CN1094467C - 纳米铈锆复合氧化物、其制备方法及用途 - Google Patents

纳米铈锆复合氧化物、其制备方法及用途 Download PDF

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CN1094467C
CN1094467C CN99102251A CN99102251A CN1094467C CN 1094467 C CN1094467 C CN 1094467C CN 99102251 A CN99102251 A CN 99102251A CN 99102251 A CN99102251 A CN 99102251A CN 1094467 C CN1094467 C CN 1094467C
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cerium zirconium
zirconium oxide
hydrazine
nanometer cerium
composite oxides
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CN1263868A (zh
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张德源
王振华
陆世鑫
吴介达
王晔明
杨宇翔
王绍刚
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Yaolong Non-Ferrous Metal Co Ltd Shanghai
Tongji University
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Yaolong Non-Ferrous Metal Co Ltd Shanghai
Tongji University
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Abstract

本发明公开了一种纳米铈锆复合氧化物、其制备方法及用途。本发明的纳米铈锆复合氧化物包括4～98%重量的CeO2和1～95%重量的ZrO2；其晶粒粒径≤100nm，该复合氧化物经900℃灼烧1小时的灼减量小于5%。

Description

纳米铈锆复合氧化物、其制备方法及用途
本发明涉及一种纳米铈锆复合氧化物、其制备方法及用途。具体地讲，本发明涉及一种纳米铈锆复合氧化物，该复合氧化物包括4～98％(重量)的CeO2，1～95％(重量)的ZrO2。
氧化铈、氧化锆及铈锆的组合物在催化领域内被用作汽车的后燃催化剂，用于处理从内燃机排出的废气。法国罗纳·布朗克化学公司申请号为96196505.3及94194552.9的中国专利申请、申请号为95119164.0、95119160.8和95119163.2的日本三德金属工业株式会社的中国专利申请和申请号为89103518.4的日本触媒化学工业株式会社的中国专利申请都公开了氧化铈、氧化锆及铈锆的组合物作为多功能催化剂的应用。
目前市场上现有的由铈锆氧化物组合物组成的催化剂不仅能够氧化存在于废气中的一氧化碳和烃，而且能够还原也存在于这些气体中的氮氧化物，所以称之为“三功能”催化剂，或“三效”催化剂。为了得到以铈和锆混合氧化物为主要成分的组合物，常规的制备方法为：
(1)制备含有铈化合物和锆化合物的液体混合物；
(2)使上述液体混合物与碳酸盐或者碳酸氢盐进行接触，生成一种在反应时其pH呈中性或碱性的反应介质，(一般调至pH8～11)；
(3)分离回收所得到的沉淀物；
(4)煅烧沉淀物；
运用上述这种方法一般可以得到比表面积较大的铈锆混合氧化物，但真如这些文献所提及的，它们往往以非化合物形式存在，即在最后得到的催化剂中可以发现这二组分是良好分离的氧化物颗粒的简单物理混合物形式。其X衍射的分析也证实了这一点。
本发明的目的是提供一种不仅比表面积大而且灼减量小的具有较大化学活性的纳米铈锆复合氧化物，该复合氧化物经900℃灼烧1小时的灼减量小于5％。
本发明的进一步目的是提供一种热稳定性优异的纳米铈锆复合氧化物，本发明的这种复合氧化物在高温下经过长时间灼烧仍然保持单相。
本发明纳米铈锆复合氧化物的特殊优良性能是通过本发明的新的制备方法来达到的。本发明的制备方法是：
在200℃～1000℃温度下热分解含肼(或肼盐)的相应的铈锆前驱化合物可制得本发明的纳米铈锆复合氧化物，所述的含肼或肼盐的相应的铈锆前驱化合物选自铈锆的硝酸盐、氯化物、草酸盐、碳酸盐、氢氧化物或它们的混合物。
上述含肼(或肼盐)的前驱化合物可以通过共同沉淀法、混合法等多种途径来制备。
(1)共同沉淀法  是在铈化合物或锆化合物溶液中先加入肼(或肼盐)再共同
               沉淀；或将肼(或肼盐)加入到铈锆化合物的混合溶液中再共
               同沉淀。
Figure C9910225100051
或
(2)混合法  是在铈化合物和锆化合物的混合物中加入肼(或肼盐)直接搅拌混匀。
Figure C9910225100053
将上述共同沉淀法或混合法所得的含肼(或肼盐)的铈锆前驱化合物经加热分解，冷却至室温，经解碎、过筛、便可得到本发明的纳米铈锆复合氧化物。
本发明制备方法的优点是：
肼(或肼盐)在180℃～300℃时会分解，同时释放出大量气体和热量，瞬时热量的释放可使前驱化合物分解更加完全，而同时产生的大量气体又使热分解产物的晶粒难以聚集及生长，从而由此制得的热分解产物的晶粒较不加肼(或肼盐)的相同的前驱化合物热分解制得的同样产物的晶粒小，因而本发明产品具有更大的活性及热稳定性，同时具有较小的灼减。
用本发明方法制得的纳米铈锆复合氧化物是一种新型的固熔体类型的多元复合氧化物，它包括4～98％(重量)的CeO2和1～95％(重量)的ZrO2。本发明的纳米铈锆复合氧化物的晶粒粒径≤100nm，用BET方法测定它们的比表面积为5～120m2/g，具有较大的化学活性与热稳定性，它在900℃灼烧1小时的灼减量小于5％。本发明的纳米铈锆复合氧化物在高温下经过长时间灼烧还可以保持单相。特别是当该复合氧化物是以铈为主体时(其中CeO2的重量含量为70～98％时)，其经1100℃灼烧12小时后，仍然能够保持单相。
本发明的纳米铈锆复合氧化物中还可以引入0.01-10％(重量)的其他元素，该其它元素选自稀土元素、铪、硅、铝、钼等元素。引入上述这些元素后的本发明的纳米铈锆复合氧化物的性能甚至更为优越。
本发明的纳米铈锆复合氧化物在用作磨研材料、催化剂及环保工业等领域中有着优良的性能，并有着广泛应用前景，尤其在当今高级研磨时，纳米氧化物是极佳的材料。
以下通过附图和实施例进一步说明本发明纳米铈锆复合氧化物的优良性能。
图1是用常规方法制得的铈锆组合物的X衍射图谱。
图2是本发明方法所制得的一种纳米铈锆复合氧化物(其组成为CeO2 75％重量，ZrO2 25％重量)的X衍射图谱。
图3是经高温灼烧的本发明的纳米铈锆复合氧化物的X衍射图。
图4是本发明的铈锆复合氧化物的电镜照片(放大10,000倍，1cm相当于100nm)。
图5是本发明含肼的铈锆前驱化合物的热失重曲线。
图6是本发明含肼的铈锆前驱化合物的差热分析曲线。
由图1可以明显见到用常规方法制得的铈锆组合物中实际上是CeO2相和ZrO2相两相同时存在的。
由图2可以明显证实本发明的纳米铈锆复合氧化物是一种固熔体。
由图3可以看到本发明的纳米铈锆复合氧化物在高温经受长时间灼烧后(分别在600℃、700℃、800℃、900℃、1000℃和1100℃时灼烧12小时后)还能够保持单相。
由图5、图6曲线显示，在200℃～300℃时含肼化合物分解，瞬时放出大量的气体与热量，这促使铈锆前驱化合物分解完全，而且晶粒难以聚集和长大，因此得到性能优异的铈锆复合氧化物。
实施例1.
称取草酸铈396g，氧氯化锆133g与含氧化钼0.2g的草酸溶液混合后搅匀，于100℃～105℃烘干后，取出冷却，加入180ml肼，搅匀，放入高温炉中逐渐升温至500℃～580℃，保温0.5h，取出冷却，得到淡黄色铈锆复合氧化物，其晶粒粒径为60～80nm。
实施例2.
取含有7.5g CeO2的硝酸铈溶液，与含有2.5g ZrO2的硝酸锆溶液混合，以H2C2O4溶液及氨水沉淀铈锆，调节溶液的pH值呈碱性，再加入20ml肼并搅匀，经过滤后于105℃烘干，加入0.5g钼酸，搅匀混合物，于400℃～450℃灼烧1h，得到淡黄色的铈锆复合氧化物，其晶粒为80～100nm。
实施例3.
同实施例1的步骤，加入肼分别为120ml及150ml，所得到的淡黄色铈锆复合氧化物，其比表面积分别为75.4m2/g与82.8m2/g，经900℃灼烧1h后测得灼减为2.9％与3.1％。
实施例4.
称取27.2gCe(OH)4，114g ZrOCl2，混合后于100℃～120℃烘干，取出冷却后加入肼20ml，混匀后放入高温炉中逐渐升温至450℃，保温0.5h，取出冷却，得到铈锆复合氧化物，其比表面积为40.8m2/g。
实施例5.
称取981g草酸铈，268g氧氯化锆，32g草酸镧，混和，搅匀，于100℃烘干，取出冷却，加入草酸肼500ml搅匀，然后放入高温炉中逐渐加热升温至500℃，保温0.5h，取出冷却，得到淡黄色的铈锆复合氧化物，其比表面积为120m2/g，经900℃灼烧1h测得其灼减为2.5％。
实施例6.
称取1105g碳酸铈，280g氧氯化锆，混合搅匀，于100℃烘干，取出冷却，加入肼300ml，搅匀，放入高温炉中加热至450℃～500℃，保温0.5h，取出冷却，得到淡黄色的铈锆复合氧化物，其比表面积为91.6m2/g。
实施例7.
称取1.4g草酸铈，7g碳酸锆，混合搅匀，于100℃烘干，取出冷却加入肼20ml，搅匀，放入高温炉中加热至850℃～900℃，保温1h，取出冷却后得到淡黄色的铈锆复合氧化物，其比表面积为30.1m2/g。
实施例8.
称取20g草酸铈，20g氧氯化锆，5g草酸镧，混合搅匀，加入肼20ml搅匀，放入高温炉中加热至450℃～500℃保温0.5h，取出冷却后得到淡黄色的铈锆复合氧化物，其比表面积为67.8m2/g。
实施例9
称取20g草酸铈，2g氧氯化锆和0.2g氢氧化铝混和并搅匀，于110℃烘干，取出冷却，加入肼30ml，搅匀，放入高温炉中加热至400℃～450℃，保温0.5h，取出冷却，得到淡黄色的铈锆复合氧化物，其比表面积为104.8m2/g。
实施例10
称取2g硝酸铈，20g氧氯化锆，0.5g草酸钇，混合搅匀，于100℃烘干，取出冷却，加入20ml肼，搅匀，放入高温炉中加热至550℃～600℃，保温0.5h，取出冷却，得到淡黄色的铈锆复合氧化物，其比表面积为26.2m2/g，灼减量为2.8％。
实施例11
称取10g氢氧化铈，2g碳酸锆混和搅匀，于100℃烘干，取出冷却后加入50ml硝酸肼，搅匀，放入高温炉中加热至500℃～550℃，保温1h，取出冷却后得到淡黄色的铈锆复合氧化物，其比表面积为54m2/g。
通过以上实施例进一步说明本发明的纳米铈锆复合氧化物的优异性能，与现有技术相比，本发明方法制得的纳米铈锆复合氧化物的效果是十分明显的。本发明的上述实施例只是为了说明本发明的内容，而不是将本发明具体限制在所说明的具体实施例方式。本领域的技术人员都会理解本发明包括对于具体实施例所作的各种不背离本发明实质和范围的改变和修正。

Claims (14)

1.一种纳米铈锆复合氧化物，其特征在于该复合氧化物包括4-98％重量的CeO2和1-95％重量的ZrO2；其晶粒粒径≤100nm，该复合氧化物经900℃灼烧1小时的灼减量小于5％。
2.如权利要求1所述的纳米铈锆复合氧化物，其特征还在于该复合氧化物中CeO2的重量含量为70～98％。
3.如权利要求1所述的纳米铈锆复合氧化物，其特征在于它还包含0.01-10％重量的其它元素，该其它元素选自铪，硅，铝，钼及稀土元素。
4.如权利要求2所述的纳米铈锆复合氧化物，其特征在于它还包含0.01-10％重量的其它元素，该其它元素选自铪，硅，铝，钼及稀土元素。
5.如权利要求1所述的纳米铈锆复合氧化物，其特征还在于该复合氧化物的比表面积为5-120m2/g。
6.如权利要求2所述的纳米铈锆复合氧化物，其特征还在于该复合氧化物的比表面积为5-120m2/g。
7.如权利要求3所述的纳米铈锆复合氧化物，其特征还在于该复合氧化物的比表面积为5-120m2/g。
8.如权利要求4所述的纳米铈锆复合氧化物，其特征还在于该复合氧化物的比表面积为5-120m2/g。
9.如权利要求2，4，6，8所述的纳米铈锆复合氧化物，其特征还在于该复合氧化物经1100℃灼烧12小时仍保持单相。
10.一种纳米铈锆复合氧化物的制备方法，其特征在于该复合氧化物是在400-1000℃温度下，通过含肼或肼盐的前驱化合物的热分解而制得，所述的前驱化合物选自铈、锆的硝酸盐、氯化物、草酸盐、碳酸盐、氢氧化物或其混合物。
11.如权利要求10所述的纳米铈锆复合氧化物的制备方法，其特征还在于其中用作热分解的含肼或肼盐的前驱化合物是在待热分解的前驱化合物制备混合过程中添加肼或肼盐所得到的相应的含肼或肼盐的铈锆前驱化合物。
12.如权利要求10所述的纳米铈锆复合氧化物的制备方法，其特征还在于其中用作热分解的含肼或肼盐的前驱化合物是将待分解的铈锆前驱化合物直接与肼或肼盐混合而得到含肼或肼盐的铈锆前驱化合物。
13.如权利要求1-8所述的纳米铈锆复合氧化物的应用，其特征在于它可用作磨研材料。
14.如权利要求1-8所述的纳米铈锆复合氧化物的应用，其特征在于它可用作催化剂。
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