β-环糊精/聚醚共聚乙酰胺填充膜的制备及渗透汽化分离水中微量苯酚

doi:10.11949/j.issn.0438-1157.20160624

化工学报 ›› 2016, Vol. 67 ›› Issue (11): 4662-4670.DOI: 10.11949/j.issn.0438-1157.20160624

β-环糊精/聚醚共聚乙酰胺填充膜的制备及渗透汽化分离水中微量苯酚

张时雨¹, 邹昀^1,2, 韦藤幼^1,2, 牟春霞¹, 刘香君¹, 童张法^1,2

1 广西大学化学化工学院广西高校资源化工应用新技术重点实验室, 广西南宁 530004;
2 广西石化资源加工及过程强化技术重点实验室, 广西南宁 530004

收稿日期:2016-05-09 修回日期:2016-08-23 出版日期:2016-11-05 发布日期:2016-11-05
通讯作者: 童张法,zhftong@sina.com
基金资助:
广西教育厅广西高校科学技术研究项目（2013YB024）；广西自然科学基金面上项目（2014GXNSFAA118061）；广西石化资源加工及过程强化技术重点实验室主任基金（2015Z010）；广西优秀博士论文培育项目（YCBZ2012006）。

Preparation of β-cyclodextrin filled PEBA membranes and pervaporation separation of phenol from dilute solution

ZHANG Shiyu¹, ZOU Yun^1,2, WEI Tengyou^1,2, MU Chunxia¹, LIU Xiangjun¹, TONG Zhangfa^1,2

1 Guangxi Colleges and Universities Key Laboratory of New Technology and Application in Resource Chemical Engineering, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China;
2 Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Nanning 530004, Guangxi, China

Received:2016-05-09 Revised:2016-08-23 Online:2016-11-05 Published:2016-11-05
Supported by:
supported by the Science and Technology Research Fund of Guangxi Education Department (2013YB024), the Natural Science Foundation of Guangxi Province(2013GXNSFBA019037), the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2015Z010)and the Guangxi Outstanding Doctoral Dissertation Cultivating Project (YCBZ2012006).

摘要/Abstract

摘要：

将β-环糊精（β-CD）添加到聚醚共聚乙酰胺（PEBA）中制备β-环糊精/聚醚共聚乙酰胺填充膜（β-CD-f-PEBA），用于苯酚-水的渗透汽化分离研究。SEM、FTIR表明β-环糊精在膜中分散均匀且与膜结合紧密，与膜间只有氢键相互作用而未发生化学交联。拉伸实验表明膜的拉伸强度和断裂强度均随着β-CD添加量的增加先减小后增大。采用基团贡献法计算了PEBA、苯酚及水的溶解度参数，证明PEBA膜对苯酚具有较高的选择吸附性。通过溶胀验证膜对苯酚的选择吸附性能，膜对苯酚的吸附量度随着料液中苯酚浓度和膜中β-CD添加量的增加而增加。考察了PEBA和β-CD-f-PEBA膜的渗透汽化性能，当β-CD填充量为0.5%（质量）时，分离效果最佳，渗透通量和分离因子分别为3062.9 g·m^-2·h^-1和43.3。通过Arrhenius方程计算苯酚和水的渗透活化能分别为97.19和52.12 kJ·mol^-1。重复实验表明β-CD-f-PEBA膜的操作稳定性良好。

关键词: β-环糊精, 渗透蒸发, 聚醚共聚乙酰胺, 苯酚, 填充膜

Abstract:

β-cyclodextrin (β-CD) filled poly(ether block amide) (PEBA) membranes (β-CD-f-PEBA) were prepared by solution casting method to recover phenol from dilute solution by pervaporation (PV). The physicochemical structure of the membrane was studied by SEM and FTIR. The results showed that the β-CD were dispersed uniformly within the polymer phase and a good adherence was obtained between the β-CD and PEBA just by physical crosslinking. The mechanical properties of the membrane were tested by tensile test. Effect of the phenol concentration and β-CD concentration on the swelling behavior were studied in terms of degree of swelling (DS). The swelling experiments indicated that DS increased significantly both with the phenol concentration in feed solutions and the β-CD concentration in PEBA basic membranes. The solubility parameters of PEBA, phenol and water were calculated by the group-contribution method. The solubility parameter difference between PEBA and phenol was smaller than that between PEBA and water, which meant the PEBA owned high phenol selectivity than water. The adsorption and diffusion separation factor of the β-CD-f-PEBA membrane was used to conform the controlling step of the PV process. The PV performance of β-CD-f-PEBA membrane were investigated at different operating conditions. With the increase of β-CD content, the β-CD-f-PEBA membranes displayed significant improvement in the permeation flux and the separation factor. The β-CD-f-PEBA membrane containing 0.5% (mass) β-CD showed the best separation results with a total flux and separation factor of 3062.9 g·m^-2·h^-1 and 43.3, respectively. With increasing temperature, both the total flux and separation factor increased. The activity energies of phenol and water flux were calculated according to Arrhenius equation with values of 97.19 kJ·mol^-1 and 52.12 kJ·mol^-1, respectively. The result of repeated experiments showed good long term stability of β-CD-f-PEBA films.

Key words: β-cyclodextrin, pervaporation, poly (ether block amide), phenol, filled membrane

中图分类号:

张时雨, 邹昀, 韦藤幼, 牟春霞, 刘香君, 童张法. β-环糊精/聚醚共聚乙酰胺填充膜的制备及渗透汽化分离水中微量苯酚[J]. 化工学报, 2016, 67(11): 4662-4670.

ZHANG Shiyu, ZOU Yun, WEI Tengyou, MU Chunxia, LIU Xiangjun, TONG Zhangfa. Preparation of β-cyclodextrin filled PEBA membranes and pervaporation separation of phenol from dilute solution[J]. CIESC Journal, 2016, 67(11): 4662-4670.

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β-环糊精/聚醚共聚乙酰胺填充膜的制备及渗透汽化分离水中微量苯酚

Preparation of β-cyclodextrin filled PEBA membranes and pervaporation separation of phenol from dilute solution

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