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

doi:10.11949/j.issn.0438-1157.20160624

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

Previous Articles Next Articles

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).

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

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）。

Abstract

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

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

CLC Number:

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.

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.

References 25

[1]	董晓蕾, 李莉, 陈晴川, 等. β-环糊精聚合物的合成及其对苯酚的选择性吸附研究[J]. 化工新型材料, 2012, 40(10):86-89. DONG X L, LI L, CHEN Q C, et al. Synthesis of β-cyclodextrin polymer and selective adsorption for phenol[J]. New Chemical Materials, 2012, 40(10):86-89.
[2]	方志平, 姜忠义. 聚环糊精填充PDMS渗透蒸发膜分离苯酚水溶液[J]. 化工学报, 2006, 57(4):843-848. FANG Z P, JIANG Z Y. Pervaporation separation of phenol aqueous solution using cyclodextrin polymer-filled PDMS membranes[J]. Journal of Chemical Industry and Engineering(China), 2006, 57(4):843-848.
[3]	王韬, 李鑫钢, 杜启云. 含酚废水治理技术研究进展[J]. 化工进展, 2008, 27(2):231-235. WANG T, LI X G, DU Q Y. Research progress of phenol-containing waste water disposal technique[J]. Chemical Industry and Engineering Progress, 2008, 27(2):231-235.
[4]	AHMARUZZAMAN M. Adsorption of phenolic compounds on low-cost adsorbents:a review[J]. Advances in Colloid and Interface Science, 2008, 143(1/2):48-67.
[5]	KUJAWSKI W, WARSZAWSKI A, RATAJCZAK W O, et al. Removal of phenol from wastewater by different separation techniques[J]. Desalination, 2004, 163(1/2/3):287-296.
[6]	FENG X, HUANG R Y M. Liquid separation by membrane pervaporation:a review[J]. Industrial & Engineering Chemistry Research, 1997, 36(4):1048-1066.
[7]	LI C, ZHANG X, HAO X, et al. Thermodynamic and mechanistic studies on recovering phenol crystals from dilute aqueous solutions using pervaporation-crystallization coupling (PVCC) system[J]. Chemical Engineering Science, 2015, 127:106-114.
[8]	WANG Y, GRUENDER M, XU S. Polybenzimidazole (PBI) membranes for phenol dehydration via pervaporation[J]. Industrial & Engineering Chemistry Research, 2014, 53(47):18291-18303.
[9]	ZHANG X, LI C, HAO X, et al. Recovering phenol as high purity crystals from dilute aqueous solutions by pervaporation[J]. Chemical Engineering Science, 2014, 108(17):183-187.
[10]	LIU K, TONG Z F, LIU L, et al. Separation of organic compounds from water by pervaporation in the production of -butyl acetate via esterification by reactive distillation[J]. Journal of Membrane Science, 2005, 256(1/2):193-201.
[11]	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.
[12]	GU J, SHI X, BAI Y, et al. Silicalite-filled PEBA membranes for recovering ethanol from aqueous solution by pervaporation[J]. Chemical Engineering & Technology, 2009, 32(1):155-160.
[13]	TAN H, WU Y, LI T. Pervaporation of n-butanol aqueous solution through ZSM-5-PEBA composite membranes[J]. Journal of Applied Polymer Science, 2013, 129(1):105-112.
[14]	刘琨, 陈松. 碳分子筛填充聚醚共聚乙酰胺膜渗透汽化分离水溶液中的醋酸正丁酯[J]. 膜科学与技术, 2010, 30(2):45-51. LIU K, CHEN S. Pervaporation separation of nbutyl acetate from aqueous solution by CMS-filled polyether block amide membrane[J]. Membrane Science and Technology, 2010, 30(2):45-51.
[15]	YEN H W, CHEN Z H, YANG I K. Use of the composite membrane of poly(ether-block-amide) and carbon nanotubes (CNTs) in a pervaporation system incorporated with fermentation for butanol production by Clostridium acetobutylicum[J]. Bioresource Technology, 2012, 109(4):105-109.
[16]	陈晴川, 王杰, 李莉, 等. 纳米球形环糊精刷的制备及其对苯酚的吸附性能[J].华东理工大学学报(自然科学版), 2012, 38(6):657-659. CHEN Q C, WANG J, LI L, et al. Synthesis of nano-sized spherical β-cyclodextrin brushes and their application in phenol removal[J]. Journal of East China University of Science and Technology(Natural Science Edition), 2012, 38(6):657-659.
[17]	SEVILLANO X, ISASI J R, PEÑAS F J. Feasibility study of degradation of phenol in a fluidized bed bioreactor with a cyclodextrin polymer as biofilm carrier[J]. Biodegradation, 2008, 19(4):589-597.
[18]	YAMASAKI H, MAKIHATA Y, FUKUNAGA K. Efficient phenol removal of wastewater from phenolic resin plants using crosslinked cyclodextrin particles[J]. Journal of Chemical Technology & Biotechnology, 2006, 81(7):1271-1276.
[19]	WILSON L D, MOHAMED M H, BERHAUT C L. Sorption of aromatic compounds with copolymer sorbent materials containing β-cyclodextrin[J]. Materials, 2011, 4(12):1528-1542.
[20]	KREVELEN D W V, NIJENHUIS K T. Properties of Polymers[M]. 4th ed. Elsevier, 2009:1707, 1719.
[21]	王敏敏, 张新儒, 李馨然, 等. PEBA/MCM-41杂化膜的制备及其对苯酚/水渗透汽化分离性能的研究[J]. 膜科学与技术, 2015, 35(6):40-47. WANG M M, ZHANG X R, LI X R, et al. Preparation of hybrid PEBA/MCM-41 membrane and its pervaporation performance for separating phenol water mixture[J]. Membrane Science and Technology, 2015, 35(6):40-47.
[22]	LIU K, FANG C J, LI Z, et al. Separation of thiophene/n-heptane mixtures using PEBAX/PVDF-composited membranes via pervaporation[J]. Journal of Membrane Science, 2014, 451(2):24-31.
[23]	BUCKINGHAM A D, DEL BENE J E, MCDOWELL S A C. The hydrogen bond[J]. Chemical Physics Letters, 2008, 463(1/2/3):1-10.
[24]	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.
[25]	张春芳, 董亮亮, 白云翔, 等. ZIF-8填充聚硅氧烷膜的制备及渗透汽化分离水中正丁醇[J]. 膜科学与技术, 2013, 33(4):88-93. ZHANG C F, DONG L L, BAI Y X, et al. ZIF-8 filled polydimethylsiloxane membranes for pervaporative separation n-butanol from aqueous solution[J]. Membrane Science and Technology, 2013, 33(4):88-93.

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

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

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 25

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Minghao SONG, Fei ZHAO, Shuqing LIU, Guoxuan LI, Sheng YANG, Zhigang LEI. Multi-scale simulation and study of volatile phenols removal from simulated oil by ionic liquids [J]. CIESC Journal, 2023, 74(9): 3654-3664.
[2]	Jiayi ZHANG, Jiali HE, Jiangpeng XIE, Jian WANG, Yu ZHAO, Dongqiang ZHANG. Research progress of pervaporation technology for N-methylpyrrolidone recovery in lithium battery production [J]. CIESC Journal, 2023, 74(8): 3203-3215.
[3]	Wenjie XU, Xianfeng JIA, Jitong WANG, Wenming QIAO, Licheng LING, Renping WANG, Zijian YU, Yinxu ZHANG. Preparation and properties of silicone/phenolic hybrid aerogel [J]. CIESC Journal, 2023, 74(8): 3572-3583.
[4]	Chuanbao XIAO, Linyang LI, Wufeng LIU, Nianbing ZHONG, Quanhua XIE, Dengjie ZHONG, Haixing CHANG. Effective removal of 2,4,6-trichlorophenol by coupling photocatalysis with ion exchange adsorption [J]. CIESC Journal, 2023, 74(4): 1587-1597.
[5]	Xinlong YAN, Zhigang HUANG, Qingxun HU, Xin ZHANG, Xiaoyan HU. Catalytic nitrophenol degradation via peroxymonosulfate activation over Cu/Co doped porous carbon [J]. CIESC Journal, 2023, 74(3): 1102-1112.
[6]	Na ZHANG, Helin PAN, Bo NIU, Yayun ZHANG, Donghui LONG. Density functional theory study on thermal cracking reaction mechanism of phenolic resin [J]. CIESC Journal, 2023, 74(2): 843-860.
[7]	Xin LIU, Yang PAN, Gongping LIU, Jing FANG, Chunli LI, Hao LI. Study on the process of preliminary separation of Fischer-Tropsch synthetic water by coupling pervaporation and dividing wall column distillation [J]. CIESC Journal, 2022, 73(5): 2020-2030.
[8]	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.
[9]	Jian WANG, Zixuan LEI, Jiayu YAO, Jian LI, Yuhong LIU. Synthesis and curing kinetics of terephthalaldehyde phenolic resin [J]. CIESC Journal, 2022, 73(3): 1403-1415.
[10]	Yunfei WU, Xiaoli LUAN, Fei LIU. Near-infrared spectroscopy online detecting for 2,6-dimethylphenol purity based on transfer learning [J]. CIESC Journal, 2022, 73(2): 782-791.
[11]	Li XU, Qianqiu WU, Zixuan LEI, Jiaxuan LI, Yuhong LIU. Crosslinking structure and mechanical properties of thermoplastic phenolic resin modified with siloxane prepolymer [J]. CIESC Journal, 2022, 73(10): 4734-4744.
[12]	Hongyun YOU, Jingjun LIN, Kaiyue HUANG, Riyang SHU, Zhipeng TIAN, Chao WANG, Ying CHEN. Mechanism of solvent effect on hydrogenation of lignin-derived phenolic compounds [J]. CIESC Journal, 2022, 73(10): 4498-4506.
[13]	Wanyue DING, Xiaohua MA. Effects of synthesis times and Si-Al ratio of SAPO-34 zeolite membrane on ethanol dehydration performance [J]. CIESC Journal, 2021, 72(8): 4410-4417.
[14]	FANG Lijun, WANG Jingmei, LIN Qiaojing, CHEN Jianhua, YANG Qian. Enrichment of phenol in water by dibenzo-18-crown ether-6/polyether block amide membrane [J]. CIESC Journal, 2021, 72(7): 3716-3727.
[15]	HUANG Wenyuan, SUN Shijie, TANG Hongzhen, SU Zhifang, ZHONG Qindi, LIU Youyan, LI Qingyun. Phenol removal by the Alcaligenes sp. DN25 immobilized on the polyurethane foams [J]. CIESC Journal, 2021, 72(5): 2783-2791.