CN114917949A - 一种钴铁氧体改性沸石的合成方法 - Google Patents
一种钴铁氧体改性沸石的合成方法 Download PDFInfo
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Abstract
本发明公布了一种钴铁氧体改性沸石的合成方法，属于新材料领域。合成方法包括，通过共沉淀得到钴铁氧体前驱体，然后将其置于水热法制备沸石的反应溶液中，混合均匀后进行水反应热。将水热反应产生的固体产物洗至中性，固液分离后烘干即可获得钴铁氧体改性的沸石颗粒。本发明方法不但实现了沸石表面的钴铁氧体包覆和功能化，而且对沸石赋磁，使其可以高效磁分离。本发明方法将沸石的改性过程分两步完成，产物结构可精确控制，经简单改造后即可进行工业生产。所得钴铁氧体包覆的沸石可具有高级氧化催化、选择性吸附、化学催化等性能，磁分离效率>98％，在环保、化工、催化合成、温室气体转化等领域具有广泛应用潜力。
Description
一、技术领域
本发明涉及新材料领域，涉及一种钴铁氧体改性沸石的合成方法，具体地说是一种利用共沉淀-水热合成法制备磁性金属氧化物改性沸石的方法。
二、背景技术
沸石由于具有高比表面积，耐高温性、耐腐蚀性等特性，在工业生产和环保领域可以当作吸附材料和多相催化过程中催化剂的支撑材料。通过过渡金属氧化物改性可使沸石产生多功能性，改性沸石在吸附过程和催化反应中表现出优异的催化活性与选择性。在高级氧化技术中，Co2+具有较好的催化活性，因此，钴氧化物成为一个研究热点。CoFe2O4是一种磁性尖晶石铁素体，铁氧体与Co的杂化可以增强对氧化剂的活化作用，是一种很好的催化剂。传统的催化剂很难分离固体和液体，需要离心机来完成这个过程，这浪费了大量的能量。CoFe2O4是一种容易从水溶液中分离出来的铁磁剂，钴与铁之间的强金属键可以减少氧化反应过程中钴的浸出，这是CoFe2O4作为活化剂的特殊优点。然而，CoFe2O4的磁性导致其容易在水中团聚，减少了对活性位点的暴露，从而降低了CoFe2O4的活化效率。因此，将CoFe2O4包覆于沸石表面即可以利用沸石比表面积大的优点增加氧化剂与被氧化物与活性点位的接触，又能借助铁酸钴的磁性轻易固液分离。
当前对沸石改性的方法多为浸渍法。公开号CN114054075A的专利，通过将沸石置于梯度变化的改性溶液中多步浸渍，得到多元金属复合改性沸石分子筛催化剂。公开号为CN110170338A的专利，通过分步浸渍并控制微结晶的方法制备了Zr-Cu改性沸石双功能沸石离子交换剂。而浸渍法通常具有耗时较长、工艺复杂、产品性质不稳定、产生废液较多且固液分离困难等缺点。对沸石改性的方法还有水热合成法。公开号CN113751033A的专利使用了水热法合成了一种MOF改性沸石负载BiOX/TiO2光催化材料。但该材料制备时间较长且回收困难。改性沸石催化剂在工业生产中通常在液体条件下使用，由于其粒径小，因此很难固液分离，这不仅将严重影响了沸石的循环利用，而且大大推高了生产成本。因此将沸石磁性化，可以利用磁分离技术实现其高效固液分离。
三、发明内容
基于当前沸石改性存在的诸多问题，如改性周期长，产品品质不稳定等不足制出，本发明是一种在沸石表面包覆钴铁氧体进行改性的工艺方法，使其即具有高催化活性且能高效磁分离。钴铁氧体改性后的沸石，即能借助沸石的高比表面积避免催化剂的团聚，增加活性点位的暴露，又能借助磁性使其更易固液分离。此方法制备的改性沸石结构稳定、回收率高、催化活性高。
本发明一种钴铁氧体改性沸石的合成方法，包括如下步骤：
步骤1：将煤矸石破碎，选出200目筛下物进行750℃-850℃煅烧2h-4h，使用1mol/L硫酸浸泡后洗净烘干。
步骤2：将步骤1处理过的煤矸石与NaOH 1：1-1:2混合均匀研磨，400℃-500℃煅烧2h，研磨。
步骤3：将钴盐与铁盐混合溶解(Co与Fe摩尔比为1：2)，钴盐添加量为步骤2处理过的煤矸石质量的1/6-1/2。加热搅拌至75℃-90℃过程中滴加1-2.5mol/L的氢氧化钠溶液，使pH>12，继续加热至沸腾五分钟，得到褐色共沉淀物，即钴铁氧体前驱体。
步骤4：将步骤2处理后的煤矸石与钴铁氧体前驱体混合，加入硅酸钠(与煤矸石质量比为1：6)混合均匀后90℃-110℃水热6h-24h。
步骤5：将水热产物洗至中性，固液分离后烘干，即可得到钴铁氧体改性沸石。
优选地，所述钴盐添加量是碱熔后煤矸石与钴盐的质量比，三价铁盐的添加量是二价钴盐摩尔量的两倍。
优选地，钴盐与碱熔煤矸石的比例可在1：6到1：2范围内可调。使用的钴盐和铁盐可为实验室常见的CoCl2、Co(NO3)2、FeCl3、Fe(NO3)3等。
优选地，所制备的改性沸石中的沸石种类为Na-A型沸石。
技术效果
与已有技术相比，本发明技术方法具有以下优势：
1、催化活性高，适用于各种高级氧化中的氧化剂。
2、金属氧化物改性和磁性化一步完成，工艺简单，产品品质稳定，产生废液较少。
3、使用煤矸石为原料，来源广泛，成本低廉，易于工业化生产。
四、附图说明
下面结合附图和实施例对本发明进一步说明。
图1钴铁氧体改性磁性沸石的扫描电镜图和EDS能谱面扫描图。
图2为钴铁氧体改性磁性沸石的生成图。
图3为钴铁氧体改性磁性沸石的室温磁滞回线图。
图4为不同剂量钴铁氧体改性磁性沸石作为催化剂降解水中难处理的2-氯-4-硝基苯酚的图。
图5钴铁氧体改性磁性沸石的可重复性测试中去除率的图。
五、具体实施方式
以下结合附图及实施例对本发明做进一步详细描述。
实施例1：
1、煤矸石预处理
(1)将煤矸石破碎，选出200目筛下物进行800℃煅烧2h，使用1mol/L硫酸浸泡后洗净烘干，然后与NaOH 1：1.5混合均匀研磨，400℃煅烧2h，研磨。
2、钴铁氧体改性磁性沸石制备
将CoCl2与FeCl3混合溶解(CoCl2与FeCl3摩尔比为1：2)，CoCl2添加量为预处理煤矸石质量的1/6-1/2。将Co和Fe混合溶解滴入1.25mol/LNaOH溶液中，加热搅拌至沸腾5min，生成褐色共沉淀物。将预处理的煤矸石与钴铁共沉淀物混合，加入硅酸钠(与煤矸石质量比为1：6)混合均匀后90℃水热9h。
3、烘干及后处理
利用手磁块将产物中的磁性颗粒分离出来，用水清洗2遍，在105℃下真空干燥3小时，钴铁氧体改性磁性沸石。
参阅图1-3，从图1中可以看出，改性沸石颗粒粒径为2μm左右，CoFe2O4包覆于沸石表面。
图2为钴铁氧体改性磁性沸石，可知在沸石生成过程中CoFe2O4也在沸石表面生成。
图3为钴铁氧体改性磁性沸石的室温磁滞回线，可知其具有强磁性，可在磁场中实现高效固液分离。
实施例2：
利用钴铁氧体改性磁性沸石活化过硫酸氢钾降解50mg/L亚甲基蓝染料，60min即可完全降解。
参阅图4-5，图4为不同剂量钴铁氧体改性磁性沸石作为催化剂降解水中难处理的2-氯-4-硝基苯酚，当用量达到0.3g/L去除率即可在60min达到100％。
图5为钴铁氧体改性磁性沸石的可重复性测试，可知经过五次循还后去除率仍能达到81％。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (3)
1.一种钴铁氧体改性沸石的合成方法，其特征在于，包括如下步骤：
步骤1：将二价钴盐和三价铁盐按钴和铁摩尔比1：2混合溶解；混合液加热搅拌，加热75℃-90℃过程中滴加1-2.5mol/L的氢氧化钠溶液，使pH>12，继续加热至沸腾五分钟，得到褐色共沉淀物，即钴铁氧体前驱体；改性的钴铁氧体添加量根据需求改变钴盐和铁盐的量，Co2+：Fe3+为1：2；
步骤2：将煤矸石破碎筛分，煅烧后经过酸浸，碱熔，得到预处理后的煤矸石；预处理后的煤矸石添加一定量硅酸钠与补充硅源，加入去离子水搅拌均匀；
步骤3：将处理后的煤矸石硅酸钠混合物与钴铁氧体前驱体混合均匀，放入反应釜中90℃-110℃水热6h-24h；
步骤4：利用磁分离技术将水热产物的磁性颗粒分离处理，用去离子水水清洗后烘干，即可获得磁性钴铁氧体包覆的沸石颗粒。
2.根据权利要求1所述的合成方法，其特征在于：所述二价钴盐和三价铁盐均为可溶性盐，包括CoCl2、Co(NO3)2、FeCl3、Fe(NO3)3。
3.根据权利要求1所述的合成方法，其特征在于：所述钴盐添加量是碱熔后煤矸石与钴盐的质量比，三价铁盐的添加量是二价钴盐摩尔量的两倍；钴盐与碱熔煤矸石的比例在1：6到1：2范围内可调。
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