CN112007656A - 一种降解VOCs的Cu-Mn-Ce-La复合催化剂及其制备方法和应用 - Google Patents
一种降解VOCs的Cu-Mn-Ce-La复合催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及挥发有机气体废气处理技术领域，公开一种降解VOCs的Cu‑Mn‑Ce‑La复合催化剂及其制备方法和应用，通过精确调控多种元素的比例，制备含催化剂的溶胶凝胶，该复合催化剂粒径小、比表面积高，表现出了非常优良的低温高效催化效率。用于去除有机挥发性废气，特别是对二甲苯废气有着非常优良的低温催化效果，T90可低至230℃。
Description
技术领域
本发明涉及挥发有机气体废气处理技术领域，具体涉及一种降解VOCs的Cu-Mn-Ce-La复合催化剂及其制备方法和应用。
背景技术
挥发性有机化合物(VOCs)是指VOCs是指常温下饱和蒸汽压大于70Pa、常压下沸点在260℃以下的有机化合物。VOC是一大类在室温下容易蒸发的碳基化学物质。
挥发性有机化合物(VOCs)主要包括卤代化合物(例如氯仿，氯苯和三氯乙烯)，醛类(例如甲醛)，芳族化合物(例如二甲苯、甲苯和苯等)，多环芳烃(例如萘，菲)，醇类(例如乙醇)和酮类(例如丙酮)。它们危害环境和人类健康，VOCs不仅有毒，而且是臭氧，光化学雾和二次气溶胶的前体，是造成空气污染的主要原因。VOCs的主要来源是人类活动，例如利用车辆运输，溶剂，建筑材料，装饰材料，纤维材料，办公用品等。因此，由VOCs引起的污染已成为严重的问题，并且VOCs的去除已经引起了广泛的关注。
数十年来，已经采用了包括吸附，吸收，生物降解，膜分离，热焚烧和燃烧，热解，光催化氧化在内的各种技术来去除VOCs。在所有这些方法中，催化氧化是最有效，最环保的方法，通过该方法，VOCs可以在相对较低的温度下转化为无害的CO2和H2O物质。迄今为止，催化剂大致分为二组，即贵金属系催化剂和过渡金属氧化物催化剂，已经被广泛开发用于VOCs的催化氧化。贵金属催化剂具有很高的活性，但是它们非常昂贵，易于烧结或在使用中因中毒而失活。与贵金属相反，过渡金属氧化物价格便宜，易于获得，在低温下具有很强的活性，因此被认为是一种竞争性候选材料。
研究发现，单-过渡金属氧化物的催化剂总是具有相对较低的活性，为了解决这个问题，已经广泛地合成并应用了混合过渡金属氧化物催化剂。常用的过渡金属氧化物包括TiO2、Co3O4、MnOx、CuO、CeO2、Fe2O3和Cr2O3等。例如，将Ce物种掺入Co氧化物中可能会改变氧化还原性质和Co-Ce混合氧化物催化剂的化学状态，因为氧化钴可以提供活性的流动氧，而氧化铈具有较高的储氧量和具有氧化还原性质的释放能力(偶合Ce4+/Ce3+)，可以为氧化反应提供更多的活性氧，因此，它们的协同作用可以增强VOCs氧化的催化活性。两种或两种以上非贵金属氧化物制备的催化剂具有较好的低温催化活性和经济性，是VOCs催化燃烧重要的发展研究方向。
公布号为CN 108940302 A公开了一种活性组分为锰、铈、钴的金属氧化物催化剂，其中活性组分中Ce:Mn:Co摩尔比为1:(1～8):(1～2)。发明还公开了该催化剂的制备方法为溶胶凝胶法制备，选择柠檬酸作为络合剂。所述的在550℃条件下焙烧而成的2MnCeCo催化剂在257℃对氯苯的转化率可达到92.1％，且在350℃条件下稳定运行80h，对氯苯的转化率稳定保持在99.0％以上。虽然上述的催化剂具有低温活性较高，原料价格低廉的优点，但是降解时间过长，降解效果仍具有较大的提升空间。
公布号为CN 101767015 A公开了一种治理“三苯”废气的铜锰基催化燃烧催化剂及其制备方法。发明选用铜锰复合氧化物为活性组分通过浸渍法负载于复合载体上得到负载型的非贵金属复合氧化物催化剂。催化剂通式为Cua(Mn)bO4/A，其中a为0～1，b为0～2。所述催化剂中A为复合载体，Cua(Mn)bO4为活性组分。所述的复合载体组成按重量百分比为：传统载体20～80％，CeO2(或ZrO2)5～40％。所述活性组分按重量百分比为：CuO5～40％、MnO25～40％。发明采用已成型的载体浸渍，省去了催化剂成型工艺，工艺简单，成本降低。同时复合载体中添加一些稀土储氧组分，可大大降低有机物燃烧反应温度，提高催化低温活性，还可大幅度延长催化寿命。在反应温度200～550℃，苯的转化率达到30％～90％，甲苯的转化率达到40％～100％，二甲苯的转化率达到40％～100％。虽然其工艺简单，成本低，但是降解效果不够理想，而且相比于溶胶凝胶法，浸渍法存在载体上活性组分负载不均匀，催化剂负载量不好控制的问题。
公布号为CN 106179393 A公开了用于降解VOCs的锰铜基催化剂的制备方法，利用高锰酸钾和乙酸铜的自蔓延反应，快速制备能催化降解甲苯的锰铜催化剂，并通过改变Mn、Cu摩尔比，来调控锰铜基催化剂的催化活性，可使催化剂在常压，空速为30000mlgcatalyst-1h-1，将1000ppm甲苯和空气混合气体在303℃—340℃反应温度范围区间完全(100％)转化成CO2和H2O，该催化剂所用原材料价格低廉、制备工艺简单、高效、实用性强，但在制备工艺中不会产生NOx等有毒有害气体，自蔓延反应工艺参数控制要求较严，而且降解效果不够理想。
发明内容
本发明旨在提供一种具有极强催化活性的复合催化剂，在低温下具有高效催化效率，能够更好的催化降解VOCs废气，制备工艺简单，易于控制。
为实现上述目的，本发明采用的技术方案是：
一种降解VOCs的Cu-Mn-Ce-La复合催化剂，各元素以原子摩尔比计，Cu:Mn:Ce:La＝1～2:1～2:1～2:1～2。
本发明利用本发明的技术原理如下：以金属硝酸盐、柠檬酸为原料,按照一定配比溶解形成均匀的溶液。在一定温度和pH值下,利用柠檬酸的羧基基团对铵离子的稳定作用,再通过N原子给出电子形成电子对,与金属离子进行络合形成柠檬酸络合盐。经脱水、干燥成蜂窝状干凝胶。将其移入一定温度的恒温烘箱中或者在空气中点燃，干凝胶自一处发火剧烈燃烧并平稳向前推进直至生成蓬松的粉末，从而得到多种元素复合的催化剂。
本发明提供的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，包括如下步骤：
(1)将硝酸铜、硝酸锰、硝酸铈和硝酸镧分别溶解于溶剂形成前驱体溶液；
(2)按照各元素原子摩尔比Cu:Mn:Ce:La＝1～2:1～2:1～2:1～2的比例配置各前驱体溶液，形成混合溶液；
(3)向步骤(2)中的混合溶液中加入柠檬酸，再搅拌下加入氨水形成溶胶；
(4)将步骤(3)得到的溶胶搅拌、干燥、煅烧、研磨得到所述Cu-Mn-Ce-La复合催化剂。
本发明以各前驱体的硝酸盐与柠檬酸络合形成柠檬酸络合物，经脱水、干燥成蜂窝状干凝胶，柠檬酸的羧基基团对铵离子的稳定作用,再通过N原子给出电子形成电子对,与金属离子进行络合形成柠檬酸络合盐，络合物之间相互交联缩聚逐渐形成三维立体网络,随着水分和其他溶剂的蒸发,溶胶慢慢失去流动性从而向凝胶转变,进一步脱水并降温之后形成干凝胶，将多种元素相对均匀的稳固在干凝胶内，从而获得铜、锰、铈和镧复合的催化剂。
其中各元素的原子摩尔比对催化剂的催化效果起到关键性作用，不同元素含量多少对催化剂的催化效果有很大区别，发明人经试验发现，当各元素原子摩尔比Cu:Mn:Ce:La＝1～2:1～2:1～2:1～2时，催化剂的催化效果良好。特别是当Cu:Mn:Ce:La＝1:2:1:1时，该复合催化剂对对二甲苯有着良好的常温和低温催化效果，降解效率最高。
步骤(1)中，所述的溶剂包括水、乙醇、乙二醇等，易溶解各硝酸金属盐即可。
所述前驱体溶液中前驱体的摩尔浓度为0.2～1.5mol/L，以各前驱体能够完全溶解为宜，浓度过低的话，需要溶液的量就会变大，去除水分的时间会变长，影响实验时间；浓度过高的话，需要溶液的量就会变小，实验误差会变大，也易导致金属盐溶解效果不好，影响催化剂最终的催化效果。
所述柠檬酸的摩尔量与混合溶液中金属总摩尔量的比为1～1.5:1。本专利中以柠檬酸为络合剂，如果柠檬酸比例过低，则无法和所有的金属离子形成络合物，进而影响催化剂的性能；如果柠檬酸比例过高，则柠檬酸会有所剩余，不仅造成原料的浪费，也对后续杂质处理产生影响。
步骤(3)中，加入氨水后的溶胶的pH为7～8。pH值的调节也是影响溶胶凝胶自燃烧反应的重要因素之一,它不但能影响原料溶液中金属络合物的形成,而且能够影响自燃烧反应的剧烈程度。此范围是经过多次试验得来，若PH不到此范围则溶液无法形成溶胶状态，若PH大于此范围，则会直接生成沉淀，也无法形成溶胶。
所述氨水的浓度为0.5～2g/ml。。
步骤(4)中，搅拌温度为60～100℃，搅拌时间为20min以上。温度过低，不利于凝胶中水分和溶剂的脱除，温度过高，可能造成溶胶溅出，存在实验安全隐患，综合考虑温度控制在60～100℃。
步骤(4)中，干燥温度为80～120℃，干燥时间为1～6h，干燥以去除凝胶中的水分、溶剂，络合物之间相互交联缩聚逐渐形成三维立体网络,随着水分和其他溶剂的蒸发,溶胶慢慢失去流动性从而向凝胶转变。
所述煅烧温度为200～600℃，煅烧时间为1～6h。本发明中采用的四种硝酸盐的最高分解温度是200℃，故最低煅烧温度要设在200℃以上，温度若低于200℃，达不到煅烧效果，催化剂催化效果较差，但温度太高会导致凝胶的结构发生变化，催化效果也不好。
优选地，煅烧温度为300～400℃，该煅烧温度下得到的催化剂低温(100～200℃)和高温(200℃以上)催化效率最佳。
本发明还提供一种催化降解对二甲苯废气的方法，将权利要求1所述的复合催化剂催化降解对二甲苯废气，催化温度为100～250℃，空速为9000～72000h-1。
与现有技术相比，本发明具有以下有益效果：
(1)本发明中的Cu-Mn-Ce-La复合催化剂粒径小、比表面积高，表现出了非常优良的低温高效催化效率。
(2)本发明的制备工艺简单，催化剂产出量大，对有机废气，特别是对二甲苯有着十分高效的去除效果，其中，Cu-Mn-Ce-La针对对二甲苯，在浓度为1000mg/m3以下的对二甲苯条件下，表现出非常优良的低温高效催化效率，T90可低至230℃。
(3)本发明的催化剂保证在催化燃烧降解苯系物的同时温度低于工业上已投入使用的大部分催化剂，通过不同的铜、锰、镧、铈原子比，获得最适合较低温催化燃烧的催化剂，投入实际生产将具有很大的应用价值与广阔的应用前景。
附图说明
图1为不同摩尔比的催化剂降解对二甲苯的降解率。
图2为不同煅烧温度的各催化剂降解对二甲苯的降解率。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。本领域技术人员在理解本发明的技术方案基础上进行修改或等同替换，而未脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围内。
实施例1
(1)配制0.5mol/L的硝酸铜水溶液、硝酸锰水溶液、硝酸铈水溶液和硝酸镧水溶液；
(2)分别取5ml硝酸铜水溶液、5ml硝酸锰水溶液、5ml硝酸镧水溶液和5ml的硝酸铈水溶液，混合配制成混合溶液，即各元素原子摩尔比Cu:Mn:Ce:La为1:1:1:1；
(3)向混合溶液中加入2.1g的柠檬酸，搅拌下缓慢滴加0.91g/ml至混合溶液的pH为7得到溶胶；
(4)将得到的溶胶磁力搅拌下80℃持续搅拌30min后，再置于烘箱中120℃干燥4h，再于马弗炉中400℃煅烧4h，研磨得到Cu-Mn-Ce-La复合催化剂。
实施例2
(1)配制0.5mol/L的硝酸铜水溶液、硝酸锰水溶液、硝酸铈水溶液和硝酸镧水溶液；
(2)分别取4ml硝酸铜水溶液、8ml硝酸锰水溶液、4ml的硝酸铈水溶液和4ml硝酸镧水溶液，混合配制成混合溶液，即各元素原子摩尔比Cu:Mn:Ce:La为1:2:1:1；
(3)向混合溶液中加入2.1g的柠檬酸，搅拌下缓慢滴加0.91g/ml至混合溶液的pH为7得到溶胶；
(4)将得到的溶胶磁力搅拌下80℃持续搅拌30min后，再置于烘箱中120℃干燥4h，再于马弗炉中400℃煅烧4h，研磨得到Cu-Mn-Ce-La复合催化剂。
实施例3
(1)配制0.5mol/L的硝酸铜水溶液、硝酸锰水溶液、硝酸铈水溶液和硝酸镧水溶液；
(2)分别取4ml硝酸铜水溶液、4ml硝酸锰水溶液、8ml的硝酸铈水溶液和4ml硝酸镧水溶液，混合配制成混合溶液，即各元素原子摩尔比Cu:Mn:Ce:La为1:1:2:1；
(3)向混合溶液中加入2.1g的柠檬酸，搅拌下缓慢滴加0.91g/ml至混合溶液的pH为7得到溶胶；
(4)将得到的溶胶磁力搅拌下80℃持续搅拌30min后，再置于烘箱中120℃干燥4h，再于马弗炉中400℃煅烧4h，研磨得到Cu-Mn-Ce-La复合催化剂。
实施例4
(1)配制0.5mol/L的硝酸铜水溶液、硝酸锰水溶液、硝酸铈水溶液和硝酸镧水溶液；
(2)分别取8ml硝酸铜水溶液、4ml硝酸锰水溶液、4ml的硝酸铈水溶液和4ml硝酸镧水溶液，混合配制成混合溶液，即各元素原子摩尔比Cu:Mn:Ce:La为2:1:1:1；
(3)向混合溶液中加入2.1g的柠檬酸，搅拌下缓慢滴加0.91g/ml至混合溶液的pH为7得到溶胶；
(4)将得到的溶胶磁力搅拌下80℃持续搅拌30min后，再置于烘箱中120℃干燥4h，再于马弗炉中400℃煅烧4h，研磨得到Cu-Mn-Ce-La复合催化剂。
实施例5
(1)配制0.5mol/L的硝酸铜水溶液、硝酸锰水溶液、硝酸铈水溶液和硝酸镧水溶液；
(2)分别取8ml硝酸铜水溶液、4ml硝酸锰水溶液、4ml的硝酸铈水溶液和8ml硝酸镧水溶液，混合配制成混合溶液，即各元素原子摩尔比Cu:Mn:Ce:La为1:1:1:2；
(3)向混合溶液中加入2.1g的柠檬酸，搅拌下缓慢滴加0.91g/ml至混合溶液的pH为7得到溶胶；
(4)将得到的溶胶磁力搅拌下80℃持续搅拌30min后，再置于烘箱中120℃干燥4h，再于马弗炉中400℃煅烧4h，研磨得到Cu-Mn-Ce-La复合催化剂。
实施例6
(1)配制0.5mol/L的硝酸铜水溶液、硝酸锰水溶液、硝酸铈水溶液和硝酸镧水溶液；
(2)分别取8ml硝酸铜水溶液、4ml硝酸锰水溶液、4ml的硝酸铈水溶液和4ml硝酸镧水溶液，混合配制成混合溶液，即各元素原子摩尔比Cu:Mn:Ce:La为1:2:1:1；
(3)向混合溶液中加入2.1g的柠檬酸，搅拌下缓慢滴加0.91g/ml至混合溶液的pH为7得到溶胶；
(4)将得到的溶胶磁力搅拌下80℃持续搅拌30min后，再置于烘箱中120℃干燥4h，再于马弗炉中300℃煅烧4h，研磨得到Cu-Mn-Ce-La复合催化剂。
实施例7
(1)配制0.5mol/L的硝酸铜水溶液、硝酸锰水溶液、硝酸铈水溶液和硝酸镧水溶液；
(2)分别取8ml硝酸铜水溶液、4ml硝酸锰水溶液、4ml的硝酸铈水溶液和4ml硝酸镧水溶液，混合配制成混合溶液，即各元素原子摩尔比Cu:Mn:Ce:La为1:2:1:1；
(3)向混合溶液中加入2.1g的柠檬酸，搅拌下缓慢滴加0.91g/ml至混合溶液的pH为7得到溶胶；
(4)将得到的溶胶磁力搅拌下80℃持续搅拌30min后，再置于烘箱中120℃干燥4h，再于马弗炉中250℃煅烧4h，研磨得到Cu-Mn-Ce-La复合催化剂。
应用例
取实施例1-7制备得到的复合催化剂0.15g，分别进行应用试验，将复合催化剂放入反应器中用石英棉固定，分别通入相同浓度和空速的含有一定浓度的对二甲苯废气，经过含有催化剂的固定反应床后再通入气相色谱，来检测对二甲苯的去除率。
其中反应气组成为：1000mg/m3的对二甲苯混合气，其中载气为79％氮气以及21％氧气，反应混合气的流速为100mL/min，空速为10000h-1。活性评价温度为100～250℃，设置不同的温度区间。
实施例1～5的复合催化剂降解实验效果如图1所示。由图1可知，Cu:Mn:Ce:La＝1:2:1:1时，该复合催化剂对对二甲苯有着良好的低温和高温催化效果，和其他几种比例相比，降解效率最高。
实施例1、6、7的复合催化剂降解对二甲苯的降解率如图2所示，由图2可知，催化剂煅烧温度为300℃时，催化剂低温降解效果最好。
Claims (10)
1.一种降解VOCs的Cu-Mn-Ce-La复合催化剂，其特征在于，各元素以原子摩尔比计，Cu:Mn:Ce:La＝1～2:1～2:1～2:1～2。
2.根据权利要求1所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，包括如下步骤：
(1)将硝酸铜、硝酸锰、硝酸铈和硝酸镧分别溶解形成前驱体溶液；
(2)按照各元素原子摩尔比Cu:Mn:Ce:La＝1～2:1～2:1～2:1～2的比例配置各前驱体溶液，形成混合溶液；
(3)向步骤(2)中的混合溶液中加入柠檬酸，再搅拌下加入氨水形成溶胶；
(4)将步骤(3)得到的溶胶搅拌、干燥、煅烧、研磨得到所述Cu-Mn-Ce-La复合催化剂。
3.根据权利要求2所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，所述前驱体溶液中前驱体的摩尔浓度为0.2～1.5mol/L。
4.根据权利要求2所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，所述柠檬酸的摩尔量与混合溶液中金属总摩尔量的比为1～1.5:1。
5.根据权利要求2所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，步骤(3)中，加入氨水后的溶胶的pH为7～8。
6.根据权利要求2所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，所述氨水的浓度为0.5～2g/ml。
7.根据权利要求2所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，步骤(4)中，搅拌温度为60～100℃，搅拌时间为20min以上。
8.根据权利要求2所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，步骤(4)中，干燥温度为80～120℃，干燥时间为1～6h。
9.根据权利要求2所述的降解VOCs的Cu-Mn-Ce-La复合催化剂的制备方法，其特征在于，所述煅烧温度为200～600℃，煅烧时间为1～6h。
10.一种催化降解对二甲苯废气的方法，其特征在于，将权利要求1所述的复合催化剂催化降解对二甲苯废气，催化温度为100～250℃，空速为9000～72000h-1。
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