[go: up one dir, main page]

EP3419752A1 - Catalyseur destiné à la réducteur d'oxydes d'azote - Google Patents

Catalyseur destiné à la réducteur d'oxydes d'azote

Info

Publication number
EP3419752A1
EP3419752A1 EP17706452.4A EP17706452A EP3419752A1 EP 3419752 A1 EP3419752 A1 EP 3419752A1 EP 17706452 A EP17706452 A EP 17706452A EP 3419752 A1 EP3419752 A1 EP 3419752A1
Authority
EP
European Patent Office
Prior art keywords
washcoat
storage catalyst
catalyst according
nitrogen
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.)
Withdrawn
Application number
EP17706452.4A
Other languages
German (de)
English (en)
Inventor
Thomas UTSCHIG
Ruediger Hoyer
Naohiro Kato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of EP3419752A1 publication Critical patent/EP3419752A1/fr
Withdrawn legal-status Critical Current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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/657—Pore diameter larger than 1000 nm
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/03—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
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2042—Barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2047—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • 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
    • B01D2255/90—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
    • B01D2255/91—NOx-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
    • B01D2255/92—Dimensions
    • B01D2255/9205—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt

Definitions

  • the present invention relates to a catalyst for the reduction of nitrogen oxides, which is contained in the exhaust lean burned internal combustion engines.
  • the exhaust of motor vehicles which are operated with lean-burn internal combustion engines, for example with diesel engines, in addition to carbon monoxide (CO) and nitrogen oxides (NO x ) also contains components resulting from the incomplete combustion of the fuel in the combustion chamber of the cylinder.
  • HC residual hydrocarbons
  • Diesel soot or “soot particles”.
  • Diesel soot particles particulate emissions
  • These are complex agglomerates of predominantly carbon-containing solid particles and an adhering liquid phase, which mostly consists of relatively long-chain hydrocarbon condensates.
  • the liquid phase adhering to the solid components is also referred to as "Soluble Organic Fraction SOF” or “Volatile Organic Fraction VOF".
  • nitrogen oxide storage catalysts are known, for which the term “lean NOx trap” or “LNT” is also common are stored in the form of nitrates and this decomposed in a subsequent rich operating phase of the engine again and the thus released nitrogen oxides with the reducing
  • Suitable storage materials are, in particular, oxides, carbonates or hydroxides of magnesium, calcium, strontium, barium, the alkali metals, the rare earth metals or mixtures thereof. Due to their basic properties, these compounds are capable of forming nitrates with the acidic nitrogen oxides of the exhaust gas and of storing them in this way. They are suitable for generating a large interaction area with the exhaust gas in the highest possible dispersion
  • nitrogen oxide storage catalysts generally contain noble metals such as platinum, palladium and / or rhodium as catalytically active components. Their task is, on the one hand, to oxidise NO to NO 2, CO and HC to CO 2 under lean conditions and, on the other hand, to reduce released NO 2 to nitrogen during the rich operating phases in which the nitrogen oxide storage catalyst is regenerated.
  • EP 0 885 650 A2 describes an exhaust gas purification catalyst for internal combustion engines with two catalytically active layers on a support body.
  • the layer directly on the support body comprises one or more highly dispersed alkaline earth oxides, at least one
  • Platinum group metal as well as at least one finely divided, oxygen-storing material.
  • the platinum group metals are in close contact with all components of the first layer.
  • the second layer is in direct contact with the exhaust gas and contains at least one platinum group metal and at least one finely divided oxygen storing material. Only part of the finely divided solids of the second layer serve as a carrier for the platinum group metals.
  • the catalyst is a three-way catalytic converter that controls the harmful components of the exhaust gas
  • a nitrogen oxide storage catalyst which comprises two superimposed catalyst layers on a carrier substrate.
  • the lower layer lying directly on the carrier substrate comprises one or more noble metals, as well as one or more nitrogen oxide storage components.
  • the upper layer comprises one or more
  • Precious metals, as well as cerium oxide and is free of alkali or alkaline earth components Catalyst substrates containing nitrogen oxide storage materials and having two or more layers are also described in WO 2012/029050.
  • the first layer is directly on the carrier substrate and comprises platinum and / or palladium, while the second layer is on the first and comprises platinum.
  • Both layers also contain one or more oxygen storage materials and one or more nitric oxide storage materials comprising one or more alkali and / or alkaline earth metals.
  • the total amount of alkali and alkaline earth metal in the nitrogen oxide storage materials is 0.18 to 2.5 g / in 3 calculated as alkali metal oxide M 2 O and alkaline earth metal oxide MO.
  • Catalyst coatings are already known which, owing to a relatively large porosity, have improved flow with exhaust gas and thus improved contact of the exhaust gas constituents with the catalytically active centers.
  • Such catalyst coatings can be obtained, for example, by coating an inert carrier body with an aqueous coating suspension (washcoat) which contains a so-called pore-forming agent. Become a pore builder
  • EP 1 832 344 A1 mentions activated carbon, graphite powder, cellulose powder, organic fibers and synthetic fibers as suitable for this purpose.
  • the porosity of a catalytically active coating is increased by means of an aqueous oil-in-water macroemulsion.
  • the present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on one
  • the upper washcoat layer B has macropores having an average pore size of less than 15 m, the macropores forming a pore volume in the upper washcoat layer B of 5 to 25% by volume.
  • the cerium oxide used in washcoat layers A and B can be any cerium oxide used in washcoat layers A and B.
  • cerium oxide is used in the washcoat layer A in an amount of from 110 to 160 g / l, for example from 125 to 145 g / l.
  • cerium oxide is used in amounts of 22 to 120 g / l, for example 40 to 100 g / l or 45 to 65 g / l.
  • oxides, carbonates and / or hydroxides of magnesium, strontium and / or barium are suitable as the alkaline earth compound in the washcoat layer A, in particular magnesium oxide, barium oxide and / or
  • Strontium oxide especially barium oxide, strontium oxide or barium oxide and strontium oxide.
  • Suitable alkali compounds in the washcoat A are, in particular, oxides, carbonates and / or hydroxides of lithium, potassium and / or sodium.
  • the alkaline earth or alkali compound in washcoat A is present in amounts of 10 to 50 g / l, especially 15 to 20 g / l, calculated as alkaline earth oxide and based on the volume of the support body.
  • washcoat layer A may include manganese oxide. In washcoat layer A, this is present in particular in amounts of 1 to 10% by weight, preferably 2.5 to 7.5% by weight, based on the sum of the washcoat layers A and B, in each case calculated as MnO.
  • the washcoat layer B also contains
  • Washcoat layer B at up to 2.5 wt .-%, preferably 0.5 to 2.5 wt .-%, based on the sum of Washcoat füren A and B.
  • Manganese oxide can serve as a carrier material for the noble metals platinum, palladium and optionally rhodium. However, in preferred embodiments of the present invention, manganese oxide is not used as a carrier material, neither for the noble metals platinum, palladium and optionally rhodium, nor for another component of washcoat A and optionally washcoat B.
  • manganese oxide in the context of the present invention means in particular MnO, MnO 2 or Mn 2 O 3 or combinations of MnO 2 , MnO and / or Mn 2 O 3 .
  • manganese oxide is not in the form of mixed oxides with other oxides of washcoat A and B layers.
  • manganese oxide is not present in the form of a mixed oxide with cerium oxide, for example not in the form of MnOx-CeCh, MnO-ZrCte and
  • the ratio platinum to palladium in the washcoat A in embodiments of the present invention is for example 4: 1 to 18: 1 or 6: 1 to 16: 1, for example 8: 1, 10: 1, 12: 1 or 14: 1.
  • washcoat layer B contains rhodium as another precious metal. Rhodium is in this case
  • the total amount of noble metal i. of platinum, palladium and
  • optionally rhodium, in the nitrogen oxide storage catalyst according to the invention is in embodiments of the present invention, 2.12 to 7.1 g / l (60 to 200 g / ft 3 ), based on the volume of the support body.
  • the noble metals are platinum and palladium and optionally rhodium
  • alumina silica
  • titanium dioxide but also mixed oxides such as aluminum-silicon mixed oxides and cerium-zirconium mixed oxides.
  • platinum and palladium and, optionally, rhodium are used as support material for the noble metals
  • Alumina is used, in particular those which is stabilized by 1 to 6 wt .-%, in particular 4 wt .-%, lanthanum oxide.
  • Manganese oxide preferably does not serve as a support for platinum and palladium and optionally rhodium.
  • the total washcoat load of the support body is in
  • Embodiments of the present invention 300 to 600 g / l, based on the volume of the support body.
  • the macropores of the upper washcoat layer B have an average pore size of 2 to 12 ⁇ m, preferably 4 to 7 ⁇ m.
  • Macropores a pore volume in the upper Washcoat für B from 5 to 20 vol .-%, for example 5 to 10 vol .-% or 10 to 15 vol .-%.
  • the average pore size of the macropores in Washcoat caring B is usually identical to the average particle size of the pore-forming agent used, because each particle of the used
  • Pore forming a macro pore in the calcined catalyst corresponds.
  • the pore volume of the washcoat layer A results as the sum of the volumes of the particles of the pore-forming agent used.
  • Average pore size and pore volume thus result from the size and amount of pore-forming agent used and can be easily determined.
  • average pore size and pore volume of course, by the usual and known in the art methods, eg
  • the present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on a support body,
  • o cerium oxide in an amount of 100 to 160 g / l
  • an upper washcoat layer B is disposed over the lower washcoat layer A and
  • the amount g / l each refers to the volume of the support body and wherein the upper Washcoat caring B macropores having an average pore size of 2 to 12 ⁇ and wherein the macropores a pore volume in the upper Washcoat caring B a pore volume of 5 to 20 Vol .-% form.
  • washcoat layer A contains manganese oxide in an amount of 5 to 15 g / l.
  • Washcoat A in amounts of 250 to 350 g / l and washcoat B in amounts of 80 to 130 g / l before.
  • the coating suspension for washcoat A in the appropriate amount is applied to the support body and dried.
  • washcoat layer A coated support applied and also dried. Then we calcined the finished coated support body.
  • the necessary coating suspensions can be obtained by methods known to those skilled in the art.
  • Supported materials supported noble metals, and optionally manganese oxide or another manganese compound in the appropriate amounts in water and milled in a suitable mill, in particular a ball mill, to a particle size of dso 3 to 5 m. It is preferred to use manganese in the form of manganese carbonate of the coating suspension in the last step, i. E. just before grinding, to admit.
  • the pore formers are made of materials that completely and in the calcination of the finished coated support body from about 350 ° C
  • Suitable pore formers consist in particular of synthetic resins, such as polyurethane, polystyrene, polyethylene, polyester, polyacrylonitrile or polyacrylic ester resins. Pore formers are particularly preferred
  • the pore formers must have an average particle size of less than 15 ⁇ m, for example 2 to 12 ⁇ m, preferably 4 to 7 ⁇ m.
  • the coating suspension for producing the washcoat layer B pore-forming agent must be added in an appropriate amount. This can be determined from the average particle size of the pore formers in a simple manner. Suitable pore formers are known and can be purchased on the market.
  • the nitrogen oxide storage catalysts according to the invention are outstandingly suitable for the conversion of NO x in exhaust gases from
  • the nitrogen oxide storage catalysts according to the invention are thus suitable for Euro 6 applications.
  • the present invention thus also relates to a method for
  • the upper Washcoat caring B macropores having an average pore size of less than 15 ⁇ , wherein the macropores form a pore volume in the upper washcoat B of 5 to 25% by volume.
  • a catalyst according to the invention a commercial honeycomb ceramic support is coated with a first coating suspension comprising Pt and Pd supported on alumina, ceria in an amount of 125 g / l, 21 g / l barium oxide, 15 g / l magnesium oxide and 7 , 5 g / l MnO in the form of manganese carbonate.
  • the loading of Pt and Pd is 35 g / ft 3 (1.236 g / l) and 3.5 g / ft 3 (0.124 g / l) and the
  • washcoat layer A dried.
  • a further washcoat layer B was applied to the first washcoat layer A.
  • a coating suspension was also coated which also contained Pt and Pd supported on alumina and Rh supported on a lanthanum stabilized alumina.
  • the loading of Pt, Pd and Rh in washcoat B was thus 35 g / ft 3 (1.236 g / l), 3.5 g / ft 3 (0.124 g / l) and 5 g / ft 3 (0.177 g / l).
  • Coating suspension also contained 55 g / l of ceria at a washcoat loading of layer B of about 81 g / l in the calcined catalyst.
  • the coating suspension contained in addition to the above
  • Components also 5 g / l of a pore builder from a crosslinked
  • Polymethyl methacrylate resin having an average particle size of 5 to 7 ⁇ .
  • the coating was dried and then calcined. After calcination, the pore volume in washcoat B was 6.5% by volume.
  • Example 1 was repeated with the difference that the coating suspension for washcoat B contained the pore former in an amount of 7.5 g / l pore former. After calcination, the pore volume in washcoat B was 9.7% by volume.
  • the catalyst thus obtained is hereinafter called K2.
  • Example 1 was repeated with the difference that the coating suspension for washcoat layer B contained no pore-forming agent.
  • the catalyst thus obtained is hereinafter called VK1.
  • the sample was conditioned at 450 ° C.
  • a lean gas composition corresponding to Table 1 and 10s a rich gas composition was passed alternately over the catalyst for a period of 15 minutes.
  • the sample was cooled to measurement temperature (175 ° C. or 300 ° C.) under a nitrogen atmosphere, or kept at 450 ° C. At a constant measuring temperature then the NOx adsorption in the
  • the "Adsorption" gas composition is measured according to Table 1.
  • the NOx storage capacity is calculated from the difference in the metered amount of NOx relative to the catalyst volume and the amount of NOx slip measured behind the catalyst sample relative to the catalyst volume at the time when the NOx -Umsatz over the sample 75%, or only 50% and is in Figure 1 as NOx
  • Example 1 was repeated with the difference that the washcoat B coating suspension contained 5 g / l of a pore former of a crosslinked polymethyl methacrylate resin having an average particle size of 8 to 12 m.
  • Example 4
  • Example 1 was repeated with the difference that the coating suspension for washcoat B 7.5 g / l of a pore former of a crosslinked polymethyl methacrylate resin with an average

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Nanotechnology (AREA)

Abstract

La présente invention concerne un catalyseur accumulateur d'oxydes d'azote composé d'au moins deux couches d'imprégnation catalytiquement actives sur un corps support. Une couche d'imprégnation inférieure A contenant de l'oxyde de cérium, un composé alcalino-terreux et/ou un composé alcalin, tout comme du platine et du palladium, et une couche d'imprégnation supérieure B disposée sur la couche d'imprégnation A contenant de l'oxyde de cérium, ainsi que du platine et du palladium et étant exempte de composés alcalins et alcalino-terreux. L'invention concerne également un procédé de conversion de NOx contenus dans les gaz d'échappement de véhicules automobiles qui sont propulsés par des moteurs fonctionnant avec un mélange pauvre.
EP17706452.4A 2016-02-22 2017-02-21 Catalyseur destiné à la réducteur d'oxydes d'azote Withdrawn EP3419752A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016103034 2016-02-22
PCT/EP2017/053825 WO2017144426A1 (fr) 2016-02-22 2017-02-21 Catalyseur destiné à la réducteur d'oxydes d'azote

Publications (1)

Publication Number Publication Date
EP3419752A1 true EP3419752A1 (fr) 2019-01-02

Family

ID=58098614

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17706452.4A Withdrawn EP3419752A1 (fr) 2016-02-22 2017-02-21 Catalyseur destiné à la réducteur d'oxydes d'azote

Country Status (5)

Country Link
US (1) US20200030745A1 (fr)
EP (1) EP3419752A1 (fr)
KR (1) KR20180116396A (fr)
CN (1) CN108778490A (fr)
WO (1) WO2017144426A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102651643B1 (ko) * 2018-08-27 2024-03-27 바스프 코포레이션 비금속으로 도핑된 산화 지르코늄 촉매 지지 물질
EP3623047B1 (fr) 2018-09-17 2021-02-24 Umicore Ag & Co. Kg Catalyseur de réduction d'oxydes d'azote
EP3695902B1 (fr) 2019-02-18 2021-09-01 Umicore Ag & Co. Kg Catalyseur destiné à la réduction d'oxydes d'azote
US12036532B2 (en) * 2019-05-31 2024-07-16 Mitsui Mining & Smelting Co., Ltd. Exhaust gas purification catalyst and exhaust gas purification system using the exhaust gas purification catalyst
JP2023507267A (ja) * 2019-12-19 2023-02-22 ビーエーエスエフ コーポレーション 微粒子状物質を捕集するための触媒物品
EP3889404A1 (fr) * 2020-03-30 2021-10-06 Johnson Matthey Public Limited Company Catalyseurs de conversion à trois voies (twc) multirégion pour des traitements de gaz d'échappement d'un moteur à essence avec atténuation h2s améliorée
CN111889092B (zh) * 2020-07-30 2022-09-20 万华化学集团股份有限公司 用于Fenton出水残余双氧水分解的催化剂制备方法、催化剂及其应用
EP4166230A1 (fr) * 2021-10-12 2023-04-19 Johnson Matthey Public Limited Company Article catalytique pour système d'échappement de moteur à gaz naturel
CN116173943A (zh) * 2023-02-24 2023-05-30 中自环保科技股份有限公司 一种提升汽车尾气净化催化剂老化性能的方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19726322A1 (de) 1997-06-20 1998-12-24 Degussa Abgasreinigungskatalysator für Verbrennungsmotoren mit zwei katalytisch aktiven Schichten auf einem Tragkörper
US6221804B1 (en) * 1998-01-27 2001-04-24 Mazda Motor Corporation Catalyst for purifying exhaust gas and manufacturing method thereof
US7137249B2 (en) * 2004-08-12 2006-11-21 Ford Global Technologies, Llc Thermally stable lean nox trap
JP2006110485A (ja) 2004-10-15 2006-04-27 Johnson Matthey Japan Inc 排気ガス触媒およびそれを用いた排気ガス処理装置
JP2007278101A (ja) * 2006-04-03 2007-10-25 Honda Motor Co Ltd 排気ガス浄化用触媒コンバータ装置
JP2007275704A (ja) 2006-04-03 2007-10-25 Johnson Matthey Japan Inc 排気ガス触媒およびそれを用いた排気ガス処理装置
US8475752B2 (en) 2008-06-27 2013-07-02 Basf Corporation NOx adsorber catalyst with superior low temperature performance
US8722001B2 (en) * 2008-10-17 2014-05-13 Umicore Shokubai Japan Co., Ltd. Catalyst for purification of exhaust gas and method for purification using the same
KR101868176B1 (ko) 2010-09-02 2018-07-19 바스프 에스이 개선된 no 산화 활성을 갖는 가솔린 린번 엔진용 촉매
WO2013191298A1 (fr) * 2012-06-20 2013-12-27 Kabushiki Kaisha Toyota Chuo Kenkyusho Support de catalyseur pour la purification de gaz d'échappement, catalyseur pour la purification de gaz d'échappement utilisant ledit support, et procédé pour la production du support de catalyseur pour la purification de gaz d'échappement
EP2769760A1 (fr) * 2013-02-21 2014-08-27 Umicore AG & Co. KG Catalyseur destiné à la réduction d'oxyde d'azote
US9561495B2 (en) 2013-03-06 2017-02-07 Basf Corporation Porous catalyst washcoats
DE102013207709A1 (de) * 2013-04-26 2014-10-30 Umicore Ag & Co. Kg Entschwefelung von NOX-Speicherkatalysatoren
US9381510B2 (en) 2013-09-11 2016-07-05 Mitsui Mining & Smelting Co., Ltd. Exhaust gas purifying catalyst comprising a catalyst layer comprising at least two inorganic porous particles

Also Published As

Publication number Publication date
US20200030745A1 (en) 2020-01-30
WO2017144426A1 (fr) 2017-08-31
KR20180116396A (ko) 2018-10-24
CN108778490A (zh) 2018-11-09

Similar Documents

Publication Publication Date Title
WO2017144426A1 (fr) Catalyseur destiné à la réducteur d'oxydes d'azote
EP3177400B1 (fr) Catalyseur destiné à la réduction d'oxyde d'azote et un procédé de réduction des nox
DE60115337T2 (de) Mischoxid und Katalysator zur Reinigung von Abgas
EP1911506B1 (fr) Catalyseur accumulateur de NOx avec une température de désulfuration réduite
DE102014104748B4 (de) Abgassystem, das ein katalysiertes filter umfasst
EP2943276B1 (fr) Catalyseur permettant de réduire les dioxydes d'azote
WO2017134065A1 (fr) Catalyseur à stockage des oxydes d'azote multicouche contenant du manganèse
DE112014000481T5 (de) Abgasreinigungskatalysator und Herstellungsverfahren dafür
EP4365421A2 (fr) Filtre à particules à activité catalytique
DE202007019526U1 (de) NOx-Speichermaterialien und -Fallen, die gegenüber Wärmealterung beständig sind
DE19726322A1 (de) Abgasreinigungskatalysator für Verbrennungsmotoren mit zwei katalytisch aktiven Schichten auf einem Tragkörper
EP3520882A1 (fr) Suppression de particules des gaz d'échappement de moteurs à combustion interne fonctionnant essentiellement sur un mélange d'air/carburant st chiométrique
WO2008113457A1 (fr) Pot catalytique monocouche au palladium-rhodium
WO2008113445A1 (fr) Pot catalytique trois voies à deux couches
DE102014102023A1 (de) Oxidationskatalysator für einen verbrennungsmotor
EP2958660A1 (fr) Catalyseur et procédé de réduction d'oxydes d'azote
WO2018172299A1 (fr) Filtre à particules à activité catalytique
DE102017201568A1 (de) Perowskit basierte sauerstoff-speichermaterialien
EP1180397A1 (fr) Matériau à base de cérium pour le stockage de l'oxygène, procédé de préparation dudit matériau et son utilisation pour le traitement des gaz d'échappement des moteurs à combustion interne
WO2020058265A1 (fr) Catalyseur de réduction des oxydes d'azote
EP3695902B1 (fr) Catalyseur destiné à la réduction d'oxydes d'azote
EP2834001B1 (fr) Méthode pour séparer du monoxyde de carbone et des hydrocarbures des gaz d'échappement de moteurs travaillant en régime pauvre
EP3191222B1 (fr) Dispersion de couchage
EP4324555A1 (fr) Composition catalytiquement active contenant du ruthénium pour catalyseurs de post-traitement de gaz d'échappement
DE102023101763A1 (de) Abgassystem für überwiegend stöchiometrisch betriebene Verbrennungsmotoren aufweisend einen Katalysator zur Verminderung der Ammoniakemissionen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180927

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190521