hydrothermal stability. Since the temperature of an exhaust gas coming out of a mobile low-burn engine, such as a diesel engine, is often 500 to 650 ° C or higher and typically contains water vapor, hydrothermal stability is a consideration important in the design of an SCR catalyst.
    [0008] While zeolites themselves often have catalytic properties, their SCR catalytic performance can be improved in some environments through a cation exchange in which a portion of ionic species that exist on the surface or within the structure is replaced by metal cations, such Cu 2+ . That is, the SCR performance of the zeolite can be promoted by loosely attaching one or more metal ions to the molecular sieve structure.
    [0009] It is also desirable for an SCR catalyst to have high catalytic activity at low operating temperatures. At low operating temperatures, for example, below 400 ° C, a higher metallic charge on a molecular sieve results in increased SCR activity. However, the metallic charge that can be obtained is often dependent on the number of exchange sites on the molecular sieve, which in turn is dependent on the SAR of the material. In general, molecular sieves with low SAR allow for higher metal charges, thus leading to a conflict between the need for high catalytic activity and high hydrothermal stability that is achieved by a relatively higher SAR value. In addition, high copper catalysts do not perform as well at high temperatures (for example,> 450 ° C). For example, loading an aluminosilicate having a CHA structure with large amounts of copper (ie, atomic copper-to-aluminum ratio of> 0.25) can result in significant NH 3 oxidation at temperatures above 450 ° C,
    Petition 870190008230, of 01/25/2019, p. 12/48 / 27 resulting in low selectivity for N2. This deficiency is particularly critical under filter regeneration conditions that involve exposing the catalyst to temperatures above 650 ° C.
    [00010] Another important consideration when designing an SCR catalyst for mobile application is the consistency of the catalyst's performance. For example, it is desirable for a fresh catalyst to produce a similar level of conversion of NOx to the same catalyst after it has aged. [00011] Therefore, there is still a need for SCR catalysts that offer improved performance over existing SCR materials.
    SUMMARY OF THE INVENTION [00012] It has been found that some zeolites having a crystalline chabazite (CHA) structure can be charged with relatively small amounts of promoter metal, such as copper, to provide good conversion at high temperatures, while still maintaining good selectivity for NO. More particularly, the present invention utilizes and / or incorporates the surprising finding that some large crystalline zeolites having a CHA structure and a relatively low SAR can be loaded with relatively low amounts of catalytically active metals and still provide good conversion of NOx to a wide temperature range while improving selectivity for N2 at high temperatures (for example> about 450 ° C). The synergistic effect between one or more of crystal size, copper exchange level, and SAR was previously unknown and unexpected.
    [00013] It has also been found that high concentrations of ceria can be incorporated into such metal-promoted zeolite to improve the hydrothermal stability of the material, catalytic performance at low temperature, and / or consistency in catalytic performance between the fresh and aged states of the catalyst . For example, some forms of
    Petition 870190008230, of 01/25/2019, p. 13/48 / 27 realization of the invention use the surprising verification that the addition of high concentrations of Ce to a low SAR CHE zeolite promoted with fully formulated copper improves the hydrothermal durability of the catalyst compared to the low SAR aluminosilicates promoted with metal similar, without Ce. It is also surprising that this improved performance is not seen when Ce is added to similar zeolite promoted by metals having a higher SAR or higher concentration of promoter metal.
    [00014] Therefore, an aspect of the present invention provides a catalyst composition comprising (a) a zeolitic material having a CHA structure containing silicon and aluminum and having a silica to alumina (SAR) molar ratio of about 10 to about 25, and preferably an average crystal size of at least about 0.5 pm; and (b) an extra-structural promoter metal (M) disposed in said zeolitic material as free and / or exchanged metal, in which the extra-structural promoter metal is selected from the group consisting of copper, iron, and mixtures thereof, and is present in an atomic ratio of promoter metal to aluminum (M: Al) of about 0.10 to about 0.24 based on the aluminum of the structure. In some embodiments, such a catalyst also comprises at least about 1 weight percent Ce, based on the total weight of the zeolite.
    [00015] In another aspect of the invention, a catalytically active reactive coating is provided which comprises (a) a metal-promoted zeolitic material having a CHA structure containing silicon and aluminum and having a silica to alumina molar ratio (SAR) of about 10 to about 25 and preferably having an average crystal size of at least about 0.5 µm; in which the zeolite is promoted with an extra-structural promoter metal (M) selected from the group consisting of copper, iron, and mixtures thereof, and in which the extra-structural promoter metal is present in an atomic ratio of promoter metal to aluminum (M: Al) of
    Petition 870190008230, of 01/25/2019, p. 14/48 / 27 about 0.10 to about 0.24 based on the aluminum of the structure; and (b) one or more stabilizers and / or binders, wherein the metal-promoted zeolite and one or more stabilizers and / or binders are present together in a slurry.
    [00016] In yet another aspect of the invention, a method is provided for reducing NOx in an exhaust gas which comprises (a) contacting an exhaust gas derived from a lean burning combustion process and containing NOx with a catalyst composition comprising (i) a zeolitic material having a CHA structure that contains silicon and aluminum and having a silica to alumina (SAR) molar ratio of about 10 to about 25 and preferably having an average crystal size of at least about 0 , 5 µm; and (ii) an extra-structural promoter metal (M) disposed in said zeolitic material as a free and / or exchanged metal, in which the extra-structural promoter metal is selected from the group consisting of copper, iron, and mixtures thereof, and is present in an atomic ratio of promoter metal to aluminum (M: Al) of about 0.10 to about 0.24 based on the aluminum of the structure; and (b) converting a portion of NOx to N2 and H2O.
    BRIEF DESCRIPTION OF THE FIGURES [00017] Figure 1 is a graphical representation of the data with respect to the NO X conversion capacity of (1) a Cu-SSZ-13 catalyst having low copper charge according to an embodiment of the invention and (2) a comparative material having a high copper load; and
    Figure 2 is a bar graph showing the NOx conversion data for various catalysts of the invention containing Ce and also comparative examples of other catalyst materials.
    DETAILED DESCRIPTION OF METHODS
    PREFERRED PROCEDURES OF THE INVENTION [00018] In a preferred embodiment, the invention is directed to a catalyst to improve ambient air quality,
    Petition 870190008230, of 01/25/2019, p. 15/48 / 27 particularly for improving exhaust gas emissions generated by diesel and other low-burn engines. Exhaust gas emissions are improved, at least in part, by reducing NOx and / or poorly burning exhaust gas with residual concentrations of NH3 over a wide operating temperature range. Useful catalysts are those that selectively reduce NOx and / or oxidize ammonia in an oxidizing environment (ie, an SCR catalyst and / or AMOX catalyst).
    [00019] According to a preferred embodiment, a catalyst composition is provided which comprises a zeolitic material having a CHA structure and a silica to alumina (SAR) molar ratio of about 10 to about 25, and preferably having an average crystalline size of about 0.5 to about 5 microns; and containing at least one promoter metal other than aluminum (M) present in said zeolitic material in a ratio of promoter metal to aluminum (M: Al) from about 0.10 to about 0.24.
    [00020] The zeolites of the present invention are aluminosilicates having a crystalline or pseudo-crystalline structure and may include structural metals other than aluminum (i.e., replaced with metal), but do not include silico-aluminophosphates (SAPOs). As used herein, the term "substituted with metal" with respect to a zeolite means a structure having one or more structural atoms of aluminum or silicon replaced by a replacement metal. In contrast, the term "exchanged for metal" means a zeolite having extra-structural metal ions. Examples of metals suitable as substitution metals include copper and iron.
    [00021] Suitable zeolites have a CHA crystalline structure. The distinction between zeolite-type materials, such as naturally occurring chabazite (ie mineral), and isotypes within the same Structure Type Code is not merely arbitrary, but reflects differences in in properties between materials, which may in turn instead, lead to differences in
    Petition 870190008230, of 01/25/2019, p. 16/48 / 27 activity in the method of the present invention. The zeolites for use in the present application include natural and synthetic zeolites, but are preferably synthetic zeolites because these zeolites have a more uniform SAR, crystalline size, and crystalline morphology, and have less impurities and these are less concentrated (for example, alkaline earth metals) . Specific zeolites having the CHA structure that are useful in the present invention include, but are not limited to, SSZ-13, LZ-218, Linde D, Linde R, Phi, and ZK-14, with SSZ-13 being preferred.
    [00022] Preferred zeolites having a crystalline CHA structure do not have an appreciable amount of phosphorus in their structure. That is, the CHA zeolitic structure of the present invention does not have phosphorus as a regular repeat unit and / or does not have an amount of phosphorus that would affect the basic physical and / or chemical properties of the material, particularly with respect to the material's capacity selectively reduce NOx over a wide temperature range. Therefore, the non-phosphorous CHA crystal structure may include crystal structures having a minimum amount of phosphorus.
    [00023] The zeolites for application in the present invention can include those that have been treated to improve hydrothermal stability. Conventional methods of improving hydrothermal stability include: (i) steam de-alumination and acid extraction using an acid or complexing agent, for example, (ethylene diaminetetraacetic acid - EDTA); treatment with acid and / or complexing agent; treatment with a SiCl4 gas stream (replaces Al in the zeolytic structure with Si); and (ii) cation exchange - use of multivalent cations such as lanthanum (La). Other methods, such as the use of phosphorus-containing compounds, are not necessary due to the synergistic effect of combining low copper charge in a CHA zeolite having relatively low SAR and large relative average crystal size.
    Petition 870190008230, of 01/25/2019, p. 17/48 / 27 [00024] In preferred embodiments, the catalyst composition comprises molecular sieve crystals having an average crystal size of more than about 0.5 pm, preferably between about 0.5 and about 15 pm, such as about 0.5 to about 5 pm, about 0.7 to about 5 pm, about 1 to about 5 pm, about 1.5 to about 5.0 pm, about 1.5 to about 4.0 pm, about 2 to about 5 pm, or about 1 pm to about 10 pm. The crystals in the catalyst composition can be individual crystals, crystal agglomeration, or a combination of both, provided that the crystal agglomeration has an average particle size that is preferably less than about 15 pm, more preferably less than about 10 pm, and even more preferably less than about 5 pm. The lower limit on the average particle size of the agglomeration is the average individual crystal size of the composition.
    [00025] The crystal size (also indicated here as the crystal diameter) is the length of one end of a crystal face. For example, the morphology of chabazite crystals is characterized by rhombohedral (but approximately cubic) faces in which each end of the face is approximately the same length. Direct measurement of crystal size can be performed using microscopic methods, such as SEM and TEM. For example, SEM measurement involves examining the morphology of materials at high amplifications (typically 1,000x to 10,000x). The SEM method can be performed by distributing a representative portion of the zeolite powder in a suitable assembly such that the individual particles are reasonably spread evenly across the 1,000x to 10,000x magnification field of view. From this population, a statistically significant sample of individual random crystals (for example, from 50 to 200) is examined and the longest dimensions of the individual crystals parallel to the horizontal line of a straight end are measured and recorded. (The particles that are
    Petition 870190008230, of 01/25/2019, p. 18/48 / 27 evidently large polycrystalline aggregates should not be included in the measurements.) Based on these measurements, the arithmetic mean of the sample crystal sizes is calculated.
    [00026] The particle size of an agglomeration of crystals can be determined in a similar way except that instead of measuring the end of a face of an individual crystal, the length of the longest side of an agglomeration is measured. Other techniques for determining the average particle size, such as laser diffraction and scattering, can also be used.
    [00027] As used here, the term "mean" with respect to crystal or particle size is intended to represent the arithmetic mean of a statistically significant sample of the population. For example, a catalyst comprising molecular sieve crystals having an average crystal size of about 0.5 to about 5.0 pm is a catalyst having a population of molecular sieve crystals, in which a statistically significant sample of the population (for example, 50 crystals) would produce an arithmetic average within the range of about 0.5 to about 5.0 pm.
    [00028] In addition to the average crystal size, the catalyst compositions preferably have a majority of crystal sizes that are more than about 0.5 pm, preferably between about 0.5 and about 15 pm, such as about from 0.5 to about 5 pm, about 0.7 to about 5 pm, about 1 to about 5 pm, about 1.5 to about 5.0 pm, about 1.5 to about from 4.0 pm, about 2 to about 5 pm, or about 1 pm to about 10 pm. Preferably, the first and third quarter of the sample of crystal sizes is more than about 0.5 pm, preferably between about 0.5 and about 15 pm, such as about 0.5 to about 5 pm , about 0.7 to about 5 pm, about 1 to about 5 pm, about 1.5 to about 5.0 pm, about 1.5 to about 4.0 pm, about 2 at about 5 pm, or about 1
    Petition 870190008230, of 01/25/2019, p. 19/48 / 27 gm to about 10 gm. As used herein, the term "first quarter" means the value below which a quarter of the elements are located. For example, the first quarter of a sample of forty crystal sizes is the size of the tenth crystal when the sizes of the forty crystals are arranged in order from smallest to largest. Similarly, the term "third quarter" means the value below which three quarters of the elements are located.
    [00029] Preferred CHA zeolites have a silica-to-alumina molar ratio of about 10 to about 25, more preferably about 14 to about 18, and even more preferably about 15 to about 17. The silica-to-alumina ratio of zeolites can be determined by conventional analysis. This reason is intended to represent, as closely as possible, the reason in the rigid atomic structure 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 silica-to-alumina ratio of zeolite after it has been combined with a binder material. Therefore, the silica-to-alumina ratio was expressed above in terms of the silica-to-alumina ratio of the parent zeolite, i.e., the zeolite used to prepare the catalyst, as measured before combining this zeolite with the other catalyst components.
    [00030] CHA zeolites, in particular SSZ-13, having a low SAR and medium-wide crystal size are commercially available. Alternatively, these materials can be synthesized by processes known in the art, such as those described in WO 2010/043981 (which is incorporated by reference) and WO 2010/074040 (which is incorporated by reference), or DW Fickel, et al., “Copper Coordination in Cu-SSZ-13 and Cu-SSZ-16 Investigated by Variable-Temperature XRD”, J Phys. Chem., 114, p, 1633-40 (2010), which demonstrates the synthesis of an SSZ-13
    Petition 870190008230, of 01/25/2019, p. 20/48 / 27 loaded with copper having a SAR of 12.
    [00031] Preferably, the catalyst composition comprises at least one extra-structural metal to improve (i.e., promote) the catalytic performance and / or thermal stability of the material. As used herein, an "extra-structural metal" is one that resides within the molecular sieve and / or at least a portion of the surface of the molecular sieve, not including aluminum, and not including atoms that constitute the structure of the molecular sieve. The extra-structural metal can be sieved through the molecular sieve using any known technique such as ion exchange, impregnation, isomorphic substitution, etc. extra-structural metals can be any of the catalytically recognized active metals that are used in the catalyst industry to form molten metal molecular sieves. In one embodiment, at least one extra-structural metal is used in conjunction with the molecular sieve to increase the performance of the catalyst. The preferred extra-structural metals are selected from the group consisting of copper, nickel, zinc, iron, tin, tungsten, molybdenum, cobalt, bismuth, titanium, zirconium, antimony, manganese, chromium, vanadium, niobium, ruthenium, rhodium, palladium, gold , silver, indium, platinum, iridium, rhenium, and mixtures thereof. The most preferred extra-structural metals include those selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and copper, and mixtures thereof. Preferably, at least one of the extra-structural metals is copper. Other preferred extra-structural metals include iron, particularly in combination with copper. For embodiments in which the aluminosilicate has a CHA structure, the preferred promoter is copper. [00032] In some embodiments, the charge of promoter metal is from about 0.1 to about 10% by weight based on the total weight of the molecular sieve, for example from about 0.5% by weight at about 5% by weight, from about 0.5 to about 1% by weight, and from about 2 to about 5% by weight
    Petition 870190008230, of 01/25/2019, p. 21/48 / 27 weight. In some embodiments, the promoter metal (M), preferably copper, is present in the aluminosilicate zeolite in an amount to produce an atomic M: Al ratio of about 0.17 to about 0.24, preferably about from 0.22 to about 0.24, particularly when the aluminosilicate zeolite has a SAR of about 15 to about 20. As used herein, the ratio of M: Al is based on the relative amount of M to Al structure in the corresponding zeolite. In some embodiments that included switched copper, copper is present in an amount of about 80 to about 120 g / ft 3 (2.82 to 4.23 g / l) of zeolite load or reactive coating, including , for example, about 86 to about 94 g / ft 3 (3.03 to 3.31 g / l), or about 92 to about 94 g / ft 3 (3.24 to 3.31 g / l) l). [00033] The type and concentration of the transmission metal may vary according to the host molecular sieve and the application.
    [00034] In one example, a metal-exchanged molecular sieve is created by mixing the molecular sieve in a solution containing soluble precursors of the catalytically active metal. The pH of the solution can be adjusted to induce precipitation of catalytically active cations in or within the molecular sieve structure. For example, in a preferred embodiment a chabazite is immersed in a solution containing copper nitrate for a time sufficient to allow the incorporation of catalytically active copper cations into the molecular sieve structure by ion exchange. Unchanged copper ions are precipitated. Depending on the application, a portion of the unchanged ions may remain in the molecular sieve material as free copper. The metal-exchanged molecular sieve can then be washed, dried and calcined. When iron and / or copper is used as the metal cation, the metal content of the catalytic material by weight preferably comprises from about 0.1 to about 10 weight percent, more preferably from about 0.5 to about 10 weight percent, for example about 1 to about 5 weight percent or about 2 to about 3 weight
    Petition 870190008230, of 01/25/2019, p. 22/48 / 27 weight percent, based on the weight of the zeolite.
    [00035] In another embodiment of the invention, the amount of promoter metal, such as copper, in the catalyst is not particularly limited as long as the catalyst can achieve a NOx conversion of at least about 65%, preferably at least about 75%, and more preferably at least about 85%, at a temperature of at least about 450 ° C, more preferably a temperature of at least about 550 ° C, and even more preferably a temperature of at least about 650 ° C. Preferably, the conversion in each of these temperature ranges is at least about 70%, more preferably 80%, and even more preferably 90% of the catalyst's conversion capacity when the catalyst is operating at a temperature of 250 °. Ç. Preferably, the catalyst can achieve 80% conversion with an N2 selectivity of at least about 85% in one or more of these temperature ranges.
    [00036] In general, the ion exchange of the catalytic metal cation in or in the molecular sieve can be carried out at room temperature or at a temperature and up to about 80 ° C for a period of about 1 to 24 hours in a pH of about 7. The resulting catalytic molecular sieve material is preferably dried at about 100 to 120 ° C overnight and calcined at a temperature of at least about 500 ° C.
    [00037] In some embodiments, the metal-promoted zeolitic catalysts of the present invention also contain a relatively large amount of Ce. In some embodiments, the zeolite, preferably a CHA aluminosilicate, has a SAR of less than 20, preferably about 15 to about 18, and is promoted with a metal, preferably copper and preferably in a copper atomic ratio: aluminum from about 0.17 to about 0.24, and also contain Ce in a concentration of more than about 1 weight percent,
    Petition 870190008230, of 01/25/2019, p. 23/48 / 27 preferably more than about 1.35 weight percent, more preferably 1.35 to 13.5 weight percent, based on the total weight of the zeolite. Such Ce-containing catalysts are more durable compared to structurally similar catalysts, such as other CHA zeolites having a higher SAR, particularly those with higher loads of promoter metals.
    [00038] Preferably, the concentration of ceria 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. For most of these ranges, the improvement in catalyst performance is directly correlated with the concentration of Ce in the catalyst. These bands are particularly preferred for copper-promoted aluminosilicates having a CHA structure, such as SSZ-13, with a SAR of about 10 to about 25, about 20 to about 25, about 15 to about 20 , or about 16 to about 18, and most preferably such embodiments, where copper is present in a copper-to-aluminum ratio of about 0.17 to about 0.24.
    [00039] In some embodiments, the concentration of ceria in the catalyst material is about 50 to about 550 g / ft 3 (1.76 to 19.42 g / l). Other Ce ranges include: over 100 g / ft 3 (3.53 g / l), over 200 g / ft 3 (7.06 g / l), over 300 g / ft 3 (11 g / l) ), above 400 g / ft 3 (14.12 g / l), above 500 g / ft 3 (17.65 g / l), from about 75 to about 350 g / ft 3 (2.64 to 12 , 35 g / l), of about
    Petition 870190008230, of 01/25/2019, p. 24/48 / 27 from 100 to about 300 g / ft 3 (3.53 to 11 g / l), and from about 100 to about 250 g / ft 3 (3.53 to 8.82 g / l ).
    [00040] In some embodiments, the Ce concentration exceeds the maximum theoretical amount available for exchange in the zeolite promoted with metal. Therefore, in some embodiments, Ce is present in more than one form, such as Ce ions, monomeric ceria, oligomeric ceria, and combinations of these, as long as the oligomeric ceria has an average crystal size of less than 5 μηι, for example less than 1 μm, about 10 nm to about 1 μ ^ about 100 nm to about 1 μ ^ about 500 nm to about 1 μm, about 10 to about 500 nm , about 100 to about 500 nm, and about 10 to about 100 nm. As used herein, the term "monomeric ceria" means CeO2 as individual molecules or portions that reside freely on and / or in the zeolite or weakly attached to the zeolite. As used herein, the term "oligomeric ceria" means CeO2 nano crystalline residing freely on and / or in the zeolite or weakly bound to the zeolite.
    [00041] For embodiments in which the catalyst is part of a reactive coating nano crystalline, the reactive coating may also comprise a binder containing Ce or ceria. For such embodiments, the particles containing Ce in the binder are significantly larger than the particles containing Ce in the catalyst.
    [00042] The ceria is preferably incorporated into a zeolite containing a promotion metal. For example, in a preferred embodiment, an aluminosilicate having a CHA structure is subjected to a copper exchange process before being impregnated with Ce. An exemplary Ce impregnation process involves adding Ce nitrate to a zeolite promoted with copper using a conventional incipient wetting technique.
    [00043] The zeolitic catalyst for use in the present invention can
    Petition 870190008230, of 01/25/2019, p. 25/48 / 27 be in the form of a reactive coating, preferably a reactive coating that is suitable for coating a substrate, such as a flow of metal or ceramic through a monolith substrate or a filtration substrate, including, for example, a wall flow filter or sintered or partial metal filter. Therefore, another aspect of the invention is a reactive coating that comprises a catalyst component as described herein. In addition to the catalyst component, reactive coating compositions may also comprise a binder selected from the group consisting of alumina, silica, silica-alumina (non-zeolitic), naturally occurring clays, TiO2, ZrO2 and SnO2.
    [00044] In one embodiment, a substrate is provided on which the zeolitic catalyst is deposited.
    [00045] The preferred substrates for use in mobile applications are monoliths having a so-called honeycomb geometry that comprises a plurality of parallel adjacent channels, each channel typically having a square cross-sectional area. The honeycomb shape provides a large catalytic surface with minimal overall size and pressure drop. The zeolitic catalyst can be deposited on a direct flow monolith substrate (for example, a honeycomb monolithic catalyst support structure with very small parallel channels flowing axially through the entire part) or filter monolith substrate such as a water flow filter, etc. In another embodiment, the zeolitic catalyst is formed into a catalyst of the type subjected to extrusion. Preferably, the zeolitic catalyst is coated on a substrate in an amount sufficient to reduce the NOx contained in an exhaust gas stream flowing through the substrate. In some embodiments, at least a portion of the substrate may also contain a platinum group metal, such as platinum (Pt), to oxidize ammonia in the exhaust gas stream.
    Petition 870190008230, of 01/25/2019, p. 26/48 / 27 [00046] Preferably, the molecular sieve catalyst is incorporated into or on a substrate in an amount sufficient to reduce the NOx contained in an exhaust gas stream flowing through the substrate. In some embodiments, at least a portion of the substrate may also contain an oxidation catalyst, such as a platinum group metal (eg platinum), to oxidize ammonia in the exhaust gas stream or perform other functions such as conversion of CO to CO2.
    [00047] The catalytic zeolites described here can promote the reaction of a reducer, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N2) and water (H2O) in relation to the competition reaction of oxygen and ammonia. In one embodiment, the catalyst can be formulated to favor the reduction of nitrogen oxides with ammonia (ie, and SCR catalyst). In another embodiment, the catalyst can be formulated to promote oxidation of ammonia with oxygen (i.e., an ammonia oxidation catalyst (AMOX)). In yet another embodiment, an SCR catalyst and an AMOX catalyst are used in series, in which both catalysts comprise the zeolite-containing metal described herein, and in which the SCR catalyst is upstream of the AMOX catalyst. In some embodiments, the AMOX catalyst is arranged as a top layer in an oxidizing sublayer, wherein the sublayer comprises a platinum group metal catalyst (PGM) or a non-PGM catalyst. Preferably, the AMOX catalyst is arranged on a high surface area support, including, but not limited to, alumina. In some embodiments, the AMOX catalyst is applied to a substrate, preferably substrates that are designed to provide a large contact surface with minimal back pressure, such as direct flow metallic honeycomb or cordierite. For example, a preferred substrate has between about 25 and about 300 cells
    Petition 870190008230, of 01/25/2019, p. 27/48 / 27 per square inch (CPSI) to ensure low back pressure. Obtaining a low back pressure is particularly important to minimize the effect of the AMOX catalyst on the performance of low pressure EGR. The AMOX catalyst can be applied to the substrate as a reactive coating, preferably to obtain a charge of about 0.3 to 2.3 g / in 3 (18.8 to 143, 8 g / L). To provide another conversion of NO X , the front of the substrate can be coated only with the SCR coating, and the rear coated with SCR and an NH3 oxidation catalyst that can also include Pt or Pt / Pd in a support alumina.
    [00048] In accordance with another aspect of the invention, a method is provided for reducing NOx compounds or NH3 oxidation in a gas, which comprises contacting the gas with a catalyst composition described herein for the catalytic reduction of NOx compounds by enough time to reduce the level of NOx compounds in the gas. In one embodiment, the nitrogen oxides are reduced with the reducing agent at a temperature of at least 100 ° C. In another embodiment, the nitrogen oxides are reduced with the reducing agent at a temperature of about 150 ° C to 750 ° C. in a particular embodiment, the temperature range is 175 to 550 ° C. In another embodiment, 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. Embodiments using temperatures greater than 450 ° C are particularly useful for treating the exhaust gases of a heavy-duty 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, where the zeolitic catalyst for use in the present invention is located downstream of the filter. In other embodiments, the
    Petition 870190008230, of 01/25/2019, p. 28/48 / 27 SCR zeolite catalyst is incorporated into a filter substrate. The methods of the present invention can comprise one or more of the following steps: (a) accumulating and / or burning the soot that is in contact with the entrance of a catalytic filter; (b) introducing a nitrogen-reducing agent into the exhaust gas stream before contacting the catalytic filter, preferably without any catalytic intervention step involving the NOx treatment and the reducer; (c) generating NH3 in an NOx absorbent catalyst, and preferably using NH3 as a reducer in a downstream SCR reaction; (d) contacting the exhaust gas stream with a DOC to oxidize the hydrocarbons with the organic fraction of soluble base (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 the exhaust gas with one or more direct flow SCR catalyst devices in the presence of a reducing agent to reduce the NOx concentration in the exhaust gas; and (f) contacting the exhaust gas with an AMOX catalyst, preferably downstream of the SCR catalyst to oxidize most, if all, of the ammonia before emitting the exhaust gas to the atmosphere or passing the exhaust gas through a recirculation loop before the exhaust gas enters / re-enters the engine.
    [00049] The reducer (also known as a reducing agent) for SCR processes broadly means any compound that promotes the reduction of NOx in an exhaust gas. Examples of reducers useful in the present invention include ammonia, hydrazine or any suitable ammonia precursor, such as urea ((NH2) 2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate, and hydrocarbons such as diesel fuel, and others. Particularly preferred reducers are nitrogen based, with ammonia being particularly preferred.
    Petition 870190008230, of 01/25/2019, p. 29/48 / 27 [00050] In another embodiment, all or at least a portion of the nitrogen-based reducer, particularly NH3, can be supplied by a NOX absorbent catalyst (NAC), a poor NOX siphon (LNT) ), or a NOX storage / reduction catalyst (NSRC), arranged upstream of the SCR catalyst, for example, an SCR catalyst of the present invention arranged in a wall flow filter. The NAC components useful in the present invention include a combination of catalysts of a basic material (such as alkali metal, alkaline earth metal or a rare earth metal, including alkali metal oxides, alkaline earth metal oxides, and combinations thereof) , and a precious metal (such as platinum), and optionally a reducing 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 in about 10 to about 200 g / ft 3 (0.35 to 7.06 g / l), such as 20 to 60 g / ft 3 (0.70 to 2.11 g / l). Alternatively, the precious metal of the catalyst is characterized by the average concentration which can be from about 40 to about 100 grams / ft 3 (1.41 to 3.53 g / l).
    [00051] Under certain conditions, during periodically rich regeneration events, NH3 can be generated in a NOx absorbent catalyst. The SCR catalyst downstream of the NOx absorbent catalyst can improve the system's NOx reduction efficiency as a whole. In the combined system, the SCR catalyst is able to store the NH3 released from the NAC catalyst during rich regeneration events and uses the stored NH3 to selectively reduce some or all of the NOx that slips through the NAC catalyst during operating conditions normal poor.
    [00052] The method can be carried out on a gaseous derivative of a combustion process, such as an internal combustion engine (either
    Petition 870190008230, of 01/25/2019, p. 30/48 / 27 mobile or stationary), a gas turbine and power generation plants using burnt coal or oil. The method can also be used to treat gas from industrial processes such as refining, from refinery boiler heaters, ovens, the chemical processing industry, coke ovens, municipal waste plants and incinerators, etc. In a particular embodiment, the method is used to treat the exhaust gas of a low-burn internal combustion vehicle engine, such as a diesel engine, a low-burn gasoline engine or an oil-gas engine liquefied or natural gas.
    [00053] According to another aspect, the invention provides an exhaust system for a low combustion internal combustion vehicle engine, whose system comprises a duct for charging a flow exhaust gas, a source of nitrogen reducer and a catalyst zeolitic described here. The system may include a controller to measure the nitrogen reducer in the flow exhaust gas only when it is determined that the zeolitic 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 determination by the control means can be aided by one or more suitable sensor inputs indicative of an engine condition selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, gas mass flow exhaust system, collector vacuum, ignition time, engine speed, lambda value of the exhaust gas, the amount of fuel injected into the engine, the position of the exhaust gas recirculation valve (EGR) and thus the amount EGR and supercharging pressure.
    [00054] In a particular embodiment, the measurement is controlled in response to the amount of nitrogen oxides in the exhaust gas determined directly (using a suitable NOx sensor) or indirectly, such as using prePetition query tables or maps 870190008230, of 25/01/2019, p. 31/48 / 27 correlated - stored in the control means - correlating any one or more of the above mentioned entries indicative of an engine condition with a predicted exhaust gas NOx content. 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 at 1: 1 NH3 / NO and 4: 3 NH3 / NO2. The control means may comprise a pre-programmed processor such as an electronic control unit (ECU).
    [00055] In another embodiment, an oxidation catalyst to oxidize nitrogen monoxide in the exhaust gas to nitrogen dioxide may be located downstream of a measurement point of the nitrogen reducer in the exhaust gas. In one embodiment, the oxidation catalyst is adapted to produce a gas stream that enters the SCR zeolitic catalyst having a NO to NO2 ratio of about 4: 1 to about 1: 3 by volume, for example, in an exhaust gas temperature at the oxidation catalyst inlet of 250 ° C to 450 ° C. the oxidation catalyst can include at least one platinum metal group (or some combination thereof), such as platinum, palladium, or rhodium, coated on a direct flow monolith substrate. 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 in a high surface area reactive coating component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, silica-alumina other than zeolite, ceria, zirconia, titania or an oxide mixed or composite containing both ceria and zirconia. [00056] In another 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
    Petition 870190008230, of 01/25/2019, p. 32/48 / 27 catalyzed, for example, with an oxidation catalyst of the type disclosed above, preferably the point of measuring the nitrogen reducer is located between the filter and the zeolitic 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.
    [00057] In another embodiment, the zeolitic catalyst for use in the present invention is coated on a filter located downstream of the oxidation catalyst. Where the filter includes the zeolitic catalyst for use in the present invention, the measurement point of the nitrogen reducer is preferably located between the oxidation catalyst and the filter.
    [00058] In another aspect, a poorly burning vehicle engine is provided which comprises an exhaust system according to the present invention. The low-combustion internal combustion engine can be a diesel engine, a low-burn gasoline engine or an engine powered by liquefied petroleum gas or natural gas.
    EXAMPLES
    Example 1:
    [00059] A sample of zeolite was prepared having the structure of CHA (isotype SSZ-13) and a SAR of about 17. The sample was charged with copper to produce a catalyst material having an atomic ratio of Cu: Al of about 0.20. After maturing at about 550 ° C for about 72 hours, the catalyst was exposed to a simulated diesel engine exhaust gas that was combined with ammonia to produce a stream having an ammonia to NOx (ANR) ratio of 1 and a space speed of 50,000 per hour. The catalyst's capacity for NOx conversion was determined at temperatures ranging from 200 ° C to 550 ° C.
    Comparative Example 1:
    [00060] For comparison, a similar SSZ-13 zeolite was prepared, but instead of being loaded with a low amount of copper, the material
    Petition 870190008230, of 01/25/2019, p. The comparative 33/48 / 27 was loaded with enough copper to produce an atomic ratio of Cu: Al> 0.44. The material was comparatively exposed to a similar exhaust gas stream under similar conditions. The capacity of the comparative material for NOx conversion was determined at temperatures ranging from 200 ° C to 550 ° C.
    [00061] It was found that at temperatures above 350 ° C, the lightly charged catalyst shows significant improvements in the conversion of NO X.
    Example 2:
    [00062] An aluminosilicate having a CHA structure (isotype SSZ-13) having a SAR of 17 (zeolite A) and containing 2.4 percent by weight of exchanged copper (based on the total weight of zeolite) was impregnated with nitrate of Ce using an incipient wetting technique and then the reactive coating was applied to a substrate to produce a catalyst sample having 75 g / ft 3 (2.64 g / l) of Ce (1.35 weight percent Ce , based on the total zeolite weight). The same technique was repeated for the catalyst samples produced having 96 g / ft 3 (3.38 g / l) of Ce, 119 g / ft 3 (4.19 g / l) of Ce, 188 g / ft 3 (6.63 g / l) of Ce, and 285 g / ft 3 (10.05 g / l) of Ce. Each of these samples was hydrothermally modified at 800 ° C in 10% H2O for five hours. These samples were then analyzed to determine their ability to convert NOx into an NH3 SCR process at 200 ° C and 500 ° C, where the NH3 SCR process is adjusted to allow 20 ppm of ammonia residue. The results of this analysis are provided in Figure 2.
    Comparative Examples 2 and 3:
    [00063] Zeolite A, without Ce impregnation, was analyzed to determine its ability to convert NOx into an NH3 SCR process at 200 ° C and 500 ° C, in which the NH3 SCR process is adjusted to admit 20 ppm of ammonia residue. The results of this
    Petition 870190008230, of 01/25/2019, p. 34/48 / 27 analysis are provided in Figure 1.
    [00064] An aluminosilicate having a CHA structure (isotype SSZ-13) having a SAR of 25 and containing 3.3 weight percent of exchanged copper (without Ce impregnation) was analyzed to determine its NOx conversion capacity in an NH3 SCR process at 200 ° C and 500 ° C, where the NH3 SCR process is adjusted to admit 20 ppm of ammonia residue. The results of this analysis are provided in Figure 2.
    [00065] The results of this test demonstrate that zeolites promoted with low SAR copper, which are impregnated with Ce have superior hydrothermal durability.
    权利要求:
    Claims (17)
    [1]
    1. Catalyst composition, comprising:
    a) a zeolitic material having an average crystal size of at least 0.5 pm, having a CHA matrix containing silicon and aluminum, and having a silica to alumina (SAR) molar ratio of 10 to 25; and
    b) an extra-matrix promoter metal (M) disposed in said zeolitic material as free and / or exchanged metal, characterized by the fact that the extra-matrix promoter metal is copper, and is present in an atomic ratio of promoter metal to aluminum (M: Al) from 0.10 to 0.24 based on the matrix aluminum.
    [2]
    2. Catalyst composition according to claim 1, characterized by the fact that the zeolite has a SAR of 14 to 18.
    [3]
    3. Catalyst composition according to claim 1, characterized by the fact that zeolite is an SSZ-13 isotype.
    [4]
    Catalyst composition according to claim 3, characterized in that the zeolite has an average crystal size from 1 pm to 5 pm.
    [5]
    Catalyst composition according to claim 1, characterized by the fact that a majority of copper is exchanged copper.
    [6]
    Catalyst composition according to claim 5, characterized in that the catalyst has an M: A ratio of 0.17 to 0.24.
    [7]
    Catalyst composition according to claim 5, characterized in that the catalyst has an M: A ratio of 0.22 to 0.24.
    [8]
    Catalyst composition according to claim 5, characterized in that the catalyst contains from 2 to 3 weight percent of copper.
    [9]
    9. Catalyst composition according to claim 4, characterized by the fact that zeolite has a SAR of 16 to 18, the promoting metal is copper, a majority of copper is copper exchanged, and copper is present in a
    Petition 870190008230, of 01/25/2019, p. 36/48
    2/3 M: A ratio from 0.22 to 0.24.
    [10]
    10. Catalyst composition according to claim 1, characterized by the fact that it further comprises:
    c) at least 1 percent by weight of cerium in said zeolitic material, based on the total weight of the zeolite, where cerium is present in a selected form of exchanged cerium ions, monomeric ceria, oligomeric ceria, and combinations thereof, provided that the oligomeric ceria has a particle size of less than 5 pm.
    [11]
    Catalyst composition according to claim 10, characterized in that the catalyst composition comprises from 1.35 to 13.5 weight percent cerium, based on the total weight of the zeolite.
    [12]
    Catalyst composition according to claim 11, characterized in that the composition is free of Zr, ZrO, Ti and TiO.
    [13]
    13. Catalytically active reactive coating comprising:
    a) a metal-promoted zeolitic material having a CHA matrix containing silicon and aluminum and having a silica to alumina (SAR) molar ratio of 10 to 25; wherein the zeolite is promoted with an extra-matrix promoter metal (M);
    b) one or more stabilizers and / or binders, in which the zeolite promoted by metal and the one or more stabilizers and / or binders are present together in a fluid paste, characterized by the fact that the extra-matrix promoting metal is copper, and the extra-matrix promoter metal is present in an atomic ratio of promoter metal to aluminum (M: Al) from 0.10 to 0.24 based on the matrix aluminum.
    [14]
    14. Catalytically active reactive coating according to claim 13, characterized in that it further comprises at least 1 weight percent cerium in the zeolitic material, based on the total weight of the zeolite, in which the cerium is present in a form selected cerium ions
    Petition 870190008230, of 01/25/2019, p. 37/48
    3/3 exchanges, monomeric ceria, oligomeric ceria, and combinations thereof, as long as the oligomeric ceria has a particle size of less than 5 pm.
    [15]
    15. Catalytically active reactive coating according to claim 14, characterized by the fact that it comprises the binder, in which the binder is selected from the group consisting of ceria, alumina, silica, silica-alumina (non-zeolite), clays that occur naturally, TiO 2 , ZrO 2 and SnO2.
    [16]
    16. Method for reducing NO X in an exhaust gas, characterized by the fact that it comprises:
    contacting an exhaust gas derived from a low combustion combustion process and containing NO X with a catalyst composition comprising:
    i) a zeolitic material having a CHA matrix containing silicon and aluminum and having a silica to alumina (SAR) molar ratio of 10 to 25; and ii) an extra-matrix promoter metal (M) disposed in the zeolitic material as free and / or exchanged metal, in which the extra-matrix promoter metal is copper, and is present in an atomic ratio of promoter metal to aluminum (M: Al) from 0.10 to 0.24 based on the matrix aluminum; and converting a portion of NO X to N2 and H2O.
    [17]
    17. Method for reducing NOx according to claim 16, characterized in that the catalyst composition further comprises:
    iii) at least 1 weight percent cerium in the zeolitic material, based on the total weight of the zeolite, where the cerium is present in a selected form of exchanged cerium ions, monomeric ceria, oligomeric ceria, and combinations thereof, provided that the oligomeric ceria has a particle size of less than 5 pm.
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    同族专利:
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    GB201311816D0|2013-08-14|
    US8906329B2|2014-12-09|
    RU2614411C2|2017-03-28|
    US8535629B2|2013-09-17|
    US20150064074A1|2015-03-05|
    DE112011103996T5|2013-08-29|
    JP6450521B2|2019-01-09|
    KR20130125377A|2013-11-18|
    RU2013129989A|2015-01-10|
    US20140037523A1|2014-02-06|
    WO2012075400A1|2012-06-07|
    DK2646149T3|2020-06-29|
    EP2646149A1|2013-10-09|
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    KR20180042440A|2018-04-25|
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    GB2502207A|2013-11-20|
    BR112013013711A2|2017-04-18|
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    法律状态:
    2018-10-30| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-03-26| B09A| Decision: intention to grant|
    2019-04-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/12/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/12/2011, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    US41901510P| true| 2010-12-02|2010-12-02|
    US61/419015|2010-12-02|
    US201161565774P| true| 2011-12-01|2011-12-01|
    US61/565774|2011-12-01|
    PCT/US2011/063079|WO2012075400A1|2010-12-02|2011-12-02|Zeolite catalyst containing metal|
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