“特殊稳定型”压力驱动薄膜复合（TFC）脱盐膜的研究进展

doi:10.16085/j.issn.1000-6613.2022-1133

摘要/Abstract

摘要：

薄膜复合（TFC）膜凭借其优异的渗透性及选择性常用于水处理过程中的脱盐环节。为解决TFC脱盐膜在贮存/运行过程中因干燥、酸/碱水解、高温破坏或氯氧化导致性能下降的问题，国内外众多学者相继开展了各类提高其稳定性的研究。本文以广泛应用的TFC纳滤/反渗透膜为参照，论述了TFC脱盐膜在上述四种特殊条件下的破坏机制，并归纳了相关的稳定性提升策略。通过系统地梳理耐干、耐酸/碱、耐高温和耐氯四类“特殊稳定型”TFC脱盐膜的最新研究进展，指出了目前存在破坏机制研究工作不够深入、对不同稳定性之间的影响关注不足等问题。最后，展望了未来在进一步研究膜材料失效机制的同时，要兼顾“特殊稳定型”TFC脱盐膜的脱盐效能和耐污染能力，并开展对多重稳定性的TFC脱盐膜材料的探索, 以期为日后的相关研究工作提供参考。

关键词: 膜, 薄膜复合（TFC）膜, 稳定性, 脱盐, 耐酸碱, 耐氯, 耐高温, 耐干

Abstract:

The thin film composite (TFC) membranes with excellent permeability and selectivity are commonly used for desalination in water treatment. To overcome the membrane performance deterioration because of drying, acid/base hydrolysis, high temperature damage and chlorine oxidation attack during the storage/operating process, numerous works focusing on stability improvement of TFC membranes have been reported. Referring to the most popular nanofiltration/reverse osmosis membranes, this review concluded the damage mechanism of polyamide TFC membranes in the drying process, acid/alkali solution, high temperature and active chlorine solution, and then the strategy of corresponding stability improvement is summarized. By systematically combing the latest research progress of four kinds of "special stable" TFC desalting membranes, i.e., dry resistance, acid/alkali resistance, high temperature resistance and chlorine resistance, it is pointed out that the current research work had problems such as lack of in-depth research on the mechanism of destruction and insufficient attention to the influence between different stabilities. Finally, the research direction in the future is prospected. While further studying the failure mechanism of membrane materials, it should pay more attention to the desalination efficiency and anti-fouling capacity of TFC desalination membranes with special stability, and explore multi-stability TFC desalination membranes, so as to provide reference for future related research work.

Key words: membrane, thin film composite (TFC) membrane, stability, desalination, acid/alkali-resistant, chlorine-resistant, thermally stability, anti-drying

中图分类号:

TQ028

宗悦, 张瑞君, 高珊珊, 田家宇. “特殊稳定型”压力驱动薄膜复合（TFC）脱盐膜的研究进展[J]. 化工进展, 2023, 42(4): 2058-2067.

ZONG Yue, ZHANG Ruijun, GAO Shanshan, TIAN Jiayu. A review on the pressure-driven thin film composite (TFC) membranes with special stability for desalination[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2058-2067.

图/表 5

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基膜	分离层	膜性能变化	参考文献
PPESK	MPD-TMC	测试温度由20℃升至90℃，纯水通量提升200%， Na₂SO₄截留率由96.8%降至93.2%	[41]
PPESK	PIP-TMC	测试温度由20℃升至90℃，纯水通量提升200%， Na₂SO₄截留率保持在97.7%±0.4%	[41]
PMIA	PIP-TMC	测试温度由25℃升至90℃，纯水通量提升约120%， Na₂SO₄截留性能不变（高于95%）	[43]
PPEA	PIP-TMC	测试温度由25℃升至85℃，纯水通量提升200%， NaCl截留率由12.2%降至6.9%，染料ACBK截留率保持不变（99.5%±0.2%）	[44]
PPENK	PIP-TMC	测试温度由20℃升至80℃，纯水通量提升400%， Na₂SO₄截留性能不变（95.1%）	[45]
PPBES	PIP-TMC	测试温度由18℃升至85℃，纯水通量提升375%， Na₂SO₄截留率由92.0%降至88.5%	[46]

基膜	分离层	膜性能变化	参考文献
PPESK	MPD-TMC	测试温度由20℃升至90℃，纯水通量提升200%， Na₂SO₄截留率由96.8%降至93.2%	[41]
PPESK	PIP-TMC	测试温度由20℃升至90℃，纯水通量提升200%， Na₂SO₄截留率保持在97.7%±0.4%	[41]
PMIA	PIP-TMC	测试温度由25℃升至90℃，纯水通量提升约120%， Na₂SO₄截留性能不变（高于95%）	[43]
PPEA	PIP-TMC	测试温度由25℃升至85℃，纯水通量提升200%， NaCl截留率由12.2%降至6.9%，染料ACBK截留率保持不变（99.5%±0.2%）	[44]
PPENK	PIP-TMC	测试温度由20℃升至80℃，纯水通量提升400%， Na₂SO₄截留性能不变（95.1%）	[45]
PPBES	PIP-TMC	测试温度由18℃升至85℃，纯水通量提升375%， Na₂SO₄截留率由92.0%降至88.5%	[46]

单体名称	原理	膜性能变化	参考文献
低聚酚醛树脂（OPR）	减少酰胺键数量	浸泡1000mg/L NaClO溶液48h，水通量从2.42L/(m²·h·bar)增加至3.54L/(m²·h·bar)，Na₂SO₄截留率降至92.0%	[55]
季戊四醇	减少酰胺键数量	浸泡3000mg/L NaClO溶液48h，水通量从1.34L/(m²·h·bar)增长至1.84L/(m²·h·bar)，Na₂SO₄截留率保持不变（约97%）	[64]
葡萄糖	减少酰胺键数量	浸泡10000mg/L NaClO溶液96h （pH=4.5），水通量从15.8L/(m²·h·bar)增加至42.3L/(m²·h·bar)，Na₂SO₄截留率从99.5%下降到91%	[65]
(3-磺丙基甜菜碱-丙基)- 三甲氧基硅（SPPT）	与水分子通过静电吸引形成水层	浸泡500mg/L NaClO溶液6h，NaCl截留率低于95%	[66]
3,5-二羟基苯甲酸（DHBA）	减少酰胺键数量	浸泡100000mg·h/L NaClO溶液（pH<7），NaCl截留率保持不变（约99%）	[67]
3,5-二氨基-1,2,4- 三氮唑（DAT）	降低酰胺键活性	浸泡200mg/L NaClO溶液120h，水通量95.1 L/(m²·h·bar)，直接红23截留率>90%	[56]
间苯二甲胺（m-XDA）	降低酰胺键活性，增加空间位阻	浸泡200mg/L NaClO溶液20h，水通量增加约100%，Na₂SO₄截留率大于90%	[57]

单体名称	原理	膜性能变化	参考文献
低聚酚醛树脂（OPR）	减少酰胺键数量	浸泡1000mg/L NaClO溶液48h，水通量从2.42L/(m²·h·bar)增加至3.54L/(m²·h·bar)，Na₂SO₄截留率降至92.0%	[55]
季戊四醇	减少酰胺键数量	浸泡3000mg/L NaClO溶液48h，水通量从1.34L/(m²·h·bar)增长至1.84L/(m²·h·bar)，Na₂SO₄截留率保持不变（约97%）	[64]
葡萄糖	减少酰胺键数量	浸泡10000mg/L NaClO溶液96h （pH=4.5），水通量从15.8L/(m²·h·bar)增加至42.3L/(m²·h·bar)，Na₂SO₄截留率从99.5%下降到91%	[65]
(3-磺丙基甜菜碱-丙基)- 三甲氧基硅（SPPT）	与水分子通过静电吸引形成水层	浸泡500mg/L NaClO溶液6h，NaCl截留率低于95%	[66]
3,5-二羟基苯甲酸（DHBA）	减少酰胺键数量	浸泡100000mg·h/L NaClO溶液（pH<7），NaCl截留率保持不变（约99%）	[67]
3,5-二氨基-1,2,4- 三氮唑（DAT）	降低酰胺键活性	浸泡200mg/L NaClO溶液120h，水通量95.1 L/(m²·h·bar)，直接红23截留率>90%	[56]
间苯二甲胺（m-XDA）	降低酰胺键活性，增加空间位阻	浸泡200mg/L NaClO溶液20h，水通量增加约100%，Na₂SO₄截留率大于90%	[57]

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