WO2018051890A1 - Catalyseur d'oxyde composite très résistant a la chaleur pour la purification des gaz d'échappement, et procédé de sa production - Google Patents

Catalyseur d'oxyde composite très résistant a la chaleur pour la purification des gaz d'échappement, et procédé de sa production Download PDF

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WO2018051890A1
WO2018051890A1 PCT/JP2017/032303 JP2017032303W WO2018051890A1 WO 2018051890 A1 WO2018051890 A1 WO 2018051890A1 JP 2017032303 W JP2017032303 W JP 2017032303W WO 2018051890 A1 WO2018051890 A1 WO 2018051890A1
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composite oxide
exhaust gas
catalyst
oxide catalyst
gas purification
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PCT/JP2017/032303
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English (en)
Japanese (ja)
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庸裕 田中
三郎 細川
謙太郎 寺村
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国立大学法人京都大学
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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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • 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
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust

Definitions

  • the present invention relates to a highly heat-resistant composite oxide catalyst for exhaust gas purification and a method for producing the same, and more particularly, to a novel composite oxide catalyst with ultra-reduced precious metal reduction aimed at purifying automobile exhaust gas and a method for producing the same.
  • noble metal species such as Pd and Rh are mainly used as automobile exhaust gas purification catalysts. It is known that Pd has high oxidation activity under rich conditions (oxygen-diluted conditions), and Rh exhibits extremely high NO x reduction activity.
  • the noble metal species has high activity as an automobile exhaust gas purification catalyst and is an indispensable element for automobiles.
  • these noble metal species are rare elements, there is a problem that price fluctuations are severe.
  • research on reducing the amount of noble metal used and substitution of noble metal elements has been actively carried out, and it has been clarified that Cu exhibits activity against NO selective reduction among transition metals.
  • a Cu 2+ ion exchange ZSM-5 zeolite catalyst is effective in a NOx selective reduction reaction using hydrocarbon (HC) as a reducing agent.
  • HC hydrocarbon
  • Al 2 O 3 is most often used as a carrier for metal catalysts, and the present inventor has reported that a Cu / Al 2 O 3 catalyst is also effective for automobile exhaust gas.
  • the Cu-based catalyst has a problem that the NO purification efficiency at a low temperature is extremely low and it is not suitable for exhaust gas purification in the cold state.
  • automobile exhaust gas purification catalysts are required not to have a catalytic activity that decreases when they come into contact with high-temperature exhaust gas.
  • catalyst supports such as Al 2 O 3 and zeolite have poor heat resistance, and a new high heat resistant catalyst support is desired for reducing and replacing the amount of noble metal used.
  • the main object of the present invention is to develop a novel catalyst that reduces the amount of noble metal used and has high heat resistance.
  • the present invention provides the following heat-resistant composite oxide catalyst for exhaust gas purification and a method for producing the same.
  • Item 1. Formula (I) M / M 1 M 2 1-x Ti x O 3-d (I) (In the formula, M represents at least one noble metal selected from the group consisting of Pd, Rh and Pt. M 1 represents Ca, Sr or Ba. M 2 represents Fe, Mn, Co, Ni or Cu. X is 0.4 to 1.0, d is 0 to 0.5, and M 1 M 2 1-x Ti x O 3-d is a perovskite-type metal composite oxide support. ) A highly heat-resistant composite oxide catalyst for exhaust gas purification represented by Item 2. Item 2.
  • Item 3. The heat-resistant composite oxide catalyst for exhaust gas purification according to Item 1 or 2, wherein M 1 is Sr or Ba.
  • Item 4. Item 4. The high heat-resistant composite oxide catalyst for exhaust gas purification according to Item 1, 2 or 3, wherein M 2 is Fe, Mn or Co.
  • Item 5. The high heat-resistant composite oxide catalyst for exhaust gas purification according to any one of Items 1 to 4, wherein x is 0.6 to 1.0.
  • the noble metal M is M 1 M 2 1-x Ti x O 3-d
  • M represents a noble metal selected from the group consisting of Pd, Rh and Pt.
  • M 1 represents Ca, Sr or Ba.
  • M 2 represents Mn, Fe, Co, Ni, or Cu.
  • X is 0.4 to 1.0, d is 0 to 0.5.) 0.1 to 2% by mass with respect to the carrier represented by Item 7.
  • the high heat-resistant composite oxide catalyst for exhaust gas purification according to any one of Items 1 to 6.
  • Item 8 M 1 compound, Ti compound, if necessary, M 2 compound is further dissolved or suspended in a solvent and heated to the following formula (II) M 1 M 2 1-x Ti x O 3-d (II) (In the formula, M 1 represents Ca, Sr, or Ba.
  • M 2 represents Mn, Fe, Co, Ni, or Cu.
  • X is 0.4 to 1.0.
  • D is 0 to 0.00. 5
  • a step of preparing a perovskite-type metal composite oxide represented by formula (1) contacting the obtained composite oxide with a solution containing at least one selected from the group consisting of a Pd compound, a Pt compound and an Rh compound, followed by firing.
  • Formula (I) M / M 1 M 2 1-x Ti x O 3-d (I) (In the formula, M represents at least one noble metal selected from the group consisting of Pd, Rh and Pt.
  • M 1 represents Ca, Sr or Ba.
  • M 2 represents Mn, Fe, Co, Ni or Cu.
  • X is 0.4 to 1.0
  • d is 0 to 0.5
  • M 1 M 2 1-x Ti x O 3-d represents a perovskite-type metal composite oxide support.
  • a perovskite-type metal composite oxide carrier represented by the general formula (II) wherein at least one noble metal (M) selected from the group consisting of Pd (palladium), Rh (rhodium) and Pt (platinum) is represented.
  • M noble metal
  • the catalyst of the present invention in which 0.5% by mass of Pd is supported on a carrier is CO and propylene oxidized even when compared with an Al 2 O 3 supported noble metal catalyst in which 1% by mass of Pd is supported. the NO x reduction temperature (T 50) is low, it is possible to realize an improvement of the reduction and heat resistance of the noble metal supporting amount at the same time.
  • the left figure shows 1 wt% Pd / SFTO, and the right figure shows 1 wt% Pd / Al 2 O 3 .
  • 1273 0.5 wt% Pd / SrFe was calcined at K 0.2 Ti 0.8 O 3-d (SFTO) and 1 wt% Pd / Al 2 O 3 catalyst activity
  • the high heat-resistant composite oxide catalyst for exhaust gas purification of the present invention comprises a noble metal (M) selected from the group consisting of Pd, Rh and Pt, represented by the following formula (II): M 1 M 2 1-x Ti x O 3-d (II) (In the formula, M represents at least one noble metal selected from the group consisting of Pd, Rh and Pt. M 1 represents Ca, Sr or Ba. M 2 represents Mn, Fe, Co, Ni or Cu. X is 0.4 to 1.0, and d is 0 to 0.5.) It is supported on a perovskite-type metal composite oxide carrier.
  • M includes at least one selected from the group consisting of Pd, Rh and Pt, preferably Pd, Rh or Pt, more preferably Pd or Rh, and most preferably Pd.
  • M 1 is Ca, Sr or Ba, preferably Sr or Ba, most preferably Sr.
  • M 2 is Mn, Fe, Co, Ni or Cu, preferably Fe, Mn or Co, most preferably Fe or Mn.
  • d depends on the metal species of M 1 and the amount of M 2 added, and is 0 to 0.5, preferably 0 to 0.2.
  • d when the support has a high Fe content such as SrFe 0.6 Ti 0.4 O 3-d , d is about 0.2, and when the Fe content is low such as SrTiO 3-d , d is approximately Becomes 0.
  • M 1 is Sr or Ba
  • the value of d depends on the valence of M 2 and Ti.
  • the Fe species in this crystal structure are in a trivalent and tetravalent mixed valence state, and the value of d can be determined to be approximately 0.2 from experimental facts.
  • the range of d of M 1 Fe 1-x Ti x O 3-d (x is 0.4 to 1.0) when M 1 is Sr or Ba is preferably 0 to 0.2.
  • M 2 is Mn, Co, Ni, Cu
  • the ratio of trivalent and tetravalent is expected to vary depending on the type of metal species and the amount of metal added. It falls within the range of 0.5.
  • X is 0.4 to 1.0, preferably 0.6 to 1.0, more preferably 0.7 to 1.0.
  • SrFe 1-x Ti x O 3-d (wherein x is 0.4 to 1.0) may be abbreviated as “SFTO”.
  • the numerical value in parentheses after the catalyst means the calcination temperature expressed in Kelvin (K) which is an absolute temperature.
  • K Kelvin
  • Pd / SFTO (773) and Pd / Al 2 O 3 (773) indicate Pd / SFTO and Pd / Al 2 O 3 fired at 773K (500 ° C.)
  • Pd / SFTO (1073) and Pd / Al 2 O 3 (1073) indicate Pd / SFTO and Pd / Al 2 O 3 fired at 1073 K (800 ° C.)
  • Pd / SFTO (1173) and Pd / Al 2 O 3 (1173) indicate Pd / SFTO and Pd / Al 2 O 3 fired at 1173K (900 ° C.)
  • Pd / SFTO (1273) and Pd / Al 2 O 3 (1273) indicate Pd / SFTO and Pd / Al 2 O 3 fired at 1273K (1000 ° C.)
  • the high heat-resistant composite oxide catalyst for exhaust gas purification of the present invention is useful as a three-way catalyst.
  • the three-way catalyst is composed of hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), which are harmful components of exhaust gas, water (H 2 O), carbon dioxide (CO 2 ), which are harmless gases, It is a catalyst that converts to nitrogen (N 2 ).
  • the three-way catalyst of the present invention has a structure in which active metal species (Pd, Pt, Rh) are supported on a perovskite-type metal composite oxide support.
  • the amount of the noble metal M supported is preferably about 0.1 to 2%, more preferably about 0.2 to 1.5%, still more preferably based on the mass of the composite oxide carrier represented by the formula (II). Is about 0.3 to 1.0%, particularly preferably about 0.4 to 0.6%.
  • the composite oxide carrier represented by the general formula (II) of the present invention can be produced by a complex polymerization method (PC method), a solvothermal method (ST method), or the like.
  • an M 1 compound, a Ti compound, and if necessary, an M 2 compound (when x ⁇ 1) are dissolved in an aqueous solution in which a hydroxycarboxylic acid such as citric acid is dissolved, and 1 to 5 at 60 to 90 ° C.
  • a hydroxycarboxylic acid such as citric acid
  • a high boiling point solvent such as ethylene glycol
  • the reaction is continued for a period of time, a high boiling point solvent such as ethylene glycol is added, and the reaction is further performed at 100 to 150 ° C. for 3 to 8 hours, followed by heating.
  • the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, citric acid, malic acid, tartaric acid, and the like, and one or more of these can be used.
  • Preferred hydroxycarboxylic acids are citric acid and malic acid.
  • the high boiling point solvent one or more of glycols such as ethylene glycol, propylene glycol and 1,4-butanediol, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, and glycerin can be used.
  • Preferred high boiling solvents are ethylene glycol and propylene glycol.
  • the total amount of M 2 compound and Ti compound is about 0.5 to 1.5 mol, preferably about 0.8 to 1.2 mol, per 1 mol of M 1 compound.
  • the PC method can be performed in an open system.
  • the ST method is a method in which an M 1 compound, an M 2 compound, and, if necessary, a Ti compound are dissolved or suspended in a solvent in a sealed container and heated, and the perovskite type metal composite oxide represented by the formula (II)
  • the carrier is produced as a precipitate.
  • the solvent one or more of water, 1,4-butanediol, glycols such as ethylene glycol and propylene glycol, alkylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, and glycerin can be used.
  • a preferred solvent is water, 1,4-butanediol.
  • the reaction is preferably carried out in a closed system.
  • the reaction is preferably performed in an atmosphere substituted with an inert gas (such as nitrogen or argon).
  • the reaction temperature is about 50 to 350 ° C., preferably about 100 to 350 ° C.
  • the reaction pressure is about 0.1 to 10 MPa, preferably about 1.0 to 5.0 MPa.
  • the reaction time is about 30 minutes to 24 hours, preferably about 1 to 12 hours.
  • the total amount of the M 2 compound and the Ti (titanium) compound may be about 0.5 to 1.5 mol, preferably about 0.8 to 1.2 mol, per 1 mol of the M 1 compound.
  • M 1 compounds dissolved / suspended in aqueous solutions and solvents include organic acid salts such as oxides, hydroxides, nitrates, acetates, carbonates, halides (fluorides, chlorides, bromides, iodides), etc. And organic acid salts such as oxides, nitrates, carbonates and acetates can be preferably used.
  • M 2 compound examples include organic acid salts such as nitrate and acetate, carbonates, halides (fluoride, chloride, bromide, iodide), acetylacetone, alkoxide (methoxide, ethoxide, tert-butoxide, etc.) ), A complex compound coordinated with a ligand, an organic acid salt such as acetate, and a nitrate can be preferably used.
  • Ti compound examples include nitrates, sulfates, acetates and other organic acid salts, carbonates, halides (fluorides, chlorides, bromides, iodides), acetylacetone, alkoxides (methoxides, ethoxides, n- A complex compound coordinated with a ligand such as propoxide, iso-propoxide, tert-butoxide and the like, and an organic acid salt such as acetate can be preferably used.
  • the catalyst represented by the general formula (I) of the present invention is obtained by impregnating or immersing the perovskite type metal composite oxide support represented by the formula (II) in a solution containing a noble metal compound, or a solution containing the noble metal compound on the support. Can be produced by spraying or the like, followed by firing.
  • noble metal compounds include platinum compounds such as hexachloroplatinic acid, tetrachloroplatinic acid, potassium tetrachloroplatinate, sodium tetrachloroplatinate, platinum chloride, and dinitrodiamineplatinum; palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, etc.
  • Palladium compounds such as rhodium chloride, rhodium sulfate, rhodium nitrate, rhodium hydroxide and acetylacetonatodium.
  • the firing temperature is about 500 to 1300 ° C., preferably about 700 to 1000 ° C.
  • the firing time is about 10 minutes to 24 hours, preferably about 30 minutes to 10 hours. Firing can be performed under air flow.
  • the catalyst of the present invention can treat CO, hydrocarbon (HC), and NOx at a low temperature, it is particularly excellent as a three-way catalyst for automobile exhaust gas purification.
  • Production Example 1 Preparation of composite oxide support by complex polymerization method (PC method) SrCO 3 (10 mmol), Fe (NO 3 ) 3 .9H 2 O (0, 2, 4, 6, 8 or 10 mmol) and Ti (OCH (CH 3 ) 2 ) 4 (10, 8, 6, 4, 2 or 0 mmol) was dissolved in ion-exchanged water (180 ml) containing 400 mmol of citric acid. In this case, the total amount of Fe (NO 3 ) 3 .9H 2 O and Ti (OCH (CH 3 ) 2 ) 4 was 10 mmol.
  • PC method complex polymerization method
  • This solution was stirred at 80 ° C. for 2 h, ethylene glycol (400 mmol) was added, and the mixture was stirred at 130 ° C. for 4 h to obtain a gel product.
  • the ⁇ -Al 2 O 3 supported noble metal catalyst has 1.0 wt% of Pd as a metal relative to ⁇ -Al 2 O 3 (reference catalyst ALO-7 (180 m 2 / g), provided by the Catalysis Society of Japan, 0.9900 g).
  • palladium (II) acetate (Pd (OAc) 2 0.0211 g was dissolved in 9 ml of acetone, impregnated and supported at room temperature, dried, and then dried in air at 500 ° C., 800 ° C., 900 ° C., 1000 ° C. or 1100 It was obtained by baking at 5 ° C. for 5 hours.
  • Pd / Al 2 O 3 (773) Pd by firing at 500 ° C.
  • a catalyst (200 mg) was filled in a quartz reaction tube, and as a pretreatment, He was allowed to flow at 30 mL min ⁇ 1 at 500 ° C. for 1 h.
  • a mixed gas of NO: 1000 ppm, CO: 1000 ppm, C 3 H 6 : 250 ppm, O 2 : 1125 ppm, He: balance was circulated through the catalyst layer at 100 mL min ⁇ 1 .
  • the outlet gas analysis was performed from 100 ° C. to 500 ° C., and the outlet gas analysis was performed after holding for 20 minutes every 50 ° C.
  • the analysis of the reaction gas was performed by two TCD-GC8A (MS-5A and Porapak Q manufactured by Shimadzu) and a NOx meter (ECL-88A Lite manufactured by Yanaco).
  • C 3 H 6 , CO, CO 2 , N 2 and N 2 O were measured with two TCD-GC8A (MS-5A and Porapak Q), and NO and NO 2 were measured with a NOx meter at 100 ° C. (373 K ), 150 ° C. (423 K), 200 ° C. (473 K), 250 ° C. (523 K), 300 ° C. (573 K), 350 ° C. (623 K), 400 ° C. (673 K), 450 ° C. (723 K), 500 ° C. (773 K).
  • was conducted on a catalyst using SrFe 0.2 Ti 0.8 O 3-d (x 0.8) as a composite oxide support.
  • Test example 2 1% by weight of Pd obtained in Example 1 was supported on SrFe 0.2 Ti 0.8 O 3-d (d is 0.1 or less), and 500 ° C. (773 K), 800 ° C. (1073 K), 1000 ° C. (1273 K) in air. ) Or 4 types of catalysts (Pd / SFTO (773), Pd / SFTO (1073), Pd / SFTO (1273), Pd / SFTO (1373)) obtained by calcination at 1100 ° C.
  • the catalyst of the present invention is exposed to exhaust gas at 1000 ° C., 1100 ° C. high temperature firing and similar temperatures for a long time. It has become clear that it has sufficient high temperature durability.
  • Test example 3 Pd / SFTO (773), Pd / SFTO (1073), Pd / SFTO (1173) obtained by carrying 1 wt% Pd obtained in Example 1 on SrFe 0.2 Ti 0.8 O 3-d (d is 0.1 or less).
  • Pd / SFTO (1273) , Pd / SFTO and (1373) was obtained in Comparative example 1, 1 wt% of Pd and Al 2 supported on O 3 was Pd / Al 2 O 3 (773), Pd / Al 2 O 3 (1073), Pd / Al 2 O 3 (1173), Pd / Al 2 O 3 (1273), Pd / Al 2 O 3 (1373) were reacted in the same manner as in Test Example 2, and the reaction was performed at 100 ° C.
  • Pd / Al 2 O 3 shows T 50 of Pd / SFTO and Pd / Al 2 O 3 baked at 773K, 1073K, 1173K, 1273K, and 1373K.
  • Pd / Al 2 O 3 is an excellent catalyst at a calcination temperature / reaction temperature up to 800 ° C., but at 1000 ° C. or 1100 ° C., the T 50 greatly increased and the heat resistance was found to be low. Exhaust gas from automobiles and the like may instantaneously exceed 1000 ° C., and it was revealed that the high heat-resistant catalyst of the present invention is excellent as a three-way catalyst.
  • Test example 4 1% by weight of Pd obtained in Comparative Example 1 was supported on Al 2 O 3 and fired in air at 800 ° C. (1073 K), 900 ° C. (1173 K), 1000 ° C. (1273 K), or 1100 ° C. (1373 K) for 5 hours.
  • XRD patterns of the catalysts (Pd / Al 2 O 3 (1073), Pd / Al 2 O 3 (1173), Pd / Al 2 O 3 (1273), Pd / Al 2 O 3 (1373)) obtained in this way was measured. The results are shown in FIG.
  • Test Example 5 Pd / SFTO (1273) obtained by carrying out 0.5 wt% Pd obtained in Example 1 on SrFe 0.2 Ti 0.8 O 3-d (d is 0.1 or less) and 1 wt% obtained in Comparative Example 1 Pd / Al 2 O 3 (1273) in which Pd was supported on ⁇ -Al 2 O 3 was reacted in the same manner as in Test Example 3, and 100 ° C. (373 K), 150 ° C. (423 K), 200 ° C. (473 K). NO to N 2 + N 2 O at temperatures of 250 ° C. (523 K), 300 ° C. (573 K), 350 ° C. (623 K), 400 ° C. (673 K), 450 ° C. (723 K), 500 ° C.
  • the conversion rate, the conversion rate from CO + C 3 H 6 to CO 2 was measured.
  • the results are shown in FIG.
  • the catalyst of the present invention in which the support is SrFe 0.2 Ti 0.8 O 3-d has a lower T 50 despite having a half Pd loading compared to the conventional catalyst using Al 2 O 3 as the support, It was revealed that the amount of noble metal supported such as Pd can be greatly reduced.

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Abstract

La présente invention concerne un catalyseur d'oxyde composite hautement résistant à la chaleur pour le nettoyage des gaz d'échappement, qui est représenté par la formule (I):M/M1M2 1-xTixO3-d (dans la formule, M représente au moins un type de métal noble choisi dans le groupe constitué par Pd, Rh et Pt. M 1 représente Ca, Sr ou Ba. M 2 représente Fe, Mn, Co, Ni ou Cu. x est de 0,4 à 1,0. d est de 0 à 0,5. M1M2 1-xTixO3-d un support d'oxyde composite métallique de type pérovskite.)
PCT/JP2017/032303 2016-09-14 2017-09-07 Catalyseur d'oxyde composite très résistant a la chaleur pour la purification des gaz d'échappement, et procédé de sa production WO2018051890A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545216A (zh) * 2020-04-22 2020-08-18 佛山市顺德区美的洗涤电器制造有限公司 一种复合催化材料及其制备方法与应用

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JPS6430627A (en) * 1987-07-24 1989-02-01 Matsushita Electric Ind Co Ltd Air filter
WO1992004965A1 (fr) * 1990-09-20 1992-04-02 Rover Group Limited Catalyseurs en metal du groupe de platine supporte
JPH11151440A (ja) * 1997-07-18 1999-06-08 Tokyo Gas Co Ltd 窒素酸化物の分解除去用触媒及び窒素酸化物の分解除去方法
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