WO2013024744A1 - Filtre en nid d'abeilles - Google Patents

Filtre en nid d'abeilles Download PDF

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Publication number
WO2013024744A1
WO2013024744A1 PCT/JP2012/070079 JP2012070079W WO2013024744A1 WO 2013024744 A1 WO2013024744 A1 WO 2013024744A1 JP 2012070079 W JP2012070079 W JP 2012070079W WO 2013024744 A1 WO2013024744 A1 WO 2013024744A1
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WIPO (PCT)
Prior art keywords
honeycomb filter
aluminum
powder
flow path
magnesium
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PCT/JP2012/070079
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English (en)
Japanese (ja)
Inventor
健太郎 岩崎
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住友化学株式会社
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Publication of WO2013024744A1 publication Critical patent/WO2013024744A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/478—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on aluminium titanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2482—Thickness, height, width, length or diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2474—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the walls along the length of the honeycomb
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • C04B38/0009—Honeycomb structures characterised by features relating to the cell walls, e.g. wall thickness or distribution of pores in the walls
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a honeycomb filter.
  • the honeycomb filter is used as a ceramic filter for removing the collected matter from the fluid containing the collected matter, for example, for purifying exhaust gas exhausted from an internal combustion engine such as a diesel engine or a gasoline engine. Used as an exhaust gas filter.
  • a honeycomb filter has a plurality of parallel flow paths partitioned by partition walls (see, for example, Patent Document 1 below).
  • the honeycomb filter when the fluid containing the collected matter flows in from the one end side and flows out from the other end side in the honeycomb filter, the pressure is increased as the collected matter is collected in the honeycomb filter. It is difficult to sufficiently suppress the increase in loss. Therefore, it is required for the honeycomb filter to reduce the pressure loss as compared with the related art.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a honeycomb filter capable of reducing pressure loss.
  • the honeycomb filter according to the present invention is a honeycomb filter having a plurality of parallel flow paths partitioned by a porous partition wall, wherein the plurality of flow paths includes the first flow path and the first flow path.
  • the honeycomb filter according to the present invention the maximum height Rz of at least a part of the inner wall of at least one of the first flow path or the second flow path is 55.00 ⁇ m or less. It becomes easy to suppress that an inner wall prevents the movement of a fluid. Moreover, it becomes easy to suppress that the flow path is blocked by the collected matter as the collected matter is collected by the honeycomb filter. Therefore, in the honeycomb filter according to the present invention, pressure loss can be reduced.
  • the average value of the maximum height Rz on the inner wall is preferably 56.00 ⁇ m or less. In this case, the pressure loss can be further reduced.
  • the arithmetic average roughness Ra of the region of the inner wall is preferably 9.000 ⁇ m or less.
  • the inner wall of the flow path is further easily prevented from interfering with fluid movement.
  • the average value of the arithmetic average roughness Ra on the inner wall is preferably 8.000 ⁇ m or less. In this case, the pressure loss can be further reduced.
  • the partition may contain aluminum titanate. In this case, durability against thermal stress of the honeycomb filter can be improved.
  • the honeycomb filter according to the present invention can reduce the pressure loss as compared with the conventional one.
  • a honeycomb filter is suitably used as a ceramic filter for removing the collected matter from the fluid containing the collected matter.
  • FIG. 1 is a perspective view showing a honeycomb filter according to an embodiment of the present invention.
  • FIG. 2 is a view taken along the line II-II in FIG.
  • FIG. 3 is an example of the surface shape of a predetermined measurement region on the inner wall of the flow path.
  • FIG. 4 is a diagram schematically showing a pressure loss measuring device.
  • FIG. 5 is a diagram showing measurement results of pressure loss.
  • FIG. 1 is a perspective view showing a honeycomb filter according to the present embodiment
  • FIG. 2 is a view taken along the line II-II in FIG.
  • the honeycomb filter 100 is a cylindrical body having a plurality of flow paths 110 arranged in parallel to each other. Each of the plurality of flow paths 110 is partitioned by a partition wall 120 that extends parallel to the central axis of the honeycomb filter 100.
  • the flow path 110 includes a flow path (first flow path) 110a constituting a part of the flow path 110 and a flow path (second flow path) 110b constituting the remaining part of the flow path 110. Have.
  • One end of the honeycomb filter 100 in the flow channel 110a is opened as a gas inlet on one end surface 100a of the honeycomb filter 100, and the other end of the honeycomb filter 100 in the flow channel 110a is opened in the honeycomb filter 100.
  • the other end surface 100b of 100 is sealed by the sealing portion 130.
  • the end portion on one end side of the honeycomb filter 100 in the channel 110b is sealed by the sealing portion 130 on the one end surface 100a, and the end portion on the other end side of the honeycomb filter 100 in the channel 110b is on the other end surface 100b. It opens as a gas outlet.
  • the flow path 110b is adjacent to the flow path 110a.
  • the flow paths 110a and the flow paths 110b are alternately arranged to form a lattice structure.
  • the flow paths 110a and 110b are perpendicular to both end faces of the honeycomb filter 100, and are arranged in a square arrangement when viewed from the end face, that is, the central axes of the flow paths 110a and 110b are respectively located at the apexes of the square. .
  • vertical to the axial direction (longitudinal direction) of the said flow path in flow path 110a, 110b is square shape, for example.
  • the maximum height Rz of at least a part of the inner wall of at least one of the flow channel 110a or the flow channel 110b is 55.00 ⁇ m or less.
  • the maximum height Rz of at least a part of the region A (see FIG. 2) in the inner wall 115a of the flow channel 110a that is a flow channel on the gas inflow side is 55.00 ⁇ m or less.
  • the maximum height Rz of at least a part of the region B (see FIG. 2) in the inner wall 115b of the flow channel 110b that is the flow channel on the gas outflow side may be 55.00 ⁇ m or less.
  • the maximum height Rz refers to the maximum height based on JIS B 0601: 2001. From the viewpoint of further reducing the pressure loss, the maximum height Rz is preferably 50.00 ⁇ m or less, and more preferably 48.00 ⁇ m or less.
  • the positions of the area A and the area B are not particularly limited, and may be the center position of the honeycomb filter 100 in the axial direction of the flow path 110, and may be located on the one end face 100a side or the other end face 100b side from the center position. It may be.
  • the size of the areas A and B is, for example, 298 ⁇ m ⁇ 224 ⁇ m.
  • Each of the flow paths 110 may include a plurality of regions having a maximum height Rz of 55.00 ⁇ m or less on one inner wall, and an inner wall having a region having a maximum height Rz of 55.00 ⁇ m or less. You may have two or more.
  • the average value of the maximum height Rz measured on at least one inner wall of the flow channel 110a or the flow channel 110b is preferably 56.00 ⁇ m or less, more preferably 55.00 ⁇ m or less, from the viewpoint of further reducing the pressure loss. More preferably, it is 0.000 ⁇ m or less.
  • the average value of the maximum height Rz is the maximum of the three regions when three regions located along the axial direction of the flow channel are arbitrarily selected from one inner wall of the flow channel to be measured. The average value of height Rz is said.
  • the arithmetic average roughness Ra of the above region that gives the maximum height Rz of 55.00 ⁇ m or less is preferably 9.000 ⁇ m or less, more preferably 8.000 ⁇ m or less, and 7.500 ⁇ m or less. Further preferred.
  • the arithmetic average roughness Ra refers to the arithmetic average roughness based on JIS B 0601: 2001.
  • the average value of the arithmetic average roughness Ra measured on at least one inner wall of the channel 110a or the channel 110b is preferably 8.000 ⁇ m or less, and more preferably 7.500 ⁇ m or less.
  • the average value of the arithmetic average roughness Ra means that the three regions located along the axial direction of the flow channel are arbitrarily selected from the inner wall of one of the flow channels to be measured.
  • the average value of arithmetic average roughness Ra is said.
  • the average value of the maximum height Rz is 56.00 ⁇ m or less and the arithmetic average roughness Ra on at least one inner wall of the flow channel 110a or the flow channel 110b. Is preferably 8.000 ⁇ m or less.
  • the length of the honeycomb filter 100 in the longitudinal direction of the flow paths 110a and 110b is, for example, 30 to 300 mm.
  • the outer diameter of the honeycomb filter 100 is, for example, 10 to 300 mm.
  • the inner diameter (the length of one side of the square) of the cross section perpendicular to the axial direction of the flow paths 110a, 110b is, for example, 0.5 to 1.2 mm.
  • the average thickness (cell wall thickness) of the partition wall 120 is, for example, 0.1 to 0.5 mm.
  • the partition wall 120 is porous, and includes, for example, porous ceramics (porous ceramic sintered body).
  • the partition wall 120 has a structure that allows fluid (for example, exhaust gas containing fine particles such as soot) to pass therethrough. Specifically, a large number of communication holes (flow channels) through which fluid can pass are formed in the partition wall 120.
  • the porosity (open porosity) of the partition wall 120 is, for example, 30 to 70% by volume.
  • the pore diameter (pore diameter) of the partition wall 120 is, for example, 5 to 30 ⁇ m.
  • the porosity and the pore diameter of the partition wall 120 can be adjusted by the particle diameter of the raw material, the added amount of the pore forming agent, the kind of the pore forming agent, and the firing conditions, and can be measured by a mercury intrusion method.
  • the partition wall 120 may contain aluminum titanate, and may further contain magnesium or silicon.
  • the partition 120 is made of, for example, porous ceramics mainly made of an aluminum titanate crystal. “Mainly composed of an aluminum titanate-based crystal” means that the main crystal phase constituting the aluminum titanate-based ceramic fired body is an aluminum titanate-based crystal phase. An aluminum titanate crystal phase, an aluminum magnesium titanate crystal phase, or the like may be used.
  • the composition formula of the partition wall 120 is, for example, Al 2 (1-x) Mg x Ti (1 + x) O 5 , and the value of x is preferably 0.03 or more. 0.03-0.20 is more preferable, and 0.03-0.18 is still more preferable.
  • the partition 120 may contain a trace component derived from a raw material or a trace component inevitably included in the manufacturing process.
  • the partition 120 may contain the glass phase derived from a silicon source powder.
  • the glass phase refers to an amorphous phase in which SiO 2 is the main component.
  • the glass phase content is preferably 4% by mass or less.
  • an aluminum titanate-based ceramic fired body that satisfies the pore characteristics required for a ceramic filter such as a particulate filter is easily obtained.
  • the glass phase content is preferably 2% by mass or more.
  • the partition wall 120 may include a phase (crystal phase) other than the aluminum titanate crystal phase or the glass phase.
  • the phase other than the aluminum titanate-based crystal phase include a phase derived from a raw material used for producing an aluminum titanate-based ceramic fired body. More specifically, the phase derived from the raw material is a phase derived from an aluminum source powder, a titanium source powder and / or a magnesium source powder that remains without forming an aluminum titanate-based crystal phase during the manufacture of the honeycomb filter.
  • the phase derived from the raw material include phases such as alumina and titania.
  • the crystal phase forming the partition wall 120 can be confirmed by an X-ray diffraction spectrum.
  • the honeycomb filter 100 is suitable as a particulate filter that collects a collection object such as soot contained in exhaust gas from an internal combustion engine such as a diesel engine or a gasoline engine.
  • a collection object such as soot contained in exhaust gas from an internal combustion engine such as a diesel engine or a gasoline engine.
  • the gas G supplied from the one end face 100a to the flow path 110a passes through the communication hole in the partition wall 120 and reaches the adjacent flow path 110b, and the other end face 100b. Discharged from.
  • the collected matter in the gas G is collected on the surface of the partition wall 120 or in the communication hole and removed from the gas G, whereby the honeycomb filter 100 functions as a filter.
  • the partition 120 is not limited to including aluminum titanate, and may include ceramics such as cordierite, silicon carbide, mullite, or a metal substance.
  • the cross section of the flow path perpendicular to the axial direction of the flow path in the honeycomb filter 100 is not limited to a rectangular shape such as a square shape, but a hexagonal shape, an octagonal shape, a triangular shape, a circular shape, an elliptical shape, or the like. It may be.
  • the honey-comb filter 100 is not restricted to a cylindrical body, A cube, a rectangular parallelepiped, etc. may be sufficient.
  • the manufacturing method of the honeycomb filter 100 includes, for example, (a) a raw material preparation step of preparing a raw material mixture containing the ceramic powder and additives, and (b) forming a raw material mixture to obtain a formed body having a flow path. A molding step, and (c) a firing step for firing the molded body, and (d) a sealing step for sealing one end of each flow path between the molding step and the firing step or after the firing step. .
  • the ceramic powder and the additive are mixed and then kneaded to prepare a raw material mixture.
  • the additive include a hole forming agent (pore forming agent), a binder, a plasticizer, a dispersant, and a solvent.
  • the ceramic powder includes at least an aluminum source powder and a titanium source powder, and may further include a magnesium source powder and a silicon source powder.
  • the aluminum source powder is a powder of a compound that becomes an aluminum component constituting the partition wall.
  • Examples of the aluminum source powder include alumina (aluminum oxide) powder.
  • Examples of the crystal type of alumina include ⁇ -type, ⁇ -type, ⁇ -type, and ⁇ -type, and may be indefinite (amorphous).
  • the crystal type of alumina is preferably ⁇ type.
  • the aluminum source powder may be a powder of a compound that is led to alumina by firing alone in air.
  • a compound that is led to alumina by firing alone in air.
  • examples of such a compound include an aluminum salt, aluminum alkoxide, aluminum hydroxide, metal aluminum and the like.
  • the aluminum salt may be an aluminum inorganic salt with an inorganic acid or an aluminum organic salt with an organic acid.
  • the aluminum inorganic salt include aluminum nitrates such as aluminum nitrate and ammonium aluminum nitrate; aluminum carbonates such as ammonium carbonate aluminum and the like.
  • the aluminum organic salt include aluminum oxalate, aluminum acetate, aluminum stearate, aluminum lactate, and aluminum laurate.
  • aluminum alkoxide examples include, for example, aluminum isopropoxide, aluminum ethoxide, aluminum sec-butoxide, aluminum tert-butoxide and the like.
  • Examples of the aluminum hydroxide crystal type include a gibbsite type, a bayerite type, a norosotrandite type, a boehmite type, and a pseudo-boehmite type, and may be amorphous (amorphous).
  • Examples of amorphous aluminum hydroxide include an aluminum hydrolyzate obtained by hydrolyzing an aqueous solution of a water-soluble aluminum compound such as an aluminum salt or an aluminum alkoxide.
  • the aluminum source powder may be one type or two or more types.
  • the aluminum source powder may contain trace components that are derived from the raw materials or inevitably contained in the production process.
  • the particle size (center particle size, D50) equivalent to a volume-based cumulative percentage of 50% measured by a laser diffraction method is preferably 20 to 60 ⁇ m.
  • D50 of the aluminum source powder is more preferably 25 to 60 ⁇ m.
  • titanium source powder is a powder of a compound that becomes a titanium component constituting the partition walls, and is, for example, a titanium oxide powder.
  • Titanium oxide is, for example, titanium (IV) oxide, titanium (III) oxide, or titanium (II) oxide, and preferably titanium (IV) oxide.
  • the crystal forms of titanium (IV) oxide are anatase, rutile, and brookite.
  • the titanium oxide may be amorphous (amorphous).
  • the titanium oxide is more preferably anatase type or rutile type titanium (IV) oxide.
  • the titanium source powder may be a powder of a compound that is led to titania (titanium oxide) by firing alone in the air.
  • titania titanium oxide
  • titanium salt titanium alkoxide, titanium hydroxide, titanium nitride, titanium sulfide, titanium It is a metal.
  • titanium salt examples include titanium trichloride, titanium tetrachloride, titanium (IV) sulfide, titanium sulfide (VI), and titanium sulfate (IV).
  • Titanium alkoxides include, for example, titanium (IV) ethoxide, titanium (IV) methoxide, titanium (IV) t-butoxide, titanium (IV) isobutoxide, titanium (IV) n-propoxide, titanium (IV) tetraisopropoxide, And these chelating products.
  • the titanium source powder may be one type or two or more types.
  • the titanium source powder may contain a trace component derived from the raw material or unavoidably contained in the production process.
  • the volume-based cumulative particle diameter (D50) measured by laser diffraction method is preferably 0.1 to 25 ⁇ m.
  • the D50 of the titanium source powder is more preferably 1 to 20 ⁇ m in order to achieve a sufficiently low firing shrinkage rate.
  • the titanium source powder may show a bimodal particle size distribution.
  • the particle size of the particles forming the peak having the larger particle size measured by the laser diffraction method is preferably 20 to 50 ⁇ m.
  • the mode diameter of the titanium source powder measured by the laser diffraction method is usually 0.1 to 60 ⁇ m.
  • the molar ratio of the aluminum source powder in terms of Al 2 O 3 (alumina) and the titanium source powder in terms of TiO 2 (titania) in the raw material mixture is preferably 35:65 to 45 : 55, more preferably 40:60 to 45:55.
  • titanium source powder excessively with respect to the aluminum source powder, it becomes possible to more effectively reduce the firing shrinkage rate of the molded body of the raw material mixture.
  • the raw material mixture may further contain a magnesium source powder.
  • the obtained aluminum titanate ceramic fired body is a fired body containing aluminum magnesium titanate crystals.
  • the magnesium source powder is not only magnesia (magnesium oxide) powder but also a powder of a compound introduced into magnesia by firing alone in air. Such compounds are, for example, magnesium salts, magnesium alkoxides, magnesium hydroxide, magnesium nitride, and metallic magnesium.
  • Magnesium salts include, for example, magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium pyrophosphate, magnesium oxalate, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium sulfate, magnesium citrate, magnesium lactate, magnesium stearate, magnesium salicylate , Magnesium myristate, magnesium gluconate, magnesium dimethacrylate, and magnesium benzoate.
  • magnesium alkoxide examples include magnesium methoxide and magnesium ethoxide.
  • the magnesium source powder a powder of a compound serving both as a magnesium source and an aluminum source can be used.
  • a compound is, for example, magnesia spinel (MgAl 2 O 4 ).
  • the magnesium source powder When using a powder of a compound that serves as both a magnesium source and an aluminum source as the magnesium source powder, it is included in the amount of Al 2 O 3 (alumina) equivalent of the aluminum source powder and a compound powder that serves as both the magnesium source and the aluminum source.
  • the molar ratio between the total amount of Al 2 O 3 (alumina) equivalent of the Al component and the amount of TiO 2 (titania) equivalent of the titanium source powder is adjusted to be within the above range in the raw material mixture.
  • the magnesium source powder may be one type or two or more types.
  • the magnesium source powder may contain trace components that are derived from the raw materials or inevitably contained in the production process.
  • the particle size (D50) equivalent to a volume-based cumulative percentage of 50% as measured by a laser diffraction method is preferably 0.5 to 30 ⁇ m.
  • the D50 of the magnesium source powder is more preferably 3 to 20 ⁇ m from the viewpoint of reducing the firing shrinkage of the molded body.
  • the content of magnesium source powder in terms of MgO (magnesia) in the raw material mixture is based on the total amount of aluminum source powder in terms of Al 2 O 3 (alumina) and titanium source powder in terms of TiO 2 (titania).
  • the molar ratio is preferably 0.03 to 0.15, more preferably 0.03 to 0.12.
  • the raw material mixture may further contain a silicon source powder.
  • the silicon source powder is a powder of a compound that becomes a silicon component and is contained in the aluminum titanate ceramic fired body. By using the silicon source powder in combination, a heat-resistant aluminum titanate ceramic fired body is obtained. Is possible.
  • the silicon source powder is, for example, a powder of silicon oxide (silica) such as silicon dioxide or silicon monoxide.
  • the silicon source powder may be a powder of a compound led to silica by firing alone in air.
  • Such compounds are, for example, silicic acid, silicon carbide, silicon nitride, silicon sulfide, silicon tetrachloride, silicon acetate, sodium silicate, sodium orthosilicate, feldspar, glass frit, preferably feldspar, glass frit, industrially Glass frit is more preferable because it is easily available and has a stable composition. Glass frit refers to flakes or powdery glass obtained by pulverizing glass. It is also preferable to use a powder made of a mixture of feldspar and glass frit as the silicon source powder.
  • the yield point of the glass frit is 600 ° C. or higher from the viewpoint of further improving the thermal decomposition resistance of the obtained aluminum titanate ceramic fired body.
  • the yield point of the glass frit is determined by measuring the expansion of the glass frit from a low temperature using a thermomechanical analyzer (TMA: Thermo Mechanical Analysis). Is defined.
  • a general silicate glass containing silicate [SiO 2 ] as a main component (50 mass% or more in all components) can be used.
  • the glass constituting the glass frit includes, as other components, alumina [Al 2 O 3 ], sodium oxide [Na 2 O], potassium oxide [K 2 O], calcium oxide [ CaO], magnesia [MgO] and the like may be included.
  • the glass constituting the glass frit may contain ZrO 2 in order to improve the hot water resistance of the glass itself.
  • the silicon source powder may be one type or two or more types.
  • the silicon source powder may contain a trace component derived from the raw material or inevitably contained in the production process.
  • the particle size (D50) equivalent to a 50% cumulative percentage on a volume basis measured by a laser diffraction method is preferably 0.5 to 30 ⁇ m.
  • the D50 of the silicon source powder is more preferably 1 to 20 ⁇ m in order to obtain a fired body having higher mechanical strength by further improving the filling factor of the molded body.
  • the content of the silicon source powder in the raw material mixture is the sum of the aluminum source powder in terms of Al 2 O 3 (alumina) and the titanium source powder in terms of TiO 2 (titania).
  • the amount is usually 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass in terms of SiO 2 (silica) with respect to 100 parts by mass.
  • a compound containing two or more metal elements among titanium, aluminum, silicon and magnesium as a raw material powder such as a composite oxide such as magnesia spinel (MgAl 2 O 4 )
  • the compound can be considered to be the same as the raw material in which the respective metal source compounds are mixed. Based on such an idea, the content of the aluminum source, the titanium source, the magnesium source and the silicon source in the raw material mixture is adjusted within the above range.
  • the raw material mixture may contain aluminum titanate or aluminum magnesium titanate.
  • the aluminum magnesium titanate when aluminum magnesium titanate is used as a constituent of the raw material mixture, the aluminum magnesium titanate contains a titanium source, an aluminum source and magnesium. Corresponds to a raw material mixture that also has a source.
  • Aluminum titanate or aluminum magnesium titanate may be prepared from a honeycomb filter obtained by this production method.
  • the honeycomb filter obtained by the present manufacturing method is damaged, the damaged honeycomb filter or its fragments can be pulverized and used.
  • the powder obtained by pulverization can be aluminum magnesium titanate powder.
  • the pore forming agent those formed by a material that disappears at a temperature lower than the temperature at which the molded body is degreased and fired in the firing step can be used.
  • the hole forming agent disappears due to combustion or the like.
  • a space is created at the location where the pore-forming agent was present, and the ceramic powder located between the spaces shrinks during firing, so that a communication hole through which fluid can flow is formed in the partition wall. Can be formed.
  • the pore-forming agent is, for example, corn starch, barley starch, wheat starch, tapioca starch, bean starch, rice starch, pea starch, coral starch, canna starch, potato starch (potato starch).
  • the average particle diameter of the pore forming agent is, for example, 5 to 25 ⁇ m.
  • the content of the hole forming agent is, for example, 1 to 25 parts by mass with respect to 100 parts by mass of the ceramic powder.
  • the binder is, for example, celluloses such as methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose; alcohols such as polyvinyl alcohol; salts such as lignin sulfonate; waxes such as paraffin wax and microcrystalline wax.
  • Content of the binder in a raw material mixture is 20 mass parts or less with respect to 100 mass parts of ceramic powder, for example.
  • plasticizer examples include alcohols such as glycerin; higher fatty acids such as caprylic acid, lauric acid, palmitic acid, alginic acid, oleic acid, and stearic acid; stearic acid metal salts such as Al stearate, and polyoxyalkylene alkyl ethers.
  • the content of the plasticizer in the raw material mixture is, for example, 0 to 10 parts by mass with respect to 100 parts by mass of the ceramic powder.
  • the dispersant examples include inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, citric acid, acetic acid, malic acid, and lactic acid; alcohols such as methanol, ethanol, and propanol; interfaces such as ammonium polycarboxylate It is an activator.
  • the content of the dispersant in the raw material mixture is, for example, 0 to 20 parts by mass with respect to 100 parts by mass of the ceramic powder.
  • the solvent is, for example, water, and ion-exchanged water is preferable in terms of few impurities.
  • the content of the solvent is, for example, 10 to 100 parts by mass with respect to 100 parts by mass of the ceramic powder.
  • a ceramic molded body having a predetermined shape having a honeycomb structure is obtained.
  • a so-called extrusion molding method in which the raw material mixture is extruded from a die while being kneaded by a single screw extruder can be employed.
  • Step (c): Firing step In the step (c), degreasing (calcination) for removing a hole forming agent or the like contained in the molded body (in the raw material mixture) may be performed before firing the molded body. Degreasing is performed in an atmosphere having an oxygen concentration of 0.1% or less.
  • % used as a unit of oxygen concentration means “volume%”.
  • an atmosphere examples include an inert gas atmosphere such as nitrogen gas and argon gas, a reducing gas atmosphere such as carbon monoxide gas and hydrogen gas, and a vacuum.
  • firing may be performed in an atmosphere with a low water vapor partial pressure, or steaming with charcoal may reduce the oxygen concentration.
  • the maximum temperature for degreasing is preferably 700 to 1100 ° C, more preferably 800 to 1000 ° C.
  • the maximum degreasing temperature is preferably 700 to 1100 ° C, more preferably 800 to 1000 ° C.
  • Degreasing is used for normal firing of tubular electric furnace, box-type electric furnace, tunnel furnace, far-infrared furnace, microwave heating furnace, shaft furnace, reflection furnace, rotary furnace, roller hearth furnace, gas combustion furnace, etc. A similar furnace is used. Degreasing may be performed batchwise or continuously. Moreover, degreasing may be performed by a stationary method or a fluid method.
  • the time required for degreasing may be a time sufficient for a part of the organic component contained in the ceramic molded body to disappear, and preferably 90 to 99% by mass of the organic component contained in the ceramic molded body. It is time to disappear. Specifically, although it varies depending on the amount of the raw material mixture, the type of furnace used for degreasing, temperature conditions, atmosphere, etc., the time for keeping at the maximum temperature is usually 1 minute to 10 hours, preferably 1 to 7 hours. is there.
  • the ceramic molded body is fired after the above degreasing.
  • the firing temperature is usually 1300 ° C. or higher, preferably 1400 ° C. or higher.
  • a calcination temperature is 1650 degrees C or less normally, Preferably it is 1550 degrees C or less.
  • the rate of temperature increase up to the firing temperature is not particularly limited, but is usually 1 to 500 ° C./hour.
  • the silicon source powder it is preferable to provide a step of holding at a temperature range of 1100 to 1300 ° C. for 3 hours or more before the firing step. Thereby, melting and diffusion of the silicon source powder can be promoted.
  • Calcination is preferably performed in an atmosphere having an oxygen concentration of 1 to 6%.
  • oxygen concentration is preferably 1% or more because carbide (soot) derived from organic components does not remain in the obtained aluminum titanate-based ceramic fired body.
  • the aluminum source powder, titanium source powder, magnesium source powder and silicon source powder it may be fired in an inert gas such as nitrogen gas or argon gas, or carbon monoxide You may bake in reducing gas, such as gas and hydrogen gas. Further, the firing may be performed in an atmosphere in which the water vapor partial pressure is lowered.
  • an inert gas such as nitrogen gas or argon gas, or carbon monoxide
  • reducing gas such as gas and hydrogen gas.
  • Firing is usually performed using conventional equipment such as a tubular electric furnace, box-type electric furnace, tunnel furnace, far-infrared furnace, microwave heating furnace, shaft furnace, reflection furnace, rotary furnace, roller hearth furnace, gas combustion furnace, etc. Done. Firing may be performed batchwise or continuously. Moreover, baking may be performed by a stationary type or may be performed by a fluid type.
  • the firing time may be a time sufficient for the ceramic molded body to transition to the aluminum titanate-based crystal, and varies depending on the amount of raw material, type of firing furnace, firing temperature, firing atmosphere, etc., but usually 10 minutes to 24 hours.
  • Step (d): Sealing step] Step (d) is performed between step (b) and step (c) or after step (c).
  • step (d) between step (b) and step (c)
  • the sealing material is fired together with the ceramic molded body to obtain a sealing portion that seals one end of the flow path.
  • the sealing material the same mixture as the raw material mixture can be used.
  • a honeycomb filter can be obtained through the above steps.
  • the honeycomb filter has a shape that substantially maintains the shape of the molded body immediately after the molding in the step (b), but after the step (b), the step (c) or the step (d), a grinding process or the like is performed, It can also be processed into a desired shape.
  • Example 1 Raw material powder of aluminum magnesium titanate (Al 2 O 3 powder, TiO 2 powder, MgO powder), SiO 2 powder, ceramic powder having a composite phase of aluminum magnesium titanate, alumina and aluminosilicate glass (composition formula at the time of preparation) : 41.4Al 2 O 3 -49.9TiO 2 -5.4MgO-3.3SiO 2 , where the numerical values represent molar ratios), pore formers, organic binders, lubricants, plasticizers, dispersants and water
  • a raw material mixture containing (solvent) was prepared. The content of main components in the raw material mixture was adjusted to the following values.
  • a columnar honeycomb filter (DPF) having the structure shown in FIGS. 1 and 2 was produced by extruding after kneading the above raw material mixture.
  • the aluminum titanate conversion rate (AT conversion rate) of the honeycomb filter of Example 1 was measured and found to be 100%.
  • AT conversion rate (%) I AT / (I T + I AT ) ⁇ 100 (1)
  • the length of the honeycomb filter in the axial direction of the flow path was 152 mm.
  • the outer diameter of the honeycomb filter was 144 mm.
  • the density of the flow path (cell density) was 300 cpsi.
  • the cross-sectional inner diameter (the length of one side of the square) of the flow path was 1.2 mm.
  • the thickness of the partition between the flow paths was 0.30 mm.
  • the porosity of the partition walls was 45% by volume, and the pore diameter of the partition walls was 15 ⁇ m.
  • a honeycomb filter (DPF) having a plurality of parallel flow paths partitioned by partition walls made of SiC was prepared.
  • the length of the honeycomb filter in the axial direction of the flow path was 140 mm.
  • the outer diameter of the honeycomb filter was 144 mm.
  • the partition wall thickness between the channels was 0.33 mm.
  • Example 2 A honeycomb filter (DPF) having a plurality of parallel flow paths partitioned by partition walls made of SiC was prepared.
  • the length of the honeycomb filter in the axial direction of the flow path was 152 mm.
  • the outer diameter of the honeycomb filter was 144 mm.
  • the thickness of the partition between the flow paths was 0.28 mm.
  • ⁇ Surface roughness measurement> One flow path from each honeycomb filter was selected as a measurement target. Three measurement regions were arbitrarily selected from one inner wall of the flow channel to be measured, and the maximum height Rz and the arithmetic average roughness Ra of each measurement region were measured in accordance with JIS B 0601: 2001. The surface shape of each measurement region was measured with a Keyence laser microscope VK-8500. An example of the surface shape of the measurement region is shown in FIG. The size of the measurement area was 298 ⁇ m ⁇ 224 ⁇ m in all cases. Table 1 shows the measurement results of the maximum height Rz and the arithmetic average roughness Ra.
  • FIG. 4 shows a schematic diagram of a pressure loss measuring apparatus.
  • a soot generator (trade name: REXS, manufactured by Matter Engineering) 200 and a large compressor device 210 were used.
  • One end face of the honeycomb filter was connected to the soot generating device 200, and the compressor device 210 was connected to a pipe connecting the honeycomb filter and the soot generating device 200.
  • soot generator 200 propane gas was supplied at a flow rate of 2 L / min, nitrogen gas was supplied at a flow rate of 2 L / min, and air was supplied at a flow rate of 1000 L / min.
  • the soot generated from the soot generator 200 is artificial soot generated by incomplete combustion of propane gas.
  • the average particle diameter of soot is controlled by the air flow rate, oxygen concentration, and the like. can do. In the measurement, the average particle diameter of the soot was adjusted to about 90 nm.
  • the flow rate of air containing soot was adjusted to 200 Nm 3 h ⁇ 1 by the compressor device 210.
  • FIG. 5 shows the results of measuring the pressure loss with the increase in the soot deposition amount using the honeycomb filters of Example 1 and Comparative Examples 1 and 2. As shown in FIG. 5, in Example 1, it is confirmed that the pressure loss value is smaller than in Comparative Examples 1 and 2. Moreover, in Example 1, it is confirmed that the increase amount of the pressure loss accompanying the increase in the amount of soot deposition is small compared with Comparative Examples 1 and 2.
  • DESCRIPTION OF SYMBOLS 100 ... Honeycomb filter, 110 ... Channel, 110a ... Channel (first channel), 110b ... Channel (second channel), 115a, 115b ... Inner wall, 120 ... Partition, A, B ... Area.

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Abstract

La présente invention concerne un filtre en nid d'abeilles (100) comprenant une pluralité de canaux d'écoulement parallèles (110) divisés par des parois de séparation poreuse (120), la pluralité de canaux d'écoulement (110) comprenant des canaux d'écoulement (110a) et d'autres canaux d'écoulement (110b) adjacents à ceux-ci, les sections d'extrémité des canaux d'écoulement (110a) étant scellées sur un côté du filtre en nid d'abeilles (100), et les sections d'extrémité des autres canaux d'écoulement (110b) étant scellées sur l'autre côté du filtre en nid d'abeilles (100), et la hauteur maximale (Rz) d'au moins une parmi une région (A) dans les parois de séparation (115a) des canaux d'écoulement (110a) et une région (B) dans les parois de séparation (115b) des autres canaux d'écoulement (110b) est inférieure à 55,00 μm.
PCT/JP2012/070079 2011-08-12 2012-08-07 Filtre en nid d'abeilles WO2013024744A1 (fr)

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JP2019103951A (ja) * 2017-12-08 2019-06-27 日本碍子株式会社 フィルタ
CN113597334A (zh) * 2019-03-28 2021-11-02 日本碍子株式会社 多孔质复合体

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JP7198626B2 (ja) * 2018-10-12 2023-01-04 イビデン株式会社 ハニカム構造体
JP6940787B2 (ja) 2019-07-31 2021-09-29 株式会社デンソー 排ガス浄化フィルタ

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JP2003001029A (ja) * 2001-06-18 2003-01-07 Hitachi Metals Ltd 多孔質セラミックハニカムフィルタ
WO2004076027A1 (fr) * 2003-02-28 2004-09-10 Ibiden Co., Ltd. Structure ceramique en nids d'abeilles
JP2004255377A (ja) * 2003-02-07 2004-09-16 Hitachi Metals Ltd セラミックハニカム構造体
WO2004111398A1 (fr) * 2003-06-05 2004-12-23 Ibiden Co., Ltd. Corps a structure en nids-d'abeilles
JP2005324154A (ja) * 2004-05-17 2005-11-24 Hitachi Metals Ltd セラミックハニカム構造体

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JP2003001029A (ja) * 2001-06-18 2003-01-07 Hitachi Metals Ltd 多孔質セラミックハニカムフィルタ
JP2004255377A (ja) * 2003-02-07 2004-09-16 Hitachi Metals Ltd セラミックハニカム構造体
WO2004076027A1 (fr) * 2003-02-28 2004-09-10 Ibiden Co., Ltd. Structure ceramique en nids d'abeilles
WO2004111398A1 (fr) * 2003-06-05 2004-12-23 Ibiden Co., Ltd. Corps a structure en nids-d'abeilles
JP2005324154A (ja) * 2004-05-17 2005-11-24 Hitachi Metals Ltd セラミックハニカム構造体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019103951A (ja) * 2017-12-08 2019-06-27 日本碍子株式会社 フィルタ
CN113597334A (zh) * 2019-03-28 2021-11-02 日本碍子株式会社 多孔质复合体

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