聚合物基疏水渗透汽化膜及其溶剂回收应用

doi:10.11949/0438-1157.20241211

摘要/Abstract

摘要：

渗透汽化是一种新兴的膜分离技术，广泛应用于溶剂回收和环境保护领域。通过选择性渗透和汽化过程，渗透汽化膜可有效分离水与有机溶剂，尤其适用于处理含水溶剂的废液，能减少环境污染，并实现资源的循环利用。立足于以聚合物材料作为基底的膜材料设计，综述疏水渗透汽化膜的研究进展，凝练出目前亟待解决的关键问题，为推动该技术领域的进一步发展提供指引。首先讨论了基于聚合物基底的渗透汽化膜的类型及特征，从提升材料疏水特性的角度，阐述了用于提升膜疏水性能的方法，如物理共混、表面结构控制和中间层构筑等，分析总结了具有所需微观结构和表面特性的聚合物基疏水渗透汽化膜的设计策略。其次，介绍了聚合物基疏水渗透汽化膜在溶剂回收领域的广泛应用及前景，包括醇类、脂类、烃类和酮类等溶剂的回收。再次，介绍了聚合物基疏水渗透汽化膜的热稳定性和中试案例。最后，对聚合物基疏水渗透汽化膜在实际应用中面临的挑战进行了分析，并概述了聚合物基疏水渗透汽化膜未来的研究和发展方向。

关键词: 膜, 选择性, 分离, 渗透汽化, 溶剂回收

Abstract:

Pervaporation membranes are an emerging membrane separation technology widely used in solvent recovery and environmental protection. Through the selective permeation and vaporization process, the pervaporation membrane can effectively separate water and organic solvents, especially suitable for treating waste liquid containing aqueous solvents, which can reduce environmental pollution and realize the recycling of resources. Unlike previous reviews on pervaporation separation membranes, this paper summarizes the research progress of hydrophobic pervaporation membranes from the perspective of polymer membranes as substrates, highlighting key issues that need to be addressed to guide further development in this field. In this paper, we first discuss the challenges faced by polymer-based hydrophobic pervaporation membranes in solvent recovery and the essential requirements for practical separation applications. We outline different methods to enhance membrane hydrophobicity, such as physical blending, surface structure control and intermediate layer construction, and summarize design strategies for polymer-based hydrophobic pervaporation membranes that possess the desired microstructure and surface characteristics. Second, we introduce the broad application prospects of polymer-based hydrophobic pervaporation membranes in solvent recovery, including the recovery of solvents such as alcohols, lipids, hydrocarbons and ketones. Third, the thermal stability and pilot-scale test cases of polymer-based hydrophobic pervaporation membranes have been introduced. Finally, we analyze the challenges faced by polymer-based hydrophobic pervaporation membranes in practical applications and outlines future research and development directions.

Key words: membrane, selectivity, separation, pervaporation, solvent recovery

中图分类号:

TQ 028

徐泽海, 刘超, 张国亮. 聚合物基疏水渗透汽化膜及其溶剂回收应用[J]. 化工学报, 2025, 76(5): 2055-2069.

Zehai XU, Chao LIU, Guoliang ZHANG. Hydrophobic pervaporation membranes on polymer substrate for solvent recovery[J]. CIESC Journal, 2025, 76(5): 2055-2069.

图/表 11

图1 聚合物基疏水渗透汽化膜设计策略

Fig.1 Design strategy of polymer-based hydrophobic pervaporation membrane

图2 （a）聚合物基复合膜示意；（b）部分疏水膜材料及乙醇/水的溶解度参数对比

Fig.2 (a) Schematic diagram of polymer-based composite membrane; (b) Comparison of solubility parameters of some hydrophobic film materials and ethanol/water

图3 聚合物基混合基质膜示意图

Fig.3 Schematic diagram of polymer-based mixed matrix membrane

表1 渗透汽化膜用MOFs和COFs结构参数

Table 1 Structural parameters of MOFs and COFs for pervaporation membranes

框架材料名称	孔尺寸/Å	BET比表面积/(m²/g)	孔隙体积/(cm³/g)	文献
ZIF-8	3.4	1344	0.554	[18]
ZIF-71	4.8	1007	0.452	[18]
ZIF-67	4.51	1245	0.665	[19]
ZIF-90	2.86	1360	0.561	[18]
MAF-6	7.6	1343	0.63	[20]
MOF-808	14	2060	0.84	[21]
MIL-53	8	1294	0.65	[22]
MIL-101	12	2500	1.22	[23]
COF-300	0.7	1360	0.72	[24]
COF-DVA	2.53	663	—	[25]
CuCOF	1.89	515	—	[26]
COF-LZU1	74.5	583	0.48	[27]
COF- LZU8	12.3	454	0.36	[28]
COF-42	2.3	659	0.29	[29]

图4 （a）PVTES-PDMS渗透汽化膜结构示意[35]；（b）MOF-NS/PVDF膜合成过程示意[37]

Fig.4 (a) Structure diagram of PVTES-PDMS pervaporation membrane[35]; (b) Schematic diagram of the synthesis process of MOF-NS/PVDF membrane[37]

图5 （a）硅酸盐/PDMDES渗透汽化膜示意[38]；（b）MA-silicalite-1/MA-PDMS膜合成过程示意[39]

Fig.5 (a) Structure diagram of silicalite-1/PDMDES pervaporation membrane[38]; (b) Schematic diagram of the synthesis process of MA-silicalite-1/MA-PDMS membrane[39]

图6 MOF/PDMS混合基质膜合成过程示意[41]

Fig.6 Scheme of MOF/PDMS mixed matrix membrane synthesis process[41]

图7 （a）PDMS/GPAN膜结构示意[8]；（b）ZIF-8-DMBIM/PEBAX膜制备流程示意[11]

Fig.7 (a) PDMS/GPAN membrane structure diagram[8]; (b) Schematic diagram of ZIF-8-DMBIM/PEBAX membrane preparation process[11]

表2 聚合物基疏水渗透汽化膜在溶剂回收方面的应用

Table 2 Application of polymer-based hydrophobic pervaporation membranes in solvent recovery

膜	温度/℃	进料浓度/%（质量分数）	回收溶剂	分离因子	渗透通量/(g/(m²·h))	文献
POSS/PDMS	50	10	乙醇	17.7	536	[43]
PVTES-HSO	35	9	乙醇	6.6	8160	[35]
TMSC/PDMS	24	5	乙醇	14	1600	[44]
UiO-66-NH₂-TMS/PDMS	40	5	乙醇	5.8	5277.9	[42]
1173IPS-MA/PDMS	40	5	乙醇	8.4	930	[45]
PMHS/PDMS	60	5	乙醇	12	1204	[46]
MAF-6/PDMS	40	5	乙醇	14.9	1200	[47]
LZU8/PDMS	60	5	乙醇	11	5000	[48]
LDDLT-ZIF-L/PDMS	40	5	乙醇	12.3	1120	[49]
MIL-53/PDMS	70	5	乙醇	11.1	5467	[50]
DMDES/PDMS	35	5	乙醇	6.5	7565.6	[51]
MOF-NS/PDMS	40	5	乙醇	8.9	6800	[37]
Suspension-dispersed ZIF-8/PDMS	40	5	丁醇	34	1358	[52]
PDMS-PMHS/ZIF-8	60	3	丁醇	64.59	2334.6	[53]
COF-LZU1/PEBA	70	3.7	丁醇	22.2	611	[54]
PIM-1/PVDF 18-A3 (2% PIM-1)	65	6	丁醇	13.3	9080	[55]
PIM-1/PDMS	60	1	丁醇	30.7	1425.3	[56]
TAO/ZIF-8/K-PDMS	70	1	丁醇	40.3	2890	[31]
PDMS/P-ZNC	60	1	丁醇	40.7	1035.4	[57]
ZIF-8@ABT/PDMS	70	1	丁醇	44	1074	[58]
ILTf₂N@MIL-101/PEBA	30	5	乙酸乙酯	207.6	2354	[59]
PEBA/ZSM-5-10	50	5	乙酸乙酯	185.5	199.5	[60]
PAN-C3-P3	50	1	乙酸乙酯	70	7850	[61]
3%ZIF-67/ PVDF	30	1.5	甲苯	41.2	467.6	[62]

图8 (a)悬浮分散ZIF-8/PDMS混合基质膜的制备示意；进料浓度（b）和温度（c）对渗透汽化性能的影响[52]

Fig.8 (a) Preparation diagram of suspended dispersed ZIF-8/PDMS mixed matrix membrane; Influence of feed concentration (b) and temperature (c) on pervaporation performance[52]

图9 红酒分离渗透汽化装置[75]

Fig.9 The pervaporation equipment for red wine separation[75]

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