[go: up one dir, main page]

EP0989903A1 - Pot catalytique a accumulation - Google Patents

Pot catalytique a accumulation

Info

Publication number
EP0989903A1
EP0989903A1 EP98928339A EP98928339A EP0989903A1 EP 0989903 A1 EP0989903 A1 EP 0989903A1 EP 98928339 A EP98928339 A EP 98928339A EP 98928339 A EP98928339 A EP 98928339A EP 0989903 A1 EP0989903 A1 EP 0989903A1
Authority
EP
European Patent Office
Prior art keywords
catalytically active
active component
storage catalyst
catalyst according
storage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98928339A
Other languages
German (de)
English (en)
Inventor
Martin Hartweg
Thomas Fetzer
Bernd Morsbach
Otto Kumberger
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.)
BASF SE
Mercedes Benz Group AG
Original Assignee
BASF SE
DaimlerChrysler AG
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 BASF SE, DaimlerChrysler AG filed Critical BASF SE
Publication of EP0989903A1 publication Critical patent/EP0989903A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
    • F01N3/0842—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2042—Barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2047—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20723—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/91—NOx-storage component incorporated in the catalyst
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/524—Spinel

Definitions

  • the invention relates to a storage catalytic converter according to the preamble of claim 1, as is known from the generic WO-97/02886.
  • a storage catalytic converter for the reduction of nitrogen oxides (N0 X ) in exhaust gases from lean-burn engines which has a N0 X storing and a N0 X catalytically reducing component.
  • the catalytically active component and the storage component are at least largely applied separately from one another on a carrier body.
  • the component storing the N0 X consists of one or more materials from the group consisting of metal oxides, metal hydrides, metal carbonates and mixed metal oxides, the corresponding metal being lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, stronzium and / or barium .
  • Such storage catalytic converters preferably having platinum and a barium compound, are subject to high thermal stress during operation, in particular in the presence of oxygen, and to rapid aging in particular here at temperatures above 600.degree.
  • loads occur when the previously bound N0 X is released and when sulfate poisoning is regenerated, so that the previously known th storage catalytic converters have a relatively short lifespan.
  • Another storage catalyst for lean mix engines is, for example. known from EP 562 805 AI.
  • This storage catalyst is a transition metal / zeolite catalyst, in which the transition metal was introduced into the zeolite carrier body by an ion exchange.
  • an exhaust system for lean mix engines and an engine control system necessary for reducing pollutants are known from this document.
  • the object of the invention is to further develop the underlying storage catalytic converter in such a way that it exhibits less thermal aging.
  • the storage catalytic converter should have this reduced aging, in particular when used in exhaust gas lines of internal combustion engines operated in lean / rich mixed operation, and in this case particularly preferably during tempering.
  • the object is achieved with an underlying storage catalytic converter with the characterizing features of claim 1.
  • the inventive combination of the catalytically active component and the N0 X-storing component with mutual low chemical activity at high temperatures (greater than 600 ° C, in particular higher 800 ° C - has the storage catalyst of the invention at these temperatures for a long thermal life in addition. it is cheaper to manufacture, among other things, by at least largely dispensing with precious metals.
  • Fig. 3 is a diagram of a N0 X (NO) reduction over the temperature for a 20% ZnO, 16% CuO and 64% A1 2 0 3 -containing catalytically active component, which has a spinel structure and additionally with 1.6 % Ce0 2 is impregnated,
  • FIG. 4 shows a diagram of a NOx (NO) reduction over the temperature in the case of a 20% ZnO, 16% CuO and 64% A1 2 0 3 -containing catalytically active component which has a spinel structure and additionally with 8% by weight. % Ce0 2 is impregnated,
  • FIG. 5 shows a diagram of a NOx (NO) reduction over the temperature in the case of a 20% ZnO, 16% CuO and 64% Al 2 0 3 -containing catalytically active component which has a spinel structure and additionally with a W0 3 , V 2 0 5 and Ti0 2 -containing solid is mixed,
  • Fig. 6 is a diagram of a NOx (NO) reduction versus temperature for a 20% ZnO, 16% CuO and 64% Al 2 0 3 -containing catalytically active component, which has a spinel structure and an additional 0.1 wt. % Vanadium,
  • FIG. 7 shows a diagram of a NOx (NO) reduction over temperature for a 20% ZnO, 16% CuO and 64% A1 2 0 3 -containing catalytically active component which has a spinel Has structure and additionally has 0.5% by weight of palladium,
  • Fig. 9 is a diagram of a dynamic NOx (NO) -Adsorbtion and NO x (NO) -Desorbtion over time at a ZnCuAl 2 0 4 - containing 'catalytically active component which has a spinel structure and, in addition as a storing component 3 , 5% BaCu0 2 and
  • FIG. 10 is a diagram of a dynamic NOx (NO) -Adsorbtion and NO x (NO) -Desorbtion over time at a ZnCuAl 2 0 4 -. Containing the catalytically active component which has a spinel structure and, in addition as a storing component 7% BaCu0 2 has.
  • the catalytically active component is simultaneously used as a carrier material for the NOx-storing component.
  • the active component is a spinel, in the sense of the invention a spinel is to be understood as a material of the general chemical formula A a Br, ⁇ which, at least microscopically, has a crystallographic or crystal-like cubic lattice structure with face-centered oxygen ions and tetrahedral and octahedral gaps, in which tetrahedral gaps the A particles and up to 50% of the B particles and in which octahedral gaps the remaining B particles are arranged.
  • an A or B particle only denotes their crystallographic arrangement.
  • substoichiometric compounds and / or compositions in which the B ß 0 3 acts as a matrix and which have the characteristic spinel lines in the X-ray spectrum are also to be regarded as spinels, the spinel
  • the formal composition A a B b ⁇ 4 is present in a Bt > 0 matrix, so that formally a stoichiometry of A a (lx) B b 0 4 results. From a material point of view, the A and B particles can be different from one another.
  • the A particle is one or more of the elements of the A group of Mg, Ca, Mn, Fe, Ni, Co Cu, Zn, Sn and Ti and the B particle is one or more elements of the B group Al, Ga, In, Co, ' Fe, Cr, Mn, Cu, Zn, Sn, Ti and Ni.
  • the elements of the exclusion group Mn, Fe and Co can be an A and a B particle at the same time.
  • the following at least spinel-like compositions have proven to be particularly expedient here: (MgCu) Al 2 0 4 , (CuCu) Al 2 0 4 , (CuZn) Al 2 0 4 , (CoZn) CuAl 2 0 4 , mixtures of (ZnCu) Al 0 4 with W0 3 and / or V 2 O 5 and / or Ti0 2 and here in particular in the composition Mg 0 . 5 CU 0.5 AI 2 O 4 , CU 0.5 CU 0 . 5 AI 2 O 4 , Cuo. 5 Zno .5 Al 2 0 4 , C ⁇ o. 25 Zn o.2 5 Cuo.s l2 ⁇ 4, or their mixtures with 10% W0 3 and 6% V 2 0s and / or 84% Ti ⁇ 2 and / or Al 2 0 3 .
  • the catalytically active component with additional catalytically active elements, in particular with palladium, platinum, rhodium, rutenium, osmium, iridium, rhenium and / or rare earths such as lantane and cerium, vanadium, titanium To provide niobium, molybdenum, tungsten and / or their salts and / or their oxides.
  • the spinel is manufactured using a process ren, as is known from DE 43 01 470 AI.
  • the bed height was approximately 15 mm.
  • a furnace is arranged which mm 'heats the reactor central part over a length of about 100, with temperatures up to 550 ° C are achievable.
  • a gas mixture was passed through the carrier material at a space velocity of approximately 10,000 per hour, which consists of 1000 pp NO, -1000 ppm propene, 10% oxygen and the rest argon as carrier gas. Behind the reactor, the NO concentration was measured with a gas detector, with any N0 formed before the detection being reduced to the nitrogen oxide NO in a converter. Oxidation of hydrocarbons to C0 2 by measuring the C0 2 content by the gas detector was observed simultaneously.
  • FIG. 1 The result of the measurement of the Cu 0 .sCu 0.5 Al 2 O 4 spinel according to Example 1 is shown in FIG. 1.
  • the diagram shows the course of the NO and the C0 2 content as a function of temperature.
  • NO NO
  • concentration reaches a low point between approx. 276 and 294 ° C. and then rises again.
  • a drastic decrease in the NO x concentration is observed from approx. 200 ° C., at the same time the hydrocarbons are decomposed to C0 2 , as is evident from the increase in the C0 2 concentration.
  • the temperature window in which there is a reduction in NO x is between 200 ° C. and 400 ° C., depending on the composition of the material.
  • a magnesium / copper / aluminum spinel in particular the composition Mg 0. SCu 0.5 Al 2 O 4 , is used as the spinel.
  • the spinel is advantageously produced analogously to a process as is known from DE 43 01 470 AI.
  • a mixture of 20% ZnO, 16% CuO and 64% A1 2 0 3 which has a spinel structure and is used as the catalytically active component - in the following examples 3 to 7, for simplicity, ZnCuAl 2 ⁇ 4 spinel - the one with 1.6 % Ce0 2 impregnated.
  • the above ZnCuAl 2 Ü 4 spinel is used as the spinel, which additionally has 8% by weight Ce0 2 .
  • the spinel is impregnated with 8% by weight Ce0.
  • the already mentioned ZnCAl 2 ⁇ 4 spinel is used as the spinel for the carrier material, which is now mixed with the oxides of tungsten, vanadium and titanium.
  • the mixture has 50% by weight of the Zn'CuAl 2 0 4 spinel, the remaining 50% by weight of the mixture of 5% by weight WO 3 , 3% by weight V 2 0 5 and 42 % By weight Ti0 2 is formed.
  • the result of the measurement of the spinel according to Example 5 is shown in FIG. 5.
  • NO N0 X
  • the temperature window in which there is a reduction in the NO x is between 150 ° C. and 500 ° C., depending on the composition of the material.
  • a spinel for 'the carrier material As a spinel for 'the carrier material is used a ZnCuAl 2 ⁇ 4 spinel of known composition, which is impregnated with 0.1% vanadium.
  • the ZnCuAl 2 0 4 spinel which is impregnated with 0.5% palladium, is used again as the spinel for the carrier material.
  • the result of the measurement of the spinel according to Example 7 is shown in FIG. 7.
  • NO NO
  • ZnCuAl 2 0 4 spinel + 0.5% by weight Pd a drastic decrease in the NO x concentration is observed from approx. 180 ° C., at the same time the hydrocarbons are decomposed to C0 2 , as is evident from the increase in C0 2 concentration shows.
  • the temperature window in which there is a reduction in the NO x is between 180 ° C. and 500 ° C., depending on the composition of the material.
  • a silver-containing spinel of the general chemical formula Ag »CuAl 0 4 is used as the catalytically active component, which was produced according to a process known from WO 94/02244.
  • the spinel has the property that NO x (NO) is stored in the nitrogen oxide-containing gas at temperatures below 145 ° C and is released again above 145 ° C.
  • the porous spinel extruded in pellets was exposed to a gas stream in a heatable reactor, the flow rate of which was approximately 30,000 l / h.
  • the composition of the gas was as follows: Ar + 800 ppm NO + 800 ppm C, H f + 10% 02 + 8% H 2 0. From the diagram, which for comparison also shows the behavior of other spinels in the presence of water the storage of NO below 145 ° C is clearly recognizable. Furthermore, the rise above 145 ° C. of the NO concentration above the initiated 800 ppm NO shows that the previously stored NO is released again. Since water is generated when fossil fuels are burned, this property of spinels is of great importance. Further investigations on the spinels mentioned showed a high resistance to N0 X , H 2 0, C0 2 and H 2 0.
  • a Z CuAl 2 ⁇ 4 spinel of the known composition is used, which is impregnated with 3.5% barium cuprate (BaCu0 2 ) as the storage component.
  • the long-term behavior of this storage catalytic converter was plotted over time in the diagram according to FIG.
  • the diagram shows the course of the temperature (measuring points are marked with the symbol "V), the course of the NO x concentration (measuring points are marked with the sign" ⁇ ”) and the course of the CO 2 concentration (measuring points are marked with the Character " ⁇ " marked) is plotted, the C0 2 concentration on the right and the temperature and the NO x concentration on the left coordinate.
  • the measurement was carried out on the basis of an endurance test and shows the above-mentioned courses in the time from 223000 s to 228000 s, ie approx. 62 hours after the start of the endurance test.
  • the test sequence was repeated periodically, the storage catalytic converter always being heated to approximately 350 ° C.
  • an oxygen-containing gas was introduced in accordance with lean operation of a lean-mix engine.
  • the gas had the following composition: Ar + 1000 ppm NO + 1000 ppm C 3 H 6 + 10% 0 2 .
  • an oxygen-free but strongly hydrocarbon-containing gas became, corresponding to a rich operation of a lean-burn engine initiated.
  • the gas had the following composition: Ar + 1000 ppm NO + 3000 ppm C 3 H 6 .
  • the desorption phase can be recognized by a steep increase in the C0 2 concentration (C0 2 peak).
  • the time period between two CO peaks is the adsorption phase. It takes about 10 minutes.
  • the adsorption phase with this composition of the storage catalytic converter should be set significantly shorter than 10 minutes.
  • the oxygen is turned off and the propene concentration (C 3 H 6 ), ie the concentration of hydrocarbon, is increased to three times the value.
  • the desorption phase is initiated by this measure.
  • the previously stored N0 X is released , which is then implemented.
  • the implementation can be recognized from the CO 2 peak occurring during the desorption phase.
  • the reaction taking place causes the storage catalyst material to self-heat.
  • NO x peak the NO x concentration
  • a ZnCuAl ⁇ 4 spinel of the known composition is used as the spinel for the carrier material and for the catalytic component, which is impregnated with 7% barium cuprate (BaCu0 2 ).
  • the measurement was carried out on the basis of an endurance test and shows the courses mentioned in the time from 341000 s to 346000 s, ie approx. 95 hours after the start of the endurance test.
  • the test procedure and the test parameters were the same as in example 9, which is why they are not discussed here any longer.
  • FIG. 10 The result of the measurement on a storage catalytic converter according to the invention according to Example 10 is shown in FIG. 10. Also in the diagram according to FIG. 10, the desorption phase, which lasts about one minute, can be recognized by a steep increase in the CO 2 concentration (CO 2 peak). The absorption phase between two desorption phases again takes about 10 minutes. In the present storage catalytic converter according to Example 10, there is at most a slight increase in the NO x concentration during the adsorption phase. By increasing the proportion of BaCu0 2 as a storage component, the saturation of the storage catalyst on NO x is reduced during the adsorption phase, as a result of which the maximum duration of the adsorption phase of this storage catalyst is increased compared to that according to Example 9.
  • the oxygen is turned off, as in Example 9, the propene concentration (C 3 H 6 ) is increased and the desorption phase is initiated.
  • NO x peak the NO x concentration
  • the NO x peak is due to insufficient impregnation of the storage catalyst with hydrocarbons at the beginning of the desorption phase and is also due to the apparatus structure of the test facility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

L'invention concerne un pot catalytique à accumulation pour un flux de gaz d'échappement notamment d'un moteur à combustion interne actionné en alternance avec un mélange pauvre et un mélange riche, de préférence un moteur Diesel ou un moteur à mélange pauvre, ou bien pour les gaz brûlés d'une usine d'incinération, comportant un constituant à action catalytique réductrice des oxydes d'azote, en présence d'hydrocarbures, et un constituant accumulant le NOx au moins en dessous de 100 DEG C. Le constituant à action catalytique présente la formule chimique AaBbO4, A désignant un ou plusieurs métaux bivalents et B désigne un ou plusieurs métaux trivalents et a + b </= 3 et a, b > 0. Le constituant à action catalytique comporte une structure réticulaire cristalline ou cubiquement de type cristallin, au moins sur le plan microscopique, avec des ions d'oxygène centrés en nappe et des interstices tétraédriques et octaédriques, les particules de A et jusqu'à 50 % des particules de B étant disposées dans les interstices tétraédriques, les particules de B résiduelles étant disposées dans les interstices octaédriques. En outre, l'enthalpie de réaction ou l'activité chimique entre le constituant à action catalytique et le constituant accumulant le NOx est faible du moins jusqu'à des températures de l'ordre de 600 DEG C, de préférence de l'ordre 800 DEG C.
EP98928339A 1997-06-11 1998-05-30 Pot catalytique a accumulation Withdrawn EP0989903A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19724545 1997-06-11
DE19724545A DE19724545A1 (de) 1997-06-11 1997-06-11 Speicherkatalysator
PCT/EP1998/003252 WO1998056492A1 (fr) 1997-06-11 1998-05-30 Pot catalytique a accumulation

Publications (1)

Publication Number Publication Date
EP0989903A1 true EP0989903A1 (fr) 2000-04-05

Family

ID=7832102

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98928339A Withdrawn EP0989903A1 (fr) 1997-06-11 1998-05-30 Pot catalytique a accumulation

Country Status (7)

Country Link
US (1) US6395244B1 (fr)
EP (1) EP0989903A1 (fr)
JP (1) JP2000512907A (fr)
CN (1) CN1263480A (fr)
CZ (1) CZ444599A3 (fr)
DE (1) DE19724545A1 (fr)
WO (1) WO1998056492A1 (fr)

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19908023A1 (de) * 1999-02-25 2000-08-31 Dornier Gmbh Verfahren und Element zur Speicherung von in einem Gas enthaltenen Stickoxiden
FR2793163B1 (fr) * 1999-05-07 2001-08-10 Ecia Equip Composants Ind Auto Composition d'epuration avec traitement des nox des gaz d'echappement d'un moteur a combustion interne
DE19929293A1 (de) * 1999-06-25 2000-12-28 Volkswagen Ag Verfahren zur Steuerung einer Regeneration eines NOx-Speicherkatalysators
FI118326B (fi) 2000-04-10 2007-10-15 Ecocat Oy Adsorbenttikatalyytti
US7247598B2 (en) * 2002-07-23 2007-07-24 Beijing University Of Chemical Technology Nano-scale magnetic solid base catalyst and its preparation method
US20040105804A1 (en) * 2002-11-29 2004-06-03 Industrial Technology Research Institute Catalyst for water-gas shift reaction and method for converting carbon monoxide and water to hydrogen and carbon dioxide
CN1812834B (zh) * 2003-06-26 2010-06-09 Scm金属制品公司 使用氧化锌助催化剂生产甲基氯硅烷的催化剂
US7399729B2 (en) 2003-12-22 2008-07-15 General Electric Company Catalyst system for the reduction of NOx
JP2005342710A (ja) * 2004-05-07 2005-12-15 Mitsubishi Chemical Engineering Corp 耐熱性脱硝触媒
ITMI20042455A1 (it) * 2004-12-22 2005-03-22 Sued Chemie Mt Srl Procedimento per la rimozione di ossidi di azoto con materiale absorbente di ossidi stessi
DE102005040582A1 (de) * 2005-08-22 2007-03-01 Itn Nanovation Gmbh Hochtemperaturstabile keramische Schichten und Formkörper
US8118035B2 (en) 2005-12-13 2012-02-21 Philip Morris Usa Inc. Supports catalyst for the combustion of carbon monoxide formed during smoking
EP2218501A4 (fr) * 2007-10-23 2014-01-29 Cataler Corp Catalyseur de purification de gaz d'échappement
KR100962082B1 (ko) * 2008-07-31 2010-06-09 희성촉매 주식회사 수소를 이용한 질소산화물의 환원제거용 촉매 및 이를이용한 질소산화물의 환원제거 방법
CN102836717B (zh) * 2012-09-10 2014-10-29 中南大学 一种尖晶石型氧化物的应用及催化脱硫脱硝的方法
US9511353B2 (en) 2013-03-15 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) Firing (calcination) process and method related to metallic substrates coated with ZPGM catalyst
US20140271387A1 (en) * 2013-03-15 2014-09-18 Cdti Optimal Composition of Copper-Manganese Spinel in ZPGM Catalyst for TWC Applications
US9511350B2 (en) 2013-05-10 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) ZPGM Diesel Oxidation Catalysts and methods of making and using same
US9511355B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) System and methods for using synergized PGM as a three-way catalyst
US9227177B2 (en) 2013-03-15 2016-01-05 Clean Diesel Technologies, Inc. Coating process of Zero-PGM catalysts and methods thereof
US9259716B2 (en) 2013-03-15 2016-02-16 Clean Diesel Technologies, Inc. Oxidation catalyst systems compositions and methods thereof
US9216383B2 (en) 2013-03-15 2015-12-22 Clean Diesel Technologies, Inc. System and method for two and three way ZPGM catalyst
DE102013207709A1 (de) * 2013-04-26 2014-10-30 Umicore Ag & Co. Kg Entschwefelung von NOX-Speicherkatalysatoren
US9545626B2 (en) 2013-07-12 2017-01-17 Clean Diesel Technologies, Inc. Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate
US20150051067A1 (en) * 2013-08-19 2015-02-19 Cdti Oxygen storage material without rare earth metals
US8853121B1 (en) * 2013-10-16 2014-10-07 Clean Diesel Technology Inc. Thermally stable compositions of OSM free of rare earth metals
US9511358B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. Spinel compositions and applications thereof
US9427730B2 (en) * 2014-11-17 2016-08-30 Clean Diesel Technologies, Inc. Bimetallic synergized PGM catalyst systems for TWC application
CN105983294A (zh) * 2015-02-10 2016-10-05 中国石油化工股份有限公司 一种脱除烟气中硫氧化物和氮氧化物的方法
GB2540350A (en) * 2015-07-09 2017-01-18 Johnson Matthey Plc Nitrogen oxides (NOx) storage catalyst
CN106582796B (zh) * 2015-10-14 2019-07-09 中国石油化工股份有限公司 乙烷和苯烷基化反应的催化剂
CN106582795B (zh) * 2015-10-14 2019-04-12 中国石油化工股份有限公司 用于乙烷和苯烷基化反应的催化剂
US20170326533A1 (en) * 2016-05-11 2017-11-16 Clean Diesel Technologies, Inc. Oxygen storage capacity of non-copper spinel oxide materials for twc applications
CN109219480B (zh) * 2016-06-06 2021-08-06 本田技研工业株式会社 废气净化催化剂
JP2018171599A (ja) * 2017-03-31 2018-11-08 トヨタ自動車株式会社 排ガス浄化触媒
US10596519B1 (en) * 2019-05-08 2020-03-24 Toyota Motor Engineering & Manufacturing North America, Inc. Modified ferrite catalysts for direct no decomposition and a method of making and using a catalyst
US11559792B2 (en) * 2021-03-19 2023-01-24 Toyota Motor Engineering & Manufacturing North America, Inc. Zinc manganese-iron spinel with an alkali metal stabilizer as an oxygen storage material resistant to rich/lean aging

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49120869A (fr) * 1973-03-22 1974-11-19
JPS5610334A (en) * 1979-07-06 1981-02-02 Toyota Motor Corp Catalyst for cleaning up exhaust gas and manufacture of said catalyst
GB8519319D0 (en) 1985-07-31 1985-09-04 Shell Int Research Catalyst
EP0614692A1 (fr) * 1990-05-03 1994-09-14 Sakai Chemical Industry Co., Ltd., Catalyseurs et procédés pour la dénitration
JP2547124B2 (ja) * 1991-02-02 1996-10-23 工業技術院長 窒素酸化物の還元除去方法
DE4224881A1 (de) * 1992-07-28 1994-02-03 Basf Ag Silberhaltiger Aluminiumoxid-Trägerkatalysator und Verfahren zur katalytischen Zersetzung von reinem oder in Gasgemischen enthaltenem Distickstoffmonoxid
US5362463A (en) 1992-08-26 1994-11-08 University Of De Process for removing NOx from combustion zone gases by adsorption
DE4301470A1 (de) * 1993-01-21 1994-07-28 Basf Ag Verfahren zur katalytischen Zersetzung von reinem oder in Gasgemischen enthaltenem Distickstoffmonoxid
JP2922759B2 (ja) * 1993-09-29 1999-07-26 京セラ株式会社 窒素酸化物除去用酸化物触媒材料並びに窒素酸化物除去方法
JP3374999B2 (ja) * 1993-10-14 2003-02-10 トヨタ自動車株式会社 排気ガス浄化用触媒
DE69503527T2 (de) * 1994-01-20 1999-04-29 Toyota Jidosha K.K., Toyota, Aichi Katalysator zur Reinigung von Abgasen
FR2718371B1 (fr) * 1994-04-08 1996-05-03 Rhone Poulenc Chimie Catalyseurs de réduction des oxydes d'azote à base de spinelles.
DE4419486C2 (de) * 1994-06-03 1996-09-05 Daimler Benz Ag Katalysator, Verfahren zu dessen Herstellung sowie Verwendung des Katalysators
DE4420932A1 (de) * 1994-06-16 1996-01-11 Basf Ag Material zur katalytischen Reduktion von Stickoxiden
JPH0824648A (ja) * 1994-07-22 1996-01-30 Nissan Motor Co Ltd 排気ガス浄化用触媒及びその製造方法
DE19546484A1 (de) * 1995-12-13 1997-07-10 Daimler Benz Ag Verfahren zum Betreiben einer Reinigungsanlage für Gase sowie eine Reinigungsanlage für Gase
JPH08173811A (ja) * 1994-12-26 1996-07-09 Nissan Motor Co Ltd 排気ガス浄化用触媒及びその製造方法
JP3417702B2 (ja) * 1994-12-28 2003-06-16 エヌ・イーケムキャット株式会社 窒素酸化物吸蔵組成物及び排気ガス浄化方法
US5874057A (en) * 1995-07-12 1999-02-23 Engelhard Corporation Lean NOx catalyst/trap method
DE19546482A1 (de) 1995-12-13 1997-06-26 Basf Ag Verfahren zum Betreiben einer Reinigungsanlage, eine Reinigungsanlage und eine Verwendung derselben
DE19546481C2 (de) * 1995-12-13 1998-08-13 Daimler Benz Ag Katalysator und Verfahren zu dessen Herstellung und Verwendung desselben
DE19606657C1 (de) * 1996-02-23 1997-07-10 Basf Ag Verfahren und Vorrichtung zum Reinigen von Gasen
JPH09248458A (ja) * 1996-03-18 1997-09-22 Toyota Central Res & Dev Lab Inc 排ガス浄化用触媒及び排ガス浄化方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9856492A1 *

Also Published As

Publication number Publication date
CZ444599A3 (cs) 2000-06-14
JP2000512907A (ja) 2000-10-03
CN1263480A (zh) 2000-08-16
US6395244B1 (en) 2002-05-28
WO1998056492A1 (fr) 1998-12-17
DE19724545A1 (de) 1998-12-24
MX9911500A (en) 2000-04-01

Similar Documents

Publication Publication Date Title
WO1998056492A1 (fr) Pot catalytique a accumulation
EP1004347B1 (fr) Catalyseur pour purifier les gaz d&#39;échappement de moteurs Diesel
EP0791390B1 (fr) Procédé et dispositif pour la purification de gaz
DE19813655C2 (de) Speichermaterial für Schwefeloxide, Verfahren zu dessen Herstellung und Verwendung
EP2616647B1 (fr) Catalyseur pour éliminer les oxydes d&#39;azote des gaz d&#39;échappement de moteurs diesels
EP0779093B1 (fr) Application d&#39;un catalyseur à base de spinelle
EP0945608B1 (fr) Procédé d&#39;opération d&#39;un dispositif d&#39;épuration des gaz d&#39;échappement comprenant un piège de soufre et un catalyseur d&#39;accumulation des oxydes d&#39;azote
DE69730539T2 (de) Abgasreinigungsanlage einer Brennkraftmaschine und Katalysator zum Reinigen des Abgases einer Brennkraftmaschine
DE202007019652U1 (de) Katalysator zur Verminderung Stickstoff-haltiger Schadgase aus dem Abgas von Dieselmotor
DE60124610T2 (de) Adsorber-Katalysator
EP0685253A1 (fr) Catalyseur, procédé de sa préparation et son utilisation
DE19546612A1 (de) Verfahren zur Reduktion von NOx aus Abgasen
EP1180397B1 (fr) Matériau à base de cérium oxide pour le stockage de l&#39;oxygène, procédé de préparation dudit matériau et utilisation pour le traitment des gaz d&#39;échappement des moteurs à combustion interne
EP0779094A2 (fr) Catalyseur à base de spinelle, sa préparation et son application
DE60036909T2 (de) Verfaren zur Entfernung von Stickoxiden mittels eines Werkstoffes mit Ilmenit-Struktur
DE60129181T2 (de) Katalysator und Verfahren zur Abgasreinigung
DE60033351T2 (de) Verfahren zur Entfernung von Stickstoffoxiden
EP1216745A2 (fr) Catalyseur-accumulateur de NOx, procédé pour sa fabrication ainsi que son application
DE10132890A1 (de) Feststoff und Verfahren zur Adsorption und Desorption von Stickoxiden in Abgasen von Verbrennungskraftmaschinen
DE69726036T2 (de) NOx-Zersetzungskatalysator und Abgasreiniger unter Verwendung dieses Katalysators
EP0272620B1 (fr) Procédé pour éliminer les oxydes d&#39;azote de gaz de fumée, provenant de la combustion de charbon
DE69839225T2 (de) Verfahren zur herstellung eines katalysators zur reinigung von abgasen
DE10261817A1 (de) Verfahren zur katalytischen Umwandlung von Stickoxiden in Stickstoff
MXPA99011500A (en) Storage catalyst
DE102005039349A1 (de) Stickstoffoxide entfernendes Material und Vorrichtung

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19991124

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

17Q First examination report despatched

Effective date: 20010706

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20030204