二元醇共价交联羧基化石墨烯复合膜和正丁醇脱水性能

doi:10.16085/j.issn.1000-6613.2021-1896

化工进展 ›› 2022, Vol. 41 ›› Issue (7): 3801-3807.DOI: 10.16085/j.issn.1000-6613.2021-1896

二元醇共价交联羧基化石墨烯复合膜和正丁醇脱水性能

韩光鲁¹^,²(), 路宽¹, 吕杰¹, 张永辉¹(), 陈墨涵¹

^1.郑州轻工业大学材料与化学工程学院，河南郑州 450001
^2.河南省化工分离过程强化工程技术研究中心，河南郑州 450001

收稿日期:2021-09-06 修回日期:2021-10-31 出版日期:2022-07-25 发布日期:2022-07-23
通讯作者: 张永辉
作者简介:韩光鲁（1985—），男，博士，讲师，硕士生导师，研究方向为功能膜材料的制备和应用。E-mail：2014115@zzuli.edu.cn。
基金资助:
国家自然科学基金(21606211);中原千人科技创新领军人才项目(194200510013);河南省科技计划基础与前沿技术研究计划(152300410127);郑州轻工业大学博士科研基金(2014BSJJ056)

Carboxyl graphene composite membranes covalently crosslinked with diols and the n-butanol dehydration properties

HAN Guanglu¹^,²(), LU Kuan¹, LYU Jie¹, ZHANG Yonghui¹(), CHEN Mohan¹

^1.School of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, Henan, China
^2.Henan Engineering Research Center of Chemical Engineering Separation Process Intensification, Zhengzhou 450001, Henan, China

Received:2021-09-06 Revised:2021-10-31 Online:2022-07-25 Published:2022-07-23
Contact: ZHANG Yonghui

摘要/Abstract

摘要：

以二元醇（乙二醇、1,3-丙二醇和1,4-丁二醇）为交联剂，通过抽滤的方式在涂覆盐酸多巴胺的聚醚砜（PES）支撑层上制备了共价交联的羧基化石墨烯/聚醚砜（CG/PES）复合膜。稳定性测试证明盐酸多巴胺的涂覆和二元醇的交联显著提高了分离层和支撑层以及CG纳米片间的结合力。采用扫描电子显微镜、X射线衍射仪、X射线光电子能谱仪和水接触角测试仪对复合膜的物化性质和微观形貌进行了表征。结果表明，所得复合膜的分离层连续无缺陷，厚度在60~64nm之间。二元醇与CG纳米片上的羧基成功发生反应，将CG纳米片锚固在一起。交联剂的引入没有大幅降低亲水性且实现了对分离层层间距的有效调控，随二元醇分子尺寸增加，所得复合膜的层间距由0.761nm提高到0.778nm。CG/PES复合膜对正丁醇/水混合物具有优良的渗透汽化分离性能。在料液温度为50℃、料液中水的质量分数为10%时，三种交联剂所得复合膜的渗透通量分别达到0.79kg/(m²·h)、0.87kg/(m²·h)和0.96kg/(m²·h)，而分离因子比未交联的复合膜高一个数量级。15天的稳定性测试结果表明，所得复合膜分离性能无显著变化，能够满足渗透汽化应用要求。

关键词: 膜, 分离, 渗透汽化, 羧基化石墨烯, 交联, 正丁醇脱水

Abstract:

Covalently crosslinked carboxyl graphene/polyethersulfone (CG/PES) composite membranes were prepared by suction filtration. Polyethersulfone (PES) support was coated with dopamine hydrochloride. Diols(ethylene glycol, 1,3-propylene glycol and 1,4-butanediol) were used as crosslinking agents. The stability test showed that the coated dopamine hydrochloride improved the adhesion between the separation layer and the support layer. The diol crosslinking structure ensured the stability of the CG separation layer. The physicochemical properties and micro morphology of the composite membranes were characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and water contact angle tester. The results indicated that the separation layer of the composite membrane was continuous and defect-free, and the thickness ranged from 60nm to 64nm. The diol reacted successfully with the carboxyl groups on the CG nanosheets and anchored the CG nanosheets together. The introduction of crosslinking agents did not significantly reduce the membrane hydrophilicity and realized the effective regulation of the d-spacing. With the increase of diol molecular size, the d-spacing of the composite membrane increased from 0.761nm to 0.778nm. CG/PES composite membrane exhibited excellent pervaporation separation performance for n-butanol/water mixture. When the feed temperature was 50℃ and the water mass fraction in feed was 10%, the permeation flux of the composite membrane obtained from the three crosslinking agents reached to 0.79kg/(m²·h), 0.87kg/(m²·h) and 0.96kg/(m²·h), respectively. The separation factor was one order of magnitude higher than that of the non-crosslinked composite membrane. The 15 day stability testing results showed that the separation performance of as-prepared composite membrane had no significant change and can meet the requirements of pervaporation application.

Key words: membranes, separation, pervaporation, carboxyl graphene, crosslinking, butanol dehydration

中图分类号:

TQ028.8

韩光鲁, 路宽, 吕杰, 张永辉, 陈墨涵. 二元醇共价交联羧基化石墨烯复合膜和正丁醇脱水性能[J]. 化工进展, 2022, 41(7): 3801-3807.

HAN Guanglu, LU Kuan, LYU Jie, ZHANG Yonghui, CHEN Mohan. Carboxyl graphene composite membranes covalently crosslinked with diols and the n-butanol dehydration properties[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3801-3807.

图/表 9

图1 改性与未改性复合膜浸泡后的照片和超声后的实物

图2 复合膜的扫描电镜图

图3 复合膜的XPS图谱

图4 复合膜的XRD图

图5 复合膜的水接触角

图6 复合膜对正丁醇/水混合物的分离性能

图7 操作条件对膜分离性能的影响

图8 CG-3/PES复合膜分离性能稳定性

图9 CG-3/PES复合膜分离性能稳定性测试前后的SEM图

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二元醇共价交联羧基化石墨烯复合膜和正丁醇脱水性能

Carboxyl graphene composite membranes covalently crosslinked with diols and the n-butanol dehydration properties

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