WO2023198575A1 - Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac - Google Patents

Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac Download PDF

Info

Publication number
WO2023198575A1
WO2023198575A1 PCT/EP2023/059084 EP2023059084W WO2023198575A1 WO 2023198575 A1 WO2023198575 A1 WO 2023198575A1 EP 2023059084 W EP2023059084 W EP 2023059084W WO 2023198575 A1 WO2023198575 A1 WO 2023198575A1
Authority
WO
WIPO (PCT)
Prior art keywords
ammonia
exhaust system
catalyst
exhaust gas
oxide
Prior art date
Application number
PCT/EP2023/059084
Other languages
German (de)
English (en)
Inventor
Julius KOEGEL
Massimo Colombo
Sonja Buchberger
Marcus Schmidt
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.)
Filing date
Publication date
Priority claimed from DE102023101772.1A external-priority patent/DE102023101772A1/de
Application filed by Umicore Ag & Co. Kg filed Critical Umicore Ag & Co. Kg
Publication of WO2023198575A1 publication Critical patent/WO2023198575A1/fr

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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9436—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/12—Silica and alumina
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—Noble metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
    • B01J29/68—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0248—Coatings comprising impregnated particles
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01D2255/206—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
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • 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
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—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
    • B01D2255/50—Zeolites
    • 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
    • B01D2255/911—NH3-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/014—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
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • 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
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/18—Ammonia

Definitions

  • the present invention is aimed at an exhaust system for reducing exhaust gases and in particular ammonia emissions in the exhaust system of a predominantly stoichiometrically operated spark ignition engine.
  • Spark ignition engines or gasoline engines powered by gasoline or natural gas are cleaned in conventional processes using three-way catalysts (TWC). These are able to simultaneously convert the engine's three main gaseous pollutants, namely hydrocarbons, carbon monoxide and nitrogen oxides, into harmless components.
  • Stoichiometric means that, on average, there is as much air available to burn the fuel present in the cylinder as is required for complete combustion.
  • the combustion air ratio ⁇ (A/F ratio; air/fuel ratio) relates the air mass m L,tats actually available for combustion to the stoichiometric air mass m L,st : If ⁇ ⁇ 1 (e.g. 0.9) this means “lack of air”, one speaks of a rich exhaust gas mixture, ⁇ > 1 (e.g. 1.1) means “excess air” and the exhaust gas mixture is considered lean designated.
  • ⁇ 1.1 means that 10% more air is present than would be necessary for the stoichiometric reaction. The same applies to the exhaust gases from internal combustion engines.
  • the catalytically active materials used in the known three-way catalysts are generally platinum group metals, in particular platinum, palladium and rhodium, which are present, for example, on ⁇ -aluminum oxide as a support material.
  • three-way catalysts contain oxygen storage materials, for example cerium/zirconium mixed oxides. In the latter, cerium oxide is the fundamental component for oxygen storage. In addition to zirconium oxide and cerium oxide, these materials can contain additional components such as other rare earth metal oxides or alkaline earth metal oxides. Oxygen storage materials are created by applying catalytically active Materials such as platinum group metals are activated and thus also serve as a carrier material for the platinum group metals.
  • Compliance with the strict emission values for ammonia requires the use of a storage material to store NH 3 during the rich operating conditions of the combustion engine, particularly in low and medium temperature ranges. engines, as the ammonia is mainly formed under these exhaust gas conditions. The stored ammonia is then converted during lean operating points by oxidation on a layer containing precious metal and/or as part of an SCR reaction. The aim here is to achieve the lowest possible selectivity to N 2 O.
  • a special requirement for the catalysts considered here is the high aging stability of the materials used: In addition to the stability against lean gas conditions, their use in the exhaust system of stoichiometrically operated internal combustion engines also requires that they also be used in the exhaust gas with rich or stoichiometric ric composition are stable under hydrothermal exhaust gas conditions.
  • the use of catalysts, which preferentially convert ammonia into nitrogen, has already been discussed, particularly in the diesel sector or for use in lean-burning DI petrol engines (US5120695; EP1892395A1; EP1882832A2; EP1876331A2; WO12135871A1; US2011271664AA; WO1111091 9A1, EP3915679A1).
  • CNG “Compressed Natural Gas”
  • SCR SCR catalytically active component
  • a component that catalyzes the oxidation of ammonia They are usually located in the underbody at the last point of the exhaust system. If for oxidation of the If there are not enough nitrogen oxides in the system from the stored ammonia, the ammonia can also be converted into nitrogen via the ASC with the oxygen present.
  • the corresponding limit values for NH 3 and N 2 O should be safely adhered to in addition to the traditional ones for CO, HC and NOx.
  • the system should also be robust and agile in order to be able to withstand the working conditions in the exhaust system of a corresponding automobile for a sufficient period of time. It should also be as cost-effective as possible to produce.
  • Claims 2 - 10 relate to preferred embodiments of the exhaust system and can accordingly also be applied to the method according to the invention.
  • an exhaust system for reducing harmful exhaust gas components from internal combustion engines in particular predominantly stoichiometrically operated gasoline engines, having a first three-way catalytic converter and, on the downstream side, a catalytic converter for reducing ammonia emissions, which has the following components: - a first component comprising a transition metal exchanged zeolite and/or zeotypes for storing ammonia; - a second component with an OSC-free noble metal catalyst and / or an OSC-containing noble metal catalyst, where the first component has a mixture of small-pore and large-pore zeolites or zeotypes, the solution to the problem is achieved relatively easily, but no less surprisingly .
  • the system according to the invention is characterized by extremely good performance in terms of reducing CO, HC and NOx emissions as well as NH3 and N2O emissions. It reacts well to the dynamic requirements in the exhaust system of a gasoline engine and is sufficiently robust to meet these requirements over a sufficient period of time become. In addition, it is more advantageous to produce in terms of production technology.
  • the large-pore zeolites or zeotypes can serve as hydrocarbon traps and thus help to reduce HC emissions during, for example, cold start conditions.
  • the components of the catalyst for reducing ammonia emissions are applied to a carrier, preferably to a flow-through substrate, using a coating step familiar to those skilled in the art (DE102019100099A1 and the literature cited there).
  • a filter substrate such as a wall flow filter is also possible in this context.
  • Flow-through substrates are catalyst supports that are common in the prior art and can consist of metal, for example WO17153239A1, WO16057285A1, WO15121910A1 and the literature cited therein) or ceramic materials.
  • “Corrugated substrates” can also be viewed as flow-through substrates. These are known to those skilled in the art as carriers made of corrugated sheets made of inert materials. Suitable inert materials are, for example, fibrous materials with an average fiber diameter of 50 to 250 ⁇ m and an average fiber length of 2 to 30 mm. Fibrous heat-resistant materials made of silicon dioxide, especially glass fibers, are preferred.
  • refractory ceramics such as cordierite, silicon carbite or aluminum titanate etc. are preferably used as honeycomb carriers.
  • the number of carrier channels per area is characterized by the cell density, which is usually between 300 and 900 cells per square inch (cells per square inch, cpsi).
  • the wall thickness of the channel walls for ceramics is between 0.5 – 0.05 mm.
  • the total amount of coating in the catalyst to reduce ammonia emissions is selected so that the catalyst according to the invention is used as efficiently as possible overall.
  • the total amount of coating (solids content) per carrier volume (total volume of the carrier) can be between 100 and 600 g/L, in particular between 150 and 400 g/L.
  • the first component is preferably used in an amount of 50 to 350 g/L, in particular between 120 and 250 g/L, particularly preferably about 145 - 230 g/L of carrier volume.
  • the second component is preferably used from 50 to 350 g/L, in particular between 120 and 250 g/L, particularly preferably from about 145 - 230 g/L carrier volume.
  • the components are present as separate coatings one above the other on the substrate. It is preferred if the second component is completely over the first and completely covers it. This is understood to mean the fact that the first component does not protrude beyond the second component at any end. It is particularly preferred if the two coatings with the respective components are of the same length (Fig. 2). The length of the layers can be chosen by the specialist.
  • a first component of the catalyst for reducing ammonia emissions consists of zeolites and/or zeotypes for storing ammonia. In principle, those skilled in the art are familiar with the zeolites and zeotypes available for this purpose from the diesel sector.
  • zeolites or zeotypes work is based on the fact that they can temporarily store ammonia in operating states of the exhaust gas purification system in which ammonia is produced, for example, by overreduction of nitrogen oxides via a three-way catalytic converter installed on the upstream side, but this is not converted by other conventional three-way catalytic converters. This can happen, for example due to a lack of oxygen or insufficient operating temperatures.
  • the ammonia stored in this way can then be stored out when the operating state of the exhaust gas purification system changes and subsequently or directly converted, for example when sufficient oxygen or nitrogen oxides are present.
  • zeolites and zeotypes are present in the first component of the catalyst to reduce ammonia emissions.
  • zeolites or zeotypes can be divided into different classes. Zeolites are then divided, for example, according to their channel system and their framework structure. For example, laumontite and mordenite are classified as zeolites, which have a one-dimensional system of channels. Your channels have no connection with each other. Zeolites with a two-dimensional channel system are characterized by the fact that their channels are connected to one another in a kind of layered system. A third group has a three-dimensional framework structure with cross-layer connections between the channels.
  • zeolites or zeotypes Two- and/or three-dimensional zeolites or zeotypes are preferred in the present invention for use [Ch. Baerlocher, WM Meier and DH Olson, Atlas of Zeolite Framework Types, Elsevier, 2001].
  • zeolite refers to porous materials with a lattice structure of corner-linked AlO4 and SiO4 tetrahedra according to the general formula (WM Meier, Pure & Appl.
  • zeolite therefore comprises a network made up of tetrahedra that encloses channels and cavities.
  • zeotype is understood to mean a zeolite-like compound that has the same structural type as a naturally occurring or synthetically produced zeolite compound, but which differs from such compounds in that the corresponding cage structure is not made up exclusively of aluminum and silicon framework atoms .
  • the aluminum and/or silicon framework atoms are proportionally replaced by other trivalent, quadrivalent or pentavalent framework atoms such as B(III), Ga(III), Ge(IV), Ti(IV) or P(V) replaced.
  • the most common method used in practice is the replacement of aluminum and/or silicon framework atoms by phosphorus atoms, for example in the silicon aluminum phosphates or in the aluminum phosphates, which crystallize in zeolite structure types.
  • suitable zeolites come from the group of two-dimensional or three-dimensional zeolites/zeotypes.
  • They preferably belong to the structure types ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, BEA, BIK, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, ESV, ETL, FER , GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON at.
  • the zeolites or zeotypes in the car exhaust gas catalyst according to the invention are selected from the group AEI, AFT, AFX, CHA, DDR, ERI, ESV, ETL, FER, KFI, LEV, UFI and the corresponding zeotypes of these structural types, such as e.g.: SAPO. Mixtures of the same can also be present. Zeolites or zeotypes can also be classified according to their pore structure. A distinction is made between small-pore, medium-pore and large-pore zeolites. The extra-large pore zeolites are of academic interest. Small-pore zeolites are those with a largest ring size of 8 tetrahedral units.
  • CHA, AEI, AFX, BIK, DDR, ERI, LEV or LTA are particularly preferred as small-pore zeolites or zeotypes for storing ammonia.
  • CHA is extremely preferred in this context.
  • Large-pore zeolites or zeol types for storing ammonia are preferably selected from the group consisting of BEA, FAU or MOR. BEA is particularly preferred in this context.
  • the aging stability of the zeolites or zeotypes used in the exhaust system of predominantly stoichiometrically burning engines is particularly in focus here, since higher temperatures generally prevail here than in a lean-burning engine. In this respect, materials are desired that can withstand the sometimes very high and rapidly changing hydrothermal conditions for as long as possible.
  • the exhaust gas composition is also different compared to lean-burn engine exhaust.
  • concentration, in particular of hydrocarbons and carbon monoxide, which arrive at the catalyst according to the invention is, on the one hand, higher than in lean-burn engines and the composition also changes depending on the driving style around the stoichiometric range (rich/lean change).
  • the hydrothermal temperature stability of zeolites and zeotypes is therefore particularly in demand.
  • the small-pore zeolites used preferably have a SAR value (silica-to-alumina ratio) or the zeotypes have a ratio corresponding to this value of >15 to ⁇ 45, very preferably of >20 to ⁇ 35. Extremely preferred is a Range from 20 – 30 in this context.
  • the large-pore zeolites used preferably have a SAR value (silica-to-alumina ratio) or the zeotypes have a ratio corresponding to this value of >10 to ⁇ 50, very preferably from >10 to ⁇ 40. Extremely preferred is a range of 10 – 30 in this context.
  • the amount of silicon atoms remaining in the framework is related to the substitution atoms. This results in the number of negative charges in the base body and thus a measure of the number of counterions to be absorbed until electroneutrality is achieved.
  • a corresponding ratio can be determined for Zeotype.
  • the zeolite or zeotype used is ion-exchanged with transition metal ions.
  • the latter are preferably selected from the group consisting of iron and/or copper. Iron is particularly preferred because it has a less oxidizing effect on ammonia compared to copper.
  • the zeolite or zeotype described acts as a catalyst for selective catalytic reduction (SCR) (see WO2008106518A2, WO2017187344A1, US2015290632AA, US2015231617AA, WO2014062949A1, US2015231617AA).
  • SCR capability is understood to mean the ability to selectively convert NOx and NH3 in the lean exhaust gas into nitrogen.
  • the metals, such as iron and/or copper, which advantageously occur in the catalyst to reduce ammonia emissions, are present in a certain proportion in the first component. This is 0.4-10, more preferably 0.8-7 and most preferably 1.5-5.0% by weight of the first component.
  • the iron and/or copper to aluminum ratio is between 0.05 - 0.8, preferably between 0.2 - 0.5 and most preferably between 0.3 - 0.5 for zeolites.
  • a corresponding ratio applies to the exchange places available there.
  • the metals are at least partially present in ion-exchanged form in the zeolites or zeotypes.
  • ion-exchanged zeolites or zeotypes are already introduced into the first component.
  • the zeolites or zeotypes are brought together with, for example, a binder and a solution of the metal ions in a liquid, preferably water, and then dried (preferably by spraying).
  • ion exchange represents a challenge for small-pore zeolites. While ion exchange for large-pore zeolites can be carried out as part of the washcoat process, since the ions readily penetrate into the large zeolite pores and occupy the ion exchange positions of the material, the occupation of small-pore zeolites requires porous zeolites require a separate process step. This can be an incipient wetness process or an ion exchange process with, if necessary, subsequent spray drying.
  • One approach to saving this additional step and the associated costs and production time is to coat with a mixture of a small-pore zeolite, a large-pore zeolite and a soluble salt of the ions to be exchanged (e.g. Fe(NO3)3 x 9 H2O, Cu acetate) with, if necessary, a common binder system onto a substrate.
  • the dissolved ions are first absorbed by the large-pore zeolite.
  • a distribution of the ions between large and small pore zeolite then occurs during the calcination process.
  • the resulting catalyst benefits from the high stability of the ammonia storage function of the small-pore zeolite as well as from the usually high SCR activity of the large-pore exchanged zeolite and thus shows good performance and selectivity in the application described.
  • Another well-known property of the ion-exchanged large-pore zeolites is their ability to store hydrocarbons, which gives the formulated ammonia storage the properties of a so-called hydrocarbon trap. During the cold start, incoming hydrocarbons can be captured, which then desorb at a higher temperature and can be converted via the then active three-way catalysts or oxidation catalysts. The first component has large and small pore zeolites.
  • the order of the layers of large and small pore zeolites and the corresponding loading amounts can be varied.
  • the quantitative ratio of the different types of zeolites to one another can be varied.
  • the small-pore zeolite can be used in a transition metal-free form or coated with transition metals, preferably iron or copper.
  • the large and small pore zeolites are preferably used in a weight ratio of 5:1 to 1:5, more preferably 2:1 to 1:2.
  • the first component can preferably have other non-catalytically active components, such as binders.
  • binders temperature-stable metal oxides that are not or only slightly catalytically active, such as SiO2, Al2O3 and ZrO2, are suitable as binders. The expert knows which materials come into question here.
  • the proportion of such binders in the first coating can, for example, be up to 15% by weight, preferably up to 10% by weight, of the coating.
  • the binder can also contain the above-mentioned transition metals, in particular iron and/or copper. Binders are suitable for ensuring stronger adhesion of the coating to a carrier or another coating. For this purpose, a certain particle size of the metal oxides in the binder is advantageous. This can be adjusted accordingly by a specialist.
  • the ammonia storage ability or capacity addressed in the context of this invention is given as a quotient of the stored mass of ammonia per liter of catalyst support volume.
  • the first component should increase the ammonia storage capacity of the exhaust gas purification system to at least 0.25 g of ammonia per L of carrier volume (measured in the fresh state).
  • the storage capacity of the ammonia storage components used in the form of zeolites or zeotypes should be sufficient to ensure that there is between 0.25 and 10.0 g of NH3 per liter of carrier volume in the system, preferably between 0.5 and 8.0 g of NH3 per liter of carrier volume and particularly preferably between 0.5 and 5.0 g of NH 3 /liter of carrier volume of ammonia can be stored (always based on the fresh state).
  • the zeolites or zeotypes are present in a sufficient amount in the catalyst to reduce ammonia emissions. The determination of the ammonia storage capacity is shown further below.
  • the second component consists of an OSC-free precious metal catalyst and/or an OSC-containing noble metal catalyst.
  • Precious metal refers in particular to the platinum group metals platinum, palladium and rhodium.
  • the noble metals in the OSC-free or OSC-containing noble metal catalyst are preferably selected from the group consisting of palladium, platinum, rhodium.
  • OSC means Oxygen Storage Component.
  • An OSC-containing noble metal catalyst therefore has oxygen storage materials.
  • the OSC-free precious metal catalyst on the other hand, essentially has no function of storing oxygen in the exhaust gas of the internal combustion engine.
  • this component has oxygen storage materials, in particular cerium-zirconium mixed oxides, of less than 10 g/L, preferably less than 5 g/L and most preferably less than 2 g/L carrier volume.
  • cerium or cerium-zirconium mixed oxides for example, is considered the storage material, including the doping elements present.
  • Corresponding OSC-free precious metal catalysts have the ability to have an oxidative effect on the substances present (NH3, HC, CO) in the already slightly lean exhaust gas of a predominantly stoichiometrically operated combustion engine. This component is preferably designed so that it becomes active at correspondingly low temperatures.
  • the ammonia stored in the zeolite or zeotype is preferably converted into non-harmful nitrogen via this component.
  • the oxidation effect should not be too great, otherwise a certain proportion of the powerful greenhouse gas N2O will be formed from ammonia oxidation.
  • the oxidation power can be adjusted, among other things, by the amount of platinum and the Pt:Pd and/or Pt:Rh ratio.
  • the second component in the form of an OSC-free precious metal catalyst therefore contains materials that have an oxidative effect on, among other things, ammonia.
  • this component contains a temperature-stable, high-surface metal oxide and at least one noble metal selected from the group rhodium, platinum and palladium.
  • the total precious metal content of this component is preferably from 0.015 - 5 g/L, more preferably from 0.035 - 1.8 g/L and particularly preferably from 0.07 - 1.2 g/L carrier volume.
  • the precious metals platinum or palladium, or platinum and palladium together, are particularly suitable for use in this component that has an oxidative effect on ammonia.
  • the person skilled in the art can preferably choose whether to use the strongly oxidative platinum alone or, if necessary, in conjunction with palladium in the second coating layer. If platinum and/or palladium is used, the former should be in the range of 0.015 - 1.42 g/L, more preferably 0.035 - 0.35 g/L carrier volume in the coating. Palladium can be present in the coating between 0.015 - 1.42 g/L, preferably 0.035 - 0.35 g/L carrier volume.
  • the weight ratio of platinum to palladium should be between 1:0 and 1:5, more preferably 1:0 and 1:4 and most preferably 1:0 and 1:2.
  • the precious metals in the OSC-free second component are fixed on one or more temperature-stable, high-surface metal oxides as carrier materials. All materials familiar to those skilled in the art for this purpose can be considered as carrier materials. Such materials are in particular metal oxides with a BET surface area of 30 to 250 m 2 /g, preferably 100 to 200 m 2 /g (determined according to DIN 66132 - latest version on the filing date).
  • Particularly suitable carrier materials for the precious metals are selected from the series consisting of aluminum oxide, doped aluminum oxide, silicon oxide, titanium dioxide and mixed oxides from one or more of these.
  • Doped aluminum oxides are, for example, lanthanum oxide, zirconium oxide, barium oxide and/or titanium oxide-doped aluminum oxides.
  • Aluminum oxide or lanthanum-stabilized aluminum oxide is advantageously used, in the latter case lanthanum in amounts of in particular 1 to 10% by weight, preferably 3 to 6% by weight, in each case calculated as La2O3 and based on the weight of the stabilized Aluminum oxide is used.
  • the proportion of barium oxide in particular 1 to 10% by weight, preferably 3 to 6% by weight, in each case calculated as BaO and based on the weight of the stabilized aluminum oxide.
  • lanthanum-stabilized aluminum oxide the surface of which is coated with lanthanum oxide, barium oxide and/or strontium oxide.
  • This component preferably comprises at least one aluminum oxide or doped aluminum oxide.
  • La-stabilized aluminum oxide with a surface area of 100 to 200 m 2 /g is particularly advantageous in this context.
  • active aluminum oxide is widely described in the literature and is available on the market.
  • the catalyst for reducing ammonia emissions has an OSC-containing noble metal catalyst as an alternative or cumulative to the OSC-free precious metal catalyst.
  • oxygen storage materials are also present in the precious metal catalyst (containing OSC).
  • Cerium or cerium-zirconium mixed oxides are consistently used as oxygen storage materials. Accordingly, an OSC-containing noble metal catalyst is characterized by the presence of a certain amount of these oxygen storage materials. In particular, this component has oxygen storage materials in an amount of more than 10 g/L, preferably more than 20 g/L and most preferably more than 25 g/L carrier volume. The entire cerium-zirconium mixed oxide with all its components is included. Corresponding OSC-containing precious metal catalysts have the ability to have an oxidative effect on the substances present (NH 3 , HC, CO) in the already slightly rich exhaust gas of a predominantly stoichiometrically operated combustion engine. This component is preferably designed so that it becomes active at correspondingly low temperatures.
  • the ammonia stored in the zeolite or zeotype is preferably converted into non-harmful nitrogen via this component.
  • the oxidation effect should not be too great, otherwise a certain proportion of the powerful greenhouse gas N 2 O will be formed from ammonia oxidation.
  • the noble metals in the OSC-containing noble metal catalyst are preferably selected from the group consisting of palladium or rhodium or platinum, platinum and rhodium, palladium and rhodium or palladium and rhodium and platinum together.
  • This catalyst is preferably a coating equipped with three-way catalytic capability. This particularly preferably has precious metals selected from the group of platinum and rhodium, palladium and rhodium, preferably Rhodium alone.
  • the noble metals can only be deposited on the temperature-stable, high-surface support materials. However, it is preferred if the noble metals are deposited both on the carrier materials mentioned and on the oxygen storage materials. If rhodium is present in this component (whether alone or in combination with the other aforementioned precious metals), this should preferably be in the range of 0.035 - 1.0 g/L, more preferably 0.1 - 0.35 g/L. L carrier volume is located in the respective component. If palladium and/or platinum are also present in this component, the ranges mentioned above for the OSC-free precious metal catalysts apply to these metals.
  • Suitable three-way catalytically active coatings are described, for example, in DE102013210270A1, DE102020101876A1, EP3247493A1, EP3727655A1.
  • Modern gasoline engines are operated under conditions with a discontinuous course of the air ratio ⁇ . They are subject in a defined manner to a periodic change in the air ratio ⁇ and thus to a periodic change in oxidizing and reducing exhaust gas conditions. In both cases, this change in the air ratio ⁇ is essential for the exhaust gas purification result.
  • the lambda value of the exhaust gas is adjusted with a very short cycle time (approx.
  • the OSC-containing noble metal catalysts (such as modern three-way catalysts) therefore contain oxygen storage materials, in particular cerium or Ce/Zr mixed oxides.
  • the mass ratio of cerium oxide to zirconium oxide can vary within wide limits in these mixed oxides. It is, for example, 0.1 to 1.5, preferably 0.15 to 1 or 0.2 to 0.9.
  • Preferred cerium/zirconium mixed oxides include one or more rare earth metal oxides and can therefore be used as Cerium/zirconium/rare earth metal mixed oxides are referred to.
  • cerium/zirconium/rare earth metal mixed oxides are characterized by a largely homogeneous, three-dimensional crystal structure, which is ideally free of phases made of pure cerium oxide, zirconium oxide or rare earth oxide (so-called solid solution). Depending on the manufacturing process, however, products that are not completely homogeneous may not be created, which can generally be used without disadvantage. The same applies to cerium/zirconium mixed oxides that do not contain any rare earth metal oxide. Furthermore, the term rare earth metal or rare earth metal oxide in the sense of the present invention does not include cerium or cerium oxide.
  • rare earth metal oxides in the cerium/zirconium/rare earth metal mixed oxides are lanthanum oxide, yttrium oxide, praseodymium oxide, neodymium oxide and/or samarium oxide.
  • Lanthanum oxide, yttrium oxide and/or praseodymium oxide are preferred.
  • Particularly preferred rare earth metal oxides are lanthanum oxide and/or yttrium oxide and very particularly preferred is the joint presence of lanthanum oxide and yttrium oxide, yttrium oxide and praseodymium oxide, as well as lanthanum oxide and praseodymium oxide in the cerium/zirconium/rare earth metal mixed oxide.
  • this noble metal catalyst has two different cerium/zirconium/rare earth metal mixed oxides, preferably one doped with La and Y and one doped with La and Pr.
  • the oxygen storage components are preferably free of neodymium oxide.
  • the proportion of rare earth metal oxide(s) in the cerium/zirconium/rare earth metal mixed oxides is advantageously 3 to 20% by weight based on the cerium/zirconium/rare earth metal mixed oxide. If the cerium/zirconium/rare earth metal mixed oxides contain yttrium oxide as the rare earth metal, its proportion is preferably 4 to 15% by weight based on the cerium/zirconium/rare earth metal mixed oxide.
  • cerium/zirconium/rare earth mixed oxides contain praseodymium oxide as the rare earth metal, its proportion is preferably 2 to 10% by weight based on the cerium/zirconium/rare earth mixed oxide. If the cerium/zirconium/rare earth metal mixed oxides contain lanthanum oxide and another rare earth oxide as the rare earth metal, such as yttrium oxide or praseodymium oxide, their mass ratio is in particular 0.1 to 1.25, preferably 0.1 to 1. This noble metal catalyst usually contains oxygen storage materials in amounts of 15 to 120 g/l, based on the volume of the carrier or substrate.
  • the OSC-containing noble metal catalysts also have the temperature-stable, high-surface support materials mentioned for the OSC-free noble metal catalysts and, in addition to these, oxygen-storing materials.
  • the mass ratio of temperature-stable, high-surface support materials and oxygen storage components in this component is usually 0.25 to 1.5, for example 0.3 to 1.3.
  • the weight ratio of the sum of the masses of all support materials, such as aluminum oxides (including doped aluminum oxides) to the sum of the masses of all cerium/zirconium mixed oxides in the OSC-containing noble metal catalyst is 10:90 to 75:25, preferably 20:80 to 65:35.
  • the first and second components preferably form an ammonia storage and a function for the oxidation of ammonia to nitrogen (eg as in WO2008106523A2). If there are not enough nitrogen oxides in the system to oxidize the stored ammonia, the ammonia can also be converted into nitrogen using the second component with the oxygen present. In both cases, if possible, no ammonia or N 2 O is released into the environment.
  • the first component and the second component of the catalyst for reducing ammonia emissions can therefore preferably consist of an ammonia-storing coating paired with a second coating that has an oxidative effect on ammonia. As such, according to the invention, they are present in separate coatings one above the other on the substrate.
  • both coatings are of the same length. It is particularly preferred if, for further improved three-way activity, the OSC-containing noble metal catalyst of component two is located as a top layer over the first component made of zeolites and / or zeotypes for storing ammonia as a bottom layer. Most preferably, no further layers are present below or above these two coatings on the substrate. In a further preferred embodiment, it has proven to be advantageous if there is a further thin, separate layer of inert, temperature-stable, high-surface metal oxides between the two layers/components just mentioned. The expert is guided by the coating methods mentioned above for their production.
  • This thin layer which is between 5 ⁇ m and 200 ⁇ m, preferably between 10 ⁇ m and 150 ⁇ m high, helps to further increase the aging stability of the catalyst to reduce ammonia emissions.
  • a disadvantage of the known systems for reducing ammonia emissions can be that the transition metals in the first component, such as iron and/or copper, become part of the exhaust system of a predominantly stoichiometrically operated internal combustion engine after a long period of use tend to diffuse into the ammonia oxidation component and poison it. The result is a lower activity of the ammonia-storing and oxidative components.
  • Suitable materials for this layer are those selected from the group consisting of aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, zeolites or mixtures thereof.
  • Very particularly preferred in this context is a layer made of aluminum oxide or silicon oxide, which is preferably located on the substrate in the same length above the lower layer and under the upper layer.
  • the present exhaust system has a first three-way catalyst and a catalyst positioned downstream to reduce ammonia emissions.
  • the first three-way catalyst can have the same components as the OSC-containing noble metal catalyst of the second component. It is preferably constructed as described in DE102013210270A1, DE102020101876A1, EP3247493A1, EP3727655A1, preferably as described in EP3247493A1.
  • Downstream refers to the fact that the exhaust gas flow first hits the upstream catalytic converter and then the downstream catalytic converter. The reverse applies to the upstream side.
  • Euro 7 legislation it has proven to be advantageous if an exhaust system for a predominantly stoichiometric engine has a unit for filtering small soot and ash particles. Preference is therefore given to an exhaust system that additionally has a possibly catalytically coated GPF between the first three-way catalytic converter and the catalytic converter to reduce ammonia emissions (Fig. 6).
  • GPF are gasoline particle filters and are well known to those skilled in the art (EP3737491A1, EP3601755A1).
  • An exhaust gas design in which the first three-way catalytic converter and the GPF are installed in a position close to the engine is particularly preferred. Close to the engine in the sense of the invention refers to an area in the exhaust system that is in a position close to the engine, i.e. approx. 10 - 80 cm, preferably 20 - 60 cm away from the engine outlet. It has proven to be advantageous if the catalytic converter is installed last in the exhaust direction in the underbody of a vehicle to reduce ammonia emissions, so that the exhaust gas is then released into the ambient air is delivered.
  • the exhaust system can also have additional exhaust units such as additional three-way catalytic converters or hydrocarbon storage (HC traps) or nitrogen oxide storage (LNT).
  • the underbody is the area below the driver's cab.
  • TWC three-way catalytic converter
  • the three-way activity has already been described earlier. There is explicit reference to what is stated there, especially with regard to the type and quantity of the individual components.
  • This three-way catalyst is preferably one as described in the prior art (DE102013210270A1, DE102020101876A1, EP3247493A1, EP3727655A1). Zoned or layered versions are now the norm for TWCs.
  • At least one of the additional catalysts with three-way activity has a 2-layer structure with two different three-way coatings, preferably as described in EP3247493A1.
  • the at least second three-way catalytic converter just described in the exhaust system according to the invention can be installed in the underbody of the vehicle, but it can also be in a position close to the engine. The range of possible Euro 7 systems is large. There can be up to 4 three-way catalytic converters in front of the catalytic converter per exhaust system to reduce ammonia emissions. In an alternative embodiment, there is at least one three-way catalyst and a possibly catalytically coated wall flow filter (GPF) in front of the catalyst to reduce ammonia emissions.
  • GPF catalytically coated wall flow filter
  • the catalyst for reducing ammonia emissions is preferably located last in the underbody and in fluid communication with the further catalyst or catalysts or the filter of the car exhaust system.
  • the car exhaust system preferably has no additional injection device for ammonia or a precursor compound for ammonia.
  • there is an addition unit for secondary air in the exhaust system upstream of the catalytic converter to reduce ammonia emissions or upstream of the wall flow filter (analogous to WO2019219816A1).
  • the present invention relates to a method for reducing harmful exhaust gas components from predominantly stoichiometric operated internal combustion engines, in particular spark-ignited gasoline engines, in which the exhaust gas is passed through an exhaust system according to the invention.
  • the present invention is directed to an exhaust gas purification system, in particular for stoichiometrically operated internal combustion engines.
  • a stoichiometrically burning engine in which a rich exhaust gas is produced within a certain temperature interval. This can lead to nitrogen oxides arriving via a three-way catalytic converter being over-reduced to ammonia.
  • This ammonia should not be released into the environment.
  • the ammonia is therefore stored above the catalyst to reduce ammonia emissions and is then oxidized to nitrogen under slightly oxidizing conditions. Here too, care must be taken to ensure that no over-oxidation to N 2 O occurs.
  • the ammonia storage catalyst is also easier to produce, since only a simplified ion exchange step is required in the production of the first component. Nevertheless, even after intensive aging, the system is robust enough to fully meet the Euro 7 requirements.
  • Fig.1 Chart to explain the measurement of ammonia storage capacity.
  • Fig.2 Catalyst for reducing ammonia emissions (1), coating with metal-free zeolites or zeotypes for storing ammonia (2) and a coating with an OSC-free noble metal catalyst and/or an OSC-containing noble metal catalyst (3) .
  • Fig.3 Schematic representation of the catalysts tested in the underbody position.
  • Fig.4 Reduction in ammonia emissions through catalytic converters A and B compared to a system without an underbody catalytic converter.
  • Fig.5 Reduction in hydrocarbon emissions through catalytic converters A and B compared to a system without an underbody catalytic converter.
  • Fig.6 Exhaust system according to the invention with a three-way catalytic converter close to the engine (A), GPF close to the engine (B) and the following catalytic converter to reduce ammonia emissions (C).
  • A. Determination of the ammonia storage capacity This is determined experimentally in a flow tube reactor. To avoid undesirable ammonia oxidation on the reactor material, a reactor made of quartz glass is used. A drill core is taken as a test specimen from the area of the catalytic converter whose ammonia storage capacity is to be determined. A drill core with a diameter of 1 inch and a length of 3 inches is preferably taken as a test specimen. The drill core is inserted into the flow tube reactor and at a temperature of 600 ° C in a gas atmosphere consisting of 500 ppm nitrogen monoxide, 5 vol.% oxygen, 5 vol.% water and the rest nitrogen with a space velocity of 30000 h -1 for 10 minutes conditioned.
  • the measuring temperature of 200 °C is then reached in a gas mixture of 0 vol.% oxygen, 5 vol.% water and the rest nitrogen at a space velocity of 30,000 h -1 .
  • the NH 3 storage phase is initiated by switching on a gas mixture of 450 ppm ammonia, 0 vol.% oxygen, 5 vol.% water and the rest nitrogen at a space velocity of 30,000 h -1 .
  • This gas mixture remains switched on until a stationary ammonia breakthrough concentration is recorded on the downstream side of the test specimen.
  • the mass of ammonia stored on the test specimen is calculated from the recorded ammonia breakthrough curve by integration from the start of the NH 3 storage phase until stationarity is reached, taking into account the measured stationary NH 3 breakthrough concentration and the known volume flow (hatched area in Figure 1).
  • the ammonia storage capacity is calculated as the quotient of the stored mass of ammonia divided by the volume of the tested core.
  • the production of the iron-containing zeolite coating was carried out using a washcoat consisting of a large-pore zeolite of the BEA structural type, iron (III) nitrate solution and a suitable amount of a binder system consisting of a Al2O3 and a SiO2 component.
  • the desired amount of washcoat was coated in one step over 100% of the substrate length.
  • the coated catalyst thus obtained was dried at 90 °C and then calcined at 350 °C for 15 min and annealed in air at 550 °C for 2 h. If necessary, further layers can be applied as a top layer to the now coated carrier. B2.
  • a silicon-aluminum mixed oxide which consists of 95% by weight aluminum oxide and 5% silicon oxide, was suspended in water. After adjusting the pH to 7.6 ⁇ 0.4, the resulting suspension was mixed with an EA platinum solution with constant stirring. The resulting suspension was ground and, after stabilization with ammonium acetate, used to coat a commercially available carrier, with the coating taking place over 100% of the carrier length. The total loading of this washcoat on the catalyst was 25 g/L, the precious metal loading was 0.106 g/L (3 g/ft 3 ). The coated catalyst thus obtained was dried and then calcined and tempered.
  • Aluminum oxide stabilized with lanthana oxide was prepared together with an oxygen storage component containing 24 wt.% cerium oxide, 60 wt.% zirconium oxide, 3.5 wt.% lanthanum oxide and 12.5 wt. % yttrium oxide, and lanthanum acetate suspended in water as an additional source of lanthanum oxide.
  • the weight ratio of aluminum oxide to oxygen storage component to additional lanthanum oxide was 43.6:55.7:0.7.
  • the suspension thus obtained was then mixed with constant stirring Rhodium nitrate solution added.
  • the resulting coating suspension was used directly to coat a commercially available substrate, with the coating taking place over 100% of the substrate length.
  • the total loading of this washcoat on the catalyst can be, for example, 122 g/L, the precious metal loading 0.177 g/L (5 g/ft 3 ).
  • the coated catalyst thus obtained was dried and then calcined and tempered. If necessary, a layer free of precious metals can be applied as a top layer to the now coated carrier.
  • Catalysts were prepared as shown schematically in Figure 3.
  • E. Aging and testing of the ASCs Aging conditions To determine the catalytic properties of the catalysts according to the invention, they were first aged in an engine test bench aging behind a TWC close to the engine in the underbody position (“fuel-cut aging”).
  • the aging consists of fuel cut-off aging with an exhaust gas temperature of 950 °C in front of the inlet of the TWC near the engine (maximum bed temperature 1030 °C).
  • the aging period and the inlet temperature for the catalytic converter in the underbody position are specified individually for each test.
  • Test conditions The different catalytic converters were tested in the underbody position on a highly dynamic engine test bench in a WLTC driving cycle. Here, a series-produced TWC containing Pd/Rh was placed in an aged state in a position close to the engine.
  • the value “reduction in NH 3 emissions” refers to the NH 3 emissions of a system with one of the catalytic converters shown in the underbody position over the entire driving cycle in relation to the emissions of the corresponding system in the absence of a catalytic converter in underbody position.

Abstract

La présente invention concerne un système de gaz d'échappement destiné à réduire les émissions de gaz d'échappement et en particulier les émissions d'ammoniac dans le circuit de gaz d'échappement d'un moteur à étincelle à fonctionnement principalement stœchiométrique.
PCT/EP2023/059084 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac WO2023198575A1 (fr)

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
DE102022108768 2022-04-11
DE102022108768.9 2022-04-11
DE102022119442 2022-08-03
DE102022119442.6 2022-08-03
DE102022119443.4 2022-08-03
DE102022119441.8 2022-08-03
DE102022119443 2022-08-03
DE102022119441 2022-08-03
DE102023101779.9 2023-01-25
DE102023101768.3 2023-01-25
DE102023101772.1A DE102023101772A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101772.1 2023-01-25
DE102023101779.9A DE102023101779A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101768.3A DE102023101768A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101763.2A DE102023101763A1 (de) 2022-04-11 2023-01-25 Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE102023101763.2 2023-01-25

Publications (1)

Publication Number Publication Date
WO2023198575A1 true WO2023198575A1 (fr) 2023-10-19

Family

ID=85984972

Family Applications (8)

Application Number Title Priority Date Filing Date
PCT/EP2023/059087 WO2023198577A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne fonctionnant principalement de manière stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059078 WO2023198569A1 (fr) 2022-04-11 2023-04-06 Catalyseur de blocage d'ammoniac pour moteurs à combustion interne stoechiométrique
PCT/EP2023/059082 WO2023198573A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059083 WO2023198574A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne principalement à fonctionnement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059084 WO2023198575A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059080 WO2023198571A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059079 WO2023198570A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à allumage par étincelle fonctionnant principalement de manière stœchiométrique, comprenant un catalyseur permettant de réduire les émissions d'ammoniac
PCT/EP2023/059081 WO2023198572A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne principalement à fonctionnement stoechiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac

Family Applications Before (4)

Application Number Title Priority Date Filing Date
PCT/EP2023/059087 WO2023198577A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne fonctionnant principalement de manière stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059078 WO2023198569A1 (fr) 2022-04-11 2023-04-06 Catalyseur de blocage d'ammoniac pour moteurs à combustion interne stoechiométrique
PCT/EP2023/059082 WO2023198573A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059083 WO2023198574A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne principalement à fonctionnement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac

Family Applications After (3)

Application Number Title Priority Date Filing Date
PCT/EP2023/059080 WO2023198571A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
PCT/EP2023/059079 WO2023198570A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à allumage par étincelle fonctionnant principalement de manière stœchiométrique, comprenant un catalyseur permettant de réduire les émissions d'ammoniac
PCT/EP2023/059081 WO2023198572A1 (fr) 2022-04-11 2023-04-06 Système de gaz d'échappement pour moteurs à combustion interne principalement à fonctionnement stoechiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac

Country Status (1)

Country Link
WO (8) WO2023198577A1 (fr)

Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024258A1 (fr) 1979-08-14 1981-02-25 Ciba-Geigy Ag Préparations des compositions pharmaceutiques pour le traitement des infections herpétiques
US5120695A (en) 1989-07-28 1992-06-09 Degusaa Aktiengesellschaft (Degussa Ag) Catalyst for purifying exhaust gases from internal combustion engines and gas turbines operated at above the stoichiometric ratio
EP1876331A2 (fr) 2006-07-08 2008-01-09 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1882832A2 (fr) 2006-07-08 2008-01-30 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1892395A1 (fr) 2006-08-16 2008-02-27 MAN Nutzfahrzeuge AG Système de traitement de gaz d'échappement
WO2008106518A2 (fr) 2007-02-27 2008-09-04 Basf Catalysts Llc Scr sur substrats de filtre de faible masse thermique
WO2008106523A2 (fr) 2007-02-27 2008-09-04 Basf Catalysts Llc Catalyseurs bifonctionnels pour oxydation d'ammoniac sélective
US20110182791A1 (en) * 2011-04-08 2011-07-28 Johnson Matthey Public Limited Company Catalysts for the reduction of ammonia emission from rich-burn exhaust
WO2011110919A1 (fr) 2010-03-08 2011-09-15 Johnson Matthey Public Limited Company Amélioration de la gestion des émissions
US20110271664A1 (en) 2010-05-05 2011-11-10 Basf Corporation Integrated SCR and AMOX Catalyst Systems
WO2012135871A1 (fr) 2011-03-29 2012-10-04 Basf Corporation Filtre multicomposant pour maîtrise des émissions
WO2014062949A1 (fr) 2012-10-19 2014-04-24 Basf Corporation Tamis moléculaire à petits pores à cycle à 8 en tant que catalyseur scr à température élevée
DE102013210270A1 (de) 2013-06-03 2014-12-04 Umicore Ag & Co. Kg Dreiwegkatalysator
WO2015121910A1 (fr) 2014-02-12 2015-08-20 新日鉄住金マテリアルズ株式会社 Matériau de base pour support de catalyseurs
US20150231617A1 (en) 2014-02-19 2015-08-20 Ford Global Technologies, Llc Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING
US20150290632A1 (en) 2014-04-09 2015-10-15 Ford Global Technologies, Llc IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION
WO2016057285A1 (fr) 2014-10-06 2016-04-14 Corning Incorporated Article filtrant en nid d'abeilles et procédés associés
US20170014766A1 (en) * 2014-03-13 2017-01-19 Umicore Ag & Co. Kg Catalyst system for gasoline combustion engines, having three-way catalysts and scr catalyst
WO2017153239A1 (fr) 2016-03-09 2017-09-14 Haldor Topsøe A/S Procédé de préparation d'un catalyseur en nid d'abeille à base de matériau fibreux non tissé
US20170274321A1 (en) * 2014-10-21 2017-09-28 Basf Corporation Emissions treatment systems with twc catalysts and scr-hct catalysts
WO2017187344A1 (fr) 2016-04-26 2017-11-02 Basf Corporation Configuration en zones pour combinaisons de catalyseurs d'oxydation
EP3247493A1 (fr) 2015-01-19 2017-11-29 Umicore AG & Co. KG Pot catalytique à trois voies double couches présentant une meilleure stabilité au vieillissement
US20180229224A1 (en) * 2015-08-21 2018-08-16 Basf Corporation Exhaust gas treatment catalysts
WO2019219816A1 (fr) 2018-05-18 2019-11-21 Umicore Ag & Co. Kg Systèmes et procédés de traitement des gaz d'échappement impliquant une supplémentation en oxygène et un piégeage d'hydrocarbures
EP3601755A1 (fr) 2017-03-23 2020-02-05 Umicore AG & Co. KG Filtre à particules à activité catalytique
DE102019100099A1 (de) 2019-01-04 2020-07-09 Umicore Ag & Co. Kg Verfahren zur Herstellung von katalytisch aktiven Wandflussfiltern
EP3727655A1 (fr) 2017-12-19 2020-10-28 UMICORE AG & Co. KG Pot catalytique à trois voies monocouche
EP3737491A1 (fr) 2019-03-29 2020-11-18 UMICORE AG & Co. KG Filtre à particules à activité catalytique
US20200384449A1 (en) * 2017-02-08 2020-12-10 Basf Corporation Catalytic articles
EP3778016A1 (fr) * 2018-10-08 2021-02-17 Sinocat Environmental Technology Co., Ltd. Catalyseur de traitement de gaz résiduaire, procédé de préparation s'y rapportant et son utilisation
DE102020101876A1 (de) 2020-01-27 2021-07-29 Umicore Ag & Co. Kg Doppelschichtiger Dreiweg-Katalysator mit weiter verbesserter Alterungsstabilität
EP3915679A1 (fr) 2020-05-26 2021-12-01 UMICORE AG & Co. KG Catalyseur, système catalytique et système de nettoyage de gaz d'échappement permettant de réduire les émissions d'ammoniaque
US20220010714A1 (en) * 2014-12-08 2022-01-13 Basf Corporation Nitrous oxide removal catalysts for exhaust systems

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1419810B1 (fr) * 2000-06-22 2007-02-07 Mitsubishi Jidosha Kogyo Kabushiki Kaisha Catalyseur pour purifier le gaz d'échappement
JP3855266B2 (ja) * 2001-11-01 2006-12-06 日産自動車株式会社 排気ガス浄化用触媒
CN101668589B (zh) 2007-02-27 2013-06-12 巴斯福催化剂公司 铜cha沸石催化剂
US9440192B2 (en) * 2009-01-16 2016-09-13 Basf Corporation Diesel oxidation catalyst and use thereof in diesel and advanced combustion diesel engine systems
DE102010007499A1 (de) 2010-02-09 2011-08-11 Umicore AG & Co. KG, 63457 Volumetrische Beschichtungsanordnung
GB201221025D0 (en) * 2012-11-22 2013-01-09 Johnson Matthey Plc Zoned catalysed substrate monolith
DE112014000481T5 (de) * 2013-05-27 2015-11-05 Mazda Motor Corporation Abgasreinigungskatalysator und Herstellungsverfahren dafür
KR102227267B1 (ko) * 2013-07-30 2021-03-12 존슨 맛쎄이 퍼블릭 리미티드 컴파니 암모니아 슬립 촉매
US9149768B1 (en) 2014-03-27 2015-10-06 General Electric Company Emission control in rich burn natural gas engines
CN107847862B (zh) * 2015-06-18 2020-12-18 庄信万丰股份有限公司 Nh3过量剂量耐受的scr催化剂
PL3357558T3 (pl) * 2017-02-03 2020-03-31 Umicore Ag & Co. Kg Katalizator do oczyszczania gazów spalinowych silników wysokoprężnych
US11073057B2 (en) * 2019-01-31 2021-07-27 Hyundai Motor Company Co clean-up catalyst, after treatment system and after treatment method
GB201903006D0 (en) * 2019-03-06 2019-04-17 Johnson Matthey Plc Lean nox trap catalyst
EP3885040A1 (fr) * 2020-03-24 2021-09-29 UMICORE AG & Co. KG Catalyseur d'oxydation d'ammoniac

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024258A1 (fr) 1979-08-14 1981-02-25 Ciba-Geigy Ag Préparations des compositions pharmaceutiques pour le traitement des infections herpétiques
US5120695A (en) 1989-07-28 1992-06-09 Degusaa Aktiengesellschaft (Degussa Ag) Catalyst for purifying exhaust gases from internal combustion engines and gas turbines operated at above the stoichiometric ratio
EP1876331A2 (fr) 2006-07-08 2008-01-09 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1882832A2 (fr) 2006-07-08 2008-01-30 MAN Nutzfahrzeuge AG Dispositif destiné à réduire les oxydes d'azote dans des gaz d'échappement
EP1892395A1 (fr) 2006-08-16 2008-02-27 MAN Nutzfahrzeuge AG Système de traitement de gaz d'échappement
WO2008106518A2 (fr) 2007-02-27 2008-09-04 Basf Catalysts Llc Scr sur substrats de filtre de faible masse thermique
WO2008106523A2 (fr) 2007-02-27 2008-09-04 Basf Catalysts Llc Catalyseurs bifonctionnels pour oxydation d'ammoniac sélective
WO2011110919A1 (fr) 2010-03-08 2011-09-15 Johnson Matthey Public Limited Company Amélioration de la gestion des émissions
US20110271664A1 (en) 2010-05-05 2011-11-10 Basf Corporation Integrated SCR and AMOX Catalyst Systems
WO2012135871A1 (fr) 2011-03-29 2012-10-04 Basf Corporation Filtre multicomposant pour maîtrise des émissions
US20110182791A1 (en) * 2011-04-08 2011-07-28 Johnson Matthey Public Limited Company Catalysts for the reduction of ammonia emission from rich-burn exhaust
WO2014062949A1 (fr) 2012-10-19 2014-04-24 Basf Corporation Tamis moléculaire à petits pores à cycle à 8 en tant que catalyseur scr à température élevée
DE102013210270A1 (de) 2013-06-03 2014-12-04 Umicore Ag & Co. Kg Dreiwegkatalysator
WO2015121910A1 (fr) 2014-02-12 2015-08-20 新日鉄住金マテリアルズ株式会社 Matériau de base pour support de catalyseurs
US20150231617A1 (en) 2014-02-19 2015-08-20 Ford Global Technologies, Llc Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING
US20170014766A1 (en) * 2014-03-13 2017-01-19 Umicore Ag & Co. Kg Catalyst system for gasoline combustion engines, having three-way catalysts and scr catalyst
US20150290632A1 (en) 2014-04-09 2015-10-15 Ford Global Technologies, Llc IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION
WO2016057285A1 (fr) 2014-10-06 2016-04-14 Corning Incorporated Article filtrant en nid d'abeilles et procédés associés
US20170274321A1 (en) * 2014-10-21 2017-09-28 Basf Corporation Emissions treatment systems with twc catalysts and scr-hct catalysts
US20220010714A1 (en) * 2014-12-08 2022-01-13 Basf Corporation Nitrous oxide removal catalysts for exhaust systems
EP3247493A1 (fr) 2015-01-19 2017-11-29 Umicore AG & Co. KG Pot catalytique à trois voies double couches présentant une meilleure stabilité au vieillissement
US20180229224A1 (en) * 2015-08-21 2018-08-16 Basf Corporation Exhaust gas treatment catalysts
WO2017153239A1 (fr) 2016-03-09 2017-09-14 Haldor Topsøe A/S Procédé de préparation d'un catalyseur en nid d'abeille à base de matériau fibreux non tissé
WO2017187344A1 (fr) 2016-04-26 2017-11-02 Basf Corporation Configuration en zones pour combinaisons de catalyseurs d'oxydation
US20200384449A1 (en) * 2017-02-08 2020-12-10 Basf Corporation Catalytic articles
EP3601755A1 (fr) 2017-03-23 2020-02-05 Umicore AG & Co. KG Filtre à particules à activité catalytique
EP3727655A1 (fr) 2017-12-19 2020-10-28 UMICORE AG & Co. KG Pot catalytique à trois voies monocouche
WO2019219816A1 (fr) 2018-05-18 2019-11-21 Umicore Ag & Co. Kg Systèmes et procédés de traitement des gaz d'échappement impliquant une supplémentation en oxygène et un piégeage d'hydrocarbures
EP3778016A1 (fr) * 2018-10-08 2021-02-17 Sinocat Environmental Technology Co., Ltd. Catalyseur de traitement de gaz résiduaire, procédé de préparation s'y rapportant et son utilisation
DE102019100099A1 (de) 2019-01-04 2020-07-09 Umicore Ag & Co. Kg Verfahren zur Herstellung von katalytisch aktiven Wandflussfiltern
EP3737491A1 (fr) 2019-03-29 2020-11-18 UMICORE AG & Co. KG Filtre à particules à activité catalytique
DE102020101876A1 (de) 2020-01-27 2021-07-29 Umicore Ag & Co. Kg Doppelschichtiger Dreiweg-Katalysator mit weiter verbesserter Alterungsstabilität
EP3915679A1 (fr) 2020-05-26 2021-12-01 UMICORE AG & Co. KG Catalyseur, système catalytique et système de nettoyage de gaz d'échappement permettant de réduire les émissions d'ammoniaque

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CH. BAERLOCHERW.M. MEIERD.H. OLSON: "Atlas of Zeolite Framework Types", 2001, ELSEVIER
R. HECK ET AL.: "Commercial Technology", 1995, article "Catalytic Air Pollution Control", pages: 90
W.M. MEIER, PURE & APPL. CHEM., vol. 58, no. 10, 1986, pages 1323 - 1328

Also Published As

Publication number Publication date
WO2023198569A1 (fr) 2023-10-19
WO2023198573A1 (fr) 2023-10-19
WO2023198572A1 (fr) 2023-10-19
WO2023198571A1 (fr) 2023-10-19
WO2023198574A1 (fr) 2023-10-19
WO2023198577A1 (fr) 2023-10-19
WO2023198570A1 (fr) 2023-10-19

Similar Documents

Publication Publication Date Title
EP3727653B1 (fr) Filtre à particules à activité catalytique
EP2335810B1 (fr) Réduction catalytique sélective d'oxydes d'azote dans du gaz d'échappement de moteurs diesel
DE102012222801B4 (de) Abgassystem und Verwendung einer Washcoatbeschichtung
DE102012218254B4 (de) Abgassystem für einen verbrennungsmotor
EP1961933B1 (fr) Filtre à particule de diesel activé de manière catalytique et doté d'une action de blocage à l'ammoniac
EP2718011B1 (fr) Procédé pour la réduction catalytique sélective d'oxydes d'azote dans les gaz d'échappement de moteurs diesel
EP3116630B1 (fr) Système catalytique pour des moteurs à combustion interne à essence comprenant des catalyseurs trois voies et un catalyseur scr
DE102014105736A1 (de) Motor mit Fremdzündung und Abgassystem, das ein katalysiertes in Zonen beschichtetes Filtersubstrat umfasst
DE102016118542A1 (de) Einen russkatalysator und einen scr-katalysator aufweisendes katalytisches filter
EP2322773B1 (fr) Procédé destiné au nettoyage de gaz d'échappement de moteurs à combustion
EP3737491B1 (fr) Filtre à particules à activité catalytique
DE112011103996T5 (de) Metall-enthaltender Zeolithkatalysator
DE102014104748A1 (de) Filtersubstrat, das einen Dreiwegekatalysator umfasst.
DE102010002425A1 (de) Filter
DE102010056223A1 (de) Abgassystem für einen Fahrzeugverbrennungsmotor mit Fremdzündung
EP3601755A1 (fr) Filtre à particules à activité catalytique
EP3695902B1 (fr) Catalyseur destiné à la réduction d'oxydes d'azote
DE102017109169A1 (de) Abgassystem
WO2018069199A1 (fr) Ensemble de catalyseurs
WO2023198575A1 (fr) Système de gaz d'échappement pour moteurs à combustion interne à fonctionnement principalement stœchiométrique, comprenant un catalyseur pour réduire les émissions d'ammoniac
DE102023101772A1 (de) Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen
DE202009018901U1 (de) Katalytisch aktives Partikelfilter zur Reinigung von Abgasen von Verbrennungsmotoren
DE102021118802A1 (de) Abgasreinigungssystem zur Reinigung von Abgasen von Benzinmotoren
DE102021118803A1 (de) Abgasreinigungssystem zur Reinigung von Abgasen von Benzinmotoren

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23717909

Country of ref document: EP

Kind code of ref document: A1