WO2020100582A1 - パティキュレートフィルタ - Google Patents

パティキュレートフィルタ Download PDF

Info

Publication number
WO2020100582A1
WO2020100582A1 PCT/JP2019/042464 JP2019042464W WO2020100582A1 WO 2020100582 A1 WO2020100582 A1 WO 2020100582A1 JP 2019042464 W JP2019042464 W JP 2019042464W WO 2020100582 A1 WO2020100582 A1 WO 2020100582A1
Authority
WO
WIPO (PCT)
Prior art keywords
washcoat layer
exhaust gas
pores
partition wall
particulate filter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/042464
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
亮太 尾上
凌 田▲崎▼
桃子 岩井
大和 松下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cataler Corp
Original Assignee
Cataler Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cataler Corp filed Critical Cataler Corp
Priority to US17/285,290 priority Critical patent/US11454149B2/en
Priority to EP19884989.5A priority patent/EP3854477B1/en
Priority to CN201980075307.9A priority patent/CN113039015A/zh
Publication of WO2020100582A1 publication Critical patent/WO2020100582A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24492—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2474—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the walls along the length of the honeycomb
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2482—Thickness, height, width, length or diameter
    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • 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
    • 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
    • F01N3/022—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 characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—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 characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • 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
    • 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
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/915—Catalyst supported on particulate filters
    • B01D2255/9155—Wall flow filters
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • 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
    • 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
    • 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
    • F01N2330/30—Honeycomb supports characterised by their structural details
    • 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
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • 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
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/22—Selection of materials for exhaust purification used in non-catalytic purification apparatus
    • 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
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • 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
    • F01N3/101—Three-way catalysts
    • 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
    • F01N3/18—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 methods of operation; Control
    • F01N3/20—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 methods of operation; Control specially adapted for catalytic conversion
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F01N3/2066—Selective catalytic reduction [SCR]
    • 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
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs

Definitions

  • the present invention relates to a particulate filter. More specifically, the present invention relates to a particulate filter that collects particulates (particulate matter) contained in exhaust gas discharged from an internal combustion engine such as a gasoline engine.
  • an internal combustion engine such as a gasoline engine.
  • Exhaust gas from an internal combustion engine that uses gasoline, diesel oil, or the like as fuel contains particulate matter containing carbon as a main component, along with gas components such as hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxides (NOx). It is known that substances (Particulate Matter: PM) etc. are contained and cause air pollution. With regard to this particulate matter (PM; hereinafter sometimes simply referred to as “PM”), the emission amount of the particulate matter such as HC, CO, and NOx is being regulated year by year, and PM is collected from the exhaust gas. Research is being carried out repeatedly on the technology for removing the impurities.
  • a particulate filter for collecting and removing PM from exhaust gas is arranged in an exhaust passage of an internal combustion engine in combination with, for example, an exhaust gas purifying catalyst body containing a precious catalyst metal for purifying gas components. Placement is being done.
  • a so-called wall-flow type structure is known, which is made of a porous base material having a honeycomb structure and alternately blocks the inlets and outlets of a large number of cells which are hollow portions thereof.
  • Patent Documents 1 and 2 In the wall-flow type particulate filter, the exhaust gas flowing from the cell inlet passes through the porous cell partition wall while moving in the cell, and is discharged to the cell outlet.
  • a wash coat may be provided on the surface of the substrate in order to provide a stable collecting surface even at high temperature.
  • a filter catalyst in which a particulate filter and an exhaust gas purifying catalyst are integrated by supporting a precious catalyst metal on the washcoat of the particulate filter.
  • the PM collection rate of such a filter catalyst gradually increases as the vehicle travels.
  • RDE Real Driving Emissions
  • Table 1 the PM collection rate can reach 95% or more. This is based on the fact that the more the PM accumulates on the filter catalyst, the higher the PM trapping effect.
  • improvements in PM collection technology are strongly demanded.
  • the present invention has been made in view of such an event, and its main purpose is to provide, for example, a particulate filter whose PM collection rate is increased from the first running.
  • the present inventors have found that in a particulate filter having a wall flow structure, PM is scattered in the pores of partition walls and is easily trapped in relatively small small pores. I found out. Further, in the particulate filter, PM trapped by continuous running accumulates on the filter, so that the PM trapping rate increases.
  • the noble metal catalyst supported on the particulate filter is highly active, PM can be burned and lost even in the traveling mode. Then, it was thought that the PM collection rate would decrease due to the decrease in the PM deposition amount due to this phenomenon. Therefore, the present inventors preferentially reduce the amount of the noble metal catalyst after arranging the wash coat preferentially in the large pores while leaving the small pores for trapping PM at a specific ratio. According to the above, it was found that the PM collection performance can be stably maintained at a high level, and the present invention was completed.
  • the particulate filter according to the present invention is a particulate filter that is arranged in the exhaust passage of an internal combustion engine and is used to collect particulate matter from the exhaust gas discharged from the internal combustion engine.
  • This particulate filter is a wall having a porous partition wall that partitions an inlet cell having an open end on the exhaust gas inlet side and an outlet cell adjacent to the inlet cell and having an open end on the exhaust gas outlet side.
  • a flow-structured base material and a washcoat layer formed inside the partition wall are provided. The washcoat layer is held on the surface of the inner pores of the partition wall.
  • the average filling factor A of the washcoat layer retained in the first pore group having a pore diameter of 5 ⁇ m or more and less than 10 ⁇ m and the second filling pore group having a pore diameter of 10 ⁇ m or more and less than 20 ⁇ m The following relationship between the average filling rate B of the washed coat layer and the average filling rate C of the washcoat layer retained in the third pore group having a pore diameter of 20 ⁇ m or more: A ⁇ B ⁇ C; B ⁇ 40%; and the proportion of the pores of the first pore group and the second pore group having the fill factor of the washcoat layer of 75% or more is 35 number% or less.
  • the washcoat layer is formed in a region occupying 50% or more of the thickness of the partition wall from at least a part of the surface of the partition wall facing at least one cell of the entrance side cell and the exit side cell,
  • the amount of the noble metal catalyst supported by the washcoat layer is 0 g / L or more and 0.2 g / L or less. According to the particulate filter having such a configuration, the PM collecting performance can be effectively improved. As a result, a high PM collection rate can be realized without waiting for PM to accumulate in the filter. Further, in the configuration including the noble metal catalyst, the filter can be effectively regenerated while suppressing the amount of the noble metal catalyst supported.
  • the washcoat layer does not contain a precious metal catalyst. With such a configuration, it is possible to provide a particulate filter excellent in PM trapping performance at low cost.
  • the washcoat layer when the flow direction is a direction from the exhaust gas inflow side to the exhaust gas outflow side, the washcoat layer includes the surface of the partition wall facing the input side cell, and, A region including the upstream washcoat layer provided in a region along the flow direction from the end of the exhaust gas inflow side, and the surface of the partition wall facing the output side cell, and a region along the flow direction from the end of the exhaust gas outflow side And a downstream washcoat layer provided in the.
  • the length L A of the end of the exhaust gas inlet side in the flow direction is preferably not more than 1/2 of the total length L of the substrate.
  • the length L B of the downstream washcoat layer from the end on the exhaust gas outflow side in the flow direction is preferably 1/2 or more of the total length L of the base material.
  • the average filling rate A is 10% ⁇ A ⁇ 35%
  • the average filling rate B is 15% ⁇ B ⁇ 40%
  • the average is The filling rate C is 20% ⁇ C ⁇ 45%.
  • the internal combustion engine is a gasoline engine.
  • the temperature of exhaust gas is relatively high, and it is difficult for PM to accumulate in the partition walls. Therefore, when the internal combustion engine is a gasoline engine, the above-mentioned effects are more effectively exhibited.
  • FIG. 1 is a diagram schematically showing an arrangement of a particulate filter in an exhaust path according to an embodiment.
  • FIG. 2 is a perspective view schematically showing the particulate filter according to the embodiment.
  • FIG. 3 is a sectional view schematically showing a section of the particulate filter according to the embodiment.
  • FIG. 4 is a schematic sectional view in which the IV region of FIG. 3 is enlarged.
  • 5A to 5D are cross-sectional SEM images of the partition walls of Example 1, Example 3, Example 11, and Example 15, respectively.
  • FIG. 6 is a graph showing the pore size distribution of the particulate filter of each example.
  • FIG. 7 is a graph showing the relationship between the Pd amount and the PM collection rate of the particulate filter of each example.
  • FIG. 8 is a graph showing the relationship between the coating amount of the particulate filter of each example and the PM collection rate.
  • FIG. 9 is a graph showing the relationship between the coating amount and the pressure loss increase rate of the particulate filter of each example
  • FIG. 1 is a diagram schematically showing an internal combustion engine (which may be an engine) 2 and an exhaust gas purifying apparatus 1 provided in an exhaust system of the internal combustion engine 2.
  • the particulate filter disclosed here is provided in the exhaust system of the internal combustion engine 2 as one component of the exhaust gas purification apparatus 1.
  • a mixture containing oxygen and fuel gas is supplied to the internal combustion engine 2.
  • the internal combustion engine 2 converts the thermal energy generated by burning this air-fuel mixture into kinetic energy.
  • the air-fuel mixture burned at this time becomes exhaust gas and is discharged to the exhaust path.
  • the internal combustion engine 2 having the structure shown in FIG. 1 is mainly composed of, but not limited to, a gasoline engine of an automobile.
  • the internal combustion engine 2 is connected to an exhaust path at an exhaust port (not shown).
  • the exhaust path in FIG. 1 includes an exhaust manifold 3 and an exhaust pipe 4.
  • the internal combustion engine 2 is connected to an exhaust pipe 4 via an exhaust manifold 3.
  • Exhaust gas flows through the inside of the exhaust pipe 4.
  • the arrows in the figure indicate the flow direction of the exhaust gas.
  • the side closer to the engine 2 along the flow of the exhaust gas may be referred to as the upstream side, and the side farther from the engine 2 may be referred to as the downstream side.
  • the exhaust gas purifying apparatus 1 typically includes a catalyst unit 5, a filter unit 6, an engine control unit (ECU) 7, and a sensor 8.
  • the exhaust gas purifying apparatus 1 purifies harmful components (for example, carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NO x )) contained in the exhaust gas, and at the same time, particulate matter ( PM) is collected.
  • harmful components for example, carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NO x )
  • the catalyst unit 5 and the filter unit 6 are provided inside the exhaust pipe 4 that communicates with the engine 2.
  • the catalyst unit 5 is configured to be able to purify the ternary components (NOx, HC, CO) contained in the exhaust gas.
  • the type of catalyst contained in the catalyst part 5 is not particularly limited.
  • the catalyst unit 5 may include, for example, a catalyst supporting a noble metal such as platinum (Pt), palladium (Pd), and rhodium (Rd).
  • the catalyst unit 5 may further include a downstream catalyst unit (not shown) in the exhaust pipe 4 on the downstream side of the filter unit 6. Since the specific configuration of the catalyst unit 5 does not characterize the present invention, detailed description thereof will be omitted here.
  • the filter unit 6 is provided on the downstream side of the catalyst unit 5. As shown in FIG. 2, the filter unit 6 includes the particulate filter 100 disclosed herein.
  • the particulate filter 100 of this example is a gasoline particulate filter (GPF) capable of collecting and removing PM contained in exhaust gas and subjected to washcoat treatment.
  • GPF gasoline particulate filter
  • the ECU 7 is electrically connected to the internal combustion engine 2 and the sensor 8.
  • the ECU 7 receives signals from various sensors (for example, oxygen sensor, temperature sensor, pressure sensor) 8 that detect the operating state of the internal combustion engine 2, and controls the drive of the internal combustion engine 2.
  • the configuration of the ECU 7 may be the same as the conventional one and is not particularly limited.
  • the ECU 7 is, for example, a processor or an integrated circuit.
  • the ECU 7 receives, for example, information on the operating state of the vehicle or the like detected by the various sensors 8 and the amount, temperature, pressure, etc. of the exhaust gas discharged from the internal combustion engine 2.
  • the ECU 7 executes operation control such as fuel injection control, ignition control, intake air amount adjustment control (for example, air-fuel ratio control) for the internal combustion engine 2 according to the received information.
  • FIG. 2 is a perspective view of the particulate filter 100 according to the embodiment.
  • X in FIG. 2 is the first direction of the particulate filter 100.
  • the particulate filter 100 is installed in the exhaust pipe 4 so that the first direction X is along the exhaust gas flow direction.
  • one of the first directions X may be referred to as an exhaust gas inflow side (upstream side) and the other direction X2 may be referred to as an exhaust gas outflow side (downstream side).
  • FIG. 3 is a schematic view in which a part of a cross section of the particulate filter 100 taken along the first direction X is enlarged.
  • FIG. 4 is an enlarged schematic diagram in which the IV region of FIG. 3 is enlarged.
  • the particulate filter 100 disclosed herein includes a base material 10 having a wall flow structure and a wash coat layer 20.
  • the substrate 10 and the wash coat layer 20 will be described in this order.
  • the base material 10 various materials and forms of filters conventionally used for this type of application can be used.
  • the base material 10 formed of a ceramic such as cordierite or silicon carbide (SiC) or an alloy (stainless steel) can be preferably used.
  • a base material having a columnar outer shape (the present embodiment) is exemplified.
  • an elliptic cylinder shape, a polygonal prism shape, or the like may be adopted instead of the cylindrical shape.
  • the base material 10 typically has a so-called honeycomb structure.
  • the cavities (cells) in the honeycomb structure extend along the first direction X.
  • the cell includes an incoming cell 12 and an outgoing cell 14 adjacent to the incoming cell 12.
  • the base material 10 is provided with a porous partition wall 16 that partitions the inlet cell 12 and the outlet cell 14.
  • the dimension of the constituent elements such as the substrate 10 along the first direction X is referred to as the length.
  • the inlet-side cell 12 is a cell of which the exhaust gas inflow side end is open and the outflow side is closed among the cells provided in the base material.
  • the outlet-side cell 14 is a cell located adjacent to the inlet-side cell 12, having an open end on the exhaust gas outlet side and a closed inlet side.
  • the inlet-side cell 12 is plugged at the end portion on the exhaust gas outlet side with a sealing portion 12a.
  • the outlet-side cell 14 is plugged at the end portion on the exhaust gas inflow side with a sealing portion 14a.
  • the sealing parts 12a and 14a are airtightly fixed to the partition wall 16 described later.
  • the inlet cell 12 and the outlet cell 14 may be set to have appropriate shapes and sizes in consideration of the flow rate and the components of the exhaust gas supplied to the particulate filter 100.
  • the shape of a cross section (hereinafter, simply referred to as a “cross section”) of the input side cell 12 and the output side cell 14 orthogonal to the first direction X is a square, a parallelogram, a rectangle, a trapezoid, a rectangle, a triangle, or the like.
  • Various geometric shapes such as a polygon (eg, hexagon, octagon), a circle, and the like may be used.
  • the cross-sectional area of the inlet side cell 12 and the cross-sectional area of the outlet side cell 14 in the cross section may be the same, or may be different structures (High Ash Capacity: HAC).
  • HAC High Ash Capacity
  • the input cells 12 and the output cells 14 are arranged in a checkered pattern (see FIG. 2).
  • Partition wall 16 A partition wall 16 is arranged between the inlet cell 12 and the outlet cell 14.
  • the partition wall 16 is configured to surround the cells 12 and 14 in a cross section.
  • the partition wall 16 extends along the first direction X.
  • the partition 16 forms and separates the inlet cell 12 and the outlet cell 14.
  • the partition wall 16 has a porous structure through which exhaust gas can pass.
  • the porosity of the partition wall 16 is not particularly limited, but it is suitable to be approximately 40% to 70%, and preferably 55% to 65%. If the porosity of the partition wall 16 is too small, pressure loss may increase, which is not preferable. On the other hand, if the porosity of the partition wall 16 is too large, the mechanical strength of the particulate filter 100 tends to decrease, which is not preferable.
  • the porosity of the partition 16 is also suitable from the viewpoint of preferentially disposing the slurry described below in the large pores of the partition 16.
  • the average pore diameter of the partition walls 16 is not particularly limited, but is generally 5 ⁇ m to 50 ⁇ m, for example, 10 ⁇ m to 30 ⁇ m, and preferably 10 ⁇ m to 25 ⁇ m, from the viewpoint of PM collection efficiency and suppression of pressure loss increase.
  • the average pore diameter of the partition walls 16 is also suitable from the viewpoint of preferentially disposing the washcoat layer 20 described below in the large pores of the partition walls 16.
  • the thickness of the partition wall 16 is not particularly limited, but is preferably about 0.2 mm to 1.6 mm.
  • the thickness of the partition wall 16 is also suitable from the viewpoint of preferentially disposing the slurry described below in the large pores of the partition wall 16.
  • the “average pore diameter” of the porous partition walls 16 in the present specification means the area circle equivalent diameter of N pores virtually separated based on the cross-sectional image analysis of the base material by electron microscope observation, which will be described later. It is a median diameter (D 50 ) based on the particle size distribution of.
  • D 50 median diameter
  • the thickness / thickness direction of the partition wall 16 is the dimension corresponding to the distance between the inlet side cell 12 and the outlet side cell 14 in the above cross section / the direction in which the distance is measured.
  • the thickness of the wash coat layer 20 described later is also a dimension measured along the thickness direction of the partition wall 16.
  • the washcoat layer 20 is a coating layer provided on at least a part of the surface of the base material 10.
  • the washcoat layer 20 may have a function of, for example, increasing the surface area of the base material 10, improving high-temperature stability, improving characteristics such as adsorptivity, and hardening the base material of the base material 10. Therefore, the washcoat layer 20 is not limited by the presence or absence of a noble metal catalyst, which will be described later, and the formation method.
  • the washcoat layer 20 disclosed herein is provided inside the porous partition wall 16 as shown in FIG. More specifically, the washcoat layer 20 is held on the surface of the internal pores 18 of the partition wall 16 as shown in FIG.
  • the washcoat layer 20 is preferably formed as a porous layer mainly composed of a heat resistant material.
  • “mainly” means that the component is contained in an amount of 50% by mass or more (typically 85% by mass or more).
  • the heat resistant material may be, for example, a refractory material specified in JIS R2001, and typically, for example, a neutral refractory material such as alumina, an acidic refractory material such as silica or zirconia, magnesia, calcia, or the like. Basic refractories can be mentioned.
  • the heat resistant material may include various rare earth metal oxides, alkaline earth metal oxides and the like. These may include any one kind alone, or may include two or more kinds as a mixture or a complex.
  • the washcoat layer 20 is mainly composed of alumina (preferably activated alumina). Further, these materials may include other materials (typically inorganic oxides) as a subcomponent.
  • the subcomponent may be added in the form of an element to the above main component, for example. Examples of such subcomponents include rare earth elements such as lanthanum (La) and yttrium (Y), alkaline earth elements such as calcium, alkali metal elements, and other transition metal elements.
  • the washcoat layer 20 includes the upstream washcoat layer 20A formed in a region including the surface of the partition wall 16 facing the entry side cell 12 and the surface of the partition wall 16 facing the exit side cell 14. And a downstream washcoat layer 20B formed in the region.
  • the upstream washcoat layer 20A is preferably arranged in the upstream portion including the exhaust gas inflow side end of the base material 10.
  • the downstream washcoat layer 20B is preferably disposed in the downstream portion including the end of the base material 10 on the exhaust gas outflow side.
  • the upstream washcoat layer 20A has a thickness of the partition wall 16 in the thickness direction of the partition wall 16 from the surface of the partition wall 16 facing the input side cell 12 toward the output side cell 14 side. It may be formed in a region occupying 50% or more of T. As a result, it is possible to secure an opportunity for contact between the exhaust gas passing through the partition wall 16 and the wash coat layer 20.
  • the downstream washcoat layer 20B occupies 50% or more of the thickness T of the partition wall 16 in the thickness direction of the partition wall 16 from the surface of the partition wall 16 facing the outlet cell 14 toward the inlet cell 12 side. It may be formed in the region. As a result, it is possible to secure an opportunity for contact between the exhaust gas passing through the partition wall 16 and the wash coat layer 20.
  • the upstream washcoat layer 20A and the downstream washcoat layer 20B preferably satisfy the following relationship: T A + T B ⁇ T; for example, the upstream washcoat layer 20A and the downstream washcoat layer 20B. Is preferably formed in a region extending from the surface of the partition wall 16 facing the entrance-side cell 12 or the exit-side cell 14 to 50% or more of the thickness T of the partition wall 16 (0.5T ⁇ T A , 0.5T ⁇ T B ).
  • the washcoat layer 20 in the region up to at least 50% of the thickness T of the partition wall 16, a conventional filter that does not satisfy the relationship of 0.5T ⁇ T A and 0.5T ⁇ T B can be obtained. In comparison, it is possible to effectively improve the exhaust gas purification performance while maintaining a good PM collection performance.
  • the upstream washcoat layer 20A includes an end portion on the exhaust gas inflow side X1 of the base material 10 and extends from the end portion toward the downstream side X2 in the first direction X.
  • the upstream washcoat layer 20A is preferably formed on at least 30% from the end of the entire length L of the base material 10.
  • the downstream washcoat layer 20B includes an end portion on the exhaust gas outflow side of the base material 10 and extends from the end portion toward the upstream side X1 in the first direction X.
  • L B 0.1 L to 0.8 L, more preferably 0.3 L to 0.8 L.
  • the upstream side wash coat layer 20A and the downstream side wash coat layer 20B do not overlap in the first direction X of the base material 10. It may be formed (for example, L A + L B ⁇ L), but it is more preferably formed so as to overlap (for example, L ⁇ L A + L B ).
  • the overlapping width of the upstream side wash coat layer 20A and the downstream side wash coat layer 20B may be about 0L to 0.3L, for example, about 0.05L to 0.15L.
  • the upstream washcoat layer 20A and the downstream washcoat layer 20B may be provided, and for example, at least the upstream washcoat layer 20A may be provided.
  • the formation region of the washcoat layer 20 may cover the entire region of the substrate 10 in the first direction X. This is preferable because the exhaust gas passing through the partition wall 16 can always come into contact with the washcoat layer 20.
  • the upstream side wash coat layer 20A and the downstream side wash coat layer 20B can have similar configurations except that the distribution regions in the partition walls 16 are different, and therefore will be collectively described below as the wash coat layer 20.
  • the partition 16 may include internal pores of various sizes.
  • the internal pores of the partition wall 16 are, for example, a first pore group having a pore diameter of 5 ⁇ m or more and less than 10 ⁇ m, a second pore group having a pore diameter of 10 ⁇ m or more and less than 20 ⁇ m, and a third pore group having a pore diameter of 20 ⁇ m or more. It can be divided into and.
  • the first pore group suitably contributes to the collection of PM having a finer particle size.
  • the second pore group suitably contributes to the collection of slightly larger PM than fine PM.
  • the third pore group can also collect PM, but mainly contributes to the low loss movement of the exhaust gas.
  • the arrangement of the washcoat layer 20 in the internal pores is adjusted so as to satisfy the following conditions. That is, of the inner pores of the partition wall 16, the average filling rate A of the washcoat layer 20 retained in the first pore group and the average filling rate B of the washcoat layer 20 retained in the second pore group.
  • the average filling factor C of the washcoat layer 20 held in the third pore group is as follows: A ⁇ B ⁇ C; B ⁇ 40%; And the proportion P of pores in the first pore group and the second pore group in which the filling rate of the washcoat layer 20 is 75% or more is 35 number% or less.
  • the washcoat layer 20 is preferentially held in the third pore group having a larger pore diameter among the internal pores.
  • the average filling rate B of the washcoat layer 20 arranged in the second pore group is 40% or less.
  • the average filling rate A of the washcoat layer 20 arranged in the first pore group is smaller than the average filling rate B and less than 40% or less.
  • the washcoat layer 20 is suppressed from filling a part of the pores and reducing the fluidity of the exhaust gas. According to the exhaust gas purifying apparatus having such a configuration, it is possible to improve the contact efficiency between the wash coat layer 20 and the exhaust gas while maintaining good PM trapping performance.
  • the reason why such an effect is obtained is not particularly limited, but it can be considered as follows, for example.
  • the first and second pore groups (small pores) having relatively small pore diameters are not filled with the washcoat layer so much that the PM The deterioration of the collection performance can be effectively suppressed without unevenness.
  • the third pore group (large pores) having a relatively large pore diameter has a larger exhaust gas flow path and a larger exhaust gas flow rate than the small pores.
  • the average filling rate C is not particularly limited as long as it is larger than the average filling rate B.
  • the average filling rate C is preferably larger than the average filling rate B by 0.3% or more (for example, C ⁇ B + 0.3), and more preferably 0.5% or more (for example, C ⁇ B + 0). .5).
  • the particulate filter 100 disclosed herein can be preferably implemented, for example, in a mode in which the average filling rate C is larger than the average filling rate B by 1% or more (for example, C ⁇ B + 1).
  • the average fill factor C may be greater than the average fill factor B by, for example, 4% or more, and typically 8% or more. As a result, better exhaust gas purification performance can be realized.
  • the value obtained by subtracting the average filling rate B from the average filling rate C is preferably 30% or less, more preferably 25% or less, and further preferably 20% or less.
  • (CB) may be 16% or less, 14% or less, or 10% or less.
  • 20% is preferable from the viewpoint that the effect (for example, the exhaust gas purification performance improving effect) of making the average filling rate C larger than the average filling rates A and B is better exhibited.
  • ⁇ C and more preferably 25% ⁇ C.
  • the upper limit of the average filling rate C is not particularly limited, but from the viewpoint of PM trapping performance, suppression of pressure loss increase, etc., it is generally C ⁇ 60%, typically C ⁇ 50%, and preferably C ⁇ 45%.
  • the technique disclosed herein is preferably implemented in a mode in which the average filling factor C of the washcoat layer in the particulate filter 100 is 20% ⁇ C ⁇ 45% (preferably 25% ⁇ C ⁇ 45%). obtain.
  • the average filling rate B may be smaller than the average filling rate C and larger than the average filling rate A.
  • the average filling rate B is preferably larger than the average filling rate A by 1% or more (for example, B ⁇ A + 1) and more preferably 3% or more (for example, B ⁇ A + 3).
  • the average fill factor B may be 3.5% or more greater than the average fill factor A, and typically 4% or more.
  • the value obtained by subtracting the average filling rate A from the average filling rate B (that is, BA) is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less.
  • BA may be 8% or less, typically 5% or less.
  • a specific example of the average filling rate B is generally B ⁇ 40%, preferably B ⁇ 38%, and typically B ⁇ 35% from the viewpoint of realizing a filter having more excellent PM trapping performance. Is.
  • the average fill factor B may be B ⁇ 30%, typically B ⁇ 25%.
  • the lower limit of the average filling rate B is not particularly limited, but from the viewpoint of realizing a filter catalyst with more excellent purification performance, preferably 10% ⁇ B, more preferably 15% ⁇ B, for example 18% ⁇ B, typically Specifically, 20% ⁇ B.
  • the technique disclosed herein can be preferably implemented in a mode in which the average filling factor C of the washcoat layer in the particulate filter is 15% ⁇ B ⁇ 40% (preferably 20% ⁇ B ⁇ 35%). ..
  • the average filling rate A is not particularly limited as long as it satisfies the relationship of A ⁇ B ⁇ C between the average filling rates B and C and A ⁇ 40%.
  • the average filling rate A is preferably A ⁇ 35%, and more preferably A ⁇ 32% from the viewpoint of realizing a filter having more excellent PM trapping performance.
  • the average fill factor A may be A ⁇ 25%, typically A ⁇ 20% (eg, A ⁇ 18%).
  • the lower limit of the average filling rate A is not particularly limited, but from the viewpoint of obtaining good exhaust gas purification performance, etc., preferably 5% ⁇ A, more preferably 8% ⁇ A, for example 10% ⁇ A, typically 12 % ⁇ A.
  • the technology disclosed herein can be preferably implemented in a mode in which the average filling rate A of the washcoat layer in the particulate filter is 10% ⁇ A ⁇ 35% (preferably 15% ⁇ A ⁇ 32%). ..
  • the proportion P of pores having a washcoat layer filling rate of 75% or more is approximately 35 number% or less. This makes it possible to suppress a decrease in the PM collection rate.
  • the ratio P of the pores having a filling rate of 75% or more in the first and second pore groups is preferably 30 number% or less, more preferably 28 number% or less, and further preferably 25 number% or less. In some embodiments, the percentage P may be, for example, 20% by number or less, and typically 15% by number or less (eg, 10% by number or less).
  • the lower limit of the ratio P is not particularly limited, but it is suitable to be approximately 1 number% or more.
  • the ratio P is preferably 3 number% or more, and more preferably 5 number% or more.
  • the proportion P of the pores having a filling rate of 75% or more among the pores having a pore diameter of 5 ⁇ m or more and less than 20 ⁇ m may be substantially 0% by number.
  • the pore diameter of the pores provided inside the partition walls and the filling rate of the washcoat layer retained in the pores are calculated as follows. That is, (1) Using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), the internal pores included in the sectional SEM image or sectional TEM image of the partition wall are observed, and the largest pore diameter in the image can be taken. Begin to separate the pores from the site. (2) When the pores are connected, the pores are partitioned when the diameter is narrowed to 50% of the maximum pore diameter and separated as one pore (in that case, the washcoat layer is divided into pores (voids). Process).
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the diameter of the ideal circle (true circle) having the same area as the area X of the pore calculated from the separated pore image is calculated as the pore diameter of the pore.
  • the area Y of the washcoat layer retained in the pores is calculated from the separated pore image, and the area Y of the washcoat layer is divided by the area X of the pores to obtain a percentage (that is, 100 ⁇ Y / X) is calculated as the filling rate (%) of the washcoat layer in the pores.
  • the pores having the larger pore diameter are separated.
  • the treatments (2) to (5) are repeated until the diameter of the separated pores becomes 5 ⁇ m or less, whereby the pore diameter of the pores provided inside the partition wall and the washcoat retained in the pores.
  • the filling factor of the layer can be determined.
  • the average filling rate of the washcoat layer for each pore size range can be derived by arithmetically averaging the filling rate of the washcoat layer for each pore size range.
  • the number of pores S1 having a pore diameter of 5 ⁇ m or more and less than 20 ⁇ m and the number of pores S2 having a pore diameter of 5 ⁇ m or more and less than 20 ⁇ m and a filling rate of 75% or more are counted, and [(S2 / S1) ⁇ 100], the ratio P can be calculated.
  • the pore size of each pore and the filling factor of the washcoat layer can be determined using image analysis software by a computer that performs a predetermined process according to a predetermined program.
  • the pores and washcoat layer image-processed in the pore image are composed of a large number of dots (pixels), and the areas X and Y of the pores and washcoat layer can be grasped from the number of dots.
  • the average filling rates A, B, C and the ratio P are usually preferably calculated in three representative fields of view (three different cross sections) from the viewpoint of improving measurement accuracy and reproducibility. Specifically, (A) the average packing ratios A, B, and C of the respective pore size ranges in three fields of view (variation (standard deviation: ⁇ )) are calculated, and (B) the average packing ratios A, B, and C are calculated. If the variation of the ratio P is within 3 ⁇ , the measurement is finished.
  • the coating amount of the washcoat layer means the mass of the washcoat layer per unit volume of the base material in the portion provided with the washcoat layer.
  • the coat amount is a value obtained by dividing the mass of the wash coat layer by the volume of the base material.
  • volume means the bulk volume of the substrate including the volume of the substrate (including internal pores) and cells. In this specification, the bulk volume of a substrate may be simply referred to as “volume” unless otherwise specified.
  • the coating amount is based on the area of the particulate filter where the washcoat layer is formed and the area of the particulate filter where the washcoat layer is not formed in the first direction X. It means the mass of the washcoat layer per unit volume of the material.
  • the coating amount (density) of the upstream side wash coat layer 20A is based on the mass of the upstream side wash coat layer 20A. Of the coating length L A divided by the bulk volume.
  • the coat amount (density) of the downstream washcoat layer 20B is a value obtained by dividing the mass of the downstream washcoat layer 20B by the bulk volume of the coat length L B portion of the base material.
  • the coating amount of the wash coat layer is not particularly limited as long as the average filling rates A, B, C and the ratio P in each pore size range satisfy the above relationship, but is about 100 g / L or less per 1 L of the volume of the base material. , Preferably 95 g / L or less, for example 90 g / L or less, for example 85 g / L or less, and typically 80 g / L or less. In some embodiments, for example, the coat weight of the washcoat layer may be 75 g / L or less, typically 70 g / L or less.
  • the wash coat layer by making the average filling rate of the washcoat layer held in the large pores having a large pore size larger than the average filling rate of the washcoat layer held in the small pores having a small pore size, It is possible to effectively improve the exhaust gas purification performance while reducing the coat amount of the wash coat layer in the entire filter (and thus reducing the pressure loss and cost). Therefore, for example, even though the wash coat layer has a small coating amount of 100 g / L or less per 1 L of the volume of the substrate, it has excellent purification performance and high performance (for example, when exhaust gas passes through the substrate. It is possible to realize the particulate filter 100 that does not cause an increase in pressure loss.
  • the lower limit of the coat amount of the wash coat layer is not particularly limited, but is preferably 25 g / L or more, more preferably 30 g / L or more, still more preferably 35 g / L or more, from the viewpoint of improving the purification performance. Since it depends on the cell volume of the base material, the thickness of partition walls, the porosity, the pore size distribution, etc., it cannot be generally stated, but in some embodiments, for example, the wash coat layer has a coating amount of 25 g / L or more and 100 g / L or more.
  • the washcoat layer is retained in the inner pores of the partition wall means that the washcoat layer is not on the surface of the partition wall (that is, in the cell) but inside the partition wall (the wall of the inner pore). Mainly present on the surface). More specifically, for example, the cross section of the substrate is observed with an electron microscope, and the total coating amount (area) of the washcoat layer is set to 100%.
  • the coating amount existing on the wall surface of the inner pores of the partition walls is typically 80% or more (for example, 90% or more), for example, 95% or more, preferably 98% or more, further 99% or more, Particularly, it is substantially 100%, that is, the washcoat layer is substantially absent on the surface of the partition wall. Therefore, it is clearly distinguished from the case where a part of the washcoat layer unintentionally penetrates into the inner pores of the partition wall when the washcoat layer is arranged on the surface of the partition wall, for example.
  • the washcoat layer 20 may or may not contain a catalyst.
  • the catalyst is not particularly limited. For example, it may be various catalysts that can be included in this type of particulate filter. Such a catalyst may be a so-called three-way catalyst, an SCR catalyst, an NSR catalyst or a combination thereof.
  • the washcoat layer 20 may include a three-way catalyst.
  • the washcoat layer 20 may include a noble metal and a carrier carrying the noble metal.
  • the noble metal contained in the washcoat layer 20 may be any substance having a catalytic function for purification of harmful components contained in exhaust gas.
  • the noble metal include metals including gold (Au) silver (Ag), palladium (Pd), rhodium (Rh), platinum (Pt), ruthenium (Ru), iridium (Ir), osmium (Os), and the like. be able to. More preferably, it is a metal containing a platinum group element such as Ru, Rh, Pd, Os, Ir and Pt. These may include any one kind or two or more kinds. Above all, it is preferable to contain at least one of Rh, Pd, and Pt.
  • the content (mass) of the noble metal arranged in the washcoat layer 20 is approximately 0 g / L or more and 0.2 g / L or less per unit volume (here, 1 liter) of the base material. From the viewpoint of realizing a catalyst having more excellent PM trapping performance, etc., preferably 0.15 g / L or less, more preferably 0.1 g / L or less, still more preferably 0.08 g / L or less, for example 0.05 g. / L or less.
  • the lower limit of the content of the noble metal is not particularly limited, and may be 0.001 g / L or more, for example, from the viewpoint of reducing the combustion temperature in the regeneration process of the particulate filter 100. However, the noble metal content may be less than 0.001 g / L, for example 0 g / L (substantially free).
  • the upstream wash coat layer 20A and the downstream wash coat layer 20B may or may not independently contain a catalyst. You don't have to.
  • both the upstream washcoat layer 20A and the downstream washcoat layer 20B contain a catalyst, the catalysts contained in each may be the same or different.
  • both the upstream washcoat layer 20A and the downstream washcoat layer 20B contain a precious metal, and the precious metal contained in the upstream washcoat layer 20A and the precious metal contained in the downstream washcoat layer 20B are different. ..
  • the upstream washcoat layer 20A preferably contains Rh.
  • the downstream washcoat layer 20B preferably contains Pd.
  • the mass ratio (Pd / Rh) of Rh arranged in the upstream washcoat layer 20A to Pd arranged in the downstream washcoat layer 20B preferably satisfies 0.1 ⁇ (Pd / Rh), and 0 0.5 ⁇ (Pd / Rh) is preferable, 1 ⁇ (Pd / Rh) is more preferable, and 1.5 ⁇ (Pd / Rh) is particularly preferable.
  • the mass ratio (Pd / Rh) preferably satisfies (Pd / Rh) ⁇ 20, preferably (Pd / Rh) ⁇ 15, more preferably (Pd / Rh) ⁇ 10, and (Pd / Rh) ⁇ 5 is particularly preferred.
  • neither the upstream washcoat layer 20A nor the downstream washcoat layer 20B contains a catalyst. As a result, the PM trapping performance of the particulate filter 100 can be improved satisfactorily.
  • the noble metal is supported on a carrier (typically a powder).
  • the noble metal-supporting carrier is not limited to this, but examples thereof include alumina (Al 2 O 3 ), rare earth metal oxides, alkali metal oxides, alkaline earth metal oxides, and zirconia (ZrO 2 ). , Ceria (CeO 2 ), silica (SiO 2 ), magnesia (MgO), titanium oxide (titania: TiO 2 ) and other metal oxides, or their solid solutions (eg ceria-zirconia (CeO 2 -ZrO 2 ) composite oxide Thing). Above all, it is preferable to use alumina and / or ceria-zirconia composite oxide.
  • an inorganic oxide may be added to the carrier as a subcomponent.
  • these may be added, for example, in the form of elements, and examples of components that can be added to the carrier include rare earth elements such as lanthanum (La) and yttrium (Y), alkaline earth elements such as calcium, alkali metal elements, and others. Examples include transition metal elements.
  • rare earth elements such as lanthanum and yttrium can be suitably used as a stabilizer because they can improve the specific surface area at high temperature without inhibiting the catalytic function.
  • Such carriers can be polycrystalline or single crystalline.
  • the amount of the noble metal supported on the carrier is not particularly limited. For example, it is suitable to set it in the range of 0.01% by mass to 2% by mass (for example, 0.05% by mass to 1% by mass) with respect to the total mass of the carrier.
  • the method of supporting the noble metal on the carrier is not particularly limited.
  • a carrier powder containing Al 2 O 3 and / or CeO 2 —ZrO 2 composite oxide is impregnated with an aqueous solution containing a noble metal salt (eg, nitrate) or a noble metal complex (eg, tetraammine complex) and then dried. It can be prepared by firing.
  • a slurry for forming the washcoat layer which contains the powder of the refractory material described above and a suitable solvent (for example, ion-exchanged water).
  • a suitable solvent for example, ion-exchanged water.
  • the catalyst for example, a powder made of a carrier carrying a noble metal
  • this slurry may be added to this slurry at a predetermined ratio.
  • the viscosity of the slurry is one important factor from the viewpoint of realizing the magnitude relationship (A ⁇ B ⁇ C) of the average filling rate of the washcoat layer described above. That is, the slurry easily flows into the large pores (for example, pores having a pore diameter of 20 ⁇ m or more) among the internal pores of the partition wall 16 and becomes small pores (for example, pores having a pore diameter of 5 ⁇ m or more and less than 20 ⁇ m).
  • the viscosity is preferably adjusted appropriately so that it will not easily flow in.
  • the slurry has a viscosity ⁇ 400 at a shear rate of 400 s ⁇ 1 of more than 50 mPa ⁇ s and 150 mPa ⁇ s or less, preferably 60 mPa ⁇ s or more and 110 mPa ⁇ s or less.
  • the slurry is preferentially arranged in the large pores of the internal pores of the partition wall 16, and the above-described magnitude relationship (A ⁇ B ⁇ C) of the average filling rate is satisfied.
  • the filled washcoat layer 100 can be stably formed.
  • the slurry may contain a thickener or a dispersant.
  • the thickener include cellulosic polymers such as carboxymethyl cellulose (CMC), methyl cellulose (MC), hydroxypropyl methyl cellulose (HPMC), and hydroxyethyl methyl cellulose (HEMC).
  • the content of the thickener in the total solid content of the slurry is not particularly limited as long as the viscosity of the slurry satisfies the above range, but is generally 0.1% by mass to 5% by mass, preferably 0.3% by mass. It is ⁇ 4% by mass, more preferably 0.5% by mass to 3% by mass.
  • the dispersant for example, polycarboxylic acid can be preferably used. By adding the polycarboxylic acid, the large pores can be preferentially coated with the slurry while leaving the small pores.
  • the production method disclosed herein can be particularly preferably carried out in an embodiment using such a polycarboxylic acid.
  • the weight average molecular weight (Mw) of the polycarboxylic acid based on gel permeation chromatography (GPC, water system, polyethylene oxide conversion) may be, for example, 1,000,000 to 2,000,000.
  • the polycarboxylic acid may be used in the form of the salt.
  • salts include metal salts (eg, lithium salt, sodium salt, potassium salt), ammonium salt and the like.
  • the slurry viscosity is a viscosity that can be measured by a commercially available shear viscometer at room temperature. For example, by using a dynamic viscoelasticity measuring device (rheometer) that is standard in the art, the viscosity can be easily measured under the above shear rate range conditions.
  • "normal temperature” refers to a temperature range of 15 to 35 ° C, typically a temperature range of 20 to 30 ° C (for example, 25 ° C).
  • the average particle size of the particles in the slurry is not particularly limited, but may be the average particle size of the partition walls 16 (median diameter: D 50 ). It is preferably about 1/50 to 1/3.
  • the average particle size of the particles in the slurry is more preferably about 1/40 or more, and even more preferably about 1/30 or more of the average pore size of the partition wall 16.
  • the average particle diameter of the particles in the slurry is more preferably about 1 ⁇ 5 or less, and even more preferably about 1/10 or less of the average pore diameter of the partition wall 16.
  • the average particle size of the particles in the slurry can be about 0.3 ⁇ m or more, preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the thickness can be about 3 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.7 ⁇ m or less.
  • the average particle diameter of the particles in the slurry is within such a range, the slurry is likely to be preferentially arranged in the large pores of the internal pores of the partition wall 16. Therefore, it is possible to more stably form the washcoat layer satisfying the magnitude relationship (A ⁇ B ⁇ C) of the average filling rate.
  • the average particle diameter (median diameter: D 50 ) of the particles in the slurry can be grasped based on the laser diffraction / scattering method.
  • the washcoat layer 20 is formed in the pores of the partition wall 16 using the above slurry.
  • the washcoat layer 20 can be formed by a suction coating method.
  • the washcoat layer is generally formed by an immersion method.
  • the base material is immersed in the slurry as described above, the slurry is permeated into the base material and allowed to flow into the pores of the partition wall, the base material is taken out and the amount of the slurry is adjusted by air blow, and the solvent is used.
  • the slurry also flows into the closed pores of the partition wall where the exhaust gas does not pass, so that a washcoat layer that does not contribute to the purification of the exhaust gas tends to be formed, and the purification performance may deteriorate.
  • the whole or a part of the slurry is a portion that becomes an end portion of the base material on the exhaust gas inflow side or the exhaust gas outflow side (hereinafter, referred to as “end portion F”).
  • the other end that is, a portion that becomes the end of the base material on the exhaust gas outflow side or the exhaust gas inflow side, hereinafter referred to as "end R" is sucked (first slurry injection).
  • end portion F an end portion of the base material on the exhaust gas inflow side or the exhaust gas outflow side
  • end R a portion that becomes the end of the base material on the exhaust gas outflow side or the exhaust gas inflow side
  • slurry is coated with the slurry, and at least 50% (eg 50% to 100%, preferably 70% to 100% of the thickness of the partition from the surface of the partition. %) Aspirate the slurry so that the area is coated up to. Further, if necessary, the slurry is applied to the other end R of the base material, and the slurry is applied from the end R toward the end F while taking into consideration the viscosity of the slurry and the wetness of the pores in the partition walls. The slurry is coated on a portion corresponding to at most 70% (eg, 5% to 70%, more preferably 5% to 50%) of the length of the base material, and at least the thickness of the partition wall from the surface of the partition wall.
  • the slurry is sucked so that the area is coated with 50% (for example, 50% to 100%, preferably 70% to 100%) (second slurry injection).
  • 50% for example, 50% to 100%, preferably 70% to 100%
  • the slurry is likely to preferentially flow into the large pores (typically the through holes) of the pores of the partition wall where the exhaust gas is likely to pass, Moreover, it becomes difficult for the slurry to flow into the small pores (typically, closed pores) through which the exhaust gas does not easily pass. Therefore, the inconvenience of forming the washcoat layer that does not contribute to the purification of the exhaust gas as when using the dipping method is eliminated or alleviated, and the purification performance can be improved.
  • the suction speed (wind speed) of the slurry is not particularly limited, but it is suitable to set it to about 10 m / s to 80 m / s (preferably 10 m / s to 50 m / s, more preferably 15 m / s to 25 m / s). .. Further, the suction time of the slurry is not particularly limited, but it is suitable to be approximately 0.1 to 10 seconds (preferably 0.5 to 5 seconds, more preferably 1 to 2 seconds).
  • the slurry is likely to be preferentially arranged in the large pores of the inner pores of the partition wall 16, and the magnitude relationship of the average filling rate (A ⁇ B
  • the washcoat layer satisfying ⁇ C) can be formed more stably.
  • the slurry is then dried and fired at a predetermined temperature.
  • the washcoat layer 20 is held on the wall surface of the pores of the partition wall 16.
  • the particulate filter 100 thus obtained is formed by preferentially flowing a slurry having a specific viscosity into the large pores of the partition wall by a suction coating method. Further, according to the manufacturing method disclosed herein, for example, the slurry is applied to the end F of the base material and sucked from the other end R. At that time, the slurry is sucked so that the region from the surface of the partition to at least 50% of the thickness of the partition is coated with the slurry. If necessary, the remaining slurry is applied to the end R of the base material and sucked from the other end F. At that time, the slurry is sucked so that the region from the surface of the partition to at least 50% of the thickness of the partition is coated with the slurry.
  • the average filling rate is large or small (A ⁇ B ⁇ C) and A washcoat layer satisfying the ratio P can be stably formed, and a filter having excellent PM trapping performance and purification performance can be obtained. Therefore, according to the manufacturing method disclosed herein, it is possible to manufacture the particulate filter 100 having a higher PM trapping rate than that of the conventional method and excellent in purification performance.
  • the average filling rate A of the washcoat layer retained in the pores having a pore diameter of 5 ⁇ m or more and less than 10 ⁇ m and the pores having a pore diameter of 10 ⁇ m or more and less than 20 ⁇ m are obtained.
  • the average filling rate B of the retained washcoat layer and the average filling rate C of the washcoat layer retained in the pores having a pore diameter of 20 ⁇ m or more have the following relationship: A ⁇ B ⁇ C; A ⁇ 40%; Exhaust gas purifying filter satisfying B ⁇ 40% and having 35% or less of pores having a fill factor of the washcoat layer of 75% or more among the pores having a pore diameter of 5 ⁇ m or more and less than 20 ⁇ m.
  • a method of manufacturing can be provided.
  • the manufacturing method includes an inlet cell in which only an end portion on the exhaust gas inflow side is opened, an outlet cell adjacent to the inlet cell and in which only an end portion on the exhaust gas outflow side is opened, the inlet cell and the outlet side.
  • Preparing (purchasing, manufacturing, etc.) a base material having a wall flow structure having a porous partition wall separating the cells;
  • the washcoat layer forming slurry is applied to the end portion F (that is, the end portion on the exhaust gas inflow side or the exhaust gas outflow side) of the base material, and the other end portion R (that is, the exhaust gas outflow side of the base material or the exhaust gas) Suction from the inflow side end); and Drying and firing the substrate from which the slurry has been sucked; Includes.
  • the washcoat layer-forming slurry has a viscosity ⁇ 400 at a shear rate of 400 s ⁇ 1 of more than 50 mPa ⁇ s and 150 mPa ⁇ s or less (preferably 80 mPa ⁇ s or more and 120 mPa ⁇ s or less).
  • the filter manufactured by such a method can be suitably used as a particulate filter of a particulate filter.
  • exhaust gas flows into the particulate filter 100 from the inlet cell 12 of the base material 10.
  • the exhaust gas flowing in from the inlet cell 12 passes through the porous partition wall 16 and reaches the outlet cell 14.
  • the route in which the exhaust gas flowing from the inlet cell 12 passes through the partition wall 16 and reaches the outlet cell 14 is indicated by an arrow.
  • the partition wall 16 has a porous structure and the small pores are not filled with the wash coat layer 20, while the exhaust gas passes through this partition wall 16, the particulate matter (PM) is separated from the partition wall 16.
  • PM particulate matter
  • the particulate filter 100 is, in the range that does not impair the essence of the present invention, in addition to the above-mentioned noble metal and carrier, a metal oxide that does not carry a noble metal, a NOx absorbent, and an SCR (Selective Catalytic Reduction: selective catalytic reduction).
  • the washcoat layer 20 may include a catalyst and the like.
  • the metal oxide that does not carry the noble metal the same metal oxide as that described for the carrier can be used.
  • the NOx absorbent has a NOx storage capacity of absorbing NOx in the exhaust gas when the air-fuel ratio of the exhaust gas is in a lean state with excess oxygen and releasing the absorbed NOx when the air-fuel ratio is switched to the rich side. Anything will do.
  • a basic material containing one or more metals capable of donating electrons to NOx can be preferably used.
  • the metal include copper (Cu), iron (Fe), and iridium (Ir).
  • barium compounds for example, barium sulfate
  • the SCR catalyst may be one that purifies nitrogen oxides (NO x ) in the exhaust gas.
  • the SCR catalyst is not particularly limited, but examples thereof include ⁇ -type zeolite and SAPO (silicoaluminophosphate) -based zeolite.
  • SAPO siliconcoaluminophosphate
  • Examples of SAPO include SAPO-5, SAPO-11, SAPO-14, SAPO-17, SAPO-18, SAPO-34, SAPO-39, SAPO-42, and SAPO-47.
  • the SCR catalyst may include any metal component. As such a metal component, copper (Cu), iron (Fe), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), cobalt (Co), nickel (Ni), zinc (Zn).
  • a reducing agent solution supply means for supplying a reducing agent solution (for example, urea water) for producing ammonia may be arranged upstream of the particulate filter 100 in the exhaust pipe.
  • Test examples relating to the present invention will be described, but the present invention is not intended to be limited to those shown in the following test examples.
  • a technique for selectively forming a washcoat layer in a group of pores having a predetermined size in the partition walls of the base material will be described.
  • Example 1 As a wall-flow type base material, a general porous cylindrical filter base material having a honeycomb structure (made of cordierite, length 114.3 mm, volume 1.3 L) was prepared. Further, a slurry for washcoat was prepared by mixing a palladium nitrate solution, alumina powder, CZ (ceria-zirconia composite oxide) powder, ion-exchanged water, and polycarboxylic acid.
  • the CZ powder has a function as a marker (white) for visually recognizing a slurry permeation region (that is, a washcoat layer formation region) in a SEM image described later.
  • the slurry is applied to the exhaust gas inlet side (inlet side: X1) end of the base material and sucked from the exhaust gas outflow side (outlet side: X2) end.
  • the slurry was caused to flow into the pores of the partition walls, and then excess slurry was removed by air blow for coating.
  • the substrate was dried and baked to form a washcoat layer in the pores of the partition wall.
  • Shear rate of slurry Viscosity ⁇ 400 at 400 s ⁇ 1 was 90 mPa ⁇ s, and coating amount of washcoat layer per unit volume of substrate was 15 g / L.
  • the viscosity ⁇ 400 of the slurry was adjusted by the amount of polycarboxylic acid.
  • the particulate filter of Example 1 including the washcoat layer was obtained.
  • Example 2 Examples 2 to 8 were carried out in the same manner as Example 1 except that the coating amount of the washcoat layer per unit volume of the substrate was changed between 30 and 150 g / L as shown in Table 2 below. The particulate filter of was produced.
  • Example 9-12 The viscosity ⁇ 400 of the slurry was changed to 200 mPa ⁇ s, and the coating amount of the washcoat layer per unit volume of the base material was changed between 40 and 100 g / L as shown in Table 2 below. In the same manner as in Example 1, the particulate filters of Examples 9 to 12 were produced.
  • Example 13 to 16 The viscosity ⁇ 400 of the slurry was changed to 10 mPa ⁇ s, and the coating amount of the washcoat layer per unit volume of the base material was changed between 40 and 150 g / L as shown in Table 2 below. In the same manner as in Example 1, the particulate filters of Examples 13 to 16 were produced.
  • ⁇ Washcoat layer formation area> The particulate filter of each example was cut along the X direction, and the cross section of the partition wall of the substrate was observed by SEM to obtain an observed image. Then, based on this observation image, the formation region of the washcoat layer formed in the internal pores of the partition wall and the pore diameter of the pores in which the washcoat layer was formed were observed. The pore diameter of the internal pores of the partition wall is measured by the above-mentioned method. The observation results are briefly shown in the column of "Washcoat formation region" in Table 2 below. For reference, sectional SEM images of the particulate filters of Example 1, Example 3, Example 11, and Example 15 are shown in FIGS. 5A to 5D, respectively. In the cross-sectional SEM image, the washcoat layer is shown as a bright (white) region with contrast, the pores are shown as black regions (within the partition), and the partition is shown as an intermediate gray region.
  • ⁇ Pore size distribution of particulate filter> For the particulate filter of Example 4, Example 11, Example 15 (coating amount 60 g / L) and the substrate prepared for making this particulate filter, the pore size distribution was measured based on the mercury intrusion method, The results are shown in Fig. 6. The pore size distribution was measured using a micropore distribution measuring device AutoPore IV manufactured by Micromeritics. Further, in FIG. 6, with respect to the pore diameter ( ⁇ m), the pore volume ratio corresponding to the pore diameter is represented by log differential pore volume distribution (dV / d (logD), where V is the pore volume, D is plotted as (pore size).
  • the slurry was supplied only from the inlet cell so that the state of the washcoat layer formation could be easily confirmed.
  • FIG. 5 it was found that the formation region of the washcoat layer formed on the substrate was changed by changing the viscosity and the coating amount of the washcoat slurry.
  • Table 1 the area where the wash coat layer is formed tends to expand in the thickness direction of the partition wall from the surface of the partition wall facing the entry side cell to the surface of the partition wall facing the exit side cell as the coating amount increases. I found out that there is.
  • the slurries used to prepare the particulate filters of Examples 1 to 8 have an appropriately adjusted viscosity and are relatively easily wet with the surface of the pores in the partition walls, but naturally permeate into the small pores due to the capillary phenomenon. Not up to. Therefore, for example, it was confirmed that the wash coat layer spreads (becomes deeper) as the coating amount increases from the surface of the partition wall of the base material facing the inlet side cell to the surface facing the outlet side cell. ..
  • the washcoat layer is relatively close to the entry side cell (for example, an area of about 30% in the partition wall thickness direction). ) Is formed only.
  • the washcoat layer was a region reaching the surface on the output cell side (that is, 100 in the partition wall thickness direction). % Area). It was also found that in both the particulate filters of Example 1 and Example 3, the washcoat layer was preferentially formed in the large pores over the small pores and did not block the large pores. .. As shown in FIG. 6, when the pore size distribution of the particulate filter of Example 3 is compared with the pore size distribution of the base material, the distribution of the pore sizes is generally compressed to the small pore size side and the frequency also decreases. I understood.
  • the pore size distribution of the particulate filter of Example 3 almost overlaps with or exceeds the pore size distribution of the base material in the region of the first pore group having a pore size of 5 ⁇ m or more and less than 10 ⁇ m.
  • the frequency in other regions was extremely low, the small pores were almost not filled with the washcoat layer, and most of them were preferentially formed from the large pore side.
  • the slurries used for producing the particulate filters of Examples 9 to 12 have high viscosity, are hard to wet the surfaces of the pores in the partition walls, and have poor fluidity. Therefore, the slurry is first sucked into the large pores having a relatively large diameter from the inlet side surface of the partition wall to fill the large pores, and then is introduced into the next continuous pore.
  • the slurry existing in the area connecting the pore introduction portion of the slurry and the connection portion with the next pore is fluidized.
  • the slurry in other areas tends to stay.
  • the slurry retained in the large pores in the surface layer portion in the vicinity of the surface facing the entry side cell) intrudes into the medium pores and the small pores as the coating amount increases, It was observed that pores and small pores were also filled.
  • the coat amount was relatively large at 60 g / L, but the wash coat layer was relatively close to the entry side cell ( For example, it was found that it is formed only in the region of about 30 to 40% in the thickness direction of the partition wall.
  • Example 6 the pore size distribution of the particulate filter of Example 11 is shifted to the large pore side as a whole as compared with the pore size distribution of Example 4, and the frequency is different from the pore size distribution of the base material.
  • the shapes are similar. From this, in Example 11, it was found that the washcoat layer was locally formed so as to substantially fill all of the large pores, the medium pores, and the small pores on the surface side facing the entry side cell of the partition wall. It was
  • the slurries used in the preparation of the particulate filters of Examples 13 to 16 had a low viscosity, so that they easily wet the surfaces of the pores in the partition walls and easily move without being retained in the large pores by suction, and thus the capillary phenomenon is generated. Therefore, it easily penetrates into small pores.
  • the washcoat layer was widely distributed from the inlet side surface to the outlet side surface of the base material, and was larger than the large pores. It was also found that they were preferentially formed in the small pores. In the pore size distribution of FIG.
  • Example 15 the pore size distribution of the particulate filter of Example 15 shifts to the large pore side and is less frequent than the pore size distribution of Example 11. From this, too, in Example 15, it was found that most of the washcoat layer was preferentially formed from the small pores.
  • the pore size of the inner pores of the partition wall and the filling rate of the washcoat layer retained in the pore are determined by the method described above. It was measured. Then, the packing factor of the washcoat layer is arithmetically averaged for each pore size range shown in Table 3 below to obtain the average packing factor A of the washcoat layer retained in the first pore group having a pore size of 5 ⁇ m or more and less than 10 ⁇ m.
  • an average filling rate B of the washcoat layer retained in the second pore group having a pore diameter of 10 ⁇ m or more and less than 20 ⁇ m, and an average filling rate C of the washcoat layer retained in the third pore group having a pore diameter of 20 ⁇ m or more. was calculated. Further, a ratio P of pores having a filling rate of 75% or more in the pores of the first and second pore groups (pore diameter 5 ⁇ m or more and less than 20 ⁇ m) was calculated. The results are shown in the relevant column of Table 3 below.
  • the slurry having a viscosity ⁇ 400 of 200 mPa ⁇ s did not flow deep inside the partition wall and remained in the surface layer portion.
  • the ratio P of the pores having a filling rate of 75% or more in the first and second pore groups is set to 35 number% or less. I found that I could do it.
  • the coating amount is small, the washcoat layer cannot be formed in a wide area of the partition wall, which is a trade-off.
  • the slurry flowed deep into the partition walls and reached the back surface side, but was retained in the first pore group.
  • the relationship between the average filling factor A of the washcoat layer, the average filling factor B of the washcoat layer retained in the second pore group, and the average filling factor C of the washcoat layer retained in the third pore group is It was confirmed that A>B> C, and it was confirmed that the washcoat layer was preferentially formed in the small pores of the inner pores of the partition wall.
  • the washcoat layer is formed widely even on the back surface side of the partition wall, and the filling rate of the washcoat layer in the first and second pore groups is 75% or more. It was found that the ratio P occupied by the pores of 3 can be suppressed to 35 number% or less.
  • the washcoat layer can be preferentially formed in the large pore group having the size of, and that the washcoat layer can be formed without filling the large pore.
  • the particulate filter including such a washcoat layer can achieve both high PM trapping performance and exhaust gas purification performance at a high level.
  • Example 2-1 By supplying the washcoat slurry from both the inlet cell and the outlet cell, a particulate filter including an upstream washcoat layer and a downstream washcoat layer was produced. Specifically, the same wall-flow type base material as in Test Example 1 above was used as the base material, and the washcoat slurry was the same slurry as in Example 1 of Test Example 1, except that CZ powder and nitric acid were used. A slurry containing no palladium solution was used. Then, a portion corresponding to 60% of the length L from the inlet end of the base material toward the outlet side is immersed in the slurry, suction coating is performed, excess slurry is removed by air blow, and drying and firing are performed.
  • the upstream washcoat layer was formed inside the partition walls of the substrate.
  • the viscosity ⁇ 400 of the slurry was 90 mPa ⁇ s, and the coating amount of the upstream washcoat layer was 50 g / L.
  • the packing ratios A, B, C and the ratio P of the upstream washcoat layer were the same as in Example 3 of Test Example 1.
  • Examples 2-2-2-5 As the washcoat slurry, the same procedure as in Example 1 of Test Example 1 was repeated except that a slurry containing a palladium nitrate solution was used, and the particulates of Examples 2-2 to 2-5 were used. A filter was made. However, the concentration of the palladium nitrate solution in the slurry was adjusted so that the amount of palladium per unit volume of the base material was 0.2 to 1.5 g / L as shown in Table 4 below. The packing ratios A, B, C and the ratio P of the upstream and downstream washcoat layers were the same as in Example 2-1.
  • ⁇ PM collection performance> The PM trapping performance of the particulate filter of each example was evaluated. Specifically, the particulate filter of each example was installed in the exhaust path of the vehicle (2L gasoline engine), and the vehicle was operated in the Phase 4 mode by WLTP. Then, the amount X of PM discharged through the particulate filter and the amount Y of PM discharged without the particulate filter are measured, and the following formula: PM collection rate (%) [(Y ⁇ X ) / Y] ⁇ 100; the PM collection rate was calculated. The results are shown in Table 4 below and FIG. 7.
  • the relationship between the average filling rate A of the washcoat layer, the average filling rate B, and the average filling rate C was A ⁇ B ⁇ C, B.
  • the condition of ⁇ 40% and the ratio P of 35 number% or less are satisfied.
  • the washcoat layer was formed in a region occupying 50% or more of the partition wall thickness on both the upstream side and the downstream side.
  • the PM collection rate of the particulate filter greatly differs depending on the amount of the noble metal catalyst supported.
  • the PM trapping performance of the particulate filter and the exhaust gas purification performance are high. It was thought to be compatible at the level. However, if attention is paid to the PM collection rate, there is a relationship that the PM collection rate decreases as the loaded amount of the noble metal catalyst increases. This is presumed to be due to the following reasons. That is, as the PM collection progresses, PM accumulates in the pores of the particulate filter, and the PM collection rate gradually increases.
  • the PM trapped in the pores coexists with the noble metal catalyst, so that the combustion of PM is promoted even in the normal operation mode, and the amount of accumulated PM decreases and is difficult to increase. ..
  • the PM collection rate in the first test also decreases depending on the noble metal catalyst. From the above, from the viewpoint of surely increasing the PM collection rate, if the precious metal catalyst is suppressed to a small amount of 0.2 g / L or less, the PM can be favorably accumulated until regeneration and the PM collection rate is increased. Therefore, it can be said that it is preferable.
  • the noble metal catalyst may be 0 g / L, for example.
  • Examples 3-1 to 3-6 As the base material and the wash coat slurry, the same wall flow type base material and slurry (that is, no precious metal catalyst) as in Example 2-1 of Test Example 2 were prepared. Then, by using a suction coater, the slurry is supplied to the exhaust gas inlet side (inlet side: X1) end of the base material and sucked from the exhaust gas outflow side (outlet side: X2) end, The slurry was caused to flow into the pores of the partition wall, and excess slurry was removed by air blow to coat the inside of the partition wall. Then, the substrate was dried and baked to form a washcoat layer in the pores of the partition wall.
  • the viscosity ⁇ 400 of the slurry was 90 mPa ⁇ s, and the coating amount of the washcoat layer per unit volume of the base material was varied between 0 and 130 g / L as shown in Table 5 below.
  • the particulate filter of Example 3-1 having no washcoat layer (that is, the bare base material) and the particulate filters of Examples 3-2 to 3-6 provided with the washcoat layer were obtained.
  • the particulate filter of each example does not contain a noble metal catalyst.
  • the relationship between the average filling factors A, B and C of the washcoat layer is A ⁇ B ⁇ C, and the average filling factors A and B are both 40%.
  • the washcoat layer was preferentially formed in the pores having a large pore size among the internal pores of the partition wall. Further, in the first and second pore groups, the proportion P of pores having a fill factor of the washcoat layer of 75% or more is suppressed to 35 number% or less.
  • the washcoat layer reached from the surface on the entry side of the partition wall to the surface on the opposite side, whereas the particulate filter of Example 3-2 Since the coating amount was as small as 25 g / L, the washcoat layer formation region was a region where the thickness was about 50% from the surface of the partition wall on the entry side.
  • ⁇ Pressure loss increase characteristics The pressure loss increasing characteristics of the particulate filter of each example were evaluated.
  • the PM collection rate of the particulate filter tends to increase as the coat amount of the wash coat layer increases. If the coating amount is more than 0 g / L, the PM collection rate is increased because the washcoat layer is formed even if only slightly. In this example, since the arrangement of the washcoat layer with respect to the bare base material was appropriately controlled, it was clear that the PM collection rate increased even when the coating amount was relatively small, for example, about 25 g / L. I was able to confirm.
  • the coating amount reaches about 100 g / L
  • the increase in the PM trapping rate almost stops increasing, and a coating amount of about 100 g / L is sufficient. I knew it was.
  • the pressure loss increase rate tends to increase almost linearly as the coat amount of the wash coat layer increases. From the viewpoint of suppressing the pressure loss increase rate to be low, it is preferable that the coat amount is small. From these facts, it can be said that the increase in the PM collection rate and the suppression in the pressure loss increase rate can both be achieved by setting the coating amount to be about 25 g / L or more, for example, about 100 g / L or less.
  • the length L A of the portion upstream washcoat layer 20A is formed
  • the length of the portion downstream washcoat layer 20B is formed
  • configuration washcoat layer 20 is not limited thereto.
  • the length L B of the portion where the downstream washcoat layer 20B is formed may be longer or shorter than the length L A of the portion where the upstream washcoat layer 20A is formed.
  • the washcoat layer 20 may be formed by one-time slurry injection without dividing the upstream side washcoat layer 20A and the downstream side washcoat layer 20B.
  • the average filling ratios A, B, and C of the washcoat layers retained in the pores in each pore size range satisfy the above relationship, and the filling ratio among the pores having a pore size of 5 ⁇ m or more and less than 20 ⁇ m is By setting the ratio of the pores of 75% or more to 35% by number or less, the PM trapping performance can be highly improved.
  • Rh as the noble metal catalyst contained in the washcoat layer 20
  • the noble metal catalyst can be used as the noble metal catalyst in the main application or main driving situation of the vehicle in which the particulate filter 100 is provided. It can be appropriately changed in consideration of the active property.
  • each member and part of the exhaust gas purification device 1 may be changed.
  • the catalyst unit 5 is provided on the upstream side of the filter unit 6, but the catalyst unit 5 may be omitted.
  • the exhaust gas purification device 1 is particularly suitable as a device for purifying harmful components in exhaust gas having a relatively high exhaust temperature, such as a gasoline engine.
  • the exhaust gas purifying apparatus 1 according to the present invention is not limited to the purpose of purifying harmful components in the exhaust gas of a gasoline engine, but various types of purifying harmful components in the exhaust gas discharged from other engines (for example, diesel engines). It can be used for various purposes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geometry (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Filtering Materials (AREA)
PCT/JP2019/042464 2018-11-15 2019-10-30 パティキュレートフィルタ Ceased WO2020100582A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US17/285,290 US11454149B2 (en) 2018-11-15 2019-10-30 Particulate filter
EP19884989.5A EP3854477B1 (en) 2018-11-15 2019-10-30 Particulate filter
CN201980075307.9A CN113039015A (zh) 2018-11-15 2019-10-30 微粒过滤器

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018215005A JP7013361B2 (ja) 2018-11-15 2018-11-15 パティキュレートフィルタ
JP2018-215005 2018-11-15

Publications (1)

Publication Number Publication Date
WO2020100582A1 true WO2020100582A1 (ja) 2020-05-22

Family

ID=70732058

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/042464 Ceased WO2020100582A1 (ja) 2018-11-15 2019-10-30 パティキュレートフィルタ

Country Status (5)

Country Link
US (1) US11454149B2 (enExample)
EP (1) EP3854477B1 (enExample)
JP (1) JP7013361B2 (enExample)
CN (1) CN113039015A (enExample)
WO (1) WO2020100582A1 (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022110535A (ja) * 2021-01-18 2022-07-29 本田技研工業株式会社 排気浄化フィルタ
WO2022176528A1 (ja) * 2021-02-16 2022-08-25 株式会社キャタラー 排ガス浄化用触媒

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113661310A (zh) * 2019-03-29 2021-11-16 本田技研工业株式会社 排气净化过滤器
JP7475138B2 (ja) * 2019-12-27 2024-04-26 株式会社キャタラー 排ガス浄化用触媒
JP2022111085A (ja) * 2021-01-19 2022-07-29 本田技研工業株式会社 排気浄化フィルタ
WO2022269947A1 (ja) 2021-06-23 2022-12-29 株式会社キャタラー パティキュレートフィルタ
JP2024070977A (ja) * 2022-11-14 2024-05-24 トヨタ自動車株式会社 排ガス浄化装置

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007185571A (ja) 2006-01-11 2007-07-26 Toyota Central Res & Dev Lab Inc 排ガス浄化用触媒及びその製造方法
JP2009082915A (ja) 2007-09-27 2009-04-23 Umicore Ag & Co Kg 主として化学量論的空気／燃料混合物により運転される内燃機関エンジンの排ガスからの粒子の除去
JP2010184183A (ja) * 2009-02-11 2010-08-26 Nippon Soken Inc 排ガス浄化装置
JP2013043138A (ja) * 2011-08-25 2013-03-04 Denso Corp 触媒担持体及びその製造方法
JP2017072033A (ja) * 2015-10-05 2017-04-13 株式会社キャタラー 排ガス浄化装置
WO2017119101A1 (ja) * 2016-01-07 2017-07-13 ジョンソン・マッセイ・ジャパン合同会社 フィルター
WO2017163984A1 (ja) * 2016-03-24 2017-09-28 株式会社キャタラー 排ガス浄化装置
JP2017171553A (ja) * 2016-03-25 2017-09-28 日本碍子株式会社 ハニカム構造体
WO2019058948A1 (ja) * 2017-09-21 2019-03-28 株式会社キャタラー 排ガス浄化用触媒体

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4768475B2 (ja) 2006-03-01 2011-09-07 Ｄｏｗａホールディングス株式会社 Ｐｍ燃焼触媒用複合酸化物およびフィルター
CN101977682A (zh) * 2008-03-19 2011-02-16 株式会社Ict 内燃机废气净化用催化剂和使用该催化剂的废气净化方法
CN103263912B (zh) * 2013-05-27 2015-02-04 四川中自尾气净化有限公司 一种柴油车尾气净化催化剂及其制备方法
CN104138754B (zh) * 2014-06-09 2018-07-13 西南石油大学 净化柴油车尾气中可溶性有机物的催化剂及其制备方法
JP6655060B2 (ja) * 2015-02-17 2020-02-26 株式会社キャタラー 排ガス浄化用触媒
JP6594163B2 (ja) 2015-10-30 2019-10-23 株式会社キャタラー 排ガス浄化装置
JP6934311B2 (ja) 2016-06-02 2021-09-15 株式会社キャタラー 排ガス浄化フィルタ
WO2018180705A1 (ja) * 2017-03-31 2018-10-04 株式会社キャタラー 排ガス浄化用触媒

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007185571A (ja) 2006-01-11 2007-07-26 Toyota Central Res & Dev Lab Inc 排ガス浄化用触媒及びその製造方法
JP2009082915A (ja) 2007-09-27 2009-04-23 Umicore Ag & Co Kg 主として化学量論的空気／燃料混合物により運転される内燃機関エンジンの排ガスからの粒子の除去
JP2010184183A (ja) * 2009-02-11 2010-08-26 Nippon Soken Inc 排ガス浄化装置
JP2013043138A (ja) * 2011-08-25 2013-03-04 Denso Corp 触媒担持体及びその製造方法
JP2017072033A (ja) * 2015-10-05 2017-04-13 株式会社キャタラー 排ガス浄化装置
WO2017119101A1 (ja) * 2016-01-07 2017-07-13 ジョンソン・マッセイ・ジャパン合同会社 フィルター
WO2017163984A1 (ja) * 2016-03-24 2017-09-28 株式会社キャタラー 排ガス浄化装置
JP2017171553A (ja) * 2016-03-25 2017-09-28 日本碍子株式会社 ハニカム構造体
WO2019058948A1 (ja) * 2017-09-21 2019-03-28 株式会社キャタラー 排ガス浄化用触媒体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3854477A4

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022110535A (ja) * 2021-01-18 2022-07-29 本田技研工業株式会社 排気浄化フィルタ
JP7178432B2 (ja) 2021-01-18 2022-11-25 本田技研工業株式会社 排気浄化フィルタ
WO2022176528A1 (ja) * 2021-02-16 2022-08-25 株式会社キャタラー 排ガス浄化用触媒
JP2022124800A (ja) * 2021-02-16 2022-08-26 株式会社キャタラー 排ガス浄化用触媒
JP7717467B2 (ja) 2021-02-16 2025-08-04 株式会社キャタラー 排ガス浄化用触媒

Also Published As

Publication number Publication date
JP2020081912A (ja) 2020-06-04
JP7013361B2 (ja) 2022-02-15
US20210381413A1 (en) 2021-12-09
EP3854477B1 (en) 2024-08-28
CN113039015A (zh) 2021-06-25
EP3854477A4 (en) 2021-07-28
EP3854477A1 (en) 2021-07-28
US11454149B2 (en) 2022-09-27

Similar Documents

Publication Publication Date Title
CN107073463B (zh) 废气净化用催化剂
JP7013361B2 (ja) パティキュレートフィルタ
US10981113B2 (en) Exhaust gas purification catalyst body
JP6297767B2 (ja) 排ガス浄化装置
JP6594149B2 (ja) 排ガス浄化装置
JP7023770B2 (ja) 排ガス浄化用触媒
JP2016077981A (ja) 排ガス浄化装置
US12239968B2 (en) Particulate filter
CN114080493B (zh) 微粒过滤器
CN113661311A (zh) 排气净化过滤器
JP2007252997A (ja) フィルタ型排ガス浄化用触媒
JP2008178766A (ja) パティキュレートフィルタ
WO2021131630A1 (ja) 排ガス浄化用触媒
JP7178432B2 (ja) 排気浄化フィルタ
CN105473222B (zh) 尾气净化用催化剂及其制备方法
JP2021143664A (ja) 排ガス浄化装置

Legal Events

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

Ref document number: 19884989

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 19884989.5

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2019884989

Country of ref document: EP

Effective date: 20210422

NENP Non-entry into the national phase

Ref country code: DE