二次界面聚合同步反扩散原位生长ZIF-8纳米粒子制备聚酰胺混合基质反渗透（RO）膜

doi:10.16085/j.issn.1000-6613.2023-0318

摘要/Abstract

摘要：

在聚砜超滤支撑膜上预负载锌离子，之后由间苯二胺（MPD）和均苯三甲酰氯（TMC）在支撑膜上进行界面聚合反应过程，得到包覆锌离子的聚酰胺层，随后在咪唑配体反扩散至聚酰胺层中原位生长ZIF-8的同时，MPD和膜上残留的酰氯基团进行二次界面聚合，并与ZIF上的Zn(Ⅱ)离子桥联，得到聚酰胺混合基质RO膜（PA²/ZIF-8）。原位生长ZIF-8纳米颗粒所带来的聚酰胺界面非选择性缺陷由二次聚合修补，同时生长的ZIF-8纳米颗粒为水分子透过建立了额外的通道，从而在不牺牲截留率前提下，显著提升了水通量。本文讨论了二次界面聚合反扩散原位生长过程中预负载锌离子、二次界面聚合时间、咪唑配体及胺单体浓度对PA²/ZIF-8混合基质膜反渗透性能的影响。据测试，PA²/ZIF-8的水通量可达到63.9L/(m²·h)，可达原始TFC膜的2倍，并保持了98%以上的截盐率，并且在测试过程中拥有良好的耐酸碱性、长期稳定性以及抗污染性。

关键词: 反渗透, ZIF-8, 原位生长, 膜, 脱盐, 纳米粒子

Abstract:

Thin-film nanocomposite polyamide mixed matrix reverse osmosis (MMRO) membranes were prepared from secondary interface polymerization between m-phenylenediamine (MPD) and the residual acyl chloride groups of trimethylene chloride (TMC) from the PA layers of TFC-PA membranes while imidazole ligand was counter diffused through the PA layer to react with the Zn(Ⅱ) cations pre-loaded on the polysulfone ultrafiltration substrates to form ZIF-8 nano-particles (NPs). None-selective defects between the in situ grown ZIF-8 NPs and the PA layers were eliminated by the MPD linkage between Zn(Ⅱ) and ZIF-8 PA polymers while additional selective water permeating channels were built inside the formed ZIF-8 NPs, resulting in improved water flux without trading off salt rejection rates. The effects of pre-loaded zinc ion, secondary polymerization, imidazole ligand and amine monomer concentration on the reverse osmosis performance of the formed PA²/ZIF-8 MMRO membranes were discussed. The water flux of PA²/ZIF-8 MMRO membranes reached 63.9L/(m²·h), almost doubled from the pristine PA membranes, keeping the same NaCl rejection above 98%, good long term operating and chemical stability, as well as anti-fouling capability.

Key words: reverse osmosis, ZIF-8, in situ growth, membranes, desalination, nanoparticles

中图分类号:

TQ028

张祚群, 高扬, 白超杰, 薛立新. 二次界面聚合同步反扩散原位生长ZIF-8纳米粒子制备聚酰胺混合基质反渗透（RO）膜[J]. 化工进展, 2023, 42(S1): 364-373.

ZHANG Zuoqun, GAO Yang, BAI Chaojie, XUE Lixin. Thin-film nanocomposite (TFN) mixed matrix reverse osmosis (MMRO) membranes from secondary interface polymerization containing in situ grown ZIF-8 nano-particles[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 364-373.

图/表 16

表1 不同聚酰胺混合基质复合反渗透膜样品的制备参数

膜样品	预负载水溶液	界面聚合溶液		后处理水溶液
膜样品	Zn(NO₃)₂∙6H₂O/mol∙L^-1	MPD水相溶液质量分数/%	TMC油相溶液质量分数/%	MPD/g·L^-1	MeIM/g·L^-1
TFC	0	2.4	0.12	0	0
PA/Zn	0.1	2.4	0.12	0	0
PA²	0	2.4	0.12	5	8.2
PA/ZIF-8	0.1	2.4	0.12	0	8.2
PA²/ZIF-8	0.1	2.4	0.12	5	8.2

图1 反渗透膜的制备流程图

图2 各膜样品表面及截面SEM图像

图3 各膜样品红外光谱图

图4 各膜样品XRD图像

表2 XPS测得聚酰胺混合基质反渗透膜样品表面元素组成

膜样品	元素质量分数/%				比值
膜样品	C	N	O	Zn	O/N	O/N 修正
TFC	70.78	15.24	13.98	—	0.917	0.917
PA/Zn	72.61	13.60	12.94	0.84	—	—
PA²	72.86	13.85	13.29	—	—	—
PA/ZIF-8	74.84	14.02	11.59	0.41	0.765	0.867
PA²/ZIF-8	78.67	10.93	10.01	0.4	0.916	1.073

图5 各膜样品的AFM图像对比

图6 各膜样品水接触角及表面自由能比较

图7 膜分离性能对比图

图8 二次界面聚合同步生长ZIF-8纳米粒子构建PA2/ZIF-8混合基质反渗透膜机理图

图9 后处理溶液浓度对膜性能的影响

图10 后处理时间对膜性能的影响对比图

图11 TFC、PA2/ZIF-8耐酸碱性能测试对比图

图12 TFC、PA2/ZIF-8稳定性测试对比图

图13 TFC、PA2/ZIF-8抗污染性能测试对比图

图14 TFC、PA2/ZIF-8膜表面zeta电位对比图

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