带有共价有机框架中间层的新型耐高温薄膜复合聚酰胺反渗透膜

Xun Li , Chen-Jie Wei , Ni-Jie Liu , Nian Zhang , Sa-Ren Qi , Bo-Ming Xie , He-Lin Zhu , Xue-Li Cao , Li-Fen Liu
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摘要

传统的薄膜复合(TFC)聚酰胺反渗透(RO)膜的拒盐和承压性能在高温下很容易被削弱。为了提高耐高温性能,本研究制备了一种带有共价有机框架(COFs)中间层的聚酰胺 TFC 反渗透膜。首先,采用单向扩散法在聚醚砜(PES)支撑膜上装饰 COFs 层,并通过与 1,3-二氨基-2-丙醇(DAPL)或乙二胺(EDA)的化学交联反应进一步修饰收缩微孔,然后在所得 COFs 层上继续进行间苯二胺(MPD)和三甲基甲酰氯(TMC)的常规界面聚合,制备出 RO 膜。此外,还系统研究了 COFs 层的微观结构与改性反渗透膜分离性能之间的相关性。与传统的聚酰胺反渗透膜和其他已报道的耐温反渗透膜相比,由于引入了具有更规整微观结构和特定亲水性的 COFTpPa-DAPL 中间层,所制备的 TFC-COFTpPa-DAPL 反渗透膜的水通量提高了 30%(达到 50.5 L m-2 h-1),盐排斥率更高(99.5%)。同时,这种 TFC-COFTpPa-DAPL 膜在反渗透过程中表现出良好的长期分离稳定性,持续时间长达 160 小时。特别是,在 70 °C条件下,其水通量增加到 98.8 L m-2 h-1,而盐排斥率(约 99.4 %)却没有降低。这项研究为基于 COFs 中间层制造具有良好综合分离性能的耐高温 TFC 聚酰胺反渗透膜提供了一种有效方法。
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A novel high temperature resistance thin film composite polyamide reverse osmosis membrane with covalent organic frameworks intermediate layer

Both salt rejection and pressure-bearing properties of the conventional thin film composite (TFC) polyamide reverse osmosis (RO) membrane are easily weakened at high temperature. In order to improve the high temperature resistance, in this work, a polyamide TFC RO membrane with covalent organic frameworks (COFs) intermediate layer was prepared. Firstly, the COFs layer was decorated on polyether sulfone (PES) support membrane by a unidirectional diffusion method and further modified for shrinking the micropore via the chemical crosslinking reaction with 1,3-diamino-2-propanol (DAPL) or ethylenediamine (EDA), and then continued the conventional interfacial polymerization of m-phenylene diamine (MPD) and trimesoyl chloride (TMC) on the resultant COFs layer for preparing the RO membrane. Furthermore, the correlationship between the microstructure of COFs layer and the separation performance of modified RO membrane was systematically investigated. Due to the introduction of the COFTpPa-DAPL intermediate layer with more regular microstructure and specific hydrophilicity, the resultant TFC-COFTpPa-DAPL RO membrane exhibited improvement in water flux by 30 ​% (reached to 50.5 ​L ​m−2 ​h−1) and higher salt rejection (>99.5 ​%) as compared with the conventional polyamide RO membrane and other reported temperature resistance RO membranes. Meanwhile, this TFC-COFTpPa-DAPL membrane showed good long-term separation stability during the RO process for 160 ​h. Especially, its water flux increased to 98.8 ​L ​m−2 ​h−1 without weakening salt rejection (about 99.4 ​%) at 70 ​°C. This study provides an effective way to fabricate the high temperature resistance TFC polyamide RO membrane with good comprehensive separation performance based on COFs intermediate layer.

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