CN106661984B - Exhaust system with modified poor NOX trap - Google Patents
Exhaust system with modified poor NOX trap Download PDFInfo
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- CN106661984B CN106661984B CN201580042915.1A CN201580042915A CN106661984B CN 106661984 B CN106661984 B CN 106661984B CN 201580042915 A CN201580042915 A CN 201580042915A CN 106661984 B CN106661984 B CN 106661984B
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- Prior art keywords
- metal
- exhaust system
- zeolite
- modification
- trap
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- 239000003054 catalyst Substances 0.000 claims abstract description 53
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010457 zeolite Substances 0.000 claims abstract description 47
- 229910002089 NOx Inorganic materials 0.000 claims abstract description 45
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000006011 modification reaction Methods 0.000 claims abstract description 37
- 230000004048 modification Effects 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 26
- 239000000969 carrier Substances 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 21
- 238000003860 storage Methods 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 12
- 239000002250 absorbent Substances 0.000 claims abstract description 10
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 50
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical compound [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 229910001884 aluminium oxide Inorganic materials 0.000 claims description 15
- 229910052788 barium Inorganic materials 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- VPBIQXABTCDMAU-UHFFFAOYSA-N magnesium;oxido(oxo)alumane Chemical compound [Mg+2].[O-][Al]=O.[O-][Al]=O VPBIQXABTCDMAU-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitrogen oxide Substances O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 5
- -1 Vanadium-titanium Chemical compound 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000001603 reducing Effects 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052813 nitrogen oxide Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 210000002700 Urine Anatomy 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- KTOLWOOLOCKNNB-UHFFFAOYSA-N [W+2]=O.[O-2].[Ti+4].[V+5] Chemical compound [W+2]=O.[O-2].[Ti+4].[V+5] KTOLWOOLOCKNNB-UHFFFAOYSA-N 0.000 claims 2
- GSWGDDYIUCWADU-UHFFFAOYSA-N [O--].[Mg++].[Al+3] Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 claims 1
- UEYXPQOIOHOQON-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[O-2].[V+5] Chemical compound [O-2].[O-2].[Ti+4].[O-2].[V+5] UEYXPQOIOHOQON-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000003009 desulfurizing Effects 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N Sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- SMYKVLBUSSNXMV-UHFFFAOYSA-J aluminum;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-J 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 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 4
- 239000010452 phosphate Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910001017 Alperm Inorganic materials 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L Barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N Barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910020203 CeO Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N Cesium Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N Neodymium Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 241000193690 San Angelo virus Species 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N Silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 210000002356 Skeleton Anatomy 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000002045 lasting Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 201000002674 obstructive nephropathy Diseases 0.000 description 2
- 230000001590 oxidative Effects 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atoms Chemical group O* 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 235000019161 pantothenic acid Nutrition 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N Niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N Nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N Palladium(II) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 210000003660 Reticulum Anatomy 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 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
- FKHIFSZMMVMEQY-UHFFFAOYSA-N Talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- MXOSECBTSFQUJS-UHFFFAOYSA-N [O-2].[Ti+4].[V+5] Chemical compound [O-2].[Ti+4].[V+5] MXOSECBTSFQUJS-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 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
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- FSFHDWHQJKXOHH-UHFFFAOYSA-N cerium(3+);oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Zr+4].[Zr+4].[Ce+3].[Ce+3] FSFHDWHQJKXOHH-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003750 conditioning Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JAUGGEIKQIHSMF-UHFFFAOYSA-N dialuminum;dimagnesium;dioxido(oxo)silane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O JAUGGEIKQIHSMF-UHFFFAOYSA-N 0.000 description 1
- CRPOUZQWHJYTMS-UHFFFAOYSA-N dialuminum;magnesium;disilicate Chemical compound [Mg+2].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] CRPOUZQWHJYTMS-UHFFFAOYSA-N 0.000 description 1
- YIXQSYHBXUBLPM-UHFFFAOYSA-N dioxido(oxo)silane;zirconium(4+) Chemical compound [Zr+4].[O-][Si]([O-])=O.[O-][Si]([O-])=O YIXQSYHBXUBLPM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
It discloses a kind of for handling the exhaust system of engine exhaust gas.The system includes modified poor NOxTrap (LNT), urea injection system and ammonia-selective catalytic reduction catalysts.The LNT of the modification includes first layer and the second layer.First layer includes NOxAbsorbent component and one or more platinums group metal.The second layer includes diesel oxidation catalyst area and NO zoneofoxidation.The diesel oxidation catalyst area includes platinum group metal, zeolite and optional alkaline-earth metal.The NO zoneofoxidation includes platinum group metal and carrier.The LNT of the modification is being below about 200 DEG C of temperature storage NOxIt is discharged with the temperature at greater than about 200 DEG C.Also disclose the method for the LNT and the LNT using the modification of the modification.
Description
Invention field
The present invention relates to a kind of exhaust systems for handling engine exhaust gas, and the method for processing engine exhaust gas.
Background of invention
Internal combustion engine generates the exhaust gas containing multiple pollutant, including nitrogen oxides (" NOx"), carbon monoxide and unburned
Hydrocarbon, this is the theme of government regulation.Emission control system is widely used in reducing amount of these pollutant emissions into atmosphere,
Once and typically their operation temperatures (typically 200 DEG C and higher) for having reached them, then realize very high efficiency.
But these systems are relatively inefficient when being lower than their operation temperature (" cold start-up " phase).
For example, application is applied to meet the selective catalytic reduction (SCR) for being currently based on urea of Euro 6b discharge standard
It is required that adding that can measure urea and being used to convert NOxBefore, the temperature at urea metering point of addition is greater than about
180℃.The NO lower than 180 DEG C is difficult to realize using current systemxConversion, and following Europe and Code of Federal Regulations will be emphasized
Low temperature NOxStorage and conversion.This is realized by heat protocol at present, but this is with CO2The ill-effect of discharge.
Due to even tightened up countries and regions regulation reduces can be from diesel engine or the pollutant of gasoline exhaust
Amount, so reduce the cold start-up phase during emission just becoming a significant challenge.Therefore, lasting research and development reduce cold start-up
The NO discharged in conditioning processxHorizontal method.
For example, PCT international application WO2008/047170 discloses a kind of system, wherein from the NO of lean exhaust gasxLow
In 200 DEG C of temperature adsorption, then it is being higher than 200 DEG C of thermal desorptions.It is said that NOxAdsorbent is by palladium and cerium oxide or contains cerium
It is formed with the mixed oxide or composite oxides of other at least one transition metal.
U.S.Application Publication 2011/0005200 teaches a kind of catalyst system, by by ammonia-selective catalysis also
Original (" NH3- SCR ") catalyst preparation object is placed in poor NOxTrap downstream, to remove deammoniation simultaneously and improve net NOxConversion ratio.It is said that
NH3SCR catalyst is adsorbed on poor NOxThe ammonia generated in rich pulse process in trap.The ammonia of storage then with the poor NO in upstreamxTrap discharge
NOxReaction, this improves NOxConversion ratio, while consuming the ammonia of storage.
PCT international application WO2004/076829 discloses a kind of waste gas cleaning system, and it includes be arranged in SCR catalyst
The NO of upstreamxStore catalyst.The NOxStoring catalyst includes at least one alkali metal, alkaline-earth metal or rare earth metal, is used
At least one platinum group metal (Pt, Pd, Rh or Ir) coats or activates.It is said that a kind of particularly preferred NOxStore catalyst packet
Oxidation-containing cerium is used platinum and is coated as the other platinum of the oxidation catalyst on the carrier based on aluminium oxide.EP1027919
Disclose a kind of NOxSorbent material, it includes porous carrier materials for example aluminium oxide, zeolite, zirconium oxide, titanium dioxide and/
Or lanthana, and the noble metal (Pt, Pd and/or Rh) of at least 0.1 weight %.Example is the platinum loaded on alumina.
Using any automotive system and method, need to obtain further improvement in exhaust treatment system, especially
In cold start conditions.It has been found that a kind of system, the NO during the cold start-up phase can be reducedxDischarge, while keeping good
Good CO oxidation activity and show the resistance to inactivation due to caused by sulphation.
Summary of the invention
The present invention is a kind of exhaust system for handling engine exhaust gas.The system includes modified poor NOxTrap (LNT), urine
Plain injected system and ammonia-selective catalytic reduction (NH3- SCR) catalyst.The LNT of the modification includes first layer and the second layer.The
One layer includes NOxAbsorbent component and one or more platinums group metal.The second layer includes that diesel oxidation catalyst area and NO are aoxidized
Area.The diesel oxidation catalyst area includes platinum group metal, zeolite and optional alkaline-earth metal.The NO zoneofoxidation includes platinum family gold
Category and carrier.The LNT of the modification is being below about 200 DEG C of temperature storage NOx, discharged in greater than about 200 DEG C of temperature.The present invention
It further include the method for the LNT and the LNT using the modification of the modification.
Detailed description of the invention
Fig. 1 shows the accumulation NO from the Engine Block Test for the LNT for using the modificationx。
Fig. 2 shows the NO of the modification of LNT2/NOxConcentration ratio, the LNT include diesel oxidation catalyst area and are including NOx
NO zoneofoxidation on the first layer of adsorbent.
Specific embodiment
The present invention is a kind of exhaust system for handling engine exhaust gas.The system includes modified poor NOxTrap (LNT).It is poor
NOxTrap is well known in the art.Poor NOxTrap is typically designed to adsorb NO under poor exhaust conditionsx, discharged under the conditions of richness
The NO of absorptionx, and the NO of reduction releasexTo form N2。
LNT typically comprises NOxStorage component, oxidation component and reduction components.The NOxStorage component preferably comprises alkaline earth
Metal (such as barium, calcium, strontium and magnesium), alkali metal (such as potassium, sodium, lithium and caesium), rare earth metal (such as lanthanum, yttrium, praseodymium and neodymium) or
A combination thereof.The metal typically exists in the form of an oxide.Typically, oxidative function is played comprising platinum, is played comprising rhodium
Restoring function.These components are included on one or more carriers.
Oxidation/reduction catalyst and NOxStorage component is preferably supported on carrier material such as inorganic oxide, to be formed
For the LNT in exhaust system.
The LNT of modification of the invention is designed to the function different from known LNT, this is them preferably through designing
Be below about 200 DEG C of temperature storage NOx, in the NO of greater than about 200 DEG C of temperature release storagex.Discharge the NO of storagexIt can
To be carried out by heat, or can also be carried out by richness purging.
The LNT of the modification includes first layer and the second layer.First layer includes NOxAbsorbent component and one or more platinum families
Metal.The NOxAbsorbent component preferably comprises alkaline-earth metal, alkali metal, rare earth metal and its mixture.The alkaline-earth metal is preferred
It is barium, calcium, strontium or magnesium.The alkali metal is preferably potassium, sodium, lithium or caesium.The rare earth metal is preferably lanthanum, yttrium, praseodymium or neodymium.Most preferably
Ground, the NOxAbsorbent component includes barium.
If used, then or mixtures thereof alkaline-earth metal, alkali metal, rare earth metal can preferably be carried on inorganic oxide
On object.The inorganic oxide material preferably contains ceria material or magnesia-alumina.It is preferred that this contains ceria material
It is or mixtures thereof ceria, ceria-zirconia, ceria-zirconia-aluminium oxide.It is highly preferred that this contains dioxy
Changing cerium material is ceria, specifically particulate cerium oxide.The magnesia-alumina is preferably spinelle, magnesia-oxygen
Change aluminium mixed-metal oxides, hydrotalcite or hydrotalcite sample material and its combination of two or more.It is highly preferred that the oxidation
Magnesium-alumina supports are spinelles.
The alkaline-earth metal, alkali metal or rare earth component can be carried on the inorganic oxide by any of means
On object material, addition manner is not considered particularly critical.For example, can be by dipping, absorption, ion exchange, initial wetting, heavy
Barium compound (such as barium acetate) is added to containing in ceria material by shallow lake etc..Preferably, first layer includes at least 2.5 weights
Measure the barium of %.
The platinum group metal is preferably or mixtures thereof platinum, palladium, rhodium.Particularly preferred platinum and palladium.
Preferably, first layer also includes carrier.The carrier is preferably the oxide of the race of the 2nd, 3,4,5,13 and 14 element.
Most preferably, the carrier be aluminium oxide, silica, titanium dioxide, zirconium oxide, magnesia, niobium oxide, tantalum oxide, molybdenum oxide,
Tungsten oxide, the arbitrarily mixed oxide of two or more or composite oxides and its mixture.
The preferred preferred surface area of carrier is 10-1500m2/ g, pore volume is 0.1-4mL/g and aperture is about 10-
1000 angstroms.Particularly preferred surface area is greater than 80m2The high surface area carrier of/g.
The second layer includes diesel oxidation catalyst area and NO zoneofoxidation.The diesel oxidation catalyst area include platinum group metal,
Zeolite and optional alkaline-earth metal.The optional alkaline-earth metal is preferably magnesium, calcium, strontium or barium；More preferably barium.The platinum group metal
Preferably include platinum and palladium.Preferably, the Pd:Pt ratio in the diesel oxidation catalyst area is 0.25-1.
The zeolite can be any natural or synthetic zeolite, and preferably comprise aluminium, silicon and/or phosphorus.The zeolite is typical
Ground has SiO4、AlO4And/or PO4Three-dimensional arrangement, combined by shared oxygen atom, but be also possible to two-dimensional structure.
The zeolite skeleton is typically anion, is balanced by charge compensation cation, the charge compensation cation allusion quotation
It is type alkali and alkaline earth metal ions element (such as Na, K, Mg, Ca, Sr and Ba), ammonium ion and proton.
Preferably, aluminosilicate zeolites, the aluminate or phosphate zeolite, gold which is selected from aluminosilicate zeolites, metal replaces
Belong to the silicoaluminophosphate zeolite that the aluminate or phosphate zeolite, silicoaluminophosphate zeolite or metal replaced replaces.
Particularly preferably with following framework types zeolite: 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、MFI、FER、
MWW, EUO, CON, BEA, FAU, MOR and EMT and its two or more any mixture or commensal.Most preferably,
The framework types of the zeolite are AEI, CHA, LEV, BEA (such as β zeolite), FAU (such as zeolite Y) or MFI (such as ZSM-
5)。
The diesel oxidation catalyst can also preferably comprise manganese.
The diesel oxidation catalyst area preferably also includes inorganic oxide carrier.The inorganic oxide carrier preferably comprises
2, the oxide of 3,4,5,13 and 14 race's elements.Most preferably, which is aluminium oxide or silica-doped carrying alumina
Body.
The NO zoneofoxidation includes platinum group metal and carrier.The platinum group metal preferably includes platinum and palladium.Preferably, which aoxidizes
Pd:Pt ratio in area is 0-0.25.
The carrier is preferably aluminium oxide, silica, containing ceria material, titanium dioxide, zirconium oxide, magnesia, oxygen
Change niobium, tantalum oxide, molybdenum oxide, tungsten oxide, the arbitrarily mixed oxide of two or more or composite oxides (such as dioxy
SiClx-aluminium oxide, magnesia-alumina) and its mixture.This contains ceria material and is preferably ceria, titanium dioxide
Or mixtures thereof cerium-zirconium oxide, ceria-zirconia-aluminium oxide,；It is highly preferred that it is oxidation that this, which contains ceria material,
Cerium, especially particulate cerium oxide.The mixture of particularly preferred carrier such as aluminium oxide and ceria.
The NO zoneofoxidation can also preferably comprise manganese.
The NO zoneofoxidation may include alkali or alkaline earth metal such as barium, but can also substantially free of alkali metal or
Alkaline earth metal component.Substantially free indicates that no alkali or alkaline earth metal is intentionally added to NO zoneofoxidation.Preferably,
Substantially free indicates that NO zoneofoxidation includes the alkali or alkaline earth metal less than 0.1 weight %, more preferably less than 0.05 weight
The alkali or alkaline earth metal for measuring %, most preferably without alkali or alkaline earth metal.
The LNT of the modification preferably comprises substrate.The substrate is preferably ceramic bases or metallic substrates.The ceramic bases can be with
It is made of any suitable refractory material, the refractory material such as aluminium oxide, silica, titanium dioxide, ceria, oxidation
Zirconium, magnesia, zeolite, silicon nitride, silicon carbide, zirconium silicate, magnesium silicate, aluminosilicate and metal aluminosilicates (such as cordierite
And spodumene) or its two or more any mixture or mixed oxide.Particularly preferred cordierite, magnesium alumino metasilicate
Salt and silicon carbide.
The metallic substrates can be made of any suitable metal, and the metal especially heating resisting metal and metal alloy are for example
Titanium and stainless steel and Alfer, the Alfer contain iron, nickel, chromium and/or aluminium and other trace metals.
The substrate is preferably flow type substrate or filter base.Most preferably, which is flow type substrate.Specifically
Ground, which is flow type material all in one piece, preferably has honeycomb body structure, has and extends axially through the substrate and run through
Many small, parallel thin-walled channels that the substrate extends.
The channel cross-section of the substrate can be any shape, it is preferred that be square, sinusoidal, triangle, rectangle,
Hexagon, trapezoidal, round or ellipse.
When being added to the substrate, the NO of the modificationxThe layer of trap can arrange in any order on this substrate, but excellent
First layer is selected to be located in the substrate, the second layer is located on first layer.The diesel oxidation catalyst area of the second layer is preferably placed in
Then the upstream of the NO zoneofoxidation contacts the NO zoneofoxidation so that exhaust gas contacts the diesel oxidation catalyst area first.
The NO of modification of the inventionxTrap can be prepared by method commonly known in the art.Preferably, the NOxTrap is logical
It crosses that two layers is deposited in the substrate using carrier coating (washcoat) program and prepares.
Preferably, the whole length of the substrate is coated with first layer slurry, so that the of carrier coating (washcoat)
One layer of whole surface for covering the substrate.The a part of the length of the substrate from front end is coated with the diesel oxidation catalyst
Area, and the rest part of base length is coated with the NO zoneofoxidation.
The LNT of the modification of the invention is being below about 200 DEG C of temperature storage NOx, discharged in greater than about 200 DEG C of temperature
The NO of storagex。
The exhaust system of the invention also includes ammonia-selective catalytic reduction (NH3- SCR) catalyst.The NH3- SCR catalysis
Agent may include any of NH3SCR catalyst is well known in the art.NH3SCR catalyst be by with nitrification
Object (such as ammonia or urea) is reacted NOxIt is reduced into N2Catalyst.
Preferably, the NH3SCR catalyst includes vanadium oxide-titanium deoxide catalyst, vanadium oxide-tungsten oxide-titanium dioxide
Titanium catalyst or metal/zeolite.Metal/the zeolite catalyst includes metal and zeolite.Preferred metal includes iron and copper.
The zeolite can be any natural or synthetic zeolite, preferably comprise aluminium, silicon and/or phosphorus.The zeolite typically has
There is SiO4、AlO4And/or PO4Three-dimensional arrangement, combined by shared oxygen atom, but be also possible to two-dimensional structure.
The zeolite skeleton is typically anion, is balanced by charge compensation cation, the charge compensation
Cation is typically alkali and alkaline earth metal ions element (such as Na, K, Mg, Ca, Sr and Ba), ammonium ion and proton.
Preferably, aluminosilicate zeolites, the aluminate or phosphate zeolite, gold which is selected from aluminosilicate zeolites, metal replaces
Belong to the silicoaluminophosphate zeolite that the aluminate or phosphate zeolite, silicoaluminophosphate zeolite or metal replaced replaces.
Particularly preferably with following framework types zeolite: 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、MFI、FER、
MWW, EUO, CON, BEA, FAU, MOR and EMT and its two or more any mixture or commensal.Most preferably,
The framework types of the zeolite are AEI, CHA, LEV, BEA (such as β zeolite) or FER (such as ferrierite).
The NH3SCR catalyst is preferably applied in ceramics or metallic substrates, as described above.The substrate is typically through designing
There is provided the channel that many vehicle exhausts are passed through, and the surface in the channel will be preferably coated with the NH3SCR catalyst.
For the NH3The substrate of SCR catalyst can be filter base or flow type substrate.Preferably, the NH3-SCR
Catalyst is coated on filter, is referred to as ammonia-selective catalytic reduction filter (NH3-SCRF).SCRF is single substrate
Device, a combination thereof NH3The function of-SCR and particulate filter.They are used to restore the NO of internal combustion enginexAnd particle emission.
System of the invention further includes urea injection system.The urea injection system preferably comprises urea injector,
It introduces urea into the NH3In the waste gas stream in SCR catalyst upstream and the downstream LNT of the modification.The urea injection system will
It is preferred that being made of nozzle, to generate the urea liquid droplet of sharp outline.The droplet size is preferably smaller than 500 microns to allow fastly
Speed evaporation and urea decompose.The syringe pressure and pump rate will be so that effectively mix in the waste gas stream.
The urea injection system also preferably by urea slot, feed-line and will be used to that urea liquid to be avoided to freeze possible
Heating system composition.
Preferably, which injects urea in greater than about 180 DEG C of temperature.
The invention also includes a kind of methods for handling engine exhaust gas.This method includes making the exhaust gas by above-mentioned modification
LNT.The LNT of the modification removes nitrogen oxides (NO in the temperature below about 200 DEG C from the exhaust gasx), and greater than about
200 DEG C of temperature discharges the NOx.In greater than about 180 DEG C of temperature, urea injects in the exhaust gas in the downstream LNT of the modification, and
And make containing the NO discharged from the LNT of the modificationxPass through NH with the exhaust gas of urea3- SCR catalyst.The NO of the releasexPass through ammonia
(being generated by urea) and NOxIn the NH3It is reacted in SCR catalyst and is converted to nitrogen.The NO of the releasexIt is in low-temperature storage in this
On modified LNT, then in the NO of higher temperature releasex, and further include by the NH3SCR catalyst is without storage
NOx。
Preferably, the LNT of the modification periodically passes through rich desulfurized step.Sulphur compound is for the modification present in fuel
LNT can be harmful, because the oxidation of sulphur compound generates the oxysulfide in the exhaust gas.In the LNT, sulfur dioxide can be with
It is oxidized to sulfur trioxide on platinum group metal, and forms surface sulfate (such as barium monoxide or carbonic acid on the surface LNT
Barium reacts to form barium sulfate with sulfur trioxide).These sulfate are more more stable than nitrate, and need higher temperature (>
500 DEG C) carry out desulfurization.If the LNT of the modification has low barium content, lower desulfurization temperature can be useful.
In rich desulfurization, the LNT of the modification is typically in enriched air: passing through greater than about 500 DEG C of temperature in fuel ratio environment
Degree, to complete desulfurization.The desulfurization preferably increases delivery temperature by injecting after fuel to carry out.Desulfurization program may include list
A, lasting is rich in phase or a series of short rich pulses.
Following embodiment only illustrates the present invention.Those skilled in the art will recognize that many variations in purport and power of the invention
In the range of sharp claim.
Embodiment 1: modified LNT is prepared
Modified LNT 1A
By NO of the flow type cordierite substrates material all in one piece comprising two layers of 400 holes/square inch (cpsi)xAdsorbent is urged
Agent formulation is coated.Lower layer's carrier coating includes Pt, Pd, 28% Ce/ magnesium-aluminate spinel and 66% dioxy
Change cerium (95% total CeO 2 supporting amount includes particulate cerium oxide, contains 7% Ba).The carrier coating uses
Method disclosed in WO99/47260 is coated on original substrate material all in one piece, then dry in 100 DEG C of forced ventilation drying machine
It 30 minutes, is then calcined 2 hours at 500 DEG C.
Preparation is by slurrying and is ground to d90Second slurry of < 20 microns of aluminium oxide composition, is then added suitable solvable
Property platinum and palladium salt and particulate cerium oxide generate 50% aluminium oxide and 50% particulate cerium oxide.Second slurry is passed through
Lower layer through calcining is administered to by exit passageway.By this it is partially dried and 500 DEG C calcine.
Preparation is by slurrying in water and is ground to d90The third of < 20 microns of silica-doped alumina powder composition
Slurry.Barium acetate is added in the slurry, suitable soluble platinum and palladium salt are then added.Then the slurry stirs 30 minutes
It is homogenized, adds β zeolite then to generate 81% silica-doped aluminium oxide and 19% β zeolite.By third slurry
The lower layer through calcining is administered to via access road.By this it is partially dried and 500 DEG C calcine, to generate 89g/ft3Pt and
30g/ft3Total PGM load capacity of Pd.
Compare LNT 2
By NO of the flow type cordierite substrates material all in one piece comprising single layer of 400 holes/square inch (cpsi)xAdsorbent is urged
Agent formulation is coated, this layer includes the particulate cerium oxide of Pt, Pd, Ce/ magnesium-aluminate spinel, Ba coating, and packet
Containing 33% Ce/ magnesium-aluminate spinel, 61% ceria, (93% total CeO 2 supporting amount includes granular dioxy
Change cerium, contain 7% Ba) and 113g/ft3Pt and Pd.The carrier coating is applied using method disclosed in WO99/47260
It is layed on original substrate material all in one piece, it is then 30 minutes dry in 100 DEG C of forced ventilation drying machine, it is then small in 500 DEG C of calcinings 2
When.
Embodiment 2: Engine Block Test
By modified LNT 1A and comparison LNT 2 (1.4L catalyst volume) 800 DEG C hydrothermal aging 5 hours.Each LNT
Using low pressure exhaust gas recycling (EGR) on 1.6L engine, preconditioned by 4 NEDC periods of operation, the NEDC period
5s richness purging with the λ 0.95 when 100kph cruises.Then it is evaluated on 2.2L engine with NEDC drive cycle.?
Without using rich purging in evaluation procedure.
The results show that the LNT 1A of the modification stores the NO of about 0.5g at most about 200 DEG Cx, then from 200 DEG C to
300 DEG C of almost hot NO for releasing storagex, this shows that the LNT of modification of the invention can be used in NH3SCR system.Fig. 2
The LNT 1A design of display, the modification makes rear LNT NO2/NOxThan increasing 20-40%, the 5-20% shape of this and comparison LNT 2
In contrast with.Table 1 describes the exhaust pipe CO discharge using the LNT 1A of the modification, which show considerably higher CO conversion ratio and
For the greatly modified stability of the oxidative deactivation of 4 NEDC without richness purging.Table 2 describes the LNT using the modification
The exhaust pipe HC of 1A is discharged, and which show considerably higher HC conversion ratios.
1 exhaust pipe CO of table discharge
2 exhaust pipe HC of table discharge
Claims (20)
1. the exhaust system for handling engine exhaust gas, it includes modified poor NOxTrap, urea injection system and ammonia-selectivity
Catalytic reduction catalysts, the wherein poor NO of the modificationxTrap is being lower than 200 DEG C of temperature storage NOxBe higher than 200 DEG C of temperature
Discharge the NO of storagex, the poor NO of the modificationxTrap includes:
(a) first layer, it includes NOxAbsorbent component and one or more platinums group metal, the wherein NOxAbsorbent component includes
Alkaline-earth metal, alkali metal, rare earth metal and its mixture；With
(b) second layer, it includes: the diesel oxidation catalyst area comprising platinum group metal, zeolite and optional alkaline-earth metal；And packet
The NO zoneofoxidation of platinum group metal and carrier.
2. exhaust system according to claim 1, wherein the urea injection system injects urine in the temperature higher than 180 DEG C
Element.
3. exhaust system according to claim 1, wherein the alkaline-earth metal, alkali metal, rare earth metal and its mixture are negative
It is loaded on inorganic oxide material.
4. exhaust system according to claim 3, wherein the inorganic oxide material is containing ceria material or oxidation
Magnesium-aluminium oxide.
5. exhaust system according to claim 4, wherein the magnesia-alumina is magnesium-aluminate spinel.
6. exhaust system according to claim 1 or 2, the wherein NOxAbsorbent component includes barium.
7. exhaust system according to claim 1 or 2, wherein one or more platinums group metal of first layer be selected from palladium,
Platinum, rhodium and its mixture.
8. exhaust system according to claim 1 or 2, wherein the zeolite in the diesel oxidation catalyst area is selected from sending down the fishbone
Frame type: AEI, CHA, LEV, BEA, FAU and MFI.
9. exhaust system according to claim 1 or 2, wherein the diesel oxidation catalyst area further includes: including oxygen
Change the inorganic oxide carrier of aluminium or silica-doped aluminium oxide.
10. exhaust system according to claim 1 or 2, wherein the carrier of the NO zoneofoxidation includes aluminium oxide and dioxy
Change cerium.
11. exhaust system according to claim 1 or 2, wherein the NO zoneofoxidation further includes manganese.
12. exhaust system according to claim 1 or 2, wherein ammonia-the selective catalytic reduction catalysts are selected from oxidation
Vanadium-titanium deoxide catalyst, vanadium oxide-tungsten oxide-titanium deoxide catalyst and metal/zeolite.
13. exhaust system according to claim 12, wherein metal/the zeolite includes the metal selected from iron or copper, and choosing
From the zeolite of following framework types: AEI, CHA, LEV, BEA or FER.
14. exhaust system according to claim 12, wherein metal/the zeolite includes metal and the β boiling selected from iron or copper
Stone.
15. exhaust system according to claim 12, wherein metal/the zeolite includes metal and magnesium selected from iron or copper
Alkali zeolite.
16. exhaust system according to claim 1 or 2, wherein ammonia-the selective catalytic reduction catalysts are ammonia-selections
Property catalysis reduction filter.
17. exhaust system according to claim 16, wherein the ammonia-selective catalytic reduction filter includes to have ammonia-
The filter of selective catalytic reduction catalysts, the ammonia-selective catalytic reduction catalysts are selected from: vanadium oxide-titanium dioxide is urged
Agent, vanadium oxide-tungsten oxide-titanium deoxide catalyst and metal/zeolite.
18. modified poor NOxTrap, it includes:
(a) first layer, it includes NOxAbsorbent component and one or more platinums group metal, the wherein NOxAbsorbent component includes
Alkaline-earth metal, alkali metal, rare earth metal and its mixture；With
(b) second layer, it includes: the diesel oxidation catalyst area comprising platinum group metal, zeolite and optional alkaline-earth metal；And packet
The NO zoneofoxidation of platinum group metal and carrier.
19. the method for handling vehicle internal combustion engine exhaust gas comprising:
(a) make poor NO of the exhaust gas Jing Guo modification according to claim 18 in the temperature lower than 200 DEG CxTrap removes this
Nitrogen oxides (NO in exhaust gasx), and the NO is discharged in the temperature higher than 200 DEG Cx；
(b) it is being higher than 180 DEG C of temperature, in the poor NO of the modificationxTrap downstream introduces urea into the exhaust gas；With
(c) make containing the poor NO from the modificationxThe NO of trap releasexExhaust gas with urea is by ammonia-selective catalytic reduction catalysis
Agent, by the NOxIt is converted to nitrogen.
20. further comprising according to the method for claim 19, the poor NO for periodically making the modificationxTrap is in enriched air: fuel
By the temperature higher than 500 DEG C in the environment of ratio, to remove accumulation in the poor NO of the modificationxSulphur on trap.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201462036184P | 2014-08-12 | 2014-08-12 | |
| US62/036,184 | 2014-08-12 | ||
| PCT/IB2015/056016 WO2016024193A1 (en) | 2014-08-12 | 2015-08-07 | Exhaust system with a modified lean noxtrap |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106661984A CN106661984A (en) | 2017-05-10 |
| CN106661984B true CN106661984B (en) | 2019-07-16 |
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