膜科学与技术

位置：首页 >> 期刊内容阅读

反相气相色谱法测定PTFEP中有机硫的无限稀释活度系数和扩散系数

作者：张伟¹，杨正金²，王乃鑫¹，纪树兰¹，李继定²

单位： 1. 北京工业大学环境与能源工程学院，北京 100124；2. 清华大学化学工程系，北京 100084

关键词：渗透汽化；无限稀释活度系数；无限稀释扩散系数；反相气相色谱；聚三氟乙氧基磷腈

DOI号：

分类号： O642.2; O643

出版年,卷(期):页码： 2015,35(5):18-23

摘要：

反相气相色谱法可以快速、准确测定高分子与溶剂间的相互作用。本文利用反相气相色谱法测定了353.15 K-373.15 K温度范围内正庚烷、噻吩、2-甲基噻吩、2,5-二甲基噻吩、乙硫醚等溶剂在聚三氟乙氧基磷腈（PTFEP）中的无限稀释活度系数和无限稀释扩散系数。计算了PTFEP对有机硫/正庚烷体系的无限稀释选择性，利用Arrhenius方程确定了上述溶剂在PTFEP中的扩散活化能和扩散常数。实验结果表明：在测定温度范围内，升高温度有利于小分子在PTFEP中的溶解和扩散。小分子在聚合物内的扩散，受分子尺寸和小分子、聚合物间相互作用的共同影响。本研究取得的参数将为渗透汽化传质模型的建立提供必要的理论基础。

Inverse gas chromatography (IGC) is a fast and reliable technique to measure the solvent-polymer interplay. In this study, the infinite dilute activity coefficients and infinite dilute diffusion coefficients of n-heptane, thiophene, 2-methylthiophene, 2, 5-dimethylphene and ethyl sulfide in poly[bis(trifluoroethoxy)phosphazene] (PTFEP) were determined in the temperature ranging from 353.15 K to 373.15 K with an increment of 5 K. The infinite dilute selectivity were measured from the experimental data, the pre-exponential factor and activation energy were also obtained according to Arrhenius equation. The experiment results showed that higher temperatures would accelerate the diffusion rate and also increase the sorption on membrane surface. And the diffusion through the membranes was affected by sizes of solvent molecules and the interactions between solvents and polymer. The obtained data would be assistance to the study of transferring mechanism in PTFEP membranes.

基金项目：

作者简介：

参考文献：

[1]Debarati M. Desulfurization of gasoline by pervaporation[J].Sep Purif Rev, 2012, 41: 97-125.
[2]刘荣坤，孔瑛，卢福伟，等. FCC汽油的膜分离法脱硫[J]. 石油学报（石油加工）, 2009, 25(4): 472-476.
[3]Li P, Zhao L L, Wei P Z, et al. Mass transfer of hydroxyethyl cellulose membranes for desulfurization of FCC gasoline: experimental and modeling[J].Chem Eng J, 2013, 231: 255-161.
[4]牟明仁，赵雪蓉，张代华，等. 解读车用汽油新标准的修订[J]. 中国标准化，2014, 453: 84-87.
[5]李继定，展侠，葛洪，等.渗透汽化和汽体渗透膜技术应用及其浮浅思考[J].膜科学与技术, 2011, 31(3): 135-139.
[6]赵长伟，李继定，赵之平，等. PDMS有机硅膜的制备及其渗透汽化脱硫的研究[J]. 膜科学与技术, 2006, 26(5): 72-75.
[7]Shi Y Q, Wang X W, Chen G W. Pervaporation characteristics and solution-diffusion behaviors through sodium alginate dense membrane[J].J Appl Polym Sci, 1996, 61: 1387-1394.
[8]Zeng C Y, Huang M, Zhao H, et al. Solution and diffusion properties of cyclohexane, cyclohexanol, and cyclohexanone in poly(ethylene glycol) by inverse gas chromatography[J].J Appl Polym Sci, 2012, 123: 124-134.
[9]Zhang S J, Akio T, Hiroaki N, et al. Activity coefficients and diffusivities of solvents in polymers[J]. Fluid Phase Equilibr, 2002, 194-197: 1179-1189.
[10]李辉，逯翠梅，谢凤，等. 反相气相色谱研究金属离子中介甲醛印迹聚合物的气相识别[J]. 分析化学, 2014, 42(6): 885-890.
[11]Zhang Q G, Fan B C, Liu Q L, et al. A novel poly(dimethyl siloxane)/poly(oligosilsesquioxanes) composite membrane for pervaporation desulfurization[J].J Membr Sci, 2011, 366: 335-341.
[12]Chen J, Li J D, Qi R B, et al. Pervaporation performance of crosslinked polydimethylsiloxane membranes for deep desulfurization of FCC gasoline I. Effect of different sulfur species[J]. J Membr Sci, 2008, 322: 113-121.
[13]张新孟，王秀峰，江红涛，等. 聚磷腈功能高分子材料的合成及应用研究进展[J]. 化工新型材料, 2010, 38(11): 27-30.
[14]Yang Z J, Zhang W Y, Li J D, et al. Polyphosphazene membrane for desulfurization: Selecting poly[bis(trifluoroethoxy)phosphazene] for pervaporative removal of thiophene[J].Sep Purif Technol, 2012, 93: 15-24.
[15]Wang D, Li J D, Zeng C Y, et al. Measurement of the infinite dilute activity coefficients and diffusion coefficients of water and straight chain alcohols in cross-linked polyvinyl alcohol by inverse gas chromatography[J].J Chem Eng Data, 2007, 52: 368-372.
[16]Van Deemter J J, Zuiderweg F J, Klinkenberg. Longitudinal diffusion and resistance to mass transfer as causes of nonideality in chromatography[J].Chem Eng Sci, 1956, 5: 271-289.
[17]Zhang Q G, Liu Q L, Lin J, et al. Analyzing solubility and diffusion of solvents in novel hybrid materials of poly(vinyl alcohol)/γ-aminopropyltriethoxysilane by inverse gas chromatography[J].J Mater Chem, 2007, 17: 4889-4895.

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com