WO2009122537A1 - Process for producing honeycomb structure - Google Patents
Process for producing honeycomb structure Download PDFInfo
- Publication number
- WO2009122537A1 WO2009122537A1 PCT/JP2008/056412 JP2008056412W WO2009122537A1 WO 2009122537 A1 WO2009122537 A1 WO 2009122537A1 JP 2008056412 W JP2008056412 W JP 2008056412W WO 2009122537 A1 WO2009122537 A1 WO 2009122537A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- aluminum titanate
- honeycomb structure
- honeycomb
- powder
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 103
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims abstract description 99
- 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 claims abstract description 99
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000010304 firing Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 239000003566 sealing material Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 12
- 238000011069 regeneration method Methods 0.000 abstract description 12
- 238000011282 treatment Methods 0.000 abstract description 11
- 238000000465 moulding Methods 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 18
- 210000002421 cell wall Anatomy 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
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- 239000000314 lubricant Substances 0.000 description 6
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
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- 238000000354 decomposition reaction Methods 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- -1 polyoxyethylene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052650 alkali feldspar Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
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- 238000005238 degreasing Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 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 2
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- 239000012535 impurity Substances 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Classifications
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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
- F01N3/2839—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
- F01N3/2842—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration specially adapted for monolithic supports, e.g. of honeycomb type
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- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
- C04B2235/5472—Bimodal, multi-modal or multi-fraction
Definitions
- the present invention relates to a method for manufacturing a honeycomb structure.
- exhaust gas discharged from an internal combustion engine such as a diesel engine contains particulate matter (hereinafter also referred to as PM).
- PM particulate matter
- various filters using honeycomb structures made of cordierite, silicon carbide, aluminum titanate, etc. have been proposed as filters for collecting PM in exhaust gas and purifying the exhaust gas.
- a honeycomb structure made of aluminum titanate has a higher melting temperature than a honeycomb structure made of cordierite, and is less resistant to melting when burning PM. ing.
- a honeycomb structure made of aluminum titanate has a lower thermal expansion coefficient than that of a honeycomb structure made of silicon carbide, so that cracks due to thermal stress are unlikely to occur and the thermal shock resistance is high.
- a method for manufacturing a honeycomb structure made of aluminum titanate as described above for example, a method disclosed in Patent Document 1 is known.
- Patent Document 1 discloses a method for manufacturing a honeycomb structure, in which a honeycomb structure mainly made of aluminum titanate is manufactured by adding alkali feldspar and MgO to a mixture of TiO 2 and Al 2 O 3 and firing the mixture. Is disclosed.
- Patent Document 1 describes that by using the method for manufacturing a honeycomb structure described in this document, a honeycomb structure mainly made of aluminum titanate having high heat resistance and thermal shock resistance can be manufactured. ing. Moreover, it is described that the honeycomb structure manufactured by the manufacturing method described in Patent Document 1 has high heat decomposition resistance and high fracture strength due to the effect of alkali feldspar-derived components and MgO-derived Mg.
- the honeycomb structure manufactured by the method for manufacturing a honeycomb structure described in Patent Document 1 is used as a filter for exhaust gas purification, and regeneration processing for burning PM collected in the honeycomb structure is repeatedly performed,
- the breaking strength may be low. That is, the honeycomb structure manufactured by the method for manufacturing a honeycomb structure described in Patent Document 1 has insufficient heat resistance against repeated regeneration processing. Therefore, a method for manufacturing a honeycomb structure having high heat resistance against repeated regeneration processing has been desired.
- the present inventors have intensively studied to solve the above problems, and have a relatively large average particle diameter of aluminum titanate coarse powder (hereinafter also simply referred to as coarse powder) and a relatively small average particle diameter. It has been found that a honeycomb structure with high fracture strength can be produced by using aluminum titanate fine powder (hereinafter also simply referred to as fine powder). In particular, by using aluminum titanate coarse powder having a specific composition ratio and aluminum titanate fine powder having a specific composition ratio, the honeycomb structure has high fracture strength and high heat resistance against repeated regeneration treatments. The present invention was completed by finding that a body can be produced.
- Aluminum oxide coarse powder, average particle size of 0.1 to 3 ⁇ m, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1 to 8% by mass Forming a wet mixture containing aluminum titanate fine powder having a composition ratio of less than 1% to produce a columnar honeycomb formed body in which a number of cells are arranged in the longitudinal direction; And a firing step of firing the honeycomb formed body at 1200 ° C. to 1700 ° C.
- an aluminum titanate fine powder means that whose average particle diameter is smaller than the average particle diameter of aluminum titanate coarse powder. Therefore, when the average particle diameter of the aluminum titanate coarse powder is 3 ⁇ m, the average particle diameter of the aluminum titanate fine powder is less than 3 ⁇ m.
- the production method of the present invention is characterized by using aluminum titanate fine powder and aluminum titanate coarse powder as aluminum titanate powder.
- aluminum titanate fine powder and titanic acid are used.
- aluminum titanate powder refers to both an aluminum titanate fine powder and an aluminum titanate coarse powder.
- honeycomb structured body In the method for manufacturing a honeycomb structured body according to claim 1, after forming a honeycomb formed body using a mixture containing a pre-prepared aluminum titanate coarse powder and aluminum titanate fine powder having a specific composition ratio. The honeycomb formed body is fired to produce a honeycomb structure.
- the aluminum titanate coarse powder and the aluminum titanate fine powder contain Mg and Si, and the aluminum titanate powder containing Mg and Si is more heated than the aluminum titanate powder not containing Mg and Si. It becomes an aluminum titanate powder that is hardly decomposed and has high heat resistance.
- the coarse powder in which the total of MgO and SiO 2 is 8% by mass or more and 15% by mass or less is more heat resistant than the fine powder in which the total of MgO and SiO 2 is 1% by mass or more and less than 8% by mass.
- honeycomb formed body including a coarse powder having a relatively high heat resistance and a fine powder having a relatively low heat resistance
- the fracture strength is high, and further, repeated reprocessing.
- a honeycomb structure having high heat resistance can be manufactured.
- the honeycomb formed body is fired at 1200 to 1700 ° C. Therefore, the particles can be bonded to each other, the degree of shrinkage during firing can be reduced, and the decomposition of aluminum titanate can be suppressed. Thereby, in the manufactured honeycomb structure, the variation in the pore size distribution is reduced. And such a honeycomb structure with a small variation in pore size distribution has a high breaking strength.
- the firing temperature is less than 1200 ° C.
- the sintering of aluminum titanate may not sufficiently proceed.
- the said calcination temperature exceeds 1700 degreeC, the shrinkage degree at the time of baking will become large, As a result, a pore diameter may not be uniform.
- aluminum titanate may be decomposed.
- composition ratio of the aluminum titanate coarse powder is 40-50% by mass of Al 2 O 3 , 40-50% by mass of TiO 2 , MgO and SiO 2 .
- the total is 8% by mass or more and 12% by mass or less.
- composition ratio of the aluminum titanate fine powder is 40-50% by mass of Al 2 O 3 , 40-50% by mass of TiO 2 , MgO and SiO 2 .
- the total is 1% by mass or more and 5% by mass or less.
- a method for manufacturing a honeycomb structured body wherein a sealing step of filling a plug material paste at one end of each cell of the honeycomb formed body is performed.
- the sealing step since the sealing step is performed, the manufactured honeycomb structure can be used as a filter for purifying exhaust gas.
- Fig. 1 (a) is a perspective view schematically showing the honeycomb structure manufactured in the first embodiment of the present invention
- Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a).
- FIG. 1 (a) is a perspective view schematically showing the honeycomb structure manufactured in the first embodiment of the present invention
- Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a).
- a honeycomb structure 10 shown in FIG. 1 (a) is made of aluminum titanate and has a cylindrical shape. In the interior thereof, as shown in FIG. 1B, a plurality of cells 11 are formed along the longitudinal direction of the honeycomb structure 10, and each cell 11 is separated by a cell wall 13. . One end of the cell 11 is sealed with a sealing material 12.
- the sealing material 12 is made of the same material as the honeycomb structure 10 and is made of aluminum titanate.
- the sealing material 12 seals the honeycomb structure 10 so that the exhaust gas does not leak from one end of the cell 11. For this reason, the exhaust gas flowing into one cell (indicated by an arrow in FIG. 1B) always passes through the cell wall 13 separating the one cell and then flows out from the other cells. Therefore, when exhaust gas passes through the cell wall 13, PM is collected inside the cell wall 13 and the exhaust gas is purified.
- a wet mixture is prepared by mixing aluminum titanate coarse powder, aluminum titanate fine powder, pore-forming agent, organic binder, plasticizer, lubricant and water and stirring sufficiently.
- the aluminum titanate coarse powder has an average particle diameter of 3 to 50 ⁇ m, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 8% by mass or more.
- An aluminum titanate powder having a composition ratio of 15% by mass or less is used.
- the aluminum titanate fine powder has an average particle diameter of 0.1 to 3 ⁇ m, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1 mass.
- An aluminum titanate powder having a composition ratio of not less than 8% and less than 8% by mass is used.
- the composition ratio of the aluminum titanate powder is measured using ICP emission spectroscopic analysis.
- ICP emission spectroscopic analysis plasma energy is applied to an analysis sample from the outside, the contained elements (atoms) are excited, and emitted light (spectrum) is emitted when the excited atoms return to a low energy level. Line) for each photon wavelength. Then, the type of the component element is determined from the position of the emission line, and the content of the component element is obtained from the intensity of the emission line.
- the reason why the composition ratio of the aluminum titanate coarse powder and the aluminum titanate fine powder is in the above range is as follows. That is, when the composition ratio of Al 2 O 3 and TiO 2 is out of the above range, when the manufactured honeycomb structure is used, the honeycomb structure is repeatedly exposed to heat such as exhaust gas, whereby aluminum titanate. Will gradually decompose into Al 2 O 3 and TiO 2 . As a result, the physical properties of aluminum titanate cannot be exhibited, and the strength of the honeycomb structure is reduced.
- the total composition ratio of fine powder MgO and SiO 2 is less than 1.0% by mass
- the honeycomb structure is repeatedly exposed to heat such as exhaust gas
- Aluminum titanate is gradually decomposed into Al 2 O 3 and TiO 2 .
- the lower limit of the total composition ratio of fine powder MgO and SiO 2 is preferably 2.5% by mass. This is because when the content is 2.5% by mass or more, the decomposition of aluminum titanate is less likely to proceed.
- the composition ratio of the aluminum titanate coarse powder is 40 to 50% by mass of Al 2 O 3 , 40 to 50% by mass of TiO 2 , and the total of MgO and SiO 2 is 8 to 12% by mass. It is more desirable.
- the composition ratio of the aluminum titanate fine powder is 40-50 mass% for Al 2 O 3, 40-50 mass% for TiO 2 , and the total of MgO and SiO 2 is 1 mass% to 5 mass%. It is more desirable.
- the wet mixture is extrusion-molded by an extruder to produce a columnar honeycomb molded body having a large number of cells arranged in parallel in the longitudinal direction. Thereafter, the long body of the honeycomb formed body is cut by a cutting device having a cutting disk as a cutting member to obtain a honeycomb formed body having a predetermined length.
- the honeycomb formed body is dried for 1 to 30 minutes under a condition of 100 to 150 ° C. in an air atmosphere using a microwave dryer and a hot air dryer.
- the honeycomb formed body in which one end of each cell is filled with the plug material paste is dried again.
- the sealing material paste a paste having the same composition as the wet mixture is used.
- the honeycomb formed body is degreased in a degreasing furnace for 3 to 15 hours under conditions of an oxygen concentration of 5% by volume to an atmospheric atmosphere at 250 to 400 ° C. Thereafter, firing is performed at a temperature of 1200 to 1700 ° C. for 0.5 to 24 hours in a firing furnace.
- the honeycomb structure 10 described above can be manufactured through such steps.
- honeycomb structured body of the present embodiment a honeycomb formed body made of a mixture containing a coarse powder having a relatively high heat resistance and a fine powder having a relatively low heat resistance is fired.
- a honeycomb structure having high fracture strength and high heat resistance against repeated regeneration treatment can be produced.
- the coarse particle of the aluminum titanate powder has an average particle diameter of 3 to 50 ⁇ m, Al 2 O 3 of 40 to 60% by mass, and TiO 2 of 30 to 30%.
- An aluminum titanate powder having a composition ratio of 50% by mass and a total of MgO and SiO 2 of 8% by mass to 15% by mass is used, and the average particle size is 0.1 to 3 ⁇ m as a fine powder of the aluminum titanate powder.
- Aluminum titanate powder having a composition ratio of Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1% by mass to less than 8% by mass is used. ing. Therefore, in the manufactured honeycomb structure, decomposition of aluminum titanate does not proceed, and cracks due to thermal expansion do not occur in the manufactured honeycomb structure.
- the honeycomb formed body is fired at 1200 to 1700 ° C., so that the particles are bonded to each other, the degree of shrinkage during firing is reduced, and the aluminum titanate is decomposed. Can be suppressed. Sintering of the honeycomb formed body produced using the mixture containing the aluminum titanate powder proceeds without excess or deficiency. Thereby, in the manufactured honeycomb structure, the variation in the pore size distribution is reduced.
- the aluminum titanate powder aluminum titanate coarse powder having an average particle diameter of 3 to 50 ⁇ m and aluminum titanate fine powder having an average particle diameter of 0.1 to 3 ⁇ m Powder is used.
- the average particle size of each powder should be appropriately selected.
- the pore diameter of the honeycomb structure can be controlled.
- a sealing step of filling a plug material paste into one end of each cell of the honeycomb formed body is performed. Therefore, the manufactured honeycomb structure can be used as a filter for purifying exhaust gas.
- aluminum titanate powders A to D having different composition ratios were prepared.
- the composition ratios of the aluminum titanate powders A to D are as shown in Table 1.
- Aluminum titanate powders A and C are aluminum titanate powders in which the total of MgO and SiO 2 is 1% by mass or more and less than 8% by mass.
- Aluminum titanate powders B and D are aluminum titanate powders in which the total of MgO and SiO 2 is 8% by mass or more and 15% by mass or less.
- the total amount of each component is not 100% by mass, because the aluminum titanate powder contains impurities.
- the impurities include alkali feldspar-derived substances (K 2 O, Na 2 O, etc.), Al 2 O 3 powder as a raw material for iron compounds and aluminum titanate powders when the aluminum titanate powder is pulverized or mixed. And substances originally contained in TiO 2 powder.
- each aluminum titanate powder the grinding
- a powder having a large average particle size was used as a coarse powder, and a powder having a small average particle size was used as a fine powder.
- Example 1 2000 parts by weight of coarse powder of aluminum titanate B having an average particle diameter of 20 ⁇ m, 500 parts by weight of fine powder of aluminum titanate A having an average particle diameter of 0.5 ⁇ m, 300 parts by weight of pore-forming agent (spherical acrylic particles), organic A wet mixture was prepared by mixing 188 parts by weight of a binder (methylcellulose), 96 parts by weight of a plasticizer (Unilube manufactured by NOF Corporation), 44 parts by weight of a lubricant (glycerin) and 725 parts by weight of water, and stirring sufficiently.
- a binder methylcellulose
- plasticizer Unilube manufactured by NOF Corporation
- a lubricant glycerin
- honeycomb formed body was cut using a cutting device provided with a cutting disk as a cutting member. Thereby, a honeycomb formed body made of columnar aluminum titanate was obtained.
- honeycomb formed body was dried with a microwave dryer and a hot air dryer under the atmosphere at 120 ° C. for 20 minutes to remove moisture contained in the honeycomb formed body.
- the degreased honeycomb formed body was fired in a firing furnace at 1500 ° C. for 1 hour. Through the steps (1) to (7), a cell having a cell wall thickness of 0.2 mm (8 mil) and a cell density of 46.5 cells / cm 2 (300 cpsi) along the longitudinal direction. A honeycomb structure made of aluminum titanate having a diameter of 143.8 mm and a length in the longitudinal direction of 150 mm was completed. Note that the porosity of the honeycomb structure manufactured in Example 1 was 40%. The porosity was measured by mercury porosimetry.
- Examples 2 to 6 Comparative Examples 1 to 4
- a honeycomb structure was manufactured in the same manner as in Example 1 except that the kind of aluminum titanate coarse powder or the fine powder of aluminum titanate and the average particle size were changed.
- the types and average particle diameters of the aluminum titanate powders used in each example and each comparative example are as shown in Table 2 below.
- honeycomb structure (Evaluation of honeycomb structure) The honeycomb structures manufactured in Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to a regeneration treatment by the following method 30 times, and then the fracture strength of the honeycomb structure was measured by the following method.
- the honeycomb structures of the example and the comparative example are respectively disposed in the exhaust passage of a 2 L engine, and further on the gas inflow side of the honeycomb structure, a catalyst support (diameter: 200 mm, Length: 100 mm, cell density: 400 cells / inch 2 , platinum carrying amount: 5 g / L) is installed as an exhaust gas purifier, and the engine collects particulates for 10 hours at a rotational speed of 3000 min ⁇ 1 and a torque of 50 Nm. did. The amount of particulates collected was 10 g / L. After that, the engine is set at a rotational speed of 1250 min ⁇ 1 and a torque of 60 Nm, and the filter temperature is kept constant for 1 minute.
- the post-injection is performed, and the exhaust gas temperature is raised using the oxidation catalyst in front.
- the particulates were burned.
- the post-injection conditions were set so that the temperature of the exhaust gas flowing into the honeycomb structure after 1 minute from the start became substantially constant at 600 ° C.
- the mixing ratio of the aluminum titanate fine powder and the aluminum titanate coarse powder is desirably 9: 1 to 6: 4.
- the mixing ratio of the two is within the above range, when the honeycomb formed body is fired, the size after firing can be prevented from being reduced by shrinkage, and the average pore diameter, pore diameter distribution, and porosity can be reduced. This is because it can be controlled.
- the firing time when firing the honeycomb formed body is preferably 0.5 to 24 hours. This is because if the firing time is less than 0.5 hours, firing may not proceed, and if it exceeds 24 hours, shrinkage after firing may increase.
- the organic binder used when preparing the said wet mixture is not specifically limited, For example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol etc. are mentioned. Of these, methylcellulose is desirable.
- the amount of the organic binder is desirably 1 to 10 parts by weight per 100 parts by weight of the aluminum titanate powder.
- the plasticizer and lubricant used in preparing the wet mixture are not particularly limited, and examples of the plasticizer include glycerin.
- examples of the lubricant include polyoxyalkylene compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether.
- Specific examples of the lubricant include polyoxyethylene monobutyl ether and polyoxypropylene monobutyl ether. In some cases, the plasticizer and the lubricant may not be contained in the wet mixture.
- the pore forming agent used when preparing the wet mixture is not particularly limited, and examples thereof include spherical acrylic particles and graphite. In some cases, the pore-forming agent may not be contained in the wet mixture.
- a dispersion medium other than water may be used.
- examples of such a dispersion medium include alcohols such as methanol and organic solvents such as benzene and toluene. It is done.
- a molding aid may be added to the wet mixture.
- the molding aid is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol and the like.
- the temperature of the wet mixture is preferably 10 ° C. or lower. It is because an organic binder may gelatinize when temperature is too high.
- the plug material paste for sealing cells is not particularly limited, but the porosity of the plug material formed through a subsequent process is 40 to 50%.
- a thing similar to the said wet mixture can be used, for example.
- an apparatus used for producing a long body of a honeycomb formed body by extrusion molding is not particularly limited, and for example, a single screw extrusion molding Machine, multi-screw type extruder, plunger type machine and the like.
- a plunger type molding machine can be particularly preferably used.
- the dryer used for drying the honeycomb formed body is not particularly limited, and examples thereof include a microwave heating dryer, a hot air dryer, an infrared dryer, and the like. Is mentioned. These may be used alone or in combination.
- the shape of the cross section perpendicular to the longitudinal direction of the honeycomb structure manufactured in the embodiment of the present invention is not particularly limited to a circular shape, and may be various shapes such as a rectangle. And a shape surrounded by a straight line.
- a shape in which a part of a simple closed curve such as an ellipse, an ellipse, a racetrack, an ellipse, or an ellipse has a concave portion (concave shape) can be given.
- a desirable value of the aperture ratio of the honeycomb structure manufactured in the embodiment of the present invention is a lower limit of 50% and an upper limit of 75%.
- the opening ratio is less than 50%, the pressure loss when the exhaust gas flows into and out of the honeycomb structure may increase, and when it exceeds 75%, the strength of the honeycomb structure may decrease.
- a desirable lower limit of the cell wall thickness is 0.15 mm. This is because if the thickness is less than 0.15 mm, the strength of the honeycomb structure may be lowered.
- the desirable upper limit of the cell wall thickness is 0.4 mm. When the thickness of the cell wall exceeds 0.4 mm, the cell aperture ratio and / or the filtration area may be reduced, and the pressure loss may increase accordingly.
- the cell density is not particularly limited, and a desirable lower limit is 23.3 / cm 2 (150 / in 2 ), and a desirable upper limit is 93.0) / cm 2 (600 / in 2 ), more desirable lower limit is 31 / cm 2 (200 / in 2 ), and a more desirable upper limit is 77.5 / cm 2 (500.0 / in 2 ). is there.
- the shape of the cell in plan view is not particularly limited to a quadrangle, and examples thereof include a triangle, a hexagon, an octagon, a dodecagon, a circle, an ellipse, and a star.
- a catalyst may be supported on the honeycomb structure as necessary.
- the type of catalyst supported on the honeycomb structure is not particularly limited, and examples thereof include noble metal elements, alkali metal elements, alkaline earth metal elements, and metal oxides. These may be used alone or in combination of two or more.
- Examples of the noble metal element include platinum, palladium, rhodium and the like, examples of the alkali metal element include potassium and sodium, and examples of the alkaline earth metal element include barium and the like. It is done.
- Examples of the metal oxide include CeO 2 , K 2 O, ZrO 2 , FeO 2 , Fe 2 O 3 , CuO, CuO 2 , Mn 2 O 3 , MnO, composition formula An B 1-n CO 3 (where 0 ⁇ n ⁇ 1, A is La, Nd, Sm, Eu, Gd or Y, B is an alkali metal or alkaline earth metal, and C is Mn, Co, Fe or Ni) ) And the like.
- the PM combustion temperature can be lowered when the honeycomb structure is used as a honeycomb filter for the regeneration treatment.
- an alumina film having a high specific surface area may be formed on the surface of the honeycomb structure, and the catalyst may be applied to the surface of the alumina film.
- FIG. 1 (a) is a perspective view schematically showing the honeycomb structure manufactured in the first embodiment of the present invention
- FIG. 1 (b) is a cross-sectional view taken along the line AA in FIG. 1 (a). It is.
Abstract
A process for producing a honeycomb structure exhibiting high heat resistance in repeated regeneration treatment. The process for producing a honeycomb structure is characterized by including the molding step of molding a wet mixture containing an aluminum titanate coarse powder of 3 to 50 μm average particle diameter whose component proportion is 40 to 60 mass% Al2O3, 30 to 50 mass% TiO2 and 8 to 15 mass% sum of MgO and SiO2 together with an aluminum titanate fine powder of 0.1 to 3 μm average particle diameter whose component proportion is 40 to 60 mass% Al2O3, 30 to 50 mass% TiO2 and 1 to less than 8 mass% sum of MgO and SiO2 into a columnar honeycomb molded item having a multiplicity of cells laid parallelly along the longitudinal direction and the firing step of firing the honeycomb molded item at 1200° to 1700°C.
Description
本発明は、ハニカム構造体の製造方法に関する。
The present invention relates to a method for manufacturing a honeycomb structure.
従来、ディーゼルエンジン等の内燃機関から排出される排ガス中には、パティキュレートマター（以下、ＰＭともいう）が含まれており、近年、このＰＭが環境や人体に害を及ぼすことが問題となっている。
そこで、排ガス中のＰＭを捕集して排ガスを浄化するフィルタとして、コージェライト、炭化ケイ素、チタン酸アルミニウムなどからなるハニカム構造体を用いたものが種々提案されている。 Conventionally, exhaust gas discharged from an internal combustion engine such as a diesel engine contains particulate matter (hereinafter also referred to as PM). In recent years, it has been a problem that this PM is harmful to the environment and the human body. ing.
Accordingly, various filters using honeycomb structures made of cordierite, silicon carbide, aluminum titanate, etc. have been proposed as filters for collecting PM in exhaust gas and purifying the exhaust gas.
そこで、排ガス中のＰＭを捕集して排ガスを浄化するフィルタとして、コージェライト、炭化ケイ素、チタン酸アルミニウムなどからなるハニカム構造体を用いたものが種々提案されている。 Conventionally, exhaust gas discharged from an internal combustion engine such as a diesel engine contains particulate matter (hereinafter also referred to as PM). In recent years, it has been a problem that this PM is harmful to the environment and the human body. ing.
Accordingly, various filters using honeycomb structures made of cordierite, silicon carbide, aluminum titanate, etc. have been proposed as filters for collecting PM in exhaust gas and purifying the exhaust gas.
これらのなかで、チタン酸アルミニウムからなるハニカム構造体は、コージェライトからなるハニカム構造体よりも溶融温度が高く、ＰＭを燃焼させた際に溶損が発生しにくいため、耐熱性が高いとされている。
また、チタン酸アルミニウムからなるハニカム構造体は、炭化ケイ素からなるハニカム構造体よりも熱膨張係数が低いので、熱応力によるクラックが発生しにくく耐熱衝撃性が高いとされている。
そして、上述したようなチタン酸アルミニウムからなるハニカム構造体を製造する方法としては、例えば、特許文献１に開示された方法が知られている。 Among these, a honeycomb structure made of aluminum titanate has a higher melting temperature than a honeycomb structure made of cordierite, and is less resistant to melting when burning PM. ing.
In addition, a honeycomb structure made of aluminum titanate has a lower thermal expansion coefficient than that of a honeycomb structure made of silicon carbide, so that cracks due to thermal stress are unlikely to occur and the thermal shock resistance is high.
As a method for manufacturing a honeycomb structure made of aluminum titanate as described above, for example, a method disclosed in Patent Document 1 is known.
また、チタン酸アルミニウムからなるハニカム構造体は、炭化ケイ素からなるハニカム構造体よりも熱膨張係数が低いので、熱応力によるクラックが発生しにくく耐熱衝撃性が高いとされている。
そして、上述したようなチタン酸アルミニウムからなるハニカム構造体を製造する方法としては、例えば、特許文献１に開示された方法が知られている。 Among these, a honeycomb structure made of aluminum titanate has a higher melting temperature than a honeycomb structure made of cordierite, and is less resistant to melting when burning PM. ing.
In addition, a honeycomb structure made of aluminum titanate has a lower thermal expansion coefficient than that of a honeycomb structure made of silicon carbide, so that cracks due to thermal stress are unlikely to occur and the thermal shock resistance is high.
As a method for manufacturing a honeycomb structure made of aluminum titanate as described above, for example, a method disclosed in Patent Document 1 is known.
特許文献１には、ＴｉＯ２とＡｌ２Ｏ３とからなる混合物に、アルカリ長石、ＭｇＯを添加し、焼成することにより主にチタン酸アルミニウムからなるハニカム構造体を製造するハニカム構造体の製造方法が開示されている。
Patent Document 1 discloses a method for manufacturing a honeycomb structure, in which a honeycomb structure mainly made of aluminum titanate is manufactured by adding alkali feldspar and MgO to a mixture of TiO 2 and Al 2 O 3 and firing the mixture. Is disclosed.
特許文献１には、この文献に記載のハニカム構造体の製造方法を用いることにより、耐熱性及び耐熱衝撃性の高い、主にチタン酸アルミニウムからなるハニカム構造体を製造することができると記載されている。
また、特許文献１に記載の製造方法で製造したハニカム構造体は、アルカリ長石由来の成分及びＭｇＯ由来のＭｇの効果により、耐熱分解性及び破壊強度が高いと記載されている。 Patent Document 1 describes that by using the method for manufacturing a honeycomb structure described in this document, a honeycomb structure mainly made of aluminum titanate having high heat resistance and thermal shock resistance can be manufactured. ing.
Moreover, it is described that the honeycomb structure manufactured by the manufacturing method described in Patent Document 1 has high heat decomposition resistance and high fracture strength due to the effect of alkali feldspar-derived components and MgO-derived Mg.
また、特許文献１に記載の製造方法で製造したハニカム構造体は、アルカリ長石由来の成分及びＭｇＯ由来のＭｇの効果により、耐熱分解性及び破壊強度が高いと記載されている。 Patent Document 1 describes that by using the method for manufacturing a honeycomb structure described in this document, a honeycomb structure mainly made of aluminum titanate having high heat resistance and thermal shock resistance can be manufactured. ing.
Moreover, it is described that the honeycomb structure manufactured by the manufacturing method described in Patent Document 1 has high heat decomposition resistance and high fracture strength due to the effect of alkali feldspar-derived components and MgO-derived Mg.
しかしながら、特許文献１に記載のハニカム構造体の製造方法によって製造されたハニカム構造体を排ガス浄化用のフィルタとして使用し、ハニカム構造体内に捕集されたＰＭを燃焼する再生処理を繰り返し行うと、破壊強度が低くなっていることがある。
すなわち、特許文献１に記載のハニカム構造体の製造方法によって製造されたハニカム構造体は、繰り返しの再生処理に対する耐熱性が不充分なものであった。
そのため、繰り返しの再生処理に対する耐熱性が高いハニカム構造体を製造する方法が望まれていた。 However, when the honeycomb structure manufactured by the method for manufacturing a honeycomb structure described in Patent Document 1 is used as a filter for exhaust gas purification, and regeneration processing for burning PM collected in the honeycomb structure is repeatedly performed, The breaking strength may be low.
That is, the honeycomb structure manufactured by the method for manufacturing a honeycomb structure described in Patent Document 1 has insufficient heat resistance against repeated regeneration processing.
Therefore, a method for manufacturing a honeycomb structure having high heat resistance against repeated regeneration processing has been desired.
すなわち、特許文献１に記載のハニカム構造体の製造方法によって製造されたハニカム構造体は、繰り返しの再生処理に対する耐熱性が不充分なものであった。
そのため、繰り返しの再生処理に対する耐熱性が高いハニカム構造体を製造する方法が望まれていた。 However, when the honeycomb structure manufactured by the method for manufacturing a honeycomb structure described in Patent Document 1 is used as a filter for exhaust gas purification, and regeneration processing for burning PM collected in the honeycomb structure is repeatedly performed, The breaking strength may be low.
That is, the honeycomb structure manufactured by the method for manufacturing a honeycomb structure described in Patent Document 1 has insufficient heat resistance against repeated regeneration processing.
Therefore, a method for manufacturing a honeycomb structure having high heat resistance against repeated regeneration processing has been desired.
本発明者らは、上記課題を解決するために鋭意検討を行い、平均粒子径が相対的に大きいチタン酸アルミニウム粗粉末（以下、単に粗粉末ともいう）と、平均粒子径が相対的に小さいチタン酸アルミニウム微粉末（以下、単に微粉末ともいう）を用いることにより、破壊強度の高いハニカム構造体を製造することができることを見出した。
特に、それぞれ特定の組成比を有するチタン酸アルミニウム粗粉末と、特定の組成比を有するチタン酸アルミニウム微粉末とを用いることにより、破壊強度が高く、さらに繰り返しの再生処理に対する耐熱性が高いハニカム構造体を製造することができることを見出し、本発明を完成した。 The present inventors have intensively studied to solve the above problems, and have a relatively large average particle diameter of aluminum titanate coarse powder (hereinafter also simply referred to as coarse powder) and a relatively small average particle diameter. It has been found that a honeycomb structure with high fracture strength can be produced by using aluminum titanate fine powder (hereinafter also simply referred to as fine powder).
In particular, by using aluminum titanate coarse powder having a specific composition ratio and aluminum titanate fine powder having a specific composition ratio, the honeycomb structure has high fracture strength and high heat resistance against repeated regeneration treatments. The present invention was completed by finding that a body can be produced.
特に、それぞれ特定の組成比を有するチタン酸アルミニウム粗粉末と、特定の組成比を有するチタン酸アルミニウム微粉末とを用いることにより、破壊強度が高く、さらに繰り返しの再生処理に対する耐熱性が高いハニカム構造体を製造することができることを見出し、本発明を完成した。 The present inventors have intensively studied to solve the above problems, and have a relatively large average particle diameter of aluminum titanate coarse powder (hereinafter also simply referred to as coarse powder) and a relatively small average particle diameter. It has been found that a honeycomb structure with high fracture strength can be produced by using aluminum titanate fine powder (hereinafter also simply referred to as fine powder).
In particular, by using aluminum titanate coarse powder having a specific composition ratio and aluminum titanate fine powder having a specific composition ratio, the honeycomb structure has high fracture strength and high heat resistance against repeated regeneration treatments. The present invention was completed by finding that a body can be produced.
請求項１に記載のハニカム構造体の製造方法は、
平均粒子径が３～５０μｍで、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下である組成比のチタン酸アルミニウム粗粉末と、平均粒子径が０．１～３μｍで、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満である組成比のチタン酸アルミニウム微粉末とを含む湿潤混合物を成形して、長手方向に多数のセルが並設された柱状のハニカム成形体を作製する成形工程と、
上記ハニカム成形体を１２００℃～１７００℃で焼成する焼成工程とを行うことを特徴とする。 The method for manufacturing a honeycomb structured body according to claim 1,
Titanium having a composition ratio in which the average particle size is 3 to 50 μm, Al 2 O 3 is 40 to 60% by mass, TiO 2 is 30 to 50% by mass, and the total of MgO and SiO 2 is 8% by mass to 15% by mass. Aluminum oxide coarse powder, average particle size of 0.1 to 3 μm, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1 to 8% by mass Forming a wet mixture containing aluminum titanate fine powder having a composition ratio of less than 1% to produce a columnar honeycomb formed body in which a number of cells are arranged in the longitudinal direction;
And a firing step of firing the honeycomb formed body at 1200 ° C. to 1700 ° C.
平均粒子径が３～５０μｍで、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下である組成比のチタン酸アルミニウム粗粉末と、平均粒子径が０．１～３μｍで、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満である組成比のチタン酸アルミニウム微粉末とを含む湿潤混合物を成形して、長手方向に多数のセルが並設された柱状のハニカム成形体を作製する成形工程と、
上記ハニカム成形体を１２００℃～１７００℃で焼成する焼成工程とを行うことを特徴とする。 The method for manufacturing a honeycomb structured body according to claim 1,
Titanium having a composition ratio in which the average particle size is 3 to 50 μm, Al 2 O 3 is 40 to 60% by mass, TiO 2 is 30 to 50% by mass, and the total of MgO and SiO 2 is 8% by mass to 15% by mass. Aluminum oxide coarse powder, average particle size of 0.1 to 3 μm, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1 to 8% by mass Forming a wet mixture containing aluminum titanate fine powder having a composition ratio of less than 1% to produce a columnar honeycomb formed body in which a number of cells are arranged in the longitudinal direction;
And a firing step of firing the honeycomb formed body at 1200 ° C. to 1700 ° C.
なお、本明細書において、チタン酸アルミニウム微粉末とは、その平均粒子径が、チタン酸アルミニウム粗粉末の平均粒子径よりも小さいものをいう。
従って、上記チタン酸アルミニウム粗粉末の平均粒子径が３μｍの場合には、上記チタン酸アルミニウム微粉末の平均粒子径は３μｍ未満となる。 In addition, in this specification, an aluminum titanate fine powder means that whose average particle diameter is smaller than the average particle diameter of aluminum titanate coarse powder.
Therefore, when the average particle diameter of the aluminum titanate coarse powder is 3 μm, the average particle diameter of the aluminum titanate fine powder is less than 3 μm.
従って、上記チタン酸アルミニウム粗粉末の平均粒子径が３μｍの場合には、上記チタン酸アルミニウム微粉末の平均粒子径は３μｍ未満となる。 In addition, in this specification, an aluminum titanate fine powder means that whose average particle diameter is smaller than the average particle diameter of aluminum titanate coarse powder.
Therefore, when the average particle diameter of the aluminum titanate coarse powder is 3 μm, the average particle diameter of the aluminum titanate fine powder is less than 3 μm.
また、本発明の製造方法は、チタン酸アルミニウム粉末として、チタン酸アルミニウム微粉末とチタン酸アルミニウム粗粉末とを使用することを特徴としているが、以下の説明において、チタン酸アルミニウム微粉末とチタン酸アルミニウム粗粉末とを特に区別する必要がないときには、単にチタン酸アルミニウム粉末と表記する。従って、本明細書において、チタン酸アルミニウム粉末と表記した場合、チタン酸アルミニウム微粉末とチタン酸アルミニウム粗粉末との両者を指すこととする。
In addition, the production method of the present invention is characterized by using aluminum titanate fine powder and aluminum titanate coarse powder as aluminum titanate powder. In the following description, aluminum titanate fine powder and titanic acid are used. When it is not necessary to particularly distinguish the aluminum coarse powder, it is simply expressed as an aluminum titanate powder. Therefore, in the present specification, the expression “aluminum titanate powder” refers to both an aluminum titanate fine powder and an aluminum titanate coarse powder.
請求項１に記載のハニカム構造体の製造方法では、予め作製しておいた特定の組成比のチタン酸アルミニウム粗粉末とチタン酸アルミニウム微粉末とを含む混合物を用いてハニカム成形体を作製した後、このハニカム成形体を焼成することによりハニカム構造体を製造する。
In the method for manufacturing a honeycomb structured body according to claim 1, after forming a honeycomb formed body using a mixture containing a pre-prepared aluminum titanate coarse powder and aluminum titanate fine powder having a specific composition ratio. The honeycomb formed body is fired to produce a honeycomb structure.
チタン酸アルミニウム粗粉末及びチタン酸アルミニウム微粉末には、Ｍｇ及びＳｉが含まれており、Ｍｇ及びＳｉを含むチタン酸アルミニウム粉末は、Ｍｇ及びＳｉを含まないチタン酸アルミニウム粉末と比較して、熱分解しにくく耐熱性の高いチタン酸アルミニウム粉末となる。
特に、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下である粗粉末は、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満である微粉末と比較して耐熱性がより高いチタン酸アルミニウム粉末となる。 The aluminum titanate coarse powder and the aluminum titanate fine powder contain Mg and Si, and the aluminum titanate powder containing Mg and Si is more heated than the aluminum titanate powder not containing Mg and Si. It becomes an aluminum titanate powder that is hardly decomposed and has high heat resistance.
In particular, the coarse powder in which the total of MgO and SiO 2 is 8% by mass or more and 15% by mass or less is more heat resistant than the fine powder in which the total of MgO and SiO 2 is 1% by mass or more and less than 8% by mass. High aluminum titanate powder.
特に、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下である粗粉末は、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満である微粉末と比較して耐熱性がより高いチタン酸アルミニウム粉末となる。 The aluminum titanate coarse powder and the aluminum titanate fine powder contain Mg and Si, and the aluminum titanate powder containing Mg and Si is more heated than the aluminum titanate powder not containing Mg and Si. It becomes an aluminum titanate powder that is hardly decomposed and has high heat resistance.
In particular, the coarse powder in which the total of MgO and SiO 2 is 8% by mass or more and 15% by mass or less is more heat resistant than the fine powder in which the total of MgO and SiO 2 is 1% by mass or more and less than 8% by mass. High aluminum titanate powder.
このような、耐熱性が相対的に高い粗粉末と、耐熱性が相対的に低い微粉末とを含む混合物からなるハニカム成形体を焼成することによって、破壊強度が高く、さらに繰り返しの再生処理に対する耐熱性が高いハニカム構造体を製造することができる。
By firing such a honeycomb formed body including a coarse powder having a relatively high heat resistance and a fine powder having a relatively low heat resistance, the fracture strength is high, and further, repeated reprocessing. A honeycomb structure having high heat resistance can be manufactured.
上記のような耐熱性の異なるチタン酸アルミニウム粗粉末とチタン酸アルミニウム微粉末を含む混合物を用いて成形したハニカム成形体を焼成すると、耐熱性が相対的に低い微粉末が先に溶融状態となるため、液相を介して粗粉末が焼結しやすい状態となるものと推測される。
When a honeycomb formed body formed using a mixture containing aluminum titanate coarse powder and aluminum titanate fine powder having different heat resistances as described above is fired, the fine powder having relatively low heat resistance is first melted. Therefore, it is assumed that the coarse powder is easily sintered through the liquid phase.
また、請求項１に記載のハニカム構造体の製造方法では、ハニカム成形体を１２００～１７００℃で焼成する。
そのため、粒子同士を結合させ、焼成時の収縮度合いを低減し、チタン酸アルミニウムの分解を抑えることができる。これにより、製造したハニカム構造体において、気孔径分布のバラツキが小さくなる。
そして、このような気孔径分布のバラツキが小さいハニカム構造体は、高い破壊強度を有することとなる。
一方、上記焼成温度が１２００℃未満では、チタン酸アルミニウムの焼結が充分に進行しないことがある。
また、上記焼成温度が１７００℃を超えると、焼成時の収縮度合が大きくなり、その結果、気孔径が揃わない場合がある。また、チタン酸アルミニウムが分解してしまうことがある。 In the method for manufacturing a honeycomb structure according to claim 1, the honeycomb formed body is fired at 1200 to 1700 ° C.
Therefore, the particles can be bonded to each other, the degree of shrinkage during firing can be reduced, and the decomposition of aluminum titanate can be suppressed. Thereby, in the manufactured honeycomb structure, the variation in the pore size distribution is reduced.
And such a honeycomb structure with a small variation in pore size distribution has a high breaking strength.
On the other hand, when the firing temperature is less than 1200 ° C., the sintering of aluminum titanate may not sufficiently proceed.
Moreover, when the said calcination temperature exceeds 1700 degreeC, the shrinkage degree at the time of baking will become large, As a result, a pore diameter may not be uniform. In addition, aluminum titanate may be decomposed.
そのため、粒子同士を結合させ、焼成時の収縮度合いを低減し、チタン酸アルミニウムの分解を抑えることができる。これにより、製造したハニカム構造体において、気孔径分布のバラツキが小さくなる。
そして、このような気孔径分布のバラツキが小さいハニカム構造体は、高い破壊強度を有することとなる。
一方、上記焼成温度が１２００℃未満では、チタン酸アルミニウムの焼結が充分に進行しないことがある。
また、上記焼成温度が１７００℃を超えると、焼成時の収縮度合が大きくなり、その結果、気孔径が揃わない場合がある。また、チタン酸アルミニウムが分解してしまうことがある。 In the method for manufacturing a honeycomb structure according to claim 1, the honeycomb formed body is fired at 1200 to 1700 ° C.
Therefore, the particles can be bonded to each other, the degree of shrinkage during firing can be reduced, and the decomposition of aluminum titanate can be suppressed. Thereby, in the manufactured honeycomb structure, the variation in the pore size distribution is reduced.
And such a honeycomb structure with a small variation in pore size distribution has a high breaking strength.
On the other hand, when the firing temperature is less than 1200 ° C., the sintering of aluminum titanate may not sufficiently proceed.
Moreover, when the said calcination temperature exceeds 1700 degreeC, the shrinkage degree at the time of baking will become large, As a result, a pore diameter may not be uniform. In addition, aluminum titanate may be decomposed.
請求項２に記載のハニカム構造体の製造方法において、上記チタン酸アルミニウム粗粉末の組成比は、Ａｌ２Ｏ３が４０～５０質量％、ＴｉＯ２が４０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１２質量％以下である。
3. The method for manufacturing a honeycomb structured body according to claim 2, wherein the composition ratio of the aluminum titanate coarse powder is 40-50% by mass of Al 2 O 3 , 40-50% by mass of TiO 2 , MgO and SiO 2 . The total is 8% by mass or more and 12% by mass or less.
請求項３に記載のハニカム構造体の製造方法において、上記チタン酸アルミニウム微粉末の組成比は、Ａｌ２Ｏ３が４０～５０質量％、ＴｉＯ２が４０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上５質量％以下である。
4. The method for manufacturing a honeycomb structured body according to claim 3, wherein the composition ratio of the aluminum titanate fine powder is 40-50% by mass of Al 2 O 3 , 40-50% by mass of TiO 2 , MgO and SiO 2 . The total is 1% by mass or more and 5% by mass or less.
請求項４に記載のハニカム構造体の製造方法は、上記ハニカム成形体の各セルのいずれか一方の端部に封止材ペーストを充填する封止工程を行う。
請求項４に記載のハニカム構造体の製造方法では、上記封止工程を行うため、製造されたハニカム構造体は、排ガスを浄化するためのフィルタとして用いることができる。 According to a fourth aspect of the present invention, there is provided a method for manufacturing a honeycomb structured body, wherein a sealing step of filling a plug material paste at one end of each cell of the honeycomb formed body is performed.
In the method for manufacturing a honeycomb structure according to claim 4, since the sealing step is performed, the manufactured honeycomb structure can be used as a filter for purifying exhaust gas.
請求項４に記載のハニカム構造体の製造方法では、上記封止工程を行うため、製造されたハニカム構造体は、排ガスを浄化するためのフィルタとして用いることができる。 According to a fourth aspect of the present invention, there is provided a method for manufacturing a honeycomb structured body, wherein a sealing step of filling a plug material paste at one end of each cell of the honeycomb formed body is performed.
In the method for manufacturing a honeycomb structure according to claim 4, since the sealing step is performed, the manufactured honeycomb structure can be used as a filter for purifying exhaust gas.
以下、本発明の一実施形態である第一実施形態について説明する。
まず、第一実施形態で製造するハニカム構造体について、図面を参照しながら簡単に説明する。
図１（ａ）は、本発明の第一実施形態で製造するハニカム構造体を模式的に示した斜視図であり、図１（ｂ）は、図１（ａ）に示すハニカム構造体のＡ－Ａ線断面図である。 Hereinafter, a first embodiment which is an embodiment of the present invention will be described.
First, the honeycomb structure manufactured in the first embodiment will be briefly described with reference to the drawings.
Fig. 1 (a) is a perspective view schematically showing the honeycomb structure manufactured in the first embodiment of the present invention, and Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a). FIG.
まず、第一実施形態で製造するハニカム構造体について、図面を参照しながら簡単に説明する。
図１（ａ）は、本発明の第一実施形態で製造するハニカム構造体を模式的に示した斜視図であり、図１（ｂ）は、図１（ａ）に示すハニカム構造体のＡ－Ａ線断面図である。 Hereinafter, a first embodiment which is an embodiment of the present invention will be described.
First, the honeycomb structure manufactured in the first embodiment will be briefly described with reference to the drawings.
Fig. 1 (a) is a perspective view schematically showing the honeycomb structure manufactured in the first embodiment of the present invention, and Fig. 1 (b) is an A of the honeycomb structure shown in Fig. 1 (a). FIG.
図１（ａ）に示すハニカム構造体１０は、チタン酸アルミニウムからなり、その形状は、円柱形状である。そして、その内部においては、図１（ｂ）に示すように、複数のセル１１がハニカム構造体１０の長手方向に沿って形成されており、各セル１１は、セル壁１３によって隔てられている。
また、セル１１の一端は、封止材１２によって目封じされている。 Ahoneycomb structure 10 shown in FIG. 1 (a) is made of aluminum titanate and has a cylindrical shape. In the interior thereof, as shown in FIG. 1B, a plurality of cells 11 are formed along the longitudinal direction of the honeycomb structure 10, and each cell 11 is separated by a cell wall 13. .
One end of thecell 11 is sealed with a sealing material 12.
また、セル１１の一端は、封止材１２によって目封じされている。 A
One end of the
封止材１２は、ハニカム構造体１０と同様の材質からなり、チタン酸アルミニウムから構成されている。この封止材１２によって、ハニカム構造体１０は、セル１１の一端から排ガスが洩れない様に目封じされている。このため、一のセルに流入した排ガス（図１（ｂ）中、矢印で示す）は、必ず一のセルを隔てるセル壁１３を通過した後、他のセルから流出するようになっている。従って、排ガスがこのセル壁１３を通過する際にＰＭがセル壁１３の内部で捕集され、排ガスが浄化されることとなる。
The sealing material 12 is made of the same material as the honeycomb structure 10 and is made of aluminum titanate. The sealing material 12 seals the honeycomb structure 10 so that the exhaust gas does not leak from one end of the cell 11. For this reason, the exhaust gas flowing into one cell (indicated by an arrow in FIG. 1B) always passes through the cell wall 13 separating the one cell and then flows out from the other cells. Therefore, when exhaust gas passes through the cell wall 13, PM is collected inside the cell wall 13 and the exhaust gas is purified.
次に、本実施形態のハニカム構造体の製造方法について工程順に説明する。
（１）チタン酸アルミニウム粗粉末、チタン酸アルミニウム微粉末、造孔剤、有機バインダ、可塑剤、潤滑剤及び水を混合し、充分攪拌することによって湿潤混合物を調製する。 Next, the manufacturing method of the honeycomb structure of the present embodiment will be described in the order of steps.
(1) A wet mixture is prepared by mixing aluminum titanate coarse powder, aluminum titanate fine powder, pore-forming agent, organic binder, plasticizer, lubricant and water and stirring sufficiently.
（１）チタン酸アルミニウム粗粉末、チタン酸アルミニウム微粉末、造孔剤、有機バインダ、可塑剤、潤滑剤及び水を混合し、充分攪拌することによって湿潤混合物を調製する。 Next, the manufacturing method of the honeycomb structure of the present embodiment will be described in the order of steps.
(1) A wet mixture is prepared by mixing aluminum titanate coarse powder, aluminum titanate fine powder, pore-forming agent, organic binder, plasticizer, lubricant and water and stirring sufficiently.
上記チタン酸アルミニウム粗粉末としては、平均粒子径が３～５０μｍであり、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下である組成比のチタン酸アルミニウム粉末を使用する。
The aluminum titanate coarse powder has an average particle diameter of 3 to 50 μm, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 8% by mass or more. An aluminum titanate powder having a composition ratio of 15% by mass or less is used.
上記チタン酸アルミニウム微粉末としては、平均粒子径が０．１～３μｍであり、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満である組成比のチタン酸アルミニウム粉末を使用する。
The aluminum titanate fine powder has an average particle diameter of 0.1 to 3 μm, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1 mass. An aluminum titanate powder having a composition ratio of not less than 8% and less than 8% by mass is used.
チタン酸アルミニウム粉末の組成比は、ＩＣＰ発光分光分析法を用いて測定する。
ＩＣＰ発光分光分析法では、分析試料にプラズマのエネルギを外部から与え、含有されている元素（原子）を励起させ、その励起された原子が低いエネルギ準位に戻る際に放出する発光線（スペクトル線）を光子の波長別に測定する。そして、発光線の位置から成分元素の種類を判定し、発光線の強度から成分元素の含有量を求める。 The composition ratio of the aluminum titanate powder is measured using ICP emission spectroscopic analysis.
In ICP emission spectroscopic analysis, plasma energy is applied to an analysis sample from the outside, the contained elements (atoms) are excited, and emitted light (spectrum) is emitted when the excited atoms return to a low energy level. Line) for each photon wavelength. Then, the type of the component element is determined from the position of the emission line, and the content of the component element is obtained from the intensity of the emission line.
ＩＣＰ発光分光分析法では、分析試料にプラズマのエネルギを外部から与え、含有されている元素（原子）を励起させ、その励起された原子が低いエネルギ準位に戻る際に放出する発光線（スペクトル線）を光子の波長別に測定する。そして、発光線の位置から成分元素の種類を判定し、発光線の強度から成分元素の含有量を求める。 The composition ratio of the aluminum titanate powder is measured using ICP emission spectroscopic analysis.
In ICP emission spectroscopic analysis, plasma energy is applied to an analysis sample from the outside, the contained elements (atoms) are excited, and emitted light (spectrum) is emitted when the excited atoms return to a low energy level. Line) for each photon wavelength. Then, the type of the component element is determined from the position of the emission line, and the content of the component element is obtained from the intensity of the emission line.
本発明の実施形態において、上記チタン酸アルミニウム粗粉末及び上記チタン酸アルミニウム微粉末の組成比が上記範囲にある理由は以下のとおりである。
即ち、Ａｌ２Ｏ３及びＴｉＯ２の組成比が上記範囲を外れる場合には、製造したハニカム構造体を使用した際、上記ハニカム構造体が排ガスなどの熱に繰り返しさらされることにより、チタン酸アルミニウムがＡｌ２Ｏ３とＴｉＯ２に徐々に分解してしまう。
その結果、チタン酸アルミニウムが持つ物性を発揮できなくなり、ハニカム構造体の強度の低下などが発生することとなる。 In the embodiment of the present invention, the reason why the composition ratio of the aluminum titanate coarse powder and the aluminum titanate fine powder is in the above range is as follows.
That is, when the composition ratio of Al 2 O 3 and TiO 2 is out of the above range, when the manufactured honeycomb structure is used, the honeycomb structure is repeatedly exposed to heat such as exhaust gas, whereby aluminum titanate. Will gradually decompose into Al 2 O 3 and TiO 2 .
As a result, the physical properties of aluminum titanate cannot be exhibited, and the strength of the honeycomb structure is reduced.
即ち、Ａｌ２Ｏ３及びＴｉＯ２の組成比が上記範囲を外れる場合には、製造したハニカム構造体を使用した際、上記ハニカム構造体が排ガスなどの熱に繰り返しさらされることにより、チタン酸アルミニウムがＡｌ２Ｏ３とＴｉＯ２に徐々に分解してしまう。
その結果、チタン酸アルミニウムが持つ物性を発揮できなくなり、ハニカム構造体の強度の低下などが発生することとなる。 In the embodiment of the present invention, the reason why the composition ratio of the aluminum titanate coarse powder and the aluminum titanate fine powder is in the above range is as follows.
That is, when the composition ratio of Al 2 O 3 and TiO 2 is out of the above range, when the manufactured honeycomb structure is used, the honeycomb structure is repeatedly exposed to heat such as exhaust gas, whereby aluminum titanate. Will gradually decompose into Al 2 O 3 and TiO 2 .
As a result, the physical properties of aluminum titanate cannot be exhibited, and the strength of the honeycomb structure is reduced.
微粉末のＭｇＯとＳｉＯ２の合計の組成比が１．０質量％未満の場合には、製造したハニカム構造体を使用した際、上記ハニカム構造体が排ガスなどの熱に繰り返しさらされることにより、チタン酸アルミニウムがＡｌ２Ｏ３とＴｉＯ２に徐々に分解してしまう。
微粉末のＭｇＯとＳｉＯ２の合計の組成比の下限は、２．５質量％が望ましい。２．５質量％以上であると、チタン酸アルミニウムの分解がより進行しにくくなるからである。 When the total composition ratio of fine powder MgO and SiO 2 is less than 1.0% by mass, when the manufactured honeycomb structure is used, the honeycomb structure is repeatedly exposed to heat such as exhaust gas, Aluminum titanate is gradually decomposed into Al 2 O 3 and TiO 2 .
The lower limit of the total composition ratio of fine powder MgO and SiO 2 is preferably 2.5% by mass. This is because when the content is 2.5% by mass or more, the decomposition of aluminum titanate is less likely to proceed.
微粉末のＭｇＯとＳｉＯ２の合計の組成比の下限は、２．５質量％が望ましい。２．５質量％以上であると、チタン酸アルミニウムの分解がより進行しにくくなるからである。 When the total composition ratio of fine powder MgO and SiO 2 is less than 1.0% by mass, when the manufactured honeycomb structure is used, the honeycomb structure is repeatedly exposed to heat such as exhaust gas, Aluminum titanate is gradually decomposed into Al 2 O 3 and TiO 2 .
The lower limit of the total composition ratio of fine powder MgO and SiO 2 is preferably 2.5% by mass. This is because when the content is 2.5% by mass or more, the decomposition of aluminum titanate is less likely to proceed.
粗粉末のＭｇＯとＳｉＯ２の合計の組成比が１５質量％を超えると、製造したハニカム構造体を使用した際、上記ハニカム構造体が排ガスなどの熱に繰り返しさらされ、熱膨張によるクラックが発生することがある。
When the total composition ratio of MgO and SiO 2 in the coarse powder exceeds 15 mass%, when the manufactured honeycomb structure is used, the honeycomb structure is repeatedly exposed to heat such as exhaust gas, and cracks due to thermal expansion occur. There are things to do.
また、上記チタン酸アルミニウム粗粉末の組成比は、Ａｌ２Ｏ３が４０～５０質量％、ＴｉＯ２が４０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１２質量％以下であることがより望ましい。
また、上記チタン酸アルミニウム微粉末の組成比は、Ａｌ２Ｏ３が４０～５０質量％、ＴｉＯ２が４０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上５質量％以下であることがより望ましい。 The composition ratio of the aluminum titanate coarse powder is 40 to 50% by mass of Al 2 O 3 , 40 to 50% by mass of TiO 2 , and the total of MgO and SiO 2 is 8 to 12% by mass. It is more desirable.
The composition ratio of the aluminum titanate fine powder is 40-50 mass% for Al 2 O 3, 40-50 mass% for TiO 2 , and the total of MgO and SiO 2 is 1 mass% to 5 mass%. It is more desirable.
また、上記チタン酸アルミニウム微粉末の組成比は、Ａｌ２Ｏ３が４０～５０質量％、ＴｉＯ２が４０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上５質量％以下であることがより望ましい。 The composition ratio of the aluminum titanate coarse powder is 40 to 50% by mass of Al 2 O 3 , 40 to 50% by mass of TiO 2 , and the total of MgO and SiO 2 is 8 to 12% by mass. It is more desirable.
The composition ratio of the aluminum titanate fine powder is 40-50 mass% for Al 2 O 3, 40-50 mass% for TiO 2 , and the total of MgO and SiO 2 is 1 mass% to 5 mass%. It is more desirable.
（２）上記湿潤混合物を押出成形機により押出成形し、長手方向に多数のセルが並設された円柱状のハニカム成形体の長尺体を作製する。その後、上記ハニカム成形体の長尺体を、切断ディスクを切断部材として備えた切断装置により切断し、所定の長さのハニカム成形体とする。
(2) The wet mixture is extrusion-molded by an extruder to produce a columnar honeycomb molded body having a large number of cells arranged in parallel in the longitudinal direction. Thereafter, the long body of the honeycomb formed body is cut by a cutting device having a cutting disk as a cutting member to obtain a honeycomb formed body having a predetermined length.
（３）上記ハニカム成形体をマイクロ波乾燥機及び熱風乾燥機を用いて、大気雰囲気下、１００～１５０℃の条件で１～３０分間乾燥する。
(3) The honeycomb formed body is dried for 1 to 30 minutes under a condition of 100 to 150 ° C. in an air atmosphere using a microwave dryer and a hot air dryer.
（４）上記ハニカム成形体の各セルのいずれか一方の端部が封止されるように、所定の端部に封止材ペーストを充填する。その後、各セルのいずれか一方の端部に封止材ペーストが充填されたハニカム成形体を再度乾燥させる。
上記封止材ペーストとしては、上記湿潤混合物と同様の組成のペーストを使用する。 (4) Fill a predetermined end portion with a plug material paste so that any one end portion of each cell of the honeycomb formed body is sealed. Thereafter, the honeycomb formed body in which one end of each cell is filled with the plug material paste is dried again.
As the sealing material paste, a paste having the same composition as the wet mixture is used.
上記封止材ペーストとしては、上記湿潤混合物と同様の組成のペーストを使用する。 (4) Fill a predetermined end portion with a plug material paste so that any one end portion of each cell of the honeycomb formed body is sealed. Thereafter, the honeycomb formed body in which one end of each cell is filled with the plug material paste is dried again.
As the sealing material paste, a paste having the same composition as the wet mixture is used.
（５）上記ハニカム成形体を、脱脂炉中で、酸素濃度５容積％～大気雰囲気下、２５０～４００℃の条件で３～１５時間脱脂する。その後、焼成炉中で、１２００～１７００℃の温度で０．５～２４時間焼成する。
このような工程を経ることにより、上述したハニカム構造体１０を製造することができる。 (5) The honeycomb formed body is degreased in a degreasing furnace for 3 to 15 hours under conditions of an oxygen concentration of 5% by volume to an atmospheric atmosphere at 250 to 400 ° C. Thereafter, firing is performed at a temperature of 1200 to 1700 ° C. for 0.5 to 24 hours in a firing furnace.
Thehoneycomb structure 10 described above can be manufactured through such steps.
このような工程を経ることにより、上述したハニカム構造体１０を製造することができる。 (5) The honeycomb formed body is degreased in a degreasing furnace for 3 to 15 hours under conditions of an oxygen concentration of 5% by volume to an atmospheric atmosphere at 250 to 400 ° C. Thereafter, firing is performed at a temperature of 1200 to 1700 ° C. for 0.5 to 24 hours in a firing furnace.
The
以下、第一実施形態のハニカム構造体の製造方法についての作用効果を列挙する。
（１）本実施形態のハニカム構造体の製造方法では、耐熱性が相対的に高い粗粉末と、耐熱性が相対的に低い微粉末とを含む混合物からなるハニカム成形体を焼成しているため、破壊強度が高く、繰り返しの再生処理に対する耐熱性が高いハニカム構造体を製造することができる。 Hereinafter, effects of the manufacturing method of the honeycomb structure according to the first embodiment will be listed.
(1) In the method for manufacturing a honeycomb structured body of the present embodiment, a honeycomb formed body made of a mixture containing a coarse powder having a relatively high heat resistance and a fine powder having a relatively low heat resistance is fired. A honeycomb structure having high fracture strength and high heat resistance against repeated regeneration treatment can be produced.
（１）本実施形態のハニカム構造体の製造方法では、耐熱性が相対的に高い粗粉末と、耐熱性が相対的に低い微粉末とを含む混合物からなるハニカム成形体を焼成しているため、破壊強度が高く、繰り返しの再生処理に対する耐熱性が高いハニカム構造体を製造することができる。 Hereinafter, effects of the manufacturing method of the honeycomb structure according to the first embodiment will be listed.
(1) In the method for manufacturing a honeycomb structured body of the present embodiment, a honeycomb formed body made of a mixture containing a coarse powder having a relatively high heat resistance and a fine powder having a relatively low heat resistance is fired. A honeycomb structure having high fracture strength and high heat resistance against repeated regeneration treatment can be produced.
（２）本実施形態のハニカム構造体の製造方法では、チタン酸アルミニウム粉末の粗粉末として、平均粒子径が３～５０μｍであり、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下である組成比のチタン酸アルミニウム粉末を使用し、チタン酸アルミニウム粉末の微粉末として、平均粒子径が０．１～３μｍであり、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満である組成比のチタン酸アルミニウム粉末を使用している。
そのため、製造したハニカム構造体において、チタン酸アルミニウムの分解が進行したり、製造したハニカム構造体に熱膨張によるクラックが発生したりすることがない。 (2) In the method for manufacturing a honeycomb structure of the present embodiment, the coarse particle of the aluminum titanate powder has an average particle diameter of 3 to 50 μm, Al 2 O 3 of 40 to 60% by mass, and TiO 2 of 30 to 30%. An aluminum titanate powder having a composition ratio of 50% by mass and a total of MgO and SiO 2 of 8% by mass to 15% by mass is used, and the average particle size is 0.1 to 3 μm as a fine powder of the aluminum titanate powder. Aluminum titanate powder having a composition ratio of Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1% by mass to less than 8% by mass is used. ing.
Therefore, in the manufactured honeycomb structure, decomposition of aluminum titanate does not proceed, and cracks due to thermal expansion do not occur in the manufactured honeycomb structure.
そのため、製造したハニカム構造体において、チタン酸アルミニウムの分解が進行したり、製造したハニカム構造体に熱膨張によるクラックが発生したりすることがない。 (2) In the method for manufacturing a honeycomb structure of the present embodiment, the coarse particle of the aluminum titanate powder has an average particle diameter of 3 to 50 μm, Al 2 O 3 of 40 to 60% by mass, and TiO 2 of 30 to 30%. An aluminum titanate powder having a composition ratio of 50% by mass and a total of MgO and SiO 2 of 8% by mass to 15% by mass is used, and the average particle size is 0.1 to 3 μm as a fine powder of the aluminum titanate powder. Aluminum titanate powder having a composition ratio of Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1% by mass to less than 8% by mass is used. ing.
Therefore, in the manufactured honeycomb structure, decomposition of aluminum titanate does not proceed, and cracks due to thermal expansion do not occur in the manufactured honeycomb structure.
（３）本実施形態のハニカム構造体の製造方法では、ハニカム成形体を１２００～１７００℃で焼成しているため、粒子同士を結合させ、焼成時の収縮度合いを低減し、チタン酸アルミニウムの分解を抑えることができる。
チタン酸アルミニウム粉末を含む混合物を用いて作製したハニカム成形体の焼結が過不足なく進行する。これにより、製造したハニカム構造体において、気孔径分布のバラツキが小さくなる。 (3) In the method for manufacturing a honeycomb structure of the present embodiment, the honeycomb formed body is fired at 1200 to 1700 ° C., so that the particles are bonded to each other, the degree of shrinkage during firing is reduced, and the aluminum titanate is decomposed. Can be suppressed.
Sintering of the honeycomb formed body produced using the mixture containing the aluminum titanate powder proceeds without excess or deficiency. Thereby, in the manufactured honeycomb structure, the variation in the pore size distribution is reduced.
チタン酸アルミニウム粉末を含む混合物を用いて作製したハニカム成形体の焼結が過不足なく進行する。これにより、製造したハニカム構造体において、気孔径分布のバラツキが小さくなる。 (3) In the method for manufacturing a honeycomb structure of the present embodiment, the honeycomb formed body is fired at 1200 to 1700 ° C., so that the particles are bonded to each other, the degree of shrinkage during firing is reduced, and the aluminum titanate is decomposed. Can be suppressed.
Sintering of the honeycomb formed body produced using the mixture containing the aluminum titanate powder proceeds without excess or deficiency. Thereby, in the manufactured honeycomb structure, the variation in the pore size distribution is reduced.
（４）本実施形態のハニカム構造体の製造方法では、チタン酸アルミニウム粉末として、平均粒子径が３～５０μｍのチタン酸アルミニウム粗粉末と、平均粒子径が０．１～３μｍのチタン酸アルミニウム微粉末とを用いている。
このように、平均粒子径が３～５０μｍのチタン酸アルミニウム粗粉末と、平均粒子径が０．１～３μｍのチタン酸アルミニウム微粉末とを用いる場合、各粉末の平均粒子径を適宜選択することにより、ハニカム構造体の気孔径を制御することができる。 (4) In the method for manufacturing a honeycomb structure of the present embodiment, as the aluminum titanate powder, aluminum titanate coarse powder having an average particle diameter of 3 to 50 μm and aluminum titanate fine powder having an average particle diameter of 0.1 to 3 μm Powder is used.
Thus, when using an aluminum titanate coarse powder with an average particle size of 3 to 50 μm and an aluminum titanate fine powder with an average particle size of 0.1 to 3 μm, the average particle size of each powder should be appropriately selected. Thus, the pore diameter of the honeycomb structure can be controlled.
このように、平均粒子径が３～５０μｍのチタン酸アルミニウム粗粉末と、平均粒子径が０．１～３μｍのチタン酸アルミニウム微粉末とを用いる場合、各粉末の平均粒子径を適宜選択することにより、ハニカム構造体の気孔径を制御することができる。 (4) In the method for manufacturing a honeycomb structure of the present embodiment, as the aluminum titanate powder, aluminum titanate coarse powder having an average particle diameter of 3 to 50 μm and aluminum titanate fine powder having an average particle diameter of 0.1 to 3 μm Powder is used.
Thus, when using an aluminum titanate coarse powder with an average particle size of 3 to 50 μm and an aluminum titanate fine powder with an average particle size of 0.1 to 3 μm, the average particle size of each powder should be appropriately selected. Thus, the pore diameter of the honeycomb structure can be controlled.
（５）本実施形態のハニカム構造体の製造方法では、上記ハニカム成形体の各セルのいずれか一方の端部に封止材ペーストを充填する封止工程を行う。そのため、製造したハニカム構造体は、排ガスを浄化するためのフィルタとして用いることができる。
(5) In the method for manufacturing a honeycomb structured body of the present embodiment, a sealing step of filling a plug material paste into one end of each cell of the honeycomb formed body is performed. Therefore, the manufactured honeycomb structure can be used as a filter for purifying exhaust gas.
以下、本発明の第一実施形態をより具体的に開示した実施例を示すが、本実施形態はこれら実施例のみに限定されるものではない。
ここでは、まず、組成比の異なるチタン酸アルミニウム粉末Ａ～Ｄを用意した。
チタン酸アルミニウム粉末Ａ～Ｄの各組成比は表１に示すとおりである。
チタン酸アルミニウム粉末Ａ、ＣはＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満であるチタン酸アルミニウム粉末である。
チタン酸アルミニウム粉末Ｂ、ＤはＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下であるチタン酸アルミニウム粉末である。 Examples that more specifically disclose the first embodiment of the present invention will be described below, but the present embodiment is not limited to these examples.
Here, first, aluminum titanate powders A to D having different composition ratios were prepared.
The composition ratios of the aluminum titanate powders A to D are as shown in Table 1.
Aluminum titanate powders A and C are aluminum titanate powders in which the total of MgO and SiO 2 is 1% by mass or more and less than 8% by mass.
Aluminum titanate powders B and D are aluminum titanate powders in which the total of MgO and SiO 2 is 8% by mass or more and 15% by mass or less.
ここでは、まず、組成比の異なるチタン酸アルミニウム粉末Ａ～Ｄを用意した。
チタン酸アルミニウム粉末Ａ～Ｄの各組成比は表１に示すとおりである。
チタン酸アルミニウム粉末Ａ、ＣはＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満であるチタン酸アルミニウム粉末である。
チタン酸アルミニウム粉末Ｂ、ＤはＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下であるチタン酸アルミニウム粉末である。 Examples that more specifically disclose the first embodiment of the present invention will be described below, but the present embodiment is not limited to these examples.
Here, first, aluminum titanate powders A to D having different composition ratios were prepared.
The composition ratios of the aluminum titanate powders A to D are as shown in Table 1.
Aluminum titanate powders A and C are aluminum titanate powders in which the total of MgO and SiO 2 is 1% by mass or more and less than 8% by mass.
Aluminum titanate powders B and D are aluminum titanate powders in which the total of MgO and SiO 2 is 8% by mass or more and 15% by mass or less.
なお、表１に示したチタン酸アルミニウム粉末Ａ～Ｄの組成比において、各成分の合計量は１００質量％となっていないが、これは、チタン酸アルミニウム粉末中に不純物が含まれるからである。
上記不純物は、アルカリ長石由来の物質（Ｋ２Ｏ、Ｎａ２Ｏ等）、チタン酸アルミニウム粉末を粉砕したり、混合したりする際に鉄化合物、チタン酸アルミニウム粉末の原料のＡｌ２Ｏ３粉末やＴｉＯ２粉末に元々含まれる物質等である。 In the composition ratio of aluminum titanate powders A to D shown in Table 1, the total amount of each component is not 100% by mass, because the aluminum titanate powder contains impurities. .
The impurities include alkali feldspar-derived substances (K 2 O, Na 2 O, etc.), Al 2 O 3 powder as a raw material for iron compounds and aluminum titanate powders when the aluminum titanate powder is pulverized or mixed. And substances originally contained in TiO 2 powder.
上記不純物は、アルカリ長石由来の物質（Ｋ２Ｏ、Ｎａ２Ｏ等）、チタン酸アルミニウム粉末を粉砕したり、混合したりする際に鉄化合物、チタン酸アルミニウム粉末の原料のＡｌ２Ｏ３粉末やＴｉＯ２粉末に元々含まれる物質等である。 In the composition ratio of aluminum titanate powders A to D shown in Table 1, the total amount of each component is not 100% by mass, because the aluminum titanate powder contains impurities. .
The impurities include alkali feldspar-derived substances (K 2 O, Na 2 O, etc.), Al 2 O 3 powder as a raw material for iron compounds and aluminum titanate powders when the aluminum titanate powder is pulverized or mixed. And substances originally contained in TiO 2 powder.
そして、各チタン酸アルミニウム粉末について、粉砕、分級工程を行い、平均粒子径が異なるチタン酸アルミニウムの粉末を調製した。
そして、湿潤混合物を調製する際に、平均粒子径の大きい粉末を粗粉末として使用し、平均粒子径の小さい粉末を微粉末として使用した。 And about each aluminum titanate powder, the grinding | pulverization and the classification process were performed, and the powder of the aluminum titanate from which an average particle diameter differs was prepared.
In preparing the wet mixture, a powder having a large average particle size was used as a coarse powder, and a powder having a small average particle size was used as a fine powder.
そして、湿潤混合物を調製する際に、平均粒子径の大きい粉末を粗粉末として使用し、平均粒子径の小さい粉末を微粉末として使用した。 And about each aluminum titanate powder, the grinding | pulverization and the classification process were performed, and the powder of the aluminum titanate from which an average particle diameter differs was prepared.
In preparing the wet mixture, a powder having a large average particle size was used as a coarse powder, and a powder having a small average particle size was used as a fine powder.
（実施例１）
（１）平均粒子径２０μｍのチタン酸アルミニウムＢの粗粉末２０００重量部、平均粒子径０．５μｍのチタン酸アルミニウムＡの微粉末５００重量部、造孔剤（球状アクリル粒子）３００重量部、有機バインダ（メチルセルロース）１８８重量部、可塑剤（日本油脂社製 ユニルーブ）９６重量部、潤滑剤（グリセリン）４４重量部及び水７２５重量部を混合し、充分攪拌することによって湿潤混合物を調製した。 Example 1
(1) 2000 parts by weight of coarse powder of aluminum titanate B having an average particle diameter of 20 μm, 500 parts by weight of fine powder of aluminum titanate A having an average particle diameter of 0.5 μm, 300 parts by weight of pore-forming agent (spherical acrylic particles), organic A wet mixture was prepared by mixing 188 parts by weight of a binder (methylcellulose), 96 parts by weight of a plasticizer (Unilube manufactured by NOF Corporation), 44 parts by weight of a lubricant (glycerin) and 725 parts by weight of water, and stirring sufficiently.
（１）平均粒子径２０μｍのチタン酸アルミニウムＢの粗粉末２０００重量部、平均粒子径０．５μｍのチタン酸アルミニウムＡの微粉末５００重量部、造孔剤（球状アクリル粒子）３００重量部、有機バインダ（メチルセルロース）１８８重量部、可塑剤（日本油脂社製 ユニルーブ）９６重量部、潤滑剤（グリセリン）４４重量部及び水７２５重量部を混合し、充分攪拌することによって湿潤混合物を調製した。 Example 1
(1) 2000 parts by weight of coarse powder of aluminum titanate B having an average particle diameter of 20 μm, 500 parts by weight of fine powder of aluminum titanate A having an average particle diameter of 0.5 μm, 300 parts by weight of pore-forming agent (spherical acrylic particles), organic A wet mixture was prepared by mixing 188 parts by weight of a binder (methylcellulose), 96 parts by weight of a plasticizer (Unilube manufactured by NOF Corporation), 44 parts by weight of a lubricant (glycerin) and 725 parts by weight of water, and stirring sufficiently.
（２）上記湿潤混合物をプランジャー式押出成形機の混合物タンクよりシリンダー内に投入し、ピストンをダイス側に押し込んで円柱形状のダイスより湿潤混合物を押し出し、セル壁で隔てられた多数のセルが長手方向に沿って形成された円柱形状のチタン酸アルミニウムからなるハニカム成形体の長尺体を作製した。
(2) The wet mixture is put into the cylinder from the mixture tank of the plunger type extruder, the piston is pushed into the die side, the wet mixture is pushed out from the cylindrical die, and a large number of cells separated by the cell walls. A long honeycomb molded body made of columnar aluminum titanate formed along the longitudinal direction was produced.
（３）上記ハニカム成形体の長尺体を、切断ディスクを切断部材として備えた切断装置を用いて切断した。これにより、円柱形状のチタン酸アルミニウムからなるハニカム成形体を得た。
(3) The long body of the honeycomb formed body was cut using a cutting device provided with a cutting disk as a cutting member. Thereby, a honeycomb formed body made of columnar aluminum titanate was obtained.
（４）上記ハニカム成形体を、マイクロ波乾燥機及び熱風乾燥機により、大気雰囲気下、１２０℃の条件で２０分間、乾燥処理し、ハニカム成形体中に含まれる水分を除去した。
(4) The honeycomb formed body was dried with a microwave dryer and a hot air dryer under the atmosphere at 120 ° C. for 20 minutes to remove moisture contained in the honeycomb formed body.
（５）上記乾燥処理後のハニカム成形体の各セルのいずれか一方の端部に封止材ペーストが充填されるように、（１）で調整した湿潤混合物と同様の組成の封止材ペーストをハニカム成形体の所定のセルに充填した。
(5) A sealing material paste having the same composition as the wet mixture prepared in (1) so that any one end of each cell of the honeycomb formed body after the drying treatment is filled with the sealing material paste. Was filled into predetermined cells of the honeycomb formed body.
（６）上記封止材ペーストを充填したハニカム成形体を大気雰囲気下、１２０℃の条件で１０分間、再度乾燥処理した。その後、脱脂炉中で、酸素濃度６容量％の下、３００℃の条件で１２時間脱脂処理した。
(6) The honeycomb formed body filled with the plug material paste was again dried for 10 minutes under the atmosphere at 120 ° C. Thereafter, degreasing treatment was performed in a degreasing furnace at 300 ° C. for 12 hours under an oxygen concentration of 6 vol%.
（７）上記脱脂処理したハニカム成形体を、焼成炉中、１５００℃の条件で１時間焼成処理した。
このような（１）～（７）の工程を経ることにより、長手方向に沿って、セル壁厚が０．２ｍｍ（８ｍｉｌ）で、セル密度が４６．５個／ｃｍ２（３００ｃｐｓｉ）のセルを有し、直径が１４３．８ｍｍで、長手方向の長さが１５０ｍｍのチタン酸アルミニウムからなるハニカム構造体を完成した。
なお、実施例１で製造したハニカム構造体の気孔率は４０％であった。上記気孔率は、水銀圧入法により測定した。 (7) The degreased honeycomb formed body was fired in a firing furnace at 1500 ° C. for 1 hour.
Through the steps (1) to (7), a cell having a cell wall thickness of 0.2 mm (8 mil) and a cell density of 46.5 cells / cm 2 (300 cpsi) along the longitudinal direction. A honeycomb structure made of aluminum titanate having a diameter of 143.8 mm and a length in the longitudinal direction of 150 mm was completed.
Note that the porosity of the honeycomb structure manufactured in Example 1 was 40%. The porosity was measured by mercury porosimetry.
このような（１）～（７）の工程を経ることにより、長手方向に沿って、セル壁厚が０．２ｍｍ（８ｍｉｌ）で、セル密度が４６．５個／ｃｍ２（３００ｃｐｓｉ）のセルを有し、直径が１４３．８ｍｍで、長手方向の長さが１５０ｍｍのチタン酸アルミニウムからなるハニカム構造体を完成した。
なお、実施例１で製造したハニカム構造体の気孔率は４０％であった。上記気孔率は、水銀圧入法により測定した。 (7) The degreased honeycomb formed body was fired in a firing furnace at 1500 ° C. for 1 hour.
Through the steps (1) to (7), a cell having a cell wall thickness of 0.2 mm (8 mil) and a cell density of 46.5 cells / cm 2 (300 cpsi) along the longitudinal direction. A honeycomb structure made of aluminum titanate having a diameter of 143.8 mm and a length in the longitudinal direction of 150 mm was completed.
Note that the porosity of the honeycomb structure manufactured in Example 1 was 40%. The porosity was measured by mercury porosimetry.
（実施例２～６、比較例１～４）
チタン酸アルミニウム粗粉末又はチタン酸アルミニウムの微粉末の種類及び平均粒子径を変更した他は、実施例１と同様にして、ハニカム構造体を製造した。
各実施例及び各比較例で使用したチタン酸アルミニウム粉末の種類及び平均粒子径は、下記表２に示したとおりである。 (Examples 2 to 6, Comparative Examples 1 to 4)
A honeycomb structure was manufactured in the same manner as in Example 1 except that the kind of aluminum titanate coarse powder or the fine powder of aluminum titanate and the average particle size were changed.
The types and average particle diameters of the aluminum titanate powders used in each example and each comparative example are as shown in Table 2 below.
チタン酸アルミニウム粗粉末又はチタン酸アルミニウムの微粉末の種類及び平均粒子径を変更した他は、実施例１と同様にして、ハニカム構造体を製造した。
各実施例及び各比較例で使用したチタン酸アルミニウム粉末の種類及び平均粒子径は、下記表２に示したとおりである。 (Examples 2 to 6, Comparative Examples 1 to 4)
A honeycomb structure was manufactured in the same manner as in Example 1 except that the kind of aluminum titanate coarse powder or the fine powder of aluminum titanate and the average particle size were changed.
The types and average particle diameters of the aluminum titanate powders used in each example and each comparative example are as shown in Table 2 below.
（ハニカム構造体の評価）
実施例１～６及び比較例１～４で製造したハニカム構造体について、下記の方法による再生処理を３０回行い、その後、下記の方法によりハニカム構造体の破壊強度を測定した。 (Evaluation of honeycomb structure)
The honeycomb structures manufactured in Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to a regeneration treatment by the following method 30 times, and then the fracture strength of the honeycomb structure was measured by the following method.
実施例１～６及び比較例１～４で製造したハニカム構造体について、下記の方法による再生処理を３０回行い、その後、下記の方法によりハニカム構造体の破壊強度を測定した。 (Evaluation of honeycomb structure)
The honeycomb structures manufactured in Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to a regeneration treatment by the following method 30 times, and then the fracture strength of the honeycomb structure was measured by the following method.
（再生処理）
実施例及び比較例のハニカム構造体をそれぞれ、２Ｌのエンジンの排気通路に配置し、さらにハニカム構造体よりガス流入側に、市販のコージェライトからなるハニカム構造体の触媒担持体（直径：２００ｍｍ、長さ：１００ｍｍ、セル密度：４００セル／ｉｎｃｈ２、白金担持量：５ｇ／Ｌ）を設置して排気ガス浄化装置とし、エンジンを回転数３０００ｍｉｎ－１、トルク５０Ｎｍでパティキュレートを１０時間捕集した。パティキュレートの捕集量は、１０ｇ／Ｌであった。
その後、エンジンを回転数１２５０ｍｉｎ－１、トルク６０Ｎｍとし、フィルタの温度が一定となった状態で、１分間保持した後、ポストインジェクションを行い、前方にある酸化触媒を利用して排気温度を上昇させ、パティキュレートを燃焼させた。
上記ポストインジェクションの条件は、開始１分間後からハニカム構造体に流入する排ガスの温度が６００℃でほぼ一定になるように設定した。 (Reproduction processing)
The honeycomb structures of the example and the comparative example are respectively disposed in the exhaust passage of a 2 L engine, and further on the gas inflow side of the honeycomb structure, a catalyst support (diameter: 200 mm, Length: 100 mm, cell density: 400 cells / inch 2 , platinum carrying amount: 5 g / L) is installed as an exhaust gas purifier, and the engine collects particulates for 10 hours at a rotational speed of 3000 min −1 and a torque of 50 Nm. did. The amount of particulates collected was 10 g / L.
After that, the engine is set at a rotational speed of 1250 min −1 and a torque of 60 Nm, and the filter temperature is kept constant for 1 minute. Then, post-injection is performed, and the exhaust gas temperature is raised using the oxidation catalyst in front. The particulates were burned.
The post-injection conditions were set so that the temperature of the exhaust gas flowing into the honeycomb structure after 1 minute from the start became substantially constant at 600 ° C.
実施例及び比較例のハニカム構造体をそれぞれ、２Ｌのエンジンの排気通路に配置し、さらにハニカム構造体よりガス流入側に、市販のコージェライトからなるハニカム構造体の触媒担持体（直径：２００ｍｍ、長さ：１００ｍｍ、セル密度：４００セル／ｉｎｃｈ２、白金担持量：５ｇ／Ｌ）を設置して排気ガス浄化装置とし、エンジンを回転数３０００ｍｉｎ－１、トルク５０Ｎｍでパティキュレートを１０時間捕集した。パティキュレートの捕集量は、１０ｇ／Ｌであった。
その後、エンジンを回転数１２５０ｍｉｎ－１、トルク６０Ｎｍとし、フィルタの温度が一定となった状態で、１分間保持した後、ポストインジェクションを行い、前方にある酸化触媒を利用して排気温度を上昇させ、パティキュレートを燃焼させた。
上記ポストインジェクションの条件は、開始１分間後からハニカム構造体に流入する排ガスの温度が６００℃でほぼ一定になるように設定した。 (Reproduction processing)
The honeycomb structures of the example and the comparative example are respectively disposed in the exhaust passage of a 2 L engine, and further on the gas inflow side of the honeycomb structure, a catalyst support (diameter: 200 mm, Length: 100 mm, cell density: 400 cells / inch 2 , platinum carrying amount: 5 g / L) is installed as an exhaust gas purifier, and the engine collects particulates for 10 hours at a rotational speed of 3000 min −1 and a torque of 50 Nm. did. The amount of particulates collected was 10 g / L.
After that, the engine is set at a rotational speed of 1250 min −1 and a torque of 60 Nm, and the filter temperature is kept constant for 1 minute. Then, post-injection is performed, and the exhaust gas temperature is raised using the oxidation catalyst in front. The particulates were burned.
The post-injection conditions were set so that the temperature of the exhaust gas flowing into the honeycomb structure after 1 minute from the start became substantially constant at 600 ° C.
（破壊強度の測定）
上記再生処理を３０回行ったハニカム構造体から３４．３ｍｍ角、長さ１５０ｍｍの試験片を切り出し、ＪＩＳ Ｒ １６０１に準拠して、インストロン５５８２を用い、スパン間距離：１３０ｍｍ、スピード０．５ｍｍ／分で３点曲げ試験を行い、各実施例及び比較例のハニカム構造体の曲げ強度を測定した。
結果を表２に示した。 (Measurement of fracture strength)
A specimen of 34.3 mm square and 150 mm length was cut out from the honeycomb structure subjected to the above regeneration treatment 30 times, and an Instron 5582 was used according to JIS R 1601, a span distance: 130 mm, a speed of 0.5 mm. A three-point bending test was performed at a rate of 1 minute, and the bending strengths of the honeycomb structures of the examples and comparative examples were measured.
The results are shown in Table 2.
上記再生処理を３０回行ったハニカム構造体から３４．３ｍｍ角、長さ１５０ｍｍの試験片を切り出し、ＪＩＳ Ｒ １６０１に準拠して、インストロン５５８２を用い、スパン間距離：１３０ｍｍ、スピード０．５ｍｍ／分で３点曲げ試験を行い、各実施例及び比較例のハニカム構造体の曲げ強度を測定した。
結果を表２に示した。 (Measurement of fracture strength)
A specimen of 34.3 mm square and 150 mm length was cut out from the honeycomb structure subjected to the above regeneration treatment 30 times, and an Instron 5582 was used according to JIS R 1601, a span distance: 130 mm, a speed of 0.5 mm. A three-point bending test was performed at a rate of 1 minute, and the bending strengths of the honeycomb structures of the examples and comparative examples were measured.
The results are shown in Table 2.
表２に示した結果より、実施例１～６のように、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下であるチタン酸アルミニウム粗粉末と、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満であるチタン酸アルミニウム微粉末とを用いてハニカム構造体を製造した場合には、３０回の再生処理を行った後でも高い破壊強度を有するハニカム構造体を製造することができることが明らかとなった。
これに対して、比較例１～４のように、同一の組成比のチタン酸アルミニウム粗粉末とチタン酸アルミニウム微粉末とを用いて製造したハニカム構造体は、３０回の再生処理を行った後において、破壊強度が低くなっていた。このような破壊強度の低下は、再生処理によって一部のチタン酸アルミニウムがＡｌ２Ｏ３とＴｉＯ２とに分解していたために生じたものと考えられる。 From the results shown in Table 2, as in Examples 1 to 6, the total amount of MgO and SiO 2 was 8% by mass to 15% by mass, and the total of MgO and SiO 2 was 1% by mass. % And less than 8% by mass of the aluminum titanate fine powder, a honeycomb structure having a high fracture strength can be produced even after 30 regeneration treatments. It became clear that we could do it.
On the other hand, as in Comparative Examples 1 to 4, the honeycomb structure manufactured using the aluminum titanate coarse powder and the aluminum titanate fine powder having the same composition ratio was subjected to the regeneration treatment 30 times. The fracture strength was low. Such a decrease in fracture strength is considered to have occurred because a part of aluminum titanate was decomposed into Al 2 O 3 and TiO 2 by the regeneration treatment.
これに対して、比較例１～４のように、同一の組成比のチタン酸アルミニウム粗粉末とチタン酸アルミニウム微粉末とを用いて製造したハニカム構造体は、３０回の再生処理を行った後において、破壊強度が低くなっていた。このような破壊強度の低下は、再生処理によって一部のチタン酸アルミニウムがＡｌ２Ｏ３とＴｉＯ２とに分解していたために生じたものと考えられる。 From the results shown in Table 2, as in Examples 1 to 6, the total amount of MgO and SiO 2 was 8% by mass to 15% by mass, and the total of MgO and SiO 2 was 1% by mass. % And less than 8% by mass of the aluminum titanate fine powder, a honeycomb structure having a high fracture strength can be produced even after 30 regeneration treatments. It became clear that we could do it.
On the other hand, as in Comparative Examples 1 to 4, the honeycomb structure manufactured using the aluminum titanate coarse powder and the aluminum titanate fine powder having the same composition ratio was subjected to the regeneration treatment 30 times. The fracture strength was low. Such a decrease in fracture strength is considered to have occurred because a part of aluminum titanate was decomposed into Al 2 O 3 and TiO 2 by the regeneration treatment.
（その他の実施形態）
本発明の実施形態のハニカム構造体の製造方法において、チタン酸アルミニウム微粉末とチタン酸アルミニウム粗粉末との混合比は、９：１～６：４が望ましい。
両者の混合比が上記範囲内であると、ハニカム成形体を焼成した際に、焼成後のサイズが収縮により小さくなることを抑制することができるとともに、平均気孔径、気孔径分布及び気孔率を制御することができるからである。 (Other embodiments)
In the method for manufacturing a honeycomb structured body of the embodiment of the present invention, the mixing ratio of the aluminum titanate fine powder and the aluminum titanate coarse powder is desirably 9: 1 to 6: 4.
When the mixing ratio of the two is within the above range, when the honeycomb formed body is fired, the size after firing can be prevented from being reduced by shrinkage, and the average pore diameter, pore diameter distribution, and porosity can be reduced. This is because it can be controlled.
本発明の実施形態のハニカム構造体の製造方法において、チタン酸アルミニウム微粉末とチタン酸アルミニウム粗粉末との混合比は、９：１～６：４が望ましい。
両者の混合比が上記範囲内であると、ハニカム成形体を焼成した際に、焼成後のサイズが収縮により小さくなることを抑制することができるとともに、平均気孔径、気孔径分布及び気孔率を制御することができるからである。 (Other embodiments)
In the method for manufacturing a honeycomb structured body of the embodiment of the present invention, the mixing ratio of the aluminum titanate fine powder and the aluminum titanate coarse powder is desirably 9: 1 to 6: 4.
When the mixing ratio of the two is within the above range, when the honeycomb formed body is fired, the size after firing can be prevented from being reduced by shrinkage, and the average pore diameter, pore diameter distribution, and porosity can be reduced. This is because it can be controlled.
本発明の実施形態のハニカム構造体の製造方法において、ハニカム成形体を焼成する際の焼成時間は、０．５～２４時間であることが望ましい。
上記焼成時間が、０．５時間未満では、焼成が進まないことがあり、２４時間を超えると、焼成後の収縮が大きくなる場合があるからである。 In the method for manufacturing a honeycomb structured body of the embodiment of the present invention, the firing time when firing the honeycomb formed body is preferably 0.5 to 24 hours.
This is because if the firing time is less than 0.5 hours, firing may not proceed, and if it exceeds 24 hours, shrinkage after firing may increase.
上記焼成時間が、０．５時間未満では、焼成が進まないことがあり、２４時間を超えると、焼成後の収縮が大きくなる場合があるからである。 In the method for manufacturing a honeycomb structured body of the embodiment of the present invention, the firing time when firing the honeycomb formed body is preferably 0.5 to 24 hours.
This is because if the firing time is less than 0.5 hours, firing may not proceed, and if it exceeds 24 hours, shrinkage after firing may increase.
上記湿潤混合物を調製する際に使用する有機バインダは、特に限定されず、例えば、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリエチレングリコール等が挙げられる。このなかでは、メチルセルロースが望ましい。
上記有機バインダの配合量は、通常、チタン酸アルミニウム粉末１００重量部に対して、１～１０重量部が望ましい。 The organic binder used when preparing the said wet mixture is not specifically limited, For example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol etc. are mentioned. Of these, methylcellulose is desirable.
In general, the amount of the organic binder is desirably 1 to 10 parts by weight per 100 parts by weight of the aluminum titanate powder.
上記有機バインダの配合量は、通常、チタン酸アルミニウム粉末１００重量部に対して、１～１０重量部が望ましい。 The organic binder used when preparing the said wet mixture is not specifically limited, For example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol etc. are mentioned. Of these, methylcellulose is desirable.
In general, the amount of the organic binder is desirably 1 to 10 parts by weight per 100 parts by weight of the aluminum titanate powder.
上記湿潤混合物を調製する際に使用する可塑剤や潤滑剤は、特に限定されず、可塑剤としては、例えば、グリセリン等が挙げられる。また、潤滑剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシプロピレンアルキルエーテル等のポリオキシアルキレン系化合物等が挙げられる。
潤滑剤の具体例としては、例えば、ポリオキシエチレンモノブチルエーテル、ポリオキシプロピレンモノブチルエーテル等が挙げられる。
なお、可塑剤、潤滑剤は、場合によっては、上記湿潤混合物に含まれていなくてもよい。 The plasticizer and lubricant used in preparing the wet mixture are not particularly limited, and examples of the plasticizer include glycerin. Examples of the lubricant include polyoxyalkylene compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether.
Specific examples of the lubricant include polyoxyethylene monobutyl ether and polyoxypropylene monobutyl ether.
In some cases, the plasticizer and the lubricant may not be contained in the wet mixture.
潤滑剤の具体例としては、例えば、ポリオキシエチレンモノブチルエーテル、ポリオキシプロピレンモノブチルエーテル等が挙げられる。
なお、可塑剤、潤滑剤は、場合によっては、上記湿潤混合物に含まれていなくてもよい。 The plasticizer and lubricant used in preparing the wet mixture are not particularly limited, and examples of the plasticizer include glycerin. Examples of the lubricant include polyoxyalkylene compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether.
Specific examples of the lubricant include polyoxyethylene monobutyl ether and polyoxypropylene monobutyl ether.
In some cases, the plasticizer and the lubricant may not be contained in the wet mixture.
上記湿潤混合物を調製する際に使用する造孔剤は、特に限定されず、例えば、球状アクリル粒子、グラファイト等が挙げられる。
なお、造孔剤は、場合によっては、上記湿潤混合物に含まれていなくてもよい。 The pore forming agent used when preparing the wet mixture is not particularly limited, and examples thereof include spherical acrylic particles and graphite.
In some cases, the pore-forming agent may not be contained in the wet mixture.
なお、造孔剤は、場合によっては、上記湿潤混合物に含まれていなくてもよい。 The pore forming agent used when preparing the wet mixture is not particularly limited, and examples thereof include spherical acrylic particles and graphite.
In some cases, the pore-forming agent may not be contained in the wet mixture.
また、上記湿潤混合物を調製する際には、水以外の分散媒液を使用してもよく、このような分散媒液としては、例えば、メタノール等のアルコール、ベンゼン、トルエン等の有機溶媒が挙げられる。
さらに、上記湿潤混合物中には、成形助剤が添加されていてもよい。
成形助剤としては特に限定されず、例えば、エチレングリコール、デキストリン、脂肪酸、脂肪酸石鹸、ポリアルコール等が挙げられる。 In preparing the wet mixture, a dispersion medium other than water may be used. Examples of such a dispersion medium include alcohols such as methanol and organic solvents such as benzene and toluene. It is done.
Furthermore, a molding aid may be added to the wet mixture.
The molding aid is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol and the like.
さらに、上記湿潤混合物中には、成形助剤が添加されていてもよい。
成形助剤としては特に限定されず、例えば、エチレングリコール、デキストリン、脂肪酸、脂肪酸石鹸、ポリアルコール等が挙げられる。 In preparing the wet mixture, a dispersion medium other than water may be used. Examples of such a dispersion medium include alcohols such as methanol and organic solvents such as benzene and toluene. It is done.
Furthermore, a molding aid may be added to the wet mixture.
The molding aid is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acid, fatty acid soap, polyalcohol and the like.
本発明の実施形態のハニカム構造体の製造方法において、上記湿潤混合物を成形してハニカム成形体を作製する際、上記湿潤混合物の温度は１０℃以下であることが望ましい。温度が高すぎると、有機バインダがゲル化してしまうことがあるからである。
In the method for manufacturing a honeycomb structured body according to an embodiment of the present invention, when the wet mixture is formed to produce a honeycomb formed body, the temperature of the wet mixture is preferably 10 ° C. or lower. It is because an organic binder may gelatinize when temperature is too high.
本発明の実施形態のハニカム構造体の製造方法において、セルを封止する封止材ペーストとしては特に限定されないが、後工程を経て形成される封止材の気孔率が４０～５０％となるものが望ましく、例えば、上記湿潤混合物と同様のものを用いることができる。
In the method for manufacturing a honeycomb structured body according to the embodiment of the present invention, the plug material paste for sealing cells is not particularly limited, but the porosity of the plug material formed through a subsequent process is 40 to 50%. A thing similar to the said wet mixture can be used, for example.
本発明の実施形態のハニカム構造体の製造方法において、押出成形により、ハニカム成形体の長尺体を作製する際に用いる装置は、特に限定されるものではなく、例えば、単軸スクリュー式押出成形機、多軸スクリュー式押出成形機、プランジャー式成形機等が挙げられる。この中でも、プランジャー式成形機を特に好適に用いることができる。
In the method for manufacturing a honeycomb structured body according to the embodiment of the present invention, an apparatus used for producing a long body of a honeycomb formed body by extrusion molding is not particularly limited, and for example, a single screw extrusion molding Machine, multi-screw type extruder, plunger type machine and the like. Among these, a plunger type molding machine can be particularly preferably used.
本発明の実施形態のハニカム構造体の製造方法において、ハニカム成形体の乾燥に用いる乾燥機としては、特に限定されるものではなく、例えば、マイクロ波加熱乾燥機、熱風乾燥機、赤外線乾燥機等が挙げられる。これらは単独で用いてもよいし、、複数組み合わせてもよい。
In the method for manufacturing a honeycomb structure according to the embodiment of the present invention, the dryer used for drying the honeycomb formed body is not particularly limited, and examples thereof include a microwave heating dryer, a hot air dryer, an infrared dryer, and the like. Is mentioned. These may be used alone or in combination.
本発明の実施形態で製造するハニカム構造体の長手方向に対して垂直な断面の形状は、特に円形に限られるものではなく、矩形等、種々の形状とすることができるが、曲線のみ又は曲線と直線とで囲まれた形状であることが望ましい。
その具体例として、円形以外には、例えば、楕円形、長円形、レーストラック形、楕円形又は長円形等の単純閉曲線の一部が凹部を有する形状（ｃｏｎｃａｖｅ形状）等を挙げることができる。 The shape of the cross section perpendicular to the longitudinal direction of the honeycomb structure manufactured in the embodiment of the present invention is not particularly limited to a circular shape, and may be various shapes such as a rectangle. And a shape surrounded by a straight line.
As a specific example, in addition to a circle, for example, a shape in which a part of a simple closed curve such as an ellipse, an ellipse, a racetrack, an ellipse, or an ellipse has a concave portion (concave shape) can be given.
その具体例として、円形以外には、例えば、楕円形、長円形、レーストラック形、楕円形又は長円形等の単純閉曲線の一部が凹部を有する形状（ｃｏｎｃａｖｅ形状）等を挙げることができる。 The shape of the cross section perpendicular to the longitudinal direction of the honeycomb structure manufactured in the embodiment of the present invention is not particularly limited to a circular shape, and may be various shapes such as a rectangle. And a shape surrounded by a straight line.
As a specific example, in addition to a circle, for example, a shape in which a part of a simple closed curve such as an ellipse, an ellipse, a racetrack, an ellipse, or an ellipse has a concave portion (concave shape) can be given.
本発明の実施形態で製造するハニカム構造体の開口率の望ましい値は、下限が５０％であり、上限が７５％である。
上記開口率が５０％未満では、ハニカム構造体に排ガスが流入出する際の圧力損失が大きくなる場合があり、７５％を超えると、ハニカム構造体の強度が低下したりする場合がある。 A desirable value of the aperture ratio of the honeycomb structure manufactured in the embodiment of the present invention is a lower limit of 50% and an upper limit of 75%.
When the opening ratio is less than 50%, the pressure loss when the exhaust gas flows into and out of the honeycomb structure may increase, and when it exceeds 75%, the strength of the honeycomb structure may decrease.
上記開口率が５０％未満では、ハニカム構造体に排ガスが流入出する際の圧力損失が大きくなる場合があり、７５％を超えると、ハニカム構造体の強度が低下したりする場合がある。 A desirable value of the aperture ratio of the honeycomb structure manufactured in the embodiment of the present invention is a lower limit of 50% and an upper limit of 75%.
When the opening ratio is less than 50%, the pressure loss when the exhaust gas flows into and out of the honeycomb structure may increase, and when it exceeds 75%, the strength of the honeycomb structure may decrease.
本発明の実施形態で製造するハニカム構造体において、セル壁の厚さの望ましい下限は０．１５ｍｍである。０．１５ｍｍ未満では、ハニカム構造体の強度が低下することがあるからである。
一方、上記セル壁の厚さの望ましい上限は０．４ｍｍである。セル壁の厚さが０．４ｍｍを超えると、セルの開口率及び／又は濾過面積が小さくなり、それに伴って圧力損失が増加することがある。 In the honeycomb structure manufactured in the embodiment of the present invention, a desirable lower limit of the cell wall thickness is 0.15 mm. This is because if the thickness is less than 0.15 mm, the strength of the honeycomb structure may be lowered.
On the other hand, the desirable upper limit of the cell wall thickness is 0.4 mm. When the thickness of the cell wall exceeds 0.4 mm, the cell aperture ratio and / or the filtration area may be reduced, and the pressure loss may increase accordingly.
一方、上記セル壁の厚さの望ましい上限は０．４ｍｍである。セル壁の厚さが０．４ｍｍを超えると、セルの開口率及び／又は濾過面積が小さくなり、それに伴って圧力損失が増加することがある。 In the honeycomb structure manufactured in the embodiment of the present invention, a desirable lower limit of the cell wall thickness is 0.15 mm. This is because if the thickness is less than 0.15 mm, the strength of the honeycomb structure may be lowered.
On the other hand, the desirable upper limit of the cell wall thickness is 0.4 mm. When the thickness of the cell wall exceeds 0.4 mm, the cell aperture ratio and / or the filtration area may be reduced, and the pressure loss may increase accordingly.
本発明の実施形態で製造するハニカム構造体において、セル密度は特に限定されず、望ましい下限は、２３．３個／ｃｍ２（１５０個／ｉｎ２）、望ましい上限は、９３．０）個／ｃｍ２（６００個／ｉｎ２）、より望ましい下値は、３１個／ｃｍ２（２００個／ｉｎ２）、より望ましい上限は、７７．５個／ｃｍ２（５００．０個／ｉｎ２）である。
In the honeycomb structure manufactured in the embodiment of the present invention, the cell density is not particularly limited, and a desirable lower limit is 23.3 / cm 2 (150 / in 2 ), and a desirable upper limit is 93.0) / cm 2 (600 / in 2 ), more desirable lower limit is 31 / cm 2 (200 / in 2 ), and a more desirable upper limit is 77.5 / cm 2 (500.0 / in 2 ). is there.
なお、上記セルの平面視形状については特に四角形に限定されず、例えば、三角形、六角形、八角形、十二角形、円形、楕円形、星型等の形状を挙げることができる。
The shape of the cell in plan view is not particularly limited to a quadrangle, and examples thereof include a triangle, a hexagon, an octagon, a dodecagon, a circle, an ellipse, and a star.
上記ハニカム構造体には、必要に応じて、触媒を担持させてもよい。ハニカム構造体に担持させる触媒の種類は特に限定されるものでないが、例えば、貴金属元素、アルカリ金属元素、アルカリ土類金属元素、金属酸化物等が挙げられる。これらは、単独で用いてもよいし、２種以上併用してもよい。
A catalyst may be supported on the honeycomb structure as necessary. The type of catalyst supported on the honeycomb structure is not particularly limited, and examples thereof include noble metal elements, alkali metal elements, alkaline earth metal elements, and metal oxides. These may be used alone or in combination of two or more.
上記貴金属元素としては、例えば、白金、パラジウム、ロジウム等が挙げられ、上記アルカリ金属元素としては、例えば、カリウム、ナトリウム等が挙げられ、上記アルカリ土類金属元素としては、例えば、バリウム等が挙げられる。また、上記金属酸化物としては、例えば、ＣｅＯ２、Ｋ２Ｏ、ＺｒＯ２、ＦｅＯ２、Ｆｅ２Ｏ３、ＣｕＯ、ＣｕＯ２、Ｍｎ２Ｏ３、ＭｎＯ、組成式ＡｎＢ１－ｎＣＯ３（式中、０≦ｎ≦１であり、ＡはＬａ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ又はＹであり、Ｂはアルカリ金属又はアルカリ土類金属であり、ＣはＭｎ、Ｃｏ、Ｆｅ又はＮｉ）で表される複合酸化物等が挙げられる。
上記触媒を担持させることにより、上記ハニカム構造体をハニカムフィルタとして再生処理に用いる際に、ＰＭの燃焼温度を低下させることができる。 Examples of the noble metal element include platinum, palladium, rhodium and the like, examples of the alkali metal element include potassium and sodium, and examples of the alkaline earth metal element include barium and the like. It is done. Examples of the metal oxide include CeO 2 , K 2 O, ZrO 2 , FeO 2 , Fe 2 O 3 , CuO, CuO 2 , Mn 2 O 3 , MnO, composition formula An B 1-n CO 3 (where 0 ≦ n ≦ 1, A is La, Nd, Sm, Eu, Gd or Y, B is an alkali metal or alkaline earth metal, and C is Mn, Co, Fe or Ni) ) And the like.
By supporting the catalyst, the PM combustion temperature can be lowered when the honeycomb structure is used as a honeycomb filter for the regeneration treatment.
上記触媒を担持させることにより、上記ハニカム構造体をハニカムフィルタとして再生処理に用いる際に、ＰＭの燃焼温度を低下させることができる。 Examples of the noble metal element include platinum, palladium, rhodium and the like, examples of the alkali metal element include potassium and sodium, and examples of the alkaline earth metal element include barium and the like. It is done. Examples of the metal oxide include CeO 2 , K 2 O, ZrO 2 , FeO 2 , Fe 2 O 3 , CuO, CuO 2 , Mn 2 O 3 , MnO, composition formula An B 1-n CO 3 (where 0 ≦ n ≦ 1, A is La, Nd, Sm, Eu, Gd or Y, B is an alkali metal or alkaline earth metal, and C is Mn, Co, Fe or Ni) ) And the like.
By supporting the catalyst, the PM combustion temperature can be lowered when the honeycomb structure is used as a honeycomb filter for the regeneration treatment.
また、上記触媒を担持させる場合には、ハニカム構造体の表面に高い比表面積のアルミナ膜を形成し、このアルミナ膜の表面に上記触媒を付与してもよい。
When the catalyst is supported, an alumina film having a high specific surface area may be formed on the surface of the honeycomb structure, and the catalyst may be applied to the surface of the alumina film.
１０ ハニカム構造体
１１ セル
１２ 封止材
１３ セル壁 10honeycomb structure 11 cell 12 sealing material 13 cell wall
１１ セル
１２ 封止材
１３ セル壁 10
Claims (4)
- 平均粒子径が３～５０μｍで、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１５質量％以下である組成比のチタン酸アルミニウム粗粉末と、平均粒子径が０．１～３μｍで、Ａｌ２Ｏ３が４０～６０質量％、ＴｉＯ２が３０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上８質量％未満である組成比のチタン酸アルミニウム微粉末とを含む湿潤混合物を成形して、長手方向に多数のセルが並設された柱状のハニカム成形体を作製する成形工程と、
前記ハニカム成形体を１２００℃～１７００℃で焼成する焼成工程とを行うことを特徴とするハニカム構造体の製造方法。 Titanium having a composition ratio in which the average particle size is 3 to 50 μm, Al 2 O 3 is 40 to 60% by mass, TiO 2 is 30 to 50% by mass, and the total of MgO and SiO 2 is 8% by mass to 15% by mass. Aluminum oxide coarse powder, average particle size of 0.1 to 3 μm, Al 2 O 3 of 40 to 60% by mass, TiO 2 of 30 to 50% by mass, and the total of MgO and SiO 2 of 1 to 8% by mass Forming a wet mixture containing aluminum titanate fine powder having a composition ratio of less than 1% to produce a columnar honeycomb formed body in which a number of cells are arranged in the longitudinal direction;
And a firing step of firing the honeycomb formed body at 1200 ° C. to 1700 ° C. - 前記チタン酸アルミニウム粗粉末の組成比は、Ａｌ２Ｏ３が４０～５０質量％、ＴｉＯ２が４０～５０質量％、ＭｇＯ及びＳｉＯ２の合計が８質量％以上１２質量％以下である請求項１に記載のハニカム構造体の製造方法。 The composition ratio of the aluminum titanate coarse powder is such that Al 2 O 3 is 40 to 50% by mass, TiO 2 is 40 to 50% by mass, and the total of MgO and SiO 2 is 8% by mass to 12% by mass. 2. A method for manufacturing a honeycomb structure according to 1.
- 前記チタン酸アルミニウム微粉末の組成比は、Ａｌ２Ｏ３が５０～６０質量％、ＴｉＯ２が３０～４０質量％、ＭｇＯ及びＳｉＯ２の合計が１質量％以上５質量％以下である請求項１又は２に記載のハニカム構造体の製造方法。 The composition ratio of the aluminum titanate fine powder is as follows: Al 2 O 3 is 50 to 60% by mass, TiO 2 is 30 to 40% by mass, and the total of MgO and SiO 2 is 1% by mass to 5% by mass. A method for manufacturing a honeycomb structure according to 1 or 2.
- 前記ハニカム成形体の各セルのいずれか一方の端部に封止材ペーストを充填する封止工程を行う請求項１～３のいずれかに記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 1 to 3, wherein a sealing step is performed in which a sealing material paste is filled into any one end of each cell of the honeycomb formed body.
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| PCT/JP2008/056412 WO2009122537A1 (en) | 2008-03-31 | 2008-03-31 | Process for producing honeycomb structure |
| JP2010505196A JPWO2009122537A1 (en) | 2008-03-31 | 2008-03-31 | Manufacturing method of honeycomb structure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011526573A (en) * | 2008-07-04 | 2011-10-13 | サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン | Particle mixture for producing an aluminum titanate type porous structure |
| WO2014014059A1 (en) * | 2012-07-20 | 2014-01-23 | 住友化学株式会社 | Honeycomb filter |
| CN109415274A (en) * | 2016-07-05 | 2019-03-01 | 揖斐电株式会社 | The manufacturing method of honeycomb structure and honeycomb structure |
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| JPH07138083A (en) * | 1993-11-11 | 1995-05-30 | Toyota Motor Corp | Production of porous aluminum titanate sintered compact |
| JPH08290963A (en) * | 1995-04-21 | 1996-11-05 | Matsushita Electric Ind Co Ltd | Material having low thermal expansion and discharge gas filter using the same |
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| JPH02129064A (en) * | 1988-11-08 | 1990-05-17 | Toyota Motor Corp | Inserted parts made of aluminum titanate |
| JPH07122536A (en) * | 1993-10-21 | 1995-05-12 | Hitachi Ltd | Fabrication system for semiconductor device |
| JP4945056B2 (en) * | 2003-09-12 | 2012-06-06 | オーセラ株式会社 | Honeycomb carrier for exhaust gas purification catalyst and manufacturing method thereof |
| JP2005269886A (en) * | 2004-02-18 | 2005-09-29 | Tdk Corp | Cylindrical magnet and its production method |
| WO2009122538A1 (en) * | 2008-03-31 | 2009-10-08 | イビデン株式会社 | Honeycomb structure |
| JPWO2009122534A1 (en) * | 2008-03-31 | 2011-07-28 | イビデン株式会社 | Honeycomb structure |
| WO2009122532A1 (en) * | 2008-03-31 | 2009-10-08 | イビデン株式会社 | Honeycomb structure |
| EP2202211A4 (en) * | 2008-03-31 | 2011-09-28 | Ibiden Co Ltd | Honeycomb structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07138083A (en) * | 1993-11-11 | 1995-05-30 | Toyota Motor Corp | Production of porous aluminum titanate sintered compact |
| JPH08290963A (en) * | 1995-04-21 | 1996-11-05 | Matsushita Electric Ind Co Ltd | Material having low thermal expansion and discharge gas filter using the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011526573A (en) * | 2008-07-04 | 2011-10-13 | サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン | Particle mixture for producing an aluminum titanate type porous structure |
| WO2014014059A1 (en) * | 2012-07-20 | 2014-01-23 | 住友化学株式会社 | Honeycomb filter |
| CN109415274A (en) * | 2016-07-05 | 2019-03-01 | 揖斐电株式会社 | The manufacturing method of honeycomb structure and honeycomb structure |
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