CN102787888A - 产生低温废气流的发动机用的氧化催化剂 - Google Patents
产生低温废气流的发动机用的氧化催化剂 Download PDFInfo
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- CN102787888A CN102787888A CN2012101551572A CN201210155157A CN102787888A CN 102787888 A CN102787888 A CN 102787888A CN 2012101551572 A CN2012101551572 A CN 2012101551572A CN 201210155157 A CN201210155157 A CN 201210155157A CN 102787888 A CN102787888 A CN 102787888A
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- oxidation
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- mixed oxide
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- 239000002245 particle Substances 0.000 claims abstract description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 33
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- 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 claims description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
可以使用铈、锆和铜的混合氧化物粒子与氧化铝负载的铂族金属催化剂的离散粒子的组合催化含氧气流,如来自柴油机或其它稀燃发动机的废气流中的一氧化碳(CO)和烃(HC)的氧化。氧化催化剂粒子的这种组合在低于300℃下有效催化氧化CO和HC。
Description
技术领域
本公开涉及来自柴油机或具有相对较低运行温度并产生低温废气的其它稀燃发动机的废气流中的一氧化碳和不完全燃烧烃(HC)的催化氧化。更具体地,本发明涉及铈、锆和铜的混合氧化物颗粒与负载在氧化铝颗粒上的至少一种铂族金属(PGM)颗粒联合用于催化在低于300℃下的此类氧化反应的用途。
发明背景
可构造和控制机动车发动机以在它们的燃烧混合物中的不同的空气和燃料(proportions of air and fuel)比例下运行。当内燃机在高于化学计量的空气-燃料质量比下运行时,这种运行模式被称作“稀燃(fuel-lean)”,并通常产生提高的燃料燃烧效率和因此改进的燃料经济性。压缩点火发动机,如柴油机,传统上主要以稀燃模式运行。也可以控制火花点火发动机,如汽油机以便以稀燃模式运行以利用相关的改进的燃料经济性。
如今,先进的内燃机可以例如由计算机模块控制以便以多种模式运行。例如,一些先进的内燃机可以选择性地以稀燃和富燃(fuel-rich)模式运行以实现更好的燃烧稳定性和燃料经济性,同时降低废气中某些燃烧排放物的量。
来自以稀燃模式运行的发动机的废气具有相对较低的温度并含有不合意的气体排放物,如一氧化碳(CO)、未燃烃(HC)和氮氧化物(NOx)。具体而言,来自以稀燃模式运行的发动机的废气温度可以为150℃或更低。可能存在运行温度更低的时期,如发动机运行的初始冷启动期间,和在发动机低速运行或空转时。希望处理这种废气组合物以使除氮气(N2)、二氧化碳(CO2)和水外排放到大气中的任何物质减至最少。为了将CO、HC和NOx的气体排放物转化成这些更无害的气体,可以使废气经过处理***,在此其可接触至少一种催化剂以助于(1)将CO氧化成CO2,(2)将HC氧化成CO2和水,和(3)将NOx还原成N2。
内燃机的废气处理***可包括用于将CO氧化成CO2和将HC氧化成CO2和水的氧化催化剂。传统氧化催化剂包括作为催化剂负载的一种或多种铂族金属(PGM)。PGM统一是指周期表中的六种金属元素并包括钌、铂、钯、铑、锇和铱。但是,市售PGM基氧化催化剂的活化温度通常高于175℃,但如上所述,来自稀燃发动机的废气温度可以为大约150℃或更低。
为了提高传统PGM基氧化催化剂在相对较低温度下的氧化性能,可以提高该催化剂中的PGM的量。但是,提高该氧化催化剂的PGM载量只能在有限程度上降低该催化剂的活化温度。由于PGM相对昂贵,提高PGM载量显著提高该催化剂的成本。需要在低温下具有同等或优选更好的CO和HC氧化活性的较便宜的氧化催化剂以处理来自具有相对较低运行温度的现代稀燃和先进内燃机的废气。
发明概述
据发现,Ce、Zr和Cu的混合氧化物颗粒可以与分散在氧化铝(Al2O3)颗粒上的至少一种铂族金属(PGM)催化剂的离散颗粒合并,在适当合并时,这些氧化催化剂可有效氧化包含CO和HC并具有通常低于300℃的相对较低温度的废气流中的CO和HC。
该混合氧化物组合物具有基本由铈(Ce)、锆(Zr)和铜(Cu)的元素构成的金属组分。在合适的实施方案中,金属组分可包含,按摩尔计,大约30至70% Ce、大约30至70% Zr且余量为Cu。在本发明的优选实施方案中,金属组分包含,按摩尔计,大约60% Ce、大约15% Zr和大约25% Cu。
优选通过从含水溶液(aqueous solution)中共沉淀这三种金属来制备CeZrCu混合氧化物以用作粉末催化剂。将沉淀物干燥,球磨并煅烧以形成CeZrCuO2的固溶体的颗粒。当氧化物分子共用单晶格时,存在Ce、Zr和Cu的混合氧化物的固溶体。
至少一种PGM的颗粒优选由铂(Pt)和钯(Pd)的组合构成,Pt-Pd/Al2O3颗粒中的Pt/Pd质量比优选为7:1。Pt和Pd的颗粒优选占含CeZrCuO2和Pt-Pd/Al2O3的微粒催化剂的0.75至1.5重量%。
在一个合适的实施方案中,制成的催化剂颗粒可以以涂布到包含从承载体入口面到出口面纵向延伸的多个细平行流通通道的蜂窝形整料承载体(support body)的通道壁上的洗涂层(washcoat layer)的形式使用。将CeZrCuO2和Pt-Pd/Al2O3的细粒分散在含水溶液中,将其施加并烘焙到承载体的通道壁上以形成洗涂层。
将该催化剂涂布的承载体适当地置于位于废气流路径中的容器中,以使废气流经通道并接触分散在通道壁上的催化剂颗粒。该承载体在尺寸上提供合适数量的通道(优选至少400/平方英寸)以一起适应废气流的所需流速和因此废气在承载体内的所需停留时间。合适的空间速度(即废气流体积与承载体通道内的可用流动体积之间的关系)为30,000 hr-1。
在本发明的优选实施方案中,通过在承载体壁上涂布分别的(discrete)洗涂层来合并这些氧化催化剂,各分别的层包含CeZrCuO2颗粒或Pt-Pd/Al2O3颗粒。在合适的“双层”布置中,包含Pt-Pd/Al2O3颗粒的第一洗涂层从承载体的入口面到出口面涂布到通道壁上,包含CeZrCuO2颗粒的第二层涂布到通道壁上以使其覆盖第一洗涂层。在合适的“分区涂布(zone-coat)”布置中,第一洗涂层涂布到入口面附近的通道壁部分或区域上,第二洗涂层涂布到承载体出口面附近的通道壁的分别的部分或区域上。
本发明包括以下方面:
1. 氧化内燃机废气流中的一氧化碳(CO)和烃(HC)的方法;所述方法包括:
运行内燃机以燃烧空气和燃料的混合物,其中所述混合物中的燃料含量相对于化学计量的空气-燃料质量比为稀,所述发动机产生温度通常低于300℃的废气流;
输送所述废气流与氧化催化剂接触足以将基本所有CO氧化成二氧化碳(CO2)和将至少一部分HC氧化成CO2和水的时间;所述氧化催化剂作为洗涂层分散在流通式承载体的通道壁上,所述洗涂层包含(i)基本由铈、锆和铜的共沉淀混合氧化物(CeZrCuO2)颗粒构成的混合氧化物层和(ii)基本由分散在氧化铝颗粒上的至少一种铂族金属颗粒(PGM/Al2O3)构成的分别的PGM层,所述洗涂层的层经布置以使在所述废气流接触PGM/Al2O3的颗粒之前氧化在废气流中存在的一部分CO。
2. 如方面1中所述的氧化方法,其中所述发动机废气流通常低于200℃。
3. 如方面1中所述的氧化方法,其中所述废气流包含各至少500 ppm的 CO和HC。
4. 如方面1中所述的氧化方法,其中所述混合氧化物层包含基本由铈(Ce)、锆(Zr)和铜(Cu)的元素构成的金属组分,且所述金属组分包含,按摩尔计,大约30至70%的 Ce、大约30至70%的 Zr和余量Cu。
5. 如方面1中所述的氧化方法,其中所述混合氧化物层包含基本由铈(Ce)、锆(Zr)和铜(Cu)的元素构成的金属组分,且所述金属组分包含,按摩尔计,大约60% 的Ce、大约15% 的Zr和大约25%的 Cu。
6. 如方面1中所述的氧化方法,其中PGM层从所述承载体的入口面到出口面分散在通道壁上,此后所述混合氧化物层分散在通道壁上以使所述混合氧化物层在流通式承载体的通道壁上覆盖PGM层。
7. 如方面1中所述的氧化方法,其中所述混合氧化物层分散在所述流通式承载体入口面附近的通道壁的第一部分上,所述PGM层分散在流通式承载体出口面附近的通道壁的第二部分上。
8. 如方面1中所述的氧化方法,其中所述至少一种铂族金属由钌、铂、钯、铑、锇和铱中的至少一种构成。
9. 如方面1中所述的氧化方法,其中所述至少一种铂族金属包含铂和钯的组合,且在所述PGM层中铂与钯的质量比为大约7比1。
10. 如方面1中所述的氧化方法,其中所述至少一种铂族金属是金和钯的组合,且在成层的氧化催化剂中金与钯的质量比为大约1比1。
11. 如方面1中所述的氧化方法,其中铈、锆和铜的共沉淀混合氧化物颗粒具有单相结晶结构。
12. 如方面1中所述的氧化方法,其中所述承载体是挤出堇青石材料并具有均匀圆柱形横截面,所述承载体具有与废气流的流向横切的入口面和出口面,包含至少400个通道/平方英寸入口面横截面积,并经尺寸化以促进流经所述承载体的废气流中的CO和HC的氧化。
从本发明的优选(但非限制性)实施方案的进一步描述中可明显看出本发明的其它目的和优点。
附图简述
图1是含有空气和燃料的混合物的气流的路径的示意图,该气流被输送至内燃机气缸,作为废气流从排气歧管离开发动机进入废气处理***中,并作为处理过的废气流经由尾管开口排放到环境大气中。
图2是位于图1中所示的废气处理***中的反应器的示意图,并描绘容纳涂有催化剂的承载体的容器,其从该容器和承载体的一部分上切出楔形以更好显示延伸穿过其中的平行流通通道。
图3是图2中所示的承载体的一段流通通道的示意图,并描绘在一部分通道壁上的洗涂层,该洗涂层基本由与Pt-Pd/Al2O3离散颗粒物理混合的CeZrCuO2颗粒构成。
图4是图2中所示的承载体的一段流通通道的示意图,并描绘基本由PGM/Al2O3颗粒构成的第一洗涂层和基本由CeZrCuO2构成的第二洗涂层的“双层”布置,其中第二层覆盖在通道壁上的第一层上。
图5是图2中所示的承载体的一段流通通道的示意图,并描绘基本由CeZrCuO2颗粒构成的第一洗涂层和基本由PGM/Al2O3颗粒构成的第二洗涂层的“分区涂布”布置,其中第一层涂布在承载体入口面附近的通道部分上,第二层涂布在承载体出口面附近的通道的分别的部分上。
图6是对于在具有125至300℃的温度范围的含有500 ppm CO、200 ppm NO、260 ppm C3H6、90 ppm C3H8、112 ppm C12H26、83 ppm C8H10、8% O2、8% H2O和余量N2的合成废气流中CeZrCuO2催化剂(点划线)、Pt-Pd/Al2O3催化剂(虚线)和含Pt-Pd/Al2O3和CeZrCuO2的催化剂(实线)的CO氧化转化百分比 vs. 温度(℃)的图。
图7是对于在具有125至300℃的温度范围的含有500 ppm CO、200 ppm NO、260 ppm C3H6、90 ppm C3H8、112 ppm C12H26、83 ppm C8H10、8% O2、8% H2O和余量N2的合成废气流中CeZrCuO2催化剂(点划线)、Pt-Pd/Al2O3催化剂(虚线)和含Pt-Pd/Al2O3和CeZrCuO2的催化剂(实线)的重质HC氧化转化百分比 vs. 温度(℃)的图。
图8是对于在具有125至300℃的温度范围的含有500 ppm CO、200 ppm NO、260 ppm C3H6、90 ppm C3H8、112 ppm C12H26、83 ppm C8H10、8% O2、8% H2O和余量N2的合成废气流中CeZrCuO2催化剂(点划线)、Pt-Pd/Al2O3催化剂(虚线)和含Pt-Pd/Al2O3和CeZrCuO2的催化剂(实线)的C3H6氧化转化百分比 vs. 温度(℃)的图。
优选实施方案描述
据发现,CeZrCu混合氧化物颗粒可以与负载在氧化铝(Al2O3)颗粒上的至少一种PGM催化剂的离散颗粒合并,在适当合并时,这些氧化催化剂可以在相对较低温度(大约125至大约300℃)下有效氧化CO和HC。
在本发明的优选实施方案中,通过在安装在位于来自稀燃发动机的废气流的路径中的容器内的挤出陶瓷蜂窝形流通式承载体的壁上涂布分别的洗涂层,来合并这些氧化催化剂。
合适的催化氧化反应器60显示在图1中。参照图1,空气燃料混合物10进入内燃机20并作为废气30离开,废气流40随后经过包括用于废气30中的CO和HC的有效氧化的氧化催化剂60的废气处理***50。
多缸往复式活塞内燃机20可以是充量压燃发动机(charge compression engine)(即柴油机)、火花点火直接喷射式发动机(即汽油机,其可含有或不含缸内燃料喷射器)或均质充量压燃发动机。这些类型的发动机各包括容纳连接到曲轴26上的往复式活塞头24的汽缸22(通常4至8个汽缸)。在各活塞头24上方设置燃烧室28,其以特定计时间隔经由进气阀12接收空气和燃料的混合物10。空气和燃料的混合物10在燃烧室28中的火花或压缩辅助点火引发它们各自的活塞头24快速向下直线运动以驱动曲轴26的旋转。短时间后,各活塞头24的反应性向上运动经由排气阀14从各燃烧室28排出燃烧产物。
以响应发动机性能要求(即给压和解压位于驾驶舱中驾驶员侧(driver-side compartment)的脚踏板以影响车辆速度和加速)的可变质量流速向发动机20供应连续空气流。如例如发动机控制策略所指示,就在发动机20上游将计算量的加压燃料快速和间歇喷射到输入气流中,以产生表现出即刻要求的空气对燃料质量比的空气和燃料的混合物(未显示)。控制喷射到输入气流中的燃料量以保持稀空气对燃料质量比(lean air to fuel mass ratio)或富空气对燃料质量比(rich air to fuel mass ratio),或在这两种状态之间切换。
空气和燃料的混合物10进入内燃机20的进气歧管16并作为废气30经由排气歧管18离开。进气歧管16经由进气阀12将空气和燃料混合物10输送到燃烧室28中,然后输送至发动机20的汽缸22。将空气和燃料混合物10压缩,加热并由此点火以向发动机20的汽缸22中的往复式活塞头24供应动力。活塞24的排气冲程将废燃烧产物(包括CO、HC和NOx)从发动机20的汽缸22经由排气阀14排出到排气歧管18中。排气歧管18将燃烧产物作为废气30输送至废气处理***50。处理***50将废气30传送至催化氧化反应器60以有效氧化CO和HC。
如图1-3中所示,废气流40进入催化氧化反应器60并经过承载体70的流通通道72,在此其接触作为含有催化剂细粒的至少一个洗涂层80分散在通道72的壁74上的氧化催化剂。通道壁74的高表面积造成废气30和催化剂颗粒之间的充分接触以便发生所需氧化反应。废气处理***50随后将废气流40作为处理过的废气流42从催化氧化反应器60中输送。处理过的废气32经由出口(vent)52从处理***50排放到环境大气中。
用于本文公开的催化氧化反应的合适的氧化反应器60显示在图2中,并在废气处理***50内呈管道状(piped)以利于废气流40连续通过其中。氧化反应器60包含合金钢容器62,该容器成形有供废气进入的上游开口64和供废气流过(through-flow)的下游开口66。容器62的主体通常具有圆形或椭圆形横截面并尺寸化(sized)以容纳用含有催化剂颗粒的洗涂层涂布的承载体70。在图2中,已切除容器62和涂有催化剂的承载体70的楔形部分以更好显示延伸穿过其中的内通道72。
如图2中所示的承载体70是具有与废气流40横切的(即沿流动轴A)入口面76和出口面78的蜂窝形整料,并包括由壁74划定并从承载体的入口面76纵向延伸至出口面78的数个小的正方形平行流通通道72。由于各通道72的供废气流40通过的横截面小,该承载体的入口面76尺寸化以提供合适数量的通道72以一起适应废气流40的所需流速。例如,承载体70可含有大约400个通道72/平方英寸入口面76横截面积。通道壁74的优选厚度为0.002至0.015英寸。尽管挤出陶瓷蜂窝形整料经证实对氧化催化剂而言有效和耐用,但可以使用不同材料的其它催化剂载体。
如图3、4和5中所示,氧化催化剂的小颗粒以洗涂层80或层82、84、86、88的形式沉积在流通通道72的壁74上,几种沉积布置可行。
在图3中所示的一个合适的实施方案中,可以将承载体70浸在含有CeZrCuO2颗粒和Pt-Pd/Al2O3离散颗粒的水溶液中,其随后烘焙以使催化剂颗粒干燥到壁74上并在流通通道72的壁74上形成洗涂层80。图3中所示的洗涂层80仅是理想化描绘;其不是按比例绘制并且无意代表催化剂颗粒的实际沉积布置。
在图4中所示的另一实施方案中,承载体70可以用分别的洗涂层82、84涂布。可以将承载体70浸在含有Pt-Pd/Al2O3颗粒的含水溶液中,其随后烘焙以使催化剂颗粒干燥到壁74上并形成基本由Pt-Pd/Al2O3颗粒构成的第一洗涂层82。可随后将承载体70浸在含有CeZrCuO2颗粒的水溶液中并干燥以形成覆盖第一洗涂层82的第二洗涂层84。这种“双层”布置提供两个分别的层82,84,它们沿整个承载体70形成连续催化剂涂层。
在图5中所示的另一实施方案中,可以在入口面76附近的一半的承载体70上形成含有CeZrCuO2颗粒的第一洗涂层86,并可以在出口面78附近的剩余那半的承载体70上形成含有Pt-Pd/Al2O3颗粒的第二洗涂层88。这种“分区涂布”布置提供两个大小相等的分别层86、88,它们一起沿整个承载体70形成连续催化剂涂层。
本发明人在此已经观察到,废气流中存在的CO可能抑制传统PGM基氧化催化剂上的HC氧化,反之亦然,尤其是在低于200℃的温度下。但是,如图6、7和8中所示,CeZrCuO2催化剂颗粒与Pt-Pd/Al2O3催化剂离散颗粒的适当合并可以在极低温度(125至300℃)下有效氧化含有显著量的CO和HC的合成废气流中的CO和HC。在分别的层中布置催化剂被认为允许催化剂之间的协作,这促进CO和HC的有效氧化。在上文论述的布置中,CeZrCuO2催化剂颗粒可以在极低温度下从废气流中有效除去CO,Pt-Pd/Al2O3催化剂颗粒在已从废气中除去一定量CO后在低温下更有效氧化HC。
本发明的氧化催化剂可用于除柴油机或汽油机废气处理以外的用途,并可用于气载可氧化组分,通常例如压缩天然气发动机、以乙醇为燃料的发动机、压缩机、燃气轮机等的废气的氧化。
该废气可能经过图1中没有明示的其它装置或机械设备,它们可能有助于或无助于产生处理过的废气流42。这些装置包括例如另外的氧化催化剂、三效催化剂、微粒过滤器、选择性催化还原(SCR)催化剂装置、废气再循环线路、涡轮增压轮机、消音器和/或共振器。技术人员无疑知道和理解废气可能经过的这些和许多其它装置。
实施例
通过在室温下在搅拌下将预定比例的铈硝酸盐、锆硝酸盐和铜硝酸盐溶解在水溶液中大约0.5小时,制备合适的CeZrCu混合氧化物催化剂材料。将1M氢氧化钠溶液在剧烈搅拌下添加到该水溶液中,直至该溶液的pH值达到10并形成悬浮的金属共沉淀物。随后使该悬浮溶液在温和搅拌下在室温下放置18小时,然后加热至80℃ 持续2小时,用热水洗涤,在110℃下干燥整夜,然后在400℃下煅烧4小时。制成的CeZrCuO2催化剂材料的X-射线衍射图可证实,这种制备方法产生单相结晶结构,或这三种金属的固溶体。以该材料中的金属组分为100摩尔%,通过此实施例得到的粉末催化剂的组成为60摩尔%铈、15摩尔%锆和25摩尔%铜。制成的CeZrCuO2固体粉末催化剂材料的密度为大约2.01 g/cc,孔隙体积为0.386cc/g。制成的CeZrCuO2催化剂材料的BET表面积为大约31平方米/克。
用于比较的基准(benchmarking)催化剂含有1.5重量%负载在氧化铝(Al2O3)载体材料上的铂和钯。这种催化剂的铂/钯摩尔比为7:1。这种Pt-Pd/Al2O3催化剂材料的密度为0.68 g/cc,孔隙体积为0.71 cc/g。
实施例1
可以通过将0.1056cc催化剂粉末置于具有3/8英寸外径的填充床石英管反应器中来测量这些粉末催化剂的氧化活性。含有500 ppm CO、260 ppm C3H6、90 ppm C3H8、112 ppm C12H26、83 ppm C8H10、200 ppm NO、8% O2、8% H2O和余量N2的合成柴油机废气由质流控制器调节并经由加热的不锈钢管路以300 cc/min流速(相当于170,000 hr-1的空间速度)送入该反应器。在125o至300℃的温度范围内测量针对该催化剂材料的氧化活性,并以5℃/min升温速率将温度逐步提高25℃。
通过测量对于各催化剂床的%CO和HC转化率,评测CeZrCuO2催化剂和1.5% Pt-Pd/Al2O3催化剂的氧化活性。为了比较,使用起燃温度(light-off temperature)或实现50%转化率的温度(T50)。对于CeZrCuO2催化剂,CO转化的T50为124℃,而1.5% Pt-Pd/Al2O3催化剂达到196℃的T50。对于CeZrCuO2催化剂,重质HC(C12H26和C8H10)转化的T50为190℃,而1.5% Pt-Pd/Al2O3催化剂达到219℃的T50。因此,CeZrCuO2催化剂可用于稀燃发动机的废气中的低温CO和重质HC氧化,因为其具有比基准催化剂更好的氧化活性。对于CeZrCuO2催化剂,C3H6转化的T50为271℃,而1.5% Pt-Pd/Al2O3催化剂达到214℃的T50。也就是说,CeZrCuO2催化剂的C3H6氧化活性在低温下并不接近于(not nearly)像标准1.5% Pt-Pd/Al2O3催化剂那样高。
实施例2
在另一实例中,通过初湿含浸法(incipient wetness impregnation method)用铂和钯的混合物浸渍CeZrCuO2催化剂颗粒以使该催化剂含有与基准催化剂相同的每比体积催化剂的Pt和Pd量。具体而言,将29.75克CeZrCuO2粉末(相当于10克氧化铝粉末的等效体积(equivalent volume))与分别含有0.0886克Pt和0.0127克Pd作为金属重量的Pt硝酸盐和Pd硝酸盐的水溶液混合。该混合溶液在110°C下干燥整夜,并在500°C下煅烧2小时。
对于1.5% Pt-Pd/CeZrCuO2催化剂,CO转化的测得T50为124℃,这几乎等于对于CeZrCuO2催化剂本身实现的%CO转化率。对于1.5% Pt-Pd/CeZrCuO2催化剂,重质HC(C12H26和C8H10)转化的T50为220℃,并类似于1.5% Pt-Pd/Al催化剂(T50 = 219℃)。但是,1.5% Pt-Pd/CeZrCuO2催化剂对重质HC的氧化活性低于CeZrCuO2催化剂本身的该活性,这意味着Pt-Pd与CeZrCuO2的直接接触阻碍重质HC氧化。
对于1.5% Pt-Pd/CeZrCuO2催化剂,C3H6转化的T50为265℃,这比基准催化剂(T50 = 214℃)高得多,但类似于CeZrCuO2催化剂本身(T50 = 271℃)。也就是说,1.5% Pt-Pd/CeZrCuO2催化剂和CeZrCuO2催化剂的C3H6 氧化活性在低温下不接近地像标准1.5% Pt-Pd/Al催化剂那样高。因此,对于CeZrCuO2基催化剂材料,Pt-Pd浸渍不利于轻质HC氧化。
实施例3
为了将CeZrCuO2催化剂的低温CO和重质HC氧化活性与1.5% Pt-Pd/Al2O3催化剂的优异C3H6氧化活性结合,将CeZrCuO2颗粒适当地与3重量% Pt-Pd/Al2O3颗粒合并。通过取一半量的CeZrCuO2和3重量% Pt-Pd/Al2O3颗粒并用手简单将它们一起摇动,制造氧化催化剂的这种组合。使用3重量%而非1.5重量% Pt-Pd/Al2O3粉末,以制造具有与基准催化剂相等的Pt-Pd量的氧化催化剂。通过这种方法,Pt-Pd仅负载在氧化铝上并防止Pt-Pd与CeZrCuO2直接接触。
如图6、7和8中所示,对于该氧化催化剂组合,实现了CO、重质HC和C3H6氧化的活化温度的显著降低。对于这种氧化催化剂,CO、重质HC和C3H6的起燃温度分别为129、186和187℃,这比基准催化剂低67、33和34℃。实际上,通过将CeZrCuO2颗粒与3% Pt-Pd/Al2O3颗粒合并,极大改进C3H6氧化活性。3% Pt-Pd/Al2O3 + CeZrCuO2氧化催化剂的重质HC转化率也略高于CeZrCuO2催化剂本身。由于CO和HC对于Pt-Pd催化剂相互竞争以被氧化,CO的存在通常阻碍对于Pt-Pd基催化剂的HC氧化速率。但是,在这种布置中,CeZrCuO2催化剂能实现CO的低温氧化,这减轻其抑制作用,并使Pt-Pd/Al2O3催化剂能在低温下更容易氧化HC。
为易于比较,对于这些催化剂的CO、重质HC和C3H6的起燃温度(T50 ℃)列在下表中:
CO | 重质HC | C3H6 | |
1.5% Pt-Pd/Al2O3 | 196 | 219 | 214 |
仅CeZrCuO2 | 124 | 190 | 271 |
1.5% Pt-Pd/CeZrCuO2 | 124 | 220 | 265 |
3% Pt-Pd/Al2O3 + CeZrCuO2 | 129 | 186 | 187 |
实施例4
为了考虑制成的催化剂在本研究中的现实应用,所有催化剂在烘箱中在750℃下在含10% H2O的流动空气中老化72小时。在水热老化后,再用与新鲜催化剂的情况中相同的活性试验规程检查氧化催化剂活性。
在基准催化剂的情况下,催化剂老化略微提高CO氧化活性,而无论是否催化剂老化,仍观察到烃氧化活性。在水热老化后,该组合的氧化催化剂—3% Pt-Pd/Al2O3 + CeZrCuO2,看起来与新鲜催化剂相比损失其CO和HC氧化活性。具体而言,对于该组合的氧化催化剂,在低于200℃的温度下的CO和HC氧化活性略低于基准催化剂。但高于200℃,对于该组合氧化催化剂的CO和HC氧化活性高于基准催化剂。因此,这种组合的氧化催化剂甚至在催化剂老化后仍被视为低温下的CO和HC氧化的有希望的候选物。
实施例5
为了降低该组合的氧化催化剂的成本,通过将CeZrCuO2与1.5% Pt-Pd/Al2O3(而非之前使用的3% Pt-Pd/Al2O3)合并,制备含有较低量Pt-Pd的催化剂。这种组合的氧化催化剂含有的Pt-Pd为基准催化剂的Pt-Pd的一半量。为了与1.5% Pt-Pd/Al2O3 + CeZrCuO2催化剂比较,合并等量的1.5% Pt-Pd/Al2O3和γ-氧化铝(Al)。基于催化剂的相同体积和重量,1.5% Pt-Pd/Al2O3 + Al催化剂含有与基准催化剂相比一半量的Pt-Pd。尽管该组合的氧化催化剂的密度不同于基准催化剂,该组合的氧化催化剂的比体积中Pt-Pd的量相当于0.75重量% Pt-Pd/Al2O3。
如图6、7和8中所示,对于1.5% Pt-Pd/Al2O3 + CeZrCu催化剂,CO和重质HC氧化活性好于基准催化剂。对于1.5% Pt-Pd/Al2O3+CeZrCu催化剂,C3H6转化率与基准催化剂相当。因此,1.5% Pt-Pd/Al2O3 + CeZrCu催化剂有潜力替代基准催化剂。
已经陈述本发明的优选实施方案和实践以便举例说明,不应被解释为限制本公开的实施方案的范围。
Claims (10)
1.氧化内燃机废气流中的一氧化碳(CO)和烃(HC)的方法;所述方法包括:
运行内燃机以燃烧空气和燃料的混合物,其中所述混合物中的燃料含量相对于化学计量的空气-燃料质量比为稀,所述发动机产生温度通常低于300℃的废气流;
输送所述废气流与氧化催化剂接触足以将基本所有CO氧化成二氧化碳(CO2)和将至少一部分HC氧化成CO2和水的时间;所述氧化催化剂作为洗涂层分散在流通式承载体的通道壁上,所述洗涂层包含(i)基本由铈、锆和铜的共沉淀混合氧化物(CeZrCuO2)颗粒构成的混合氧化物层和(ii)基本由分散在氧化铝颗粒上的至少一种铂族金属颗粒(PGM/Al2O3)构成的分别的PGM层,所述洗涂层的层经布置以使在所述废气流接触PGM/Al2O3的颗粒之前氧化在废气流中存在的一部分CO。
2.如权利要求1中所述的氧化方法,其中所述发动机废气流通常低于200℃。
3.如权利要求1中所述的氧化方法,其中所述废气流包含各至少500 ppm的 CO和HC。
4.如权利要求1中所述的氧化方法,其中所述混合氧化物层包含基本由铈(Ce)、锆(Zr)和铜(Cu)的元素构成的金属组分,且所述金属组分包含,按摩尔计,大约30至70%的 Ce、大约30至70%的 Zr和余量Cu。
5.如权利要求1中所述的氧化方法,其中所述混合氧化物层包含基本由铈(Ce)、锆(Zr)和铜(Cu)的元素构成的金属组分,且所述金属组分包含,按摩尔计,大约60% 的Ce、大约15% 的Zr和大约25%的 Cu。
6.如权利要求1中所述的氧化方法,其中PGM层从所述承载体的入口面到出口面分散在通道壁上,此后所述混合氧化物层分散在通道壁上以使所述混合氧化物层在流通式承载体的通道壁上覆盖PGM层。
7.如权利要求1中所述的氧化方法,其中所述混合氧化物层分散在所述流通式承载体入口面附近的通道壁的第一部分上,所述PGM层分散在流通式承载体出口面附近的通道壁的第二部分上。
8.如权利要求1中所述的氧化方法,其中所述至少一种铂族金属由钌、铂、钯、铑、锇和铱中的至少一种构成。
9.如权利要求1中所述的氧化方法,其中铈、锆和铜的共沉淀混合氧化物颗粒具有单相结晶结构。
10.如权利要求1中所述的氧化方法,其中所述承载体是挤出堇青石材料并具有均匀圆柱形横截面,所述承载体具有与废气流的流向横切的入口面和出口面,包含至少400个通道/平方英寸入口面横截面积,并经尺寸化以促进流经所述承载体的废气流中的CO和HC的氧化。
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US13/111,143 US8479493B2 (en) | 2011-05-19 | 2011-05-19 | Oxidation catalysts for engines producing low temperature exhaust streams |
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CN102787888B (zh) | 2015-05-27 |
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