Functionalized ionic liquids based on [EMIM][OAC] for vapor-liquid phase equilibrium of acetonitrile and water by COSMO-RS method

doi:10.11949/j.issn.0438-1157.20151535

Abstract

Abstract:

Based on 1-ethyl-3-methylimidazolium acetate ([EMIM][OAC]), ionic liquids composed by 15 cations and 21 anions were designed by modifying [OAC] and [EMIM] with different groups, including amine (-NH₂), hydroxy (-OH), nitrile (-CN), halogen (Br, F) and so on. The effect of the designed ionic liquids on the vapor-liquid phase equilibrium of acetonitrile and water mixtures was predicted by COSMOthermX based on COSMO-RS model. The influence of group type and IL structure on relative volatility of acetonitrile was also investigated. The results showed that the ILs carrying -NH₂ in cation or carrying -OH in anion can promote the separation of acetonitrile from water and the separation effect becomes more obvious with increasing number of-NH₂ group. The ionic liquids composed by 2 cations (1-(2-aminoethyl)-3-methylimidazolium, 2,2,2-triaminoethyl-3-methylimidazolium) and 3 anions (hydroxyacetic acid, 2-hydroxypropanoic acid, 2-hydro-3-aminopropanoic acid) had better performance in separation water from acetonitrile than [EMIM][OAC].

Key words: ionic liquid, COSMO-RS, acetonitrile, water, vapor-liquid equilibrium

摘要：

以1-乙基-3-甲基咪唑醋酸盐([EMIM][OAC])为基准,通过分别在阴阳离子上修饰胺基(-NH₂)、羟基(-OH)、腈基(-CN)、卤素(Br、F)等,虚拟设计了15 种阳离子和21 种阴离子组成的离子液体(IL)。采用基于COSMO-RS 模型的COSMOthermX 软件计算了所设计的离子液体对乙腈-水混合物恒压汽液相平衡的影响,探索了修饰基团的种类、离子液体结构对乙腈相对挥发度的影响规律。研究发现,在阳离子碳链上修饰-NH₂,阴离子(醋酸根和丙酸根)羰基的邻碳上进行单一的-OH 修饰能促进乙腈与水的分离,且阳离子修饰的-NH₂ 数越多,促进分离的效果越明显,其他嫁接方式未取得好的分离效果。虚拟设计的两种阳离子(1-胺乙基-3-甲基咪唑、2,2,2-三胺乙基-3-甲基咪唑)与3 种阴离子(羟基乙酸、2-羟基丙酸、2-羟基-3-胺基丙酸)组合的离子液体分离效果明显比[EMIM][OAC]好。

关键词: 离子液体, COSMO-RS, 乙腈, 水, 汽液相平衡

CLC Number:

TQ013.1

LI Tingting, YANG Qing, PENG Changjun, LIU Honglai. Functionalized ionic liquids based on [EMIM][OAC] for vapor-liquid phase equilibrium of acetonitrile and water by COSMO-RS method[J]. CIESC Journal, 2016, 67(2): 425-434.

李婷婷, 杨青, 彭昌军, 刘洪来. 基于COSMO-RS模型研究基团修饰[EMIM][OAC]的离子液体对乙腈-水汽液平衡的影响[J]. 化工学报, 2016, 67(2): 425-434.

References 25

[1]	穆光照. 实用溶剂手册[M]. 上海:上海科技出版社, 1990:346. MU G Z. Practical Manual of Solvent[M]. Shanghai:Shanghai Science & Technology Press, 1990:346.
[2]	李忠杰. 高纯乙腈精制工艺技术开发与应用[J]. 石油化工, 2001, 30:785-788. LI Z J. Development and application of high-purity acetonitrile purification and refining processes[J]. Petrochemical Technology, 2001, 30:785-788.
[3]	KAI Z, JON W, PAUL Y, et al. Multiresidue pesticide analysis of agricultural commodities using acetonitrile salt-out extraction, dispersive solid-phase sample clean-up, and high-performance liquid chromatography-tandem mass spectrometry[J]. J. Agric. Food Chem., 2011, 59(14):7636-7646. DOI:10.1021/jf2010723.
[4]	崔现宝, 李杨, 冯天扬, 等. 加盐萃取精馏分离乙腈-水物系[J]. 石油化工, 2007, 36(12):1229-1233. CUI X B, LI Y, FENG T Y, et al. Separation of acetonitrile-water by saline extractive distillation[J]. Petrochemical Technology, 2007, 36(12):1229-1233.
[5]	ACOSTA J, ARCE A, RODIL E, et al. A thermodynamic study on binary and ternary mixtures of acetonitrile, water and butyl acetate[J]. Fluid Phase Equilibria, 2002, 203:83-98. DOI:PII S0378-3812(02) 00171-1.
[6]	张锁江, 刘晓敏, 姚晓倩, 等. 离子液体的前沿、进展及应用[J]. 中国科学(B辑:化学), 2009, 39(10):1134-1144. ZHANG S J, LIU X M, YAO X Q, et al. Forefront, development and application of ionic liquid[J]. Science in China, Series B:Chemistry, 2009, 39(10):1134-1144.
[7]	叶庆国, 韩平. 加盐萃取精馏技术进展[J]. 化学工业与工程, 2009, 30(2):44-47. YE Q G, HAN P. Technology progress of saline extractive distillation[J]. Journal of Chemical Industry and Engineering, 2009, 30(2):44-47.
[8]	周金波,崔现宝, 董炳利, 等. 间歇萃取精馏分离乙腈-水体系[J]. 化学工业与工程, 2009, 26(6):482-486. ZHOU J B, CUI X B, DONG B L, et al. Separation of acetonitrile-water mixture by batch extractive distillation[J]. Journal of Chemical Industry and Engineering, 2009, 26(6):482-486.
[9]	ZHANG Z G, LV M, HUANG D H, et al. Isobaric vapor-liquid equilibrium for the extractive distillation of acetonitrile+water mixtures using dimethyl sulfoxide at 101.3 kPa[J]. J. Chem. Eng. Data, 2013, 58:3364-3369. DOI:10.1021/je400531a.
[10]	李文秀, 张琦, 张亲亲, 等. 含离子液体乙腈-正丙醇体系的等压汽液平衡[J].化工学报, 2015, 66(S1):38-45. DOI:10.11949/j.issn. 0438-1157.20141907. LI W X, ZHANG Q, ZHANG Q Q, et al. Isobaric vapor-liquid equilibrium for system of acetonitrile-n-propanol system containing ionic liquids[J]. CIESC Journal, 2015, 66(S1):38-45. DOI:10.11949/j.issn.0438-1157.20141907.
[11]	DUPONT J, DE-SOUZA R F, SUAREZ P A Z. Ionic liquid (molten salt) phase organometallic catalysis[J]. Chemical Reviews, 2002, 102(10):3667-3692. DOI:10.1021/cr010338r.
[12]	JORK C, SEILER M, BESTE Y A, et al. Influence of ionic liquids on the phase behavior of aqueous azeotropic systems[J]. J. Chem. Eng. Data, 2004, 49:852-857. DOI:10.1021/je034183r.
[13]	KURZIN A V, EVDOKIMOV A N, POLTORATSKIY G M, et al. Isothermal vapor-liquid equilibrium data for the systems 1,4-dioxane + water + tetrabutylammonium nitrate and acetonitrile + water + tetrabutylammonium bromide[J]. J. Chem. Eng. Data, 2004, 49:208-211. DOI:10.1021/je0301287.
[14]	KURZIN A V, EVDOKIMOV A N, ANTIPINA V B, et al. Measurement and correlation of isothermal vapor-liquid equilibrium data for the system acetonitrile + water + tetrapropylammonium bromide[J]. J. Chem. Eng. Data, 2006, 51:1361-1363. DOI:10.1021/je0600855.
[15]	尹伟超, 崔现宝, 吴添, 等. 离子液体对乙腈-水体系汽液平衡的影响[J]. 化工进展, 2009, 28:190-193. YIN W C, CUI X B,WU T, et al. Effect of ionic liquid on the vapor-liquid equilibrium of acetonitrile-water[J]. Chemical Industry and Engineering Process, 2009, 28:190-193.
[16]	李春利, 李聚魁, 刘艳稳, 等. 离子液体对乙腈-水共沸物系汽液平衡的影响[J].化工进展, 2011, 30(12):2611-2614. LI C L, LI J K, LIU Y W, et al. Effect of ionic liquid on the vapor-liquid equilibrium of acetonitrile-water[J]. Chemical Industry and Engineering Process, 2011, 30(12):2611-2614.
[17]	FANG J, LIU J, LI C L, et al. Isobaric vapor-liquid equilibrium for the acetonitrile + water system containing different ionic liquids at atmospheric pressure[J]. J. Chem. Eng. Data, 2013, 58:1483-1489. DOI:10.1021/je3009792.
[18]	YANG Q, CHEN K X, HE C C, et al. Vapor pressure measurement and correlation of acetonitrile +1-butyl-3-methylimidazolium chloride, +1-butyl-3-methylimidazolium tetrafluoroborate, and +1-hexyl-3-methylimidazolium chloride[J]. Chin. J. Chem. Eng., 2015, 23:412-416. DOI:10.1016/j.cjche.2014.11.008.
[19]	KLAMT A. Conductor-like screening model for real solvents:a new approach to the quantitative calculation of solvation phenomena[J]. J. Phys. Chem., 1995, 99:2224-2235.
[20]	KLAMT A, JONAS V, BÜRGER T, et al. Refinement and parametrization of COSMO-RS[J]. J. Phys. Chem. A, 1998, 102(26):5074-5085.
[21]	KLAMT A, ECKERT F. COSMO-RS:a novel and efficient method for the apriori prediction of thermophysical data of liquids[J]. Fluid Phase Equilibria, 2000, 172(1):43-72. DOI:10.1016/S0378-3812(00)00357-5.
[22]	ECKERT F, KLAMT A. Fast solvent screening via quantum chemistry:COSMO-RS approach[J]. AIChE Journal, 2002, 48(2):369-385. DOI:10.1002/aic.690480220.
[23]	LI J L, YANG X Q, CHEN K X, et al. Sifting ionic liquid as additives for separations of acetonitrile and water azeotropic mixture using COSMO-RS method[J]. Ind. Eng. Chem. Res., 2012, 51:9376-9385. DOI:10.1021/ie3000985.
[24]	杨青. 促进乙腈水溶液分离的离子液体设计与实验研究[D]. 上海:华东理工大学, 2014. YANG Q. Design and experimental study of ionic liquid used in separation of acetonitrile and water[D]. Shanghai:East China University of Science and Technology, 2014.
[25]	VENKATASUBRAMANIAN V, RENGASWAMY R, KAVURI S N, et al. A review of process fault detection and diagnosis (Ⅲ):Process history based methods[J]. Comp. Chem. Eng., 2003, 27:327-346. DOI:PII S0098-1354(02) 00162-X.