CN106975491A - 一种多孔Ce-Zr基复合氧化物催化剂的制备方法 - Google Patents
一种多孔Ce-Zr基复合氧化物催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种多孔Ce-Zr基复合金属氧化物催化剂及其制备方法，属于挥发性有机污染物(VOCs)控制技术及催化领域。该催化剂采用无模板剂-溶胶凝胶法，在混合金属盐溶液中加入造孔剂制得，成本低，工艺简单，步骤简明。本发明提供的Ce-Zr基复合金属氧化物具有多孔结构，孔径可调，有益于催化氧化过程中VOCs及其产物的传质扩散，以及催化活性和稳定性的提高，在挥发性有机污染物控制和催化领域具有广阔的应用前景。
Description
技术领域
本发明涉及一种多孔Ce-Zr基复合氧化物催化剂及其制备方法，属于挥发性有机物(VOCs)控制技术及催化领域。
背景技术
近年来，挥发性有机物(volatile organic compounds，简称VOCs)已成为仅次于SOx、NOx的另一类大气污染物。VOCs不仅会与NOx发生光化学反应导致大气的氧化性显著增强，形成大量的二次PM2.5，加重灰霾的形成，还会造成大气臭氧层的消耗和地面臭氧的生成。同时，其毒性(致畸、致癌和致突变)和强的生物体内累积性，也给人的身体健康带来了极大的危害。因此，研究出效果优良、价格低廉、工艺简单的去除VOCs的方法很有实际意义。在众多的VOCs治理技术中，催化氧化过程可降解大部分VOCs，且降解效率高、运行成本低廉，在VOCs污染控制领域被广泛采用。
催化氧化技术的核心是催化剂，其性能优劣决定了催化脱除VOCs的效率和运行成本。用于催化氧化脱除VOCs的催化剂主要有两大类：负载型金属催化剂以及过渡金属及其氧化物或复合氧化物催化剂。与负载型催化剂活性组分分散不均匀、反应活性低、易积碳失活不同，多孔体相复合氧化物具有发达的孔道结构和高的比表面积，有利于反应物的扩散、吸附和活化，因而具有更好的催化性能。稀土金属助剂Ce由于其丰富的氧空位缺陷，高的储氧/释氧能力及Ce3+与Ce4+价态之间的转化而引起了研究者的广泛关注，研究发现，CuO-CeO2复合金属氧化物在氧化反应中的催化活性可以与负载型贵金属催化剂的活性相匹敌，这是因为Ce引入CuO中可以稳定Cu的活性位点，影响Cu的氧化还原性，增加了复合金属氧化物催化剂的氧的扩散率和存储容量，故在CuO中掺入稀土金属氧化物中CeO2可提高其催化活性。但单助剂CeO2热稳定性差，在高温后会因烧结而失去储氧性能。有研究表明，用Zr4+取代CeO2中的Ce4+，不仅可以提高CeO2的储氧性能、氧化还原性、热稳定性。有研究表明，将ZrO2添加到CeO2中形成固溶体，会极大地促进活性组分CuO的分散及增加铜的氧化物的还原性。
合成多孔氧化物采用的方法主要有共沉淀法、硬模板法、一步水热法等，但这些合成方法具有工艺繁琐、生产成本较高等缺点。专利201310401213.0公开了一种锆稳定的Ce-Zr-Cr复合氧化物的共沉淀制备方法，方法虽然简单，但步骤较为繁琐，在制备过程中除了要用氨水调节金属盐溶液的pH值，还要用蒸馏水不断地洗涤沉淀物直至其成为中性。专利201310601236.6公开了一种通过硬模板制备多元介孔氧化物的方法，以介孔泡沫氧化硅为硬模板，借助介孔氧化硅泡沫材料的超大孔径和三维连通的特殊结构，从而得到有序介孔多元氧化物，但是，受硬模板法本身的限制，存在产物收率低、重复性欠佳和难以工业放大等突出问题。
发明内容
本发明的目的是为了克服上述合成方法存在的缺陷，提供了一种工艺简单、步骤简明、可工业放大的有效脱除VOCs的多孔Ce-Zr基复合氧化物催化剂。该催化剂具有多孔结构、孔径可调，是一种具有高活性、高稳定性的催化剂。
为了实现上述目的，本发明采取了如下技术方案。
本发明提供了多孔Ce-Zr基复合氧化物催化剂的合成方法，以过渡金属的金属盐为原料，利用溶胶-凝胶法制备多孔Ce-Zr基复合氧化物，制备步骤如下：
(1)将铈、锆金属盐和过渡金属盐按一定的摩尔比溶解在40～70mL有机溶剂中，溶解温度在50～80℃之间；
(2)待(1)中金属盐完全溶解后加入0.15-0.25mol/L的造孔剂，形成凝胶，凝胶在60～80℃下加热并搅拌3～4h，形成粘稠状胶体；
(3)将(2)中粘稠状胶体在室温下老化0～48h后于60-100℃下在烘箱中干燥0～12h，并在空气流中于350～650℃下煅烧2～8h。
所述的过渡金属为铜、钴、铁、锌、锰、铬、镍、锶、钇和钐等。
所述的金属盐为金属的硝酸盐或乙酸盐。
所述的有机溶剂无水乙醇。
所述的造孔剂为草酸、柠檬酸与另一种或多种有机溶液的混合溶液。
所述的造孔剂中另一种或多种有机溶液是乙醇，或乙醇与乙二醇、环己烷、石油醚、正己烷等其中一种或多种有机溶剂的混合溶液。
本发明具有以下有益效果：
1)本发明采用无模板剂-溶胶凝胶法制备多孔催化剂，成本低、合成工艺简单，步骤简明，所使用的设备简单，易于实现大规模生产；
2)本发明合成的多孔Ce-Zr基复合氧化物催化剂具有多孔结构、孔径可调，有利于VOCs及其降解产物的传质扩散，从而提高催化活性和稳定性。
附图说明
图1(a)为实施例7合成的多孔Ce-Zr基复合氧化物催化降解甲苯的转化率曲线。
图1(b)为实施例7合成的多孔Ce-Zr基复合氧化物催化降解甲苯的CO2选择性。
实施例
下面列举实例，说明本发明涉及的多孔Ce-Zr基复合氧化物催化剂的制备方法。
实施例1：7.986g硝酸铜、10.742g硝酸铈和12.27g硝酸锆在50℃下溶解在70mL的无水乙醇中，将造孔剂草酸溶解在无水乙醇中，配制为0.15mol/L的溶液，将其按等摩尔比倒入上述金属硝酸盐溶液中形成凝胶，将凝胶在60℃下搅拌加热3h，在空气气氛下老化12h，然后置于烘箱在80℃下中干燥8h，将干燥后的凝胶再在马弗炉里于空气气氛下在350℃下煅烧2h；
实施例2：用实施例1相同的操作，不同之处在于：将一定量的乙酸锰、硝酸铈和硝酸锆在50℃下溶解在70mL的无水乙醇中；
实施例3：用实施例1相同的操作，不同之处在于：将草酸溶解在无水乙醇和乙二醇中，配制为0.15mol/L的溶液；
实施例4：用实施例1相同的操作，不同之处在于：将草酸溶解在无水乙醇和正己烷中，配制为0.23mol/L的溶液；
实施例5：用实施例1相同的操作，不同之处在于：将柠檬酸溶解在无水乙醇中，配制为0.2mol/L的溶液；
实施例6：用实施例1相同的操作，不同之处在于：将柠檬酸溶解在无水乙醇和石油醚中，配制为0.24mol/L的溶液；
实施例7：用实施例1相同的操作，不同之处在于：将凝胶直接在马弗炉里于空气气氛下在550℃下煅烧2h。
注：以上列举的仅是发明的具体实施例，显然，本发明不限于以上实施例，还可以有许多变形，本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。
Claims (5)
1.一种多孔Ce-Zr基复合氧化物催化剂的制备方法，其特征在于，采用无模板剂-溶胶凝胶法，在混合金属盐溶液中加入造孔剂制得。
2.根据权利要求1所述Ce-Zr基复合氧化物催化剂的制备方法，其特征在于，造孔剂为草酸、柠檬酸与另一种或多种有机溶液的混合溶液。
3.根据权利要求2所述的造孔剂，其特征在于，所述的另一种或多种有机溶液是乙醇，或乙醇与乙二醇、环己烷、石油醚、正己烷等其中一种或多种有机溶剂的混合溶液。
4.根据权利要求1所述的一种多孔Ce-Zr基复合氧化物催化剂的制备方法，其特征在于，所述的金属盐溶液为过渡金属的硝酸盐或乙酸盐溶解到乙醇所形成的溶液中。
5.根据权利要求1或2或4所述的一种多孔Ce-Zr基复合氧化物催化剂的制备方法，其特征在于，所述的过渡金属/(Ce+Zr)的摩尔比为1∶1，Ce/Zr的摩尔比为1∶0～0∶1。
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