WO2020071389A1 - Dispositif d'épuration des gaz d'échappement - Google Patents

Dispositif d'épuration des gaz d'échappement

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Publication number
WO2020071389A1
WO2020071389A1 PCT/JP2019/038808 JP2019038808W WO2020071389A1 WO 2020071389 A1 WO2020071389 A1 WO 2020071389A1 JP 2019038808 W JP2019038808 W JP 2019038808W WO 2020071389 A1 WO2020071389 A1 WO 2020071389A1
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WO
WIPO (PCT)
Prior art keywords
exhaust gas
inlet
outlet
cell
gas purifying
Prior art date
Application number
PCT/JP2019/038808
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English (en)
Japanese (ja)
Inventor
小川　誠
岩知道　均一
Original Assignee
三菱自動車工業株式会社
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 JP2018188914A external-priority patent/JP2020056381A/ja
Priority claimed from JP2018188915A external-priority patent/JP7167614B2/ja
Application filed by 三菱自動車工業株式会社 filed Critical 三菱自動車工業株式会社
Publication of WO2020071389A1 publication Critical patent/WO2020071389A1/fr

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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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • 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

Definitions

  • the present invention relates to an exhaust gas purifying apparatus that collects and burns particulate matter (PM) contained in exhaust gas of an internal combustion engine.
  • PM particulate matter
  • an exhaust gas purifying apparatus for purifying exhaust gas (exhaust gas) of an internal combustion engine an apparatus for removing harmful components using a carrier carrying a catalyst is known. That is, a catalyst component is fixed inside a carrier having a large number of micropores formed therethrough and exhaust gas is circulated, and carbon monoxide, unburned combustion components, nitrogen oxides, particulate matter contained in the exhaust gas are contained. (PM).
  • Examples of the type of the carrier include a ceramic molded product and a metal product (metal carrier).
  • the type of the catalyst supported on the carrier is variously selected according to the substance to be purified (see Patent Documents 1 to 3).
  • One of the objects of the present invention was created in view of the above-mentioned problems, and it is an object of the present invention to provide an exhaust gas purifying apparatus that efficiently improves exhaust gas purifying performance.
  • the disclosed exhaust gas purification apparatus purifies an exhaust gas in which a noble metal is supported inside a partition of a wall flow type carrier having an inlet cell and an outlet cell, and the particulate matter contained in exhaust gas of an internal combustion engine is collected and burned.
  • the present apparatus is provided with an inlet upstream portion in which a catalyst is supported on an upstream side of the partition wall surface facing the inlet cell.
  • an outlet downstream portion on which a catalyst is supported is provided on a downstream side of the partition wall surface facing the outlet cell.
  • the noble metal supported inside the partition include gold (Au), silver (Ag), platinum group elements [ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium ( Ir), platinum (Pt)]. At least one of these is carried inside the partition.
  • rhodium (Rh) or palladium (Pd) having a higher catalytic performance than platinum (Pt) is supported inside the partition.
  • the inlet upstream portion is provided so as to cover a range from the inlet end face of the carrier to a position shorter than the innermost portion of the inlet cell.
  • a portion on which no catalyst is supported is provided on the downstream side of the partition wall surface facing the inlet cell.
  • the outlet downstream portion is provided so as to cover a range from the outlet end surface of the carrier to a position closer to the front than the innermost portion of the outlet cell.
  • a portion on which no catalyst is supported is provided on the upstream side of the partition wall surface facing the outlet cell.
  • the downstream portion of the outlet contains a noble metal.
  • the noble metal supported on the downstream of the outlet include gold (Au), silver (Ag), platinum group elements [ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium. (Ir), platinum (Pt)] and the like.
  • ruthenium (Ru) rhodium (Rh) or palladium (Pd) having higher catalytic performance than platinum (Pt) is used.
  • the upstream portion of the inlet contains silver (Ag) or cerium oxide (CeO 2 ).
  • both silver (Ag) and cerium oxide (CeO 2 ) are included in the inlet upstream.
  • the upstream portion of the inlet contains a rare earth element.
  • the rare earth element here include scandium (Sc), yttrium (Y), lanthanoid [lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium ( Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), Lutetium (Lu)] Can be It is preferable that at least one of these is carried in the inlet upstream part.
  • the inlet upstream portion contains silver or cerium oxide and a rare earth element
  • the inside of the partition contains barium (Ba) or potassium (K) for trapping nitrogen oxides. Barium (Ba) and potassium (K) act as NOx trap catalysts for temporarily adsorbing nitrogen oxides (NOx).
  • the inlet upstream portion and the outlet downstream portion are arranged so as to overlap in the vertical direction in a side view.
  • the length L 1 of the inlet upstream portion to 60% to the total length L UP of the inlet cells in a side view also the length L 2 of the outlet downstream portion with respect to the total length L DOWN of the outlet cells 60%.
  • the preferred length range L 1 of the inlet upstream portion is, for example, 0.5L UP ⁇ L 1 ⁇ 0.75L UP
  • preferred length range of L 2 of the outlet downstream portion for example 0.5 L DOWN ⁇ L 2 ⁇ 0.75 L DOWN .
  • the disclosed exhaust gas purifying apparatus is an exhaust gas purifying apparatus in which a noble metal is carried inside a partition of a carrier, and the particulate matter contained in exhaust gas of an internal combustion engine is collected and burned.
  • a combustion promoting catalyst for promoting the combustion of the particulate matter is supported at a higher density on the upstream side than on the downstream side.
  • Specific examples of the combustion promoting catalyst include silver (Ag), cerium oxide (CeO 2 ), silver ceria (Ag / CeO 2 ), tin ceria (Sn / CeO 2 ), and ceria zirconia (CeO 2 / ZrO 2 ). Is mentioned.
  • the noble metal supported inside the partition include gold (Au), silver (Ag), platinum group elements [ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium ( Ir), platinum (Pt)]. At least one of these is carried inside the partition.
  • rhodium (Rh) or palladium (Pd) having a higher catalytic performance than platinum (Pt) is supported inside the partition.
  • the combustion promoting catalyst is carried inside the partition. That is, it is preferable that the combustion promoting catalyst is supported at a high density on the upstream side inside the partition wall.
  • the support is a wall flow type support having an inlet cell and an outlet cell, and the combustion promoting catalyst is supported within a range in which a distance to the inlet cell is equal to or less than a predetermined value. For example, when the inside of the partition is partitioned at the center in the thickness direction, it is conceivable to carry the combustion promoting catalyst on the side near the inlet cell.
  • inlet upstream portion provided on the upstream side of the partition wall surface of the carrier facing the inlet cell and supporting the combustion promoting catalyst.
  • outlet downstream portion provided on the side facing the outlet cell and on the downstream side of the partition wall surface of the carrier and supporting a noble metal.
  • inlet upstream portion and the outlet downstream portion are arranged so as to overlap vertically in a side view.
  • a nitrogen oxide trap catalyst for trapping nitrogen oxides is included in the partition.
  • the nitrogen oxide trap catalyst include alkali metals and alkaline earth metals.
  • the nitrogen oxide trap catalyst is supported at a higher density on the downstream side than on the upstream side.
  • the nitrogen oxide trap catalyst contains barium and potassium, and the content ratio of potassium relative to the entire nitrogen oxide trap catalyst is set higher on the downstream side than on the upstream side.
  • the exhaust gas purification performance can be improved efficiently.
  • (A) to (C) are graphs for explaining changes in pressure loss, purification performance, and PM collection efficiency when the catalyst coverage on the inlet cell side is changed. It is sectional drawing which expands and shows the internal structure (A part of FIG. 2) of the support
  • 5 is a graph for explaining the distribution of the carrying density of a PM combustion promoting catalyst. 5 is a graph for explaining the distribution of the loading density of the NOx trap catalyst. 4 is a graph for explaining a content ratio of barium and potassium.
  • the exhaust gas purifying apparatus 3 of the present application is applied to a vehicle 10 equipped with an engine 1 (internal combustion engine).
  • the type of the engine 1 may be a diesel engine or a gasoline engine.
  • the exhaust gas purifying apparatus 3 of the present case is suitable for a gasoline engine capable of lean burn operation.
  • the exhaust gas purification device 3 is interposed in the exhaust passage 2 of the engine 1.
  • the exhaust gas purification device 3 is a catalyst device for efficiently purifying various harmful components contained in exhaust gas, and has a function as a three-way catalyst, a function as a NOx storage reduction catalyst, and a function as a PM removal filter. Have both.
  • the disposition position of the exhaust gas purifying device 3 may be set at a position close to the engine 1 (directly downstream of the exhaust manifold or immediately downstream of the supercharger, for example) as shown in FIG. It may be set at a position away from the engine 1. Further, a three-way catalytic converter may be separately provided upstream or downstream of the exhaust gas purifying device 3 to improve the exhaust gas purifying performance.
  • a porous body in which a number of flow paths through which the exhaust gas can pass are formed.
  • the porous body is obtained by supporting the catalyst 9 on a porous carrier 7 and is formed in a cylindrical shape, an elliptic cylindrical shape, or a rectangular parallelepiped shape.
  • the material of the carrier 7 may be a ceramic such as silicon carbide or cordierite (cordierite) or a metal.
  • the porosity of the carrier 7 is preferably as high as possible.
  • the carrier 7 of the present embodiment has a porosity exceeding 50 [%] and a pore volume of pores having a diameter of 1 [ ⁇ m] or more exceeding 0.2 [mL / g].
  • Examples of a base material for supporting the catalyst 9 on the carrier 7 include aluminum oxide (alumina, Al 2 O 3 ), cerium oxide (ceria, CeO 2 ), and zirconium oxide (zirconia, ZrO 2 ).
  • an oxygen storage material that stores oxygen in a reducing environment may be included in the base material.
  • Examples of the oxygen storage material include a ceria-zirconia composite solid solution (CeO 2 -ZrO 2 -based substance) and rare earth oxysulfate (Ln 2 O 2 SO 4 ).
  • the structure of the porous body provided in the exhaust gas purification device 3 is a wall flow type as shown in FIG.
  • the inside of the carrier 7 is divided into a plurality of cells (small chamber-like passages) along the flow direction of the exhaust gas, and each cell is partitioned by a porous partition wall 6 (rib). Further, each cell is closed at one end on the inlet side or the outlet side by a plug 8.
  • the cell whose outlet end is closed is called an inlet cell 4, and the cell whose inlet end is closed is called an outlet cell 5.
  • Each inlet cell 4 is arranged adjacent to at least one or more outlet cells 5, and is preferably arranged adjacent to a number of outlet cells 5.
  • the exhaust gas flowing from the inlet end face 11 of the carrier 7 first enters the inlet cell 4, passes through the partition 6, then enters the outlet cell 5, and flows out of the outlet end face 12 of the carrier 7. I do. That is, all the exhaust gas passes through the inside of the partition 6, and the PM collection efficiency is improved.
  • the catalyst 9 of a type corresponding to the site is supported on the carrier 7.
  • different catalysts 9 are carried between the inside and the surface of the partition 6.
  • different catalysts 9 are carried on the inlet cell 4 side and the outlet cell 5 side.
  • the inside of the partition 6 is referred to as "partition interior 13".
  • a noble metal catalyst is supported in the partition interior 13.
  • the noble metal include platinum group elements [platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), osmium (Os), iridium (Ir)], gold (Au), silver (Ag) ).
  • rhodium or palladium having higher catalytic performance than platinum is used.
  • rhodium and palladium have a higher catalytic activity per supported amount (conversion efficiency with respect to total hydrocarbons) than platinum. Therefore, by using rhodium or palladium, the exhaust gas purification performance can be efficiently increased.
  • its carrying density is about 1.0 [g / L].
  • an inlet upstream portion 14 is provided on the upstream side of the partition wall surface of the carrier 7 facing the inlet cell 4.
  • the inlet upstream portion 14 is provided so as to cover a range from the inlet end face 11 to a position closer to the front than the innermost portion of the inlet cell 4. That is, the catalyst is not carried on the downstream side of the inlet upstream portion 14 in the partition wall surface facing the inlet cell 4.
  • the length L 1 of the inlet upstream portion 14 in side view satisfies the relationship of at least "0 ⁇ L 1 ⁇ L UP" to the total length L UP inlet cells, preferably "0.5 L UP ⁇ L 1 ⁇ 0.75 L UP ”.
  • An outlet downstream portion 15 is provided on the downstream side of the partition wall surface of the carrier 7 facing the outlet cell 5.
  • the outlet downstream part 15 is provided so as to cover a range from the outlet end face 12 to a position closer to the front than the innermost part of the outlet cell 5. That is, the catalyst is not carried on the upstream side of the outlet downstream portion 15 in the partition wall surface facing the outlet cell 5.
  • the length L 2 of the outlet downstream section 15 in side view satisfies the relationship of at least "0 ⁇ L 2 ⁇ L DOWN" to the total length L DOWN outlet cells, preferably "0.5 L DOWN ⁇ L 2 ⁇ 0.75 L DOWN ”.
  • the inlet upstream portion 14 and the outlet downstream portion 15 are arranged so as to overlap in the vertical direction in a side view.
  • the length L 2 of the outlet downstream portion 15 is also set to 60% of the total length L DOWN of the outlet cell 5.
  • the downstream end of the inlet upstream section 14 and the upstream end of the outlet downstream section 15 are vertically overlapped in FIGS. 2 to 4.
  • silver (Ag), cerium oxide (CeO 2 ), or a rare earth element (Rare-Earth Elements, REE) is supported on the inlet upstream portion 14.
  • Silver or cerium oxide functions as a PM promoter, and can burn PM at a lower temperature than the noble metal supported in the partition interior 13.
  • rare earth elements function as P / Zn traps (phosphorus and zinc traps) and suppress poisoning by phosphorus and zinc contained in exhaust gas.
  • its carrying density is about 2.0 [g / L].
  • both the former (silver and cerium oxide) and the latter (rare earth) are supported on the inlet upstream portion 14, it is preferable to expose the portion containing silver and cerium oxide to the inlet cell 4 side.
  • a portion containing a rare earth element be the base layer 16 and a portion containing silver and cerium oxide be the surface layer 17.
  • the surface layer 17 containing silver and cerium oxide may be formed again by the wash coat method.
  • rare earth element here include scandium (Sc), yttrium (Y), lanthanoid [lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium ( Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu)] Can be By supporting at least one of these at the inlet upstream portion 14, the P / Zn trap performance is improved.
  • a noble metal is carried in the outlet downstream portion 15.
  • the noble metal supported on the outlet downstream portion 15 include platinum group elements [platinum, palladium, ruthenium, rhodium, osmium, iridium], gold, silver and the like.
  • the type of the noble metal carried here may be the same as or different from that carried on the inside 13 of the partition wall.
  • rhodium or palladium is used. When rhodium is used, its loading density is about 0.4 [g / L].
  • the partition interior 13 may contain not only a noble metal but also barium (Ba) or potassium (K). Barium and potassium act as a NOx trap that temporarily adsorbs NOx. As shown in FIG. 6, potassium is suitable for NOx purification at a higher temperature than barium, and is suitable for exhaust gas purification in a gasoline engine having a high combustion temperature. Further, potassium has higher NO 2 trapping performance and higher NOx purification efficiency than barium. On the other hand, potassium is thermally unstable and may fall or scatter from the loading position. In this case, the scattered potassium may hinder the catalytic action (ternary activity, especially THC purification performance) of another catalyst or a noble metal. Therefore, it is preferable to use not only potassium but also barium.
  • a blank column in the table may be a non-supported catalyst or a certain catalyst (eg, platinum, transition metal sulfate, alkali metal sulfate, etc.). It is assumed that at least the inlet upstream portions 14 of No. 1, No. 6, No. 11, and No. 16 carry some catalyst. Similarly, it is also assumed that some catalyst is carried in the outlet downstream portions 15 of No. 1 to No. 10. If the inlet upstream portion 14 does not contain both silver and cerium oxide and a rare earth element, it is not necessary to form a two-layer structure (forming the base layer 16 and the surface layer 17).
  • a certain catalyst eg, platinum, transition metal sulfate, alkali metal sulfate, etc.
  • the pressure loss of the exhaust passage can be reduced by providing the inlet upstream portion on the upstream side on the inlet cell side and providing the outlet downstream portion on the downstream side on the outlet cell side. Further, the pressure loss can be reduced while improving the PM collection efficiency, and the exhaust gas purification performance can be efficiently increased. More specifically, the exhaust gas purifying apparatus described above has various functions and effects as described below.
  • FIGS. 7A to 7C show that the length L 1 of the inlet upstream portion 14 is fixed to half (50%) of the total length L UP of the inlet cell 4 and the length L 2 of the outlet downstream portion 15 is reduced from zero.
  • 10 is a graph showing how the pressure loss, the exhaust gas purification performance, and the PM collection efficiency change when the total length L DOWN of the outlet cell 5 is changed (from 0% to 100%).
  • the pressure loss can be suppressed to a small value by the length L 2 of the outlet downstream section 15 below 7-8% of the total length L DOWN. Furthermore, purification performance and PM trapping efficiency is drastically increased by the length L 2 of the outlet downstream section 15 in more than half of the total length L DOWN. Thus, the preferred length range L 2 of the outlet downstream section 15 is considered to 0.5L DOWN ⁇ L 2 ⁇ 0.75L DOWN .
  • the broken lines in FIGS. 7A to 7C show the pressure loss, the exhaust gas purification performance, and the PM collection efficiency when the amount of the noble metal supported on the inside 13 of the partition wall is increased. As described above, even when the outlet downstream portion 15 is not formed in a wide range over the entire length L DOWN of the outlet cell 5, good exhaust gas purification performance can be maintained by adjusting the amount of noble metal carried in the partition interior 13.
  • FIGS. 8A to 8C show that the length L 2 of the outlet downstream portion 15 is fixed to half (50%) of the total length L DOWN of the outlet cell 5 and the length L 1 of the inlet upstream portion 14 is changed from zero.
  • 6 is a graph showing how the pressure loss, the exhaust gas purification performance, and the PM collection efficiency change when the total length L UP of the inlet cell 4 is changed (from 0% to 100%). It is possible to suppress the pressure loss by the length L 1 of the inlet upstream section 14 below 7-8% of the total length L DOWN. Furthermore, purification performance and PM trapping efficiency is rapidly increased by the length L 1 of the inlet upstream section 14 to more than half of the total length L UP. Thus, the preferred length range L 1 of the inlet upstream section 14 is considered to 0.5L UP ⁇ L 1 ⁇ 0.75L UP .
  • the pressure loss of the exhaust passage 2 is reduced by providing the inlet upstream section 14 on the upstream side of the inlet cell 4 side of the surface of the partition wall 6 and providing the outlet downstream section 15 on the downstream side of the outlet cell 5 side. be able to. Further, the pressure loss can be reduced while improving the PM collection efficiency, and the exhaust gas purification performance can be efficiently increased. Note that, on the partition wall surface facing the inlet cell 4, no catalyst is supported downstream of the inlet upstream portion 14. Similarly, the catalyst is not carried on the upstream side of the outlet downstream portion 15 in the partition wall surface facing the outlet cell 5. These “catalyst non-supporting portions” function as flow paths having a small exhaust gas flow resistance and a small pressure loss. Therefore, pressure loss can be reduced with a simple configuration.
  • the NOx reduction efficiency at the outlet cell 5 side can be increased by including the noble metal catalyst in the outlet downstream portion 15.
  • the amount of slip of NOx from the exhaust gas purification device 3 can be reduced, and the exhaust gas purification performance can be efficiently increased.
  • silver or cerium oxide is contained in the inlet upstream section 14. By doing so, the combustion of PM can be promoted, and the PM can be burned at a lower temperature than the inside 13 of the partition wall. This makes it possible to regenerate the carrier 7 more quickly and in a shorter time than before, and it is possible to efficiently improve exhaust gas purification performance. In addition, an increase in pressure loss due to deposition of PM can be prevented.
  • the PM upstream efficiency and the exhaust gas purification efficiency can be increased by vertically overlapping the inlet upstream section 14 and the outlet downstream section 15 in a side view.
  • the length L 1 of the inlet upstream section 14 and sets in the range of 0.5L UP ⁇ L 1 ⁇ 0.75L UP
  • the length L 2 of the outlet downstream section 15 0.5L DOWN ⁇ L 2 ⁇ 0.75L DOWN 7 and 8
  • the purification performance and the PM collection efficiency can be maintained at high levels without excessively increasing the pressure loss.
  • the exhaust gas purifying device described above can achieve the object of reducing pressure loss while improving PM collection efficiency. It is to be noted that the above-described exhaust gas purifying apparatus is not limited to this object, and has the function and effect derived from each configuration shown in the “Embodiment for Carrying Out the Invention”. Can be positioned as other purposes.
  • FIG. 9 illustrates a structure of the exhaust gas purifying apparatus 3 of the present embodiment.
  • the partition interior 13 is classified into two regions, a side near the entrance cell 4 and a side near the exit cell 5.
  • the former is a portion where the distance to the partition wall surface (or the inlet cell 4) on the entrance cell 4 side is equal to or less than a predetermined value T, and the latter is a portion where the distance to the entrance cell 4 exceeds the predetermined value T.
  • the value of the predetermined value T is arbitrary, and is set, for example, so as to satisfy the relationship of “T ⁇ 0.5 T WALL ”, where the thickness of the partition wall 6 is T WALL .
  • the side of the partition interior 13 that is closer to the inlet cell 4 is referred to as “inner inlet side 18”, and the side closer to the outlet cell 5 is referred to as “inner outlet side 19”.
  • Different catalyst layers are formed on the surface of the partition 6 on the inlet cell 4 side and the outlet cell 5 side.
  • an inlet upstream portion 14 is provided on the upstream side of the partition wall surface of the carrier 7 facing the inlet cell 4.
  • the inlet upstream portion 14 is provided so as to cover a range from the inlet end face 11 to a position closer to the front than the innermost portion of the inlet cell 4. That is, the catalyst 9 is not carried on the outlet end face 12 side of the inlet upstream portion 14 in the partition wall surface facing the inlet cell 4.
  • the length L 1 of the inlet upstream portion 14 in side view satisfies the relationship of at least "0 ⁇ L 1 ⁇ L UP" to the total length L UP inlet cells, preferably "0.5 L UP ⁇ L 1 ⁇ 0.75 L UP ”.
  • the inlet upstream section 14 may have a multilayer structure including the base layer 16 and the surface layer 17.
  • the surface layer 17 is the surface of the inlet upstream portion 14 in contact with the inlet cell 4 or a portion close to the surface (a portion where the distance to the surface is equal to or less than a second predetermined value).
  • the base layer 16 is a portion located closer to the carrier 7 than the surface layer 17, and is preferably provided so as to be in contact with the carrier 7.
  • a portion other than the surface layer 17 is the base layer 16. In such a multilayer structure, it is preferable to support different catalysts 9 on the base layer 16 and the surface layer 17.
  • An outlet downstream portion 15 is provided on the downstream side of the partition wall surface of the carrier 7 facing the outlet cell 5.
  • the outlet downstream part 15 is provided so as to cover a range from the outlet end face 12 to a position closer to the front than the innermost part of the outlet cell 5. That is, the catalyst 9 is not carried on the inlet end face 11 side of the outlet downstream portion 15 in the partition wall surface facing the outlet cell 5.
  • the length L 2 of the outlet downstream section 15 in side view satisfies the relationship of at least "0 ⁇ L 2 ⁇ L DOWN" to the total length L DOWN outlet cells, preferably "0.5 L DOWN ⁇ L 2 ⁇ 0.75 L DOWN ”.
  • the inlet upstream portion 14 and the outlet downstream portion 15 are arranged so as to overlap in the vertical direction in a side view.
  • the length L 2 of the outlet downstream portion 15 is also set to 60% of the total length L DOWN of the outlet cell 5.
  • the downstream end portion of the inlet upstream portion 14 and the upstream end portion of the outlet downstream portion 15 overlap each other in the vertical direction in FIGS.
  • a noble metal catalyst is supported in the partition interior 13.
  • the noble metal include platinum group elements [platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), osmium (Os), iridium (Ir)], gold (Au), and silver (Ag). ).
  • platinum group elements platinum group elements [platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), osmium (Os), iridium (Ir)], gold (Au), and silver (Ag).
  • rhodium or palladium having higher catalytic performance than platinum is used.
  • rhodium and palladium have a higher catalytic activity per supported amount (conversion efficiency with respect to total hydrocarbons) than platinum. Therefore, by using rhodium or palladium, the exhaust gas purification performance can be efficiently increased.
  • its carrying density is about 1.0 [g / L].
  • silver and cerium oxide function as a PM combustion promoting material (combustion promoting catalyst), and can burn PM at a lower temperature than the noble metal supported in the partition wall interior 13.
  • combustion promoting materials include tin ceria (Sn / CeO 2 ) and ceria zirconia (CeO 2 / ZrO 2 ).
  • rare earth elements function as P / Zn traps (phosphorus and zinc traps) and suppress poisoning by phosphorus and zinc contained in exhaust gas.
  • its carrying density is about 2.0 [g / L].
  • both the former (silver, cerium oxide, silver ceria) and the latter (rare earth) are supported on the inlet upstream section 14, it is preferable to expose the part containing the former to the inlet cell 4 side.
  • a portion containing a rare earth element be the base layer 16 and a portion containing silver, cerium oxide, and silver ceria be the surface layer 17.
  • the surface layer 17 containing silver, cerium oxide and silver ceria may be formed again by the wash coat method.
  • the inlet upstream portion 14 may have a single-layer structure instead of a multilayer structure. Good.
  • rare earth element here include scandium (Sc), yttrium (Y), lanthanoid [lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium ( Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu)] Can be By supporting at least one of these at the inlet upstream portion 14, the P / Zn trap performance is improved.
  • a noble metal is carried in the outlet downstream portion 15.
  • the noble metal supported on the outlet downstream portion 15 include platinum group elements [platinum, palladium, ruthenium, rhodium, osmium, iridium], gold, silver and the like.
  • the type of the noble metal carried here may be the same as or different from that carried on the inside 13 of the partition wall.
  • rhodium or palladium is used. When rhodium is used, its loading density is about 0.4 [g / L].
  • the NOx trap catalyst (nitrogen oxide trap catalyst) that temporarily stores and adsorbs NOx may be included in the partition interior 13.
  • Specific examples of the NOx trap catalyst include an alkali metal and an alkaline earth metal.
  • barium (Ba), potassium (K), rubidium (Rb), strontium (Sr), cesium (Cs), francium (Fr), radium (Ra) and the like are preferable, and barium and potassium are preferably used in combination.
  • potassium is suitable for NOx purification at a higher temperature than barium, and is suitable for exhaust gas purification in a gasoline engine having a high combustion temperature. Further, potassium has higher NO 2 trapping performance and higher NOx purification efficiency than barium. On the other hand, potassium is thermally unstable and may fall or scatter from the loading position. In this case, the scattered potassium may hinder the catalytic action (ternary activity, particularly THC purification performance) of another catalyst or a noble metal. Therefore, it is preferable to use barium and potassium together.
  • Tables 3 to 10 below show combinations of the type of the catalyst 9 and the supporting position.
  • 64 types of embodiments No. 21 to No. 84
  • “Pd / Rh” in the table means that palladium and rhodium are included.
  • the noble metal is contained in the partition interior 13.
  • “Ag / CeO 2 ” in the table means that it contains silver ceria which is a PM combustion promotion catalyst. The silver ceria is carried on the inside of the partition wall 13 and on the inlet upstream portion 14 (Nos. 22 to 36, 38 to 52, 54 to 68, 70 to 84).
  • ⁇ " Ba / K in the table means that it contains barium and potassium. Barium and potassium are supported in the partition interior 13, preferably at least on the internal outlet side 19 (Nos. 53 to 84). “REE” in the table means that rare earth elements are included. The rare earth element is carried in the inlet upstream portion 14 (Nos. 23 to 24, 27 to 28, 31 to 32, 35 to 36, 39 to 40, 42 to 44, 47 to 48, 51 to 52, 55 to 56). , 59-60, 63-64, 67-68, 71-72, 75-76, 79-80, 83-84). If the entrance upstream portion 14 does not contain both silver ceria and a rare earth element, it is not necessary to form a two-layer structure (forming the base layer 16 and the surface layer 17).
  • a catalyst may not be supported, or some catalyst (for example, platinum, transition metal sulfate, alkali metal sulfate, etc.) may be supported.
  • some catalyst for example, platinum, transition metal sulfate, alkali metal sulfate, etc.
  • some PM combustion promoting catalyst for example, silver (Ag), cerium oxide (CeO 2 ), tin ceria (Sn / CeO 2 ) and ceria zirconia (CeO 2 / ZrO 2 ). Therefore, all embodiments include some PM combustion promoting catalyst on the support 7.
  • Examples that do not include barium and potassium are described in Tables 3-6, and examples that include barium and potassium are described in Tables 7-10.
  • Examples in which the outlet downstream portion 15 does not include a noble metal are described in Tables 3 and 4, and examples in which the outlet downstream portion 15 includes a noble metal are described in Tables 5 to 10.
  • Examples in which silver ceria is not included in the internal outlet side 19 are described in Tables 3, 5, 7, and 9; examples in which silver ceria is included in the internal outlet side 19 are shown in Tables 4, 6, and 6. It is described in Tables 8 and 10.
  • the PM combustion promoting catalyst is supported at a higher density on the upstream side than on the downstream side.
  • the upstream side and the downstream side are an upstream (distribution source) and a downstream (distribution destination) based on the flow direction of the exhaust gas.
  • the following (A) to (G) can be considered.
  • the carrier In the inlet upstream portion 14, the carrier is supported at a higher density on the surface layer 17 (upstream side) than on the base layer 16 (downstream side).
  • the carrier In the partition interior 13, the carrier is carried at a higher density on the inner inlet side 18 (upstream side) than on the inner outlet side 19 (downstream side).
  • the support In the upstream part 14 of the inlet and the inside 13 of the partition wall, the support is carried out such that the carrying density becomes lower in the order of the surface layer 17, the base layer 16, the inner inlet side 18, and the inner outlet side 19.
  • FIG. 10 is a graph showing a setting example of the carrying density of the PM combustion promoting catalyst.
  • the broken lines in FIG. 10 correspond to the settings according to the above (A) and (D).
  • the dashed line in FIG. 10 corresponds to the setting according to the above (B) and (F), and the thick solid line corresponds to the setting according to the above (C) to (G).
  • the PM combustion promoting catalyst carried on the upstream side where the PM tends to accumulate higher than on the downstream side, the PM is uniformly burned on the upstream side and the downstream side of the carrier 7. It will be easier. This makes it easier for the PM accumulated at various places of the carrier 7 to be incinerated in the same incineration time, thereby preventing local excessive temperature rise.
  • the NOx trap catalyst may be supported at a higher density on the downstream side than on the upstream side.
  • Specific methods for setting the loading density of the NOx trap catalyst include, for example, the following (H) to (J).
  • the carrier In the partition interior 13, the carrier is carried at a higher density on the internal outlet side 19 (downstream side) than on the internal inlet side 18 (upstream side).
  • the carrier On the inner outlet side 19, the carrier is carried at a higher density in a portion (downstream side) closer to the outlet cell 5 than in a portion (upstream side) farther from the outlet cell 5.
  • a higher density On the inner inlet side 18, a higher density is carried at a portion (downstream side) farther from the inlet cell 4 than at a portion (upstream side) closer to the inlet cell 4.
  • FIG. 11 is a graph showing a setting example of the carrying density of the NOx trap catalyst.
  • the dashed line in FIG. 11 corresponds to the setting according to the above (H)
  • the dashed line corresponds to the setting according to the above (H) to (I)
  • the solid line is the above (H) to (J).
  • the content ratio of barium and potassium may be different for each part of the carrier 7 as shown in FIG. That is, the barium content may be set high on the upstream side and low on the downstream side. In other words, the potassium content may be set low on the upstream side and high on the downstream side. Such a setting suppresses a decrease in other catalytic action due to the scattering of potassium.
  • the distribution of PM collected on the carrier is not necessarily uniform, and a deviation occurs depending on the shape of the carrier, the flow of exhaust gas, and the like.
  • PM easily accumulates on the surface of the carrier facing the inlet cell or near the inlet of the exhaust gas flow path inside the carrier. Therefore, there is a problem that it is difficult to burn PM uniformly on the upstream side and the downstream side of the carrier. It should be noted that the incineration time is prolonged more easily on the upstream side where the deposition amount of PM tends to increase, and there is a risk of performance degradation due to excessive heating.
  • the PM (particulate matter) can be efficiently burned by supporting the combustion promoting catalyst at a high density on the upstream side, and the purification efficiency of PM and the purification efficiency of exhaust gas can be improved efficiently. Can be enhanced. More specifically, the exhaust gas purifying apparatus described above has various functions and effects as described below.
  • FIG. 7 (A) ⁇ (C) observed the relationship shown in FIG. 8 (A) ⁇ (C) , preferably the length L 2 range of outlet downstream section 15 0.5L It is considered that DOWN ⁇ L 2 ⁇ 0.75L DOWN . Even when the outlet downstream portion 15 is not formed in a wide area over the entire length L DOWN of the outlet cell 5, good exhaust gas purification performance can be maintained by adjusting the amount of noble metal carried in the partition interior 13. Also preferred length range L 1 of the inlet upstream section 14 is considered to be 0.5L UP ⁇ L 1 ⁇ 0.75L UP .
  • the PM combustion promotion catalyst is supported on the inside 13 of the partition wall to deposit it on the inside 13 of the partition wall.
  • the burned PM can be burned at a lower temperature. Therefore, PM combustion efficiency can be improved, and clogging and pressure loss increase due to PM can be prevented.
  • the PM combustion efficiency can be further increased by supporting the PM combustion promoting catalyst on the inner inlet side 18 where PM easily accumulates inside the partition wall 13.
  • the PM combustion promoting catalyst can be carried in the inlet upstream portion 14 having the highest probability of contact with PM in the exhaust gas, so that the PM combustion efficiency can be further improved. Temperature. Further, the PM can be burned before entering the partition interior 13, and the pressure loss in the exhaust passage 2 can be reduced. Therefore, comprehensive exhaust gas purification performance can be improved.
  • the NOx reduction efficiency on the outlet cell 5 side can be increased by including a noble metal catalyst in the outlet downstream portion 15. As a result, the amount of slip of NOx from the exhaust gas purification device 3 can be reduced, and the exhaust gas purification performance can be efficiently increased.
  • the PM upstream efficiency and the exhaust gas purification efficiency can be increased by vertically overlapping the inlet upstream portion 14 and the outlet downstream portion 15 in a side view.
  • the length L 1 of the inlet upstream section 14 and sets in the range of 0.5L UP ⁇ L 1 ⁇ 0.75L UP
  • the length L 2 of the outlet downstream section 15 0.5L DOWN ⁇ L 2 ⁇ 0.75L DOWN 7 and 8
  • the purification performance and the PM collection efficiency can be maintained at high levels without excessively increasing the pressure loss.
  • the above exhaust gas purifying device can achieve the purpose of burning PM uniformly. It is to be noted that the above-described exhaust gas purifying apparatus is not limited to this object, and has the function and effect derived from each configuration shown in the “Embodiment for Carrying Out the Invention”. Can be positioned as other purposes.
  • the vehicle 10 equipped with the engine 1 is illustrated, but the application target of the present invention is not limited to the vehicle 10.
  • the above-mentioned exhaust gas purifying device 3 can be interposed in the exhaust passage 2 of the engine 1 mounted on a ship or an aircraft, for example. Alternatively, it can be used as an exhaust gas purifying device 3 of the engine 1 built in a generator or an industrial machine.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

L'invention concerne un dispositif (3) d'épuration des gaz d'échappement permettant de capter et de brûler des matières particulaires contenues dans des gaz d'échappement en provenance d'un moteur à combustion interne (1). Dans le dispositif, un métal noble est amené à être porté à l'intérieur d'une paroi de séparation d'un support (6) du type à écoulement de paroi, comportant une cellule d'entrée (4) et une cellule de sortie (5). Une section amont d'entrée (14), sur laquelle un catalyseur est pris en charge, est agencée en amont du côté d'une surface de la paroi de séparation, faisant face à la cellule d'entrée (4). Une section aval de sortie (15), sur laquelle un catalyseur est pris en charge, est agencée en aval du côté de la surface de la paroi de séparation, faisant face à la cellule de sortie (5). Par conséquent, le rendement d'épuration des gaz d'échappement est amélioré efficacement.
PCT/JP2019/038808 2018-10-04 2019-10-01 Dispositif d'épuration des gaz d'échappement WO2020071389A1 (fr)

Applications Claiming Priority (4)

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JP2018-188915 2018-10-04
JP2018-188914 2018-10-04
JP2018188914A JP2020056381A (ja) 2018-10-04 2018-10-04 排ガス浄化装置
JP2018188915A JP7167614B2 (ja) 2018-10-04 2018-10-04 排ガス浄化装置

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015064A1 (fr) * 2020-12-15 2022-06-22 UMICORE AG & Co. KG Filtre à particules catalytiquement actif à efficacité de filtration élevée

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012055842A (ja) * 2010-09-09 2012-03-22 Toyota Motor Corp 排ガス浄化用触媒
WO2016133086A1 (fr) * 2015-02-17 2016-08-25 株式会社キャタラー Catalyseur pour purification de gaz d'échappement
JP2017185467A (ja) * 2016-04-08 2017-10-12 株式会社豊田中央研究所 排ガス浄化用触媒
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012055842A (ja) * 2010-09-09 2012-03-22 Toyota Motor Corp 排ガス浄化用触媒
WO2016133086A1 (fr) * 2015-02-17 2016-08-25 株式会社キャタラー Catalyseur pour purification de gaz d'échappement
JP2017185467A (ja) * 2016-04-08 2017-10-12 株式会社豊田中央研究所 排ガス浄化用触媒
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015064A1 (fr) * 2020-12-15 2022-06-22 UMICORE AG & Co. KG Filtre à particules catalytiquement actif à efficacité de filtration élevée
WO2022129010A1 (fr) * 2020-12-15 2022-06-23 Umicore Ag & Co. Kg Filtre à particules catalytiquement actif à haut degré d'efficacité de filtration

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