三维网络萃取膜的制备及传质效率研究

doi:10.11949/0438-1157.20221622

摘要/Abstract

摘要：

以亲水聚四氟乙烯(PTFE)膜为支撑体、以乙烯基三乙氧基硅烷(VTES)为偶联剂，利用乙烯基封端聚二甲基硅氧烷(PDMS)和聚甲基氢硅氧烷(PMHS)锁闭萃取剂磷酸二异辛酯(D2EHPA)，制备三维网络萃取膜(3D-NEM)，并将其用于重金属离子废水中镍元素的萃取分离。研究结果显示60℃、15 min的处理条件可以不破坏原支撑体结构并在其表面成功引入羟基，使构建的三维网络复合层锚定在改性后的支撑体表面。在料液相Ni²⁺浓度150 mg/L、萃取剂含量37%(质量)的条件下3D-NEM的6 h平均传质通量达最高值1560.28 mg∙m^-2∙h^-1。相互交联的三维网格结构有效地阻止了萃取剂流失，6 h运行平均通量衰减率仅有31.91%。与传统支撑液膜相比，本研究制备的3D-NEM在亲水膜表面成功锚定超薄萃取功能层，体现出降低传质阻力与提升运行稳定性的双重优势。

关键词: 萃取, 膜, 三维网络, 稳定性, 聚硅氧烷

Abstract:

The three-dimensional network extracting membrane (3D-NEM) was prepared by using hydrophilic polytetrafluoroethylene (PTFE) membrane as the support, vinyl triethoxysilane (VTES) as coupling agent, vinyl terminated polydimethylsiloxane (PDMS) and polymethylhydrosiloxane (PMHS) as grid locking extractant bis(2-ethychexyl)phosphate (D2EHPA). The designed 3D-NEM was tested for the extraction of nickel from heavy metal ion wastewater. The results showed that the surface treatment at 60℃ for 15 min would not destroy the membrane structure but only introduced hydroxyl groups on its surface successfully. Further, the 3D network composite layer could be anchored on the modified support surface. To treat the feed of 150 mg/L Ni²⁺, the 6 h average mass transfer flux of 3D-NEM prepared with 37%(mass) extractant content reached the highest value of 1560.28 mg∙m^-2∙h^-1. The cross-linked 3D grid structure effectively prevented the loss of extractants, and the flux attenuation was only 31.91% after 6 h of operation. Compared with the traditional support liquid membrane (SLM), the 3D-NEM prepared in this study anchored the ultra-thin extraction functional layer on the hydrophilic membrane surface, presenting dual advantages of reducing mass transfer resistance and improving operation stability.

Key words: extraction, membranes, three-dimensional network, stability, polysiloxane

中图分类号:

TQ 028.8

陈向上, 马振杰, 任希华, 贾悦, 吕晓龙, 陈华艳. 三维网络萃取膜的制备及传质效率研究[J]. 化工学报, 2023, 74(3): 1126-1133.

Xiangshang CHEN, Zhenjie MA, Xihua REN, Yue JIA, Xiaolong LYU, Huayan CHEN. Preparation and mass transfer efficiency of three-dimensional network extraction membrane[J]. CIESC Journal, 2023, 74(3): 1126-1133.

图/表 10

表1 亲水聚四氟乙烯膜的性能参数

Table 1 Performance parameters of hydrophilic PTFE membrane

参数	数值
亲疏水性	亲水
平均孔径/μm	0.22
有效膜面积/m²	4.42×10^-3
皮层厚度/μm	16
孔隙率/%	76

图1 3D-NEM制备机理示意图

Fig.1 Mechanism diagram of 3D-NEM preparation

图2 3D-NEM萃取流程①料液相;②反萃相;③蠕动泵;④缓冲罐;⑤流量计;⑥萃取室;⑦反萃室;⑧隔膜阀 ;⑨U形压力计;⑩3D-NEM

Fig.2 Schematic diagram of 3D-NEM system

表2 不同改性条件下膜的始泡点最大孔径

Table 2 Maximum pore size of the membranes at the initial bubble point under different modified conditions

反应条件	始泡点压力/MPa	最大孔径/μm
PTFE基膜	0.085	0.375
60℃，15 min	0.105	0.304
60℃，30 min	0.039	0.818
80℃，15 min	0.040	0.797

图3 不同改性条件下PTFE膜的红外谱图

Fig.3 FTIR spectra of PTFE under different modified conditions

图4 PTFE亲水基膜、3D-NEM的表面及断面SEM形貌图

Fig.4 SEM morphology of surface and cross-section of PTFE hydrophilic membrane and 3D-NEM

图5 PTFE原膜及3D-NEM的特征EDS谱图

Fig.5 Characteristic EDS spectrum of PTFE original membrane and 3D-NEM

图6 3D-NEM截面P元素的EDS面扫描图像

Fig.6 EDS image of P element of 3D-NEM section

图7 不同D2EHPA含量下3D-NEM的萃取效率及稳定性

Fig.7 Extraction efficiency and stability of 3D-NEM with different D2EHPA contents

图8 料液相中镍的浓度对3D-NEM传质效率的影响

Fig.8 Effect of nickel concentration in feed on mass transfer efficiency of 3D-NEM

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