WO2016158656A1 - Catalyseur de purification de gaz d'échappement - Google Patents

Catalyseur de purification de gaz d'échappement Download PDF

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WO2016158656A1
WO2016158656A1 PCT/JP2016/059353 JP2016059353W WO2016158656A1 WO 2016158656 A1 WO2016158656 A1 WO 2016158656A1 JP 2016059353 W JP2016059353 W JP 2016059353W WO 2016158656 A1 WO2016158656 A1 WO 2016158656A1
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ceria
composite oxide
zirconia composite
rare earth
earth element
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PCT/JP2016/059353
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English (en)
Japanese (ja)
Inventor
鈴木　宏昌
吉田　健
真秀 三浦
悠生 青木
勇夫 鎮西
森川　彰
田辺　稔貴
須田　明彦
佳恵 小西
佑樹 田中
浩隆 小里
達也 大橋
千葉　明哉
光祐 飯塚
Original Assignee
トヨタ自動車株式会社
株式会社キャタラー
鈴木　宏昌
吉田　健
真秀 三浦
悠生 青木
勇夫 鎮西
森川　彰
田辺　稔貴
須田　明彦
佳恵 小西
佑樹 田中
浩隆 小里
達也 大橋
千葉　明哉
光祐 飯塚
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Application filed by トヨタ自動車株式会社, 株式会社キャタラー, 鈴木　宏昌, 吉田　健, 真秀 三浦, 悠生 青木, 勇夫 鎮西, 森川　彰, 田辺　稔貴, 須田　明彦, 佳恵 小西, 佑樹 田中, 浩隆 小里, 達也 大橋, 千葉　明哉, 光祐 飯塚 filed Critical トヨタ自動車株式会社
Publication of WO2016158656A1 publication Critical patent/WO2016158656A1/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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an exhaust gas purification catalyst.
  • Automobile exhaust gas purification catalysts oxidize hydrocarbons (HC) and carbon monoxide (CO) contained in exhaust gas discharged from engines to reduce nitrogen oxides (NOx) to water and carbon dioxide. To nitrogen.
  • an exhaust gas purifying catalyst having such catalytic activity usually particles of catalytic noble metals such as palladium (Pd), rhodium (Rh) and platinum (Pt) are used.
  • Pd palladium
  • Rh rhodium
  • platinum platinum
  • the catalyst layer of the noble metal-supported catalyst usually contains, in addition to the catalyst noble metal particles as described above, an OSC material having an oxygen storage capacity (hereinafter also referred to as “OSC”) as a support or a promoter.
  • OSC oxygen storage capacity
  • the OSC material supports the exhaust gas purification reaction by catalytic noble metals by occluding and releasing oxygen.
  • ceria-zirconia composite oxide (CeO 2 —ZrO 2 ) is widely used.
  • the catalyst layer of the exhaust gas purifying catalyst is usually configured such that a plurality of catalyst layers are laminated on a substrate (hereinafter referred to as “layered” for the purpose of avoiding a decrease in catalyst activity due to components such as sulfur in the exhaust gas. Also referred to as “catalyst”).
  • Patent Document 1 discloses that a first oxygen storage / release material having no pyrometal phase-supported ordered arrangement structure in which noble metal is supported and an oxygen storage / release rate higher than that of the first oxygen storage / release material.
  • An exhaust gas purification catalyst comprising a second oxygen storage / release material having a low capacity for absorption / release and having a platinum group noble metal supported on the second oxygen storage / release material is described.
  • Patent Document 2 discloses a first catalyst layer on which rhodium is supported on a support base material, platinum and palladium are supported, and the ratio of the supported amount of palladium (y) to the supported amount of platinum (x).
  • a NOx occlusion reduction type exhaust gas purifying catalyst having a second catalyst layer satisfying (y / x; molar ratio) satisfying 0 ⁇ y / x ⁇ 1.0 in order from the supporting base material side will be described.
  • Patent Document 3 discloses a support substrate, and at least one of NOx occlusion material selected from an alkali metal, an alkaline earth metal, and a rare earth element, platinum and palladium formed on the surface of the support substrate. And a catalyst coating layer that supports rhodium, and the NOx storage material stores NOx in a lean atmosphere in which the exhaust gas atmosphere is excessive in oxygen, and the exhaust gas atmosphere is changed from a stoichiometric to a rich atmosphere in which reducing components are excessive.
  • a NOx occlusion reduction type exhaust gas purification catalyst that releases and reduces NOx occluded in the NOx occlusion material, the catalyst coat layer comprising: a lower layer formed on the surface of the carrier substrate; And an upper layer formed on the surface, and at least one of platinum and palladium is supported on at least the upper layer, and rhodium is based on the total supported amount of rhodium in the catalyst coat layer.
  • An exhaust gas purifying catalyst is described in which an amount of 40% by mass or less is supported on the upper layer and an amount of 60% by mass or more is supported on the lower layer.
  • layered catalysts used for exhaust gas purification catalysts are known.
  • the conventional layered catalyst there are some problems.
  • a layered catalyst it is usually brought into contact with exhaust gas on the surface of the uppermost catalyst layer.
  • Each component contained in the exhaust gas enters the lower catalyst layer from the surface of the uppermost catalyst layer and undergoes an oxidation or reduction reaction in each catalyst layer.
  • the temperature of the exhaust gas gradually decreases.
  • the material used for the lower catalyst layer needs to exhibit sufficient performance even in a low temperature range.
  • the exhaust gas purification catalyst is applied to an automobile exhaust gas purification catalyst system, it is exposed to a high temperature environment for a long period of time. For this reason, it is necessary to maintain the catalyst performance even after use at a high temperature for a long time.
  • an object of the present invention is to provide means for maintaining catalyst performance even after long-term use in an exhaust gas purification catalyst.
  • the present inventors have determined that a pyrochlore containing at least one rare earth element as the OSC material of the lower catalyst layer in the exhaust gas purification catalyst having a two-layer structure.
  • a ceria-zirconia composite oxide having a phase structure By adding a ceria-zirconia composite oxide having a phase structure, sufficient oxygen storage capacity is exhibited even in the lower catalyst layer, which is lower in temperature than the upper catalyst layer, and the catalyst performance can be maintained even after long-term use. As a result, the present invention has been completed.
  • the gist of the present invention is as follows. (1) Consists of upper and lower layers,
  • the upper layer has a support containing an alumina-added ceria-zirconia composite oxide, rhodium supported on the support, and lanthanum-added alumina.
  • the lower layer comprises a carrier containing lanthanum-added alumina, palladium supported on the carrier, a ceria-zirconia composite oxide containing at least one rare earth element, a further ceria-zirconia composite oxide, barium sulfate,
  • the ceria-zirconia composite oxide containing at least one rare earth element is in the form of primary particles having an average particle size in the range of 2.2 to 4.5 ⁇ m
  • the ceria-zirconia composite oxide containing at least one rare earth element contains at least one rare earth element selected from the group consisting of lanthanum, yttrium, and praseodymium, and contains cerium and zirconium in the ceria-zirconia composite oxide.
  • the ceria-zirconia composite oxide containing at least one rare earth element contains 90 atomic% or more of the total amount of the at least one rare earth element in the vicinity of the surface within 50 nm from the surface of the primary particles.
  • the content of the ceria-zirconia composite oxide containing at least one rare earth element is in the range of 7 to 25 parts by mass with respect to 100 parts by mass of the lower layer lanthanum-added alumina support.
  • the exhaust gas purifying catalyst as described in 1).
  • the substrate further includes a base material on which the upper layer and the lower layer are arranged, and the upper layer is at least 60% from the end of the base material on the exhaust gas outflow side with respect to the entire length of the base material.
  • the lower layer is disposed over a position of at least 60% from the end of the base material on the exhaust gas inflow side with respect to the total length of the base material, (1) Or the exhaust gas purifying catalyst as described in (2).
  • FIG. 1 is a schematic diagram showing the configuration of an embodiment of the exhaust gas purifying catalyst of the present invention.
  • FIG. 2 is a diagram showing the results of EDX analysis of primary particles of La-containing ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the rare earth element-containing ceria-zirconia composite oxide of Preparation Example 2.
  • FIG. 3 is a diagram showing the result of HR-TEM observation of primary particles of La-containing ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the rare earth element-containing ceria-zirconia composite oxide of Preparation Example 2. It is.
  • FIG. 1 is a schematic diagram showing the configuration of an embodiment of the exhaust gas purifying catalyst of the present invention.
  • FIG. 2 is a diagram showing the results of EDX analysis of primary particles of La-containing ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the rare earth element-containing ceria-zir
  • FIG. 4 is a diagram showing the results of EDX analysis of primary particles of La-containing ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the rare earth element-containing ceria-zirconia composite oxide of Preparation Example 5.
  • FIG. 5 is a diagram showing the result of HR-TEM observation of primary particles of La-containing ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the rare earth element-containing ceria-zirconia composite oxide of Preparation Example 5. It is.
  • FIG. 6 is a diagram showing the results of EDX analysis of primary particles of La-containing ceria-zirconia composite oxide after endurance test 1 (1100 ° C.
  • FIG. 7 is a diagram showing the results of HR-TEM observation of primary particles of La-containing ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the rare earth element-containing ceria-zirconia composite oxide of Preparation Example 7. It is.
  • FIG. 8 is a diagram showing the results of EDX analysis of primary particles of ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the ceria-zirconia composite oxide of Preparation Comparative Example 1.
  • FIG. 8 is a diagram showing the results of EDX analysis of primary particles of ceria-zirconia composite oxide after endurance test 1 (1100 ° C. air) for the ceria-zirconia composite oxide of Preparation Comparative Example 1.
  • FIG. 9 is a diagram showing the results of HR-TEM observation of the primary particles of the ceria-zirconia composite oxide after the durability test 1 (1100 ° C. air) for the ceria-zirconia composite oxide of Preparation Comparative Example 1.
  • FIG. 10 shows the addition of ceria-zirconia composite oxide containing at least one rare earth element to the lower catalyst layer in the heat durability treatment test of the catalysts of Comparative Example 1, Examples 1 to 3 and Reference Examples 1 to 3. It is a graph which shows the relationship between the amount and NOx emission at the time of air-fuel ratio (A / F) switching.
  • FIG. 10 shows the addition of ceria-zirconia composite oxide containing at least one rare earth element to the lower catalyst layer in the heat durability treatment test of the catalysts of Comparative Example 1, Examples 1 to 3 and Reference Examples 1 to 3. It is a graph which shows the relationship between the amount and NOx emission at the time of air-fuel ratio (A / F) switching.
  • FIG. 11 shows the amount of ceria-zirconia composite oxide containing at least one rare earth element added to the lower catalyst layer and the steady rich NOx in the heat durability treatment test of the catalysts of Comparative Example 1 and Examples 1 to 3. It is a graph which shows the relationship with a purification rate.
  • FIG. 12 shows the addition of ceria-zirconia composite oxide containing at least one rare earth element to the lower catalyst layer in the heat endurance treatment test of the catalysts of Comparative Example 1, Examples 4 to 6 and Reference Examples 1 to 3. It is a graph which shows the relationship between the amount and NOx emission at the time of air-fuel ratio (A / F) switching.
  • FIG. 1 is a schematic diagram showing the configuration of an embodiment of the exhaust gas purifying catalyst of the present invention.
  • the exhaust gas purifying catalyst 1 of the present invention needs to be composed of an upper layer 11 and a lower layer 12.
  • the upper layer 11 and the lower layer 12 may be collectively referred to as “two-layer catalyst layer 13” or simply “catalyst layer 13”.
  • the exhaust gas purifying catalyst 1 of the present invention can further include a base material 14.
  • the catalyst layer 13 composed of the upper layer 11 and the lower layer 12 is usually disposed on the surface of the substrate 14.
  • the exhaust gas purifying catalyst 1 of the present invention has a base material 14, a lower layer 12 disposed on the surface of the base material 14, and an upper layer 11 disposed on the surface of the lower layer 12.
  • the upper layer needs to have a support containing alumina-added ceria-zirconia composite oxide (CeO 2 —ZrO 2 ).
  • ceria-zirconia composite oxide means a composite oxide containing ceria (CeO 2 ) and zirconia (ZrO 2 ).
  • the alumina-added ceria-zirconia composite oxide is used as a support for a noble metal catalyst and as an OSC material having an upper layer oxygen storage capacity (OSC).
  • OSC upper layer oxygen storage capacity
  • the alumina-added ceria-zirconia composite oxide preferably contains 20 to 60% by mass of CeO 2 and 30 to 70% by mass of ZrO 2 with respect to the total mass of the composite oxide.
  • the mass ratio of CeO 2 and ZrO 2 is preferably in the range of 1: 0.5 to 1: 3.5, and more preferably in the range of 1: 0.5 to 1: 1.
  • the content of alumina is preferably in the range of 10 to 50% by mass, and in the range of 20 to 50% by mass with respect to the total mass of the composite oxide. Is more preferable, and the range of 30 to 50% by mass is even more preferable.
  • the alumina-added ceria-zirconia composite oxide is preferably contained in the range of 20 to 80% by mass, more preferably in the range of 50 to 70% by mass with respect to the total mass of the upper layer. .
  • the oxygen storage capacity of the exhaust gas purifying catalyst of the present invention can be improved.
  • the upper layer needs to have rhodium (Rh) as a noble metal catalyst supported on a support containing an alumina-added ceria-zirconia composite oxide.
  • Rh is preferably contained in the range of 0.03 to 0.5 parts by mass and preferably in the range of 0.07 to 0.35 parts by mass with respect to the support containing 100 parts by mass of the alumina-added ceria-zirconia composite oxide. Is more preferable.
  • Rh is preferably contained in the above amount, a high exhaust gas purification ability can be exhibited.
  • the upper layer needs to have lanthanum-added alumina (La—Al 2 O 3 ).
  • Lanthanum-added alumina is used as the upper layer OSC material.
  • the lanthanum-added alumina is preferably contained in the range of 20 to 150 parts by weight, and preferably in the range of 30 to 100 parts by weight with respect to the support containing 100 parts by weight of the alumina-added ceria-zirconia composite oxide. More preferably.
  • the lanthanum-added alumina preferably contains 0.5 to 10% by mass of La with respect to the total mass of the lanthanum-added alumina.
  • each material in the upper layer is not limited, for example, after dissolving the upper layer using an acid or the like, a method for inductively coupled plasma (ICP) emission analysis of the components in the obtained solution Can be determined by.
  • ICP inductively coupled plasma
  • the lower layer needs to have a carrier containing lanthanum-added alumina.
  • Lanthanum-added alumina is used as a support for the noble metal catalyst and as the underlying OSC material.
  • the lanthanum-added alumina is preferably contained in the range of 20 to 50% by mass, more preferably in the range of 30 to 50% by mass with respect to the total mass of the lower layer.
  • the lanthanum-added alumina preferably contains 0.5 to 10% by mass of La with respect to the total mass of the lanthanum-added alumina.
  • the lower layer needs to have palladium (Pd) as a noble metal catalyst supported on a support containing lanthanum-added alumina.
  • Pd is preferably contained in the range of 0.2 to 5 parts by mass, and more preferably in the range of 0.4 to 3 parts by mass with respect to the support containing 100 parts by mass of the lanthanum-added alumina.
  • the lower layer needs to have a ceria-zirconia composite oxide containing at least one rare earth element.
  • the ceria-zirconia composite oxide containing at least one rare earth element has the following characteristics: (I) The ceria-zirconia composite oxide containing at least one rare earth element is in the form of primary particles having an average particle size in the range of 2.2 to 4.5 ⁇ m, (Ii) The ceria-zirconia composite oxide containing at least one rare earth element contains at least one rare earth element selected from the group consisting of lanthanum (La), yttrium (Y), and praseodymium (Pr), 0.1 to 4.0 atomic percent of the total amount of cerium (Ce) and zirconium (Zr) in the ceria-zirconia composite oxide, (Iii) The ceria-zirconia composite oxide containing at least one rare earth element has a 90 atom number of the total amount of the at least one rare earth element.
  • the content ratio of Ce and Zr in the ceria-zirconia composite oxide containing at least one rare earth element is a molar ratio in the range of 43:57 to 48:52
  • the at least 2 ⁇ obtained from an X-ray diffraction pattern using CuK ⁇ obtained by X-ray diffraction measurement after heating a ceria-zirconia composite oxide containing one kind of rare earth element in the atmosphere at a temperature of 1100 ° C. for 5 hours.
  • a ceria-zirconia composite oxide containing at least one rare earth element satisfying the above characteristics is a novel material recently discovered by the present inventors (Japanese Patent Laid-Open No. 2015-71520). This material has a sufficiently excellent oxygen storage capacity in a low temperature region and a sufficiently high heat resistance.
  • the temperature of the lower layer during operation is lower than the temperature of the upper layer. Therefore, by containing this material in the lower layer, a sufficient oxygen storage capacity can be expressed even in the lower catalyst layer that is at a lower temperature than the upper catalyst layer. In addition, even after being used under high temperature conditions for a long time, high exhaust gas purification ability can be exhibited.
  • the “I (14/29) value” and the “I (28/29) value” each represent a ceria-zirconia composite oxide containing at least one rare earth element at 1100 ° C. in the atmosphere.
  • the I (14/29) value which is the intensity ratio between the two diffraction lines, is defined as an index indicating the maintenance ratio (presence ratio) of the ordered phase in the ceria-zirconia composite oxide.
  • the average diffraction line intensity of 2 ⁇ 10 ° to 12 ° is subtracted as a background value from the actually measured value of each diffraction line intensity.
  • the completely ordered phase includes a ⁇ phase (Ce 2 Zr 2 O 8 ) completely filled with oxygen and a pyrochlore phase (Ce 2 Zr 2 O 7 ) from which oxygen is completely desorbed. And exist.
  • the PDF card for the ⁇ phase is PDF2: 01-070-4048
  • the PDF card for the pyrochlore phase is PDF2: 01-075-2694.
  • the I (14/29) value of the ⁇ phase calculated from each PDF card is 0.04, and the I (14/29) value of the pyrochlore phase is 0.05.
  • the ordered phase that is, the crystalline phase having an ordered arrangement structure formed by Ce ions and Zr ions, has a 2 ⁇ angle of 14.5 ° determined from an X-ray diffraction pattern using CuK ⁇ obtained by the X-ray diffraction measurement. , 28 °, 37 °, 44.5 °, and 51 °, respectively.
  • Crystal arrangement structure ( ⁇ 'phase (same phase as ⁇ phase) type ordered arrangement phase: superlattice formed in fluorite structure Structure).
  • the “peak” of the X-ray diffraction pattern means that the height from the baseline to the peak top is 30 cps or more.
  • the reason why the ceria-zirconia composite oxide containing at least one rare earth element satisfying the characteristics (i) to (v) has the above-described characteristics is as follows. Can be explained. Note that the present invention is not limited to the following actions and principles.
  • the pyrochlore phase structure of CeO 2 -ZrO 2 (Ce 2 Zr 2 O 7 ) in the ceria-zirconia composite oxide undergoes phase conversion with the ⁇ phase according to the partial pressure of oxygen in the gas phase, and oxygen storage capacity Is expressed.
  • Ceria-zirconia composite oxide with pyrochlore phase structure is effective in improving NOx purification performance at the time of A / F switching where the air-fuel ratio (A / F) is switched from rich to lean because the oxygen release rate is slow It was thought that.
  • the Ce 2 Zr 2 O 7 type pyrochlore phase structure is a metastable phase
  • the ceria-zirconia composite oxide having the Ce 2 Zr 2 O 7 type pyrochlore phase structure is exposed to a high-temperature oxidizing atmosphere. There was a problem that the structure returned from the surface of the primary particle to the fluorite structure and the oxygen storage capacity was lowered.
  • At least one kind of rare earth element (RE) selected from the group consisting of La, Y and Pr ) And Zr ions can form a RE 2 Zr 2 O 7 type pyrochlore phase structure.
  • RE rare earth element
  • a crystal phase having an ordered arrangement structure can be formed. Since the RE 2 Zr 2 O 7 type pyrochlore phase structure is a stable phase, it has better heat resistance than the Ce 2 Zr 2 O 7 type pyrochlore phase structure.
  • the at least one rare earth element is localized in the region near the surface of the primary particle (feature (iii)).
  • the ordered phase consisting of the 2 Zr 2 O 7 type pyrochlore phase structure is also localized in the region near the surface of the primary particle.
  • the exhaust gas purifying catalyst of the present invention can be switched between A / F even after it has been used for a long period of time by containing the material satisfying the characteristics (i) to (v) in the lower layer. NOx emissions at the time can be greatly reduced, and high exhaust gas purification capability can be demonstrated.
  • the ceria-zirconia composite oxide containing at least one rare earth element must have an I (14/29) value of 0.02 or more, It is preferable that it is 0.033 or more.
  • the I (14/29) value is less than the lower limit, the maintenance rate of the ordered phase is low, and the oxygen storage capacity after exposure to a high temperature environment may be insufficient.
  • the upper limit of the I (14/29) value is not particularly limited, but the I (14/29) value of the pyrochlore phase determined based on the PDF card of the pyrochlore phase (PDF2: 01-075-2694) is 0.05 Therefore, the I (14/29) value is preferably 0.05 or less.
  • the ceria-zirconia composite oxide containing at least one rare earth element must have an I (28/29) value of 0.08 or less, and 0.06 or less. It is preferable that it is 0.04 or less.
  • I (28/29) value exceeds the upper limit, the phase separation of ceria is not sufficiently suppressed, and the oxygen storage capacity after exposure to a high temperature environment may be insufficient.
  • the lower limit value of the I (28/29) value is not particularly limited, and is preferably a smaller value.
  • the ceria-zirconia composite oxide containing at least one rare earth element contains the ordered phase (Ce) relative to the total crystalline phase determined from the peak intensity ratio of the X-ray diffraction pattern.
  • 2 Zr 2 O 7 type pyrochlore phase and RE 2 Zr 2 O 7 type pyrochlore phase is preferably 50 to 100%, more preferably 80 to 100%.
  • the content ratio of the ordered phase is less than the lower limit, the effect of suppressing deterioration of the oxygen storage capacity and the heat resistance effect of the material may be reduced.
  • the content ratio of the RE 2 Zr 2 O 7 type pyrochlore phase in the ordered phase is preferably in the range of 0.1 to 8.0%, and more preferably in the range of 0.8 to 5.0%.
  • the content ratio of the RE 2 Zr 2 O 7 type pyrochlore phase is less than the lower limit value, the oxygen storage capacity deterioration suppressing effect and heat resistance effect of this material may be reduced.
  • the content ratio of the RE 2 Zr 2 O 7 type pyrochlore phase exceeds the upper limit, the oxygen storage capacity may be lowered.
  • the ceria-zirconia composite oxide containing at least one rare earth element contains at least one rare earth element selected from the group consisting of La, Y and Pr. -It is necessary to contain 0.1 to 4.0 atomic%, and preferably 0.25 to 2.5 atomic%, based on the total amount of Ce and Zr in the zirconia composite oxide.
  • the at least one rare earth element the rare earth elements included in the group may be used alone, or two or more rare earth elements may be used in combination. When two or more rare earth elements are used in combination, the primary particles of the ceria-zirconia composite oxide containing at least one rare earth element are different from each other in the vicinity of the surface and other areas.
  • the at least one rare earth element is preferably Pr or La.
  • the I (14/29) value and oxygen storage capacity after exposure to a high temperature environment may be reduced.
  • the effect of this material is sufficient to have a sufficiently excellent oxygen storage capacity in a low temperature range and a sufficiently high heat resistance and to exhibit an excellent oxygen storage capacity even after being exposed to a high temperature environment. It may not be obtained.
  • the content of the at least one rare earth element exceeds the upper limit, the I (14/29) value and oxygen storage capacity after exposure to a high temperature environment may be reduced.
  • the exhaust gas purifying catalyst of the present invention can be used even after being used under a high temperature condition for a long time. NOx emissions during A / F switching can be greatly reduced, and high exhaust gas purification capability can be demonstrated.
  • the ceria-zirconia composite oxide containing at least one kind of rare earth element at least one kind of rare earth element is usually present in a solid solution or dispersed state with respect to the ceria-zirconia composite oxide. .
  • the ceria-zirconia composite oxide containing at least one rare earth element is a group consisting of a further rare earth element and an alkaline earth element in addition to the at least one rare earth element. It may contain at least one further element selected from more. By containing such additional elements, the exhaust gas purification ability of the exhaust gas purification catalyst of the present invention can be further improved.
  • the further rare earth elements include scandium (Sc), neodymium (Nd), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy) ytterbium (Yb), and lutetium (Lu). be able to.
  • the alkaline earth element include magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
  • the content of the at least one further element is the total of the ceria-zirconia composite oxide.
  • the range is preferably 1 to 20% by mass, more preferably 3 to 7% by mass, based on the mass.
  • the exhaust gas purifying catalyst of the present invention can exhibit high exhaust gas purifying ability by containing the present material containing at least one additional element in the above content in the lower layer.
  • the content and content ratio of the at least one rare earth element and / or at least one further element may be, for example, energy dispersive X-rays It can be determined by performing composition analysis using an analytical instrument such as a detector (EDX) or a secondary ion mass spectrometer (SIMS). Alternatively, it may be determined by eluting at least one rare earth element and / or at least one further element using an acid or the like.
  • an analytical instrument such as a detector (EDX) or a secondary ion mass spectrometer (SIMS).
  • a ceria-zirconia composite oxide containing at least one rare earth element and / or at least one further element is brought into contact with an acidic solution such as an aqueous nitric acid solution to elute the element.
  • an acidic solution such as an aqueous nitric acid solution
  • the elemental component in the obtained solution is quantified by chemical analysis such as ICP emission analysis to determine the content and content ratio of at least one rare earth element and / or at least one further element. it can.
  • the ceria-zirconia composite oxide containing at least one rare earth element is usually present in the form of primary particles.
  • the average particle size of the primary particles needs to be in the range of 2.2 to 4.5 ⁇ m, preferably in the range of 2.5 to 4.5 ⁇ m, and more preferably in the range of 2.5 to 4.0 ⁇ m. If the average particle diameter of the primary particles of the ceria-zirconia composite oxide containing at least one rare earth element is less than the lower limit, the heat resistance of the pyrochlore phase structure of CeO 2 —ZrO 2 may be reduced.
  • the exhaust gas purifying catalyst of the present invention contains A / F even after being used under a high temperature condition for a long period of time by containing the material having the average particle diameter of the primary particles in the lower layer in the lower layer.
  • the NOx emission amount at the time of switching can be greatly reduced, and a high exhaust gas purification ability can be exhibited.
  • the average particle diameter of the primary particles of the ceria-zirconia composite oxide containing at least one kind of rare earth element is, for example, a predetermined number (for example, 50) by observing the primary particles with a scanning electron microscope (SEM). It can be determined by measuring the particle diameter of any of the primary particles and calculating the average value of the measured values. For example, when the cross section of the primary particle is not a perfect circle, the minimum circumscribed circle of the primary particle is assumed, and the diameter may be regarded as the particle diameter to perform the measurement.
  • the specific surface area of the primary particles of the ceria-zirconia composite oxide containing at least one rare earth element is preferably in the range of 0.01 to 20 m 2 / g, A range of 0.05 to 10 m 2 / g is more preferable.
  • the specific surface area is less than the lower limit, the oxygen storage capacity may be reduced.
  • the specific surface area exceeds the upper limit, primary particles having a small particle diameter may increase and heat resistance may decrease.
  • the exhaust gas purification catalyst of the present invention has a high exhaust gas purification even after being used under a high temperature condition for a long period of time by containing the material having the specific surface area of the primary particles in the above range in the lower layer. Can demonstrate ability.
  • the specific surface area of the primary particles of the ceria-zirconia composite oxide containing at least one rare earth element can be determined, for example, as the BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.
  • the ceria-zirconia composite oxide containing at least one rare earth element has the at least one rare earth in a region near the surface within 50 ⁇ m from the surface of the primary particles. It is necessary to contain 90 atomic% or more of the total amount of elements, and 80 atomic% or more of the total amount of the at least one rare earth element in the vicinity of the surface within 30 ⁇ m from the surface of the primary particles. It is preferable to contain. If the distribution of the at least one rare earth element does not satisfy the above conditions, a sufficient structure stabilization effect may not be obtained.
  • the dispersion form of the at least one rare earth element is not particularly limited.
  • substantially all of the primary particles of the ceria-zirconia composite oxide containing at least one rare earth element contain at least one rare earth element in a distribution satisfying the above conditions.
  • primary particles that do not satisfy the above conditions may be mixed in a group of ceria-zirconia composite oxide particles containing at least one rare earth element as long as the effect of the present material is not impaired.
  • the content and content ratio of the at least one rare earth element present in the region near the surface of the primary particles can be analyzed by, for example, EDX or SIMS It can be determined by performing composition analysis using an instrument and comparing the content and content ratio of at least one rare earth element between the region near the surface of the primary particle and the other region. Alternatively, it may be determined by eluting at least one rare earth element using an acid or the like.
  • primary particles of ceria-zirconia composite oxide containing at least one rare earth element are brought into contact with an acidic solution such as an aqueous nitric acid solution to elute the rare earth elements from the primary particles. Thereafter, the metal component in the obtained solution is quantified by chemical analysis such as ICP emission analysis to determine the content and content ratio of at least one rare earth element present in the region near the surface of the primary particles. it can.
  • the ceria-zirconia composite oxide containing at least one rare earth element is a combination of Ce and Zr in the ceria-zirconia composite oxide containing at least one rare earth element.
  • the content ratio needs to be a molar ratio in the range of 43:57 to 48:52, and is preferably a molar ratio in the range of 44:56 to 48:52.
  • the content ratio of Ce is less than the lower limit, the effect of lowering the oxygen storage capacity by becoming a Zr-rich composition exceeds the stability improvement effect of the composite oxide by suppressing the phase separation of ceria, Oxygen storage capacity after exposure to high temperature environment may be insufficient.
  • the exhaust gas purifying catalyst of the present invention can be used even if the exhaust gas purifying catalyst of the present invention is used under a high temperature condition for a long period of time by including the material in which the content ratio of Ce and Zr is in the above range in the lower layer. NOx emissions during F switching can be greatly reduced, and high exhaust gas purification capability can be demonstrated.
  • the ceria-zirconia composite oxide containing at least one rare earth element is contained in a range of 7 to 32 parts by mass with respect to 100 parts by mass of the lanthanum-added alumina support.
  • the content is preferably in the range of 7 to 30 parts by mass, and more preferably in the range of 7 to 25 parts by mass.
  • the ceria-zirconia composite oxide containing at least one rare earth element is 14 to 25 parts by mass with respect to 100 parts by mass of the lanthanum-added alumina support. More preferably, it is contained in the range of parts.
  • the ceria-zirconia composite oxide containing at least one rare earth element is 7.7 to 7.8 to 100 parts by mass of the lanthanum-added alumina support. More preferably, it is contained in the range of 14 parts by mass.
  • the ceria-zirconia composite oxide containing at least one rare earth element in the lower layer is 5 to 20 ⁇ g with respect to the capacity of the base material. It is preferably contained in the range of / L base material, and more preferably in the range of 5 to 15 g / L base material.
  • the ceria-zirconia composite oxide containing at least one rare earth element is 7 to 13 g / L substrate relative to the substrate capacity. More preferably, it is contained in the range. Further, for example, in the case where at least one rare earth element is La, the ceria-zirconia composite oxide containing at least one rare earth element is 5 to 7 g / L with respect to the capacity of the substrate. More preferably, it is contained in the range of the substrate. If the content of the ceria-zirconia composite oxide containing at least one rare earth element exceeds the upper limit, the NOx purification rate may decrease when the A / F of the inflowing gas atmosphere is continued in a rich state There is.
  • the exhaust gas purifying catalyst of the present invention is used after being used under a high temperature condition for a long time.
  • NOx emissions when A / F is continued in a rich state can be reduced, and high exhaust gas purification capability can be exhibited.
  • the lower layer needs to have further ceria-zirconia composite oxide.
  • the further ceria-zirconia composite oxide preferably has the same characteristics as the ceria-zirconia composite oxide used as an upper layer material.
  • the further ceria-zirconia composite oxide is preferably contained in the range of 20 to 70% by mass and more preferably in the range of 30 to 50% by mass with respect to the total mass of the lower layer.
  • the lower layer needs to have barium sulfate.
  • barium sulfate is preferably contained in the range of 1 to 15% by mass, more preferably in the range of 2 to 7% by mass with respect to the total mass of the lower layer.
  • each material in the lower layer is not limited.
  • the material component in the obtained solution is determined by a method of ICP emission analysis. Can do.
  • the substrate is preferably in the form of a honeycomb, pellets or particles, and more preferably a monolith substrate in the form of a honeycomb.
  • a base material contains heat resistant inorganic substances, such as a cordierite, or a metal.
  • exhaust gas is allowed to flow from one end side of the exhaust gas purifying catalyst, and exhaust gas is allowed to flow from the other end side.
  • an exhaust gas inflow side may be referred to as an “exhaust gas inflow side”
  • an exhaust gas outflow side may be referred to as an “exhaust gas outflow side”.
  • the exhaust gas flowing in from the exhaust gas inflow side of the exhaust gas purifying catalyst of the present invention is oxidized or reduced in the upper and lower catalyst layers while moving along the upper surface, and the exhaust gas is purified as exhaust gas. It flows out from the outflow side.
  • the upper layer is preferably arranged over a position of at least 60% from the end of the base material on the exhaust gas outflow side with respect to the entire length of the base material, and up to at least 90%. More preferably, it is disposed over a position, and more preferably, it is disposed over a position up to about 100%.
  • the exhaust gas component remaining in the outflowing gas can be efficiently purified.
  • the lower layer is preferably disposed over a position up to at least 60% from the end of the base material on the exhaust gas inflow side with respect to the entire length of the base material. It is more preferable that they are arranged over a position up to about 100%.
  • the exhaust gas purifying catalyst of the present invention includes a ceria-zirconia composite oxide containing at least one rare earth element in the lower layer, and thus after being used under a high temperature condition for a long time.
  • the exhaust gas purifying catalyst of the present invention can be used as an S / C catalyst in an exhaust gas purifying catalyst system comprising a start-up converter (S / C) and a lower body mounted converter (UF / C). preferable.
  • S / C start-up converter
  • UF / C lower body mounted converter
  • the exhaust gas purifying catalyst of the present invention is not limited.
  • the slurry of each material contained in the lower layer is wash-coated on the base material, it is heated and fired to form the lower layer, and the upper layer
  • the slurry of each material contained is wash-coated on a substrate, it can be produced by a method commonly used in the art, such as a method comprising a step of heating and baking to form an upper layer.
  • the slurry of each material of the upper layer and the lower layer can be prepared by, for example, preparing the powder of each material by an impregnation method and then suspending the powder and the binder in water.
  • the ceria-zirconia composite oxide containing at least one rare earth element contained in the lower layer can be produced by the method described below.
  • the method for producing a ceria-zirconia composite oxide containing at least one rare earth element has the following steps: the content ratio of cerium and zirconium is a molar ratio in the range of 43:57 to 48:52, and A ceria-zirconia composite oxide powder preparation step of preparing a ceria-zirconia composite oxide powder in the form of primary particles having an average particle size in the range of 2.2 to 4.5 ⁇ m; the ceria-zirconia composite oxide powder preparation step; The ceria-zirconia composite oxide powder obtained by the above step is loaded with at least one rare earth element selected from the group consisting of La, Y and Pr, and is obtained in the rare earth element loading step.
  • the method for preparing the ceria-zirconia composite oxide powder having the above characteristics is not particularly limited.
  • a solid solution powder containing ceria and zirconia (hereinafter also referred to as “ceria-zirconia-based solid solution powder”) is prepared by a method such as coprecipitation so that the content ratio of Ce and Zr is within the above range.
  • the ceria-zirconia-based solid solution powder is molded and heated under reducing conditions to obtain a ceria-zirconia composite oxide powder having the above characteristics.
  • Examples of coprecipitation methods for producing ceria-zirconia solid solution powder include coprecipitation in the presence of ammonia in an aqueous solution containing a salt of Ce (eg, nitrate) and a salt of Zr (eg, nitrate).
  • a method of obtaining ceria-zirconia solid solution powder by filtering and washing the obtained coprecipitate, drying, further firing, and then grinding the fired product using a pulverizer such as a ball mill.
  • the aqueous solution may optionally contain a salt of at least one further element selected from the group consisting of the further rare earth elements and alkaline earth elements described above.
  • the aqueous solution may also contain a surfactant (for example, a nonionic surfactant) and the like as desired.
  • the ceria-zirconia-based solid solution powder obtained by the above method is preferably a solid solution in which ceria and zirconia are mixed at an atomic level because a regular phase can be sufficiently formed.
  • the ceria-zirconia solid solution powder obtained by the above method preferably has an average primary particle diameter in the range of 2 to 100 nm. When the average particle diameter is less than the lower limit, solid solution of ceria and zirconia in the powder does not proceed sufficiently, and the ordered phase may not be obtained. On the other hand, when the average particle diameter exceeds the upper limit, the contact state of the primary particles at the time of pressure molding is deteriorated, and there is a possibility that the grain growth at the time of the reduction treatment becomes insufficient. Therefore, by obtaining a ceria-zirconia solid solution powder having an average particle diameter in the above range, a ceria-zirconia composite oxide powder having a desired ordered phase can be obtained.
  • the ceria-zirconia solid solution powder obtained by the above method is in the range of 400 to 3500 kgf / cm 2 , preferably 500 to 3000 kgf /
  • a method of pressure molding at a pressure in the range of cm 2 can be mentioned.
  • the pressure during pressure molding is less than the lower limit, the powder packing density is not sufficiently improved, so that crystal growth during the reduction treatment is not sufficiently promoted, and the resulting ceria-zirconia composite oxide has a high temperature. Oxygen storage capacity may be insufficient after exposure to the environment.
  • ceria-zirconia composite oxide powder having a desired ordered phase can be obtained by pressure molding at a pressure in the above range.
  • the heating temperature is less than the lower limit, the stability of the ordered phase is lowered, and the resulting ceria-zirconia composite oxide may have insufficient oxygen storage capacity after being exposed to a high temperature environment.
  • the heating temperature exceeds the upper limit, the balance between energy required for the reduction treatment and performance improvement may be deteriorated.
  • the heating time is less than the lower limit value, the generation of the ordered phase may be insufficient.
  • ceria-zirconia composite oxide powder having a desired ordered phase can be obtained by heat reduction under the above conditions.
  • the heat treatment method under reducing conditions is not particularly limited, and examples thereof include a heat treatment method in a reducing gas atmosphere.
  • the reducing gas e.g., CO
  • HC and H 2 and the like gases can be mentioned.
  • the method for supporting at least one rare earth element on the ceria-zirconia composite oxide powder is not particularly limited, and a known method usually used in the technical field can be appropriately employed.
  • liquid phase methods such as impregnation support method, ion exchange method, water absorption support method, sol-gel method and precipitation support method, solid phase methods such as powder mixing method and solid phase ion exchange method, and gas phase methods such as CVD method.
  • impregnation support method ion exchange method
  • water absorption support method sol-gel method and precipitation support method
  • solid phase methods such as powder mixing method and solid phase ion exchange method
  • gas phase methods such as CVD method.
  • the water absorption of the ceria-zirconia composite oxide powder is measured in advance, and a raw material solution in which a predetermined amount of at least one rare earth element salt, complex, simple substance or oxide is dissolved is ceria-zirconia composite oxidation. It is preferable to use a water absorption support method in which the product powder absorbs water. By such a method, diffusion of the raw material solution into the primary particles is prevented, and the resulting primary particles of ceria-zirconia composite oxide containing at least one rare earth element are within 50 nm from the surface. In the region near the surface, 90 atomic% or more of the total amount of the at least one rare earth element can be contained.
  • the temperature for firing the ceria-zirconia composite oxide powder carrying the rare earth element needs to be in the range of 600 to 1200 ° C., preferably in the range of 800 to 1100 ° C., More preferably, it is in the range of ⁇ 1100 ° C.
  • the firing temperature is less than the lower limit, there is a possibility that the supported at least one rare earth element does not sufficiently react.
  • the firing temperature exceeds the upper limit the pyrochlore phase structure of CeO 2 —ZrO 2 may be deteriorated. Therefore, a ceria-zirconia composite oxide powder having a desired ordered phase can be obtained by firing under the above conditions.
  • the ceria-zirconia composite oxide containing at least one rare earth element used in the exhaust gas purifying catalyst of the present invention is suppressed in the phase transformation of the CeO 2 —ZrO 2 pyrochlore phase structure,
  • the heat resistance against high temperature is improved, and as a result, a sufficiently high oxygen storage capacity can be exhibited even after being exposed to a high temperature environment. Therefore, by containing this material in the lower layer, the exhaust gas purifying catalyst of the present invention can exhibit high exhaust gas purifying ability even after being used under high temperature conditions for a long time.
  • a predetermined amount of material 1, ceria-zirconia composite oxide (CeO 2 -ZrO 2 , ZC), barium sulfate and Al 2 O 3 binder were added to distilled water and suspended with stirring to obtain slurry 1.
  • Slurry 1 is poured into a ceramic honeycomb test piece base material (60H / 3-9R-08, manufacturer: DENSO, capacity: 875 mL), and excess surface is blown away with a blower to coat the surface of the base material with slurry 1 did.
  • Slurry 1 shows that each material coated on the substrate is 0.58 g / L Pd, 65 g / L La-Al 2 O 3 , 70 g / L ZC, 5 g It was prepared so as to have an amount of barium sulfate / L.
  • the amount of each material coated on the base material was 0.89 parts by mass of Pd, 108 parts by mass of ZC, 7.7 parts per 100 parts by mass of La-Al 2 O 3 (46.2% by mass with respect to the total mass of the lower layer). Mass parts of barium sulfate was obtained.
  • the substrate coated with the slurry 1 was allowed to stand in a dryer set at 120 ° C. for 2 hours to evaporate the water content of the slurry.
  • a lower catalyst layer (total coating amount: 81 g; 92.57 g / L base material) was prepared.
  • the lower catalyst layer was coated over the entire length of the base material up to 90% from the end of the base material on the exhaust gas inflow side.
  • Rh / AZC catalyst layer material material 2 in which Rh was supported on alumina-added ceria-zirconia composite oxide (AZC) was prepared by an impregnation method using rhodium nitrate in the same procedure as the preparation of the material 1.
  • a predetermined amount of the material 2, La—Al 2 O 3 and Al 2 O 3 binder was added to distilled water and suspended while stirring to obtain slurry 2.
  • Slurry 2 was poured into the base material on which the lower catalyst layer was formed, and the excess was blown off with a blower to coat slurry 2 on the upper surface of the lower catalyst layer.
  • Slurry 2 is based on the amount of 0.2 g / L Rh, 65 g / L AZC, 25 g / L La-Al 2 O 3 with respect to the volume of the substrate. It was prepared as follows.
  • the amount of each material coated on the base material is 0.31 parts by mass of Rh and 38.5 parts by mass of La-Al 2 O 3 with respect to 100 parts by mass of AZC (72% by mass with respect to the total mass of the upper layer). It was.
  • the substrate coated with the slurry 2 was allowed to stand in a dryer set at 120 ° C. for 2 hours to evaporate the water content of the slurry. Thereafter, the substrate was allowed to stand in an electric furnace set at 500 ° C. for 2 hours, and the substrate and the coating were baked.
  • an upper catalyst layer total coating amount: 37 g; 42 g / L substrate
  • the upper catalyst layer was coated over the entire length of the base material up to 60% from the end of the base material on the exhaust gas outflow side.
  • a ceria-zirconia solid solution powder in which the content ratio of cerium and zirconium was 46:54 in molar ratio ([cerium]: [zirconium]) was prepared by the following procedure.
  • the obtained coprecipitate was centrifuged, and the precipitate was washed with ion exchange water.
  • the obtained coprecipitate was dried at 110 ° C. in the atmosphere for 10 hours or more.
  • the dried coprecipitate was baked in the atmosphere at 400 ° C. for 5 hours to obtain a solid solution of cerium and zirconium (ceria-zirconia solid solution or CeO 2 —ZrO 2 solid solution).
  • the solid solution was pulverized with a sieve to a particle size of 75 ⁇ m or less using a pulverizer (Wonder Blender, manufactured by ASONE Co., Ltd.) to obtain a ceria-zirconia solid solution powder.
  • the obtained molded bodies (2 sheets) were placed in a basket filled with 70 g of activated carbon (inner volume: diameter 8 cm, height 7 cm), covered, and then placed in a fast heating furnace .
  • the molded body is heated to 1000 ° C. with a temperature rising time of 1 hour, then heated to 1700 ° C. with a temperature rising time of 4 hours and held for 5 hours, then cooled to 1000 ° C. with a cooling time of 4 hours, and then spontaneously released. Cooled to room temperature.
  • a reduction-treated product was obtained by the treatment.
  • the obtained reduction-treated product was oxidized by heating in the atmosphere at a temperature of 500 ° C. for 5 hours, and the content ratio of cerium and zirconium in the composite oxide was 46 in molar ratio ([cerium]: [zirconium]). : 54, a ceria-zirconia composite oxide was obtained.
  • the obtained ceria-zirconia composite oxide was pulverized to 75 ⁇ m or less with a sieve.
  • a lanthanum nitrate aqueous solution containing lanthanum (La) having 0.25 atomic% as an element with respect to the total amount of Ce and Zr in the obtained ceria-zirconia composite oxide was prepared.
  • 10 g of the ceria-zirconia composite oxide obtained above was added.
  • a predetermined amount of La was supported on the ceria-zirconia composite oxide by a water absorption supporting method in which the mixture was stirred at room temperature for 1 hour.
  • the reaction mixture was filtered to separate the La-supported powder.
  • the obtained La-supported powder was dried in air at 110 ° C. for 12 hours.
  • the obtained La-supported ceria-zirconia composite oxide was calcined in the atmosphere at 900 ° C. for 5 hours to obtain particulate La-supported ceria-zirconia composite oxide.
  • the structure and morphology of the particles were observed using HR-TEM (high resolution transmission electron microscope), and EDX analysis (energy dispersive X-ray detector) was performed.
  • the composition analysis of the used particles, the analysis of the region near the surface, and the average particle diameter of the primary particles using a scanning electron microscope (SEM) were observed.
  • the average particle size of the primary particles was measured by measuring the particle size of any 50 primary particles by SEM observation and calculating the average value of the particle sizes. When the observed cross section of the primary particles was not circular, the diameter of the minimum circumscribed circle was used.
  • the La content in the La-supported ceria-zirconia composite oxide was 0.25 atomic% as an element with respect to the total amount of Ce and Zr. Further, of the total amount of La contained in the La-supported ceria-zirconia composite oxide, the proportion of those present in the surface vicinity region within 50 nm from the surface of the primary particles of the La-supported ceria-zirconia composite oxide is 100 atoms It was a few percent. The average particle diameter of the primary particles of the obtained La-supported ceria-zirconia composite oxide was 3.0 ⁇ m.
  • Preparation Example 2 Preparation Example, except that in the rare earth element loading step, an aqueous lanthanum nitrate solution containing 0.5% by number of lanthanum (La) as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was used. In the same manner as in Example 1, particulate La-containing ceria-zirconia composite oxide was obtained.
  • the obtained particulate La-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the La content in the La-containing ceria-zirconia composite oxide was 0.5 atomic% as an element with respect to the total amount of Ce and Zr.
  • the proportion of those present in the surface vicinity region within 50 nm from the surface of the primary particles of the La-supported ceria-zirconia composite oxide is 100 atoms It was a few percent.
  • the average particle diameter of the primary particles of the obtained La-containing ceria-zirconia composite oxide was 3.2 ⁇ m.
  • Preparation Example 3 Preparation examples except that in the rare earth element loading step, an yttrium nitrate aqueous solution containing yttrium (Y) containing 0.5 atomic% as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was used. In the same manner as in Example 1, a particulate Y-containing ceria-zirconia composite oxide was obtained.
  • the obtained particulate Y-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the Y content in the Y-containing ceria-zirconia composite oxide was 0.5 atomic% as an element with respect to the total amount of Ce and Zr.
  • the proportion of those present in the region near the surface within 50 ⁇ m from the surface of the primary particles of the Y-supported ceria-zirconia composite oxide is 95 atoms It was a few percent.
  • the average particle diameter of the primary particles of the obtained Y-containing ceria-zirconia composite oxide was 3.1 ⁇ m.
  • Preparation Example 4 Preparation example except that in the rare earth element loading step, an aqueous praseodymium nitrate solution containing praseodymium (Pr) containing 0.5 atomic% as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was used. In the same manner as in Example 1, a particulate Pr-containing ceria-zirconia composite oxide was obtained.
  • the obtained particulate Pr-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the content ratio of the praseodymium element in the Pr-containing ceria-zirconia composite oxide was 0.5 atomic% as an element with respect to the total amount of Ce and Zr.
  • the ratio of those present in the surface vicinity region within 50 nm from the surface of the primary particles of the Pr-supported ceria-zirconia composite oxide is 100 atoms It was a few percent.
  • the average particle diameter of the primary particles of the obtained La-containing ceria-zirconia composite oxide was 3.3 ⁇ m.
  • Preparation Example 5 In the rare earth element loading step, a lanthanum nitrate aqueous solution containing 0.5% lanthanum (La) as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide is prepared and used. A particulate La-containing ceria-zirconia composite oxide was obtained in the same manner as in Preparation Example 1, except that the temperature was 1100 ° C.
  • the obtained particulate La-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the La content in the La-containing ceria-zirconia composite oxide was 0.5 atomic% as an element with respect to the total amount of Ce and Zr.
  • the ratio of those present in the vicinity of the surface within 50 ⁇ m from the surface of the primary particles of the La-supported ceria-zirconia composite oxide is 100 atoms %Met.
  • the average particle size of the primary particles of the obtained La-containing ceria-zirconia composite oxide was 3.4 ⁇ m.
  • Preparation Example 6 Preparation Example, except that an aqueous lanthanum nitrate solution containing 1.0% lanthanum (La) as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was prepared and used in the rare earth element loading step In the same manner as in Example 1, particulate La-containing ceria-zirconia composite oxide was obtained.
  • aqueous lanthanum nitrate solution containing 1.0% lanthanum (La) as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was prepared and used in the rare earth element loading step
  • particulate La-containing ceria-zirconia composite oxide was obtained.
  • the obtained particulate La-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the La content in the La-containing ceria-zirconia composite oxide was 1.0 atomic% as an element with respect to the total amount of Ce and Zr.
  • the ratio of those present in the vicinity of the surface within 50 ⁇ m from the surface of the primary particles of the La-supported ceria-zirconia composite oxide is 100 atoms %Met.
  • the average particle diameter of the primary particles of the obtained La-containing ceria-zirconia composite oxide was 3.3 ⁇ m.
  • Preparation Example 7 Preparation Example, except that a lanthanum nitrate aqueous solution containing 2.5% lanthanum (La) as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was prepared and used in the rare earth element loading step In the same manner as in Example 1, particulate La-containing ceria-zirconia composite oxide was obtained.
  • a lanthanum nitrate aqueous solution containing 2.5% lanthanum (La) as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was prepared and used in the rare earth element loading step
  • La lanthanum nitrate aqueous solution containing 2.5% lanthanum (La) as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide
  • the obtained particulate La-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the La content in the La-containing ceria-zirconia composite oxide was 2.5 atomic% as an element with respect to the total amount of Ce and Zr.
  • the ratio of those present in the vicinity of the surface within 50 ⁇ m from the surface of the primary particles of the La-supported ceria-zirconia composite oxide is 100 atoms %Met.
  • the average particle diameter of the primary particles of the obtained La-containing ceria-zirconia composite oxide was 3.6 ⁇ m.
  • Preparation Comparative Example 1 The ceria-zirconia composite oxide obtained in Preparation Example 1 (without carrying lanthanum and firing) was prepared as a particulate ceria-zirconia composite oxide for comparison.
  • the obtained ceria-zirconia composite oxide for comparison was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the rare earth element content in the ceria-zirconia composite oxide of Preparation Comparative Example 1 was 0.0 atomic% as an element with respect to the total amount of Ce and Zr.
  • the average particle diameter of the primary particles of the ceria-zirconia composite oxide obtained in Preparation Comparative Example 1 was 3.2 ⁇ m.
  • Preparation Comparative Example 2 Preparation Example, except that in the rare earth element loading step, an aqueous lanthanum nitrate solution containing lanthanum (La) containing 5.0 atomic% as an element with respect to the total amount of Ce and Zr in the ceria-zirconia composite oxide was used. In the same manner as in Example 1, particulate La-containing ceria-zirconia composite oxide was obtained.
  • La lanthanum
  • the obtained particulate La-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the La content in the La-containing ceria-zirconia composite oxide was 5.0 atomic% as an element with respect to the total amount of Ce and Zr.
  • the proportion of those present in the region near the surface within 50 ⁇ m from the surface of the primary particles of the La-supported ceria-zirconia composite oxide is 89 atoms %Met.
  • the average particle diameter of the primary particles of the obtained La-containing ceria-zirconia composite oxide was 3.5 ⁇ m.
  • the obtained particulate Fe-containing ceria-zirconia composite oxide was subjected to HR-TEM observation, EDX analysis, and SEM observation in the same manner as in Preparation Example 1.
  • the content ratio of iron element in the Fe-containing ceria-zirconia composite oxide was 2.5 atomic% as an element with respect to the total amount of Ce and Zr.
  • the proportion of those present in the region near the surface within 50 ⁇ m from the surface of the primary particles of the Fe-supported ceria-zirconia composite oxide was 92 atoms It was a few percent.
  • the average particle size of the primary particles of the obtained Fe-containing ceria-zirconia composite oxide was 3.1 ⁇ m.
  • the oxygen absorption / release amount represents the amount of oxygen absorbed / released at 400 ° C. per 1 g of CZ in the catalyst (O 2 -mg / CZ-g).
  • the amount of oxygen absorbed and released was measured at a flow rate of 200 ml / min with respect to 15 mg of catalyst under the temperature condition of 400 ° C by placing the catalyst sample in the sample cell of a thermogravimetric analyzer (TG, manufactured by Okura Riken).
  • the lower catalyst layer La-pyrochlore ZC coated on the base material was in an amount of 5, 10 or 20 g / L, respectively, with respect to the base material capacity.
  • the other materials of the lower catalyst layer and all the materials of the upper catalyst layer were produced in the same amount as in Comparative Example 1.
  • the amount of Pr-pyrochlore ZC in the lower catalyst layer coated on the substrate was 100 parts by mass of La-Al 2 O 3 (per the total mass of the lower layer).
  • Example 1 was 45% by mass
  • Example 2 was 43% by mass
  • Example 3 was 40% by mass).
  • the amount of La-pyrochlore ZC in the lower catalyst layer coated on the substrate was 100 parts by mass of La-Al 2 O 3 (based on the total mass of the lower layer).
  • Example 4 was 45% by mass
  • Example 5 was 43% by mass
  • Example 6 was 40% by mass), which was 0.077, 15 or 31 parts by mass, respectively.
  • the amount of pyrochlore ZC in the lower catalyst layer coated on the substrate was 100 parts by mass of La-Al 2 O 3 (reference example 1 relative to the total mass of the lower layer). Of 45% by mass, 43% by mass of Reference Example 2 and 40% by mass of Reference Example 3), respectively, 0.077, 15 or 31 parts by mass.
  • the NOx emission amount at the time of A / F switching was the NOx emission amount at the time when it was determined that the A / F in the inflowing gas atmosphere was switched between rich and lean by the sub O 2 sensor.
  • the steady rich NOx purification rate was defined as the purification rate when the inflowing gas atmosphere A / F was continued in a rich state.
  • FIG. 10 shows the relationship between the amount of pyrochlore ZC added to the lower catalyst layer and the NOx emission during A / F switching in the heat endurance treatment tests of the catalysts of Comparative Example 1, Examples 1 to 3 and Reference Examples 1 to 3. Shown in In the figure, the black squares show the test results of Comparative Example 1, the black triangles show the test results of Examples 1 to 3, and the black diamonds show the test results of Reference Examples 1 to 3, respectively. In addition, in the thermal endurance treatment tests of the catalysts of Comparative Example 1, Examples 4 to 6 and Reference Examples 1 to 3, the relationship between the amount of pyrochlore ZC added to the lower catalyst layer and the NOx emission at the time of A / F switching is shown. As shown in FIG.
  • the black squares indicate the test results of Comparative Example 1
  • the black triangles indicate the test results of Examples 4 to 6
  • the black diamonds indicate the test results of Reference Examples 1 to 3, respectively.
  • the two-layer catalysts of Examples 1 to 3 and Examples 4 to 6 have lower NOx emissions during A / F switching than the two-layer catalyst of Comparative Example 1.
  • the two-layer catalysts of Examples 1 to 3 and Examples 4 to 6 were compared with the two-layer catalysts of Reference Examples 1 to 3 containing the conventional pyrochlore ZC containing no Pr or La in the lower catalyst layer. However, NOx emissions during A / F switching decreased.
  • the two-layer catalyst of the present invention contains the pyrochlore ZC containing Pr or La in the lower catalyst layer, so that the NOx at the time of A / F switching can be obtained even after being used under a high temperature condition for a long time. It became clear that the exhaust amount can be greatly reduced and the high exhaust gas purification ability can be exhibited.
  • FIG. 11 shows the relationship between the amount of pyrochlore ZC added to the lower catalyst layer and the steady rich NOx purification rate in the heat endurance treatment tests of the catalysts of Comparative Example 1 and Examples 1 to 3.
  • the black squares indicate the test results of Comparative Example 1
  • the black triangles indicate the test results of Examples 1 to 3, respectively.
  • FIG. 13 shows the relationship between the amount of pyrochlore ZC added to the lower catalyst layer and the steady rich NOx purification rate in the heat endurance treatment tests of the catalysts of Comparative Example 1 and Examples 4 and 5.
  • the black squares indicate the test results of Comparative Example 1
  • the black diamonds indicate the test results of Examples 4 and 5, respectively.
  • the two-layer catalysts of Examples 1 and 2 and Examples 4 and 5 were improved in the steady rich NOx purification rate as compared with the two-layer catalyst of Comparative Example 1.
  • the two-layer catalyst of Example 3 had a lower steady rich NOx purification rate than the two-layer catalyst of Comparative Example 1. From this result, in the two-layer catalyst of the present invention, when the amount of pyrochlore ZC containing Pr or La increases in the lower catalyst layer, NOx purification when the A / F of the inflowing gas atmosphere is continued in a rich state It became clear that the rate decreased. From the results of FIGS.
  • the optimum range of the addition amount of the pyrochlore ZC containing Pr or La to the lower catalyst layer is 5 to 15 parts by mass with respect to the capacity of the substrate, and 100 parts by mass of La It was revealed that it was 7.7 to 23 parts by mass with respect to -Al 2 O 3 .
  • Catalyst for purifying exhaust gas of the present invention 11... Upper layer 12 ... Lower layer 13 . Catalyst layer 14... Base material

Abstract

Le problème décrit par la présente invention est de fournir un catalyseur de purification de gaz d'échappement, un moyen étant prévu pour maintenir les performances du catalyseur même après une utilisation à long terme du catalyseur. La présente invention concerne un catalyseur de purification de gaz d'échappement comprenant une couche supérieure et une couche inférieure, la couche inférieure comportant un oxyde composite de cérium et de zirconium contenant au moins un type d'élément des terres rares et comportant en outre des oxydes composites de cérium et de zirconium, et l'oxyde composite de cérium et de zirconium contenant au moins un type d'élément des terres rares contenant au moins un type d'élément des terres rares choisi dans le groupe constitué par le lanthane, l'yttrium, et le praséodyme, à raison de 0,1 à 4,0 % atomique par rapport à la quantité totale de cérium et de zirconium dans l'oxyde composite de cérium et de zirconium, et contenant au moins 90 % atomique de la quantité totale dudit type d'élément des terres rares dans une zone proche de la surface à 50 nm des surfaces de ses particules primaires.
PCT/JP2016/059353 2015-03-27 2016-03-24 Catalyseur de purification de gaz d'échappement WO2016158656A1 (fr)

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JP2020163342A (ja) 2019-03-29 2020-10-08 株式会社キャタラー 排ガス浄化触媒装置
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