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    • 专利摘要:
    DIESEL PARTICLE FILTER COATED BY A REDUCTION CATALYST WITH ENHANCED CHARACTERISTICS. The present invention relates to a diesel particulate filter which comprises a ceramic wall flow filter substrate and two coatings. The first coating that is applied to the inlet flow channels and is composed of high-point materials has such a nature that it closes the inlet flow channels and the pores in the wall that connects the inlet flow channels and the flow channels. outflow to soot particles on the inlet side without impeding the escape of gaseous components from the exhaust gas. The second coating is inserted into the wall between the input flow channels and the output flow channels and has such a nature that it can effectively catalyze the selective reduction of nitrogen oxides by means of a reducing agent. The resulting component is a catalytically active particulate filter by SCR and exhibits excellent accumulated pressure properties combined with high filtration efficiency and satisfactory regeneration properties. In addition, the component exhibits satisfactory aging stability of the conversion activity (...).
    公开号:BR112012025871B1
    申请号:R112012025871-0
    申请日:2011-03-30
    公开日:2021-02-17
    发明作者:Marcus Pfeifer；Stephan Basso；Franz Dornhaus
    申请人:Umicore Ag & Co. Kg；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a diesel particulate filter coated with a reduction catalyst that has improved properties and is suitable for removing diesel soot and nitrogen oxides from the exhaust gas of diesel engines, in particular in vehicles.
    [0002] [0002] The exhaust gas of motor vehicles powered by diesel engines contains not only carbon monoxide (CO) and nitrogen oxides (NOx) but also constituents that originate from the incomplete combustion of the fuel in the combustion chamber of the cylinder. These include residual hydrocarbons (HC), which are also generally present predominantly in gaseous form, and particulate emissions, also referred to as "diesel soot" or "soot particles". These are complex agglomerates predominantly of solid particles containing carbon and an adherent liquid phase that generally consists of relatively long hydrocarbon condensates of relatively long chain. The liquid phase adhering to the solid constituents is also referred to as "soluble organic fraction, SOF" or "volatile organic fraction, VOF".
    [0003] [0003] Residual gaseous hydrocarbons (HC) and carbon monoxide (CO) are typically removed when the exhaust gas is passed through a conventional diesel oxidation catalyst. Particle filters are used to remove particulate emissions. The reduction in the amount of nitrogen oxides in exhaust gases from a low-burn diesel engine, that is, exhaust gases that have a super-stoichiometric content of oxygen, can be achieved, for example, through the "SCR process" ( SCR = selective catalytic reduction). In the SCR process, the exhaust gas from which nitrogen oxides are to be removed is transported after the addition of ammonia or a compound that can be decomposed into ammonia as a reducing agent on a specially formulated catalyst ("SCR catalyst") that catalyzes effectively combining nitrogen oxides with ammonia to form nitrogen.
    [0004] [0004] As a result of increasingly demanding legal emission regulations, the systematic combination of a plurality of exhaust gas purification functions is becoming important. Thus, to join future limits, combining measurements inside the engine with catalytic exhaust gas after treating only a few exhaust gas components will no longer be sufficient. In particular, it appears necessary to remove nitrogen oxides and particles by means of the catalytic exhaust gas after treatment for purification of diesel exhaust gases.
    [0005] [0005] Various solutions for this have been proposed in the prior art. Thus, for example, EP 1 054 722 describes an exhaust gas purification system for the treatment of flue exhaust gas containing NOx and solid particles, that purification system comprises an oxidation catalyst, a particulate filter and a catalyst SCR in combination and in that order. The oxidation catalyst is effective for converting at least part of NO to NOx into NO2 and thus increasing the d2 content of the exhaust gas. On the downstream side of this, there is a fine filter and an SCR catalyst. Between these two devices, there is an injection device for a reduction liquid through which the reducing agent required for the reduction of nitrogen oxide is introduced into the exhaust gas from a source independent of the engine before the exhaust gas. exhaust enter the SCR catalytic converter.
    [0006] [0006] DE 103 23 607 also describes an apparatus for purifying the exhaust gases containing nitrogen oxides and soot particles from an internal combustion engine, which comprises an oxidation catalyst, a particulate filter and an SCR catalyst. This apparatus is characterized by the fact that the SCR catalyst together with the particulate filter are combined to form a structural unit that cannot be separated into an SCR catalyst and particle filter without destroying the SCR catalyst and / or the particulate filter.
    [0007] [0007] EP 0 789 135 describes an exhaust gas purification apparatus comprising filter elements for collecting exhaust gas particles from a diesel engine, electric wire meshes that are arranged on the inlet flow side of the exhaust elements. filter and porous, ceramic elements on the outflow side of the filter elements. The ceramic elements are characterized by the fact that they are formed by a large number of cells that are filled with granules that have a brownmillerite structure and are therefore suitable for reducing the amount of NOx in the exhaust gas.
    [0008] [0008] DE 102 38 770 by the applicant describes an apparatus for removing soot particles from the exhaust gas of a diesel engine, which has a wall flow filter that has alternately closed flow channels for the exhaust gas. The exhaust gas introduced into the inlet flow channels must flow through the porous channel walls of the flow channels into the outlet flow channels. Additional exhaust gas treatment structures are provided in the inlet and / or outlet flow channels of the filter. The channel walls of the flow channels and additional structures are provided with a layer of catalyst. The filter function of the porous channel walls and the catalytic function of the catalyst layer present in the additional structures are widely separated. Here, the different functions are preferably supplemented, as a result of which greater efficiency in the treatment of exhaust gas is obtained in a low volume of construction of the apparatus according to the invention. Depending on the desired catalytic functions, the filter may contain different catalytically active coatings, also catalytically active coatings by SCR.
    [0009] [0009] EP 1 663 458 describes a catalytic product comprising a wall flow filter substrate and an SCR catalyst composition. The SCR catalyst composition is applied as a coating that penetrates through the walls of the wall flow filter substrate in a concentration of at least 79.26 g / l. The wall flow filter substrate has a wall porosity of at least 50% at an average pore size of at least 5 µm. In addition, a method of use based on the use of this component and a corresponding exhaust gas purification system are described, in which not only the catalytic product mentioned above but also an upstream oxidation catalyst and an injection installation that is arranged between the oxidation catalyst and catalytic product and is designed for injection of reducing agent from a source independent of the engine are used.
    [0010] [00010] US 7,264,785 describes a process for the selective catalytic reduction of nitrogen oxides in exhaust gases from low combustion vehicle engines using an exhaust gas purification system. This exhaust gas purification system comprises a first SCR catalyst that effectively catalyzes the selective catalytic reduction of NOx by means of a nitrogen-containing reducing agent and is placed more than 1 meter downstream of the exhaust gas curve or outlet engine turbine. The system comprises a particulate filter that is in a lower body position and contains a second SCR catalyst.
    [0011] [00011] The functionalization of ceramic wall flow filter substrates appears increasingly to be a suitable alternative for the serial arrangement of various catalytic exhaust gas purification devices when effective particle removal and reduction in the amount of gaseous constituents exhaust gas are guaranteed at the same time. However, conventional filters provided with SCR catalyst coatings often exhibit an exorbitant increase in pressure built up during the soot loading phase and have an unsatisfactory pressure buildup behavior in the soot-loaded state. Fundamentally, an accumulated high pressure and also a rapid increase in the accumulated pressure are undesirable in diesel particulate filters that are used in motor vehicles since in operation this results in an expenditure of engine power to "push" the exhaust gas through the system exhaust gas purification. This engine power is lost to move the vehicle. However, optimum utilization of engine power to move the vehicle is equivalent to an increase in the use of effective fuel and offers advantages in fuel consumption as well as reduced CO2 emissions from the vehicle. An additional result of unsatisfactory accumulated pressure behavior is that the filter must be reactivated more frequently by active soot burning. In addition, conventional reduction catalyst coated filters have significantly compromised passive regeneration behavior compared to uncoated filters or oxidation catalyst coated modes: compared to an uncoated filter, the amount of soot that is oxidized locally by NO2 during operation with soot loading and is burned in this way is considerably less. This also results in conventional reduction catalyst coated filters that often must be actively regenerated, that is, regenerated by heating directed above the soot ignition temperature. In addition, a reduced filtration efficiency compared to other catalytically coated filters has not been infrequently observed for actively coated catalyst-reduced filters. Finally, the reduction catalyst coating exhibits a more unsatisfactory long-term stability with respect to NOx conversion compared to conventional SCR catalysts since the more frequent active particle filter regenerations represent considerable thermal stress on the catalytically active coating and results in accelerated thermal deactivation of catalytically active sites.
    [0012] [00012] An object of the present invention is to provide a diesel particulate filter that is functionalized with a SCR catalytically active coating does not have the disadvantages mentioned above.
    [0013] [00013] This objective is achieved by a diesel particulate filter containing a ceramic wall flow filter substrate and two coatings. The first coating is composed of material with a high melting point and is applied to the inlet flow channels. It has a nature that it closes the pores in the wall that connects the inlet flow channels and the outflow flow channels to the soot particles on the inlet flow side without preventing the escape of gaseous components from the exhaust gas [figure 5]. The second coating is introduced into the wall between the inlet flow channels and the outflow flow channels and based on this nature, it effectively catalyzes the selective reduction of nitrogen oxides by means of a reducing agent, that is, this second coating is a SCR catalytically active coating.
    [0014] [00014] To functionalize the wall flow filter substrates with SCR catalysts, it is necessary to use highly porous filter bodies that have relatively large pore diameters to be able to introduce sufficient quantities of the catalytically active coating by reduction into the substrate without the accumulated pressure of the exhaust gas on the component without the soot becoming bulky. This relatively high substrate porosity is, as studies carried out by the inventors show, responsible for the reduced filtration efficiency that is not infrequently observed for conventional reduction catalyst coated filters. In addition, there is an increase in deep-bed filtration on the wall which causes the dramatic deterioration in the accumulated pressure behavior of filters coated by a reduction catalyst during the soot loading phase.
    [0015] [00015] Wall flow filter substrates are honeycomb-shaped ceramic bodies that have inlet and outlet flow channels that are alternately closed in a gas-tight manner. Figure 1 schematically shows this wall flow filter substrate. The exhaust gas containing a particle flowing into the inlet flow channels (1) is forced by the gas-tight closing plug (3) located on the outlet flow side to pass through the porous wall (4) and exit the substrate wall flow filter of the outflow channels (2) that are closed on the inlet flow side. Diesel soot is removed by filtering the exhaust gas in this way.
    [0016] [00016] Soot filtration on the wall flow filter substrate during passage through the wall can be described as a two-stage process. In a first phase, the "deep bed filtration phase", the soot particles remain adhered to the pores of the wall in the passage of the exhaust gas containing particles through the wall [figure 2b]. This results in a reduction in the pore diameter on the wall and as a result of a gradual increase in the pressure accumulated on the wall flow filter substrate. As soon as the pore diameter decreases a lot for medium and relatively large soot particles to enter the pores, the crooked filter formation [figure 2c] begins throughout the inlet flow channel. During the accumulation of the filter cake, the pressure accumulated on the wall flow filter substrate now increases only linearly with the amount of diesel soot removed by filtration. Figure 3 schematically shows the course of pressure accumulated on the wall flow filter starting from the soot-free filter as a function of the amount of soot removed. (1) is the accumulated pressure of the filter without soot, (2) is the increase during the deep bed filtration phase and (3) is the linear increase in the pressure accumulated during the filter cake formation phase.
    [0017] [00017] The two-stage process described above of soot filtration on the wall flow filter substrate is generally valid; this is seen in uncoated wall flow filter substrates and wall flow filter substrates that have a catalytically active coating, for example, a catalytically active reduction coating as described in EP 1 663 458. The initial configuration of the wall flow filter mainly influences the initial accumulated pressure of the component in the soot-free state, as can be seen from figure 4. The conventional catalytically coated wall flow filter substrates (2) exhibit a significantly higher initial accumulated pressure in the soot-free state than uncoated wall flow filter substrates (1); however, the general course of the accumulated pressure curve with increasing soot loading is for the most part comparable with the general course of the accumulated pressure curve of the uncoated substrate (1). However, in the case of wall flow filter substrates coated with a reduction catalyst according to the prior art, deep-bed filtration in the wall is, as indicated above, more strongly evident, this results in a more pronounced increase in the curve pressure accumulated in the deep bed filtration curve.
    [0018] [00018] The filter of the invention has, in addition to a (second) catalytic coating by SCR that is inserted in the wall between the inlet flow channels and the outflow flow channels, a first coating that has such a nature that it closes the pores in the wall connecting the inlet flow channels and the outflow flow channels to the soot particles on the inlet side without preventing the escape of gaseous components from the exhaust gas. This is achieved by means of a coating that mainly contains one or more oxides with a high melting point whose particle sizes correspond to the pore sizes on the wall of the wall flow filter substrate so that the d50 of the particle size distribution of the oxides is equal to or greater than the d5 of the pore size distribution of the wall flow filter substrate, where at the same time the d90 of the oxide particle size distribution is equal to or greater than the d95 of the pore size distribution pore size of the wall flow filter substrate. Here, the d50 or d90 of the oxide particle size distribution is the particle size where 50% or 90%, respectively, of the total volume of the oxides contains only particles whose diameter is less than or equal to the value indicated as d50 or d90, respectively. The d5 or d95 of the pore size distribution of the wall flow filter substrate is the pore size in which 5% or 95%, respectively, of the total pore volume that can be determined by mercury porosimetry are formed by pores whose diameter is less than or equal to the value indicated as d5 or d95, respectively.
    [0019] [00019] As an alternative, the function of this first coating can serve to close the pores in the wall between the inlet flow channels and the outflow flow channels for soot particles without preventing the passage of the gaseous components of the exhaust gas; in that case, the first coating can also be a coating that mainly contains a high melting point fiber material that is deposited as a gas-permeable blanket over the pore openings and thus makes even soot particles very fine to penetrate. in the pores significantly more difficult or, in the most favorable case, prevents it completely. A suitable fiber material is selected so that the average length of the fibers in the range of 50 to 250 µm and the average diameter based on the mass of the fibers is equal to or less than the d50 of the pore size distribution of the filter substrate. wall flow, where the d50 of the pore size distribution of the wall flow filter substrate is the pore size in which 50% of the total pore volume that can be determined by mercury porosimetry are formed by pores whose diameter is less than or equal to the value indicated as d50.
    [0020] [00020] In both cases, this first coating results in the deep bed filtration which is significantly reduced and the accumulated pressure increase observed during the deep bed filtration phase which is thereby significantly reduced. Figure 6 shows schematically the effect obtained by the applied coating.
    [0021] (a) compostos de zeólito submetidos à troca de ferro e/ou cobre selecionados a partir de MOR, USY, ZSM-5, ZSM-20, betazeólito, CHA, FER e misturas desses; ou (b) compostos tipo zeólito submetidos à troca de ferro e/ou cobre selecionados a partir de SAPO-34 e ALPO-34 e misturas desses; ou (c) óxido de vanádio, óxido de titânio, óxido de tungstênio, óxido de molibdênio, óxido de cério, óxido de zircônio, óxido de nióbio, óxido de ferro, óxido de manganês ou misturas ou óxidos mistos desses; ou (d) misturas de (a) e/ou (b) e/ou (c). [00021] The diesel particulate filter of the invention contains a second coating that is inserted into the wall between the inlet flow channels and the outflow flow channels and with this nature it effectively catalyzes the selective catalytic reduction of oxides of nitrogen by means of a reducing agent. This coating contains one or more SCR catalytically active compounds. These are preferably selected from the group consisting of: (a) zeolite compounds subjected to iron and / or copper exchange selected from MOR, USY, ZSM-5, ZSM-20, betazeolite, CHA, FER and mixtures thereof; or (b) zeolite-type compounds subjected to iron and / or copper exchange selected from SAPO-34 and ALPO-34 and mixtures thereof; or (c) vanadium oxide, titanium oxide, tungsten oxide, molybdenum oxide, cerium oxide, zirconium oxide, niobium oxide, iron oxide, manganese oxide or mixtures or mixed oxides thereof; or (d) mixtures of (a) and / or (b) and / or (c).
    [0022] [00022] In the mentioned subgroup (a), particular reference is made to MOR, ZSM-5, beta-zeolite, CHA and FER and a particular preference is given to beta-zeolite, CHA and FER. In the mentioned subgroup (b), SAPO-34 is particularly preferred. In the mentioned subgroup (c), particular preference is given to mixed oxides of cerium oxide, zirconium oxide, optionally tungsten oxide, optionally iron oxide and optionally niobium oxide.
    [0023] [00023] Preferred embodiments of the components of the invention contain wall flow filter substrates that are made of silicon carbide, cordierite or aluminum titanate and have pores with an average diameter in the range of 5 to 50 µm, particularly preferably , from 10 to 25 µm, on the walls between the inlet and outlet flow channels.
    [0024] [00024] The two coatings present in the component of the invention, whose first coating (hereinafter referred to as "outer coating") serves to prevent deep bed filtration while the second coating (hereinafter referred to as "SCR coating") serves to catalyze the selective catalytic reduction of nitrogen oxides in an effective way and act synergistically. As intended, the outer coating not only suppresses deep-bed filtration on the wall, but also increases the filtering efficiency of the filter. The SCR coating significantly reduces, as desired, the amount of nitrogen oxides in the exhaust gas that penetrates through the filter. Furthermore, the combined action of the two coatings results in the decoupling of the two reactions [(1) and (2)], the competition between these has a considerable adverse effect on the passive regeneration behavior of filters coated with conventional reduction catalysts: the reaction oxidation of soot particles with NO2 during the regeneration reaction (1) and the "SCR reaction", that is, the proportion of NO and NO2 with ammonia (2), which, as is generally known, proceeds faster when NO and NO2 are present in a ratio of approximately 1: 1: (1) C + NO2 → CO2 + 2 NO (2) 2 NO + 2 NO2 → 4 N2 + 6 H2O
    [0025] [00025] The combined action of the two layers present in the component of the invention results in the functions that are separated and the competition between the two reactions that are eliminated. Thus, soot can be reacted considerably more effectively with NO2 without interference by the deNOx efficiency of the SCR coating and the passive regeneration behavior of the filter can be significantly improved again. The filter should undergo cycles of active regeneration more rarely. As a result, the thermal stress on the SCR coating decreases and, therefore, the long-term stability of the component in relation to NOx conversion and, thus, the effective action of deNOx that will be considered on the cycle are increased.
    [0026] [00026] When selecting the material for the first coating that closes the pores in the wall that connects the inlet flow channels and the outflow flow channels to soot particles on the inlet flow side without preventing the passage of gaseous constituents from exhaust gas, it will be observed that the materials used in the external coating must not have any catalytic oxidation activity in relation to that of ammonia so that the ammonia that enters the filter is available in its entirety for the SCR reaction. The outer coating, therefore, does not advantageously contain any platinum. However, the outer coating can optionally contain palladium which does not have any catalytic oxidation activity compared to that of ammonia.
    [0027] [00027] In an embodiment of the present invention, the materials used in the external coating are not catalytically active by reduction, in particular not active by SCR. In an alternative embodiment of the present invention, the materials used in the outer coating are catalytically active by reduction, in particular active by SCR. In this case, particular preference is given to SCR-active coatings of the first and second layers that are different, that is, not identical.
    [0028] [00028] In a preferred embodiment, the materials used in the external coating do not have a NOx storage action.
    [0029] [00029] A preferred particle filter according to the invention comprises an outer coating that contains mainly one or more oxides with a high melting point. For the external coating that will have a nature in which the pores connecting the inlet flow channels and the outlet flow channels are closed to soot particles without the escape of gaseous exhaust gas constituents, the materials used for the outer coating they must also be carefully selected in relation to the nature of the particles. In particular, the oxides to be sweated must have a particle size distribution compatible with the pore size distribution on the substrate wall. The correct function of the outer coating is performed when the d50 of the oxide particle size distribution is equal to or greater than the d5 of the pore size distribution of the wall flow filter substrate and at the same time the d90 of the oxide distribution. The particle size of the oxides is equal to or greater than the d95 of the pore size distribution of the wall flow filter substrate. (What is meant by the corresponding dx values of the particle size distribution and the pore size distribution has been explained above.) Preference is given to the use of oxides whose particle size distribution has a d50 greater than or equal to 5 µm at a d90 greater than or equal to 20 µm. Particular preference is given to oxides that have a d50 in the range of 10 to 15 µm and a d90 in the range of 25 to 40 µm. Oxides having a d50 of 10 to 15 µm and a d90 of 30 to 35 µm are preferably used. The latter not only has an optimized function in relation to the reduction of deep bed filtration, but also exhibits particularly satisfactory adhesion to the wall flow filter substrate.
    [0030] [00030] In the case of some oxides, the required particle size ranges can be easily adjusted by targeted pre-grinding of the oxide prior to introduction into the wall flow filter substrate. In order to be able to use this advantage comprehensively and also to obtain the required reaction properties of the outer coating, the oxides of the outer coating are preferably selected from the group consisting of aluminum oxide, metal stabilized aluminum oxide of rare earth, rare earth metal sesquioxide and mixtures of these. Particular preference is given to aluminum oxide or rare earth metal-stabilized aluminum oxide.
    [0031] [00031] In order to guarantee an optimal function of the oxide external coating combined with a very low influence of the coating imposed on deep bed filtration on the initial accumulated pressure, the external coating is preferably applied in a layer thickness of 10 to 150 µm, particularly preferably from 20 to 100 µm, in the inlet flow channels of the wall flow filter substrate. In the case of the aforementioned option of possible external oxide coating materials, these layer thicknesses can be obtained in a loading of 1 to 50 g / l of solid, based on the volume of the wall flow filter substrate. Particular preference is given to loads of 1 to 20 g / l of solid, in a very particular and advantageous way, layer thicknesses of 1 to 10 g / l of solid, based on the volume of the wall flow filter substrate.
    [0032] [00032] To produce a diesel particulate filter according to the invention with an external oxidic coating, it is possible, for example, to use a conventional functionalized diesel particulate filter that has a catalytically active SCR coating on the wall between the flow channels input and output as a base component. The outer coating that reduces the deep bed filtration is then applied. To produce the outer coating, a suitable oxide is selected and suspended in an amount of water that is at least twice the pore volume of the selected oxide. The aqueous suspension of the oxide obtained in this way is optionally ground by means of a Dyno mill until the required particle size distribution is obtained. The addition of auxiliaries to increase the sedimentation stability of the suspension at this stage of the production process is not detrimental to the function of the external coating that will be produced as long as these auxiliaries can be completely removed thermally during calcination in the last stage of preparation. The addition of adhesion-promoting agents such as silica and other inorganic solutions is also not harmful as long as their oxidic calcination residues are not catalytically active by ammonia oxidation or catalytically active by SCR in the component. The suspension is, after the optional adjustment of the particle size distribution by grinding, pumped into the inlet flow channels of the wall flow filter substrate to be coated. After the inflow channels are completely filled with the suspension, the excess suspension is sucked out again from the wall flow filter substrate. Here, the suction power must be selected so that the prescribed loading remains solid in the inlet flow channel at the end of the procedure. The wall flow filter substrate according to the invention which has been produced in this way is dried from 80 to 180 ° C in a flow of hot air and subsequently calcined from 250 to 600 ° C, preferably from 300 to 500 ° Ç. After calcination, it is ready for use without further treatment.
    [0033] [00033] An additional preferred particle filter according to the invention comprises an outer coating which mainly contains a fiber material with a high melting point. The fiber material must have a nature that in the inlet flow channels it forms a gas-permeable blanket over the pore openings in the wall and thus makes the entry of even very fine soot particles into the pores significantly more difficult or, in the most favorable case, it prevents it completely. To ensure this, the fiber material must be selected so that the average length of the fibers is in the range of 50 to 250 µm and the average diameter based on the mass of the fibers is equal to or less than the d50 of the pore size distribution of the wall flow filter substrate The d50 of the pore size distribution of the wall flow filter substrate is the pore size in which 50% of the total pore volume that can be determined by mercury porosimetry is formed by pores whose diameter is less than or equal to the value indicated as d50. Preference is given to the use of fibers that have an average fiber length of 100 to 150 µm and an average diameter based on fiber mass of 5 to 15 µm.
    [0034] [00034] Also as described above, as an alternative to oxides that will be used, the fiber material cannot exhibit catalytic oxidation activity in relation to that of ammonia nor be catalytically active by reduction, in particular, catalytically active by SCR. In addition, the fiber material must be heat resistant to the extent that it resists normal operating temperatures and regeneration of the diesel particulate filter in the range of 100 to 900 ° C, ie the melting point of the fibers must be above 900 ° C. Many fiber materials that meet these technical requirements, for example, asbestos, mullite, mineral wool that has small fiber diameters and aluminum oxide fibers, release carcinogenic fiber powders and / or exhibit catalytic reduction activity in relation to that of oxides nitrogen in the presence of ammonia. The fiber material used in the diesel particulate filter of the invention is therefore preferably selected from the group of materials that are not problematic in terms of health, which consists of rock wool, natural stone fibers and mineral wool with fiber diameters greater than 5 µm. Particular preference is given to the use of natural stone fibers. These natural stone fibers consist predominantly of silicon dioxide, aluminum oxide, calcium oxide and magnesium oxide. These may additionally contain iron oxide and alkali metal oxides, in particular potassium oxide and sodium oxide. Suitable natural stone fibers are obtained, for example, from molten basalt. These can be obtained in various ways as insulation materials in the building materials trade.
    [0035] [00035] The use of fiber material with a high melting point to produce the outer coating allows the outer coating layer thicknesses in the component of the invention to be reduced to 1 to 50 µm. An outer coating composed of fiber material with a high melting point preferably has a layer thickness of 3 to 30 µm. This can be achieved by loading an external coating of 1 to 30 g / l of solid, based on the volume of the wall flow filter substrate. Particular preference is given to loads of 2 to 15 g / l of solid, in a very particular and advantageous way, loads of 2 to 5 g / l of solid, based on the volume of the wall flow filter substrate.
    [0036] [00036] The production of a diesel particulate filter according to the invention that has an external coating containing fiber material with a high melting point can also be carried out using a conventional wall flow filter substrate that has a catalytically active coating by SCR on the wall by suspending the fiber material in a sufficient amount of water and pumping the suspension through the wall flow filter substrate from the inlet flow side. Here, the amount of suspension pumped into the substrate must be selected so that the amount of fiber material obtained corresponds to the loading of solids that will be applied. A correspondingly high pump pressure is required to pump the aqueous suspension through the wall. Small amounts of adhesion promoting aids can optionally be added to the coating suspension so that their particle sizes are large enough that they remain in the interstices between the fibers and do not penetrate the pores between the inlet and outlet flow channels. Silica and other inorganic solutions may also be possible as auxiliary adhesion promoters as long as their oxidative calcination residues in the component are neither catalytically active by oxidation of ammonia nor catalytically active by SCR. After pumping the coating suspension, the wall flow filter substrate is dried at 80 to 180 ° C in a flow of hot air and subsequently calcined at 250 to 600 ° C, preferably from 300 to 500 ° C. After calcination, it is ready for use without further treatment.
    [0037] [00037] Compared to the production of a diesel particulate filter according to the invention that has an external oxidic coating, in the case of production of a diesel particulate filter according to the invention that has an external fiber coating, the suspension of coating should not be sucked out of the inlet flow channels of the wall flow filter substrate as suction stress could result in tearing and opening of the introduced fiber mat and thus exposure of pores. The pores exposed in this way could continue to be accessible to soot particles; as a result, an increased degree of deep bed filtration, a deterioration in passive regeneration behavior and at least partial deterioration in the long-term stability of the resulting component with respect to NOx conversion activity could be observed.
    [0038] [00038] In an additional preferred embodiment, palladium can be added as a catalytically active component by oxidation to the first coating which mainly comprises one or more oxides with a high melting point (i.e., the oxide outer coating) by mixing or impregnation. Palladium exhibits catalytic oxidation activity in relation to residual hydrocarbons (HC) and carbon monoxide (CO), but not in relation to ammonia. The synergistic combined action of external coating and SCR coating, therefore, is not adversely affected by palladium. In addition, this filter according to the invention acquires the ability to oxidize HC and CO, which are formed in increased amounts as a secondary emission during active regeneration, so as not to inhibit CO2 and, thus, remove them directly.
    [0039] [00039] The filter of the invention is particularly suitable for reducing the amount of nitrogen oxides and particles in the exhaust gas of diesel engines. In the particular Pd-containing modality, the filter of the invention also decreases the amount of HC and CO and is therefore suitable for purifying the exhaust gases of diesel engines.
    [0040] [00040] The invention is illustrated below with the aid of some figures and an example. The figures show:
    [0041] (1) denota um canal de fluxo de entrada; (2) denota um canal de fluxo de saída; (3) denota um tampão de fechamento estanque ao gás; (4) denota a parede porosa, ou seja, permeável a gás. [00041] figure 1: schematic description of a wall flow filter substrate; the part (1a) of the figure shows the plan view on the final face with alternating open channels (shown in white) and closed channels in a gas-tight manner (shown in black); the part (1b) of the figure shows a section of the wall flow filter substrate as an outline in principle that indicates the mode of operation; here: the arrows denote the direction of flow of the exhaust gas: (1) denotes an input flow channel; (2) denotes an outflow channel; (3) denotes a gas-tight closing plug; (4) denotes the porous wall, that is, permeable to gas.
    [0042] (1) denota um canal de fluxo de entrada; (2) denota um canal de fluxo de saída; A parte (2a) da figura mostra um corte ampliado da parede do substrato de filtro de fluxo de parede com poro;A parte (2b) da figura mostra esquematicamente o curso da filtração leito profundo;A parte (2c) da figura mostra esquematicamente o curso da formação de torta de filtro.[00042] figure 2: schematic description of the soot filtration process on a wall flow filter substrate; here: the arrows denote the direction of flow of the exhaust gas: (1) denotes an input flow channel; (2) denotes an outflow channel; The part (2a) of the figure shows an enlarged section of the wall of the pore wall flow filter substrate; The part (2b) of the figure schematically shows the course of the deep bed filtration; The part (2c) of the figure schematically shows the course of filter cake formation.
    [0043] (1) denota a pressão acumulada inicial no estado isento de fuligem; (2) denota o aumento de pressão acumulada durante a fase de filtração leito profundo; (3) denota o aumento na pressão acumulada durante a fase de formação de torta de filtro. [00043] figure 3: schematic description of the development of pressure accumulated on a wall flow filter substrate as a function of the amount of soot removed; here (1) denotes the initial accumulated pressure in the soot-free state; (2) denotes the increase in pressure accumulated during the deep bed filtration phase; (3) denotes the increase in pressure accumulated during the filter cake formation phase.
    [0044] (1) denota o desenvolvimento da pressão acumulada sobre um substrato de filtro de fluxo de parede não revestido; (2) denota o desenvolvimento da pressão acumulada sobre um substrato de filtro de fluxo de parede com revestimento catalítico ou revestimento de ignição de fuligem. [00044] figure 4: schematic description of the development of pressure accumulated on a different wall flow filter substrate as a function of the amount of soot removed; here (1) denotes the development of accumulated pressure on an uncoated wall flow filter substrate; (2) denotes the development of accumulated pressure on a wall flow filter substrate with catalytic coating or soot ignition coating.
    [0045] [00045] figure 5: schematic description of a section of a diesel particulate filter according to the invention containing a ceramic wall flow filter substrate and a coating (6) composed of material with a high melting point, this coating is applied in the inlet flow channels (1) and has such a nature that it closes the pores (5) in the wall (4) that connects the inlet flow channels (1) and the outflow channels 2) to particles soot (7) on the inlet flow side without impeding the escape of gaseous components from the exhaust gas. (the SCR catalytically active coating on the wall is not shown in view of the improved clarity of the design).
    [0046] (1) sobre um substrato de filtro de fluxo de parede de acordo com a técnica anterior sem um revestimento que reduz a filtração de leito profundo; (2) sobre um substrato de filtro de fluxo de parede de acordo com a invenção que possui um revestimento que reduz a filtração leito profundo [00046] figure 6: schematic description of the development of accumulated pressure (1) on a wall flow filter substrate according to the prior art without a coating that reduces deep-bed filtration; (2) on a wall flow filter substrate according to the invention that has a coating that reduces deep bed filtration
    [0047] [00047] A ceramic wall flow filter substrate type C650 from NGK that has a diameter of 14.3764 cm and a length of 15.24 cm and has 46.5 cells per square centimeter and a wall thickness of 0, 3048 mm was supplied in a first stage with a catalytically active coating by SCR. For this purpose, a beta-zeolite exchanged with 3% by weight of iron was first suspended in water and the resulting suspension was ground by means of a Dyno mill until the particle size distribution had a d100 below 7 µm. The suspension was, after adjusting to a suitable solids content of about 30%, introduced into the walls of the aforementioned wall flow filter substrate by pumping it into the subsequent inlet and suction outflow channels. The filter was subsequently dried for one hour at 120 ° C in a fluidized bed and calcined for 30 minutes at 350 ° C in a heating blower. The amount of catalytically active SCR coating applied is about 100 g / l on the finished diesel particulate filter, based on the volume of the component.
    [0048] [00048] In a second coating step, the catalytically active diesel particulate filter obtained in this way was supplied with an external oxidic coating that reduces deep bed filtration.
    [0049] [00049] To produce a coating suspension suitable for the external coating, an adequate amount of aluminum oxide stabilized with 3% by weight of lanthanum sesquioxide was suspended by stirring in an amount of water corresponding to approximately 2.5 times the absorption of water from the used oxide. The resulting suspension was ground by means of a Dyno mill until the particle size distribution had a d50 appropriately compatible with the used substrate pore size distribution of 7.36 µm and a d90 of 17.82 µm.
    [0050] [00050] The suspension was, after adjusting to a suitable solids content of about 4% solids, applied to the diesel particulate filter coated by SCR catalyst when pumping the coating suspension into the inlet and suction flow channels subsequent outward. The filter was subsequently dried for two hours at 120 ° C in a heating blower and, after heat treatment for half an hour in the heating blower at 350 ° C, calcined for two hours at 500 ° C in a static oven. The loading assigned to the outer coating on the finished catalytically active diesel particulate filter by reduction is 10 g / l based on the volume of the component.
    权利要求:
    Claims (13)
    [0001]
    Diesel particulate filter containing a ceramic wall flow filter substrate and a first coating applied to the inlet flow channel (1) of refractory material, with the coating closing the pores on the wall (4) of the inlet flow channels (1) and the outflow channels (2) on the inlet side for soot particles without preventing the escape of gaseous exhaust components, in which a second coating is introduced into the wall (4) between the flow channels inlet (1) and outlet flow channels (2) so that it effectively catalyzes the selective reduction of nitrogen oxides with a reducing agent, the filter being characterized by the fact that the first coating contains mainly one or more refractory oxides whose particle size is adapted to the pore sizes on the wall substrate of the wall flow filter, so that the d50 value of the oxide particle size distribution is equal to or greater than the value of d5 of the pore size distribution of the wall flow filter substrate, wherein, at the same time, the d90 value of the oxide particle size distribution is equal to or greater than the d95 value of the particle size distribution of the wall flow filter substrate, wherein the d50 value or the d90 value of the particle size distribution of the oxide particle size is understood in such a way that 50% or 90% of the total volume of the oxides contains only particles whose diameters are less than or equal to the given value of d50 or d90, and wherein the d5 value or the d95 value of the oxide particle size distribution is understood in such a way that 5% or 95% of the total pore volume determinable by mercury porosimetry are formed by pores whose diameters are smaller or equal to the value of d5 or d95 provided.
    [0002]
    Diesel particulate filter, according to claim 1, characterized by the fact that the materials that are used in the first coating do not have any catalytic oxidation activity on the ammonia.
    [0003]
    Diesel particulate filter according to claim 1 or 2, characterized by the fact that the second coating contains one or more catalytically active components selected by SCR from the group consisting of: (a) zeolite compounds subjected to exchange with iron and / or copper selected from MOR, USY, ZSM-5, ZSM-20, betazeolite, CHA, FER or mixtures thereof; or (b) zeolite compounds subjected to exchange with iron and / or copper selected from SAPO-34 and ALPO-34 or mixtures thereof; or (c) vanadium oxide, titanium oxide, tungsten oxide, molybdenum oxide, cerium oxide, zirconium oxide, niobium oxide, iron oxide, manganese oxide or mixed oxide mixtures thereof; or (d) mixtures of (a) and / or (b) and / or (c).
    [0004]
    Diesel particulate filter, according to claim 1, characterized by the fact that the oxides in the first coating have a particle size distribution with a value of d50 that is greater than or equal to 5 µm for a value of d90 greater or equal at 20 µm.
    [0005]
    Diesel particulate filter according to claim 4, characterized by the fact that the oxides in the first coating are selected from the group consisting of aluminum oxide, aluminum oxide stabilized by rare earth metal, earth metal sesquioxide rare and mixtures of these.
    [0006]
    Diesel particulate filter, according to claim 5, characterized by the fact that the first coating has a layer thickness of 10 to 150 µm.
    [0007]
    Diesel particulate filter according to any one of claims 1 to 3, characterized by the fact that the first coating contains mainly a refractory fiber material, in which the average length of the fibers is in the range of 50 to 250 µm and the diameter fiber mass-related mean is equal to or less than the d50 of the pore size distribution of the wall flow filter substrate, where the d50 of the pore size distribution of the wall flow filter substrate is the pore size where 50% of the total pore volume that can be determined by mercury porosimetry are formed by pores whose diameter is less than or equal to value indicated as d50.
    [0008]
    Diesel particulate filter according to claim 8, characterized by the fact that the fiber material is selected from the group consisting of rock wool, natural stone fibers and mineral wool with fiber diameters greater than 5 µm .
    [0009]
    Diesel particulate filter, according to claim 8, characterized by the fact that the coating has a layer thickness of 1 to 50 µm.
    [0010]
    Diesel particulate filter according to any one of the preceding claims, characterized by the fact that the wall flow filter substrate is made of silicon carbide, cordierite or aluminum titanate and the pores present in the walls between the flow channels inlet and outlet have an average diameter in the range of 5 to 50 µm
    [0011]
    Diesel particulate filter according to any one of the preceding claims, characterized by the fact that palladium is added as a catalytically active component by oxidation to the first coating which mainly comprises one or more oxides with a high melting point by mixing or impregnation.
    [0012]
    Use of a diesel particulate filter, as defined in any of claims 1 to 11, characterized by the fact that it is to reduce the amount of nitrogen oxides and particles in the exhaust gas of diesel engines.
    [0013]
    Use of a diesel particulate filter, according to claim 11, characterized by the fact that it is to purify the exhaust gases of diesel engines.
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    同族专利:
    公开号 | 公开日
    CN102762827A|2012-10-31|
    EP2558691B1|2016-08-03|
    WO2011128026A1|2011-10-20|
    EP2558691A1|2013-02-20|
    CN102762827B|2014-12-24|
    BR112012025871A2|2016-06-28|
    US20130004391A1|2013-01-03|
    PL2558691T3|2017-01-31|
    US9347354B2|2016-05-24|
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    法律状态:
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-08-18| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-11-24| B09A| Decision: intention to grant|
    2021-02-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10003923|2010-04-14|
    EP10003923.9|2010-04-14|
    PCT/EP2011/001578|WO2011128026A1|2010-04-14|2011-03-30|Reduction-catalyst-coated diesel particle filter having improved characteristics|
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