JP6885927B2 - 一体型scr及びアンモニア酸化触媒システム - Google Patents
一体型scr及びアンモニア酸化触媒システム Download PDFInfo
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- JP6885927B2 JP6885927B2 JP2018512135A JP2018512135A JP6885927B2 JP 6885927 B2 JP6885927 B2 JP 6885927B2 JP 2018512135 A JP2018512135 A JP 2018512135A JP 2018512135 A JP2018512135 A JP 2018512135A JP 6885927 B2 JP6885927 B2 JP 6885927B2
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- catalyst
- molecular sieve
- platinum
- catalyst according
- sieve material
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- 239000003054 catalyst Substances 0.000 title claims description 201
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 140
- 229910021529 ammonia Inorganic materials 0.000 title claims description 70
- 238000007254 oxidation reaction Methods 0.000 title claims description 31
- 230000003647 oxidation Effects 0.000 title claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 159
- 239000000463 material Substances 0.000 claims description 131
- 239000002808 molecular sieve Substances 0.000 claims description 103
- 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 103
- 239000010948 rhodium Substances 0.000 claims description 76
- 239000000758 substrate Substances 0.000 claims description 73
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- 239000010949 copper Substances 0.000 claims description 63
- 229910052697 platinum Inorganic materials 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- 229910052802 copper Inorganic materials 0.000 claims description 53
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 50
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 48
- 229910052703 rhodium Inorganic materials 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims description 44
- 150000004706 metal oxides Chemical class 0.000 claims description 44
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 43
- -1 platinum group metals Chemical class 0.000 claims description 43
- 239000011148 porous material Substances 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000003870 refractory metal Substances 0.000 claims description 39
- 229910052742 iron Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 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 8
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- 229910052721 tungsten Inorganic materials 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 description 61
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 29
- 230000003197 catalytic effect Effects 0.000 description 23
- 229910021536 Zeolite Inorganic materials 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
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- 238000012360 testing method Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
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- 125000004429 atom Chemical group 0.000 description 11
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 10
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
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- 238000010304 firing Methods 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000004071 soot Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
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- 229910052741 iridium Inorganic materials 0.000 description 5
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- 150000002739 metals Chemical group 0.000 description 5
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000004323 axial length Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- ZVAVDTDDBJNPJQ-UHFFFAOYSA-N ethanol;platinum Chemical compound [Pt].CCO ZVAVDTDDBJNPJQ-UHFFFAOYSA-N 0.000 description 4
- 230000009970 fire resistant effect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052762 osmium Inorganic materials 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
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- 239000010452 phosphate Substances 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241000269350 Anura Species 0.000 description 2
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- 239000005751 Copper oxide Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
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- 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 2
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- 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
- 229910001873 dinitrogen Inorganic materials 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
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
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- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010015946 Eye irritation Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
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- 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
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- 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
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- 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
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- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 description 1
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- 239000011777 magnesium Substances 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
- 239000000391 magnesium silicate Substances 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- KIDPOJWGQRZHFM-UHFFFAOYSA-N platinum;hydrate Chemical compound O.[Pt] KIDPOJWGQRZHFM-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052645 tectosilicate Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Description
本発明の態様は、排気ガス流を処理するための触媒システム、及びかかる気体の処理のための触媒を調製する方法を含む。本明細書中で使用する「触媒システム」という用語は、1つの基材上の又は1つを超える別個の基材上の2つ以上の化学的触媒機能を含むものとする。
4NO+4NH3+O2→4N2+6H2O(標準SCR反応)
2NO2+4NH3→3N2+6H2O(緩やかなSCR反応)
NO+NO2+NH3→2N2+3H2O(高速SCR反応)
本発明の1つ以上の実施形態によると、SCR機能を触媒するために有効な成分(本明細書において「SCR成分」と称する)は、NOx低減触媒組成物の一部としてウォッシュコート中で利用される。典型的に、SCR成分は、ウォッシュコート内に他の成分を含む組成物の部分である。しかしながら、1つ以上の実施形態において、NOx低減触媒組成物は、SCR成分のみを含んでもよい。
本発明の1つ以上の実施形態によると、NH3酸化反応を触媒するために有効な組成物は、1つ以上の実施形態の触媒として利用される。排気ガス流に含有されるアンモニアは、NH3酸化触媒上で酸素と反応してN2を形成する。
1つ以上の実施形態では、触媒材料をウォッシュコートとして基材に施与することができる。本明細書で使用する「基材」という用語は、その上に触媒が、典型的にはウォッシュコートの形態で置かれるモノリシック材料を指す。ウォッシュコートは、液体媒体中に触媒の特定の固形分(例えば、30〜90質量%)を含有するスラリーを調製し、次いでそのスラリーを基材上に被覆し、乾燥させてウォッシュコート層を提供することによって、形成される。
1つ以上の実施形態によると、NH3酸化触媒は、基材上に被覆されて基材に付着されるウォッシュコート層内に施与することができる。本明細書で使用する「ウォッシュコート」という用語は当業技術における通常の意味を有し、ハニカム型の担体部材等の基材材料に施与される触媒性の又は他の材料の薄い付着性被覆を指し、そのハニカム型の担体部材は、処理されるガス流を通過させるのに十分に多孔質である。
本発明の別の態様は、希薄燃焼エンジンの排気ガス流において生成される排出物を処理する方法を含む。排気ガス流は、NOx、CO、炭化水素、及びアンモニアのうちの1つ以上を含む可能性がある。1つ以上の実施形態において、前記方法は排気ガス流にアンモニア又はアンモニア前駆体を注入し、次いで排気ガス流を1つ以上の実施形態の触媒に通すことを含む。
本発明の別の態様は、ディーゼル排気ガス排出物を処理するための1つ以上の追加の構成要素を含む排出物処理システムを対象とする。ディーゼルエンジン排気は、一酸化炭素、未燃炭化水素及びNOx等のガス状排出物だけでなく、粒子又は粒子状物質を構成する凝縮相物質(液体及び固体)も含む不均一混合物である。しばしば、触媒組成物及びその組成物が上に施される基材は、ディーゼルエンジン排気システムの特定の又は全部のこれら排気組成物を無害成分に転化するために提供される。例えば、ディーゼル排気システムは、NOxの還元のための触媒に加えて、ディーゼル酸化触媒及び煤煙フィルタのうちの1つ以上を含むことができる。本発明の実施形態は、ディーゼル排気ガス処理システムに組み込むことができる。このようなシステムの1つは、参照により本明細書に組み込まれる、米国特許第7229597号に開示されている。
触媒の調製
実施例1:PGMなし
ジルコニアアセテート溶液(1.3kg)を脱イオン水(9kg)と容器内で混合した。3質量%のCuOを有するCu−SSZ−13(8.6kg)を、この混合物に添加して分散液を形成し、5ミクロンより小さい粒子の粒度分布の粒度測定結果が90%となるまで、得られた分散液をボールミルで粉砕した。
ジルコニアアセテートの溶液(1.3Kg)を脱イオン水(9Kg)と容器内で混合した。この混合物に、3質量%のCuOを有するCu−SSZ−13(8.6Kg)を添加し、5ミクロンより小さい粒子の粒度分布の粒度測定結果が90%となるまで、得られた分散液をボールミルで粉砕した。
実施例1及び2のスラリーから以下の方法で区域触媒を調製した:
実施例1からのスラリーをハニカムの入口部分に50%まで被覆し、実施例2の白金含有スラリーをハニカムの後部区域の残りの50%に被覆した。このようにして、白金はハニカムの後部の50%にのみ位置した。
ジルコニアアセテートの溶液(1.3kg)を脱イオン水(9kg)と容器内で混合した。この混合物に、3質量%のCuOを有するCu−SSZ−13(8.6Kg)を添加し、5ミクロンより小さい粒子の粒度分布の粒度測定結果が90%となるまで、得られた分散液をボールミルで粉砕した。
ジルコニアアセテートの溶液(1.3kg)を脱イオン水(9kg)と容器内で混合した。この混合物に、3質量%のCuOを有するCu−SSZ−13(8.6Kg)を添加し、5ミクロンより小さい粒子の粒度分布の粒度測定結果が90%となるまで、得られた分散液をボールミルで粉砕した。
ジルコニアアセテートの溶液(1.3kg)を脱イオン水(9kg)と容器内で混合した。この混合物に、3質量%のCuOを有するCu−SSZ−13(8.6Kg)を添加し、5ミクロンより小さい粒子の粒度分布の粒度測定結果が90%となるまで、得られた分散液をボールミルで粉砕した。
第1のスラリー:17質量%のPtを有する白金モノエタノールの溶液(330g)を脱イオン水(100mL)と混合した。この混合物を、1.5質量%のシリカでドープしたアルミナ粉末(716g)上に滴下して添加した。この粉末に、水(800mL)及び氷酢酸(450g)を加えた。続いて、この粉末を脱イオン水(4.5kg)に入れ、ボールミルでpH4で粉砕し、7.5ミクロンより小さい粒子が90%の粒度分布を得た。
ジルコニアアセテート溶液(1.3kg)を容器内で脱イオン水(9kg)と混合した。3質量%のCuOを有するCu−SSZ−13(8.6Kg)をこの混合物に添加して分散液を形成し、5ミクロンより小さい粒子の粒度分布の粒度測定結果が90%となるまで、得られた分散液をボールミルで粉砕した。
水熱条件(10%のO2及び80%のN2を有する10%のH2O)下で16時間エージングさせた後、定常状態のエンジン運転条件下でSCR活性を試験した。この試験のために、エンジンは、250〜300ppmのNOx排出量で所望の排気ガス温度を達成するように調整した。一定の温度が達成された場合、DOC/フィルタ缶詰後に尿素を注入した。尿素量はNH3対NOx比が1.2を達成するように調整し、触媒後に20ppmのNH3が測定された後10分間維持した。尿素投与の停止後、NOx転化率が5%未満の転化率に低下するまで測定を延長した。
表4は、定置エンジンベンチ評価の残りの結果を示す。
エンジンに密接に接続されたフィルタ上のDOC、SCR、及びエンジンの1.5m下流の位置にあるAMOx−SCR触媒からなるシステムを備えた2LEU6エンジンを用いて、アルテミス試験(Artemis test)を行った。全てのAMOx触媒は測定前に、750℃で16時間、オーブン内で水熱エージング(10%のO2及び80%のN2を含む10%のH2O)させた。
エンジンに密接に接続されたフィルタ上のDOC、SCR、及びエンジンの1.5m下流の位置にあるAMOx−SCR触媒からなるシステムを備えた2L EU6エンジンを用いて、アルテミス試験を行った。全てのAMOx触媒は測定前に、750℃で16時間、オーブン内で水熱エージング(10%のO2及び80%のN2を含む10%のH2O)させた。
最大のNOxエンジン出口濃度は1500ppmで、平均NOx濃度は145ppmであった。最大AMOx入口(フィルタ出口上のSCR)濃度は1100ppmで、平均NOx濃度は50ppmであった。最大AMOx空間速度は150,000h−1で、平均空間速度は32000h−1であった。最大AMOx入口温度は420℃で、平均温度は192℃であった。
種々の実施例の追加の評価は、直径1インチ及び長さ4インチの試料を有する実験用反応器で実施した。
Claims (25)
- アンモニアを酸化するための触媒であって、
アルミナ、シリカ、ジルコニア、チタニア、及びそれらの物理的な混合物又は原子的にドープされた組み合わせを含むそれらの化学的組み合わせを含む耐火性金属酸化物担体上の白金及びロジウムと物理的に混合された、最大8員の環サイズの、四面体状の原子を有する小細孔分子篩材料上の銅を含むウォッシュコートを含む、触媒。 - 前記ウォッシュコートはモノリシック基材上に施される、請求項1に記載の触媒。
- 前記モノリシック基材は、前記基材の縦軸に沿って伸長する複数の微細で実質的に平行なガス流路を含むハニカム貫流基材である、請求項2に記載の触媒。
- 前記触媒は、所定量の白金及び所定量のロジウムを含む、請求項1〜3のいずれか一項に記載の触媒。
- 前記量は、白金は10.594g/m 3 〜706.294g/m 3 (0.3g/ft3〜20g/ft3 )の範囲の量で存在し、ロジウムは10.594g/m 3 〜706.294g/m 3 (0.3g/ft3〜20g/ft3 )の範囲の量で存在し、且つ他の白金族金属は存在しない、請求項4に記載の触媒。
- 分子篩材料上の銅と、前記耐火性金属酸化物担体上の白金及びロジウムは、前記ウォッシュコート中で均質に混合されている、請求項1〜5のいずれか一項に記載の触媒。
- 分子篩材料上の銅と、前記耐火性金属酸化物担体上の白金及びロジウムは互いに分離された構成と、前記耐火性金属酸化物担体上の白金及びロジウムは、分子篩材料上の銅と物理的に混合された構成を有する、請求項1〜5のいずれか一項に記載の触媒。
- 前記耐火性金属酸化物担体は、Ce、La、Ba、Zr、Hf、Ta、Mn、Si、Ti、W、Mo、及びReのうちの1つ以上から選択されるドーパントでドープされる、請求項1〜7のいずれか一項に記載の触媒。
- 前記ウォッシュコートは実質的に銅アルミネートを含まない、請求項1〜8のいずれか一項に記載の触媒。
- 前記分子篩材料は骨格タイプCHA、AEI、AFX、ERI、KFI、LEV、AFT、EAB、DDR、PAU、RHO、SAV、SAT、TSC、UEI及びこれらの組み合わせから選択される、請求項1〜9のいずれか一項に記載の触媒。
- 前記分子篩材料はCHA骨格タイプである、請求項1〜10のいずれか一項に記載の触媒。
- 前記分子篩材料はシリカ対アルミナ比を2〜200の範囲で有する、請求項1〜11のいずれか一項に記載の触媒。
- 前記ウォッシュコートは最大8員の環サイズの、四面体状の原子を有する小細孔分子篩材料上の銅を含む、請求項1〜12のいずれか一項に記載の触媒。
- 前記ウォッシュコートは最大8員の環サイズの、四面体状の原子を有する小細孔分子篩材料上の鉄を含む、請求項1〜12のいずれか一項に記載の触媒。
- アンモニアを酸化するための触媒であって、
最大8員の環サイズの、四面体状の原子を有する小細孔分子篩材料上の銅又は鉄を含む第1ウォッシュコート区域であって、実質的に白金族金属を含まない前記第1ウォッシュコート区域と、
アルミナ、シリカ、ジルコニア、チタニア、及びそれらの物理的混合物又は原子的にドープされた組み合わせを含む化学的組み合わせを含む耐火性金属酸化物担体上の白金と物理的に混合された、最大8員の環サイズの、四面体状の原子を有する小細孔分子篩材料上の銅又は鉄を含む第2ウォッシュコート区域と
を含む、触媒。 - 前記第1ウォッシュコート区域及び第2ウォッシュコート区域は、モノリシック基材上に施される、請求項15に記載の触媒。
- 前記第1ウォッシュコート区域及び前記第2ウォッシュコート区域は前記モノリシック基材上に隣接して施され、前記第1ウォッシュコート区域は前記第2ウォッシュコート区域の上流にある、請求項16に記載の触媒。
- 前記第2ウォッシュコート区域は白金を含み、他の白金族金属を含まない、請求項15〜17のいずれか一項に記載の触媒。
- 前記第2ウォッシュコート区域は更にロジウムを含み、他の白金族金属を含まない、請求項15〜17のいずれか一項に記載の触媒。
- 前記分子篩材料は、骨格タイプCHA、AEI、AFX、ERI、KFI、LEV、AFT、EAB、DDR、PAU、RHO、SAV、SAT、TSC、UEI、及びこれらの組み合わせから選択される、請求項13〜19のいずれか一項に記載の触媒。
- 前記分子篩材料はCHA骨格タイプである、請求項13〜20のいずれか一項に記載の触媒。
- 前記分子篩材料はシリカ対アルミナ比を2〜200の範囲で有する、請求項13〜21のいずれか一項に記載の触媒。
- 希薄燃焼エンジンの排気ガス流中に生成される排出物を処理する方法であって、
アンモニア又はアンモニア前駆体を、NOx、CO又は炭化水素の1つ以上を含有する排気ガス流に注入する工程、及び、
前記排気ガス流を請求項1〜22のいずれか一項の触媒に通過させる工程、
とを含む、方法。 - 希薄燃焼エンジンの排気ガス流中に生成される排出物を処理するためのシステムであって、
アンモニア源及び前記アンモニア源を前記排気ガス流に注入するためのインジェクタと、
前記アンモニア源の下流で前記アンモニアと窒素酸化物との反応を促進して選択的に窒素とH2Oを形成する選択的接触還元触媒と、
請求項1〜22のいずれか一項に記載の触媒と、
を含む、システム。 - 前記システムは更にアンモニア酸化AMOx触媒を含む、請求項24に記載のシステム。
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