基于COSMO-RS方法筛选离子液体分离乙酸乙酯-乙腈共沸物
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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-therm X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。
The application of different ionic liquids in the separation of acetate-acetonitrile azeotrope was investigated by COSMO-RS method. The accuracy of COSMO-therm X prediction of ionic liquid separation wasverified 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 ethylacetate 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 wassmall. The effect of anions [OAc]-and [Cl]-on azeotrope was further studied by applying the surface charge densitydistribution(σ-profile), revealing that the order of influence of the anions [OAc]-and [Cl]-on the separation of ethylacetate-acetonitrile was [OAc]->[Cl]-. The comprehensive prediction results show that ionic liquid [BMIM][OAc] isexpected to be used as a highly efficient extractant in the separation of ethyl acetate-acetonitrile mixture.
The application of different ionic liquids in the separation of acetate-acetonitrile azeotrope was investigated by COSMO-RS method. The accuracy of COSMO-therm X prediction of ionic liquid separation wasverified 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 ethylacetate 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 wassmall. The effect of anions [OAc]-and [Cl]-on azeotrope was further studied by applying the surface charge densitydistribution(σ-profile), revealing that the order of influence of the anions [OAc]-and [Cl]-on the separation of ethylacetate-acetonitrile was [OAc]->[Cl]-. The comprehensive prediction results show that ionic liquid [BMIM][OAc] isexpected to be used as a highly efficient extractant in the separation of ethyl acetate-acetonitrile mixture.
引文
[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.Wang X H, Tian G Z, Xie L, 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.
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[6] Fang J, Zhao R, Su W 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] Zhang L Z, Han J, Deng D, 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] Seiler M, Jork C, Kavarnou A, et al. Separation of azeotropic mixtures using hyperbranched polymers or ionic liquids[J].AIChE Journal, 2004, 50(10):2439-2454.
[9] Calvar N, González B, Gómez E, 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] Simoni L D, Ficke L E, Lambert C 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] Zhang Y, Yu D, Guo F, 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.Li R, Cui X B, Wu T, 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.Cao L, Li Q S. Isobaric vapor-liquid equilibrium for ethyl acetateacetonitrile-1-octyl-3-methylimidazolium hexafluorophosphate system[J]. Petrochemical Technology, 2016, 45(2):194-199.
[14] Li Q S, Cao L. Isobaric vapor-liquid equilibrium for ethyl acetate+acetonitrile+1-butyl-3-methylimidazolium hexafluorophosphate at 101. 3 kPa[J]. J. Chem. Eng. Data, 2013, 58(5):1112-1116.
[15] Zhu J J, Li Q S, Li M, et al. The isobaric vapor liquid equilibria of ethyl acetate+acetonitrile+bis(trifluoromethylsulfonyl)imidebased ionic liquids at 101. 3kPa[J]. Fluid Phase Equilibria, 2016,425:289-296.
[16] Klamt A, Jonas V, Burger T. Refinement and parametrization of COSMO-RS[J]. Journal of Physical Chemistry A, 1998, 102(26):5074-5085.
[17] Klamt A. 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] Banerjee T, Singh M K, Khanna A. Prediction of binary VLE for imidazolium based ionic liquid systems using COSMO-RS[J].Industrial&Engineering Chemistry Research, 2006, 45(9):3207-3219.
[19] Klamt A. 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.Gu L L, Dai W Y, Guo X T. COSMO-RS based ionic-liquid selection for extractive distillation of eucalyptus oil[J]. Chemical Engineering(China), 2016, 44(3):15-21.
[21] Zhang Z G, Zhang L, Zhang Q, et al. Separation of 2-propanol and water azeotropic system using ionic liquids as entrainers[J]. Fluid Phase Equilibria, 2016, 412:94-100.
[22] Lei Z G, Dai C, Zhu J, et al. Extractive distillation with ionic liquids:a review[J]. AIChE Journal, 2014, 60(9):3312-3329.
[23] Li J L, Yang X Q, Chen K 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] Li T T, Yang Q, Ding H 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] Dhanalakshmi J, Sai P S T, Balakrishnan A R. Study of ionic liquids as entrainers for the separation of methyl acetatemethanol and ethyl acetate-ethanol systems using the COSMORS 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.Li J, He W J, Qi Z W, et al. Screening ionic liquids for separation of methanol and dimethyl-carbonate mixtures based on COSMORS method[J]. Petrochemical Technology, 2016, 45(12):1499-1505.
[27] Freire M G, Santos L M, Marrucho I 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] Zheng Z Q, Wu T H, Zhou X 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.Yang X Q, He C C, Chen K X, et al. Screening ionic liquids for separation of acetonitrile and water mixtures based on COSMORS method[J]. Chemical Industry and Engineering Progress,2011, 30(s2):55-61.
[30] Zhang Z G, Wu K F, Zhang Q 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.Li T T, Yang Q, Peng C 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.
[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.Ding B Q, Zhang S, Li Z, 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.Di J 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.Ma W C, Sun J J, Wei H 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.Ding B Q, Zhang S, Xu W, 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] Fang J, Zhao R, Su W 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] Zhang L Z, Han J, Deng D, 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] Seiler M, Jork C, Kavarnou A, et al. Separation of azeotropic mixtures using hyperbranched polymers or ionic liquids[J].AIChE Journal, 2004, 50(10):2439-2454.
[9] Calvar N, González B, Gómez E, 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] Simoni L D, Ficke L E, Lambert C 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] Zhang Y, Yu D, Guo F, 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.Li R, Cui X B, Wu T, 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.Cao L, Li Q S. Isobaric vapor-liquid equilibrium for ethyl acetateacetonitrile-1-octyl-3-methylimidazolium hexafluorophosphate system[J]. Petrochemical Technology, 2016, 45(2):194-199.
[14] Li Q S, Cao L. Isobaric vapor-liquid equilibrium for ethyl acetate+acetonitrile+1-butyl-3-methylimidazolium hexafluorophosphate at 101. 3 kPa[J]. J. Chem. Eng. Data, 2013, 58(5):1112-1116.
[15] Zhu J J, Li Q S, Li M, et al. The isobaric vapor liquid equilibria of ethyl acetate+acetonitrile+bis(trifluoromethylsulfonyl)imidebased ionic liquids at 101. 3kPa[J]. Fluid Phase Equilibria, 2016,425:289-296.
[16] Klamt A, Jonas V, Burger T. Refinement and parametrization of COSMO-RS[J]. Journal of Physical Chemistry A, 1998, 102(26):5074-5085.
[17] Klamt A. 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] Banerjee T, Singh M K, Khanna A. Prediction of binary VLE for imidazolium based ionic liquid systems using COSMO-RS[J].Industrial&Engineering Chemistry Research, 2006, 45(9):3207-3219.
[19] Klamt A. 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.Gu L L, Dai W Y, Guo X T. COSMO-RS based ionic-liquid selection for extractive distillation of eucalyptus oil[J]. Chemical Engineering(China), 2016, 44(3):15-21.
[21] Zhang Z G, Zhang L, Zhang Q, et al. Separation of 2-propanol and water azeotropic system using ionic liquids as entrainers[J]. Fluid Phase Equilibria, 2016, 412:94-100.
[22] Lei Z G, Dai C, Zhu J, et al. Extractive distillation with ionic liquids:a review[J]. AIChE Journal, 2014, 60(9):3312-3329.
[23] Li J L, Yang X Q, Chen K 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] Li T T, Yang Q, Ding H 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] Dhanalakshmi J, Sai P S T, Balakrishnan A R. Study of ionic liquids as entrainers for the separation of methyl acetatemethanol and ethyl acetate-ethanol systems using the COSMORS 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.Li J, He W J, Qi Z W, et al. Screening ionic liquids for separation of methanol and dimethyl-carbonate mixtures based on COSMORS method[J]. Petrochemical Technology, 2016, 45(12):1499-1505.
[27] Freire M G, Santos L M, Marrucho I 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] Zheng Z Q, Wu T H, Zhou X 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.Yang X Q, He C C, Chen K X, et al. Screening ionic liquids for separation of acetonitrile and water mixtures based on COSMORS method[J]. Chemical Industry and Engineering Progress,2011, 30(s2):55-61.
[30] Zhang Z G, Wu K F, Zhang Q 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.Li T T, Yang Q, Peng C 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.