EP2560755A1 - Nouveaux matériaux d'oxyde mixte pour la réduction catalytique sélective d'oxydes d'azote dans des gaz d'échappement - Google Patents

Nouveaux matériaux d'oxyde mixte pour la réduction catalytique sélective d'oxydes d'azote dans des gaz d'échappement

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Publication number
EP2560755A1
EP2560755A1 EP11716376A EP11716376A EP2560755A1 EP 2560755 A1 EP2560755 A1 EP 2560755A1 EP 11716376 A EP11716376 A EP 11716376A EP 11716376 A EP11716376 A EP 11716376A EP 2560755 A1 EP2560755 A1 EP 2560755A1
Authority
EP
European Patent Office
Prior art keywords
oxide
zeolite
catalyst
compound
catalytically active
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Withdrawn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
EP11716376A
Other languages
German (de)
English (en)
Inventor
Katja Adelmann
Gerald Jeske
Rainer Domesle
Nicola Soeger
Michael Seyler
Anke Schuler
Thomas R. Pauly
Barry W. L. Southward
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
Priority to EP11716376A priority Critical patent/EP2560755A1/fr
Publication of EP2560755A1 publication Critical patent/EP2560755A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01D53/9472—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 zones
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
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    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J37/02—Impregnation, coating or precipitation
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2251/00—Reactants
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    • 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
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • F01N3/2066—Selective catalytic reduction [SCR]
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Definitions

  • the invention relates to the use of mixed oxides as a catalytically active material for the selective catalytic reduction of nitrogen oxides with ammonia or a decomposable to ammonia compound as a reducing agent in the exhaust gas of predominantly lean-burn internal combustion engines in motor vehicles.
  • the invention also relates to catalytically active compositions comprising a mixed oxide and a zeolite compound and / or a zeolite-like compound, as well as various embodiments of catalysts prepared from said mixed oxides or compositions.
  • Exhaust gases from motor vehicles with a predominantly lean-burn internal combustion engine contain not only the usual primary emissions of carbon monoxide CO, hydrocarbons HC and nitrogen oxides NO x a relatively high oxygen content of up to 15 vol .-%. Carbon monoxide and hydrocarbons can easily be neutralized by oxidation. The reduction of nitrogen oxides to nitrogen is more difficult because of the high oxygen content.
  • One known method of removing nitrogen oxides from exhaust gases in the presence of oxygen is the Selective Catalytic Reduction (SCR) process using ammonia on a suitable catalyst, abbreviated to SCR catalyst.
  • SCR Selective Catalytic Reduction
  • the nitrogen oxides to be removed from the exhaust gas are reacted with ammonia to nitrogen and water.
  • the ammonia used as the reducing agent can be made available by metering into the exhaust gas stream a compound which is decomposable to ammonia, for example urea, ammonium carbamate or ammonium formate, and subsequent hydrolysis.
  • exhaust-gas cleaning concepts for motor vehicles are known in which ammonia is generated during a rich operating phase of the engine on an upstream catalytic converter, for example a nitrogen oxide storage catalytic converter, as secondary emission and stored in the SCR catalytic converter until the point of consumption during the lean operating phases.
  • an upstream catalytic converter for example a nitrogen oxide storage catalytic converter
  • the use in a discontinuous SCR system in which the ammonia used as a reducing agent is generated exclusively as a secondary emission in the exhaust system requires SCR catalysts whose ammonia storage capacity is sufficient to provide as much as possible of the total reducing agent need for Abgasentstickung during the lean phase.
  • Particularly suitable for this purpose are zeolite-based SCR catalysts, as are known from numerous publications and patent applications. For example, US Pat. No.
  • 4,961,917 describes a method for reducing nitrogen oxides with ammonia using a catalyst which contains iron and / or copper as promoter in addition to a zeolite having defined properties.
  • SCR catalysts based on transition metal-exchanged zeolites and processes for the selective catalytic reduction using such SCR catalysts are described, for example, in EP 1 495 804 A1, US Pat. No. 6,914,026 B2 or EP 1 147 801 B1.
  • the SCR catalyst it is not necessary for the SCR catalyst to have a large ammonia storage capacity. Accordingly, efforts are being made to avoid the use of zeolite-based SCR catalysts, which are very expensive because of the high production prices of zeolite compounds.
  • SCR catalysts containing vanadium oxide in addition to titanium dioxide or tungsten oxide or mixtures thereof are suitable.
  • EP 0 385 164 B1 describes such a catalyst which, in addition to titanium dioxide, contains at least one oxide of tungsten, silicon, boron, aluminum, phosphorus, zirconium, barium, yttrium, lanthanum or cerium, and at least one oxide of vanadium, niobium, molybdenum, Contains iron or copper and is prepared as a shaped body by compression or extrusion of the components optionally after addition of suitable auxiliaries.
  • EP 1 153 648 A1 describes a structured SCR catalyst which contains, under a hydrolysis catalyst coating, a reduction coating whose composition corresponds to the formulation known from EP 0 385 164 B1.
  • EP 0 246 859 describes an SCR catalyst containing vanadium applied to a mixture of ceria and alumina.
  • vanadium-containing SCR catalysts for cleaning the exhaust gases of motor vehicles is the possible emission of volatile, toxic vanadium compounds at higher exhaust gas temperatures, which must be expected to be harmful to humans and the environment. Accordingly, the acceptance of vanadium-containing autocatalysts in the market is decreasing. Efforts to provide cost-effective vanadium-free SCR catalysts have been around for some time. Thus, some mixed oxide compositions based on cerium-zirconium mixed oxide and their use in the SCR reaction are already known in the art.
  • WO 2008/049491 discloses homogeneous cerium-zirconium mixed oxides containing 10 to 90% by weight of cerium oxide, based on the total weight of the cerium-zirconium mixed oxide, and by incorporating sulfur or a transition metal selected from the group consisting of chromium, molybdenum, Tungsten or mixtures thereof or combinations thereof are activated for the SCR reaction.
  • Particularly preferred embodiments of these mixed oxides contain 0.02 to 3 wt .-% sulfur and / or 5 to 15 wt .-% molybdenum or tungsten and 0.5 to 3 wt .-% iron or copper, each based on the total weight of cerium -Zirkon mixed oxide.
  • Cerium-zirconium mixed oxides containing 45-55% by weight of CeO 2 and 1-9% by weight of rare earth oxide are particularly preferably used for the preparation of the SCR-active compounds.
  • EP 2 116 293 discloses a vanadium-free SCR catalyst which contains tungsten oxide WO 3 and a homogeneous cerium-zirconium mixed oxide (Ce, Zr) O 2 , the content of tungsten oxide WO 3 being between 5 and 25% by weight, the content of the homogeneous cerium-zirconium mixed oxide can be between 50 and 95% by weight.
  • Cerium-zirconium mixed oxides having a weight ratio of cerium oxide CeO 2 to zirconium oxide ZrO 2 between 0.67 and 1.5 are preferred.
  • EP 2 072 120 likewise discloses a temperature-stable catalyst for the reduction of nitrogen oxides in the presence of ammonia, which contains 10 to 30% by weight of cerium oxide and 5 to 14% of tungsten oxide, and zirconium oxide as complex oxide.
  • WO 2008/051752 discloses a NO x reduction catalyst comprising a cerium-zirconium-based mixed oxide of the formula Ce a Zr b R t AiMeO x wherein R is tungsten or manganese and A is molybdenum, tantalum or niobium, optionally also tungsten, if R is manganese.
  • M denotes a trivalent rare earth ion, preferably selected from Sm, Gd, Dy, Er, Yb, Ho, Er, Tm and Lu, but not La or Y.
  • the mixed oxide of This composition is catalytically active and is suitable for the selective catalytic reduction of nitrogen oxides with ammonia. It can be used in a corresponding exhaust aftertreatment system either as an essential component of the catalytically active coating of an SCR catalyst or as part of the coating of a catalytically active particulate filter.
  • EP 0 277 765 discloses a process for removing nitrogen oxides from the exhaust gas of diesel engines by catalytic reduction over a honeycomb catalyst containing as active material 60 to 95% by weight of an oxide selected from TiO 2 , ZrO 2 , (Ti, Zr ) 0 2 , (Ti, Si) 0 2 and (Ti, Zr, Si) 0 2 . Furthermore, the catalyst contains 0.5 to 40 wt .-% vanadium, tungsten, molybdenum, manganese, cerium and / or tin oxide.
  • US 5,552,128 describes a process for reacting nitrogen oxides to nitrogen by contacting the nitrogen oxides with a reducing agent in the presence of a catalyst which effectively catalyzes the reduction of the nitrogen oxides.
  • the catalyst consists essentially of solid acid components comprising a metal oxide of the 4th subgroup of the Periodic Table of the Elements, which is modified with an oxyanion of a metal of the 6th subgroup and further at least one metal selected from the 1st, the 5th, the 7th or contains the 8th subgroup or even the 4th main group of the periodic table of the elements.
  • US 2006/0228283 describes a catalyst system and a method for reducing nitrogen oxides in exhaust gases by reduction with hydrocarbons or oxygen-containing organic compounds.
  • the "modification catalyst” comprises a "modification oxide” selected from the group consisting of iron oxide, cerium oxide, copper oxide, manganese oxide, chromium oxide, lanthanide oxides, actinide oxides, molybdenum oxide, Tin oxide, indium oxide, rhenium oxide, tantalum oxide, osmium oxide, barium oxide, calcium oxide, strontium oxide, potassium oxide, calcium oxide, vanadium oxide, nickel oxide, tungsten oxide, and mixtures thereof.
  • This "modifying oxide” is applied to inorganic carrier oxides, at least one acidic and preferably selected from the group consisting of titanium-zirconium mixed oxide, zirconium-aluminum mixed oxide, sulphated zirconium oxide, phosphated zirconium oxide, tungsten-modified zirconium mixed oxide, silicon-alumin
  • the invention has for its object to provide cost-effective, vanadium-free SCR catalysts available, which are characterized by dynamic light-off while aging resistant ammonia storage capacity and can also be produced as exhaust gas purification components with low back pressure.
  • cerium-zirconium mixed oxides can show an effect catalyzing the selective catalytic reduction of nitrogen oxides after a targeted activation.
  • the inventors have now surprisingly found that the targeted Veresell- tion of the aforementioned mixed oxides with niobium (V) oxide (Nb 2 0 5 ) to a mixed oxide of ceria, zirconia, rare earth sesquioxide and niobium oxide, which without an additional activation step an excellent Activity with high aging stability in the SCR reaction shows.
  • Such mixed oxides are described in US Pat. No. 6,468,941 B1, but are not used there to catalyze the selective catalytic reduction of nitrogen oxides, but as oxygen-ion-conducting or oxygen-storing materials in three-way catalysts.
  • the present invention accordingly relates to the use of a catalytically active mixed oxide consisting of cerium oxide, niobium oxide, rare earth sesquioxide and zirconium oxide for the selective catalytic reduction of nitrogen oxides.
  • the use according to the invention takes place, for example, in such a way that the mixed oxide is contained in the form of a fully extruded, catalytically active honeycomb body in a catalyst.
  • the use according to the invention takes place in such a way that the mixed oxide is contained in a catalytically active coating which is applied to a catalytically inert support body which forms a catalyst together with the coating.
  • the preparation of the mixed oxide used according to the invention can be carried out by the simplest means.
  • a suitable complex mixed oxide is obtained, for example, by impregnation of a commercially available cerium-zirconium mixed oxide, which is doped with rare earth sesquioxide for stabilization, with an aqueous solution of a water-soluble niobium compound and subsequent calcination of the (wet) powder thus obtained.
  • Preferred mixed oxides to be used according to the invention which are very suitable for catalyzing the selective reduction of nitrogen oxides in lean exhaust gases, have the following composition of their components, calculated as parts by weight of the primary oxides: 15-50% by weight CeO 2 , 3 25 wt .-% Nb 2 0 5l 3 - 10 wt .-% SE 2 0 3 and rest Zr0 2 , where SE is a rare earth element.
  • the mixed oxides contain 25-45 wt .-% Ce0 2 , 3 - 20 wt .-% Nb 2 0 5l 3 - 10 wt .-% SE 2 0 3 and the radical Zr0 2 , and most preferably 35- 40 wt % Ce0 2 , 10-15% by weight Nb 2 0 5 , 3-6% by weight SE 2 O 3 and the radical ZrO 2 .
  • the mixed oxides to be used according to the invention are processed, for example, into a mechanically stable catalyst.
  • Preferred embodiments of such a catalyst are obtained by applying at least one catalytically active coating which contains the mixed oxide to be used according to the invention to a catalytically inert support body.
  • a catalytically inert support preferably ceramic or metallic fürflußwaben redesign, ceramic Wandflußfiltersubstrate and ceramic or metallic foam structures are used.
  • preferred embodiments of the catalyst are obtained when a catalytically active, monolithic honeycomb body is produced by extrusion from the mixed oxide to be used according to the invention. These embodiments are characterized by a particularly low back pressure.
  • an extrudable, pasty mass is produced which in addition to the catalytically active composition optionally extrusion aids such For example, bentonite, boehmite, ⁇ -alumina, zirconium oxide or conventional cerium-zirconium mixed oxide contains.
  • extrusion aids such for example, bentonite, boehmite, ⁇ -alumina, zirconium oxide or conventional cerium-zirconium mixed oxide contains.
  • the catalysts prepared in this way exhibit excellent NO x conversion rates in the temperature range from 250 ° C to 450 ° C. They are characterized in particular by excellent aging stability under hydrothermal conditions.
  • the combination of these properties causes a dynamic light-off behavior of the catalyst in the SCR reaction after metering of the reductant from a source independent of the engine (e.g., in the form of urea injection into the exhaust line) at all important operating points.
  • a source independent of the engine e.g., in the form of urea injection into the exhaust line
  • the metering strategy for the reducing agent can be made significantly simpler than in the systems according to the prior art in which, for example, exclusively zeolite-based SCR catalysts are used.
  • the mixed oxide to be used according to the invention can be used in combination with a zeolite compound and / or a zeolite-like compound.
  • the present invention also relates to a catalytically active composition
  • a catalytically active composition comprising (i) a mixed oxide consisting of cerium oxide, niobium oxide, rare earth sesquioxide and zirconium oxide and (ii) a zeolite compound and / or a zeolite-like compound containing exchangeable cations selected from the group consisting of H + , NH 4 ⁇ Fe 2+ , Fe 3+ , Cu + , Cu 2+ , Ag + or mixtures thereof.
  • the present invention further relates to a catalyst characterized in that it comprises (i) a mixed oxide consisting of cerium oxide, niobium oxide, rare earth sesquioxide and zirconium oxide and (ii) a zeolite compound and / or a zeolite-like compound which contains exchangeable cations selected from the group consisting of H + , NH 4 + , Fe 2+ , Fe 3+ , Cu + , Cu 2+ , Ag + or mixtures thereof.
  • Preferred catalytically active compositions according to the invention and preferred catalysts according to the invention comprise the mixed oxides described above as being preferred or particularly preferred.
  • the zeolite compound and / or the zeolite-like compound particularly preferably contains H + , Fe- and / or Cu cations.
  • the zeolite compound and / or the zeolite-like compound itself is preferably selected from the group consisting of zeolite beta, USY, ZSM-5, CHA, FER, ERI, SAPO-11, SAPO-17, SAPO-34, SAPO-56, ALPO- 11, ALPO-17, ALPO-34 and ALPO-56. Particular preference is given to zeolite beta, CHA, FER and SAPO-34.
  • the mixed oxide consisting of cerium oxide, niobium oxide, rare earth sesquioxide and zirconium oxide in the form of a fully extruded, catalytically active honeycomb body is present and the zeolite compound and / or zeolite-like compound is contained in a catalytically active coating applied to the honeycomb body.
  • the catalyst according to the invention is present as a coated inert supporting body, wherein the mixed oxide is contained in at least one catalytically active coating applied thereto, and the zeolite compound and / or the zeolite-like compound is contained in a spatially separate, further catalytically active coating ,
  • the mixed oxide is contained in at least one catalytically active coating applied thereto
  • the zeolite compound and / or the zeolite-like compound is contained in a spatially separate, further catalytically active coating
  • so-called "zone catalysts” in which the catalytically active coatings are designed as zones following one another in the flow direction of the exhaust gas on the support body ( Figure 1).
  • so-called “layered catalysts” may also be preferred, in which the catalytically active coatings are arranged on the support body as layers lying one above the other over the entire length of the component (FIG. 2).
  • FIGS. 1 and 2 show embodiments in which (A) is the coating containing the mixed oxide composition according to the invention, while (B) is the coating which is spatially separated therefrom and which comprises the zeolite compound and / or zeolite-like compound contains.
  • Embodiments according to FIG. 1 a) or FIG. 2 a), in which the coating containing the mixed oxide composition first comes into contact with the inflowing exhaust gas, are preferably used in applications with medium operating temperatures, in which a dynamic light-off behavior and rapid ignition With such an arrangement of the coatings, the maximum NO x conversion in the SCR reaction that is characteristic for the corresponding operating temperature can be achieved in the shortest possible time
  • the downstream zone in the flow direction of the exhaust gas or layer (B) containing the zeolite compound and / or the zeolite-like compound is used in such applications mainly to store unreacted ammonia in the first zone or layer and to break through by the first zone or layer Nitrogen oxides at operating points with particularly high ⁇ quantities and / or ge to provide characteristic NO x conversions and to catalyze the corresponding reaction.
  • Embodiments according to Figures 1 b) and 2b), in which the coating, which is the zeolite and / or the zeolite-like compound is contained, from the inflowing Exhaust gas is first contacted are preferred when a high ammonia storage is required to maintain the SCR reaction, for example, in very cold operating conditions (long cold start phases, low temperature applications), in which due to a low exhaust gas temperature level no urea can be metered.
  • An arrangement according to Figure 1 b) is further preferred in arrangements in which the SCR catalyst is exposed to very high exhaust gas temperatures.
  • the coating which contains the more age stable zeolite compounds and exhibits lower tendencies to overoxidize ammonia, is placed in the hotter upstream zone, while the downstream zone serves to complete the SCR reaction.
  • the catalytically active composition according to the invention is present in the form of a coating on a catalytically inert support body, it may be advantageous to add a binder to the coating in order to ensure improved adhesion of the catalytically active coating to the catalytically inert support body. This is especially true when metallic support bodies are used.
  • the binder is preferably selected from the group consisting of alumina, zirconia and silica. Silica is used in particular in the form of silica sol.
  • the mixed oxide of cerium oxide, zirconium oxide, rare earth sesquioxide and niobium oxide or the catalytically active composition according to the invention which additionally contains a zeolite compound and / or a zeolite-like compound, is particularly suitable for the selective catalytic reduction of nitrogen oxides.
  • the catalysts which can be produced therefrom in the described manner are particularly suitable for purifying the exhaust gases of predominantly lean-burn internal combustion engines, as used, for example, in motor vehicles (diesel vehicles, predominantly lean-burn gasoline vehicles).
  • the preferred field of application of these catalysts is the selective catalytic reduction of nitrogen oxides in the exhaust gas of predominantly lean-burn internal combustion engines after the addition of ammonia as reducing agent to the exhaust gas to be purified, optionally in the form of a decomposable compound to ammonia.
  • zone catalysts wherein (A) represents the catalytically active coating containing the composition of ceria, zirconia, rare earth sesquioxide and niobium oxide, while (B) represents a spatially separated catalytically active coating comprising a zeolite compound and / or a zeolite-like compound contains;
  • a schematic section of a monolithic fürflußwaben redesign whose flow channels are separated by gas-impermeable walls on which the catalytically active coatings (A) and (B) are applied is shown schematically.
  • Embodiments of layered catalysts according to the invention wherein (A) represents the catalytically active coating containing the composition of cerium oxide, zirconium oxide, rare earth sesquioxide and niobium oxide, while (B) is one of spatially separated catalytically active coating comprising a zeolite compound and / or a zeolite-like compound contains;
  • a schematic section of a monolithic Siriflußwaben endeavor whose flow channels are separated by gas-impermeable walls on which the catalytically active coatings (A) and (B) are applied is shown schematically.
  • Nitrogen oxide conversions in the SCR reaction measured on a composition of 38 wt .-% Ce0 2 , 14.5 wt .-% Nb 2 0 5 , 4.5 wt .-% Nd 2 0 3 and 43 wt. % Zr0 2 freshly prepared (K1 (f)), after aging at 750 ° C / 16 h (K1 (A-1)) and after aging at 600 ° C / 200 h (K1 (A-2)).
  • FIG. 7 Difference of the NH 3 storage capacity between the fresh catalyst
  • K3 (f) and its thermally pretreated at 750 ° C for 16 hours K3 (A-1) and its thermally pretreated at 750 ° C for 16 hours (K3 (A-1)) compared to VK3 (f) / VK3 (A-1).
  • FIG. 8 Dynamic light-off behavior after NH 3 -dosing of the
  • FIG. 9 Dynamic light-off behavior after NH 3 -dosing of the
  • the mixed oxide compositions prepared in the Examples and Comparative Examples described below were suspended in water, ground and applied to a ceramic honeycomb body having a volume of 0.5 L and a cell number of 62 cells per square centimeter with a wall thickness of 0.17 mm. After calcination of the honeycomb body at 500 ° C for two hours in air, cylindrical cores were removed from the coated honeycomb body for testing in a model gas plant having a diameter of 25.4 mm and a length of 76.2 mm.
  • the testing was carried out in a laboratory model gas plant under the following conditions.
  • the nitrogen oxide concentrations of the model exhaust gas were detected after catalyst with a suitable analysis. From the known, metered nitrogen oxide contents, which were verified during conditioning at the beginning of the respective test run with a pre-catalyst exhaust gas analysis, and the measured nitrogen oxide contents after catalyst, the nitrogen oxide conversion, based on the ratio of NH 3 to NO, calculated over the catalyst for each temperature measuring point as follows:
  • a commercially available cerium-zirconium mixed oxide having a weight ratio of Ce0 2 : Zr0 2 of 1: 1, 1 and a Nd 2 0 3 content of 5.3 wt .-% was impregnated with an aqueous solution of ammonium niobium oxalate and at 500 ° C calcined for a period of 2 hours.
  • the mixed oxide composition according to the invention thus obtained consisted of 38% by weight of CeO 2 , 14.5% by weight of Nb 2 O s , 4.5% by weight of Nd 2 O 3 and 43% by weight of ZrO 2 . From the mixed oxide, a coating suspension was prepared and thus coated a catalytically inert honeycomb body.
  • the catalyst thus prepared was taken from three cores. From a first drill core (K1 (f)) the catalytic activity according to the previously described test routine in the freshly prepared state was investigated. A second core (K1 (A-1)) was thermally treated in nitrogen at 750 ° C for 16 hours in an oven in an atmosphere containing 10% by volume of oxygen and 10% by volume of steam in the presence of catalytic activity. A third core (K1 (A-2)) was also thermally treated prior to analysis of catalytic activity. He became, however subjected to a thermal treatment adapted to the SCR application in the diesel vehicle, ie a thermal treatment at 600 ° C.
  • Figure 3 shows the result of the investigations of the catalytic activity:
  • the catalyst according to the invention already exhibits a nitrogen oxide conversion of more than 97% at 250 ° C.
  • the temperature window between> 250 ° C. and 400 °
  • the nitrogen oxides are completely converted by ° C.
  • the conversion curves of the thermally pretreated drill cores also show that the catalyst according to the invention has a very, very high aging stability
  • the catalyst reaches after the shortened aging at high temperatures (750 ° C, K1 (A-1)) loss of sales in the low temperature range up to 250 ° C and reach ht above 300 ° C complete NO x conversion.
  • K1 (A-2) After prolonged aging at lower temperatures (K1 (A-2)), in contrast, in the low-temperature range up to 400 ° C. virtually no conversion degradation due to thermal aging can be observed. Aging of the catalyst under these conditions can only be observed by a faster drop in the NO x conversion curve in the high-temperature range above 400 ° C.
  • Example 2 Analogously to the procedure described in Example 1, a mixed oxide of the following composition was obtained: 38% by weight CeO 2 , 14.5% by weight Nb 2 O 5 , 4.5% by weight Y 2 O 3 and 43% by weight. -% Zr0 2 .
  • Example 2 From the mixed oxide, a coating suspension was prepared as indicated in Example 1 and thus coated a catalytically inert honeycomb body.
  • the catalyst thus obtained is hereinafter referred to as K2.
  • Example 1 As indicated in Example 1, here again, a second core (K2 (A-1)) was tested for 16 hours in an oven in an atmosphere containing 10% by volume of oxygen and 10% by volume of water vapor in nitrogen thermally treated at 750 ° C.
  • the catalytic performance of the inventive catalysts according to Examples 1 and 2 in the SCR reaction was compared with two prior art catalysts:
  • a commercial SCR catalyst was selected based on vanadium oxide, which contained a catalytically active coating consisting of V 2 0 5 , W0 3 , Ti0 2 and Si0 2 .
  • a second comparative catalyst according to WO 2008/051752 was prepared which comprises a catalytically active coating consisting of 15% by weight WO 3 , 46.75% by weight ZrO 2 , 27.2% by weight CeO 2 , 5, 1 wt .-% Y 2 0 3 and 5.95 wt .-% Nb 2 0 3 on a catalytically inert honeycomb body contained.
  • the catalyst was also sampled from two cores, one of which was tested as freshly prepared (VK2 (f)), and the second core (VK2 (A-1)) was placed in an oven in an atmosphere containing 10 for 16 hours prior to testing Vol .-% oxygen and 10 vol .-% steam in nitrogen at 750 ° C was thermally treated.
  • FIG. 4 shows a comparison of the NO x conversion powers of the freshly prepared catalysts K1 (f), VK1 (f) and VK2 (f).
  • the catalyst according to the invention shows the highest working temperature window with a complete NO x conversion in the range> 250 to 400 ° C.
  • the catalyst according to the invention by far the best NO x -Konvert ists excel in the low temperature range up to 250 ° C. In the temperature range above 450 ° C, a marked “kinking" of the NO x conversion curve is observed - a reaction behavior of the comparative catalyst according to WO 2008/051752 (VK2 (f)) corresponds.
  • FIG. 5 shows a comparison of the inventive catalyst K1 (A-2) aged at 600 ° C.
  • FIG. 6 shows a comparison of the inventive catalysts K1 (A-1) and K2 (A-1) aged at 750 ° C. (16 hours) with the correspondingly aged comparative catalyst VK2 (A-1) according to WO 2008/051752. While the activity of the comparative catalyst according to WO 2008/051752 has clearly collapsed (maximum of 86% NO x conversion at 400 ° C.), the catalysts according to the invention still still reach NO x after this hot thermal treatment in the temperature range between 300 and 400 ° C. Sales close to 100% and over 95%.
  • Example 1 a second core (VK3 (A-1)) was also tested for 16 hours in an oven in an atmosphere containing 10% by volume of oxygen and 10% by volume of steam in nitrogen thermally treated at 750 ° C.
  • a layered catalyst according to FIG. 2a was produced.
  • a catalyst obtained analogously to Comparative Example 3 (amount applied 150 g / l instead of 222 g / l) was provided with an additional coating by applying a coating suspension according to Example 1 in an amount of 70 g / l again by means of a conventional dipping method and was calcined.
  • the layered catalyst thus obtained is hereinafter referred to as K3.
  • a second core (K3 (A-1)) was tested for 16 hours in an oven in an atmosphere containing 10% by volume of oxygen and 10% by volume of water vapor in nitrogen thermally treated at 750 ° C.
  • the thermal stability of the NH 3 storage capacity of K3 compared to VK3 was determined as follows:
  • test was carried out on supported catalysts in a laboratory model gas facility.
  • test gas compositions were adjusted:
  • Phase 1 empty memory, hold time 10 min (600 ° C)
  • Phase 2 cooling to target temperature (1 OK / min), hold time 5 min
  • Phase 3 NH 3 adsorption phase, holding time 20 min
  • Phase 5: heating to 600 ° C
  • the concentration is determined that leaves at padded memory the catalyst: c (NH 3) Ph3, e nd-
  • the stored amount of NH 3 at any time t is given by the difference between c (NH 3) Ph3, e nd and after the catalyst detected amount of NH 3 c (NH 3) 3 P, t:
  • a layered catalyst according to FIG. 2b) was produced.
  • the coating described in Example 2 was applied to a ceramic fürflußwaben redesign with 62 cells per square centimeter and a cell wall thickness of 0.17 millimeters in an amount of 70 g / L and calcined as described in Example 3 by a conventional dipping method.
  • a suspension containing an iron-containing ⁇ -zeolite was then applied to this coating in a quantity of 150 g / l by means of a conventional dipping process, dried and calcined as indicated in Comparative Example 3.
  • a zone catalyst according to FIG. 1a) was produced.
  • the coating described in Example 2 was applied to a ceramic fürflußwaben redesign with 62 cells per square centimeter and a cell wall thickness of 0.17 millimeters in an amount of 200 g / L, but starting from the entrance end face of the honeycomb body only 50% of its length.
  • the coating suspension described in Comparative Example 4 was then applied by a conventional dipping method, but starting from the exit end face of the honeycomb body to 50% of its length, i. up to the coating applied in the first step.
  • the zone catalyst thus obtained is referred to as K5.
  • a second core K5 (A-1) was also used in an oven for 16 hours prior to analysis of catalytic activity Atmosphere containing 10 vol .-% oxygen and 10 vol .-% steam in nitrogen at 750 ° C thermally treated.
  • Example 5 The process described in Example 5 was repeated with the difference that in the second step, instead of the coating suspension described in Comparative Example 4, the coating suspension described in Comparative Example 3 was applied.
  • the zone catalyst thus obtained is referred to as K6.
  • a second core (K6 (A-1)) was tested for 16 hours in an oven in an atmosphere containing 10% by volume of oxygen and 10% by volume of water vapor in nitrogen thermally treated at 750 ° C.
  • a coating suspension was prepared by suspending commercially available SAPO-34 in water and adding an aqueous copper (II) nitrate solution. The added amount of the copper nitrate solution was calculated such that the final catalyst contained 2% by weight of Cu based on the total weight of the exchanged zeolite-like compound.
  • the suspension was stirred for 30 minutes to complete the ion exchange, and then, after adding silica sol as a binder, directly to a ceramic flow honeycomb body of 62 cells per square centimeter and cell wall thickness of 0.165 millimeters, having a diameter of 92.96 millimeters and a length of 76 , 2 millimeters, applied.
  • the thus coated honeycomb body was dried at 90 ° C, calcined at 350 ° C and annealed for 2 hours at 640 ° in air.
  • the catalyst thus obtained is designated as VK4.
  • a second core VK4 (A-1) was also tested for 16 hours in an oven in an atmosphere containing 10% by volume of oxygen and 10% by volume of steam in nitrogen thermally treated at 750 ° C.
  • the dynamic light-off behavior after NH 3 dosing of the inventive catalysts K2 (A-1) and K6 (A-1), and of the comparative catalyst VK3 (A-1) was determined as follows:
  • test gas composition was adjusted:
  • phases A through D The test was conducted at different temperatures, which were tuned to the most application-relevant target temperature range for an SCR system downstream of other exhaust gas purification units in an exhaust system, namely 250 ° C, 300 ° C and 350 ° C. At each temperature, a cycle has been run through four distinct phases, hereafter referred to as phases A through D:
  • Phase A gas mixture 1; Duration: 5 minutes;
  • Phase B Nhb-SCR phase: gas mixture 2; Duration: up to a NHh breakthrough of 20 vppm or break-off by time;
  • Phase C gas mixture 3; Empty the NH3 storage tank by temperature ramp up
  • Phase D gas mixture 3; Adjustment of the next measurement temperature Within a cycle, the catalyst temperature was first adjusted to the defined target temperature. Then, the catalyst was charged with gas mixture 1 for 5 minutes (phase A). In Phase B, gas mixture 2 was switched to determine the Nhh-SCR conversion. This phase was terminated either by detection of an NH3 breakthrough of 20 Vppm or by a previously fixed time criterion ended. Then gas mixture 3 was adjusted and the catalyst heated to 500 ° C to empty the ammonia storage (Phase C). Subsequently, the catalyst was cooled down to the next temperature to be tested (phase D), the next cycle started with phase A by adjusting the gas mixture 1 after adjusting the target temperature. The dynamic NOx conversion was determined for all measurement temperatures from the concentrations of the respective exhaust gas components before and after the catalyst determined during phase B.
  • the NOx conversion X (NOx) is calculated, which results from the measured NOx concentration 5 seconds after the start of phase B.
  • FIG. 8 shows the determined characteristic numbers for K2 (A-1), K6 (A-1) and VK3 (A-1), in each case at 250 and 300X.
  • SCR catalysts with good properties are also obtained by replacing the mixed oxide described there in each case by one of the mixed oxides of Examples 7 to 13 in Examples 3 to 6.

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Abstract

La présente invention concerne l'utilisation d'oxydes mixtes d'oxyde de cérium, d'oxyde de zirconium, de sesquioxyde de terres rares et d'oxyde de niobium en tant que matériau catalytiquement actif pour la réduction catalytique sélective d'oxydes d'azote avec de l'ammoniac ou un composé décomposable en ammoniac dans les gaz d'échappement de moteurs à combustion principalement à mélange pauvre d'automobiles, ainsi que des compositions ou des catalyseurs qui contiennent ces oxydes mixtes en combinaison avec des composés de zéolithe et/ou des composés de type zéolithe, et qui sont appropriés pour la dénitrification de gaz d'échappement automobiles pauvres dans toutes les conditions d'exploitation essentielles.
EP11716376A 2010-04-20 2011-04-16 Nouveaux matériaux d'oxyde mixte pour la réduction catalytique sélective d'oxydes d'azote dans des gaz d'échappement Withdrawn EP2560755A1 (fr)

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EP11716376A EP2560755A1 (fr) 2010-04-20 2011-04-16 Nouveaux matériaux d'oxyde mixte pour la réduction catalytique sélective d'oxydes d'azote dans des gaz d'échappement
PCT/EP2011/001944 WO2011131324A1 (fr) 2010-04-20 2011-04-16 Nouveaux matériaux d'oxyde mixte pour la réduction catalytique sélective d'oxydes d'azote dans des gaz d'échappement

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FR2965189A1 (fr) * 2010-09-29 2012-03-30 Rhodia Operations Procede de traitement d'un gaz contenant des oxydes d'azote (nox) utilisant comme catalyseur une composition a base d'oxyde de cerium et d'oxyde de niobium
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JP5771267B2 (ja) 2015-08-26
WO2011131324A1 (fr) 2011-10-27
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US8617497B2 (en) 2013-12-31
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