CN113543880A - 催化剂层形成材料及催化剂装置构成材料及催化剂装置以及它们的制造方法 - Google Patents

催化剂层形成材料及催化剂装置构成材料及催化剂装置以及它们的制造方法 Download PDF

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CN113543880A
CN113543880A CN202080002866.XA CN202080002866A CN113543880A CN 113543880 A CN113543880 A CN 113543880A CN 202080002866 A CN202080002866 A CN 202080002866A CN 113543880 A CN113543880 A CN 113543880A
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catalyst
catalyst layer
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CN113543880B (zh
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西原和宏
霍鹏
内山昌一
铃木洋未
山下美穗
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Sakura Kogyo Co ltd
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Abstract

本发明的技术课题在于开发一种各个催化剂金属粒子与排出气体的接触率极为良好的新颖燃烧气体净化用催化剂构成材料及使用其的催化剂装置及其制造方法。本发明的特征是对含有陶瓷微粒子的浆料的催化剂负载材料(2)，混入催化剂金属粒子(3)和高温消失的多孔形成材(5)而成；所述多孔形成材(5)包含纤维素纳米纤维的长纤维(5L)和/或纤维素纳米纤维的短纤维(5S)。

Description

催化剂层形成材料及催化剂装置构成材料及催化剂装置以及 它们的制造方法
技术领域
本发明是涉及一种供净化二轮摩托车、汽车等的排出气体等使用的催化剂装置及其构成材料。
背景技术
用于处理二轮摩托车、汽车等的排出气体等的催化剂装置，为了极大化与排出气体的接触，将对蜂巢结构的载体负载有催化剂金属粒子的催化剂组件作为主要的构成要素。
在得到这种催化剂组件时，会采用将催化剂载体连同催化剂金属粒子涂布在由不锈钢或陶瓷材料所形成的蜂巢柱体的手法(例如参照专利文献1)。
然而，由于所使用的所述催化剂金属为铂、铑、钯等的贵金属，因此使它们有效率地接触排出气体，以减少这些催化剂金属的使用量成为课题。
作为可如此减少催化剂金属的使用量的一尝试例，可列举一种手法，其是对以陶瓷粉末和纸浆为主成分的材料进行抄纸，并形成多孔质的纸质片材，将该纸质片材成形为波纹状，并通过卷起形成蜂巢柱体后，以陶瓷原料与催化剂金属粒子涂布蜂巢柱体(例如参照非专利文献1)。
然而，该手法需要原料的打浆、抄纸、干燥步骤，因此导致制造成本上升。
现有技术文献
专利文献
专利文献1：日本特开2005－87826公报
非专利文献
非专利文献1：科学技术振兴机构报(“科学技術振興機構報”)第775号
发明内容
发明所要解决的问题
本发明提供一种手法从根本改善这种传统手法，技术课题在于开发一种各个催化剂金属粒子与排出气体等的接触率极为良好的新颖催化剂层形成材料及催化剂装置构成材料及催化剂装置以及它们的制造方法。
用于解决问题的方案
即，方案1的催化剂层形成材料，其特征在于，对含有陶瓷微粒子的浆料的催化剂负载材料，混入催化剂金属粒子和高温消失的多孔形成材而成；所述多孔形成材包含纤维素纳米纤维的长纤维和/或纤维素纳米纤维的短纤维。
此外，方案2的催化剂装置构成材料，其特征在于，在基材的表面或形成于基材的表面的催化剂金属粒子含有层的表面，涂布方案1所述的催化剂层形成材料并形成催化剂层；通过烧成催化剂层形成材料，使多孔形成材消失并形成多孔。
此外，方案3的催化剂装置构成材料，其特征在于，除了方案2所述的要件外，所述催化剂层是多层形成。
此外，方案4的催化剂装置构成材料，其特征在于，除了方案2或3所述的要件外，所述基材是金属箔；所述基材形成波纹状，且重叠卷绕成筒状并形成蜂巢断面。
此外，方案5的催化剂装置构成材料，其特征在于，除了方案2或3所述的要件外，所述基材是由陶瓷所形成的蜂巢结构体。
此外，方案6的催化剂装置，其特征在于，在套管(casing)内收容方案4或5所述的催化剂装置构成材料。
此外，方案7的催化剂层形成材料的制造方法，其特征在于，对含有陶瓷微粒子的浆料的催化剂负载材料，混入催化剂金属粒子，以及作为高温消失的多孔形成材的纤维素纳米纤维的长纤维和/或纤维素纳米纤维的短纤维。
此外，方案8的催化剂装置构成材料的制造方法，其特征在于，将方案7所述的催化剂层形成材料的制造方法所制造的催化剂层形成材料涂布于基材表面，并烧成催化剂层形成材料，从而使多孔形成材消失并形成多孔。
此外，方案9的催化剂装置构成材料的制造方法，其特征在于，除了方案8所述的要件外，所述催化剂层为多层形成。
此外，方案10的催化剂装置构成材料的制造方法，其特征在于，除了方案8或9所述的要件外，所述基材形成波纹状，且重叠卷绕成筒状并形成蜂巢断面。
此外，方案11的催化剂装置构成材料的制造方法，其特征在于，除了方案8或9所述的要件外，使所述基材为由陶瓷所形成的蜂巢结构体。
此外，方案12的催化剂装置的制造方法，其特征在于，将方案9所述的催化剂装置构成材料的制造方法所制造的催化剂装置构成材料收容于套管。
并且，以这些各方案所述的发明为手段，试图解决所述课题。
发明效果
首先，根据方案1所述的发明，由于纤维素纳米纤维的长纤维和纤维素纳米纤维的短纤维均匀地分散于浆料中，因此可使烧成催化剂层形成材料后形成于催化剂层中的多孔均等地分布，并且形成多孔网络。
此外，根据方案2所述的发明，可容易地形成在催化剂层中多孔均等地分布，且各个多孔连接形成多孔网络的催化剂装置的构成要素。
此外，可形成多孔网络，该多孔网络通过纤维素纳米纤维的短纤维消失所形成的短尺寸多孔连接纤维素纳米纤维的长纤维消失所形成的长尺寸多孔。
此外，根据方案3所述的发明，多层形成的各个催化剂层内所形成的多孔网络可为互相连接者。
此外，各层所内含的金属催化剂粒子的种类可不同。
此外，根据方案4或5所述的发明，可形成蜂巢结构体，该蜂巢结构体是排出气体等可通过多孔网络抵达催化剂层内均等分布的各个催化剂金属粒子者。
此外，根据方案6所述的发明，可降低蜂巢结构形成的成本等，而不导致各个催化剂金属粒子与排出气体的接触率降低，得到耐久性更优良的催化剂装置。
此外，根据方案7所述的发明，由于纤维素纳米纤维的长纤维和纤维素纳米纤维的短纤维均匀地分散于浆料中，因此可使烧成催化剂层形成材料后形成在催化剂层中的多孔均等地分布，并且形成多孔网络。
此外，根据方案8所述的发明，可容易地形成在催化剂层中多孔均等地分布的催化剂装置的构成要素。
此外，可形成多孔网络，该多孔网络通过纤维素纳米纤维的短纤维消失所形成的短尺寸多孔连接纤维素纳米纤维的长纤维消失所形成的长尺寸多孔。
此外，根据方案9所述的发明，多层形成的各个催化剂层内所形成的多孔网络可为互相连接者。
此外，各层所内含的金属催化剂粒子的种类可不同。
此外，根据方案10或11所述的发明，可形成蜂巢结构体，该蜂巢结构体是可通过多孔网络抵达均等分布的各个催化剂金属粒子者。
此外，根据方案12所述的发明，可降低蜂巢结构形成的成本等，而不导致各个催化剂金属粒子与排出气体的接触率降低，得到耐久性更优良的催化剂装置。
附图说明
图1是表示本发明的催化剂装置构成材料及催化剂装置的立体图以及催化剂装置构成材料的部分放大图。
图2是表示本发明的催化剂层形成材料的制造步骤的立体图。
图3是表示本发明的催化剂装置构成材料的制造步骤的侧视图。
图4是放大表示本发明的催化剂装置构成材料的断面图。
图5是表示本发明的催化剂装置的净化性能试验结果的图表。
具体实施方式
本发明的“催化剂层形成材料及催化剂装置构成材料及催化剂装置以及它们的制造方法”的最佳方式如下所示，但亦可在本发明的技术思想范围内对此方式追加适当的变更。
[实施例]
首先，本发明的催化剂层形成材料1是用以形成供净化二轮摩托车、汽车等的排出气体等使用的催化剂装置100的构成要素的催化剂装置构成材料10；是含有催化剂金属粒子3的浆料状物质；是对催化剂负载材料2，混入催化剂金属粒子3和高温消失的多孔形成材5所成者。
所述催化剂负载材料2是含有陶瓷微粒子的浆料。需要说明的是，亦可在该浆料混合金属氧化物的前驱体等。
所述陶瓷微粒子采用将Al2O3(氧化铝)、SiO2(二氧化硅)等粉碎成指定粒径者。
此外，所述金属氧化物的前驱体采用氧化铝溶胶或二氧化硅溶胶等通过缩合反应形成陶瓷结构的材料。
此外，所述催化剂金属粒子3采用Pt(铂)、Rh(铑)、Pd(钯)、Ir(铱)、Os(锇)、Ru(钌)等的贵金属，与Al(铝)、Ce(铈)、Zr(锆)等的卑金属的任一种或多种。
此外，所述多孔形成材5采用纤维素纳米纤维(以下称为CNF：CelluloseNanofibers)的长纤维5L和/或CNF的短纤维5S。
所述长纤维5L及短纤维5S是通过机械解纤或化学解纤得到者。
所述长纤维5L较佳为通过机械解纤得到的极细纤维；另一方面，所述短纤维5S较佳为通过化学解纤得到者。
所述短纤维5S更佳为通过TEMPO(四甲基哌啶氧化物)氧化处理解纤得到者。
以下，说明本发明的催化剂层形成材料1及使用该催化剂层形成材料1构成的催化剂装置构成材料10及使用该催化剂装置构成材料10构成的催化剂装置100的制造方法。
〔催化剂层形成材料的调制〕
调制所述催化剂层形成材料1时，如图2所示，作为一例，将以期望的比例混合催化剂负载材料2、催化剂金属粒子3及多孔形成材5(长纤维5L、短纤维5S)的浆料，连同氧化锆球Z投入罐P，并使用具有使该罐P自转并公转的旋转台T的行星式球磨机M来均匀混合。
通过使用这种行星式球磨机M，除了氧化锆球Z与罐P内壁的撞击外，以相反方向进行自转、公转从而可施加强烈的离心力，进而可在短时间内进行亚微米等级的混合、搅拌处理。
〔催化剂装置构成材料的形成〕
接着，将如上述所调制的催化剂层形成材料1涂布于基材11的表面并形成催化剂层12，以下说明其顺序。需要说明的是，基材11较佳为使用具有一定程度的柔软性、保形性及耐热性的不锈钢、铝等的金属箔，但亦可使用具有它们特性的其他材料。
(1)蜂巢结构体的形成
首先，通过波纹辊(省略图示)将波纹基材11a形成波纹状并赋予凹凸。接着，重叠赋予凹凸的波纹基材11a和平坦的衬垫基材11b并卷成筒状，在形成期望的直径时裁断，而得到形成蜂巢断面的圆柱状的蜂巢结构体13。
(2)催化剂层的形成
接着如图3的(a)所示，将蜂巢结构体13浸渍于投入液槽V中的催化剂层形成材料1，而在蜂巢内壁面涂布催化剂层形成材料1，取出后，适当除去多余的催化剂层形成材料1，并依常规方法将此干燥，从而对内壁面形成催化剂层12。
接着通过重复如此的浸渍及干燥，可积层催化剂层12，形成期望的厚度；此时，通过切换成所含有的催化剂金属粒子3等不同的催化剂层形成材料1，可积层特性不同的催化剂层12而形成。
需要说明的是，此实施例如图4的(a)所示，仅有对基材11形成的下层催化剂层12L形成多孔15，而上层催化剂层12U不形成多孔15。即，用于形成下层催化剂层12L的催化剂层形成材料1含有催化剂负载材料2、催化剂金属粒子3及多孔形成材5，同时，用于形成上层催化剂层12U的催化剂层形成材料1仅含有催化剂负载材料2及催化剂金属粒子3，而不含多孔形成材5。
此外，催化剂层12是如图1所示形成于基材11的两面，图4为省略表示基材11的一面(下面)的催化剂层12。进一步地，为了便于说明，图1、图4中是以与实际的尺寸比不同的比例绘制催化剂金属粒子3、长尺寸多孔15L及短尺寸多孔15S以及基材11、上层催化剂层12U及下层催化剂层12L。
需要说明的是，蜂巢结构体13由于如后所述会组装于套管101中，因此在不希望在与套管101的接触面的蜂巢结构体13的侧周面附着催化剂层形成材料1的情况下，可采用以下手法。
具体如图3的(b)所示，使用与蜂巢结构体13的外径略为相同尺寸的内径所成的筒状支架H，在形成于该支架H的下部内侧的凸缘部F上使蜂巢结构体13为载置状态。另一方面，支架H的上部扩展成漏斗状，从此处通过给液管S供给催化剂层形成材料1至支架H内，而在蜂巢结构体13的蜂巢内壁面涂布催化剂层形成材料1。
需要说明的是，从支架H的下部排出的催化剂层形成材料1可适当回收再利用。
(3)烧成
接着，作为一例，通过以500℃加热1小时烧成蜂巢结构体13，使位于催化剂层12内的作为多孔形成材5的长纤维5L、短纤维5S消失，从而在催化剂层12(此实施例中为下层催化剂层12L)形成多孔15(长尺寸多孔15L、短尺寸多孔15S)。
如此得到的催化剂装置构成材料10，如图4的(a)中放大所示，通过长尺寸多孔15L之间接触，或者通过短尺寸多孔15S连接邻接的长尺寸多孔15L，从而形成犹如多孔15连接成网目状般的多孔网络15N。
〔催化剂装置的形成〕
接着，通过将如上述所得到的催化剂装置构成材料10如图1所示设置于金属制等的圆筒状的套管101内，从而构成催化剂装置100。
〔评价试验〕
以下表示将如上述所得到的本发明的催化剂装置100(样品2)安装于小型二轮摩托车B进行评价试验的结果(对CO、THC(total hydrocarbons：碳氢化合物总量)、NOx的净化性能(EU3(欧洲排放标准)：Fresh(新鲜)、Aging(老化)))。
需要说明的是，作为比较对象的样品1为下层催化剂层12L及上层催化剂层12U皆含有催化剂负载材料2及催化剂金属粒子3，但未形成多孔15。
结果如图5所示，已确认对所有的排出气体成分，样品2的净化性能比样品1高。
〔其他实施例〕
本发明将上述实施例作为基本实施例，但亦可基于本发明的技术思想采用如下所示的实施例。
首先，上述的基本实施例中，使催化剂装置构成材料10为圆筒状，但可根据其所组装的催化剂装置100的形态等而采用适当的形状。
例如在将催化剂装置构成材料10用于二次电池的电极的情况下，形成为平板状。
此外，上述的基本实施例中，蜂巢结构体13以不锈钢为材料形成，但亦可通过陶瓷等其他材料形成，作为一例，如图1中所并记，可采用通过挤出成型陶瓷材料形成蜂巢结构后，通过烧成得到的蜂巢结构体13。
此外，上述的基本实施例中，如图4的(a)所示，仅有对基材11形成的下层催化剂层12L形成多孔15，而上层催化剂层12U为不形成多孔15的催化剂金属粒子含有层，但亦可如图4的(b)所示，使下层催化剂层12L及上层催化剂层12U两者形成多孔15，或者亦可如图4的(c)所示，仅上层催化剂层12U形成多孔15，而下层催化剂层12L为不形成多孔15的催化剂金属粒子含有层。
需要说明的是，在所述图4的(b)所示的构成的情况下，个别的层内所形成的多孔网络15N之间，互相连通并连接。
此外，在所述图4的(b)、(c)所示的构成的情况下，最上部的催化剂层12的上层催化剂层12U的表层部中，由于多孔15为露出状态，因此外部气体(排出气体)被导入多孔网络15N的所有区域，可促进外部气体(排出气体)与位于催化剂层12的几乎所有的催化剂金属粒子3的接触。
附图标记说明：
1……催化剂层形成材料；
2……催化剂负载材料(浆料)；
3……催化剂金属粒子；
5……多孔形成材；
5S……短纤维；
5L……长纤维；
10……催化剂装置构成材料；
11……基材；
11a……波纹基材；
11b……衬垫基材；
12……催化剂层；
12L……下层催化剂层；
12U……上层催化剂层；
13……蜂巢结构体；
15……多孔；
15S……短尺寸多孔；
15L……长尺寸多孔；
15N……多孔网络；
100……催化剂装置；
101……套管；
B……小型二轮摩托车；
F……凸缘部；
H……支架；
M……行星式球磨机；
P……罐；
S……给液管；
T……旋转台；
V……液槽；
Z……氧化锆球。

Claims (12)

1.一种催化剂层形成材料，其特征在于，对含有陶瓷微粒子的浆料的催化剂负载材料，混入催化剂金属粒子和高温消失的多孔形成材而成；
所述多孔形成材包含纤维素纳米纤维的长纤维和/或纤维素纳米纤维的短纤维。
2.一种催化剂装置构成材料，其特征在于，在基材的表面或形成于基材的表面的催化剂金属粒子含有层的表面，涂布权利要求1所述的催化剂层形成材料并形成催化剂层；通过烧成催化剂层形成材料，使多孔形成材消失并形成多孔。
3.根据权利要求2所述的催化剂装置构成材料，其中，所述催化剂层是多层形成。
4.根据权利要求2或3所述的催化剂装置构成材料，其中，所述基材是金属箔；所述基材形成波纹状，且重叠卷绕成筒状并形成蜂巢断面。
5.根据权利要求2或3所述的催化剂装置构成材料，其中，所述基材是由陶瓷所形成的蜂巢结构体。
6.一种催化剂装置，其特征在于，在套管内收容权利要求4或5所述的催化剂装置构成材料。
7.一种催化剂层形成材料的制造方法，其特征在于，对含有陶瓷微粒子的浆料的催化剂负载材料，混入催化剂金属粒子，以及作为高温消失的多孔形成材的纤维素纳米纤维的长纤维和/或纤维素纳米纤维的短纤维。
8.一种催化剂装置构成材料的制造方法，其特征在于，将权利要求7所述的催化剂层形成材料的制造方法所制造的催化剂层形成材料涂布于基材表面，并烧成催化剂层形成材料，使多孔形成材消失并形成多孔，从而形成催化剂层。
9.根据权利要求8所述的催化剂装置构成材料的制造方法，其中，所述催化剂层为多层形成。
10.根据权利要求8或9所述的催化剂装置构成材料的制造方法，其中，所述基材是金属箔；所述基材形成波纹状，且重叠卷绕成筒状并形成蜂巢断面。
11.根据权利要求8或9所述的催化剂装置构成材料的制造方法，其中，使所述基材为由陶瓷所形成的蜂巢结构体。
12.一种催化剂装置的制造方法，其特征在于，将权利要求10或11所述的催化剂装置构成材料的制造方法所制造的催化剂装置构成材料收容于套管。
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