氢键有机框架纳滤膜净化磷酸中金属离子的研究

doi:10.19964/j.issn.1006-4990.2024-0662

摘要/Abstract

摘要：

湿法磷酸生产工艺比热法磷酸生产工艺具有更高的经济效益，但在生产过程中会引入大量的金属离子，需要经济环保的方式去除。纳滤膜能够高效地分离离子和分子，对环境负面影响小，在磷酸净化领域显现出巨大的潜力。但粗制磷酸极低的pH和高黏度使得传统商业纳滤膜易被破坏且渗透速率极低。为此采用C₃H₈N₆SO₄（HOF）作为水相单体和六亚甲基二异氰酸酯（HDI）作为有机相单体通过界面聚合反应制备了一种高渗透耐酸的纳滤膜（HOF-HDI）用于磷酸净化，通过FT-IR和XPS表征证明纳滤膜成功合成，优化单体浓度和热固化温度得到最佳制备条件。结果表明：磷酸溶液（以P₂O₅计，质量分数为20%）液中HOF-HDI膜的渗透速率达到0.85 L/（h·m²·bar），对Al³⁺、Mg²⁺、Fe³⁺离子的截留率由大到小的顺序依次为Al³⁺（51.00%）、Mg²⁺（47.99%）、Fe³⁺（46.33%）；通过静态和动态耐酸性测试证明改性膜具有优异的酸稳定性。通过探究单体类型对膜层性能影响揭示了具有空腔的单体有利于增强纳滤膜的渗透性。HOF-HDI纳滤膜在磷酸净化中展现出良好的应用前景。

关键词: 纳滤膜, 耐酸, 高渗透, 氢键有机框架, 磷酸

Abstract:

Wet-process phosphoric acid offers greater economic advantages over its thermal-process counterpart.However，it introduces substantial quantities of metal ions during production，which requires economical and environmentally sustainable removal strategies.Nanofiltration membranes，which efficiently separate ions and molecules with minimal environmental impact，have demonstrated considerable potential in the purification of phosphoric acid.However，the extremely low pH and high viscosity of crude phosphoric acid significantly hinder the applicability of conventional nanofiltration membranes，often leading to membrane degradation and reduced permeability.For this reason，a highly permeable，acid-resistant nanofiltration membrane（HOF-HDI） was synthesized for phosphoric acid purification by interfacial polymerization，employing C₃H₈N₆SO₄（HOF） as the aqueous-phase monomer and hexamethylene diisocyanate（HDI） as the organic-phase monomer.The successful fabrication of the membrane was confirmed through FT-IR and XPS.By optimizing the monomer concentration and thermal curing temperature，the optimal preparation conditions were established.The experimental results revealed that the HOF-HDI membrane achieved a permeation rate of 0.85 L/（h·m²·bar） in phosphoric acid solution（20% mass fraction in terms of P₂O₅）.The rejection rates for Al³⁺，Mg²⁺，and Fe³⁺ ions decreased in the following order：Al³⁺（51.00%），Mg²⁺ （47.99%），Fe³⁺（46.33%）.Static and dynamic acid resistance tests demonstrated the superior acid stability of the modified membrane.Investigating the influence of monomer type on membrane structure revealed that cavity-containing monomers enhance membrane permeability.Collectively，these findings underscored the great promise of the HOF-HDI nanofiltration membrane for effective phosphoric acid purification.

Key words: nanofiltration membrane, acid-resistant, high permeability, hydrogen-bonded organic framework, phosphoric acid

中图分类号:

TQ126.31

王建东, 龚建平, 陈建钧, 李军, 刘代俊. 氢键有机框架纳滤膜净化磷酸中金属离子的研究[J]. 无机盐工业, 2025, 57(11): 23-30.

WANG Jiandong, GONG Jianping, CHEN Jianjun, LI Jun, LIU Daijun. Study on removing metal ions from phosphoric acid by hydrogen-bonded organic framework nanofiltration membrane[J]. Inorganic Chemicals Industry, 2025, 57(11): 23-30.

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