WO2017164114A1 - Honeycomb structure and honeycomb structure production method - Google Patents
Honeycomb structure and honeycomb structure production method Download PDFInfo
- Publication number
- WO2017164114A1 WO2017164114A1 PCT/JP2017/010907 JP2017010907W WO2017164114A1 WO 2017164114 A1 WO2017164114 A1 WO 2017164114A1 JP 2017010907 W JP2017010907 W JP 2017010907W WO 2017164114 A1 WO2017164114 A1 WO 2017164114A1
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- WIPO (PCT)
- Prior art keywords
- honeycomb
- honeycomb structure
- type zeolite
- fired body
- raw material
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 57
- 239000010457 zeolite Substances 0.000 claims abstract description 57
- 238000005192 partition Methods 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 28
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 238000010304 firing Methods 0.000 claims description 14
- 239000012784 inorganic fiber Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
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- 229930195733 hydrocarbon Natural products 0.000 description 39
- 150000002430 hydrocarbons Chemical class 0.000 description 39
- 239000004215 Carbon black (E152) Substances 0.000 description 34
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 24
- 230000002093 peripheral effect Effects 0.000 description 21
- 239000010410 layer Substances 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
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- 238000000465 moulding Methods 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 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
- 239000012266 salt solution Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B01J35/56—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to a honeycomb structure and a method for manufacturing a honeycomb structure.
- Hydrocarbon (HC) contained in exhaust gas discharged from a gasoline engine or the like is usually purified by oxidation using a honeycomb structure on which a three-way catalyst made of a noble metal such as platinum is supported.
- a honeycomb structure on which a three-way catalyst made of a noble metal such as platinum is supported.
- HC is not sufficiently purified at a temperature lower than that. Therefore, at a temperature where the exhaust gas temperature is low, such as immediately after the engine is started, HC is discharged without being purified even though the amount of HC discharged is large.
- the exhaust gas temperature tends to be lowered, so that the HC purification rate is likely to decrease.
- HC is adsorbed in a low temperature region until reaching the temperature at which the three-way catalyst is activated, and the adsorbed HC is released when the temperature becomes high, thereby improving the HC purification rate.
- Techniques for making them disclosed are disclosed.
- ⁇ -type zeolite containing Fe is used as the HC adsorbent.
- Patent Document 2 as a method for producing a zeolite containing a metal such as Fe or Ni, after performing dealumination treatment on the zeolite with steaming and mineral acid, the obtained zeolite slurry is treated with an aqueous metal salt solution and A method for performing a treatment for increasing the pH is disclosed.
- Patent Document 3 discloses that a metal-containing zeolite is used as an inorganic binder. A method of manufacturing a honeycomb structure by forming into a honeycomb shape with alumina and inorganic fibers is disclosed.
- the HC adsorption amount and the HC release temperature are important. That is, it is important to adsorb a large amount of HC and adsorb HC to a temperature at which the three-way catalyst is activated, and a honeycomb structure having such characteristics is required.
- the honeycomb structure when using a honeycomb structure, the honeycomb structure may be damaged due to volume shrinkage / expansion due to moisture adsorption / desorption, and it is also required to suppress such damage to the honeycomb structure. Yes.
- the present invention has been made to solve the above problems, and an object of the present invention is to provide a honeycomb structure excellent in HC adsorption performance and hardly damaged during use, and a method for manufacturing the same.
- a honeycomb structure of the present invention is a honeycomb structure including a honeycomb fired body in which a plurality of through holes are arranged in parallel in a longitudinal direction with partition walls interposed therebetween, and the honeycomb fired body includes CuO, ⁇ -type zeolite, and inorganic
- the ⁇ -type zeolite has an SiO 2 / Al 2 O 3 molar ratio of 300 or more.
- the honeycomb structure of the present invention a large amount of HC can be adsorbed up to a temperature at which the three-way catalyst is activated by coexisting CuO with ⁇ -type zeolite having a high SiO 2 / Al 2 O 3 molar ratio. Therefore, the honeycomb structure of the present invention is excellent in HC adsorption performance.
- the high SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite means that the amount of Al in the ⁇ -type zeolite is small. Therefore, in the honeycomb structure of the present invention, damage to the honeycomb structure that occurs during use can be suppressed. Moisture is easily adsorbed on Al constituting the ⁇ -type zeolite. When moisture is adsorbed on Al, the skeleton structure of ⁇ -type zeolite is distorted, and the volume of ⁇ -type zeolite changes.
- the amount of Al in the ⁇ -type zeolite is small as described above, it is difficult for moisture to be adsorbed on the ⁇ -type zeolite, and volume shrinkage / expansion due to moisture adsorption / desorption is suppressed. Conceivable.
- the honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to the ⁇ -type zeolite.
- the amount of Cu contained in the honeycomb structure is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
- the honeycomb fired body further includes inorganic fibers.
- the strength of the honeycomb structure can be improved.
- a three-way catalyst is supported on the surface of the partition wall. HC can be purified by the three-way catalyst.
- a method for manufacturing a honeycomb structure of the present invention is a method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and includes a CuO source, ⁇ -type zeolite,
- a raw material paste containing an inorganic binder By forming a raw material paste containing an inorganic binder, a forming step for producing a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and by firing the honeycomb formed body, a honeycomb And a firing step for producing a fired body, wherein the ⁇ -type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more.
- the amount of the CuO source contained in the raw material paste is preferably 1 to 7% by weight with respect to the ⁇ -type zeolite in terms of Cu.
- the amount of the CuO source contained in the raw material paste is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
- the raw material paste preferably further contains inorganic fibers.
- the strength of the obtained honeycomb structure can be improved.
- the method for manufacturing a honeycomb structure of the present invention preferably further includes a supporting step of supporting a three-way catalyst on the surface of the partition wall. HC can be purified by the three-way catalyst.
- FIG. 1 is a perspective view schematically showing an example of the honeycomb structure of the present invention.
- FIG. 2 is a perspective view schematically showing another example of the honeycomb structure of the present invention.
- FIG. 3 is a perspective view schematically showing an example of a honeycomb fired body constituting the honeycomb structure shown in FIG.
- FIG. 4 is a graph showing the relationship between temperature and hydrocarbon release.
- FIG. 5 is a graph showing the results of Cu state analysis by H 2 -TPR measurement.
- the honeycomb structure of the present invention includes a honeycomb fired body in which a plurality of through holes are arranged in parallel in the longitudinal direction with partition walls therebetween.
- the honeycomb fired body is formed of an extrusion-molded body containing CuO, ⁇ -type zeolite, and an inorganic binder.
- the honeycomb fired body is manufactured by extruding and firing a raw material paste containing a CuO source, ⁇ -type zeolite, and an inorganic binder.
- the honeycomb structure of the present invention may include a single honeycomb fired body, or may include a plurality of honeycomb fired bodies bonded through an adhesive layer.
- an outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body.
- FIG. 1 is a perspective view schematically showing an example of the honeycomb structure of the present invention.
- a honeycomb structure 10 shown in FIG. 1 includes a single honeycomb fired body 11 in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b interposed therebetween.
- the honeycomb fired body 11 is made of an extrusion-molded body containing CuO, ⁇ -type zeolite, and an inorganic binder. Further, an outer peripheral coat layer 12 is formed on the outer peripheral surface of the honeycomb fired body 11.
- FIG. 2 is a perspective view schematically showing another example of the honeycomb structure of the present invention.
- FIG. 3 is a perspective view schematically showing an example of a honeycomb fired body constituting the honeycomb structure shown in FIG.
- honeycomb fired bodies 21 in which a plurality of through holes 21 a are arranged in parallel in the longitudinal direction with partition walls 21 b interposed therebetween are bonded via an adhesive layer 23. Except for this, it has the same configuration as the honeycomb structure 10 shown in FIG. Furthermore, an outer peripheral coat layer 22 is formed on the outer peripheral surface of the honeycomb fired body 21.
- the outer peripheral coat layers 12 and 22 may not be formed, respectively.
- the ⁇ -type zeolite has a SiO 2 / Al 2 O 3 molar ratio of 300 or more.
- the SiO 2 / Al 2 O 3 molar ratio is desirably 350 or more, and more desirably 400 or more. Further, the SiO 2 / Al 2 O 3 molar ratio is desirably 1000 or less, and more desirably 800 or less.
- the SiO 2 / Al 2 O 3 molar ratio of ⁇ -type zeolite can be measured by fluorescent X-ray analysis (XRF).
- beta type for SiO 2 / Al 2 O 3 molar ratio of the zeolite is not changed before and after sintering, the SiO 2 / Al 2 O 3 molar ratio of beta-type zeolite contained in the raw material paste, a honeycomb structure of the present invention
- the ⁇ -type zeolite can also have a SiO 2 / Al 2 O 3 molar ratio.
- the average particle size of ⁇ -type zeolite contained in the raw material paste is preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m.
- the average particle size of ⁇ -type zeolite is the average particle size of primary particles measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Seishin Enterprises: Laser Micronizer LMS-30).
- the amount of ⁇ -type zeolite contained in the raw material paste is preferably 25 to 60% by weight, more preferably 30 to 50% by weight.
- the honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to ⁇ -type zeolite, and more preferably contains 2 to 4% by weight.
- the Cu content in the honeycomb structure can be measured by fluorescent X-ray analysis (XRF). Further, the Cu content in the honeycomb structure can also be determined from the amount of CuO source contained in the raw material paste.
- the ⁇ -type zeolite is preferably not ion-exchanged with Cu ions, and CuO is preferably supported on the surface of the ⁇ -type zeolite. Note that the state of Cu supported on the ⁇ -type zeolite can be analyzed from a peak obtained by performing H 2 -TPR measurement on the honeycomb structure.
- the inorganic binder contained in the raw material paste is not particularly limited, and examples thereof include solids contained in alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite, etc. You may use together.
- the amount of the inorganic binder contained in the raw material paste is desirably 5 to 20% by weight, and more desirably 7 to 15% by weight.
- the honeycomb fired body further includes inorganic fibers. That is, the raw material paste preferably further includes inorganic fibers.
- the aspect ratio of the inorganic fiber is preferably 2 to 300, more preferably 5 to 200, and still more preferably 10 to 100.
- the amount of inorganic fibers contained in the raw material paste is preferably 2 to 15% by weight, and more preferably 5 to 10% by weight.
- the shape of the honeycomb structure of the present invention is not limited to a cylindrical shape, and examples thereof include a prismatic shape, an elliptical cylindrical shape, a long cylindrical shape, and a rounded chamfered prismatic shape (for example, a rounded chamfered triangular prism shape). .
- the shape of the through hole of the honeycomb fired body is not limited to a quadrangular prism shape, and examples thereof include a triangular prism shape and a hexagonal prism shape.
- the density of the through holes in the cross section perpendicular to the longitudinal direction of the honeycomb fired body is preferably 31 to 155 holes / cm 2 .
- the thickness of the partition walls of the honeycomb fired body is preferably 0.10 to 0.50 mm, and more preferably 0.20 to 0.40 mm.
- the thickness of the outer peripheral coat layer is preferably 0.1 to 2.0 mm.
- a three-way catalyst refers to a catalyst that mainly purifies hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx).
- Examples of the three-way catalyst include noble metals such as platinum, palladium, and rhodium.
- noble metals such as platinum, palladium, and rhodium.
- carrier which consists of heat resistant inorganic oxides, such as an alumina, can also be used as a three-way catalyst.
- the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
- the supported amount of the three-way catalyst refers to the weight of the three-way catalyst per apparent volume of the honeycomb structure.
- the apparent volume of the honeycomb structure is a volume including the void volume, and includes the volume of the outer peripheral coat layer and / or the adhesive layer.
- a method for manufacturing a honeycomb structure of the present invention is a method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and includes a CuO source, ⁇ -type zeolite, By forming a raw material paste containing an inorganic binder, a forming step for producing a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and by firing the honeycomb formed body, a honeycomb And a firing step for producing a fired body.
- a raw material paste containing a CuO source, ⁇ -type zeolite, and an inorganic binder is formed, so that a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween.
- a honeycomb formed body is produced. Specifically, a honeycomb formed body is manufactured by extrusion molding using a raw material paste containing a CuO source, ⁇ -type zeolite, and an inorganic binder, and further containing inorganic fibers and the like as necessary.
- the ⁇ 2 -type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. Since the structure of ⁇ -type zeolite has already been described, its detailed description is omitted. Moreover, since it is as having already demonstrated the inorganic binder, inorganic fiber, etc. which are contained in a raw material paste, the detailed description is abbreviate
- Examples of the CuO source include copper oxide, copper nitrate, copper acetate, and copper sulfate. Among these, copper oxide is desirable.
- the amount of the CuO source contained in the raw material paste is preferably 1 to 7% by weight with respect to ⁇ -type zeolite in terms of Cu, and is preferably 2 to 4% by weight. It is more desirable.
- the raw material paste may further contain an organic binder, a dispersion medium, a molding aid and the like as necessary.
- Methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol, a phenol resin, an epoxy resin etc. are mentioned, You may use 2 or more types together.
- Alcohol such as water
- organic solvents such as benzene, methanol, etc.
- the raw material paste When preparing the raw material paste, it is desirable to mix and knead, and it may be mixed using a mixer, an attritor or the like, or may be kneaded using a kneader or the like.
- the honeycomb formed body can be dried to produce a honeycomb dried body. desirable.
- a dryer such as a microwave dryer, hot air dryer, dielectric dryer, vacuum dryer, vacuum dryer, freeze dryer, etc.
- honeycomb formed body and the honeycomb dried body before the firing step are collectively referred to as a honeycomb formed body.
- the honeycomb fired body is fired to produce a honeycomb fired body.
- this process performs degreasing and firing of the honeycomb formed body, it can also be referred to as a “degreasing / firing process”, but it is referred to as a “firing process” for convenience.
- the temperature of the firing step is desirably 600 to 1000 ° C., and more desirably 600 to 800 ° C.
- the firing process time is preferably 1 to 10 hours, and more preferably 1.5 to 5 hours.
- the atmosphere of the firing step is not particularly limited, but it is desirable that the oxygen concentration is 1 to 10% by volume.
- the honeycomb structure of the present invention can be manufactured.
- the method for manufacturing a honeycomb structure of the present invention preferably further includes a supporting step of supporting a three-way catalyst on the surface of the partition wall.
- Examples of the method for supporting the three-way catalyst on the surface of the partition wall include a method in which the honeycomb fired body or the honeycomb structure is immersed in a slurry containing the three-way catalyst, and then heated up and heated.
- a three-way catalyst may be supported on the surface of the partition wall of the honeycomb fired body before forming the outer peripheral coat layer, or the honeycomb fired body after forming the outer peripheral coat layer or A three-way catalyst may be supported on the surface of the partition walls of the honeycomb structure.
- the three-way catalyst may be supported on the surface of the partition walls of the honeycomb fired body before forming the adhesive layer, or the honeycomb fired body or honeycomb after forming the adhesive layer A three-way catalyst may be supported on the surface of the partition walls of the structure.
- the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
- the outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body, the outer peripheral coat layer is coated with the outer peripheral coat layer paste on the outer peripheral surface excluding both end faces. Thereafter, it can be formed by drying and solidifying.
- the honeycomb structured body in which a plurality of honeycomb fired bodies are bonded via an adhesive layer has an adhesive layer paste on the outer peripheral surface excluding both end faces of the plurality of honeycomb fired bodies. After applying and adhering, it can be produced by drying and solidifying.
- Example 1 1 part by weight of CuO (average particle diameter: 2 ⁇ m) as a CuO source, 40 parts by weight of ⁇ -type zeolite (SiO 2 / Al 2 O 3 molar ratio: 440, average particle diameter: 2 ⁇ m), and boehmite as an inorganic binder 7.5 parts by weight of alumina fibers having an average fiber diameter of 3 ⁇ m and an average fiber length of 120 ⁇ m, 5 parts by weight of methyl cellulose as an organic binder, 5 parts by weight of oleic acid as a molding aid, and 31 parts of ion-exchanged water Part by weight was mixed and kneaded to prepare a raw material paste.
- CuO average particle diameter: 2 ⁇ m
- ⁇ -type zeolite SiO 2 / Al 2 O 3 molar ratio: 440, average particle diameter: 2 ⁇ m
- boehmite as an inorganic binder 7.5 parts by weight of alumina fibers having an average fiber diameter of 3
- the raw material paste was extruded using an extruder, and a regular quadrangular prism-shaped honeycomb formed body was produced.
- the honeycomb molded body was dried for 17 minutes at an output of 40 kW and a reduced pressure of 6.7 kPa using a vacuum microwave dryer, and then degreased and fired at 700 ° C. for 3 hours and 40 minutes to produce a honeycomb fired body.
- the honeycomb fired body had a regular square pillar shape with a side of 33 mm and a length of 43 mm, a density of through holes of 62 holes / cm 2 , and a partition wall thickness of 0.36 mm.
- Comparative Example 1 a honeycomb fired body was manufactured using a raw material paste not including a CuO source as follows.
- a raw material paste was prepared by mixing and kneading 7.5 parts by weight of alumina fibers, 5 parts by weight of methylcellulose as an organic binder, 5 parts by weight of oleic acid and 32 parts by weight of ion-exchanged water as a molding aid.
- the raw material paste was extruded using an extruder, and a regular quadrangular prism-shaped honeycomb formed body was produced.
- the honeycomb molded body was dried for 17 minutes at an output of 40 kW and a reduced pressure of 6.7 kPa using a vacuum microwave dryer, and then degreased and fired at 700 ° C. for 3 hours and 40 minutes to produce a honeycomb fired body.
- the honeycomb fired body had a regular square pillar shape with a side of 33 mm and a length of 43 mm, a density of through holes of 62 holes / cm 2 , and a partition wall thickness of 0.36 mm.
- Comparative Example 2 In Comparative Example 2, a honeycomb fired body was manufactured in the same manner as in Example 1 except that a raw material paste containing ⁇ -type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 40 was used. Thus, an evaluation sample of Comparative Example 2 was obtained.
- Example 1 the evaluation sample of Comparative Example 1 and Comparative Example 2 450 ° C. in an N 2 gas atmosphere, after maintaining for 30 minutes, in an N 2 gas atmosphere containing CO 0.3 vol% 450 Hold at 2 ° C. for 2 minutes.
- a gas containing 1125 ppmC of propylene, 375 ppmC of propane, 0.2% by volume of CO, 10% by volume of H 2 O, 20% by volume of O 2 and the balance being N 2 Hydrocarbon (HC) propylene and propane were adsorbed by flowing at 30 ° C. for 30 seconds.
- HC N 2 Hydrocarbon
- the gas was switched to a gas containing 10% by volume of H 2 O and the balance being N 2 , and the temperature was raised to 450 ° C. at a rate of 60 ° C./min.
- the total hydrocarbon (THC) of the gas flowing out from the evaluation sample was measured, and the value was used as the amount of hydrocarbon released from the evaluation sample.
- FIG. 4 is a graph showing the relationship between temperature and hydrocarbon release. From FIG. 4, it was confirmed that in Example 1, hydrocarbons were released on the high temperature side as compared with Comparative Example 1, and the amount of released hydrocarbons increased significantly. Further, in Example 1, it was confirmed that hydrocarbons were released on the high temperature side as compared with Comparative Example 2, and that the amount of released hydrocarbons was large. From the above results, it is considered that by making CuO coexist in ⁇ -type zeolite having a high SiO 2 / Al 2 O 3 molar ratio, a honeycomb structure excellent in hydrocarbon adsorption performance can be obtained.
- Example 1 [Cu state analysis by H 2 -TPR measurement] Using a catalyst analyzer (manufactured by Microtrack Bell: BELCAT-A), as a pretreatment, the sample for evaluation of Example 1 was held in a He gas atmosphere at 210 ° C. for 2 hours, then cooled to 50 ° C., The temperature was raised to 1000 ° C. at a rate of 10 ° C./min in an atmosphere of H 2 : 4.95% by volume (the rest being Ar). At that time, changes in the amount of gas flowing out from the evaluation sample were measured with a thermal conductivity detector (TCD) and plotted.
- TCD thermal conductivity detector
- FIG. 5 is a graph showing the results of Cu state analysis by H 2 -TPR measurement. From FIG. 5, in Example 1, it was confirmed that the maximum peak exists in 200 degreeC vicinity. This peak is considered to be a peak derived from CuO that is not ion-exchanged and is deposited on the surface of the ⁇ -type zeolite. From this result, in Example 1, it is considered that ⁇ -type zeolite is not ion-exchanged by Cu ions, and CuO is supported on the surface of ⁇ -type zeolite.
- Example 1 The samples for evaluation of Example 1 and Comparative Example 2 are immersed in water, the volume change rate [%] when the water absorption rate is set to a predetermined value is obtained, and the value is taken as the water absorption displacement amount.
- the water absorption is calculated by measuring the weight at the time of absolutely dry and the weight at the time of water absorption using an electronic balance (HR202i manufactured by A & D). As a result, in Example 1, it can be confirmed that the amount of water absorption displacement is smaller than that in Comparative Example 2.
Abstract
This honeycomb structure, comprising a honeycomb fired body that has multiple through-holes separated by partition walls and arranged side-by-side in the length direction, is characterized in that the honeycomb fired body comprises an extrusion-molded body that contains CuO, β-zeolite and an inorganic binder, and in that the molar ratio SiO2/Al2O3 of the β-zeolite is greater than or equal to 300.
Description
本発明は、ハニカム構造体及びハニカム構造体の製造方法に関する。
The present invention relates to a honeycomb structure and a method for manufacturing a honeycomb structure.
ガソリンエンジン等から排出される排ガス中に含まれる炭化水素（ＨＣ）は、通常、白金等の貴金属からなる三元触媒が担持されたハニカム構造体を用いて酸化することによって浄化される。ＨＣを浄化するためには三元触媒が２００℃程度まで昇温される必要があり、それ以下の温度ではＨＣが充分に浄化されない。そのため、エンジン始動直後のように排ガス温度が低い温度では、ＨＣの排出量が多いにも関わらず、ＨＣが浄化されずに排出されてしまう。特に、将来的に燃費の向上が進むと、排ガス温度は低くなる傾向にあるため、ＨＣの浄化率が低下しやすくなると考えられる。
Hydrocarbon (HC) contained in exhaust gas discharged from a gasoline engine or the like is usually purified by oxidation using a honeycomb structure on which a three-way catalyst made of a noble metal such as platinum is supported. In order to purify HC, it is necessary to raise the temperature of the three-way catalyst to about 200 ° C., and HC is not sufficiently purified at a temperature lower than that. Therefore, at a temperature where the exhaust gas temperature is low, such as immediately after the engine is started, HC is discharged without being purified even though the amount of HC discharged is large. In particular, if the fuel efficiency is improved in the future, the exhaust gas temperature tends to be lowered, so that the HC purification rate is likely to decrease.
そこで、特許文献１のように、三元触媒が活性化する温度に達するまでの低温領域ではＨＣを吸着し、高温になったときに吸着したＨＣを放出することによって、ＨＣの浄化率を向上させる技術が開示されている。例えば、特許文献１では、ＨＣ吸着材として、Ｆｅを含むβ型ゼオライトが用いられている。
Therefore, as in Patent Document 1, HC is adsorbed in a low temperature region until reaching the temperature at which the three-way catalyst is activated, and the adsorbed HC is released when the temperature becomes high, thereby improving the HC purification rate. Techniques for making them disclosed are disclosed. For example, in Patent Document 1, β-type zeolite containing Fe is used as the HC adsorbent.
特許文献２には、ＦｅやＮｉ等の金属を含有するゼオライトの製造方法として、ゼオライトに対してスチーミング及び鉱酸によって脱アルミニウム処理を行った後、得られたゼオライトスラリーに金属塩水溶液処理及びｐＨを上昇させる処理を施す方法が開示されている。
In Patent Document 2, as a method for producing a zeolite containing a metal such as Fe or Ni, after performing dealumination treatment on the zeolite with steaming and mineral acid, the obtained zeolite slurry is treated with an aqueous metal salt solution and A method for performing a treatment for increasing the pH is disclosed.
また、ＨＣを吸着させるためではなく、還元剤の存在下に窒素酸化物（ＮＯｘ）を分解させるための固体触媒の製造方法として、特許文献３には、金属を含有するゼオライトを、無機バインダとしてのアルミナと無機繊維とともにハニカム状に成形することによりハニカム構造体を製造する方法が開示されている。
Further, as a method for producing a solid catalyst for decomposing nitrogen oxide (NOx) in the presence of a reducing agent, not for adsorbing HC, Patent Document 3 discloses that a metal-containing zeolite is used as an inorganic binder. A method of manufacturing a honeycomb structure by forming into a honeycomb shape with alumina and inorganic fibers is disclosed.
ＨＣの吸着を目的とするハニカム構造体においては、ＨＣの吸着量及びＨＣの放出温度が重要である。すなわち、ＨＣを多量に吸着すること、及び、三元触媒が活性化する温度までＨＣを吸着することが重要であり、このような特性を有するハニカム構造体が求められている。
In a honeycomb structure intended for HC adsorption, the HC adsorption amount and the HC release temperature are important. That is, it is important to adsorb a large amount of HC and adsorb HC to a temperature at which the three-way catalyst is activated, and a honeycomb structure having such characteristics is required.
また、ハニカム構造体の使用時には、水分の吸着／脱離による体積の収縮／膨張に起因してハニカム構造体が破損することがあり、このようなハニカム構造体の破損を抑えることも求められている。
Further, when using a honeycomb structure, the honeycomb structure may be damaged due to volume shrinkage / expansion due to moisture adsorption / desorption, and it is also required to suppress such damage to the honeycomb structure. Yes.
本発明は、上記の問題を解決するためになされたものであり、ＨＣの吸着性能に優れ、かつ、使用時に破損が生じ難いハニカム構造体及びその製造方法を提供することを目的とする。
The present invention has been made to solve the above problems, and an object of the present invention is to provide a honeycomb structure excellent in HC adsorption performance and hardly damaged during use, and a method for manufacturing the same.
本発明のハニカム構造体は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体であって、上記ハニカム焼成体は、ＣｕＯとβ型ゼオライトと無機バインダとを含む押出成形体からなり、上記β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、３００以上であることを特徴とする。
A honeycomb structure of the present invention is a honeycomb structure including a honeycomb fired body in which a plurality of through holes are arranged in parallel in a longitudinal direction with partition walls interposed therebetween, and the honeycomb fired body includes CuO, β-type zeolite, and inorganic The β-type zeolite has an SiO 2 / Al 2 O 3 molar ratio of 300 or more.
本発明のハニカム構造体においては、ＳｉＯ２／Ａｌ２Ｏ３モル比が高いβ型ゼオライトにＣｕＯを共存させることにより、三元触媒が活性化する温度まで多量のＨＣを吸着することができる。したがって、本発明のハニカム構造体は、ＨＣの吸着性能に優れる。
In the honeycomb structure of the present invention, a large amount of HC can be adsorbed up to a temperature at which the three-way catalyst is activated by coexisting CuO with β-type zeolite having a high SiO 2 / Al 2 O 3 molar ratio. Therefore, the honeycomb structure of the present invention is excellent in HC adsorption performance.
また、β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比が高いということは、β型ゼオライト中のＡｌ量が少ないことを意味する。そのため、本発明のハニカム構造体においては、使用時に生じるハニカム構造体の破損を抑えることができる。
β型ゼオライトを構成するＡｌには水分が吸着しやすい。Ａｌに水分が吸着すると、β型ゼオライトの骨格構造に歪みが生じるため、β型ゼオライトの体積が変化する。本発明のハニカム構造体では、上記のとおりβ型ゼオライト中のＡｌ量が少ないため、β型ゼオライトに水分が吸着しにくくなり、水分の吸着／脱離による体積の収縮／膨張が抑制されると考えられる。 Further, the high SiO 2 / Al 2 O 3 molar ratio of β-type zeolite means that the amount of Al in the β-type zeolite is small. Therefore, in the honeycomb structure of the present invention, damage to the honeycomb structure that occurs during use can be suppressed.
Moisture is easily adsorbed on Al constituting the β-type zeolite. When moisture is adsorbed on Al, the skeleton structure of β-type zeolite is distorted, and the volume of β-type zeolite changes. In the honeycomb structure of the present invention, since the amount of Al in the β-type zeolite is small as described above, it is difficult for moisture to be adsorbed on the β-type zeolite, and volume shrinkage / expansion due to moisture adsorption / desorption is suppressed. Conceivable.
β型ゼオライトを構成するＡｌには水分が吸着しやすい。Ａｌに水分が吸着すると、β型ゼオライトの骨格構造に歪みが生じるため、β型ゼオライトの体積が変化する。本発明のハニカム構造体では、上記のとおりβ型ゼオライト中のＡｌ量が少ないため、β型ゼオライトに水分が吸着しにくくなり、水分の吸着／脱離による体積の収縮／膨張が抑制されると考えられる。 Further, the high SiO 2 / Al 2 O 3 molar ratio of β-type zeolite means that the amount of Al in the β-type zeolite is small. Therefore, in the honeycomb structure of the present invention, damage to the honeycomb structure that occurs during use can be suppressed.
Moisture is easily adsorbed on Al constituting the β-type zeolite. When moisture is adsorbed on Al, the skeleton structure of β-type zeolite is distorted, and the volume of β-type zeolite changes. In the honeycomb structure of the present invention, since the amount of Al in the β-type zeolite is small as described above, it is difficult for moisture to be adsorbed on the β-type zeolite, and volume shrinkage / expansion due to moisture adsorption / desorption is suppressed. Conceivable.
本発明のハニカム構造体は、上記β型ゼオライトに対してＣｕを１～７重量％含むことが望ましい。
ハニカム構造体に含まれるＣｕの量が上記範囲にある場合、ＨＣの吸着性能が向上する効果、及び、水分の吸着／脱離による体積の収縮／膨張が抑制される効果が充分に得られる。 The honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to the β-type zeolite.
When the amount of Cu contained in the honeycomb structure is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
ハニカム構造体に含まれるＣｕの量が上記範囲にある場合、ＨＣの吸着性能が向上する効果、及び、水分の吸着／脱離による体積の収縮／膨張が抑制される効果が充分に得られる。 The honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to the β-type zeolite.
When the amount of Cu contained in the honeycomb structure is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
本発明のハニカム構造体において、上記ハニカム焼成体は、無機繊維をさらに含むことが望ましい。この場合、ハニカム構造体の強度を向上させることができる。
In the honeycomb structured body of the present invention, it is desirable that the honeycomb fired body further includes inorganic fibers. In this case, the strength of the honeycomb structure can be improved.
本発明のハニカム構造体においては、上記隔壁の表面に三元触媒が担持されていることが望ましい。三元触媒によって、ＨＣを浄化することができる。
In the honeycomb structure of the present invention, it is desirable that a three-way catalyst is supported on the surface of the partition wall. HC can be purified by the three-way catalyst.
本発明のハニカム構造体の製造方法は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体の製造方法であって、ＣｕＯ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設された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焼成することにより、ハニカム焼成体を作製する焼成工程と、を含み、上記原料ペーストに含まれる上記β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、３００以上であることを特徴とする。
A method for manufacturing a honeycomb structure of the present invention is a method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and includes a CuO source, β-type zeolite, By forming a raw material paste containing an inorganic binder, a forming step for producing a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and by firing the honeycomb formed body, a honeycomb And a firing step for producing a fired body, wherein the β-type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more.
上記の方法によって、ＨＣの吸着性能に優れ、かつ、使用時に破損が生じ難いハニカム構造体を簡便に製造することができる。
By the above method, a honeycomb structure that is excellent in HC adsorption performance and hardly breaks during use can be easily produced.
本発明のハニカム構造体の製造方法において、上記原料ペーストに含まれる上記ＣｕＯ源の量は、Ｃｕ換算で、上記β型ゼオライトに対して１～７重量％であることが望ましい。
原料ペーストに含まれるＣｕＯ源の量が上記範囲にある場合、ＨＣの吸着性能を向上させる効果、及び、水分の吸着／脱離による体積の収縮／膨張を抑制する効果が充分に得られる。 In the method for manufacturing a honeycomb structure of the present invention, the amount of the CuO source contained in the raw material paste is preferably 1 to 7% by weight with respect to the β-type zeolite in terms of Cu.
When the amount of the CuO source contained in the raw material paste is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
原料ペーストに含まれるＣｕＯ源の量が上記範囲にある場合、ＨＣの吸着性能を向上させる効果、及び、水分の吸着／脱離による体積の収縮／膨張を抑制する効果が充分に得られる。 In the method for manufacturing a honeycomb structure of the present invention, the amount of the CuO source contained in the raw material paste is preferably 1 to 7% by weight with respect to the β-type zeolite in terms of Cu.
When the amount of the CuO source contained in the raw material paste is in the above range, the effect of improving the HC adsorption performance and the effect of suppressing the volume shrinkage / expansion due to moisture adsorption / desorption can be sufficiently obtained.
本発明のハニカム構造体の製造方法において、上記原料ペーストは、無機繊維をさらに含むことが望ましい。この場合、得られるハニカム構造体の強度を向上させることができる。
In the method for manufacturing a honeycomb structured body of the present invention, the raw material paste preferably further contains inorganic fibers. In this case, the strength of the obtained honeycomb structure can be improved.
本発明のハニカム構造体の製造方法は、上記隔壁の表面に三元触媒を担持させる担持工程をさらに含むことが望ましい。三元触媒によって、ＨＣを浄化することができる。
The method for manufacturing a honeycomb structure of the present invention preferably further includes a supporting step of supporting a three-way catalyst on the surface of the partition wall. HC can be purified by the three-way catalyst.
（発明の詳細な説明）
［ハニカム構造体］
まず、本発明のハニカム構造体について説明する。 (Detailed description of the invention)
[Honeycomb structure]
First, the honeycomb structure of the present invention will be described.
［ハニカム構造体］
まず、本発明のハニカム構造体について説明する。 (Detailed description of the invention)
[Honeycomb structure]
First, the honeycomb structure of the present invention will be described.
本発明のハニカム構造体は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えている。
The honeycomb structure of the present invention includes a honeycomb fired body in which a plurality of through holes are arranged in parallel in the longitudinal direction with partition walls therebetween.
本発明のハニカム構造体において、ハニカム焼成体は、ＣｕＯとβ型ゼオライトと無機バインダとを含む押出成形体からなる。後述するように、ハニカム焼成体は、ＣｕＯ源とβ型ゼオライトと無機バインダとを含む原料ペーストを押出成形した後、焼成することにより作製されている。
In the honeycomb structure of the present invention, the honeycomb fired body is formed of an extrusion-molded body containing CuO, β-type zeolite, and an inorganic binder. As will be described later, the honeycomb fired body is manufactured by extruding and firing a raw material paste containing a CuO source, β-type zeolite, and an inorganic binder.
本発明のハニカム構造体は、単一のハニカム焼成体を備えていてもよいし、接着層を介して接着された複数個のハニカム焼成体を備えていてもよい。
The honeycomb structure of the present invention may include a single honeycomb fired body, or may include a plurality of honeycomb fired bodies bonded through an adhesive layer.
本発明のハニカム構造体において、ハニカム焼成体の外周面には、外周コート層が形成されていることが望ましい。
In the honeycomb structure of the present invention, it is desirable that an outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body.
図１は、本発明のハニカム構造体の一例を模式的に示す斜視図である。
図１に示すハニカム構造体１０は、複数の貫通孔１１ａが隔壁１１ｂを隔てて長手方向に並設された単一のハニカム焼成体１１を備えている。ハニカム焼成体１１は、ＣｕＯとβ型ゼオライトと無機バインダとを含む押出成形体からなる。さらに、ハニカム焼成体１１の外周面には、外周コート層１２が形成されている。 FIG. 1 is a perspective view schematically showing an example of the honeycomb structure of the present invention.
Ahoneycomb structure 10 shown in FIG. 1 includes a single honeycomb fired body 11 in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b interposed therebetween. The honeycomb fired body 11 is made of an extrusion-molded body containing CuO, β-type zeolite, and an inorganic binder. Further, an outer peripheral coat layer 12 is formed on the outer peripheral surface of the honeycomb fired body 11.
図１に示すハニカム構造体１０は、複数の貫通孔１１ａが隔壁１１ｂを隔てて長手方向に並設された単一のハニカム焼成体１１を備えている。ハニカム焼成体１１は、ＣｕＯとβ型ゼオライトと無機バインダとを含む押出成形体からなる。さらに、ハニカム焼成体１１の外周面には、外周コート層１２が形成されている。 FIG. 1 is a perspective view schematically showing an example of the honeycomb structure of the present invention.
A
図２は、本発明のハニカム構造体の別の一例を模式的に示す斜視図である。
図３は、図２に示すハニカム構造体を構成するハニカム焼成体の一例を模式的に示す斜視図である。 FIG. 2 is a perspective view schematically showing another example of the honeycomb structure of the present invention.
FIG. 3 is a perspective view schematically showing an example of a honeycomb fired body constituting the honeycomb structure shown in FIG.
図３は、図２に示すハニカム構造体を構成するハニカム焼成体の一例を模式的に示す斜視図である。 FIG. 2 is a perspective view schematically showing another example of the honeycomb structure of the present invention.
FIG. 3 is a perspective view schematically showing an example of a honeycomb fired body constituting the honeycomb structure shown in FIG.
図２に示すハニカム構造体２０は、複数の貫通孔２１ａが隔壁２１ｂを隔てて長手方向に並設されたハニカム焼成体２１（図３参照）が接着層２３を介して複数個接着されている以外は、図１に示すハニカム構造体１０と同一の構成を有する。さらに、ハニカム焼成体２１の外周面には、外周コート層２２が形成されている。
In the honeycomb structure 20 shown in FIG. 2, a plurality of honeycomb fired bodies 21 (see FIG. 3) in which a plurality of through holes 21 a are arranged in parallel in the longitudinal direction with partition walls 21 b interposed therebetween are bonded via an adhesive layer 23. Except for this, it has the same configuration as the honeycomb structure 10 shown in FIG. Furthermore, an outer peripheral coat layer 22 is formed on the outer peripheral surface of the honeycomb fired body 21.
なお、ハニカム構造体１０及び２０においては、それぞれ外周コート層１２及び２２が形成されていなくてもよい。
In the honeycomb structures 10 and 20, the outer peripheral coat layers 12 and 22 may not be formed, respectively.
本発明のハニカム構造体においては、β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比が３００以上であることを特徴とする。上記ＳｉＯ２／Ａｌ２Ｏ３モル比は、３５０以上であることが望ましく、４００以上であることがより望ましい。また、上記ＳｉＯ２／Ａｌ２Ｏ３モル比は、１０００以下であることが望ましく、８００以下であることがより望ましい。
β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、蛍光Ｘ線分析（ＸＲＦ）により測定することができる。また、β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は焼成前後で変化しないため、原料ペーストに含まれるβ型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比を、本発明のハニカム構造体中のβ型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比とすることもできる。 In the honeycomb structure of the present invention, the β-type zeolite has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. The SiO 2 / Al 2 O 3 molar ratio is desirably 350 or more, and more desirably 400 or more. Further, the SiO 2 / Al 2 O 3 molar ratio is desirably 1000 or less, and more desirably 800 or less.
The SiO 2 / Al 2 O 3 molar ratio of β-type zeolite can be measured by fluorescent X-ray analysis (XRF). Moreover, beta type for SiO 2 / Al 2 O 3 molar ratio of the zeolite is not changed before and after sintering, the SiO 2 / Al 2 O 3 molar ratio of beta-type zeolite contained in the raw material paste, a honeycomb structure of the present invention The β-type zeolite can also have a SiO 2 / Al 2 O 3 molar ratio.
β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、蛍光Ｘ線分析（ＸＲＦ）により測定することができる。また、β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は焼成前後で変化しないため、原料ペーストに含まれるβ型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比を、本発明のハニカム構造体中のβ型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比とすることもできる。 In the honeycomb structure of the present invention, the β-type zeolite has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. The SiO 2 / Al 2 O 3 molar ratio is desirably 350 or more, and more desirably 400 or more. Further, the SiO 2 / Al 2 O 3 molar ratio is desirably 1000 or less, and more desirably 800 or less.
The SiO 2 / Al 2 O 3 molar ratio of β-type zeolite can be measured by fluorescent X-ray analysis (XRF). Moreover, beta type for SiO 2 / Al 2 O 3 molar ratio of the zeolite is not changed before and after sintering, the SiO 2 / Al 2 O 3 molar ratio of beta-type zeolite contained in the raw material paste, a honeycomb structure of the present invention The β-type zeolite can also have a SiO 2 / Al 2 O 3 molar ratio.
本発明のハニカム構造体において、原料ペーストに含まれるβ型ゼオライトの平均粒子径は、０．１～１０μｍであることが望ましく、０．５～５μｍであることがより望ましい。
β型ゼオライトの平均粒子径は、レーザー回折・散乱式粒度分布測定器（セイシン企業製：レーザーマイクロンサイザー ＬＭＳ－３０）を用いて測定した一次粒子の平均粒子径である。 In the honeycomb structure of the present invention, the average particle size of β-type zeolite contained in the raw material paste is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.
The average particle size of β-type zeolite is the average particle size of primary particles measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Seishin Enterprises: Laser Micronizer LMS-30).
β型ゼオライトの平均粒子径は、レーザー回折・散乱式粒度分布測定器（セイシン企業製：レーザーマイクロンサイザー ＬＭＳ－３０）を用いて測定した一次粒子の平均粒子径である。 In the honeycomb structure of the present invention, the average particle size of β-type zeolite contained in the raw material paste is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.
The average particle size of β-type zeolite is the average particle size of primary particles measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Seishin Enterprises: Laser Micronizer LMS-30).
本発明のハニカム構造体において、原料ペーストに含まれるβ型ゼオライトの量は、２５～６０重量％であることが望ましく、３０～５０重量％であることがより望ましい。
In the honeycomb structure of the present invention, the amount of β-type zeolite contained in the raw material paste is preferably 25 to 60% by weight, more preferably 30 to 50% by weight.
本発明のハニカム構造体は、β型ゼオライトに対してＣｕを１～７重量％含むことが望ましく、２～４重量％含むことがより望ましい。
ハニカム構造中のＣｕの含有量は、蛍光Ｘ線分析（ＸＲＦ）により測定することができる。また、ハニカム構造中のＣｕの含有量は、原料ペーストに含まれるＣｕＯ源の量から求めることもできる。 The honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to β-type zeolite, and more preferably contains 2 to 4% by weight.
The Cu content in the honeycomb structure can be measured by fluorescent X-ray analysis (XRF). Further, the Cu content in the honeycomb structure can also be determined from the amount of CuO source contained in the raw material paste.
ハニカム構造中のＣｕの含有量は、蛍光Ｘ線分析（ＸＲＦ）により測定することができる。また、ハニカム構造中のＣｕの含有量は、原料ペーストに含まれるＣｕＯ源の量から求めることもできる。 The honeycomb structure of the present invention preferably contains 1 to 7% by weight of Cu with respect to β-type zeolite, and more preferably contains 2 to 4% by weight.
The Cu content in the honeycomb structure can be measured by fluorescent X-ray analysis (XRF). Further, the Cu content in the honeycomb structure can also be determined from the amount of CuO source contained in the raw material paste.
本発明のハニカム構造体において、β型ゼオライトはＣｕイオンによりイオン交換されていないことが望ましく、ＣｕＯがβ型ゼオライトの表面に担持されていることが望ましい。
なお、β型ゼオライトに担持されているＣｕの状態は、ハニカム構造体に対してＨ２－ＴＰＲ測定を行うことにより得られるピークから分析することができる。 In the honeycomb structure of the present invention, the β-type zeolite is preferably not ion-exchanged with Cu ions, and CuO is preferably supported on the surface of the β-type zeolite.
Note that the state of Cu supported on the β-type zeolite can be analyzed from a peak obtained by performing H 2 -TPR measurement on the honeycomb structure.
なお、β型ゼオライトに担持されているＣｕの状態は、ハニカム構造体に対してＨ２－ＴＰＲ測定を行うことにより得られるピークから分析することができる。 In the honeycomb structure of the present invention, the β-type zeolite is preferably not ion-exchanged with Cu ions, and CuO is preferably supported on the surface of the β-type zeolite.
Note that the state of Cu supported on the β-type zeolite can be analyzed from a peak obtained by performing H 2 -TPR measurement on the honeycomb structure.
本発明のハニカム構造体において、原料ペーストに含まれる無機バインダとしては、特に限定されないが、アルミナゾル、シリカゾル、チタニアゾル、水ガラス、セピオライト、アタパルジャイト、ベーマイト等に含まれる固形分が挙げられ、二種以上併用してもよい。
In the honeycomb structure of the present invention, the inorganic binder contained in the raw material paste is not particularly limited, and examples thereof include solids contained in alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, boehmite, etc. You may use together.
本発明のハニカム構造体において、原料ペーストに含まれる無機バインダの量は、５～２０重量％であることが望ましく、７～１５重量％であることがより望ましい。
In the honeycomb structure of the present invention, the amount of the inorganic binder contained in the raw material paste is desirably 5 to 20% by weight, and more desirably 7 to 15% by weight.
本発明のハニカム構造体において、ハニカム焼成体は、無機繊維をさらに含むことが望ましい。すなわち、上記原料ペーストは、無機繊維をさらに含むことが望ましい。
In the honeycomb structure of the present invention, it is desirable that the honeycomb fired body further includes inorganic fibers. That is, the raw material paste preferably further includes inorganic fibers.
無機繊維を構成する材料としては、特に限定されないが、アルミナ、シリカ、炭化ケイ素、シリカアルミナ、ガラス、チタン酸カリウム、ホウ酸アルミニウム等が挙げられ、二種以上併用してもよい。
Although it does not specifically limit as a material which comprises inorganic fiber, Alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate, etc. are mentioned, You may use 2 or more types together.
無機繊維のアスペクト比は、２～３００であることが望ましく、５～２００であることがより望ましく、１０～１００であることがさらに望ましい。
The aspect ratio of the inorganic fiber is preferably 2 to 300, more preferably 5 to 200, and still more preferably 10 to 100.
本発明のハニカム構造体において、原料ペーストに含まれる無機繊維の量は、２～１５重量％であることが望ましく、５～１０重量％であることがより望ましい。
In the honeycomb structure of the present invention, the amount of inorganic fibers contained in the raw material paste is preferably 2 to 15% by weight, and more preferably 5 to 10% by weight.
本発明のハニカム構造体の形状としては、円柱状に限定されず、角柱状、楕円柱状、長円柱状、丸面取りされている角柱状（例えば、丸面取りされている三角柱状）等が挙げられる。
The shape of the honeycomb structure of the present invention is not limited to a cylindrical shape, and examples thereof include a prismatic shape, an elliptical cylindrical shape, a long cylindrical shape, and a rounded chamfered prismatic shape (for example, a rounded chamfered triangular prism shape). .
本発明のハニカム構造体において、ハニカム焼成体の貫通孔の形状としては、四角柱状に限定されず、三角柱状、六角柱状等が挙げられる。
In the honeycomb structure of the present invention, the shape of the through hole of the honeycomb fired body is not limited to a quadrangular prism shape, and examples thereof include a triangular prism shape and a hexagonal prism shape.
本発明のハニカム構造体において、ハニカム焼成体の長手方向に垂直な断面の貫通孔の密度は、３１～１５５個／ｃｍ２であることが望ましい。
In the honeycomb structure of the present invention, the density of the through holes in the cross section perpendicular to the longitudinal direction of the honeycomb fired body is preferably 31 to 155 holes / cm 2 .
本発明のハニカム構造体において、ハニカム焼成体の隔壁の厚さは、０．１０～０．５０ｍｍであることが望ましく、０．２０～０．４０ｍｍであることがより望ましい。
In the honeycomb structure of the present invention, the thickness of the partition walls of the honeycomb fired body is preferably 0.10 to 0.50 mm, and more preferably 0.20 to 0.40 mm.
本発明のハニカム構造体において、ハニカム焼成体の外周面に外周コート層が形成されている場合、外周コート層の厚さは、０．１～２．０ｍｍであることが望ましい。
In the honeycomb structure of the present invention, when the outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body, the thickness of the outer peripheral coat layer is preferably 0.1 to 2.0 mm.
本発明のハニカム構造体においては、上記隔壁の表面に三元触媒が担持されていることが望ましい。
三元触媒とは、主に炭化水素（ＨＣ）、一酸化炭素（ＣＯ）及び窒素酸化物（ＮＯｘ）を浄化する触媒をいう。三元触媒としては、例えば、白金、パラジウム、ロジウム等の貴金属が挙げられる。また、これらの貴金属をアルミナ等の耐熱性無機酸化物からなる担体に担持させたものを三元触媒として用いることもできる。 In the honeycomb structure of the present invention, it is desirable that a three-way catalyst is supported on the surface of the partition wall.
A three-way catalyst refers to a catalyst that mainly purifies hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). Examples of the three-way catalyst include noble metals such as platinum, palladium, and rhodium. Moreover, what carried | supported these noble metals on the support | carrier which consists of heat resistant inorganic oxides, such as an alumina, can also be used as a three-way catalyst.
三元触媒とは、主に炭化水素（ＨＣ）、一酸化炭素（ＣＯ）及び窒素酸化物（ＮＯｘ）を浄化する触媒をいう。三元触媒としては、例えば、白金、パラジウム、ロジウム等の貴金属が挙げられる。また、これらの貴金属をアルミナ等の耐熱性無機酸化物からなる担体に担持させたものを三元触媒として用いることもできる。 In the honeycomb structure of the present invention, it is desirable that a three-way catalyst is supported on the surface of the partition wall.
A three-way catalyst refers to a catalyst that mainly purifies hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). Examples of the three-way catalyst include noble metals such as platinum, palladium, and rhodium. Moreover, what carried | supported these noble metals on the support | carrier which consists of heat resistant inorganic oxides, such as an alumina, can also be used as a three-way catalyst.
本発明のハニカム構造体において、三元触媒の担持量は、０．１～１５ｇ／Ｌであることが望ましく、１～１０ｇ／Ｌであることがより望ましい。
本明細書において、三元触媒の担持量とは、ハニカム構造体の見掛けの体積当たりの三元触媒の重量をいう。なお、ハニカム構造体の見掛けの体積は、空隙の体積を含む体積であり、外周コート層及び／又は接着層の体積を含むこととする。 In the honeycomb structure of the present invention, the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
In this specification, the supported amount of the three-way catalyst refers to the weight of the three-way catalyst per apparent volume of the honeycomb structure. The apparent volume of the honeycomb structure is a volume including the void volume, and includes the volume of the outer peripheral coat layer and / or the adhesive layer.
本明細書において、三元触媒の担持量とは、ハニカム構造体の見掛けの体積当たりの三元触媒の重量をいう。なお、ハニカム構造体の見掛けの体積は、空隙の体積を含む体積であり、外周コート層及び／又は接着層の体積を含むこととする。 In the honeycomb structure of the present invention, the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
In this specification, the supported amount of the three-way catalyst refers to the weight of the three-way catalyst per apparent volume of the honeycomb structure. The apparent volume of the honeycomb structure is a volume including the void volume, and includes the volume of the outer peripheral coat layer and / or the adhesive layer.
［ハニカム構造体の製造方法］
次に、本発明のハニカム構造体の製造方法について説明する。
本発明のハニカム構造体の製造方法は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体の製造方法であって、ＣｕＯ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設された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焼成することにより、ハニカム焼成体を作製する焼成工程と、を含む。 [Manufacturing method of honeycomb structure]
Next, the manufacturing method of the honeycomb structure of the present invention will be described.
A method for manufacturing a honeycomb structure of the present invention is a method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and includes a CuO source, β-type zeolite, By forming a raw material paste containing an inorganic binder, a forming step for producing a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and by firing the honeycomb formed body, a honeycomb And a firing step for producing a fired body.
次に、本発明のハニカム構造体の製造方法について説明する。
本発明のハニカム構造体の製造方法は、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体の製造方法であって、ＣｕＯ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設された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焼成することにより、ハニカム焼成体を作製する焼成工程と、を含む。 [Manufacturing method of honeycomb structure]
Next, the manufacturing method of the honeycomb structure of the present invention will be described.
A method for manufacturing a honeycomb structure of the present invention is a method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and includes a CuO source, β-type zeolite, By forming a raw material paste containing an inorganic binder, a forming step for producing a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and by firing the honeycomb formed body, a honeycomb And a firing step for producing a fired body.
（成形工程）
本発明のハニカム構造体の製造方法において、成形工程では、ＣｕＯ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム成形体を作製する。具体的には、ＣｕＯ源とβ型ゼオライトと無機バインダとを含み、必要に応じて、無機繊維等をさらに含む原料ペーストを用いて押出成形することにより、ハニカム成形体を作製する。 (Molding process)
In the method for manufacturing a honeycomb structure of the present invention, in the forming step, a raw material paste containing a CuO source, β-type zeolite, and an inorganic binder is formed, so that a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween. A honeycomb formed body is produced. Specifically, a honeycomb formed body is manufactured by extrusion molding using a raw material paste containing a CuO source, β-type zeolite, and an inorganic binder, and further containing inorganic fibers and the like as necessary.
本発明のハニカム構造体の製造方法において、成形工程では、ＣｕＯ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム成形体を作製する。具体的には、ＣｕＯ源とβ型ゼオライトと無機バインダとを含み、必要に応じて、無機繊維等をさらに含む原料ペーストを用いて押出成形することにより、ハニカム成形体を作製する。 (Molding process)
In the method for manufacturing a honeycomb structure of the present invention, in the forming step, a raw material paste containing a CuO source, β-type zeolite, and an inorganic binder is formed, so that a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween. A honeycomb formed body is produced. Specifically, a honeycomb formed body is manufactured by extrusion molding using a raw material paste containing a CuO source, β-type zeolite, and an inorganic binder, and further containing inorganic fibers and the like as necessary.
本発明のハニカム構造体の製造方法においては、原料ペーストに含まれるβ型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比が３００以上であることを特徴とする。β型ゼオライトの構造については既に説明したとおりであるため、その詳細な説明は省略する。
また、原料ペーストに含まれる無機バインダ、無機繊維等についても既に説明したとおりであるため、その詳細な説明は省略する。 In the method for manufacturing a honeycomb structure of the present invention, the β 2 -type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. Since the structure of β-type zeolite has already been described, its detailed description is omitted.
Moreover, since it is as having already demonstrated the inorganic binder, inorganic fiber, etc. which are contained in a raw material paste, the detailed description is abbreviate | omitted.
また、原料ペーストに含まれる無機バインダ、無機繊維等についても既に説明したとおりであるため、その詳細な説明は省略する。 In the method for manufacturing a honeycomb structure of the present invention, the β 2 -type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. Since the structure of β-type zeolite has already been described, its detailed description is omitted.
Moreover, since it is as having already demonstrated the inorganic binder, inorganic fiber, etc. which are contained in a raw material paste, the detailed description is abbreviate | omitted.
ＣｕＯ源としては、酸化銅、硝酸銅、酢酸銅、硫酸銅等が挙げられる。これらの中では、酸化銅が望ましい。
Examples of the CuO source include copper oxide, copper nitrate, copper acetate, and copper sulfate. Among these, copper oxide is desirable.
本発明のハニカム構造体の製造方法において、原料ペーストに含まれるＣｕＯ源の量は、Ｃｕ換算で、β型ゼオライトに対して１～７重量％であることが望ましく、２～４重量％であることがより望ましい。
In the method for manufacturing a honeycomb structure of the present invention, the amount of the CuO source contained in the raw material paste is preferably 1 to 7% by weight with respect to β-type zeolite in terms of Cu, and is preferably 2 to 4% by weight. It is more desirable.
上記原料ペーストは、必要に応じて、有機バインダ、分散媒、成形助剤等をさらに含んでいてもよい。
The raw material paste may further contain an organic binder, a dispersion medium, a molding aid and the like as necessary.
有機バインダとしては、特に限定されないが、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、フェノール樹脂、エポキシ樹脂等が挙げられ、二種以上併用してもよい。
Although it does not specifically limit as an organic binder, Methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol, a phenol resin, an epoxy resin etc. are mentioned, You may use 2 or more types together.
分散媒としては、特に限定されないが、水、ベンゼン等の有機溶媒、メタノール等のアルコール等が挙げられ、二種以上併用してもよい。
Although it does not specifically limit as a dispersion medium, Alcohol, such as water, organic solvents, such as benzene, methanol, etc. are mentioned, You may use 2 or more types together.
成形助剤としては、特に限定されないが、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、二種以上併用してもよい。
Although it does not specifically limit as a shaping | molding adjuvant, Ethylene glycol, dextrin, a fatty acid, fatty acid soap, a polyalcohol etc. are mentioned, You may use together 2 or more types.
原料ペーストを調製する際には、混合混練することが望ましく、ミキサー、アトライタ等を用いて混合してもよく、ニーダー等を用いて混練してもよい。
When preparing the raw material paste, it is desirable to mix and knead, and it may be mixed using a mixer, an attritor or the like, or may be kneaded using a kneader or the like.
次に、マイクロ波乾燥機、熱風乾燥機、誘電乾燥機、減圧乾燥機、真空乾燥機、凍結乾燥機等の乾燥機を用いて、ハニカム成形体を乾燥してハニカム乾燥体を作製することが望ましい。
Next, using a dryer such as a microwave dryer, hot air dryer, dielectric dryer, vacuum dryer, vacuum dryer, freeze dryer, etc., the honeycomb formed body can be dried to produce a honeycomb dried body. desirable.
本明細書においては、焼成工程を行う前のハニカム成形体及びハニカム乾燥体をまとめてハニカム成形体とも呼ぶ。
In the present specification, the honeycomb formed body and the honeycomb dried body before the firing step are collectively referred to as a honeycomb formed body.
（焼成工程）
本発明のハニカム構造体の製造方法において、焼成工程では、ハニカム成形体を焼成することにより、ハニカム焼成体を作製する。なお、この工程は、ハニカム成形体の脱脂及び焼成が行われるため、「脱脂・焼成工程」ということもできるが、便宜上「焼成工程」という。 (Baking process)
In the method for manufacturing a honeycomb structure of the present invention, in the firing step, the honeycomb fired body is fired to produce a honeycomb fired body. In addition, since this process performs degreasing and firing of the honeycomb formed body, it can also be referred to as a “degreasing / firing process”, but it is referred to as a “firing process” for convenience.
本発明のハニカム構造体の製造方法において、焼成工程では、ハニカム成形体を焼成することにより、ハニカム焼成体を作製する。なお、この工程は、ハニカム成形体の脱脂及び焼成が行われるため、「脱脂・焼成工程」ということもできるが、便宜上「焼成工程」という。 (Baking process)
In the method for manufacturing a honeycomb structure of the present invention, in the firing step, the honeycomb fired body is fired to produce a honeycomb fired body. In addition, since this process performs degreasing and firing of the honeycomb formed body, it can also be referred to as a “degreasing / firing process”, but it is referred to as a “firing process” for convenience.
焼成工程の温度は、６００～１０００℃であることが望ましく、６００～８００℃であることがより望ましい。また、焼成工程の時間は、１～１０時間であることが望ましく、１．５～５時間であることがより望ましい。焼成工程の雰囲気は特に限定されないが、酸素濃度が１～１０体積％であることが望ましい。
The temperature of the firing step is desirably 600 to 1000 ° C., and more desirably 600 to 800 ° C. The firing process time is preferably 1 to 10 hours, and more preferably 1.5 to 5 hours. The atmosphere of the firing step is not particularly limited, but it is desirable that the oxygen concentration is 1 to 10% by volume.
以上の工程により、本発明のハニカム構造体を製造することができる。
Through the above steps, the honeycomb structure of the present invention can be manufactured.
（担持工程）
本発明のハニカム構造体の製造方法は、上記隔壁の表面に三元触媒を担持させる担持工程をさらに含むことが望ましい。
隔壁の表面に三元触媒を担持する方法としては、例えば、三元触媒を含むスラリーにハニカム焼成体又はハニカム構造体を浸漬した後、引き上げて加熱する方法等が挙げられる。
ハニカム構造体が外周コート層を備える場合、外周コート層を形成する前のハニカム焼成体の隔壁の表面に三元触媒を担持してもよいし、外周コート層を形成した後のハニカム焼成体又はハニカム構造体の隔壁の表面に三元触媒を担持してもよい。また、ハニカム構造体が接着層を備える場合、接着層を形成する前のハニカム焼成体の隔壁の表面に三元触媒を担持してもよいし、接着層を形成した後のハニカム焼成体又はハニカム構造体の隔壁の表面に三元触媒を担持してもよい。 (Supporting process)
The method for manufacturing a honeycomb structure of the present invention preferably further includes a supporting step of supporting a three-way catalyst on the surface of the partition wall.
Examples of the method for supporting the three-way catalyst on the surface of the partition wall include a method in which the honeycomb fired body or the honeycomb structure is immersed in a slurry containing the three-way catalyst, and then heated up and heated.
When the honeycomb structure includes an outer peripheral coat layer, a three-way catalyst may be supported on the surface of the partition wall of the honeycomb fired body before forming the outer peripheral coat layer, or the honeycomb fired body after forming the outer peripheral coat layer or A three-way catalyst may be supported on the surface of the partition walls of the honeycomb structure. When the honeycomb structure includes an adhesive layer, the three-way catalyst may be supported on the surface of the partition walls of the honeycomb fired body before forming the adhesive layer, or the honeycomb fired body or honeycomb after forming the adhesive layer A three-way catalyst may be supported on the surface of the partition walls of the structure.
本発明のハニカム構造体の製造方法は、上記隔壁の表面に三元触媒を担持させる担持工程をさらに含むことが望ましい。
隔壁の表面に三元触媒を担持する方法としては、例えば、三元触媒を含むスラリーにハニカム焼成体又はハニカム構造体を浸漬した後、引き上げて加熱する方法等が挙げられる。
ハニカム構造体が外周コート層を備える場合、外周コート層を形成する前のハニカム焼成体の隔壁の表面に三元触媒を担持してもよいし、外周コート層を形成した後のハニカム焼成体又はハニカム構造体の隔壁の表面に三元触媒を担持してもよい。また、ハニカム構造体が接着層を備える場合、接着層を形成する前のハニカム焼成体の隔壁の表面に三元触媒を担持してもよいし、接着層を形成した後のハニカム焼成体又はハニカム構造体の隔壁の表面に三元触媒を担持してもよい。 (Supporting process)
The method for manufacturing a honeycomb structure of the present invention preferably further includes a supporting step of supporting a three-way catalyst on the surface of the partition wall.
Examples of the method for supporting the three-way catalyst on the surface of the partition wall include a method in which the honeycomb fired body or the honeycomb structure is immersed in a slurry containing the three-way catalyst, and then heated up and heated.
When the honeycomb structure includes an outer peripheral coat layer, a three-way catalyst may be supported on the surface of the partition wall of the honeycomb fired body before forming the outer peripheral coat layer, or the honeycomb fired body after forming the outer peripheral coat layer or A three-way catalyst may be supported on the surface of the partition walls of the honeycomb structure. When the honeycomb structure includes an adhesive layer, the three-way catalyst may be supported on the surface of the partition walls of the honeycomb fired body before forming the adhesive layer, or the honeycomb fired body or honeycomb after forming the adhesive layer A three-way catalyst may be supported on the surface of the partition walls of the structure.
本発明のハニカム構造体の製造方法において、担持工程では、三元触媒の担持量が０．１～１５ｇ／Ｌであることが望ましく、１～１０ｇ／Ｌであることがより望ましい。
In the method for manufacturing a honeycomb structured body of the present invention, in the supporting step, the supported amount of the three-way catalyst is preferably 0.1 to 15 g / L, and more preferably 1 to 10 g / L.
（その他の工程）
本発明のハニカム構造体の製造方法において、ハニカム焼成体の外周面に外周コート層を形成する場合、外周コート層は、ハニカム焼成体の両端面を除く外周面に外周コート層用ペーストを塗布した後、乾燥固化することにより形成することができる。 (Other processes)
In the method for manufacturing a honeycomb structured body of the present invention, when the outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body, the outer peripheral coat layer is coated with the outer peripheral coat layer paste on the outer peripheral surface excluding both end faces. Thereafter, it can be formed by drying and solidifying.
本発明のハニカム構造体の製造方法において、ハニカム焼成体の外周面に外周コート層を形成する場合、外周コート層は、ハニカム焼成体の両端面を除く外周面に外周コート層用ペーストを塗布した後、乾燥固化することにより形成することができる。 (Other processes)
In the method for manufacturing a honeycomb structured body of the present invention, when the outer peripheral coat layer is formed on the outer peripheral surface of the honeycomb fired body, the outer peripheral coat layer is coated with the outer peripheral coat layer paste on the outer peripheral surface excluding both end faces. Thereafter, it can be formed by drying and solidifying.
本発明のハニカム構造体の製造方法において、複数個のハニカム焼成体が接着層を介して接着されてなるハニカム構造体は、複数個のハニカム焼成体の両端面を除く外周面に接着層用ペーストを塗布して、接着させた後、乾燥固化することにより作製することができる。
In the method for manufacturing a honeycomb structured body according to the present invention, the honeycomb structured body in which a plurality of honeycomb fired bodies are bonded via an adhesive layer has an adhesive layer paste on the outer peripheral surface excluding both end faces of the plurality of honeycomb fired bodies. After applying and adhering, it can be produced by drying and solidifying.
（実施例）
以下、本発明をより具体的に開示した実施例を示す。なお、本発明は、以下の実施例のみに限定されるものではない。 (Example)
Examples in which the present invention is disclosed more specifically are shown below. In addition, this invention is not limited only to a following example.
以下、本発明をより具体的に開示した実施例を示す。なお、本発明は、以下の実施例のみに限定されるものではない。 (Example)
Examples in which the present invention is disclosed more specifically are shown below. In addition, this invention is not limited only to a following example.
［評価用サンプルの作製］
（実施例１）
ＣｕＯ源としてＣｕＯ（平均粒子径：２μｍ）を１重量部、β型ゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比：４４０、平均粒子径：２μｍ）を４０重量部、無機バインダとしてベーマイトを１０．５重量部、平均繊維径が３μｍ、平均繊維長が１２０μｍのアルミナ繊維を７．５重量部、有機バインダとしてメチルセルロースを５重量部、成形助剤としてオレイン酸を５重量部及びイオン交換水を３１重量部混合混練して、原料ペーストを作製した。 [Preparation of sample for evaluation]
Example 1
1 part by weight of CuO (average particle diameter: 2 μm) as a CuO source, 40 parts by weight of β-type zeolite (SiO 2 / Al 2 O 3 molar ratio: 440, average particle diameter: 2 μm), and boehmite as an inorganic binder 7.5 parts by weight of alumina fibers having an average fiber diameter of 3 μm and an average fiber length of 120 μm, 5 parts by weight of methyl cellulose as an organic binder, 5 parts by weight of oleic acid as a molding aid, and 31 parts of ion-exchanged water Part by weight was mixed and kneaded to prepare a raw material paste.
（実施例１）
ＣｕＯ源としてＣｕＯ（平均粒子径：２μｍ）を１重量部、β型ゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比：４４０、平均粒子径：２μｍ）を４０重量部、無機バインダとしてベーマイトを１０．５重量部、平均繊維径が３μｍ、平均繊維長が１２０μｍのアルミナ繊維を７．５重量部、有機バインダとしてメチルセルロースを５重量部、成形助剤としてオレイン酸を５重量部及びイオン交換水を３１重量部混合混練して、原料ペーストを作製した。 [Preparation of sample for evaluation]
Example 1
1 part by weight of CuO (average particle diameter: 2 μm) as a CuO source, 40 parts by weight of β-type zeolite (SiO 2 / Al 2 O 3 molar ratio: 440, average particle diameter: 2 μm), and boehmite as an inorganic binder 7.5 parts by weight of alumina fibers having an average fiber diameter of 3 μm and an average fiber length of 120 μm, 5 parts by weight of methyl cellulose as an organic binder, 5 parts by weight of oleic acid as a molding aid, and 31 parts of ion-exchanged water Part by weight was mixed and kneaded to prepare a raw material paste.
押出成形機を用いて、原料ペーストを押出成形して、正四角柱状のハニカム成形体を作製した。そして、減圧マイクロ波乾燥機を用いて、ハニカム成形体を出力４０ｋＷ、減圧６．７ｋＰａで１７分間乾燥させた後、７００℃で３時間４０分脱脂・焼成することにより、ハニカム焼成体を作製した。ハニカム焼成体は、一辺が３３ｍｍ、長さが４３ｍｍの正四角柱状であり、貫通孔の密度が６２個／ｃｍ２、隔壁の厚さが０．３６ｍｍであった。
The raw material paste was extruded using an extruder, and a regular quadrangular prism-shaped honeycomb formed body was produced. The honeycomb molded body was dried for 17 minutes at an output of 40 kW and a reduced pressure of 6.7 kPa using a vacuum microwave dryer, and then degreased and fired at 700 ° C. for 3 hours and 40 minutes to produce a honeycomb fired body. . The honeycomb fired body had a regular square pillar shape with a side of 33 mm and a length of 43 mm, a density of through holes of 62 holes / cm 2 , and a partition wall thickness of 0.36 mm.
（比較例１）
比較例１では、以下のように、ＣｕＯ源を含まない原料ペーストを用いてハニカム焼成体を作製した。 (Comparative Example 1)
In Comparative Example 1, a honeycomb fired body was manufactured using a raw material paste not including a CuO source as follows.
比較例１では、以下のように、ＣｕＯ源を含まない原料ペーストを用いてハニカム焼成体を作製した。 (Comparative Example 1)
In Comparative Example 1, a honeycomb fired body was manufactured using a raw material paste not including a CuO source as follows.
β型ゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比：４４０、平均粒子径：２μｍ）を４０重量部、無機バインダとしてベーマイトを１０．５重量部、平均繊維径が３μｍ、平均繊維長が１２０μｍのアルミナ繊維を７．５重量部、有機バインダとしてメチルセルロースを５重量部、成形助剤としてオレイン酸を５重量部及びイオン交換水を３２重量部混合混練して、原料ペーストを作製した。
40 parts by weight of β-type zeolite (SiO 2 / Al 2 O 3 molar ratio: 440, average particle size: 2 μm), 10.5 parts by weight of boehmite as an inorganic binder, an average fiber diameter of 3 μm, and an average fiber length of 120 μm A raw material paste was prepared by mixing and kneading 7.5 parts by weight of alumina fibers, 5 parts by weight of methylcellulose as an organic binder, 5 parts by weight of oleic acid and 32 parts by weight of ion-exchanged water as a molding aid.
押出成形機を用いて、原料ペーストを押出成形して、正四角柱状のハニカム成形体を作製した。そして、減圧マイクロ波乾燥機を用いて、ハニカム成形体を出力４０ｋＷ、減圧６．７ｋＰａで１７分間乾燥させた後、７００℃で３時間４０分脱脂・焼成することにより、ハニカム焼成体を作製した。ハニカム焼成体は、一辺が３３ｍｍ、長さが４３ｍｍの正四角柱状であり、貫通孔の密度が６２個／ｃｍ２、隔壁の厚さが０．３６ｍｍであった。以上により、比較例１の評価用サンプルを得た。
The raw material paste was extruded using an extruder, and a regular quadrangular prism-shaped honeycomb formed body was produced. The honeycomb molded body was dried for 17 minutes at an output of 40 kW and a reduced pressure of 6.7 kPa using a vacuum microwave dryer, and then degreased and fired at 700 ° C. for 3 hours and 40 minutes to produce a honeycomb fired body. . The honeycomb fired body had a regular square pillar shape with a side of 33 mm and a length of 43 mm, a density of through holes of 62 holes / cm 2 , and a partition wall thickness of 0.36 mm. Thus, an evaluation sample of Comparative Example 1 was obtained.
（比較例２）
比較例２では、ＳｉＯ２／Ａｌ２Ｏ３モル比が４０であるβ型ゼオライトを含む原料ペーストを用いたこと以外は実施例１と同様にハニカム焼成体を作製した。以上により、比較例２の評価用サンプルを得た。 (Comparative Example 2)
In Comparative Example 2, a honeycomb fired body was manufactured in the same manner as in Example 1 except that a raw material paste containing β-type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 40 was used. Thus, an evaluation sample of Comparative Example 2 was obtained.
比較例２では、ＳｉＯ２／Ａｌ２Ｏ３モル比が４０であるβ型ゼオライトを含む原料ペーストを用いたこと以外は実施例１と同様にハニカム焼成体を作製した。以上により、比較例２の評価用サンプルを得た。 (Comparative Example 2)
In Comparative Example 2, a honeycomb fired body was manufactured in the same manner as in Example 1 except that a raw material paste containing β-type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 40 was used. Thus, an evaluation sample of Comparative Example 2 was obtained.
［炭化水素の放出量の測定］
前処理として、実施例１、比較例１及び比較例２の評価用サンプルをＮ２ガス雰囲気中で４５０℃、３０分間保持した後、ＣＯを０．３体積％含むＮ２ガス雰囲気中で４５０℃、２分間保持した。前処理後の評価用サンプルに対し、プロピレンを１１２５ｐｐｍＣ、プロパンを３７５ｐｐｍＣ、ＣＯを０．２体積％、Ｈ２Ｏを１０体積％、Ｏ２を２０体積％含み、残部がＮ２であるガスを３０℃で３０秒間流通させることにより、炭化水素（ＨＣ）であるプロピレン及びプロパンを吸着させた。その後、Ｈ２Ｏを１０体積％含み、残部がＮ２であるガスに切り替え、６０℃／分の速度で４５０℃まで昇温した。その際、評価用サンプルから流出するガスの全炭化水素（ＴＨＣ）を測定し、その値を評価用サンプルからの炭化水素の放出量とした。 [Measurement of hydrocarbon emissions]
As a pretreatment, Example 1, the evaluation sample of Comparative Example 1 and Comparative Example 2 450 ° C. in an N 2 gas atmosphere, after maintaining for 30 minutes, in an N 2 gas atmosphere containing CO 0.3 vol% 450 Hold at 2 ° C. for 2 minutes. With respect to the sample for evaluation after the pretreatment, a gas containing 1125 ppmC of propylene, 375 ppmC of propane, 0.2% by volume of CO, 10% by volume of H 2 O, 20% by volume of O 2 and the balance being N 2 Hydrocarbon (HC) propylene and propane were adsorbed by flowing at 30 ° C. for 30 seconds. Thereafter, the gas was switched to a gas containing 10% by volume of H 2 O and the balance being N 2 , and the temperature was raised to 450 ° C. at a rate of 60 ° C./min. At that time, the total hydrocarbon (THC) of the gas flowing out from the evaluation sample was measured, and the value was used as the amount of hydrocarbon released from the evaluation sample.
前処理として、実施例１、比較例１及び比較例２の評価用サンプルをＮ２ガス雰囲気中で４５０℃、３０分間保持した後、ＣＯを０．３体積％含むＮ２ガス雰囲気中で４５０℃、２分間保持した。前処理後の評価用サンプルに対し、プロピレンを１１２５ｐｐｍＣ、プロパンを３７５ｐｐｍＣ、ＣＯを０．２体積％、Ｈ２Ｏを１０体積％、Ｏ２を２０体積％含み、残部がＮ２であるガスを３０℃で３０秒間流通させることにより、炭化水素（ＨＣ）であるプロピレン及びプロパンを吸着させた。その後、Ｈ２Ｏを１０体積％含み、残部がＮ２であるガスに切り替え、６０℃／分の速度で４５０℃まで昇温した。その際、評価用サンプルから流出するガスの全炭化水素（ＴＨＣ）を測定し、その値を評価用サンプルからの炭化水素の放出量とした。 [Measurement of hydrocarbon emissions]
As a pretreatment, Example 1, the evaluation sample of Comparative Example 1 and Comparative Example 2 450 ° C. in an N 2 gas atmosphere, after maintaining for 30 minutes, in an N 2 gas atmosphere containing CO 0.3 vol% 450 Hold at 2 ° C. for 2 minutes. With respect to the sample for evaluation after the pretreatment, a gas containing 1125 ppmC of propylene, 375 ppmC of propane, 0.2% by volume of CO, 10% by volume of H 2 O, 20% by volume of O 2 and the balance being N 2 Hydrocarbon (HC) propylene and propane were adsorbed by flowing at 30 ° C. for 30 seconds. Thereafter, the gas was switched to a gas containing 10% by volume of H 2 O and the balance being N 2 , and the temperature was raised to 450 ° C. at a rate of 60 ° C./min. At that time, the total hydrocarbon (THC) of the gas flowing out from the evaluation sample was measured, and the value was used as the amount of hydrocarbon released from the evaluation sample.
図４は、温度と炭化水素の放出量との関係を示すグラフである。
図４より、実施例１では、比較例１に比べて高温側で炭化水素が放出されること、及び、炭化水素の放出量が大幅に増加することが確認された。また、実施例１では、比較例２と比べても高温側で炭化水素が放出されること、及び、炭化水素の放出量が多いことが確認された。
以上の結果から、ＳｉＯ２／Ａｌ２Ｏ３モル比が高いβ型ゼオライトにＣｕＯを共存させることにより、炭化水素の吸着性能に優れたハニカム構造体とすることができると考えられる。 FIG. 4 is a graph showing the relationship between temperature and hydrocarbon release.
From FIG. 4, it was confirmed that in Example 1, hydrocarbons were released on the high temperature side as compared with Comparative Example 1, and the amount of released hydrocarbons increased significantly. Further, in Example 1, it was confirmed that hydrocarbons were released on the high temperature side as compared with Comparative Example 2, and that the amount of released hydrocarbons was large.
From the above results, it is considered that by making CuO coexist in β-type zeolite having a high SiO 2 / Al 2 O 3 molar ratio, a honeycomb structure excellent in hydrocarbon adsorption performance can be obtained.
図４より、実施例１では、比較例１に比べて高温側で炭化水素が放出されること、及び、炭化水素の放出量が大幅に増加することが確認された。また、実施例１では、比較例２と比べても高温側で炭化水素が放出されること、及び、炭化水素の放出量が多いことが確認された。
以上の結果から、ＳｉＯ２／Ａｌ２Ｏ３モル比が高いβ型ゼオライトにＣｕＯを共存させることにより、炭化水素の吸着性能に優れたハニカム構造体とすることができると考えられる。 FIG. 4 is a graph showing the relationship between temperature and hydrocarbon release.
From FIG. 4, it was confirmed that in Example 1, hydrocarbons were released on the high temperature side as compared with Comparative Example 1, and the amount of released hydrocarbons increased significantly. Further, in Example 1, it was confirmed that hydrocarbons were released on the high temperature side as compared with Comparative Example 2, and that the amount of released hydrocarbons was large.
From the above results, it is considered that by making CuO coexist in β-type zeolite having a high SiO 2 / Al 2 O 3 molar ratio, a honeycomb structure excellent in hydrocarbon adsorption performance can be obtained.
［Ｈ２－ＴＰＲ測定によるＣｕの状態分析］
触媒分析装置（マイクロトラック・ベル製：ＢＥＬＣＡＴ－Ａ）を用いて、前処理として、実施例１の評価用サンプルをＨｅガス雰囲気中で２１０℃、２時間保持した後、５０℃まで冷却し、Ｈ２：４．９５体積％（残りはＡｒ）雰囲気中で１０℃／分の速度で１０００℃まで昇温した。その際、評価用サンプルから流出するガス量の変化を熱伝導度型検出器（Ｔｈｅｒｍａｌ Ｃｏｎｄｕｃｔｉｖｉｔｙ Ｄｅｔｅｃｔｏｒ：ＴＣＤ）で測定し、プロットした。 [Cu state analysis by H 2 -TPR measurement]
Using a catalyst analyzer (manufactured by Microtrack Bell: BELCAT-A), as a pretreatment, the sample for evaluation of Example 1 was held in a He gas atmosphere at 210 ° C. for 2 hours, then cooled to 50 ° C., The temperature was raised to 1000 ° C. at a rate of 10 ° C./min in an atmosphere of H 2 : 4.95% by volume (the rest being Ar). At that time, changes in the amount of gas flowing out from the evaluation sample were measured with a thermal conductivity detector (TCD) and plotted.
触媒分析装置（マイクロトラック・ベル製：ＢＥＬＣＡＴ－Ａ）を用いて、前処理として、実施例１の評価用サンプルをＨｅガス雰囲気中で２１０℃、２時間保持した後、５０℃まで冷却し、Ｈ２：４．９５体積％（残りはＡｒ）雰囲気中で１０℃／分の速度で１０００℃まで昇温した。その際、評価用サンプルから流出するガス量の変化を熱伝導度型検出器（Ｔｈｅｒｍａｌ Ｃｏｎｄｕｃｔｉｖｉｔｙ Ｄｅｔｅｃｔｏｒ：ＴＣＤ）で測定し、プロットした。 [Cu state analysis by H 2 -TPR measurement]
Using a catalyst analyzer (manufactured by Microtrack Bell: BELCAT-A), as a pretreatment, the sample for evaluation of Example 1 was held in a He gas atmosphere at 210 ° C. for 2 hours, then cooled to 50 ° C., The temperature was raised to 1000 ° C. at a rate of 10 ° C./min in an atmosphere of H 2 : 4.95% by volume (the rest being Ar). At that time, changes in the amount of gas flowing out from the evaluation sample were measured with a thermal conductivity detector (TCD) and plotted.
図５は、Ｈ２－ＴＰＲ測定によるＣｕの状態分析の結果を示すグラフである。
図５より、実施例１では、２００℃付近に最大ピークが存在することが確認された。このピークは、イオン交換されずにβ型ゼオライトの表面に析出しているＣｕＯに由来するピークと考えられる。この結果から、実施例１では、β型ゼオライトがＣｕイオンによりイオン交換されておらず、ＣｕＯがβ型ゼオライトの表面に担持されていると考えられる。 FIG. 5 is a graph showing the results of Cu state analysis by H 2 -TPR measurement.
From FIG. 5, in Example 1, it was confirmed that the maximum peak exists in 200 degreeC vicinity. This peak is considered to be a peak derived from CuO that is not ion-exchanged and is deposited on the surface of the β-type zeolite. From this result, in Example 1, it is considered that β-type zeolite is not ion-exchanged by Cu ions, and CuO is supported on the surface of β-type zeolite.
図５より、実施例１では、２００℃付近に最大ピークが存在することが確認された。このピークは、イオン交換されずにβ型ゼオライトの表面に析出しているＣｕＯに由来するピークと考えられる。この結果から、実施例１では、β型ゼオライトがＣｕイオンによりイオン交換されておらず、ＣｕＯがβ型ゼオライトの表面に担持されていると考えられる。 FIG. 5 is a graph showing the results of Cu state analysis by H 2 -TPR measurement.
From FIG. 5, in Example 1, it was confirmed that the maximum peak exists in 200 degreeC vicinity. This peak is considered to be a peak derived from CuO that is not ion-exchanged and is deposited on the surface of the β-type zeolite. From this result, in Example 1, it is considered that β-type zeolite is not ion-exchanged by Cu ions, and CuO is supported on the surface of β-type zeolite.
［吸水変位量の測定］
実施例１及び比較例２の評価用サンプルを水に浸漬し、吸水率を所定の値としたときの体積変化率［％］を求め、その値を吸水変位量とする。吸水率は、電子天秤（Ａ＆Ｄ製 ＨＲ２０２ｉ）を用いて、絶乾時の重量と吸水時の重量とを測定することにより算出する。
その結果、実施例１では、比較例２に比べて吸水変位量が小さいことが確認できる。この結果から、ＳｉＯ２／Ａｌ２Ｏ３モル比が高いβ型ゼオライトにＣｕＯを共存させることにより、β型ゼオライトに水分が吸着しにくくなり、水分の吸着／脱離による体積の収縮／膨張が抑制されると考えられる。 [Measurement of water absorption displacement]
The samples for evaluation of Example 1 and Comparative Example 2 are immersed in water, the volume change rate [%] when the water absorption rate is set to a predetermined value is obtained, and the value is taken as the water absorption displacement amount. The water absorption is calculated by measuring the weight at the time of absolutely dry and the weight at the time of water absorption using an electronic balance (HR202i manufactured by A & D).
As a result, in Example 1, it can be confirmed that the amount of water absorption displacement is smaller than that in Comparative Example 2. From this result, by making CuO coexist in β-type zeolite having a high SiO 2 / Al 2 O 3 molar ratio, it becomes difficult for moisture to be adsorbed to β-type zeolite, and volume shrinkage / expansion due to moisture adsorption / desorption is reduced. It is thought to be suppressed.
実施例１及び比較例２の評価用サンプルを水に浸漬し、吸水率を所定の値としたときの体積変化率［％］を求め、その値を吸水変位量とする。吸水率は、電子天秤（Ａ＆Ｄ製 ＨＲ２０２ｉ）を用いて、絶乾時の重量と吸水時の重量とを測定することにより算出する。
その結果、実施例１では、比較例２に比べて吸水変位量が小さいことが確認できる。この結果から、ＳｉＯ２／Ａｌ２Ｏ３モル比が高いβ型ゼオライトにＣｕＯを共存させることにより、β型ゼオライトに水分が吸着しにくくなり、水分の吸着／脱離による体積の収縮／膨張が抑制されると考えられる。 [Measurement of water absorption displacement]
The samples for evaluation of Example 1 and Comparative Example 2 are immersed in water, the volume change rate [%] when the water absorption rate is set to a predetermined value is obtained, and the value is taken as the water absorption displacement amount. The water absorption is calculated by measuring the weight at the time of absolutely dry and the weight at the time of water absorption using an electronic balance (HR202i manufactured by A & D).
As a result, in Example 1, it can be confirmed that the amount of water absorption displacement is smaller than that in Comparative Example 2. From this result, by making CuO coexist in β-type zeolite having a high SiO 2 / Al 2 O 3 molar ratio, it becomes difficult for moisture to be adsorbed to β-type zeolite, and volume shrinkage / expansion due to moisture adsorption / desorption is reduced. It is thought to be suppressed.
１０，２０ ハニカム構造体
１１，２１ ハニカム焼成体
１１ａ，２１ａ 貫通孔
１１ｂ，２１ｂ 隔壁
１２，２２ 外周コート層
２３ 接着層
DESCRIPTION OF SYMBOLS 10,20 Honeycomb structure 11,21 Honeycomb fired body 11a, 21a Through- hole 11b, 21b Partition 12, 22, Outer peripheral coat layer 23 Adhesive layer
１１，２１ ハニカム焼成体
１１ａ，２１ａ 貫通孔
１１ｂ，２１ｂ 隔壁
１２，２２ 外周コート層
２３ 接着層
DESCRIPTION OF
Claims (8)
- 複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体であって、
前記ハニカム焼成体は、ＣｕＯとβ型ゼオライトと無機バインダとを含む押出成形体からなり、
前記β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、３００以上であることを特徴とするハニカム構造体。 A honeycomb structure including a honeycomb fired body in which a plurality of through holes are arranged in parallel in a longitudinal direction with a partition wall therebetween,
The honeycomb fired body is an extrusion-molded body containing CuO, β-type zeolite, and an inorganic binder,
The honeycomb structure according to claim 1, wherein the β-type zeolite has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. - 前記ハニカム構造体は、前記β型ゼオライトに対してＣｕを１～７重量％含む請求項１に記載のハニカム構造体。 The honeycomb structure according to claim 1, wherein the honeycomb structure contains 1 to 7 wt% of Cu with respect to the β-type zeolite.
- 前記ハニカム焼成体は、無機繊維をさらに含む請求項１又は２に記載のハニカム構造体。 The honeycomb structure according to claim 1 or 2, wherein the honeycomb fired body further includes inorganic fibers.
- 前記隔壁の表面に三元触媒が担持されている請求項１～３のいずれか１項に記載のハニカム構造体。 The honeycomb structure according to any one of claims 1 to 3, wherein a three-way catalyst is supported on a surface of the partition wall.
- 複数の貫通孔が隔壁を隔てて長手方向に並設されたハニカム焼成体を備えたハニカム構造体の製造方法であって、
ＣｕＯ源とβ型ゼオライトと無機バインダとを含む原料ペーストを成形することにより、複数の貫通孔が隔壁を隔てて長手方向に並設された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焼成することにより、ハニカム焼成体を作製する焼成工程と、を含み、
前記原料ペーストに含まれる前記β型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、３００以上であることを特徴とするハニカム構造体の製造方法。 A method for manufacturing a honeycomb structure including a honeycomb fired body in which a plurality of through holes are arranged in parallel in a longitudinal direction with a partition wall therebetween,
A forming step of forming a honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall formed by forming a raw material paste containing a CuO source, β-type zeolite, and an inorganic binder,
Firing the honeycomb formed body to produce a honeycomb fired body, and
The honeycomb structure manufacturing method, wherein the β-type zeolite contained in the raw material paste has a SiO 2 / Al 2 O 3 molar ratio of 300 or more. - 前記原料ペーストに含まれる前記ＣｕＯ源の量は、Ｃｕ換算で、前記β型ゼオライトに対して１～７重量％である請求項５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 claim 5, wherein the amount of the CuO source contained in the raw material paste is 1 to 7% by weight with respect to the β-type zeolite in terms of Cu.
- 前記原料ペーストは、無機繊維をさらに含む請求項５又は６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 claim 5 or 6, wherein the raw material paste further includes inorganic fibers.
- 前記隔壁の表面に三元触媒を担持させる担持工程をさらに含む請求項５～７のいずれか１項に記載のハニカム構造体の製造方法。
The method for manufacturing a honeycomb structure according to any one of claims 5 to 7, further comprising a supporting step of supporting a three-way catalyst on the surface of the partition wall.
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|---|---|---|---|---|
| JPH11228128A (en) * | 1997-11-07 | 1999-08-24 | Ngk Insulators Ltd | Highly heat-resistant beta-zeolite and adsorption material for auto exhaust purification using same |
| JP2011125846A (en) * | 2009-11-19 | 2011-06-30 | Ibiden Co Ltd | Honeycomb structure and apparatus for cleaning exhaust gas |
| JP2012213754A (en) * | 2011-03-29 | 2012-11-08 | Ibiden Co Ltd | Honeycomb structure and exhaust gas-cleaning device |
| WO2015145181A1 (en) * | 2014-03-27 | 2015-10-01 | Johnson Matthey Public Limited Company | Process for producing a catalyst and catalyst as such |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228128A (en) * | 1997-11-07 | 1999-08-24 | Ngk Insulators Ltd | Highly heat-resistant beta-zeolite and adsorption material for auto exhaust purification using same |
| JP2011125846A (en) * | 2009-11-19 | 2011-06-30 | Ibiden Co Ltd | Honeycomb structure and apparatus for cleaning exhaust gas |
| JP2012213754A (en) * | 2011-03-29 | 2012-11-08 | Ibiden Co Ltd | Honeycomb structure and exhaust gas-cleaning device |
| WO2015145181A1 (en) * | 2014-03-27 | 2015-10-01 | Johnson Matthey Public Limited Company | Process for producing a catalyst and catalyst as such |
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