CN101489670B - 排气净化用催化剂 - Google Patents
排气净化用催化剂 Download PDFInfo
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Abstract
本发明的课题是将催化剂中的贵金属担载密度最佳化。在涂层的排气上游侧,以每1升载体基材的担载量超过0.75g的量担载Pt,使排气下游侧的涂层中的Rh担载密度比排气上游侧高。通过在容易变为浓气氛的排气下游侧以高密度担载Rh,可使暖机后的净化性能提高。
Description
技术领域
本发明涉及能够从低温区到高温区高效率地净化来自内燃机等的排气中的有害成分的排气净化用催化剂。
背景技术
一直以来,作为汽车的排气净化用催化剂,使用在理论空燃比(理论配比)下同时地进行排气中的CO和HC的氧化和NOx的还原从而进行净化的三元催化剂。作为这样的三元催化剂,众所周知的是在例如由堇青石等制成的耐热性基材上,由γ-氧化铝等多孔质氧化物形成涂层,使该涂层上担载铂(Pt)、铑(Rh)等贵金属而成的三元催化剂。
该三元催化剂,在稀薄气氛下主要作为氧化催化剂发挥功能,在理论配比~浓气氛下作为还原催化剂发挥功能,可利用排气中的CO和HC来还原NOx进行净化。
然而,在三元催化剂中呈现催化作用的是所担载的贵金属,但贵金属呈现催化作用的温度区处于较高的温度区,因此存在在低温区难以净化有害成分的问题。为此,在冬季或起动时等的排气处于低温区的场合,存在净化活性低的不良情况。
于是,在排气流入的上游部以高密度担载贵金属。通过这样地在上游部以高密度担载贵金属,在上游部贵金属与排气相接触的几率提高,发生CO以及HC的氧化反应的几率提高。而且一旦发生氧化反应,其点火就传播,氧化反应进一步进行。另外,由于氧化反应是放热反应,因此也有三元催化剂被该反应热加热从而升温,迅速地升温到贵金属的活化温度区的作用。因此,如果在上游部以高密度担载贵金属,则由于这些协同效应,低温区的净化活性提高。
例如日本特开2004-181374号公报中记载了:在串联地配置了二个催化剂的串联式催化剂中,在上游侧的催化剂上担载比下游侧的催化剂多的贵金属。另外,日本特开2001-25265号公报中记载了在涂层的排气流入的上游部的表面上进一步形成了上层涂层的催化剂。根据该催化剂,能够通过上层涂层所担载的贵金属来提高上游部的贵金属的担载密度。
然而,若只单单提高贵金属的担载密度,则存在贵金属的绝对量增加,从而成本上升的问题。另外,如果提高上游侧的贵金属的担载密度,则低温区的对HC的净化性能提高。但是,即使提高上游侧的贵金属的担载密度,也对催化剂的温度上升到贵金属的活化温度区后(以下称为暖机后)的净化性能基本上没有影响,因此贵金属变得浪费。并且,还存在暖机后的对NOx的净化性能不充分的问题。
专利文献1:日本特开2004-181374号
专利文献2:日本特开2001-252565号
发明内容
本发明是鉴于上述状况而完成的,其课题是要解决将催化剂中的贵金属的担载密度最佳化的问题。
解决上述课题的本发明的排气净化用催化剂的特征在于,在包括载体基材、和在载体基材表面形成的涂层,涂层包含多孔质氧化物载体和担载在多孔质氧化物载体上的至少含有Pt和Rh的贵金属的排气净化用催化剂中,在涂层的排气上游侧,以每1升载体基材的担载量超过0.75g的量担载Pt,同时担载有Rh,涂层的排气下游侧的Rh担载密度比排气上游侧高。
排气上游侧的Rh担载量与排气下游侧的Rh担载量之比,优选为0.9以下,更优选为0.5以下。
另外,关于涂层中的Pt担载密度,优选排气上游侧比排气下游侧高。另外,排气上游侧的Pt担载量与排气下游侧的Pt担载量之比,优选为0.8以上,更优选为1.4以上。
发明效果
以下将排气上游侧称为“上游侧”,将排气下游侧称为“下游侧”。根据本发明的排气净化用催化剂,相比于上游侧,下游侧的Rh担载密度高。Rh对氧不足的浓气氛中的NOx的净化活性优异。并且,流入到催化剂中的排气,在上游侧HC和CO被氧化而消耗氧,因此在下游侧容易变为浓气氛。所以,通过在下游侧以高密度担载Rh,可使暖机后的净化NOx的性能提高。
另外,只要在下游侧以高密度担载Rh即可,上游侧的Rh担载密度可以低。因此,Rh担载量可以与以往同等,不会增大成本。
此外,如果在上游侧以高密度担载Pt,则低温区的对HC和CO的净化性能提高。另外,即使在下游侧以低密度担载Pt,对暖机后的净化活性也基本上没有影响。因此Pt担载量也可以与以往同等。成本的增大得到抑制。
附图说明
图1是本发明的一实施例的催化剂的模式剖面图。
图2是表示对于在上游侧65mm和下游侧65mm分开涂布了涂层的催化剂,最高净化率相对于下游侧的Rh担载量和上游侧的Pt担载量的曲线图。
图3是表示对于在上游侧65mm和下游侧65mm分开涂布了涂层的催化剂,HC50%到达时间相对于下游侧的Rh担载量和上游侧的Pt担载量的曲线图。
图4是表示对于在上游侧30mm和下游侧100mm分开涂布了涂层的催化剂,最高净化率相对于下游侧的Rh担载量和上游侧的Pt担载量的曲线图。
图5是表示对于在上游侧30mm和下游侧100mm分开涂布了涂层的催化剂,HC50%到达时间相对于下游侧的Rh担载量和上游侧的Pt担载量的曲线图。
附图标记说明
2-蜂窝基材、2-上游侧涂层、3-下游侧涂层。
具体实施方式
本发明的排气净化用催化剂,包括载体基材和在载体基材的表面形成的涂层。作为载体基材,可举出一般的蜂窝形状或泡沫形状的基材,可以使用由堇青石等耐热性陶瓷或金属箔形成的基材。
涂层由多孔质氧化物载体和在多孔质氧化物载体上担载的至少含有Pt和Rh的贵金属构成。作为多孔质氧化物,可以使用氧化铝、氧化锆、二氧化硅、二氧化钛、二氧化铈、二氧化铈-氧化锆等用于现有的排气净化用催化剂中的多孔质氧化物。
涂层,优选每1升载体基材上形成100~300g。涂层的形成量少于该范围时,贵金属的担载密度变得过高,使用时有时发生粒生长。另外,若减少贵金属的担载量,则净化率降低。另外,涂层的形成量多于该范围时,热容量增加,暖机特性恶化,低温区的净化性能降低。另外,还有时由于使用时的振动等而发生剥离等不良情况。
该涂层,可通过由多孔质氧化物载体的粉末和氧化铝溶胶等粘合剂以及水等溶剂形成浆液,将该浆液洗涂于载体基材上后进行烧成,在其上面担载贵金属而形成。或者,也可以将在多孔质氧化物载体的粉末上预先担载了贵金属的催化剂粉末浆液化,然后将该浆液洗涂。
本发明的最大特征在于贵金属的担载分布,本发明中,在涂层的上游侧以每1升载体基材的担载量超过0.75g的量担载Pt,同时担载有Rh,使下游侧的涂层中的Rh担载密度比上游侧高。
在此,所谓上游侧,是指:从排气入口侧端面朝向出口侧端面的长度的范围相对于载体基材的全长为1/8~1/2的范围。因此,所谓下游侧,为从排气出口侧端面朝向入口侧端面的长度的范围相对于载体基材的全长为1/2~7/8的范围。上游侧的范围相对于全长不到1/8时、或者下游侧的范围 相对于全长超过7/8时,低温区的净化性能会不足。另外,上游侧的范围相对于全长超过1/2时、或下游侧的范围相对于全长不到1/2时,暖机后的净化性能不足。
再者,本发明的排气净化用催化剂,可以形成为串联地配置了二个催化剂的串联式结构,也可以形成为在一个载体基材的上游侧和下游侧分别形成了各涂层的区段涂层结构。
在本发明的排气净化用催化剂中,关于涂层中的Rh担载密度,下游侧比上游侧高。由此,暖机后的净化性能大幅度地提高,特别是净化NOx的性能提高。在此,所谓Rh担载密度,是指所担载的Rh质量与存在于该区域中的多孔质氧化物载体的质量之比。下游侧的Rh担载密度优选为0.001~0.004的范围。当其担载密度超过0.004时,有时使用时粒生长而使活性降低。
作为上游侧与下游侧的Rh担载密度相差的程度,可以将担载量之比作为指标。即,优选上游侧的Rh担载量与下游侧的Rh担载量之比为0.9以下。当该比超过0.9时,上游侧与下游侧的担载量之差过小,以高密度担载于下游侧的意义丧失,暖机后的净化性能不足。该比更优选为0.5以下。
一般的三元催化剂的情况下的Rh担载量,每1升载体基材为0.1~0.5g,若换算成担载密度,则为0.001~0.004。Rh担载量比该范围少时,净化NOx性能不充分,即使比该范围多地担载,活性也饱和,同时费用增高。因此,在本发明的排气净化用催化剂中,也优选使上游侧与下游侧的合计Rh量为该范围。
例如,在催化剂整体中为0.4g/L的担载量的场合,在下游侧的一半上担载了0.6g/L的场合,在上游侧的一半上担载0.2g/L。在该情况下,上游侧Rh担载量与下游侧的Rh担载量之比为0.33。另外,如果每1升载体基材上的涂层形成量为例如250g,则下游侧的Rh担载密度为0.0024,上游侧的Rh担载密度为0.0008。
因此,上游侧的Rh担载量与下游侧的Rh担载量之比为0.9以下这一范围,例如在整体中为0.4g/L的担载量的场合,与下游侧的Rh担载量为0.42g以上、且上游侧的Rh担载量为0.38g/L以下这一范围同义。
在本发明的排气净化用催化剂中,除了Rh以外,还以Pt为必需成分,在上游侧以每1升载体基材的担载量超过0.75g的量担载了Pt。上游侧的Pt担载量为0.75g/L以下时,低温区的净化HC性能变得不充分。再者,Pt担载量,优选在催化剂整体中为0.5~3g/L的范围。
关于Pt担载密度,优选使排气上游侧高于排气下游侧。通过这样地构成,低温区的净化性能提高。上游侧的Pt担载密度优选为0.003~0.03的范围。当其担载密度超过0.03时,有时使用时粒生长而使活性降低。
上游侧的Pt担载量与下游侧的Pt担载量之比优选为0.8以上。当该比小于0.8时,上游侧与下游侧的担载量之差过小,以高密度担载于上游侧的意义丧失,低温区的净化性能不足。该比更优选为1.4以上。再者,该比的上限没有特别限制,也可以为无限大。
再者,对于本发明的排气净化用催化剂,也可以在不损害性能的范围内在涂层上担载Pd等其他贵金属或过渡金属。
实施例
以下通过实施例和比较例具体地说明本发明。
(实施例1)
图1表示本实施例的排气净化用催化剂的模式剖面图。该排气净化用催化剂,包括堇青石制的蜂窝基材1(长度130mm)、在从蜂窝基材1的上游侧端面起65mm的范围形成的上游侧涂层2、和在从蜂窝基材的下游侧端面起65mm的范围形成的下游侧涂层3。在上游侧涂层2和下游侧涂层3上,分别以不同的担载密度担载有Pt和Ph。以下说明该排气净化用催化剂的制造方法来代替构成的详细说明。
使用规定浓度的二硝基二胺铂溶液,吸附担载于CeO2-ZrO2固溶体粉末(按重量比计,CeO2∶ZrO2=60∶40)上,在120℃下干燥,在500℃下烧成2小时,调制出担载了1.6重量%的Pt的Pt/CeO2-ZrO2粉末(A)。
使用规定浓度的二硝基二胺铂溶液,吸附担载于CeO2-ZrO2固溶体粉末(按重量比计,CeO2∶ZrO2=60∶40)上,在120℃下干燥,在500℃下烧成2小时,调制出担载了0.4重量%的Pt的Pt/CeO2-ZrO2粉末(B)。
使用规定浓度的硝酸铑水溶液,吸附担载于CeO2-ZrO2固溶体粉末(按重量比计,CeO2∶ZrO2=25∶75)上。在120℃下干燥,在500℃下烧成2小时,调制出担载了0.2重量%的Rh的Rh/CeO2-ZrO2粉末(A)。
使用规定浓度的硝酸铑水溶液,吸附担载于CeO2-ZrO2固溶体粉末(按重量比计,CeO2∶ZrO2=25∶75)上。在120℃下干燥,在500℃下烧成2小时,调制出担载了0.8重量%的Rh的Rh/CeO2-ZrO2粉末(B)。
将Pt/CeO2-ZrO2粉末(A)80质量份、Rh/CeO2-ZrO2粉末(A)80质量份、Al2O3粉末20质量份、和氧化铝粘合剂20质量份与适量的水混合,调制浆液,并洗涂到从堇青石制的蜂窝基材1(小室密度600cpsi、壁厚75μm、直径103mm、全长130mm)的排气上游侧端面起65mm的位置。
另一方面,将Pt/CeO2-ZrO2粉末(B)150质量份、Rh/CeO2-ZrO2粉末(B)80质量份、Al2O3粉末20质量份、和氧化铝粘合剂20质量份与适量的水混合,调制浆液,并洗涂到其余的65mm,即从排气下游侧端面起65mm的位置。
将其干燥后,在500℃下烧成2小时,形成上游侧涂层2和下游侧涂层3,制备出实施例1的排气净化用催化剂。在该排气净化用催化剂中,形成有250g/L的上游侧涂层2,形成有250g/L的下游侧涂层3。另外,如表1所示,上游侧涂层2中的担载量是:Pt为2.4g/L、Rh为0.16g/L,下游侧涂层3中的担载量是:Pt为0.6g/L、Rh为0.64g/L。在催化剂整体中,分别担载有1.5g/L的Pt、0.4g/L的Rh。
因此,上游侧涂层2中的担载密度是:Pt为0.0096、Rh为0.00064,下游侧涂层3中的担载密度是:Pt为0.0024、Rh为0.00256。即,相比于上游侧,下游侧的Rh担载密度高,相比于下游测,上游侧的Pt担载密度高。另外,上游侧的Rh担载量与下游侧的Rh担载量之比为0.25,上游侧的Pt担载量与下游侧的Pt担载量之比为4。
(实施例2、参考例1~3、比较例1~10)
使用与实施例1同样的CeO2-ZrO2固溶体粉末,分别担载Pt或Rh,担载量不同,除此以外,调制出与实施例1同样的催化剂粉末。然后,在与实施例1同样的蜂窝基材上同样地形成涂层,分别制备出如表1所示那样Pt和Rh的担载量以及担载分布不同的催化剂。任一例在催化剂整体中均分别担载有1.5g/L的Pt、0.4g/L的Rh。
(以往例)
使用与实施例1同样的CeO2-ZrO2固溶体粉末,分别担载Pt或Rh,担载量不同,除此以外,调制出与实施例1同样的催化剂粉末。然后,在与实施例1同样的蜂窝基材上同样地形成涂层,制备出如表1所示那样在整体上均匀地担载有1.5g/L的Pt,在整体上均匀地担载有0.4g/L的Rh的催化剂。
(参考例4、比较例11~18)
使用与实施例1同样的CeO2-ZrO2固溶体粉末,分别担载Pt或Rh,担载量不同,除此以外,调制出与实施例1同样的催化剂粉末。然后,在在从与实施例1同样的蜂窝基材的上游侧端面起30mm的范围形成上游侧涂层2,在其余的100mm的范围形成下游侧涂层,除此以外,与实施例1同样地形成涂层,分别制备出如表2所示那样Pt和Rh的担载量以及担载分布不同的催化剂。任一例在催化剂整体中分别担载有1.5g/L的Pt、0.4g/L的Rh。
<试验、评价>
将上述的催化剂分别装在搭载了V型8气缸4.3L发动机的发动机台架(Engine bench)的排气系统中,进行了在进气温度900℃、使A/F在15与14之间以1H2振动的条件下保持50小时的耐久试验。
将耐久试验后的催化剂分别装在搭载了串联4气缸2.4L发动机的发动机台架的排气系统中,以理论空燃比进行燃烧直到催化剂进气温度达到400℃,然后,一边采用热交换器将催化剂进气温度保持在400℃,一边从A/F=13.5到A/F=15以A/F=0.01/秒的速度扫描(Sweep)(ΔA/F=±0.5,0.5Hz)。连续地测定了此时的HC、NOx、CO的净化率,求出能够同时地净化该三种成分的最高净化率(COP),即与三种成分的净化率曲线交叉的点相当的净化率。
另外,以理论空燃比进行燃烧直到催化剂进气温度达到400℃后,通过旁通切换,将催化剂冷却到50℃,然后测定导入排气时直到HC净化率达到50%所需要的时间(HC50%到达时间)。
将这些结果示于图2~5。图2~5中也图示出依据等压线或等高线连接了同等的数值范围的曲线。
由图2可知,显示出比以往例高的最高净化率的是下游侧的Rh担载量大致为0.42/L以上的情况。该情况下的上游侧的Rh担载量与下游侧的Rh担载量之比为0.9,因此明确可知优选该比为0.9以下。另外,由图4也可知优选为该范围。
另一方面,通过比较例1与比较例2的比较、比较例3与比较例4的比较、或比较例7与比较例8的比较可知,上游侧的Pt担载密度比下游侧的Pt担载密度高时,净化50%的HC的到达时间较短。
另外,实施例1的催化剂,50%HC到达时间比以往例短,低温区的净化性能优异。另外,由图3可知,具有相比于以往例,50%HC到达时间较短的区领,该领域包括在上述的优选的范围内。但是,从图3来看,上游侧的Pt担载量优选为约1.3g/L~约2.7g/L的范围,特别优选为约2g/L~约2.7g/L的范围。这相当于上游侧的Pt担载量与下游侧的Pt担载量之比为约0.83~约2.37,优选为约1.48~约2.37。
另外,由图3还知道,下游侧的Rh担载量优选为约0.52g/L以上。可知该情况的上游侧的Rh担载量与下游侧的Rh担载量之比为约0.54,更优选上游侧的Rh担载量与下游侧的Rh担载量之比为0.54以下。
再者,由图5来看,难以明确区分优选的担载量。可以认为这是因为在30mm这一较短的上游侧范围以高密度担载了Pt的场合,耐久试验时Pt发生粒生长所导致的影响较大的缘故。
本发明中表示数值范围的“以上”和“以下”均包括本数。
Claims (6)
1.一种排气净化用催化剂,其包括载体基材和在该载体基材表面形成的涂层,该涂层包含多孔质氧化物载体和担载于该多孔质氧化物载体上的至少含有Pt和Rh的贵金属,
所述排气净化用催化剂的特征在于,
在该涂层的排气上游侧,以每1升该载体基材的担载量超过0.75g的量担载Pt,同时担载有Rh,
该涂层中,排气下游侧的Rh担载密度比排气上游侧高,
所述排气上游侧,是指从排气入口侧端面朝向出口侧端面的长度的范围相对于载体基材的全长为1/8~1/2的范围,所述排气下游侧,是指从排气出口侧端面朝向入口侧端面的长度的范围相对于载体基材的全长为1/2~7/8的范围。
2.根据权利要求1所述的排气净化用催化剂,其中,排气上游侧的Rh担载量与排气下游侧的Rh担载量之比为0.9以下。
3.根据权利要求2所述的排气净化用催化剂,其中,排气上游侧的Rh担载量与排气下游侧的Rh担载量之比为0.5以下。
4.根据权利要求1所述的排气净化用催化剂,其中,所述涂层中,排气上游侧的Pt担载密度比排气下游侧高。
5.根据权利要求4所述的排气净化用催化剂,其中,排气上游侧的Pt担载量与排气下游侧的Pt担载量之比为0.8以上。
6.根据权利要求5所述的排气净化用催化剂,其中,排气上游侧的Pt担载量与排气下游侧的Pt担载量之比为1.4以上。
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-
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- 2007-07-20 CN CN2007800269482A patent/CN101489670B/zh not_active Expired - Fee Related
- 2007-07-20 EP EP07791095.8A patent/EP2047903B1/en not_active Expired - Fee Related
- 2007-07-20 US US12/373,926 patent/US7846865B2/en not_active Expired - Fee Related
- 2007-07-20 WO PCT/JP2007/064358 patent/WO2008010576A1/ja active Search and Examination
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Also Published As
Publication number | Publication date |
---|---|
EP2047903B1 (en) | 2015-10-28 |
CN101489670A (zh) | 2009-07-22 |
KR20090025344A (ko) | 2009-03-10 |
JP4935219B2 (ja) | 2012-05-23 |
EP2047903A1 (en) | 2009-04-15 |
JP2008023451A (ja) | 2008-02-07 |
US20090197764A1 (en) | 2009-08-06 |
WO2008010576A1 (fr) | 2008-01-24 |
US7846865B2 (en) | 2010-12-07 |
EP2047903A4 (en) | 2010-12-15 |
KR101006220B1 (ko) | 2011-01-07 |
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