CN105682790A - 用于柴油氧化催化剂用途的协同pgm催化剂体系 - Google Patents

用于柴油氧化催化剂用途的协同pgm催化剂体系 Download PDF

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CN105682790A
CN105682790A CN201580002403.2A CN201580002403A CN105682790A CN 105682790 A CN105682790 A CN 105682790A CN 201580002403 A CN201580002403 A CN 201580002403A CN 105682790 A CN105682790 A CN 105682790A
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spgm
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Z·纳扎波尔
S·高登
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Clean Diesel Technologies Inc
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Abstract

公开了协同铂族金属(SPGM)氧化催化剂体系。所公开的SPGM氧化催化剂体系可包括具有Cu-Mn尖晶石结构的载体涂层和包括负载在载体材料氧化物上的PGM，如钯(Pd)、铂(Pt)、铑(Rh)或其组合的外覆涂层。SPGM体系表现出未燃烃(HC)和一氧化碳(CO)减排以及NO氧化成NO2的显著改进，这能够降低燃料消耗。所公开的SPGM氧化催化剂体系与PGM氧化体系相比表现出增强的催化活性，表明在所公开的SPGM氧化催化剂体系内的PGM和Cu-Mn尖晶石组合物之间存在协同效应。所公开的SPGM氧化催化剂体系可用于许多DOC用途。

Description

用于柴油氧化催化剂用途的协同PGM催化剂体系
对相关申请的交叉引用
本申请与2014年4月11日提交的名称为SynergizedPGMCatalystSystemsforDieselOxidationCatalystApplications的美国专利申请No.14/251169相关，其要求2013年11月26日提交的名称为SystemandMethodsforUsingSynergizedPGMasaThree-WayCatalyst的美国专利申请No.14/090861的优先权。
背景
技术领域
本公开大体上涉及低载量PGM催化剂体系，更特别涉及具有至少两层复合材料并用于柴油氧化催化剂(DOC)用途、具有改进的起燃性能和催化活性的协同PGM催化剂体系。
背景信息
柴油机废气排出物是不仅包括一氧化碳(CO)、未燃烃(HC)和氮氧化物(NOX)，还包括被称作颗粒物(PM)的液体和固体形式的凝相材料的多相混合物。
通常，在柴油机排气系统中提供的DOC包括分散在金属氧化物载体上的铂族金属(PGM)以将一些或所有这些排气组分转化成较无害的组分。除HC、CO和PM的转化外，包括PGM的DOC促进NOX氧化成NO2。PGM独自或与其它贵金属结合用作氧化催化剂中的活性组分，但贵金属在该催化剂体系中以不同效率催化不同的氧化反应。
早期的柴油氧化催化剂由在高表面积载体上的铂构成并通常在高达500℃至600℃的温度下工作。更最近，已要求柴油氧化催化剂在更高温度下工作以再生传统上位于该氧化催化剂下游的微粒过滤器。
混合铂(Pt)和钯(Pd)催化剂已知与单独的铂相比提供改进的热稳定性，因此催化剂工业已转向制造Pt/Pd基柴油氧化催化剂。但是，目前可得的Pt/Pd基氧化催化剂受困于铂和钯之间的不良合金化和在铂浓度提高时和在使用过程中金属粒子的尺寸增长的趋势的问题。这两个因素都限制催化剂的性能和热稳定性进一步增强的可能性。尽管Pd的成本低于Pt，但Pd基催化剂复合材料通常表现出用于CO和HC氧化的较高起燃温度，可能造成HC和/或CO起燃的延迟。另外，Pd基催化剂复合材料可能毒化Pt的转化烃和/或氧化NOX的活性并也可能使该催化剂复合材料在用于柴油机排气系统时更易于硫中毒。
铑(Rh)在催化剂体系中用于在过量氧存在下通过CO还原NOX。由于Rh是Pt开采的副产物，任何催化剂体系中的Rh必须在该催化剂体系的使用寿命期间有效使用。另外，由于Rh在氧化条件下在升高的温度下强相互作用，其可能扩散并溶解以致在催化剂体系上再次建立还原条件时仅部分回收Rh。因此，包括Rh的催化剂体系暴露在高温条件下可能导致在该催化剂体系的寿命期间作为有效催化剂材料的Rh的损失。
因此，随着排放法规变更严格，对开发具有为有效利用改进的性质，特别具有改进的初始活性、改进的热稳定性、受控和稳定的金属粒度和降低的老化的柴油氧化催化剂很感兴趣。持续目标是开发包括提供改进的起燃性能以及残留烃、一氧化碳和NOX的脱除的催化剂复合材料的DOC。另外，随着NO排放标准变严格且PGM变稀少，同时市场流通量小、价格不断波动并始终存在稳定供应的风险等，越来越需要用于DOC用途的新型组合物，包括具有低量PGM催化剂的组合催化剂体系，其可以在提供在柴油氧化条件下增强的催化剂活性方面表现出协同性能并可成本有效地制造。
概述
本公开提供协同铂族金属(SPGM)氧化催化剂体系，其与PGM体系相比表现出在DOC起燃条件下的高催化活性和因此改进的烃、一氧化碳和氮氧化物的起燃性能和氧化。
根据各种实施方案，本公开中的SPGM氧化催化剂可包括至少基底、载体涂层(washcoat)和外覆涂层(overcoat)，其中基底可包括许多材料，如陶瓷材料，载体涂层可包括负载在许多载体金属氧化物，如掺杂ZrO2上的Cu-Mn尖晶石结构，外覆涂层可包括负载在载体材料氧化物，如氧化铝上的特定PGM材料，如钯(Pd)或不同PGM材料的组合，如铂(Pt)和铑(Rh)的双金属复合材料。
为了比较性能和测定具有PGM层的Cu-Mn尖晶石结构的协同效应，可以制备无Cu-Mn尖晶石结构的PGM氧化催化剂作为对照样品。该PGM氧化体系可包括陶瓷基底、包含掺杂ZrO2的载体涂层和包含负载在载体材料氧化物，如氧化铝上的PGM材料，如Pd或Pt和Rh的双金属复合材料的外覆涂层。
所公开的SPGM氧化催化剂和PGM对照体系可以使用如本领域中已知的合适的合成方法，如共研磨法和共沉淀法等制备。
根据本公开的一个方面，为了测定PGM载量和Cu-Mn尖晶石结构在协同和非协同PGM氧化体系的催化性能中对氧化活性的影响，可以使用Pd和Pt/Rh材料的不同载量制备所公开的SPGM体系的新鲜样品和不包括Cu-Mn尖晶石结构的PGM对照体系的新鲜样品。在本公开中，总PGM载量可以低至1.0克/立方英尺。
根据本公开的另一方面，可以对本公开中所用的新鲜SPGM和PGM对照样品进行DOC标准起燃试验。对于在NO、CO和HC转化中的催化活性，可以在稳态条件下进行标准起燃试验。可以为新鲜SPGM样品和PGM对照样品开发催化活性的分析，包括由用于查证Cu-Mn尖晶石的协同效应对催化剂活性的影响和用于测量NO转化成NO2的转化率的起燃试验程序得出的HC和CO起燃温度T50。
本公开的SPGM柴油氧化催化剂可提供在稀燃运行条件下的NO转化率的显著改进，这归因于Pd基和Pt/Rh基PGMDOC中包含的Cu-Mn尖晶石结构的协同效应。此外，所公开的包括Cu-Mn尖晶石结构的SPGM催化剂体系能使催化转化器使用低量的PGM材料。
根据上文，由于ZPGM组合物提供的性能影响(改进柴油氧化催化中的催化层)，本公开中用作协同增效材料的Cu-Mn尖晶石结构形式的催化活性ZPGM材料组合物可获得SPGM氧化催化剂的高分散体系，其可以成本有效地制造以使它们易用于许多DOC用途。
从与附图一起作出的下列详述中可看出本公开的许多其它方面、特征和益处。
附图简述
参照示意性并且无意按比例绘制的附图举例描述本公开的非限制性实施方案。除非被指明代表背景技术，附图代表本公开的方面。
图1相当于根据一个实施方案的具有氧化铝载钯外覆涂层和掺杂氧化锆载Cu-Mn尖晶石载体涂层的SPGM氧化催化剂配置，被称作1型SPGM氧化催化剂体系。
图2图解根据一个实施方案的具有氧化铝载钯外覆涂层和掺杂氧化锆载体涂层的PGM对照体系配置，被称作2型PGM体系。
图3描绘根据一个实施方案的具有氧化铝载铂和铑外覆涂层和掺杂氧化锆载Cu-Mn尖晶石载体涂层的SPGM氧化催化剂配置，被称作3型SPGM氧化催化剂体系。
图4显示根据一个实施方案的具有氧化铝载铂和铑外覆涂层和掺杂氧化锆载体涂层的PGM对照体系配置，被称作4型PGM体系。
图5代表根据一个实施方案1型SPGM氧化催化剂体系和2型PGM对照体系的新鲜样品在大约150℃至大约500℃的温度范围内和大约54,000h-1的空速(SV)和大约1.0克/立方英尺的PGM载量下的CO和HC转化率比较。图5A显示1型SPGM氧化催化剂体系和2型PGM对照体系的新鲜样品的CO转化率比较图，图5B描绘HC转化率比较图。
图6描绘1型SPGM氧化催化剂体系和2型PGM对照体系的新鲜样品在大约150℃至大约500℃的温度范围内和大约54,000h-1的空速(SV)、大约1.0克/立方英尺的PGM载量下的NO转化率和NO2产量比较。图6A代表1型SPGM氧化催化剂体系和2型PGM对照体系的新鲜样品的NO转化率比较图，图6B描绘NO2产量比较图。
图7图解根据一个实施方案3型SPGM氧化催化剂体系和4型PGM对照体系的新鲜样品在大约150℃至大约500℃的温度范围内和大约54,000h-1的空速(SV)和大约0.5克/立方英尺的Pt载量和大约0.5克/立方英尺的Rh载量下的CO和HC转化率比较。图7A显示3型SPGM氧化催化剂体系和4型PGM对照体系的新鲜样品的CO转化率比较图，图7B描绘HC转化率比较图。
图8显示3型SPGMDOC体系和4型PGM对照体系的新鲜样品在大约150℃至大约500℃的温度范围内和大约54,000h-1的空速(SV)、大约0.5克/立方英尺的Pt载量和大约0.5克/立方英尺的Rh载量下的NO转化率和NO2产量比较。图8A代表3型SPGMDOC体系和4型PGM对照体系的新鲜样品的NO转化率比较图，图8B描绘NO2产量比较图。
详述
在下列详述中，参考构成本文的一部分的附图。在不按比例的附图中，除非上下文中另行规定，类似符号通常指定类似组件。详述、附图和权利要求书中描述的示例性实施方案无意构成限制。可以使用其它实施方案和/或可以作出其它改变而不背离本公开的精神或范围。
定义
本文所用的下列术语可具有下列定义：
“催化剂体系”是指具有至少两层的体系，包括至少一个基底、载体涂层和/或外覆涂层。
“基底”是指提供足以沉积载体涂层和/或外覆涂层的表面积的任何形状或构造的任何材料。
“载体涂层”是指可沉积在基底上的至少一个包括至少一种氧化物固体的涂层。
“外覆涂层”是指可沉积在至少一个载体涂层上的至少一个涂层。
“催化剂”是指可用于一种或多种其它材料的转化的一种或多种材料。
“研磨”是指将固体材料粉碎成所需的颗粒或粒子大小的操作。
“共沉淀”是指在所用条件下通常可溶的物质随沉淀物沉淀下来。
“煅烧”是指在空气存在下在低于固体材料的熔点的温度下施加于固体材料以引起热分解、相变或除去挥发分的热处理过程。
“铂族金属(PGM)”是指铂、钯、钌、铱、锇和铑。
“Zero铂族(ZPGM)催化剂”是指完全或基本不含铂族金属的催化剂。
“协同铂族金属(SPGM)催化剂”是指在不同配置下用非PGM族金属化合物协同增效的PGM催化剂体系。
“处理”是指干燥、烧制、加热、蒸发、煅烧或它们的混合。
“柴油氧化催化剂”是指利用化学过程破坏来自柴油机或稀燃汽油机的排气流中的污染物以将它们转化成较无害的组分的装置。
“转化”是指至少一种材料化学变化成一种或多种其它材料。
“尖晶石”是指任何具有AB2O4结构的与铝、铬、铜或铁结合的镁、铁、锌或锰的各种矿物氧化物。
“T50”是指50％的材料转化时的温度。
附图描述
本公开可提供包括在载体氧化物上的化学计量Cu-Mn尖晶石(在所选贱金属载量下)的催化剂层的材料组合物和它们对柴油氧化催化剂(DOC)体系的起燃性能的影响以能够提供可确保高化学反应性的合适的催化层。本公开中论述的方面可能表现出适用于许多DOC用途并与PGM体系相比具有增强的催化性能的许多协同PGM(SPGM)氧化催化剂体系的总体催化转化能力在该方法中的改进。
本公开的实施方案将更活性的组分并入具有DOC性质的相材料中并提供可包括在外覆涂层中不同的钯(Pd)载量或铂(Pt)/铑(Rh)载量的所公开的SPGM体系和PGM对照体系的催化剂性能比较。
根据本公开中的实施方案，可以用包括化学计量含掺杂氧化锆载体氧化物的Cu-Mn尖晶石的载体涂层、包括PGM催化剂，如含氧化铝基载体的Pd或含氧化铝基载体的Pt/Rh复合材料的外覆涂层和合适的陶瓷基底构造SPGM氧化催化剂，在此分别被称作1型SPGM氧化催化剂体系和3型SPGM氧化催化剂体系。根据本公开中的其它实施方案，可以用包括掺杂氧化锆载体氧化物的载体涂层、包括PGM催化剂，如含氧化铝基载体的Pd或含氧化铝基载体的Pt/Rh复合材料的外覆涂层和合适的陶瓷基底构造PGM对照体系，在此分别被称作2型PGM对照体系和4型PGM对照体系。
SPGM氧化催化剂和PGM对照催化剂配置
图1显示根据一个实施方案的氧化催化剂配置100，在此被称作1型SPGM氧化催化剂体系。
如图1中所示，1型SPGM氧化催化剂体系可包括至少基底102、载体涂层104和外覆涂层106，其中载体涂层104可包括负载在掺杂氧化锆上的Cu-Mn尖晶石结构且外覆涂层106可包括负载在载体材料氧化物上的PGM催化剂材料。
根据本公开中的实施方案，1型SPGM催化剂体系的基底102材料可包括折射材料、陶瓷材料、蜂窝结构、金属材料、陶瓷泡沫、金属泡沫、网状泡沫或合适的组合，其中基底102可具有许多孔隙率合适的通道。孔隙率可根据基底102材料的特定性质而变。另外，通道数可随基底102而变，其类型和形状对本领域普通技术人员是可显而易见的。根据本公开，优选基底102可以是陶瓷基底。
1型SPGM氧化催化剂体系的载体涂层104可包括在掺杂氧化锆的载体氧化物上的Cu-Mn化学计量尖晶石Cu1.0Mn2.0O4。根据本公开，适用于所公开的载体涂层104的材料可以是Nb2O5-ZrO2。
1型SPGM氧化催化剂体系的外覆涂层106可包括PGM催化剂，如钯(Pd)、铂(Pt)、铑(Rh)及其组合，其可负载在载体材料氧化物，如掺杂氧化铝、氧化锆、掺杂氧化锆、氧化钛、氧化锡、二氧化硅、沸石及其混合物上。在本公开中，所公开的外覆涂层106可包括负载在氧化铝上的合适PGM催化剂Pd。
图2图解根据一个实施方案的PGM体系配置200，在此被称作2型PGM对照体系。
如图2中所示，2型PGM对照体系可包括至少基底102、载体涂层202和外覆涂层106，其中载体涂层202可包括掺杂氧化锆且外覆涂层206可包括负载在载体材料氧化物上的PGM催化剂材料。
根据本公开中的实施方案，2型PGM对照体系的基底102材料可包括折射材料、陶瓷材料、蜂窝结构、金属材料、陶瓷泡沫、金属泡沫、网状泡沫或合适的组合。根据本公开，优选基底102可以是陶瓷基底。
2型PGM对照体系的载体涂层202可包括载体氧化物，如氧化锆或掺杂氧化锆。根据本公开，适用于所公开的载体涂层202的材料可以是Nb2O5-ZrO2。
2型PGM对照体系的外覆涂层106可包括PGM催化剂，如钯(Pd)、铂(Pt)、铑(Rh)及其组合，其可负载在载体材料氧化物，如掺杂氧化铝、氧化锆、掺杂氧化锆、氧化钛、氧化锡、二氧化硅、沸石及其混合物上。在本公开中，所公开的外覆涂层106可包括负载在氧化铝上的合适PGM催化剂Pd。
图3描绘根据一个实施方案的氧化催化剂配置300，在此被称作3型SPGM氧化催化剂体系。
如图3中所示，3型SPGM氧化催化剂体系可包括至少基底102、载体涂层104和外覆涂层302，其中载体涂层104可包括负载在掺杂氧化锆上的Cu-Mn尖晶石结构且外覆涂层302可包括负载在载体材料氧化物上的PGM催化剂材料。
根据本公开中的实施方案，3型SPGM催化剂体系的基底102材料可包括折射材料、陶瓷材料、蜂窝结构、金属材料、陶瓷泡沫、金属泡沫、网状泡沫或合适的组合，其中基底102可具有许多孔隙率合适的通道。孔隙率可根据基底102材料的特定性质而变。另外，通道数可随基底102而变，其类型和形状对本领域普通技术人员是可显而易见的。根据本公开，优选基底102可以是陶瓷基底。
3型SPGM氧化催化剂体系的载体涂层104可包括在掺杂氧化锆的载体氧化物上的Cu-Mn化学计量尖晶石Cu1.0Mn2.0O4。根据本公开，适用于所公开的载体涂层104的材料可以是Nb2O5-ZrO2。
3型SPGM氧化催化剂体系的外覆涂层302可包括PGM催化剂，如钯(Pd)、铂(Pt)、铑(Rh)及其组合，其可负载在载体材料氧化物，如掺杂氧化铝、氧化锆、掺杂氧化锆、氧化钛、氧化锡、二氧化硅、沸石及其混合物上。在本公开中，所公开的外覆涂层302可包括负载在氧化铝上的合适PGM催化剂Pt/Rh。
图4图解根据一个实施方案的PGM体系配置400，在此被称作4型PGM对照体系。
如图4中所示，4型PGM对照体系可包括至少基底102、载体涂层202和外覆涂层302，其中载体涂层202可包括掺杂氧化锆且外覆涂层302可包括负载在载体材料氧化物上的PGM催化剂材料。
根据本公开中的实施方案，4型PGM对照体系的基底102材料可包括折射材料、陶瓷材料、蜂窝结构、金属材料、陶瓷泡沫、金属泡沫、网状泡沫或合适的组合。根据本公开，优选基底102可以是陶瓷基底。
4型PGM对照体系的载体涂层202可包括载体氧化物，如氧化锆或掺杂氧化锆。根据本公开，适用于所公开的载体涂层202的材料可以是Nb2O5-ZrO2。
4型PGM对照体系的外覆涂层302可包括PGM催化剂，如钯(Pd)、铂(Pt)、铑(Rh)及其组合，其可负载在载体材料氧化物，如掺杂氧化铝、氧化锆、掺杂氧化锆、氧化钛、氧化锡、二氧化硅、沸石及其混合物上。在本公开中，所公开的外覆涂层302可包括负载在氧化铝上的合适的PGM催化剂Pt/Rh。
可以通过制备所公开的SPGM氧化催化剂体系和PGM对照体系的样品(它们可以在起燃条件下测试)来验证Cu-Mn化学计量尖晶石Cu1.0Mn2.0O4的所选贱金属载量的协同效应。
DOC标准起燃试验程序
在稳态条件下的DOC标准起燃试验可以使用流动反应器进行，其中温度可以以大约40℃/分钟的速率从大约100℃提高到大约500℃，送入大约100ppmNOX、1,500ppmCO、大约4％CO2、大约4％H2O、大约14％O2和大约430ppmC3H6的气体组合物，在大约54,000h-1的空速(SV)下。在DOC起燃试验的过程中，既不形成N2O，也不形成NH3。
下列实施例旨在例示本公开的范围。要理解的是，也可以替代性地使用本领域技术人员已知的其它程序。可以根据上文公开的许多DOC体系配置制备本公开中的实施例。
实施例
实施例#1-1型SPGM氧化催化剂体系
实施例#1可例示具有氧化催化剂配置100的1型SPGM氧化催化剂体系的新鲜样品的制备。
载体涂层104的制备可通过研磨Nb2O5-ZrO2载体氧化物以制造水性浆料开始。该Nb2O5-ZrO2载体氧化物可具有大约15重量％至大约30重量％，优选大约25％的Nb2O5载量和大约70重量％至大约85重量％，优选大约75％的ZrO2载量。
可通过将适量的硝酸锰溶液(Mn(NO3)2)和硝酸铜溶液(CuNO3)混合大约1至2小时来制备Cu-Mn溶液。随后，可以将硝酸铜-锰溶液与Nb2O5-ZrO2载体氧化物浆料混合大约2至4小时，其中硝酸铜-锰溶液可以在Nb2O5-ZrO2载体氧化物水性浆料上沉淀。可以添加合适的碱溶液，如氢氧化钠(NaOH)溶液、碳酸钠(Na2CO3)溶液、氢氧化铵(NH4OH)溶液和四乙基氢氧化铵(TEAH)溶液等以将该浆料的pH调节到合适的范围。沉淀的Cu-Mn/Nb2O5-ZrO2浆料可以在室温下连续搅拌下老化大约12至24小时。
随后，可以将该沉淀浆料涂布在陶瓷基底102上。可以使用真空计量和涂布系统将Cu-Mn/Nb2O5-ZrO2的水性浆料沉积在合适的陶瓷基底102上以形成载体涂层104。在本公开中，可以在合适的陶瓷基底102上涂布多种载体涂层104载量(capacity)。随后，在陶瓷基底102上沉积合适载量的Cu-Mn/Nb2O5-ZrO2浆料后，载体涂层104可以在大约120℃下干燥整夜，随后在大约550℃至大约650℃范围内的合适温度下，优选在大约600℃下煅烧大约5小时。
外覆涂层106可包括Pd在氧化铝基载体上的组合。外覆涂层106的制备可通过单独研磨氧化铝基载体氧化物以制造水性浆料开始。随后，可以将硝酸钯溶液以在大约0.5克/立方英尺至大约25.0克/立方英尺范围内，在本公开中优选大约1.0克/立方英尺的载量与氧化铝的水性浆料混合。在Pd和氧化铝浆料混合后，可以用适量的一种或多种碱溶液，如氢氧化钠(NaOH)溶液、碳酸钠(Na2CO3)溶液、氢氧化铵(NH4OH)溶液和四乙基氢氧化铵(TEAH)溶液等锁定Pd。然后，所得浆料可以老化大约12至24小时以随后作为外覆涂层106涂布在载体涂层104上，在大约550℃下干燥并烧制大约4小时。
实施例#2-2型SGM对照体系
实施例#2可例示具有PGM体系配置200的2型PGM对照体系的新鲜样品的制备。
载体涂层202的制备可通过研磨Nb2O5-ZrO2载体氧化物以制造水性浆料开始。该Nb2O5-ZrO2载体氧化物可具有大约15重量％至大约30重量％，优选大约25％的Nb2O5载量和大约70重量％至大约85重量％，优选大约75％的ZrO2载量。可以在大约4微米至大约5微米的范围内调节载体涂层202粒度(d50)。
随后，可以将载体涂层202浆料涂布在基底102上。可以使用真空计量和涂布系统将载体涂层202浆料沉积在合适的陶瓷基底102上以形成载体涂层202。在本公开中，可以在合适的陶瓷基底102上涂布多种载体涂层202载量。载体涂层202可以在大约120℃下干燥整夜，随后在大约550℃至大约650℃范围内的合适温度下，优选在大约550℃下煅烧大约4小时。
外覆涂层106可包括Pd在氧化铝基载体上的组合。外覆涂层106的制备可通过单独研磨氧化铝基载体氧化物以制造水性浆料开始。随后，可以将硝酸钯溶液以在大约0.5克/立方英尺至大约25.0克/立方英尺范围内，在本公开中优选大约1.0克/立方英尺的载量与氧化铝的水性浆料混合。在Pd和氧化铝浆料混合后，可以用适量的一种或多种碱溶液，如氢氧化钠(NaOH)溶液、碳酸钠(Na2CO3)溶液、氢氧化铵(NH4OH)溶液和四乙基氢氧化铵(TEAH)溶液等锁定Pd。然后，所得浆料可以老化大约12至24小时以随后作为外覆涂层106涂布在载体涂层104上，在大约550℃下干燥并烧制大约4小时。
可通过制备各催化剂配方和配置的新鲜样品来比较1型SPGM氧化催化剂体系和2型PGM对照体系的DOC起燃性能，以测量/分析将Cu-Mn尖晶石添加到可用于DOC用途的PGM催化剂材料中的协同效应并显示所带来的氧化活性的改进。为了比较所公开的1型SPGMDOC体系和2型PGM对照体系的起燃性能和DOC活性，可以进行DOC标准起燃试验。
实施例#3-3型SPGM氧化催化剂体系
实施例#3可例示具有氧化催化剂配置300的3型SPGM氧化催化剂体系的新鲜样品的制备。
载体涂层104的制备可通过研磨Nb2O5-ZrO2载体氧化物以制造水性浆料开始。该Nb2O5-ZrO2载体氧化物可具有大约15重量％至大约30重量％，优选大约25％的Nb2O5载量和大约70重量％至大约85重量％，优选大约75％的ZrO2载量。
可通过将适量的硝酸锰溶液(Mn(NO3)2)和硝酸铜溶液(CuNO3)混合大约1至2小时来制备Cu-Mn溶液。随后，可以将硝酸铜-锰溶液与Nb2O5-ZrO2载体氧化物浆料混合大约2至4小时，其中硝酸铜-锰溶液可以在Nb2O5-ZrO2载体氧化物水性浆料上沉淀。可以添加合适的碱溶液，如氢氧化钠(NaOH)溶液、碳酸钠(Na2CO3)溶液、氢氧化铵(NH4OH)溶液和四乙基氢氧化铵(TEAH)溶液等以将该浆料的pH调节到合适的范围。沉淀的Cu-Mn/Nb2O5-ZrO2浆料可以在室温下连续搅拌下老化大约12至24小时。
随后，可以将该沉淀浆料涂布在陶瓷基底102上。可以使用真空计量和涂布系统将Cu-Mn/Nb2O5-ZrO2的水性浆料沉积在合适的陶瓷基底102上以形成载体涂层104。在本公开中，可以在合适的陶瓷基底102上涂布多种载体涂层104载量。随后，在陶瓷基底102上沉积合适载量的Cu-Mn/Nb2O5-ZrO2浆料后，载体涂层104可以在大约120℃下干燥整夜，随后在大约550℃至大约650℃范围内的合适温度下，优选在大约600℃下煅烧大约5小时。
外覆涂层302可包括Pt和Rh在氧化铝基载体上的组合。外覆涂层302的制备可通过单独研磨氧化铝基载体氧化物以制造水性浆料开始。随后，可以将硝酸铂和硝酸铑的溶液以在大约0.5克/立方英尺至大约25.0克/立方英尺范围内，优选大约0.5克/立方英尺Pt和大约0.5克/立方英尺Rh的载量与氧化铝的水性浆料混合。在Pt/Rh和氧化铝浆料混合后，可以用适量的一种或多种碱溶液，如氢氧化钠(NaOH)溶液、碳酸钠(Na2CO3)溶液、氢氧化铵(NH4OH)溶液和四乙基氢氧化铵(TEAH)溶液等锁定Pt/Rh。然后，所得浆料可以老化大约12至24小时以随后作为外覆涂层106涂布在载体涂层104上，在大约550℃下干燥并烧制大约4小时。
实施例#4-4型PGM对照体系
实施例#4可例示具有PGM体系配置400的4型PGM对照体系的新鲜样品的制备。
载体涂层202的制备可通过研磨Nb2O5-ZrO2载体氧化物以制造水性浆料开始。该Nb2O5-ZrO2载体氧化物可具有大约15重量％至大约30重量％，优选大约25％的Nb2O5载量和大约70重量％至大约85重量％，优选大约75％的ZrO2载量。可以在大约4微米至大约5微米的范围内调节载体涂层202粒度(d50)。
随后，可以将载体涂层202浆料涂布在基底102上。可以使用真空计量和涂布系统将载体涂层202浆料沉积在合适的陶瓷基底102上以形成载体涂层202。在本公开中，可以在合适的陶瓷基底102上涂布多种载体涂层202载量。载体涂层202可以在大约120℃下干燥整夜，随后在大约550℃至大约650℃范围内的合适温度下，优选在大约550℃下煅烧大约4小时。
外覆涂层302可包括Pt和Rh在氧化铝基载体上的组合。外覆涂层302的制备可通过单独研磨氧化铝基载体氧化物以制造水性浆料开始。随后，可以将硝酸铂和硝酸铑的溶液以在大约0.5克/立方英尺至大约25.0克/立方英尺范围内，优选大约0.5克/立方英尺Pt和大约0.5克/立方英尺Rh的载量与氧化铝的水性浆料混合。在Pt/Rh和氧化铝浆料混合后，可以用适量的一种或多种碱溶液，如氢氧化钠(NaOH)溶液、碳酸钠(Na2CO3)溶液、氢氧化铵(NH4OH)溶液和四乙基氢氧化铵(TEAH)溶液等锁定Pt/Rh。然后，所得浆料可以老化大约12至24小时以随后作为外覆涂层106涂布在载体涂层104上，在大约550℃下干燥并烧制大约4小时。
可通过制备各催化剂配方和配置的新鲜样品来比较3型SPGM氧化催化剂体系和4型PGM对照体系的DOC起燃性能，以测量/分析将Cu-Mn尖晶石添加到可用于DOC用途的PGM催化剂材料中的协同效应并显示所带来的氧化活性的改进。为了比较所公开的3型SPGMDOC体系和4型PGM对照体系的起燃性能和DOC活性，可以进行DOC标准起燃试验。SPGM氧化催化剂和PGM对照体系的新鲜样品的氧化性质的分析
图5代表根据一个实施方案1型SPGM氧化催化剂体系和2型PGM对照体系的新鲜样品分别在起燃条件下、在大约150℃至大约500℃的温度范围内和大约54,000h-1的空速(SV)下的CO和HC转化率比较500。图5A显示1型SPGM氧化催化剂体系和2型PGM对照体系的CO转化率比较曲线502，图5B描绘HC转化率比较曲线504。
相应地，如图5A中可以看出，分别地，转化率曲线506代表1型SPGM氧化催化剂体系新鲜样品的CO转化率，转化率曲线508描绘2型PGM对照体系新鲜样品的CO转化率。在图5A中可以观察到，1型SPGM氧化催化剂体系的新鲜样品的COT50为大约235℃，而2型PGM对照体系的新鲜样品的COT50为大约325℃。协同PGM样品的CO起燃温度低于PGM对照样品，表明1型SPGM的CO氧化性能增强。尽管PGM样品在CO转化方面表现出合意的氧化活性，但协同PGM样品在CO转化方面明显优于PGM样品，证实Cu-Mn尖晶石和Pd之间的协同效应。
如图5B中可以看出，分别地，转化率曲线510代表1型SPGM氧化催化剂体系新鲜样品的HC转化率，转化率曲线512描绘2型PGM对照体系新鲜样品的HC转化率。在图5B中可以观察到，1型SPGM氧化催化剂体系的新鲜样品的HCT50为大约235℃，而2型PGM对照体系的HCT50为大约350℃。协同PGM样品的HC起燃温度低于PGM对照样品，表明1型SPGM氧化催化剂体系的HC氧化活性增强，证实Cu-Mn尖晶石和Pd之间的协同效应。
1型SPGM氧化催化剂体系带来的CO和HC氧化改进水平表明Cu-Mn尖晶石和Pd之间的协同效应可提供用于DOC用途的具有大约1.0克/立方英尺的超低Pd载量的改进的氧化催化剂。
图6描绘根据一个实施方案1型SPGM氧化催化剂体系和2型PGM对照体系的新鲜样品在大约150℃至大约500℃的温度范围和大约54,000h-1的空速(SV)下的NO转化率和NO2产量比较600。图6A代表1型SPGM氧化催化剂体系和2型PGM对照体系的新鲜样品的NO转化率比较602，图6B描绘NO2产量比较604。
相应地，如图6A中可以看出，分别地，转化率曲线606代表1型SPGM氧化催化剂体系新鲜样品的NO转化率，转化率曲线608描绘2型PGM对照体系新鲜样品在DOC起燃条件下的NO转化率。
如图6B中可以看出，分别地，浓度分布曲线610代表1型SPGM氧化催化剂体系的NO2产量，浓度分布曲线612描绘2型PGM对照体系在DOC起燃条件下的NO2产量。
在图6A中可以观察到，1型SPGM氧化催化剂体系的NO转化率在大约390℃下达到大约34％的最大转化率，而2型PGM对照体系新鲜样品在大约465℃下达到大约18％的最大NO转化率。
1型SPGM氧化催化剂体系表现出明显高于2型PGM对照体系的在NO氧化方面的催化活性。大约83％的明显高的NOX转化率改进表明1型SPGM氧化催化剂体系可提供增强的氧化活性，证实Cu-Mn与pd的协同效应。
如图6B中可以看出，来自浓度分布曲线610的NO2产量在大约390℃下为大约35ppm，而来自浓度分布曲线612的NO2产量在大约465℃下为大约18ppm。通过考虑进料流中的NO浓度(100ppm)，来自图6B的NO2浓度与来自图6A的NO转化率的比较证实NO转化成NO2并且没有形成其它产物，如NH3或N2O。
可以指出，1型SPGM氧化催化剂体系可提供比2型PGM对照体系高的NO氧化产生NO2的水平。1型SPGM氧化催化剂体系的提高的NO2产量和带来的NO转化水平可表明由Cu-Mn尖晶石提供的协同效应也可提供在柴油氧化条件和大约1.0克/立方英尺的Pd载量下改进的NO氧化活性。这些结果可以证实，改进源自Cu-Mn尖晶石和Pd之间的协同效应，这也能够提供用于在真实条件下运行的许多发动机用途的协同PGM柴油氧化催化剂体系。可以在OC层中使用更高的Pd载量获得更高的NO氧化水平。
图7图解根据一个实施方案3型SPGM氧化催化剂体系和4型PGM对照体系的新鲜样品分别在DOC起燃条件下、在大约150℃至大约500℃的温度范围和大约54,000h-1的空速(SV)下的CO和HC转化率比较700。分别地，图7A显示3型SPGM氧化催化剂体系和4型PGM对照体系的新鲜样品的CO转化率比较曲线702，图7B描绘HC转化率比较曲线704。
相应地，如图7A中可以看出，分别地，转化率曲线706代表3型SPGM氧化催化剂体系的CO转化率，转化率曲线708描绘4型PGM对照体系在DOC起燃条件下的CO转化率。在图7A中可以观察到，3型SPGM氧化催化剂体系的COT50为大约245℃，而4型PGM对照体系的COT50为大约265℃。协同PGM样品的CO起燃温度低于PGM对照样品，表明3型SPGM氧化催化剂体系的CO氧化性能增强。尽管PGM样品在CO转化方面表现出显著的氧化活性，但协同PGM样品在CO转化方面优于PGM样品，证实Cu-Mn尖晶石和Pt/Rh之间的协同效应。
如图7B中可以看出，分别地，转化率曲线710代表3型SPGM氧化催化剂体系的HC转化率，转化率曲线712描绘4型PGM对照体系在DOC起燃条件下的HC转化率。在图7B中可以观察到，3型SPGM氧化催化剂体系的HCT50为大约250℃，而4型PGM对照体系的HCT50为大约285℃。协同PGM样品的HC起燃温度低于PGM对照样品，表明增强的HC氧化性能。尽管PGM样品在HC转化方面表现出显著的氧化活性，但协同PGM样品在HC转化方面优于PGM样品，证实Cu-Mn尖晶石和Pt/Rh之间的协同效应。
3型SPGM氧化催化剂体系带来的CO和HC氧化改进水平表明Cu-Mn尖晶石和Pt/Rh之间的协同效应可提供用于DOC用途的具有大约1.0克/立方英尺的超低PGM载量的改进的氧化催化剂。
图8描绘根据一个实施方案3型SPGM氧化催化剂体系和4型PGM对照体系的新鲜样品在DOC起燃条件和大约54,000h-1的空速(SV)下的NO转化率和NO2产量比较800。图8A代表3型SPGM氧化催化剂和4型PGM对照体系的新鲜样品的NO转化率比较802，图8B描绘NO2产量比较804。
相应地，如图8A中可以看出，分别地，转化率曲线806代表3型SPGM氧化催化剂的NO转化率，转化率曲线808描绘4型PGM对照体系在DOC起燃条件下的NO转化率。
如图8B中可以看出，分别地，浓度分布曲线810代表3型SPGM氧化催化剂体系的NO2产量，浓度分布曲线812描绘4型PGM对照体系在DOC起燃条件下的NO2产量。
在图8A中可以观察到，3型SPGM氧化催化剂体系新鲜样品的NO转化率在大约385℃下达到大约32％的最大转化率，而4型PGM对照体系新鲜样品在大约460℃下达到大约19％的最大NOX转化率。
3型SPGM氧化催化剂体系表现出高于4型PGM对照体系样品的在NO氧化方面的催化活性。大约55％的NOX转化率改进表明3型SPGM氧化催化剂体系可提供增强的NO氧化活性。
如图8B中可以看出，来自浓度分布曲线810的NO2产量在大约385℃下为大约35ppm，而来自浓度分布曲线812的NO2产量在大约460℃下为大约20ppm。这些结果可以证实，3型SPGM氧化催化剂体系的新鲜样品的催化性能优于4型PGM对照体系的样品的催化性能。Cu-Mn尖晶石在3型SPGM氧化催化剂体系中的存在提高用于产生NO2的DOC活性。
可以指出，3型SPGM氧化催化剂体系可提供比4型PGM对照体系高的NO氧化产生NO2的水平。3型SPGM氧化催化剂体系的提高的NO2产量和带来的NO转化水平可表明由Cu-Mn尖晶石提供的协同效应也可提供在柴油氧化条件和大约1.0克/立方英尺的Pt/Rh载量下改进的NO氧化活性。这些结果可以证实，改进源自Cu-Mn尖晶石和PGM之间的协同效应，这也能够提供用于在真实条件下运行的许多发动机用途的协同PGM柴油氧化催化剂体系。可以在OC层中使用更高的Pt/Rh载量获得更高的NO氧化水平。
使用这些催化剂在DOC起燃条件下进行1型和3型SPGM氧化催化剂体系的催化氧化以显示和证实所公开的体系的DOC催化性能比2型和4型PGM对照体系的氧化活性提高。如通过它们的相应起燃性能与无Cu-Mn组合物的相同PGM体系的比较测定，这两种SPGM体系都已表明是用于柴油氧化的显著活性催化剂。在所有公开的SPGM体系中可以观察到，Cu-Mn尖晶石的存在与非协同PGM体系没有表现出的增强的氧化活性相关联。所公开的SPGM氧化催化剂体系可以为稀燃发动机运行中的许多用途提供基础。
尽管已经公开了各种方面和实施方案，但可能想出其它方面和实施方案。本文中公开的各种方面和实施方案用于举例说明而无意构成限制，由下列权利要求书指示真实范围和精神。

Claims (15)

1.一种协同铂族金属(SPGM)催化剂体系，其包含：
至少一个基底，其包含至少一种金属；
至少一个载体涂层，其包含至少一种储氧材料，所述储氧材料进一步包含具有铌-氧化锆载体氧化物的Cu-Mn；和
至少一个外覆涂层，其包含至少一种铂族金属催化剂；
其中所述至少一种铂族金属催化剂包括选自钯、铂和铑的双金属复合材料及其组合的至少一种；
其中所述至少一个外覆涂层负载在至少一种包括氧化铝的载体材料氧化物上。
2.权利要求1的催化剂体系，其中Cu-Mn尖晶石包括CuMn2O4。
3.权利要求1的催化剂体系，其中所述至少一种铂族金属催化剂以大约0.5克/立方英尺至大约25.0克/立方英尺存在。
4.权利要求1的催化剂体系，其中所述至少一种铂族金属催化剂以大约1.0克/立方英尺存在。
5.权利要求1的催化剂体系，其中CO的T50为大约235℃至大约325℃。
6.权利要求1的催化剂体系，其中HC的T50为大约235℃至大约325℃。
7.权利要求1的催化剂体系，其中在390℃下的NO转化率为大约34％。
8.权利要求1的催化剂体系，其中在465℃下的NO转化率为大约18％。
9.权利要求1的催化剂体系，其中在460℃下的NOx转化率为大约19％。
10.权利要求1的催化剂体系，其中所述Cu-Mn为尖晶石形式。
11.权利要求1的催化剂体系，其中所述铌-氧化锆载体氧化物包括Nb2O5-ZrO2。
12.权利要求1的催化剂体系，其进一步包含至少一个浸渍层。
13.权利要求1的催化剂，其中所述至少一种基底包括陶瓷。
14.权利要求1的催化剂，其中所述至少一种铂族金属催化剂通过共研磨制备。
15.权利要求1的催化剂，其中所述至少一种铂族金属催化剂通过共沉淀制备。
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Application publication date: 20160615