疏水SiO2填充PDMS膜分离水中乙酸正丁酯的性能

doi:10.11949/j.issn.0438-1157.20161508

化工学报 ›› 2017, Vol. 68 ›› Issue (6): 2407-2414.DOI: 10.11949/j.issn.0438-1157.20161508

疏水SiO₂填充PDMS膜分离水中乙酸正丁酯的性能

牟春霞, 张时雨, 邹昀, 刘香君, 董颜箔, 崔学民, 童张法

广西大学化学化工学院, 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:2016-10-26 修回日期:2017-02-26 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 邹昀,童张法
基金资助:
广西自然科学基金项目（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项目（2015Z010）；广西自然科学基金创新团队项目（2016GXNSFGA380003）

Separation of n-butyl acetate from aqueous solution using PDMS membrane filled with hydrophobic SiO₂

MU Chunxia, ZHANG Shiyu, ZOU Yun, LIU Xiangjun, DONG Yanbo, CUI Xuemin, TONG Zhangfa

Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China

Received:2016-10-26 Revised:2017-02-26 Online:2017-06-05 Published:2017-06-05
Contact: 10.11949/j.issn.0438-1157.20161508
Supported by:
supported by the Natural Science Foundation of Guangxi (2014GXNSFAA118061), the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2015Z010) and the Innovation Team Project of Guangxi Natural Science Foundation (2016GXNSFGA380003)

摘要/Abstract

摘要：

以聚偏氟乙烯（PVDF）为支撑层，选用疏水性纳米SiO₂粉体作为改性剂，制备出聚二甲基硅氧烷（PDMS）复合膜材料，并用于乙酸正丁酯/水溶液的渗透汽化分离。采用SEM、FTIR、XRD、拉伸实验、接触角及正电子湮没寿命谱测定等对膜材料物理化学性能进行了表征，考察了膜材料的溶胀行为及渗透汽化性能。结果表明，SiO₂在PDMS膜中分散均匀，且没有发生化学作用，并提高了膜材料的机械强度和疏水性。随着SiO₂添加量增加，膜在乙酸正丁酯溶液中的溶胀度先升后降，渗透通量呈下降趋势，而分离因子先增大后减小。当SiO₂添加量为4%（质量）时，随进料浓度的增加，渗透通量增大，分离因子先增大后减小；随着温度升高，渗透通量增大，分离因子减小；渗透通量和分离因子最大值分别为240 g·m^-2·h^-1和542。

关键词: 聚二甲基硅氧烷, 疏水SiO₂, 渗透蒸发, 乙酸正丁酯

Abstract:

The modified polydimethysiloxane (PDMS) hybrid membranes with hydrophobic nano SiO₂ as filler and using PVDF film as support layer were prepared for pervaporation of n-butyl acetate from aqueous solution. The physciochemical properties of membranes were characterized by SEM, FTIR, XRD, tensile testing, contact angle and positron annihilation lifetime spectroscopy(PALS). The effects of the loading of SiO₂, feed concentration, feed temperature on swelling behavior and pervaporation performance were studied. The results indicated that SiO₂ particles dispersed uniformly in the membrane material and no chemical change occurred between SiO₂ and PDMS polymer chain. The mechanical strength and hydrophobic properties of the filled film were obviously improved by incorporation of SiO₂. With the increase of SiO₂ content, the adsorption capacity of n-butyl acetate increased and then decreased, while the permeation flux decreased and the separation factor increased initially and then decreased. When SiO₂ content was 4%(mass), the permeation flux increased while the separation factor increased initially and then decreased with the rise of the feed concentration. The permeation flux increased with increase of the feed temperature, however, the separation factor decreased. The maximum values of the permeation flux and the separation factor were 240 g·m^-2·h^-1 and 542 respectively.

Key words: polydimethylsiloxane, hydrophobic SiO₂, pervaporation, n-butyl acetate

中图分类号:

TQ028.8

牟春霞, 张时雨, 邹昀, 刘香君, 董颜箔, 崔学民, 童张法. 疏水SiO₂填充PDMS膜分离水中乙酸正丁酯的性能[J]. 化工学报, 2017, 68(6): 2407-2414.

MU Chunxia, ZHANG Shiyu, ZOU Yun, LIU Xiangjun, DONG Yanbo, CUI Xuemin, TONG Zhangfa. Separation of n-butyl acetate from aqueous solution using PDMS membrane filled with hydrophobic SiO₂[J]. CIESC Journal, 2017, 68(6): 2407-2414.

参考文献 30

[1]	STEINIGEWEG S, GMEHLING J. n-Butyl acetate synthesis via reactive distillation: thermodynamic aspects, reaction kinetics, pilot-plant experiments, and simulation studies[J]. Industrial & Engineering Chemistry Research, 2002, 41(22): 5483-5490.
[2]	韦藤幼, 童张法. 连续催化反应精馏生产醋酸丁酯新工艺[J]. 化工设计, 2003, 13(3): 14-16.
	WEI T Y, TONG Z F. Butyl acetate production new process by continuous catalytic reaction and distillation[J]. Chemical Engineering Design, 2003, 13(3): 14-16．
[3]	邹昀, 童张法, 刘琨, 等. 间歇反应器内醋酸丁酯酯化反应与渗透汽化集成过程的模型计算[J]. 催化学报, 2010, 31(8): 999-1005.
	ZOU Y, TONG Z F, LIU K, et al. Modeling of esterification in a batch reactor coupled with pervaporation for production of n-butyl acetate[J]. Chinese Journal of Catalysis, 2010, 31(8): 999-1005.
[4]	方静, 王宝东, 李春利, 等. 隔板塔共沸精馏分离二氯甲烷-乙腈-水-硅醚体系[J]. 化工学报, 2013, 64(3): 963-969.
	FANG J, WANG B D, LI C L, et al. Separation of dichloromethane-acetonitrile-water-hexamethyl disiloxane with dividing wall column by azeotropic distillation[J]. CIESC Journal, 2013, 64(3): 963-969.
[5]	LI S Y, SRIVASTAVA R, PARNAS R S. Separation of 1-butanol by pervaporation using a novel tri-layer PDMS composite membrane[J]. Journal of Membrane Science, 2010, 363(1): 287-294.
[6]	刘琨, 杨超, 陈松, 等. 聚醚共聚酰胺(PEBA)膜的溶胀和渗透汽化行为研究[J]. 高校化学工程学报, 2010, 24(1): 16-21.
	LIU K, YANG C, CHEN S, et al. Swelling and pervaporation behavior of poly(ether block amide) membrane[J]. Journal of Chemical Engineering of Chinese Universities, 2010, 24(1): 16-21.
[7]	张时雨, 邹昀, 韦藤幼, 等. 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 S Y, ZOU Y, WEI T Y, et al. Preparation of β-cyclodextrinfilled PEBA membranes and the pervaporation separation of phenol from dilute solution[J]. CIESC Journal, 2016, 67(11): 4662-4670.
[8]	ZHUANG X J, CHEN X R, SU Y, et al. Surface modification of silicalite-1 with alkoxysilanes to improve the performance of PDMS/silicalite-1 pervaporation membranes: preparation, characterization and modeling[J]. Journal of Membrane Science, 2016, 499: 386-395.
[9]	DUBEY V, SAXENA C, SINGH L, et al. Pervaporation of binary water-ethanol mixtures through bacterial cellulose membrane[J]. Separation and Purification Technology, 2002, 27(2): 163-171.
[10]	LIU K, TONG Z F, LIU L, et al. Separation of organic compounds from water by pervaporation in the production of n-butyl acetate via esterification by reactive distillation[J]. Journal of Membrane Science, 2005, 256(1/2): 193-201.
[11]	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 n-butyl acetate from aqueous solution by CMS-filled polyether block amide membrane[J]. Membrane Science and Technology, 2010, 30(2): 45-51.
[12]	MURTHY Z V P, MODI A D. Effect of ionic liquid in Sn-ZSM-5 zeolite membrane in the separation of butyl acetate-water mixtures by pervaporation[J]. Synthesis and Reactivity in Inorganic Metal-Organic and Nano-Metal Chemistry, 2013, 43(6): 657-661.
[13]	SUN D, LI B B, XU Z L. Pervaporation of ethanol/water mixture by organophilic nano-silica filled PDMS composite membranes[J]. Desalination, 2013, 322(8): 159-166.
[14]	WANG X L, CHEN J X, FANG M Q, et al. ZIF-7/PDMS mixed matrix membranes for pervaporation recovery of butanol from aqueous solution[J]. Separation and Purification Technology, 2016, 163: 39-47.
[15]	DONG Z Y, LIU G P, LIU S N, et al. High performance ceramic hollow fiber supported PDMS composite pervaporation membrane for bio-butanol recovery[J]. Journal of Membrane Science, 2014, 450(2): 38-47.
[16]	ZHOU H L, SU Y, CHEN X R, et al. Separation of acetone, butanol and ethanol (ABE) from dilute aqueous solutions by silicalite-1/PDMS hybrid pervaporation membranes[J]. Separation and Purification Technology, 2011, 79(3): 375-384.
[17]	NAIK P V, KERKHOFS S, MARTENS J A, et al. PDMS mixed matrix membranes containing hollow silicalite sphere for ethanol/water separation by pervaporation[J]. Journal of Membrane Science, 2016, 502: 48-56.
[18]	李磊, 谭淑娟, 蒋冬华, 等. 支撑层对硅橡胶复合膜渗透汽化分离性能的影响[J]. 化工学报, 2006, 57(1): 61-65.
	LI L, TAN S J, JIANG D H, et al. Influence of support layer of composite PDMS membrane on performance of hydrophobic pervaporation[J]. Journal of Chemical Industry and Engineering(China), 2006, 57(1): 61-65.
[19]	LI B, XU D, JIANG Z Y, et al. Pervaporation performance of PDMS-Ni2+Y zeolite hybrid membranes in the desulfurization of gasoline[J]. Journal of Membrane Science, 2008, 322(2): 293-301.
[20]	韩小龙, 张杏梅, 马晓迅, 等. 碳纳米管填充PDMS膜的渗透汽化性能[J]. 化工学报, 2014, 65(1): 271-278.
	HAN X L, ZHANG X M, MA X X, et al. Pervaporation performance of carbon nanotube filled PDMS membrane[J]. CIESC Journal, 2014, 65(1): 271-278.
[21]	徐国强, 余江, 王康, 等. 蒙脱石-聚二甲基硅氧烷复合膜制备及其乙醇/水分离性能[J]. 化工学报, 2007, 58(2): 391-395.
	XU G Q, YU J, WANG K, et al. Preparation of montmorillonite filled PDMS hybrid membrane and its pervaporation on ethanol over water[J]. Journal of Chemical Industry and Engineering(China), 2007, 58(2): 391-395.
[22]	FURUKAWA H, CORDOVA K E, O'KEEFFE M, et al. The chemistry and applications of metal-organic frameworks[J]. Science, 2013, 341(6149): 1230444.
[23]	杨占照, 刘艳梅, 顾学红, 等. 管式支撑体内表面NaA分子筛膜的合成与表征[J]. 化工学报, 2011, 62(3): 840-845.
	YANG Z Z, LIU Y M, GU X H, et al. Synthesis and characterization of NaA zeolite membranes on inner side of tubular supports[J]. CIESC Journal, 2011, 62(3): 840-845.
[24]	WANG N X, LIU J D, LI J, et al. Tuning properties of silicalite-1 for enhanced ethanol/water pervaporation separation in its PDMS hybrid membrane[J]. Microporous and Mesoporous Materials, 2015, 201: 35-42.
[25]	DING C, ZHANG X R, LI C C, et al. ZIF-8 incorporated polyether block amide membrane for phenol permselective pervaporation with high efficiency[J]. Separation and Purification Technology, 2016, 166: 252-261.
[26]	PANEK D, KONIECZNY K. Pervaporation of toluene and toluene/acetone/ethyl acetate aqueous mixtures through dense composite polydimethylsiloxane membranes[J]. Desalination, 2006, 200(1/2/3): 367-373.
[27]	ZIRAKI S, ZEBARJAD S M, HADIANFARD M J. A study on the tensile properties of silicone rubber/polypropylene fibers/silica hybrid nano composites[J]. Journal of the Mechanical Behavior of Biomedical Materials, 2016, 57: 289-296.
[28]	杨磊, 许湧深, 邱守季, 等. 微滴乳液聚合制备PDMS/SiO2纳米复合材料[J]. 化工学报, 2013, 64(4): 1473-1477.
	YANG L, XU Y S, QIU S J, et al. Preparation of PDMS/SiO2 nanocomposites via miniemulsion polymerization[J]. CIESC Journal, 2013, 64(4): 1473-1477.
[29]	CAMENZIND A, SCHWEIZER T, SZTUCHI M, et al. Structure & strength of silica-PDMS nano composites[J]. Polymer, 2010, 51(8): 1796-1804.
[30]	ZHANG K, LIVELY R P, ZHANG C, et al. Investigating the intrinsic ethanol/water separation capability of ZIF-8: an adsorption and diffusion study[J]. The Journal of Physical Chemistry C, 2013, 117(14): 7214-7225.

疏水SiO₂填充PDMS膜分离水中乙酸正丁酯的性能

Separation of n-butyl acetate from aqueous solution using PDMS membrane filled with hydrophobic SiO₂

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