CN113522038B - 一种用于去除水中污染物的复合膜制备方法及应用 - Google Patents
一种用于去除水中污染物的复合膜制备方法及应用 Download PDFInfo
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Abstract
本发明涉及膜吸附分离材料制备技术领域。具体涉及一种用于去除水中污染物的复合膜制备方法及应用。将氧化石墨烯水溶液与纳米颗粒按比例共混，PEG充当交联剂，通过真空自组装法将氧化石墨烯负载到多孔微滤基膜上，并在60℃的环境下干燥，制得氧化石墨烯复合膜。本发明制备方法简单快速，反应条件温和，不需要复杂的仪器设备即可完成，且所得氧化石墨烯复合膜具有良好的亲水性、稳定性和对水中污染物较高的去除效果。
Description
技术领域
本发明属于膜吸附分离材料制备技术领域，具体涉及一种用于去除水中污染物的复合膜制备方法及应用。
背景技术
传统工业废水中含有大量氮化物、氟化物、重金属（铜、镉、铅等）等无机污染物，医药工业废水中则含有高浓度的酚类、苯胺以及抗生素等有机污染物。经过生化和混凝沉淀等方法处理后，有机物、重金属、硬度、含盐量等指标仍然较高，必须采取有效的深度处理工艺加以去除，达到国家排放标准后才能将其排放。
处理工业废水的主要方法有物理化学法、氧化法和吸附法等，具有成本较高、去除效率低、易二次污染等缺点。膜吸附是膜技术与吸附技术相结合的集成工艺，膜吸附采用具有一定孔径的膜作为介质，嵌入或连接功能颗粒和配基，以此与目标污染物相互作用，达到分离目的。是21世纪最有发展前途的高新生产技术之一，成为世界各国研究的热点。
氧化石墨烯（GO）含有丰富的含氧官能团，具有性质稳定、比表面积高（2630 m2/g）、亲水性好等优点。通过GO的功能化改性或嵌入吸附功能颗粒，制备出具有高吸附容量并兼具分离性能的复合膜材料。申请号为CN201910648052.2的专利公布了一种高效去除痕量有机污染物的CNT-GO复合膜的制备方法，通过将碳纳米管与GO按比例混合后，采用沉积法和抽滤法制备出对微污染物去除效率高、稳定性能强的复合膜。申请号为CN201910896429.6的专利公布了一种具有吸附功能的氧化石墨烯分离膜制备方法及其制得的产品。通过混合沉淀法将纳米水合氧化锰与氧化石墨烯，在多孔无机或有机载体上制得了膜材料。申请号为CN201510611648.7的专利公布了一种氧化石墨烯金属/金属氧化物纳米粒子改性的中空纤维超滤膜及其制备方法，将氧化石墨烯和金属氧化物纳米粒混合得到铸膜液，然后纺制成膜。以上表明可以在氧化石墨烯中添加高分子材料或纳米粒来，以此来提高膜材料的吸附性能，然而往往GO层在复合材料表面附着不稳容易脱落。
申请号为CN201910573071.3的专利公布了一种氧化铝/氧化石墨烯/聚乙烯醇复合纳滤膜的制备方法，先通过加热反应将氧化铝负载到氧化石墨烯上，得到氧化铝/氧化石墨烯溶液，采用涂覆法将该溶液与聚乙二醇交替涂覆在聚醚砜超滤膜上，制得表面带有负电荷的纳滤膜材料。此方法优点在于膜材料表面的负电荷提高了膜层的盐截留率，但溶液制备时间过长，并伴有加热反应，操作繁杂。
申请号为CN201710264132.9的专利公开了一种氧化石墨烯改性的高性能超滤复合膜及其制备方法，首先将PVDF超滤膜分别在氢氧化钾、四丁基氟化铵混合液和亚硫酸氢钠、浓硫酸混合液中浸泡一段时间进行活化，再依次接枝酰氯基官能团、氧化石墨烯、氨基官能团、氧化石墨烯，重复数次，置于纯水中得到所需膜材料。此方法的优点在于乙二胺使得氧化石墨烯更加稳定，可以得到不同层数的氧化石墨烯复合膜。但是制备过程中用到浓硫酸等危险试剂，且操作过程过于繁杂。
发明内容
本发明所要解决的技术问题在于克服传统繁杂的制膜方法，设计一种具有较强稳定性，吸附容量良好的新型复合膜。本发明以多孔滤膜为基膜，将GO与纳米材料以不同比例混合真空自组装在基体上，加入适量交联剂制得新型复合膜，用于水中污染物的去除，操作简单快捷。
本发明采用以下技术方案：一种用于去除水中污染物的复合膜制备方法，其中，制备包括如下步骤：
步骤一：将氧化石墨烯加入纯水，室温超声，得到氧化石墨烯分散液；
步骤二：将PEG400溶于纯水中，室温超声，得到PEG溶液；
步骤三：将纳米材料，沸石或PS-DVB加入到纯水中，室温超声，得到纳米颗粒悬浊液；
步骤四：将步骤一、步骤二和步骤三的溶液共混；室温超声，得到氧化石墨烯与纳米颗粒混合溶液；
步骤五：将多孔微滤基膜放入真空抽滤头中，把步骤四的溶液均匀铺到基膜上，采用真空自组装法抽滤成膜；
步骤六：将膜片放入真空干燥箱中，真空干燥，得到复合膜。
进一步的，步骤一中氧化石墨烯分散液浓度为10 mg/mL，制备一份浓度为10 mg/mL的分散液步骤为量取8 mL氧化石墨烯溶液，加入纯水32 mL，超声30 min，得到分散液。
进一步的，步骤二中PEG溶液浓度为2 mg/mL，制备PEG溶液步骤为称取200 mg PEG加入到100 mL纯水中，配制成浓度为2 mg/mL的溶液。
进一步的，步骤三中纳米颗粒悬浊液浓度为200 μg/mL，制备纳米颗粒悬浊液步骤为称取100 mg纳米颗粒加入到100 mL纯水中，逐级稀释成浓度为200 μg/mL的沸石悬浊液。
进一步的，步骤四中氧化石墨烯与纳米颗粒混合溶液质量比为1:50，制备一份氧化石墨烯与纳米颗粒质量比1:50的溶液步骤为将2 mL步骤一的分散液、2 mL步骤二的PEG溶液和2 mL步骤三的悬浊液共混，超声30 min，得到所需溶液。
进一步的，步骤五中将多孔微滤基膜放入真空抽滤头中，使用移液枪把步骤四的溶液均匀铺到基膜上，在0.1MPa压力下抽滤成膜。
进一步的，所述多孔微滤基膜为尼龙膜或者PAN膜。
进一步的，步骤六中将膜片放入60℃的真空干燥箱中，真空干燥两个小时，得到复合膜。
一种用于去除水中污染物的复合膜在吸附水中四环素的应用。
本发明有益效果：将氧化石墨烯水溶液与纳米颗粒按比例共混，PEG充当交联剂，通过真空自组装法将氧化石墨烯负载到多孔微滤基膜上，并在60℃的环境下干燥，制得氧化石墨烯复合膜。本发明制备方法简单快速，反应条件温和，不需要复杂的仪器设备即可完成，且所得氧化石墨烯复合膜具有良好的亲水性、稳定性和对水中污染物较高的去除效果。
附图说明
图1氧化石墨烯/沸石复合膜表面SEM图；
图2氧化石墨烯/沸石复合膜截面SEM图；
图3 GO/PS-DVB/PAN复合膜表面SEM图；
图4 GO/PS-DVB/PAN复合膜截面SEM图
图5 氧化石墨烯/沸石复合膜表面全反射IR图；
图6 不同膜材料对水中四环素的吸附容量对比图。
具体实施方式
下面的实施例中对本发明的技术方案作进一步的阐述，但本发明不限于此。以下实施例所得复合膜表面及断面形貌表征用场发射扫描电子显微镜测定，水中铜离子浓度测定用紫外-可见分光光度计测定，水中抗生素浓度采用高效液相测定。
实施例1：GO/沸石/尼龙复合膜的制备
制备工艺：量取8 mL氧化石墨烯溶液，加入纯水32 mL，超声30 min，得到浓度为10mg/mL的分散液。称量200 mg PEG400溶入100 mL纯水中，配制成浓度为2 mg/mL的溶液。称取100 mg沸石放入100 mL 纯水中，逐级稀释成浓度为200 μg/mL的悬浊液。量取2 mL分散液、2 mL PEG400溶液和2 mL悬浊液共混，超声30min，得到氧化石墨烯与纳米颗粒质量比为1:50的溶液；将多孔微滤基膜——尼龙膜放入真空抽滤头中，使用移液枪把上述1：50溶液均匀铺到基膜上，采用真空自组装法在0.1MPa压力下抽滤成膜，，取出膜片后在60℃的环境下干燥，得到以尼龙膜为基膜的氧化石墨烯/沸石复合分离膜，用于水中四环素（10 mL,5 μg/mL）的吸附过程，吸附容量达到4.52 mg/g，比未加纳米可颗粒复合膜（GO,3.7 mg/g）提高22.1%。
常压渗透实验：在U型管中，膜片把其分为两个隔室，一边放入铜离子浓度为150 μg/mL的氯化铜盐溶液，一边放入等体积的纯水。每隔4小时测量两边铜离子浓度，经过36小时的常压渗透，发现膜对铜离子的截留率达到98.22%，比纯氧化石墨烯膜的截留率提高5.42%。
实施例2：GO/PS-DVB/PAN复合膜的制备
制备工艺：量取8 mL氧化石墨烯溶液，加入纯水32 mL，超声30 min，得到浓度为10mg/mL的分散液。称量200 mg PEG400溶入100 mL纯水中，配制成浓度为2 mg/mL的溶液。称取200 mg PS-DVB放入100 mL 纯水中，逐级稀释成浓度为200 μg/mL的悬浊液。量取2 mL分散液、2 mL PEG400溶液和2 mL悬浊液共混，超声30min，采用真空自组装法，在PAN膜上制得质量比GO:PAN=1:50的膜片，取出后在60℃的环境下干燥，得到以PAN膜为基膜的GO/PS-DVB复合膜，用于水中四环素（10 mL,5 μg/mL）的吸附过程,吸附容量达到5.42 mg/g，比未加纳米可颗粒复合膜（GO,3.7 mg/g）提高46.4 %。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。
Claims (5)
1.一种用于去除水中污染物的复合膜制备方法，其特征在于，制备包括如下步骤：
步骤一：将氧化石墨烯加入纯水，室温超声，得到氧化石墨烯分散液；氧化石墨烯分散液浓度为10 mg/mL，制备一份浓度为10 mg/mL的分散液步骤为量取8 mL氧化石墨烯溶液，加入纯水32 mL，超声30 min，得到分散液；
步骤二：将PEG400溶于纯水中，室温超声，得到PEG溶液；所述PEG溶液浓度为2 mg/mL，制备PEG溶液步骤为称取200 mg PEG加入到100 mL纯水中，配制成浓度为2 mg/mL的溶液；
步骤三：将纳米材料，沸石或PS-DVB加入到纯水中，室温超声，得到纳米颗粒悬浊液；所述纳米颗粒悬浊液浓度为200 μg/mL，制备纳米颗粒悬浊液步骤为称取100 mg纳米颗粒加入到100 mL纯水中，逐级稀释成浓度为200 μg/mL的沸石悬浊液；
步骤四：将步骤一、步骤二和步骤三的溶液共混；室温超声，得到氧化石墨烯与纳米颗粒混合溶液；氧化石墨烯与纳米颗粒混合溶液质量比为1:50，制备一份氧化石墨烯与纳米颗粒质量比1:50的溶液步骤为将2 mL步骤一的分散液、2 mL步骤二的PEG溶液和2 mL步骤三的悬浊液共混，超声30 min，得到所需溶液；
步骤五：将多孔微滤基膜放入真空抽滤头中，把步骤四的溶液均匀铺到基膜上，采用真空自组装法抽滤成膜；
步骤六：将膜片放入真空干燥箱中，真空干燥，得到复合膜。
2.根据权利要求1所述的一种用于去除水中污染物的复合膜制备方法，其特征在于，步骤五中将多孔微滤基膜放入真空抽滤头中，使用移液枪把步骤四的溶液均匀铺到基膜上，在0.1MPa压力下抽滤成膜。
3.根据权利要求2所述的一种用于去除水中污染物的复合膜制备方法，其特征在于，所述多孔微滤基膜为尼龙膜或者PAN膜。
4.根据权利要求1所述的一种用于去除水中污染物的复合膜制备方法，其特征在于，步骤六中将膜片放入60℃的真空干燥箱中，真空干燥两个小时，得到复合膜。
5.如权利要求1所述方法制备的复合膜在吸附水中四环素的应用。
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