Determination and calculation of isobaric vapor equilibrium for acetonitrile + water + ionic liquid

doi:10.11949/0438-1157.20190123

Abstract

Abstract:

Acetonitrile is easy to form an azeotropic mixture with water and it is impossible to separate them through ordinary distillation technology. In this work, ionic liquids (ILs) are employed as entrainer to separate acetonitrile and water. The isobaric vapor liquid equilibria (VLE) of acetonitrile + water + 1-ethyl-3-methylimidazolium diethylphosphate ([EMIM][DEP]), acetonitrile + water + {1-ethyl-3-methylimidazolium acetate ([EMIM][OAC]) + [EMIM][DEP]} are determined at atmospheric pressure (101.3 kPa) in a glass equilibrium still with a vapor cycle, indicating that the selected ILs can well improve the separation of acetonitrile and water mixture, and further eliminate its azeotropy. The VLE data of ternary and quaternary mixtures containing ILs are well correlated with NRTL model, and the binary interaction parameters of acetonitrile-[EMIM][DEP], water-[EMIM][DEP] and [EMIM][OAC]-[EMIM][DEP] are obtained. The experimental VLE was predicted using COSMO-SAC and the results were satisfactory. The interactions among different molecules are analyzed through quantum calculations showing that the interactions between water and ILs are stronger than ones between water and acetonitrile so that the used ILs here can improve the separation of acetonitrile and water.

Key words: thermodynamic properties, vapor liquid equilibria, ionic liquids, acetonitrile, COSMO

摘要：

采用改进的Ellis平衡蒸馏仪测定了乙腈+水+1-乙基-3-甲基咪唑磷酸二乙酯盐([EMIM][DEP])、乙腈+水+{1-乙基-3-甲基咪唑醋酸盐([EMIM][OAC])+[EMIM][DEP]}常压(101.3 kPa)等压汽液平衡(VLE)数据。实验结果表明，备选离子液体可促进水+乙腈混合物的分离并消除其共沸点。借助NRTL模型成功关联了含离子液体的三元和四元VLE实验数据，获得了乙腈-[EMIM][DEP]、水-[EMIM][DEP]和[EMIM][OAC]-[EMIM][DEP]二元交互作用参数。应用COSMO-SAC预测了实验VLE，结果令人满意。量化计算表明可与水形成强相互作用的离子液体更易促进乙腈与水的分离。

关键词: 热力学性质, 汽液平衡, 离子液体, 乙腈, COSMO

CLC Number:

Jinlong LI, Jiashu LI, Qing YANG, Changjun PENG, Honglai LIU. Determination and calculation of isobaric vapor equilibrium for acetonitrile + water + ionic liquid[J]. CIESC Journal, 2019, 70(6): 2110-2116.

李进龙, 李佳书, 杨青, 彭昌军, 刘洪来. 乙腈+水+离子液体等压汽液平衡测定与计算[J]. 化工学报, 2019, 70(6): 2110-2116.

Figures/Tables 11

References 36

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x ₃	T ^exp / K	x ₁'	y ₁	T ^cal / K	y ^cal ₁
0.05	367.34	0.0411	0.2247	369.44	0.2178
	360.35	0.0656	0.4110	364.08	0.3764
	355.08	0.1212	0.5615	356.95	0.5496
	352.33	0.1653	0.6242	354.05	0.6123
	350.26	0.2489	0.6650	351.36	0.6731
	350.13	0.4063	0.7102	350.06	0.7262
	350.23	0.4772	0.7277	350.11	0.7436
	350.10	0.5507	0.7475	350.38	0.7618
	350.82	0.6028	0.7774	350.68	0.7759
	351.07	0.6788	0.8044	351.27	0.7994
	351.72	0.7627	0.8453	352.13	0.8316
	352.38	0.8750	0.9207	353.73	0.8912
	354.02	0.9509	0.9619	355.26	0.9498
0.10	368.97	0.0688	0.2624	371.79	0.3066
	361.90	0.0972	0.4758	366.51	0.4525
	358.50	0.1392	0.5778	361.23	0.5762
	355.44	0.1861	0.6334	357.62	0.6527
	354.57	0.2293	0.6757	355.51	0.6971
	353.28	0.2811	0.7112	353.91	0.7337
	352.34	0.4098	0.7822	352.31	0.7908
	352.38	0.4907	0.8257	352.28	0.8165
	352.04	0.6075	0.8714	352.98	0.8499
	353.59	0.7434	0.9202	354.61	0.8908
	355.20	0.8629	0.9584	356.63	0.9338

x ₃	T ^exp / K	x ₁'	y ₁	T ^cal / K	y ^cal ₁
0.05	367.34	0.0411	0.2247	369.44	0.2178
	360.35	0.0656	0.4110	364.08	0.3764
	355.08	0.1212	0.5615	356.95	0.5496
	352.33	0.1653	0.6242	354.05	0.6123
	350.26	0.2489	0.6650	351.36	0.6731
	350.13	0.4063	0.7102	350.06	0.7262
	350.23	0.4772	0.7277	350.11	0.7436
	350.10	0.5507	0.7475	350.38	0.7618
	350.82	0.6028	0.7774	350.68	0.7759
	351.07	0.6788	0.8044	351.27	0.7994
	351.72	0.7627	0.8453	352.13	0.8316
	352.38	0.8750	0.9207	353.73	0.8912
	354.02	0.9509	0.9619	355.26	0.9498
0.10	368.97	0.0688	0.2624	371.79	0.3066
	361.90	0.0972	0.4758	366.51	0.4525
	358.50	0.1392	0.5778	361.23	0.5762
	355.44	0.1861	0.6334	357.62	0.6527
	354.57	0.2293	0.6757	355.51	0.6971
	353.28	0.2811	0.7112	353.91	0.7337
	352.34	0.4098	0.7822	352.31	0.7908
	352.38	0.4907	0.8257	352.28	0.8165
	352.04	0.6075	0.8714	352.98	0.8499
	353.59	0.7434	0.9202	354.61	0.8908
	355.20	0.8629	0.9584	356.63	0.9338

x ₃	T ^exp / K	x ₁'	y ₁	T ^cal / K	y ^cal ₁
0.05	369.44	0.0097	0.2244	370.15	0.1783
	363.08	0.0343	0.3822	363.22	0.3837
	356.20	0.0705	0.5409	358.05	0.5133
	350.66	0.1288	0.6457	353.69	0.6113
	350.13	0.1975	0.6635	351.16	0.6683
	349.71	0.2671	0.6828	349.94	0.7016
	349.75	0.3576	0.7036	349.37	0.7302
	349.79	0.4456	0.7214	349.38	0.7523
	350.30	0.5188	0.7427	349.65	0.7701
	350.51	0.6000	0.7804	350.14	0.7915
	350.51	0.6671	0.7809	350.70	0.8116
	351.05	0.7223	0.8078	351.25	0.8308
	351.70	0.7810	0.8446	351.94	0.8544
	352.29	0.8315	0.8759	352.65	0.8787
	353.34	0.8942	0.9269	353.69	0.9149
	354.04	0.9303	0.9571	354.39	0.9398
0.10	370.86	0.0128	0.2920	372.20	0.2630
	366.54	0.0369	0.4089	364.25	0.4741
	359.12	0.0719	0.5444	358.72	0.5968
	354.24	0.1315	0.6394	354.27	0.6880
	353.48	0.2226	0.7001	351.31	0.7540
	353.45	0.3668	0.7673	349.99	0.8091
	353.40	0.4340	0.7927	350.05	0.8277
	353.26	0.5986	0.8552	351.18	0.8688
	353.36	0.6800	0.8843	352.12	0.8896
	353.05	0.7627	0.9058	353.29	0.9126
	353.90	0.8265	0.9399	354.32	0.9322
	354.01	0.8846	0.9544	355.38	0.9521

x ₃	T ^exp / K	x ₁'	y ₁	T ^cal / K	y ^cal ₁
0.05	369.44	0.0097	0.2244	370.15	0.1783
	363.08	0.0343	0.3822	363.22	0.3837
	356.20	0.0705	0.5409	358.05	0.5133
	350.66	0.1288	0.6457	353.69	0.6113
	350.13	0.1975	0.6635	351.16	0.6683
	349.71	0.2671	0.6828	349.94	0.7016
	349.75	0.3576	0.7036	349.37	0.7302
	349.79	0.4456	0.7214	349.38	0.7523
	350.30	0.5188	0.7427	349.65	0.7701
	350.51	0.6000	0.7804	350.14	0.7915
	350.51	0.6671	0.7809	350.70	0.8116
	351.05	0.7223	0.8078	351.25	0.8308
	351.70	0.7810	0.8446	351.94	0.8544
	352.29	0.8315	0.8759	352.65	0.8787
	353.34	0.8942	0.9269	353.69	0.9149
	354.04	0.9303	0.9571	354.39	0.9398
0.10	370.86	0.0128	0.2920	372.20	0.2630
	366.54	0.0369	0.4089	364.25	0.4741
	359.12	0.0719	0.5444	358.72	0.5968
	354.24	0.1315	0.6394	354.27	0.6880
	353.48	0.2226	0.7001	351.31	0.7540
	353.45	0.3668	0.7673	349.99	0.8091
	353.40	0.4340	0.7927	350.05	0.8277
	353.26	0.5986	0.8552	351.18	0.8688
	353.36	0.6800	0.8843	352.12	0.8896
	353.05	0.7627	0.9058	353.29	0.9126
	353.90	0.8265	0.9399	354.32	0.9322
	354.01	0.8846	0.9544	355.38	0.9521

component i	component j	(g _ij -g _jj )/ (J·mol^-1)	(g _ji -g _ii )/ (J·mol^-1)	α_ij
acetonitrile	water	2214.21	5202.99	0.3545
acetonitrile	[EMIM][OAC]	11936.91	-4743.74	0.3
water	[EMIM][OAC]	24633.47	-13615.84	0.3
acetonitrile	[EMIM][DEP]	-16256.15	-3321.27	0.9
water	[EMIM][DEP]	-8388.62	-18920.54	0.1
[EMIM][OAC]	[EMIM][DEP]	-25040.97	44917.49	0.6750