WO2013027570A1 - Procédé de production d'une structure en nid d'abeilles - Google Patents

Procédé de production d'une structure en nid d'abeilles Download PDF

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Publication number
WO2013027570A1
WO2013027570A1 PCT/JP2012/070075 JP2012070075W WO2013027570A1 WO 2013027570 A1 WO2013027570 A1 WO 2013027570A1 JP 2012070075 W JP2012070075 W JP 2012070075W WO 2013027570 A1 WO2013027570 A1 WO 2013027570A1
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Prior art keywords
end surface
honeycomb structure
sintering
molded body
side end
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PCT/JP2012/070075
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English (en)
Japanese (ja)
Inventor
鈴木　敬一郎
淳 池下
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住友化学株式会社
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Publication of WO2013027570A1 publication Critical patent/WO2013027570A1/fr

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    • 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
    • B01D46/2486—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure characterised by the shapes or configurations
    • B01D46/2492—Hexagonal
    • 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
    • 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
    • B01D46/0001—Making filtering elements
    • 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
    • B01D46/2459—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the plugs
    • 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
    • B01D46/247—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the 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
    • B01D46/2476—Monolithic structures
    • 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
    • B01D46/2484—Cell density, area or aspect ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/248—Supports for drying
    • 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
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • 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
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass

Definitions

  • One embodiment of the present invention relates to a method for manufacturing a honeycomb structure, and relates to a method for manufacturing a honeycomb structure in which a green molded body is sintered to manufacture a honeycomb structure.
  • the honeycomb structure is often used by being housed in a container such as in a discharge pipe. Therefore, for example, in Patent Document 1, when the honeycomb structure is accommodated in a container by providing an uneven portion on the outer peripheral surface of the outer peripheral wall of the honeycomb structure, the honeycomb structure is not easily damaged and does not shift.
  • a honeycomb structure as described above is disclosed.
  • the dimensional accuracy of the diesel particle filter itself is required.
  • the side surface of the cylindrical diesel particle filter is exactly perpendicular to the end surface, and the diameter of the diesel particle filter is uniform from one end surface to the other end surface.
  • the diameter of the honeycomb structure manufactured by sintering the green molded body contracts smaller on one end face side than on the other end face side, and the diameter may not be uniform. It is rare.
  • One embodiment of the present invention has been made in view of the above problems, and an object thereof is to provide a method for manufacturing a honeycomb structure capable of improving the dimensional accuracy of the honeycomb structure after sintering.
  • the green molded body In the cross section perpendicular to the first end face and the second end face, among the second end faces, the green molded body is supported while supporting the side where the end portion of the through hole is closed by the sealing portion and having a large cross-sectional area ratio.
  • a honeycomb structure manufacturing method in which a honeycomb structure is manufactured by sintering. That.
  • a plurality of through-holes that are substantially parallel to each other are formed, the honeycomb-shaped columnar body having partition walls that separate the plurality of through-holes, and a sealing portion that closes one end of the through-hole.
  • some of the through holes are closed at the first end surface of the first end surface and the second end surface of the columnar body substantially orthogonal to the through hole, open at the second end surface, and other through holes
  • the hole is a method for manufacturing a honeycomb structure by manufacturing a honeycomb structure by sintering a green molded body that is closed by a sealing portion at a second end surface and opened at the first end surface.
  • the green molded body is sintered while supporting the side where the end portion of the through hole is closed by the sealing portion and having a large cross-sectional area ratio.
  • a honeycomb structure is manufactured.
  • the side where the end portion of the through hole is closed by the sealing portion has a larger ratio. At this time, the shrinkage is large and the dimensional accuracy may be deteriorated.
  • the side having a large ratio of the cross-sectional area in which the end portion of the through hole is blocked by the sealing portion is supported.
  • shrinkage during the sintering on the side can be suppressed, and the dimensional accuracy of the honeycomb structure after sintering can be improved.
  • a honeycomb structure can be manufactured by sintering a green molded body while placing the green molded body with the larger side facing down.
  • the end portion of the through hole is blocked by the sealing portion in the cross section perpendicular to the first end surface and the second end surface within the first end surface and the second end surface in the sintering furnace.
  • a honeycomb structure is manufactured by sintering a green molded body while placing the green molded body on the lower side of the area having a large area ratio.
  • the ratio of the cross-sectional area in which the end portion of the through hole is closed by the sealing portion can suppress shrinkage during sintering on the side and improve the dimensional accuracy of the honeycomb structure after sintering. it can.
  • the end portion of the through hole is blocked by the sealing portion in the cross section perpendicular to the first end surface and the second end surface within the first end surface and the second end surface in the sintering furnace.
  • a honeycomb structure is manufactured by sintering a green molded body while supporting a side having a large area ratio with a support. For this reason, in the cross section perpendicular to the first end face and the second end face in the first end face and the second end face within the sintering furnace, the end area of the through hole is closed by the sealing portion. Dimensional accuracy of the honeycomb structure after sintering while suppressing the shrinkage during the sintering of the side while placing the green molded body in the sintering furnace more freely without lowering the higher ratio side Can be improved.
  • the ratio of the cross-sectional area in which the end portion of the through hole is blocked by the sealing portion is large in the first end surface and the second end surface.
  • the green molded body is sintered while the temperature on the side is set to be lower than the temperature on the side where the end portion of the through hole is closed by the sealing portion, and the honeycomb structure is manufactured.
  • the ratio of the cross-sectional area in which the end portion of the through hole is closed by the sealing portion is large and shrinks during sintering.
  • the partition walls separating the plurality of through holes have a hexagonal shape, and the end portions of the through holes are sealed in the cross section perpendicular to the first end surface and the second end surface among the first end surface and the second end surface.
  • the through holes are adjacent to each other on the side where the ratio of the cross-sectional area closed by the part is large.
  • the sealing portions may not be adjacent to each other.
  • the partition walls separating the plurality of through holes have a hexagonal shape, and in the cross section perpendicular to the first end face and the second end face among the first end face and the second end face,
  • the side where the ratio of the cross-sectional area where the end portion is closed by the sealing portion is large is that the sealing portions are adjacent to each other, and the cross section perpendicular to the first end surface and the second end surface among the first end surface and the second end surface.
  • the sealing portions are not adjacent to each other on the side where the ratio of the cross-sectional area where the end portion of the through hole is closed by the sealing portion.
  • the green molded body having such a structure has a large ratio of shrinkage due to sintering on the side having a larger cross-sectional area in which the end portion of the through hole is closed by the sealing portion.
  • a highly accurate honeycomb structure can be manufactured.
  • the partition wall and the sealing portion are made of porous ceramics. For this reason, it can have a favorable characteristic as a diesel particulate filter.
  • partition wall and the sealing portion can be made of porous aluminum titanate containing magnesium and silicon.
  • a diesel particle filter made of a sintered magnesium magnesium titanate has an extremely small coefficient of thermal expansion, a high melting point, and a regeneration compared to a diesel particle filter made of SiC, cordierite or aluminum titanate alone. It has excellent thermal shock resistance at the time, and is excellent in that the limit accumulation amount of soot is large, so that it can have better characteristics as a diesel particle filter.
  • the dimensional accuracy of the honeycomb structure after sintering can be improved.
  • (A) is a perspective view of the green molded object of the honeycomb structure which concerns on embodiment, (b) is a front view of the entrance-side end surface of the columnar body of (a).
  • (A) is a perspective view of the green molded object of the honeycomb structure which concerns on embodiment, (b) is a front view of the exit side end surface of the columnar body of (a).
  • 3 is a cross-sectional view taken along line III-III in FIG. It is a perspective view which shows the aspect which mounts a green molded object on the shelf board in the furnace in embodiment. It is a perspective view which shows the aspect which makes the support tool in the furnace in embodiment support a green molded object.
  • (A) and (b) show that when the green molded body is placed on the shelf plate in the furnace and sintered with the end face on the inlet side facing down and the end face on the outlet side facing upward, It is a figure which shows the phenomenon in which the dimensional accuracy of an exit side end surface deteriorates. It is a graph which shows the average diameter with respect to the measurement height of the green molded object before sintering of an experiment example. It is a graph which shows the average diameter with respect to the measurement height of the honeycomb structure after sintering of an experiment example. It is a graph which shows the average diameter with respect to the measurement height of the green molded object before sintering of a comparative example. It is a graph which shows the average diameter with respect to the measurement height of the honeycomb structure after sintering of a comparative example.
  • the honeycomb structure 100 of the embodiment of the present invention shown in FIG. 3 is obtained by sintering the green molded body 70 shown in FIGS. 1A and 1B and FIGS. 2A and 2B by the method of the present embodiment. Is obtained.
  • the green molded body means a raw molded body before being sintered.
  • the honeycomb structure 100 of the present embodiment is installed by being pushed into the exhaust pipe of an automobile and used as a diesel particle filter.
  • the green molded body 70 is a columnar body (cylindrical body) having a honeycomb structure.
  • the green molded body 70 which is a columnar body, is parallel to the central axis and has a plurality of regular hexagonal partition walls 70d. That is, the green molded body 70 has a honeycomb structure in which regular hexagons are arranged without gaps in a cross section perpendicular to the central axis direction.
  • the green molded body 70 is formed with a large number of through holes 70c (flow paths) extending in the same direction (center axis direction), and the partition walls 70d separate the through holes 70c.
  • Each through hole 70c is perpendicular to the inlet side end surface 70a and the outlet side end surface 70b of the green molded body 70.
  • the green molded body 70 has substantially the same diameter from the inlet side end surface 70a to the outlet side end surface 70b.
  • the through-hole 70c and the partition wall 70d reduce the pressure loss at the time of deposition of the trapped substance because the fluid containing the trapped substance can easily flow from the gas inflow side channel to the gas outflow side channel. From the viewpoint of facilitating reduction, a regular hexagonal shape in which the lengths of the sides forming the cross section are substantially equal to each other may be used, but a flat hexagonal shape may also be used.
  • some of the plurality of through-holes 70c are closed with a sealing material 70e on the inlet-side end surface 70a orthogonal to the through-holes.
  • a sealing material 70e on the inlet-side end surface 70a orthogonal to the through-holes.
  • the through hole 70c closed by the sealing material 70e is not adjacent to the other through hole 70c closed by the sealing material 70e. Adjacent to the through-hole 70c not blocked by 70e.
  • the six through holes 70c closed by the sealing material 70e surround the through holes 70c not closed by the sealing material 70e. So that they are adjacent to each other.
  • the plurality of through holes 70c are closed with the sealing material 70e on either one of the inlet side end surface 70a and the outlet side end surface 70b.
  • the inlet side end surface 70a in a part of the through hole 70c is opened as an inflow port of the gas G, and the through hole opened at the inlet side end surface 70a.
  • An outlet side end surface 70b of the through hole 70c adjacent to 70c is opened as a gas G outlet.
  • the green molded body 70 is obtained by molding a raw material mixture prepared by mixing an inorganic compound powder, a pore-forming agent, an organic binder, a solvent and the like with a kneader or the like.
  • the inorganic compound powder includes a raw material powder of an aluminum titanate ceramic.
  • the raw material powder of ceramics becomes a ceramic by sintering.
  • the raw material powder of the aluminum titanate ceramic is, for example, a titanium source powder and an aluminum source powder.
  • the inorganic compound powder may further contain a magnesium source powder and a silicon source powder.
  • the raw material mixture may include the aluminum titanate ceramic itself. Thereby, the shrinkage
  • the aluminum titanate ceramic is, for example, aluminum titanate or aluminum magnesium titanate.
  • the aluminum source is a compound that becomes an aluminum component constituting the aluminum titanate sintered body.
  • Examples of the aluminum source include alumina (aluminum oxide).
  • Examples of the crystal type of alumina include ⁇ -type, ⁇ -type, ⁇ -type, and ⁇ -type, and may be indefinite (amorphous). For example, ⁇ -type alumina is used.
  • the aluminum source may be a compound that is led to alumina by being sintered alone in air.
  • Examples of such a compound include an aluminum salt, aluminum alkoxide, aluminum hydroxide, and metal aluminum.
  • the aluminum salt may be an inorganic salt with an inorganic acid or an organic salt with an organic acid.
  • the aluminum inorganic salt include aluminum nitrates such as aluminum nitrate and ammonium aluminum nitrate, and aluminum carbonates such as ammonium aluminum carbonate.
  • the aluminum organic salt include aluminum oxalate, aluminum acetate, aluminum stearate, aluminum lactate, and aluminum laurate.
  • aluminum alkoxide examples include 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 the 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.
  • an aluminum source only 1 type may be used and 2 or more types may be used together.
  • alumina is used as the aluminum source, and ⁇ -type alumina is used.
  • the aluminum source may contain trace components derived from the raw materials or inevitably contained in the production process.
  • the particle size of the aluminum source powder is not particularly limited.
  • the particle diameter of the aluminum source powder corresponding to a volume-based cumulative percentage of 50% measured by laser diffraction method may be in the range of 20 to 60 ⁇ m. This particle diameter is also called D50 or average particle diameter. From the viewpoint of reducing shrinkage during sintering, an aluminum source powder having a D50 in the range of 30 to 60 ⁇ m can be used.
  • An alumina sol or a silica sol described later can be added to the raw material mixture.
  • fine particles in the raw material mixture are adsorbed to each other, and the amount of particles having a particle diameter of 0.1 ⁇ m or less in the green molded body is reduced to an inorganic compound powder (solid content).
  • the strength of the molded body after degreasing at 500 ° C. can be, for example, 0.2 kgf or more.
  • the alumina sol is a colloid using fine particle alumina as a dispersoid and a liquid as a dispersion medium.
  • Alumina sol can be used alone as an aluminum source, but can also be used in combination with other aluminum sources.
  • the dispersion medium of alumina sol is removed by evaporation or the like at the time of mixing or calcination, for example.
  • the dispersion medium for the alumina sol examples include aqueous solutions and various organic solvents such as aqueous hydrochloric acid, aqueous acetic acid, aqueous nitric acid, alcohol, xylene, toluene, and methyl isobutyl ketone.
  • aqueous hydrochloric acid aqueous hydrochloric acid
  • aqueous acetic acid aqueous nitric acid
  • alcohol xylene, toluene
  • methyl isobutyl ketone examples include aqueous solutions and various organic solvents such as aqueous hydrochloric acid, aqueous acetic acid, aqueous nitric acid, alcohol, xylene, toluene, and methyl isobutyl ketone.
  • a colloidal alumina sol having an average particle diameter of 1 to 100 nm is used.
  • Examples of commercially available products of alumina sol include “Alumina sol 100”, “Alumina sol 200”, “Alumina sol 520” manufactured by Nissan Chemical Industries, Ltd., “NanoTekAl 2 O 3 ” manufactured by CI Kasei. Among these, “Alumina sol 200” manufactured by Nissan Chemical Industries, Ltd. can be used.
  • the alumina sol can be used in an amount of 0 to 10 parts by weight and 0 to 5 parts by weight based on 100 parts by weight of the inorganic compound powder (solid content). Two or more kinds of alumina sols may be mixed and used.
  • the titanium source is a compound that becomes a titanium component constituting the aluminum titanate sintered body, and examples of such a compound include titanium oxide.
  • examples of titanium oxide include titanium (IV) oxide, titanium (III) oxide, and titanium (II) oxide.
  • titanium (IV) oxide is used.
  • Examples of the crystal form of titanium (IV) oxide include anatase type, rutile type, brookite type and the like, and may be indefinite (amorphous).
  • the titanium oxide can be anatase type or rutile type titanium (IV) oxide.
  • the titanium source may be a compound that is led to titania (titanium oxide) by sintering alone in air.
  • titania titanium oxide
  • examples of such compounds include titanium salts, titanium alkoxides, titanium hydroxide, titanium nitride, titanium sulfide, titanium metal and the like.
  • titanium source only 1 type may be used and 2 or more types may be used together.
  • titanium oxide is used, for example, titanium (IV) oxide.
  • a titanium source can contain the trace component contained unavoidable in the raw material origin or manufacturing process.
  • the particle size of the titanium source powder is not particularly limited.
  • the particle diameter (D50) of the titanium source powder corresponding to a volume-based cumulative percentage of 50% as measured by a laser diffraction method may be in the range of 0.5 to 25 ⁇ m.
  • the D50 of the titanium source powder can be in the range of 1 to 20 ⁇ m.
  • the titanium source powder may show a bimodal particle size distribution. When using a titanium source powder showing such a bimodal particle size distribution, the particle size distribution measured by the laser diffraction method is used.
  • the particle diameter of the peak with the larger particle diameter can be in the range of 20 to 50 ⁇ m.
  • the mode diameter of the titanium source powder measured by the laser diffraction method is not particularly limited, but may be in the range of 0.3 to 60 ⁇ m.
  • the raw material mixture may contain a magnesium source.
  • the honeycomb structure 200 manufactured from the green molded body 100 containing a magnesium source is a sintered body of aluminum magnesium titanate crystals.
  • magnesium source examples include magnesia (magnesium oxide) and a compound that is led to magnesia by sintering alone in air.
  • magnesia magnesium oxide
  • a compound that is led to magnesia by sintering alone in air examples include magnesium salt, magnesium alkoxide, magnesium hydroxide, magnesium nitride, metal magnesium and the like.
  • magnesium salts include magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium pyrophosphate, magnesium oxalate, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium sulfate, magnesium citrate, magnesium lactate, magnesium stearate, Examples include magnesium salicylate, magnesium myristate, magnesium gluconate, magnesium dimethacrylate, and magnesium benzoate.
  • magnesium alkoxide examples include magnesium methoxide and magnesium ethoxide.
  • a magnesium source can contain the trace component contained unavoidable in the raw material origin or manufacturing process.
  • magnesium source a compound serving both as a magnesium source and an aluminum source can also be used.
  • An example of such a compound is magnesia spinel (MgAl 2 O 4 ).
  • the particle size of the magnesium source powder is not particularly limited.
  • the particle diameter (D50) of the magnesium source powder corresponding to a volume-based cumulative percentage of 50% measured by laser diffraction may be in the range of 0.5 to 30 ⁇ m. From the viewpoint of reducing shrinkage during sintering, a magnesium source powder having a D50 in the range of 3 to 20 ⁇ m can be used.
  • the molar amount of the magnesium source in terms of MgO (magnesia) in the green molded body is based on the total molar amount of the aluminum source in terms of Al 2 O 3 (alumina) and the titanium source in terms of TiO 2 (titania). 0.03 to 0.15, for example, 0.03 to 0.12.
  • the raw material mixture may further contain a silicon source.
  • the silicon source is a compound that becomes a silicon component and is contained in the aluminum titanate sintered body. By using the silicon source in combination, it becomes possible to obtain an aluminum titanate sintered body with improved heat resistance.
  • Examples of the silicon source include silicon oxides (silica) such as silicon dioxide and silicon monoxide.
  • the silicon source may be a compound that is led to silica by sintering alone in air.
  • examples of such compounds include silicic acid, silicon carbide, silicon nitride, silicon sulfide, silicon tetrachloride, silicon acetate, sodium silicate, sodium orthosilicate, feldspar, and glass frit.
  • feldspar, glass frit, etc. are used, and glass frit is used because it is easily available industrially and has a stable composition.
  • Glass frit means flakes or powdery glass obtained by pulverizing glass.
  • As the silicon source a powder made of a mixture of feldspar and glass frit can also be used.
  • the silicon source is glass frit
  • the one having a yield point of 700 ° C. or higher can be used from the viewpoint of further improving the heat decomposition resistance of the obtained aluminum titanate sintered body.
  • the yield point of the glass frit is defined as a temperature (° C.) at which the expansion of the glass frit is measured from a low temperature by using a thermomechanical analyzer (TMA: Thermo Mechanical Analysis), and then the expansion stops.
  • a general silicate glass containing silicate (SiO 2 ) as a main component (0% by weight or more in all components) can be used.
  • the glass constituting the glass frit includes other components such as 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.
  • Such glass is, for example, aluminosilicate glass.
  • the glass constituting the glass frit may contain ZrO 2 in order to improve the hot water resistance of the glass itself.
  • silicon source only 1 type may be used and 2 or more types may be used together.
  • the particle size of the silicon source powder is not particularly limited.
  • the particle diameter (D50) of the silicon source corresponding to a volume-based cumulative percentage of 50% measured by laser diffraction method may be in the range of 0.5 to 30 ⁇ m.
  • the D50 of the silicon source can be in the range of 1 to 20 ⁇ m.
  • the content of the silicon source in the raw material mixture is 100 parts by weight of the total amount of the aluminum source in terms of Al 2 O 3 (alumina) and the titanium source in terms of TiO 2 (titania).
  • the silicon source in terms of SiO 2 (silica) it is usually 0.1 to 10 parts by weight, for example, 5 parts by weight or less.
  • content of the silicon source in a raw material mixture can be 2 to 5 weight% in the inorganic compound source contained in a raw material mixture.
  • the silicon source may contain trace components that are derived from the raw materials or inevitably contained in the production process.
  • a composite oxide such as magnesia spinel (MgAl 2 O 4 )
  • a compound containing two or more metal elements among titanium, aluminum, silicon, and magnesium can be used as a raw material.
  • alumina sol and / or silica sol is added to the raw material mixture and mixed. can do.
  • Silica sol is a colloid using fine particle silica as a dispersoid and liquid as a dispersion medium. Silica sol can be used alone as a silicon source, but can be used in combination with other silica sources. The dispersion medium of silica nasol is removed by evaporation or the like at the time of mixing or calcination, for example.
  • silica sol dispersion medium examples include aqueous solutions and various organic solvents such as an aqueous ammonia solution, alcohol, xylene, toluene, and triglyceride.
  • a colloidal silica sol having an average particle diameter of 1 to 100 nm is used.
  • silica sol examples include “Snowtex 20, 30, 40, 50, N, O, S, C, 20L, OL, XS, XL, YL, ZL, QAS-40, LSS manufactured by Nissan Chemical Industries, Ltd. -35, LSS-45 "," Adelite AT-20, AT-30, AT-40, AT-50, AT-20N, AT-20A, AT-30A, AT-20Q, AT-300, manufactured by Asahi Denka Co., Ltd. “AT-300Q”, “Cataloid S-20L, S-20H, S-30L, S-30H, SI-30, SI-40, SI-50, SI-350, SI-500, SI-manufactured by Catalyst Kasei Kogyo Co., Ltd.
  • the content of the silica sol in the raw material mixture may be 0 to 10 parts by weight and 0 to 5 parts by weight in solid content with respect to 100 parts by weight of the inorganic compound powder (solid content). Two or more kinds of silica sols may be mixed and used.
  • the organic binder can be a water-soluble organic binder.
  • the water-soluble organic binder include celluloses such as methylcellulose, hydroxypropylmethylcellulose, and hydroxyethylmethylcellulose; alcohols such as polyvinyl alcohol; salts such as lignin sulfonate.
  • the amount of the organic binder is usually 20 parts by weight or less, for example, 15 parts by weight or less and 6 parts by weight with respect to 100 parts by weight of the inorganic compound powder. Further, the lower limit amount of the organic binder is usually 0.1 parts by weight, for example, 3 parts by weight.
  • solvent for example, alcohols such as methanol, ethanol, butanol and propanol, glycols such as propylene glycol, polypropylene glycol and ethylene glycol, and polar solvents such as water can be used. Among these, ion-exchanged water is used because it can be made of water and has few impurities.
  • the amount of the solvent used is usually 10 to 100 parts by weight, for example 20 to 80 parts by weight, based on 100 parts by weight of the inorganic compound powder.
  • a nonpolar solvent may be used as the solvent.
  • the raw material mixture can contain an organic additive other than the organic binder.
  • organic additives are, for example, pore formers, lubricants and plasticizers, and dispersants.
  • the pore-forming agent examples include carbon materials such as graphite, resins such as polyethylene, polypropylene, and polymethyl methacrylate, plant materials such as starch, nut shells, walnut shells, and corn, ice, and dry ice.
  • the amount of pore-forming agent added is usually 0 to 40 parts by weight, for example 0 to 25 parts by weight, based on 100 parts by weight of the inorganic compound powder.
  • the pore-forming agent disappears when the green molded body is sintered. Therefore, in the aluminum titanate sintered body, micropores are formed at locations where the pore-forming agent was present.
  • Lubricants and plasticizers include alcohols such as glycerin, caprylic acid, lauric acid, palmitic acid, higher fatty acids such as alginate, oleic acid and stearic acid, stearic acid metal salts such as Al stearate; polyoxyalkylene alkyl Examples include ether.
  • the addition amount of the lubricant and the plasticizer is usually 0 to 10 parts by weight, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the inorganic compound 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, and ammonium polycarboxylate. Surfactant etc. are mentioned.
  • the added amount of the dispersant is usually 0 to 20 parts by weight, for example, 2 to 8 parts by weight with respect to 100 parts by weight of the inorganic compound powder.
  • the sealing material 70b includes an aluminum titanate ceramic.
  • the ceramic is, for example, aluminum titanate ceramic powder or particles.
  • the sealing material 70e contains said pore making material, an organic binder, a solvent, etc. similarly to the green molded object 70. FIG. By mixing these components at a predetermined ratio, a pasty sealing material 70e is obtained. It should be noted that ceramic powder obtained by pulverizing ceramic scraps or damaged honeycomb structure obtained in the manufacturing process of the honeycomb structure may be reused as ceramic powder for the sealing material 70e. Thereby, the raw material cost of the honeycomb structure is reduced.
  • the sealing material 70e may or may not include a raw material powder (inorganic compound powder) of aluminum titanate ceramics.
  • the sealing material 70e can contain ceramic powder and no ceramic raw material powder.
  • the average particle size of the ceramic powder is not particularly limited, but may be about 5 to 50 ⁇ m.
  • the sealing material 70e can be made into a viscous liquid.
  • the mass of the binder in the sealing material 70e is 0.3 to 3 parts by mass, and the lubricant. 3 to 20 parts by mass, and the sealing material 70e can have a viscosity of 20 to 200 Pa ⁇ s.
  • the sealing material 70e is sintered with the partition wall 70d and integrated to form a sealing portion.
  • a honeycomb structure 100 multi-cell ceramic monolith
  • the honeycomb structure 100 includes alumina.
  • a crystal pattern such as titania may be included.
  • the honeycomb structure 100 may contain silicon.
  • the honeycomb structure 100 has the same structure as the green molded body 70 and can be applied to a diesel particle filter.
  • diesel particulate filters made of sintered aluminum magnesium titanate have an extremely low coefficient of thermal expansion, a high melting point, and a thermal shock during regeneration compared to diesel particulate filters made of SiC, cordierite or aluminum titanate alone. It is excellent in the point that the limit accumulation amount of soot is large.
  • a platinum-based metal catalyst supported on a carrier such as alumina or a promoter such as ceria or zirconia may be attached to the partition wall surface of the honeycomb structure 100 for a diesel particle filter.
  • the aluminum content in the aluminum titanate-based ceramics is not particularly limited, but is, for example, 40 to 60 mol% in terms of aluminum oxide.
  • the content of titanium in the aluminum titanate ceramic is not particularly limited, but is, for example, 35 to 55 mol% in terms of titanium oxide.
  • the magnesium content in the aluminum titanate-based ceramics can be 1 to 5% by mass in terms of magnesium oxide.
  • the silicon content in the aluminum titanate ceramic can be 2 to 5% by mass in terms of silicon oxide.
  • the aluminum titanate-based ceramics can contain components derived from raw materials or trace components that are inevitably mixed into work-in-process in the manufacturing process.
  • the length of the honeycomb structure 100 in the longitudinal direction of the through hole 70c is, for example, 50 to 300 mm.
  • the outer diameter of the honeycomb structure 100 is, for example, 50 to 250 mm.
  • the density (cell density) of the through holes 70c is, for example, 50 to 400 cpsi (cell per square inch). “Cpsi” represents the number of through holes 70c (cells) per square inch.
  • the total cross-sectional area of the flow path by the through hole 70c opened at the inlet side end surface 70a is due to the through hole 70c opened at the outlet side end surface 70b. This is approximately 6 times the total cross-sectional area of the flow path.
  • the length of one side of the regular hexagonal through hole 70c can be set to 0.2 to 2.0 mm, and 0.4 to 1.6 mm from the viewpoint of further reducing the thermal stress generated in the honeycomb structure 100 during combustion regeneration. it can.
  • the thickness (cell wall thickness) of the partition wall 70d in the structural unit can be 0.8 mm or less, and can be 0.5 mm or less.
  • the thickness of the partition wall 70d can be set to 0.1 mm or more and can be set to 0.2 mm or more from the viewpoint of maintaining the collection efficiency of the collection object and the strength of the honeycomb structure 100 at a high level.
  • the porosity of the partition wall 70d in the above structural unit can be set to 20% by volume or more and 30% by volume or more from the viewpoint of further reducing the pressure loss.
  • the porosity of the partition walls 70d can be set to 60% by volume or less and 50% by volume or less from the viewpoint of further reducing the thermal stress generated in the honeycomb structure 100 during combustion regeneration.
  • the porosity of the partition wall 70d 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 pore diameter (pore diameter) of the partition wall 70d in the above structural unit can be 5 to 30 ⁇ m, and can be 10 to 20 ⁇ m.
  • the pore diameter of the partition wall 70d can be adjusted by the raw material particle diameter, the amount of the pore-forming agent added, the kind of the pore-forming agent, and the firing conditions, and can be measured by a mercury intrusion method.
  • Effective filtration area of the honeycomb structure 100 is further from the viewpoint of reducing the pressure loss with further reduces the thermal stress generated in the honeycomb structure 100 in the combustion regeneration, can a 1.1 m 2 / L or more, 1.2 m 2 / L or more.
  • ⁇ Manufacturing method of honeycomb structure> (Raw material mixture preparation process and molding process)
  • an inorganic compound powder, a pore former, an organic binder, a solvent, and the like are mixed by a kneader or the like to prepare a raw material mixture.
  • the green molded body 70 is formed by molding the raw material mixture using an extruder having a die having a lattice-like opening. In addition, you may knead
  • the sealing material 70e is prepared by the same method as the raw material mixture for the green molded body 70 except that ceramic powder is contained and the compounding ratio of the components is adjusted.
  • the first mask is attached to the entrance-side end face 70a in which the plurality of through holes 70c are open in the green molded body 70.
  • a plurality of mask portions and openings having dimensions substantially similar to those of the through holes 70c are alternately arranged.
  • a first mask is affixed to the inlet side end surface 70a of the green molded body 70 so that each through hole 70c and each mask portion and opening portion overlap each other.
  • a second mask is attached to the outlet side end surface 70b opposite to the inlet side end surface 70a. The arrangement relationship between the opening and the mask portion of the second mask is opposite to that of the first mask.
  • any of the plurality of through holes 70c formed in the green molded body 70 is opened at one of the inlet side end surface 70a and the outlet side end surface 70b, and is closed by the mask portion on the other side.
  • the sealing material 70e is introduced into the end of each through hole 70c that overlaps the opening of the first mask.
  • the entire green molded body 70 may be vibrated by a vibrator. As a result, the sealing material 70e is easily filled in the gaps at the ends of the through holes 70c.
  • the sealing step for the outlet side end surface 70b to which the second mask is attached is performed in the same manner as the sealing step for the inlet side end surface 70a.
  • each mask is peeled off from each end face. Thereby, the green molded object 100 shown to Fig.1 (a) (b) and FIG.2 (a) (b) is completed.
  • the green molded body 70 subjected to the above extrusion molding, drying, cutting and sealing is green on a torch 170 which is a short green molded body laid on a shelf board 200 in a gas furnace.
  • the molded body 70 is placed and sintered so that the outlet side end face 70b is on the shelf board 200 side.
  • the Z axis in the figure is upward in the vertical direction, and the normal line of the shelf board 200 is oriented in a direction parallel to the Z axis.
  • the outlet side end face 70b may be supported or held by the support 300 in the gas furnace, and may be sintered.
  • the Z axis in the drawing is upward in the vertical direction, and the green molded body 70 is supported so that the longitudinal direction thereof is perpendicular to the Z axis. 4 and 5, the sintering can be performed under the condition that the sintering temperature of the outlet side end face 70b is lower than the sintering temperature of the inlet side end face 70a.
  • the temperature control in this case can be performed by (1) adjusting the gas flow using a baffle plate, (2) adding a burner and changing its installation position, and (3) changing the shape of the furnace.
  • the conditions under which the sintering temperature of the inlet side end face 70a is higher than the sintering temperature of the outlet side end face 70b of the body 70 can be selected.
  • the honeycomb structure 100 shown in FIG. 3 can be obtained by calcining (degreasing) and sintering the green molded body 70 in the furnace whose sintering temperature is adjusted as described above.
  • the calcination (degreasing) is a process for removing the organic binder in the green molded body 70 and the organic additive blended as necessary by burning, decomposition, or the like.
  • a typical calcining process corresponds to an initial stage of the sintering process, that is, a temperature raising stage (for example, a temperature range of 100 to 900 ° C.) until the green molded body 70 reaches the sintering temperature.
  • the rate of temperature rise can be suppressed as much as possible, and the O 2 concentration can be suppressed as much as possible.
  • the sintering temperature of the green molded body 70 is usually 1300 ° C. or higher, for example, 1400 ° C. or higher.
  • the sintering temperature is usually 1650 ° C. or lower, for example 1550 ° C. or lower.
  • the rate of temperature increase up to the sintering temperature is not particularly limited, but is usually 1 ° C./hour to 500 ° C./hour.
  • Sintering is usually performed in the atmosphere, but depending on the type and usage ratio of the raw material powder used, that is, aluminum source powder, titanium source powder, magnesium source powder and silicon source powder, inert gas such as nitrogen gas or argon gas You may sinter in gas and you may sinter in reducing gas, such as carbon monoxide gas and hydrogen gas. Moreover, you may sinter in the atmosphere which made the water vapor partial pressure low.
  • Sintering is usually carried out using a conventional sintering furnace such as a tubular electric furnace, box electric furnace, tunnel furnace, far-infrared furnace, microwave heating furnace, shaft furnace, reflection furnace, rotary furnace, roller hearth furnace, etc. It is. Sintering may be performed batchwise or continuously. Moreover, you may carry out by a stationary type and may carry out by a fluid type.
  • a conventional sintering furnace such as a tubular electric furnace, box electric furnace, tunnel furnace, far-infrared furnace, microwave heating furnace, shaft furnace, reflection furnace, rotary furnace, roller hearth furnace, etc. It is. Sintering may be performed batchwise or continuously. Moreover, you may carry out by a stationary type and may carry out by a fluid type.
  • the time required for the sintering may be a time sufficient for the green molded body 70 to transition to the aluminum titanate-based crystal.
  • the amount of the green molded body 70, the type of the sintering furnace, the sintering temperature, and the sintering atmosphere Usually, it is 10 minutes to 24 hours, although it varies depending on the situation.
  • the green molded body 70 may be calcined and sintered separately or continuously.
  • the green molded body 70 may be heated at a temperature equal to or higher than the thermal decomposition temperature of the organic binder and other organic additives and lower than the sintering temperature of the inorganic compound powder.
  • the green molded body 70 after the calcining process may be heated at a temperature equal to or higher than the sintering temperature of the inorganic compound powder.
  • the outlet side end surface 70b which is the side where the end portion of the 70c is closed by the sealing material 70e, has a large shrinkage due to sintering and tends to have low dimensional accuracy.
  • the lower side has a shape called an elephant foot. This is because the through-hole 70c has a regular hexagonal shape, and as shown in FIG. 1B and FIG. 2B, in the honeycomb structure in which the shape of the sealing is different between the inlet side end surface 70a and the outlet side end surface 70b. It is remarkable.
  • the present inventor intentionally arranges the outlet side end surface 70b on the shelf board 200 side and sinters it as a technique for reducing the shrinkage due to sintering of the outlet side end surface 70b, thereby greatly improving the dimensional accuracy. Found that you can.
  • the through holes 70c sealed by the sealing material 70e are adjacent to each other, and can contract significantly to each other.
  • the outlet side end surface 70b is pulled in the direction opposite to the contraction due to friction with the shelf plate 200, and thus the contraction can be suppressed.
  • FIG. 2B On the other hand, as shown in FIG.
  • the outlet side end surface 70b which is the side where the end portion of the through hole 70c is closed by the sealing material 70e in the inlet side end surface 70a and the outlet side end surface 70b in the sintering furnace is large.
  • the dimensional accuracy of the honeycomb structure 100 after sintering is improved by suppressing the shrinkage at the time of sintering by a simple method of simply placing the green molded body 70 on the shelf board 200 with the side facing down. Can be made.
  • the exit side end surface which is a side with the larger ratio by which the edge part of the through-hole 70c is obstruct
  • the green molded body 70 is sintered while the 70b is supported by the support 300, and the honeycomb structure 100 is manufactured.
  • the outlet side end surface 70b which is the side where the end portion of the through hole 70c is blocked by the sealing material 70e in the sintering furnace, is not necessarily on the lower side, more freely in the sintering furnace. While the green molded body 70 is disposed, shrinkage during sintering on the side can be suppressed, and the dimensional accuracy of the honeycomb structure 100 after sintering can be improved.
  • the outlet side on the side where the ratio of the end portion of the through hole 70c being blocked by the sealing material 70e is larger in the inlet side end surface 70a and the outlet side end surface 70b in the sintering furnace.
  • the green molded body 70 is sintered by setting the temperature on the end face 70b side lower than the temperature on the inlet side end face 70a side where the end portion of the through hole 70c is closed by the sealing material 70e.
  • the structure 100 can also be manufactured.
  • the ratio of the end portion of the through-hole 70c in the inlet side end surface 70a and the outlet side end surface 70b that is blocked by the sealing material 70e is large, and the temperature on the outlet side end surface 70b side that shrinks greatly during sintering is lowered. Thereby, the shrinkage
  • the partition wall 70d separating the plurality of through holes 70c has a hexagonal shape, and the end portion of the through hole 70c is the sealing material among the inlet side end surface 70a and the outlet side end surface 70b. Sealing portions are adjacent to each other on the outlet side end surface 70b side, which is the side where the ratio of being blocked by 70e is large, and the end portion of the through hole 70c is the sealing material 70e among the inlet side end surface 70a and the outlet side end surface 70b. The sealing portion is not adjacent to the inlet side end face 70a side, which is the side where the ratio of blocking is small.
  • the honeycomb structure 100 by sintering such a green molded body 70 and manufacturing the honeycomb structure 100, a diesel particle filter having high efficiency of filtering soot by the partition walls 70d can be manufactured.
  • the green molded body 70 having such a structure has a high rate of shrinkage due to sintering on the side where the end portion of the through hole 70c is closed by the sealing material 70e. Therefore, according to the manufacturing method of this embodiment.
  • the honeycomb structure 100 with high dimensional accuracy can be manufactured.
  • the outer peripheral diameter of the honeycomb structure 100 is high in the side surface of the manufactured honeycomb structure 100 from the inlet side end surface 70a to the outlet side end surface 70b, the dimensional accuracy is high. It does not change with a substantially constant diameter. For this reason, the gap between the exhaust pipe accommodating the honeycomb structure 100 and the honeycomb structure 100 can be reduced, and the sealing performance is improved.
  • the green molded body 70 is made of porous ceramics, and is made of porous aluminum titanate containing magnesium and silicon.
  • Diesel particle filter made of sintered aluminum magnesium titanate has an extremely low coefficient of thermal expansion, a high melting point, and thermal shock resistance during regeneration compared to diesel particle filter made of SiC, cordierite or aluminum titanate alone. Since it is excellent in that it has a large limit accumulation amount of soot, it can have even better characteristics as a diesel particle filter.
  • the green molded body 70 and the sealing material 70e may include ceramics such as cordierite ceramics and silicon carbide instead of aluminum titanate ceramics. Further, the green molded body 70 and the sealing material 70e may include these ceramic raw material powders.
  • the raw material powder for cordierite-based ceramics the above-described aluminum source powder, silica source powder and magnesium source powder may be used.
  • the shape of the honeycomb structure 100 is not limited to a cylinder, and can take any shape depending on the application.
  • the shape of the honeycomb structure 100 may be a polygonal column, an elliptical column, or the like.
  • the application of the honeycomb structure 100 is not limited to the diesel particle filter.
  • the honeycomb structure 100 includes an exhaust gas filter or a catalyst carrier used for exhaust gas purification of an internal combustion engine such as a gasoline engine, a filter used for filtering food and drink such as beer, and gas components (for example, carbon monoxide, It can be applied to ceramic filters such as a selective transmission filter for selectively transmitting carbon, nitrogen, oxygen, etc.).
  • ceramic filters such as a selective transmission filter for selectively transmitting carbon, nitrogen, oxygen, etc.
  • aluminum titanate-based ceramics have a high pore volume and an open porosity, so that good filter performance can be maintained over a long period of time.
  • Example 1 In order to form the green molded body 70, a raw material powder of aluminum magnesium titanate (Al 2 O 3 , TiO 2 , MgO), an aluminosilicate glass powder, a composite phase of aluminum magnesium titanate, alumina, and aluminosilicate glass Ceramic powder (composition formula at the time of preparation: 41.4 Al 2 O 3 -49.9 TiO 2 -5.4 MgO-3.3SiO 2 , the numerical value in the formula represents a molar ratio), organic binder, lubricant, pore formation
  • a raw material mixture containing an agent, a plasticizer, a dispersant, and water (solvent) was prepared. The content of main components in the raw material mixture was adjusted to the following values.
  • FIGS. A green molded body 70 having a partition wall 70d formed and separating the through hole 70c was produced.
  • the sealing material 70b of Example 1 was prepared by mixing ceramic powder, a pore former, an organic binder, a lubricant, and a solvent.
  • This ceramic powder is a powder having a composite phase of aluminum magnesium titanate, alumina, and aluminosilicate glass (composition formula when charged: 41.4 Al 2 O 3 -49.9 TiO 2 -5.4 MgO-3.3SiO 2 , The numerical value in the formula represents the molar ratio.).
  • the green molded body 70 is placed on the shelf board 200 in the gas furnace so that the outlet side end face 70b is on the shelf board 200 side and the inlet side end face 70a is on the upper side of the gas furnace.
  • the outlet side end surface 70b which is the side where the end portion of the through hole 70c is blocked by the sealing material 70e in the inlet side end surface 70a and the outlet side end surface 70b, is placed on the torch 170 and placed on the shelf 200.
  • a plurality of honeycomb structures 100 shown in FIG. 3 were manufactured by supporting and sintering.
  • the green molded body 70 is placed such that the inlet side end surface 70a is on the shelf plate 200 side and the outlet side end surface 70b is on the upper side of the gas furnace, and the inside of the inlet side end surface 70a and the outlet side end surface 70b is Then, the outlet side end face 70a, which is the side where the end portion of the through hole 70c is blocked by the sealing material 70e, is placed on the torch 170 and supported by the shelf board 200 and sintered, and then the honeycomb structure 100. A plurality of were manufactured.
  • FIG. 7 to 10 show relative average diameters of the green molded body 70 before sintering or the honeycomb structure 100 after sintering from the inlet side end face 70a (measurement height 0) to the outlet side end face 70b. This is indicated by a numerical value.
  • the honeycomb formed body 100 of the example obtained by sintering the green molded body 70 of the example shown in FIG. 7 with the outlet side end surface 70b shown in FIG.
  • the diameter is slightly reduced as compared with the central portion of the honeycomb structure 100, it can be seen that the outlet-side end face 70b has a reduced diameter compared to the central portion of the honeycomb structure 100.
  • the comparative honeycomb structure 100 obtained by sintering the green molded body 70 of the comparative example shown in FIG. 9 with the inlet side end face 70a shown in FIG. 10 on the shelf board 200 side is the inlet side end face 70a. It can be seen that a larger diameter is seen on the left side than the central part of the honeycomb structure 100, and a significantly smaller diameter is seen on the outlet side end face 70b than on the central part of the honeycomb structure 100.
  • Table 1 The above measured values are summarized in Table 1.
  • the amount of change of the diameter of the outlet side end face 70b on the upper side with respect to the diameter of the central portion of the honeycomb structure 100 is as large as ⁇ 1.1 to ⁇ 0.6. It shows a tendency to shrink significantly compared to the examples.
  • the amount of change of the diameter of the inlet side end face 70a of the comparative example on the lower side with respect to the diameter of the central portion of the honeycomb structure 100 shows a tendency to expand to +0.3 to +1.0.
  • the dimensional accuracy of the honeycomb structure after sintering can be improved.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

Corps façonné cru de type nid d'abeilles comportant une pluralité de trous traversants, les trous traversants du corps façonné cru étant formés de façon qu'une partie desdits trous traversants soit scellée par un matériau d'étanchéité sur la face d'extrémité côté entrée et soit ouverte sur la face d'extrémité côté sortie et que l'autre partie desdits trous traversants soit scellée par un matériau d'étanchéité sur la face d'extrémité côté sortie et soit ouverte sur la face d'extrémité côté entrée. Le corps façonné cru est fritté en supportant la face d'extrémité côté sortie comportant une importante proportion de surface en coupe où les extrémités des trous traversants sont scellées par le matériau d'étanchéité, dans une coupe verticale par rapport à la face d'extrémité côté entrée et à la face d'extrémité côté sortie. Dans la coupe verticale par rapport à la face d'extrémité côté entrée et à la face d'extrémité côté sortie, la proportion de surface en coupe où les trous traversants sont scellés par le matériau d'étanchéité est importante et le frittage est effectué en supportant la face d'extrémité côté sortie qui est un côté subissant une forte contraction lors du frittage, supprimant ainsi la contraction sur ledit côté pendant le frittage et permettant d'améliorer la précision dimensionnelle de la structure en nid d'abeilles après frittage.
PCT/JP2012/070075 2011-08-19 2012-08-07 Procédé de production d'une structure en nid d'abeilles WO2013027570A1 (fr)

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JP2011179822A JP5860633B2 (ja) 2011-08-19 2011-08-19 ハニカム構造体の製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3173202A3 (fr) * 2015-11-27 2017-08-30 Lakeview Innovation Ltd. Composant en céramique spécial

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08119750A (ja) * 1994-10-24 1996-05-14 Nippon Soken Inc セラミックハニカム構造体の焼成方法
JP2010083738A (ja) * 2008-10-02 2010-04-15 Hitachi Metals Ltd チタン酸アルミニウム質セラミックハニカム構造体の製造方法
JP2010227767A (ja) * 2009-03-26 2010-10-14 Ngk Insulators Ltd ハニカムフィルタ
WO2011037177A1 (fr) * 2009-09-25 2011-03-31 住友化学株式会社 Procédé de production d'article céramique cuit
WO2011040145A1 (fr) * 2009-09-29 2011-04-07 日本碍子株式会社 Structure de nid d'abeilles et procédé pour sa fabrication

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08119750A (ja) * 1994-10-24 1996-05-14 Nippon Soken Inc セラミックハニカム構造体の焼成方法
JP2010083738A (ja) * 2008-10-02 2010-04-15 Hitachi Metals Ltd チタン酸アルミニウム質セラミックハニカム構造体の製造方法
JP2010227767A (ja) * 2009-03-26 2010-10-14 Ngk Insulators Ltd ハニカムフィルタ
WO2011037177A1 (fr) * 2009-09-25 2011-03-31 住友化学株式会社 Procédé de production d'article céramique cuit
WO2011040145A1 (fr) * 2009-09-29 2011-04-07 日本碍子株式会社 Structure de nid d'abeilles et procédé pour sa fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3173202A3 (fr) * 2015-11-27 2017-08-30 Lakeview Innovation Ltd. Composant en céramique spécial
US10870218B2 (en) 2015-11-27 2020-12-22 Lakeview Innovation Ltd. Speciality ceramic components

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