Exhaust system for predominantly stoichiometrically operated internal combustion engines comprising a catalyst for reducing ammonia emissions

Abstract

The present invention relates 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.

Description

[0001] The present invention relates 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.

[0002] Exhaust gases from internal combustion engines that operate predominantly (>50% of operating time) with a stoichiometric air / fuel mixture, such as spark-ignition engines or gasoline engines powered by gasoline or natural gas, are conventionally cleaned using three-way catalysts (TWC). These are capable of simultaneously converting the engine's three main gaseous pollutants, namely hydrocarbons, carbon monoxide, and nitrogen oxides, into harmless components. Stoichiometric means that, on average, exactly as much air is available for the combustion of the fuel present in the cylinder as is required for complete combustion. The combustion air / fuel ratio λ (A / F ratio; air / fuel ratio) sets the air mass m actually available for combustion. L,tats in relation to the stoichiometric air mass m L,st : λ=mL,tatsmL,st

[0003] If λ < 1 (e.g., 0.9), this means a "lack of air," and the exhaust mixture is referred to as rich. λ > 1 (e.g., 1.1) means "excess air," and the exhaust mixture is referred to as lean. A value of λ = 1.1 means that 10% more air is present than required for stoichiometric reaction. The same applies to the exhaust gas from combustion engines.

[0004] The catalytically active materials used in known three-way catalysts are typically platinum group metals, particularly platinum, palladium, and rhodium, supported, for example, on γ-aluminum oxide. Three-way catalysts also contain oxygen storage materials, such as cerium / zirconium mixed oxides. In the latter, cerium 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 activated by applying catalytically active materials such as platinum group metals and thus also serve as support materials for the platinum group metals.

[0005] When operating predominantly stoichiometrically fueled internal combustion engines, NH3 and / or N2O are produced under certain operating conditions via a close-coupled three-way catalyst. Toxic ammonia and the potent greenhouse gas N2O are referred to as secondary emissions, and their emissions cannot be adequately reduced by current exhaust aftertreatment systems. Maintaining the lowest possible levels for these secondary emissions across a wide range of driving situations requires the development of a robust technical solution in the form of a new catalyst for the gasoline exhaust system, as the regulation of ammonia emissions from gasoline-powered cars, in particular, is expected to be the subject of future legislation such as China 7. The extremely dynamic environmental conditions, especially in the underbody of a gasoline-powered car, pose a major challenge.

[0006] Maintaining low ammonia emission levels requires the use of a storage material to store NH3 during rich operating conditions of the combustion engine, particularly in low and medium temperature ranges, since ammonia is primarily formed under these exhaust gas conditions. The stored ammonia is then converted during lean operating points by oxidation on a noble metal-containing layer and / or as part of an SCR reaction. The aim is to achieve the lowest possible selectivity to N2O. A particular requirement for the catalysts considered here is the high aging stability of the materials used: In addition to stability under lean gas conditions, their application in the exhaust system of stoichiometrically operated combustion engines requires that they are also stable in exhaust gases with a rich or stoichiometric composition under hydrothermal exhaust gas conditions.

[0007] The use of catalysts that preferentially convert ammonia to nitrogen has already been discussed, particularly in the diesel sector or for use in lean-burn DI gasoline engines (US5120695; EP1892395A1; EP1882832A2; EP1876331A2; WO12135871A1; US2011271664AA; WO11110919A1, EP3915679A1). The use of ammonia slip catalysts, or ASCs for short, has also been described in the field of CNG engines (CNG = "Compressed Natural Gas") (EP24258A1). These catalysts often consist of an SCR-catalytically active component and an ammonia-catalyzing oxidation component. They are usually located in the underbody at the very end of the exhaust system. If there are not enough nitrogen oxides in the system to oxidize the stored ammonia, the ammonia can also be converted to nitrogen using available oxygen above the ASC.

[0008] In DE102023101772A1, it is an object of the present invention to present new exhaust systems that allow the operation of a predominantly stoichiometrically operated, in particular spark-ignition, internal combustion engine, in which as few harmful exhaust components as possible reach the atmosphere. In particular, the correspondingly low values ​​for NH3 and N2O should be reliably maintained, in addition to ensuring good conversion of CO, HC, and NOx. Furthermore, the system should also be sufficiently robust and agile to withstand the operating conditions in the exhaust system of a corresponding automobile for a sufficient period of time. It should also be as cost-effective to produce as possible.

[0009] These and other objects arising from the prior art for the person skilled in the art are achieved by an exhaust system and a method for exhaust gas purification according to claims 1 and 11, respectively. Claims 2-10 relate to preferred embodiments of the exhaust system and are accordingly also applicable to the method according to the invention.

[0010] By specifying an exhaust system for reducing harmful exhaust gas components comprising a predominantly stoichiometrically operated internal combustion engine, comprising a first three-way catalyst and, downstream thereof, a catalyst for reducing ammonia emissions, and comprising the following components: - a first component comprising a transition metal exchanged zeolite and / or zeotype for ammonia storage; - a second component with an OSC-free precious metal catalyst and / or an OSC-containing precious metal catalyst, wherein The first component comprises a mixture of medium-pore and large-pore zeolites or zeotypes, with the second component lying completely over the first and the large-pore and medium-pore zeolites being deposited in separate layers or as a homogeneous coating on the substrate, the solution to the problem is achieved relatively simply, but no less surprisingly. The system according to the invention is characterized by extremely good performance with regard to the reduction of CO, HC and NOx emissions as well as NH3 and N2O emissions. It reacts well under the dynamic demands in the exhaust system of a gasoline engine and is accordingly robust in order to meet these demands over a sufficient period of time. Furthermore, it is more advantageous to manufacture from a production technology perspective. In addition, the large-pore zeolites or zeotypes can also serve as hydrocarbon traps and thus help to reduce HC emissions during, for example,to reduce cold start conditions.

[0011] The components of the catalyst for reducing ammonia emissions are applied to a support, preferably to a flow-through substrate, in a coating step familiar to those skilled in the art (DE102019100099A1 and the literature cited therein). A filter substrate such as a wall-flow filter is also possible in this context. Flow-through substrates are catalyst supports commonly used in the art and can consist of metal (e.g., WO17153239A1, WO16057285A1, WO15121910A1 and the literature cited therein) or ceramic materials. Corrugated substrates can also be considered flow-through substrates. These are known to those skilled in the art as supports made of corrugated sheets composed of inert materials. Suitable inert materials include, for example, fibrous materials with an average fiber diameter of 50 to 250 µm 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 carbide, or aluminum titanate, etc., are preferred as honeycomb supports. The number of channels in the supports per unit area is characterized by the cell density, which is typically between 300 and 900 cells per square inch (cpsi). The wall thickness of the channel walls for ceramics is between 0.5 and 0.05 mm.

[0012] The total amount of coating in the catalyst for reducing ammonia emissions is selected so that the catalyst according to the invention is used as efficiently as possible. In the case of one or more flow-through substrates, for example, the total amount of coating (solids content) per support volume (total volume of the support) 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 support volume. The second 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 support volume.

[0013] According to the invention, the components are present as separate coatings lying one above the other on the substrate. It is preferred if the second component lies completely over the first and completely covers it. This means that the first component does not protrude beyond the second component at any end. It is particularly preferred if the two coatings with the respective components are of equal length ( Fig. 2). The length of the layers can be selected by the person skilled in the art. They are preferably located on a flow-through substrate and occupy a length of at least 10% and a maximum of 100%, more preferably 30%-100%, and most preferably 40%-100% of the substrate length. A coating lying over another layer comes into contact with the exhaust gas first, before the latter.

[0014] As already indicated above, a first component of the catalyst for reducing ammonia emissions consists of zeolites and / or zeotypes for storing ammonia. In principle, the zeolites and zeotypes available for this purpose are familiar to those skilled in the art from the diesel sector. The mode of operation of the zeolites or zeotypes is based on their ability to 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 catalyst installed upstream, but which cannot be converted by other conventional three-way catalysts, for example due to a lack of oxygen or insufficient operating temperatures. The ammonia stored in this way can then be released when the operating state of the exhaust gas purification system changes and converted subsequently or directly, for example when sufficient oxygen or nitrogen oxides are available.

[0015] According to the invention, zeolites and zeotypes are present in the first component of the catalyst for reducing ammonia emissions. According to the classification of the IZA (https: / / europe.iza-structure.org / IZA-SC / ftc_table.php), the International Zeolite Association, zeolites and zeotypes can be divided into different classes. Zeolites are then classified, for example, according to their channel system and framework structure. For example, laumontite and mordenite are assigned to the zeolites that have a one-dimensional system of channels. Their channels have no connections to one another. Zeolites with a two-dimensional channel system are characterized by the fact that their channels are connected to one another in a type of layered system. A third group has a three-dimensional framework structure with cross-layer connections between the channels. In the present invention, two- and / or three-dimensional zeolites orZeotype was used [Ch. Baerlocher, WM Meier and DH Olson, Atlas of Zeolite Framework Types, Elsevier, 2001].

[0016] The term “zeolite” refers to porous materials with a lattice structure of corner-sharing AlO4 and SiO4 tetrahedra according to the general formula (WM Meier, Pure & Appl. Chem., Vol. 58, No. 10, pp. 1323-1328, 1986): M m / z [mAlO2 * nSiO2] * qH2O

[0017] The structure of a zeolite thus comprises a network of tetrahedra that encloses channels and cavities. A distinction is made between naturally occurring and synthetically produced zeolites. The term "zeotype" refers to a zeolite-like compound that has the same structural type as a naturally occurring or synthetically produced zeolite compound, but differs from these in that the corresponding cage structure is not composed exclusively of aluminum and silicon framework atoms. In such compounds, the aluminum and / or silicon framework atoms are partially replaced by other tri-, tetra-, or pentavalent framework atoms, such as B(III), Ga(III), Ge(IV), Ti(IV), or P(V).In practice, the most common method used is the replacement of aluminum and / or silicon framework atoms by phosphorus atoms, for example in silicon aluminum phosphates or in aluminum phosphates that crystallize in zeolite structure types.

[0018] Examples of suitable zeolites come from the group of two-dimensional or three-dimensional zeolites / zeotypes. This structural group includes, for example, ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, BEA, BIK, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, ESV, ETL, FER, 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.

[0019] Zeolites or zeotypes can also be classified according to their pore structure. A distinction is made between small-pore, medium-pore, and large-pore zeolites. Extra-large-pore zeolites are of academic interest. Small-pore zeolites are those with a maximum ring size of 8 tetrahedral units. Medium-pore zeolites have a maximum ring size of 10 tetrahedral units. Large-pore zeolites have a maximum ring size of 12 tetrahedral units (https: / / en.wikipedia.org / w / index.php?title=Zeolite&oldid=1103217432 and literature cited there). The medium-pore zeolites or zeotypes for storing ammonia are AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CSV, DAC, EOS, ETV, EUO, EWO, EWS, FER, HEU, IFW, IMF, -ION, ITH, ITR, JRY, JST, LAU, -LIT, MEL, MFI, MFS, MTT, MVY, MWW, NES, OBW, -PAR, PCR, PON, PSI, PTF, PTY, PWW, RFE, RRO, SFF, SFG, STF, STI, STW, -SVR, TER, TON, TUN, UOS, WEI and -WEN in question.Preferred in this context are FER, MFI, and MTT, with FER being most preferred. Large-pore zeolites or zeol types for ammonia storage are preferably selected from the group consisting of BEA, FAU, or MOR. BEA is most preferred in this context.

[0020] The aging stability of the zeolites or zeotypes used in the exhaust system of predominantly stoichiometrically combusting engines is of particular focus here, as higher temperatures generally prevail here than in a lean-burn engine. Therefore, materials that can withstand the sometimes very high and highly fluctuating hydrothermal conditions for as long as possible are desired. On the other hand, however, the exhaust gas composition is also different compared to lean-burn engine exhaust. The concentration of hydrocarbons and carbon monoxide in particular, which reach the catalyst according to the invention, is higher than in lean-burn engines, and the composition also fluctuates around the stoichiometric range depending on the driving style (rich / lean switching). The hydrothermal temperature stability of zeolites and zeotypes as well as their stability towards rich and stoichiometric gas compositions are therefore particularly in demand.The medium-pore zeolites used preferably have a SAR value (silica-to-alumina ratio) or the zeotype a ratio corresponding to this value of > 10 to < 50, very preferably from > 15 to < 35. A range of 15 - 25 is extremely preferred in this context. The large-pore zeolites used preferably have a SAR value (silica-to-alumina ratio) or the zeotype a ratio corresponding to this value of > 10 to < 50, very preferably from > 10 to < 40. A range of 15 - 30 is extremely preferred in this context. To calculate the SAR value, the amount of silicon atoms remaining in the framework of zeolites is compared to the number of substitution atoms. This gives the number of negative charges in the basic body and thus a measure of the number of counterions that must be absorbed until electroneutrality is achieved. A corresponding ratio can be determined for Zeotype.

[0021] According to the invention, 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, compared to copper, it has a less oxidizing effect on ammonia. These compounds have the ability to comproportionate nitrogen oxides present in the exhaust gas and the stored ammonia in lean conditions to nitrogen. In this case, the described zeolite or zeotype acts like a catalyst for selective catalytic reduction (SCR) (see WO2008106518A2, WO2017187344A1, US2015290632AA, US2015231617AA, WO2014062949A1, US2015231617AA). SCR capability is understood here to mean the ability to selectively reduce NO x and convert NH3 in the lean exhaust gas into nitrogen.

[0022] The metals advantageously present in the catalyst for reducing ammonia emissions, such as iron and / or copper, are present in the first component in a specific proportion. This is 0.4 - 10, more preferably 0.8 - 7, and very preferably 1.5 - 5.0 wt.% of the first component. The iron and / or copper to aluminum ratio is between 0.05 - 0.8, preferably between 0.2 - 0.5, and very preferably between 0.3 - 0.5 for zeolites. A corresponding ratio applies to the exchange sites available for the zeotype. The metals are present at least partially in ion-exchanged form in the zeolites or zeotypes. Preferably, already ion-exchanged zeolites or zeotypes are introduced into the first component. However, it is also possible for the zeolites or zeotypes to be mixed with, for example,A binder and a solution of the metal ions in a liquid, preferably water, are combined and then (preferably spray-) dried. In this case, certain amounts of the metals are also found on the binder in the form of oxides. Both procedures are possible.

[0023] However, ion exchange presents a challenge for medium-pore zeolites. While ion exchange for large-pore zeolites can be achieved within the washcoat process, as the ions readily penetrate the large zeolite pores and occupy the ion-exchange sites of the material, the coating of medium-pore zeolites requires a separate process step. This can be an incipient wetness process or an ion exchange process, possibly with subsequent spray drying. The processes for producing metal-exchanged zeolites and zeotypes are well known to those skilled in the art. However, a preferred production approach is to coat the substrate with a mixture of a medium-pore zeolite, a large-pore zeolite, and a soluble salt of the ions to be exchanged (e.g., Fe(NO3)3 × 9 H2O, Cu nitrate), optionally with a common binder system.The dissolved ions are initially absorbed by the large-pore zeolite. A distribution of the ions between the large-pore and medium-pore zeolite then occurs during the calcination process. In addition to eliminating a process step, a catalyst obtained in this way is expected to benefit from the high stability of the ammonia storage function of the medium-pore zeolite and the typically high SCR activity of the large-pore exchanged zeolite, thus demonstrating good performance and selectivity in the described application. Another well-known property of ion-exchanged large-pore zeolites is their ability to store hydrocarbons, which gives the formulated ammonia storage system the properties of a so-called hydrocarbon trap.During cold start, incoming hydrocarbons can be captured, which can then desorb at higher temperatures and be converted via the then active three-way catalysts or oxidation catalysts.

[0024] The first component comprises large- and medium-pore zeolites. These can be deposited in separate layers on the substrate. The sequence of the layers of large- and medium-pore zeolites and the corresponding loading amounts can be varied. Furthermore, it is possible to mix the different zeolite types and apply them to the support as a homogeneous coating. The ratio of the different zeolite types to one another can be varied. The zeolites can be used in transition-metal-free form or coated with transition metals, preferably iron or copper. The large- and medium-pore zeolites are preferably used in a weight ratio of 5:1 to 1:5, more preferably 2:1 to 1:2.A balance between the HC storage capacity and the ammonia storage capacity can be specifically adjusted and adapted to the specific application by the ratio of the large-pore and medium-pore zeolites or zeotypes in the mixture or layers.

[0025] In addition to the zeolites or zeotypes, the first component can preferably comprise other non-catalytically active components, such as binders. Suitable binders include, for example, non-catalytically active or only slightly catalytically active, temperature-stable metal oxides such as SiO2, Al2O3 and ZrO2. Those skilled in the art will know which materials are suitable here. The proportion of such binders in the first coating can, for example, make up up to 15% by weight, preferably up to 10% by weight, of the coating. The binder can also comprise the transition metals specified above, 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 those skilled in the art.

[0026] The ammonia storage capacity addressed in this invention is specified as the quotient of 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 liter of support volume (measured in the fresh state). Overall, the storage capacity of the ammonia storage components used in the form of zeolites or zeotypes should be sufficient to allow the system to store between 0.25 and 10.0 g of NH3 per liter of support volume, preferably between 0.5 and 8.0 g of NH3 per liter of support volume, and particularly preferably between 0.5 and 5.0 g of NH3 per liter of support volume (always based on the fresh state). The zeolites or zeotypes are present in the catalyst in sufficient quantities to reduce ammonia emissions. The determination of the ammonia storage capacity is described further below.

[0027] The second component consists of an OSC-free precious metal catalyst and / or an OSC-containing precious metal catalyst. Precious metal refers in particular to the platinum group metals platinum, palladium, and rhodium. Accordingly, the precious metals in the OSC-free or OSC-containing precious metal catalyst are preferably selected from the group consisting of palladium, platinum, and rhodium. OSC stands for oxygen storage component. An OSC-containing precious metal catalyst therefore comprises oxygen storage materials.

[0028] The OSC-free precious metal catalyst, on the other hand, essentially has no oxygen storage function in the exhaust gas of the combustion engine. In particular, this component comprises oxygen storage materials, especially cerium-zirconium mixed oxides, with a carrier volume of less than 10 g / L, preferably less than 5 g / L, and most preferably less than 2 g / L. The storage material is considered to be the entire amount of, for example, cerium or cerium-zirconium mixed oxides, including the doping elements present. The oxygen storage capacity is determined at a temperature of 510 °C.

[0029] Corresponding OSC-free precious metal catalysts have the ability to oxidize 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 to become active at correspondingly low temperatures. The ammonia stored in the zeolite or zeotype is preferentially converted into harmless nitrogen via this component. The oxidation effect should not be too great, as otherwise a certain amount of the potent greenhouse gas N2O is formed from ammonia oxidation. The oxidation power can be adjusted, among other things, by the amount of platinum and the Pt:Pd and / or Pt:Rh ratio.

[0030] The second component, in the form of an OSC-free precious metal catalyst, accordingly comprises materials that have an oxidative effect on, among other things, ammonia. This component normally contains a temperature-stable, high-surface-area metal oxide and at least one precious metal selected from the group consisting of rhodium, platinum, and palladium. The total precious metal content of this component is preferably from 0.015 to 5 g / L, more preferably from 0.035 to 1.8 g / L, and particularly preferably from 0.07 to 1.2 g / L of 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 skilled person can preferably choose whether to use the strongly oxidative platinum alone or, if appropriate, in combination with palladium in the second coating layer.If platinum and / or palladium are used, the former should be present in the coating in a range of 0.015–1.42 g / L, more preferably 0.035–0.35 g / L carrier volume. Palladium, if present in the coating, can be present in a range of 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.

[0031] As mentioned above, the precious metals in the OSC-free second component are fixed on one or more temperature-stable, high-surface-area metal oxides as support materials. All materials familiar to the person skilled in the art for this purpose can be considered as support materials. Such materials are, in particular, metal oxides with a BET surface area of ​​30 to 250 m². 2 / g, preferably from 100 to 200 m 2 / g (determined according to DIN 66132 - latest version on the filing date). Particularly suitable support materials for the precious metals are selected from the series consisting of aluminum oxide, doped aluminum oxide, silicon oxide, titanium dioxide, and mixed oxides of one or more thereof. Doped aluminum oxides are, for example, aluminum oxides doped with lanthanum oxide, zirconium oxide, barium oxide, and / or titanium oxide. Advantageously, aluminum oxide or lanthanum-stabilized aluminum oxide is used, with lanthanum being used in amounts of, in particular, 1 to 10 wt.%, preferably 3 to 6 wt.%, in each case calculated as La2O3 and based on the weight of the stabilized aluminum oxide. In the case of aluminum oxide doped with barium oxide, the proportion of barium oxide is also, in particular, 1 to 10 wt.%, preferably 3 to 6 wt.%, in each case calculated as BaO and based on the weight of the stabilized aluminum oxide.Another suitable support 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. Particularly advantageous in this context is La-stabilized γ-aluminum oxide with a surface area of ​​100 to 200 m². 2 / g. Such active aluminum oxide is widely described in the literature and available on the market.

[0032] The catalyst for reducing ammonia emissions comprises, as an alternative or in addition to the OSC-free precious metal catalyst, an OSC-containing precious metal catalyst. In addition to the precious metals and the aforementioned temperature-stable, high-surface-area metal oxides, 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 precious metal catalyst is characterized by the presence of a certain amount of these oxygen storage materials. In particular, this component comprises oxygen storage materials in an amount of more than 10 g / L, preferably more than 20 g / L, and most preferably more than 25 g / L of carrier volume. This includes the entire cerium-zirconium mixed oxide with all its constituents.

[0033] Corresponding OSC-containing precious metal catalysts have the ability to oxidize the substances present (NH3, HC, CO) in the already slightly rich exhaust gas of a predominantly stoichiometrically operated combustion engine. This component is preferably designed to become active at correspondingly low temperatures. The ammonia stored in the zeolite or zeotype is preferentially converted into harmless nitrogen via this component. The oxidation effect should not be too great, otherwise a certain amount of the potent greenhouse gas N2O is formed from ammonia oxidation.

[0034] The precious metals in the OSC-containing precious 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. This particularly preferably comprises precious metals selected from the group consisting of platinum and rhodium, palladium and rhodium, and preferably rhodium alone. In the OSC-containing precious metal catalyst, the precious metals can be deposited only on the temperature-stable, high-surface-area support materials. However, it is preferred if the precious metals are deposited on both the aforementioned support materials and the oxygen storage materials.

[0035] If rhodium is present in this component (whether alone or in combination with the other previously mentioned precious metals), it should preferably be in the range of 0.015 - 1.0 g / L, more preferably 0.1 - 0.35 g / L of carrier volume in the respective component. If palladium and / or platinum are also present in this component, the ranges specified above for the OSC-free precious metal catalysts apply to these metals. Suitable three-way catalytically active coatings are described, for example, in DE102013210270A1, DE102020101876A1, EP3247493A1, and EP3727655A1.

[0036] Modern gasoline engines operate under conditions with a discontinuous air / fuel ratio (λ). They are subject to a defined periodic change in the air / fuel ratio (λ) and thus a periodic change between oxidizing and reducing exhaust gas conditions. In both cases, this change in the air / fuel ratio (λ) is essential for the exhaust gas purification result. For this purpose, the lambda value of the exhaust gas is regulated with a very short cycle time (approx. 0.5 to 5 Hertz) and an amplitude Δλ of 0.005 ≤ Δλ < 0.05 around the value λ = 1 (reducing and oxidizing exhaust gas components are present in a stoichiometric ratio to one another). Due to the dynamic operation of the engine in the vehicle, deviations from this condition also occur.To ensure that the above-mentioned deviations from the stoichiometric point do not have a detrimental effect on the exhaust gas purification result when the exhaust gas is passed over the three-way catalyst, oxygen storage materials contained in the catalyst 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).

[0037] The OSC-containing noble metal catalysts (as in modern three-way catalysts) therefore contain oxygen storage materials, in particular cerium or Ce / Zr mixed oxides. The mass ratio of cerium oxide to zirconium oxide in these mixed oxides can vary within wide limits. 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 comprise one or more rare earth metal oxides and can thus be referred to as cerium / zirconium / rare earth metal mixed oxides. The term "cerium / zirconium / rare earth metal mixed oxide" within the meaning of the present invention excludes physical mixtures of cerium oxide, zirconium oxide, and rare earth oxide. Rather, “cerium / zirconium / rare earth metal mixed oxides” are characterized by a largely homogeneous, three-dimensional crystal structure, which is ideally free of phases of pure cerium oxide, zirconium oxide or rare earth oxide (so-called solid solution).Depending on the manufacturing process, however, not completely homogeneous products may be produced, 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 within the meaning of the present invention does not include cerium or cerium oxide. Examples of possible rare earth metal oxides in the cerium / zirconium / rare earth metal mixed oxides are 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 combined presence of lanthanum oxide and yttrium oxide, yttrium oxide and praseodymium oxide, and lanthanum oxide and praseodymium oxide in the cerium / zirconium / rare earth metal mixed oxide.In a preferred embodiment, this noble metal catalyst comprises two different cerium / zirconium / rare earth metal mixed oxides, preferably one doped with La and Y and one doped with La and Pr. In embodiments of the present invention, the oxygen storage components are preferably free of neodymium oxide.

[0038] The proportion of rare earth metal oxide(s) in the cerium / zirconium / rare earth metal mixed oxides is advantageously 3 to 20 wt.%, based on the cerium / zirconium / rare earth metal mixed oxide. If the cerium / zirconium / rare earth metal mixed oxides contain yttrium oxide as a rare earth metal, its proportion is preferably 4 to 15 wt.%, based on the cerium / zirconium / rare earth metal mixed oxide. If the cerium / zirconium / rare earth metal mixed oxides contain praseodymium oxide as a rare earth metal, its proportion is preferably 2 to 10 wt.%, based on the cerium / zirconium / rare earth metal mixed oxide. If the cerium / zirconium / rare earth metal mixed oxides contain lanthanum oxide as the rare earth metal and another rare earth oxide, 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 support or substrate.

[0039] The OSC-containing noble metal catalysts also comprise the temperature-stable, high-surface-area support materials mentioned for the OSC-free noble metal catalysts, as well as the oxygen-storing materials. The mass ratio of temperature-stable, high-surface-area support materials to oxygen-storage components in this component is typically 0.25 to 1.5, for example 0.3 to 1.3. In an exemplary embodiment, 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.

[0040] The first and second components preferably form an ammonia storage facility and a function for the oxidation of ammonia to nitrogen (e.g. as in WO2008106523A2). If there are insufficient nitrogen oxides present in the system to oxidize the stored ammonia, the ammonia can also be converted to nitrogen using the oxygen present above the second component. In both cases, as little ammonia or N2O is released into the environment as possible. In the broadest sense, 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. As such, according to the invention, they are present as separate coatings one above the other on the substrate. It is particularly preferred if both coatings are the same length.It is particularly preferred if, for further improved three-way activity, the OSC-containing noble metal catalyst of component two is located as a top layer above the first component consisting of zeolites and / or zeotypes for ammonia storage as a bottom layer. Most preferably, no further layers are present below or above these two coatings on the substrate.

[0041] In a further preferred embodiment, it has proven advantageous if a thin, separate layer of inert, temperature-stable, high-surface-area metal oxides is present between the two layers / components just mentioned. The person skilled in the art will use the coating methods mentioned above for their production as a guide. This thin layer, between 5 µm and 200 µm, preferably between 10 µm and 150 µm thick, helps to further increase the aging stability of the catalyst for reducing ammonia emissions. As has been found, 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 diffuse into the ammonia oxidation component and poison it after prolonged use in the exhaust system of a predominantly stoichiometrically operated internal combustion engine.The result is lower activity of both the ammonia-storing and oxidative components. Materials selected from the group consisting of aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, zeolites, or mixtures thereof are particularly suitable for this layer. A layer of aluminum oxide or silicon oxide is particularly preferred in this context, preferably located on the substrate at the same length above the lower layer and below the upper layer. The intermediate layer is preferably free of any additional precious metals.

[0042] The present exhaust system comprises a first three-way catalyst and a downstream catalyst for reducing ammonia emissions. The first three-way catalyst can comprise the same components as the OSC-containing precious metal catalyst of the second component. It is preferably constructed as described in DE102013210270A1, DE102020101876A1, EP3247493A1, EP3727655A1, and preferably as described in EP3247493A1 or EP4096811A1. Downstream refers to the fact that the exhaust gas flow first encounters the upstream catalyst and only then the downstream catalyst. The reverse applies to the upstream catalyst.

[0043] With regard to the objective of the present invention, it has proven advantageous if an exhaust system for a predominantly stoichiometrically burning engine has a unit for filtering small soot and ash particles. Accordingly, an exhaust system is preferred that additionally has a possibly catalytically coated GPF between the first three-way catalyst and the catalyst for reducing ammonia emissions ( Fig. 6). GPFs are gasoline particulate filters and are well known to those skilled in the art (EP3737491A1, EP3601755A1). An exhaust design in which the first three-way catalyst and the GPF are installed close to the engine is particularly preferred.

[0044] For the purposes of the invention, "close to the engine" refers to an area in the exhaust system located close to the engine, i.e., approximately 10–80 cm, preferably 20–60 cm, from the engine outlet. It has proven advantageous to install the catalytic converter for reducing ammonia emissions in the underbody of a vehicle at the last point in the exhaust direction, so that the exhaust gas is then released into the ambient air. Likewise, the exhaust system can also incorporate additional exhaust components, such as additional three-way catalytic converters, hydrocarbon traps (HC traps), or nitrogen oxide traps (LNTs). The underbody is the area below the driver's cab.

[0045] In a further preferred embodiment, at least a second three-way catalyst (TWC) is located between the first three-way catalyst and upstream of the catalyst for reducing ammonia emissions in the automotive exhaust system according to the invention. The three-way activity has already been described above. Explicit reference is made to the above description, particularly 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, EP4096811A1). Zoned or layered designs are now the norm for TWCs.In a further preferred embodiment, at least one of the additional catalysts with three-way activity in the vehicle exhaust system according to the invention has a two-layer structure with two different three-way coatings, preferably as described in EP3247493A1 or EP4096811A1. The at least second three-way catalyst 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 variety of possible exhaust systems is large. Thus, preferably up to four three-way catalysts can be present in each exhaust line upstream of the catalyst for reducing ammonia emissions. It is also conceivable that the catalyst described for reducing ammonia emissions is installed directly behind the three-way catalyst in a close-to-engine position, with further components for reducing emissions, such as a particulate filter, installed behind it.Therefore, the present invention preferably relates to a system which, viewed in the flow direction of the exhaust gas, comprises a first TWC (1) close to the engine, followed by the described catalyst for reducing ammonia emissions, also in a position close to the engine, and downstream of this, a particulate filter in the underbody of the vehicle, optionally followed by a further TWC (2).

[0046] In an alternative embodiment, at least one three-way catalyst and a possibly catalytically coated wall-flow filter (GPF) are located upstream of the catalyst for reducing ammonia emissions. The catalyst for reducing ammonia emissions is preferably located last in the underbody and in fluid communication with the other catalyst(s) or the filter of the vehicle's exhaust system. Preferably, the vehicle's exhaust system does not have an additional ammonia injection device or a precursor compound for ammonia. However, it is possible for a secondary air addition unit to be located in the exhaust system upstream of the catalyst for reducing ammonia emissions or upstream of the wall-flow filter (analogous to WO2019219816A1).

[0047] In a further aspect, the present invention relates to a method for reducing harmful exhaust gas components from predominantly stoichiometrically operated internal combustion engines, in particular spark-ignition gasoline engines, in which the exhaust gas is passed through an exhaust system according to the invention. It should be noted that the preferred embodiments of the automotive exhaust system also apply mutatis mutandis to the present method.

[0048] The present invention is directed to an exhaust gas purification system, particularly for stoichiometrically operated internal combustion engines. There are operating points of a stoichiometrically burning engine in which a rich exhaust gas is produced within a specific temperature range. This can lead to nitrogen oxides arriving via a three-way catalyst 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 subsequently oxidized to nitrogen under slightly oxidizing conditions. Here, too, care must be taken to prevent over-oxidation to N2O. Likewise, the ammonia storage catalyst is easy to manufacture, since, if necessary,only a simplified ion exchange step is required during the production of the first component, or the introduction of the iron can be done entirely via the washcoat process. Nevertheless, the system proves robust enough, even after intensive aging, to fully meet the requirements. Figures: Fig. 1: Chart explaining 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 precious metal catalyst and / or an OSC-containing precious metal catalyst (3). Fig. 3: Schematic representation of the catalysts tested in underbody position. Fig. 4: Reduction of ammonia emissions by catalysts A to E compared to a system without underbody catalyst. Fig. 5: Reduction of hydrocarbon emissions by catalysts A to E compared to a system without underbody catalyst. Fig. 6: Exhaust system according to the invention with close-coupled three-way catalyst (A), close-coupled GPF (B) and subsequent catalyst for reducing ammonia emissions (C).

[0049] Examples: A. Determination of ammonia storage capacity

[0050] This is determined experimentally in a flow tube reactor. To avoid undesirable ammonia oxidation on the reactor material, a quartz glass reactor is used. A core sample is taken from the area of ​​the catalyst whose ammonia storage capacity is to be determined. A core sample with a diameter of 1 inch and a length of 3 inches is preferably taken as the test sample. The core sample is placed in the flow tube reactor and heated at a temperature of 600 °C in a gas atmosphere consisting of 500 ppm nitrogen monoxide, 5 vol% oxygen, 5 vol% water, and the remainder nitrogen at a space velocity of 30,000 h -1 for 10 minutes. Subsequently, the sample is conditioned in a gas mixture of 0 vol.% oxygen, 5 vol.% water and the remainder nitrogen at a space velocity of 30000 h -1the measuring temperature of 200 °C is reached. After stabilization of the temperature, the NH3 storage phase is started by switching on a gas mixture of 450 ppm ammonia, 0 vol.% oxygen, 5 vol.% water and the rest nitrogen at a space velocity of 30000 h -1 This gas mixture remains switched on until a steady-state ammonia breakthrough concentration is recorded downstream of the test specimen. The mass of ammonia stored on the test specimen is calculated from the recorded ammonia breakthrough curve by integration from the start of the NH3 storage phase until stationarity is reached, taking into account the measured steady-state NH3 breakthrough concentration and the known volume flow (hatched area in the Fig. 1). The ammonia storage capacity is calculated as the quotient of the stored mass of ammonia divided by the volume of the tested core. B. Production of the zeolite-containing layers B1. Production of the coating based on a large-pore zeolite

[0051] The iron-containing zeolite coating was produced using a washcoat consisting of a large-pore zeolite of the BEA structure type, iron(III) nitrate solution, and a suitable amount of a binder system consisting of an Al2O3 and a SiO2 component. The desired amount of washcoat was applied in one step over 100% of the substrate length. The resulting coated catalyst was dried at 90 °C, then calcined for 15 minutes at 350 °C, and then annealed in air at 550 °C for 2 hours. Additional layers can be applied to the coated support as a top layer if desired. B2. Production of the coating based on a small-pore zeolite

[0052] A coating with white (=transition metal-free) zeolite of the chabazite type was applied after grinding the zeolite material suspended in water with Nyacol ® -AL20 binder on a cordierite substrate with the desired washcoat loading (88% zeolite, 12% binder). The resulting coated catalyst was dried at 90 °C, calcined at 350 °C for 15 min, and then annealed in air at 600 °C for 2 h. Additional layers can be applied to the now coated support as a top layer, if desired. B3. Production of the coating based on a mixture of large-pore and medium-pore zeolites

[0053] A washcoat for coating the zeolite-containing layer is produced by combining a medium-pore ferrous zeolite with a SiO2 / Al2O3 ratio of 18, a large-pore BEA zeolite, and a soluble iron salt (e.g., Fe(NO3)3 x 9 H2O) with a suitable binder system (e.g., Aeroperl / Pural or Nyacol AL20). The washcoat is milled linearly and stirred for 24 hours at room temperature before being coated onto a support. The layer is dried at 90 °C, then the support is calcined for 15 minutes at 350 °C and annealed in air for 2 hours at 600 °C. Additional layers can be applied to the coated support as a top layer if desired.

[0054] The medium pore and large pore zeolite can be applied homogeneously in one layer or in two separate layers, as in Fig. 3. In the case of a homogeneous layer, the medium-pore zeolite can be used in its already iron-exchanged form, or the complete amount of iron can be introduced during the washcoat process using an iron salt. C. Preparation of the platinum-containing SiO2 / Al2O3 layer without TWC activity

[0055] A silicon-aluminum mixed oxide consisting of 95 wt.% aluminum oxide and 5% silicon oxide was suspended in water. After adjusting the pH to 7.6 ± 0.4, an EA-platinum solution was added to the resulting suspension with continuous stirring. The resulting suspension was ground and, after stabilization with ammonium acetate, used to coat a commercially available support, with the coating covering 100% of the support length. The total loading of this washcoat on the catalyst was 25 g / L, and the precious metal loading was 0.106 g / L (3 g / ft³). 3The coated catalyst thus obtained was dried and then calcined and tempered. D. Production of precious metal-containing coatings with TWC activity

[0056] Lanthanum oxide-stabilized aluminum oxide was suspended in water together with an oxygen storage component comprising 26.5 wt% cerium oxide, 57 wt% zirconium oxide, 4 wt% lanthanum oxide, and 12.5 wt% yttrium oxide, and lanthanum acetate as an additional lanthanum oxide source. The weight ratio of aluminum oxide to oxygen storage component to additional lanthanum oxide was 43.6:55.7:0.7. The resulting suspension was then treated with a rhodium nitrate solution under continuous stirring. The resulting coating suspension was used directly to coat a commercially available substrate, with the coating being applied over 100% of the substrate length. The total loading of this washcoat on the catalyst can be, for example, 122 g / L, and the precious metal loading 0.177 g / L (5 g / ft 3 The coated catalyst thus obtained was dried and then calcined and tempered.

[0057] Catalysts such as those in Fig. 3 shown schematically. E. Aging and testing of ASCsAging conditions:

[0058] To determine the catalytic properties of the catalysts according to the invention, they were first aged in an engine test bench behind a close-coupled TWC in the underbody position ("fuel-cut aging"). The aging consists of a deceleration cut-off aging with an exhaust gas temperature of 950 °C upstream of the inlet of the close-coupled TWC (maximum bed temperature 1030 °C). The aging duration and the inlet temperature for the catalyst in the underbody position are specified individually for each test. Test conditions:

[0059] The different catalysts were tested in an underbody position on a highly dynamic engine test bench in a WLTC driving cycle. A series-produced Pd / Rh-containing TWC in an aged state was placed close to the engine. The "NH3 emission reduction" value refers to the NH3 emissions of a system with one of the catalysts shown in the underbody position over the entire driving cycle relative to the emissions of the corresponding system without an underbody catalyst. F. Results

[0060] Comparison of catalysts with zeolite-containing sublayers consisting of different combinations of medium and large pore zeolites and a Rh-containing TWC top layer: See Fig. 4 and Fig. 5

[0061] All catalysts with TWC layer contain 5 g / ft 3 Rh. Aging: Fuel-cut aging, 19 h, 860 °C bed temperature for the catalysts in underbody position Volume of the underbody catalyst: 0.83 L

[0062] Catalysts in which a mixture of a medium and a large pore zeolite with a TWC layer of 5 g / ft 3 Rh, with the zeolites present in separate layers (C+D) or in a homogeneous mixture (E), exhibit three-way catalytic activity and are also capable of reducing NH3 emissions and, through the storage of hydrocarbons, reducing HC emissions during cold starts. Compared to corresponding reference catalysts that exclusively contain a medium-pore zeolite (A) or exclusively a large-pore zeolite (B), the CE catalysts reduce NH3 and HC emissions more than would be expected for a mixture of zeolites based on a linear extrapolation of the properties. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] US 5120695

[0007] EP 1892395A1

[0007] EP 1882832A2

[0007] EP 1876331A2

[0007] WO 12135871A1

[0007] US 2011271664

[0007] WO 11110919A1

[0007] EP 3915679A1

[0007] DE 102023101772A1

[0008] DE 102019100099A1

[0011] WO 17153239A1

[0011] WO 16057285A1

[0011] WO 15121910A1

[0011] WO 2008106518A2

[0021] WO 2017187344A1

[0021] US 2015290632

[0021] US 2015231617

[0021] WO 2014062949A1

[0021] DE 102013210270A1 [0035, 0042, 0045] DE 102020101876A1 [0035, 0042, 0045] EP 3247493A1 [0035, 0042, 0045] EP 3727655A1 [0035, 0042, 0045] WO 2008106523A2

[0040] EP 4096811A1 [0042, 0045] EP 3737491A1

[0043] EP 3601755A1

[0043] WO 2019219816A1

[0046] Zitierte Nicht-Patentliteratur

[0000] Ch. Baerlocher, W.M. Meier and D.H. Olson, Atlas of Zeolite Framework Types, Elsevier, 2001

[0015] W.M. Meier, Pure & Appl. Chem., Vol. 58, No. 10, pp. 1323-1328, 1986

[0016] https: / / en.wikipedia.org / w / index.php?title=Zeolite&oldid=1103217432

[0019] Catalytic Air Pollution Control, Commercial Technology, R. Heck et al., 1995, S. 90

[0036]

Claims

[1] Exhaust system for reducing harmful exhaust gas components, comprising a predominantly stoichiometrically operated internal combustion engine, comprising a first three-way catalyst and, downstream thereof, a catalyst for reducing ammonia emissions, which comprises the following components: - a first component comprising a transition metal exchanged zeolite and / or zeotype for ammonia storage; - a second component with an OSC-free precious metal catalyst and / or an OSC-containing precious metal catalyst, wherein the first component comprises a mixture of medium-pore and large-pore zeolites or zeotypes, characterized by , that the second component lies completely over the first and the large and medium pore zeolites are deposited in separate layers or as a homogeneous coating on the substrate. [2] Exhaust system according to claim 1, characterized bythat the medium pore zeolites or zeotypes for ammonia storage are selected from the group consisting of FER, MFI or MTT. [3] Exhaust system according to one of the preceding claims, characterized by that the large pore zeolites or zeotypes for ammonia storage are selected from the group consisting of BEA, FAU or MOR. [4] Exhaust system according to one of the preceding claims, characterized by that iron and / or copper are present as transition metals. [5] Exhaust system according to one of the preceding claims, characterized by that the first component in the fresh state has an ammonia storage capacity of between 0.25 and 10.0 g NH3 per liter of carrier volume. [6] Exhaust system according to one of the preceding claims, characterized by that the precious metals in the OSC-free or OSC-containing precious metal catalyst are selected from the group consisting of palladium, platinum and rhodium. [7] Exhaust system according to one of the preceding claims, characterized by that in the case of the presence of OSC-containing precious metal catalysts, the precious metals are deposited on both temperature-stable, high-surface area support materials and on the oxygen storage materials. [8] Exhaust system according to one of the preceding claims, characterized by that it additionally has a GPF between the first three-way catalyst and the catalyst for reducing ammonia emissions. [9] Exhaust system according to one of the preceding claims, characterized by that the first three-way catalyst and the GPF are installed close to the engine. [10] Exhaust system according to one of the preceding claims, characterized by that the catalyst for reducing ammonia emissions is installed last in the underbody of a vehicle in the direction of the exhaust gases. [11] Exhaust system according to one of claims 1-7, characterized bythat, viewed in the direction of flow of the exhaust gas, there is a first three-way catalyst close to the engine, followed by the catalyst for reducing ammonia emissions, also in a position close to the engine, and downstream of this there is a particulate filter in the underbody of the vehicle, possibly followed by a further three-way catalyst. [12] Process for reducing harmful exhaust gas components from predominantly stoichiometrically operated internal combustion engines, in particular spark-ignition petrol engines, characterized by that the exhaust gas is passed through an exhaust system according to one of the preceding claims.

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