WO2016143722A1 - Support noyau-enveloppe, son procédé de production, catalyseur de purification des gaz d'échappement utilisant ledit support noyau-enveloppe, son procédé de production, et procédé de purification des gaz d'échappement utilisant le catalyseur de purification des gaz d'échappement - Google Patents

Support noyau-enveloppe, son procédé de production, catalyseur de purification des gaz d'échappement utilisant ledit support noyau-enveloppe, son procédé de production, et procédé de purification des gaz d'échappement utilisant le catalyseur de purification des gaz d'échappement Download PDF

Info

Publication number
WO2016143722A1
WO2016143722A1 PCT/JP2016/056908 JP2016056908W WO2016143722A1 WO 2016143722 A1 WO2016143722 A1 WO 2016143722A1 JP 2016056908 W JP2016056908 W JP 2016056908W WO 2016143722 A1 WO2016143722 A1 WO 2016143722A1
Authority
WO
WIPO (PCT)
Prior art keywords
core
catalyst
exhaust gas
shell
purification
Prior art date
Application number
PCT/JP2016/056908
Other languages
English (en)
Inventor
Naoki KUMATANI
Toshitaka Tanabe
Masahide Miura
Original Assignee
Toyota Jidosha Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2016019455A external-priority patent/JP6676394B2/ja
Application filed by Toyota Jidosha Kabushiki Kaisha filed Critical Toyota Jidosha Kabushiki Kaisha
Priority to US15/550,148 priority Critical patent/US20180021758A1/en
Priority to DE112016001168.7T priority patent/DE112016001168T5/de
Priority to CN201680014994.XA priority patent/CN107427822A/zh
Publication of WO2016143722A1 publication Critical patent/WO2016143722A1/fr

Links

Classifications

    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0248—Coatings comprising impregnated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • 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
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/36—Three-dimensional structures pyrochlore-type (A2B2O7)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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 supporting oxide such as r0 2 or T1O2 covers the entirety of the core member made of the oxygen storage/release material (OSC material) such as Ce0 2 .
  • OSC material oxygen storage/release material
  • the oxygen storage/release capacity brought by the core member greatly decreases, and the oxygen storage/release capacity (OSC) is not necessarily sufficient.
  • the present invention has been made in view of the above - described problems of the conventional technologies, and an object of the present invention is to provide a core-shell support which enables both sufficiently good oxygen storage/release capacity. (OSC) and sufficiently good NOx removal activity to be exhibited, a method for producing the core-shell support, a catalyst for purification of exhaust gas using the core-shell support, a method for producing the catalyst, and a method for purification of exhaust gas using the catalyst for purification of exhaust gas.
  • OSC oxygen storage/release capacity
  • NOx removal activity to be exhibited, a method for producing the core-shell support, a catalyst for purification of exhaust gas using the core-shell support, a method for producing the catalyst, and a method for purification of exhaust gas using the catalyst for purification of exhaust gas.
  • a core-shell support comprises: a core which comprises at least one oxygen storage/release material selected from the group consisting of ceria- zirconia based solid solutions and alumina-doped ceria- zirconia based solid solutions; and a shell which comprises a rare earth- zirconia based composite oxide with a specific composition and with which an outside of the core is coated, the rare earth- z irconia based composite oxide comprises crystal particles having a pyrochlore structure, and the average crystallite diameter of the rare earth- zirconia based composite oxide is in a specific range, it is possible to obtain a core-shell support which enables both oxygen storage/release capacity (OSC) and NOx removal activity to be exhibited sufficiently, a method for producing the core-shell support, a catalyst for purification of exhaust gas using the core-shell support, a method for producing the catalyst, and a method for pur
  • OSC oxygen storage/release capacity
  • x in the composition formula is preferably a number of 0.5 to 0.7.
  • the core-shell support being obtained by performing the second coating step until an amount of the rare earth- zirconia based composite oxide constituting the shell after the calcination to the oxide reaches 4 to 24 parts by mass relative to 100 parts by mass of the oxygen storage/release material constituting the core.
  • the rare earth- zirconia based composite oxide comprises crystal particles having a pyrochlore structure, and the average crystallite diameter of the rare earth- z irconia based composite oxide is limited in the range from 3 to 9 nm .
  • the present inventors speculate that the NOx removal activity and the oxygen storage/release capacity, which have conventionally been considered to be in a trade-off relationship, can be achieved simultaneously at high levels, and this makes it possible to provide a core-shell support which enables both sufficiently good oxygen storage/release capacity (OSC) and sufficiently good NOx removal activity to be exhibited, a method for producing the core-shell support, a catalyst for purification of exhaust gas using the core-shell support, a method for producing the catalyst, and a method for purification of exhaust gas using the catalyst for purification of exhaust gas .
  • OSC oxygen storage/release capacity
  • Fig. 1 is a graph showing the 50% NOx removal temperatures (NOx_T50) of catalysts obtained in Examples 1 to 6 and Comparative Examples 1 to 4.
  • the alumina - doped ceria- zirconia based solid solution in the core of the core-shell support of the present invention is not particularly limited, and specific examples thereof include Al 2 03-doped Ce0 2 -Zr02 solid solutions, Al 2 0 3 doped- Ce02 - Zr02 -La203 solid solutions, Al 2 0 3 -doped Ce0 2 - Zr0 2 - La 2 0 3 - Y2O3 -Nd 2 0 3 solid solutions, and Al 2 0 3 -doped Ce0 2 - r02 - Pr0 2 - La 2 0 3 - Y20 3 solid solutions'.
  • the composition of the rare earth- z irconia based composite oxide can be determined by a composition analysis based on ICP emission spectroscopy (plasma emission spectroscopy) using an inductively coupled plasma (ICP) emission spectrometer, or a composition analysis using any one of or a suitable combination of any ones of an X-ray fluorescence analyzer (XRF: X-ray Fluorescence Analysis) , an EDX (energy-dispersive X-ray spectrometer) , an XPS ( photoelectron spectrometer) , a SIMS (secondary ion mass spectrometer), an HR-TEM
  • the rare earth- z irconia based composite oxide in the shell according to the core-shell support of the present invention needs to have an average crystallite diameter in a range from 3 to 9 nm .
  • the average crystallite diameter of the rare earth- z irconia based composite oxide is less than the lower limit. If a catalyst is prepared by supporting a noble metal on such a rare earth- z irconia based composite oxide, the noble metal (Rh or the like) becomes difficult to reduce because of the interaction between CeCb and the noble metal (Rh or and the like) , so that the NOx removal activity decreases, and the NOx removal performance cannot be obtained sufficiently.
  • the second catalyst for purification of exhaust gas of the present invention preferably contains 0.01 to 2.0 g/L of the noble metal, 50 to 180 g/L of the core-shell support of the present invention, and 20 to 150 g/L of alumina, per liter of the capacity of the substrate.
  • a solution preparation step of preparing a solution containing a rare earth element salt and a zirconium salt a first coating step of bringing the prepared solution into contact with a powder of at least one oxygen storage/release material selected from the group consisting of ceria- zirconia based solid solutions and alumina - doped ceria- zirconia based solid solutions to obtain a core-shell powder supporting the prepared solution in an amount which gives, after calcination to an oxide, 1 to 8 parts by mass of the rare earth- zirconia based composite oxide constituting a part of the shell relative to 100 parts by mass of the oxygen storage/release material constituting the core, followed by calcination at a temperature in a range from 600 to 1100 °C and then by grinding; and
  • a solution containing a rare earth element salt and a zirconium salt is prepared (solution preparation step) .
  • concentrations in the solution containing a rare earth element salt and a zirconium salt are not particularly limited, and the concentration of the rare earth element ions is preferably in a range from 0.001 to 0.1 mol/L, and the concentration of zirconium (Zr) ions is preferably in a range from 0.001 to 0.1 mol/L.
  • the amount of the solution supported is preferably an amount which gives, after calcination to an oxide, 2 to 6 parts by mass, and further preferably an amount which gives, after calcination to an oxide, 4 to 6 parts by mass of the rare earth- zirconia based composite oxide constituting a part of the shell relative to 100 parts by mass of the oxygen storage/release material constituting the core, from the viewpoint of supporting the solution with a uniform supporting density.
  • the core-shell support is obtained by performing this second coating step until an amount of the rare earth- zirconia based composite oxide constituting the shell after the calcination to the oxide reaches 4 to 24 parts by mass relative to 100 parts by mass of the oxygen storage/release material constituting the core.
  • the second coating step is preferably performed once or twice. If so, a surface layer enriched with the rare earth element and zirconium can be deposited more uniformly on the core surface, so that the pyrochlore structure (Rei- x Ce x ) 2Zr207 + x formed in the rare earth- zirconia based composite oxide constituting the shell can be further stabilized.
  • the catalyst for purification of exhaust gas is obtained by bringing a noble metal salt solution into contact with the core-shell support (catalyst preparation step) .
  • a specific method for bringing the noble metal salt solution into contact with the core-shell support in this catalyst preparation step is not particularly limited, and a method is preferably used in which the core-shell support is immersed in a solution obtained by dissolving a salt (nitrate, chloride, acetate, or the like) of the noble metal or a complex of the noble metal in a solvent such as water or an alcohol, and, after removal of the solvent, the core-shell support is calcined and ground, for example .
  • drying conditions for removing the solvent are preferably about 180 minutes or less at 150 to 200°C, whereas calcination conditions are preferably about 3 to 5 hours at 300 to 400°C in an oxidizing atmosphere (for example, air) .
  • a step of supporting the noble metal may be repeated, until a desired amount of the noble metal supported is achieved .
  • the method for purification of exhaust gas of the present invention can be employed suitably as a method for removing, for example, harmful components such as harmful gases (hydrocarbons (HCs) , carbon monoxide (CO) , and nitrogen oxides (NOx) ) contained in an exhaust gas emitted from an internal combustion engine in an automobile etc. , or the like.
  • harmful components such as harmful gases (hydrocarbons (HCs) , carbon monoxide (CO) , and nitrogen oxides (NOx) contained in an exhaust gas emitted from an internal combustion engine in an automobile etc. , or the like.
  • a core-shell support was obtained by performing a single series of processes in which the solution was supported on the obtained core-shell powder by impregnation in the same manner as in the above-described first coating step, and then the impregnated powder was evaporated to dryness, followed by calcination and grinding (second coating step) .
  • a core-shell support was obtained in the same manner as in Example 1, except that an alumina-doped ceria - z irconia based solid solution powder with a composition (% by mass) of
  • a powdery catalyst for comparison was obtained by supporting Rh as the noble metal on 10 g of the powder of the catalyst support for comparison in the same manner as in Example 1. Note that the amount of rhodium supported in the obtained powder of the catalyst for comparison was 0.15% by mass relative to 100% by mass of the catalyst support for comparison.
  • A1 2 0 3 : Ce0 2 : Zr0 2 : La 2 0 3 : Y 2 O 3 : Nd 2 0 3 30 : 20 : 44 : 2 : 2 : 2 , an average particle diameter of 8 m, and a specific surface area of 70 m 2 /g) was used.
  • a powdery catalyst for comparison was obtained by supporting Rh as the noble metal on 10 g of the powder of the catalyst support for comparison in the same manner as in Example 1. Note that the amount of rhodium supported in the obtained powder of the catalyst for comparison was 0.15% by mass relative to 100% by mass of the catalyst support for comparison.
  • the average crystallite diameter (average primary particle diameter) of the shell ( rare earth- z irconia based composite oxide) of each of the catalysts obtained in Examples 1 to 6 and Comparative Examples 3 and 4 was measured as follows.
  • XRD X-ray diffraction
  • composition formula: ( Re i- x Ce x ) 2Zr 2 0 7+ x (where Re represents a rare earth element, and x represents a number of 0.0 to 0.8) ) of the shell (rare earth- zirconia based composite oxide) of each of the catalysts obtained in Examples 1 to 6 and Comparative Examples 3 and 4 and x in the composition formula were determined as follows. Specifically, on an assumption that a lattice constant changed linearly between the lattice constant calculated from the peak position of Re 2 Zr 2 0 7 and the lattice constant calculated from the peak position of Ce2 r20s, the amount of Ce in the shell material, i. e . , the value of x was determined from the lattice constant calculated from the peak position of the shell material. Table 1 shows the obtained results.
  • a model gas treatment was conducted in which a lean (L) gas and a rich (R) gas having the gas compositions shown in Table 2 were passed alternately for 5 minutes each and 5 hours in total under a temperature condition of 1100°C at a flow rate of 10 L ( liters ) /minute .
  • a high- temperature endurance treatment (endurance test) was conducted.
  • a model exhaust gas of three harmful gases having the gas composition shown in Table 3 was supplied under a temperature condition of 600°C at a flow rate of 10 L/minute for 6 minutes (pretreatment ) . After that, the temperature of each sample was cooled to 100°C. Then, while the model exhaust gas was being supplied at a flow rate of 10 L/minute, the sample was heated from 100°C to 600°C at a rate of temperature rise of 6°C/minute. The temperature (50% NOx removal temperature, °C, referred to as "NOx_T50”) at which the NO removal ratio in the supplied model exhaust gas reached 50% was measured.
  • NOx_T50 50% NOx removal temperature
  • the transient NOx removal ratio of each of the catalysts obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was measured by conducting a transient NOx removal activity evaluation test on the pellet catalyst sample subjected to the high- temperature endurance treatment by using a flow reactor and an exhaust gas analyzer as follows.
  • a rich gas (CO (2% by volume) + N 2 ( the balance ) ) and a lean gas (O2 (1% by volume) + N 2 (the balance) ) were passed alternately through the fixed bed flow type reactor under a temperature condition of 500°C, while being switched from one to the other every three minutes.
  • the amount of oxygen (O2) generated in the rich gas atmosphere was measured, and the oxygen (O 2 ) generation rate, which was the amount of oxygen (0 2 ) generated in 5 seconds after the introduction of the rich gas, was determined as the oxygen storage/release (OSC) rate ( ⁇ /g/sec or ymol-0 2 /g/s) .
  • OSC oxygen storage/release
  • the gas flow rate was 10 L/min, and an analyzer manufactured by BEST INSTRUMENTS CO., Ltd. under the trade name of "Bex5900Csp" was used.
  • each of the catalysts of Examples 1 to 6 were excellent in both the performances of the NOx removal ratio and the OSC (oxygen storage/release capacity) property, because the catalyst comprised a core which comprised a ceria- zirconia based solid solution or an alumina - doped ceria- zirconia based solid solution, and a shell which comprised a rare earth- zirconia based composite oxide represented by the composition formula: ( Re i-xCe x ) 2Zr207 + x (where Re represents a rare earth element, and x represents a number of 0.0 to 0.8) and with which the outside of the core was coated, the rare earth- z irconia based composite oxide comprised crystal particles having a pyrochlore structure, and the average crystallite diameter of the rare earth- zirconia based composite oxide was limited in the range from 3 to 9 nm .
  • alumina-doped zirconia based solid solution As an alumina-doped zirconia based solid solution (AZL) , a composite oxide containing 30% by mass of Al 2 0 3 , 65% by mass of Zr0 2 , and 5% by mass of La 2 0 3 was used (hereinafter, also referred to as "Material 4”) .
  • an aqueous rhodium nitrate solution manufactured by Cataler Corporation having a noble metal content of 2.75% by mass was used (hereinafter, also referred to as "Material 5") .
  • an aqueous palladium nitrate solution manufactured by Cataler Corporation having a noble metal content of 8.8% by mass was used (hereinafter, also referred to as "Material 6") .
  • a material in which rhodium (Rh) was supported on alumina-doped zirconia based solid solution (AZL) was prepared (Rh/AZL, hereinafter, also referred to as "Material 9") .
  • Rh/AZL alumina-doped zirconia based solid solution
  • a double-layer catalyst having a rhodium- containing catalyst layer as the upper layer and a palladium- containing catalyst layer as the lower layer was obtained by the same procedure as that in Comparative Example 5, except that a slurry containing Material 9, Material 2, Material 1, and the alumina-based binder was used in the step of forming the upper layer.
  • a double-layer catalyst having a rhodium- containing catalyst layer as the upper layer and a palladium- containing catalyst layer as the lower layer was obtained by the same procedure as that in Comparative Example 5, except that a slurry containing Material 10, Material 1, and the alumina-based binder was used in the step of forming the upper layer.
  • the preparation was conducted under such conditions that the resultant substrate coated with the upper layer contained 0.10 g/L of rhodium, 28 g/L of Material 1, and 110 g/L of Material 3, per liter of the capacity of the substrate.
  • a double-layer catalyst having a rhodium-containing catalyst layer as the upper layer and a palladium-containing catalyst layer as the lower layer was obtained by the same procedure as that in Comparative Example 5, except that a slurry containing Material 9, Material 10, Material 1, and the alumina -based binder was used in the step of forming the upper layer.
  • the preparation was conducted under such conditions that the resultant substrate coated with the upper layer contained 0.10 g/L of rhodium, 28 g/L of Material 1, 55 g/L of Material 3, and 55 g/L of Material 4, per liter of the capacity of the substrate.
  • Comparative Examples 5 to 7 was evaluated (after the accelerated deterioration treatment) .
  • An air-fuel ratio (A/F) was feedback-controlled aiming at an A/F of 14.1, and the NOx emission in the exhaust gas having passed through each catalyst was determined under a condition of 600 °C .
  • a core-shell support which enables both sufficiently good oxygen storage/release capacity (OSC) and sufficiently good NOx removal activity to be exhibited, a method for producing the core-shell support, a catalyst for purification of exhaust gas using the core-shell support, a method for producing the catalyst, and a method for purification of exhaust gas using the catalyst for purification of exhaust gas.
  • the core-shell support of the present invention and the catalyst for purification of exhaust gas using the core-shell support of the present invention offer both sufficiently good oxygen storage/release capacity (OSC) and sufficiently good NOx removal activity as described above, and hence enable both sufficiently good oxygen storage/release capacity (OSC) and sufficiently good NOx removal activity to be exhibited.
  • the catalyst for purification of exhaust gas of the present invention can sufficiently exhibit both sufficiently high oxygen storage/release capacity (OSC) and sufficiently high NOx removal activity, and can sufficiently remove harmful gases such as NOx contained in the exhaust gas.
  • OSC oxygen storage/release capacity

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un support noyau-enveloppe, comprenant : un noyau qui comprend au moins un matériau de stockage/libération d'oxygène choisi dans le groupe constitué des solutions solides à base de zircone-cérine et des solutions solides à base de zircone-cérine dopée à l'alumine; et une enveloppe qui comprend un oxyde composite à base de terre rare-zircone représenté par la formule brute suivante : (Re1-xCex) 2Zr207+x (où Re représente un élément des terres rares et x représente un nombre de 0,0 à 0,8) et avec laquelle l'extérieur du noyau est revêtu, l'oxyde composite à base de terre rare-zircone comprenant des particules cristallines à structure pyrochlore, et l'oxyde composite à base de terre rare-zircone présentant un diamètre des cristallites moyen variant de 3 à 9 nm.
PCT/JP2016/056908 2015-03-12 2016-03-01 Support noyau-enveloppe, son procédé de production, catalyseur de purification des gaz d'échappement utilisant ledit support noyau-enveloppe, son procédé de production, et procédé de purification des gaz d'échappement utilisant le catalyseur de purification des gaz d'échappement WO2016143722A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/550,148 US20180021758A1 (en) 2015-03-12 2016-03-01 Core-shell support, method for producing the same, catalyst for purification of exhaust gas using the core-shell support, method for producing the same, and method for purification of exhaust gas using the catalyst for purification of exhaust gas
DE112016001168.7T DE112016001168T5 (de) 2015-03-12 2016-03-01 Kern-schale-träger, verfahren zu seiner herstellung, katalysator zur abgasreinigung unter verwendung des kern-schale-trägers, verfahren zu seiner herstellung und verfahren zur abgasreinigung unter verwendung des katalysators zur abgasreinigung
CN201680014994.XA CN107427822A (zh) 2015-03-12 2016-03-01 核‑壳载体、其制造方法、使用该核‑壳载体的排气净化催化剂、其制造方法和使用所述排气净化催化剂净化排气的方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015049275 2015-03-12
JP2015-049275 2015-03-12
JP2016019455A JP6676394B2 (ja) 2015-03-12 2016-02-04 コアシェル担体及びその製造方法、そのコアシェル担体を用いた排ガス浄化用触媒及びその製造方法、並びに、その排ガス浄化用触媒を用いた排ガス浄化方法
JP2016-019455 2016-02-04

Publications (1)

Publication Number Publication Date
WO2016143722A1 true WO2016143722A1 (fr) 2016-09-15

Family

ID=55650634

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/056908 WO2016143722A1 (fr) 2015-03-12 2016-03-01 Support noyau-enveloppe, son procédé de production, catalyseur de purification des gaz d'échappement utilisant ledit support noyau-enveloppe, son procédé de production, et procédé de purification des gaz d'échappement utilisant le catalyseur de purification des gaz d'échappement

Country Status (1)

Country Link
WO (1) WO2016143722A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018047425A (ja) * 2016-09-21 2018-03-29 新日本電工株式会社 酸素吸放出材料
EP3378557A4 (fr) * 2015-11-17 2019-06-26 Mitsui Mining and Smelting Co., Ltd. Poudre pour catalyseurs, et catalyseur pour purification de gaz d'échappement
CN111372893A (zh) * 2017-11-06 2020-07-03 新日本电工株式会社 吸放氧材料、催化剂、废气净化系统及废气处理方法
CN111420704A (zh) * 2020-03-31 2020-07-17 包头稀土研究院 复合催化剂及其制备方法和用途
WO2023031584A1 (fr) * 2021-08-31 2023-03-09 Johnson Matthey Public Limited Company Alumine incorporée à un métal de transition pour catalyseurs à trois voies améliorés

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005102524A1 (fr) * 2004-04-27 2005-11-03 Toyota Jidosha Kabushiki Kaisha Particule d'oxyde métallique, processus de production de celle-ci et catalyseur de purification des gaz d’évacuation
JP2007144290A (ja) 2005-11-25 2007-06-14 Nissan Motor Co Ltd 排ガス浄化触媒及び排ガス浄化触媒の製造方法
US20100061903A1 (en) * 2007-02-01 2010-03-11 Daiichi Kigenso Kagaku Kogyo Co., Ltd Catalyst system to be used in automobile exhaust gas purification apparatus, exhaust gas purification apparatus using the same and exhaust gas purification method
US20140037524A1 (en) * 2011-02-01 2014-02-06 Umicore Shokubai Japan Co., Ltd. Catalyst for purifying exhaust gas
WO2014087822A1 (fr) * 2012-12-07 2014-06-12 トヨタ自動車株式会社 Matériau d'oxyde composite et catalyseur de purification de gaz d'échappement l'utilisant
WO2015049575A1 (fr) * 2013-10-04 2015-04-09 Toyota Jidosha Kabushiki Kaisha Oxyde composite de type oxyde de cérium-oxyde de zirconium, son procédé de production, et catalyseur pour la purification des gaz d'échappement l'utilisant
EP2959962A1 (fr) * 2014-06-26 2015-12-30 Toyota Jidosha Kabushiki Kaisha Matériau d'oxyde complexe de cérium-zircone et son procédé de production

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005102524A1 (fr) * 2004-04-27 2005-11-03 Toyota Jidosha Kabushiki Kaisha Particule d'oxyde métallique, processus de production de celle-ci et catalyseur de purification des gaz d’évacuation
JP2007144290A (ja) 2005-11-25 2007-06-14 Nissan Motor Co Ltd 排ガス浄化触媒及び排ガス浄化触媒の製造方法
US20100061903A1 (en) * 2007-02-01 2010-03-11 Daiichi Kigenso Kagaku Kogyo Co., Ltd Catalyst system to be used in automobile exhaust gas purification apparatus, exhaust gas purification apparatus using the same and exhaust gas purification method
US20140037524A1 (en) * 2011-02-01 2014-02-06 Umicore Shokubai Japan Co., Ltd. Catalyst for purifying exhaust gas
WO2014087822A1 (fr) * 2012-12-07 2014-06-12 トヨタ自動車株式会社 Matériau d'oxyde composite et catalyseur de purification de gaz d'échappement l'utilisant
EP2930149A1 (fr) * 2012-12-07 2015-10-14 Toyota Jidosha Kabushiki Kaisha Matériau d'oxyde composite et catalyseur de purification de gaz d'échappement l'utilisant
WO2015049575A1 (fr) * 2013-10-04 2015-04-09 Toyota Jidosha Kabushiki Kaisha Oxyde composite de type oxyde de cérium-oxyde de zirconium, son procédé de production, et catalyseur pour la purification des gaz d'échappement l'utilisant
EP2959962A1 (fr) * 2014-06-26 2015-12-30 Toyota Jidosha Kabushiki Kaisha Matériau d'oxyde complexe de cérium-zircone et son procédé de production

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3378557A4 (fr) * 2015-11-17 2019-06-26 Mitsui Mining and Smelting Co., Ltd. Poudre pour catalyseurs, et catalyseur pour purification de gaz d'échappement
US10780423B2 (en) 2015-11-17 2020-09-22 Mitsui Mining & Smelting Co., Ltd. Powder for catalysts and catalyst for exhaust gas purification
JP2018047425A (ja) * 2016-09-21 2018-03-29 新日本電工株式会社 酸素吸放出材料
CN111372893A (zh) * 2017-11-06 2020-07-03 新日本电工株式会社 吸放氧材料、催化剂、废气净化系统及废气处理方法
CN111420704A (zh) * 2020-03-31 2020-07-17 包头稀土研究院 复合催化剂及其制备方法和用途
WO2023031584A1 (fr) * 2021-08-31 2023-03-09 Johnson Matthey Public Limited Company Alumine incorporée à un métal de transition pour catalyseurs à trois voies améliorés
EP4140567A3 (fr) * 2021-08-31 2023-03-29 Johnson Matthey Public Limited Company Alumine incorporée à un métal de transition pour catalyseurs à trois voies améliorés
US11986802B2 (en) 2021-08-31 2024-05-21 Johnson Matthey Public Limited Company Transition metal incorporated alumina for improved three way catalysts

Similar Documents

Publication Publication Date Title
US20180021758A1 (en) Core-shell support, method for producing the same, catalyst for purification of exhaust gas using the core-shell support, method for producing the same, and method for purification of exhaust gas using the catalyst for purification of exhaust gas
CA2562556C (fr) Processus de production d'une particule d'oxyde metallique et un catalyseur de purification des gaz d'evacuation
CA2648314C (fr) Catalyseur pour purification des gaz d'echappement, methode de regeneration pour le catalyseur, et appareil et methode pour purification des gaz d'echappement au moyen du catalyseur
US7202194B2 (en) Oxygen storage material, process for its preparation and its application in a catalyst
US20090286680A1 (en) Exhaust Gas Purification Catalyst and Exhaust Gas Purification Catalyst Member
WO2016143722A1 (fr) Support noyau-enveloppe, son procédé de production, catalyseur de purification des gaz d'échappement utilisant ledit support noyau-enveloppe, son procédé de production, et procédé de purification des gaz d'échappement utilisant le catalyseur de purification des gaz d'échappement
WO2005092481A1 (fr) Materiau de stockage d'oxyde d'azote et catalyseur de stockage d'oxyde d'azote fait de ce materiau
EP3181224B1 (fr) Procédé de production de matériau de stockage d'oxygène, et matériau de stockage d'oxygène
WO2013023010A1 (fr) Catalyseur comprenant de la zircone dopée avec un lanthanide et ses procédés de fabrication
WO2012120349A1 (fr) Catalyseur de purification d'un gaz d'échappement
WO2008067375A1 (fr) Matériaux de stockage de nox, et pièges résistant au vieillissement thermique
JP3265534B2 (ja) 排ガス浄化用触媒
JP2004243305A (ja) 排ガス浄化用触媒
WO2016158656A1 (fr) Catalyseur de purification de gaz d'échappement
JP4938013B2 (ja) 酸素貯蔵材料
WO2007145145A1 (fr) Oxyde INORGANIque et catalyseur de purification de gaz d'échappement produit en l'utilisant
US7625836B2 (en) Heat-resistant oxide
JP4737984B2 (ja) 耐熱性酸化物
JP5827286B2 (ja) 自動車用排ガス浄化触媒
JP2018038999A (ja) 排ガス浄化用触媒
JP3688945B2 (ja) 排気ガス浄化用触媒
WO2022209534A1 (fr) Composition de catalyseur pour purification de gaz d'échappement et catalyseur de purification de gaz d'échappement
JP4969496B2 (ja) 排ガス浄化用触媒
JPWO2008004390A1 (ja) 排ガス浄化用触媒及びその製造方法
JP2001232199A (ja) 排ガス浄化用触媒

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16714029

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15550148

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 112016001168

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16714029

Country of ref document: EP

Kind code of ref document: A1