CN106413881A - 使用协同的pgm作为三效催化剂的系统和方法 - Google Patents
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Abstract
公开了由包括铜‑锰材料组合物和PGM催化剂的催化剂体系的组合所形成的协同效应。测试了催化剂体系构造的变体,来确定用于最佳的协同的PGM(SPGM)催化剂体系的最有效的材料组成,配料和构造。所选择的SPGM催化剂体系的协同效应是在稳态和振荡测试条件测定的,由其最佳的NO/CO交换R‑值显示了与目前的用于TWC应用的PGM催化剂相比,所选择的SPGM催化剂体系的增强的催化行为。根据本发明的原理,将Pd作为外涂层施用到氧化铝基载体上和将负载在Nb2O5‑ZrO2上的Cu‑Mn尖晶石结构作为活化涂层施用到合适的陶瓷基底上,产生了与市售的PGM催化剂相比更高的催化活性,效率和在TWC条件中,特别是在贫含条件下更好的性能。
Description
交叉参考的相关申请
这个国际专利申请要求2013年11月26日提交的美国专利申请No.14/098861的优先权,其全部公开内容在此以引文形式并入。
本发明涉及美国专利申请No.14/090887,标题为“Oxygen StorageCapacity and Thermal Stability of Synergized PGM Catalyst Systems”,和美国专利申请No.14/090915,标题为“Method for Improving Lean performance ofPGM Catalyst Systems:Synergized PGM”,以及美国专利申请No.14/090938,标题为“Systems and Methods for Managing a Synergistic Relationship betweenPGM and Copper-Manganese in a Three Way Catalyst Systems”,全部都是2013年11月26日提交的,其全部公开内容在此以引文形式并入。
发明背景
技术领域
本发明通常涉及三效催化剂(TWC)体系,和更具体的涉及协同的PGM催化剂的TWC性能。
背景信息
许多现代功能材料是由多相实体制成的,在其中需要不同组分之间的协作行为来获得最佳的性能。协作行为的典型情形是现代TWC体系,其用于车辆排气中来降低废气排放。TWC体系将车辆排气中三种主要的污染物一氧化碳(CO),未燃烧的烃(HC)和氮的氧化物(NOx)转化成H2O,CO2和氮气。典型的TWC体系包括氧化铝载体,在其上沉积了铂族金属(PGM)材料和促进性氧化物二者。对于期望的催化转化来说关键的是促进性氧化物和PGM金属之间的结构-反应性相互影响,特别是涉及在加工条件下的氧的存储/释放。
目前的TWC曝露于高的运行温度,这归因于使用了接近于发动机的闭路偶合催化剂。此外,TWC对于PGM和稀土金属的需求持续增加,这归因于它们在除去内燃机排气中的污染物中的效力,这同时导致了PGM金属的供给紧张,其抬高了它们的成本和催化剂应用的成本。
因为PGM催化剂通常在接近于化学计量比的条件工作,因此期望的是增加它们在接近于化学计量比条件的贫含条件下的活性。在贫含条件下,NOX转化率可以通过协同的PGM来增加。这种协同效应改进了燃料消耗和提供了燃料经济性。由于前述原因,需要组合的催化剂体系,其可以表现出最佳的协同行为,产生增强的活性和性能,并且高到实际催化剂的理论限度。
发明内容
本发明的一个目标是提供一种包括钯(Pd)的PGM催化剂,其可以协同的加入Cu1.0Mn2.0O4尖晶石来增加具体处于贫含条件下的PGM催化剂的TWC性能,和用于催化剂体系在TWC条件中的最佳性能。
根据一种实施方案,一种催化剂体系可以包括基底,活化涂层(WC),外涂层(OC)和浸渍层。该优化的催化剂体系可以使用具有氧化铝基载体的PGM催化剂,在多个催化剂构造中施用具有铌-氧化锆载体氧化物的Cu1.0Mn2.0O4化学计量比的尖晶石来实现,其包括不同的活化涂层(WC),外涂层(OC)或者浸渍(IM)层。在氧化铝基载体上的PGM催化剂和具有铌-氧化锆载体氧化物的Cu1.0Mn2.0O4尖晶石二者可以使用本领域已知的合适的合成方法来制备。
根据本发明的实施方案,协同的PGM(SPGM)催化剂体系可以配置有WC层(其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石),OC层(其包括具有氧化铝基载体的PGM催化剂)和合适的陶瓷基底;或者WC层(其包括具有氧化铝基载体的PGM催化剂),OC层(其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石)和合适的陶瓷基底;或者仅仅具有氧化铝基载体的WC层,OC层(其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石),IM层(其包括本发明的PGM,Pd)和合适的陶瓷基底;或者仅仅WC层(其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石,其是用Pd/氧化铝共研磨的)和合适的陶瓷基底。
所公开的SPGM催化剂体系的最佳的NO/CO交换R-值可以通过使用根据本发明的实施方案所制备的新和水热老化的催化剂样品,进行等温稳态扫描测试来测定。该稳态测试可以使用在多个空速从富含条件到贫含条件的11点R-值,在所选择的入口温度来开发。来自于等温稳态测试的结果可以比较来显示对于在TWC条件下,特别是在贫含条件下的最佳性能来说,所公开的SPGM催化剂体系的最佳的组成和构造,其用于降低使用所公开的SPGM催化剂体系的燃料消耗。
根据一种实施方案,在稳态和振荡条件下,在所选择的NO/CO交换R-值(其可以产生NO,CO和HC转化中增强的催化性能)进行TWC标准起燃测试。
从本发明可以发现虽然催化剂的催化活性和热和化学稳定性在实际使用过程中会受到因素例如催化剂的化学组成的影响,如PGM催化剂通常是接近于化学计量比的条件来工作的,但是令人期望的是在接近于化学计量比的条件的贫含条件下增加催化剂活性。在贫含条件下,NOX转化率可以通过协同PGM催化剂来增加。这种PGM催化剂上的协同效应可以改进燃料消耗和提供燃料经济性。所公开的SPGM催化剂体系的TWC性能可以提供指示,其用于催化剂应用,和更具体的用于在接近于化学计量比的条件的贫含条件下运行的催化剂体系,所公开的SPGM催化剂体系的化学组成可以是更运行有效的,并且从催化剂制造商的观点来说,基本的优点给出了所涉及的经济因素。
本发明的许多其他方面,特征和益处可以从下面的具体实施方式和结合附图而显而易见。
附图说明
本发明可以参考下图来更好的理解。图中的部件不必需是按照尺寸绘制的,代替的,将重点放在说明本发明的原理上。在图中,附图标记表示了整个的不同图中相应的零件。
图1显示了根据一种实施方案,被称作SPGM催化剂体系类型1的一种SPGM催化剂体系构造。
图2显示了根据一种实施方案,被称作SPGM催化剂体系类型2的一种SPGM催化剂体系构造。
图3显示了根据一种实施方案,被称作SPGM催化剂体系类型3的一种SPGM催化剂体系构造。
图4显示了根据一种实施方案,被称作SPGM催化剂体系类型4的一种SPGM催化剂体系构造。
图5显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和空速(SV)是大约40000h-1,SPGM催化剂体系类型1新样品的TWC性能。
图6显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和空速(SV)是大约40000h-1,SPGM催化剂体系类型2新样品的TWC性能。
图7显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和空速(SV)是大约40000h-1,SPGM催化剂体系类型3新样品的TWC性能。
图8显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,SPGM催化剂体系类型4新样品的TWC性能。
图9显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,SPGM催化剂体系类型1,类型2,类型3,类型4和PGM催化剂的新样品的NO转化率的性能比较。
图10显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,SPGM催化剂体系类型1,类型2,类型3,类型4和PGM催化剂的水热老化的样品的NO转化率的性能比较。
图11显示了根据一种实施方案,在SV大约40000h-1和R-值是大约1.05的稳态条件(图11A),和在频率信号是大约1Hz,SV是大约90000h-1和R-值是大约1.05的振荡条件下(图11B),SPGM催化剂体系类型1新样品的TWC标准起燃测试结果的比较。
具体实施方式
本发明在此参考附图所示的实施方案来详细说明,其形成了此处的一部分。可以使用其他实施方案和/或可以进行其他变化,而不脱离本发明的主旨或范围。具体实施方式中所述的示例性实施方案不表示对于本发明主题的限制。
定义
作为此处所用的,下面的术语可以具有下面的定义:
“铂族金属(PGM)”指的是铂,钯,钌,铱,锇和铑。
“协同的铂族金属(SPGM)催化剂”指的是一种PGM催化剂体系,其是通过非PGM族金属化合物在不同的构造下协同的。
“催化剂”指的是一种或多种这样的材料,其可以用于一种或多种其他材料的转化中。
“基底”指的是任何形状或构造的任何材料,其产生了用于沉积活化涂层和/或外涂层的足够的表面积。
“活化涂料”指的是至少一种涂料,其包括至少一种氧化物固体,其可以沉积到基底上。
“外涂料”指的是至少一种涂料,其可以沉积在至少一种活化涂层或者浸渍层上。
“催化剂体系”指的是至少两层的体系,包括至少一种基底,活化涂层和/或外涂层。
“研磨”指的是将固体材料粉碎成期望的粒子或粒度的操作。
“共沉淀”指的是通过将在使用条件下通常可溶性的物质沉淀来取出。
“浸渍”指的是用液体化合物浸透或者饱和固体层的方法或者将一些元素扩散穿过介质或者物质。
“处理着,处理的或者处理”指的是干燥,燃烧,加热,蒸发,煅烧或者其混合。
“煅烧”指的是在空气存在下,对固体材料施加热处理方法,来产生热分解,相变或者在低于该固体材料熔点的温度除去挥发性部分。
“空气/燃料比或者A/F比”指的是空气的重量除以燃料的重量。
“R值”指的是催化剂中材料的氧化潜力除以还原潜力所获得的值。当R等于1时,所述反应可以被认为是化学计量比的。
“富含条件”指的是R值高于1的废气条件。
“贫含条件”指的是R值低于1的废气条件。
“三效催化剂”指的是这样的催化剂,其可以实现三个同时的任务:将氮氧化物还原成氮和氧,将一氧化碳氧化成二氧化碳,和将未燃烧的烃氧化成二氧化碳和水。
“T50”可以指的是50%的材料被转化时的温度。
“转化”指的是至少一种材料向一种或多种其他材料的化学变化。
附图说明
本发明通常可以提供一种协同的PGM(SPGM)催化剂体系,其具有增强的催化性能和热稳定性,将更大活性的组分引入具有三效催化剂(TWC)性能例如改进的氧迁移性的相材料中,来增强所公开的SPGM催化剂体系的催化活性。
根据本发明的实施方案,SPGM催化剂体系可以配置有活化涂层(WC)(其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石),外涂层(OC)(其包括钯(Pd)和氧化铝基载体的PGM催化剂)和合适的陶瓷基底,在此称作SPGM催化剂体系类型1;或者WC层(其包括具有氧化铝基载体的Pd的PGM催化剂),OC层(其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石)和合适的陶瓷基底,在此称作SPGM催化剂体系类型2;或者仅仅具有氧化铝基载体的WC层,OC层(其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石),浸渍(IM)层(其包括本发明的PGM,Pd)和合适的陶瓷基底,在此称作SPGM催化剂体系类型3;或者仅仅WC层,其包括具有铌-氧化锆载体氧化物的Cu-Mn化学计量比的尖晶石,其是用包括Pd和氧化铝的浆体研磨的,和合适的陶瓷基底,在此称作SPGM催化剂体系类型4。
SPGM催化剂体系构造,材料组成和制备
图1显示了用于SPGM催化剂体系类型1的催化剂结构100。在这种系统构造中,WC层102可以包括Cu-Mn尖晶石结构Cu1.0Mn2.0O4,其使用共沉淀方法或者本领域已知的任何其他制备技术负载在Nb2O5-ZrO2上。
WC层102的制备可以通过将Nb2O5-ZrO2载体氧化物研磨来制造含水浆体开始。该Nb2O5-ZrO2载体氧化物的Nb2O5负载量可以是大约15%-大约30%重量,优选大约25%,和ZrO2负载量是大约70%-大约85%重量,优选大约75%。
该Cu-Mn溶液可以通过将适量的硝酸锰溶液(MnNO3)和硝酸铜溶液(CuNO3)混合来制备,这里合适的铜负载量可以包括大约10%-大约15%重量的负载量。合适的锰负载量可以包括大约15%-大约25%重量的负载量。接下来的步骤是硝酸Cu-Mn溶液在Nb2O5-ZrO2载体氧化物含水浆体上沉淀,其可以向其中加入适当的碱溶液,例如来将该浆体的pH调节到合适的范围。该沉淀的浆体可以在连续搅拌下在室温老化大约12-24小时的时间。
随后,该沉淀的浆体可以使用具有蜂窝结构的堇青石材料涂覆到陶瓷基底106上,这里陶瓷基底106可以具有多个具有合适孔隙率的通道。Cu-Mn/Nb2O5-ZrO2的含水浆体可以使用真空加料和涂覆系统沉积到陶瓷基底106上来形成WC层102。在本发明中,多个容量的WC负载量可以涂覆到陶瓷基底106上。该多个WC负载量可以在大约60g/L-大约200g/L变化,在本发明中特别是大约120g/L。随后,在陶瓷基底106上沉积了合适负载量的Cu-Mn/Nb2O5-ZrO2浆体之后,WC层102可以干燥和随后在大约550℃-大约650℃的合适的温度,优选在大约600℃煅烧大约5小时。WC层102的处理可以使用合适的干燥和加热方法。市售的气刀干燥系统可以用于干燥WC层102。热处理(煅烧)可以使用市售燃烧(炉子)系统来进行。
沉积在陶瓷基底106上的WC层102的化学组成(总负载量是大约120g/L)包括Cu-Mn尖晶石结构,其的铜负载量是大约10g/L-大约15g/L和锰负载量是大约20g/L-大约25g/L。Nb2O5-ZrO2载体氧化物的负载量可以是大约80g/L-大约90g/L。
OC层104可以包括Pd在氧化铝基载体上的组合。OC层104的制备可以通过将氧化铝基载体氧化物分别研磨来制造含水浆体而开始。随后,硝酸钯溶液然后可以与氧化铝的含水浆体混合,负载量是大约0.5g/ft3-大约10g/ft3。在这个实施方案中,Pd负载量是大约6g/ft3和WC材料的总负载量是120g/L。在Pd和氧化铝浆体混合后,Pd可以用适量的一种或多种碱溶液锁住,例如氢氧化钠(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。不需要pH调节。在这个实施方案中,Pd可以使用四乙基氢氧化铵(TEAH)的碱溶液锁住。然后所形成的浆体可以老化大约12小时-大约24小时,随后作为外涂层涂覆到WC层102上,干燥和在大约550℃燃烧大约4小时。
图2显示了用于SPGM催化剂体系类型2的催化剂结构200。在这种系统构造中,WC层202可以包括Pd在氧化铝基载体上的组合。WC层202的制备可以通过将氧化铝基载体氧化物分别研磨来制造含水浆体而开始。随后,硝酸钯溶液然后可以与氧化铝的含水浆体混合,负载量是大约0.5g/ft3-大约10g/ft3。在这个实施方案中,Pd负载量是大约6g/ft3和WC材料的总负载量是120g/L。在Pd和氧化铝浆体混合后,Pd可以用适量的一种或多种碱溶液锁住,例如氢氧化钠(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。不需要pH调节。在这个实施方案中,Pd可以使用四乙基氢氧化铵(TEAH)的碱溶液锁住。然后所形成的浆体可以老化大约12小时-大约24小时,随后作为WC层202涂覆到陶瓷基底206上,其使用了具有蜂窝结构的堇青石材料,这里陶瓷基底106可以具有多个具有合适的孔隙率的通道,干燥和在大约550℃燃烧大约4小时。WC层202可以使用真空加料和涂覆系统沉积在陶瓷基底106上。
OC层204可以包括Cu-Mn化学计量比的尖晶石结构Cu1.0Mn2.0O4,其使用共沉淀方法或者本领域已知的任何其他制备技术负载在Nb2O5-ZrO2上。
OC层204的制备可以通过将Nb2O5-ZrO2载体氧化物研磨来制造含水浆体开始。该Nb2O5-ZrO2载体氧化物的Nb2O5负载量可以是大约15%-大约30%重量,优选大约25%,和ZrO2负载量是大约70%-大约85%重量,优选大约75%。
该Cu-Mn溶液可以通过将适量的硝酸锰溶液(MnNO3)和硝酸铜溶液(CuNO3)混合来制备,这里合适的铜负载量可以包括大约10%-大约15%重量的负载量。合适的锰负载量可以包括大约15%-大约25%重量的负载量。接下来的步骤是硝酸Cu-Mn溶液在Nb2O5-ZrO2载体氧化物含水浆体上沉淀,其可以向其中加入适当的碱溶液,例如来将该浆体的pH调节到合适的范围。该沉淀的浆体可以在连续搅拌下在室温老化大约12-24小时的时间。
随后,该沉淀的浆体可以涂覆到WC层202上。Cu-Mn/Nb2O5-ZrO2的含水浆体可以使用真空加料和涂覆系统来沉积到WC层202上。在本发明中,多个容量的OC负载量可以涂覆到WC层202上。该多个OC负载量可以在大约60g/L-大约200g/L变化,在本发明中特别是大约120g/L。随后,在WC层202上沉积了合适负载量的Cu-Mn/Nb2O5-ZrO2浆体之后,OC层204可以干燥和随后在大约550℃-大约650℃的合适温度,优选在大约600℃煅烧大约5小时。OC层204的处理可以使用合适的干燥和加热方法。市售的气刀干燥系统可以用于干燥OC层204。热处理(煅烧)可以使用市售燃烧(炉子)系统来进行。
沉积在WC层202上的OC层204的化学组成(总负载量是大约120g/L)包括Cu-Mn尖晶石结构,其的铜负载量是大约10g/L-大约15g/L和锰负载量是大约20g/L-大约25g/L。该Nb2O5-ZrO2载体氧化物的负载量可以是大约80g/L-大约90g/L。
图3显示了用于SPGM催化剂体系类型3的催化剂结构300。在这个实施方案中,WC层302可以仅仅包括氧化铝基载体。WC层302的制备可以通过将氧化铝基载体氧化物研磨来制造含水浆体而开始。然后,所形成的浆体可以作为WC层302涂覆到陶瓷基底308上,其使用了具有蜂窝结构的堇青石材料,这里陶瓷基底308可以具有多个具有合适孔隙率的通道。WC负载量是大约120g/L和随后干燥和在大约550℃燃烧大约4小时。WC层302可以使用真空加料和涂覆系统来沉积到陶瓷基底308上。
OC层304可以包括Cu-Mn化学计量比的尖晶石结构Cu1.0Mn2.0O4,其使用共沉淀方法或者本领域已知的任何其他制备技术负载在Nb2O5-ZrO2上。
OC层304的制备可以通过将Nb2O5-ZrO2载体氧化物研磨来制造含水浆体开始。该Nb2O5-ZrO2载体氧化物的Nb2O5负载量可以是大约15%-大约30%重量,优选大约25%,和ZrO2负载量是大约70%-大约85%重量,优选大约75%。
该Cu-Mn溶液可以通过将适量的硝酸锰溶液(MnNO3)和硝酸铜溶液(CuNO3)混合来制备,这里合适的铜负载量可以包括大约10%-大约15%重量的负载量。合适的锰负载量可以包括大约15%-大约25%重量的负载量。接下来的步骤是硝酸Cu-Mn溶液在Nb2O5-ZrO2载体氧化物含水浆体上沉淀,其可以向其中加入适当的碱溶液,例如来将该浆体的pH调节到合适的范围。该沉淀的浆体可以在连续搅拌下在室温老化大约12-24小时的时间。在老化后,Cu-Mn/Nb2O5-ZrO2浆体可以作为OC层304涂覆。在本发明中,多个容量的OC负载量可以涂覆到WC层302上。该多个OC负载量可以在大约60g/L-大约200g/L变化,在本发明中特别是大约120g/L,来包括这样的Cu-Mn尖晶石结构,其的铜负载量是大约10g/L-大约15g/L和锰负载量是大约20g/L-大约25g/L。该Nb2O5-ZrO2载体氧化物的负载量可以是大约80g/L-大约90g/L。
OC层304可以干燥和随后在大约550℃-大约650℃的合适温度,优选在大约600℃煅烧大约5小时。OC层304的处理可以使用合适的干燥和加热方法。市售的气刀干燥系统可以用于干燥OC层304。热处理(煅烧)可以使用市售燃烧(炉子)系统来进行。
随后,IMP层306可以用硝酸Pd溶液来制备,其可以湿浸渍到WC层302和OC层304顶上来干燥和在大约550℃燃烧大约4小时来完成催化剂结构300。Pd在催化剂体系中的最终负载量可以是大约0.5g/ft3-大约10g/ft3。在这个实施方案中,Pd负载量是大约6g/ft3。
图4显示了用于SPGM催化剂体系类型4的催化剂结构400。在这个系统构造中,WC层402可以包括Cu-Mn化学计量比的尖晶石结构Cu1.0Mn2.0O4,其使用共沉淀方法或者本领域已知的任何其他制备技术负载于Nb2O5-ZrO2和在氧化铝上负载的PGM上。
WC层402的制备可以通过将Nb2O5-ZrO2载体氧化物研磨来制造含水浆体开始。该Nb2O5-ZrO2载体氧化物的Nb2O5负载量可以是大约15%-大约30%重量,优选大约25%,和ZrO2负载量是大约70%-大约85%重量,优选大约75%。
该Cu-Mn溶液可以通过将适量的硝酸锰溶液(MnNO3)和硝酸铜溶液(CuNO3)混合来制备,这里合适的铜负载量可以包括大约10%-大约15%重量的负载量。合适的锰负载量可以包括大约15%-大约25%重量的负载量。接下来的步骤是硝酸Cu-Mn溶液在Nb2O5-ZrO2载体氧化物含水浆体上沉淀,其可以向其中加入适当的碱溶液,例如来将该浆体的pH调节到合适的范围。该沉淀的浆体可以在连续搅拌下在室温老化大约12-24小时的时间。
在沉淀步骤之后,该Cu-Mn/Nb2O5-ZrO2浆体可以进行过滤和清洗,然后所形成的材料可以在大约120℃干燥一整夜和随后在大约550℃-大约650℃的合适温度,优选在大约600℃煅烧大约5小时。所制备的Cu-Mn/Nb2O5-ZrO2粉末可以研磨成细粒子粉末,来加入到WC层402所包括的Pd和氧化铝中。
Cu-Mn/Nb2O5-ZrO2的细粒子粉末可以随后加入到Pd和氧化铝基载体氧化物浆体的组合中。Pd和氧化铝浆体的制备可以通过分别研磨氧化铝基载体氧化物来制造含水浆体而开始。随后,硝酸Pd溶液然后可以与氧化铝的含水浆体混合,负载量是大约0.5g/ft3-大约10g/ft3。在这个实施方案中,Pd负载量是大约6g/ft3和WC材料的总负载量是120g/L。在Pd和氧化铝浆体混合后,Pd可以用适量的一种或多种碱溶液锁住,例如氢氧化钠(NaOH)溶液,碳酸钠(Na2CO3)溶液,氢氧化铵(NH4OH)溶液,四乙基氢氧化铵(TEAH)溶液等。不需要pH调节。在这个实施方案中,Pd可以使用四乙基氢氧化铵(TEAH)的碱溶液锁住。然后所形成的浆体(包括Cu-Mn/Nb2O5-ZrO2的细粒子粉末)可以老化大约12小时-大约24小时,用于随后作为WC层402涂覆。该老化的浆体可以涂覆到陶瓷基底404上,其使用了具有蜂窝结构的堇青石材料,这里陶瓷基底404可以具有多个具有合适的孔隙率的通道。Cu-Mn/Nb2O5-ZrO2和Pd/氧化铝的含水浆体可以使用真空加料和涂覆系统沉积到陶瓷基底404上来形成WC层402。在本发明中,多个容量的WC负载量可以涂覆到陶瓷基底404上。该多个WC负载量可以在大约60g/L-大约200g/L变化,在本发明中特别是大约120g/L。
WC层402的处理可以使用合适的干燥和加热方法。市售的气刀干燥系统可以用于干燥WC层402。热处理(煅烧)可以使用市售燃烧(炉子)系统来进行。
沉积在陶瓷基底404上的WC层402的化学组成(总负载量是大约120g/L)包括Cu-Mn尖晶石结构,其的铜负载量是大约10g/L-大约15g/L,锰负载量是大约20g/L-大约25g/L,和Pd负载量是大约6g/ft3。
根据本发明的原理,所公开的SPGM催化剂体系的最佳NO/CO交换R值可以使用根据本发明的实施方案所制备的新和水热老化的催化剂样品,如图1,图2,图3和图4所述,通过进行等温稳态扫描测试来测定。等温稳态扫描测试可以在所选择的入口温度,使用从富含条件到贫含条件的11点R-值,以多个空速来开发。扫描测试的结果可以比较来显示对于在TWC条件下的最佳性能,所公开的SPGM催化剂体系的最佳组成和构造。
等温稳态扫描测试程序
该等温稳态扫描测试可以使用入口温度是大约450℃的使用流动反应器来进行,并且在从大约2.0(富含条件)到大约0.80(贫含条件)的11点R值测试气体流,来测量CO,NO和HC转化率。
等温稳态扫描测试中的空速(SV)可以在大约40000h-1调节。用于该测试的气体供料可以是标准TWC气体组合物,具有可变的O2浓度,来在测试过程中将R-值从富含条件调节到贫含条件。标准TWC气体组合物可以包括大约8000ppm的CO,大约400ppm的C3H6,大约100ppm的C3H8,大约1000ppm的NOx,大约2000ppm的H2,10%的CO2和10%的H2O。该气体混合物中O2的量可以改变来调节空气/燃料比(A/F)。
TWC标准起燃测试程序
TWC稳态起燃测试可以使用流动反应器来进行,在其中温度可以以大约40℃/min的速率从大约100℃增加到大约500℃,供给下面的气体组合物:8000ppm的CO,400ppm的C3H6,100ppm的C3H8,1000ppm的NOx,2000ppm的H2,10%的CO2,10%的H2O和0.7%的O2。在大约40000h-1的SV的平均R-值是1.05(化学计量比)。
TWC标准振荡起燃测试可以使用流动反应器来进行,在其中温度可以以大约40℃/min的速率从大约100℃增加到大约500℃,供给下面的气体组合物:8000ppm的CO,400ppm的C3H6,100ppm的C3H8,1000ppm的NOx,2000ppm的H2,10%的CO2,10%的H2O和O2量在0.3%-0.45%变化振荡。在大约90000h-1的SV的平均R-值是1.05(化学计量比)。振荡起燃测试可以在大约1Hz和±0.4A/F比跨度进行。
SPGM催化剂体系的TWC性能
图5显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和空速(SV)是大约40000h-1,新SPGM催化剂体系样品类型1的TWC性能500。
如图5中可见,在新样品中,NO/CO交换是在0.950的特定R-值进行的。用于典型的PGM催化剂的NO/CO交换是在化学计量比R-值(大约1.00)进行的,但是SPGM催化剂体系类型1代表了低于化学计量比条件的R-值,其是在化学计量比贫含条件(R=0.950)下NO和CO的100%转化率的指示。在化学计量比贫含条件下NOx转化率是非常高的。在R-值=0.9时可见,NOX转化率是大约96%。
图6显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,新SPGM催化剂体系样品类型2的TWC性能600。
如图6中可见,在新样品中,NO/CO交换是在1.160的特定R-值进行的,这里新NO/CO转化率是99.6%。
图7显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,新SPGM催化剂体系样品类型3的TWC性能700。
如图7中可见,在新样品中,NO/CO交换是在1.099的特定R-值进行的,这里新NO/CO转化率是100%。可以观察到这个NO/CO交换是在倾向于稍微富含条件的化学计量比条件下进行的。典型的PGM催化剂的R-值是1.00。
图8显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,新SPGM催化剂体系样品类型4的TWC性能800。
如图8中可见,在新样品中,NO/CO交换是在1.044的特定R-值进行的,这里新NO/CO转化率是100%。可以观察到这个NO/CO交换非常接近于化学计量比条件和稍微倾向于在富含条件下。一种典型的PGM催化剂的R-值是1.00。在化学计量比贫含条件下的NOX转化率是大的。可以看到,在R-值=0.9,NOX转化率是大约82%。
在本发明中,所形成的用于稳态扫描条件下的SPGM催化剂体系各自的R-值显示了所公开的SPGM催化剂体系表现出最佳的性能,因为NO/CO交换R-值非常接近于化学计量比条件,并且在SPGM催化剂体系类型1的情况中,0.95的R-值是在贫含条件下100%的NO和CO转化率的指示。
SPGM和PGM催化剂体系的TWC性能比较
图9显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,SPGM催化剂体系类型1,类型2,类型3,类型4和市售的PGM催化剂的新样品的NO转化中的性能比较900。
该等温稳态扫描测试可以使用流动反应器来进行,入口温度是大约450℃,来模拟标准TWC气体组合物的废气,具有不同的O2来调节A/F比,其使用了从大约2.0(富含条件)到大约0.80(贫含条件)的11点R值,来测量NO转化率。
在这种实施方案中,市售的PGM催化剂的新样品可以是催化剂,其包括Pd负载量为大约6g/ft3和铑(Rh)负载量是大约6g/ft3的OC层,具有氧化铝基载体氧化物和大约30-大约40重量%的储氧材料。WC层仅仅包括氧化铝基载体氧化物和储氧材料。
在性能比较900中,NO转化率曲线902显示了SPGM催化剂体系类型1新样品的性能,NO转化率曲线904显示了SPGM催化剂体系类型2新样品的性能,NO转化率曲线906显示了SPGM催化剂体系类型3新样品的性能,NO转化率曲线908显示了SPGM催化剂体系类型4新样品的性能,和NO转化率曲线910显示了市售的PGM催化剂的新样品的性能,全部处于稳态扫描条件下。
如在性能比较900中可观察的,与PGM催化剂相比,SPGM催化剂体系类型1和SPGM催化剂体系类型4在化学计量比贫含条件下的NO转化中具有改进的性能。这种改进的性能是两种SPGM催化剂体系中各自组合物中PGM组分和Cu-Mn尖晶石组分之间的协同效应的结果,在其中Cu-Mn尖晶石组分的加入导致了与NO转化率曲线910中所示的PGM催化剂的NO转化率水平相比,在贫含条件下NO转化率改进的性能。SPGM催化剂体系类型1和类型4的表现优于PGM催化剂,这归因于它们在贫含条件下改进的NO转化率。例如在R=0.9,虽然SPGM催化剂体系类型1表现出NO转化率是96%,但是SPGM催化剂体系类型4表现出NO转化率是82%,PGM催化剂表现出NO转化率是38%。另外SPGM催化剂体系类型1和类型4都代表了在R-值小于1.00时的NO转化率,其是用于PGM催化剂的典型的R-值。
图10显示了根据一种实施方案,在等温稳态扫描条件,在入口温度是大约450℃和SV是大约40000h-1,SPGM催化剂体系类型1,类型2,类型3,类型4和市售的PGM催化剂的水热老化样品的NO转化中的性能比较1000。
在这种实施方案中,市售的PGM催化剂的新样品可以是催化剂,其包括Pd负载量为大约6g/ft3和铑(Rh)负载量是大约6g/ft3的OC层,具有氧化铝基载体氧化物和大约30-大约40重量%的储氧材料。WC层仅仅包括氧化铝基载体氧化物和储氧材料。
SPGM催化剂体系类型1,类型2,类型3,类型4和市售的PGM催化剂的样品可以使用大约10%蒸汽/空气或者燃料流,在大约800℃-大约1000℃的多个温度进行水热老化大约4小时。在这个实施方案中,全部样品可以优选在900℃老化大约4小时。
该等温稳态扫描测试可以使用流动反应器来进行,入口温度是大约450℃,来模拟标准TWC气体组合物的废气,具有不同的O2来调节A/F比,其使用了从大约2.0(富含条件)到大约0.80(贫含条件)的11点R值,来测量NO转化率。
在性能比较1000中,NO转化率曲线1002显示了SPGM催化剂体系类型1新样品的性能,NO转化率曲线1004显示了SPGM催化剂体系类型2新样品的性能,NO转化率曲线1006显示了SPGM催化剂体系类型3新样品的性能,NO转化率曲线1008显示了SPGM催化剂体系类型4新样品的性能,和NO转化率曲线1010显示了市售的PGM催化剂新样品的性能,全部在稳态扫描条件下。
如在性能比较1000中可观察的,与PGM催化剂相比,SPGM催化剂体系类型1在化学计量比贫含下老化后的NO转化中具有改进的性能。这种改进的性能是SPGM催化剂体系类型1中各自组合物中PGM组分和Cu-Mn尖晶石组分之间的协同效应的结果,在其中Cu-Mn尖晶石组分的加入导致了与NO转化率曲线1010中所示的PGM催化剂的NO转化率水平相比,NO转化率改进的性能。例如在R-值=0.9时,SPGM催化剂体系类型1表现出NO转化率是95%,同时PGM催化剂表现出NO转化率是35%。
另外,从性能比较900和性能比较1000可见,NO转化率的最佳的性能是用SPGM催化剂体系类型1的新和老化的样品来获得的,其表现出在贫含区域(R-值<1.00)下改进的NO转化率。SPGM催化剂体系类型1新和水热老化的样品的NO/CO交换R-值分别是0.950和0.965,这表明与PGM催化剂样品相比,在贫含条件下增强的性能。PGM催化剂新和水热老化的样品的NO/CO交换R-值分别是0.998和1.000。
SPGM催化剂体系类型1,类型2,类型3和类型4和PGM催化剂的新和水热老化的样品在等温稳态扫描条件下获得的NO/CO交换R-值可以证实当与本发明的其他SPGM催化剂体系和PGM催化剂相比时,SPGM催化剂体系类型1的最佳的性能,因为SPGM催化剂体系类型1新和水热老化的样品的NO/CO交换R-值低于PGM催化剂的新和水热老化的样品的NO/CO交换R-值,这表明SPGM催化剂体系类型1是一种改进,在其中根据本发明的原理所显示的协同效应是非常相关的。此外,SPGM催化剂体系类型1表现出与PGM催化剂相比在贫含条件中NO转化率的明显改进。
可以观察到,SPGM催化剂体系类型2,类型3和类型4表现出老化后增加的R-值。所获得的R-值表明它们可以在化学计量比条件或者在稍富含条件交换下进行。但是,SPGM催化剂体系类型1表现出朝着贫含条件的明显改进,其超过了PGM催化剂的性能,这归因于在贫含条件下实现的高的NO转化率,其也会导致较低的燃料消耗。
用于SPGM催化剂体系类型1的TWC标准起燃测试
图11显示了根据一种实施方案,在SV大约40000h-1和R值是大约1.05的等温稳态条件(图11A),和在频率信号是大约1Hz和±0.4A/F比跨度,SV是大约90000h-1和R值是大约1.05的振荡条件下(图11B),SPGM催化剂体系类型1新样品所进行的TWC标准起燃测试结果的活性比较1100。
在图11A中,NO转化率曲线已经用虚线标记为NO曲线1102,CO转化率曲线已经用点虚线标记为CO曲线1104,和HC转化率曲线已经用实线标记为HC曲线1106。在图11B中,NO转化率曲线已经用虚线标记为NO曲线1108,CO转化率曲线已经用点细线标记为CO曲线1110,和HC转化率曲线已经用实线标记为HC曲线1112。
可见在稳态起燃测试中,在NO曲线1102中,在大约211.9℃的T50发生了50%的NO转化率,在CO曲线1104中,在大约228.1℃的T50发生了50%的CO转化率,和在HC曲线1106中,在大约265.9℃的T50发生了50%的HC转化率。在振荡起燃测试下,在NO曲线1108中,在大约295.4℃的T50发生了50%的NO转化率,在CO曲线1110中,在大约257.3℃的T50发生了50%的CO转化率,和在HC曲线1112中,在大约286.9℃的T50发生了50%的HC转化率。
图11A和图11B的转化率结果的比较表明SPGM类型1催化剂体系表现出在低于300℃发生了全部污染物高的NO/CO/HC转化率和T50转化率,但是图11B中全部污染物较高的T50是归因于用于在振荡起燃条件下SPGM催化剂体系类型1测试的较高的SV。
根据本发明的原理,将氧化铝基载体上的Pd作为外涂层和将负载于Nb2O5-ZrO2上的Cu-Mn化学计量比的尖晶石结构Cu1.0Mn2.0O4作为活化涂层施用到陶瓷基底上,产生了较高的催化活性,效率和在TWC条件中更好的性能,特别是在与市售的PGM催化剂相同的条件下。所获得的新和老化的SPGM样品的较低水平的温度T50和在贫含条件下较高的NO转化率也可以显示SPGM催化剂体系改进的性能和热稳定性。SPGM催化剂体系类型1的催化剂体系构造,材料组成和制备可以选为用于许多TWC应用中的最佳的催化剂体系。
SPGM催化剂体系类型1的催化剂体系构造,材料组成和制备可以提供最佳的用于贫含性能的选择,其是Pd和Cu-Mn化学计量比的尖晶石结构之间的协同关系的结果,其是产生了更高催化活性的一种协作行为。
虽然已经公开了不同的方面和实施方案,但是可以预期其他方面和实施方案。此处所公开的不同的方面和实施方案是用于说明的目的,并非打算限制下面的权利要求所示的真实范围和主旨。
Claims (22)
1.一种催化剂体系,其包含:
至少一种基底;
至少一种活化涂层,其包含至少一种储氧材料,进一步包含具有铌-氧化锆载体氧化物的Cu-Mn尖晶石;和
至少一种外涂层,其包含至少一种铂族金属催化剂和Al2O3。
2.权利要求1的催化剂体系,其中该Cu-Mn尖晶石包含CuMn2O4。
3.权利要求1的催化剂体系,其中该Cu-Mn尖晶石是化学计量比的。
4.权利要求1的催化剂体系,其中该铌-氧化锆载体氧化物包含Nb2O5-ZrO2。
5.权利要求1的催化剂体系,其进一步包含至少一种浸渍层。
6.权利要求1的催化剂体系,其中该至少一种基底包含陶瓷。
7.权利要求1的催化剂体系,其中NO的转化是在贫含排气条件下基本完成的。
8.权利要求1的催化剂体系,其中CO的转化是在贫含排气条件下基本完成的。
9.权利要求1的催化剂体系,其中NO的转化率在贫含排气条件下接近95%。
10.权利要求1的催化剂体系,其中NO的转化率是在这样的催化剂体系上改进的,其包含至少一种铂族金属催化剂和基本上没有Cu-Mn尖晶石。
11.权利要求1的催化剂体系,其中该NO交换R-值是大约0.950。
12.权利要求1的催化剂体系,其中该CO交换R-值是大约0.965。
13.一种催化剂体系,其包含:
至少一种基底;
至少一种活化涂层,其包含至少一种铂族金属催化剂和Al2O3;和
至少一种外涂层,其包含至少一种储氧材料,进一步包含具有铌-氧化锆载体氧化物的Cu-Mn尖晶石。
14.权利要求13的催化剂体系,其中该Cu-Mn尖晶石包含CuMn2O4。
15.权利要求13的催化剂体系,其中该Cu-Mn尖晶石是化学计量比的。
16.权利要求13的催化剂体系,其中该铌-氧化锆载体氧化物包含Nb2O5-ZrO2。
17.权利要求13的催化剂体系,其进一步包含至少一种浸渍层。
18.权利要求13的催化剂体系,其中该至少一种基底包含陶瓷。
19.权利要求13的催化剂体系,其中NO的转化是在贫含排气条件下基本完成的。
20.权利要求13的催化剂体系,其中CO的转化是在贫含排气条件下基本完成的。
21.权利要求13的催化剂体系,其中NO的转化率是在这样的催化剂体系上改进的,其包含至少一种铂族金属催化剂和基本上没有Cu-Mn尖晶石。
22.一种催化剂体系,其包含:
至少一种包含陶瓷的基底;
至少一种包含Al2O3的活化涂层;
至少一种外涂层,其包含至少一种储氧材料,进一步包含具有铌-氧化锆载体氧化物的Cu-Mn尖晶石;和
至少一种包含至少一种铂族金属催化剂的浸渍层;
其中该至少一种铂族金属催化剂包含钯。
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US20090324468A1 (en) * | 2008-06-27 | 2009-12-31 | Golden Stephen J | Zero platinum group metal catalysts |
WO2010029431A2 (en) * | 2008-09-10 | 2010-03-18 | Advent Technologies | Internal reforming alcohol high temperature pem fuel cell |
US20130115144A1 (en) * | 2011-08-10 | 2013-05-09 | Clean Diesel Technologies, Inc. | Catalyst with Lanthanide-Doped Zirconia and Methods of Making |
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CN111644182A (zh) * | 2020-03-05 | 2020-09-11 | 王金波 | 一种用于高空速条件下快速催化氧化co的蜂窝陶瓷整体催化剂及其制备方法 |
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US9555400B2 (en) | 2017-01-31 |
US20150290630A1 (en) | 2015-10-15 |
WO2015157614A1 (en) | 2015-10-15 |
US20150148223A1 (en) | 2015-05-28 |
CN106413881B (zh) | 2020-01-24 |
CN105682790A (zh) | 2016-06-15 |
US20150238941A1 (en) | 2015-08-27 |
WO2015081156A1 (en) | 2015-06-04 |
US9511355B2 (en) | 2016-12-06 |
US20150238940A1 (en) | 2015-08-27 |
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