CN109395765A - 一种适用于低温等离子处理有机废气的催化剂的制备及其应用 - Google Patents
一种适用于低温等离子处理有机废气的催化剂的制备及其应用 Download PDFInfo
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Abstract
本发明属于催化剂领域,涉及一种适用于低温等离子处理有机废气的催化剂的制备及其应用。通过浸渍法制备催化剂。将过渡金属银和锰与SBA‑15分子筛按一定比例混合搅拌、超声振动、静置、干燥、焙烧、冷却后制得催化剂。本发明制得催化剂可大幅提高降解VOC效率、抑制有害副产物的产生,能够进一步改进低温等离子体处理有机废气存在的能量利用率低,处理效果差的缺点,同时降低能耗,减少二次污染。
Description
技术领域
本发明属于催化剂领域,涉及一种适用于低温等离子处理有机废气的催化剂的制备及其应用。
技术背景
近年来,大范围的空气质量不达标情况在全国范围内广泛出现,其中挥发性有机污染物(VOCs)是目前大气区域复合污染的重要前提物之一。由于其来源广泛、排放量大及排放行业相对分散等特点,排放后主要以气体状态或附着于颗粒物上而存在于空气中且直接或间接地危害人体健康,可随气流扩散进一步扩大污染范围。因此,对VOCs的控制已成为治理当前大气区域复合污染的一项重要工作。
挥发性有机物VOCs(volatile organic compounds),是指常温下,沸点50℃~260℃的各种有机化合物。按其化学结构,可以进一步分为:烷类、芳烃类、酯类、醛类和其他等。目前已鉴定出的有300多种。最常见的有苯、甲苯、二甲苯、苯乙烯、三氯乙烯、三氯甲烷、三氯乙烷、二异氰酸酯(TDI)、二异氰甲苯酯等。
针对VOCs的治理,目前还主要依靠末端治理技术。由于排放VOCs的行业分散,浓度差异大,且含有大量微粒物质,成分复杂,因此仅仅依靠单一技术难以达到治理效果,而等离子体降解技术越来越受重视。但等离子体单独降解VOCs因选择性低,且同时会产生一些有毒副产物而限制了它的实际应用。催化剂由于具有较好的产物选择性,同时可以降低反应的活化能,从而达到节能的要求。因此,可以利用等离子体能在常温常压下进行反应和催化剂具有高选择性的特点,将两者的优势结合起来,应用于VOCs降解。
低温等离子体协同催化降解VOCs具有操作设备简单、操作条件可在常温常压下进行等优点。将低温等离子体技术与催化剂的应用相结合,使得该技术具有CO2选择性高、生成副产物极少、降解效率高、反应条件温和等特点。
SBA-15是属于介孔分子筛的一种,它的合成是近年来兴起的又一项重要化工技术。SBA-15的合成过程:用中性表面活性剂P123(S0),和中性无机硅物种(I0)通过氢键键合,不存在强的静电作用,并随硅烷醇的进一步水解、缩合导致短程六边形胶粒的堆积和骨架的形成。SBA-15的合成条件温和,表面活性剂易除去,且不易引起结构坍塌;中性表面活性剂与中性无机前驱体间的排斥力比离子表面活性剂与带电荷的无机前驱体间的排斥力小得多,能够形成较厚的孔壁,进而提高了分子筛骨架结构的热及水热稳定性。其在催化、分离、生物及纳米材料等领域有广泛的应用前景,而其水热稳定性高等优势为催化、吸附分离以及高等无机材料等学科开拓了新的研究领域。
发明内容
本发明的目的是针对现有低温等离子体处理有机废气存在的不足,提供一种钙态矿型催化剂。
本发明的又一目的是提供应用于该催化剂的制备方法。
本发明的又一目的是提供该催化剂的应用。
本发明的目的可通过如下技术方案实现:
一种适用于低温等离子处理有机废气的催化剂,主要由分子筛以及负载在分子筛上的过渡金属和稀土金属组成;所述的分子筛为SBA-15分子筛;所述的稀土金属为铈,所述的过渡金属为锰或银;过渡金属与分子筛摩尔比为1:(1~10);稀土金属与过渡金属元素摩尔比为(0.2~2):1。
所述的催化剂通过以下方法制备得到:取足够量的SBA-15分子筛,在真空、80℃状态下干燥12小时;分别配制稀土金属硝酸盐溶液、过渡金属硝酸盐溶液,将稀土金属硝酸盐溶液、过渡金属硝酸盐溶液按照稀土金属与过渡金属元素摩尔比为(0.2~1.5):1混合制备稀土金属与过渡金属混合液;按照过渡金属与分子筛摩尔比在1:(1~10)的比例,将SBA-15分子筛加入到上述配置好的溶液中,在超声振动条件下放置12小时;将上述所得混合物在120℃下干燥12小时,得到的分子筛接着先在400℃下焙烧4小时,然后按照100℃/h升温焙烧4小时后得到所述催化剂。
所述的过渡金属硝酸盐溶液是将过渡金属硝酸盐用去离子水溶解,得到稀土金属硝酸盐溶液,其中过渡金属摩尔浓度为1~5mol/L。
所述的稀土金属硝酸盐溶液是将稀土金属硝酸盐用去离子水溶解,得到稀土金属硝酸盐溶液,其中稀土金属摩尔浓度为0.5~5mol/L。
本发明所述的催化剂应用于低温等离子体处理废气的应用中。
所述的有机废气优选挥发性有机物VOCs;进一步优选甲苯、三甲胺。
有益效果
本发明催化剂用于强化低温等离子处理有机废气性能,具有以下优点:
1、本发明研究开发的催化剂应用于低温等离子反应体系中,其区别于传统处理废气的方法如催化燃烧法、吸附法等,可在常温常压的电场环境下应用催化剂去降解废气中的有机污染物。
2、通过负载特定的稀土金属铈,过渡金属银或锰在特定条件、配比并优化制备过程,使得催化剂表面能够形成钙态矿型结构,强化低温等离子反应体系电学性能。同时铈元素能够提高过渡金属的分散度。
3、分子筛多孔特性能够延长介质阻挡放电反应器的停留时间,同时抑制臭氧等副产物的产生,反应过程中产生的少量臭氧可以进一步裂解为氧化活性强的氧原子,进一步降解污染物,减少二次污染。
4、本催化剂的使用,能够进一步改进低温等离子体处理有有机废气产生二次污染的问题,更大程度减少CO的产生,提高该反应体系能量利用效率,改善处理效果,同时降低能耗。
5、该发明研究开发的催化剂可以提高介质阻挡放电反应器输出功率,提高污染物去除效率。
具体实施方式:
实施例1
以下实施例使用的催化剂通过以下方法制备得到:
配制硝酸锰溶液1mol/L,硝酸铈溶液1mol/L。取150ml硝酸锰(0.15mol)溶液,250ml硝酸铈(0.25mol)溶液混合均匀后加入1molSBA-15分子筛,超声振动12h后静置8h。接着在于120℃下干燥8小时,干燥后的分子筛颗粒在400℃下焙烧4h,再按照100℃/h升温焙烧4小时得到催化剂。
废气为甲苯,空气占混合废气总量(甲苯+空气)的80%(V/V),混合废气流量为1L/min。
DBD反应器外管内径20mm,外径25mm;内管外径7mm,内径5mm。长200mm,内管外管之间均匀装填有催化剂,高压电源输出电压为5kV,甲苯的转化率为90%,尾气经由尾气收集装置吸附排空。
对比例:
废气为甲苯,空气占混合废气总量(甲苯+空气)的80%(V/V),混合废气流量为1L/min。
DBD反应器外管内径20mm,外径25mm;内管外径7mm,内径5mm。长200mm,不填充催化剂,高压电源输出电压为5kV,甲苯的转化率为30%,尾气经由尾气收集装置吸附排空。
实施例2
配制硝酸银溶液1.5mol/L,硝酸铈溶液1mol/L。取500ml硝酸银(0.75mol)溶液,500ml硝酸铈(0.5mol)溶液混合均匀后加入2molSBA-15级分子筛,超声振动8h后静置12h。接着在于110℃下干燥6小时,干燥后的分子筛颗粒在600℃下焙烧4h,再按照50℃/h升温焙烧4小时得到催化剂。
废气为三甲胺,空气占混合废气总量(三甲胺+空气)的85%(V/V),混合废气流量为1L/min。
DBD反应器外管内径20mm,外径25mm,内管外径7mm,内径5mm。长150mm,内管外管之间均匀装填有催化剂,高压电源输出电压为7.5kV,三甲胺的转化率为80%,尾气经由尾气收集装置吸附排空。
对比例:
废气为三甲胺,空气占混合废气总量(三甲胺+空气)的85%(V/V),混合废气流量为1L/min。
DBD反应器外管内径20mm,外径25mm,内管外径7mm,内径5mm。长150mm,不填充催化剂,高压电源输出电压为7.5kV,三甲胺的转化率为46%,尾气经由尾气收集装置吸附排空。
实施例3
配制硝酸银溶液2mol/L,硝酸锰溶液1mol/L。取250ml硝酸银(0.5mol)溶液,250ml硝酸锰(0.25mol),500ml硝酸铈(0.5mol)溶液混合均匀后加入2molSBA-15分子筛,超声振动6后静置10h。接着在于140℃下干燥6小时,干燥后的分子筛颗粒在400℃下焙烧4h,再按照80℃/h升温焙烧5小时得到催化剂。
废气为甲苯,空气占混合废气总量(甲苯+空气)的80%(V/V),混合废气流量为1L/min。
DBD反应器外管内径20mm,外径25mm;内管外径7mm,内径5mm。长200mm,内管外管之间均匀装填有催化剂,高压电源输出电压为5kV,甲苯的转化率为95%,尾气经由尾气收集装置吸附排空。
对比例:
废气为甲苯,空气占混合废气总量(甲苯+空气)的80%(V/V),混合废气流量为1L/min。
DBD反应器外管内径20mm,外径25mm;内管外径7mm,内径5mm。长200mm,不填充催化剂,高压电源输出电压为5kV,甲苯的转化率为30%,尾气经由尾气收集装置吸附排空。
实施例4
配制硝酸银溶液4mol/L,硝酸锰溶液1mol/L。取125ml硝酸银(0.5mol)溶液,250ml硝酸锰(0.25mol)溶液混合均匀后加入3mol二氧化硅粉末,搅拌8h后静置16h。接着在于150℃下干燥4小时,干燥后的二氧化硅粉末在700℃下焙烧8h得到催化剂。
废气为甲苯,空气占混合废气总量(甲苯+空气)的80%(V/V),混合废气流量为1L/min。
DBD反应器外管内径20mm,外径25mm;内管外径7mm,内径5mm。长200mm,反应管出气端用石英棉填塞催化剂,高压电源输出电压为5kV,甲苯的转化率为40%,尾气经由尾气收集装置吸附排空。
Claims (10)
1.一种适用于低温等离子处理有机废气的催化剂,其特征在于主要由分子筛以及负载在分子筛上的过渡金属和稀土金属组成;所述的分子筛为SBA-15分子筛;所述的稀土金属为铈,所述的过渡金属为锰或银;过渡金属与分子筛摩尔比为1:(1~10);稀土金属与过渡金属元素摩尔比为(0.2~2):1。
2.根据权利要求1所述的催化剂,其特征在于所述的催化剂通过以下方法制备得到:取SBA-15分子筛,在真空、80℃状态下干燥12小时;分别配制稀土金属硝酸盐溶液、过渡金属硝酸盐溶液,将稀土金属硝酸盐溶液、过渡金属硝酸盐溶液按照稀土金属与过渡金属元素摩尔比为(0.2~1.5):1混合制备稀土金属与过渡金属混合液;按照过渡金属与分子筛摩尔比在1:(1~10)的比例,将SBA-15分子筛加入到上述配置好的溶液中,在超声振动条件下放置12小时;将上述所得混合物在120℃下干燥12小时,得到的分子筛接着先在400℃下焙烧4小时,然后按照100℃/h升温焙烧4小时后得到所述催化剂。
3.根据权利要求2所述的催化剂,其特征在于所述的过渡金属硝酸盐溶液是将过渡金属硝酸盐用去离子水溶解,得到稀土金属硝酸盐溶液,其中过渡金属摩尔浓度为1~5mol/L。
4.根据权利要求2所述的催化剂,其特征在于所述的稀土金属硝酸盐溶液是将稀土金属硝酸盐用去离子水溶解,得到稀土金属硝酸盐溶液,其中稀土金属摩尔浓度为0.5~5mol/L。
5.权利要求1所述的催化剂的制备方法,其特征在于取SBA-15分子筛,在真空、80℃状态下干燥12小时;分别配制稀土金属硝酸盐溶液、过渡金属硝酸盐溶液,将稀土金属硝酸盐溶液、过渡金属硝酸盐溶液按照稀土金属与过渡金属元素摩尔比为(0.2~1.5):1混合制备稀土金属与过渡金属混合液;按照过渡金属与分子筛摩尔比在1:(1~10)的比例,将SBA-15分子筛加入到上述配置好的溶液中,在超声振动条件下放置12小时;将上述所得混合物在120℃下干燥12小时,得到的分子筛接着先在400℃下焙烧4小时,然后按照100℃/h升温焙烧4小时后得到所述催化剂。
6.根据权利要求5所述的催化剂的制备方法,其特征在于所述的过渡金属硝酸盐溶液是将过渡金属硝酸盐用去离子水溶解,得到稀土金属硝酸盐溶液,其中过渡金属摩尔浓度为1~5mol/L。
7.根据权利要求5所述的催化剂的制备方法,其特征在于所述的稀土金属硝酸盐溶液是将稀土金属硝酸盐用去离子水溶解,得到稀土金属硝酸盐溶液,其中稀土金属摩尔浓度为0.5~5mol/L。
8.权利要求1所述的催化剂在低温等离子体处理有机废气中的应用。
9.根据权利要求8所述的应用,其特征在于所述的有机废气为挥发性有机物VOCs。
10.根据权利要求9所述的应用,其特征在于所述的有机废气包括甲苯、三甲胺。
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