CN105555403B - 氨逸出催化剂 - Google Patents
氨逸出催化剂 Download PDFInfo
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- CN105555403B CN105555403B CN201480045713.8A CN201480045713A CN105555403B CN 105555403 B CN105555403 B CN 105555403B CN 201480045713 A CN201480045713 A CN 201480045713A CN 105555403 B CN105555403 B CN 105555403B
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- catalyst
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- exhaust
- substrate
- oxidation
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- 229910021529 ammonia Inorganic materials 0.000 title abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 33
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 32
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- 238000007254 oxidation reaction Methods 0.000 claims description 161
- 230000003647 oxidation Effects 0.000 claims description 152
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000000446 fuel Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 27
- 230000009467 reduction Effects 0.000 claims description 22
- 238000006555 catalytic reaction Methods 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 18
- 229910000510 noble metal Inorganic materials 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 16
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- 150000004706 metal oxides Chemical class 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
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- 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 4
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明提供氨逸出(ammonia slip)催化剂制品,所述氨逸出催化剂制品具有:在顶层或上游层中的用于对一氧化碳和/或烃进行氧化的负载的钯;在所述顶层中或单独的下层或下游层中的SCR催化剂;以及在底层中的氨氧化催化剂。还提供用于使用所述催化剂制品来处理排气的方法,其中所述处理包括降低氨和任选一氧化碳和/或烃在所述排气中的浓度。
Description
背景
发明领域:
提供氧化催化剂,所述氧化催化剂用于处理燃烧排气,并且尤其是用于减少与选择性催化还原过程有关的氨逸出(ammonia slip)。
相关领域描述:
烃类燃料的燃烧产生发动机排气或烟道气,所述发动机排气或烟道气大部分地含有相对良性的氮气(N2)、水蒸气(H2O)和二氧化碳(CO2)。但所述排气还相对小部分地含有有害物质和/或有毒物质,例如来自不完全燃烧的一氧化碳(CO)、来自未燃烧的燃料的烃(HC)、来自过度燃烧温度的氮氧化物(NOx)以及颗粒物质(大多是烟尘)。为减轻释放在大气中的排气的环境影响,期望优选地通过不进而产生其他有害物质或有毒物质的工艺来消除或减少不良组分的量。
NOx(其包括一氧化氮(NO)、二氧化氮(NO2)和一氧化二氮(N2O))是难以从由稀燃发动机产生的排气中除去的组分。将NOx还原成N2在稀燃排气中尤其有问题,因为排气含有足够氧气以利于氧化反应而不是还原。尽管如此,可以通过通常称为选择性催化还原(SCR)的工艺来还原NOx。SCR工艺涉及在催化剂存在下并借助于含氮还原剂(例如氨)将NOx转化成元素氮(N2)和水。在SCR工艺中,在使排气与SCR催化剂接触之前将气体还原剂(例如氨)添加至排气流中。还原剂被吸收在催化剂上,并且当气体通过催化基材或在催化的基材之上时,发生NOx还原反应。对于使用氨的化学计量SCR反应的化学方程式是:
4NO+4NH3+O2→4N2+6H2O
2NO2+4NH3+O2→3N2+6H2O
NO+NO2+2NH3→2N2+3H2O
大多数SCR工艺使用化学计量过量的氨以便使NOx的转化最大化。通过SCR工艺的未反应的氨(也称为“氨逸出”)是不期望的,因为逸出的氨气可以与其他燃烧物质反应和/或如果释放,会负面地影响大气。为减少氨逸出,SCR系统可以包括SCR催化剂下游的氨氧化催化剂(AMOX)(又称为氨逸出催化剂(ASC))。
已知用于使排气中过量的氨氧化的催化剂。例如,美国专利号7,393,511描述氨氧化催化剂,该氨氧化催化剂含有二氧化钛、氧化铝、二氧化硅、氧化锆等载体上的贵金属(例如铂、钯、铑或金)。这些催化剂如下氧化NH3以产生N2和/或次级NOx+H2O:
4NH3+7O2→4NO2+6H2O
4NH3+5O2→4NO+6H2O
2NH3+2O2→N2O+3H2O
4NH3+3O2→2N2+6H2O
为补救此次级NOx形成,典型的ASC包括:顶部催化剂层,其包含常规SCR催化剂;和底部催化剂层,其包含氨氧化催化剂。含有逸出的NH3和极少NOx或无NOx的排气通过ASC的顶部SCR层,其中SCR催化剂存储NH3的一部分。NH3的另一部分继续渗透穿过催化剂,直到它到达底层,在此处它被氧化成次级NOx和H2O。次级NOx回渗穿过顶层,在此处次级NOx与存储的NH3反应以产生N2和H2O。
将ASC的顶层和底层隔开以防止NH3的立即氧化,所述NH3的立即氧化将导致在排出气流中形成未处理的次级NOx。为此,ASC中的顶层不含贵金属,例如铂族金属(PGM)。此外,含有PGM基氧化催化剂的底层由顶层完全覆盖以防止未处理的次级NOx进入排出气流。
发明内容
本发明部分地涉及多相氧化催化剂,所述多相氧化催化剂特别有效地同时减少氨逸出而无显著的NOx形成以及氧化CO和HC。令人惊奇的是,将钯包含在双层或三层ASC的顶层中增加了催化剂的CO和HC氧化势,同时使来自NH3的氧化的次级NOx产生极小增加或不增加。此结果尤其令人意外,因为Pd已知为强NH3氧化催化剂。在本催化剂中,NH3的大部分通过Pd层到达下层,在所述下层处被氧化。
本发明的ASC可按若干方式来使用。例如,该催化剂可用于稀燃排气后处理系统,所述稀燃排气后处理系统不包括ASC组件上游的氧化催化剂(例如柴油机氧化催化剂(DOC))。在这种系统中,DOC不是必需的,因为排气中的CO和烃由ASC完全转化成CO2和H2O。通过消除对额外组件的期望,本发明的ASC可以减少后处理系统的占地面积以及其成本。
在另一实例中,ASC也用作柴油机放热催化剂(DEC)以产生用于再生下游柴油机颗粒过滤器(DPF)的所需热量。通过充当下游DEC(即,初级SCR催化剂和任选DOC催化剂的下游,但在DPF的上游),上游组件不暴露于在过滤器再生期间要求的高温下。也就是说,本发明的催化剂使注入到后处理系统中的燃料氧化以产生热量,其进而燃烧已经累积在DPF上的烟尘。减少氨逸出并且产生放热的组合能力允许DEC和DPF组合位于下游,并且远离更加热敏感的SCR和DOC催化剂。
因此,提供用于处理排气的催化剂制品,所述催化剂制品包括基材,所述基材具有设置在基材上或内的第一催化剂层和涂覆在第二催化剂层的至少一部分之上的第二催化剂层,其中第一催化剂层包含第一氧化催化剂,并且第二催化剂层含有以下(i)和(ii)的混合物:(i)由第一载体上的钯组成的第二氧化催化剂和(ii)用于选择性还原NOx和/或存储NH3的催化剂。
根据本发明的另一方面,提供用于处理排气的催化剂制品,所述催化剂制品包括:(a)基材;(b)第一催化剂层,其设置在基材上或内,其中第一层含有NH3氧化催化剂;(c)第二催化剂层,其设置在第一催化剂层上,其中第二层含有用于选择性还原NOx和/或存储NH3的催化剂;和(d)第三催化剂层,其设置在第二催化剂层之上,其中第三催化剂层包含负载的Pd。
根据本发明的另一方面,提供用于处理排气的系统,所述系统包括:(a)排气歧管;和(b)基材,其具有设置在基材上或内的第二催化剂层和涂覆在第二催化剂层之上的第一催化剂层,其中第一催化剂层含有以下(i)和(ii)的混合物:(i)由第一载体上的钯组成的第一氧化催化剂和(ii)用于选择性还原NOx和/或存储NH3的催化剂,并且第二催化剂层包含第二氧化催化剂;其中基材与排气歧管流体连通,并且其中在基材与排气歧管之间无氧化催化剂。
根据本发明的另一实施方案,提供用于包括以下组件的发动机排气的后处理系统:(a)柴油机氧化催化剂,其用于产生约4:1至约1:30的NO/NO2体积比;(b)用于将氮基还原剂引入系统中的注射器;(c)初级SCR催化剂;(d)用于将燃料引入系统中的注射器;(e)第二流通式整料,其具有设置在所述基材上或内的第二催化剂层和涂覆在第二催化剂层的至少一部分之上的第一催化剂层,其中第一催化剂层含有以下(i)和(ii)的混合物:(i)由第一载体上的钯组成的第一氧化催化剂和(ii)用于选择性还原NOx和/或存储NH3的催化剂,并且第二催化剂层包含第二氧化催化剂;其中基材与排气歧管流体连通;和(f)柴油机颗粒过滤器;其中组分(a)–(f)处于从上游到下游的连续顺序。
根据本发明的另一方面,提供用于处理排气的方法,所述方法包括使含有NH3的排气与催化剂制品接触的步骤,所述催化剂制品包含基材,所述基材具有设置在基材上和/或内的第一催化剂层和涂覆在第一催化剂层上的第二催化剂层;其中第一催化剂层包含第一氧化催化剂,并且第二催化剂层含有以下(i)和(ii)的混合物:(i)由负载的钯组成的第二氧化催化剂和(ii)用于选择性还原NOx和/或存储NH3的催化剂;并且其中第一氧化催化剂和第二氧化催化剂是不同的配制物;其中所述接触(a)将NH3的至少一部分存储在第二催化剂层中;(b)氧化NH3的至少一部分以形成N2和/或次级NOx;并且(c)用存储的NH3选择性还原次级NOx的至少一部分以产生N2和H2O。在某些实施方案中,所述方法还包括使排气中的CO和/或烃的至少一部分氧化的步骤。
根据本发明的另一方面,提供用于再生颗粒过滤器的方法,所述方法包括:将烃基燃料注入到本文描述的ASC催化剂上游的排气中,并且优选地注入在初级SCR催化剂下游;使用燃烧反应来加热排气;和使用加热的排气来燃烧已经累积在过滤器上的烟尘及其他颗粒物质。
附图简要说明
图1A-1E是根据本发明的某些实施方案的催化剂制品的图;
图2A-2B是根据本发明的实施方案的排气后处理系统的图;
图3是描述了对于本发明的实施方案的比较性CO转化率的图表;
图4是描述了对于本发明的实施方案的比较性HC转化率的图表;
图5是描述了对于本发明的实施方案的比较性NH3转化率的图表;
图6是描述了对于本发明的实施方案的比较性NOx输出的图表;
图7是描述了对于本发明的实施方案的比较性N2选择性的图表;和
图8是描述了对于本发明的实施方案的比较性CO转化率的图表。
本发明优选实施方案的详细说明
在优选实施方案中,本发明涉及催化剂制品,所述催化剂制品用于改善环境空气质量,尤其是用于改善由发电厂、燃气轮机、稀燃内燃发动机等等产生的排气排放。至少部分地通过在广泛的操作温度范围内降低排气中的HC、CO、NH3和/或NOx浓度来改善排放。本发明可以通过在单个单元中进行多个功能来降低用于排气后处理系统的总成本和要求的空间。此外,本发明可以通过将高温过滤器再生操作定位在温度敏感DOC和SCR催化剂的下游来改善排气后处理系统的热持久性。
在优选实施方案中,本发明包括基材,所述基材负载:第一氧化催化剂,其用于尤其在低温(例如低于250℃)下将NH3初步氧化成次级NOx和H2O;SCR催化剂,其用于存储NH3和/或在O2存在下用NH3选择性还原NOx;和第二氧化催化剂,其主要用于将CO氧化成CO2并且将HC氧化成CO2和H2O而基本上不氧化NH3,其中第二氧化催化剂在第一氧化催化剂的上方或上游。如本文使用,术语“次级NOx”是指通过NH3的氧化产生的NOx,并且不包括如通过燃料的燃烧产生的NOx。优选地,选择第二氧化催化剂来完全氧化CO和HC,并且第二氧化催化剂并非部分氧化催化剂。
第二氧化催化剂包含钯,优选地为负载的钯。任选地,第二氧化催化剂基本上由负载的钯组成。优选地,第二氧化催化剂基本上不含除Pd外的任何催化活性金属。如本文使用,术语“催化活性金属”是指直接参与NH3、HC或CO的催化氧化的金属。如本文使用,关于第二氧化催化剂中的金属的术语“基本上不含”是指所述金属不存在或者以足够低的浓度存在以便不影响催化剂的氧化功能。基本上不含特定金属的催化剂的实例包括其中特定金属以基于第二氧化催化剂中的Pd的总重量计小于约1重量%,小于约0.1重量%或小于约0.01重量%的量存在的那些催化剂。
除Pd外,第二氧化催化剂优选地不含贵金属,所述贵金属包括钌、铼、铑、银、锇、铱、铂和金。优选地,氧化催化剂不含或基本上不含一种或多种碱金属和碱土金属,例如钠、钾、钙和镁。优选地,氧化催化剂不含或基本上不含钒、钨和/或钼。在某些实施方案中,氧化催化剂不含或基本上不含锰、硅、锆、铝和其氧化物,除非所述金属以金属氧化物载体的形式存在。在某些实施方案中,氧化催化剂不含或基本上不含过渡金属,例如选自铜、铁、镍、钴、铬、铪、镧、镓、铈和锌的一种或多种金属。在某些实施方案中,氧化催化剂不含或基本上不含稀土金属。
优选地,第二氧化催化剂中的钯由高表面面积载体负载,所述高表面面积载体例如金属氧化物或沸石,尤其优选金属氧化物。可以通过任何常规方式使钯组分并入至载体上,例如将含有金属的盐水溶液与载体混合来形成金属胶体载体涂层,所述金属胶体载体涂层可随后被施加至基材。在某些实施方案中,经由在载体涂层配料之前的浸渍,将钯预固定在载体上。优选地,钯是高表面面积载体上的涂层。
用于钯的载体的类型无具体限制,前提条件是其是具有大表面面积的颗粒,是惰性的并且适合在后处理系统中使用。载体材料的实例包括耐火金属氧化物,例如氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化铈及它们的物理混合物或复合物,尤其优选氧化铝以及二氧化铈。在某些实施方案中,载体具有宽孔(例如100–350),或宽孔和窄孔两者。在某些实施方案中,载体具有至少50m2/g,优选地约50-500m2/g,更优选地约50–300m2/g或约150–250m2/g的BET表面积。耐火金属氧化物载体优选地具有优选地通过压汞孔隙率测定法(mercury intrusion porosimetry)测量的约0.1-0.5g/cc(例如约0.2–0.4g/cc)的孔体积。载体材料的基于颗粒计数的平均粒度优选地为约0.01-10μm,例如约0.5–5μm、约0.1–1μm或约5–10μm,并且优选地具有在这些范围之一内的大多数颗粒计数。在某些实施方案中,载体的D90粒度在这些范围之一内。
用于第二氧化催化剂的其他钯载体包括分子筛,例如具有沸石类型骨架的铝硅酸盐、硅铝磷酸盐和铝磷酸盐,例如AEI、AFX、CHA、KFI、LEV、ERI、DDR、UEI、RHO、EAB、PAU、MER、GOO、YUG、GIS、UFI、VIN、AEI/CHA共生物、BEA、MFI、MOR和FER。
在某些实施方案中,第二氧化催化剂是设置在基材上或设置在另一催化剂层上的单独且不同的层,所述另一催化剂层在基材上和/或内。在这种实施方案中,第二氧化催化剂优选地不含任何其他催化材料。
在其他实施方案中,第二氧化设置在基材上作为催化剂层,所述催化剂层含有第二氧化催化剂和SCR催化剂的物理混合物。对于其中第二氧化催化剂设置在基材上作为包含SCR催化剂的混合物的实施方案,所述混合物不含任何贵金属,尤其是PGM。优选地,所述混合物是负载的Pd和SCR催化剂的非均相混合物,其中Pd均匀地分配在混合物中。
本发明的SCR催化剂无具体限制,前提条件是所述SCR催化剂可以在氧化环境中在还原剂存在下选择性还原NOx。并入至ASC中的SCR催化剂用于处理次级NOx,并且与用于处理由燃料的燃烧产生的NOx的SCR催化剂是单独且不同的。因此,并入至ASC中的SCR催化剂可被称为“次级SCR”催化剂,并且用于处理由燃料的燃烧产生的NOx的SCR催化剂可被称为“初级SCR”催化剂。这些不同的SCR催化剂可以具有相同配制物或不同配制物。
在某些实施方案中,SCR催化剂包含高表面面积载体上的至少一种促进剂金属,所述高表面面积载体包括耐火金属氧化物和分子筛,例如铝硅酸盐(沸石)、硅铝磷酸盐(SAPO)或铝磷酸盐(AlPO)。在某些实施方案中,SCR催化剂具有极小至没有的NH3氧化能力,但可以随温度变化、随稀环境或富环境变化或随这二者变化而存储和释放NH3。如本文使用,术语“稀环境”是指由燃烧超过化学计量空气燃料混合物的燃料(例如过量空气)产生的排气或含有至少等于稀燃排气的量的氧气的排气。如本文使用,术语“富环境”是指由空气燃料的富混合物的燃烧产生的排气。
优选的促进剂金属选自由V、Cr、Co、Cu、Fe、Hf、La、Ce、In、V、Mn、Ni、Zn、Ga、它们单独或组合组成的组。促进剂金属可以是游离金属或金属离子,并且可以在载体材料的合成期间通过各种技术将促进剂金属结合在载体上或内,所述技术包括离子交换、始润法(incipient wetness)、直接涂覆或原位。优选的促进剂金属包括Cu和Fe,尤其是当促进剂金属负载在分子筛(优选小孔沸石)上和/或内时。
在某些实施方案中,促进剂金属氧化物是钒,例如游离钒、钒离子或钒的氧化物或它们的衍生物。优选地,钒的形式是氧化钒(V2O5)。除钒之外,促进剂金属氧化物可以包括其他催化活性金属氧化物,例如钨的氧化物和/或钼的氧化物。如本文使用,“催化活性”金属氧化物是在NOx的催化还原和/或NH3或其他氮基SCR还原剂的氧化中作为分子组分直接参与的金属氧化物。在某些实施方案中,SCR催化剂是V2O5/WO3/TiO2,并且任选地包括MoO3。
优选的分子筛载体包括沸石和SAPO,其具有选自由AEI、AFX、CHA、KFI、LEV、ERI、DDR、UEI、RHO、EAB、PAU、MER、GOO、YUG、GIS、UFI、VIN、AEI/CHA共生物、BEA、MFI、MOR和FER组成的组的骨架。在某些实施方案中,所述骨架选自AEI、CHA和它们的共生物。优选的铝硅酸盐分子筛具有约10至约50,优选地约15至约25的二氧化硅比氧化铝的比值。
尤其优选的SCR催化剂包括:V2O5/WO3/TiO2,任选地包括MoO3;负载在铝硅酸盐分子筛上的Cu,铝硅酸盐分子筛具有选自AEI、CHA或它们的组合或共生物的骨架;和负载在铝硅酸盐分子筛上的Fe,所述铝硅酸盐分子筛具有选自BEA和FER的骨架。
优选地选择第一氧化催化剂来包括在例如低于约250℃、低于约200℃或低于约150℃的低温下将NH3完全氧化成NOx和H2O。优选地,第一氧化催化剂并非部分氧化催化剂。第一氧化催化剂优选地含有贵金属,例如钌、铼、铑、钯、银、锇、铱、铂、金或它们的组合。用于第一氧化催化剂的优选金属包括PGM,尤其是Pt以及Pt与Pd的组合。在某些实施方案中,第一氧化催化剂含有基于存在于第一氧化催化剂中的贵金属的总重量计的至少约30重量%,至少约50重量%、至少约60重量%、至少约75重量%或至少约90重量%的Pt。
第一氧化催化剂的金属优选地由高表面面积载体来负载。用于第一氧化催化剂金属的载体的类型无具体限制,前提条件是其是具有大表面面积的颗粒,是惰性的并且适合在后处理系统中使用。载体材料的实例包括耐火金属氧化物,例如氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化铈及它们的物理混合物或复合物,尤其优选氧化铝。在某些实施方案中,载体具有宽孔(例如100–350)或具有宽孔和窄孔两者。在某些实施方案中,载体具有至少50m2/g,优选地约50-500m2/g,更优选地约50–300m2/g或约150–250m2/g的BET表面积。耐火金属氧化物载体优选地具有优选地通过压汞孔隙率测定法测量的约0.1-0.5g/cc(例如约0.2–0.4g/cc)的孔体积。载体材料的基于颗粒计数的平均粒度优选地为约0.01-10μm,例如约0.5–5μm、约0.1–1μm或约5–10μm,并且优选地在这些范围之一内具有大多数颗粒计数。在某些实施方案中,载体的D90粒度在这些范围之一内。
用于第一氧化催化剂中的金属的其他载体包括分子筛,例如具有沸石类型骨架的铝硅酸盐、硅铝磷酸盐和铝磷酸盐,例如AEI、AFX、CHA、KFI、LEV、ERI、DDR、UEI、RHO、EAB、PAU、MER、GOO、YUG、GIS、UFI、VIN、AEI/CHA共生物、BEA、MFI、MOR和FER。
本发明的催化剂可以在非均相催化反应系统(即,与气体反应物接触的固体催化剂)中使用。为改善接触表面面积、机械稳定性和流体流动特性,可以将催化剂组分设置在基材上和/或内,例如作为涂层。在某些实施方案中,将含有一种或多种催化剂组分的载体涂层作为涂层施加至惰性基材,例如波纹金属板或蜂窝堇青石砖。载体涂层优选地为溶液、混悬液或浆料。合适的涂层包括:覆盖基材的一部分或整个基材的表面涂层;渗透基材的一部分的涂层;渗透基材的涂层;或它们的一些组合。除催化剂组分之外,载体涂层还可以包含以下组分,例如填充剂、粘合剂、稳定剂、流变改性剂及其他添加剂,所述其他添加剂包括氧化铝、二氧化硅、非沸石二氧化硅氧化铝、二氧化钛、氧化锆、二氧化铈中的一种或多种。在某些实施方案中,载体涂层包含孔形成剂,例如石墨、纤维素、淀粉、聚丙烯酸酯和聚乙烯等等。这些额外的组分并非必然催化催化所需反应,而是,例如通过增加其工作温度范围、增加催化剂的接触表面面积、增加催化剂至基材的粘附、改变流变以更好地处理等等来改善催化材料的有效性。通常,可基于粒度来区分用作粘合剂的金属氧化物颗粒与用作载体的金属氧化物颗粒,其中粘合剂颗粒相对于载体颗粒而言显著更大。
在某些实施方案中,用于第一氧化催化剂的载体与其他组分(例如填充剂、粘合剂和增强剂)一起捏和成可挤出的糊剂,然后将所述糊剂穿过模具挤出以形成蜂窝砖。在干燥和/或煅烧蜂窝砖之前或之后,将第一氧化催化剂的贵金属组分添加至砖的任一个或多个部分或添加至整个砖以便形成第一氧化催化剂。在其他实施方案中,在挤压之前使含有负载的贵金属的第一氧化催化剂并入至可挤出的糊剂中。然后将SCR催化剂和第二氧化催化剂作为涂层施加在挤出的第一氧化催化剂砖上。
用于本发明的两个基材设计是板式和蜂窝式。板型催化剂具有相对较低的压降,并且比蜂窝式更不易堵塞和弄脏,但板构造更大并且更昂贵。板通常由金属或波纹金属构成。
蜂窝基材包括多个邻近的并行通道,所述通道一般从基材的入口面延伸至基材的出口面,并且两端开放(流通式基材)或以棋盘型方式来封闭交替的端(壁-流动过滤器)。此几何形状产生高表面积比体积之比。蜂窝构造比板类型更紧凑,但具有更高的压降并且更易堵塞。然而,对于大多数可移动应用,优选的基材是蜂窝。
对于某些应用,蜂窝流动即使整料具有高孔隙密度,例如每平方英寸约600至800个孔隙,和/或约0.18–0.35mm、优选约0.20–0.25mm的平均内壁厚度。对于某些其他应用,蜂窝流通式整料优选地具有每平方英寸约150–600个孔隙,更优选地每平方英寸约200–400个孔隙的低孔隙密度。优选地,蜂窝整料是多孔的。除堇青石、碳化硅、氮化硅、陶瓷和金属之外,可用于基材的其他材料包括氮化铝、氮化硅、钛酸铝、α-氧化铝、莫来石(mullite)(例如针状莫来石)、铯榴石(pollucite)、thermet(例如Al2OsZFe、Al2O3/Ni或B4CZFe)或包含它们中任何两种或更多种的段的复合物。优选的材料包括堇青石、碳化硅和氧化铝钛酸盐。在某些实施方案中,基材是惰性的。
蜂窝的基材壁优选地具有有利于载体涂层的孔隙率和孔径。孔隙率是对多孔基材中的空隙空间百分比的量度。优选地,多孔基材具有约30至约80%的孔隙率,例如约40至约75%、约40至约65%或从约50至约60%。作为基材的总空隙体积百分比来测量的孔连通性是将孔、空隙和/或通道接合起来形成穿过多孔基材(即,从过滤器的入口面向过滤器的出口面)的连续通路的程度。优选地,多孔基材具有至少约30%,更优选地至少约40%的孔连通性体积。
基材壁的平均孔径可以通过任何可接受的方式(包括通过水银孔率法)来测定。优选的多孔基材具有约10至约40μm的平均孔径,例如约20至约30μm,约10至约25μm,约10至约20μm,约20至约25μm,约10至约15μm和约15至约20μm。
转到图1A,示出本发明的实施方案,其具有:载体壁(14);第一层,其具有第一氧化催化剂12;和第二层,其具有第二氧化催化剂和SCR催化剂的混合物。一般而言,本发明的催化剂层渗透基材;渗透基材的一部分,例如大多数部分;涂覆基材的表面;或它们的一些组合。此处,第一层12直接设置在基材14上作为下层,并且第二层10设置在第一层12上作为覆盖层。优选地,第一层12和第二层10是物理上不同且单独但连续的层。如本文使用,关于层的术语“连续的”是指每一层与其邻近的一层或多层接触,并且所述层以一个在另一个之上的方式作为整体布置在基材上。如本文使用,术语“第一层”和“第二层”用于描述催化剂制品中的催化剂层的相对于流动穿过催化剂制品、流动通过催化剂制品和/或在催化剂制品之上流动的排气的垂直方向的相对定位。在正常排气流动条件下,排气在接触第一层之前接触第二层并且至少部分地渗透第二层,并且随后返回穿过第二层以离开催化剂组分。
在图1A中,第一层和第二层设置在基材的整个轴向长度之上。然而,在其他实施方案中,一种或多种催化剂层仅覆盖基材的一部分(参见图1D)。例如,可以从基材的前方46或基材的尾部48相对于排气流50穿过基材的总方向将催化剂层施加至基材的长度的约10%。在某些实施方案中,至少第一氧化催化剂层涂覆在基材尾部48的部分上。在其他实施方案中,催化剂层优选地从基材的尾部48或基材的前方46覆盖基材的约25%、约50%或约75%。可以将催化剂涂层施加至基材的相同或不同的部分,但优选地,含有SCR催化剂的涂层完全覆盖含有第一氧化催化剂的涂层,以使得由催化剂层处理的所有排气将在能够到达第一层之前首先通过第二层。
优选地,含有第二氧化催化剂的涂层优选地处于含有第一氧化催化剂的涂层或层之上顶部和/或在其上游。优选地,第二层完全覆盖第一层,以使得由催化剂层处理的所有排气将在能够到达第一层之前首先通过第二层。
在图1B中,示出本发明的优选实施方案,其中第一氧化催化剂设置在高度多孔的基材壁25内。涂覆基材覆盖有含有SCR催化剂和第二氧化催化剂二者的混合物的层。此实施方案的实例包括渗透进高孔隙率基材(优选流通式基材)的壁中或涂覆在其内的Pt。然后用SCR催化剂和第二氧化催化剂的混合物涂覆含有Pt的基材。或者,含有Pt的基材可以含有单独的SCR催化剂层和第二氧化催化剂层。在另一实施方案中,含有Pt的基材是挤压催化剂,然后用SCR/第二氧化混合层或单独的SCR和第二氧化催化剂层涂覆。
图1C示出本发明的实施方案,其中第二氧化催化剂30在SCR催化剂层31之上形成单独且不同但连续的层。此处,第二氧化催化剂和SCR催化剂并未混合且未作为单个载体涂层施加,而是,作为单独层形成在基材上。重要的是,SCR催化剂层设置在整个第一氧化催化剂层32之上,并且第二氧化催化剂层设置在SCR层之上。SCR层覆盖整个第一氧化催化剂层以防止经由下层中的氨氧化形成的未处理次级NOx离开系统而不接触SCR催化剂。在某些实施方案中,例如图1C中见到的一个实施方案,第一氧化催化剂设置在基材的仅一部分上,优选的是在尾部部分上,而SCR催化剂层覆盖整个基材。在其他实施方案中,将第一氧化催化剂施加至基材的整个长度。
重要的是,第二氧化催化剂设置在SCR催化剂层之上和/或其上游。在图1D中,第二氧化催化剂40直接涂覆在SCR和第一氧化催化剂上游的基材上,其中与“下游”相对的“上游”是相对于穿过基材或在基材之上的排气流50的垂直方向。在某些实施方案中,将第二氧化催化剂并入至基材壁的部分或区域中,其处于含有SCR和第一氧化催化剂的基材的下游部分或区域的上游。
替代于被涂覆在基材壁上,第二氧化催化剂可以被并入至高孔隙率基材壁中,例如作为渗透该壁或可以被并入至形成基材的可挤出的糊剂中的内部涂层。第二氧化催化剂可以限制在上游区域或可以被并入至基材的整个长度,前提条件是SCR和第一氧化催化剂设置在下游部分或区域。在某些实施方案中,可以将第二氧化催化剂并入至基材的整个长度,可以将第一氧化催化剂涂覆或浸渍在第二氧化催化剂之上的壁内,前提条件是将第一氧化催化剂限制在基材尾部的区域,并且可以将SCR催化剂涂覆在含有第一氧化催化剂的区域之上。图1E示出高孔隙率基材壁64,所述高孔隙率基材壁64具有:从前端66到尾端68沿基材的整个长度的壁中的第二氧化催化剂60;壁内尾部区域上的第一氧化催化剂62,其中在尾部区域也含有第一氧化催化剂60;和至少覆盖尾部区域的SCR涂层61。在这种实施方案中,尾部区域含有除Pd之外的贵金属,例如Pt。
在某些实施方案中,用于每一层或用于两层或更多层的组合的基材上和/或内的载体涂层或浸渍负载量是0.1至8g/in3,更优选地0.5至6g/in3,并且甚至更优选地1至4g/in3。在某些实施方案中,用于每一层或用于两层或更多层的组合的基材上和/或基材内的载体涂层或浸渍负载量>1.00g/in3,例如>1.2g/in3、>1.5g/in3、>1.7g/in3或>2.00g/in3或例如1.5-2.5g/in3。
在某些实施方案中,第二氧化催化剂以足够产生约0.1至约50gPd/ft3,更优选地约0.5至约20g Pd/ft3,并且甚至更优选地约1至约10g Pd/ft3的Pd负载量的量存在。
在某些实施方案中,第一氧化催化剂以足够产生约0.1至约75g贵金属/ft3,更优选地约0.5至约20g贵金属/ft3或约30–50g贵金属/ft3,并且甚至更优选地约1至约10g贵金属/ft3的催化剂负载量的量存在,虽然一些应用(其中催化剂用于产生放热)可以含有第一氧化催化剂,所述第一氧化催化剂具有至多75g/ft3,例如至多约50g/ft3的贵金属负载量。当贵金属是Pt时,上述贵金属范围尤其相关。
在某些实施方案中,SCR催化剂含有基于促进剂金属和载体的总重量计的约0.1至约10重量%,更优选地约1至约7重量%,并且甚至更优选地约2.5至约5重量%的促进剂金属。在本发明的至少一个实施方案中,SCR催化剂层与第一氧化催化剂层的重量比为从约0.5:1至约10:1,并且更优选地从约2:1至约7:1。
在某些实施方案中,本发明是后处理排气系统,所述后处理排气系统被调适以处理由稀燃燃烧过程产生的NOx、CO、NH3和/或HC,例如来自柴油发动机或固定式燃气轮机的排气。在图2A中,示出该系统的实施方案,所述系统包括:排气歧管500;排气歧管500下游的SCR催化剂520;含氮还原剂510的任选来源,其在歧管500和SCR催化剂520之间的点515处被引入排气流中(未示出);和SCR催化剂520下游的ASC催化剂(如本文描述的540)。此处,SCR催化剂520和ASC催化剂530作为单独的方块示出。这些单独的方块可以彼此靠近和接触或以特定距离隔开,前提条件是它们彼此流体连通并且前提条件是SCR催化剂方块设置在氨逸出催化剂方块的上游。在其他实施方案中,SCR催化剂520和ASC催化剂530组件以上游/下游的布置来组合在相同的方块上。例如,SCR催化剂可以处于流通式基材的上游侧上,并且ASC催化剂可以处于流通式基材的下游侧上。在其他实施方案中,将SCR催化剂涂覆在壁流式过滤器的入口侧上,并且将ASC催化剂涂覆在流通式过滤器的出口侧上。也可以包括其他组件,例如下游或上游DPF。此处,“上游”和“下游”是指后处理系统中的组件基于穿过系统的排气流575的垂直方向的相对位置。
排气歧管优选地为用于引导排气离开发动机进入后处理系统的管道。在排气歧管500处或附近可以任选地包括其他组件,例如涡轮增压器。在通过歧管之后,排气接触初级SCR催化剂以选择性还原来自排气的NOx。类型SCR催化剂无具体限制,但优选地为如本文描述的SCR催化剂。独立的上游SCR催化剂520可以相对于ASC组件540中使用的SCR催化剂具有相同配制物或不同配制物。
在某些实施方案中,例如在图2A中示出的一个实施方案,所述系统包括含氮还原剂510的来源,例如脲、氨或其前体或衍生物,其被注入或以其他方式引入SCR催化剂上游的排气流中(未示出)。在其他实施方案中,所述系统不含将氮基还原剂注入系统中的组件,而是,在SCR工艺中用于消耗的氮基还原剂(尤其是NH3)的至少一部分由设置在SCR催化剂上游的NOX吸附器催化剂(NAC)、稀NOX捕获器(LNT)或NOX存储/还原催化剂(NSRC)供应。用于本发明的NAC组分包括碱性材料(例如碱金属、碱土金属或稀土金属,包括碱金属的氧化物、碱土金属的氧化物和它们的组合)和贵金属(例如铂)的催化剂组合,以及任选的还原催化剂组分,例如铑。用于NAC的碱性材料的特定类型包括氧化铯、氧化钾、氧化镁、氧化钠、氧化钙、氧化锶、氧化钡和它们的组合。贵金属优选地以约10至约200g/ft3,例如20至60g/ft3存在。或者,催化剂的贵金属特征为可从约40至约100克/ft3的平均浓度。
在某些条件下,在周期性富再生事件期间,NH3可以在NOx吸附器催化剂之上产生。NOx吸附器催化剂下游的SCR催化剂可以改善整个系统NOx还原效率。在组合系统中,SCR催化剂在富再生事件期间能够存储从NAC催化剂释放的NH3,并且在正常贫稀操作条件期间使用存储的NH3来选择性还原逸出通过NAC催化剂的一些或全部NOx。
ASC组件530在SCR催化剂的下游,并且作用在于还原逸出通过系统的氨并且氧化可能在排气中的CO和/或HC的至少一部分,并且优选地氧化可能在排气中的CO和/或HC的至少大多数。优选地,所述系统在ASC组件540上游不含氧化催化剂,例如单独基材上的柴油机氧化催化剂。
图2B示出本发明的另一实施方案,其涉及排气后处理系统,其用于:接收含有NOx、CO和HC的排气90,例如由稀燃发动机产生的排气;和处理排气以产生清洁排气160,清洁排气160相对于排气90含有较低浓度的NOx、CO和/或HC。图2B中的后处理系统包括燃料来源130,所述燃料来源130在SCR催化剂120和DOC催化剂105下游的点135处被引入。优选地,燃料来源130在SCR催化剂120和ASC催化剂130之间的点135处被引入后处理系统中,其中系统在SCR催化剂120和ASC催化剂140之间优选地不含任何催化剂组分。
燃料来源通常是烃基燃料,所述烃基燃料与产生排气的发动机使用的燃料相同或类似。将燃料周期性地引入DPF组件150上游的排气系统,并且在放热反应中充当反应物。更特别地,燃料由ASC 140氧化以经由放热反应来产生热量。该热量进而用于燃烧已经累积在DPF上的烟尘或其他颗粒物质,从而除去烟尘并且再生DPF。再生DPF防止堵塞和过度系统背压。本发明的DPF优选地为陶瓷壁流式过滤器。过滤器可以为无涂层的或涂有一种或多种催化剂。过滤器的再生可以主动地或被动地进行。
系统还包括任选的子系统,所述子系统用于在SCR催化剂120上游和DOC组件105下游的点115处将氮基还原剂110(例如脲、氨或其前体或衍生物)引入系统中。
所述系统包含用于将排气中的一氧化氮氧化成二氧化氮的氧化催化剂105(例如柴油机氧化催化剂(DOC)),所述氧化催化剂105可以位于向排气中计量供应含氮还原剂的点115的上游。DOC还可以完全或部分地氧化排气中的CO和/或HC。在一个实施方案中,例如在250℃至450℃的氧化催化剂入口处在排气温度下,在进入SCR催化剂之前,氧化催化剂被调适以产生具有从约4:1至约1:3的NO与NO2的体积比的气流。氧化催化剂可以包含涂覆在流通式整料基材上的至少一种铂族金属(或这些铂族金属的一些组合),例如铂、钯或铑。在一个实施方案中,所述至少一种铂族金属为铂、钯或铂和钯两者的组合。铂族金属可以被负载在高表面面积载体涂层组分上,高表面面积载体涂层组分例如氧化铝、沸石(例如铝硅酸盐沸石)、二氧化硅、非沸石二氧化硅氧化铝、二氧化铈、氧化锆、二氧化钛或含有二氧化铈和氧化锆两者的混合氧化物或复合物氧化物。
在本发明的另一实施方案中,提供用于处理排气的方法,所述方法优选地通过降低由稀燃燃烧过程产生的排气中的NOx、NH3、CO、HC和颗粒物质中的至少一种的浓度来实现。优选地,该过程包括用于氧化未由上游SCR反应转化的过量NH3(氨氧化或AMOX)的步骤。
在优选实施方案中,本发明是用于处理排气的方法,所述方法包括将气体中的NOx化合物还原和/或NH3氧化的步骤,所述方法包括使所述气体与本文描述的用于NOx化合物催化还原的催化剂组合物接触足够的时间,以降低气体中的NOx化合物和/或NH3的水平。
在某些实施方案中,SCR和/或AMOX过程在至少100℃的温度下进行。在另一实施方案中,所述一个或多个过程在从约150℃至约750℃的温度下发生。在特定实施方案中,温度范围是从约175至约550℃。在另一定实施方案中,温度范围是从175至400℃。在另一实施方案中,温度范围是450至900℃,优选地500至750℃、500至650℃、450至550℃或650至850℃。
根据本发明的另一方面,提供用于将气体中的NOX化合物还原和/或NH3氧化的方法,所述方法包括使所述气体与本文描述的催化剂接触足够时间,以降低气体中的NOx化合物的水平。本发明的方法可以包括一个或多个以下步骤:(a)累积和/或燃烧与催化过滤器的入口接触的烟尘;(b)使含氮还原剂在接触催化过滤器之前引入排气流中,优选地无涉及处理NOx和还原剂的插入的催化步骤;(c)在NOx吸附器或稀NOx捕获器之上产生NH3,并且优选地使用此NH3作为下游SCR反应中的还原剂;(d)使排气流与DOC接触以将烃基可溶解有机级分(SOF)和/或一氧化碳氧化成CO2和/或将NO氧化成NO2,其进而可用于使颗粒过滤器中的颗粒物质氧化;和/或减少排气中的颗粒物质(PM);(e)在还原剂存在下使排气与一个或多个流通式SCR催化剂装置接触,以降低排气中的NOx的浓度;和(f)使排气与优选在SCR催化剂下游的氨逸出催化剂接触来在将排气排入大气之前氧化大多数(若非全部)氨或在排气进入/再进入发动机之前使排气通过再循环回路。
在另一实施方案中,本发明是用于再生过滤器的方法。在这种实施方案中,催化剂制品用于燃烧烃基燃料,所述烃基燃料被注入在ASC上游并且优选地在初级SCR催化剂下游的排气中。所述燃烧加热该排气,其进而接触颗粒过滤器。高温排气促进过滤器上的烟尘及其他颗粒物质的燃烧,从而除去烟尘和颗粒物质。除去烟尘和颗粒物质再生了过滤器。
本文描述的用于处理排气的方法可以在来源于燃烧过程的排气上进行,所述来源于燃烧过程的排气例如来自内燃发动机(无论可移动的或固定的)、燃气轮机和燃煤或燃油发电厂。方法还可以用于处理来自例如精炼的工业过程的气体,来自精炼厂加热器和锅炉、炉子、化学处理工业、焦炉、城市废物发电厂和焚烧炉等等的气体。在特定实施方案中,该方法用于处理来自车辆稀燃内燃发动机(例如柴油发动机)、稀燃汽油发动机或液化石油气或天然气供能的发动机的排气。
在某些实施方案中,本发明涉及用于富燃燃烧的后处理系统,所述后处理系统包括:三效(TWC)催化剂,其用于减少氮氧化物(NOx)、烃(HC)和一氧化碳(CO)的排放;和本文描述的下游ASC催化剂。在富条件下操作例如发动机的燃烧过程,其中空气比燃料的比具有大于化学计量的燃料量(即,空气比燃料的比低于化学计量比),从发动机出来的NOx的显著部分在三效催化剂之上被转化成氨(NH3),但对于ASC催化剂,其作为次级排放物而排出。对于装备有TWC催化剂的典型富燃发动机,尾管NH3可以为大约400ppm。
根据本发明的实施方案,用于减少氨(NH3)排放的系统包括:(a)第一组件,其包括第一基材和设置其上的三效催化剂,其中第一组件设置在第二组件的上游并且与之流体连通,所述第二组件包括第二基材和ASC催化剂,其有设置在第二基材上和/或内的第一催化剂层和涂覆在该第一催化剂层之上的第二催化剂层;其中第一催化剂层包含第一氧化催化剂,并且第二催化剂层含有以下(i)和(ii)的混合物:(i)由负载的钯组成的第二氧化催化剂和(ii)用于选择性还原NOx和/或存储NH3的催化剂;并且其中第一氧化催化剂和第二氧化催化剂是不同的配制物;和任选(b)含氧气体入口,其设置在所述第一组件和第二组件之间。在本发明的另一实施方案中,系统另外包括:(c)第一气态进料流,其包含来源于富燃燃烧过程的排气,其中所述进料流在第一组件的上游并且与之流体连通;和(d)管道,其设置在第一组件和第二组件之间并且与之流体连通,并且与含氧气体入口流体连通。在至少一个实施方案中,用于NH3氧化的小孔分子筛是Cu负载的CHA骨架型小孔分子筛,例如Cu负载的SAPO-34。
在本发明的另一实施方案中,用于减少氨(NH3)排放的方法包括:将含氧气体引入具有NH3和λ<1的排气中以提供氧化的气流;和使氧化的气流暴露于NH3氧化催化剂(包括负载至少一种过渡金属的至少一种小孔分子筛)以将NH3的至少一部分选择性氧化成N2。在本发明的另一实施方案中,该方法还在引入含氧气体的步骤上游包括以下步骤:将富燃排气暴露于用于转化氮氧化物(NOx)、烃(HC)和一氧化碳(CO)的三效催化剂以产生具有NH3和λ<1的气流。可以将含氧气体引入以产生具有至少约1:1,优选地从约2:1至约1:1的O2:NH3比的氧化的气流。在至少一个实施方案中,含氧气体包含至少0.1%氧气,例如为环境空气。优选地当富燃排气处于至少约350℃,优选地在约400-650℃范围内的温度时,进行暴露步骤。
TWC优选地包括负载在载体材料上的单层或多层活性催化剂材料(即,铂族金属(PGM)或非PGM),或由其组成,其可以或可以不具有涂覆整料形式或者挤出形式的用于增强比催化剂活性(例如H2S抑制、NOx存储、HC存储)的另外添加剂。
实施例
实施例1:顶层中具有Pd的ASC催化剂的制备
用第一氧化催化剂涂覆流通式蜂窝芯(4.66英寸×3.0英寸,400cpsi,4mil壁厚度)以形成底层,并且随后用第二氧化催化剂/SCR催化剂涂覆以形成底层之上的顶层。
底层的催化剂如下制备:将研磨的γ氧化铝载体涂层添加至合适的容器中。γ氧化铝的d50被测定为约3.2-4.0μm。使用高剪切混合器将去离子水混入载体涂层中,并且将琥珀酸添加至载体涂层以形成凝胶。将各种量的硝酸铂和任选硝酸钯添加至凝胶中,并且然后将材料混合以形成浆料。将浆料施加至蜂窝芯作为底部催化剂层,并且干燥和煅烧该涂覆芯。样品中的Pt和Pd的各种量在表1中示出。
顶层的催化剂如下制备:将醋酸铜溶液与SAPO-34混合以产生具有约2.5重量%Cu的催化剂。单独地,Pd硝酸盐和琥珀酸在去离子水中以1.1琥珀酸/Pd重量比混合以制备始润溶液。将此溶液通过始润法添加至γ氧化铝载体,目标是超过始润点5%的溶液量以产生湿糊剂。将该糊剂干燥、研磨并且在静态烘箱中使用3℃/分钟的升温速率在500℃下烧2小时。
单独地,在去离子水中形成氧化铝的分散体。将干燥的Cu/SAPO-34添加至分所述散体,随后添加干燥的Pd/氧化铝。将所得的载体涂层施加至蜂窝芯作为顶部催化剂层,并且干燥和煅烧该涂覆芯。顶部载体涂层具有约2.6–2.8g/in3的负载量,包括约0.35g/in3的氧化铝和约2g/in3的Cu/SAPO-34。底部载体涂层具有约0.7g/in3的负载量。
表1
实施例2:催化剂性能
针对NH3转化率、CO转化率和HC转化率来评估催化剂样品,所述催化剂样品具有:顶层,其含有钒基SCR催化剂和Pd氧化催化剂的混合物;和底层,其含有Pt AMOX催化剂。将这些结果与类似但顶层中无Pd氧化催化剂的催化剂比较进行。与顶层中无Pd的催化剂相比,顶层中具有Pd的催化剂示出显著更佳的CO和HC转化性能(图3和图4)。令人惊奇的是,制备有Pd顶层和没有Pd顶层的催化剂示出在NH3转化率和NOx输出方面极类似的性能(图5)。
针对就在广泛温度范围内NH3转化以及就CO转化的N2选择性来评估催化剂样品,所述催化剂样品具有:顶层,其含有Cu/SAPO-34 SCR催化剂和Pd氧化催化剂的混合物;和底层,其含有Pt AMOX催化剂。将这些结果与类似但顶层中无Pd氧化催化剂的催化剂进行比较。与顶层中无Pd的催化剂相比,顶层中具有Pd的催化剂示出显著较佳的CO转化性能(图8)。令人惊奇的是,制备有Pd顶层和没有Pd顶层的催化剂示出在就NH3转化的N2选择性方面极类似的性能(图7)。
Claims (15)
1.用于处理排气的催化剂制品,所述催化剂制品包含基材,所述基材具有设置在所述基材之上或之内的第一催化剂层和涂覆在所述第一催化剂层上的第二催化剂层;其中所述第一催化剂层包含第一氧化催化剂,并且所述第二催化剂层含有以下(i)和(ii)的混合物:(i)由负载的钯组成的第二氧化催化剂和(ii)用于选择性还原NOx和/或存储NH3的催化剂,其中所述用于选择性还原NOx和/或存储NH3的催化剂是负载有Fe和/或Cu的沸石;并且其中所述第一氧化催化剂和所述第二氧化催化剂是不同的配制物。
2.用于处理排气的催化剂制品,所述催化剂制品包含:
a.基材;
b.第一氧化催化剂层,所述第一氧化催化剂层设置在所述基材上和/或内;
c.第二催化剂层,所述第二催化剂层涂覆或设置在所述第一催化剂层之上,其中所述第二层含有用于选择性还原NOx和/或存储NH3的催化剂;和
d.第三催化剂层,所述第三催化剂层涂覆或设置在所述第二催化剂层之上,其中所述第三催化剂层包含由负载的Pd组成的第二氧化催化剂;
其中所述第一氧化催化剂和所述第二氧化催化剂是不同的配制物。
3.用于处理排气的催化剂制品,所述催化剂制品包含:
a.基材;
b.第一催化剂层,所述第一催化剂层包含设置在所述基材上和/或内的第一氧化催化剂;
c.第二催化剂层,所述第二催化剂层涂覆或设置在所述第一催化剂层之上,其中所述第二层含有用于选择性还原NOx和/或存储NH3的催化剂;和
d.第三催化剂层,所述第三催化剂层涂覆或设置在所述第一催化剂层和第二催化剂层的上游,其中所述第三催化剂层包含由负载的Pd组成的第二氧化催化剂;
其中所述第一氧化催化剂和所述第二氧化催化剂是不同的配制物。
4.权利要求2或权利要求3所述的催化剂制品,其中所述第三催化剂层基本上不含钌、铼、铑、银、锇、铱、铂、金、碱金属和碱土金属以及过渡金属,除了用于钯的金属氧化物颗粒载体的形式的过渡金属之外。
5.权利要求1或权利要求2或权利要求3所述的催化剂制品,其中所述第二催化剂层基本上不含Ag、Au、Pt、Rh、Ru、Ir和Os。
6.权利要求1或权利要求2或权利要求3所述的催化剂制品,其中所述第一氧化催化剂是负载的贵金属。
7.权利要求1或权利要求2或权利要求3所述的催化剂制品,其中所述第一氧化催化剂是负载在金属氧化物颗粒上的Pt或负载在金属氧化物颗粒上的Pt和Pd的混合物。
8.权利要求2或权利要求3所述的催化剂制品,其中用于选择性还原NOx和/或存储NH3的所述催化剂是负载有Fe和/或Cu的沸石。
9.权利要求1或权利要求2或权利要求3所述的催化剂制品,其中所述基材是具有50–65%的壁孔隙率的流通式蜂窝。
10.权利要求1或权利要求2或权利要求3所述的催化剂制品,其中所述第一催化剂层的大部分设置在所述基材壁内,并且所述第二催化剂层的大部分设置在所述基材壁的表面上。
11.用于处理排气的系统,所述系统包括:
a.排气歧管;
b.子系统,其用于将氮基还原剂引入所述排气中;
c.SCR催化剂;和
d.前述权利要求中任一项中定义的催化剂制品;
其中组件(a)–(d)串联地流体连通,并且分别处于从上游到下游的连续顺序;并且其中所述系统在所述基材与所述排气歧管之间不含氧化催化剂。
12.用于处理排气的系统,所述系统包括:
a.第一氧化催化剂,其用于产生4:1至1:3的NO/NO2比;
b.子系统,其用于将氮基还原剂引入所述排气中;
c.SCR催化剂;
d.用于将燃料引入所述排气中的注射器;
e.第二流通式整料,其具有设置在所述基材上或内的第二催化剂层和涂覆在第二催化剂层的至少一部分之上的第一催化剂层;其中所述第一催化剂层含有以下(i)和(ii)的混合物:(i)由第一载体上的钯组成的第一氧化催化剂和(ii)用于选择性还原NOx和/或存储NH3的催化剂,并且所述第二催化剂层包含第二氧化催化剂,其中所述用于选择性还原NOx和/或存储NH3的催化剂是负载有Fe和/或Cu的沸石;其中所述基材与所述排气歧管流体连通;和
f.柴油机颗粒过滤器;
其中组件(a)–(e)分别处于从上游到下游的连续顺序。
13.用于处理排气的方法,所述方法包括使含有NH3的排气与根据权利要求1至10中任一项所述的催化剂制品接触;其中所述接触(a)将所述NH3的至少一部分存储在所述第二催化剂层中;(b)使所述NH3的至少一部分氧化以形成N2和/或次级NOx;并且(c)用所述存储的NH3选择性还原所述次级NOx的至少一部分以产生N2和H2O。
14.权利要求13所述的方法,其中所述排气还包含CO和/或烃;并且其中所述接触使所述CO和/或烃的至少一部分氧化以形成CO2和任选的H2O。
15.权利要求13或权利要求14所述的方法,还包括以下步骤:
d.将燃料引入所述催化剂制品上游的所述排气中;
e.使所述燃料与所述催化剂制品接触以氧化所述燃料,并且产生加热的排气;和
f.使用所述加热的排气来再生下游的颗粒过滤器。
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