CN104607160B - 具有阴阳离子共吸附特性的双功能水相吸附材料 - Google Patents

具有阴阳离子共吸附特性的双功能水相吸附材料 Download PDF

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CN104607160B
CN104607160B CN201510032257.XA CN201510032257A CN104607160B CN 104607160 B CN104607160 B CN 104607160B CN 201510032257 A CN201510032257 A CN 201510032257A CN 104607160 B CN104607160 B CN 104607160B
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zwitterion
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于岩
何亚军
巫秋平
梁志瑜
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Fuzhou University
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Abstract

本发明公开了一种具有阴阳离子共吸附特性的双功能水相吸附材料，是以三嵌段共聚物P123、正硅酸乙脂、异丙醇铝为主要原料，采用直接合成法将无机Al离子掺杂在基体骨架中，制造出阳离子活性吸附位点，然后通过后嫁接法在其孔道表面接枝大空间位阻有机基团，制造出阴离子活性吸附位点。该吸附材料在同一基体中引入了两种电性相反的吸附中心，并利用有机基团的空间位阻效应，成功避免酸碱中心的自发复合失效反应，从而制造出同时具有阴、阳离子吸附位点的分子筛吸附材料（Al‑SBA‑15‑G），其对阴阳离子共存的污水体系具有优异的净化性能，解决了传统吸附材料只能吸附单一电性的离子，污水吸附处理成本高的问题，具有较好的应用前景。

Description

具有阴阳离子共吸附特性的双功能水相吸附材料
技术领域
本发明属于污水处理技术领域，具体涉及一种具有阴阳离子共吸附特性的双功能水相吸附材料。
背景技术
近年来，随着工业的飞速发展，冶金、化工、化肥、机械制造、电子仪表、涂料等工业生产过程以及大气中降落的无机粉尘，造成河流、湖泊甚至地下水的严重污染，使得我国饮用水资源遭到严重的危害。在众多环境治理技术中，吸附法是最为传统也是当前最为有效的污水处理方法。目前，吸附法治理多种可溶性无机污染物的主要策略是分步吸附处理法，即先利用一种吸附材料选择性吸附污水中的一种电性的离子，而后再选用另外一种吸附材料吸附相反电性的离子。如采用富含酸性中心的吸附材料去除阳离子，再用含有碱性中心的吸附材料去除阴离子。这种方法对于简单的污染体系可能是有效的，但是对于多离子共存的复杂水溶液体系，其因受腐殖酸浓度、酸碱度、离子强度、温度和溶解氧循环等各种因素的影响，不同离子和不同基团之间会发生电荷传质、氢键作用、疏水作用等，导致阴、阳离子在吸附材料上发生吸附/络合、解吸释放和迁移转化等复杂的变化，因此很难取得满意的净化效果。此外，分步吸附处理法的吸附反应、分离和回收过程重复进行，耗时耗力且成本高。因此，发展同时具有多活性吸附位点的材料，使之既具有阳离子吸附位点同时也具有特定阴离子吸附位点，则可以实现对污水中阴、阳离子的同时吸附脱除，从而达到对无机废水的理想净化效果。
介孔分子筛（SBA-15）具有有序的孔道、巨大的比表面积、可调变的孔径、稳定的骨架结构、易于掺杂的骨架组成和可修饰的表面结构，是双功能吸附材料的理想基体。本发明首次提出采用直接法和后嫁接法，在分子筛SBA-15基体中引入阴、阳离子的吸附中心，并利用有机基团的空间位阻效应，避免了两种电性相反的吸附中心间发生自发复合和中和反应，从而达到同时高效去除废水中阴阳离子的目的。将本发明提出的具有阴阳离子共吸附特性的双功能水相吸附材料应用到污水处理过程中，可以缓解水污染程度，减少对环境的污染，具有重要的实际应用价值。
发明内容
本发明的目的在于提供一种具有多种阴阳离子共吸附特性的双功能水相吸附材料，其可解决传统吸附材料只能吸附单一电性离子的问题，有效减低污水吸附处理的成本，为污水吸附剂的研制提供了一种全新的思路。
为实现上述目的，本发明采用如下技术方案：
一种具有阴阳离子共吸附特性的双功能水相吸附材料，是以三嵌段共聚物P123、正硅酸乙脂、异丙醇铝为主要原料，采用直接合成法将无机Al离子掺杂在基体骨架中，制造出阳离子活性吸附位点，然后通过后嫁接法在其孔道表面接枝大空间位阻有机基团，制造出阴离子活性吸附位点，得到所述双功能水相吸附材料。
所述双功能水相吸附材料的制备方法具体包括如下步骤：
第一步 直接合成法：
1）将三嵌段共聚物P123溶于去离子水和2M的HCl中，室温下搅拌4h使P123完全溶解，然后在40℃下缓慢滴加正硅酸乙脂(TEOS)，剧烈搅拌45min，再加入异丙醇铝，继续剧烈搅拌24h；
2）将所得混合液转移至聚四氟乙烯反应釜中，在100℃下晶化反应48h；
3）过滤，滤饼用去离子水洗至中性后，于60℃下干燥12h，在550℃下以2℃/min的升温速度煅烧6h，得到白色粉末Al-SBA-15；
第二步 后嫁接法：
1）将Al-SBA-15溶于甲苯溶液中，然后缓慢滴加硅烷偶联剂3-氨丙基三乙氧基硅烷（APTES），在室温下搅拌12h，过滤，滤饼用足量异丙醇洗涤后于110℃下干燥，得到Al-SBA-15-NH2；
2）将三聚氯氰和N,N-二异丙基乙胺(DIPEA)溶于四氢呋喃(THF)，在0℃下搅拌3h后加入制好的Al-SBA-15-NH2，继续搅拌24h，过滤，滤饼依次用甲醇、二氯甲烷、四氢呋喃洗涤；
3）洗涤后的固体与乙二胺(EDA)溶于四氢呋喃中，回流反应24h，过滤，滤饼依次用甲醇、二氯甲烷、四氢呋喃洗涤，干燥后于0.1M的HCl中搅拌6h，过滤、干燥，得到所述双功能水相吸附材料Al-SBA-15-G。
无机Al离子的掺杂浓度按Si/Al=10。
所述大空间位阻有机基团的接枝量为0.05mmol/g。
本发明的显著优点在于：
（1）无机Al离子掺杂在SBA-15基体骨架中产生了一定强度的阳离子吸附中心，无机离子的掺杂量对基体骨架有序性及阳离子的吸附效果都有很大的影响。掺杂量过大，基体骨架有序性破坏大，不利于后面大空间位阻有机基团的嫁接；掺杂量过小，阳离子的吸附中心少，不利于阳离子的吸附去除。本发明确定了无机离子的掺杂浓度以Si/Al=10为宜。
（2）大空间位阻有机基团的接枝对基体的孔径、比表面积、孔容等都有重大的影响。接枝量过大，基体比表面积骤减，孔道堵塞，破坏了基体材料的骨架刚性结构，使得两种电性相反的吸附中心发生自发复合和中和反应，不利于阴、阳离子的共吸附；接枝量过小，阴离子吸附中心少，不利于阴离子的吸附去除。本发明确定了大空间位阻有机基团的接枝量为0.05mmol/g。
（3）本发明制备出具有阴阳离子共吸附特性的介孔吸附材料，在同一基体上实现了阴离子吸附中心和阳离子吸附中心的良好协同作用，并利用有机基团的空间位阻效应，避免了两种电性相反的吸附位点间发生自发复合和中和反应，使其可同时高效去除废水中阴阳离子的功效。
附图说明
图1为SBA-15的骨架结构图，其中（a）为未掺杂，（b）为掺杂无机Al离子后。
图2为本发明双功能水相吸附材料的主要合成路线。
图3为本发明双功能水相吸附材料Al-SBA-15-G的共吸附机理图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
一种具有阴阳离子共吸附特性的双功能水相吸附材料，其制备方法具体包括如下步骤：
第一步 直接合成法：
1）将4g三嵌段共聚物P123溶于30mL去离子水和120mL 2M的HCl中，室温下搅拌4h使P123完全溶解，然后在40℃下缓慢滴加9.0g正硅酸乙脂(TEOS)，剧烈搅拌45min，再加入异丙醇铝，继续剧烈搅拌24h；
2）将所得混合液转移至聚四氟乙烯反应釜中，在100℃下晶化反应48h；
3）过滤，滤饼用去离子水洗至中性后，于60℃下干燥12h，在550℃下以2℃/min的升温速度煅烧6h，得到白色粉末Al-SBA-15；
第二步 后嫁接法：
1）将1g Al-SBA-15溶于100mL甲苯溶液中，然后按每克Al-SBA-15使用0.05mmol硅烷偶联剂的比例缓慢滴加3-氨丙基三乙氧基硅烷（APTES），在室温下搅拌12h，过滤，滤饼用足量异丙醇洗涤后于110℃下干燥，得到Al-SBA-15-NH2；
2）将5.5g三聚氯氰和7.1mL N,N-二异丙基乙胺(DIPEA)溶于300mL四氢呋喃(THF)，在0℃下搅拌3h后加入1g 已制好的Al-SBA-15-NH2，继续搅拌24h，过滤，滤饼依次用甲醇、二氯甲烷、四氢呋喃洗涤；
3）洗涤后的固体与4mL乙二胺(EDA)溶于300mL四氢呋喃中，回流反应24h，过滤，滤饼依次用甲醇、二氯甲烷、四氢呋喃洗涤，干燥后于200mL 0.1M的HCl中搅拌6h，过滤、干燥，得到所述双功能水相吸附材料Al-SBA-15-G。
用CuSO4和Na2SO4配制Cu2+和SO4 2-的共混模拟废水，进行阴阳离子混合吸附功效的测试和评价，吸附机理图如图3所示。
1. 吸附时间的确定：以Si/Al=10的Al-SBA-15，按大空间位阻有机基团接枝量为0.05mmol/g制备出Al-SBA-15-G吸附材料。模拟废水的pH和浓度分别为7和30mg/L，吸附时间分别为5min、10min、15min、20min、30min、60min、90min、120min、150min、180min，评价不同吸附平衡时间对阴阳离子共吸附的去除效果，吸附测试效果见表1。
表1 不同吸附时间对阴阳离子共吸附效果的影响
本实施例将吸附时间分别设定为5min、10min、15min、20min、30min、60min、90min、120min、150min、180min，最终确定该吸附过程的阴阳离子吸附平衡时间都为90min。
2. 废水pH值的确定：以Si/Al=10的Al-SBA-15，按大空间位阻有机基团接枝量为0.05mmol/g制备出Al-SBA-15-G吸附材料。模拟废水浓度为30mg/L，吸附时间90min，模拟废水的pH值分别为2、3、4、5、6、7、8、9、10、11，评价不同pH值对阴阳离子共吸附的去除效果，吸附测试效果见表2。
表2 不同pH值对阴阳离子共吸附效果的影响
pH值影响溶液中离子存在状态，对吸附效果产生重大的影响，pH值过大，不利于阴离子的吸附，pH值过小，不利于阳离子的吸附。本实施例将pH值分别设定为2、3、4、5、6、7、8、9、10、11，最终确定阴阳离子共吸附实验中最佳的pH值为7。
3. Si/Al的确定：对基体以不同Si/Al比进行Al掺杂，异丙醇铝的加入量分别为1.6666g（Si/Al=5）、0.8333g（Si/Al=10）、0.5555g（Si/Al=15）、0.4167g（Si/Al=20）、0.2778g(Si/Al=30)，按大空间位阻有机基团的接枝量为0.05mmol/g制备出Al-SBA-15-G吸附材料。模拟废水的pH值和浓度分别为7和30mg/L，吸附时间为90min，评价不同Si/Al比掺杂合成的Al-SBA-15-G对阴阳离子共吸附的去除效果，吸附测试效果见表3。
表3 不同Si/Al对阴阳离子共吸附效果的影响
由表3可见，当Si/Al=10时，对Cu2+和SO4 2的吸附即可达到较好的效果。
4. 有机基团接枝量的确定：设定有机基团的接枝量分别为0.02、0.04、0.05、0.06、0.08、0.10mmol/g，以Si/Al=10的Al-SBA-15制备出Al-SBA-15-G吸附材料。模拟废水的pH和浓度分别为7和30mg/L，吸附时间为90min，评价不同有机基团接枝量合成的Al-SBA-15-G对阴阳离子共吸附的去除效果，吸附测试效果见表4。
表4 不同有机基团接枝量对阴阳离子共吸附效果的影响
由表4可见，当有机基团接枝量为0.05mmol/g时，对Cu2+和SO4 2的吸附达到最高。
本发明具有阴阳离子共吸附特性的双功能水相吸附材料，在同一基体上实现了阴离子吸附中心和阳离子吸附中心的良好协同作用，并利用有机基团的空间位阻效应，避免了两种电性相反的吸附位点间发生自发复合和中和反应，使其具有同时高效去除废水中阴阳离子的功效。通过实验证实，本发明具有阴阳离子共吸附特性的双功能水相吸附材料对Cu2+和SO4 2的吸附均可达到95%以上，说明该双功能水相吸附材料具有较好的污水处理效果。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (1)

1.一种具有阴阳离子共吸附特性的双功能水相吸附材料的制备方法，其特征在于：以三嵌段共聚物P123、正硅酸乙酯、异丙醇铝为主要原料，采用直接合成法将无机Al离子掺杂在基体骨架中，制造出阳离子活性吸附位点，然后通过后嫁接法在其孔道表面接枝大空间位阻有机基团，制造出阴离子活性吸附位点，得到所述双功能水相吸附材料；
其具体包括如下步骤：
第一步 直接合成法：
1）将三嵌段共聚物P123溶于去离子水和2M的HCl中，室温下搅拌4h使P123完全溶解，然后在40℃下缓慢滴加正硅酸乙酯，剧烈搅拌45min，再加入异丙醇铝，继续剧烈搅拌24h；
2）将所得混合液转移至聚四氟乙烯反应釜中，在100℃下晶化反应48h；
3）过滤，滤饼用去离子水洗至中性后，于60℃下干燥12h，在550℃下以2℃/min的升温速度煅烧6h，得到白色粉末Al-SBA-15；
第二步 后嫁接法：
1）将Al-SBA-15溶于甲苯溶液中，然后缓慢滴加硅烷偶联剂3-氨丙基三乙氧基硅烷，在室温下搅拌12h，过滤，滤饼用异丙醇洗涤后于110℃下干燥，得到Al-SBA-15-NH2；
2）将三聚氯氰和N,N-二异丙基乙胺溶于四氢呋喃，在0℃下搅拌3h后加入制好的Al-SBA-15-NH2，继续搅拌24h，过滤，滤饼依次用甲醇、二氯甲烷、四氢呋喃洗涤；
3）洗涤后的固体与乙二胺溶于四氢呋喃中，回流反应24h，过滤，滤饼依次用甲醇、二氯甲烷、四氢呋喃洗涤，干燥后于0.1M的HCl中搅拌6h，过滤干燥，得到所述双功能水相吸附材料；
其中，无机Al离子的掺杂浓度按Si/Al=10；
所述大空间位阻有机基团的接枝量为0.05mmol/g。
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