• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    method for the production of alveolar catalyst an extruded alveolar catalyst for the reduction of nitrogen oxide according to the method of selective catalytic reduction (scr) in the exhaust gases of the engine supports comprises an extruded active support in the alveolar form comprising a first catalytically active component of scr and with a plurality of channels through which the exhaust gas flows during operation, and a washable coating comprising a second catalytically active component of scr to be applied to the extruded body, wherein the first catalytically active component of scr and the second catalytically active component of scr are each independently selected from the group consisting of: (i) vanadium catalyst with vanadium as a catalytically active component, (ii) mixed oxide catalyst with one or more oxides, in particular those of transition metals or lanthanides, as a catalytic component active, and (iii) a cu- or zeolite catalyst.
    公开号:BR112014002409B1
    申请号:R112014002409-0
    申请日:2012-07-31
    公开日:2020-03-10
    发明作者:Guy Richard Chandler；Neil Robert Collins；Ralf Dotzel；Jörg Werner Münch；Paul Richard Phillips；Gudmund Smedler；Andrew Peter Walker
    申请人:Johnson Matthey Plc；
    IPC主号:
    专利说明:

    METHOD FOR THE PRODUCTION OF EXTRUSED ALVEOLAR CATALYST
    [0001] The invention relates to an extruded honeycomb catalyst, in particular for cleaning exhaust gases, in particular in the field of motor vehicles, where it is used, in particular, for the reduction of nitrogen oxide, in accordance with with the selective catalytic reduction method (SCR), that is, the reduction of nitrogen oxides, using a nitrogen reducer. The invention also concerns a set of such variously incorporated honeycomb catalysts and a method for the production of honeycomb catalysts.
    [0002] Extruded honeycomb catalysts are one-piece, monolithic objects, which have a plurality of channels through which the exhaust gas passes during operation. These channels have an opening width of just a few millimeters. The bands that border the individual channels also typically have a width of only 300 pm. In extruded honeycomb catalysts, where the solid material is catalytically active, a high volume ratio of the solid body consists of catalytically active components. The result of this is that modifications of the catalytic components, for example, to make adaptations to different requirements and, in general, to pursue refinements, have a critical effect on the extrusion capacity. Altogether, which makes the development time for a new extruded honeycomb catalyst, in which the solid material is catalytically active, expensive.
    [0003] WO 2010/099395 A1 discloses extruded honeycomb bodies and methods for making them. The catalyst body includes a first oxide selected from the group consisting of tungsten oxides, vanadium oxides and combinations thereof, a second oxide selected from the group consisting of cerium oxides, lanthanum oxides, zirconium oxides and combinations thereof and a zeolite. In one embodiment, an extruded zeolite core is coated with a layer of a mixture of a cerium oxide, a zirconium oxide and a tungsten oxide.
    [0004] Based on this, the invention is based on the problem of specifying an alveolar catalyst, which can be adapted to new requirements, with low development costs.
    [0005] The problem is solved according to the invention by claim 1. According to this claim, it is provided that the alveolar catalyst, as a whole, is formed from, an active support extruded in alveolar form, which has at least one catalytically active component and in which, in addition to a catalytically active coating, in particular a reactive coating, is applied, which thus also has at least one catalytic component.
    [0006] The problem is further solved according to the invention through a set of alveolar catalysts, which differs in terms of their functionality, but that each one has an identical support, and by a method for the production of alveolar catalysts of this type .
    [0007] This realization is based on the idea of developing and providing a support that can be used universally for various fields of application and making specific adaptations to the respective requirements, through the special reactive washing coating. The particular advantage is to be seen in the fact that a different extrusion mass does not have to be developed and supplied by different honeycomb catalysts. At the same time, because of the possibility of different combinations between the active support and the catalytically active coatings in the same way, all catalytic activity can be adapted and designed as appropriate. In principle, this provides the possibility, first of all, of the development of the catalyst with a view to technically optimized functionality or alternatively, with a view to a catalyst optimized in terms of cost. To achieve the latter, in particular, it is anticipated that the proportion of the catalytically active component in the support is reduced compared to conventional solid catalytically active extrusion products.
    [0008] It is also possible to improve the activity of an SCR catalyst that is otherwise sensitive to gas composition, for example, NO2 ratio: NO (see Fe / ZSM-5 (MFI) SCR in EP 1147801).
    [0009] Preferred embodiments can be derived from the dependent claims.
    [00010] The support and reactive coating are formed as catalysts for SCR. In particular, there are three different known types of catalysts, with application in the present invention: - a catalyst referred to below as a vanadium catalyst, with vanadium as a catalytically active component. This usually contains, as main components, vanadium oxide, titanium oxide and tungsten oxide. In solid catalytically active extrudates the volume ratio of these main catalytically active components is about 75 to 85% by volume. - the second type of catalyst is an oxide catalyst mixed with one or more oxides of lanthanides or as components / catalytically active. Metal oxides generally used are, for example, cerium oxide, zirconium oxide or tungsten oxide, which in conventional catalysts have a volume ratio of about 75 to 85%. Mixed oxide catalysts of this type are generally free of zeolites and also free of vanadium. - As a third type of SCR catalyst, metal zeolite catalysts are known with a metal zeolite as a catalytically active component. In particular, this is an iron zeolite or copper zeolite. In a zeolite catalyst of this type, the volume ratio of these active components is in the range of about 60 to 70% in conventional extruded solids.
    [00011] The rest of the solid extrudate is formed by catalytically inactive components, such as binders, fillers, if necessary, to increase strength and, optionally, a plasticizer for the support during extrusion.
    [00012] Advantageously, the volume ratio of active components in the support is lower in conventional extruded solid catalysts, where the proportions are in the range of the upper limits indicated above. Altogether, the volume ratio in the holder can be adjusted from 10% by volume to the upper limit indicated above. In particular, however, a range of less than 50% by volume or in a range between 10 and 60 or 10 and 40% is defined. In some embodiments of variants, therefore, the largest proportion by volume of the catalyst is formed by inactive components.
    [00013] In embodiments of variants with the reduced proportion catalytically active, this is preferably replaced by components that are neutral in relation to the extrusion process. This means that these are easily putties and / or extrudable materials. These include, in particular, clays (this means phyllosilicates with a grain diameter of less than 2 pm), aluminum oxide or even kaolin. [00014] The honeycomb catalyst according to the invention, in particular the second reactive coating of SCR catalyst, is free of noble metals, at least in the frontal area. In a preferred embodiment, a noble metal coating is applied, especially as a reactive coating, in a rear view seen in the direction of the exhaust gas flow during operation of the area. This is to prevent ammonia from escaping. Therefore, the posterior zone forms what is known as an ASC catalyst (ammonia slip catalyst).
    [00015] Advantageously, this noble metal coating is thus incorporated in the form of a sandwich between the support and a reactive coating that extends along the entire length, which is, in particular, realized as an SCR catalyst . That is, the reactive coating containing noble metal is applied as a layer directly on the support and the second layer of reactive SCR catalyst coating is applied over a total length of the extruded active support, including the reactive coating containing a noble metal. . This arrangement has the advantage that the ammonia that slides past the zone upstream of the first and second SCR catalysts can be oxidized to NOx at the bottom, the noble metal layer and this NOx then passes through the second catalyst layer of SCR to leave the catalyst structure and contacts with the incoming ammonia, so NOx is reduced to N2 on the second SCR catalyst.
    [00016] For all variant embodiments, the reactive coating has a relatively high porosity, so that the exhaust gas to be cleaned also comes into contact with the catalytically active support.
    [00017] In order to achieve good catalytic activity, the support also has a high porosity. Both the support and the reactive coating typically have a large BET surface area in the range of about 40 to 80 m2 / g.
    [00018] The thickness of the reactive coating layer is preferably in the range of 30 to 100 pm, in particular in the range of about 40 to 60 pm. Advantageously, only a single reactive coating is applied to the support. Since the support is also active, a reactive multilayer coating is not necessary and preferably not provided. It is, however, possible.
    [00019] In particular, in the case of solid catalytically active extrusion products with a reduced proportion of active components in the solid extrusion product, the bandwidth of the bands in the wells can be reduced. In conventional extruded honeycomb catalysts manufactured from a solid catalytically active extrudate, the band widths are in the range of about 300 pm. This is preferably reduced to a range of about 150-220 pm, in particular, to a range of about 180 pm.
    [00020] Using the concept of an active reactive coating on a support, different active honeycomb catalysts can be designed according to requirements to meet different needs.
    [00021] These different combinations take into account the various advantages and disadvantages of the individual catalysts, which are preferably combined in such a way that their advantages are increased and their disadvantages are reduced. Thus, individual catalysts differ primarily from an economic point of view in relation to their price. Here, for example, the copper-zeolite catalyst is the most expensive, while the vanadium catalyst is the cheapest. With regard to its technical characteristics, NOx activity across the temperature range is especially important, that is, the ability to reduce NOx at both low and high temperatures. In addition, sulfur tolerance and in particular NO2 tolerance are of particular importance. Finally, the temperature stability of different materials is also relevant.
    [00022] Depending on the intended use, the following preferred combination possibilities are suitable: a) Embodiment of the support as a mixed oxide catalyst with a reactive coating, which can be either a Fe zeolite catalyst or Cu zeolite. The advantage of the mixed oxide catalyst here lies in its low storage capacity, in particular the ammonia storage capacity. Ammonia is used regularly in the SCR method as a typical reducing agent. This allows simple dosing as a function of current demand. The mixed oxide catalyst has deficiencies in the higher temperature range, which are equalized by the reactive coating. On the other hand, in the lower temperature range it is better compared to Fe zeolites, so that, in general, improved activity is achieved over the entire temperature range. b) a reactive coating made from a vanadium catalyst is applied to a support made from a mixed oxide catalyst. The advantage of the vanadium catalyst is its good tolerance for sulfur, which is, on the other hand, a weakness of the mixed oxide catalyst. On the other hand, the mixed oxide catalyst has greater activity at lower temperatures. Another advantage of the mixed oxide catalyst can be seen in its good tolerance to NO2. c) a reactive coating made from copper zeolite is applied to a support made from Fe zeolite. The very good activity in the lower temperature range of copper zeolite is completed by the good sulfur tolerance of iron zeolite. Furthermore, a combination of this type is particularly tolerant to NO2, since iron has a particularly good activity in the presence of medium and high levels of NO2, while copper has a very good activity when there are low levels of NO2 in the gases exhaust. d) a Fe zeolite is applied to a Cu zeolite as a reactive coating. Here, the same advantages apply as in the above combination. e) a vanadium catalyst as a reactive coating is applied to one of Fe zeolite as a support. This combination improved the sulfur resistance and a high tolerance to NO2, since the iron zeolite catalyst has high activity when there are high levels of NO2 in the exhaust gases, unlike the vanadium catalyst. f) the combination of identical catalysts, for example, Fe zeolite catalyst with Fe zeolite catalyst. This increases the total catalytic activity. g) a Fe zeolite catalyst is applied to a support made of a vanadium catalyst. This provides very good activity over a wide range of NO2 / NOx ratios.
    [00023] The concept described here, that is, the provision of an active support in combination with an active reactive coating, therefore, is also expressed in the method according to the invention. To produce honeycomb catalysts with different characteristics, therefore, a type of support is provided and stored, which is then provided, according to the field of application, with different reactive coatings.
    [00024] According to another aspect, an exhaust system is provided for an internal combustion combustion engine with low vehicle burning, comprising an extruded honeycomb catalyst according to the invention arranged in a flow channel thereof.
    [00025] In one embodiment, the exhaust system comprises means for injecting a nitrogen reducer or a precursor thereof into the exhaust gas upstream of the extruded honeycomb.
    [00026] In accordance with another aspect according to the present invention, there is provided an internal combustion engine of low burn comprising an exhaust system according to the invention, which comprises a catalyst for the generation of NH3 in situ, in gases upstream of the extruded honeycomb catalyst and control means for changing an exhaust gas composition to a composition that promotes NH3 in situ over the catalyst for NH3 generation in situ.
    [00027] In one embodiment, the catalyst for the generation of NH3 in situ, in the exhaust gases upstream of the extruded honeycomb catalyst is a diesel oxidation catalyst or a NOx absorption catalyst and, in particular, comprises a platinum group metal and preferably also a lanthanide element, preferably cerium, optionally, in combination with one or more stabilizers such as zirconia and / or a rare earth element.
    [00028] According to another aspect, a support is provided which comprises an exhaust system according to the invention, or a low combustion internal combustion engine according to the invention.
    [00029] In order that the present invention can be more fully understood, the following examples are provided by way of illustration only and with reference to the accompanying drawings, in which: [00030] Figure 1 is a graph showing the activity of conversion of NOx at various temperatures to an extruded alveolar catalyst according to the present invention, which comprises an extruded active support comprising a first SCR catalyst V2O5 / WO3 / TiO2 or Fe-ZSM-5 (MFI) with reactive coating with a reactive coating second SCR catalyst WO3 / CeO2-ZrO2 compared to the second SCR catalyst coated in an inert cordierite honeycomb and the active supports extruded without the SCR catalyst coating, [00031] Figure 2 is a graph showing the activity of conversion of NOx at various temperatures to an extruded honeycomb catalyst according to the present invention, which comprises an extruded active support comprising a first catalyst r SCR zeolite Fe -ZSM-5 (MFI) with reactive coating with a second SCR catalyst Cu-SAPO-34 (CHA) compared to the second SCR catalyst coated in an inert cordierite honeycomb and the extruded active support without the second coating of the SCR catalyst, [00032] Figure 3 is a graph showing NOx conversion activity at various temperatures for an extruded alveolar catalyst according to the present invention, which comprises an extruded active support comprising a first catalyst Reactive coating zeolite Fe-Beta SCR with a second SCR catalyst Cu-SSZ-13 (CHA) in two different reactive coating loads compared to the same loads as the second SCR catalyst coated in an inert cordierite honeycomb and the extruded support without the second SCR catalyst coating, and [00033] Figure 4 is a graph showing NOx conversion activity at various temperatures for an extruded alveolar catalyst based on the present invention, which comprises an extruded active support comprising a first SCR catalyst V2O5 / WO3 / TiO2 with reactive coating with a second SCR catalyst Cu-SSZ-13 (CHA) in two different reactive coating loads compared with the same loads as the second SCR catalyst coated in an inert cordierite honeycomb and the extruded support without the second SCR catalyst coating.
    EXAMPLES
    EXAMPLE 1 - PREPARATION OF THE EXTRUDED ACTIVE SUPPORT IN ALVEOLAR FORM UNDERSTANDING FIRST SCR CATALYST
    Example 1A - Extruded active support containing Fe-Beta zeolite [00034] Beta powdered zeolite commercially available in the form of hydrogen is mixed with iron oxide (FeAl ·), glass fibers, kaolin, powdered synthetic bohemite and the plasticizers of polyethylene oxide (2.25% by weight) and oleic acid (1.62% by weight) (both based on 100% of the total content of inorganic solids) and is processed in an aqueous solution with a pH value of 5 to 6 for a conformable and fluid slip. When the mixture is well plasticized, cellulose is added at 2.25% by weight based on 100% of the total content of inorganic solids. The quantitative proportions of the starting materials are selected in such a way that the active material of the finished catalyst solid body contains 70.34% by weight of iron, zeolite and iron compounds, 2.76% by weight of kaolin, 15, 94% by weight of γ - A12O3; and 4.84% by weight of glass fibers. The conformable mixture is extruded into an alveolar flow catalyst body, that is, with continuous channels and with a circular cross section showing a cell density of 400 cpsi (cells per square centimeter). Subsequently, the catalyst body is freeze-dried for 1 hour at 0.2 kPa according to the method described in WO 2009/080155 (the entire content of which is incorporated by reference) and calcined at a temperature of 580 ° C to form a solid catalyst body. It was found that using the method described that at least some of the iron introduced into the mixture becomes an ion exchanger with the zeolite.
    Example 1B - Extruded active support containing ViOg / WO ^ / TiO . [00035] Commercially available TiO2 powder containing 10% by weight of tungsten is mixed with glass fibers, kaolin, a low alkalinity clay filler and synthetic bohemite z-ammonium metavanadate powder: 1.88% by weight; 2-Aminoethanol: 1.5 liters; Lactic acid 90%: 0.48% by weight; 25% ammonia: 8.97% by weight and polyethylene oxide plasticizers (0.86% by weight) and oleic acid (0.14% by weight) (all based on 100% of the total content of inorganic solids ) and are processed in an aqueous solution with a pH value of 5 to 6 for a conformable and fluid slip. When the mixture is well plasticized, cellulose is added to 0.86% by weight based on 100% of the total content of inorganic solids. The quantitative proportions of the starting materials are selected in such a way that the active material of the finished catalyst solid body contains about 72% by weight of V2O5 / WO3 / TiO2; silica 1.20% by weight; kaolin 2.85% by weight; clay 2.85% by weight; and glass fibers 6.93% by weight. The conformable mixture is extruded into an alveolar flow catalyst body, that is, with continuous channels and with a circular cross section showing a cell density of 400 cpsi (cells per square centimeter). Subsequently, the catalyst body is freeze-dried for 1 hour at 2 kPa according to the method described in WO 2009/080155 (the total content of which is incorporated by reference) and calcined at a temperature of 580 ° C to form a solid catalyst body.
    Example 1C - Extruded active support containing Fe-ZSM-5 (MFI) zeolite [00036] Synthetic ion exchanger ZSM-5 zeolite, the active material containing 5% by weight of iron, is selected as a zeolite. ZSM-5 zeolite powder is mixed with glass fibers and powdered synthetic bohemite and is processed in an aqueous acetic solution with a pH value of 3.5 for a conformable and fluid slip by mixing cellulose and polyethylene plasticizers -glycol and oleic acid. The quantitative proportions of the starting materials are selected in such a way that the active material of the finished catalyst solid body contains 75% by weight of a zeolite containing the compounds of iron and iron, 11.8% by weight of y-AÍ2Ü3 and 8% by weight of glass fibers. The conformable mixture is extruded into an alveolar catalyst body with continuous channels and a circular cross section that has a cell density of 400 cpsi (cells per square centimeter). Subsequently, the catalyst body is dried at a temperature of 90 ° C and calcined to form a solid catalyst body at a temperature of 600 ° C.
    EXAMPLE 2 - PREPARATION OF COMPOSITIONS REACTIVE COATING UNDERSTANDING ACCORDING TO SCR CATALYST Method of making fresh 3% by weight Cu zeolites / (Examples 2A and 2B) [00037] SAPO-34 (CHA) commercially available (Example 2A) and SSZ- 13 (CHA) (Example 2B) were ion exchange NH4 + with a NH4NO3 solution, then filtered. The resulting materials were added to an aqueous solution of Cu (NO3) 2, with stirring. The suspension was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal charge. The final product was calcined.
    Example 2C - Method of making WOx / CeO2-ZrO
    [00038] A catalyst comprising 15% by weight of tungsten supported on a mixed ceria-zirconia oxide comprising 50: 50% by weight of ceria-zirconia was prepared using an incipient moisture impregnation method comprising sufficient dissolution of ammonium metatungstate to give the desired loads of 15% by weight in deionized H2O. The total volume of the solution was equivalent to the pore volume of the support sample (incipient moisture technique). The solution was added to the mixed oxide support material and the resulting mixture was dried overnight at 105 ° C and then calcined at 700 ° C for 3 hours.
    EXAMPLE 3 - PREPARATION OF EXTRUDED ALVEOLAR CATALYSTS
    [00039] Extruded active supports of example 1 were coated with a reactive coating coating comprising the second SCR catalyst of example 2 using the method described in WO 99/47260, that is, comprising the steps of (a) locating a containment means at the top of an extruded active support, (b) administering a quantity of a liquid component within the predetermined interior of said containment means, or in the order of (a), then (b) ) or (b) then (a), and (c) by applying pressure or vacuum, pulling said liquid component into at least a portion of the extruded active support, and maintaining substantially all said amounts within the extruded active support . The coated extruded active supports were then dried in air at 100 ° C for 1 hour and calcined at 500 ° C for 2 hours.
    [00040] The following combinations of active extruded support and reactive coating have been prepared.
    Table 1 Example 5 - Synthetic catalytic activity tests [00041] A 2.54 cm x 14 cm core was cut from each of the extruded alveolar catalysts of example 3 and the catalysts were tested at steady state at the following temperature points: 180 ° C, 215 ° C, 250 ° C, 300 ° C, 400 ° C and 500 ° C in a synthetic catalytic activity tester using the following synthetic gas mixture: O2 9.3%; H2O 7.0%, NOx 100 ppm (NO only); 100 ppm NH3; N2 balance (swept volume: 60,000 liters / h).
    [00042] Results including comparative data are shown in Figures 1 to 4.
    [00043] Figure 1 shows the results for examples 3A and 3B, compared to an identical reactive coating composition (i.e., example 2C) coated on an inert cordierite alveolar support at 400 cpsi at 3.4 g / in3 of charge, and the extruded catalyst supports of Examples 1B and 1C per se. As can be seen from the results, examples 3A and 3B show a better performance when converting NOx over the entire temperature range [00044] Figure 2 shows the results for example 3C, compared to a coating composition identical reactive (i.e., example 2A) coated on an inert cordierite alveolar support at 400 cpsi at 1.8 g / in3 load, and the extruded catalyst support of example 1C alone. As can be seen from the results, it is not a positive effect in the temperature range 200 to 500 ° C tested.
    [00045] Figure 3 shows the results for examples 3D1 and 3D2, compared to identical reactive coating compositions (i.e. example 2B) coated on an inert cordierite alveolar support at 400 cpsi at 1.5 g / in3 and 0.5 g / in3 of charges, and the extruded catalyst support of example 1A per se. As can be seen from the results, examples 3D1 and 3D2 show higher NOx conversion performance at <300 ° C and> 400 ° C.
    [00046] Figure 4 shows the results for examples 3E1 and 3E2, in comparison with identical reactive coating compositions (i.e., example 2B) coated on an inert cordierite alveolar support at 400 cpsi at 1.5 g / in3 and 0.5 g / in3 of loads, and the extruded catalyst support of example 1B per se. As can be seen from the results, examples 3E1 and 3E2 show increased performance at NOX conversion at> 400 ° C. [00047] To avoid any doubt, all the contents of all documents cited here are incorporated by reference in their entirety.
    权利要求:
    Claims (10)
    [1]
    1. Method for the production of extruded alveolar catalyst for nitrogen oxide reduction according to the selective catalytic reduction (SCR) method of exhaust from engine supports, the method comprising: (a) extruding an active support in form honeycomb with a plurality of channels through which the exhaust gas flows during operation, characterized by the fact that the active support comprises 10 to 50% by volume of a first catalytically active SCR component and the rest is formed in each case by components catalytically inactive, such as binders, fillers and a clay, aluminum oxide or kaolin component that is neutral with respect to the extrusion process; and (b) applying a washable coating comprising a second catalytically active SCR component to the extruded body; wherein identical active supports are provided and coated with different wash coatings; wherein the first catalytically active SCR component and the second catalytically active SCR component are each independently selected from the group consisting of: (i) vanadium catalyst with vanadium as the catalytically active component; (ii) oxide catalyst mixed with one or more oxides, in particular those of transition metals or lanthanides as a catalytically active component; and (iii) a Fe zeolite or Cu zeolite catalyst.
    [2]
    2. Method according to claim 1, characterized by the fact that the washable coating, at least in a frontal area - in relation to an exhaust gas flow direction during operation - is free of noble metals.
    [3]
    Method according to either of claims 1 or 2, characterized in that the support has a posterior zone - in relation to an exhaust gas flow direction during operation - in which there is a noble metal coating for prevent ammonia from slipping.
    [4]
    Method according to any one of claims 1 to 3, characterized in that the honeycomb structure has bands and the band width is between 150-220 pm.
    [5]
    Method according to any one of claims 1 to 4, characterized in that the extruded catalyst supports are a mixed oxide catalyst and at least one of the supports is provided with a washing coating which is a metal catalyst of zeolite, in particular a Fe or Cu catalyst.
    [6]
    Method according to any one of claims 1 to 4, characterized in that the extruded catalyst supports are a mixed oxide catalyst and at least one of the supports is provided with a washable coating which is a vanadium catalyst.
    [7]
    Method according to any one of claims 1 to 4, characterized in that the extruded catalyst supports are a Fe Zeolite catalyst and at least one of the supports is provided with a washable coating which is a Zeolite catalyst. Cu.
    [8]
    Method according to any one of claims 1 to 4, characterized in that the extruded catalyst supports are a Cu Zeolite catalyst and at least one of the supports is provided with a coating which is a Fe Zeolite catalyst. .
    [9]
    Method according to any one of claims 1 to 4, characterized in that the extruded catalyst supports are a Fe Zeolite catalyst and at least one of the supports is provided with a washable coating which is a vanadium catalyst.
    [10]
    Method according to any one of claims 1 to 4, characterized in that the extruded catalyst supports are a vanadium catalyst and at least one of the supports is provided with a washable coating which is a Fe-zeolite catalyst.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS553872A|1978-06-27|1980-01-11|Mitsubishi Heavy Ind Ltd|Preparing denitrification catalyst|
    JPS6348584B2|1980-05-31|1988-09-29|Mitsubishi Yuka Kk|
    US4510261A|1983-10-17|1985-04-09|W. R. Grace & Co.|Catalyst with high geometric surface area|
    JPS6372342A|1986-09-13|1988-04-02|Sakai Chem Ind Co Ltd|Catalyst for removing nitrogen oxide|
    US6248684B1|1992-11-19|2001-06-19|Englehard Corporation|Zeolite-containing oxidation catalyst and method of use|
    RU2043146C1|1992-12-11|1995-09-10|Институт катализа СО РАН|Catalyst for reduction of nitrogen oxides with hydrocarbons in oxidizing atmosphere and a method of its preparing|
    US5552128A|1993-08-03|1996-09-03|Mobil Oil Corporation|Selective catalytic reduction of nitrogen oxides|
    US5589147A|1994-07-07|1996-12-31|Mobil Oil Corporation|Catalytic system for the reducton of nitrogen oxides|
    US5772972A|1995-01-09|1998-06-30|Ford Global Technologies, Inc.|Catalyst/hydrocarbon trap hybrid system|
    EP0756891A1|1995-07-26|1997-02-05|Corning Incorporated|Iron zeolite for conversion of NOx|
    JPH09220468A|1996-02-19|1997-08-26|Babcock Hitachi Kk|Catalyst for removal of nox in exhaust gas, its production and method for removing nox in exhaust gas using same|
    JPH09276703A|1996-04-19|1997-10-28|Honda Motor Co Ltd|Catalyst for clening of exhaust gas|
    JPH10323570A|1997-05-26|1998-12-08|Babcock Hitachi Kk|Catalyst for denitration of flue gas and its production|
    DE19749607C1|1997-11-10|1999-03-18|Siemens Ag|Catalytic agglomeration combustion waste gas particles|
    GB9802439D0|1998-02-06|1998-04-01|Ici Plc|Absorbents|
    GB9802504D0|1998-02-06|1998-04-01|Johnson Matthey Plc|Improvements in emission control|
    FR2774606B1|1998-02-11|2000-03-17|Rhodia Chimie Sa|PROCESS FOR REMOVING HALOGENATED COMPOUNDS FROM GASES OR LIQUIDS|
    DE19806062A1|1998-02-13|1999-08-19|Siemens Ag|Reduction catalyst for reducing pollutants from diesel engine exhaust gases|
    GB9805815D0|1998-03-19|1998-05-13|Johnson Matthey Plc|Manufacturing process|
    US6110862A|1998-05-07|2000-08-29|Engelhard Corporation|Catalytic material having improved conversion performance|
    AT236706T|1998-05-29|2003-04-15|Siemens Ag|METHOD FOR PURIFYING DIESEL ENGINE EXHAUST GAS|
    JP2002530175A|1998-11-20|2002-09-17|コーニンクレッカフィリップスエレクトロニクスエヌヴィ|Catalyst-carrying filter|
    JP2000176298A|1998-12-11|2000-06-27|Mazda Motor Corp|Exhaust gas purification catalyst and its production|
    WO2001047634A1|1999-12-28|2001-07-05|Corning Incorporated|Zeolite/alumina catalyst support compositions and method of making the same|
    EP1242182B1|1999-12-29|2005-11-02|Corning Incorporated|High strength and high surface area catalyst, catalyst support or adsorber compositions|
    DE10020100A1|2000-04-22|2001-10-31|Dmc2 Degussa Metals Catalysts|Process and catalyst for the reduction of nitrogen oxides|
    JP4573320B2|2000-09-08|2010-11-04|昭和電工株式会社|Nitrous oxide decomposition catalyst, production method thereof, and decomposition method of nitrous oxide|
    DE10063220A1|2000-12-19|2002-06-20|Basf Ag|NOx storage catalyst, process for its production and its use|
    JP3936238B2|2002-05-20|2007-06-27|株式会社デンソー|Catalyst body and method for producing catalyst body|
    PL1493484T3|2003-07-02|2007-05-31|Topsoe Haldor As|Process and filter for the catalytic treatment of diesel exhaust gas|
    DE10340653B4|2003-09-03|2006-04-27|Hte Ag The High Throughput Experimentation Company|Catalyst for the removal of pollutants from exhaust gases of lean-burn engines with ruthenium as active metal|
    US7490464B2|2003-11-04|2009-02-17|Basf Catalysts Llc|Emissions treatment system with NSR and SCR catalysts|
    DE102004005997A1|2004-02-06|2005-09-01|Hte Ag The High Throughput Experimentation Company|Iron oxide stabilized noble metal catalyst for the removal of pollutants from exhaust gases from lean-burn engines|
    WO2006068256A1|2004-12-22|2006-06-29|Hitachi Metals, Ltd.|Method for manufacturing honeycomb filter and honeycomb filter|
    US20060179825A1|2005-02-16|2006-08-17|Eaton Corporation|Integrated NOx and PM reduction devices for the treatment of emissions from internal combustion engines|
    MX2007010465A|2005-02-28|2008-01-14|Catalytic Solutions Inc|Catalyst and method for reducing nitrogen oxides in exhaust streams with hydrocarbons or alcohols.|
    WO2007000826A1|2005-06-27|2007-01-04|Ibiden Co., Ltd.|Honeycomb structure body|
    US7389638B2|2005-07-12|2008-06-24|Exxonmobil Research And Engineering Company|Sulfur oxide/nitrogen oxide trap system and method for the protection of nitrogen oxide storage reduction catalyst from sulfur poisoning|
    JP4617253B2|2005-12-26|2011-01-19|エヌ・イーケムキャット株式会社|NOx removal catalyst, honeycomb structure type NOx removal catalyst, and NOx removal method using the same|
    US7829062B2|2006-02-14|2010-11-09|Exxonmobil Chemical Patent Inc.|Method of preparing a molecular sieve composition|
    JP4801461B2|2006-02-16|2011-10-26|三菱重工業株式会社|Method for producing exhaust gas treatment catalyst|
    JP2007285295A|2006-03-24|2007-11-01|Ngk Insulators Ltd|Exhaust emission control system|
    DE102006020158B4|2006-05-02|2009-04-09|Argillon Gmbh|Extruded full catalyst and process for its preparation|
    US7759280B2|2006-09-20|2010-07-20|Basf Corporation|Catalysts, systems and methods to reduce NOX in an exhaust gas stream|
    CN101528326B|2006-10-23|2012-08-29|尤米科尔股份公司及两合公司|Vanadium-free catalyst for selective catalytic reduction and process for its preparation|
    US7527776B2|2007-01-09|2009-05-05|Catalytic Solutions, Inc.|Ammonia SCR catalyst and method of using the catalyst|
    US7645718B2|2007-03-26|2010-01-12|Pq Corporation|Microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same|
    EP3300791B1|2007-04-26|2019-03-27|Johnson Matthey Public Limited Company|Transition metal/zeolite scr catalysts|
    WO2008154739A1|2007-06-18|2008-12-24|Valorbec Societe En Commandite|Co-catalysts for hybrid catalysts, hybrid catalysts comprising same, monocomponent catalysts, methods of manufacture and uses thereof|
    GB2450484A|2007-06-25|2008-12-31|Johnson Matthey Plc|Non-Zeolite base metal catalyst|
    WO2009057650A1|2007-10-29|2009-05-07|Ict Co., Ltd.|Catalyst for the removal of nitrogen oxides and method for the removal of nitrogen oxides with the same|
    WO2009073099A1|2007-11-30|2009-06-11|Corning Incorporated|Zeolite-based honeycomb body|
    DE102007061776A1|2007-12-20|2009-06-25|Argillon Gmbh|Process for drying ceramic honeycomb bodies|
    GB2457651A|2008-01-23|2009-08-26|Johnson Matthey Plc|Catalysed wall-flow filter|
    US7695703B2|2008-02-01|2010-04-13|Siemens Energy, Inc.|High temperature catalyst and process for selective catalytic reduction of NOx in exhaust gases of fossil fuel combustion|
    JPWO2009118868A1|2008-03-27|2011-07-21|イビデン株式会社|Honeycomb structure|
    JPWO2009141895A1|2008-05-20|2011-09-22|イビデン株式会社|Exhaust gas purification device|
    WO2009141889A1|2008-05-20|2009-11-26|イビデン株式会社|Honeycomb structure|
    WO2009141884A1|2008-05-20|2009-11-26|イビデン株式会社|Honeycomb structure|
    JP5356065B2|2008-05-20|2013-12-04|イビデン株式会社|Honeycomb structure|
    JP2010000499A|2008-05-20|2010-01-07|Ibiden Co Ltd|Honeycomb structure|
    JP5175797B2|2008-05-20|2013-04-03|イビデン株式会社|Honeycomb structure|
    CN101678351B|2008-05-20|2012-07-04|揖斐电株式会社|Honeycomb structure|
    WO2009141886A1|2008-05-20|2009-11-26|イビデン株式会社|Honeycomb structure|
    GB0812544D0|2008-07-09|2008-08-13|Johnson Matthey Plc|Exhaust system for a lean burn IC engine|
    US8343448B2|2008-09-30|2013-01-01|Ford Global Technologies, Llc|System for reducing NOx in exhaust|
    CN101485980B|2009-02-27|2012-09-05|中国科学院大连化学物理研究所|Catalyst structure composed of zeolite and redox oxide|
    US10343117B2|2009-02-27|2019-07-09|Corning Incorporated|Ceria-zirconia-zeolite catalyst body|
    US8703636B2|2009-02-27|2014-04-22|Corning Incorporated|Method of manufacturing a catalyst body by post-impregnation|
    WO2010108083A1|2009-03-20|2010-09-23|Basf Catalysts Llc|EMISSIONS TREATMENT SYSTEM WITH LEAN NOx TRAP|
    GB2482094B|2009-04-17|2014-05-14|Johnson Matthey Plc|Small pore molecular sieve supported copper catalysts durable against lean/rich ageing for the reduction of nitrogen oxides|
    US20100296992A1|2009-05-22|2010-11-25|Yi Jiang|Honeycomb Catalyst And Catalytic Reduction Method|
    JP5531501B2|2009-08-21|2014-06-25|三菱自動車工業株式会社|Exhaust gas purification device|
    DE102009040352A1|2009-09-05|2011-03-17|Johnson Matthey Catalysts Gmbh|Process for the preparation of an SCR active zeolite catalyst and SCR active zeolite catalyst|
    GB2475740B|2009-11-30|2017-06-07|Johnson Matthey Plc|Catalysts for treating transient NOx emissions|
    GB201000019D0|2010-01-04|2010-02-17|Johnson Matthey Plc|Coating a monolith substrate with catalyst component|
    EP2531280B1|2010-02-01|2014-12-24|Johnson Matthey Public Limited Company|NOx ABSORBER CATALYSTS|
    US8815763B2|2010-05-28|2014-08-26|Corning Incorporated|Method of manufacturing a transition metal catalyzed zeolite body|JP6476115B2|2012-08-17|2019-02-27|ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ|V / TiW catalyst activated by zeolite|
    MX2015011354A|2013-03-14|2016-01-15|Basf Corp|Selective catalytic reduction catalyst system.|
    CA2900291A1|2013-03-14|2014-10-02|Basf Corporation|Selective catalytic reduction catalyst system|
    JP5919215B2|2013-03-29|2016-05-18|日本碍子株式会社|Honeycomb catalyst body|
    KR101522857B1|2013-05-02|2015-05-26|희성촉매 주식회사|A hybrid SCR catalyst|
    GB2518502B|2013-07-26|2017-08-09|Johnson Matthey Plc|Tungsten/titania oxidation catalyst|
    EP2875863A1|2013-11-25|2015-05-27|Umicore AG & Co. KG|SCR catalytic converter|
    JP6453233B2|2013-12-09|2019-01-16|株式会社キャタラー|Exhaust gas purification device|
    DE102014201263A1|2014-01-23|2015-07-23|Johnson Matthey CatalystsGmbh|catalyst|
    CN103769114A|2014-02-14|2014-05-07|中国科学院生态环境研究中心|Vanadium-modified iron-based activated carbon catalyst, preparation method and application thereof|
    DE102014205760A1|2014-03-27|2015-10-01|Johnson Matthey Public Limited Company|Process for producing a catalyst and catalyst|
    DE102014205783A1|2014-03-27|2015-10-01|Johnson Matthey Public Limited Company|Catalyst and method for producing a catalyst|
    US10626772B2|2014-07-18|2020-04-21|Cummins Inc.|SCR exhaust aftertreatment apparatus, system and methods including multiple washcoat formulations|
    WO2016011366A1|2014-07-18|2016-01-21|Cummins Inc.|Scr exhaust aftertreatment apparatuses, systems and methods including multiple washcoat formulations|
    WO2016020806A1|2014-08-07|2016-02-11|Johnson Matthey Public Limited Company|Zoned catalyst for treating exhaust gas|
    BR112017002843B1|2014-08-15|2022-01-04|Johnson Matthey Public Limited Company|SYSTEM AND METHOD FOR TREATMENT OF EXHAUST GAS|
    JP5748894B1|2014-11-07|2015-07-15|三菱重工業株式会社|Exhaust gas treatment method and denitration / SO3 reduction device|
    JP2016150277A|2015-02-16|2016-08-22|イビデン株式会社|Honeycomb catalyst|
    JP6292159B2|2015-04-13|2018-03-14|トヨタ自動車株式会社|Exhaust gas purification catalyst|
    JP6916117B2|2015-06-18|2021-08-11|ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ|Ammonia slip catalyst with low N2O forming property|
    JP6787935B2|2015-06-18|2020-11-18|ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ|Single-layer or double-layer ammonia slip catalyst|
    US9987626B2|2015-08-20|2018-06-05|Ford Global Technologies, Llc|Use of transition metals to reduce cold start emissions|
    CN105126818B|2015-08-28|2017-08-22|湖北省轻工业科学研究设计院|A kind of wear-resisting anti-poisoning honeycomb fashion SCR denitration and preparation method thereof|
    US9764287B2|2015-11-06|2017-09-19|Paccar Inc|Binary catalyst based selective catalytic reduction filter|
    US10188986B2|2015-11-06|2019-01-29|Paccar Inc|Electrochemical reductant generation while dosing DEF|
    US9757691B2|2015-11-06|2017-09-12|Paccar Inc|High efficiency and durability selective catalytic reduction catalyst|
    US10058819B2|2015-11-06|2018-08-28|Paccar Inc|Thermally integrated compact aftertreatment system|
    DE102015224370A1|2015-12-04|2017-06-08|Johnson Matthey CatalystsGmbh|Catalyst and process for the preparation of a catalyst|
    KR20180096696A|2015-12-17|2018-08-29|바스프 코포레이션|Selective catalytic reductioncatalyst comprising V and Sb-containing complex oxides, a process for its preparation and its use for the removal of nitrogen oxides|
    US10105691B2|2016-03-31|2018-10-23|Ford Global Technologies, Llc|Multiple zeolite hydrocarbon traps|
    KR20190008425A|2016-06-13|2019-01-23|바스프 코포레이션|Catalyst articles comprising co-precipitates of vanadia, tungsten and titania|
    CN107051578B|2016-09-28|2020-08-04|长沙理工大学|Niobium-cerium supported iron exchange molecular sieve low-temperature denitration catalyst and preparation method and application thereof|
    CN106732755B|2016-12-23|2019-03-05|中节能万润股份有限公司|A kind of preparation method of the compound integral extruding type denitrating catalyst of molecular sieve-multivariant oxide|
    GB201705158D0|2017-03-30|2017-05-17|Johnson Matthey Plc|Catalyst article for use in a emission treatment system|
    GB201716063D0|2017-03-30|2017-11-15|Johnson Matthey Plc|A catalyst for treating an exhaust gas, an exhaust system and a method|
    US10675586B2|2017-06-02|2020-06-09|Paccar Inc|Hybrid binary catalysts, methods and uses thereof|
    US10835866B2|2017-06-02|2020-11-17|Paccar Inc|4-way hybrid binary catalysts, methods and uses thereof|
    GB201805312D0|2018-03-29|2018-05-16|Johnson Matthey Plc|Catalyst article for use in emission treatment system|
    CN109499606A|2018-11-13|2019-03-22|中节能万润股份有限公司|A kind of copper and iron composite SCR honeycomb type denitrification catalyst and its preparation method and application|
    US11007514B2|2019-04-05|2021-05-18|Paccar Inc|Ammonia facilitated cation loading of zeolite catalysts|
    US10906031B2|2019-04-05|2021-02-02|Paccar Inc|Intra-crystalline binary catalysts and uses thereof|
    EP3741449A1|2019-05-21|2020-11-25|Haldor Topsøe A/S|A process for the removal of dinitrogen oxide in process off-gas|
    EP3782727A1|2019-08-20|2021-02-24|Umicore Ag & Co. Kg|Ammonia emissions reduction catalyst|
    WO2021058484A1|2019-09-27|2021-04-01|Johnson Matthey CatalystsGmbh|MULTI-FUNCTION CATALYST ARTICLE FOR TREATING BOTH CO AND NOx IN STATIONARY EMISSION SOURCE EXHAUST GAS|
    US10934918B1|2019-10-14|2021-03-02|Paccar Inc|Combined urea hydrolysis and selective catalytic reduction for emissions control|
    KR102297690B1|2020-04-17|2021-09-02|희성촉매 주식회사|A method for reinforcing adhesion force of slurry for selective catalytic reduction catalyst|
    US20210339234A1|2020-04-30|2021-11-04|Johnson Matthey Public Limited Company|Method|
    EP3915679A1|2020-05-26|2021-12-01|UMICORE AG & Co. KG|Ammonia emissions reduction catalyst, catalyst system, and exhaust gas purification system|
    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-04-30| B06T| Formal requirements before examination|
    2019-08-20| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-02-27| B09A| Decision: intention to grant|
    2020-03-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE202011103994|2011-08-03|
    DE202011103994.7|2011-08-03|
    GB201202182A|GB201202182D0|2011-06-01|2012-02-08|Extruded honeycomb catalyst|
    GB1202182.0|2012-02-08|
    US201261599124P| true| 2012-02-15|2012-02-15|
    US61/599124|2012-02-15|
    PCT/GB2012/051857|WO2013017873A1|2011-08-03|2012-07-31|Extruded honeycomb catalyst|
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