EP3676000A1 - Palladium/zeolite-based passive nitrogen oxide adsorber catalyst for purifying exhaust gas - Google Patents

Palladium/zeolite-based passive nitrogen oxide adsorber catalyst for purifying exhaust gas

Info

Publication number
EP3676000A1
EP3676000A1 EP18758622.7A EP18758622A EP3676000A1 EP 3676000 A1 EP3676000 A1 EP 3676000A1 EP 18758622 A EP18758622 A EP 18758622A EP 3676000 A1 EP3676000 A1 EP 3676000A1
Authority
EP
European Patent Office
Prior art keywords
palladium
zeolite
catalyst
catalyst according
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18758622.7A
Other languages
German (de)
French (fr)
Inventor
Christoph Hengst
Frank-Walter Schuetze
Michael Lennartz
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 EP3676000A1 publication Critical patent/EP3676000A1/en
Pending legal-status Critical Current

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    • 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
    • B01J29/67—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • 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)
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    • B01D2255/9025—Three 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
    • B01D2255/904—Multiple catalysts
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1453—Sprayers or atomisers; Arrangement thereof in the exhaust apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a passive nitrogen oxide adsorber for the passive incorporation of nitrogen oxides from the exhaust gas of a combustion engine, which comprises a palladium-coated 10-ring zeolite.
  • CO carbon monoxide
  • NO x nitrogen oxides
  • HC residual hydrocarbons
  • diesel soot particulate emissions
  • liquid phase adhering to the solid components is also referred to as "Soluble Organic Fraction SOF” or “Volatile Organic Fraction VOR.”
  • Soluble Organic Fraction SOF Soluble Organic Fraction SOF
  • Volatile Organic Fraction VOR Volatile Organic Fraction VOR
  • Soot particles can be removed very effectively with the help of particle filters from the exhaust gas.
  • Wall flow filters made of ceramic materials have proven particularly useful. These are from a variety of parallel
  • first channels Built up channels formed by porous walls.
  • the channels are mutually closed at one of the two ends of the filter, so that first channels are formed, which are open on the first side of the filter and closed on the second side of the filter, and second
  • the exhaust gas flowing into the first channels can only return the filter via the second channels
  • it must flow through the porous walls between the first and second channels. As the exhaust passes through the wall, the particles are retained.
  • particle filters can be provided with catalytically active coatings.
  • EP1820561 Al describes the coating of a diesel particulate filter with a catalyst layer, which facilitates the burning of the filtered soot particles.
  • One known method for removing nitrogen oxides from exhaust gases in the presence of oxygen is Selective Catalytic Reduction (SCR) using ammonia on a suitable catalyst.
  • SCR Selective Catalytic Reduction
  • the nitrogen oxides to be removed from the exhaust gas are reacted with ammonia to nitrogen and water.
  • iron and in particular copper-exchanged zeolites can be used as SCR catalysts, see, for example, WO2008 / 106519 A1, WO2008 / 118434 A1 and WO2008 / 132452 A2.
  • SCR catalysts for the conversion of nitrogen oxides with ammonia contain no noble metals, in particular no platinum and no palladium. Namely, in the presence of these metals, the oxidation of ammonia with oxygen to nitrogen oxides would proceed preferentially and the SCR reaction
  • SCR catalysts this does not refer to the N H3-SCR reaction, but to the reduction of nitrogen oxides by means of hydrocarbons, however, the latter reaction is only slightly selective, so that instead of “SCR reaction "true” HC-DeNOx reaction "is called.
  • ammonia used as a reducing agent can be prepared by metering in an ammonia precursor compound, such as, for example, urea,
  • Ammonium carbamate or ammonium formate are made available in the exhaust line and subsequent hydrolysis.
  • SCR catalysts have the disadvantage that they only work from an exhaust gas temperature of about 180 to 200 ° C and thus do not implement nitrogen oxides that are formed in the cold start phase of the engine.
  • nitrogen oxide storage catalysts for which the term “lean NOx trap” or “LNT is customary, are known, whose cleaning effect is based on the fact that in a lean operating phase of the engine, the nitrogen oxides from the storage material of the storage catalyst predominantly in shape are stored by nitrates and this decomposes again in a subsequent rich phase of operation of the engine and the thus released nitrogen oxides with the reducing
  • Exhaust gas components are converted to the storage catalyst to nitrogen, carbon dioxide and water. This procedure is described for example in SAE SAE 950809.
  • storage materials are in particular oxides, carbonates or
  • Hydroxides of magnesium, calcium, strontium, barium, the alkali metals, the rare earth metals or mixtures thereof in question Due to their basic properties, these compounds are able to form nitrates with the acidic nitrogen oxides of the exhaust gas and produce them in this way
  • 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.
  • the US2014 / 322112 describes a zoning of the coating of the particulate filter with nitrogen oxide storage catalyst such that a zone, starting from the upstream end of the particulate filter in the
  • Operating phase of the engine stored and released in a subsequent rich operating phase is also referred to as active nitrogen oxide storage.
  • active nitrogen oxide storage also known as passive nitric oxide storage
  • nitrogen oxides are stored in a first temperature range and released again in a second temperature range, wherein the second temperature range at higher
  • Temperatures are the first temperature range.
  • passive nitrogen oxide storage catalysts are used, which are also referred to as PNA (for "passive NOx adsorber").
  • nitrogen oxides in particular at temperatures below 200 ° C., at which an SCR catalytic converter has not yet reached its operating temperature, can be stored and released again as soon as the SCR catalytic converter is ready for operation.
  • nitrogen oxides in particular at temperatures below 200 ° C., at which an SCR catalytic converter has not yet reached its operating temperature
  • a zeolite containing, for example, palladium and another metal, such as iron is known to use as a passive nitrogen oxide storage catalyst.
  • WO2015 / 085303 AI discloses passive nitrogen oxide storage catalysts containing a noble metal and a small pore molecular sieve with a maximum ring size of eight tetrahedral atoms.
  • Passive nitrogen oxide storage catalysts are also in DE102016112065A1, DE102014118096A1, DE102015119913A1, DE102008010388A1 and
  • the present invention relates to a catalyst comprising a carrier substrate of length L, palladium and a zeolite whose major channels are formed by 10 tetrahedrally coordinated atoms.
  • Zeolites are two- or three-dimensional structures whose smallest structures Si0 4 and Al0 4 tetrahedra can be considered. These tetrahedra combine to form larger structures, with two each connected via a common oxygen atom.
  • rings of different sizes can be formed, for example rings of four, six or even nine tetrahedrally coordinated silicon or aluminum atoms.
  • the different zeolite types are often defined by the largest ring size, because this size determines which guest molecules can and can not penetrate into the zeolite structure. It is common to distinguish large pore zeolites with a maximum ring size of 12, medium pore zeolites with a maximum ring size of 10 and small pore zeolites with a maximum ring size of 8.
  • Zeolites are further subdivided into structure types by the Structure Commission of the International Zeolite Association, each of which has a three-letter code, see, for example, Atlas of Zeolite
  • the catalyst according to the invention preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which correspond to the structural types * MRE, AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CSV, DAC, EUO, FER, HEU, IFW, IMF, ITH, ITR, JRY, JST, LAU, MEL, MFS, MTT, MVY, MWW, NES, OBW, -PAR, PCR, PON, PSI, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TONE, TUN, UOS, WEI or -WEN belong.
  • Zeolites of the structural type AEL are AIPO-11 and SAPO-11. Structure-type zeolites AFO are AIPO-41 and SAPO-41. A zeolite of the structural type AHT is AIPO-H2. CGS-type zeolites are TUN-1 and TsG-1. DAC zeolites are Dachiardite and Svetlozarit. Structure-type zeolites EU-1 are EU-1, TPZ-3 and ZSM-50. Zeolites of the structural type FER are ferrierite, FU-9, ISI-6, NU-23, Sr-D and ZSM-35. Zeolites of the structural type HEU are heulandite, clinoptilolite and LZ-219.
  • a structural-type zeolite IMF is IM-5.
  • ITH-type zeolites are ITQ-13 and IM-7.
  • Structural-type zeolites are Laumontite and Leonhardite.
  • Zeolites of the structural type MEL are ZSM-11, SSZ-46 and TS-2. Zeolites from
  • Structure type MFS are ZSM-57 and COK-5. Structure-type zeolites MTT are ZSM-23, EU-13, ISI-4 and KZ-1. MWW-type zeolites are MCM-22, ERB-1, ITQ-1, PSH-3 and SSZ-25. Zeolites of the structural type NES are NU-87 and Gottardite. A zeolite of the structural type OBW is OSB-2. A zeolite of the structure type -PAR is Partheit. A zeolite of the structural type PON is IST-1. A zeolite of the structural type RRO is RUB-41. A zeolite of the structural type SFF is SSZ-44. A zeolite of the structural type SFG is SSZ-58.
  • STF-type zeolites are SSZ-35, ITQ-9 and Mu-26.
  • STI-type zeolites are stilbite, barrerite, stellite and TNU-10.
  • a zeolite of the structural type SZR is SUZ-4.
  • a zeolite of the structural type TER is terranovaite.
  • TON type zeolites are theta-1, ISI-1, KZ-2, NU-10 and ZSM-22.
  • a TUN-type zeolite is TNU-9.
  • a zeolite of the structure type WEI is Weinebeneit.
  • a zeolite of the structural type -WEN is Wenkit.
  • the catalyst according to the invention particularly preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which belong to the structural type MEL, MTT, MWW or SZR.
  • the catalyst according to the invention particularly preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which belong to the structural type FER.
  • the catalyst according to the invention very particularly preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which belong to the structure type MWW.
  • Particularly preferred zeolites belonging to the structure type MEL are known from the literature. Thus, ZSM-11 is described in Nature 275, 119-120, 1978, SSZ-46 in US 5,968,474 and TS-2 in BE 1001038.
  • zeolites belonging to the structure type MWW are known from the literature.
  • SSZ-25 is described in US 4,826,667, MCM-22 in Zeolites 15, Issue 1, 2-8, 1995, ITQ-1 in US 6,077,498 and PSH-3 in US 4,439,409.
  • zeolites belonging to the structure type FER are known from the literature.
  • ZSM-35 is described in US 4,107,196, NU-23 in EP 103981 Al, FU-9 in EP 55529 Al, ISI-6 in US 4,695,440 and ferrierite for example in US 3,933,974, US 4,000,248 and US 4,251,499.
  • the catalyst according to the invention is preferred free of zeolites, whose largest channels are not formed by 10 tetrahedrally coordinated atoms.
  • the catalyst according to the invention does not comprise zeolites of the structural type LTL.
  • the catalyst according to the invention comprises palladium.
  • the palladium is preferably present as a palladium cation in the zeolite structure, that is in ion-exchanged form.
  • the palladium may also be wholly or partly present as palladium metal and / or as palladium oxide in the zeolite structure and / or on the surface of the zeolite structure.
  • the palladium may be present in amounts of from 0.01% to 20% by weight, based on the sum of the weights of zeolite and palladium and calculated as palladium metal.
  • Palladium is preferably present in amounts of from 0.5 to 10% by weight, more preferably from 1.5 to 10% by weight or 1.5 to 4% by weight and most preferably from 1.5 to 2% by weight. -% before, based on the sum of the weights of zeolite and palladium and calculated as palladium metal.
  • the catalyst according to the invention preferably contains no further metal other than palladium, in particular neither copper nor iron, nor platinum.
  • a preferred catalyst according to the invention comprises a structure-type zeolite MWW, for example MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25, and palladium as the sole metal in an amount of 1.5 to 10% by weight. , based on the sum of the weights of zeolite and palladium and calculated as palladium metal, as well as no zeolite whose largest channels are not formed by 10 tetrahedrally coordinated atoms.
  • this catalyst according to the invention does not comprise any
  • the catalyst according to the invention comprises a support body. This may be a flow-through substrate or a wall-flow filter.
  • a wall-flow filter is a support body comprising channels of length L extending in parallel between a first and a second end of the channel
  • Wall flow filters which are alternately closed either at the first or at the second end and which are separated by porous walls.
  • a flow-through substrate differs from a wall-flow filter in that the channels of length L are open at both ends.
  • the pores of the wall-flow filter are so-called open pores, that is to say they have a connection to the channels. Furthermore, the pores are usually interconnected. On the one hand, this enables the light coating of the inner pore surfaces and on the other hand easy passage of the exhaust gas through the porous walls of the wall flow filter.
  • Flow substrates are known in the art as well as wall flow filters and are available on the market. They consist for example of silicon carbide, aluminum titanate or cordierite.
  • support bodies can be used, which are constructed of corrugated sheets of inert materials.
  • Suitable inert materials are, for example, fibrous materials having an average fiber diameter of 50 to 250 pm and an average
  • Fiber length from 2 to 30 mm.
  • fibrous materials are heat-resistant and consist of silicon dioxide, in particular of
  • sheets of said fiber materials are corrugated in a known manner and the individual corrugated sheets are formed into a cylindrical monolithically structured body with the body passing channels.
  • a monolithic structured body having a criss-cross corrugation structure is formed.
  • undulating i. be arranged flat leaves.
  • Carrier bodies of corrugated sheets can be coated directly with the catalyst according to the invention, but they are preferably initially coated with an inert material, for example titanium dioxide, and only then with the catalytic material.
  • an inert material for example titanium dioxide
  • the zeolite and the palladium are in the form of a coating on the carrier substrate.
  • the coating may extend over the entire length L of the carrier substrate or only over a part thereof.
  • the coating may be on the surfaces of the input channels, on the surfaces of the output channels, and / or in the porous wall between input and output channels.
  • autoboss catalysis By coating, the person skilled in the art of autoboss catalysis understands a material zone, which is also called washcoats, and is generally applied to the support body by means of an aqueous suspension.
  • Catalysts according to the invention in which the zeolite and the palladium are present in the form of a coating on the carrier substrate can be prepared by methods familiar to the person skilled in the art, for example by the customary dip coating methods or pumping and suction coating methods followed by thermal aftertreatment ( calcination). It is known to the person skilled in the art that, in the case of wall-flow filters, their average pore size and the average particle size of the materials to be coated are superimposed on one another
  • the average particle size of the materials to be coated can also be chosen such that they are located in the porous walls that form the channels of the wall-flow filter, that is to say that a coating of the inner pore surfaces takes place (in-wall coating).
  • the mean particle size of the materials to be coated must be small enough to penetrate into the pores of the wall flow filter.
  • the zeolite and the palladium are coated over the entire length L of the carrier substrate, with no further catalytically active coating on the carrier substrate.
  • the carrier substrate may also carry one or more further catalytically active coatings.
  • the carrier substrate may comprise, in addition to a coating comprising the zeolite and the palladium, a further coating which is active in oxidation-catalytically.
  • the oxidation-catalytically active coating comprises, for example, platinum, palladium or platinum and palladium on a carrier material.
  • the mass ratio of platinum to palladium for example, at 4: 1 to 14: 1.
  • Suitable carrier materials are all those familiar to the person skilled in the art for this purpose. They have a BET surface area of 30 to 250 m 2 / g, preferably from 100 to 200 m 2 / g (determined according to DIN 66132) and are in particular alumina, silica, magnesium oxide, titanium oxide, and mixtures or mixed oxides of at least two of these Materials. Preference is given to aluminum oxide, magnesium / aluminum mixed oxides and aluminum / silicon mixed oxides. If alumina is used, it is particularly preferably stabilized, for example with 1 to 6 wt .-%, in particular 4 wt .-%, lanthanum oxide.
  • the coating comprising the zeolites and the palladium
  • coating A the oxidation-catalytically active coating
  • coating B the oxidation-catalytically active coating
  • both coatings may be coated over the entire or only over a part of the length L of the carrier substrate.
  • coating A may extend from 10 to 80% of its length L and coating B, starting from the other end of the supporting body 10 to 80% of its length LA.
  • L LA + LB
  • LA the length of the coating A
  • LB the length of the coating B.
  • L> LA + LB can also apply if part of the support body remains free of coatings. In the latter case, between the coatings A and B remains a gap which is at least 0.5 cm long, that is for example 0.5 to 1 cm.
  • the coatings A and B may also both be coated over the entire length L.
  • the coatings A and B may also both be coated over the entire length L.
  • Coating B directly on the carrier substrate and the coating A on coating B are present.
  • the coating A may also be present directly on the carrier substrate and the coating B on the coating A.
  • a coating extends over the entire length of the support body and the other only over a part thereof.
  • a zeolite of the type FER, MEL, MTT, MWW or SZR, in particular MWW, which is occupied by 1 to 2% by weight, in particular 1.5 to 2% by weight, of palladium lies directly on the
  • Carrier substrate over its entire length L and on this coating is a platinum or platinum and palladium in the mass ratio of 4: 1 to 14: 1 containing coating also over the entire length L.
  • the lower layer for example Pd-FER or Pd-MWW
  • the upper layer in an amount of 50 to 100 g / l Carrier substrate before.
  • the carrier substrate is a wall-flow filter
  • the coatings can on the walls of the input channels, on the walls of the output channels or in the walls between input and output channels.
  • the carrier substrate is the zeolite, whose largest channels are from 10
  • tetrahedrally coordinated atoms are formed, palladium and a matrix component formed.
  • catalyst substrates used inert materials can be used. These are, for example, silicates, oxides, nitrides or carbides, with particular preference being given to magnesium-aluminum silicates.
  • the extruded carrier substrate comprising the zeolites, the largest channels of which are formed of tetrahedrally coordinated atoms, and palladium may in embodiments of the present invention be coated with one or more catalytically active coatings, for example with the above-described oxidation-catalytically active coating.
  • the catalyst of the invention is outstandingly useful as a passive nitrogen oxide storage catalyst, i. it is able to store nitrogen oxides at temperatures below 200 ° C and to recycle them at temperatures above 200 ° C.
  • the present invention thus also relates to the use of a
  • a catalyst comprising a carrier substrate of length L, palladium and a zeolite, the largest channels of which are formed by 10 tetrahedrally coordinated atoms, as a passive nitrogen oxide storage catalyst containing nitrogen oxides in stores a first temperature range and in a second
  • the present invention relates to the use of a catalyst comprising a carrier substrate of length L, a structure-type zeolite MWW, for example MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25, and palladium as the sole metal in in an amount of 1.5 to 10% by weight, based on the sum of the weights of zeolite and palladium and calculated as palladium metal, and no zeolites whose largest channels are not formed by 10 tetrahedrally coordinated atoms.
  • a catalyst comprising a carrier substrate of length L, a structure-type zeolite MWW, for example MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25, and palladium as the sole metal in in an amount of 1.5 to 10% by weight, based on the sum of the weights of zeolite and palladium and calculated as palladium metal, and no zeolites whose largest channels are not formed by 10 tetrahedrally coordinated atoms
  • the catalyst according to the invention in combination with a downstream SCR catalyst, allows nitrogen oxides over the entire
  • Temperature range of the exhaust gas including the cold start temperatures to implement effectively.
  • the present invention thus also relates to an exhaust gas system comprising a) a catalyst tetrahedrally coordinating a carrier substrate of length L, palladium and a zeolite whose largest channels of 10
  • Atoms are formed, includes and
  • the SCR catalyst in the exhaust system according to the invention can in principle be selected from all in the SCR reaction of nitrogen oxides with
  • Catalysts based on zeolites in particular transition metal-exchanged zeolites.
  • SCR catalysts that have a small pore zeolite with a maximum
  • Ring size of eight tetrahedral atoms and a transition metal included used.
  • SCR catalysts are described, for example, in WO2008 / 106519 A1, WO2008 / 118434 A1 and WO2008 / 132452 A2.
  • large and medium pore zeolites can be used, in particular those of the structure type BEA come into question.
  • iron BEA and copper BEA are of interest.
  • zeolites belong to the framework types BEA, AEI, CHA, KFI, ERI, LEV, MER or DDR and are particularly preferred with cobalt, iron, copper or mixtures of two or three of these metals
  • zeolites also includes molecular sieves, sometimes referred to as "zeolite-like" compounds
  • Preferred zeolites are furthermore those which have a SAR (silica-to-alumina ratio) value of from 2 to 100, in particular from 5 to 50.
  • SAR silicon-to-alumina ratio
  • the zeolites or molecular sieves contain transition metal, in particular in amounts of from 1 to 10% by weight, in particular from 2 to 5% by weight, calculated as metal oxide, ie for example as Fe 2 O 3 or CuO.
  • Preferred embodiments of the present invention include SCR catalysts with copper, iron or copper and iron exchanged zeolites or beta-type molecular sieves (BEA), chabazite type (CHA) or Levyne type (LEV).
  • BEA beta-type molecular sieves
  • CHA chabazite type
  • LEV Levyne type
  • Corresponding zeolites or molecular sieves are
  • the exhaust system according to the invention is located between the catalyst, which is a carrier substrate of length L,
  • the injection device can be chosen arbitrarily by the person skilled in the art, suitable devices being able to be taken from the literature (see, for example, T. Mayer, Solid-SCR System Based on Ammonium Carbamate, Dissertation, TU Kaiserslautern, 2005).
  • the ammonia can be introduced via the injection device as such or in the form of a compound in the exhaust stream from which ammonia is formed at ambient conditions.
  • aqueous solutions of urea or ammonium formate in question, as well as solid ammonium carbamate As such, for example, aqueous solutions of urea or ammonium formate in question, as well as solid ammonium carbamate.
  • the SCR catalyst is preferably in the form of a coating on a supporting body, which may be a flow-through substrate or a wall-flow filter and may consist, for example, of silicon carbide, aluminum titanate or cordierite.
  • the support body itself may consist of the SCR catalyst and a matrix component as described above, that is, in extruded form.
  • the present invention also relates to a method for purifying exhaust gases of motor vehicles which are operated with lean-burn engines, such as diesel engines, characterized in that the exhaust gas is passed through an exhaust system according to the invention.
  • a zeolite of the structural type FER is impregnated with 3% by weight of palladium (from commercially available palladium nitrate) ("incipient
  • Ceramic substrate (flow-through substrate) over its entire length coated by a conventional method.
  • the washcoat loading is 50 g / L, based on the Pd-containing zeolite (equivalent to 54 g / L including binder), which corresponds to a precious metal loading of 42.5 g / ft 3 Pd.
  • the catalyst thus obtained is calcined at 550 ° C.
  • Example 1 is repeated with the difference that the ceramic substrate is coated with 100 g / l Pd-containing zeolite (corresponds to 108 g / L including binder). This corresponds to a noble metal loading of 85 g / ft 3 Pd.
  • Example 1 is repeated with the difference that the ceramic substrate is coated with 200 g / l Pd-containing zeolite (corresponds to 216 g / L including binder). This corresponds to a noble metal loading of 170 g / ft 3 Pd.
  • Example 4 Example 2 is repeated with the difference that the zeolite is impregnated with 1.5% by weight of palladium. This corresponds to a noble metal loading of 42.5 g / ft 3 Pd.
  • Example 5
  • Example 3 is repeated with the difference that the zeolite is impregnated with 1.5% by weight of palladium. This corresponds to a noble metal loading of 85 g / ft 3 Pd.
  • Example 6 is repeated with the difference that the zeolite is impregnated with 1.5% by weight of palladium. This corresponds to a noble metal loading of 85 g / ft 3 Pd.
  • Example 3 is repeated with the difference that the zeolite is impregnated with 0.75 wt .-% palladium. This corresponds to a noble metal loading of 42.5 g / ft 3 Pd.
  • Example 7
  • the catalyst obtained according to Example 5 is also coated in a further step by a conventional method also over its entire length with a washcoat containing platinum supported on alumina.
  • the washcoat loading of the second layer is 75 g / L, the platinum loading is 20 g / ft 3 .
  • the catalyst of Example 7 is combined with a second coated flow-through substrate to form an exhaust system.
  • the second flow-through substrate is exchanged with a zeolite of the structure type chabazite exchanged with 3% by weight of copper (calculated as CuO).
  • the washcoat loading of the second flow substrate is 150 g / L.
  • Example 1 is repeated with the difference that a structure-type zeolite MWW was used.

Abstract

The invention relates to a catalyst which comprises a carrier substrate, palladium, and a zeolite, the largest channels of which are formed by 10 tetradrically coordinated atoms; to the use of said catalyst as a passive nitrogen oxide adsorber, an exhaust gas system which contains said catalyst and an SCR catalyst, and to a method for purifying the exhaust gas of motor vehicles using said exhaust gas system.

Description

PALLADIUM-ZEOLITH-BASIERTER PASSIVER STICKOXID-ADSORBER-KATALYSATOR  PALLADIUM ZEOLITE BASED PASSIVE STAIN OXIDE ADSORBER CATALYST
ZUR ABGASREINIGUNG  FOR EMISSION CONTROL
Die vorliegende Erfindung betrifft einen passiven Stickoxid-Adsorber zur passiven Einlagerung von Stickoxiden aus dem Abgas eines Verbrennungs- motors, der einen mit Palladium belegten 10-Ring-Zeolithen umfasst. The present invention relates to a passive nitrogen oxide adsorber for the passive incorporation of nitrogen oxides from the exhaust gas of a combustion engine, which comprises a palladium-coated 10-ring zeolite.
Das Abgas von Kraftfahrzeugen, die mit mager betriebenen Verbrennungsmotoren, beispielsweise mit Dieselmotoren, betrieben werden, enthält neben Kohlenmonoxid (CO) und Stickoxiden (NOx) auch Bestandteile, die aus der unvollständigen Verbrennung des Kraftstoffs im Brennraum des Zylinders herrühren. Dazu gehören neben Rest-Kohlenwasserstoffen (HC), die meist ebenfalls überwiegend gasförmig vorliegen, Partikelemissionen, auch als„Dieselruß" oder„Rußpartikel" bezeichnet. Dabei handelt es sich um komplexe Agglomerate aus überwiegend Kohlenstoff-haltigen Feststoff- Teilchen und einer anhaftenden Flüssigphase, die meist mehrheitlich aus längerkettigen Kohlenwasserstoff-Kondensaten besteht. Die auf den festen Bestandteilen anhaftende Flüssigphase wird auch als„Soluble Organic Fraction SOF" oder„Volatile Organic Fraction VOR' bezeichnet. Zur Reinigung dieser Abgase müssen die genannten Bestandteile möglichst vollständig in unschädliche Verbindungen umgewandelt werden, was nur unter Einsatz geeigneter Katalysatoren möglich ist. 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. In addition to residual hydrocarbons (HC), which are also mostly present in gaseous form, these include particulate emissions, also referred to as "diesel soot" or "soot particles". 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 VOR." To purify these exhaust gases, the constituents mentioned must be converted as completely as possible into harmless compounds, which is possible only with the use of suitable catalysts.
Rußpartikel können sehr effektiv mit Hilfe von Partikelfiltern aus dem Abgas entfernt werden. Besonders bewährt haben sich Wandflussfilter aus keramischen Materialien. Diese sind aus einer Vielzahl von parallelen Soot particles can be removed very effectively with the help of particle filters from the exhaust gas. Wall flow filters made of ceramic materials have proven particularly useful. These are from a variety of parallel
Kanälen aufgebaut, die durch poröse Wände gebildet werden. Die Kanäle sind wechselseitig an einem der beiden Enden des Filters verschlossen, so dass erste Kanäle gebildet werden, die an der ersten Seite des Filters offen und auf der zweiten Seite des Filters verschlossen sind, sowie zweite  Built up channels formed by porous walls. The channels are mutually closed at one of the two ends of the filter, so that first channels are formed, which are open on the first side of the filter and closed on the second side of the filter, and second
Kanäle, die an der ersten Seite des Filters verschlossen und auf der zweiten Seite des Filters offen sind . Das beispielsweise in die ersten Kanäle einströmende Abgas kann den Filter nur über die zweiten Kanäle wieder verlassen und muss zu diesem Zweck durch die porösen Wände zwischen den ersten und zweiten Kanälen durchfließen. Beim Durchtritt des Abgases durch die Wand werden die Partikel zurückgehalten. Channels closed on the first side of the filter and open on the second side of the filter. The exhaust gas flowing into the first channels, for example, can only return the filter via the second channels For this purpose, it must flow through the porous walls between the first and second channels. As the exhaust passes through the wall, the particles are retained.
Es ist bekannt, dass Partikelfilter mit katalytisch aktiven Beschichtungen versehen werden können. So beschreibt beispielsweise die EP1820561 AI die Beschichtung eines Dieselpartikelfilters mit einer Katalysatorschicht, die das Abbrennen der gefilterten Rußpartikel erleichtert. It is known that particle filters can be provided with catalytically active coatings. For example, EP1820561 Al describes the coating of a diesel particulate filter with a catalyst layer, which facilitates the burning of the filtered soot particles.
Ein bekanntes Verfahren zur Entfernung von Stickoxiden aus Abgasen in Gegenwart von Sauerstoff ist die selektive katalytische Reduktion (SCR- Verfahren) mittels Ammoniak an einem geeigneten Katalysator. Bei diesem Verfahren werden die aus dem Abgas zu entfernenden Stickoxide mit Ammoniak zu Stickstoff und Wasser umgesetzt. One known method for removing nitrogen oxides from exhaust gases in the presence of oxygen is Selective Catalytic Reduction (SCR) using ammonia on a suitable catalyst. In this method, the nitrogen oxides to be removed from the exhaust gas are reacted with ammonia to nitrogen and water.
Als SCR-Katalysatoren können beispielsweise Eisen- und insbesondere Kupfer-ausgetauschte Zeolithe verwendet werden, siehe zum Beispiel WO2008/106519 AI, WO2008/118434 AI und WO2008/132452 A2.  For example, iron and in particular copper-exchanged zeolites can be used as SCR catalysts, see, for example, WO2008 / 106519 A1, WO2008 / 118434 A1 and WO2008 / 132452 A2.
SCR-Katalysatoren für die Umsetzung von Stickoxiden mit Ammoniak enthalten keine Edelmetalle, insbesondere kein Platin und kein Palladium. In Gegenwart dieser Metalle würde nämlich die Oxidation von Ammoniak mit Sauerstoff zu Stickoxiden bevorzugt ablaufen und die SCR-Reaktion SCR catalysts for the conversion of nitrogen oxides with ammonia contain no noble metals, in particular no platinum and no palladium. Namely, in the presence of these metals, the oxidation of ammonia with oxygen to nitrogen oxides would proceed preferentially and the SCR reaction
(Umsetzung von Ammoniak mit Stickoxid) ins Hintertreffen geraten. Soweit in der Literatur bisweilen von Platin- bzw. Palladium-ausgetauschten  (Implementation of ammonia with nitric oxide) fall behind. As far as in the literature sometimes of platinum or palladium exchanged
Zeolithen als„SCR-Katalysatoren" die Rede ist, so bezieht sich dies nicht auf die N H3-SCR-Reaktion, sondern auf die Reduktion von Stickoxiden mittels Kohlenwasserstoffen. Allerdings ist letztgenannte Umsetzung nur wenig selektiv, so dass sie statt„SCR-Reaktion" zutreffender„HC-DeNOx- Reaktion" genannt wird . Zeolites are referred to as "SCR catalysts", this does not refer to the N H3-SCR reaction, but to the reduction of nitrogen oxides by means of hydrocarbons, however, the latter reaction is only slightly selective, so that instead of "SCR reaction "true" HC-DeNOx reaction "is called.
Der als Reduktionsmittel verwendete Ammoniak kann durch Eindosierung einer Ammoniakvorläuferverbindung, wie beispielsweise Harnstoff,  The ammonia used as a reducing agent can be prepared by metering in an ammonia precursor compound, such as, for example, urea,
Ammoniumcarbamat oder Ammoniumformiat, in den Abgasstrang und anschließende Hydrolyse verfügbar gemacht werden. SCR-Katalysatoren haben den Nachteil, dass sie erst ab einer Abgastemperatur von ca. 180 bis 200°C arbeiten und somit Stickoxide, die in der Kaltstartphase des Motors gebildet werden, nicht umsetzen. Zur Entfernung der Stickoxide sind daneben sogenannte Stickoxid-Speicherkatalysatoren, für die auch der Begriff„Lean NOx Trap" oder„LNT üblich ist, bekannt. Deren Reinigungswirkung beruht darauf, dass in einer mageren Betriebsphase des Motors die Stickoxide vom Speichermaterial des Speicherkatalysators vorwiegend in Form von Nitraten gespeichert werden und diese in einer darauf folgenden fetten Betriebsphase des Motors wieder zersetzt und die so freiwerdenden Stickoxide mit den reduzierenden Ammonium carbamate or ammonium formate, are made available in the exhaust line and subsequent hydrolysis. SCR catalysts have the disadvantage that they only work from an exhaust gas temperature of about 180 to 200 ° C and thus do not implement nitrogen oxides that are formed in the cold start phase of the engine. For the removal of the nitrogen oxides, so-called nitrogen oxide storage catalysts, for which the term "lean NOx trap" or "LNT is customary, are known, whose cleaning effect is based on the fact that in a lean operating phase of the engine, the nitrogen oxides from the storage material of the storage catalyst predominantly in shape are stored by nitrates and this decomposes again in a subsequent rich phase of operation of the engine and the thus released nitrogen oxides with the reducing
Abgasanteilen am Speicherkatalysator zu Stickstoff, Kohlendioxid und Wasser umgesetzt werden. Diese Arbeitsweise ist beispielsweise in der SAE- Schrift SAE 950809 beschrieben. Exhaust gas components are converted to the storage catalyst to nitrogen, carbon dioxide and water. This procedure is described for example in SAE SAE 950809.
Als Speichermaterialien kommen insbesondere Oxide, Carbonate oderAs storage materials are in particular oxides, carbonates or
Hydroxide von Magnesium, Calcium, Strontium, Barium, der Alkalimetalle, der Seltenerdmetalle oder Mischungen davon in Frage. Diese Verbindungen sind aufgrund ihrer basischen Eigenschaften in der Lage, mit den sauren Stickoxiden des Abgases Nitrate zu bilden und sie auf diese Weise Hydroxides of magnesium, calcium, strontium, barium, the alkali metals, the rare earth metals or mixtures thereof in question. Due to their basic properties, these compounds are able to form nitrates with the acidic nitrogen oxides of the exhaust gas and produce them in this way
abzuspeichern. Sie sind zur Erzeugung einer großen Wechselwirkungsfläche mit dem Abgas in möglichst hoher Dispersion auf geeigneten save. They are suitable for generating a large interaction area with the exhaust gas in the highest possible dispersion
Trägermaterialien abgeschieden. Stickoxid-Speicherkatalysatoren enthalten darüber hinaus in der Regel Edelmetalle wie Platin, Palladium und/oder Rhodium als katalytisch aktive Komponenten. Deren Aufgabe ist es einerseits, unter mageren Bedingungen NO zu NO2, sowie CO und HC zu CO2 zu oxidieren und andererseits während der fetten Betriebsphasen, in denen der Stickoxid-Speicherkatalysator regeneriert wird, freigesetztes NO2 zu Stickstoff zu reduzieren. Support materials deposited. In addition, 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.
Moderne Stickoxid-Speicherkatalysatoren sind beispielsweise in EP0885650 A2, US2009/320457, WO2012/029050 AI und WO2016/020351 AI beschrieben. Es ist bereits bekannt, Rußpartikelfilter und Stickoxid-Speicherkatalysatoren zu kombinieren. So beschreiben beispielsweise die EP1420 149 A2 und die US2008/141661 Systeme aus einem Dieselpartikelfilter und einem abströmseitig angeordneten Stickoxid-Speicherkatalysator. Modern nitrogen oxide storage catalysts are described for example in EP0885650 A2, US2009 / 320457, WO2012 / 029050 AI and WO2016 / 020351 AI. It is already known to combine soot particle filters and nitrogen oxide storage catalysts. For example, EP1420 149 A2 and US2008 / 141661 describe systems comprising a diesel particle filter and a nitrogen oxide storage catalytic converter arranged downstream.
Darüber hinaus ist bereits in beispielsweise EP1393069 A2, EP1433519 AI, EP2505803 A2 und US2014/322112 vorgeschlagen worden, Partikelfilter mit Stickoxid-Speicherkatalysatoren zu beschichten. In addition, it has already been proposed in, for example, EP1393069 A2, EP1433519 A1, EP2505803 A2 and US2014 / 322112 to coat particle filters with nitrogen oxide storage catalysts.
Die US2014/322112 beschreibt eine Zonierung der Beschichtung des Partikelfilters mit Stickoxid-Speicherkatalysator dergestalt, dass sich eine Zone ausgehend vom anströmseitigen Ende des Partikelfilters in den The US2014 / 322112 describes a zoning of the coating of the particulate filter with nitrogen oxide storage catalyst such that a zone, starting from the upstream end of the particulate filter in the
Eingangskanälen und eine andere Zone ausgehend vom abströmseitigen Ende des Partikelfilters in den Ausgangskanälen befindet. Input channels and another zone from the downstream end of the particulate filter located in the output channels.
Die in der SAE-Schrift SAE 950809 beschriebene Arbeitsweise, bei der Stickoxide von einem Stickoxid-Speicherkatalysator in einer magerenThe procedure described in SAE SAE 950809, in which nitrogen oxides from a nitrogen oxide storage catalyst in a lean
Betriebsphase des Motors gespeichert und in einer darauf folgenden fetten Betriebsphase wieder freigesetzt werden, wird auch als aktive Stickoxid- Speicherung bezeichnet. Daneben ist auch ein als passive Stickoxid-Speicherung bekanntes Operating phase of the engine stored and released in a subsequent rich operating phase is also referred to as active nitrogen oxide storage. In addition, also known as passive nitric oxide storage
Verfahren beschrieben worden. Dabei werden Stickoxide in einem ersten Temperaturbereich gespeichert und in einem zweiten Temperaturbereich wieder freigesetzt, wobei der zweite Temperaturbereich bei höheren  Method has been described. In this case, nitrogen oxides are stored in a first temperature range and released again in a second temperature range, wherein the second temperature range at higher
Temperaturen liegt als der erste Temperaturbereich. Zur Durchführung dieses Verfahrens werden passive Stickoxid-Speicherkatalysatoren verwendet, die auch als PNA (für„passive NOx-Adsorber") bezeichnet werden. Temperatures are the first temperature range. To carry out this process, passive nitrogen oxide storage catalysts are used, which are also referred to as PNA (for "passive NOx adsorber").
Mittels passiver Stickoxid-Speicherkatalysatoren können Stickoxide insbesondere bei Temperaturen unter 200°C, bei denen ein SCR-Katalysator seine Betriebstemperatur noch nicht erreicht hat, gespeichert werden und wieder freigesetzt werden, sobald der SCR-Katalysator betriebsbereit ist. Somit wird durch die Zwischenspeicherung der vom Motor emittierten Stickoxide unterhalb von 200°C, sowie die konzertierte Freisetzung jener Stickoxide oberhalb von 200°C eine gesteigerte Gesamt-Stickoxid- Umsetzung des Abgasnachbehandlungssystems realisiert. By means of passive nitrogen oxide storage catalysts, nitrogen oxides, in particular at temperatures below 200 ° C., at which an SCR catalytic converter has not yet reached its operating temperature, can be stored and released again as soon as the SCR catalytic converter is ready for operation. Thus, by caching the emissions of nitrogen emitted by the engine below 200 ° C, as well as the concerted release of Nitrogen oxides realized above 200 ° C an increased overall nitrogen oxide conversion of the exhaust aftertreatment system.
Als passiver Stickoxid-Speicherkatalysator ist auf Ceroxid geträgertes Palladium beschrieben worden, siehe zum Beispiel WO2008/047170 AI und WO2014/184568 AI, das gemäß WO2012/071421 A2 und WO2012/156883 AI auch auf einen Partikelfilter beschichtet werden kann. As a passive nitrogen oxide storage catalyst palladium supported on cerium oxide has been described, see for example WO2008 / 047170 AI and WO2014 / 184568 AI, which can be coated on a particulate filter according to WO2012 / 071421 A2 and WO2012 / 156883 AI.
Aus WO2012/166868 AI ist bekannt, als passiven Stickoxid-Speicherkatalysator einen Zeolithen zu verwenden, der beispielsweise Palladium und ein weiteres Metall, wie zum Beispiel Eisen, enthält. From WO2012 / 166868 Al it is known to use as a passive nitrogen oxide storage catalyst, a zeolite containing, for example, palladium and another metal, such as iron.
Die WO2015/085303 AI offenbart passive Stickoxid-Speicherkatalysatoren, die ein Edelmetall und ein kleinporiges Molekularsieb mit einer maximalen Ringgröße von acht tetraedrischen Atomen enthalten.  WO2015 / 085303 AI discloses passive nitrogen oxide storage catalysts containing a noble metal and a small pore molecular sieve with a maximum ring size of eight tetrahedral atoms.
Passive Stickoxid-Speicherkatalysatoren sind auch in DE102016112065A1, DE102014118096A1, DE102015119913A1, DE102008010388A1 und Passive nitrogen oxide storage catalysts are also in DE102016112065A1, DE102014118096A1, DE102015119913A1, DE102008010388A1 and
DE102015113415A1 offenbart. Palladium enthaltende Zeolithe sind daneben aus EP427970A2, US2015/217282, DE102008010388A1 und  DE102015113415A1 discloses. Palladium-containing zeolites are also known from EP427970A2, US2015 / 217282, DE102008010388A1 and
DE102015113415A1 bekannt. Moderne und zukünftige Dieselmotoren werden immer effizienter, wodurch auch die Abgastemperaturen sinken. Parallel dazu werden die Gesetzgebungen hinsichtlich des Umsatzes von Stickoxiden kontinuierlich strenger. Dies führt dazu, dass SCR-Katalysatoren alleine nicht mehr ausreichen, um die Stickoxid-Grenzwerte einzuhalten. Es besteht insbesondere weiter Bedarf nach technischen Lösungen, die gewährleisten, dass in der Kaltstartphase des Motors gebildete Stickoxide nicht in die Umwelt entweichen . DE102015113415A1 known. Modern and future diesel engines are becoming increasingly efficient, as a result of which exhaust gas temperatures are also falling. At the same time, legislation on nitrogen oxide sales is becoming increasingly stringent. As a result, SCR catalysts alone are no longer sufficient to meet the nitrogen oxide limits. In particular, there is still a need for technical solutions which ensure that nitrogen oxides formed in the cold start phase of the engine do not escape into the environment.
Es wurde nun gefunden, dass mit Palladium belegte Zeolithe, deren It has now been found that palladium-coated zeolites whose
Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden, hervorragende passive Stickoxidadsorbereigenschaften aufweisen. Die vorliegende Erfindung betrifft demnach einen Katalysator, der ein Trägersubstrat der Länge L, Palladium und einen Zeolithen, dessen größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden, umfasst. Zeolithe sind zwei- oder dreidimensionale Strukturen, als deren kleinste Strukturen Si04- und AI04-Tetraeder angesehen werden können. Diese Tetraeder fügen sich zu größeren Strukturen zusammen, wobei jeweils zwei über ein gemeinsames Sauerstoffatom verbunden sind. Dabei können Ringe verschiedener Größe gebildet werden, beispielsweise Ringe aus vier, sechs oder auch neun tetraedrisch koordinierten Silizium- oder Aluminiumatomen. Die verschiedenen Zeolithtypen werden häufig über die größte Ringgröße definiert, weil diese Größe bestimmt, welche Gastmoleküle in die Zeolith- struktur eindringen können und welche nicht. Es ist geläufig, großporige Zeolithe mit einer maximalen Ringgröße von 12, mittelporige Zeolithe mit einer maximalen Ringgröße von 10 und kleinporige Zeolithe mit einer maximalen Ringgröße von 8 zu unterscheiden. Channels of 10 tetrahedrally coordinated atoms are formed, have excellent passive nitrogen oxide adsorber properties. Accordingly, the present invention relates to a catalyst comprising a carrier substrate of length L, palladium and a zeolite whose major channels are formed by 10 tetrahedrally coordinated atoms. Zeolites are two- or three-dimensional structures whose smallest structures Si0 4 and Al0 4 tetrahedra can be considered. These tetrahedra combine to form larger structures, with two each connected via a common oxygen atom. In this case, rings of different sizes can be formed, for example rings of four, six or even nine tetrahedrally coordinated silicon or aluminum atoms. The different zeolite types are often defined by the largest ring size, because this size determines which guest molecules can and can not penetrate into the zeolite structure. It is common to distinguish large pore zeolites with a maximum ring size of 12, medium pore zeolites with a maximum ring size of 10 and small pore zeolites with a maximum ring size of 8.
Zeolithe werden des Weiteren von der Strukturkommision der International Zeolite Association in Strukturtypen unterteilt, die jeweils mit einem Code aus drei Buchstaben belegt sind, siehe zum Beispiel Atlas of Zeolite  Zeolites are further subdivided into structure types by the Structure Commission of the International Zeolite Association, each of which has a three-letter code, see, for example, Atlas of Zeolite
Framework Types, Elsevier, 5. Auflage, 2001. Framework Types, Elsevier, 5th edition, 2001.
Der erfindungsgemäße Katalysator umfasst bevorzugt Zeolithe, deren größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden und die den Strukturtypen *MRE, AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CSV, DAC, EUO, FER, HEU, IFW, IMF, ITH, ITR, JRY, JST, LAU, MEL, MFS, MTT, MVY, MWW, NES, OBW, -PAR, PCR, PON, PSI, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TON, TUN, UOS, WEI oder -WEN angehören. The catalyst according to the invention preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which correspond to the structural types * MRE, AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CSV, DAC, EUO, FER, HEU, IFW, IMF, ITH, ITR, JRY, JST, LAU, MEL, MFS, MTT, MVY, MWW, NES, OBW, -PAR, PCR, PON, PSI, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TONE, TUN, UOS, WEI or -WEN belong.
Zeolithe vom Strukturtyp AEL sind AIPO-11 und SAPO-11. Zeolithe vom Strukturtyp AFO sind AIPO-41 und SAPO-41. Ein Zeolith vom Strukturtyp AHT ist AIPO-H2. Zeolithe vom Strukturtyp CGS sind TUN-1 und TsG-1. Zeolithe vom Strukturtyp DAC sind Dachiardit und Svetlozarit. Zeolithe vom Strukturtyp EUO sind EU-1, TPZ-3 und ZSM-50. Zeolithe vom Strukturtyp FER sind Ferrierit, FU-9, ISI-6, NU-23, Sr-D und ZSM-35. Zeolithe vom Strukturtyp HEU sind Heulandit, Clinoptilolit und LZ-219. Ein Zeolith vom Strukturtyp IMF ist IM-5. Zeolithe vom Strukturtyp ITH sind ITQ-13 und IM- 7. Zeolithe vom Strukturtyp LAU sind Laumontit und Leonhardit. Zeolithe vom Strukturtyp MEL sind ZSM-11, SSZ-46 und TS-2. Zeolithe vom Zeolites of the structural type AEL are AIPO-11 and SAPO-11. Structure-type zeolites AFO are AIPO-41 and SAPO-41. A zeolite of the structural type AHT is AIPO-H2. CGS-type zeolites are TUN-1 and TsG-1. DAC zeolites are Dachiardite and Svetlozarit. Structure-type zeolites EU-1 are EU-1, TPZ-3 and ZSM-50. Zeolites of the structural type FER are ferrierite, FU-9, ISI-6, NU-23, Sr-D and ZSM-35. Zeolites of the structural type HEU are heulandite, clinoptilolite and LZ-219. A structural-type zeolite IMF is IM-5. ITH-type zeolites are ITQ-13 and IM-7. Structural-type zeolites are Laumontite and Leonhardite. Zeolites of the structural type MEL are ZSM-11, SSZ-46 and TS-2. Zeolites from
Strukturtyp MFS sind ZSM-57 und COK-5. Zeolithe vom Strukturtyp MTT sind ZSM-23, EU-13, ISI-4 und KZ-1. Zeolithe vom Strukturtyp MWW sind MCM-22, ERB-1, ITQ-1, PSH-3 und SSZ-25. Zeolithe vom Strukturtyp NES sind NU-87 und Gottardit. Ein Zeolith vom Strukturtyp OBW ist OSB-2. Ein Zeolith vom Strukturtyp -PAR ist Partheit. Ein Zeolith vom Strukturtyp PON ist IST-1. Ein Zeolith vom Strukturtyp RRO ist RUB-41. Ein Zeolith vom Strukturtyp SFF ist SSZ-44. Ein Zeolith vom Strukturtyp SFG ist SSZ-58. Zeolithe vom Strukturtyp STF sind SSZ-35, ITQ-9 und Mu-26. Zeolithe vom Strukturtyp STI sind Stilbit, Barrerit, Stellerit und TNU-10. Ein Zeolith vom Strukturtyp SZR ist SUZ-4. Ein Zeolith vom Strukturtyp TER ist Terranovait. Zeolithe vom Strukturtyp TON sind Theta-1, ISI-1, KZ-2, NU-10 und ZSM- 22. Ein Zeolith vom Strukturtyp TUN ist TNU-9. Ein Zeolith vom Strukturtyp WEI ist Weinebeneit. Ein Zeolith vom Strukturtyp -WEN ist Wenkit. Der erfindungsgemäße Katalysator umfasst besonders bevorzugt Zeolithe, deren größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden und die dem Strukturtyp MEL, MTT, MWW oder SZR angehören.  Structure type MFS are ZSM-57 and COK-5. Structure-type zeolites MTT are ZSM-23, EU-13, ISI-4 and KZ-1. MWW-type zeolites are MCM-22, ERB-1, ITQ-1, PSH-3 and SSZ-25. Zeolites of the structural type NES are NU-87 and Gottardite. A zeolite of the structural type OBW is OSB-2. A zeolite of the structure type -PAR is Partheit. A zeolite of the structural type PON is IST-1. A zeolite of the structural type RRO is RUB-41. A zeolite of the structural type SFF is SSZ-44. A zeolite of the structural type SFG is SSZ-58. STF-type zeolites are SSZ-35, ITQ-9 and Mu-26. STI-type zeolites are stilbite, barrerite, stellite and TNU-10. A zeolite of the structural type SZR is SUZ-4. A zeolite of the structural type TER is terranovaite. TON type zeolites are theta-1, ISI-1, KZ-2, NU-10 and ZSM-22. A TUN-type zeolite is TNU-9. A zeolite of the structure type WEI is Weinebeneit. A zeolite of the structural type -WEN is Wenkit. The catalyst according to the invention particularly preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which belong to the structural type MEL, MTT, MWW or SZR.
Der erfindungsgemäße Katalysator umfasst besonders bevorzugt Zeolithe, deren größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden und die dem Strukturtyp FER angehören. The catalyst according to the invention particularly preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which belong to the structural type FER.
Der erfindungsgemäße Katalysator umfasst ganz besonders bevorzugt Zeolithe, deren größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden und die dem Strukturtyp MWW angehören. Besonders bevorzugte Zeolithe, die dem Strukturtyp MEL angehören sind literaturbekannt. So ist ZSM-11 in Nature 275, 119-120, 1978, SSZ-46 in US 5,968,474 und TS-2 in BE 1001038 beschrieben. The catalyst according to the invention very particularly preferably comprises zeolites whose largest channels are formed by 10 tetrahedrally coordinated atoms and which belong to the structure type MWW. Particularly preferred zeolites belonging to the structure type MEL are known from the literature. Thus, ZSM-11 is described in Nature 275, 119-120, 1978, SSZ-46 in US 5,968,474 and TS-2 in BE 1001038.
Besonders bevorzugte Zeolithe, die dem Strukturtyp MTT angehören sind literaturbekannt. So ist ZSM-23 in US 4,076,842, EU-13 in US 4,705,674 und ISI-4 in US 4,657,750 beschrieben. Daneben befasst sich die US Particularly preferred zeolites belonging to the structure type MTT are known from the literature. Thus, ZSM-23 is described in US 4,076,842, EU-13 in US 4,705,674 and ISI-4 in US 4,657,750. Next to it is the US
5,314,674 mit der Synthese von Zeolithen des Strukturtyps MTT. 5,314,674 with the synthesis of zeolites of the structure type MTT.
Ganz besonders bevorzugte Zeolithe, die dem Strukturtyp MWW angehören sind literaturbekannt. So ist SSZ-25 in US 4,826,667, MCM-22 in Zeolites 15, Issue 1, 2-8,1995, ITQ-1 in US 6,077,498 und PSH-3 in US 4,439,409 beschrieben. Very particularly preferred zeolites belonging to the structure type MWW are known from the literature. Thus, SSZ-25 is described in US 4,826,667, MCM-22 in Zeolites 15, Issue 1, 2-8, 1995, ITQ-1 in US 6,077,498 and PSH-3 in US 4,439,409.
Besonders bevorzugte Zeolithe, die dem Strukturtyp SZR angehören sind literaturbekannt. So ist SUZ-4 in J.Chem.Soc, Chem. Commun., 1993, 894- 896 beschrieben.  Particularly preferred zeolites belonging to the structural type SZR are known from the literature. Thus, SUZ-4 is described in J. Chem. Soc., Chem. Commun., 1993, 894-896.
Besonders bevorzugte Zeolithe, die dem Strukturtyp FER angehören sind literaturbekannt. So ist ZSM-35 in US 4,107,196, NU-23 in EP 103981 AI, FU-9 in EP 55529 AI, ISI-6 in US 4,695,440 und Ferrierit zum Beispiel in US 3,933,974, US 4,000,248 und US 4,251,499 beschrieben Der erfindungsgemäße Katalysator ist bevorzugt frei von Zeolithen, dessen größte Kanäle nicht von 10 tetraedrisch koordinierten Atomen gebildet werden. Beispielsweise umfasst der erfindungsgemäße Katalysator keinen Zeolithen vom Strukturtyp LTL. Der erfindungsgemäße Katalysator umfasst Palladium. Das Palladium liegt dabei bevorzugt als Palladium-Kation in der Zeolithstruktur vor, das heißt in ionenausgetauschter Form. Das Palladium kann aber auch ganz oder teilweise als Palladium-Metall und/oder als Palladium-Oxid in der Zeolithstruktur und/oder auf der Oberfläche der Zeolithstruktur vorliegen. Particularly preferred zeolites belonging to the structure type FER are known from the literature. Thus, ZSM-35 is described in US 4,107,196, NU-23 in EP 103981 Al, FU-9 in EP 55529 Al, ISI-6 in US 4,695,440 and ferrierite for example in US 3,933,974, US 4,000,248 and US 4,251,499. The catalyst according to the invention is preferred free of zeolites, whose largest channels are not formed by 10 tetrahedrally coordinated atoms. For example, the catalyst according to the invention does not comprise zeolites of the structural type LTL. The catalyst according to the invention comprises palladium. The palladium is preferably present as a palladium cation in the zeolite structure, that is in ion-exchanged form. However, the palladium may also be wholly or partly present as palladium metal and / or as palladium oxide in the zeolite structure and / or on the surface of the zeolite structure.
Das Palladium kann in Mengen von 0,01 bis 20 Gew.-% vorliegen, bezogen auf die Summe der Gewichte von Zeolith und Palladium und berechnet als Palladium-Metall. Bevorzugt liegt Palladium in Mengen von 0,5 bis 10 Gew.-%, besonders bevorzugt von 1,5 bis 10 Gew.-% oder 1,5 bis 4 Gew.-% und ganz besonders bevorzugt von 1,5 bis 2 Gew.-% vor, bezogen auf die Summe der Gewichte von Zeolith und Palladium und berechnet als Palladium-Metall. The palladium may be present in amounts of from 0.01% to 20% by weight, based on the sum of the weights of zeolite and palladium and calculated as palladium metal. Palladium is preferably present in amounts of from 0.5 to 10% by weight, more preferably from 1.5 to 10% by weight or 1.5 to 4% by weight and most preferably from 1.5 to 2% by weight. -% before, based on the sum of the weights of zeolite and palladium and calculated as palladium metal.
Der erfindungsgemäße Katalysator umfasst bevorzugt außer Palladium kein weiteres Metall, insbesondere weder Kupfer, noch Eisen, noch Platin. The catalyst according to the invention preferably contains no further metal other than palladium, in particular neither copper nor iron, nor platinum.
Ein bevorzugter erfindungsgemäßer Katalysator umfasst einen Zeolithen vom Strukturtyp MWW, beispielsweise MCM-22, ERB-1, ITQ-1, PSH-3 oder SSZ-25, und Palladium als alleiniges Metall in einer Menge von 1,5 bis 10 Gew.-%, bezogen auf die Summe der Gewichte von Zeolith und Palladium und berechnet als Palladium-Metall, sowie keinen Zeolithen, dessen größte Kanäle nicht von 10 tetraedrisch koordinierten Atomen gebildet werden. Beispielsweise umfasst dieser erfindungsgemäße Katalysator keinen A preferred catalyst according to the invention comprises a structure-type zeolite MWW, for example MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25, and palladium as the sole metal in an amount of 1.5 to 10% by weight. , based on the sum of the weights of zeolite and palladium and calculated as palladium metal, as well as no zeolite whose largest channels are not formed by 10 tetrahedrally coordinated atoms. For example, this catalyst according to the invention does not comprise any
Zeolithen vom Strukturtyp LTL. Zeolites of the structural type LTL.
Der erfindungsgemäße Katalysator umfasst einen Tragkörper. Dieser kann ein Durchflusssubstrat oder ein Wandflussfilter sein. The catalyst according to the invention comprises a support body. This may be a flow-through substrate or a wall-flow filter.
Ein Wandflussfilter ist ein Tragkörper, der Kanäle der Länge L umfasst, die sich parallel zwischen einem ersten und einem zweiten Ende des A wall-flow filter is a support body comprising channels of length L extending in parallel between a first and a second end of the channel
Wandflussfilters erstrecken, die abwechselnd entweder am ersten oder am zweiten Ende verschlossen sind und die durch poröse Wände getrennt sind. Wall flow filters which are alternately closed either at the first or at the second end and which are separated by porous walls.
Ein Durchflusssubstrat unterscheidet sich von einem Wandflussfilter insbesondere darin, dass die Kanäle der Länge L an seinen beiden Enden offen sind. A flow-through substrate differs from a wall-flow filter in that the channels of length L are open at both ends.
Wandflussfilter weisen in unbeschichtetem Zustand beispielsweise  Wandflussfilter exhibit uncoated, for example
Porositäten von 30 bis 80, insbesondere 50 bis 75% auf. Ihre durchschnittliche Porengröße beträgt in unbeschichtetem Zustand beispielsweise 5 bis 30 Mikrometer. Porosities of 30 to 80, especially 50 to 75%. Their average pore size when uncoated, for example, 5 to 30 microns.
In der Regel sind die Poren des Wandflussfilters sogenannte offene Poren, das heißt sie haben eine Verbindung zur den Kanälen. Des Weiteren sind die Poren in der Regel untereinander verbunden. Dies ermöglicht einerseits die leichte Beschichtung der inneren Porenoberflächen und andererseits eine leichte Passage des Abgases durch die porösen Wände des Wandflussfilters. As a rule, the pores of the wall-flow filter are so-called open pores, that is to say they have a connection to the channels. Furthermore, the pores are usually interconnected. On the one hand, this enables the light coating of the inner pore surfaces and on the other hand easy passage of the exhaust gas through the porous walls of the wall flow filter.
Durchflusssubstrate sind dem Fachmann ebenso wie Wandflussfilter bekannt und sind am Markt erhältlich. Sie bestehen beispielsweise aus Silicium-Carbid, Aluminium-Titanat oder Cordierit. Flow substrates are known in the art as well as wall flow filters and are available on the market. They consist for example of silicon carbide, aluminum titanate or cordierite.
Alternativ können auch Tragkörper verwendet werden, die aus gewellten Blättern aus inerten Materialien aufgebaut sind. Geeignete inerte Materialien sind zum Beispiel faserförmige Materialien mit einem durchschnittlichen Faserdurchmesser von 50 bis 250 pm und einer durchschnittlichen Alternatively, support bodies can be used, which are constructed of corrugated sheets of inert materials. Suitable inert materials are, for example, fibrous materials having an average fiber diameter of 50 to 250 pm and an average
Faserlänge von 2 bis 30 mm. Bevorzugt sind faserförmige Materialien hitzebeständig und bestehen aus Siliziumdioxid, insbesondere aus Fiber length from 2 to 30 mm. Preferably, fibrous materials are heat-resistant and consist of silicon dioxide, in particular of
Glasfasern. Glass fibers.
Zur Herstellung solcher Tragkörper werden zum Beispiel Blätter aus den genannten Fasermaterialien in bekannter Weise gewellt und die einzelnen gewellten Blätter zu einem zylindrischen monolithisch strukturierten Körper mit den Körper durchziehenden Kanälen geformt. Vorzugsweise wird durch Aufschichten einer Anzahl der gewellten Blätter zu parallelen Schichten mit unterschiedlicher Orientierung der Wellung zwischen den Schichten ein monolithisch strukturierter Körper mit einer kreuzweisen Wellungsstruktur geformt. In einer Ausführungsform können zwischen den gewellten Blättern ungewellte, d.h. flache Blätter angeordnet sein. To produce such support bodies, for example, sheets of said fiber materials are corrugated in a known manner and the individual corrugated sheets are formed into a cylindrical monolithically structured body with the body passing channels. Preferably, by laminating a number of the corrugated sheets to parallel layers having different orientation of corrugation between the layers, a monolithic structured body having a criss-cross corrugation structure is formed. In one embodiment, undulating, i. be arranged flat leaves.
Tragkörper aus gewellten Blättern können direkt mit dem erfindungs- gemäßen Katalysator beschichtet werden, vorzugsweise werden sie aber zunächst mit einem inerten Material, zum Beispiel Titandioxid, und erst dann mit dem katalytischen Material beschichtet. Carrier bodies of corrugated sheets can be coated directly with the catalyst according to the invention, but they are preferably initially coated with an inert material, for example titanium dioxide, and only then with the catalytic material.
In einer weiteren Ausführungsform des erfindungsgemäßen Katalysators liegen der Zeolith und das Palladium in Form einer Beschichtung auf dem Trägersubstrat vor. Dabei kann sich die Beschichtung über die gesamte Länge L des Trägersubstrates oder nur über einen Teil davon erstrecken. Im Falle eines Wandflussfilters kann sich die Beschichtung auf den Oberflächen der Eingangskanäle, auf den Oberflächen der Ausgangskanäle und/oder in der porösen Wand zwischen Ein- und Ausgangskanälen befinden. In a further embodiment of the catalyst according to the invention, the zeolite and the palladium are in the form of a coating on the carrier substrate. In this case, the coating may extend over the entire length L of the carrier substrate or only over a part thereof. In the case of a wall-flow filter, the coating may be on the surfaces of the input channels, on the surfaces of the output channels, and / or in the porous wall between input and output channels.
Unter Beschichtung versteht der Fachmann auf dem Gebiet der Autoabgaskatalyse eine Materialzone, die auch Washcoats genannt wird und in der Regel mittels einer wässrigen Suspension auf den Tragkörper aufgebracht wird . By coating, the person skilled in the art of autoboss catalysis understands a material zone, which is also called washcoats, and is generally applied to the support body by means of an aqueous suspension.
Erfindungsgemäße Katalysatoren, bei denen der Zeolith und das Palladium in Form einer Beschichtung auf dem Trägersubstrat vorliegen, können nach dem Fachmann geläufigen Methoden hergestellt werden, so etwa nach den üblichen Tauchbeschichtungsverfahren bzw. Pump- und Saug- Beschichtungsverfahren mit sich anschließender thermischer Nachbe- handlung (Kalzination). Dem Fachmann ist bekannt, dass im Falle von Wandflussfiltern deren durchschnittliche Porengröße und die mittlere Teilchengröße der zu beschichtenden Materialien so aufeinander Catalysts according to the invention in which the zeolite and the palladium are present in the form of a coating on the carrier substrate can be prepared by methods familiar to the person skilled in the art, for example by the customary dip coating methods or pumping and suction coating methods followed by thermal aftertreatment ( calcination). It is known to the person skilled in the art that, in the case of wall-flow filters, their average pore size and the average particle size of the materials to be coated are superimposed on one another
abgestimmt werden können, dass diese auf den porösen Wänden, die die Kanäle des Wandflussfilters bilden, liegen (auf-Wand-Beschichtung). Die mittlere Teilchengröße der zu beschichtenden Materialien kann aber auch so gewählt werden, dass sich diese in den porösen Wänden, die die Kanäle des Wandflussfilters bilden, befinden, dass also eine Beschichtung der inneren Porenoberflächen erfolgt (in-Wand-Beschichtung). In diesem Fall muss die mittlere Teilchengröße der der zu beschichtenden Materialien klein genug sein, um in die Poren des Wandflussfilters einzudringen. can be tuned that they are on the porous walls that form the channels of the wall flow filter (on-wall coating). However, the average particle size of the materials to be coated can also be chosen such that they are located in the porous walls that form the channels of the wall-flow filter, that is to say that a coating of the inner pore surfaces takes place (in-wall coating). In this case, the mean particle size of the materials to be coated must be small enough to penetrate into the pores of the wall flow filter.
In einer Ausführungsform der vorliegenden Erfindung liegen der Zeolith und das Palladium über die gesamte Länge L des Trägersubstrats beschichtet vor, wobei sich keine weitere katalytisch aktive Beschichtung auf dem Trägersubstrat befindet. In anderen Ausführungsformen der vorliegenden Erfindung kann das Trägersubstrat aber auch eine oder mehrere weitere katalytisch aktive Beschichtungen tragen. Beispielsweise kann das Trägersubstrat neben einer Beschichtung, die den Zeolithen und das Palladium umfasst eine weitere Beschichtung umfassen, die oxidationskatalytisch aktiv ist. In one embodiment of the present invention, the zeolite and the palladium are coated over the entire length L of the carrier substrate, with no further catalytically active coating on the carrier substrate. However, in other embodiments of the present invention, the carrier substrate may also carry one or more further catalytically active coatings. By way of example, the carrier substrate may comprise, in addition to a coating comprising the zeolite and the palladium, a further coating which is active in oxidation-catalytically.
Die oxidationskatalytisch aktive Beschichtung umfasst beispielsweise Platin, Palladium oder Platin und Palladium auf einem Trägermaterial . Im  The oxidation-catalytically active coating comprises, for example, platinum, palladium or platinum and palladium on a carrier material. in the
letztgenannten Fall liegt das Masseverhältnis von Platin zu Palladium beispielsweise bei 4 : 1 bis 14 : 1. the latter case, the mass ratio of platinum to palladium, for example, at 4: 1 to 14: 1.
Als Trägermaterial kommen alle dem Fachmann für diesen Zweck geläufigen Materialien in Betracht. Sie weisen eine BET-Oberfläche von 30 bis 250 m2/g, bevorzugt von 100 bis 200 m2/g auf (bestimmt nach DIN 66132) und sind insbesondere Aluminiumoxid, Siliziumoxid, Magnesiumoxid, Titanoxid, sowie Mischungen oder Mischoxide von mindestens zwei dieser Materialien. Bevorzugt sind Aluminiumoxid, Magnesium/Aluminium-Mischoxide und Aluminium/Silizium-Mischoxide. Sofern Aluminiumoxid verwendet wird, so ist es besonders bevorzugt stabilisiert, beispielsweise mit 1 bis 6 Gew.-%, insbesondere 4 Gew.-%, Lanthanoxid. Suitable carrier materials are all those familiar to the person skilled in the art for this purpose. They have a BET surface area of 30 to 250 m 2 / g, preferably from 100 to 200 m 2 / g (determined according to DIN 66132) and are in particular alumina, silica, magnesium oxide, titanium oxide, and mixtures or mixed oxides of at least two of these Materials. Preference is given to aluminum oxide, magnesium / aluminum mixed oxides and aluminum / silicon mixed oxides. If alumina is used, it is particularly preferably stabilized, for example with 1 to 6 wt .-%, in particular 4 wt .-%, lanthanum oxide.
Die den Zeolithen und das Palladium umfassende Beschichtung  The coating comprising the zeolites and the palladium
(nachstehend Beschichtung A genannt) und die oxidationskatalytisch aktive Beschichtung (nachstehend Beschichtung B genannt) können auf dem Trägersubstrat in verschiedener Weise angeordnet sein. (hereinafter referred to as coating A) and the oxidation-catalytically active coating (hereinafter called coating B) may be arranged on the carrier substrate in various ways.
Ist das Trägersubstrat ein Durchflusssubstrat so können beispielsweise beide Beschichtungen über die gesamte oder nur über einen Teil der Länge L des Trägersubstrats beschichtet vorliegen. If the carrier substrate is a flow-through substrate, for example, both coatings may be coated over the entire or only over a part of the length L of the carrier substrate.
Beispielsweise kann sich Beschichtung A ausgehend von einem Ende des Tragkörpers auf 10 bis 80% seiner Länge L und Beschichtung B ausgehend vom anderen Ende des Tragkörpers 10 bis 80% seine Länge LA erstrecken. Es kann in diesem Fall sein, dass L = LA + LB gilt, wobei LA die Länge der Beschichtung A und LB die Länge der Beschichtung B ist. Es kann aber auch L < LA + LB gelten. In diesem Fall überlappen sich die Beschichtungen A und B. Schließlich kann auch L > LA + LB gelten, wenn ein Teil des Tragkörpers frei von Beschichtungen bleibt. Im letztgenannten Fall bleibt zwischen den Beschichtungen A und B ein Spalt, der mindestens 0,5 cm lang ist, also beispielsweise 0,5 bis 1 cm. For example, starting from one end of the supporting body, coating A may extend from 10 to 80% of its length L and coating B, starting from the other end of the supporting body 10 to 80% of its length LA. In this case, it may be that L = LA + LB, where LA is the length of the coating A and LB is the length of the coating B. But it can too L <LA + LB apply. In this case, the coatings A and B overlap. Finally, L> LA + LB can also apply if part of the support body remains free of coatings. In the latter case, between the coatings A and B remains a gap which is at least 0.5 cm long, that is for example 0.5 to 1 cm.
Die Beschichtungen A und B können aber auch beide über die gesamte Länge L beschichtet sein. In diesem Fall kann beispielsweise die However, the coatings A and B may also both be coated over the entire length L. In this case, for example, the
Beschichtung B direkt auf dem Trägersubstrat und die Beschichtung A auf Beschichtung B vorliegen. Alternativ kann auch die Beschichtung A direkt auf dem Trägersubstrat und die Beschichtung B auf Beschichtung A vorliegen. Coating B directly on the carrier substrate and the coating A on coating B are present. Alternatively, the coating A may also be present directly on the carrier substrate and the coating B on the coating A.
Es ist darüber hinaus möglich, dass sich eine Beschichtung über die gesamte Länge des Tragkörpers erstreckt und die andere nur über einen Teil davon. It is also possible that a coating extends over the entire length of the support body and the other only over a part thereof.
In einer bevorzugten Ausführungsform liegt ein mit 1 bis 2 Gew.-%, insbesondere 1,5 bis 2 Gew.-% Palladium belegter Zeolith vom Typ FER, MEL, MTT, MWW oder SZR, insbesondere MWW, direkt auf dem In a preferred embodiment, a zeolite of the type FER, MEL, MTT, MWW or SZR, in particular MWW, which is occupied by 1 to 2% by weight, in particular 1.5 to 2% by weight, of palladium lies directly on the
Trägersubstrat über dessen gesamte Länge L und auf dieser Beschichtung liegt eine Platin oder Platin und Palladium im Masseverhältnis von 4: 1 bis 14: 1 enthaltende Beschichtung ebenfalls über die gesamte Länge L.  Carrier substrate over its entire length L and on this coating is a platinum or platinum and palladium in the mass ratio of 4: 1 to 14: 1 containing coating also over the entire length L.
Insbesondere liegt dabei die untere Schicht (zum Beispiel Pd-FER oder Pd- MWW) in einer Menge von 50 bis 250 g/l Trägersubstrat und die obere Schicht (Pt bzw. Pt/Pd) in einer Menge von 50 bis 100 g/l Trägersubstrat vor. In particular, the lower layer (for example Pd-FER or Pd-MWW) is present in an amount of 50 to 250 g / l carrier substrate and the upper layer (Pt or Pt / Pd) in an amount of 50 to 100 g / l Carrier substrate before.
Ist das Trägersubstrat ein Wandflussfilter, so können sich die If the carrier substrate is a wall-flow filter, then the
Beschichtungen A und B in analoger Weise wie oben für Durchflusssubstrate beschrieben über die gesamte Länge L des Wandflussfilters oder nur über einen Teil davon erstrecken. Daneben können sich die Beschichtungen auf den Wänden der Eingangskanäle, auf den Wänden der Ausgangskanäle oder in den Wänden zwischen Ein- und Ausgangskanälen liegen. Coating A and B in an analogous manner as described above for flow-through substrates over the entire length L of the wall flow filter or only over a part thereof. In addition, the coatings can on the walls of the input channels, on the walls of the output channels or in the walls between input and output channels.
In einer anderen Ausführungsform der vorliegenden Erfindung ist das Trägersubstrat aus dem Zeolithen, dessen größte Kanäle von 10 In another embodiment of the present invention, the carrier substrate is the zeolite, whose largest channels are from 10
tetraedrisch koordinierten Atomen gebildet werden, Palladium und einer Matrix-komponente gebildet. tetrahedrally coordinated atoms are formed, palladium and a matrix component formed.
Trägersubstrate, Durchflusssubstrate ebenso wie Wandflussfilter, die nicht nur aus inertem Material, wie beispielsweise Cordierit bestehen, sondern die daneben auch ein katalytisch aktives Material enthalten, sind dem  Support substrates, flow substrates as well as wall flow filters, which not only consist of inert material, such as cordierite, but also contain a catalytically active material, are the
Fachmann bekannt. Zu ihrer Herstellung wird eine Mischung aus Specialist known. For their preparation is a mixture of
beispielsweise 10 bis 95 Gew.-% inerter Matrixkomponente und 5 bis 90 Gew.-% katalytisch aktiven Materials nach an sich bekannten Verfahren extrudiert. Als Matrixkomponenten können dabei alle auch sonst zur For example, 10 to 95 wt .-% inert matrix component and 5 to 90 wt .-% of catalytically active material extruded by methods known per se. As matrix components, all else can be used for
Herstellung von Katalysatorsubstraten verwendeten inerten Materialien verwendet werden. Es handelt sich dabei beispielsweise um Silikate, Oxide, Nitride oder Carbide, wobei insbesondere Magnesium-Aluminium-Silikate bevorzugt sind . Das extrudierte Trägersubstrat, das den Zeolithen, dessen größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden, sowie Palladium umfasst, kann in Ausführungsformen der vorliegenden Erfindung mit einer oder mehreren katalytisch aktiven Beschichtungen beschichtet sein, beispielsweise mit der oben beschriebenen oxidationskatalytisch aktiven Beschichtung. Preparation of catalyst substrates used inert materials can be used. These are, for example, silicates, oxides, nitrides or carbides, with particular preference being given to magnesium-aluminum silicates. The extruded carrier substrate comprising the zeolites, the largest channels of which are formed of tetrahedrally coordinated atoms, and palladium may in embodiments of the present invention be coated with one or more catalytically active coatings, for example with the above-described oxidation-catalytically active coating.
Der erfindungsgemäße Katalysator eignet sich in hervorragender Weise als passiver Stickoxidspeicherkatalysator, d.h. er vermag bei Temperaturen von unter 200°C Stickoxide einzuspeichern und diese bei Temperaturen von über 200°C wieder auszuspeichern.  The catalyst of the invention is outstandingly useful as a passive nitrogen oxide storage catalyst, i. it is able to store nitrogen oxides at temperatures below 200 ° C and to recycle them at temperatures above 200 ° C.
Die vorliegende Erfindung betrifft somit auch die Verwendung eines The present invention thus also relates to the use of a
Katalysators, der ein Trägersubstrat der Länge L, Palladium und einen Zeolithen, dessen größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden, als passiver Stickoxidspeicherkatalysator, der Stickoxide in einem ersten Temperaturbereich speichert und in einem zweiten A catalyst comprising a carrier substrate of length L, palladium and a zeolite, the largest channels of which are formed by 10 tetrahedrally coordinated atoms, as a passive nitrogen oxide storage catalyst containing nitrogen oxides in stores a first temperature range and in a second
Temperaturbereich wieder freisetzt, wobei der zweite Temperaturbereich bei höheren Temperaturen liegt als der erste Temperaturbereich. Insbesondere betrifft die vorliegende Erfindung die Verwendung eines Katalysators, der ein Trägersubstrat der Länge L, einen Zeolithen vom Strukturtyp MWW, beispielsweise MCM-22, ERB-1, ITQ-1, PSH-3 oder SSZ- 25, und Palladium als alleiniges Metall in einer Menge von 1,5 bis 10 Gew.- %, bezogen auf die Summe der Gewichte von Zeolith und Palladium und berechnet als Palladium-Metall, sowie keinen Zeolithen, dessen größte Kanäle nicht von 10 tetraedrisch koordinierten Atomen gebildet werden. Releases temperature range again, the second temperature range is at higher temperatures than the first temperature range. In particular, the present invention relates to the use of a catalyst comprising a carrier substrate of length L, a structure-type zeolite MWW, for example MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25, and palladium as the sole metal in in an amount of 1.5 to 10% by weight, based on the sum of the weights of zeolite and palladium and calculated as palladium metal, and no zeolites whose largest channels are not formed by 10 tetrahedrally coordinated atoms.
Der erfindungsgemäße Katalysator erlaubt es in Kombination mit einem abströmseitigen SCR-Katalysator, Stickoxide über den gesamten The catalyst according to the invention, in combination with a downstream SCR catalyst, allows nitrogen oxides over the entire
Temperaturbereich des Abgases, einschließlich der Kaltstarttemperaturen, wirkungsvoll umzusetzen. Temperature range of the exhaust gas, including the cold start temperatures to implement effectively.
Die vorliegende Erfindung betrifft somit auch ein Abgassystem, das a) einen Katalysator, der ein Trägersubstrat der Länge L, Palladium und einen Zeolithen, dessen größte Kanäle von 10 tetraedrisch koordiniertenThe present invention thus also relates to an exhaust gas system comprising a) a catalyst tetrahedrally coordinating a carrier substrate of length L, palladium and a zeolite whose largest channels of 10
Atomen gebildet werden, umfasst und Atoms are formed, includes and
b) einen SCR-Katalysator b) an SCR catalyst
umfasst. Der SCR-Katalysator im erfindungsgemäßen Abgassystem kann prinzipiell ausgewählt sein aus allen in der SCR-Reaktion von Stickoxiden mit includes. The SCR catalyst in the exhaust system according to the invention can in principle be selected from all in the SCR reaction of nitrogen oxides with
Ammoniak aktiven Katalysatoren, insbesondere aus solchen, die dem Ammonia-active catalysts, in particular from those which the
Fachmann auf dem Gebiet der Autoabgaskatalyse als gebräuchlich bekannt sind . Dies schließt Katalysatoren vom Mischoxid-Typ ebenso ein, wie Those skilled in the art of car exhaust catalysis are known to be in use. This includes mixed oxide type catalysts as well
Katalysatoren auf Basis von Zeolithen, insbesondere von Übergangsmetall- ausgetauschten Zeolithen. In Ausführungsformen der vorliegenden Erfindung werden SCR- Katalysatoren, die einen kleinporigen Zeolithen mit einer maximalen Catalysts based on zeolites, in particular transition metal-exchanged zeolites. In embodiments of the present invention, SCR catalysts that have a small pore zeolite with a maximum
Ringgröße von acht tetraedrischen Atomen und ein Übergangsmetall enthalten, verwendet. Solche SCR-Katalysatoren sind beispielsweise in WO2008/106519 AI, WO2008/118434 AI und WO2008/132452 A2 beschrieben. Ring size of eight tetrahedral atoms and a transition metal included, used. Such SCR catalysts are described, for example, in WO2008 / 106519 A1, WO2008 / 118434 A1 and WO2008 / 132452 A2.
Daneben können aber auch groß- und mittelporige Zeolithe verwendet werden, wobei insbesondere solche vom Strukturtyp BEA in Frage kommen. So sind Eisen-BEA und Kupfer-BEA von Interesse.  In addition, however, large and medium pore zeolites can be used, in particular those of the structure type BEA come into question. For example, iron BEA and copper BEA are of interest.
Besonders bevorzugte Zeolithe gehören den Gerüsttypen BEA, AEI, CHA, KFI, ERI, LEV, MER oder DDR an und sind besonders bevorzugt mit Kobalt, Eisen, Kupfer oder Mischungen aus zwei oder drei dieser Metalle Particularly preferred zeolites belong to the framework types BEA, AEI, CHA, KFI, ERI, LEV, MER or DDR and are particularly preferred with cobalt, iron, copper or mixtures of two or three of these metals
ausgetauscht. replaced.
Unter den Begriff Zeolithe fallen hier auch Molsiebe, die bisweilen auch als „zeolithähnliche" Verbindungen bezeichnet werden. Molsiebe sind The term zeolites also includes molecular sieves, sometimes referred to as "zeolite-like" compounds
bevorzugt, wenn sie einem der oben genannten Gerüsttypen angehören. Beispiele sind Silicaaluminiumphosphat-Zeolithe, die unter dem Begriff SAPO bekannt sind und Aluminiumphosphat-Zeolithe, die unter dem Begriff AIPO bekannt sind. preferred if they belong to one of the above scaffold types. Examples are silica-aluminum-phosphate zeolites known by the term SAPO and aluminum phosphate zeolites known by the term AIPO.
Auch diese sind insbesondere dann bevorzugt, wenn sie mit Kobalt, Eisen, Kupfer oder Mischungen aus zwei oder drei dieser Metalle ausgetauscht sind .  These are also particularly preferred when they are exchanged with cobalt, iron, copper or mixtures of two or three of these metals.
Bevorzugte Zeolithe sind weiterhin solche, die einen SAR (silica-to-alumina ratio)-Wert von 2 bis 100, insbesondere von 5 bis 50, aufweisen. Preferred zeolites are furthermore those which have a SAR (silica-to-alumina ratio) value of from 2 to 100, in particular from 5 to 50.
Die Zeolithe bzw. Molsiebe enthalten Übergangsmetall insbesondere in Mengen von 1 bis 10 Gew.-%, insbesondere 2 bis 5 Gew.-%, berechnet als Metalloxid, also beispielsweise als Fe203 oder CuO. Bevorzugte Ausführungsformen der vorliegenden Erfindung enthalten als SCR-Katalysatoren mit Kupfer, Eisen oder Kupfer und Eisen ausgetauschte Zeolithe oder Molsiebe vom Beta-Typ (BEA), Chabazit-Typ (CHA) oder vom Levyne-Typ (LEV). Entsprechende Zeolithe oder Molsiebe sind The zeolites or molecular sieves contain transition metal, in particular in amounts of from 1 to 10% by weight, in particular from 2 to 5% by weight, calculated as metal oxide, ie for example as Fe 2 O 3 or CuO. Preferred embodiments of the present invention include SCR catalysts with copper, iron or copper and iron exchanged zeolites or beta-type molecular sieves (BEA), chabazite type (CHA) or Levyne type (LEV). Corresponding zeolites or molecular sieves are
beispielsweise unter den Bezeichnungen ZSM-5, Beta, SSZ-13, SSZ-62, Nu-3, ZK-20, LZ-132, SAPO-34, SAPO-35, AIPO-34 und AIPO-35 bekannt, siehe etwa US 6,709,644 und US 8,617,474. for example, under the designations ZSM-5, Beta, SSZ-13, SSZ-62, Nu-3, ZK-20, LZ-132, SAPO-34, SAPO-35, AIPO-34 and AIPO-35, see for example US 6,709,644 and US 8,617,474.
In einer Ausführungsform des erfindungsgemäßen Abgassystems befindet sich zwischen dem Katalysator, der ein Trägersubstrat der Länge L,  In one embodiment of the exhaust system according to the invention is located between the catalyst, which is a carrier substrate of length L,
Palladium und einen Zeolithen, dessen größte Kanäle von 8 tetraedrisch koordinierten Atomen gebildet werden und dem SCR-Katalysator eine Einspritzeinrichtung für Reduktionsmittel. Palladium and a zeolite whose largest channels are formed by 8 tetrahedrally coordinated atoms and the SCR catalyst, a reducing agent injector.
Die Einspritzvorrichtung kann vom Fachmann beliebig gewählt werden, wobei geeignete Vorrichtungen der Literatur entnommen werden können (siehe etwa T. Mayer, Feststoff-SCR-System auf Basis von Ammonium- carbamat, Dissertation, TU Kaiserslautern, 2005). Der Ammoniak kann über die Einspritzvorrichtung als solches oder in Form einer Verbindung in den Abgasstrom eingebracht werden, aus der bei den Umgebungsbedingungen Ammoniak gebildet wird . Als solche kommen beispielsweise wässrige Lösungen von Harnstoff oder Ammoniumformiat in Frage, ebenso wie festes Ammoniumcarbamat. In der Regel wird das Reduktionsmittel bzw. ein Vorläufer davon in einem mitgeführten Behälter, der mit der  The injection device can be chosen arbitrarily by the person skilled in the art, suitable devices being able to be taken from the literature (see, for example, T. Mayer, Solid-SCR System Based on Ammonium Carbamate, Dissertation, TU Kaiserslautern, 2005). The ammonia can be introduced via the injection device as such or in the form of a compound in the exhaust stream from which ammonia is formed at ambient conditions. As such, for example, aqueous solutions of urea or ammonium formate in question, as well as solid ammonium carbamate. In general, the reducing agent or a precursor thereof in a entrained container, with the
Einspritzvorrichtung verbunden ist, vorrätig gehalten. Der SCR-Katalysator liegt bevorzugt in Form einer Beschichtung auf einem Tragkörper vor, der ein Durchflusssubstrat oder ein Wandflussfilter sein und beispielsweise aus Silicium-Carbid, Aluminium-Titanat oder Cordierit bestehen kann. Injection device is connected, kept in stock. The SCR catalyst is preferably in the form of a coating on a supporting body, which may be a flow-through substrate or a wall-flow filter and may consist, for example, of silicon carbide, aluminum titanate or cordierite.
Alternativ kann aber auch der Tragkörper selbst aus dem SCR-Katalysator und einer Matrixkomponente wie oben beschrieben bestehen, also in extrudierter Form vorliegen. Die vorliegende Erfindung betrifft auch ein Verfahren zur Reinigung von Abgasen von Kraftfahrzeugen, die mit mager betriebenen Motoren, etwa Dieselmotoren, betrieben werden, das dadurch gekennzeichnet ist, dass das Abgas über ein erfindungsgemäßes Abgassystem geleitet wird . Alternatively, however, the support body itself may consist of the SCR catalyst and a matrix component as described above, that is, in extruded form. The present invention also relates to a method for purifying exhaust gases of motor vehicles which are operated with lean-burn engines, such as diesel engines, characterized in that the exhaust gas is passed through an exhaust system according to the invention.
Beispiel 1 example 1
a) Ein Zeolith vom Strukturtyp FER wird mit 3 Gew.-% Palladium (aus kommerziell erhältlichem Palladium-Nitrat) imprägniert ("incipient a) A zeolite of the structural type FER is impregnated with 3% by weight of palladium (from commercially available palladium nitrate) ("incipient
wetness"). Das so erhaltene Pulver wird anschließend bei 120 °C getrocknet und bei 500 °C kalziniert. b) Das erhaltene Pd-haltige, kalzinierte Pulver wird in VE-Wasser The powder thus obtained is then dried at 120 ° C. and calcined at 500 ° C. b) The resulting Pd-containing, calcined powder is dissolved in deionised water
suspendiert, mit 8% eines kommerziell erhältlichen Binders auf Böhmit- Basis versetzt und mittels einer Kugelmühle gemahlen. Anschließend wird mit dem so erhaltenen Washcoat ein handelsübliches wabenförmigessuspended, mixed with 8% of a commercially available boehmite-based binder and ground by means of a ball mill. Subsequently, with the washcoat thus obtained a commercial honeycomb
Keramiksubstrat (Durchflusssubstrat) über dessen ganze Länge nach einem üblichen Verfahren beschichtet. Die Washcoat-Beladung beträgt 50 g/L, bezogen auf den Pd-haltigen Zeolithen (entspricht 54 g/L inkl . Binder), was einer Edelmetallbeladung von 42,5 g/ft3 Pd entspricht. Der so erhaltene Katalysator wird bei 550 °C kalziniert. Ceramic substrate (flow-through substrate) over its entire length coated by a conventional method. The washcoat loading is 50 g / L, based on the Pd-containing zeolite (equivalent to 54 g / L including binder), which corresponds to a precious metal loading of 42.5 g / ft 3 Pd. The catalyst thus obtained is calcined at 550 ° C.
Beispiel 2 Example 2
Beispiel 1 wird wiederholt mit dem Unterschied, dass das Keramiksubstrat mit 100 g/L Pd-haltigem Zeolithen beschichtet wird (entspricht 108 g/L inkl. Binder). Dies entspricht einer Edelmetallbeladung von 85 g/ft3 Pd. Example 1 is repeated with the difference that the ceramic substrate is coated with 100 g / l Pd-containing zeolite (corresponds to 108 g / L including binder). This corresponds to a noble metal loading of 85 g / ft 3 Pd.
Beispiel 3 Example 3
Beispiel 1 wird wiederholt mit dem Unterschied, dass das Keramiksubstrat mit 200 g/L Pd-haltigem Zeolithen beschichtet wird (entspricht 216 g/L inkl. Binder). Dies entspricht einer Edelmetallbeladung von 170 g/ft3 Pd . Example 1 is repeated with the difference that the ceramic substrate is coated with 200 g / l Pd-containing zeolite (corresponds to 216 g / L including binder). This corresponds to a noble metal loading of 170 g / ft 3 Pd.
Beispiel 4 Beispiel 2 wird wiederholt mit dem Unterschied, dass der Zeolith mit 1,5 Gew.-% Palladium imprägniert wird. Dies entspricht einer Edelmetallbeladung von 42,5 g/ft3 Pd . Beispiel 5 Example 4 Example 2 is repeated with the difference that the zeolite is impregnated with 1.5% by weight of palladium. This corresponds to a noble metal loading of 42.5 g / ft 3 Pd. Example 5
Beispiel 3 wird wiederholt mit dem Unterschied, dass der Zeolith mit 1,5 Gew.-% Palladium imprägniert wird. Dies entspricht einer Edelmetallbeladung von 85 g/ft3 Pd . Beispiel 6 Example 3 is repeated with the difference that the zeolite is impregnated with 1.5% by weight of palladium. This corresponds to a noble metal loading of 85 g / ft 3 Pd. Example 6
Beispiel 3 wird wiederholt mit dem Unterschied, dass der Zeolith mit 0,75 Gew.-% Palladium imprägniert wird. Dies entspricht einer Edelmetallbeladung von 42,5 g/ft3 Pd . Beispiel 7 Example 3 is repeated with the difference that the zeolite is impregnated with 0.75 wt .-% palladium. This corresponds to a noble metal loading of 42.5 g / ft 3 Pd. Example 7
Der gemäß Beispiel 5 erhaltene Katalysator wird in einem weiteren Schritt nach einem üblichen Verfahren ebenfalls über seine ganze Länge mit einem Washcoat beschichtet, der Platin geträgert auf Aluminiumoxid enthält. Die Washcoatbeladung der zweiten Schicht beträgt 75 g/L, die Platinbeladung beträgt 20 g/ft3. The catalyst obtained according to Example 5 is also coated in a further step by a conventional method also over its entire length with a washcoat containing platinum supported on alumina. The washcoat loading of the second layer is 75 g / L, the platinum loading is 20 g / ft 3 .
Beispiel 8 Example 8
Der Katalysator gemäß Beispiel 7 wird mit einem zweiten beschichteten Durchflusssubstrat zu einem Abgassystem kombiniert. Dabei ist das zweite Durchflusssubstrat mit einem mit 3 Gew.-% Kupfer (berechnet als CuO) ausgetauschten Zeolithen vom Strukturtyp Chabazit ausgetauscht. Die Washcoatbeladung des zweiten Durchflusssubstrates beträgt 150 g/L.  The catalyst of Example 7 is combined with a second coated flow-through substrate to form an exhaust system. In this case, the second flow-through substrate is exchanged with a zeolite of the structure type chabazite exchanged with 3% by weight of copper (calculated as CuO). The washcoat loading of the second flow substrate is 150 g / L.
Beispiel 9 Example 9
Beispiel 1 wird wiederholt mit dem Unterschied, dass ein Zeolith vom Strukturtyp MWW verwendet wurde. Example 1 is repeated with the difference that a structure-type zeolite MWW was used.

Claims

Patentansprüche claims
1. Katalysator, der ein Trägersubstrat der Länge L, Palladium und einen Zeolithen, dessen größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden, umfasst. A catalyst comprising a carrier substrate of length L, palladium and a zeolite whose major channels are formed of ten tetrahedrally coordinated atoms.
2. Katalysator gemäß Anspruch 1, dadurch gekennzeichnet, dass der Zeolith dem Strukturtyp *MRE, AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CSV, DAC, EUO, FER, HEU, IFW, IMF, ITH, ITR, JRY, JST, LAU, MEL, MFS, MTT, MVY, MWW, NES, OBW, -PAR, PCR, PON, PSI, RRO, SFF, SFG, STF, STI, STW, - SVR, SZR, TER, TON, TUN, UOS, WEI oder -WEN angehört. 2. Catalyst according to claim 1, characterized in that the zeolite of the structure type * MRE, AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CSV, DAC, EUO, FER, HEU, IFW, IMF, ITH, ITR, JRY, JST, LAU, MEL, MFS, MTT, MVY, MWW, NES, OBW, -PAR, PCR, PON, PSI, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TONE, TUN, UOS, WEI or -WEN.
3. Katalysator gemäß Anspruch 1 und/oder 2, dadurch gekennzeichnet, dass der Zeolith dem Strukturtyp MEL, MTT, MWW oder SZR angehört. 3. Catalyst according to claim 1 and / or 2, characterized in that the zeolite belongs to the structural type MEL, MTT, MWW or SZR.
4. Katalysator gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Zeolith dem Strukturtyp MWW angehört. 4. Catalyst according to one or more of claims 1 to 3, characterized in that the zeolite belongs to the structure type MWW.
5. Katalysator gemäß einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Palladium als Palladium-Kation in der Zeolith- struktur vorliegt. 5. Catalyst according to one or more of claims 1 to 4, characterized in that the palladium is present as a palladium cation in the zeolite structure.
6. Katalysator gemäß einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Palladium in Mengen von 1,5 bis 10 Gew.-%, bezogen auf die Summe der Gewichte von Zeolith und Palladium und berechnet als Palladium-Metall, vorliegt. 6. Catalyst according to one or more of claims 1 to 5, characterized in that the palladium in amounts of 1.5 to 10 wt .-%, based on the sum of the weights of zeolite and palladium and calculated as palladium metal, is present ,
7. Katalysator gemäß einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass er einen Zeolithen vom Strukturtyp MWW und 7. Catalyst according to one or more of claims 1 to 6, characterized in that it comprises a zeolite structure type MWW and
Palladium als alleiniges Metall in einer Menge von 1,5 bis 10 Gew.-%, bezogen auf die Summe der Gewichte von Zeolith und Palladium und berechnet als Palladium-Metall, sowie keinen Zeolithen, dessen größte Kanäle nicht von 10 tetraedrisch koordinierten Atomen gebildet werden, umfasst. Palladium as the sole metal in an amount of 1.5 to 10 wt .-%, based on the sum of the weights of zeolite and palladium and calculated as palladium metal, and no zeolite, the largest Channels are not formed by 10 tetrahedrally coordinated atoms.
8. Katalysator gemäß Anspruch 7, dadurch gekennzeichnet, dass der Zeolith vom Strukturtyp MWW MCM-22, ERB-1, ITQ-1, PSH-3 oder SSZ-25 ist. 8. A catalyst according to claim 7, characterized in that the zeolite structural type MWW MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25.
9. Katalysator gemäß einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Zeolith und das Palladium in Form einer 9. A catalyst according to one or more of claims 1 to 8, characterized in that the zeolite and the palladium in the form of a
Beschichtung auf dem Trägersubstrat vorliegen. Coating on the carrier substrate present.
10. Katalysator gemäß Anspruch 9, dadurch gekennzeichnet, dass das Trägersubstrat eine weitere katalytisch aktive Beschichtung trägt, die eine oxidationskatalytisch aktive Beschichtung ist, die Platin, Palladium oder Platin und Palladium auf einem Trägermaterial umfasst. 10. A catalyst according to claim 9, characterized in that the carrier substrate carries a further catalytically active coating, which is an oxidation-catalytically active coating comprising platinum, palladium or platinum and palladium on a support material.
11. Katalysator gemäß einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass sich ein mit 1,5 bis 2 Gew.-% Palladium belegter Zeolith vom Strukturtyp FER, MEL, MTT, MWW oder SZR direkt auf dem Trägersubstrat über dessen gesamte Länge L erstreckt und sich auf dieser Beschichtung eine Platin oder Platin und Palladium im 11. Catalyst according to one or more of claims 1 to 10, characterized in that a occupied with 1.5 to 2 wt .-% palladium zeolite structure type FER, MEL, MTT, MWW or SZR directly on the carrier substrate over its entire Length L extends and on this coating a platinum or platinum and palladium in the
Masseverhältnis von 4: 1 bis 14: 1 enthaltende Beschichtung über die gesamte Länge L befindet.  Mass ratio of 4: 1 to 14: 1 containing coating over the entire length L is located.
12. Verwendung eines Katalysators gemäß einem oder mehreren der 12. Use of a catalyst according to one or more of
Ansprüche 1 bis 11 als passiver Stickoxidspeicherkatalysator, der Stickoxide in einem ersten Temperaturbereich speichert und in einem zweiten Claims 1 to 11 as a passive nitrogen oxide storage catalyst that stores nitrogen oxides in a first temperature range and in a second
Temperaturbereich wieder freisetzt, wobei der zweite Temperaturbereich bei höheren Temperaturen liegt als der erste Temperaturbereich . Releases temperature range again, the second temperature range is at higher temperatures than the first temperature range.
13. Verwendung gemäß Anspruch 12, dadurch gekennzeichnet, dass der Katalysator einen Zeolithen vom Strukturtyp MWW und Palladium als alleiniges Metall in einer Menge von 1,5 bis 10 Gew.-%, bezogen auf die Summe der Gewichte von Zeolith und Palladium und berechnet als Palladium-Metall, sowie keinen Zeolithen, dessen größte Kanäle nicht von 10 tetraedrisch koordinierten Atomen gebildet werden, enthält. 13. Use according to claim 12, characterized in that the catalyst comprises a zeolite structure type MWW and palladium as the sole metal in an amount of 1.5 to 10 wt .-%, based on the sum of the weights of zeolite and palladium and calculated as Palladium-metal, as well as no zeolite whose largest channels are not formed by 10 tetrahedrally coordinated atoms containing.
14. Abgassystem, das 14. exhaust system, the
a) einen Katalysator gemäß einem oder mehreren der Ansprüche 1 bis 11 und a) a catalyst according to one or more of claims 1 to 11 and
b) einen SCR-Katalysator b) an SCR catalyst
umfasst. includes.
15. Abgassystem gemäß Anspruch 14, dadurch gekennzeichnet, dass der SCR-Katalysator ein Zeolith ist, der dem Gerüsttyp BEA, AEI, CHA, KFI, ERI, LEV, MER oder DDR angehört und der mit Kobalt, Eisen, Kupfer oder 15. The exhaust system according to claim 14, characterized in that the SCR catalyst is a zeolite belonging to the framework type BEA, AEI, CHA, KFI, ERI, LEV, MER or DDR and with cobalt, iron, copper or
Mischungen aus zwei oder drei dieser Metalle ausgetauscht ist. Mixtures of two or three of these metals is exchanged.
16. Abgassystem gemäß Anspruch 14 und/oder 15, dadurch 16. Exhaust system according to claim 14 and / or 15, characterized
gekennzeichnet, dass sich zwischen dem Katalysator, der ein Trägersubstrat der Länge L, Palladium und einen Zeolithen, dessen größte Kanäle von 10 tetraedrisch koordinierten Atomen gebildet werden, umfasst und dem SCR- Katalysator eine Einspritzeinrichtung für Reduktionsmittel befindet. characterized in that between the catalyst comprising a support substrate of length L, palladium and a zeolite whose largest channels are formed of 10 tetrahedrally coordinated atoms, and the SCR catalyst is a reducing agent injector.
17. Verfahren zur Reinigung von Abgasen von Kraftfahrzeugen, die mit mager betriebenen Motoren betrieben werden, dadurch gekennzeichnet, dass das Abgas über ein Abgassystem gemäß einem oder mehreren der Ansprüche 14 bis 16 geleitet wird . 17. A method for purifying exhaust gases of motor vehicles, which are operated with lean-burn engines, characterized in that the exhaust gas is passed through an exhaust system according to one or more of claims 14 to 16.
EP18758622.7A 2017-08-31 2018-08-24 Palladium/zeolite-based passive nitrogen oxide adsorber catalyst for purifying exhaust gas Pending EP3676000A1 (en)

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