CN106029223B - 废气净化催化剂及其制造方法 - Google Patents

废气净化催化剂及其制造方法 Download PDF

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CN106029223B
CN106029223B CN201480075828.1A CN201480075828A CN106029223B CN 106029223 B CN106029223 B CN 106029223B CN 201480075828 A CN201480075828 A CN 201480075828A CN 106029223 B CN106029223 B CN 106029223B
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藤本美咲
花木保成
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Abstract

本发明提供一种废气净化催化剂，其含有氧化物1和氧化物2。该废气净化催化剂具有细孔P1－260，该细孔P1－260具有可以通过氮吸附法进行测定的1nm～260nm的细孔直径，该细孔的细孔容积PV1－260的总和ΣPV1－260为0.79cm3/g以上。氧化物1是具有氧气释放能力的氧化物。氧化物2由LaxM1－xM’O3－δ…(2)表示(式中的M是选自Ba、Sr及Ca中的至少一种元素，M'是选自Fe、Co、Ni及Mn中的至少一种元素，δ表示氧缺失量，x满足0≤x≤1，δ满足0≤δ≤1的关系)。

Description

废气净化催化剂及其制造方法
技术领域
本发明涉及废气净化催化剂及其制造方法，更详细地说，涉及具有适当的细孔容积，且气体扩散性优异的废气净化催化剂及其制造方法。
背景技术
目前，使LaMM’Ox(M表示Ba、Sr及Ca等，M’表示Fe、Co、Ni及Mn等)担载在储氧材料(OSC材料)上，使氧化还原功能得到了提高的废气净化催化剂是公知的(例如，参照专利文献1)。
现有技术文献
专利文献1:国际公开2012/133526号说明书
发明内容
发明要解决的技术问题
但是，本发明人进一步研究的结果发现，在如上所述的现有技术中，使OSC材料担载或含浸于上述La系氧化物时，由于La系氧化物所具有的影响气体扩散性的100nm左右的细孔破坏，在高的空间速度中，有时固有的催化剂功能变差。
本发明是鉴于该见解而开发的，其目的在于提供气体扩散性优异，能够发挥固有的催化剂功能的废气净化催化剂及其制造方法。
解决技术问题的技术方案
为了实现上述目的，本发明者反复进行了专心研究，结果发现，通过适当控制指定的细孔的细孔容积，可以实现上述目的，直至完成了本发明。
即，本发明的废气净化催化剂是含有氧化物1和氧化物2的废气净化催化剂，所述氧化物1是具有氧气释放能力的氧化物，所述氧化物2由下述的通式(2)表示，
LaxM1－xM’O3－δ…(2)
(式中的M是选自Ba、Sr及Ca中的至少一种元素，M’是选自Fe、Co、Ni及Mn中的至少一种元素，δ表示氧缺失量，x满足0≤x≤1，δ满足0≤δ≤1的关系)。
其特征在于，具有细孔P1－260，该细孔P1－260具有可以通过氮吸附法测定的1nm～260nm的细孔直径，
该细孔的细孔容积PV1－260的总和ΣPV1－260为0.79cm3/g以上。
另外，本发明的废气净化催化剂的制造方法，是制造如上所述的废气净化催化剂的方法。
其特征在于，对氧化物1进行烧成前，对氧化物2的前体与氧化物1进行混合，接着，对该混合物进行烧成。
发明的效果
根据本发明，由于对指定的细孔的细孔容积进行了适当控制，因此能够提供气体扩散性优异，可发挥固有的催化剂功能的废气净化催化剂及其制造方法。
附图说明
图1是示出各例的废气净化催化剂的HC功能保持率的标绘图；
图2是示出各例的废气净化催化剂的HC功能保持率的标绘图。
具体实施方式
以下，对本发明的废气净化催化剂进行说明。
(1)本发明的废气净化催化剂含有氧化物1和氧化物2。
在此，作为氧化物1只要是具有氧气储存释放功能的储氧材料(OSC材料)即可，没有特别限定，可以列举含有铈(Ce)和/或锆(Zr)的氧化物或复合氧化物。
另一方面，作为氧化物2而言，可以列举氧化物2含有选自镧(La)、钡(Ba)、锶(Sr)、钙(Ca)、铁(Fe)、钴(Co)、镍(Ni)及锰(Mn)中的至少一种元素的氧化物。
另外，具体而言，可以列举由下面的通式(2)表示的氧化物，且本发明中使用该氧化物。
LaxM1－xM’O3－δ…(2)
(式中的M是选自Ba、Sr及Ca中的至少一种元素，M’是选自Fe、Co、Ni及Mn中的至少一种元素，δ表示氧缺失量，x满足0≤x≤1，δ满足0≤δ≤1的关系)。
(2)本发明的废气净化催化剂具有细孔(P1－260)，所述细孔(P1－260)具有可以通过氮(N2)吸附法测定的1nm～260nm的细孔直径，该细孔的细孔容积(PV1－260)的总和(ΣPV1－260)为0.79cm3/g以上。
如上所述，本发明的废气净化催化剂由于细孔直径1nm～260nm的细孔容积为0.79cm3/g以上，因此在高的空间速度时(高SV时)也可以有效地保持催化剂功能。
(3)典型而言，本发明的废气净化催化剂是将氧化物2担载或含浸于氧化物1的粉末中而得到的。
该情况下，本发明的废气净化催化剂由于上述担载而产生的具有100～260nm的细孔直径的细孔的细孔容积总和的增加率(ΔΣPV100－260)满足ΔΣPV100－260≥1，该细孔容积总和的增加率(ΔΣPV100－260)由下述式(1)表示。
ΔΣPV100－260＝(担载后的废气净化催化剂的细孔容积的总和(σPV100－260))÷0.11…(1)
典型而言，就100～260nm的细孔容积总和的增加率(ΔΣPV100－260)而言，只要由氧化物1形成的催化剂层的指定细孔径范围的细孔容积(ΣPV100－260)、与氧化物2担载于氧化物1而形成的催化剂层的规定细孔径范围的细孔容积(σPV100－260)进行对比即可，若该增加率(ΔΣPV100－260)为1以上，高SV时的HC(碳化氢)氧化功能则提高。
即，通过提高在高SV时的催化剂层的气体扩散性，HC氧化功能的保持率得到提高。
另外，这意味着在氧化物2担载于氧化物1的情况下，可以不降低与氧化物1的细孔直径100～260nm的细孔对应的细孔容积而担载氧化物2。
另外，(1)式中的0.11是作为氧化物1能够获得的上述细孔直径范围的细孔容积的基准值所定义的值。
接着，对本发明的废气净化催化剂的制造方法进行说明。
(4)该制造方法是制造上述的本发明的废气净化催化剂的方法，在对氧化物1进行烧成前，对氧化物2的前体与氧化物1进行混合，接着，对该混合物进行烧成。
如上所述，在本发明的制造方法中，在对氧化物1进行烧成前添加氧化物2的成分，形成细孔。若形成(烧成)氧化物1之后再担载氧化物2，有时氧化物2会填满氧化物1的细孔，因此不理想。
作为氧化物2的前体，可以例示镧(La)和选自钡(Ba)、锶(Sr)、钙(Ca)、铁(Fe)、钴(Co)、镍(Ni)及锰(Mn)中的至少一种元素的羧酸盐。
它们的羧酸盐的溶液具有一定程度的粘性，易含浸于氧化物1。
另外，作为羧酸可以列举具有1～4个羧基的羧酸，例如，葡糖酸、苹果酸、马来酸、乙酸、琥珀酸、富马酸、丙酸、甲基丙烯酸、丙烯酸、柠檬酸、酒石酸、衣康酸、甲酸及丙二酸等。
实施例
以下，通过实施例及比较例更详细地说明本发明，但本发明不限定于这些实施例。
(实施例1～3)
制备表1所示的氧化物2的羧酸盐，将其与氧化物1的前体混合并进行干燥，将进一步在700℃下进行烧成，使得到的粉末浆料化，并涂布于整体型蜂窝状载体上进行干燥，在400℃下进行烧成，由此获得各例的废气净化催化剂。
(比较例1及2)
对于比较例1，将氧化物2的羧酸盐含浸于对表1所示的氧化物1的前体进行干燥并进一步在700℃下进行烧成而得到的粉末中，进行干燥，在700℃下进行烧成而获得粉末。通过使所得的粉末催化剂浆料化，涂布在整体型蜂窝状载体上，进行干燥，并在400℃下进行烧成，得到废气净化催化剂。
另外，对于比较例2，对表1所示的氧化物1的前体进行干燥，将进一步在700℃下烧成而得到的粉末催化剂浆料化，涂布在蜂窝载体上进行干燥，在400℃下进行烧制，由此获得废气净化催化剂。
将氧化物1和氧化物2的配合比、氧化物1、氧化物2的组成、蜂窝载体的形态、HC净化试验条件等集中示于表1。
＜功能评价＞
[总细孔容积]
是通过氮吸附法测定得到的1～260nm直径的细孔容积的总和。
对粉末进行加热、减压等，去除吸附气体，在已冷却的状态下，通过氮气导入、和氮气吸附于材料表面成为相对压力时的吸附量计算出总细孔容积。
[100－260nm直径的细孔容积的总和]
是上述测定得到的总细孔容积中，具有100nm～260nm以下的细孔直径的细孔容积的总和。
[100－260nm直径的细孔容积的总和的增加率]
是将100～260nm直径的细孔容积的基准值(实际上是氧化物1的平均值)定义为0.11，本发明制作的催化剂的100～260nm直径的细孔容积的总和(ΣPV100－260)除以0.11得到的值若为1以上，则表示ΣPV100－260增加的值。
[功能保持率]
按照下式计算。
功能保持率(％)＝[SV为30252h-1时的HC净化功能]÷[SV为20168h-1时的HC净化功能]×100
将表1所示的HC功能保持率，按总细孔容积、100－260nm直径细孔容积的增加率的不同图表化并示于图1及图2。
以上，通过若干实施方式及实施例说明了本发明，但本发明不限定于这些，在本发明的宗旨的范围内可以进行各种变形。

Claims (6)

1.一种废气净化催化剂，其含有氧化物1和氧化物2，
所述氧化物1是具有氧气释放能力的氧化物，
所述氧化物2由下述的通式(2)表示，
LaxM1－xM’O3－δ…(2)
式中的M是选自Ba、Sr及Ca中的至少一种元素，M’是选自Fe、Co、Ni及Mn中的至少一种元素，δ表示氧缺失量，x满足0<x≤1，δ满足0≤δ≤1的关系，并且，
所述废气净化催化剂具有细孔P1－260，该细孔P1－260具有可以通过氮吸附法测定的1nm～260nm的细孔直径，
该细孔的细孔容积PV1－260的总和ΣPV1－260为0.79cm3/g以上。
2.如权利要求1所述的废气净化催化剂，其中，
所述废气净化催化剂是在氧化物1上担载氧化物2而得到的，
由于所述担载而产生的具有100～260nm的细孔直径的细孔的细孔容积总和的增加率ΔΣPV100－260满足ΔΣPV100－260≥1，该细孔容积总和的增加率ΔΣPV100－260由下式(1)表示，
ΔΣPV100－260＝(担载后的废气净化催化剂的细孔容积的总和σPV100－260)÷0.11…(1)。
3.如权利要求1或2所述的废气净化催化剂，其中，
氧化物1含有铈(Ce)和/或锆(Zr)。
4.如权利要求1或2所述的废气净化催化剂，其中，
氧化物1是含有铈(Ce)和/或锆(Zr)的复合氧化物。
5.一种废气净化催化剂的制造方法，其包括：
在制造权利要求1～4中任一项所述的废气净化催化剂时，
在对氧化物1进行烧成前，将氧化物2的前体与氧化物1混合，接着，对该混合物进行烧成。
6.根据权利要求5所述的废气净化催化剂的制造方法，其中，
所述氧化物2的前体是镧(La)和选自钡(Ba)、锶(Sr)、钙(Ca)、铁(Fe)、钴(Co)、镍(Ni)及锰(Mn)中的至少一种元素的羧酸盐。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0525677A1 (en) * 1991-07-29 1993-02-03 Daihatsu Motor Company, Ltd. Exhaust gas purifying catalyst and method of preparing the same
CN101219380A (zh) * 2007-01-10 2008-07-16 日产自动车株式会社 废气净化催化剂及其制造方法
CN101484241A (zh) * 2006-07-03 2009-07-15 丰田自动车株式会社 废气净化催化剂
CN103402630A (zh) * 2011-03-31 2013-11-20 日产自动车株式会社 废气净化催化剂、废气净化整体式催化剂以及废气净化催化剂的制造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2663245B1 (fr) * 1990-06-13 1992-09-18 Rhone Poulenc Chimie Composition a base d'alumine pour catalyseur et procede de fabrication.
JP3260148B2 (ja) * 1991-07-29 2002-02-25 ダイハツ工業株式会社 排気ガス浄化用触媒
JPH1085611A (ja) * 1996-09-19 1998-04-07 Sumitomo Metal Mining Co Ltd ボリア−シリカ−アルミナ組成物よりなるハニカム構造担体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0525677A1 (en) * 1991-07-29 1993-02-03 Daihatsu Motor Company, Ltd. Exhaust gas purifying catalyst and method of preparing the same
CN101484241A (zh) * 2006-07-03 2009-07-15 丰田自动车株式会社 废气净化催化剂
CN101219380A (zh) * 2007-01-10 2008-07-16 日产自动车株式会社 废气净化催化剂及其制造方法
CN103402630A (zh) * 2011-03-31 2013-11-20 日产自动车株式会社 废气净化催化剂、废气净化整体式催化剂以及废气净化催化剂的制造方法

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