CN115090123B - 一种基于荷正电纳米材料中间层的纳滤膜制备及其应用 - Google Patents
一种基于荷正电纳米材料中间层的纳滤膜制备及其应用 Download PDFInfo
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Abstract
本发明公开了一种基于荷正电纳米材料中间层的纳滤膜制备及其应用。通过阳离子改性剂对纳米材料进行电荷改性,获得荷正电纳米材料分散液;将荷正电纳米材料分散液通过真空抽滤复合到多孔载体膜表面,形成双层复合膜;在双层复合膜进行界面聚合制备聚酰胺表层,获得复合双电荷纳滤膜。本发明的方法操作简单,绿色环保,可有效改善纳滤膜的渗透和分离性能,大幅度提高对重金属阳离子的截留效果,可应用于重金属废水处理领域。
Description
技术领域
本发明涉及了一种纳滤膜制备方法,尤其是涉及一种基于荷正电纳米材料中间层的纳滤膜制备。
背景技术
纳滤膜对物质的分离机制主要是尺寸筛分效应和静电排斥效应,纳滤膜具有操作压力低、渗透通量大等优点,因此被广泛用于硬水软化、废水处理等领域。通过在纳滤膜中引入纳米材料作为中间层,利用中间层亲水性好,孔径小,等优点,提高纳滤膜的整体水通量。另一方面,商用纳滤膜表面大部分为荷负电,对染料等阴离子有较高截留效果。使用阳离子改性剂对中间层纳米材料进行正电荷改性,便可得到正电荷密度分布均匀的中间层,大幅度提高纳滤膜整体对重金属阳离子的截留效果。该发明提出的实验方法操作简便,底膜选择范围广,制备过程灵活可控,有望成为一种新的纳滤膜制备方法,应用于重金属废水处理领域。
例如,公开号为CN114130227A的中国专利公开了一硫酸化纤维素纳米纤丝作为纳滤膜中间支撑层的应用,所述纤维素纳米纤丝经过硫酸化改性后,表面存在硫酸基团,能够调节表层,同时,具有较为优异的机械性能,能够增加纳滤膜的机械性能。硫酸化纤维素纳米纤丝作为纳滤膜中间支撑层能够大大增加纳滤膜分离性能,对硫酸钠的截留能够提高21%以上。
公开号为CN113318616A的中国专利公开了一种rGO/ZIF-8复合纳米材料作中间层改性纳滤膜,,包括:配制铸膜液,通过相转化法制备多孔支撑底膜;将rGO/ZIF-8复合材料均匀分散在缓冲溶液中超声处理;加入盐酸多巴胺后共沉积于多孔支撑底膜上,热处理,形成PDA-rGO/ZIF-8膜置于多元胺水溶液中,多元酰氯-油相溶液于PDA-rGO/ZIF-8膜表面进行界面聚合,热处理后制得改性有机分离纳滤膜。该复合纳米材料极大的改善了其亲水性,使其在水相溶液中的分散性增强,减少材料因团聚而对纳滤膜表面造成的缺陷,使膜选择性无大幅下降的同时,提高膜的渗透性。
公开号为CN114534514A的中国专利公开了一种含单宁酸-铜络合网络中间层的复合耐溶剂膜、制备方法及应用,所述的以单宁酸和铜离子原位生成络合网络作为中间层的超薄复合耐溶剂膜的制备步骤包括原位生成单宁酸-铜络合中间层步骤、界面聚合反应步骤、化学交联步骤和溶剂活化步骤;本发明通过引入单宁酸-铜络合网络中间层,显著地提高了膜的通量和截留率,并可以使用极低浓度的水相和油相单体溶液;所述的单宁酸由于具有大量酚羟基,可以增加基膜的亲水性,增加水相单体的储存;单宁酸与铜离子络合生成络合网络,可以增加中间层的稳定性,有利于界面聚合反应,从而有效提高膜的分离性能。本发明制备工艺简单,在有机溶液体系分离领域具有很好的应用前景。
公开号为CN112452164A的中国专利公开了一种含纤维素纳米晶体中间层及多巴胺原位改性层的两步改性复合纳滤膜及其制备方法。方法:将纤维素纳米晶体分散液抽滤到微滤膜底层表面,然后依次在哌嗪溶液和均苯三甲酰氯溶液中浸渍,取出后进行热处理,最后浸没在多巴胺混合溶液中,得到复合纳滤膜。本发明的方法极大地提高纳滤膜的渗透性能,与此同时也能一定程度地提升其截留性能。
已经报道的纳滤膜制备方法中,引入中间层的方法被广泛应用于科研实验,社会生产,而专门针对正电荷改性后的纳米材料中间层复合纳滤膜的制备方法较少。
发明内容
为了解决背景技术中存在的问题,即目前商用纳滤膜对阳离子截留率不够高、渗透率和分离性能之间存在权衡效应的问题,本发明提供了一种基于荷正电纳米材料中间层的纳滤膜制备及其在重金属废水处理领域的应用。
本发明解决了渗透量和分离性能之间的权衡效应的难题,在商用纳滤膜的高效阴离子的截留效果的基础上,提高重金属阳离子的截留以及渗透量的提升。本发明有望大批量进行生产,应用于重金属废水处理领域。
本发明的技术方案包括以下步骤:
本发明方法是在多孔载体膜上引入一种基于荷正电纳米材料中间层,在其上方继续进行典型的界面聚合反应获得荷负电聚酰胺表层,最终得到双电荷的复合纳滤膜。
本发明中阳离子化纳米材料的改性方法简单,条件温和,得到荷正电纳米材料与基材具有良好的稳定性;最终制备得到的复合纳滤膜对重金属阳离子的截留有大幅度的提升。
首先,荷正电的中间层的引入,大大提高了纳滤膜对阳离子的截留效果;其次,纳米材料的引入可以提高水通量,超高透水通量使纳滤能够在较低的工作压力下进行,从而使其成为一种节能过程,为工业上大规模生产降低成本。
本发明的有益效果是:
本发明通过在传统的复合纳滤膜中加入中间层,通过阳离子改性纳米材料的手段获得了低传质阻力的荷正电中间层,以及在保证聚酰胺表层的致密度的前提下减小分离层厚度,不仅提高膜的水通量,而且提高了对高价阳离子的截留效果。
由二胺和酰氯界面聚合反应形成典型聚酰胺表层带负电,对阴离子有高效的截留效果。荷正电纳米材料中间层不仅大幅度提高纳滤膜的渗透通量,还可以提高阳离子高价盐截留率。超高透水通量使纳滤能够在较低的工作压力下进行,是一种非常节能的制备工艺过程。
本发明的方法操作简单,绿色环保,可有效改善纳滤膜的渗透和分离性能,大幅度提高对重金属阳离子的截留效果,可应用于重金属废水处理领域。
附图说明
图1为本发明实施例中纳滤膜分离性能随着纳米材料浓度变化的性能图。
纳米材料浓度分别为0,20,30,40,50制备得到不同复合双电荷纳滤膜,分别对硫酸钠和氯化镁的截留效果。
具体实施方式
下面结合附图和具体实施对本发明作进一步说明。
本发明的实施例如下:
实施例1:
1)将浓度为10wt%的阳离子改性剂环氧丙基三烷基氯化铵加入到纳米纤维素材料分散液中进行季铵化改性,在90℃条件下反应12h得到荷正电季铵化纳米纤维素分散液;
2)取25ml的10wt%季铵化纳米纤维素分散液真空抽滤至聚醚砜膜表面,形成荷正电纳米材料中间层获得双层复合膜,放入真空烘箱中40℃烘干固化;
3)将烘干固化后的双层复合膜放入膜具,取浓度为1wt%的哌嗪2ml倒入双层复合膜表面浸渍1min,将多余哌嗪溶液倒出,放于室温晾干;取浓度为1wt%均苯三甲酰氯2ml倒入双层复合膜表面浸渍1min,将多余均苯三甲酰氯溶液倒出,哌嗪和均苯三甲酰氯在双层复合膜表面进行界面聚合形成聚酰胺表层,放入烘箱70℃烘干1h,最终得到复合双电荷纳滤膜。
实施例2~5:将阳离子化试剂分别替换为3-氯-2羟基丙基三甲基氯化铵、环氧丙基三甲基氯化铵、聚乙烯亚胺、十八烷基二甲基-(3-三甲氧硅烷基-丙基)氯化铵,其余条件同实施例1。
实施例6~9:将阳离子改性剂浓度分别替换为20,30,40,50wt%,其余条件同实施例1。
实施例10~13:将纳米材料分别替换为碳纳米管,氢氧化镉纳米线,水铝英石纳米管,氧化石墨烯,其余条件同实施例1。
实施例14~17:将纳米材料浓度分别替换为20,30,40,50,其余条件同实施例1。
实施例18~21:将界面聚合单体浓度分别替换为2,3,4,5wt%,其余条件同实施例1
实施例22~25:将界面聚合单体反应时间分别替换为2,3,4,5h,其余条件同实施例1。
实施例26~29:将聚醚砜载体膜替换为聚砜、聚丙烯腈、聚乙烯、聚氯乙烯,其余条件同实施例1。
由此实施可见,本发明的一种基于荷正电纳米材料中间层的纳滤膜,具有高通量,高重金属截留率的特点,制备方法操作简单。可应用于重金属废水处理等领域。
Claims (5)
1.一种基于荷正电纳米材料中间层的纳滤膜制备方法,其特征在于:方法包括以下步骤:
1)通过阳离子改性剂对纳米材料进行电荷改性,获得荷正电纳米材料分散液;
所述的步骤1)具体为:由纳米纤维素制备纳米纤维素分散液,将浓度为10wt%的阳离子改性剂加入到纳米纤维素分散液中进行改性处理,改性反应时间为12小时,温度为90摄氏度,得到荷正电纳米纤维素分散液;
所述的阳离子改性剂为3-氯-2羟基丙基三甲基氯化铵、环氧丙基三甲基氯化铵、环氧丙基三烷基氯化铵、十八烷基二甲基-(3-三甲氧硅烷基-丙基)氯化铵中的至少一种,阳离子改性剂的浓度为10~60wt%;
2)将荷正电纳米材料分散液通过真空抽滤复合到多孔载体膜表面,形成双层复合膜;
所述的步骤2)具体为:将荷正电纳米纤维素分散液真空抽滤至聚醚砜膜表面形成双层复合膜,使得荷正电纳米纤维素在聚醚砜膜上形成纳米纤维素中间层,再将双层复合膜放置在真空烘箱中进行烘干固化;
3)在双层复合膜进行界面聚合制备聚酰胺表层,获得复合双电荷纳滤膜;
所述的步骤3)是利用哌嗪和均苯三甲酰氯在纳米纤维素中间层之上进行界面聚合反应形成聚酰胺膜,得到复合双电荷纳滤膜;
所述的步骤3)具体为:将双层复合膜放入容器中,先将哌嗪溶液倒到双层复合膜的表面,静置1~6min后去除哌嗪溶液晾干;然后将均苯三甲酰氯溶液导入晾干后的双层复合膜的表面,静置1~6min后去除均苯三甲酰氯溶液晾干,从而进行界面聚合反应,得到复合双电荷纳滤膜。
2.根据权利要求1所述的一种基于荷正电纳米材料中间层的纳滤膜制备方法,其特征在于:所述的荷正电纳米纤维素分散液的浓度为10~60wt%。
3.根据权利要求1所述的一种基于荷正电纳米材料中间层的纳滤膜制备方法,其特征在于:所述哌嗪溶液和均苯三甲酰氯溶液中各自的质量浓度均为1~6wt%。
4.一种基于荷正电纳米材料中间层的纳滤膜,其特征在于由权利要求1-3任一项所述的制备方法获得。
5.权利要求4所述一种基于荷正电纳米材料中间层的纳滤膜的应用,其特征在于:在重金属废水处理领域的应用。
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