WO2012093600A1 - Exhaust gas purification catalyst and exhaust gas purification catalyst structure - Google Patents

Exhaust gas purification catalyst and exhaust gas purification catalyst structure Download PDF

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WO2012093600A1
WO2012093600A1 PCT/JP2011/079875 JP2011079875W WO2012093600A1 WO 2012093600 A1 WO2012093600 A1 WO 2012093600A1 JP 2011079875 W JP2011079875 W JP 2011079875W WO 2012093600 A1 WO2012093600 A1 WO 2012093600A1
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exhaust gas
catalyst
gas purification
ymno
gas purifying
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PCT/JP2011/079875
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French (fr)
Japanese (ja)
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啓太 石崎
直樹 大矢
貴弘 中
直樹 光田
弘志 大野
高橋　進
彦睦 渡邉
啓充 高木
晶子 杉岡
晃 阿部
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本田技研工業株式会社
三井金属鉱業株式会社
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Priority to DE112011104673T priority Critical patent/DE112011104673T5/en
Priority to CN201180064342.4A priority patent/CN103370131B/en
Priority to JP2012551833A priority patent/JP5864444B2/en
Publication of WO2012093600A1 publication Critical patent/WO2012093600A1/en

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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
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • 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
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B01J35/30—
    • B01J35/393—
    • B01J35/56—
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • B01J37/16—Reducing
    • 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
    • B01D2255/104—Silver
    • 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
    • B01D2255/2061—Yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—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
    • B01D2255/915—Catalyst supported on particulate filters

Definitions

  • the present invention relates to an exhaust gas purification catalyst and an exhaust gas purification catalyst structure used for purifying exhaust gas discharged from an internal combustion engine such as an automobile.
  • the exhaust gas discharged from internal combustion engines such as automobiles contains harmful components such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NO). Therefore, conventionally, a three-way catalyst for purifying and detoxifying these harmful components has been used.
  • harmful components such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NO). Therefore, conventionally, a three-way catalyst for purifying and detoxifying these harmful components has been used.
  • a precious metal such as Pt, Pd, or Rh and an alumina, ceria, zirconia, or a composite oxide thereof are arbitrarily combined and applied on a honeycomb carrier such as ceramics or metal. Has been.
  • exhaust gas discharged from diesel engines contains particulates (particulate matter), and if these materials are released into the atmosphere as they are, they cause air pollution.
  • particulates particulate matter
  • DPF diesel particulate filter
  • Patent Documents 1 and 2 As a system proposed so far, a catalyst (for example, Patent Documents 1 and 2) in which an expensive noble metal such as Pt is supported on a carrier, for example, a carrier made of an inorganic oxide such as zirconium oxide, vanadium oxide, or cerium oxide. And 3) and a system that uses a catalyst by supporting inexpensive silver. Conventionally, it has been pointed out that although silver is inexpensive, it is inferior in heat resistance (see Non-Patent Document 1).
  • the present invention provides an exhaust gas purifying catalyst and an exhaust gas purifying catalyst structure capable of purifying gas components harmful to exhaust gas discharged from an internal combustion engine such as an automobile and oxidizing and removing particulates. It is aimed.
  • the present inventors have achieved excellent exhaust gas purification performance and Ag by supporting Ag on yttrium manganate YMnO 3 .
  • the present inventors have found that the problem of heat durability, which has been a drawback, can also be overcome.
  • the exhaust gas purifying catalyst component of the present invention comprises a catalyst support made of a ceramic or metal material and the exhaust gas purifying catalyst supported on the catalyst support.
  • the exhaust gas purifying catalyst and the exhaust gas purifying catalyst structure according to the present invention can purify gas components harmful to exhaust gas discharged from an internal combustion engine such as an automobile and oxidize and remove particulates. Since the gas purification performance is excellent, it is effective for purifying exhaust gas discharged from an internal combustion engine such as an automobile.
  • FIG. 4 is an electron micrograph of a part of the exhaust gas purifying catalyst structure obtained in Example 3.
  • FIG. 4 is an electron micrograph of a part of the exhaust gas purifying catalyst structure obtained in Example 3.
  • Yttrium manganate used in the exhaust gas purifying catalyst and the exhaust gas purifying catalyst structure of the present invention is a known double oxide represented by the chemical formula YMnO 3 , and this double oxide YMnO 3 includes, for example, yttrium nitrate and nitric acid.
  • a mixture of manganese, citric acid and water is first calcined at a temperature in the range of 200-400 ° C. for a time in the range of 1-10 hours, and then at a temperature in the range of 800-1000 ° C., 1-10 It can manufacture by carrying out secondary baking for the time within the range of time.
  • yttrium nitrate hexahydrate, manganese nitrate hexahydrate, citric acid and water are used as a mixture in a molar ratio of 1: 1: 6: 40. Can do.
  • the crystal system of YMnO 3 obtained by the above-described method for producing the double oxide YMnO 3 is in the form of hexagonal crystal, orthorhombic crystal or a mixture thereof, any of which is useful as a support in the present invention. It is.
  • Y 2 O 3 and MnO 2 as raw materials are weighed so that the atomic ratio of Y / Mn is 1/1, and pulverized and mixed for 3 hours or more using, for example, a ball mill Can be mentioned.
  • the double oxide YMnO 3 can be obtained by firing at 900 ° C. for 5 hours in the air atmosphere.
  • a liquid phase method can be mentioned.
  • nitrates of Y and Mn as raw materials are weighed so that the atomic ratio of Y / Mn becomes 1/1, and an aqueous solution such as ammonia is dropped into an aqueous solution.
  • a double oxide YMnO 3 can be obtained by making a precipitate of Mn, filtering, washing and drying, and removing and crystallizing nitrate radicals by sufficient heating, for example, at about 800 ° C.
  • the method for producing the double oxide YMnO 3 is not particularly limited.
  • the exhaust gas purifying catalyst of the present invention is such that Ag is supported on a carrier containing such yttrium manganate YMnO 3 .
  • the carrier may be YMnO 3 used alone, or may be used by mixing with other known carriers such as alumina (Al 2 O 3 ), CeO 2 , (CeZr) O 2 .
  • the exhaust gas purifying catalyst of the present invention comprising a carrier containing yttrium manganate YMnO 3 and Ag supported on the surface of the carrier is, for example, from yttrium manganate YMnO 3 in a solution of a soluble silver compound. It can be manufactured by adding the carrier powder to be stirred and drying and baking the slurry. As another production method, a carrier powder composed of yttrium manganate YMnO 3 and an Ag compound powder such as Ag powder or silver carbonate can be blended and fired. As the firing atmosphere, for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example. At that time, a part of silver may be contained in the crystal lattice of YMnO 3 or may be dissolved in the crystal.
  • the exhaust gas purifying catalyst component of the present invention comprising a catalyst support made of ceramics or a metal material and the exhaust gas purifying catalyst supported on the surface of the catalyst support is, for example, soluble A carrier powder made of yttrium manganate YMnO 3 is placed in a silver compound solution and stirred. The slurry is coated on the surface of a catalyst support made of a ceramic or metal material in the form of a honeycomb or DPF, and then dried and fired. Can be manufactured.
  • As the firing atmosphere for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
  • the exhaust gas purifying catalyst component of the present invention comprising a catalyst support made of ceramics or a metal material and the exhaust gas purifying catalyst supported on the surface of the catalyst support is, for example, a ceramic.
  • a carrier powder made of yttrium manganate YMnO 3 is supported on the surface of a catalyst support made of a metal material, a solution of a soluble silver compound is brought into contact with the catalyst support carrying the carrier powder, and then dried and calcined. It can also be manufactured.
  • the firing atmosphere for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
  • a soluble silver compound solution When a soluble silver compound solution is used in the above production method, a soluble silver compound and a solvent that dissolves the silver compound are used.
  • a soluble silver compound and a solvent that dissolves the silver compound are used.
  • silver nitrate, silver acetate, silver fluoride or the like when silver nitrate, silver acetate, silver fluoride or the like is used as the silver compound, water or the like can be used as the solvent, and when silver oxide or the like is used as the silver compound, nitric acid, aqueous ammonia or the like is used as the solvent.
  • silver chloride or the like aqueous ammonia or the like can be used as the solvent, and the combination of the soluble silver compound and the solvent is obvious to those skilled in the art.
  • the Ag particles supported on the surface of the carrier containing yttrium manganate YMnO 3 include those having a size of 10 to 20 nm. Is preferred. That is, if the Ag particle is 10 nm or more, it is difficult to enter the pores of the yttrium manganate YMnO 3 particle, and if it is 20 nm or less, good contact with YMnO 3 is maintained and effective.
  • the exhaust gas purifying catalyst structure of the present invention particularly the DPF
  • a binder component By applying a binder component to the surface of the carrier, the adhesion between the substrate and the carrier is improved, the durability of the catalyst is improved, and the heat resistance is improved.
  • the DPF may have any shape known as DPF, but preferably has a three-dimensional structure.
  • the filter having a three-dimensional structure include a wall-through type, a flow-through honeycomb type, a wire mesh type, a ceramic fiber type, a metal porous body type, a particle filling type, and a foam type.
  • the material of the base material include cordierite, SiC and other ceramics, Fe—Cr—Al alloy, stainless steel alloy and the like.
  • the total coating amount of the catalyst is preferably about 10 to 100 g / L for the wall-through type DPF and about 50 to 150 g / L for the wire mesh type. If the total coating amount of the catalyst is too small, sufficient performance cannot be obtained. Moreover, when there is too much, the back pressure with respect to waste gas will become high.
  • the catalyst is preferably in a state where it is deposited only on the surface layer without entering the gap inside the wall.
  • the exhaust gas purifying catalyst component of the present invention is produced as a three-dimensional DPF
  • a carrier powder composed of yttrium manganate YMnO 3 is put in a solution of a soluble silver compound and stirred, and the slurry is three-dimensional. It can be produced by coating a catalyst support, which is a DPF having a structure, followed by drying and firing.
  • a catalyst support which is a DPF having a structure
  • the firing atmosphere for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
  • a carrier support made of yttrium manganate YMnO 3 is supported on a catalyst support which is a three-dimensional DPF, and the carrier It can also be produced by bringing a solution of a soluble silver compound into contact with a catalyst support on which a powder is supported, followed by drying and firing.
  • the firing atmosphere for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
  • the supported amount of Ag is 1 to 10 at% based on the number of Y atoms. It is preferably 4 to 9 at%.
  • the amount of Ag loaded is less than 1 at%, the exhaust gas purification performance is insufficient, and even when the amount is more than 10 at%, the exhaust gas purification performance tends to reach its peak.
  • Examples 1 to 5 and Comparative Example 1 A carrier powder made of yttrium manganate YMnO 3 was added to an aqueous silver nitrate solution so that the amount of Ag would be the ratio shown in Table 1 based on the number of Y atoms, and stirred for 30 minutes. Each obtained slurry was coated on the surface of a particulate filter made of cordierite having a diameter of 25.4 mm and a length of 76.2 mm. These were dried at 120 ° C. for 3 hours and then calcined in air at 500 ° C. for 1 hour.
  • the supported amount of YMnO 3 was 40 g / L, and the supported amount of Ag was as shown in Table 1 in terms of metal.
  • An electron micrograph of a part of the exhaust gas purifying catalyst structure obtained in Example 5 is shown in FIG.
  • the length of one scale is 6 nm, and the scale of 10 is 60 nm.
  • the size of the Ag particles supported on the YMnO 3 support is about 10 to 20 nm.
  • the exhaust gas purification catalyst components were separately loaded into a model gas measuring device (MEXA-7500D manufactured by Horiba, Ltd.), and the exhaust model gas having the composition shown in Table 2 below was circulated at a space velocity of 29000 / h.
  • the temperature was lowered from 600 ° C. at a rate of 17 ° C./min, and the CO and HC purification rates were measured continuously. From the obtained measurement results, the temperature (T50) at which each CO / HC reached a 50% purification rate was determined. The results were as shown in Table 1.
  • the exhaust gas purifying catalyst component of the present invention having yttrium manganate YMnO 3 supporting Ag is an exhaust gas of a comparative example having yttrium manganate YMnO 3 not supporting Ag.
  • the exhaust gas purification performance is superior to that of the purification catalyst component, and a sufficient exhaust gas purification effect is obtained when the amount of Ag supported is 1 to 10 at%. When it is ⁇ 9 at%, a significant exhaust gas purification effect is obtained.
  • the exhaust gas of the 2.4 L diesel engine was passed through the exhaust gas purification catalyst structure, and 2 g of soot was collected per 1 L of the exhaust gas purification catalyst structure. Thereafter, a soot combustion rate was measured by circulating a gas consisting of O 2 : 3.8%, NO: 200 ppm, and the balance: N 2 at 600 ° C. at a space velocity (SV) of 21300 / h.
  • SV space velocity
  • MEXA-7500D manufactured by HORIBA, Ltd. was used.
  • the 90% regeneration time (the time until 90% of the collected soot burned) was as shown in Table 3.
  • the exhaust gas purifying catalyst structure of Example 5 of the present invention including yttrium manganate YMnO 3 supporting Ag is provided with yttrium manganate YMnO 3 not supporting Ag.
  • Exhaust gas purification catalyst structure of Comparative Example 1 Exhaust gas purification catalyst structure of Comparative Example 2 comprising Pd-supported yttrium manganate YMnO 3 , Exhaust of Comparative Example 3 comprising Pt-supported Al 2 O 3 It is superior in the soot combustion rate than the gas purification catalyst structure.
  • the amount of Ag carried in the exhaust gas purification catalyst structure of Example 5 is the same as the amount of Pd carried by the exhaust gas purification catalyst structure of Comparative Example 2 and the Pt of the exhaust gas purification catalyst structure of Comparative Example 3.
  • the exhaust gas purifying catalyst structure of Example 5 is less expensive than those of Comparative Examples 2 and 3. Therefore, it became clear that a catalyst having excellent exhaust gas purification performance and heat resistance can be obtained by combining yttrium manganate YMnO 3 and Ag.

Abstract

An exhaust gas purification catalyst comprising a carrier including yttrium manganese oxide (YMnO3) and Ag supported on the surface of said carrier; and an exhaust gas purification catalyst structure comprising a catalyst support body comprising a ceramic or a metal material, and the exhaust gas purification catalyst supported on top of the catalyst support body.

Description

排気ガス浄化用触媒及び排気ガス浄化用触媒構成体Exhaust gas purification catalyst and exhaust gas purification catalyst structure
　本発明は自動車等の内燃機関から排出される排気ガスを浄化するために使用される排気ガス浄化用触媒及び排気ガス浄化用触媒構成体に関する。 The present invention relates to an exhaust gas purification catalyst and an exhaust gas purification catalyst structure used for purifying exhaust gas discharged from an internal combustion engine such as an automobile.
　自動車等の内燃機関から排出される排ガス中には、炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯ）等の有害成分が含まれている。それで、従来から、これら有害成分を浄化して無害化する三元触媒が用いられている。 The exhaust gas discharged from internal combustion engines such as automobiles contains harmful components such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NO). Therefore, conventionally, a three-way catalyst for purifying and detoxifying these harmful components has been used.
　このような三元触媒として、Ｐｔ、Ｐｄ、Ｒｈ等の貴金属とアルミナ、セリア、ジルコニア又はこれらの複合酸化物とを任意に組み合わせて、セラミックス又は金属等のハニカム担体上に塗布させたものが使用されている。 As such a three-way catalyst, a precious metal such as Pt, Pd, or Rh and an alumina, ceria, zirconia, or a composite oxide thereof are arbitrarily combined and applied on a honeycomb carrier such as ceramics or metal. Has been.
　また、ディーゼルエンジンから排出される排気ガスはパティキュレート（粒子状物質）を含んでおり、これらの物質がそのまま大気中に放出されると大気汚染の原因になる。パティキュレートを取り除くための有効な手段として、ススを捕集するためのディーゼル・パティキュレート・フィルター（ＤＰＦ）を用いたディーゼル排ガストラップシステムがある。しかし、このＤＰＦでは捕集したパティキュレートを酸化除去してＤＰＦを再生する必要がある。 Also, exhaust gas discharged from diesel engines contains particulates (particulate matter), and if these materials are released into the atmosphere as they are, they cause air pollution. As an effective means for removing particulates, there is a diesel exhaust gas trap system using a diesel particulate filter (DPF) for collecting soot. However, in this DPF, it is necessary to regenerate the DPF by oxidizing and removing the collected particulates.
　これまでに提案されたシステムとしては、担体、例えば、酸化ジルコニウム、酸化バナジウム、酸化セリウム等の無機酸化物からなる担体にＰｔなどの高価な貴金属を担持させた触媒（例えば、特許文献１、２及び３参照）や、安価な銀を担持させて触媒を用いるシステムがある。また、従来、銀を用いるものは安価であるものの、耐熱性に劣ることが指摘されている（非特許文献１参照）。 As a system proposed so far, a catalyst (for example, Patent Documents 1 and 2) in which an expensive noble metal such as Pt is supported on a carrier, for example, a carrier made of an inorganic oxide such as zirconium oxide, vanadium oxide, or cerium oxide. And 3) and a system that uses a catalyst by supporting inexpensive silver. Conventionally, it has been pointed out that although silver is inexpensive, it is inferior in heat resistance (see Non-Patent Document 1).
特開平１０－０４７０３５号公報Japanese Patent Laid-Open No. 10-047035 特開２００３－３３４４４３号公報JP 2003-334443 A 特開２００４－０５８０１３号公報JP 2004-058013 A
　本発明は自動車等の内燃機関から排出される排気ガスに対して有害なガス成分を浄化し且つパティキュレートを酸化除去し得る排気ガス浄化用触媒及び排気ガス浄化用触媒構成体を提供することを目的としている。 The present invention provides an exhaust gas purifying catalyst and an exhaust gas purifying catalyst structure capable of purifying gas components harmful to exhaust gas discharged from an internal combustion engine such as an automobile and oxidizing and removing particulates. It is aimed.
　本発明者らは上記の目的を達成するために種々の物質の組み合わせを用いて種々の実験を行った結果、マンガン酸イットリウムＹＭｎＯ３にＡｇを担持させることにより優れた排気ガス浄化性能とＡｇの欠点であった熱耐久性の問題も克服されることを見出し、本発明を完成した。 As a result of various experiments using various combinations of substances in order to achieve the above-mentioned object, the present inventors have achieved excellent exhaust gas purification performance and Ag by supporting Ag on yttrium manganate YMnO 3 . The present inventors have found that the problem of heat durability, which has been a drawback, can also be overcome.
　即ち、本発明の排気ガス浄化用触媒は、マンガン酸イットリウムＹＭｎＯ３を含む担体と、該担体の表面上に担持されているＡｇとからなることを特徴とする。 That is, the exhaust gas purifying catalyst of the present invention comprises a carrier containing yttrium manganate YMnO 3 and Ag supported on the surface of the carrier.
　本発明の排気ガス浄化用触媒においては、Ａｇの担持量がＹの原子数を基準にして１～１０ａｔ％であることが好ましく、４～９ａｔ％であることが一層好ましい。 In the exhaust gas purifying catalyst of the present invention, the supported amount of Ag is preferably 1 to 10 at%, more preferably 4 to 9 at%, based on the number of Y atoms.
　また、本発明の排気ガス浄化用触媒構成体は、セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている上記の排気ガス浄化用触媒とを備えていることを特徴とする。 The exhaust gas purifying catalyst component of the present invention comprises a catalyst support made of a ceramic or metal material and the exhaust gas purifying catalyst supported on the catalyst support. And
　本発明の排気ガス浄化用触媒構成体においては、セラミックス又は金属材料からなる触媒支持体がハニカム形状であるか、又はＤＰＦであることが好ましい。 In the exhaust gas purifying catalyst structure of the present invention, it is preferable that the catalyst support made of ceramics or a metal material has a honeycomb shape or a DPF.
　本発明の排気ガス浄化用触媒及び排気ガス浄化用触媒構成体は自動車等の内燃機関から排出される排気ガスに対して有害なガス成分を浄化し且つパティキュレートを酸化除去し得るので、即ち排気ガス浄化性能に優れているので、自動車等の内燃機関から排出される排気ガスを浄化するのに有効である。 The exhaust gas purifying catalyst and the exhaust gas purifying catalyst structure according to the present invention can purify gas components harmful to exhaust gas discharged from an internal combustion engine such as an automobile and oxidize and remove particulates. Since the gas purification performance is excellent, it is effective for purifying exhaust gas discharged from an internal combustion engine such as an automobile.
実施例３で得た排気ガス浄化用触媒構成体の一部分の電子顕微鏡写真である。4 is an electron micrograph of a part of the exhaust gas purifying catalyst structure obtained in Example 3. FIG.
　以下に、本発明の排気ガス浄化用触媒及び排気ガス浄化用触媒構成体について具体的に説明する。 Hereinafter, the exhaust gas purifying catalyst and the exhaust gas purifying catalyst structure of the present invention will be described in detail.
　本発明の排気ガス浄化用触媒及び排気ガス浄化用触媒構成体で用いるマンガン酸イットリウムは化学式ＹＭｎＯ３で表わされる公知の複酸化物であり、この複酸化物ＹＭｎＯ３は、例えば、硝酸イットリウムと硝酸マンガンとクエン酸と水とからなる混合物を、２００～４００℃の範囲内の温度、１～１０時間の範囲内の時間で一次焼成し、次いで８００～１０００℃の範囲内の温度、１～１０時間の範囲内の時間で二次焼成することにより製造することができる。 Yttrium manganate used in the exhaust gas purifying catalyst and the exhaust gas purifying catalyst structure of the present invention is a known double oxide represented by the chemical formula YMnO 3 , and this double oxide YMnO 3 includes, for example, yttrium nitrate and nitric acid. A mixture of manganese, citric acid and water is first calcined at a temperature in the range of 200-400 ° C. for a time in the range of 1-10 hours, and then at a temperature in the range of 800-1000 ° C., 1-10 It can manufacture by carrying out secondary baking for the time within the range of time.
　上記の複酸化物ＹＭｎＯ３の製造方法においては、例えば、硝酸イットリウム６水和物と硝酸マンガン６水和物とクエン酸と水とを１：１：６：４０のモル比の混合物として用いることができる。上記の製造方法において硝酸イットリウムと硝酸マンガンとのモル比が１：１からずれた場合や、反応温度、反応時間等の反応条件の変化によっては副生物として複酸化物ＹＭｎ２Ｏ５、複酸化物Ｙ２Ｍｎ２Ｏ７、Ｙ２Ｏ３、Ｍｎ２Ｏ３が生じることがあるが、これらの副生物を含む混合物も本発明において担体として同様に有用である。従って、本発明においてはマンガン酸イットリウムＹＭｎＯ３を含む担体と表示する。また、上記の複酸化物ＹＭｎＯ３の製造方法で得られるＹＭｎＯ３の結晶系は六方晶、斜方晶又はこれらの混合の形の何れかになるが、何れのものも本発明において担体として有用である。
In the above method for producing the double oxide YMnO 3 , for example, yttrium nitrate hexahydrate, manganese nitrate hexahydrate, citric acid and water are used as a mixture in a molar ratio of 1: 1: 6: 40. Can do. In the above production method, when the molar ratio of yttrium nitrate to manganese nitrate deviates from 1: 1, or depending on changes in reaction conditions such as reaction temperature and reaction time, double oxide YMn 2 O 5 , double oxidation The products Y 2 Mn 2 O 7 , Y 2 O 3 , Mn 2 O 3 may be produced, but mixtures containing these by-products are also useful as carriers in the present invention. Therefore, in the present invention, it is expressed as a support containing yttrium manganate YMnO 3 . Further, the crystal system of YMnO 3 obtained by the above-described method for producing the double oxide YMnO 3 is in the form of hexagonal crystal, orthorhombic crystal or a mixture thereof, any of which is useful as a support in the present invention. It is.
　また、他の製造方法としては、原料としてＹ２Ｏ３及びＭｎＯ２をＹ／Ｍｎの原子比が１／１になるように秤取し、例えばボールミルを用いて３時間以上粉砕・混合する方法を挙げることができる。この方法では、その後大気雰囲気下、９００℃で５時間焼成することにより複酸化物ＹＭｎＯ３を得ることができる。 As another production method, Y 2 O 3 and MnO 2 as raw materials are weighed so that the atomic ratio of Y / Mn is 1/1, and pulverized and mixed for 3 hours or more using, for example, a ball mill Can be mentioned. In this method, the double oxide YMnO 3 can be obtained by firing at 900 ° C. for 5 hours in the air atmosphere.
　さらに、他の製造方法としては、液相法を挙げることができる。例えば、液相法では、原料としてＹ、Ｍｎの硝酸塩をＹ／Ｍｎの原子比が１／１になる様に秤取し、水溶液としたものに、アンモニア等のアルカリ水溶液を滴下してＹとＭｎの沈殿を作り、これを濾過、洗浄、乾燥後例えば８００℃程度の十分な加熱により硝酸根を除去・結晶化することで複酸化物ＹＭｎＯ３を得ることができる。　 Furthermore, as another manufacturing method, a liquid phase method can be mentioned. For example, in the liquid phase method, nitrates of Y and Mn as raw materials are weighed so that the atomic ratio of Y / Mn becomes 1/1, and an aqueous solution such as ammonia is dropped into an aqueous solution. A double oxide YMnO 3 can be obtained by making a precipitate of Mn, filtering, washing and drying, and removing and crystallizing nitrate radicals by sufficient heating, for example, at about 800 ° C.
　何れにしても、複酸化物ＹＭｎＯ３の製造方法は特に限定されるものではない。 In any case, the method for producing the double oxide YMnO 3 is not particularly limited.
　本発明の排気ガス浄化用触媒は、このようなマンガン酸イットリウムＹＭｎＯ３を含む担体にＡｇを担持させたものである。担体はＹＭｎＯ３を単独で用いたものでもよく、アルミナ（Ａｌ２Ｏ３）、ＣｅＯ２、（ＣｅＺｒ）Ｏ２など他の公知の担体と混合して用いてもよい。 The exhaust gas purifying catalyst of the present invention is such that Ag is supported on a carrier containing such yttrium manganate YMnO 3 . The carrier may be YMnO 3 used alone, or may be used by mixing with other known carriers such as alumina (Al 2 O 3 ), CeO 2 , (CeZr) O 2 .
　マンガン酸イットリウムＹＭｎＯ３を含む担体と、該担体の表面上に担持されているＡｇとからなる本発明の排気ガス浄化用触媒は、例えば、可溶性銀化合物の溶液中に、マンガン酸イットリウムＹＭｎＯ３からなる担体粉末を入れて撹拌し、そのスラリーを加熱乾燥し、焼成することにより製造することができる。また、別の製法として、マンガン酸イットリウムＹＭｎＯ３からなる担体粉末とＡｇ粉末又は炭酸銀等のＡｇ化合物粉末とを配合し、焼成することにより製造することもできる。それらの焼成雰囲気として、例えば空気、酸素富化空気を用いることができ、また焼成を例えば４５０～６００℃で実施することができる。その際、銀の一部が、ＹＭｎＯ３の結晶の格子内に含有されるか又は結晶に固溶していることもあり得る。 The exhaust gas purifying catalyst of the present invention comprising a carrier containing yttrium manganate YMnO 3 and Ag supported on the surface of the carrier is, for example, from yttrium manganate YMnO 3 in a solution of a soluble silver compound. It can be manufactured by adding the carrier powder to be stirred and drying and baking the slurry. As another production method, a carrier powder composed of yttrium manganate YMnO 3 and an Ag compound powder such as Ag powder or silver carbonate can be blended and fired. As the firing atmosphere, for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example. At that time, a part of silver may be contained in the crystal lattice of YMnO 3 or may be dissolved in the crystal.
　また、セラミックス又は金属材料からなる触媒支持体と、該触媒支持体表面に担持されている上記の排気ガス浄化用触媒とを備えている本発明の排気ガス浄化用触媒構成体は、例えば、可溶性銀化合物の溶液中に、マンガン酸イットリウムＹＭｎＯ３からなる担体紛体を入れて撹拌し、そのスラリーをセラミックス又は金属材料からなるハニカム形状又はＤＰＦである触媒支持体表面にコートさせ、その後乾燥し、焼成することにより製造することができる。焼成雰囲気として、例えば空気、酸素富化空気を用いることができ、また焼成を例えば４５０～６００℃で実施することができる。 The exhaust gas purifying catalyst component of the present invention comprising a catalyst support made of ceramics or a metal material and the exhaust gas purifying catalyst supported on the surface of the catalyst support is, for example, soluble A carrier powder made of yttrium manganate YMnO 3 is placed in a silver compound solution and stirred. The slurry is coated on the surface of a catalyst support made of a ceramic or metal material in the form of a honeycomb or DPF, and then dried and fired. Can be manufactured. As the firing atmosphere, for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
　あるいは、セラミックス又は金属材料からなる触媒支持体と、該触媒支持体表面に担持されている上記の排気ガス浄化用触媒とを備えている本発明の排気ガス浄化用触媒構成体は、例えば、セラミックス又は金属材料からなる触媒支持体表面にマンガン酸イットリウムＹＭｎＯ３からなる担体紛体を担持させ、該担体紛体を担持した触媒支持体に可溶性銀化合物の溶液を接触させ、その後乾燥し、焼成することにより製造することもできる。焼成雰囲気として、例えば空気、酸素富化空気を用いることができ、また焼成を例えば４５０～６００℃で実施することができる。 Alternatively, the exhaust gas purifying catalyst component of the present invention comprising a catalyst support made of ceramics or a metal material and the exhaust gas purifying catalyst supported on the surface of the catalyst support is, for example, a ceramic. Alternatively, a carrier powder made of yttrium manganate YMnO 3 is supported on the surface of a catalyst support made of a metal material, a solution of a soluble silver compound is brought into contact with the catalyst support carrying the carrier powder, and then dried and calcined. It can also be manufactured. As the firing atmosphere, for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
　上記の製造方法において可溶性銀化合物の溶液を用いる場合には、可溶性銀化合物及び該銀化合物を溶解する溶媒を用いる。例えば、銀化合物として硝酸銀、酢酸銀、フッ化銀等を用いる場合には溶媒として水等を用いることができ、銀化合物として酸化銀等を用いる場合には溶媒として硝酸、アンモニア水等を用いることができ、銀化合物として塩化銀等を用いる場合には溶媒としてアンモニア水等を用いることができ、可溶性銀化合物と溶媒との組み合わせは当業者には自明である。 When a soluble silver compound solution is used in the above production method, a soluble silver compound and a solvent that dissolves the silver compound are used. For example, when silver nitrate, silver acetate, silver fluoride or the like is used as the silver compound, water or the like can be used as the solvent, and when silver oxide or the like is used as the silver compound, nitric acid, aqueous ammonia or the like is used as the solvent. When silver chloride or the like is used as the silver compound, aqueous ammonia or the like can be used as the solvent, and the combination of the soluble silver compound and the solvent is obvious to those skilled in the art.
　本発明の排気ガス浄化用触媒及び排気ガス浄化用触媒構成体において、マンガン酸イットリウムＹＭｎＯ３を含む担体の表面上に担持されているＡｇ粒子については、１０～２０ｎｍの大きさのものを含むことが好ましい。すなわち、Ａｇ粒子が１０ｎｍ以上であるとマンガン酸イットリウムＹＭｎＯ３粒子の細孔に入りにくく、２０ｎｍ以下であるとＹＭｎＯ３と良好な接触を保ち効果的だからである。 In the exhaust gas purifying catalyst and the exhaust gas purifying catalyst structure of the present invention, the Ag particles supported on the surface of the carrier containing yttrium manganate YMnO 3 include those having a size of 10 to 20 nm. Is preferred. That is, if the Ag particle is 10 nm or more, it is difficult to enter the pores of the yttrium manganate YMnO 3 particle, and if it is 20 nm or less, good contact with YMnO 3 is maintained and effective.
　本発明の排気ガス浄化用触媒構成体、特にＤＰＦを製造することを考慮すると、担体の表面にバインダー成分としてＳｉＯ２、ＴｉＯ２、ＺｒＯ２、Ａｌ２Ｏ３などを付与しておくことが好ましい。担体の表面にバインダー成分を付与することにより基材と担体との密着性が向上して触媒の耐久性が向上し、耐熱性が向上する。 Considering the production of the exhaust gas purifying catalyst structure of the present invention, particularly the DPF, it is preferable to give SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 or the like as a binder component to the surface of the carrier. . By applying a binder component to the surface of the carrier, the adhesion between the substrate and the carrier is improved, the durability of the catalyst is improved, and the heat resistance is improved.
　ＤＰＦはＤＰＦとして公知のいかなる形状であっても良いが、三次元立体構造を有するものが好ましい。三次元立体構造を有するフィルターの具体例として、ウォールスルー型、フロースルーハニカム型、ワイヤメッシュ型、セラミックファイバー型、金属多孔体型、粒子充填型、フォーム型等を挙げることができる。また、基材の材質としてコージエライト、ＳｉＣなどのセラミックやＦｅ－Ｃr－Ａｌ合金やステンレス合金などを挙げることができる。触媒の総コート量としては、ウォールスルー型ＤＰＦの場合には１０～１００ｇ／Ｌ、ワイヤメッシュ型の場合には５０～１５０ｇ／Ｌくらいが好ましい。触媒の総コート量が少なすぎると充分な性能を得ることができない。また、多すぎると排ガスに対する背圧が高くなってしまう。なお、ウォールスルー型ＤＰＦの場合には触媒はウォール内部の間隙に入り込まず表層のみに堆積した状態であることが好ましい。 The DPF may have any shape known as DPF, but preferably has a three-dimensional structure. Specific examples of the filter having a three-dimensional structure include a wall-through type, a flow-through honeycomb type, a wire mesh type, a ceramic fiber type, a metal porous body type, a particle filling type, and a foam type. Further, examples of the material of the base material include cordierite, SiC and other ceramics, Fe—Cr—Al alloy, stainless steel alloy and the like. The total coating amount of the catalyst is preferably about 10 to 100 g / L for the wall-through type DPF and about 50 to 150 g / L for the wire mesh type. If the total coating amount of the catalyst is too small, sufficient performance cannot be obtained. Moreover, when there is too much, the back pressure with respect to waste gas will become high. In the case of a wall-through type DPF, the catalyst is preferably in a state where it is deposited only on the surface layer without entering the gap inside the wall.
　本発明の排気ガス浄化用触媒構成体を三次元構造のＤＰＦとして製造する場合には、可溶性銀化合物の溶液中にマンガン酸イットリウムＹＭｎＯ３からなる担体紛体を入れて撹拌し、そのスラリーを三次元構造のＤＰＦである触媒支持体にコートさせ、その後乾燥し、焼成することにより製造することができる。焼成雰囲気として、例えば空気、酸素富化空気を用いることができ、また焼成を例えば４５０～６００℃で実施することができる。 When the exhaust gas purifying catalyst component of the present invention is produced as a three-dimensional DPF, a carrier powder composed of yttrium manganate YMnO 3 is put in a solution of a soluble silver compound and stirred, and the slurry is three-dimensional. It can be produced by coating a catalyst support, which is a DPF having a structure, followed by drying and firing. As the firing atmosphere, for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
　本発明の排気ガス浄化用触媒構成体を三次元構造のＤＰＦとして製造するその他の方法として、三次元構造のＤＰＦである触媒支持体にマンガン酸イットリウムＹＭｎＯ３からなる担体紛体を担持させ、該担体紛体を担持した触媒支持体に可溶性銀化合物の溶液を接触させ、その後乾燥し、焼成することにより製造することもできる。それらの焼成雰囲気として、例えば空気、酸素富化空気を用いることができ、また焼成を例えば４５０～６００℃で実施することができる。 As another method for producing the exhaust gas purifying catalyst component of the present invention as a three-dimensional DPF, a carrier support made of yttrium manganate YMnO 3 is supported on a catalyst support which is a three-dimensional DPF, and the carrier It can also be produced by bringing a solution of a soluble silver compound into contact with a catalyst support on which a powder is supported, followed by drying and firing. As the firing atmosphere, for example, air or oxygen-enriched air can be used, and firing can be performed at 450 to 600 ° C., for example.
　本発明の排気ガス浄化用触媒及び排気ガス浄化用触媒構成体においては、後記の実施例のデータからも明らかなように、Ａｇの担持量がＹの原子数を基準にして１～１０ａｔ％であることが好ましく、４～９ａｔ％であることが一層好ましい。Ａｇの担持量が１ａｔ％よりも少ない場合には排気ガス浄化性能が不十分であり、また１０ａｔ％よりも多くなっても排気ガス浄化性能が頭打ちとなる傾向がある。 In the exhaust gas purifying catalyst and the exhaust gas purifying catalyst structure of the present invention, as is clear from the data of the examples described later, the supported amount of Ag is 1 to 10 at% based on the number of Y atoms. It is preferably 4 to 9 at%. When the amount of Ag loaded is less than 1 at%, the exhaust gas purification performance is insufficient, and even when the amount is more than 10 at%, the exhaust gas purification performance tends to reach its peak.
　以下に、実施例及び比較例に基づいて本発明を具体的に説明する。 Hereinafter, the present invention will be described in detail based on examples and comparative examples.
　実施例１～５及び比較例１
　硝酸銀水溶液中にＡｇの量がＹの原子数を基準にしてそれぞれ第１表に示す割合となるようにマンガン酸イットリウムＹＭｎＯ３からなる担体粉末を投入し、３０分間攪拌した。得られた各々のスラリーを直径２５．４ｍｍ×長さ７６．２ｍｍのコージェライト製パティキュレートフィルター表面にコートさせた。これらを１２０℃で３時間乾燥した後、空気中５００℃で１時間焼成した。得られた各々のパティキュレートフィルター形状の排ガス浄化用触媒構成体のＹＭｎＯ３の担持量は４０ｇ／Ｌであり、Ａｇの担持量は金属換算で第１表に示す通りであった。なお、実施例５で得た排気ガス浄化用触媒構成体の一部分の電子顕微鏡写真を図１に示す。図１の電子顕微鏡写真において１目盛の長さは６ｎｍであり、１０目盛りで６０ｎｍであることを示している。図１から明らかなように、ＹＭｎＯ３担体上に担持されているＡｇ粒子の大きさは１０～２０ｎｍ程度である。 Examples 1 to 5 and Comparative Example 1
A carrier powder made of yttrium manganate YMnO 3 was added to an aqueous silver nitrate solution so that the amount of Ag would be the ratio shown in Table 1 based on the number of Y atoms, and stirred for 30 minutes. Each obtained slurry was coated on the surface of a particulate filter made of cordierite having a diameter of 25.4 mm and a length of 76.2 mm. These were dried at 120 ° C. for 3 hours and then calcined in air at 500 ° C. for 1 hour. In each of the obtained particulate filter-shaped exhaust gas purification catalyst components, the supported amount of YMnO 3 was 40 g / L, and the supported amount of Ag was as shown in Table 1 in terms of metal. An electron micrograph of a part of the exhaust gas purifying catalyst structure obtained in Example 5 is shown in FIG. In the electron micrograph of FIG. 1, the length of one scale is 6 nm, and the scale of 10 is 60 nm. As is clear from FIG. 1, the size of the Ag particles supported on the YMnO 3 support is about 10 to 20 nm.
　＜排ガス浄化性能試験＞
　実施例１～５及び比較例１で得られた各々の排気ガス浄化用触媒構成体を大気中、７００℃で３０時間耐久処理した。耐久処理後の排気ガス浄化用触媒構成体の触媒活性を以下のようにして評価した。 <Exhaust gas purification performance test>
Each exhaust gas purifying catalyst structure obtained in Examples 1 to 5 and Comparative Example 1 was subjected to a durability treatment at 700 ° C. for 30 hours in the atmosphere. The catalytic activity of the exhaust gas purifying catalyst structure after the durability treatment was evaluated as follows.
　それらの排ガス浄化用触媒構成体を別々にモデルガス測定装置（堀場製作所製ＭＥＸＡ－７５００Ｄ）に装填し、下記の第２表に示す組成の排気モデルガスを空間速度２９０００／ｈで流通させながら、６００℃から１７℃／分の降温速度で降温させ、ＣＯ、ＨＣ浄化率を連続的に測定した。得られた測定結果より、ＣＯ／ＨＣそれぞれの５０％浄化率に到達する温度（Ｔ５０）を求めた。それらの結果は第１表に示す通りであった。 The exhaust gas purification catalyst components were separately loaded into a model gas measuring device (MEXA-7500D manufactured by Horiba, Ltd.), and the exhaust model gas having the composition shown in Table 2 below was circulated at a space velocity of 29000 / h. The temperature was lowered from 600 ° C. at a rate of 17 ° C./min, and the CO and HC purification rates were measured continuously. From the obtained measurement results, the temperature (T50) at which each CO / HC reached a 50% purification rate was determined. The results were as shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　第１表に示すデータから明らかなように、Ａｇを担持したマンガン酸イットリウムＹＭｎＯ３を備える本発明の排気ガス浄化用触媒構成体はＡｇを担持しないマンガン酸イットリウムＹＭｎＯ３を備える比較例の排気ガス浄化用触媒構成体よりも排気ガス浄化性能に優れており、また、Ａｇの担持量が１～１０ａｔ％である場合に十分な排気ガス浄化効果が得られており、特にＡｇの担持量が４～９ａｔ％である場合に顕著な排気ガス浄化効果が得られている。 As is apparent from the data shown in Table 1, the exhaust gas purifying catalyst component of the present invention having yttrium manganate YMnO 3 supporting Ag is an exhaust gas of a comparative example having yttrium manganate YMnO 3 not supporting Ag. The exhaust gas purification performance is superior to that of the purification catalyst component, and a sufficient exhaust gas purification effect is obtained when the amount of Ag supported is 1 to 10 at%. When it is ˜9 at%, a significant exhaust gas purification effect is obtained.
　＜スス燃焼速度の測定法＞
　実施例５で得られたＡｇ／ＹＭｎＯ３担持排気ガス浄化用触媒構成体（Ａｇ担持量２．３ｇ／Ｌ）、比較例１で得られたＹＭｎＯ３担持排気ガス浄化用触媒構成体（貴金属担持なし）、硝酸銀の代わりに硝酸パラジウムを用いた以外は実施例５と同様にして得られたＰｄ／ＹＭｎＯ３担持排気ガス浄化用触媒構成体（Ｐｄ担持量０．４ｇ／Ｌ）（比較例２）、及び硝酸銀の代わりにジニトロジアンミン白金を用い、ＹＭｎＯ３の代わりにＡｌ２Ｏ３を用いた以外は実施例５と同様にして得られたＰｔ／Ａｌ２Ｏ３担持排気ガス浄化用触媒構成体（Ｐｔ担持量０．５ｇ／Ｌ）（比較例３）をそれぞれ大気中、７００℃で３０時間耐久処理した。耐久処理後の各々の排気ガス浄化用触媒構成体について下記の方法でスス燃焼速度を測定した。 <Measurement method of soot burning rate>
Ag / YMnO 3 supported exhaust gas purification catalyst structure obtained in Example 5 (Ag supported amount 2.3 g / L), YMnO 3 supported exhaust gas purification catalyst structure obtained in Comparative Example 1 (noble metal support) None), Pd / YMnO 3 -supported exhaust gas purification catalyst structure (Pd support amount 0.4 g / L) obtained in the same manner as in Example 5 except that palladium nitrate was used instead of silver nitrate (Comparative Example 2) And Pt / Al 2 O 3 supported exhaust gas purifying catalyst structure obtained in the same manner as in Example 5 except that dinitrodiammine platinum was used instead of silver nitrate and Al 2 O 3 was used instead of YMnO 3. Each of the bodies (Pt supported amount 0.5 g / L) (Comparative Example 3) was endured for 30 hours at 700 ° C. in the air. The soot combustion rate was measured by the following method for each exhaust gas purifying catalyst structure after the endurance treatment.
　２．４Ｌディーゼルエンジンの排気ガスを上記の排気ガス浄化用触媒構成体中に通してススを排気ガス浄化用触媒構成体１Ｌ当たり２ｇ捕集させた。その後、６００℃でＯ２：３．８％、ＮＯ：２００ｐｐｍ、残部：Ｎ２からなるガスを空間速度（ＳＶ）２１３００／ｈで流通させてスス燃焼速度を測定した。測定には堀場製作所製ＭＥＸＡ－７５００Ｄを用いた。９０％再生時間（捕集されていたススの９０％が燃焼するまでの時間）は第３表に示す通りであった。 The exhaust gas of the 2.4 L diesel engine was passed through the exhaust gas purification catalyst structure, and 2 g of soot was collected per 1 L of the exhaust gas purification catalyst structure. Thereafter, a soot combustion rate was measured by circulating a gas consisting of O 2 : 3.8%, NO: 200 ppm, and the balance: N 2 at 600 ° C. at a space velocity (SV) of 21300 / h. For the measurement, MEXA-7500D manufactured by HORIBA, Ltd. was used. The 90% regeneration time (the time until 90% of the collected soot burned) was as shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　第３表に示すデータから明らかなように、Ａｇを担持したマンガン酸イットリウムＹＭｎＯ３を備える本発明の実施例５の排気ガス浄化用触媒構成体は、Ａｇを担持しないマンガン酸イットリウムＹＭｎＯ３を備える比較例１の排気ガス浄化用触媒構成体、Ｐｄを担持したマンガン酸イットリウムＹＭｎＯ３を備える比較例２の排気ガス浄化用触媒構成体、Ｐｔを担持したＡｌ２Ｏ３を備える比較例３の排気ガス浄化用触媒構成体よりもスス燃焼速度において優れている。なお、実施例５の排気ガス浄化用触媒構成体のＡｇの担持量は、比較例２の排気ガス浄化用触媒構成体のＰｄの担持量及び比較例３の排気ガス浄化用触媒構成体のＰｔの担持量よりも多いが、実施例５の排気ガス浄化用触媒構成体は比較例２及び３のものよりも安価である。従って、マンガン酸イットリウムＹＭｎＯ３とＡｇとを組み合わせることで優れた排気ガス浄化性能と耐熱性を有する触媒が得られることが明らかになった。 As is clear from the data shown in Table 3 , the exhaust gas purifying catalyst structure of Example 5 of the present invention including yttrium manganate YMnO 3 supporting Ag is provided with yttrium manganate YMnO 3 not supporting Ag. Exhaust gas purification catalyst structure of Comparative Example 1, Exhaust gas purification catalyst structure of Comparative Example 2 comprising Pd-supported yttrium manganate YMnO 3 , Exhaust of Comparative Example 3 comprising Pt-supported Al 2 O 3 It is superior in the soot combustion rate than the gas purification catalyst structure. Note that the amount of Ag carried in the exhaust gas purification catalyst structure of Example 5 is the same as the amount of Pd carried by the exhaust gas purification catalyst structure of Comparative Example 2 and the Pt of the exhaust gas purification catalyst structure of Comparative Example 3. However, the exhaust gas purifying catalyst structure of Example 5 is less expensive than those of Comparative Examples 2 and 3. Therefore, it became clear that a catalyst having excellent exhaust gas purification performance and heat resistance can be obtained by combining yttrium manganate YMnO 3 and Ag.

Claims (6)

  1. 　マンガン酸イットリウムＹＭｎＯ３を含む担体と、該担体の表面上に担持されているＡｇとからなることを特徴とする排気ガス浄化用触媒。 An exhaust gas purification catalyst comprising a carrier containing yttrium manganate YMnO 3 and Ag supported on the surface of the carrier.
  2. 　Ａｇの担持量がＹの原子数を基準にして１～１０ａｔ％である請求項１記載の排気ガス浄化用触媒。 The exhaust gas purifying catalyst according to claim 1, wherein the supported amount of Ag is 1 to 10 at% based on the number of Y atoms.
  3. 　マンガン酸イットリウムＹＭｎＯ３を含む担体の表面上に担持されているＡｇ粒子が１０～２０ｎｍの大きさの粒子を含む請求項１又は２記載の排気ガス浄化用触媒。 The exhaust gas purifying catalyst according to claim 1 or 2, wherein the Ag particles supported on the surface of the carrier containing yttrium manganate YMnO 3 include particles having a size of 10 to 20 nm.
  4. 　セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている請求項１、２又は３に記載の排気ガス浄化用触媒とを備えていることを特徴とする排気ガス浄化用触媒構成体。 An exhaust gas purifying apparatus comprising: a catalyst support made of ceramics or a metal material; and the exhaust gas purifying catalyst according to claim 1, 2 or 3 supported on the catalyst support. Catalyst component.
  5. 　触媒支持体がハニカム形状である請求項４記載の排気ガス浄化用触媒構成体。 The exhaust gas purifying catalyst structure according to claim 4, wherein the catalyst support has a honeycomb shape.
  6. 　触媒支持体がＤＰＦである請求項４記載の排気ガス浄化用触媒構成体。 The exhaust gas purifying catalyst component according to claim 4, wherein the catalyst support is DPF.
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