CN105050710B - 作为用于处理废气的催化剂的铝硅酸盐或者硅铝磷酸盐分子筛/锰八面体分子筛 - Google Patents
作为用于处理废气的催化剂的铝硅酸盐或者硅铝磷酸盐分子筛/锰八面体分子筛 Download PDFInfo
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- CN105050710B CN105050710B CN201480014627.0A CN201480014627A CN105050710B CN 105050710 B CN105050710 B CN 105050710B CN 201480014627 A CN201480014627 A CN 201480014627A CN 105050710 B CN105050710 B CN 105050710B
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- zeolite
- zeolites
- ammonia
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- 239000003054 catalyst Substances 0.000 title claims abstract description 179
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 36
- 229910000323 aluminium silicate Inorganic materials 0.000 title abstract description 7
- 239000011572 manganese Substances 0.000 title description 16
- 229910052748 manganese Inorganic materials 0.000 title description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 58
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims description 138
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 111
- 229910021536 Zeolite Inorganic materials 0.000 claims description 94
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 claims description 84
- 239000000758 substrate Substances 0.000 claims description 61
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 55
- 239000011148 porous material Substances 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 229910021529 ammonia Inorganic materials 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 19
- 238000006722 reduction reaction Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000006069 physical mixture Substances 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- KWYKSRAECRPMIS-UHFFFAOYSA-N azane;hydrazine Chemical compound N.NN KWYKSRAECRPMIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 2
- 239000003546 flue gas Substances 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 61
- 229910052751 metal Inorganic materials 0.000 description 36
- 239000002184 metal Substances 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 238000001354 calcination Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 229910052878 cordierite Inorganic materials 0.000 description 11
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000011144 upstream manufacturing Methods 0.000 description 10
- 229910002089 NOx Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- -1 zeolite (that is Chemical compound 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical group 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
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- 241000790917 Dioxys <bee> Species 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 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
- 239000011651 chromium Substances 0.000 description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- 238000005259 measurement Methods 0.000 description 2
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
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- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- OQRWAMBQGTYSRD-UHFFFAOYSA-N dipotassium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[K+].[K+].[Ti+4].[Ti+4].[Ti+4].[Ti+4] OQRWAMBQGTYSRD-UHFFFAOYSA-N 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 239000003949 liquefied natural gas Substances 0.000 description 1
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- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
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- 239000010841 municipal wastewater Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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
Classifications
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- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- A63B71/06—Indicating or scoring devices for games or players, or for other sports activities
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- A63B71/0669—Score-keepers or score display devices
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- A63F—CARD, BOARD, OR ROULETTE GAMES; INDOOR GAMES USING SMALL MOVING PLAYING BODIES; VIDEO GAMES; GAMES NOT OTHERWISE PROVIDED FOR
- A63F13/00—Video games, i.e. games using an electronically generated display having two or more dimensions
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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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- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
公开了用于选择性催化还原(SCR)和其他废气处理的催化剂和制品。该催化剂包含含氧化锰的八面体分子筛(OMS)和铝硅酸盐和/或硅铝磷酸盐大孔或者中孔分子筛。
Description
发明领域
本发明涉及用于处理废气的催化剂,和特别是涉及铝硅酸盐或者 硅铝磷酸盐/锰八面体分子筛。
发明背景
烃在柴油机,固定燃气轮机和其他系统中的燃烧产生了废气,其 必须处理来除去氮氧化物(NOx),包括NO,NO2和N2O。在贫燃发动 机中产生的废气通常是氧化性的,并且需要用非均相催化剂和还原剂 (其通常是氨或者短链烃)来选择性还原NOx。已经彻底研究了该被称 作选择性催化还原(SCR)的方法。
许多已知的SCR催化剂使用了涂覆在高孔隙率载体例如氧化铝或 沸石上的过渡金属(例如Cu,Fe或V)。例如WO02/41991描述了用于 SCR方法的预处理的金属促进的β-沸石。美国专利申请公开 No.2011/0250127教导了通常使用的过渡金属沸石包括Cu/ZSM-5,Cu/β-沸石,Fe/ZSM-5,Fe/β-沸石等。这些沸石催化剂据称倾向于烃 吸附和结焦。该参考文献的结论是具有某些过渡金属的小孔沸石可以 提供NOx在NH3-SCR方法中良好的转化,同时具有良好的热稳定性, 低的烃吸附和低的N2O形成。沸石是一种公知种类的分子筛,其大部 分是由TO4四面体构成的规则骨架,在其中T通常是硅、铝或者磷。
氧化锰八面体分子筛(“OMS”)也是已知的。如其名称所示的,八 面体单元组合来产生整体结构,其特征在于一维通道。一些氧化锰 OMS是自然存在的,包括锰钡矿(锰钡矿,锰钾矿,锰钠矿,铅硬锰 矿)和结晶不佳的钡镁锰矿。氧化锰OMS也已经合成(参见例如美国专 利No.5340562;5523509;5545393;5578282;5635155;和5702674 和R.DeGuzman等人,Chem.Mater.6(1994)815)。在一些情况中,OMS 骨架中的一些锰可以用其他金属离子取代。这通常是通过在用于制备 氧化锰OMS的方法中掺杂其他离子来完成的。例如美国专利No.5702674教导了用Fe,Cu,Mo,Zn,La或者其他金属取代氧化 锰OMS骨架中的Mn。如这个参考文献中教导的,氧化锰OMS潜在 地可用于用氨来还原一氧化氮,虽然关于它们用于SCR方法的知识是 相当小的。
天然锰矿石(锰钡矿,锰钾矿)已经被用于氮氧化物用氨的低温 SCR(参见例如TaeSung Park等人, Ind.Eng.Chem.Res.40(2001)4491)。
氧化锰OMS催化剂具有一些缺点。例如该OMS催化剂会是热不 稳定的,使得NOx转化率在该催化剂老化或暴露于高温时会快速减 小。此外,低温(即,在100℃-250℃的温度)NOx转化率通常是低于期 望的。这是重要的,因为当废气温度处于它的最低值时,贫燃发动机(其 特征在于空气/燃料比>15,通常为19-50)在刚刚启动后产生了相当多 的NOx。氧化锰OMS催化剂在NOx转化方法中也会产生N2O,并且 理想地所形成的N2O的量会最小化。
更最近地,已经提出将其他金属用作氧化锰OMS的掺杂剂。例如 已经合成了钒掺杂的锰钾矿类型锰氧化物(V-OMS-2),并且用于通过 氨的低温SCR或者NO(NH3-SCR)(参见Liang Sun等人, Appl.Catal.A393(2011)323)。类似的是,Chao Wang等人描述了锰钡 矿类型的锰氧化物(其在通道中具有K+或H+)和它们用于低温 NH3-SCR的用途(Appl.Catal.B101(2011)598。
虽然大孔沸石和含过渡金属的沸石是普遍存在的,但是它们看起 来没有与锰OMS催化剂组合用于SCR方法,特别是NH3-SCR方法 中。工业上将受益于改进的SCR催化剂,特别是低温NH3-SCR催化 剂。
发明内容
在一方面,本发明涉及可用于选择性催化还原的催化剂。该催化 剂包含1-99wt%的含氧化锰的八面体分子筛(OMS)和1-99wt%的(一 种或多种)大孔和/或中孔沸石。在另一方面,本发明涉及SCR方法。 该方法包含在还原剂和上述(一种或多种)氧化锰OMS/大孔和/或中孔 沸石催化剂的存在下,选择性还原包含氮氧化物的气态混合物。还包 括了可用于SCR的包含催化剂和基底的制品。
我们惊讶地发现氧化锰OMS/大孔沸石催化剂和氧化锰OMS/中孔 沸石催化剂提供了用于选择性催化还原,特别是NH3-SCR的优点。 具体地,与使用不使用大孔沸石来制备的类似氧化锰OMS催化剂获 得的结果相比,该催化剂提供了在大于300℃温度的改进的NOx转化 率和在150℃-400℃温度的降低的N2O形成。与单独的大孔沸石催化 剂(没有氧化锰OMS)相比,本发明的催化剂在低温(150℃-250℃)提供 了改进的NOx转化。此外,当氧化锰OMS和大孔或中孔沸石组合使 用时,存在着协同效应。例如与单个组分的任一个相比,这样的组合 在可用的温度范围(例如250-400℃)产生了更高的NOx转化率。
附图说明
图1是对于本发明的OMS-2/β-沸石复合催化剂和基于单独的 OMS-2的对比催化剂,N2O形成相对于温度的图。
图2是对于本发明的OMS-2/β-沸石复合催化剂和基于单独的 OMS-2的对比催化剂,NOx转化率相对于温度的图。
图3是对于基于单独的OMS-2或者OMS-2和堇青石的1:1物理 混合物的对比催化剂,N2O形成相对于温度的图。
图4是对于基于单独的OMS-2或者OMS-2和堇青石的1:1物理 混合物的对比催化剂,NOx转化率相对于温度的图。
图5是对于本发明的各种的OMS-2/β-沸石载5%Fe催化剂和基 于单独OMS-2或者单独β-沸石载Fe的对比催化剂,N2O形成相对于 温度的图。
图6是对于本发明的各种的OMS-2/β-沸石载5%Fe催化剂和基 于单独OMS-2或者单独β-沸石载Fe的对比催化剂,NOx转化率相 对于温度的图。
图7显示了对于本发明的各种的OMS-2/β-沸石载5%Fe催化剂, 煅烧条件对于N2O形成相对于温度的图的影响。
图8显示了对于本发明的各种的OMS-2/β-沸石载5%Fe催化剂, 煅烧条件对于NOx转化率相对于温度的图的影响
图9是对于本发明的OMS-2和大孔沸石的复合催化剂和基于单独 的OMS-2的对比催化剂,N2O形成相对于温度的图。
图10是对于本发明的OMS-2和大孔沸石的复合催化剂和基于单 独的OMS-2的对比催化剂,NOx转化率相对于温度的图。
图11是对于本发明的OMS-2和大孔沸石的热老化的复合催化剂 和基于单独的OMS-2或者基于OMS-2和小孔沸石的对比催化剂,N2O 形成相对于温度的图。
图12是对于本发明的OMS-2和大孔沸石的热老化的复合催化剂 和基于单独的OMS-2或者基于OMS-2和小孔沸石的对比催化剂, NOx转化率相对于温度的图。
图13是对于本发明的各种的OMS-2/β-沸石,OMS-2/FER-沸石和 OMS-2/ZSM5-沸石催化剂和基于单独的OMS-2或者OMS-2/CHA-沸 石的对比催化剂,N2O形成相对于温度的图。
图14是对于本发明的各种的OMS-2/β-沸石,OMS-2/FER-沸石和 OMS-2/ZSM5-沸石催化剂和基于单独的OMS-2或者OMS-2/CHA-沸 石的对比催化剂,NOx转化率相对于温度的图。
具体实施方式
本发明的催化剂包含大孔沸石和氧化锰八面体分子筛。
用于制备本发明催化剂的合适的八面体分子筛是天然或者合成组 合物,其主要包含锰氧化物。氧化锰八面体分子筛(“OMS”)自然地以 钡镁锰矿,锰钡矿(BaMn8O16),锰钾矿(KMn8O16),锰钠矿(NaMn8O16) 和铅锰矿(PbMn8O16)存在的。该矿物具有由MnO6八面体组合的三维 骨架通道结构,并且区别在于存在于通道中的阳离子。
优选该OMS是合成的。可以使用由Steven Suib教授和同事们开 发,并且在许多科学论文和专利中报道的方法。参见例如:美国专利 No.5340562;5523509;5545393;5578282;5635155;5702674;6797247; 7153345;和7700517,其的教导在此引入作为参考。还参见: R.DeGuzman等人,Chem.Mater.6(1994)815)。合成的八面体分子筛 优选用于选择性催化还原和其他催化方法,这是因为它们具有基本均 匀的通道结构,这与天然矿物的更加无规分布的结构是相反的。
OMS的通道结构将取决于所用的合成方法而变化。例如 OMS-2(其具有锰钡矿的(2x2)通道结构)可以在硫酸锰、硝酸和高锰酸 钾的水热反应中制备(参见美国专利No.5702674)。相反,OMS-1具有 钡镁锰矿的(3x3)通道结构,并且可以通过如下来制备:将高锰酸镁溶 液加入到碱性氢氧化锰(II)中,随后进行老化和清洗步骤(参见例如美 国专利No.5340562)。还可以使用具有(4x4)通道结构的OMS(参见例如 美国专利No.5578282),以及具有(2x3)结构的OMS(参见例如美国专利 No.6797247)。如果期望,该OMS的骨架可以用其他金属取代(参见例 如美国专利No.5702674)。具有(2x2)和(3x3)通道结构的八面体分子筛 特别优选用于SCR方法。OMS-2是特别优选的。
通常,将锰阳离子源(例如MnCl2,Mn(NO3)2,MnSO4,Mn(OAc)2等),高锰酸盐离子和抗衡阳离子源(例如碱金属或碱土金属高锰酸盐) 和任何骨架取代金属阳离子源进行合并,并且在有效地产生具有期望 结构的氧化锰OMS的温度,压力,pH和其他因素的条件下反应。该 混合物可以在封闭系统中加热,这产生了自生压力,或者该反应可以 在大气条件下进行。
OMS主要是氧化锰基的。因此存在于OMS骨架结构中>50mol%, 优选>75%和更优选>95%的金属阳离子是锰阳离子。这些量包括掺杂 的金属阳离子的任何量,但是不包括可以沉积在OMS表面上的金属 的量。
高锰酸盐离子与锰阳离子的摩尔比经常在测定所形成的OMS的 性质方面是重要的。浓度比[MnO4 -1]/[Mn+2]优选是0.05-3.0,并且低比 例(0.3-0.4)对于制造钡镁锰矿是理想的,和稍高的比例(0.1-1.5)更优选 用于制造锰钡矿。
pH也影响所生产的OMS的性质。低pH(0-4)对于制造锰钡矿是 优选的,而高pH(>13)对于制造钡镁锰矿来说是期望的。
制造OMS的反应温度可以在宽范围内变化,并且也可以用于影响 所产生的产品的类型。通常该温度可以是25℃-300℃,并且70℃-160℃ 对于制造锰钡矿OMS结构是优选的,和130℃-170℃对于制造钡镁锰 矿是优选的。
该氧化锰OMS可以用金属掺杂来改进活性,赋予热稳定性,扩大 用于NOx转化的可用的温度范围,降低N2O的产生或者实现其他目 标。这通常是通过在OMS制备中包括含有水溶性金属盐的水溶液来 完成。用于掺杂的优选的金属包括Ca,Ti,V,Cr,Fe,Co,Ni, Cu,Zn,Ce,Zr,Mo,W和Pr。特别优选的是Cu,Ce,Fe和W。 在某些方面,本发明的氧化锰OMS,除了Mn之外没有或者基本上没 有金属,没有或者基本上没有过渡金属,没有或者基本上没有贵金属, 没有或者基本上没有碱金属,没有或者基本上没有碱土金属,和/或没 有或者基本上没有稀土金属。在某些方面,本发明的氧化锰OMS包 含Ce。在某些方面,本发明的氧化锰OMS是没有或者基本上没有 Ce。
其他氧化物和混合的氧化物可以混入该催化剂中,包括二氧化钛, 氧化锆,二氧化硅,氧化铝,二氧化硅-氧化铝,氧化铌等及其混合物。
本发明的催化剂包括中孔或者大孔分子筛例如沸石(即,铝硅酸盐) 和硅铝磷酸盐(SAPO),并且沸石在一些应用中是优选的。优选的催化 剂具有这样的分子筛骨架结构,其包括至少10元环(即,中孔分子筛), 或者优选包括至少12元环(即,大孔分子筛)。合适的大孔分子筛包括 β-沸石,Y沸石,超稳定的Y沸石(USY),脱铝的Y沸石,X沸石, 发光沸石,ZSM-3,ZSM-4,ZSM-18,ZSM-20等。参见美国专利 No.3923636,3972983,3308069,3293192,3449070,3442795和 4401556,其的教导在此引入作为参考,例如大孔分子筛和它们的制备方法。优选的大孔分子筛是β-沸石,Y沸石和超稳定的Y沸石,并且 β-沸石是更优选的。合适的中孔分子筛包括具有选自下面的骨架的那 些:FER,MFI,OFF,FAU或者MOR,例如ZSM-5或者镁碱沸石。
作为此处使用的,术语“沸石”表示合成的铝硅酸盐分子筛,其具 有由氧化铝和二氧化硅构成的骨架(即,重复的SiO4和AlO4四面体单 元),并且优选二氧化硅-氧化铝摩尔比(SAR)是至少8,例如大约10- 大约50。本发明的沸石不是二氧化硅-铝磷酸盐(SAPO)和因此在它们 的骨架中不具有可评估量的磷。
在某些方面,本发明的沸石晶体是均匀尺寸和形状的,并且具有 相对低量的聚集体。这样的沸石晶体的平均结晶尺寸可以是大约0.1- 大约10μm,例如大约0.5-大约5μm,大约0.1-大约1μm,大约1-大 约5μm,大约3-大约7μm等。直接测量晶体尺寸可以使用显微镜法来进行,例如SEM和TEM。在某些实施方案中,大晶体是使用喷射 研磨机或者其他颗粒对颗粒研磨技术来研磨到平均尺寸是大约1.0-大 约1.5微米,来促进含有该催化剂的浆料到基底例如流过式整料上的 载体涂覆(washcoat)。
该中孔和大孔分子筛可以是金属交换的沸石,特别是过渡金属交 换的分子筛。优选该中孔和大孔分子筛不包含可评估量的骨架过渡金 属。代替地,该过渡金属是作为离子物质存在于该分子筛骨架的内通 道和腔室中。因此,该含过渡金属的沸石不是金属取代的沸石(例如具 有取代到它的骨架结构中的金属的沸石),而代之以可以是金属交换的 沸石(例如经历了过渡金属后合成离子交换的沸石)。在某些实施方案 中,该金属是在沸石合成过程存在的,但是没有混入沸石骨架中。在 某些实施方案中,该沸石没有或者基本上没有除了铜,铁和铝之外的 金属。
可以是后分子筛合成交换或者浸渍的金属的例子包括过渡金属, 其包括铜,镍,锌,铁,钨,钼,钴,钛,锆,锰,铬,钒,铌以及 锡,铋和锑;贵金属,其包括铂族金属(PGM),例如钌,铑,钯,铟, 铂,和贵重金属例如金和银;碱土金属例如铍,镁,钙,锶和钡;和 稀土金属例如镧,铈,镨,钕,铕,铽,铒,镱和钇。用于后合成交 换的优选的过渡金属是贱金属,和优选的贱金属包括选自下面的那些: 锰,铁,钴,镍及其混合物。在后合成混入的金属可以经由任何已知 的技术例如离子交换,浸渍,同形取代等加入分子筛中。在沸石上后 合成交换的金属的量可以是大约0.1-大约20重量%,例如大约1-大约 10重量%,大约0.1-大约1.5重量%,或者大约2-大约6重量%,基 于该沸石的总重量。
氧化锰OMS和中孔或大孔分子筛的相对量可以在宽的范围变化。 因此合适的催化剂包含1-99wt%的OMS和1-99wt%的大孔分子筛。 优选该催化剂包含10-90wt%的OMS和10-90wt%的大孔沸石。更优 选的催化剂包含30-70wt%的OMS和30-70wt%的中孔或大孔分子筛。
该催化剂可以通过多种技术来制备。在一些情况中,氧化锰OMS 和中孔或大孔沸石的简单物理混合可以是最合适的。通常,在使用前 将所述组分以期望的质量比合并和煅烧。在一些情况中,一种或多种 单个组分(OMS和/或分子筛)在它们合并之前可以煅烧。
在另一方案中,将OMS的悬浮液或分散体沉积到沸石上,并且将 该混合物浓缩,干燥和煅烧。类似地,大孔分子筛的悬浮液或分散体 可以沉积到OMS上,随后浓缩,干燥和煅烧。当使用小比例的沸石 或者OMS组分之一时(例如在大孔沸石上1-5wt%的OMS或者在氧化 锰OMS上1-5wt%的大孔或者中孔沸石),这些方法会是期望的。
在另一方法中,制备了复合催化剂。在一个例子中,该氧化锰OMS 是在悬浮的或者分散的中孔或者大孔分子筛的存在下合成的。可选择 地,该中孔或者大孔沸石可以在悬浮的或者分散的预先成形的氧化锰 OMS的存在下合成。在一些情况中,可以甚至令人期望的是在“一锅” 法中,以基本相同的时间合成OMS和中孔或者大孔分子筛。
通常令人期望的是在用于SCR方法之前煅烧本发明的催化剂。优 选煅烧是通过将该催化剂在含氧气氛中,通常在空气中,在300℃ -750℃,更优选400℃-700℃和最优选500℃-600℃的温度加热来进行 的。如图8所示,高的煅烧温度可以钝化该催化剂对于NOx的还原或 者使得用于可接受的NOx转化率的温度窗变窄。
该催化剂可以以任何期望的形式使用,例如粉末,粒料,挤出物, 或者作为沉积在载体或基底上的涂层或者膜。
在催化剂制备后,令人期望的是可以在测试之前均化所述粉末。 因此新制备的催化剂的粉末样品在测试或使用之前可以粒化,粉碎和 过筛(例如255-350μm筛)。
本发明的催化剂特别适用于非均相催化反应体系(即,与气体反应 物接触的固体催化剂)。为了提高接触表面积,机械稳定性和/或流体 流动特性,该催化剂可以置于基底之上和/或之内,优选是多孔基底。 在某些实施方案中,将含有该催化剂的载体涂层施用到惰性基底例如 波纹化金属板或者蜂窝堇青石块上。可选择地,将该催化剂与其他组 分例如填料,粘合剂和增强剂一起捏合成挤出糊料,其然后挤出通过 口模来形成蜂窝块。因此在某些实施方案中提供的是催化剂制品,其 包含涂覆到基底上和/或混入基底中的此处所述的催化剂。
本发明的某些方面提供了一种催化活性涂层。该包含此处所述的 催化剂的载体涂层优选是溶液,悬浮液或者浆料。合适的涂层包括表 面涂层,渗透到一部分基底中的涂层,渗透到基底中的涂层或者其的 一些组合。
载体涂层还可以包括非催化组分例如填料,粘合剂,稳定剂,流 变改性剂和其他添加剂,包括一种或多种的氧化铝,二氧化硅,非沸 石二氧化硅氧化铝,二氧化钛,氧化锆,二氧化铈。在某些实施方案 中,该催化剂组合物可以包含成孔剂例如石墨,纤维素,淀粉,聚丙 烯酸酯和聚乙烯等。这些另外的组分不必催化期望的反应,而代之以 改进了该催化材料的效力,例如通过增加它的操作温度范围,增加该 催化剂的接触表面积,增加该催化剂到基底的粘附力等来改进。在优 选的实施方案中,载体涂层负载量>0.3g/in3,例 如>1.2g/in3,>1.5g/in3,>1.7g/in3或者>2.00g/in3,和优选<3.5g/in3,例 如<2.5g/in3。在某些实施方案中,该载体涂层以下面的负载量施用到 基底上:大约0.8-1.0g/in3,1.0-1.5g/in3或者1.5-2.5g/in3。
最普遍的两种基底设计是板式和蜂窝式。优选的基底(特别是用于 移动应用的)包括流过式整料,其具有所谓的蜂窝几何形状,包含多个 相邻的平行通道,该通道是两端开口的,并且通常从基底的入口面延 伸到出口面,和产生高的表面积-体积比。对于某些应用来说,该蜂窝 流过式整料优选具有高的孔密度,例如大约600-800个孔/平方英寸, 和/或平均内壁厚度是大约0.18-0.35mm,优选大约0.20-0.25mm。对 于某些应用来说,蜂窝流过式整料优选具有大约150-600个孔/平方英 寸,更优选大约200-400个孔/平方英寸的低孔密度。优选该蜂窝整料 是多孔的。除了堇青石,碳化硅,氮化硅,陶瓷和金属之外,可以用于所述基底的其他材料包括氮化铝,氮化硅,钛酸铝,α-氧化铝,多 铝红柱石例如针状多铝红柱石,铯榴石,thermet例如Al2OsZFe, Al2O3/Ni或者B4CZFe,或者包含其任何两种或更多的片段的复合材 料。优选的材料包括堇青石,碳化硅和氧化铝钛酸酯。
板类型的催化剂与蜂窝类型相比具有较低的压力下降,并且不太 容易堵塞和结垢,其在高效固定应用中是有利的,但是板构造会是明 显更大和更昂贵的。蜂窝构造通常小于板类型,其在移动应用中是有 利的,但是具有较高的压力下降和更易堵塞。在某些实施方案中,板 式基底是由金属构成的,优选波纹化金属。
在某些实施方案中,本发明是通过此处所述的方法制造的催化剂 制品。在一种具体的实施方案中,该催化剂制品是通过这样的方法生 产的,其包括步骤:在用于处理废气的另外一种组合物的至少另一层 施涂到基底上之前或之后,将该催化剂组合物,优选作为载体涂层, 作为层施涂到基底上。该基底上的一个或多个催化剂层(包括本发明的 催化剂层)是以连续层排列的。作为此处使用的,与基底上的催化剂层 有关的术语“连续的”表示每个层是与它相邻的(一个或多个)层接触 的,并且该催化剂层作为整体在基底上叠置排列。
在某些实施方案中,本发明的催化剂作为第一层布置在基底上, 并且另一种组合物例如氧化催化剂,还原催化剂,清除组分或者NOx存储组分作为第二层布置在该基底上。在其他实施方案中,本发明的 催化剂作为第二层置于基底上,并且另一种组合物例如氧化催化剂, 还原催化剂,清除组分或者NOx存储组分作为第一层置于该基底上。 作为此处使用的,术语“第一层”和“第二层”被用于描述催化剂层在催 化剂制品中相对于流过穿过、流过该催化剂制品和/或流过其上的废气 的法线方向的相对位置。在正常的废气流动条件下,废气在接触第二 层之前接触第一层。在某些实施方案中,将第二层作为底层施用到惰性基底上,并且第一层是顶层,其作为连续系列的子层施用到第二层 上。在这样的实施方案中,废气透过(和因此接触)第一层,然后接触 第二层,随后穿过第一层返回来离开该催化剂组分。在其他实施方案 中,第一层是置于基底上游部分上的第一区,和第二层作为第二区置 于该基底上,其中该第二区在第一区下游。
在另一实施方案中,该催化剂制品是通过这样的方法生产的,其 包括步骤:将本发明的催化剂组合物优选作为载体涂层施涂到基底上 作为第一区,和随后将用于处理废气的至少一种另外的组合物施涂到 基底上作为第二区,其中至少一部分的该第一区在第二区的下游。可 选择地,本发明的催化剂组合物可以施涂到第二区中的基底上,该第 二区在含有另外的组合物的第一区的下游。另外的组合物的例子包括 氧化催化剂,还原催化剂,清除组分(例如用于硫,水等)或者NOx存 储组分。
为了减少排气系统所需空间的量,单个排气部件在某些实施方案 中被设计来执行大于一种的功能。例如将SCR催化剂施用到代替流过 式基底的壁流式过滤器基底上,通过使得一个基底起动两种功能(即, 催化减少废气中的NOx浓度和机械除去废气中的煤烟),来减少排气处 理系统的整体尺寸。因此在某些实施方案中,该基底是蜂窝壁流式过滤器或者部分过滤器。壁流式过滤器类似于流过式蜂窝基底之处在于 它们包含多个相邻的平行通道。但是,该流过式蜂窝基底的通道是两 端开口的,而壁流式基底的通道一端是封闭的,其中该封闭是以交替 方式发生在相邻通道的对端上的。封闭通道的交替端防止了进入基底 入口面的气体直接流过该通道和离开。代替地,该废气进入基底前部, 行进到通道大约一半处,在这里它被驱使穿过通道壁,然后进入通道 的另一半处,并且离开基底的背面。
该基底壁具有一定的孔隙率和孔尺寸,其是气体可透过的,但是 在气体送过该壁时截留了气体中大部分的颗粒物质例如煤烟。优选的 壁流式基底是高效过滤器。用于本发明的壁流式过滤器优选的效率是 至少70%,至少大约75%,至少大约80%或者至少大约90%。在某 些实施方案中,该效率将是大约75-大约99%,大约75-大约90%, 大约80-大约90%或者大约85-大约95%。这里效率是相对于煤烟和 其他类似尺寸的颗粒和相对于常规柴油废气中典型存在的颗粒浓度 的。例如柴油废气中的颗粒的尺寸可以是0.05微米-2.5微米。因此该 效率可以基于这个范围或子范围,例如0.1-0.25微米,0.25-1.25微米 或者1.25-2.5微米。
孔隙率是多孔基底中空隙空间百分比的量度,并且与排气系统中 的背压有关:通常孔隙率越低,背压越高。优选该多孔基底的孔隙率 是大约30-大约80%,例如大约40-大约75%,大约40-大约65%或者 大约50-大约60%。
孔互连率是作为基底的总空隙体积的百分比来测量的,其是孔、 空隙和/或通道连接来形成穿过多孔基底的连续通路(即,从入口面到 出口面)的程度。与孔互连率相反的是闭孔体积和具有到基底仅仅一个 表面的导管的孔的体积的总和。优选该多孔基底的孔互连率体积是至 少大约30%,更优选至少大约40%。
该多孔基底的平均孔尺寸对于过滤来说也是重要的。平均孔尺寸 可以通过任何可接受的手段来测量,包括通过汞孔隙率法来测量。多 孔基底的平均孔尺寸应当是足够高的值来促进低的背压,同时通过基 底本身,通过促进基底表面上的煤烟饼层,或者二者的组合来提供足 够的效率。优选的多孔基底的平均孔尺寸是大约10-大约40μm,例如 大约20-大约30μm,大约10-大约25μm,大约10-大约20μm,大约 20-大约25μm,大约10-大约15μm和大约15-大约20μm。
通常,含有该催化剂的挤出实心体的生产包括将该催化剂,粘合 剂,任选的有机粘度增强化合物共混成均匀的糊料,其然后被加入粘 合剂/基质组分或者其前体和任选的一种或多种的稳定的二氧化铈,和 无机纤维。该共混物在混合或者捏合设备或者挤出机中压实。该混合 物具有有机添加剂例如粘合剂,成孔剂,增塑剂,表面活性剂,润滑 剂,分散剂作为加工助剂来增强润湿性,和因此生产均匀批次料。所 形成的塑性材料然后模制,特别是使用挤压机或者挤出机(包括挤出口 模)来进行,并且将所形成的模制件干燥和煅烧。该有机添加剂在挤出 的实心体煅烧过程中“烧掉”。该催化剂也可以进行载体涂覆或者以其他方式作为一个或多个子层(其存在于挤出的实心体的表面上或者 整个或者部分地渗透到其中)施用到挤出的实心体。
含有本发明的催化剂的挤出实心体通常包含蜂窝形式的整体结 构,其具有从其第一端延伸到第二端的均匀大小和平行的通道。限定 出通道的通道壁是多孔的。通常,外“皮”包围着该挤出的实心体的多 个通道。该挤出的实心体可以由任何期望的横截面形成,例如圆形, 正方形或椭圆形。多个通道中的单个通道可以是正方形,三角形,六 边形,圆形等。在第一上游端处的通道可以是封闭的,例如用合适的 陶瓷水泥封闭,并且在第一上游端处没有封闭的通道也可以在第二下 游端处封闭,来形成壁流式过滤器。通常,在第一上游端处封闭的通 道的排列类似于棋盘,封闭和开放的下游通道端具有类似的排列。
该粘合剂/基质组分优选是选自堇青石,氮化物,碳化物,硼化物, 金属间化物,铝硅酸锂,尖晶石,任选掺杂的氧化铝,二氧化硅源, 二氧化钛,氧化锆,二氧化钛-氧化锆,锆石及其任意两种或更多种的 混合物。该糊料可以任选地包含选自下面的增强性无机纤维:碳纤维, 玻璃纤维,金属纤维,硼纤维,氧化铝纤维,二氧化硅纤维,二氧化 硅-氧化铝纤维,碳化硅纤维,钛酸钾纤维,硼酸铝纤维和陶瓷纤维。
该氧化铝粘合剂/基质组分优选是γ氧化铝,但是可以是任何其他 过渡氧化铝,即,α氧化铝,β氧化铝,χ氧化铝,η氧化铝,ρ氧 化铝,κ氧化铝,θ氧化铝,δ氧化铝,镧β氧化铝和任何两种或更 多种这样的过渡氧化铝的混合物。优选的是该氧化铝是用至少一种非 铝元素掺杂的,来增加氧化铝的热稳定性。合适的氧化铝掺杂剂包括 硅,锆,钡,镧系元素及其任何两种或更多种的混合物。合适的镧系 元素掺杂剂包括La,Ce,Nd,Pr,Gd及其任何两种或更多种的混合 物。
二氧化硅源可以包括二氧化硅溶胶,石英,熔凝或者无定形二氧 化硅,硅酸钠,无定形铝硅酸盐,烷氧基硅烷,有机硅树脂粘合剂例 如甲基苯基有机硅树脂,粘土,滑石及其任何两种或更多种的混合物。 在这个列表中,二氧化硅可以是SiO2本身,长石,多铝红柱石,二氧 化硅-氧化铝,二氧化硅-氧化镁,二氧化硅-氧化锆,二氧化硅-氧化钍, 二氧化硅-氧化铍,二氧化硅-二氧化钛,三元二氧化硅-氧化铝-氧化锆, 三元二氧化硅-氧化铝-氧化镁,三元-二氧化硅-氧化镁-氧化锆,三元 二氧化硅-氧化铝-氧化钍及其任何两种或更多种的混合物。
优选该催化剂是彻底分散和优选均匀彻底分散在整个挤出的催化 剂体中的。
在任何上面的挤出的实心体制成壁流式过滤器的情况中,该壁流 式过滤器的孔隙率可以是30-80%,例如40-70%。孔隙率和孔体积和 孔半径可以例如使用压汞孔隙率法来测量。
此处所述的催化剂会促进还原剂(优选氨)与氮氧化物的反应,来选 择性形成元素氮(N2)和水(H2O)。因此在一种实施方案中,该催化剂可 以配制来促进氮氧化物用还原剂的还原(即,SCR催化剂)。这样的还 原剂的例子包括烃(例如C3-C6烃)和含氮还原剂例如氨和氨肼或者任 何合适的氨前体例如尿素((NH2)2CO),碳酸铵,氨基甲酸铵,碳酸氢 铵或者甲酸铵。
此处所述的沸石催化剂也会促进氨的氧化。因此在另一实施方案 中,该催化剂可以配制来促进氨用氧气的氧化,特别是在SCR催化剂 (例如氨氧化(AMOX)催化剂,例如氨泄露催化剂(ASC))下游遇到的通 常的氨浓度。在某些实施方案中,本发明的催化剂作为顶层置于氧化 性下层之上,其中该下层包含铂族金属(PGM)催化剂或者非PGM催 化剂。优选下层中的该催化剂组分位于高表面积载体上,其包括但不 限于氧化铝。
在仍然的另一实施方案中,SCR和AMOX操作是串联进行的, 其中两种方法都使用了包括此处所述的催化剂的催化剂,和其中该 SCR方法在AMOX方法的上游进行。例如该催化剂的SCR配制物可 以位于过滤器的入口侧上,和该催化剂的AMOX配制物可以位于该 过滤器的出口侧上。
因此提供的是还原气体中NOx化合物或者氧化NH3的方法,其包 括将该气体与此处所述的用于催化还原NOx化合物的催化剂组合物接 触足够的时间,来降低气体中NOx化合物和/或NH3的水平。在某些 实施方案中,提供的是催化剂制品,其具有位于选择性催化还原(SCR) 催化剂下游的氨泄露催化剂。在这样的实施方案中,该氨泄露催化剂 氧化了至少一部分的任何含氮还原剂(其没有被选择性催化还原方法 所消耗)。例如在某些实施方案中,该氨泄露催化剂位于壁流式过滤器 的出口侧上,和SCR催化剂位于过滤器的上游侧。在某些其他实施方 案中,该氨泄露催化剂位于流过式基底的下游端上,和SCR催化剂位 于该流过式基底的上游端上。在其他实施方案中,该氨泄露催化剂和 SCR催化剂位于排气系统内分别的块上。这些分别的块可以彼此相 邻,和彼此接触,或者以特定的距离间隔开,条件是它们是彼此流体 连通的,和条件是SCR催化剂块位于氨泄露催化剂块的上游。
在某些实施方案中,该SCR和/或AMOX方法是在至少100℃的 温度进行的。在另一实施方案中,该(一种或多种)方法在大约150℃- 大约750℃的温度进行。在一种具体实施方案中,该温度范围是大约 175-大约550℃。在另一实施方案中,该温度范围是175-400℃。在仍 然的另一实施方案中,该温度范围是450-900℃,优选500-750℃, 500-650℃,450-550℃或者650-850℃。使用大于450℃的温度的实施 方案特别地可用于处理来自于重型和轻型柴油机的废气,其装备有包 含(任选催化的)柴油颗粒过滤器的排气系统,该过滤器是例如通过将 烃注入过滤器上游的排气系统中来主动再生的,其中用于本发明的沸 石催化剂位于过滤器的下游。
根据本发明的另一方面,提供的是还原气体中NOx化合物和/或氧 化NH3的方法,其包括将该气体与此处所述的催化剂接触足够的时间, 来降低气体中NOx化合物的水平。本发明的方法可以包含一个或多个 下面的步骤:(a)聚集和/或燃烧与催化过滤器入口接触的煤烟;(b)在 接触该催化过滤器之前,将含氮还原剂引入废气流中,优选不具有插 入的包括处理NOx和还原剂的催化步骤;(c)在NOx吸附剂催化剂或者 贫NOx阱上产生NH3,和优选使用这样的NH3作为下游SCR反应中 的还原剂;(d)将该废气流与DOC接触来将烃基可溶性有机级分(SOF) 和/或一氧化碳氧化成CO2,和/或将NO氧化成NO2,其进而可以用 于氧化颗粒过滤器中的颗粒物质;和/或减少废气中的颗粒物质(PM); (e)将该废气与一个或多个流过式SCR催化剂装置在还原剂的存在下 接触,来降低废气中的NOx浓度;和(f)将该废气与氨泄露催化剂(优 选在SCR催化剂下游)接触,来氧化大部分(如果不是全部的话)氨,然 后将该废气排放到大气中或者将该废气送过再循环回路,然后废气进 入/再进入发动机中。
在另一实施方案中,全部或者至少一部分的用于在SCR方法中消 耗的氮基还原剂,特别是NH3可以通过NOX吸附剂催化剂(NAC),贫 NOX阱(LNT)或者NOX存储/还原催化剂(NSRC)(其位于SCR催化剂 上游,例如位于本发明的在壁流式过滤器上布置的SCR催化剂上游) 来提供。可用于本发明的NAC组分包括碱性(basic)材料(例如碱金属, 碱土金属或者稀土金属,包括碱金属氧化物,碱土金属氧化物及其组 合)和贵金属(例如铂)和任选的还原催化剂组分例如铑的催化剂组合 物。可用于该NAC中的具体类型的碱性材料包括氧化铯,氧化钾, 氧化镁,氧化钠,氧化钙,氧化锶,氧化钡及其组合。贵金属优选是 以大约10-大约200g/ft3,例如20-60g/ft3存在的。可选择地,该催化 剂的贵金属特征在于其平均浓度可以是大约40-大约100g/ft3。
在某些条件下,在定期富集再生事件中,NH3可以在NOx吸附剂 催化剂上产生。NOx吸附剂催化剂下游的SCR催化剂可以改进整个系 统NOx还原效率。在该组合的系统中,该SCR催化剂能够存储在富 集再生事件中从NAC催化剂释放的NH3,并且使用该存储的NH3来选择性还原一些或全部的在常规的贫化操作条件过程中通过NAC催 化剂泄露的NOx。
此处所述的处理废气的方法可以在来源于燃烧方法的废气上进 行,例如来源于内燃机(无论是移动的,还是固定的),燃气轮机和燃 煤或者燃油发电机。该方法也可以用于处理来自于下面的气体:工业 方法例如精炼,精炼厂加热器和锅炉,炉子,化工工业,焦炭炉,市 政废水厂和焚化炉等。在一种具体的实施方案中,该方法被用于处理 来自于下面的废气:车辆贫燃内燃机例如柴油机,贫燃汽油机或者液 体石油气或天然气供能的发动机。
在某些方面,本发明是用于处理燃烧方法所产生的废气的系统, 例如来自于下面的废气:内燃机(移动的或固定的),燃气轮机,燃煤 或者燃油发电厂等。这样的系统包括催化制品(其包含此处所述的催化 剂)和用于处理废气的至少一种另外的组分,其中该催化制品和至少一 种另外的组分被设计来充当了相关单元。
在某些实施方案中,该系统包含催化制品(其包含此处所述的催化 剂),用于引导流动废气的导管,位于该催化制品上游的含氮还原剂源。 该系统可以包括控制器,用于仅仅当确定沸石催化剂能够以处于或高 于期望的效率催化NOx还原,例如在高于100℃,高于150℃或高于 175℃时,将含氮还原剂计量到流动废气中。可以安排含氮还原剂的计 量,以使得60%-200%的理论的氨存在于进入SCR催化剂的废气中, 其是以1:1的NH3/NO和4:3的NH3/NO2来计算的。
在另一实施方案中,该系统包含用于将废气中的一氧化氮氧化成 二氧化氮的氧化催化剂(例如柴油氧化催化剂(DOC)),其可以位于将含 氮还原剂计量到废气中的点的上游。在一种实施方案中,该氧化催化 剂适用于例如在氧化催化剂入口处的废气温度为250℃-450℃时,产 生进入SCR沸石催化剂的气流,其的NO/NO2体积比是大约4:1-大 约1:3。该氧化催化剂可以包括至少一种铂族金属(或者它们的某些 组合),例如铂,钯或者铑,其涂覆在流过式整料基底上。在一种实施 方案中,该至少一种铂族金属是铂,钯或者铂和钯二者的组合。该铂 族金属可以负载在高表面积的载体涂层组分例如氧化铝,沸石例如铝 硅酸盐沸石,二氧化硅,非沸石二氧化硅氧化铝,二氧化铈,氧化锆, 二氧化钛或者含有二氧化铈和氧化锆二者的混合的或者复合的氧化物 上。
下面的实施例仅仅说明本发明;本领域技术人员将认可处于本发 明主旨和权利要求范围内的许多变化。
OMS-2的合成
在安装有冷凝器和磁搅拌棒的圆底烧瓶中,将水合硫酸锰(44.0g, 0.26mol)溶解在水(150mL)和浓硝酸(12mL)的混合物中。加入高锰酸钾 (29.5g,0.185mol)在水(500mL)中的溶液,并且将该混合物在三天的时 间内回流16h(第一天:6.5h;第二天:7.5h;第三天:2h)。固体是通 过过滤和用水洗直到电导率为大约20μS来回收的。将该产物在105℃ 干燥。收率:41.2g。在使用前,将该催化剂在500℃(“F500C”)煅烧 2h或者在600℃(“F600C”)煅烧2h。
制备β-沸石载5%Fe
在市售的β-沸石载5wt%铁催化剂是使用初湿含浸法技术,如下 来制备的:将产生5wt%Fe负载量所需量的硝酸铁(Fe(NO3)3·9H2O) 溶解在去离子水中。该溶液的总体积等价于样品的孔体积。将该溶液 加入到β-沸石中,并且将所形成的混合物在105℃干燥过夜,然后在 500℃在空气中煅烧1h。
制备β-沸石上5%Fe和OMS-2的物理混合物
将OMS-2和如上所述制备的β-沸石载5%Fe催化剂以2:1,1: 1或者1:2的质量比合并,并且将该物理混合物在500℃,550℃或在 600℃煅烧2h。
制备OMS-2/β-沸石(1:1)复合物
在安装有冷凝器和磁搅拌棒的圆底烧瓶中,将水合硫酸锰(11.02g, 0.065mol)溶解在水(37.5mL)和浓硝酸(3.0mL)的混合物中。一旦硫酸锰 溶解,则加入β-沸石(10.0g)来形成粉红色浆料,将其搅拌直到均匀。 加入高锰酸钾(7.36g,0.047mol)在水(125mL)中的溶液,并且将该混合 物回流过夜。该固体是通过过滤和用水洗直到电导率为大约20μS来回收的。将该产物在105℃干燥。收率:大约20g。在使用前将该复合 催化剂在500℃煅烧2h。对于一些实验,将该催化剂在600℃进一步 煅烧2h。
制备OMS-2/USY(1:1)复合物
使用了用于制备OMS-2/β-沸石复合物的程序,除了使用超稳定的 Y-沸石来代替β-沸石之外。在使用前将该复合催化剂在500℃煅烧2h。 对于一些实验,将该催化剂在600℃进一步煅烧2h。
OMS-2和堇青石的物理混合物
将预先粒化的堇青石以1:1的质量比与预先粒化的OMS-2(其已 经在500℃煅烧了2h)进行物理混合。
NH3-SCR活性测试条件
催化剂的粉末样品是通过如下来获得的:将初始样品粒化,压碎 粒料,然后将所形成的粉末送过255-350μm筛子。将过筛的粉末装载 入合成催化剂活性测试(SCAT)反应器中,并且使用下面的合成柴油废 气混合物(在入口)处来测试,所述合成柴油废气混合物包括作为还原 剂的氨:350ppm的NO,385ppm的NH3,12%的O2,4.5%的CO2, 4.5%的H2O,余量的N2,空速是30000h-1。
将样品以5℃/min从150℃逐渐加热到550℃,并且使用FTIR光 谱法来分析废气的组成,来测定NOx气体的百分比转化率。
结果
图1显示了通过在β-沸石的存在下合成OMS-2所制造的复合催化 剂产生了远少于单独的OMS-2催化剂的N2O。该N2O还原是令人惊 讶的和有益的,这是因为虽然已知OMS催化剂产生了N2O,但是不 清楚如何在使用它们时使得N2O形成最小化或者避免其形成。
图2显示了当使用OMS-2和β-沸石的复合催化剂时,用于NOx 转化的温度范围变宽。具体地,对于该复合物来说,高温范围(300℃ -400℃)扩大,虽然付出了在低温端(150℃-200℃)的一些损失的代价。
图3是对比例图,其显示了OMS-2和堇青石的1:1物理混合物 在降低使用单独的OMS-2所见的N2O形成方面是无效的。实际上, 该1:1混合物产生了与单独的OMS-2一样多的N2O。
图4是另一对比例图。它显示了OMS-2和堇青石的1:1物理混 合物,不同于OMS-2/β-沸石复合物那样,其在扩大用于NOx转化的 高温范围方面是无效的。对于在低温(150℃-250℃)下的NOx转化率来 说,该OMS-2/堇青石混合物的效率也稍低于OMS-2。
图5显示了将OMS-2与β-沸石载5wt%铁以各重量比合并时的影 响。与单独的OMS-2相比,全部的OMS-2/Feβ-沸石混合物成功地降 低了N2O形成。较高比例的β-沸石(1份OMS-2比2份Feβ-沸石)表 现出提供了最少的N2O产生。在β-沸石上5%Fe的对比例图也显示了低的N2O形成。
图6显示了将OMS-2与在β-沸石上5wt%铁以各重量比合并,对 于NOx转化率的影响。当与单独的OMS-2对比时,全部的OMS-2/Fe β-沸石混合物扩大了用于NOx转化的高温范围(200℃-400℃)。在每个 情况中,在低温端(150℃-200℃)的小折衷伴随着在高温端的收获。较 高比例的β-沸石(1份OMS-2比2份Feβ-沸石)将高温性能扩大到更大 的程度。在β-沸石上5wt%Fe的对比例图显示了这种催化剂对于在低 温(150-250℃)范围的NOx转化具有非常低的活性。
图7显示了煅烧会具有对于N2O产生的益处。没有煅烧时,OMS-2/ Feβ-沸石混合物在150℃-350℃范围产生了可容忍水平(70ppm)的 N2O,并且远小于单独的OMS-2(参见图1)。但是,在500℃,550℃ 和600℃煅烧该催化剂渐进地减少了在150℃-350℃范围的N2O产生。
图8显示了煅烧所提供的N2O中另外的还原(图7)是以付出了渐进 地更窄的适于NOx转化的温度窗为代价的。因此当该催化剂在高温煅 烧时,它产生了最小量的N2O,但是它也牺牲了在该测试的低温和高 温端二者的NOx转化率。
图9显示了与单独的OMS-2相比,由OMS-2和大孔沸石(β-沸石 或超稳定的Y-沸石)制备的本发明的复合催化剂形成了降低水平的 N2O,具有用于OMS-2和β-沸石(1:2)复合物的最佳选择性。在600℃ 煅烧的OMS-2催化剂也形成了很少的N2O,但是如图10所示,它在较高的煅烧温度下钝化。
图10显示了与单独的OMS-2相比,本发明的复合催化剂具有改 进的热稳定性。此外,对于复合催化剂,NOx转化率通常在较高温度 (350-400℃)下改进。在这里所测试的催化剂中,在500℃煅烧的 OMS-2/β-沸石(1:2)复合物是在最宽的温度范围上对于NOx还原是最 有效的。
图11显示了热老化(在550℃煅烧16h)对于N2O形成的影响。与 老化的OMS-2和菱沸石(小孔沸石)复合物相比,该基于OMS-2和超 稳定的Y-沸石或β-沸石(大孔沸石)复合物的老化的催化剂产生了更少 的N2O。
图12显示了对于NOx转化来说,复合催化剂在热老化时保持活 性优于单独的OMS-2。与OMS-2和菱沸石的老化的复合物相比,基 于OMS-2和超稳定的Y-沸石或者β-沸石的复合物的老化的催化剂在 较宽的温度范围上有效的降低了NOx。
图13显示了将OMS-2与金属负载的β-沸石,金属负载的FER- 沸石和金属负载的ZSM-5沸石合并的效果。在宽的温度范围上,与单 独的OMS-2或者OMS-2加上金属负载的小孔沸石(CHA)相比,具有 OMS-2的中孔和大孔沸石成功地降低了N2O形成。
图14显示了将OMS-2与金属负载的β-沸石,金属负载的FER- 沸石和金属负载的ZSM-5沸石合并的效果。具有OMS-2的中孔和大 孔沸石成功地表现出与OMS-2加上金属负载的小孔沸石(CHA)相比 在低温(例如低于200℃)改进的NOx转化率,和表现出与OMS-2加上金属负载的小孔沸石(CHA)和单独的OMS-2二者相比,在高温(例如 高于360℃)改进的NOx转化率。
前述实施例目的仅仅是作为说明;所附的权利要求限定了本发明 的范围。
Claims (29)
1.用于选择性催化还原的催化剂,其包含:
(a)1-99wt%的包含氧化锰的八面体分子筛(OMS);和
(b)1-99wt%的一种或多种中孔和/或大孔分子筛,其中所述中孔和/或大孔分子筛是沸石或硅铝磷酸盐(SAPO)。
2.权利要求1的催化剂,其中该中孔和/或大孔分子筛进一步包含铁或者铜。
3.权利要求2的催化剂,其包含分子筛载0.1-10wt%的铁或铜。
4.权利要求1的催化剂,其包含10-90wt%的OMS和90-10wt%的该中孔和/或大孔分子筛。
5.权利要求1的催化剂,其中该八面体分子筛是OMS-2。
6.权利要求1的催化剂,其中该OMS是在该中孔和/或大孔分子筛的存在下形成的。
7.权利要求1的催化剂,其包含OMS和该中孔和/或大孔分子筛的物理混合物。
8.权利要求1的催化剂,其中该OMS沉积在该中孔和/或大孔分子筛上。
9.权利要求1的催化剂,其中该OMS是用选自下面的一种或多种金属掺杂的:Ca、Ti、V、Cr、Fe、Co、Ni、Cu、Zn、Ce、Zr、Mo、W和Pr。
10.权利要求1的催化剂,其中该分子筛的骨架选自β、超稳定的Y、FER和MFI中的一种或多种。
11.方法,其包括在还原剂和权利要求1的催化剂的存在下,选择性还原包含氮氧化物的气态混合物。
12.权利要求11的方法,其是在100℃-650℃的温度进行的。
13.权利要求11的方法,其中该还原剂选自氨和C1-C8烃中的一种或多种。
14.权利要求13的方法,其中该还原剂是氨。
15.权利要求11的方法,其中该催化剂包括OMS-2和β-沸石、FER-沸石、Y-沸石、FAU-沸石或者MFI-沸石。
16.权利要求15的方法,其中该OMS-2是在β-沸石、FER-沸石、Y-沸石、FAU-沸石或者MFI-沸石的存在下形成的。
17.权利要求15的方法,其中该催化剂是在300℃-750℃下煅烧的。
18.权利要求11的方法,其中该催化剂包含β-沸石、FER-沸石、Y-沸石、FAU-沸石或者MFI-沸石载铁,和OMS-2。
19.权利要求18的方法,其中该催化剂是在300℃-700℃下煅烧的。
20.权利要求11的方法,其中与其中使用了没有沸石的OMS催化剂的类似方法相比,改进了氮氧化物在大于300℃的温度的百分比转化率。
21.权利要求11的方法,其中与其中使用了没有沸石的OMS催化剂的类似方法相比,降低了在150℃-400℃下的N2O形成。
22.权利要求11的方法,其中与其中使用了没有OMS的沸石催化剂的类似方法相比,改进了氮氧化物在150℃-250℃的温度下的百分比转化率。
23.用于处理含有氮氧化物的废气的制品,其包含基底和沉积在该基底上的权利要求1的催化剂。
24.权利要求23的制品,其中该基底是整料、板或者片。
25.方法,其包括处理废气混合物中的氮氧化物,该方法包含在还原剂的存在下,将至少一部分的氮氧化物与权利要求23的制品接触,来将至少一部分的氮氧化物选择性还原成N2和水。
26.权利要求25的方法,其中所述还原剂为含氮还原剂或者氨前体。
27.权利要求26的方法,其中所述含氮还原剂为氨或者氨肼,并且所述氨前体为尿素、碳酸铵、氨基甲酸铵、碳酸氢铵或者甲酸铵。
28.处理含有氨的废气的制品,其包含基底和沉积在该基底上的包含权利要求1的催化剂的第一层或者区,和包含氨氧化催化剂的第二层或者区。
29.方法,其包括处理SCR方法下游废气中的氨,其包含将至少一部分的氨与权利要求28的制品接触,来氧化至少一部分的氨。
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PCT/IB2014/059834 WO2014141199A1 (en) | 2013-03-14 | 2014-03-14 | Aluminosilicate or silicoaluminophosphate molecular sieve/manganese octahedral molecular sieve as catalysts for treating exhaust gas |
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US10081006B2 (en) * | 2014-12-17 | 2018-09-25 | University Of Connecticut | Adsorptive desulfurization |
KR101744813B1 (ko) | 2015-09-14 | 2017-06-20 | 현대자동차 주식회사 | 수동변속기 차량의 엔진 제어 시스템 및 방법 |
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CN106975481B (zh) * | 2017-04-22 | 2019-10-25 | 武汉理工大学 | 具有高效光热协同催化净化VOCs的碱土金属掺杂MnO2催化剂的制备方法 |
CN108744953B (zh) * | 2018-05-22 | 2020-06-30 | 中南大学 | 一种oms-2和/或金属掺杂oms-2催化烟气脱硝的应用方法 |
CN111099637B (zh) | 2018-10-25 | 2023-03-03 | 中国石油化工股份有限公司 | 硅磷铝分子筛及其制备方法 |
CN109569582A (zh) * | 2018-11-23 | 2019-04-05 | 南昌大学 | 一种基于静电锚定-氧化还原固化技术复合氧化物的制备方法及应用 |
CN110038556B (zh) * | 2019-05-06 | 2020-07-28 | 中国科学院兰州化学物理研究所 | 具有混合结晶相的oms-2型复合材料、其制法及应用 |
CN112844449B (zh) * | 2019-11-27 | 2022-04-22 | 中国科学院大连化学物理研究所 | 一种PdO-CeO2-OMS纤维膜催化剂的制备方法及在汽车尾气中的应用 |
CN114251158B (zh) * | 2020-09-24 | 2022-09-16 | 广东加南环保生物科技有限公司 | 柴油机排气颗粒物催化型过滤器及其制造方法 |
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GB201518177D0 (en) | 2015-11-25 |
JP6377086B2 (ja) | 2018-08-22 |
DE112014001315T5 (de) | 2015-12-24 |
JP2016515923A (ja) | 2016-06-02 |
EP2969189A1 (en) | 2016-01-20 |
GB2532595B (en) | 2018-12-05 |
US20160288107A1 (en) | 2016-10-06 |
CN105050710A (zh) | 2015-11-11 |
RU2662821C2 (ru) | 2018-07-31 |
RU2015143209A (ru) | 2017-04-20 |
WO2014141199A1 (en) | 2014-09-18 |
BR112015022314A2 (pt) | 2017-07-18 |
GB2532595A (en) | 2016-05-25 |
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