CN1131726C - Composition for use as NOX trap, combining two compositions based on manganese and another element selected among alkalines, alkaline-earths and rare earths and use thereof for treating exhaust gases - Google Patents

Composition for use as NOX trap, combining two compositions based on manganese and another element selected among alkalines, alkaline-earths and rare earths and use thereof for treating exhaust gases Download PDF

Info

Publication number
CN1131726C
CN1131726C CN008084165A CN00808416A CN1131726C CN 1131726 C CN1131726 C CN 1131726C CN 008084165 A CN008084165 A CN 008084165A CN 00808416 A CN00808416 A CN 00808416A CN 1131726 C CN1131726 C CN 1131726C
Authority
CN
China
Prior art keywords
composition
carrier
manganese
wash coat
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN008084165A
Other languages
Chinese (zh)
Other versions
CN1354689A (en
Inventor
C·伯特
T·伯切姆
C·布里
M·吉昂
C·赫杜因
N·莫拉尔
T·庞蒂尔
C·萨达
T·希吉隆
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.)
ECIA Equipements et Composants pour lIndustrie Automobile SA
Rhodia Chimie SAS
Renault SAS
Original Assignee
ECIA Equipements et Composants pour lIndustrie Automobile SA
Renault SAS
Rhone Poulenc Chimie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR9905843A external-priority patent/FR2793161B1/en
Priority claimed from FR9905872A external-priority patent/FR2793164B1/en
Priority claimed from FR9905869A external-priority patent/FR2793163B1/en
Application filed by ECIA Equipements et Composants pour lIndustrie Automobile SA, Renault SAS, Rhone Poulenc Chimie SA filed Critical ECIA Equipements et Composants pour lIndustrie Automobile SA
Publication of CN1354689A publication Critical patent/CN1354689A/en
Application granted granted Critical
Publication of CN1131726C publication Critical patent/CN1131726C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B01D2255/2022—Potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B01D2255/2027—Sodium
    • 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
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9207—Specific surface
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Landscapes

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

Abstract

The invention relates to a compound and its use as NOx trap in the treatment of exhaust gases. Said compound is characterized in that it comprises a combination of: a first composition comprising a support and an active phase, the active phase being based on manganese and at least another element A selected among the alkalines and alkaline earths, the manganese and the element A being chemically bound; a second composition comprising a support and an active phase based on manganese and at least another element B selected among the alkalines, the alkaline-earths and rare earths, said second composition having or capable of having a specific surface area of at least 10 m<2>/g after being calcined for eight hours at 800 DEG C.

Description

Two kinds have been made up based on the composition of manganese and the another kind of element that is selected from alkali metal, alkaline-earth metal and rare earth element and can be used as composition and the purposes of said composition in exhaust-gas treatment of NOx trapping agent
Invention field
The present invention relates to a kind of composition of the NOx of can be used as trapping agent and the purposes in exhaust-gas treatment thereof, said composition has made up two kinds of compositions, the active element that is selected from alkali metal, alkaline-earth metal and rare earth element based on manganese and another kind of each composition.
Background technology
Known reduction is from vehicle electric motor nitrogen oxides from exhaust gas (NOx), specifically utilizes " ternary " catalyst to carry out, and this catalyst utilization is present in reducibility gas in the mixture with stoichiometry.Any excessive oxygen all can cause the obvious deterioration of catalyst performance.
Now, the diesel oil motor or the gasoline motor of some motor such as poor combustion operation are economical from the fuel consumption aspect, but can discharge waste gas that these waste gas contain a large amount of unnecessary oxygen through regular meeting, for example are at least 5%.Therefore the three-way catalyst of standard is invalid to the NOx that discharges in this case.To limit the NOx discharging be necessary to the after-combustion standard that is used for the motor automobile now by strictness in addition.
In order to address this problem, specifically proposed to be known as the system of NOx trapping agent, this system can be oxidized to NO with NO 2, sponge the NO of formation like this then 2Under certain condition, NO 2Form salt, the reducing agent that is contained in the waste gas then reduction.But these NOx trapping agents still have some shortcomings.Therefore observed after old, they trend towards only operating under very high temperature, so their opereating specification has reduced.Therefore obtaining a kind of can operated system should be useful in wideer temperature range.In addition, they are usually based on noble metal.These metals are very expensive now, and their feasibility may have problems.In order to reduce cost, obtaining also to be useful there not being catalyst feasible under the situation of noble metal.
Summary of the invention
Therefore a theme of the present invention is a kind of composition of exploitation, and said composition can be used in whole wide temperature range, and optional can the use under the situation of no any noble metal.
At this purpose, the composition that the present invention can be used as the NOx trapping agent is characterised in that it comprises the combination of following composition:
-the first composition, said composition contain a kind of carrier with a kind of mutually active, and this activity is based on manganese and at least a another elements A that is selected from alkali metal and alkaline-earth metal, and manganese and elements A are chemical bonding;
-the second composition, said composition contains a kind of carrier with a kind of mutually active, this activity is based on manganese and at least a another element B that is selected from alkali metal, alkaline-earth metal and rare earth element, and this second composition has maybe after 8 hours in calcining under 800 ℃ can have 10m at least 2The specific area of/g.
The specific embodiment
Reading hereinafter specification and concrete but behind the non-circumscribed embodiment that is described, other characteristics of the present invention, details and advantage will be clearer.
In whole specification, it is the element set that 57 to 71 element is formed that rare earth can be regarded as by yttrium and cycle atom ordinal number.
In addition, specific area can be regarded as the BET specific area, determine according to the nitrogen absorption that the ASTM D 3663-78 standard that with the BRUNAUER-EMMETT-TELLER method described in the periodical " The Journalof the American Chemical Society; 60; 309 (1938) " is benchmark is determined
Composition of the present invention is characterised in that and has made up two kinds of specific compositions, will describe these compositions in more detail hereinafter.
These compositions include a kind of carrier with a kind of mutually active.In composition, the term carrier should adopt its broad sense to define essential element and/or itself do not have catalysis or trapping ability or catalysis that it had or trapping ability with active be not equal to mutually and its on deposit other element.For simplicity, in the following description with reference to a kind of carrier with a kind of active mutually or by the carrier band phase, but be understood that if the described activity that belongs to is present in the carrier mutually or by the element of carrier band phase,, still be within the scope of the present invention as in the preparing carriers process, being introduced into.
First composition is described below.
This composition contains a kind of mutually active based on manganese and at least a another elements A that is selected from alkali metal and alkaline-earth metal.For alkali metal, what can more specifically mention is sodium and potassium.For alkali earth metal, what can more specifically mention is barium.For said composition, can contain one or more elements A, mentioned elements A all is interpreted as also being applicable to the situation of several elements A in therefore hereinafter describing.
In addition, manganese and elements A are present in first composition with the form of chemical bonding.This means between manganese and elements A, to exist that these elements are not simply and are listed in the simple mixture by the formed chemical bond of the reaction between them.Therefore manganese may reside in the compound with elements A or the mixed oxide type mutually in.This compound or this specifically can be expressed as general formula A mutually xMn yO 2 ± δ(1), 0.5≤y/x≤6 wherein, the value of δ depends on the character of elements A and the oxidation state of manganese.For the phase or the compound of general formula (1), the example that can mention has vernadite, hollandite, romanechite or psilomelane, birnessite, todorokite, buserite or lithiophorite.This compound is optional can be hydrate.This compound can have Cdl in addition 2The layer structure of type.Explanation has provided general formula (1) by way of example herein, if manganese and elements A remain chemical bonding, but has different general formulas, then should not exceed scope of the present invention.
XR or Electronic Micro-Analysis can confirm the existence of this compounds.
The oxidation number of manganese can from 2 to 7 variations, more particularly from 3 to 7 variations.
Under the situation of potassium, this element and manganese can be with compound Ks 2Mn 4O 8Form exist.Under the situation of barium, then can be BaMnO 3The compound of type.
The situation that the present invention is contained is that the activity of wherein first composition is mainly formed manganese and elements A chemical bonding by manganese and one or more another elements A that are selected from alkali metal and alkaline-earth metal mutually." main form " can be regarded as composition of the present invention can activity mutually in demanganization and elements A do not have still have NO under the situation of other element in addition xTrapping ability, as do not have the precious metal element or be usually used in other metal of catalysis.
Further contain a kind of carrier in this first composition.Can use any porous carrier that can be used in catalytic field for carrier.Preferably have enough chemical inertnesses for this carrier with respect to manganese and elements A, to avoid the key reaction of one or both and carrier in these elements, this class reaction may stop the formation of the chemical bond between manganese and the elements A.But, under the situation of carrier and these element reactions,, may use more substantial manganese and elements A in order to obtain chemical bond required between these elements.
This carrier can aluminium oxide be the basis.The aluminium oxide that can have any kind of the specific area that is enough to be used in catalysis herein all can use.Can should be mentioned that by at least a aluminium hydroxide, as the hydroxide of bayerite, gibbsite or gibbsite, promise gibbsite and/or at least a aluminium such as boehmite, intend the aluminium oxide that boehmite and diaspore fast dewatering obtain.
Aluminium oxide after stable also can use.For what stable element can be mentioned rare earth, barium, silicon, titanium and zirconium arranged.The mixture that cerium, lanthanum or lanthanum/neodymium are arranged that can mention especially for rare earth.
The preparation of stablizing aluminium oxide is to be undertaken by known mode own.Specifically utilize the salt of the stable element that preamble mentions such as the solution impregnation aluminium oxide of nitrate, perhaps by the precursor of dry aluminium oxide and the salt of these elements simultaneously, calcining is carried out then.
The oxide that this carrier also can be selected from cerium oxide, zirconia or their mixture is the basis.
Can should be mentioned that specifically that for cerium oxide and zirconia blend described in patent application EP-A-605274 and the EP-A-735984, the application combines wherein disclosed content.More specifically can use the carrier based on cerium and Zirconium oxide, wherein cerium/the atomic percent zirconium of these oxides existence is at least 1.For identical carrier, with also can using that the solid solution form exists.In these cases, the X diffraction spectrogram of carrier has disclosed the single homogeneous existence of carrier inside.For containing the maximum carrier of cerium, this actual mutually corresponding cubic oxide cerium CeO of crystalization 2, with respect to the pure zirconia cerium, its cell parameter more or less is changed, and therefore the zirconium of institute's combination is changed into the crystal network of cerium oxide, thereby obtains real solid solution.
For cerium oxide and zirconic mixture, can should be mentioned that in addition based on two kinds of oxides, also have mixture based on scandium oxide or the rare earth except that cerium, be specially described in the patent application WO 97/43214 those, the application combines wherein disclosed content.This application has specifically described the composition based on cerium oxide, zirconia and yittrium oxide, also have except cerium oxide and zirconia, be selected from the composition of cerium oxide and the rare earth oxide except that cerium based at least a other, wherein cerium/atomic percent zirconium is at least 1.Calcining is after 6 hours down at 900 ℃ for these compositions, and specific area is at least 35m 2/ g, under 400 ℃, its oxygen storage capacity is 1.5ml O at least 2/ g.
According to the concrete embodiment of the present invention, carrier further contains silica based on cerium oxide.Described this class carrier in patent application EP-A-207857 and EP-A-547924, the application combines wherein disclosed content.
The total content of manganese, alkali metal and alkaline-earth metal can change in big proportion.Minimum content is not observe NO when being lower than this content xThe absorption behavior.This content can be between 2 and 50%, more specifically between 5 and 30% particularly.This content is expressed as with respect to oxide in the carrier and the active atomic percentage of the total moles of middle coherent element mutually.Manganese, alkali metal and alkaline-earth metal content separately also can change in big proportion, and manganese contains the content that measuring can equal or approach alkali metal or alkaline-earth metal particularly.
According to the useful variation pattern of the present invention, alkali metal is potassium, and its content (by above representing) can be between 10-50%, more specifically between 30-50%.
First composition of the present composition can be prepared by a kind of method, wherein carrier contacts with precursor and at least a another elements A of manganese and at least a elements A or at least a manganese, and wherein whole composition is at a temperature lower calcination, and this temperature is enough to form chemical bond between manganese and elements A.
A kind of method that can be used for above-mentioned contact process is a dipping.Therefore at first form by the solution of the salt of the element of carrier band phase or compound or slurries.
For salt, can select inorganic acid salt, as nitrate, sulfate or chloride.
Acylate also can use, and is specially aliphatic saturated monocarboxylic acid salt or carboxylate.That can mention as an example, has formates, acetate, propionate, oxalates or a citrate.
Utilize this solution or slurry carrier then.
What more specifically use is the dry method dipping.Dry method dipping comprises in the element aqueous solution that adds certain volume in impregnated product, and this volume equals the pore volume of impregnated solid.
Useful is branch two stages are carried out the deposition of active phase element.Therefore manganese is deposited in the phase I, and elements A is deposited in second stage.
After dipping, optional with carrier drying, calcining then.It should be noted and also may use the carrier of not calcined before the dipping.
Also can reach the salt of carrier element mutually or the suspension of compound deposits active phase based on activity by atomizing.Calcine resulting aerosol then.
As indicated above, under the temperature that is enough to make formation chemical bond between manganese and the elements A, calcine.This temperature changes with the character of elements A, but when calcining in air, this temperature is at least 600 ℃ usually, more specifically is at least 700 ℃, specifically can be between 800 ℃ and 850 ℃.Along with the chemical bond between manganese and the elements A forms, do not need higher temperature usually, and on the other hand, they may cause the carrier specific area to reduce, this may reduce the catalytic performance of composition.The calcining duration is specifically depended on temperature, and it determines should be enough to form chemical bond between element.
Various details second composition.
Said composition comprises that also a kind of carrier is with a kind of mutually active.
The content of the active phase of relevant first composition mentioned above also is suitable for herein, the character of concrete relevant this phase element and their amount.Therefore more specifically element B can be sodium, potassium or barium.
Second composition active mutually also can manganese and at least a rare earth element be basic.More specifically, this rare earth element can be selected from cerium, terbium, gadolinium, samarium, didymum.The total content of manganese, alkali metal, alkaline-earth metal or rare earth element can be between 1 to 50%, more specifically change between 5 to 30%.This content be expressed as with respect to support oxide and with by the atomic percentage of the total mole number of the mutually relevant element of carrier band.Manganese, alkali metal, alkaline-earth metal and rare earth element content separately also can change in big proportion, and the content of manganese can equal or approach the content of element B particularly.
The situation that the present invention is contained is that wherein activity mainly is made up of manganese and one or more another element B that are selected from alkaline-earth metal and rare earth element mutually." main form " mean composition of the present invention can activity mutually in demanganization and element B do not have still have NO under the situation of other element in addition xTrapping ability, as do not have the precious metal element or be usually used in other metal of catalysis.
As indicated above, the characteristics of second composition be it 800 ℃ down calcining have maybe after 8 hours and can have 10m at least 2The specific area of/g.Under identical temperature, calcine the identical time after, this specific area is specifically as follows 20m at least 2/ g.More particularly, calcining is after 8 hours down at 800 ℃, and this specific area is at least 80m 2/ g, even more specifically be 100m at least 2/ g.
Specific area can be regarded as the BET specific area, determine according to the nitrogen absorption that the ASTM D 3663-78 standard that with the BRUNAUER-EMMETT-TELLER method described in the periodical " The Journal of theAmerican Chemical Society; 60; 309 (1938) " is benchmark is determined
This surface area feature is to reach by the carrier of selecting appropriate carriers, particularly having a sufficiently high specific area.
This carrier can aluminium oxide be the basis.The aluminium oxide that can have any kind of the specific area that is enough to be used in catalysis here all can use.Can should be mentioned that by at least a aluminium hydroxide, as the hydroxide of bayerite, gibbsite or gibbsite, promise gibbsite and/or at least a aluminium such as boehmite, intend the aluminium oxide that boehmite and diaspore fast dewatering obtain.
According to the concrete embodiment of the present invention, use be aluminium oxide after stable.For what stable element can be mentioned rare earth, barium, silicon and zirconium arranged.The mixture that cerium, lanthanum-neodymium are arranged that can specifically mention for rare earth.
The preparation of stablizing aluminium oxide is to be undertaken by known mode own.Specifically utilize the salt of the stable element that preamble mentions such as the solution impregnation aluminium oxide of nitrate, perhaps by the precursor of dry aluminium oxide and the salt of these elements simultaneously, calcining is carried out then.
It is when the stabilizing agent of being made up of lanthanum compound and optional neodymium compound exists that method of alumina is stablized in the another kind of preparation that can mention, alumina powder to hydroxy Al or the formation of aluminium hydroxide fast dewatering carries out the slaking operation, more specifically, stabilizer compounds wherein can be a salt.Can be suspended in the water by making aluminium oxide, be heated to the temperature between 70-110 ℃ then, carry out slaking.After the slaking, aluminium oxide is heat-treated.
Another kind of preparation method is made up of similar processing method, only is to use barium.
Stabiliser content is expressed as the weight with respect to the stabilizer oxide content of the aluminium oxide after stable, is generally 1.5-15%, more specifically is 2.5-11%.
This carrier can silica be the basis also.
Also can be to be silica and titanium oxide between the 0.1-15% based on the Ti/Ti+Si atomic ratio.This ratio more specifically is 0.1-10%.Specifically described this carrier in patent application WO99/01216, the application combines wherein disclosed content.
For other carrier that is fit to, based on also can using of cerium oxide and zirconia, these oxides can mixed oxide or the solid solution of zirconia in cerium oxide or the form existence of the solid solution of cerium oxide in zirconia.These carriers are obtained by first kind method, and this method comprises that a formation contains the stage of the mixture of zirconia and cerium oxide, and utilize carbon number greater than 2 alkoxide compound the mixture of formation like this to be washed or flood.Mixture after calcining is flooded then.
Alkoxylated compounds specifically can be to be selected from general formula (2) R 1-((CH 2) x-O) n-R 2Product, R wherein 1And R 2Represent linear or non-linear alkyl or H or OH or Cl or Br or I; N is the number between 1 to 100; X is the number between 1 to 4, perhaps can be general formula (3) (R 3, R 4)--((CH 2) x-O) nThe product of-OH, wherein refers to phenyl ring, R 3And R 4Be identical or different substituting group in this ring, represent hydrogen or carbon number is 1 to 20 linearity or non-linear alkyl, and x and n such as preamble are defined; Perhaps can be general formula (4) R 4O-((CH 2) x-O) nThe product of-H, wherein R 4For carbon number is 1 to 20 linear or non-linear alcohol radical, x and n such as preamble are defined; And general formula (5) R 5-S-((CH 2) x-O) nThe product of-H, wherein R 5For carbon number is 1 to 20 linear or non-linear alkyl, x and n such as preamble are defined.Can be for these products with reference to patent application WO98/16472, the application combines wherein disclosed content.
These carriers also can be obtained by second class methods, this method comprises a stage, a kind of solution and cerium solution, zirconium salt solution and a kind of anion surfactant, non-ionic surface active agent, polyethylene glycol, carboxylic acid and their salt of being selected from react in this stage, and this reaction is chosen wantonly under the condition of alkali and/or oxidant existence and carried out.
More specifically, carboxylate, phosphate, sulfate and sulfonate all can be used as anion surfactant.In non-ionic surface active agent, preferably can use ethyoxyl alkyl phenol and amine ethoxylate.
Reaction between zirconium and the cerium salt can be undertaken by the solution that heating contains these salt, therefore relates to the hydrolysis that is heated.Also can be undertaken by in the solution that contains these salt, introducing alkali formation precipitation.
For these products, can be with reference to patent application WO98/45212, the application combines wherein disclosed content.
The same procedure that can use being used to of above providing to prepare first composition prepares second composition.It should be noted after carrier and active element contact mutually, should with should integral body at the temperature lower calcination that is enough to element is existed with oxide form.Usually, this temperature is at least 500 ℃, more specifically is at least 600 ℃.
Composition of the present invention as described above exists with powder type, but choose wantonly its shaping is existed with particle, bead, cylinder or the honeycomb style of various sizes.
The invention still further relates to a kind of system that captures NOx that can be used in, this system comprises a wash coat that has catalytic performance and combine the present composition (wash coat), this wash coat is deposited on the matrix, as the monolithic matrix of metal or pottery.
This system may reside in the different embodiments.
In first kind of embodiment, this system comprises matrix and by two wash coats that lamination constitutes up and down.In this case, ground floor contains first composition of composition, and the second layer contains second composition.These layers can be in any order, and promptly the internal layer that contacts with matrix can contain first or second composition, and be deposited on another composition that skin on the ground floor contains composition.
According to second kind of embodiment, composition is present in the wash coat with the form of individual layer, and in this case, this individual layer contains above-mentioned two kinds of compositions with the form of mixture, for example obtains mixture by mechanical mixture.
The third embodiment can be imagined out.In this case, system contains two matrixes of discharging side by side, and each matrix all contains one deck wash coat.The wash coat of first matrix contains first composition, and the wash coat of second matrix contains second composition.
In addition, the invention still further relates to composition mentioned above purposes in making this type systematic.
The invention still further relates to that a kind of to utilize composition of the present invention be the gas processing method of purpose to reduce discharged nitrous oxides.
The gas that can handle within the scope of the invention has the gas of gas turbine, power station boiler or engine exhaust.Under in the end a kind of situation, can comprise diesel engine and poor burn engine.
When composition of the present invention contacted with hyperoxic gas, it can be used as the NOx trapping agent.Hyperoxic gas means that this gas contains excessive oxygen with respect to the necessary oxygen amount of motor chemistry of fuel metering combustion, and or rather, with respect to stoichiometry ratio λ=1, this gas has excessive oxygen, and promptly the λ value of this gas is greater than 1.This λ value and air/fuel ratio are undertaken related by itself known mode in field of internal combustion engine particularly.This class gas can be the gas of poor combustion motor, and its oxygen content (expression by volume) is at least 2%, and the higher gas of oxygen content, the gas of diesel engine for example, be that oxygen content is at least 5% or greater than 5%, more specifically be at least 10%, for example this content can be between 5% and 20%.
The present invention is applicable to that also above-mentioned gas also contains the situation of 10% water.
To provide an embodiment below.
In this embodiment, NO xThe assessment test of trapping agent is carried out in the following manner:
With every kind of NO xEach 0.15g of trapping agent (first composition and second composition) packs into powder type in the quartz reactor.Employed powder preferably is compacted, and grinds then and sieves, thereby isolate the particulate fraction that is of a size of 0.125-0.25mm.
The reactant mixture at reactor inlet place has following composition (volume):
-NO：300vpm
-O 2：10％
-CO 2：10％
-H 2O：10％
-N 2: surplus
Total flow rate is 30Nl/h.
The VVH magnitude is 150,000h -1
Write down NO and NO in the reactor always x( ) and temperature signal.
NO and NO xSignal is by ECOPHYSICS NO xAnalyzer provides on chemiluminescent principle.
To NO xThe assessment of trapping agent is the NO by determining that capture is absorbed when mutually saturated xTotal amount (being expressed as mgNO/g captures mutually or active phase) is carried out.Repeated experiments under the different temperatures between 250-500 ℃.Therefore can determine NO xThe optimum temperature range that trapping agent works.
A) first composition
Raw material:
Use manganese nitrate Mn (NO 3) 24H 2O and potassium nitrate KNO 399.5%.
Employed carrier is the type described in the embodiment 4 of patent application WO97/43214, based on the carrier of cerium oxide, zirconia and lanthana, is 72/24/4 with respect to oxide part by weight separately promptly.
Preparation of compositions:
Carry out two depositional phases.
Stage 1:Deposit first kind of active element
This stage comprises that equaling 10% according to atomic weight deposits active element Mn, and its account form is as follows:
[Mn]/([Mn]+[CeO 2]+[ZrO 2]+[La 2O 3])＝0.10
Stage 2:Deposit second kind of active element;
This stage is to equal 10% according to atomic ratio to deposit second kind of active element K, and its account form is as follows:
[K]/([Mn]+[K]+[CeO 2]+[ZrO 2]+[La 2O 3])＝0.10
Utilizing dry method to flood deposits.This method be utilize the activity be dissolved in the solution mutually unit usually flood related carrier, the pore volume that liquor capacity equals carrier (utilizes water to determine: 0.5cm 3/ g), its concentration can reach desired concentration.
In this case, element is immersed on the carrier one by one.
Operation sequence is as follows:
First kind of element of-dry method dipping
-in baking oven dry (110 ℃, 2 hours)
-calcined 2 hours down at 600 ℃
Second kind of element of-dry method dipping
-in baking oven dry (110 ℃, 2 hours)
-calcined 2 hours down at 800 ℃
B) second composition
Raw material:
Use manganese nitrate Mn (NO 3) 24H 2O and potassium nitrate KNO 399.5%.
Employed carrier is a Condea SB3 aluminium oxide, and this carrier has utilized the Ce dipping of 10% atomic weight stable, calcines 2 hours down at 500 ℃ then.
The preparation composition:
(pore volume of dry method dipping, carrier utilizes 0.8cm to mode identical during according to preparation first composition 3/ g water is determined), utilize the Mn of same amount and K element to carry out two depositional phases, calcining is for the first time carried out under 500 ℃, carries out under 800 ℃ for the second time.The BET surface area of the composition that obtains like this is 117m 2/ g.
Provided catalytic result below.
T℃ NO xReserves (mg NO xThe active phase of/g)
250 10
300 12
350 22
400 19
450 16
500 9
So just tested NO in the whole temperature range between 250-500 ℃ xThe capture activity.This activity is to produce under the situation of non precious metal.

Claims (19)

1. composition that can be used as the NOx trapping agent is characterized in that it comprises the combination of following composition:
-the first composition, said composition contain a kind of carrier with a kind of mutually active, and this activity is based on manganese and at least a another elements A that is selected from alkali metal and alkaline-earth metal, manganese and elements A chemical bonding;
-the second composition, said composition contains a kind of carrier with a kind of mutually active, this activity is based on manganese and at least a another element B that is selected from alkali metal, alkaline-earth metal and rare earth element, and this second composition has maybe after 8 hours in calcining under 800 ℃ can have 10m at least 2The specific area of/g;
At the described NO that can be used as xIn the composition of trapping agent, described first composition and described second composition exist simultaneously, and the content of the two is all greater than 0.
2. the composition of claim 1 is characterized in that second composition descends calcining to have maybe after 8 hours at 800 ℃ and can have 20m at least 2The specific area of/g.
3. claim 1 or 2 composition, it is characterized in that second composition 800 ℃ down calcining have maybe after 8 hours and can have 80m at least 2The specific area of/g.
4. claim 1 or 2 composition, it is characterized in that second composition 800 ℃ down calcining have maybe after 8 hours and can have 100m at least 2The specific area of/g.
5. claim 1 or 2 composition is characterized in that elements A and B are selected from potassium, sodium or barium.
6. claim 1 or 2 composition, the carrier that it is characterized in that second composition are based on aluminium oxide or the aluminium oxide after silicon, zirconium, barium or a kind of rare earth element are stable.
7. claim 1 or 2 composition, the carrier that it is characterized in that second composition is based on silica.
8. claim 1 or 2 composition, the carrier that it is characterized in that second composition is based on Ti/Ti+Si atomic ratio silica and titanium oxide between 0.1-15%.
9. claim 1 or 2 composition, the carrier that it is characterized in that second composition is based on cerium oxide and zirconia, this carrier obtains by a kind of method, in this method, formation contains the mixture of zirconia and cerium oxide, and utilizes carbon number greater than 2 alkoxide compound the mixture of formation like this to be washed or flood.
10. claim 1 or 2 composition, the carrier that it is characterized in that second composition is based on cerium oxide and zirconia, this carrier obtains by a kind of method, in this method, cerium solution and zirconium salt solution and a kind of additive reaction that is selected from anion surfactant, non-ionic surface active agent, polyethylene glycol, carboxylic acid and their salt, this reaction are chosen wantonly under the condition of alkali and/or the existence of a kind of oxidant and are carried out.
11. the composition of claim 1 or 2, the carrier that it is characterized in that first composition are based on the oxide that is selected from aluminium oxide, cerium oxide, zirconia or their mixture.
12. the composition of claim 1 or 2, the carrier that it is characterized in that first composition be based on cerium oxide, and further contain silica.
13. system that comprises matrix and wash coat, wherein wash coat combines the composition of one of claim 1-12, composition is present in the wash coat on the matrix, and its existing way is that ground floor contains aforementioned first composition, the second layer contains aforementioned second composition.
14. a system that comprises matrix and wash coat, wherein wash coat combines the composition of one of claim 1-12, and said composition is present in the wash coat on the matrix with the form of the mixture of aforementioned two kinds of compositions.
15. system that contains two matrixes of placing side by side, the composition that one of wash coat and claim 1-12 are arranged on described each matrix, described composition is present in the wash coat on first matrix with the form of aforementioned first composition, is present in the wash coat on second matrix with the form of aforementioned second composition.
16. one kind is the gas processing method of purpose to reduce discharged nitrous oxides, it is characterized in that using the system of one of the composition of one of claim 1-12 or claim 13-15.
17. the method for claim 16, what it is characterized in that handling is waste gas from internal combustion engine.
18. the method for claim 17 is characterized in that handled gas contains excessive oxygen with respect to stoichiometric number.
19. the composition of one of claim 1-12 is used for handling the purposes of the system of engine exhaust gas in production.
CN008084165A 1999-05-07 2000-05-05 Composition for use as NOX trap, combining two compositions based on manganese and another element selected among alkalines, alkaline-earths and rare earths and use thereof for treating exhaust gases Expired - Fee Related CN1131726C (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
FR9905843A FR2793161B1 (en) 1999-05-07 1999-05-07 EXHAUST PURIFICATION DEVICE FOR AN INTERNAL COMBUSTION ENGINE
FR99/05869 1999-05-07
FR9905872A FR2793164B1 (en) 1999-05-07 1999-05-07 COMPOSITION FOR PURIFYING EXHAUST GASES FROM AN INTERNAL COMBUSTION ENGINE
FR9905869A FR2793163B1 (en) 1999-05-07 1999-05-07 PURIFICATION COMPOSITION WITH TREATMENT OF NOX FROM EXHAUST GASES OF AN INTERNAL COMBUSTION ENGINE
FR99/05843 1999-05-07
FR99/05872 1999-05-07

Publications (2)

Publication Number Publication Date
CN1354689A CN1354689A (en) 2002-06-19
CN1131726C true CN1131726C (en) 2003-12-24

Family

ID=27253530

Family Applications (1)

Application Number Title Priority Date Filing Date
CN008084165A Expired - Fee Related CN1131726C (en) 1999-05-07 2000-05-05 Composition for use as NOX trap, combining two compositions based on manganese and another element selected among alkalines, alkaline-earths and rare earths and use thereof for treating exhaust gases

Country Status (9)

Country Link
EP (1) EP1187675A1 (en)
JP (1) JP2002543964A (en)
KR (1) KR20020042528A (en)
CN (1) CN1131726C (en)
AU (1) AU4413800A (en)
BR (1) BR0010365A (en)
CA (1) CA2373080A1 (en)
MX (1) MXPA01011243A (en)
WO (1) WO2000067904A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6727202B2 (en) 2001-08-21 2004-04-27 Engelhard Corporation Enhanced NOx trap having increased durability
FR2845932A1 (en) * 2002-10-17 2004-04-23 Rhodia Elect & Catalysis Catalyst useful for removing nitrogen oxides from automobile exhaust gases comprises rare-earth-doped alumina, manganese, alkali metal and platinum
JP4746264B2 (en) * 2003-11-17 2011-08-10 三井金属鉱業株式会社 Exhaust gas purification catalyst and exhaust gas purification device for internal combustion engine
EP2279785A3 (en) * 2005-03-29 2011-09-21 Yanmar Co. Ltd. Exhaust gas purifier
JP2006272115A (en) * 2005-03-29 2006-10-12 Yanmar Co Ltd Exhaust gas purifying apparatus
RU2398629C2 (en) * 2006-02-17 2010-09-10 Родиа Операсьон Composition base on oxides of zirconium, cerium, yttrium, lanthanum and other rare-earth metals, method of its production and use in catalysis
JP5626093B2 (en) * 2011-04-19 2014-11-19 株式会社豊田中央研究所 Exhaust gas purification catalyst, production method thereof, and exhaust gas purification method using the same
CN110038555A (en) * 2019-04-22 2019-07-23 沈阳师范大学 A kind of preparation method and application of birnessite type manganese oxide catalyst
EP3888787A4 (en) * 2019-09-04 2022-05-04 Grirem Advanced Materials Co., Ltd. Rare earth manganese/cerium-zirconium-based composite compound, preparation method therefor and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2257696B (en) * 1991-06-28 1995-05-31 Riken Kk Method and apparatus for cleaning exhaust gas
US5362463A (en) * 1992-08-26 1994-11-08 University Of De Process for removing NOx from combustion zone gases by adsorption
FR2738756B1 (en) * 1995-09-20 1998-12-11 Rhone Poulenc Chimie PROCESS FOR THE TREATMENT OF HIGH OXYGEN CONTENT FOR REDUCING NITROGEN OXIDE EMISSIONS USING A CATALYTIC COMPOSITION COMPRISING MANGANESE OXIDE AND CERIUM AND / OR ZIRCONIUM OXIDE
US5837212A (en) * 1995-09-21 1998-11-17 Ford Global Technologies, Inc. Potassium/manganese nitrogen oxide traps for lean-burn engine operation

Also Published As

Publication number Publication date
EP1187675A1 (en) 2002-03-20
MXPA01011243A (en) 2003-07-14
JP2002543964A (en) 2002-12-24
CA2373080A1 (en) 2000-11-16
BR0010365A (en) 2002-02-13
WO2000067904A1 (en) 2000-11-16
AU4413800A (en) 2000-11-21
CN1354689A (en) 2002-06-19
KR20020042528A (en) 2002-06-05

Similar Documents

Publication Publication Date Title
CN1218779C (en) Catalyst for absorption storage reduction type Nox purification
CN1166441C (en) Nitrogen oxide storage material and nitrogen oxide storage catalytic agent produced with it
CN1130247C (en) Support composition based on cerium oxide, zirconium oxide and scandium or rare earth oxide and use for treating exhaust gas
KR101688850B1 (en) Nitrogen oxide storage catalytic converter for use in a motor vehicle in a position near the engine
CN1182910C (en) Nitrogen oxide storing catalyst
CN1317073C (en) Particulate matter-oxidizing material and oxidizing catalyst
CN1009338B (en) Rhodium-free three-member catalyst
RU2698675C2 (en) Inorganic oxide material
CN1032748A (en) Rhodium-free three-member catalyst
CN104971729A (en) Monolithic catalyst for catalytic combustion of propane, and preparation method thereof
CN1131726C (en) Composition for use as NOX trap, combining two compositions based on manganese and another element selected among alkalines, alkaline-earths and rare earths and use thereof for treating exhaust gases
CN101068617A (en) Catalyst for purifying exhaust gas
CN1131724C (en) Compositions used as NOX trap, based on manganese and alkaline or alkaline-earth and use for treating exhaust gases
CN1283131A (en) Composition based on manganese and use for trapping Nox for treating exhaust
CN1925910A (en) Exhausting purifying catalyst
JP4737984B2 (en) Heat resistant oxide
CN1132681C (en) Composition usable as NOx trap, based on manganese and an alkaline-earth or a rare earth and use in the treatment of exhaust gases
EP2029261A1 (en) Catalyst for purification of exhaust gas
CN1927459A (en) Exhaust gas purification catalyst and catalyst-equipped diesel particulate filter
CN100337726C (en) Catalyst for purifying exhaust gases and process for producing the same
US10975744B2 (en) Exhaust gas purification apparatus for motor vehicles
JP2006035018A (en) Carrier for catalyst and catalyst using the same
CN1145524C (en) Zinc aluminate with high specific surface area, preparation method and use for treating motor vehicle exhaust gases
JP4836187B2 (en) Exhaust gas purification catalyst, production method thereof and regeneration method thereof
CN1261205C (en) Water gas purifying catalyst

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee