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    • 专利摘要:
    catalyst composition, method and system for treating an exhaust gas; and, catalyst article. a catalyst composition is provided having an aluminosilicate molecular sieve having a steel structure and a silica to alumina molar ratio of about 20 to about 30 charged with about 1 to about 5 weight percent of a promoter metal, with based on the total weight of the molecular sieve material. methods, articles, and systems using the catalyst composition are also provided.
    公开号:BR112015022557B1
    申请号:R112015022557-8
    申请日:2014-03-14
    公开日:2020-09-29
    发明作者:John Leonello Casci；Jillian Elaine Collier；Lucia GABEROVA
    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 catalysts, articles, and methods for treating combustion exhaust gas. Description of Related Art:
    [002] Hydrocarbon-based fuel combustion in power stations and engines produces flue or exhaust gas that largely contains relatively benign nitrogen (No), water vapor (H2O), and carbon dioxide (CO2). But flue and exhaust gases also contain, in relatively small part, harmful and / or toxic substances, such as carbon monoxide (CO) from incomplete combustion, hydrocarbons (HC) from nitrogen oxides from unburned fuel. (NOx) from excessive combustion temperatures, and particulate matter (mainly soot). To mitigate the environmental impact of combustion and exhaust gas released into the atmosphere, it is desirable to eliminate or reduce the amount of undesirable components, preferably by a process that in turn does not generate other harmful or toxic substances.
    [003] Typically, combustion gases from electric power stations and exhaust gas-poor burning gas engines have a liquid oxidation effect due to the high proportion of oxygen that is provided to ensure proper combustion of the hydrocarbon fuel. . In such gases, one of the most expensive components to remove is NOx, which includes nitric oxide (NO), nitrogen dioxide (NO2), and nitrous oxide (N2O). The reduction from NOx to N2 is particularly problematic since the exhaust gas contains enough oxygen to favor oxidation reactions instead of reduction. However, NOx can be reduced by a process commonly known as Selective Catalytic Reduction (SCR). An SCR process involves the conversion of NOx, in the presence of a catalyst and with the aid of a reducing agent, such as ammonia, 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 NOx reduction reaction occurs as the gases pass through or over the catalyzed substrate. The chemical equation for stoichiometric SCR reactions using ammonia is:

    [004] Zeolites (i.e. aluminosilicates) having BEA, MOR, CHA or certain other substances are known to be useful as SCR catalysts. Such zeolites have a molecularly porous pseudo-crystalline or crystalline structure constructed primarily of alumina and silica. The catalytic performance of these zeolites can be enhanced by incorporating a metal - for example, by a cation exchange in which a portion of ionic species existing for the surface of the structure is replaced by metal cations, such as Cu2 +. Typically, higher metal concentrations correspond to higher catalytic performance.
    [005] While the SCR performance of such catalysts is acceptable at normal exhaust gas temperatures for a diesel engine, the catalyst can become exposed to unexpected temperature spikes (eg> 800 ° C) during its lifetime useful. In general, a hydrothermal stability of zeolite can be improved by increasing the ratio of silica to zeolite alumina (SAR). However, larger SARs typically limit the amount of metal that can be loaded into the zeolite.
    [006] CHA Zeolites loaded with copper are known to provide adequate CSR performance provided that the catalyst is not exposed to temperatures in excess of 800 ° C. However, there is still a need for improved SCR catalysts that are capable of withstanding even higher temperatures with little or no deactivation. The present invention satisfies this need, among others. SUMMARY OF THE INVENTION
    [007] Surprisingly, it has been found that zeolites promoted by metal having an AEI structure and a silica to alumina (SAR) ratio of about 20 to about 30 are more hydrothermally stable compared to other zeolite catalysts with similar SARs and similar metal shipments. The catalysts of the present invention provide improved catalytic performance in applications such as selective catalytic reduction (SCR) of NOx and ammonia oxidation when compared to other catalysts, particularly after the catalysts are subjected to high temperatures.
    [008] Appropriately, in one aspect of the invention, a catalyst composition is provided comprising an aluminosilicate molecular sieve having an AEI structure and a silica to alumina molar ratio of about 20 to about 30 and about 1 to about 5 weight percent of a promoter metal, based on the total weight of the molecular sieve material.
    [009] According to another aspect of the invention, a method is provided for treating an exhaust gas comprising (a) contacting an exhaust gas comprising NOx and a reducer with a catalyst composition described herein; and (b) selectively reduce at least a portion of NOx to N2 and H2O.
    [0010] According to another aspect of the invention, a catalyst article is provided comprising a catalyst composition described herein and a substrate with which and / or on which the catalyst is arranged.
    [0011] In accordance with a further aspect of the invention, a system is provided for treating exhaust gas comprising (a) a catalyst article described herein; and (b) one or more upstream components selected from a diesel oxidation catalyst, a NOx absorber catalyst, a poor NOx trap, a filter, an NH3 injector, and an SCR catalyst; and (c) optionally a downstream ammonia leak catalyst. BRIEF DESCRIPTION OF THE FIGURES
    [0012] Figure 1 shows an XRD pattern of an AEI aluminosilicate having a SAR of 22.
    [0013] Figures 2a and 2b show NOx conversion performance of AEI aluminosilicates loaded with copper and CHA aluminosilicates loaded with copper after high temperature and moderate hydrothermal aging.
    [0014] Figure 3 shows the NH3 conversion performance of AEI aluminosilicates loaded with copper after high temperature hydrothermal aging.
    [0015] E, Figures 4a, 4b, and 4c show the NOx and NH3 performance of AEI, CHA, and BEA aluminosilicates loaded with copper after poor / rich aging. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
    [0016] In a preferred embodiment, the invention is directed to a catalytic article to improve the quality of ambient air, particularly to improve emissions of flue gas or other exhaust gas generated by power plants, gas turbines, combustion engines internal burning, and the like. Exhaust gas emissions are improved, at least in part, by reducing the NOx and / or NH3 concentrations of poorly burned exhaust gas over a wide operating temperature range. Useful catalysts are those that selectively reduce NOx and / or oxidize ammonia in an oxidation environment (i.e., an SCR catalyst and / or AMOX catalyst).
    [0017] In certain embodiments, a catalyst composition comprising the zeolite material having an AEI structure and a silica to alumina (SAR) molar ratio of about 20 to about 30 and about 1 to about 10 percent is provided by weight of a promoter metal based on the total weight of the zeolite material.
    Preferred zeolites are aluminosilicates having an AEI crystalline or pseudo-crystalline structure. As used here, the term “AEI” refers to a type of AEI structure as recognized by the International Zeolite Association (IZA) Structure Commission. Most of the aluminosilicate zeolite structure is constructed of alumina and silica, but may include metals of different structure than aluminum (i.e., metal substituted zeolites). As used here, the term "substituted by metal" in relation to a zeolite means a zeolite structure having one or more atoms of aluminum or silicon structure replaced by a replacement metal. In contrast, the term "exchanged metal" means a zeolite having extra structure or free metal ions associated with the frame structure, but they are not part of the structure itself. Examples of the metal-substituted AEI frames include those comprising iron and / or copper atoms in the frame. Any AEI aluminosilicate isotype is suitable for the present invention.
    [0019] Preferably, the primary crystalline phase of the molecular sieve is AEI, although other crystalline phases such as FAU may also be present. In certain embodiments, the primary crystalline phase comprises at least about 90 weight percent AEI, preferably at least about 95 weight percent AEI, and even more preferably at least about 98 or at least about 99 weight percent AEI. The molecular sieve may contain FAU in minimal amounts, preferably less than 5 weight percent, and even more preferably less than about 2 weight percent, or even less than about 1 weight percent. Preferably, the AEI molecular sieve is substantially free of other crystalline phases and is not an intergrowth of two or more types of frame. By "substantially free" with respect to other crystalline phases, it is meant that the molecular sieve contains at least 99 weight percent AEI.
    Preferred zeolites have a silica to alumina (SAR) molar ratio of about 20 to about 30, more preferably about 20 to about 25, for example, about 20 to about 22, about 22 to about 25, or about 25 to about 30. The ratio of silica to alumina of the zeolites can be determined by conventional analysis. This reason should represent, as close as possible, the reason in the rigid atomic frame of the zeolite crystal and to exclude silicon or aluminum in the binder or in the cationic form or otherwise within the channels. Since it can be difficult to directly measure the ratio of zeolite silica to alumina after it has been combined with a binder material, particularly an alumina binder, these silica to alumina ratios are expressed in terms of zeolite SAR alone, ie , before combining zeolite with the other catalyst components.
    [0021] In addition to AEI zeolite, the catalyst composition comprises at least one promoter metal disposed in and / or within the zeolite material as extra structure metals. As used here, an “extra structure metal” is one that resides within the molecular sieve and / or on at least a portion of the molecular sieve surface, preferably since the ionic species, does not include aluminum, and does not include atoms that constitute the structure of the molecular sieve. Preferably, the presence of promoter metals facilitates the treatment of exhaust gases, such as exhaust gas from a diesel engine, including processes such as NOx reduction, NH3 oxidation, and NOx storage.
    [0022] The promoter metal can be any of the recognized catalytically active metals that are used in the catalyst industry to form metal exchange zeolites, particularly these metals that are known to be catalytically active to treat exhaust gases derived from a combustion process . Particularly preferred metals are useful in reducing NOx and storage processes. Promoter metal should be interpreted widely and specifically includes copper, nickel, zinc, iron, tungsten, molybdenum, cobalt, titanium, zirconium, manganese, chromium, vanadium, niobium, as well as tin, bismuth and antimony; platinum group metals, such as ruthenium, rhodium, palladium, indium, platinum, and precious metals such as gold and silver. Preferred transition metals are base metals, and preferred base metals include those selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and copper, and mixtures thereof. In a preferred embodiment, at least one of the promoting metals is copper. Other preferred promoting metals include iron, particularly in combination with copper.
    [0023] In certain embodiments, the promoter metal is present in the zeolite material in a concentration of about 0.1 to about 10 weight percent (% by weight) based on the total weight of the zeolite, for example from from about 0.5% by weight to about 5% by weight, from about 0.5 to about 1% by weight, from about 1 to about 5% by weight, about 2 , 5% by weight to about 3.5% by weight, and about 3% by weight to about 3.5% by weight. For embodiments using copper, iron, or a combination thereof, the concentration of these transition metals in the zeolite material is preferably about 1 to about 5 weight percent, more preferably about 2.5 to about 3, 5 percent by weight.
    [0024] In certain embodiments, the promoting metal, such as copper, is present in an amount from about 2,856 (80) to about 4,284 g / m3 (120 g / ft3) of the zeolite or washable coating load, including for example, about 3,034.5 (85) to about 3,391.5 g / m3 (95 g / ft3), or about 3,213 (90) to about 3,391.5 g / m3 (95 g / ft3) .
    [0025] In certain embodiments, the promoter metal is present in an amount relative to the amount of aluminum in the zeolite, namely the structure aluminum. As used here, the ratio of promoter metal: aluminum (M: A1) is based on the relative molar amount of promoter metal to Al of molar structure in the corresponding zeolite. In certain embodiments, the material catalyst has an M: A1 ratio of about 0.1 to about 1.0, preferably about 0.2 to about 0.5. A M: A1 ratio of about 0.2 to about 0.5 is particularly useful where M is copper, and more particularly where M is copper and the zeolite SAR is about 20 to 25.
    [0026] In one example, a metal exchange zeolite is created by mixing the zeolite in a solution containing soluble precursors of the catalytically active metals. The pH of the solution can be adjusted to induce precipitation of catalytically active metal cations in or within the zeolite structure (but not including the zeolite frame). For example, in a preferred embodiment, an AEI zeolite material 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 exchange zeolite can then be washed, dried, and calcined.
    [0027] In general, ion exchange of catalytic metal cation to or in the molecular sieve can be carried out at room temperature or at a temperature up to about 80 ° C over a period of about 1 to 24 hours at 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.
    [0028] In certain embodiments, the catalyst composition comprises the combination of at least one promoter metal and at least one alkali metal or alkaline earth metal, wherein the transition metals and alkali metals or alkaline earth metals are disposed in or within the material of zeolite. Alkali or alkaline earth metal can be selected from sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, or some combination thereof. As used here, the phrase "alkali metal or alkaline earth metal" does not mean alkali metals and alkaline earth metals are used in the alternative, but instead one or more alkali metals can be used alone or in combination with one or more alkali metals that one or more alkaline earth metals can be used alone or in combination with one or more alkali metals. In certain embodiments, alkali metals are preferred. In certain embodiments, alkaline earth metals are preferred. Preferred alkali or alkaline earth metals include calcium, potassium, and combinations thereof. In certain embodiments, the catalyst composition is essentially free of magnesium and / or barium. In certain embodiments, the catalyst is essentially free of any alkali or alkaline earth metals except calcium and potassium. In certain embodiments, the catalyst is essentially free of any alkaline or alkaline earth metals except calcium, and in certain other embodiments, the catalyst is essentially free of any alkaline or alkaline earth metals except potassium. As used here, the term "essentially free" means that the material does not have an appreciable amount of the particular metal. That is, the particular metal is not present in the amount that can affect the basic physical and / or chemical properties of the material, particularly with respect to the material's ability to selectively reduce or store NOx.
    [0029] In certain embodiments, the zeolite material has an alkali content of less than 3 weight percent, more preferably less than 1 weight percent, and even more preferably less than 0.1 weight percent.
    [0030] In certain embodiments, the alkaline and / or alkaline earth metal (collectively AM) is present in the zeolite material in an amount with respect to the amount of promoter metal (M) in the zeolite. Preferably, M 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 from 3: 1, or about 6: 1 to about 4: 1, particularly were M is copper and AM is calcium. In certain embodiments that include an alkali and / or alkaline earth metal such as calcium, the amount of copper present is less than 2.5 weight percent, for example less than 2 weight percent or less than 1 weight percent , based on the weight of the zeolite.
    [0031] In certain embodiments, the relative cumulative amount of promoter metal (M) and alkaline and / or alkaline earth metal (AM) is present in the zeolite material in an amount relative to the amount of aluminum in the zeolite, namely the structure aluminum . As used here, the ratio of (M + AM): A1 is based on the relative molar amounts of M + AM to Al of molar structure in the corresponding zeolite. In certain embodiments, the material catalyst has a ratio of (M + AM): A1 of no more than about 0.6. In certain embodiments, the ratio of (M + AM): A1 is not more than 0.5, for example, about 0.05 to about 0.5, about 0.1 to about 0.4, or about 0.1 to about 0.2.
    [0032] Promoter metal and alkaline / alkaline earth metal can be added to the molecular sieve through any known technique such as ion exchange, impregnation, isomorphic substitution, etc. The promoter metal and the alkali or alkaline earth metal can be added to the zeolite material in any order (for example, the metal can be exchanged before, after, or concurrently with the alkali or alkaline earth metal), but preferably the alkali or alkaline earth is added before or concurrently with the promoter metal, particularly when the alkaline earth metal is calcium and the promoter metal is copper.
    [0033] In certain embodiments, the metal-promoted zeolite catalysts of the present invention also contain a relatively large amount of cerium (Ce). In certain embodiments, the concentration of cerium in the material catalyst 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 percent to about 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 from 2 to about 9.5 weight percent, and from 5 to about 9.5 weight percent, based on the total weight of the zeolite. In certain embodiments, the concentration of cerium in the material catalyst is about 1,785 (50) to about 19,635 g / m3 (550 g / ft3). Other Ce ranges include: above 3,570 g / m3 (100 g / ft3), above 7,140 g / m3 (200 g / ft3), above 10,710 g / m3 (300 g / ft3) above 14,280 g / m3 (400 g / ft3), above 17,850 g / m3 (500 g / ft3), from about 2,677.5 (75) to about 12,495 g / m3 (350 g / ft3), from about 3,570 (100) to about 10,710 g / m3 (300 g / ft3), and from about 3,570 (100) to about 8,925 g / m3 (250 g / ft3).
    [0034] In certain modalities, the Ce concentration exceeds the maximum theoretical amount available for exchange in zeolite promoted by metal. Appropriately, in some embodiments, Ce is present in more than one form, such as Ce ions, monomeric ceria, oligomeric ceria, and combinations thereof, provided that said oligomeric ceria has an average crystal size of less than than 5 pm, for example less than 1 pm, about 10 nm to about 1 pm, about 100 nm to about 1 pm, about 500 nm to about 1 pm, about 10 to about 500 nm , about 100 to about 500 nm, and about 10 to about 100 nm. As used here, the term "monomeric ceria" means CeCh as individual molecules or portions that reside freely in and / or in the zeolite or weakly attached to the zeolite. As used here, the term "oligomeric ceria" means nanocrystalline CeCh which resides freely in and / or in the zeolite or weakly linked with the zeolite.
    [0035] Catalysts of the present invention are applicable to heterogeneous catalytic reaction systems (i.e., solid catalyst in contact with a gaseous reagent). To improve the contact surface area, mechanical stability, and / or fluid flow characteristics, catalysts can be arranged in and / or within a substrate, preferably a porous substrate. In certain embodiments, a washable coating containing the catalyst is applied to an inert substrate, such as corrugated metal plate or a honeycomb cordierite brick. Alternatively, the catalyst is kneaded together with other components such as fillers, binders, and reinforcing agents, into an extrudable paste that is then extruded through a die to form a metal block brick. Suitably, in certain embodiments, a catalyst article is provided comprising a metal-promoted AEI zeolite catalyst described herein coated in and / or embedded in a substrate.
    [0036] Certain aspects of the invention provide a washable catalytic coating. The washable coating comprising the AEI catalyst described herein is preferably a solution, suspension, or slurry. Suitable coatings include surface coatings, coatings that penetrate a portion of the substrate, coatings that permeate the substrate, or some combination thereof.
    [0037] In a certain aspect, the invention is a catalyst composition comprising AEI molecular sieve of aluminosilicate crystals having an average crystal size (i.e., individual crystals including twin crystals) of more than about 0.5 pm, preferably between about 0.1 and about 15 pm, such as about 0.5 to about 5 pm, about 0.7 to about 1.5 pm, about 1 to about 5 pm, or about from 1 pm to about 10 pm, particularly for catalysts that are free or substantially free of halogens, such as fluorine. The crystal size is the length of one edge of a crystal face, preferably the longest edge provided that the crystals are not needle shaped. 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 magnifications (typically 10000x to 10000x). The SEM method can be carried out by distributing a representative portion of the zeolite powder in an appropriate amount such that individual particles are reasonably evenly spread across the field of view at 100 to 1000 magnification. From this population, a statistically significant sample of individual random crystals (for example, 50 to 200) are examined and the longest dimensions of the individual crystals parallel to the horizontal line of the straight edge are measured and recorded. (Particles that are clearly large polycrystalline aggregates should not be included in the measurements.) Based on these measurements, the arithmetic mean of the sample crystal sizes is calculated.
    [0038] In addition to the average crystal size, catalyst compositions preferably have a majority of the crystal sizes are greater 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 jam, about 2 to about 5 jam, or about 1 jam to about 10 jam. Preferably, the first and third quartiles of the sample of crystal sizes are greater 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 until about 5 pm, or about 1 pm until about 10 pm.
    [0039] In certain respects, the catalyst is an AEI zeolite promoted by metal having a SAR of about 15 to about 25, such as about 15 to about 17, and having an average crystal size of about 0 , 1 to about 10 pm, such as about 0.5 to 5 pm, or 0.5 to 1.5 pm, particularly where such a catalyst is free or substantially free of halogens, such as fluorine. Preferred promoting metals for such a catalyst include copper and iron. Preferably, such AEI zeolites are synthesized using an N, N-Dimethyl-3,5-dimethylpiperidinium hydroxide model. Such catalysts demonstrate high hydrothermal durability and also produce high conversions of NOx when used as SCR catalysts.
    [0040] In certain aspects, the invention is an SCR catalyst comprising two or more catalytic materials arranged in separate zones or formulated as mixtures. For example, in certain aspects, the SCR catalyst comprises a first zone comprising a metal-promoted AEI zeolite as defined herein, and a second zone containing a second catalyst such as an SCR catalyst. The first and second zones can be on a single substrate, such as a wall flow filter or a honeycomb flowing through, or on separate substrates, but are preferably arranged on or within a single substrate unit. Examples of a second catalyst include molecular sieves, such as aluminosilicates, silicoaluminophosphates, and ferrosilicates including small pore molecular sieves, medium pore molecular sieves, and large pore molecular sieves. For certain applications, small pore zeolites and SAPOs are preferred, an example of a small pore molecular sieve is CHA. Another example of a small pore molecular sieve is AFX. Other small pore molecular sieves include AEI, DDR, LEV, ERI, RHO, AFX, AFT, and KFI. Other useful molecular sieves include BEA, MFI, MOR, and FER. The molecular sieve of the second catalyst can be in the form of H +, and / or can be exchanged with a transition metal, such as Cu, Fe, Ni, Co, and Mn, a noble metal such as Au, Ag, Pt, Pd , and Ru, or some combination thereof. Particularly useful metals include Fe and Cu. Other examples of a second catalyst include vanadium catalysts, such as V2O5 supported on silica, titania, or alumina, and optionally in combination with other metals such as tungsten and / or molybdenum. The first zone can be upstream or downstream of the second zone with respect to the exhaust gas flow, but is preferably downstream. The upstream and downstream zones can correspond with the front and rear ends, respectively, of a honeycomb flowing through substrate, or they can correspond with the inlet and outlet sides, respectively, of a filter. wall drainage. The two zones can partially or completely overlap. For partial overlap, the overlap section will create a third intermediate zone. Alternatively, the two zones can be adjacent to each other, with little or no gap between them (i.e., less than 0.2 inches). Alternatively, the first and second catalysts can be mixed and washable coatings as a single catalyst layer or extruded as a homogeneous honeycomb substrate. In certain aspects, the catalyst additionally comprises a third catalyst material which is mixed with one or both of the first and second catalytic materials or is arranged in a third zone, where the third zone is downstream or upstream of the first catalyst and / or the second catalyst, but is preferably on the same substrate.
    [0041] A washable coating may 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 may comprise pore forming agents such as graphite, cellulose, starch, polyacrylate, and polyethylene, and the like. These additional components do not necessarily catalyze the desired reaction, but instead provide the effectiveness of the catalytic material, for example, increasing its operating temperature range, increasing the catalyst's contact surface area, increasing the catalyst's adhesion to a substrate, etc. In preferred embodiments, the washable coating load is> 0.3 g / in3, such as> 1.2 g / in3,> 1.5 g / in3,> 1.7 g / in3 or> 2.00 g / in3, and preferably <3.5 g / in3, such as <2.5 g / in3. In certain embodiments, the washable coating is applied to a substrate in a load of about 0.8 to 1.0 g / in3, 1.0 to 1.5 g / in3, or 1.5 to 2.5 g / in3.
    [0042] Of the most common substrate designs are slabs and honeycomb. Preferred substrates, particularly for mobile applications, include monoliths flowing through having a so-called honeycomb geometry that comprise multiple adjacent parallel channels that are opened at both ends and generally extend from the entrance face to the face of substrate and result in a high surface area to volume ratio. For certain applications, the honeycomb flow monolith preferably has a high cell density, for example, about 600 to 800 cells per square inch, and / or an average internal wall thickness of about 0.18 to 0.35 mm, preferably about 0.20 to 0.25 mm. For certain other applications, the honeycomb flow monolith preferably has a low cell density of about 150 to 600 cells per square inch, more preferably about 200 to 400 cells per square inch. Preferably, the honeycomb monoliths are porous. In addition to cordierite, silicon carbide, silicon nitride, ceramic, and metal, other materials that can be used for the substrate include aluminum nitride, silicon nitride, aluminum titanate, a-alumina, mullite, for example, mullite acicular, polucite, a thermet such as AflOsZFe, AI2O3 / NÍ or BztCZFe, or composites comprising segments of any two or more of them. Preferred materials include cordierite, silicon carbide, and alumina titanate.
    [0043] Plate type catalysts have lower pressure drops and are less susceptible to clogging and fouling than honeycomb types, which is advantageous in high efficiency stationary applications, but plate configurations can be much larger and more faces. A honeycomb configuration is typically smaller than a plate type, which is an advantage in mobile applications, but has greater pressure drops and clogs more easily. In certain embodiments, the plate substrate is constructed of metal, preferably corrugated metal.
    [0044] In certain embodiments, the invention is a catalyst article made by a process described here, in a particular embodiment, the catalyst article is produced by a process that includes the steps of applying an AEI zeolite composition promoted by metal, preferably as a washable coating, for a substrate such as a layer both before and after at least one additional layer of another exhaust gas treatment composition was applied to the substrate, as one or more catalyst layers on the substrate, the AEI catalyst layer promoted by metal, are arranged in consecutive layers. As used here, the term "consecutive" with respect to the layers of the catalyst on a substrate means that each layer is in contact with its adjacent layers and that the catalyst layers as a whole are arranged one above the other on the substrate.
    [0045] In certain embodiments, the metal-promoted AEI catalyst is arranged on the substrate as a first layer and other composition, such as an oxidation catalyst, reduction catalyst, capture component, or NOx storage component, is arranged on the substrate as a second layer. In other embodiments, the metal-promoted AEI catalyst is disposed on the substrate as a second layer and other composition, such as as an oxidation catalyst, reduction catalyst, capture component, or NOx storage component, is disposed in the substrate as a first layer. As used here, the terms “first layer” and “second layer” are used to describe the relative positions of the catalyst layers in the catalyst article with respect to the normal direction of exhaust gas flowing through, in addition to, and / or over the catalyst article . Under normal exhaust gas flow conditions, 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 a top layer that is applied over the second layer as a consecutive series of sublayers. In such embodiments, the exhaust gas penetrates (and thus contacts) the first layer, before contacting the second layer, and subsequently returns through the first layer to leave the catalyst component. In other embodiments, the first layer is a first zone arranged on a portion upstream of the substrate and the second layer is arranged on the substrate as a second zone, where the second zone is downstream of the first.
    [0046] In another embodiment, the catalyst article is produced by a process that includes the steps of applying a metal-promoted AEI zeolite catalyst composition, preferably as a washable coating, to a substrate as a first zone, and subsequently applying at least at least one additional composition for treating an exhaust gas for the substrate as a second zone, wherein at least a portion of the first zone is downstream of the second zone. Alternatively, the metal-promoted AEI zeolite catalyst composition can be applied to the substrate in a second zone that is downstream of a first zone containing the additional composition. Examples of additional compositions include oxidation catalysts, reduction catalysts, capture components (for example, for sulfur, water, etc.), or NOx storage components.
    [0047] To reduce the amount of space required for an exhaust system, individual exhaust components in certain modes are designed to perform more than one function. For example, the application of an SCR catalyst to a substrate wall flow filter instead of a flow through substrate serves to reduce the overall size of an exhaust treatment system by allowing a substrate to serve two functions, namely reducing catalytically the concentration of NOx in the exhaust gas and mechanically removing soot from the exhaust gas. Appropriately, in certain embodiments, the substrate is a honeycomb flow filter or partial filter. Wall drain filters are similar with honeycomb substrates flowing through the fact that they contain a plurality of adjacent parallel channels. However, the channels of flow-through honeycomb substrates are open at both ends, where the channels of the wall flow substrates have a capped end, where the limitation of the end occurs at opposite ends of adjacent channels in an alternating pattern. Alternating capped ends of channels prevent gas from entering the substrate inlet face from the straight flow through the channel and existing. Instead, the exhaust gas enters the front of the substrate and travels to about half of the channels where it is forced through the channel walls before entering the second half of the channels and exiting the back face of the substrate.
    [0048] The substrate wall has a porosity and pore size that is permeable to gas, but traps a larger portion of particulate matter, such as soot, from the gas when the gas passes through the wall. Preferred wall drainage 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 from 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 particles of similar size and to particulate concentrations typically found in conventional diesel exhaust gas. For example, diesel exhaust particulates can vary in size from 0.05 micron to 2.5 micron. Thus, efficiency can be based on this range or a sub-range, such as 0.1 to 0.25 micron, 0.25 to 1.25 micron, or 1.25 to 2.5 micron.
    [0049] Porosity is a measure of the percentage of empty space in a porous substrate and is related to back pressure in an exhaust system: in general, the lower the porosity, the higher the back pressure. Preferably, the porous substrate has a porosity of about 30 to about 80%, for example, about 40 to about 75%, about 40 to about 65%, or from about 50 to about 60 %.
    [0050] The pore interconnectivity, measured as a percentage of the total void volume of the substrate, is the degree to which the pores, void, and / or channels, are joined to form continuous paths through a porous substrate, that is, from the input face to the output face. In contrast to pore interconnectivity is the sum of closed pore volume and the volume of pores that have a conduit for only one of the substrate surfaces. Preferably, the porous substrate has a pore volume interconnectivity of at least about 30%, more preferably at least about 40%.
    [0051] The average pore size of the porous substrate is also important for filtration. The average pore size can be determined by any acceptable means, including mercury porosity. The average pore size of the porous substrate must be large enough to promote low back pressure, while providing adequate efficiency for any of the substrate alone, by promoting a layer of soot cake on the substrate surface. , or a combination of both. Preferred porous substrates have an average pore size of about 10 to about 40 pm, for example, about 20 to about 30 pm, about 10 to about 25 pm, about 10 to about 20 pm, about from 20 to about 25 pm, about 10 to about 15 pm, and from about 15 to about 20 pm.
    [0052] In general, the production of an extruded solid body containing the metal-promoted AEI catalyst involves mixing with the AEI zeolite and the promoting metal (both separately and together as a metal exchange zeolite), a binder, a Optional organic viscosity enhancing compound for a homogeneous paste that is then added to a binder / matrix component or a precursor to it and optionally one or more of stabilized ceria, and inorganic fibers. The mixture is compacted in a kneading or mixing device or in an extruder. The mixtures have organic additives such as binders, pore builders, plasticizers, surfactants, lubricants, dispersants as processing aids to improve humidification and therefore produce 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 calcination of the extruded solid body. A metal-promoted AEI zeolite catalyst can also be by washable coating or otherwise applied to the extruded solid body as one or more sublayers that reside on the surface or penetrate completely or partially into the extruded solid body. Alternatively, a metal-promoted AEI zeolite can be added to the paste prior to extrusion.
    [0053] Extruded solid bodies containing AEI zeolites promoted by metal according to the present invention generally comprise a unitary structure in the form of a honeycomb having uniformly sized parallel channels extending from a first end to a second end of it. Channel walls defining the channels are porous. Typically, an external "skin" surrounds a plurality of channels of the extruded solid body. The extruded solid body can be formed from any desired cross section, such as circular, square or oval. 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 at a second downstream end to form a wall flow filter. Typically, the arrangement of the blocked channels at the first upstream end looks like an on-board checker with a similar arrangement of blocked and open downstream channel ends.
    [0054] The binder / matrix component is preferably selected from the group consisting of cordierite, nitrides, carbides, borides, intermetallic, lithium aluminosilicate, a spinel, an optionally doped alumina, a source of silica, titania, zirconia, titania - zirconia, zirconia and mixtures of any two or more of them. The paste may optionally contain inorganic reinforcing fibers selected from the group consisting of carbon fibers, glass fibers, metal fibers, boron fibers, alumina fibers, silica fibers, silica - alumina fibers, carbide fibers silicon, potassium titanate fibers, aluminum borate fibers and ceramic fibers.
    [0055] The alumina binder / matrix component is preferably gamma alumina, but it can be any other transition alumina, i.e., alpha alumina, beta alumina, chi alumina, eta alumina, rho alumina, kappa alumina, theta alumina, delta alumina, beta lanthanum alumina and mixtures of any two or more such transition alumines. It is preferred that the alumina is doped with at least one element other than aluminum to increase the thermal stability of the alumina. Suitable alumina dopants include silicon, zirconium, barium, lanthanides and mixtures of any two or more thereof. Suitable lanthanide dopants include La, Ce, Nd, Pr, Gd and mixtures of any two or more thereof.
    [0056] 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 them. From this list, silica can be SiCE in this way, feldspar, mullite, silica - alumina, silica - magnesia, silica - zirconia, silica - thorium, silica - biliary, silica - titania, silica - alumina - ternary zirconia, silica - alumina - ternary magnesia, silica - magnesia - ternary zirconia, silica - ternary alumina - mixtures of any two or more of them.
    [0057] Preferably, the metal-promoted AEI zeolite is dispersed over, and preferably equally throughout, the entire extruded catalyst body.
    [0058] Where any of the above extruded solid bodies are made in a wall drain filter, the pore of the wall drain filter can be from 30 to 80%, such as from 40 to 70%. Porosity and pore volume and pore radius can be measured, for example, using mercury intrusion porosimetry.
    [0059] The metal-promoted AEI catalyst described here can promote the reaction of a reducer, 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 (that is, an SCR catalyst). Examples of such reducers include hydrocarbons (for example, C3 to C6 hydrocarbons) and nitrogen reducers such as ammonia and hydrazine ammonia or any suitable ammonia precursor, such as urea ((NH2) 2CO), ammonium carbonate, ammonium carbamate, hydrogen ammonium carbonate or ammonium formate.
    [0060] The metal-promoted AEI catalyst described here can also promote ammonia oxidation. Thus, in another embodiment, the catalyst can be formulated to favor oxidation of ammonia with oxygen, particularly an ammonia concentration typically found downstream of an SCR catalyst (for example, ammonia oxidation catalyst (AMOX), such as a ammonia leak catalyst (ASC)). In certain embodiments, the metal-promoted AEI zeolite catalyst is arranged as a top layer over an underlying oxidative layer, wherein the underlying layer comprises a platinum group metal catalyst (PGM) or a non-PGM catalyst. Preferably, the catalyst component in the underlying layer is arranged on a high surface sound support, including but not limited to alumina.
    [0061] In yet another modality, an SCR and AMOX operations are carried out in series, in which both processes use a catalyst comprising the metal-promoted AEI zeolite described here, and in which the SCR process occurs upstream of the process of AMOX. For example, an SCR formulation of the catalyst can be arranged on the inlet side of a filter and an AMOX formulation of the catalyst can be arranged on the outlet side of the filter.
    [0062] Appropriately, a method is provided for the reduction of NOx compounds or the oxidation of NH3 in a gas, which comprises contacting the gas with a catalyst composition described here for the catalytic reduction of NOx compounds for a sufficient time to reduce the level of NOx and / or NH3 compounds in the gas. In certain embodiments, a catalyst article is provided having an ammonia leak catalyst disposed downstream of the selective catalytic reduction (SCR) catalyst. In such embodiments, the ammonia leak catalyst oxidizes at least a portion of any nitrogen reducer that is not consumed by the selective catalytic reduction process. For example, in certain embodiments, the ammonia leak 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, in certain other embodiments, the ammonia leak is disposed at the downstream end of a flow-through substrate and an SCR catalyst is disposed at the upstream end of the flow-through substrate. In other embodiments, the ammonia leak catalyst and SCR catalyst are arranged on separate bricks within the exhaust system. These separate bricks can be adjacent to, and be in contact with each other or separated by a specific distance, provided that they are in fluid communication with each other and provided that the SCR catalyst brick is disposed upstream of the leakage catalyst brick ammonia.
    [0063] In certain modalities, the SCR and / or the AMOX process is carried out at a temperature of at least 100 ° C. In another embodiment, the processes take place at a temperature from 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 light and heavy-duty diesel engine that is equipped with an exhaust system comprising (optionally catalyzed) diesel particulate filters that are regenerated actively, for example, injecting hydrocarbon into the exhaust system upstream of the filter, where the zeolite catalyst for use in the present invention is located downstream of the filter.
    [0064] According to another aspect of the invention, a method is provided for the reduction of NOX compounds and / or NH3 oxidation in a gas, which comprises contacting the gas with a catalyst described here for a time sufficient to reduce the level of NOX compounds in the gas. Methods of the present invention may comprise one or more of the following steps: (a) accumulating and / or burning soot that is in contact with the entry of a catalytic filter; (b) introducing a nitrogen reducing agent into the exhaust gas stream before contacting the catalytic filter, preferably without the intervention of catalytic steps involving the NOx treatment and the reducer; (c) generating NH3 by a NOx adsorber catalyst or poor NOx trap, and preferably using such NH3 as a reducer in a downstream SCR reaction; (d) contacting the exhaust gas stream with 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 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 flow SCR catalyst devices through the presence of a reducing agent to reduce the NOx concentration in the exhaust gas; and (f) contacting the exhaust gas with an ammonia leak catalyst, preferably downstream of the SCR catalyst to oxidize most, if not all, of the ammonia before emitting the exhaust gas to the atmosphere or passing the gas exhaust through a recirculation cycle before the exhaust gas enters / re-enters the engine.
    [0065] In another embodiment, 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 adsorbent catalyst (NAC), a poor NOx trap ( LNT), or a NOX storage / reduction catalyst (NSRC), arranged upstream of the SCR catalyst, for example, the SCR catalyst of the present invention arranged in a wall flow filter. NAC components useful in the present invention include a catalyst combination of a base material (such as alkali metal, alkaline earth metal or a rare earth metal, including alkali metal oxides, alkaline earth metal oxides, and combinations thereof), 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 at about 357 (10) to about 7140 g / m3 (200 g / ft3), such as 714 to 2,142 g / m3 (20 to 60 g / ft3). Alternatively, the precious metal of the catalyst is characterized by the average concentration which can be from about 40 to about 100 grams / ft3.
    [0066] Under certain conditions, during periodically rich regeneration events, NH3 can be generated on a NOx adsorbing catalyst. The SCR catalyst downstream of the NOx adsorbing catalyst can improve the overall NOx reduction efficiency of the system. 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 escapes through the NAC catalyst during poor operating conditions normal.
    [0067] The method for treating exhaust gas as described here can be carried out on an exhaust gas derived from a combustion process, such as from an internal combustion engine (either mobile or stationary), a gas turbine and coal or oil-based power plants. The method can also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, furnaces, the chemical processing industry, coke ovens, municipal waste plants and incinerators, etc. In a particular embodiment, the method is used to treat exhaust gas from a low-combustion vehicle internal combustion engine, such as a diesel engine, a low-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
    [0068] In certain aspects, the invention is a system for treating exhaust gas generated by the combustion process, such as from an internal combustion engine (either mobile or stationary), a gas turbine, coal or power plants oil based, and the like. Such systems include a catalyst article comprising the metal-promoted AEI zeolite described herein and at least one additional component to treat the exhaust gas, wherein the catalyst article and at least one additional component are designed to function as a coherent unit.
    [0069] In certain embodiments, the system comprises a catalyst article comprising an AEI zeolite promoted by metal described here, a conduit for directing an exhaust gas flow, a source of nitrogen reducer disposed upstream of the catalyst article. The system can include a controller for measuring nitrogen reducer for exhaust gas flow only when it is determined that the zeolite catalyst is capable of catalyzing NOx reduction at one or above a desired efficiency, such as above 100 ° C, above 150 ° C or above 175 ° C. The measurement of the nitrogen reducer can be arranged such that 60% to 200% of the theoretical ammonia is present in the exhaust gas that enters the SCR catalyst calculated in 1: 1 NH3 / NO and 4: 3 NH3 / NO2.
    [0070] In another embodiment, the system comprises an oxidation catalyst (for example, a diesel oxidation catalyst (DOC)) to oxidize nitrogen monoxide in the exhaust gas to nitrogen dioxide may be located upstream of a measurement of the nitrogen reducer for the exhaust gas. In one embodiment, the oxidation catalyst is adapted to produce a gas stream that enters the SCR zeolite catalyst having a NO to NO2 ratio from about 4: 1 to about 1: 3 by volume, for example , at an exhaust gas temperature at the entrance of the oxidation catalyst from 250 ° C to 450 ° C. The oxidation catalyst can include at least one platinum group metal (or some combination thereof), such as platinum, palladium, or rhodium, coated in a substrate-flow monolith. 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 washable high surface area coating component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, silica, non-zeolite alumina, ceria, zirconia, titania or a mixed oxide or composite containing both ceria and zirconia.
    [0071] In an additional 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 drain filter. Where the filter is catalyzed, for example, with an oxidation catalyst of the type discussed above, preferably the nitrogen reducer measuring point is located between the filter and the zeolite catalyst. Alternatively, if the filter is not catalyzed, the means for measuring the nitrogen reducer can be located between the oxidation catalyst and the filter. EXAMPLES Example 1 - Synthesis of AEI zeolite (SAR = 22)
    [0072] A composition (molar) reaction gel of 60 parts SiOo, 1.2 parts AI2O3, 13.41 parts Na2Ü, 9.5 parts N, N-diethyl-2,6-dimethylpiperidinium hydroxide (22 , 23% by weight solution), and 2721 parts H2O was prepared as follows: About 130.6 grams of a silica source (30% by weight of SiO2) were changed to a 1 liter stainless steel autoclave with the agitator set to spin at 300rpm. About 341.4 g of NaOH IN were mixed in a beaker with 98.3 g of the model. About 7.6 g of ammonium exchange zeolite Y was added to this mixture. The mixture was stirred at room temperature for 10 to 15 min before being added to the colloidal silica in the autoclave. The autoclave was sealed and mixing continued, at room temperature, for another 10 minutes before being heated to 135 ° C. The temperature was maintained for 12 days then the autoclave was cooled to room temperature, the discharged product then filtered, washed with demineralized water and dried at 110 ° C overnight.
    [0073] The resulting product was analyzed by powder X-ray powder diffraction and found to be a highly crystalline AEI type zeolite. The XRD standard for this material is shown in Figure 1.
    [0074] A portion of the material was then activated by conventional ion exchange and calcination methods. The sample was first calcined by heating the sample, in air, from room temperature to 110 ° C to 2 ° C per minute and maintained at that temperature for 10 hours then raised to 450 ° C to 5 ° C per minute and maintained at that temperature for 16 hours followed by being heated to 550 ° C, at 5 ° C per minute, and kept at that temperature for a period of 16 hours before being cooled to room temperature. The ion exchange was carried out by contacting the calcined zeolite, at room temperature, with a 1M solution of ammonium chloride solution using 10cc solution per gram of calcined zeolite. After one hour, the stirring was stopped, the zeolite was allowed to rest and the supernatant was siphoned. The procedure was repeated using a fresh batch of ammonium chloride solution following which the zeolite was filtered, washed with demineralized water and then dried at 110 ° C overnight to generate the NH4-AEI zeolite.
    [0075] To convert this material to H-AEI, the material was calcined by heating, in air, up to 150 ° C at 2 ° C per minute then held at 150 ° C for 10 hours before being raised to 450 ° C at 5 ° C per minute and maintained at that temperature for 16 hours. XRF analysis of the material showed a composition SAR of 22. Example 2 - Synthesis of AEI zeolite (SAR = 20)
    [0076] A reaction gel was prepared by a similar method and using reagents similar to those as described in Example 1 above except that the model was a 22.23% by weight solution. In this case the reaction gel had a (molar) composition: 60 parts of SiO2, 1.21 parts of AI2O3, 15.0 parts of NazO, 9.5 parts of model, and 2721 parts of H2O. The reaction was carried out in a 1.5 L autoclave with agitation at 300 rpm. The reaction was carried out at 135 ° C for 8 days before being cooled to room temperature, discharged from the autoclave and filtered, washed and dried at 110 ° C overnight.
    [0077] The material was then activated in a manner like that described in Example 1 resulting in an H-AEI zeolite that was shown by XRD to be highly crystalline and by XRF to have a SAR of 20. Comparative Example 1- Synthesis of AEI zeolite (SAR = 14)
    [0078] A composition (molar) reaction gel having 60 parts of SiO2, 1.704 parts of AI2O3, 15.7 parts of Na2Ü, 9.5 parts of model (N hydroxide, N-diethyl-2,6-dimethylpiperidinium (19.34% w / w solution), and 2721 parts of H2O was prepared as follows: About 123.9 g of a silica source (30% by weight of SiO2) was loaded into a stainless steel autoclave 1 L and with the agitator set to rotate at 300rpm. About 399.65 g of NaOH IN were mixed in a beaker with 113.09 g of the model. To this mixture was added 10.7 g of ammonium exchange zeolite Y. The mixture was stirred at room temperature for approximately 10 min before being added to the colloidal silica in the autoclave. The autoclave was sealed and mixing continued, at room temperature, for another 10 minutes before being heated to 135 oC. The temperature was maintained for approximately 7 days then the autoclave was cooled to room temperature, the discharged product then filtered, washed with demineralized water and dried at 110 ° C overnight.
    [0079] The resulting product was analyzed by powder X-ray powder diffraction and found to be quite an AEI-type zeolite. XRF analysis showed the product to have a SAR of 14.
    [0080] A portion of the material was then activated by conventional ion exchange and calcination methods. The sample was first calcined by heating the sample, in air, from room temperature to 110 ° C at 2 ° C per minute and held at 110 ° C for 10 hours, then raised to 450 ° C at 5 ° C per minute and kept at that temperature for 16 hours followed by being heated to 550 ° C, at 5 ° C per minute, and again kept at that temperature for a period of 16 hours before being cooled to room temperature. The ion exchange was carried out by contacting the calcined zeolite, at room temperature, with a 1M solution of ammonium chloride solution using 10cc solution per gram of calcined zeolite. After one hour, the stirring was stopped, the zeolite was allowed to rest and the supernatant was siphoned. The procedure was repeated using a fresh batch of ammonium chloride solution following which the zeolite was filtered, washed with demineralized water and then dried at 110 ° C overnight to generate NH4-AEI zeolite.
    [0081] To convert this material to H-AEI the material was calcined by heating, in air, up to 150 ° C at 2 ° C per minute then maintained at 150 ° C for 10 hours before being raised to 450 ° C at 5 ° C per minute and maintained at that temperature for 16 hours. The resulting material was highly crystalline, as shown by powder XRD. Comparative Example 2 - Synthesis of AEI zeolite (SAR = 17)
    [0082] A reaction gel was prepared by a similar method as that described in Comparative Example 1 above. In this case the reaction gel had a (molar) composition: 60 parts of SiCh, 1.34 parts of AI2O3, 15.7 parts of Na2Ü, 9.5 parts of model, and 2721 parts of H2O and was prepared using similar reagents except that the model was a 19.34% w / w aqueous solution. The quantities of reagents used were: 128.8 g of silica phone, 8.42 g of zeolite Y, 399.6 g of 1M sodium hydroxide solution, 113 g of N hydroxide model, N-diethyl-2.6 -dimethylpiperidine, and 33.1 g demineralized water.
    [0083] As in Example 1, a 1 L stainless steel autoclave was used with stirring at 300 rpm. Once all the reagents were added, the autoclave was sealed and left under stirring at room temperature for 30 minutes before being heated to 135 ° C and kept at this temperature for 7 days, following which it was cooled to room temperature, discharged from autoclave and filtered, washed and dried at 110 ° C overnight. The material was then activated in a manner as described in Example 1 resulting in an H-AEI zeolite which was shown by XRD to be highly crystalline and by XRF to have a SAR of 17. Comparative Example 3 - Synthesis of AEI zeolite (SAR = 18)
    [0084] A reaction gel was prepared by a similar method and using reagents similar to those as described in Comparative Example 1 above. In this case the reaction gel had a composition (molar): 60 parts of SiO2, 1.34 parts of A12O3, 15.08 parts of Na2O, 9.5 parts of model, and 2721 parts of H2O.
    [0085] The reaction was carried out in the IL autoclave and was reacted at 135 ° C for 7 days before being cooled to room temperature, discharged from the autoclave and filtered, washed and dried at 110 ° C overnight. The material was then activated in a manner as described in Example 1 resulting in an H-AEI zeolite which was shown by XRD to be highly crystalline and by XRF to have an SAR of 18. Example 3 - NOx conversion performance after aging at high temperature
    [0086] A 5 gram sample of AEI (SAR = 22) aluminosilicate powder similar to that described in Example 1 was treated with copper acetate using an incipient impregnation technique to produce a catalyst loaded with 3 weight percent copper. Samples loaded with copper from AEI (SAR 18), AEI (SAR 19), and AEI (SAR 20) were prepared using similar techniques. In addition, a sample loaded with copper of 3 percent by weight of an aluminosilicate having a CHA structure (SAR = 16) and a sample loaded with copper of an aluminosilicate having a CHA structure (SAR = 22) were also prepared using a similar technique.
    [0087] A portion of the material from each catalyst sample was aged hydrothermally at 500 ° C / 4.5% water in air for 2 hours. After aging, the powder samples were loaded separately into a synthetic catalytic activity test reactor (SCAT) and tested using a synthetic diesel exhaust gas mixture (at the inlet) containing the following: 500 ppm NO, 385 ppm NH3, 10% O2, 10% H2O, N2 equilibrium at a spatial speed of 60,000 h1. The NOx conversion performance of each sample was tested over a temperature range. The results of these tests are provided in Figure 2a.
    [0088] Another portion of the material from each catalyst sample described above was aged hydrothermally at 900 ° C / 4.5% water in air for 3 hours. After aging, the powder samples were loaded separately into a synthetic catalytic activity test reactor (SCAT) and tested using a synthetic diesel exhaust gas mixture (at the inlet) containing the following: 500 ppm NO, 385 ppm NH3, 10% O2, 10% H2O, N2 equilibrium at a spatial speed of 60,000 h1. The NOx conversion performance of each sample was tested over a temperature range. The results of these tests are provided in Figure 2b.
    [0089] The results show that the conversion of NOx to an AEI catalyst after aging at high temperature (ie 900 ° C) was significantly better for samples with a SAR of at least 20 compared to samples having a SAR of less than than 20. In addition, a high temperature aged AEI aluminosilicate catalyst having a SAR of at least 20 performed better compared to a high temperature aged CHA aluminosilicate catalyst having a comparable SAR and copper loading. Example 4 - NH3 Conversion Performance after high temperature aging
    [0090] A sample of 5 grams of AEI powder (SAR = 22) similar to that described in Example 1 was treated with copper acetate using an incipient impregnation technique to produce a catalyst loaded with 3 weight percent copper. Samples loaded with copper from AEI (SAR 18), AEI (SAR 19), and AEI (SAR 20) were prepared using similar techniques.
    [0091] A portion of the material from each catalyst sample was aged hydrothermally at 900 ° C / 4.5% water in air for 3 hours. After aging, the powder samples were loaded separately into a synthetic catalytic activity test reactor (SCAT) and tested using a synthetic diesel exhaust gas mixture (at the inlet) containing the following: 500 ppm NO, 385 ppm NH3, 10% O2, 10% H2O, balance N2 at a space speed of 60,000 h1. The NH3 conversion performance of each sample was tested over a temperature range. The results of these tests are provided in Figure 3.
    [0092] The results of this test show a significant improvement in the conversion of NH3 to high temperature aged AEI aluminosilicate catalyst, provided that the catalyst SAR is at least 20. Example 5 - Catalytic performance after rich / poor aging
    [0093] A sample of AEI aluminosilicate powder (SAR = 20) similar to that described in Example 1 was treated with copper acetate using an incipient impregnation technique to produce a catalyst loaded with 3 weight percent copper, CHA samples loaded with 3 weight percent copper (SAR = 26) and BEA aluminosilicates were also prepared using similar techniques.
    [0094] A portion of the material from each catalyst sample was aged hydrothermally at 500 ° C / 4.5% water in air for 2 hours. Another portion of each sample was subjected to alternating poor and rich aging conditions (5 seconds poor / 15 seconds rich) for 12 hours exposing the powder to the following gas compositions at 600 ° C and at a spatial speed of 30,000 h1: Table 1

    [0095] After poor / rich aging, the powder samples were loaded separately into a synthetic catalytic activity test reactor (SCAT) and tested using a synthetic diesel exhaust gas mixture (at the inlet) similar to that described in the Example 3. The NOx and NH3 conversion performance of each sample was tested over a temperature range. The results of these tests are provided in Figure 4a, 4b, and 4c.
    [0096] The data from these tests show that a copper-loaded AEI aluminosilicate catalyst having a SAR of 20 has NOx and NH3 conversion performance that is comparable with a copper-loaded AEI aluminosilicate catalyst having a SAR of 26. Example 6 - AEI aluminosilicate loaded with copper
    [0097] Samples of an AEI aluminosilicate were loaded with copper using an incipient impregnation technique to produce the following fillers: 2.5% by weight of copper, 3.0% by weight of copper, 3.5% by weight of copper, and 4.0 wt% copper. A portion of each of these samples was hydrothermally aged at 500 ° C for 2 hours. Another portion of each sample was aged hydrothermally at 750 ° C for 80 hours. Another portion of each sample was hydrothermally aged at 900 ° C for 2 hours.
    [0098] Each of the samples was tested on SCAT equipment under conditions similar to those described in Example 3. The test indicates that loading copper from about 2.5 to about 3.5 percent by weight produces conversion of Higher NOx at both 200 ° C and 475 ° C.
    权利要求:
    Claims (27)
    [0001]
    1. Catalytic composition to treat an exhaust gas, characterized by the fact that it comprises an aluminosilicate molecular sieve having an AEI structure and a silica to alumina molar ratio of 20 to 30 and 1 to 5 weight percent of a metal promoter, based on the total weight of the molecular sieve material.
    [0002]
    2. Catalyst composition according to claim 1, characterized by the fact that the molecular sieve has a molar ratio of silica to alumina from 20 to 22.
    [0003]
    3. Catalyst composition according to claim 1, characterized by the fact that the molecular sieve has a molar ratio of silica to alumina from 22 to 25.
    [0004]
    4. Catalyst composition according to claim 1, characterized by the fact that the molecular sieve has a molar ratio of silica to alumina from 25 to 30.
    [0005]
    5. Catalyst composition according to claim 1, characterized by the fact that the promoting metal is selected from the group consisting of copper, nickel, zinc, iron, tungsten, molybdenum, cobalt, titanium, zirconium, manganese, chromium, vanadium, niobium, tin, bismuth, antimony, ruthenium, rhodium, palladium, indium, platinum, gold, silver, or combinations of two or more of these.
    [0006]
    6. Catalyst composition according to claim 1, characterized by the fact that the promoting metal is copper, iron, or a combination of copper and iron.
    [0007]
    7. Catalyst composition according to claim 1, characterized by the fact that the promoting metal is copper.
    [0008]
    8. Catalyst composition according to claim 1, characterized by the fact that the promoting metal is iron.
    [0009]
    Catalyst composition according to claim 1, characterized by the fact that copper is present in a load of 2.5 to 3.5 weight percent, based on the total weight of the zeolite material.
    [0010]
    10. Catalyst composition according to claim 1, characterized by the fact that copper is present in a loading of 3.0 to 3.5 weight percent, based on the total weight of the zeolite material.
    [0011]
    11. Catalyst composition according to claim 1, characterized by the fact that the molecular sieve is a physical mixture of AEI and FAU structures, provided that the molecular sieve is at least 90 mol percent of AEI.
    [0012]
    12. Catalyst composition according to claim 10, characterized by the fact that the molecular sieve is at least 99 mol percent of AEI.
    [0013]
    13. Catalytic composition to treat an exhaust gas, characterized by the fact that it comprises: a. an aluminosilicate molecular sieve having an AEI structure and a silica to alumina molar ratio of about 19 to about 30; B. extra frame (PM) promoter metal disposed in and / or inside the molecular sieve, where the promoter metal is present in a PM to aluminum molar ratio of 0.15 to 1.
    [0014]
    Catalyst composition according to claim 13 characterized by the fact that aluminum is structural aluminum.
    [0015]
    Catalyst composition according to claim 1, characterized in that the composition is a washable coating comprising the catalyst.
    [0016]
    16. Method for treating an exhaust gas, characterized in that it comprises: contacting an exhaust gas comprising NOx and a reducer with a catalyst composition as defined in claim 1; selectively reduce at least a portion of NOx to N2 eH2O.
    [0017]
    17. Method according to claim 16, characterized in that the exhaust gas is derived from a low-combustion internal combustion engine.
    [0018]
    18. Method according to claim 16, characterized by the fact that the reducer is NH3.
    [0019]
    19. Method according to claim 18, characterized in that at least a portion of said NH3 is derived from a poor NOx trap (LNT), NAC, or a NOx storage material.
    [0020]
    20. Method according to claim 19, characterized in that said exhaust gas which contacts the catalyst alternates between rich and poor.
    [0021]
    21. Method for treating an exhaust gas, characterized by the fact that it comprises: contacting an exhaust gas comprising a first concentration of NOx and a first concentration of NH3 with a catalyst to produce a partially treated exhaust gas having a second concentration of NOx and a second concentration of NH3, wherein the second concentration of NOx and the second concentration of NH3 is less than the first concentration of NOx and a first concentration of NH3, contacting the partially treated exhaust gas with a catalyst comprising a composition as defined in claim 1 to oxidize at least a portion of NH3 to produce a purified exhaust gas having a third concentration of NH3, wherein the third concentration of NH3 is less than the second concentration of NH3.
    [0022]
    22. Catalyst article to treat an exhaust gas, characterized by the fact that it comprises: a. a catalyst composition as defined in claim 1; B. a substrate with which and / or on which the catalyst is disposed.
    [0023]
    23. Catalyst article according to claim 22, characterized by the fact that the substrate is a monolith flowing through.
    [0024]
    24. Catalyst article according to claim 22, characterized in that the substrate is a wall flow filter.
    [0025]
    25. Catalyst article according to claim 22, characterized in that the catalyst is a washable coating loaded on the substrate.
    [0026]
    26. Catalyst article according to claim 22, characterized by the fact that the substrate is extruded with the catalyst.
    [0027]
    27. System for treating an exhaust gas, characterized by the fact that it comprises: a. a catalyst article as defined in claim 22; B. one or more upstream components selected from a diesel oxidation catalyst, a NOx absorber catalyst, a poor NOx trap, a filter, an NH3 injector, and an SCR catalyst; and c. optionally an ammonia leak catalyst downstream.
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    同族专利:
    公开号 | 公开日
    DE102014103626A1|2014-09-18|
    GB2558467A|2018-07-11|
    US20140271426A1|2014-09-18|
    EP2983819A1|2016-02-17|
    RU2675821C2|2018-12-25|
    US20150238947A1|2015-08-27|
    CN104703694A|2015-06-10|
    KR20150132498A|2015-11-25|
    GB2532342A|2016-05-18|
    US9044744B2|2015-06-02|
    JP2019217500A|2019-12-26|
    GB2532342B|2018-07-18|
    KR102173965B1|2020-11-04|
    KR102264058B1|2021-06-11|
    RU2018143819A|2019-01-29|
    KR20200126432A|2020-11-06|
    GB201518175D0|2015-11-25|
    JP6567431B2|2019-08-28|
    WO2014141200A1|2014-09-18|
    US9597671B2|2017-03-21|
    CN104703694B|2018-12-21|
    CN109590018A|2019-04-09|
    RU2015143212A|2017-04-20|
    JP6797253B2|2020-12-09|
    BR112015022557A2|2017-07-18|
    GB201805773D0|2018-05-23|
    RU2018143819A3|2021-11-16|
    GB2558467B|2019-01-30|
    JP2021049525A|2021-04-01|
    JP2016516565A|2016-06-09|
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    法律状态:
    2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-08-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-29| 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 14/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361792904P| true| 2013-03-15|2013-03-15|
    US61/792,904|2013-03-15|
    PCT/IB2014/059837|WO2014141200A1|2013-03-15|2014-03-14|Catalyst for treating exhaust gas|
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