JP2018527161A - Scの前にscr触媒を備えるシステム内でdocとして作用するascを有する、docを伴わない排気システム - Google Patents
Scの前にscr触媒を備えるシステム内でdocとして作用するascを有する、docを伴わない排気システム Download PDFInfo
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- JP2018527161A JP2018527161A JP2017565202A JP2017565202A JP2018527161A JP 2018527161 A JP2018527161 A JP 2018527161A JP 2017565202 A JP2017565202 A JP 2017565202A JP 2017565202 A JP2017565202 A JP 2017565202A JP 2018527161 A JP2018527161 A JP 2018527161A
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- catalyst article
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- 239000003054 catalyst Substances 0.000 title claims abstract description 356
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000758 substrate Substances 0.000 claims abstract description 90
- 239000007789 gas Substances 0.000 claims abstract description 77
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 59
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 152
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 74
- 229910052697 platinum Inorganic materials 0.000 claims description 71
- 239000002808 molecular sieve Substances 0.000 claims description 68
- 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 68
- 229910052763 palladium Inorganic materials 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 33
- 239000004215 Carbon black (E152) Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 239000010953 base metal Substances 0.000 claims description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052720 vanadium Inorganic materials 0.000 claims description 20
- 238000011068 loading method Methods 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052878 cordierite Inorganic materials 0.000 claims description 6
- 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 group [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 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910004625 Ce—Zr Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 63
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 28
- 230000032683 aging Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 10
- 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 10
- 229910052676 chabazite Inorganic materials 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- -1 copper amine Chemical class 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 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
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 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
- 238000013316 zoning Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000002355 dual-layer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
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Abstract
Description
この組成物は、2つのSCR触媒、すなわち第1のゾーン(例えばSCRゾーン)の第1のSCR触媒と、アンモニアスリップ触媒(ASC)の一部としての第2のSCR触媒とを含む。
アンモニアスリップ触媒は、酸化触媒を含む最下層と第2のSCR触媒を含む最上層とを有する二重層であってよい。
アルミナ上のPGMを含むウオッシュコートを最初に基材上に配置して最下層を形成し、その後ウオッシュコートを乾燥させることにより、触媒物品をコージエライト基材(400cpsi)上に調製した。銅チャバザイト(Cu−CHA)(120g/ft3Cu)を含むウオッシュコートを適用し、その後最上層を乾燥させることにより、最上層を最下層の上に配置した。最上層が乾いた後、物品をか焼した。
実施例1に記載のとおりに調製された触媒の試料を、ディーゼル酸化触媒(DOC)及び触媒化スートフィルター(CSF)と共に排気システムに配置した。触媒は、SCR:ASC:DOC:CSFの順序で排気システムに配置した。排気システムをエンジンに接続し、尿素をSCR触媒の前の排気ストリームに注入した。燃料噴射器の出口はまた、SCRの前のシステム内に配置されていた。450℃で1時間エンジンを運転させることによりシステムを調整し、その後、エンジン速度を低下させて、エンジン温度を約300℃で安定させた。温度が安定した後、SCR触媒の前の排気システムに燃料を注入し、CSFの後ろの温度を約450℃に上昇させた。CSFの後ろの温度を約15分間維持した後、排気システムへの燃料添加を停止し、温度を約300℃に戻した。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。ウオッシュコート中のバナジウムの担持量は、好ましくは0.5〜5重量%(境界値も含む)である。フロースルー基材の出口端から延在する第2のゾーンを、最初にフロースルー基材上に白金を含むウオッシュコートを配置して第1の層を形成し、その後第1の層上にCu−CHAを含むウオッシュコートを配置することによって形成する。好ましくは、銅はチャバサイトの中/上に1〜5重量%(境界値も含む)の量で存在し、Cu−CHAは層中に約60g/ft3〜約300g/ft3の量で存在する。白金は、ASCゾーンにおいて約10g/ft3〜約20g/ft3の量で層中に存在する。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。フロースルー基材の出口端から延在する第2のゾーンを、最初にフロースルー基材上に白金を含むウオッシュコートを配置して第1の層を形成し、その後第1の層上にCu−CHAを含むウオッシュコートを配置することによって形成する。使用することができるバナジウム、銅、及びチャバザイトの量は、実施例3に記載されている。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。フロースルー基材の出口端から延在する第2のゾーンを、最初にフロースルー基材上に白金及びパラジウムを含むウオッシュコートを配置して第1の層を形成し、その後第1の層上にCu−CHAを含むウオッシュコートを配置することによって調製する。白金及びパラジウムは、PtとPdが1:1〜1:10の重量比で存在するASCゾーンにおいて、合わせて10g/ft3〜20g/ft3の量で層中に存在する。使用することができるバナジウム、銅、及びチャバザイトの量は、実施例3に記載されている。
実施例5に記載のとおりに触媒物品を調製し、パラジウムも第1の層の上に配置されたCu−CHAを含むウオッシュコート中に存在する。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。フロースルー基材の出口端から延在する第2のゾーンを、最初にフロースルー基材上に白金及びパラジウムを含むウオッシュコートを配置して第1の層を形成し、その後第1の層上にCu−CHAを含むウオッシュコートを配置することによって調製する。白金及びパラジウムは、PtとPdが1:1〜1:10の重量比で存在するASCゾーンにおいて、合わせて10g/ft3〜20g/ft3の量で層中に存在する。使用することができるバナジウム、銅、及びチャバザイトの量は、実施例3に記載されている。
実施例7に記載のとおりに触媒物品を調製し、パラジウムも第1の層の上に配置されたCu−CHAを含むウオッシュコート中に存在する。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。フロースルー基材の出口端から延在する第2のゾーンは、フロースルー基材上に白金とCu−CHAとの混合物(ブレンド)を含むウオッシュコートを配置して層を形成するように調製される。白金は、ASCゾーンにおいて10g/ft3〜20g/ft3の量で層中に存在する。使用することができるバナジウム、銅、及びチャバザイトの量は、実施例3に記載されている。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。フロースルー基材の出口端から延在する第2のゾーンは、フロースルー基材上に白金とCu−CHAとの混合物(ブレンド)を含むウオッシュコートを配置することによって層を形成するように調製される。白金は、ASCゾーンにおいて10g/ft3〜20g/ft3の量で層中に存在する。使用することができるバナジウム、銅、及びチャバザイトの量は、実施例3に記載されている。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。フロースルー基材の出口端から延在する第2のゾーンは、フロースルー基材上に白金、パラジウム及びCu−CHAの混合物(ブレンド)を含むウオッシュコートを配置することによって層を形成するように調製される。白金及びパラジウムは、PtとPdが約1:1〜約1:10の重量比で存在するASCゾーンにおいて、合わせて約10g/ft3〜約20g/ft3の量で層中に存在する。使用することができるバナジウム、銅、及びチャバザイトの量は、実施例3に記載されている。
フロースルー基材の入口端から延在する第1のゾーンにバナジウムを含むウオッシュコートを配置することによって、触媒物品を調製する。フロースルー基材の出口端から延在する第2のゾーンは、フロースルー基材上に白金、パラジウム及びCu−CHAの混合物(ブレンド)を含むウオッシュコートを配置することによって層を形成するように調製される。白金及びパラジウムは、PtとPdが約1:1〜約1:10の重量比で存在するASCゾーンにおいて、合わせて約10g/ft3〜約20g/ft3の量で層中に存在する。使用することができるバナジウム、銅、及びチャバザイトの量は、実施例3に記載されている。
比較システムにおいては、DOCは、ASCの後ろ、残りの後処理システムの前に配置されている。
実施例3〜10に記載されたシステムは、ASC内のゾーニングを提供するように変更されており、ASCの出口端でPGM担持量がより多い。このゾーニングは、出口に最も近いゾーン内の1種以上のPGMのレベルを増加させながら、隣接する2つ以上のウオッシュコートを配置することによって、実施例3〜6に記載したような層状システム又は実施例7〜10の組み合わせた単一層のいずれかにおいて作られる。
Claims (47)
- 入口端及び出口を含む基材と、第1のSCR触媒を含む第1のゾーンと、アンモニアスリップ触媒(ASC)を含む第2のゾーンとを含む触媒物品であって、アンモニアスリップ触媒が第2のSCR触媒と酸化触媒とを含み、かつ、DOC機能性を有し、第1のゾーンは基材の入口側に配置され、第2のゾーンは基材の出口側に配置されている、触媒物品。
- 第1のゾーン及び第2のゾーンが同じ基材上に配置され、かつ、第1のゾーンが基材の入口側に配置され、第2のゾーンが基材の出口側に配置されている、請求項1に記載の触媒物品。
- 第2の基材をさらに含み、第1のゾーンが第1の基材上に配置され、第2のゾーンは第2の基材上に配置され、かつ、第1の基材が第2の基材の上流に配置されている、請求項1に記載の触媒物品。
- 第1の片部と第2の片部とを含み、第1のゾーンが第1の片部に配置され、第2のゾーンは第2の片部に配置され、かつ、第1の片部が第2の片部の上流に配置されている、請求項3に記載の触媒物品。
- ASCが、酸化触媒を含む最下層と第2のSCR触媒を含む最上層とを有する二重層である、請求項1に記載の触媒物品。
- 最上層がパラジウムをさらに含む、請求項5に記載の触媒物品。
- 第2のゾーンが酸化触媒と第2のSCR触媒とのブレンドを含む、請求項1から6のいずれか一項に記載の触媒物品。
- ブレンドがMnO2上にPd、Nb−Ce−Zr又はNbをさらに含む、請求項7に記載の触媒物品。
- 酸化触媒が、担体上、好ましくは低アンモニア貯蔵を有する担体上に白金を含む、請求項6から8のいずれか一項に記載の触媒物品。
- 低アンモニア貯蔵を有する担体が珪酸質担体である、請求項9に記載の触媒物品。
- 珪酸質担体が、(a)少なくとも100、(b)少なくとも200、(c)少なくとも250、(d)少なくとも300、(e)少なくとも400、(f)少なくとも500、(g)少なくとも750、及び(h)少なくとも1000のうちの少なくとも1つのシリカ対アルミナ比を有するシリカ又はゼオライトを含む、請求項10に記載の触媒物品。
- 珪酸質担体が、BEA、CDO、CON、FAU、MEL、MFI又はMWWを含む、請求項10又は11に記載の触媒物品。
- 低アンモニア貯蔵を有する担体上の白金の量に対するSCR触媒の量の比率が、これらの成分の重量に基づいて、(a)0:1〜300:1、(b)3:1〜300:1、(c)7:1〜100:1、及び(d)10:1〜50:1(比の各端点を含む)のうちの少なくとも1つの範囲内にある、請求項9から12のいずれか一項に記載の触媒物品。
- 白金が、白金の担体の重量+白金の重量+ブレンド中の第1のSCR触媒の重量の(a)0.01−0.3%、(b)0.03−0.2%、(c)0.05−0.17%、及び(d)0.07−0.15%のうちの少なくとも1つとして存在する、請求項9から13のいずれか一項に記載の触媒物品。
- 酸化触媒が白金族金属を含む、請求項1から14のいずれか一項に記載の触媒物品。
- 酸化触媒が白金若しくはパラジウム又はこれらの混合物を含む、請求項1から15のいずれか一項に記載の触媒物品。
- Ptが約0.1g/ft3から約20g/ft3の量でASCゾーンに存在する、請求項16に記載の触媒物品。
- Pdが約0.1g/ft3から約20g/ft3の量でASCゾーンに存在する、請求項16又は請求項17に記載の触媒物品。
- PtとPdが約1:0.01から約1:10の重量比で存在する、請求項16から18のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が卑金属、卑金属の酸化物、モレキュラーシーブ、金属交換モレキュラーシーブ又はこれらの混合物である、請求項1から19のいずれか一項に記載の触媒物品。
- 卑金属が、バナジウム(V)、モリブデン(Mo)、タングステン(W)、クロム(Cr)、セリウム(Ce)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)及びジルコニウム(Zr)、並びにこれらの混合物からなる群より選択される、請求項20に記載の触媒物品。
- 少なくとも1種の卑金属促進剤をさらに含む、請求項20又は請求項21に記載の触媒製品。
- モレキュラーシーブ又は金属交換モレキュラーシーブが小細孔、中細孔、大細孔又はこれらの混合物である、請求項20から22のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が、アルミノシリケートモレキュラーシーブ、金属置換アルミノシリケートモレキュラーシーブ、アルミノホスフェート(AlPO)モレキュラーシーブ、金属置換アルミノホスフェート(MeAlPO)モレキュラーシーブ、シリコアルミノホスフェート(SAPO)モレキュラーシーブ及び金属置換シリコアルミノホスフェート(MeSAPSO)モレキュラーシーブ、並びにこれらの混合物からなる群より選択される小細孔モレキュラーシーブを含む、請求項20から23のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が、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及びZON、並びにこれらの混合物及び/又は連晶からなる骨格型の群より選択される小細孔モレキュラーシーブを含む、請求項20から24のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が、CHA、LEV、AEI、AFX、ERI、SFW、KFI、DDR、及びITEからなる骨格型の群より選択される小細孔モレキュラーシーブを含む、請求項20から25のいずれか一項に記載の触媒物品。
- SCR触媒が、AEL、AFO、AHT、BOF、BOZ、CGF、CGS、CHI、DAC、EUO、FER、HEU、IMF、ITH、ITR、JRY、JSR、JST、LAU、LOV、MEL、MFI、MFS、MRE、MTT、MVY、MWW、NAB、NAT、NES、OBW、PAR、PCR、PON、PUN、RRO、RSN、SFF、SFG、STF、STI、STT、STW、SVR、SZR、TER、TON、TUN、UOS、VSV、WEI及びWEN、並びにこれらの混合物及び/又は連晶からなる骨格型の群より選択される中細孔モレキュラーシーブを含む、請求項20から24のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が、AFI、AFR、AFS、AFY、ASV、ATO、ATS、BEA、BEC、BOG、BPH、BSV、CAN、CON、CZP、DFO、EMT、EON、EZT、FAU、GME、GON、IFR、ISV、ITG、IWR、IWS、IWV、IWW、JSR、LTF、LTL、MAZ、MEI、MOR、MOZ、MSE、MTW、NPO、OFF、OKO、OSI、RON、RWY、SAF、SAO、SBE、SBS、SBT、SEW、SFE、SFO、SFS、SFV、SOF、SOS、STO、SSF、SSY、USI、UWY及びVET、並びにこれらの混合物及び/又は連晶からなる骨格型の群より選択される大細孔モレキュラーシーブを含む、請求項20から24のいずれか一項に記載の触媒物品。
- 第2のSCR触媒がCu−SCR触媒、Fe−SCR触媒、卑金属、卑金属の酸化物若しくは混合酸化物又はバナジウム触媒である、請求項1から28のいずれか一項に記載の触媒物品。
- Cu−SCR触媒が銅及びモレキュラーシーブを含み、Fe−SCR触媒が鉄及びモレキュラーシーブを含む、請求項29に記載の触媒物品。
- モレキュラーシーブがアルミノシリケート、アルミノホスフェート(AlPO)、シリコアルミノホスフェート(SAPO)又はこれらの混合物である、請求項30に記載の触媒物品。
- モレキュラーシーブが、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及びZON、並びにこれらの混合物及び/又は連晶からなる骨格型の群より選択される、請求項30又は31に記載の触媒物品。
- モレキュラーシーブが、AEI、AFX、CHA、DDR、ERI、ITE、KFI、LEV及びSFWからなる骨格型の群より選択される、請求項30から32のいずれか一項に記載の触媒物品。
- 基材がコーディエライト、高多孔性コーディエライト、金属基材、押出SCR、ウォールフロー型フィルター、フィルター又はSCRFである、請求項1から33のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が第1のコーティングとして存在し、低アンモニア貯蔵を有する担体上の白金が第2のコーティングに存在し、NH3を含むガスが第2のコーティングを通過する前に第1のコーティングを通過する比較構成を含む触媒と比較して、約250℃から約350℃の温度でのアンモニアからのN2収率の改善をもたらす、請求項1から34のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が第1のコーティングとして存在し、担持された白金が第2のコーティングに存在し、NH3を含むガスが第2のコーティングを通過する前に第1のコーティングを通過する比較構成を含む触媒と比較して、(a)約350℃から約450℃の温度でのアンモニアからのN2収率の改善、及び(b)約350℃から約450℃の温度でのNOx生成の低減のうちの少なくとも1つをもたらす、請求項1から35のいずれか一項に記載の触媒物品。
- 第1のSCR触媒が第1のコーティングとして存在し、担持された白金が第2のコーティングに存在し、NH3を含むガスが第2のコーティングを通過する前に第1のコーティングを通過する比較構成を含む触媒と比較して、NH3からのN2Oの生成を低減させる、請求項1から36のいずれか一項に記載の触媒物品。
- 発熱を生じる、請求項1から37のいずれか一項に記載の触媒物品。
- 請求項1から38のいずれか一項に記載の触媒物品と、排気ガス中にNH3を生成するか又は排気ガスにNH3を導入するための第1の手段とを備える排気システムであって、排気ガス中にNH3を生成するか又は排気ガスにNH3を導入するための第1の手段が触媒物品の前に配置されている、排気システム。
- CSF又はSCRFをさらに備え、CSF又はSCRFが触媒物品の下流に配置され、前記システムがSCRFを備える場合、排気ガス中にNH3を生成するか又は排気ガスにNH3を導入するための第2の手段が触媒物品とSCRFとの間に配置されている、請求項38又は請求項39に記載の排気システム。
- CSFがCSFの前方に高PGM担持量を含む、請求項40に記載の排気システム。
- 請求項1に記載の触媒物品と、排気ガス中にNH3を生成するか又は排気ガスにNH3を導入するための手段とを備える排気システムを含むエンジン。
- 炭化水素を含む排気ガスを請求項1から38のいずれか一項に記載の触媒物品と接触させることを含む、排気ガス中の炭化水素排出物を制御する方法。
- 炭化水素を含む排気ガスを請求項1から38のいずれか一項に記載の触媒物品と接触させることを含む、排気ガス中の炭化水素排出物を処理する触媒において発熱を生じさせる方法。
- NOx又はNH3を含む排気ガスを請求項1から38のいずれか一項に記載の触媒物品と接触させることを含む、排気ガス中のNOx排出物を制御する方法。
- NOx又はNH3を含む排気ガスを請求項1から38のいずれか一項に記載の触媒物品と接触させることを含む、排気ガス中のN2O排出物を制御する方法。
- 請求項1から38のいずれか一項に記載の触媒物品が、DOCを含む排気システムの一部ではない、請求項46に記載の方法。
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GB2544837B (en) | 2020-01-22 |
CN113181769B (zh) | 2023-02-21 |
KR20180034396A (ko) | 2018-04-04 |
RU2018101714A (ru) | 2019-07-18 |
GB201610558D0 (en) | 2016-08-03 |
RU2734384C2 (ru) | 2020-10-15 |
DE102016111147A1 (de) | 2016-12-22 |
BR112017026961A2 (pt) | 2018-08-21 |
CN107847864A (zh) | 2018-03-27 |
EP3310459A1 (en) | 2018-04-25 |
CN113181769A (zh) | 2021-07-30 |
RU2018101714A3 (ja) | 2020-01-22 |
US20180221860A1 (en) | 2018-08-09 |
BR112017026961B1 (pt) | 2022-12-27 |
US20160367974A1 (en) | 2016-12-22 |
JP7086162B2 (ja) | 2022-06-17 |
US10589261B2 (en) | 2020-03-17 |
JP6853195B2 (ja) | 2021-03-31 |
WO2016203254A1 (en) | 2016-12-22 |
KR102525515B1 (ko) | 2023-04-26 |
CN107847864B (zh) | 2021-05-25 |
JP2021062368A (ja) | 2021-04-22 |
GB2544837A (en) | 2017-05-31 |
US9937489B2 (en) | 2018-04-10 |
EP3310459B1 (en) | 2021-08-04 |
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