WO2015125206A1 - 排気ガス浄化触媒及びその製造方法 - Google Patents

排気ガス浄化触媒及びその製造方法 Download PDF

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WO2015125206A1
WO2015125206A1 PCT/JP2014/053748 JP2014053748W WO2015125206A1 WO 2015125206 A1 WO2015125206 A1 WO 2015125206A1 JP 2014053748 W JP2014053748 W JP 2014053748W WO 2015125206 A1 WO2015125206 A1 WO 2015125206A1
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oxide
exhaust gas
gas purification
purification catalyst
pore volume
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French (fr)
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美咲 藤本
花木　保成
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Priority to JP2016503801A priority Critical patent/JP6136083B2/ja
Priority to US15/118,213 priority patent/US10245579B2/en
Priority to EP14882869.2A priority patent/EP3108961B1/en
Priority to CN201480075828.1A priority patent/CN106029223B/zh
Priority to PCT/JP2014/053748 priority patent/WO2015125206A1/ja
Publication of WO2015125206A1 publication Critical patent/WO2015125206A1/ja
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • 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
    • 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]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • 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
    • F01N3/103—Oxidation catalysts for HC and CO only
    • 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
    • F01N3/24—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 characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
    • 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
    • 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
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • 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
    • B01D2255/908—O2-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
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    • B01D2255/92—Dimensions
    • B01D2255/9202—Linear dimensions
    • 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
    • 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
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/12—Hydrocarbons
    • 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 particularly to an exhaust gas purification catalyst having an appropriate pore volume and excellent gas diffusibility and a method for producing the same.
  • LaMM'Ox (M is Ba, Sr, Ca, etc., M 'is Fe, Co, Ni, Mn, etc.) is supported on an oxygen storage material (OSC material), and the exhaust gas has an improved redox function.
  • OSC material oxygen storage material
  • a purification catalyst is known (see, for example, Patent Document 1).
  • the La-based oxide has gas diffusion properties. It has been found that the pores of about 100 nm may be crushed and the original catalyst performance may deteriorate at high space velocities.
  • the present invention has been made in view of such knowledge, and an object of the present invention is to provide an exhaust gas purification catalyst that is excellent in gas diffusibility and can exhibit its original catalytic performance, and a method for producing the same. .
  • the present inventor has found that the above object can be achieved by appropriately controlling the pore volume of a predetermined pore, and has completed the present invention. .
  • the exhaust gas purification catalyst of the present invention is an exhaust gas purification catalyst containing oxide 1 and oxide 2. Having pores P 1-260 having a pore diameter of 1 nm to 260 nm, which can be measured by a nitrogen adsorption method, The total ⁇ PV 1-260 of the pore volume PV 1-260 of these pores is 0.79 cm 3 / g or more.
  • the method for producing an exhaust gas purification catalyst of the present invention is a method for producing the exhaust gas purification catalyst as described above.
  • the oxide 2 precursor is mixed with the oxide 1 before the oxide 1 is fired, and the mixture is then fired.
  • the pore volume of the predetermined pores is appropriately controlled, it is possible to provide an exhaust gas purification catalyst that is excellent in gas diffusibility and can exhibit the original catalytic performance, and a method for producing the same. it can.
  • the exhaust gas purification catalyst of the present invention contains oxide 1 and oxide 2.
  • the oxide 1 is not particularly limited as long as it is an oxygen storage material (OSC material) having an oxygen storage / release function.
  • OSC material oxygen storage material
  • the oxide 1 contains cerium (Ce) and / or zirconium (Zr). And composite oxides.
  • oxide 2 is lanthanum (La), barium (Ba), strontium (Sr), calcium (Ca), iron (Fe), cobalt (Co), nickel (Ni), and manganese (Mn And at least one element selected from the group consisting of: Specifically, the following general formula (2) La x M 1-x M′O 3- ⁇ (2) (Wherein M is at least one element selected from the group consisting of Ba, Sr and Ca, M ′ is at least one element selected from the group consisting of Fe, Co, Ni and Mn, and ⁇ is oxygen) The amount of defects is shown, and x satisfies 0 ⁇ x ⁇ 1 and ⁇ satisfies the relationship 0 ⁇ ⁇ ⁇ 1.)
  • the exhaust gas purification catalyst of the present invention has pores (P 1-260 ) having a pore diameter of 1 nm to 260 nm that can be measured by a nitrogen (N 2 ) adsorption method, and the pore volume ( PV 1-260 ) ( ⁇ PV 1-260 ) is 0.79 cm 3 / g or more.
  • the exhaust gas purification catalyst of the present invention has a pore volume of 1 nm to 260 nm and a pore volume of 0.79 cm 3 / g or more, the catalyst performance can be effectively maintained even at a high space velocity (at high SV). .
  • the exhaust gas purification catalyst of the present invention is typically obtained by impregnating or supporting the oxide 2 on the oxide 1 powder.
  • the increase rate ( ⁇ PV 100-260 ) of the pore volume sum of the pores having a pore diameter of 100 to 260 nm by the loading satisfies ⁇ PV 100-260 ⁇ 1
  • the increase rate of the pore volume sum of 100 to 260 nm is equal to the pore volume ( ⁇ PV 100-260 ) in the predetermined pore diameter range in the catalyst layer formed of oxide 1, and the oxidation rate. What is necessary is just to compare the pore volume ( ⁇ PV 100-260 ) in a predetermined pore diameter range in the catalyst layer formed by supporting the oxide 2 on the product 1, and the increase rate ( ⁇ PV 100-260 ) is 1 or more.
  • the HC (hydrocarbon) oxidation performance at high SV is improved.
  • the gas diffusibility in the catalyst layer at the time of high SV is improved, so that the retention rate of HC oxidation performance is improved.
  • oxide 2 when oxide 2 is supported on oxide 1, oxide 2 can be supported without reducing the pore volume corresponding to pores having a pore diameter of 100 to 260 nm of oxide 1.
  • 0.11 in the formula (1) is a value defined as a reference value of the pore volume in the above pore diameter range that the oxide 1 can take.
  • This manufacturing method is a method for manufacturing the above-described exhaust gas purifying catalyst of the present invention.
  • the precursor of the oxide 2 is mixed with the oxide 1, This mixture is fired.
  • the oxide 2 component is added before the oxide 1 is fired to form pores. If the oxide 2 is supported after the oxide 1 is formed (fired), the oxide 2 may fill the pores of the oxide 1, which is not preferable.
  • the precursor of the oxide 2 is made of lanthanum (La), barium (Ba), strontium (Sr), calcium (Ca), iron (Fe), cobalt (Co), nickel (Ni) and manganese (Mn).
  • Examples thereof include carboxylates of at least one element selected from the group. These carboxylate solutions have a certain degree of viscosity and are easily impregnated with the oxide 1.
  • carboxylic acids include those having 1 to 4 carboxyl groups, such as gluconic acid, malic acid, maleic acid, acetic acid, succinic acid, fumaric acid, propionic acid, methacrylic acid, acrylic acid, citric acid, and tartaric acid. , Itaconic acid, formic acid and malonic acid.
  • Example 3 The oxide 2 carboxylate shown in Table 1 was prepared, mixed with the oxide 1 precursor, dried, and then fired at 700 ° C. to obtain a slurry, which was then coated on a monolith honeycomb carrier.
  • the exhaust gas purification catalyst of each example was obtained by drying and baking at 400 degreeC.
  • Comparative Examples 1 and 2 For Comparative Example 1, the precursor of oxide 1 shown in Table 1 was dried and further calcined at 700 ° C., impregnated with the carboxylate of oxide 2, dried, and calcined at 700 ° C. To obtain a powder. The obtained powder was made into a catalyst slurry, coated on a monolith type honeycomb carrier, dried, and fired at 400 ° C. to obtain an exhaust gas purification catalyst. For Comparative Example 2, the precursor of oxide 1 shown in Table 1 was dried, and the powder obtained by firing at 700 ° C. was made into a catalyst slurry, coated on a honeycomb carrier and dried, at 400 ° C. By firing, an exhaust gas purification catalyst was obtained. Table 1 summarizes the compounding ratio of oxide 1 and oxide 2, the composition of oxides 1 and 2, the specifications of the honeycomb carrier, the HC purification test conditions, and the like.
  • Total pore volume This is the total pore volume with a diameter of 1 to 260 nm measured by the nitrogen adsorption method.
  • the powder was heated, depressurized, etc. to remove the adsorbed gas, and after cooling, the total pore volume was calculated from the amount of nitrogen introduced in the cooled state and the amount of adsorption when nitrogen was adsorbed on the material surface and became a relative pressure.
  • Total pore volume of 100-260 nm diameter Of the total pore volumes measured above, the total pore volume having pore diameters of 100 nm to 260 nm or less.
  • the reference value of the pore volume of 100 to 260 nm diameter (actually the average value of oxide 1) is defined as 0.11, and the total pore volume of 100 to 260 nm diameter of the catalyst prepared according to the present invention ( ⁇ PV 100 If a value obtained by dividing ⁇ 260 ) by 1 or more is 1, it is a value indicating that ⁇ PV 100-260 is increasing.
  • Performance retention rate (%) [HC purification performance when SV is 30252h ⁇ 1 ] ⁇ [HC purification performance when SV is 20168h ⁇ 1 ] ⁇ 100
  • the HC performance retention shown in Table 1 is shown as a graph in FIG. 1 and FIG. 2 by the total pore volume and the increase rate of 100-260 nm diameter pore volume.

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Abstract

　酸化物１と酸化物２を含有する排気ガス浄化触媒である。窒素吸着法で測定できる１ｎｍ～２６０ｎｍの細孔径を持つ細孔Ｐ１－２６０を有し、この細孔の細孔容積ＰＶ１－２６０の総和ΣＰＶ１－２６０が０．７９ｃｍ３／ｇ以上である。　酸化物１は酸素放出能を有する酸化物である。酸化物２は、ＬａｘＭ１－ｘＭ'Ｏ３－δ…（２） （式中のＭはＢａ、Ｓｒ及びＣａから成る群より選ばれた少なくとも１種の元素、Ｍ'はＦｅ、Ｃｏ、Ｎｉ及びＭｎから成る群より選ばれた少なくとも１種の元素、δは酸素欠損量を示し、ｘは０≦ｘ≦１、δは０≦δ≦１の関係を満足する。）で表される。

Description

排気ガス浄化触媒及びその製造方法
　本発明は、排気ガス浄化触媒及びその製造方法に係り、更に詳細には、適切な細孔容積を有しガス拡散性に優れた排気ガス浄化触媒及びその製造方法に関する。
　従来、酸素吸蔵材（ＯＳＣ材）にＬａＭＭ’Ｏｘ（ＭはＢａ、Ｓｒ及びＣａ等、Ｍ’はＦｅ、Ｃｏ、Ｎｉ及びＭｎ等を示す。）を担持させ、レドックス機能を向上させた排気ガス浄化触媒が知られている（例えば、特許文献１参照。）。
国際公開２０１２／１３３５２６号明細書
　しかしながら、本発明者が更に検討したところ、このような従来技術にあっては、ＯＳＣ材を上記Ｌａ系酸化物に担持ないし含浸する際、Ｌａ系酸化物が有しガス拡散性に影響を及ぼす１００ｎｍ程度の細孔を潰してしまうことがあり、高い空間速度においては本来の触媒性能が悪化することがあることを知見した。
　本発明は、かかる知見に鑑みてなされたものであり、その目的とするところは、ガス拡散性に優れ、本来の触媒性能を発揮し得る排気ガス浄化触媒及びその製造方法を提供することにある。
　本発明者は、上記目的を達成すべく鋭意検討を重ねた結果、所定の細孔の細孔容積を適切に制御することにより、上記目的が達成できることを見出し、本発明を完成するに至った。
　即ち、本発明の排気ガス浄化触媒は、酸化物１と酸化物２を含有する排気ガス浄化触媒である。
　窒素吸着法で測定できる１ｎｍ～２６０ｎｍの細孔径を持つ細孔Ｐ１－２６０を有し、
　この細孔の細孔容積ＰＶ１－２６０の総和ΣＰＶ１－２６０が０．７９ｃｍ３／ｇ以上であることを特徴とする。
　また、本発明の排気ガス浄化触媒の製造方法は、上述の如き排気ガス浄化触媒を製造する方法である。
　酸化物１を焼成する前に酸化物２の前駆体を酸化物１に混合し、次いで、この混合物を焼成することを特徴とする。
　本発明によれば、所定の細孔の細孔容積を適切に制御することとしたため、ガス拡散性に優れ、本来の触媒性能を発揮し得る排気ガス浄化触媒及びその製造方法を提供することができる。
各例の排気ガス浄化触におけるＨＣ性能保持率を示すグラフである。 各例の排気ガス浄化触におけるＨＣ性能保持率を示すグラフである。
　以下、本発明の排気ガス浄化触媒について説明する。
（１）本発明の排気ガス浄化触媒は、酸化物１と酸化物を２を含有する。
　ここで、酸化物１としては、酸素吸蔵放出機能を有する酸素吸蔵材（ＯＳＣ材）であれば特に限定されるものではないが、セリウム（Ｃｅ）及び／又はジルコニウム（Ｚｒ）を含有する酸化物や複合酸化物を挙げることができる。
　一方、酸化物２としては、酸化物２がランタン（Ｌａ）、バリウム（Ｂａ）、ストロンチウム（Ｓｒ）、カルシウム（Ｃａ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）から成る群より選ばれた少なくとも１種の元素を含有するものを挙げることができる。
　また、具体的には、次の一般式（２）
　ＬａｘＭ１－ｘＭ’Ｏ３－δ…（２）
（式中のＭはＢａ、Ｓｒ及びＣａから成る群より選ばれた少なくとも１種の元素、Ｍ’はＦｅ、Ｃｏ、Ｎｉ及びＭｎから成る群より選ばれた少なくとも１種の元素、δは酸素欠損量を示し、ｘは０≦ｘ≦１、δは０≦δ≦１の関係を満足する。）で表される酸化物を挙げることができる。
（２）本発明の排気ガス浄化触媒は、窒素（Ｎ２）吸着法で測定できる１ｎｍ～２６０ｎｍの細孔径を持つ細孔（Ｐ１－２６０）を有し、この細孔の細孔容積（ＰＶ１－２６０）の総和（ΣＰＶ１－２６０）が０．７９ｃｍ３／ｇ以上である。
　このように、本発明の排気ガス浄化触媒は、細孔径１ｎｍ～２６０ｎｍの細孔容積が０．７９ｃｍ３／ｇ以上なので、高い空間速度時（高ＳＶ時）においても触媒性能を有効に保持できる。
（３）本発明の排気ガス浄化触媒は、典型的には、酸化物２を酸化物１の粉末に含浸ないし担持して得られる。
　この場合、本発明の排気ガス浄化触媒は、上記担持による１００～２６０ｎｍの細孔径を持つ細孔の細孔容積総和の増加率（ΔΣＰＶ１００－２６０）がΔΣＰＶ１００－２６０≧１を満足し、この細孔容積総和の増加率（ΔΣＰＶ１００－２６０）が、次式（１）
　ΔΣＰＶ１００－２６０＝（担持後の排気ガス浄化触媒における細孔容積の総和（σＰＶ１００－２６０））÷０．１１…（１）
　で表される。
　典型的には、１００～２６０ｎｍの細孔容積総和の増加率（ΔΣＰＶ１００－２６０）は、酸化物１で形成した触媒層における所定細孔径範囲の細孔容積（ΣＰＶ１００－２６０）と、酸化物１に酸化物２を担持して形成した触媒層における所定細孔径範囲の細孔容積（σＰＶ１００－２６０）とを対比すればよく、その増加率（ΔΣＰＶ１００－２６０）が１以上であれば、高ＳＶ時におけるＨＣ（炭化水素）酸化性能が向上する。
　即ち、高ＳＶ時の触媒層でのガス拡散性が向上することにより、ＨＣ酸化性能の保持率が向上する。
　また、このことは、酸化物１に酸化物２を担持する場合に、酸化物１の細孔径１００～２６０ｎｍの細孔に対応した細孔容積を低減せずに酸化物２を担持できることを意味する。
　なお、（１）式における０．１１とは、酸化物１が取りうる上記細孔径範囲の細孔容積の基準値として定義した値である。
　次に、本発明の排気ガス浄化触媒の製造方法について説明する。
（４）この製造方法は、上述のした本発明の排気ガス浄化触媒を製造する方法であるが、酸化物１を焼成する前に酸化物２の前駆体を酸化物１に混合し、次いで、この混合物を焼成する。
　このように、本発明の製造方法では、酸化物１を焼成する前に酸化物２の成分を添加し、細孔を形成する。酸化物１を形成（焼成）してから酸化物２を担持すると、酸化物１の細孔を酸化物２が埋めてしまうことがあり好ましくない。
　酸化物２の前駆体としては、ランタン（Ｌａ）、バリウム（Ｂａ）、ストロンチウム（Ｓｒ）、カルシウム（Ｃａ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）から成る群より選ばれた少なくとも１種の元素のカルボン酸塩を例示できる。
　これらのカルボン酸塩の溶液は、ある程度の粘性があり、酸化物１に含浸させ易い。
　なお、カルボン酸としては、１～４個のカルボキシル基を有するもの、例えば、グルコン酸、リンゴ酸、マレイン酸、酢酸、コハク酸、フマル酸、プロピオン酸、メタクリル酸、アクリル酸、クエン酸、酒石酸、イタコン酸、蟻酸及びマロン酸などを挙げることができる。
　以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。
（実施例１～３）
　表１に示す酸化物２のカルボン酸塩を調製し、酸化物１の前駆体と混合、乾燥し、更に７００℃で焼成して得られた粉末をスラリ化し、モノリス型ハニカム担体にコートして乾燥し、４００℃で焼成することにより、各例の排気ガス浄化触媒を得た。
（比較例１及び２）
　比較例１については、表１に示す酸化物１の前駆体を乾燥し、更に７００℃で焼成して得られた粉末に、酸化物２のカルボン酸塩を含浸し、乾燥、７００℃で焼成して粉末を得た。得られた粉末を触媒スラリ化し、モノリス型ハニカム担体にコートして乾燥し、４００℃で焼成することにより、排気ガス浄化触媒を得た。
　また、比較例２については、表１に示す酸化物１の前駆体を乾燥し、更に７００℃で焼成して得られた粉末を触媒スラリ化し、ハニカム担体にコートして乾燥し、４００℃で焼成することにより、排気ガス浄化触媒を得た。
　酸化物１と酸化物２の配合比、酸化物１、２の組成、ハニカム担体の仕様、ＨＣ浄化試験条件などを表１にまとめて示す。
＜性能評価＞
［全細孔容積］
　窒素吸着法で測定した１～２６０ｎｍ径の細孔容積の総和である。
　粉末に加熱、減圧等を行って吸着ガスを取り除き、冷却した状態で窒素導入と、窒素が材料表面に吸着し相対圧となったときの吸着量より全細孔容積を計算した。
［１００－２６０ｎｍ径の細孔容積の総和］
　上記で測定した全細孔容積のうち、１００ｎｍ～２６０ｎｍ以下の細孔径を持つ細孔容積の総和である。
［１００－２６０ｎｍ径の細孔容積の総和の増加率］
　１００～２６０ｎｍ径の細孔容積の基準値（実際には酸化物１の平均値）を０．１１と定義し、本発明により作成した触媒の１００～２６０ｎｍ径の細孔容積の総和（ΣＰＶ１００－２６０）をこれで割った値が１以上であれば、ΣＰＶ１００－２６０が増加していることを表す値である。
［性能保持率］
　次式にしたがって算出した。
　性能保持率（％）＝［ＳＶが３０２５２ｈ－１時のＨＣ浄化性能］÷［ＳＶが２０１６８ｈ－１時のＨＣ浄化性能］×１００
Figure JPOXMLDOC01-appb-T000001
　表１に示したＨＣ性能保持率を、全細孔容積、１００－２６０ｎｍ径細孔容積の増加率の別で図１及び図２にグラフ化して示す。
　以上、本発明を若干の実施形態及び実施例によって説明したが、本発明はこれらに限定されるものではなく、本発明の要旨の範囲内で種々の変形が可能である。

Claims (9)

  1. 　酸化物１と酸化物２を含有する排気ガス浄化触媒において、
    　窒素吸着法で測定できる１ｎｍ～２６０ｎｍの細孔径を持つ細孔Ｐ１－２６０を有し、
    　この細孔の細孔容積ＰＶ１－２６０の総和ΣＰＶ１－２６０が０．７９ｃｍ３／ｇ以上であることを特徴とする排気ガス浄化触媒。
  2. 　上記排気ガス浄化触媒が酸化物１に酸化物２を担持して得られたものであり。
    　上記担持による１００～２６０ｎｍの細孔径を持つ細孔の細孔容積総和の増加率ΔΣＰＶ１００－２６０がΔΣＰＶ１００－２６０≧１を満足し、この細孔容積総和の増加率ΔΣＰＶ１００－２６０が、次式（１）
    　ΔΣＰＶ１００－２６０＝（担持後の排気ガス浄化触媒における細孔容積の総和σＰＶ１００－２６０）÷０．１１…（１）
    　で表されることを特徴とする請求項１に記載の排気ガス浄化触媒。
  3. 　酸化物１が酸素放出能を有する酸化物であることを特徴とする請求項１又は２に記載の排気ガス浄化触媒。
  4. 　酸化物１がセリウム（Ｃｅ）及び／又はジルコニウム（Ｚｒ）を含有することを特徴とする請求項３に記載の排気ガス浄化触媒。
  5. 　酸化物１がセリウム（Ｃｅ）及び／又はジルコニウム（Ｚｒ）を含有する複合酸化物であることを特徴とする請求項３に記載の排気ガス浄化触媒。
  6. 　酸化物２がランタン（Ｌａ）、バリウム（Ｂａ）、ストロンチウム（Ｓｒ）、カルシウム（Ｃａ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）から成る群より選ばれた少なくとも１種の元素を含有することを特徴とする請求項１～５のいずれか１つの項に記載の排気ガス浄化触媒。
  7. 　酸化物２が、次の一般式（２）
    　ＬａｘＭ１－ｘＭ’Ｏ３－δ…（２）
    （式中のＭはＢａ、Ｓｒ及びＣａから成る群より選ばれた少なくとも１種の元素、Ｍ’はＦｅ、Ｃｏ、Ｎｉ及びＭｎから成る群より選ばれた少なくとも１種の元素、δは酸素欠損量を示し、ｘは０≦ｘ≦１、δは０≦δ≦１の関係を満足する。）で表されることを特徴とする請求項６に記載の排気ガス浄化触媒。
  8. 　請求項１～７のいずれか１つの項に記載の排気ガス浄化触媒を製造するに当たり、
    　酸化物１を焼成する前に酸化物２の前駆体を酸化物１に混合し、次いで、この混合物を焼成することを特徴とする排気ガス浄化触媒の製造方法。
  9. 　上記酸化物２の前駆体が、ランタン（Ｌａ）、バリウム（Ｂａ）、ストロンチウム（Ｓｒ）、カルシウム（Ｃａ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）から成る群より選ばれた少なくとも１種の元素のカルボン酸塩であることを特徴とする請求項８に記載の排気ガス浄化触媒の製造方法。
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