CN110339730A - 一种三价铬离子印迹复合膜的制备方法及应用 - Google Patents
一种三价铬离子印迹复合膜的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种三价铬离子印迹复合膜的制备方法及应用，属于膜分离技术领域。本发明所述方法以市售商业膜为支撑膜，三价铬离子为印迹离子，α‑甲基丙烯酸为功能单体，偶氮二异丁腈为引发剂，乙二醇二甲基丙烯酸酯为交联剂，采用表面接枝法，利用离子印迹技术并通过热引发方式使功能单体和模板离子在支撑膜表面进行聚合，使膜表面包裹三价铬离子聚合物薄层，制备得到三价铬离子印迹复合膜，该印迹复合膜表面具有与三价铬离子形状、大小、尺寸相匹配的孔穴，能够对目标溶液中的三价铬离子进行专一性识别；该方法易于操作，实施简单，环境友好，克服了现行三价铬离子吸附材料制备困难，选择性差等缺点。
Description
技术领域
本发明公开一种三价铬离子印迹复合膜的制备方法及应用，属于膜分离技术领域。
背景技术
铬由人类工业活动引入环境系统，主要来源于电镀、制革工业、颜料、涂料生产及采矿工业等。铬在环境中主要以二价、三价及六价的形式存在，其中最稳定的是三价和六价，六价铬离子是一种潜在的剧毒物质，我国要求制革及皮毛加工工业排放污水中六价铬的浓度应低于0.1mg/L；虽然少量的三价铬是人体葡萄糖及胆固醇代谢所必需的元素之一，但是当三价铬浓度过大时会导致人体皮肤过敏，在一定条件下会转变成毒性巨大的六价铬。因此，去除环境中的三价铬离子具有重要的意义。
目前三价铬离子的去除技术主要有化学沉淀法、电絮凝法、离子交换法、膜技术和生物吸附法等。其中膜技术与生物吸附法因其具有高效率而被广泛应用于三价铬离子的去除。中国专利CN 109046293 A公开了一种三价铬离子吸附剂的制备方法，利用硅烷偶联剂对介孔材料进行氨基功能化，然后将2-酰噻吩嫁接到介孔材料上，获得高性能三价铬离子吸附剂。该方法解决了有机分子在实际应用中兼容性差、毒副作用强、不易回收等缺点。但常规吸附剂对目标离子的选择性性差，不具有专一性识别能力。鉴于三价铬离子的严重污染，急需寻找一种更为有效的处理技术。
发明内容
本发明的目的在于提供一种三价铬离子印迹复合膜的制备方法， 该方法以市售商业微孔滤膜为支撑膜，三价铬离子为印迹离子，α-甲基丙烯酸为功能单体，采用表面接枝方法，利用离子印迹技术并通过热引发方式使功能单体和模板离子在支撑膜表面进行聚合，使膜表面包裹三价铬离子聚合物薄层，制备得到三价铬离子印迹复合膜，具体步骤如下：
（1）预聚合溶液的制备：将CrCl3溶于有机溶剂和水的混合致孔溶剂中，其中，CrCl3的浓度为10~100mmol/L；再加入功能单体α-甲基丙烯酸，在室温下置于恒温振荡器中恒温反应2～3h，加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈，充分溶解并摇匀，超声脱气除氧，形成预聚合溶液；
（2）制备三价铬离子印迹复合膜：将支撑膜置于步骤（1）的预聚合溶液中，在室温下浸泡1～60min，取出置于两块玻璃板之间，然后于60～70℃下反应12～36h，最后用甲醇和醋酸的混合溶液洗脱除去支撑膜上负载的三价铬离子，制备得到三价铬离子印迹复合膜。
优选的，本发明所述支撑膜为Nylon-6膜、聚四氟乙烯膜或聚偏氟乙烯膜。
优选的，本发明混合致孔溶剂中有机溶剂和水的体积比为1:1~3:1。
优选的，本发明甲醇和醋酸混合溶液中甲醇和醋酸的体积比为9:1。
优选的，本发明步骤（1）中CrCl3、α-甲基丙烯酸和乙二醇二甲基丙烯酸酯摩尔比为1: 1～8: 20～50，偶氮二异丁腈与CrCl3的摩尔比为1～6:2～10。
优选的，本发明步骤（1）中所述机溶剂为N-N-二甲基甲酰胺、甲醇、乙醇、异丙醇或乙腈。
本发明的另一目的在于将所述方法制备的三价铬离子印迹复合膜用于吸附分离溶液中三价铬离子。
本发明的有益效果为：（1）本发明采用离子印迹表面接枝技术，以商业微孔滤膜为支撑膜，克服了现行三价铬离子吸附材料制备困难、方法繁琐等缺点。（2）该方法制备的离子印迹复合膜使识别位点暴露在膜表面不仅能提高其专一识别性能，而且还能提高其对三价铬离子的吸附容量。（3）以α-甲基丙烯酸为功能单体制备的离子印迹复合膜经济实用、工艺简单，可用于水体中三价铬离子的选择性吸附与分离。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。
实施例1
一种三价铬离子印迹复合膜的制备方法，具体步骤如下：
（1）将CrCl3溶于体积比为1:1的有机溶剂（甲醇）和水的混合致孔溶剂中，其中，CrCl3的浓度为20mmol/L，再加入功能单体α-甲基丙烯酸，在室温下置于恒温振荡器中恒温反应2h，加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈，充分溶解并摇匀，超声脱气除氧10min，形成预聚合溶液；其中CrCl3、α-甲基丙烯酸和乙二醇二甲基丙烯酸酯摩尔比为1:1:20，偶氮二异丁腈与CrCl3的摩尔比为3: 4。
（2）将Nylon-6膜置于步骤（1）制备得到的预聚合溶液中，在室温下浸泡1min，取出置于两块玻璃板之间，然后于60℃下反应12h，最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去Nylon-6膜上负载的三价铬离子，制备得到三价铬离子印迹复合膜。
将本实施例制备得到的2.10g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中，其吸附量为118.48μmol/g，印迹因子为1.28。
实施例2
一种三价铬离子印迹复合膜的制备方法，具体步骤如下：
（1）将CrCl3溶于体积比为1:1的有机溶剂（乙腈）和水的混合致孔溶剂中，其中，CrCl3的浓度为30mmol/L，再加入功能单体α-甲基丙烯酸，在室温下置于恒温振荡器中恒温反应3h，加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈，充分溶解并摇匀，超声脱气除氧10min，形成预聚合溶液；其中CrCl3、α-甲基丙烯酸和乙二醇二甲基丙烯酸酯摩尔比为1:8:50，偶氮二异丁腈与CrCl3的摩尔比为5: 10。
（2）将聚四氟乙烯膜置于步骤（1）制备得到的预聚液中，在常温下浸泡60min，取出置于两块玻璃板之间，然后于70℃下反应36h，最后150mL用体积比为9:1的甲醇和醋酸混合溶液洗脱除去聚四氟乙烯膜上负载的三价铬离子，制备得到三价铬离子印迹复合膜。
将本实施例制备得到的1.80g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中，其吸附量为80.04μmol/g，印迹因子为1.32。
实施例3
一种三价铬离子印迹复合膜的制备方法，具体步骤如下：
（1）将CrCl3溶于体积比为1:1的有机溶剂（异丙醇）和水的混合致孔溶剂中，其中，CrCl3的浓度为100mmol/L，再加入功能单体α-甲基丙烯酸，在室温下置于恒温振荡器中恒温反应2.5h，加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈，充分溶解并摇匀，超声脱气除氧10min，形成预聚合溶液；其中CrCl3、α-甲基丙烯酸和乙二醇二甲基丙烯酸酯摩尔比为1:4:20，偶氮二异丁腈与CrCl3的摩尔比为1:2。
（2）将聚偏氟乙烯膜置于步骤（1）制备得到的预聚合溶液中，在常温下浸泡30min，取出置于两块玻璃板之间，然后于65℃下反应24h，最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去聚偏氟乙膜上负载的三价铬离子，制备得到三价铬离子印迹复合膜。
将本实施例制备得到的2.50g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中，其吸附量为108.84μmol/g，印迹因子为1.85。
实施例4
一种三价铬离子印迹复合膜的制备方法，具体步骤如下：
（1）将CrCl3溶于体积比为1:1的有机溶剂（乙醇）和水的混合致孔溶剂中，其中，CrCl3的浓度为45mmol/L，再加入功能单体α-甲基丙烯酸，在室温下置于恒温振荡器中恒温反应3h，加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈，充分溶解并摇匀，超声脱气除氧10min，形成预聚合溶液；其中CrCl3、α-甲基丙烯酸和乙二醇二甲基丙烯酸酯摩尔比为1:4:40，偶氮二异丁腈与CrCl3的摩尔比为1:4。
（2）将Nylon-6膜置于步骤（1）制备得到的预聚合溶液中，在室温下浸泡3min，取出置于两块玻璃板之间，然后于60℃下反应24h，最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去Nylon-6膜上负载的三价铬离子，制备得到三价铬离子印迹复合膜。
将本实施例制备得到的2.80g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中，其吸附量为105.05μmol/g，印迹因子为1.25。
实施例5
一种三价铬离子印迹复合膜的制备方法，具体步骤如下：
（1）将CrCl3溶于体积比为1:1的有机溶剂（N-N-二甲基甲酰胺）和水的混合致孔溶剂中，其中，CrCl3的浓度为60mmol/L，再加入功能单体α-甲基丙烯酸，在室温下置于恒温振荡器中恒温反应2h，加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈，充分溶解并摇匀，超声脱气除氧10min，形成预聚合溶液；其中CrCl3、α-甲基丙烯酸和乙二醇二甲基丙烯酸酯摩尔比为1:6:30，偶氮二异丁腈与CrCl3的摩尔比为5:3。
（2）将Nylon-6膜置于步骤（1）制备得到的预聚合溶液中，在室温下浸泡45min，取出置于两块玻璃板之间，然后于65℃下反应24h，最后用150mL体积比为9:1的甲醇和醋酸混合溶液洗脱除去Nylon-6膜上负载的三价铬离子，制备得到三价铬离子印迹复合膜。
将本实施例制备得到的3.00g三价铬离子印迹复合膜应用在浓度为54.00mmol/L的三价铬离子溶液中，其吸附量为95.21μmol/g，印迹因子为1.41。
以上对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (7)
1.一种三价铬离子印迹复合膜的制备方法，其特征在于，具体包括以下步骤：
（1）预聚合溶液的制备：将CrCl3溶于有机溶剂和水的混合致孔溶剂中，其中，CrCl3的浓度为10~100mmol/L；再加入功能单体α-甲基丙烯酸，在室温下置于恒温振荡器中恒温反应2～3h，加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈，充分溶解并摇匀，超声脱气除氧，形成预聚合溶液；
（2）制备三价铬离子印迹复合膜：将支撑膜置于步骤（1）的预聚合溶液中，在室温下浸泡1～60min，取出置于两块玻璃板之间，然后于60～70℃下反应12～36h，最后用甲醇和醋酸的混合溶液洗脱除去支撑膜上负载的三价铬离子，制备得到三价铬离子印迹复合膜。
2.根据权利要求1所述三价铬离子印迹复合膜的制备方法，其特征在于：步骤（1）中CrCl3、α-甲基丙烯酸和乙二醇二甲基丙烯酸酯摩尔比为1: 1～8: 20～50，偶氮二异丁腈与CrCl3的摩尔比为1～6:2～10。
3.根据权利要求1所述三价铬离子印迹复合膜的制备方法，其特征在于：所述支撑膜为Nylon-6膜、聚四氟乙烯膜或聚偏氟乙烯膜。
4.根据权利要求1所述三价铬离子印迹复合膜的制备方法，其特征在于：混合致孔溶剂中有机溶剂和水的体积比为1:1~3:1。
5.根据权利要求1所述三价铬离子印迹复合膜的制备方法，其特征在于：甲醇和醋酸混合溶液中甲醇和醋酸的体积比为9:1。
6.根据权利要求1所述三价铬离子印迹复合膜的制备方法，其特征在于：所述步骤（1）中所述有机溶剂为N-N-二甲基甲酰胺、甲醇、乙醇、异丙醇或乙腈。
7.根据权利要求1~6任一项所述方法制备的三价铬离子印迹复合膜用于吸附分离溶液中三价铬离子。
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