亲疏水性CuBTC/PVDF复合膜应用于膜蒸馏抗油实验

doi:10.11949/0438-1157.20191439

化工学报 ›› 2020, Vol. 71 ›› Issue (6): 2811-2820.DOI: 10.11949/0438-1157.20191439

• 材料化学工程与纳米技术 • 上一篇下一篇

亲疏水性CuBTC/PVDF复合膜应用于膜蒸馏抗油实验

汪义泽^1,²(),王德武¹(),侯得印^2,³(),安广宇²,唐敏²,王军³

^1.河北工业大学化工学院，天津 300130
^2.中国科学院生态环境研究中心，中国科学院饮用水科学与技术重点实验室，北京 100085
^3.中国科学院生态环境研究中心，环境水质学国家重点实验室，北京 100085

收稿日期:2019-11-26 修回日期:2020-03-23 出版日期:2020-06-05 发布日期:2020-06-05
通讯作者: 王德武,侯得印
作者简介:汪义泽（1995—），男，硕士研究生，18222951370@163.com
基金资助:
国家自然科学基金面上项目(51978650);河北省自然科学基金项目(B2017202185)

Hydrophilic-hydrophobic CuBTC/PVDF composite membrane applied to membrane distillation anti-oil experiment

Yize WANG^1,²(),Dewu WANG¹(),Deyin HOU^2,³(),Guangyu AN²,Min TANG²,Jun WANG³

^1.School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
^2.Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
^3.State Key Laboratory of Environment Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China

Received:2019-11-26 Revised:2020-03-23 Online:2020-06-05 Published:2020-06-05
Contact: Dewu WANG,Deyin HOU

摘要/Abstract

摘要：

采用水热法合成亲水性的CuBTC金属有机骨架(MOFs)颗粒，采用聚乙烯醇(PVA)作为黏合剂，用抽滤的方法将CuBTC颗粒附载在聚偏氟乙烯(PVDF)膜上，之后用戊二醛(GA)对PVA进行交联，制备出表层亲水、底层疏水的CuBTC/PVDF复合膜。通过场发射电子显微镜、比表面积及孔径分析仪、接触角测量仪、孔径分析仪、X射线衍射仪等对CuBTC颗粒和不同CuBTC含量的复合膜的表面特征、结构形态和稳定性进行了表征。结果表明，CuBTC颗粒有着较大的比表面积和孔容，CuBTC颗粒可以牢固地抽滤在PVDF膜表面，热稳定性高且有较好的柔韧性。与抽滤前的PVDF膜相比，随着CuBTC颗粒的增多，膜厚度有所增加，孔径和孔隙率有所减小，但对其膜蒸馏膜通量的影响不大，且在CuBTC含量在0.6 g时表现出较好的性能。在以1 g/L原油和35 g/L氯化钠混合溶液为进料液对原膜和复合膜进行直接接触膜蒸馏抗油污实验，发现原膜很快被油污染堵塞毛孔，而复合膜具有良好的抗油污染能力，可以进行长期的膜蒸馏实验。

关键词: 膜, 蒸馏, 水热, MOF, 聚偏氟乙烯, CuBTC

Abstract:

To solve the problem of water scarcity, membrane distillation(MD) technology has been paid more and more attention to the application of seawater desalination and wastewater treatment, and membrane is an important part of membrane distillation. In the membrane distillation process, the membrane is easily contaminated by oily substances, so it is important to modify the membrane to achieve oil resistance. In this paper, the hydrophilic CuBTC organometallic framework (MOF) particles were synthesized by hydrothermal method. Then, using polyvinyl alcohol (PVA) as binder, CuBTC particles were attached to the membrane by suction filtration. Finally, PVA was crosslinked with glutaraldehyde (GA) to prepare a CuBTC/PVDF composite membrane having a hydrophilic-hydrophobic layer. X-ray diffraction analysis, scanning electron microscopy and specific surface area tests show that CuBTC has high purity, specific morphology and excellent properties. To solve the problem of water solubility of PVA, PVA is crosslinked with glutaraldehyde to cure PVA, and the obtained product has excellent stability. The contact angle, pore size, pore size distribution and porosity of the composite membrane with four different CuBTC contents were analyzed. The results show that CuBTC particles have a large specific surface area and pore volume. CuBTC particles can be firmly suction filtered on the surface of PVDF membrane, which has high thermal stability and good flexibility. The oil-containing high-salt solution prepared with 1 g/L crude oil and 35 g/L sodium chloride was used as the feed liquid to conduct DCMD anti-oil pollution test on the original membrane and the composite membrane. It was found that the original membrane was quickly blocked by oil pollution, and the composite membrane had good resistance, which can be applied to long-term membrane distillation experiments.

Key words: membrane, distillation, hydrothermal, MOF, poly(vinylidene fluoride), CuBTC

中图分类号:

TQ 028.8

汪义泽, 王德武, 侯得印, 安广宇, 唐敏, 王军. 亲疏水性CuBTC/PVDF复合膜应用于膜蒸馏抗油实验[J]. 化工学报, 2020, 71(6): 2811-2820.

Yize WANG, Dewu WANG, Deyin HOU, Guangyu AN, Min TANG, Jun WANG. Hydrophilic-hydrophobic CuBTC/PVDF composite membrane applied to membrane distillation anti-oil experiment[J]. CIESC Journal, 2020, 71(6): 2811-2820.

图/表 15

图1 CuBTC 颗粒和CuBTC/PVDF复合膜的制备机理图

Fig.1 Preparation mechanism diagram of CuBTC particles and CuBTC/PVDF composite membrane

图2 原油液滴粒径分布

Fig.2 Crude-oil diameter distribution in NaCl solution

图3 直接接触式膜蒸馏装置示意图a—膜组件；b—温度计；c—流量计；d—磁力循环泵；e—恒温加热槽；f—进料液槽；g—渗透液槽；i—馏分收集器；j—天平；k—恒温冷却槽；m—计算机

Fig.3 Schematic diagram of experimental setup of DCMD

图4 CuBTC自组装过程

Fig.4 Self-assembly process of CuBTC

图5 PVA和GA交联原理

Fig.5 Cross-linking principle of PVA and GA

图6 CuBTC样品的XRD谱图

Fig.6 XRD patterns of CuBTC sample

图7 CuBTC样品的N2的吸附-脱附等温曲线与BJH孔径分布

Fig.7 N2 adsorption-desorption isotherms and BJH pore size distributions of CuBTC samples

表1 CuBTC颗粒的比表面积、孔径及孔容

Table 1 BET, pore size and pore volume of CuBTC particles

比表面积/(m²/g)

孔容/(cm³/g)

孔径/nm

BJH吸

附孔容

BJH脱

附孔容

BJH吸

附孔径

BJH脱

附孔径

图8 膜的空气中水接触角和水下油接触角

Fig.8 Water contact angle and underwater oil contact angle of membranes

图9 各膜的孔径分布

Fig.9 Pore size distribution of membranes

表2 膜的厚度、平均孔径及孔隙率

Table 2 Thickness, average pore diameter and porosity of membranes

膜	CuBTC 含量/g	膜厚度/mm	平均孔径/μm	孔隙率/%
PVDF	0	0.121±0.02	0.860±0.02	63.055±0.82
PVDF-M1	0.2	0.144±0.03	0.839±0.02	59.796±0.69
PVDF-M2	0.4	0.167±0.03	0.814±0.02	56.129±1.14
PVDF-M3	0.6	0.184±0.03	0.789±0.03	52.413±0.54
PVDF-M4	0.8	0.223±0.05	0.702±0.03	44.741±0.43

图10 CuBTC颗粒的扫描电镜图

Fig.10 SEM images of CuBTC particles

图11 PVDF膜和复合膜的电镜图

Fig.11 SEM images of PVDF membrane and composite membrane

图12 直接接触式膜蒸馏抗油实验中通量和电导随时间的变化

Fig.12 Flux and conductivity changes with time in anti-oil DCMD experiments

图13 膜蒸馏前后膜表面对比

Fig.13 Menbrane surface comparison before and after DCMD

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亲疏水性CuBTC/PVDF复合膜应用于膜蒸馏抗油实验

Hydrophilic-hydrophobic CuBTC/PVDF composite membrane applied to membrane distillation anti-oil experiment

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