EP3411143A1 - Multi-layer nitrogen oxide storage catalyst with manganese - Google Patents

Multi-layer nitrogen oxide storage catalyst with manganese

Info

Publication number
EP3411143A1
EP3411143A1 EP17705036.6A EP17705036A EP3411143A1 EP 3411143 A1 EP3411143 A1 EP 3411143A1 EP 17705036 A EP17705036 A EP 17705036A EP 3411143 A1 EP3411143 A1 EP 3411143A1
Authority
EP
European Patent Office
Prior art keywords
oxide
storage catalyst
washcoat
catalyst according
nitrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17705036.6A
Other languages
German (de)
French (fr)
Inventor
Thomas UTSCHIG
Elena Mueller
Ruediger Hoyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of EP3411143A1 publication Critical patent/EP3411143A1/en
Withdrawn legal-status Critical Current

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
    • 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
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • 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
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
    • F01N3/0842—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/1023—Palladium
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    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
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    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/2042—Barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2047—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
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    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
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    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/9022—Two layers
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    • B01D—SEPARATION
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    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/91—NOx-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings

Definitions

  • the present invention relates to a catalyst for the reduction of nitrogen oxides, which is contained in the exhaust lean burned internal combustion engines.
  • nitrogen oxide storage catalysts for which the term “lean NOx trap” or "LNT” is common known.
  • Their cleaning effect is based on the fact that in a lean phase of operation of the engine, the nitrogen oxides are stored by the storage material of the storage catalyst mainly in the form of nitrates and decomposed in a subsequent rich phase of operation of the engine again and released so the nitrogen oxides with the reducing
  • Suitable storage materials are, in particular, oxides, carbonates or hydroxides of magnesium, calcium, strontium, barium, the alkali metals, the rare earth metals or mixtures thereof. Due to their basic properties, these compounds are capable of forming nitrates with the acidic nitrogen oxides of the exhaust gas and of storing them in this way. They are suitable for generating a large interaction area with the exhaust gas in the highest possible dispersion
  • nitrogen oxide storage catalysts generally contain noble metals such as platinum, palladium and / or rhodium as catalytically active components. Their task is, on the one hand, to oxidise NO to NO 2, CO and HC to CO 2 under lean conditions and, on the other hand, to reduce released NO 2 to nitrogen during the rich operating phases in which the nitrogen oxide storage catalyst is regenerated.
  • EP 0 885 650 A2 describes an exhaust gas purification catalyst for internal combustion engines with two catalytically active layers on a support body.
  • the layer directly on the support body comprises one or more highly dispersed alkaline earth oxides, at least one
  • Platinum group metal as well as at least one finely divided, oxygen-storing material.
  • the platinum group metals are in close contact with all components of the first layer.
  • the second layer is in direct contact with the exhaust gas and contains at least one platinum group metal and at least one finely divided oxygen storing material. Only part of the finely divided solids of the second layer serve as a carrier for the platinum group metals.
  • the catalyst is a three-way catalytic converter that controls the harmful components of the exhaust gas
  • a nitrogen oxide storage catalyst which comprises two superimposed catalyst layers on a carrier substrate.
  • the lower layer lying directly on the carrier substrate comprises one or more noble metals, as well as one or more nitrogen oxide storage components.
  • the upper layer comprises one or more
  • Precious metals, as well as cerium oxide and is free of alkali or alkaline earth components Catalyst substrates containing nitrogen oxide storage materials and having two or more layers are also described in WO 2012/029050.
  • the first layer is directly on the carrier substrate and comprises platinum and / or palladium, while the second layer is on the first and comprises platinum.
  • Both layers also contain one or more oxygen storage materials and one or more nitric oxide storage materials comprising one or more alkali and / or alkaline earth metals.
  • the total amount of alkali and alkaline earth metal in the nitrogen oxide storage materials is 0.18 to 2.5 g / in 3 , calculated as alkali metal oxide M2O and alkaline earth metal oxide MO.
  • manganese compounds in particular manganese oxide
  • DE102011109200A1 and US2015 / 165422 describe manganese-containing diesel oxidation catalysts.
  • DE102012204524A1 describes LNT catalysts which contain manganese-containing mixed oxides, for example MnOx-CeO 2 .
  • US2013 / 336865 also describes NOx absorber catalysts which may contain manganese.
  • the present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on one
  • cerium oxide as well as platinum and palladium and is free of alkali and alkaline earth compounds.
  • the cerium oxide used in washcoat layers A and B can be any cerium oxide used in washcoat layers A and B.
  • cerium oxide is used in the washcoat layer A in an amount of from 110 to 160 g / l, for example from 125 to 145 g / l.
  • cerium oxide is used in amounts of 22 to 120 g / l, for example 40 to 100 g / l or 45 to 65 g / l.
  • Suitable alkaline earth compounds in the washcoat A are, in particular, oxides, carbonates and / or hydroxides of magnesium, strontium and / or barium, in particular magnesium oxide, barium oxide and strontium oxide.
  • Suitable alkali compounds in the washcoat A are, in particular, oxides, carbonates and / or hydroxides of lithium, potassium and / or sodium.
  • the alkaline earth or alkali compound in washcoat A is present in amounts of 10 to 50 g / l, especially 15 to 20 g / l, calculated as alkaline earth oxide and based on the volume of the support body.
  • manganese oxide in washcoat A is present in amounts of from 1 to 10 weight percent, preferably 2.5 to 7.5 Wt .-%, based on the sum of Washcoattiken A and B, each calculated as MnO before.
  • the washcoat layer B also contains
  • Washcoat layer B at up to 2.5 wt .-%, preferably 0.5 to 2.5 wt .-%, based on the sum of Washcoat füren A and B.
  • manganese oxide is not used as a carrier material, neither for the noble metals platinum, palladium and optionally rhodium, nor for another component of washcoat A and optionally washcoat B.
  • manganese oxide in the context of the present invention means in particular MnO, MnCh or Mn 2 O 3 or combinations of MnO 2 , MnO
  • manganese oxide is not in the form of mixed oxides with other oxides of washcoat A and B layers.
  • manganese oxide is not present in the form of a mixed oxide with cerium oxide, for example not in the form of MnOx-CeO 2 , MnO-ZrO 2 and
  • the ratio platinum to palladium in the washcoat A in embodiments of the present invention is for example 4: 1 to 18: 1 or 6: 1 to 16: 1, for example 8: 1, 10: 1, 12: 1 or 14: 1.
  • the ratio platinum to palladium in the washcoat layer B is also in embodiments of the present invention, for example 4: 1 to 18: 1 or 6: 1 to 16: 1, for example 8: 1, 10: 1, 12: 1 or 14: 1 but independent of the ratio in washcoat A
  • washcoat B contains rhodium as another precious metal. Rhodium is in this case
  • the total amount of noble metal i. of platinum, palladium and
  • optionally rhodium, in the nitrogen oxide storage catalyst according to the invention is in embodiments of the present invention, 2.12 to 7.1 g / l (60 to 200 g / ft 3 ), based on the volume of the support body.
  • the noble metals are platinum and palladium and optionally rhodium
  • alumina silica
  • titanium dioxide but also mixed oxides such as aluminum-silicon mixed oxides and cerium-zirconium mixed oxides.
  • platinum and palladium and, optionally, rhodium are used as support material for the noble metals
  • Alumina is used, in particular those which is stabilized by 1 to 6 wt .-%, in particular 4 wt .-%, lanthanum oxide.
  • Manganese oxide preferably does not serve as a support for platinum and palladium and optionally rhodium.
  • the total washcoat load of the support body is in
  • Embodiments of the present invention 300 to 600 g / l, based on the volume of the support body.
  • the present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on a support body,
  • o cerium oxide in an amount of 100 to 160 g / l
  • o contains manganese oxide in an amount of 10 to 20 g / l and
  • washcoat caring A in amounts of 250 to 350 g / l and the Washcoat caring B in amounts of 80 to 130 g / l is present and wherein the amount g / l each refers to the volume of the support body.
  • thermal aftertreatment (calcination and optionally reduction with forming gas or hydrogen). These methods are well known in the art.
  • the necessary coating suspensions can after the
  • the nitrogen oxide storage catalysts according to the invention are outstandingly suitable for converting NOx into exhaust gases of
  • the nitrogen oxide storage catalysts according to the invention are thus suitable for Euro 6 applications.
  • the present invention thus also relates to a method for
  • Figure 1 NOx conversion of the catalysts Kl (dashed line) and VK1 (solid line) as a function of temperature.
  • Figure 2 NOx conversion of the catalysts K2 (solid line) and K3 (dashed) as a function of temperature.
  • Figure 3 NOx conversion of the catalysts K2 (solid line) and K4 (dashed) as a function of temperature.
  • the loading of Pt and Pd is 35 g / ft 3 (1.236 g / l) and 3.5 g / ft 3 (0.124 g / l) and the total loading of the washcoat layer about 293 g / l based on the volume of the ceramic - Carrier.
  • a further washcoat layer B is applied to the first washcoat layer, also containing Pt and Pd supported on alumina, and Rh supported on a lanthanum stabilized alumina.
  • the loading of Pt, Pd and Rh in this washcoat layer is 35 g / ft 3 (1.236 g / l), 3.5 g / ft 3 (0.124 g / l) and 5 g / ft 3 (0.177 g / l).
  • the washcoat layer B also contains 55 g / l of cerium oxide with a layer B washcoat loading of about 81 g / l.
  • the catalyst thus obtained is hereinafter called Kl.
  • Example 1 was repeated with the difference that washcoat A did not contain manganese oxide.
  • the catalyst thus obtained is hereinafter called VK1.
  • Atmosphere aged b) The NOx conversion of Kl or VK1 as a function of the temperature before the catalyst was determined in a model gas reactor in the so-called NOx conversion test.
  • Hydrocarbon mixture (consisting of 33 ppm propene and 17 ppm propane) and a residual oxygen content of 7 vol .-% at one
  • FIG. 1 shows the NO x conversions of the inventive catalyst K 1 and of the comparative catalyst VK 1 thus determined.
  • the turnover of Kl in the entire temperature range is higher than the sales of VK1.
  • a honeycomb ceramic support is coated with a first washcoat A, the Pt and Pd supported on alumina, ceria in an amount of 125 g / l, 21 g / l barium oxide, 7.5 g / l magnesium oxide and 7.5 g / l manganese oxide in the form of manganese carbonate.
  • the loading of Pt and Pd is 35 g / ft 3 (1.236 g / l) and 3.5 g / ft 3 (0.124 g / l) and the
  • Total loading of the washcoat layer about 299 g / l based on the volume of the ceramic carrier.
  • another washcoat layer B is applied, which also contains Pt and Pd, and Rh supported on alumina.
  • the loading of Pt, Pd and Rh in this washcoat layer is 35 g / ft 3 (1.236 g / l), 3.5 g / ft 3 (0.124 g / l) and 5 g / ft 3 (0.177 g / l).
  • Washcoat layer B also contains 55 g / l of cerium oxide at one
  • the catalyst thus obtained is hereinafter called K2.
  • Example 2 was repeated with the difference that washcoat B additionally contained 2.5 g / l of manganese oxide in the form of manganese carbonate.
  • the catalyst thus obtained is hereinafter called K3.
  • Example 2 was repeated with the difference that washcoat A contained 15 g / l of manganese oxide in the form of manganese carbonate.
  • the catalyst thus obtained is hereinafter called K4.
  • Example 1 was repeated with the difference that the amounts of cerium oxide and manganese oxide indicated in Table 1 below were used.

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Abstract

The Invention relates to a nitrogen oxide storage catalyst composed of at least two catalytically active washcoat layers on a support body, wherein a lower washcoat layer A comprises cerium oxide, an alkaline earth metal compound and/or an alkali compound, platinum and palladium, and manganese oxide, and an upper washcoat layer B disposed on the washcoat layer A comprises cerium oxide, platinum and palladium and does not contain any alkali and alkaline-earth compounds, and to a method for converting NOx in exhaust gases from motor vehicles which are operated with lean-burn engines.

Description

MEHRSCHICHTIGER STICKOXIDSPEICHERKATALYSATOR MIT MANGAN  MULTILAYER STICKING OXIDE STORAGE Catalyst WITH MANGANE
Die vorliegende Erfindung betrifft einen Katalysator zur Reduktion von Stickoxiden, das im Abgas mager betriebener Verbrennungsmotoren enthalten ist. The present invention relates to a catalyst for the reduction of nitrogen oxides, which is contained in the exhaust lean burned internal combustion engines.
Das Abgas von Kraftfahrzeugen, die mit mager betriebenen Verbrennungsmotoren, beispielsweise mit Dieselmotoren, betrieben werden, enthält neben Kohlenmonoxid (CO) und Stickoxiden (NOx) auch Bestandteile, die aus der unvollständigen Verbrennung des Kraftstoffs im Brennraum des Zylinders herrühren. Dazu gehören neben Rest-Kohlenwasserstoffen (HC), die meist ebenfalls überwiegend gasförmig vorliegen, Partikelemissionen, auch als„Dieselruß" oder„Rußpartikel" bezeichnet. Dabei handelt es sich um komplexe Agglomerate aus überwiegend Kohlenstoff-haltigen Feststoff- Teilchen und einer anhaftenden Flüssigphase, die meist mehrheitlich aus längerkettigen Kohlenwasserstoff-Kondensaten besteht. Die auf den festen Bestandteilen anhaftende Flüssigphase wird auch als„Soluble Organic Fraction SOF" oder„Volatile Organic Fraction VOF" bezeichnet. Zur Reinigung dieser Abgase müssen die genannten Bestandteile möglichst vollständig in unschädliche Verbindungen umgewandelt werden, was nur unter Einsatz geeigneter Katalysatoren möglich ist. The exhaust of motor vehicles which are operated with lean-burn internal combustion engines, such as diesel engines, in addition to carbon monoxide (CO) and nitrogen oxides (NOx) also contains components resulting from the incomplete combustion of the fuel in the combustion chamber of the cylinder. In addition to residual hydrocarbons (HC), which are also mostly present in gaseous form, these include particulate emissions, also referred to as "diesel soot" or "soot particles". These are complex agglomerates of predominantly carbon-containing solid particles and an adhering liquid phase, which mostly consists of relatively long-chain hydrocarbon condensates. The liquid phase adhering to the solid components is also referred to as "Soluble Organic Fraction SOF" or "Volatile Organic Fraction VOF". To purify these exhaust gases, the constituents mentioned must be converted as completely as possible into harmless compounds, which is possible only with the use of suitable catalysts.
Zur Entfernung der Stickoxide sind sogenannte Stickoxid-Speicher- katalysatoren, für die auch der Begriff„Lean NOx Trap" oder„LNT" üblich ist, bekannt. Deren Reinigungswirkung beruht darauf, dass in einer mageren Betriebsphase des Motors die Stickoxide vom Speichermaterial des Speicherkatalysators vorwiegend in Form von Nitraten gespeichert werden und diese in einer darauf folgenden fetten Betriebsphase des Motors wieder zersetzt und die so freiwerdenden Stickoxide mit den reduzierenden To remove the nitrogen oxides so-called nitrogen oxide storage catalysts, for which the term "lean NOx trap" or "LNT" is common known. Their cleaning effect is based on the fact that in a lean phase of operation of the engine, the nitrogen oxides are stored by the storage material of the storage catalyst mainly in the form of nitrates and decomposed in a subsequent rich phase of operation of the engine again and released so the nitrogen oxides with the reducing
Abgasanteilen am Speicherkatalysator zu Stickstoff, Kohlendioxid und Wasser umgesetzt werden. Diese Arbeitsweise ist beispielsweise in der SAE- Schrift SAE 950809 beschrieben. Als Speichermaterialien kommen insbesondere Oxide, Carbonate oder Hydroxide von Magnesium, Calcium, Strontium, Barium, der Alkalimetalle, der Seltenerdmetalle oder Mischungen davon in Frage. Diese Verbindungen sind aufgrund ihrer basischen Eigenschaften in der Lage, mit den sauren Stickoxiden des Abgases Nitrate zu bilden und sie auf diese Weise abzuspeichern. Sie sind zur Erzeugung einer großen Wechselwirkungsfläche mit dem Abgas in möglichst hoher Dispersion auf geeigneten Exhaust gas components are converted to the storage catalyst to nitrogen, carbon dioxide and water. This procedure is described for example in SAE SAE 950809. Suitable storage materials are, in particular, oxides, carbonates or hydroxides of magnesium, calcium, strontium, barium, the alkali metals, the rare earth metals or mixtures thereof. Due to their basic properties, these compounds are capable of forming nitrates with the acidic nitrogen oxides of the exhaust gas and of storing them in this way. They are suitable for generating a large interaction area with the exhaust gas in the highest possible dispersion
Trägermaterialien abgeschieden. Stickoxid-Speicherkatalysatoren enthalten darüber hinaus in der Regel Edelmetalle wie Platin, Palladium und/oder Rhodium als katalytisch aktive Komponenten. Deren Aufgabe ist es einerseits, unter mageren Bedingungen NO zu NO2, sowie CO und HC zu CO2 zu oxidieren und andererseits während der fetten Betriebsphasen, in denen der Stickoxid-Speicherkatalysator regeneriert wird, freigesetztes NO2 zu Stickstoff zu reduzieren. Carrier materials deposited. In addition, nitrogen oxide storage catalysts generally contain noble metals such as platinum, palladium and / or rhodium as catalytically active components. Their task is, on the one hand, to oxidise NO to NO 2, CO and HC to CO 2 under lean conditions and, on the other hand, to reduce released NO 2 to nitrogen during the rich operating phases in which the nitrogen oxide storage catalyst is regenerated.
Mit der Veränderung der Abgasgesetzgebung nach Euro 6 werden With the change of the exhaust gas legislation after Euro 6 become
zukünftige Abgassysteme sowohl bei kalten Temperaturen im Stadtzyklus, als auch bei hohen Temperaturen, wie sie bei hohen Lasten auftreten, ausreichende NOx-Konvertierung aufweisen müssen. Bekannte Stickoxid- Speicherkatalysatoren zeigen aber entweder eine ausgeprägte NOx-Future exhaust systems must have sufficient NOx conversion both at cold city cycle temperatures and at high temperatures such as those encountered at high loads. However, known nitrogen oxide storage catalysts show either a pronounced NOx
Speicherung bei niedrigen oder bei hohen Temperaturen. Es besteht Bedarf nach Katalysatoren, die eine gute NOx-Konvertierung über einen breiten Temperaturbereich von 200 bis 450°C bereitstellen. Die EP 0 885 650 A2 beschreibt einen Abgasreinigungskatalysator für Verbrennungsmotoren mit zwei katalytisch aktiven Schichten auf einem Tragkörper. Die direkt auf dem Tragkörper befindliche Schicht umfasst ein oder mehrere hochdisperse Erdalkalioxide, mindestens ein Storage at low or high temperatures. There is a need for catalysts that provide good NOx conversion over a wide temperature range of 200 to 450 ° C. EP 0 885 650 A2 describes an exhaust gas purification catalyst for internal combustion engines with two catalytically active layers on a support body. The layer directly on the support body comprises one or more highly dispersed alkaline earth oxides, at least one
Platingruppenmetall, sowie wenigstens ein feinteiliges, Sauerstoff speicherndes Material. Dabei stehen die Platingruppenmetalle mit allen Bestandteilen der ersten Schicht in enger Berührung. Die zweite Schicht steht mit dem Abgas in direktem Kontakt und enthält mindestens ein Platingruppenmetall, sowie wenigstens ein feinteiliges, Sauerstoff speicherndes Material . Nur ein Teil der feinteiligen Feststoffe der zweiten Schicht dient als Träger für die Platingruppenmetalle. Der Katalysator ist ein Dreiwegekatalysator, der die schädlichen Abgaskomponenten im Platinum group metal, as well as at least one finely divided, oxygen-storing material. The platinum group metals are in close contact with all components of the first layer. The second layer is in direct contact with the exhaust gas and contains at least one platinum group metal and at least one finely divided oxygen storing material. Only part of the finely divided solids of the second layer serve as a carrier for the platinum group metals. The catalyst is a three-way catalytic converter that controls the harmful components of the exhaust gas
Wesentlichen bei stöchiometrischen Bedingungen, d.h. bei der Luftzahl λ von 1 umsetzt. Essentially at stoichiometric conditions, i. at the air ratio λ of 1.
Aus der US2009/320457 ist ein Stickoxid-Speicherkatalysator bekannt, der zwei übereinander liegende Katalysatorschichten auf einem Trägersubstrat umfasst. Die untere, direkt auf dem Trägersubstrat liegende Schicht umfasst ein oder mehrere Edelmetalle, sowie ein oder mehrere Stickoxid- Speicherkomponenten. Die obere Schicht umfasst ein oder mehrere From US2009 / 320457 a nitrogen oxide storage catalyst is known which comprises two superimposed catalyst layers on a carrier substrate. The lower layer lying directly on the carrier substrate comprises one or more noble metals, as well as one or more nitrogen oxide storage components. The upper layer comprises one or more
Edelmetalle, sowie Ceroxid und ist frei von Alkali- oder Erdalkalikomponenten. Katalysatorsubstrate, die Stickoxid-Speichermaterialien enthalten und zwei oder mehr Schichten aufweisen, sind auch in der WO 2012/029050 beschrieben. Die erste Schicht befindet sich direkt auf dem Trägersubstrat und umfasst Platin und/oder Palladium, während sich die zweite Schicht auf der ersten befindet und Platin umfasst. Beide Schichten enthalten außerdem ein oder mehrere Sauerstoffspeichermaterialien und ein oder mehrere Stickoxid-Speichermaterialien, die ein oder mehrere Alkali- und/oder Erdalkalimetalle umfassen. Die Gesamtmenge an Alkali- und Erdalkalimetall in den Stickoxid-Speichermaterialien beträgt 0,18 bis 2,5 g/in3, berechnet als Alkalimetalloxid M2O und Erdalkalimetalloxid MO. Precious metals, as well as cerium oxide and is free of alkali or alkaline earth components. Catalyst substrates containing nitrogen oxide storage materials and having two or more layers are also described in WO 2012/029050. The first layer is directly on the carrier substrate and comprises platinum and / or palladium, while the second layer is on the first and comprises platinum. Both layers also contain one or more oxygen storage materials and one or more nitric oxide storage materials comprising one or more alkali and / or alkaline earth metals. The total amount of alkali and alkaline earth metal in the nitrogen oxide storage materials is 0.18 to 2.5 g / in 3 , calculated as alkali metal oxide M2O and alkaline earth metal oxide MO.
Es ist bereits bekannt, Manganverbindungen, insbesondere Manganoxid, als Bestandteile von Katalysatoren für die Autoabgaskatalyse zu verwenden. So beschreiben die DE102011109200A1 und die US2015/165422 Mangan- haltige Dieseloxidationskatalysatoren. It is already known to use manganese compounds, in particular manganese oxide, as constituents of catalysts for car exhaust gas catalysis. For example, DE102011109200A1 and US2015 / 165422 describe manganese-containing diesel oxidation catalysts.
Die DE102012204524A1 beschreibt LNT-Katalysatoren, die Mangan-haltige Mischoxide, zum Beispiel MnOx-Ce02 enthalten. Auch die US2013/336865 beschreibt NOx-Absorber-Katalysatoren die Mangan enthalten können. Die vorliegende Erfindung betrifft einen Stickoxid-Speicherkatalysator aus mindestens zwei katalytisch aktiven Washcoatschichten auf einem DE102012204524A1 describes LNT catalysts which contain manganese-containing mixed oxides, for example MnOx-CeO 2 . US2013 / 336865 also describes NOx absorber catalysts which may contain manganese. The present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on one
Tragköper, wobei Tragköper, where
- eine untere Washcoatschicht A Ceroxid, eine Erdalkaliverbindung  a lower washcoat A ceria, an alkaline earth compound
und/oder eine Alkaliverbindung, Platin und Palladium, sowie Manganoxid enthält; und  and / or an alkali compound, platinum and palladium, as well as manganese oxide; and
- eine obere Washcoatschicht B, die über der Washcoatschicht A  an upper washcoat layer B over the washcoat layer A
angeordnet ist, Ceroxid, sowie Platin und Palladium enthält und frei ist von Alkali- und Erdalkaliverbindungen.  is arranged, contains cerium oxide, as well as platinum and palladium and is free of alkali and alkaline earth compounds.
Das in den Washcoatschichten A und B eingesetzte Ceroxid kann The cerium oxide used in washcoat layers A and B can
handelsüblicher Qualität sein, d.h. einen Ceroxid-Anteil von 90 bis 100 Gew.-% aufweisen. be of commercial quality, i. have a cerium oxide content of 90 to 100 wt .-%.
In Ausführungsformen der vorliegenden Erfindung wird Ceroxid in der Washcoatschicht A in einer Menge von 110 bis 160 g/l, beispielsweise 125 bis 145 g/l, eingesetzt. In der Washcoatschicht B wird Ceroxid in Mengen von 22 bis 120 g/l, beispielsweise 40 bis 100 g/l oder 45 bis 65 g/l eingesetzt. Als Erdalkaliverbindung in der Washcoatschicht A kommen insbesondere Oxide, Carbonate und/oder Hydroxide von Magnesium, Strontium und/oder Barium in Frage, besonders Magnesiumoxid, Bariumoxid und Strontiumoxid. Als Alkaliverbindung in der Washcoatschicht A kommen insbesondere Oxide, Carbonate und/oder Hydroxide von Lithium, Kalium und/oder Natrium in Frage.  In embodiments of the present invention, cerium oxide is used in the washcoat layer A in an amount of from 110 to 160 g / l, for example from 125 to 145 g / l. In the washcoat layer B, cerium oxide is used in amounts of 22 to 120 g / l, for example 40 to 100 g / l or 45 to 65 g / l. Suitable alkaline earth compounds in the washcoat A are, in particular, oxides, carbonates and / or hydroxides of magnesium, strontium and / or barium, in particular magnesium oxide, barium oxide and strontium oxide. Suitable alkali compounds in the washcoat A are, in particular, oxides, carbonates and / or hydroxides of lithium, potassium and / or sodium.
In Ausführungsformen der vorliegenden Erfindung liegt die Erdalkali- bzw. Alkaliverbindung in Washcoatschicht A in Mengen von 10 bis 50 g/l, besonders 15 bis 20 g/l, berechnet als Erdalkali- bzw. Alkalioxid und bezogen auf das Volumen des Tragkörpers, vor. In embodiments of the present invention, the alkaline earth or alkali compound in washcoat A is present in amounts of 10 to 50 g / l, especially 15 to 20 g / l, calculated as alkaline earth oxide and based on the volume of the support body.
In Ausführungsformen der vorliegenden Erfindung liegt Manganoxid in Washcoatschicht A in Mengen von 1 bis 10 Gew.-%, bevorzugt 2,5 bis 7,5 Gew.-%, bezogen auf die Summe der Washcoatschichten A und B, jeweils geerechnet als MnO, vor. In embodiments of the present invention, manganese oxide in washcoat A is present in amounts of from 1 to 10 weight percent, preferably 2.5 to 7.5 Wt .-%, based on the sum of Washcoatschichten A and B, each calculated as MnO before.
In weiteren Ausführungsformen enthält auch die Washcoatschicht B  In further embodiments, the washcoat layer B also contains
Manganoxid. In diesen Fällen beträgt die Menge an Manganoxid in Manganese oxide. In these cases, the amount of manganese oxide is in
Washcoatschicht B bei bis zu 2,5 Gew.-%, bevorzugt 0,5 bis 2,5 Gew.-%, bezogen auf die Summe der Washcoatschichten A und B. Washcoat layer B at up to 2.5 wt .-%, preferably 0.5 to 2.5 wt .-%, based on the sum of Washcoatschichten A and B.
In bevorzugten Ausführungsformen der vorliegenden Erfindung dient Manganoxid nicht als Trägermaterial, weder für die Edelmetalle Platin, Palladium und gegebenenfalls Rhodium, noch für eine andere Komponente von Washcoatschicht A und gegebenenfalls Washcoatschicht B. In preferred embodiments of the present invention, manganese oxide is not used as a carrier material, neither for the noble metals platinum, palladium and optionally rhodium, nor for another component of washcoat A and optionally washcoat B.
Der Begriff Manganoxid bedeutet im Rahmen der vorliegenden Erfindung insbesondere MnO, MnCh oder Mn203 oder Kombinationen von Mn02, MnO The term manganese oxide in the context of the present invention means in particular MnO, MnCh or Mn 2 O 3 or combinations of MnO 2 , MnO
In Ausführungsformen der vorliegenden Erfindung liegt Manganoxid nicht in Form von Mischoxiden mit anderen Oxiden von Washcoatschicht A und B vor. Insbesondere liegt Manganoxid nicht in Form eines Mischoxides mit Ceroxid vor, beispielsweise nicht in Form von MnOx-Ce02, MnO-Zr02 und In embodiments of the present invention, manganese oxide is not in the form of mixed oxides with other oxides of washcoat A and B layers. In particular, manganese oxide is not present in the form of a mixed oxide with cerium oxide, for example not in the form of MnOx-CeO 2 , MnO-ZrO 2 and
Das Verhältnis Platin zu Palladium in der Washcoatschicht A beträgt in Ausführungsformen der vorliegenden Erfindung beispielsweise 4: 1 bis 18 : 1 oder 6 : 1 bis 16 : 1, beispielsweise 8 : 1, 10 : 1, 12 : 1 oder 14: 1. The ratio platinum to palladium in the washcoat A in embodiments of the present invention is for example 4: 1 to 18: 1 or 6: 1 to 16: 1, for example 8: 1, 10: 1, 12: 1 or 14: 1.
Das Verhältnis Platin zu Palladium in der Washcoatschicht B beträgt ebenfalls in Ausführungsformen der vorliegenden Erfindung beispielsweise 4: 1 bis 18 : 1 oder 6 : 1 bis 16 : 1, beispielsweise 8 : 1, 10 : 1, 12 : 1 oder 14: 1 ist aber vom Verhältnis in Washcoatschicht A unabhängig.  The ratio platinum to palladium in the washcoat layer B is also in embodiments of the present invention, for example 4: 1 to 18: 1 or 6: 1 to 16: 1, for example 8: 1, 10: 1, 12: 1 or 14: 1 but independent of the ratio in washcoat A
In Ausführungsformen der vorliegenden Erfindung enthält Washcoatschicht B als weiteres Edelmetall Rhodium. Rhodium liegt in diesem Fall In embodiments of the present invention, washcoat B contains rhodium as another precious metal. Rhodium is in this case
insbesondere in Mengen von 0,003 bis 0,35 g/l (0,1 bis 10 g/ft3), insbesondere 0,18 bis 0,26 g/l (5 bis 7,5 g/ft3), jeweils bezogen auf das Volumen des Tragkörpers, vor. especially in amounts of 0.003 to 0.35 g / l (0.1 to 10 g / ft 3 ), in particular 0.18 to 0.26 g / l (5 to 7.5 g / ft 3 ), in each case based on the volume of the supporting body before.
Die Gesamtmenge an Edelmetall, d.h. von Platin, Palladium und The total amount of noble metal, i. of platinum, palladium and
gegebenenfalls Rhodium, im erfindungsgemäßen Stickoxid-Speicherkatalysator beträgt in Ausführungsformen der vorliegenden Erfindung 2,12 bis 7,1 g/l (60 bis 200 g/ft3), bezogen auf das Volumen des Tragkörpers. optionally rhodium, in the nitrogen oxide storage catalyst according to the invention is in embodiments of the present invention, 2.12 to 7.1 g / l (60 to 200 g / ft 3 ), based on the volume of the support body.
Sowohl in der Washcoatschicht A, als auch in der Washcoatschicht B liegen die Edelmetalle Platin und Palladium und gegebenenfalls Rhodium Both in the washcoat layer A and in the washcoat layer B, the noble metals are platinum and palladium and optionally rhodium
üblicherweise auf geeigneten Trägermaterialien vor. Als solche werden insbesondere Oxide mit einer BET-Oberfläche von 30 bis 250 m2/g, bevorzugt von 100 bis 200 m2/g auf (bestimmt nach DIN 66132) usually on suitable carrier materials. As such, in particular oxides having a BET surface area of 30 to 250 m 2 / g, preferably from 100 to 200 m 2 / g (determined according to DIN 66132)
verwendet, beispielsweise Aluminiumoxid, Siliziumdioxid, Titandioxid, aber auch Mischoxide wie beispielsweise Aluminium-Silizium-Mischoxide und Cer- Zirkon-Mischoxide. used, for example, alumina, silica, titanium dioxide, but also mixed oxides such as aluminum-silicon mixed oxides and cerium-zirconium mixed oxides.
In Ausführungsformen der vorliegenden Erfindung wird als Trägermaterial für die Edelmetalle Platin und Palladium und gegebenenfalls Rhodium  In embodiments of the present invention, platinum and palladium and, optionally, rhodium are used as support material for the noble metals
Aluminiumoxid verwendet, insbesondere solches, das durch 1 bis 6 Gew.- %, insbesondere 4 Gew.-%, Lanthanoxid stabilisiert ist. Alumina is used, in particular those which is stabilized by 1 to 6 wt .-%, in particular 4 wt .-%, lanthanum oxide.
Es ist bevorzugt, wenn die Edelmetalle Platin, Palladium und gegebenenfalls Rhodium lediglich auf einem oder mehreren der oben genannten It is preferred if the precious metals platinum, palladium and optionally rhodium only on one or more of the above
Trägermaterialien geträgert sind und somit nicht mit allen Bestandteilen der jeweiligen Washcoatschicht in enger Berührung stehen. Insbesondere dient Manganoxid bevorzugt nicht als Träger für Platin und Palladium und gegebenenfalls Rhodium . Carrier materials are supported and thus are not in close contact with all components of the respective Washcoatschicht. In particular, manganese oxide preferably does not serve as a support for platinum and palladium and optionally rhodium.
Die Gesamt-Washcoatbeladung des Tragkörpers beträgt in The total washcoat load of the support body is in
Ausführungsformen der vorliegenden Erfindung 300 bis 600 g/l, bezogen auf das Volumen des Tragkörpers. In einer bevorzugten Ausführungsform betrifft die vorliegende Erfindung einen Stickoxid-Speicherkatalysator aus mindestens zwei katalytisch aktiven Washcoatschichten auf einem Tragkörper, Embodiments of the present invention 300 to 600 g / l, based on the volume of the support body. In a preferred embodiment, the present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on a support body,
wobei in which
- eine untere Washcoatschicht A a lower washcoat layer A
o Ceroxid in einer Menge von 100 bis 160 g/l,  o cerium oxide in an amount of 100 to 160 g / l,
o Platin und Palladium im Massenverhältnis 10 : 1,  o platinum and palladium in a mass ratio of 10: 1,
o Magnesiumoxid und/oder Bariumoxid; sowie  o magnesium oxide and / or barium oxide; such as
o Manganoxid in einer Menge von 10 bis 20 g/l enthält und  o contains manganese oxide in an amount of 10 to 20 g / l and
- eine obere Washcoatschicht B über der unteren Washcoatschicht A an upper washcoat layer B over the lower washcoat layer A.
angeordnet ist und  is arranged and
o keine Erdalkaliverbindung und keine Alkaliverbindung,  o no alkaline earth compound and no alkali compound,
o Platin und Palladium im Massenverhältnis 10 : 1 sowie  o platinum and palladium in a mass ratio of 10: 1 and
o Ceroxid in einer Menge von 45 bis 65 g/l  o Cerium oxide in an amount of 45 to 65 g / l
enthält, wobei die Washcoatschicht A in Mengen von 250 bis 350 g/l und die Washcoatschicht B in Mengen von 80 bis 130 g/l vorliegt und wobei sich die Mengenangabe g/l jeweils auf das Volumen des Tragkörpers bezieht. wherein the Washcoatschicht A in amounts of 250 to 350 g / l and the Washcoatschicht B in amounts of 80 to 130 g / l is present and wherein the amount g / l each refers to the volume of the support body.
Die Aufbringung der katalytisch aktiven Washcoatschichten A und B auf den Tragkörper erfolgt nach den üblichen Tauchbeschichtungsverfahren bzw. Pump- und Saug-Beschichtungsverfahren mit sich anschließender The application of the catalytically active Washcoatschichten A and B on the support body is carried out according to the usual dip coating method or pump and suction coating method with it
thermischer Nachbehandlung (Kalzination und gegebenenfalls Reduktion mit Formiergas oder Wasserstoff). Diese Verfahren sind aus dem Stand der Technik hinreichend bekannt. thermal aftertreatment (calcination and optionally reduction with forming gas or hydrogen). These methods are well known in the art.
Die dafür notwendigen Beschichtungssuspensionen können nach dem The necessary coating suspensions can after the
Fachmann bekannten Verfahren erhalten werden. So werden die Known to those skilled in the art. So will the
Bestandteile, wie Ceroxid, Erdalkali- und/oder Alkaliverbindung, auf geeigneten Trägermaterialien geträgerte Edelmetalle, sowie Manganoxid bzw. eine andere Manganverbindung in den entsprechenden Mengen in Wasser aufgeschlämmt und in einer geeigneten Mühle, insbesondere einer Kugelmühle, auf eine Teilchengröße von dso = 3 bis 5 Mm gemahlen. Es ist bevorzugt, Mangan in Form von Mangancarbonat der Beschichtungssuspension im letzten Schritt, d.h. unmittelbar vor dem Mahlen, zuzugeben. Components such as cerium oxide, alkaline earth and / or alkali compound, supported on suitable support materials noble metals, and manganese oxide or other manganese compound in the appropriate amounts in water slurried and in a suitable mill, in particular a ball mill, to a particle size of dso = 3 to 5 mm ground. It is preferred manganese in the form of manganese carbonate of Add coating suspension in the last step, ie immediately before grinding.
Die erfindungsgemäßen Stickoxid-Speicherkatalysatoren eignen sich in hervorragender Weise zur Konvertierung von NOx in Abgasen von The nitrogen oxide storage catalysts according to the invention are outstandingly suitable for converting NOx into exhaust gases of
Kraftfahrzeugen, die mit mager betriebenen Motoren, etwa Dieselmotoren, betrieben werden. Sie erreichen eine gute NOx-Konvertierung bei  Motor vehicles operated by lean-burn engines, such as diesel engines. They achieve good NOx conversion
Temperaturen von circa 200 bis 450°C, ohne dass die NOx-Konvertierung bei hohen Temperaturen negativ beeinflusst wird. Die erfindungsgemäßen Stickoxid-Speicherkatalysatoren sind somit für Euro 6 Anwendungen geeignet. Temperatures of about 200 to 450 ° C, without the NOx conversion is adversely affected at high temperatures. The nitrogen oxide storage catalysts according to the invention are thus suitable for Euro 6 applications.
Die vorliegende Erfindung betrifft somit auch ein Verfahren zur  The present invention thus also relates to a method for
Konvertierung von NOx in Abgasen von Kraftfahrzeugen, die mit mager betriebenen Motoren, etwa Dieselmotoren, betrieben werden, das dadurch gekennzeichnet ist, dass das Abgas über einen Stickoxid-Speicherkatalysator aus mindestens zwei katalytisch aktiven Washcoatschichten auf einem Tragköper geleitet wird, wobei Conversion of NOx in exhaust gases of motor vehicles, which are operated with lean-burn engines, such as diesel engines, which is characterized in that the exhaust gas is passed through a nitrogen oxide storage catalyst of at least two catalytically active Washcoatschichten on a support body
- eine untere Washcoatschicht A Ceroxid, eine Erdalkaliverbindung  a lower washcoat A ceria, an alkaline earth compound
und/oder eine Alkaliverbindung, Platin und Palladium, sowie Manganoxid enthält; und  and / or an alkali compound, platinum and palladium, as well as manganese oxide; and
- eine obere Washcoatschicht B, die über der Washcoatschicht A  an upper washcoat layer B over the washcoat layer A
angeordnet ist, Ceroxid, sowie Platin und Palladium enthält und frei ist von Alkali- und Erdalkaliverbindungen. Ausgestaltungen des erfindungsgemäßen Verfahrens hinsichtlich des Stickoxid-Speicherkatalysators entsprechen den oben stehenden  is arranged, contains cerium oxide, as well as platinum and palladium and is free of alkali and alkaline earth compounds. Embodiments of the method according to the invention with regard to the nitrogen oxide storage catalyst correspond to the above
Beschreibungen. Descriptions.
Die Erfindung wird in den nachstehenden Beispielen und Figuren näher erläutert. The invention is explained in more detail in the following examples and figures.
Figur 1 : NOx-Konvertierung der Katalysatoren Kl (gestrichelte Linie) und VK1 (durchgezogene Linie) in Abhängigkeit von der Temperatur. Figur 2 : NOx-Konvertierung der Katalysatoren K2 (durchgezogene Linie) und K3 (gestrichelte) in Abhängigkeit von der Temperatur. Figur 3 : NOx-Konvertierung der Katalysatoren K2 (durchgezogene Linie) und K4 (gestrichelte) in Abhängigkeit von der Temperatur. Figure 1: NOx conversion of the catalysts Kl (dashed line) and VK1 (solid line) as a function of temperature. Figure 2: NOx conversion of the catalysts K2 (solid line) and K3 (dashed) as a function of temperature. Figure 3: NOx conversion of the catalysts K2 (solid line) and K4 (dashed) as a function of temperature.
Beispiel 1 example 1
a) Zur Herstellung eines erfindungsgemäßen Katalysators wird ein wabenförmiger Keramikträger mit einer ersten Washcoatschicht A a) To produce a catalyst according to the invention is a honeycomb ceramic carrier with a first Washcoatschicht A
beschichtet, die Pt und Pd geträgert auf Aluminiumoxid, Ceroxid in einer Menge 125 g/l, 21 g/l Bariumoxid, 15 g/l Magnesiumoxid und 7,5 g/l MnO in Form von Mangancarbonat enthält. Die Beladung von Pt und Pd beträgt dabei 35 g/ft3 (1,236 g/l) und 3,5 g/ft3 (0,124 g/l) und die Gesamtbeladung der Washcoatschicht ca. 293 g/l bezogen auf das Volumen des Keramik- Trägers. coated, containing Pt and Pd supported on alumina, ceria in an amount of 125 g / l, 21 g / l barium oxide, 15 g / l magnesium oxide and 7.5 g / l MnO in the form of manganese carbonate. The loading of Pt and Pd is 35 g / ft 3 (1.236 g / l) and 3.5 g / ft 3 (0.124 g / l) and the total loading of the washcoat layer about 293 g / l based on the volume of the ceramic - Carrier.
b) Auf die erste Washcoatschicht wird eine weitere Washcoatschicht B aufgebracht, die ebenfalls Pt und Pd geträgert auf Aluminiumoxid, sowie Rh geträgert auf einem Lanthan-stabilisierten Aluminiumoxid enthält. Die Beladung von Pt, Pd und Rh in dieser Washcoatschicht beträgt 35 g/ft3 (1,236 g/l), 3,5 g/ft3 (0,124 g/l) und 5 g/ft3 (0,177 g/l). Die Washcoatschicht B enthält außerdem 55 g/l Ceroxid bei einer Washcoatbeladung der Schicht B von ca. 81 g/l. b) A further washcoat layer B is applied to the first washcoat layer, also containing Pt and Pd supported on alumina, and Rh supported on a lanthanum stabilized alumina. The loading of Pt, Pd and Rh in this washcoat layer is 35 g / ft 3 (1.236 g / l), 3.5 g / ft 3 (0.124 g / l) and 5 g / ft 3 (0.177 g / l). The washcoat layer B also contains 55 g / l of cerium oxide with a layer B washcoat loading of about 81 g / l.
Der so erhaltene Katalysator wird nachstehend Kl genannt.  The catalyst thus obtained is hereinafter called Kl.
Vergleichsbeispiel 1 Comparative Example 1
Beispiel 1 wurde wiederholt mit dem Unterschied, dass Washcoatschicht A kein Manganoxid enthielt. Der so erhaltene Katalysator wird nachstehend VK1 genannt.  Example 1 was repeated with the difference that washcoat A did not contain manganese oxide. The catalyst thus obtained is hereinafter called VK1.
Bestimmung der NOx-Konvertierung von Kl und VK1 Determination of NOx conversion of Kl and VK1
a) Zunächst wurden Kl und VK1 16h bei 800°C in hydrothermaler a) First, Kl and VK1 were hydrothermal at 800 ° C for 16h
Atmosphäre gealtert. b) Die NOx-Konvertierung von Kl bzw. VK1 in Abhängigkeit von der Temperatur vor dem Katalysator wurde in einem Modellgasreaktor im sog. NOx- Umsatztest bestimmt. Atmosphere aged. b) The NOx conversion of Kl or VK1 as a function of the temperature before the catalyst was determined in a model gas reactor in the so-called NOx conversion test.
In diesem wird synthetisches Abgas mit einer Stickstoffmonoxid- konzentration von 500ppm, jeweils 10 Vol.-% Kohlenstoffdioxid und  This is synthetic exhaust gas with a nitrogen monoxide concentration of 500 ppm, 10 vol .-% carbon dioxide and
Wasser, einer Konzentration von 50ppm eines kurzkettigen Water, a concentration of 50ppm of a short-chain
Kohlenwasserstoffgemisches (bestehend aus 33 ppm Propen und 17 ppm Propan) sowie einem Restsauerstoffgehalt von 7 Vol.-% bei einer Hydrocarbon mixture (consisting of 33 ppm propene and 17 ppm propane) and a residual oxygen content of 7 vol .-% at one
Raumgeschwindigkeit von 50k/h in einem Modellgasreaktor über die jeweilige Katalysatorprobe geleitet, wobei die Gasmischung abwechselnd 80s lang einen Sauerstoffüberschuss enthält („mageres" Gasgemisch mit Luftzahl λ von 1,47) währenddessen Stickoxide eingespeichert werden, und zur Regeneration der Katalysatorprobe 10s lang ein Sauerstoffdefizit aufweist („fettes" Gasgemisch mit Luftzahl λ von 0,92; durch Zumischen von 5,5 Vol.-% Kohlenstoffmonoxid bei gleichzeitiger Absenkung des Restsauerstoffgehalts auf 1 Vol.-%). Space velocity of 50k / h passed in a model gas reactor over the respective catalyst sample, wherein the gas mixture alternately an oxygen excess 80s long ("lean" gas mixture with air ratio λ of 1.47) while nitrogen oxides are stored, and to regenerate the catalyst sample for 10s long an oxygen deficit ("rich" gas mixture with air ratio λ of 0.92, by mixing 5.5% by volume of carbon monoxide while reducing the residual oxygen content to 1% by volume).
Dabei wird die Temperatur mit 7,5 °C/min von 600°C auf 150°C abgesenkt und der Umsatz über jeden 90s dauernden Mager- Fett-Zyklus ermittelt. Figur 1 zeigt die so bestimmten NOx-Konvertierungen des erfindungs- gemäßen Katalysators Kl, sowie des Vergleichskatalysators VK1. Demnach liegt der Umsatz von Kl im gesamten Temperaturbereich über dem Umsatz von VK1.  The temperature is lowered at 7.5 ° C / min from 600 ° C to 150 ° C and determines the conversion over each 90s long lean-fat cycle. FIG. 1 shows the NO x conversions of the inventive catalyst K 1 and of the comparative catalyst VK 1 thus determined. Thus, the turnover of Kl in the entire temperature range is higher than the sales of VK1.
Beispiel 2 Example 2
a) Zur Herstellung eines weiteren erfindungsgemäßen Katalysators wird ein wabenförmiger Keramikträger mit einer ersten Washcoatschicht A beschichtet, die Pt und Pd geträgert auf Aluminiumoxid, Ceroxid in einer Menge 125 g/l, 21 g/l Bariumoxid, 7,5 g/l Magnesiumoxid und 7,5 g/l Manganoxid in Form von Mangancarbonat enthält. Die Beladung von Pt und Pd beträgt dabei 35 g/ft3 (1,236 g/l) und 3,5 g/ft3 (0,124 g/l)und diea) To produce a further inventive catalyst, a honeycomb ceramic support is coated with a first washcoat A, the Pt and Pd supported on alumina, ceria in an amount of 125 g / l, 21 g / l barium oxide, 7.5 g / l magnesium oxide and 7.5 g / l manganese oxide in the form of manganese carbonate. The loading of Pt and Pd is 35 g / ft 3 (1.236 g / l) and 3.5 g / ft 3 (0.124 g / l) and the
Gesamtbeladung der Washcoatschicht ca. 299 g/l bezogen auf das Volumen des Keramik-Trägers. b) Auf die erste Washcoatschicht wird eine weitere Washcoatschicht B aufgebracht, die ebenfalls Pt und Pd, sowie Rh geträgert auf Aluminiumoxid enthält. Die Beladung von Pt, Pd und Rh in dieser Washcoatschicht beträgt 35 g/ft3 (1,236 g/l), 3,5 g/ft3 (0,124 g/l) und 5 g/ft3 (0,177 g/l). Die Total loading of the washcoat layer about 299 g / l based on the volume of the ceramic carrier. b) On the first washcoat layer another washcoat layer B is applied, which also contains Pt and Pd, and Rh supported on alumina. The loading of Pt, Pd and Rh in this washcoat layer is 35 g / ft 3 (1.236 g / l), 3.5 g / ft 3 (0.124 g / l) and 5 g / ft 3 (0.177 g / l). The
Washcoatschicht B enthält außerdem 55 g/l Ceroxid bei einer Washcoat layer B also contains 55 g / l of cerium oxide at one
Washcoatbeladung der Schicht B von ca. 94 g/l . Washcoat loading of layer B of approx. 94 g / l.
Der so erhaltene Katalysator wird nachstehend K2 genannt. The catalyst thus obtained is hereinafter called K2.
Beispiel 3 Example 3
Beispiel 2 wurde wiederholt mit dem Unterschied, dass Washcoatschicht B zusätzlich 2,5 g/l Manganoxid in Form von Mangancarbonat enthielt. Example 2 was repeated with the difference that washcoat B additionally contained 2.5 g / l of manganese oxide in the form of manganese carbonate.
Der so erhaltene Katalysator wird nachstehend K3 genannt. The catalyst thus obtained is hereinafter called K3.
Die NOx-Konvertierung von K2 und K3 wurde wie oben beschrieben gemessen. Figur 2 zeigt das Ergebnis. NOx conversion of K2 and K3 was measured as described above. Figure 2 shows the result.
Beispiel 4 Example 4
Beispiel 2 wurde wiederholt mit dem Unterschied, dass Washcoatschicht A 15 g/l Manganoxid in Form von Mangancarbonat enthielt.  Example 2 was repeated with the difference that washcoat A contained 15 g / l of manganese oxide in the form of manganese carbonate.
Der so erhaltene Katalysator wird nachstehend K4 genannt. The catalyst thus obtained is hereinafter called K4.
Die NOx-Konvertierung von K2 und K4 wurde wie oben beschrieben gemessen. Figur 3 zeigt das Ergebnis. Beispiele 5 bis 10 The NOx conversion of K2 and K4 was measured as described above. FIG. 3 shows the result. Examples 5 to 10
Beispiel 1 wurde wiederholt mit dem Unterschied, dass die in nachstehender Tabelle 1 angegebenen Ceroxid- und Manganoxidmengen eingesetzt wurden.  Example 1 was repeated with the difference that the amounts of cerium oxide and manganese oxide indicated in Table 1 below were used.
Die so erhaltenen Katalysatoren werden K2 bis K6 genannt. Tabelle 1 The catalysts thus obtained are called K2 to K6. Table 1
CeOz CeOz MnO MnO CeOz CeOz MnO MnO
Katalysator Washcoat A Washcoat B Washcoat A Washcoat B Catalyst Washcoat A Washcoat B Washcoat A Washcoat B
[g/i] [g/i] [g/i] [g/i] [g / i] [g / i] [g / i] [g / i]
K5 110 25 5 1K5 110 25 5 1
K6 125 40 7,5 -K6 125 40 7.5 -
K7 140 60 2,5 -K7 140 60 2.5 -
K8 155 100 2,5 2,5K8 155 100 2.5 2.5
K9 155 22 7,5 0,5K9 155 22 7.5 0.5
K10 110 129 2 2,5 K10 110 129 2 2.5

Claims

Patentansprüche claims
1. Stickoxid-Speicherkatalysator aus mindestens zwei katalytisch aktiven Washcoatschichten auf einem Tragköper, wobei 1. nitrogen oxide storage catalyst of at least two catalytically active Washcoatschichten on a support body, wherein
- eine untere Washcoatschicht A Ceroxid, eine Erdalkaliverbindung  a lower washcoat A ceria, an alkaline earth compound
und/oder eine Alkaliverbindung, Platin und Palladium, sowie Manganoxid enthält; und  and / or an alkali compound, platinum and palladium, as well as manganese oxide; and
- eine obere Washcoatschicht B, die über der Washcoatschicht A  an upper washcoat layer B over the washcoat layer A
angeordnet ist, Ceroxid, sowie Platin und Palladium enthält und frei ist von Alkali- und Erdalkaliverbindungen.  is arranged, contains cerium oxide, as well as platinum and palladium and is free of alkali and alkaline earth compounds.
2. Stickoxid-Speicherkatalysator nach Anspruch 1, dadurch gekennzeichnet, dass die Washcoatschicht A Ceroxid in einer Menge von 110 bis 160 g/l enthält. 2. nitrogen oxide storage catalyst according to claim 1, characterized in that the Washcoatschicht A contains ceria in an amount of 110 to 160 g / l.
3. Stickoxid-Speicherkatalysator nach Anspruch 1 und/oder 2, dadurch gekennzeichnet, dass die Washcoatschicht B Ceroxid in einer Menge von 22 bis 120 g/l enthält. 3. nitrogen oxide storage catalyst according to claim 1 and / or 2, characterized in that the Washcoatschicht B contains ceria in an amount of 22 to 120 g / l.
4. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass in Washcoatschicht A die 4. nitrogen oxide storage catalyst according to one or more of claims 1 to 3, characterized in that in Washcoatschicht A the
Erdalkaliverbindung ein Oxid, Carbonat und/oder Hydroxid von Magnesium, Strontium und/oder Barium ist.  Alkaline earth compound is an oxide, carbonate and / or hydroxide of magnesium, strontium and / or barium.
5. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Erdalkaliverbindung in 5. nitrogen oxide storage catalyst according to one or more of claims 1 to 4, characterized in that the alkaline earth compound in
Washcoatschicht A Magnesiumoxid, Bariumoxid und/oder Strontiumoxid ist.  Washcoat layer A is magnesium oxide, barium oxide and / or strontium oxide.
6. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass in Washcoatschicht A Die 6. nitrogen oxide storage catalyst according to one or more of claims 1 to 5, characterized in that in Washcoatschicht A Die
Alkaliverbindung ein Oxid, Carbonat und/oder Hydroxid von von Lithium, Kalium und/oder Natrium ist. Alkali compound is an oxide, carbonate and / or hydroxide of lithium, potassium and / or sodium.
7. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Erdalkali- bzw. Alkaliverbindung in Washcoatschicht A in Mengen von 10 bis 50 g/l, berechnet als Erdalkalibzw. Alkalioxid und bezogen auf das Volumen des Tragkörpers, vorliegt. 7. nitrogen oxide storage catalyst according to one or more of claims 1 to 6, characterized in that the alkaline earth or alkali compound in washcoat A in amounts of 10 to 50 g / l, calculated as Erdalkalibzw. Alkali oxide and based on the volume of the support body, is present.
8. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass Manganoxid in Washcoatschicht A in Mengen von 1 bis 10 Gew.-%, bezogen auf die Summe der Washcoat- schichten A und B und gerechnet als MnO, vorliegt. 8. nitrogen oxide storage catalyst according to one or more of claims 1 to 7, characterized in that manganese oxide in washcoat A in amounts of 1 to 10 wt .-%, based on the sum of Washcoat- layers A and B and calculated as MnO, is present.
9. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass Manganoxid in Washcoatschicht B in Mengen von bis zu 2,5 Gew.-%, bezogen auf die Summe der Washcoat- schichten A und B und gerechnet als MnO, vorliegt. 9. nitric oxide storage catalyst according to one or more of claims 1 to 8, characterized in that manganese oxide in washcoat B in amounts of up to 2.5 wt .-%, based on the sum of Washcoat- layers A and B and calculated as MnO, present.
10. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das Verhältnis Platin zu Palladium in Washcoatschicht A und in Washcoatschicht B unabhängig voneinander jeweils 4: 1 bis 18 : 1 beträgt. 10. nitric oxide storage catalyst according to one or more of claims 1 to 9, characterized in that the ratio of platinum to palladium in Washcoatschicht A and in Washcoatschicht B independently 4: 1 to 18: 1.
11. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass Washcoatschicht B Rhodium enthält. 11. Nitrogen storage catalyst according to one or more of claims 1 to 10, characterized in that Washcoatschicht B contains rhodium.
12. Stickoxid-Speicherkatalysator nach Anspruch 11, dadurch 12. Nitrogen storage catalyst according to claim 11, characterized
gekennzeichnet, dass Rhodium in Mengen von 0,003 bis 0,35 g/l, bezogen auf das Volumen des Tragkörpers, vorliegt. characterized in that rhodium in amounts of 0.003 to 0.35 g / l, based on the volume of the support body, is present.
13. Stickoxid-Speicherkatalysator nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Gesamt-Washcoatbeladung des Tragkörpers 300 bis 600g/l, bezogen auf das Volumen des Tragkörpers, beträgt. 13. Nitrogen storage catalyst according to one or more of claims 1 to 12, characterized in that the total Washcoatbeladung of the support body 300 to 600g / l, based on the volume of the support body is.
14. Stickoxid-Speicherkatalysator nach Anspruch 1, dadurch gekennzeichnet, dass er 14. Nitrogen storage catalyst according to claim 1, characterized in that it
eine untere Washcoatschicht A  a lower washcoat layer A
o Ceroxid in einer Menge von 100 bis 160 g/l,  o cerium oxide in an amount of 100 to 160 g / l,
o Platin und Palladium im Massenverhältnis 10 : 1,  o platinum and palladium in a mass ratio of 10: 1,
o Magnesiumoxid und/oder Bariumoxid; sowie  o magnesium oxide and / or barium oxide; such as
o Manganoxid in einer Menge von 10 bis 20 g/l enthält und  o contains manganese oxide in an amount of 10 to 20 g / l and
eine obere Washcoatschicht B, die über der unteren Washcoatschicht A angeordnet ist und  an upper washcoat layer B disposed over the lower washcoat layer A and
o keine Erdalkaliverbindung und keine Alkaliverbindung,  o no alkaline earth compound and no alkali compound,
o Platin und Palladium im Massenverhältnis 10 : 1, sowie  o platinum and palladium in a mass ratio of 10: 1, and
o Ceroxid in einer Menge von 45 bis 65 g/l  o Cerium oxide in an amount of 45 to 65 g / l
enthält, wobei die Washcoatschicht A in Mengen von 250 bis 350 g/l und die Washcoatschicht B in Mengen von 80 bis 130 g/l vorliegt und wobei sich die Mengenangabe g/l jeweils auf das Volumen des Tragkörpers bezieht. wherein the Washcoatschicht A in amounts of 250 to 350 g / l and the Washcoatschicht B in amounts of 80 to 130 g / l is present and wherein the amount g / l each refers to the volume of the support body.
15. Verfahren zur Konvertierung von NOx in Abgasen von Kraftfahrzeugen, die mit mager betriebenen Motoren betrieben werden, dadurch 15. Method for converting NOx into exhaust gases of motor vehicles operated with lean-burn engines
gekennzeichnet, dass das Abgas über einen Stickoxid-Speicherkatalysator gemäß einem oder mehreren der Ansprüche 1 bis 14 geleitet wird. characterized in that the exhaust gas is passed over a nitrogen oxide storage catalyst according to one or more of claims 1 to 14.
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