JP7224298B2 - 単一ブリックscr/asc/pna/doc近位連結触媒 - Google Patents
単一ブリックscr/asc/pna/doc近位連結触媒 Download PDFInfo
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- JP7224298B2 JP7224298B2 JP2019553395A JP2019553395A JP7224298B2 JP 7224298 B2 JP7224298 B2 JP 7224298B2 JP 2019553395 A JP2019553395 A JP 2019553395A JP 2019553395 A JP2019553395 A JP 2019553395A JP 7224298 B2 JP7224298 B2 JP 7224298B2
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- 239000003054 catalyst Substances 0.000 title claims description 860
- 239000011449 brick Substances 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims description 480
- 239000002184 metal Substances 0.000 claims description 480
- 239000000758 substrate Substances 0.000 claims description 476
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 463
- 230000003197 catalytic effect Effects 0.000 claims description 192
- 239000000203 mixture Substances 0.000 claims description 153
- 239000002808 molecular sieve Substances 0.000 claims description 139
- 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 139
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 92
- 238000011144 upstream manufacturing Methods 0.000 claims description 58
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 42
- 239000010457 zeolite Substances 0.000 claims description 40
- 229910021529 ammonia Inorganic materials 0.000 claims description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- -1 platinum group metals Chemical class 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 84
- 229910002089 NOx Inorganic materials 0.000 description 60
- 229910052763 palladium Inorganic materials 0.000 description 38
- 239000011148 porous material Substances 0.000 description 33
- 238000009472 formulation Methods 0.000 description 32
- 229910052697 platinum Inorganic materials 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000010949 copper Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- 239000010953 base metal Substances 0.000 description 18
- 239000003638 chemical reducing agent Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 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 13
- 238000010531 catalytic reduction reaction Methods 0.000 description 12
- 229910052676 chabazite Inorganic materials 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 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 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 239000004202 carbamide 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
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 206010021198 ichthyosis Diseases 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 241000269350 Anura Species 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000000746 purification Methods 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
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 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
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
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- 239000003870 refractory metal Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9436—Ammonia
-
- 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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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Description
4NO+4NH3+O2→4N2+6H2O
2NO2+4NH3+O2→3N2+6H2O
NO+NO2+2NH3→2N2+3H2O
本発明の実施態様は、入口端及び出口端を有する基材、第1のゾーン及び第2のゾーンを含む触媒物品に関し、第1のゾーンは第2のゾーンの上流に位置する。第1のゾーンは、受動的NOx吸着体(PNA)と、担体上の白金族金属、及びSCR触媒を有するSCR層を含むアンモニアスリップ触媒(ASC)とを含むことができ、SCR層は、ASC最下層及び第1のSCR触媒より上に位置する。第2のゾーンは、ディーゼル酸化触媒(DOC)又はディーゼル発熱触媒(DEC)を含み得る。
本発明の実施態様は、第1のゾーン、第2のゾーン及び第3のゾーンを有する触媒物品に関する。第1のゾーンは、SCR触媒を含み得る。第2のゾーンは、担体上の白金族金属と第1のSCR触媒とのブレンドを有するASCを含み得る。第3のゾーンは、DOC又はDECなどの触媒(「第3のゾーン触媒」)を含み得る。触媒物品はPNAを含む。第1のゾーンは第2のゾーンの上流に位置し、第2のゾーンは第3のゾーンの上流に位置する。
本発明のシステム構成は、上流SCR触媒、及び前項に記載される2ゾーン又は3ゾーン構成を有する触媒物品であり得る。上流SCR触媒は、前項に記載される2ゾーン又は3ゾーン構成を有する触媒物品の上流に位置してもよく、いくつかの実施態様では、上流SCR触媒及び触媒物品は近位連結されてもよい。いくつかの実施態様では、上流SCR触媒及び触媒物品は単一基材上に位置しており、上流SCR触媒は、触媒物品の第1及び第2(及び存在する場合は第3)のゾーンの上流に位置する。
触媒物品は、一又は複数の、アンモニアスリップ触媒(「ASC」)とも呼ばれる、アンモニア酸化触媒を含み得る。一又は複数のASCは、SCR触媒に又はその下流に含まれて、余剰のアンモニアを酸化させ、且つそれが大気中へ放出されるのを妨げ得る。いくつかの実施態様では、ASCは、SCR触媒と同じ基材上に含まれ得るか、又はSCR触媒とブレンドされ得る。特定の実施態様では、アンモニア酸化触媒材料は、NOx又はN2Oの形成の代わりにアンモニアの酸化を有利にするよう選択され得る。好ましい触媒材料には、白金、パラジウム、又はそれらの組み合わせが含まれる。アンモニア酸化触媒は、金属酸化物に担持された白金及び/又はパラジウムを含む。いくつかの実施態様では、触媒は、高表面積の担体上に配置され、アルミナを含むが、それらに限定されない。
本発明のシステムは、一又は複数のSCR触媒を含み得る。いくつかの実施態様では、触媒物品は、第1のSCR触媒、第2のSCR触媒、及び/又は第3のSCR触媒を含み得る。いくつかの実施態様では、SCR触媒は、互いに同一の配合を含み得る。いくつかの実施態様では、SCR触媒は、互いに異なる配合を含み得る。
本発明の実施態様は、(1)担体上の白金族金属と(2)SCR触媒とのブレンドを含み得る。いくつかの実施態様では、ブレンド内で、SCR触媒の担体上の白金族金属に対する重量比は、約3:1から約300:1;約3:1から約250:1;約3:1から約200:1;約4:1から約150:1;約5:1から約100:1;約6:1から約90:1;約7:1から約80:1;約8:1から約70:1;約9:1から約60:1;約10:1から約50:1;約3:1;約4:1;約5:1;約6:1;約7:1;約8:1;約9:1;約10:1;約15:1;約20:1;約25:1;約30:1;約40:1;約50:1;約75:1;約100:1;約125:1;約150:1;約175:1;約200:1;約225:1;約250:1;約275:1;又は約300:1である。この重量比は、ブレンドがPNAを含む実施態様では、PNAからの白金族金属を含み得る。
NOx吸着体(PNA)は、金属含有モレキュラーシーブ又はセリア担持パラジウムを含む。PNAが金属含有モレキュラーシーブを含むとき、金属は、セリウム、クロム、コバルト、銅、鉄、ランタン、マンガン、モリブデン、ニッケル、ニオブ、パラジウム、タングステン、銀、バナジウム、及び亜鉛、並びにそれらの混合物からなる群より選択され得る。いくつかの実施態様では、金属は、コバルト、マンガン、パラジウム又は亜鉛である。いくつかの実施態様では、金属はパラジウム又は亜鉛である。いくつかの実施態様では、SCR触媒中の金属は銅であり、PNA中の金属はパラジウムである。PNA中の金属含有モレキュラーシーブ中のモレキュラーシーブは、SCR触媒中のモレキュラーシーブの記載において上に記載されるようなアルミノシリケート(例えばゼオライト)、アルミノホスフェート、又はシリコアルミノホスフェートを含み得る。SCR触媒が金属含有モレキュラーシーブを含むとき、SCR触媒中の金属含有モレキュラーシーブ中のモレキュラーシーブは、PNA中の金属含有モレキュラーシーブ中のモレキュラーシーブと同一である可能性があるか、又は、SCR触媒中の金属含有モレキュラーシーブ中のモレキュラーシーブは、PNA中の金属含有モレキュラーシーブ中のモレキュラーシーブとは異なる可能性がある。いくつかの実施態様では、同一の配合物及び/又は成分は、PNA及びSCR触媒の両方として機能し得る。
本発明の触媒物品は、SCR触媒とNOx吸着体触媒(PNA)の混合物を含み得る。いくつかの実施態様では、PNAがSCR/ASCブレンドに含まれるとき等に、混合物はASCを含み得る。
本発明の触媒物品及びシステムは、一又は複数のディーゼル酸化触媒を含み得る。酸化触媒、及び特にディーゼル酸化触媒(DOC)が、当該技術分野でよく知られている。酸化触媒は、COをCO2に酸化し、気相炭化水素(HC)及びディーゼル微粒子の有機フラクション(可溶性有機成分)をCO2とH2Oに酸化させるように設計されている。典型的な酸化触媒は、アルミナ、シリカ-アルミナ、及びゼオライトなどの高表面積の無機酸化物担体上白金及び任意選択的にパラジウムも含む。
本発明の触媒はそれぞれ、フロースルー基材又はフィルタ基材をさらに含み得る。一実施態様では、触媒は、フロースルー又はフィルタ基材上にコーティングされてもよく、好ましくは、ウォッシュコート法を使用して、フロースルー又はフィルタ基材上に堆積される。
システムは、SCR及び/又はSCRF触媒の上流の排気システムに窒素還元剤を導入するための手段を備え得る。排気システム中へ窒素還元剤を導入するための手段はSCR又はSCRF触媒のすぐ上流にある(例えば、窒素還元剤を導入するための手段とSCR又はSCRF触媒との間に介在する触媒は存在しない)ことが好ましい場合がある。
本発明の触媒物品は、PNAを含まないこと以外は一般的に同等である触媒物品と比較して、利点を含む多くの有益性を提供し得る。本発明の触媒物品は、排気システム内のEGR回路の削減又は除去を可能することができ、これは、燃費及び出力の改善、並びに炭化水素及び粒子状物質の排出の低下において有益であり得る。さらに、本発明の触媒物品は、触媒物品がエンジン後の近位連結位置に置かれているとき、SCR触媒と比較して同等又は同等に近いNO変換を提供し得る。触媒物品は、NH3下噴射中、SCR触媒と比較して、同等又は同等に近いN2O形成を提供し得る。本発明の触媒物品は、NH3上噴射中、著しく削減されたN2O形成を提供し得る。本発明の触媒物品は、尿素下噴射条件下でSCR/DOC触媒として機能すると言われることがあるが、余分なNH3が存在するとき、高いNH3選択性を有するSCR/ASC/DOCとして機能する。本発明の触媒物品は、単一ブロック中でSCR/ASC/DOC機能性を達成することができ、これは空間が限定されているときに特に望ましい。加えて、触媒物品は、エンジンの熱スウィングに対する高速応答を提供する可能性があり、これは、コールドスタート期間中のNOx変換に有益であり得る。触媒物品は、尿素噴射温度に到達する前にNOx貯蔵を提供し、追加のコールドスタートNOx制御を提供し得る。いくつかの実施態様では、触媒物品は、コールドスタート中にHC貯蔵を提供し得る。
以下の構成を用いて近位連結触媒構成を調製した:SCR/DOC、SCR-ASC/DOC及びPNA/SCR-ASC/DOC。特定の構成を図45に示す。
触媒がNOxを含有するシミュレーションされたエンジン出力ガス混合物に80℃で100秒間曝露され、その後500℃まで温度を上昇させた、シミュレーションしたNOx貯蔵-放出条件下で、上記のPNA/SCR-ASC/DOC触媒を試験した。具体的には、試験条件は以下の通りであった:200ppmのNO、500ppm(C1ベース)のC10H22、200ppmのCO、10%のO2、5%のCO2、5%のH2O、T≧180℃での300ppmのNH3噴射(あってもなくてもよい);SV=40,000h-1。触媒を、650℃/空気中10%H2O/50時間でエイジングした。
Claims (23)
- 入口端及び出口端を含む基材、第1のゾーン、第2のゾーン並びに第3のゾーンを含む触媒物品であって、
第1のゾーンが、第2のSCR触媒を含み、
第2のゾーンが、(1)担体上の白金族金属及び(2)第1のSCR触媒のブレンドを含むアンモニアスリップ触媒(ASC)を含み、
第3のゾーンが、ディーゼル酸化触媒(DOC)からなる触媒(「第3のゾーン触媒」)を含み、
第1のゾーンが第2のゾーンの上流に位置し、第2のゾーンが第3のゾーンの上流に位置しており、
触媒物品が受動的NOx吸着体(「PNA」)を含み、
ASCが第1の層に含まれており、
第3のゾーン触媒が、出口端から基材の全長未満まで延びる第2の層に含まれ、第2の層が第1の層の上に位置し、第1の層よりも長さが短く、且つ
第2のSCR触媒が、入口端から基材の全長未満まで延び、第1の層と少なくとも部分的に重なる層に含まれる、
触媒物品。 - 第1のゾーンがPNAを含む、請求項1に記載の触媒物品。
- 第2のゾーンがPNAを含む、請求項1に記載の触媒物品。
- 第1の層が出口端から基材の全長未満まで延びている、請求項1に記載の触媒物品。
- 第1の層が入口端から基材の全長未満まで延びている、請求項1に記載の触媒物品。
- 第1の層が基材の全長にわたって延びている、請求項1に記載の触媒物品。
- 第1の層が第1のゾーン及び第2のゾーンの全長を覆っている、請求項1に記載の触媒物品。
- 第1の層がPNAを更に含む、請求項1に記載の触媒物品。
- 第1の層がPNAを含むセクション(「PNAセクション」)を含み、PNAセクションがブレンドの上流に位置している、請求項8に記載の触媒物品。
- ブレンドがPNAを更に含む、請求項1に記載の触媒物品。
- 第1の層がPNA及び第3のSCR触媒を含むセクション(「PNA/SCRセクション」)を含む、請求項1に記載の触媒物品。
- 第1の層がPNA/SCRセクション及びブレンドを含み、PNA/SCR層がブレンドの上流に位置している、請求項11に記載の触媒物品。
- 第1の層がPNA/SCRセクションを含み、ブレンドがPNA/SCRセクションの上に位置している、請求項11に記載の触媒物品。
- 第1の層がブレンドを含み、PNA/SCRセクションが該ブレンドの上に位置している、請求項11に記載の触媒物品。
- 担体が、(1)シリカ、及び(2)200より高いシリカ対アルミナ比を有するゼオライトからなる群より選択されるケイ質材料を含む、請求項1に記載の触媒物品。
- 白金族金属が、白金族金属及び担体の総重量の0.5wt%から10wt%の量で担体上に存在する、請求項1に記載の触媒物品。
- ブレンド内で、第1のSCR触媒の、担体上の白金族金属に対する重量比が10:1から50:1である、請求項1に記載の触媒物品。
- 第1のSCR触媒とPNAが5:1から1:5の比で存在する、請求項1に記載の触媒物品。
- PNAがモレキュラーシーブ上の白金族金属を含む、請求項1に記載の触媒物品。
- PNAがゼオライト上のPdを含む、請求項1に記載の触媒物品。
- 窒素酸化物(NOx)、炭化水素(HC)、及び一酸化炭素(CO)を含む排気流から窒素酸化物(NOx)、炭化水素(HC)、及び一酸化炭素(CO)の排出を減少させる方法であって、
排気流を、請求項1に記載の触媒物品と接触させることを含む、
方法。 - 触媒物品に入る排気流の温度が≦180℃であるとき、排気流が≧1のアンモニア:NOxのモル比を含む、請求項21に記載の方法。
- 触媒物品に入る排気流の温度が≧180℃であるとき、排気流が>0.5のアンモニア:NOxのモル比を含む、請求項21に記載の方法。
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BR112019020349A2 (pt) | 2020-04-28 |
GB2571640B (en) | 2021-04-14 |
GB2566568A (en) | 2019-03-20 |
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WO2018183639A1 (en) | 2018-10-04 |
GB2566568B (en) | 2021-06-16 |
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US10926221B2 (en) | 2021-02-23 |
RU2759670C2 (ru) | 2021-11-16 |
EP3600657A1 (en) | 2020-02-05 |
CN111050908A (zh) | 2020-04-21 |
BR112019020349B1 (pt) | 2023-01-10 |
DE102018107779A1 (de) | 2018-10-04 |
CN111050908B (zh) | 2023-04-21 |
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