CN103974768B - 包含scr催化剂的基底整料 - Google Patents
包含scr催化剂的基底整料 Download PDFInfo
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- CN103974768B CN103974768B CN201280060777.6A CN201280060777A CN103974768B CN 103974768 B CN103974768 B CN 103974768B CN 201280060777 A CN201280060777 A CN 201280060777A CN 103974768 B CN103974768 B CN 103974768B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 172
- 239000000758 substrate Substances 0.000 title claims abstract description 133
- 239000000463 material Substances 0.000 title claims abstract description 117
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 137
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000007789 gas Substances 0.000 claims abstract description 76
- 239000002184 metal Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 27
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000002912 waste gas Substances 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 238000005275 alloying Methods 0.000 claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 64
- 238000000605 extraction Methods 0.000 claims description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 29
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- 238000002485 combustion reaction Methods 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 23
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 14
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- 238000012360 testing method Methods 0.000 description 14
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 11
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- 239000013618 particulate matter Substances 0.000 description 8
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- 239000000446 fuel Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 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 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VPGRYOFKCNULNK-ACXQXYJUSA-N Deoxycorticosterone acetate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)COC(=O)C)[C@@]1(C)CC2 VPGRYOFKCNULNK-ACXQXYJUSA-N 0.000 description 2
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- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
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- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
-
- 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
-
- 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
-
- 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
-
- 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
- B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
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Abstract
基底整料(6),其具有长度L并且包括在一端由该基底整料的第一端限定的基本均匀长度的第一区(11),该第一区包含用于将从内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原的选择性催化还原(SCR)催化剂,和在一端由该基底整料第二端限定的基本均匀长度小于L的第二区(8),该第二区包含:(a)用于捕集气相铂族金属(PGM)的至少一种颗粒状金属氧化物或其任意两种或更多种的混合物,该至少一种颗粒状金属氧化物不充当用于任何其他催化组分的载体;或者(b)能够捕集和/或与气相PGM合金化的组分。
Description
发明领域
本发明涉及基底整料,其包含用于将从内燃机例如车辆内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原的选择性催化还原(SCR)催化剂,该基底整料经设计以减少或避免由会从上游的含PGM催化剂中挥发的铂族金属(PGM)特别是铂造成的SCR催化剂的污染,以及因此的NOx转化活性的损失。
发明背景
通常,有四类污染物被全世界的政府间组织立法限制:一氧化碳(CO),未燃的烃(HC),氮的氧化物(NOx)和颗粒物质(PM)。
随着对来自车辆发动机的废气中污染物的可容许排放的排放标准越来越严格,提出和研发了发动机管理和多重催化剂废气后处理***的组合以满足这些排放标准。对于包括颗粒过滤器的排气***,通常定期(例如每隔500km)进行发动机管理以提高过滤器中的温度以燃烧掉保持在该过滤器上的基本上所有剩余的烟灰,由此将该***返回基线水平。这些经过发动机管理的烟灰燃烧事件经常称作“过滤器再生”。尽管过滤器再生的主要焦点是燃烧保持在该过滤器上的烟灰,但未曾预期的结果是根据该***中发动机管理的水平,排气***中存在的一个或多个催化剂涂层(例如过滤器(所谓的催化烟灰过滤器(CSF))本身的过滤涂层)、位于过滤器上游或下游的氧化催化剂(例如柴油机氧化催化剂(DOC))或NOx吸附催化剂(NAC)(例如第一DOC之后是柴油颗粒过滤器,之后又是第二DOC,最后是SCR催化剂)能够定期暴露于高废气温度。这些条件也可能经历未曾预期的偶然的发动机不正常模式(upsetmode)或不受控制或控制不良的再生事件。然而,一些柴油发动机(特别是以高负荷操作的重型柴油发动机)甚至可以在正常操作条件下将催化剂暴露于高温(例如>600℃)。
因为车辆制造商研发其发动机和发动机管理***以满足排放标准,本申请人/受让人被车辆制造商要求提出催化组分和催化组分的组合,以帮助满足排放标准的目标。这些组分包括用于氧化CO、HC而且任选也氧化NO的DOC;用于氧化CO、HC、任选也氧化NO并用于捕集颗粒物质用于随后燃烧的CSF;用于氧化CO和HC并用于氧化一氧化氮(NO)和将其从贫燃废气中吸收并解吸吸附的NOx并将其在富废气中还原成N2的NAC(见下面);和用于在含氮还原剂(例如氨)存在下将NOx还原成N2的选择性催化还原(SCR)催化剂(见下面)。
在实践中,DOC和CSF中使用的催化剂组合物是非常相似的。然而,通常DOC和CSF的使用之间的主要差异是该催化剂组合物所涂覆的基底整料:在DOC的情况中,该基底整料通常是流通式基底整料,包括具有延伸贯通的细长通道阵列的金属或陶瓷蜂窝状整料,该通道在两端都开口;CSF基底整料是过滤器整料例如壁流式过滤器,例如陶瓷多孔过滤器基底,其包括与多个出口通道平行排列的多个入口通道,其中各入口通道和各出口通道部分地由多孔结构的陶瓷壁限定,其中各入口通道与出口通道通过多孔结构的陶瓷壁交替隔开,反之亦然。换言之,壁流式过滤器是蜂窝状布置,限定了多个在上游端堵塞的第一通道和多个在上游端未堵塞但在下游端堵塞的第二通道。与第一通道垂直和横向相邻的通道在下游端堵塞。当从任一端观察时,通道的交替地堵塞和开口的端呈现棋盘的外观。
在流通式基底整料上可以涂覆非常复杂的多层催化剂布置,例如DOC和NAC。尽管可以用多于一层的催化剂组合物涂覆过滤器整料的表面(例如壁流式过滤器的入口通道表面),但涂覆过滤器整料的问题是要避免在使用时通过用催化剂活化涂层过度加载该过滤器整料而不必要地提高背压,由此限制气体流通。因此,尽管用一种或多种不同的催化剂层顺序涂覆过滤器基底整料的表面并不是不可能的,但更通常地将不同的催化剂组合物分割成区,例如过滤器整料的轴向分隔的前半区和后半区,或者通过用第一催化剂组合物涂覆壁流式过滤器基底整料的入口通道,用第二催化剂组合物涂覆其出口通道。然而,在本发明的具体实施方案中,用一个或多个可以是相同或不同催化剂组合物的层涂覆过滤器入口。还提出了在过滤基底整料上涂覆NAC组合物(例如参见EP0766993)。
在包含多种催化剂组分的排气***(均包括单独的基底整料)中,通常SCR催化剂位于DOC和/或CSF和/或NAC的下游,因为已知通过将废气中的一些氧化氮(NO)氧化成二氧化氮(NO2),使得离开DOC和/或CSF和/或NAC的NO:NO2比为约1:1,促进了下游的SCR反应(见下面)。从EP341832(所谓的连续再生捕集器或)中还公知,通过将废气中的NO氧化成NO2而产生的NO2能够用于在下游过滤器上被动燃烧烟灰。在EP341832的方法重要的排气***布置中,如果SCR催化剂位于过滤器的上游,那么这将会减少或阻止捕集的烟灰在NO2中燃烧的过程,因为用于燃烧烟灰的NOx的大部分将很可能在SCR催化剂上除去。
然而,轻型柴油车辆优选的***布置是柴油机氧化催化剂(DOC)之后是含氮还原剂喷射器,然后是SCR催化剂,最后是催化烟灰过滤器(CSF)。这种布置的简称为“DOC/SCR/CSF”。这种布置优选用于轻型柴油车辆,因为重要的考虑是在车辆发动机启动之后在排气***中尽可能快地实现NOx转化,以确保(i)将含氮还原剂(例如氨)的前体喷射/分解以释放氨用于NOx转化;和(ii)尽可能高的NOx转化率。如果将大热质量过滤器放在SCR催化剂上游(即DOC和SCR催化剂之间)(“DOC/CSF/SCR”),(i)和(ii)的过程将会花费长得多的时间实现,且对于整个排放标准加州周期的NOx转化率将会降低。可以使用氧和采用发动机管理技术对过滤器的偶尔强制再生来实现颗粒物质去除。
已经提出将SCR催化剂活化涂层涂覆到过滤基底整料自身上(例如参见WO2005/016497),在这种情况中,氧化催化剂可以位于涂覆有SCR的过滤器基底上游(无论该氧化催化剂是否DOC、CSF或NAC的组分),以改进NO/NO2比用于提高SCR催化剂上的NOx还原活性。还已经提出将NAC设置在位于流通式基底整料上的SCR催化剂的上游,该NAC能够在NAC再生过程中原位产生NH3(见下面)。GB2375059中公开了一种该提议。
NAC是例如从US5,473,887已知的,且经设计以从贫废气(λ>1)中吸附NOx并在废气中氧浓度降低时解吸该NOx。解吸的NOx可以用合适的还原剂(例如发动机燃料)还原成N2,通过NAC自身或位于NAC下游的催化剂组分(例如铑)进行促进。在实践中,能够间歇地根据计算的NAC剩余的NOx吸附容量将对氧浓度的控制调节到所需的氧化还原组成,例如比正常发动机运行操作更富燃(但仍贫于化学计量的或λ=1的组成)、化学计量的或富于化学计量的(λ<1)。氧浓度可以通过多种手段调节,例如节流、将另外的烃燃料注入发动机气缸(例如在排气冲程过程中)或将烃燃料直接注入发动机集管下游的废气。
典型的NAC配方包含催化氧化组分(例如铂)、显著量(即充分大于作为助剂(例如三效催化剂中的助剂)所需的量)的NOx储存组分(例如钡)和还原催化剂(例如铑)。对于该配方来说,用于从贫废气中储存NOx通常的机理为:
NO+1/2O2→NO2(1);和
BaO+2NO2+1/2O2→Ba(NO3)2(2),
其中在反应(1)中,一氧化氮与氧气在铂上的活性氧化位上反应生成NO2。反应(2)包括由储存材料以无机硝酸盐的形式来吸附NO2。
在较低的氧浓度和/或升高的温度时,该硝酸盐物类变得热力学不稳定并分解,依照下面的反应(3)生成NO或NO2。在适合的还原剂存在下,这些氮氧化物随后被一氧化碳、氢和烃还原成N2,这可以在还原催化剂上发生(参见反应(4))。
Ba(NO3)2→BaO+2NO+3/2O2或Ba(NO3)2→BaO+2NO2+1/2O2(3);和
NO+CO→1/2N2+CO2(4);
(其他反应包括Ba(NO3)2+8H2→BaO+2NH3+5H2O,然后
NH3+NOx→N2+yH2O或2NH3+2O2+CO→N2+3H2O+CO2等)。
在本文上面包括的反应(1)-(4)中,活性钡物类作为氧化物提供。然而,应当理解在空气存在下,大部分钡为碳酸盐或者可能为氢氧化物的形式。技术人员能够调整由此对于除氧化物之外的其他钡物类的上述反应方案和废气流中催化涂层的顺序。
氧化催化剂促进CO氧化为CO2和未燃烧的HC氧化为CO2和H2O。典型的氧化催化剂包括在高表面积载体上的铂和/或钯。
SCR技术用于处理车辆内燃(IC)发动机(特别是贫燃IC发动机)的NOx排放的应用是公知的。可以用于SCR反应中的含氮还原剂的实例包括化合物例如氮氢化物,例如氨(NH3)或肼或NH3前体。
NH3前体是能够例如通过水解得到NH3的一种或多种化合物。前体分解为氨和其他副产物能够通过水热或催化水解进行。NH3前体包括作为水溶液或者作为固体的尿素(CO(NH2)2)或者氨基甲酸铵(NH2COONH4)。如果使用作为水溶液的尿素,优选低共熔混合物,例如32.5%NH3(含水)。在该水溶液中可以包括添加剂以降低结晶温度。目前,尿素是用于移动应用的优选NH3源,因为它毒性比NH3低,它易于运输和处理,它廉价且通常可获得。在为满足相关的排放测试循环的测试中,尿素的不完全水解可以导致PM排放提高,因为部分水解的尿素固体或液滴将被PM的立法集管测试所用的滤纸捕获并计入PM质量。进一步地,不完全的尿素水解的某些产物(例如氰尿酸)的释放在环境上是不适宜的。
SCR具有三个主要反应(示于下面包括的反应(5)-(7)中),其将NOx还原为单质氮。
4NH3+4NO+O2→4N2+6H2O(即1:1NH3:NO)(5)
4NH3+2NO+2NO2→4N2+6H2O(即1:1NH3:NOx)(6)
8NH3+6NO2→7N2+12H2O(即4:3NH3:NOx)(7)
相关不适宜的非选择性副反应为:
2NH3+2NO2→N2O+3H2O+N2(8)
实践中,反应(7)与反应(5)相比比较慢,反应(6)是所有中最快的。因此,当技术人员设计车辆废气后处理***时,他们经常优先将氧化催化剂元件(例如DOC和/或CSF和/或NAC)设置在SCR催化剂的上游。
当某些DOC和/或NAC和/或CSF暴露于例如在过滤器再生和/或发动机不正常情况期间遇到的高温和/或(在某些重型柴油机应用中)正常的高温废气时,可以提供高温的足够时间使低含量的铂族金属组分(特别是Pt)从DOC和/或NAC和/或CSF组分中挥发出来,并随后使该铂族金属捕集在下游的SCR催化剂上。这会对SCR催化剂的性能具有高度有害的影响,因为Pt的存在导致对竞争性的非选择性氨氧化例如反应(9)中的氨氧化(其显示了NH3的完全氧化)具有高活性,由此产生二级排放和/或无谓消耗NH3。
4NH3+5O2→4NO+6H2O(9)
一个车辆制造商在SAEpaper2009-01-0627中报道了对该现象的观察,其名称为“ImpactandPreventionofUltra-LowContaminationofPlatinumGroupMetalsonSCRcatalystsDuetoDOCDesign”且包括了串联位于四个供应商的含铂族金属(PGM)的DOC之后的Fe/沸石SCR催化剂在与流动模型废气在850℃接触16小时的NOx转化活性与温度的比较数据。所呈现的数据显示设置在总PGM为70gft-3的20Pt:PdDOC之后的Fe/沸石SCR催化剂的NOx转化活性在较高的评价温度时与较低的评价温度相比有不利的变化,这是由Pt污染所导致的。还测试了总PGM为105gft-3的来自不同供应商的两种2Pt:PdDOC。在第一种2Pt:PdDOC中,对SCR催化剂活性的影响程度与对20Pt:PdDOC测试的程度相似,而对于第二种测试的2Pt:PdDOC,SCR催化剂活性污染程度较低,不过第二种2Pt:PdDOC与空白对照样(无DOC,仅为裸露的基底)相比还是显示出降低的NOx转化活性。作者总结道,显示出更缓和的NOx转化率降低的第二种2Pt:PdDOC的供应商在用35gft-3Pd来稳定所存在的70gft-3Pt方面更成功。150gft-3的仅含Pd的DOC证实与空白对照样相比对下游的SCR没有影响。SAE2009-01-0627作者的早期工作公开在SAEpaperno.2008-01-2488中。
发明内容
车辆制造商已经开始要求申请人提供方法来解决来自SCR催化剂上游的组分的相对低含量PGM的挥发问题。非常希望研发出策略来防止这种PGM在高温向下游SCR催化剂上的移动。本发明人已经研发了多种策略来满足这种需要。
本发明人已经发现,在极端温度条件下会发生铂从包含铂和钯的含PGM的催化剂的挥发。例如在一些实施方案中,Pt的挥发会在Pt:Pd重量比大于约2:1时发生。还据信,在PGM由铂组成的情况下,也可以观察到铂的挥发。本发明人已经设计了包含SCR催化剂的基底整料和包括该基底整料的排气***,其避免或减少了PGM(特别是Pt)从上游相对高负载的Pt催化剂向下游SCR催化剂的迁移问题。
根据第一方面,本发明提供了一种基底整料,其具有长度L并且包括在一端由该基底整料的第一端限定的基本均匀长度的第一区,该第一区包含用于将从内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原的选择性催化还原(SCR)催化剂,和在一端由该基底整料的第二端限定的基本均匀长度小于L的第二区,该第二区包含:(a)用于捕集气相铂族金属(PGM)的至少一种颗粒状金属氧化物或其任意两种或更多种的混合物,该至少一种颗粒状金属氧化物不充当用于任何其他催化组分的载体;或者(b)能够捕集和/或与气相PGM合金化的组分。该基底整料的第一区或第一端通常与该基底整料的第二区或第二端不同。
根据另一方面,本发明提供一种用于车辆贫燃内燃机的排气***,该***包括本发明的基底整料,和其中将该基底整料的第二区和/或第二端取向为上游侧(例如将该基底整料的第一区和/或第一端取向为下游侧)。典型地,该排气***进一步包括催化基底整料,其中该催化基底整料包含含铂催化剂,和其中该催化基底整料和/或该铂位于本发明的基底整料的上游。
本发明进一步提供一种包括本发明的排气***的贫燃内燃机。该贫燃内燃机可以是压缩点火发动机。
根据另一方面,提供了一种车辆,其包括本发明的排气***。典型地,该车辆进一步包括发动机(例如内燃机),例如贫燃内燃机,特别是压缩点火发动机。
另一方面,提供一种减少或防止铂族金属使选择性催化还原(SCR)催化剂中毒的方法,该选择性催化环氧催化剂用于在贫燃内燃机的排气***中将从内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原,该铂族金属(PGM)存在于贫燃内燃机排气***的催化基底整料上,并且典型地在使用时易于挥发和迁移到包含SCR催化剂的基底整料的表面,其中包含SCR催化剂的基底整料位于催化基底整料的下游,该基底整料具有长度L并且包括在一端由该基底整料的第一端限定的基本均匀长度的第一区,该第一区包含用于将从内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原的选择性催化还原(SCR)催化剂,和在一端由该基底整料的第二端限定的基本均匀长度小于L的第二区,该第二区包含:(a)用于捕集气相PGM的至少一种颗粒状金属氧化物或其任意两种或更多种的混合物,该至少一种颗粒状金属氧化物不充当用于任何其他催化组分的载体;或者(b)能够捕集和与气相PGM合金化的组分,并且其中第二区经取向为在第一区之前与离开该催化基底整料的废气接触,该方法包括在第二区中捕集和/或合金化PGM。
本发明的另一方面涉及颗粒状金属氧化物(例如至少一种颗粒状金属氧化物或其任意两种或更多种的混合物)或者能够捕集和/或与气相铂族金属(PGM)合金化的组分的用途,该用途用于典型地在贫燃内燃机的排气***中减少或防止选择性催化还原(SCR)催化剂被铂族金属(PGM)中毒,其中该排气***包括基底整料,该基底整料具有长度L并且包括在一端由该基底整料的第一端限定的基本均匀长度的第一区,该第一区包含用于将从内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原的选择性催化还原(SCR)催化剂,和在一端由该基底整料的第二端限定的基本均匀长度小于L的第二区,该第二区包含:(a)用于捕集气相铂族金属(PGM)的颗粒状金属氧化物,和优选该颗粒状金属氧化物不充当用于任何其他催化组分的载体;或者(b)能够捕集和/或与气相PGM合金化的组分。典型地,将该基底整料的第二区和/或第二端取向为上游侧(例如将该基底整料的第一区和/或第一端取向为下游侧)。
附图说明
为了可以更充分地理解本发明,仅通过示例的方式参考以下实施例并参考附图。
图1是根据本发明的一种排气***的示意图。
图2是一种实验室反应器的示意图,其用于测试Fe/β沸石SCR催化剂或Cu/CHA沸石SCR催化剂上的铂污染。
图3的图比较了三个老化的SCR催化剂芯的作为温度函数的NOx转化活性,其每个已经在实验室规模的排气***构造中进行了老化,该构造中含有位于实施例1的Fe/β沸石SCR催化剂上游的催化壁流式过滤器,一种***,其包括在入口和出口通道上涂覆有实施例3的1:1重量比的Pt:Pd的过滤器;第二***,其包括在入口和出口通道上涂覆有实施例4的5:1重量比的Pt:Pd的过滤器;和第三对比***,其包括在入口和出口通道上涂覆有对比例2的仅Pt催化剂的过滤器。将经老化的SCR活性的结果相对于新鲜的即未老化的SCR催化剂的活性进行作图。
图4的条形图比较了两个老化的SCR催化剂芯的作为温度函数的NOx转化活性,其每个已经在图1所示的实验室规模的排气***中进行了老化,该***含有在900℃管式炉中在流动的合成废气中加热2小时的对比例3和实施例4的柴油机氧化催化剂的芯样品,并且具有位于下游的保持在300℃的Cu/CHA沸石SCR催化剂芯。
具体实施方式
典型地,颗粒状金属氧化物(即,(a)的至少一种颗粒状金属氧化物)可以选自任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛、任选稳定化的二氧化铈-氧化锆混合氧化物及其任意两种或更多种的混合物。这里用“不充当用于任何其他催化组分的载体”来表示该至少一种颗粒状金属氧化物不负载包含碱金属、碱土金属或过渡金属(包括镧系元素)或者周期表的IIIA、IVA、VA或VIA族(根据ChemicalAbstractsService(c.1999))的任何催化剂组合物。
第二区可以典型地包含总量为0.1-5gin-3,优选0.2-4gin-3(例如0.5-3.5gin-3),更优选1-2.5gin-3的颗粒状金属氧化物。
能够捕集和/或与气相PGM合金化的组分(例如组分(b))典型地包括选自金、钯和银的金属。优选组分(b)包括钯和金的混合物或合金。
典型地,组分(b)的总量是10-350gft-3。优选组分(b)的总量是20-300gft-3,更优选30-250gft-3,仍然更优选45-200gft-3和甚至更优选50-175gft-3。
基底整料中的第二区和包含SCR催化剂的第一区可以以多种不同方式来布置。例如,第一区可以在整个长度L上延伸,第二区可以叠加在第一区上。SCR催化剂可以是挤出类型(有时候也称作“催化剂体”),或者是施涂到惰性基底整料上的涂层。能够捕集和与气相铂合金化的组分(b)例如钯、金、银或者钯和金可以由SCR催化剂本身负载,或者组分(b)包含其上负载了该能够捕集和与气相PGM合金化的组分的至少一种金属氧化物。例如从EP1399246中已知以下方法:用PGM浸渍SCR催化剂以形成用于将滑逸过SCR催化剂的NH3选择性氧化成二氮的区,反之亦然。
在第二区包含涂层的情况下,该区通常作为包含载体材料的活化涂层来施用。本领域已知的载体材料包括任选稳定化的氧化铝、二氧化钛、二氧化铈、任选稳定化的氧化锆、含有二氧化铈的混合氧化物例如二氧化铈-氧化锆(其可能用一种或多种稀土元素来进一步稳定)、二氧化硅、无定形二氧化硅氧化铝等。
用于本发明的基底整料可以是陶瓷的,例如堇青石、钛酸铝、碳化硅等;或者金属的,例如由铁素体铁-铬-铝合金的薄金属箔制成。这种基底整料的布置可以是非过滤的,例如所谓的流通式整料,其中开口的通道从第一端延伸到第二端,或者可以使用具有入口表面和出口表面的过滤基底整料,其中该入口表面通过多孔结构与该出口表面隔开。优选的过滤基底整料是壁流式过滤器,如上文所述。
催化过滤器(优选壁流式过滤器)可以使用申请人/受让人的WO2011/080525中公开的方法涂覆。即,用包含催化剂组分的液体涂覆包括多个通道的蜂窝整料基底的方法,该方法包括以下步骤:(i)将蜂窝状整料基底基本上保持竖直;(ii)将预定体积的液体经由基底下端的通道的开口端引入该基底中;(iii)将引入的液体密封保持在该基底内;(iv)将包含所保持的液体的基底倒置;和(v)在该基底的倒置的下端对基底的通道的开口端施加真空,以沿该基底的通道抽取该液体。催化剂组合物可以从第一端涂覆到过滤器通道上,然后可以干燥经涂覆的过滤器。
这种方法的应用可以使用例如真空强度、真空持续时间、活化涂层粘度、活化涂层固体、涂料颗粒或者聚集体尺寸和表面张力来控制,以使得催化剂主要涂覆在入口表面上,以及任选地涂覆在多孔结构内但接近于入口表面。替代地,可以将活化涂层组分研磨到例如D90<5μm的尺寸,以使得它们“透过”过滤器的多孔结构(参见WO2005/016497)。
作为此处使用的,术语“基本均匀长度”指的是相对于层长度的平均值偏离不超过10%的层长度,优选偏离不超过5%,更优选偏离不超过1%。
当基底整料包含(a)或(b)时,第一区中的SCR催化剂可以作为基底整料上基本均匀长度小于L的涂层而存在。典型地,包含(a)或(b)的第一区和第二区之间基本没有重叠。优选组分(b)包含至少一种金属氧化物,其上负载有能够捕集和与气相PGM合金化的组分。
当基底整料是壁流式过滤器时,SCR催化剂可以位于该壁流式过滤器的第一端的开口通道中,和第二区位于该壁流式过滤器的第二端的开口通道中,其中该多孔结构限定了第一活化涂层区和第二活化涂层区之间的过渡区。
根据本发明的基底整料包含用于将氮的氧化物用含氮还原剂选择性催化还原成二氮的催化剂,其也称作选择性催化还原(SCR)催化剂。SCR催化剂可以作为涂层涂覆于基底整料上,如上文所述。替代地,SCR催化剂作为挤出物(也称作“催化剂体”)提供,即将催化剂与基底整料结构的组分混合,将二者挤出,以使得该催化剂是基底整料壁的一部分。还可以由挤出SCR催化剂来制备壁流式过滤器(参见申请人/受让人的WO2009/093071和WO2011/092521)。用于本发明的SCR催化剂可以选自以下的至少一种:Cu、Hf、La、Au、In、V、镧系元素和VIII族过渡金属例如Fe,其负载在难熔氧化物或者分子筛上。特别关注的优选金属选自Ce、Fe和Cu。合适的难熔氧化物包括Al2O3、TiO2、CeO2、SiO2、ZrO2和含有其两种或更多种的混合氧化物。非沸石催化剂还可以包括氧化钨例如V2O5/WO3/TiO2。特别关注的优选金属选自Ce、Fe和Cu。可以用上述金属对分子筛进行离子交换。
通常,至少一种分子筛是硅铝酸盐沸石或SAPO。该至少一种分子筛可以例如是小孔、中孔或大孔分子筛。这里“小孔分子筛”表示含有8个四面体原子的最大环尺寸的分子筛例如CHA;这里“中孔分子筛”表示含有10个四面体原子的最大环尺寸的分子筛例如ZSM-5;这里“大孔分子筛”表示具有12个四面体原子的最大环尺寸的分子筛例如β。小孔分子筛对于在SCR催化剂中使用是潜在有利的,参见例如申请人/受让人的WO2008/132452。优选用于根据本发明的SCR催化剂中的分子筛包括掺入分子筛骨架中的一种或多种金属,例如Fe在“骨架内”的β和Cu在“骨架内”的CHA。
用于本发明的具体分子筛选自AEI、ZSM-5、ZSM-20、ERI(包括ZSM-34)、丝光沸石、镁碱沸石、BEA(包括β)、Y、CHA、LEV(包括Nu-3)、MCM-22和EU-1,目前优选CHA分子筛例如硅铝酸盐CHA,特别是与作为助剂的Cu例如进行离子交换相组合。
典型地,本发明的排气***进一步包括用于将含氮还原剂注入到废气中的装置(例如喷射器)。通常,用于注入含氮还原剂的装置位于基底整料的上游。因此,含氮还原剂可以加入废气中和供入到基底整料的(典型地第二端的)入口。
用于本发明的含氮还原剂及其前体包括在上文就发明背景部分所述的那些的任一种。因此,例如含氮还原剂优选是氨或尿素。
优选用于注入含氮还原剂(例如氨或其前体例如尿素)的装置位于催化基底整料和包含SCR催化剂的基底整料之间。氨的前体可以是上文背景技术部分中所述的那些的任一种。
含铂催化剂可以是柴油机氧化催化剂或NOx吸收剂催化剂,任选每个均具有上文背景部分中所述的组成。在柴油机氧化催化剂位于过滤基底例如壁流式过滤器上的情况下,它在这里称作催化烟灰过滤器或CSF。
典型地,该催化剂(即含铂催化剂)包含铂和钯。
因为根据本发明的基底整料包含了措施以减少或防止铂挥发和从含铂催化剂迁移到下游SCR催化剂,因此可以在含铂催化剂中采用相对高的Pt:Pd重量比,以例如产生NO2来促进经过滤的颗粒物质的下游燃烧,例如≤10:1,例如8:1、6:1、5:1或4:1。可以使用该相对高的Pt:Pd重量比,即使PGM会从其中挥发,因为根据本发明第一方面的基底整料的设计基本上防止了挥发的PGM与SCR催化剂接触。
含铂催化剂可以位于包含SCR催化剂的基底整料紧邻的上游(即在催化基底整料和本发明的基底整料(例如包含SCR催化剂)之间没有任何中间的基底整料)。
通常和特别是当含铂催化剂位于基底整料(即包含SCR催化剂)紧邻的上游时,该催化剂(即含铂催化剂)以≤2的Pt:Pd重量比包含铂和钯,例如≤1.5:1,例如约1:1。该特征的重要性显示在实施例中:本发明人已经发现通过经验测试,该优选的Pt:Pd重量比的挥发小于Pt:Pd重量比为4:1的类似催化剂。在层状催化剂布置中,优选外层的Pt:Pd重量比≤2,或者任选所有层的全部Pt:Pd重量比总和≤2。
典型地,Pt:Pd重量比≥35:65(例如≥7:13)。优选Pt:Pd重量比≥40:60(例如≥2:3),更优选≥42.5:57.5(例如≥17:23),特别是≥45:55(例如≥9:11),例如≥50:50(例如≥1:1),和仍然更优选≥1.25:1。Pt:Pd重量比典型地是10:1-7:13。优选Pt:Pd重量比是8:1-2:3,更优选6:1-17:23,甚至更优选5:1-9:11,例如4:1-1:1,和仍然更优选2:1-1.25:1。
通常,铂族金属(PGM)的总量(例如Pt和/或Pd的总量)是1-500gft-3。优选PGM的总量是5-400gft-3,更优选10-300gft-3,仍然更优选25-250gft-3,和甚至更优选35-200gft-3。
本发明还提供一种贫燃内燃机,其包括根据本发明的排气***。该贫燃内燃机可以是强制点火例如火花点火发动机,其典型地运行于汽油燃料或者汽油燃料和其他组分例如乙醇的混合物,但是优选是压缩点火例如柴油机类型发动机。贫燃内燃机包括均质充量压缩点火(HCCI)发动机,其由汽油等燃料或柴油燃料来供能。
可以提供发动机管理装置,在使用时将催化基底整料与浓废气接触以原位产生氨。这种布置可以与排气***组合使用,该排气***包括用于将含氮还原剂(例如氨或其前体例如尿素)注入到催化基底整料和包含SCR催化剂的基底整料之间的装置,或者不具有该装置。提供发动机管理装置用于浓缩废气,以使得通过将NOx在催化基底整料的PGM催化剂上还原来原位产生氨气。
与经适当设计和管理的柴油压缩点火发动机相组合,浓废气(即与正常贫燃运行模式相比一氧化碳和烃的量增加的废气)接触NAC。NAC内的组分例如用PGM促进的二氧化铈或者二氧化铈-氧化锆可以促进水煤气变换反应,即CO(g)+H2O(v)→CO2(g)+H2(g),释放出H2。从上文所述的反应(3)和(4)脚注的副反应例如Ba(NO3)2+8H2→BaO+2NH3+5H2O可知,可以原位产生NH3和储存用于下游SCR催化剂上的NOx还原。
图1显示了本发明的一种排气***。排气***10包括从上游到下游依次布置的壁流式过滤器2,其涂覆有包含重量比为4:1的铂和钯的氧化催化剂配制物(在本领域称作催化烟灰过滤器或者“CSF”);氨源4,其包括用于氨前体尿素的喷射器;和下游壁流式过滤器基底整料6,在其入口通道上的第二区8上仅涂覆有活化涂层负载量为1.0g/in3、重量比为9:1的二氧化铈:氧化锆混合氧化物,在延伸过该壁流式过滤器的整个长度的第一区11中涂覆有穿过该壁流式过滤器的多孔结构的CuCHASCR催化剂。即第二区叠加在第一区上。各基底整料2、6位于包括锥形扩散器的金属容器或“罐”中,并且它们通过一系列管道3相连,管道3的横截面积小于基底整料2、4任一个的横截面积。锥形扩散器用于散布进入“罐装”基底整料的外壳中的废气流,从而引导该废气整体越过各基底整料的基本上整个前“面”。将离开基底整料4的废气在“尾管”5排放到大气中。
实施例
实施例1–制备涂覆有5wt%Fe/β沸石的基底整料
将商购的β沸石在搅拌下加入Fe(NO3)3水溶液中。混合后,加入粘合剂和流变改性剂以形成活化涂层组合物。
将400孔/平方英寸堇青石流通式基底整料用5wt%的Fe/β沸石样品的含水浆料,使用申请人/受让人的WO99/47260中公开的方法来涂覆,即包括以下步骤:(a)将容纳装置置于载体上,(b)将预定量的液体组分计量加入所述容纳装置中,以先(a)后(b)或者先(b)后(a)的顺序,和(c)通过施加压力或者真空,将所述液体组分抽取到载体的至少一部分中,并且将所述量的基本上全部保持在载体中。将该涂覆产物(仅从一端涂覆)干燥和然后煅烧,从另一端重复该方法,以使得基本上整个基底整料被涂覆,并且在两个涂层之间的结合处在轴向上重叠很小。从最终制品上切下1英寸(2.54cm)直径×3英寸长的芯。
对比例2–制备仅Pt催化的壁流式过滤器
制备活化涂层组合物,其包含研磨到相对高粒度分布的氧化铝颗粒、硝酸铂、粘合剂和流变改性剂在去离子水中的混合物。使用在申请人/受让人的WO2011/080525中公开的方法和设备,将钛酸铝壁流式过滤器用活化涂层负载量为0.2g/in3的催化剂组合物涂覆到最终总Pt负载量5g/ft-3,其中用包含硝酸铂和颗粒状氧化铝的活化涂层从其预定的上游端将预定取向为上游侧的第一端的通道涂覆它们总长度的75%;用与入口通道相同的活化涂层将相对端和预定取向为下游侧的通道涂覆它们总长度的25%。即该方法包括以下步骤:(i)将蜂窝状整料基底基本上保持竖直;(ii)将预定体积的液体经由基底下端的通道的开口端引入该基底中;(iii)将引入的液体密封保持在该基底内;(iv)将包含所保持的液体的基底倒置;和(v)在该基底的倒置的下端对基底的通道的开口端施加真空,以沿该基底的通道抽取该液体。催化剂组合物可以从第一端涂覆到过滤器通道上,然后可以干燥经涂覆的过滤器。然后调转从第一端涂覆的干燥过滤器,重复该方法以将相同的催化剂从第二端涂覆到过滤器通道,随后干燥和煅烧。
从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。所得到的部分描述为“新鲜的”,即未老化的。
实施例3–制备含有1:1重量%的Pt:Pd的催化的壁流式过滤器
使用与对比例2相同的方法来制备经涂覆的过滤器,除了施涂到过滤器的入口通道和出口通道上的活化涂层除硝酸铂之外还包含硝酸钯。入口和出口通道中的活化涂层负载以这种方式进行,以达到在入口表面和出口表面上5g/ft3Pt、5g/ft3Pd负载量,即总PGM负载量是10g/ft3。
从最终制品上切下1英寸(2.54cm)直径×3英寸长的芯。所得到的部分描述为“新鲜的”,即未老化的。
实施例4–制备含5:1重量%的Pt:Pd的催化壁流式过滤器
使用与对比例2相同的方法来制备经涂覆的过滤器,除了施涂到过滤器的入口通道和出口通道上的活化涂层除硝酸铂之外还包含硝酸钯。入口和出口通道中的活化涂层负载以这种方式进行,以达到在入口表面和出口表面上5g/ft3Pt、1g/ft3Pd负载量,即总PGM负载量是6g/ft3。
从最终制品上切下1英寸(2.54cm)直径×3英寸长的芯。所得到的部分描述为“新鲜的”,即未老化的。
实施例5–***测试
在图2所示的第一合成催化剂活性测试(SCAT)实验室反应器上进行测试,其中将实施例1的经涂覆的Fe/β沸石SCR催化剂的新鲜的芯置于对比例2或者实施例3或4的催化壁流式过滤器的芯下游的管道中。将合成气混合物以催化剂活塞排量30,000h-1送过该管道。使用炉在过滤器入口温度900℃的稳态温度加热(或“老化”)催化壁流式过滤器样品60分钟,在此期间入口SCR催化剂温度是300℃。使用空气(热交换器)或者水冷机构来进行过滤器和SCR催化剂之间的温度降低。在老化期间气体混合物是10%的O2、6%的H2O、6%的CO2、100ppm的CO、400ppm的NO、100ppm的作为C1的HC,余量为N2。
老化后,将经老化的SCR催化剂从第一SCAT反应器中移除,并且置入第二SCAT反应器中来专门测试经老化样品的NH3-SCR活性。然后使用合成气混合物(O2=14%;H2O=7%;CO2=5%;NH3=250ppm;NO=250ppm;NO2=0ppm;N2=余量)测试经老化的SCR催化剂在150、200、250、300、350、450、550和650℃的SCR活性,并且在图3中对每个温度数据点,将所得到的NOx转化率对温度作图。该图通过SCR反应(反应(5))所需的可用NH3的消耗,来基本上度量反应(9)和反应(5)之间的竞争,和因此度量反应(9)对于NOx转化率的影响程度。
结果显示在图3中。参见图3,可以看到在Pt:Pd重量比为1:0的催化烟灰过滤器后面老化的Fe/β沸石SCR催化剂(即对比例2)具有比新鲜样品明显降低的整体NOx转化活性。Pt:Pd重量比为5:1的实施例4的催化烟灰过滤器具有相比对比例2改进的NOx转化活性。但是,Pt:Pd重量比为1:1的实施例3已经证实了性能类似于未老化的SCR催化剂。在新鲜的Fe/β催化剂和不存在任何上游催化剂在300℃老化1小时的Fe/β催化剂之间基本上没有观察到活性损失(结果未示出)。
实施例6–制备涂覆有3wt%Cu/CHA沸石的基底整料
将商购的硅铝酸盐CHA沸石在搅拌下加入到Cu(NO3)2的水溶液中。将该浆料过滤,然后清洗和干燥。可以重复该工序来实现所需的金属负载量。将最终产物煅烧。混合后,加入粘合剂和流变改性剂以形成活化涂层组合物。
将400孔/平方英寸堇青石流通式基底整料用3wt%的Cu/CHA沸石样品的含水浆料,使用上文实施例1所述的申请人/受让人的WO99/47260中公开的方法来涂覆。将经涂覆的产品(仅从一端涂覆)干燥和然后煅烧,并且从另一端重复该方法,从而涂覆基本上整个基底整料,在两个涂层之间的结合处轴向上具有较小的重叠。从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。
实施例7–Pt:Pd重量比的进一步研究
如下来制备两种柴油机氧化催化剂:
柴油机氧化催化剂A
如下来制备单层DOC。将硝酸铂和硝酸钯加入二氧化硅-氧化铝浆料中。将β沸石加入该浆料中,以使得它包含<30质量%的作为沸石的固体含量。将该活化涂层浆料使用上文实施例1的方法计量加入到400cpsi流通式基底上。将计量加入的部分干燥,然后在500℃煅烧。该活化涂层中的总铂族金属负载量是60gft-3和总Pt:Pd重量比是4:1。从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。所得到的部分可以描述为“新鲜的”,即未老化的。
柴油机氧化催化剂B
如下来制备单层DOC。将硝酸铂和硝酸钯加入二氧化硅-氧化铝浆料中。将β沸石加入该浆料中,以使得它包含<30质量%的作为沸石的固体含量。将该活化涂层浆料使用与用于DOCA相同的方法计量加入到400cpsi流通式基底上。将计量加入的部分干燥,然后在500℃煅烧。该单层DOC中的总PGM负载量是120g/ft3和Pt:Pd重量比是2:1。从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。所得到的部分可以描述为“新鲜的”,即未老化的。
根据实施例8所述的方案来测试两种催化剂。结果示于图4中,并且参考对照样(经老化的SCR催化剂,其没有在DOCA或DOCB任一的下游进一步老化)。
实施例8–***测试
在图2所示的第一合成催化剂活性测试(SCAT)实验室反应器上进行测试,其中将实施例10的经涂覆的Cu/CHA沸石SCR催化剂的经老化的芯置于柴油机氧化催化剂(DOC)A或者B(根据实施例7)任一的芯下游的管道中。将合成气混合物以6升/分钟的速率送过该管道。使用炉在催化剂出口温度900℃的稳态温度加热(或“老化”)DOC样品2小时。SCR催化剂位于DOC样品的下游,并且在老化过程中通过调整炉出口和SCR入口之间的管长来将催化剂温度保持在300℃,不过根据需要也可以使用水冷热交换器夹套。使用适当定位的热电偶来测定温度(T1和T2)。老化期间所用的气体混合物是40%的空气、50%的N2、10%的H2O。
DOC老化后,将SCR催化剂从第一SCAT反应器中移除,并且置入第二SCAT反应器中来专门测试经老化样品的NH3-SCR活性。然后使用合成气混合物(O2=10%;H2O=5%;CO2=7.5%;CO=330ppm;NH3=400ppm;NO=500ppm;NO2=0ppm;N2=余量,即使用0.8的α值(NH3:NOx之比),以使得最大可能的可用NOx转化率是80%)测试SCR催化剂在500℃的SCR活性,并且在图4中并列的条形图上将所得到的NOx转化率对温度作图。该图通过SCR反应(反应(5))所需的可用NH3的消耗,来基本上度量反应(9)和反应(5)之间的竞争,和因此度量反应(9)对于NOx转化率的影响程度。
Pt:Pd重量比研究-结论
总体而言,图3所示的实施例5关于实施例3和4和对比例2的结果表明,1:1至5:1的Pt:Pd重量比有益于减少由从铂族金属(主要是铂)从含铂族金属的催化剂挥发到下游SCR催化剂而导致的NOx转化活性损失问题;和
图4所示的实施例8关于柴油机氧化催化剂A和B的结果显示,对于在具有总体2:1的Pt:Pd重量比的DOC下游老化的SCR催化剂,NOx转化活性损失在67%的NOx转化活性与对照的72%的NOx转化活性相比,相对轻微(使用相同方案在1:1的Pt:Pd总体重量比的DOC(这里未描述)后面老化的SCR催化剂的NOx转化活性是69%)。但是,当总体Pt:Pd重量比增加到4:1时,SCR活性明显降低到48%。
本发明人因此得出结论,在约2:1的Pt:Pd总体重量比处存在着分界线,高于其时更可能发生Pt挥发。因此,通过整体上将DOC中的Pt:Pd总体重量比限制为2:1,和在第二活化涂层中限制为≤2:1的Pt:Pd重量比,DOC中的Pt不太可能挥发和迁移到下游SCR催化剂。
为了避免任何疑义,这里引用的任何和全部文献的整体内容全部引入本申请作为参考。
Claims (17)
1.一种用于车辆贫燃内燃机的排气***,该***包括:
(1)催化基底整料,其包含位于基底整料上游的催化剂,其中该催化剂包含至少一种铂族金属(PGM),该铂族金属包含重量比为Pt:Pd≥1.25:1的铂(Pt)和钯(Pd);和
(2)基底整料,其具有长度L并且包括在一端由该基底整料的第一端限定的基本均匀长度的第一区,该第一区包含用于将从内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原的选择性催化还原(SCR)催化剂,和在一端由该基底整料的第二端限定的基本均匀长度小于L的第二区,其中该基底整料的第二端取向为上游侧,和其中:
(a)第二区由用于捕集气相铂族金属(PGM)的至少一种颗粒状金属氧化物或其任意两种或更多种的混合物组成,其中该至少一种颗粒状金属氧化物选自任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化钛及其任意两种或更多种的混合物,该至少一种颗粒状金属氧化物不充当用于任何其他催化组分的载体;或者
(b)第二区包含能够捕集和/或与气相铂族金属(PGM)合金化的组分,该组分包含:(i)选自金和银的金属;或者(ii)钯和金的混合物或合金。
2.根据权利要求1所述的排气***,其中Pt:Pd的重量比大于2:1。
3.根据权利要求1所述的排气***,其中第一区在整个长度L上延伸,和其中第二区叠加在第一区上。
4.根据权利要求3所述的排气***,其中第一区中的SCR催化剂作为该基底整料上的涂层存在。
5.根据权利要求1或2所述的排气***,其中第二区由用于捕集气相铂族金属(PGM)的至少一种颗粒状金属氧化物或其任意两种或更多种的混合物组成,第一区中的SCR催化剂作为基本均匀长度小于L的该基底整料上的涂层而存在,并且其中第一区与第二区之间基本上没有重叠。
6.根据权利要求3或4所述的排气***,其中该能够捕集和/或与气相铂族金属(PGM)合金化的组分由SCR催化剂本身来负载。
7.根据权利要求3或4所述的排气***,其中该能够捕集和/或与气相铂族金属(PGM)合金化的组分包含至少一种金属氧化物,该能够捕集和/或与气相铂族金属(PGM)合金化的组分负载在该至少一种金属氧化物上。
8.根据权利要求1或2所述的排气***,其中第一区中的SCR催化剂作为基本均匀长度小于L的该基底整料上的涂层而存在,其中该能够捕集和/或与气相铂族金属(PGM)合金化的组分包含至少一种金属氧化物,该能够捕集和/或与气相铂族金属(PGM)合金化的组分负载在该至少一种金属氧化物上,并且其中第一区与第二区之间基本上没有重叠。
9.根据权利要求1-4中任一项所述的排气***,其中该基底整料是具有入口表面和出口表面的过滤基底整料,其中该入口表面通过多孔结构与该出口表面隔开。
10.根据权利要求9所述的排气***,其中该过滤基底整料是壁流式过滤器,其中该SCR催化剂位于该壁流式过滤器的第一端的开口通道中,和第二区位于该壁流式过滤器的第二端的开口通道中,其中该多孔结构限定了第一区和第二区之间的过渡区。
11.根据权利要求1-4或10中任一项所述的排气***,其中含有铂族金属(PGM)的该催化剂是柴油机氧化催化剂或NOx吸收剂催化剂。
12.根据权利要求1-4或10中任一项所述的排气***,其中包含含有铂族金属(PGM)的催化剂的该基底整料是过滤基底整料。
13.根据权利要求12所述的排气***,其中该过滤基底整料是壁流式过滤器。
14.根据权利要求1-4、10或13中任一项所述的排气***,其进一步包括用于将氨或其前体注入到(1)该催化基底整料和(2)包含SCR催化剂的该基底整料之间的装置。
15.包括根据前述权利要求中任一项所述的排气***的压缩点火发动机,其进一步包括发动机管理装置,该发动机管理装置经布置以在使用时将过滤器与浓废气接触来原位产生氨。
16.一种车辆,其包括根据权利要求15所述的发动机。
17.一种减少或防止铂族金属(PGM)使选择性催化还原(SCR)催化剂中毒的方法,该选择性催化还原催化剂用于在车辆贫燃内燃机的排气***中将从该内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原,该铂族金属(PGM)存在于该内燃机的排气***的催化基底整料上,并且在使用时易于挥发和迁移到包含该SCR催化剂的基底整料的表面,该基底整料位于该催化基底整料的下游,其中:
(1)该催化基底整料包含位于该基底整料上游的催化剂,其中该催化剂包含至少一种铂族金属(PGM),该铂族金属包含重量比为Pt:Pd≥1.25:1的铂(Pt)和钯(Pd);和
(2)该基底整料具有长度L并且包括在一端由该基底整料的第一端限定的基本均匀长度的第一区,该第一区包含用于将从内燃机排放的废气中的氮的氧化物用含氮还原剂进行还原的选择性催化还原(SCR)催化剂,和在一端由该基底整料的第二端限定的基本均匀长度小于L的第二区,和其中:
(a)第二区由用于捕集气相铂族金属(PGM)的至少一种颗粒状金属氧化物或其任意两种或更多种的混合物组成,其中该至少一种颗粒状金属氧化物选自任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化钛及其任意两种或更多种的混合物,该至少一种颗粒状金属氧化物不充当用于任何其他催化组分的载体;或者
(b)第二区包含能够捕集和/或与气相铂族金属(PGM)合金化的组分,该组分包含:(i)选自金和银的金属;或者(ii)钯和金的混合物或合金;并且
其中第二区经取向为在第一区之前与离开该催化基底整料的废气接触,并且该方法包括在第二区中捕集和/或合金化铂族金属(PGM)。
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Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5938819B2 (ja) | 2011-10-06 | 2016-06-22 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | 排気ガス処理用酸化触媒 |
GB201200781D0 (en) | 2011-12-12 | 2012-02-29 | Johnson Matthey Plc | Exhaust system for a lean-burn ic engine comprising a pgm component and a scr catalyst |
GB2497597A (en) | 2011-12-12 | 2013-06-19 | Johnson Matthey Plc | A Catalysed Substrate Monolith with Two Wash-Coats |
GB201200784D0 (en) | 2011-12-12 | 2012-02-29 | Johnson Matthey Plc | Exhaust system for a lean-burn internal combustion engine including SCR catalyst |
GB2513364B (en) * | 2013-04-24 | 2019-06-19 | Johnson Matthey Plc | Positive ignition engine and exhaust system comprising catalysed zone-coated filter substrate |
GB201207313D0 (en) * | 2012-04-24 | 2012-06-13 | Johnson Matthey Plc | Filter substrate comprising three-way catalyst |
EP2657474A1 (de) * | 2012-04-26 | 2013-10-30 | Bernhard Kahlert | Beschichteter Partikelfilter, Katalysator und Einrichtung mit denselben |
US9034269B2 (en) * | 2012-11-29 | 2015-05-19 | Basf Se | Diesel oxidation catalyst comprising palladium, gold and ceria |
US8992869B2 (en) * | 2012-12-20 | 2015-03-31 | Caterpillar Inc. | Ammonia oxidation catalyst system |
GB2512648B (en) * | 2013-04-05 | 2018-06-20 | Johnson Matthey Plc | Filter substrate comprising three-way catalyst |
GB2514177A (en) * | 2013-05-17 | 2014-11-19 | Johnson Matthey Plc | Oxidation catalyst for a compression ignition engine |
EP3689456B1 (en) * | 2013-07-30 | 2024-05-22 | Johnson Matthey Public Limited Company | Ammonia slip catalyst |
EP2875863A1 (de) * | 2013-11-25 | 2015-05-27 | Umicore AG & Co. KG | SCR-Katalysator |
FR3017899A1 (fr) * | 2014-02-24 | 2015-08-28 | Peugeot Citroen Automobiles Sa | Structure de filtration d'un gaz et de reduction des oxydes d'azote |
US9662636B2 (en) * | 2014-04-17 | 2017-05-30 | Basf Corporation | Zoned catalyst composites |
US20150361842A1 (en) * | 2014-06-11 | 2015-12-17 | Homayoun Ahari | Exhaust system for a vehicle |
US9708949B2 (en) * | 2014-06-14 | 2017-07-18 | GM Global Technology Operations LLC | Exhaust aftertreatment system for a compression-ignition engine |
CN104258899B (zh) * | 2014-10-27 | 2016-08-31 | 四川绵阳华元航升环保科技有限公司 | 基于离子交换分子筛的尿素scr催化剂 |
GB201504658D0 (en) * | 2015-03-19 | 2015-05-06 | Johnson Matthey Plc | Exhaust system for a compression ignition engine having a capture face for volatilised platinum |
JP6436824B2 (ja) * | 2015-03-23 | 2018-12-12 | 日本碍子株式会社 | ハニカム構造体 |
US9616386B2 (en) * | 2015-03-23 | 2017-04-11 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Catalyst for purification of exhaust gas, NOx storage-reduction catalyst, and method for purifying exhaust gas |
DE102015012736A1 (de) * | 2015-10-01 | 2017-04-06 | Man Truck & Bus Ag | Verfahren zum Betreiben eines Abgasnachbehandlungssystems |
GB201521123D0 (en) * | 2015-11-30 | 2016-01-13 | Johnson Matthey Plc | Diesel oxidation catalyst having a capture region for exhaust gas impurities |
DE102015225579A1 (de) * | 2015-12-17 | 2017-06-22 | Umicore Ag & Co. Kg | Verfahren zur Verhinderung der Kontamination eines SCR-Katalysators mit Platin |
WO2017192508A1 (en) * | 2016-05-03 | 2017-11-09 | Masdar Institute Of Science And Technology | Catalytic converter substrates comprising triply periodic minimal surfaces |
GB201613849D0 (en) * | 2016-08-12 | 2016-09-28 | Johnson Matthey Plc | Exhaust system for a compression ignition engine having a capture region for volatilised platinum |
GB201614677D0 (en) * | 2016-08-30 | 2016-10-12 | Johnson Matthey Plc | Oxidation catalyst for a diesel engine exhaust |
JP6458827B2 (ja) | 2017-06-05 | 2019-01-30 | マツダ株式会社 | エンジンの排気ガス処理装置 |
US10456746B2 (en) * | 2018-02-12 | 2019-10-29 | GM Global Technology Operations LLC | Selective catalytic reduction filter for reducing nitrous oxide formation and methods of using the same |
US11161098B2 (en) * | 2018-05-18 | 2021-11-02 | Umicore Ag & Co. Kg | Three-way catalyst |
CN111219236A (zh) * | 2018-11-23 | 2020-06-02 | 汪利峰 | 柴油机尾气的后处理*** |
CN113784789B (zh) * | 2019-06-26 | 2023-12-12 | 庄信万丰股份有限公司 | 用于压缩点火内燃机的复合分区氧化催化剂 |
CN110560056B (zh) * | 2019-08-30 | 2022-11-01 | 无锡威孚环保催化剂有限公司 | 通用小型汽油机尾气催化剂及其制备方法 |
EP3889404A1 (en) * | 2020-03-30 | 2021-10-06 | Johnson Matthey Public Limited Company | Multi-region twc catalysts for gasoline engine exhaust gas treatments with improved h2s attenuation |
EP3936221A1 (en) | 2020-07-07 | 2022-01-12 | UMICORE AG & Co. KG | Catalysed particulate filter with enhanced passive soot functionality |
WO2023016489A1 (en) * | 2021-08-11 | 2023-02-16 | Basf Corporation | Particulate filter having partially coated catalytic layer |
WO2023050324A1 (en) * | 2021-09-30 | 2023-04-06 | Basf Corporation | Platinum group metal capture materials |
EP4310210A1 (en) | 2022-07-19 | 2024-01-24 | Yara International ASA | Volatile and precious metal recovery system made of stacked silver-comprising elements |
EP4310209A1 (en) | 2022-07-19 | 2024-01-24 | Yara International ASA | Method for recovering volatile pt or pd and system thereof |
Family Cites Families (81)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8516333D0 (en) | 1985-06-28 | 1985-07-31 | Johnson Matthey Plc | Nitric oxide |
JPS6268544A (ja) | 1985-09-20 | 1987-03-28 | Toyota Motor Corp | 排気ガス浄化用モノリス触媒 |
US4902487A (en) | 1988-05-13 | 1990-02-20 | Johnson Matthey, Inc. | Treatment of diesel exhaust gases |
WO1993007363A1 (fr) | 1991-10-03 | 1993-04-15 | Toyota Jidosha Kabushiki Kaisha | Dispositif pour purifier les gaz d'echappement d'un moteur a combustion interne |
DE69422938T2 (de) | 1993-04-28 | 2000-07-20 | Cataler Industrial Co., Ltd. | Katalysator zur Reinigung von Abgasen aus Dieselmotoren |
US6667018B2 (en) | 1994-07-05 | 2003-12-23 | Ngk Insulators, Ltd. | Catalyst-adsorbent for purification of exhaust gases and method for purification of exhaust gases |
US5478549A (en) | 1994-12-15 | 1995-12-26 | E. I. Du Pont De Nemours And Company | Production of nitric oxide |
GB9511412D0 (en) | 1995-06-06 | 1995-08-02 | Johnson Matthey Plc | Improvements in emission control |
JP3387290B2 (ja) | 1995-10-02 | 2003-03-17 | トヨタ自動車株式会社 | 排ガス浄化用フィルター |
JPH09271674A (ja) | 1996-04-04 | 1997-10-21 | Toyota Motor Corp | ディーゼル排ガス用酸化触媒 |
ES2131980T3 (es) | 1996-11-11 | 1999-08-01 | Degussa | Catalizador purificador de gas de escape con una mejor capacidad de conversion para hidrocarburos |
US6093378A (en) | 1997-05-07 | 2000-07-25 | Engelhard Corporation | Four-way diesel exhaust catalyst and method of use |
US6348430B1 (en) | 1997-06-20 | 2002-02-19 | Degussa Ag | Exhaust gas treatment catalyst for internal combustion engines with two catalytically active layers on a carrier structure |
GB9805815D0 (en) | 1998-03-19 | 1998-05-13 | Johnson Matthey Plc | Manufacturing process |
JP2002540918A (ja) | 1998-07-10 | 2002-12-03 | エイエスイーシー・マニュファクチュアリング | 内燃エンジン排出ガス処理用の改善された触媒式吸着剤システム及びその製造方法 |
GB9919013D0 (en) * | 1999-08-13 | 1999-10-13 | Johnson Matthey Plc | Reactor |
JP4022707B2 (ja) | 2000-04-28 | 2007-12-19 | ヤマトミシン製造株式会社 | ミシンのルーパ引出し装置 |
US6835689B1 (en) | 2000-10-10 | 2004-12-28 | Corning Incorporated | NH3 generation catalysts for lean-burn and diesel applications |
DE10113947B4 (de) | 2001-03-22 | 2004-03-25 | Daimlerchrysler Ag | Verfahren zur Verringerung des Stickoxidgehalts im Abgas einer im Mager-Fett-Wechsel betreibbaren Brennkraftmaschine |
EP1264628A1 (de) | 2001-06-09 | 2002-12-11 | OMG AG & Co. KG | Redox-Katalysator für die selektive katalytische Reduktion der im Abgas von Dieselmotoren enthaltenen Stickoxide mittels Ammoniak sowie Verfahren zu seiner Herstellung |
DE602004005107T2 (de) * | 2003-07-02 | 2007-06-28 | Haldor Topsoe A/S | Verfahren und Filter zur katalytischen Behandlung von Dieselabgasen |
US7229597B2 (en) | 2003-08-05 | 2007-06-12 | Basfd Catalysts Llc | Catalyzed SCR filter and emission treatment system |
US7722829B2 (en) | 2004-09-14 | 2010-05-25 | Basf Catalysts Llc | Pressure-balanced, catalyzed soot filter |
GB2406803A (en) | 2004-11-23 | 2005-04-13 | Johnson Matthey Plc | Exhaust system comprising exotherm-generating catalyst |
JP2006272064A (ja) | 2005-03-28 | 2006-10-12 | Mazda Motor Corp | 酸化触媒 |
US20070157607A1 (en) | 2006-01-11 | 2007-07-12 | Pfefferle William C | Clean air system |
JP4711860B2 (ja) | 2006-03-03 | 2011-06-29 | エヌ・イーケムキャット株式会社 | 排気ガス浄化用酸化触媒、排気ガス浄化用触媒構造体および排気ガス浄化方法 |
US7576031B2 (en) | 2006-06-09 | 2009-08-18 | Basf Catalysts Llc | Pt-Pd diesel oxidation catalyst with CO/HC light-off and HC storage function |
PL2038046T3 (pl) | 2006-06-29 | 2018-09-28 | Umicore Ag & Co. Kg | Dwuwarstwowy katalizator trójdrożny i jego zastosowanie |
US7550124B2 (en) | 2006-08-21 | 2009-06-23 | Basf Catalysts Llc | Layered catalyst composite |
US7758834B2 (en) | 2006-08-21 | 2010-07-20 | Basf Corporation | Layered catalyst composite |
JP5037888B2 (ja) | 2006-09-26 | 2012-10-03 | 株式会社キャタラー | 排ガス浄化用触媒 |
GB0620883D0 (en) * | 2006-10-20 | 2006-11-29 | Johnson Matthey Plc | Exhaust system for a lean-burn internal combustion engine |
US7534738B2 (en) | 2006-11-27 | 2009-05-19 | Nanostellar, Inc. | Engine exhaust catalysts containing palladium-gold |
KR20080047950A (ko) | 2006-11-27 | 2008-05-30 | 나노스텔라 인코포레이티드 | 팔라듐-금을 포함하는 엔진 배기가스 촉매 |
MX2009009095A (es) | 2007-02-27 | 2009-09-14 | Basf Catalysts Llc | Catalizadores de zeolita cha de cobre. |
EP2517776B2 (en) | 2007-04-26 | 2019-08-07 | Johnson Matthey Public Limited Company | Transition metal/kfi-zeolite scr catalyst |
JP2008279352A (ja) | 2007-05-10 | 2008-11-20 | Asahi Kasei Corp | リーンバーン自動車排NOx用浄化触媒 |
GB2457651A (en) | 2008-01-23 | 2009-08-26 | Johnson Matthey Plc | Catalysed wall-flow filter |
US20090196812A1 (en) | 2008-01-31 | 2009-08-06 | Basf Catalysts Llc | Catalysts, Systems and Methods Utilizing Non-Zeolitic Metal-Containing Molecular Sieves Having the CHA Crystal Structure |
EP2116293B1 (de) | 2008-04-11 | 2010-03-17 | Umicore AG & Co. KG | Abgasreinigungssystem zur Behandlung von Motorenabgasen mittels SCR-Katalysator |
US8776498B2 (en) | 2008-04-16 | 2014-07-15 | Ford Global Technologies, Llc | Air-injection system to improve effectiveness of selective catalytic reduction catalyst for gasoline engines |
GB0808427D0 (en) | 2008-05-09 | 2008-06-18 | Johnson Matthey Plc | Apparatus |
WO2010071205A1 (ja) | 2008-12-19 | 2010-06-24 | 株式会社 キャタラー | 排ガス浄化用触媒 |
WO2010075345A2 (en) | 2008-12-24 | 2010-07-01 | Basf Catalysts Llc | Emissions treatment systems and methods with catalyzed scr filter and downstream scr catalyst |
WO2010077843A2 (en) | 2008-12-29 | 2010-07-08 | Basf Catalysts Llc | Oxidation catalyst with low co and hc light-off and systems and methods |
US8844274B2 (en) | 2009-01-09 | 2014-09-30 | Ford Global Technologies, Llc | Compact diesel engine exhaust treatment system |
US8252258B2 (en) | 2009-01-16 | 2012-08-28 | Basf Corporation | Diesel oxidation catalyst with layer structure for improved hydrocarbon conversion |
US8211392B2 (en) | 2009-01-16 | 2012-07-03 | Basf Corporation | Diesel oxidation catalyst composite with layer structure for carbon monoxide and hydrocarbon conversion |
US9440192B2 (en) | 2009-01-16 | 2016-09-13 | Basf Corporation | Diesel oxidation catalyst and use thereof in diesel and advanced combustion diesel engine systems |
US8415269B2 (en) | 2009-01-21 | 2013-04-09 | WGCH Technology Limited | Palladium-gold catalyst synthesis |
US10773209B2 (en) | 2009-02-20 | 2020-09-15 | Basf Corporation | Aging-resistant catalyst article for internal combustion engines |
US8920759B2 (en) | 2009-03-02 | 2014-12-30 | GM Global Technology Operations LLC | Method and apparatus for reducing NOx emissions from a lean burning hydrocarbon fueled power source |
US9662611B2 (en) * | 2009-04-03 | 2017-05-30 | Basf Corporation | Emissions treatment system with ammonia-generating and SCR catalysts |
US8246923B2 (en) | 2009-05-18 | 2012-08-21 | Umicore Ag & Co. Kg | High Pd content diesel oxidation catalysts with improved hydrothermal durability |
DE102009033635B4 (de) | 2009-07-17 | 2020-11-05 | Umicore Ag & Co. Kg | Katalytisch aktives Partikelfilter mit Schwefelwasserstoff-Sperrfunktion, seine Verwendung und Verfahren zur Entfernung von Stickoxiden und Partikeln |
US20110064632A1 (en) | 2009-09-14 | 2011-03-17 | Ford Global Technologies, Llc | Staged Catalyst System and Method of Using the Same |
US20110064633A1 (en) * | 2009-09-14 | 2011-03-17 | Ford Global Technologies, Llc | Multi-Functional Catalyst Block and Method of Using the Same |
US8557203B2 (en) | 2009-11-03 | 2013-10-15 | Umicore Ag & Co. Kg | Architectural diesel oxidation catalyst for enhanced NO2 generator |
US8765625B2 (en) | 2009-12-10 | 2014-07-01 | Shubin, Inc. | Engine exhaust catalysts containing copper-ceria |
US20120302439A1 (en) | 2009-12-31 | 2012-11-29 | Nanostellar, Inc. | Engine exhaust catalysts doped with bismuth or manganese |
GB201000019D0 (en) | 2010-01-04 | 2010-02-17 | Johnson Matthey Plc | Coating a monolith substrate with catalyst component |
WO2011092525A1 (en) | 2010-02-01 | 2011-08-04 | Johnson Matthey Plc | Filter comprising combined soot oxidation and nh3-scr catalyst |
US8263033B2 (en) | 2010-02-23 | 2012-09-11 | Ford Global Technologies, Llc | Palladium-contaning oxidation catalyst |
WO2011131324A1 (de) * | 2010-04-20 | 2011-10-27 | Umicore Ag & Co. Kg | Neue mischoxid-materialien zur selektiven katalytischen reduktion von stickoxiden in abgasen |
US8293182B2 (en) * | 2010-05-05 | 2012-10-23 | Basf Corporation | Integrated SCR and AMOx catalyst systems |
US20110286900A1 (en) | 2010-05-21 | 2011-11-24 | Basf Corporation | PGM-Zoned Catalyst for Selective Oxidation of Ammonia in Diesel Systems |
WO2011162030A1 (ja) | 2010-06-24 | 2011-12-29 | エヌ・イー ケムキャット株式会社 | 選択還元触媒を用いた排気ガス浄化触媒装置、排気ガス浄化方法、および排気ガス浄化触媒装置を搭載したディーゼル自動車 |
EP2535102A1 (en) | 2010-06-30 | 2012-12-19 | N.E. Chemcat Corporation | Flue gas-cleaning device and flue gas-cleaning method that use selective catalytic reduction catalyst |
US8137648B2 (en) * | 2010-10-12 | 2012-03-20 | Ford Global Technologies, Llc | Diesel engine exhaust treatment system and method including a platinum group metal trapping device |
US8323599B2 (en) | 2010-11-22 | 2012-12-04 | Umicore Ag & Co. Kg | Three-way catalyst having an upstream multi-layer catalyst |
JP5310767B2 (ja) | 2011-03-29 | 2013-10-09 | トヨタ自動車株式会社 | 排ガス浄化触媒 |
US9523302B2 (en) | 2011-04-28 | 2016-12-20 | N.E. Chemcat Corporation | Off gas purification device |
BR112013029307A2 (pt) | 2011-05-13 | 2017-01-31 | Basf Corp | filtro para fuligem catalisada, processo para fabricação de um filtro para fuligem catalisada. sistema e método para tratamento dos gases de escapamento de um motor diesel |
US9114376B2 (en) | 2011-06-05 | 2015-08-25 | Johnson Matthey Public Limited Company | Platinum group metal (PGM) catalyst for treating exhaust gas |
GB2492175B (en) * | 2011-06-21 | 2018-06-27 | Johnson Matthey Plc | Exhaust system for internal combustion engine comprising catalysed filter substrate |
US9044734B2 (en) | 2011-09-23 | 2015-06-02 | Basf Se | Diesel oxidation catalyst with layered structure containing ceria composition as palladium support material for enhanced HC and CO gas conversion |
JP5938819B2 (ja) | 2011-10-06 | 2016-06-22 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | 排気ガス処理用酸化触媒 |
GB201200784D0 (en) | 2011-12-12 | 2012-02-29 | Johnson Matthey Plc | Exhaust system for a lean-burn internal combustion engine including SCR catalyst |
GB2497597A (en) | 2011-12-12 | 2013-06-19 | Johnson Matthey Plc | A Catalysed Substrate Monolith with Two Wash-Coats |
GB201200781D0 (en) | 2011-12-12 | 2012-02-29 | Johnson Matthey Plc | Exhaust system for a lean-burn ic engine comprising a pgm component and a scr catalyst |
-
2012
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- 2012-12-11 KR KR1020147019096A patent/KR101951515B1/ko active IP Right Grant
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EP2790826A2 (en) | 2014-10-22 |
GB2497656A (en) | 2013-06-19 |
DE102012222804A1 (de) | 2013-06-27 |
KR101951515B1 (ko) | 2019-02-22 |
GB201200783D0 (en) | 2012-02-29 |
BR112014013233A2 (pt) | 2017-06-13 |
GB2497656B (en) | 2015-09-16 |
RU2608998C2 (ru) | 2017-01-30 |
GB201222229D0 (en) | 2013-01-23 |
JP2015505723A (ja) | 2015-02-26 |
WO2013088129A3 (en) | 2013-12-27 |
WO2013088129A2 (en) | 2013-06-20 |
RU2014128568A (ru) | 2016-02-10 |
US20130149207A1 (en) | 2013-06-13 |
JP6173336B2 (ja) | 2017-08-02 |
CN103974768A (zh) | 2014-08-06 |
KR20140105554A (ko) | 2014-09-01 |
BR112014013233B1 (pt) | 2020-10-27 |
DE102012222804B4 (de) | 2021-05-20 |
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