CN104437351B - 一种分级孔凹凸棒石的制备方法及应用 - Google Patents
一种分级孔凹凸棒石的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了种分级孔凹凸棒石的制备方法，凹凸棒石黏土首先经酸溶液处理，除去其中的杂质和部分八面体阳离子，而后加入氟化物以除去其间的含硅化合物，经过滤、洗涤和干燥即得分级孔凹凸棒石材料。将其用作吸附剂，可选择性吸附二氧化碳；将其作为甲苯与苄基溴进行Friedel‑Crafts烷基化反应的催化剂，得到较高的转化率。本发明的分级孔凹凸棒石的制备方法，其包括以下步骤：称取凹凸棒石黏土于玻璃烧瓶中，加入酸溶液，在60‑110℃下回流搅拌2‑12h后，冷至室温，转至烧杯中，向其中加入氟化物进行反应，再经过滤、洗涤和干燥，即得到分级孔凹凸棒石。
Description
技术领域
本发明涉及一种凹凸棒石的制备方法及应用，更具体地说涉及一种分级孔凹凸棒石的制备方法及其应用。
背景技术
凹凸棒石黏土是一种具有链层状结构的富镁铝硅酸盐天然矿物。我国江苏、安徽、山东、甘肃和辽宁等地已探明许多凹凸棒石黏土矿藏。我国凹凸棒石黏土矿资源储量能够满足近期工业生产的需求，并且与世界其他各国相比具有较明显的优势(王艺洁，任珺，陶玲等，矿产保护与利用，2012，(4)：44-47)。凹凸棒石具有特殊的晶体结构：其基本构成单元是由平行于c轴的硅氧四面体双链组成，各个链间通过氧原子连接，硅氧四面体的自由氧原子的指向(即硅氧四面体的角顶)每四个一组，上下交替地排列。指向相对的硅氧四面体之间通过八面体阳离子连接，指向相背的硅氧四面体之间形成沿c轴方向的孔道，这种排列方式使四面体片在链间被连续地连接，但四面体的自由氧原子指向的不一致性决定了八面体片是不连续的，形成很多孔道，孔道截面大约为0.38nm×0.63nm。凹凸棒石凭借其独特结构和化学组成赋予其特殊的性能，且储量丰富、价格低廉，作为吸附剂、粘结剂、助剂、添加剂和催化剂载体等在水处理、油脂加工、医药以及石油化工等领域具有广泛的应用前景。
对凹凸棒石黏土进行活化处理是非常必要的，通常使用不同浓度的酸溶液进行活化。在酸溶液处理凹凸棒土过程中，碳酸盐杂质完全溶解，八面体阳离子部分溶解，大部分硅氧四面体基本保留，使得凹凸棒石的晶体结构得以保持，活化后的凹凸棒石黏土比表面积有所增大，孔体积和表面性能均有所改变。但是，在酸活化过程中，随着八面体阳离子的溶解，会有硅溶胶、无定型二氧化硅、纳米棒状活性二氧化硅以及介于凹凸棒石和活性纳米棒状二氧化硅之间的过渡状态等产物形成(陈天虎，冯有亮，史晓莉，凹凸棒石与酸反应产物和结构演化的研究，硅酸盐学报，2003,31(10):959-964)。这些含硅产物的形成将影响凹凸棒石黏土的吸附性能和催化性能。因此，需要建立一种新的凹凸棒石黏土制备方法以解决现有技术中存在的问题。
发明内容
本发明所要解决的技术问题是：克服现有技术存在的问题，提供一种分级孔凹凸棒石的制备方法，凹凸棒石黏土首先经酸溶液处理，除去其中的杂质和部分八面体阳离子，而后加入氟化物以除去其间的含硅化合物，经过滤、洗涤和干燥即得分级孔凹凸棒石材料。将其用作吸附剂，可选择性吸附二氧化碳；将其作为甲苯与苄基溴进行Friedel-Crafts烷基化反应的催化剂，得到较高的转化率。
本发明是通过以下技术方案实现的：
本发明的分级孔凹凸棒石的制备方法，其包括以下步骤：称取凹凸棒石黏土于玻璃烧瓶中，加入酸溶液，在60-110℃下回流搅拌2-12h后，冷至室温，转至烧杯中，向其中加入氟化物进行反应，再经过滤、洗涤和干燥，即得到分级孔凹凸棒石。
本发明的分级孔凹凸棒石的制备方法，其进一步的技术方案是所述的酸溶液浓度范围为1.0-5.0mol·L-1，使凹凸棒石黏土在酸溶液中的质量浓度为10-50mg·mL-1。
本发明的分级孔凹凸棒石的制备方法，其进一步的技术方案还可以是所述的酸溶液为盐酸、硝酸和硫酸中的一种。
本发明的分级孔凹凸棒石的制备方法，其进一步的技术方案还可以是所述的氟化物为氟化铵或氟化钠，其浓度范围在0.5-1.5mol·L-1，反应时间为5-180min。
本发明上述的制备方法制备的分级孔凹凸棒石在二氧化碳/甲烷/氮气体系中选择性吸附二氧化碳中的应用，其可用作吸附剂，选择性吸附二氧化碳/甲烷/氮气体系中的二氧化碳。
本发明上述的制备方法制备的分级孔凹凸棒石作为甲苯与苄基溴进行Friedel-Crafts烷基化反应的催化剂中的应用，其可用作甲苯与苄基溴进行Friedel-Crafts烷基化反应的催化剂
本发明与现有技术相比具有以下有益效果：
本发明是利用酸溶液和氟化物组合处理凹凸棒石黏土，在凹凸棒石结构未被破坏的前提下制得分级孔凹凸棒石，可用作特定的吸附剂和催化剂，具有一定的应用前景。本发明提供的制备方法条件温和，操作简单，提高了凹凸棒石对二氧化碳的吸附量和选择性，同时，提升了凹凸棒石对Friedel-Crafts烷基化反应的催化活性。
具体实施方式
下面结合具体实施例对本发明作进一步描述，但是本发明的范围不限于所给出的实施例。
实施例1-34制备分级孔凹凸棒石材料
具体制备过程如下：
称取一定质量的凹凸棒石黏土于玻璃烧瓶中，向其中加入适量的酸溶液(A)，凹凸棒石黏土的质量浓度为B，酸溶液的浓度为C，在设定温度(D)下回流搅拌一定时间(E)，冷至室温，转至塑料烧杯中，向其中加入氟化物(F)，使其浓度为G，反应H min，经过滤、洗涤和干燥，即得分级孔凹凸棒石。
其中，所用的酸至少为盐酸(A1)、硝酸(A2)和硫酸(A3)中的一种；加入的氟化物至少为氟化铵(F1)和氟化钠(F2)中的一种；
凹凸棒石黏土的质量浓度B范围为10-50mg·mL-1；酸溶液浓度C的范围为1.0-5.0mol·L-1；回流温度D范围为60-110℃；回流时间E范围为2-12h；氟化物浓度G的范围为0.5-1.5mol·L-1；氟化物反应时间H的范围为5-180min。
实施例1-34中各代号说明和各实施例的实验条件如表1和表2所示：
表1各代号说明及其单位
表2实施例1-34的实验条件
应用实施例：实施例1-34所得的分级孔凹凸棒石材料的吸附性能
将实施例1-34中所得的分级孔凹凸棒石材料各取100mg，置于美国麦克公司的ASAP 2020比表面及孔隙分析仪中，在一定的压力和温度下进行吸附性能测试，测定各材料对CO2，CH4和N2的吸附量，并计算CO2/N2的平衡选择性，结果如表3所示。
应用实施例：实施例1-34所得的分级孔凹凸棒石材料的催化性能
将实施例1-34所得的分级孔凹凸棒石材料各取100mg于三口烧瓶中，加入适量的甲苯和苄基溴，在80℃下反应3h，产物用气相色谱仪(Agilent 7890A)测定，并计算反应的转化率，结果如表3所示。
表3实施例1-34中所得的分级孔凹凸棒石材料的吸附性能和催化性能
对比例1
分别称取1.0g凹凸棒石黏土于3个玻璃烧瓶中，依次加入50mL1.0mol·L-1盐酸、硝酸和硫酸溶液，于110℃下回流搅拌2h，冷至室温，过滤、洗涤、干燥，即得到酸处理的凹凸棒石，分别记作A1-T，A2-T和A3-T。
称取A1-T，A2-T和A3-T各100mg，置于美国麦克公司的ASAP 2020比表面及孔隙分析仪中，在一定的压力和温度下分别测定它们对CO2，CH4和N2的吸附量，并计算CO2/N2的平衡选择性。称取A1-T，A2-T和A3-T各100mg于三口烧瓶中，加入适量的甲苯和苄基溴，在80℃下反应3h，产物用气相色谱仪(Agilent 7890A)测定，并计算反应的转化率，结果如表4所示。
表4酸溶液处理的凹凸棒石黏土的吸附性能和催化性能
对比例2
分别称取1.0g凹凸棒石黏土于2个烧杯中，依次加入50mL1.0mol·L-1氟化铵和氟化钠溶液，室温下搅拌2h，过滤、洗涤、干燥，即得到氟化物处理的凹凸棒石，分别记作F1-T，和F2-T。
称取F1-T和F2-T各100mg，置于美国麦克公司的ASAP 2020比表面及孔隙分析仪中，在一定的压力和温度下分别测定它们对CO2，CH4和N2的吸附量，并计算CO2/N2的平衡选择性。各称取F1-T，和F2-T 100mg于三口烧瓶中，加入适量的甲苯和苄基溴，在80℃下反应3h，产物用气相色谱仪(Agilent 7890A)测定，并计算反应的转化率，结果如表5所示。
表5氟化物处理的凹凸棒石黏土的吸附性能和催化性能
通过对比例可以看出，本发明制得的分级孔凹凸棒石黏土其吸附性能和催化性能比仅单一处理的凹凸棒石黏土均有大幅度提高。
Claims (3)
1.一种分级孔凹凸棒石的制备方法，其特征在于包括以下步骤：称取凹凸棒石黏土于玻璃烧瓶中，加入酸溶液，在60-110℃下回流搅拌2-12h后，冷至室温，转至烧杯中，向其中加入氟化物进行反应，再经过滤、洗涤和干燥，即得到分级孔凹凸棒石；其中所述的酸溶液为盐酸、硝酸和硫酸中的一种，酸溶液浓度范围为1.0-5.0mol·L-1，使凹凸棒石黏土在酸溶液中的质量浓度为10-50mg·mL-1；所述的氟化物为氟化铵或氟化钠，其浓度范围在0.5-1.5mol·L-1，反应时间为5-180min。
2.一种如权利要求1所述的制备方法制备的分级孔凹凸棒石在二氧化碳-甲烷-氮气体系中选择性吸附二氧化碳的应用。
3.一种如权利要求1所述的制备方法制备的分级孔凹凸棒石作为甲苯与苄基溴进行Friedel-Crafts烷基化反应的催化剂的应用。
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