WO2018069199A1 - Ensemble de catalyseurs - Google Patents

Ensemble de catalyseurs Download PDF

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Publication number
WO2018069199A1
WO2018069199A1 PCT/EP2017/075583 EP2017075583W WO2018069199A1 WO 2018069199 A1 WO2018069199 A1 WO 2018069199A1 EP 2017075583 W EP2017075583 W EP 2017075583W WO 2018069199 A1 WO2018069199 A1 WO 2018069199A1
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WIPO (PCT)
Prior art keywords
catalyst
oxide
material zone
cerium
arrangement according
Prior art date
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PCT/EP2017/075583
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German (de)
English (en)
Inventor
Thomas UTSCHIG
Frank Adam
Ruediger Hoyer
Original Assignee
Umicore Ag & 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.)
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Publication date
Application filed by Umicore Ag & Co. Kg filed Critical Umicore Ag & Co. Kg
Priority to DE112017005130.4T priority Critical patent/DE112017005130A5/de
Publication of WO2018069199A1 publication Critical patent/WO2018069199A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/101—Three-way catalysts
    • 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
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
    • 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
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • 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
    • B01D2255/1025—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
    • B01D2255/2022—Potassium
    • 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
    • B01D2255/2025—Lithium
    • 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
    • B01D2255/2027—Sodium
    • 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
    • B01D2255/2042—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
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2061—Yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • 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
    • 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
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • 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
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a catalyst arrangement for purifying exhaust gas from lean-burn gasoline engines.
  • the exhaust gas of motor vehicles fueled by lean-burn direct-injection gasoline engines also contains residual hydrocarbons (HC) resulting from incomplete combustion of the fuel in the combustion chamber of the cylinder.
  • HC residual hydrocarbons
  • nitrogen oxide storage catalysts for which the term “Lean NOx trap” or “LNT is common .
  • Their cleaning effect is based on the fact that in a lean operating phase of the engine, the nitrogen oxides from the storage material of the storage catalyst predominantly in the form of Nitrates are stored and these decomposed in a subsequent rich phase of the engine engine again and the thus released 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 able to form nitrates with the acid nitrogen oxides of the exhaust gas and to store 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 NO2 under lean conditions as well as CO and HC to CO2 and H2O and on the other hand during the rich
  • CN 105916578A (equivalent to EP 3 097 977 A1) discloses inter alia a two-layer catalyst which is present in both layers
  • Cerium oxide, barium oxide and precious metal The document broadly indicates that this catalyst can be combined with other catalysts, for example, a three-way catalyst. A similar disclosure is also contained in US 2014/260214. Another known method for removing nitrogen oxides from exhaust gases in the presence of oxygen is the selective catalytic
  • SCR process using ammonia on a suitable catalyst.
  • the nitrogen oxides to be removed from the exhaust gas are reacted with ammonia to nitrogen and water.
  • the ammonia used as the reducing agent can be made available in the "SCR active process” by metering an ammonia precursor compound, such as urea, ammonium carbamate or ammonium formate, into the exhaust gas line and subsequent hydrolysis.
  • an ammonia precursor compound such as urea, ammonium carbamate or ammonium formate
  • the ammonia is formed from nitrogen oxide storage catalyst arranged on the upstream side of nitrogen oxides, that is to say it does not have to be added from an off-engine source WO2010 / 114873A2 discloses such a process.
  • JP2008-121575A describes a catalyst arrangement which comprises a nitrogen oxide storage catalyst and a hydrogen-forming catalyst arranged upstream thereof.
  • the hydrogen formed in a rich operating phase serves as a reducing agent for the reduction of nitrogen oxide, which is released from the nitrogen oxide storage catalyst.
  • the hydrogen-forming catalyst has a two-layer structure in which the lower layer contains a noble metal other than rhodium, for example, platinum, and the upper layer contains rhodium.
  • the downstream part of the upper rhodium-containing layer further comprises small amounts of ceria.
  • RDE Real Driving Emissions
  • the present invention relates to a catalyst arrangement which
  • Material zones includes Bl and B2, wherein material zone B2 is seconded over material zone Bl and
  • Material zone B2 cerium oxide or cerium / zirconium mixed oxide having a cerium oxide content of> 60 wt .-%, based on the weight of the mixed oxide, and palladium or platinum and palladium in
  • Weight ratio Pt contains Pd ⁇ 1 and is free of alkaline earth and alkali compounds, and / or
  • Material zones C1 and C2 comprises, wherein material zone C2 is seconded over material zone Cl and
  • Material zone C2 Cerium oxide or cerium / zirconium mixed oxide having a cerium oxide content of> 60% by weight, based on the weight of the mixed oxide, platinum and palladium in the weight ratio Pt: Pd> 2 u rhodium in an amount> 0.1 g / l, based on the volume of carrier substrate contains Tc and is free of alkaline earth and alkali compounds,
  • Three-way catalysts can be used. These contain in particular one or more precious metals, in particular platinum, palladium and / or Rhodium, as well as an oxygen storage component. As the latter, in particular mixed oxides of cerium oxide, zirconium oxide and optionally other oxides such as lanthanum oxide, niobium oxide, praseodymium oxide, yttrium oxide or neodymium oxide come into question.
  • Dreiwegekatalysator A a single material zone, all components, ie in particular platinum, palladium and / or rhodium, and a
  • the three-way catalyst A comprises two material zones AI and A2, wherein material zone A2 is arranged over material zone AI and wherein
  • Material zone AI at least one platinum group metal, and a
  • Material zone A2 at least one platinum group metal, and a
  • SE is a rare earth metal other than cerium and the proportion of SE oxide in the cerium / zirconium / SE mixed oxide of layer AI is smaller than the proportion of the SE oxide in cerium / zirconium / SE mixed oxide of layer A2, respectively Wt .-% and based on the cerium / zirconium / SE mixed oxide.
  • the material zones AI and A2 contain as platinum group metal independently of one another in particular platinum, palladium, rhodium or mixtures of at least two of these platinum group metals.
  • both material zones AI and A2 contain palladium as the only platinum group metal. However, it may also be, for example, material zone AI platinum, palladium or platinum and palladium and material zone A2
  • material zone AI contains palladium and material zone A2 rhodium or palladium and rhodium.
  • the three-way catalyst A is free of platinum, for example.
  • cerium / zirconium / SE mixed oxide in the context of the present invention excludes physical mixtures of cerium oxide, zirconium oxide and SE oxide.
  • Cerium / zirconium / SE mixed oxides are characterized by a substantially homogeneous, three-dimensional crystal structure which
  • Suitable rare earth metal oxides in the cerium / zirconium / SE mixed oxides are, for example, lanthanum oxide, yttrium oxide, praseodymium oxide, neodymium oxide, samarium oxide and mixtures of one or more of these metal oxides.
  • Lanthanum oxide, yttrium oxide, praseodymium oxide and mixtures of one or more of these metal oxides are preferred. Particularly preferred are lanthanum oxide, yttrium oxide and very particularly preferred is a mixture of lanthanum oxide and yttrium oxide.
  • the proportion of the SE oxide in the cerium / zirconium / SE mixed oxide of material zone AI is smaller than the proportion of the SE oxide in the cerium / zirconium / SE mixed oxide of material zone A2, in each case calculated in% by weight and based on the cerium / Zirconium / SE mixed oxide.
  • the proportion of the SE oxide in material zone Al is in particular 1 to 12 wt .-%, preferably 3 to 10 wt .-% and particularly preferably 6 to 9 wt .-%, each based on the cerium / zirconium / SE mixed oxide.
  • the proportion of the SE oxide in material zone A2 is in particular 2 to 25% by weight, preferably 10 to 20% by weight and particularly preferably 14 to 18% by weight, in each case based on the cerium / zirconium / SE mixed oxide.
  • the ratio of ceria to zirconia in the cerium / zirconium / Se mixed oxides can vary widely.
  • material zone AI it is, for example, 0.1 to 1.0, preferably from 0.2 to 0.7, particularly preferably from 0.3 to 0.5.
  • material zone A2 it is for example 0.1 to 1.0, preferably from 0.2 to 0.7, particularly preferably from 0.3 to 0.5.
  • cerium / zirconium / SE mixed oxides of the three-way catalyst A contain no aluminum oxide.
  • material zone AI and / or A2 an alkaline earth compound such.
  • Barium sulfate Preferred embodiments contain barium sulfate in material zone AI.
  • the amount of barium sulfate is in particular 5 to 20 g / l based on the volume of the carrier substrate TA.
  • material zone AI and / or A2 additionally contain additives such as rare earth compounds such. B. lanthanum oxide and / or binders, such as. B. aluminum compounds.
  • additives such as rare earth compounds such. B. lanthanum oxide and / or binders, such as. B. aluminum compounds.
  • Material zone AI palladium, and a cerium / zirconium / lanthanum / yttrium mixed oxide
  • Cerium / zirconium / lanthanum / yttrium mixed oxide of material zone AI is smaller than the proportion of the sum of lanthanum oxide and yttrium oxide in
  • Cerium / zirconium / lanthanum / yttrium mixed oxide of material zone A2 in each case calculated in% by weight and based on the cerium / zirconium / lanthanum / yttrium mixed oxide. In this case, it is preferable if the proportion of the total
  • Cerium / zirconium / lanthanum / yttrium mixed oxide of material zone AI and in Cerium / zirconium / lanthanum / yttrium mixed oxide of material zone A2 is from 14 to 18% by weight, based on the cerium / zirconium / lanthanum / yttrium mixed oxide of material zone A2, in each case calculated in% by weight and based on the cerium / zirconium / Lanthanum / yttrium mixed oxide.
  • Material zone AI directly on the carrier substrate TA i. There is no further layer or "undercoat” between the carrier substrate TA and material zone AI.
  • material zone A2 is in direct contact with the exhaust stream, i. E. on
  • Material zone A2 is no further layer or "overcoat”.
  • the cerium oxide used in the material zones B1, B2, C1 and C2 is usually of commercial quality, ie. may have a cerium oxide content of 90 to 100 wt .-%.
  • the cerium / zirconium mixed oxide used in the material zones B2 and C2 is likewise usually of commercial quality. Its ceria content is> 60 wt .-%, based on the total weight of the mixed oxide, is therefore for example 60 to 90 wt .-%, in particular 65 to 75 wt .-%.
  • the cerium / zirconium mixed oxide used in the material zones B2 and C2 may also contain other rare earth oxides other than cerium oxide.
  • lanthanum oxide, neodymium oxide, praseodymium oxide, niobium oxide and yttrium oxide come into question. They are used, for example, in amounts of up to 10% by weight, for example from 2 to 8% by weight, based on the total weight of the mixed oxide.
  • Strontium oxide As the alkali compound in the material zones Bl and Cl are in particular oxides, carbonates or hydroxides of lithium, potassium and sodium in question.
  • the material zones Bl and Cl are independent of one another with regard to the alkaline earth or alkali compounds.
  • both material zones Bl and Cl can contain the same or different alkaline earth metal or alkali compounds.
  • the alkaline earth or alkali compound in amounts of 10 to 50 g / l, especially 15 to 20 g / l, calculated as alkaline earth or alkali oxide, based on the volume of the carrier substrate TB and the carrier substrate Tc, before.
  • the material zones B1 and C1 are also independent of one another with regard to the amounts of alkaline earth or alkali compounds.
  • both material zones Bl and Cl may contain the same or different amounts of alkaline earth or alkali compounds.
  • the material zones Bl and Cl independently contain platinum or palladium or platinum and palladium. In the latter case, the
  • Platinum to palladium ratio for example, 4: 1 to 18: 1 or 6: 1 to 16: 1, for example, 8: 1, 10: 1, 12: 1 or 14: 1.
  • Material zone B2 contains Pd and optionally Rh or Pt and Pd with a weight ratio of Pt: Pd ⁇ 2 and optionally Rh. Das
  • Weight ratio of Pt: Pd in material zone B2 is in particular 2: 1 to 1: 6.
  • the weight ratio of Pt: Pd> 2 the expert speaks of a platinum-rich material zone.
  • the weight ratio of Pt: Pd in material zone C2 is for example 2: 1 to 20: 1 or 2.1 to 14: 1, but in particular 2: 1 to 12: 1.
  • material zone C2 contains rhodium as another precious metal
  • material zones B2 optionally contain rhodium.
  • Rhodium is in these cases in particular in amounts of 0.1 to 12 g / ft 3 (corresponding to 0.003 to 0.42 g / l), based on the volume of the carrier substrate TB or of the carrier substrate Tc, before.
  • the noble metals platinum and palladium and optionally rhodium are present on suitable carrier materials in all material zones AI, A2, B1, B2, C1 and C2.
  • suitable carrier materials are all materials which are familiar to a person skilled in the art for this purpose.
  • Such materials have a BET surface area of 30 to 250 m 2 / g, preferably from 100 to 200 m 2 / g (determined according to DIN 66132) and are in particular alumina, silica, magnesium oxide, titanium oxide, cerium oxide, and mixtures or mixed oxides of at least two of these materials.
  • material zones AI and A2 can serve as support materials for the platinum group metals beyond the cerium / zirconium / SE mixed oxides.
  • catalyst B comprises the material zones B1 and B2, wherein both material zones contain cerium oxide and material zone B2 is present in an amount of 50 to 200 g / l, based on the volume of the carrier substrate TB, and the minimum mass fraction in%. of cerium oxide in the material zone B2 is of the formula
  • amount of washcoat B in g / l in this formula means the dimensionless number which corresponds to the amount of material zone B2 indicated in g / l. For a washcoat loading of 50 g / l, this results in a minimum mass fraction of cerium oxide of 35%, corresponding to 17.5 g / l based on the volume of the carrier substrate TB.
  • the mass fraction of cerium oxide in the material zone B2 is at least 50%, whichever is the case
  • Total loading of material zone B2 amounts of at least 25 to 100 g / l, based on the volume of the carrier substrate TB, corresponds.
  • the material zone B2 is in an amount of 75 to 150 g / l, based on the volume of
  • the amounts of ceria are at least 28.1 to 67.5 g / l, each based on the volume of the carrier substrate TB.
  • the material zone B2 is in an amount of 80 to 130 g / l, based on the volume of
  • the amounts of ceria are at least 30.4 to 55.9 g / l, each based on the volume of the carrier substrate TB.
  • the upper limit of the amount of cerium oxide contained in material zone B2 results from the maximum washcoat loading of 200 g / l less the amounts of noble metal and the support materials for the noble metals, and optionally contained further constituents of material zone B2.
  • material zone B2 contains no further constituents besides cerium oxide, noble metal and support materials for the noble metal.
  • cerium oxide in the material zone Bl can therefore be calculated in a simple manner.
  • cerium oxide in the material zone Bl can therefore be calculated in a simple manner.
  • catalyst B comprises the material zones Bl and B2, wherein both material zones contain cerium oxide and the ratio of cerium oxide in material zone B2 to cerium oxide in material zone Bl, calculated in g / l and based on the volume of carrier substrate TB, respectively. 1: 2 to 3: 1.
  • the sum of cerium oxide in material zone B1 and material zone B2, calculated in g / l and based on the volume of the carrier substrate TB, is in particular 100 to 240 g / l. In this embodiment of the present invention, this is
  • cerium oxide is used in the material zone B2 in an amount of 46 to 180 g / l, preferably of 46 to 90 g / l and particularly preferably of 46 to 70 g / l, in each case based on the volume of the carrier substrate TB.
  • cerium oxide is used in amounts of from 14 to 95 g / l, preferably from 25 to 95 g / l and particularly preferably from 46 to 95 g / l, in each case based on the volume of the carrier substrate TB.
  • cerium oxide is used in material zone B1 in an amount of 25 to 120 g / l and in material zone B2 in an amount of 50 to 180 g / l, in each case based on the volume of carrier substrate TB
  • the total washcoat loading of the carrier substrate TB is in
  • Embodiments of the present invention 300 to 600 g / l, based on the volume of the carrier substrate TB.
  • the loading is with material zone B1 150 to 500 g / l and the loading with material zone B2 50 to 300 g / l, in each case based on the volume of the carrier substrate TB.
  • the loading with material zone B1 is 250 to 300 g / l, and with material zone B2 100 to 200 g / l, in each case based on the volume of carrier substrate TB.
  • catalyst C comprises the material zones Cl and C2, both of which material zones contain ceria.
  • the distribution of the cerium oxide onto the material zones C1 and C2 takes place in particular as described above for the material zones B1 and B2, but independently of this.
  • Catalyst arrangement according to the invention the three-way catalyst A and the catalyst B. In particular, there is no further catalyst between the catalysts A and B.
  • the catalyst arrangement according to the invention comprises the three-way catalyst A and the catalyst C. In particular, there is no further catalyst between the catalysts A and C.
  • the catalyst arrangement according to the invention comprises in this order
  • Three-way catalyst A, catalyst B and catalyst C Three-way catalyst A, catalyst B and catalyst C.
  • the material zones AI, A2, B1, B2, C1 and C2 generally extend over the entire length of the carrier substrate TA, TB or Tc.
  • the material zones AI, Bl and Cl independently starting from one end of the Carrier substrate TA, TB or Tc to 10 to 80% of their length and the material zones A2, B2 and C2 over the entire length of
  • Support substrates TA, TB and Te extend.
  • Carrier substrate TA, TB or Tc to 10 to 80% of their length and the material zones AI, Bl and Cl over the entire length of
  • Support substrates TA, TB and Te extend.
  • Suitable carrier substrates TA, TB or Tc are in principle all known catalytically inert carrier bodies for heterogeneous catalysts.
  • monolithic flow honeycomb bodies made of ceramic or metal are usually used for cleaning exhaust gases from internal combustion engines.
  • ceramic flow honeycomb bodies made of cordierite are usually used for cleaning exhaust gases from internal combustion engines.
  • catalyst B or, if catalyst C is present, catalyst C is followed by a catalyst D on a carrier substrate TD, the catalyst D comprising an SCR catalytically active material zone D1.
  • SCR catalysts are, for example, mixed oxides, in particular titanium dioxide and / or oxides of vanadium, for example
  • Vanadium pentoxide may contain other oxides, such as those of silicon, molybdenum, manganese, tungsten and others. These catalysts are described in detail in the literature, see for example WO89 / 03366 Al, EP 0 345 695 A2, EP 0 385 164 A2 and WO2011 / 013006 A2.
  • SCR catalysts are based on metal-exchanged zeolites, for example, zeolites of the zeolites beta zeolite, ZSM-5, ZSM-20, USY and MOR exchanged with copper and / or iron.
  • SCR catalysts are used according to the invention, which contain a small-pore zeolite having a maximum ring size of eight tetrahedral atoms and a transition metal.
  • SCR catalysts are described, for example, in EP 2 117 707 A1 and WO2008 / 132452.
  • Particularly preferred zeolites include the framework types AEI, AFX, CHA, KFI, ERI, LEV, MER or DDR, very particularly preferably the framework types AEI, CHA or LEV, which are particularly preferably cobalt, iron, copper or mixtures of two or three these metals are exchanged.
  • they are copper, iron or copper and iron
  • zeolites also includes molecular sieves, which are sometimes referred to as "zeolite-like" compounds Molecular sieves are preferred if they belong to one of the abovementioned types of skeletons Examples are silica-aluminum-phosphate zeolites which are known by the term SAPO and Aluminum phosphate zeolites known by the term AIPO.
  • Preferred zeolites or molecular sieves are furthermore those which have a SAR (silica-to-alumina) value of 2 to 100, in particular of 5 to 50.
  • the zeolites or molecular sieves contain transition metal, in particular in amounts of 1 to 10 wt .-%, in particular 2 to 5 wt .-%, calculated as metal oxide, that is, for example, as Fe 2 C> 3 or CuO.
  • Preferred embodiments of the present invention include SCR catalysts with copper, iron or copper and iron exchanged zeolites or molecular sieves of the chabazite or levyne type.
  • Appropriate Zeolites or molecular sieves are known, for example, under the designations SSZ-13, SSZ-62, SAPO-34, AIPO-34, Nu-3, ZK-20, LZ-132, SAPO-35 and AIPO-35.
  • catalyst D comprises, in addition to the SCR catalytically active material zone D1, an oxidation-catalytically active material zone D2.
  • Material zone D2 comprises in particular one or more platinum group metals, in particular platinum or platinum and palladium. Material zone D2 additionally comprises, in particular, cerium oxide. As support materials for the platinum group metals are all the platinum group metals.
  • Such materials have a BET surface area of 30 to 250 m 2 / g, preferably from 100 to 200 m 2 / g (determined according to DIN 66132) and are in particular alumina, silica, magnesium oxide, titanium oxide, cerium oxide, and mixtures or mixed oxides of at least two of these materials.
  • the material zones D1 and D2 are in zoned form, i. Material zones Dl and material zone D2 are arranged one behind the other on the carrier substrate TD in such a way that
  • Material zone Dl points in the direction of the catalyst B and in the direction of the catalyst C.
  • the material zone Dl extends
  • material zone D2 is arranged wholly or partly on material zone Dl.
  • the material zone Dl extends for example over 90 to 100% and material zone D2 over 2 to 35% of the total length of the carrier substrate TD.
  • Material zone D2 is arranged on the catalyst B or catalyst C side facing away from the catalyst D.
  • catalyst D is followed by catalyst E on a carrier substrate TE, wherein catalyst E comprises a nitrogen oxide storage catalyst.
  • Catalyst E comprises in particular material zones E1 and E2, wherein E1 and E2 are defined as the material zones B1 and B2, but independently of B1 and B2.
  • the carrier substrates TD and TE like the carrier substrates TA, TB and Tc, can be flow substrates, in particular cordierite.
  • the carrier substrates TD and / or TE can also be wall-flow filters.
  • the channels are in the flow-through substrate, in which open channels extend at both ends in parallel between its two ends, the channels are in the
  • Wand Lett alternately sealed either at the first or at the second end gas-tight. Gas entering a channel at one end can thus leave the wall-flow filter only if it enters through the channel wall into a channel which is open at the other end.
  • the channel walls are usually porous and have uncoated
  • porosities for example, porosities of 30 to 80, especially 50 to 75%. Their average pore size when uncoated, for example, 5 to 30 microns.
  • the pores of the wall-flow filter are so-called open pores, that is to say they have a connection to the channels. Furthermore, the pores are usually interconnected. This allows, on the one hand, the slight coating of the inner pore surfaces and, on the other hand, an easy passage of the exhaust gas through the porous walls of the wall-flow filter.
  • material zone D and / or material zone E exist on the porous channel walls of the wallflow filter. Preferably, however, they lie in the porous walls of the carrier substrate Tü or of the carrier substrate TE VOT.
  • Wall-flow filters which can be used in accordance with the present invention are known and available on the market. They consist for example of silicon carbide, aluminum titanate or cordierite.
  • the application of the material zones A1, A2, B1, B2, C1, C2, D1, D2 and E or El and E2 to the corresponding carrier substrate is usually carried out with the aid of appropriate coating suspensions (washcoat) according to the customary dip coating methods or pumping and suction Coating process with subsequent thermal aftertreatment (calcination and optionally reduction with forming gas or hydrogen). These methods are well known in the art.
  • Form wall flow filters lie (on-wall coating). Alternatively, they are chosen so that the material zone D or E in the porous walls, which form the channels of the wall flow filter are, that is a
  • Coating of the inner pore surfaces takes place (in-wall coating).
  • the average particle size must be small enough to be able to penetrate into the pores of the wall-flow filter.
  • catalysts B and C may be used on a
  • the catalyst arrangement according to the invention is outstandingly suitable for the purification of exhaust gas of a lean-burn gasoline engine.
  • the three-way catalyst A in all modes of the
  • Catalyst arrangement is in particular capable of reducing hydrogen by means of the hydrogen formed via the water gas shift reaction
  • Nitrogen oxides to optimize ammonia are thus fuel-efficient and with high selectivity.
  • This ammonia thus formed can be used to operate a downstream SCR catalyst, which reacts with this ammonia still remaining nitrogen oxides to nitrogen and water.
  • the SCR catalyst can thus be operated "passively”, ie the addition of
  • Ammonia or an ammonia precursor compound from a separately entrained reservoir can be omitted.
  • the exhaust gas is to be passed through the catalyst arrangement according to the invention such that it is first by the three-way catalyst A, then by catalyst B or catalyst C or if the catalysts B and C are both present, by catalyst B and then catalyst C and finally optionally through catalyst D and optionally through catalyst E.
  • the catalyst arrangement according to the invention from the three-way catalyst A and the catalysts B and / or C close to the engine, i. directly behind the exhaust manifold or
  • Catalyst arrangement a catalyst D and optionally a
  • Catalyst E includes, they may be arranged in the underbody of the vehicle.
  • the present invention thus also relates to a method for purifying exhaust gas from lean-burn gasoline engines, characterized is characterized in that the exhaust gas via an inventive
  • Catalyst arrangement is passed.
  • a commercially available honeycomb flow-through ceramic carrier is coated over its entire length with a first material zone, the 4.803 g / l palladium supported on a lanthanum-stabilized
  • the coated carrier is coated with a second material zone which also extends the full length of the flow-through ceramic carrier.
  • the material zone contains 0.353 g / l rhodium and 0.141 g / l palladium supported on a lanthanum stabilized
  • Alumina as well as a cerium, zirconium, yttrium and lanthanum
  • a commercial honeycomb flow-through ceramic carrier is coated over its entire length with a first zone of material carrying 0.883 g / L of platinum supported on a cerium-doped aluminum / magnesium mixed oxide, 0.0883 g / L of palladium, ceria a cerium doped aluminum / magnesium mixed oxide supported barium oxide, and magnesium oxide.
  • the coated support is coated with a second material zone which also extends the full length of the flow-through ceramic support.
  • the material zone contains 0.424 g / l rhodium and 2.119 g / l palladium supported on a lanthanum stabilized
  • a commercially available honeycomb flow-through ceramic carrier along its entire length with a first material zone coated containing 0.883 g / l of platinum and 0.0883 g / l of palladium supported on a lanthanum-stabilized alumina, ceria, on a cerium doped aluminum / magnesium mixed oxide supported barium oxide, and magnesium oxide.
  • the coated carrier is coated with a second material zone which also extends the full length of the flow-through ceramic carrier.
  • the material zone contains 0.1766 g / l rhodium, 0.883 g / l platinum and 0.0883 g / l palladium supported on a lanthanum-stabilized alumina, as well as ceria.
  • the catalyst arrangement KAI from Example 1 was extended by an SCR catalyst D. This comprised a 3 wt% copper exchanged chabazite supported on a commercial honeycomb flow-through ceramic carrier.
  • the catalyst arrangement according to the invention thus formed is designated KA2.
  • the catalyst arrangement KAI from Example 1 was extended by an SCR catalyst D. This included a Levyne exchanged with 3% by weight copper, which was on a commercial honeycomb
  • the catalyst arrangement according to the invention thus formed is designated KA3.
  • Catalyst C The catalyst arrangement of the invention thus formed is designated KA4.
  • Example 5 The catalyst arrangement of the invention thus formed is designated KA4.
  • Catalyst C The catalyst arrangement of the invention thus formed is designated KA5.
  • Example 2 was repeated with the difference that catalyst D on the side facing away from Catalyst C to 10% of the length of
  • the precious metal amount was 0.883 g / l of platinum and 0.0883 g / l of palladium.
  • the catalyst arrangement according to the invention thus formed is designated KA6.
  • Example 3 was repeated with the difference that catalyst D on the side facing away from Catalyst C to 10% of the length of
  • the precious metal amount was 0.883 g / l of platinum and 0.0883 g / l of palladium.
  • the catalyst arrangement according to the invention thus formed is designated KA7.
  • Example 2 was repeated with the difference that catalyst D on the side facing away from Catalyst C to 10% of the length of
  • Carrier substrate TD one under the SCR catalyst applied
  • Material zone contained (undercoat) containing on 4% lanthanum oxide stabilized alumina supported platinum and palladium, and ceria.
  • the precious metal amount was 0.883 g / l of platinum and 0.0883 g / l of palladium.
  • the catalyst arrangement according to the invention thus formed is designated KA8.
  • Example 3 was repeated with the difference that catalyst D on the side facing away from Catalyst C to 10% of the length of
  • Carrier substrate TD one under the SCR catalyst applied
  • Material zone contained (undercoat) containing on 4% lanthanum oxide stabilized alumina supported platinum and palladium, and ceria.
  • the precious metal amount was 0.883 g / l of platinum and 0.0883 g / l of palladium.
  • the catalyst arrangement according to the invention thus formed is designated KA9.
  • Example 1 was repeated with the difference that catalyst B was omitted.
  • the catalyst arrangement thus formed comprises only the catalysts A and C and is designated KA10. Comparative Example 1
  • Example 1 For the preparation of a catalyst arrangement not according to the invention the three-way catalyst A of Example 1 according to the invention is prepared in the first step. b) In the second step, a commercial honeycomb flow ceramic carrier is coated over its entire length with a first zone of material containing 1.06 g / l of platinum, one doped with cerium
  • Aluminum / magnesium mixed oxide 0.106 g / l palladium, an yttrium- and lanthanum-doped cerium / zirconium mixed oxide, supported on a cerium-doped aluminum / magnesium mixed oxide supported barium oxide, 0.0353 g / l rhodium and magnesium oxide.
  • the coated support is coated with a second material zone which also extends the full length of the flow-through ceramic support.
  • the material zone contains 3.072 g / l of palladium supported on a lanthanum stabilized alumina, a neodymium, yttrium and lanthanum doped cerium / zirconium mixed oxide, yttrium and lanthanum doped cerium / zirconium mixed oxide, lanthana and strontium oxide.
  • the catalyst BV is present.
  • a commercially available honeycomb flow-through ceramic carrier is coated over its entire length with a first material zone which carries 0.883 g / l of platinum supported on a cerium-doped aluminum / magnesium mixed oxide, a lanthanum-doped aluminum-cerium mixed oxide. 0.0883 g / l palladium, cerium oxide, a ceria-supported barium oxide, and magnesium oxide.
  • the coated carrier is coated with a second material zone which also extends the full length of the flow-through ceramic carrier.
  • the material zone contains 0.106 g / l rhodium, 0.699 g / l platinum and 0.349 g / l palladium supported on a lanthanum-stabilized alumina and ceria.
  • a lean exhaust gas mixture from a lean-burned combustion engine with spray-guided combustion process (Lean GDI) is transmitted via the
  • the catalyst assemblies lean NOx as long as the NOx sensor detects NOx slippage across the exhaust system of 100 ppm.
  • the engine then switches from lean combustion to rich combustion.
  • the rich exhaust gas mixture over the
  • Catalyst system passes and reduces the stored there in the form of nitrates NOx.
  • the engine then returns to lean combustion mode. This process is repeated 7 times at a specified temperature, with the converted NOx mass calculated from the last 5 lean / rich changes.
  • Comparative Example 2 (catalyst arrangement VK2) compared.
  • the components A, B and C were located close to the engine and the components D and E were arranged in a position comparable to the subfloor.
  • the components A, B and C were arranged close to the engine and the component E in a position comparable to the subfloor.
  • the catalyst volumes of the two subfloor systems i.e., catalysts D + E and catalyst E, respectively
  • the underfloor volume is equally divided between the SCR catalyst D and the NSC catalyst E, whereby the amount of precious metal used here in the underbody is halved in comparison to the catalyst arrangement VK2.
  • the catalyst arrangement KA4 according to the invention shows significant advantages in NOx conversion, despite the significantly lower amount of precious metal, especially in the more dynamic sections of the test cycle.

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Abstract

La présente invention concerne un ensemble de catalyseurs qui comporte a) un convertisseur catalytique à trois voies A sur un substrat porteur TA, b) un catalyseur B sur un substrat porteur TB, lequel comporte deux zones de matériau B1 et B2 et/ou c) un catalyseur C sur un substrat porteur TC, lequel comporte deux zones de matériau C1 et C2.
PCT/EP2017/075583 2016-10-10 2017-10-09 Ensemble de catalyseurs WO2018069199A1 (fr)

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* Cited by examiner, † Cited by third party
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WO2021151876A1 (fr) * 2020-01-27 2021-08-05 Umicore Ag & Co. Kg Catalyseur à trois voies double couche présentant une meilleure stabilité au vieillissement
WO2022056066A1 (fr) * 2020-09-11 2022-03-17 Basf Corporation Article catalytique en couches et procédé de préparation de l'article catalytique
WO2023001617A1 (fr) 2021-07-21 2023-01-26 Umicore Ag & Co. Kg Système d'épuration des gaz d'échappement pour épurer les gaz d'échappement de moteurs à combustion interne

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021151876A1 (fr) * 2020-01-27 2021-08-05 Umicore Ag & Co. Kg Catalyseur à trois voies double couche présentant une meilleure stabilité au vieillissement
WO2022056066A1 (fr) * 2020-09-11 2022-03-17 Basf Corporation Article catalytique en couches et procédé de préparation de l'article catalytique
WO2023001617A1 (fr) 2021-07-21 2023-01-26 Umicore Ag & Co. Kg Système d'épuration des gaz d'échappement pour épurer les gaz d'échappement de moteurs à combustion interne
DE102021118801A1 (de) 2021-07-21 2023-01-26 Umicore Ag & Co. Kg Abgasreinigungssystem zur Reinigung von Abgasen von Benzinmotoren

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