WO2012076648A1 - Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides - Google Patents
Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides Download PDFInfo
- Publication number
- WO2012076648A1 WO2012076648A1 PCT/EP2011/072190 EP2011072190W WO2012076648A1 WO 2012076648 A1 WO2012076648 A1 WO 2012076648A1 EP 2011072190 W EP2011072190 W EP 2011072190W WO 2012076648 A1 WO2012076648 A1 WO 2012076648A1
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- WIPO (PCT)
- Prior art keywords
- metal
- mixture
- catalyst
- zeolite
- samples
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 116
- 239000010457 zeolite Substances 0.000 title claims abstract description 79
- 230000008569 process Effects 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 title claims description 97
- 239000002184 metal Substances 0.000 title claims description 97
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title description 20
- 230000003197 catalytic effect Effects 0.000 title description 12
- 238000005067 remediation Methods 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 86
- 238000000859 sublimation Methods 0.000 claims abstract description 35
- 230000008022 sublimation Effects 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000000203 mixture Substances 0.000 claims description 64
- 239000003054 catalyst Substances 0.000 claims description 51
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 49
- 229910021536 Zeolite Inorganic materials 0.000 claims description 48
- 229910052802 copper Inorganic materials 0.000 claims description 48
- 238000001354 calcination Methods 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011872 intimate mixture Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
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- 238000011068 loading method Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052676 chabazite Inorganic materials 0.000 claims description 3
- 239000012013 faujasite Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 86
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- 239000000843 powder Substances 0.000 description 28
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 10
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- 238000000354 decomposition reaction Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 9
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- 239000000243 solution Substances 0.000 description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 7
- 239000012691 Cu precursor Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000013074 reference sample Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229930194542 Keto Natural products 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 3
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- -1 nitrogen-containing compound Chemical class 0.000 description 3
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- 239000012692 Fe precursor Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 2
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- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 229910014570 C—OH Inorganic materials 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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Classifications
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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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- 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
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180059452.1A CN103260757B (en) | 2010-12-11 | 2011-12-08 | For the application for nitrogen oxides catalysis treatment of the method for the zeolite and class zeolite that manufacture doping metals and the method |
JP2013542542A JP5837088B2 (en) | 2010-12-11 | 2011-12-08 | Use of metal-doped zeolites and zeotypes for catalytic improvement of nitrogen oxides |
EP11802884.4A EP2648845B1 (en) | 2010-12-11 | 2011-12-08 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides |
US13/992,025 US8865120B2 (en) | 2010-12-11 | 2011-12-08 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides |
RU2013131779/04A RU2595336C2 (en) | 2010-12-11 | 2011-12-08 | Method of producing zeolites and zeolite-like structures doped with metals, and methods for use thereof for catalytic reduction of nitrogen oxides |
KR1020137017797A KR101950670B1 (en) | 2010-12-11 | 2011-12-08 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides |
BR112013014529-3A BR112013014529B1 (en) | 2010-12-11 | 2011-12-08 | Process for the production of zeolites and zeotypes donated with metals. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10015547.2 | 2010-12-11 | ||
EP10015547A EP2463028A1 (en) | 2010-12-11 | 2010-12-11 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides |
Publications (1)
Publication Number | Publication Date |
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WO2012076648A1 true WO2012076648A1 (en) | 2012-06-14 |
Family
ID=44069411
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/072190 WO2012076648A1 (en) | 2010-12-11 | 2011-12-08 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides |
Country Status (8)
Country | Link |
---|---|
US (1) | US8865120B2 (en) |
EP (2) | EP2463028A1 (en) |
JP (1) | JP5837088B2 (en) |
KR (1) | KR101950670B1 (en) |
CN (1) | CN103260757B (en) |
BR (1) | BR112013014529B1 (en) |
RU (1) | RU2595336C2 (en) |
WO (1) | WO2012076648A1 (en) |
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CN103260757A (en) | 2013-08-21 |
JP2014507361A (en) | 2014-03-27 |
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JP5837088B2 (en) | 2015-12-24 |
US20130251611A1 (en) | 2013-09-26 |
US8865120B2 (en) | 2014-10-21 |
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