离子液体萃取精馏分离甲醇-乙腈共沸物

doi:10.16085/j.issn.1000-6613.2024-0197

摘要/Abstract

摘要：

为实现甲醇-乙腈共沸体系的高效分离，本文选取N-辛基吡啶六氟磷酸盐（[Opy][PF₆]）为萃取剂，在101.325kPa下对甲醇-乙腈-[Opy][PF₆]三元物系进行等压气液相平衡的测定，获得了三元体系等压气液相平衡（VLE）数据，探究离子液体对甲醇-乙腈气液相平衡的影响，将实验数据与非随机双液（NRTL）模型相关联，得到二元相互作用参数。通过过量焓、高斯分析解释分离机理，结果表明[Opy][PF₆]的加入可提高甲醇相对于乙腈的相对挥发度，[Opy][PF₆]的含量增加使盐析效果更明显，NRTL模型与实验结果具有良好的一致性，通过Aspen Plus软件中的NRTL模型关联这些数据，发现当[Opy][PF₆]的物质的量分数为0.0345时，体系不再共沸，使用Aspen Plus软件模拟萃取精馏流程并优化工艺参数，得到萃取精馏过程的最佳操作条件。模拟结果可作为下一步萃取精馏实验和流程设计的指导。

关键词: 甲醇, 乙腈, 萃取精馏, 离子液体, Aspen Plus

Abstract:

In order to effectively separate the methanol-acetonitrile azeotrope system, N-octylpyridinium hexafluorophosphate imide salt ([Opy][PF₆]) was selected as entraining agent, and the isobaric vapor-liquid equilibrium of methanol-acetonitrile-[Opy][PF₆] ternary system was determined. The isobaric vapor-liquid equilibrium (VLE) data of ternary system were obtained, and the influence of ionic liquid on the vapor-liquid equilibrium of methanol-acetonitrile was investigated. The experimental data were correlated with the non-random two-liquid (NRTL) models and the binary interaction parameters were obtained. The separation mechanism was explained by intermolecular interaction energy and excess enthalpy analysis. And the results showed that the addition of [Opy][PF₆] could increase the relative volatility of methanol relative to acetonitrile and make the salting-out effect more pronounced. The NRTL model was in good agreement with the experimental results, and these data were correlated by NRTL model in Aspen Plus software. It was found that when the molar fraction of [Opy][PF₆] was 0.0345, the system was no longer azeotropic. Aspen Plus software was used to simulate the extractive distillation process and optimize the process parameters, and the best operating conditions of the extractive distillation process were obtained. The simulation results could be used as guidance for further extractive distillation experiment and process design.

Key words: methanol, acetonitrile, extractive distillation, ionic liquids, Aspen Plus

中图分类号:

TQ028.3

韩英娜, 李丽, 张林子, 安金泽, 李文秀, 张弢. 离子液体萃取精馏分离甲醇-乙腈共沸物[J]. 化工进展, 2025, 44(2): 660-668.

HAN Yingna, LI Li, ZHANG Linzi, AN Jinze, LI Wenxiu, ZHANG Tao. Separation of methanol-acetonitrile azeotrope by ionic liquid extractive distillation[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 660-668.

图/表 16

参考文献 18

1	WANG Yinglong, BU Guangle, GENG Xueli, et al. Design optimization and operating pressure effects in the separation of acetonitrile/methanol/water mixture by ternary extractive distillation[J]. Journal of Cleaner Production, 2019, 218: 212-224.
2	ZHU Jiujuan, FAN Hanhan, SUN Bing, et al. Effect and mechanism of 1-hexyl-3-methylimidazolium-based ionic liquids on the isobaric vapor-liquid equilibria of methanol+ acetonitrile at 101.3 kPa[J]. Journal of Chemical & Engineering Data, 2020, 65(11): 5405-5412.
3	赵建军, 刘沐鑫, 丁伯胜, 等. 乙腈与甲醇反应选择性合成丙烯腈催化剂制备及性能研究[J]. 塑料工业, 2018, 46(5): 147-150, 137.
	ZHAO Jianjun, LIU Muxin, DING Bosheng, et al. Study on preparation and properties of the catalyst for the synthesis of acrylonitrile from acetonitrile and methanol[J]. China Plastics Industry, 2018, 46(5): 147-150, 137.
4	ZHANG Yuxin, YU Dan, GUO Fan, et al. Vapor-Liquid Equilibria Measurement of (Methanol + Ethanenitrile + Bis(trifluoromethylsulfonyl) Imide)-Based Ionic Liquids at 101.3 kPa[J]. Journal of Chemical & Engineering Data, 2016, 61(7): 2202-2208.
5	LI Yanrui, WANG Qiang, LI Xiaoping, et al. Thermodynamic properties of N-octyl pyridinium hexafluorophosphate ionic liquid: Characterization and application in separation of the azeotrope[J]. Journal of Molecular Liquids, 2022, 350: 118434.
6	孙小情, 党明岩. 萃取精馏分离丙酮-正庚烷的模拟与优化[J]. 沈阳理工大学学报, 2023, 42(3): 68-74.
	SUN Xiaoqing, DANG Mingyan. Simulation and optimization of extractive distillation for separation of acetone and N-heptane[J]. Journal of Shenyang Ligong University, 2023, 42(3): 68-74.
7	王丽达. 以离子液体为萃取剂萃取精馏分离四氢呋喃-甲醇共沸体系的研究[D]. 沈阳: 沈阳化工大学, 2022.
	WANG Lida. Extractive distillation of tetrahydrofuran-methanol azeotropic system using ionic liquid as entrainer [D]. Shenyang: Shenyang University of Chemical Technology, 2022.
8	KLAMT Andreas, ECKERT Frank. Prediction of vapor liquid equilibria using COSMOtherm[J]. Fluid Phase Equilibria, 2004, 217(1): 53-57.
9	BOUDREAUX Andrew, CAMPBELL Craig. Student understanding of liquid-vapor phase equilibrium[J]. Journal of Chemical Education, 2012, 89(6): 707-714.
10	BESLER Brent H, MERZ Kenneth M Jr, KOLLMAN Peter A. Atomic charges derived from semiempirical methods[J]. Journal of Computational Chemistry, 1990, 11(4): 431-439.
11	RENON Henri, J-M PRAUSNITZ. Local compositions in thermodynamic excess functions for liquid mixtures[J]. AIChE Journal, 1968, 14(1): 135-144.
12	LI Qing, ZHU Wei, LIU Bing, et al. Measurement and correlation of the vapor-liquid equilibrium for methanol+acetonitrile+imidazolium-based ionic liquids at 101.3kPa[J]. The Journal of Chemical Thermodynamics, 2016, 101: 25-30.
13	LI Yumei, BAI Peng, ZHUANG Qionghong. Isobaric vapor-liquid equilibrium for binary system of methanol and acetonitrile[J]. Fluid Phase Equilibria, 2013, 340: 42-45.
14	VALDERRAMA José O, SANGA Wilson W, LAZZÚS Juan A. Critical properties, normal boiling temperature, and acentric factor of another 200 ionic liquids[J]. Industrial & Engineering Chemistry Research, 2008, 47(4): 1318-1330.
15	RUIZ Elia, FERRO Victor R, PALOMAR Jose, et al. Interactions of ionic liquids and acetone: Thermodynamic properties, quantum-chemical calculations, and NMR analysis[J]. The Journal of Physical Chemistry B, 2013, 117(24): 7388-7398.
16	Gonzalo GARCÍA-MIAJA, TRONCOSO Jacobo, Luis ROMANÍ. Excess properties for binary systems ionic liquid+ethanol: Experimental results and theoretical description using the ERAS model[J]. Fluid Phase Equilibria, 2008, 274(1/2): 59-67. DOI: https://doi.org/10.1016/j.fluid.2008.09.004 .
17	ORTEGA Juan, VREEKAMP Remko, MARRERO Elena, et al. Thermodynamic properties of 1-butyl-3-methylpyridinium tetrafluoroborate and its mixtures with water and alkanols[J]. Journal of Chemical & Engineering Data, 2007, 52(6): 2269-2276.
18	S-F BOYS, BERNARDI F. The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors[J]. Molecular Physics, 1970, 19(4): 553-566.

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T/K	x₁	y₁	γ₁	γ₂
338.00	0.972	0.964	0.980	2.229
337.90	0.946	0.934	0.979	2.136
337.60	0.910	0.898	0.991	1.994
337.30	0.860	0.855	1.010	1.846
337.20	0.761	0.784	1.050	1.620
337.50	0.695	0.744	1.079	1.483
338.00	0.588	0.687	1.154	1.322
339.70	0.413	0.592	1.325	1.140
341.10	0.312	0.524	1.471	1.082
342.90	0.230	0.456	1.621	1.039
345.40	0.146	0.355	1.807	1.022
348.10	0.088	0.257	1.954	1.009
351.00	0.045	0.156	2.067	0.998

T/K	x₁	y₁	γ₁	γ₂
338.00	0.972	0.964	0.980	2.229
337.90	0.946	0.934	0.979	2.136
337.60	0.910	0.898	0.991	1.994
337.30	0.860	0.855	1.010	1.846
337.20	0.761	0.784	1.050	1.620
337.50	0.695	0.744	1.079	1.483
338.00	0.588	0.687	1.154	1.322
339.70	0.413	0.592	1.325	1.140
341.10	0.312	0.524	1.471	1.082
342.90	0.230	0.456	1.621	1.039
345.40	0.146	0.355	1.807	1.022
348.10	0.088	0.257	1.954	1.009
351.00	0.045	0.156	2.067	0.998

T/K	x₃	x₁	x₁ʹ	y₁	α₁₂	γ₁	γ₂
338.35	0.200	0.759	0.948	0.981	2.392	1.264	0.805
338.35	0.200	0.737	0.921	0.970	2.426	1.293	0.809
338.15	0.200	0.710	0.887	0.958	2.468	1.330	0.809
338.05	0.200	0.668	0.835	0.937	2.533	1.382	0.830
338.15	0.200	0.626	0.783	0.916	2.599	1.441	0.841
338.45	0.200	0.555	0.693	0.876	2.713	1.544	0.875
338.75	0.200	0.477	0.596	0.826	2.836	1.666	0.919
339.75	0.200	0.393	0.492	0.763	3.011	1.804	0.961
340.95	0.200	0.311	0.388	0.685	3.156	1.951	1.014
342.85	0.200	0.213	0.266	0.562	3.366	2.146	1.092
345.85	0.200	0.135	0.168	0.423	3.536	2.291	1.152
349.65	0.200	0.078	0.098	0.287	3.661	2.343	1.167
352.75	0.200	0.036	0.045	0.152	3.761	2.377	1.187
353.65	0.200	0.020	0.024	0.085	3.809	2.420	1.223
338.35	0.050	0.873	0.919	0.936	1.283	1.044	1.436
338.35	0.050	0.842	0.886	0.912	1.326	1.055	1.404
338.35	0.049	0.801	0.842	0.882	1.399	1.073	1.353
338.35	0.048	0.748	0.786	0.845	1.489	1.101	1.305
338.45	0.050	0.681	0.717	0.808	1.653	1.150	1.228
338.85	0.050	0.599	0.631	0.759	1.847	1.211	1.160
339.45	0.051	0.511	0.538	0.706	2.059	1.290	1.111
340.55	0.050	0.420	0.442	0.646	2.301	1.375	1.065
342.15	0.051	0.318	0.335	0.571	2.645	1.511	1.026
344.45	0.049	0.230	0.242	0.488	2.986	1.635	0.993
347.55	0.050	0.147	0.155	0.378	3.322	1.766	0.977
350.85	0.050	0.084	0.089	0.257	3.556	1.856	0.972
353.95	0.049	0.041	0.043	0.147	3.809	1.944	0.963
355.55	0.050	0.023	0.024	0.089	3.940	1.992	0.960
337.55	0.021	0.911	0.931	0.930	0.996	1.026	1.812
337.35	0.021	0.882	0.901	0.905	1.056	1.040	1.731
337.25	0.020	0.844	0.862	0.875	1.129	1.055	1.642
337.25	0.023	0.796	0.815	0.843	1.223	1.077	1.547
337.35	0.020	0.740	0.755	0.806	1.345	1.104	1.442
337.65	0.023	0.674	0.690	0.766	1.475	1.139	1.358
338.15	0.022	0.579	0.593	0.714	1.713	1.210	1.245
339.05	0.020	0.476	0.485	0.649	1.963	1.294	1.167
340.15	0.022	0.378	0.386	0.588	2.269	1.414	1.109
342.15	0.021	0.245	0.251	0.481	2.769	1.649	1.069
344.65	0.022	0.174	0.178	0.403	3.132	1.777	1.030
348.35	0.021	0.100	0.102	0.279	3.423	1.869	1.007
351.45	0.022	0.055	0.057	0.183	3.741	1.971	0.984
353.15	0.021	0.030	0.031	0.108	3.842	2.022	0.990

T/K	x₃	x₁	x₁ʹ	y₁	α₁₂	γ₁	γ₂
338.35	0.200	0.759	0.948	0.981	2.392	1.264	0.805
338.35	0.200	0.737	0.921	0.970	2.426	1.293	0.809
338.15	0.200	0.710	0.887	0.958	2.468	1.330	0.809
338.05	0.200	0.668	0.835	0.937	2.533	1.382	0.830
338.15	0.200	0.626	0.783	0.916	2.599	1.441	0.841
338.45	0.200	0.555	0.693	0.876	2.713	1.544	0.875
338.75	0.200	0.477	0.596	0.826	2.836	1.666	0.919
339.75	0.200	0.393	0.492	0.763	3.011	1.804	0.961
340.95	0.200	0.311	0.388	0.685	3.156	1.951	1.014
342.85	0.200	0.213	0.266	0.562	3.366	2.146	1.092
345.85	0.200	0.135	0.168	0.423	3.536	2.291	1.152
349.65	0.200	0.078	0.098	0.287	3.661	2.343	1.167
352.75	0.200	0.036	0.045	0.152	3.761	2.377	1.187
353.65	0.200	0.020	0.024	0.085	3.809	2.420	1.223
338.35	0.050	0.873	0.919	0.936	1.283	1.044	1.436
338.35	0.050	0.842	0.886	0.912	1.326	1.055	1.404
338.35	0.049	0.801	0.842	0.882	1.399	1.073	1.353
338.35	0.048	0.748	0.786	0.845	1.489	1.101	1.305
338.45	0.050	0.681	0.717	0.808	1.653	1.150	1.228
338.85	0.050	0.599	0.631	0.759	1.847	1.211	1.160
339.45	0.051	0.511	0.538	0.706	2.059	1.290	1.111
340.55	0.050	0.420	0.442	0.646	2.301	1.375	1.065
342.15	0.051	0.318	0.335	0.571	2.645	1.511	1.026
344.45	0.049	0.230	0.242	0.488	2.986	1.635	0.993
347.55	0.050	0.147	0.155	0.378	3.322	1.766	0.977
350.85	0.050	0.084	0.089	0.257	3.556	1.856	0.972
353.95	0.049	0.041	0.043	0.147	3.809	1.944	0.963
355.55	0.050	0.023	0.024	0.089	3.940	1.992	0.960
337.55	0.021	0.911	0.931	0.930	0.996	1.026	1.812
337.35	0.021	0.882	0.901	0.905	1.056	1.040	1.731
337.25	0.020	0.844	0.862	0.875	1.129	1.055	1.642
337.25	0.023	0.796	0.815	0.843	1.223	1.077	1.547
337.35	0.020	0.740	0.755	0.806	1.345	1.104	1.442
337.65	0.023	0.674	0.690	0.766	1.475	1.139	1.358
338.15	0.022	0.579	0.593	0.714	1.713	1.210	1.245
339.05	0.020	0.476	0.485	0.649	1.963	1.294	1.167
340.15	0.022	0.378	0.386	0.588	2.269	1.414	1.109
342.15	0.021	0.245	0.251	0.481	2.769	1.649	1.069
344.65	0.022	0.174	0.178	0.403	3.132	1.777	1.030
348.35	0.021	0.100	0.102	0.279	3.423	1.869	1.007
351.45	0.022	0.055	0.057	0.183	3.741	1.971	0.984
353.15	0.021	0.030	0.031	0.108	3.842	2.022	0.990

组分i	组分j	α_ij	(Δg_ij /R) /J·mol^-1	(Δg_ji /R) /J·mol^-1	ARD/％
甲醇	乙腈	0.4950	171.70	166.84	0.98
甲醇	[Opy][PF₆]	0.1000	-240.33	-21.77
乙腈	[Opy][PF₆]	0.1926	856.77	-1233.94