CN1132681C - Composition usable as NOx trap, based on manganese and an alkaline-earth or a rare earth and use in the treatment of exhaust gases - Google Patents

Composition usable as NOx trap, based on manganese and an alkaline-earth or a rare earth and use in the treatment of exhaust gases Download PDF

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Publication number
CN1132681C
CN1132681C CN008079072A CN00807907A CN1132681C CN 1132681 C CN1132681 C CN 1132681C CN 008079072 A CN008079072 A CN 008079072A CN 00807907 A CN00807907 A CN 00807907A CN 1132681 C CN1132681 C CN 1132681C
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composition
carrier
manganese
gas
rare earth
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CN1351518A (en
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T·伯切姆
C·海杜因
T·赛格隆
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J23/16—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01D2255/204—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

Abstract

The invention concerns a composition usable as NOx trap in the treatment of exhaust gases. Said composition comprises a support and an active phase, and is characterised in that the active phase is based on manganese and at least another element A selected among alkaline-earths and rare earths, and it has or is capable of having a specific surface area of at least 10m<2>/g after being calcined for 8 hours at 800 DEG C. The support can be based on alumina or alumina stabilised with silicon, zirconium, barium or a rare earth; or based on silica or silica and titanium oxide.

Description

With manganese and alkaline earth or rare earth be base, as NO xThe composition of trapping agent, and the application in handling waste gas
Technical field
The present invention relates to a kind of based on composition manganese and alkaline earth or rare earth, that be used as the Nox trapping agent and the application in handling waste gas thereof.
Background technology
Can by stoichiometry utilize " ternary " catalyst of the reducing gas that exists in the waste gas mist, reduce particularly from the nitrogen oxide (NO in the vehicle engine exhaust gas x) emission.Any excessive oxygen all can cause the obvious deterioration of catalyst performance.
Yet, some engine, capable of saving fuel as Diesel engine or poor combustion petrol engine, but emit the waste gas that always contains a large amount of excess of oxygen, for example at least 5%.Therefore, in this case, the three-way catalyst of standard is for NO xEmission is useless.In addition, the severization of automobile after-combustion regulations has forced to limit NO xDischarge, these regulations have extended to such engine now.
In order to overcome this problem, proposed to be called NO xThe system of trapping agent, it can be oxidized to NO to NO 2, absorb formed NO then 2Under certain conditions, discharge NO 2, be reduced into N by the reducing substances that contains in the waste gas then 2But, these NO xTrapping agent has some shortcomings.They move through high temperature the time unsatisfactorily, so their ageing properties are poor.In addition, their possibility sulfur resistances are poor.
Summary of the invention
Therefore, the object of the invention is to provide the NO of the ageing resistance with improvement xTrapping agent.
The present invention also aims to provide the NO of sulfur resistance with improvement xTrapping agent.
For this reason, of the present invention as NO xThe composition of trapping agent comprises carrier with mutually active, is characterised in that this activity is based on manganese and at least a other elements A that is selected from alkaline earth and rare earth mutually, and feature is that also it has after 8 hours or can have 10m at least 800 ℃ of calcinings 2The specific area of/g.
From following description and the non-limiting example that provides by describing mode, it is clearer that further feature of the present invention, details and advantage will become.
Composition of the present invention comprises that carrier is with mutually active.Its wide significance should be got in term " carrier ", i.e. essential element (or multiple essential element) in it is formed, perhaps do not have catalytic activity or capture active, perhaps not with the catalysis of active equivalent or capture active; And deposit other a kind of element or multiple element on it.For simplicity, the remainder of this description will discuss carrier with active mutually or by a year phase, but should be appreciated that, scope of the present invention also comprises following situation, described as activity mutually or a kind of element that is carried the part of phase be present in the carrier, for example, in the preparation process of carrier itself, be incorporated on the carrier.
The activity of said composition is based on manganese and at least a elements A.This elements A can be alkali metal or alkaline-earth metal.Barium can be used as alkaline earth element.More particularly, rare earth element can be selected from cerium, terbium, gadolinium, samarium, didymum.The total content of manganese, alkaline earth or rare earth can be in the 1%-50% scope, more particularly in the 5%-30% scope.The molal quantity summation of the element that these ratios comprise in carrying mutually with respect to support oxide and quilt is represented with atom %.Manganese, alkaline earth or rare earth content separately also can be in the scope of broad; Especially, manganese content can equal or near the content of elements A.
The present invention includes following situation: activity is the situation that manganese and at least a or several elements A are selected from alkaline earth and rare earth mutually substantially." be " to be meant that composition of the present invention can have NO under the situation without any element (for example noble metal type element or other metal of using always) in activity except manganese and described one or more elements A in catalysis substantially xCapture active.
As mentioned above, to be it have after 8 hours or can have 10m at least 800 ℃ of calcinings for said composition feature 2The specific area of/g.Especially, this surface can have 20m at least after the identical time calcining of uniform temp 2The specific area of/g.More particularly, this specific area 80m at least 2/ g still more particularly is at least 100m 800 ℃ of calcinings after 8 hours 2/ g.
Term " specific area " is meant the BET specific area of the nitrogen determining adsorption of the standard A STM D 3663-78 that sets up according to the BRUNAUER-EMMETT-TELLER method of describing in the periodical " American Chemical Society's journal " 60,309 (1938).
Obtain this surface characteristic by the suitable carrier of selecting to have sufficiently high specific area.
This carrier can be based on aluminium oxide.Can use the aluminium oxide of any kind that can have the specific area of enough in catalysis, using.What can mention is by making the aluminium oxide of at least a aluminium hydroxide fast dewatering formation, as bayerite, gibbsite, gibbsite, promise gibbsite, and/or at least a aluminum oxyhydroxide, as boehmite, pseudobochmite or diaspore.
In particular of the present invention, use the aluminium oxide of stabilisation.The stabilizing element that can address comprises rare earth, barium, silicon and zirconium.The specific rare earth that can mention is cerium, lanthanum or lanthanum-neodymium mixture.
Prepare the aluminium oxide of stabilisation with a kind of known method itself,, perhaps calcine after dry by the salt of alumina precursor and these elements is common particularly salt (as the nitrate) solution impregnation of aluminium oxide with above-mentioned stabilizing element.
Adducible another kind of preparation method of alumina is, wherein pass through the Powdered aluminium oxide that aluminium hydroxide or aluminum oxyhydroxide fast dewatering form, in the presence of the stabilizing agent that comprises lanthanum compound and the neodymium compound of choosing wantonly, handle more particularly a kind of salt of described compound through ageing.Can be suspended in aluminium oxide in the water, the temperature that for example are heated to then in 70 ℃ of-110 ℃ of scopes are carried out ageing.After the ageing, aluminium oxide is through Overheating Treatment.
Another kind of preparation method is made up of similar processing, but is to use barium.
The amount of stabilizing agent is represented with respect to the weight of stabilized aluminium oxide with steady oxide, generally in the 1.5%-15% scope, more particularly in the 2.5%-11% scope.
Carrier also can be a silicon-dioxide-substrate.
Also can be silica and titania based, the Ti/Ti+Si atomic ratio be in the 0.1%-15% scope.More particularly, this ratio can be in the 0.1%-10% scope.This carrier is described in international monopoly WO 99/01216, and this paper is incorporated by reference for its content.
Operable another kind of suitable carriers is a base with cerium oxide and zirconia; These oxides can exist with the form of mixed oxide, perhaps exist with the solid solution or the solid solution form of cerium oxide in zirconia of zirconia in cerium oxide.These carriers can obtain with first method, are included in and wherein form mixture that contains zirconia and cerium oxide and the step of washing or flooding this mixture with the alkoxylated compounds that contains two above carbon atoms.Calcine the mixture that is flooded then.
This alkoxylated compounds can be selected from has formula for (2) R 1-((CH 2) x-O) n-R 2Product, wherein, R 1And R 2Expression line style or non-linearity alkyl or H or OH or Cl or Br or I; N is the numeral in the 1-100 scope; X is the numeral in the 1-4 scope; Perhaps have formula and be (3) (R 3, R 4)-v ((CH 2) x-O) nThe product of-OH, wherein, v represents phenyl ring, R 3And R 4Be the identical or different substituting group on the phenyl ring and represent hydrogen or contain the alkyl of the line style or the non-linearity of 1-20 carbon atom that x and n definition are as above; Perhaps have formula and be (4) R 4O-((CH 2) x-O) nThe product of-H, wherein, R 4Expression contains the line style or the non-linearity alcohol of 1-20 carbon atom, and x and n definition are as above; With having formula is (5) R 5-S-((CH 2) x-O) nThe product of-H, wherein, R 5Expression contains the alkyl of 1-20 carbon atom, and x and n definition are as above.Described these products in international monopoly WO 98/16472, this paper is incorporated by reference for its content.
These carriers also can obtain by second method, may further comprise the steps: make cerium solution, zirconium salt solution and be selected from the additive reaction of anionic surfactant, nonionic surface active agent, polyethylene glycol, carboxylic acid and salt thereof, this reaction may be carried out in the presence of alkali and/or oxidant.
More particularly, operable anionic surfactant is carboxylate, phosphate, sulfate and sulfonate.Operable preferred nonionic surfactants is ethoxylated alkylphenol and ethoxylated amine.
Zirconates and cerium salt can contain solution reaction in the pyrohydrolysis reaction of described salt by heating.Also can precipitate and react by introducing alkali in the solution that contains described salt.
Described these products in international monopoly WO 98/45212, this paper is incorporated by reference for its content.
Composition of the present invention can be by following method preparation, comprise carrier is contacted with at least a other elements A with manganese or contacting, and make its whole calcining being enough to make precursor or described element to change under the temperature of oxide with the precursor of manganese and at least a other elements A.In general, at least 500 ℃ of this temperature, more particularly at least 600 ℃.
A kind of method that can be used for carrying out above-mentioned contact is a dipping.Therefore, at first form the salt of the element that is carried phase or the solution or the slurry of compound.
Described salt is selected from inorganic acid salt, as nitrate, sulfate and chloride.
Also can use acylate, particularly representative examples of saturated aliphatic carboxylic salt or hydroxycarboxylate.Adducible example is formates, acetate, propionate, oxalates and citrate.
Use this solution or slurry impregnated carrier then.
More particularly, use dried dipping.Dried dipping comprises in product to be impregnated the aqueous solution of the described element that adds certain volume, and this volume equals the pore volume of solid to be impregnated.
It may be favourable dividing the element of two active phases of deposition.Therefore advantageously, sedimentation manganese in the first step, deposition of elements A in second step then.
Behind dipping, randomly dry support, calcining then.Should note to use the carrier that before dipping, does not have calcining.
Also can deposit mutually active with the salt of the element of activity phase and carrier or the suspension that compound is base by spray-drying.Calcine the spray-drying product of gained then.
The composition of the invention described above is a powder type, but randomly, it can form granule, pearl, cylinder or the honeycomb ceramics of various sizes.
The invention still further relates to the method that reduces discharged nitrous oxides with compositions-treated gas of the present invention.
Manageable in the present invention gas is, for example from the gas of combustion gas turbine, power station stove or internal combustion engine.Under latter event, they can be Diesel engine or poor burn engine.
Composition of the present invention when contacting with the gas of elevated oxygen level as NO xTrapping agent.Term " gas of elevated oxygen level " is meant the amount oxygen excessive gas required with respect to the stoichiometric(al) combustion of fuel, and more accurately, with respect to the gas of stoichiometric number λ=1 contained oxygen excess, promptly the λ value is greater than 1 gas.The λ value in known manner with air/fuel than relevant, the spy is for internal combustion engine in addition.These gases can be the gas from the oxygen content of for example poor burn engine (representing with volume) at least 2%, for example from Diesel engine at least 5% or greater than 5%, the gas of the elevated oxygen level of at least 10% oxygen content more particularly, this content may be in the 5%-20% scope.
The present invention also can be used for containing in addition the gas of the above-mentioned type of water, and water content is for example in 10% scope.
Composition of the present invention can be used to handle the waste gas from the internal combustion engine that uses sulfurous fuels, i.e. sulfur content 50ppm at least, the more particularly fuel of 200ppm (representing with elementary sulfur) at least.Its wide significance should be got in term " sulphur ", promptly refers to the sulphur and the sulfur-containing compound that exist in the fuel.
The invention still further relates to the catalysis system that comprises according to the processing engine exhaust gas of composition of the present invention.More accurately, this system for example comprises having catalytic property and washing dip-coating layer (wash coat) based on these compositions on bulk metal and ceramic mould carrier.
The invention still further relates to the application of above-mentioned composition in producing this catalysis system.
The specific embodiment
Now provide embodiment.
In an embodiment, preparation of compositions is as follows.
Preparation of compositions:
Use following material: manganese nitrate Mn (NO 3) 2H 2O, 99.5% potassium nitrate KNO 3And 99.5% barium nitrate Ba (NO 3) 2
Used carrier is the SB3 aluminium oxide from Condea.
Deposit in two steps.
The first step: the deposition of first kind of active element
This step comprises with the scale deposits active element Mn by the 10 atom % that calculate below:
[Mn]/([Mn]+[Al 2O 3])＝0.10
Second step: the deposition of second kind of active element
This step comprises that by second kind of active element X of dried immersion deposition, it can be K (Comparative composition) or Ba, and ratio is 10 atom %, is calculated as follows:
[X]/([Mn]+[X]+[Al 2O 3])＝0.10
This method comprises the carrier of being considered with the element dipping that is dissolved in the active phase in the solution, and liquor capacity equals the pore volume of carrier, and concentration is for obtaining to wish the concentration of concentration.
In this case, use following rules, element floods successively and enters carrier:
● the dried dipping of first kind of element;
● oven drying (110 ℃, 2 hours);
● 500 ℃ of calcinings 2 hours;
● the dried dipping of second kind of element;
● oven drying (110 ℃, 2 hours);
● 850 ℃ of calcinings 2 hours.
Resulting composition:
Composition Active phase (850 ℃ of calcinings are after 2 hours) BET surface area
1 (contrast) 10％Mn，10％K 148m 2/g
2 10％Mn，10％Ba 112m 2/g
Embodiment 1
Present embodiment illustrates the ageing resistance of composition of the present invention.
In the present embodiment, catalytic test carries out as follows:
Every kind of above-mentioned NO of 0.15g xCollector composition is packed into powder type in the quartz reactor.Used powder is repressed, grinds then and sieves, and isolates the screening of particle size at the 0.125-0.250 millimeter.
The reactant mixture at reactor inlet place has following composition (representing with volume):
●NO：300vpm
●O 2：10％
●CO 2：10％
●H 2O：10％
●N 2：qsp 100％
Total flow be 30 marks rise/hour.
HSV is 150000 hours -1The order of magnitude.
Along with the temperature in the reactor is noted down NO and NO continuously xSignal ( )。
By measuring NO adsorbed when capture is mutually saturated xTotal amount (NSC) (with every gram trapping agent or active phase NO the milligram numerical table show), the assessment NO xTrapping agent.Experiment is carried out at 250 ℃.
In addition, described composition uses follow procedure aging through the hydrothermal oxidization reduced form.
At N 2In 60 minutes, the temperature of composition is elevated to 950 ℃ down.Then composition is incubated 6 hours under this temperature, has respectively under 15 minutes oxygen and aqueous vapor atmosphere in nitrogen, under 15 minutes hydrogen and aqueous vapor atmosphere in nitrogen, hocket 24 cycles.When processing finishes, at H 2/ N 2Middle temperature is reduced to 80 ℃, then at N 2In.
The result is shown in the following table.
Composition NSC, non-ageing prod NSC, ageing prod Difference
1 (contrast) 9.2 2.9 -68％
2 7.0 3.6 -45％
As can be seen, composition of the present invention has the ageing resistance of improvement.
Embodiment 2
Present embodiment illustrates the sulfur resistance of composition of the present invention.
Use the composition of (unaged) identical with embodiment 1.The reactant mixture at reactor inlet place and embodiment 1 have the SO that identical composition or said composition have extra 30ppm 2
The result is shown in following table.
Composition NSC, no SO 2 NSC has SO 2 Difference
1 (contrast) 9.2 6.2 -33％
2 7.0 5.4 -22％
As can be seen, composition of the present invention has the anti-SO of improvement 2Performance.

Claims (15)

1. handle gas to reduce the method for discharged nitrous oxides for one kind, be characterised in that and use a kind of composition as NO xTrapping agent, described composition comprise carrier with mutually active, and described activity is based on manganese and at least a other elements A that is selected from alkaline earth and rare earth mutually, and described composition has 10m at least 800 ℃ of calcinings after 8 hours 2The specific area of/g.
2. the method according to claim 1 is characterised in that described composition has 80m at least 800 ℃ of calcinings after 8 hours 2The specific area of/g.
3. the method according to claim 1 is characterised in that described composition has 100m at least 800 ℃ of calcinings after 8 hours 2The specific area of/g.
4. the method according to claim 1 or 2 is characterised in that the active of described composition is manganese and at least a described elements A mutually basically.
5. the method according to claim 1 or 2 is characterised in that described elements A is a barium.
6. method according to claim 1 or 2 is characterised in that described carrier is based on aluminium oxide or with silicon, zirconium, barium or rare earth-stabilized aluminium oxide.
7. the method according to claim 1 or 2 is characterised in that described carrier is based on silica.
8. the method according to claim 1 or 2 is characterised in that described carrier based on silica and titanium oxide, and wherein the Ti/Ti+Si atomic ratio is in the 0.1%-15% scope.
9. method according to claim 1 or 2, be characterised in that described carrier based on cerium oxide and zirconia, described carrier is by comprising that forming the mixture and the described mixture that comprise zirconia and cerium oxide obtains with containing greater than the alkoxylated compounds washing of 2 carbon atoms or the method for dipping.
10. method according to claim 1 or 2, be characterised in that described carrier is based on cerium oxide and zirconia, described carrier obtains by comprising the method that makes cerium solution, zirconium salt solution and be selected from the additive reaction of anionic surfactant, nonionic surface active agent, polyethylene glycol, carboxylic acid and salt thereof, and described reaction is chosen wantonly in the presence of alkali and/or oxidant and carried out.
11. the method according to claim 1 or 2 is characterised in that the waste gas of processing from internal combustion engine.
12. the method according to claim 1 or 2 is characterised in that the gas that processing is excessive with respect to stoichiometric number oxygen.
13. the method according to claim 11 is characterised in that the oxygen content at least 2 volume % of described gas.
14. the method according to claim 12 is characterised in that the oxygen content at least 2 volume % of described gas.
15. a catalysis system of handling engine exhaust gas is characterised in that described catalysis system uses a kind of composition as NO xTrapping agent, described composition comprise carrier with mutually active, and described activity is based on manganese and at least a other elements A that is selected from alkaline earth and rare earth mutually, and described composition has 10m at least 800 ℃ of calcinings after 8 hours 2The specific area of/g.
CN008079072A 1999-04-23 2000-04-18 Composition usable as NOx trap, based on manganese and an alkaline-earth or a rare earth and use in the treatment of exhaust gases Expired - Fee Related CN1132681C (en)

Applications Claiming Priority (2)

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FR99/05187 1999-04-23
FR9905187A FR2792547B1 (en) 1999-04-23 1999-04-23 COMPOSITION FOR USE AS A NOx TRAP, BASED ON MANGANESE AND AN ALKALINE EARTH OR RARE EARTH, AND USE IN THE TREATMENT OF EXHAUST GASES

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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
JP3377676B2 (en) * 1996-04-05 2003-02-17 ダイハツ工業株式会社 Exhaust gas purification catalyst
FR2791907B1 (en) * 1999-04-12 2002-06-21 Rhodia Chimie Sa COMPOSITIONS FOR USE AS A NOx TRAP, BASED ON MANGANESE AND AN ALKALINE OR AN ALKALINE EARTH AND USE IN THE TREATMENT OF EXHAUST GASES

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FR2792547B1 (en) 2001-07-06
WO2000064580A1 (en) 2000-11-02
KR20020007386A (en) 2002-01-26
KR100420909B1 (en) 2004-03-02
EP1181094A1 (en) 2002-02-27
NO20015161D0 (en) 2001-10-22
FR2792547A1 (en) 2000-10-27
NO20015161L (en) 2001-12-20
CN1351518A (en) 2002-05-29

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