CN114054012A - 整体式基材、整体式基材的制造方法以及使用整体式基材的排气净化催化剂 - Google Patents

整体式基材、整体式基材的制造方法以及使用整体式基材的排气净化催化剂 Download PDF

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CN114054012A
CN114054012A CN202110799758.6A CN202110799758A CN114054012A CN 114054012 A CN114054012 A CN 114054012A CN 202110799758 A CN202110799758 A CN 202110799758A CN 114054012 A CN114054012 A CN 114054012A
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Prior art keywords
alumina
ceria
monolith substrate
composite oxide
zirconia composite
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CN202110799758.6A
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Inventor
垣花大
砂田智章
吉田健
今村豪
后藤真之助
植村公一
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Ibiden Co Ltd
Denso Corp
Toyota Motor Corp
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Ibiden Co Ltd
Denso Corp
Toyota Motor Corp
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Publication of CN114054012A publication Critical patent/CN114054012A/zh
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Abstract

本发明提供一种用于提高净化性能的排气净化催化剂用整体式基材、该整体式基材的制造方法以及使用该整体式基材的排气净化催化剂。本发明涉及包含氧化铝‑氧化铈‑氧化锆复合氧化物和氧化铝的整体式基材，整体式基材的制造方法以及使用该整体式基材的排气净化催化剂。

Description

整体式基材、整体式基材的制造方法以及使用整体式基材的 排气净化催化剂
技术领域
本发明涉及整体式基材、整体式基材的制造方法以及使用整体式基材的排气净化催化剂。
背景技术
从汽车等的内燃机排出的排气中，包含一氧化碳(CO)、氮氧化物(NOx)、未燃的烃(HC)等有害气体。将这种有害气体分解的排气净化催化剂也被称为三元催化剂，一般是在由堇青石等构成的蜂窝状整体式基材上采用洗涂形成包含具有催化活性的贵金属粒子的浆料而设置催化剂层。为了提高这种催化剂的性能，迄今为止进行了各种尝试。
例如，专利文献1记载了一种在载体表面直接担载催化剂成分而得到的催化剂体，其特征在于，对所述载体内的元素和细孔中的至少一者直接担载所述催化剂成分，并且采用密度泛函数法的模拟中的所述载体内的元素或孔隙与所述催化剂成分的担载强度大于5eV。
专利文献2记载了一种流通式的排气净化用催化剂，是在蜂窝基材上担载催化剂载体和催化剂成分而得到的排气净化用催化剂，其特征在于，所述催化剂载体和所述催化剂成分各自的至少90重量％配置在所述蜂窝基材的单元壁的气孔内。
专利文献3记载了一种在陶瓷载体上担载主催化剂成分及助催化剂成分而得到的陶瓷催化剂体，该陶瓷载体能够在基材陶瓷表面直接担载催化剂成分，所述陶瓷催化剂体的特征在于，所述基材陶瓷是具有多个气孔的结构，在包含这些气孔的内表面的所述基材陶瓷表面，直接担载有所述主催化剂成分和所述助催化剂成分。
专利文献4记载了一种排气净化催化剂，其包含氧化铈-氧化锆复合氧化物粒子和θ相氧化铝粒子，在氧化铈-氧化锆复合氧化物粒子的含量相对于整体重量为25重量％以上的整体式基材上担载有贵金属粒子。
专利文献5记载了一种蜂窝催化剂的制造方法，所述蜂窝催化剂是在隔着隔壁沿长度方向并列设置有多个贯穿孔的蜂窝结构体上担载贵金属而得到的，所述制造方法的特征在于，包括混合工序、挤出成形工序和烧成工序，所述混合工序将氧化铈-氧化锆复合氧化物粒子、氧化铝粒子和无机粘合剂混合而调制原料糊，所述挤出成形工序通过将所述原料糊挤压成形而得到隔着隔壁沿长度方向并列设置有多个贯穿孔的挤出成形体，所述烧成工序对所述挤出成形体进行烧成，所述氧化铈-氧化锆复合氧化物粒子的DCZ50为1.5～5.0μm，并且，粒度分布的标准偏差σCZ为2以下，所述氧化铝粒子的DAO50为1.5～5.0μm，并且粒度分布的标准偏差σAO为2以下。
现有技术文献
专利文献1：日本专利公开2003-236381号公报
专利文献2：日本专利公开2003-170043号公报
专利文献3：日本专利公开2004-066069号公报
专利文献4：日本专利公开2015-085241号公报
专利文献5：日本专利公开2019-063683号公报
发明内容
如专利文献1～5记载的在蜂窝状整体式基材上担载有贵金属粒子(有时贵金属粒子担载在载体上)的排气净化催化剂，尽管能够在维持低压力损失的状态下提高预热性能，但其排气净化性能尚存在改善余地。
从以上观点出发，本发明的课题是提供用于提高净化性能、特别是HC净化性能的排气净化催化剂用整体式基材、该整体式基材的制造方法以及使用该整体式基材的排气净化催化剂。
如专利文献1～5记载的排气净化催化剂中使用的整体式基材，可使用氧化铈(CeO2)-氧化锆(ZrO2)复合氧化物作为具有氧吸放性能的材料。
因此，本发明人研究了如上所述问题，结果发现，通过作为整体式基材的材料，替代氧化铈-氧化锆复合氧化物而使用氧吸放速度比氧化铈-氧化锆复合氧化物快的氧化铝(Al2O3)-氧化铈(CeO2)-氧化锆(ZrO2)复合氧化物，可以提供解决了所述课题的整体式基材和排气净化催化剂，从而完成了本发明。
本发明的要点如下。
(1)一种整体式基材，包含氧化铝-氧化铈-氧化锆复合氧化物和氧化铝。
(2)根据(1)所述的整体式基材，相对于整体式基材的总重量，氧化铝-氧化铈-氧化锆复合氧化物的含量为8～60重量％。
(3)根据(1)或(2)所述的整体式基材，相对于整体式基材的总重量，氧化铝的含量为40重量％以上。
(4)根据(1)～(3)中任一项所述的整体式基材，还包含氧化铈-氧化锆复合氧化物。
(5)根据(4)所述的整体式基材，相对于氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈和氧化铈-氧化锆复合氧化物中的氧化铈(CeO2(ACZ+CZ))，氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈(CeO2(ACZ))的重量比(CeO2(ACZ)/CeO2(ACZ+CZ))为0.1以上。
(6)一种整体式基材的制造方法，是制造(1)～(5)中任一项所述的整体式基材的方法，包括：
将氧化铝-氧化铈-氧化锆复合氧化物粒子、氧化铝粒子、氧化铝粘合剂和溶剂混合，从而调制混合物的步骤；
将调制出的混合物成形，从而调制整体式基材成形体的步骤；以及
将调制出的整体式基材成形体干燥并烧成，从而制造整体式基材的步骤。
(7)根据(6)所述的整体式基材的制造方法，氧化铝-氧化铈-氧化锆复合氧化物粒子中的氧化铈-氧化锆复合氧化物的微晶直径为30nm以下。
(8)根据(6)或(7)所述的整体式基材的制造方法，氧化铝-氧化铈-氧化锆复合氧化物粒子的BET比表面积为30m2/g以上。
(9)根据(6)～(8)中任一项所述的整体式基材的制造方法，氧化铝粒子的BET比表面积为40～200m2/g。
(10)一种排气净化催化剂，包含(1)～(5)中任一项所述的整体式基材和贵金属粒子。
根据本发明，可以提供用于提高净化性能、特别是HC净化性能的排气净化催化剂用整体式基材、该整体式基材的制造方法以及使用该整体式基材的排气净化催化剂。
附图说明
图1是表示比较例1和实施例1～4的排气净化催化剂中的、氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈(CeO2(ACZ))相对于氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈和氧化铈-氧化锆复合氧化物中的氧化铈(CeO2(ACZ+CZ))的重量比(CeO2(ACZ)/CeO2(ACZ+CZ))与脱气HC标准化浓度的关系的坐标图。
具体实施方式
以下，详细说明本发明的优选实施方式。
本发明的整体式基材、该整体式基材的制造方法以及使用该整体式基材的排气净化催化剂并不限定于下述实施方式，在不脱离本发明主旨的范围内，可以在施加了本领域技术人员能够进行的变更、改良等的各种方式下实施。
本发明涉及包含氧化铝-氧化铈-氧化锆复合氧化物和氧化铝的整体式基材、该整体式基材的制造方法以及使用该整体式基材的排气净化催化剂。
在此，整体式基材例如是具有公知的蜂窝形状的整体式基材(例如蜂窝结构体、蜂窝过滤器、高密度蜂窝等)。
本发明的整体式基材包含氧化铝-氧化铈-氧化锆复合氧化物。
汽车等的内燃机中，空气和燃料的混合比率即空燃比(A/F)可根据运转状况而变动。例如，汽车在希望提高燃油效率、减少有害气体时，在空气比率增大了的空燃比、即稀(lean)的状态下运转，在需要大输出时，例如起步时和加速时，在燃料比率增大了的空燃比、即浓(rich)的状态下运转。
这样在空燃比变动的内燃机中，从其中排出的排气的组成也可能变动。因此，希望一种即使是组成可能变动的排气也能够充分净化的排气净化催化剂。
整体式基材通过替代氧化铈-氧化锆复合氧化物而包含氧吸放速度比氧化铈-氧化锆复合氧化物快的氧化铝-氧化铈-氧化锆复合氧化物，使整体式基材即使在空燃比变动的条件(A/F过渡条件)、特别是空燃比以小的变动幅度变动的条件即排气的浓度变化小的条件下，也能够迅速进行氧吸放，使氧浓度保持一定，因此，通过在整体式基材上担载贵金属粒子而制造出的排气净化催化剂，能够具有高的化学计量保持能力，且具有高的排气净化性能、特别是HC净化性能。
本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物由氧化铝-氧化铈-氧化锆复合氧化物的粒子构成。
本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物中，氧化铈和氧化锆分散在氧化铝中，氧化铈和氧化锆的一部分形成了氧化铈-氧化锆固溶体。再者，可以通过例如粉末X射线衍射(XRD)确认氧化铈和氧化锆形成了氧化铈-氧化锆固溶体。
本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物的组成，以摩尔比计通常为Ce：Zr＝1：5～3：1，通常为Al：(Ce+Zr)＝1：1～1：10。再者，本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物的组成依赖于作为整体式基材制造时的材料的氧化铝-氧化铈-氧化锆复合氧化物的组成。
通过将氧化铝-氧化铈-氧化锆复合氧化物的组成设为所述范围，能够充分获得氧化铝带来的粒子生长抑制(提高耐热性、确保比表面积)、氧化铈带来的氧吸放性能(OSC)确保、以及氧化锆带来的氧化铈稳定化作用确保这些效果。
本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物可以进一步包含选自铈以外的稀土元素中的1种以上的元素。作为稀土元素，可举出钪(Sc)、钇(Y)、镧(La)、镨(Pr)、钕(Nd)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、镱(Yb)、镥(Lu)等。作为稀土元素，优选Y和La。相对于氧化铝-氧化铈-氧化锆复合氧化物的总重量，稀土元素的含量以氧化物形式通常为1～20重量％。
通过氧化铝-氧化铈-氧化锆复合氧化物含有稀土元素，能够提高氧化铝-氧化铈-氧化锆复合氧化物的耐热性和OSC。
相对于整体式基材的总重量，本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物的含量通常为8～60重量％，优选为20～50重量％。再者，本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物的含量依赖于作为整体式基材制造时的材料的氧化铝-氧化铈-氧化锆复合氧化物的添加量。
通过氧化铝-氧化铈-氧化锆复合氧化物在整体式基材中的含量处于所述范围，整体式基材即使在空燃比变动的条件、特别是空燃比以小的变动幅度变动的条件即排气的浓度变化小的条件下，也能够迅速进行氧吸放，使氧浓度保持一定，因此，通过使整体式基材担载贵金属粒子而制造出的排气净化催化剂，能够具有更高的化学计量保持能力，且具有更高的排气净化性能、特别是HC净化性能。
本发明的整体式基材包含氧化铝。
在此，本发明的整体式基材所含的氧化铝包含氧化铝的粒子。
通过整体式基材包含氧化铝的粒子，耐热性比氧化铝-氧化铈-氧化锆复合氧化物高的氧化铝的粒子发挥作为贵金属担载场所的作用，能够提高催化剂的耐久性。
本发明的整体式基材所含的氧化铝，除了氧化铝的粒子以外，可以还含有整体式基材制造时可添加的氧化铝粘合剂和/或氧化铝纤维衍生的氧化铝的非晶质(无定形物)和/或纤维。
通过整体式基材含有氧化铝的非晶质和/或纤维，氧化铝发挥作为氧化物粒子彼此的粘合剂和/或整体式基材的整体结构的增强材料的作用，能够提高催化剂的物理稳定性。
相对于整体式基材的总重量，本发明的整体式基材所含的氧化铝的含量通常为40重量％以上，优选为45～60重量％。再者，本发明的整体式基材所含的氧化铝的含量依赖于作为整体式基材制造时的材料的氧化铝的粒子、氧化铝粘合剂和氧化铝纤维的添加量。
通过氧化铝在整体式基材中的含量处于所述范围，如上所示，氧化铝能够充分确保贵金属的担载场所由此确保充分的耐久性。
本发明的整体式基材可以进一步包含氧化铈-氧化锆复合氧化物。
本发明的整体式基材中可包含的氧化铈-氧化锆复合氧化物由氧化铈-氧化锆复合氧化物的粒子构成。
通过整体式基材包含氧化铈-氧化锆复合氧化物，能够确保充分的OSC。
本发明的整体式基材所含的氧化铈-氧化锆复合氧化物优选含有15重量％以上、特别优选含有20重量％以上的量的氧化铈，进而优选含有70重量％以下、特别优选含有60重量％以下的量的氧化铈。另外，氧化铈-氧化锆复合氧化物优选含有80重量％以下、特别优选含有70重量％以下的量的氧化锆。由于这种氧化铈-氧化锆复合氧化物的热容量小，所以容易使整体式基材的温度上升，从而能够提高催化剂的预热性能。再者，本发明的整体式基材所含的氧化铈-氧化锆复合氧化物的组成依赖于作为整体式基材制造时的材料的氧化铈-氧化锆复合氧化物的组成。
本发明的整体式基材所含的氧化铈-氧化锆复合氧化物可以进一步包含选自铈以外的稀土元素中的1种以上的元素。作为稀土元素，可举出钪(Sc)、钇(Y)、镧(La)、镨(Pr)、钕(Nd)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、镱(Yb)、镥(Lu)等。作为稀土元素，优选Y和La。相对于氧化铈-氧化锆复合氧化物的总重量，稀土元素的含量以氧化物形式通常为5～25重量％。
通过氧化铈-氧化锆复合氧化物含有稀土元素，能够提高氧化铈-氧化锆复合氧化物的耐热性和OSC。
本发明的整体式基材所含的氧化铈-氧化锆复合氧化物的含量在存在的情况下，被调整为整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈(CeO2(ACZ))相对于整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈和氧化铈-氧化锆复合氧化物中的氧化铈(CeO2(ACZ+CZ))的重量比(CeO2(ACZ)/CeO2(ACZ+CZ))通常为0.1以上，优选为0.2以上，特别优选为0.5以上。再者，本发明的整体式基材也可以不含氧化铈-氧化锆复合氧化物，因此该重量比的上限值没有限定。再者，本发明的整体式基材所含的氧化铈-氧化锆复合氧化物的含量依赖于作为整体式基材制造时的材料的氧化铈-氧化锆复合氧化物的添加量。
通过基于氧化铝-氧化铈-氧化锆复合氧化物的含量将氧化铈-氧化锆复合氧化物的含量设定在所述范围，整体式基材即使在空燃比变动的条件、特别是空燃比以小的变动幅度变动的条件即排气的浓度变化小的条件下，也能够迅速进行氧吸放，使氧浓度保持一定，因此，通过使整体式基材担载贵金属粒子而制造出的排气净化催化剂，能够具有更高的化学计量保持能力，且具有更高的排气净化性能、特别是HC净化性能。
本发明的整体式基材尽管在作为材料使用下述说明的氧化铝-氧化铈-氧化锆复合氧化物、氧化铝以及根据情况使用的氧化铈-氧化锆复合氧化物方面不同，但都可以采用与以往的堇青石基材同样的步骤制造。例如，可以通过在氧化铝-氧化铈-氧化锆复合氧化物的粒子和氧化铝的粒子的混合物中加入作为溶剂的水和粘合剂，例如氧化铝粘合剂和/或氧化铝纤维，混合搅拌后用挤出机等成形，使用例如微波干燥机、热风干燥机、介电干燥机减压干燥机、真空干燥机、冷冻干燥机等干燥后，在例如通常900～1200℃下烧成通常1～24小时来制造。
在本发明的整体式基材的制造中使用的材料中，作为氧化铝-氧化铈-氧化锆复合氧化物，可以是在该技术领域中公知的物质，例如在日本特开平10-202102号公报、日本特开2001-232199号公报中记载的物质。
例如，氧化铝-氧化铈-氧化锆复合氧化物可以采用醇盐法或共沉淀法调制。氧化铝-氧化铈-氧化锆复合氧化物通过采用醇盐或共沉淀法调制，能够调制由均匀且微细的一次粒子构成的复合氧化物，并且能够容易地调制包含氧化铈-氧化锆固溶体的复合氧化物。
醇盐法中，例如通过将铝、铈、锆和根据情况加入的稀土元素的所有金属醇盐进行混合，水解后进行烧成，由此可以调制氧化铝-氧化铈-氧化锆复合氧化物。另外，即使不将铝、铈、锆和根据情况加入的稀土元素全部以金属醇盐形式使用，只要将其至少一种以金属醇盐形式使用，其余的金属也可以以硝酸盐或乙酰乙酸盐等的溶液形式使用。
作为该金属醇盐，可以是甲氧基化物、乙氧基化物、丁氧基化物等中的任意种，优选在作为溶剂的醇中的溶解度高的金属醇盐。再者，作为溶剂的醇也可以使用任意的醇。
共沉淀法中，例如通过将铝、铈、锆和根据情况加入的稀土元素的所有金属的硝酸盐等水溶性盐进行混合，用氨水等以氢氧化物形式共沉淀，并对其烧成，由此可以调制氧化铝-氧化铈-氧化锆复合氧化物。另外，即使不将铝、铈、锆和根据情况加入的稀土元素全部以水溶性盐形式使用，只要将其至少一种以水溶性盐形式使用，也可以将其余的金属以金属粉末或氧化物粉末等的固体形式使用。
这样得到的氧化铝-氧化铈-氧化锆复合氧化物，优选预先在通常500～900℃下进行热处理。通过预先对氧化铝-氧化铈-氧化锆复合氧化物进行热处理，能够抑制粒子的过度结晶生长，并且能够进一步抑制耐久后OSC的降低。
氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈-氧化锆复合氧化物的微晶优选为微细的，其微晶直径通常为30nm以下，优选为5nm～20nm。再者，氧化铈-氧化锆复合氧化物的微晶直径例如可以用XRD的半值宽来测定。
通过将氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈-氧化锆复合氧化物的微晶直径设在所述范围，能够充分获得氧化铈带来的OSC确保效果。
氧化铝-氧化铈-氧化锆复合氧化物的BET比表面积通常为30m2/g以上，优选为40～80m2/g。
通过将氧化铝-氧化铈-氧化锆复合氧化物的BET比表面积设在所述范围，能够充分获得由氧化铈带来的OSC确保效果。
在本发明的整体式基材的制造中使用的材料中，作为氧化铝，可以使用氧化铝粒子、氧化铝粘合剂、氧化铝纤维等。
氧化铝粒子可以使用在该技术领域中一般作为催化剂载体市售的粒子。
通过使用氧化铝粒子作为氧化铝，耐热性比氧化铝-氧化铈-氧化锆复合氧化物高的氧化铝粒子发挥作为贵金属担载场所的作用，能够提高催化剂的耐久性。
氧化铝粒子没有限定，包含α相的氧化铝粒子、θ相的氧化铝粒子、δ相的氧化铝粒子等。氧化铝粒子优选为θ相的氧化铝粒子和/或δ相的氧化铝粒子。再者，氧化铝粒子的晶体结构例如可以通过粉末X射线衍射(XRD)来确认。
由于氧化铝粒子一般是表面积高的θ相的氧化铝粒子和/或δ相的氧化铝粒子，所以即使在配合到本发明的整体式基材后，也能够维持高的表面积，能够抑制贵金属的劣化。
氧化铝粒子的BET比表面积通常为40～200m2/g，优选为50～150m2/g。
通过将氧化铝粒子的BET比表面积设在所述范围，氧化铝粒子发挥作为金属担载场所的作用，能够提高催化剂的耐久性。
氧化铝粘合剂和氧化铝纤维可以使用在该技术领域中一般市售的产品。
通过使用氧化铝粘合剂作为氧化铝，氧化铝粘合剂发挥作为氧化物粒子彼此的粘合剂的作用，能够提高整体式基材的物理稳定性。进而，通过使用氧化铝纤维作为氧化铝，氧化铝纤维发挥作为整体式基材的整体结构的增强材料的作用，能够提高整体式基材的物理稳定性。
在本发明的整体式基材的制造中使用的材料中，氧化铈-氧化锆复合氧化物是在以往的排气净化催化剂中作为助催化剂(储氧材料)使用的材料，其详情对于本领域技术人员是公知的。氧化铈-氧化锆复合氧化物优选氧化铈和氧化锆形成固溶体。氧化铈-氧化锆复合氧化物可以采用醇盐法或共沉淀法调制，若为共沉淀法，则可以通过在例如溶解了铈盐(硝酸铈等)和锆盐(硝酸氧锆等)的水溶液中加入氨水，生成共沉淀，将得到的沉淀物干燥后，通常在400～500℃下烧成通常5小时左右来调制。
再者，氧化铝-氧化铈-氧化锆复合氧化物与氧化铈-氧化锆复合氧化物相比，即使在整体式基材的烧成温度那样的高温环境下，也难以发生粒子(晶体)生长。因此，制造后的整体式基材的氧化铝-氧化铈-氧化锆复合氧化物的粒子，即使考虑在整体式基材制造时因烧成引起的粒子(晶体)生长，也具有比作为整体式基材的材料使用的氧化铝-氧化铈-氧化锆复合氧化物的粒子粒径的同等稍大的粒径。因此，这样得到的本发明的整体式基材所含的氧化铝-氧化铈-氧化锆复合氧化物的粒子，即使在制造后也具有小的粒径、即大的比表面积，能够具有高的OSC。
使用本发明的整体式基材制造的排气净化催化剂具有贵金属粒子被担载于本发明的整体式基材的结构。贵金属粒子优选为选自铂族金属，特别是Pt、Rh和Pd中的1种以上的金属。贵金属粒子向整体式基材的担载可以通过如以往那样与助催化剂(储氧材料)、载体、粘合剂等一起混合而调制浆料，采用洗涂将其形成于整体式基材上来进行，但由于本发明的整体式基材本身具有助催化剂和/或载体的功能，所以即使直接担载贵金属粒子也能够期待高的净化性能。特别是在Cold-HC降低中三元催化剂的低热容量化是有效的，因此，通过消除洗涂层可以使催化剂低热容量化，可期待更高的HC净化性能。再者，贵金属可以使用硝酸钯和氯化铑等一般试剂担载。
本发明的排气净化催化剂即使在空燃比变动的条件、特别是空燃比以小的变动幅度变动的条件、例如空燃比在14.6±0.2(14.4～14.8)之间变动的条件下，也会使排气净化催化剂所含的整体式基材迅速进行氧吸放，使氧浓度保持一定，因此能够具有更高的化学计量保持能力，且具有更高的排气净化性能、特别是HC净化性能。
[实施例]
以下，使用实施例更详细地说明本发明，但本发明并不限定于这些实施例。
1.三元催化剂的制作
使用具有表1所示组成的Al2O3-CeO2-ZrO2复合氧化物粒子(ACZ)和CeO2-ZrO2复合氧化物粒子(CZ)，按照表2和表3所示规格制作了比较例1和实施例1～4的排气净化催化剂。
比较例1的排气净化催化剂是通过使用CeO2-ZrO2复合氧化物粒子、Al2O3粒子、作为稀土元素的La2O3粒子和Y2O3粒子、Al2O3粘合剂以及Al2O3纤维，在1150℃下烧成而制造出整体式基材，并使用该整体式基材而制作的。再者，认为该整体式基材本身具有贵金属粒子(催化剂)载体功能和助催化功能，所以不进行洗涂而是直接将预定量的贵金属担载于基材上。具体而言，通过将基材浸渍在分散有必要量的硝酸钯和氯化铑的水溶液中放置一定时间，由此在基材上担载贵金属。比较例1的排气净化催化剂的基材容量为0.9L。
实施例1～4的排气净化催化剂是通过使用Al2O3-CeO2-ZrO2复合氧化物粒子、Al2O3粒子、作为稀土元素的La2O3粒子和Y2O3粒子、Al2O3粘合剂、Al2O3纤维以及根据情况使用的CeO2-ZrO2复合氧化物粒子，在1150℃下烧成而制造出整体式基材，并使用该整体式基材而制作的。再者，认为该整体式基材本身具有催化剂载体功能和助催化剂功能，所以不进行洗涂而是直接将预定量的贵金属担载于基材上。具体而言，通过将基材浸渍在分散有必要量的硝酸钯和氯化铑的水溶液中放置一定时间，由此在基材上担载贵金属。实施例1～4的排气净化催化剂的基材容量均为0.9L。
表1
Al<sub>2</sub>O<sub>3</sub> CeO<sub>2</sub> ZrO<sub>2</sub> La<sub>2</sub>O<sub>3</sub> Y<sub>2</sub>O<sub>3</sub>
ACZ组成* 30 27 35 4 4
CZ组成* —— 30 60 5 5
*单位是各材料中的重量％
表2
Figure BDA0003164229980000131
*单位是各基材中的重量％
表3
Figure BDA0003164229980000132
2.耐久试验
在V8 4.6L发动机正下方安置了制成的比较例1和实施例1～4的排气净化催化剂。A/F为循环变化的复合模式，在床层温度950℃下进行50小时的耐久试验。
3.排气净化催化剂评价
在串联4缸2.5L发动机中安置所述2.耐久试验结束了的各排气净化催化剂，在进入气体温度550℃下反复进行浓(空燃比：14.4)/稀(空燃比：14.8)的条件下，测定了排气净化催化剂的脱气HC浓度。
接着，通过将比较例1和实施例1～4的排气净化催化剂的脱气HC浓度分别除以实施例4的排气净化催化剂的脱气HC浓度，计算出比较例1和实施例1～4的排气净化催化剂的脱气HC标准化浓度。
图1表示比较例1和实施例1～4的排气净化催化剂中的、Al2O3-CeO2-ZrO2复合氧化物中的CeO2(CeO2(ACZ))相对于Al2O3-CeO2-ZrO2复合氧化物中的CeO2和CeO2-ZrO2复合氧化物中的CeO2(CeO2(ACZ+CZ))的重量比(CeO2(ACZ)/CeO2(ACZ+CZ))与脱气HC标准化浓度的关系。
由图1可知，通过排气净化催化剂的整体式基材中的CeO2(ACZ)/CeO2(ACZ+CZ)为0.1以上，优选为0.2以上，能够实现高的HC净化性能。

Claims (10)

1.一种整体式基材，包含：
氧化铝-氧化铈-氧化锆复合氧化物、和
氧化铝。
2.根据权利要求1所述的整体式基材，相对于整体式基材的总重量，氧化铝-氧化铈-氧化锆复合氧化物的含量为8～60重量％。
3.根据权利要求1或2所述的整体式基材，相对于整体式基材的总重量，氧化铝的含量为40重量％以上。
4.根据权利要求1～3中任一项所述的整体式基材，还包含氧化铈-氧化锆复合氧化物。
5.根据权利要求4所述的整体式基材，相对于氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈和氧化铈-氧化锆复合氧化物中的氧化铈，氧化铝-氧化铈-氧化锆复合氧化物中的氧化铈的重量比为0.1以上。
6.一种整体式基材的制造方法，是制造权利要求1～5中任一项所述的整体式基材的方法，包括：
将氧化铝-氧化铈-氧化锆复合氧化物粒子、氧化铝粒子、氧化铝粘合剂和溶剂混合，从而调制混合物的步骤；
将调制出的混合物成形，从而调制整体式基材成形体的步骤；以及
将调制出的整体式基材成形体干燥并烧成，从而制造整体式基材的步骤。
7.根据权利要求6所述的整体式基材的制造方法，氧化铝-氧化铈-氧化锆复合氧化物粒子中的氧化铈-氧化锆复合氧化物的微晶直径为30nm以下。
8.根据权利要求6或7所述的整体式基材的制造方法，氧化铝-氧化铈-氧化锆复合氧化物粒子的BET比表面积为30m2/g以上。
9.根据权利要求6～8中任一项所述的整体式基材的制造方法，氧化铝粒子的BET比表面积为40～200m2/g。
10.一种排气净化催化剂，包含权利要求1～5中任一项所述的整体式基材和贵金属粒子。
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