基于COSMO-RS方法筛选离子液体分离乙酸乙酯-乙腈共沸物

doi:10.11949/j.issn.0438-1157.20180911

摘要/Abstract

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。

关键词: 乙酸乙酯, 乙腈, 离子液体, COSMO-RS模型, 选择性

Abstract:

The application of different ionic liquids in the separation of acetate-acetonitrile azeotrope was investigated by COSMO-RS method. The accuracy of COSMO-thermX prediction of ionic liquid separation was verified by comparison between predicted and experimental values. The selectivity (based on acetonitrile) of 221 ionic liquids composed of 17 cations and 13 anions and the effect of ionic liquids on the relative volatility of ethyl acetate to acetonitrile near azeotropic point were calculated and analyzed. It was found that the ionic liquids containing [OAc]^- and [Cl]^- had a better promoting effect on the separation of ethyl acetate - acetonitrile mixture, while the difference in the promoting effect of cations on the separation of ethyl acetate - acetonitrile mixture was small. The effect of anions [OAc]^- and [Cl]^- on azeotrope was further studied by applying the surface charge density distribution (σ-profile), revealing that the order of influence of the anions [OAc]^- and [Cl]^- on the separation of ethyl acetate-acetonitrile was [OAc]^->[Cl]^-. The comprehensive prediction results show that ionic liquid [BMIM][OAc] is expected to be used as a highly efficient extractant in the separation of ethyl acetate-acetonitrile mixture.

Key words: ethylacetate, acetonitrile, ionic liquid, COSMO-RS model, selectivity

中图分类号:

TQ 013.1

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/表 8

图1 101.3 kPa下乙酸乙酯（1）-乙腈（2）二元物系的汽液相平衡曲线

Fig.1 Vapor-liquid equilibrium diagram for binary system of ethyl acetate(1) + acetonitrile(2) at 101.3 kPa

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

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

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]

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3 不同离子液体对乙酸乙酯+乙腈物系的选择性预测

Fig.3 Selective prediction of ethyl acetate and acetonitrile systems by different ionic liquids

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5 乙酸乙酯、乙腈、[BMIM]+、[OAc]?和[Cl]?的σ-profile谱图

Fig.5 σ-profile of ethylacetate, acetonitrile, [BMIM]+, [OAc]? and [Cl]?

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

参考文献 31

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.

编辑推荐 0

Metrics

阅读次数

全文

276

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	13	0	0	263

来源	本网站	其他网站

次数	144	132
比例	52%	48%

摘要

637

最新录用	在线预览	正式出版

0	0	637

来源	本网站	其他网站

次数	412	225
比例	65%	35%

[1]	王琪, 张斌, 张晓昕, 武虎建, 战海涛, 王涛. 氯铝酸-三乙胺离子液体/P₂O₅催化合成伊索克酸和2-乙基蒽醌[J]. 化工学报, 2023, 74(S1): 245-249.
[2]	车睿敏, 郑文秋, 王小宇, 李鑫, 许凤. 基于离子液体的纤维素均相加工研究进展[J]. 化工学报, 2023, 74(9): 3615-3627.
[3]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[4]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[5]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[6]	王俐智, 杭钱程, 郑叶玲, 丁延, 陈家继, 叶青, 李进龙. 离子液体萃取剂萃取精馏分离丙酸甲酯+甲醇共沸物[J]. 化工学报, 2023, 74(9): 3731-3741.
[7]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[8]	陆俊凤, 孙怀宇, 王艳磊, 何宏艳. 离子液体界面极化及其调控氢键性质的分子机理[J]. 化工学报, 2023, 74(9): 3665-3680.
[9]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[10]	宋明昊, 赵霏, 刘淑晴, 李国选, 杨声, 雷志刚. 离子液体脱除模拟油中挥发酚的多尺度模拟与研究[J]. 化工学报, 2023, 74(9): 3654-3664.
[11]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[12]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[13]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[14]	张缘良, 栾昕奇, 苏伟格, 李畅浩, 赵钟兴, 周利琴, 陈健民, 黄艳, 赵祯霞. 离子液体复合萃取剂选择性萃取尼古丁的研究及DFT计算[J]. 化工学报, 2023, 74(7): 2947-2956.
[15]	毛磊, 刘冠章, 袁航, 张光亚. 可捕集CO₂的纳米碳酸酐酶粒子的高效制备及性能研究[J]. 化工学报, 2023, 74(6): 2589-2598.