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    • 专利摘要:
    A novel catalyst for treating NOx in an exhaust gas is provided, wherein the catalyst comprises a metal promoted high SAR zeolite having an AFX backbone.
    公开号:BR112017007017B1
    申请号:R112017007017-0
    申请日:2015-10-06
    公开日:2021-05-18
    发明作者:Joseph Fedeyko；Alejandra RIVAS-CARDONA；Hai-Ying Chen
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    FOUNDATION Field of Invention:
    [001] The present invention relates to catalysts and methods to treat combustion exhaust gases. Description of Related Technique
    [002] Combustion of hydrocarbon-based fuel in engines produces exhaust gases that largely contain relatively benign nitrogen (N2), water vapor (H2O) and carbon dioxide (CO2). But exhaust gases also contain, in relatively small part, harmful and/or toxic substances, such as carbon monoxide (CO) from incomplete combustion, hydrocarbons (HC) from unburned fuel, nitrogen oxides (NOx) from temperatures excessive combustion and particulate matter (mainly soot). To mitigate the environmental impact of waste and exhaust gases released into the atmosphere, it is desirable to eliminate or reduce the amount of unwanted components, preferably through a process that, in turn, does not generate other harmful or toxic substances.
    [003] Typically, exhaust gases from lean-burning gas engines have a net oxidizing effect due to the high proportion of oxygen that is supplied to ensure proper combustion of the hydrocarbon fuel. In such gases, one of the most costly components to remove is NOx, which includes nitric oxide (NO), nitrogen dioxide (NO2) and nitrous oxide (N2O). Reducing NOx to N2 is particularly problematic because exhaust gases contain enough oxygen to favor oxidizing rather than reducing reactions. 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 help of a reducing agent, such as ammonia, into elemental nitrogen (N2) and water. In an SCR process, a gaseous reducing agent, such as ammonia, is added to an exhaust gas stream before contacting the exhaust gas with the SCR catalyst. The reductant is adsorbed onto the catalyst and the NOx reduction reaction occurs when gases pass through or over the catalyzed substrate. The chemical equation for SCR stoichiometric reactions using ammonia is: 4NO + 4NH3 + O2 ^ 4N2 + 6H2O 2NO2 + 4NH3 + O2 ^ 3N2 + 6H2O NO + NO2 + 2NH3 ^ 2N2 + 3H2O
    [004] Zeolites that have an exchanged transition metal are known to be useful as SCR catalysts. Conventional copper exchanged small pore zeolites are particularly useful for achieving high NOx conversion at low temperatures. The use of a zeolite having an AFX backbone has been previously described. However, this zeolite has been reported to result in poor hydrotrothermal stability, particularly at temperatures above 350°C. Therefore, there remains a need for improved SCR catalysts capable of operating effectively as an SCR at temperatures between 350°C and 550°C (a typical exhaust temperature for a diesel engine). The present invention satisfies this need, among others. SUMMARY OF THE INVENTION
    Applicants have found that a molecular sieve with an AFX backbone and a high SAR is useful in treating NOx through a selective catalytic reduction process. For example, AFX zeolites with a SAR of at least 15 demonstrated superior hydrothermal stability and excellent SCR performance, in particular compared to known AFX zeolite catalysts. Furthermore, the AFX zeolites of the present invention produced comparatively less N2O by-product relative to known AFX zeolites.
    [006] Accordingly, in one aspect there is provided an exhaust gas treatment catalyst comprising a metal-loaded zeolite having an AFX backbone and a silica to alumina (SAR) ratio of about 15 to about 50.
    [007] In another aspect of the invention, there is provided a catalyst wash coating comprising a metal loaded zeolite having an AFX backbone and a silica to alumina (SAR) ratio of about 15 to about 50 and one or more binders. selected from alumina, silica, ceria, zirconia, titania and their combinations.
    [008] In another aspect of the invention, there is provided an exhaust gas treatment system comprising (a) a substrate selected from alveolar pass-through monoliths and wall flow filters; and (b) a catalyst coating disposed on and/or within the substrate, wherein the catalyst coating comprises an exhaust gas treatment catalyst comprising a metal-loaded zeolite having an AFX backbone and a silica to alumina ratio ( SAR) from about 15 to about 50.
    [009] In yet another aspect of the invention, there is provided a method for treating an exhaust gas comprising the step of contacting a mixture of an SCR reducer and an exhaust gas containing NOx with a catalyst comprising a metal-laden zeolite having a chain AFX principal and a silica to alumina (SAR) ratio of about 15 to about 50, wherein said contact reduces at least a portion of the NOx to nitrogen and water. BRIEF DESCRIPTION OF THE FIGURES
    [0010] Figure 1 is a graph showing the comparative NOx conversion performance of the present invention; and
    [0011] Figure 2 is a graph showing the comparative generation of N2O by-products of the present invention. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
    [0012] A catalyst, exhaust gas treatment system and method for improving ambient air quality and, in particular, for treating exhaust gas emissions generated by power plants, gas turbines, internal combustion combustion engines, is provided. poor and the like. Exhaust gas emissions are improved, at least in part, by reducing NOx concentrations over a wide range of operating temperatures. NOx conversion is achieved by contacting the exhaust gas with a metal-loaded zeolite catalyst having an AFX backbone.
    [0013] Preferred catalysts comprise a molecular sieve having an AFX backbone as the predominant crystalline phase. As used herein, the term "AFX" refers to a type of AFX backbone as recognized by the INTERNATIONAL ZEOLITE ASSOCIATION (IZA) STRUCTURE COMMISSION. Most of the aluminosilicate zeolite backbone is constructed of alumina and silica, but may include backbone metals other than aluminum (ie metal substituted zeolites). As used herein, the term "metal substituted" in relation to a zeolite means a zeolite backbone having one or more aluminum or silicon backbone atoms replaced by a metal replacement. In contrast, the term "metal exchanged" means a zeolite that has extra backbone or metal ions associated with the backbone structure but not part of the backbone itself. Examples of metal-substituted AFX backbones include those comprising iron and/or copper backbone atoms. Any AFX aluminosilicate isotope is suitable for the present invention.
    Preferably, the primary crystalline phase of the molecular sieve is AFX, although other crystalline phases may also be present. In certain embodiments, the primary crystalline phase comprises at least about 90 percent by weight of AFX, preferably at least about 95 percent by weight of AFX, and even more preferably at least about 98 or at least about 99 per cent. percent by weight of AFX. In certain embodiments, the AFX molecular sieve is substantially free of other crystalline phases and in certain embodiments it is not an intergrowth of two or more main chain types. In other embodiments, the zeolite crystal is an intergrowth of AFX and at least one other main chain phase. By "substantially free" with respect to other crystalline phases, the molecular sieve is meant to contain at least 99 percent by weight of AFX.
    Preferred zeolites have a silica to alumina (SAR) molar ratio of greater than about 15, for example about 15 to about 50, about 20 to about 50, about 20 to about 30, or about from 20 to about 26. The silica to alumina ratio of zeolites can be determined by conventional analysis. This ratio is intended to represent, as closely as possible, the ratio in the rigid atomic backbone of the zeolite crystal and to exclude silicon or aluminum in the binder, or in cationic or other form within the channels. Since it may be difficult to directly measure the silica to alumina ratio of zeolite after it has been combined with a binder material, particularly an alumina binder, these silica to alumina ratios are expressed in terms of the SAR of the zeolite itself, i.e. , before combining the zeolite with the other catalyst components.
    [0016] In addition to the AFX zeolite, the catalyst composition comprises at least one promoter metal disposed on and/or within the zeolite material as extra backbone metals. As used herein, an "extra main chain metal" is one that resides within the molecular sieve and/or on at least a portion of the surface of the molecular sieve, preferably as an ionic species, does not include aluminum and does not include constituent atoms. the backbone of the molecular sieve. Preferably, the presence of the promoter metal(s) facilitates the treatment of exhaust gases, such as a diesel engine exhaust gas, including processes such as NOx reduction, NH3 oxidation and NOx storage.
    [0017] The promoter metal can be any of the recognized catalytically active metals that are used in the catalyst industry to form metal exchanged zeolites, particularly those metals that are known to be catalytically active to treat exhaust gases derived from a combustion process. Metals useful in the NOx reduction and storage processes are particularly preferred. The promoter metal should be broadly interpreted 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 promoter metals is copper. Other preferred promoter metals include iron, particularly in combination with copper.
    [0018] In certain embodiments, the promoter metal is present in the zeolite material at a concentration of from about 0.1 to about 10 percent by weight (% by weight) based on the total weight of the zeolite, e.g. from 0.5% by weight to about 5%, from about 0.5 to about 1% by weight, from about 1 to about 5% by weight, from about 2.5% 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 percent by weight, more preferably about 2.5 to about 3.5 by weight. hundred by weight.
    [0019] In certain embodiments, the promoter metal, such as copper, is present in an amount of from about 80 to about 120 g/ft3 of zeolite loading or wash, including for example about 85 to about 95 g/ ft3, or about 90 to about 95 g/ft3.
    [0020] In certain embodiments, the promoter metal is present in an amount relative to the amount of aluminum in the zeolite, namely the aluminum backbone. As used herein, the promoter metal:aluminum (M:Al) ratio is based on the relative molar amount of promoter metal to Al molar backbone in the corresponding zeolite. In certain embodiments, the catalyst material has an M:Al ratio of about 0.1 to about 1.0, preferably about 0.2 to about 0.5. An M:Al ratio of about 0.2 to about 0.5 is particularly useful when M is copper, and more particularly where M is copper and the SAR of the zeolite is about 20-25.
    [0021] Preferably, the incorporation of Cu takes place during synthesis or after, for example, by ion exchange or impregnation. In one example, a metal-exchanged zeolite is synthesized within an ionic copper mixture. The metal-exchanged zeolite can then be washed, dried and calcined.
    [0022] Generally, ion exchange of the catalytic metal cation into or over the molecular sieve can be carried out at room temperature or at a temperature up to about 80 °C for 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.
    [0023] In certain embodiments, the catalyst composition comprises the combination of at least one promoter metal and at least one alkali or alkaline earth metal, wherein the transition metal(s) and alkali metal(s) or alkaline earth is/are disposed on or within the zeolitic material. The alkali or alkaline earth metal can be selected from sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, or some combination thereof. As used herein, the phrase "alkali or alkaline earth metal" does not mean that alkali metals and alkaline earth metals are used alternatively, but rather that one or more alkali metals may be used alone or in combination with one or more alkaline earth metals, and 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 alkaline 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 an alkali or alkaline earth metal except calcium and potassium. In certain embodiments, the catalyst is essentially free of any alkali or alkaline earth metals except calcium. And, in certain other embodiments, the catalyst is essentially free of any alkali or alkaline earth metals except potassium. As used herein, the term "essentially free" means that the material lacks an appreciable amount of the particular metal. That is, the particular metal is not present in an amount that affects the basic physical and/or chemical properties of the material, particularly with regard to the material's ability to selectively reduce or store NOx.
    [0024] In certain embodiments, the zeolite material has a post-synthesis alkali content of less than 3 percent by weight, more preferably less than 1 percent by weight and even more preferably less than 0.1 percent by weight . Here, post-synthesis alkali content refers to the amount of alkali metal that occurs in the zeolite as a result of synthesis (i.e., alkali derived from the synthesis starting materials) and does not include alkali metal added after synthesis. In certain embodiments, the alkali metal can be added after synthesis to work in combination with the promoter metal.
    [0025] In certain embodiments, the alkali and/or alkaline earth metal (collectively AM) is present in the zeolite material in an amount relative to the amount of promoter metal (M) in the zeolite. Preferably, M and AM are present, respectively, in a molar ratio of from about 15:1 to about 1:1, for example from about 10:1 to about 2:1, about 10:1 to about from 3:1, or about 6:1 to about 4:1, particularly where 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 percent by weight, for example, less than 2 percent by weight or less than 1 percent by weight, based on the weight of the zeolite.
    [0026] In certain embodiments, the relative cumulative amount of promoter metal (M) and alkali 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 main chain aluminum. As used herein, the ratio (M + AM):Al is based on the relative molar amounts of M + AM to molar backbone Al in the corresponding zeolite. In certain embodiments, the catalyzing material has a (M + AM):Al ratio of no more than about 0.6. In certain embodiments, the ratio (M + AM):Al is not greater than 0.5, for example, about 0.05 to about 0.5, about 0.1 to about 0.4, or about from 0.1 to about 0.2.
    [0027] The promoter metal and the alkali/alkaline earth metal can be added to the molecular sieve by any known technique such as ion exchange, impregnation, isomorphic substitution, etc. The promoter metal and alkali or alkaline earth metal can be added to the zeolite material in any order (eg the metal can be exchanged before, after or simultaneously with the alkali or alkaline earth metal), but preferably the alkali metal or alkaline earth is added before or at the same time as the promoter metal, particularly when the alkaline earth metal is calcium and the promoter metal is copper.
    [0028] 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 catalyst material is present at a concentration of at least about 1 percent by weight, based on the total weight of the zeolite. Examples of preferred concentrations include at least about 2.5 percent by weight, at least about 5 percent by weight, at least about 8 percent by weight, at least about 10 percent by weight, about 1 .35 to about 13.5 percent by weight, about 2.7 to about 13.5 percent by weight, 2.7 to about 8.1 percent by weight, about 2 to about 4 percent by weight, about 2 to about 9.5 percent by weight, and about 5 to about 9.5 percent by weight, based on the total weight of the zeolite. In certain embodiments, the concentration of cerium in the catalyst material is from about 50 to about 550 g/ft3 . Other Ce ranges include: above 100 g/ft3, above 3333 from 200 g/ft, above 300 g/ft, above 400 g/ft, above 500 g/ft, from about 75 to about 350 g/ft3, from about 100 to About 300 g/ft3, and from about 100 to about 250 g/ft3.
    [0029] In certain embodiments, the concentration of Ce exceeds the theoretical maximum amount available for exchange in the metal-promoted zeolite. Consequently, in some embodiments, Ce is present in more than one form, such as Ce ions, monomeric cerium, oligomeric cerium and combinations thereof, provided that said oligomeric cerium has an average crystal size of less than 5 µm, for example less than about 10 nm to about 1 µm, about 100 nm to about 1 µm, about 500 nm to about 1 µm, about 10 to about 500 nm, about 100 to about 500 nm and about 10 at about 100 nm. As used herein, the term "monomeric cerium" means CeO2 as individual molecules or moieties which reside freely on and/or in the zeolite or weakly bond to the zeolite. As used herein, the term "oligomeric cerium" means nanocrystalline CeO2 which resides freely on and/or in the zeolite or weakly bound to the zeolite.
    [0030] Catalysts of the present invention are applicable to heterogeneous catalytic reaction systems (i.e., solid catalyst in contact with a gaseous reactant). To improve contact surface area, mechanical stability and/or fluid flow characteristics, catalysts can be placed on and/or within a substrate, preferably a porous substrate. In certain embodiments, a wash coat containing the catalyst is applied to an inert substrate, such as a corrugated metal plate or cordierite hollow brick. Alternatively, the catalyst is kneaded together with other components such as fillers, binders and reinforcing agents into an extrudable paste which is then extruded through a die to form a hollow brick. Accordingly, in certain embodiments there is provided a catalyst article comprising a metal-promoted AFX zeolite catalyst described herein coated and/or incorporated into a substrate.
    [0031] Certain aspects of the invention provide a catalytic wash coat. The wash coat comprising the AFX 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 of these.
    [0032] In certain aspects, the invention is a catalyst composition comprising AFX aluminosilicate molecular sieve crystals having an average crystal size (i.e., individual crystals including twin crystals) greater than about 0.5 µm, preferably between about 0.1 and about 15 µm, such as about 0.5 to about 5 µm, about 0.7 to about 1.5 µm, about 1 to about 5 µm, or about 1 µm to about 10 µm, particularly for catalysts that are free or substantially free of halogens such as fluorine. Crystal size is the length of the longest diagonal of the three-dimensional crystal. Direct measurement of crystal size can be performed using microscopy methods such as SEM and TEM. For example, SEM measurement involves examining the morphology of materials at high magnifications (typically 1000x to 10,000x). The SEM method can be performed by distributing a representative portion of the zeolite powder onto a suitable support such that the individual particles are reasonably evenly spread across the field of view at a magnification of 1000 x 10,000 x. From this population, a statistically significant sample of random individual crystals (eg 50 - 200) is examined and the largest diagonal of the individual crystals is 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's crystal sizes is calculated.
    [0033] In addition to the average crystal size, catalyst compositions preferably have a majority of crystal sizes greater than about 0.5 µm, preferably between about 0.5 and about 15 µm, such as about 0, 5 to about 5 µm, about 0.7 to about 5 µm, About 1 to about 5 µm, about 1.5 to about 5.0 µm, about 1.5 to about 4, 0 µm, about 2 to about 5 µm, or about 1 µm to about 10 µm. Preferably, the first and third quartile of sample crystal sizes is greater than about 0.5 µm, preferably between about 0.5 and about 15 µm, such as about 0.5 to about 5 µm , about 0.7 to about 5 µm, about 1 to about 5 µm, about 1.5 to about 5.0 µm, about 1.5 to about 4.0 µm, about 2 to about 5 µm, or about 1 µm to about 10 µm.
    [0034] In certain embodiments, AFX crystals are milled to adjust the particle size of the composition. In other modalities, AFX crystals are not milled.
    [0035] In certain aspects, the catalyst is a metal-promoted AFX zeolite 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 µm, such as about 0.5 to 5 µm, or 0.5 to 1.5 µm, particularly when such catalyst is free or substantially free of halogens, such as fluorine. Preferred promoter metals for such a catalyst include copper and iron.
    [0036] High SAR AFX zeolites of the present invention can be synthesized using an organic template such as 1,3-bis (1-adamantyl) imidazolium hydroxide. Such catalysts demonstrate high hydrothermal durability and also produce high NOx conversions when used as SCR catalysts. In certain embodiments, the AFX zeolite is not SSZ-16 and the catalyst composition is substantially free of SSZ-16.
    [0037] In certain aspects, the invention is an SCR catalyst comprising two or more catalytic materials disposed in separate zones or formulated as mixtures. For example, in certain aspects, the SCR catalyst comprises a first zone comprising a metal promoted AFX zeolite as defined herein, and a second zone containing a second catalyst such as an oxidation catalyst, a NOx absorber or NOx capture catalyst and/or an SCR catalyst. The first and second zones can be on a single substrate, such as a wall flow filter or a flow cell, or on separate substrates, but are preferably disposed on or within a single substrate unit.
    [0038] 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 AEI. Other small pore molecular sieves include DDR, LEV, ERI, RHO, RTH, SFW, AFT and KFI. Other useful molecular sieves include BEA, MFI, MOR and FER. The molecular sieve of the second catalyst booth 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 of these. Particularly useful metals include Fe and Cu. Other examples of a second catalyst include vanadium catalysts such as V2 O5 supported on silica, titania or alumina and optionally in combination with other metals such as tungsten and/or molybdenum.
    [0039] The first zone can be upstream or downstream of the second zone in relation to the exhaust gas flow. In certain examples, the second catalyst is a second SCR catalyst or oxidation catalyst disposed downstream of the AFX catalyst. The upstream region and the downstream region may correspond to the leading end and the trailing end, respectively, of a pass-through honeycomb substrate, or they may correspond to the inlet and outlet sides, respectively, of a wall-flow filter. The two zones can partially or fully overlap. For partial overlap, the overlapped section will create a third intermediate zone. The two zones can be adjacent to each other, with little or no space between them (ie, less than 0.2 inches). The first and second catalysts can be mixed together and wash-coated as a single catalyst layer or extruded as a homogeneous honeycomb substrate.
    [0040] In certain aspects, the catalyst further comprises a third catalyst material which may also be an oxidation catalyst, a NOx absorber or NOx capture catalyst and/or an SCR catalyst. The AFX catalyst, second catalyst and/or third catalyst can be combined as a mixture, zoned, and/or layered onto a substrate.
    [0041] A wash coat containing the AFX catalyst may include non-catalytic components such as fillers, binders, stabilizers, rheology modifiers and other additives, including one or more of alumina, silica, silica, non-zeolitic alumina, titania, zirconia, ceria. In certain embodiments, the catalyst composition can 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 improve the effectiveness of the catalytic material, for example, increasing its operating temperature range, increasing the catalyst contact surface area, increasing the catalyst's adhesion to a substrate, etc. . The wash coat 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 of preferably <3.5 g/in3, such as <3.0 g/in3. In certain embodiments, the wash coat is applied to a substrate at a load of about 0.8 to 1.0 g/in3, 1.0 to 1.5 g/in3 or 1.5 to 3.0 g/ in3.
    [0042] Two of the most common substrate designs are plate and honeycomb. Preferred substrates, particularly for mobile applications, include flow (through) monoliths that have a so-called honeycomb geometry comprising multiple adjacent parallel channels that are open at both ends and generally extend from the inlet face to the inlet face. substrate output and result in a high surface area/volume ratio. For certain applications, the honeycomb pass monolith preferably has a high cell density, for example about 600 to 1000 cells per square inch, and/or an average inner wall thickness of about 0.18 to 0.35 mm , preferably about 0.20 to 0.25 mm. For certain other applications, the honeycomb pass monolith preferably has a low cell density of about 150 - 750 cells per square inch, more preferably about 200 - 600 cells per square inch. Preferably, the alveolar monoliths are porous. In addition to cordierite, silicon carbide, silicon nitride, ceramic and metal, other materials that can be used for the substrate include aluminum nitride, silicon nitride, aluminum titanate, α-alumina, mullite, eg acicular mullite, polucite, a "thermet" such as Al2OsZFe, Al2O3/Ni or B4CZFe, or composites comprising segments of any two or more of these. 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 higher 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 herein. In a particular embodiment, the catalyst article is produced by a process that includes the steps of applying a metal-promoted AFX zeolite composition, preferably as a wash coat, to a substrate, as a layer either before or after at least an additional layer of another composition, such as a binder or other catalyst to treat exhaust gas, has been applied to the substrate. The one or more layers on the substrate, including the metal-promoted AFX catalyst layer, are arranged in consecutive layers. As used herein, the term "consecutive" with respect to the catalyst layers on a substrate means that each layer is in contact with its adjacent layers and that the catalyst layers as a whole are disposed one on top of the other on the substrate. Each of the consecutive layers can completely or partially overlap its respective adjacent layer.
    [0045] In certain embodiments, the metal-promoted AFX catalyst is disposed on the substrate as a first layer and another composition, such as an oxidation catalyst, a reduction catalyst, a scavenging component, or a NOx storage component , is arranged on the substrate as a second layer. In other embodiments, the metal-promoted AFX catalyst is disposed on the substrate as a second layer and another composition, such as, for example, an oxidation catalyst, a reduction catalyst, a scavenging component, or a NOx storage component. , is arranged on the substrate as a first layer. As used herein, the terms "first layer" and "second layer" are used to describe the relative positions of the catalyst layers in the catalyst article with respect to the normal direction of exhaust gas flow through, past and/or over the catalyst article. Under normal exhaust gas flow conditions, the exhaust gas contacts the first layer before contacting the second layer. In certain embodiments, the second layer is applied to an inert substrate as a bottom layer, and the first layer is top layer which is applied over the second layer as a consecutive series of sub-layers. In such embodiments, exhaust gas penetrates (and therefore contacts) the first layer, before contacting the second layer, and then returns through the first layer to exit the catalyst component. In other embodiments, the first layer is a first region disposed in an upstream portion of the substrate and the second layer is disposed on the substrate as a second region, wherein the second region is downstream of the first.
    [0046] In another embodiment, the catalyst article is produced by a process that includes the steps of applying a metal-promoted AFX zeolite catalyst composition, preferably as a wash coat, to a substrate as a first zone and then applying at least one additional composition to treat an exhaust gas to the substrate as a second zone, wherein at least a portion of the first zone is downstream of the second zone. Alternatively, the metal-promoted AFX 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, scavenging components (eg 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 embodiments are designed to perform more than one function. For example, applying an SCR catalyst to a wall flow filter substrate rather than a through substrate serves to reduce the overall size of an exhaust treatment system, allowing one substrate to serve two functions, namely the catalytic reduction of the NOx concentration in the exhaust gas and the mechanical removal of soot from the exhaust gas. Consequently, in certain embodiments, the substrate is a honeycomb wall flow filter or partial filter. Wall flux filters are similar to alveolar flux substrates in that they contain a plurality of adjacent parallel channels. However, the flow-through honeycomb substrate channels are open at both ends, while the wall flow substrate channels have a covered end, where the covering occurs at opposite ends of adjacent channels in an alternating pattern. Covering alternate ends of channels prevents gas entering the substrate inlet face from flowing directly through the channel and out. 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 rear face of the substrate.
    [0048] The substrate wall has a porosity and pore size that is permeable to gas, but traps a major portion of the particulate matter, such as soot, from the gas as the gas passes through the wall. Preferred wall flux substrates are high efficiency filters. Wall flow filters for use with the present invention preferably have an efficiency of at least 70%, at least about 75%, at least about 80% or at least about 90%. In certain embodiments, the efficiency will be about 75 to about 99%, about 75 to about 90%, about 80 to about 90%, or about 85 to about 95%. Here, efficiency is relative to soot and other similarly sized particles, and particulate concentrations typically found in conventional diesel exhaust gas. For example, particles in diesel exhaust can range in size from 0.05 microns to 2.5 microns. Thus, efficiency can be based on this range or on a sub-range such as 0.1 to 0.25 microns, 0.25 to 1.25 microns or 1.25 to 2.5 microns.
    [0049] Porosity is a measure of the percentage of empty space in a porous substrate and is related to the back pressure in an exhaust system: generally, the smaller the porosity, the greater the back pressure. Preferably, the porous substrate has a porosity of about 30 to about 80%, for example, about 40 to about 75%, about 40 to about 65%, or about 50 to about 60%.
    [0050] Pore interconnectivity, measured as a percentage of the total substrate void volume, is the degree to which pores, voids and/or channels are connected to form continuous paths through a porous substrate, i.e., the input face to output face. In contrast to pore interconnectivity it is the sum of the closed pore volume and the pore volume that has a conduit for only one of the substrate surfaces. Preferably, the porous substrate has a pore interconnect volume 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. Average pore size can be determined by any acceptable means, including mercury porosimetry. The average pore size of the porous substrate should be of a sufficiently high value to promote low back pressure while providing adequate efficiency either by the substrate itself or by promoting a layer of soot cake on the substrate surface, or by a combination of both. Preferred porous substrates have an average pore size of about 10 to about 40 µm, for example, about 20 to about 30 µm, about 10 to about 25 µm, about 10 to about 20 µm, about 20 to about 25 µm, about 10 to about 15 µm, and about 15 to about 20 µm.
    [0052] In general, the production of an extruded solid body containing the metal-promoted AFX catalyst involves mixing the AFX zeolite and the promoter metal (separately or together, as a metal-exchanged zeolite), a binder, a compound an optional organic viscosity-increasing slurry which is then added to a binder/matrix component or a precursor thereof and, optionally, to one or more of stabilized cerium, and inorganic fibers. The mixture is compacted in a mixing or kneading apparatus or in an extruder. The blends have organic additives such as binders, pore builders, plasticizers, surfactants, lubricants, dispersants as well as processing aids to increase wetting 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 calcinations of the extruded solid body. A metal-promoted AFX zeolite catalyst may also be wash-coated, or otherwise applied to the extruded solid body as one or more sublayers that reside on the surface or fully or partially penetrate the extruded solid body. Alternatively, a metal-promoted AFX zeolite can be added to the slurry prior to extrusion.
    [0053] Extruded solid bodies containing metal-promoted AFX zeolites according to the present invention generally comprise a unitary main chain in the form of a honeycomb, having uniformly sized and parallel channels extending from a first end to a second end of the same. The channel walls that define the channels are porous. Typically, an outer "skin" involves a plurality of extruded solid body channels. The extruded solid body can be formed from any desired cross section, such as circular, square or oval. 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 blocked channels at the first upstream end resembles a checker board 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, intermetallics, lithium aluminum silicate, spinel, optionally doped alumina, a source of silica, titania, zirconia, titania-zirconia, zirconium and mixtures of two or more of them. The slurry 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.
    The alumina binder/matrix component is preferably gamma alumina, but may be any other transitional 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 of these transitional aluminas. It is preferred that the alumina be doped with at least one non-aluminium element to increase the thermal stability of the alumina. Suitable alumina dopants include silicon, zirconium, barium, lanthanides and mixtures of any two or more of these. Suitable lanthanide dopants include La, Ce, Nd, Pr, Gd and mixtures of any two or more of these.
    [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 these. In this list, silica can be SiO2 as such, feldspar, mullite, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium, silica-berylium, silica-titania, silica-alumina-ternary zirconia, alumina-magnesia, silica - ternary magnesia-zirconia, ternary silica-alumina-torium and mixtures of any two or more of these.
    [0057] Preferably, the metal-promoted AFX zeolite is dispersed throughout, and preferably evenly throughout the entire extruded catalyst body.
    [0058] When any of the above extruded solids are made into a wall flow filter, the porosity of the wall flow filter can be 30-80%, such as 40-70%. Porosity and pore volume and pore radius can be measured, for example, using mercury intrusion porosimetry
    [0059] The metal-promoted AFX catalyst described here can promote the reaction of a reductant, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N2) and water (H2O). Thus, in one embodiment, the catalyst can be formulated to favor the reduction of nitrogen oxides with a reducer (ie, an SCR catalyst). Examples of such reductants include hydrocarbons (eg C3-C6 hydrocarbons) and nitrogen reductants such as ammonia and ammonia hydrazine or any suitable ammonia precursor such as urea ((NH2)2CO), ammonium carbonate, ammonium carbamate, hydrogen carbonate of ammonium or ammonium formate.
    [0060] The metal-promoted AFX catalyst described herein can also promote the oxidation of ammonia. Thus, in another embodiment, the catalyst can be formulated to favor the oxidation of ammonia with oxygen, particularly ammonia concentrations typically found downstream of an SCR catalyst (eg, an ammonia oxidation catalyst (AMOX) such as a catalyst ammonia slip (ASC)). In certain embodiments, the metal promoted AFX zeolite catalyst is disposed as an upper layer over a lower oxidizing layer, wherein the lower layer comprises a platinum group metal (PGM) catalyst or a non-PGM catalyst. Preferably, the catalyst component in the lower layer is disposed on a high surface area support, including but not limited to alumina.
    [0061] In yet another modality, SCR and AMOX operations are performed in series, in which both processes use a catalyst comprising the metal-promoted AFX zeolite described herein, and in which the SCR process occurs upstream of the AMOX process. For example, an SCR catalyst formulation may be disposed on the inlet side of a filter and an AMOX catalyst formulation may be disposed on the outlet side of the filter.
    [0062] Accordingly, there is provided a method for the reduction of NOx compounds or oxidation of NH3 in a gas, which comprises contacting the gas with a catalyst composition described herein for the catalytic reduction of NOx compounds for a sufficient 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 slip catalyst disposed downstream of a selective catalytic reduction (SCR) catalyst. In such embodiments, the ammonia slip catalyst oxidizes at least a portion of any nitrogenous reductant that is not consumed by the selective catalytic reduction process. For example, in certain embodiments, an ammonia slip catalyst is disposed on the outlet side of a wall flow filter and an SCR catalyst is disposed on the upstream side of a filter. In certain other embodiments, an ammonia slip catalyst is disposed at the downstream end of a pass-through substrate and an SCR catalyst is disposed at the upstream end of the pass substrate. In other embodiments, the ammonia slip catalyst and SCR catalyst are arranged on separate bricks within the exhaust system. These separate bricks can be adjacent and in contact with each other or separated by a specific distance, as long as they are in fluid communication with each other and as long as the SCR catalyst brick is disposed upstream of the ammonia slip catalyst brick .
    [0063] In certain embodiments, the SCR and/or AMOX process is carried out at a temperature of at least 100°C. In another embodiment, the process(es) take place at a temperature between about 150°C and about 750°C. In a particular embodiment, the temperature range is between about 175 and about 550°C. In another embodiment, the temperature range is 175 to 400°C. In yet another embodiment, the temperature range is from 450 to 900°C, preferably from 500 to 750°C, from 500 to 650°C, from 450 to 550°C, or from 650 to 850°C. Modalities using temperatures above 450 °C are particularly useful for treating exhaust gases from a heavy and light diesel engine that is equipped with an exhaust system comprising diesel particulate filters (optionally catalyzed) that are actively regenerated by example, by injecting hydrocarbon into the exhaust system upstream of the filter, wherein the zeolite catalyst for use in the present invention is located downstream of the filter.
    [0064] According to another aspect of the invention, there is provided a method for reducing NOX compounds and/or oxidizing NH3 in a gas, which comprises contacting the gas with a catalyst described herein for a time sufficient to reduce the level of NOX compounds in the gas. The methods of the present invention may comprise one or more of the following steps: (a) accumulating and/or burning soot that is in contact with the inlet of a catalytic filter; (b) introducing a nitrogenous reducing agent into the exhaust gas stream before contacting the catalytic filter, preferably without any catalytic steps involving the treatment of NOx and the reducer; (c) generating NH3 over a NOx absorbing catalyst or a poor NOx uptake and preferably using such NH3 as a reductant in a downstream SCR reaction; (d) contacting the exhaust gas stream with a DOC to oxidize soluble hydrocarbon-based organic fraction (SOF) and/or carbon monoxide to CO2 and/or oxidize NO to NO2, which in turn can be used to oxidize particulate material in a particulate filter; and/or reduce particulate matter (PM) in the exhaust gases; (e) contacting the exhaust gases with one or more SCR flow 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 ammonia slip catalyst, preferably downstream of the SCR catalyst to oxidize most, if not all, of the ammonia before emitting the exhaust gas to atmosphere or passing the gas exhaust through a recirculation loop before exhaust gas enters/re-enters the engine.
    [0065] In another modality, at least a portion of the nitrogen-based reducer, in particular NH3, can be provided for consumption in the SCR process, by a NOX absorbing catalyst (NAC), a lean NOX scavenger (LNT) or a storage/reduction (NSRC) catalyst disposed upstream of the SCR catalyst, e.g., an SCR catalyst of the present invention disposed in a wall flow filter. NAC components useful in the present invention include a catalyst combination of a basic material (such as an 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 reduction catalyst component such as rhodium. Specific types of base material useful in NAC include cesium oxide, potassium oxide, magnesium oxide, sodium oxide, calcium oxide, strontium oxide, barium oxide and combinations thereof. The precious metal is preferably present at about 10 to about 200 g/ft3, such as 20 to 60 g/ft3. Alternatively, the precious metal of the catalyst is characterized by an average concentration which can be from about 40 to about 100 grams/ft 3 .
    [0066] Under certain conditions, during the periodically rich regeneration events, NH3 can be generated over a NOx adsorber catalyst. The SCR catalyst downstream of the NOx adsorber catalyst can improve the overall NOx reduction efficiency of the system. In the combined system, the SCR catalyst is capable of storing 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 normal lean operating conditions. .
    [0067] The method for treating exhaust gas as described herein can be performed on an exhaust gas derived from a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine and power plants that burn coal or oil. The method can also be used to treat gases from industrial processes such as refining, refinery heaters and boilers, furnaces, chemical processing industry, coke ovens, municipal waste facilities and incinerators, etc. In a particular embodiment, the method is used to treat exhaust gas from a lean-burn vehicular internal combustion engine, such as a diesel engine, a lean-burn gasoline engine, or an engine powered by liquid petroleum gas or gas. Natural.
    [0068] In certain aspects, the invention is a system for treating exhaust gas generated by a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine, coal-burning power plants or oil, and the like. Such systems include a catalytic article comprising the metal-promoted AFX zeolite described herein, and at least one additional component to treat the exhaust gas, wherein the catalytic article and at least one additional component are designed to function as a coherent unit.
    [0069] In certain embodiments, the system comprises a catalytic article comprising a metal-promoted AFX zeolite described herein, a conduit for directing a flowing exhaust gas, a nitrogen reductant source disposed upstream of the catalytic article. The system may include a controller for dosing the nitrogen reducer in the exhaust gas which flows only when it is determined that the zeolite catalyst is capable of catalyzing the NOx reduction at or above a desired efficiency thereof, such as above 100 °C, above 150°C, or above 175°C. The dosage of the nitrogen reducer can be arranged such that 60% to 200% of theoretical ammonia is present in the exhaust gas entering the SCR catalyst calculated as 1:1 NH3/NO and 4:3 NH3/NO2.
    [0070] In another embodiment, the system comprises an oxidation catalyst (e.g., a diesel oxidation catalyst (DOC)) to oxidize nitrogen monoxide in the exhaust gas to nitrogen dioxide may be located upstream of a point of dosage of the nitrogen reducer inside the exhaust gas. In one embodiment, the oxidation catalyst is adapted to produce a gas stream entering the SCR zeolite catalyst having a NO to NO2 ratio of from about 4:1 to about 1:3 by volume, e.g., a temperature of exhaust gas at the inlet of the oxidation catalyst from 250°C to 450°C. The oxidation catalyst can include at least one platinum group metal (or some combination thereof), such as platinum, palladium or rhodium, coated onto a pass-through substrate monolith. In one embodiment at least one platinum group metal is platinum, palladium or a combination of both platinum and palladium. The platinum group metal can be supported on a high surface area wash coating component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, non-zeolitic alumina silica, ceria, zirconia, titanium oxide, or an oxide mixed or composite containing both ceria and zirconia.
    [0071] In another embodiment, a suitable filter substrate is located between the oxidation catalyst and the SCR catalyst. Filter substrates can be selected from any of those mentioned above, for example wall flow filters. Where the filter is catalyzed, for example, with an oxidation catalyst of the type discussed above, preferably the nitrogen reducing dose point is located between the filter and the zeolite catalyst. Alternatively, if the filter is not catalyzed, the means for dosing the nitrogen reductant may be located between the oxidation catalyst and the filter. EXAMPLES Example 1: Preparation of high SAR AFX zeolite.
    [0072] Sodium silicate (silica source) and zeolite Y (alumina source) were reacted in the presence of 1,3-bis(1-adamantyl) imidazolium hydroxide (organic molding agent) at about 145 °C during 7-10 days. The resulting crystalline material was separated from the mother liquor and then washed and dried. Analysis confirmed that the product contained high purity AFX zeolite having a SAR of about 22. Example 2: Catalytic Performance
    [0073] A copper promoted AFX zeolite having a SAR of 22 was hydrothermally aged at 800°C for 5 hours. For comparison, a conventional AFX zeolite sample having a SAR of 8 was loaded with a similar amount of copper and then hydrothermally aged at 800°C for 5 hours under similar conditions.
    [0074] The sample and the comparative sample were exposed to a simulated diesel exhaust gas stream under similar conditions and tested for their respective performance in the conversion of NOx and in the generation of N2O by-product. As shown in Figures 1 and 2, the Cu/AFX high SAR catalyst had a higher NOx conversion than the conventional AFX material. Furthermore, the Cu/AFX high SAR catalyst had lower N2O by-product generation compared to the conventional AFX material. These surprising and unexpected results demonstrate that the high SAR AFX catalyst of the present invention is superior to a conventional AFX zeolite for SCR reactions.
    权利要求:
    Claims (15)
    [0001]
    1. Catalyst for exhaust gas treatment, characterized in that it comprises a Cu-loaded zeolite having an AFX backbone and a silica to alumina (SAR) ratio of 15 to 50, wherein the zeolite has a post-alkaline content. synthesis of less than 3% by weight, and wherein the zeolite has an average crystal size of 0.1 to 15 microns.
    [0002]
    2. Catalyst according to claim 1, characterized in that the zeolite loaded with Cu contains from 0.1 to 8% by weight of Cu.
    [0003]
    3. Catalyst according to claim 2, characterized in that the Cu-loaded zeolite contains from 0.5 to 5 percent by weight of Cu.
    [0004]
    4. Catalyst according to claim 3, characterized in that Cu is non-main chain copper.
    [0005]
    5. Catalyst according to claim 1, characterized in that the SAR is from 20 to 40.
    [0006]
    6. Catalyst according to claim 1, characterized in that the SAR is from 20 to 30.
    [0007]
    7. Catalyst according to claim 1, characterized in that most of the crystalline phase of the zeolite has an AFX main chain.
    [0008]
    8. Catalyst according to claim 1, characterized in that the zeolite has an average particle size of 0.1 to 15 microns.
    [0009]
    9. Catalyst according to claim 1, characterized in that the catalyst is effective to selectively promote the reaction of NH3 with NOx to form nitrogen and water.
    [0010]
    10. Catalyst according to claim 1, characterized in that the catalyst is extruded into an alveolar monolith.
    [0011]
    11. Coating composition catalyst, characterized in that it comprises the catalyst defined in claim 1 and one or more binders selected from alumina, silica, ceria, zirconia, titanium and combinations thereof.
    [0012]
    12. Exhaust gas treatment system, characterized in that it comprises: a. a substrate selected from pass-through alveolar monoliths and wall flow filters; and b. a catalyst coating disposed on and/or within the substrate, wherein the catalyst coating comprises a catalyst composition defined in claim 1.
    [0013]
    13. Exhaust gas treatment system according to claim 12, characterized in that the system further comprises an oxidation catalyst downstream of at least a portion of the catalyst coating.
    [0014]
    14. Exhaust gas treatment system according to claim 12, characterized in that the system additionally comprises a NOx capture or NOx absorption catalyst disposed upstream of the catalyst coating.
    [0015]
    15. Method for treating an exhaust gas, characterized in that it comprises the step of contacting a mixture of an SCR reducer and an exhaust gas containing NOx with a catalyst comprising a Cu-loaded zeolite having an AFX backbone and a silica to alumina (SAR) ratio of 15 to 50, wherein the zeolite has a post-synthesis alkaline content of less than 3% by weight, wherein the zeolite has an average crystal size of 0.1 to 15 microns. , and where the contact reduces at least a portion of the NOx to nitrogen and water.
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    同族专利:
    公开号 | 公开日
    JP6615193B2|2019-12-04|
    JP2017536227A|2017-12-07|
    WO2016057456A1|2016-04-14|
    US20160096169A1|2016-04-07|
    RU2723648C2|2020-06-17|
    GB2548261B|2020-07-15|
    KR20170067818A|2017-06-16|
    EP3204157A1|2017-08-16|
    CN107107043A|2017-08-29|
    BR112017007017A2|2018-01-16|
    RU2017115769A3|2019-01-31|
    GB201707172D0|2017-06-21|
    GB2535821A|2016-08-31|
    DE102015116926A1|2016-04-07|
    GB201517652D0|2015-11-18|
    RU2017115769A|2018-11-14|
    GB2548261A|2017-09-13|
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    法律状态:
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| 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 06/10/2015, OBSERVADAS AS CONDICOES LEGAIS. |
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