CN113731191B - 一种纳米纤维素络合物复合聚酰胺膜及其制备方法 - Google Patents
一种纳米纤维素络合物复合聚酰胺膜及其制备方法 Download PDFInfo
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Abstract
本发明属于膜分离技术领域,涉及一种纳米纤维素络合物复合聚酰胺膜及其制备方法。本发明具有多孔结构的纳米纤维素络合物利用内部的超亲水纳米通道实现兼具高通量、高分离精度聚酰胺复合膜的制备,且超亲水特征赋予复合膜优异的抗污性,其对于高性能分离膜的构筑具有重要的科学指导意义和实际应用价值。
Description
技术领域
本发明属于膜分离技术领域,涉及一种纳米纤维素络合物复合聚酰胺膜及其制备方法。
背景技术
随着工农业的迅速发展,水污染问题日益加剧,世卫组织称全球已有三成人(21亿)缺乏安全饮用水,每年有340多万人死于与水源有关的疾病。作为一种高效、环保、节能的分离技术,膜分离法可在分子水平上实现物质的选择性渗透分离,广泛应用于生物医药、电池隔膜、食品加工、气体分离、水处理、化工等领域。聚酰胺(PA)膜是分离膜的一个重要分支,由多元胺和多元酰氯单体在水与有机溶剂界面发生缩聚反应得到。由于界面聚合法具有操作简单、快速高效、自抑制性等优点,制备得到的PA膜已成为商品化纳滤膜和反渗透膜的主流产品。然而,PA膜存在着渗透性与选择性相互制约、易污染的共性难题,是制约分离效率的瓶颈。因此,亟需开发高性能的复合PA膜以推进其进一步发展和推广应用。
随着纳米技术的快速发展,将纳米材料原位引入到PA基质内构建薄层纳米复合(TFN)膜逐渐引起了广大学者的研究兴趣。该方法不仅可实现膜本体结构和表面结构的同步调控,而且只需在水相/有机相中原位加入纳米材料,是一种适于工业化应用的简便方法。现已有大量关于无机纳米材料(如SiO2、CNT、GO、Mxene等)TFN膜的报道,研究发现无机纳米材料的引入在不同程度上提高了复合膜的渗透通量(Water Res.,2020,173:115557;Adv.Mater.Interfaces,2021,8:2001671)。但无机纳米材料的分散性和与有机PA基体间的相容性较差,易产生界面缺陷,从而限制了复合膜的渗透选择性。
发明内容
本发明的目的是针对现有技术存在的上述问题,提出了一种高水渗透通量和分离精度的纳米纤维素络合物复合聚酰胺膜及其制备方法。
本发明的目的可通过下列技术方案来实现:一种纳米纤维素络合物复合聚酰胺膜,所述复合聚酰胺膜为通过含纳米纤维素络合物/胺类单体的水溶液和含多元酰氯单体的有机溶液在超滤膜表面进行界面聚合反应得到。
本发明还提供了一种纳米纤维素络合物复合聚酰胺膜的制备方法,所述方法包括如下步骤:
S1、将荷正电或负电的纳米纤维素水溶液滴加至与之相反电荷的纳米纤维素水溶液中,经离心、洗涤后得到纳米纤维素络合物水分散液;
S2、将超滤膜浸入到含纳米纤维素络合物和胺类单体的水相溶液中,排除膜表面过量水溶液,将多元酰氯有机溶液倒在膜表面静置,然后除去膜表面过量有机溶液,将膜热处理,经去离子水洗涤后得到纳米纤维素络合物复合聚酰胺膜。
本发明利用在水溶液中荷正电和荷负电纳米纤维素间静电作用力形成纳米纤维素络合物,在超滤膜表面进行含纳米纤维素络合物/胺类单体的水溶液和含多元酰氯单体的有机溶液间的界面聚合反应,得到纳米纤维素络合物复合聚酰胺膜。由于纳米纤维素络合物具有超亲水和多级孔特征,可提供超亲水纳米通道和超亲水表面,从而显著提升水渗透通量、分离精度和抗污性,实现聚酰胺膜的高性能化。
在上述的一种纳米纤维素络合物复合聚酰胺膜中,步骤S1荷正电纳米纤维素为季铵纤维素纳米纤维。
在上述的一种纳米纤维素络合物复合聚酰胺膜中,步骤S1荷负电纳米纤维素为TEMPO-纤维素纳米纤维、磷酸纤维素纳米纤维、羧甲基纤维素纳米纤维、磺酸纤维素纳米纤维、纤维素纳米晶中的任意一种。
在上述的一种纳米纤维素络合物复合聚酰胺膜中,步骤S1荷正电或负点的纳米纤维素水溶液浓度为0.01-0.5%,pH为2-12。
作为优选,步骤S1荷电型纳米纤维素的电荷量为0.1-4.0mmol/g。
作为优选,超滤膜为聚砜、聚醚砜、聚丙烯腈、聚偏氟乙烯超滤膜中的任意一种。
在上述的一种纳米纤维素络合物复合聚酰胺膜中,步骤S2水相溶液中纳米纤维素络合物的浓度为0.01-3%。
在上述的一种纳米纤维素络合物复合聚酰胺膜中,步骤S2水相溶液中胺类单体浓度为0.1-5%。
作为优选,胺类单体为哌嗪、间苯二胺、聚乙烯亚胺中的任意一种。
在上述的一种纳米纤维素络合物复合聚酰胺膜中,多元酰氯有机溶液的浓度为0.01-3%。
在上述的一种纳米纤维素络合物复合聚酰胺膜中,多元酰氯为均苯三甲酰氯、对苯二甲酰氯中的任意一种。
作为优选,多元酰氯有机溶液的溶剂为正己烷、环己烷、庚烷中的任意一种。
作为优选,将超滤膜浸入到纳米纤维素络合物和胺类单体的水相溶液中时间为1-10min,后排除膜表面过量水溶液,将多元酰氯有机溶液倒在膜表面静置时间为1-10分钟。
作为优选,步骤S2热处理温度为50-80℃,时间为5-20min。
作为优选,纳米纤维素络合物复合聚酰胺膜孔径为0.5-20nm、水接触角为2-40°、水渗透通量为35-100L/m2 h,无机盐截留率为5-100%。
与现有技术相比,本发明具有以下有益效果:
1.本发明通过多孔结构的纳米纤维素络合物利用内部的超亲水纳米通道实现兼具高通量、高分离精度聚酰胺复合膜的制备,且超亲水特征赋予复合膜优异的抗污性,其对于高性能分离膜的构筑具有重要的科学指导意义和实际应用价值。
2.本发明制备纳米纤维素络合物复合聚酰胺膜的工艺简单高效、快速便捷,是一种适于工业化应用的简便方法,可广泛应用于水处理、化工、制药和食品等分离领域。
具体实施方式
以下是本发明的具体实施例,对本发明的技术方案作进一步的描述,但本发明并不限于这些实施例。
实施例1:
将10ml、浓度为0.01%、pH为7.0的季铵纤维素纳米纤维(电荷量1.0mmol/g)水溶液以5滴/秒的速度滴加至搅拌状态下的10ml、浓度为0.01%、pH为7.0的TEMPO-纤维素纳米纤维(电荷量1.0mmol/g)水溶液中,通过离心、洗涤除去未络合的纳米纤维素,得到纳米纤维素络合物水溶液。
将聚砜超滤膜浸入到25mL的纳米纤维素络合物和哌嗪单体的水相溶液中1分钟,其中水相溶液中纳米纤维素络合物的浓度为0.1%,哌嗪单体的浓度为0.3%,然后排除膜表面过量水溶液,将25mL、浓度为0.05%的均苯三甲酰氯正己烷溶液倒在膜表面静置1分钟,随后除去膜表面过量有机溶液,将膜置于60℃烘箱中热处理10分钟,经去离子水洗涤后,得到纳米纤维素络合物复合聚酰胺膜。
实施例2:
将10ml浓度为0.01%、pH为7.0的季铵纤维素纳米纤维(电荷量1.0mmol/g)水溶液以5滴/秒的速度滴加至搅拌状态下的10ml浓度为0.01%、pH为7.0的TEMPO-纤维素纳米纤维(电荷量1.0mmol/g)水溶液中,通过离心、洗涤除去未络合的纳米纤维素,得到纳米纤维素络合物水溶液。
将聚砜超滤膜浸入到25mL的纳米纤维素络合物和哌嗪单体的水相溶液中1分钟,其中水相溶液中纳米纤维素络合物的浓度为0.01%、哌嗪单体的浓度为0.2%,然后排除膜表面过量水溶液,将25mL浓度为0.05%的均苯三甲酰氯正己烷溶液倒在膜表面静置1分钟,随后除去膜表面过量有机溶液,将膜置于60℃烘箱中热处理100分钟,经去离子水洗涤后,得到纳米纤维素络合物复合聚酰胺膜。
实施例3:
将10ml、浓度为0.01%、pH为7.0的季铵纤维素纳米纤维(电荷量1.0mmol/g)水溶液以5滴/秒的速度滴加至搅拌状态下的10ml、浓度为0.01%、pH为7.0的TEMPO-纤维素纳米纤维(电荷量1.0mmol/g)水溶液中,通过离心、洗涤除去未络合的纳米纤维素,得到纳米纤维素络合物水溶液。
将聚砜超滤膜浸入到25mL的纳米纤维素络合物和哌嗪单体的水相溶液中1分钟,其中水相溶液中纳米纤维素络合物的浓度为3%,哌嗪单体的浓度为3%,然后排除膜表面过量水溶液,将25mL、浓度为0.05%的均苯三甲酰氯正己烷溶液倒在膜表面静置1分钟,随后除去膜表面过量有机溶液,将膜置于60℃烘箱中热处理10分钟,经去离子水洗涤后,得到纳米纤维素络合物复合聚酰胺膜。
对比例1:
与实施例1的区别,仅在于,对比例1未经制备纳米纤维素络合物,直接以哌嗪为水相单体,经过和均苯三甲酰氯正己烷溶液间的界面聚合制备聚酰胺膜。
对比例2:
与实施例1的区别,仅在于,对比例2未经制备纳米纤维素络合物,直接以季铵纤维素纳米纤维和哌嗪为水相单体,经过和均苯三甲酰氯正己烷溶液间的界面聚合制备季铵纤维素纳米纤维复合聚酰胺膜
对比例3:
与实施例1的区别,仅在于,对比例3未经制备纳米纤维素络合物,直接以TEMPO-纤维素纳米纤维和哌嗪为水相单体,经过和均苯三甲酰氯正己烷溶液间的界面聚合制备TEMPO-纤维素纳米纤维复合聚酰胺膜。
表1:实施例1-4、对比例1-3制备的纳米纤维素络合物复合聚酰胺膜物理性能检测结果
实施例 | 膜孔径(nm) | 水接触角(°) |
实施例1 | 0.66 | 25 |
实施例2 | 0.50 | 40 |
实施例3 | 1.02 | 15 |
对比例1 | 0.45 | 65 |
对比例2 | 0.40 | 40 |
对比例3 | 0.55 | 37 |
通量测试:裁取标准大小膜片(面积为A:m2),固定于超滤杯中,在0.4MPa下用去离子水预压30min,然后在相同压力下收集t(h)时间内的去离子水,测量其体积V(L),计算水通量J(L/m2h)。
无机盐分离:将膜片固定在超滤杯中,在0.4MPa下用一定浓度cf(mg/L)的无机盐(硫酸钠、氯化钠)水溶液预压30min,然后在相同压力下收集10mL过滤液,用电导率仪测量其浓度cp(mg/L),计算无机盐截留率R(%)。
抗污性:将膜片固定在超滤杯中,在0.4MPa下用去离子水预压30min,继续运行2h后,记录膜的水渗透通量J0(L/m2 h),然后以一定浓度的污染物(BSA、LYZ、HA、NaAlg)水溶液为进料液,在0.4MPa下运行6h,每隔1h记录一次渗透通量,将污染膜的最低通量记为Js(L/m2h)。将2h的水溶液测试和6h的污染物测试作为一个循环,在2.5个循环后,再次记录膜的渗透通量Jr(L/m2 h)。抗污能力可用膜的通量降低率(FDR)、通量恢复率(FRR)表示:
表2:实施例1-2、对比例1-3制备的聚酰胺膜性能检测结果
从上述结果可以看出,实施例1、对比例1-3制备的聚酰胺膜四种方法均可制得聚酰胺膜,但其水渗透通量、无机盐截留率和抗污性能有明显的差别,原因在于聚酰胺膜的物化结构不同造成的。
对比例1中未经制备纳米纤维素络合物,直接以哌嗪为水相单体,所得聚酰胺膜由致密的聚酰胺链组成,表现出低的水渗透通量和抗污性能;
对比例2中未经制备纳米纤维素络合物,直接以季铵纤维素纳米纤维和哌嗪为水相单体,由于季铵纤维素纳米纤维会和均苯三甲酰氯水解产生的羧基间形成静电相互作用力,所得季铵纤维素纳米纤维复合聚酰胺膜的结构变得更为致密且容易产生缺陷,使得水渗透通量和截留率均降低,但超亲水季铵纤维素纳米纤维的引入提高了膜表面亲水性,从而使复合聚酰胺膜的抗污性提升;
对比例3中未经制备纳米纤维素络合物,直接以TEMPO-纤维素纳米纤维和哌嗪为水相单体,亲水性TEMPO-纤维素纳米纤维的引入有利于形成低传质阻力界面通道,且增强复合膜的表面荷负电性,因此所得TEMPO-纤维素纳米纤维复合聚酰胺膜的纯水渗透通量、无机盐截留率均、抗污性均有所升高,但仍显著低于实施例1。
综上所述,本发明亲水性纳米纤维素络合物内部的多孔结构可为水分子的透过提供低传质阻力的超亲水纳米通道,从而显著提高复合聚酰胺膜的水渗透通量、无机盐截留率和抗污能力。
本处实施例对本发明要求保护的技术范围中点值未穷尽之处以及在实施例技术方案中对单个或者多个技术特征的同等替换所形成的新的技术方案,同样都在本发明要求保护的范围内;同时本发明方案所有列举或者未列举的实施例中,在同一实施例中的各个参数仅仅表示其技术方案的一个实例(即一种可行性方案),而各个参数之间并不存在严格的配合与限定关系,其中各参数在不违背公理以及本发明述求时可以相互替换,特别声明的除外。
本发明方案所公开的技术手段不仅限于上述技术手段所公开的技术手段,还包括由以上技术特征任意组合所组成的技术方案。以上所述是本发明的具体实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。
Claims (1)
1.一种纳米纤维素络合物复合聚酰胺膜,其特征在于,所述复合聚酰胺膜为通过含纳米纤维素络合物/胺类单体的水溶液和含多元酰氯单体的有机溶液在超滤膜表面进行界面聚合反应得到;
所述复合聚酰胺膜制备方法包括如下步骤:
S1、将季铵纤维素纳米纤维水溶液滴加至TEMPO-纤维素纳米纤维水溶液中,经离心、洗涤后得到纳米纤维素络合物水分散液;
S2、将超滤膜浸入到含纳米纤维素络合物和哌嗪单体的水相溶液中,排除膜表面过量水溶液,将均苯三甲酰氯正己烷溶液倒在膜表面静置,然后除去膜表面过量有机溶液,将膜热处理,经去离子水洗涤后得到纳米纤维素络合物复合聚酰胺膜;
步骤S1季铵纤维素纳米纤维水溶液浓度为0.01%,pH为7;
步骤S2水相溶液中纳米纤维素络合物的浓度为0.01%;
步骤S2水相溶液中哌嗪单体浓度为0.3%;
均苯三甲酰氯正己烷溶液的浓度为0.05%;
纳米纤维素络合物复合聚酰胺膜膜孔径为0.66nm、水接触角为25°、水渗透通量为50.2L/m2 h,硫酸钠截留率为99.2%,氯化钠截留率为15.8%,FDR为10.5%。
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