CN102740953B - NOx捕集器 - Google Patents
NOx捕集器 Download PDFInfo
- Publication number
- CN102740953B CN102740953B CN201080059008.5A CN201080059008A CN102740953B CN 102740953 B CN102740953 B CN 102740953B CN 201080059008 A CN201080059008 A CN 201080059008A CN 102740953 B CN102740953 B CN 102740953B
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- rare earth
- trap
- catchment
- oxide
- upstream
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- 239000000758 substrate Substances 0.000 claims abstract description 47
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 41
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011232 storage material Substances 0.000 claims abstract description 11
- 238000002485 combustion reaction Methods 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000002912 waste gas Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- -1 magnesium aluminate Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 3
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- MXQGCMQXTPTJJT-UHFFFAOYSA-N 1-(2,3-dihydro-1,4-benzodioxin-3-ylmethyl)-3-hydroxythieno[3,2-d]pyrimidine-2,4-dione Chemical compound C1OC2=CC=CC=C2OC1CN1C(=O)N(O)C(=O)C2=C1C=CS2 MXQGCMQXTPTJJT-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 101150035458 lnt1 gene Proteins 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
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- 238000007906 compression Methods 0.000 description 5
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- 229910052760 oxygen Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
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- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 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
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ROLJWXCAVGNMAK-UHFFFAOYSA-N [Ce]=O Chemical compound [Ce]=O ROLJWXCAVGNMAK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
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- B01D53/34—Chemical or biological purification of waste gases
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- 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]
- B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
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- 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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- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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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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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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Abstract
一种NOx捕集器,包含包括至少一种铂族金属、至少一种NOx储存材料和大块氧化铈或大块含铈混合氧化物的成分,该成分均匀沉积于蜂窝状基材整料第一层,所述第一层的均匀沉积成分具有第一上游区和第二下游区,所述第一上游区相对于第二下游区具有提高的活性以氧化烃和一氧化碳,所述第二下游区相对于第一上游区而言具有提高的活性以在脱硫活动期间产生热,其中第二下游区包含分散的稀土氧化物,其中在第二下游区的以gin-3计的稀土氧化物负载量多于在第一上游区的稀土氧化物负载量。还公开了一种用于稀燃式内燃机的排气系统、一种包含稀燃式内燃机和排气系统的车辆和制备根据本发明的NOx捕集器的方法。
Description
本发明涉及构成内燃废气后处理系统的一部分的NOx捕集器的改进,并且更尤其涉及针对储存硫具有改进的再生能力的NOx捕集器。
现今,在用于稀燃式内燃机的废气后处理系统中使用内嵌NOx储存单元(通常被称作稀NOx捕集器,但如今更常被称作NOx捕集器或NOx吸附催化剂(NAC))是众所周知的。最早的专利公开可能是丰田(Toyota)的EP0560991,其描述了可如何通过将材料如氧化钡(其与NOx反应形成硝酸盐)与NOx转化催化剂如铂合并而构成NOx储存单元。通过将燃料/空气比(通常称作“拉姆达”或λ)调节至化学计量配比(λ=1)或富余(λ>1)来定期再生该捕集器,从而释放NOx并同时通过与催化剂接触而将其还原为氮气。
传统的NOx捕集器是通过将包括氧气储存成分(“OSC”)和催化成分的NOx捕集成分沉积到蜂窝状流通式基材整料上,并以相似的方式用废气催化剂涂覆蜂窝状基材整料而构成。我们之前已经公开过,至少在某些情况下,通过利用材料的选择层形成NOx捕集器可能是有利的。
本发明可应用于汽油、火花点火发动机,但对压缩点火发动机具有特别的相关性,所述压缩点火发动机通常被称为柴油机,虽然某些压缩点火发动机可以用其他燃料,例如天然气、生物柴油或混有生物柴油的柴油和/或Fischer-Tropsch燃料操作。压缩点火发动机以稀燃料/空气比操作,并具有良好的燃料经济性,但较汽油发动机而言,由于所得的稀废气而在NOx储存和转化方面存在更大的困难。汽油发动机通常接近于λ=1操作,并且虽然NOx转化较柴油发动机而言存在稍少的困难,但NOx捕集器上的硫堆积和由NOx捕集器的释放可能存在某些困难。
虽然柴油燃料目前通常被精制和配方为“低硫”或“极低硫”,但是该燃料以及由此得到的废气确实含有硫化合物。发动机中使用的润滑剂也能向废气贡献硫成分。通常含有氧化钡和作为氧气储存成分(“OSC”)的氧化铈的NOx捕集器通过反应有效但巧合地捕集硫化合物。这可被认为是硫“中毒”,或简单地说就是通过硫与NOx储存位点的竞争而降低了NOx捕集器的NOx储存能力。因为在车辆废气条件下硫酸钡比硝酸钡更稳定,不得不使用比已有的用于释放储存的NOx更强的(更富集、更持久和/或更热的废气温度)而定期除去硫。因此,NOx储存捕集器技术的发展水平包括硫释放活动,以维持NOx捕集器的效力。该活动是发动机的定期操作以使硫从NOx捕集器中释放,并通常包括升高NOx捕集器的温度同时频繁调节λ(“稀/富”转换),这可在NOx捕集器中引起放热。在该硫释放活动中NOx捕集器的温度通常升至至少550℃。
众多公司已经致力于改善硫从NOx捕集器的释放、集中于开始和终止硫的释放活动和对于硫的成功释放所必要的发动机管理。例如可参考US2009044518(PeugeotCitroenAutomobilesSA)。然而,并不认为所做的任何这种改进已经涉及NOx捕集器本身结构的改变。对于各成分均匀分布于其中的NOx捕集器的典型技术发展水平,达到硫释放所需温度的NOx捕集器前端(上游端)和达到该温度的NOx捕集器后端之间存在时间延迟。因此,实践中,将积聚硫从捕集器中移除,但往往在捕集器后端未充分脱硫。
发明人已经注意到沿NOx捕集器基材长度的温度传播是缓慢的。因此在脱硫活动期间,需要提高NOx捕集器下游部分的热产生,而非依赖于传统的来自捕集器前端的热转移。本发明的一个目的是实现一种改进的NOx捕集器,提供更有效释放捕集硫的能力和/或更少地需求脱硫活动。
本发明提供了一种NOx捕集器,包含包括至少一种铂族金属、至少一种NOx储存材料和大块氧化铈或大块含铈混合氧化物的成分,该成分均匀沉积于蜂窝状基材整料第一层,所述第一层的均匀沉积成分具有第一上游区和第二下游区,所述第一上游区相对于第二下游区而言具有提高的活性以氧化烃和一氧化碳,所述第二下游区相对于第一上游区而言具有提高的活性以在脱硫活动期间产生热,其中第二下游区包含分散的稀土氧化物,其中在第二下游区以gin-3计的稀土氧化物负载量多于在第一上游区的稀土氧化物负载量。
本文涉及到可还原氧化物例如氧化铈(或任何其它成分)所用的术语“大块(bulk)”指氧化铈以其固态颗粒存在。这些颗粒通常非常精细,达到至少90%的颗粒直径为约0.5-15微米的级别。术语“大块(bulk)”旨在与氧化铈“分散”在耐火支撑体材料上的情况相区别,所述“分散”通过从溶液例如硝酸铈溶液或该成分的某些其他分散液浸渍到支撑体材料和然后干燥并煅烧以将浸渍的硝酸铈转化为在耐火支撑体表面上氧化铈颗粒的分散体。从而所得氧化铈分散在耐火支撑体的表面层上,并或多或少地分散于耐火支撑体的表面层中。分散的氧化铈不以大块形式存在,因为大块氧化铈包含精细、固态的氧化铈颗粒。该分散体也可为溶胶形式,即例如纳米级氧化铈的精细分散颗粒。
GB2450578公开了一种包括两个独立基材的稀NOx捕集器系统,其中上游基材比下游基材具有更低的铈氧气储存成分和更低的铂族金属负载量。然而,GB’578中没有实施例研究主张将稀NOx捕集器系统中的总氧化铈负载量在上游基材和下游基材之间进行分割的好处。此外,其也没有明确对于稀NOx捕集器中的“铈”,作者是指“大块”氧化铈、分散的氧化铈还是两者。在本发明的NOx捕集器中,发明人已经发现存在均匀沉积于蜂窝状基材整料第一层的“大块”氧化铈或大块含铈混合氧化物提高了富NOx转化。将其移除,则富燃NOx转化率令人不快地降低。
US2004/0082470公开了一种两区NOx捕集器,其似乎被设计为主要用于汽油发动机,该NOx捕集器具有不含氧气储存成分的上游区和具有“少量锆和铈的混合氧化物”的下游区。出于上述讨论的原因,发明人相信在上游区中缺乏OSC,例如氧化铈将降低NOx捕集器的总体NOx还原活性。此外,在上游区的PGM负载量似乎比下游区的PGM多。
在实施方案中,稀土氧化物分散体可包含选自铈、镨、钕、镧、钐和其混合物的元素的氧化物。优选的稀土氧化物包括氧化铈和/或氧化镨,氧化铈是特别优选的。稀土氧化物体可以例如作为在NOx捕集器中的浸渍成分(其中NOx捕集器的一种或多种成分负载该稀土氧化物)或作为溶胶(纳米级稀土氧化物的精细分散颗粒)存在。
发明人已经注意到,存在例如分散的稀土氧化物如氧化铈会有损于例如Pt或PtPd/CeZrO2中对HC和CO的氧化。他们还注意到促进NOx储存的关键是从废气中移除HC和CO。作为该发现的结果,技术人员可能考虑将铂族金属以更高负载量放置在入口端。然而,这增加了成本却益处甚微。同样地,从第二下游区完全移除铂族金属也对总体NOx储存有害,因为总体NOx储存是对催化剂体积有依赖的,且需要铂族金属将NO氧化成NO2以促进NOx储存。因此,优选地,在第一上游区以gin-3计的稀土氧化物分散体的负载量为零。然而,在某些实施方案中,例如为了在包括连接着在地板下位置的NOx捕集器的紧密耦合柴油机氧化催化剂的废气系统中(参见下文)使用,稀土氧化物也可存在于第一上游区,但比第二下游区负载量低,例如为第二下游区中稀土氧化物分散体以gin-3计负载量的<30%,例如5-25%,<20%或10-20%。
通过定位大部分(如果非全部)的第二下游区中的稀土氧化物分散体,第一上游区的烃和一氧化碳氧化活性相对于第二下游区提高。另外,第二下游区中的稀土氧化物分散体增加了活性以产生热以在脱硫活动期间促进脱硫。并且,发明人相信稀土氧化物可产生氢气(例如通过水煤气变换),其也可使存在于NOx捕集器中的硫酸盐脱稳,从而也促进脱硫。
依赖于对汽车上使用最适宜的设置(例如最大废气温度、废气温度窗口(即从高到低的温度范围)、空速、排气系统中的位置(紧密耦合或地板下位置),就第一层长度而言,第一和第二区的比例可为20∶80-80∶20,优选30∶70-70∶30,特别是50∶50。
在进一步的实施方案中,在第一层中的均匀沉积成分中的铂族金属包括铂和/或钯。优选铂和钯的结合,因为钯降低铂发生烧结、损失表面积和活性的趋势。
大块氧化铈和含铈混合氧化物成分是可还原氧化物,具有氧气储存活性,即在废气环境中当废气富于化学计量λ设定点时它们释放氧气而当废气贫于化学计量λ设定点时从废气吸收氧气。与混合氧化物中的铈结合以提高大块铈氧化物水热稳定性的优选成分是锆,且依赖于所用的铈与锆的比例,任选地也可包括一种或多种稀土元素。
该或每个至少一种NOx储存材料可选自碱土金属和碱金属。合适的碱土金属包括钡、锶、钙和镁,且钡和/或锶是优选的。碱金属可选自钾、铯、钠和锂,且钾和/或铯是优选的。
为了提高NOx捕集器的水热稳定性,优选第一层中的均匀沉积成分包括铝酸镁。
为了在相对高的温度下提高NOx的还原并维持水热老化后NOx的还原,优选覆盖第一层的第二层包含负载的铑成分。铑载体可为氧化铝或氧化锆,任选地掺杂有一种或多种稀土元素。优选地,铑的载体或含铑载体涂层(washcoat)包括可还原氧化物例如氧化铈。在氧化铈不存在于铑载体中时,可例如以溶胶包含于载体涂层中。
为了进一步改进热管理,第二下游区可具有比第一上游区更低的热质量,例如可应用更低的载体涂层负载量。
蜂窝状基材整料可由陶瓷材料例如堇青石或碳化硅、或金属例如FecralloyTM制备。排列优先为所谓的流通式结构,其中多个通道由开放的入口端向开放的出口端平行延伸。然而,蜂窝状基材整料也可为过滤基材的形式,例如所谓的壁流式过滤器或陶瓷泡沫。
根据进一方面,本发明提供了一种用于稀燃式内燃机的排气系统,该排气系统包括根据本发明的NOx捕集器,其中第一上游区适用于在第二下游区前接收来自发动机的废气。当设置成所谓的紧密耦合位置,即在发动机排气歧管大约50cm以内以最大化热利用以促进催化活性时,根据本发明的NOx捕集器特有用。可供选择的、次优选的安排是将NOx捕集器放置于所谓的地板下位置,即悬于车辆底盘下,而柴油机氧化催化剂设置于地板下NOx捕集器的上游(任选地紧密耦合于发动机)。在后面的这种安排中,根据本发明理想的是也分散某些稀土氧化物在第一上游区。
根据另一方面,本发明提供了一种车辆,包括稀燃式内燃机和根据本发明的排气系统,其中发动机包括发动机管理系统,其设计成当发动机在使用时,间歇地将发动机的燃料/空气比由普通的稀燃运行模式(λ<1)调节至富燃运行模式(λ<1,λ=1或λ>1),以便释放不经意间储存在NOx捕集器上的硫。车辆的稀燃式内燃机优选为压缩点火发动机,例如柴油发动机,其也可用天然气、生物柴油或柴油和生物柴油的混合物和/或Fischer-Tropsch基燃料混合物做燃料。
根据进一方面,本发明提供了一种制备根据前述权利要求任一项的NOx捕集器的方法,该方法包括以下步骤:(a)用包含至少一种铂族金属、至少一种NOx储存材料和大块氧化铈或大块含铈混合氧化物的均匀载体涂层涂覆蜂窝状基材整料;(b)干燥和煅烧该涂覆的基材整料;(c)用稀土元素的水溶液浸渍该涂覆基材整料的第二区;或使该涂覆基材整料的第二区与稀土元素氧化物的溶胶接触;和(d)干燥和煅烧步骤(c)的涂覆基材整料。
在一个实施方案中,在步骤(c)和步骤(d)间插入额外的步骤,其中用稀土元素的水溶液浸渍涂覆基材整料的第一区;或使涂覆基材整料的第一区与稀土元素氧化物的溶胶接触,并且在每种情况下所得稀土氧化物以gin-3计的负载量(即排除大块氧化铈或大块含铈混合氧化物)在第一区为:(i)<30%的在第二区的稀土氧化物负载量;或(ii)>70%的在第二区的稀土氧化物负载量。
根据另一方面,本发明提供了一种制备根据本发明的NOx捕集器的方法,该方法包括以下步骤:(a)用包含至少一种铂族金属、至少一种NOx储存材料和大块氧化铈或大块含铈混合氧化物的载体涂层自第一端涂覆蜂窝状基材整料的第一区;(b)干燥和煅烧该部分涂覆的基材整料;(c)用包含至少一种铂族金属、至少一种NOx储存材料、大块氧化铈或大块含铈混合氧化物和稀土元素水溶液或稀土元素氧化物溶胶的载体涂层自其第二端涂覆该部分涂覆基材整料的第二区;和(d)干燥和煅烧步骤(c)的涂覆基材整料。
在一个实施方案中,步骤(a)的载体涂层包含稀土元素水溶液或稀土元素氧化物溶胶,其浓度导致稀土氧化物在第一上游区以gin-3计的负载量为:(i)<30%的在第二区的稀土氧化物的负载量;或(ii)>70%的在第二区的稀土负载量。
在任一种制备根据本发明的NOx捕集器的方法的实施方案中,进一步骤包括用包含负载铑成分的第二层涂覆该涂覆有第一层的基材整料并干燥和煅烧所得基材整料。
该第一和第二区可通过利用已知的催化剂和其他用于废气催化剂成分的差沉积技术(differentialdeposition)而容易地形成,例如使用申请人的WO99/47260,即包含步骤:(a)将容纳设备(containmentmeans)置于载体顶部,(b)将预定数量的液态成分定量给料至该容纳设备中,无论是以(a)然后(b)的顺序还是以(b)然后(a)的顺序,和(c)通过加压或真空,将所述液态成分吸入该载体的至少一部分,和保留基本上所有所述数量的液体成分在该载体内。
为了能够充分理解本发明,仅以阐明并参考附图的方式提供以下实施例,其中:
图1是显示重复SOx/deSOx循环导致的NOx转化率损失相对于进行脱硫活动次数的图,所述脱硫活动在500℃下、在合成催化活性测试装置上对两个双层稀NOx捕集器进行,其中一个含有存在于底层的氧化铈溶胶;和
图2为含有和不含有氧化铈溶胶的稀NOx捕集器的800℃老化的低层的CO转化的比较图。
实施例
实施例1——稀NO
x
捕集器的配方
用两层NOx捕集器配方涂覆一个每平方英寸400格的流通式堇青石基材整料,所述两层NOx捕集器配方包含第一低层和第二层,所述第一低层包含2gin-3的氧化铝、2gin-3的颗粒氧化铈、90gft-3的Pt、25gft-3的Pd和800gft-3的Ba,所述第二层包含0.5gin-3的掺杂稀土元素的85wt%氧化锆、10gft-3的Rh和400gft-3的氧化铈溶胶。使用WO99/47260中公开的方法将第一层涂覆于原始基材整料上,然后在强制空气干燥器中于100℃下干燥30分钟,然后于500℃下煅烧2小时,然后涂覆第二层并重复同样的干燥煅烧程序。该NOx捕集器标记为LNT1。
除了将400gft-3的氧化铈溶胶也加入到低层配方中以外,使用相同的程序制备LNT2。
实施例2——合成催化活性试验(SCAT)重复SO
x
/deSO
x
试验
从每个LNT1和LNT2上切下一块,使用合成催化活性试验(SCAT)装置轮流测试每块,所用条件如下:
1)在350℃的入口温度下,在300秒稀/20秒富之间循环
——5个循环无硫,以评价净NOx性能;和
——5个循环有硫,以硫酸盐化样品至2g/升
2)500℃下脱硫5分钟
50秒富/10秒稀之间循环
3)350℃下300秒稀/20秒富
——5循环无硫,以评价脱硫的NOx性能;和
——5循环有硫,以硫酸盐化至2g/l
4)重复
所用气态条件显示于表1。
表1
重复硫酸盐化/脱硫循环的结果和其对NOx转化率的影响示于图1,由图1可见重复脱硫之后,LNT1比LNT2保持了更大的NOx转化活性。也就是说,LNT1的低层中额外分散的氧化铈的存在有助于在重复SOx/deSOx循环之后保持NOx的转化率。发明人从这一观察推断分散的氧化铈有助于脱硫,其在脱硫活动期间通过产生放热和/或氢气,从而有助于使NOx捕集器脱硫。
实施例3——NO
x
捕集器低层CO氧化活性
将在实施例1中描述的干燥煅烧后制备的仅涂覆有LNT1和LNT2的底层的基材整料在800℃下、10%H2O、10%O2、剩余为N2中老化5小时。通过移除现有NOx捕集器并用LNT1(低层)或LNT2(低层)基材整料替换,在实验室台式安装的1.9升Euro4柴油发动机上试验每个基材整料。
选择1200rpm的发动机速度,变化发动机扭矩以实现所需的催化剂入口温度。催化剂入口温度达350℃时开始评价。调整发动机扭矩以使入口温度降至<150℃,足以实现一氧化碳氧化“点亮”(lightout)。实践中这通过将发动机扭矩用10分钟时间由100Nm降至5Nm而实现。“点亮”之后,将发动机扭矩以约7℃/min的速度升回350℃以实现一氧化碳氧化“熄火”(lightoff)。废气组成、质量流速、温度等全部由车辆测功机监控。
该试验程序的CO转化(%)结果显示于图2,由图2可见在<150℃点亮之后,当试验升至约165℃时催化剂的CO氧化活性重新“熄火”,并且LNT1低层的CO转化活性在整个试验期间从未降至80%以下。然而,LNT2低层(其除了其他LNT1载体涂层成分外还含有氧化铈溶胶)的CO转化活性在<150℃点亮之后,直至约180℃催化剂未能重新熄灭至与LNT1低层相似的程度,并且CO转化效率降至50%以下。
实施例1、2和3的结果共同显示了对于包含负载于氧化铝和大块氧化铈上的Pt、Pd、和钡NOx储存成分的稀NOx捕集器,分散氧化铈的存在既对CO转化活性有害,又对脱硫有益。通过将分散氧化铈分区到载有NOx捕集器的基材整料的后端,获得了功能的有利结合。
为了避免任何疑问,本文涉及的每个专利文件的全文在此引入作为参考。
Claims (18)
1.一种NOx捕集器,包含包括至少一种铂族金属、至少一种NOx储存材料和大块氧化铈或大块含铈混合氧化物的成分,该成分均匀沉积于蜂窝状基材整料第一层,所述第一层还包含稀土氧化物分散体,所述第一层的均匀沉积成分具有第一上游区和第二下游区,所述第一上游区相对于第二下游区具有提高的活性以氧化烃和一氧化碳,所述第二下游区相对于第一上游区具有提高的活性以在脱硫酸盐化活动期间产生热,其中第二下游区包含稀土氧化物分散体,其中在第二下游区以gin-3计的稀土氧化物分散体负载量多于在第一上游区的稀土氧化物分散体负载量,其中大块氧化铈或大块含铈混合氧化物指其以固态颗粒存在,其中至少90%的所述固态颗粒直径为0.5-15微米的级别,稀土氧化物分散体为纳米级的精细分散颗粒。
2.根据权利要求1的NOx捕集器,其中稀土氧化物分散体包括选自铈、镨、钕、镧、钐和其混合物的元素的氧化物。
3.根据权利要求1或2的NOx捕集器,其中在第一上游区中以gin-3计的稀土氧化物分散体的负载量为第二下游区中稀土氧化物分散体负载量的0-30%。
4.根据权利要求1或2的NOx捕集器,其中就第一层长度而言,第一上游区和第二下游区的比例为20:80-80:20。
5.根据权利要求1或2的NOx捕集器,其中第一层中均匀沉积成分中的铂族金属包括铂和/或钯。
6.根据权利要求1或2的NOx捕集器,其中大块含铈混合氧化物还包括锆和任选的一种或多种稀土元素。
7.根据权利要求1或2的NOx捕集器,其中所述NOx储存材料选自碱土金属和碱金属。
8.根据权利要求1或2的NOx捕集器,其中第一层中均匀沉积成分包含铝酸镁。
9.根据权利要求1或2的NOx捕集器,其中覆盖第一层的第二层包含负载的铑成分。
10.根据权利要求1或2的NOx捕集器,其中第二下游区具有比第一上游区低的热质量。
11.根据权利要求1或2的NOx捕集器,其中蜂窝状基材整料为流通式蜂窝状基材整料。
12.一种用于稀燃式内燃机的排气系统,其中排气系统包含根据前述权利要求任一项的NOx捕集器,其中第一上游区适用于在第二下游区前接收来自发动机的废气。
13.一种车辆,包括稀燃式内燃机和根据权利要求12的排气系统,其中发动机包括发动机管理设备,其设计成当发动机在使用时,间歇地将发动机的燃料/空气比由普通的稀燃运行模式调节至富燃运行模式,以便释放不经意间储存在NOx捕集器上的硫。
14.一种制备根据前述权利要求1-11任一项的NOx捕集器的方法,该方法包括以下步骤:
(a)用包含至少一种铂族金属、至少一种NOx储存材料和大块氧化铈或大块含铈混合氧化物的均匀载体涂层涂覆蜂窝状基材整料;
(b)干燥和煅烧该涂覆的基材整料;
(c)用稀土元素的水溶液浸渍该涂覆基材整料的第二下游区;或使该涂覆基材整料的第二下游区与稀土元素氧化物的溶胶接触;和
(d)干燥和煅烧步骤(c)的涂覆的基材整料。
15.根据权利要求14的方法,其中在步骤(c)和步骤(d)之间,用稀土元素的水溶液浸渍涂覆基材整料的第一上游区;或使涂覆的基材整料的第一上游区与稀土元素氧化物的溶胶接触,并且在每种情况下所得稀土氧化物在第一上游区的以gin-3计的负载量为:(i)<30%的在第二下游区的稀土氧化物的负载量;或(ii)>70%的在第二下游区的稀土氧化物的负载量。
16.一种制备根据权利要求1-11任一项的NOx捕集器的方法,该方法包括以下步骤:
(a)用包含至少一种铂族金属、至少一种NOx储存材料和大块氧化铈或大块含铈混合氧化物的载体涂层自第一端涂覆蜂窝状基材整料的第一上游区;
(b)干燥和煅烧该部分涂覆的基材整料;
(c)用包含至少一种铂族金属、至少一种NOx储存材料、大块氧化铈或大块含铈混合氧化物和稀土元素水溶液或稀土元素氧化物溶胶的载体涂层自第二端涂覆该部分涂覆的基材整料的第二下游区;和
(d)干燥和煅烧步骤(c)的涂覆基材整料。
17.根据权利要求16的方法,其中步骤(a)的载体涂层包含稀土元素水溶液或稀土元素氧化物溶胶,其浓度导致在第一上游区的稀土氧化物以gin-3计的负载量为:(i)<30%的在第二下游区的稀土氧化物的负载量;或(ii)>70%的在第二下游区的稀土氧化物的负载量。
18.根据权利要求14、15、16或17的方法,包括用包含负载的铑成分的第二层涂覆涂有第一层的基材整料并干燥和煅烧所得基材整料的步骤。
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EP (1) | EP2516043A1 (zh) |
JP (1) | JP5735983B2 (zh) |
KR (1) | KR101838558B1 (zh) |
CN (1) | CN102740953B (zh) |
BR (1) | BR112012015195A2 (zh) |
DE (1) | DE102010063805A1 (zh) |
GB (2) | GB0922195D0 (zh) |
RU (1) | RU2554576C2 (zh) |
WO (1) | WO2011077139A1 (zh) |
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WO2011077139A1 (en) | 2011-06-30 |
GB2476573A (en) | 2011-06-29 |
US20170043322A1 (en) | 2017-02-16 |
JP5735983B2 (ja) | 2015-06-17 |
CN102740953A (zh) | 2012-10-17 |
GB201021604D0 (en) | 2011-02-02 |
GB2476573B (en) | 2014-04-09 |
BR112012015195A2 (pt) | 2021-06-01 |
JP2013514881A (ja) | 2013-05-02 |
EP2516043A1 (en) | 2012-10-31 |
GB0922195D0 (en) | 2010-02-03 |
KR20120116965A (ko) | 2012-10-23 |
US20110154807A1 (en) | 2011-06-30 |
KR101838558B1 (ko) | 2018-03-14 |
DE102010063805A1 (de) | 2011-09-01 |
RU2554576C2 (ru) | 2015-06-27 |
RU2012131133A (ru) | 2014-01-27 |
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