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    • 专利摘要:
    GASOLINE ENGINE EXHAUST TREATMENT SYSTEM; AND PROCESS FOR THE REDUCTION OF HARMFUL POLLUTANTS EMITTED BY GASOLINE ENGINES. The present invention is directed to a pollutant reduction system for vehicles provided by a gasoline combustion engine, in particular a gasoline direct injection (GDI) engine. Furthermore, this invention concerns a process of mitigating harmful components in the exhaust of these engines efficiently applying the inventive reduction system to meet future legislative regulations on exhaust.
    公开号:BR112014024554B1
    申请号:R112014024554-1
    申请日:2013-04-10
    公开日:2021-05-04
    发明作者:Raoul Klingmann；Stephanie Spiess；Ka-Fai Wong；Joerg-Michael Richter
    申请人:Umicore Ag & Co. Kg；
    IPC主号:
    专利说明:

    DESCRIPTION
    [001] The present invention is directed to a pollutant reduction system for vehicles powered by a gasoline combustion engine, in particular, an engine with gasoline direct injection (GDI). Furthermore, this invention relates to an efficient mitigation process of harmful components in the exhaust of these engines applying the inventive reduction system to meet future legislative regulations on exhaust.
    [002] Exhaust gases from internal combustion engines operated with a predominantly stoichiometric air/fuel mixture, such as multi-point fuel injection (PFI) engines, are purified according to conventional methods, with the help of three-way catalytic converters. These are capable of converting the three essentially gaseous engine pollutants, specifically hydrocarbons, carbon monoxide and nitrogen oxides, simultaneously into harmless components. In addition to gaseous hydrocarbon (HC), carbon monoxide (CO) and nitrogen oxide (NOx) pollutants, gasoline engine exhaust gas also contains little ultra-fine particulate matter (MP), which results from incomplete combustion of the fuel and consists of essentially soot.
    [003] Some engine technologies with direct gasoline injection (GDI) were introduced later, which involve more efficient combustion conditions, resulting in improved fuel consumption. These conditions, however, can lead to the generation of even more particulates. In contrast to particulates generated by diesel engines, particulates generated by engines with direct gasoline injection tend to be much finer. This is due to the different combustion conditions of a diesel engine compared to a gasoline engine. For example, gasoline engines run at a higher temperature than diesel engines. Also, hydrocarbon components are different in emissions from gasoline engines compared to diesel engines.
    [004] Vehicles with direct gasoline injection (GDI) engines with and without turbochargers are gaining market share in Europe due to their superior fuel economy and conductivity compared to vehicles with multi-point fuel injection (PFI) engines . This trend is expected to continue due to the European Union's mandate to vehicle manufacturers for passenger transport to further reduce CO2 emissions and meet an average fleet of 130 g/km of CO2 emissions in the year 2012. Average targets ambitious CO2 fleet are being discussed. With CAFE standards becoming more stringent it is generally anticipated that in the US GDI vehicle sharing will grow at the expense of PFI vehicles.
    [005] A concern related to vehicles with GDI is the mentioned particle emission originating from this type of engine, especially due to the relatively small particle sizes and therefore the potentially more dangerous nature of these particles. Since the implementation of stage 5b emission legislation in early 2011 all new registered diesel passenger cars must comply with a particulate mass limit of 4.5 mg/km as well as a solid particle number limit. of 6xlOn #/km (table 1). The introduction of a particle number limit for gasoline vehicles has been postponed to stage 6 emission legislation which will come into effect in September 2014. It is anticipated that the limits for spark-ignition vehicles will be the same as those for spark ignition vehicles. compression-ignition vehicles to meet emission neutral technology legislation. TABLE 1 - EURO 6 EMISSION LIMITS FOR CARS FOR PASSENGER TRANSPORTATION

    [006] Gasoline vehicles with multi-point fuel injection typically meet the proposed particle emission target of 600 billion particles per kilometer. A study by Braisher et al. revealed that particle number emissions by vehicles with direct injection were above a magnitude higher than with vehicles with multipoint fuel injection, with a large portion of the particles being emitted during the cold start of the driving cycle (Braisher, M ., Stone, R., Price, P., "Particle Number Emissions from a Range of European Vehicles," Technical Document SAE 2010-01-0786, 2010, doi: 10.4271/2010-01-0786). Particulate mass emissions showed the same trend.
    [007] Several studies have shown that only wall flow filters are effective in reducing the particle number emissions of these engines below the target of 6xlOn #/km. Cordierite type wall flow filters have become a standard solution for heavy duty diesel vehicles and have also been widely considered for passenger car diesel applications. Recent studies have shown the successful application of cordierite filters for the treatment of particle exhaust from GDI vehicles (Saito, C, Nakatani, T., Miyairi, Y., Yuuki, K., Makino, M., Kurachi, H. , Heuss, W., Kuki, T., Furuta, Y., Kattouah, P., and Vogt, C.-D., "New Filter for Particulate Concept to Reduce Particle Number Emissions," Technical Document SAE 2011-01- 0814, 2011, doi: 10.4271/201101-0814).
    [008] In addition to regulations for the treatment of exhaust gas particulates, emission standards for unburnt hydrocarbon contaminants, carbon monoxide, and nitrogen oxide also continue to become more stringent (table 1). In order to meet these standards, catalytic converters containing a dedicated three-way catalyst (CTV) need to be installed in the exhaust gas line of gasoline combustion engines. As mentioned above, said catalyst promotes the oxidation of unburned hydrocarbons and carbon monoxide by oxygen, as well as the reduction of nitrogen oxides to nitrogen in the exhaust gas stream. In addition, filter types have now been proposed especially designed for application in engines with direct gasoline injection, dealing with all types of emitted pollutants. As the size of the soot particulate emitted is smaller compared to diesel engines, more research should be done on how to balance the filtering effect appropriately, in view of the loss related to apparent back pressure (US201000239478, US20100275579, US8066963, US20110030346, US20090193796, SAE2011010814).
    [009] Catalytic systems have already been proposed, which try to efficiently face all pollutants emitted by GDI engines. In some cases, these systems are designed in a layout in which a close-coupled CTV is accompanied by a wall flow filter (filter for catalyzed gasoline particulates; FPG). In some cases the wall flow filter also carries catalytic functionality, for example another CTV.
    [010] For example, the document US20100293929 deals with exhaust gas emission aftertreatment systems for engines with spark ignition. Various embodiments of the system mentioned herein comprise both a closed-circuit coupled CTV device and an under-floor treatment device. The treatment device below the floor can have either a CTV or NOx reduction functionality. According to fig. 1 disclosed, the system comprises a wall flow CTV coated filter element (8). It is mentioned that with respect to fig. 4, CTV catalytic formulation in the filter is operable to reduce particulate matter as well as gases treated by conventional CTV devices. So the wall flow filter is able to reduce HC, CO, NOx when its light off temperature is reached, and effectively reduce particulate matter emissions under all operating conditions. However, no further details are given with respect to the content of the closed-loop coupled CTV and the CTV coated filter in this disclosure.
    [011] The document US20110252773 also discloses an exhaust system suitable for use in conjunction with gasoline engines to capture particulates, furthermore, to reduce gaseous emissions such as hydrocarbons, nitrogen oxides, and carbon monoxide. The CTV coated particulate filter has washcoat loadings in the range of at least 1 to 4 g/in3 to minimize back pressure related losses. The porosity of the coated filter can be in the range of 55 to 70%, and can comprise certain average pore size distributions. The catalyzed filter may need to be used in conjunction with a second CTV in order to meet regulations and vehicle manufacturers' requirements (fig 1). However, the upstream CTV may be less than otherwise required due to the downstream CTV coated particulate filter, or it may even be omitted if the filter provides full CTV functionality. The catalyzed particulate filter may comprise a zoned arrangement, wherein the upstream zone comprises the palladium component in an amount which is greater than the amount of the palladium component in the downstream zone. The catalyzed filter is said to contain between 2-100 g/ft3 of palladium in the upstream zone and 1-20 g/ft3 of palladium in the downstream zone. The systems tested in this order comprise CTV precious metal loadings and the >30g/ft3 catalyzed filter. Palladium to rhodium ratios are in each case 27/3 for both catalytic devices.
    [012] Also, the document US20110158871 relates to an exhaust system for a vehicle positive ignition internal combustion engine. The system comprises a three-way washcoat catalyst disposed on a monolithic substrate located upstream of the filter, which is also coated with a CTV washcoat. The upstream device is claimed to comprise equally or less than 75% of the total mass of the three-way washcoat catalyst in the exhaust system. The behavior of the wall flow filter was examined in view of the average pore size of the filter substrate and its washcoat loading. In view of the disclosed patent application, the closed-loop coupled CTV comprises a CTV washcoat as the downstream CTV coated ceramic wall flow filter. In the examples, the wall flow filter substrate comprises, for example, a Pd-Rh ratio of 16:1 at a loading of 85 g/ft3. The closed-circuit coupled CTV was coated with an identical charge.
    [013] It was an objective of the present invention to provide a system for the reduction of pollutants emitted by a gasoline direct injection engine that shows superior effects over the systems disclosed in the prior art, both from an economic and ecological point of view. In particular, the system of the invention must serve to safely meet the future standards of legislation discussed. Furthermore, this goal must advantageously be achieved with lower precious metal costs than associated with systems present in the prior art. Likewise, a process for the efficient treatment of engine exhaust with direct gasoline injection must be provided.
    [014] These and other objectives, being obvious to those skilled in the art, are met by a system as described in claim 1. Preferred embodiments of the system of the invention are protected in sub-claims 2-10 relating to claim 1. The claim 11 is directed to an inventive process.
    [015] In a first aspect, the present invention relates to a gasoline engine exhaust treatment system comprising a three-way catalyst coupled in a closed circuit (CTV) and a filter for flow and wall particles of gasoline catalyzed to downstream (FPG). This system is characterized by a certain ratio of precious metal content of the closed-loop coupled CTV compared to the downstream catalyzed gasoline particulate filter. In particular, the amount of platinum group metals, eg Pd and Rh, in CTV exceeds the amount of platinum group metals, eg Pd and Rh, in FPG by a factor of at least 5. This system is capable to satisfy the above mentioned goals in a relatively easy, yet surprising, way. It could be shown that by distributing the precious metal content of the system in a manner according to the present invention, some results can be achieved with smaller amounts of precious metal, which in turn leads to cheaper production of the system. invention or, for the same costs, acts for a better mitigation of harmful pollutants.
    [016] Both the CTV upstream and the FPG downstream advantageously comprise the precious metals palladium, rhodium, platinum or mixtures thereof. Other precious metals, eg iridium, rhenium, ruthenium, silver, gold, may also be present. However, if present, the latter PGMs are contained in lesser amounts compared to palladium and rhodium, respectively. It is more preferable that the platinum group metals present in an upstream CTV and downstream FPG are just palladium and rhodium.
    [017] In another preferred embodiment of the present invention, the ratio of platinum group metals in the upstream CTV and the downstream FPG is at least 6, more preferable, at least 7, even more preferable, at least 8 or 9 , and most preferable of all, at least 10. It is particularly preferable that the platinum group metals involved in the system are only Pd and Rh.
    [018] It was found that the metal content of the platinum group of the downstream gasoline particulate filter helps to accelerate the combustion of the soot accumulated in the filter. Hence, an upper bound of the CTV vs. FPG on platinum group metals is drawn by the fact that the FPG must further comprise a beneficial CTV functionality that is sufficient to supplement the upstream CTV functionality in an economical and ecological manner, and must further show the ability to accelerate combustion of soot particles. It is obvious that, in this regard, also the amount of platinum group metals in the upstream CTV must be balanced by cost factors and by efficiency in mitigating harmful exhaust pollutants via the inventive system. It should be noted that this factor can depend heavily on the kind of engine involved and the composition of its exhaust gas, as well as the extent to which PGMs are effective in the devices in question (eg, decreased activity over lifetime useful, support used, etc.). The skilled worker will know how to find the upper limit for the platinum group metal ratio according to the parameters mentioned above. However, this upper limit advantageously ranges between 10-23, preferably between 15-20, and more preferably between 16-19. Given this, the amounts of platinum group metals, eg Pd and Rh, in the upstream CTV advantageously range between 20-200 g/ft3, more preferably between 25-120 g/ft3, and most preferably around 30-80 g/ft3. The downstream FPG instead shows platinum group metal contents of preferably 2-20 g/ft3, more preferably 2-15 g/ft3, and most preferably around 2-10 g/ft3.
    [019] In an advantageous alternative embodiment, the platinum group metals in the upstream CTV are present in a certain ratio to each other. For example, in case palladium and rhodium are the only platinum group metals in question, the upstream CTV has a weight ratio of Pd to Rh ranging between 8-40:1, preferably between 10-25 : 1, and more preferably, around 11-19: 1. The downstream FPG carrying a lower concentration of platinum group metals also comprises certain ratios of these platinum group metals. Again, for example, in case palladium and rhodium are the only platinum group metals in question, the downstream FPG shows a weight ratio of Pd to Rh between 1-10 : 1, preferably between 1-5 : 1, and more preferably around 1-3 : 1.
    [020] The present invention provides an exhaust treatment system for engines with direct gasoline injection. The system comprises a CTV device followed by an FPG which is also coated with a catalyst comprising CTV functionality. The CTV - according to the invention - is positioned in an upstream part of the exhaust system. In a preferred embodiment of the present invention, the CTV device is located in a position called closed loop coupled. This means that the device for emission treatment coupled in a closed circuit is positioned close to the exhaust outlet manifold, the exhaust outlet itself or the turbocharger. That is, the CTV is preferably located approximately 2-40 cm downstream of the engine, more preferably approximately 5-30 cm and most preferably 5-20 cm away from the respective exhaust/turbocharger outlet.
    [021] Typically, vehicles have an engine compartment containing the engine and related subsystems and devices, including the closed loop coupled emission treatment device mentioned above. Vehicle wall protection separates the engine compartment and driver/passenger compartment from sub-floor subsystems and devices. The latter is naming a position below the floor or below the body of a device if the device is positioned under the floor of said vehicle. In a preferred aspect of the present invention, the downstream FPG is located in such a position below the floor. The FPG downstream of the invention is therefore in fluid communication with the upstream CTV which is associated with the engine, turbocharger or manifold output, so that the exhaust gases produced by the direct injection engine are first transported through the CTV device, preferably, located in a closed-loop coupled position, and then loaded through an exhaust pipe to the downstream FPG, preferably positioned in a location below the floor. For reasons of flux fluid dynamics or exhaust gas diffusion, it was found that there is an optimal distance between the CTV and the FPG. This distance strongly depends on several aspects, for example, the involved engine and system parameters, such as CTV activity vs. FPG. Consequently, it is contemplated to be in a position below the floor position if the FPG is located approximately 60-200 cm downstream of the engine outlet or exhaust manifold discharge channel. In a further preferred embodiment, the FPG is located 60-150 cm downstream of said outlet. More preferably, the distance between said outlet and FPG inlet is 60-120 cm.
    [022] All, some or only one of the platinum group metals that are applied to the upstream CTV and/or the downstream FPG may be distributed evenly on the respective device, may be present therein in a zoned arrangement, or may be arranged in layers.
    [023] In a most preferred embodiment, the upstream CTV shows a zoned arrangement with respect to all, some or only one of the platinum group metals located therein. In particular, for example, in case only palladium and rhodium are present as platinum group metals, the palladium content can be distributed over the upstream CTV in a non-uniform manner, while the rhodium content is distributed equally from advantageous mode over the entire device. This means that only the upstream CTV has Pd-zoning. More preferably, the palladium content in an upstream CTV input zone is greater than the palladium content in an upstream CTV output zone. The weight ratio of this palladium content should lie within the limits of 2-10: 1, preferably 3-7: and more preferably around 4-5 : 1. The inlet zone is located from the device inlet to less than its total length to the discharge channel. The discharge zone is located from the discharge channel of the device to less than its full length to the inlet channel. Both zones can overlap each other or can be arranged with or without a gap between them. Preferably, the inlet zone has a relative length compared to the substrate of 1/5 - 1/2, more preferably 1/5 - 1/3 and most preferably 1/5 - 1/4. The discharge zone is preferably the same length as the inlet zone. In a more preferred embodiment, both zones are 7-8 cm long and provide a 4-5 : 1 load-Pd difference between the respective zones.
    [024] As the size of the particulate matter produced by an engine with direct gasoline injection is quite small, the pores and porosity of the filter for catalyzed gasoline particulates become important, in the sense that an advantageous balance has to be found between filtering efficiency and back pressure related damage. Furthermore, the CTV functionality being present in the filter can give rise to even more back pressure if applied to the filter with a disadvantageous washcoat. It was found that the back pressure problem can be overcome by choosing specifically optimized washcoat, having three-way functionality in FPGs comprising adapted porosities and medium pore sizes. Not wishing to be bound by theory, it is believed that although the particle size of the particulate material in the gasoline exhaust is smaller compared to the diesel engine exhaust (see discussion above), the average wall pore size of FPGs according to this invention can show a very large average pore size of > 14 or even > 20 MP (SAE2007010921). At least the adopted pore sizes seem to be in conflict with the recommendations given in the literature (SAE2011010814). Due to the fact that washcoats having appropriately sized particles more or less penetrate the pores of FPG walls, they help to capture soot but prevent the development of back pressure. In a more preferred aspect, the average pore size of the FPG is between 14-25, more preferably between 15-21. The amount of washcoat present on or in the FPG can be appropriately determined in accordance with the teaching of document US20110252773 with respect to the topics mentioned above.
    [025] Consequently, at least to a certain extent, the washcoat is not covering the walls of the FPG according to the invention, but is located in their own pores. To be able to enter the porous structure of the FPG walls, the washcoat particles need to be smaller than the average pore size of the filter. It is, therefore, advantageous if the particle size of particles in the washcoat is smaller than the average pore size of the FPG involved. Preferably, the particle size of the washcoat is therefore between 0.1-20 MP, more preferably between 0.1-15 MP and most preferably between 0.1-10 MP.
    [026] It is presented that the size of particles presented here shows a certain variation in diameter values. It is important that it be understood by those skilled in the art that at least 80%, preferably at least 90% and more preferably at least 95% of the particles present in the washcoat have a diameter in the ranges mentioned above.
    [027] In another aspect of the present invention, the filter for involved wall flow gasoline particulates has a certain porosity. Not only are the instant FPG average pore sizes crucial to balancing the backpressure-related harm. Also the amount of pores determines the back pressure of a wall flow filter. Advantageously, the gasoline wall flow particulate filter according to the present invention has a porous wall structure comprising porosities between 45%-75%, preferably, the porous structure has a porosity between 55%-70%, and more preferably between 60%-65%.
    [028] An especially preferred aspect of the present invention is directed to an engine exhaust treatment system with direct gasoline injection comprising a three-way catalyst coupled in a closed circuit (CTV), for example, with Pd-zoning, and a downstream CTV gasoline particulate (FPG) filter, where the average pore size of the wall flow particulate filter is around 18-22 MP, the particle size in the washcoat applied to the filter is between 1- 7 MP, and the filter porosity is around 60-70%.
    [029] In another embodiment of the present invention, the present invention is directed to a process for the reduction of harmful pollutants emitted by gasoline engines, in which the exhaust gas comes in contact with a system according to the invention. It is important to be understood by those skilled in the art that all of the anticipated and advantageously mentioned aspects and embodiments of the inventive system also readily apply mutatis mutandis to the present process. CTV SUBSTRATE
    [030] The CTV catalytic composites are arranged on a substrate. The substrate can be any of those materials commonly used to prepare catalysts, and will preferably comprise a ceramic or metal honeycomb structure. Any suitable substrate may be employed, such as a monolithic substrate of the type having thin, parallel gas flow passages extending therethrough, from an inlet or outlet face of the substrate, such that passages are open to drain the flow through it (referred to as honeycomb-type flow substrates). The passages, which are essentially straight pathways from their fluid inlets to their fluid outlets, are defined by walls on which the catalytic material is coated as a washcoat so that gases flowing through the passages come into contact with the catalytic material. Monolithic substrate flow passages are thin-walled channels, which can be of any shape and size in cross section, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. These structures can contain from about 60 - 900 or more gas inlet openings (ie cells) per square inch of cross section.
    [031] The ceramic substrate can be produced from any suitable refractory material, for example, cordierite, cordierite-alumina, silicon nitrite, zirconium mullite, spodumene, alumina-silica magnesia, zirconium silicate, silimanite, a magnesium silicate, zirconium , petalite, alumina, an aluminosilicate, etc. Substrates useful for the catalytic composite of the present invention may also be metallic in nature, and may be composed of one or more metals or metal alloys. Metallic substrates can be used in various formats, such as corrugated sheet or monolithic form. Preferred metal supports include heat resistant metals and metal alloys such as titanium and stainless steel, as well as other alloys in which iron is a substantial or major component. These alloys may contain one or more of nickel, chromium, and/or aluminum, and the total amount of these metals may advantageously comprise at least about 15% by weight of the alloy, for example approximately 10 - 25% by weight of chromium, approximately 3-8% by weight aluminum and up to approximately 20% by weight nickel. Alloys can also contain small amounts or traces of one or more other metals, such as manganese, copper, vanadium, titanium, and the like. The surface of metal substrates can be oxidized at high temperature, for example approximately 1000°C and higher, to improve the corrosion resistance of the alloys by forming an oxide layer on the substrate surfaces. This high temperature induced oxidation can increase the adhesion of the refractory oxide support, and catalytically promote the metal components to the substrate. In alternative embodiments, one or more catalytic compositions can be deposited onto an open cell foam substrate. These substrates are well known in the art, and are typically formed from refractory ceramic or metallic materials. FPG SUBSTRATE
    [032] According to the present invention, a treatment system is provided comprising a filter for wall flow particulates which is adapted especially for the treatment of gasoline engine exhaust gas streams, in particular those originating from engines with direct gasoline injection. Advantageously, any wall flow filter substrate can be used in the present invention, as long as it allows the effective filtration of particulate material contained in gasoline engine exhaust gas streams. Preferably, a gasoline particulate filter (FPG) is used as the filter substrate, wherein, in accordance with the present invention, in reference to a so-called particulate filter medium configured to trap particulates generated by combustion reactions in the gasoline engine, preferably in gasoline engines with direct injection technologies.
    [033] Consequently, the FPG substrate is a wall flow monolith or wall flow filter, and more preferably, a wall flow filter having a honeycomb structure. Wall flow substrates include those with a plurality of thin, substantially parallel gas flow passages extending along the longitudinal axis of the substrate. Preferably, each pass is blocked at one end of the substrate body, with alternate passes blocked at opposite end faces. The U.S. Pat. No. 4,329,162 is incorporated by reference herein with respect to the disclosure of suitable wall flux substrates that can be used in accordance with the present invention.
    [034] The filter substrate for particulates can be designed of any material or combination of materials that allow the filtration of particulate material contained in the gasoline engine exhaust gas, preventing the function of a gasoline engine in fluid communication with the filter for particulates. For this purpose, porous materials are preferably used as the substrate material, in particular ceramic-type materials such as cordierite, alpha alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina -silica-magnesia and zirconium silicate, as well as porous refractory metals and their oxides. According to the present invention, "refractory metal" refers to one or more metals selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The particulate filter substrate can also be formed from ceramic fiber composite materials. According to the present invention, the particulate filter substrate is preferably formed from cordierite, silicon carbide, and/or aluminum titanate. In general, the materials that are preferred are those that are capable of withstanding the high temperatures to which a particulate filter is exposed when used in the treatment of gasoline engine exhaust gas.
    [035] More specifically, the particulate filter preferably comprises a particulate filter substrate, a first layer disposed on or on said surface of the filter substrate, and optionally a second layer disposed on or on said surface of the filter substrate. filter. In a most preferred embodiment of the invention, the coating is disposed wholly or at least predominantly within the porous walls of the wall flow filter substrate. CTV WASHCOAT
    [036] According to the present invention the filter for gasoline wall flow particulates and the upstream CTV are coated with an appropriate washcoat carrying a catalyst comprising three-way functionality. The washcoat of both devices can be the same or different. In principle, within the scope of the present invention any CTV washcoat can be employed in the treatment system, provided that effective treatment of the gasoline engine exhaust gas can be carried out. Suitable CTV washcoats in single-layer or multi-layer design can be found, for example, in EP1974810B1 PCT/EP2011/070541, EP1974809B1, or PCT/EP2011/070539. For further information, see the literature cited in the prior art. CTV catalysts comprising platinum group metals, e.g. Rh and Pd, are employed, more preferably they comprise only Pd and R.
    [037] In preferred embodiments of the present invention, the CTV washcoat comprises a catalyst composed of a metal oxide support material, said support material preferably being selected from the group consisting of alumina, zirconia, zirconia-alumina, barium oxide- alumina, lantana-alumina, lantana-zirconia-alumina, and mixtures thereof. In particularly preferred embodiments, the metal oxide support material is gamma alumina. Preferably, the support material is doped with rare earth, alkaline earth or refractory metal oxide in an amount preferably ranging from 0.01 to 30% by weight, more preferably from 0.05 to 15% by weight, even more preferably from 0.1 to 10% by weight. In particular, rare earth, alkaline earth or refractory metal oxide are preferably selected from the group consisting of ceria, lantana, praseodymia, neodymia, barium oxide, strontium oxide, zirconia and mixtures thereof, where rare earth, alkaline earth or refractory metal oxide are preferably lantana, barium oxide and/or zirconia. According to a particularly preferred embodiment of the present invention, the metal oxide support material is gamma alumina which is preferably doped with a rare earth. , alkaline earth or refractory metal oxide, more preferably with lantana, barium oxide and/or zirconia. In addition to said support material, the CTV catalyst according to the present invention preferably comprises an oxygen storage component (CAO), said CAO being preferably selected from the group consisting of ceria, praseodymia and mixtures thereof, and mixtures of those materials with other metal oxides, most preferably from the group consisting of ceria-zirconia-, ceria-zirconia-lantana-, ceria-zirconia-neodymia-, ceria-zirconia-praseodymia, ceria-zirconia-yttria-, ceria-zirconia-lantana-neodymia- , ceria-zirconia-lantana-praseodymia- or mixture of ceria-zirconia-lantana-yttria.
    [038] The catalytic composite can be readily coated on a carrier. For a first coat of a specific washcoat, finely divided particles of a high surface area metal oxide such as gamma alumina are disposed in a suitable vehicle, eg water. To incorporate components such as platinum group metals (e.g. palladium, rhodium, platinum, and/or combinations thereof), stabilizers and/or promoters, these components can be incorporated into the slurry as a mixture of water soluble or compounds or complexes dispersible in water. Typically, when PGM components, eg Pd and/or Rh, are included in the washcoat, the component in question is used in the form of a compound or complex to achieve dispersion of the component on the metal oxide support, eg alumina activated, such as gamma alumina. With respect to the CTV washcoat, the term "component" means any compound, complex, or the like which, on calcification or use thereof, decomposes or otherwise converts to a catalytically active form, typically metal or metal oxide . This therefore applies to all platinum group elements used alone or in combination with each other in accordance with the present invention. Water-soluble compounds or water-dispersible compounds or complexes of the metal component can be used insofar as the liquid medium used to impregnate or deposit the metal component on the refractory metal oxide support particles does not inadvertently react with the metal or its compound or its complex, or other elements which may be present in the catalytic composition and which are capable of being removed from the metal component by volatilization or decomposition shortly after heating and/or application of a vacuum. In some cases, completion of liquid removal cannot occur until the catalyst is put into use and subjected to the elevated temperatures encountered during operation. In general, from the point of view of economics and environmental aspects, aqueous solutions of soluble compounds or complexes of precious metals are found. For example, suitable compounds are palladium nitrate or rhodium nitrate.
    [039] In general, any conceivable method can be employed for the production of the treatment system according to the present invention (for FPG: US2009129995, EP1789191, WO2006021336). Using those known techniques, catalyst slurry can permeate the substrate walls. As used in this document, the term "permeate" when used to describe the dispersion of the catalytic slurry on the substrate means that the catalytic composition is dispersed throughout the substrate wall.
    [040] Coated substrates are typically dried at approximately 100°C, and calcined at a higher temperature (eg 300 to 450°C and up to 550°C). After calcification, catalyst loading can be determined by calculating the coated and uncoated weights of the substrate. As will be apparent to those skilled in the art, catalyst loading can be modified by changing the solids content of the coating slurry. Alternatively, repeated immersions of the substrate in the coating slurry can be conducted, accompanied by removal of excess slurry, as described above.
    [041] The catalytic composites of the present invention can be formed in a single layer or in multiple layers or zones. In some cases, it may be appropriate to prepare a slurry of catalytic material and use this slurry to form multiple layers on the carrier. Composites can be readily prepared by processes well known in the prior art. A representative process is expressed below. As used herein, the term "washcoat" has its usual meaning in the art of a thin, adherent coating of a catalytic or other material applied to a substrate carrier material, such as a honeycomb carrier member, which is porous or porous. sufficient to allow the gas stream to be treated to pass through it.
    [042] It is expressly mentioned that more catalysts or functionalities may be associated with the present system, such as, for example, the SCR functionality and/or CAO functionality and/or NSC functionality, etc. (US20110158871; US20090193796).
    [043] The implementation of catalyzed gasoline particulate (FPG) filter in the exhaust aftertreatment system can be a cost-effective and sustainable solution to reduce particulate emissions from direct injection gasoline engines. The most challenging task is to provide sufficient particle number reduction at adequate pressure drop so as not to compromise the CO2 advantage of GDI engines while providing a high degree of conversion efficiency for regulated pollutants at the same time. By applying a dedicated three-way functional washcoat on a ceramic wall flow filter and an upstream CTV, all of the above mentioned requirements could be satisfied to meet at least future Euro 6 legislation.
    [044] The beneficial impact of catalytic coating on particle filtration efficiency, as well as the conversion efficiency of catalyzed FPG to hydrocarbons, carbon monoxide and nitrous oxides could be proven. The replacement of a three-way catalyst in a position below the floor of a two-converter exhaust system with a catalyzed FPG could be performed without any impact on the conversion efficiency for all regulated pollutants. Data obtained with exhaust systems comprising conventional three-way catalysts for particulates in modern GDI applications further illustrate that together with the new filtration performance acquired, the emission reduction performance for all regulated pollutants can be improved. In particular, NOx emissions in the tailpipe could be substantially reduced with an additional catalyzed FPG. FIGURES:
    [045] Fig. 1 shows an experimental setup and instrumentation location diagram.
    [046] Fig. 2 shows particle number emissions in NEDC test and filtration efficiency.
    [047] Fig. Shows NEDC 1.4L GDTI emissions profile.
    [048] Fig. 4 shows raw exhaust emissions in NEDC 4 test - 1.4L.
    [049] Fig. 5 shows 1.4L GDTI exchange emission comparison between reference and NEDC staged systems. FIG. 1
    [050] 1: gasoline engine
    [051] 2: emission analyzer
    [052] 3: Reference CTV
    [053] 4: emission analyzer
    [054] 5: Uncatalyzed FPG
    [055] 6: emission analyzer
    [056] 7: CTV
    [057] 8: Catalyzed FPG
    [058] 9: CTV zoned EXAMPLES EXPERIMENTAL CONFIGURATION
    [059] Emission analyzers (AVL/Pierburg AMA4000) were used to measure the gaseous emission CO, CO2, NOx, THC and O2. Exhaust gas sensors are located 2" before (2) and after (4) the CTV and after the FPG (6). Thermocouples and pressure sensor have been placed in similar locations for temperature and back pressure measurement. Additional lambda sensors have been used to measure the air-fuel ratio A Horiba MEXA1000 was used to measure number of particulates according to MPP As the number of particulates was PN was measured after FPG, the additional dilution step from MEXA1000 was used. The instrument was able to provide time-based particle number data.
    [060] Four systems were built (fig.1) and evaluated in a 1.4L DI engine. The reference system used a substrate 101.6mm in diameter by 152mm in length (3). Cell density is 600 cpsi. Examples 1 and 2 used the same reference CTV catalyst technology, but with a slightly different PGM loading ((3) and (9)) with an uncatalyzed (5) and catalyzed (8) FPG device, respectively, in the location below the floor. Example 3 used a PGM zoned CTV catalyst (9) with a catalyzed FPG (8). All FPG substrates are made of cordierite material with a porosity of 65% and an average pore size of approximately 20 prn. The substrate dimensions are 118.4mm in diameter by 152mm in length. Cell density and wall thickness are 300 cpsi with 12mil wall thickness. The filter substrates were coated with washcoat mud having a three-way functional composition specifically optimized for use in FPGs. Precious metal loadings of both closed-loop coupled CTV and underbody FPG can be found in Table 2. All catalyzed FPG systems evaluated in this study have lower precious metal costs than the reference system. All systems were dated in parallel following a fuel cut-off dating procedure with a bed temperature of 1030 °C inside the closed-loop coupled CTV catalyst. TABLE 2 - PRECIOUS METAL LOADING AND SYSTEM COSTS SHOWN IN FIG. 1.
    TEST RESULTS IN GDI 1.4L VEHICLE
    [061] Only for the application of catalyzed FPGs a 1.4L GDI vehicle was chosen: It was a 2005 MY 1.4L direct injection engine with turbocharger. The engine is calibrated for Euro 4 emissions and uses a 1.25l production closed-loop coupled catalytic converter. This engine was installed in a high dynamic engine seat equipped with a CVS system for bag analysis, three online analyzer lines (raw gas, after CTV and after FPG) for gaseous emission components and a particulate counter ( Horiba MEXA 1000) which was used in undiluted exhaust after FPG. To measure according to MPP the additional dilution step is also used. All results shown for the high dynamic engine seat were average values from at least five tests. PARTICULATE EMISSION TEST RESULTS
    [062] The particle number emissions measured in the European Driving Cycle of the four exhaust systems described in fig. 1 have been shown in fig. 2. CTV particulate number emissions profile only refers to system is identical to vehicle raw emissions. There is no measurable particle number reduction since the three-way catalyst on a flow-through substrate. Examples 1 to 3 equipped with gasoline particulate filters reduce the amount of particulates emitted drastically. Fig. 2 summarizes particulate emissions and filtration efficiency. The NEDC-based particulate emission profile for all systems is shown in fig. 3. The filtration efficiency of each aftertreatment system was calculated proportional to the measurements of the engine off. Each value represents the average of five NEDC tests. With the cordierite type filter chosen, the filtration efficiency of Example 1 is 88% resulting in an emission of 1.7 x 1011 #/km. Applying a washcoat to the filter the filtration efficiency increased to 99% and 99% for Example 2 and Example 3 resulting in 1.4 x 1010 #/km and 1.2 x 1010 #/km respectively. Both systems safely meet the proposed limits. CO, HC AND NOx CONVERSION EFFICIENCY
    [063] The raw emissions obtained for all regulated pollutants measured in the European Driving Cycle are shown in fig. 4.All modal emission data between 0 sec and 1200 sec was collected in off-engine location using AVL/Pierburg AMA4000 gas analyzers. While the cumulative mass of CO and HC emissions increases almost linearly over the cycle, there is a significant increase in the mass of NOx emissions during the last phase of high-speed acceleration.
    [064] The emissions per bag of CO, HC and NOx from the researched after-treatment systems are summarized in fig. 5. All values were weighted from at least five test results. Due to the addition of below-floor canning comprising a filter this application changes the combustion behavior and lambda control slightly compared to the simple converter configuration. Thus, the HC emissions through the tailpipe (and also CO and NOx in ECE) are different for Reference and Example 1, respectively, both having the same CTV coupled in a closed circuit, although these systems show the same conversion efficiency. of HC. In contrast, a clear advantage in HC conversion could be seen using the zoned CTV of Example 3. It is clearly visible that using a PGM zoned closed-loop coupled CTV at PGM costs similar to tailpipe CO emissions can be significantly reduced to achieve a reduction of approximately 12% in CO emissions compared to other systems.
    [065] The competitive advantage of the catalyzed FPGs, Examples 2 and 3, is the observed improvement in NOx emissions. Differences are apparent during the EUDC portion of the European Driving Cycle. Although NOx disruptions could be observed during high-speed phase acceleration for Reference and Example 1, catalyzed FPGs are able to attenuate this effect considerably. Figure 5 shows that using a catalytic FPG in the system the total NOx emissions in the tailpipe are 10 mg/km lower than for the reference system.
    权利要求:
    Claims (19)
    [0001]
    1. GASOLINE ENGINE EXHAUST TREATMENT SYSTEM comprising a closed-loop coupled three-way catalyst (CTV) and a downstream catalyzed wall flow (FPG) filter for gasoline particulates, characterized by the amount of group metals platinum in the CTV exceeds the amount of platinum group metals in the FPG by a factor of at least 5 and where the platinum group metal charge of the CTV is 25-120 g/ft3 and the platinum group metal charge of the FPG is 2-20 g/ft3.
    [0002]
    2. TREATMENT SYSTEM according to claim 1, characterized in that both devices comprise the platinum group metals Pd and Rh.
    [0003]
    3. TREATMENT SYSTEM according to claim 1, characterized in that the upstream CTV is located approximately 5-20 cm downstream of the engine discharge channel, the manifold discharge channel or the turbocharger.
    [0004]
    4. TREATMENT SYSTEM according to claim 1, characterized in that the downstream FPG is located approximately 60-120 cm downstream of the engine.
    [0005]
    5. TREATMENT SYSTEM according to claim 1, characterized in that the weight ratio of Pd to Rh in the CTV is 8-40: 1.
    [0006]
    6. TREATMENT SYSTEM according to claim 1, characterized in that the weight ratio of Pd to Rh in the FPG is 1-10: 1.
    [0007]
    7. TREATMENT SYSTEM according to claim 1, characterized in that the CTV upstream has a zoning-Pd.
    [0008]
    8. TREATMENT SYSTEM according to claim 1, characterized in that the downstream FPG has a porous structure with an average pore size of 14-25 µm.
    [0009]
    9. TREATMENT SYSTEM according to claim 8, characterized in that the particle size of particles that support the platinum group metals received by the FPG is smaller than the average pore size of the FPG involved.
    [0010]
    10. TREATMENT SYSTEM according to claim 1, characterized in that the downstream FPG has a porous structure with a porosity between 45%-75%.
    [0011]
    11. PROCESS FOR THE REDUCTION OF HARMFUL POLLUTANTS EMITTED BY GASOLINE ENGINES, characterized in that the exhaust gas comes into contact with a system as defined in claim 1, the system comprising a three-way catalyst coupled in a closed circuit (CTV) and a catalyzed downstream wall flow (FPG) gasoline particulate filter, in which the amount of platinum group metals in the CTV exceeds the amount of platinum group metals in the FPG by a factor of at least 5; and where the platinum group metal charge of the CTV is 25-120 g/ft3 and the platinum group metal charge of the FPG is 2-20 g/ft3.
    [0012]
    12. TREATMENT SYSTEM according to claim 1, characterized in that the amount of platinum group metals in the CTV exceeds the amount of platinum group metals in the FPG by a factor of 10-23.
    [0013]
    13. TREATMENT SYSTEM according to claim 1, characterized in that the amount of platinum group metals in the CTV exceeds the amount of platinum group metals in the FPG by a factor of 15-20.
    [0014]
    14. TREATMENT SYSTEM according to claim 1, characterized in that the amount of platinum group metals in the CTV exceeds the amount of platinum group metals in the FPG by a factor of 16-19.
    [0015]
    15. TREATMENT SYSTEM according to claim 1, characterized in that the metal load of the platinum group of the CTV is 30-80 g/ft3.
    [0016]
    16. TREATMENT SYSTEM according to claim 1, characterized in that the FPG has a platinum group metal charge that is disposed entirely or at least predominantly within the porous walls of the FPG.
    [0017]
    17. TREATMENT SYSTEM according to claim 1, characterized in that the metal load of the platinum group of the FPG is 2-15 g/ft3.
    [0018]
    18. TREATMENT SYSTEM according to claim 1, characterized in that the metal load of the platinum group of the FPG is 2-10 g/ft3.
    [0019]
    19. TREATMENT SYSTEM according to claim 1, characterized in that the FPG has an average pore size of 18-22 µm and a porosity of 60-70%.
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    同族专利:
    公开号 | 公开日
    US9581063B2|2017-02-28|
    JP2018035808A|2018-03-08|
    EP2650042B2|2020-09-02|
    US20150107228A1|2015-04-23|
    EP2650042B1|2014-11-26|
    RU2618685C2|2017-05-10|
    RU2014145429A|2016-06-10|
    CN104661730A|2015-05-27|
    JP6785749B2|2020-11-18|
    EP2650042A1|2013-10-16|
    JP2020008022A|2020-01-16|
    JP2015528868A|2015-10-01|
    KR102107978B1|2020-05-08|
    CN104661730B|2016-10-26|
    WO2013153081A1|2013-10-17|
    EP2836288A1|2015-02-18|
    KR20150008382A|2015-01-22|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-09-29| B07B| Technical examination (opinion): publication cancelled [chapter 7.2 patent gazette]|
    2020-10-06| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    EP12164142.7|2012-04-13|
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