CN108712927A - 具有scr活性涂层的催化剂 - Google Patents
具有scr活性涂层的催化剂 Download PDFInfo
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- CN108712927A CN108712927A CN201780010184.1A CN201780010184A CN108712927A CN 108712927 A CN108712927 A CN 108712927A CN 201780010184 A CN201780010184 A CN 201780010184A CN 108712927 A CN108712927 A CN 108712927A
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- Prior art keywords
- catalyst
- zeolite
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- scr
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 238000000576 coating method Methods 0.000 title description 14
- 239000011248 coating agent Substances 0.000 title description 13
- 230000000694 effects Effects 0.000 title description 11
- 239000000463 material Substances 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 55
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010457 zeolite Substances 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011149 active material Substances 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 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 claims abstract description 22
- 229910052676 chabazite Inorganic materials 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012876 carrier material Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 42
- 239000007789 gas Substances 0.000 description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 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 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 6
- 239000000203 mixture Substances 0.000 description 6
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 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 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 zeolite Class compound Chemical class 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
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- 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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- 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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
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Abstract
本发明涉及一种催化剂,所述催化剂包含长度为L的催化剂基材和两种SCR催化活性材料A和B,其中SCR催化活性材料A包含含有离子交换的铁和/或铜的插晶菱沸石结构类型的沸石,并且SCR催化活性材料B包含含有离子交换的铁和/或铜的菱沸石结构类型的沸石,其中(i)SCR催化活性材料A和B为两个材料区A和B的形式,其中材料区A从催化剂基材的第一端延伸至少超过长度L的一部分,并且材料区B从催化剂基材的第二端延伸至少超过长度L的一部分,或者其中(ii)催化剂基材由SCR催化活性材料A或B和基质组分形成,并且SCR催化活性材料B或A以材料区B或A的形式延伸至少超过催化剂基材的长度L的一部分。
Description
本发明涉及用于降低内燃机废气中的氮氧化物的具有SCR活性涂层的催化剂。
配备主要以稀燃操作的内燃机的机动车辆的废气具体地含有除了颗粒排放物之外的主要排放物一氧化碳(CO)、烃(HC)以及氮氧化物(NOx)。由于相对较高的氧气含量为至多15体积%,因此一氧化碳和烃可相对容易地通过氧化而变得无害。然而,将氮氧化物还原成氮气要困难得多。
用于在存在氧气的情况下从废气中去除氮氧化物的一种已知方法是在合适的催化剂上借助于氨的选择性催化还原方法(SCR方法)。在该方法中,利用氨将废气中待去除的氮氧化物转化为氮气和水。
用作还原剂的氨可通过将氨前体化合物如尿素、氨基甲酸铵或甲酸铵按剂量加入到排气***中并随后水解而可用。
借助颗粒过滤器可非常有效地从废气中除去颗粒。由陶瓷材料制成的壁流式过滤器已特别成功。它们由多个平行通道构造,这些平行通道由多孔壁形成。通道在过滤器的两端中的一个上以气密方式交替地密封,使得形成第一通道,其在过滤器的第一侧上敞开并且在过滤器的第二侧上封闭;以及第二通道,其在过滤器的第一侧封闭并且在过滤器的第二侧上敞开。例如,流入第一通道的废气只能通过第二通道离开过滤器,并且为了这样做必须流过第一通道和第二通道之间的多孔壁。当废气穿过壁时,颗粒保持不变。
还已知使用SCR活性材料涂覆壁流式过滤器,从而同时从废气去除颗粒和氮氧化物。此类产品通常称为SDPF。
就所需量的SCR活性材料施加到通道之间的多孔壁(所谓的壁上涂层)而言,然而这会导致过滤器中的反压力的不可接受的增加。
在此背景下,JPH01-151706和WO2005/016497例如提出用SCR催化剂涂覆壁流式过滤器,使得SCR催化剂穿透多孔壁(所谓的壁内涂层)。
还提出(参见US 2011/274601)将第一SCR催化剂引入多孔壁中,即涂覆孔的内表面,并将第二SCR催化剂置于多孔壁的表面上。在这种情况下,第一SCR催化剂的平均粒度小于第二SCR催化剂的平均粒度。
此外,在WO2013/014467A1中已经提出在颗粒过滤器上连续布置两个或更多个SCR活性区。这些区可包含不同浓度的相同SCR活性材料或不同的SCR活性材料。在任何情况下,热稳定性更高的SCR活性材料优选布置在过滤器入口处。
颗粒过滤器必须以某些时间间隔再生,即必须烧掉收集的烟尘颗粒,以便将废气反压保持在可接受的范围内。为了再生过滤器并引发烟尘燃烧,需要约600℃的废气温度。在燃烧期间,可能发生非常高的温度,其可为>800℃。
如今常见的NH3-SCR催化剂可通过不期望的副反应产生一氧化二氮(N2O)形成。对于颗粒过滤器和NH3SCR催化剂的组合,例如在过滤器再生中也是如此。由于N2O是已知的温室气体,因此应尽可能地防止其形成。
WO2015/145113公开了一种减少废气中N2O排放的方法,其特征在于使用具有约3至约15的SAR的小孔沸石,其包含约1重量%至5重量%的交换过渡金属。
仍然需要NH3SCR催化剂,特别是对于由颗粒过滤器和NH3SCR催化剂组成的组合,其形成尽可能少的N2O。
令人惊讶地发现,当不同的沸石结构类型,即CHA和LEV结构类型的那些以特定方式布置在催化剂上时,获得具有SCR功能并形成较少N2O的催化剂。
本发明涉及一种催化剂,它包括长度为L的催化剂基材和两种彼此不同的SCR催化活性材料A和B,
其中SCR催化活性材料A包含含有离子交换的铁和/或铜的插晶菱沸石结构类型的沸石,并且SCR催化活性材料B包含含有离子交换的铁和/或铜的菱沸石结构类型的沸石,其中
(i)SCR催化活性材料A和B以两个材料区A和B的形式存在,其中从催化剂基材的第一端开始的材料区A延伸至少超过长度L的一部分,并且从催化剂基材的第二端开始的材料区B延伸至少超过长度L的一部分,
或者其中
(ii)催化剂基材由SCR催化活性材料A和基质组分形成,并且SCR催化活性材料B以材料区B的形式延伸至少超过催化剂基材的长度L的一部分,
或者其中
(iii)催化剂基材由SCR催化活性材料B和基质组分形成,并且SCR催化活性材料A以材料区A的形式延伸至少超过催化剂基材的长度L的一部分。
在本发明的实施方案中,菱沸石结构类型的沸石具有6至40,优选12至40,并且特别优选25至40的SAR值(二氧化硅与氧化铝的比率)。
在本发明的实施方案中,插晶菱沸石结构类型的沸石具有大于15,优选大于30,诸如30至50的SAR值。
可能的菱沸石结构类型的沸石是,例如,以菱沸石和SSZ-13的名称已知的那些产物。可能的插晶菱沸石结构类型的沸石是例如Nu-3、ZK-20和LZ-132。
在本发明的范围内,不仅硅铝酸盐而且硅铝磷酸盐和铝磷酸盐(有时也称为沸石类化合物)也属于术语“沸石”。示例特别是SAPO-34和AlPO-34(结构类型CHA)和SAPO-35和AlPO-35(结构类型LEV)。
在本发明的实施方案中,菱沸石结构类型的沸石以及插晶菱沸石结构类型的沸石都含有离子交换的铜。
在菱沸石结构类型的沸石中和在插晶菱沸石结构类型的沸石中的铜的量彼此独立地,具体地以CuO并且相对于交换的沸石的总重量计算的0.2重量%至6重量%,优选1重量%至5重量%。在菱沸石结构类型的沸石中和在插晶菱沸石结构类型的沸石中,沸石中交换的铜与沸石中的晶格铝的原子比,在下文中称为Cu/Al比彼此独立,具体地为0.25至0.6。
这对应于铜与沸石的理论交换水平为50%至120%,沸石中的完全电荷平衡由二价Cu离子在100%的交换水平下开始。特别优选的为0.35至0.5的Cu/Al值,这对应于70%至100%的理论铜交换水平。
就所采用的沸石包含离子交换的铁的程度而言,在菱沸石结构类型的沸石中和在插晶菱沸石结构类型的沸石中的铁的量彼此独立地,具体地以Fe2O3并且相对于交换的沸石的总重量计算的0.5重量%至10重量%,优选1重量%至5重量%。
在菱沸石结构类型的沸石中和在插晶菱沸石结构类型的沸石中,沸石中交换的铁与沸石中的晶格铝的原子比,在下文中称为Fe/Al比彼此独立,具体地为0.25至3。特别优选的是0.4至1.5的Fe/Al值。
材料区A包括,例如,除了用铜或铁交换的插晶菱沸石结构类型的沸石外,没有催化活性组分。然而,在适用的情况下,它可能含有添加剂,诸如粘结剂。合适的粘结剂是例如氧化铝、氧化钛和氧化锆,其中氧化铝是优选的。在本发明的实施方案中,材料区A由用铜或铁交换的插晶菱沸石结构类型的沸石以及粘结剂组成。氧化铝优选作为粘结剂。
材料区B也包括,例如,除了用铜或铁交换的菱沸石结构类型的沸石外,没有催化活性组分。然而,在适用的情况下,它可能含有添加剂,诸如粘结剂。合适的粘结剂是例如氧化铝、氧化钛和氧化锆。在本发明的实施方案中,材料区A由用铜或铁交换的菱沸石结构类型的沸石以及粘结剂组成。氧化铝优选作为粘结剂。
在本发明的实施方案中,20重量%至80重量%的催化活性材料在材料区B中,优选40重量%至80重量%,特别优选50重量%至70重量%。
在一个优选的实施方案中,本发明涉及一种催化剂,其包含长度L的催化剂基材和两种彼此不同的SCR催化活性材料A和B,其中SCR催化活性材料A包含含有离子交换的铁和/或铜的插晶菱沸石结构类型的沸石,以及SCR催化活性材料B包含含有离子交换的铁和/或铜的菱沸石结构类型的沸石,其中
SCR催化活性材料A和B以两个材料区A和B的形式存在,其中从催化剂基材的第一端开始的材料区A延伸至少超过长度L的一部分,并且从催化剂基材的第二端开始的材料区B延伸至少超过长度L的一部分。
在该实施方案中,废气优选在催化剂基材的第一端流入催化剂,并且在催化剂基材的第二端流出催化剂。
在该实施方案中,两个材料区A和B还可以不同的方式布置在催化剂基材上,其中所谓的流通式基材或壁流式过滤器可用作催化剂基材。
壁流式过滤器是催化剂基材,其包括长度为L的通道,该通道在壁流式过滤器的第一端与第二端之间平行延伸,它们在第一端或第二端以气密方式交替地密封,并且由多孔壁隔开。流通式基材与壁流式过滤器的不同之处尤其在于,长度为L的通道在其两端是敞开的。
在本发明的以下实施方案中,催化剂基材可以是壁流式过滤器或流通式基材。
在第一实施方案中,材料区A延伸超过催化剂基材的整个长度L,而从催化剂基材的第二端开始的材料区B延伸超过其长度L的10%至80%。在这种情况下,材料区B优选地布置在材料区A上。
在第二实施方案中,从催化剂基材的第一端开始的材料区A延伸超过其长度L的20%至90%,而从第二端开始的材料区B延伸超过其长度L的10%至70%。就在该实施方案中材料区A和B重叠的程度而言,材料区A优选地布置在材料区B上。
在第三实施方案中,从催化剂基材的第一端开始的材料区A延伸超过其长度L的20%至100%,而材料区B延伸超过其整个长度L。在这种情况下,材料区A优选地布置在材料区B上。
在根据本发明的催化剂的另一个实施方案中,催化剂基材被设计为壁流式过滤器。在壁流式过滤器的第一端敞开并在第二端封闭的通道涂覆有材料区A,而在壁流式过滤器的第一端封闭并在第二端敞开的通道涂覆有材料区B。
可根据本发明使用的流通式基材和壁流式过滤器是已知的并且可在市场上获得。它们由例如碳化硅、钛酸铝或堇青石组成。
在未涂覆状态下,壁流式过滤器具有例如30%至80%,具体地是50%至75%的孔隙率。它们在未涂覆状态下的平均孔径为例如5μm至30μm。
一般来讲,壁流式过滤器的孔为所谓的开口孔,即它们与通道有连接。此外,孔通常彼此连接。一方面,这使得能够容易地涂覆内孔表面,并且另一方面,使废气容易通过壁流式过滤器的多孔壁。
根据本发明的催化剂可根据本领域技术人员熟悉的方法制备,例如,根据常用的浸涂方法或泵涂和吸涂方法,随后进行热后处理(煅烧)。本领域技术人员知道,在壁流式过滤器的情况下,它们的平均孔径和SCR催化活性材料的平均粒度可彼此适应,使得材料区A和/或B位于多孔壁上,其形成壁流式过滤器的通道(壁上涂层)。然而,优选地,选择SCR催化活性材料的平均粒度,使得材料区A和材料区B都位于形成壁流式过滤器的通道的多孔壁中,使得内部孔表面被涂覆(壁内涂层)。在这种情况下,SCR催化活性材料的平均粒度必须足够小以渗透到壁流式过滤器的孔中。
然而,本发明还包括其中材料区A和B中的一个被涂覆在壁内,而另一个被涂覆在壁上的实施方案。
本发明还涉及其中催化剂基材由惰性基质组分形成的实施方案,并且SCR催化活性材料A或B和其它SCR催化活性材料即材料B或A以材料区B或A的形式延伸至少超过催化剂基材的长度L的一部分。
不仅由惰性材料如堇青石组成而且还另外含有催化活性材料的催化剂基材、流通式基材和壁流式基材是本领域技术人员已知的。为了制备它们,根据本身已知的方法挤出由例如10重量%至95重量%的惰性基质组分和5重量%至90重量%的催化活性材料组成的混合物。在这种情况下,所有也用于生产催化剂基材的惰性材料都可用作基质组分。这些基质组分是例如硅酸盐、氧化物、氮化物或碳化物,其中特别优选硅酸镁铝。
包含SCR催化活性材料A或B的挤出催化剂基材也可根据常规方法如惰性催化剂基材进行涂覆。
因此,包含SCR催化活性材料B的催化剂基材可例如用含有SCR催化活性材料A的洗涂层在其整个长度或其一部分上涂覆。
同样,包含SCR催化活性材料A的催化剂基材可例如用含有SCR催化活性材料B的洗涂层在其整个长度或其一部分上涂覆。
具有SCR活性涂层的根据本发明的催化剂可有利地用于纯化来自稀燃操作的内燃机,特别是柴油发动机的废气。在这种情况下,它们将被布置在废气流中,使得材料区A在材料区B之前与待纯化的废气接触。在这种情况下,废气中包含的氮氧化物被转化为无害化合物氮气和水。
因此,本发明还涉及一种用于纯化来自稀燃操作的内燃机的废气的方法,其特征在于,废气在根据本发明的催化剂上进行,其中材料区A在材料区B之前与待被纯化的废气接触。
在根据本发明的方法中,氨优选用作还原剂。所需的氨可例如在根据本发明的催化剂上游的废气***中形成,例如借助于上游氮氧化物捕集催化剂(少NOx捕集器-LNT)。这种方法被称为“被动SCR”。
然而,氨也可以尿素水溶液的形式夹带在载体上,尿素水溶液根据需要通过根据本发明的催化剂上游的喷射器给剂量。
因此,本发明还涉及一种用于纯化来自稀燃操作的内燃机的废气的***,其特征在于,其包括根据本发明的具有SCR活性涂层的催化剂以及用于尿素水溶液的喷射器,其中喷射器位于催化剂基材的第一端之前。
例如,从SAE-2001-01-3625可知,当氮氧化物存在于由一氧化氮和二氧化氮组成的1:1或者在任何情况下接近该比率的混合物中时,与氨的SCR反应更快。由于来自稀燃操作的内燃机的废气通常具有与二氧化氮相比过量的一氧化氮,因此该文献提出借助于布置在SCR催化剂上游的氧化催化剂来增加二氧化氮的部分。
因此,根据本发明的用于纯化来自稀燃操作的内燃机的废气的***的一个实施方案包括-在废气流动方向上-氧化催化剂、用于尿素水溶液的喷射器和根据本发明的具有SCR活性涂层的催化剂,其中喷射器位于催化剂基材的第一端之前。
在本发明的实施方案中,载体材料上的铂用作氧化催化剂。
本领域的技术人员对此目的熟悉的所有材料均可用作铂的载体材料。它们具有30m2/g至250m2/g,优选100m2/g至200m2/g的BET表面积(根据DIN 66132测定),并且特别是氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈以及这些氧化物中至少两种的混合物或混合氧化物。
氧化铝和铝/硅混合氧化物是优选的。如果使用氧化铝,则特别优选用例如氧化镧稳定化。
氧化催化剂通常位于流通式基材上,特别是由堇青石组成的流通式基材。
实施例1
a)从一端开始,由堇青石组成的常规壁流式过滤器在其长度的50%上用洗涂层通过常规浸渍法涂覆,其中洗涂层含有用4.0重量%的铜交换的菱沸石结构类型的沸石。沸石的SAR值为30。然后,在120℃下干燥过滤器。
b)从另一端开始,步骤a)中获得的壁流式过滤器也在第二步骤中以50%的长度上用洗涂层通过常规浸渍方法涂覆,其中洗涂层含有用3.5重量%的铜交换的插晶菱沸石结构类型的沸石。沸石的SAR值为31。随后在500℃下干燥和煅烧2小时。
c)以这种方式获得的壁流式过滤器在模型气体***中的动态SCR测试中表现出250℃至550℃以上的范围内的非常有效的NOx转化率,其中模型气体首先与铜插晶菱沸石接触然后与铜菱沸石接触。在这种情况下,N2O的形成在整个温度范围内保持在可容许的范围内。
实施例2
重复实施例1,不同之处在于使用由堇青石组成的常规流通式基材代替由堇青石组成的常规壁流式过滤器。用4.0重量%铜交换的菱沸石结构类型的沸石和用3.5重量%铜交换的插晶菱沸石结构类型沸石均以200g/L基材的量涂覆。与实施例1相比,插晶菱沸石结构类型的沸石具有30的SAR值。
比较例1
重复实施例2,不同之处在于,在步骤a)中施加250g/L的用4.0重量%的铜交换的菱沸石结构类型的沸石,并且在步骤b)中以150g/L的量施加在步骤a)中已经使用的用4.0重量%的铜交换的菱沸石结构类型的沸石。
NOx的转化率测试
a)将根据实施例2和比较例1的催化剂在800℃下水热老化16小时。
b)在模型气体反应器中在所谓的NOx转化率测试中测定取决于催化剂之前的温度的老化催化剂的NOx转化率以及N2O的形成。该测试由包括预处理和针对各种目标温度运行的测试循环的测试程序组成。所施加的气体混合物记录在下表中。
测试程序:
1.在600℃下在N2中预处理10分钟
2.针对目标温度重复测试循环
a.目标温度接近气体混合物1
b.加入NOx(气体混合物2)
c.加入NH3(气体混合物3),等到NH3超过>20ppm,或最多30分钟持续时间
d.已编程的温度脱附温度最高500℃(气体混合物3)
表:NOx转化率测试的气体混合物。
气体混合物 | 1 | 2 | 3 |
N2 | 余量 | 余量 | 余量 |
O2 | 10体积% | 10体积% | 10体积% |
NOx | 0ppm | 500ppm | 500ppm |
NO2 | 0ppm | 0ppm | 0ppm |
NH3 | 0ppm | 0ppm | 750ppm |
CO | 350ppm | 350ppm | 350ppm |
C3H6 | 100ppm | 100ppm | 100ppm |
H2O | 5体积% | 5体积% | 5体积% |
对于低于500℃的每个温度(在每种情况下空间速度为60kh-1),对于测试程序范围2c确定NH3滑移为20ppm的转化率。对于高于500℃的每个温度点(空间速度为100kh-1),在测试温度范围2c中确定平衡状态下的转化率。通过FT-IR在所有温度点下测定N2O浓度。如图1所示的应用源于NOx转化率的应用以及不同温度点的N2O浓度。
一旦测试了根据实施例2的催化剂,使得模型气体首先与铜插晶菱沸石接触,并且然后与铜菱沸石接触。该测量被指定为图1中的示例2/1。
此外,还“反向”测试了根据实施例2的催化剂,使得模型气体首先与铜菱沸石接触,然后与铜插晶菱沸石接触。该测量被指定为图1中的示例2/2。
同样的程序也用于根据比较例1的催化剂。在图1中,首先将250g/L的铜菱沸石的负载首先与模型气体接触的测量指定为比较例1/1,并且150g/L铜菱沸石的负载首先与模型气体接触的测量被指定为比较例为1/2。
在图1中,可看出,根据实施例2和比较例1的催化剂的NOx转化率(参见实线)独立于与模型气体进入相应催化剂的一侧没有太大差别。然而,非常清楚的是,当模型气体首先与铜插晶菱沸石接触然后与铜菱沸石(实施例2/1)接触时,根据实施例2的催化剂在整个温度范围内形成显着更少的一氧化二氮(参见虚线)。
Claims (15)
1.一种催化剂,所述催化剂包括长度为L的催化剂基材和两种彼此不同的SCR催化活性材料A和B,
其中所述SCR催化活性材料A包含含有离子交换的铁和/或铜的插晶菱沸石结构类型的沸石,并且所述SCR催化活性材料B包含含有离子交换的铁和/或铜的菱沸石结构类型的沸石,其中
(i)所述SCR催化活性材料A和B以两个材料区A和B的形式存在,其中从所述催化剂基材的第一端开始的材料区A延伸至少超过长度L的一部分,并且从所述催化剂基材的第二端开始的材料区B延伸至少超过长度L的一部分,
或者其中
(ii)所述催化剂基材由所述SCR催化活性材料A和基质组分形成,并且所述SCR催化活性材料B以材料区B的形式延伸至少超过所述催化剂基材的长度L的一部分,
或者其中
(iii)所述催化剂基材由所述SCR催化活性材料B和基质组分形成,并且所述SCR催化活性材料A以材料区A的形式延伸至少超过所述催化剂基材的长度L的一部分。
2.根据权利要求1所述的催化剂,其特征在于,所述菱沸石结构类型的沸石具有6至40的SAR值。
3.根据权利要求1和/或2所述的催化剂,其特征在于,所述插晶菱沸石结构类型的沸石具有大于15的SAR值。
4.根据权利要求1至3中的一项或多项所述的催化剂,其特征在于,所述菱沸石结构类型的沸石和所述插晶菱沸石结构类型的沸石均包含离子交换的铜。
5.根据权利要求4所述的催化剂,其特征在于,所述菱沸石结构类型的沸石和所述插晶菱沸石结构类型的沸石中的铜在每种情况下以CuO并且相对于所交换的沸石的总重量计算的0.2重量%至6重量%的量独立地存在。
6.根据权利要求1至5中的一项或多项所述的催化剂,其特征在于,在所述菱沸石结构类型的沸石中以及所述插晶菱沸石结构类型的沸石中铜与铝的原子比彼此独立地为0.25至0.6。
7.根据权利要求1至6中的一项或多项所述的催化剂,其特征在于,20重量%至80重量%的催化活性材料在材料区B中。
8.根据权利要求1至7中的一项或多项所述的催化剂,其特征在于,材料区A延伸超过所述催化剂基材的整个长度L,并且从所述催化剂基材的第二端开始的材料区B延伸超过其长度L的10%至80%。
9.根据权利要求1至7中的一项或多项所述的催化剂,其特征在于,从所述催化剂基材的第一端开始的材料区A延伸超过其长度L的20%至90%,并且从所述催化剂基材的第二端开始的材料区B延伸超过其长度L的10%至70%。
10.根据权利要求1至7中的一项或多项所述的催化剂,其特征在于,从所述催化剂基材的第一端开始的材料区A延伸超过其长度L的20%至100%,并且材料区B延伸超过所述催化剂基材的整个长度。
11.根据权利要求1至10中的一项或多项所述的催化剂,其特征在于,所述催化剂基材是壁流式过滤器,并且在所述壁流式过滤器的第一端敞开并在第二端封闭的通道涂覆有材料区A,并且在所述壁流式过滤器的第一端封闭并在第二端敞开的通道涂覆有材料区B。
12.一种用于纯化来自稀燃操作的内燃机的废气的方法,其特征在于,所述废气在根据权利要求1至11中的一项或多项所述的催化剂上方进行,其中材料区A在材料区B之前与待被纯化的废气接触。
13.一种用于纯化来自稀燃操作的内燃机的废气的***,其特征在于,所述***包括根据权利要求1至11中的一项或多项所述的催化剂以及用于尿素水溶液的喷射器,其中所述喷射器位于所述催化剂基材的第一端之前。
14.根据权利要求13所述的***,其特征在于,所述***在所述废气的流的方向上具有氧化催化剂、用于尿素水溶液的喷射器和根据权利要求1至10中的一项或多项所述的催化剂,其中所述喷射器位于所述催化剂基材的第一端之前。
15.根据权利要求14所述的***,其特征在于,载体材料上的铂用作氧化催化剂。
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