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    • 专利摘要:
    CATALYST ARTICLE, METHOD TO REDUCE NOx IN AN EXHAUST GAS, AND ENGINE EXHAUST GAS TREATMENT SYSTEM. An SCR-coated filter article having different SCR catalyst compositions arranged on a wall flow filter substrate is provided in zones that are arranged in series with respect to the substrate inlet and outlet faces. Also provided is a method of reducing the back pressure and shedding of ammonia that involves the use of such SCR-coated filter articles.
    公开号:BR112014002129B1
    申请号:R112014002129-5
    申请日:2012-07-27
    公开日:2020-12-29
    发明作者:Guy Richard Chandler；Keith Anthony Flanagan；Paul Richard Phillips
    申请人:Johnson Matthey Limited Company；
    IPC主号:
    专利说明:

    FUNDAMENTALS A.) Field of use:
    [0001] The present invention relates to articles and methods that are usable for treating exhaust gases generated during hydrocarbon combustion. More particularly, the invention relates to catalytic filters to reduce NOx and soot in exhaust gas streams, such as those generated by diesel engines. B.) Description of related technique:
    [0002] Exhaust gas produced by road vehicles in the United States currently contributes about a third of air pollution by producing polluting fog and smoke. Efforts to reduce pollution include using more fuel-efficient engines, such as diesel engines compared to gasoline engines, and improved exhaust gas treatment systems.
    [0003] Most combustion exhaust gases contain relatively healthy nitrogen (N2), water vapor (H2O), and carbon dioxide (CO2), but the exhaust gas also contains harmful and / or toxic substances in a relatively small part, such as incomplete combustion carbon monoxide (CO), unburned fuel hydrocarbons (HC), nitrogen oxides (NOx) from excessive combustion temperatures, and particulate matter (mostly soot). One of the heaviest components of vehicle exhaust gas is NOx, which includes nitric oxide (NO), nitrogen dioxide (NO2), and nitrous oxide (N2O). NOx production is particularly problematic for clean-burning engines, such as diesel engines. In order to remedy the environmental impact of NOx in the exhaust gas, it is desirable to eliminate these undesirable components, preferably by a process that does not generate other harmful or toxic substances.
    [0004] Exhaust gas from diesel engines tends to have more soot compared to gasoline engines. Soot emissions can be remedied by passing the soot-containing exhaust gas through a particulate filter. However, the accumulation of soot particles in the filter can cause an undesirable increase in exhaust system back pressure during operation, thus decreasing efficiency. To regenerate the filter, the accumulated carbon-based soot must be removed from the filter, for example, by periodically burning the soot by passive or active oxidation. Such a technique involves catalytic oxidation of soot at low temperatures. For example, US Patent No. 4,902,487 teaches the use of NO2 as an oxidizer serving to effectively burn soot collected at low temperatures. It has also been suggested that the performance of a catalytic soot filter could be improved by superimposing different oxidation catalysts on a wall-mounted soot filter (US Patent Publication No. 2009/0137386) or zoning the oxidation catalyst using different catalyst concentrations (EP Patent No. 1,859,864).
    [0005] For clean-burning exhaust gas, such as diesel exhaust gas, reduction reactions are generally difficult to achieve. However, a method for converting NOx into a diesel exhaust gas into healthier substances is commonly referred to as selective catalytic reduction (SCR). An SCR process involves the conversion of NOx, in the presence of a catalyst and with the aid of a reducing agent, to elemental nitrogen (N2) and water. In an SCR process, a gaseous reducer, typically anhydrous ammonia, aqueous ammonia, or urea, is added to a standard exhaust gas before contacting the catalyst. The reducer is absorbed into a catalyst and the NOx reduction reaction occurs as the gases pass through or over the catalyzed substrate. The chemical equation for a stoichiometric reaction using either anhydrous or aqueous ammonia for an SCR process is: 4NO + 4NH3 + 3O2 ^ 4N2 + 6H2O 2NO2 + 4NH3 + 3O2 ^ 3N2 + 6H2O NO + NO2 + 2NH3 ^ 2N2 + 3H2O
    [0006] Known SCR catalysts include zeolites or other molecular sieves arranged on or within a monolithic substrate. Examples of such molecular sieves include materials having a basket structure (for example, SSZ-13 and SAPO-34), beta structure, mordenite structure (for example, ZSM-5), and the like. To improve the catalytic performance of the material and hydrothermal stability, molecular sieves for SCR applications often include exchange of metal ions that are loosely attached to the molecular sieve structure.
    [0007] Since SCR catalysts generally serve as heterogeneous catalysts (i.e., solid catalyst in contact with a gas and / or liquid reagent), the catalysts are generally supported by a substrate. Preferred substrates for use in mobile applications include flow monoliths having a so-called honeycomb geometry that comprises multiple adjacent, parallel channels, which are open at both ends and generally extend from the entrance face to the exit face of the substrate. Each channel typically has a square, round, hexagonal, or triangular cross section. Catalytic material is applied to the substrate typically as a "reactive coating type" catalytic material or other coating that can be incorporated into and / or the substrate walls.
    [0008] Exhaust systems containing multiple components, or multiple SCR catalysts, are known. For example, US Patent No. 7,767,176 describes an exhaust system having two substrates, preferably non-filtering honeycombs, arranged in series where each substrate contains a SCRO catalyst. Zoning of non-filtering flow substrates with SCR catalysts followed by oxidation catalysts is also known (for example, US 5,516,497).
    [0009] To reduce the amount of space required for an exhaust system, it is desirable to design individual exhaust components to perform more than one function. For example, applying an SCR catalyst to a wall flow filter substrate instead of a flow substrate serves to reduce the overall size of an exhaust treatment system by allowing a substrate to serve two functions, ie catalytic conversion of NOx by the SCR catalyst and soot removal by the filter. US patent publication 2010/0180580 describes an SCR catalyst that can be applied to an alveolar substrate in the form of a wall flow filter. Wall flow filters are similar to honeycomb flow substrates in that they contain a plurality of adjacent, parallel channels. However, the channels of alveolar flow substrates are open at both ends, whereas the flow substrate channels per wall have a capped end, where the buffering occurs at opposite ends of adjacent channels in an alternating pattern. Capping the alternating ends of channels prevents gas from entering the substrate inlet face flowing directly through the channel and exiting. In contrast, the exhaust gas enters the front of the substrate and travels through half the channels where it is forced through the channel walls before entering the second half of the channels and exiting back to the substrate face.
    [00010] A wall flow filter having an SCR (SCR coated filter) and an oxidation catalyst, wherein the SCR catalyst is disposed upstream of an oxidation catalyst, is described in Patent Application GB 1003784.4, which is incorporated herein in its entirety by reference. However, the need remains for improved SCR-coated filter systems having good catalytic performance while also having minimal back pressure. SUMMARY OF THE INVENTION
    [00011] Applicants have surprisingly found that the functionality of an SCR-coated filter component in an exhaust system can be improved by providing two or more catalytic zones that are sequentially arranged on the filter substrate with respect to the direction of global gas flow through the substrate. For example, compared to a filter substrate in which an SCR catalyst is homogeneously loaded in the axial direction, a zone-delimited filter described here leads to a reduction in the back pressure created by exhaust gas flow through the substrate. Such zones can be created by loading a front portion of a filter substrate (relative to the global gas flow direction) with a first SCR catalyst that is thermally stable at high temperatures and a rear portion with SCR catalyst having different performance, or by loading the portions front and rear of the filter with an SCR catalyst composition having the same catalytic components, but carrying a relatively higher concentration of one or more of the components in the front. This reduction in back pressure is surprising because it occurs when the concentration or type of catalyst is varied along the axial direction of the filter instead of the direction in which the gas contacts the filter catalyst (s) (i.e., permeation direction through the filter walls). That is, in a wall flow filter, gas flows into the substrate through a filter inlet face and the substrate outlet through the filter outlet face, thereby creating a global gas flow direction that is parallel to the largest substrate axis. However, the gas contacts the catalytic component as it passes through the filter walls that are in a direction that is orthogonal to the substrate axis. It has been found that varying the catalyst concentration in such an axial direction reduces back pressure compared to a catalyst concentration that is a homogeneous distribution along the axis.
    [00012] Accordingly, an aspect of the invention provides a catalyst article comprising (a) a flow monolith per wall having an inlet face end and an outlet face and a gas flow axis from said inlet face for said exit face; (b) a first SCR catalyst composition comprising a molecular sieve material in a first sieve concentration and a metal exchanged in a first metal concentration, wherein said first SCR catalyst is arranged in a first zone; and (c) a second SCR catalyst composition comprising said molecular sieve material at a concentration that is at least 20% less than said first sieve concentration, and said metal exchanged at said first metal concentration, wherein said second SCR catalyst it is arranged in a second zone; wherein said first zone and second zone are arranged within a portion of said flow monolith per wall and in earnest along said axis, and wherein said first zone is arranged proximal to said entry face, and said second zone is arranged proximal to said exit face.
    [00013] According to another aspect of the invention, there is provided a catalyst article comprising (a) a flow monolith per wall having an inlet face end and an outlet face and a gas flow axis from said entry face for said exit face; (b) a first SCR catalyst composition comprising a molecular sieve material in a first sieve concentration and a metal exchanged in a first metal concentration, wherein said first SCR catalyst is arranged in a first zone; and (c) a second SCR catalyst composition comprising said molecular sieve material at a concentration that is at least 20% less than said first sieve concentration, and said metal exchanged at a concentration that is at least 20% less than said first sieve concentration. metal concentration, in which said second SCR catalyst is disposed in a second zone; wherein said first zone and second zone are arranged within a portion of said flow monolith per wall and in earnest along said axis, and wherein said first zone is arranged proximal to said entry face, and said second zone is arranged proximal to said exit face.
    [00014] According to another aspect of the invention, there is provided a catalyst article comprising (a) a flow monolith per wall having an inlet face end and an outlet face and a gas flow axis from said entry face for said exit face; (b) a first SCR catalyst composition comprising a molecular sieve material in a first sieve concentration and a metal exchanged in a first metal concentration, wherein said first SCR catalyst is arranged in a first zone; and (c) a second SCR catalyst composition comprising said molecular sieve material at said first sieve concentration, and said metal exchanged at a concentration that is at least 20% less than said first metal concentration, wherein said second SCR catalyst it is arranged in a second zone; wherein said first zone and second zone are arranged within a portion of said flow monolith per wall and in earnest along said axis, and wherein said first zone is arranged proximal to said entry face, and said second zone is arranged proximal to said exit face.
    [00015] According to another aspect of the invention, there is provided a catalyst article comprising (a) a flow monolith per wall having an inlet face end and an outlet face and a gas flow axis from said entry face for said exit face; (b) a first SCR catalyst composition comprising a molecular sieve material and an exchanged metal, wherein said first SCR catalyst is arranged in a first zone; and (c) a second SCR catalyst composition comprising a second molecular sieve material and a second exchanged metal, wherein said second SCR catalyst is disposed in a second zone, wherein said first most thermally stable molecular sieve relative to said second sieve molecular, wherein said first zone and second zone are arranged within a portion of said flow monolith per wall and in series along said axis, and wherein said first zone is arranged proximal to said entrance face, and said second zone is arranged proximal to said exit face.
    [00016] In accordance with another aspect of the invention, a method is provided to reduce ammonia shedding comprising (a) operating a diesel engine under conditions to generate an exhaust gas supply stream comprising NOx and soot and having the temperature of about 250 to 550 ° C and having a spatial speed of about 20,000 to about 120,000 / hour; (b) injecting a reducer in said supply current to create an intermediate current; and (c) passing said intermediate stream through a catalyst article according to an SCR-coated filter as described herein to produce a purified exhaust gas stream having a reduced soot and NOx concentration relative to said feed stream; wherein said purified exhaust gas stream has no ammonia or an ammonia concentration that is less than an amount of ammonia that would be present if the intermediate stream was passed through an SCR-coated filter as described here except that the SCR catalyst is homogeneously distributed with respect to the overall gas flow direction.
    [00017] According to another aspect of the invention, a method is provided to reduce back pressure in an exhaust treatment system comprising (a) operating a diesel engine under conditions to generate the exhaust gas stream comprising NOx and soot and having a temperature of about 250 to 550 ° C and having a spatial speed of about 20,000 to about 120,000 / hour; (b) injecting a reducer in said stream to create an intermediate stream; and (c) passing said intermediate stream through the catalyst article according to an SCR-coated filter described as herein to produce a purified exhaust gas stream having a reduced soot and NOx concentration relative to said supply stream, in that said passage step produces a gas flow resistance that is less than the amount of gas flow resistance that would be produced if the intermediate current was passed through a catalyst article similar to the SCR-coated filter as described here, but having an SCR catalyst homogeneously distributed with respect to the overall gas flow direction.
    [00018] According to another aspect of the invention, a method is provided to reduce NOx in an exhaust gas comprising contacting the gas with a catalyst article according to an SCR-coated filter as described here for a time and temperature sufficient to reduce the level of NOx compounds in the gas.
    [00019] According to yet another aspect of the invention, an engine exhaust gas treatment system is provided comprising (a) a catalyst article according to an SCR-coated filter as described herein; and (b) a source of ammonia or urea upstream of said catalyst article. BRIEF DESCRIPTION OF THE DRAWINGS
    [00020] Figures 1A and 1B show views of a portion of a conventional wall flow filter substrate;
    [00021] Figures 2A and 2B show cross-sectional views of a portion of a wall flow filter unit having catalyst bounded in zones according to an embodiment of the invention;
    [00022] Figure 3 shows cross-sectional views of a portion of a wall flow filter unit having catalyst bounded in zones according to another embodiment of the invention;
    [00023] Figure 4 shows cross-sectional views of a portion of a wall flow filter unit having catalyst bounded in zones according to another embodiment of the invention;
    [00024] Figure 5 is a graph comparing back pressure data for a wall flow filter unit having zone-bound catalyst according to an embodiment of the invention and a catalyst homogeneously distributed in a wall flow filter; and
    [00025] Figure 6 is a graph comparing cumulative NOx mass data for a wall flow filter unit having zone-bound catalyst according to an embodiment of the invention and a catalyst homogeneously distributed in a wall flow filter . DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
    [00026] The present invention provides a catalytic filtration device that effectively and economically removes NOx and particulates from an exhaust gas stream, such as from a clean-burning engine (eg, diesel engine). In a preferred embodiment, a wall flow filter substrate having a plurality of catalytic zones is provided. The zones are created by incorporating different SCR catalysts and / or different concentrations of the same SCR catalyst components in separate portions of the substrate walls. Preferably, the zones are arranged in series with respect to the overall direction of exhaust gas flow through the filter substrate.
    [00027] Turning to Figures 1a and 1b, views of a portion of a conventional wall flow filter substrate 10 for use in vehicle exhaust systems are shown. The wall flow substrate has multiple channels 11 that are approximately parallel to each other and extend from an inlet face 12 of the substrate to an outlet face 13 of the substrate along an axis 17 of gas flow through the substrate (ie, the direction of exhaust gas entering and purified gas leaving). Conventional wall flow filter substrate for diesel engines typically contains 400 - 800 channels, but for simplicity only a few channels are shown in these Figures. The channels are defined by porous walls 15 and each channel has a lid 14 on either the inlet or outlet face of the substrate. The porous walls are also defined by a side 18 upstream and a side 19 downstream, relative to the direction of gas flow through the walls. Wall flow filter substrates for use in vehicle exhaust systems such as these are commercially available from a variety of sources.
    [00028] Figures 2A and 2B show cross-sectional views of a portion of the catalyst article according to an embodiment of the invention. Here, the catalyst article comprises a wall flow filter substrate 10, a first SCR catalyst zone 20 incorporated in a portion of the substrate wall 15 which is close to the inlet face 12, and a second SCR catalyst zone 22 incorporated in another portion of the substrate wall 15 which is close to the outlet face 13. Thus, the first zone and second zone are not necessarily arranged in series with respect to the direction of gas flow through the wall (that is, on the side upstream to the side downstream of the wall). In contrast, the first and second zones are arranged in series with respect to the overall direction of expected exhaust gas flow through the substrate as shown by arrow 28 which is parallel to axis 17.
    [00029] Exhaust gas not treated by the catalytic filter 26 flows into the substrate channels where it contacts the upstream side 18 of a substrate wall 15. During operation of an engine, a differential pressure exists between the inlet and outlet faces of the substrate (greater pressure on the inlet face relative to the outlet face), and thus a differential pressure also exists between the upstream side 18 and the downstream side 19 of the substrate wall 15. This differential pressure, together with the permeable nature of wall gas, allows the exhaust gas 26 flowing in a channel that is open to the entrance face, to pass from the upstream side 18 of a porous wall 15 to the downstream side 19 of that wall, and then into an adjacent channel that is opened to the outlet face of the substrate. The exhaust gas passes through the wall in a direction that is orthogonal to axis 17, i.e., the overall direction of gas flow 28 through the substrate 10.
    [00030] The substrate wall has a porosity and pore size that makes it gas permeable, but collects a larger portion of the particulate material, such as soot, from the gas as the gas passes through the wall. Preferred wall-flow 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 some embodiments, the efficiency will be about 75 to about 99%, about 75 to about 90%, about 80 to about 90%, or about 85 to about 95%. Here, efficiency is relative to soot and other similarly sized particles and to particulate concentrations typically found in conventional diesel exhaust gas. For example, diesel exhaust particulates can vary in size from 0.05 microns to 2.5 microns. Thus, efficiency can be based on this range or a sub-range, such as 0.1 to 0.25 microns, 0.25 to 1.25 microns, or 1.25 to 2.5 microns.
    [00031] During normal operation of the exhaust system, soot and other particles accumulate on the sides upstream of the walls which lead to an increase in back pressure. To alleviate this increase in back pressure, filter substrates are continuously or periodically regenerated by active or passive techniques including burning the soot accumulated by known techniques including the use of an oxidation catalyst.
    [00032] Exhaust gas passing through the porous substrate walls also contacts the SCR catalyst incorporated in the walls, thereby eliminating a greater portion of the NOx components from the exhaust gas. It has been unexpectedly found that zoning SCR catalyst on a wall flow filter substrate of the present invention provides improved back pressure performance with the same or better catalytic performance, particularly NOx reduction performance, relative to the same amount of a similar SCR catalyst which is arranged more evenly from the beginning to the end of the filter wall. The improved performance of this zoned filter is also surprising because the catalytic performance is not dependent on the direction of gas flow through the filter (i.e., the direction of gas flow in contact with the catalytic compositions of the invention), but on the contrary is dependent on the overall flow of exhaust gas through the substrate.
    [00033] SCR-coated filter articles delimited in zones of the present invention also offer improved ammonia storage performance compared to homogeneously loaded SCR-coated filter articles. More particularly, zoning the SCR catalyst according to certain embodiments of the invention as described in greater detail below (for example, increasing the molecular sieve concentration in the zone close to the entrance face relative to the zone close to the exit face) , provides increased ammonia storage capacity in the section of the filter substrate that is likely to heat up quickly during engine operation, while also providing decreased ammonia storage capacity near the outlet face of the filter substrate which reduces the likelihood of detachment of ammonia, particularly when the SCR-coated filter is treating exhaust gas having a high temperature and a high spatial speed.
    [00034] Preferred SCR catalysts for use with the present invention include one or more molecular sieves containing one or more transition metals. The type of molecular sieve suitable for use in the present invention is not particularly limited. However, preferred molecular sieves have a structure type selected from BEA, MFI (e.g., ZSM-5), or small pore molecular sieves such as CHA, ERI, and LEV, as defined by the International Zeolite Association. In certain preferred embodiments, the molecular sieve has a type of small pore structure that has a maximum ring size of eight tetrahedral atoms. Particularly preferred types of small pore structure include CHA, ERI and LEV, more preferably CHA. Where the molecular sieve frame type code is CHA, a CHA isotype frame structure can be selected from the group consisting of, for example, SAPO-34, SSZ-62, and SSZ-13. A molecular sieve having an ERI frame type can be, for example, erionite, ZSM-34 or Linde type T. LEV frame type code isotype frame structures or material type can be, for example, levinite, Nu -3, LZ-132 or ZK-20.
    [00035] In certain preferred embodiments, the molecular sieve is an aluminosilicate or a silico-aluminum-phosphate. Preferred aluminosilicate molecular sieves have a mole ratio of silica to alumina greater than about 10, more preferably about 15 to about 250, more preferably about 20 to about 50, and even more preferably about 25 to about 40. The ratio of silica to alumina from molecular sieves can be determined by conventional analysis. This reason is to represent, as closely as possible, the silica-to-alumina ratio in the atomic structure of the molecular sieve crystal and preferably excludes aluminum in the binder or in cationic or other form within the channels. It will be appreciated that it can be extremely difficult to directly measure the ratio of silica to alumina from the molecular sieve after having been combined with a binder material. Consequently, the silica to alumina ratio was expressed above in terms of the silica to alumina ratio of the original molecular sieve, that is, the molecular sieve used to prepare the catalyst, as measured before combining that molecular sieve with the other catalyst components. .
    [00036] Preferably, the catalyst composition comprises a molecular sieve and at least one additional framework metal to improve the catalytic performance and / or thermal stability of the material. As used herein, an "additional scaffold metal" is one that resides within the molecular sieve and / or on at least a portion of the molecular sieve surface, does not include aluminum, and does not include atoms constituting the molecular sieve structure. The additional framework metal can be added to the molecular sieve using a known technique such as ion exchange, impregnation, isomorphic substitution, etc. Additional framework metals can be any of the recognized catalytically active metals that are used in the catalyst industry to form molecular sieves from exchanged metal. In one embodiment, at least one additional frame metal is used in conjunction with the molecular sieve to increase the performance of the catalyst. Preferred additional framework metals are selected from the group consisting of copper, nickel, zinc, iron, tin, tungsten, cerium, molybdenum, cobalt, bismuth, titanium, zirconium, antimony, manganese, chromium, vanadium, niobium, ruthenium, rhodium, palladium , gold, silver, indium, platinum, iridium, rhenium, and mixtures of these. More preferred additional framework metals include those selected from the group consisting of chromium, cerium, manganese, iron, cobalt, nickel, and copper, and mixtures thereof. Preferably, at least one of the additional framework metals is copper. Other preferred additional framework metals include iron and cerium, particularly in combination with copper. For embodiments in which the aluminosilicate has a CHA framework, the preferred additional framework metal is copper.
    [00037] In one example, a molecular sieve with metal exchange is created by mixing the molecular sieve in a solution containing soluble precursors of the catalytically active metal. The pH of the solution can be adjusted to induce precipitation of the catalytically active cations in or within the molecular sieve structure. For example, in a preferred embodiment the basket is immersed in a solution containing copper nitrate for a sufficient time to allow incorporation of the copper cations of catalytically active substances 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-substituted molecular sieve can then be washed, dried and calcined. When iron or copper is used as the metal cation, the metal content of the catalytic material by weight preferably comprises from about 0.1 to about 15 weight percent, more preferably from about 1 to about 10 percent by weight, and even more preferably about 1 to about 5 weight percent of the molecular sieve material.
    [00038] Generally, ion exchange of the catalytic metal cation in 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 molecular sieve catalytic material is preferably dried at about 100 to 120 ° C overnight and calcined at a temperature of at least about 550 ° C.
    [00039] Preferably, the molecular sieve catalyst is incorporated into the substrate in an amount sufficient to reduce the NOx contained in an exhaust gas stream flowing through the substrate. In some embodiments, at least a portion of the substrate may also contain an oxidation catalyst, such as a platinum group metal (for example, platinum), to oxidize ammonia in the exhaust gas stream or perform other functions such as conversion CO to CO2.
    [00040] Wall flow substrates useful in the present invention can have any shape suitable for use in an exhaust system, provided that the substrate has an entrance face, an exit face, and a length between the entrance and exit faces. output. Examples of suitable shapes include circular cylinders, elliptical cylinders, and prisms. In certain preferred embodiments, the inlet and outlet faces are in parallel planes. However, in other embodiments, the input and output faces are not parallel and the length of the substrate is curved.
    [00041] The substrate preferably contains a plurality of channels that are approximately parallel to each other. The channels are defined by thin porous walls that preferably have a thickness of about 0.005 to about 0.254 cm, preferably about 0.005 and 0.038 cm. The cross-sectional shape of the channels is not particularly limited and can be, for example, square, circular, oval, rectangular, triangular, hexagonal, or the like. Preferably, the substrate contains about 25 to about 750 channels per 6.45 cm2, and more preferably about 100 to about 400 channels per 6.45 cm2.
    [00042] Flow substrates per wall are preferably constructed of one or more materials which include, as a predominant phase, ceramic, glass-ceramic, glass, cermet, metal, oxides, and combinations thereof. Combinations include physical and chemical combinations, for example, mixtures, compounds, or composites. Some materials that are especially suitable for the practice of the present invention although it is to be understood that the invention is not limited to such, are those made of cordierite, mullite, clay, talc, zircon, zirconia, spinel, alumina, silica, borides, aluminosilicates lithium, silica alumina, feldspar, titania, fused silica, nitrides, borides, carbides, for example, silicon carbide, silicon nitride or mixtures thereof. A particularly preferred material is cordierite and silicon carbide.
    [00043] Preferably, the substrate is constructed of a material having a porosity of at least about 50%, more preferably about 50 - 75%, and an average pore size of at least 10 microns.
    [00044] Preferably, the SCR catalyst resides in at least a portion of the pores of the wall, more preferably on the pore surfaces on the filter wall. It is highly preferred that the catalyst in the pores is arranged in a manner that does not clog the pores, which could excessively restrict the flow of exhaust gas through the wall. More than one catalyst can be layered on top of each other in the pores. The catalyst material can also be arranged on the wall to form one or more concentration gradients between the upstream side and the downstream side of the wall. Different catalyst can be loaded on the upstream and corresponding sides downstream of the wall.
    [00045] In one embodiment, the SCR catalyst is zoned as shown in Figure 2A. For this embodiment, the SCR catalyst of the first zone comprises a molecular sieve material loaded with a changed metal. Regarding the SCR catalyst in the first zone, the SCR catalyst in the second zone comprises the same molecular sieve material loaded with the same metal exchange, but the molecular sieve concentration in the SCR catalyst in the second zone is at least 20% (for example , about 20 to about 80%, about 25 to about 75%, about 25 to about 50%, about 30 to about 40%, about 20 to about 30%, about 30 to about 40%, about 50 to about 75%, and about 40 to about 60%) less than the molecular sieve concentration in the SCR catalyst in the first zone, while the concentration of metal exchanged in the SCR catalysts in the first and second zones is about the same. As used here, the term “at least 20% less” does not include 0%. For example, in the first zone, the molecular sieve concentration is preferably about 0.5 to about 2.5 g / in3 (about 30.51 to about 152.56 g / cm3), and the metal concentration exchanged is about 10 to about 120 g / ft3 (about 0.35 to about 4.24 kg / m3), but in the second zone, the molecular sieve concentration is at least 20% less than that of the first zone , while the concentration of exchanged metal is about the same.
    [00046] In another embodiment, the SCR catalyst is zoned as shown in Figure 2A. For this embodiment, the SCR catalyst of the first zone comprises a molecular sieve material loaded with a changed metal. Regarding the SCR catalyst in the first zone, the SCR catalyst in the second zone comprises the same molecular sieve material loaded with the same exchanged metal, but the concentration of the molecular sieve and the concentration of metal exchanged in the SCR catalyst in the second zone is at least 20% (for example, about 20 to about 80%, about 25 to about 75%, about 25 to about 50%, about 30 to about 40%, about 20 to about 30%, about 30 to about 40%, about 50 to about 75%, and about 40 to about 60%) less than the molecular sieve concentration and metal concentration exchanged, respectively, in the SCR catalyst in the first zone. For example, in the first zone, the molecular sieve concentration is preferably about 0.5 to about 2.5 g / in3 (30.51 to about 152.56 kg / m3), and the concentration of exchanged metal is about 10 to about 120 g / ft3 (0.35 to about 4.24 kg / m3), but in the second zone, the molecular sieve concentration and the concentration of metal exchanged is at least 20% lower than that of first zone.
    [00047] In another embodiment, the SCR catalyst is zoned as shown in Figure 2A. For this embodiment, the SCR catalyst of the first zone comprises a molecular sieve material loaded with a changed metal. Regarding the SCR catalyst in the first zone, the SCR catalyst in the second zone comprises the same molecular sieve material loaded with the same exchanged metal, but the concentration of metal exchanged in the SCR catalyst in the second zone is at least 20% (for example, about 20 to about 80%, about 25 to about 75%, about 25 to about 50%, about 30 to about 40%, about 20 to about 30%, about 30 to about 40 %, about 50 to about 75%, and about 40 to about 60%) less than the concentration of metal exchanged in the SCR catalyst in the first zone, while the molecular sieve concentration in the SCR catalysts in the first and second zones is the same. For example, in the first zone, the molecular sieve concentration is preferably about 0.5 to about 2.5 g / in3 (30.51 to about 152.56 kg / m3), and the concentration of exchanged metal is about 10 to about 120 g / ft3 (0.35 to about 4.24 kg / m3), but in the second zone, the concentration of metal exchanged is at least 20% less than that of the first zone, while the concentration molecular sieve is about the same.
    [00048] In another embodiment, the SCR catalyst is zoned as shown in Figure 2A. For this embodiment, the SCR catalyst of the first zone comprises a molecular sieve material loaded with a changed metal. Regarding the SCR catalyst in the first zone, the SCR catalyst in the second zone comprises a different molecular and / or metal sieve. Preferably, the SCR catalyst in the first zone is more thermally stable relative to the SCR catalyst in the second zone. For example, the SCR in the first zone can be 3% copper in a molecular sieve having a CHA framework, and the SCR in the second zone can be 1% iron in a molecular sieve having a CHA framework.
    [00049] In addition to a molecular sieve and with metal exchange, the SCR catalyst composition can comprise other components, such as binders (for example, alumina) and modifiers. In some embodiments, the overall concentration of the SCR catalyst composition in the first zone is about the same as the overall concentration of the SCR catalyst composition in the second zone. In other embodiments, the overall concentration of an SCR catalyst composition in the first zone is greater than the overall concentration of an SCR catalyst composition in the second zone.
    [00050] In some embodiments the first zone and the second zone are adjacent to each other. In other embodiments, the first zone overlaps a portion of the second zone, preferably by less than 25%, and more preferably by less than 10%. In other embodiments, the second zone overlaps a portion of the first zone, preferably by less than 25%, and more preferably by less than 10%. In still other embodiments, the first and second zones are separated by a relatively small section of substrate wall that is either uncoated or coated with an inert substance. Preferably, the small section is less than about 10 percent (for example, about 1 to about 10 percent), and more preferably less than about 5 percent (for example, about 1 to about 5 percent cent) of the channel length.
    [00051] The embodiments shown in Figures 2A and 2B comprise a first catalyst zone and a second catalyst zone each extending about half the length of the channel wall in which they are incorporated. Preferably, the first zone comprises from about 10 to about 90 percent, more preferably about 25 to 75, even more preferably about 40 to 60, the length of the channel in which it is incorporated. Preferably the second zone comprises from about 10 to about 90 percent, more preferably about 25 to 75, even more preferably about 40 to 60, the length of the channel in which it is incorporated.
    [00052] In some embodiments, two or more catalytic zones are incorporated into the substrate. For example, the substrate may comprise three, four, five, six, seven, or eight zones, preferably arranged in series with respect to the axis of global gas flow through the substrate. The number of zones is not particularly limited, but on the contrary it is dependent on the particular application for which the substrate is designed. Figure 3 shows an embodiment of the invention comprising a wall flow substrate 30 having four zones, 31, 32, 33, and 34 arranged in series with respect to the overall gas flow 35 through the substrate. Considering that more than two zones are provided, the zones are preferably arranged to form a concentration gradient with the highest concentration being close to the substrate inlet face and the lowest concentration being close to the substrate outlet face. Preferably, each zone is differentiated from adjacent zones by at least 20 percent in relative concentration of catalyst and / or catalyst component.
    [00053] In some embodiments, two or more different SCR catalysts can be used. Preferably, the SCR catalysts comprise a metal exchange molecular sieve material. The different catalyst may have different molecular sieve material, different exchange metals, or both. Preferably the different SCR catalysts have different thermal stability and preferably the different SCR catalysts are arranged in series with respect to the overall gas flow through the substrate. Preferably the most thermally stable SCR catalyst is disposed close to the inlet face and the least thermally stable is disposed close to the outlet face. In Figure 4, shown is an embodiment of the invention having a more thermally stable SCR 41 catalyst and a less thermally stable SCR 42 catalyst disposed on a wall flow substrate 40, where the more thermally stable SCR 41 catalyst is disposed nearby to the entrance face of the substrate. Applications:
    [00054] The catalytic molecular sieves described here can promote the reaction of a reducer, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N2) and water (H2O) against the competition reaction of oxygen and ammonia. In one embodiment, the catalyst can be formulated in favor of the reduction of nitrogen oxides with ammonia (ie, and SCR Catalyst). In another embodiment, the catalyst can be formulated in favor of oxidation of ammonia with oxygen (i.e., an ammonia oxidation catalyst (AMOX)). In yet another embodiment, an SCR catalyst and an AMOX catalyst are used in series, in which both catalysts comprise the metal containing molecular sieve described here, and in which the SCR catalyst is upstream of the AMOX catalyst. In some embodiments, the AMOX catalyst is arranged as a top layer in an oxidative sublayer, wherein the sublayer comprises a platinum group metal (PGM) catalyst or a non-PGM catalyst.
    [00055] The reducer (also known as a reducing agent) for SCR processes broadly means any compound that promotes the reduction of NOx in an exhaust gas. Examples of reducers useful in the present invention include ammonia, hydrazine or any suitable ammonia precursor, such as urea ((NH2) 2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate, and hydrocarbons such as fuel diesel, and the like. Particularly preferred reducers are based on nitrogen, with ammonia being particularly preferred.
    [00056] According to another aspect of the invention, a method is provided for the reduction of NOx Compounds or NH3 oxidation in a gas, which comprises contacting the gas with a catalyst composition described here for catalytic reduction of NOx compounds by enough time to reduce the level of NOx compounds in the gas. In one embodiment, nitrogen oxides are reduced with the reducing agent at a temperature of at least 100 ° C. In another embodiment, nitrogen oxides are reduced with the reducing agent at a temperature of about 150 to 750 ° C. In a particular embodiment, the temperature range is 175 to 650 ° C. In another embodiment, the temperature range is 175 to 550 ° C. In yet another embodiment, the temperature range is 450 to 750 ° C, preferably 450 to 700 ° C, even more preferably 450 to 650 ° C.
    [00057] In another embodiment, the reduction of nitrogen oxides is carried out in the presence of oxygen. In an alternative embodiment, the reduction of nitrogen oxides is carried out in the absence of oxygen.
    [00058] The method can be carried out on a gas derived from a combustion process, such as an internal combustion engine (whether mobile or stationary), a gas and coal turbine or oil-burning energy installations. The method can also be used to treat industrial gas processes such as refining, refinery heaters and boilers, furnaces, chemical processing industry, coke ovens, municipal refuse plants and incinerators, etc. In a particular embodiment, the method is used to treat exhaust gas from a clean-burning internal combustion engine, such as a diesel engine, a clean-burning gasoline engine or an engine powered by liquid petroleum gas or natural gas.
    [00059] According to another aspect, the invention provides an exhaust system for a clean-burning internal combustion vehicle engine, whose system comprising a duct for effecting a fluent exhaust gas, a source of nitrogen reducer, and a catalytic converter. molecular sieve described here. The system may include means, when in use, to control the measurement means so that the nitrogen reducer is measured in the flowing exhaust gas only when it is determined that the molecular sieve catalyst is capable of catalyzing NOx reduction at or above a desired efficiency, such as above 100 ° C, above 150 ° C or above 175 ° C. The determination by the control means can be assisted by one or more suitable sensor inputs indicative of an engine condition selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass gas flow exhaust system, collector vacuum, ignition time, engine speed, exhaust gas lambda value, the amount of fuel injected into the engine, the position of the exhaust gas recirculation valve (EGR) and thereby the amount EGR and thrust pressure.
    [00060] In a particular embodiment, measurement is controlled in response to the amount of nitrogen oxides in the determined exhaust gas either directly (using a suitable NOx sensor) or indirectly, such as using pre-correlated or stored query tables on maps in the control media - correlating any or more of the above mentioned entries indicative of an engine condition with predicted NOx content of the exhaust gas. The measurement of the nitrogen reducer can be arranged such that 60% to 200% of theoretical ammonia is present in exhaust gas entering the SCR catalyst calculated at 1: 1 NH3 / NO and 4: 3 NH3 / NO2. The control means can comprise a pre-programmed processor such as an electronic control unit (ECU).
    [00061] In another embodiment, an oxidation catalyst to oxidize nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a point of measuring the nitrogen reducer in the exhaust gas. In one embodiment, the oxidation catalyst is adapted to yield a gas stream entering the molecular sieve SCR catalyst having a NO to NO2 ratio of about 4: 1 to about 1: 3 by volume, for example, at an exhaust gas temperature at the oxidation catalyst inlet of 250 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 on a flow monolith substrate. In one embodiment, the at least one platinum group metal is platinum, palladium or a combination of both, platinum and palladium. The platinum group metal can be supported on a high surface area reactive coating type catalytic material component such as alumina, a molecular sieve such as an aluminosilicate, silica, non-zeolite silica, ceria, zirconia, titania or a mixed or composite oxide containing both ceria and zirconia.
    [00062] In another aspect, a clean-burning vehicle engine comprising an exhaust system according to the present invention has been provided. The clean-burning internal combustion engine can be a diesel engine, a clean-burning gasoline engine, or an engine powered by liquid petroleum gas or natural gas. EXAMPLES
    [00063] The following non-limiting examples are given to further illustrate certain aspects of the invention. Example 1: Preparation of homogeneous and coated SCR filter in zones
    [00064] Two commercially available silicon carbide wall flow filters (NGK Insulators Ltd), with cross section 4.02 inches x 7.81 inches (10.2 cm x 19.8 cm) and 6.85 inches (17 , 4 cm) in axial length, having a cell density of 300 cells per 6.45 cm2, channel wall thickness of 0.305 mm, porosity of 52% and average pore size of 23μm were used to investigate the properties of coated filter with SCR coated zone against homogeneously coated SCR coated filter. Both wall flow filters were coated at an overall load of 0.9g / in3 (54.92 kg / m3) with a 'reactive coating' catalytic material comprising a dispersion of copper zeolite (2.5% by weight) copper) and alumina and zirconia binder material (18% of total “reactive coating” type catalytic solids).
    [00065] SCR catalyst was homogeneously coated by (1) applying 15% by weight of solid slurry to a depth sufficient to coat substrate channels along the complete axial length of the substrate from the exit direction. (2) then excess slurry was removed by vacuum, and (3) the filter then dried in air flowing at 100 ° C. Process steps (1) to (3) were repeated for the opposite end of the flow wall filter and the SCR-coated filter was burned at 500 ° C for 1 hour. The final SCR catalyst load was homogeneously distributed at 0.9g / in3 (54.92 kg / m3).
    [00066] The zone-coated SCR-coated filter was prepared by (1) applying 34% by weight of solid slurry to a depth sufficient to coat the substrate channels along with 40% of the substrate axial length of the input direction . (2) then vacuum applied to remove excess reactive coating-like catalytic material, and (3) the filter dried in flowing air at 100 ° C. (4) A 17% slurry of solids then at a depth sufficient to coat the substrate channels along with 60% of the substrate axial length of the exit direction. (5) Vacuum applied to remove excess reactive coating-like catalytic material, followed by (6) the filter dried in air flowing at 100 ° C and burning at 500 ° C for 1 hour. This process resulted in a zone-coated SCR-coated filter, with the front 40% axial length coated for a load of 1.4g / in3 (85.43 kg / m3) and the rear 60% axial length coated for a load 0.56g / in3 (34.17 kg / m3). Example 2: Performance testing
    [00067] The rate of increase of back pressure related to soot loading for each of the Example 1 filters using diesel exhaust gas containing particulate matter was tested using the diesel particulate generator (DPG) and test cell described in European Patete 1850068 Al e manufactured by Cambustion Ltd. That is, an apparatus for generating and collecting particulate material derived from the combustion of a fuel containing liquid carbon, whose apparatus comprising a fuel burner comprising a nozzle, the nozzle of which is housed in a container, whose container comprising a gas inlet and a gas outlet, said gas outlet connecting with a conduit to transport gas from the gas outlet to the atmosphere, means for detecting a gas flow rate through the gas inlet and means for forcing an oxidizing gas flow from the gas inlet through the container, the gas outlet and the flue to the atmosphere, a station to collect particulate material from gas flow through the conduit and means for controlling the flow of gas-means of forcing in response to a gas flow rate detected at the gas inlet, thereby the gas flow rate at the gas inlet is maintained at a desired rate for provide sub-stoichiometric fuel combustion inside the container, in order to promote the formation of particulate material.
    [00068] The filters were adjusted each time in the station with the entrance channels pre-coated by the supplier with a membrane layer arranged to receive exhaust gas containing particulate first. The apparatus was operated with a standard diesel fuel atrium pump containing a maximum of 50 ppm sulfur. The DPG unit was operated with a gas mass flow rate of 250 kg / hour, a particulate generation rate of 10 g / h with a silicon carbide filter in-line particulate filter maintained at about 240 ° C. During the loading of particulate material from each filter, the back pressure was determined by a differential pressure sensor and logged into a computer every 10 seconds.
    [00069] DOC and SCR-coated filter systems using the filters in Example 1 were evaluated on simulated MVEG cycles using 2L 4-cylinder bikes and a transient dynamometer.
    [00070] A 1.25L Pt Pd oven aged with DOC was adjusted upstream of a 2.5L high porosity SiC filter coated with an SCR-coated filter catalyst aged in the engine. A commercially available urea dosing system was used, with urea injection to allow a mixture of 25 cm in length upstream of the SCR-coated filter; minimum dosing temperature was 180C. Repeated MVEG cycles were performed.
    [00071] As can be seen from the data in Figures 5 and 6, the zone-bounded SCR filter according to the present invention offers substantially reduced back pressure compared to an equivalent zone-less SCR-coated filter. In addition, the zone-bound SCR-coated filter provides much improved NOx reduction performance.
    权利要求:
    Claims (11)
    [0001]
    1. Catalyst article, comprising: a. a wall flow monolith (10) having an inlet face (12) and an outlet face (13) and a gas flow shaft (17) from the inlet face (12) to the outlet face ( 13); B. a first SCR catalyst composition comprising a molecular sieve material in a first molecular sieve concentration and a metal exchanged in a first metal concentration, wherein the first SCR catalyst is disposed in a first zone (20); and, c. a second SCR catalyst composition comprising the molecular sieve material at a concentration that is at least 20% less than the first molecular sieve concentration, and comprising the metal exchanged in the first metal concentration, wherein the second SCR catalyst is arranged in a second zone (22); characterized by the fact that the first zone (20) and the second zone (22) are arranged within a portion of the flow monolith per wall (10) and in series along the axis (17), and in which the first zone ( 20) is arranged proximal to the entry face (12), and the second zone (22) is arranged proximal to the exit face (13).
    [0002]
    2. Catalyst article according to claim 1, characterized by the fact that the molecular sieve is a zeolite having a framework selected from the group consisting of BEA, MFI, CHA, ERI, and LEV and the exchanged metal is selected from copper and iron .
    [0003]
    3. Catalyst article according to claim 1 or 2, characterized by the fact that the first sieve concentration is 30.51 to 152.56 kg / m3 (0.5 to 2.5 g / in3).
    [0004]
    4. Catalyst article according to any one of claims 1 to 3, characterized by the fact that the exchanged metal is copper or iron.
    [0005]
    Catalyst article according to any one of claims 1 to 4, characterized in that the first metal concentration is 0.353 to 17.66 kg / m3 (10 to 500 g / foot3).
    [0006]
    Catalyst article according to any one of claims 1 to 5, characterized in that the flow monolith per wall (10) has a pore size of at least 10 micrometers and a porosity of at least 50%.
    [0007]
    Catalyst article according to any one of claims 1 to 6, characterized in that the first zone (20) and the second zone (22) are adjacent.
    [0008]
    Catalyst article according to claim 7, characterized by the fact that the first zone (20) is arranged 25 to 75% of the distance between the entrance face (12) and the exit face (13).
    [0009]
    Catalyst article according to any one of claims 1 to 6, characterized in that it additionally comprises one or more intermediate zones arranged between the first and second zones (20, 22) and in series along the axis, where each of the intermediate zones comprises an SCR catalyst composition having the molecular sieve in different concentrations and the metal exchanged in the first concentration, and in which the intermediate zones are arranged to form a molecular sieve concentration gradient having a high concentration end and a low concentration end with the high concentration end being closer to the entry face relative to the low concentration end.
    [0010]
    Catalyst article according to any one of claims 1 to 9, characterized in that it is used to reduce NOx in an exhaust gas.
    [0011]
    11. Engine exhaust gas treatment system, characterized by the fact that it comprises: a. a catalyst article as defined in any one of claims 1 to 9; and, b. a source of ammonia or urea upstream of the catalyst article.
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    同族专利:
    公开号 | 公开日
    BR112014002129A2|2017-02-21|
    EP2736628B1|2018-04-11|
    KR101992504B1|2019-09-30|
    US20120186229A1|2012-07-26|
    US9242212B2|2016-01-26|
    US20140227155A1|2014-08-14|
    WO2013014467A1|2013-01-31|
    RU2014107749A|2015-09-10|
    JP2014528350A|2014-10-27|
    EP2736628A1|2014-06-04|
    US8789356B2|2014-07-29|
    CN103781532B|2016-08-31|
    CN103781532A|2014-05-07|
    RU2609476C2|2017-02-02|
    JP6127046B2|2017-05-10|
    KR20140064796A|2014-05-28|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| 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 27/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161512688P| true| 2011-07-28|2011-07-28|
    US61/512688|2011-07-28|
    US13/354720|2012-01-20|
    US13/354,720|US8789356B2|2011-07-28|2012-01-20|Zoned catalytic filters for treatment of exhaust gas|
    PCT/GB2012/051818|WO2013014467A1|2011-07-28|2012-07-27|Zoned catalytic filters for treatment of exhaust gas|
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