WO2023198573A1 - 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
WO2023198573A1
WO2023198573A1 PCT/EP2023/059082 EP2023059082W WO2023198573A1 WO 2023198573 A1 WO2023198573 A1 WO 2023198573A1 EP 2023059082 W EP2023059082 W EP 2023059082W WO 2023198573 A1 WO2023198573 A1 WO 2023198573A1
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WIPO (PCT)
Prior art keywords
exhaust system
catalyst
ammonia
exhaust gas
oxide
Prior art date
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PCT/EP2023/059082
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German (de)
English (en)
Inventor
Julius KOEGEL
Massimo Colombo
Sonja Buchberger
Marcus Schmidt
Frank-Walter Schuetze
Original Assignee
Umicore Ag & Co. Kg
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Publication date
Priority claimed from DE102023101763.2A external-priority patent/DE102023101763A1/de
Application filed by Umicore Ag & Co. Kg filed Critical Umicore Ag & Co. Kg
Publication of WO2023198573A1 publication Critical patent/WO2023198573A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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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    • 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 ASC catalysts are usually located in the underbody at the last point of the exhaust system. If for oxidation of the If there are not enough nitrogen oxides in the system due to the stored ammonia, the ammonia can also be converted into nitrogen using the oxygen present via the ASC. As it turns out, the aging stability of the ASC catalysts also depends significantly on the materials used.
  • the present invention to present new exhaust systems which allow the operation of an internal combustion engine, in particular a predominantly stoichiometrically operated internal combustion engine, even under the new Euro 7 legislation.
  • the corresponding limit values should be safely adhered to, especially for NH3 and N2O.
  • 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 - 11 relate to preferred embodiments of the exhaust system and can accordingly also be applied to the method according to the invention.
  • the system according to the invention is characterized by good performance both in terms of the original exhaust gas components and in terms of the NHs and IX ⁇ O emissions. It reacts well to the dynamic requirements in the exhaust system of a spark ignition engine and is particularly robust in order to meet these requirements for a sufficient period of time.
  • the components of the catalyst for reducing ammonia emissions are applied to a carrier, preferably to a flow-through substrate, using a coating step familiar to those skilled in the art (DE102019100099A1 and the 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.
  • refractory ceramics such as cordierite, silicon carbite or aluminum titanate etc. are preferably used as honeycomb carriers.
  • the number of carrier channels 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 components are present as separate coatings one above the other on the substrate.
  • the first component is in the first layer, the second component in the second. It is preferred if the second layer lies completely above the first and completely covers it.
  • the reverse arrangement is also possible.
  • the first layer does not protrude beyond the second layer at any end.
  • the two coatings with the respective ones Components are of the same length (Fig. 2).
  • the length of the layers can be chosen by the specialist. 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. In this case, a coating that lies above another comes into contact with the exhaust gas first before the latter.
  • 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.
  • three-dimensional zeolites or zeotypes are used in the present invention [Ch. Baerlocher, WM Meier and DH Olson, Atlas of Zeolite Framework Types, Elsevier, 2001]
  • 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.
  • 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 are, on the one hand higher than with 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 is therefore particularly in demand.
  • the zeolites preferably have a SAR value (silica-to-alumina ratio) or the zeotypes have a ratio corresponding to this value of >32 to ⁇ 45, most preferably from >35 to ⁇ 40.
  • SAR value silicon-to-alumina ratio
  • the amount of silicon atoms remaining in the framework is compared to the substitution atoms (Al ions). This results in the number of negative charges in the base body and thus a measure of the number of counterions to be absorbed until electroneutrality is achieved.
  • a corresponding ratio can be determined for Zeotype.
  • the zeolite or zeotype used is ion-exchanged with transition metal ions.
  • the latter are preferably selected from the group consisting of iron and/or copper. Iron is particularly preferred because it has a less oxidizing effect on ammonia compared to copper. These compounds have the possibility of comproportioning nitrogen oxides present in the exhaust gas and the stored ammonia into nitrogen when lean.
  • the zeolite or zeotype described acts as a catalyst for selective catalytic reduction (SCR) (see WG2008106518A2, WO2017187344A1, US2015290632AA, US2015231617AA,
  • SCR capability is understood to mean the ability to selectively convert NO X and NH3 in the lean exhaust gas into nitrogen.
  • the metals such as iron and/or copper, which advantageously occur in the catalyst to reduce ammonia emissions, are present in a certain proportion in the first component. This is 0.4-5, more preferably 0.8-4 and very preferably 1.5-3.5% by weight of the first component.
  • the iron and/or copper to aluminum ratio is between 0.1 - 0.8, preferably between 0.2 - 0.5 and most preferably between 0.3 - 0.5 for zeolites. For the zeotype, a corresponding ratio applies to the exchange places available there.
  • the metals are at least partially present in ion-exchanged form in the zeolites or zeotypes. Preferably, ion-exchanged zeolites or zeotypes are already introduced into the first component.
  • the zeolites or zeotypes are brought together with, for example, a binder and a solution of the metal ions in a liquid, preferably water, and then dried (preferably by spraying).
  • a binder preferably water
  • certain proportions of the metals can also be found on the binder in the form of oxides.
  • ion exchange represents a challenge for small-pore zeolites. While ion exchange for large-pore zeolites can be carried out as part of the washcoat process, since the ions readily penetrate into the large zeolite pores and occupy the ion exchange positions of the material, the occupation of small-pore zeolites requires a separate process step. This can be, for example, an incipient wetness process or an ion exchange process with, if necessary, subsequent spray drying. The expert knows how to proceed here.
  • 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 SiC>2, Al2O3 and ZrC>2, 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 can also contain the above-mentioned transition metals, in particular iron and/or copper. Binders are suitable for ensuring stronger adhesion of the coating to a carrier or another coating. For this purpose, a certain particle size of the metal oxides in the binder is advantageous. This can be adjusted accordingly by a specialist.
  • 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 first component should increase the ammonia storage capacity of the exhaust gas purification system to at least 0.25 g of ammonia per L of carrier volume (measured in the fresh state).
  • the storage capacity of the ammonia storage components used in the form of zeolites or zeotypes should be sufficient to ensure 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 especially preferably between 0.5 and 5.0 g NHs/liter 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 further below.
  • the second component consists of an OSC-containing noble metal catalyst containing rhodium.
  • OSC means Oxygen Storage Component.
  • An OSC-containing noble metal catalyst therefore has oxygen storage materials.
  • the OSC-containing precious metal catalyst therefore has a function of storing oxygen in the exhaust gas of the internal combustion engine.
  • oxygen storage materials are also present in the noble 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 10 g/L, preferably more than 15 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 second component in the form of the OSC-containing noble metal catalyst therefore has materials that have an oxidative effect on, among other things, ammonia.
  • This component preferably contains a temperature-stable, high-surface metal oxide, oxygen storage material and at least the noble metal rhodium. Platinum and/or palladium may also be present. However, only rhodium is most preferably present in the second component.
  • 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 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 when present in the Coating between 0.015 - 1.42 g/L, preferably 0.035 - 0.35 g/L carrier volume must be present.
  • Rhodium is present in the second component according to the invention (alone or in combination with the other aforementioned noble metals).
  • the carrier volume in this component should preferably be in the range of 0.035 - 1.0 g/L, more preferably 0.1 - 0.35 g/L. If palladium and/or platinum are also present in this component, the above ranges apply to these metals. Equipped in this way, this component has three-way activity. Suitable three-way catalytically active coatings (TWC) are described, for example, in DE102013210270A1, DE102020101876A1, EP3247493A1, EP3727655A1.
  • the noble metals in the OSC-containing second component are usually also 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.
  • 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 ⁇ -aluminum oxide 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.
  • 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.
  • the lambda value of the exhaust gas is measured with a very short cycle time (approx. 0.5 to 5 Hertz) and an amplitude A ⁇ .
  • the OSC-containing noble metal catalysts (modern three-way catalysts) of the second component 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 therefore be referred to as cerium/zirconium/rare earth metal mixed oxides.
  • the term “cerium/zirconium/rare earth metal mixed oxide” in the sense of the present invention excludes physical mixtures of cerium oxide, 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 therefore preferably have the temperature-stable, high-surface support materials mentioned and, in addition to these, the oxygen-storing materials just explained.
  • 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 noble metals can only be deposited on the temperature-stable, high-surface support materials.
  • the first and second components preferably form an ammonia storage with SCR functionality and a function for oxidizing ammonia to nitrogen (eg as in WO2008106523A2). 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.
  • both coatings are of the same length.
  • the OSC-containing noble metal catalyst of component two is located as a top layer over the first component made of zeolites and / or zeotypes for storing ammonia as a bottom layer. Most preferably, no further layers are present below or above these two coatings on the substrate.
  • This thin layer helps to further increase the aging stability of the catalyst to reduce ammonia emissions.
  • a disadvantage of the known systems for reducing ammonia emissions can be that the transition metals in the first component, such as iron and/or copper, tend to enter the exhaust system of a predominantly stoichiometrically operated internal combustion engine after a long period of use Component for the oxidation of ammonia to diffuse and poison it. The result is a lower activity of the ammonia-storing and oxidative components.
  • Suitable materials for this layer are, in particular, those selected from the group consisting of aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, zeolites or mixtures of one or more of these.
  • a layer made of aluminum oxide is particularly preferred in this context.
  • the inert layer is preferably located at the same length above the first layer and below the second layer on the substrate.
  • 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 or EP3727655A1. Zoned or layered versions are now the norm for TWCs.
  • the first catalyst with three-way activity has, in a further preferred embodiment, a 2-layer structure with two different three-way coatings, 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.
  • 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. 5).
  • GPF are gasoline particle filters and are well known to those skilled in the art (EP3737491A1, EP3601755A1).
  • Particularly preferred is an exhaust gas design in which the first three-way catalytic converter and the GPF on the downstream side are installed in a housing close to the engine, if necessary.
  • 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) upstream of the catalytic converter to reduce ammonia emissions.
  • the underbody is the area below the driver's cab.
  • a second three-way catalytic converter 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 (TWC).
  • TWC 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 located in the underbody, preferably last, and in fluid communication with the other catalyst(s) 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 WO2019219816A1).
  • 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.
  • There are operating points of one stoichiometric combustion 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.
  • the present exhaust system is robust enough to fully meet the Euro 7 requirements.
  • the exhaust system shown here leads to a significantly improved suppression of ammonia emissions and the formation of nitrous oxide and promises a long active service life.
  • Fig. 1 Chart to explain the measurement of ammonia storage capacity.
  • Fig. 2 Catalyst for reducing ammonia emissions (1), coating with an OSC-containing noble metal catalyst containing rhodium (2), coating with transition metal-exchanged zeolites or zeotypes for storing ammonia (3).
  • Fig. 3 Schematic representation of the catalysts tested in the underbody position, where TWC and SCR coatings can be combined with each other in different ways.
  • Fig. 4 Emission values for the catalysts shown in Fig. 3 in comparison.
  • Fig. 5 Preferred exhaust system with TWC close to the engine, followed by a possibly catalytically coated GPF and a catalytic converter to reduce ammonia emissions in the underbody area.
  • 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 iron using an incipient wetness process with an iron(111) 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 550 °C in air.
  • a composition with 2.5 wt% Fe2Ü3 based on the total mass of zeolite and Fe2Ü3 was prepared.
  • a composition with 4.0 wt% Fe2Ü3 based on the total mass of zeolite and Fe2Ü3 was prepared
  • the coating with an Fe-loaded zeolite was carried out after co-grinding with Nyacol®-AL20 binder on a cordierite substrate with 164.8 g/L 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 600 °C for 2 h.
  • a layer containing precious metal 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.
  • 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.
  • the value “Selectivity to N2O” relates the additional IXhO molecules formed by the ASC in the bottom position to the NHs molecules converted by the ASC according to the formula:
  • All catalysts contain a TWC layer of 5 g/ft 3 Rh.
  • a catalyst containing an SCR layer with a chabazite structural type iron-containing zeolite with a SAR value of 38 and combined in a layered design with a 5 g/ft 3 Rh TWC layer shows improved catalytic performance in comparison to a corresponding catalyst in which an iron-containing chabazite with a SAR value of 24 is used.
  • the catalyst according to the invention is also superior to corresponding catalysts based on commercially available iron-containing zeolites of the BEA structural type, since the latter no longer have any catalytic performance after the aging conditions used here.
  • Table 1 shows the temperatures at which catalysts A and B show 50% conversion for hydrocarbons, carbon monoxide and nitrogen oxides in a light-off test after fuel cut aging in the underbody position. Both catalysts therefore have additional three-way catalytic activity.

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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/EP2023/059082 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 WO2023198573A1 (fr)

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

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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/EP2023/059079 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/EP2023/059087 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
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/EP2023/059083 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/EP2023/059078 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/EP2023/059082 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

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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/EP2023/059079 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/EP2023/059087 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
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/EP2023/059083 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/EP2023/059078 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

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WO2023198571A1 (fr) 2023-10-19
WO2023198575A1 (fr) 2023-10-19
WO2023198577A1 (fr) 2023-10-19
WO2023198569A1 (fr) 2023-10-19

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