APTES改性ZIF-L/PEBA混合基质膜强化渗透汽化分离苯酚研究

doi:10.11949/0438-1157.20211358

摘要/Abstract

摘要：

渗透汽化(PV)膜分离是一种高效节能、无污染的化工分离技术，在有机废水处理领域的应用潜力巨大。以3-氨丙基三乙氧基硅烷(APTES)改性二维ZIF-L(AZLs)，将其引入聚醚嵌段酰胺(PEBA)内制备AZLs/PEBA混合基质膜，用于分离水溶液中的苯酚。系统表征了所制膜的微结构与物化特性，考察了APTES添加量、AZLs填充量、操作温度、料液浓度等对膜分离性能的影响。结果表明：AZLs均匀分散在PEBA基质中，表明两者具有良好的界面相容性。AZLs的加入使得膜疏水性增强而表面自由能降低，从而提高了PEBA膜的选择性。当分离80℃、1000 mg/kg苯酚水溶液时，AZLs/PEBA膜总通量可达2046 g/(m²·h)，分离因子为25.4，并且具有一定的稳定性。所制AZLs/PEBA混合基质膜在含酚废水处理方面具有应用前景。

关键词: 膜, 分离, 废水, 聚醚嵌段酰胺, 金属有机框架材料, 混合基质膜, 渗透汽化, 苯酚

Abstract:

As an efficient, energy-saving, and pollution-free chemical separation technology, pervaporation(PV) has great application potential for organic wastewater treatment. In this study, the AZLs were synthesized by modifying two-dimensional ZIF-L with 3-aminopropyltriethoxysilane(APTES). The AZLs were incorporated into the poly(ether-block-amide)(PEBA) to prepare AZLs/PEBA mixed matrix membranes for phenol separation from aqueous solution. The membrane microstructures and physicochemical properties were characterized in detail. Effects of the APTES addition amount, AZLs loading, operating temperature, and feed concentration on separation performance of the membranes were investigated. The AZLs were uniformly dispersed within PEBA matrix, indicating their good interfacial compatibility. The addition of AZLs increased the hydrophobicity and reduced the surface free energy of PEBA membrane, thereby enhancing membrane selectivity. The AZLs/PEBA membrane had a total flux of 2046 g/(m²·h) and a separation factor of 25.4 in separating 1000 mg/kg phenol aqueous solution at 80℃. The AZLs/PEBA membrane also displayed a certain stability. The as-prepared AZLs/PEBA mixed matrix membranes were promising candidates in the phenolic wastewater treatment.

Key words: membrane, separation, wastewater, poly(ether-block-amide), metal-organic frameworks, mixed matrix membranes, pervaporation, phenol

中图分类号:

TQ 028.8

毛恒, 王月, 王森, 刘伟民, 吕静, 陈甫雪, 赵之平. APTES改性ZIF-L/PEBA混合基质膜强化渗透汽化分离苯酚研究[J]. 化工学报, 2022, 73(3): 1389-1402.

Heng MAO, Yue WANG, Sen WANG, Weimin LIU, Jing LYU, Fuxue CHEN, Zhiping ZHAO. APTES-modified ZIF-L/PEBA mixed matrix membranes for enhancing phenol perm-selective pervaporation[J]. CIESC Journal, 2022, 73(3): 1389-1402.

图/表 15

图1 APTES与ZIF-L之间的相互作用(a)和AZLs/PEBA混合基质膜的制备(b)

Fig.1 Mutual interactions between ZIF-L and APTES (a), and preparation process of AZLs/PEBA MMMs (b)

图2 ZIF-L(a)、 AZLs-0.25(b)、 AZLs-0.5(c)、 AZLs-0.75 (d)和AZLs-1.0 (e)的SEM图像

Fig.2 SEM images of ZIF-L (a), AZLs-0.25 (b), AZLs-0.5 (c), AZLs-0.75 (d), and AZLs-1.0 (e)

图3 AZLs的XRD谱图(a)、水接触角(b)、氮气吸附等温线(c)和孔径分布曲线(d)

Fig.3 XRD patterns (a), water contact angle (b), N2 adsorption isotherm (c), and pore size distribution curves(d) of AZLs

图4 PEBA膜(a)、 ZIF-L/PEBA-20 (b)、 AZLs-0.25/PEBA-20 (c)、 AZLs-0.5/PEBA-20 (d)、 AZLs-0.75/PEBA-20 (e)和AZLs-1.0/PEBA-20 (f)的表面SEM图像

Fig.4 Surface SEM images of PEBA membrane (a), ZIF-L/PEBA-20 (b), AZLs-0.25/PEBA-20 (c), AZLs-0.5/PEBA-20 (d), AZLs-0.75/PEBA-20 (e), and AZLs-1.0/PEBA-20 (f)

图5 PEBA膜(a)、 ZIF-L/PEBA-20 (b)、 AZLs-0.25/PEBA-20 (c)、 AZLs-0.5/PEBA-20 (d)、 AZLs-0.75/PEBA-20 (e)和AZLs-1.0/PEBA-20 (f)的断面SEM图像

Fig.5 Cross-sectional SEM images of PEBA membrane (a), ZIF-L/PEBA-20 (b), AZLs-0.25/PEBA-20 (c), AZLs-0.5/PEBA-20 (d), AZLs-0.75/PEBA-20 (e), and AZLs-1.0/PEBA-20 (f)

图6 PEBA和AZLs-X/PEBA-20膜的XRD谱图(a)和应力-应变曲线(b)

Fig.6 XRD patterns (a) and stress-strain curves (b) of PEBA and AZLs-X/PEBA-20 membranes

表1 PEBA和AZLs-X/PEBA-20膜的物化性质

Table1 Physicochemical properties of PEBA and AZLs-X/PEBA-20 membranes

样品	分离层厚度/μm	表面自由能/(mN/m)	断裂强度/MPa	最大伸长率/%	弹性模量/MPa
PEBA膜	18.6	46.5	2.1±0.3	548±23	98.0±4.5
ZIF-L/PEBA-20	19.4	37.3	6.9±0.2	990±34	146.0±6.3
AZLs-0.25/PEBA-20	16.7	34.8	8.0±0.4	1088±57	161.0±8.7
AZLs-0.5/PEBA-20	20.5	30.5	6.8±0.5	726±43	188.0±5.7
AZLs-0.75/PEBA-20	24.1	33.4	7.6±0.6	891±62	136.0±7.3
AZLs-1.0/PEBA-20	25.3	35.1	6.1±0.6	1047±48	124.0±9.5

图7 PEBA和AZLs-X/PEBA-20膜的水接触角(a)和溶剂吸附量(b)

Fig.7 Water contact angle (a) and solvent uptake (b) of PEBA and AZLs-X/PEBA-20 membranes

图8 不同填料对AZLs/PEBA膜分离性能的影响：渗透通量和分离因子(a);渗透性和选择性(b)(操作条件:填料量,20%(质量);苯酚浓度,1000 mg/kg;料液温度,50℃)

Fig.8 Effects of different fillers on separation performance of AZLs/PEBA membranes: permeation flux and separation factor (a); permeability and selectivity (b)(Operating conditions: filler loading, 20%(质量); phenol concentration, 1000 mg/kg; feed temperature, 50℃)

图9 AZLs-0.5填充量对AZLs-0.5/PEBA膜分离性能的影响：渗透通量和分离因子(a);渗透性和选择性 (b)(操作条件:苯酚浓度,1000 mg/kg;料液温度,50℃)

Fig.9 Effects of AZLs-0.5 loading on separation performance of AZLs-0.5/PEBA membranes: permeation flux and separation factor (a);permeability and selectivity (b)(Operating conditions: phenol concentration, 1000 mg/kg; feed temperature, 50℃)

图10 料液温度对AZLs-0.5/PEBA-20膜分离性能的影响：渗透通量和分离因子(a)，渗透性和选择性(b);AZLs-0.5/PEBA-20膜(c)和PEBA膜(d)的lnJ-l/T关系(操作条件:苯酚浓度,1000 mg/kg)

Fig.10 Effects of feed temperature on separation performance of AZLs-0.5/PEBA-20: permeation flux and separation factor (a), permeability and selectivity (b); Arrhenius plots ofAZLs-0.5/PEBA-20 (c) and PEBA membrane (d)(Operating conditions: phenol concentration, 1000 mg/kg)

表2 PEBA和AZLs-0.5/PEBA-20膜内分子渗透能量分析

Table 2 Energy analysis for molecular permeation of PEBA and AZLs-0.5/PEBA-20 membranes

样品	E_A,_i /( kJ/ mol)		ΔH_evp,_i (80 ^oC) /( kJ/ mol)		E_P,_i /( kJ/mol)
样品	苯酚	水	苯酚	水	苯酚	水
PEBA膜	45.31	34.25	54.67	41.63	-9.36	-7.38
AZLs-0.5/PEBA-20	43.32	27.94	54.67	41.63	-11.35	-13.69

图11 料液浓度对AZLs-0.5/PEBA-20膜分离性能的影响：(a)渗透通量和分离因子;(b)渗透性和选择性(操作条件:料液温度,80℃)

Fig.11 Effects of feed concentration on separation performance of AZLs-0.5/PEBA-20: permeation flux and separation factor (a); permeability and selectivity (b)(Operating conditions: feed temperature, 80℃)

图12 AZLs-0.5/PEBA-20膜的长时稳定性测试

Fig.12 Extended trial of AZLs-0.5/PEBA-20

表3 不同渗透汽化膜分离苯酚水溶液分离性能对比

Table 3 Performance comparison of various pervaporation membranes in separating phenol aqueous solution

膜	温度/ ℃	浓度/ %(质量)	总通量/ (g/(m²?h))	分离因子	PSI	文献
PDMS	70	1	370	21	7400	[34]
PEBA-4033	60	2	350	23	7700	[35]
PEBA-4033	60	1	620	20	11780	[36]
PERVAP-1060	60	2	6840	6	34200	[35]
OA-PDMS	70	0.5	320	6.3	1696	[37]
ZSM-5/PDMS	80	0.01	1590	4.5	5565	[38]
Polyimide	70	1	370	7.5	2405	[39]
PIM-1	70	1	210	16	3150	[40]
PEBA-2533	70	0.1	800	52.6	41280	[1]
PEBA-2533	80	0.1	1430	25	34320	[41]
PU/ZSM-ECD	80	0.3	980	9.3	8134	[42]
PUCD	70	3	70	49	3360	[43]
PEBA/PVDF	80	0.1	6560	9	52480	[3]
AZLs/PEBA	70	0.1	1362	22.3	29011	本文
AZLs/PEBA	80	0.1	2046	25.4	49922	本文

参考文献 43

1	Cao X T, Wang K A, Feng X S. Removal of phenolic contaminants from water by pervaporation[J]. Journal of Membrane Science, 2021, 623: 119043.
2	Jin M Y, Lin Y Q, Liao Y, et al. Development of highly-efficient ZIF-8@PDMS/PVDF nanofibrous composite membrane for phenol removal in aqueous-aqueous membrane extractive process[J]. Journal of Membrane Science, 2018, 568: 121-133.
3	Khan R, Ul Haq I, Mao H, et al. Enhancing the pervaporation performance of PEBA/PVDF membrane by incorporating MAF-6 for the separation of phenol from its aqueous solution[J]. Separation and Purification Technology, 2021, 256: 117804.
4	Mao H, Li S H, Xu L H, et al. Zeolitic imidazolate frameworks in mixed matrix membranes for boosting phenol/water separation: crystal evolution and preferential orientation[J]. Journal of Membrane Science, 2021, 638: 119611.
5	Han T T, Xiao Y L, Tong M M, et al. Synthesis of CNT@MIL-68(Al) composites with improved adsorption capacity for phenol in aqueous solution[J]. Chemical Engineering Journal, 2015, 275: 134-141.
6	Tian W, Lin J, Zhang H, et al. Enhanced removals of micropollutants in binary organic systems by biomass derived porous carbon/peroxymonosulfate[J]. Journal of Hazardous Materials, 2021, 408: 124459.
7	齐亚兵, 杨清翠. 煤化工废水脱酚技术研究进展[J]. 应用化工, 2021, 50(5): 1414-1419.
	Qi Y B, Yang Q C. Research progress on removal of phenols from coal chemical wastewater[J]. Applied Chemical Industry, 2021, 50(5): 1414-1419.
8	Mao H, Li S H, Zhang A S, et al. Furfural separation from aqueous solution by pervaporation membrane mixed with metal organic framework MIL-53(Al) synthesized via high efficiency solvent-controlled microwave[J]. Separation and Purification Technology, 2021, 272: 118813.
9	方丽君, 王景梅, 林巧靖, 等. 二苯并-18-冠醚-6/聚醚嵌段酰胺膜富集水中苯酚性能研究[J]. 化工学报, 2021, 72(7): 3716-3727.
	Fang L J, Wang J M, Lin Q J, et al. Enrichment of phenol in water by dibenzo-18-crown ether-6/polyether block amide membrane[J]. CIESC Journal, 2021, 72(7): 3716-3727.
10	Ji Y, Chen G, Liu G, et al. Ultrathin membranes with a polymer/nanofiber interpenetrated structure for high-efficiency liquid separations[J]. ACS Applied Materials & Interfaces, 2019, 11(40): 36717-36726.
11	Yang D C, Tian D X, Xue C, et al. Tuned fabrication of the aligned and opened CNT membrane with exceptionally high permeability and selectivity for bioalcohol recovery[J]. Nano Letters, 2018, 18(10): 6150-6156.
12	牟春霞, 张时雨, 邹昀, 等. 疏水SiO₂填充PDMS膜分离水中乙酸正丁酯的性能[J]. 化工学报, 2017, 68(6): 2407-2414.
	Mu C X, Zhang S Y, Zou Y, et al. Separation of n-butyl acetate from aqueous solution using PDMS membrane filled with hydrophobic SiO₂ [J]. CIESC Journal, 2017, 68(6): 2407-2414.
13	Xu S, Zhang H, Yu F, et al. Enhanced ethanol recovery of PDMS mixed matrix membranes with hydrophobically modified ZIF-90[J]. Separation and Purification Technology, 2018, 206: 80-89.
14	Wang H, Liu Y L, Li J. Designer metal-organic frameworks for size-exclusion-based hydrocarbon separations: progress and challenges[J]. Advanced Materials, 2020, 32(44): 2002603.
15	Jayaramulu K, Geyer F, Schneemann A, et al. Hydrophobic metal-organic frameworks[J]. Advanced Materials, 2019, 31(32): 1900820.
16	Liu Q, Li Y, Li Q, et al. Mixed-matrix hollow fiber composite membranes comprising of PEBA and MOF for pervaporation separation of ethanol/water mixtures[J]. Separation and Purification Technology, 2019, 214: 2-10.
17	Zhang A S, Li S H, Ahmad A, et al. Coordinate covalent grafted ILs-modified MIL-101/PEBA membrane for pervaporation: adsorption simulation and separation characteristics[J]. Journal of Membrane Science, 2021, 619: 118807.
18	Wang H, Tang S H, Ni Y X, et al. Covalent cross-linking for interface engineering of high flux UiO-66-TMS/PDMS pervaporation membranes[J]. Journal of Membrane Science, 2020, 598: 117791.
19	Chen R Z, Yao J F, Gu Q F, et al. A two-dimensional zeolitic imidazolate framework with a cushion-shaped cavity for CO₂ adsorption[J]. Chemical Communications, 2013, 49(82): 9500.
20	王艳芳, 毛恒, 蔡玮玮, 等. ZIF-L/PDMS混合基质膜蒸气渗透耦合发酵强化乙醇生产效率的研究[J]. 化工学报, 2021, 72(10): 5226-5236.
	Wang Y F, Mao H, Cai W W, et al. Enhancing ethanol production efficiency by ZIF-L/PDMS mixed matrix membrane via vapor permeation-fermentation coupling process[J]. CIESC Journal, 2021, 72(10): 5226-5236.
21	Mao H, Zhen H G, Ahmad A, et al. Highly selective and robust PDMS mixed matrix membranes by embedding two-dimensional ZIF-L for alcohol permselective pervaporation[J]. Journal of Membrane Science, 2019, 582: 307-321.
22	Li Q Q, Cheng L, Shen J, et al. Improved ethanol recovery through mixed-matrix membrane with hydrophobic MAF-6 as filler[J]. Separation and Purification Technology, 2017, 178: 105-112.
23	Owens D K, Wendt R C. Estimation of the surface free energy of polymers[J]. Journal of Applied Polymer Science, 1969, 13(8): 1741-1747.
24	路姣姣, 毛恒, 王涛, 等. HNTs填充PDMS膜的制备及其分离ABE-水体系的研究[J]. 膜科学与技术, 2020, 40(1): 53-63.
	Lu J J, Mao H, Wang T, et al. Preparation of HNTs filled PDMS membranes for the separation of ABE from aqueous solution[J]. Membrane Science and Technology, 2020, 40(1): 53-63.
25	Kulkarni S S, Kittur A A, Aralaguppi M I, et al. Synthesis and characterization of hybrid membranes using poly(vinyl alcohol) and tetraethylorthosilicate for the pervaporation separation of water-isopropanol mixtures[J]. Journal of Applied Polymer Science, 2004, 94(3): 1304-1315.
26	Wang S F, Mahalingam D, Sutisna B, et al. 2D-dual-spacing channel membranes for high performance organic solvent nanofiltration[J]. Journal of Materials Chemistry A, 2019, 7(19): 11673-11682.
27	Pan F, Cheng Q, Jia H, et al. Facile approach to polymer–inorganic nanocomposite membrane through a biomineralization-inspired process[J]. Journal of Membrane Science, 2010, 357: 171-177.
28	Liu S N, Liu G P, Shen J, et al. Fabrication of MOFs/PEBA mixed matrix membranes and their application in bio-butanol production[J]. Separation and Purification Technology, 2014, 133: 40-47.
29	Kolokolov D I, Stepanov A G, Jobic H. Mobility of the 2-methylimidazolate linkers in ZIF-8 probed by 2H NMR: saloon doors for the guests[J]. The Journal of Physical Chemistry C, 2015, 119(49): 27512-27520.
30	Khan A, Ali M, Ilyas A, et al. ZIF-67 filled PDMS mixed matrix membranes for recovery of ethanol via pervaporation[J]. Separation and Purification Technology, 2018, 206: 50-58.
31	Feng X S, Huang R Y M. Estimation of activation energy for permeation in pervaporation processes[J]. Journal of Membrane Science, 1996, 118(1): 127-131.
32	Liu W P, Li Y F, Meng X X, et al. Embedding dopamine nanoaggregates into a poly(dimethylsiloxane) membrane to confer controlled interactions and free volume for enhanced separation performance[J]. Journal of Materials Chemistry A, 2013, 1(11): 3713.
33	Wang X L, Chen J X, Fang M Q, et al. ZIF-7/PDMS mixed matrix membranes for pervaporation recovery of butanol from aqueous solution[J]. Separation and Purification Technology, 2016, 163: 39-47.
34	Wu P, Field R W, England R, et al. A fundamental study of organofunctionalised PDMS membranes for the pervaporative recovery of phenolic compounds from aqueous streams[J]. Journal of Membrane Science, 2001, 190(2): 147-157.
35	Kujawski W, Warszawski A, Ratajczak W, et al. Application of pervaporation and adsorption to the phenol removal from wastewater[J]. Separation and Purification Technology, 2004, 40(2): 123-132.
36	Böddeker K W, Bengtson G, Bode E. Pervaporation of low volatility aromatics from water[J]. Journal of Membrane Science, 1990, 53(1/2): 143-158.
37	Ye H, Yan X, Zhang X, et al. Pervaporation properties of oleyl alcohol-filled polydimethylsiloxane membranes for the recovery of phenol from wastewater[J]. Iranian Polymer Journal, 2017, 26(8): 639-649.
38	Li D, Yao J, Sun H, et al. Recycling of phenol from aqueous solutions by pervaporation with ZSM-5/PDMS/PVDF hollow fiber composite membrane[J]. Applied Surface Science, 2018, 427: 288-297.
39	Pithan F, Staudt-Bickel C. Crosslinked copolyimide membranes for phenol recovery from process water by pervaporation[J]. ChemPhysChem, 2003, 4(9): 967-973.
40	Budd P, Elabas E, Ghanem B, et al. Solution-processed, organophilic membrane derived from a polymer of intrinsic microporosity[J]. Advanced Materials, 2004, 16(5): 456-459.
41	Hao X G, Pritzker M, Feng X S. Use of pervaporation for the separation of phenol from dilute aqueous solutions[J]. Journal of Membrane Science, 2009, 335(1/2): 96-102.
42	Ye H, Zhang X, Zhao Z X, et al. Pervaporation performance of surface-modified zeolite/PU mixed matrix membranes for separation of phenol from water[J]. Iranian Polymer Journal, 2017, 26(3): 193-203.
43	Ye H, Wang J, Wang Y, et al. Effects of simultaneous chemical cross-linking and physical filling on separation performances of PU membranes[J]. Iranian Polymer Journal, 2013, 22(8): 623-633.

[1]	邵苛苛, 宋孟杰, 江正勇, 张旋, 张龙, 高润淼, 甄泽康. 水平方向上冰中受陷气泡形成和分布实验研究[J]. 化工学报, 2023, 74(S1): 161-164.
[2]	吴延鹏, 李晓宇, 钟乔洋. 静电纺丝纳米纤维双疏膜油性细颗粒物过滤性能实验分析[J]. 化工学报, 2023, 74(S1): 259-264.
[3]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[4]	赵亚欣, 张雪芹, 王荣柱, 孙国, 姚善泾, 林东强. 流穿模式离子交换层析去除单抗聚集体[J]. 化工学报, 2023, 74(9): 3879-3887.
[5]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[6]	何松, 刘乔迈, 谢广烁, 王斯民, 肖娟. 高浓度水煤浆管道气膜减阻两相流模拟及代理辅助优化[J]. 化工学报, 2023, 74(9): 3766-3774.
[7]	胡建波, 刘洪超, 胡齐, 黄美英, 宋先雨, 赵双良. 有机笼跨细胞膜易位行为的分子动力学模拟研究[J]. 化工学报, 2023, 74(9): 3756-3765.
[8]	齐聪, 丁子, 余杰, 汤茂清, 梁林. 基于选择吸收纳米薄膜的太阳能温差发电特性研究[J]. 化工学报, 2023, 74(9): 3921-3930.
[9]	刘爽, 张霖宙, 许志明, 赵锁奇. 渣油及其组分黏度的分子层次组成关联研究[J]. 化工学报, 2023, 74(8): 3226-3241.
[10]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[11]	邢雷, 苗春雨, 蒋明虎, 赵立新, 李新亚. 井下微型气液旋流分离器优化设计与性能分析[J]. 化工学报, 2023, 74(8): 3394-3406.
[12]	张佳怡, 何佳莉, 谢江鹏, 王健, 赵鹬, 张栋强. 渗透汽化技术用于锂电池生产中N-甲基吡咯烷酮回收的研究进展[J]. 化工学报, 2023, 74(8): 3203-3215.
[13]	张瑞航, 曹潘, 杨锋, 李昆, 肖朋, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析[J]. 化工学报, 2023, 74(8): 3386-3393.
[14]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[15]	张缘良, 栾昕奇, 苏伟格, 李畅浩, 赵钟兴, 周利琴, 陈健民, 黄艳, 赵祯霞. 离子液体复合萃取剂选择性萃取尼古丁的研究及DFT计算[J]. 化工学报, 2023, 74(7): 2947-2956.