CN114225696B - 一种酶催化型正渗透膜及其制备方法与应用 - Google Patents
一种酶催化型正渗透膜及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种酶催化型正渗透膜及其制备方法与应用，该膜是以静电纺丝纳米纤维膜为支撑层，将活性酶固定在正渗透膜表面形成的集催化和分离为一体正渗透复合膜，具有膜传质系数高、膜载酶量高以及特异性降解等优点，能高效降解去除抗生素，提升出水水质。
Description
技术领域
本发明属于膜分离技术领域，具体涉及一种酶催化型正渗透膜及其制备方法与应用。
背景技术
环境中的抗生素绝大部分最终都会进入水环境，抗生素在水环境中难以降解，已成为一类新型难降解有机微污染物；水体中长期残留的微量抗生素可诱导产生抗生素抗性细菌和抗性基因，抗性基因可通过水平基因转移等方式进入病原菌并赋予宿主对抗生素的耐药性，从而威胁着人类健康与生态安全。因此，针对水中难以降解的微量抗生素，研发高效的新材料与新技术，对于提升水质和确保水环境安全具有十分重要的意义。
正渗透(FO)是一种新型的浓度驱动型膜分离过程，水分子在渗透压差的作用下自发地从低浓度溶液(原料液)通过半渗透膜进入高浓溶液(驱动液)，其他离子被截留；继而原料液被浓缩，驱动液被稀释。与传统的压力驱动膜分离技术相比，正渗透操作过程不需外界施压，具有能耗低、膜污染较轻、操作条件温和及盐截率高等优点。近些年，正渗透膜已被用于水中抗生素的去除，然而单独的FO膜过程实质上只是将抗生素进行了浓缩，并未实现其降解，需要联合其他技术(如电催化、光催化、酶催化)进一步处理去除。
发明内容
本发明的目的在于提供一种高效催化降解抗生素的酶催化型正渗透膜及其制备方法，该膜是以静电纺丝纳米纤维膜为支撑层，将活性酶固定在正渗透膜表面形成集催化和分离为一体的正渗透复合膜具有膜传质系数高、膜载酶量高以及特异性降解等优点，能高效降解去除抗生素，提升出水水质。
为了实现上述目的，本发明采用以下技术方案：
一种酶催化型正渗透膜的制备方法，包括以下步骤：
(1)将高分子聚合物溶解于溶剂中，搅拌得到均匀纺丝液，其中高分子聚合物浓度为6～15wt％；
(2)通过静电纺丝设备将步骤(1)中的纺丝液制备纳米纤维膜，热处理后得到纳米纤维膜；
(3)将纳米纤维膜作为支撑层，先浸泡在水相单体中，然后置于有机相单体溶液中聚合形成致密皮层，获得正渗透膜；
(4)采用表面担载法(比如采用水解、表面接枝、表层涂覆以及化学交联等方法在膜表面进一步引入活性基团，通过化学键力固定化所选酶，提高载酶量和固定化酶的稳定性)将活性酶固定在正渗透膜表面上，获得集催化和分离为一体正渗透复合膜；
步骤(1)所述的高分子聚合物为聚丙烯腈、聚酰胺或者聚酰亚胺，所述的溶剂为N-N二甲基甲酰胺，N-N二甲基乙酰胺，丙酮，环己烷中的一种或者几种；
步骤(3)中所述的水相单体为双酚、哌嗪、间苯二胺、邻苯二胺及其衍生物中的一种或几种，其浓度为1～5wt％；有机相单体为对苯二甲酰氯、间苯二甲酰氯、均苯三甲酰氯中的一种或几种，其浓度为0.01～5wt％。
优选地，步骤(1)所述的高分子聚合物为聚丙烯腈、聚酰胺，所述的溶剂为N-N二甲基甲酰胺，N-N二甲基乙酰胺，丙酮中的一种或者几种；步骤(3)中所述的水相单体为间苯二胺或邻苯二胺，其浓度为1～3wt％；有机相单体为对苯二甲酰氯、均苯三甲酰氯中的一种或两种，其浓度为0.01～0.3wt％，有机相单体溶于正己烷中形成有机相单体溶液。
优选地，步骤(2)中纺丝电压为5～30kV，溶液的给料流速为0.3～2mL/h，纺丝喷射电极与接收装置的距离为5～30cm。
优选地，步骤(4)中所述的活性酶包括β-内酰胺酶、谷胱甘肽S-转移酶、漆酶和过氧化物酶中的一种或几种；优选地，活性酶的添加量为高分子聚合物的0.01～0.1wt％。
与现有技术相比，本发明的优点具有以下优点及有益效果：
(1)通过构建酶催化与渗透过滤为一体的催化型正渗透复合膜去除水中难生物降解、低浓度的典型抗生素污染物，建立一种以抗生素浓缩–催化–分离为一体的正渗透体系，为水中抗生素的去除提供新方法。
(2)本发明所述的正渗透膜支撑层采用静电纺丝技术制备，采用亲水性高分子材料制备复合纳米纤维膜，制备工艺更为简便，不但使支撑层的亲水性得到改善，相互交错的网状结构以及相互贯通的开孔，显著提高了正渗透膜的水通量和盐截率，由于支撑层使用了亲水材料，使浓差化现象大大降低。
具体实施方式
下面通过具体实例对本发明进行详细的描述，但本发明并不仅限于此。
实施例1
将1g聚丙烯腈(PAN)溶于10g N-N二甲基甲酰胺(DMF)与N-N二甲基乙酰胺(DMAc)的混合溶剂中(DMF：DMAc＝1:1)，搅拌均匀，制得浓度为10％的纺丝液。将上述溶液加入注射器内，调整注射器的流速为1.2mL/h，注射器距接收装置15cm，在15kV的高压静电下进行纺丝制备纳米纤维。将所得的复合纤维膜置于烘箱中60℃干燥12h，将干燥后的复合纤维膜经过塑封机进行层压，制得压实的复合纤维膜。
将上述压实的复合纤维膜作为支撑层，浸泡于浓度为3％的间苯二胺(MPD)水溶液中2min，取出，去除表面多余溶液，然后置于0.3％的均苯三甲酰氯(TMC)的正己烷溶液中，反应60s，取出后进行80℃水浴，处理10min后储存于4℃去离子水中。
将漆酶固定在上述正渗透膜的聚丙烯腈纳米纤维支撑层上：聚丙烯腈纳米纤维膜表面只有-CN，没有能结合酶的活性基团，先采用0.6mol/L盐酸羟胺处理2h后取出，在纤维表面形成-NH2，再将活化的正渗透膜用0.4％戊二醛接枝，再将处理后的正渗透膜浸泡在0.05％(比高分子聚合物)的活性β-内酰胺酶PBS缓冲液洗涤中，摇床转速180r/min，恒温20℃反应2h，酶固定的正渗透膜用PBS缓冲液洗涤3次后放置4℃冰箱储存备用。
水接触角测试采用光学接触角测定仪，先将样品干燥，在video模式下用5μL超纯水进行测试，经测试，本实施例制备的酶催化型的水接触角为30.8°；其支架状的支撑层能有效的降低水的传质阻力，很大程度的降低内部浓差极化，提高水通量。以2mol/L的氯化钠溶液为驱动液，纯水通量为36L/m2·h；酶催化与渗透过滤为一体的催化型正渗透复合膜能高效特异性降解，分离水中的β-内酰胺类抗生素，实验表明对浓度为50μg/L的青霉素G的截留率高达99.9％，对青霉素G的催化降解率为99.99％。
实施例2
将2g聚酰胺(PA6)溶于10g丙酮溶液中，搅拌均匀，制得浓度为20％的纺丝液。将上述溶液加入注射器内，调整注射器的流速为0.6mL/h，注射器距接收装置15cm，在10kV的高压静电下进行纺丝制备纳米纤维。将所得的复合纤维膜置于烘箱中60℃干燥12h，将干燥后的复合纤维膜经过塑封机进行层压，制得压实的复合纤维膜。
将上述压实的复合纤维膜作为支撑层，浸泡于浓度为1％的邻苯二胺水溶液中1.5min，取出，去除表面多余溶液，然后置于0.01％的对苯二甲酰氯的正己烷溶液中，反应30s，取出后进行80℃水浴，处理15min后储存于4℃去离子水中。
将过氧化物酶固定在上述正渗透膜的聚酰胺纳米纤维支撑层上：聚酰胺纳米纤维膜表面只有-CN，没有能结合酶的活性基团，先采用0.6mol/L盐酸羟胺处理2h后取出，在纤维表面形成-NH2，再将活化的正渗透膜用0.4％戊二醛接枝，再将处理后的正渗透膜浸泡在0.05％(比高分子聚合物)的活性氧化物酶PBS缓冲液洗涤中，摇床转速180r/min，恒温20℃反应2h，酶固定的正渗透膜用PBS缓冲液洗涤3次后放置4℃冰箱储存备用。
水接触角测试采用光学接触角测定仪，先将样品干燥，在video模式下用5μL超纯水进行测试，经测试，本实施例制备的酶催化型的水接触角为40.8°；其支架状的支撑层能有效的降低水的传质阻力，很大程度的降低内部浓差极化，提高水通量。以2mol/L的氯化钠溶液为驱动液，纯水通量为30L/m2·h；酶催化与渗透过滤为一体的催化型正渗透复合膜能高效特性降解，分离水中的β-内酰胺类抗生素，实验表明对浓度为50μg/L的青霉素G的截留率高达99.9％，对青霉素G的催化降解率为80.6％。
实施例3
将1g聚丙烯腈(PAN)溶于10g N-N二甲基甲酰胺(DMF)与N-N二甲基乙酰胺(DMAc)的混合溶剂中(DMF：DMAc＝1:1)，搅拌均匀，制得浓度为10％的纺丝液。将上述溶液加入注射器内，调整注射器的流速为1.2mL/h，注射器距接收装置15cm，在15kV的高压静电下进行纺丝制备纳米纤维。将所得的复合纤维膜置于烘箱中60℃干燥12h，将干燥后的复合纤维膜经过塑封机进行层压，制得压实的复合纤维膜。
将上述压实的复合纤维膜作为支撑层，浸泡于浓度为3％的间苯二胺(MPD)水溶液中2min，取出，去除表面多余溶液，然后置于0.3％的均苯三甲酰氯(TMC)的正己烷溶液中，反应60s，取出后进行80℃水浴，处理10min后储存于4℃去离子水中。
将谷胱甘肽S-转移酶固定在上述正渗透膜的聚丙烯腈纳米纤维支撑层上：聚丙烯腈纳米纤维膜表面只有-CN，没有能结合酶的活性基团，先采用0.6mol/L盐酸羟胺处理2h后取出，在纤维表面形成-NH2，再将活化的正渗透膜用0.4％戊二醛接枝，再将处理后的正渗透膜浸泡在0.05％(比高分子聚合物)的活性谷胱甘肽S-转移酶PBS缓冲液洗涤中，摇床转速180r/min，恒温20℃反应2h，酶固定的正渗透膜用PBS缓冲液洗涤3次后放置4℃冰箱储存备用。
水接触角测试采用光学接触角测定仪，先将样品干燥，在video模式下用5μL超纯水进行测试，经测试，本实施例制备的酶催化型的水接触角为33.5°；其支架状的支撑层能有效的降低水的传质阻力，很大程度的降低内部浓差极化，提高水通量。以2mol/L的氯化钠溶液为驱动液，纯水通量为32L/m2·h；酶催化与渗透过滤为一体的催化型正渗透复合膜能高效特性降解，分离水中的β-内酰胺类抗生素，实验表明对浓度为50μg/L的青霉素G的截留率高达90.3％，对青霉素G的催化降解率为90.1％。
Claims (3)
1.一种酶催化型正渗透膜的制备方法，其特征在于，包括以下步骤：
（1）将高分子聚合物溶解于溶剂中，搅拌得到均匀纺丝液，其中高分子聚合物浓度为6～15 wt%；
（2）通过静电纺丝设备将步骤（1）中的纺丝液制备纳米纤维膜，热处理后得到纳米纤维膜；
（3）将纳米纤维膜作为支撑层，先浸泡在水相单体中，然后置于有机相单体溶液中聚合形成致密皮层，获得正渗透膜；
（4）采用表面担载法将活性酶浸泡固定在正渗透膜表面上，所述的表面担载法包括先在纳米纤维膜表面形成-NH2，再用戊二醛接枝，然后将处理后的纳米纤维膜浸泡在活性酶的缓冲液中，获得集催化和分离为一体正渗透复合膜；
步骤（1）所述的高分子聚合物为聚丙烯腈、聚酰胺或者聚酰亚胺，所述的溶剂为N-N二甲基甲酰胺，N-N二甲基乙酰胺，丙酮，环己烷中的一种或者几种；
步骤（3）中所述的水相单体为双酚、哌嗪、间苯二胺、邻苯二胺及其衍生物中的一种或几种，其浓度为1～5wt%；有机相单体为对苯二甲酰氯、间苯二甲酰氯、均苯三甲酰氯中的一种或几种，其浓度为0.01～5wt%；
步骤（4）中所述的活性酶包括β-内酰胺酶、谷胱甘肽S-转移酶、漆酶和过氧化物酶中的一种或几种。
2.根据权利要求1所述的酶催化型正渗透膜的制备方法，其特征在于，步骤（1）所述的高分子聚合物为聚丙烯腈、聚酰胺，所述的溶剂为N-N二甲基甲酰胺，N-N二甲基乙酰胺，丙酮中的一种或者几种；步骤（3）中所述的水相单体为间苯二胺或邻苯二胺，其浓度为1～3wt%；有机相单体为对苯二甲酰氯、均苯三甲酰氯中的一种或两种，其浓度为0.01～0.3wt%，有机相单体溶于正己烷中形成有机相单体溶液。
3.根据权利要求1所述的酶催化型正渗透膜的制备方法，其特征在于，步骤（2）中纺丝电压为5～30kV，溶液的给料流速为0.3～2mL/h，纺丝喷射电极与接收装置的距离为5～30cm。
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