WO2023198571A1 - Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac - Google Patents

Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac Download PDF

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Publication number
WO2023198571A1
WO2023198571A1 PCT/EP2023/059080 EP2023059080W WO2023198571A1 WO 2023198571 A1 WO2023198571 A1 WO 2023198571A1 EP 2023059080 W EP2023059080 W EP 2023059080W WO 2023198571 A1 WO2023198571 A1 WO 2023198571A1
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WIPO (PCT)
Prior art keywords
catalyst
ammonia
osc
exhaust system
exhaust gas
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PCT/EP2023/059080
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German (de)
English (en)
Inventor
Julius KOEGEL
Massimo Colombo
Sonja Buchberger
Marcus Schmidt
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Umicore Ag & Co. Kg
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Priority claimed from DE102023101772.1A external-priority patent/DE102023101772A1/de
Application filed by Umicore Ag & Co. Kg filed Critical Umicore Ag & Co. Kg
Publication of WO2023198571A1 publication Critical patent/WO2023198571A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9436—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
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    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
    • B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
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    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
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    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/18—Ammonia

Definitions

  • the present invention is directed to an exhaust system for reducing exhaust gases and in particular ammonia emissions in the exhaust system of a predominantly stoichiometrically operated spark ignition engine.
  • Exhaust gases from internal combustion engines operated with predominantly (>50% of the operating time) stoichiometric air/fuel mixture i.e. e.g. B. spark ignition engines or gasoline engines powered by gasoline or natural gas are cleaned in conventional processes using three-way catalysts (TWC). These are able to simultaneously convert the engine's three main gaseous pollutants, namely hydrocarbons, carbon monoxide and nitrogen oxides, into harmless components.
  • Stoichiometric means that on average there is as much air available to burn the fuel in the cylinder as is needed for complete combustion.
  • the combustion air ratio A (A/F ratio; air/fuel ratio) relates the air mass mL.tats actually available for combustion to the stoichiometric air mass mi_,st:
  • a ⁇ 1 (e.g. 0.9) this means “lack of air”
  • a > 1 (e.g. 1.1) means “excess air” and the exhaust gas mixture is referred to as lean.
  • the statement A 1.1 means that 10% more air is present than would be necessary for the stoichiometric reaction. The same applies to the exhaust gases from internal combustion engines.
  • the catalytically active materials used in the known three-way catalysts are generally platinum group metals, in particular platinum, palladium and rhodium, which are present, for example, on ⁇ -aluminum oxide as a support material.
  • three-way catalysts contain oxygen storage materials, for example cerium/zirconium mixed oxides. In the latter, cerium oxide, a rare earth metal oxide, is the fundamental component for oxygen storage. In addition to zirconium oxide and cerium oxide, these materials can contain additional components such as other rare earth metal oxides or alkaline earth metal oxides.
  • Oxygen storage materials are made by Application of catalytically active materials such as platinum group metals activates and thus also serves as a carrier material for the platinum group metals.
  • Compliance with the strict emission values for ammonia requires the use of a storage material to store NH3 during the rich operating conditions of the internal combustion engine, especially for low and medium temperature ranges, as the ammonia is mainly formed under these exhaust gas conditions.
  • the stored ammonia is then converted during lean operating points by oxidation on a layer containing precious metal and/or as part of an SCR reaction.
  • the aim here is to achieve the lowest possible selectivity to N2O.
  • a special requirement for the catalysts considered here is the high aging stability of the materials used: In addition to the stability against lean gas conditions, their use in the exhaust system of stoichiometrically operated internal combustion engines requires that they also be stable in exhaust gas with a rich or stoichiometric composition under hydrothermal exhaust gas conditions.
  • the ammonia can also be converted into nitrogen via the ASC with the oxygen present.
  • a further disadvantage of the known systems for reducing ammonia emissions is that the transition metals in the SCR component, such as iron and/or copper, tend to dissolve in the exhaust system of a predominantly stoichiometrically operated internal combustion engine after a long period of use to diffuse the component for the oxidation of ammonia and poison it. The result is a lower activity of the SCR and the oxidative component.
  • NH3 and N2O should be safely adhered to in addition to the traditional ones for CO, HC and NOx.
  • the system should also be robust and agile in order to be able to withstand the working conditions in the exhaust system of a corresponding automobile for a sufficient period of time.
  • Claims 2 - 8 relate to preferred embodiments of the exhaust system and can accordingly also be applied to the method according to the invention.
  • an exhaust system for reducing the harmful exhaust gas components of internal combustion engines in particular predominantly stoichiometrically operated internal combustion engines, such as spark-ignited gasoline engines, having a first three-way catalytic converter and, on the downstream side, a catalyst for reducing ammonia emissions, which has the following components:
  • the system according to the invention is characterized by an extremely good Performance in terms of reducing CO, HC and NOx emissions as well as NH3 and IX ⁇ O emissions. It reacts well to the dynamic requirements in the exhaust system of a gasoline engine and is sufficiently robust to meet these requirements for a sufficient period of time.
  • a first component of the catalyst for reducing ammonia emissions consists of zeolites and/or zeotypes for storing ammonia.
  • zeolites and/or zeotypes for storing ammonia.
  • those skilled in the art are familiar with the zeolites and zeotypes available for this purpose from the diesel sector.
  • the way the zeolites or zeotypes work is based on the fact that they can temporarily store ammonia in operating states of the exhaust gas purification system in which ammonia is produced, for example, by over-reduction of nitrogen oxides via a three-way catalytic converter installed on the upstream side, but this cannot be converted by other conventional three-way catalytic converters, for example because of the Lack of oxygen or insufficient operating temperatures.
  • the ammonia stored in this way can then be removed from storage when the operating state of the exhaust gas purification system changes and subsequently or directly converted, for example when sufficient oxygen or nitrogen oxides are present.
  • zeolites and zeotypes are present in the first component of the catalyst to reduce ammonia emissions.
  • IZA https://europe.iza-structure.org/IZA-SC/ftc_table.php
  • the international zeolite association, zeolites or zeotypes can be divided into different classes. Zeolites are then divided, for example, according to their channel system and their framework structure. For example, laumontite and mordenite are classified as zeolites, which have a one-dimensional system of channels. Your channels are not connected to each other. Zeolites with a two-dimensional channel system are characterized by the fact that their channels are connected to each other in a kind of layered system.
  • a third group has a three-dimensional framework structure with cross-layer connections between the channels.
  • Two- and/or three-dimensional zeolites or zeotypes are preferably used in the present invention [Ch. Baerlocher, WM Meier and DH Olson, Atlas of Zeolite Framework Types, Elsevier, 2001], According to the invention, the term “zeolite” refers to porous materials with a lattice structure of corner-linked AIO4 and SiCU tetrahedra according to the general formula (WM Meier, Pure & Appl. Chem., Vol. 58, No. 10, pp. 1323-1328 , 1986):
  • the structure of a zeolite therefore comprises a network made up of tetrahedra that encloses channels and cavities.
  • zeotype is understood to mean a zeolite-like compound that has the same structural type as a naturally occurring or synthetically produced zeolite compound, but which differs from such compounds in that the corresponding cage structure is not made up exclusively of aluminum and silicon framework atoms.
  • the aluminum and/or silicon framework atoms are proportionally replaced by other trivalent, quadrivalent or pentavalent framework atoms such as B(III), Ga(III), Ge(IV), Ti(IV) or P(V).
  • the most common method used in practice is the replacement of aluminum and/or silicon framework atoms by phosphorus atoms, for example in the silicon aluminum phosphates or in the aluminum phosphates, which crystallize in zeolite structure types.
  • zeolites come from the group of two-dimensional or three-dimensional zeolites/zeotypes. They preferably belong to the structure types AGO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, BEA, BIK, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, ESV, ETL, GIS , GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON.
  • the zeolites or zeotypes in the car exhaust gas catalyst according to the invention are selected from the group AEI, AFT, AFX, CHA, DDR, ERI, ESV, ETL, KFI, LEV, UFI and the corresponding zeotypes of these structural types, such as: SAPO. Mixtures of the same can also be present.
  • CHA, FER, LEV and AEI is particularly preferred.
  • metal-free means the absence of metals in ionic, oxidic or metallic form, which could catalyze the SCR reaction or ammonia oxidation. It therefore essentially contains no transition metals, in particular iron and/or copper, and also no precious metals. The need for prior contact with these metals is therefore eliminated.
  • the zeolite/zeotype may contain residues of metals such as sodium or potassium etc. in low concentrations. This is usually the case Zeolite/zeotype after calcination is preferably essentially in the H form (so-called white zeolite).
  • the aging stability of the zeolites or zeotypes used in the exhaust system of predominantly stoichiometrically burning engines is particularly in focus here, since higher temperatures generally prevail here than in a lean-burning engine. In this respect, materials are desired that can withstand the sometimes very high and rapidly changing hydrothermal conditions for as long as possible.
  • the exhaust gas composition is also different compared to lean-burn engine exhaust.
  • concentration, in particular of hydrocarbons and carbon monoxide, which arrive at the catalyst according to the invention is, on the one hand, higher than in lean-burn engines and the composition also changes depending on the driving style around the stoichiometric range (rich/lean change).
  • the hydrothermal temperature stability of zeolites and zeotypes depends heavily on the SAR value (silica-to-alumina ratio) of the zeolite or the ratio corresponding to this value for zeotypes.
  • SAR value silicon-to-alumina ratio
  • the amount of silicon atoms remaining in the framework is then related to the substitution atoms. It has proven to be advantageous if the zeolites have a SAR value of 10 - 50, preferably 12 - 35 and most preferably 13 - 30. The same applies to the zeotype with the corresponding ratio.
  • the first component can preferably have other non-catalytically active components, such as binders.
  • binders temperature-stable metal oxides that are not or only slightly catalytically active, such as SiO2, Al2O3 and ZrÜ2, are suitable as binders.
  • the expert knows which materials come into question here.
  • the proportion of such binders in the first coating can, for example, be up to 15% by weight, preferably up to 10% by weight, of the coating.
  • the binder should also not contain the transition metals specified above, in particular iron and/or copper, and no precious metals. Binders are suitable for ensuring stronger adhesion of the coating to a carrier or another coating.
  • the ammonia storage ability or capacity addressed in the context of this invention is given as a quotient of the stored mass of ammonia per liter of catalyst support volume.
  • the zeolites or zeotypes should increase the ammonia storage capacity of the exhaust gas purification system to at least 0.25 g of ammonia per liter of carrier volume (measured in the fresh state).
  • the storage capacity of the ammonia storage components used should be sufficient so that the system contains between 0.25 and 10.0 g of NH3 per liter of carrier volume, preferably between 0.5 and 8.0 g of NH3 per liter of carrier volume and particularly preferably between 0.5 and 5.
  • 0 g NH3/U-ter carrier volume of ammonia can be stored (always based on the fresh state).
  • the zeolites or zeotypes are present in sufficient quantities in the catalyst to reduce ammonia emissions. The determination of the ammonia storage capacity is shown below.
  • the second component consists of an OSC-free precious metal catalyst and/or an OSC-containing noble metal catalyst.
  • Precious metal refers in particular to the platinum group metals platinum, palladium and rhodium. Accordingly, the noble metals in the OSC-free or OSC-containing noble metal catalyst are selected from the group consisting of palladium, platinum, rhodium.
  • OSC means Oxygen Storage Catalyst - oxygen storage catalyst.
  • An OSC-containing noble metal catalyst therefore has oxygen storage materials.
  • the OSC-free precious metal catalyst essentially has no function of storing oxygen in the exhaust gas of the internal combustion engine.
  • this component has oxygen storage materials, in particular cerium-zirconium mixed oxides, of less than 20 g/L, preferably less than 10 g/L and most preferably less than 5 g/L carrier volume.
  • the entire amount of cerium or cerium-zirconium mixed oxides, for example, is considered the storage material, including the doping elements present.
  • Corresponding OSC-free precious metal catalysts have the ability to have an oxidative effect on the substances present (NH3, HC, CO) in the already slightly lean exhaust gas of a predominantly stoichiometrically operated combustion engine.
  • This component is preferably designed so that it becomes active at correspondingly low temperatures.
  • the ammonia stored in the zeolite or zeotype is preferably converted into non-harmful nitrogen via this component.
  • the oxidation effect should not be too great, otherwise a certain proportion of the powerful greenhouse gas N2O will be formed from ammonia oxidation.
  • the second component in the form of an OSC-free precious metal catalyst therefore has materials that have an oxidative effect on, among other things, ammonia.
  • This component normally contains a temperature-stable, high-surface metal oxide and at least one noble metal selected from the group rhodium, platinum and palladium.
  • the total noble metal content of this component is preferably from 0.015 - 5 g/L, more preferably from 0.035 - 1.8 g/L and particularly preferably from 0.07 - 1.2 g/L carrier volume.
  • the precious metals platinum or palladium, or platinum and palladium together, are particularly suitable for use in this component that has an oxidative effect on ammonia.
  • the person skilled in the art can preferably choose whether to use the strongly oxidative platinum alone or, if necessary, in conjunction with palladium in the second coating layer. If platinum and/or palladium is used, the former should be in the range of 0.015 - 1.42 g/L, more preferably 0.035 - 0.35 g/L carrier volume in the coating. Palladium can be present in the coating in between 0.015 - 1.42 g/L, preferably 0.035 - 0.35 g/L carrier volume. The weight ratio of platinum to palladium should be between 1:0 and 1:5, more preferably 1:0 and 1:4 and most preferably 1:0 and 1:2.
  • the precious metals in the OSC-free second component are fixed on one or more temperature-stable, high-surface metal oxides as carrier materials.
  • All materials familiar to those skilled in the art for this purpose can be considered as carrier materials.
  • Such materials are in particular metal oxides with a BET surface area of 30 to 250 m 2 /g, preferably 100 to 200 m 2 /g (determined according to DIN 66132 - latest version on the filing date).
  • Particularly suitable carrier materials for the precious metals are selected from the series consisting of aluminum oxide, doped aluminum oxide, silicon oxide, titanium dioxide and mixed oxides from one or more of these.
  • Doped aluminum oxides are, for example, lanthanum oxide, zirconium oxide, barium oxide and/or titanium oxide-doped aluminum oxides.
  • Aluminum oxide or lanthanum-stabilized aluminum oxide is advantageously used, in the latter case lanthanum in amounts of in particular 1 to 10% by weight, preferably 3 to 6% by weight, in each case calculated as La2Ü3 and based on the weight of the stabilized aluminum oxide, is used. Even in the case of aluminum oxide doped with barium oxide, the proportion of barium oxide is in particular 1 to 10% by weight, preferably 3 to 6% by weight, in each case calculated as BaO and based on the weight of the stabilized aluminum oxide.
  • a Another suitable carrier material is lanthanum-stabilized aluminum oxide, the surface of which is coated with lanthanum oxide, barium oxide and/or strontium oxide. This component preferably comprises at least one aluminum oxide or doped aluminum oxide.
  • La-stabilized y-alumina with a surface area of 100 to 200 m 2 /g is particularly advantageous in this context. Such active aluminum oxide has been widely described in the literature and is available on the market.
  • the catalyst for reducing ammonia emissions has an OSC-containing noble metal catalyst as an alternative or cumulative to the OSC-free precious metal catalyst.
  • oxygen storage materials are also present in the precious metal catalyst (containing OSC). Cerium or cerium-zirconium mixed oxides (see below) are consistently used as oxygen storage materials. Accordingly, an OSC-containing noble metal catalyst is characterized by the presence of a certain amount of these oxygen storage materials. In particular, this component has oxygen storage materials in an amount of more than 5 g/L, preferably more than 10 g/L and most preferably more than 20 g/L carrier volume. The entire cerium-zirconium mixed oxide with all its components is included.
  • Corresponding OSC-containing precious metal catalysts have the ability to have an oxidative effect on the substances present (NH3, HC, CO) in the already slightly rich exhaust gas of a predominantly stoichiometrically operated internal combustion engine.
  • This component is preferably designed so that it becomes active at correspondingly low temperatures.
  • the ammonia stored in the zeolite or zeotype is preferably converted into non-harmful nitrogen via this component.
  • the oxidation effect should not be too great, otherwise a certain proportion of the powerful greenhouse gas N2O will be formed from ammonia oxidation.
  • the noble metals in the OSC-containing noble metal catalyst are preferably selected from the group consisting of palladium or rhodium or platinum, platinum and rhodium, palladium and rhodium or palladium and rhodium and platinum together.
  • This catalyst is preferably a coating equipped with three-way catalytic capability.
  • the precious metals can only be deposited on the temperature-stable, high-surface support materials present. However, it is preferred if the noble metals are deposited both on the carrier materials mentioned and on the oxygen storage materials.
  • rhodium is present in this component (whether alone or in combination with the other aforementioned noble metals), this should preferably be in the range of 0.035 - 1.0 g/L, more preferably 0.1 - 0.35 g/L carrier volume located in the respective component. If palladium and/or platinum are also present in this component, the ranges mentioned above for the OSC-free precious metal catalysts apply to these metals.
  • Suitable three-way catalytically active coatings are, for example, in DE102013210270A1, DE102020101876A1, EP3247493A1,
  • Modern gasoline engines are operated under conditions with a discontinuous course of the air ratio X. They are subject to a periodic change in the air ratio X in a defined manner and thus to a periodic change in oxidizing and reducing exhaust gas conditions.
  • This change in the air ratio X is essential for the exhaust gas purification result in both cases.
  • oxygen storage materials contained in the catalytic converter compensate for these deviations to a certain extent by absorbing oxygen from the exhaust gas or releasing it into the exhaust gas as required ( Catalytic Air Pollution Control, Commercial Technology, R. Heck et al., 1995, p. 90).
  • the OSC-containing noble metal catalysts therefore contain oxygen storage materials, in particular cerium or Ce/Zr mixed oxides.
  • the mass ratio of cerium oxide to zirconium oxide can vary within wide limits in these mixed oxides. It is, for example, 0.1 to 1.5, preferably 0.15 to 1 or 0.2 to 0.9.
  • Preferred cerium/zirconium mixed oxides include one or more rare earth metal oxides and can thus be referred to as cerium/zirconium/rare earth mixed oxides.
  • the term “cerium/zirconium/rare earth metal mixed oxide” in the sense of the present invention includes physical mixtures of cerium oxide and zirconium oxide and rare earth oxide.
  • cerium/zirconium/rare earth metal mixed oxides are characterized by a largely homogeneous, three-dimensional crystal structure, which is ideally free of phases made of pure cerium oxide, zirconium oxide or rare earth oxide (so-called solid solution). Depending on the manufacturing process, products may not be completely homogeneous, which can generally be used without disadvantage. The same applies to cerium/zirconium mixed oxides that do not contain any rare earth metal oxide. Furthermore, the term rare earth metal or rare earth metal oxide in the sense of the present invention does not include cerium or cerium oxide.
  • Suitable rare earth metal oxides in the cerium/zirconium/rare earth metal mixed oxides include, for example, lanthanum oxide, yttrium oxide, praseodymium oxide, neodymium oxide and/or samarium oxide.
  • Lanthanum oxide, yttrium oxide and/or praseodymium oxide are preferred.
  • Particularly preferred rare earth metal oxides are lanthanum oxide and/or yttrium oxide and very particularly preferred is the joint presence of lanthanum oxide and yttrium oxide, yttrium oxide and praseodymium oxide, as well as lanthanum oxide and praseodymium oxide in the cerium/zirconium/rare earth metal mixed oxide.
  • this noble metal catalyst has two different cerium/zirconium/rare earth metal mixed oxides, preferably one doped with La and Y and one doped with La and Pr.
  • the oxygen storage components are preferably free of neodymium oxide.
  • the proportion of rare earth metal oxide(s) in the cerium/zirconium/rare earth metal mixed oxides is advantageously 3 to 20% by weight based on the cerium/zirconium/rare earth metal mixed oxide. If the cerium/zirconium/rare earth metal mixed oxides contain yttrium oxide as the rare earth metal, its proportion is preferably 4 to 15% by weight based on the cerium/zirconium/rare earth metal mixed oxide. If the cerium/zirconium/rare earth metal mixed oxides contain praseodymium oxide as the rare earth metal, its proportion is preferably 2 to 10% by weight based on the cerium/zirconium/rare earth metal mixed oxide.
  • cerium/zirconium/rare earth metal mixed oxides contain lanthanum oxide and another rare earth oxide as the rare earth metal, such as yttrium oxide or praseodymium oxide, their mass ratio is in particular 0.1 to 1.25, preferably 0.1 to 1.
  • This noble metal catalyst usually contains oxygen storage materials in amounts of 15 to 120 g/l, based on the volume of the carrier or substrate.
  • the OSC-containing noble metal catalysts also have the temperature-stable, high-surface support materials mentioned for the OSC-free noble metal catalysts and, in addition to these, oxygen-storing materials.
  • the mass ratio of temperature-stable, high-surface carrier materials and oxygen storage components in this component is usually 0.25 to 1.5, for example 0.3 to 1.3.
  • the weight ratio of the sum of the masses of all support materials, such as aluminum oxides (including doped aluminum oxides) to the sum of the masses of all cerium/zirconium mixed oxides in the OSC-containing noble metal catalyst is 10:90 to 75:25, preferably 20 :80 to 65:35..
  • the first and second components preferably form an ammonia storage and a function for the oxidation of ammonia to nitrogen (e.g. as in WO2008106523A2), although the ammonia storage is metal-free within the scope of the invention. If there are not enough nitrogen oxides in the system to oxidize the stored ammonia, the ammonia can also be converted into nitrogen with the oxygen present via the second component. In both cases, if possible, no ammonia or N2O is released into the environment.
  • the first component and the second component of the catalyst for reducing ammonia emissions can therefore preferably consist of an ammonia-storing coating paired with a second coating that has an oxidative effect on ammonia.
  • the respective layer/component can be freely chosen by the person skilled in the art within the scope of the invention. They are preferably located on a flow-through substrate and here take up a length of at least 10% and a maximum of 100%, more preferably 20% - 90%, extremely preferably 30% - 80% of the substrate length.
  • the components are in separate layers, separated from each other but lying on top of each other. It is particularly advantageous if both components are the same length and completely overlap each other.
  • the OSC-free and/or OSC-containing noble metal catalyst of component two is located as a lower layer under the first component made of zeolites and/or zeotypes for storing ammonia as an upper layer.
  • the second component is preferably placed directly on the substrate as a coating. There is preferably no further layer between the first component and the second component (Fig. 2). However, the reverse orientation also provides good results and is also preferred (Fig. 3 - A2).
  • the components of the catalyst for reducing ammonia emissions are applied to a carrier using a coating step familiar to those skilled in the art. preferably applied to a flow-through substrate (DE102019100099A1 and literature cited there).
  • a filter substrate such as a wall flow filter is also possible in this context.
  • Flow-through substrates are catalyst supports that are common in the prior art and can consist of metal, for example WO17153239A1, WO16057285A1, WO15121910A1 and the literature cited therein) or ceramic materials.
  • “Corrugated substrates” can also be viewed as flow-through substrates. These are known to those skilled in the art as carriers made of corrugated sheets made of inert materials.
  • Suitable inert materials are, for example, fibrous materials with an average fiber diameter of 50 to 250 pm and an average fiber length of 2 to 30 mm. Fibrous heat-resistant materials made of silicon dioxide, especially glass fibers, are preferred. However, refractory ceramics such as cordierite, silicon carbite or aluminum titanate etc. are preferably used as honeycomb carriers. The number of channels of these carriers per area is characterized by the cell density, which is usually between 300 and 900 cells per square inch (cells per square inch, cpsi). The wall thickness of the channel walls for ceramics is between 0.5 - 0.05 mm.
  • the total amount of coatings in the catalyst to reduce ammonia emissions is selected so that the catalyst according to the invention is used as efficiently as possible overall.
  • the total amount of coatings (solids content) per carrier volume (total volume of the carrier) can be between 100 and 600 g/L, in particular between 150 and 400 g/L.
  • the first component is preferably used in an amount of 50 to 350 g/L, in particular between 120 and 250 g/L, particularly preferably about 145 - 230 g/L of carrier volume.
  • the second component is preferably used from 50 to 350 g/L, in particular between 120 and 250 g/L, particularly preferably from about 145 - 230 g/L carrier volume.
  • the present exhaust system has a first three-way catalyst and a catalyst positioned downstream to reduce ammonia emissions.
  • the first three-way catalyst can have the same components as the OSC-containing noble metal catalyst of the second component. It is preferably constructed as described in DE102013210270A1, DE102020101876A1, EP3247493A1, EP3727655A1, preferably as described in EP3247493A1.
  • Downstream refers to the fact that the exhaust gas flow first hits the upstream catalytic converter and then the downstream catalytic converter. The reverse applies to the upstream side.
  • Euro 7 legislation it has proven to be advantageous if an exhaust system for a predominantly stoichiometric engine has a unit for filtering small soot and ash particles.
  • An exhaust system is therefore preferred that additionally has a possibly catalytically coated GPF between the first three-way catalytic converter and the catalytic converter to reduce ammonia emissions (FIG. 6).
  • GPF are gasoline particle filters and are well known to those skilled in the art (EP3737491A1, EP3601755A1).
  • An exhaust gas design in which the first three-way catalytic converter and the GPF are installed in a position close to the engine is particularly preferred.
  • Close to the engine in the sense of the invention refers to an area in the exhaust system that is in a position close to the engine, i.e. approx. 10 - 80 cm, preferably 20 - 60 cm away from the engine outlet. It has proven to be advantageous if the catalytic converter is installed last in the exhaust direction in the underbody of a vehicle to reduce ammonia emissions, so that the exhaust gas is then released into the ambient air.
  • the exhaust system can also have additional exhaust units such as additional three-way catalytic converters or hydrocarbon storage (HC traps) or nitrogen oxide storage (LNT).
  • the underbody is the area below the driver's cab.
  • At least a second three-way catalytic converter is located between the first three-way catalytic converter and in front of the catalytic converter to reduce ammonia emissions in the car exhaust system according to the invention.
  • the three-way activity has already been described earlier. There is explicit reference to what is stated there, especially with regard to the type and quantity of the individual components.
  • This three-way catalyst is preferably one as described in the prior art (DE102013210270A1, DE102020101876A1, EP3247493A1, EP3727655A1). Zoned or layered versions are now the norm for TWCs.
  • At least one of the additional catalysts with three-way activity has a 2-layer structure with two different three-way coatings, preferably as described in EP3247493A1.
  • the at least second three-way catalytic converter just described in the exhaust system according to the invention can be installed in the underbody of the vehicle, but it can also be located close to the engine. The range of possible Euro 7 systems is large. There can be up to 4 three-way catalytic converters in front of the catalytic converter per exhaust system to reduce ammonia emissions.
  • the catalyst for reducing ammonia emissions is preferably located last in the underbody and in fluid communication with the further catalyst or catalysts or the filter of the car exhaust system.
  • the car exhaust system preferably has no additional injection device for ammonia or a precursor compound for ammonia.
  • an addition unit for secondary air in the exhaust system upstream of the catalytic converter to reduce ammonia emissions or upstream of the wall flow filter (analogous to WO2019219816).
  • the present invention relates to a method for reducing harmful exhaust gas components from predominantly stoichiometrically operated internal combustion engines, in particular spark-ignited gasoline engines, in which the exhaust gas is passed through an exhaust system according to the invention.
  • the preferred embodiments of the automobile exhaust system also apply mutatis mutandis to the present method.
  • the present invention is directed to an exhaust gas purification system, in particular for stoichiometrically operated internal combustion engines.
  • a stoichiometric engine in which a rich exhaust gas is produced within a certain temperature interval. This can lead to nitrogen oxides arriving via a three-way catalytic converter being over-reduced to ammonia. This ammonia should not be released into the environment.
  • the ammonia is therefore stored above the catalyst to reduce ammonia emissions and is then oxidized to nitrogen under slightly oxidizing conditions. Here too, care must be taken to ensure that over-oxidation to N2O does not occur. Even after intensive aging, the exhaust system is robust enough to fully meet Euro 7 requirements.
  • the catalysts advocated here for reducing ammonia emissions work without transition metal-exchanged zeolites and/or zeotypes.
  • This has the advantage that the second component for ammonia oxidation is prevented from being poisoned with the transition metals, which means that its high activity remains still well preserved under harsh aging conditions. This promises a long active lifespan for the targeted exhaust system.
  • Fig. 1 Chart to explain the measurement of ammonia storage capacity.
  • Fig. 2 Catalyst for reducing ammonia emissions (1), coating with metal-free zeolites or zeotypes for storing ammonia (2) and a coating with an OSC-free noble metal catalyst and/or an OSC-containing noble metal catalyst (3) .
  • Fig. 3 Schematic representation of the catalysts tested in the underbody position
  • Fig. 5 Emission values for catalysts with TWC coating with and without zeolite coating in comparison
  • Fig. 6 Exhaust system according to the invention with a three-way catalytic converter close to the engine (A), GPF close to the engine (B) and the following catalyst to reduce ammonia emissions (C).
  • a reactor made of quartz glass is used.
  • a drill core is taken as a test specimen from the area of the catalytic converter whose ammonia storage capacity is to be determined.
  • a drill core with a diameter of 1 inch and a length of 3 inches is preferably taken as a test specimen.
  • the drill core is inserted into the flow tube reactor and at a temperature of 600 ° C in a gas atmosphere consisting of 500 ppm nitrogen monoxide, 5 ol.-% oxygen, 5 vol.-% water and the rest nitrogen with a space velocity of 30,000 h -1 for 10 minutes conditioned.
  • the measuring temperature of 200 °C is then approached in a gas mixture of 0 vol.% oxygen, 5 vol.% water and the rest nitrogen at a space velocity of 30,000 h -1 .
  • the NHs storage phase is initiated by switching on a gas mixture of 450 ppm ammonia, 0 vol.% oxygen, 5 vol.% water and the rest nitrogen with a space velocity of 30,000 IT 1 . This gas mixture remains switched on until a steady ammonia breakthrough concentration is recorded downstream from the test specimen.
  • the mass of ammonia stored on the test specimen is calculated from the recorded ammonia breakthrough curve by integrating from the start of the NHs storage phase until stationarity is reached, taking into account the measured stationary NHs breakthrough concentration and the known volume flow (hatched area in Figure 1).
  • the ammonia storage capacity is calculated as the quotient of the stored mass of ammonia divided by the volume of the tested core.
  • the zeolite was coated with copper using an incipient wetness process with a copper(II) nitrate solution in a solids mixer. This was followed by treatment in the oven for 8 h at 120°C and for 2 h at 600°C in air.
  • a zeolite of the chabazite structural type a composition with 3.8 wt% CuO based on the total mass of zeolite and CuO was prepared. B2. Production of the copper-containing SCR coating
  • the coating with a Cu-loaded zeolite was carried out after joint grinding with Nyacol®-AL20 binder on a cordierite substrate with the desired washcoat loading (88% zeolite, 12% binder).
  • the coated catalyst thus obtained was dried at 90 °C and then calcined at 350 °C for 15 min and annealed in air at 550 °C for 2 h. If necessary, a layer containing precious metal can be applied as a top layer to the now coated carrier.
  • the coating with white zeolite of the Chabazite type was carried out after joint grinding of the zeolite material suspended in water with Nyacol®-AL20 binder on a cordierite substrate with the desired washcoat loading (88% zeolite, 12% binder).
  • the coated catalyst thus obtained was dried at 90 °C, annealed at 350 °C for 15 min and then calcined in air at 600 °C for 2 h. If necessary, further layers can be applied as a top layer to the now coated carrier.
  • Lanthanum oxide-stabilized alumina was suspended in water along with an oxygen storage component comprising 24 wt% ceria, 60 wt% zirconia, 3.5 wt% lanthana, and 12.5 wt% yttria, and lanthanum acetate as an additional source of lanthana.
  • the weight ratio of aluminum oxide to oxygen storage component to additional lanthanum oxide was 43.6:55.7:0.7.
  • a rhodium nitrate solution was then added to the suspension thus obtained with constant stirring.
  • the resulting coating suspension was used directly to coat a commercially available substrate, with the coating taking place over 100% of the substrate length.
  • a silicon-aluminum mixed oxide consisting of 95% by weight aluminum oxide and 5% silicon oxide was suspended in water. After adjusting the pH to 7.6 ⁇ 0.4, the resulting suspension was mixed with an EA platinum solution with constant stirring. The resulting suspension was ground and, after stabilization with ammonium acetate, used to coat a commercially available carrier, with the coating taking place over 100% of the carrier length. The total loading of this washcoat on the catalyst was 25 g/L, the precious metal loading was 0.106 g/L (3 g/ft 3 ). The coated catalyst thus obtained was dried and then calcined. If necessary, further layers can be applied as a top layer to the now coated carrier.
  • Catalysts were prepared as shown schematically in Figures 4 and 5.
  • the aging consists of fuel cut-off aging with an exhaust gas temperature of 950 °C in front of the inlet of the TWC close to the engine (maximum bed temperature 1030 °C).
  • the aging time and the inlet temperature for the catalytic converter in the underbody position are specified individually for each test.
  • the different catalytic converters were tested in the underbody position on a highly dynamic engine test bench in a WLTC driving cycle.
  • a series-produced TWC containing Pd/Rh was placed in an aged state in a position close to the engine.
  • the value “reduction in NHs emissions” refers to the NH3 emissions of a system with one of the catalytic converters shown in the underbody position over the entire driving cycle in relation to the emissions of the corresponding system in the absence of a catalytic converter in the underbody position.
  • All catalysts with oxidation layer contain 1 g/ft 3 pt.
  • a catalyst in which a copper-free zeolite layer is combined in a layered design with a 1 g/ft 3 Pt oxidation layer shows improved catalytic performance compared to a corresponding catalyst in which a copper-containing SCR in place of the white zeolite layer is used.
  • Both catalysts with TWC layer contain 5 g/ft 3 Rh.
  • a catalyst in which a copper-free zeolite layer is combined in a layered design with a TWC layer at 5 g/ft 3 Rh shows improved catalytic performance compared to a pure TWC coating without zeolite.
  • Catalysts with a TWC layer with different precious metal contents are compared with each other.
  • Table 1 shows the temperatures at which the catalysts show 50% conversion for hydrocarbons, carbon monoxide and nitrogen oxides in a light-off test after fuel-cut aging in the underbody position. A lower one Tso value corresponds to a higher catalytic activity. A catalytic converter containing only rhodium shows the best starting behavior in this test.

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Abstract

La présente invention concerne un système de gaz d'échappement destiné à réduire les émissions de gaz d'échappement et en particulier les émissions d'ammoniac dans le circuit de gaz d'échappement d'un moteur à étincelle à fonctionnement principalement stœchiométrique.
PCT/EP2023/059080 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac WO2023198571A1 (fr)

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
DE102022108768.9 2022-04-11
DE102022108768 2022-04-11
DE102022119441.8 2022-08-03
DE102022119443.4 2022-08-03
DE102022119442.6 2022-08-03
DE102022119443 2022-08-03
DE102022119441 2022-08-03
DE102022119442 2022-08-03
DE102023101772.1A DE102023101772A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101772.1 2023-01-25
DE102023101779.9 2023-01-25
DE102023101768.3A DE102023101768A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101768.3 2023-01-25
DE102023101763.2A DE102023101763A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101779.9A DE102023101779A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101763.2 2023-01-25

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PCT/EP2023/059083 WO2023198574A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne principalement à fonctionnement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059082 WO2023198573A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059079 WO2023198570A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à allumage par étincelle fonctionnant principalement de manière stœchiométrique, comprenant un catalyseur permettant de réduire les émissions d'ammoniac
PCT/EP2023/059081 WO2023198572A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne principalement à fonctionnement stoechiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059084 WO2023198575A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059078 WO2023198569A1 (fr) 2022-04-11 2023-04-06 Catalyseur de blocage d'ammoniac pour moteurs à combustion interne stoechiométrique
PCT/EP2023/059080 WO2023198571A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059087 WO2023198577A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne fonctionnant principalement de manière stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac

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PCT/EP2023/059082 WO2023198573A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059079 WO2023198570A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à allumage par étincelle fonctionnant principalement de manière stœchiométrique, comprenant un catalyseur permettant de réduire les émissions d'ammoniac
PCT/EP2023/059081 WO2023198572A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne principalement à fonctionnement stoechiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059084 WO2023198575A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059078 WO2023198569A1 (fr) 2022-04-11 2023-04-06 Catalyseur de blocage d'ammoniac pour moteurs à combustion interne stoechiométrique

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Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024258A1 (fr) 1979-08-14 1981-02-25 Ciba-Geigy Ag Préparations des compositions pharmaceutiques pour le traitement des infections herpétiques
US5120695A (en) 1989-07-28 1992-06-09 Degusaa Aktiengesellschaft (Degussa Ag) Catalyst for purifying exhaust gases from internal combustion engines and gas turbines operated at above the stoichiometric ratio
EP1876331A2 (fr) 2006-07-08 2008-01-09 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1882832A2 (fr) 2006-07-08 2008-01-30 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1892395A1 (fr) 2006-08-16 2008-02-27 MAN Nutzfahrzeuge AG Système de traitement de gaz d'échappement
WO2008106523A2 (fr) 2007-02-27 2008-09-04 Basf Catalysts Llc Catalyseurs bifonctionnels pour oxydation d'ammoniac sélective
WO2011110919A1 (fr) 2010-03-08 2011-09-15 Johnson Matthey Public Limited Company Amélioration de la gestion des émissions
US20110271664A1 (en) 2010-05-05 2011-11-10 Basf Corporation Integrated SCR and AMOX Catalyst Systems
WO2012135871A1 (fr) 2011-03-29 2012-10-04 Basf Corporation Filtre multicomposant pour maîtrise des émissions
DE102013210270A1 (de) 2013-06-03 2014-12-04 Umicore Ag & Co. Kg Dreiwegkatalysator
WO2015121910A1 (fr) 2014-02-12 2015-08-20 新日鉄住金マテリアルズ株式会社 Matériau de base pour support de catalyseurs
WO2016057285A1 (fr) 2014-10-06 2016-04-14 Corning Incorporated Article filtrant en nid d'abeilles et procédés associés
US9440192B2 (en) * 2009-01-16 2016-09-13 Basf Corporation Diesel oxidation catalyst and use thereof in diesel and advanced combustion diesel engine systems
US20170014766A1 (en) * 2014-03-13 2017-01-19 Umicore Ag & Co. Kg Catalyst system for gasoline combustion engines, having three-way catalysts and scr catalyst
WO2017153239A1 (fr) 2016-03-09 2017-09-14 Haldor Topsøe A/S Procédé de préparation d'un catalyseur en nid d'abeille à base de matériau fibreux non tissé
US20170274321A1 (en) * 2014-10-21 2017-09-28 Basf Corporation Emissions treatment systems with twc catalysts and scr-hct catalysts
EP3247493A1 (fr) 2015-01-19 2017-11-29 Umicore AG & Co. KG Pot catalytique à trois voies double couches présentant une meilleure stabilité au vieillissement
WO2019219816A1 (fr) 2018-05-18 2019-11-21 Umicore Ag & Co. Kg Systèmes et procédés de traitement des gaz d'échappement impliquant une supplémentation en oxygène et un piégeage d'hydrocarbures
EP3601755A1 (fr) 2017-03-23 2020-02-05 Umicore AG & Co. KG Filtre à particules à activité catalytique
DE102019100099A1 (de) 2019-01-04 2020-07-09 Umicore Ag & Co. Kg Verfahren zur Herstellung von katalytisch aktiven Wandflussfiltern
US20200282385A1 (en) * 2019-03-06 2020-09-10 Johnson Matthey Public Limited Company LEAN NOx TRAP CATALYST
EP3727655A1 (fr) 2017-12-19 2020-10-28 UMICORE AG & Co. KG Pot catalytique à trois voies monocouche
EP3737491A1 (fr) 2019-03-29 2020-11-18 UMICORE AG & Co. KG Filtre à particules à activité catalytique
DE102020101876A1 (de) 2020-01-27 2021-07-29 Umicore Ag & Co. Kg Doppelschichtiger Dreiweg-Katalysator mit weiter verbesserter Alterungsstabilität
EP3915679A1 (fr) 2020-05-26 2021-12-01 UMICORE AG & Co. KG Catalyseur, système catalytique et système de nettoyage de gaz d'échappement permettant de réduire les émissions d'ammoniaque
US20220010714A1 (en) * 2014-12-08 2022-01-13 Basf Corporation Nitrous oxide removal catalysts for exhaust systems

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60126515T2 (de) * 2000-06-22 2007-11-22 Mitsubishi Jidosha Kogyo K.K. Katalysator zur Abgasreinigung
JP3855266B2 (ja) * 2001-11-01 2006-12-06 日産自動車株式会社 排気ガス浄化用触媒
US7998423B2 (en) 2007-02-27 2011-08-16 Basf Corporation SCR on low thermal mass filter substrates
PL2117707T5 (pl) 2007-02-27 2019-01-31 Basf Corporation Katalizatory zeolit cha -miedź
DE102010007499A1 (de) 2010-02-09 2011-08-11 Umicore AG & Co. KG, 63457 Volumetrische Beschichtungsanordnung
US8101146B2 (en) * 2011-04-08 2012-01-24 Johnson Matthey Public Limited Company Catalysts for the reduction of ammonia emission from rich-burn exhaust
KR102134127B1 (ko) 2012-10-19 2020-07-15 바스프 코포레이션 고온 ｓｃｒ 촉매로서의 8-고리 소공극 분자체
GB201221025D0 (en) * 2012-11-22 2013-01-09 Johnson Matthey Plc Zoned catalysed substrate monolith
CN104661749B (zh) * 2013-05-27 2017-03-15 马自达汽车株式会社 尾气净化用催化剂及其制备方法
RU2675363C2 (ru) * 2013-07-30 2018-12-19 Джонсон Мэтти Паблик Лимитед Компани Катализатор обработки проскочившего аммиака
US20150231617A1 (en) 2014-02-19 2015-08-20 Ford Global Technologies, Llc Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING
US9149768B1 (en) 2014-03-27 2015-10-06 General Electric Company Emission control in rich burn natural gas engines
US20150290632A1 (en) 2014-04-09 2015-10-15 Ford Global Technologies, Llc IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION
GB2541500B (en) * 2015-06-18 2019-06-26 Johnson Matthey Plc NH3 overdosing-tolerant SCR catalyst
CA2996032C (fr) * 2015-08-21 2023-09-26 Basf Corporation Catalyseurs de traitement de gaz d'echappement
JP6929302B2 (ja) 2016-04-26 2021-09-01 ビーエーエスエフ コーポレーション 酸化触媒の組合せのためのゾーン化構成
EP3357558B1 (fr) * 2017-02-03 2019-06-26 Umicore Ag & Co. Kg Catalyseur pour la purification des effluents gazeux d'un moteur diesel
MX2019009466A (es) * 2017-02-08 2019-11-28 Basf Corp Articulos cataliticos.
CN109225316B (zh) * 2018-10-08 2020-03-31 中自环保科技股份有限公司 一种尾气处理催化剂及其制备方法和用途
US11073057B2 (en) * 2019-01-31 2021-07-27 Hyundai Motor Company Co clean-up catalyst, after treatment system and after treatment method
EP3885040A1 (fr) * 2020-03-24 2021-09-29 UMICORE AG & Co. KG Catalyseur d'oxydation d'ammoniac

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024258A1 (fr) 1979-08-14 1981-02-25 Ciba-Geigy Ag Préparations des compositions pharmaceutiques pour le traitement des infections herpétiques
US5120695A (en) 1989-07-28 1992-06-09 Degusaa Aktiengesellschaft (Degussa Ag) Catalyst for purifying exhaust gases from internal combustion engines and gas turbines operated at above the stoichiometric ratio
EP1876331A2 (fr) 2006-07-08 2008-01-09 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1882832A2 (fr) 2006-07-08 2008-01-30 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1892395A1 (fr) 2006-08-16 2008-02-27 MAN Nutzfahrzeuge AG Système de traitement de gaz d'échappement
WO2008106523A2 (fr) 2007-02-27 2008-09-04 Basf Catalysts Llc Catalyseurs bifonctionnels pour oxydation d'ammoniac sélective
US9440192B2 (en) * 2009-01-16 2016-09-13 Basf Corporation Diesel oxidation catalyst and use thereof in diesel and advanced combustion diesel engine systems
WO2011110919A1 (fr) 2010-03-08 2011-09-15 Johnson Matthey Public Limited Company Amélioration de la gestion des émissions
US20110271664A1 (en) 2010-05-05 2011-11-10 Basf Corporation Integrated SCR and AMOX Catalyst Systems
WO2012135871A1 (fr) 2011-03-29 2012-10-04 Basf Corporation Filtre multicomposant pour maîtrise des émissions
DE102013210270A1 (de) 2013-06-03 2014-12-04 Umicore Ag & Co. Kg Dreiwegkatalysator
WO2015121910A1 (fr) 2014-02-12 2015-08-20 新日鉄住金マテリアルズ株式会社 Matériau de base pour support de catalyseurs
US20170014766A1 (en) * 2014-03-13 2017-01-19 Umicore Ag & Co. Kg Catalyst system for gasoline combustion engines, having three-way catalysts and scr catalyst
WO2016057285A1 (fr) 2014-10-06 2016-04-14 Corning Incorporated Article filtrant en nid d'abeilles et procédés associés
US20170274321A1 (en) * 2014-10-21 2017-09-28 Basf Corporation Emissions treatment systems with twc catalysts and scr-hct catalysts
US20220010714A1 (en) * 2014-12-08 2022-01-13 Basf Corporation Nitrous oxide removal catalysts for exhaust systems
EP3247493A1 (fr) 2015-01-19 2017-11-29 Umicore AG & Co. KG Pot catalytique à trois voies double couches présentant une meilleure stabilité au vieillissement
WO2017153239A1 (fr) 2016-03-09 2017-09-14 Haldor Topsøe A/S Procédé de préparation d'un catalyseur en nid d'abeille à base de matériau fibreux non tissé
EP3601755A1 (fr) 2017-03-23 2020-02-05 Umicore AG & Co. KG Filtre à particules à activité catalytique
EP3727655A1 (fr) 2017-12-19 2020-10-28 UMICORE AG & Co. KG Pot catalytique à trois voies monocouche
WO2019219816A1 (fr) 2018-05-18 2019-11-21 Umicore Ag & Co. Kg Systèmes et procédés de traitement des gaz d'échappement impliquant une supplémentation en oxygène et un piégeage d'hydrocarbures
DE102019100099A1 (de) 2019-01-04 2020-07-09 Umicore Ag & Co. Kg Verfahren zur Herstellung von katalytisch aktiven Wandflussfiltern
US20200282385A1 (en) * 2019-03-06 2020-09-10 Johnson Matthey Public Limited Company LEAN NOx TRAP CATALYST
EP3737491A1 (fr) 2019-03-29 2020-11-18 UMICORE AG & Co. KG Filtre à particules à activité catalytique
DE102020101876A1 (de) 2020-01-27 2021-07-29 Umicore Ag & Co. Kg Doppelschichtiger Dreiweg-Katalysator mit weiter verbesserter Alterungsstabilität
EP3915679A1 (fr) 2020-05-26 2021-12-01 UMICORE AG & Co. KG Catalyseur, système catalytique et système de nettoyage de gaz d'échappement permettant de réduire les émissions d'ammoniaque

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CH. BAERLOCHERW.M. MEIERD.H. OLSON: "Atlas of Zeolite Framework Types", 2001, ELSEVIER
R. HECK ET AL.: "Catalytic Air Pollution Control", COMMERCIAL TECHNOLOGY, 1995, pages 90
W.M. MEIER, PURE & APPL. CHEM., vol. 58, no. 10, 1986, pages 1323 - 1328

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