JP2016518244A - 選択接触還元触媒系 - Google Patents
選択接触還元触媒系 Download PDFInfo
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- JP2016518244A JP2016518244A JP2016502087A JP2016502087A JP2016518244A JP 2016518244 A JP2016518244 A JP 2016518244A JP 2016502087 A JP2016502087 A JP 2016502087A JP 2016502087 A JP2016502087 A JP 2016502087A JP 2016518244 A JP2016518244 A JP 2016518244A
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- scr catalyst
- catalyst composition
- scr
- titania
- catalyst system
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 342
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 198
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 160
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 99
- 239000000758 substrate Substances 0.000 claims description 83
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 54
- 239000002808 molecular sieve Substances 0.000 claims description 51
- 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 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 50
- 239000010457 zeolite Substances 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 44
- 229910021536 Zeolite Inorganic materials 0.000 claims description 41
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- 239000002184 metal Substances 0.000 claims description 39
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- 238000011144 upstream manufacturing Methods 0.000 claims description 29
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- 238000002485 combustion reaction Methods 0.000 claims description 25
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 8
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000010949 copper Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000000523 sample Substances 0.000 description 16
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- 238000012360 testing method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
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- 230000000694 effects Effects 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
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- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- -1 platinum group metals Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000019635 sulfation Effects 0.000 description 5
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- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000005094 computer simulation Methods 0.000 description 4
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- 238000002347 injection Methods 0.000 description 4
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- 239000011777 magnesium Substances 0.000 description 4
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- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000269350 Anura Species 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 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
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- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
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- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000003795 desorption Methods 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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- 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
- 238000009826 distribution Methods 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- 238000000746 purification Methods 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 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
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Images
Classifications
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- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
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- 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
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- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
- B01D53/9472—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different zones
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- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
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Abstract
Description
本発明のいくつかの例示的な態様を記述する前に、本発明が、以下の記述に記載される構成またはプロセス工程の詳細に限定されないことを理解すべきである。本発明は、その他の態様であり、かつ種々の方法で行われ、または実施されることができる。
金属交換された8環小孔分子ふるいのプロモーター金属(たとえばCu)含有量は、金属酸化物として算出すると、具体的態様において、少なくとも約2質量%、さらにより具体的には少なくとも約2.5質量%およびさらにより具体的な態様において少なくとも約3質量%であり、揮発性なしのベースで報告されている。さらにより具体的な態様において、金属-交換8環小孔分子ふるいの金属(たとえばCu)含有量は、金属酸化物として算出すると、焼分子ふるいの総質量に基づいて約8質量%までの範囲であり、揮発性なしのベースで報告されている。したがって、具体的態様において、Cu 、Fe、Co、CeおよびNiから選択される金属で促進される8環小孔分子ふるいの範囲は、金属酸化物として算出すると、約2〜約8質量%、より具体的には約2〜約5質量%、およびさらにより具体的には約2.5〜約3.5質量%であり、それぞれの場合において酸化物ベースで報告されている。
本発明の一つの側面において、排気ガス処理系は、希薄燃焼機関および希薄燃焼機関と液体連結する排気ガス導管、および一つまたは複数の態様にしたがって、系に配置された第1のSCR触媒組成物および第2のSCR触媒組成物を含む選択接触還元触媒系を含む。具体的態様において、希薄燃焼機関は、大型ディーゼル機関である。
本発明は、ここで以下の実施例に関して記述される。本発明のいくつかの例示的な態様を記述する前に、本発明が、以下の記述に記載される構成またはプロセス工程の詳細に限定されないことが理解されるべきである。本発明は、他の態様であり、かつ種々の方法において行われ、または実施されることができる。
実施例1‐触媒材料の調製
バナジア-チタニア触媒
標準バナジア/チタニア/タングステン(V2O5(2.5%)/ WO3(10%)/ TiO2)触媒を調製し、およびスラリーを臼でひくことによって約30〜40%の固体に作製して薄め塗膜スラリーを提供する。
CuCHA(SSZ-13)粉末触媒を30のシリカ/アルミナモル比を有し、約1.0Mの酢酸銅(II)溶液400mLと100gのNaフォームCHAを混合することによって調製した。pHを硝酸で約3.5に調整した。NaフォームCHAと銅イオンとの間のイオン交換反応を約1時間約80℃にてスラリーを撹拌することによって実施した。次いで、生じる混合物を濾過して濾過ケークを提供し、濾過ケークを、濾液が澄んで無色になるまで、3つの部分で脱イオン水で洗浄し、および洗浄した試料を乾燥させた。
上記のスラリーを400 cpsi(平方インチあたりのセル)のセル密度および4ミルの壁の厚さを有する12”Dx6”Lセルのセラミック基体上へ別々に被覆した。被覆された基体を3時間110℃にて乾燥させ、およそ1時間400℃にて焼成した。被覆プロセスを繰り返してバナジア-チタニア被覆コア上の3g/ in3の範囲で、およびCuCHA被覆コア上の2.1g/ in3の範囲で標的薄め塗膜充填を一旦得た。試料を、大型ディーゼル機関試験セル上で550℃にて200時間寝かせた。
実施例2を、両方の基体を同じ充填にてCuCHAで被覆したことを除いて繰り返した。
実施例3および4における触媒系を自動車電気動力計と共に9L大型機関において試験した。テストベンチは、定常状態および過渡的試験サイクルを実行することができる。今回の研究では、大型過渡的試験サイクル(HDTP)およびノンロード過渡的試験サイクル(NRTC)の両方を実行した。触媒試料は、フルサイズの12”直径部分(400/4)であり、それは、評価の前に200時間-550℃で寝かせた機関とした。12”x6”Cu-CHA塊の上流で12”x6” V-SCR塊の側方に区分された系の利点を証明するために、また、参照経時的12”x6”Cu + 12”x6”Cu SCR系を評価した。このような比較研究において、第1のSCR触媒塊のみをV-SCRとCu-SCRとの間で切り替えて、第2のSCR塊、尿素注射系、試料プローブ位置などのその他の系を同じに保った。
実施例1からの薄め塗膜を利用し、図3について述べたように層をなした配置において単一の基体上へ被覆する。層をなすことは、以下の試料について以下の通りに様々であった。
比較用試料5B底面被覆CuCHA 2.1g/in3;上部被覆0.2g/in3チタニア
試料5C CuCHA底面被覆‐CuCHA 2.1g/in3;上部被覆0.1g/in3バナジアチタニア
試料5D CuCHA 底面被覆2.1g/in3;上部被覆0.2g/in3バナジアチタニア
試料5E CuCHA底面被覆2.1g/in3;上部被覆0.5g/in3バナジア-チタニア
試料5F CuCHA底面被覆2.1g/in3;上部被覆1g/ in3バナジアチタニア
窒素酸化物の選択接触還元(SCR)効率および新しい触媒コアの選択性を、1”D x 3”L触媒コアを含む定常状態反応器にN2で平衡を保たせ、500ppmのNO、500ppmのNH3、10% O2、5% H2Oの供給気体混合物を添加することによって測定した。反応を150℃ 〜460℃の温度範囲にわたって80,000 hr-1の空間速度にて実施した。
図10および11は、一つまたは複数の態様にしたがった系の動的反応挙動における改善を図示する。図10および11は、コンピューターモデルを使用して準備した。系内の個々の成分の性能を記述するための研究室反応器および機関研究室DeNOx性能測定は、使用するコンピューターモデルのための入力である。図10における実施例は、シミュレーション/尿素薬品注入の開始の前に格納されたアンモニアがない新鮮な系で得られた時間の関数として、DeNOx性能を示す。Cu-SSZ13系およびバナジアに基づいたSCR系を、バナジア/ Cu-SSZ13ハイブリッド系と比較する。バナジアに基づいたSCR触媒は、モデル化されたハイブリッド系内で50/50の大きさの比でCu-SSZ13触媒の前に置いた。225℃排気温度にて低温操作および10%のNO2/NOx比率にて500ppmのNOx入口濃度にて50000 1/h空間速度を比較のために使用した。これらのSCR入口状態は、SCRの前における、またはSCRのみの系における酸化系に対して低貴金属を充填して機関適用において作動される系に典型的であるように見られ得る。NSRを、研究された系の相対的に急速な最大DeNOx性能に到達するために、1.1に選択した。Cu-SSZ13系が薬品注入の700秒後により高いDeNOx性能に到達するが、0秒にて薬品注入の開始後のDeNOx反応挙動は、異なる順位を有する。バナジアに基づいたSCR系の反応は、Cu-SSZ13系(たとえば350秒まで)と比較して薬品注入の開始後のDeNOx増加に対してより速い。Cu-SSZ13との組み合わせたハイブリッド系バナジアに基づいたSCRは、バナジアに基づいたSCRの動的反応挙動に近く、たとえば、1000秒後に図10に示すように、より高い定常状態DeNOx性能をさらにを送達する利点を有する。
Claims (17)
- 第1のSCR触媒組成物および第2のSCR触媒組成物を系内に配置されて含む選択接触還元(SCR)触媒系であって、
前記第2のSCR触媒組成物より高いN2形成およびより低いN2O形成を促進する前記第1のSCR触媒組成物と、
前記第1のSCR触媒組成物とは異なる組成の前記第2のSCR触媒組成物であって、前記第2のSCR触媒組成物が、前記第1のSCR触媒組成物より低いN2形成およびより高いN2O形成を促進し、
前記第1の触媒組成物が、前記第2の触媒組成物の上流で側方に位置することを特徴とする選択接触還元(SCR)触媒系。 - 前記第1のSCR触媒組成物および前記第2のSCR触媒組成物は、共通の基体上に配置される、請求項1のSCR触媒系。
- 前記第1のSCR触媒組成物および前記第2のSCR触媒組成物は、異なる基体上に配置される、請求項1のSCR触媒系。
- 前記第1のSCR触媒組成物は、混合した酸化物を含む、請求項1〜3のいずれか1項に記載のSCR触媒系。
- 前記混合した酸化物は、Fe/チタニア、Fe/アルミナ、Mg/チタニア、Cu/チタニア、Ce/Zr、バナジア/チタニアおよびそれらの混合物から選択される、請求項4に記載のSCR触媒系。
- 前記混合した酸化物は、バナジア/チタニアを含む、請求項4または5に記載のSCR触媒系。
- 前記バナジア/チタニアは、タングステンで安定される、請求項5または6に記載のSCR触媒系。
- 前記第2のSCR触媒は、金属交換された8環小孔分子ふるいを含む、請求項1〜7のいずれか1項に記載のSCR触媒系。
- 基体上に配置されるバナジア/チタニアを含む第1のSCR触媒組成物および基体上に配置される金属交換された8環小孔分子ふるいを含む第2のSCR触媒組成物を含む選択接触還元(SCR)触媒系であって、前記第1の触媒組成物は、第2の触媒組成物の上流で側方に位置するすることを特徴とする選択接触還元(SCR)触媒系。
- 前記分子ふるいは、AEI、AFT、AFX、CHA、EAB、ERI、KFI、LEV、SAS、SAT、DDRおよびSAVからなる群より選択される構造型を有する、請求項8または9に記載のSCR触媒系。
- 前記分子ふるいは、アルミノケイ酸ゼオライトであり、かつCHA構造型を有する、請求項8〜10のいずれか1項に記載のSCR触媒系。
- 前記ゼオライトは、SSZ-13およびSSZ-62から選択される、請求項11の触媒系。
- 前記金属は、Cu、Fe、Co、CeおよびNiからなる群より選択される、請求項8〜12のいずれか1項に記載の触媒系。
- 前記金属は、Cuから選択され、かつ2質量%〜8重量%の範囲で交換される、請求項8〜13のいずれか1項に記載の触媒系。
- 希薄燃焼エンジンおよび前記希薄燃焼エンジンと液体連通する排気ガス導管であって、前記触媒系は、機関の下流にある、請求項1〜14のいずれか1項に記載の触媒系を含む希薄燃焼エンジン排気ガス処理系。
- 希薄燃焼エンジンからの排気ガスから窒素酸化物を除去する方法であって、排気ガス流を請求項1〜14のいずれか1項の触媒系に接触させることを特徴とする方法。
- バナジア/チタニアは、前記金属交換された8環小孔分子ふるいより高いN2形成およびより低いN2O形成を促進する系であって、前記金属交換された8環小孔分子ふるいは、前記バナジア/チタニアより低いN2形成およびより高いN2O形成を促進し、前記8環小孔分子ふるいは、前記バナジア/チタニアより高いアンモニア貯蔵容量を有する、請求項9に記載の触媒系。
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JP2019518587A (ja) * | 2016-04-13 | 2019-07-04 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトUmicore AG & Co.KG | Scr活性コーティングを有する触媒 |
JP7013378B2 (ja) | 2016-04-13 | 2022-02-15 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Scr活性コーティングを有する触媒 |
JP2022058647A (ja) * | 2016-04-13 | 2022-04-12 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Scr活性コーティングを有する触媒 |
JP7322206B2 (ja) | 2016-04-13 | 2023-08-07 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Scr活性コーティングを有する触媒 |
JP2020515767A (ja) * | 2017-04-04 | 2020-05-28 | ビーエーエスエフ コーポレーション | 水素支援型の統合された排ガス調整システム |
JP7295027B2 (ja) | 2017-04-04 | 2023-06-20 | ビーエーエスエフ コーポレーション | 水素支援型の統合された排ガス調整システム |
JP2021531966A (ja) * | 2018-07-24 | 2021-11-25 | ビーエーエスエフ コーポレーション | ディーゼルエンジンの排気ガスを処理するためのscr触媒 |
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EP2969195A1 (en) | 2016-01-20 |
US10512901B2 (en) | 2019-12-24 |
CA2902836A1 (en) | 2014-10-02 |
CA2902414A1 (en) | 2014-10-02 |
MX2015011155A (es) | 2015-11-09 |
KR102211490B1 (ko) | 2021-02-04 |
RU2015143697A (ru) | 2017-04-20 |
KR20150128697A (ko) | 2015-11-18 |
RU2015143692A (ru) | 2017-04-17 |
US9468915B2 (en) | 2016-10-18 |
EP2969196A1 (en) | 2016-01-20 |
EP2969197A1 (en) | 2016-01-20 |
KR102300817B1 (ko) | 2021-09-13 |
JP2016513585A (ja) | 2016-05-16 |
US20140271422A1 (en) | 2014-09-18 |
WO2014160292A1 (en) | 2014-10-02 |
BR112015022045A2 (pt) | 2019-09-10 |
BR112015022048A2 (pt) | 2019-09-10 |
KR20150128701A (ko) | 2015-11-18 |
CN112371164A (zh) | 2021-02-19 |
CN105188924A (zh) | 2015-12-23 |
US20140274665A1 (en) | 2014-09-18 |
JP6437520B2 (ja) | 2018-12-12 |
BR112015022048B1 (pt) | 2022-03-03 |
CN105188924B (zh) | 2017-10-27 |
WO2014160293A1 (en) | 2014-10-02 |
ZA201507602B (en) | 2017-06-28 |
CN105188925A (zh) | 2015-12-23 |
BR112015022045B1 (pt) | 2021-12-21 |
MX2015011354A (es) | 2016-01-15 |
JP6594292B2 (ja) | 2019-10-23 |
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