WO2020031975A1 - Filtre à particules d'essence revêtu de catalyseur et son procédé de production - Google Patents

Filtre à particules d'essence revêtu de catalyseur et son procédé de production Download PDF

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Publication number
WO2020031975A1
WO2020031975A1 PCT/JP2019/030770 JP2019030770W WO2020031975A1 WO 2020031975 A1 WO2020031975 A1 WO 2020031975A1 JP 2019030770 W JP2019030770 W JP 2019030770W WO 2020031975 A1 WO2020031975 A1 WO 2020031975A1
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Prior art keywords
catalyst
particulate filter
exhaust gas
layer
flow type
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PCT/JP2019/030770
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English (en)
Japanese (ja)
Inventor
浩幸 原
大司 望月
豪人 高山
裕基 中山
永田　誠
Original Assignee
エヌ・イーケムキャット株式会社
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Application filed by エヌ・イーケムキャット株式会社 filed Critical エヌ・イーケムキャット株式会社
Priority to CN201980036754.3A priority Critical patent/CN112236231B/zh
Priority to JP2020535764A priority patent/JP7065551B2/ja
Publication of WO2020031975A1 publication Critical patent/WO2020031975A1/fr
Priority to JP2022069830A priority patent/JP7228065B2/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/025—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using fuel burner or by adding fuel to exhaust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to a catalyst-coated gasoline particulate filter in which a catalyst layer is provided on a wall flow type substrate and a method for producing the same.
  • a diesel particulate filter (hereinafter, may be referred to as “DPF”) that accumulates and collects particulate matter is used in an exhaust gas passage to reduce particulate matter contained in exhaust gas.
  • DPF diesel particulate filter
  • GPF gasoline particulate filter
  • a catalyst slurry such as a three-way catalyst is applied to a particulate filter, and the catalyst layer is provided by calcining the catalyst slurry.
  • a catalyst-coated gasoline particulate filter (hereinafter referred to as "GPF catalyst”) It may be referred to.).
  • Patent Documents 1 to 3 disclose the types of catalyst layers and the positions at which they are provided for the purpose of suppressing an increase in pressure loss and improving exhaust gas purification performance.
  • Patent Document 4 discloses that the average particle diameter of powder in a slurry for forming a catalyst coat layer and the amount of catalyst coated on a substrate are adjusted for the purpose of suppressing an increase in pressure loss. Proposed.
  • the conventional GPF catalyst has insufficient PN collection rate as the basic performance of the GPF, and there is a need for the development of a GPF catalyst based on a new design guideline capable of responding to the planned tightening of the global PN regulation. Have been.
  • an object of the present invention is to provide a catalyst-coated gasoline particulate filter in which the PN collection rate is dramatically improved as compared with a conventional GPF catalyst, and a method for producing the same.
  • Another object of the present invention is to provide a new catalyst structure capable of dramatically increasing the PN collection rate, and at the same time, realizing the same pressure loss and exhaust gas purification performance as the conventional one. It is in.
  • the present invention is not limited to the object described above, and is an operation and effect derived from each configuration shown in the embodiment for carrying out the invention described later, and also has an operation and effect that cannot be obtained by the conventional technology. It can be positioned for other purposes.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, it has been found that the above problem can be solved by zone-coating a porous dense trapping layer capable of trapping extremely fine PM over the stretching direction of the partition wall of the wall flow type base material, thereby completing the present invention. Reached.
  • a catalyst-coated gasoline particulate filter provided with a catalyst layer for purifying exhaust gas discharged from a gasoline engine, wherein an inlet cell having an open end on the exhaust gas inlet side and an end on the exhaust gas discharge side And the discharge-side cell having an opening, a wall-flow-type substrate defined by a porous partition wall, and a plurality of porous dense portions filled with inorganic fine particles in pores of the partition wall, the wall-flow type A porous dense trapping layer formed in the direction of extension of the partition walls of the base material, and having a length La of 0.4 to 0.9 L with respect to the total length L of the wall flow type base material in cross section.
  • a catalyst-coated gasoline particulate filter comprising at least the porous dense collection layer.
  • a method for producing a catalyst-coated gasoline particulate filter provided with a catalyst layer for purifying exhaust gas discharged from a gasoline engine comprising: an inlet cell having an open end on the exhaust gas inlet side; The step of preparing a wall flow type substrate defined by a porous partition wall, the discharge side cell having an open end portion, the inorganic from the end of the wall flow type base material on the exhaust gas introduction side or exhaust gas discharge side.
  • the precursor composition of the porous dense trapping layer containing the fine particles is supplied, and over the extending direction of the partition wall of the wall flow type substrate, the total length L in a cross-sectional view of the wall flow type substrate is 0.4.
  • This catalyst-coated gasoline particulate filter is not only a particulate filter with particularly excellent PN collection rate, but also a three-way catalyst (TWC: Three Way Catalyst Catalyst) that reduces NOx, CO, HC and the like in exhaust gas. ), It can be replaced with a three-way catalyst installed in a direct-type catalytic converter under an engine or a direct-type catalytic converter in a tandem arrangement, thereby saving space, reducing canning costs, and reducing costs. Can be planned.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a catalyst-coated gasoline particulate filter 100.
  • FIG. 2 is a sectional view taken along the line (II)-(II) of FIG. 1.
  • FIG. 3 is a sectional view taken along (III)-(III) of FIG. 1. It is a flowchart which shows an example of the manufacturing method of a catalyst coating gasoline particulate filter 100.
  • the step S11 of the method for producing the catalyst-coated gasoline particulate filter 100 is shown.
  • Step S12 of the method for producing the catalyst-coated gasoline particulate filter 100 is shown.
  • Step S12 of the method for producing the catalyst-coated gasoline particulate filter 100 is shown.
  • FIG. 3 is a schematic cross-sectional view showing another embodiment of the catalyst-coated gasoline particulate filter 100. It is (XI)-(XI) sectional drawing of FIG.
  • FIG. 12 is a sectional view taken along (XII)-(XII) in FIG. 10.
  • FIG. 4 is a schematic cross-sectional view showing another embodiment of the catalyst-coated gasoline particulate filter 100.
  • FIG. 14 is a sectional view taken along (XIV)-(XIV) in FIG. 13.
  • FIG. 14 is a sectional view taken along line (XV)-(XV) of FIG. 13.
  • FIG. 9 is a schematic cross-sectional view showing still another embodiment of the catalyst-coated gasoline particulate filter 100.
  • FIG. 17 is a sectional view taken along line (XVII)-(XVII) of FIG. 16.
  • FIG. 17 is a sectional view taken along line (XVIII)-(XVIII) of FIG. 16.
  • a numerical range notation of “1 to 100” includes both the upper limit value “100” and the lower limit value “1”. The same applies to the notation of other numerical ranges.
  • the “D50 particle diameter” refers to a particle diameter when an integrated value from a small particle diameter reaches 50% of the whole in a cumulative distribution of a particle diameter on a volume basis, and a so-called median diameter.
  • “D90 particle size” refers to the particle size when the integrated value from the small particle size reaches 90% of the total in the cumulative distribution of the particle size on a volume basis, and these are the laser diffraction type. It means a value measured by a particle size distribution measuring device (eg, a laser diffraction type particle size distribution measuring device SALD-3100 manufactured by Shimadzu Corporation).
  • FIG. 1 is a schematic cross-sectional view illustrating a schematic configuration of a catalyst-coated gasoline particulate filter 100 (hereinafter, may be referred to as a “GPF catalyst”) according to an embodiment of the present invention.
  • the catalyst-coated gasoline particulate filter 100 of the present embodiment includes at least a wall flow type substrate 10 and a porous dense trapping layer 31 zone-coated on a part of the wall flow type substrate 10. Note that the black arrows in FIG. 1 indicate the introduction direction and the discharge direction of the exhaust gas.
  • the overall configuration of the catalyst-coated gasoline particulate filter 100 will be described in detail.
  • the wall flow type base material 10 is such that an introduction-side cell 11 having an open end 11a on the exhaust gas introduction side and a discharge-side cell 12 having an open end 12a on the exhaust gas discharge side are porous. It is composed of a plurality of structures (catalyst carriers) arranged in parallel with the partition walls 13 interposed therebetween.
  • the opening at one end 11a and the opening at the other end 12a in the cell extending direction are alternately sealed by plugging walls 51.
  • the introduction-side cells 11 and the discharge-side cells 12 adjacent to each other are alternately formed.
  • the exhaust gas introduced from the end 11a side of the introduction side cell 11 passes through the introduction side cell 11, the partition 13 and the discharge side cell 12 in this order, and from the end 12a side of the discharge side cell 12. It is discharged out of the system.
  • the partition wall 13 of the wall flow type substrate 10 is provided with a first catalyst layer 21 containing a platinum group element by a wash coat (hereinafter, the first catalyst layer 21 is coated on the wall flow type substrate 10 after coating the first catalyst layer 21). May be referred to as “post-catalyst-coated wall-flow-type substrate 41”.) As shown in FIGS. 2 and 3, the first catalyst layer 21 is provided on the pore surface of the partition wall 13 of the wall flow type substrate 10. Therefore, the wall flow type base material 41 after the catalyst application functions as an exhaust gas purifying catalyst for purifying the exhaust gas discharged from the gasoline engine in the first catalyst layer 21 and the particulate matter (PM: Particulate) contained in the exhaust gas. Matter) functions as a GPF (Gasoline Particulate Filter) which collects and separates (removes) the surface and pores of the partition 13.
  • GPF Gasoline Particulate Filter
  • the porous dense trapping layer having a predetermined length La in the cross-sectional view shown in FIG. 31 is provided by a wash coat.
  • the porous dense trapping layer 31 is provided on the first catalyst layer 21 formed in the pores of the partition 13 of the wall flow type base material 41 after the catalyst application (see FIG. 3).
  • the porous dense trapping layer 31 is for trapping PM contained in exhaust gas with high efficiency.
  • the porous dense trapping layer 31 has pores in the partition walls 13 of the wall flow type base material 10 (in pores of the partition walls 13 of the wall flow type base material 41 after the catalyst application).
  • a plurality of dense porous portions 31a filled with inorganic fine particles at a high density By filling the pores of the partition 13 with the inorganic fine particles at a high density, the porous dense portion 31a having voids (pores) whose pore diameter is extremely small as compared with the pores of the partition 13 is formed. .
  • the presence of the porous dense portion 31a enables the collection of minute PM, which has been difficult to collect in the past, so that the PN collection rate is dramatically improved.
  • the porous dense trapping layer 31 is conceptualized as a set of porous dense parts 31 a formed in a plurality of pores of the partition wall 13 of the wall flow type substrate 10. . As shown in the schematic cross-sectional view of FIG. 1, the porous dense trapping layer 31 is macroscopically represented as a region where a plurality of porous dense parts 31a exist.
  • the porous dense trapping layer 31 is coated with a La zone having a predetermined length in the direction in which the partition wall 13 of the wall flow type substrate 10 extends.
  • the length La is 0.4 to 0.9 L with respect to the total length L of the wall flow type substrate 10 in a sectional view.
  • the PN collection rate can be dramatically improved, and the balance between pressure loss and exhaust gas purification performance can be maintained.
  • the length La of the porous dense collection layer 31 is greater than the total length L of the wall flow type substrate 10 in a cross-sectional view. Therefore, it is preferably 0.45 to 0.85 L, more preferably 0.5 to 0.8 L.
  • the thickness Da of the porous dense collection layer 31 can be appropriately set according to desired performance, and is not particularly limited. From the viewpoint of maintaining a high balance between the PN collection rate, the pressure loss, and the exhaust gas purification performance, the thickness Da of the porous dense collection layer 31 is 0.1 to 0 with respect to the thickness D of the partition wall 13 in a cross-sectional view. 0.9D is preferable, 0.1 to 0.7D is more preferable, and 0.2 to 0.5D is further preferable.
  • the location where the porous dense trapping layer 31 is formed is not particularly limited, but from the viewpoint of easy production of the porous dense trapping layer 31 (porous dense part 31a). Preferably, it is unevenly distributed on the cell wall surface side of the introduction-side cell 11 or unevenly distributed on the cell wall surface side of the discharge-side cell 12.
  • the uneven distribution of the porous dense collection layer 31 can be confirmed by, for example, a scanning electron microscope on a cross section of the partition wall 13 of the catalyst-coated gasoline particulate filter 100.
  • a second catalyst layer 32 is further provided by a wash coat (see FIG. 1).
  • the porous dense trapping layer 31 is provided in an uncoated exhaust gas introduction side end 11 a side region of the wall flow type substrate 41 after the catalyst application.
  • the second catalyst layer 21 is formed on the first catalyst layer 21 provided on the pore surface of the partition wall 13 of the wall flow type base material 41 after the catalyst coating.
  • a catalyst layer 32 is provided.
  • the second catalyst layer 32 contains base particles of inorganic fine particles and third composite catalyst particles having a platinum group element carried on the base particles.
  • the second catalyst layer 32 is for reinforcing the exhaust gas purification performance of the first catalyst layer 21 and is an optional catalyst layer. Further, if necessary, a third catalyst layer and a fourth catalyst layer can be provided.
  • the second catalyst layer 32 is provided with a predetermined length Lb from the end 11a side on the exhaust gas introduction side in the direction in which the partition walls 13 of the wall flow type substrate 10 extend.
  • the length Lb can be appropriately set according to the desired performance, and is not particularly limited. 0.55 L, more preferably 0.2-0.5 L.
  • the thickness of the second catalyst layer 32 can be appropriately set according to desired performance, and is not particularly limited. In the present embodiment, the example in which the second catalyst layer 32 is provided in a region corresponding to the thickness D of the partition 13 has been described, but the thickness of the second catalyst layer 32 may be smaller than the thickness D of the partition 13. At this time, the second catalyst layer 32 may be unevenly distributed on the cell wall surface side of the introduction-side cell 11 or the cell wall surface side of the discharge-side cell 12 in the thickness direction of the partition wall 13 in cross-sectional view. The uneven distribution of the second catalyst layer 32 can be confirmed by, for example, a scanning electron microscope on the cross section of the partition wall 13 of the catalyst-coated gasoline particulate filter 100.
  • the exhaust gas discharged from the gasoline engine flows into the introduction-side cell 11 from the exhaust-gas introduction-side end 11a (opening), and the pores of the partition wall 13 are formed. Then, it flows into the adjacent discharge-side cell 12 and flows out of the system from the end portion 12a (opening) on the exhaust gas discharge side. In this process, the exhaust gas comes into contact with the first catalyst layer 21 (and the second catalyst layer) formed in the pores of the partition 13, thereby causing carbon monoxide (CO) and hydrocarbon (HC) contained in the exhaust gas. Is oxidized to water (H 2 O), carbon dioxide (CO 2 ), etc., nitrogen oxide (NOx) is reduced to nitrogen (N 2 ), and harmful components are purified (detoxified).
  • the particulate matter (PM) contained in the exhaust gas accumulates on the partition 13 in the introduction-side cell 11 and / or in the pores of the partition 13.
  • the pores of the partition walls 13 of the wall flow type substrate 10 are provided with the porous dense trapping layer 31 composed of a plurality of porous dense parts 31a densely filled with inorganic fine particles.
  • the particle diameter is smaller than that of the conventional PM trapping only by the pores of the partition 13 or that of the conventional PM trapping only by the first catalyst layer 21 provided on the pore surface of the partition 13. Since PM can be collected with high efficiency, the PN collection rate is dramatically increased.
  • the deposited particulate matter is removed according to a conventional method, for example, by the catalytic function of the catalyst layer 21 or by burning at a predetermined temperature (for example, about 500 to 700 ° C.).
  • the porous dense collecting layer 31 (porous dense portion 31a) has many fine voids and coarse voids. It is desirable to have a low microporosity.
  • the porosity of the porous dense trapping layer 31 is determined by the pore diameter determined by the mercury intrusion method (for example, the mode diameter (pore diameter having the largest appearance ratio in the pore diameter frequency distribution (maximum distribution value)). )) And measuring the pore volume.
  • the porous dense trapping layer 31 preferably has microporosity in which the pore volume by a mercury intrusion method satisfies the following relationship.
  • the measurement of the microporosity of the porous dense trapping layer 31 is performed by collecting a measurement sample of a predetermined size from the partition wall 13 on which the porous dense trapping layer 31 is formed. It means the value calculated by the mercury intrusion method under the conditions described.
  • a microporous porous material having a large pore volume with a pore diameter of 0.1 ⁇ m or more and less than 5 ⁇ m is used.
  • the highly dense collection layer 31 is particularly preferably used.
  • Pore volume of less than or pore diameter 0.1 [mu] m 5 [mu] m is more preferably at least 0.06 cm 3 / g, more preferably 0.07 cm 3 / g or more, 0.08 cm 3 / g or more is particularly preferable.
  • the upper limit of such pore volume is not particularly limited, but usually is a measure is 5.00 cm 3 / g or less, preferably 3.00 cm 3 / g or less, more preferably 2.00 cm 3 / g or less is there.
  • the porous dense trapping layer 31 having such fine porosity uses fine inorganic fine particles capable of forming a void having a pore diameter of 0.1 ⁇ m or more and less than 5 ⁇ m when forming the porous dense portion 31a.
  • various known methods can be applied, such as using a fine pore former capable of forming a void having a pore diameter of 0.1 ⁇ m or more and less than 5 ⁇ m.
  • the pore volume of less than the pore diameter 0.1 [mu] m 1 [mu] m is more preferably at least 0.015cm 3 / g, 0.02cm 3 / more preferably more than g, 0.25 cm 3 / g or more Is particularly preferred, and 0.30 cm 3 / g or more is most preferred.
  • the upper limit of such pore volume is not particularly limited, but usually is a measure is 5.00 cm 3 / g or less, preferably 3.00 cm 3 / g or less, more preferably 2.00 cm 3 / g or less is there.
  • the porous dense trapping layer 31 having such microporosity is formed by using fine inorganic fine particles capable of forming a void having a pore diameter of 0.1 ⁇ m or more and less than 1 ⁇ m when forming the porous dense portion 31a.
  • various known methods can be applied, such as using a fine pore former capable of forming a void having a pore diameter of 0.1 ⁇ m or more and less than 1 ⁇ m.
  • the pore volume of less than or pore diameter 1 [mu] m 5 [mu] m is more preferably more than 0.025 cm 3 / g, more preferably 0.03 cm 3 / g or more, particularly preferably 0.034cm 3 / g or more, 0.36 cm 3 / G or more is most preferred.
  • the upper limit of such pore volume is not particularly limited, but usually is a measure is 5.00 cm 3 / g or less, preferably 3.00 cm 3 / g or less, more preferably 2.00 cm 3 / g or less is there.
  • the porous dense trapping layer 31 having such microporosity is formed by using fine inorganic fine particles capable of forming a void having a pore diameter of 1 ⁇ m or more and less than 5 ⁇ m when forming the porous dense part 31a.
  • 31a can be realized by applying various known methods, such as using a fine pore-forming material capable of forming a void having a pore diameter of 1 ⁇ m or more and less than 5 ⁇ m.
  • the pore volume having a pore diameter of 5 ⁇ m or more and less than 10 ⁇ m is more preferably 0.055 cm 3 / g or more, and 0.06 cm 3 or more. / g or more, and particularly preferably 0.07 cm 3 / g or more, 0.08 cm 3 / g or more is most preferred.
  • the upper limit of such pore volume is not particularly limited, but usually is a measure is 7.00cm 3 / g or less, preferably 5.00 cm 3 / g or less, more preferably 3.00 cm 3 / g or less is there.
  • the porous dense trapping layer 31 having such microporosity is formed by using fine inorganic fine particles capable of forming a void having a pore diameter of 5 ⁇ m or more and less than 10 ⁇ m when forming the porous dense part 31a.
  • 31a can be realized by applying various known methods, such as using a fine pore-forming material capable of forming a void having a pore diameter of 5 ⁇ m or more and less than 10 ⁇ m.
  • pore volume pore diameter 10 ⁇ m is more preferably less than 0.400cm 3 / g, more preferably less than 0.300cm 3 / g , particularly preferably less than 0.250cm 3 / g, and most particularly preferred less than 0.200 cm 3 / g.
  • the porous dense trapping layer 31 having such microporosity is filled with fine inorganic fine particles in the pores so that no void having a pore diameter of 10 ⁇ m or more is formed when the porous dense portion 31a is formed.
  • the pore volume (total volume having a pore diameter of 0.1 ⁇ m or more) of the porous dense trapping layer 31 varies depending on the size of the wall flow type substrate 10 to be used, and is not particularly limited. 0.8 cm 3 / g, more preferably 0.25 ⁇ 0.7cm 3 / g, more preferably from 0.3 ⁇ 0.6cm 3 / g, particularly preferably from 0.3 to zero. 55 cm 3 / g.
  • the wall flow type base material 10 has an introduction-side cell 11 having an open end 11a on the exhaust gas introduction side, and a discharge-side cell 12 having an open end 12a on the exhaust gas discharge side adjacent to the introduction-side cell 11. It is a structure partitioned by a quality partition 13. As such a structure, various materials and shapes used in conventional applications of this kind can be used.
  • the material of the wall flow type base material 10 is used when the internal combustion engine is exposed to a high temperature (for example, 400 ° C. or more) exhaust gas generated when the internal combustion engine is operated under a high load condition, or burns and removes particulate matter at a high temperature.
  • a high temperature for example, 400 ° C. or more
  • a material made of a heat-resistant material is preferable so as to cope with the case.
  • the heat-resistant material include cordierite, silicon carbide, silicon nitride, mullite, aluminum titanate, and ceramics such as silicon carbide (SiC); and alloys such as stainless steel.
  • the shape of the wall flow type substrate 10 can be appropriately adjusted from the viewpoints of exhaust gas purification performance, suppression of pressure loss rise, and the like.
  • the outer shape of the wall flow type substrate 10 can be a cylindrical shape, an elliptical cylindrical shape, a polygonal cylindrical shape, or the like.
  • the capacity (total volume of cells) of the wall flow type substrate 10 is usually preferably 0.1 to 5 L, and more preferably 0.5 to 3 L, although it differs depending on the space into which it is incorporated.
  • the total length of the wall flow type substrate 10 in the stretching direction also varies depending on the space into which the wall flow type substrate 10 is to be incorporated, but is usually preferably 10 to 500 mm, more preferably 50 to 300 mm. is there.
  • the introduction-side cell 11 and the discharge-side cell 12 are regularly arranged along the axial direction of the cylindrical shape. As described above, adjacent cells are connected to one open end of the extending direction and another open end. Are sealed alternately.
  • the introduction-side cell 11 and the discharge-side cell 12 can be set to appropriate shapes and sizes in consideration of the flow rate and components of the supplied exhaust gas.
  • the opening shapes of the inlet-side cell 11 and the outlet-side cell 12 can be triangular; rectangular such as square, parallelogram, rectangular, and trapezoidal; other polygons such as hexagonal and octagonal; circular. .
  • the cross-sectional area of the introduction-side cell 11 and the cross-sectional area of the discharge-side cell 12 may have a High Ash Capacity (HAC) structure.
  • HAC High Ash Capacity
  • the number of the introduction-side cells 11 and the number of the discharge-side cells 12 can be appropriately set so as to promote the generation of turbulent flow of exhaust gas and to suppress clogging due to fine particles and the like contained in the exhaust gas. However, usually, 200 cpsi to 400 cpsi is preferable.
  • the partition wall 13 that separates adjacent cells is not particularly limited as long as it has a porous structure through which exhaust gas can pass, and the configuration thereof includes exhaust gas purification performance, suppression of increase in pressure loss, and mechanical strength of the substrate. It can be adjusted appropriately from the viewpoint of improvement of the quality.
  • the pore diameter for example, the mode diameter (the appearance ratio in the frequency distribution of When the largest pore diameter (maximum value of the distribution)) and the pore volume are large, the pores are generally less likely to be blocked by the first catalyst layer 21, and the resulting exhaust gas purifying catalyst has an increased pressure loss.
  • the pore diameter (mode diameter) of the partition wall 13 of the wall flow type substrate 10 before the first catalyst layer 21 is formed is preferably 8 to 25 ⁇ m, more preferably 10 to 22 ⁇ m. And more preferably 13 to 20 ⁇ m.
  • the thickness D of the partition wall 13 of the wall flow type substrate 10 is preferably 6 to 12 mil, and more preferably 6 to 10 mil.
  • the pore volume of the partition walls 13 of the wall flow type substrate 10 before the formation of the first catalyst layer 21 is preferably 0.2 to 1.5 cm 3 / g by a mercury intrusion method, and more preferably 0.1 to 1.5 cm 3 / g.
  • the porosity of the partition walls 13 is preferably 20 to 80%, more preferably 40 to 70%, and further preferably 60 to 70%.
  • the pore volume or the porosity is equal to or more than the lower limit, an increase in pressure loss tends to be further suppressed.
  • the pore volume or the porosity is equal to or less than the upper limit, the strength of the base material tends to be further improved.
  • the pore diameter (mode diameter), the pore volume, and the porosity mean values calculated by the mercury intrusion method under the conditions described in the following Examples.
  • the first catalyst layer 21 is formed at least at a plurality of locations in the pores of the partition wall 13, and in the present embodiment, the first catalyst layer 21 having the total length L and the thickness D extends over the entire region in cross-section of the wall flow type substrate 10.
  • a catalyst layer 21 is formed (see FIGS. 1 to 3).
  • the formation position of the first catalyst layer 21 may be appropriately set according to the desired performance, and the first catalyst layer 21 does not necessarily need to be formed over the entire region in a cross-sectional view of the wall flow type substrate 10. Alternatively, the first catalyst layer 21 may be formed only on a part.
  • the first catalyst layer 21 of the present embodiment contains at least a first base material particle and a first composite catalyst particle having a platinum group element supported on the first base material particle.
  • the platinum group element includes platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), and osmium (Os).
  • palladium (Pd) and platinum (Pt) are preferable from the viewpoint of oxidation activity
  • rhodium (Rh) is preferable from the viewpoint of reduction activity.
  • One platinum group element can be used alone, or two or more kinds can be used in an optional combination and ratio. Examples of combinations of platinum group elements include, but are not limited to, combinations of two or more platinum group elements having excellent oxidation activity, combinations of two or more platinum group elements having excellent reduction activity, and platinum group elements having excellent oxidation activity. And a platinum group element having excellent reduction activity.
  • a combination of a platinum group element having excellent oxidation activity and a platinum group element having excellent reduction activity is preferable.
  • a combination of Pd and Rh, a combination of Pt and Rh, and a combination of Pd, Pt and Rh are preferable. With such a combination, the exhaust gas purification performance, particularly the light-off performance, tends to be further improved.
  • the fact that the first catalyst layer 21 contains a platinum group element can be confirmed by a scanning electron microscope or the like on the cross section of the partition wall 13 of the catalyst-coated gasoline particulate filter 100. Specifically, it can be confirmed by performing energy dispersive X-ray analysis in the field of view of a scanning electron microscope.
  • oxygen storage materials such as cerium oxide (ceria: CeO 2 ) and ceria-zirconia composite oxide (CZ composite oxide), aluminum oxide (alumina: Al 2 O 3 ), zirconium oxide (zirconia: ZrO 2 ) 2 ), metal oxides such as silicon oxide (silica: SiO 2 ) and titanium oxide (titania: TiO 2 ), composite oxides containing these oxides as main components, perovskite oxides, zeolites and the like.
  • the type is not particularly limited.
  • These may be a composite oxide or a solid solution to which a rare earth element such as lanthanum or yttrium, a transition metal element, or an alkaline earth metal element is added.
  • a rare earth element such as lanthanum or yttrium, a transition metal element, or an alkaline earth metal element is added.
  • One type of these base particles can be used alone, or two or more types can be used in any combination and in any ratio.
  • the oxygen storage material means that when the air-fuel ratio of the exhaust gas is lean (that is, the atmosphere on the oxygen excess side), oxygen in the exhaust gas is stored and the air-fuel ratio of the exhaust gas is rich ( That is, the atmosphere that releases the oxygen stored in the fuel-excess atmosphere).
  • the first base material particles function as carrier particles that support the catalyst active particles in a highly dispersed state.
  • the D90 particle diameter of the first base material particles in the first catalyst layer 21 can be appropriately set according to desired performance, and is not particularly limited, but is preferably 1 to 7 ⁇ m from the viewpoints of exhaust gas purification performance and suppression of pressure loss rise. , More preferably 1 to 6 ⁇ m, and still more preferably 1 to 5 ⁇ m.
  • the content of the platinum group element in the first catalyst layer 21 (wall flow type base)
  • the mass of the platinum group element per liter of the material is usually preferably from 0.1 to 10 g / L, more preferably from 0.2 to 8 g / L, even more preferably from 0.3 to 6 g / L.
  • porous dense collection layer 31 Next, the porous dense collection layer 31 will be described. As described above, in the present embodiment, on the first catalyst layer 21 formed on the pore surface of the partition wall 13, a plurality of porous dense portions 31a constituting the porous dense trapping layer 31 are formed. The porous dense portion 31a is formed by highly filling the pores of the partition walls 13 with the inorganic fine particles after the first catalyst layer 21 is applied.
  • inorganic compounds conventionally used in this type of exhaust gas purifying catalyst can be considered.
  • oxygen storage materials such as cerium oxide (ceria: CeO 2 ) and ceria-zirconia composite oxide (CZ composite oxide), aluminum oxide (alumina: Al 2 O 3 ), zirconium oxide (zirconia: ZrO 2 ) 2 ), oxides such as silicon oxide (silica: SiO 2 ), titanium oxide (titania: TiO 2 ), and composite oxides containing these oxides as main components, but the type is not particularly limited.
  • the oxygen storage material means that when the air-fuel ratio of the exhaust gas is lean (that is, the atmosphere on the oxygen excess side), oxygen in the exhaust gas is stored and the air-fuel ratio of the exhaust gas is rich ( That is, the atmosphere that releases the oxygen stored in the fuel-excess atmosphere).
  • the D90 particle size of the inorganic fine particles constituting the porous dense portion 31a can be appropriately set according to the desired performance, and is not particularly limited. However, from the viewpoint of achieving the above-mentioned microporosity with good reproducibility and easy, 1 to 7 ⁇ m. Is more preferably 1 to 6 ⁇ m, and further preferably 1 to 5 ⁇ m.
  • the porous dense collection layer 31 may contain a platinum group element as needed.
  • inorganic fine particles described above inorganic fine particles and second composite catalyst particles having a platinum group element supported on the surface of the inorganic fine particles can be used.
  • the porous dense trapping layer 31 can also have a catalytic function, thereby purifying the exhaust gas. Performance can be enhanced.
  • the above-mentioned inorganic fine particles also function as carrier particles that carry the catalytically active particles in a highly dispersed state.
  • the platinum group elements include platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), and osmium (Os).
  • palladium (Pd) and platinum (Pt) are preferable from the viewpoint of oxidation activity
  • rhodium (Rh) is preferable from the viewpoint of reduction activity.
  • One platinum group element can be used alone, or two or more kinds can be used in an optional combination and ratio. Examples of combinations of platinum group elements include, but are not limited to, combinations of two or more platinum group elements having excellent oxidation activity, combinations of two or more platinum group elements having excellent reduction activity, and platinum group elements having excellent oxidation activity. And a platinum group element having excellent reduction activity.
  • a combination of a platinum group element having excellent oxidation activity and a platinum group element having excellent reduction activity is preferable.
  • a combination of Pd and Rh, a combination of Pt and Rh, and a combination of Pd, Pt and Rh are preferable. With such a combination, the exhaust gas purification performance, particularly the light-off performance, tends to be further improved.
  • porous dense trapping layer 31 contains a platinum group element
  • a scanning electron microscope or the like on the cross section of the partition wall 13 of the catalyst-coated gasoline particulate filter 100. Specifically, it can be confirmed by performing energy dispersive X-ray analysis in the field of view of a scanning electron microscope.
  • the content ratio of the platinum group element in the porous dense trapping layer 31 (the wall flow type base material)
  • the mass of the platinum group element per liter) is usually preferably 0.5 to 10 g / L, more preferably 1 to 8 g / L, and still more preferably 1 to 6 g / L.
  • the pore diameter (mode diameter) of the partition wall 13 on which the porous dense trapping layer 31 is formed is preferably 10 to 23 ⁇ m, more preferably 12 to 20 ⁇ m, and still more preferably the mercury intrusion method described above. 14 to 18 ⁇ m.
  • the porosity of the partition wall 13 on which the porous dense trapping layer 31 is formed is preferably from 20 to 80%, more preferably from 30 to 70%, and preferably from 35 to 60%, by the mercury intrusion method described above. It is.
  • the second catalyst layer 32 is an arbitrary component in which the porous dense trapping layer 31 is provided in the region on the end 11a side on the uncoated exhaust gas introduction side. The purpose of this is to reinforce the exhaust gas purification performance.
  • the second catalyst layer 32 of the present embodiment contains base particles of inorganic fine particles and third composite catalyst particles having a platinum group element supported on the base particles.
  • the inorganic fine particles used here function as carrier particles that carry the platinum group element in a highly dispersed state.
  • third composite catalyst particles By forming the second catalyst layer 32 using such a platinum group element-supported catalyst (third composite catalyst particles), high exhaust gas purification performance, for example, high light-off performance is realized while suppressing an increase in pressure loss. can do.
  • the third composite catalyst particles of the second catalyst layer 32 may be the same as or different from the first composite catalyst particles of the first catalyst layer 21 and the second composite catalyst particles of the porous dense portion 31a.
  • the same third composite catalyst particles as the second composite catalyst particles in the porous dense portion 31a are used as the third composite catalyst particles in the second catalyst layer 32, so that the second catalyst layer 32
  • the manufacturing process of the porous dense collection layer 31 (porous dense portion 31a) can be simplified, and the productivity can be improved.
  • the platinum group element includes platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), and osmium (Os).
  • palladium (Pd) and platinum (Pt) are preferable from the viewpoint of oxidation activity
  • rhodium (Rh) is preferable from the viewpoint of reduction activity.
  • One platinum group element can be used alone, or two or more kinds can be used in an optional combination and ratio. Examples of combinations of platinum group elements include, but are not limited to, combinations of two or more platinum group elements having excellent oxidation activity, combinations of two or more platinum group elements having excellent reduction activity, and platinum group elements having excellent oxidation activity. And a platinum group element having excellent reduction activity.
  • a combination of a platinum group element having excellent oxidation activity and a platinum group element having excellent reduction activity is preferable.
  • a combination of Pd and Rh, a combination of Pt and Rh, and a combination of Pd, Pt and Rh are preferable. With such a combination, the exhaust gas purification performance, particularly the light-off performance, tends to be further improved.
  • the fact that the second catalyst layer 32 contains a platinum group element can be confirmed by a scanning electron microscope or the like on the cross section of the partition wall 13 of the catalyst-coated gasoline particulate filter 100. Specifically, it can be confirmed by performing energy dispersive X-ray analysis in the field of view of a scanning electron microscope.
  • inorganic compounds conventionally used in this type of exhaust gas purifying catalyst can be considered.
  • oxygen storage materials such as cerium oxide (ceria: CeO 2 ) and ceria-zirconia composite oxide (CZ composite oxide), aluminum oxide (alumina: Al 2 O 3 ), zirconium oxide (zirconia: ZrO 2 ) 2 ), oxides such as silicon oxide (silica: SiO 2 ), titanium oxide (titania: TiO 2 ), and composite oxides containing these oxides as main components, but the type is not particularly limited.
  • the oxygen storage material means that when the air-fuel ratio of the exhaust gas is lean (that is, the atmosphere on the oxygen excess side), oxygen in the exhaust gas is stored and the air-fuel ratio of the exhaust gas is rich ( That is, the atmosphere that releases the oxygen stored in the fuel-excess atmosphere).
  • the D90 particle diameter of the inorganic fine particles in the second catalyst layer 32 can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 1 to 7 ⁇ m, more preferably, from the viewpoints of exhaust gas purification performance and suppression of pressure loss rise. Is 1 to 6 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the content ratio of the platinum group element in the second catalyst layer 32 (wall flow type base)
  • the mass of the platinum group element per liter of the material is usually preferably 0.5 to 10 g / L, more preferably 1 to 8 g / L, and still more preferably 1 to 6 g / L.
  • the porosity of the partition wall 13 on which only the first catalyst layer 21 is formed and the porosity of the partition wall 13 on which the first catalyst layer 21 and the second catalyst layer 32 are formed are determined by the above-mentioned porous dense collection. It is preferable that the layer 31 (porous dense portion 31a) does not have microporosity, that is, the pore volume by the mercury intrusion method does not satisfy the above relationship (the relationship in the numerical range described as preferable). Thus, the porosity of the partition wall 13 on which only the first catalyst layer 21 or the first catalyst layer 21 and the second catalyst layer 32 are formed, and the microporosity of the partition wall 13 on which the porous dense trapping layer 31 is formed. By separating the functions from each other, it is possible to achieve both suppression of pressure loss increase, high exhaust gas purification performance, and dramatically improved PN collection rate.
  • the pore volume by the mercury intrusion method is as follows (A) to (A). It is preferable to have a porosity satisfying at least one of D).
  • the total content of platinum group elements (the mass of platinum group elements per liter of the wall flow type substrate) contained in the first catalyst layer 21, the second catalyst layer 32, and the porous dense trapping layer 31 is the desired exhaust gas. It may be appropriately adjusted in consideration of purification performance, cost, and the like, but is usually preferably 1 to 10 g / L, more preferably 1 to 8 g / L, and still more preferably 1 to 6 g / L.
  • the first catalyst layer 21, the porous dense trapping layer 31, and the second catalyst layer 32 may further contain various known binders known in the art, in addition to the components described above.
  • the type of the binder is not particularly limited, and examples thereof include various sols such as boehmite, alumina sol, titania sol, silica sol, and zirconia sol.
  • soluble salts such as aluminum nitrate, aluminum acetate, titanium nitrate, titanium acetate, zirconium nitrate, and zirconium acetate can also be used as the binder.
  • acids such as acetic acid, nitric acid, hydrochloric acid, and sulfuric acid can be used as the binder.
  • the amount of the binder used is not particularly limited, but is preferably from 0.01 to 15% by mass in total, more preferably from 0.05 to 10% by mass, and more preferably from 0.05 to 10% by mass, respectively, based on the total amount of each layer. More preferably, the content is 0.1 to 8% by mass.
  • the first catalyst layer 21, the porous dense collection layer 31, and the second catalyst layer 32 may further contain a Ba-containing compound in addition to the above-described components.
  • a Ba-containing compound By blending a Ba-containing compound, improvement in heat resistance and activation of catalytic performance can be expected.
  • the Ba-containing compound include a sulfate, a carbonate, a composite oxide, and an oxide, but are not particularly limited thereto. More specifically, BaO, Ba (CH 3 COO) 2 , BaO 2 , BaSO 4 , BaCO 3 , BaZrO 3 , BaAl 2 O 4 and the like can be mentioned, and among them, BaSO 4 is preferable.
  • the amount of the binder Ba-containing compound used is not particularly limited, but is preferably 1 to 20% by mass in total, more preferably 3 to 15% by mass in total, and 5 to 5% in total, based on the total amount of each layer. -13 mass% is more preferred.
  • first catalyst layer 21, the porous dense trapping layer 31, and the second catalyst layer 32 may contain a catalyst, a co-catalyst, and various additives known in the art, in addition to the components described above.
  • various additives include, but are not particularly limited to, dispersion stabilizers such as nonionic surfactants and anionic surfactants; pH adjusters; and viscosity adjusters.
  • the catalyst-coated gasoline particulate filter 100 of the present embodiment comprises a first catalyst layer 21 and a porous dense trapping layer 31 on the above-described wall flow type substrate 10 according to a conventional method. It can be manufactured by providing two catalyst layers 32.
  • the precursor composition for example, a slurry composition
  • the precursor composition is sequentially coated (supported) on the surface of the wall flow type substrate 10 and, if necessary, is subjected to a drying treatment or a heat treatment.
  • a catalyst-coated gasoline particulate filter 100 can be obtained.
  • the method of applying the precursor composition to the wall flow type substrate 10 is preferably a wash coat method, but may be performed according to a conventional method, and is not particularly limited. Various known coating methods, zone coating methods, and the like can be applied. After the application of the precursor composition, drying and baking can be performed according to a conventional method.
  • the introduction-side cell 11 having the open end 11 a on the exhaust gas introduction side and the discharge-side cell 12 having the open end 12 a on the exhaust gas discharge side are formed by a porous partition wall 13.
  • the above-mentioned wall flow type substrate 41 after application of the catalyst (the wall flow type substrate 10 after the application of the first catalyst layer 21) is used as the wall flow type substrate 10.
  • the catalyst-coated gasoline particulate filter 100 in which the first catalyst layer 21 and the porous dense collection layer 31 are formed in this order can be obtained.
  • a step of applying the precursor composition Sl to the pores of the partition 13 (S21) is performed.
  • the slurry composition Sla of the first catalyst layer 21 containing at least catalyst particles is supplied to coat the slurry composition Sla of the first catalyst layer in the pores of the partition 13, and a drying treatment or a heat treatment is performed as necessary.
  • the step (S12) of forming the first catalyst layer 21 may be performed.
  • the precursor of the porous dense trapping layer 31 is formed on the first catalyst layer 21 in the pores of the wall flow type substrate 41 (the wall flow type substrate 10 on which the first catalyst layer 21 has been coated) after the application of the catalyst.
  • the body composition Sl it is possible to obtain the catalyst-coated gasoline particulate filter 100 in which the first catalyst layer 21 and the porous dense trapping layer 31 are laminated in this order.
  • a slurry composition Slb containing a platinum group element is used as the precursor composition Sl, so that a porous catalyst having a catalytic function can be obtained.
  • the dense dense collection layer 31 can be formed.
  • the precursor composition Sl inorganic fine particles and the second composite catalyst particles having a platinum group element supported on the inorganic fine particles, water, and, if necessary, a water-soluble polymer and / or pore-forming material described later.
  • the wall flow type base material is impregnated with the slurry composition Slb (in this example, the end portion 12a on the exhaust gas discharge side).
  • the precursor composition Sl is uniformly applied to the pores of the partition walls 13 (the surface of the first catalyst layer 21) by introducing a gas into the cells of the material 10 and air blowing an excess of the precursor composition Sl. (S22).
  • a slurry composition Slb containing at least inorganic fine particles and a platinum group element is used as the precursor composition Sl
  • a part of the coated precursor composition Sl is used as the precursor composition Sl.
  • Blow coating can also be performed on an uncoated region (in this example, a region having a length Lb on the end 11a side on the exhaust gas introduction side).
  • the precursor composition Sl (slurry composition Slb) applied to the region of the length Lb on the end portion 11a side on the exhaust gas introduction side is subjected to a drying treatment or a heat treatment as necessary, so that a porous dense collection layer is formed.
  • 31 can function as a different catalyst layer (in this example, a second catalyst layer 32 containing inorganic fine particles and a platinum group element).
  • the coated wall flow-type substrate 10 is subjected to a drying treatment and a heat treatment as needed, so that the first catalyst layer 21, the porous dense collection layer 31,
  • the catalyst-coated gasoline particulate filter 100 having the second catalyst layer 32 formed thereon can be obtained (S31).
  • First catalyst layer forming step S12 As shown in FIGS. 6 and 7, in the step S12 of forming the first catalyst layer 21, the first catalyst containing a platinum group element from the end 11 a, 12 a of the wall flow type substrate 10 on the exhaust gas introduction side or the exhaust gas discharge side.
  • the slurry composition Sla of the layer 21 is supplied, and the slurry composition Sla of the first catalyst layer is applied to a plurality of locations in the pores of the partition 13 over the extending direction of the partition 13 of the wall flow type substrate 10.
  • the first catalyst layer 21 is formed by performing a drying process or a heat treatment according to the above.
  • the method for applying the slurry composition Sla may be a conventional method, and is not particularly limited, and a wash coat method or the like is preferably used.
  • the end of the wall flow type substrate 10 can be immersed in the slurry composition Sla, and an air blow process or a suction process can be performed as necessary.
  • the wall flow-type substrate 10 is subjected to a drying treatment or a heat treatment as necessary to form the first catalyst layer 21.
  • the drying condition at this time is not particularly limited as long as the dispersion medium can be removed from the slurry composition Sla.
  • the drying temperature is not particularly limited, but is preferably from 100 to 225 ° C, more preferably from 100 to 200 ° C, and further preferably from 125 to 175 ° C.
  • the drying time is not particularly limited, but is preferably 0.5 to 2 hours, and more preferably 0.5 to 1.5 hours.
  • the heat treatment conditions are preferably from 400 to 650 ° C, more preferably from 450 to 600 ° C, and still more preferably from 500 to 600 ° C.
  • the firing time is not particularly limited, but is preferably 0.5 to 2 hours, preferably 0.5 to 1.5 hours.
  • This slurry composition Sla is a slurry-like mixture containing a platinum group element.
  • Preferable examples thereof include a slurry-like mixture including at least a first base material particle, a first composite catalyst particle having a platinum group element supported on the first base material particle, and a dispersion medium such as water. .
  • Examples of the platinum group element contained in the slurry composition Sla include those similar to those exemplified for the platinum group element contained in the first catalyst layer 21. Further, as the first base material particles contained in the slurry composition Sla, those similar to those exemplified for the first base material particles contained in the first catalyst layer 21 can be mentioned. These platinum group elements and first base material particles can be used alone or in any combination of two or more kinds in any ratio. From the viewpoint of exhaust gas purification performance, the specific surface area of the first base material particles contained in the slurry composition Sla is preferably from 10 to 500 m 2 / g, and more preferably from 30 to 200 m 2 / g.
  • the D90 particle diameter of the first composite catalyst particles contained in the slurry composition Sla can be appropriately set according to desired performance, and is not particularly limited, but is preferably 1 to 7 ⁇ m from the viewpoints of exhaust gas purification performance and suppression of pressure loss rise. , More preferably 1 to 6 ⁇ m, and still more preferably 1 to 5 ⁇ m.
  • the D90 particle diameter is 1 ⁇ m or more, the crushing time when the first composite catalyst particles are crushed by a milling device can be shortened, and the working efficiency tends to be further improved.
  • the D90 particle diameter is 7 ⁇ m or less, it is suppressed that the coarse particles block the pores in the partition wall 13 and the increase in pressure loss tends to be suppressed.
  • the solid content of the slurry composition Sla can be appropriately set according to the desired performance and is not particularly limited, but is preferably 1 to 50% by mass from the viewpoint of coatability of the pores of the partition walls 13 and the like. , More preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass. With such a solid content ratio, the slurry composition Sla tends to be easily applied to the pore surfaces in the partition walls 13.
  • the slurry composition Sla contains, in addition to the components described above, various known binders known in the art, Ba-containing compounds, catalysts and cocatalysts known in the art, various additives, and the like. Is also good. These types and usage amounts are as described in the section of the catalyst-coated gasoline particulate filter 100, and a duplicate description thereof will be omitted.
  • the wall flow type base material 10 (the wall flow type base material 41 after the application of the catalyst (the wall flow type base material after the application of the first catalyst layer 21) is used.
  • the precursor composition Sl of the porous dense trapping layer 31 containing the inorganic fine particles is supplied from the end portions 11a and 12a of the material 10)) on the exhaust gas introduction side or the exhaust gas discharge side, and the partition wall 13 of the wall flow type substrate 10 is formed.
  • the precursor composition Sl is applied to the pores of the partition walls 13 by a length La of 0.4 to 0.9 L with respect to the total length L of the wall flow type substrate 10 in a sectional view.
  • the precursor composition S1 is applied on the first catalyst layer 21 on the pore surface of the partition wall 13.
  • the method for applying the precursor composition Sl may be a conventional method, and is not particularly limited, and a wash coat method or the like is preferably used.
  • the end of the wall flow type substrate 10 can be immersed in the precursor composition Sl, and an air blow process or a suction process can be performed as necessary.
  • the length La of the precursor composition Sl when it is applied to the partition walls 13 is as described in the section of the length La of the porous dense trapping layer 31, and can be appropriately set.
  • the precursor composition S1 for forming the porous dense collection layer 31 will be described.
  • the precursor composition Sl is a slurry mixture containing at least inorganic fine particles and a dispersion medium such as water.
  • the porous dense trapping layer 31 may contain a platinum group element as necessary.
  • the precursor composition S1 includes inorganic fine particles and platinum group metals supported on the inorganic fine particles.
  • a slurry composition Slb containing at least a second composite catalyst particle having an element and a dispersion medium such as water is preferably used.
  • Examples of the platinum group element that can be included in the precursor composition S1 include those similar to those exemplified as the platinum group element included in the porous dense collection layer 31.
  • examples of the inorganic fine particles included in the precursor composition S1 include the same inorganic fine particles that can be included in the porous dense trapping layer 31.
  • One of these platinum group elements and inorganic fine particles can be used alone, or two or more can be used in any combination and in any ratio.
  • the specific surface area of the inorganic fine particles contained in the precursor composition Sl is preferably from 10 to 500 m 2 / g, more preferably from 30 to 200 m 2 / g.
  • the D90 particle size of the second composite catalyst particles that can be included in the precursor composition S1 can be appropriately set according to desired performance, and is not particularly limited, but from 1 to 7 ⁇ m from the viewpoint of exhaust gas purification performance and suppression of pressure loss rise. Is more preferably 1 to 6 ⁇ m, and further preferably 1 to 5 ⁇ m.
  • the D90 particle diameter is 1 ⁇ m or more, the pulverization time when the second composite catalyst particles are crushed by a milling device can be reduced, and the working efficiency tends to be further improved.
  • the D90 particle diameter is 7 ⁇ m or less, it is suppressed that the coarse particles block the pores in the partition wall 13 and the increase in pressure loss tends to be suppressed.
  • the solid content of the precursor composition Sl can be appropriately set according to the desired performance, and is not particularly limited. However, from the viewpoint of coatability of the pores of the partition walls 13, it is preferable.
  • the content is 1 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass. With such a solid content ratio, the coatability of the precursor composition Sl (slurry composition Slb) tends to be improved.
  • the precursor composition Sl preferably further contains a water-soluble polymer compound. Since the water-soluble polymer compound functions as a thickener to reduce the permeability (penetration) into the wall flow-type substrate 10, the water-soluble polymer compound is added to the inside of the wall-flow type substrate 10. The penetration of the precursor composition Sl into the porous dense trapping layer 31 (porous dense part 31a) having the above-mentioned microporosity tends to be easily obtained.
  • the type of the water-soluble polymer compound is not particularly limited as long as it is a polymer material capable of thickening the precursor composition Sl, which is an aqueous dispersion.
  • Specific examples thereof include celluloses, synthetic polymers, natural polymers, polysaccharides, and derivatives thereof, but are not particularly limited thereto.
  • celluloses and derivatives thereof for example, methylcellulose, ethylcellulose, isopropylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, carboxymethylcellulose sodium, Cellulose acetate phthalate, hypromellose acetate succinate, etc.
  • synthetic polymers eg, (meth) acrylic acid, itaconic acid, maleic acid, styrenesulfonic acid, acrylamide 2-methylpropanesulfonic acid, 2-hydroxypropyl- ⁇ -cyclo Dextrin, polyvinyl alcohol, (meth) acrylamide, dimethyl acrylia , Diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, polyvinylpyrrolidone, vinylformamide, vinylacetamide, polyethylene oxide, polyacrylic acid, polyalg
  • the content of the water-soluble polymer compound in the precursor composition Sl can be appropriately set according to the desired performance, and is not particularly limited. Usually, 0.05 to 1.0% by mass, more preferably 0.1 to 0.7% by mass, and further preferably 0.15 to 0.5% by mass in terms of solid content based on the total amount of the precursor composition Sl. % By mass.
  • the precursor composition Sl further includes a pore-forming material (porous material). It is preferred to contain.
  • the pore former is burned or decomposed by heat treatment after the precursor composition Sl is applied and disappears, thereby forming pores (voids). By blending such a pore former, it becomes easy to adjust the pore diameter and pore volume of the obtained porous dense trapping layer 31 (porous dense part 31a).
  • the type of the pore forming material is not particularly limited as long as it can be burned or decomposed by heat treatment and disappears, thereby forming pores (voids).
  • the pore-forming material for example, hollow resin particles, foamed resin, water-absorbent resin, starches, silica gel, and the like are known, and can be appropriately selected from those known in the art.
  • An acrylic or styrene-based polymer obtained by polymerization or suspension polymerization may be used, but is not particularly limited thereto.
  • the particle size of the pore-forming material can be appropriately set according to the desired performance, and is not particularly limited.
  • the above-mentioned porous dense trapping layer 31 (porous dense portion 31a) having microporosity is easily obtained with good reproducibility.
  • the D50 particle diameter is preferably 0.5 to 10 ⁇ m, more preferably 1 to 9 ⁇ m, and further preferably 2 to 8 ⁇ m.
  • the content ratio of the pore former in the precursor composition Sl can be appropriately set according to the desired performance, and is not particularly limited. It is usually preferably from 10 to 70% by mass, more preferably from 20 to 60% by mass, and still more preferably from 30 to 50% by mass in terms of solid content based on the total amount of the precursor composition Sl.
  • the precursor composition Sl contains, in addition to the components described above, various binders known in the art, Ba-containing compounds, catalysts and cocatalysts known in the art, various additives, and the like. You may. These types and usage amounts are as described in the section of the catalyst-coated gasoline particulate filter 100, and a duplicate description thereof will be omitted.
  • blowing step S22 As shown in FIG. 9, in the blowing step S22, the precursor composition Sl is applied by a length La of 0.4 to 0.9 L with respect to the total length L of the cross-sectional view of the wall flow type substrate 10, and then, A gas is introduced into the cell of the wall flow type substrate 10 from the end side (in this example, the end 12a on the exhaust gas discharge side) impregnated with the precursor composition Sl, and the precursor composition Sl is air blown. Thereby, the precursor composition Sl can be dried. At this time, when the slurry composition Slb containing the inorganic fine particles and the platinum group element is used as the precursor composition Sl, the blowing pressure is set to be high, and the precursor composition Sl is not used.
  • Blow coating can be performed by blowing off the coating area (in this example, the area of the length Lb on the end 11a side on the exhaust gas introduction side). That is, in the blowing step S22, a catalyst layer (in this example, the second catalyst layer 32 containing inorganic fine particles and a platinum group element) different from the porous dense trapping layer 31 is applied to the region of the length Lb. It is possible to The slurry composition Slb applied to the region of the length Lb on the end portion 11a side on the exhaust gas introduction side is subjected to a drying treatment or a heat treatment as necessary, so that a catalyst different from the porous dense trapping layer 31 is obtained. It functions as a layer (in this example, the second catalyst layer 32 containing inorganic fine particles and a platinum group element).
  • Step S31 of forming porous dense collection layer 31 Thereafter, the coated wall flow type substrate 10 is dried as necessary, and then heat-treated to form a porous dense collection layer 31.
  • the second catalyst layer 32 is also formed at the same time.
  • the drying conditions at this time are not particularly limited as long as the dispersion medium can be removed from the precursor composition Sl (slurry composition Slb).
  • the drying temperature is not particularly limited, but is preferably from 100 to 225 ° C, more preferably from 100 to 200 ° C, and further preferably from 125 to 175 ° C.
  • the drying time is not particularly limited, but is preferably 0.5 to 2 hours, and preferably 0.5 to 1.5 hours.
  • the heat treatment conditions are preferably from 400 to 650 ° C, more preferably from 450 to 600 ° C, and still more preferably from 500 to 600 ° C.
  • the firing time is not particularly limited, but is preferably 0.5 to 2 hours, and preferably 0.5 to 1.5 hours.
  • FIG. 10 is a schematic cross-sectional view illustrating a schematic configuration of a catalyst-coated gasoline particulate filter 200 (hereinafter, may be referred to as a “GPF catalyst”) according to one embodiment of the present invention.
  • GPF catalyst catalyst-coated gasoline particulate filter
  • the formation of the second catalyst layer 32 is omitted, and the pore surfaces of the partition walls 13 of the wall flow type base material 10 are porous. Except that the dense collection layer 31 (porous dense part 31a) is provided, it has the same configuration as the above-described first embodiment. With such a configuration, the same operation and effect as those of the above-described first embodiment can be obtained.
  • FIG. 13 is a schematic cross-sectional view illustrating a schematic configuration of a catalyst-coated gasoline particulate filter 300 (hereinafter, may be referred to as a “GPF catalyst”) according to one embodiment of the present invention.
  • GPF catalyst catalyst-coated gasoline particulate filter
  • FIG. 16 is a schematic cross-sectional view illustrating a schematic configuration of a catalyst-coated gasoline particulate filter 400 (hereinafter, may be referred to as a “GPF catalyst”) according to one embodiment of the present invention.
  • GPF catalyst catalyst-coated gasoline particulate filter 400
  • the formation of the second catalyst layer 32 is omitted, and the pore surface of the partition wall 13 of the wall flow type substrate 10 has a porous surface.
  • the dense collection layer 31 porous dense part 31a
  • the same operation and effect as those of the above-described third embodiment can be obtained.
  • the catalyst-coated gasoline particulate filters 100, 200, 300, and 400 of the above embodiments can purify carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOx), and the like.
  • particulate matter (PM) is collected with high efficiency, and the PN collection rate is dramatically increased. Therefore, it is useful in an exhaust gas purification application of an internal combustion engine that emits exhaust gas by burning a mixture containing oxygen and fuel gas, particularly an exhaust gas purification application of a direct injection gasoline engine, and particularly useful in an exhaust gas purification application of a direct injection gasoline engine.
  • the catalyst-coated gasoline particulate filters 100, 200, 300, and 400 of each of the above embodiments can be effectively used as a TWC for an engine direct-type catalytic converter or a tandem-type direct catalytic converter.
  • Example 1 an alumina powder having a D50 particle size of 28 ⁇ m and a BET specific surface area of 141 m 2 / g is impregnated with an aqueous solution of palladium nitrate, and then calcined at 500 ° C. for 1 hour to obtain a Pd-supported alumina powder (Pd content: 4. 3% by mass). Also, a zirconia-lanthanum-modified alumina powder having a D50 particle size of 29 ⁇ m and a BET specific surface area of 145 m 2 / g is impregnated with an aqueous rhodium nitrate solution, and then calcined at 500 ° C. for 1 hour to obtain a Rh-supported zirconia-lanthanum modification. An alumina powder (Rh content: 0.7% by mass) was obtained.
  • a cordierite wall flow type honeycomb substrate (number of cells / mil thickness: 300 cpsi / 8 mil, diameter: 118.4 mm, total length: 127 mm, porosity: 65%) was prepared.
  • the end of the base material on the exhaust gas discharge side is immersed in the above-mentioned catalyst slurry for the porous dense trapping layer, suctioned from the opposite end under reduced pressure, and the length La (from the end on the exhaust gas discharge side) 0.5 L) of the catalyst slurry for the porous dense collection layer.
  • the base material coated with the catalyst slurry is dried at 150 ° C., and baked at 550 ° C. in the air atmosphere, so that the porous dense trapping layer and the second catalyst layer are formed into a zone on the wall flow type base material.
  • Example 1 A catalyst slurry for a first catalyst layer of Comparative Example 1 was obtained in the same manner as in Example 1 except that the compounding of the thickener was omitted. Same as Example 1, except that the catalyst slurry for the first catalyst layer of Comparative Example 1 was used instead of the catalyst slurry for the porous dense trapping layer of Example 1, and the entire substrate was impregnated with the catalyst slurry. The first catalyst layer was coated over the entire length L of the wall-flow-type substrate, and a wall-flow-type substrate after coating with a catalyst of Comparative Example 1 having a structure equivalent to that of FIG. 6 was prepared (catalyst slurry coating). Amount 60 g / L).
  • the exhaust gas purifying catalyst prepared in each of the examples and comparative examples was mounted on a vehicle equipped with a 1.5-liter direct injection turbo engine, and using a solid particle number measuring device (manufactured by AVL, trade name: APC 489) during running in WLTC mode.
  • the soot discharge quantity (PNtest) was measured.
  • Example 3 an alumina powder having a D50 particle size of 28 ⁇ m and a BET specific surface area of 141 m 2 / g is impregnated with an aqueous solution of palladium nitrate, and then calcined at 500 ° C. for 1 hour to obtain a Pd-supported alumina powder (Pd content: 4. 3% by mass). Also, a zirconia-lanthanum-modified alumina powder having a D50 particle size of 29 ⁇ m and a BET specific surface area of 145 m 2 / g is impregnated with an aqueous rhodium nitrate solution, and then calcined at 500 ° C. for 1 hour to obtain a Rh-supported zirconia-lanthanum modification. An alumina powder (Rh content: 0.7% by mass) was obtained.
  • the catalyst slurry for the first catalyst layer of Example 3 I got Further, a water-soluble polymer compound (thickener) was added to the catalyst slurry for the first catalyst layer of Example 3 to obtain a catalyst slurry for the porous dense collection layer of Example 3.
  • thicker a water-soluble polymer compound
  • a cordierite wall flow type honeycomb substrate (number of cells / mil thickness: 300 cpsi / 8 mil, diameter: 118.4 mm, total length: 127 mm, porosity: 65%) was prepared.
  • gas was introduced into the base material from the end surface on the exhaust gas discharge side.
  • the excess catalyst slurry for the first catalyst layer was blown off and dried at 150 ° C., whereby the first catalyst layer was coated over the entire length L of the wall-flow-type substrate.
  • a wall flow-type substrate was prepared (catalyst slurry coating amount 40 g / L).
  • the end on the exhaust gas discharge side of the wall flow type substrate after the catalyst coating of Example 3 is further immersed in the catalyst slurry for the porous dense trapping layer of Example 3 above, and the opposite end side , And the catalyst slurry for the porous dense collection layer was impregnated and held by a length La (0.8 L) from the end on the exhaust gas discharge side.
  • a gas is caused to flow into the base material from the end face side on the exhaust gas discharge side, and excess catalyst slurry for the porous dense trapping layer is blown off, and the length Lb (0.2 L) is measured from the end on the exhaust gas introduction side.
  • an excess amount of catalyst slurry for the porous dense trapping layer (catalyst slurry for the second catalyst layer) was blow-coated to coat the second catalyst layer.
  • Example 4 Performed in the same manner as in Example 3, except that the blending amount of the thickener was changed to 1/3 times, and that the crosslinked acrylic resin beads having a D50 particle diameter of 1 ⁇ m were blended as a pore former at 30% by mass with respect to the total amount, A catalyst slurry for a porous dense collection layer of Example 4 was obtained. The same procedure as in Example 3 was carried out except that the catalyst slurry for the porous dense trapping layer of Example 4 was used instead of the catalyst slurry for the porous dense trapping layer of Example 3, and the first catalyst layer was formed of a wall.
  • Example 5 A catalyst slurry for a porous dense trapping layer of Example 5 was obtained in the same manner as in Example 4 except that the amount of the pore former was changed to 30% by mass. The same procedure as in Example 4 was carried out except that the catalyst slurry for the porous dense trapping layer of Example 5 was used instead of the catalyst slurry for the porous dense trapping layer of Example 4, and the first catalyst layer was formed of a wall.
  • Example 6 Except that the pore former was changed to crosslinked acrylic resin beads having a D50 particle size of 5 ⁇ m, the same procedure as in Example 4 was carried out to obtain a catalyst slurry for a porous dense trapping layer of Example 6. The same procedure as in Example 4 was carried out except that the catalyst slurry for the porous dense trapping layer of Example 6 was used instead of the catalyst slurry for the porous dense trapping layer of Example 4, and the first catalyst layer was formed of a wall.
  • a cordierite wall flow type honeycomb substrate (cell number / mil thickness: 300 cpsi / 8 mil, diameter: 118.4 mm, total length: 127 mm, porosity: 65%) was used as it was.
  • Comparative Example 2 The end of the cordierite-made wall flow type honeycomb substrate on the exhaust gas discharge side is immersed in the catalyst slurry for the first catalyst layer of Example 3 to impregnate and hold the catalyst slurry. A gas flows into the base material from the end face side of the base material, and the excess catalyst slurry for the first catalyst layer is blown off and dried at 150 ° C. so that the first catalyst layer has a total length L of the wall flow type base material. A catalyst-coated wall flow type substrate of Comparative Example 2 having a structure equivalent to that of FIG. 6 was prepared (coating amount of catalyst slurry: 60 g / L).
  • the PN collection rate of the post-catalyst wall-flow base material of Comparative Example 2 was 61.3%, and the post-catalyst wall-flow base material of the uncoated catalyst layer was 61.3%. From comparison with a certain reference example, it can be seen that the PN collection rate is reduced by coating the first catalyst layer.
  • the catalyst-coated gasoline particulate filters of Examples 3 to 6 in which a porous dense trapping layer was formed on the wall flow type base material after the catalyst coating of Comparative Example 2 were compared with Reference Example and Comparative Example 2. As a result, it was confirmed that the PN collection rate was dramatically improved. From these facts, it was confirmed that the provision of the porous dense collection layer on the outermost surface side significantly improved the PN collection performance.
  • the low pressure region (0 to 400 Kpa) was measured by PASCAL140, and the high pressure region (0.1 Mpa to 400 Mpa) was measured by PASCAL440.
  • the pore diameter (mode diameter) and the pore volume were calculated.
  • the pore volume and the porosity were calculated for pores having a pore diameter (mode diameter) of 0.1 ⁇ m or more.
  • the values of the pore diameter and the pore volume are the average of the values obtained in the exhaust gas introduction side portion, the exhaust gas discharge side portion, and the intermediate portion in the reference example 1 for the partition wall of the wall flow type substrate. The value was adopted.
  • Comparative Example 2 the average value of the values obtained for the exhaust gas introduction side portion, the exhaust gas discharge side portion, and the intermediate portion was used for the partition wall on which the first catalyst layer was coated. Further, in Examples 3 to 6, the porous dense trapping layer and the partition wall on which the first catalyst layer is coated are targeted, and the exhaust gas discharge side portion with respect to the length La direction of the porous dense trapping layer, The average value of the values obtained for the other end portion and the intermediate portion was employed. Table 3 shows the measurement results.
  • Example 4 From a comparison between Example 4 and Example 5, it was confirmed that when a large amount of the pore former was added, the PN collection rate was higher and the pressure loss was lower. Further, from the comparison between Example 4 and Example 6, the pore diameter of the minute voids (pores) formed can be adjusted according to the D50 particle diameter of the pore-forming material. It was confirmed that the pressure can be increased and the pressure loss can be decreased.
  • the catalyst-coated gasoline particulate filter of the present invention and the method for producing the same can be widely and effectively used in three-way catalyst applications for reducing NOx, CO, HC and the like in exhaust gas discharged from a gasoline engine,
  • the PN collection rate is dramatically improved as compared with the conventional GPF catalyst, it can be particularly effectively used in a GPF catalyst application corresponding to the strengthened global PN regulations scheduled in the future. .

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Abstract

La présente invention concerne : un filtre à particules d'essence revêtu de catalyseur qui présente un taux de collecte de PN considérablement amélioré par rapport aux catalyseurs GPF classiques; un procédé de production de ce filtre à particules d'essence revêtu de catalyseur; et similaire. Un filtre à particules d'essence revêtu de catalyseur 100 selon la présente invention est pourvu d'une couche de catalyseur qui purifie un gaz d'échappement déchargé à partir d'un moteur à essence. Le filtre à particules d'essence revêtu de catalyseur 100 est pourvu d'au moins : un matériau de base de type à écoulement de paroi 10 dans lequel une cellule côté introduction 11 qui s'ouvre une extrémité côté introduction de gaz d'échappement 11a et une cellule côté décharge 12 qui s'ouvre dans une extrémité côté décharge de gaz d'échappement 12a sont définies par une paroi de séparation poreuse 13; et une couche de collecte dense poreuse 31 qui est composée d'une pluralité de parties denses poreuses 31a dans lesquelles des pores de la paroi de séparation 13 sont remplis de particules fines inorganiques, et qui est formée le long du matériau de base de type à écoulement de paroi 10 dans la direction d'extension de la paroi de séparation 13 de façon à avoir une longueur La de 0,4 L à 0,9 l par rapport à la longueur totale L du matériau de base de type à écoulement de paroi 10 lorsqu'elle est vue en coupe transversale.
PCT/JP2019/030770 2018-08-09 2019-08-05 Filtre à particules d'essence revêtu de catalyseur et son procédé de production WO2020031975A1 (fr)

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WO2022176528A1 (fr) * 2021-02-16 2022-08-25 株式会社キャタラー Catalyseur de purification de gaz d'échappement

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