WO2013098987A1 - Support pour catalyseurs de purification de gaz d'échappement, catalyseur de purification de gaz d'échappement et procédé de production correspondant - Google Patents

Support pour catalyseurs de purification de gaz d'échappement, catalyseur de purification de gaz d'échappement et procédé de production correspondant Download PDF

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WO2013098987A1
WO2013098987A1 PCT/JP2011/080384 JP2011080384W WO2013098987A1 WO 2013098987 A1 WO2013098987 A1 WO 2013098987A1 JP 2011080384 W JP2011080384 W JP 2011080384W WO 2013098987 A1 WO2013098987 A1 WO 2013098987A1
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exhaust gas
gas purifying
catalyst
aluminum borate
mass
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PCT/JP2011/080384
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English (en)
Japanese (ja)
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佐藤　隆広
中原　祐之輔
町田　正人
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三井金属鉱業株式会社
国立大学法人 熊本大学
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Priority to PCT/JP2011/080384 priority Critical patent/WO2013098987A1/fr
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    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J23/58—Platinum group metals with alkali- or alkaline earth 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
    • 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
    • B01J35/19—
    • B01J35/30—
    • B01J35/613—
    • B01J35/615—
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • 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
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2068—Neodymium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to an exhaust gas purification catalyst and a method for producing the same, and more specifically, an exhaust gas purification catalyst excellent in exhaust gas purification performance after high-temperature durability and excellent in dispersion of noble metals, particularly Pd, such as automobiles.
  • the present invention relates to a catalyst for purifying harmful components contained in exhaust gas discharged from an internal combustion engine and a method for producing the same.
  • Exhaust gas discharged from an internal combustion engine such as an automobile contains harmful components such as hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide (NO x ). Therefore, conventionally, a three-way catalyst for purifying and detoxifying these harmful components has been used.
  • HC hydrocarbon
  • CO carbon monoxide
  • NO x nitrogen oxide
  • noble metals such as Pt, Pd, and Rh are used as a catalytic active component, and alumina, ceria, zirconia, a ceria-zirconia composite oxide having oxygen storage ability, and the like are used as a carrier.
  • a catalyst support having a shape such as a honeycomb, a plate, or a pellet made of a ceramic or metal material is used.
  • Patent Documents 1, 2, and 3 There is also an example in which aluminum borate is used as a carrier, and the catalyst component is supported on a green compact including a powdery body that is covered with an aluminum borate whisker and has a hollow portion formed therein. The diffusibility is improved (see Patent Document 4).
  • An object of the present invention is to provide a carrier for an exhaust gas purifying catalyst excellent in exhaust gas purifying performance after high-temperature durability and excellent in dispersibility of noble metals, particularly Pd, an exhaust gas purifying catalyst, and a method for producing the same. It is in.
  • a specific composition of aluminum borate excellent in heat resistance with a ratio of aluminum oxide to boron oxide of 10: 2 to 9: 2 is La 2 O 3 .
  • a modified product is used as a carrier and Pd is supported thereon
  • La-stabilized alumina is used as a carrier and Pd is supported thereon, which is superior in exhaust gas purification performance after high-temperature durability and Pd. It was found that the degree of dispersion was excellent, and the present invention was completed.
  • the support for the exhaust gas purifying catalyst of the present invention is an aluminum oxide and boron oxide modified with La 2 O 3 in an amount of 0.3 to 2% by mass based on the mass of aluminum borate.
  • the ratio of aluminum borate is 10: 2 to 9: 2.
  • aluminum borate having a ratio of aluminum oxide to boron oxide of 10: 2 to 9: 2 is expressed by the formula 10Al 2 O 3 .2B 2 O 3 (5Al 2 O 3 : B 2 O 3 , Al 20 B 4 those represented by O 36), or is intended to include those represented by the formula 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33), hereinafter referred to as a specific composition of aluminum borate , which those modified with La 2 O 3, La 2 O 3 that modified a specific composition of aluminum borate in.
  • the exhaust gas purifying catalyst of the present invention comprises a carrier containing aluminum borate having a specific composition modified with La 2 O 3 in an amount of 0.3 to 2% by mass based on the mass of aluminum borate, And Pd supported on a carrier.
  • the exhaust gas purifying catalyst of the present invention comprises a carrier containing aluminum borate having a specific composition modified with La 2 O 3 in an amount of 0.3 to 2% by mass based on the mass of aluminum borate. And Pd and Ba supported on the carrier.
  • the exhaust gas purifying catalyst component of the present invention includes a catalyst support made of a ceramic or a metal material, and the exhaust gas purifying catalyst layer of the present invention supported on the catalyst support.
  • the exhaust gas purifying catalyst component of the present invention includes a catalyst support made of a ceramic or a metal material, the layer of the exhaust gas purifying catalyst supported on the catalyst support, and the exhaust gas purifying. And a rhodium catalyst layer supported on the catalyst layer.
  • the method for producing an exhaust gas purifying catalyst of the present invention comprises mixing a boric acid with a specific composition and a solution of a lanthanum compound, evaporating to dryness, firing, and boric acid having a specific composition modified with La 2 O 3 Producing aluminum, and then mixing the modified specific composition aluminum borate and Pd compound solution, or mixing the modified specific composition aluminum borate, Ba compound and Pd compound solution And then evaporated to dryness and fired.
  • the carrier for the exhaust gas purifying catalyst of the present invention is excellent in exhaust gas purifying performance after high temperature durability, and is useful for producing an exhaust gas purifying catalyst excellent in precious metal, especially Pd dispersibility
  • the exhaust gas purifying catalyst of the present invention and the exhaust gas purifying catalyst component of the present invention are excellent in exhaust gas purifying performance after high-temperature durability and excellent in the degree of dispersion of Pd, and the production method of the present invention is the present invention. It is suitable for producing an exhaust gas purifying catalyst.
  • FIG. 3 is a diagram showing the measurement results of X-ray diffraction of aluminum borate in Example 1. It is a figure which shows the measurement result of the X-ray diffraction of the aluminum borate of a manufacture example.
  • aluminum borate having a specific composition for use in the present invention have the formula 10Al 2 O 3 ⁇ 2B 2 O 3 (5Al 2 O 3: B 2 O 3, Al 20 B 4 O 36) intended to be displayed in, or formula it is intended to include those represented by 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33).
  • aluminum borate having a specific composition has a cavity having a diameter of about 0.4 nm inside the crystal structure.
  • Such an aluminum borate in an amount of 0.3 to 2% by weight, preferably 0.4 to 2% by weight, more preferably 0.5 to 1.5% by weight, based on the weight of the aluminum borate.
  • the carrier for the exhaust gas purifying catalyst of the present invention can be obtained by modifying with La 2 O 3 .
  • the amount of La 2 O 3 is less than 0.3% by mass or more than 2% by mass based on the mass of aluminum borate, high temperature durability is evident from the examples and comparative examples described later. The degree of improvement in the exhaust gas purification performance of the later catalyst is insufficient.
  • the carrier for the exhaust gas purifying catalyst of the present invention consists only of aluminum borate having a specific composition modified with La 2 O 3
  • the carrier modified with La 2 O 3 is used. It may be a mixture of aluminum borate having a composition and a binder such as alumina commonly used in a three-way catalyst or a support such as CeO 2 —ZrO 2 having an oxygen storage capacity (OSC). That is, the carrier for the exhaust gas purifying catalyst of the present invention contains aluminum borate modified with La 2 O 3 described above.
  • the carrier for the exhaust gas purifying catalyst of the present invention described above can suppress the deterioration rate of the precious metal dispersion after high temperature endurance regardless of any precious metal of Pd, Rh and Pt, and precious metal sintering after high temperature endurance However, the effect is remarkable when the noble metal is Pd.
  • the exhaust gas purifying catalyst of the present invention is a catalyst in which Pd is supported on a carrier containing aluminum borate having a specific composition modified with La 2 O 3 described above.
  • the amount of Pd supported is preferably 0.3 to 3% by mass, more preferably 0.4 to 2% by mass based on the mass of the carrier in terms of the mass of Pd metal.
  • Pd is supported on CeO 2 —ZrO 2 having oxygen storage capacity by supporting Pd on aluminum borate having a specific composition modified with La 2 O 3 as described above, Pd is supported on La-stabilized alumina. Compared with the case where it is made, Pd dispersion degree deterioration rate after high temperature durability is suppressed, and Pd sintering after high temperature durability is suppressed.
  • the exhaust gas purifying catalyst of the present invention is one in which Pd and Ba are supported on a carrier containing aluminum borate having a specific composition modified with La 2 O 3 .
  • Pd and Ba By supporting Pd and Ba, the oxygen dissociation temperature of PdO can be increased, and the catalytic action of Pd can be enhanced.
  • the amount and effect of Pd are as described above.
  • the supported amount of Ba is preferably 2 to 3% by mass, more preferably 2 to 2.5% by mass based on the mass of Pd metal in terms of the mass of BaO.
  • the exhaust gas purifying catalyst structure of the present invention is formed by forming and supporting a layer made of the above-described exhaust gas purifying catalyst of the present invention on a catalyst support made of ceramics or a metal material.
  • the supported amount is preferably 70 to 300 g / L, more preferably 100 to 230 g / L.
  • the shape of the catalyst support made of a ceramic or metal material is not particularly limited, but is generally a shape of a honeycomb, a plate, a pellet, etc. A honeycomb shape is preferred.
  • Examples of the material for such a catalyst support include ceramics such as alumina (Al 2 O 3 ), mullite (3Al 2 O 3 -2SiO 2 ), cordierite (2MgO-2Al 2 O 3 -5SiO 2 ), and the like. And metal materials such as stainless steel.
  • a layer made of the above-described exhaust gas purifying catalyst of the present invention is supported on a catalyst support made of a ceramic or metal material,
  • the Rh catalyst layer is formed on and supported.
  • the shape and material of the catalyst support made of ceramic or metal material in the exhaust gas purifying catalyst component are the same as described above.
  • the amount of Rh supported in the Rh catalyst layer is preferably 0.1 to 0.6% by mass, more preferably 0.1 to 0.4% by mass, based on the mass of the carrier in the Rh catalyst layer.
  • the ratio of Pd: Rh is preferably 3 to 20: 1, more preferably 5 to 20: 1.
  • the loading amount of the lower layer is preferably 70 to 200 g / L, more preferably 100 to 160 g / L, and the loading amount of the upper layer is preferably 30 in consideration of heat resistance, gas diffusibility to the lower layer, exhaust pressure and the like. -100 g / L, more preferably 50-70 g / L.
  • the method for producing an exhaust gas purifying catalyst of the present invention comprises mixing a boric acid with a specific composition and a solution of a lanthanum compound, evaporating to dryness, firing, and boric acid having a specific composition modified with La 2 O 3
  • An aluminum is prepared and then the modified aluminum borate and Pd compound solution are mixed, or the modified aluminum borate, Ba compound and Pd compound solution are mixed and then evaporated to dryness. Solidifying and firing.
  • the solvent constituting the “solution” is not particularly limited as long as it can form a solution, but water is generally used.
  • the aluminum borate having a specific composition used in the method for producing the exhaust gas purifying catalyst of the present invention is commercially available, and can be produced, for example, by the following method on a laboratory scale.
  • 1.5 L of solvent for example, 2-propanol, butanol, ethanol
  • solvent for example, 2-propanol, butanol, ethanol
  • Al alkoxide for example, aluminum ethoxide, aluminum isopropoxide, aluminum, pulverized in an agate mortar
  • Al alkoxide 200 g of triisopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum tributoxide, aluminum phenoxide, aluminum ethoxyethoxyethoxide
  • alkoxides of B eg, boron n-propoxide, boron trimethyl
  • Siloxide boron ethoxy ethoxide, boron vinyl dimethyl siloxide, boron allyl oxide, boron n-butoxide, boron t-butoxide, boron ethoxide, boron isopro Kishido placed boron methoxide) 40.9 g, and stirred while replacing with N 2 gas.
  • 2-propanol is produced when the aluminum isopropoxide is hydrolyzed. Therefore, it is most preferable to use 2-propanol as a solvent.
  • a mixed solution of solvent for example, 2-propanol
  • the obtained precipitate was washed with ethanol, then washed with pure water, filtered, dried at 120 ° C. overnight (about 15 hours), calcined in air at 300 ° C. for 3 hours, and further in air 1 Calcination at 000 ° C.
  • the aluminum borate can be identified as the aluminum borate of the formula 10Al 2 O 3 ⁇ 2B 2 O 3 by X-ray diffraction.
  • the formula 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33) is present as a standard X-ray diffraction chart, the product of the formula 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33 ) can also be identified.
  • a mixture of aluminum borate having a specific composition and a lanthanum compound (soluble lanthanum compound such as lanthanum nitrate, lanthanum acetate, lanthanum chloride, lanthanum bromide, lanthanum sulfate) is mixed.
  • the aluminum borate-containing slurry and the lanthanum compound solution may be mixed, or aluminum borate may be added to the lanthanum compound solution.
  • the ratio of the amount of aluminum borate to the amount of lanthanum compound at this time is 0.3 to 2% by mass, preferably 0.4 to 2% by mass, more preferably based on the mass of aluminum borate after firing.
  • the amount of La 2 O 3 is 0.5 to 1.5% by mass.
  • the aluminum borate having a specific composition modified with La 2 O 3 obtained as described above is then mixed with a solution of a Pd compound (soluble Pd compound, for example, Pd nitrate, Pd chloride, Pd sulfate).
  • a Pd compound soluble Pd compound, for example, Pd nitrate, Pd chloride, Pd sulfate.
  • an ordinary carrier ordinarily used in the three-way catalyst or a carrier such as CeO 2 —ZrO 2 having an oxygen storage capacity (OSC) can coexist.
  • the ratio of the amount of the carrier and the amount of the Pd compound at this time is such that the amount of Pd supported after calcination is preferably 0.5 to 3% by mass, more preferably 0.7 to 2% by mass.
  • aluminum borate having a specific composition modified with La 2 O 3 obtained as described above is then added to a Ba compound (for example, It is mixed with a solution of barium oxide, barium nitrate, barium acetate, barium oxalate, barium hydroxide, barium carbonate) and a Pd compound (soluble Pd compounds such as Pd nitrate, Pd chloride, Pd sulfate).
  • a Ba compound for example, It is mixed with a solution of barium oxide, barium nitrate, barium acetate, barium oxalate, barium hydroxide, barium carbonate
  • Pd compound soluble Pd compounds such as Pd nitrate, Pd chloride, Pd sulfate
  • the ratio of the amount of the carrier and the amount of the Pd compound at this time is as described above, and the amount of the Ba compound is preferably 2 to 3% by mass, more preferably based on the mass of the Pd metal in terms of the BaO amount. 2 to 2.5% by mass.
  • the Pd compound, or both of the Pd compound and the Ba compound was evaporated to dryness at 120 ° C. overnight (about 15 hours) so that the Pd compound and both of the Ba compound and the Ba compound were almost uniformly attached, and then calcined in air at 600 ° C. for 3 hours.
  • the exhaust gas purifying catalyst of the present invention in which Pd or both of Pd and Ba are supported on aluminum borate having a specific composition modified with La 2 O 3 is obtained.
  • the exhaust gas purifying catalyst component of the present invention can be produced, for example, by the following method.
  • a mixture of aluminum borate having a specific composition modified with La 2 O 3 , a binder, a carrier such as CeO 2 —ZrO 2 having an oxygen storage capacity if necessary, and a Ba compound if necessary with a solution of a Pd compound, and wet-grinding treatment To prepare a slurry.
  • the obtained slurry is applied to a catalyst support made of ceramics or a metal material, preferably a honeycomb-shaped catalyst support, dried and fired according to a known method, and the catalyst support and the catalyst support are coated on the catalyst support.
  • An exhaust gas purifying catalyst structure including an exhaust gas purifying catalyst layer carried on the substrate is obtained.
  • An exhaust gas purifying catalyst structure having an Rh catalyst layer on the catalyst layer can also be produced.
  • the aluminum borate which is a white product.
  • the aluminum borate were identified as aluminum borate of the formula 10Al 2 O 3 ⁇ 2B 2 O 3 by X-ray diffraction. Also, this product is one that can be identified with the formula 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33).
  • Al 1 shows a measurement result of X-ray diffraction of the aluminum borate formula 10Al 2 O 3 ⁇ 2B 2 O 3 (Al 20 B 4 O 36) aluminum borate and formula represented by 9Al 2 O 3 ⁇ 2B
  • the standard card data of aluminum borate represented by 2 O 3 (Al 18 B 4 O 33 ) are shown.
  • the aluminum borate obtained above was immersed in an aqueous lanthanum nitrate solution.
  • the amount of lanthanum nitrate in this aqueous lanthanum nitrate solution is such that the amount of La 2 O 3 in the target aluminum borate modified with La 2 O 3 is 0.5% based on the mass of aluminum borate. It was the quantity used as the mass%. Then, it was evaporated to dryness at 120 ° C. overnight (about 15 hours), and calcined in air at 600 ° C. for 3 hours to obtain aluminum borate having a specific composition modified with 0.5% by mass of La 2 O 3 . .
  • the aluminum borate having a specific composition modified with 0.5% by mass of La 2 O 3 obtained above was immersed in an aqueous solution of Pd nitrate.
  • the amount of Pd nitrate in this aqueous solution of Pd nitrate is an amount that is 0.4% by mass of aluminum borate having a specific composition modified with 0.5% by mass of La 2 O 3 in terms of the mass of Pd metal. there were.
  • it was evaporated to dryness at 120 ° C. overnight (about 15 hours), and calcined in air at 600 ° C. for 3 hours to produce the exhaust gas purifying catalyst of the present invention.
  • Example 2 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, and La 1 wt% amount of La 2 O 3 of the modified specific composition of boric acid in the aluminum based on the weight of aluminum borate in 2 O 3 for the purpose
  • the exhaust gas purifying catalyst of the present invention was produced in the same manner as in Example 1 except that the amount was as follows.
  • Example 3 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, and La 2 wt% amount of La 2 O 3 of the modified specific composition of boric acid in the aluminum based on the weight of aluminum borate in 2 O 3 for the purpose
  • the exhaust gas purifying catalyst of the present invention was produced in the same manner as in Example 1 except that the amount was as follows.
  • Comparative Example 1 Comparative example in the same manner as in Example 1 except that the step of modifying with La 2 O 3 was not performed (that is, Pd was supported on aluminum borate having a specific composition without modification with La 2 O 3 ). An exhaust gas purification catalyst was manufactured.
  • Comparative Example 2 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, and La 3 wt% the amount of La 2 O 3 of the modified specific composition of boric acid in the aluminum based on the weight of aluminum borate in 2 O 3 for the purpose
  • the exhaust gas purifying catalyst of the comparative example was manufactured in the same manner as in Example 1 except that the amount was changed.
  • Comparative Example 3 The amount of lanthanum nitrate in the aqueous solution of lanthanum nitrate, and La 2 O 3 5 wt% amount of La 2 O 3 of the modified specific composition of boric acid in the aluminum based on the weight of aluminum borate in the intended
  • the exhaust gas purifying catalyst of the comparative example was manufactured in the same manner as in Example 1 except that the amount was changed.
  • Comparative Example 4 La-stabilized alumina was immersed in an aqueous Pd nitrate solution.
  • the amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 0.4% by mass of La stabilized alumina in terms of the mass of Pd metal.
  • the catalyst was evaporated to dryness at 120 ° C. overnight (about 15 hours) and calcined in air at 600 ° C. for 3 hours to produce a comparative exhaust gas purifying catalyst.
  • the outlet gas component was measured using a CO / HC / NO analyzer. From the obtained light-off performance evaluation results, the temperatures (T10, T50, and T90) that reached the NO 10%, 50%, and 90% purification rates were determined. The results were as shown in Table 1.
  • the Pd catalyst using a specific composition of aluminum borate modified with a predetermined amount of La 2 O 3 as a carrier showed excellent catalytic activity after high temperature durability.
  • Example 2 Each exhaust gas purifying catalyst obtained in Example 2 and Comparative Example 4 was endured for 25 hours at 900 ° C., 1000 ° C., 1100 ° C. or 1200 ° C. in an air atmosphere containing 10% of water vapor.
  • the catalytic activity of was evaluated as follows.
  • catalyst powder is set in a reaction tube, CO: 0.51%, NO: 500 ppm, C 3 H 6 : 1170 ppm C, O 2 : 0.4%, from the remaining N 2
  • the outlet gas component was measured using a CO / HC / NO analyzer. From the obtained light-off performance evaluation result, the temperature (T50) at which the NO purification rate reaches 50% was determined. The results were as shown in Table 2.
  • aluminum borate has a lower BET value reduction rate due to endurance treatment than La-stabilized alumina, and aluminum borate has higher heat resistance than La-stabilized alumina. I found it excellent. Moreover, when aluminum borate is modified with 1% by mass of La 2 O 3 , a BET value that is the same as that before the durability treatment is obtained after the durability treatment, and further improvement in heat resistance by modification with La 2 O 3 was recognized.
  • Pd dispersity Pd amount (mole) corresponding to CO adsorption amount / total amount of Pd contained (mole) Is a value calculated by.
  • the Pd dispersion degree deterioration rate was obtained from these values. The results were as shown in Table 4.
  • the degree of precious metal dispersion indirectly represents the level of contact probability with exhaust gas, and it can be said that the higher the degree of precious metal dispersion, the higher the contact efficiency with exhaust gas.
  • aluminum borate modified with Pd / 1% by mass of La 2 O 3 has a reduced Pd dispersity degradation rate, and after high-temperature durability by adopting a high heat-resistant material. Pd sintering is suppressed.
  • Example 4 (Pd monolayer, Pd support concentration 1.3 g / L) It corresponds to 59.8 parts by mass of aluminum borate having a specific composition modified with 1% by mass of La 2 O 3 , 29.6 parts by mass of CeO 2 —ZrO 2 -based composite oxide, and 3.3 parts by mass as barium oxide. An amount of barium nitrate and 6.0 parts by mass of an alumina binder were added to an aqueous solution of Pd nitrate, and wet pulverization was performed to obtain a Pd-containing slurry.
  • the amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 1.3% by mass in terms of solid content in terms of the mass of Pd metal.
  • the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired to produce an exhaust gas purifying catalyst structure of the present invention.
  • Comparative Example 5 (Pd single layer, Pd support concentration 1.3 g / L) 29.6 parts by mass of CeO 2 —ZrO 2 -based composite oxide, 59.8 parts by mass of La-stabilized alumina, barium nitrate in an amount corresponding to 3.3 parts by mass as barium oxide, and 6.0 parts by mass of an alumina binder It was added to a Pd nitrate aqueous solution and subjected to a wet pulverization treatment to obtain a Pd-containing slurry. The amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 1.3% by mass in terms of solid content in terms of the mass of Pd metal. The obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired to produce a catalyst structure for exhaust gas purification of a comparative example.
  • a ceramic honeycomb catalyst support
  • Example 4 Exhaust gas purification in Example 4 and Comparative Example 5 above was measured using a CO / HC / NO analyzer (Horiba Seisakusho MOTOR EXHAUST GAS ANALYZER MEXA9100). The light-off performance of the catalyst assembly was determined. From the result of the obtained light-off performance evaluation, the temperature (T50) at which 50% purification rate of CO / HC / NO was reached was determined. The results were as shown in Table 5.
  • the amount of Pd nitrate in the aqueous Pd nitrate solution was 0.83% by mass in terms of solid content in terms of the mass of Pd metal.
  • the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired.
  • Nd 2 O 3 —ZrO 2 -based composite oxide 70.3 parts by mass of Nd 2 O 3 —ZrO 2 -based composite oxide, 23.4 parts by mass of La-stabilized alumina, and 6.0 parts by mass of an alumina-based binder were added to the aqueous Rh nitrate solution, and wet pulverization was performed.
  • an Rh-containing slurry was obtained.
  • the amount of nitric acid Rh in the aqueous nitric acid Rh solution was such that the solid content after firing was 0.33% by mass in terms of the mass of Rh metal.
  • the obtained slurry is applied to the Pd-supported ceramic honeycomb obtained above in an amount of 50 g / L, dried and fired to produce the exhaust gas purifying catalyst structure of the present invention consisting of two Pd / Rh layers. did.
  • the amount of Pd nitrate in the aqueous Pd nitrate solution was 0.91% by mass in terms of solid content in terms of the mass of Pd metal.
  • the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired.
  • Nd 2 O 3 —ZrO 2 -based composite oxide 70.4 parts by mass of Nd 2 O 3 —ZrO 2 -based composite oxide, 23.5 parts by mass of La-stabilized alumina, and 6.0 parts by mass of an alumina binder were added to the aqueous Rh nitrate solution, and wet pulverization was performed.
  • an Rh-containing slurry was obtained.
  • the amount of nitric acid Rh in the aqueous nitric acid Rh solution was 0.18% by mass in terms of the solid content after firing in terms of the mass of Rh metal.
  • the obtained slurry is applied to the Pd-supported ceramic honeycomb obtained above in an amount of 50 g / L, dried and fired to produce the exhaust gas purifying catalyst structure of the present invention consisting of two Pd / Rh layers. did.
  • the amount of Pd nitrate in the aqueous Pd nitrate solution was 0.95% by mass in terms of solid content in terms of the mass of Pd metal.
  • the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired.
  • Nd 2 O 3 —ZrO 2 -based composite oxide 70.4 parts by mass of Nd 2 O 3 —ZrO 2 -based composite oxide, 23.5 parts by mass of La-stabilized alumina, and 6.0 parts by mass of an alumina binder were added to the aqueous Rh nitrate solution, and wet pulverization was performed.
  • a slurry containing Rh was obtained.
  • the amount of nitric acid Rh in the aqueous nitric acid Rh solution was an amount that would be 0.10% by mass of the solid content after calcination in terms of the mass of Rh metal.
  • the obtained slurry is applied to the Pd-supported ceramic honeycomb obtained above in an amount of 50 g / L, dried and fired to produce the exhaust gas purifying catalyst structure of the present invention consisting of two Pd / Rh layers. did.
  • Example 8 Pd monolayer, Pd support concentration 1.0 g / L It corresponds to 45.3 parts by mass of aluminum borate having a specific composition modified with 1% by mass of La 2 O 3 , 45.3 parts by mass of CeO 2 —ZrO 2 -based composite oxide, and 2.4 parts by mass as barium oxide.
  • An amount of barium nitrate and 6.0 parts by mass of an alumina binder were added to an aqueous solution of Pd nitrate, and wet pulverization was performed to obtain a Pd-containing slurry.
  • the amount of Pd nitrate in this aqueous solution of Pd nitrate was an amount that would be 1.00% by mass of the solid content in terms of the mass of Pd metal.
  • the obtained slurry was applied to a ceramic honeycomb (catalyst support) in an amount of 100 g / L, dried and fired to produce an exhaust gas purifying catalyst structure of the present invention.
  • Comparative Example 9 (Pd single layer, Pd carrying concentration 1.0 g / L) Exhaust gas purifying catalyst structure of a comparative example in the same manner as in Example 8 except that the same amount of La stabilized alumina was used instead of aluminum borate having a specific composition modified with 1% by mass of La 2 O 3 Manufactured.
  • the outlet gas components at 100 to 500 ° C. were measured using a CO / HC / NO analyzer (MOTOR EXHAUST GAS ANALYZER MEXA9100, manufactured by Horiba, Ltd.).
  • the light-off performance of the exhaust gas purification catalyst components of Examples 6 to 9 was determined.
  • the purification rate ( ⁇ 400) at 400 ° C. of each of CO / HC / NO was determined from the result of the obtained light-off performance evaluation. The results were as shown in Table 6.
  • the purification performance is at the same level as that of the Rh high loading specification, the performance degradation is suppressed, and the aluminum borate having a specific composition modified with La 2 O 3 which is a high heat resistant material is used. A significant reduction in the amount of Rh can be expected by adoption.
  • the obtained precipitate was washed with ethanol, then washed with pure water, and filtered. Then, it dried at 120 degreeC overnight (about 15 hours), baked at 300 degreeC in the air for 3 hours, and also baked at 1,000 degreeC in the air for 5 hours, and obtained the aluminum borate which is a white product.
  • the aluminum borate were identified as aluminum borate of the formula 10Al 2 O 3 ⁇ 2B 2 O 3 by X-ray diffraction. Also, this product is one that can be identified with the formula 9Al 2 O 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33).
  • the measurement result of the X-ray diffraction of the aluminum borate of this production example the aluminum borate represented by the formula 10Al 2 O 3 .2B 2 O 3 (Al 20 B 4 O 36 ), and the formula 9Al 2 O represents the standard of the card data of aluminum borate represented by 3 ⁇ 2B 2 O 3 (Al 18 B 4 O 33).

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Abstract

La présente invention concerne un support qui contient un borate d'aluminium modifié par La2O3 présentant une composition spécifique, ledit borate d'aluminium modifié par La2O3 étant obtenu par modification d'un borate d'aluminium qui contient de l'oxyde d'aluminium et de l'oxyde de bore dans un rapport de 10:2 à 9:2 avec du La2O3 de sorte que la quantité de La2O3 par rapport à la masse du borate d'aluminium est de 0,3 à 2 % en masse. La présente invention concerne également un catalyseur de purification de gaz d'échappement qui contient le support et Pd ou Pd + Ba qui sont supportés par le support. L'invention concerne également une configuration de catalyseur qui contient un corps supportant le catalyseur qui est constitué d'un matériau céramique ou métallique et d'une couche du catalyseur de purification de gaz d'échappement, ladite couche étant disposée sur le corps supportant le catalyseur. La configuration de catalyseur peut contenir en outre une couche de catalyseur à base de Rh qui est disposée sur la couche du catalyseur de purification de gaz d'échappement. L'invention concerne également un procédé de production d'un catalyseur de purification de gaz d'échappement.
PCT/JP2011/080384 2011-12-28 2011-12-28 Support pour catalyseurs de purification de gaz d'échappement, catalyseur de purification de gaz d'échappement et procédé de production correspondant WO2013098987A1 (fr)

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US20160082420A1 (en) * 2013-05-16 2016-03-24 Mitsui Mining & Smelting Co., Ltd. Catalyst system for exhaust gas purification and method for exhaust gas purification

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Cited By (8)

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US20160082420A1 (en) * 2013-05-16 2016-03-24 Mitsui Mining & Smelting Co., Ltd. Catalyst system for exhaust gas purification and method for exhaust gas purification
US9597665B2 (en) * 2013-05-16 2017-03-21 Mitsui Mining & Smelting Co., Ltd. Catalyst system for exhaust gas purification and method for exhaust gas purification
WO2015064385A1 (fr) * 2013-10-31 2015-05-07 三井金属鉱業株式会社 Support pour catalyseur de purification de gaz d'échappement et catalyseur de purification de gaz d'échappement
CN105682793A (zh) * 2013-10-31 2016-06-15 三井金属矿业株式会社 废气净化催化剂用载体和废气净化催化剂
US20160279606A1 (en) * 2013-10-31 2016-09-29 Mitsui Mining & Smelting Co., Ltd. Carrier for exhaust gas purification catalyst, and exhaust gas purification catalyst
JPWO2015064385A1 (ja) * 2013-10-31 2017-03-09 三井金属鉱業株式会社 排ガス浄化触媒用担体及び排ガス浄化触媒
EP3064270A4 (fr) * 2013-10-31 2017-06-07 Mitsui Mining and Smelting Co., Ltd. Support pour catalyseur de purification de gaz d'échappement et catalyseur de purification de gaz d'échappement
US9687817B2 (en) 2013-10-31 2017-06-27 Mitsui Mining & Smelting Co., Ltd. Carrier for exhaust gas purification catalyst, and exhaust gas purification catalyst

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