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WO2016056573A1 - Dispositif de purification de gaz d'échappement - Google Patents

Dispositif de purification de gaz d'échappement Download PDF

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Publication number
WO2016056573A1
WO2016056573A1 PCT/JP2015/078410 JP2015078410W WO2016056573A1 WO 2016056573 A1 WO2016056573 A1 WO 2016056573A1 JP 2015078410 W JP2015078410 W JP 2015078410W WO 2016056573 A1 WO2016056573 A1 WO 2016056573A1
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WIPO (PCT)
Prior art keywords
catalyst layer
exhaust gas
partition wall
cell
base material
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/JP2015/078410
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English (en)
Japanese (ja)
Inventor
達也 大橋
新吾 坂神
伊藤　毅
亮太 尾上
三好　直人
竹内　雅彦
あけみ 佐藤
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
Priority claimed from JP2015136905A external-priority patent/JP6564637B2/ja
Application filed by Cataler Corp filed Critical Cataler Corp
Priority to CN201580054598.5A priority Critical patent/CN106794421B/zh
Priority to US15/515,830 priority patent/US10357744B2/en
Priority to EP15848560.7A priority patent/EP3205388A4/fr
Publication of WO2016056573A1 publication Critical patent/WO2016056573A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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

Definitions

  • the present invention relates to an exhaust gas purification apparatus. More specifically, the present invention relates to an exhaust gas purification device that purifies exhaust gas discharged from an internal combustion engine such as a gasoline engine.
  • an exhaust gas purification device that purifies exhaust gas discharged from an internal combustion engine such as a gasoline engine.
  • exhaust gas discharged from an internal combustion engine contains particulate matter (PM) containing carbon as a main component, ash composed of non-combustible components, and is known to cause air pollution.
  • PM particulate matter
  • ash composed of non-combustible components
  • NOx nitrogen oxides
  • a particulate filter for collecting the particulate matter is provided in the exhaust passage of the internal combustion engine.
  • a gasoline particulate filter GPF
  • a gasoline particulate filter there is known a structure called a wall flow type in which a base material is composed of a large number of porous cells, and the inlets and outlets of a large number of cells are alternately closed (Patent Literature). 1, 2).
  • Patent Literature Patent Literature 1
  • the exhaust gas flowing in from the cell inlet passes through the partitioned porous cell partition wall and is discharged to the cell outlet. And while exhaust gas passes a porous cell partition, a particulate matter is collected in the pore inside a partition.
  • Patent Document 1 describes an exhaust gas purifying catalyst in which platinum (Pt) and rhodium (Rh) as noble metal catalysts are separately supported in a partition wall.
  • Patent Document 2 describes an exhaust gas purifying catalyst in which a palladium (Pd) layer as a noble metal catalyst is disposed inside a partition wall and a rhodium (Rh) layer is laminated on the surface of the partition wall.
  • the present invention has been made in view of such a case, and the main object of the present invention is to improve exhaust gas purification performance while reducing pressure loss in an exhaust gas purification apparatus having a wall flow structure type particulate filter. It is an object to provide an exhaust gas purification device that can be made to operate.
  • An exhaust gas purification apparatus is an exhaust gas purification apparatus that is disposed in an exhaust passage of an internal combustion engine and purifies exhaust gas discharged from the internal combustion engine.
  • the apparatus includes an inlet cell in which only an end portion on an exhaust gas inflow side is opened, an outlet cell in which only an end portion on an exhaust gas outlet side is adjacent to the inlet side cell, and the inlet cell and the outlet cell.
  • a wall flow structure base material having a porous partition wall, an upstream catalyst layer provided in the partition wall, and a downstream catalyst layer provided in the partition wall.
  • the upstream catalyst layer is disposed in an upstream portion in the exhaust gas circulation direction including an end portion of the base material on the exhaust gas inflow side.
  • the said downstream catalyst layer is arrange
  • Each of the upstream catalyst layer and the downstream catalyst layer contains a carrier and at least one noble metal selected from platinum (Pt), palladium (Pd), and rhodium (Rh) supported on the carrier. To do.
  • the noble metal contained in the upstream catalyst layer is different from the noble metal contained in the downstream catalyst layer.
  • “the noble metals are different” between the upstream catalyst layer and the downstream catalyst layer means that the combination of the noble metals contained in each catalyst layer is different from the embodiment in which the types of noble metals contained in each catalyst layer are different. Means different.
  • the term “noble metal is different” here means, for example, an embodiment in which the noble metal in the upstream catalyst layer is Rh and the noble metals in the downstream catalyst layer are Rh and Pd; the noble metal in the upstream catalyst layer is Rh.
  • an embodiment in which the noble metal of the downstream catalyst layer is Pt and Rh can be included.
  • the exhaust gas purifying apparatus it is possible to provide an exhaust gas purifying apparatus in which the purification performance of exhaust gas is remarkably improved while reducing pressure loss.
  • the coating amount of the upstream catalyst layer per 1 L of the base material is larger than the coating amount of the downstream catalyst layer per 1 L of the base material. Few. Thus, by making the coating amount of the upstream catalyst layer smaller than the coating amount of the downstream catalyst layer, the exhaust gas preferentially flows to the upstream portion of the partition wall. Thereby, the flow of the exhaust gas from the entry side cell to the exit side cell becomes smooth, and the pressure loss can be further reduced.
  • the coating amount of the upstream catalyst layer per liter of the base material is 60 g / L or more and less than 99.9 g / L. The effect mentioned above can be exhibited more favorably within the range of the coating amount of the upstream catalyst layer.
  • the upstream catalyst layer corresponds to 20% to 80% of the length of the base material from the exhaust gas inflow side end of the base material toward the downstream side. It is formed in the part.
  • the downstream catalyst layer is formed in a portion corresponding to 20% to 80% of the length of the base material from the end of the base material on the exhaust gas discharge side toward the upstream side.
  • the upstream catalyst layer includes Rh as the noble metal
  • the downstream catalyst layer includes Pt and / or Pd as the noble metal
  • the upstream catalyst layer is in contact with the inlet cell and not in contact with the outlet cell in the thickness direction of the partition. It is unevenly distributed inside. Further, the downstream catalyst layer is unevenly distributed inside the partition wall so as to be in contact with the outlet cell and not to be in contact with the inlet cell.
  • a plurality of noble metals for example, Pt and Rh
  • the noble metal is densely arranged in the partition wall, the contact between the noble metal and the exhaust gas becomes good. For this reason, the purification performance of exhaust gas can be further improved.
  • the upstream catalyst layer is 30% to 70% of the thickness of the partition wall from the surface of the partition wall in contact with the inlet cell toward the outlet cell side. It is formed in the part which hits.
  • the downstream catalyst layer is formed in a portion corresponding to 30% to 70% of the thickness of the partition wall from the surface of the partition wall in contact with the exit cell toward the input cell side.
  • the internal combustion engine is a gasoline engine.
  • the temperature of exhaust gas is relatively high, and PM hardly accumulates in the partition walls. Therefore, when the internal combustion engine is a gasoline engine, the above-described effects are more effectively exhibited.
  • FIG. 1 is a diagram schematically showing an exhaust gas purification apparatus according to an embodiment.
  • FIG. 2 is a perspective view schematically showing a filter of the exhaust gas purifying apparatus according to one embodiment.
  • FIG. 3 is a cross-sectional view schematically showing a filter cross section of the exhaust gas purifying apparatus according to an embodiment.
  • FIG. 4 is a graph showing the relationship between the coating amount of the upstream catalyst layer and the HC 50% purification temperature.
  • FIG. 5 is a graph showing the relationship between the coating amount of the upstream catalyst layer and the pressure loss increase rate.
  • FIG. 6 is a cross-sectional SEM image of the partition wall of Sample 1.
  • FIG. 7 is a cross-sectional SEM image of the partition wall of Sample 12.
  • FIG. 8 is a cross-sectional SEM image of the partition wall of Sample 13.
  • FIG. 1 is a diagram schematically showing an internal combustion engine 2 and an exhaust gas purification device 1 provided in an exhaust system of the internal combustion engine 2.
  • An air-fuel mixture containing oxygen and fuel gas is supplied to the internal combustion engine (engine) according to the present embodiment.
  • the internal combustion engine burns the air-fuel mixture and converts the combustion energy into mechanical energy.
  • the air-fuel mixture combusted at this time becomes exhaust gas and is discharged to the exhaust system.
  • the internal combustion engine 2 having the configuration shown in FIG. 1 is mainly composed of an automobile gasoline engine.
  • An exhaust manifold 3 is connected to an exhaust port (not shown) for communicating the engine 2 with an exhaust system.
  • the exhaust manifold 3 is connected to an exhaust pipe 4 through which exhaust gas flows.
  • the exhaust manifold 3 and the exhaust pipe 4 form the exhaust passage of this embodiment.
  • the arrows in the figure indicate the exhaust gas distribution direction.
  • the exhaust gas purification apparatus 1 disclosed here is provided in the exhaust system of the engine 2.
  • the exhaust gas purification apparatus 1 includes a catalyst unit 5, a filter unit 6, and an ECU 7, and includes harmful components (for example, carbon monoxide (CO), hydrocarbon (HC), nitrogen oxide (NO) contained in the exhaust gas discharged. x )) is purified and particulate matter (PM) contained in the exhaust gas is collected.
  • harmful components for example, carbon monoxide (CO), hydrocarbon (HC), nitrogen oxide (NO) contained in the exhaust gas discharged. x )
  • PM particulate matter
  • the ECU 7 is a unit that performs control between the engine 2 and the exhaust gas purification device 1 and includes a digital computer and other electronic devices as constituent elements in the same manner as a general control device.
  • the ECU 7 is provided with an input port and is electrically connected to a sensor (for example, a pressure sensor 8) installed in each part of the engine 2 and the exhaust gas purification device 1.
  • a sensor for example, a pressure sensor 8
  • the ECU 7 is also provided with an output port.
  • the ECU 7 is connected to each part of the engine 2 and the exhaust gas purification device 1 via the output port, and controls the operation of each member by transmitting a control signal.
  • the catalyst unit 5 is configured to be able to purify ternary components (NOx, HC, CO) contained in the exhaust gas, and is provided in the exhaust pipe 4 communicating with the engine 2. Specifically, as shown in FIG. 1, it is provided on the downstream side of the exhaust pipe 4.
  • the kind of the catalyst part 5 is not specifically limited.
  • the catalyst unit 5 may be a catalyst on which a noble metal such as platinum (Pt), palladium (Pd), rhodium (Rd) is supported, for example.
  • a downstream side catalyst part may be further arranged in the exhaust pipe 4 on the downstream side of the filter part 6. Since the specific configuration of the catalyst unit 5 does not characterize the present invention, a detailed description thereof is omitted here.
  • the filter unit 6 is provided on the downstream side of the catalyst unit 5.
  • the filter unit 6 includes a gasoline particulate filter (GPF) capable of collecting and removing particulate matter (hereinafter simply referred to as “PM”) contained in the exhaust gas.
  • GPF gasoline particulate filter
  • PM particulate matter
  • FIG. 2 is a perspective view of the particulate filter 100.
  • FIG. 3 is an enlarged schematic view of a part of a cross section of the particulate filter 100 cut in the axial direction.
  • the particulate filter 100 includes a base material 10 having a wall flow structure, an upstream catalyst layer 20, and a downstream catalyst layer 30.
  • the base material 10, the upstream catalyst layer 20, and the downstream catalyst layer 30 will be described in this order.
  • a base material formed of a ceramic or alloy (stainless steel or the like) such as cordierite or silicon carbide (SiC) can be suitably employed.
  • a substrate whose outer shape is a cylindrical shape is illustrated.
  • the outer shape of the entire substrate may be an elliptical cylinder or a polygonal cylinder instead of the cylinder.
  • Such a base material 10 includes an inlet cell 12 that is open only at the end portion on the exhaust gas inflow side, an outlet cell 14 that is adjacent to the inlet cell 12 and is open only at the end portion on the exhaust gas outlet side, and the inlet cell 12. And a porous partition wall 16 that partitions the outlet cell 14.
  • the inlet side cell 12 is open only at the end on the exhaust gas inflow side, and the outlet cell 14 is adjacent to the inlet side cell 12 and is open only at the end on the exhaust gas outflow side.
  • the inlet side cell 12 is sealed with the sealing part 12a at the end on the exhaust gas outflow side
  • the outlet side cell 14 is sealed with the sealing part 14a at the end on the exhaust gas inflow side.
  • the inlet cell 12 and the outlet cell 14 may be set to appropriate shapes and sizes in consideration of the flow rate and components of the exhaust gas supplied to the filter 100.
  • the shapes of the entrance cell 12 and the exit cell 14 are various geometric shapes such as a rectangle such as a square, a parallelogram, a rectangle, and a trapezoid, a triangle, other polygons (for example, a hexagon, an octagon), and a circle. It may be.
  • Partition wall 16 A partition wall 16 is formed between the adjacent entrance cell 12 and exit cell 14. The entrance cell 12 and the exit cell 14 are partitioned by the partition wall 16.
  • 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 is generally 50% to 70%, preferably 55% to 65%. If the porosity of the partition wall 16 is too small, PM may slip through. On the other hand, if the porosity of the partition wall 16 is too large, the mechanical strength of the filter 100 tends to decrease, which is not preferable.
  • the thickness of the partition wall 16 is not particularly limited, but is preferably about 200 ⁇ m to 800 ⁇ m. Within such a range of the partition wall thickness, an effect of suppressing an increase in pressure loss can be obtained without impairing the PM collection efficiency.
  • the upstream catalyst layer 20 is provided inside the partition wall 16.
  • the upstream catalyst layer 20 is disposed in the upstream portion including the end of the base material 10 on the exhaust gas inflow side.
  • the upstream catalyst layer 20 includes a carrier (not shown) and a noble metal (not shown) supported on the carrier.
  • the upstream catalyst layer 20 is formed in a portion (1/2 L) corresponding to 50% of the length L of the base material 10 from the end on the exhaust gas inflow side of the base material 10 toward the downstream side. . Further, the upstream catalyst layer 20 is unevenly distributed in the partition wall 16 so as to contact the inlet cell 12 and not to contact the outlet cell 14 in the thickness direction of the partition wall 16. In this embodiment, the upstream catalyst layer 20 is formed in a portion (1 / 2D) corresponding to 50% of the thickness D of the partition wall 16 from the surface of the partition wall 16 in contact with the inlet cell 12 toward the outlet cell 14 side. ing.
  • the upstream catalyst layer 20 may contain any one or two precious metals of platinum (Pt), palladium (Pd), and rhodium (Rh).
  • the upstream catalyst layer 20 contains Rh as a noble metal.
  • the content of Rh per liter of the base material is preferably about 0.05 to 0.2 g (preferably 0.1 to 0.15 g). If the content of Rh is too small, the catalytic activity obtained by Rh may be insufficient. On the other hand, if the amount of Rh supported is too large, Rh tends to cause grain growth and disadvantageous in terms of cost. is there.
  • the upstream catalyst layer 20 may contain a noble metal other than Rh, Pt, and Pd. As noble metals other than Rh, Pt and Pd, for example, ruthenium (Ru), iridium (Ir), osmium (Os) and the like can be used.
  • the upstream catalyst layer 20 is formed by supporting Rh on a carrier.
  • a carrier metal oxides such as alumina (Al 2 O 3 ), zirconia (ZrO 2 ), ceria (CeO 2 ), silica (SiO 2 ), magnesia (MgO), titanium oxide (titania: TiO 2 ), Alternatively, a solid solution thereof (eg, ceria-zirconia (CeO 2 —ZrO 2 ) composite oxide) can be given. Of these, use of alumina is preferable. Two or more of these may be used in combination. Note that another material (typically an inorganic oxide) may be added to the carrier as a subcomponent.
  • rare earth elements such as lanthanum (La) and yttrium (Y), alkaline earth elements such as calcium, and other transition metal elements can be used.
  • rare earth elements such as lanthanum and yttrium are preferably used as stabilizers because they can improve the specific surface area at high temperatures without impairing the catalytic function.
  • the shape (outer shape) of the carrier is not particularly limited, but a powdery one is preferably used from the viewpoint of securing a larger specific surface area.
  • the average particle size of the carrier (average particle size measured by laser diffraction / scattering method) is preferably 8 ⁇ m or less (eg, 4 ⁇ m to 7 ⁇ m).
  • the average particle size of the carrier is too large, the dispersibility of the noble metal supported on the carrier tends to be lowered, and the purification performance of the catalyst is lowered.
  • the average particle size of the carrier is too small, the heat resistance of the carrier itself composed of the carrier is lowered, so that the heat resistance of the catalyst is lowered, which is not preferable. Therefore, it is usually preferable to use a carrier having an average particle diameter of about 3 ⁇ m or more (for example, 4 ⁇ m or more).
  • the method for supporting Rh on the carrier is not particularly limited.
  • it can be prepared by impregnating the carrier with an aqueous solution containing an Rh salt (for example, nitrate) or an Rh complex (for example, a tetraammine complex), then drying and baking.
  • an Rh salt for example, nitrate
  • an Rh complex for example, a tetraammine complex
  • a promoter that does not support a noble metal can be added to the upstream catalyst layer 20 disclosed herein.
  • the cocatalyst include ceria-zirconia (CeO 2 —ZrO 2 ) composite oxide and silica (SiO 2 ). In particular, use of ceria-zirconia composite oxide is preferable.
  • the content of the cocatalyst when the total of Rh, the support and the cocatalyst is 100% by mass is usually 20% by mass to 80% by mass, for example, 30% by mass to 70% by mass. It is preferable that
  • the upstream catalyst layer 20 is formed by coating the inside of the partition wall 16 (typically suction coating by reducing the pressure of the slurry) containing the powder comprising Rh supported on the carrier and the metal oxide powder. Can be formed.
  • a binder may be included in the slurry in order to allow the slurry to adhere appropriately to the inside of the partition wall 16.
  • the binder for example, use of alumina sol, silica sol or the like is preferable.
  • the viscosity of the slurry may be adjusted as appropriate so that the slurry can easily flow into the partition wall 16 of the substrate 10.
  • the inflow amount of the slurry may be appropriately adjusted according to the volume of the base material 10 and the coating amount of the upstream catalyst layer 20 so that the inflowing slurry appropriately stays inside the partition wall 16 of the base material 10.
  • the downstream catalyst layer 30 is provided inside the partition wall 16.
  • the downstream catalyst layer 30 is disposed in the downstream portion including the end of the base material 10 on the exhaust gas outflow side.
  • the downstream catalyst layer 30 includes a support (not shown) and a noble metal (not shown) supported on the support.
  • the downstream catalyst layer 30 is formed in a portion (1/2 L) corresponding to 50% of the length L of the base material 10 from the end on the exhaust gas outflow side of the base material 10 toward the upstream side. . Further, the downstream side catalyst layer 30 is unevenly distributed inside the partition wall 16 so as to be in contact with the outlet side cell 14 and not in contact with the inlet side cell 12 in the thickness direction of the partition wall 16. In this embodiment, the downstream catalyst layer 30 is formed in a portion (1 / 2D) corresponding to 50% of the thickness D of the partition wall 16 from the surface of the partition wall 16 in contact with the outlet cell 14 toward the inlet cell 12 side. ing.
  • the noble metal contained in the downstream catalyst layer 30 is different from the noble metal contained in the upstream catalyst layer 20.
  • the downstream catalyst layer 30 includes a precious metal other than the precious metal (here, Rh) included in the upstream catalyst layer 20 among Pt, Pd, and Rh.
  • the downstream catalyst layer 30 contains Pt as a noble metal.
  • the Pt content per liter of the base material is preferably about 0.1 to 2 g (preferably 0.5 to 1 g). If the supported amount of Pt is too small, the catalytic activity obtained by Pt becomes insufficient. On the other hand, if the supported amount of Pt is too large, the noble metal is liable to cause grain growth and at the same time is disadvantageous in terms of cost.
  • the downstream catalyst layer 30 may contain a noble metal other than Rh, Pt, and Pd.
  • noble metals other than Rh, Pt and Pd for example, ruthenium (Ru), iridium (Ir), osmium (Os) and the like can be used.
  • the downstream catalyst layer 30 is formed by supporting Pt on a carrier.
  • a carrier metal oxides such as alumina (Al 2 O 3 ), zirconia (ZrO 2 ), ceria (CeO 2 ), silica (SiO 2 ), magnesia (MgO), titanium oxide (titania: TiO 2 ), Alternatively, a solid solution thereof (eg, ceria-zirconia (CeO 2 —ZrO 2 ) composite oxide) can be given. Of these, the use of ceria-zirconia composite oxide is preferred. Two or more of these may be used in combination. Note that another material (typically an inorganic oxide) may be added to the carrier as a subcomponent.
  • rare earth elements such as lanthanum (La) and yttrium (Y), alkaline earth elements such as calcium, and other transition metal elements can be used.
  • rare earth elements such as lanthanum and yttrium are preferably used as stabilizers because they can improve the specific surface area at high temperatures without impairing the catalytic function.
  • the shape (outer shape) of the carrier is not particularly limited, but a powdery one is preferably used from the viewpoint of securing a larger specific surface area.
  • the average particle size of the carrier (average particle size measured by laser diffraction / scattering method) is preferably 8 ⁇ m or less (eg, 4 ⁇ m to 7 ⁇ m).
  • the average particle size of the carrier is too large, the dispersibility of the noble metal supported on the carrier tends to be lowered, and the purification performance of the catalyst is lowered.
  • the average particle size of the carrier is too small, the heat resistance of the carrier itself composed of the carrier is lowered, so that the heat resistance of the catalyst is lowered, which is not preferable. Therefore, it is usually preferable to use a carrier having an average particle diameter of about 3 ⁇ m or more (for example, 4 ⁇ m or more).
  • the method for supporting Pt on the carrier is not particularly limited.
  • it can be prepared by impregnating the carrier with an aqueous solution containing a Pt salt (for example, nitrate) or a Pt complex (for example, a tetraammine complex), then drying and baking.
  • a Pt salt for example, nitrate
  • a Pt complex for example, a tetraammine complex
  • a cocatalyst not supporting a noble metal can be added to the downstream catalyst layer 30 disclosed here.
  • the cocatalyst include alumina and silica (SiO 2 ).
  • the content of the co-catalyst when the total of Pt, the support and the co-catalyst (for example, alumina) is 100% by mass is usually 20% by mass to 80% by mass, for example, 30% by mass. It is preferable that the amount be ⁇ 70 mass%.
  • Barium may be added to the downstream catalyst layer 30 disclosed here.
  • barium poisoning of the noble metal is suppressed and the catalytic activity is improved. Further, the dispersibility of the noble metal is improved, and the durability of the catalyst can be improved by better suppressing the sintering accompanying the noble metal grain growth at a high temperature.
  • the amount of barium added is 10 with respect to the total mass of the downstream catalyst layer 30 excluding the barium (that is, the total of Pt, support, and metal oxide particles). Those satisfying 12% by mass to 15% by mass are preferable, and those satisfying 12% by mass to 15% by mass are particularly preferable.
  • the downstream catalyst layer 30 to which barium is added is prepared, for example, by preparing a barium aqueous solution in which a water-soluble barium salt (for example, barium sulfate) is dissolved in water (typically ion-exchanged water), and this barium aqueous solution is used as a carrier. It can produce by adding and baking to etc.
  • a water-soluble barium salt for example, barium sulfate
  • water typically ion-exchanged water
  • the downstream catalyst layer 30 is formed by coating the inside of the partition wall 16 with a slurry containing the powder formed by supporting Pt on the carrier and the metal oxide powder (typically suction coating by reducing the pressure of the slurry). Can be formed.
  • the slurry may contain a binder in order to properly adhere the slurry to the inside of the partition wall 16.
  • the binder for example, use of alumina sol, silica sol or the like is preferable.
  • the viscosity of the slurry may be adjusted as appropriate so that the slurry can easily flow into the partition wall 16 of the substrate 10. Further, the inflow amount of the slurry may be appropriately adjusted according to the volume of the base material 10 and the coating amount of the downstream side catalyst layer 30 so that the inflowing slurry appropriately stays inside the partition wall 16 of the base material 10.
  • exhaust gas flows from the inlet side 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.
  • an arrow indicates a route through which the exhaust gas flowing from the entry side cell 12 passes through the partition wall 16 and reaches the exit side cell 14.
  • the partition wall 16 has a porous structure, PM is collected on the surface of the partition wall 16 or in the pores inside the partition wall 16 while the exhaust gas passes through the partition wall 16.
  • harmful components in the exhaust gas are purified while the exhaust gas passes through the interior and surface of the partition wall 16. .
  • the exhaust gas that has passed through the partition wall 16 and has reached the exit side cell 14 is discharged from the opening on the exhaust gas outflow side to the outside of the filter 100.
  • the particulate filter 100 Pt and Rh are separated and supported by the upstream portion (upstream catalyst layer 20) and the downstream portion (downstream catalyst layer 30) of the base material 10, so that Pt and Rh Is effectively suppressed. Therefore, even when exposed to high temperatures, catalyst deterioration is suppressed.
  • both the upstream catalyst layer 20 and the downstream catalyst layer 30 are disposed inside the partition wall 16, compared with the case where the catalyst layers 20 and 30 are formed on the surface (outside) of the partition wall 16, the exhaust gas becomes easier to flow. Thereby, flow path resistance can be made low and pressure loss can be reduced. Therefore, according to the present configuration, it is possible to provide the particulate filter 100 in which the exhaust gas purification performance is remarkably improved while reducing the pressure loss, and the exhaust gas purification device 1 including the particulate filter 100.
  • the catalyst layer is disposed inside the partition wall means that the catalyst layer is mainly present inside the partition wall rather than outside (typically the surface) of the partition wall. More specifically, for example, the cross section of the partition wall of the upstream catalyst layer is observed with an electron microscope, and is 1/10 the length (0. The entire coating amount in the range of 1L) is set to 100%. At this time, the coating amount existing inside the partition wall is typically 80% or more, such as 85% or more, preferably 90% or more, further 95% or more, and particularly substantially 100%. Say. Therefore, for example, when the catalyst layer is arranged on the surface of the partition wall, it is clearly distinguished from the case where a part of the catalyst layer unintentionally penetrates into the partition wall.
  • the upstream catalyst layer 20 is 20% to 80% (preferably 50% to 70% of the length L of the base material 10 from the end of the base material 10 on the exhaust gas inflow side toward the downstream side, that is, 1% of the whole base material. / 2 to 7/10).
  • the downstream catalyst layer 30 is 20% to 80% (preferably 30% to 50% of the length L of the base material 10 from the end on the exhaust gas discharge side of the base material 10 toward the upstream side, that is, the whole base material. 3/10 to 1/2).
  • the downstream catalyst layer 30 is preferably formed in a portion other than the upstream catalyst layer 20 in the length direction of the base material 10 (the extending direction of the partition walls 16).
  • the total length of the substrate 10 is L
  • the total length of the upstream catalyst layer 20 is La
  • the total length of the downstream catalyst layer 30 is Lb
  • La 0.2L to 0.8L
  • Lb 0.2L to 0.00.
  • 8L and La + Lb L.
  • the upstream catalyst layer 20 is unevenly distributed inside the partition wall 16 so as to be in contact with the inlet cell 12 and not to be in contact with the outlet cell 14.
  • the downstream catalyst layer 30 is unevenly distributed inside the partition wall 16 so as to be in contact with the outlet cell 14 and not to be in contact with the inlet cell 12.
  • the upstream catalyst layer 20 is 30% to 100% (for example, 30% to 70%, preferably 30%) of the thickness D of the partition wall 16 from the surface of the partition wall 16 in contact with the inlet cell 12 toward the outlet cell 14 side. Is preferably 30% to 80%, more preferably 40% to 80%, that is, a portion corresponding to 2/5 to 4/5) of the partition wall thickness.
  • the downstream catalyst layer 30 is 30% to 100% (for example, 30% to 70%, preferably, the thickness D of the partition wall 16 from the surface of the partition wall 16 in contact with the exit side cell 14 toward the input side cell 12 side. It may be formed in a portion corresponding to 30% to 80%, more preferably 40% to 80%, that is, 2/5 to 4/5) of the partition wall thickness.
  • the downstream catalyst layer 30 is preferably formed so as not to overlap the upstream catalyst layer 20 in the thickness direction of the partition wall 16.
  • the partition wall 16 has a thickness D
  • the upstream catalyst layer 20 has a thickness Da
  • the downstream catalyst layer 30 has a thickness Db
  • Da 0.3D to 1.0D
  • Db 0.3D to 1.0D.
  • Da + Db ⁇ D is preferable. If the thicknesses Da and Db of the upstream side catalyst layer 20 and the downstream side catalyst layer 30 are within the range, the purification performance can be improved and the pressure loss can be reduced at a higher level.
  • the coating amount of the upstream catalyst layer 20 per 1 L of the base material may be smaller than the coating amount of the downstream catalyst layer 30 per 1 L of the base material.
  • the coating amount of the upstream catalyst layer 20 is generally 60 g / L or more and less than 100 g / L, preferably 60 g / L or more and 80 g.
  • the coating amount of the downstream catalyst layer 30 per liter of the base material is preferably about 100 g / L or more and less than 140 g / L, preferably 120 g / L or more and 140 g / L or less, more preferably 125 g. / L to 135 g / L (for example, 130 g / L).
  • the coating amount of the upstream catalyst layer 20 per liter of the substrate is Xg / L and the coating amount of the downstream catalyst layer 30 per liter of the substrate is Yg / L, The following formula is satisfied: 60 ⁇ X ⁇ Y ⁇ 140.
  • Example 1 Alumina as a support for forming the upstream catalyst layer was prepared, impregnated with a Rh nitrate solution as a noble metal catalyst solution, and then evaporated to dryness to prepare an Rh / alumina support powder carrying 0.8% by mass of Rh. .
  • the upstream catalyst layer forming slurry was prepared by mixing 36.9 parts by mass of this Rh / alumina carrier powder, 36.61 parts by mass of ceria-zirconia composite oxide and ion-exchanged water. Next, by using this slurry, the length of the base material from the end on the exhaust gas inflow side of the cordierite base material (wall flow type base material shown in FIGS.
  • a ceria-zirconia composite oxide as a support for forming a downstream catalyst layer was prepared, impregnated with a Pt nitrate solution as a noble metal catalyst solution, and then evaporated to dryness to support 1.91% by mass of Pt.
  • Pt / ceria-zirconia composite oxide support powder was prepared.
  • a slurry for forming a downstream catalyst layer by mixing 62.2 parts by mass of this Pt / ceria-zirconia composite oxide support powder, 36.61 parts by mass of alumina, 18.32 parts by mass of BaSO 4 , and ion-exchanged water. was prepared.
  • the mass of the downstream catalyst layer per liter of the substrate was 52.85 g, and the mass of Pt per liter of the substrate was 0.5251 g.
  • the coating amount of the downstream catalyst layer per 1 L of the volume of the base material was 130 g / L.
  • Example 2 Particulates as in Sample 1, except that the coating amount of the upstream catalyst layer per liter of the substrate was changed to 40 g / L and the coating amount of the downstream catalyst layer per liter of the substrate was changed to 160 g / L. A filter was produced.
  • Example 3 Particulates as in Sample 1, except that the coating amount of the upstream catalyst layer per 1 L of the base material was changed to 60 g / L and the coating amount of the downstream catalyst layer per 1 L of the base material was changed to 140 g / L. A filter was produced.
  • Example 4 Particulates in the same manner as Sample 1 except that the coating amount of the upstream catalyst layer per 1 L of the base material was changed to 80 g / L and the coating amount of the downstream catalyst layer per 1 L of the base material was changed to 120 g / L. A filter was produced.
  • Example 5 Particulates as in Sample 1, except that the coating amount of the upstream catalyst layer per liter of the base material was changed to 99 g / L and the coating amount of the downstream catalyst layer per liter of the base material was changed to 101 g / L. A filter was produced.
  • Example 6 Particulate as in Sample 1 except that the coating amount of the upstream catalyst layer per 1 L of the substrate volume was changed to 120 g / L and the coating amount of the downstream catalyst layer per 1 L of the substrate volume was changed to 80 g / L. A filter was produced.
  • Example 7 A particulate filter containing Pd in the upstream catalyst layer and Rh in the downstream catalyst layer was produced. Specifically, a ceria-zirconia composite oxide as a support for forming the upstream catalyst layer is prepared, impregnated with a Pd nitrate solution as a noble metal catalyst solution, and then evaporated to dryness to give 1.91% by mass of Pd. A supported Pd / ceria-zirconia composite oxide support powder was prepared.
  • a slurry for forming an upstream catalyst layer by mixing 62.2 parts by mass of this Pd / ceria-zirconia composite oxide support powder, 36.61 parts by mass of alumina, 18.32 parts by mass of BaSO 4 , and ion-exchanged water. was prepared.
  • this upstream catalyst layer forming slurry on the upstream portion of the substrate and coating the Rh-containing upstream catalyst layer forming slurry used in Sample 1 on the downstream portion of the substrate, the upstream catalyst layer A particulate filter containing Pd and Rh in the downstream catalyst layer was produced.
  • the coating amount of the upstream catalyst layer per 1 L of the substrate volume was 70 g / L
  • the coating amount of the downstream catalyst layer per 1 L of the substrate volume was 130 g / L.
  • an exhaust gas purification device was produced in which a mixed catalyst layer of Pt and Rh was uniformly formed on the entire substrate.
  • a mixed catalyst layer of Pt and Rh was uniformly formed on the entire substrate.
  • 61 parts by mass, 18.32 parts by mass of BaSO 4 and ion-exchanged water were mixed to prepare a mixed catalyst layer forming slurry.
  • a dip coating was applied to the entire substrate, followed by drying and baking, thereby uniformly forming a mixed catalyst layer inside the partition walls.
  • the mass of Pt and Rh per liter of the substrate volume was the same as that of Sample 1.
  • the purification rate of HC gas at a temperature rise of 100 ° C. to 600 ° C. was continuously measured, and the 50% purification temperature was measured.
  • the 50% purification temperature is the gas temperature at the catalyst inlet when the HC gas purification rate reaches 50%.
  • Table 1 and FIG. FIG. 4 is a graph showing the relationship between the ratio of the upstream catalyst layer to the total coating amount and the 50% purification temperature for Samples 1-7.
  • Sample 8 in which a mixed catalyst layer of Pt and Rh was uniformly formed on the entire base material had a HC 50% purification temperature exceeding 390 ° C.
  • the 50% purification temperature of HC was lower and the catalyst activity was more excellent. From the comparison of Samples 1 to 7 in FIG. 4, an extremely low 50% purification temperature of 330 ° C.
  • the coating amount of the upstream catalyst layer could be 60 g / L or more and less than 100 g / L (Sample 1). 3-5). From the viewpoint of improving the purification performance, it is desirable that the coating amount of the upstream catalyst layer be 60 g / L or more and less than 100 g / L (particularly 60 g / L or more and 80 g / L or less).
  • the pressure loss increase rate fluctuated when the coating amount of the upstream catalyst layer was changed.
  • an extremely low pressure loss increase rate of 12.25% or less could be achieved by setting the coating amount of the upstream catalyst layer to 60 g / L or more and 80 g / L or less (Sample 1). 3, 4).
  • the coating amount of the upstream catalyst layer be 60 g / L or more and 80 g / L or less.
  • ⁇ Test Example 2> Furthermore, in order to confirm the influence of the increase / decrease in the upstream catalyst layer inside the partition wall on the pressure loss, the following test was performed. That is, the particulate filter was produced by changing the ratio of the upstream catalyst layer existing inside the partition walls and the upstream catalyst layer existing outside (surface) of the partition walls. The coating amount of the entire upstream catalyst layer was constant at 70 g / L.
  • the upstream catalyst layer is disposed only inside the partition wall. That is, as shown in Table 2, when the entire coating amount of the upstream catalyst layer is 100%, the coating amount existing inside the partition walls is 100%.
  • the coating amount inside and outside the partition wall is 96%, and the coating amount existing outside the partition wall is 4%. The ratio of the amount was adjusted.
  • the ratio of the coating amount inside and outside the partition wall was adjusted so that the coating amount existing inside the partition wall was 88% and the coating amount existing outside the partition wall was 12%.
  • the cross section of the partition wall of the upstream catalyst layer is observed with an electron microscope (SEM), and the ratio of the coating amount is 0 from the end on the exhaust gas inflow side toward the downstream side. This was ascertained by measuring the coating amount in the range of 1 L.
  • SEM electron microscope
  • FIG. 7 is a cross-sectional SEM image of the partition wall of Sample 12
  • FIG. The arrow in each figure has shown the flow (gas flow) of exhaust gas.
  • the coating amount existing inside the partition walls is preferably 85% or more, more preferably 95% or more, and particularly preferably 100%. It is.
  • Rh is arranged in the upstream catalyst layer 20 and Pt is arranged in the downstream catalyst layer 30
  • Pt may be disposed in the upstream catalyst layer 20 and Rh may be disposed in the downstream catalyst layer 30.
  • Pd may be contained in the catalyst layer together with Pt instead of Pt.
  • each member and part of the exhaust gas purification device 1 may be changed.
  • the catalyst unit is provided on the upstream side of the filter unit, but the catalyst unit 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 purification apparatus 1 according to the present invention is not limited to the use of purifying harmful components in exhaust gas of a gasoline engine, but various types of purifying harmful components in exhaust gas discharged from other engines (for example, diesel engines). It can be used in applications.
  • an exhaust gas purification apparatus capable of improving exhaust gas purification performance while reducing pressure loss.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

　La présente invention concerne un dispositif de purification de gaz d'échappement qui est pourvu de : un matériau de base 10 ayant une structure d'écoulement de paroi, et ayant une cellule côté entrée 12, une cellule côté sortie 14, et une paroi de séparation poreuse 16 ; une couche de catalyseur côté amont 20 disposée à l'intérieur de la paroi de séparateur 16, et agencée dans une section côté amont qui comprend l'extrémité du côté d'entrée de gaz d'échappement du matériau de base 10 ; et une couche de catalyseur côté aval 30 disposée à l'intérieur de la paroi de séparation 16, est agencée dans une section côté aval qui comprend l'extrémité au niveau du côté de sortie de gaz d'échappement du matériau de base 10. La couche de catalyseur côté amont 20 et la couche de catalyseur côté aval 30 contiennent chacune un support, et au moins un métal noble choisi parmi Pt, Pd et Rh, soutenu sur le support. Le métal noble inclus dans la couche de catalyseur côté amont 20 et le métal noble inclus dans la couche de catalyseur côté aval 30 sont différents.
PCT/JP2015/078410 2014-10-09 2015-10-06 Dispositif de purification de gaz d'échappement Ceased WO2016056573A1 (fr)

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US15/515,830 US10357744B2 (en) 2014-10-09 2015-10-06 Exhaust gas purification device
EP15848560.7A EP3205388A4 (fr) 2014-10-09 2015-10-06 Dispositif de purification de gaz d'échappement

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WO2018056246A1 (fr) * 2016-09-26 2018-03-29 株式会社キャタラー Catalyseur de purification de gaz d'échappement
JP2018051442A (ja) * 2016-09-26 2018-04-05 株式会社キャタラー 排ガス浄化用触媒
CN109789388A (zh) * 2016-09-26 2019-05-21 株式会社科特拉 排气净化用催化剂
EP3513873A4 (fr) * 2016-09-26 2019-07-24 Cataler Corporation Catalyseur de purification de gaz d'échappement
AU2017332907B2 (en) * 2016-09-26 2020-07-16 Cataler Corporation Exhaust gas purifying catalyst
US10814311B2 (en) 2016-09-26 2020-10-27 Cataler Corporation Exhaust gas purifying catalyst
CN109789388B (zh) * 2016-09-26 2022-03-25 株式会社科特拉 排气净化用催化剂
CN110475612A (zh) * 2017-03-27 2019-11-19 株式会社科特拉 排气净化用催化剂
CN110475612B (zh) * 2017-03-27 2022-07-12 株式会社科特拉 排气净化用催化剂
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JP7436522B2 (ja) 2020-01-14 2024-02-21 三井金属鉱業株式会社 排ガス浄化システム
JP7284837B2 (ja) 2020-02-04 2023-05-31 日本碍子株式会社 多孔質複合体および多孔質複合体の製造方法
JPWO2021157479A1 (fr) * 2020-02-04 2021-08-12
WO2021157479A1 (fr) * 2020-02-04 2021-08-12 日本碍子株式会社 Composite poreux
US12390793B2 (en) 2020-02-04 2025-08-19 Ngk Insulators, Ltd. Porous composite and method of producing porous composite
CN115434790A (zh) * 2021-06-04 2022-12-06 丰田自动车株式会社 排气净化装置
JP7719188B2 (ja) 2021-08-03 2025-08-05 日本碍子株式会社 多孔質複合体
WO2023013207A1 (fr) * 2021-08-03 2023-02-09 日本碍子株式会社 Composite poreux
JPWO2023013207A1 (fr) * 2021-08-03 2023-02-09
JP2023061613A (ja) * 2021-10-20 2023-05-02 株式会社キャタラー パティキュレートフィルタ
WO2023068269A1 (fr) * 2021-10-20 2023-04-27 株式会社キャタラー Filtre à particules
JP7254143B1 (ja) 2021-10-20 2023-04-07 株式会社キャタラー パティキュレートフィルタ

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