JP7094969B2 - 触媒組成物 - Google Patents
触媒組成物 Download PDFInfo
- Publication number
- JP7094969B2 JP7094969B2 JP2019543038A JP2019543038A JP7094969B2 JP 7094969 B2 JP7094969 B2 JP 7094969B2 JP 2019543038 A JP2019543038 A JP 2019543038A JP 2019543038 A JP2019543038 A JP 2019543038A JP 7094969 B2 JP7094969 B2 JP 7094969B2
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- Prior art keywords
- catalyst
- molecular sieve
- catalytic
- mass
- substrate
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 234
- 239000000203 mixture Substances 0.000 title claims description 151
- 239000002808 molecular sieve Substances 0.000 claims description 133
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 133
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 119
- 239000000758 substrate Substances 0.000 claims description 117
- 239000010410 layer Substances 0.000 claims description 103
- 239000011247 coating layer Substances 0.000 claims description 87
- 230000003197 catalytic effect Effects 0.000 claims description 83
- 238000000576 coating method Methods 0.000 claims description 72
- 239000011248 coating agent Substances 0.000 claims description 67
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 66
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 63
- 239000011148 porous material Substances 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 36
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- 229910052763 palladium Inorganic materials 0.000 claims description 30
- 229930195733 hydrocarbon Natural products 0.000 claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims description 29
- 238000002485 combustion reaction Methods 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 150000002739 metals Chemical class 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000004071 soot Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 86
- 239000000047 product Substances 0.000 description 81
- 239000000843 powder Substances 0.000 description 64
- 239000002002 slurry Substances 0.000 description 57
- 239000002245 particle Substances 0.000 description 56
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 51
- 239000010457 zeolite Substances 0.000 description 51
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 48
- 239000007789 gas Substances 0.000 description 47
- 229910052676 chabazite Inorganic materials 0.000 description 45
- 229910021536 Zeolite Inorganic materials 0.000 description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 34
- 229910044991 metal oxide Inorganic materials 0.000 description 34
- 150000004706 metal oxides Chemical class 0.000 description 34
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 28
- 239000003870 refractory metal Substances 0.000 description 19
- 238000011068 loading method Methods 0.000 description 18
- 229910052684 Cerium Inorganic materials 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 15
- 238000006477 desulfuration reaction Methods 0.000 description 15
- 230000023556 desulfurization Effects 0.000 description 15
- 229910000323 aluminium silicate Inorganic materials 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- -1 Platinum Group Metals Chemical class 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 230000004323 axial length Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012530 fluid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910001657 ferrierite group Inorganic materials 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 7
- 230000009970 fire resistant effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 6
- 150000000703 Cerium Chemical class 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052680 mordenite Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 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 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 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 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 210000002421 cell wall Anatomy 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LIAWQASKBFCRNR-UHFFFAOYSA-N Bucetin Chemical compound CCOC1=CC=C(NC(=O)CC(C)O)C=C1 LIAWQASKBFCRNR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 241000282341 Mustela putorius furo Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CPGKMLVTFNUAHL-UHFFFAOYSA-N [Ca].[Ca] Chemical compound [Ca].[Ca] CPGKMLVTFNUAHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960005470 bucetin Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
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Images
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
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- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
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- 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
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
- F01N2370/04—Zeolitic material
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- 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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N2510/00—Surface coverings
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- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
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Description
少なくとも1つのコーティング層は、先行の実施形態のいずれかに記載の触媒組成物を含む触媒コーティング層である、触媒製品。
本開示の触媒材料は、パラジウムおよびセリアを含有するモレキュラーシーブを含む触媒組成物を含む(本明細書では「Pdおよびセリアモレキュラーシーブ組成物と呼ぶ)。一部の実施形態では、触媒材料は、耐火性金属酸化物支持体上の白金族金属(PGM)を含む触媒組成物(本明細書では「PGM組成物」と呼ぶ)をさらに含む。Pdおよびセリアモレキュラーシーブ組成物およびPGM組成物の両方を用いる実施形態では、これらの組成物は、例えば、層状構成で基材上に配置して、下に本明細書において詳細に説明するように、触媒製品を生成することができる。
Pdおよびセリアモレキュラーシーブ組成物は全体として、Pd成分(例えば、Pd)およびセリアを含有する1つまたは複数のモレキュラーシーブを含む。
PGM組成物は一般に、少なくとも1つの耐熱金属支持体上に少なくとも1種のPGM成分を含む。「白金族金属成分」とは、白金族金属またはそれらの化合物、例えば、酸化物を指す。白金族金属は、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、および白金である。
本開示は、1種または複数の触媒製品を提供し、各触媒製品は、その上に配置された1種または複数の触媒組成物(すなわち、本明細書に開示のモレキュラーシーブを含む触媒組成物)を有する基材を含む。用語「基材」とは全体として、その上に触媒コーティングが配置されるモノリシック材料を、例えば、フロースルーモノリスまたはモノリシック壁流フィルタを、指す。フロースルー基材および壁流基材はまた、例えば、参照により本明細書に組み入れられる、国際特許出願公開第WO2016/070090号にも教示されている。
触媒組成物は典型的には、上記のように触媒粒子の形態で製造される。こういった触媒粒子を水と混合して、ハニカム型基材などの基材をコーティングする目的でスラリーを形成することができる。触媒コーティングは、活性触媒種を含有する1種または複数の担体を含有する。触媒コーティングは典型的には、その上に触媒活性種を有する担体を含有するウォッシュコートの形態で適用することができる。ウォッシュコートは、液体ビヒクル中に、規定の固形分含量(例えば、10~60質量%)の担体を含有するスラリーを製造することによって形成される。次いで、このスラリーを基材上にコーティングし、乾燥しそして焼成してコーティング層を提供する。多重のコーティング層を適用する場合、各層を適用後におよび/または所望の多重層の数を適用後に、基材を乾燥しそして焼成する。
本発明はまた、排気ガス流を生じるエンジンと、排気ガス流で流体連通するエンジンから下流に位置決めされた本発明の触媒製品とを、概して含む排出処理システムなどの、本明細書に記載の触媒製品が組み込まれている排出処理システムも提供する。エンジンは、例えば、空気が化学量論的燃焼に必要な空気を上回っている状態、すなわち、リーン条件にある燃焼条件で運転する、ディーゼルエンジンとすることができる。他の実施形態では、エンジンは固定発生源(例えば、発電所またはポンプ場)に関連するエンジンとすることができる。一部の実施形態では、排出処理システムは、1種または複数のさらなる触媒成分をさらに含む。排出処理システム内に存在する種々の触媒成分の相対的配置については、様々とすることができる。
粉末試料1:ゼオライト上のPd
標準H+形態のチャバザイトに、初期湿潤手順を使用して、硝酸Pd溶液(19.8wt.%)を含浸させた。目標のPd濃度は、Pdチャバザイトの質量に対して2質量パーセントとした。
高表面積セリア(>100m2/g)に、標準的な初期湿潤手順を使用して、硝酸Pd溶液(19.8wt.%)を含浸させた。ゼオライトの目標Pd濃度は、全組成に対して2質量パーセントとした。
標準H+形態チャバザイトに、標準的な初期湿潤手順を使用して、10%での目標セリア担持量へと、硝酸セリウム溶液を含浸させた。500℃で1時間乾燥した後、標準的な初期湿潤手順を使用して、Pdを、コーティング支持体の2質量パーセントの目標Pd濃度に含浸させた。
小開孔8員環チャバザイトから中サイズ開孔10員環H-ZSM-5にゼオライトを変更して、粉末試料3を繰り返した。
小開孔8員環チャバザイトから大サイズ開孔12員環H-ベータにゼオライトを変更して、粉末試料3を繰り返した。
粉末試料5を繰り返した、この場合、セリア担持量を10wt.%から20wt.%に増加した。
粉末試料3を繰り返した、この場合、チャバザイトはイオン交換型Cuを3%含有した。
粉末触媒の性能は、48倍のハイスループット粉末試験ユニットを使用して測定した。粒径250~500μmを有する粉末触媒を、COを700ppm、HCを420ppm(C1比として2/1である、プロペン80ppm、デカン340ppm/トルエンの混合物)、NOを70ppm、O2を10容積%、CO2を10容積%および水を5容積%(残部N2)含有するフィードガスを使用して、そのCO酸化性能およびHC酸化性能について試験した。GHSVを45,000h-1とした。125~350℃の温度範囲での定常試験を、48の反応装置それぞれにガス混合物を通流させることによって実施した。各温度で、および各反応装置について、測定時間には、3分の平衡時間+30秒のサンプリング時間を含めた。
コーティングされたハニカムコアを製造した。用いたハニカムコアは、約400セル毎1平方インチのセル密度を有し、長さ3“および直径1”であった。
PdおよびPtを含むボトムコーティング層を製造した。硝酸Pd溶液をアルミナ粉末上に含浸させた。この含浸粉末に水酸化バリウムを添加した。粉末は、水中のスラリーとして用意した。Pt-アミン溶液をスラリーに添加し、希硝酸でpHを4.5~5に調整した。スラリーを粉砕して、38~40%の固形分濃度および約20ミクロンのD90での粒度分布を有するウォッシュコートスラリーを用意した。
非PGMボトムコーティング層を製造した。ウォッシュコートスラリーは、Ce-Al粉末(50/50wt.%)およびアルミナで、ならびに酢酸ジルコニウムバインダーで製造した。ウォッシュコートをハニカムコアに適用した。コーティングされたコア試料を120℃で4時間乾燥し、500℃で1時間焼成して、約1.5g/in3のコーティング担持量がもたらされた。
チャバザイト上にPdおよびCeを含むボトムコートを製造した。1/1のPd/Mgモル比を有する、Pd硝酸塩/硝酸マグネシウム溶液を製造した。実施例1で製造した通りにチャバザイト粉末上の20%Ceを溶液に添加して、スラリーを用意した。よく混合した後、MnコーティングCe粉末(米国出願番号PCT/US2016/016949(WO2016130456)に記載の通り)およびゼオライトH+-ベータと一緒にアルミナ粉末を添加した。少量の酢酸セリウムバインダーを添加して、約34~38%の固形分濃度、4.5~5.0のpH、および約1700センチポアズの粘度を有するスラリーを用意した。
コーティングされたコア試料を、フレッシュ試料および既使用の試料の両方について、動的NEDC(New European Driving Cycle)プロトコルの下で、模擬ディーゼル車の排気ガス反応装置で評価した。模擬の排気ガス流の状態を、NEDCサイクル向けのフィード組成物とともに、図10および図11に示す。エージングは、10%蒸気/10%酸素/残部窒素からなる流れの下で、800℃で16時間、管状炉で実施した。
本発明のコーティング1の本発明のコーティング組成物を有するフルサイズ(直径5.66”×長さ3”)400cpsiのハニカムを、比較コーティング2に対してエンジンベンチにおいて試験した。ライトオフ試験を、触媒活性化後に、エンジンの粒子フィルタ再生モードを使用して10分間(T入口およそ650℃、リーンラムダ)実施した。COおよびHCライトオフ試験の場合、フィードガスは:CO=1200ppm;THC=150ppm;NOx=50ppm;質量流量30~40m3/hを含有し;NO2/NOx測定の場合、フィードガスは:CO 200~1000ppm;THC 50ppm;NOx 200~1000ppmを有した。
Claims (19)
- 内燃機関の排気ガスに含まれる炭化水素、一酸化炭素およびNOxを処理するための触媒組成物であって、
パラジウムおよびセリアを含有する小細孔モレキュラーシーブを含み、
前記パラジウムが、前記触媒組成物の総質量に対して、約0.1質量%から約5.0質量%まで存在し、
前記セリアが、前記触媒組成物の総質量に対して、約1質量%から約10質量%まで存在する、ことを特徴とする触媒組成物。 - 前記小細孔モレキュラーシーブが、骨格型、ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG、ZONおよびそれらの混合物または連晶からなる群から選択される小細孔モレキュラーシーブである、請求項1に記載の触媒組成物。
- 前記小細孔モレキュラーシーブが、骨格型、CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDRおよびITEの群から選択される小細孔モレキュラーシーブである、請求項1又は2に記載の触媒組成物。
- 前記小細孔モレキュラーシーブが、CHAである、請求項1から3のいずれか一項に記載の触媒組成物。
- 前記小細孔モレキュラーシーブが、約1から約1000までのシリカとアルミナとの比を有する、請求項1から4のいずれか一項に記載の触媒組成物。
- 前記小細孔モレキュラーシーブが、銅、鉄、マンガン、マグネシウム、コバルト、ニッケル、白金およびロジウムからなる群から選択される1種または複数の触媒活性金属をさらに含有する、請求項1から5のいずれか一項に記載の触媒組成物。
- 前記小細孔モレキュラーシーブが、マンガン、マグネシウムおよび白金からなる群から選択される1種または複数の触媒活性金属をさらに含有する、請求項1から6のいずれか一項に記載の触媒組成物。
- 前記小細孔モレキュラーシーブが、さらなる触媒活性金属を含有しない、請求項1から5のいずれか一項に記載の触媒組成物。
- 基材上に配置された触媒コーティングを含む触媒製品であって、前記触媒コーティングは、1つまたは複数のコーティング層を含み、
少なくとも1つのコーティング層は、請求項1から8のいずれか一項に記載の前記触媒組成物を含む触媒コーティング層である、触媒製品。 - 前記触媒組成物が、ボトムコーティング層として存在する、請求項9に記載の触媒製品。
- 前記触媒組成物が、トップコーティング層として存在する、請求項9に記載の触媒製品。
- 前記触媒組成物が、前記基材の容積に対して、約0.05g/in3から約7.0g/in3まで存在する、請求項9から11のいずれか一項に記載の触媒製品。
- 白金族金属が合計で、前記基材に対して、約2g/ft3から約200g/ft3まで存在する、請求項9から12のいずれか一項に記載の触媒製品。
- 前記基材が、フロースルーモノリスである、請求項9から13のいずれか一項に記載の触媒製品。
- 前記ボトムコーティング層が、前記基材と直接接触している、請求項10に記載の触媒製品。
- 前記触媒コーティングが、アンダーコート層を含む、請求項9から14のいずれか一項に記載の触媒製品。
- 請求項9から16のいずれか一項に記載の触媒製品を含む排気ガス処理システムであって、前記触媒製品が内燃機関の下流にあり、内燃機関と流体連通している、排気ガス処理システム。
- 尿素インジェクター、選択接触還元触媒、煤煙フィルタ、アンモニア酸化触媒、およびリーンNOxトラップからなる群から選択される第2の触媒製品をさらに含む、請求項17に記載の排気ガス処理システム。
- 炭化水素および/または一酸化炭素および/またはNOxを含む排気ガス流を処理する方法であって、請求項9から16のいずれか一項に記載の触媒製品に排気流を通流させる工程、または請求項17または18に記載の排気ガス処理システムに排気流を通流させる工程を含む方法。
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MX (1) | MX2019009464A (ja) |
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JP6693406B2 (ja) * | 2016-12-20 | 2020-05-13 | 三菱自動車工業株式会社 | 排気ガス浄化装置 |
CN111801164A (zh) * | 2018-03-14 | 2020-10-20 | 庄信万丰股份有限公司 | 具有原位Pt固定的氨漏失催化剂 |
US20220212162A1 (en) * | 2019-05-09 | 2022-07-07 | Basf Corporation | LOW TEMPERATURE NOx ADSORBER WITH ENHANCED HYDROTHERMAL STABILITY |
US20220241761A1 (en) * | 2019-05-22 | 2022-08-04 | Basf Corporation | Coordinated emission control system including diesel oxidation catalyst and low temperature nox adsorber |
KR102529419B1 (ko) * | 2020-11-24 | 2023-05-08 | 고려대학교 산학협력단 | 양이온 비율을 제어한 제올라이트를 포함하는 탄화수소 흡탈착 복합체 및 이의 제조방법 |
WO2023136060A1 (ja) * | 2022-01-13 | 2023-07-20 | 株式会社キャタラー | ガソリンエンジンの排ガス浄化用触媒体およびこれを用いた排ガス浄化システム |
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PL3579971T3 (pl) | 2024-03-11 |
KR102524756B1 (ko) | 2023-04-25 |
EP3579971B1 (en) | 2023-10-18 |
WO2018146602A1 (en) | 2018-08-16 |
JP2020510518A (ja) | 2020-04-09 |
EP3579971A4 (en) | 2020-08-12 |
BR112019015650A2 (pt) | 2020-03-31 |
RU2019128130A (ru) | 2021-03-09 |
US20190358615A1 (en) | 2019-11-28 |
KR20190107160A (ko) | 2019-09-18 |
CA3052906A1 (en) | 2018-08-16 |
EP3579971A1 (en) | 2019-12-18 |
MX2019009464A (es) | 2019-10-15 |
CN110730689A (zh) | 2020-01-24 |
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