CN104780997A - 用于处理含nox和颗粒的柴油排气的催化剂体系 - Google Patents
用于处理含nox和颗粒的柴油排气的催化剂体系 Download PDFInfo
- Publication number
- CN104780997A CN104780997A CN201380058683.XA CN201380058683A CN104780997A CN 104780997 A CN104780997 A CN 104780997A CN 201380058683 A CN201380058683 A CN 201380058683A CN 104780997 A CN104780997 A CN 104780997A
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- Prior art keywords
- catalyst
- noble metal
- catalyst system
- particulate filter
- diesel particulate
- Prior art date
- 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.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 239000002245 particle Substances 0.000 title description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 207
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 77
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000003860 storage Methods 0.000 claims abstract description 62
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 38
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims description 38
- 229910021536 Zeolite Inorganic materials 0.000 claims description 28
- 239000010457 zeolite Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- -1 zeolite compound Chemical class 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract 4
- 239000000758 substrate Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000012876 carrier material Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 235000019504 cigarettes Nutrition 0.000 description 6
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000027648 face development Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 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 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium 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
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- B01D53/9459—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
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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
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- 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
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J37/02—Impregnation, coating or precipitation
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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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Abstract
本发明涉及一种用于处理柴油排气的催化剂体系,该催化剂体系在该排气的流动方向上包含:-一种含有氮氧化物存储组分和贵金属的氮氧化物存储催化剂,-以及一种含有选自铂、钯、以及铂和钯的系列的贵金属的柴油微粒过滤器,其特征在于该氮氧化物存储催化剂的贵金属装载量是100至180g/ft3(3.53至6.36g/l)并且该柴油微粒过滤器的贵金属装载量是5至35g/ft3(0.18至1.24g/l)。
Description
本发明涉及一种用于处理柴油排气的催化剂体系,该催化剂体系在该排气的流动方向上包含一种氮氧化物存储催化剂和一种柴油微粒过滤器,其中这两种成分包括催化活性的贵金属。
由柴油发动机驱动的机动车辆的排气不仅包含一氧化碳(CO)和氮氧化物(NOx),而且还包含来源于在汽缸的燃烧室中的燃料的不完全燃烧的多种成分。这些不仅包含通常同样主要呈气体形式的残余的烃类(HC),而且还包含也被称为“柴油炭烟”或者“炭烟颗粒”的微粒排放物。这些是,由主要地含碳的固体颗粒以及通常主要由相对长链的烃缩合物组成的一种粘附液相构成的复合团聚体。粘附到这些固体成分上的液相也被称为“可溶的有机部分SOF”或者“挥发性的有机部分VOF”。
为了清洁这些排气,所述成分必须非常实质性地转化为无害的化合物,这仅仅使用适合的催化剂是可能的。
例如,粘附在炭烟颗粒上的一氧化碳(CO)、气态烃类(HC)以及任何有机团聚体(被称为“挥发性有机部分”,VOF)可以在氧化催化剂的帮助下氧化地去除。
通过使用微粒过滤器从柴油车辆的排气中去除微粒排放物。微粒过滤器总体上是壁流式过滤器基底,即,具有气密密封的、被多孔壁界定的并且彼此分开的交替的流入和流出通道的蜂窝状物。通过存在于出口侧上的气密闭合塞迫使正流动进入到流入通道中的含微粒的排气穿过多孔壁,并且从在该流入侧上封闭的流出通道处再次离开该壁流式过滤器基底。在这个过程中,柴油炭烟从该排气中过滤出去。
随着过滤的炭烟颗粒量的增加,在该排气***中的背压上升,并且所以该过滤器必须定期通过烧掉炭烟进行再生。由于炭烟与氧的着火和烧尽所要求的超过550℃的温度典型地可能仅在现代客运车辆柴油发动机中的全负荷工作中实现,为了防止该过滤器被炭烟堵塞,附加的措施对于过滤的炭烟颗粒的氧化是绝对必要的。为此目的,该过滤器可以涂覆有一个能够降低炭烟着火温度的催化剂层。配备有一个催化剂层的微粒过滤器也被称为cDPF(催化的柴油微粒过滤器)并且,例如,在SAE文件SAE 2005-01-1756中进行了描述。
去除氮氧化物的一种可能的方式是使用氮氧化物存储催化剂,其中术语“贫NOx捕捉器”或LNT已经建立。其清洁作用是基于通过主要呈硝酸盐形式的该存储催化剂的存储材料在该发动机的一个贫工作阶段中对氮氧化物的存储,以及其再次在该发动机的一个随后的富工作阶段的分解,以及由此释放的氮氧化物与这些还原性的排气成分在该存储催化剂上反应以便产生氮气、二氧化碳以及水。这种工作模式例如在SAE文件SAE 950809中进行了描述。
有用的存储材料尤其包括镁、钙、锶、钡、碱金属、稀土金属的氧化物、碳酸盐或氢氧化物或其混合物。因为它们的碱性特性,这些化合物能够与排气中的酸性氮氧化物形成硝酸盐并且以此方式储存它们。它们以非常高的分散度(dispersion)沉积在适合的载体材料上来产生与排气的大的相互作用面积。氮氧化物存储催化剂总体上附加地包含贵金属如铂、钯和/或铑作为催化活性组分。它们具有以下任务,首先在贫条件下将NO氧化为NO2,并且将CO和HC氧化为CO2,并且其次将在其中氮氧化物存储催化剂再生的富工作阶段过程中释放的NO2还原为氮气。
在氧的存在下从排气除去氮氧化物的另一种已知方法是通过氨在一种合适催化剂(SCR催化剂)上的选择性催化还原的方法(SCR方法)。在这个方法中,有待从排气中去除的氮氧化物与氨进行反应产生氮和水。用作还原剂的氨可以作为排气***中的次级排放物而产生,或可以通过将一种可以形成氨的前体化合物计量引入至排气线和随后的水解供使用,该前体化合物例如尿素、氨基甲酸铵或甲酸铵。
该SCR方法的后者的变体的完成要求一个用于提供还原剂的来源、一种用于将该还原剂如所要求地计量引入到排气中的注射装置、以及一种布置在该排气的流动路径中的SCR催化剂。
为了能将所讨论的有害的排气组分去除到所要求的程度,所述催化剂和过滤器必须以一种适合的方式彼此结合以便形成一个排气处理***。这对于要满足Euro6标准或甚至后继标准的车辆尤其是如此。
例如,US 2006/248874描述了一种体系,该体系在排气的流动方向上包含一种氮氧化物存储催化剂、一种微粒过滤器以及另一种氮氧化物存储催化剂。设计该第一氮氧化物存储催化剂以便在较低的温度下存储氮氧化物并且在超过300℃的温度下甚至在贫条件下再次释放它。在后者的情况下,该氮氧化物可以用于氧化在下游微粒过滤器上的微粒。然而,如果该氮氧化物在富条件下被释放,它可能通过还原催化剂(例如铑)被还原为N2。设计该第二氮氧化物存储催化剂以便在贫条件下在300℃至550℃的温度下存储氮氧化物。这种体系的缺点是与两种氮氧化物催化剂的使用相关联的空间要求,这在许多情况下不适用。附带地,两种氮氧化物存储催化剂的使用出于经济原因也不是最佳的。
US 2010/236224描述了一种体系,该体系在该排气的流动方向上可以包含一种氮氧化物存储催化剂和一种微粒过滤器。该体系尤其特征在于它在朝向该氮氧化物存储催化剂的流出侧上具有一种用于将空气计量引入至排气流中用于还原烃类的装置。
因此,对于有效地去除所述污染物的体系存在一种需求,其中可得的空间是足够的,并且其可以按照一种经济上可行的方式进行制造。
现已发现一种由氮氧化物存储催化剂和安置在其流出端的柴油微粒过滤器组成的体系满足这些条件并且更特别地非常有效地从排气中去除CO和NOx排放物,当催化活性贵金属以一种最佳的方式分布在两者的成分上时。
本发明涉及一种用于处理柴油排气的催化剂体系,该催化剂体系在该排气的流动方向上包含:
-一种含有氮氧化物存储组分和贵金属的氮氧化物存储催化剂,以及
-一种含有选自铂、钯、以及铂和钯的组的贵金属的柴油微粒过滤器,
其特征在于该氮氧化物存储催化剂的贵金属装载量是100至180g/ft3(3.53至6.36g/L)并且该柴油微粒过滤器的贵金属装载量是5至35g/ft3(0.18至1.24g/L)。
因此,该氮氧化物存储催化剂的贵金属装载量高于该柴油微粒过滤器的贵金属装载量。
单位g/ft3和g/L各自对应地表示以ft3和L计的每载体基底的单位体积以g计的对应组分的量。
可以在这些氮氧化物存储催化剂中使用的氮氧化物存储组分是例如碱金属、碱土金属、镧和镧系元素(Ce至Lu)的氧化物、氢氧化物、氧化物的氢氧化物(oxide hydroxide)、碳酸盐以及碳酸氢盐。给予优选的是钠、钾、锶、钡和镧的氧化物、氢氧化物、氧化物的氢氧化物、碳酸盐和碳酸氢盐。给予特别优选的是使用锶和钡的氧化物、氢氧化物、氧化物的氢氧化物和碳酸盐、以及其混合物。
在本发明的实施例中,所使用的氮氧化物存储组分是基于对应的氧化物呈15至20g/L的量的碱金属或碱土金属的氧化物、氢氧化物、氧化物的氢氧化物、碳酸盐和/或碳酸氢盐。在其他实施例中,使用了附加的组分,例如氧化铈。在这些情况下,氮氧化物存储组分的量基于对应的氧化物是150至250g/L。
对于该氮氧化物存储催化剂有用的贵金属包括,例如铂、钯和/或铑。尤其可能的是使用铂或钯作为单独的贵金属亦或以一种与彼此的混合物使用它们。如果使用了铂和钯,Pt:Pd重量比尤其是2:1至10:1。
在本发明的实施例中,该氮氧化物存储催化剂的贵金属装载量是150至180g/ft3(5.30至6.36g/L)。
氮氧化物存储组分和贵金属典型地存在于适合的载体材料上。所使用的载体材料尤其是高表面积的、高熔点的氧化物,例如氧化铝、二氧化硅、二氧化钛,而且还有铈-锆混合氧化物以及镁-铝混合氧化物。在本发明的上下文中,氮氧化物存储组分和贵金属可以一起存在于一种载体材料上亦或存在于不同的载体材料上。
在本发明的实施例中,该氮氧化物存储催化剂作为一种陶瓷或金属的流通式基底作为载体存在,催化活性成分已经以一种涂层的形式施用到其上。适合的流通式基底是已知的并且在市场上是可获得的。
在本发明的实施例中,该氮氧化物存储催化剂的总载体涂料(washcoat)装载量是250至400g/L。
该柴油微粒过滤器包含铂、钯、或铂和钯作为贵金属。在本发明的一个实施例中,它包含仅铂或仅钯。
在本发明的另一个实施例中,它包含铂和钯,其中Pt:Pd重量比为1:2至12:1,例如1:1、6:1、10:1以及12:1。
在本发明的另一个实施例中,该柴油微粒过滤器的贵金属装载量是10至25g/ft3(0.35至0.88g/L)。
在本发明的另一个实施例中,该柴油微粒过滤器包含一种沸石化合物,尤其以5至25g/L、尤其是10至20g/L的量。适合的沸石化合物是热稳定的、大孔或中孔的沸石结构类型,尤其β-沸石、沸石Y、丝光沸石和ZSM-5。
在本发明的另一个实施例中,该柴油微粒过滤器包含产生H2S阻挡作用的组分。适合的组分是本领域技术人员已知的并且在文献中进行了描述。例如,EP 2 275 194 A1描述了一种H2S阻挡作用,其通过一种含有铜化合物(例如氧化铜)的涂层和一种耐火载体材料(例如γ-氧化铝)实现。
也在该柴油微粒过滤器中,这些催化活性成分(即,尤其是贵金属)和任何沸石化合物都存在于一种载体材料上。为此目的有用的材料是以上关于该氮氧化物存储催化剂已经提及的那些。
在本发明的实施例中,该柴油微粒过滤器采取一种陶瓷或金属的壁流式过滤器基底作为载体的形式,这些催化活性成分已经以一个或多个涂层的形式施用到其上。在具体的实施例中,这些催化活性成分存在于在流入与流出通道之间的多孔壁中。适合的壁流式过滤器基底是已知的并且是在市场上可获得的。
在本发明的一个实施例中,这些催化活性成分遍及该壁流式过滤器基底的整个长度均匀分布。
在另一个实施例中,它们还可能以分区的形式存在。这意味着在一个入口端面与出口端面之间延伸的长度L的壁流式过滤器基底具有一个从该入口端面出发延伸长度E的第一催化活性区域和一个就其组成而言不同于该第一催化活性区域并且从该出口端面出发延伸长度Z的第二催化活性区域,其中E+Z≤L。在该流入端处的区域的长度是例如在该过滤器基底的总长度的20%与50%之间。
在这两个区域中的沸石含量可以相等或类似。总体上,在该流入端处的区域具有显著更高的贵金属装载量,尤其是该过滤器涂层的总贵金属含量的60%至90%。
如果该过滤器具有根据EP 2 275 194 A1所述的H2S阻挡作用,则一个分区的实施例是有利的。为此目的,该铜化合物被施用在一个占该基底长度的20%至80%、优选40%至60%的区域中并且该区域可以形成在该入口端或出口端处的区域。然后,该过滤器基底的剩余长度基本上配备有以上描述的含贵金属的涂层。
在本发明的实施例中,该柴油微粒过滤器的载体涂料装载量是8至40g/L。
在本发明的一个实施例中,用于处理柴油排气的催化剂体系包含在该排气的流动方向上布置在该柴油微粒过滤器下游的一种SCR催化剂。
有用的SCR催化剂尤其包括基于混合氧化物和基于沸石的SCR催化剂。
适合的混合氧化物是例如含钒或无钒的混合氧化物,例如含铈和含镧系元素的混合氧化物。
基于沸石的SCR催化剂尤其是,例如CHA、SAPO、ZSM-5和沸石β类型的铜或离子交换的沸石。
在包含一种SCR催化剂的本发明的催化剂体系的一个实施例中,该微粒过滤器优选地包含一个富铂的涂层。这意味着它以20至50g/cft的装载量包含或者仅仅铂或者呈至少4:1的比例的铂和钯。
本发明的催化剂体系优选地不包含任何用于将空气计量引入至该排气流中的装置。
在另一个实施例中,本发明涉及一种用于处理柴油排气的催化剂体系,该催化剂体系在该排气的流动方向上包含:
-一种含有氮氧化物存储组分和呈150至180g/ft3(5.30至6.36g/L)的量的贵金属的氮氧化物存储催化剂,以及
-一种含有呈1:1的Pt:Pd重量比并且呈10至25g/ft3(0.35至0.88g/L)的量的铂和钯、以及呈10至25g/L的量的沸石化合物的柴油微粒过滤器。
本发明的催化剂体系出色地适合于处理柴油排气并且就NOx、HC、CO和微粒的处理而言能够满足Euro 6法规的规定。
因此,本发明还涉及一种处理柴油排气的方法,其特征在于使该柴油排气通过一种催化剂体系,该催化剂体系在该排气的流动方向上包含:
-一种含有氮氧化物存储组分和贵金属的氮氧化物存储催化剂,以及
-一种含有选自铂、钯、以及铂和钯的组的贵金属的柴油微粒过滤器,
其中该氮氧化物存储催化剂的贵金属装载量是100至180g/ft3(3.53至6.36g/L)并且该柴油微粒过滤器的贵金属装载量是5至35g/ft3(0.18至1.24g/L)。
在本发明的方法中,该氮氧化物存储催化剂承担了在贫/富排气中的NOx和CO转化的功能,同时该柴油微粒过滤器专门负责HC和残余痕量的CO的转化并且负责微粒过滤和再生。这尤其通过存在于该催化剂体系中的贵金属以一种最佳的方式在氮氧化物存储催化剂与柴油微粒过滤器之间的分布实现。
本发明方法的构型对应于以上描述的本发明的催化剂体系的构型。
对比实例
a)对于氮氧化物存储催化剂的生产,一种商业的流通式基底以一种常规的方式使用催化剂配方以347g/L的总量进行涂覆。该载体涂料包含负载在一种标准镧稳定的氧化铝上的100g/ft3的铂、22g/ft3的钯和5g/ft3的铑,以及还有17g/L的BaO和220g/L的氧化铈。该氮氧化物存储催化剂的总贵金属装载量是127g/ft3。
b)对于柴油微粒过滤器的生产,一种商业的壁流式过滤器基底按照以下方式涂覆:
输入区域:对于该过滤器基底的长度的三分之一,100g/ft3的呈2:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及9g/L的一种可商购的β-沸石。流出区域:对于该过滤器基底的长度的剩余的三分之二,10g/cft的呈2:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及10g/L的一种可商购的β-沸石。
这导致40g/cft的呈2:1的重量比的铂和钯的总装载量。
c)将根据a)的氮氧化物存储催化剂和根据b)的柴油微粒过滤器结合以产生一种催化剂体系(其中该柴油微粒过滤器在该流出端处)。
实例1
a)对于氮氧化物存储催化剂的生产,该程序类似于在对比实例中的a),除了将该铂装载量增加至126g/ft3并且将该钯装载量增加至37.8g/ft3之外,同时将该铑装载量保持恒定在5g/ft3。这导致168.8g/ft3的贵金属的总装载量。
b)对于柴油微粒过滤器的生产,一种商业的壁流式过滤器基底如下进行涂覆:
输入区域:对于该过滤器基底的长度的三分之一,55g/ft3的呈1:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及9g/L的一种可商购的β-沸石。流出区域:对于该过滤器基底的长度的剩余的三分之二,10g/ft3的呈1:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及10g/L的一种可商购的β-沸石。
这导致25g/cft的呈1:1的重量比的铂和钯的总装载量。
c)将根据a)的氮氧化物存储催化剂和根据b)的柴油微粒过滤器结合以产生一种催化剂体系(其中该柴油微粒过滤器在该流出端处)。
体系性能的确定
根据实例1和对比实例的催化剂体系的体系性能在一个发动机试验台上根据NEDC(新欧洲行驶循环)测量。为此目的,排放的CO、HC和NOx的量以mg/km计确定。结果可以在表1中找到。
表1
这示出了根据实例1的催化剂体系就CO转化率和NOx转化率两者而言明显优于根据对比实例的催化剂体系。
实例2
将根据实例1a)的氮氧化物存储催化剂与根据实例1c)的柴油微粒过滤器结合以产生一种催化剂体系,该催化剂体系已经被如下生产:
一种商业的壁流式过滤器基底如下进行涂覆:
遍及该壁流式过滤器基底的整个长度L均匀涂覆:10g/ft3的呈1:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及9g/L的一种可商购的β-沸石。
这导致10g/ft3的呈1:1的重量比的铂和钯的总装载量。
由此获得的催化剂体系特征为与实例1的催化剂体系的特性可比较的特性。
实例3
将根据实例1a)的氮氧化物存储催化剂与根据实例1c)的柴油微粒过滤器结合以产生一种催化剂体系,该催化剂体系已经被如下生产:
一种商业的壁流式过滤器基底如下进行涂覆:
输入区域:对于该过滤器基底的长度的三分之一,40g/ft3的呈2:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及9g/L的一种可商购的β-沸石。流出区域:对于该过滤器基底的长度的剩余的三分之二,10g/ft3的呈2:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及10g/L的一种可商购的β-沸石。
这导致20g/ft3的呈2:1的重量比的铂和钯的总装载量。
由此获得的催化剂体系特征为与实例1的催化剂体系的特性可比较的特性。
实例4
a)将根据实例1a)的氮氧化物存储催化剂与一种柴油微粒过滤器以及一种SCR催化剂结合以产生一种催化剂体系,在该排气的流动方向上具有以下顺序:氮氧化物存储催化剂、柴油微粒过滤器、SCR催化剂。
b)对于该柴油微粒过滤器的生产,一种商业的壁流式过滤器基底如下进行涂覆:
遍及该壁流式过滤器基底的整个长度L均匀涂覆:50g/ft3的呈6:1的重量比的铂和钯(在一种镧稳定的氧化铝上)以及33g/L的一种可商购的β-沸石。
这导致50g/ft3的呈6:1的重量比的铂和钯的总装载量。
c)对于该SCR催化剂的生产,一种商业的流动式基底以一种常规的方式使用含铜的沸石载体涂料以200g/L的总量进行涂覆。
Claims (14)
1.一种用于处理柴油排气的催化剂体系,该催化剂体系在该排气的流动方向上包含:
-一种含有氮氧化物存储组分和贵金属的氮氧化物存储催化剂,以及
-一种含有选自铂、钯、以及铂和钯的组的贵金属的柴油微粒过滤器,
其特征在于该氮氧化物存储催化剂的贵金属装载量是100至180g/ft3(3.53至6.36g/L)并且该柴油微粒过滤器的贵金属装载量是5至35g/ft3(0.18至1.24g/L)。
2.如权利要求1所述的催化剂体系,其特征在于所使用的这些氮氧化物存储组分是碱金属、碱土金属、镧和镧系元素(Ce至Lu)的氧化物、氢氧化物、氧化物的氢氧化物、碳酸盐以及碳酸氢盐。
3.如权利要求1和/或2所述的催化剂体系,其特征在于所使用的这些氮氧化物存储组分是锶和钡的氧化物、氢氧化物、氧化物的氢氧化物或碳酸盐。
4.如权利要求1至3中一项或多项所述的催化剂体系,其特征在于该氮氧化物存储催化剂的贵金属装载量是150至180g/ft3(5.30至6.36g/L)。
5.如权利要求1至4中一项或多项所述的催化剂体系,其特征在于该柴油微粒过滤器的贵金属装载量是10至25g/ft3(0.35至0.88g/L)。
6.如权利要求1至5中一项或多项所述的催化剂体系,其特征在于该柴油微粒过滤器包含一种沸石化合物。
7.如权利要求6所述的催化剂体系,其特征在于所使用的沸石化合物是β-沸石、沸石Y、丝光沸石或ZSM-5。
8.如权利要求6和/或7所述的催化剂体系,其特征在于该沸石化合物以5至25g/L的量使用。
9.如权利要求1至8中一项或多项所述的催化剂体系,其特征在于该柴油微粒过滤器具有一种H2S阻挡作用。
10.如权利要求1至9中一项或多项所述的催化剂体系,其特征在于它包含在该排气的流动方向上布置在该柴油微粒过滤器的下游的一种SCR催化剂。
11.如权利要求10所述的催化剂体系,其特征在于所使用的SCR催化剂是来自含钒和无钒的混合氧化物的组的混合氧化物。
12.如权利要求10所述的催化剂体系,其特征在于所使用的SCR催化剂是CHA、SAPO、ZSM-5或沸石β类型的铜或离子交换的沸石。
13.如权利要求1至12中一项或多项所述的催化剂体系,其特征在于它在该排气的流动方向上包含:
-一种含有氮氧化物存储组分和呈160至180g/ft3(5.65至6.36g/L)的量的贵金属的氮氧化物存储催化剂,以及
-一种含有呈1:1的Pt:Pd重量比并且呈10至25g/ft3(0.35至0.88g/L)的量的铂和钯、以及呈10至25g/L的量的沸石化合物的柴油微粒过滤器。
14.一种处理柴油排气的方法,其特征在于使该柴油排气通过一种催化剂体系,该催化剂体系在该排气的流动方向上包含:
-一种含有氮氧化物存储组分和贵金属的氮氧化物存储催化剂,以及
-一种含有选自铂、钯、以及铂和钯的组的贵金属的柴油微粒过滤器,
其中该氮氧化物存储催化剂的贵金属装载量是100至180g/ft3(3.53至6.36g/L)并且该柴油微粒过滤器的贵金属装载量是5至35g/ft3(0.18至1.24g/L)。
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CN105188930B (zh) * | 2013-03-14 | 2018-04-03 | 巴斯夫公司 | 用于柴油应用的分区的催化剂 |
CN109069999A (zh) * | 2016-04-29 | 2018-12-21 | 庄信万丰股份有限公司 | 排气*** |
CN108404975A (zh) * | 2018-04-27 | 2018-08-17 | 中自环保科技股份有限公司 | 一种具有良好低温起燃性能的氧化型催化***及其制备工艺 |
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WO2014072067A1 (de) | 2014-05-15 |
KR102088152B1 (ko) | 2020-03-12 |
DE202013011730U1 (de) | 2014-04-03 |
JP2016502460A (ja) | 2016-01-28 |
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