CN106731877A - 基于Ag/AgX的可见光催化平板式超滤膜及制备方法 - Google Patents
基于Ag/AgX的可见光催化平板式超滤膜及制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于Ag/AgX的可见光催化平板式超滤膜及制备方法，属于膜分离技术领域。将8.0%～20.0%(w/w)的聚砜或聚醚砜、5.0%～15.0%(w/w)的致孔剂、0.05%～2.0%(w/w)的表面活性剂、0.05%～5.0%(w/w)的Ag/AgX和58.0%～86.9%(w/w)的溶剂按照一定的顺序加入到三口圆底烧瓶中，在30～80℃温度下搅拌溶解5～16小时至完全溶解，静置脱泡8～24小时，制成铸膜液；采用相转化法在洁净的玻璃板上刮膜，制备可见光催化平板式超滤膜。本发明所制备超滤膜的纯水通量≥500L/m2·hr·0.1MPa，牛血清蛋白截留率≥90.00％，对黄腐酸的降解去除率≥70%（模拟可见光下，运行1小时），具有良好的抗污染性能和可见光催化性能。本发明产品特别适用于微污染水源水处理、海水淡化预处理及生物、化工、医药领域废水的处理与回用等。
Description
技术领域
本发明涉及一种高分子混合基质超滤膜及其制备方法，特别是涉及一种基于Ag/AgX的可见光催化平板式超滤膜及制备方法。
背景技术
水资源的匮乏和日益严重的水污染已成为制约社会进步和经济发展的瓶颈，新水源开发和废污水资源化利用也成为全球普遍关注的问题。由于地球上海水资源极为丰富，且产生大量的废污水，污水资源化和海水淡化已成为解决水资源危机的战略选择。在诸多的污水资源化技术中，膜分离技术是最好的选择之一。
混合基质膜，又称杂化膜，是将有机和无机成分化学交联或微观混合形成的膜，又称“有机-无机杂化膜”，因兼具无机膜的耐腐蚀、耐热性和有机膜的高分离性和韧性等优点，成为了研究膜材料改性的热点之一。近年来，国内外学者采用共混法或溶胶凝胶法制备对紫外光响应的纳米无机材料/聚合物杂化超滤膜，使之同时具有光催化和膜分离的多功能性，有着很好的开发与应用前景；如中国专利ZL201410312781.8采用纳米无机材料与膜材料共混制备了对紫外光响应的超滤膜，使之在紫外光催化作用下具有对有机污染物的降解性能；鉴于紫外光的光能只占不到5%的太阳光能，严重限制了二氧化钛改性膜的实际应用。因此，通过掺杂或涂覆可见光催化剂制备可见光催化超滤膜，在提高超滤膜的抗污染性的同时，又使超滤膜具有可见光催化活性，拓展超滤膜的应用范围，是近年来超滤膜研究的热点。
中国专利CN104383821A采用氧化石墨烯负载核壳结构的磁性粒子@TiO2制备改性分离膜，认为分离膜对目标污染物牛血清蛋白表现出了良好的光催化降解性能和抗蛋白污染性能，但未在专利申请中阐明所制备膜的分离性能和可见光催化降解性能的优劣，且所述分离膜制备工艺复杂；同时，氧化石墨烯负载核壳结构的磁性粒子@TiO2制备方法复杂、成本高。中国专利CN104117291A采用TiO2/C杂化气凝胶改性制备了聚偏氟乙烯膜，所制备的膜在氙灯（可见光）照射下改性PVDF 膜对活性艳红X-3B 的降解率仅为13.96% ，而在汞灯（紫外光）照射下对活性艳红X-3B 降解率则为93.28%，可证明所制备的膜仍然是对紫外光响应的超滤膜，而不是可见光催化超滤膜。中国专利CN102989329A通过将AgNO3、TiO2共混改性制备超滤膜，事实上是主要利用了AgNO3的可见光催化活性，且降解速率较慢（专利中采用了光照10小时对亚甲基蓝的降解率进行光催化性能表征），无法制备同时用于分离和可见光催化的分离膜；中国专利CN104383820A则将Ag3PO4/TiO2复合物（Ag3PO4纳米颗粒沉积到TiO2表面）与聚偏氟乙烯材料共混改性，使改性膜具备可见光催化抗菌防污性能，主要利用沉积在TiO2表面的Ag3PO4颗粒降解分离膜应用过程中吸附的有机物，以减少膜污染，没有用于制备同时具有分离和可见光催化性能的分离膜；同时，这两个专利均没有通过协同效应以充分利用银盐和TiO2的催化性能，仅仅通过共混或沉积而利用了银盐或银盐与TiO2各自的催化活性，可见光催化效率较低。中国专利CN102895888A则先制备二氧化钛/聚偏氟乙烯膜，然后在其表面吸附、还原银离子来制备可见光响应性聚偏氟乙烯膜，所制备膜的亚甲基蓝降解率为33%～51%（可见光照射100mins）；同时，本发明需要在完成二氧化钛/聚偏氟乙烯膜制备后，再通过吸附银离子、还原银离子为银单质、真空干燥等步骤才能完成专利产品的制备，且制备过程中需要暗室、紫外照射、真空干燥等条件，工艺复杂、制备成本高，产业化难度较大。
以nTiO2为代表的大多数光催化剂只有在紫外光照射下才能产生光催化活性，因此，发展可见光响应型光催化剂具有十分重要的意义。卤化银（AgX）是重要的感光材料，作为一种新型的光催化剂，在光催化降解有机污染物方面具有优良的光催化性能。而金属纳米颗粒具有独特的光学性质-表面等离子体共振，单质Ag 对半导体AgX起杂化作用，使其响应光波长发生红移，从而使能量低于禁带宽度的近紫外光激发其电子跃迁，诱发光化学反应，而太阳光在此范围的光较强。银/银卤化物（Ag/AgX）是基于纳米金属表面等离子体效应和半导体光催化效应的新型可见光光催化材料，其对有机染料的可见光分解速度是远高于普通可见光光催化剂。将Ag/AgX与高分子材料共混进行可见光催化混合基质超滤膜的研制，对提高膜分离效率、拓宽分离膜的应用领域、减轻膜污染具有一定的意义。
本发明采用Ag/AgX改善高分子超滤膜的可见光催化特性，制备具有可见光催化活性的平板式混合基质超滤膜，国内外尚未见相关文献报道。
发明内容
本发明的目的是提供一种基于Ag/AgX的可见光催化平板式超滤膜，本发明的另一个目的是提供该可见光催化平板式超滤膜的制备方法。
为实现上述目的，本发明采取的技术方案为：
一种基于Ag/AgX的可见光催化平板式超滤膜，是由以下质量百分比的物质组成的：聚合物膜材料8.0%～20.0%(w/w)、致孔剂5.0%～15.0%(w/w)、表面活性剂0.05%～2.0%(w/w)、Ag/AgX 0.05%～5.0%(w/w)、溶剂58.0%～86.9%(w/w)；
所述的聚合物膜材料为聚砜、聚醚砜的一种，含量为8.0%～20.0%(w/w)；
所述的致孔剂为聚乙二醇、聚乙烯吡咯烷酮的一种，含量为5.0%～15.0%(w/w)；
所述的表面活性剂为非离子表面活性剂，如聚山梨酯（吐温）、脂肪酸甘油酯、脂肪酸山梨坦等的一种，含量为0.05%～2.0%(w/w)；
所述的Ag/AgX是基于纳米金属表面等离子体效应和半导体光催化效应的新型可见光光催化材料，为Ag/AgCl、Ag/AgBr、Ag/AgI等的一种，含量为0.05%～5.0%(w/w)；
所述的溶剂为N,N-二甲基乙酰胺（DMAc）、N,N-二甲基甲酰胺（DMF）、N-甲基吡咯烷酮（NMP）的一种或两种混合，含量为58.0%～86.9%(w/w)。
一种基于Ag/AgX的可见光催化平板式超滤膜的制备方法，包括以下步骤：
（1）将一定量的溶剂、致孔剂、表面活性剂、Ag/AgX按照一定的比例、顺序分别加入到三口圆底烧瓶中，搅拌均匀；
（2）将一定量的聚合物膜材料加入到三口圆底烧瓶中，在30～80℃温度下搅拌溶解5～16小时至完全溶解，配制成初始铸膜液；然后，将得到的铸膜液在搅拌溶解温度下静止放置8～24小时使其完全脱泡；
（3）将脱泡后的铸膜液倒在洁净的玻璃板上，采用特制的平板膜刮刀刮制成膜，在空气中停留5～60秒后，将玻璃板轻轻放入15～50℃恒温凝固浴中凝固成形，膜成形后自动脱离玻璃板，将膜取出后经去离子水洗涤24小时、50%甘油浸泡处理48小时，即可制得基于Ag/AgX的可见光催化平板式超滤膜。
所述的凝固浴为去离子水。
本发明提供了一种基于Ag/AgX的可见光催化平板式超滤膜及制备方法，将Ag/AgX可见光催化材料引入到聚合物中制备混合基质超滤膜，并赋予混合基质超滤膜良好的抗污染性和可见光催化降解有机污染物的性能，这是本发明的创新之处。为了检验所制备的可见光催化平板式超滤膜的抗污染性和可见光催化性能，本发明对所制备超滤膜的阻力增大系数和接触角进行了测试，结果表明阻力增大系数和接触角都明显降低，超滤膜的抗污染性得到了较大的提高。同时，以黄腐酸为目标污染物，将所制备的可见光催化平板式超滤膜进行可见光催化降解去除率和超滤膜通量变化测试，结果表明，所制备的超滤膜在模拟可见光下运行时表现出良好的光催化降解性能和抗污染性能，膜的通量衰减明显降低。
本发明和已有技术相比，具有如下有益的效果：
（1）本发明所提供的Ag/AgX共混改性所制备的可见光催化平板式超滤膜与传统聚砜、聚醚砜超滤膜相比，其抗污染性和可见光催化活性得到了明显的改善，可在进行膜分离的同时实现对有机污染物的催化降解。
（2）本发明所提供的Ag/AgX共混改性制备可见光催化平板式超滤膜的方法，所用的设备简单、易控，膜制备工艺简单，成膜的同时赋予所制备超滤膜可见光催化活性和抗污染性，易实现产业化。
具体实施方式：
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1：
将71.0%(w/w)的二甲基乙酰胺、13.0%(w/w)的聚乙二醇400、0.5%(w/w)的吐温-80和2.5%(w/w)的Ag/AgCl按照一定的顺序分别加入到三口圆底烧瓶中，搅拌均匀；然后加入13.0%(w/w)的聚砜，在70℃温度下搅拌溶解7小时至完全溶解；然后，将得到的铸膜液在搅拌溶解温度下静止放置16小时，脱除铸膜液中残存的气泡。
将脱泡后的铸膜液倒在洁净的玻璃板上，采用特制的平板膜刮刀刮制成膜，在空气中停留15秒后，浸入到25℃恒温凝固浴中凝固成形，膜成形后自动脱离玻璃板，将膜取出后经去离子水洗涤24小时、50%甘油浸泡处理48小时，即可制得基于Ag/AgCl的可见光催化平板式超滤膜。
本实施例所制备的可见光催化平板式超滤膜的纯水通量为556.43L/m2·hr·0.1MPa，牛血清蛋白截留率为91.57%，阻力增大系数为1.25，接触角为71.1°；对黄腐酸的降解去除率由44.67%（无光照，运行1小时）提高到75.13%（模拟可见光下，运行1小时）。
实施例2：
将Ag/AgCl含量由2.5%(w/w)降为0.05%(w/w)，二甲基乙酰胺的含量由71.0%(w/w)提高到73.45%(w/w)，其余的同实施例1。则所制备的基于Ag/AgCl的可见光催化平板式超滤膜的纯水通量为441.41 L/m2·hr·0.1MPa，牛血清蛋白截留率为91.63%，阻力增大系数为1.61，接触角为83.2°；对黄腐酸的降解去除率由30.76%（无光照，运行1小时）提高到40.35%（模拟可见光下，运行1小时）。
实施例3：
将Ag/AgCl含量由2.5%(w/w)提高到5.0%(w/w)，二甲基乙酰胺的含量由71.0%(w/w)降为68.5%(w/w)，其余的同实施例1。则所制备的基于Ag/AgCl的可见光催化平板式超滤膜的纯水通量为581.39 L/m2·hr·0.1MPa，牛血清蛋白截留率为91.31%，阻力增大系数为1.23，接触角为71.0°；对黄腐酸的降解去除率由45.69%（无光照，运行1小时）提高到77.83%（模拟可见光下，运行1小时）。
实施例4：
将Ag/AgX由Ag/AgCl替换为Ag/AgBr，其余的同实施例1。则所制备的基于Ag/AgBr的可见光催化平板式超滤膜的纯水通量为539.56 L/m2·hr·0.1MPa，牛血清蛋白截留率为91.41%，阻力增大系数为1.27，接触角为71.4°；对黄腐酸的降解去除率由43.19%（无光照，运行1小时）提高到72.76%（模拟可见光下，运行1小时）。
实施例5：
将Ag/AgX由Ag/AgCl替换为Ag/AgI，其余的同实施例1。则所制备的基于Ag/AgI的可见光催化平板式超滤膜的纯水通量为521.23 L/m2·hr·0.1MPa，牛血清蛋白截留率为91.53%，阻力增大系数为1.28，接触角为71.6°；对黄腐酸的降解去除率由42.59%（无光照，运行1小时）提高到72.08%（模拟可见光下，运行1小时）。
比较例1：
将73.5%(w/w)的二甲基乙酰胺、13.0%(w/w)的聚乙二醇、0.5%(w/w)的吐温-80和13.0%(w/w)的聚砜按照一定的顺序分别加入到三口圆底烧瓶中，在70℃温度下搅拌溶解7小时至完全溶解；然后，将得到的铸膜液在搅拌溶解温度下静止放置16 小时，脱除铸膜液中残存的气泡。
将脱泡后的铸膜液倒在洁净的玻璃板上，采用特制的平板膜刮刀刮制成膜，在空气中停留15秒后，浸入到25℃恒温凝固浴中凝固成形，膜成形后自动脱离玻璃板，将膜取出后经去离子水洗涤24小时、50%甘油浸泡处理48小时即可制得平板式聚砜超滤膜。
本比较例所制备的平板式聚砜超滤膜的纯水通量为356.25 L/m2·hr·0.1MPa，牛血清蛋白截留率为92.65%，阻力增大系数为1.82，接触角为88.9°；对黄腐酸的降解去除率由23.87%（无光照，运行1小时）提高到24.09%（模拟可见光下，运行1小时）。
Claims (6)
1.一种基于Ag/AgX的可见光催化平板式超滤膜，其特征在于，其铸膜液中含有Ag/AgX，并影响超滤膜的结构和性能；铸膜液由以下质量百分比的物质组成：聚合物膜材料8.0%～20.0%(w/w)、致孔剂5.0%～15.0%(w/w)、表面活性剂0.05%～2.0%(w/w)、Ag/AgX 0.05%～5.0%(w/w)，其余为溶剂。
2. 根据权利要求1 所述的基于Ag/AgX的可见光催化平板式超滤膜，其特征在于：所述的超滤膜是采用传统的相转化法即干-湿法制备的。
3. 根据权利要求1 所述的基于Ag/AgX的可见光催化平板式超滤膜，其特征在于：所述的Ag/AgX是基于纳米金属表面等离子体效应和半导体光催化效应的新型可见光光催化材料，为Ag/AgCl、Ag/AgBr、Ag/AgI等的一种，含量占铸膜液总重量的0.05%～5.0%(w/w)。
4. 根据权利要求1 所述的基于Ag/AgX的可见光催化平板式超滤膜，其特征在于：所述的聚合物膜材料为聚砜、聚醚砜的一种；所述致孔剂为聚乙二醇、聚乙烯吡咯烷酮的一种；所述的表面活性剂为非离子表面活性剂，如聚山梨酯（吐温）、脂肪酸甘油酯、脂肪酸山梨坦等的一种；所述的溶剂为N,N-二甲基乙酰胺（DMAc）、N,N-二甲基甲酰胺（DMF）、N-甲基吡咯烷酮（NMP）的一种或两种混合。
5.一种基于Ag/AgX的可见光催化平板式超滤膜的制备方法，其特征在于它包括：
步骤（1）将一定量的溶剂、致孔剂、表面活性剂和Ag/AgX按照一定的比例、顺序分别加入到三口圆底烧瓶中，搅拌均匀；
步骤（2）将聚砜或聚醚砜加入到三口圆底烧瓶中，在30～80℃温度下搅拌溶解5～16小时至完全溶解，静止放置脱泡8～24 小时，即得到可见光催化平板式超滤膜铸膜液；
步骤（3）将脱泡后的铸膜液倒在洁净的玻璃板上，采用特制的平板膜刮刀刮制成膜，在空气中停留5～60秒后，将玻璃板轻轻放入15～50℃恒温凝固浴中凝固成形，膜成形后自动脱离玻璃板，将膜取出后经去离子水洗涤、50%甘油浸泡处理即可制得基于Ag/AgX的可见光催化平板式超滤膜。
6. 根据权利要求5 所述的基于Ag/AgX的可见光催化平板式超滤膜的制备方法，其特征在于：所述的凝固浴为去离子水。
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