WO2010101223A1 - 排気ガス浄化触媒及びその製造方法 - Google Patents
排気ガス浄化触媒及びその製造方法 Download PDFInfo
- Publication number
- WO2010101223A1 WO2010101223A1 PCT/JP2010/053568 JP2010053568W WO2010101223A1 WO 2010101223 A1 WO2010101223 A1 WO 2010101223A1 JP 2010053568 W JP2010053568 W JP 2010053568W WO 2010101223 A1 WO2010101223 A1 WO 2010101223A1
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- Prior art keywords
- compound
- catalyst
- noble metal
- exhaust gas
- metal particles
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- 239000001301 oxygen Substances 0.000 claims description 72
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- 229910052788 barium Inorganic materials 0.000 claims description 5
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- 229910052749 magnesium Inorganic materials 0.000 claims description 4
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Classifications
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- 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
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
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Definitions
- the present invention relates to an exhaust gas purification catalyst suitable for purifying exhaust gas from an internal combustion engine and a method for producing the same.
- a catalyst in which transition metals such as cerium (Ce) functioning as an oxygen storage material and manganese (Mn) functioning as an active oxygen supply material are arranged in the vicinity of noble metal particles by an impregnation method ( Patent Document 1).
- transition metals such as cerium (Ce) functioning as an oxygen storage material and manganese (Mn) functioning as an active oxygen supply material
- Patent Document 1 the durability of the noble metal particles is improved by suppressing the fluctuation of the atmosphere around the noble metal particles with the transition metal.
- the exhaust gas purification catalyst produced by such a method can be expected to improve the activity of the noble metal particles in addition to the improvement of the durability of the noble metal particles.
- the exhaust gas purification catalyst manufactured using the impregnation method does not become fine particles even if the noble metal particles and the transition metal particles can be brought into contact with each other.
- the noble metal particles and the transition metal particles become fine particles, they cannot be contacted or the amount that can be contacted is small.
- the durability since it is difficult to arrange the transition metal particles as designed in the vicinity of the noble metal particles, the durability has not been sufficiently improved.
- the present invention has been made in view of such problems of the conventional technology. And the objective is to provide the exhaust-gas purification catalyst which can optimize arrangement
- the exhaust gas purification catalyst according to the first aspect of the present invention is a second catalyst having noble metal particles, a first compound supporting the noble metal particles, and a second compound that is disposed in non-contact with the noble metal particles and has an oxygen storage capacity. And an average distance between the first compound and the second compound is 5 nm to 300 nm.
- the method for producing an exhaust gas purification catalyst according to the second aspect of the present invention includes a step of individually or integrally pulverizing the first compound and the second compound, and the pulverized first compound and second compound. And a step of simultaneously including the compound of (3) with a precursor of a third compound.
- FIG. 1 is a schematic view showing an exhaust gas purification catalyst according to an embodiment of the present invention
- FIG. 1 (a) is a perspective view showing an exhaust gas purification catalyst
- FIG. 1 (b) is a perspective view of FIG. It is the schematic which expanded the part of the code
- FIG.1 (c) is the schematic which shows catalyst powder.
- FIG. 2 is a photomicrograph showing the distance between the first compound and the second compound in the catalyst powder.
- FIG. 3 is a graph showing the relationship between the distance between the first compound and the second compound and the appearance frequency.
- FIG. 4 is a graph showing the relationship between the distance between the first compound and the second compound and the appearance frequency.
- FIG. 5 is a schematic view showing examples of catalyst powders having different degrees of dispersion.
- FIG. 6 is a graph showing the relationship between the degree of dispersion and the NOx conversion rate.
- FIG. 7 is a graph showing the relationship between the distance between the first compound and the second compound and the NOx conversion rate.
- FIG. 1 shows an exhaust gas purification catalyst (hereinafter also referred to as catalyst) 1 according to an embodiment of the present invention.
- the exhaust gas purification catalyst 1 includes a honeycomb carrier (refractory inorganic carrier) 2 having a plurality of cells 2a. The exhaust gas flows through each cell 2a along the exhaust gas flow direction F, and is purified by contacting with the catalyst layer there.
- the exhaust gas purification catalyst 1 is formed by forming a plurality of catalyst layers 3 and 4 on the inner surface of the carrier 2 as shown in FIG. As shown in FIG. 1 (c), the catalyst layer is disposed in contact with the noble metal particles 6, the first compound 7 supporting the noble metal particles 6, and the noble metal particles 6, and has an oxygen storage capacity.
- the catalyst powder 5 containing the 2nd compound 9 to have is included. Further, the average distance between the first compound 7 and the second compound 9 is 5 nm to 300 nm.
- the first compound 7 has an effect of suppressing the movement of the noble metal particles by contacting the noble metal particles 6, and hereinafter, the one having such an effect is referred to as an anchor material.
- an oxygen storage material that is disposed in the vicinity of noble metal particles and that adsorbs and desorbs active oxygen when the exhaust gas atmosphere fluctuates is a particularly essential material for improving the purification performance of the catalyst. It is.
- the amount of OSC material in the catalyst oxygen absorption / release amount
- the oxygen absorption / release rate of the OSC material oxygen absorption / release rate
- the three conditions of distance are extremely important.
- the present invention pays particular attention to the distance (3) between the noble metal particle and the OSC material.
- the amount of the OSC material (1) when the amount of the OSC material (1) is increased or decreased, it is considered that there is an optimum amount. That is, if the amount of the OSC material in the catalyst is less than the optimum amount, sufficient active oxygen cannot be supplied to the noble metal particles when the atmosphere becomes rich, such as during acceleration, and the purification performance of HC and CO mainly decreases. To do. On the other hand, if the amount of OSC material is too large relative to the optimum amount, the active oxygen adsorbed by the OSC material is greatly reduced when the OSC material fluctuates from a lean atmosphere to a stoichiometric or rich atmosphere, such as acceleration immediately after deceleration or fuel injection performed during deceleration. It is released excessively, and the NOx purification performance mainly decreases.
- the general amount of OSC material varies depending on the type of noble metal in the catalyst and the use ratio of noble metal, but is 5 to 100 g / L in terms of CeO 2 per catalyst volume.
- the amount of oxygen absorbed / released from the OSC material can generally be determined by simultaneous differential thermal-thermogravimetric measurement (TG-DTA), temperature reduction measurement (TPR measurement), or the like.
- TPR temperature reduction measurement
- the OSC material is pretreated in an oxygen atmosphere, the temperature is raised in a reducing atmosphere such as H 2 circulation, and the amount of released H 2 O or CO 2 is quantified. It is possible to measure the quantity.
- the precious metal particles outside the range cannot make effective use of active oxygen, and there is a concern that the precious metal particles used are not sufficiently utilized for the purification of CO and HC or NOx.
- the distance (3) between the noble metal particle and the OSC material attention was paid to the distance (3) between the noble metal particle and the OSC material.
- the amount of the OSC material in the exhaust gas purification catalyst is the same, the supply efficiency of active oxygen increases as the distance between the noble metal particle and the OSC material is shorter. Therefore, when the atmosphere changes, active oxygen can be supplied to the noble metal particles in a shorter time. Therefore, it is considered that the fact that the distance between the noble metal particle and the OSC material is close has the same performance improvement effect as (2) improvement of the oxygen absorption / release rate among the above three conditions.
- the structure in which the noble metal particles are supported on the OSC material may not always be optimal for the following reasons.
- the OSC material having the ability to adsorb and desorb oxygen generally has a reduced specific surface area due to crystal growth in a high-temperature exhaust gas atmosphere as compared with known alumina or the like as a base material supporting metal particles. Is big. Therefore, when the noble metal particles are supported on the OSC material, the active surface area is likely to decrease due to aggregation of the noble metal particles.
- Rhodium has a high catalytic activity in the reduced state and tends to decrease in the highly oxidized state.
- active oxygen is supplied around the noble metal particle-OSC material interface, and the noble metal particles are in a highly oxidized state, resulting in a decrease in catalyst performance. .
- the present invention improves purification performance by preventing any decrease in active surface area due to aggregation of noble metal particles, high oxidation state of noble metal particles, and delay in supply of active oxygen to noble metal particles. It is an invention aimed at making it happen.
- one of the constituent features of the present invention is that the average distance between the first compound supporting the noble metal particles and the second compound having oxygen storage capacity is 5 nm to 300 nm. .
- the oxygen supply efficiency to the noble metal particles is increased, and the deterioration of the catalyst performance due to excessive oxygen is prevented.
- the average distance is less than 5 nm, the precious metal particles may be in a highly oxidized state and the purification performance may be deteriorated.
- the average distance exceeds 300 nm the supply of oxygen to the noble metal particles becomes insufficient, and the purification performance may also deteriorate.
- a method for measuring the distance between the first compound and the second compound will be described later.
- the catalyst layer is formed from the finely pulverized raw material in this way, the pore volume in the catalyst layer formed by the voids between the particles is reduced, so that the gas diffusibility is likely to be reduced. Since peeling tends to occur, the performance may be degraded.
- an OSC material (second compound) separately contained from the first compound supporting the noble metal particles is disposed in the catalyst powder. Therefore, the distance between the noble metal particles and the OSC material can be in the range of 5 nm to 300 nm without causing problems of gas diffusibility and catalyst layer peeling when the catalyst layer is formed.
- the catalyst powder 5 shown in FIG. 1 (c) includes both the first compound 7 and the second compound 9 in addition to the first compound 7 and the second compound 9 that have contacted the noble metal particles 6.
- the catalyst unit 11 which consists of the secondary particle of the noble metal particle 6 and the 1st compound 7, and the secondary catalyst of the 2nd compound 9 were contained.
- the unit 12 is included.
- the first compound 7 and the second compound 9 may exist as primary particles in a region separated by the third compound 10.
- the catalyst structure can be maintained after the endurance by simultaneously enclosing the first compound 7 as the anchor material and the second compound 9 as the OSC material by the third compound 10.
- the third compound 10 prevents the first compound 7 carrying the noble metal particles 6 and the second compound 9 that is the OSC material from aggregating and contacting each other, high catalytic performance is maintained even after durability. Can be maintained.
- the catalyst powder 5 will be described in more detail.
- the noble metal particles 6 and the first compound 7 are chemically bonded to each other when the noble metal particles 6 and the first compound 7 are brought into contact with each other.
- the movement of the noble metal particles 6 is suppressed.
- the noble metal particles 6 pass beyond the section separated by the third compound 10. Physically restrains movement. That is, since the 3rd compound 10 acts as a partition material, it can control that noble metal particles 6 oxidize, move to a gaseous phase, and aggregate with other noble metal particles 6.
- the first compounds 7 come into contact with each other and aggregate over the section separated by the third compound 10. Suppress. This not only prevents aggregation of the first compound 7, but also prevents aggregation of the noble metal particles 6 supported on the first compound 7.
- the physical movement of the second compound 9 is also suppressed by covering and enclosing the particles of the second compound 9 having oxygen storage capacity with the third compound 10. To do. That is, by including the second compound 9 in the section separated by the third compound 10, the second compounds 9 are brought into contact with each other and aggregated across the section separated by the third compound 10. It can suppress and the fall of a specific surface area can be prevented.
- the third compound 10 used in the catalyst powder 5 does not completely surround the first compound 7 and the second compound 9. That is, the third compound 10 has pores enough to allow exhaust gas and active oxygen to pass through while covering the extent of suppressing the physical movement of each of the first compound 7 and the second compound 9. ing.
- the third compound 10 appropriately includes the first compound 7 and the second compound 9, and suppresses aggregation of the respective particles, Since it has a plurality of pores 10a, exhaust gas and active oxygen can pass through. Therefore, the average pore diameter of the pores 10a is preferably smaller than the average particle diameter of the first compound 7 and the second compound 9.
- the average pore diameter of the pores 10a is preferably 30 nm or less, and more preferably 10 nm to 30 nm. This pore diameter can be determined by a gas adsorption method.
- One method for supplying active oxygen to the active site without increasing the total amount of OSC material in the catalyst layer is to use an OSC material having an oxygen storage capacity as an anchor material supporting noble metal particles.
- an OSC material having an oxygen storage capacity as an anchor material supporting noble metal particles.
- oxidation of the noble metal particles tends to proceed at the noble metal particle-OSC material interface due to the supply of active oxygen to the noble metal particles.
- the average distance between the first compound supporting the noble metal particles and the second compound having the oxygen storage capacity is controlled to be a constant distance, and the same catalyst powder is used.
- the active oxygen released from the OSC material can be efficiently supplied to the active point.
- the first compound 7 is brought into contact with the noble metal particles 6 and chemically bonded thereto, so that the movement of the noble metal particles 6 is suppressed.
- the third compound 10 physically suppresses the movement of the noble metal particles 6 by including the periphery of the first compound 7 and the second compound 9 that are in contact with the noble metal particles 6.
- the distance measurement between the first compound and the second compound in the catalyst powder is as follows: (1) TEM-EDX analysis or HAADF-STEM analysis of catalyst powder, (2) contour extraction of the first compound and the second compound from the image; (3) Set a circle approximation and center point from the surface area based on the extracted contour, (4) Find nearest center point and measure distance, It can be done with the procedure.
- the distance measuring method is not limited to such a method, and any other method may be used as long as it is an objective and reproducible method.
- TEM-EDX analysis or HAADF analysis of catalyst powder The catalyst powder is embedded in an epoxy resin, and after curing, an ultrathin section is prepared with an ultramicrotome. Using the section, the catalyst powder was observed with a transmission electron microscope (TEM) or HAADF-STEM (High-Angle Angular Dark-Field Scanning Transmission Electron Microscopy), and the first compound, the second compound, and the second compound. Discrimination of 3 compounds is performed.
- TEM transmission electron microscope
- HAADF-STEM High-Angle Angular Dark-Field Scanning Transmission Electron Microscopy
- Discrimination of 3 compounds is performed.
- the analysis conditions when using TEM-EDX will be described. First, focus on the contrast (shadow) part in the obtained image, analyze the element type of that part, find the Identify compound particles containing elements.
- the first compound and the second compound may overlap in element type.
- the presence or absence of the noble metal type is determined by EDX (energy dispersive X-ray analyzer). By detection, it can be distinguished from the second compound.
- EDX energy dispersive X-ray analyzer
- the noble metal particle size is smaller than the X-ray beam diameter of EDX
- noble metal may not be detected.
- the first compound and the second compound contain cerium (Ce) or praseodymium (Pr) as the OSC material
- the first compound and the second compound obtained in advance in the preparation stage It is preferable to make a determination by comparing the content of the carbon and the detected intensity ratio of Ce or Pr. In the case of a HAADF-STEM image, it can be determined by contrast.
- contours of the first compound and the second compound are extracted from the image obtained by the analysis of (1) above.
- image processing software may be used, and the extraction may be automatically performed according to contrast.
- the image may be copied to an OHP sheet and extracted manually.
- the distance between the first compound and the second compound when the first compound and the second compound are primary particles, the distance between the primary particles is the interparticle distance.
- the catalyst unit 11 including secondary particles of the noble metal particles 6 and the first compound 7 and the secondary particles of the second compound 9 are used.
- the distance between the promoter unit 12 is the interparticle distance.
- the first compound and the second compound are included by the third compound, and the average secondary particle size of the first compound and the second compound is 5 to 300 nm.
- the dispersity described later is 40% or more, it can be considered that the first compound and the second compound are uniformly dispersed. That is, since it is physically difficult to create a catalyst powder in which the first compound and the second compound are arbitrarily biased under the above conditions, in such a case, the first Strict discrimination between the compound and the second compound can be omitted.
- FIG. 2 shows an example of a TEM-EDX photograph of the catalyst powder.
- the image obtained by using TEM-EDX was subjected to image processing, and the first compound 7 and the second compound 9 were subjected to the measurement of each particle. Extract contours.
- the surface area of each particle is obtained, and a circle having the same area as this surface area is assumed.
- the second compound 9 closest to the specific first compound 7 is searched, and the center distance of each circle is measured.
- a straight line connecting the first compound 7 and the second compound 9 is indicated by a solid line
- a straight line connecting the first compounds 7 or the second compounds 9 is indicated by a broken line.
- FIG. 3 is a graph in which the horizontal axis represents the distance between the first compound 7 and the second compound 9 obtained by the above measurement method, and the vertical axis represents the appearance frequency.
- the catalyst of the present invention has a shorter distance between the anchor material (first compound) and the OSC material (second compound) than the conventional catalyst. As a result, active oxygen is more efficiently supplied to the noble metal particles than the conventional catalyst, and excellent purification performance can be exhibited.
- the ratio between the amount of the oxygen storage material contained in the first compound and the amount of the oxygen storage material contained in the second compound satisfies the relationship of the following formula (1).
- noble metal particles such as rhodium whose catalytic performance is improved in a reduced state
- the OSC material when the OSC material is contained in a large amount in the first compound, the noble metal particles are caused by active oxygen in the OSC material. Becomes a highly oxidized state. As a result, the performance of the noble metal particles tends to be reduced.
- noble metal particles can be obtained while the active oxygen is sufficiently supplied by adding the OSC material to the second compound and further setting the average distance between the first compound and the second compound to 5 nm to 300 nm. The reduced state of can be maintained.
- the catalyst of the present invention is not limited to the case where the first compound does not contain an OSC material, and may contain a small amount of an OSC material. And by adjusting the amount of the OSC material of the first compound and the second compound so as to satisfy the above formula (1), it is possible to suppress the oxidative deterioration of the noble metal particles while securing the amount of active oxygen. .
- the molar ratio of the amount of the OSC material in the second compound to the first compound is 1.5 or less, the amount of the OSC material in the first compound is relatively increased, and the noble metal particles are oxidized. There is a risk that the performance will deteriorate due to progress.
- the average secondary particle size of the first compound is preferably 300 nm or less, and the average secondary particle size of the second compound is preferably 1000 nm or less.
- the average secondary particle diameter of the first compound exceeds 300 nm, the function as an anchor material for holding fine noble metal particles may be rapidly reduced.
- the average secondary particle diameter of the second compound exceeds 1000 nm, it becomes difficult to include the first compound and the second compound simultaneously with the third compound.
- the average secondary particle diameter of the first compound is 300 nm or less and the average secondary particle diameter of the second compound is 1000 nm or less, the noble metal particles remain in a reduced state. , Active oxygen can be supplied.
- the average secondary particle diameter of the first compound is more preferably 200 nm or less.
- the average secondary particle diameter of the second compound is more preferably 300 nm or less.
- the surface area of the second compound is greatly improved, so that the oxygen supply rate is improved and the catalyst performance can be enhanced.
- the average secondary particle size of the first compound and the second compound can be obtained by applying a slurry containing these particles to a laser diffraction particle size distribution measuring device in the process of producing the catalyst powder.
- the average secondary particle diameter in this case means a median diameter (D50).
- the average secondary particle diameter of these particles can also be measured from the TEM photograph of the produced catalyst powder.
- the catalyst powder 5 preferably has an average particle size of 6 ⁇ m or less.
- the average particle size of the catalyst powder is the particle size of the catalyst powder 5 when the inner wall surface of the through hole of the honeycomb-shaped refractory inorganic support 2 is coated with the catalyst powder.
- the average particle diameter of the catalyst powder 5 exceeds 6 ⁇ m, the distance from the outer peripheral portion to the central portion of the catalyst powder 5 is increased, and the gas diffusibility to the powder central portion is remarkably reduced, so that the purification performance may be reduced. is there.
- the thickness exceeds 6 ⁇ m, peeling or unevenness easily occurs when the honeycomb carrier is coated.
- the average particle diameter of the catalyst powder 5 is more preferably in the range of 1 ⁇ m to 4 ⁇ m, which can form appropriate inter-powder voids and can further suppress peeling.
- the catalyst powder 5 preferably has a degree of dispersion of the first compound 7 and the second compound 9 in the catalyst powder of 40% or more.
- the degree of dispersion can be obtained from Equation (2).
- ⁇ is a standard deviation of the distribution of the distance between the first compound 7 and the second compound 9 in the catalyst powder 5.
- Av. Is the average distance between the first compound 7 and the second compound 9 in the catalyst powder 5.
- FIG. 4 is a graph showing the relationship between the distance between the first compound 7 and the second compound 9 in the catalyst powder 5 and the appearance frequency of the distance.
- ⁇ the degree of dispersion
- the standard deviation is ⁇ means that 68.26% of the distance between the first compound 7 and the second compound 9 is distributed within the average distance Av (nm) ⁇ ⁇ (nm). Means that.
- FIG. 5 shows a schematic diagram of an example of catalyst powder having a high degree of dispersion (FIG. 5A) and a schematic diagram of an example of catalyst powder having a low degree of dispersion (FIG. 5B).
- the degree of dispersion of the catalyst is 100% (this means that the distance variation is 0). Means).
- the degree of dispersion of the catalyst approaches 0%. That is, when all the distances between the first compound and the second compound are geometrically evenly arranged, ⁇ is 0 and the degree of dispersion is 100%.
- the degree of dispersion defined in this way is preferably 40% or more. If the degree of dispersion is 40% or more, the distance between the particles is sufficiently maintained, and the deviation is small, so that aggregation of the compounds after durability is suppressed.
- This dispersity is determined by the first compound and the second compound immediately before the slurry mixed with the first compound and the second compound, and further the precursor of the third compound in the process of producing the catalyst powder 5. There is a correlation with the degree of aggregation. Since the degree of aggregation depends on the stirring force of the slurry, the degree of dispersion can be improved by vigorously stirring the slurry.
- the main component may be at least one selected from among the above.
- Al 2 O 3 and ZrO 2 are excellent in high-temperature heat resistance and can maintain a high specific surface area, it is preferable that Al 2 O 3 or ZrO 2 is a main component in the particles of the first compound 7.
- the main component means a component having a content of 50 atomic percent or more in the particles.
- the second compound 9 preferably contains at least one of cerium (Ce) and praseodymium (Pr) having oxygen storage / release ability.
- the second compound is preferably composed mainly of a compound having a high oxygen storage / release capability such as cerium oxide (CeO 2 ) or praseodymium oxide (Pr 6 O 11 ).
- Ce and Pr are materials that take oxides having a plurality of valences, change the oxidation number due to fluctuations in the exhaust gas atmosphere, and can store and release active oxygen.
- the noble metal particle 6 at least one selected from platinum (Pt), palladium (Pd), rhodium (Rh), gold (Au), silver (Ag), iridium (Ir) and ruthenium (Ru) is used.
- platinum (Pt), palladium (Pd), and rhodium (Rh) can exhibit high NOx purification performance.
- the noble metal particles 6 are rhodium (Rh) and the first compound 7 is an oxide containing at least zirconium (Zr).
- Rh tends to have poor catalyst performance in a highly oxidized state, high oxidation and aggregation of Rh can be suppressed by appropriately adjusting the distance between the first compound and the second compound.
- Rh binding energy analysis by X-ray photoelectron spectroscopy XPS
- the 3d5 orbital coupling energy of Rh is known to have a metal state Rh of 307.2 eV and a high oxidation state Rh of around 310.2 eV.
- an oxide such as Al 2 O 3 or ZrO 2
- the catalytic performance is lowered when the 3d5 orbital coupling energy of Rh is 308.8 eV or more. Therefore, the 3d5 orbital coupling energy is 308. It is desirable that it is 8 eV or less.
- the 3d5 orbital coupling energy of Rh can be reduced to 308.8 eV or less.
- a hydrocarbon contained in oil mist or the like derived from a pump for keeping the inside of the X-ray photoelectron spectrometer at a high vacuum is used, and the C1s peak of the hydrocarbon is compared with a literature value for correction.
- the first compound 7 is preferably an oxide containing zirconium as a main component.
- the first compound 7 is mainly composed of alumina or the like, rhodium and alumina are dissolved, rhodium is highly oxidized, and the catalytic activity may be lowered.
- Zr is contained in an oxide containing Zr, more preferably 50% or more by atomic percent in the first compound, high oxidation and aggregation of Rh can be suppressed.
- Examples of such an oxide mainly containing Zr include zirconia (ZrO 2 ), lanthanum-added zirconia (Zr—La—O x ), and lanthanum-ceria-added zirconia (Zr—La—Ce—O x ). be able to.
- the third compound 10 preferably contains at least one of aluminum (Al) and silicon (Si).
- a material capable of including the first compound and the second compound and ensuring gas permeability is preferable.
- a compound containing at least one of Al and Si such as alumina (Al 2 O 3 ) and silica (SiO 2 ), has a large pore volume and can ensure high gas diffusibility.
- the third compound may be a composite compound (composite oxide) of Al and Si.
- the third compound 10 can permeate the exhaust gas and active oxygen while covering the extent to suppress the physical movement of each of the first compound 7 and the second compound 9. A plurality of pores 10a.
- alumina or silica can be used.
- boehmite AlOOH
- the first compound 7 and the second compound 9 carrying the noble metal particles 6 are put into a slurry in which boehmite is dispersed in a solvent such as water and stirred. Thereby, boehmite adheres around the first compound 7 and the second compound 9.
- boehmite is dehydrated and condensed around the first compound 7 and the second compound 9, and a third compound made of alumina derived from boehmite (for example, ⁇ -alumina) is obtained. It is formed.
- a third compound made of boehmite-derived alumina covers the first compound 7 and the second compound 9 and has many pores of 30 nm or less, and thus has excellent gas permeability. ing.
- the third compound is made of silica
- silica sol and zeolite are used as precursors. That is, the first compound 7 and the second compound 9 supporting the noble metal particles 6 are put into a slurry in which silica sol and zeolite are dispersed in a solvent, stirred, dried and fired, whereby the third compound made of silica is obtained. Is formed.
- the third compound composed of such silica sol and zeolite-derived silica also covers the first compound 7 and the second compound 9 and has many pores of 30 nm or less, so that the gas permeability is improved. Are better.
- the first compound and the second compound is an oxide further including at least one selected from iron (Fe), manganese (Mn), cobalt (Co), and nickel (Ni).
- the first compound 7 is mainly composed of alumina or zirconia
- the second compound is mainly composed of cerium oxide or praseodymium oxide.
- the transition metal is desirable to contain the transition metal as an additive in at least one of the first compound and the second compound. By containing at least one of these transition metals, the catalytic performance, particularly the CO and NO purification rate, can be improved by the active oxygen contained in the transition metal.
- At least one of the first compound and the second compound includes at least one NOx adsorbent selected from barium (Ba), magnesium (Mg), calcium (Ca), strontium (Sr), and sodium (Na). Furthermore, it is preferable to include. Any compound containing these elements acts as a NOx adsorbent. Therefore, NOx purification performance can be improved by including the NOx adsorbent in at least one of the first compound and the second compound. This is because the NOx adsorption reaction is highly sensitive to gas contact.
- a catalyst containing these NOx adsorbents is suitable as a catalyst for a lean burn engine in which a large amount of NOx is generated than an engine that burns near the stoichiometric air-fuel ratio.
- the catalyst powder 5 is applied to the inner surface of the refractory inorganic carrier 2 as shown in FIG. It is mounted in the exhaust passage of the internal combustion engine.
- the catalyst layer applied to the refractory inorganic carrier may be composed of a plurality of layers having different component compositions. Further, when a plurality of catalyst layers 3 and 4 are formed on the refractory inorganic carrier, it is only necessary that at least one of the catalyst layers 3 and 4 contains the catalyst powder 5.
- the exhaust gas purifying catalyst of the present invention prepares precious metal particles, a first compound, a second compound, and, if necessary, a third compound in advance.
- the catalyst powder can be obtained by the step of supporting the noble metal particles on the first compound and the step of mixing the first compound and the second compound supporting the noble metal particles. Further, when the catalyst contains a third compound, the first compound and the second compound supporting noble metal particles are mixed, and then the third compound is added and mixed to obtain a catalyst powder.
- the first compound and the second compound are pulverized integrally or individually, and then the pulverized first compound and second compound are converted into precursors of the third compound. It is further preferable to include a step of simultaneous inclusion.
- first, noble metal particles 6 are supported on the first compound 7.
- the noble metal particles can be supported by an impregnation method.
- supported the noble metal particle 6 on the surface is grind
- the second compound 9 is also pulverized using a bead mill or the like to obtain a desired particle size.
- the first compound 7 and the second compound 9 may be pulverized in a mixed state or may be pulverized individually. When individually pulverized, the first compound and the second compound can each have a desired secondary particle size.
- the crushing step can be omitted by using a fine raw material such as an oxide colloid as the raw material of the first compound 7 and / or the second compound 9.
- the clathrate containing the first compound and the clathrate containing the second compound are mixed.
- the first compound and the second compound are put into a slurry in which the precursor of the third compound is dispersed and stirred.
- the precursor of the third compound adheres around the first compound 7 and the second compound 9.
- each particle is dispersed in the slurry, and as a result, the degree of dispersion can be improved.
- the mixed slurry is dried and calcined, whereby the catalyst powder 5 in which the third compound is formed around the first compound 7 and the second compound 9 can be obtained.
- the obtained catalyst powder 5 is pulverized.
- This pulverization may be either wet or dry.
- the catalyst powder 5 is mixed with a solvent such as ion exchange water and stirred, and then pulverized using a ball mill or the like to obtain a catalyst slurry.
- a binder is added to the catalyst slurry as necessary.
- the average particle size (D50) of the catalyst powder 5 in the catalyst slurry is preferably 6 ⁇ m or less as described above.
- the catalyst slurry is applied to the inner surface of the honeycomb carrier, dried and fired, whereby an exhaust gas purification catalyst can be obtained.
- the catalyst powders of Examples 1 to 14 and Comparative Examples 1 to 3 shown in Table 1 and the catalyst powders of Examples 15 to 18 shown in Table 2 were prepared and applied to the inner wall surface of the honeycomb carrier.
- the catalyst of each Example and comparative example shown in Table 1 and Table 2 was produced as follows.
- Example 1 The first compound powder having a specific surface area of about 70 m 2 / g was impregnated with a rhodium nitrate solution so that the loading concentration was 1.0 wt%. This was dried at 150 ° C. all day and night, and then calcined at 400 ° C. for 1 hour to obtain a first compound having a rhodium carrying concentration of 1.0 wt%. Then, the first compound carrying rhodium was pulverized to obtain an average particle diameter (D50) shown in Table 1. The average particle size was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd.
- the second compound powder having a specific surface area of 80 m 2 / g was pulverized to obtain an average particle diameter (D50) shown in Table 1.
- the apparatus similar to the measurement of a 1st compound was used for the measurement of this average particle diameter.
- boehmite as a precursor of the third compound, nitric acid and water were mixed and stirred for 1 hour to prepare a precursor slurry.
- each of the pulverized Rh-supported first compound and the pulverized second compound is slowly added to the precursor slurry, and the mixture is further stirred for 2 hours using a high-speed stirrer to obtain a mixed slurry. It was. Thereafter, this mixed slurry was rapidly dried, further dried at 150 ° C. for a whole day and night to remove moisture, and further calcined in air at 550 ° C. for 3 hours to obtain the catalyst powder of Example 1.
- the catalyst slurry was deposited on the Pt-coated catalyst carrier, excess slurry in the cell was removed with an air stream, dried at 130 ° C., and calcined at 400 ° C. for 1 hour. As a result, a catalyst obtained by coating 50 g / L of the catalyst layer containing Rh on the catalyst layer containing 100 g / L of Pt was obtained.
- Example 2 In Example 2, the Rh loading concentration in the first compound powder in Example 1 was 1.4 wt%. Furthermore, the weight ratio of the total amount of the first compound powder and the second compound powder to the third compound (Al 2 O 3 ) was set to 50:50.
- the material composition of the first compound and the second compound was as shown in Table 1. Except this, it is the same as the first embodiment.
- the catalyst of Example 2 contains yttrium (Y) in the second compound for the purpose of improving the heat resistance of the second compound.
- Examples 3 to 12 are the same as Example 1 except that the material composition and secondary particle size of the first compound and the second compound in Example 1 are as described in Table 1.
- the catalyst of Example 7 contains neodymium (Nd) in the second compound, and the catalyst of Example 12 contains yttrium (Y) in the second compound, in order to improve the heat resistance of the second compound. It is included.
- Example 13 In Example 13, a composite oxide colloid having a primary particle size of 21 nm as the first compound and a primary particle size of 65 nm as the second compound was used, and rhodium was supported only on the first compound. And it is the same as that of Example 1 except the grinding
- Example 14 is the same as Example 1 except that a commercially available silica sol was used instead of boehmite slurry as a precursor of the third compound in the preparation of the catalyst slurry in Example 1.
- the secondary particle size and the like are the values described in Table 1.
- Comparative Example 1 is an example in which the OSC material is included in the catalyst layer formed on the monolith support, not in the catalyst powder.
- the first compound powder having a specific surface area of about 70 m 2 / g was impregnated with a rhodium nitrate solution so that the loading concentration was 1.0 wt%. This was dried at 150 ° C. all day and night, and then calcined at 400 ° C. for 1 hour to obtain a first compound having a rhodium carrying concentration of 1.0 wt%. Then, the first compound carrying rhodium was pulverized to obtain an average particle diameter (D50) shown in Table 1. In addition, the apparatus similar to Example 1 was used for the measurement of this average particle diameter.
- this catalyst powder 100 g of Zr—Ce—O x powder, 25 g of alumina sol, 230 g of water, and 10 g of nitric acid were added to a magnetic ball mill and mixed to obtain a catalyst slurry.
- the catalyst slurry was adhered onto the catalyst carrier coated with Pt, excess slurry in the cell was removed with an air stream, dried at 130 ° C., and then fired at 400 ° C. for 1 hour.
- a catalyst obtained by coating 50 g / L of the catalyst layer containing Rh on the catalyst layer containing 100 g / L of Pt was obtained.
- Comparative Example 2 is an example in which the first compound and the second compound are not covered simultaneously with the third compound but are covered separately. Note that the degree of dispersion of the catalyst of Comparative Example 2 is the value of the powder in which the first compound is clathrated with the third compound.
- the first compound powder having a specific surface area of about 70 m 2 / g was impregnated with a rhodium nitrate solution so that the loading concentration was 1.0 wt%. This was dried at 150 ° C. all day and night, and then calcined at 400 ° C. for 1 hour to obtain a first compound having a rhodium carrying concentration of 1.0 wt%. Then, the first compound carrying rhodium was pulverized to obtain an average particle diameter (D50) shown in Table 1. In addition, the apparatus similar to Example 1 was used for the measurement of this average particle diameter.
- the second compound was pulverized to obtain an average particle size (D50) described in the table.
- the apparatus similar to Example 1 was used for the measurement of this average particle diameter.
- the catalyst slurry was deposited on the Pt-coated catalyst carrier, excess slurry in the cell was removed with an air stream, dried at 130 ° C., and calcined at 400 ° C. for 1 hour.
- a catalyst obtained by coating 50 g / L of the catalyst layer containing Rh on the catalyst layer containing 100 g / L of Pt was obtained.
- Comparative Example 3 is an example in which the second compound is not included and the noble metal particles are supported on the first compound having oxygen storage capacity.
- the first compound powder having a specific surface area of about 70 m 2 / g was impregnated with a rhodium nitrate solution so that the loading concentration was 1.0 wt%. This was dried at 150 ° C. all day and night, and then calcined at 400 ° C. for 1 hour to obtain a first compound having a rhodium carrying concentration of 1.0 wt%. Then, the first compound carrying rhodium was pulverized to obtain an average particle diameter (D50) shown in Table 1. In addition, the apparatus similar to Example 1 was used for the measurement of this average particle diameter.
- this catalyst powder 100 g of Al 2 O 3 powder, 25 g of alumina sol, 230 g of water, and 10 g of nitric acid were added to a magnetic ball mill and mixed to obtain a catalyst slurry.
- Example 15 to 18 the catalyst carrier having a catalyst layer containing Pt prepared in advance in Example 1 was subjected to the following treatment, and Ba was contained in the catalyst layer containing Pt. That is, the catalyst carrier coated with Pt was immersed in a solution in which pure water and an aqueous barium acetate solution (concentration: 40 wt%) were mixed for a certain period of time, then water was distilled off and dried at 400 ° C. for 1 hour. Thereby, a catalyst carrier having a catalyst layer containing Pt and Ba was prepared. The other steps are the same as in Example 1.
- Examples 16 to 18 used the first compound and / or the second compound containing Ba, Mg, and Na, which are NOx adsorbents, respectively.
- Examples 1 to 14 and Comparative Examples 1 to 3 were subjected to endurance treatment and then examined for NOx conversion.
- a catalyst is attached to an exhaust system of a gasoline engine having a displacement of 3500 cc, the catalyst inlet temperature is set to 800 ° C., and the system is operated for 50 hours. Unleaded gasoline was used as the fuel.
- the NOx conversion rate was measured according to Equation (3) with a catalyst attached to the exhaust system of a gasoline engine with a displacement of 3500 cc and a catalyst inlet temperature of 400 ° C.
- the distance between the first compound and the second compound in each catalyst was measured with a TEM-EDX analyzer (HF-2000 manufactured by Hitachi, Ltd.).
- the acceleration voltage at this time was 200 kV It was.
- the cutting conditions by the ultra microtome were normal temperature.
- the contours of the first compound and the second compound were extracted from the image obtained from the TEM-EDX analyzer using an image analyzer (KS-400 manufactured by Carl Zeiss Co., Ltd.).
- the area between the first compound and the second compound is calculated by calculating the area based on the extracted contour, setting the circle approximation and the center point, searching for the nearest center point, and measuring the distance.
- the degree of dispersion of the catalyst was determined based on the formula described above.
- Table 1 shows the NOx conversion rate after the endurance treatment for the catalysts of Examples 1 to 14 and Comparative Examples 1 to 3, the distance between the first compound and the second compound in each catalyst, and the dispersion of the catalyst. It was written together with the degree.
- Example 1 the average distance between the first compound and the second compound was 135 nm. Moreover, the ratio of the oxygen storage material amount (mol) in the first compound to the oxygen storage material amount (mol) in the second compound exceeded 100. Furthermore, the average secondary particle diameter of the first compound was 135 nm, and the average secondary particle diameter of the second compound was 220 nm. The average particle diameter of the catalyst powder containing the noble metal particles was 2.7 ⁇ m, and the degree of dispersion was 56%. Further, in the exhaust gas purification test, an excellent purification performance with a NOx conversion rate of 93% was shown.
- Example 2 has oxygen storage capacity because the first compound supporting the noble metal particles contains zirconium as a main component and cerium.
- the average distance between the first compound and the second compound was 145 nm.
- the ratio of the oxygen storage material amount (mol) in the first compound to the oxygen storage material amount (mol) in the second compound was 2.9.
- the NOx conversion rate showed the outstanding purification performance of 97%.
- Example 3 since the first compound and the second compound are the same compound, the oxygen storage material amount (mol) in the first compound relative to the oxygen storage material amount (mol) in the second compound.
- the ratio is 1.0. Therefore, the amount of Ce in the first compound is relatively large, and as a result, Rh is in a highly oxidized state. Accordingly, the purification performance of Example 1 was higher than that of Example 3.
- Example 4 although the secondary particle diameter of the first compound was as large as 350 nm, it was included by the third compound, so that further aggregation was suppressed and the purification performance was high.
- Example 5 the particle size of the catalyst powder is as large as 7.0 ⁇ m. Therefore, the gas diffusibility inside the catalyst powder was reduced, so that the purification performance was reduced as compared with Example 1.
- Example 6 since the stirring of the slurry was stopped before the drying step of the mixed slurry, the dispersity was lowered to 25%. As a result, since the aggregation of the first compound and the second compound occurred after the endurance, the purification performance was lowered as compared with Example 1.
- Example 7 was an example in which praseodymium was applied to the OSC material of the second compound, and showed an excellent purification performance almost equivalent to that of Example 1.
- Examples 8 to 11 are those in which various transition metal elements are further contained in the second compound.
- the second compound is made of an oxide containing these transition metal elements, active oxygen is supplied and the purification performance is improved.
- Example 14 uses SiO 2 as the third compound. Although the conversion rate is low as compared with Examples 1 to 13 in which Al 2 O 3 is used as the third compound, the purification performance is improved as compared with Comparative Example 1.
- Comparative Example 1 is an example in which the powder in which the first compound is covered with the third compound and the Zr—Ce—O x powder used in Example 1 are mixed in the catalyst layer.
- the Zr—Ce—O x powder which is an OSC material
- the Zr—Ce—O x powder which is an OSC material
- Comparative Example 2 is an example in which the first compound and the second compound are separately covered with the third compound.
- the degree of dispersion in the catalyst of Comparative Example 2 is the value of the powder in which the first compound is clathrated with the third compound.
- the catalyst of Comparative Example 2 has a performance in which aggregation of the noble metal particles is suppressed because the first compound supporting the noble metal particles is included by the third compound. Will improve.
- the distance of the 1st compound and the 2nd compound became long, and purification performance fell.
- Comparative Example 3 is an example in which the second compound is not contained and all Rh particles are present on the first compound (Zr—Ce (30) —O x ).
- Rh particles and the first compound were detected at the same location on TEM-EDX, but the distance between them was 2 nm or less because the EDX beam diameter was 2 nm. .
- the Rh particles are supported on the first compound having an oxygen storage capacity, the Rh particles are in a highly oxidized state and the catalyst performance is lowered.
- FIG. 6 shows the relationship between the degree of dispersion and the NOx conversion rate for the four different types of catalysts of Example 6, Example 12, Example 2 and Example 10 having different degrees of dispersion.
- the degree of dispersion is 40% or more, the variation in the distance between the first compound and the second compound is reduced, so that the particle agglomeration is suppressed and the purification performance is improved.
- FIG. 7 shows the relationship between the average distance and the NOx conversion rate for Comparative Example 1, Comparative Example 2, Example 4, Example 13, and Comparative Example 3. From the same figure, when the average distance between the first compound and the second compound is in the range of 5 nm to 300 nm, the active oxygen is efficiently supplied from the OSC material to the noble metal particles, and an excessive amount is obtained. The supply of active oxygen can be prevented. As a result, the NOx purification performance can be improved.
- a catalyst was mounted on an exhaust system of a gasoline engine with a displacement of 3500 cc, a catalyst inlet temperature was set to 700 ° C., and durability treatment was performed for 50 hours.
- the operation was changed from a lean atmosphere of 40 seconds to a rich atmosphere of 2 seconds at a catalyst inlet temperature of 300 ° C to 350 ° C.
- the exhaust gas purification rate (NOx conversion rate) was determined.
- the air-fuel ratio (A / F) in the lean atmosphere was 25, and the air-fuel ratio in the rich atmosphere was 11. Note that the formula for calculating the NOx conversion rate is the same as described above.
- the distance between the first compound and the second compound in each catalyst, the degree of dispersion of the catalyst, and the like were measured by the same method as in Examples 1 to 14.
- the NOx conversion rate of each catalyst is shown in Table 2 together with the distance between the first compound and the second compound in each catalyst, the degree of dispersion of the catalyst, and the like.
- Example 15 that does not contain barium (Ba), magnesium (Mg), or sodium (Na) in the first compound and / or the second compound.
- Example 16 to 18 containing NO in the first compound and / or the second compound, the NOx conversion rate was remarkably improved.
- the second compound having oxygen storage capacity is placed in a non-contact state with the noble metal particles having catalytic action, and the first compound in contact with the noble metal particles and the first compound.
- the interval between the two compounds is adjusted to a predetermined range.
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Abstract
Description
図1では、本発明の実施形態に係る排気ガス浄化触媒(以下、触媒ともいう。)1を示す。排気ガス浄化触媒1は、図1(a)に示すように、複数のセル2aを有するハニカム担体(耐火性無機担体)2を備えている。排気ガスは、排気ガス流通方向Fに沿って各セル2a内を流通し、そこで触媒層と接触することにより浄化される。
(1)触媒粉末のTEM-EDX分析又はHAADF-STEM分析、
(2)画像からの第1の化合物及び第2の化合物の輪郭抽出、
(3)抽出した輪郭を基に表面積から円近似及び中心点を設定、
(4)最近接中心点の検索と距離測定、
の手順で行うことができる。なお、上記距離測定方法はこのような方法に限られず、他の方法であっても客観的かつ再現性が得られる方法であれば良い。
触媒粉末をエポキシ樹脂にて包埋処理し、硬化後、ウルトラミクロトームにより超薄切片を作成する。その切片を用いて、透過型電子顕微鏡(TEM)又はHAADF-STEM(High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy)により触媒粉末を観察し、第1の化合物及び第2の化合物、更には第3の化合物の判別を行う。具体例として、TEM-EDXを用いた場合の分析条件を説明すると、まず、得られた映像の中でコントラスト(影)の部分に焦点を当て、その部分の元素種を分析して求め、その元素を含む化合物粒子を特定する。
上記(1)の分析で得られた像より第1の化合物及び第2の化合物の輪郭を抽出する。抽出方法は画像処理ソフトを用い、コントラストにより自動で抽出しても良い。また、画像をOHPシートなどに写し取って、手動で抽出しても良い。
これら(3)及び(4)の手順については、いずれも市販の画像処理ソフトにより行うことができる。つまり、抽出した輪郭により第1の化合物及び第2の化合物の面積を算出し、その面積と同じ面積を円を仮定する。そして、特定の第1の化合物に最も近接している第2の化合物を検索し、それぞれの円の中心距離を測定することにより、粒子間距離を求めることができる。
次に、本発明の排気ガス浄化触媒の製造方法について説明する。本発明の排気ガス浄化触媒は、貴金属粒子と第1の化合物と第2の化合物と、更には必要に応じて第3の化合物とを予め用意する。そして、この貴金属粒子を第1の化合物に担持する工程と、貴金属粒子を担持した第1の化合物及び第2の化合物を混合する工程により、触媒粉末を得ることができる。さらに前記触媒が第3の化合物を含む場合には、貴金属粒子を担持した第1の化合物及び第2の化合物を混合した後、更に第3の化合物を加えて混合し触媒粉末を得る。
比表面積が約70m2/gの第1の化合物粉末に、担持濃度が1.0wt%となるように硝酸ロジウム溶液を含浸した。これを150℃で一昼夜乾燥後、400℃で1時間焼成して、ロジウム担持濃度が1.0wt%の第1の化合物を得た。そして、このロジウムを担持した第1の化合物を粉砕し、表1中に記載の平均粒子径(D50)とした。なお、この平均粒子径の測定には、株式会社堀場製作所製レーザ回折/散乱式粒度分布測定装置LA-920を用いた。
実施例2は、実施例1における第1の化合物粉末中のRh担持濃度を1.4wt%とした。さらに、第1の化合物粉末及び第2の化合物粉末の合計量と、第3の化合物(Al2O3)との重量比を50:50にした。また、第1の化合物及び第2の化合物の材料組成を、表1中の記載のとおりとした。これ以外は、実施例1と同様である。この実施例2の触媒は、第2の化合物中にイットリウム(Y)を、当該第2の化合物の耐熱性を向上させる目的で含有させている。
実施例3~12は、実施例1における第1の化合物及び第2の化合物の材料組成と、二次粒径を表1中の記載のとおりとした以外は、実施例1と同様である。実施例7の触媒は第2の化合物中にネオジム(Nd)を、実施例12の触媒は第2の化合物中にイットリウム(Y)を、それぞれ当該第2の化合物の耐熱性を向上させる目的で含有させている。
実施例13は、第1の化合物に一次粒径が21nm、第2の化合物に一次粒径が65nmの複合酸化物コロイドをそれぞれ用い、第1の化合物のみにロジウムを担持させた。そして、ロジウムを担持させた第1の化合物の粉砕工程を省略して、第1の化合物及び第2の化合物と、前駆体スラリとを混合した以外は、実施例1と同様である。
実施例14は、実施例1における触媒スラリの調製の際の、第3の化合物の前駆体としてのベーマイトスラリに代えて市販のシリカゾルを用いた以外は、実施例1と同様である。二次粒径などは、表1中に記載の値とした。
比較例1は、OSC材を触媒粉末中ではなく、モノリス担体に形成された触媒層中に含む例である。
比較例2は、第1の化合物と第2の化合物とを第3の化合物で同時に覆うのではなく、別々に覆った例である。なお、比較例2の触媒の分散度は、第1の化合物を第3の化合物で包接した粉末の値である。
比較例3は、第2の化合物を有しておらず、貴金属粒子が酸素吸蔵能を有する第1の化合物に担持されている例である。
実施例15~18は、実施例1における、予め用意したPtを含む触媒層を有する触媒担体に次の処理を行って、Ptを含む触媒層中にBaを含有させた。つまり、Ptがコートされた触媒担体を、純水と酢酸バリウム水溶液(濃度40wt%)とを混合した溶液中に一定時間浸漬した後に水分を留去し、400℃で1時間乾燥させた。これにより、Pt及びBaを含む触媒層を有する触媒担体を調製した。 それ以外の工程は、実施例1と同様である。
これらの実施例及び比較例のうち、実施例1~14及び比較例1~3については、耐久処理を施した後、NOx転化率を調べた。この耐久処理の方法は、排気量3500ccのガソリンエンジンの排気系に触媒を装着し、触媒入口温度を800℃とし、50時間運転したものである。使用燃料には無鉛ガソリンを使用した。また、NOx転化率は、排気量3500ccのガソリンエンジンの排気系に触媒を装着し、触媒入口温度を400℃として、数式(3)に従いNOx転化率を測定した。
次に、表2に示す実施例15~18の触媒を用い、リーンバーンエンジンへの触媒の適用を想定して、リーン雰囲気からリッチ雰囲気まで変動する条件下での浄化性能について評価を行った。
5 触媒粉末
6 貴金属粒子
7 第1の化合物
9 第2の化合物
10 第3の化合物
10a 細孔
Claims (14)
- 貴金属粒子と、前記貴金属粒子を担持する第1の化合物と、前記貴金属粒子と非接触に配設され、酸素吸蔵能を有する第2の化合物とを含有し、
前記第1の化合物と前記第2の化合物との間の平均距離が5nm~300nmであることを特徴とする排気ガス浄化触媒。 - 前記貴金属粒子と接触した前記第1の化合物及び第2の化合物を共に包接し、前記第1の化合物及び第2の化合物を互いに隔てる第3の化合物を更に含有することを特徴とする請求項1に記載の排気ガス浄化触媒。
- 前記第1の化合物の平均二次粒子径が300nm以下であり、かつ、前記第2の化合物の平均二次粒子径が1000nm以下であることを特徴とする請求項1乃至3のいずれか一項に記載の排気ガス浄化触媒。
- 前記貴金属粒子、第1の化合物及び第2の化合物を含有する触媒粉末の平均粒子径は、6μm以下であることを特徴とする請求項1乃至4のいずれか一項に記載の排気ガス浄化触媒。
- 前記貴金属粒子がロジウムであり、前記第1の化合物がジルコニウムを含む酸化物であることを特徴とする請求項1乃至5のいずれか一項に記載の排気ガス浄化触媒。
- 前記第2の化合物に含有され、酸素吸蔵能を有する酸素吸蔵材は、セリウム及びプラセオジムの少なくともいずれか一方を含むことを特徴とする請求項1乃至6のいずれか一項に記載の排気ガス浄化触媒。
- 前記第3の化合物は、アルミニウム及びケイ素の少なくともいずれか一方を含むことを特徴とする請求項1乃至6のいずれか一項に記載の排気ガス浄化触媒。
- 前記貴金属粒子、第1の化合物及び第2の化合物を含有する触媒粉末中における第1の化合物及び第2の化合物の分散度は、40%以上であることを特徴とする請求項1乃至8のいずれか一項に記載の排気ガス浄化触媒。
- 前記第1の化合物及び第2の化合物の少なくともいずれか一方は、鉄、マンガン、コバルト及びニッケルからなる群から選ばれる少なくとも一種を含む酸化物であることを特徴とする請求項1乃至9のいずれか一項に記載の排気ガス浄化触媒。
- 前記第1の化合物及び第2の化合物の少なくともいずれか一方は、バリウム、マグネシウム、カルシウム、ストロンチウム及びナトリウムからなる群から選ばれる少なくとも一種を含む化合物であることを特徴とする請求項1乃至10のいずれか一項に記載の排気ガス浄化触媒。
- 前記貴金属粒子、第1の化合物及び第2の化合物を含有する触媒粉末が、耐火性無機担体に塗布されてなることを特徴とする請求項1乃至11のいずれか一項に記載の排気ガス浄化触媒。
- 前記耐火性無機担体に形成され、前記触媒粉末を含む触媒層が、成分組成の異なる複数層からなることを特徴とする請求項12に記載の排気ガス浄化触媒。
- 請求項2乃至11のいずれか一項に記載の排気ガス浄化触媒の製造方法において、
前記第1の化合物及び第2の化合物を個別に又は一体的に粉砕する工程と、
粉砕された前記第1の化合物及び第2の化合物を、前記第3の化合物の前駆体により同時に包接する工程と、
を有することを特徴とする排気ガス浄化触媒の製造方法。
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2298444A1 (en) * | 2009-08-18 | 2011-03-23 | Mazda Motor Corporation | Exhaust gas purification catalyst |
WO2012160709A1 (en) * | 2011-05-24 | 2012-11-29 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purification system |
JP2012240027A (ja) * | 2011-05-24 | 2012-12-10 | Nissan Motor Co Ltd | 排ガス浄化触媒及びその製造方法 |
WO2013042461A1 (ja) * | 2011-09-20 | 2013-03-28 | 日産自動車株式会社 | 排ガス浄化用触媒及びその製造方法 |
JP2013542064A (ja) * | 2010-09-15 | 2013-11-21 | ビーエーエスエフ ソシエタス・ヨーロピア | 焼成に対して安定な不均一触媒 |
JP2014079717A (ja) * | 2012-10-18 | 2014-05-08 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
JP2016517346A (ja) * | 2013-03-13 | 2016-06-16 | ビーエーエスエフ コーポレーション | 特定の粒径分布を有する金属酸化物支持体粒子を含む触媒組成物 |
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Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200813091A (en) | 2006-04-10 | 2008-03-16 | Amgen Fremont Inc | Targeted binding agents directed to uPAR and uses thereof |
EP2615114B1 (en) | 2007-08-23 | 2022-04-06 | Amgen Inc. | Antigen binding proteins to proprotein convertase subtilisin kexin type 9 (PCSK9) |
WO2010013574A1 (ja) * | 2008-07-31 | 2010-02-04 | 日産自動車株式会社 | 排気ガス浄化触媒 |
JP2012513194A (ja) | 2008-12-23 | 2012-06-14 | アストラゼネカ アクチボラグ | α5β1に向けられた標的結合剤およびその使用 |
US8683787B2 (en) | 2009-11-17 | 2014-04-01 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and method for manufacturing the same |
WO2015174102A1 (ja) * | 2014-05-13 | 2015-11-19 | 日産自動車株式会社 | 排ガス浄化用触媒 |
WO2016130566A2 (en) * | 2015-02-11 | 2016-08-18 | SDCmaterials, Inc. | Lean nox traps, trapping materials, washcoats, and methods of making and using the same |
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PL3411404T3 (pl) | 2016-02-03 | 2023-02-13 | Amgen Research (Munich) Gmbh | Konstrukty dwuswoistych przeciwciał wobec PSMA i CD3 angażujących komórki T |
US10301391B2 (en) | 2016-02-03 | 2019-05-28 | Amgen Research (Munich) Gmbh | BCMA and CD3 bispecific T cell engaging antibody constructs |
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JOP20190189A1 (ar) | 2017-02-02 | 2019-08-01 | Amgen Res Munich Gmbh | تركيبة صيدلانية ذات درجة حموضة منخفضة تتضمن بنيات جسم مضاد يستهدف الخلية t |
WO2019043346A1 (fr) | 2017-09-01 | 2019-03-07 | Rhodia Operations | Oxyde mixte a base de cerium et de zirconium |
CA3137494A1 (en) | 2019-06-13 | 2020-12-17 | Amgen Inc. | Automated biomass-based perfusion control in the manufacturing of biologics |
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US20220396599A1 (en) | 2019-11-13 | 2022-12-15 | Amgen Inc. | Method for Reduced Aggregate Formation in Downstream Processing of Bispecific Antigen-Binding Molecules |
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JP6956826B2 (ja) * | 2020-04-03 | 2021-11-02 | 株式会社キャタラー | 排ガス浄化触媒装置 |
CA3183756A1 (en) | 2020-05-19 | 2021-11-25 | Amgen Inc. | Mageb2 binding constructs |
WO2022074206A1 (en) | 2020-10-08 | 2022-04-14 | Affimed Gmbh | Trispecific binders |
AU2021374036A1 (en) | 2020-11-06 | 2023-06-08 | Amgen Inc. | Polypeptide constructs selectively binding to cldn6 and cd3 |
US20230406929A1 (en) | 2020-11-06 | 2023-12-21 | Amgen Inc. | Polypeptide constructs binding to cd3 |
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WO2022096716A2 (en) | 2020-11-06 | 2022-05-12 | Amgen Inc. | Multitargeting bispecific antigen-binding molecules of increased selectivity |
AU2022246675A1 (en) | 2021-04-02 | 2023-10-19 | Amgen Inc. | Mageb2 binding constructs |
IL307672A (en) | 2021-05-06 | 2023-12-01 | Amgen Res Munich Gmbh | CD20 and CD22 targeting antigen-binding molecules for use in proliferative diseases |
AU2022320948A1 (en) | 2021-07-30 | 2024-01-18 | Affimed Gmbh | Duplexbodies |
WO2023079493A1 (en) | 2021-11-03 | 2023-05-11 | Affimed Gmbh | Bispecific cd16a binders |
CA3233696A1 (en) | 2021-11-03 | 2023-05-11 | Joachim Koch | Bispecific cd16a binders |
TW202346368A (zh) | 2022-05-12 | 2023-12-01 | 德商安美基研究(慕尼黑)公司 | 具有增加的選擇性的多鏈多靶向性雙特異性抗原結合分子 |
WO2024059675A2 (en) | 2022-09-14 | 2024-03-21 | Amgen Inc. | Bispecific molecule stabilizing composition |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005000829A (ja) | 2003-06-12 | 2005-01-06 | Toyota Motor Corp | 排ガス浄化用触媒とその製造方法 |
JP2007050382A (ja) * | 2005-08-19 | 2007-03-01 | Nissan Motor Co Ltd | 排ガス浄化触媒 |
WO2007052627A1 (ja) | 2005-11-01 | 2007-05-10 | Nissan Motor Co., Ltd. | 排気ガス浄化用触媒及びその製造方法 |
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 |
JP2007229653A (ja) * | 2006-03-02 | 2007-09-13 | Nissan Motor Co Ltd | 排気ガス浄化触媒 |
JP2008272745A (ja) * | 2007-04-05 | 2008-11-13 | Nissan Motor Co Ltd | 排ガス浄化用触媒 |
JP2009051071A (ja) | 2007-08-27 | 2009-03-12 | Dainippon Printing Co Ltd | 複写帳票 |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2005538C1 (ru) | 1992-02-05 | 1994-01-15 | Елена Алексеевна Дробаха | Способ приготовления катализатора для очистки выхлопных газов двигателей внутреннего сгорания |
US5948377A (en) * | 1996-09-04 | 1999-09-07 | Engelhard Corporation | Catalyst composition |
US6025297A (en) * | 1996-11-14 | 2000-02-15 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gas and process for producing the same |
JPH10249198A (ja) | 1997-03-10 | 1998-09-22 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒及びその製造方法 |
US6107239A (en) * | 1998-01-19 | 2000-08-22 | Luchuang Environment Protection Science Co. Ltd. | Heat resistant metallic oxide catalyst for reducing pollution emission |
US20020128151A1 (en) * | 1998-05-01 | 2002-09-12 | Michael P. Galligan | Catalyst members having electric arc sprayed substrates and methods of making the same |
US20050163677A1 (en) * | 1998-05-01 | 2005-07-28 | Engelhard Corporation | Catalyst members having electric arc sprayed substrates and methods of making the same |
EP1046423B8 (en) | 1999-04-23 | 2007-11-21 | Umicore AG & Co. KG | Layered noble metal-containing exhaust gas catalyst and its preparation |
JP3688974B2 (ja) | 1999-05-24 | 2005-08-31 | ダイハツ工業株式会社 | 排ガス浄化用触媒 |
DE10024994A1 (de) | 1999-05-24 | 2001-01-04 | Daihatsu Motor Co Ltd | Katalytischer Umwandler zum Reinigen von Abgasen |
US6528029B1 (en) * | 1999-10-13 | 2003-03-04 | Engelhard Corporation | Catalyst compositions employing sol gel particles and methods of using the same |
US6458741B1 (en) | 1999-12-20 | 2002-10-01 | Eltron Research, Inc. | Catalysts for low-temperature destruction of volatile organic compounds in air |
EP1371415B1 (en) * | 2001-02-19 | 2006-12-06 | Toyota Jidosha Kabushiki Kaisha | Catalyst for hydrogen generation and catalyst for purification of exhaust gas |
US6528451B2 (en) | 2001-03-13 | 2003-03-04 | W.R. Grace & Co.-Conn. | Catalyst support material having high oxygen storage capacity and method of preparation thereof |
EP1287886A1 (de) * | 2001-08-09 | 2003-03-05 | OMG AG & Co. KG | Katalysator für die Reinigung der Abgase eines Verbrennungsmotors |
US7022644B2 (en) | 2002-02-20 | 2006-04-04 | Engelhard Corporation | Hydrogen sulfide-suppressing catalyst compositions |
US20040074230A1 (en) | 2002-10-16 | 2004-04-22 | Guinther Gregory H. | Method of oxidizing soot and reducing soot accumulation in a diesel fuel combustion after treatment system |
DE10335785A1 (de) * | 2003-08-05 | 2005-03-10 | Umicore Ag & Co Kg | Katalysatoranordnung und Verfahren zur Reinigung des Abgases von mager betriebenen Verbrennungsmotoren |
JP4236543B2 (ja) * | 2003-09-08 | 2009-03-11 | 本田技研工業株式会社 | 窒素酸化物の接触分解のための触媒と方法 |
JP4959129B2 (ja) * | 2004-02-16 | 2012-06-20 | 株式会社キャタラー | 排ガス浄化用触媒 |
JP4547930B2 (ja) * | 2004-02-17 | 2010-09-22 | 日産自動車株式会社 | 触媒、触媒の調製方法及び排ガス浄化用触媒 |
JP4547935B2 (ja) * | 2004-02-24 | 2010-09-22 | 日産自動車株式会社 | 排ガス浄化用触媒、排ガス浄化触媒、及び触媒の製造方法 |
JP4465352B2 (ja) * | 2004-03-11 | 2010-05-19 | 株式会社キャタラー | 排ガス浄化触媒 |
JP4513372B2 (ja) * | 2004-03-23 | 2010-07-28 | 日産自動車株式会社 | 排ガス浄化用触媒及び排ガス浄化触媒 |
JP4513384B2 (ja) * | 2004-03-31 | 2010-07-28 | 日産自動車株式会社 | 高耐熱性排ガス浄化用触媒及びその製造方法 |
JP2007534477A (ja) * | 2004-04-26 | 2007-11-29 | ハーテーエー・アクチェンゲゼルシャフト・ザ・ハイ・スループット・イクスペリメンテイション・カンパニー | 酸素リッチな排ガスから一酸化炭素および炭化水素を同時除去するための触媒、ならびにその製造方法 |
US7605108B2 (en) * | 2004-07-08 | 2009-10-20 | Nissan Motor Co., Ltd. | Catalyst, exhaust gas purification catalyst, and method for manufacturing same |
US7566424B2 (en) | 2004-07-23 | 2009-07-28 | Mazda Motor Corporation | Exhaust gas purification catalyst |
JP4513453B2 (ja) | 2004-08-02 | 2010-07-28 | マツダ株式会社 | 排気ガス浄化用触媒 |
US7713908B2 (en) * | 2004-08-30 | 2010-05-11 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Porous composite metal oxide and method of producing the same |
JP4277771B2 (ja) | 2004-09-09 | 2009-06-10 | トヨタ自動車株式会社 | 排ガス浄化用触媒、排ガス浄化装置および内燃機関を備えるシステム |
WO2006064684A1 (ja) * | 2004-12-14 | 2006-06-22 | Nissan Motor Co., Ltd. | 触媒、排ガス浄化触媒、及び触媒の製造方法 |
JP5200315B2 (ja) * | 2004-12-22 | 2013-06-05 | 日産自動車株式会社 | 排気ガス浄化触媒、及び排気ガス浄化触媒の製造方法 |
JP4999331B2 (ja) | 2005-03-24 | 2012-08-15 | 東京濾器株式会社 | 排気ガス浄化用触媒 |
EP1704910B1 (en) | 2005-03-24 | 2018-09-19 | Tokyo Roki Co., Ltd. | Exhaust gas purification catalyst |
WO2006130858A2 (en) * | 2005-06-02 | 2006-12-07 | Symyx Technologies, Inc. | Catalysts for co oxidation, voc combustion and nox reduction and methods of making and using same |
EP1907323B1 (de) * | 2005-07-16 | 2018-04-25 | Archroma IP GmbH | Verfahren zur herstellung von nanopartikeln aus aluminiumoxid und oxiden von elementen der i. und ii. hauptgruppe des periodensystems |
JP2007105632A (ja) | 2005-10-13 | 2007-04-26 | Nissan Motor Co Ltd | 排ガス浄化触媒 |
US8119075B2 (en) | 2005-11-10 | 2012-02-21 | Basf Corporation | Diesel particulate filters having ultra-thin catalyzed oxidation coatings |
JP4720545B2 (ja) | 2006-03-02 | 2011-07-13 | 日産自動車株式会社 | 排気ガス浄化用触媒及びその製造方法 |
EP2022562B1 (en) | 2006-04-03 | 2021-06-09 | Nissan Motor Company Limited | Exhaust gas purifying catalyst |
JP2007313493A (ja) | 2006-04-28 | 2007-12-06 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
JP4881758B2 (ja) * | 2006-04-28 | 2012-02-22 | 日産自動車株式会社 | 排気ガス浄化用触媒及びその製造方法 |
JP2007301526A (ja) * | 2006-05-15 | 2007-11-22 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒及びその製造方法 |
US7550124B2 (en) * | 2006-08-21 | 2009-06-23 | Basf Catalysts Llc | Layered catalyst composite |
US7517510B2 (en) * | 2006-08-21 | 2009-04-14 | Basf Catalysts Llc | Layered catalyst composite |
US20080044330A1 (en) * | 2006-08-21 | 2008-02-21 | Shau-Lin Franklin Chen | Layered catalyst composite |
JP4760625B2 (ja) | 2006-09-06 | 2011-08-31 | マツダ株式会社 | 排ガス浄化用触媒装置 |
JP4956130B2 (ja) | 2006-10-05 | 2012-06-20 | 日産自動車株式会社 | 排ガス浄化用触媒 |
JP5551329B2 (ja) * | 2006-11-14 | 2014-07-16 | 日産自動車株式会社 | 排気ガス浄化触媒及びその製造方法 |
RU2322296C1 (ru) | 2006-12-04 | 2008-04-20 | Институт физико-химических проблем керамических материалов Российской академии наук (ИПК РАН) | Способ приготовления катализатора очистки отработавших газов двигателей внутреннего сгорания и катализатор, полученный этим способом |
JP2008168278A (ja) * | 2006-12-15 | 2008-07-24 | Nissan Motor Co Ltd | 排ガス浄化用触媒及びその製造方法 |
JP4853291B2 (ja) | 2007-01-10 | 2012-01-11 | 日産自動車株式会社 | 排気ガス浄化触媒及びその製造方法 |
EP1952876A1 (en) * | 2007-01-25 | 2008-08-06 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and manufacturing method thereof |
US7754171B2 (en) * | 2007-02-02 | 2010-07-13 | Basf Corporation | Multilayered catalyst compositions |
WO2010013574A1 (ja) | 2008-07-31 | 2010-02-04 | 日産自動車株式会社 | 排気ガス浄化触媒 |
CN101404410A (zh) | 2008-10-27 | 2009-04-08 | 张强胜 | 绿色能源与网电并联供电方法 |
US8683787B2 (en) | 2009-11-17 | 2014-04-01 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and method for manufacturing the same |
-
2010
- 2010-03-04 MY MYPI2011004118 patent/MY152352A/en unknown
- 2010-03-04 RU RU2011140138/04A patent/RU2477176C1/ru active
- 2010-03-04 US US13/254,313 patent/US8486853B2/en active Active
- 2010-03-04 CN CN201080010360XA patent/CN102341172A/zh active Pending
- 2010-03-04 JP JP2011502804A patent/JP4956801B2/ja active Active
- 2010-03-04 BR BRPI1011478-5A patent/BRPI1011478B1/pt active IP Right Grant
- 2010-03-04 EP EP10748816.5A patent/EP2404668B1/en active Active
- 2010-03-04 WO PCT/JP2010/053568 patent/WO2010101223A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005000829A (ja) | 2003-06-12 | 2005-01-06 | Toyota Motor Corp | 排ガス浄化用触媒とその製造方法 |
JP2007050382A (ja) * | 2005-08-19 | 2007-03-01 | Nissan Motor Co Ltd | 排ガス浄化触媒 |
WO2007052627A1 (ja) | 2005-11-01 | 2007-05-10 | Nissan Motor Co., Ltd. | 排気ガス浄化用触媒及びその製造方法 |
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 |
JP2007229653A (ja) * | 2006-03-02 | 2007-09-13 | Nissan Motor Co Ltd | 排気ガス浄化触媒 |
JP2008272745A (ja) * | 2007-04-05 | 2008-11-13 | Nissan Motor Co Ltd | 排ガス浄化用触媒 |
JP2009051071A (ja) | 2007-08-27 | 2009-03-12 | Dainippon Printing Co Ltd | 複写帳票 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2404668A4 |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8912116B2 (en) | 2009-08-18 | 2014-12-16 | Mazda Motor Corporation | Exhaust gas purification catalyst |
EP2298444A1 (en) * | 2009-08-18 | 2011-03-23 | Mazda Motor Corporation | Exhaust gas purification catalyst |
JP2013542064A (ja) * | 2010-09-15 | 2013-11-21 | ビーエーエスエフ ソシエタス・ヨーロピア | 焼成に対して安定な不均一触媒 |
WO2012160709A1 (en) * | 2011-05-24 | 2012-11-29 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purification system |
JP2012240027A (ja) * | 2011-05-24 | 2012-12-10 | Nissan Motor Co Ltd | 排ガス浄化触媒及びその製造方法 |
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EP2759340A4 (en) * | 2011-09-20 | 2015-04-01 | Nissan Motor | CATALYST FOR PURIFYING EXHAUST GAS AND METHOD FOR MANUFACTURING THE SAME |
EP2759340A1 (en) * | 2011-09-20 | 2014-07-30 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and method for producing same |
US9233357B2 (en) | 2011-09-20 | 2016-01-12 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and method for producing same |
WO2013042461A1 (ja) * | 2011-09-20 | 2013-03-28 | 日産自動車株式会社 | 排ガス浄化用触媒及びその製造方法 |
JP2014079717A (ja) * | 2012-10-18 | 2014-05-08 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及びその製造方法 |
JP2016517346A (ja) * | 2013-03-13 | 2016-06-16 | ビーエーエスエフ コーポレーション | 特定の粒径分布を有する金属酸化物支持体粒子を含む触媒組成物 |
JPWO2015087781A1 (ja) * | 2013-12-09 | 2017-03-16 | 株式会社キャタラー | 排ガス浄化用触媒 |
Also Published As
Publication number | Publication date |
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RU2477176C1 (ru) | 2013-03-10 |
BRPI1011478A2 (pt) | 2016-03-22 |
EP2404668B1 (en) | 2014-05-07 |
JP4956801B2 (ja) | 2012-06-20 |
JPWO2010101223A1 (ja) | 2012-09-10 |
US8486853B2 (en) | 2013-07-16 |
EP2404668A1 (en) | 2012-01-11 |
CN102341172A (zh) | 2012-02-01 |
EP2404668A4 (en) | 2013-04-17 |
MY152352A (en) | 2014-09-15 |
BRPI1011478B1 (pt) | 2018-01-30 |
US20120053050A1 (en) | 2012-03-01 |
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