CN117065794A - 单层或双层氨泄漏催化剂 - Google Patents
单层或双层氨泄漏催化剂 Download PDFInfo
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- CN117065794A CN117065794A CN202311029938.1A CN202311029938A CN117065794A CN 117065794 A CN117065794 A CN 117065794A CN 202311029938 A CN202311029938 A CN 202311029938A CN 117065794 A CN117065794 A CN 117065794A
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- Prior art keywords
- catalyst
- scr catalyst
- molecular sieve
- scr
- platinum
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 288
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title abstract description 116
- 229910021529 ammonia Inorganic materials 0.000 title abstract description 57
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000010410 layer Substances 0.000 claims abstract description 91
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 56
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 239000002356 single layer Substances 0.000 claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims description 102
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 102
- 239000000203 mixture Substances 0.000 claims description 84
- 239000002184 metal Chemical group 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000011148 porous material Substances 0.000 claims description 42
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 25
- 239000010457 zeolite Substances 0.000 claims description 25
- 229910021536 Zeolite Inorganic materials 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000010953 base metal Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 241001185310 Symbiotes <prokaryote> Species 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 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 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 229910004625 Ce—Zr Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 48
- 239000007789 gas Substances 0.000 description 45
- 239000000758 substrate Substances 0.000 description 22
- 238000009472 formulation Methods 0.000 description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 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 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012530 fluid Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- -1 copper amine salts Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 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
- 239000000725 suspension Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 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 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001956 copper hydroxide 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
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 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
- KMHJKRGRIJONSV-UHFFFAOYSA-N dioxygen(.1+) Chemical compound [O+]=O KMHJKRGRIJONSV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052642 spodumene 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
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- 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
- B01D53/9404—Removing only nitrogen compounds
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Abstract
一种催化剂制品,其具有:具有在发动机运行过程中废气流过的多个通道的挤出的载体,和该载体上的单层涂层或双层涂层,其中该挤出的载体含有第三SCR催化剂,该单层涂层和该双层涂层含有氨储存性低的载体上的铂和第一SCR催化剂。该催化制品可用于选择性催化还原(SCR)废气中的NOx和减少氨泄漏的量。描述了生产这样的制品的方法。还描述了在SCR方法中使用该催化制品的方法,在该SCR方法中氨泄漏的量减小。
Description
本申请是基于申请号为201680043641.2、申请日为2016年6月16日、发明名称为“单层或双层氨泄漏催化剂”的中国专利申请的分案申请。
发明领域
本发明涉及氨泄漏催化剂(ASC),含有氨泄漏催化剂的制品,和制造和使用这样的制品来减少氨泄漏的方法。
发明背景
柴油发动机、固定式燃气轮机和其他***中的烃燃烧产生废气,必须处理该废气来除去氮氧化物(NOx),其包括NO(一氧化氮)和NO2(二氧化氮),并且NO占形成的NOx的主要部分。已知NOx引起人们的许多健康问题,以及引起许多有害的环境效应,包括形成烟雾和酸雨。为了减轻来自于废气中的NOx对于人和环境的影响,令人期望的是消除这些不期望的组分,优选通过不产生其他有害或有毒物质的方法。
贫燃和柴油发动机产生的废气通常是氧化性的。NOx需要在被称作选择性催化还原(SCR)的方法中用催化剂和还原剂选择性还原,该方法将NOx转化成单质氮(N2)和水。在SCR方法中,将气态还原剂,典型地是无水氨、氨水或尿素添加到废气流中,然后使该废气接触催化剂。还原剂吸收到催化剂上,并且在气体经过催化型基底之中或之上时还原NOx。为了使NOx的转化率最大,经常必需向气流中添加大于化学计量量的氨。但是,过量的氨释放到大气中将对人的健康和对环境有害。另外,氨是苛性的,特别是它的含水形式。排气催化剂下游的排气管线区域中氨和水的冷凝会产生腐蚀性混合物,其会损坏排气***。所以,应当消除废气中氨的释放。在许多常规排气***中,氨氧化催化剂(也被称作氨泄漏催化剂或“ASC”)安装在SCR催化剂下游,来通过将氨转化成氮来从废气中除去氨。使用氨泄漏催化剂会使得典型的柴油机驱动循环中NOx转化率大于90%。
令人期望的是拥有提供通过SCR除去NOx和将氨选择性转化成氮二者的催化剂,其中氨转化在车辆驾驶周期中的宽温度范围进行,并且形成最少的氧化氮和一氧化二氮副产物。
发明内容
在第一方面中,本发明涉及一种催化剂制品,其包含:(a)挤出的载体,其具有入口、出口和在发动机运行过程中废气流过的多个通道,和(b)在该载体上的单层涂层或双层涂层,其中该挤出的载体包含第三SCR催化剂,该单层涂层包含氨储存性低的载体上的铂与第一SCR催化剂的共混物,和该双层涂层包含底层和顶层,其中该底层位于该顶层与该挤出的载体之间,该底层包含氨储存性低的载体上的铂与第一SCR催化剂的共混物,该顶层包含第二SCR催化剂。
在另一方面中,本发明涉及一种排气***,其包含本发明第一方面的催化剂和用于在废气在形成NH3的装置。
在又一方面中,本发明涉及一种包含排气***的车辆,该排气***包含本发明第一方面的催化剂和用于在废气在形成NH3的装置。
在又一方面中,本发明涉及一种提高在约250℃-约350℃的温度由废气中的氨到N2的产率的方法,该方法包括使含氨废气与本发明第一方面的催化剂制品接触。
在另一方面中,本发明涉及一种减少由废气中的NH3形成N2O的方法,该方法包括使含氨废气与本发明第一方面的催化剂制品接触。
本发明的实施方案包括:
1)催化剂制品,其包含:(a)挤出的载体,其具有入口、出口和在发动机运行过程中废气流过的多个通道,和(b)该载体上的单层涂层或双层涂层,其中该单层涂层包含氨储存性低的载体上的铂与第一SCR催化剂的共混物,和该双层涂层包含底层和顶层,其中该底层位于该顶层与该挤出的载体之间,该底层包含氨储存性低的载体上的铂与第一SCR催化剂的共混物,该顶层包含第二SCR催化剂,和该挤出的载体包含第三SCR催化剂。
2)根据实施方案1所述的催化剂,其中该氨储存性低的载体是含硅载体。
3)根据实施方案2所述的催化剂,其中该含硅载体包含二氧化硅或沸石,该沸石的二氧化硅与氧化铝之比是以下的至少一种:(a)至少100,(b)至少200,(c)至少250,至少300,(d)至少400,(e)至少500,(f)至少750,和(g)至少1000。
4)根据实施方案2所述的催化剂,其中该含硅载体包括BEA、CDO、CON、FAU、MEL、MFI或MWW。
5)根据实施方案1所述的催化剂,其中第一SCR催化剂的量与该氨储存性低的载体上的铂的量之比是以下的至少一种:(a)0:1-300:1,(b)3:1-300:1,(c)7:1-100:1;和(d)10:1-50:1,包括端值,基于这些组分的重量计。
6)根据实施方案1所述的催化剂,其中第一SCR催化剂是包含铜和小孔分子筛的Cu-SCR催化剂,包含铁和小孔分子筛的Fe-SCR催化剂,或混合氧化物。
7)根据实施方案6所述的催化剂制品,其中该小孔分子筛是铝硅酸盐、铝磷酸盐(AlPO)、硅-铝磷酸盐(SAPO)或其混合物。
8)根据实施方案6所述的催化剂制品,其中该小孔分子筛选自骨架类型ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON及其混合物和/或共生体。
9)根据实施方案6所述的催化剂制品,其中该小孔分子筛选自骨架类型CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR和ITE。
10)根据实施方案1所述的催化剂,其中铂以以下的至少一种存在:(a)0.01-0.3wt%,(b)0.03-0.2wt%,(c)0.05-0.17wt%,和(d)0.07-0.15wt%,包括端值,相对于该共混物中铂的载体的重量+铂的重量+第一SCR催化剂的重量计。
11)根据实施方案1所述的催化剂制品,其中第二SCR催化剂和第三SCR催化剂彼此独立地是贱金属、贱金属氧化物、分子筛、金属交换的分子筛或其混合物。
12)根据实施方案11所述的催化剂制品,其中该贱金属选自钒(V)、钼(Mo)、钨(W)、铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)和铜(Cu)及其混合物。
13)根据实施方案11所述的催化剂制品,其进一步包含至少一种贱金属促进剂。
14)根据实施方案11所述的催化剂制品,其中该分子筛或该金属交换的分子筛是小孔的、中孔的、大孔的或其混合的。
15)根据实施方案11所述的催化剂制品,其中第二和/或第三SCR催化剂包含选自以下的小孔分子筛:铝硅酸盐分子筛、金属取代的铝硅酸盐分子筛、铝磷酸盐(AlPO)分子筛、金属取代的铝磷酸盐(MeAlPO)分子筛、硅-铝磷酸盐(SAPO)分子筛和金属取代的硅-铝磷酸盐(MeAPSO)分子筛,及其混合物。
16)根据实施方案15所述的催化剂制品,其中第二和/或第三SCR催化剂包含选自以下骨架类型的小孔分子筛:ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON及其混合物和/或共生体。
17)根据实施方案15所述的催化剂制品,其中第二和/或第三SCR催化剂包含选自以下骨架类型的小孔分子筛:CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR和ITE。
18)根据实施方案15所述的催化剂制品,其中第二和/或第三SCR催化剂包含选自以下骨架类型的中孔分子筛:AEL、AFO、AHT、BOF、BOZ、CGF、CGS、CHI、DAC、EUO、FER、HEU、IMF、ITH、ITR、JRY、JSR、JST、LAU、LOV、MEL、MFI、MFS、MRE、MTT、MVY、MWW、NAB、NAT、NES、OBW、PAR、PCR、PON、PUN、RRO、RSN、SFF、SFG、STF、STI、STT、STW、SVR、SZR、TER、TON、TUN、UOS、VSV、WEI和WEN及其混合物和/或共生体。
19)根据实施方案15所述的催化剂制品,其中第二和/或第三SCR催化剂包含选自以下骨架类型的大孔分子筛:AFI、AFR、AFS、AFY、ASV、ATO、ATS、BEA、BEC、BOG、BPH、BSV、CAN、CON、CZP、DFO、EMT、EON、EZT、FAU、GME、GON、IFR、ISV、ITG、IWR、IWS、IWV、IWW、JSR、LTF、LTL、MAZ、MEI、MOR、MOZ、MSE、MTW、NPO、OFF、OKO、OSI、RON、RWY、SAF、SAO、SBE、SBS、SBT、SEW、SFE、SFO、SFS、SFV、SOF、SOS、STO、SSF、SSY、USI、UWY和VET及其混合物和/或共生体。
20)根据实施方案1所述的催化剂制品,其中第三SCR催化剂包含钒,Fe沸石,Cu沸石,或者用Fe、W或Nb掺杂的Ce-Zr基催化剂。
21)根据实施方案1所述的催化剂制品,其中该催化剂与包含相当的配方的催化剂相比,在约250℃-约300℃的温度提高氨到N2的产率,在该包含相当的配方的催化剂中,第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。
22)根据实施方案1所述的催化剂制品,其中当第一SCR催化剂包含钒时,该催化剂制品与包含相当的配方的催化剂相比失活减少,在该包含相当的配方的催化剂中,第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。
23)根据实施方案1所述的催化剂制品,其中保护该铂来防止被该催化剂中存在的一种或多种能够毒化铂的物质毒化。
24)根据实施方案23所述的催化剂制品,其中能够毒化铂的物质是钒。
25)排气***,其包含根据实施方案1所述的催化剂制品,和用于在废气中形成NH3的装置。
26)根据实施方案25所述的排气***,其进一步包含选自以下的第二催化剂:柴油氧化催化剂(DOC)、柴油放热催化剂(DEC)、过滤器上的选择性催化还原(SCRF)或催化型烟灰过滤器(CSF),其中第二催化剂位于根据实施方案1所述的催化剂的下游。
27)根据实施方案25所述的排气***,其进一步包含选自以下的第二催化剂:SCR催化剂、柴油氧化催化剂(DOC)、柴油放热催化剂(DEC)、NOx吸附剂催化剂(NAC)(例如贫NOx阱(LNT))、NAC、被动NOx吸附剂(PNA)、催化型烟灰过滤器(CSF)、过滤器上的选择性催化还原(SCRF)或冷启动概念(CSC)催化剂,其中第二催化剂位于根据实施方案1所述的催化剂的上游。
28)排气***,其包含根据实施方案1所述的催化剂、SCR催化剂和DOC催化剂,其中该SCR催化剂位于根据实施方案1所述的催化剂与该DOC催化剂之间。
29)根据实施方案25所述的排气***,其中该排气***包含该SCR催化剂之前的铂族金属,并且该铂族金属的量足以产生放热。
30)根据实施方案29所述的排气***,其进一步包含位于根据实施方案1所述的催化剂的下游的促进的Ce-Zr或促进的MnO2。
31)发动机,其包含根据实施方案25所述的排气***。
32)根据实施方案31所述的发动机,其中该发动机是车辆发动机、固定发动机、电厂发动机或燃气轮机。
33)车辆,其包含根据实施方案25所述的排气***。
34)根据实施方案33所述的车辆,其中该车辆是轿车、轻型卡车、重型卡车或船。
35.在约250℃-约300℃的温度提高由废气中的氨到N2的产率的方法,该方法包括使含氨废气与根据实施方案1所述的催化剂接触。
36)根据实施方案35所述的方法,其中与包含相当的配方的催化剂相比,产率提高约10%-约20%,在该包含相当的配方的催化剂中,第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。
37)减少由废气中的NH3形成N2O的方法,该方法包括使含氨废气与根据实施方案1所述的催化剂接触。
38)根据实施方案37所述的方法,其中与包含相当的配方的催化剂相比,N2O形成减少约20%-约40%,在该包含相当的配方的催化剂中,第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。
附图说明
图1是一幅构造图,其中氨泄漏催化剂的单层共混物位于含有第三SCR催化剂的基底的每侧上。
图2是一幅构造图,其中具有包含在低氨储存载体上的铂与第一SCR催化剂的共混物的底层以及包含第二SCR催化剂的顶层的双层涂层位于含有第三SCR催化剂的基底的每侧上。
具体实施方式
作为本说明书和附加的权利要求书中所用的,单数形式“一个”、“一种”和“该”包括复数指代物,除非上下文另有明确指示。因此,例如提及“一种催化剂”时包括两种或更多种催化剂的混合物等。
作为本文使用的,术语“氨泄漏”表示经过SCR催化剂的未反应的氨的量。
术语“载体”表示催化剂固定到的材料。
术语“氨储存性低的载体”表示每m3载体储存小于0.001mmol NH3的载体。氨储存性低的载体优选是具有选自以下的骨架类型的分子筛或沸石:AEI、ANA、ATS、BEA、CDO、CFI、CHA、CON、DDR、ERI、FAU、FER、GON、IFR、IFW、IFY、IHW、IMF、IRN、IRY、ISV、ITE、ITG、ITN、ITR、ITW、IWR、IWS、IWV、IWW、JOZ、LTA、LTF、MEL、MEP、MFI、MRE、MSE、MTF、MTN、MTT、MTW、MVY、MWW、NON、NSI、RRO、RSN、RTE、RTH、RUT、RWR、SEW、SFE、SFF、SFG、SFH、SFN、SFS、SFV、SGT、SOD、SSF、SSO、SSY、STF、STO、STT、SVR、SVV、TON、TUN、UOS、UOV、UTL、UWY、VET、VNI。更优选地,分子筛或沸石具有选自BEA、CDO、CON、FAU、MEL、MFI和MWW的骨架类型,甚至更优选骨架类型选自BEA和MFI。
术语“煅烧”表示将材料在空气或氧气中加热。这个定义与煅烧的IUPAC定义一致。(IUPAC.Compendium of Chemical Terminology,第2版(“Gold Book”)。由A.D.McNaught和A.Wilkinson编纂,Blackwell Scientific Publications,牛津(1997)。XML在线修订版:http://goldbook.iupac.org(2006-),由M.Nic,J.Jirat,B.Kosata创建;由A.Jenkins更新编纂。ISBN 0-9678550-9-8。doi:10.1351/goldbook。)进行煅烧来分解金属盐和促进催化剂内的金属离子交换,以及将催化剂粘附到基底。煅烧所用温度取决于要煅烧的材料的组分,通常在约400℃-约900℃进行约1-8小时。在一些情况中,煅烧可以在高至约1200℃的温度进行。在包括本文所述方法的应用中,煅烧通常在约400℃-约700℃的温度进行约1-8小时,优选在约400℃-约650℃的温度进行约1-4小时。
术语“约”表示大致,指的是在与该术语相关的值任选地±25%,优选±10%,更优选±5%,或最优选±1%的范围内。
当提供用于不同的数字元素的范围时,该范围可以包括该值,除非另有规定。
术语“N2选择性”表示氨到氮的百分转化率。
在本发明的第一方面中,一种催化剂制品,其包含:(a)挤出的载体,其具有入口、出口和在发动机运行过程中废气流过的多个通道,和(b)在该载体上的单层涂层或双层涂层,其中该挤出的载体包含第三SCR催化剂,该单层涂层包含氨储存性低的载体上的铂与第一SCR催化剂的共混物,和该双层涂层包含底层和顶层,其中该底层位于该顶层与该挤出的载体之间,该底层包含氨储存性低的载体上的铂与第一SCR催化剂的共混物,该顶层包含第二SCR催化剂。氨储存性低的载体可以是含硅载体,其中含硅载体可以包含二氧化硅或沸石,该沸石的二氧化硅与氧化铝之比是100,优选200,更优选250,甚至更优选300,特别是400,更特别是500,甚至更特别是750,最优选是1000。含硅载体包括BEA、CDO、CON、FAU、MEL或MWW。该催化剂制品可以在约250℃-约300℃的温度与包含相当的配方的催化剂相比提高氨到N2的产率,在该包含相当的配方的催化剂中,第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。催化剂制品能够保护铂被催化剂中存在的一种或多种能毒化铂的物质例如钒毒化。催化制品可以保护铂防止其他毒物例如钾、钠、铁和钨。当第一SCR催化剂包含钒时,催化剂制品可以与包含相当的配方的催化剂相比减少失活,在该包含相当的配方的催化剂中第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。
术语“活性组分负载量”指的是共混物中铂的载体的重量+铂的重量+第一SCR催化剂的重量。铂可以以约0.01-约0.3wt%(包括端值),优选约0.03-0.2wt%(包括端值),更优选约0.05-0.17wt%(包括端值),最优选约0.07-0.15wt%(包括端值)的活性组分负载量存在于催化剂中。
另外的催化剂例如钯(Pd)、金(Au)、银(Ag),钌(Ru)或铑(Rh)可以与Pt一起存在,优选在与Pt的共混物中。
SCR催化剂
在不同的实施方案中,组合物可以包含一种,两种或三种SCR催化剂。第一SCR催化剂,其总是存在于组合物中,可以存在于(1)与氨储存性低的载体上的Pt的共混物中,或者(2)当催化剂存在于双层中时处于顶层中,并且Pt存在于底层中。第一SCR催化剂优选是Cu-SCR催化剂、Fe-SCR催化剂或混合氧化物,更优选Cu-SCR催化剂或混合氧化物,最优选Cu-SCR催化剂。Cu-SCR催化剂包含铜和分子筛。Fe-SCR催化剂包含铁和分子筛。下面描述进一步分子筛。分子筛可以是铝硅酸盐、铝磷酸盐(AlPO)、硅-铝磷酸盐(SAPO)或其混合物。铜或铁可以位于分子筛骨架内和/或分子筛内的骨架外(可交换)位置。
第二和第三SCR催化剂可以相同或不同。第二和第三SCR催化剂可以是贱金属、贱金属的氧化物、贵金属、分子筛、金属交换的分子筛或其混合物。贱金属可以选自钒(V)、钼(Mo)、钨(W)、铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)和铜(Cu)及其混合物。由负载于难熔金属氧化物例如氧化铝、二氧化硅、氧化锆、二氧化钛、氧化铈及其组合上的钒组成的SCR组合物是公知的,并且在商业上广泛用于移动应用。典型的组合物描述在美国专利4,010,238和4,085,193中,其整个内容在此通过参考引入。商业上特别是移动应用中所用的组合物包含TiO2,其上分别以5-20wt%和0.5-6wt%的浓度分散有WO3和V2O5。第二SCR催化剂可以包含促进的Ce-Zr或促进的MnO2。优选地,促进剂包含Nb。贵金属可以是铂(Pt)、钯(Pd)、金(Au)、银(Ag)、钌(Ru)或铑(Rh)或其混合物。这些催化剂可以含有充当粘结剂和促进剂的其他无机材料例如SiO2和ZrO2。
当SCR催化剂是贱金属时,催化剂制品可以进一步包含至少一种贱金属促进剂。作为本文使用的,“促进剂”被理解为表示当添加到催化剂时增加催化剂的活性的物质。贱金属促进剂可以为金属、金属氧化物或其混合物的形式。至少一种贱金属催化剂促进剂可以选自钕(Nd)、钡(Ba)、铈(Ce)、镧(La)、镨(Pr)、镁(Mg)、钙(Ca)、锰(Mn)、锌(Zn)、铌(Nb)、锆(Zr)、钼(Mo)、锡(Sn)、钽(Ta)、锶(Sr)及其氧化物。至少一种贱金属催化剂促进剂可以优选是MnO2、Mn2O3、Fe2O3、SnO2、CuO、CoO、CeO2及其混合物。至少一种贱金属催化剂促进剂可以以盐的水溶液形式例如硝酸盐或乙酸盐添加到催化剂中。至少一种贱金属催化剂促进剂和至少一种贱金属催化剂例如铜可以从水溶液浸渍到氧化物载体材料上,可以添加到包含氧化物载体材料的载体涂料(washcoat)中,或者可以浸渍到事先用载体涂料涂覆的载体中。
SCR催化剂可以包含分子筛或金属交换的分子筛。作为本文所使用的,“分子筛”被理解为表示含有精确和均匀尺寸的细孔的亚稳材料,其可以用作气体或液体的吸附剂。足够小以穿过孔的分子被吸附,而较大分子不会。分子筛可以是沸石分子筛、非沸石分子筛或其混合物。
沸石分子筛是一种微多孔铝硅酸盐,其具有由国际沸石学会(IZA)公布的沸石结构数据库中的任何一种骨架结构。骨架结构包括但不限于CHA、FAU、BEA、MFI、MOR类型的那些。具有这些结构的沸石的非限定性例子包括菱沸石、八面沸石、Y沸石、超稳定的Y沸石、β沸石、丝光沸石、硅质岩、X沸石和ZSM-5。铝硅酸盐沸石的二氧化硅/氧化铝摩尔比(SAR,定义为SiO2/Al2O3)可以是至少约5,优选至少约20,并且有用的范围是约10-200。
任何SCR催化剂可以包括小孔、中孔或大孔分子筛或其组合。“小孔分子筛”是含有8个四面体原子的最大环尺寸的分子筛。“中孔分子筛”是含有10个四面体原子的最大环尺寸的分子筛。“大孔分子筛”是具有12个四面体原子的最大环尺寸的分子筛。第二和/或第三SCR催化剂可以包括选自以下的小孔分子筛:铝硅酸盐分子筛、金属取代的铝硅酸盐分子筛、铝磷酸盐(AlPO)分子筛、金属取代的铝磷酸盐(MeAlPO)分子筛、硅-铝磷酸盐(SAPO)分子筛和金属取代的硅-铝磷酸盐(MeAPSO)分子筛和其混合物。
任何SCR催化剂可以包含选自以下的骨架类型的小孔分子筛:ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON及其混合物和/或共生体。优选地,小孔分子筛选自骨架类型CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR和ITE。
任何SCR催化剂可以包含选自以下的骨架类型的中孔分子筛:AEL、AFO、AHT、BOF、BOZ、CGF、CGS、CHI、DAC、EUO、FER、HEU、IMF、ITH、ITR、JRY、JSR、JST、LAU、LOV、MEL、MFI、MFS、MRE、MTT、MVY、MWW、NAB、NAT、NES、OBW、PAR、PCR、PON、PUN、RRO、RSN、SFF、SFG、STF、STI、STT、STW、-SVR、SZR、TER、TON、TUN、UOS、VSV、WEI和WEN及其混合物和/或共生体。优选地,中孔分子筛选自骨架类型MFI、FER和STT。
任何SCR催化剂可以包含选自以下的骨架类型的大孔分子筛:AFI、AFR、AFS、AFY、ASV、ATO、ATS、BEA、BEC、BOG、BPH、BSV、CAN、CON、CZP、DFO、EMT、EON、EZT、FAU、GME、GON、IFR、ISV、ITG、IWR、IWS、IWV、IWW、JSR、LTF、LTL、MAZ、MEI、MOR、MOZ、MSE、MTW、NPO、OFF、OKO、OSI、RON、RWY、SAF、SAO、SBE、SBS、SBT、SEW、SFE、SFO、SFS、SFV、SOF、SOS、STO、SSF、SSY、USI、UWY和VET及其混合物和/或共生体。优选地,大孔分子筛选自骨架类型MOR、OFF和BEA。
Cu-SCR和Fe-SCR催化剂中的分子筛优选选自ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG、ZON、BEA、MFI和FER及其混合物和/或共生体。更优选地,Cu-SCR和Fe-SCR中的分子筛选自AEI、AFX、BEA、CHA、DDR、ERI、FER、ITE、KFI、LEV、MFI和SFW及其混合物和/或共生体。
金属交换的分子筛可以具有选自周期表第VB、VIB、VIIB、VIIIB、IB或IIB族的至少一种金属,其沉积在外表面上或者在分子筛的通道、腔室或笼中的骨架外位置。金属可以为几种形状之一,包括但不限于零价金属原子或簇,分离的阳离子,单核或多核氧阳离子,或者作为延伸的金属氧化物。优选地,金属可以是铁、铜及其混合物或组合。
可以使用金属前体在合适的溶剂中的混合物或溶液来将金属与沸石合并。术语“金属前体”表示可以分散在沸石上来产生催化活性金属组分的任何化合物或络合物。优选地,由于使用其他溶剂的经济和环境方面的原因,溶剂是水。当使用优选的金属,铜时,合适的络合物或化合物包括但不限于无水和水合硫酸铜、硝酸铜、醋酸铜、乙酰基丙酮酸铜、氧化铜、氢氧化铜和铜胺盐(例如[Cu(NH3)4]2+)。本发明不限于特定类型、组成或纯度的金属前体。可以将分子筛添加到金属组分溶液中来形成悬浮液,然后使其反应,以使得金属组分分布在沸石上。金属可以分布在分子筛的孔通道中以及外表面上。金属可以以离子形式或作为金属氧化物分布。例如,铜可以作为铜(II)离子、铜(I)离子,或者作为氧化铜来分布。含有金属的分子筛可以与悬浮液的液相分离,经过清洗和干燥。然后可以煅烧形成的含金属的分子筛来将金属固定在分子筛中。优选地,第二和第三催化剂包含:包含铜和分子筛的Cu-SCR催化剂,包含铁和分子筛的Fe-SCR催化剂,钒基催化剂,促进的Ce-Zr,或促进的MnO2。
金属交换的分子筛可以包含约0.10-约10wt%的第VB、VIB、VIIB、VIIIB、IB或IIB族金属,其位于分子筛外表面上或者通道、腔室或笼中的骨架外位置上。优选地,骨架外金属的存在量可以是约0.2-约5wt%。
金属交换的分子筛可以是负载于小孔分子筛上的铜(Cu)或铁(Fe),其具有基于催化剂总重量计约0.1wt%-约20.0wt%的铜或铁。更优选地,铜或铁以基于催化剂总重量计约0.5wt%-约15wt%存在。最优选地,铜或铁以基于催化剂总重量计约1wt%-约9wt%存在。
第一SCR催化剂可以是包含铜和小孔分子筛的Cu-SCR催化剂,或者包含铁和小孔分子筛的Fe-SCR催化剂。小孔分子筛可以是铝硅酸盐、铝磷酸盐(AlPO)、硅-铝磷酸盐(SAPO)或其混合物。小孔分子筛可以选自骨架类型ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON及其混合物和/或共生体。优选地,小孔分子筛可以选自骨架类型CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR和ITE。第一SCR催化剂的量与氨储存性低的载体上的铂的量之比可以是以下的至少一种:(a)0:1-300:1,(b)3:1-300:1,(c)7:1-100:1;和(d)10:1-50:1(包括端值),基于这些组分的重量计。铂可以以以下的至少一种存在:(a)0.01-0.3wt%,(b)0.03-0.2wt%,(c)0.05-0.17wt%,和(d)0.07-0.15wt%(包括端值),相对于混合物中铂的载体的重量+铂的重量+第一SCR催化剂的重量计。
第二SCR催化剂和第三SCR催化剂可以彼此独立地是贱金属、贱金属氧化物、分子筛、金属交换的分子筛或其混合物。贱金属可以选自钒(V)、钼(Mo)、钨(W)、铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)和铜(Cu)及其混合物。催化剂制品可以进一步包含至少一种贱金属促进剂。分子筛或金属交换的分子筛可以是小孔的、中孔的、大孔的或其混合的。第二和/或第三SCR催化剂可以包含选自以下的小孔分子筛:铝硅酸盐分子筛、金属取代的铝硅酸盐分子筛、铝磷酸盐(AlPO)分子筛、金属取代的铝磷酸盐(MeAlPO)分子筛、硅-铝磷酸盐(SAPO)分子筛和金属取代的硅-铝磷酸盐(MeAPSO)分子筛及其混合物。第二和/或第三SCR催化剂可以包含选自以下骨架类型的小孔分子筛:ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON及其混合物和/或共生体。第二和/或第三SCR催化剂可以优选包含选自以下骨架类型的小孔分子筛:CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR和ITE。第二和/或第三SCR催化剂可以包含选自以下骨架类型的中孔分子筛:AEL、AFO、AHT、BOF、BOZ、CGF、CGS、CHI、DAC、EUO、FER、HEU、IMF、ITH、ITR、JRY、JSR、JST、LAU、LOV、MEL、MFI、MFS、MRE、MTT、MVY、MWW、NAB、NAT、NES、OBW、-PAR、PCR、PON、PUN、RRO、RSN、SFF、SFG、STF、STI、STT、STW、SVR、SZR、TER、TON、TUN、UOS、VSV、WEI和WEN及其混合物和/或共生体。第二和/或第三SCR催化剂优选包含选自以下骨架类型的大孔分子筛:AFI、AFR、AFS、AFY、ASV、ATO、ATS、BEA、BEC、BOG、BPH、BSV、CAN、CON、CZP、DFO、EMT、EON、EZT、FAU、GME、GON、IFR、ISV、ITG、IWR、IWS、IWV、IWW、JSR、LTF、LTL、MAZ、MEI、MOR、MOZ、MSE、MTW、NPO、OFF、OKO、OSI、-RON、RWY、SAF、SAO、SBE、SBS、SBT、SEW、SFE、SFO、SFS、SFV、SOF、SOS、STO、SSF、SSY、USI、UWY和VET及其混合物/或共生体。第三SCR催化剂优选包括钒,Fe沸石,Cu沸石,或者用Fe、W或Nb掺杂的Ce-Zr基催化剂。
本文所述的催化剂可以用于多种发动机废气的SCR处理中。发动机可以是车辆发动机、固定发动机、电厂发动机或燃气轮机。包含含硅载体上的铂与第一SCR催化剂(其中第一SCR催化剂是Cu-SCR或Fe-SCR催化剂)的共混物的催化剂的性质之一是,与包含相当的配方的催化剂(其中第一SCR催化剂作为第一层存在,和铂负载在存在于第二层中的储存氨的层上,含NH3气体先经过第一层,然后经过第二层)相比,它可以在约250℃-约350℃的温度提高氨到N2的产率。包含氨储存性低的载体上的铂与第一SCR催化剂(其中第一SCR催化剂是Cu-SCR催化剂或Fe-SCR催化剂)的共混物的催化剂另一性质是,与包含相当的配方的催化剂(其中第一SCR催化剂作为第一层存在,和铂负载在存在于第二层中的储存氨的载体上,含NH3气体先经过第一层,然后经过第二层)相比,它可以减少由NH3形成的N2O。
用于催化剂的基底可以是典型地用于制备汽车催化剂的任何材料,其包括流通式或滤过式结构,例如蜂窝体结构、挤出的载体、金属基底或SCRF。优选地,基底具有多个细的、平行气体流动通道,其从基底的入口延伸到出口面,由此通道对于流体流动是开放的。这样的整料载体可以含有至多约700或更多个流动通道(或“孔腔”)/平方英寸横截面,不过可以使用少得多的数目。例如,载体可以具有约7-600个,更通常地约100-400个孔腔/平方英寸(“cpsi”)。通道从它们的流体入口到它们的流体出口基本上是直线路径,通过SCR催化剂作为“载体涂料”涂覆到的壁来限定,由此流过通道的气体接触催化材料。整料基底的流动通道是薄壁通道,其可以是任何合适的横截面形状,例如梯形、矩形、正方形、三角形、正弦形、六边形、椭圆形、圆形等。本发明不限于具体的基底类型、材料或几何形状。
陶瓷基底可以由任何合适的难熔材料制成,例如堇青石、堇青石-α氧化铝、α氧化铝、碳化硅、氮化硅、氧化锆、莫来石、锂辉石、氧化铝-二氧化硅氧化镁、硅酸锆、硅线石、硅酸镁、锆石、透锂长石、硅酸铝及其混合物。
壁流式基底也可以由陶瓷纤维复合材料形成,例如由堇青石和碳化硅形成的那些。这样的材料能够经受在处理废气流中遇到的环境,特别是高温。
基底可以是高孔隙率基底。术语“高孔隙率基底”指的是孔隙率是约40%-约80%的基底。高孔隙率基底的孔隙率优选可以是至少约45%,更优选至少约50%。高孔隙率基底的孔隙率优选可以小于约75%,更优选小于约70%。作为本文使用的,术语孔隙率指的是总孔隙率,优选用水银孔隙率法测量。
优选地,基底可以是堇青石、高孔隙率堇青石、金属基底、挤出的SCR、过滤器或SCRF。
包含含硅载体上的铂与第一SCR催化剂的共混物的载体涂料,其中第一SCR催化剂优选是Cu-SCR催化剂或Fe-SCR催化剂,可以使用本领域已知的方法施用到基底的入口侧。在施涂载体涂料后,可以干燥和煅烧组合物。当组合物包含第二SCR时,第二SCR可以在单独的载体涂料中施涂到具有底层的经煅烧的制品上,如上所述。在施涂第二载体涂料后,可以如对第一层进行的那样对它进行干燥和煅烧。
可以在300℃-1200℃,优选400℃-700℃,更优选450℃-650℃的温度干燥和煅烧具有含铂层的基底。煅烧优选在干燥条件下进行,但是它也可以水热,即在一些水分含量存在下进行。煅烧可以进行约30分钟到约4小时,优选约30分钟到约2小时,更优选约30分钟到约1小时的时间。
一种排气***可以包含本发明第一方面的催化剂和用于在废气中形成NH3的装置。一种排气***可以进一步包含选自以下的第二催化剂:柴油氧化催化剂(DOC)、柴油放热催化剂(DEC)、过滤器上的选择性催化还原(SCRF)或催化型烟灰过滤器(CSF),其中第二催化剂位于本发明第一方面的催化剂的下游。一种排气***可以进一步包含选自以下的第二催化剂:SCR催化剂、过滤器上的选择性催化还原(SCRF)、柴油氧化催化剂(DOC)、柴油放热催化剂(DEC)、NOx吸附剂催化剂(NAC)(例如贫NOx阱(LNT))、NAC、被动NOx吸附剂(PNA)、催化型烟灰过滤器(CSF)或冷启动概念(CSC)催化剂,其中第二催化剂位于本发明第一方面的催化剂的上游。
一种排气***可以包含本发明第一方面的催化剂、SCR催化剂和DOC催化剂,其中SCR催化剂位于本发明第一方面的催化剂与DOC催化剂之间。排气***可以包含在SCR催化剂之前的铂族金属,其中铂族金属的量足以产生放热。排气***可以进一步包含位于本发明第一方面催化剂的下游的促进的Ce-Zr或促进的MnO2。
一种发动机可以包含上述排气***。发动机可以是车辆发动机、固定发动机、电厂发动机或燃气轮机。
一种车辆可以包含排气***,该排气***包含本发明第一方面的催化剂和用于在废气中形成NH3的装置。车辆可以是轿车、轻型卡车、重型卡车或船。
一种在约250℃-约300℃的温度提高由废气中的氨到N2的产率的方法包括使含氨废气与本发明第一方面的催化剂接触。与包含相当的配方的催化剂相比,产率可以提高约10%-约20%,在该包含相当的配方的催化剂中,第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。
一种减少由废气中的NH3形成N2O的方法包括使含氨废气与本发明第一方面的催化剂接触。与包含相当的配方的催化剂相比,N2O形成可以减少约20%-约40%,在该包含相当的配方的催化剂中,第一SCR催化剂作为第一层存在,含硅载体上的铂存在于第二层中,和含NH3气体先经过第一层,然后经过第二层。
下面的实施例仅说明本发明;本领域技术人员将认识到在本发明主旨和权利要求书的范围内的许多变化。
实施例
实施例1:挤出的SCR催化剂上的选择性ASC
含有钒的挤出的SCR催化剂从出口侧涂覆有包含氨储存性低的载体上的铂与Cu-CHA的共混物的载体涂料。
实施例2:挤出的SCR催化剂上的选择性ASC
含有Fe-沸石的挤出的SCR催化剂从出口侧涂覆有包含氨储存性低的载体上的铂与Cu-CHA的工具物的载体涂料。
与常规单层ASC(其中该单层涂层包含载体例如氧化铝上的铂,该涂层中没有任何SCR催化剂)相比,本文所述的ASC降低了N2O和NOx二者的选择性。这使得在全部温度范围内对于N2的选择性增大。
实施例3:挤出的SCR催化剂上的选择性ASC
含有钒的挤出的SCR催化剂从出口侧涂覆有包含氨储存性低的载体上的铂的载体涂料来形成底层。包含Cu-CHA的第二载体涂料置于该底层上来形成顶层。
实施例4:挤出的SCR催化剂上的选择性ASC
含有Fe-沸石的挤出的SCR催化剂从出口侧涂覆有包含氨储存性低的载体上的铂的载体涂料来形成底层。包含Cu-CHA的第二载体涂料置于该底层上来形成顶层。
与常规双层ASC(其中底涂层包含例如氧化铝上的铂,和顶涂层包含SCR催化剂)相比,本文所述的ASC降低了N2O和NOx二者的选择性。这使得在全部温度范围内对于N2的选择性增大。另外,由于整体更薄的涂层,背压将降低。
在上面的实施例中,铂在氨储存性低的载体上。使用氨储存性低的载体有助于保护铂防止暴露于会毒化铂或者对铂产生不利影响的材料,例如钒。
实施例5:具有ASC的SCRF
SCRF过滤器在该过滤器的出口面上涂覆有包含氨储存性低的载体上的铂的载体涂料来形成底层。将包含Cu-CHA的第二载体涂料置于该底层上来形成顶层。
实施例6:具有ASC的SCRF
SCRF过滤器在该过滤器的出口面上涂覆有包含氨储存性低的载体上的铂与Cu-CHA的共混物的载体涂料。
实施例5和6的具有ASC的SCRF提供了与实施例1-4所述的***相同的结果和益处。
前述实施例目的仅是说明性的;权利要求书限定了本发明的范围。
Claims (14)
1.催化剂制品,其包含:(a)挤出的载体,其具有入口、出口和在发动机运行过程中废气流过的多个通道,和(b)该载体上的单层涂层或双层涂层,其中该单层涂层包含含硅载体上的铂与第一SCR催化剂的共混物,和该双层涂层包含底层和顶层,其中该底层位于该顶层与该挤出的载体之间,该底层包含含硅载体上的铂与第一SCR催化剂的共混物,该顶层包含第二SCR催化剂,和该挤出的载体包含第三SCR催化剂,其中该含硅载体包含二氧化硅或二氧化硅与氧化铝之比至少300的沸石。
2.根据权利要求1所述的催化剂,其中该含硅载体包含二氧化硅或二氧化硅与氧化铝之比是以下至少一种的沸石:(a)至少400,(b)至少500,(c)至少750,和(d)至少1000。
3.根据权利要求1所述的催化剂,其中该含硅载体包括BEA、CDO、CON、FAU、MEL、MFI或MWW。
4.根据权利要求1所述的催化剂,其中第一SCR催化剂的量与该含硅载体上的铂的量之比是以下至少一种:(a)0:1-300:1,(b)3:1-300:1,(c)7:1-100:1;和(d)10:1-50:1,包括端值,基于这些组分的重量计。
5.根据权利要求1所述的催化剂,其中第一SCR催化剂是包含铜和小孔分子筛的Cu-SCR催化剂,包含铁和小孔分子筛的Fe-SCR催化剂,或混合氧化物。
6.根据权利要求5所述的催化剂制品,其中该小孔分子筛选自骨架类型CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR和ITE。
7.根据权利要求1所述的催化剂,其中铂以以下至少一种存在:(a)0.01-0.3wt%,(b)0.03-0.2wt%,(c)0.05-0.17wt%,和(d)0.07-0.15wt%,包括端值,相对于该共混物中铂的载体的重量+铂的重量+第一SCR催化剂的重量计。
8.根据权利要求1所述的催化剂制品,其中第二SCR催化剂和第三SCR催化剂彼此独立地是贱金属、贱金属氧化物、分子筛、金属交换的分子筛或其混合物。
9.根据权利要求8所述的催化剂制品,其中该贱金属选自钒(V)、钼(Mo)、钨(W)、铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)和铜(Cu)及其混合物。
10.根据权利要求8所述的催化剂制品,其进一步包含至少一种贱金属促进剂。
11.根据权利要求8所述的催化剂制品,其中该分子筛或该金属交换的分子筛是小孔的、中孔的、大孔的或其混合的。
12.根据权利要求8所述的催化剂制品,其中第二和/或第三SCR催化剂包含选自以下骨架类型的小孔分子筛:CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR和ITE,
或者选自以下骨架类型的中孔分子筛:AEL、AFO、AHT、BOF、BOZ、CGF、CGS、CHI、DAC、EUO、FER、HEU、IMF、ITH、ITR、JRY、JSR、JST、LAU、LOV、MEL、MFI、MFS、MRE、MTT、MVY、MWW、NAB、NAT、NES、OBW、PAR、PCR、PON、PUN、RRO、RSN、SFF、SFG、STF、STI、STT、STW、SVR、SZR、TER、TON、TUN、UOS、VSV、WEI和WEN及其混合物和/或共生体,
或者选自以下骨架类型的大孔分子筛:AFI、AFR、AFS、AFY、ASV、ATO、ATS、BEA、BEC、BOG、BPH、BSV、CAN、CON、CZP、DFO、EMT、EON、EZT、FAU、GME、GON、IFR、ISV、ITG、IWR、IWS、IWV、IWW、JSR、LTF、LTL、MAZ、MEI、MOR、MOZ、MSE、MTW、NPO、OFF、OKO、OSI、RON、RWY、SAF、SAO、SBE、SBS、SBT、SEW、SFE、SFO、SFS、SFV、SOF、SOS、STO、SSF、SSY、USI、UWY和VET及其混合物和/或共生体。
13.根据权利要求1所述的催化剂制品,其中第三SCR催化剂包含钒,Fe沸石,Cu沸石,或者用Fe、W或Nb掺杂的Ce-Zr基催化剂。
14.排气***,其包含根据权利要求1所述的催化剂制品,和用于在废气中形成NH3的装置。
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US201562181303P | 2015-06-18 | 2015-06-18 | |
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CN201680043641.2A CN107847918A (zh) | 2015-06-18 | 2016-06-16 | 单层或双层氨泄漏催化剂 |
PCT/US2016/037861 WO2016205506A1 (en) | 2015-06-18 | 2016-06-16 | Single or dual layer ammonia slip catalyst |
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CN (2) | CN117065794A (zh) |
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DE (1) | DE102016111151A1 (zh) |
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JP6219871B2 (ja) | 2015-03-27 | 2017-10-25 | トヨタ自動車株式会社 | 排ガス浄化用触媒 |
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- 2016-06-16 US US15/184,267 patent/US9789441B2/en active Active
- 2016-06-16 RU RU2018101715A patent/RU2743125C2/ru active
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RU2018101715A3 (zh) | 2019-10-09 |
JP2018526193A (ja) | 2018-09-13 |
GB2542231B (en) | 2019-08-14 |
BR112017027160B1 (pt) | 2021-09-28 |
KR20180020215A (ko) | 2018-02-27 |
WO2016205506A1 (en) | 2016-12-22 |
BR112017027160A2 (pt) | 2018-08-21 |
GB201610559D0 (en) | 2016-08-03 |
RU2018101715A (ru) | 2019-07-18 |
DE102016111151A1 (de) | 2016-12-22 |
RU2743125C2 (ru) | 2021-02-15 |
EP3310477A1 (en) | 2018-04-25 |
US9789441B2 (en) | 2017-10-17 |
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US20160367938A1 (en) | 2016-12-22 |
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