化工学报 ›› 2019, Vol. 70 ›› Issue (1): 146-153.DOI: 10.11949/j.issn.0438-1157.20180911
收稿日期:
2018-08-13
修回日期:
2018-10-15
出版日期:
2019-01-05
发布日期:
2019-01-05
通讯作者:
张亲亲
作者简介:
张志刚(1968—),男,博士,教授,<email>zhzhgang@126.com</email>|张亲亲(1988—),女,博士,讲师,<email>zhangshoudao@126.com</email>
基金资助:
Zhigang ZHANG(),Debiao ZHANG,Qinqin ZHANG(
),Tao ZHANG,Ru YANG,Wenxiu LI
Received:
2018-08-13
Revised:
2018-10-15
Online:
2019-01-05
Published:
2019-01-05
Contact:
Qinqin ZHANG
摘要:
采用COSMO-RS方法探究了不同离子液体在分离乙酸乙酯-乙腈共沸物系中的应用;通过预测值与实验值的对比,验证了COSMO-thermX预测离子液体分离效果的准确性。离子液体的选择性和不同离子液体对乙酸乙酯-乙腈近沸点处相对挥发度的影响为指标,计算和分析了17种阳离子和13种阴离子组成的221种离子液体对乙酸乙酯-乙腈共沸物系的分离效果的影响规律。结果表明,含有[OAc]-和[Cl]-的离子液体对于乙酸乙酯-乙腈混合物的分离具有更好的促进效果,而阳离子的变化对于乙酸乙酯-乙腈混合物分离的促进效果差异较小。应用表面电荷密度分布(σ-profile)进一步研究了阴离子[OAc]-和[Cl]-对共沸物的影响,研究发现,阴离子[OAc]-和[Cl]-对乙酸乙酯-乙腈的分离效果影响顺序为[OAc]->[Cl]-;综合筛选结果,得出离子液体[BMIM][OAc]有望在乙酸乙酯-乙腈共沸混合物分离过程中成为一种高效的萃取剂。
中图分类号:
张志刚, 张德彪, 张亲亲, 张弢, 杨茹, 李文秀. 基于COSMO-RS方法筛选离子液体分离乙酸乙酯-乙腈共沸物[J]. 化工学报, 2019, 70(1): 146-153.
Zhigang ZHANG, Debiao ZHANG, Qinqin ZHANG, Tao ZHANG, Ru YANG, Wenxiu LI. Screening of ionic liquids for separation of ethyl acetate-acetonitrile azeotrope based on COSMO-RS[J]. CIESC Journal, 2019, 70(1): 146-153.
图2 101.3kPa下乙酸乙酯(1)-乙腈(2)-离子液体(3)三元汽液相平衡曲线
Fig.2 Vapor-liquid equilibrium data of ethyl acetate (1)-acetonitrile (2)-ionic liquids (3) ternary system at 101.3 kPa
阳离子 | 简称 | 阴离子 | 简称 |
---|---|---|---|
1,3-methyl-imidazolium 1-ethyl-3-methyl-imidazolium 1-butyl-3-methyl-imidazolium 1-hexyl-3-methyl-imidazolium 1-octyl-3-methyl-imidazolium 1-ethyl-2-3-methyl-imidazolium 1-butyl-2-3-methyl-imidazolium 1-hexyl-2-3-methyl-imidazolium tetra-methylammonium tetra-ethylammonium tetrabutyl-phosphonium triisobutyl-methyl-phosphonium ethyl-pyridinium 1-ethyl-pyridinium 1-butyl-pyridinium 1-ethyl-3-methylpyridinium 1-butyl-3-methyl-pyridinium | [MMIM] [EMIM] [BMIM] [HMIM] [OMIM] [EMMIM] [BMMIM] [HMMIM] [N1111] [N2222] [P4444] [P4441] [MPY] [EPY] [BPY] [EMPY] [BMPY] | Cl Br I NO3 BF4 dimethylphosphate diethylphosphate dibutylphosphate PF6 methylsulfate ethylsulfate bis[(trifluoromethyl)sulfonyl]imide acetate | [Cl] [Br] [I] [NO3] [BF4] [DMP] [DEP] [DBP] [PF6] [MeSO4] [EtSO4] [Tf2N] [OAc] |
表1 离子液体阴阳离子的名称及缩写
Table 1 Names and abbreviations of anions and cations in ionic liquids
阳离子 | 简称 | 阴离子 | 简称 |
---|---|---|---|
1,3-methyl-imidazolium 1-ethyl-3-methyl-imidazolium 1-butyl-3-methyl-imidazolium 1-hexyl-3-methyl-imidazolium 1-octyl-3-methyl-imidazolium 1-ethyl-2-3-methyl-imidazolium 1-butyl-2-3-methyl-imidazolium 1-hexyl-2-3-methyl-imidazolium tetra-methylammonium tetra-ethylammonium tetrabutyl-phosphonium triisobutyl-methyl-phosphonium ethyl-pyridinium 1-ethyl-pyridinium 1-butyl-pyridinium 1-ethyl-3-methylpyridinium 1-butyl-3-methyl-pyridinium | [MMIM] [EMIM] [BMIM] [HMIM] [OMIM] [EMMIM] [BMMIM] [HMMIM] [N1111] [N2222] [P4444] [P4441] [MPY] [EPY] [BPY] [EMPY] [BMPY] | Cl Br I NO3 BF4 dimethylphosphate diethylphosphate dibutylphosphate PF6 methylsulfate ethylsulfate bis[(trifluoromethyl)sulfonyl]imide acetate | [Cl] [Br] [I] [NO3] [BF4] [DMP] [DEP] [DBP] [PF6] [MeSO4] [EtSO4] [Tf2N] [OAc] |
图4 101.3 kPa下乙酸乙酯(1)+乙腈(2)+阴离子为[OAc]?、[Cl]?、[Tf2N]?离子液体的相对挥发度
Fig.4 Relative volatility of ethyl acetate (1) + acetonitrile (2) + anions are [OAc]?, [Cl]?, [Tf2N]? ionic liquid at 101.3 kPa
图6 101.3 kPa下乙酸乙酯(1)+乙腈(2)+[BMIM][OAc](3)三元汽液相平衡预测图
Fig.6 Isobaric VLE diagram for ternary system of ethyl acetate (1) + acetonitrile (2)+ [BMIM][OAC] (3) at 101.3 kPa
图7 不同离子液体(3)对乙酸乙酯(1)-乙腈(2)汽液相平衡影响的对比
Fig.7 Comparison of effects of different ionic liquids(3) on isobaric vapor-liquid equilibrium of ethyl acetate(1)-acetonitrile(2) system at x3≈0.15 mol
1 | 王晓红, 田光珍, 谢力, 等. 萃取精馏分离乙酸乙酯-乙腈共沸物系的优化与控制研究[J]. 青岛科技大学学报(自然科学版),2017, 38(4): 71-77. |
WangX H, TianG Z, XieL, et al. Design and control of extractive distillation for separating ethyl acetate-acetonitrile azeotropic systems [J]. Journal of Qingdao University of Science and Technology (Natural Science Edition), 2017, 38(4): 71-77. | |
2 | 丁邦琴, 张双, 李卓, 等. 乙酸乙酯-乙腈-1-乙基-3-甲基咪唑三氟甲磺酸盐物系等压气液平衡数据的测定[J]. 石油化工, 2014, 43(12): 1405-1409. |
DingB Q, ZhangS, LiZ, et al. Isobaric vapor-liquid equilibrium for ethyl acetate-acetonitrile-1-ethyl-3-methylimidazolium trifluoromethanesulfonate ternary system [J]. Petrochemical Technology, 2014, 43(12): 1405-1409. | |
3 | 迪建东. 间歇共沸精馏分离乙腈和乙酸乙酯混合物的研究[D]. 天津: 天津大学, 2006. |
DiJ D. Study on separation of acetonitrile and ethylacetate mixture by batch zeotropic distillation [D]. Tianjin: Tianjin University, 2006. | |
4 | 马文婵, 孙建杰, 魏洪普, 等. 萃取法分离乙腈、乙酸乙酯和水混合物的研究[J]. 应用化工, 2010, 39(6): 781-782. |
MaW C, SunJ J, WeiH P, et al. Study on separation of acetonitrile and ethylacetate mixture by extractive distillation [J]. Applied Chemical Industry, 2010, 39(6): 781-782. | |
5 | 丁邦琴, 张双, 许文, 等. 乙酸乙酯-乙腈-1-丁基-3-甲基咪唑三氟甲磺酸盐物系等压气液平衡数据的测定及关联[J]. 北京化工大学学报(自然科学版), 2014, 41(6): 42-46. |
DingB Q, ZhangS, XuW, et al. Isobaric vapor-liquid equilibrium for ethyl acetate-acetonitrile-1-butyl-3-methylimidazolium trifluoromethanesulfonate ternary system [J]. Journal of Beijing University of Chemical Technology (Natural Science), 2014, 41(6): 42-46. | |
6 | FangJ, ZhaoR, SuW Y, et al. A molecular design method based on the COSMO-SAC model for solvent selection in ionic liquid extractive distillation [J]. AIChE Journal, 2016, 62(8): 2853-2869. |
7 | ZhangL Z, HanJ, DengD, et al. Selection of ionic liquids as entrainers for separation of water and 2-propanol [J]. Fluid Phase Equilibria, 2007, 255(2): 179-185. |
8 | SeilerM, JorkC, KavarnouA, et al. Separation of azeotropic mixtures using hyperbranched polymers or ionic liquids [J]. AIChE Journal, 2004, 50(10): 2439-2454. |
9 | CalvarN, GonzálezB, GómezE, et al. Study of the behaviour of the azeotropic mixture ethanol-water with imidazolium-based ionic liquids [J]. Fluid Phase Equilibria, 2007, 259(1): 51-56. |
10 | SimoniL D, FickeL E, LambertC A, et al. Measurement and prediction of vapor-liquid equilibrium of aqueous 1-ethyl-3-methylimidazolium-based ionic liquid systems [J]. Industrial and Engineering Chemistry Research, 2010, 49(8): 3893-3901. |
11 | ZhangY, YuD, GuoF, et al. Vapor-liquid equilibria measurement of (methanol + ethanenitrile + bis(trifluoromethylsulfonyl) imide)-based ionic liquids at 101. 3 kPa [J]. Journal of Chemical and Engineering Data, 2016, 61(7): 2202-2208. |
12 | 李瑞, 崔现宝, 吴添, 等. 基于COSMO-SAC模型的离子液体萃取剂的选择[J]. 化工学报, 2013, 64(2): 452-469. |
LiR, CuiX B, WuT, et al. Selection of ionic liquid solvent for liquid-liquid extraction based on COSMO-SAC model [J]. CIESC Journal, 2013, 64(2): 452-469. | |
13 | 曹玲, 李群生. 乙酸乙酯-乙腈-1-辛基-3-甲基咪唑六氟磷酸盐物系等压气液相平衡数据的测定与关联[J]. 石油化工, 2016, 45(2): 194-199. |
CaoL, LiQ S. Isobaric vapor-liquid equilibrium for ethyl acetate-acetonitrile-1-octyl-3- methylimidazolium hexafluorophosphate system [J]. Petrochemical Technology, 2016, 45(2): 194-199. | |
14 | LiQ S, CaoL. Isobaric vapor-liquid equilibrium for ethyl acetate + acetonitrile + 1-butyl-3-methylimidazolium hexafluorophos-phate at 101. 3 kPa [J].Chem J.Eng.Data, 2013, 58(5): 1112-1116. |
15 | ZhuJ J, LiQ S, LiM, et al. The isobaric vapor liquid equilibria of ethyl acetate + acetonitrile + bis (trifluoromethylsulfonyl) imide-based ionic liquids at 101. 3kPa [J]. Fluid Phase Equilibria, 2016, 425: 289-296. |
16 | KlamtA, JonasV, BurgerT. Refinement and parametrization of COSMO-RS [J]. Journal of Physical Chemistry A, 1998, 102(26): 5074-5085. |
17 | KlamtA. Conductor-like screening model for real solvents: a new approach to the quantitative calculation of solvation phenomena [J]. Journal of Physical Chemistry, 1995, 99(7): 2224-2235. |
18 | BanerjeeT, SinghM K, KhannaA. Prediction of binary VLE for imidazolium based ionic liquid systems using COSMO-RS [J]. Industrial & Engineering Chemistry Research, 2006, 45(9): 3207-3219. |
19 | KlamtA. The COSMO and COSMO-RS solvation models [J]. Wiley Interdisciplinary Reviews Computational Molecular Science, 2011, 1(10): 699-709. |
20 | 顾丽莉, 代文阳, 郭小涛. COSMO-RS筛选桉叶油萃取精馏的离子液体[J]. 化学工程, 2016, 44(3): 15-21. |
GuL L, DaiW Y, GuoX T. COSMO-RS based ionic-liquid selection for extractive distillation of eucalyptus oil [J]. Chemical Engineering (China), 2016, 44(3): 15-21. | |
21 | ZhangZ G, ZhangL, ZhangQ, et al. Separation of 2-propanol and water azeotropic system using ionic liquids as entrainers [J]. Fluid Phase Equilibria, 2016, 412: 94-100. |
22 | LeiZ G, DaiC, ZhuJ, et al. Extractive distillation with ionic liquids: a review [J]. AIChE Journal, 2014, 60(9): 3312-3329. |
23 | LiJ L, YangX Q, ChenK X, et al. Sifting ionic liquids as additives for separation of acetonitrile and water azeotropic mixture using the COSMO-RS method [J]. Industrial and Engineering Chemistry Research, 2012, 51(27): 9376-9385. |
24 | LiT T, YangQ, DingH R, et al. Amino acid based ionic liquids as additives for the separation of an acetonitrile and water azeotropic mixture: COSMO-RS prediction and experimental verification [J]. Industrial and Engineering Chemistry Research, 2015, 54: 12143-12149. |
25 | DhanalakshmiJ, SaiP S T, BalakrishnanA R. Study of ionic liquids as entrainers for the separation of methyl acetate-methanol and ethyl acetate-ethanol systems using the COSMO-RS model [J]. Industrial and Engineering Chemistry Research, 2013, 52 (46): 16396-16405. |
26 | 李骏, 何文军, 漆志文, 等. 基于COSMO-RS的分离甲醇-碳酸二甲酯的离子液体溶剂筛选[J]. 石油化工, 2016, 45(12): 1499-1505. |
LiJ, HeW J, QiZ W, et al. Screening ionic liquids for separation of methanol and dimethyl-carbonate mixtures based on COSMO-RS method [J]. Petrochemical Technology, 2016, 45(12): 1499-1505. | |
27 | FreireM G, SantosL M, MarruchoI M, et al. Evaluation of COSMO-RS for the prediction of LLE and VLE of alcohols+ionic liquids [J]. Fluid Phase Equilibria, 2007, 255(2): 167-178. |
28 | ZhengZ Q, WuT H, ZhouX P. The synthesis of quaternary ammonium salts from ammonium salts and dialkyl carbonate [J]. Chemical Communications, 2006, 17(17): 1864-1865. |
29 | 杨小倩, 何昌春, 陈科侠, 等. 基于COSMO-RS方法筛选易于乙腈-水分离的离子液体[J]. 化工进展, 2011, 30(s2): 55-61. |
YangX Q, HeC C, ChenK X, et al. Screening ionic liquids for separation of acetonitrile and water mixtures based on COSMO-RS method [J]. Chemical Industry and Engineering Progress, 2011, 30(s2): 55-61. | |
30 | ZhangZ G, WuK F, ZhangQ Q, et al. Separation of ethyl acetate and ethanol azeotrope mixture using dialkylphosphates-based ionic liquids as entrainers [J]. Fluid Phase Equilibria, 2017, 454: 91-98. |
31 | 李婷婷, 杨青, 彭昌军, 等. 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): 426-434. |
LiT T, YangQ, PengC J, et al. 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): 426-434. |
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