WO2014104179A1 - ハニカムフィルタ及びその製造方法、並びに、チタン酸アルミニウム系セラミックス及びその製造方法 - Google Patents
ハニカムフィルタ及びその製造方法、並びに、チタン酸アルミニウム系セラミックス及びその製造方法 Download PDFInfo
- Publication number
- WO2014104179A1 WO2014104179A1 PCT/JP2013/084856 JP2013084856W WO2014104179A1 WO 2014104179 A1 WO2014104179 A1 WO 2014104179A1 JP 2013084856 W JP2013084856 W JP 2013084856W WO 2014104179 A1 WO2014104179 A1 WO 2014104179A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- satisfies
- catalyst
- honeycomb filter
- honeycomb
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 47
- 239000000919 ceramic Substances 0.000 title claims description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052782 aluminium Inorganic materials 0.000 title claims description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 17
- 239000004411 aluminium Substances 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 118
- 238000005192 partition Methods 0.000 claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims description 54
- 229910052710 silicon Inorganic materials 0.000 claims description 48
- 239000010936 titanium Substances 0.000 claims description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000010703 silicon Substances 0.000 claims description 37
- 239000011777 magnesium Substances 0.000 claims description 35
- 238000010304 firing Methods 0.000 claims description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- 239000010457 zeolite Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 27
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 8
- 238000001228 spectrum Methods 0.000 claims description 8
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 241000264877 Hippospongia communis Species 0.000 description 188
- 239000000843 powder Substances 0.000 description 114
- 239000007789 gas Substances 0.000 description 54
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 30
- 239000011734 sodium Substances 0.000 description 29
- 238000007789 sealing Methods 0.000 description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 239000000395 magnesium oxide Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000006866 deterioration Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000314 lubricant Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000004014 plasticizer Substances 0.000 description 11
- 238000000746 purification Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 150000002484 inorganic compounds Chemical class 0.000 description 10
- 229910010272 inorganic material Inorganic materials 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229920002472 Starch Polymers 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000004891 communication Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000061456 Solanum tuberosum Species 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000005273 Canna coccinea Nutrition 0.000 description 1
- 240000008555 Canna flaccida Species 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz 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
- 229940100486 rice starch Drugs 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/14—Silica and magnesia
-
- 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
-
- 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
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/478—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on aluminium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
Definitions
- the present invention relates to a honeycomb filter and a manufacturing method thereof, and an aluminum titanate ceramic and a manufacturing method thereof.
- the honeycomb filter is used to remove the collected matter from the fluid containing the collected matter.
- the honeycomb filter collects fine particles such as carbon particles contained in exhaust gas discharged from an internal combustion engine such as a diesel engine. It is used as a ceramic filter (diesel particulate filter).
- the honeycomb filter has a plurality of parallel flow paths partitioned by partition walls, and one end of a part of the plurality of flow paths and the other end of the remaining part of the plurality of flow paths are sealed. .
- a honeycomb structure constituting such a honeycomb filter for example, structures described in Patent Documents 1 and 2 below are known.
- the diesel particulate filter may carry a precious metal catalyst supported on a ⁇ -alumina catalyst for the purpose of promoting the combustion of the collected carbon particles. Further, the exhaust gas is usually supplied to the oxidation catalyst before being supplied to the diesel particulate filter, and the hydrocarbon in the exhaust gas is oxidized and removed. However, there are cases where the oxidation removal of the hydrocarbon by the oxidation catalyst is not sufficient. Therefore, for the purpose of adsorbing and burning hydrocarbons that could not be oxidized by the oxidation catalyst, the diesel particulate filter may carry zeolite in addition to the aforementioned noble metal catalyst. Such a diesel particulate filter carrying a catalyst is referred to as a catalyzed diesel particulate filter (Catalyzed Diesel Particulate Filter).
- Catalyzed Diesel Particulate Filter Catalyzed Diesel Particulate Filter
- ammonia SCR Selective Catalytic Reduction
- the honeycomb structure In diesel vehicles, in order to perform the reduction of the NO X by the SCR efficiently, the honeycomb structure was supported zeolite is used. Further, as the zeolite, a metal ion exchanged zeolite ion-exchanged with a metal ion such as a copper ion is used in order to improve NO X reduction.
- the honeycomb structure for SCR and the diesel particulate filter are arranged in series to construct an exhaust gas purification system.
- a honeycomb filter having both a SCR function and a diesel particulate filter function by supporting a metal ion exchange zeolite on the partition wall surface of the diesel particulate filter has also been proposed. (For example, refer to Patent Document 3).
- the honeycomb filter carrying the catalyst has a problem that when the carbon particles are removed by combustion as described above, the honeycomb filter is exposed to a high temperature and the catalyst is likely to be deteriorated.
- An object of the present invention is to provide a honeycomb filter capable of suppressing deterioration of a catalyst when exposed to a high temperature, a manufacturing method thereof, an aluminum titanate ceramic, and a manufacturing method thereof.
- the present invention is supported by a partition wall forming a plurality of parallel flow paths, at least a part of the surface of the partition wall, and / or at least a part of the pores of the partition wall.
- a honeycomb filter comprising a catalyst, wherein the honeycomb filter has a first end face and a second end face located on the opposite side of the first end face, and the plurality of flow paths are A plurality of first flow passages whose end portions on the second end face side are sealed; and a plurality of second flow passages whose end portions on the first end face side are sealed;
- the elemental composition ratio of Al, Mg, Ti, Si, Na, K, Ca and Sr in the composition is represented by the following composition formula (I); Al 2 (1-x) Mg x Ti (1 + y) O 5 + aAl 2 O 3 + BSiO 2 + CNa 2 O + dK 2 O + eCaO + fSrO (I) , X satisfies
- the honeycomb filter can suppress deterioration of the catalyst even when the catalyst supported on the partition wall is exposed to a high temperature because the partition wall has the specific composition.
- a peak indicating a crystalline silica-containing phase does not appear in the powder X-ray diffraction spectrum of the partition wall. Since the partition wall does not contain a crystalline silica-containing phase, it is difficult to decompose at high temperatures and to become stable.
- the catalyst preferably contains zeolite.
- the honeycomb filter can improve the NO X resolution when used as a honeycomb filter function with the in SCR, also hydrocarbon adsorption when used as catalyzed diesel particulate filter Performance can be improved.
- the present invention also includes a partition wall that forms a plurality of parallel flow paths, and a catalyst supported on at least a part of the surface of the partition wall and / or at least a part of the pores of the partition wall,
- the first end face and a second end face located on the opposite side of the first end face, and the plurality of flow paths have a plurality of first ends sealed at the end on the second end face side.
- a plurality of second flow channels whose ends on the first end face side are sealed, and Al, Mg, Ti, Si, Na, K, Ca, and Sr in the partition walls.
- c and d satisfy 0 ⁇ (c + d), c, d, e and f satisfy 0.5 ⁇ (c + d + e + f) / b ⁇ ⁇ 100 ⁇ 10
- the production method of the method comprising an aluminum source, a magnesium source, a titanium source, a silicon source, a pore former, a binder and a solvent, wherein the total amount of Na 2 O and K 2 O in the aluminum source is 0.001% by mass or more
- the total amount of Na 2 O and K 2 O in the magnesium source is 0.001% by mass or more and 0.25% by mass or less, and the Na 2 O and K 2 in the titanium source are not more than 0.25% by mass.
- the total amount of O is 0.001 mass% or more and 0.25 mass% or less
- a step of a raw material mixture is molded and fired to obtain a honeycomb fired body the total amount of Na 2 O and K 2 O in Motogen is up to 0.25 mass% 0.001 mass% or more, above the honeycomb fired body
- a step of obtaining the honeycomb filter by supporting the catalyst on at least a part of the partition wall surface and / or at least a part of the pores of the partition wall.
- the honeycomb filter having the above-described configuration can be efficiently manufactured.
- the silicon source preferably contains 95% by mass or more of SiO 2 . Thereby, the influence of impurities becomes small, and the composition of the partition wall can be easily controlled.
- the silicon source preferably contains 90% by mass or more of an amorphous phase. This improves the reactivity of the silicon source during the manufacture of the honeycomb filter and facilitates the manufacture of the honeycomb filter having a uniform silicon-containing phase.
- the method for manufacturing the honeycomb filter preferably includes a step of washing the honeycomb fired body before supporting the catalyst. As a result, the silicon-containing phase on the partition wall surface can be removed, and the deterioration of the catalyst can be further suppressed.
- the honeycomb fired body is preferably washed with an alkaline solution having a pH of 9 or more. This facilitates the removal of the silicon-containing phase on the partition wall surface.
- the catalyst preferably contains zeolite.
- the honeycomb filter can improve the NO X resolution when used as a honeycomb filter function with the in SCR, also hydrocarbon adsorption when used as catalyzed diesel particulate filter Performance can be improved.
- the elemental composition ratio of Al, Mg, Ti, Si, Na, K, Ca and Sr is expressed by the following composition formula (I); Al 2 (1-x) Mg x Ti (1 + y) O 5 + aAl 2 O 3 + BSiO 2 + CNa 2 O + dK 2 O + eCaO + fSrO (I) , X satisfies 0 ⁇ x ⁇ 1, y satisfies 0.5x ⁇ y ⁇ 3x, a satisfies 0.1x ⁇ a ⁇ 2x, and b satisfies 0.05 ⁇ b.
- the aluminum titanate-based ceramic is useful as a catalyst carrier because it can suppress the deterioration of the catalyst even when the catalyst supported on the ceramic is exposed to a high temperature.
- the aluminum titanate-based ceramics preferably does not show a peak indicating a crystalline silica-containing phase in a powder X-ray diffraction spectrum. Since the aluminum titanate-based ceramic does not contain a crystalline silica-containing phase, it is difficult to decompose at high temperatures and is likely to be stable.
- the present invention further includes an aluminum source, a magnesium source, a titanium source and a silicon source, wherein the total amount of Na 2 O and K 2 O in the aluminum source is 0.001% by mass or more and 0.25% by mass or less, The total amount of Na 2 O and K 2 O in the magnesium source is 0.001% by mass or more and 0.25% by mass or less, and the total amount of Na 2 O and K 2 O in the titanium source is 0.001% by mass or more.
- the elemental composition ratio of Mg, Ti, Si, Na, K, Ca and Sr is expressed by the following composition formula (I); Al 2 (1-x) Mg x Ti (1 + y) O 5 + aAl 2 O 3 + BSiO 2 + CNa 2 O + dK 2 O + eCaO + fSrO (I) , X satisfies 0 ⁇ x ⁇ 1, y satisfies 0.5x ⁇ y ⁇ 3x, a satisfies 0.1x ⁇ a ⁇ 2x, and b satisfies 0.05 ⁇ b.
- c and d satisfy 0 ⁇ (c + d), c, d, e and f satisfy 0.5 ⁇ (c + d + e + f) / b ⁇ ⁇ 100 ⁇ 10
- a method for producing an aluminum titanate ceramic which includes a step of obtaining a ceramic.
- the aluminum titanate-based ceramics having the above-described configuration can be efficiently manufactured.
- the silicon source preferably contains 95% by mass or more of SiO 2 . Thereby, the influence of impurities becomes small, and the control of the composition of the aluminum titanate ceramics becomes easy.
- the silicon source preferably contains 90% by mass or more of an amorphous phase.
- the method for producing the aluminum titanate-based ceramics preferably includes a step of washing the fired product after firing the raw material mixture. Thereby, the silicon-containing phase on the surface of the aluminum titanate ceramic can be removed. Further, when the catalyst is supported on such an aluminum titanate ceramic, it is possible to further suppress the deterioration of the catalyst.
- the fired product is preferably washed with an alkaline solution having a pH of 9 or more. This facilitates removal of the silicon-containing phase on the surface of the aluminum titanate ceramic.
- a honeycomb filter capable of suppressing deterioration of a catalyst when exposed to a high temperature, a manufacturing method thereof, an aluminum titanate ceramic and a manufacturing method thereof.
- FIG. 2 (a) is an enlarged view of the end face on the opposite side of Fig. 1 (b) in the honeycomb filter shown in Fig. 1, and Fig. 2 (b) is an enlarged view of a partition wall cross section.
- FIG. 3 is a view taken along arrow III-III in FIG. It is a figure which shows typically the honey-comb filter which concerns on 2nd Embodiment of this invention.
- Fig.5 (a) is an enlarged view of the end surface on the opposite side to FIG.4 (b) in the honey-comb filter shown in FIG. 4, FIG.5 (b) is an enlarged view of a partition cross section.
- FIG. 6 is a view taken along the line VI-VI in FIG. It is the schematic of the exhaust gas purification system provided with the honey-comb filter of this invention.
- Fig. 1 is a diagram schematically showing a honeycomb filter according to the first embodiment.
- Fig. 1 (a) is a perspective view and an enlarged view of an end face of the honeycomb filter
- Fig. 1 (b) is a diagram of Fig. 1 (b). It is an enlarged view of area
- Fig. 2 (a) is an enlarged view of the end face on the opposite side of Fig. 1 (b) in the honeycomb filter shown in Fig. 1, and Fig. 2 (b) is an enlarged view of a partition wall cross section.
- FIG. 3 is a view taken in the direction of arrows III-III in FIG.
- the honeycomb filter 100 has one end face (first end face) 100a and the other end face (second end face) 100b located on the opposite side of the end face 100a.
- the honeycomb filter 100 is a cylindrical body having a plurality of flow paths 110 extending in parallel to each other.
- the plurality of flow paths 110 are partitioned by partition walls 120 extending in parallel to the central axis of the honeycomb filter 100.
- the plurality of channels 110 have a plurality of channels (first channels) 110a and a plurality of channels (second channels) 110b adjacent to the channels 110a.
- the flow path 110a and the flow path 110b extend from the end face 100a to the end face 100b perpendicular to the end faces 100a and 100b.
- One end of the flow path 110a constituting a part of the flow path 110 is opened at the end face 100a, and the other end of the flow path 110a is sealed by the sealing portion 130 at the end face 100b.
- One end of the flow path 110b constituting the remaining part of the plurality of flow paths 110 is sealed by the sealing portion 130 at the end face 100a, and the other end of the flow path 110b is opened at the end face 100b.
- an end portion on the end surface 100a side of the flow path 110a is opened as a gas inlet
- an end portion on the end face 100b side of the flow path 110b is opened as a gas outlet.
- the cross section perpendicular to the axial direction of the flow path 110a and the flow path 110b has a hexagonal shape.
- the cross section of the flow path 110b is, for example, a regular hexagonal shape in which the lengths of the sides 140 forming the cross section are substantially equal to each other, but may be a flat hexagonal shape.
- the cross section of the flow path 110a has, for example, a flat hexagonal shape, but may have a regular hexagonal shape.
- the lengths of the sides facing each other in the cross section of the channel 110a are substantially equal to each other.
- the cross section of the flow path 110a includes two long sides 150a having substantially the same length as the sides 150 forming the cross section, and four (two pairs) short sides 150b having substantially the same length. ,have.
- the short side 150b is disposed on each side of the long side 150a.
- the long sides 150a face each other in parallel, and the short sides 150b face each other in parallel.
- the partition 120 has the partition 120a as a part which partitions off the flow path 110a and the flow path 110b. That is, the channel 110a and the channel 110b are adjacent to each other through the partition wall 120a. By arranging one channel 110a between adjacent channels 110b, the channels 110b are alternately arranged with the channels 110a in the arrangement direction of the channels 110b (a direction substantially orthogonal to the side 140). ing.
- Each of the sides 140 of the flow channel 110b faces the long side 150a of any one of the plurality of flow channels 110a in parallel. That is, each of the wall surfaces forming the flow channel 110b faces the one wall surface forming the flow channel 110a in parallel in the partition wall 120a located between the flow channel 110a and the flow channel 110b.
- the flow path 110 has a structural unit including one flow path 110b and six flow paths 110a surrounding the flow path 110b. In the structural unit, all the sides 140 of the flow path 110b are included. Opposite the long side 150a of the channel 110a.
- at least one length of the side 140 of the flow path 110b may be substantially equal to the length of the opposed long side 150a, and each length of the side 140 is equal to the length of the opposed long side 150a. It may be substantially equal.
- the partition wall 120 has a partition wall 120b as a part for partitioning the adjacent flow paths 110a. That is, the flow paths 110a surrounding the flow path 110b are adjacent to each other via the partition wall 120b.
- Each of the short side 150b of the flow path 110a is facing in parallel with the short side 150b of the adjacent flow path 110a. That is, the wall surfaces forming the flow paths 110a face each other in parallel in the partition wall 120b located between the adjacent flow paths 110a.
- at least one length of the short side 150b of the flow path 110a between the adjacent flow paths 110a may be substantially equal to the length of the opposing short side 150b. The length may be substantially equal to the length of the opposing short side 150b.
- Catalysts are supported on the surfaces of the partition walls 120a and 120b in the channel 110a, the surfaces of the partition walls 120a and 120b in the channel 110b, and the pores (inside the communication holes) of the partition walls 120a and 120b.
- a catalyst layer 160 is formed by the catalyst.
- the catalyst layer 160 may be formed on at least part of the surfaces of the partition walls 120a and 120b and / or at least part of the pores of the partition walls 120a and 120b. More specifically, the catalyst layer 160 includes at least one of the surfaces of the partition walls 120a and 120b in the channel 110a, the surfaces of the partition walls 120a and 120b in the channel 110b, and the pores of the partition walls 120a and 120b. What is necessary is just to be formed in the location.
- the catalyst layer 160 is inside the pores of the partition walls 120a and 120b or inside the pores and the partition walls 120a and 120b on the gas outlet side. It is preferably formed on the surface.
- the catalyst layer 160 is preferably formed on the surfaces of the partition walls 120a and 120b on the gas inlet side.
- Fig. 4 is a diagram schematically showing the honeycomb filter according to the second embodiment.
- Fig. 4 (a) is a perspective view and an enlarged view of the end face of the honeycomb filter
- Fig. 4 (b) is a diagram of Fig. 4 (b). It is an enlarged view of area
- Fig.5 (a) is an enlarged view of the end surface on the opposite side to FIG.4 (b) in the honey-comb filter shown in FIG. 4,
- FIG.5 (b) is an enlarged view of a partition cross section. 6 is a view taken in the direction of arrows VI-VI in FIG.
- the honeycomb filter 200 has one end face (first end face) 200a and the other end face (second end face) 200b located on the opposite side of the end face 200a.
- the honeycomb filter 200 is a cylindrical body having a plurality of flow paths 210 extending in parallel to each other.
- the plurality of flow paths 210 are partitioned by partition walls 220 extending in parallel with the central axis of the honeycomb filter 200.
- the plurality of flow paths 210 include a plurality of flow paths (first flow paths) 210a and a plurality of flow paths (second flow paths) 210b adjacent to the flow paths 210a.
- the channel 210a and the channel 210b extend from the end surface 200a to the end surface 200b perpendicular to the end surfaces 200a and 200b.
- One end of the flow path 210a forming a part of the flow path 210 is open at the end face 200a, and the other end of the flow path 210a is sealed by the sealing portion 230 at the end face 200b.
- One end of the flow path 210b forming the remaining part of the plurality of flow paths 210 is sealed by the sealing portion 230 at the end face 200a, and the other end of the flow path 210b is opened at the end face 200b.
- an end portion on the end surface 200a side of the flow path 210a is opened as a gas inlet
- an end portion of the flow path 210b on the end surface 200b side is opened as a gas outlet.
- the cross section perpendicular to the axial direction of the flow path 210a and the flow path 210b has a hexagonal shape.
- the cross section of the flow path 210b is, for example, a regular hexagonal shape in which the lengths of the sides 240 forming the cross section are substantially equal to each other, but may be a flat hexagonal shape.
- the cross section of the flow path 210a is, for example, a flat hexagonal shape, but may be a regular hexagonal shape.
- the lengths of the sides facing each other in the cross section of the flow path 210a are different from each other.
- the cross section of the channel 210a has three long sides 250a having substantially the same length and three short sides 250b having substantially the same length as the sides 250 forming the cross section.
- the long side 250a and the short side 250b face each other in parallel, and the short side 250b is disposed on each side of the long side 250a.
- the partition 220 has the partition 220a as a part which partitions off the flow path 210a and the flow path 210b. That is, the flow path 210a and the flow path 210b are adjacent to each other through the partition wall 220a. Between the adjacent flow paths 210b, two flow paths 210a adjacent to each other in a direction substantially orthogonal to the arrangement direction of the flow paths 210b are arranged, and the two adjacent flow paths 210a are adjacent to each other. They are arranged symmetrically across a line connecting the centers of the cross sections of the path 210b.
- Each of the sides 240 of the flow path 210b faces the long side 250a of any one of the plurality of flow paths 210a in parallel. That is, each of the wall surfaces forming the flow path 210b faces the one wall surface forming the flow path 210a in parallel in the partition wall 220a positioned between the flow path 210a and the flow path 210b.
- the flow path 210 includes a structural unit including one flow path 210b and six flow paths 210a surrounding the flow path 210b. In the structural unit, all the sides 240 of the flow path 210b are included. It faces the long side 250a of the flow path 210a.
- each vertex of the cross section of the flow path 210b is opposed to the apex of the adjacent flow path 210b in the arrangement direction of the flow paths 210b.
- at least one length of the side 240 of the flow path 210b may be substantially equal to the length of the opposed long side 250a, and each length of the side 240 is equal to the length of the opposed long side 250a. It may be substantially equal.
- the partition 220 has the partition 220b as a part which partitions off the mutually adjacent flow paths 210a. That is, the flow paths 210a surrounding the flow path 210b are adjacent to each other through the partition 220b.
- Each of the short side 250b of the flow path 210a is facing in parallel with the short side 250b of the adjacent flow path 210a.
- the wall surfaces forming the flow path 210a face each other in parallel in the partition 220b located between the adjacent flow paths 210a.
- One flow path 210a is surrounded by three flow paths 210b.
- at least one length of the short side 250b of the flow path 210a may be substantially equal to the length of the opposing short side 250b.
- the length may be substantially equal to the length of the opposing short side 250b.
- Catalysts are supported on the surfaces of the partition walls 220a and 220b in the flow path 210a, the surfaces of the partition walls 220a and 220b in the flow path 210b, and the pores (inside the communication holes) of the partition walls 220a and 220b.
- a catalyst layer 260 is formed by the catalyst. Note that the catalyst layer 260 may be formed on at least a part of the surfaces of the partition walls 220a and 220b and / or at least a part of the pores of the partition walls 220a and 220b.
- the catalyst layer 260 includes at least one of the surfaces of the partition walls 220a and 220b in the channel 210a, the surfaces of the partition walls 220a and 220b in the channel 210b, and the pores of the partition walls 220a and 220b. What is necessary is just to be formed in the location.
- the catalyst layer 260 is disposed inside the pores of the partition walls 220a and 220b or inside the pores and the partition walls 220a and 220b on the gas outlet side. It is preferably formed on the surface.
- the catalyst layer 260 is preferably formed on the surfaces of the partition walls 220a and 220b on the gas inlet side.
- the length of the honeycomb filters 100 and 200 in the axial direction of the flow path is, for example, 50 to 300 mm.
- the outer diameter of the honeycomb filters 100 and 200 is, for example, 50 to 250 mm.
- the length of the side 140 is, for example, 0.4 to 2.0 mm.
- the length of the long side 150a is, for example, 0.4 to 2.0 mm, and the length of the short side 150b is, for example, 0.3 to 2.0 mm.
- the length of the side 240 is, for example, 0.4 to 2.0 mm.
- the length of the long side 250a is, for example, 0.4 to 2.0 mm
- the length of the short side 250b is, for example, 0.3 to 2.0 mm.
- the thickness of the partition walls 120 and 220 is, for example, 0.1 to 0.8 mm.
- the cell density in the honeycomb filters 100 and 200 is preferably 50 to 600 cpsi (cells per square inch), and more preferably 100 to 500 cpsi. preferable.
- Loading amount of the catalyst layers 160, 260 per unit volume of the honeycomb filter 100, 200, when used as a honeycomb filter having a function of SCR is sufficient NO X resolution without impairing the function of the diesel particulate filter From the viewpoint of obtaining the above, it is preferably 20 to 300 mg / cm 3 , and more preferably 50 to 200 mg / cm 3 . When used as a catalyzed diesel particulate filter, it is preferably 5 to 100 mg / cm 3 , more preferably 10 to 60 mg / cm 3 .
- the sum total of the opening area of the some flow path 110a in the end surface 100a is larger than the sum total of the opening area of the flow path 110b in the end surface 100b.
- the sum total of the opening area of the some flow path 210a in the end surface 200a is larger than the sum total of the opening area of the flow path 210b in the end surface 200b.
- the hydraulic diameter of the flow paths 110a and 210a on the end faces 100a and 200a is preferably 1.4 mm or less.
- the hydraulic diameters of the flow paths 110a and 210a are preferably 0.5 mm or more, and more preferably 0.7 mm or more, from the viewpoint of further suppressing accumulation of collected substances in the region on the end face side in the flow path.
- the hydraulic diameter of the flow paths 110b and 210b on the end faces 100b and 200b is preferably larger than the hydraulic diameter of the flow paths 110a and 210a on the end faces 100a and 200a.
- the hydraulic diameter of the flow paths 110b and 210b at the end faces 100b and 200b is preferably 1.7 mm or less, and more preferably 1.6 mm or less.
- the hydraulic diameter of the channels 110b and 210b is preferably 0.5 mm or more, and more preferably 0.7 mm or more, from the viewpoint of reducing the pressure loss of exhaust gas ventilation.
- the shape of the honeycomb filter is such that the cross section of the first channel perpendicular to the axial direction of the first channel (channels 110a and 210a) is the first side as in the honeycomb filters 100 and 200 described above. (Long sides 150a, 250a) and second sides (short sides 150b, 250b) respectively disposed on both sides of the first side, and a second channel (channels 110b, 210b). ) Each of the sides (sides 140 and 240) forming a cross section of the second flow path perpendicular to the axial direction of the first flow path are opposed to the first side of the first flow path. Each of the second sides may be in a form facing the second side of the adjacent first flow path, but is not necessarily limited to the shape described above.
- the cross section of the channel perpendicular to the axial direction of the channel in the honeycomb filter is not limited to the hexagonal shape, and may be a triangular shape, a rectangular shape, an octagonal shape, a circular shape, an elliptical shape, or the like. .
- those having different diameters may be mixed, or those having different cross-sectional shapes may be mixed.
- the arrangement of the flow path is not particularly limited, and the arrangement of the central axis of the flow path is arranged at the apex of an equilateral triangle or at the apex of a square according to the cross-sectional shape of the flow path. It may be a staggered arrangement or the like.
- the honeycomb filter is not limited to a cylindrical body, and may be an elliptical column, a triangular column, a quadrangular column, a hexagonal column, an octagonal column, or the like.
- the partition walls are porous, and include, for example, a porous ceramic sintered body.
- the partition has a structure that allows fluid to pass therethrough. Specifically, a large number of communication holes (flow channels) through which fluid can pass are formed in the partition wall.
- the porosity of the partition walls is preferably 20% by volume or more and more preferably 30% by volume or more from the viewpoint of improving the collection efficiency of the honeycomb filter and realizing a lower pressure loss.
- the porosity of the partition walls is preferably 70% by volume or less, and more preferably 60% by volume or less.
- the average pore diameter of the partition walls is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of improving the collection efficiency of the honeycomb filter and realizing a lower pressure loss.
- the average pore diameter of the partition walls is preferably 35 ⁇ m or less, and more preferably 30 ⁇ m or less.
- the porosity and average pore diameter of the partition walls can be adjusted by the particle diameter of the raw material, the amount of pore former added, the kind of pore former, and the firing conditions, and can be measured by mercury porosimetry.
- the partition includes aluminum magnesium titanate, alumina, Si element, and one or both of Na element and K element, and Al, Mg, Ti, Si, Na, K, Ca in the partition And the elemental composition ratio of Sr: Al 2 (1-x) Mg x Ti (1 + y) O 5 + aAl 2 O 3 + BSiO 2 + CNa 2 O + dK 2 O + eCaO + fSrO (I) , X satisfies 0 ⁇ x ⁇ 1, y satisfies 0.5x ⁇ y ⁇ 3x, a satisfies 0.1x ⁇ a ⁇ 2x, and b satisfies 0.05 ⁇ b.
- ⁇ 0.4 is satisfied, c and d satisfy 0 ⁇ (c + d), and c, d, e, and f satisfy 0.5 ⁇ (c + d + e + f) / b ⁇ ⁇ 100 ⁇ 10.
- the partition wall contains one or both of Na element and K element
- the silicon-containing phase is stabilized, and as a result, the honeycomb filter is not easily decomposed at high temperature and tends to be stable.
- Al, Mg, Ti, Si, Na, K, Ca, and Sr do not necessarily exist in the state of the compound shown in the composition formula (I).
- Na, K, Ca and Sr are each not a single oxide, but can be present, for example, as part of a silicon-containing phase.
- Mg and Al can exist not only as aluminum magnesium titanate and alumina, but also as part of the silicon-containing phase, for example.
- the above x satisfies 0 ⁇ x ⁇ 1, preferably satisfies 0.03 ⁇ x ⁇ 0.5, and more preferably satisfies 0.05 ⁇ x ⁇ 0.2.
- the y satisfies 0.5x ⁇ y ⁇ 3x, preferably satisfies 0.5x ⁇ y ⁇ 2x, and more preferably satisfies 0.7x ⁇ y ⁇ 2x.
- a satisfies 0.1x ⁇ a ⁇ 2x.
- a 0.1x or more, the effect of improving the mechanical strength of the honeycomb filter is obtained, and when it is less than 2x, the thermal expansion coefficient of the honeycomb filter can be reduced.
- a preferably satisfies 0.5x ⁇ a ⁇ 2x, and more preferably satisfies 0.5x ⁇ a ⁇ 1.5x.
- b satisfies 0.05 ⁇ b ⁇ 0.4.
- the honeycomb filter can obtain excellent mechanical strength, and when it is 0.4 or less, the thermal expansion coefficient of the honeycomb filter can be reduced.
- b preferably satisfies 0.05 ⁇ b ⁇ 0.2, more preferably satisfies 0.05 ⁇ b ⁇ 0.15, and 0.05 ⁇ b It is particularly preferable that ⁇ 0.1 is satisfied.
- C, d, e, and f satisfy 0.5 ⁇ (c + d + e + f) / b ⁇ ⁇ 100 ⁇ 10.
- ⁇ (c + d + e + f) / b ⁇ ⁇ 100 is larger than 0.5, the effect of improving the stability of the honeycomb filter at high temperature is obtained, and when it is less than 10, the effect of reducing the deterioration of the catalyst. Is obtained.
- c, d, e, and f preferably satisfy 1 ⁇ (c + d + e + f) / b ⁇ ⁇ 100 ⁇ 10, and 1 ⁇ (c + d + e + f) / b ⁇ ⁇ 100. It is more preferable to satisfy ⁇ 5.
- the partition may further contain an element other than Al, Mg, Ti, Si, Na, K, Ca, Sr and O as long as the effects of the present invention are not impaired.
- elements that may be included include Li, B, F, P, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Y, Zr, Nb, Sn, La, Ta, Examples include Be, Pb, and Bi.
- the total amount of these impurities is preferably 3% by mass or less in terms of oxide (F and P are in terms of pure substances).
- the partition includes a glass phase.
- the glass phase refers to an amorphous phase in which SiO 2 (silicon dioxide) is a main component.
- the partition wall does not show a peak indicating crystalline SiO 2 (crystalline silica-containing phase) in its powder X-ray diffraction spectrum, that is, all SiO 2 is present in the partition wall as a glass phase, Is preferred.
- the content of the glass phase in the partition walls is preferably 1% by mass or more from the viewpoint of improving the stability at a high temperature, and less than 5% by mass from the viewpoint of reducing the thermal expansion coefficient of the honeycomb filter. preferable.
- the partition may contain crystal phases other than an aluminum magnesium titanate crystal phase, an alumina phase, and a glass phase.
- a crystal phase include a phase derived from a raw material used for producing a ceramic fired body.
- the phase derived from the raw material is, for example, a phase derived from a titanium source powder, a magnesium source powder, or the like that remains without forming an aluminum magnesium titanate crystal phase in the manufacture of a honeycomb filter, and includes phases such as titania and magnesia. .
- the crystal phase forming the partition can be confirmed by an X-ray diffraction spectrum.
- Constituent materials of the catalyst layer include porous zeolite, phosphate-based porous material, alumina supporting noble metal, oxide containing titanium, oxide containing zirconium, oxide containing cerium, zirconium and cerium And oxides containing. These can be used individually by 1 type or in combination of 2 or more types.
- the zeolite used as the SCR catalyst further includes at least one metal element selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, rhodium, palladium, silver and platinum. It may be supported.
- the zeolite is a metal ion-exchanged zeolite ion-exchanged with the ions of the above metal elements, the NO X reducing property is improved.
- the metal ion exchanged zeolite cations such as sodium ions contained in the zeolite are replaced with other metal ions.
- the metal element is preferably at least one selected from the group consisting of copper, iron, vanadium, cobalt, nickel and silver, and particularly preferably copper. .
- Examples of the structure of zeolite and zeolite-like substances include MFI, BEA, MOR, FER, CHA, ERI, AEI, LTA, FAU, and MWW types defined by the International Zeolite Society.
- MSM includes ZSM-5
- AEI includes SSZ-39, AlPO-18, SAPO-18, and CHA.
- SSZ-13, AlPO-34, and SAPO-34 may be mentioned.
- MFI, BEA, MOR, FER, and FAU types are preferable from the viewpoint of the amount of HC adsorption.
- Typical examples of these include ZSM-5, ⁇ zeolite, mordenite, ferrierite, USY. Zeolite may be mentioned.
- the molar ratio of silica (SiO 2 ) and alumina (Al 2 O 3 ) of the zeolite (silica / alumina) is 5 to 10,000 from the viewpoint of obtaining an excellent NO X reducing ability. It is preferably 10 to 5,000.
- the honeycomb filter 100, 200 for example, a diesel engine, as well as collecting the trapped material such as soot contained in exhaust gas from an internal combustion engine such as a gasoline engine, for purifying NO X in the exhaust gas, the exhaust gas purification filter Suitable as
- the honeycomb filter 100 as shown in FIG. 3, the gas G supplied from the end face 100a to the flow path 110a passes through the communication holes in the catalyst layer 160 and the partition wall 120 and reaches the adjacent flow path 110b. And is discharged from the end face 100b.
- NO X in the gas G is reduced by the catalyst layer 160 to be decomposed into N 2 and H 2 O, and the collected material is collected on the surface of the partition wall 120 and in the communication hole, and from the gas G.
- the honeycomb filter 100 functions as an exhaust gas purification filter.
- the honeycomb filter 200 functions as an exhaust gas purification filter.
- FIG. 7 is a schematic view showing an embodiment of an exhaust gas purification system.
- the exhaust gas purification system of the present embodiment includes the honeycomb filter 100 described above.
- the exhaust gas purification system may include a honeycomb filter 200 instead of the honeycomb filter 100.
- a gas G discharged from an internal combustion engine 500 such as a diesel engine or a gasoline engine is first supplied to an oxidation catalyst (DOC: Diesel Oxidation Catalyst) 510.
- DOC Diesel Oxidation Catalyst
- a noble metal catalyst such as platinum or palladium is used. These noble metal catalysts are used, for example, supported on a honeycomb structure.
- the oxidation catalyst 510 removes most of hydrocarbons (hydrocarbon), carbon monoxide and the like contained in the gas G by oxidation.
- the gas G is supplied to the honeycomb filter 100, and removal of trapped substances such as soot and NO X purification are performed.
- Ammonia as a reducing agent for purifying NO X is produced by ejecting from the urea water supply device 520 urea water U in the gas G.
- NO X in the gas G is decomposed into N 2 and H 2 O.
- the exhaust gas purification system may further include an oxidation catalyst (DOC) at the subsequent stage of the honeycomb filter 100.
- DOC oxidation catalyst
- the oxidation catalyst provided in the subsequent stage of the honeycomb filter 100 is effective for removing the remaining ammonia.
- the honeycomb filter of the present invention has a SCR function, and has a function of adsorbing and burning hydrocarbons that could not be oxidized and removed by an oxidation catalyst and a function of a diesel particulate filter, and a catalyzed diesel particulate filter. It may be. Further, it may be a catalyzed diesel particulate filter carrying a noble metal catalyst for the purpose of promoting combustion of collected carbon particles and the like.
- a method for manufacturing a honeycomb filter includes, for example, a raw material preparation step for preparing a raw material mixture containing an inorganic compound powder and an additive, a forming step for forming a raw material mixture to obtain a formed body having a flow path, and firing the formed body.
- a firing step, and a sealing step of sealing one end of each flow path between the molding step and the firing step, or after the firing step, and a step of forming a catalyst layer after the firing step and the sealing step, Is further provided.
- the honeycomb filter manufacturing method preferably includes a step of washing the honeycomb fired body after the firing step and before the step of forming the catalyst layer.
- the inorganic compound powder includes, for example, an aluminum source powder, a titanium source powder (titanium source powder), a magnesium source powder, and a silicon source powder.
- the aluminum source powder include ⁇ -alumina powder.
- the titanium source powder include anatase type titania powder and rutile type titania powder.
- the magnesium source powder include magnesia powder and magnesia spinel powder.
- the silicon source powder include silicon oxide powder and glass frit.
- Examples of the calcium source powder include calcia powder, calcium carbonate powder, anorthite, and the like.
- strontium source powder examples include strontium oxide powder and strontium carbonate powder.
- yttrium source powder examples include yttrium oxide powder.
- barium source powder examples include barium oxide powder, barium carbonate powder, and feldspar.
- bismuth source powder examples include bismuth oxide powder.
- Each raw material powder may be one type or two or more types. Each raw material powder may contain a trace component derived from the raw material or inevitably contained in the production process.
- the total amount of Na 2 O and K 2 O in the aluminum source powder is not more than 0.25 mass% 0.001 mass% or more of aluminum source powder based on the total amount, Na 2 O and K 2 O in the magnesium source powder
- the total amount of Na 2 O and K 2 O in the titanium source powder is 0 based on the total amount of the titanium source powder. 0.001% by mass or more and 0.25% by mass or less, and the total amount of Na 2 O and K 2 O in the silicon source powder is 0.001% by mass or more and 0.25% by mass based on the total amount of the silicon source powder. It is necessary that:
- each upper limit of the total amount of Na 2 O and K 2 O of each raw material powder is preferably 0.20 mass%, and more preferably 0.15 mass%.
- the lower limit of the total amount of Na 2 O and K 2 O in each raw material powder is preferably 0.01% by mass.
- the silicon source powder is preferably one containing SiO 2 more than 95 wt%, and more preferably those containing SiO 2 more than 97 wt%.
- the silicon source powder preferably contains 90% by mass or more of the amorphous phase, and more preferably contains 95% by mass or more of the amorphous phase.
- a volume-based cumulative particle size equivalent to 50% (center particle size, D50) measured by a laser diffraction method is preferably in the following range.
- D50 of the aluminum source powder is, for example, 20 to 60 ⁇ m.
- D50 of the titanium source powder is, for example, 0.1 to 25 ⁇ m.
- the D50 of the magnesium source powder is, for example, 0.5 to 30 ⁇ m.
- D50 of the silicon source powder is, for example, 0.5 to 30 ⁇ m.
- the raw material mixture may contain aluminum titanate and / or aluminum magnesium titanate.
- the aluminum magnesium titanate corresponds to a raw material mixture having an aluminum source, a titanium source, and a magnesium source.
- additives examples include a pore-forming agent (pore-forming agent), a binder, a lubricant, a plasticizer, a dispersant, and a solvent.
- the pore-forming agent one formed by a material that disappears at a temperature lower than the temperature at which the molded body is degreased or fired in the firing process can be used.
- the pore forming agent disappears due to combustion or the like.
- a space is created at the location where the pore-forming agent was present, and the communication hole through which the fluid can flow is formed in the partition wall by shrinking the inorganic compound powder located between the spaces during firing. Can be formed.
- the pore-forming agent is, for example, corn starch, barley starch, wheat starch, tapioca starch, bean starch, rice starch, pea starch, coral starch, canna starch, potato starch (potato starch).
- the volume-based particle size (D50) equivalent to 50% of the cumulative percentage measured by laser diffraction method is, for example, 10 to 70 ⁇ m.
- the content of the pore-forming agent is, for example, 10 to 50 parts by mass with respect to 100 parts by mass of the inorganic compound powder.
- the binder is, for example, celluloses such as methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose; alcohols such as polyvinyl alcohol; salts such as lignin sulfonate; waxes such as paraffin wax and microcrystalline wax.
- Content of the binder in a raw material mixture is 20 mass parts or less with respect to 100 mass parts of inorganic compound powder, for example.
- Lubricants and plasticizers include, for example, alcohols such as glycerin; higher fatty acids such as caprylic acid, lauric acid, palmitic acid, alginic acid, oleic acid, stearic acid; stearic acid metal salts such as Al stearate; polyoxyalkylene Alkyl ether (for example, polyoxyethylene polyoxypropylene butyl ether).
- the content of the lubricant and the plasticizer in the raw material mixture is, for example, 10 parts by mass or less with respect to 100 parts by mass of the inorganic compound powder.
- the dispersant examples include inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, citric acid, acetic acid, malic acid, and lactic acid; alcohols such as methanol, ethanol, and propanol; ammonium polycarboxylate.
- Content of the dispersing agent in a raw material mixture is 20 mass parts or less with respect to 100 mass parts of inorganic compound powder, for example.
- the solvent is, for example, water, and ion-exchanged water is preferable in terms of few impurities.
- the content of the solvent is, for example, 10 to 100 parts by mass with respect to 100 parts by mass of the inorganic compound powder.
- a green honeycomb formed body having a honeycomb structure is obtained.
- a so-called extrusion molding method in which the raw material mixture is extruded from a die while being kneaded by a single screw extruder can be employed.
- the honeycomb structured green honeycomb formed body obtained in the forming step is fired to obtain a honeycomb fired body.
- calcination degreasing for removing a binder or the like contained in the molded body (in the raw material mixture) may be performed before the molded body is fired.
- the firing temperature is usually 1300 ° C. or higher, preferably 1400 ° C. or higher.
- a calcination temperature is 1650 degrees C or less normally, Preferably it is 1550 degrees C or less.
- the temperature raising rate is not particularly limited, but is usually 1 to 500 ° C./hour.
- the firing time may be a time sufficient for the inorganic compound powder to transition to the aluminum titanate-based crystal, and varies depending on the amount of raw material, type of firing furnace, firing temperature, firing atmosphere, etc., but usually 10 minutes to 24 hours.
- the sealing step is performed between the molding step and the firing step or after the firing step.
- a sealing step is performed between the forming step and the firing step, one end of each flow path of the green honeycomb molded body obtained in the forming step is sealed with a sealing material, and then green honeycomb forming is performed in the firing step.
- a honeycomb structure including a sealing portion that seals one end of the flow path is obtained.
- the sealing step after the firing step after sealing one end of each flow path of the honeycomb fired body obtained in the firing step with the sealing material, the flow path is obtained by firing the sealing material together with the honeycomb fired body.
- a honeycomb structure provided with a sealing portion that seals one end of the above is obtained.
- As the sealing material a mixture similar to the raw material mixture for obtaining the green honeycomb molded body can be used.
- the cleaning step is a step of cleaning the honeycomb fired body after the firing step and before the step of forming the catalyst layer.
- the honeycomb fired body can be washed using an alkaline solution, an acid solution, steam, or the like, but is preferably washed using an alkaline solution, and more preferably an alkaline solution having a pH of 9 or more.
- the alkaline solution include an aqueous ammonia solution and an aqueous sodium hydroxide solution.
- the catalyst layer forming step is performed after the firing step and the sealing step.
- a catalyst is mixed with water to produce a slurry, and then the produced slurry is applied to the honeycomb structure.
- silica sol and / or alumina sol may be added to the slurry. An example of a slurry application method is shown below.
- the prepared slurry is divided into the inside of the flow path (first flow path) where the gas inlet side of the honeycomb structure is open and the inside of the flow path (second flow path) where the gas outlet side is open. And apply to the partition wall surface.
- the film is dried at 400 to 600 ° C. for about 0.1 to 5 hours to remove moisture.
- the catalyst layer also enters inside the pores of the partition walls (inside the communication holes), and is formed not only on the surface of the partition walls in the flow path but also on the surfaces inside the pores of the partition walls.
- a honeycomb filter provided with a catalyst layer in the partition wall surfaces and partition pores in the first and second flow paths can be obtained.
- the aluminum titanate-based ceramic is a main component for forming the partition walls of the honeycomb filter described above, and satisfies the composition formula (I). Moreover, the aluminum titanate-based ceramics can be manufactured by a method similar to the method described in the honeycomb filter manufacturing method. The aluminum titanate-based ceramics can also be used as a material other than the partition walls of the honeycomb filter, and the shape thereof can be made according to the purpose of use.
- Example 1 Raw material powder of aluminum magnesium titanate (Al 2 O 3 powder (a), TiO 2 powder, MgO powder), SiO 2 powder (a), pore former, organic binder, plasticizer, lubricant and water (solvent) The raw material mixture was prepared by mixing. The content of each component in the raw material mixture was adjusted to the following values. Table 2 below shows the Na 2 O content and the K 2 O content of the Al 2 O 3 powder (a), the TiO 2 powder, the MgO powder, and the SiO 2 powder (a).
- Al 2 O 3 powder (a) (Navaltech, trade name: NO105RS): 38.7 parts by mass TiO 2 powder (Chronos, trade name: SR-240): 36.2 parts by mass MgO powder (Ube) Manufactured by Kosan Co., Ltd., trade name: UC95S): 2.0 parts by mass SiO 2 powder (a) (manufactured by Fuji Silysia Co., Ltd., trade name: Silicia 350): 3.0 parts by mass Pore forming agent (average particle diameter obtained from potato 25 ⁇ m starch): 20.0 parts by mass Organic binder (a) (hydroxypropylmethylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 65SH-30000): 6.3 parts by mass Plasticizer (polyoxyethylene polyoxypropylene monobutyl ether) : 4.5 parts by mass Lubricant (glycerin): 0.4 parts by mass Water: 31 parts by mass
- the above raw material mixture was kneaded and then extrusion molded to obtain a cylindrical honeycomb molded body having a number of through holes (cross-sectional shape: square) in the longitudinal direction.
- the obtained honeycomb formed body was heated to 1500 ° C. at a temperature rising rate of 80 ° C./hour in the air with a box-type electric furnace, and fired by holding at the same temperature for 5 hours to prepare a honeycomb fired body.
- the obtained honeycomb fired body was subjected to elemental analysis by ICP emission spectroscopic analysis, atomic absorption analysis, and flame analysis, and x, y, a, b when the elemental composition ratio was expressed by the composition formula (I) , C, d, e and f were determined.
- Table 3 The results are shown in Table 3.
- a fired body was obtained.
- the slurry of Cu-ZSM-5 30 parts by mass of ZSM-5 type zeolite and 70 parts by mass of water are wet-mixed so that the copper ion is 3% by mass (solid content ratio) in terms of CuO with respect to the zeolite. It was prepared by ion exchange.
- the supported amount of the catalyst with respect to 100 parts by weight of the honeycomb fired body was 7.1 parts by weight.
- the above raw material mixture was kneaded and then extrusion molded to obtain a cylindrical honeycomb molded body having a number of through holes (cross-sectional shape: square) in the longitudinal direction.
- the obtained honeycomb formed body was heated to 1500 ° C. at a temperature rising rate of 80 ° C./hour in the air with a box-type electric furnace, and fired by holding at the same temperature for 5 hours to prepare a honeycomb fired body.
- the obtained honeycomb fired body was subjected to elemental analysis by ICP emission spectroscopic analysis, atomic absorption analysis, and flame analysis, and x, y, a, b when the elemental composition ratio was expressed by the composition formula (I) , C, d, e and f were determined.
- Table 3 The results are shown in Table 3.
- honeycomb fired body was coated with the same Cu-ZSM-5 slurry as that used in Example 1 as a catalyst by a dipping method to obtain a catalyst-coated honeycomb fired body.
- the supported amount of the catalyst with respect to 100 parts by weight of the honeycomb fired body was 9.2 parts by weight.
- Example 2 Raw material powder of aluminum magnesium titanate (Al 2 O 3 powder (a), TiO 2 powder, MgO powder), SiO 2 powder (a), pore former, organic binder, plasticizer, lubricant and water (solvent) The raw material mixture was prepared by mixing. The content of each component in the raw material mixture was adjusted to the following values. Further, Al 2 O 3 powder (a), TiO 2 powder, MgO powder, and, as the SiO 2 powder (a), a material shown in Table 1.
- Al 2 O 3 powder (a) (Navaltech, trade name: NO105RS): 38.7 parts by mass TiO 2 powder (Chronos, trade name: SR-240): 36.5 parts by mass MgO powder (Ube) Manufactured by Kosan Co., Ltd., trade name: UC95S): 1.9 parts by mass SiO 2 powder (a) (manufactured by Fuji Silysia Co., Ltd., trade name: Silicia 350): 2.8 parts by mass Pore-forming agent (average particle diameter obtained from potato 25 ⁇ m starch): 20.0 parts by mass Organic binder (a) (hydroxypropylmethylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 65SH-30000): 6.3 parts by mass Plasticizer (polyoxyethylene polyoxypropylene monobutyl ether) : 4.5 parts by mass Lubricant (glycerin): 0.4 parts by mass Water: 31 parts by mass
- the above raw material mixture was kneaded and then extrusion molded to obtain a cylindrical honeycomb molded body having a number of through holes (cross-sectional shape: square) in the longitudinal direction.
- the obtained honeycomb formed body was heated to 1500 ° C. at a temperature rising rate of 80 ° C./hour in the air with a box-type electric furnace, and fired by holding at the same temperature for 5 hours to prepare a honeycomb fired body.
- the obtained honeycomb fired body was subjected to elemental analysis by ICP emission spectroscopic analysis, atomic absorption analysis, and flame analysis, and x, y, a, b when the elemental composition ratio was expressed by the composition formula (I) , C, d, e and f were determined.
- Table 3 The results are shown in Table 3.
- the obtained honeycomb fired body was coated with a slurry of ⁇ zeolite as a catalyst by a dip method to obtain a catalyst-coated honeycomb fired body.
- the ⁇ zeolite slurry is prepared by wet-mixing 20 parts by mass of ⁇ zeolite and 80 parts by mass of water.
- the supported amount of the catalyst with respect to 100 parts by weight of the honeycomb fired body was 7.8 parts by weight.
- Example 2 A honeycomb fired body was produced in the same manner as in Comparative Example 1. The obtained honeycomb fired body was coated with the same ⁇ zeolite slurry as that used in Example 2 as a catalyst by a dipping method to obtain a catalyst-coated honeycomb fired body. In the catalyst-coated honeycomb fired body, the supported amount of the catalyst with respect to 100 parts by weight of the honeycomb fired body was 5.0 parts by weight.
- a catalyst-only sample was prepared as Reference Example 1.
- the catalyst-coated honeycomb fired bodies obtained in the respective Examples and Comparative Examples were pulverized to obtain samples for evaluation.
- Samples of Examples, Comparative Examples and Reference Examples are shown in Tables 4 and 5 below in an environment where the H 2 O concentration and the O 2 concentration are both 10% by volume and the N 2 concentration is 80% by volume.
- Heat treatment was performed under heat treatment conditions (900 ° C. for 5 hours or 750 ° C. for 16 hours). For each sample before and after the heat treatment, the BET specific surface area was measured for the samples of Example 1 and Comparative Example 1, and the NH 3 -TPD measurement was performed for the samples of Example 2, Comparative Example 2 and Reference Example 1.
- NH 3 -TPD is a method for measuring desorbed gas generated by increasing the temperature after adsorbing NH 3 to each sample. Specific measurement conditions for NH 3 -TPD are as follows.
- the measurement results of NH 3 -TPD shown in Table 5 are obtained as relative values with respect to the NH 3 desorption amount ( ⁇ mol / g) measured for the sample before heat treatment of Reference Example 1 as 100%. .
- the higher this value the higher the acid amount on the sample surface, the better the adsorption performance of hydrocarbons, etc., and the better the catalyst performance.
- Example 3 Raw material powder of aluminum magnesium titanate (Al 2 O 3 powder (a), TiO 2 powder, MgO powder), SiO 2 powder (c), pore former, organic binder (a), plasticizer, lubricant and water ( Solvent) was mixed to prepare a raw material mixture.
- Al 2 O 3 powder (a), TiO 2 powder, MgO powder), SiO 2 powder (c), pore former, organic binder (a), plasticizer, lubricant and water ( Solvent) was mixed to prepare a raw material mixture.
- the content of each component in the raw material mixture is shown in Table 6 below (unit: parts by mass). Details of each component shown in Table 6 are as follows.
- Table 7 below shows the Al 2 O 3 powder, the TiO 2 powder, the MgO powder, the SiO 2 powder, and the Na 2 O content and K 2 O content of the organic binder.
- Al 2 O 3 powder (a) (manufactured by Naval Tech, trade name: NO105RS) Al 2 O 3 powder (b) (manufactured by Sumitomo Chemical Co., Ltd., trade name: A-21) TiO 2 powder (Chronos Co., Ltd., trade name: SR-240) MgO powder (product name: UC95S, manufactured by Ube Industries) SiO 2 powder (b) (manufactured by Nippon Fritt, trade name: CK0160M1) SiO 2 powder (c) (manufactured by Tatsumori, trade name: Y-40) Pore-forming agent (starch with average particle size of 25 ⁇ m obtained from potato) Organic binder (a) (hydroxypropylmethylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 65SH-30000) Organic binder (b) (hydroxypropylmethylcellulose, manufactured by Samsung Seimitsu Chemical Co., Ltd., trade name: PMB-30
- the above raw material mixture was kneaded and then extrusion molded to obtain a cylindrical honeycomb molded body having a number of through holes (cross-sectional shape: square) in the longitudinal direction.
- the obtained honeycomb formed body was heated to 1500 ° C. at a temperature rising rate of 80 ° C./hour in the air with a box-type electric furnace, and fired by holding at the same temperature for 5 hours to prepare a honeycomb fired body.
- the obtained honeycomb fired body was subjected to elemental analysis by ICP emission spectroscopic analysis, atomic absorption analysis, and flame analysis, and x, y, a, b when the elemental composition ratio was expressed by the composition formula (I) , C, d, e and f were determined. The results are shown in Table 8.
- honeycomb fired body was coated with the same Cu-ZSM-5 slurry as that used in Example 1 as a catalyst by a dipping method to obtain a catalyst-coated honeycomb fired body.
- the supported amount of catalyst with respect to 100 parts by mass of the honeycomb fired body was as shown in Table 9.
- honeycomb fired bodies were manufactured in the same manner as Example 3 with the raw material types and mixing ratios shown in Table 6.
- the obtained honeycomb fired body was subjected to elemental analysis by ICP emission spectroscopic analysis, atomic absorption analysis, and flame analysis, and x, y, a, b when the elemental composition ratio was expressed by the composition formula (I) , C, d, e and f were determined.
- the results are shown in Table 8.
- honeycomb fired body was coated with the same Cu-ZSM-5 slurry as that used in Example 1 as a catalyst by a dipping method to obtain a catalyst-coated honeycomb fired body.
- the supported amount of catalyst with respect to 100 parts by mass of the honeycomb fired body was as shown in Table 9.
- Reactive gas A mixed gas (reaction gas) in which the H 2 O concentration and the O 2 concentration were both 8% by volume, the NO concentration and the NH 3 concentration were both 900 ppm by volume, and the N 2 concentration was 83.8% by volume was prepared. This reaction gas was supplied to the NO meter at a gas flow rate of 513 ml / min to measure the NO concentration, and recorded as the pre-gas NO concentration indicating the NO concentration immediately before the start of the reaction.
- reaction temperature Each measurement was performed at a reaction temperature of 300 ° C.
- NO removal performance was evaluated by the following methods, respectively. First, an evaluation sample was filled in a quartz reaction tube so that the amount of Cu-ZSM-5 was 41 mg, and the above reaction gas was supplied to the reaction tube at a gas flow rate of 513 ml / min while the above reaction was carried out in the reaction tube. The temperature was raised to 5 ° C / min. 10 minutes, 20 minutes, and 30 minutes after the reaction temperature is reached, the NO concentration of the reaction gas after passing through the sample for evaluation is measured with the NO meter, and the average value of the three points is the NO gas concentration during the reaction. It was. The NO removal performance was calculated by the following formula. ⁇ 1- (NO gas concentration during reaction / pre-gas NO concentration) ⁇ ⁇ 100 (%)
- Table 10 shows the measurement results of NO removal performance. The higher this value, the better the NO removal performance and the better the catalyst performance. Further, the smaller the decrease in the NO removal performance after the heat treatment relative to the NO removal performance before the heat treatment, the more the deterioration of the catalyst when the catalyst-coated honeycomb fired body is exposed to a high temperature can be suppressed. This effect can be similarly achieved even when a honeycomb filter is formed by sealing the catalyst-coated honeycomb fired body.
- a honeycomb filter capable of suppressing deterioration of a catalyst when exposed to a high temperature, a manufacturing method thereof, an aluminum titanate ceramic, and a manufacturing method thereof.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Filtering Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Geometry (AREA)
- Catalysts (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Processes For Solid Components From Exhaust (AREA)
Abstract
Description
CO(NH2)2+H2O→2NH3+CO2 (1)
4NH3+4NO+O2→4N2+6H2O (2)
2NH3+NO+NO2→2N2+3H2O (3)
8NH3+6NO2→7N2+12H2O (4)
この他、SCRとしては、炭化水素を還元剤として用いる、炭化水素SCRも知られている。
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足する、ハニカムフィルタを提供する。
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足する、ハニカムフィルタの製造方法であって、アルミニウム源、マグネシウム源、チタン源、ケイ素源、造孔剤、バインダ及び溶媒を含み、上記アルミニウム源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、上記マグネシウム源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、上記チタン源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、且つ、上記ケイ素源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下である原料混合物を成形及び焼成してハニカム焼成体を得る工程と、上記ハニカム焼成体の上記隔壁表面の少なくとも一部及び/又は前記隔壁の細孔内部の少なくとも一部に上記触媒を担持して上記ハニカムフィルタを得る工程と、を含むハニカムフィルタの製造方法を提供する。
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足する、チタン酸アルミニウム系セラミックスを提供する。
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足するチタン酸アルミニウム系セラミックスを得る工程を含む、チタン酸アルミニウム系セラミックスの製造方法を提供する。
図1は、第1実施形態に係るハニカムフィルタを模式的に示す図であり、図1(a)はハニカムフィルタの斜視図及び端面の拡大図であり、図1(b)は、図1(a)における領域R1の拡大図である。図2(a)は、図1に示したハニカムフィルタにおける図1(b)の反対側の端面の拡大図であり、図2(b)は、隔壁断面の拡大図である。図3は、図1(a)のIII-III矢視図である。ハニカムフィルタ100は、一方の端面(第1の端面)100aと、端面100aの反対側に位置する他方の端面(第2の端面)100bと、を有している。
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足する。
次に、ハニカムフィルタの製造方法の一実施形態について説明する。ハニカムフィルタの製造方法は、例えば、無機化合物粉末及び添加剤を含む原料混合物を調製する原料調製工程と、原料混合物を成形して、流路を有する成形体を得る成形工程と、成形体を焼成する焼成工程と、を備え、成形工程と焼成工程の間、又は、焼成工程の後に、各流路の一端を封口する封口工程と、焼成工程及び封口工程後に、触媒層を形成する工程と、を更に備える。また、ハニカムフィルタの製造方法は、焼成工程の後、且つ、触媒層を形成する工程の前に、ハニカム焼成体を洗浄する工程を含むことが好ましい。以下、各工程について説明する。
原料調製工程では、無機化合物粉末と添加剤とを混合した後に混練して原料混合物を調製する。無機化合物粉末は、例えば、アルミニウム源粉末、チタン源粉末(チタニウム源粉末)、マグネシウム源粉末、及び、ケイ素源粉末を含む。アルミニウム源粉末としては、例えば、α-アルミナ粉末等が挙げられる。チタン源粉末としては、例えば、アナターゼ型のチタニア粉末、ルチル型のチタニア粉末等が挙げられる。マグネシウム源粉末としては、例えば、マグネシア粉末、マグネシアスピネル粉末等が挙げられる。ケイ素源粉末としては、例えば、酸化ケイ素粉末、ガラスフリット等が挙げられる。カルシウム源粉末としては、例えば、カルシア粉末、炭酸カルシウム粉末、灰長石等が挙げられる。ストロンチウム源粉末としては、例えば、酸化ストロンチウム粉末、炭酸ストロンチウム粉末等が挙げられる。イットリウム源粉末としては、例えば、酸化イットリウム粉末等が挙げられる。バリウム源粉末としては、例えば、酸化バリウム粉末、炭酸バリウム粉末、長石等が挙げられる。ビスマス源粉末としては、例えば、酸化ビスマス粉末等が挙げられる。各原料粉末は、1種又は2種以上のいずれでもよい。各原料粉末は、その原料由来又は製造工程において不可避的に含まれる微量成分を含有し得る。
成形工程では、ハニカム構造を有するグリーンハニカム成形体を得る。成形工程では、例えば、一軸押出機により原料混合物を混練しながらダイから押出す、いわゆる押出成形法を採用することができる。
焼成工程では、成形工程において得られたハニカム構造のグリーンハニカム成形体を焼成してハニカム焼成体を得る。焼成工程では、成形体の焼成前に、成形体中(原料混合物中)に含まれるバインダ等を除去するための仮焼(脱脂)が行われてもよい。成形体の焼成において、焼成温度は、通常1300℃以上であり、好ましくは1400℃以上である。また、焼成温度は、通常1650℃以下であり、好ましくは1550℃以下である。昇温速度は特に限定されるものではないが、通常1~500℃/時間である。焼成時間は、無機化合物粉末がチタン酸アルミニウム系結晶に遷移するのに充分な時間であればよく、原料の量、焼成炉の形式、焼成温度、焼成雰囲気等により異なるが、通常は10分~24時間である。
封口工程は、成形工程と焼成工程の間、又は、焼成工程の後に行われる。成形工程と焼成工程の間に封口工程を行う場合、成形工程において得られた未焼成のグリーンハニカム成形体の各流路の一方の端部を封口材で封口した後、焼成工程においてグリーンハニカム成形体と共に封口材を焼成することにより、流路の一方の端部を封口する封口部を備えるハニカム構造体が得られる。焼成工程の後に封口工程を行う場合、焼成工程において得られたハニカム焼成体の各流路の一方の端部を封口材で封口した後、ハニカム焼成体と共に封口材を焼成することにより、流路の一方の端部を封口する封口部を備えるハニカム構造体が得られる。封口材としては、上記グリーンハニカム成形体を得るための原料混合物と同様の混合物を用いることができる。
洗浄工程は、焼成工程の後、且つ、触媒層を形成する工程の前に、ハニカム焼成体を洗浄する工程である。焼成工程の後に封口工程を行う場合には、洗浄工程は封口工程の後に行うことが好ましい。ハニカム焼成体の洗浄は、アルカリ溶液、酸溶液、スチーム等を用いて行うことができるが、アルカリ溶液を用いて洗浄することが好ましく、pH9以上のアルカリ溶液を用いて行うことがより好ましい。アルカリ溶液としては、例えば、アンモニア水溶液、水酸化ナトリウム水溶液等が挙げられる。上記洗浄工程を行うことにより、隔壁表面に存在するNa元素及びK元素を除去することができ、隔壁表面におけるNa元素及びK元素の存在量を低減することができる。これにより、触媒の劣化をより低減させる効果が得られる。
触媒層形成工程は、焼成工程及び封口工程の後に行われる。触媒層形成工程では、まず、触媒を水と混ぜ合わせてスラリーを作製し、次に、作製したスラリーをハニカム構造体に塗布する。スラリーには、触媒及び水に加えて、シリカゾル及び/又はアルミナゾルを添加してもよい。スラリーの塗布方法の一例を以下に示す。
チタン酸アルミニウム系セラミックスは、上述したハニカムフィルタの隔壁を形成する主成分となるものであり、組成式(I)を満たすものである。また、チタン酸アルミニウム系セラミックスは、ハニカムフィルタの製造方法において説明した方法と同様の方法により製造することができる。なお、チタン酸アルミニウム系セラミックスは、ハニカムフィルタの隔壁以外の材料として用いることも可能であり、その形状は使用目的に応じた形状にすることができる。
チタン酸アルミニウムマグネシウムの原料粉末(Al2O3粉末(a)、TiO2粉末、MgO粉末)、SiO2粉末(a)、造孔剤、有機バインダ、可塑剤、潤滑剤及び水(溶媒)を混合して原料混合物を調製した。原料混合物中の各成分の含有量は下記の値に調整した。また、Al2O3粉末(a)、TiO2粉末、MgO粉末、及び、SiO2粉末(a)のNa2O含有量及びK2O含有量を下記表1に示す。
Al2O3粉末(a)(ナバルテック社製、商品名:NO105RS):38.7質量部
TiO2粉末(クロノス社製、商品名:SR-240):36.2質量部
MgO粉末(宇部興産社製、商品名:UC95S):2.0質量部
SiO2粉末(a)(富士シリシア社製、商品名:サイリシア350):3.0質量部
造孔剤(馬鈴薯から得た平均粒径25μmの澱粉):20.0質量部
有機バインダ(a)(ヒドロキシプロピルメチルセルロース、信越化学社製、商品名:65SH-30000):6.3質量部
可塑剤(ポリオキシエチレンポリオキシプロピレンモノブチルエーテル):4.5質量部
潤滑剤(グリセリン):0.4質量部
水:31質量部
チタン酸アルミニウムマグネシウムの原料粉末(Al2O3粉末(b)、TiO2粉末、MgO粉末)、SiO2粉末(b)、造孔剤、有機バインダ、可塑剤、潤滑剤及び水(溶媒)を混合して原料混合物を調製した。原料混合物中の各成分の含有量は下記の値に調整した。また、Al2O3粉末(b)、TiO2粉末、MgO粉末、及び、SiO2粉末(b)のNa2O含有量及びK2O含有量を下記表2に示す。
Al2O3粉末(b)(住友化学社製、商品名:A-21):39.5質量部
TiO2粉末(クロノス社製、商品名:SR-240):36.2質量部
MgO粉末(宇部興産社製、商品名:UC95S):1.9質量部
SiO2粉末(b)(日本フリット社製、商品名:CK0160M1):2.3質量部
造孔剤(馬鈴薯から得た平均粒径25μmの澱粉):20.0質量部
有機バインダ(a)(ヒドロキシプロピルメチルセルロース、信越化学社製、商品名:65SH-30000):6.3質量部
可塑剤(ポリオキシエチレンポリオキシプロピレンモノブチルエーテル):4.5質量部
潤滑剤(グリセリン):0.4質量部
水:31質量部
チタン酸アルミニウムマグネシウムの原料粉末(Al2O3粉末(a)、TiO2粉末、MgO粉末)、SiO2粉末(a)、造孔剤、有機バインダ、可塑剤、潤滑剤及び水(溶媒)を混合して原料混合物を調製した。原料混合物中の各成分の含有量は下記の値に調整した。また、Al2O3粉末(a)、TiO2粉末、MgO粉末、及び、SiO2粉末(a)としては、上記表1に示す材料を用いた。
Al2O3粉末(a)(ナバルテック社製、商品名:NO105RS):38.7質量部
TiO2粉末(クロノス社製、商品名:SR-240):36.5質量部
MgO粉末(宇部興産社製、商品名:UC95S):1.9質量部
SiO2粉末(a)(富士シリシア社製、商品名:サイリシア350):2.8質量部
造孔剤(馬鈴薯から得た平均粒径25μmの澱粉):20.0質量部
有機バインダ(a)(ヒドロキシプロピルメチルセルロース、信越化学社製、商品名:65SH-30000):6.3質量部
可塑剤(ポリオキシエチレンポリオキシプロピレンモノブチルエーテル):4.5質量部
潤滑剤(グリセリン):0.4質量部
水:31質量部
比較例1と同様にして、ハニカム焼成体を作製した。得られたハニカム焼成体に、触媒として実施例2で用いたものと同じβゼオライトのスラリーをディップ法によりコートし、触媒コートハニカム焼成体を得た。触媒コートハニカム焼成体において、ハニカム焼成体100質量部に対する触媒の担持量は5.0質量部であった。
各実施例及び各比較例で得られたハニカム焼成体を粉砕し、粉末X線回折スペクトルを得たところ、いずれのハニカム焼成体でも、チタン酸アルミニウムマグネシウムの結晶相を示す回折ピークが現れたが、結晶性SiO2(結晶性のシリカ含有相)を示すピークは現れなかった。
比較のために、触媒のみのサンプルを参考例1として用意した。また、各実施例及び各比較例で得られた触媒コートハニカム焼成体を粉砕して評価用のサンプルとした。各実施例、各比較例及び参考例のサンプルを、H2O濃度及びO2濃度がいずれも10体積%、N2濃度が80体積%である環境下で、下記表4及び表5に示す熱処理条件(900℃で5時間、又は、750℃で16時間)で熱処理を行った。熱処理前後の各サンプルについて、実施例1及び比較例1のサンプルについてはBET比表面積の測定を行い、実施例2、比較例2及び参考例1のサンプルについてはNH3-TPD測定を行った。BET比表面積の測定結果を表4に、NH3-TPDの測定結果を表5にそれぞれ示す。なお、NH3-TPDは、各サンプルにNH3を吸着させた後、温度を上昇させることによって生じる脱離ガスを測定する方法である。NH3-TPDの具体的な測定条件は以下の通りである。
サンプル約0.05gを測定用セルに入れ、He気流中(50ml/min)で室温から500℃に昇温(10℃/min)し、500℃で60分間、保持した。その後、He気流中(50ml/min)のまま、100℃まで降温した。
[NH3吸着]
100℃で0.5%NH3/Heガス(100ml/min)を30分間、吸着させた。
[NH3脱気]
100℃で30分間、He気流中(50ml/min)にて排気した。
[昇温脱離測定]
He気流中(50ml/min)で100℃から800℃まで昇温(10℃/min)し、脱離するNH3量を四重極MSで検出した(m/z=16)。
[酸量の解析]
各測定で得られたNH3脱離ピークの面積値(カウント数)を算出した。このとき、200~500℃でのNH3脱離量の積算を酸量とした。毎回、測定の最後に定量用測定を行い、既知濃度のガス(0.5%NH3/Heガス)を30分流通(50ml/min)させた。既知のガス濃度(0.5%NH3/Heガス)、流通時間(30分間)、流量(50ml/min)から、この時の一定時間の面積値(カウント数)から、1カウントあたりのガスのmol数を算出した。その値をファクター(mol/カウント)とし、NH3脱離ピークのカウント数にかけて、サンプリング重量で割ることにより、1gあたりのNH3脱離量(μmol/g)を算出した。
チタン酸アルミニウムマグネシウムの原料粉末(Al2O3粉末(a)、TiO2粉末、MgO粉末)、SiO2粉末(c)、造孔剤、有機バインダ(a)、可塑剤、潤滑剤及び水(溶媒)を混合して原料混合物を調製した。原料混合物中の各成分の含有量は下記表6に示す(単位:質量部)。表6に示した各成分の詳細は、以下に示す通りである。また、用いたAl2O3粉末、TiO2粉末、MgO粉末、及び、SiO2粉末、有機バインダのNa2O含有量及びK2O含有量を下記表7に示す。
Al2O3粉末(a)(ナバルテック社製、商品名:NO105RS)
Al2O3粉末(b)(住友化学社製、商品名:A-21)
TiO2粉末(クロノス社製、商品名:SR-240)
MgO粉末(宇部興産社製、商品名:UC95S)
SiO2粉末(b)(日本フリット社製、商品名:CK0160M1)
SiO2粉末(c)(龍森社製、商品名:Y-40)
造孔剤(馬鈴薯から得た平均粒径25μmの澱粉)
有機バインダ(a)(ヒドロキシプロピルメチルセルロース、信越化学社製、商品名:65SH-30000)
有機バインダ(b)(ヒドロキシプロピルメチルセルロース、三星精密化学社製、商品名:PMB-30U)
可塑剤(ポリオキシエチレンポリオキシプロピレンモノブチルエーテル)
潤滑剤(グリセリン)
各実施例及び比較例において、表6に示す通りの原料種及び混合比で、実施例3と同じ要領でハニカム焼成体を作製した。得られたハニカム焼成体について、ICP発光分光分析法、原子吸光分析法及び炎光分析法により元素分析を行い、元素組成比を組成式(I)で表したときのx、y、a、b、c、d、e及びfの値を求めた。その結果を表8に示す。
各実施例及び各比較例で得られた触媒コートハニカム焼成体を粉砕し、500μm~1000μmに篩別して評価用のサンプルとした。得られた各サンプルをH2O濃度及びO2濃度がいずれも10体積%、N2濃度が80体積%、ガス流量550ml/minである環境下において550℃で5時間保持して熱処理した。
上記熱処理前後の各サンプルについて、NO除去性能を測定した。具体的な測定条件は以下の通りである。
NOガスの濃度は、NO計としてアナテック・ヤナコ製ECL-88AO-Liteを用いて測定した。
H2O濃度及びO2濃度がいずれも8体積%、NO濃度及びNH3濃度がいずれも900体積ppm、N2濃度が83.8体積%である混合ガス(反応ガス)を調製した。この反応ガスを513ml/minのガス流量で上記NO計に供給してNO濃度の測定を行い、反応開始直前のNO濃度を示す、前ガスNO濃度として記録した。
300℃の反応温度でそれぞれ測定を行った。
上記の前処理で得られた熱処理前後の評価用サンプルについて、それぞれ以下の方法でNO除去性能を評価した。まず、評価用サンプルをCu-ZSM-5の量が41mgとなるように石英製反応管に充填し、上記反応ガスを513ml/minのガス流量で反応管に供給しながら、反応管内を上記反応温度まで5℃/minで昇温した。反応温度到達時から10分後、20分後、30分後に、評価用サンプルを通過した後の反応ガスのNO濃度を上記NO計により測定し、3点の平均値を反応時のNOガス濃度とした。NOの除去性能は下記の式で算出した。
{1-(反応時のNOガス濃度/前ガスNO濃度)}×100(%)
Claims (16)
- 互いに平行な複数の流路を形成する隔壁と、前記隔壁の表面の少なくとも一部及び/又は前記隔壁の細孔内部の少なくとも一部に担持された触媒と、を備えるハニカムフィルタであって、
前記ハニカムフィルタが、第1の端面と、当該第1の端面の反対側に位置する第2の端面と、を有し、
前記複数の流路が、前記第2の端面側の端部が封口された複数の第1の流路と、前記第1の端面側の端部が封口された複数の第2の流路と、を有し、
前記隔壁中のAl、Mg、Ti、Si、Na、K、Ca及びSrの元素組成比を下記組成式(I);
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足する、ハニカムフィルタ。 - 前記隔壁の粉末X線回折スペクトルに、結晶性のシリカ含有相を示すピークが現れない、請求項1に記載のハニカムフィルタ。
- 前記触媒がゼオライトを含む、請求項1又は2に記載のハニカムフィルタ。
- 互いに平行な複数の流路を形成する隔壁と、前記隔壁の表面の少なくとも一部及び/又は前記隔壁の細孔内部の少なくとも一部に担持された触媒と、を備え、
第1の端面と、当該第1の端面の反対側に位置する第2の端面と、を有し、
前記複数の流路が、前記第2の端面側の端部が封口された複数の第1の流路と、前記第1の端面側の端部が封口された複数の第2の流路と、を有し、
前記隔壁中のAl、Mg、Ti、Si、Na、K、Ca及びSrの元素組成比を下記組成式(I);
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足する、ハニカムフィルタの製造方法であって、
アルミニウム源、マグネシウム源、チタン源、ケイ素源、造孔剤、バインダ及び溶媒を含み、前記アルミニウム源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、前記マグネシウム源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、前記チタン源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、且つ、前記ケイ素源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下である原料混合物を成形及び焼成してハニカム焼成体を得る工程と、
前記ハニカム焼成体の前記隔壁表面の少なくとも一部及び/又は前記隔壁の細孔内部の少なくとも一部に前記触媒を担持して前記ハニカムフィルタを得る工程と、
を含むハニカムフィルタの製造方法。 - 前記ケイ素源がSiO2を95質量%以上含む、請求項4に記載の製造方法。
- 前記ケイ素源が非晶質相を90質量%以上含む、請求項4又は5に記載の製造方法。
- 前記触媒を担持させる前に、前記ハニカム焼成体を洗浄する工程を含む、請求項4~6のいずれか一項に記載の製造方法。
- 前記ハニカム焼成体の洗浄は、pH9以上のアルカリ溶液により行う、請求項7記載の製造方法。
- 前記触媒がゼオライトを含む、請求項4~8のいずれか一項に記載の製造方法。
- Al、Mg、Ti、Si、Na、K、Ca及びSrの元素組成比を下記組成式(I);
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足する、チタン酸アルミニウム系セラミックス。 - 粉末X線回折スペクトルに、結晶性のシリカ含有相を示すピークが現れない、請求項10に記載のチタン酸アルミニウム系セラミックス。
- アルミニウム源、マグネシウム源、チタン源及びケイ素源を含み、前記アルミニウム源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、前記マグネシウム源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、前記チタン源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下であり、且つ、前記ケイ素源中のNa2O及びK2Oの総量が0.001質量%以上0.25質量%以下である原料混合物を焼成することで、Al、Mg、Ti、Si、Na、K、Ca及びSrの元素組成比を下記組成式(I);
Al2(1-x)MgxTi(1+y)O5+aAl2O3
+bSiO2
+cNa2O+dK2O+eCaO+fSrO ・・・(I)
で表したときに、xは0<x<1を満足し、yは0.5x<y<3xを満足し、aは0.1x≦a<2xを満足し、bは0.05≦b≦0.4を満足し、c及びdは0<(c+d)を満足し、c、d、e及びfは0.5<{(c+d+e+f)/b}×100<10を満足するチタン酸アルミニウム系セラミックスを得る工程を含む、チタン酸アルミニウム系セラミックスの製造方法。 - 前記ケイ素源がSiO2を95質量%以上含む、請求項12に記載の製造方法。
- 前記ケイ素源が非晶質相を90質量%以上含む、請求項12又は13に記載の製造方法。
- 前記原料混合物を焼成した後に、焼成物を洗浄する工程を含む、請求項12~14のいずれか一項に記載の製造方法。
- 前記焼成物の洗浄は、pH9以上のアルカリ溶液により行う、請求項15記載の製造方法。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014554539A JP6041902B2 (ja) | 2012-12-27 | 2013-12-26 | ハニカムフィルタ及びその製造方法 |
KR1020157017304A KR20150099765A (ko) | 2012-12-27 | 2013-12-26 | 허니컴 필터 및 그 제조 방법, 그리고 티탄산알루미늄계 세라믹스 및 그 제조 방법 |
MX2015008461A MX2015008461A (es) | 2012-12-27 | 2013-12-26 | Filtro en forma de panal y metodo para produccion para el mismo, y ceramica basada en titanato de aluminio y metodo de produccion para la misma. |
CN201380068511.0A CN104870402A (zh) | 2012-12-27 | 2013-12-26 | 蜂窝过滤器及其制造方法、以及钛酸铝系陶瓷及其制造方法 |
BR112015015372A BR112015015372A2 (pt) | 2012-12-27 | 2013-12-26 | filtro do tipo colmeia e método de produção do mesmo, e cerâmica à base de titanato de alumínio e produção da mesma |
EP13866987.4A EP2939992B1 (en) | 2012-12-27 | 2013-12-26 | Honeycomb filter and production method therefor |
ES13866987.4T ES2632812T3 (es) | 2012-12-27 | 2013-12-26 | Filtro de panal y método de producción del mismo |
US14/752,187 US20150367334A1 (en) | 2012-12-27 | 2015-06-26 | Honeycomb filter and production method therefor, and aluminium titanate-based ceramic and production method therefor |
ZA2015/05291A ZA201505291B (en) | 2012-12-27 | 2015-07-22 | Honeycomb filter and production method therefor, and aluminium titanate-based ceramic and production method therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012285229 | 2012-12-27 | ||
JP2012-285229 | 2012-12-27 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/752,187 Continuation US20150367334A1 (en) | 2012-12-27 | 2015-06-26 | Honeycomb filter and production method therefor, and aluminium titanate-based ceramic and production method therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014104179A1 true WO2014104179A1 (ja) | 2014-07-03 |
Family
ID=51021253
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/084856 WO2014104179A1 (ja) | 2012-12-27 | 2013-12-26 | ハニカムフィルタ及びその製造方法、並びに、チタン酸アルミニウム系セラミックス及びその製造方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US20150367334A1 (ja) |
EP (1) | EP2939992B1 (ja) |
JP (1) | JP6041902B2 (ja) |
KR (1) | KR20150099765A (ja) |
CN (1) | CN104870402A (ja) |
BR (1) | BR112015015372A2 (ja) |
ES (1) | ES2632812T3 (ja) |
MX (1) | MX2015008461A (ja) |
PL (1) | PL2939992T3 (ja) |
WO (1) | WO2014104179A1 (ja) |
ZA (1) | ZA201505291B (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015082892A3 (en) * | 2013-12-02 | 2015-09-24 | Johnson Matthey Public Limited Company | Wall-flow filter comprising catalytic washcoat |
US20150367334A1 (en) * | 2012-12-27 | 2015-12-24 | Sumitomo Chemical Company, Limited | Honeycomb filter and production method therefor, and aluminium titanate-based ceramic and production method therefor |
JP2016131918A (ja) * | 2015-01-19 | 2016-07-25 | 大塚化学株式会社 | 排ガス浄化フィルタの製造方法、排ガス浄化フィルタ及び排ガス浄化装置 |
CN107847925A (zh) * | 2015-07-08 | 2018-03-27 | 大塚化学株式会社 | 废气净化过滤器的制造方法、废气净化过滤器和废气净化装置 |
WO2018198999A1 (ja) * | 2017-04-26 | 2018-11-01 | 大塚化学株式会社 | ハニカム構造体及び排ガス浄化装置 |
JP2021000631A (ja) * | 2014-07-31 | 2021-01-07 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | 触媒を製造するための方法及び触媒物品 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6231908B2 (ja) * | 2014-03-14 | 2017-11-15 | 日本碍子株式会社 | 目封止ハニカム構造体 |
GB2547288B (en) | 2016-02-03 | 2021-03-17 | Johnson Matthey Plc | Catalyst for oxidising ammonia |
JP6169227B1 (ja) * | 2016-06-13 | 2017-07-26 | 日本碍子株式会社 | ハニカムフィルタ |
JP6756530B2 (ja) * | 2016-07-05 | 2020-09-16 | イビデン株式会社 | ハニカム構造体及びハニカム構造体の製造方法 |
JP6994497B2 (ja) * | 2017-03-08 | 2022-01-14 | 日本碍子株式会社 | 多孔質ハニカム蓄熱構造体 |
EP3581272B1 (en) * | 2017-03-27 | 2021-05-05 | Cataler Corporation | Catalyst for exhaust gas purification |
CN109209575B (zh) | 2018-09-29 | 2021-05-14 | 大连理工大学 | 一种颗粒捕集器过滤体的非对称孔道结构 |
KR102555516B1 (ko) * | 2022-10-05 | 2023-07-13 | 대가파우더시스템 주식회사 | 다공성 세라믹 필터 제조방법 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01249657A (ja) * | 1988-03-31 | 1989-10-04 | Toshiba Corp | セラミックス焼結体 |
JP2001046886A (ja) | 1999-08-11 | 2001-02-20 | Denso Corp | セラミックハニカム構造体 |
WO2005105704A1 (ja) * | 2004-04-28 | 2005-11-10 | Ohcera Co., Ltd. | チタン酸アルミニウムマグネシウム結晶構造物及びその製造方法 |
JP2006239603A (ja) | 2005-03-04 | 2006-09-14 | Ngk Insulators Ltd | ハニカム構造体 |
JP2009084064A (ja) * | 2007-09-27 | 2009-04-23 | Kyocera Corp | 耐熱性セラミック部材およびフィルタ |
WO2009063997A1 (ja) * | 2007-11-14 | 2009-05-22 | Hitachi Metals, Ltd. | チタン酸アルミニウム質セラミックハニカム構造体、その製造方法、及びそれを製造するための原料粉末 |
JP2009196881A (ja) * | 2008-01-21 | 2009-09-03 | Sumitomo Chemical Co Ltd | チタン酸アルミニウムマグネシウム−アルミナ複合セラミックス |
JP2010116289A (ja) * | 2008-11-12 | 2010-05-27 | Sumitomo Chemical Co Ltd | チタン酸アルミニウム系セラミックスの製造方法 |
JP2010227767A (ja) | 2009-03-26 | 2010-10-14 | Ngk Insulators Ltd | ハニカムフィルタ |
WO2011008938A1 (en) * | 2009-07-15 | 2011-01-20 | E.I. Du Pont De Nemours And Company | Aluminium magnesium titanate composite ceramics |
JP2011523616A (ja) * | 2008-05-29 | 2011-08-18 | サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン | チタン酸アルミニウムを含有する多孔質構造体 |
WO2011111633A1 (ja) * | 2010-03-08 | 2011-09-15 | 住友化学株式会社 | 多孔質チタン酸アルミニウムマグネシウムの製造方法および多孔質チタン酸アルミニウムマグネシウム |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4523911B2 (ja) * | 2005-12-14 | 2010-08-11 | 本田技研工業株式会社 | 排ガス浄化装置 |
WO2009122535A1 (ja) * | 2008-03-31 | 2009-10-08 | イビデン株式会社 | ハニカム構造体の製造方法 |
WO2010098347A1 (ja) * | 2009-02-26 | 2010-09-02 | 京セラ株式会社 | ハニカム構造体およびガス処理装置 |
JP2012219736A (ja) * | 2011-04-11 | 2012-11-12 | Sumitomo Chemical Co Ltd | ハニカム構造体 |
PL2939992T3 (pl) * | 2012-12-27 | 2017-09-29 | Sumitomo Chemical Company, Limited | Filtr typu plastra miodu i sposób jego wytwarzania |
-
2013
- 2013-12-26 PL PL13866987T patent/PL2939992T3/pl unknown
- 2013-12-26 EP EP13866987.4A patent/EP2939992B1/en not_active Not-in-force
- 2013-12-26 KR KR1020157017304A patent/KR20150099765A/ko not_active Application Discontinuation
- 2013-12-26 MX MX2015008461A patent/MX2015008461A/es unknown
- 2013-12-26 JP JP2014554539A patent/JP6041902B2/ja not_active Expired - Fee Related
- 2013-12-26 BR BR112015015372A patent/BR112015015372A2/pt not_active IP Right Cessation
- 2013-12-26 WO PCT/JP2013/084856 patent/WO2014104179A1/ja active Application Filing
- 2013-12-26 CN CN201380068511.0A patent/CN104870402A/zh active Pending
- 2013-12-26 ES ES13866987.4T patent/ES2632812T3/es active Active
-
2015
- 2015-06-26 US US14/752,187 patent/US20150367334A1/en not_active Abandoned
- 2015-07-22 ZA ZA2015/05291A patent/ZA201505291B/en unknown
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01249657A (ja) * | 1988-03-31 | 1989-10-04 | Toshiba Corp | セラミックス焼結体 |
JP2001046886A (ja) | 1999-08-11 | 2001-02-20 | Denso Corp | セラミックハニカム構造体 |
WO2005105704A1 (ja) * | 2004-04-28 | 2005-11-10 | Ohcera Co., Ltd. | チタン酸アルミニウムマグネシウム結晶構造物及びその製造方法 |
JP2006239603A (ja) | 2005-03-04 | 2006-09-14 | Ngk Insulators Ltd | ハニカム構造体 |
JP2009084064A (ja) * | 2007-09-27 | 2009-04-23 | Kyocera Corp | 耐熱性セラミック部材およびフィルタ |
WO2009063997A1 (ja) * | 2007-11-14 | 2009-05-22 | Hitachi Metals, Ltd. | チタン酸アルミニウム質セラミックハニカム構造体、その製造方法、及びそれを製造するための原料粉末 |
JP2009196881A (ja) * | 2008-01-21 | 2009-09-03 | Sumitomo Chemical Co Ltd | チタン酸アルミニウムマグネシウム−アルミナ複合セラミックス |
JP2011523616A (ja) * | 2008-05-29 | 2011-08-18 | サン−ゴバン サントル ドゥ ルシェルシェ エ デトゥードゥ ユーロペン | チタン酸アルミニウムを含有する多孔質構造体 |
JP2010116289A (ja) * | 2008-11-12 | 2010-05-27 | Sumitomo Chemical Co Ltd | チタン酸アルミニウム系セラミックスの製造方法 |
JP2010227767A (ja) | 2009-03-26 | 2010-10-14 | Ngk Insulators Ltd | ハニカムフィルタ |
WO2011008938A1 (en) * | 2009-07-15 | 2011-01-20 | E.I. Du Pont De Nemours And Company | Aluminium magnesium titanate composite ceramics |
WO2011111633A1 (ja) * | 2010-03-08 | 2011-09-15 | 住友化学株式会社 | 多孔質チタン酸アルミニウムマグネシウムの製造方法および多孔質チタン酸アルミニウムマグネシウム |
Non-Patent Citations (1)
Title |
---|
See also references of EP2939992A4 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150367334A1 (en) * | 2012-12-27 | 2015-12-24 | Sumitomo Chemical Company, Limited | Honeycomb filter and production method therefor, and aluminium titanate-based ceramic and production method therefor |
WO2015082892A3 (en) * | 2013-12-02 | 2015-09-24 | Johnson Matthey Public Limited Company | Wall-flow filter comprising catalytic washcoat |
JP2021000631A (ja) * | 2014-07-31 | 2021-01-07 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | 触媒を製造するための方法及び触媒物品 |
JP2016131918A (ja) * | 2015-01-19 | 2016-07-25 | 大塚化学株式会社 | 排ガス浄化フィルタの製造方法、排ガス浄化フィルタ及び排ガス浄化装置 |
CN107847925A (zh) * | 2015-07-08 | 2018-03-27 | 大塚化学株式会社 | 废气净化过滤器的制造方法、废气净化过滤器和废气净化装置 |
US20180185826A1 (en) * | 2015-07-08 | 2018-07-05 | Otsuka Chemical Co., Ltd. | Method for producing exhaust gas purifying filter, exhaust gas purifying filter, and exhaust gas purification device |
WO2018198999A1 (ja) * | 2017-04-26 | 2018-11-01 | 大塚化学株式会社 | ハニカム構造体及び排ガス浄化装置 |
Also Published As
Publication number | Publication date |
---|---|
EP2939992A4 (en) | 2016-10-26 |
ES2632812T3 (es) | 2017-09-15 |
EP2939992B1 (en) | 2017-04-26 |
US20150367334A1 (en) | 2015-12-24 |
KR20150099765A (ko) | 2015-09-01 |
ZA201505291B (en) | 2016-12-21 |
MX2015008461A (es) | 2015-09-23 |
EP2939992A1 (en) | 2015-11-04 |
BR112015015372A2 (pt) | 2017-07-11 |
JP6041902B2 (ja) | 2016-12-14 |
JPWO2014104179A1 (ja) | 2017-01-12 |
CN104870402A (zh) | 2015-08-26 |
PL2939992T3 (pl) | 2017-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6041902B2 (ja) | ハニカムフィルタ及びその製造方法 | |
KR102428707B1 (ko) | 배기가스를 처리하기 위한 분자체 촉매 | |
US8629074B2 (en) | Zeolite honeycomb structure | |
US9844768B2 (en) | Honeycomb catalyst body | |
KR20160041945A (ko) | 파티큘레이트 필터 | |
US20140357476A1 (en) | Formed ceramic substrate composition for catalyst integration | |
JP6121542B2 (ja) | 排ガス浄化フィルタ及び排ガス浄化装置 | |
CN108698841B (zh) | 制备铁(iii)交换的沸石组合物的方法 | |
KR20090092291A (ko) | 개선된 매연 필터 | |
US20190291050A1 (en) | Oxidation catalyst, catalyst support structure, method of producing oxidation catalyst, and method of producing catalyst support structure | |
US20100304965A1 (en) | Ceramic Articles And Methods Of Producing Ceramic Articles | |
WO2014014059A1 (ja) | ハニカムフィルタ | |
KR20180027434A (ko) | 배기 가스 정화 필터의 제조 방법, 배기 가스 정화 필터 및 배기 가스 정화 장치 | |
US9999879B2 (en) | Formed ceramic substrate composition for catalyst integration | |
US20140357474A1 (en) | Formed ceramic substrate composition for catalyst integration | |
WO2018198999A1 (ja) | ハニカム構造体及び排ガス浄化装置 | |
JP2014018768A (ja) | 排ガス浄化システム | |
US11480081B2 (en) | Porous ceramic structure | |
WO2018116884A1 (ja) | ハニカム構造体及び排ガス浄化装置 | |
WO2014199740A1 (ja) | ハニカム構造体及びハニカムフィルタ | |
JP2018202399A (ja) | 自動車用酸化触媒構造体及びその製造方法、ならびに、自動車用ハニカムフィルタ、自動車用排気ガス処理装置及び触媒成形体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13866987 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014554539 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2015/008461 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 20157017304 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015015372 Country of ref document: BR |
|
REEP | Request for entry into the european phase |
Ref document number: 2013866987 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013866987 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 112015015372 Country of ref document: BR Kind code of ref document: A2 Effective date: 20150625 |