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端基接枝对半芳香纳滤膜的耐氯性能影响

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半芳香聚酰胺纳滤膜因其高截留选择性、大水通量、易集成和放大等优势,在饮用水处理中扮演重要角色.然而,聚酰胺膜对活性氯的耐受性较低,限制了其广泛应用.本文探讨了乙二酰氯和磺酰氯接枝对提升膜耐氯性能的效果.乙二酰氯接枝后的 自制膜NFlab对木糖和Mg2+的截留率下降,耐氯性能略有提升,而接枝后的商业化膜NFH的耐氯性则因有机溶剂造成的膜溶胀而显著下降.磺酰氯接枝基本不改变原膜的过滤性能,接枝后NFlab的耐氯性能有显著提升.对膜单体的DFT计算表明,酰胺N是次氯酸的主要反应位点,接枝并未显著改变单体的几何构型和反应位点,但略微增加了酰胺N的负电荷.过渡态优化显示,磺酰氯接枝提高了酰胺键与次氯酸反应的能垒,这有助于提升膜的耐氯性能.
The impact of end-group grafting on the chlorine resistance of semi-aromatic nanofiltration membranes
Semi-aromatic polyamide nanofiltration membranes play a crucial role in drinking water treatment due to their high retention selectivity,large water flux,ease of integration,and scalability.However,their low resistance to active chlorine limits widespread application.This study investigated the effects of grafting with oxalyl chloride and sulfonyl chloride on enhancing membrane chlorine resistance.Grafting with oxalyl chloride decreased retention rates for xylose and Mg2+,albeit with slightly improved chlorine resistance in lab-made NFlab membranes.In addition,commercial NFH membranes exhibited significantly reduced chlorine resistance after oxalyl chloride grafting.Sulfonyl chloride grafting maintained the filtration performance of the original membrane and notably enhanced chlorine resistance in NFlab membranes.DFT calculations on membrane monomers revealed that the nitrogen in the amide bond was a primary reactive site for hypochlorous acid.Grafting led to minor changes in geometric configuration and reaction sites but increased the negative charge on the amide nitrogen.Transition state optimizations demonstrated that sulfonyl chloride grafting increased the reaction barrier for amide bond with hypochlorous acid,thereby improving membrane chlorine resistance.

semi-aromatic nanofiltration membranechlorinationretention rategraftingreaction energy barrier

王源、李梦菲、王志强、杨少霞、王小(毛)

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深圳市利源水务设计咨询有限公司,深圳 518034

华北电力大学水利与水电工程学院,北京 102206

清华大学环境学院,北京 100084

半芳香纳滤膜 氯化 截留率 接枝 能垒

2024

膜科学与技术
中国蓝星(集团)股份有限公司

膜科学与技术

CSTPCD北大核心
影响因子:0.634
ISSN:1007-8924
年,卷(期):2024.44(6)