EP3727655A1 - Pot catalytique à trois voies monocouche - Google Patents

Pot catalytique à trois voies monocouche

Info

Publication number
EP3727655A1
EP3727655A1 EP18826640.7A EP18826640A EP3727655A1 EP 3727655 A1 EP3727655 A1 EP 3727655A1 EP 18826640 A EP18826640 A EP 18826640A EP 3727655 A1 EP3727655 A1 EP 3727655A1
Authority
EP
European Patent Office
Prior art keywords
zirconium
cerium
rare earth
oxide
mixed oxide
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.)
Pending
Application number
EP18826640.7A
Other languages
German (de)
English (en)
Inventor
Jan Schoenhaber
Martin Roesch
Joerg-Michael Richter
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=60923283&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3727655(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of EP3727655A1 publication Critical patent/EP3727655A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
    • B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths
    • 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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with 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
    • 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
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    • 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
    • F01N3/24—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 characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of 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
    • 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
    • F01N3/24—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 characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • 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
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    • 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
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2066—Praseodymium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
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    • B01D2255/20715—Zirconium
    • 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
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • 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
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/908—O2-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/915—Catalyst supported on particulate filters
    • B01D2255/9155—Wall flow filters
    • 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
    • B01D2258/014—Stoichiometric gasoline engines
    • 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
    • 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
    • F01N2330/30—Honeycomb supports characterised by their structural details
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    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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    • 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
    • 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 three-way catalyst which is particularly suitable for the removal of carbon monoxide, hydrocarbons and nitrogen oxides from the exhaust gas of stoichiometric air / fuel mixture operated internal combustion engines. He is by
  • Aging and consists only of a single catalytically active layer.
  • Gasoline engines are cleaned in conventional processes using three-way catalysts. These are able to absorb the three main gaseous pollutants of the engine, namely hydrocarbons,
  • Combustion air ratio l (A / F ratio, air / fuel ratio) sets the actual air mass m L, tats available for combustion in relation to the stoichiometric air mass mi_, st:
  • platinum group metals in particular platinum, palladium and rhodium are used, which are present for example on g-aluminum oxide as a carrier material.
  • g-aluminum oxide as a carrier material.
  • rhodium is present for example on g-aluminum oxide as a carrier material.
  • Three-Way Catalysts Oxygen storage materials for example
  • Cerium / zirconium mixed oxides In the latter is ceria, a
  • Oxygen storage materials contain additional constituents such as other rare earth metal oxides or alkaline earth metal oxides.
  • Oxygen storage materials are activated by the application of catalytically active materials such as platinum group metals and thus also serve as a carrier material for the
  • the components of a three-way catalyst may be present in a single coating layer on an inert catalyst support. Such catalysts are distinguished from multilayer catalysts by lower coating costs.
  • EP1541220B1 describes a single-layer three-way catalyst in which palladium and rhodium are predominantly in a non-alloyed form.
  • EP1974810B1 describes a single-layer three-way catalyst in which a first cerium / zirconium mixed oxide with rhodium and a second
  • Cerium / zirconium mixed oxide has a higher zirconium oxide content than the second.
  • EP2948653A1 describes a single-layer three-way catalyst in which a temperature-resistant metal oxide and optionally a first cerium / zirconium mixed oxide with rhodium and a second cerium / zirconium mixed oxide with palladium is activated, wherein the proportion of cerium / zirconium mixed oxides in the layer is the same or greater than that of the temperature-resistant metal oxide in the layer.
  • the present invention relates to a three-way catalyst for removing carbon monoxide, hydrocarbons and nitrogen oxides from the exhaust gas operated with stoichiometric air / fuel mixture
  • Injection tube injection comprising a ceramic flow-through substrate of length L and a catalytic coating, the coating being on the walls of the substrate and extending from one end of the substrate over a length at least 50% of L and active alumina, at least two mutually different cerium / zirconium / rare earth metal mixed oxides and at least one
  • the coating is catalytically active, especially at
  • Oxygen storage components The oxygen storage components differ with respect to at least one of the contained
  • oxygen storage components are cerium / zirconium / rare earth metal mixed oxides.
  • cerium / zirconium / rare earth metal mixed oxides are particularly suitable oxygen storage components.
  • cerium / zirconium / rare earth mixed oxides are characterized by a substantially homogeneous, three-dimensional crystal structure which is ideally free of phases of pure ceria, zirconia or rare earth oxide. Depending on the manufacturing process but also not completely homogeneous products, but with a homogeneity of> 80 Wt .-% arise, which can be used usually without disadvantage.
  • rare earth metal or rare earth metal oxide does not include cerium or cerium oxide.
  • rare earth metal oxides in the cerium / zirconium / rare earth metal mixed oxides are lanthanum oxide, yttrium oxide, praseodymium oxide,
  • Neodymium oxide and / or samarium oxide into consideration.
  • Lanthanum oxide, yttrium oxide and / or praseodymium oxide are preferred, and very particular preference is given to lanthanum oxide and yttrium oxide, yttrium oxide and praseodymium oxide, and also lanthanum oxide and praseodymium oxide.
  • the oxygen storage components are preferably free of neodymium oxide.
  • the weight ratio of alumina is the sum of the two
  • Cerium / zirconium / rare earth mixed oxides in the range of 10:90 to 60:40, preferably in the range of 20:80 to 50:50 and more preferably in the range of 25:75 to 35:65.
  • the coating comprises in preferred embodiments in each case lanthanum-stabilized aluminum oxide in amounts of from 10 to 60% by weight, preferably from 20 to 50, particularly preferably from 25 to 35% by weight, and also oxygen storage components in amounts from 40 to 90% by weight, preferably 50 to 80 wt .-%, particularly preferably 65 to 75 wt .-%, each based on the sum of the weights of alumina and oxygen storage components in the coating.
  • the coating in embodiments preferably comprises two different oxygen storage components, wherein the weight ratio of the first cerium / zirconium / rare earth mixed oxide to the second cerium / zirconium / rare earth mixed oxide is in the range of 4: 1 to 1: 4, preferably in the range of 3: 1 to 1: 3 and more preferably in the range of 2: 1 to 1: 2.
  • the coating comprises a first and a second oxygen storage component, wherein the first oxygen storage component has a higher content of zirconia than the second oxygen storage component.
  • the mass ratio of ceria to zirconia in the cerium / zirconium / rare earth mixed oxides can vary widely. It is for example 0.1 to 1.5, preferably 0.2 to 1.25 or 0.3 to 1. It is further preferred if the first
  • Oxygen storage component has a weight ratio of ceria to zirconia of 0.7 to 0.1, which is smaller than in the second cerium / zirconium / rare earth mixed oxide having a weight ratio of ceria to zirconia of 0.5 to 1.5. More more
  • Oxygen storage component having a weight ratio of ceria to zirconia of 0.6 to 0.2 and a second
  • Oxygen storage component having a weight ratio of ceria to zirconia of from 0.6 to 1.2. Still others very much preferred
  • Embodiments include a first oxygen storage component having a weight ratio of ceria to zirconia of from 0.5 to 0.3, and the second oxygen storage component has a weight ratio of ceria to zirconia of from 0.7 to 1.0.
  • Three-way catalyst designed so that the first
  • Cerium / zirconium / rare earth mixed oxide has a ceria content of 10% to 40% by weight of the first
  • Cerium / zirconium / rare earth mixed oxide more preferably from 15% to 35% and most preferably from 20% to 30% by weight of the first cerium / zirconium / rare earth metal composite oxide.
  • the zirconium oxide content is in the first
  • Cerium / zirconium / rare earth mixed oxide at 40% to 90% based on the weight of the first cerium / zirconium / rare earth mixed oxide.
  • Cerium / zirconium / rare earth mixed oxide between 50% to 75%, from 55% to 65% by weight of the first
  • Cerium / zirconium / rare earth mixed oxide lies.
  • a cerium oxide content of 25% to 60% by weight of the second cerium-zirconium-rare earth mixed oxide should prevail. It is more advantageous if in the second cerium / zirconium / rare earth mixed oxide a cerium oxide content of 30% to 55%, more preferably from 35% to 50% based on the weight of the second cerium / zirconium / rare earth metal oxide is given.
  • Cerium / zirconium / rare earth mixed oxide has a zirconia content of 20% to 70% by weight of the second
  • Cerium / zirconium / rare earth mixed oxide is preferable when the second cerium / zirconium / rare earth mixed oxide has a
  • Zirconium oxide content of 30% to 60%, and most preferably from 40% to 55% by weight of the second
  • Cerium / zirconium / rare earth mixed oxide Cerium / zirconium / rare earth mixed oxide.
  • cerium / zirconium / rare earth metal mixed oxides when both cerium / zirconium / rare earth metal mixed oxides are doped with lanthanum, so that preferably the content of lanthanum oxide> 0% to 10% based on the weight of
  • Cerium / zirconium / rare earth mixed oxide Cerium / zirconium / rare earth mixed oxide. These lanthanum oxide-containing oxygen storage components are particularly
  • a mass ratio of lanthanum oxide to cerium oxide of 0.05 to 0.5.
  • the coating comprises lanthanum stabilized alumina, as well as rhodium, palladium or Palladium and rhodium and two different, zirconia, ceria, lanthanum, and yttria or praseodymium oxide comprehensive
  • the first cerium / zirconium / rare earth mixed oxide is doped with yttria in addition to lanthana.
  • a preferred catalyst has an yttria content in the first cerium / zirconium / rare earth mixed oxide of from 2% to 25% by weight of the first
  • Cerium / zirconium / rare earth oxide More preferably, the
  • Yttria content of the first cerium / zirconium / rare earth mixed oxide between 4% and 20%, more preferably 10% to 15% by weight of the first cerium / zirconium / rare earth mixed oxide.
  • Cerium / zirconium / rare earth metal mixed oxide in addition to lanthanum oxide is doped with a further metal oxide from the group of rare earth metal oxides, preferably with praseodymium.
  • the content of the second rare earth metal in the second cerium-zirconium-rare earth mixed oxide may be from 2% to 15% by weight of the second cerium-zirconium-rare earth mixed oxide. It is more advantageous if the content of the second
  • Rare earth metal of the second cerium / zirconium / rare earth metal composite oxide is 3% to 10%, more preferably 4% to 8%, based on the weight of the second cerium / zirconium / rare earth metal composite oxide.
  • the yttrium oxide content is the first
  • Oxygen storage component in particular 5 to 15 wt .-%, based on the weight of the oxygen storage component.
  • the weight ratio of lanthanum oxide to yttrium oxide is in particular 0.1 to 1,
  • the praseodymium content is the second
  • Oxygen storage component in particular 2 to 10 wt .-%, based on the weight of the oxygen storage component.
  • the weight ratio from lanthanum oxide to praseodymium oxide is more preferably 0.1 to 2.0, preferably 0.2 to 1.8, and more preferably 0.5 to 1.5.
  • the zirconia content of the yttria-containing oxygen storage component is greater than the zirconia content of the zirconia
  • the coating contains as catalytically active
  • Elements precious metals Particularly suitable for this purpose are platinum, palladium and rhodium or mixtures thereof, preference being given to palladium, rhodium, palladium and rhodium, or platinum, palladium and rhodium, and palladium and rhodium being particularly preferred. Furthermore, both cerium / zirconium / rare earth metal mixed oxides with palladium and
  • Rhodium, platinum and rhodium or platinum, palladium and rhodium may be activated.
  • the catalytically active coating is located on the walls in the channels of the flow-through substrate. If in the context of the present invention of a coating on the walls is mentioned, then it is meant that only a small proportion of the coating of max. 20% by weight, more preferably max. 15% by weight and most preferably max. 10 wt .-% and most preferably max. 5 wt .-% is present in the walls of the flow-through substrate.
  • Suitable catalytically inert catalyst carriers are honeycomb bodies made of ceramic or metal with a volume V which have parallel flow channels for the exhaust gases of the internal combustion engine. According to the invention, the catalytically active coating is located on the walls in the channels of a flow-through substrate. Ceramic honeycomb bodies that can be used in accordance with the present invention are known
  • Flow-through substrates and available on the market. They exist, for example of silicon carbide, aluminum titanate or cordierite, for example, have a cell density of 200 to 900 cells per square inch (cpsi), and
  • the noble metals are usually used in amounts of 0.1 g / l to 15 g / l, based on the volume of the ceramic honeycomb body, preferably 0.15 g / L to 10 g / L. In a preferred embodiment, the noble metals are on both the alumina and on the
  • Suitable carrier materials for the noble metals are all those skilled in the art for this purpose materials. Such materials are in particular metal oxides having a BET surface area of from 30 to 250 m 2 / g, preferably from 100 to 200 m 2 / g (determined in accordance with DIN 66132 - latest version on the filing date).
  • Particularly suitable support materials for the noble metals are selected from the series consisting of alumina, doped alumina, silica, titania and mixed oxides of one or more thereof.
  • Doped aluminum oxides are, for example, with lanthanum oxide, barium oxide, zirconium oxide and / or titanium oxide-doped aluminum oxides.
  • Lanthanum-stabilized aluminum oxide is advantageously used, with lanthanum being used in amounts of from 1 to 10% by weight, preferably from 3 to 6% by weight, in each case calculated as La 2 O 3 and based on the weight of the stabilized aluminum oxide.
  • the coating contains oxygen storage components in amounts of 30 to 225 g / l, based on the volume of the honeycomb body, preferably 40 to 200 g / l and particularly preferably 50 to 160 g / l.
  • the mass ratio of carrier materials and oxygen storage components in the coating is usually preferably 0.2 to 1.5, for example 0.3 to 0.8.
  • active aluminum oxide is known to the person skilled in the art and refers in particular to g-aluminum oxide having a surface area of 100 to 200 m 2 / g. Active aluminum oxide has been widely described in the literature and is available on the market.
  • the coating contains one or more alkaline earth compounds, such as e.g. Strontium oxide,
  • Barium oxide or barium sulfate Barium oxide or barium sulfate.
  • the amount of barium sulfate per coating is in particular 2 to 20 g / l volume of the ceramic honeycomb body.
  • the coating contains strontium oxide or barium oxide.
  • the coating contains additives such as rare earth compounds such as e.g. B. lanthanum oxide and / or binders, such as. B. aluminum compounds.
  • additives such as rare earth compounds such as e.g. B. lanthanum oxide and / or binders, such as. B. aluminum compounds.
  • the coating extends from the first end of the ceramic honeycomb body over at least 50%, preferably at least 70% and most preferably 100% of the length L of the substrate.
  • the loading of the substrate with the catalytic coating is 40 g / l to 300 g / l based on the volume of the carrier, preferably 50 g / l to 260 g / l and particularly preferably 60 g / l to 220 g / l.
  • the catalyst according to the invention can be further different coatings in a layered or zoned
  • the coating does not contain a zeolite or a molecular sieve.
  • the preparation of the catalyst according to the invention can according to the
  • the catalyst according to the invention is outstandingly suitable for removing carbon monoxide, hydrocarbons and nitrogen oxides from the exhaust gas of stoichiometric air / fuel mixture
  • the present invention thus also relates to a process for removing carbon monoxide, hydrocarbons and nitrogen oxides from the exhaust gas of stoichiometric air / fuel mixture
  • Figure 1 shows a catalyst according to the invention comprising a ceramic substrate (1) of length L extending in parallel between a first end (2) and a second end (3) of the substrate and separated by walls (4).
  • the coating (5) is located on the walls of the ceramic substrate (1).
  • the substrates were each ceramic
  • Cordierite flow-through substrates 4 inches in diameter and 6 inches in length, with a 600 cpsi cell count and a
  • Alumina stabilized with lanthana was combined with an oxygen storage component containing 25% by weight of ceria, 68% by weight.
  • Aluminum oxide to oxygen storage component was 50: 50.
  • the suspension thus obtained was then added with continuous stirring with a palladium nitrate solution and a rhodium nitrate solution.
  • the resulting coating suspension was used directly to coat a commercial substrate, the coating being over 100% of the substrate length.
  • the total loading of this catalyst was 161 g / l, the noble metal loading 1.509 g / l with a ratio of
  • Two lanthana stabilized aluminas were suspended in water along with an oxygen storage component comprising 40% by weight of ceria, 50% by weight of zirconia, 5% by weight of lanthana and 5% by weight of praseodymium oxide.
  • an oxygen storage component comprising 40% by weight of ceria, 50% by weight of zirconia, 5% by weight of lanthana and 5% by weight of praseodymium oxide.
  • Alumina to oxygen storage component was 50: 50.
  • the suspension thus obtained was then with constant stirring a palladium nitrate solution and a rhodium nitrate solution.
  • the resulting coating suspension was used directly to coat a commercial substrate, the coating being over 100% of the substrate length.
  • the total loading of this catalyst was 161 g / l, the noble metal loading 1.509 g / l with a ratio of
  • Alumina stabilized with lanthana was combined with a first oxygen storage component comprising 40% by weight of ceria, 50% by weight of zirconia, 5% by weight of lanthana and 5% by weight of praseodymium oxide, and a second oxygen storage component containing 24% by weight.
  • Oxygen storage components were used in equal parts.
  • the weight ratio of alumina to oxygen storage components was 30:70.
  • the suspension thus obtained was then under constant stirring with a palladium nitrate solution and a
  • the resulting coating suspension was used directly to coat a commercial substrate, the coating being over 100% of the substrate length.
  • Comparative Example 1 Comparative Example 2 and Example 1 were aged in an engine test bench aging.
  • the aging consists of a fuel cut-off aging with 950 ° C exhaust gas temperature before the catalyst inlet (maximum bed temperature 1030 ° C).
  • the aging time was 38 hours.
  • the light-off behavior at a constant average air ratio l and the dynamic conversion were added to an engine test bench
  • Table 1 contains the temperatures Tso at which 50% of the considered component is converted in each case. It was the
  • Example 1 shows a clear improvement in the starting behavior compared with the two comparative examples.
  • the dynamic turnover behavior was determined in a range of 7.99 from 0.99 to 1.01 at a constant temperature of 510 ° C.
  • the amplitude of 1 was ⁇ 6.8%.
  • Table 2 shows the conversion at the intersection of the CO and NOx conversion curves, as well as the associated HC conversion.
  • Example 1 shows a clear improvement in the dynamic CO / NOx conversion after aging than the two
  • Table 3 shows the values for the lambda jump test which characterizes the static oxygen storage capability.
  • the stored oxygen quantity is calculated from the delay time of the post-catalytic lambda probe in relation to the pre-catalyst lambda probe.
  • Alumina stabilized with lanthana was combined with an oxygen storage component containing 40% by weight of ceria, 50% by weight.
  • Alumina to oxygen storage component was 30:70.
  • the resulting suspension was then treated with continuous stirring with a palladium nitrate solution and a rhodium nitrate solution.
  • the resulting coating suspension was used directly to coat a commercial substrate with the coating applied over 100% of the substrate length.
  • the total loading of this Catalyst was 76.27 g / l, the noble metal loading of 1.271 g / l with a ratio of palladium to rhodium of 5: 1
  • coated catalyst was dried and then calcined.
  • Alumina stabilized with lanthana was combined with an oxygen storage component containing 24% by weight of ceria, 60% by weight.
  • Alumina to oxygen storage component was 30:70.
  • the resulting suspension was then treated with continuous stirring with a palladium nitrate solution and a rhodium nitrate solution.
  • the resulting coating suspension was used directly to coat a commercial substrate with the coating applied over 100% of the substrate length. The total loading of this
  • Catalyst was 76.27 g / l, the noble metal loading of 1.271 g / l with a ratio of palladium to rhodium of 5: 1
  • coated catalyst was dried and then calcined.
  • Alumina stabilized with lanthana was combined with a first oxygen storage component comprising 40% by weight of ceria, 50% by weight of zirconia, 5% by weight of lanthana and 5% by weight of praseodymium oxide, and a second oxygen storage component containing 24% by weight.
  • Oxygen storage components were used in equal parts.
  • the weight ratio of alumina to oxygen storage components was 30:70.
  • the suspension thus obtained was then under constant stirring with a palladium nitrate solution and a
  • Comparative Example 1 Comparative Example 2 and Example 1 were aged in an engine test bench aging.
  • the aging consists of a fuel cut-off aging with 950 ° C exhaust gas temperature before the catalyst inlet (maximum bed temperature 1030 ° C).
  • the aging time was 19 hours.
  • Table 1 contains the temperatures Tso at which 50% of the considered component is converted in each case. It was the
  • the dynamic turnover behavior was determined in a range of 7.99 from 0.99 to 1.01 at a constant temperature of 510 ° C.
  • the amplitude of 1 was ⁇ 6.8%.
  • Table 2 shows the conversion at the intersection of the CO and NOx conversion curves, as well as the associated HC conversion.
  • Example 1 shows a marked improvement in the dynamic CO / NOx conversion after aging, while the
  • Table 3 shows the values for the lambda jump test which characterizes the static oxygen storage capability.
  • the stored oxygen quantity is calculated from the delay time of the post-catalytic lambda probe in relation to the pre-catalyst lambda probe.
  • the dynamic oxygen storage capacity is determined.
  • the exhaust gas is subjected to various 1 amplitudes at a frequency of 1 Hz.
  • the amplitude signal of the Nachkat lambda probe is determined by the
  • Example 1 and Comparative Examples 1 and 2 The example according to the invention shows both a high static and a very good dynamic oxygen storage capacity after aging.

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Abstract

La présente invention concerne un pot catalytique servant à éliminer le monoxyde de carbone, les hydrocarbures et les oxydes d'azote présents dans les gaz d'échappement de moteurs à combustion interne fonctionnant avec un mélange air/carburant stœchiométrique, ce pot catalytique comprenant un substrat de longueur L et un revêtement catalytique. L'invention se caractérise en ce que le revêtement se trouve sur les parois du substrat et s'étend à partir d'une extrémité du substrat sur une longueur qui représente au moins 50 % de la longueur L, et en ce qu'il contient de l'oxyde d'aluminium actif, deux oxydes mixtes de cérium/zirconium/métaux de terres rares différents l'un de l'autre et au moins un métal du groupe du platine.
EP18826640.7A 2017-12-19 2018-12-19 Pot catalytique à trois voies monocouche Pending EP3727655A1 (fr)

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EP17208615.9A EP3501648B2 (fr) 2017-12-19 2017-12-19 Filtre à particules catalityquement actif
PCT/EP2018/085962 WO2019121995A1 (fr) 2017-12-19 2018-12-19 Pot catalytique à trois voies monocouche

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EP23212574.0A Active EP4365421B1 (fr) 2017-12-19 2018-12-14 Filtre à particules à activité catalytique
EP18816073.3A Active EP3727653B1 (fr) 2017-12-19 2018-12-14 Filtre à particules à activité catalytique
EP18826338.8A Pending EP3727654A1 (fr) 2017-12-19 2018-12-19 Pot catalytique à trois voies multicouche
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EP3501648B1 (fr) 2023-10-04
US11628400B2 (en) 2023-04-18
EP3501648B2 (fr) 2026-06-10
US20210069678A1 (en) 2021-03-11
US20230285899A1 (en) 2023-09-14
EP4365421B1 (fr) 2026-05-13
WO2019121372A1 (fr) 2019-06-27
CN115990408A (zh) 2023-04-21
CN111511469A (zh) 2020-08-07
CN111511457A (zh) 2020-08-07
CN111491714A (zh) 2020-08-04
US20210079822A1 (en) 2021-03-18
US12128357B2 (en) 2024-10-29
EP3727654A1 (fr) 2020-10-28
US11291952B2 (en) 2022-04-05
US20200306693A1 (en) 2020-10-01
US20210086135A1 (en) 2021-03-25
EP4365421A2 (fr) 2024-05-08
EP3727653A1 (fr) 2020-10-28
CN111491715B (zh) 2022-12-27
WO2019121995A1 (fr) 2019-06-27
US11185820B2 (en) 2021-11-30
CN111491714B (zh) 2023-02-10
EP3501648A1 (fr) 2019-06-26
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EP3727653B1 (fr) 2024-02-14
US11179676B2 (en) 2021-11-23

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