WO2016052735A1 - 排ガス浄化用触媒 - Google Patents
排ガス浄化用触媒 Download PDFInfo
- Publication number
- WO2016052735A1 WO2016052735A1 PCT/JP2015/078070 JP2015078070W WO2016052735A1 WO 2016052735 A1 WO2016052735 A1 WO 2016052735A1 JP 2015078070 W JP2015078070 W JP 2015078070W WO 2016052735 A1 WO2016052735 A1 WO 2016052735A1
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- WIPO (PCT)
- Prior art keywords
- exhaust gas
- catalyst
- pore
- metal
- purifying catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 167
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9202—Linear dimensions
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
Definitions
- the present invention relates to an exhaust gas purifying catalyst provided in an exhaust system of an internal combustion engine. Specifically, the present invention relates to an exhaust gas purifying catalyst in which the pore size distribution of the carrier is controlled.
- Exhaust gas discharged from an internal combustion engine such as an automobile engine contains harmful components such as hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide (NO x ).
- HC hydrocarbon
- CO carbon monoxide
- NO x nitrogen oxide
- the exhaust gas purifying catalyst typically includes a catalyst layer including a noble metal functioning as a catalyst (hereinafter sometimes simply referred to as “catalyst metal”) and a carrier supporting the catalyst metal.
- Such an exhaust gas purifying catalyst has a problem that, for example, when it is exposed to high temperature exhaust gas for a long period of time, the catalytic metal deteriorates and the purification performance is lowered.
- One of the main causes is sintering of the catalyst metal under high temperature conditions (for example, 800 to 1000 ° C.) (grain growth by sintering). That is, as the sintering of the catalytic metal proceeds, the specific surface area decreases and the catalytic active point decreases. As a result, exhaust gas purification performance may deteriorate. Therefore, various studies have been made to suppress this phenomenon.
- Patent Document 1 describes that the growth of catalyst metal grains can be suppressed by using alumina whose average interlayer distance is controlled to 0.01 to 0.1 ⁇ m as a support.
- the present invention has been created to solve this problem, and an object of the present invention is to provide an exhaust gas purifying catalyst in which grain growth of catalyst metal is better suppressed and purification performance is high.
- the exhaust gas purifying catalyst according to the present invention is an exhaust gas purifying catalyst that is disposed in an exhaust pipe of an internal combustion engine such as an automobile engine and purifies exhaust gas discharged from the internal combustion engine.
- Such an exhaust gas purifying catalyst includes a base material, a catalyst layer formed on the base material, which functions as an oxidation and / or reduction catalyst, and a catalyst layer including a carrier supporting the catalyst metal. I have.
- the carrier is in the pore size distribution of the measured volume basis, based on the nitrogen gas adsorption method, the cumulative 90% from the small pore side and a pore diameter P 10 corresponding to the 10% accumulated from the small pore side
- Each of the corresponding pore diameters P 90 is made of a porous ceramic having a range of 5 to 50 nm.
- Both the P 10 and P 90 in the above range can be aligned homogeneous pore diameter of the carrier.
- the catalyst metal can be supported in a highly dispersed manner.
- the movement of the catalyst metal can be suppressed as compared with the conventional case, and for example, the grain growth and alloying of the catalyst metal can be suppressed even under high temperature conditions (for example, 800 to 1000 ° C.).
- high temperature conditions for example, 800 to 1000 ° C.
- pore size distribution means a volume-based pore size obtained by analyzing an adsorption isotherm measured by a gas adsorption method using nitrogen gas by a BJH (Barrett-Joyner-Halenda) method. Distribution.
- the P 10 may be in the 5 ⁇ 20nm. As a result, a carrier having a small structural change even under high temperature conditions and excellent in heat resistance can be realized. Therefore, the effect of the present invention can be realized at a higher level.
- the P 90 may be 20 to 50 nm. By suppressing the P 90 in the above range, it is possible to improve the dispersibility of the catalytic metal, it is possible to suppress a decrease in catalytic performance at high temperature conditions. Therefore, the effect of the present invention can be realized at a higher level.
- the ratio of the P 10 for the P 90 is 0.25 to 0.6.
- P 10 / P 90 is closer to 1 as the pore size distribution is narrower (sharp), and conversely approaches 0 as the pore size distribution is wider (broader). That is, P 10 / P 90 is one index representing the spread of the pore size distribution.
- It P 10 / P 90 is 0.25 or more, pore size, means that the more uniform. Thereby, the catalyst metal can be more uniformly dispersed. As a result, the sintering accompanying the grain growth of the catalyst metal can be further suppressed.
- It ceramics P 10 / P 90 is 0.6 or less, pore size, means that with more width. Thereby, reduction of pressure loss and suppression of sintering can be balanced at a high level. It is also preferable from the viewpoint of improving production efficiency and yield.
- the proportion of the pore volume of 100 nm or more is 5% or less of the total pore volume.
- the pore volume of the ceramic is 0.2 ml / g or more.
- the ratio of the catalytic metal is 0.1 to 3% by mass with respect to the total mass of the catalyst layer. In a more preferred embodiment, the ratio of the catalyst metal is 0.3 to 1% by mass with respect to the total mass of the catalyst layer.
- Catalytic metals especially precious metals belonging to the platinum group
- the catalytic activity relative to the amount of supported catalytic metal can be improved, so that even if the amount of catalytic metal used is reduced to the above range, good exhaust gas purification performance can be realized. .
- FIG. 1 is a perspective view schematically showing an exhaust gas purifying catalyst according to an embodiment.
- FIG. 2 is a graph comparing the catalytic activity (HC oxidation activity) of the exhaust gas purifying catalysts according to Examples 1 and 8.
- FIG. 3 is a graph comparing the catalytic activity (CO oxidation activity) of the exhaust gas purifying catalysts according to Example 1 and Example 8.
- the exhaust gas-purifying catalyst disclosed herein is characterized in that the pore size distribution of the carrier contained in the catalyst layer is highly controlled. Therefore, other configurations are not particularly limited.
- a base material, a carrier, a catalytic metal, etc. which will be described later, can be appropriately selected and formed into a desired shape according to the application.
- FIG. 1 is a schematic view of an exhaust gas purifying catalyst according to a preferred embodiment.
- the direction through which exhaust gas flows is drawn by the arrow direction. That is, the left side of FIG. 1 is the upstream side of the exhaust gas passage (exhaust pipe), and the right side is the downstream side of the exhaust gas passage.
- An exhaust gas purification catalyst 10 shown in FIG. 1 is a so-called straight flow type exhaust gas purification catalyst.
- the exhaust gas-purifying catalyst 10 includes a cylindrical honeycomb substrate 1.
- the honeycomb substrate 1 includes a plurality of regularly arranged through holes (cells) 2 in the cylinder axis direction (exhaust gas flow direction) and partition walls (rib walls) 4 that partition the cells 2.
- a catalyst layer (not shown) having a predetermined property (for example, length and thickness) is formed on the rib wall 4.
- the exhaust gas supplied to the exhaust gas purification catalyst 10 comes into contact with the catalyst layer provided on the rib wall 4 while flowing (passing) through the flow path (in the cell 2) of the honeycomb substrate 1. As a result, harmful components in the exhaust gas are purified.
- HC and CO contained in the exhaust gas are oxidized by the catalytic function of the catalyst layer and converted (purified) into water (H 2 O), carbon dioxide (CO 2 ), and the like. Further, for example, NO x is reduced by the catalytic function of the catalyst layer and converted (purified) into nitrogen (N 2 ).
- each component of the exhaust gas purifying catalyst 10 will be described in order.
- the honeycomb substrate 1 constitutes the skeleton of the exhaust gas purifying catalyst.
- the honeycomb substrate 1 is not particularly limited, and those made of various materials conventionally used for this type of application can be employed. Among these, those made of a high heat resistant material are preferable.
- ceramics specifically, aluminum oxide (alumina: Al 2 O 3 ), cerium oxide (ceria: CeO 2 ), titanium oxide (titania: TiO 2 ), zirconium oxide (zirconia: ZrO 2 ), silicon oxide
- oxide ceramics such as (silica: SiO 2 ); made of composite oxide ceramics such as cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2 ); made of carbide ceramics such as silicon carbide (silicon carbide: SiC) Can be preferably employed. Alternatively, it may be made of an alloy such as stainless steel.
- the shape of the honeycomb substrate 1 may be the same as that of a conventional exhaust gas purification catalyst.
- the outer shape is a cylindrical shape.
- the outer shape of the honeycomb substrate 1 may be, for example, an elliptical cylinder shape or a polygonal cylinder shape instead of the cylindrical shape as shown in FIG.
- the capacity of the honeycomb substrate 1 (volume of the flow path 2) is not particularly limited, but is usually 0.01 L or more, for example 0.02 L or more, preferably 0.1 L or more, for example, 5 L or less, preferably 3 L or less, More preferably, it is 2L or less.
- the total length of the honeycomb substrate 1 in the cylinder axis direction is not particularly limited, but it is usually about 10 to 500 mm, for example, about 50 to 300 mm.
- the base material 1 can also be made into a foam shape, a pellet shape, etc. other than the honeycomb shape shown in FIG.
- the catalyst layer forms the main body of the exhaust gas purifying catalyst as a place for purifying the exhaust gas.
- the catalyst layer includes a porous carrier and a catalyst metal supported on the surface of the carrier.
- the carrier is composed of porous ceramic powder.
- the kind of ceramic may be the same as the conventional exhaust gas purification catalyst. Among these, those having a large specific surface area (specific surface area measured by a nitrogen adsorption method (BET method); the same shall apply hereinafter) and excellent heat resistance can be preferably used.
- Preferable examples include alumina (Al 2 O 3 ), ceria (CeO 2 ), titania (TiO 2 ), zirconia (ZrO 2 ), silica (SiO 2 ), and solid solutions thereof (for example, ceria-zirconia composite oxide ( CZ composite oxide)), or a combination thereof.
- the ceramic powder it is only necessary to satisfy a predetermined pore size distribution, and one obtained by purchasing a commercially available product, one obtained by processing a commercially available product, one synthesized in accordance with a conventionally known method, or the like may be used. it can.
- the pore size distribution of the ceramic can be controlled by adjusting, for example, the production conditions of the ceramic and the physical and chemical properties (for example, the average particle size and specific surface area) of the ceramic. .
- the average particle size of the ceramic is made smaller and the specific surface area is made larger by grinding or sieving (classification).
- the pore size distribution is adjusted to the above range, for example, by crushing the ceramic at a portion having a large pore size.
- a conventionally known pulverizer such as a ball mill, a bead mill, a jet mill, a planetary mixer, or a homogenizer can be used.
- a wet type solvent type
- Processing conditions for example, output intensity and processing time of the processing apparatus may be appropriately adjusted depending on the ceramic used.
- the ceramic powder having the pore size distribution as described above can be suitably obtained.
- the pore diameter P 90 corresponding to a cumulative 90% from the pore side is composed of 5 to 50 nm of porous ceramic powder.
- the P 10 may be in the range (more than 5 nm). However, there is for example 10nm or more, generally 20nm or less, for example, may is 15nm or less. Thereby, the catalyst layer excellent in mechanical strength (durability) can be realized better.
- the average pore diameter P 50 corresponding to 50% cumulative from the small pore side may be in the above range, but is typically 20 nm or more, for example, 25 nm or more, and is generally 40 nm or less, for example, 30 nm or less. obtain. Thereby, reduction of pressure loss and suppression of sintering can be balanced at a high level.
- the P 90 may be in the above range (50 nm or less), but is generally about 20 nm or more, typically 30 nm or more, such as 34 nm or more, and typically 45 nm or less, such as 40 nm or less.
- the pore diameter P 95 corresponding to 95% cumulative from the small pore side is not particularly limited, but is typically 35 nm or more, such as 40 nm or more, and may be generally 100 nm or less, such as 50 nm or less.
- the proportion of coarse pore volume approximately 100 nm or more, typically 50 nm or more, for example 40 nm or more may be 5% or less of the total pore volume.
- the ratio of the P 10 for the P 90 is generally 0.25 or more, for example 0.275 or more, further comprising at least 0.3, typically 0.6 or less, for example 0.5 or less.
- P 10 / P 90 is a predetermined value or more, indicating the pore size distribution is relatively narrow, the pore diameter has a predetermined homogeneity that (are aligned).
- P 10 / P 90 being equal to or less than a predetermined value indicates that the pore diameter distribution is relatively broad and the pore diameter has a predetermined spread (varies).
- Such ceramic powder can be prepared relatively easily without requiring a special manufacturing apparatus or the like. This is preferable from the viewpoint of improving production efficiency and reducing costs.
- the mechanical strength (durability) of the catalyst layer and the suppression of pressure loss can be better balanced.
- the properties of the ceramic are not particularly limited as long as the pore size distribution is satisfied.
- the smaller the average particle size the larger the specific surface area, which is effective for increasing the contact area with the exhaust gas.
- the specific surface area of the ceramic is usually 50 to 500 m 2 / g, typically 100 to 400 m 2 / g, for example, about 100 to 200 m 2 / g.
- the pore volume based on the gas adsorption method is usually about 0.2 to 1.0 ml / g, for example, about 0.5 to 0.7 ml / g.
- the average particle diameter volume-based average particle diameter (median diameter) based on the laser diffraction / scattering particle size distribution measurement method) is usually about 1 to 50 ⁇ m, for example, about 5 to 10 ⁇ m.
- the catalytic metal various kinds of metal species that can function as an oxidation catalyst or a reduction catalyst can be considered.
- Typical examples include noble metals such as rhodium (Rh), palladium (Pd), and platinum (Pt), which are a platinum group.
- ruthenium (Ru), osmium (Os), iridium (Ir), silver (Ag), gold (Au), or the like may be used.
- it may contain other metal species such as alkali metals, alkaline earth metals, and transition metals.
- rhodium having a high reducing activity and palladium or platinum having a high oxidizing activity can be suitably used, and it is particularly preferable to use a combination of two or more of these.
- various harmful components contained in the exhaust gas can be efficiently purified.
- alloying of two or more kinds of catalyst metals under high temperature conditions is highly suppressed. For this reason, the performance of the catalyst metal can be sufficiently exhibited.
- Such a catalyst metal is preferably used as fine particles having a sufficiently small particle diameter from the viewpoint of increasing the contact area with the exhaust gas.
- the average particle diameter D 50 of the catalyst metal particles (the average value of the number-based particle diameters determined by transmission electron microscope (TEM) observation, the same applies hereinafter) is usually smaller than the above P 10 and about It is about 1 to 15 nm, typically 10 nm or less, for example 7 nm or less, and further preferably 5 nm or less. That said P 10 is greater than the D 50 indicates that can accommodate pores of the catalyst metal is often present.
- Such an embodiment is effective for supporting the catalyst metal in a highly dispersed manner on the support. That is, the effect of the present invention can be exhibited at a higher level by adjusting the pore diameter of the support so as to match the size of the catalyst metal.
- the ratio of the P 50 for the D 50 is generally greater than 1, typically 2 or more, preferably 5 or more, there is for example 7 or more, generally 40 Hereinafter, it is typically 30 or less, preferably 25 or less, more preferably 20 or less, for example 15 or less.
- the ratio of the P 90 for the D 50 is approximately 50 or less, preferably 40 or less, for example 34 or less.
- a plurality of metal species are used in combination as the catalyst metal.
- the arrangement of the catalyst metal can be adjusted as appropriate according to, for example, the operating conditions of the internal combustion engine.
- a plurality of metal species may be arranged so as to be mixed over the entire catalyst layer.
- the catalyst layer has a two-layer structure in the thickness direction, and one metal species (for example, Rh) is formed on the upper layer side.
- Other metal species for example, Pd and / or Pt
- one metal species may be included on the upstream side and another metal species may be included on the downstream side along the cylindrical direction of the base material (the flow direction of the exhaust gas).
- the content ratio of the first metal species and the second metal species is preferably 5: 1 to 2: 1, and is 3: 1 to 2: 1. It is preferable. According to the study by the present inventors, sintering tends to occur easily in an embodiment in which the amounts of two kinds of metals used are extremely different. By setting it as the said range, the purification capacity of a catalyst can be exhibited fully and the effect of this invention can be fully acquired.
- the content (supported amount) of the catalyst metal is not particularly limited because it may vary depending on the amount of exhaust gas or the use, but is generally 0.1% by mass or more, typically 0.2% by mass of the total mass of the catalyst layer. As mentioned above, it is 0.3 mass% or more, for example, Preferably it is 0.4 mass% or more, Comprising: It is good in general being 3 mass% or less, typically 2 mass% or less, for example, 1 mass% or less. If the content of the catalyst metal is too small, it is difficult to obtain desired exhaust gas purification performance, and emission of harmful components may occur. On the other hand, if the content of the catalyst metal is too large, grain growth or alloying of the catalyst metal particles proceeds, and the desired catalytic activity may not be stably obtained. Furthermore, it is disadvantageous in terms of cost. By setting it as the said range, the effect of this invention can be exhibited at a high level.
- the exhaust gas-purifying catalyst disclosed herein can be produced by a method similar to the conventional method, except that a ceramic satisfying the pore size distribution is used as a carrier.
- the formation of the catalyst layer is, for example, a method in which a slurry containing a carrier powder (ceramic powder) is wash-coated on the surface of a substrate, and then a catalyst metal is supported on the carrier by a conventionally known impregnation loading method or the like.
- a catalyst metal may be supported in advance on carrier particles constituting the carrier powder, and a slurry containing the catalyst metal-containing carrier powder may be wash coated on the surface of the substrate.
- a slurry for forming a washcoat layer is prepared using a desired ceramic powder as a carrier powder and a binder (for example, alumina sol, silica sol, etc.).
- the binder is approximately 1 to 10 g / L-cat. For example, 5 to 8 g / L-cat. Should be included.
- the slurry can be properly adhered to the surface of the substrate.
- other optional components may be appropriately added to the slurry.
- a typical example of such an additive component is a conventionally known oxygen storage / release material (OSC material: Oxygen® Storage® Capacity).
- OSC material oxygen storage / release material
- an appropriate base material is prepared, and the prepared slurry is supplied from one end portion of the base material and sucked from the other end portion.
- the amount of slurry applied is not particularly limited, but is usually 70 to 500 g / L-cat. For example, 100 to 200 g / L-cat. It is good to have a degree. By setting it as such a coating amount, the particle growth of the catalyst metal carry
- the substrate to which the slurry is applied is dried at a predetermined temperature and time, and heat-treated (fired).
- the drying and firing conditions of the slurry coated on the surface of the substrate are not particularly limited because it can vary depending on, for example, the shape and size of the substrate or carrier, but is usually about 50 to 120 ° C. (eg 60 to 100 ° C.). And then drying for about 1 to 10 hours, followed by baking at about 400 to 1000 ° C. (eg, 400 to 600 ° C.) for about 2 to 4 hours, thereby forming a desired washcoat layer in a relatively short time. it can.
- a desired catalyst metal component (typically a solution containing a catalyst metal such as Pd, Pt, Rh, etc. as ions) is applied to the surface of the washcoat layer, impregnated and supported with the catalyst metal, Dry again at temperature and time and heat-treat.
- the drying and firing conditions can be the same as, for example, when forming the washcoat layer. Thereby, an exhaust gas purifying catalyst can be produced.
- the exhaust gas purifying catalyst disclosed herein is capable of exhibiting excellent exhaust gas purifying performance, with the grain growth of the catalyst metal being better suppressed. Therefore, it can arrange
- the exhaust gas purifying catalyst of Example 1 includes a cylindrical honeycomb base material and a catalyst layer having a single layer structure provided on the base material.
- Such an exhaust gas-purifying catalyst was prepared as follows. First, commercially available alumina powder (average particle size 90 ⁇ m) was pulverized using Attritor (registered trademark) under the conditions of pulverization medium: water, rotation speed: 200 rpm, and pulverization time: 30 minutes. The obtained alumina powder has an average particle size of 5.5 ⁇ m, a pore diameter P 10 corresponding to a cumulative 10% from the small pore side of 10 nm, an average pore diameter P 50 of 25 nm, and a small pore side. The pore diameter P 90 corresponding to 90% cumulative from the pores was 34 nm, the pore diameter P 95 corresponding to the cumulative 95% from the small pore side was 40 nm, and the pore volume was 0.7 ml / g.
- This alumina powder, aluminum nitrate (40 mass% aqueous solution) and alumina sol as a binder are weighed at a mass ratio of 100: 25: 6, dispersed in ion-exchanged water, and using Attritor (registered trademark). A slurry was prepared. The amount of binder at this time was 6.57 g / L-cat. It was.
- the obtained slurry was introduced from one end face of the base material and sucked from the other end face to give the entire surface of the base material (rib wall).
- a cylindrical straight flow type honeycomb substrate made of cordierite having a volume (referring to the entire bulk volume including the volume of the cell passage) of about 0.02 L was used.
- excess slurry was dropped from the substrate, dried at 70 ° C. for 2 hours to remove moisture, and then heat treated at 500 ° C. to remove the template. As a result, 120 g / L-cat. A washcoat layer was formed.
- the base material on which the washcoat layer was formed was impregnated with an aqueous nitric acid solution of dinitrodiaminoplatinum to carry 0.55% by mass of Pt. Further, it was impregnated with an aqueous palladium nitrate solution to carry 0.28% by mass of Pd.
- the catalyst for exhaust gas purification Example 1 in which the catalyst layer was formed on the base material was obtained by performing baking at 500 ° C. for 1 hour. Incidentally, a part of the catalyst layer was TEM observation was determined an average particle diameter D 50 of the catalyst metal particles was 1 nm.
- Example 2 ceria powder (average particle size 5 ⁇ m, P 10 11 nm, P 50 25 nm, P 90 40 nm, P 95 45 nm, pore volume 0.5 ml / g) was used as the carrier.
- Example 3 the amount of binder contained in the slurry for forming the washcoat layer was 9.86 g / L-cat. Except that, an exhaust gas purifying catalyst (Example 3) was produced in the same manner as in Example 1.
- Example 4 the amount of the slurry for forming the washcoat layer was 180 g / L-cat. Except that, an exhaust gas purifying catalyst (Example 4) was produced in the same manner as in Example 1.
- Example 5 an exhaust gas purification catalyst (Example 5) was produced in the same manner as in Example 1 except that the supported amount of Pt was 0.28% by mass and the supported amount of Pd was 0.14% by mass.
- Example 6 an exhaust gas purification catalyst (Example 6) was produced in the same manner as in Example 1 except that the supported amount of Pt was 1.89% by mass and the supported amount of Pd was 0.94% by mass.
- Example 7 an exhaust gas purification catalyst (Example 7) was prepared in the same manner as in Example 1 except that the supported amount of Pt was 2.36% by mass and the supported amount of Pd was 0.47% by mass.
- Example 8 alumina powders having different properties (average particle size 5 ⁇ m, P 10 8 nm, P 50 17 nm, P 90 54 nm, P 95 70 nm, pore volume 0.8 ml / g) are used as the carrier.
- Exhaust gas purifying catalyst Example 8 was prepared in the same manner as Example 1 except for the above.
- Example 9 an exhaust gas purification catalyst (Example 9) was produced in the same manner as in Example 1 except that no binder was used.
- Example 10 the amount of the slurry for forming the washcoat layer was 60 g / L-cat. Except that, an exhaust gas purifying catalyst (Example 10) was prepared in the same manner as in Example 1.
- Example 11 an exhaust gas purification catalyst (Example 11) was produced in the same manner as in Example 1 except that the supported amount of Pt was 0.14% by mass and the supported amount of Pd was 0.07% by mass.
- Example 12 the catalyst for purifying exhaust gas (Example 12) was prepared in the same manner as in Example 1 except that the amount of Pt supported was 2.83 mass% and Pd was not supported (not impregnated with an aqueous palladium nitrate solution). Produced.
- Example 13 an exhaust gas purification catalyst (Example 13) was produced in the same manner as in Example 1 except that the supported amount of Pt was 2.57% by mass and the supported amount of Pd was 0.26% by mass.
- the exhaust gas-purifying catalysts (Examples 1 to 13) thus obtained were subjected to durability treatment, and then the 50% purification temperature was evaluated. Specifically, first, the exhaust gas-purifying catalyst was put in an electric furnace and heat-treated in air at 600 ° C. for 50 hours. Next, the exhaust gas purification catalyst after the endurance treatment is installed in the rig apparatus, and the simulated exhaust gas having the configuration shown in Table 1 below is set to have an SV value of 75000 / h while being heated at a temperature rising rate of 30 ° C./min. HC (here, propylene) concentration and CO concentration at the outlet were measured. And the temperature when it became 50 mol% of HC concentration or CO concentration of inflow gas was measured, respectively.
- HC here, propylene
- Table 2 below shows test examples in which the pore size distribution of the ceramic constituting the support is different.
- HC_T50 represents the 50% purification temperature (° C.) of propylene
- CO_T50 represents the 50% purification temperature (° C.) of carbon monoxide. It can be said that the lower the 50% purification temperature, the better the purification performance.
- Example 1 and Example 8 are compared.
- Example 1 is an example in which P 10 and P 90 are both in the range of 5 to 50 nm.
- Example 1 has a pore diameter distribution in which P 10 / P 90 is relatively close to 1 (sharp).
- Example 8 is a comparative example P 90 is not in the range of 5 ⁇ 50 nm.
- Example 8 has a pore size distribution in which P 10 / P 90 is relatively close to 0 (broad).
- Table 2 in Example 1, it was possible to realize higher HC purification performance and CO purification performance than in Example 8. The reason for this is considered to be that the catalyst metal can be supported in a highly dispersed manner by making the pore diameters of the carrier uniform, and the sintering of the catalyst metal can be effectively suppressed.
- Example 2 is a test example in which the type of ceramic is different from Example 1. As can be seen from Example 2, when ceria was used as the support ceramic, purification performance substantially equivalent to that using alumina could be achieved. From this, it has been found that the effect of improving the purification performance described above is not limited to the type of ceramic, but the carrier only needs to satisfy a predetermined pore size distribution.
- Table 3 shows test examples in which the content of the catalyst metal and the content ratio of a plurality of metal species are different. In addition, about the description of purification performance, it is the same as that of the said Table 2.
- Example 1, Example 5, Example 6, and Example 11 having different catalyst metal contents will be compared.
- the total amount of catalyst metals is 0.4 mass% or more (more specifically 0.42 mass% or more), so that the 50% HC purification temperature is 200 ° C.
- the 50% purification temperature of CO was less than 150 ° C. Therefore, it was found that the total amount of the catalyst metal is preferably 0.4% by mass or more from the viewpoint of realizing excellent HC purification performance and CO purification performance.
- the total amount of catalyst metals should be 3% by mass or less (specifically, 2.83% by mass or less) from the balance between purification performance and cost.
- Examples 6, 7, 12, and 13 having different metal species content ratios will be compared.
- the purification performance could be further improved by using a plurality of metal species in combination as the catalyst metal.
- the content ratio of Pt and Pd is preferably about 5: 1 to 2: 1, and more preferably 3: 1 to 2: 1.
- Table 4 shows test examples in which the binder content and the coating amount of the slurry for forming the washcoat layer are different. In addition, about the description of purification performance, it is the same as that of the said Table 2.
- Example 1 based on a comparison between Example 1, Example 3, and Example 9, the slurry for forming the washcoat layer was adjusted to, for example, 6 to 10 g / L-cat. It can be said that it is preferable to contain a binder at a ratio of Further, in this study example, from the comparison of Example 1, Example 4, and Example 10, the coating amount of the washcoat layer (amount of slurry applied) was 100 to 200 g / L-cat. It can be said that (in detail, 120 to 180 g / L-cat.) Is preferable.
- ⁇ Evaluation of purification performance 2 ⁇ Durability was evaluated using a separately prepared exhaust gas-purifying catalyst (Examples 1 and 8). Specifically, first, an exhaust gas purifying catalyst is installed in a rig device, and the SV value of the simulated exhaust gas having the configuration shown in Table 5 below is set to the first idle from the start of the engine while the temperature is increased at a temperature increase rate of 40 ° C./min. It was made to flow so that it might become 60000 / h, and HC_T50 and CO_T50 were measured similarly to the said evaluation 1. Next, the exhaust gas-purifying catalyst was put in an electric furnace and subjected to endurance treatment (heat treatment in air at 600 ° C.
- FIG. 2 is a graph comparing HC oxidation activities.
- FIG. 3 is a graph comparing CO oxidation activity.
- Example 1 according to the present invention was superior in durability compared to Example 8 related to the conventional product. That is, as shown in FIG. 2, according to the technique disclosed herein, the HC purification performance of the catalytic metal can be stably exhibited over a long period of time, and a relatively long life can be realized. . Moreover, as shown in FIG. 3, according to the technique disclosed here, the fall of the CO purification performance of a catalyst metal can be suppressed compared with the past. These results show the technical significance of the present invention.
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Abstract
Description
なお、本国際出願は2014年10月2日に出願された日本国特許出願2014-204287号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
本発明はかかる課題を解決すべく創出されたものであり、その目的は、触媒金属の粒成長がより良く抑制され、浄化性能の高い排ガス浄化用触媒を提供することである。
本発明に係る排ガス浄化用触媒は、自動車エンジンなどの内燃機関の排気管に配置されて該内燃機関から排出される排ガスの浄化を行う排ガス浄化用触媒である。かかる排ガス浄化用触媒は、基材と、該基材上に形成された触媒層であって酸化及び/又は還元触媒として機能する触媒金属と該触媒金属を担持する担体を含む触媒層と、を備えている。上記担体は、窒素ガス吸着法に基づいて測定された体積基準の細孔径分布において、小細孔側からの累積10%に相当する細孔直径P10と小細孔側からの累積90%に相当する細孔直径P90とがいずれも5~50nmの範囲にある多孔質セラミックで構成されている。
なお、本明細書において「細孔径分布」とは、窒素ガスを用いたガス吸着法で測定された吸着等温線をBJH(Barrett-Joyner-Halenda)法で解析して得られる体積基準の細孔径分布をいう。
また、上記P90は20~50nmであり得る。P90を上記範囲に抑えることにより、触媒金属の分散性を向上することができ、高温条件下での触媒性能の低下を抑制することができる。したがって、本発明の効果をさらに高いレベルで実現することができる。
P10/P90は、細孔径分布が狭い(シャープな)ほど1に近くなり、逆に細孔径分布が幅広い(ブロードな)ほど0に近づく。すなわち、P10/P90は、細孔径分布の広がりを表す1つの指標となる。P10/P90が0.25以上であることは、細孔径が、より揃っていることを意味する。これにより、触媒金属を、より均質に分散させることができる。その結果、触媒金属の粒成長にともなうシンタリングを一層抑制することができる。また、セラミックのP10/P90が0.6以下であることは、細孔径が、より幅を持つことを意味する。これにより、圧損の低減とシンタリングの抑制とを高いレベルでバランスすることができる。また、生産効率の向上や歩留まりを改善する観点からも好ましい。
触媒金属(特には白金族に属する貴金属)は、資源として貴重であるとともに近年その価格も高騰している。このため、省エネや低コストの観点から使用量の低減が望まれている。ここに開示される発明によれば触媒金属担持量対比の触媒活性を向上することができるため、触媒金属の使用量を上記範囲まで低減しても、良好な排ガス浄化性能を実現することができる。
排ガス浄化用触媒10に供給された排ガスは、ハニカム基材1の流路内(セル2内)を流動(通過)している間にリブ壁4上に設けられた触媒層と接触する。これによって、排ガス中の有害成分が浄化される。例えば、排ガスに含まれるHCやCOは、触媒層の触媒機能によって酸化され、水(H2O)や二酸化炭素(CO2)などに変換(浄化)される。また、例えばNOxは、触媒層の触媒機能によって還元され、窒素(N2)に変換(浄化)される。以下、排ガス浄化用触媒10の各構成要素について順に説明する。
ハニカム基材1は、排ガス浄化用触媒の骨格を構成するものである。ハニカム基材1としては特に限定されず、従来この種の用途に用いられる種々の材料からなるものを採用することができる。なかでも高耐熱性素材からなるものが好ましい。例えば、セラミックス製、具体的には、酸化アルミニウム(アルミナ:Al2O3)、酸化セリウム(セリア:CeO2)、酸化チタン(チタニア:TiO2)、酸化ジルコニウム(ジルコニア:ZrO2)、酸化ケイ素(シリカ:SiO2)等の酸化物系セラミックス製;コージェライト(2MgO・2Al2O3・5SiO2)等の複合酸化物系セラミックス製;炭化ケイ素(シリコンカーバイド:SiC)等の炭化物系セラミックス製;のものを好適に採用することができる。あるいは、ステンレス鋼等の合金製であってもよい。
触媒層は、排ガスを浄化する場として排ガス浄化用触媒の主体をなすものである。触媒層は、多孔質な担体と、該担体の表面に担持された触媒金属とを備えている。
小細孔側からの累積50%に相当する平均細孔直径P50は上記範囲であればよいが、典型的には20nm以上、例えば25nm以上であって、概ね40nm以下、例えば30nm以下であり得る。これにより、圧損の低減とシンタリングの抑制とを高いレベルでバランスすることができる。
小細孔側からの累積95%に相当する細孔直径P95は特に限定されないが、典型的には35nm以上、例えば40nm以上であって、概ね100nm以下、例えば50nm以下であり得る。換言すれば、概ね100nm以上、典型的には50nm以上、例えば40nm以上の粗大な細孔容積の割合が、全細孔容積の5%以下であり得る。このように比較的大きな細孔(例えばマクロ孔)の割合を低減することで、本発明の効果をさらに高いレベルで発揮することができる。
また、P10/P90が所定値以下であることは、細孔径分布が比較的ブロードで、細孔直径が所定の広がりを持っている(バラついている)ことを示す。このようなセラミック粉末は、特殊な製造装置等を必要とせず、比較的簡便に準備することができる。このことは、生産効率向上やコスト低減の観点から好ましい。さらに、触媒層の機械的強度(耐久性)と圧損の抑制とを、より良くバランスすることができる。
好適な一態様では、上記D50に対する上記P90の比(P90/D50)が、概ね50以下、好ましくは40以下、例えば34以下である。
上記比が所定値以上であると、触媒金属を十分高度に分散した状態で担持することができる。上記比が所定値以下であると、触媒金属の粒成長にともなうシンタリングを好適に抑制することができる。したがって、本発明の効果をより高いレベルで発揮することができる。
ここに開示される排ガス浄化用触媒は、担体として上記細孔径分布を満たすセラミックを用いること以外、従来と同様の方法で製造することができる。なお、触媒層の形成は、例えば、担体粉末(セラミック粉末)を含んだスラリーを基材の表面にウォッシュコートした後、従来公知の含浸担持法等によって担体に触媒金属を担持する方法であってもよいし、担体粉末を構成する担体粒子に触媒金属を予め担持させて、当該触媒金属含有担体粉末を含んだスラリーを基材の表面にウォッシュコートしてもよい。
ここに開示される排ガス浄化用触媒は、触媒金属の粒成長がより良く抑制され、優れた排ガス浄化性能を発揮し得るものである。したがって、種々の内燃機関、例えば自動車のディーゼルエンジンやガソリンエンジンの排気系(排気管)に好適に配置することができる。
先ず、アトライター(登録商標)を用いて、粉砕媒体:水、回転数:200rpm、粉砕時間:30分の条件で、市販のアルミナ粉末(平均粒径90μm)を粉砕した。得られたアルミナ粉末は、平均粒径が5.5μmであり、小細孔側からの累積10%に相当する細孔直径P10が10nm、平均細孔直径P50が25nm、小細孔側からの累積90%に相当する細孔直径P90が34nm、小細孔側からの累積95%に相当する細孔直径P95が40nmであり、細孔容積が0.7ml/gだった。
上記得られた排ガス浄化用触媒(例1~例13)に耐久処理を施した後、50%浄化温度を評価した。具体的には、先ず上記排ガス浄化用触媒を電気炉に入れ、空気中において600℃で50時間熱処理した。次に、耐久処理後の排ガス浄化触媒をリグ装置に設置し、昇温速度30℃/minで昇温させながら、下表1に示す構成の模擬排ガスをSV値が75000/hとなるように流入させ、出口におけるHC(ここではプロピレン)濃度とCO濃度を測定した。そして、流入ガスのHC濃度あるいはCO濃度の50mol%になった時の温度をそれぞれ測定した。
表2から明らかなように、例1では、例8に比べて高いHC浄化性能及びCO浄化性能を実現することができた。この理由としては、担体の細孔直径を均質に揃えることにより、触媒金属を高分散担持することができ、触媒金属のシンタリングを効果的に抑制できたことが考えられる。
表3から明らかなように、本検討例では、触媒金属の合計量を0.4質量%以上(詳細には0.42質量%以上)とすることで、HCの50%浄化温度を200℃未満、COの50%浄化温度を150℃未満とすることができた。したがって、優れたHC浄化性能及びCO浄化性能を実現する観点からは、触媒金属の合計量を0.4質量%以上とすることが好ましいとわかった。一方で、省エネや低コストの観点からは、触媒金属量を低減することが好ましい。例1と例6との比較によれば、浄化性能向上の効果は、やや頭打ちの傾向が認められる。したがって、浄化性能とコストとのバランスからは、触媒金属の合計を3質量%以下(詳細には2.83質量%以下)とすることがよいとわかった。
表3から明らかなように、本検討例では、触媒金属として複数の金属種を併用することで、浄化性能を更に向上することができた。さらに、複数種の金属種を併用する場合には、各金属種の使用量に極端な差がないことが好ましいといえる。例えば、PtとPdとの含有比率を、5:1~2:1程度とすることが好ましく、3:1~2:1とすることがより好ましい。
また、本検討例では、例1、例4、例10の比較から、ウォッシュコート層のコート量(スラリーの付与量)は、100~200g/L-cat.(詳細には120~180g/L-cat.)とすることが好ましいといえる。
別途作成した排ガス浄化用触媒(例1及び例8)を用いて、耐久性を評価した。具体的には、先ず、排ガス浄化触媒をリグ装置に設置し、昇温速度40℃/minで昇温させながら、エンジン始動からファーストアイドルで、下表5に示す構成の模擬排ガスをSV値が60000/hとなるように流入させ、上記評価1と同様にHC_T50とCO_T50を測定した。次に、上記排ガス浄化用触媒を電気炉に入れ耐久処理(空気中において600℃で25時間の熱処理)を行った後、ふたたびリグ装置に設置し、同様の条件でHC_T50とCO_T50を測定した。同様にして、耐久処理を50時間、100時間、200時間施したものをそれぞれ測定し、排ガス浄化用触媒の耐久性を評価した。結果を図2及び図3に示す。なお、図2はHC酸化活性を比較したグラフである。また、図3は、CO酸化活性を比較したグラフである。
2 貫通孔(セル)
4 隔壁(リブ壁)
10 排ガス浄化用触媒
Claims (10)
- 内燃機関の排気管に配置されて該内燃機関から排出される排ガスの浄化を行う排ガス浄化用触媒であって、
基材と、該基材上に形成された触媒層とを備え、
前記触媒層は、酸化及び/又は還元触媒として機能する触媒金属と、該触媒金属を担持する担体とを含み、
前記担体は、窒素ガス吸着法に基づいて測定された体積基準の細孔径分布において、小細孔側からの累積10%に相当する細孔直径P10と小細孔側からの累積90%に相当する細孔直径P90とがいずれも5~50nmの範囲にある多孔質セラミックで構成されている、排ガス浄化用触媒。 - 前記P90に対する前記P10の比(P10/P90)が、0.25≦(P10/P90)≦0.6を満たしている、請求項1に記載の排ガス浄化用触媒。
- 前記P90が20~50nmである、請求項1又は2に記載の排ガス浄化用触媒。
- 前記多孔質セラミックは、100nm以上の細孔容積の割合が、全細孔容積の5%以下である、請求項1~3のいずれか一項に記載の排ガス浄化用触媒。
- 前記P10が5~20nmである、請求項1~4のいずれか一項に記載の排ガス浄化用触媒。
- 前記多孔質セラミックの細孔容積が0.2ml/g以上である、請求項1~5のいずれか一項に記載の排ガス浄化用触媒。
- 前記触媒金属の割合が、前記触媒層の全質量に対して0.3~1質量%である、請求項1~6のいずれか一項に記載の排ガス浄化用触媒。
- 前記細孔径分布において、小細孔側からの累積50%に相当する平均細孔直径P50と、
前記触媒金属の電子顕微鏡観察に基づく個数基準の平均粒径D50との比(P50/D50)が、5≦(P50/D50)≦30を満たしている、請求項1~7のいずれか一項に記載の排ガス浄化用触媒。 - 前記細孔径分布において、小細孔側からの累積50%に相当する平均細孔直径P50が、20nm以上である、請求項1~8のいずれか一項に記載の排ガス浄化用触媒。
- 前記触媒金属の電子顕微鏡観察に基づく個数基準の平均粒径D50が、前記P10よりも小さい、請求項1~9のいずれか一項に記載の排ガス浄化用触媒。
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Cited By (2)
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WO2023085089A1 (ja) * | 2021-11-11 | 2023-05-19 | ユミコア日本触媒株式会社 | 排気ガス浄化用触媒およびそれを用いた排気ガス浄化方法 |
JP7299443B1 (ja) * | 2021-11-11 | 2023-06-27 | ユミコア日本触媒株式会社 | 排気ガス浄化用触媒およびそれを用いた排気ガス浄化方法 |
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EP3202495A4 (en) | 2017-10-04 |
US20170297011A1 (en) | 2017-10-19 |
US10668459B2 (en) | 2020-06-02 |
JP6594328B2 (ja) | 2019-10-23 |
JPWO2016052735A1 (ja) | 2017-07-27 |
EP3202495A1 (en) | 2017-08-09 |
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