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

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