WO2007055033A1 - Filtre, materiau de purification de gaz d’echappement pour moteur a combustion interne et procede de purification de gaz d’echappement - Google Patents

Filtre, materiau de purification de gaz d’echappement pour moteur a combustion interne et procede de purification de gaz d’echappement Download PDF

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Publication number
WO2007055033A1
WO2007055033A1 PCT/JP2005/021189 JP2005021189W WO2007055033A1 WO 2007055033 A1 WO2007055033 A1 WO 2007055033A1 JP 2005021189 W JP2005021189 W JP 2005021189W WO 2007055033 A1 WO2007055033 A1 WO 2007055033A1
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WO
WIPO (PCT)
Prior art keywords
filter
exhaust gas
honeycomb structure
ash
internal combustion
Prior art date
Application number
PCT/JP2005/021189
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English (en)
Japanese (ja)
Inventor
Atsushi Kudo
Yukio Oshimi
Original Assignee
Ibiden Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ibiden Co., Ltd. filed Critical Ibiden Co., Ltd.
Priority to PCT/JP2005/021189 priority Critical patent/WO2007055033A1/fr
Publication of WO2007055033A1 publication Critical patent/WO2007055033A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/66—Regeneration of the filtering material or filter elements inside the filter
    • B01D46/80—Chemical processes for the removal of the retained particles, e.g. by burning
    • B01D46/84—Chemical processes for the removal of the retained particles, e.g. by burning by heating only
    • 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
    • F01N3/0215—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 the filtering elements having the form of disks or plates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/0232—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles removing incombustible material from a particle filter, e.g. ash
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2279/00—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses
    • B01D2279/30—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses for treatment of exhaust gases from IC Engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction

Definitions

  • the present invention relates to a filter, an exhaust gas purification device for an internal combustion engine, and an exhaust gas purification method.
  • the present invention relates to a filter for removing particulate matter in exhaust gas discharged from an internal combustion engine such as a diesel engine, an exhaust gas purification device using the filter, and an exhaust gas purification method performed using the device.
  • the present invention proposes a technique characterized by a filter that can effectively remove the ash contained in the particulate matter at a specific location in the filter without causing a pressure loss.
  • a particulate filter for collecting particulate matter contained in the exhaust gas is provided in the exhaust passage.
  • the filter raises the temperature of the filter by increasing the exhaust temperature of the engine or heating it using a beater, and the collected particulate matter is collected. It is intended to burn and remove.
  • ash refers to various additives and impurity components contained in the fuel and lubricating oil of an internal combustion engine that combine in the combustion chamber of the internal combustion engine or the filter to form various compounds, These compounds are produced by agglomeration of these compounds in the filter.
  • fuels and lubricating oils for internal combustion engines contain components such as sulfur, phosphorus, calcium, and magnesium, and the components contained in the lubricating oil and the components contained in the mixture are combined in the combustion chamber.
  • the screened-off ash is accumulated in the longitudinal direction of the through-holes from the vicinity of the sealing portion of the honeycomb structure, so that the filtration area decreases as it is used. As a result, there is a problem that the life of the filter is shortened.
  • a metal having a negative electronegativity equal to or lower than that of a predetermined component contained in the lubricating oil is preferably used as the trapping material, preferably a metal having a lower electronegativity than the predetermined component and a high ionization tendency. Since it is supported, it is used that the component to be bonded is not the predetermined component but is bonded to the metal having a low electronegativity.
  • potassium sulfate is more expensive than calcium sulfate.
  • the degree of aggregation is low, it can be easily decomposed and removed by using a high-temperature treatment or reducing atmosphere.
  • an object of the present invention is to reduce the filter volume resulting from the accumulation of ash produced by the combustion of particulate matter in the exhaust gas in the filter, or the exhaust gas flow path (cell).
  • the purpose is to propose a filter that does not cause clogging and does not cause the accompanying increase in pressure loss.
  • Another object of the present invention is not only the need for maintenance after replacement for a new product after a certain period of use, and removal for removal of an ash, but also a longer service life with a simple configuration. It is to propose a filter.
  • Still another object of the present invention is to propose an exhaust gas purification device and an exhaust gas purification method using the filter. Disclosure of the invention
  • Ash is Obtaining the knowledge that the ruta is deposited sequentially from the rear (discharge side) of the cell, the removal of the ash accompanied by such a deposition phenomenon is not a method of physically peeling and removing as in the prior art.
  • the present invention based on the knowledge that it is effective to remove ash in a compact location in a filter while suppressing filter volume reduction and exhaust flow blockage. did.
  • a filter for purifying exhaust gas discharged from an internal combustion engine wherein an ash trap layer is provided in an exhaust gas inflow side cell of the filter,
  • an exhaust gas purification apparatus for an internal combustion engine in which an exhaust gas flow path of the internal combustion engine is provided with a filter that collects particulate matter contained in the exhaust gas, an exhaust gas inflow side cell of the filter
  • An exhaust gas purifying device for an internal combustion engine characterized in that an ash trap layer is provided therein.
  • the ash trap layer is preferably made of a glassy material, and is made of a low melting point glass, and the ash trap layer can be made of a low melting point inorganic compound flux material. .
  • the ash trap layer is preferably provided in the vicinity of the in-cell sealing portion of the integral-type, aggregate-type honeycomb structure, or laminated honeycomb structure.
  • the filter has an ash trap layer formed of the honeycomb structure. It is preferable to be provided on the partition wall surface.
  • an ash trap layer is provided at a specific location in the filter, that is, in each cell on the exhaust gas inflow side, particularly in the vicinity of the sealing portion of the cell end (downstream end portion).
  • the particulate matter in the exhaust gas is burned and removed (for example, about 550 ° C), softened or further melted to produce ash, that is, the particulate matter burns to become unburned.
  • the ash generated in this way is adsorbed sequentially in this ash trap layer, and is accumulated so as to be confined there and accumulated and solidified at a high density, thereby reducing the filter volume (filtering area) or blocking the exhaust passage. It can be used for a long time with no pressure loss in the exhaust system, and the filter life can be extended.
  • exhaust gas can be highly purified through complete removal of ash.
  • FIG. 1 is a perspective view schematically showing an example of a honeycomb filter according to the present invention.
  • FIG. 2 (a) is a perspective view schematically showing an example of the porous ceramic member constituting the honeycomb filter shown in Fig. 1, and Fig. 2 (b) is shown in Fig. 2 (a).
  • FIG. 3 is a cross-sectional view taken along line AA of the porous ceramic member.
  • FIG. 3 (a) is a perspective view schematically showing another example of the honeycomb filter according to the present invention, and Fig. 3 (b) shows the honeycomb shown in Fig. 3 (a).
  • FIG. 6 is a cross-sectional view of the mu filter taken along line B-B.
  • Fig. 4 (a) is a perspective view schematically showing still another example of the honeycomb filter according to the present invention
  • Fig. 4 (b) is a diagram of C and C of the honeycomb filter shown in Fig. 4 (a).
  • FIG. 5 is a diagram for explaining a part of the manufacturing process of the honeycomb filter shown in FIG.
  • FIG. 5 (a) is a schematic view showing the paper sheets to be laminated
  • FIG. 5 (b) is a schematic perspective view of the honeycomb filter formed by stacking the paper sheets.
  • FIG. 6 is a cross-sectional view schematically showing an example of an exhaust gas purification device using the honeycomb filter according to the present invention.
  • the present invention relates to a filter that collects particulate matter contained in exhaust gas exhausted from an internal combustion engine and an exhaust gas purification device for an internal combustion engine equipped with the filter.
  • the generated ash is captured, and the ash is captured (captured) at a specific position in the filter, that is, in the vicinity of the sealing portion provided in the cell end portion of each cell on the exhaust gas inflow side.
  • An ash trap layer is provided.
  • the above ash trap layer means that at least a part of the liquid phase at the filter regeneration temperature (2500 ° C to 800 ° C) at which the ash described above is removed (regenerated) by burning the particulates. It is preferably made of a material that generates or softens.
  • such a trap layer constituent material is a vitreous material that changes from a solid phase to a liquid phase at the regeneration temperature of the filter or softens at least, preferably a phosphate glass or a calcium sulfate glass. Low melting point glass, etc. Alternatively, it is preferable to use a low melting point inorganic compound flux material.
  • the phosphoric acid glasses include P 2 0 3 — BaO (glass transition temperature: 3 7 7), ⁇ 2 0 3 - ⁇ 0 (glass transition temperature: 3 6 6 ° C), P 2 0 3 — BaO—BaF 2 (glass transition temperature: 3 66 ° C.) or the like can be used.
  • CaS0 4 -NaC I lowest liquid phase temperature: 7 2 6 ° C
  • CaS0 4 - KCI minimum liquidus temperature: 6 8 7 ° C
  • CaS0 4 - NaC ⁇ KC I minimum liquidus temperature: 60 5 ° C
  • chloride-containing flux a sulfate-based flux-reactive chloride-containing sulfate-based flux (hereinafter referred to as “chloride-containing flux”).
  • the sulfate fluxes include Li 2 S0 4 -0.5Na 2 S0 4 + 0.5K 2 S0 4 (minimum melting temperature: 5 2 1 ° C), Na 2 S0 4 -ZnS0 4 (minimum melting temperature: 4 5 6 ° C) can be used.
  • Li 2 S0 4 -K 2 S0 4 -NaCI minimum melting temperature: 4 3 2 ° C
  • i 2 S0 4 -NaCI minimum melting temperature: 4 9 9 ° C
  • Li 2 S0 4 -NaC ⁇ KCI minimum melting temperature: 4 26 ° C
  • a filter according to the present invention and an exhaust gas purification apparatus for an internal combustion engine using the filter will be specifically described with reference to the drawings.
  • the filter according to the present invention is a honeycomb structure and the exhaust gas purification device according to the present invention is applied to a vehicle diesel engine will be described.
  • the filter according to the present invention uses a honeycomb structure in which a large number of cells (through holes) are arranged in parallel in the longitudinal direction with partition walls (filtration walls) therebetween. With such a structure, the filtration area per volume of the filter can be increased. ⁇ Ticulate can be collected thinly.
  • honeycomb structure In such a honeycomb structure, a large number of cells are separated by partition walls.
  • One made of porous ceramic members hereinafter referred to as “integrated honeycomb structure” and a number of plate-like (sheet-like) porous ceramic members
  • stacked honeycomb structure A columnar honeycomb structure in which the cell holes are arranged in parallel in the longitudinal direction with the partition walls therebetween
  • Fig. 1 is a perspective view schematically showing an example of an aggregate type honeycomb structure which is an example of a honeycomb structure
  • Fig. 2 (a) is a porous diagram of the aggregate type honeycomb structure shown in Fig. 1.
  • 1 is a perspective view of a ceramic member (unit)
  • FIG. 2B is a cross-sectional view taken along line AA of the porous ceramic member shown in FIG.
  • the honeycomb structure 10 shown in FIG. 1 is composed of a prismatic porous ceramic member (unit) 20 shown in FIG. 2 and a cylindrical ceramic block 1 that is bundled together via a sealing material layer 1 4. 5 and a sealing material layer 13 is provided on the outer periphery of the ceramic block 15.
  • the prismatic porous ceramic member 20 is provided with a large number of cells (through holes) 21 along the longitudinal direction thereof.
  • the porous ceramic member 20 is formed of these cells as shown in FIG. 2 (b). Either one of the openings at both ends of 2 1 is sealed with a sealing material (plug) 2 2.
  • the honeycomb structure 1 0 is hand of (exhaust gas inflow side) cells 2 1 of the ceramic block 1 5 its downstream end (Seruen de) is locked Li sealed by the sealing material 2 2, In the other (exhaust gas outflow side) cell 2 1, the upstream end is sealed with the sealing material 2 2.
  • the exhaust gas flowing into the exhaust gas inflow side cell 21a passes through the partition wall 23 that separates the cells 21a, and moves to the cell 21b on the exhaust gas outflow side.
  • the partition wall 2 3 separating these cells 21a and 21b is made to function as a particle collecting filter.
  • the sealing material layer 13 formed around the ceramic block 15 is used to prevent exhaust gas from leaking from the outer periphery of the ceramic block 15 when the honeycomb structure 10 is used as a honeycomb filter. Or, it is formed to adjust the shape.
  • Fig. 3 (a) is a perspective view schematically showing another embodiment of the honeycomb structure, that is, a specific example of the integral honeycomb structure, and Fig. 3 (b) is a view taken along the line B-B. It is sectional drawing.
  • the monolithic honeycomb structure 30 has a single columnar structure in which a large number of cells 31a and 31b are provided along the longitudinal direction with a partition wall 33 therebetween. It is composed of a cylindrical ceramic block 35 made of a porous ceramic sintered body.
  • the ceramic block 35 is composed of cells 31a, as shown in Fig. 3 (b). Either one of the ends of 3 1 b is sealed with sealing material 3 2 on one side.
  • the downstream end of the exhaust gas inflow side cell 3 1 a is sealed by the sealing material 3 2, and the exhaust gas outflow side cell 3 1 b At the end, the upstream end is preferably sealed with the sealing material 32.
  • the exhaust gas flowing into one cell 3 1 a passes through the partition wall 3 3 separating these cells 3 1 a and then flows out from the other cell 3 1 b (so-called wall). Flow type), these cells 3 1 a, 3 1 b
  • the partition wall 3 3 separating the two can function as a particle collecting filter.
  • a sealing material layer may be formed to adjust the shape.
  • the honeycomb structure constituting the filter according to the present invention described above may be used as a ceramic member material, for example, oxide ceramics such as cordierite, alumina, silicon force, mullite, zirconia, and yttria, silicon carbide, Carbide ceramics such as zirconium carbide, titanium carbide, tantalum carbide, tungsten carbide, etc., nitride ceramics such as aluminum nitride, silicon nitride, boron nitride, titanium nitride, etc., aluminum titanate, composite of ceramic and silicon, etc. Can be used.
  • oxide ceramics such as cordierite, alumina, silicon force, mullite, zirconia, and yttria
  • silicon carbide Carbide ceramics such as zirconium carbide, titanium carbide, tantalum carbide, tungsten carbide, etc.
  • nitride ceramics such as aluminum nitride, silicon nitride, boron
  • the honeycomb structure forming the filter according to the present invention is an aggregate-type honeycomb structure as shown in FIG. 1, among the above ceramic particles, heat resistance is high, and mechanical characteristics and chemical stability are improved. Silicon carbide is desirable because it has excellent thermal conductivity.
  • the honeycomb structure forming the filter according to the present invention is an integral honeycomb structure as shown in FIG. 3, an oxide ceramic such as cordierite is used. It can be manufactured at low cost and has a relatively small coefficient of thermal expansion. For example, it is not broken during use as a honeycomb filter, and it is not oxidized. It is.
  • the thermal conductivity of the substrate of the honeycomb structure forming the filter according to the present invention is determined by the type of ceramic particles used, etc., but when ceramic ceramics or nitride ceramics are used as ceramic particles Is preferably 3 WZ m ⁇ K to 60 WZ m W / m 2 K ⁇ 40 W / m 2 K is more desirable.
  • the thermal conductivity is less than 3 WZm ⁇ K, the temperature of the filter will be too high and the filter will be damaged, and the performance of the catalyst supported on the filter will be reduced. ⁇ If the temperature exceeds K, the temperature of the filter will not rise easily, so it will be difficult for the particulate soot to burn, and it will be difficult to purify the exhaust gas.
  • the thermal conductivity is preferably 0.1 WZm ⁇ K to 10W Wm ⁇ ⁇ , and 0.3 WZm ⁇ ⁇ ⁇ 3 W / m ⁇ More preferably ⁇ .
  • the thermal conductivity is less than 0.1 WZm ⁇ K, the temperature of the filter is too high and the filter is damaged, or the performance of the catalyst supported on the filter decreases. This is because if the temperature exceeds 1 OWZm ⁇ K, the temperature of the filter becomes difficult to rise, so it becomes difficult for the particulate soot to burn and purification of the exhaust gas becomes difficult.
  • the shape of the ceramic block is a columnar shape.
  • the ceramic block is not limited to a columnar shape as long as it is a columnar shape. It may be of a shape such as a prismatic shape.
  • the porosity of the ceramic block is preferably about 20 to 80%. The reason is that when the porosity is less than 20%, when the above honeycomb structure is used as a honeycomb filter, clogging occurs immediately, and when the porosity exceeds 80%, ceramic This is because the strength of the block decreases and it is easily broken.
  • the porosity can be measured by a conventionally known method such as a mercury intrusion method, an Archimedes method, or a measurement using a scanning electron microscope (SEM).
  • the average pore size of the ceramic block is preferably about 5 to 100 m. The reason is that if the average pore diameter is less than 5 jum, when the above honeycomb structure is used as a filter, the particulates are easily clogged, while the average pore diameter is 1 OO jUm. This is because the particulates pass through the pores, and the particulates cannot be collected and cannot function as a filter.
  • the sealing material is preferably made of a porous ceramic. .
  • the sealed ceramic block is made of porous ceramic, so that the sealing material is the same porous ceramic as the ceramic block, so that the adhesive strength between them can be increased.
  • the thermal expansion coefficient of the ceramic block can be matched with the thermal expansion coefficient of the sealing material. It is possible to prevent cracks from occurring in the wall part where the sealing material is in contact with the sealing material due to thermal stress during use. This is because it can be done.
  • the sealing material is made of porous ceramic, it is desirable to use, for example, the same material as the ceramic particles constituting the ceramic block described above.
  • the sealing material layers 1 3 and 14 are provided between the porous ceramic members 20 or ceramics. These are arranged on the outer periphery of the block 15 so as to surround them.
  • the sealing material layer 14 interposed between the porous ceramic members 20 functions as an adhesive that binds the plurality of porous ceramic members 20 together.
  • the sealing material layer 13 formed on the outer periphery of the block 15 is a ceramic block 1 when the honeycomb structure 10 is installed in the exhaust passage of the internal combustion engine. It functions to prevent the exhaust gas from leaking from the outer periphery of 5.
  • the sealing material layer is formed between the porous ceramic members and on the outer periphery of the ceramic block.
  • These sealing material layers are the same. It may be made of a material or a different material. For example, an inorganic binder, an organic binder, and inorganic fibers and / or inorganic particles are used. Furthermore, when the sealing material layers are made of the same material, the blending ratio of the materials may be the same and may be different.
  • silica sol for example, silica sol, alumina sol or the like is used. These may be used alone or in combination of two or more. Of the above inorganic binders, silica is preferred.
  • Examples of the organic binder constituting the sealing material layer include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and the like. These may be used alone or in combination of two or more. Among the organic binders, carboxymethyl cellulose is desirable.
  • the inorganic fibers constituting the sealing material layer for example, silica alumina, mullite, alumina, a ceramic fiber such as siri force, or the like is used. These may be used alone or in combination of two or more. Among the inorganic fibers, silica monoalumina fiber is desirable.
  • the inorganic particles constituting the sealing material layer include carbides, nitrides, and the like. Specifically, silicon carbide, silicon nitride, nitriding An inorganic powder made of boron or the like or a whisker is used. These may be used alone or in combination of two or more.
  • silicon carbide having excellent thermal conductivity is desirable.
  • the sealing material layer 14 interposed between the members may be made of a dense material, but when used as the honeycomb filter, the exhaust gas can flow into the inside thereof. A porous body is used.
  • the sealing material layer 13 disposed on the outer periphery of the filter is made of a dense body. This is because the sealing material layer 13 is used for the purpose of preventing the exhaust gas from leaking from the outer periphery of the ceramic block 15 when the honeycomb structure 10 is installed in the exhaust passage of the internal combustion engine. is there.
  • the honeycomb structure according to the present invention has a structure in which a sealing material is filled and sealed at one end of each cell of the ceramic block, as shown in FIGS. It is suitable for collecting particulates in exhaust gas discharged from internal combustion engines such as diesel engines.
  • the partition walls of the ceramic block of the honeycomb structure may carry a catalyst such as Pt for promoting combustion of the particulate when the honeycomb filter is regenerated.
  • a catalyst such as Pt for promoting combustion of the particulate when the honeycomb filter is regenerated.
  • exhaust gas discharged from a heat engine such as an internal combustion engine or a combustion device such as a boiler by supporting a catalyst such as a noble metal such as Pt, Rh, or Pd or an alloy thereof on a ceramic block of a honeycomb structure It can be used to purify HC, CO, NOx, etc.
  • FIG. 4 is a perspective view schematically showing a specific example of the laminated honeycomb structure
  • FIG. 4 (a) is a perspective view of the porous ceramic sintered body shown in FIG. Figure (b)
  • FIG. 3 is a cross-sectional view taken along line C-C of the porous ceramic member shown in (a).
  • This filter is a laminate in which plate-like sheets (thickness of about 0.1 to 20 mm) are laminated in the thickness direction, that is, in the longitudinal direction of the filter, and the cell through holes overlap in the longitudinal direction.
  • the cells 4 1 are shaped to form a honeycomb structure.
  • the term “stacked so that the cell through holes overlap each other” means that the through holes formed in the adjacent sheet-shaped objects communicate with each other to form the cell 41.
  • the sheet-like material is preferably made of ceramic, metal or the like, but in the present invention, it is preferably made mainly of inorganic fibers. This is because when the sheet-like material is made of inorganic fibers, it can be easily produced by a papermaking method or the like, and a honeycomb structure made of a laminated body can be produced by laminating them. .
  • the laminate may be formed by bonding with an inorganic adhesive material or the like, or may be merely physically laminated.
  • the honeycomb structure 40 has a large number of cells 41a, in which either one end of the cells, that is, the downstream end on the exhaust gas inflow side is plugged, arranged in parallel in the longitudinal direction with the partition wall 43 therebetween. It has a cylindrical shape that functions as a filter.
  • the cell is sealed at either the end corresponding to the exhaust gas inlet side or the outlet side, and the exhaust gas flowing into one cell 41a is After passing through the partition wall 43 that separates these cells, it flows out from the other cell 4 1 b and functions as a filter.
  • the wall thickness is preferably in the range of 0.2 to 10 mm, and more preferably in the range of 0.3 to 6.0 mm.
  • the thickness is less than 0.2 mm, the strength is weak and may be damaged during use. If the thickness exceeds 10 O mm, the exhaust gas hardly permeates and the pressure loss is large. Because it becomes.
  • the density of cells in the cross section perpendicular to the longitudinal direction of the honeycomb structure is 0.16 cells / cm 2 (1.0 cells ⁇ 2 ) to 62 cells cm 2 (400 cells / in 2 ).
  • 0.6 2 pieces cm 2 (4.0 pieces Z in 2 ) to 3 1 pieces Zcm 2 (200 pieces Z in 2 ) is a more desirable range.
  • the reason for this is that if the area is less than 0.1 6 cm 2 , the filtration area is small and the pressure loss tends to be large, and if it exceeds 62 2 cm 2 , the cross-sectional area per through hole is small. This is because the particulates and ash are easily clogged.
  • the size of the through hole is 1.4mm x 1.4mm ⁇ 16mmx16mm force, desired.
  • Examples of the material of the inorganic fiber include oxide ceramics such as silica-alumina, clay, alumina, and silica, nitride ceramics such as aluminum nitride, silicon nitride, boron nitride, and titanium nitride, silicon carbide, Carbide ceramics such as zirconium carbide, titanium carbide, tantalum carbide, and tungsten carbide can be used. These may be used alone or in combination of two or more.
  • oxide ceramics such as silica-alumina, clay, alumina, and silica
  • nitride ceramics such as aluminum nitride, silicon nitride, boron nitride, and titanium nitride
  • silicon carbide Carbide ceramics such as zirconium carbide, titanium carbide, tantalum carbide, and tungsten carbide can be used. These may be used alone or in combination of two or more.
  • the fiber length of the inorganic fiber is preferably 0.1 mm to 100 mm, and more preferably 0.5 mm to 5 O mm.
  • the thickness is less than 0.1 mm, the elasticity due to the use of the fiber is lowered and it becomes difficult to maintain the shape, and if it exceeds 100 mm, the additivity is lowered.
  • the fiber diameter of the inorganic fiber is preferably 1 m to 30 m, and more preferably 2 / m to 10 m. The reason is that if it is less than 1 fi m, the strength is insufficient, and if it exceeds 30 ju m, the workability deteriorates.
  • the honeycomb structure may include a binder that bonds these inorganic fibers to maintain a certain shape.
  • the binder include inorganic glass such as silicate glass, alkali silicate glass, and borosilicate glass, alumina sol, silica sol, and titasol.
  • the content is preferably 5 w t% to 50 w t%, and more preferably 10 w t% to 40 w t% o
  • the bonding strength is insufficient if it is less than 5 wt%, and conversely, if it exceeds 50 wt%, there are too many indas and the bonding between the fibers becomes insufficient.
  • the honeycomb structure may contain a small amount of inorganic particles and metal particles.
  • inorganic particles for example, carbides, nitrides, oxides and the like can be used.
  • inorganic powders made of silicon carbide, silicon nitride, boron nitride, alumina, silica, zirconia, titania, etc. Can be used.
  • metal particles examples include metal silicon, aluminum, iron, and titanium. These may be used alone or in combination of two or more.
  • the apparent density of the honeycomb structure is preferably 0.05 gZ cm 3 to 1.0 O gZ cm 3 , and is preferably 0.1 g / cm 3 to 0.5 0 g Z cm 3 . It is more desirable.
  • the porosity of the honeycomb structure is preferably a 6 0% by volume to 9 8 volume%, 8 0 volume% to 9 5 volume 0/0 is a more desirable arbitrariness.
  • the reason is that if it is less than 60% by volume, the passage of exhaust gas decreases, while if it exceeds 98% by volume, the strength is insufficient.
  • the apparent density and porosity can be measured by a conventionally known method such as a gravimetric method, an Archimedes method, or a measurement using a scanning electron microscope (S E M).
  • a catalyst made of a noble metal such as platinum, palladium, or rhodium may be supported on the inorganic fiber constituting the honeycomb structure.
  • a noble metal such as platinum, palladium, or rhodium
  • alkali metals Group 1 of the Periodic Table of Elements
  • alkaline earth metals Group 2 of the Periodic Table of Elements
  • rare earth elements Group 3 of the Periodic Table of Elements
  • transition metal elements may be added. .
  • the filter using the honeycomb structure functions as a filter that can collect particulates in the exhaust gas and perform regeneration treatment with the catalyst. It can function as a catalytic converter for purifying C0, HC, NOx, etc. contained in exhaust gas.
  • the shape of the honeycomb structure 10 shown in FIG. 4 is a columnar shape, but is not limited to the circular columnar shape. For example, it has an arbitrary columnar shape or size such as an elliptical columnar shape or a prismatic shape. Also good.
  • An important structure in the filter according to the present invention is to use any one of the aggregate type honeycomb structure 10, the integral type honeycomb structure 30, and the laminated honeycomb structure 40 as described above.
  • the exhaust gas inflow side cells 2 1 a, 3 1 a, 4 formed in this structure are preferable.
  • Made of vitreous material such as low-melting glass or low-melting-point inorganic compound-based flux material in the vicinity of the sealing part in the cell of 1a or on the partition wall surface, and further on the downstream part of the partition wall surface. This is in that an ash trap layer 1 0 0 is provided.
  • the low melting point glass is vitrified by softening or melting at a temperature at which particulates collected during regeneration can be burned and removed, that is, at a filter regeneration temperature (2500 to 800 ° C).
  • Inorganic compounds such as phosphate glass and calcium sulfate glass are preferred, and the low melting inorganic compound flux material is softened or melted within the above temperature range. Sulfate flux or chloride containing flux is preferred. In addition, two or more of these materials can be used in combination.
  • the reason why the above-described ash trap layer is provided in the cell is as follows.
  • particulate matter particulate soot
  • the ash component left as unburned material is blown away by the exhaust gas.
  • the ash thus blown is vitrified and fluidized in a softened and melted state.
  • the ash in such a flow state attracts and binds with each other in order to trap the ash, so that all the softened ash that has detached (from the particulates) accumulates in this portion (ash trap, etc.). That is, the softened glass or flux generated in this way is accumulated at a high density in that portion, and is fixed there, so that even if the filter is used for a long time, the filtration area is small. There is no longer a loss of pressure.
  • the honeycomb structure forming the filter is a so-called wall flow type in which any one of the cell end portions is sealed with a sealing material
  • the ash trap layer is formed on the partition wall of the ceramic block. Rather than forming, it is preferable to form it at a position adjacent to the sealing part of the exhaust gas outflow side.
  • the honeycomb structure is an integrated honeycomb structure 30 formed as one ceramic block as a whole
  • the ceramic structure as described above is used. Extrusion molding is performed using a raw material paste ⁇ containing particles as a main component, and a ceramic molded body having substantially the same shape as the honeycomb structure 30 shown in Fig. 3 is produced.
  • the raw material paste preferably has a porosity of 20 to 80% of ceramic block after production.
  • ceramic particle powder having a large average particle size and ceramic particle having a small average particle size A mixed powder consisting of and added with a binder and a dispersion medium is used.
  • the binder for example, methyl cellulose, carboxymethyl cellulose, hydroxychetyl cellulose, polyethylene glycol, phenol resin, epoxy resin and the like are used.
  • the amount of the binder is desirably about 1 to 10 parts by weight with respect to 100 parts by weight of the ceramic particle powder.
  • the dispersion medium liquid for example, an organic solvent such as benzene, alcohol such as methanol, water or the like is used, and this dispersion medium liquid is blended so that the viscosity of the raw material paste ⁇ ⁇ ⁇ falls within a certain range.
  • the mixed powder consisting of the ceramic powder and the silicon powder, the binder and the dispersion medium liquid are mixed with an attritor or the like, and sufficiently mixed with a kneader to obtain a raw material paste, and then the raw material paste is extruded. Molding to produce the above ceramic molded body.
  • a molding aid may be added to the raw material paste as necessary, and examples of the molding aid include ethylene glycol, dextrins phosphorus, fatty acid sarcophagus, polyvinyl alcohol, and the like. Is used.
  • a pore-forming agent such as balloons that are fine hollow spheres containing oxide-based ceramics, spherical acrylic particles, and graphite may be added to the raw material paste as necessary.
  • an alumina balloon for example, an alumina balloon, a glass micro balloon, a shirasu balloon, a fly ash balloon (FA balloon), and a murato balloon are used.
  • alumina balloons are preferred.
  • the ceramic molded body is dried using a microphone mouth wave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, a freeze dryer, or the like to obtain a ceramic dried body, and then a predetermined cell.
  • One end of the cell is filled with a paste serving as a sealing material, and the cell is sealed.
  • the ceramic dry body filled with the sealing material paste ⁇ is heated to about 150 to 700 ° C. to remove the binder contained in the ceramic dry body, and the ceramic degreased body and Apply degreasing treatment.
  • the above ceramic degreased body is heated to about 1400-200 ° C. And manufacturing a ceramic porous body.
  • the honeycomb structure manufactured in this way has a structure in which a sealing material is filled and sealed at the outflow side end of the exhaust gas inflow side cell of the ceramic block.
  • the honeycomb filter for exhaust gas purification described above As such, it can be suitably used.
  • the cell wall of the ceramic block that is, the surface of each partition wall, may be supported with a catalyst such as Pt for promoting the combustion of the particulates when the honeycomb filter is regenerated.
  • the honeycomb structure is an aggregated honeycomb structure 10 in which a plurality of porous ceramic members are bundled through a sealing material layer as shown in FIG.
  • extrusion molding is performed using the above-mentioned raw material paste containing ceramic particles and silicon as main components, and a shaped product having a shape like the porous ceramic member 20 shown in FIG. 2 is produced.
  • the raw material paste may be the same as the raw material paste described in the above-described integrated honeycomb structure 30.
  • the generated shaped body is dried using a microwave dryer or the like to obtain a dried body, and then a sealing material and a sealing material are provided at the end on the outflow side of the through hole on the gas inflow side serving as a cell of the dried body.
  • a sealing process is performed to fill the sealing material paste and seal the cells.
  • the upstream end of the exhaust gas outflow side cell adjacent to the exhaust gas inflow side is similarly sealed with a sealing material.
  • a dry body in which each cell is alternately sealed as described above, is subjected to a degreasing process under the same conditions as those of the above-described integrated honeycomb structure 30, and then fired to obtain a plurality of It is possible to manufacture a porous ceramic member in which the cells are arranged in parallel in the longitudinal direction across the partition walls. Then, on the side surface of the porous ceramic member 20, a seal layer is formed. The process of applying and laminating a paste paste with a uniform thickness is repeated to produce a laminated body of prismatic porous ceramic members 20 having a predetermined size. Since the material constituting the sealing material paste has been described when the honeycomb structure is described, the description thereof is omitted here.
  • the laminated body of the porous ceramic member 20 is heated to dry and solidify the sealing material paste layer 51 to form the sealing material layer 14. Then, for example, using a diamond cutter or the like, A ceramic block 15 is manufactured by cutting the outer peripheral portion into a shape as shown in FIG. Furthermore, a honeycomb structure in which a plurality of porous ceramic members are bundled through a seal material layer by forming the seal material layer 13 on the outer periphery of the ceramic block 15 using the above seal material paste. Structures can be manufactured.
  • the aggregated honeycomb structure 10 manufactured in this way is obtained by filling the end portion of a predetermined cell of a ceramic block (porous ceramic member) with a sealing material and sealing it. It can be suitably used as a honeycomb filter for gas purification.
  • the wall of the ceramic block (the partition wall of the porous ceramic member) may carry a catalyst such as Pt for promoting the combustion of the particulates when the honeycomb filter is regenerated. Good.
  • the downstream end portions of the exhaust gas inflow side cells 21a and 31a are adjacent to the portion (sealing portion) sealed with the sealing material.
  • the ash trap layer 100 it is desirable that the ash trap layer 100 be formed, but in some cases, the ash trap layer may be formed on the partition wall surface (cell wall).
  • This ash trap layer 100 is formed by cooling after melting, coating, filling, or spraying molten glassy material into the exhaust gas inflow side cells 2 1a, 3 1a. can do. If a trap layer is formed at the time of sealing, it is then fired at ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , so the trap layer softens at 25 ° to 80 ° C., which is not preferred.
  • the sealing material may be pushed in and sealed.
  • Inorganic fibers such as alumina fibers are impregnated in a slurry prepared by melting phosphate glass, for example, and then pulled up and cooled to prepare inorganic fibers on which a glassy ash trap layer is adhered and supported.
  • the supported amount of ash trap is preferably 0.01 to 90 g per 10 g of inorganic fiber.
  • the ash trap layer 100 can be more evenly dispersed because the ash trap layer 100 can be directly applied to the inorganic fiber that is a constituent material before molding. In this state, it can be supported and adhered.
  • the ash trap layer 100 is controlled so as not to melt and flow out of the filter, and utilizes the property of softening and melting during regeneration. Therefore, when the surface of the ash trap layer is softened and melted (that is, at the time of regeneration), it is desirable that the ash be immediately taken into the ash trap layer when the particulate reaction occurs. . In other words, ash can be reliably taken into the trap layer by providing ash traps uniformly within the filter.
  • the combustion function of particulates and the purification function of harmful gases can be increased.
  • the provision of the strap layer may be performed after the papermaking sheet is produced.
  • the inorganic fiber carrying the catalyst obtained in step (1) is dispersed at a rate of 5 to 100 g per 1 liter of water, and an inorganic binder such as sili-force sol is added to the inorganic fiber 1.
  • an inorganic binder such as sili-force sol is added to the inorganic fiber 1.
  • organic binder such as acrylic latex
  • coagulant such as aluminum sulfate, polyacrylamide, etc.
  • organic binder examples include methyl cellulose, carboxymethyl cellulose, hydroxy shetil cellulose, polyethylene glycol, phenol resin, epoxy resin, polyvinyl alcohol, and styrene butadiene rubber.
  • the slurry obtained in the above (2) is made by a punching mesh in which holes having a predetermined shape are formed at predetermined intervals, and the obtained slurry is heated to a temperature of about 100 to 200 ° C. By drying with, a paper sheet 40 a having a predetermined thickness as shown in FIG. 5 (a) is obtained.
  • the thickness of the papermaking sheet 40 a is preferably 0.1 to 20 mm.
  • a papermaking sheet 40b for both ends can be obtained.
  • a honeycomb structure that functions as a filter can be obtained without forming a cell and then closing a predetermined cell at both ends. Can do.
  • a cylindrical case with a holding bracket on one side As shown in Fig. 5 (b), a cylindrical case with a holding bracket on one side. First, a plurality of sheet-forming sheets 40 b for both ends are stacked in the casing 43, and then a predetermined number of sheet-forming sheets 40 a for internal use are stacked. Finally, several sheets of paper 40b for both ends were stacked, further pressed, and then the other side was installed and fixed with holding metal fittings to complete the canning. A honeycomb structure can be produced. Of course, in this process, the papermaking sheets 40 a and 40 b are laminated so that the cells overlap.
  • the honeycomb structure forming the filter of the present invention is simply simply formed by stacking paper sheets, the honeycomb structure is disposed in the exhaust passage when the honeycomb structure is disposed in the exhaust passage. Even if a certain temperature distribution occurs in the structure, the temperature distribution of a single sheet is small and cracks are not likely to occur.
  • the inorganic fibers are oriented almost parallel to the main surface of the papermaking sheet, and when the laminate is produced, the inorganic fibers are compared with the surfaces parallel to the cell formation direction.
  • the orientation is more along the plane perpendicular to the cell formation direction.
  • the exhaust gas can easily permeate the walls of the honeycomb structure, so that the initial pressure loss can be reduced and the particulates can be easily filtered through the inside of the partition walls. Can be suppressed, and an increase in pressure loss during particulate collection can be suppressed.
  • the shape of the hole is not particularly limited to a quadrangle, and may be any shape such as a triangle, hexagon, octagon, dodecagon, circle, or ellipse.
  • FIG. 6 is a cross-sectional view schematically showing an example of an exhaust gas purifying device for a vehicle in which the filter of the present invention is installed.
  • an exhaust gas purification device 600 mainly includes a honeycomb filter 60 according to the present invention, a casing 630 which covers the outside of the honeycomb filter 60, and A holding sealing material 6 20 disposed between the cam filter 60 and the casing 6 30 and heating means 6 10 provided on the exhaust gas inflow side of the honeycomb filter 60 are configured.
  • An exhaust introduction pipe 6 40 connected to an internal combustion engine such as an engine is connected to an end of the casing 6 30 on the side where the exhaust gas is introduced.
  • a discharge pipe 65 0 connected to the outside is connected to the end.
  • the arrows indicate the flow of exhaust gas.
  • an exhaust pipe in front of the honeycomb filter or a catalyst carrier carrying platinum in the casing. This is because, among exhaust gases, the heat generated by gases that react at low temperatures, such as HC, is transmitted to the honeycomb filter, which makes the filter cool to high temperatures.
  • the particulate filter described above is not particularly limited in shape and structure as long as it has a structure capable of collecting particulate matter, but preferably has a surface area as large as possible.
  • the first flow path has a two-cam structure, a porous material is used as a base material, the upstream end is open, and the downstream end is closed, and the upstream end is closed.
  • a so-called wall flow type in which the second flow path having the open end on the downstream side is alternately arranged in a honeycomb shape can be provided.
  • These first flow paths become exhaust gas inflow side cells whose downstream ends are closed by a sealing material, and the second flow paths are exhaust gases whose upstream ends are closed by a sealing material.
  • the structure of the honeycomb filter 60 may be the same as the aggregated honeycomb structure 10 shown in FIG. 1 or the integrated honeycomb structure 30 shown in FIG.
  • exhaust gas discharged from an internal combustion engine such as an engine is introduced into the casing 6 30 through the introduction pipe 6 40, and the honeycomb filter. After passing through the wall (partition wall) from the 60 cell, the particulates are collected and purified by this partition wall, and then discharged to the outside through the discharge pipe 6 50.
  • the regeneration process of the honeycomb filter 60 is performed.
  • the gas heated by the heating means 61 is flowed into the cells of the honeycomb filter 60 to heat the honeycomb filter 60, and the particulates deposited on the partition walls are burned by the heating. Removed.
  • the heating means 6 10 when a catalyst such as Pt for promoting the combustion of particulates is supported on the partition walls of the honeycomb filter 60, the combustion temperature of the particulates is lowered, so the honeycomb filter 60 by the heating means 6 10 is used. In some cases, heating by the heating means 6 10 can be eliminated.
  • the regeneration of the filter means that the collected particulates are burned, but the regeneration method is a method in which the honeycomb structure is heated by a heating means provided on the exhaust gas inflow side.
  • an oxidation catalyst is supported on the two-cam structure, and the heat generated by the oxidation of hydrocarbons in the exhaust gas by the oxidation catalyst is used to regenerate in parallel with the purification of the exhaust gas.
  • the particulates are burned and removed in the temperature range of 2500 ° C. to 800 ° C., which is the melting temperature of the ash trap layer 100.
  • (Regeneration treatment) is preferably configured, and more preferably, the regeneration treatment is performed in a temperature range of 500 ° C to 700 ° C.
  • the exhaust gas has a relatively high oxygen concentration. Therefore, the regeneration process of the exhaust gas purification device for the diesel engine has a relatively high oxygen concentration or an oxygen storage effect of rare earth elements or the like. Usually, it is carried out in an excess oxygen atmosphere by the action of a catalyst having
  • the vitreous material or flux material constituting the ash trap layer 100 is melted and easily flows from the porous filter. Below 2500 ° C, the glass or flux will not melt, so it will not function to take in and fix the ash.
  • a glassy material or an inorganic compound-based flux material is melted and reduced in viscosity within a temperature range of 250 ° C. to 800 ° C.
  • 11 types of testable glassy materials (Test Examples 1 to 1 1) and inorganic compound flux materials were used. 5 types (Test Examples 1 2 to 16) were selected. The results are shown in Table 1.
  • thermogravimetric / differential thermal analyzer (TGZD TA) (manufactured by Seiko Denshi Co., Ltd., product name: TGZDTA220U). The lowest liquidus temperature, the lowest melting temperature, and the glass transition temperature were obtained and the applicability was judged.
  • Examples 1 to 16 below are examples of an integral honeycomb structure
  • Examples 1 7 to 3 2 are examples of an aggregated honeycomb structure
  • Examples 3 3 to 4 8 are It is an example of a laminated honeycomb structure.
  • the P 2 0 3 based glass such as that shown in Test Example 1 was slurried dissolved in 400 ° C, sealing the slurry Seruen de of exhaust gas inflow-side cells of the honeycomb structure Spraying to a thickness of 5 mm adjacent to the stop, an ash trap layer is formed and used as a filter.
  • Example 7 A honeycomb structure similar to (1) of Example 1 was used.
  • Example 16 (1) A honeycomb structure similar to (1) of Example 1 was used.
  • a honeycomb structure was only produced in the same manner as (1) of Example 1, but no ash trap layer was formed.
  • a raw material paste was prepared by adding 24 parts by weight of water and kneading.
  • the raw material paste was filled into an extrusion molding machine, and a green body having substantially the same shape as the porous ceramic member 30 shown in FIG. 23 was produced at an extrusion speed of 10 cm / min.
  • a sealing material paste having the same composition as that of the formed form is filled into one end of a predetermined through hole, and then again. It was dried using a drier and further degreased at 55 ° C. for 3 hours in an oxidizing atmosphere to obtain a ceramic degreased body.
  • the porosity is 45%
  • the average pore diameter is 10 m
  • the size is 34.3.
  • a porous ceramic member of mm X 3 4.3 mm x 25 4 mm was produced.
  • the thickness of the sealing material layer for binding the porous ceramic member was adjusted to 1.0 mm.
  • ceramic fiber made of alumina silicate as inorganic fiber (Shock content: 3%, fiber length: 5 to 100 jum) 2 3.3% by weight, average as inorganic particles
  • Silicon carbide powder with a particle size of 0.3 m 30.2% by weight silica sol as inorganic binder (content of Sio 2 in sol: 30% by weight) 7% by weight, carboxymethyl cereal as organic binder 0.5% by weight of roulose and 39% by weight of water were mixed and kneaded to prepare a sealing material case ⁇ .
  • a seal material paste layer having a thickness of 1.0 mm was formed on the outer periphery of the ceramic block using the seal material paste.
  • the seal material paste layer was dried at 120 ° C. to produce a honeycomb structure having a cylindrical shape and functioning as a honeycomb filter for exhaust gas purification.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • the GaSO 4 glass shown in Test Example 5 is melted at 700 ° C. to form a slurry, and the slurry is sealed at the downstream end in the exhaust inflow side cell.
  • the filter was applied and filled with a thickness of 5 mm adjacent to the stopper to form an ash trap layer, which was used as a filter.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • the CaSO 4 glass shown in Test Example 7 is melted at 7700C to make a slurry, and the slurry is placed at the downstream end in the exhaust inflow side cell.
  • the ash trap layer was formed by pouring in a thickness of 5 mm adjacent to the sealing portion to obtain a filter.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as (1) to (2) in Example 17 Made.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • a honeycomb structure was manufactured in the same manner as in (1) to (2) of Example 17.
  • Test Example 16 6 Chloride-containing flux was melted at 4800C to make a slurry, and the slurry was placed at the downstream end in the exhaust inflow side cell. An ash trap layer was formed by pouring in a thickness of 5 mm adjacent to the sealing portion to obtain a filter.
  • a honeycomb structure was only manufactured in the same manner as (1) to (2) in Example 17 and no ash trap layer was formed.
  • Alumina fibers (average fiber diameter: 5 m, average fiber length: 0. 3 mm), and was impregnated 2 minutes to the slurry one was melted to P 2 0 3 system glass 400 ° C, as shown in Test Example 1
  • Alumina slurry carrying Pt (Pt concentration: 5 Wt%) was impregnated for 2 minutes, and then heated to the slurry preparation temperature of each ash trap to prepare an alumina fiber with a catalyst attached. As a result, the supported amount of Pt is 0.
  • the alumina fiber obtained in step (1) is dispersed at a rate of 10 g per 1 liter of water, and in addition, silica sol is added to the fiber as an inorganic binder.
  • Acrylate latex was added at a rate of 3 wt% as an organic binder.
  • a slurry for papermaking was prepared by adding a small amount of aluminum sulfate as a coagulant and a small amount of polyacrylamide as a coagulant and stirring sufficiently.
  • a casing (cylindrical metal container) with a holding bracket attached on one side was erected so that the side on which the bracket was attached was down. Then, after three sheets of paper sheet B were laminated, 150 sheets of paper sheet A 1 were laminated, and finally three paper sheets were laminated, and further pressed, and then the other sheet was also used for restraining. By installing and fixing the bracket, the length is 1
  • a honeycomb structure composed of a 50 mm laminate was manufactured and used as a filter. The amount of Pt supported on this honeycomb structure was 5 gZl. In this step, the sheets were laminated so that the through holes overlapped.
  • Example 5 Except that the slurries by dissolving CAS0 4 glass as shown in Test Example 5 7 00 ° C, the same procedure as in Example 3 3 to manufacture a laminated honeycomb structured body, and a filter.
  • Example 3 3 Except that the slurries by dissolving GaS0 4 glass as shown in Test Example 6 in 5 8 0 ° C, the same procedure as in Example 3 3 to manufacture a laminated honeycomb structured body, and a filter.
  • Example 7 Except that the slurries by dissolving CAS0 4 glass as shown in Test Example 7 by 7 7 0 ° C, the laminated honeycomb structured body in the same manner as in Example 3 3 Manufactured and used as a filter.
  • Example 8 7 3 0 ° C Except that the slurries by dissolving CAS0 4 glass as shown in Test Example 8 7 3 0 ° C, the same procedure as in Example 3 3 to manufacture a laminated honeycomb structured body, and a filter.
  • Example 9 Except that the slurries by dissolving CAS0 4 glass as shown in Test Example 9 6 5 0 ° C, the same procedure as in Example 3 3 to manufacture a laminated honeycomb structured body, and a filter.
  • Example 3 3 Except that the slurries by dissolving CAS0 4 glass as shown in Test Example 1 0 One at 0 0 ° C, the same procedure as in Example 3 3 to manufacture a laminated honeycomb structured body, and a filter.
  • Example 3 3 Except that the slurries by dissolving CAS0 4 glass as shown in Test Example 1 1 5 0 0 ° C, the same procedure as in Example 3 3 to manufacture a laminated honeycomb structured body, and a filter.
  • a laminated honeycomb structure was produced as a filter in the same manner as in Example 33 except that a sulfide-based flux as shown in Test Example 12 was melted at 5700C to make a slurry.
  • a laminated honeycomb structure was manufactured and used as a filter in the same manner as in Example 33, except that a sulfide-based flux as shown in Test Example 13 was melted at 530 ° C to form a slurry.
  • Test Example 14 Dissolve a chloride-containing flux as shown in 4 at 55 ° C.
  • a laminated honeycomb structure was produced in the same manner as in Example 33 except that the slurry was made into a slurry.
  • Test Example 15 A laminated honeycomb structure was produced in the same manner as in Example 33, except that a chloride-containing flux as shown in 5 was dissolved at 4800 ° C. into a slurry. It was.
  • a laminated honeycomb structure was produced in the same manner as in Example 33 except that a chloride-containing flux as shown in Test Example 16 was dissolved at 4800 ° C to form a slurry. Filter.
  • a honeycomb structure was manufactured in the same manner as in Example 33, except that the ash trap was not formed in (1) of Example 33.
  • honeycomb structure manufactured according to each of the above-described Examples 1 to 48 and Comparative Examples 1 to 3 was disposed in the exhaust passage of the engine as a particulate filter to form an exhaust gas purification device. Then, the above engine is operated at a rotational speed of 300 min-1 and torque of 50 Nm until a particulate of 8 g I is collected in the filter, and then a regeneration process for burning the particulates. was applied 1 5 0 times.
  • the filter was cut and the presence or absence of ash was visually confirmed.
  • Tables 2 to 4 show the manufacturing conditions and the presence or absence of ash absorption by the ash trap layer for each example. (Table 2)
  • the filter according to the present invention not only removes particulates in exhaust gas discharged from an internal combustion engine such as a diesel engine, but also by combustion during regeneration to remove the particulates.
  • the produced ash is useful for being taken in and fixed by an ash-wrapped layer made of a glassy material or an inorganic compound-based flux material.

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Abstract

La présente invention concerne un filtre destiné à purifier un gaz d'échappement provenant d’un moteur à combustion interne, dans lequel une couche de piège à cendre est disposée dans une cellule du côté d'entrée des gaz d'échappement. En conséquence, le filtre peut avoir une plus grande longévité sans sacrifier la zone de filtration ou sans perte de pression en raison de l’accumulation efficace des cendres produites lors de la régénération du filtre.
PCT/JP2005/021189 2005-11-14 2005-11-14 Filtre, materiau de purification de gaz d’echappement pour moteur a combustion interne et procede de purification de gaz d’echappement WO2007055033A1 (fr)

Priority Applications (1)

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PCT/JP2005/021189 WO2007055033A1 (fr) 2005-11-14 2005-11-14 Filtre, materiau de purification de gaz d’echappement pour moteur a combustion interne et procede de purification de gaz d’echappement

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CN110617122A (zh) * 2018-06-20 2019-12-27 日本碍子株式会社 蜂窝过滤器
CN113996125A (zh) * 2021-10-15 2022-02-01 湖北三江航天红林探控有限公司 一种用于高能燃发器的截面式过滤装置

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JPS6174613A (ja) * 1984-09-18 1986-04-16 Ngk Insulators Ltd 微粒子濾過器
JPH1033923A (ja) * 1996-07-24 1998-02-10 Toyota Motor Corp パティキュレートトラップ装置
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CN110617122A (zh) * 2018-06-20 2019-12-27 日本碍子株式会社 蜂窝过滤器
CN113996125A (zh) * 2021-10-15 2022-02-01 湖北三江航天红林探控有限公司 一种用于高能燃发器的截面式过滤装置
CN113996125B (zh) * 2021-10-15 2022-11-22 湖北三江航天红林探控有限公司 一种用于高能燃发器的截面式过滤装置

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