JP5261189B2 - Nox選択的触媒還元効率の改善されたゼオライト触媒 - Google Patents
Nox選択的触媒還元効率の改善されたゼオライト触媒 Download PDFInfo
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- JP5261189B2 JP5261189B2 JP2008545808A JP2008545808A JP5261189B2 JP 5261189 B2 JP5261189 B2 JP 5261189B2 JP 2008545808 A JP2008545808 A JP 2008545808A JP 2008545808 A JP2008545808 A JP 2008545808A JP 5261189 B2 JP5261189 B2 JP 5261189B2
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- zeolite
- metal
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- copper
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 171
- 239000010457 zeolite Substances 0.000 title claims description 165
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 157
- 239000003054 catalyst Substances 0.000 title claims description 89
- 238000010531 catalytic reduction reaction Methods 0.000 title claims description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 138
- 229910052782 aluminium Inorganic materials 0.000 claims description 76
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 76
- 239000010949 copper Substances 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 62
- 229910052802 copper Inorganic materials 0.000 claims description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 50
- 239000011734 sodium Substances 0.000 claims description 50
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 49
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 229910052708 sodium Inorganic materials 0.000 claims description 39
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 34
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000005342 ion exchange Methods 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000012013 faujasite Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 230000010757 Reduction Activity Effects 0.000 claims description 5
- 238000005341 cation exchange Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000010828 elution Methods 0.000 description 11
- 238000010335 hydrothermal treatment Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- -1 for example Chemical compound 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 229910002530 Cu-Y Inorganic materials 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- 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
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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Description
本願は、「NOX選択的触媒還元効率の改善されたゼオライト触媒」をタイトルとする2005年12月14日に出願された米国仮出願60/750,261の優先権主張を伴うものである。
2NO2+4NH3+O2→3N2+6H2O (2)
NO+NO2+NH3→2N2+3H2O (3)
本発明によれば、ゼオライトは、まず金属イオン交換により金属で処理される。一般に、何れの公知金属を、1種単独で用いても良く2種以上併用してもよい。例えば、本発明のゼオライトを、バナジウム(V)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)及びセリウム(Ce)からなる群から選ばれる金属イオンでイオン交換することができる。ある実施様態においては、ゼオライトYと銅の使用が好ましい。しかしながら、当業界の熟練者には理解できるように、上述のような他の金属イオンや他のゼオライトも銅とゼオライトYに代えて使用可能である。
未反応アンモニアの排出が起こることもある。混合不足によりガス流中に高アンモニア濃度の流路ができるが、特に複数の微細な平行ガス流路を持つ耐火性ボディーに収納したモノリスハニカム型の担体の触媒を使用する場合には、粒状触媒の床の場合とは異なり流路間でガスの混合の可能性がないため、このような流路ができる懸念が大きい。したがって、窒素酸化物の選択的触媒還元の触媒のために使用される触媒が、酸素とアンモニアの反応を触媒して、効果的に過剰または未反応のアンモニアをN2及びH2Oに酸化することが望ましい。
(実施例1)
触媒A.
銅ゼオライトYの合成
低ナトリウムY(Na2O<2.4質量%)のアンモニウム型を、銅で次のように処理した:
B.攪拌を続けながら、工程Aのスラリーを80℃に加熱し、一時間保持し、その後冷却した。溶液のpHは調整しなかったが、反応中2.75〜3.5の範囲であった。
C.冷却した工程Bのスラリーを真空濾過して、液体から固形分を分離し、固形分を、分離された液体と同量の脱イオン水で洗浄した。
D.工程Cの粉末を4時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
E.工程DのCuYを、工程Aのものと同一の銅溶液に再スラリー化(連続的に攪拌しながら)し、その後、工程B〜工程Dを五回交換を繰り返した。各々の交換のpHは、いずれの反応も2.75〜3.5であった。
F.最終の交換の後、粉末を16時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
G.工程FのCuYは、16時間640℃でか焼した。化学分析の結果、このCuY粉末が、4.89質量%のCu(揮発分非含有の金属酸化物として)と0.41質量%Na2Oを含んでいることがわかった。
H.次いで、か焼したCuYを、10%水蒸気の空気中で800℃で50時間水熱処理した。これを触媒Aと称する。
触媒B.
銅ゼオライトYの合成
低ナトリウムY(Na2O<2.4質量%)のアンモニウム型を、銅で次のように処理した:
B.攪拌を続けながら、工程Aのスラリーを80℃に加熱し、一時間保持し、その後冷却した。溶液のpHは調整しなかったが、反応中3〜4の範囲であった。
C.冷却した工程Bのスラリーを真空濾過して、液体から固形分を分離し、固形分を分離された液体と同量の脱イオン水で洗浄した。
D.工程Cの粉末を4時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
E.工程DのCuYを、工程Aのものと同一の銅溶液に再スラリー化(連続的に攪拌しながら)し、その後工程B〜工程Dを二回、それぞれ1時間行った。各々の交換のpHは、いずれの反応も3〜4であった。
F.最終の交換の後、粉末を16時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
G.工程FのCuYは、16時間640℃でか焼した。化学分析の結果、このCuY粉末が、4.75質量%のCu(揮発分非含有の金属酸化物として)と0.1質量%Na2Oを含んでいることがわかった。
H.か焼したCuYを、次いで、10%水蒸気の空気中で800℃で50時間水熱処理した。これを触媒Bと称する。
実施例1と実施例2銅ゼオライト触媒を用いて、約2〜2.5g/in.3の量でハニカムに塗布した。試験室反応器において、これらの触媒のNOXのNH3でのSCR還元性能を試験した。供給ガスは、窒素中に500ppmのNOX(NOとして添加)と500ppmのNH3と5体積%の水と10体積%のO2を含んでいた。空間速度GHSVは、80,000h-1であった。図1は、銅ゼオライトY触媒の水熱安定性にとってナトリウム含量が重要であることを示す。低いナトリウムレベルでは水熱養生後にNOx還元効率が改善している。フレッシュな触媒はいずれも、類似の銅負荷量(約4.8質量%のCuO)及び類似の骨格外アルミニウム含量を有するが、ナトリウム含量では異なっている。
触媒C.
銅ゼオライトYの合成
低ナトリウムY(Na2O<0.2質量%)のアンモニウム型を、銅で次のように処理した:
B.攪拌を続けながら、工程Aのスラリーを80℃に加熱し、一時間保持し、その後冷却した。溶液のpHは調整しなかったが、反応中2.75〜3.5の範囲であった。
C.冷却した工程Bのスラリーを真空濾過して、液体から固形分を分離し、固形分を、分離された液体と同量の脱イオン水で洗浄した。
D.工程Cの粉末を4時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
E.工程DのCuYを、工程Aのものと同一の銅溶液に再スラリー化(連続的に攪拌しながら)し、その後、工程B〜工程Dを五回、それぞれ1時間交換を繰り返した。各々の交換のpHは、いずれの反応も2.75〜3.5であった。
F.最終の交換の後、粉末を16時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
G.工程FのCuYは、16時間640℃でか焼した。化学分析の結果、このCuY粉末が、4.4質量%のCu(揮発分非含有の金属酸化物として)と0.1質量%のNa2Oを含んでいることがわかった。
H.か焼したCuYを、次いで10%水蒸気の空気中で800℃で50時間水熱処理した。これを触媒Cと称する。
触媒D.
銅ゼオライトYの合成
低ナトリウムY(Na2O<0.2質量%)のアンモニウム型を、銅で次のように処理した:
B.攪拌を続けながら、工程Aのスラリーを80℃に加熱し、一時間保持し、その後冷却した。溶液のpHは調整しなかったが、反応中3〜3.5の範囲であった。
C.冷却した工程Bのスラリーは、フィルタープレスを用いて液体から固形分を分離し、固形分を、分離された液体と同量の脱イオン水で洗浄した。
D.工程Cの粉末を4時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
E.工程DのCuYを、工程Aのものと同一の銅溶液に再スラリー化(連続的に攪拌しながら)し、その後、工程B〜工程Dを二回繰り返した。二回目の交換の際のpHは、いずれの反応も3〜3.5であった。
F.最終の交換の後、粉末を16時間90℃の空気中で乾燥し、銅処理ゼオライトY粉末(CuY)を得た。
G.工程FのCuYは、16時間640℃でか焼した。化学分析の結果、このCuY粉末が、4.3質量%のCu(揮発分非含有の金属酸化物として)と0.1質量%Na2Oを含んでいることがわかった。
H.か焼したCuYを、次いで、10%水蒸気の空気中で800℃で50時間水熱処理した。これを触媒Dと称する。
実施例4と実施例5の銅ゼオライト触媒を用いて、約2〜2.5g/in.3の量でハニカムに塗布した。試験室反応器において、これらの触媒のNOXのNH3SCR還元性能を試験した。The供給ガスは、窒素中に500ppmのNOX(NOとして添加)と500ppmのNH3と5体積%の水と10体積%のO2を含んでいた。空間速度GHSVは、80,000h-1であった。図2は、ゼオライト空孔から骨格外アルミニウムを除去することが重要であることを示している。骨格外アルミニウムが除かれない場合には水蒸気養生後に触媒の不活性化が見られ、骨格外アルミニウムがゼオライト空孔から除かれると触媒性能が改善した。骨格外アルミニウムのゼオライト空孔中における好ましくない残存レベルを決めるのに、実施例7と実施例8で作成したデータを使用した。表1は、触媒の水熱安定性のために必要な骨格外アルミニウムの限度を示すX線回折(XRD)データ及びX線光電子分光法(XPS)データである。
ゼオライトYの水熱前処理
マイクロポアから骨格外アルミニウムを除くための低ナトリウムY(NA2O<0.2質量%)の水熱脱アルミニウム処理
この方法で、XPSのAl/Siが0.58でEFAの計算値が5質量%Al2O3であるサンプルを得た。
B.冷却した試料を反応器から取り出した。
ゼオライトYの酸溶出前処理
骨格外アルミニウム除去のための低ナトリウムY(NA2O<0.2質量%)の酸溶出脱アルミニウム処理
バルクのAl2O3の化学分析では、揮発分非含有のAl2O3として22.72質量%の含量であった。24.53Åの単位格子において、揮発分非含有の骨格アルミニウム含量は、14.8質量%Al2O3であった。この方法により、EFAの計算値が2.08質量%Al2O3である試料が得られた、この値は、XPS例で定義した上限より小さい。
B.濃塩酸を添加してpHを2.5に調整した。塩酸を添加して、pHを2.5〜2.8に1時間維持した。
C.このスラリーを真空で濾過し、液体から固形分を除き、この固形分を分離された液体と同体積の脱イオン水で洗浄した。
D.工程Cの粉末を90℃の空気中で4時間乾燥した。
E.工程Dの粉末を工程Aと同一の脱イオン水に再懸濁(連続して攪拌しながら)した。その後、工程B〜工程Eを繰り返した。この反応中、pHを2.5〜2.8にコントロールした。
ゼオライトYの酸溶出前処理
骨格外アルミニウム除去のための低ナトリウムY(NA2O<0.2質量%)の酸溶出脱アルミニウム処理
バルクAl2O3の化学分析では、揮発分非含有のAl2O3の含量は22.72質量%であった。24.53Åの単位格子において、揮発分非含有の骨格アルミニウム含量は、14.8質量%Al2O3であった。この方法により、EFAの計算値が2.08質量%Al2O3である試料が得られた、この値は、XPS例で定義した上限より小さい。
B.攪拌を継続しながら、濃塩酸を添加して、pHを2.5に調整した。塩酸を添加して、pHを2.5〜2.8に24時間維持した。
C.このスラリーを真空で濾過し、液体から固形分を除き、この固形分を分離された液体と同体積の脱イオン水で洗浄した。
D.工程Cの粉末を90℃の空気中で4時間乾燥した。
E.工程Dの粉末を工程Aと同一の脱イオン水に再懸濁(連続して攪拌しながら)した。その後、工程B〜工程Eを繰り返した。この反応中、pHを2.5〜2.8にコントロールした。
Claims (10)
- NOxの選択的触媒還元のための新規な金属処理ゼオライト触媒の製造方法であって、
まず、ゼオライトを、酸処理またはアンモニウムカチオン交換処理して、ゼオライトのナトリウムレベルをNa2Oとして3質量%未満まで低下させ、
a.前記金属としての鉄、コバルト及び銅から選択された金属をファージャサイトを含むゼオライト中にイオン交換で導入し、
b.続いて、前記金属交換ゼオライトを水熱処理する工程を含み、
c.工程bで処理されない金属交換ゼオライト触媒と比較して、
前記触媒において、選択的触媒還元におけるNOx還元活性が改善されていることを特徴とする方法。 - 前記ゼオライトが、ゼオライトY、ウルトラ−ステイブルY、ZSM−3、ZSM−20、CSZ−1、ECR−30、LZ−210からなる群から選ばれる請求項1に記載の方法。
- 前記金属イオン交換を、pHが2.5〜3.5である水系の交換溶液中で行う請求項1又は2に記載の方法。
- 前記金属交換ゼオライトを、温度が540℃〜1000℃で、水蒸気濃度が5〜100%で、5分間〜250時間水熱処理する請求項1〜3のいずれか1項に記載の方法。
- 請求項1〜4のいずれか1項に記載の方法により製造することを特徴とする銅含有アルミノケイ酸塩ゼオライト触媒。
- 請求項1〜4のいずれか1項に記載の方法により製造された窒素酸化物の選択的還元用の水熱的に安定なゼオライト触媒であって、該触媒が金属処理ゼオライト触媒を含み、該金属処理ゼオライトが、骨格外アルミニウムを形成するように処理されて、骨格外アルミニウムの大部分がゼオライトの空孔から除かれることを特徴とする触媒。
- アルミニウム総量の65質量%未満がゼオライトの空孔中に存在する請求項6に記載のゼオライト触媒。
- 前記ゼオライトがゼオライトYであり、前記金属が銅である請求項6又は7に記載のゼオライト触媒。
- 前記ゼオライトが直径が2〜50nmのメソポアを含み、前記メソポアの空孔容量が少なくとも0.07cm3/gである請求項6〜8のいずれか1項に記載のゼオライト触媒。
- アンモニアと酸素を用いて選択的触媒還元により排ガスまたは排煙流中のNOxを還元する方法であって、該排ガスまたは排煙流を、請求項1〜4のいずれか1項に記載の方法により製造された金属処理ゼオライト触媒、又は請求項5〜9のいずれか1項に記載のゼオライト触媒に接触させることを特徴とする方法。
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US6914026B2 (en) * | 2001-09-07 | 2005-07-05 | Engelhard Corporation | Hydrothermally stable metal promoted zeolite beta for NOx reduction |
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WO2007070639A2 (en) | 2005-12-14 | 2007-06-21 | Basf Catalysts Llc | Zeolite catalyst with improved nox reduction in scr |
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2006
- 2006-12-14 WO PCT/US2006/047711 patent/WO2007070639A2/en active Application Filing
- 2006-12-14 EP EP06845422A patent/EP1973633A2/en not_active Ceased
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- 2006-12-14 CN CNA200680051790XA patent/CN101336129A/zh active Pending
- 2006-12-14 RU RU2008128363/15A patent/RU2008128363A/ru not_active Application Discontinuation
- 2006-12-14 KR KR1020087016846A patent/KR101394774B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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EP1973633A2 (en) | 2008-10-01 |
WO2007070639A8 (en) | 2007-08-02 |
BRPI0619944A2 (pt) | 2011-10-25 |
US20070134146A1 (en) | 2007-06-14 |
JP2009519817A (ja) | 2009-05-21 |
KR101394774B1 (ko) | 2014-05-15 |
US20100172814A1 (en) | 2010-07-08 |
BRPI0619944B1 (pt) | 2018-02-27 |
CN101336129A (zh) | 2008-12-31 |
KR20080081031A (ko) | 2008-09-05 |
US7968068B2 (en) | 2011-06-28 |
RU2008128363A (ru) | 2010-01-20 |
WO2007070639A3 (en) | 2007-09-20 |
BRPI0619944B8 (pt) | 2018-03-20 |
ZA200806013B (en) | 2009-10-28 |
WO2007070639A2 (en) | 2007-06-21 |
US7704475B2 (en) | 2010-04-27 |
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