WO2013024745A1 - Structure à nid d'abeilles - Google Patents

Structure à nid d'abeilles Download PDF

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Publication number
WO2013024745A1
WO2013024745A1 PCT/JP2012/070080 JP2012070080W WO2013024745A1 WO 2013024745 A1 WO2013024745 A1 WO 2013024745A1 JP 2012070080 W JP2012070080 W JP 2012070080W WO 2013024745 A1 WO2013024745 A1 WO 2013024745A1
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Prior art keywords
flow path
honeycomb structure
aluminum
curvature
radius
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PCT/JP2012/070080
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English (en)
Japanese (ja)
Inventor
健太郎 岩崎
鈴木　敬一郎
小山　聡
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住友化学株式会社
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Publication of WO2013024745A1 publication Critical patent/WO2013024745A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
    • 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
    • B01D46/2451—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
    • B01D46/2486—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
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/30—Honeycomb supports characterised by their structural details
    • F01N2330/34—Honeycomb supports characterised by their structural details with flow channels of polygonal cross section

Definitions

  • the present invention relates to a honeycomb structure.
  • the honeycomb structure is used as a ceramic filter that removes the collected matter from the fluid containing the collected matter.
  • a ceramic filter that removes the collected matter from the fluid containing the collected matter.
  • an internal combustion engine such as a diesel engine or a gasoline engine. It is used as an exhaust gas filter and a filter used for filtering food and drink.
  • Such a honeycomb structure has a plurality of parallel flow paths partitioned by porous partition walls (see, for example, Patent Document 1 below).
  • the honeycomb structure when the honeycomb structure is exposed to a high temperature and thermal stress is applied to the honeycomb structure, the honeycomb structure may be damaged. Therefore, the conventional honeycomb structure is required to reduce the thermal stress applied to the honeycomb structure when the honeycomb structure is exposed to a high temperature and to prevent the honeycomb structure from being damaged. ing.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a honeycomb structure that can be prevented from being damaged under a high temperature environment.
  • the present inventor has found that the honeycomb structure is more susceptible to the central portion than the central portion of the honeycomb structure when exposed to a high temperature. It has also been found that the portion located on the outer peripheral side of the honeycomb structure tends to be damaged.
  • the present inventor when the cross section of the flow path perpendicular to the axial direction of the flow path is a polygonal shape having arc-shaped corners, the radius of curvature of the corners in the flow path disposed in the center portion It has been found that the above problem can be solved by adjusting the radius of curvature of the corners in the flow path disposed in the portion located on the outer peripheral side.
  • the honeycomb structure according to the present invention is a honeycomb structure having a plurality of parallel flow paths partitioned by porous partition walls, and the cross section of the flow path perpendicular to the axial direction of the flow path has an arc shape.
  • a plurality of flow paths are disposed at the outer peripheral side of the honeycomb structure with respect to the first flow path and the first flow path.
  • the radius of curvature of the corner of the second channel is greater than the radius of curvature of the corner of the first channel.
  • the radius of curvature of the corner of the second channel disposed on the outer peripheral side of the honeycomb structure with respect to the first channel is the radius of curvature of the corner of the first channel. Bigger than.
  • the thermal stress is more easily applied to the partition walls constituting the flow path, and the thermal stress is locally applied to specific portions of the partition walls. Is suppressed. Therefore, in the honeycomb structure according to the present invention, even in the case where thermal stress is applied to the outer peripheral region that tends to be damaged more easily than the central portion in the conventional honeycomb structure, the region is damaged. Is suppressed. Therefore, in the honeycomb structure according to the present invention, the honeycomb structure can be prevented from being damaged.
  • the ratio of the radius of curvature of the corner of the first channel to the hydraulic diameter (hydraulic diameter) of the first channel (the curvature of the corner of the first channel) is preferably 0.01 to 0.30. In this case, damage to the honeycomb structure can be further suppressed.
  • the “hydrodynamic diameter of the flow path” refers to the diameter of a perfect circle having a cross-sectional area equivalent to the cross-sectional area of the cross section of the target flow path.
  • the ratio of the radius of curvature of the corner of the second channel to the hydraulic diameter of the second channel (the radius of curvature of the corner of the second channel / the radius of the second channel)
  • the hydraulic diameter is preferably 0.01 to 0.80. In this case, damage to the honeycomb structure can be further suppressed.
  • the partition wall may contain aluminum titanate. In this case, damage to the honeycomb structure can be further suppressed.
  • one end of a part of the plurality of channels and the other end of the remaining part of the plurality of channels may be sealed.
  • the honeycomb structure according to the present invention can prevent the honeycomb structure from being damaged under a high temperature environment (for example, a temperature of 800 ° C. or higher).
  • FIG. 1 is a diagram schematically showing a honeycomb structure according to the first embodiment of the present invention.
  • FIG. 2 is an enlarged view of regions A1 and A2 of FIG. 3 is a view taken in the direction of arrows III-III in FIG.
  • FIG. 4 is a diagram schematically showing a honeycomb structure according to the second embodiment of the present invention.
  • FIG. 5 is an enlarged view of regions B1 and B2 in FIG. 6 is a view taken in the direction of arrows VI-VI in FIG.
  • FIG. 7 is a view showing a photograph of the main part of the end face of the honeycomb structure.
  • FIG. 1 is a diagram schematically showing a honeycomb structure according to the first embodiment.
  • FIG. 2 is an enlarged view of regions A1 and A2 of FIG. 3 is a view taken in the direction of arrows III-III in FIG.
  • the honeycomb structure 100 is a cylindrical body having a plurality of flow paths 105 arranged substantially parallel to each other.
  • the plurality of flow paths 105 are partitioned by partition walls 120 that extend substantially parallel to the central axis of the honeycomb structure 100.
  • a plurality of flow channels 105 were arranged in the center P 11 of the honeycomb structure 100 flow path 105a (a first flow path, the center-side channel) and than the flow path 105a of the outer peripheral side of the honeycomb structure 100 flow path 105b, which is disposed in the region P 12 (second flow path, the outer peripheral side flow passage) has a, a.
  • the “flow path disposed in the center” is disposed near the midpoint of the outer diameter of the honeycomb structure (the maximum thickness of the honeycomb structure in the direction perpendicular to the axial direction of the flow path).
  • the flow path is arranged in a region having a thickness of 30% of the outer diameter of the honeycomb structure from the center of the honeycomb structure.
  • the “flow path arranged in the region on the outer peripheral side” may be a flow path arranged on the outer peripheral side of the honeycomb structure with respect to the central portion, for example, from the outer periphery of the honeycomb structure.
  • the flow path is disposed in a region up to a depth of 30% of the outer diameter of the honeycomb structure.
  • Each of the flow path 105a and the flow path 105b has a plurality of flow paths 110a and a plurality of flow paths 110b adjacent to the flow paths 110a.
  • the channel 110 a and the channel 110 b extend substantially perpendicular to both end faces of the honeycomb structure 100.
  • One end of the flow path 110 a constituting a part of the flow path 105 is sealed by the sealing portion 130 on the one end surface 100 a of the honeycomb structure 100, and the other end of the flow path 110 a is the other end of the honeycomb structure 100. It opens in the end surface 100b.
  • one end of the flow path 110b constituting the remaining part of the plurality of flow paths 105 is open at one end face 100a, and the other end of the flow path 110b is sealed by the sealing portion 130 at the other end face 100b.
  • the end on the one end face 100a side of the flow path 110b is opened as a gas inflow opening
  • the end on the other end face 100b side of the flow path 110a is opened as a gas outflow opening.
  • the cross section substantially perpendicular to the axial direction (longitudinal direction) of the flow path 110a and the flow path 110b is a polygonal shape having arc-shaped corners, for example, a hexagonal shape.
  • the virtual hexagonal H 11 in contact with each of the sides constituting the cross section of the flow path 110a causes the fluid containing the trapped substance to flow equally from the gas inflow side flow path to the gas outflow side flow path.
  • the sides 140 are preferably regular hexagons having substantially the same length, but may be flat hexagons.
  • the virtual hexagon H 12 in contact with each of the sides constituting the cross section of the flow path 110b is, for example, a flat hexagon, but may be a regular hexagon.
  • the length of the opposing sides in a virtual hexagonal H 12 is substantially equal to each other.
  • Virtual hexagonal H 12 in the narrow side (second side of each other length of approximately equal two (a pair) of the long side (first side) 150a, is substantially equal four (two pairs) in length of each other ) 150b.
  • the short side 150b is disposed on each side of the long side 150a.
  • the long sides 150a face each other substantially in parallel, and the short sides 150b face each other substantially in parallel.
  • the length of the long side 150a is adjusted to be longer than the length of the short side 150b.
  • the flow path 105 includes a plurality of structural units including one flow path 110a and six flow paths 110b surrounding the flow path 110a.
  • each of the sides 140 of the virtual hexagonal H 11 in contact with the flow path 110a is substantially parallel to face the long sides 150a of the virtual hexagonal H 12 in contact with the flow path 110b.
  • Each of the short sides 150b of the virtual hexagonal H 12 is substantially parallel to and facing the short sides 150b of the virtual hexagonal H 12 in contact with the adjacent flow path 110b.
  • one flow path 110b is disposed between the adjacent flow paths 110a, whereby the flow paths 110a and 110b are alternately disposed in the arrangement direction of the flow paths 110a. Has been.
  • the length of the honeycomb structure 100 in the axial direction of the flow paths 110a and 110b 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 channels 110a and 110b is, for example, 50 to 400 cpsi (cell per square inch). “Cpsi” represents the number of flow paths (cells) per square inch.
  • the total area of the flow paths 110b is preferably larger than the total area of the flow paths 110a.
  • the length of the side 140 in the virtual hexagon H 11 is preferably 0.2 to 2.0 mm, and more preferably 0.4 to 1.6 mm, from the viewpoint of further reducing the thermal stress generated in the honeycomb structure during combustion regeneration. .
  • Length of the long side 150a of the virtual hexagonal H 12 from the viewpoint of further reducing the thermal stress generated in the honeycomb structure in the combustion regeneration preferably 0.4 ⁇ 2.0mm, 0.4 ⁇ 1.6mm Gayori preferable.
  • Length of a short side 150b of the virtual hexagonal H 12 from the viewpoint of further reducing the thermal stress generated in the honeycomb structure in the combustion regeneration, preferably 0.3 ⁇ 2.0mm, 0.5 ⁇ 1.0mm Gayori preferable.
  • the radius of curvature of the corner of the channel 105b in the outer peripheral region P 12 (FIG. 2B) is larger than the radius of curvature of the corner of the channel 105a in the center P 11 (FIG. 2A). Have been adjusted so that.
  • the radius of curvature R 122 radius of curvature R 121 and the corner portion C 122 of the corner portion C 121 of the channel 110b in the region P 12 is larger than the radius of curvature R 112 radius of curvature R 111 and the corner portion C 112 of the channel 110b of the corner portion C 111 at the center P 11, the radius of curvature R 113 of the corner portion C 113 of the flow path 110a at the center P 11 Bigger than.
  • the flow path 110a in the region P 12 the radius of curvature R 123 of the corner portion C 123 has the flow path 110b at the center P 11 larger than the radius of curvature R 112 radius of curvature R 111 and the corner portion C 112 of the corner portion C 111, greater than the radius of curvature R 113 of the corner portion C 113 of the flow path 110a at the center P 11.
  • the ratio of the radius of curvature of the corner of the channel 105a to the hydraulic diameter of the channel 105a is such that the thermal stress generated in the honeycomb structure during combustion regeneration is further reduced.
  • the hydraulic diameter is 1, it is preferably 0.01 or more, and more preferably 0.05 or more.
  • the ratio of the radius of curvature of the corner of the channel 105a to the hydraulic diameter of the channel 105a is preferably 0.30 or less, and more preferably 0.25 or less.
  • the hydraulic diameter of the flow path 105a is, for example, 0.5 to 3.0 mm.
  • the ratio of the radius of curvature of the corner of the channel 105b to the hydraulic diameter of the channel 105b is such that the thermal stress generated in the honeycomb structure during combustion regeneration is further reduced.
  • the hydraulic diameter is 1, it is preferably 0.01 or more, and more preferably 0.10 or more.
  • the ratio of the radius of curvature of the corner of the channel 105b to the hydraulic diameter of the channel 105b is preferably 0.80 or less, and more preferably 0.50 or less.
  • the hydraulic diameter of the channel 105b is, for example, 0.5 to 3.0 mm.
  • the partition wall 120 has a partition wall 120a as a part for partitioning the flow path 110a and the flow path 110b, and has a partition wall 120b as a part for partitioning the adjacent flow paths 110b.
  • the thickness of the partition wall 120a (the distance between the side 140 and the long side 150a) is preferably 1.0 mm or less, and more preferably 0.5 mm or less, from the viewpoint of further reducing the pressure loss.
  • the thickness of the partition wall 120a is preferably 0.01 mm or more, and more preferably 0.1 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 thickness of the partition wall 120b (distance between the short sides 150b facing each other) is preferably 2.0 mm or less, more preferably 1.0 mm or less, from the viewpoint of further reducing the pressure loss.
  • the thickness of the partition wall 120b is preferably 0.1 mm or more, and more preferably 0.2 mm or more from the viewpoint of maintaining the collection efficiency of the collected object and the strength of the honeycomb structure 100 high.
  • the porosity of the partition wall 120 is preferably 20% by volume or more, and more preferably 30% by volume or more from the viewpoint of further reducing pressure loss.
  • the porosity of the partition walls 120 is preferably 60% by volume or less, and more preferably 50% by volume or less, from the viewpoint of further reducing thermal stress generated in the honeycomb structure during combustion regeneration.
  • the porosity of the partition wall 120 can be adjusted by the particle diameter of the raw material, 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.
  • the pore diameter (pore diameter) of the partition wall 120 is preferably 5 to 30 ⁇ m, and more preferably 10 to 20 ⁇ m.
  • 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.
  • FIG. 4 is a diagram schematically showing a honeycomb structure according to the second embodiment.
  • FIG. 5 is an enlarged view of regions B1 and B2 in FIG. 6 is a view taken in the direction of arrows VI-VI in FIG.
  • the honeycomb structure 200 is a cylindrical body having a plurality of flow paths 205 arranged substantially parallel to each other.
  • the plurality of flow paths 205 are partitioned by partition walls 220 that extend substantially parallel to the central axis of the honeycomb structure 200.
  • a plurality of flow channels 205 were arranged in the center P 21 of the honeycomb structure 200 flow path 205a (a first flow path, the center-side channel) and than the flow path 205a of the outer peripheral side of the honeycomb structure 200 flow path 205b, which is disposed in the region P 22 (second flow path, the outer peripheral side flow passage) has a, a.
  • Each of the flow path 205a and the flow path 205b has a plurality of flow paths 210a and a plurality of flow paths 210b adjacent to the flow path 210a.
  • the flow path 210 a and the flow path 210 b extend substantially perpendicular to both end faces of the honeycomb structure 200.
  • One end of the flow path 210 a constituting a part of the flow path 205 is sealed by the sealing portion 230 on the one end surface 200 a of the honeycomb structure 200, and the other end of the flow path 210 a is the other end of the honeycomb structure 200.
  • the end surface 200b is open.
  • one end of the flow path 210b constituting the remaining part of the plurality of flow paths 205 is open at the one end face 200a, and the other end of the flow path 210b is sealed by the sealing portion 230 at the other end face 200b.
  • the end on the one end face 200a side of the flow path 210b is opened as a gas inlet
  • the end on the other end face 200b side of the flow path 210a is opened as a gas outlet.
  • the cross section substantially perpendicular to the axial direction (longitudinal direction) of the flow path 210a and the flow path 210b is a polygonal shape having arc-shaped corners, for example, a hexagonal shape.
  • Virtual hexagons H 21 in contact with each of the sides constituting the cross section of the flow path 210a allow the fluid containing the trapped substance to flow evenly from the gas inflow side flow path to the gas outflow side flow path.
  • the sides 240 are preferably regular hexagons having substantially the same length, but may be flat hexagons.
  • the virtual hexagon H 22 in contact with each of the sides constituting the cross section of the flow path 210b is, for example, a flat hexagon, but may be a regular hexagon.
  • the lengths of sides facing each other in the virtual hexagon H 22 are different from each other.
  • the virtual hexagon H 22 has three long sides (first sides) 250a having substantially the same length, and three short sides (second sides) 250b having substantially the same length. .
  • the long side 250a and the short side 250b face each other substantially in parallel, and the short side 250b is disposed on each side of the long side 250a.
  • the length of the long side 250a is adjusted to be longer than the length of the short side 250b.
  • the channel 205 includes a plurality of structural units including one channel 210a and six channels 210b surrounding the channel 210a.
  • each of the sides 240 of the virtual hexagon H 21 in contact with the flow path 210a is opposed to the long side 250a of the virtual hexagon H 22 in contact with the flow path 210b substantially in parallel.
  • Each of the short sides 250b of the virtual hexagonal H 22 is substantially parallel to and facing the short sides 250b of the virtual hexagonal H 22 in contact with the adjacent flow path 210b.
  • two flow paths 210b adjacent to each other in a direction substantially perpendicular to the arrangement direction of the flow paths 210a are arranged between the adjacent flow paths 210a.
  • the two flow paths 210b are arranged symmetrically across a line connecting the centers of the cross sections of the adjacent flow paths 210a.
  • One flow path 210b is surrounded by three flow paths 210a.
  • the length of the honeycomb structure 200 in the axial direction of the flow paths 210a and 210b is, for example, 50 to 300 mm.
  • the outer diameter of the honeycomb structure 200 is, for example, 50 to 250 mm.
  • the density (cell density) of the flow paths 210a and 210b is, for example, 50 to 400 cpsi.
  • the total area of the flow paths 210b is preferably larger than the total area of the flow paths 210a.
  • the length of the side 240 in the virtual hexagon H 21 is preferably 0.2 to 2.0 mm, more preferably 0.4 to 1.6 mm, from the viewpoint of further reducing the thermal stress generated in the honeycomb structure during combustion regeneration. .
  • Length of a short side 250b of the virtual hexagonal H 22, from the viewpoint of further reducing the thermal stress generated in the honeycomb structure in the combustion regeneration preferably 0.3 ⁇ 2.0mm, 0.5 ⁇ 1.0mm Gayori preferable.
  • the radius of curvature of the corner of the channel 205b in the outer peripheral region P 22 (FIG. 5B) is larger than the radius of curvature of the corner of the channel 205a in the center P 21 (FIG. 5A). Have been adjusted so that.
  • the radius of curvature R 222 radius of curvature R 221 and the corner portion C 222 of the corner portion C 221 of the channel 210b in the region P 22 is larger than the radius of curvature R 212 radius of curvature R 211 and the corner portion C 212 of the channel 210b of the corner portion C 211 at the center P 21, the radius of curvature R 213 of the corner portion C 213 of the flow path 210a at the center P 21 Bigger than.
  • the flow path 210a in the region P 22 the radius of curvature R 223 of the corner portion C 223 has the flow path 210b at the center P 21 larger than the radius of curvature R 212 radius of curvature R 211 and the corner portion C 212 of the corner portion C 211, greater than the radius of curvature R 213 of the corner portion C 213 of the flow path 210a at the center P 21.
  • the ratio of the radius of curvature of the corner of the flow path 205a to the hydraulic diameter of the flow path 205a is such that the thermal stress generated in the honeycomb structure during combustion regeneration is further reduced.
  • the hydraulic diameter is 1, it is preferably 0.01 or more, and more preferably 0.05 or more.
  • the ratio of the radius of curvature of the corner of the flow path 205a to the hydraulic diameter of the flow path 205a is preferably 0.30 or less, and more preferably 0.25 or less.
  • the hydraulic diameter of the channel 205a is, for example, 0.5 to 3.0 mm.
  • the ratio of the radius of curvature of the corner of the flow path 205b to the hydraulic diameter of the flow path 205b is such that the thermal stress generated in the honeycomb structure during combustion regeneration is further reduced.
  • the hydraulic diameter is 1, it is preferably 0.01 or more, and more preferably 0.10 or more.
  • the ratio of the radius of curvature of the corner of the channel 205b to the hydraulic diameter of the channel 205b is preferably 0.80 or less, and more preferably 0.50 or less.
  • the hydraulic diameter of the flow path 205b is, for example, 0.5 to 3.0 mm.
  • the partition wall 220 has a partition wall 220a as a part for partitioning the flow path 210a and the flow path 210b, and has a partition wall 220b as a part for partitioning the adjacent flow paths 210b.
  • the thickness of the partition 220a (distance between the side 240 and the long side 250a) is preferably 1.0 mm or less, and more preferably 0.5 mm or less, from the viewpoint of further reducing pressure loss.
  • the thickness of the partition 220a is preferably 0.01 mm or more, and more preferably 0.1 mm or more, from the viewpoint of maintaining the collection efficiency of the object to be collected and the strength of the honeycomb structure 200 high.
  • the thickness of the partition 220b (distance between the short sides 250b facing each other) is preferably 2.0 mm or less, and more preferably 1.0 mm or less, from the viewpoint of further reducing the pressure loss.
  • the thickness of the partition 220b is preferably 0.1 mm or more, and more preferably 0.2 mm or more, from the viewpoint of maintaining the collection efficiency of the object to be collected and the strength of the honeycomb structure 200 high.
  • the porosity of the partition 220 is preferably 20% by volume or more, and more preferably 30% by volume or more from the viewpoint of further reducing pressure loss.
  • the porosity of the partition walls 220 is preferably 60% by volume or less, and more preferably 50% by volume or less, from the viewpoint of further reducing thermal stress generated in the honeycomb structure during combustion regeneration.
  • the porosity of the partition 220 can be adjusted by the particle diameter of the raw material, the amount of the pore-forming agent added, the type 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 220 is preferably 5 to 30 ⁇ m, and more preferably 10 to 20 ⁇ m.
  • the pore diameter of the partition wall 220 can be adjusted by the particle diameter of the raw material, 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.
  • the partition walls are porous, and include, for example, porous ceramics (porous ceramic sintered body).
  • the partition wall 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.
  • the partition wall may contain aluminum titanate, and may further contain magnesium or silicon.
  • the partition walls are 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 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 0.03 to 0.20 is more preferable, and 0.03 to 0.18 is still more preferable.
  • the partition walls may contain trace components derived from raw materials or trace components inevitably included in the production process.
  • the partition may contain a 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 may contain 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 structure. .
  • the phase derived from the raw material include phases such as alumina and titania.
  • the crystal phase forming the partition can be confirmed by an X-ray diffraction spectrum.
  • the above honeycomb structure is suitable as a particulate filter that collects collected substances such as soot contained in exhaust gas from an internal combustion engine such as a diesel engine or a gasoline engine.
  • the honeycomb structure 100 as shown in FIG. 3, the gas G supplied from the one end face 100a to the flow path 110b passes through the communication hole in the partition wall 120 and reaches the adjacent flow path 110a, and the other end face It is discharged from 100b.
  • the substance to be collected 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 structure 100 functions as a filter.
  • the honeycomb structure 200 functions as a filter.
  • the honeycomb structure is not only used for the particulate filter described above, but also a filter used for filtering food and drink such as beer; gas components generated during petroleum refining (for example, carbon monoxide, carbon dioxide, nitrogen, oxygen)
  • a selective permeation filter for selectively permeating the catalyst used for a catalyst carrier and the like.
  • the partition wall is not limited to containing aluminum titanate, and may contain ceramics such as cordierite, silicon carbide, mullite, or a metal substance.
  • the arrangement configuration and the cross-sectional configuration of the flow paths 110a and 110b in the honeycomb structure 100 are not limited to the above.
  • the side 140 and the long side 150a face each other, and the short sides 150b face each other in the adjacent flow path 110b, but the side 140 and the short side 150b face each other and are adjacent to each other.
  • the long sides 150a may face each other.
  • the lengths of the side 140 and the long side 150a facing each other may be different from each other, and the lengths of the short sides 150b facing each other may be different from each other.
  • the side 140 and the long side 150a facing each other may not extend substantially parallel to each other but may extend in directions intersecting each other.
  • the short sides 150b facing each other may not extend substantially parallel to each other but may extend in directions intersecting each other. If the virtual hexagonal H 12 is flattened hexagon, in the virtual hexagonal H 12, it may be different from each other the length of the opposing sides.
  • the arrangement configuration and the cross-sectional configuration of the flow path 210a and the flow path 210b are not limited to the above.
  • the side 240 and the long side 250a face each other, and the short sides 250b face each other in the adjacent flow path 210b, but the side 240 and the short side 250b face each other.
  • the long sides 250a may be opposed to each other in the adjacent flow path 210b.
  • the lengths of the side 240 and the long side 250a facing each other may be different from each other, and the lengths of the short sides 250b facing each other may be different from each other.
  • the sides 240 and the long sides 250a facing each other may not extend substantially in parallel but may extend in directions intersecting each other.
  • the short sides 250b facing each other may not extend substantially in parallel but may extend in directions intersecting each other. If the virtual hexagonal H 22 is flattened hexagon, in the virtual hexagonal H 22, it may be substantially equal to each other the length of the opposing sides.
  • the cross section of the flow path substantially perpendicular to the axial direction (longitudinal direction) of the flow path may be a polygonal shape having arc-shaped corners and is not limited to a hexagonal shape.
  • the cross section of the flow path may be rectangular, octagonal, triangular, or the like.
  • the honeycomb structure is not limited to a cylindrical body, and may be a cube, a rectangular parallelepiped, or the like.
  • the both ends of each flow path do not need to be sealed.
  • the manufacturing method of the honeycomb structure includes, for example, (a) a raw material preparation step of preparing a raw material mixture containing ceramic powder and additives, and (b) a forming step of forming the raw material mixture to obtain a formed body having a flow path. And (c) a firing step of firing the molded body. Moreover, the manufacturing method of the honeycomb structure may further include (d) a sealing step of sealing one end of each flow path between the forming step and the firing step or after the firing step.
  • a sealing step of sealing one end of each flow path between the forming 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. Further, 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 composite oxide such as magnesia spinel (MgAl 2 O 4 ) is used as a raw material powder.
  • 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 structure obtained by the present production method.
  • the honeycomb structure obtained by the present manufacturing method is damaged, the damaged honeycomb structure or its fragments can be pulverized and used.
  • the powder obtained by pulverization can be aluminum magnesium titanate powder.
  • the hole forming agent those formed by a material disappearing at a temperature equal to or lower than the temperature at which the molded body is degreased and fired in the step (c) 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.
  • step (b) Molding process
  • a honeycomb structure having a plurality of flow paths is obtained as a ceramic molded body.
  • 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.
  • degreasing 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) is performed between step (b) and step (c) or after step (c).
  • step (d) is performed between step (b) and step (c) or after 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 is baked together with the ceramic molded body. By doing so, the sealing part which seals one edge part of a flow path is obtained.
  • the sealing material the same mixture as the raw material mixture can be used.
  • a honeycomb structure can be obtained through the above steps.
  • the honeycomb structure has a shape that substantially maintains the shape of the formed body immediately after forming in the step (b), but is subjected to grinding or the like after the step (b), the step (c), or the step (d). Also, it can be processed into a desired shape.
  • ⁇ Preparation of raw material mixture 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-forming agents, 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 cylindrical columnar body (DPF) having the structure shown in FIGS. 1 to 3 was produced by kneading the above raw material mixture and then performing extrusion molding.
  • a mold having a plurality of openings having a hexagonal cross section was used. The cross section of each opening in the mold had arcuate corners.
  • the aluminum titanate conversion rate (AT conversion rate) of the columnar body 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 columnar body in the axial direction of the flow path was 153 mm.
  • the outer diameter of the end face of the columnar body was 144 mm.
  • the density of the flow path (cell density) was 290 cpsi.
  • the length of one side in the regular hexagonal virtual hexagon was 0.9 mm.
  • the length of the long side was 0.9 mm, and the length of the short side was 0.6 mm.
  • the thickness of the partition between flow paths was 12 mil (milli-inch, 0.30 mm).
  • the porosity of the partition walls was 45% by volume.
  • the pore diameter of the partition wall was 15 ⁇ m.
  • FIG. 7 is a photograph of the main part of the end face of the columnar body
  • FIG. 7A is a photograph of the center part of the end face (region having a thickness of 10% of the outer diameter of the columnar body from the center of the columnar body).
  • FIG. 7B is a photograph of a region on the outer peripheral side of the end surface (region having a depth of 10% of the outer diameter of the columnar body from the outer periphery of the columnar body).
  • Hydraulic diameter of the hydraulic diameter and the flow path F 12 of the flow path F 11 was 1.4 mm.
  • the ratio of the radius of curvature R1 to the hydraulic diameter of the channel F 11 is 0.17
  • the ratio of the radius of curvature R2 to the hydraulic diameter of the channel F 12 was 0.17.
  • the radius of curvature R3 is The curvature radius R4 was 268 ⁇ m.
  • Hydraulic diameter of the hydraulic diameter and the flow path F 22 of the flow path F 21 was 1.4 mm.
  • the ratio of the radius of curvature R3 to the hydraulic diameter of the flow path F 21 is 0.18
  • the ratio of the curvature radius R4 to the hydraulic diameter of the flow path F 22 was 0.19.
  • 100, 200 ... honeycomb structure 105, 205 ... flow path, 105a, 205a ... flow path (first flow path), 105b, 205b ... flow path (second flow path), 120, 220 ... partition walls, C 111 , C 112 , C 113 , C 121 , C 122 , C 123 , C 211 , C 212 , C 213 , C 221 , C 222 , C 223 ... corner part, P 11 , P 21 ...

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  • Chemical & Material Sciences (AREA)
  • Geometry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filtering Materials (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

La présente invention concerne une structure en nid d'abeilles (100) comprenant une pluralité de canaux d'écoulement parallèles (105) divisés par des parois de séparation poreuses (120), dans lesquelles les sections transversales des canaux d'écoulement (105), perpendiculaires à la direction axiale des canaux d'écoulement (105), présentent une forme polygonale présentant des sections coins de forme arquée, la pluralité de canaux d'écoulement (105) comprend un canal d'écoulement (105a) disposé dans la section centrale (P11) de la structure en nid d'abeilles (100) et un autre canal d'écoulement (105b) disposé plus loin sur le côté périphérique externe de la structure en nid d'abeilles (100) que le premier canal d'écoulement (105a), et le rayon de courbure des sections coin de l'autre canal d'écoulement (105b) est supérieur au rayon de courbure des sections coin du premier canal d'écoulement (105a).
PCT/JP2012/070080 2011-08-12 2012-08-07 Structure à nid d'abeilles WO2013024745A1 (fr)

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JP2011177007A JP2013039514A (ja) 2011-08-12 2011-08-12 ハニカム構造体
JP2011-177007 2011-08-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3919158A4 (fr) * 2019-07-12 2022-05-04 Denso Corporation Filtre de purification de gaz d'échappement
US11845033B2 (en) 2019-08-20 2023-12-19 Denso Corporation Exhaust gas purification filter

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5816054B2 (ja) * 2011-10-31 2015-11-17 住友化学株式会社 ハニカム構造体
JP6140509B2 (ja) * 2013-04-04 2017-05-31 日本碍子株式会社 ウォールフロー型排ガス浄化フィルタ
US9683474B2 (en) * 2013-08-30 2017-06-20 Dürr Systems Inc. Block channel geometries and arrangements of thermal oxidizers
WO2016013516A1 (fr) 2014-07-23 2016-01-28 イビデン株式会社 Filtre en nid d'abeilles
EP3173137B1 (fr) * 2014-07-23 2022-06-22 Ibiden Co., Ltd. Filtre en nid d'abeilles
WO2016013513A1 (fr) 2014-07-23 2016-01-28 イビデン株式会社 Filtre en nid d'abeilles
JP2018158445A (ja) * 2015-08-20 2018-10-11 住友化学株式会社 ハニカム構造体及びハニカムフィルタ
JP2018183710A (ja) * 2015-09-24 2018-11-22 住友化学株式会社 ハニカムフィルタ及びハニカムフィルタの製造方法

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JPS62234552A (ja) * 1986-04-02 1987-10-14 Mitsubishi Heavy Ind Ltd 触媒構造体
JPH10264125A (ja) * 1997-03-28 1998-10-06 Ngk Insulators Ltd セラミックハニカム構造体
JP2003010616A (ja) * 2001-06-29 2003-01-14 Ngk Insulators Ltd ハニカム構造体
JP2006519953A (ja) * 2003-02-18 2006-08-31 コーニング インコーポレイテッド セラミックハニカム体および製造方法

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS62234552A (ja) * 1986-04-02 1987-10-14 Mitsubishi Heavy Ind Ltd 触媒構造体
JPH10264125A (ja) * 1997-03-28 1998-10-06 Ngk Insulators Ltd セラミックハニカム構造体
JP2003010616A (ja) * 2001-06-29 2003-01-14 Ngk Insulators Ltd ハニカム構造体
JP2006519953A (ja) * 2003-02-18 2006-08-31 コーニング インコーポレイテッド セラミックハニカム体および製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3919158A4 (fr) * 2019-07-12 2022-05-04 Denso Corporation Filtre de purification de gaz d'échappement
US11845032B2 (en) 2019-07-12 2023-12-19 Denso Corporation Exhaust gas purification filter
US11845033B2 (en) 2019-08-20 2023-12-19 Denso Corporation Exhaust gas purification filter

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