【作者】 许振良； 胡登； 汤永健； 任翘楚； 魏永明；

【Author】 XU Zhenliang;HU Deng;TANG Yongjian;REN Qiaochu;WEI Yongming;State Key Laboratory of Chemical Engineering,Membrane Science,Engineering R&D Lab,Chemical Engineering Research Center,East China University of Science,Technology(ECUST);

【机构】 化学工程联合国家重点实验室,华东理工大学 化学工程研究所 膜科学与工程研发中心；

【摘要】 以聚醚砜（PES）超滤膜为基膜,水相单体为2,2-二（1-羟基-1-三氟甲基-2,2,2-三氟乙基）-4,4-亚甲基双苯胺（BHTTM）,有机相单体为均苯三甲酰氯（TMC）时,通过界面聚合的方法制备复合纳滤膜,研究了纳滤膜的制备条件并对纳滤膜的性能进行评估,采用ATRIR、SEM及AFM等对膜进行了表征;当水相中含有1%（w/v）的BHTTM,有机相中含有0.15%（w/v）的TMC,将水相和有机相单体聚合10 s,然后将其放入80℃下热处理5 min制备含氟纳滤膜,操作压力0.6MPa,纳滤膜Na₂SO₄的截留率85.3%,纯水通量10.1 L/（m²·h）;经过5 000 mg/L的活性氯处理后纳滤膜Na₂SO₄的截留和纯水通量分别达到94.5%和94.8 L/（m²·h）,处理前后的纳滤膜对不同盐的截留率为Na₂SO₄>MgSO₄>MgCl₂>NaCl,因此该纳滤膜为荷负电纳滤膜.同时,在研究纳滤膜中添加硅溶胶及选择新型聚合单体后,为了进一步提高纳滤膜的渗透性能,实验以BHTTM为水相单体,TMC为有机相单体,通过水相中添加硅溶胶制备SiO₂-含氟纳滤膜;通过对不同聚合条件进行优化,研究了制膜条件,在优化条件下,0.6MPa测得纳滤膜对Na₂SO₄的截留率为85.0%,纯水通量为15.2 L/（m²·h）,相比于不添加纳米颗粒,膜的渗透性能有一定的提高;当纳滤膜经过5 000 ppm活性氯处理后,纳滤膜Na₂SO₄的截留率为94.0%,纯水通量为105 L/（m²·h）(17.5 L·m^-2·h^-1·bar^-1),相比于大多数纳滤膜的纯水通量(5¹0 L·m^-2·h^-1.bar^-1)得到了很大的提升.此外,以聚砜（PSF）中空纤维超滤膜为基膜,BHTTM为水相单体,TMC为有机相单体,采用界面聚合方法制备了中空纤维复合纳滤膜,分析了基膜和纳滤膜的微观结构、表面粗糙度、红外光谱和亲水性,讨论了不同反应时间、热处理时间、单体浓度等制备奈件对纳滤膜性能的影响.结果表明:当水相1%（w/v）BHTTM、油相0.15%（w/v）TMC和界面聚合时间10 s,并在60℃下热处理10 min时,所得纳滤膜具有良好的分离性能,对于无机盐的截留率大小均为Na₂SO₄>MgSO₄>NaCl>MgCl₂.更多还原

【Abstract】 Using polyethersulfone（PES） UF membrane as a supporting membrane,a novel composite nanofiltration（NF） membrane was prepared by interfacial polymerization of BHTTMand trimesoyl chloride（TMC）.Different preparation conditions and NF membrane performances were discussed.The membrane structures of composite NF membranes were characterized by ATR-IR,SEM and AFM.The BHTTM-TMC composite NF membrane was prepared under the condition:1%（w/v） BHTTM in the aqueous phase;0.15%TMC in the organic phase;reaction time for 10 s and curing temperature at 80°C for 5 min.The optimum condition exhibited Na₂SO₄ rejection of 85.3%and the water flux of 10.1 L/（m²· h） under 0.6 MPa.The NF membrane was treated by 5000 ppm chlorine solution for 1 h.The salt rejection and water flux of the treated membrane reached to 94.5%and 94.8 L/（m² · h）.The rejection of two NF membranes for inorganic electrolyte solutions decreased in the order of Na₂SO₄,MgSO₄,MgCl₂,NaCl,which were typical characteristics of negatively charged membranes.At the same time,the possibility of obtaining a membrane with high water flux was investigated.The composite polyamide NF membranes were prepared by interfacial polymerization of BHTTM and TMC with adding silica sol in aqueous phase.The performances of NF membranes were optimized by studying the preparation conditions.The results showed that the NF membrane prepared under the optimum condition exhibited Na₂S_O4 rejection of 85.0%and the water flux of 15.2 L/（m2 · h） under 0.6 MPa.Compared with the membrane not added nanoparticle in the aqueous phase,the permeability of silica-BHTTM-TMC NF membrane has improved.The NF membrane was treated by 5000 ppm chlorine solution for 1 h.The salt rejection and water flux of the treated membrane reached to 94.0%and 105 L/（m² · h） under 0.6 MPa(17.5 L · m^-2 · h^-1 · bar^-1).Compared to most other NF membrane water flux(5¹0 L · m^-2 · h^-1 ·bar^-1),the pure water flux has been greatly improved.Besides,using polysulfone（PSF） hollow fiber membrane as the supporting membrane,fluoropolyamide /polysulfone（PSF） hollow fiber thin film composite（TFC） nanofiltration（NF） membrane was prepared by the interfacial polymerization of BHTTM and TMC.The morphologies and surface properties of hollow fiber TFC NF membranes were characterized by scanning electron microscope（SEM）,atomic force microscopy（AFM）,attenuated total reflectance infrared（ATR-IR） and contact angle instrument.The experimental results showed that the hollow fiber TFC NF membrane prepared under the following condition gained the best performance:1.0%（w/v） BHTTM and 0.15%（w/v） TMC for 10 s reaction and 10 min heat treatment in 60 ℃.The rejection of the resulting NF membrane for different inorganic electrolyte solutions decreased in the following order:Na₂SO₄,MgSO₄,NaCl,MgCl₂,which were typical characteristics of negatively charged membranes.更多还原