WO2006101026A1 - ハニカム構造体及びその製造方法 - Google Patents
ハニカム構造体及びその製造方法 Download PDFInfo
- Publication number
- WO2006101026A1 WO2006101026A1 PCT/JP2006/305348 JP2006305348W WO2006101026A1 WO 2006101026 A1 WO2006101026 A1 WO 2006101026A1 JP 2006305348 W JP2006305348 W JP 2006305348W WO 2006101026 A1 WO2006101026 A1 WO 2006101026A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- partition
- honeycomb structure
- cam structure
- outer peripheral
- cell
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000005192 partition Methods 0.000 claims abstract description 114
- 230000002093 peripheral effect Effects 0.000 claims description 71
- 238000001125 extrusion Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 abstract description 19
- 210000004027 cell Anatomy 0.000 description 97
- 239000003054 catalyst Substances 0.000 description 56
- 239000007789 gas Substances 0.000 description 34
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 230000001747 exhibiting effect Effects 0.000 description 13
- 239000005022 packaging material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
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- 238000005452 bending Methods 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241001133184 Colletotrichum agaves Species 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000001419 dependent effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 noradium Chemical compound 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- 239000011230 binding agent Substances 0.000 description 1
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 210000001316 polygonal cell Anatomy 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- 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
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- C04B2111/2084—Thermal shock resistance
-
- 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
- C04B2111/32—Expansion-inhibited materials
- C04B2111/325—Expansion-inhibited materials the expansion being inhibited in one direction only
-
- 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
- C04B2111/34—Non-shrinking or non-cracking materials
- C04B2111/343—Crack resistant materials
-
- 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
- F01N2330/32—Honeycomb supports characterised by their structural details characterised by the shape, form or number of corrugations of plates, sheets or foils
-
- 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
- F01N2330/48—Honeycomb supports characterised by their structural details characterised by the number of flow passages, e.g. cell density
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/2414—Structurally defined web or sheet [e.g., overall dimension, etc.] including fringe
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
- Y10T428/24157—Filled honeycomb cells [e.g., solid substance in cavities, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
- Y10T428/24165—Hexagonally shaped cavities
Definitions
- the present invention relates to a support for exhaust gas purification of various internal combustion engines including automobile exhaust gas, a catalyst support for deodorization, a filter for various filtration devices, a heat exchange unit, or a reforming catalyst for a fuel cell.
- the present invention relates to a honeycomb structure that can be used as a carrier for a chemical reaction device such as a carrier for use.
- a cam structure is widely used as a catalyst for purification of exhaust gas discharged from various internal combustion engines including automobile exhaust gas and catalyst carrier for deodorization.
- honeycomb structure conventionally, for example, when used as an automobile exhaust gas purification catalyst, it is generally the case that the partition partitioning each cell is formed linearly throughout the whole of the honeycomb structure.
- One of the causes is that the catalyst is not activated sufficiently because the exhaust gas temperature is low, especially immediately after engine start-up, and as a result, harmful substances pass through the catalyst without being purified. is there.
- the combustion state of the fuel is not stable immediately after the start of the engine, and the exhaust gas AZF (air-fuel ratio), which is an important factor affecting the purification performance of the three-way catalyst, Fluctuation in the proportion of oxygen content is also a factor.
- Patent Document 1 discloses that the cell density is increased in the central portion to make the exhaust gas flow uniform.
- Patent Document 1 discloses that the cell density is increased in the central portion to make the exhaust gas flow uniform.
- there is a discontinuity in the cell structure at the boundary between the high cell density part and the low cell density part and there is a concern that the thermal shock resistance may be lowered.
- a special forming die is required.
- Patent Document 2 Japanese Utility Model Application Publication No. 60-145216
- the present invention provides a continuous cam cell structure that can achieve both low pressure loss and high purification performance.
- the present invention provides a method of manufacturing a half cam structure capable of extruding such a half cam structure with a conventional die without requiring a special die processing.
- a honeycomb structure comprising a plurality of partition walls respectively defining a plurality of axially extending cells, wherein at least a part of continuous partition force in the cross section perpendicular to the axial direction is outside from the center of the cross section Nom-cam structure showing a convexly curved shape toward the.
- a manufacturing method of a honeycomb structure including a step of forming a honeycomb formed body having a partition which respectively defines a plurality of axially extending cells by extrusion molding, which is a central portion of an extrusion surface And forming a partition wall having a curved shape in a cross section perpendicular to the axial direction by extruding at different extrusion speeds in the outer peripheral portion and the outer peripheral portion.
- FIGS. 1 (a) and 1 (b) are views schematically showing a first embodiment of a honeycomb structure of the present invention, and FIG. 1 (a) is parallel to the axial direction. 1 (b) is a schematic cross-sectional view.
- FIG. 2 is a cross-sectional view schematically showing a second embodiment of the cam structure of the present invention.
- FIG. 3 This is a view schematically showing the general behavior of fracture of a cam structure in a fracture mode dependent on buckling stress.
- FIG. 5 is a schematic view illustrating strength characteristics in the second embodiment of the cam structure of the present invention.
- FIG. 8 is a cross-sectional view schematically showing another form of curvature of the partition wall.
- FIG. 12 is a schematic view illustrating still another example of the method of manufacturing a green cam structure according to the present invention.
- cross section means a cross section perpendicular to the axial direction of the honeycomb structure, unless otherwise specified.
- FIGS. 1 (a) and 1 (b) are views schematically showing a first embodiment of a honeycomb structure of the present invention
- FIG. 1 (a) is a schematic view showing a cross section parallel to the axial direction.
- Parallel cross-sectional view and
- FIG. 1 (b) is a schematic cross-sectional view.
- the honeycomb structure 1 according to the embodiment shown in FIGS. 1 (a) and 1 (b) includes a plurality of partition walls 2 which respectively define a plurality of axially extending cells 3.
- FIG. 1 (b) the shape (hereinafter referred to as "positive curve") in which the partition wall 2 is curved convexly from the cross-sectional center 4 toward the outer side (direction of the outer peripheral wall 5) is shown.
- FIG. 2 is a cross-sectional view schematically showing a second embodiment of the honeycomb structure of the present invention.
- the cam structure 1 of the embodiment shown in FIG. 2 has a shape (hereinafter referred to as a negative curve) in which the partition wall 2 is convexly curved from the outer side (the outer peripheral wall 5 side) toward the center 4 of the cross section.
- the surface area of the partition in the central part can be increased, and the pressure loss during PM deposition can be reduced
- the following effects can be obtained in the strength of the honeycomb structure.
- the cell has a fracture mode (local fracture form and relatively low strength fracture) depending on the bending stress of the partition.
- the failure mode dependent on the buckling stress originally possessed by the honeycomb structure the failure mode of the entire structure becomes relatively high strength.
- FIG. 3 The general behavior of the fracture of the honeycomb structure in the fracture mode depending on the buckling stress when the cross-sectional shape of the cell is quadrangle is schematically shown in FIG.
- the cam structure in this failure mode, generally produces an isotropic overload which weakens in the direction of 45 degrees with respect to the longitudinal direction of the partition in the cross section, ie the diagonal direction of the cell 3. When received, it often deforms in this direction and breaks.
- the cell located in the vicinity of the outer peripheral portion 7 of the shape has a shape pointed in the direction of 90 degrees with respect to the line 6, that is, a shape deformed into a rhombus crushed in the direction of the line 6.
- the honeycomb structure receives an isotropic overload, the diamond-shaped cells in the vicinity of the outer peripheral portion 7 are likely to be crushed, so that the isostatic strength is not so favorable.
- the cells are deformed smoothly over the entire cam structure, and there is no extreme bending of the partition, resulting in a significant decrease in isostatic strength. It can be suppressed.
- the half cam structure (the second embodiment) having a partition exhibiting a negative curvature, as shown in FIG. 5, a line extending in a 45.degree.
- the cells located in the vicinity of the outer peripheral portion 7 of the are formed in a shape pointed in the direction of the line 6, that is, a cell deformed into a rhombus crushed in the direction of 90 degrees with respect to the line 6. Therefore, the isostatic strength is improved because such an outer peripheral diamond cell is resistant to collapse when subjected to isotropic overload.
- under isotropic load when the whole honeycomb structure is a compressive stress field and the force honeycomb structure is heated, the center of the honeycomb structure becomes a tensile stress field due to thermal expansion. In this case, since the partition exhibiting a negative curvature is highly resistant to tensile stress, the thermal shock resistance of the cam structure is improved.
- the average curvature (Wav) is preferably 0.6 mm or more. It is more preferable that the average curvature is 1. O mm or more. Further, in relation to the cell pitch (P), it is more preferable that (WavZP) is 1.2 mm or more, preferably 1.5 mm or more. On the other hand, if the degree of curvature is too large, the deformation of the cells located at the outer peripheral part of the hard cam structure becomes too large, so local breakage is likely to occur and the probability of low strength breakage becomes large. Curvature is preferably avoided.
- the limit value of curvature is Since it changes according to the size of two cams, material, cell shape, partition wall thickness and cell pitch, it can be determined experimentally based on them.
- the average curvature (Wav) is more preferably 15 mm or less, more preferably 10 mm or less.
- (WavZP) in relation to the cell pitch (P), it is more preferable that (WavZP) be 5 mm or less, preferably 3 mm / mm or less.
- the average curvature degree means the average of the maximum deviation width (Wn) from the straight line of each continuous partition wall (n), and the partition wall of honeycomb structure force ⁇ ⁇ n
- the average curvature Wav in the case of preparing and expressed by the following equation.
- Wav (W1 + W2 + W3H hWn) / n
- the partition wall 2 is connected from one point 5a of the outer peripheral wall to another point 5b of the outer peripheral wall. It is a smooth linear shape, that is, a linear shape having no inflection point.
- a partition forming one line having no inflection point connected from one point 5a of the outer peripheral wall to another point 5b of the outer peripheral wall is one continuous partition n.
- the shift width force between the straight line connecting the and the line formed by one continuous partition wall n can also determine the degree of curvature.
- the present invention is directed to a cell pattern in which cell patterns conventionally arranged in series in cross section are arranged in a curved line. That is, the straight line formed by connecting the cross-sectional centers of the cells aligned in a row in the conventional honeycomb structure is formed into a curved line.
- the cross-sectional center of each cell in a row By having at least a part of the cell pattern arranged such that the connected lines are curved, it is possible to obtain a half cam structure having the above-described effect.
- all of the partition walls need to be curved, and at least a part of continuous partition walls may be curved.
- the area of 25 area% or more is curved with respect to the entire partition in the cross section of the cam structure 50 area% or more
- the bulkhead of the wall is curved. According to the present invention, it is of course possible to bend only in a narrow local area, but for example when low pressure loss is aimed at, the contribution of the low pressure loss in the curved area to the overall pressure loss of the cam structure.
- one continuous partition may be curved with a constant curvature, but may be curved so as to change the curvature. In particular, as shown in FIG.
- the basic shape of the cell cross section of the cam structure is not particularly limited, but from the viewpoint of production, it is preferable to have any shape of triangle, square, hexagon and circle. These shapes may be used alone or in combination. Among these, a square basic shape is particularly preferable. Further, the cross-sectional shape of the honeycomb structure can also be any shape such as an oval, an oval, an oval, an almost triangular shape, an almost quadrangular shape, or any other shape in addition to a circular shape without particular limitation.
- materials for the hard cam structure cordierite, alumina, mullite, lithium 'aluminium' silicate, aluminum titanate, titanium oxide, zircon, silicon nitride, aluminum nitride
- Various ceramic materials such as minium and silicon carbide, various heat resistant metallic materials such as stainless steel, and various adsorptive materials such as activated carbon, silica gel and zeolite are suitably used. These materials are good either alone or in combination with them.
- the structure of the molding die can provide a honeycomb structure, so that different material particles and fibers are dispersed and composited in the above material.
- polymer materials such as materials, resins and the like, and those coated on the surface of partition walls after extrusion molding.
- the porosity of the partition walls is preferably 45 to 80%.
- the partition thickness of the hard cam structure is preferably about 0.2 to 20 mm, and the cell density is preferably about 50 to 600 cpsi (cell Z square inch).
- the wall surface of the hard cam structure uneven, it is possible to further improve the ability to remove particulates.
- supporting the catalyst on the partition wall can assist the regeneration of the honeycomb structure by PM combustion.
- the honeycomb structure of the present invention is also suitable as a three-way catalyst carrier, and the catalyst is supported on the partition wall surface of the honeycomb structure or on the inner surface of the pores in the partition wall, for example, It is used as a catalyst carrier for purification.
- the partition thickness in this case is approximately 0. 010-0. 120 mm, and the cell density is preferably approximately 200-3000 cpsi (cell Z square inch). It is preferable to set the porosity of the partition to 5 to 45% because the strength is reduced because the partition is made relatively thin because of low heat capacity.
- a catalyst component is supported on partition walls of a honeycomb structure to obtain a catalyst body, a method of forming the honeycomb structure itself with a catalyst component, or Any of these combined methods may be used.
- a composite having a high specific surface area coated with ⁇ -alumina on the surface of the partition wall of a cordierite-like two-cam structure and a hybrid having a noble metal component supported on the alumina layer as an automobile exhaust gas purification catalyst, solid catalysts in which a no-cam structure is composed of titanium dioxide or the like as an exhaust gas purification catalyst of fixed source power have been put to practical use.
- the catalyst component is usually a noble metal such as platinum, noradium, rhodium or vanadium It is composed of a combination of oxides, ceria, yttria, zirconia, titanium, alkali metals, perovskite-based composites, and tourmaline components.
- the catalyst is usually a three-way catalyst that oxidizes and reduces hydride carbon, carbon monoxide, and nitrogen oxides; oxidation that oxidizes carbon component, carbon monoxide, NO, SOF, and carbon components.
- Catalysts for reducing NOx; and at least one member selected from the group consisting of catalyst catalysts for decomposing and removing sulfides and volatile organic compounds (VOC) components and dioxins, or , These compounds.
- VOC volatile organic compounds
- the catalyst component as described above can be used as a carrier for the catalyst. It is effective to use a cam structure.
- the honeycomb structure of the present invention is also applicable to the following exhaust gas purification systems.
- the cam structure is generally positively charged, and electrically generally negatively charged particulate matter is collected.
- the honeycomb structure may be negatively charged.
- As an exhaust gas cleaning system using a similar honeycomb structure a system for collecting particulate matter using non-thermal plasma or microwave discharge plasma is cited. It is also possible to apply the honeycomb structure of the present invention to these.
- Another application of the honeycomb structure of the present invention is as a catalyst carrier in a reformer for a fuel cell system or a fuel cell main body.
- the extrusion speed at which the material is extruded from the extrusion surface 10 is extruded so as to be uniform throughout.
- the raw material is extruded at different extrusion speeds at the central portion and the outer peripheral portion of the extrusion surface 10.
- the extrusion speed in the vicinity of the outer peripheral wall is kept constant, and the extrusion speed is changed on the inner side, so that the partition wall in the vicinity of the contact portion between the outer peripheral wall and the partition wall.
- the partition wall in the vicinity of the contact portion between the outer peripheral wall and the partition wall Can suppress excessive deformation of Also, if the partition is excessively bent in the vicinity of the contact portion between the outer peripheral wall and the partition, the outer peripheral portion of the cam structure is removed by calories to remove the curved portion, and the outer peripheral wall is newly coated. By doing so, it is possible to produce an excessively curved partition wall! And a two cam structure.
- the extrusion molding can be performed, for example, using a ram extrusion molding machine, a twin screw continuous extrusion molding apparatus, or the like.
- a raw material water and a binder are mixed with a raw material of cordierite clay mainly composed of talc, kaolin and alumina, mixed and kneaded, and the formed raw material is introduced into an extruder equipped with a conventional die and extruded. Then, a green compact was obtained, which was dried and cut to a predetermined length, and the cells were alternately sealed and fired.
- the outer peripheral wall of the obtained sintered body and partition walls for several cells from the outermost periphery are ground and removed, and a ceramic coating material is applied to the outer periphery to form an outer peripheral wall, to obtain a hcam structure having the following configuration.
- Partition thickness 0.2 mm
- Partition thickness 0.37 mm
- Outer shape of honeycomb structure cylindrical (outside diameter: 144 mm, length: 152 mm)
- a hard cam structure was obtained in the same manner as in Comparative Example 3 except that the resistance screen was attached to the central portion on the back side of the die.
- the cell density in the central part of the double cam structure was 260 280 cpsi, while in the peripheral part it became 230 240 cpsi, because the partition exhibited a negative curve.
- the degree of curvature was also measured in the same manner as in Example 1. The degree of curvature obtained at each measurement point as in Example 1 is shown in Table 2. The degree of curvature was 1. Omm on average.
- the honeycomb structures of Comparative Example 3 and Example 3 are subjected to the isostatic fracture strength test based on the method defined by the automobile standard (JASO standard) M505-87 issued by Japan Automobile Engineering Association. Did.
- This test is a test in which a hard cam structure is put in a rubber cylindrical container and covered with an aluminum plate, and isostatic pressing and compression is carried out in water. This is a test that simulates the compressive load weight when the outer peripheral surface is gripped.
- the isostatic strength is indicated by the pressure value at which the cam structure breaks.
- Catalytic converters for automotive exhaust gas cleaning usually adopt a clamping structure by gripping the outer peripheral surface of a cam structure, and it is a matter of course that the isostatic fracture strength is high on molding. Is preferred.
- Example 3 The cam structure of Example 3 exhibited an approximately 10% higher isostatic fracture strength than the cam structure of Comparative Example 3. Also, the heat resistance mentioned above As a result of the impact test also, in Example 3, a safety temperature improvement of about 30 ° C. was observed as compared to Comparative Example 3.
- the three-way catalyst carrier of Comparative Example 4 is the same as Comparative Example 1 except that the outer peripheral wall and the partition wall in the vicinity thereof are not removed and are not sealed, and the honeycomb structure having the configuration shown below is used. -Got a cam structure.
- Outer shape of honeycomb structure cylindrical (outside diameter: 100 mm, length: 100 mm)
- Average coefficient of thermal expansion in the axial direction at 40-800 ° C . about 0.4 ⁇ 10 "V ° C.
- the test was conducted. Note that the catalytic converter is a separate engine 900 ° CX 50 hours prior to this mode test Aging treatment was performed.
- the emissions of carbon dioxide (HC), carbon dioxide (CO) and nitrogen oxides (NOx) are large compared to the conventional catalyst of Comparative Example 4. It was confirmed to reduce to the width.
- the cam structure of the present invention is a carrier for an exhaust gas purification catalyst for various internal combustion engines including automobile exhaust gas, a catalyst carrier for deodorizing, a filter for various filtration devices, a heat exchanger It can be used as a carrier for a chemical reaction device such as a unit or a carrier for a reforming catalyst of a fuel cell.
- the manufacturing method of the present invention can suitably manufacture such a honeycomb structure.
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- Life Sciences & Earth Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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KR1020077021032A KR100930554B1 (ko) | 2005-03-22 | 2006-03-17 | 허니콤 구조체 및 그 제조 방법 |
EP06729338.1A EP1862279B1 (en) | 2005-03-22 | 2006-03-17 | Honeycomb structure and method of manufacturing the same |
CN2006800090247A CN101146656B (zh) | 2005-03-22 | 2006-03-17 | 蜂窝结构体及其制造方法 |
US11/889,291 US7601195B2 (en) | 2005-03-22 | 2007-08-10 | Honeycomb structure and method of manufacturing the same |
Applications Claiming Priority (2)
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JP2005-081330 | 2005-03-22 | ||
JP2005081330A JP4511396B2 (ja) | 2005-03-22 | 2005-03-22 | ハニカム構造体及びその製造方法 |
Related Child Applications (1)
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US11/889,291 Continuation US7601195B2 (en) | 2005-03-22 | 2007-08-10 | Honeycomb structure and method of manufacturing the same |
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WO2006101026A1 true WO2006101026A1 (ja) | 2006-09-28 |
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US (1) | US7601195B2 (ja) |
EP (1) | EP1862279B1 (ja) |
JP (1) | JP4511396B2 (ja) |
KR (1) | KR100930554B1 (ja) |
CN (1) | CN101146656B (ja) |
WO (1) | WO2006101026A1 (ja) |
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EP1862279B1 (en) | 2019-11-20 |
CN101146656A (zh) | 2008-03-19 |
US20070294989A1 (en) | 2007-12-27 |
EP1862279A4 (en) | 2011-08-17 |
KR20070112178A (ko) | 2007-11-22 |
EP1862279A1 (en) | 2007-12-05 |
US7601195B2 (en) | 2009-10-13 |
CN101146656B (zh) | 2011-04-20 |
JP4511396B2 (ja) | 2010-07-28 |
KR100930554B1 (ko) | 2009-12-09 |
JP2006263947A (ja) | 2006-10-05 |
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