CN100546700C - From the waste gas of combustion engine, remove the catalyst of the method and the described method of enforcement of harmful substance - Google Patents
From the waste gas of combustion engine, remove the catalyst of the method and the described method of enforcement of harmful substance Download PDFInfo
- Publication number
- CN100546700C CN100546700C CNB200580016603XA CN200580016603A CN100546700C CN 100546700 C CN100546700 C CN 100546700C CN B200580016603X A CNB200580016603X A CN B200580016603XA CN 200580016603 A CN200580016603 A CN 200580016603A CN 100546700 C CN100546700 C CN 100546700C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- poor
- component
- storage
- under
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 278
- 238000000034 method Methods 0.000 title claims abstract description 103
- 239000002912 waste gas Substances 0.000 title claims abstract description 61
- 239000000126 substance Substances 0.000 title claims description 20
- 238000002485 combustion reaction Methods 0.000 title description 24
- 238000003860 storage Methods 0.000 claims abstract description 169
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 60
- 239000007789 gas Substances 0.000 claims abstract description 46
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 148
- 239000010457 zeolite Substances 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 60
- 229910021536 Zeolite Inorganic materials 0.000 claims description 58
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 34
- 238000005516 engineering process Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 15
- 239000011964 heteropoly acid Substances 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 15
- 229910000510 noble metal Inorganic materials 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052703 rhodium Inorganic materials 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 239000012876 carrier material Substances 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 150000002484 inorganic compounds Chemical class 0.000 claims description 7
- 229910010272 inorganic material Inorganic materials 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- -1 mixed oxide Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 5
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 description 24
- 238000012360 testing method Methods 0.000 description 24
- 230000006870 function Effects 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 239000000446 fuel Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000004215 Carbon black (E152) Substances 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010948 rhodium Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000004176 ammonification Methods 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 5
- 239000011232 storage material Substances 0.000 description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 2
- YBVAXJOZZAJCLA-UHFFFAOYSA-N nitric acid nitrous acid Chemical compound ON=O.O[N+]([O-])=O YBVAXJOZZAJCLA-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite group Chemical group N(=O)[O-] IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical compound O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007115 recruitment Effects 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- 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
- B01D53/9431—Processes characterised by a specific device
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
- F01N3/0842—Nitrogen oxides
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D41/00—Electrical control of supply of combustible mixture or its constituents
- F02D41/02—Circuit arrangements for generating control signals
- F02D41/021—Introducing corrections for particular conditions exterior to the engine
- F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
- F02D41/027—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus
- F02D41/0275—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus the exhaust gas treating apparatus being a NOx trap or adsorbent
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
- F01N2240/25—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an ammonia generator
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to handle the integral system of waste gas, it is preferably by at least a NO
x-storage component, at least a original position generate component, at least a ammonia storage component and at least a ammonia (NH of ammonia
3)-SCR-component is formed, and also relates to the method for handling waste gas, and this method comprises the steps: (i) at least under poor exhaust gas conditions, at least a NO
xStore NO in the-storage component
x(ii) under rich exhaust gas conditions, the NO that converted in-situ is stored
xBe ammonia (NH
3); (iii) under rich exhaust gas conditions, at least a NH
3Store NH in the-storage component
3(iv) under poor exhaust gas conditions, make NH
3With NO
xReaction.Thereby to small part and/or interim simultaneously and/or carry out part steps abreast and " store NO
x" and " use NO
xTransform NH
3".In addition, the preferred catalyst of implementing the inventive method is disclosed.
Description
The present invention relates to handle the integral system of waste gas, it is preferably by at least a NO
x-storage component, at least a original position generate the component of ammonia, the component and at least a ammonia (NH of at least a storage of ammonia
3)-SCR component (hereinafter being also referred to as the SCR-component) is formed, and also relates to the method for using this system handles waste gas.The invention still further relates to the catalyst of removing the harmful substance that contains nitrogen oxide in the waste gas of poor engine waste gas, the particularly-Fu operator scheme poor that is used for from combustion engine from circulating.Another purpose of the present invention is the method for the described catalyst of preparation.Other purpose of the present invention is to comprise the antigravity system of catalyst and by using described catalyst from the combustion engine waste gas that contains nitrogen oxide, particularly remove the method for harmful substance-Fu operator scheme poor from circulating in the waste gas of poor engine.Therefore, this method of operation in catalyst, it comprises: at NO
xStore nitrogen oxides in the-storage component, nitrogen oxides reduction is an ammonia, storage of ammonia in the component of storage of ammonia, and use NO
xOxidation ammonia becomes nitrogen.
From poor combustion engine, preferably the particular that removes No. three catalytic converters of harmful substance from bus engine is NO
x-storage catalyst.Utilize the management system of engine, described catalyst alternately is exposed under rich and the poor exhaust gas conditions.In poor operator scheme, they are stored in the nitrogen oxide NO that generates in the combustion process
xIn having the complex engine management systems process of complicated process, in short " enrichment stage " (mean and lack oxygen), catalytic decomposition becomes nitrogen to stored nitrogen oxide under reducing condition subsequently.Therefore, this catalyst also is called as " NO
x-absorber " or also be called as " NO
x-storage/reducing catalyst ".
In SAE document SAE950809, describe NO in detail
xThe function of-storage catalyst.
According at specific " temperature window ", employed NO in 200-500 ℃ typically
x-storage facilities, NO
x-storage catalyst works.At NO
xIn the heat ageing process of-catalyst, the narrowed width of temperature window.Limited temperature window is to wish the diesel engine of high low temperature active and the problem of wherein using in the poor four-stroke engine of the high low temperature active of major requirement therein.Conventional NO
xAnother problem of-storage catalyst is that in enrichment stage (this is essential for the stored nitrogen oxide of reduction) process, high secondary emission is for example with NH
3And H
2The S form may occur.
By using NH
3As selective reduction agent decomposing N O
xSCR-technology (selection catalytic reduction) also be that prior art is known.
Described SCR-technology is high efficiency technology, so that reductive NO
xEmission.For example in the fixed combustion facility, use SCR-technology.In SCR-technology, utilize ammonia as the selective reduction agent, make reaction of nitrogen oxides generate nitrogen.The stoichiometry of SCR-reaction (this means NH
3With NO
xMolar content than) for realizing roughly NO completely
xBeing converted, it is essential to say so, and it especially depends on reaction temperature and employed catalyst.Usually, can think ammonia mole must with the amount of nitrogen oxide in identical scope, so that guarantee high conversion ratio.
In US4782039 and US5451387, be the NH of 0.75-1.25 in scope
3/ NO
xFind high NO under the mol ratio
xConversion ratio.In practical experience, pass through NH especially
3Penetrate (breakthrough) (so-called " ammonia spills (slip) ") and limit the maximum NH that must regulate
3/ NO
xMol ratio, wherein said NH
3Penetrate along with NH
3/ NO
xRatio increase and increase.
DE19909933A1 discloses and has utilized inner ammonia to generate the method for operating of the facility of purifying waste gas.In the embodiment of DE19909933A1, utilize the generation of the Combustion Source realization ammonia of independent control.At least a Combustion Source generates rich waste gas, and this richness waste gas is conducted through the catalyst that is used to generate ammonia.The ammonia of Sheng Chenging is fed into and contains NO in such a way
xThe waste gas stream of poor Combustion Source in.Utilize the catalyst of nitrogen oxides reduction, with NO
xAnd NH
3Change into N
2
Described embodiment is subject to actual practice, and this is because the NH that generates at the catalyst place that is used to generate ammonia
3Amount and be present in NH in other logistics
3Amount must always exist with specific stoichiometry, otherwise NH
3Perhaps NO
xWill be with the concentration discharge that increases.
In another embodiment of DE19909933A1, NO
x-adsoption catalyst, ammonia reducing catalyst and catalyst for reduction of oxides of nitrogen switch according to the order of sequence.Therefore, in the poor operator scheme of Combustion Source, the nitrogen oxide that is included in a large number in the waste gas can cushion in the catalyst of nitric oxide adsorption, can desorb in the rich operator scheme of corresponding subsequent, and can be used in the catalyst of follow-up generation ammonia for generating ammonia to small part.Thereby catalyst switches while store nitrogen oxides under poor exhaust gas conditions, and the impossible reaction that ammonia and nitrogen oxide take place according to the order of sequence.
The another kind of exhaust gas purification of this type is disclosed in WO97/17532.In this document, the difference setting of catalyst is disclosed, wherein each catalyst has specific function.In one embodiment, switch catalyst, the NO that generates ammonia according to the order of sequence
x-adsoption catalyst, NH
3-storage catalyst and another kind of catalyst.This setting is very suitable for suppressing NH
3The secondary emission of form.In addition, can be in the ammonia-adsoption catalyst that adds, by the desorb of ammonia, reduction is no longer by NO
xThe NO that-adsoption catalyst stores
xTherefore, reductive NO
xTwo kinds of distinct methods press sort run each other: at first, store NO at the storage catalyst place
xIf described catalyst is filled the NO that then penetrates
xAvailable NH
3Be degraded into N
2Utilize described system, can under poor and rich operator scheme, reduce NO
xAnd NH
3The amount of penetrating.But storage and nitrogen oxides reduction are impossible simultaneously herein.
In US2002/0116920A1, the method for handling waste gas has been described, wherein arrange catalyst, oxidation catalyst and the SCR-catalyst that generates ammonia according to the order of sequence.In rich operator scheme, utilize NH
3Generate catalyst and generate NH
3Described ammonia is stored on the SCR-catalyst.In poor operator scheme, the NO that the utilization of SCR catalyst is discharged from engine
xThe NH that stores before transforming
3Become N
2Oxidation catalyst becomes NO by oxidation NO
2Increase the efficient of SCR-catalyst.
The shortcoming of the method for describing in US2002/0116920A1 is in the operating process of reality, only under high technical sophistication degree and obvious excessive fuel consumption, just can meet and utilize NO
xAnd NH
3Between SCR-reaction effectively transform NO
xNecessary stoichiometry.Therefore, in rich operator scheme process, the NH of formation
3With the mole of discharging in subsequently the poor operator scheme be suitable much at one.But this means essential the realization the long relatively rich stage, this will inevitably cause the fuel consumption that increases and the CO and the HC discharging of increase.
As principle, mainly the catalyst that uses in the method for prior art comprises active metal component and NO
x-storage component, described NO
x-storage component great majority contain the oxide of alkali metal, alkali earth metal or rare earth element.
As reactive metal, great majority use platinum.The major function of reactive metal is that oxidation NO becomes NO in the poor stage
2Usually be utilized as the NO of the oxidation of nitrate or nitrite form
x-storage component stores the NO that so forms
2Utilizing nitrate (nitrite) to make NO
xUnder the situation that the saturation degree of-storage component increases, NO
xConversion performance drop under the unacceptable level, therefore utilize the internal action of engine, the enrichment of waste gas takes place.Described enrichment causes the unexpected decomposition and the NO of nitrate (nitrite)
xRelease (deliberation).Because in enrichment process, enough reducing agents and in addition only seldom oxygen exist, therefore can utilize the direct reductive NO of carbon monoxide (CO) and hydrocarbon (HC)
xBecome N
2In order to quicken described reduction, NO
x-storage catalyst contains platinum in addition, and great majority also contain the rhodium of low content.Platinum and rhodium are present on the most of highly porous support oxide of temperature stabilization, for example on the oxide of Al, Si, Zr or Ti or its mixture.Especially, aluminium oxide usually is used as the carrier of platinum.The NO of prior art is for example disclosed in EP1317953A1, EP0716876B1, EP0730901B1, US2002/0048542A1, EP0982066A1, DE10036886A1, EP1010454A2, US6004521, EP1036591A1
x-storage catalyst.
Especially, be included in NO
xActive metal component in the-storage catalyst and additive guarantee also that with mainly the oxygen storage material based on the cerium Zirconium oxide is the same carbon monoxide (CO) and hydrocarbon (HC) can effecting reaction be carbon dioxide and water under richness and stoichiometry and poor exhaust gas conditions.According to identical mode, under rich and stoichiometric exhaust gas conditions, successfully make NO
xReaction becomes N
2
According to DE10113947B4, the method for amount of nitrogen oxides in the also known reduction combustion engine waste gas, it can carry out under the poor-Fu operator scheme that replaces, and wherein arranges start catalysts, NO according to the order of sequence
x-storage catalyst and SCR-catalyst.Therefore, under rich exhaust gas conditions, at NO
xUnder-storage catalyst and the start catalysts, nitrogen oxide is reduced ammonification.In another step, nitrogen oxide becomes nitrogen with the ammonia react that so forms under the SCR-catalyst.For each step,, regulate desired reducing condition (rich operator scheme) and oxidizing condition (poor operator scheme) respectively by regulating engine management system suitably.
Also knownly in the catalyst of purifying automobile exhaust gas, use zeolite.
US6689709B1 discloses the zeolite-β of hydrothermally stable, and it contains iron and cerium, its catalysis ammonia reductive NO
x(ammonia-SCR-reacts (passing through ammine selectivity catalytic reduction)).Thereby reductive NO
xThe method plan ammonia for good and all is metered in the waste gas stream.
US6004521 discloses the NO at the engine exhaust that is used for conventional richness-poor cycle operation
xUse zeolite in the-storage catalyst.Thereby zeolite is as the carrier of reactive metal.Thereby reductive NO
xMethod plan to make constantly the NO of storage in enrichment
xBe reacted into N with hydrocarbon and CO
2Therefore, do not form NH
3Do not cushion with in zeolite, having.
EP0970737A2 discloses a kind of catalyst, and it comprises the carrier that contains zeolite and metal oxide and stores and discharge component and at the noble metal of zeolite pores outside.Therefore, zeolite can only serve as the carrier of reactive metal.
EP1129764A1 discloses the catalyst of purifying diesel exhaust, and it contains at least a zeolite and other at least a support oxide (aluminium oxide, silica, titanium oxide, zirconia and alumina silicate with and mixed oxide) and at least a noble metal platinum, palladium, rhodium, iridium, gold or silver-colored.
EP0970737A2 and technical literature SAE900496 disclose on so-called HC-SCR (passing through hydrocarbon-selective catalytic reduction) meaning and have directly transformed NO with hydrocarbon
xWith zeolite.Thereby and NH
3-SCR technology is corresponding, and it is continuous processing method, wherein with the direct reductive NO of hydrocarbon
xBecome N
2About this point, use the zeolite of exchange of transition metal and noble metal or load, for example ZSM-5 and zeolite-β.
An object of the present invention is development process waste gas from the waste gas of poor engine, to remove NO
xMethod, this method with the circulation richness-poor operation mode, it removes NO
xBe higher than the catalyst of prior art with the efficient that reduces secondary emission.
Another object of the present invention provides catalyst with from the waste gas of combustion engine, particularly remove the harmful substance that contains nitrogen oxide in the waste gas of poor engine from the richness-poor operator scheme of circulation, thereby, can realize reducing the simplification and the more efficient methods of harmful substance contents in the described engine exhaust with respect to prior art by using described catalyst.
Utilize and comprise that in preferred embodiments the method for following part step realizes one object of the present invention at least:
(i) under poor exhaust gas conditions, at least a NO
xStore NO in the-storage component
x
(ii) under rich exhaust gas conditions, the NO that converted in-situ is stored
xBe ammonia (NH
3);
(iii) under rich exhaust gas conditions, at least a NH
3Store NH in the-storage component
3
(iv) under poor exhaust gas conditions, make NH
3With NO
xReaction.
Thereby preferably to small part and/or interim simultaneously and/or carry out part steps abreast and " store NO
x" and " make NH
3With NO
xReaction ".
The inventive method is characterised in that NO high in wide temperature range
xConversion ratio.
Preferably, use method of the present invention to reduce the four-stroke engine of coming the automobile operated under the comfortable poor mode and the NO of Diesel engine
xDischarging.
Also solve another purpose of the present invention by integrated antigravity system, wherein at least two kinds of different components have following function at least: (i) under poor exhaust gas conditions, store NO
x, (ii) under rich exhaust gas conditions, the NO that in-situ reducing is stored
xBe ammonia (NH
3), (iii) under rich exhaust gas conditions, at NH
3Store NH in the-storage facilities
3, (iv) under poor exhaust gas conditions, make NH
3With NO
xReaction.Each component combination on function in the system, and also preferred local, preferably be in direct contact with one another and further preferred respectively on the common matrix within continuous matrix or continuous matrix on.
System's (hereinafter being also referred to as " system ") that the present invention handles waste gas is suitable under the richness/lean conditions of circulation from waste gas, preferably always removing nitrogen oxide (NO in the waste gas of engine
x).
Integrated antigravity system of the present invention is made up of two kinds of components that have function (i)-(iv) at least at least.In addition, antigravity system can have any other component of any other function.Every kind of component itself also can for example carrier component and active component be formed by component.
According to the present invention, in the integral system of handling waste gas, above-described NO
x-storing technology combines with above-described SCR-technology.Thereby for SCR-technology essential ammonia not only with tangible amount available from NO
xThe nitrogen oxide of combination in the-storage component, promptly original position obtains.Therefore be possible with any amount from the additional ammonia raw material of outside.
In document scope, term
(catalyst) componentAny material that finger has at least a function essential for the effect of integral system.
Within the scope of the invention, term
NO x Conversion performanceShould be meant in the poor operator scheme of the system that is used to handle waste gas as waste gas composition, EGT, oxygen partial pressure, NO
xThe volume flow of engine emission, waste gas and the function of operating time, a certain amount of NO in the unit interval
xThe degree of removing.
Term
The poor operating timeShould be meant continuing of time, the system that wherein handles waste gas is exposed under the poor waste gas incessantly.The poor operating time is NO
xThe important factor of the fill level of-storage catalyst, it means passes through NO
xThe NO of-storage catalyst absorption
xTotal amount.
As the main standard of engine type and catalyst classification, utilize "
The air value" λ expresses the ratio of air and fuel.Therefore, numerical value λ=1.0 this means just to have enough air in the combustion space exactly corresponding to the stoichiometric proportion of fuel and dry air, so that all fuel can burn into carbon dioxide and water in the stoichiometry mode.
PoorWaste gas is that the waste gas and the rich waste gas of air value λ＞1 is the waste gas of air value λ＜1.Say that usually, purpose is that the enrichment time section is short as far as possible, the low as far as possible and poor time period of concentration level is long as far as possible minimizing on the meaning of fuel consumption.Especially, the ratio of richness-poor time period and concentration level depend on the NO of the system that handles waste gas consumingly
x-conversion performance and NO
xPower of regeneration.In the enrichment stage, the carbon monoxide (CO) and the hydrogen (H of combustion engine discharging recruitment
2) and other hydrocarbon (HC).These reproducibility components are reduced into nitrogen and ammonia with nitrogen oxide, and self resolve into carbon dioxide (CO
2) and water (H
2O).
Short as far as possible and alap another reason of concentration level of preferred enrichment time section is, must minimize the amount of penetrating of CO and HC and NH for example
3, H
2The increase of the secondary emission of S and COS form.
According to the preferred embodiment of system of the present invention, at least a NO
x-storage component, at least a original position generate the component and at least a SCR component of the component of ammonia, at least a storage of ammonia must be integrated on space and/or function, and its mode is by utilizing NO
xThe synchronizing process of-storage and SCR-reaction is guaranteed high NO
xConversion performance, thereby preferably minimize NH
3The secondary emission of form.
Although the complexity height of exhaust treatment system of the present invention, but in another preferred embodiment, for the design of this system, can be on the matrix that common or continuous matrix promptly links to each other successively must (catalysis) component in conjunction with all, thereby provide effectively and the exhaust treatment system of cost savings.Preferred be implemented on the common matrix in the following manner, integrated (catalysis) component (NO on the common matrix of preferred monoblock honeycomb ceramics form
x-storage component, original position generate component, the component of storage of ammonia, the SCR-component of ammonia): preferably utilize known wash coat technology, the component that the front is mentioned is simultaneously or be administered to according to the order of sequence on the common matrix.
NO used in the present invention
x-storage component can be formed by known noble metal component and/or according to the known storage facilities of prior art basically.
Basically, as NO
x-storage facilities, all because of its chemistry, preferred basic property can store nitrogen oxides be suitable with the material of nitric oxide adsorption respectively, thereby the nitrogen oxide that stores must be stable under suitable temperature conditions.Therefore,, for example be oxide, hydroxide or carbonate form preferably, as storage material with the compound of alkali metal (Na, K, Rb, Cs), alkaline-earth metal (Mg, Ca, Sr, Ba), rare earth metal (La, Ce, Pr etc.) and zirconium.As active metal component, preferably be administered to the platinum (Pt, Pd, Rh, Ru, Ir) on the porous carrier oxide.
In poor operator scheme process, NO
xThe function of-storage component is the NO that stores the combustion engine discharging
xBecause NO
xIncrease NO
x-component saturation degree causes NO
xConversion performance drop under the situation of unacceptable level, utilize the internal action of engine, carry out the enrichment of waste gas.Because enrichment causes stored NO
xReduce.Can preferably be arranged on the NO in exhaust treatment system of the present invention downstream by use
xSensor, mensuration reaches unacceptable NO
xThe degree of-storage level.
When use is furnished with NO
xDuring the exhaust treatment system of-storage catalyst, enrichment should cause as far as possible optionally that nitrogen oxides reduction becomes N
2In these systems, do not wish to form NH
3
But the objective of the invention is in the enrichment phase process, to form NH
3Opposite with the document of mentioning in the prior art, mainly or at least mainly be stored in NO by the front
xNitrogen oxide in the-storage component forms NH
3
Especially, the inventive method is characterised in that, can generate NH in the very short time period
3, this is because the NO that accumulates in long period section (it is one of poor stage of front)
xMeasure and can be used for reducing ammonification.
Within the scope of the invention, the nitrogen oxide high selectivity is reduced into N in the enrichment phase process
2Not compulsory, in principle or even undesirable.On the one hand, can utilize the hydrogen (H that in enrichment process, discharges
2) and carbon monoxide (CO) amount, on the other hand, can utilize the catalyst formulation of optimization, control NO
xEffectively be reduced into NH
3
Preferably, be present in NO in addition
xOne of active metal component in the-storage component has the function that original position generates the function of ammonia components or generates ammonia.
Must mention that ammonia not necessarily must only come from and is stored in NO
xNitrogen oxide in the-storage component also can be formed with less important or low at least amount (＜50%, preferred＜20%) by those nitrogen oxide from engine emission in the enrichment phase process in addition.
The ammonia of Xing Chenging now is stored in suitable NH in such a way
3In-the storage component.Preferably, under the condition of poor and rich waste gas, in wide temperature range, NH
3-storage component can be adsorbed the NH that discharges
3
Can or absorb or with the absorption of adduct form or can store NH in addition to small part absorption
3Any material all can be used as NH
3-storage component.Thereby preferred Lewis acids or Bronsted acid.
Preferably, within the scope of the invention, NH
3The function of-storage component is as far as possible quantitatively to be adsorbed on the NH that generates in the rich stage
3, but adsorb sizable amount at least.Thereby enrichment time section and degree should be low as far as possible, so that minimize additional fuel consumption.
In implication of the present invention, enrichment time section and enrichment degree should be enough high, so that allow: (i) be emptied completely NO as far as possible
x-storage catalyst and the nitrogen oxide ammonification that (ii) allows effectively reduction to discharge constantly in enrichment.The ratio of poor time period and the preferred time period of rich time period in 5: 1 to 100: 1 scopes, preferred 30: 1 to 80: 1.Preferred enrichment degree is in 0.8＜λ＜0.99 scope.
If become poor operator scheme,, that is preferably reduce the NO that from engine, discharges simultaneously then by different modes from rich operator scheme
xDischarge capacity: a part of NO
xItself stores NO
xIn-the storage component, and another part directly with at NH
3The NH of combination in the-storage component
3Reaction.Owing to reduce NO simultaneously and with two kinds of different response paths according to the present invention now
x,, can realize obviously higher NO therefore with respect to the method for prior art
xConversion performance.
According to the present invention at NH
3The NH of combination discharging in the-storage component
3In poor phase process subsequently, according to so-called SCR-reaction, NH
3Can with the NO that under poor exhaust gas conditions, from engine, discharges
xResolve into N together
2Within the SCR-component or part the SCR-reaction takes place.As the SCR-component, can utilize the known any material of SCR-reaction those skilled in the art, V/Ti catalyst for example is because they are that fixedly exhaust-gas treatment is known.In preferred embodiments, the SCR-component is lewis acid or Bronsted acid, thereby also serves as NH
3-storage component.
According to the present invention, in preferred embodiments, with not oxidation or the NH that only stores with considerably less amount oxidation with the oxygen that is included in the waste gas
3Become NO
xAnd the mode of discharging, the NH of chemistry accumulation combination
3-storage component/SCR-component.
Owing at first be stored in NO to small part in such a way
xNO in the-storage component
xChange ammonia into, become N in SCR-reaction reaction simultaneously then
2, method therefore of the present invention allows the NO of increase
xConversion performance, this is because NO is supported in the SCR-reaction
xStorage.
In order to allow SCR-reaction and NO
xStorage the time operating sequence, preferably make NO
x-storage component and/or NH
3-storage component and/or SCR-component contact separately from each other, and preferably the mode with physical mixed contacts.In addition, can for example, realize this contact by alternate manner well known by persons skilled in the art by any combination of chemistry and/or mechanical means or physics, chemistry and mechanical means.
In contrast, it is not preferred that the unique or main order of these components is arranged, and this is because under tactic situation, can only carry out simultaneously SCR-reaction and NO under low-down degree toward each other
xStorage, carry out but can lead if it were not for mode one by one.But some operation in tandem sequences of reaction still within the scope of the present invention.
At for example NO
x-storage component is arranged on NO
xUnder the situation of-storage component and the two upstream of SCR-component, in poor operator scheme, NO
x-storage component load NO
x, and along with the increase of poor operator scheme, up to NO
xStore and reduce, the SCR-reaction just obviously helps total NO
xConversion ratio.
In preferred embodiments, NH
3-storage component is identical with the SCR-component, this means suitable material can: (i) under rich exhaust gas conditions, store NH
3And (ii) reaction transforms according to SCR-under poor exhaust gas conditions.
In preferred embodiments, NO
x-storage component contains at least a reactive metal.This will guarantee that CO and HC can be reacted into carbon dioxide and water effectively under the condition of enrichment, stoichiometry and poor waste gas.According to identical mode, be contained in NO
xReactive metal place in the-storage component under enrichment and stoichiometric exhaust gas conditions, can successfully carry out NO
xTo N
2Conversion or NH
3Formation.
In addition, antigravity system of the present invention also can contain additive, and oxygen-storage material for example is for example based on the oxygen-storage material of cerium Zirconium oxide.
In order in the rich stage, to minimize CO and the HC amount of penetrating, in preferred embodiments, for example another catalyst of oxidation catalyst form can be set in the downstream.
With former NO
x-storage catalyst system compares, and system of the present invention has higher NO
xConversion performance.
Method and system of the present invention preferably can be used for following application:
For example store NO as if causing that because of unexpected load variations EGT is lower than or is higher than
xRequired or favourable temperature then specifically demonstrates advantage of the present invention.Condition is enough NH
3Be present in NH
3In-the storage facilities, in this case, the SCR-reaction can provide high NO separately
xTo N
2Conversion ratio.
The method of the application of the invention can be seen other advantage, can move engine for a long time in poor operator scheme and minimize secondary emission.
Another advantage of the inventive method and system is four kinds of essential for waste gas system of the present invention components, i.e. NO
x-storage component, NH
3-generation component, NH
3-storage component and SCR-component can be incorporated into the continuous system of one-tenth on common carrier element or matrix such as the honeycomb ceramics.In addition, compare with other method in the continuous feed from outside returning charge to ammonia, the advantage of method of the present invention is not need accurately to keep the stoichiometry determined, because of this situation can active control NH
3With respect to NO
xStoichiometry.
Under the poor/rich operator scheme of circulation, utilize from the waste gas of poor engine, to remove to comprise nitrogen oxide (NO
x) the catalyst of harmful substance, can realize another purpose, it is characterized in that described catalyst:
(i) at NO
xStore nitrogen oxides (NO in the-storage component
x),
(ii) make NO
xTransform ammonification (NH
3),
(iii) at NH
3Storage of ammonia in the-storage component,
(iv) make NH
3With NO
xReaction.
Opposite with prior art, in a kind of catalyst rather than several catalyst, store nitrogen oxides, reduction ammonification, storage of ammonia and ammoxidation.In raw catelyst, cause the component physics contact of the catalyst of described process, catalytic component of the prior art is then separated from one another.
Can under the efficient that increases, remove NO by using raw catelyst to handle waste gas
xSurprisingly, compare with catalyst with the method for prior art, described catalyst also can make undesirable secondary NH
3Discharging obviously descends.
Use contains NO
x-and NH
3The catalyst of-storage component is removed NO from waste gas
xMethod also can be called as the NSR-C-SCR-method (" with the NO of selection-catalysis-reductive coupling
x-storage-reduction ").
Term " NO
x-store or NO
xStorage " implication be both to have adsorbed NO
x, absorption of N O again
xIf NO
xWith lip-deep surface mass form physical absorption of the component in being present in catalyst or chemisorbed, then there is NO
xAbsorption.Term " NO
xAbsorption " be meant and form NO
xNitrogenous " the body phase " of-storage facilities.Therefore, similarly implication is used for NH
3Storage and NH
3-storage component.
In special embodiment, be used for from the waste gas of the poor engine of the poor/rich operator scheme of circulation, removing and contain nitrogen oxide (NO
x) the catalyst of harmful substance be characterised in that catalyst contains material and the acid solid of at least a (2) group and the material that at least a (3) optional and (4) are organized of at least a (1) group:
(1) Pt, Pd, Rh, Ir and Ru are present in separately or with form of mixtures separately and are selected from the following carrier material: the oxide of Al, Si, Zr, Ti, Ce, alkali earth metal and rare earth element, mixed oxide, phosphate and sulfate; Heteropoly acid; Zeolite; And composition thereof;
(2) zeolite; Heteropoly acid; Sulfated zirconia or basic zirconium phosphate; And composition thereof;
(3) alkali metal, alkali earth metal, rare earth element, zirconium, titanyl compound and mixed oxide;
(4) inorganic compound of V, Cr, Mn, Fe, Co, Ni, Cu, In, Ga, Ag and Sn and composition thereof;
This catalyst wherein
(i) at NO
xStore nitrogen oxides (NO in the-storage component
x),
(ii) with NO
xTransform ammonification (NH
3),
(iii) at NH
3Storage of ammonia in the-storage component,
(iv) make NH
3With NO
xReaction.
Thereby the material of (1) group and optional (3) group and optional (4) group serves as NO
xThe acid solid of-storage component and (2) group serves as NH
3-storage component.The material that (1) group and optional (3) and (4) are organized also serves as NO
xThe acid solid of-absorption or absorbent components and (2) group serves as NH
3-absorption or absorbent components.
In another embodiment of catalyst, one of carrier material of (1) group itself is the acid solid of (2) group.
Be used for from the waste gas of poor engine of the poor/rich operator scheme of circulation, removing and contain nitrogen oxide (NO
x) the described further embodiment of catalyst of harmful substance be characterised in that described catalyst contains the material of at least a (1) group and the material that at least a (3) optional and (4) are organized:
(1) Pt, Pd, Rh, Ir and Ru are present in separately or with form of mixtures separately and are selected from the following carrier material: the oxide of Al, Si, Zr, Ti, Ce, alkali earth metal and rare earth element, mixed oxide, phosphate and sulfate; Heteropoly acid; Zeolite; And composition thereof;
(3) alkali metal, alkali earth metal, rare earth element, zirconium, titanyl compound and mixed oxide;
(4) inorganic compound of V, Cr, Mn, Fe, Co, Ni, Cu, In, Ga, Ag and Sn and composition thereof;
The carrier material of wherein at least a (1) group is acid solid, and it has abovely organizes defined implication and this catalyst at (2):
(i) at NO
xStore nitrogen oxides (NO in the-storage component
x),
(i i) is with NO
xTransform ammonification (NH
3),
(iii) at NH
3Storage of ammonia in the-storage component,
(iv) make NH
3With NO
xReaction.
In another embodiment, can utilize catalyst equally, described catalyst is characterised in that material and the acid solid of at least a (2) group and the material that at least a (3) optional and (4) are organized that contains at least a (1) group:
(1) Pt, Pd, Rh, Ir and Ru are present in separately or with form of mixtures separately and are selected from the following carrier material: the oxide of Al, Si, Zr, Ti, Ce, alkali earth metal and rare earth element, mixed oxide, phosphate and sulfate; Heteropoly acid; Zeolite; And composition thereof;
(2) zeolite; Heteropoly acid; Sulfated zirconia or basic zirconium phosphate; And composition thereof;
(3) alkali metal, alkali earth metal, rare earth element, zirconium, titanyl compound and mixed oxide;
(4) inorganic compound of V, Cr, Mn, Fe, Co, Ni, Cu, In, Ga, Ag and Sn and composition thereof;
Especially, the efficient of catalyst depends on macroscopic view design and catalyst form.Especially, utilize catalyst, can realize good result by known " wash coat " method preparation.
In another embodiment, utilize a kind of catalyst, it is characterized in that described catalyst contains material and the acid solid of at least a (2) group and the material that at least a (3) optional and (4) are organized of at least a (1) group:
(1) Pt, Pd, Rh, Ir and Ru are present in separately or with form of mixtures separately and are selected from the following carrier material: the oxide of Al, Si, Zr, Ti, Ce, alkali earth metal and rare earth element, mixed oxide, phosphate and sulfate; Heteropoly acid; Zeolite; And composition thereof;
(2) zeolite; Heteropoly acid; Sulfated zirconia or basic zirconium phosphate; And composition thereof;
(3) alkali metal, alkali earth metal, rare earth element, zirconium, titanyl compound and mixed oxide;
(4) inorganic compound of V, Cr, Mn, Fe, Co, Ni, Cu, In, Ga, Ag and Sn and composition thereof;
Wherein catalyst can be produced according to the wash coat method.
The reactive metal of (1) group serves as reactive metal, the therefore main catalytic activity of being responsible for.Term
Reactive metalBe appreciated that to being not only various elements, and be the possible oxide and the suboxide of described noble metal.
(1) and (2) group heteropoly acid have the implication of inorganic multivariate acid respectively, this inorganic multivariate acid has two kinds of central atoms.They can form by the following material of acidifying: the acid of multi-element metal oxygen, and as those of chromium, molybdenum, tungsten and vanadium, and element cation, for example Ti
4+, Zr
4+, Al
3+, Co
2+Or Co
3+, Cu
1+Or Cu
2+Those and other or nonmetal oxygen acid.
As the ammonia-storage component of (2) group, acid solid is suitable, and they are formed by zeolite, heteropoly acid, sulfated zirconia and calcium phosphate.
Zeolite is the solid with different acid strengths, and this is because for example the zeolite of ion-exchange usually has lower solid-state acidity.When having the aluminium of high-load, the acidity of zeolite can be very low.In addition, can minimize the acidity of zeolite by heat or chemical treatment, thereby described zeolite does not demonstrate the typical performance of the solid with high acidity.
Therefore, when utilizing zeolite to be used for active component (being noble metal component) as support oxide, the zeolite of the Li Yonging ability that can serve as ammonia-storage component simultaneously depends on the acid performance of zeolite itself respectively.
In one of embodiment, one or more zeolites of (1) group are identical with one or more zeolites and the heteropoly acid of (2) group with heteropoly acid.
In described embodiment, NO
x-storage component also has NH simultaneously
3The function of-storage component.
As the acid solid of (2) group, the ratio that preferably utilizes Si/Al is greater than one or more zeolites of 3.The ratio of the Si/Al of acid zeolite should be at least 3, and this is because utilize this zeolite can guarantee the hydrothermal stability that zeolite is enough.
The zeolite of preferred (2) group is selected from pentasile, Y-zeolite, USY, DAY, modenite and zeolite-β.
Can utilize described zeolite with pure state or with form of mixtures, wherein also comprise the form of using the doping zeolite, described doping zeolite obtains by ion-exchange or any other processing.Thereby zeolite can be sodium type, ammonium type or H type.In addition, can perhaps by ion-exchange, sodium, ammonium or H type be transformed into other ionic species by with slaine and oxide dipping.Example is by in moisture rare earth element chloride solution intermediate ion exchange, and the Na-Y-zeolite is transformed into SE-zeolite (SE=rare earth element).Especially preferably utilize alkali earth metal, rare earth element, gallium, indium and iron to carry out ion-exchange.Various elements can with iron, oxide, suboxide or carbonate form be present on the zeolite or within.
Acid zeolite can both serve as NH
3-storage component is served as the SCR-catalyst again.
As the case may be, except containing NO
x-storage component and NH
3Beyond-the storage component, catalyst also can contain the 3rd component.Described component is made up of ion exchanged zeolite at least.Described component is served as additional NH
3-SCR-component.Thereby preferably use the zeolite of ion-exchange and/or rare earth element-exchange.
The material of (4) group serves as adulterant.Usually, they exist with inorganic compound or with element form.Preferably, they exist with oxide form.
Term
OxideAlso comprise all suboxides, hydroxide and carbonate.
In catalyst, in the catalyst total amount, total weight range of noble metal is 0.05-10wt%, and wherein the content range of noble metal is 0.1-5wt% in the gross mass of catalyst.
The feature of catalyst is that also in the gross mass of catalyst, the content range of the acid solid of (2) group is 5-95wt%, wherein the scope of preferred 10-75wt%.
In another embodiment, catalyst contains at the palladium as (1) group on the zirconia of support oxide or cerium oxide or aluminium oxide or the silica alumina mixed oxide.
In the particular of last embodiment, catalyst contains PdRu or Rh or Pt in addition.
In another embodiment, catalyst contains cerium oxide or the cerium oxide of (2) group and iron or the cerium oxide of (2) group and the iron of praseodymium oxide and (3) group of (3) group of (2) group in addition.
In another embodiment, catalyst is present on the monoblock honeycomb ceramics.
Can prepare raw catelyst according to the method that comprises the steps (i):
(i) make NO in the catalyst
x-storage component and NH
3-storage component contact, the material that perhaps makes at least a (1) group and the acid solid of at least a (2) group and at least a (3) contacting of choosing wantonly with material that (4) are organized.
According to the embodiment of catalyst, can by solid material that mixes (1) group and (3 of choosing wantonly) and/or (4) and (2) material of organizing, perhaps, contact according to pure mechanical system by wash coat technology.
For macroscopic view design and catalyst form (these may have high influence to efficient), all embodiments are preferred, usually, and the value of verified these embodiments in Catalyst Production.Especially, described embodiment is known " wash coat " and/or " honeycomb " technology.
The technology of mentioning at last is ground into several microns granularity based on a large amount of carrier materials in aqueous suspension, be applied in then on pottery or the metal forming body.Basically, can be before coating or afterwards, with other component applied of water-soluble or water-insoluble form in wash coat.In application of catalyst all the components to formed body after, as principle, dry described formed body, and look concrete condition, calcining at elevated temperatures.
Especially preferably has high BET-surface area and the catalyst material layout on the high BET-of reservation surface after heat ageing.About the structure of hole, especially preferably as the macropore of duct formation, they coexist with mesopore and/or micropore.Thereby mesopore and/or micropore contain reactive metal.In addition, (it must play NH to the acid solid of preferred especially (2) group
3-memory function and SCR-function) and one or more NO
x-storage component is mixed as far as possible up hill and dale.
The catalyst that is used for the inventive method preferably exists with the honeycomb ceramics form of powder, particle, extrudate, formed body or coating.
Preferably utilize known wash coat technology, by making each component contact, with the mode of each component applied in the catalyst on the common matrix, on the common matrix of common matrix, preferred monoblock honeycomb ceramics form, realize the integrated of catalytic component with aforementioned.
But also but each component of mechanical mixture is NO
x-and NH
3-storage component is used for example mixture of mixed-powder, particle, extrudate or formed body form then.
Although the complexity height of catalyst can mix all components essential for Catalyst Design on common matrix.Therefore, the exhaust treatment system of effective and cost savings can be provided.
Another purpose of the present invention also is an antigravity system, and wherein foregoing catalyst combines existence with at least a other catalyst.
In one embodiment, at least a other catalyst is NO
x-storage catalyst.Can utilize NO described in the prior
x-storage catalyst.
In antigravity system, raw catelyst and NO
x-storage catalyst is preferably arranged according to the order of sequence.
In another embodiment, catalyst with NO
xThe form of mixtures of-storage catalyst is present in the antigravity system.
In another embodiment, oxidation catalyst is arranged on the downstream of catalyst or antigravity system, perhaps NO
x-sensor is arranged on the downstream of at least a other catalyst.
Another purpose of the present invention is to use raw catelyst or antigravity system, and described antigravity system contains described catalyst, is used for removing from the waste gas of the poor engine of poor-Fu operator scheme of circulation that is combustion engine containing nitrogen oxide (NO
x) harmful substance.
Another purpose of the present invention relates in the poor engine exhaust from the poor-Fu operator scheme of circulation removes and contains nitrogen oxide (NO
x) the method for harmful substance, it is characterized in that using aforesaid catalyst or antigravity system.
In specific embodiment, described method is characterised in that uses aforesaid catalyst or antigravity system, thereby the method comprising the steps of (i)-(iv):
(i) at NO
xStore NO in the-storage component
x
(ii) transform stored NO
xBe ammonia (NH
3);
(iii) at NH
3Store NH in the-storage component
3
(iv) make NH
3With NO
xReaction.
The feature of the method for purifying waste gas also is carrying out carrying out step (ii) under step (i) and the condition at rich waste gas under the condition of poor waste gas, and under negative and poor exhaust gas conditions, carry out step (iii) and (iv) the two.
In addition, step (i) and (iv) can be at least simultaneously interim and/or carry out abreast.
Term
Combustion engineImplication be the heat energy converter, it changes into heat and mechanical energy by the burning chemical energy that will be stored in the fuel.About
Has internally fired engine, airtight air is working media (it defines on hot machine meaning) in air tight and tradable working space (for example plunger), and is the carrier of the essential oxygen of burning simultaneously.Burn with circulation pattern, thus before each circulation fresh load fuel and (air) oxygen the two.According to the guiding of circulation, for example according to the pV-work sheet of Carnot, can on thermokinetics, distinguish four-stroke engine and Diesel engine exactly.The real work of each of described engine type is defined as follows described.
For the air value that is used to divide engine type and special catalyst, be suitable for foregoing.For disclosed special catalyst type, the mixture of concrete λ＞1.2 be expressed as "
Poor", and λ＜1.0 be expressed as "
Rich", so that obtain clearly stoichiometric range boundary.Therefore, on meaning of the present invention, negative thus defined and/or lean mixture also is expressed as the non-stoichiometry mixture.
Conventional four-stroke engine is characterised in that, beyond working space, promptly takes place therein to form uniform benzine-air mixture beyond the plunger space of burning, also is the outside supply ignition of controlling.Four-stroke engine needs lower boiling fuel and is not easy the fuel (the ignition limit of four-stroke engine is typically between λ=0.6 and λ=1.4) of ignition.In the context of the present invention, for exhaust fume catalytic, the particularly importantly main operation (=stoichiometric operation) under about 1 λ value of Chang Gui four-stroke engine (it has No. three catalytic converters that utilize λ-sensor to control).
Term " poor engine " comprises this four-stroke engine of mainly utilizing the excessive oxygen running.For purpose of the present invention, poor engine defines by its λ value particularly, that is to say that the poor engine in meaning of the present invention is the engine that turns round down at least partially in lean conditions (that is the λ value is 1.2 or bigger), it is overrun when stop supplies fuel also.In addition, under poor engine conditions, rich operator scheme and stoichiometric operation pattern can appear naturally equally: can pass through modern injecting systems, cause the short-term enrichment of engine and waste gas by Motronic control maps, (for example under the situation that load increases, in full load or when starting) perhaps also can take place under the driving operation of nature.On meaning of the present invention, blocked operation modal representation negative and poor circulation is " negative-poor operator scheme ".
Especially, on meaning of the present invention, the poor engine of term generally comprises following embodiment:
All four-stroke engine with direct injection (BDE-engine) and operating condition λ＞1, and all four-stroke engine of outside preparation fuel mixture.Wherein, described classification comprises the engine of all other classification chargings (stratified-charge), promptly has the engine of the mixture of ignition easily near the ignition piston, have all engines of lean mixture in a word, and have and the four-stroke engine of directly injecting relevant high compression.Hereinafter, for example (GDI=gasoline is directly injected according to Mitsubishi technology; Common line injection) engine comprises by FSI (injection of=fuel staging) engine of VW exploitation or the IDE that is imagined by Renault (=inject direct key element)-engine.
All Diesel engines (vide infra).
Easily or be not easy many materials engine of ignition, the i.e. engine of combustion fuel, fuel mixture (for example any mixtures of alcohol, biological alcohol, vegetable oil, kerosene, oil and two or more aforementioned materials).
Diesel engineBe characterised in that the formation of internal mix thing, uneven fuel-air mixture and self-igniting.Therefore, Diesel engine requires the fuel of easy ignition.In the context of the present invention, specific meanings is that diesel exhaust demonstrates and the similar feature of poor engine exhaust, this means they be continuously poor be oxygen enrichment.Therefore, about removing of nitrogen oxide, for the remove NO relevant with Diesel engine
xWith catalyst (under poor operator scheme, being used for four-stroke engine) must have similar requirement.But compare with the four-stroke-cycle bus engine, the fundamental difference of diesel-powered bus engine is, compare the EGT of diesel-powered bus engine generally lower (100 ℃-350 ℃) with the EGT (250 ℃-650 ℃) of generable four-stroke-cycle bus engine in the driving range of DO of legal provisions.Lower EGT makes use not have or is only particularly attractive by the catalyst of sulfate contamination slightly that this is because can effectively carry out above-mentioned desulfurization acidifying more than about 600 ℃ EGT.In the present invention, with respect to the catalyst that is used for poor engine, all the elements of the present invention are also to be applicable to the catalyst that is used for Diesel engine respectively.
According to the formation of mixture and the characteristic load running speed of engine,, must need the concrete catalyst of regulating to be used for exhaust-gas treatment for different engines.Therefore, the catalyst that for example is used for conventional four-stroke engine, be adjusted to λ ≈ 1 and the optional fuel mixture of air value continuously by injection and choke valve by λ-sensor control, with for example be used in λ＞1.2 time promptly comparing at the normal catalyst that has the poor engine that turns round under the excessive oxygen under the operation that drives, have diverse reductive NO
xFunction.Obviously under the excessive situation of oxygen, in reactive metal place Reduction of NO
xBe difficult.
Term "
Diesel oxidation catalyst" relating generally to remove the catalyst of two kinds of important harmful substances in the combustion engine waste gas, described harmful substance is by being oxidized to carbon monoxide that carbon dioxide removes and in the ideal case by being oxidized to the hydrocarbon that water and carbon dioxide are removed.When in Diesel engine, using catalyst, remove two kinds of mentioned functions and can add the third function, promptly remove carbon black by oxidation.
Term "
No. three catalytic converters" relating generally to remove three kinds of catalyst that mainly contain harmful substances in the combustion engine waste gas, described harmful substance is by being reduced into the nitrogen oxide (NO that nitrogen is removed
x), by being oxidized to carbon monoxide that carbon dioxide removes and in the ideal case by being oxidized to the hydrocarbon that water and carbon dioxide are removed.When in Diesel engine, using catalyst, remove three kinds of mentioned functions and can add the 4th kind of function, promptly remove carbon black by oxidation.
In the stoichiometric operation, promptly under the λ value in about 1.0 close limit, be used for routine No. three catalytic converters of the four-stroke engine of prior art.Thereby utilize injection and choke valve, by regulating the oil air mixture in the combustion space, regulate the λ value.
Non-chemically Metrological operationIn, that is in unconventional operation, it is possible obviously being different from 1.0 λ value, λ＞1.2 or λ＞2.0 for example, but λ＜0.9 also is possible.The discontinuous operation of engine, that is between the poor and negative operator scheme of engine blocked operation, be called as
Richness-poor operation Pattern
Compare with catalyst with known method, hereinafter further set forth and discussed technological merit of the present invention.
Known according to prior art, reactive metal Pt, Pd, Rh, Ir and Ru have several functionalities in the waste gas of the poor engine of purifying.On the one hand, they itself can serve as NO
x-adsorbent, and in the poor stage, can store NO
xOn the other hand, they support NO
xAt NO
xStore in-the storage component.For example the Pt catalytic oxidation NO becomes NO
2, in step subsequently, NO
2With the absorption of nitrate or nitrite form or be absorbed in NO
xOn-the storage material or within.
In addition, the NO that in the rich stage, stores of reactive metal catalysis
xBe reduced into NH
3Because of rather than only by at NO
xThe nitrogen oxide that stores in-the storage catalyst forms ammonia, and promptly is being lower than the ammonia that those nitrogen oxide that discharge in stoichiometric operator scheme (the being rich operator scheme) process form minor amount by what discharge from engine in addition in rich phase process.
In addition, noble metal also is supported in CO and HC oxidation and whole three tunnel functions in stoichiometric engines operator scheme process in the poor phase process.
Formed ammonia is stored in the NH of catalyst
3In-the storage component.Described component can be adsorbed on the NH that discharges under the poor and rich exhaust gas conditions in wide temperature range
3This means NH
3-storage component is used for being adsorbed on as far as possible quantitatively the NH that rich phase process generates
3As mentioned above, enrichment time section and degree should be low as far as possible, so that minimize the additional consumption of fuel.On the other hand, on meaning of the present invention, enrichment time section and degree should be enough high, so that be emptied completely NO as far as possible
x-storage catalyst becomes ammonia so that guarantee the nitrogen oxide that effectively reduction discharges constantly in enrichment.
If rich operator scheme switches to poor operator scheme, then can imagine simultaneously in two kinds of different modes and reduce NO by engine emission
xDischarge capacity: a part of NO
xBe stored in NO
xIn-the storage catalyst, and another part is direct and NH
3The NH of combination in the-storage facilities
3Be reacted into N
2Owing to reduce NO simultaneously and with two kinds of different reactive modes
x, with the known NO of use
xAlready known processes during-storage catalyst is compared, and can realize obviously higher NO
xConversion performance.
According to the present invention, the NH that is discharged
3At NH
3Combination in the-storage component.In poor phase process subsequently, can utilize the NO that under poor exhaust gas conditions, from combustion engine, discharges
xAccording to so-called SCR-reaction (SCR), degraded NH
3
Under poor operational circumstances, with stored NH
3Not oxidized or only on very little degree, be comprised in dioxygen oxidation in the waste gas and become again and be NO
xAnd the mode of discharging, chemistry forms the NH at technology combination of the present invention
3-storage/SCR-catalyst.Because in such a way, at first be stored in NO to small part
xNO in the-storage catalyst
xTransform ammonification, on the meaning of SCR-reaction, be reacted into N then
2, so this technology allows to increase NO
xConversion performance, this is because NO is supported in the SCR-reaction
xStorage.
In order to ensure SCR-reaction and NO
x-carry out when storing, wish not only from the integrated NO of economic aspect
x-storage catalyst, NH
3-storage facilities and SCR-catalyst, for example integrated with the physical mixture form.On the contrary, arranging described component according to the order of sequence will not be target orientation, and this is because under the situation of arranging according to the order of sequence, SCR-reaction and NO
xStorage can only on low-down degree, take place simultaneously, but in quite wide scope, carry out continuously.As if for example NO
x-storage catalyst is arranged on NO
xThe upstream of-storage component and SCR-catalyst, then in poor operator scheme, NO at first
x-storage catalyst will be by NO
xFill.NO in the poor operator scheme process that increases only
xStorage situation about descending under, the SCR-reaction can total relatively NO
xConversion ratio is obviously measured.
In an embodiment of technology of the present invention, NO is set with downstream at catalyst or antigravity system
xThe mode of sensor is carried out described technology, and measured numerical value is delivered on the engine management system of combustion engine of richness-poor adjusting of carrying out waste gas.In preferred embodiments, when surpassing adjustable NO
xDuring threshold value, induce enrichment.
With utilize known NO
xThe existing technology of-storage catalyst is compared, and when using the above catalyst that defines, this technology particularly has higher NO in low temperature range
xConversion performance.
If for example cause that EGT is lower than or surpass NO because of unexpected load variations
x-storing essential temperature, advantage then of the present invention is obvious especially.If enough NH
3Be present in NH
3In-the storage component, in this case, the SCR-reaction can be guaranteed high NO separately
xTo N
2Conversion ratio.Another advantage is to drive engine in poor operator scheme for a long time, and therefore minimizes secondary emission.
To be used in combination the NO of catalyst of the present invention and conventional catalyst such as prior art
xThe mode of-storage catalyst can be moved technology of removing harmful substance of the present invention.Found that with respect to the high conversion performance in low temperature range this being combined in also has high conversion performance in the high temperature range.Clearly this combination has synergy, and this is unexpected.
In order to minimize the amount of penetrating of CO and HC in the rich phase process, another catalyst can be set in the downstream of catalyst of the present invention, be preferably another catalyst of oxidation catalyst form.
For the technology of removing harmful substance, this catalyst preferably is arranged near the position of engine or in the underbody position of vehicle.
The catalyst of the inventive method also can move in conjunction with at least a other following catalyst or filter: conventional start catalysts such as ignition catalyst, HC-SCR-catalyst, carbon black or carbon black granules filter.
Thereby can utilize the catalyst coated carbon black granules filter that is used for the inventive method.
Description of drawings
Fig. 1 shows when using conventional storage catalyst down for 250 ℃, NO in the engine exhaust
xContent (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor);
Fig. 2 shows when using conventional storage catalyst down for 250 ℃, NH in the engine exhaust
3Content (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor);
Fig. 3 shows at 250 ℃ and descends when implementing method of the present invention and using integral system NO in the engine exhaust
xContent (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor);
Fig. 4 shows at 250 ℃ and descends when implementing method of the present invention and using integral system of the present invention NH in the engine exhaust
3Content (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor);
Fig. 5 shows according to embodiment 2 (B2) when 150 ℃ and 200 ℃ (test condition I) use catalyst of the present invention down, under the richness/poor operator scheme of circulation, and NO
xConcentration over time;
Fig. 6 shows according to Comparative Examples 1 (VB1) when 150 ℃ and 200 ℃ (test condition I) use conventional storage catalyst (reference) down, under the richness/poor operator scheme of circulation, and NO
xConcentration over time;
Fig. 7 shows according to embodiment 2 (B2) when 200 ℃ and 250 ℃ (test condition II) use catalyst of the present invention down, under the richness/poor operator scheme of circulation, and NH
3Concentration over time;
Fig. 8 shows according to embodiment 3 (B3) when 200 ℃ and 250 ℃ (test condition II) use catalyst of the present invention down, under the richness/poor operator scheme of circulation, and NH
3Concentration over time;
Fig. 9 shows according to Comparative Examples 01 (VB01) when 200 ℃ and 250 ℃ (test condition II) use conventional storage catalyst (reference) down, under the richness/poor operator scheme of circulation, and NH
3Concentration over time;
Figure 10 shows according to Comparative Examples 02 (VB02) when 150 ℃, 200 ℃ and 250 ℃ (test condition II) use the storage component (KI) of catalyst of the present invention down, under the richness/poor operator scheme of circulation, and NH
3Concentration over time;
Figure 11 shows according to embodiment 2 (B02) and Comparative Examples 2 (VB02), under fresh catalyst, and under test condition I, in richness/poor circulation, average N O
xConversion ratio is with the variation of reaction temperature;
Figure 12 shows according to embodiment 6 (B06) and Comparative Examples 3 (VB03), under fresh catalyst, and under test condition I, in richness/poor circulation, average N O
xConversion ratio is with the variation of reaction temperature;
Figure 13 shows according to embodiment 79 (B79), embodiment 81 (B81) and Comparative Examples 1 (VB01), under fresh catalyst, and under test condition I, in richness/poor circulation, average N O
xConversion ratio is with the variation of reaction temperature.
Described accompanying drawing relates to the embodiment of describing subsequently.
Implement the embodiment of the inventive method
Below in the embodiment that exemplifies, compare with catalyst with the method that prior art is known, described the method for handling waste gas according to the present invention and exemplified Preparation of Catalyst and improved performance.Employed specific embodiment and concrete numerical value must be interpreted as the restriction that is not the general expression made in specification and claim.
In packed bed laboratory reaction device, in the engine exhaust of simulation, measure the technology of the present invention that relates to of using system of the present invention by the stainless steel preparation.Test this system (5s richness/60s is poor) under the richness/poor operator scheme of circulation.
Test parameter is as described below:
Temperature range: 150-450 ℃
The composition of admixture of gas
Poor: 1000ppmv CO, 100ppmv propylene (propen), 300ppmv NO, 10%O
2,
Surplus N
2
Rich: 0.03%O
2,～6%CO ,～2%H
2
Gas flow: 45.000h
-1
Utilize the Lambda-Meter of Btas company, carry out O
2Measurement.Utilize the chemiluminescence device measuring N O of Ecophysics company
xUtilize the mass spectrograph of Balzers company, carry out NH
3Measure.
Measurement shown in Fig. 1-4 allows relatively to use conventional NO
xCommon process of-storage catalyst (Fig. 1 and 2) and the technology of the present invention (Fig. 3 and 4) of using exhaust treatment system of the present invention, wherein said exhaust treatment system of the present invention is by NO
x-storage component, NH
3-generation component, NH
3-storage component and SCR-component are formed.Under the situation of described embodiment, four kinds of components of mentioning are included on the single honeycomb substrate together.For relatively more conventional reference system and system of the present invention, applied NO
xThe quality of-storage component and reactive metal is identical respectively.System of the present invention is except NO
xBeyond-the storage component, also contain another component in addition, this component has NH simultaneously
3The function of-storage component and SCR-catalyst.
Fig. 1 shows when using conventional storage catalyst down for 250 ℃, NO in the engine exhaust
xConcentration (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor).Therefore, Fig. 2 shows when using identical conventional storage catalyst down for 250 ℃, NH in the engine exhaust
3Concentration (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor).
Fig. 3 shows at 250 ℃ and descends when implementing method of the present invention NO in the engine exhaust
xConcentration (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor).Therefore, Fig. 4 shows at 250 ℃ and descends when implementing method of the present invention NH in the engine exhaust
3Concentration (longitudinal axis, the arbitrary unit) variation of (transverse axis) in time (5s richness/60s is poor).
These measurement results clearly illustrate that: (i) with conventional NO
x-storage catalyst is compared, and exhaust treatment system of the present invention does not have NH in rich phase process
3Discharging (perhaps not obvious) guarantees (ii) that in addition (in fact) removes NO fully in whole operating times in poor stage
xBut along with the time of poor operator scheme increases, conventional NO
x-storage catalyst is lost most efficient.
Catalyst embodiment
Embodiment 1 (B01)
Catalyst is made up of two kinds of component I and II.
For the preparation of component I (KI), the zirconia that suspends in water (XZ16075, Norton company) is also pulverized in ball mill.After drying, provide 1.25g material crushed with the support oxide form.
Mix 147 microlitre 1.6mol palladium nitrate aqueous solutions and 178 microlitre 2.5mol cerous nitrate solutions, and dilute with 675 microliters of water.With 1000 microlitre gained solution impregnating carrier oxides, this absorbs corresponding to zirconic water.The support oxide that drying is so flooded under 80 ℃ are 16 hours then.
The gained load is 2wt% palladium and 5wt% cerium with respect to the amount of support oxide.
As component I I, utilize beta-zeolite (H-BEA-25, S ü d-Chemie company).
In order to prepare catalyst, in mortar, mix 1.25g component I, 0.53g component I I and 3ml water.Then, descended dry gained materials 16 hours at 80 ℃.
Subsequently, in air, calcined this material down 2 hours (with " fresh " expression) at 500 ℃.
In addition in containing the air stream of 10% water, at 650 ℃ of materials 16 hours (being expressed as " wearing out ") that following calcining part is fresh.
Embodiment 2-45 (B02-B45)
Be similar to embodiment 1 preparation catalyst; wherein for the preparation of component I (KI); the aqueous solution with one or more salt; for example palladium nitrate, three nitrato nitrosyl radical rutheniums (II), rhodium nitrate, platinum nitrate, ferric nitrate, praseodymium nitrate, cerous nitrate, potassium nitrate oxide impregnation zirconium, and wherein change component I I.
Table (table 1) with embodiment shows the composition based on each catalyst of percetage by weight.
Embodiment 46 (B46)
Catalyst is made up of two kinds of component I and II.
For the preparation of component I (KI), calcined cerous nitrate (III) (Aldrich company) 2 hours down at 500 ℃.After calcining, provide the 1g material as support oxide.
Dilute 118 microlitre 1.6mol palladium nitrate aqueous solutions with 982 microliters of water.With 1100 microlitre gained solution impregnating carrier oxides, this water corresponding to carrier material absorbs.Then, the support oxide that drying is so flooded under 80 ℃ are 16 hours.
The gained load is the palladium of 2wt% with respect to the amount of support oxide.
As component I I, utilize beta-zeolite (H-BEA-25, S ü d-Chemie company).
In order to prepare catalyst, in mortar, mix 1g component I, 1g component I I and 3ml water.Dry gained material is 16 hours under 80 ℃.
Subsequently, in air, calcined this material down 2 hours (with " fresh " expression) at 500 ℃.
In addition in the air logistics that contains 10% water vapour, at 650 ℃ of materials 16 hours (being expressed as " wearing out ") that following calcining part is fresh.
Embodiment 47-75 (B47-B75)
Be similar to embodiment 46 preparation catalyst; wherein for the preparation of component I (KI); the aqueous solution with one or more salt; for example palladium nitrate, three nitrato nitrosyl radical rutheniums (II), rhodium nitrate, platinum nitrate, ferric nitrate, praseodymium nitrate, cerous nitrate oxide impregnation zirconium, and wherein change component I I.
Embodiment 76
Catalyst is made up of two kinds of component I and II.
For the preparation of component I (KI), the silica-alumina that in water, suspends (Siralox5/170, Sasol company), and in ball mill, pulverize.After drying, provide the 5g material crushed as support oxide.
Mix the 513 microlitre 1.0mol platinum nitrate aqueous solution and 15600 microlitre 0.35mol barium nitrate aqueous solutions, and dilute with 387 microliters of water.Mix described support oxide and the described solution of 16500 microlitres, and when stirring evaporation water.In drying oven, dry support oxide of so flooding are 16 hours under 80 ℃.Subsequently, in muffle furnace, in air, calcined component I I 2 hours down at 500 ℃.
The gained load is the platinum of 2wt% and the barium of 15wt% with respect to the amount of support oxide.
As component I I, utilize beta-zeolite (Zeocat PB/H, Zeochem company).
In order to prepare catalyst, mix 0.25g component I and 0.25g component I I.
Embodiment 77
Catalyst is made up of two kinds of component I and II.
For the preparation of component I (KI), the silica-alumina that in water, suspends (siralox5/170, Sasol company), and in ball mill, pulverize.After drying, provide the 5g material crushed as support oxide.
Mix the 384 microlitre 1.0mol platinum nitrate aqueous solution and 243 microlitre 1.0mol rhodium nitrate aqueous solutions and 54610 microlitre 0.1mol barium nitrate aqueous solutions.Mix described support oxide and the described solution of 55237 microlitres, and when stirring evaporation water.Then, in drying oven, dry support oxide of so flooding are 16 hours under 80 ℃.Subsequently, in muffle furnace, in air, calcine component I down at 500 ℃.
The gained load is the platinum of 1.5wt%, the rhodium of 0.5wt% and the barium of 15wt% with respect to the amount of support oxide.
As component I I, utilize beta-zeolite (Zeocat PB/H, Zeochem company).
In order to prepare catalyst, mechanical mixture 0.25g component I and 0.25g component I I.
Embodiment 78
This catalyst is made up of three kinds of components.
In order to prepare component I (KI), the zirconia that in water, suspends (XZ16075, Norton company), and in ball mill, pulverize.After drying, provide the 5g material crushed as support oxide.
Mix the 752 microlitre 1.0mol platinum nitrate aqueous solution and 198 microlitre 1.0mol, three nitrato nitrosyl radical ruthenium (II) aqueous solution, the 714 microlitre 2.5mol cerous nitrate aqueous solution, and dilute with 2336 microliters of water.With 4000 these support oxide of microlitre gained solution impregnation, this relates to zirconic water and absorbs.Dry support oxide of so flooding are 16 hours under 80 ℃.
The gained load is the palladium of 1.6wt%, the ruthenium of 0.4wt% and the cerium of 5wt% with respect to the amount of support oxide.
As component I I, utilize beta-zeolite (H-BEA25, S ü d-Chemie company).
In order to prepare component III (KIII), with 0.5gNH
4-beta-zeolite (NH
4-BEA25, S ü d-Chemie company) be fed in the 1mol cerous nitrate solution, and stirred 2 hours down at 80 ℃.Afterwards, filter zeolitic material, and with the water washing of complete desalination, and 120 ℃ of dryings 16 hours down.In muffle furnace, in air, calcined the gained material 2 hours down at 500 ℃.
In order to prepare catalyst, in mortar, mix 1.25g component I, 0.75g component I I, 0.5g component III and 5ml water.Then, descended dry gained materials 16 hours at 80 ℃.
Subsequently, in air, calcined this material down 2 hours (with " fresh " expression) at 500 ℃.
In addition in the air logistics that contains 10% water, at 650 ℃ of materials 16 hours (being expressed as " wearing out ") that following calcining part is fresh.
Embodiment 79 (B79)
Catalyst is made up of the mechanical impurity of two kinds of catalyst.
In order to prepare catalyst (with " fresh " expression), the catalyst and the 0.15g reference catalyst (VB01) of mixing 0.18g embodiment 1 (B01).
Embodiment 80 (B80)
Catalyst is made up of the mechanical impurity of two kinds of catalyst.In order to prepare catalyst (with " fresh " expression), the aging catalyst and the 0.15g reference catalyst (VB01) of mixing 0.18g embodiment 34 (B34).
Embodiment 81 (B81)
Catalyst is made up of the mechanical impurity of two kinds of catalyst.
In order to prepare catalyst (with " fresh " expression), the aging catalyst and the 0.15g reference catalyst (VB01) of mixing 0.18g embodiment 35 (B35).
Comparative Examples 01 (VB01)
Comparative Examples 01 contains the known NO based on Pt/Pd/Rh/Ba/Ce of prior art
x-storage catalyst (reference catalyst).
Comparative Examples 02 (VB02)
Comparative Examples 02 comprises the component I (KI) of the catalyst of embodiment 2 (B02), and it was calcined 2 hours down at 500 ℃.
With respect to zirconic amount, load is the palladium of 2wt%, the ruthenium of 0.4wt% and the cerium of 5wt%.
Comparative Examples 03 (VB03)
Comparative Examples 03 comprises the component I (KI) of the catalyst of embodiment 6 (B06), and it was calcined 2 hours down at 500 ℃.
With respect to zirconic amount, load is the palladium of 2wt%, the ruthenium of 0.4wt%, the iron of 2wt% and the cerium of 5wt%.
In having the table (table 1) of embodiment, show the composition of each catalyst based on percetage by weight.
Table 1: composition (B01-77) with catalyst of two kinds of components
Catalyst test
Utilize the engine exhaust of simulation, in by the fixture bed experiment chamber reactor of stainless steel preparation, measure the catalyst that is used for the inventive method.In 150-400 ℃ temperature range, detecting catalyst in the richness/poor operator scheme of circulation.
Test parameter is as described below.
Test condition I
Richness-poor adjusting: 2s richness/60s is poor
The composition of admixture of gas:
Poor: 300ppmv NO, 1000ppmv CO, 100ppmv propylene, 10%O
2, 5%H
2O,
Surplus N
2
Rich: 0.03%O
2,～6%CO ,～2%H
2
Gas flow: 45L/h
Catalyst quality: 0.15-0.5g
Test condition II
Richness-poor adjusting 2s richness/60s is poor
The composition of admixture of gas:
Poor: 300ppmv NO, 1000ppmv CO, 100ppmv propylene, 10%O
2, surplus
N
2
Rich: 0.03%O
2,～6%CO ,～2%H
2
Gas flow: 45L/h
Catalyst quality: 0.15-0.5g
Measurement is used for the catalyst of the inventive method as bulk material.On formed body, do not use wash coat.For activity measurement, great majority use the screening part of granularity as the 315-700 micron.
As reference catalyst (VB01), use the NO of commercial honeycomb shape
x-storage catalyst.Grind reference catalyst, and also measure active as bulk material.About the comparison between reference system and the catalyst of the present invention, the quality of the noble metal of being used respectively with activity measurement in identical.
Utilize the Lambda-Meter of Etas company, carry out O
2Measurement.Utilize the chemiluminescence device measuring N O of Ecophysic company
xUnder test condition II, utilize the mass spectrograph of Balzers company, carry out NH
3Measurement.
Hydrothermal aging
In muffle furnace, flow down at the air of steam with 10 volume %, under 650 ℃ temperature, carry out the hydrothermal aging of catalyst.Thereby described catalyst kept 16 hours under described temperature, and cool to room temperature.
About the evaluation of catalyst, under different reaction temperatures, in richness/poor circulation, calculate average N O
xRatio.In table 2-5 and in Figure 11-13, summarized under fresh condition and the analog value of catalyst after hydrothermal aging.
Table 2. in richness/poor operator scheme, under fresh catalyst, NO
xThe catalysis test result of the conversion ratio (noble metal amount in the test condition I, catalyst: 0.05g)
Table 3. in richness/poor operator scheme, under fresh catalyst, NO
xThe catalysis test result of the conversion ratio (noble metal amount in the test condition I, catalyst: 0.0025g)
Table 4. is under the catalyst of 650 ℃ of following hydrothermal agings NO in richness/poor operator scheme
xThe catalysis test result of the conversion ratio (noble metal amount in the test condition I, catalyst: 0.05g)
Table 5. in richness/poor operator scheme, under the catalyst of hydrothermal aging, NO
xThe catalysis test result of the conversion ratio (noble metal amount in the test condition I, catalyst: 0.025g)
The catalyst measurement result shows, under low EGT (＜300 ℃), comprises that the catalyst of component I and II has than reference NO
xThe NO that-storage catalyst is obviously higher
xConversion ratio.This can be used under the fresh condition and after hydrothermal aging.
NO in richness/poor circulation shown in the table 5-6
xThe measurement of concentration allows under 150-200 ℃ EGT, relatively the NO between the storage catalyst (VB1) of catalyst (B2) and routine
xConversion ratio.
Fig. 7-8 shows under catalyst and generates NH
3
Fig. 9 shows that the storage catalyst (VB01) in routine forms NH down
3
Measurement result obviously shows:
(i) and NO
x-storage-catalyst is compared, and contains NO
x-and NH
3The catalyst of-storage component does not demonstrate NH
3Discharging; In addition
(ii) particularly under low EGT, guarantee more effectively to remove NO
x
Catalyst of the present invention contains the component based on zeolite, and it serves as NH
3-storage component and SCR-catalyst.Figure 11 and 12 shows catalyst (B02 and B06) and does not use NO between the storage component (KI) (VB02 and VB03) of zeolite component
xThe comparison of conversion ratio.
Result shown in Figure 13 shows, contains NO by use
x-and NH
3The catalyst of-storage component and conventional NO
x-storage catalyst) mechanical impurity of (B79 and B81) is with reference NO
x-storage catalyst is compared, and is implemented in 150-400 ℃ the interior NO of temperature range
xThe improvement of conversion ratio.
Claims (18)
1. be used for from the waste gas of poor engine of the poor/rich operator scheme of circulation, removing NO
xCatalysis process, this method comprises the steps (i)-(iv) at least:
(i) under poor exhaust gas conditions, at least a NO
xStore NO in the-storage component
x
(ii) under rich exhaust gas conditions, the NO that converted in-situ is stored
xBe ammonia NH
3
(iii) under rich exhaust gas conditions, at least a NH
3Store NH in the-storage component
3
(iv) under poor exhaust gas conditions, make NH
3With NO
xReaction,
It is characterized in that mainly or at least mainly being stored in NO by the front
xNitrogen oxide in the-storage component forms NH
3
2. the process of claim 1 wherein that carrying out the desired catalyst component of different step (i)-(iv) forms continuous system on space and/or the function.
3. the method for claim 2, wherein at least two catalyst components are present on the common matrix or on the matrix system of associating.
4. the process of claim 1 wherein and utilize identical catalyst component that NH takes place
3Storage and according to the NH of SCR technology
3Transform.
5. the process of claim 1 wherein for NO
xStorage, all material of application all can interact with nitrogen oxide owing to its chemical property.
6. the method for claim 2, wherein continuous system contains and is useful on the catalyst component that generates ammonia, storage of ammonia and ammonia is changed into nitrogen on space and/or the function.
7. the method for claim 6 wherein is administered to each catalyst component on the formed body that is selected from honeycomb, pellet, bead or extrudate.
8. the method for claim 7 is characterized in that catalyst component comprises material and the acid solid of at least a (2) group and the material that at least a (3) optional and (4) are organized of at least a (1) group:
(1) Pt, Pd, Rh, Ir and Ru are present in separately or with form of mixtures separately and are selected from the following carrier material: the oxide of Al, Si, Zr, Ti, alkali earth metal and rare earth element, mixed oxide, phosphate and sulfate; Heteropoly acid; Zeolite; And composition thereof;
(2) zeolite; Heteropoly acid; Sulfated zirconia or basic zirconium phosphate; And composition thereof;
(3) alkali metal, alkali earth metal, rare earth element, zirconium, titanyl compound and mixed oxide;
(4) inorganic compound of V, Cr, Mn, Fe, Co, Ni, Cu, In, Ga, Ag and Sn and composition thereof.
9. the method for claim 8, the ratio of Si/Al of described zeolite that it is characterized in that (2) group is greater than 3.
10. the method for claim 8 is characterized in that the described zeolite of (2) group is selected from five yuan of silica-rich zeolites, Y-zeolite, modenite and zeolite-β.
11. the method for claim 8 is characterized in that described catalyst component comprises other component of being made up of the zeolite of ion-exchange.
12. the method for claim 8 is characterized in that in the gross mass of catalyst component total weight range of noble metal is 0.5-10wt%.
13. the method for claim 8 is characterized in that in the gross mass of catalyst component, the content range of the acid solid of (2) group is 5-95wt%.
14. the method for claim 8 is characterized in that the material of described at least a (1) group is Ce.
15. the method for claim 8 is characterized in that the described zeolite of (2) group is selected from ultrastable and dealuminium Y type beta stone.
16. catalyst component is being used for removing NO from the waste gas of poor engine of the poor/rich operator scheme of circulation
xCatalysis process in purposes, wherein said method comprises the steps (i)-(iv) at least:
(i) under poor exhaust gas conditions, at least a NO
xStore NO in the-storage component
x
(ii) under rich exhaust gas conditions, the NO that converted in-situ is stored
xBe ammonia NH
3
(iii) under rich exhaust gas conditions, at least a NH
3Store NH in the-storage component
3
(iv) under poor exhaust gas conditions, make NH
3With NO
xReaction;
It is characterized in that mainly or at least mainly being stored in NO by the front
xNitrogen oxide in the-storage component forms NH
3
17. catalyst component is being used for removing NO from the waste gas of poor engine of the poor/rich operator scheme of circulation
xCatalysis process in purposes, wherein said catalyst component comprises material and the acid solid of at least a (2) group and the material that optional at least a (3) and (4) are organized of at least a (1) group:
(1) Pt, Pd, Rh, Ir and Ru are present in separately or with form of mixtures separately and are selected from the following carrier material: the oxide of Al, Si, Zr, Ti, alkali earth metal and rare earth element, mixed oxide, phosphate and sulfate; Heteropoly acid; Zeolite; And composition thereof;
(2) zeolite; Heteropoly acid; Sulfated zirconia or basic zirconium phosphate; And composition thereof;
(3) alkali metal, alkali earth metal, rare earth element, zirconium, titanyl compound and mixed oxide;
(4) inorganic compound of V, Cr, Mn, Fe, Co, Ni, Cu, In, Ga, Ag and Sn and composition thereof;
Wherein said catalysis process comprises the steps (i)-(iv) at least:
(i) under poor exhaust gas conditions, at least a NO
xStore NO in the-storage component
x
(ii) under rich exhaust gas conditions, the NO that converted in-situ is stored
xBe ammonia NH
3
(iii) under rich exhaust gas conditions, at least a NH
3Store NH in the-storage component
3
(iv) under poor exhaust gas conditions, make NH
3With NO
xReaction;
It is characterized in that mainly or at least mainly being stored in NO by the front
xNitrogen oxide in the-storage component forms NH
3
18. the purposes of claim 17 is characterized in that the material of described at least a (1) group is Ce.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004018648A DE102004018648A1 (en) | 2004-04-16 | 2004-04-16 | Integrated catalyst system to remove e.g. nitric oxides from exhaust gases comprises nitric oxide storing component, ammonia-generating component, ammonia-storing component and selective catalytic reduction component on common substrate |
| DE102004018648.0 | 2004-04-16 | ||
| DE102004058210.6 | 2004-12-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1956769A CN1956769A (en) | 2007-05-02 |
| CN100546700C true CN100546700C (en) | 2009-10-07 |
Family
ID=35456098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200580016603XA Expired - Fee Related CN100546700C (en) | 2004-04-16 | 2005-04-14 | From the waste gas of combustion engine, remove the catalyst of the method and the described method of enforcement of harmful substance |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100546700C (en) |
| DE (1) | DE102004018648A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004058210A1 (en) * | 2004-12-02 | 2006-06-14 | Hte Ag The High Throughput Experimentation Company | Integrated catalyst system to remove e.g. nitric oxides from exhaust gases comprises nitric oxide storing component, ammonia-generating component, ammonia-storing component and selective catalytic reduction component on common substrate |
| JP5037283B2 (en) * | 2007-09-26 | 2012-09-26 | 本田技研工業株式会社 | Exhaust gas purification device for internal combustion engine |
| JP5547084B2 (en) * | 2007-11-30 | 2014-07-09 | コーニング インコーポレイテッド | Zeolite honeycomb body |
| CN101829537B (en) * | 2009-03-12 | 2014-01-15 | 中国石油化工股份有限公司 | Adsorbent composition containing I B-group metal component and application thereof |
| CN102588129B (en) * | 2012-02-07 | 2016-12-14 | 上海艾铭思汽车控制***有限公司 | Design of High Pressure Common Rail Diesel Engine nitrogen oxides and the optimization cooperative control method of particulate emission |
| EP2690089A1 (en) * | 2012-07-25 | 2014-01-29 | Urea Casale SA | Use of urea synthesis purge gas in an integrated ammonia-urea process and related plant. |
| CN103920392B (en) * | 2014-04-17 | 2016-08-17 | 山东大学 | A kind of technique utilizing lean oxygen-enriched alternation response to carry out denitrating flue gas |
| JP6546738B2 (en) * | 2014-11-12 | 2019-07-17 | 日立造船株式会社 | Aldehyde decomposition catalyst, exhaust gas treatment facility and exhaust gas treatment method |
| CN109675612A (en) * | 2018-12-31 | 2019-04-26 | 萍乡市华星环保工程技术有限公司 | A kind of molecular sieve catalyst and its production method of middle low-temperature denitration |
| CN115518631B (en) * | 2022-11-02 | 2024-01-23 | 四川大学 | NO (NO) x Adsorption-selective catalytic reduction catalyst, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3886260A (en) * | 1971-09-25 | 1975-05-27 | Monsanto Co | Process for reducing nitrogen oxides |
| CN1306455A (en) * | 1998-04-28 | 2001-08-01 | 约翰逊马西有限公司 | Process and appts. for reducing nitrogen oxide content in exhaust gases by controlled addition of NH3 |
| CN1084827C (en) * | 1995-11-09 | 2002-05-15 | 丰田自动车株式会社 | Method and device for purifying exhaust gas of engine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19820828B4 (en) * | 1998-05-09 | 2004-06-24 | Daimlerchrysler Ag | Nitrogen oxide emission reducing emission control system |
| DE10104160B4 (en) * | 2001-01-30 | 2008-07-10 | Umicore Ag & Co. Kg | Method for operating an exhaust gas purification system for an internal combustion engine |
-
2004
- 2004-04-16 DE DE102004018648A patent/DE102004018648A1/en not_active Ceased
-
2005
- 2005-04-14 CN CNB200580016603XA patent/CN100546700C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3886260A (en) * | 1971-09-25 | 1975-05-27 | Monsanto Co | Process for reducing nitrogen oxides |
| CN1084827C (en) * | 1995-11-09 | 2002-05-15 | 丰田自动车株式会社 | Method and device for purifying exhaust gas of engine |
| CN1306455A (en) * | 1998-04-28 | 2001-08-01 | 约翰逊马西有限公司 | Process and appts. for reducing nitrogen oxide content in exhaust gases by controlled addition of NH3 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102004018648A1 (en) | 2005-11-10 |
| CN1956769A (en) | 2007-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100546700C (en) | From the waste gas of combustion engine, remove the catalyst of the method and the described method of enforcement of harmful substance | |
| JP4733110B2 (en) | Method for removing harmful substances from exhaust gas of combustion engine and catalyst for carrying out the method | |
| CN101296748B (en) | Denitrification catalyst, honeycomb structure type denitrification catalyst, and method of denitrification with the same | |
| US8466083B2 (en) | Bi-functional catalyst materials for lean exhaust NOx reduction | |
| US20120042631A1 (en) | Catalyst materials for ammonia oxidation in lean-burn engine exhaust | |
| CN101014409B (en) | Exhaust gas cleaning catalyst, exhaust gas cleaning device, and system comprising internal combustion engine | |
| US20120060472A1 (en) | CATALYST MATERIALS FOR NOx OXIDATION IN AN EXHAUST AFTERTREATMENT SYSTEM THAT USES PASSIVE AMMONIA SCR | |
| CN106582794B (en) | Use for diesel engine catalyst and preparation and application based on modified molecular screen and hydrotalcite Derived Oxides | |
| CN105050710B (en) | As for handling the aluminosilicate of the catalyst of exhaust gas or silicoaluminophosphamolecular molecular sieve/manganese octahedron molecular screen | |
| EP1718395A1 (en) | Precious metal catalyst stabilized with iron oxide for the removal of pollutants from exhaust gases from leanburn engines | |
| KR19980071608A (en) | Oxygen excess exhaust gas purification catalyst | |
| CN104661749A (en) | Exhaust gas purification catalyst and production method thereof | |
| CN101454081A (en) | NOx reduction catalyst, NOx reduction catalyst system, and method for reducing NOx | |
| JP4236543B2 (en) | Catalysts and methods for the catalytic cracking of nitrogen oxides | |
| CN109589988B (en) | Diesel engine double-coating catalyst based on hydrotalcite derived oxide and preparation method thereof | |
| KR101473440B1 (en) | Mixed oxide catalyst materials for treating an exhaust gas, preparing methods thereof and methods for treating the exhaust gas using the same | |
| CN109590017A (en) | Use for diesel engine catalyst and preparation method thereof based on compound primary catalysts and hydrotalcite Derived Oxides | |
| EP2075065A1 (en) | Exhaust gas purification catalyst, and catalytic honey-comb structure for exhaust gas purification | |
| US6797247B2 (en) | Material with a channel structure for eliminating oxides of nitrogen | |
| CN109589976B (en) | Catalyst for diesel engine based on oxide composite main catalyst and preparation method thereof | |
| JPH11169669A (en) | Exhaust gas cleaning method | |
| WO1997020619A1 (en) | Method of controlling emission from gasoline engine | |
| JPH11290686A (en) | Exhaust gas cleaning catalyst | |
| DE102004058210A1 (en) | Integrated catalyst system to remove e.g. nitric oxides from exhaust gases comprises nitric oxide storing component, ammonia-generating component, ammonia-storing component and selective catalytic reduction component on common substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: BASF AKTIENGESELLCHAFT Free format text: FORMER OWNER: HTE AG THE HIGH THROUGHPUT EXP Effective date: 20070713 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20070713 Address after: Ludwigshafen, Germany Applicant after: Basf AG Address before: Heidelberg Applicant before: HTE AG The High Throughput Exp |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091007 Termination date: 20130414 |