Extractive distillation with the mixture of ionic liquid and solid inorganic salt as entrainers

The use of the mixture of ionic liquid (IL) and solid inorganic salt in place of the single IL as entrainers for extractive distillation, which integrates the advantages of a liquid solvent, that is, IL (easy operation and nonvolatility) and a solid salt (high separation ability) has been proposed in this work. The vapor–liquid equilibrium experiments indicated that the combination of [EMIM]+[Ac]− and KAc is the most promising for the separation of ethanol and water among all of the entrainers investigated. Based on the thermodynamic study, the conceptual process design was developed to evaluate the competitiveness of the suggested entrainers for the separation of ethanol and water. It was determined that the overall heat duty on reboilers in the extractive distillation process using the new mixed entrainers decreases 19.04% compared with the benchmark entrainer [EMIM]+[Ac]−. Moreover, the density functional theory and COSMO-RS model were used to achieve theoretical insights at the molecular level. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2994–3004, 2014

[1]  W. F. Furter EXTRACTIVE DISTILLATION BY SALT EFFECT , 1992 .

[2]  K. R. Seddon Ionic Liquids for Clean Technology , 1997 .

[3]  Xianbao Cui,et al.  Isobaric VLE data for the system of butan-1-ol + butyl ethanoate + 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide , 2013 .

[4]  So-Jin Park,et al.  Azeotrope breaking for the system ethyl tert-butyl ether (ETBE)+ethanol at 313.15K and excess properties at 298.15K for mixtures of ETBE and ethanol with phosphonium-based ionic liquids , 2013 .

[5]  Wolfgang Arlt,et al.  Separation of Azeotropic Mixtures Using Hyperbranched Polymers or Ionic Liquids , 2004 .

[6]  A. Marciniak Influence of Cation and Anion Structure of the Ionic Liquid on Extraction Processes Based on Activity Coefficients at Infinite Dilution , 2010 .

[7]  Victor R. Ferro,et al.  Integration of COSMO‐based methodologies into commercial process simulators: Separation and purification of reuterin , 2012 .

[8]  Donald G Truhlar,et al.  Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions. , 2006, Journal of chemical theory and computation.

[9]  Qunsheng Li,et al.  Isobaric Vapor–Liquid Equilibrium for the Ethanol + Water + 1,3-Dimethylimidazolium Dimethylphosphate System at 101.3 kPa , 2012 .

[10]  A. Vicent Orchillés,et al.  Using 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate as an Entrainer for the Extractive Distillation of Ethanol + Water Mixtures , 2010 .

[11]  John M. Slattery,et al.  Temperature dependence of the viscosity and conductivity of mildly functionalized and non-functionalized [Tf2N](-) ionic liquids. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[12]  Iván D. Gil,et al.  Separation of ethanol and water by extractive distillation with salt and solvent as entrainer: process simulation , 2008 .

[13]  A. Klamt,et al.  COSMO-RS: an alternative to simulation for calculating thermodynamic properties of liquid mixtures. , 2010, Annual review of chemical and biomolecular engineering.

[14]  M. Dietz Ionic Liquids as Extraction Solvents: Where do We Stand? , 2006 .

[15]  Zhigang Lei,et al.  Isobaric Vapor–Liquid Equilibrium for Isopropanol + Water + 1-Ethyl-3-methylimidazolium Tetrafluoroborate , 2008 .

[16]  Sheng-kai Yang,et al.  Isobaric VLE data for 1-methyl-3-ethylbenzene or 1-methyl-4-ethylbenzene + 1, 2, 4-trimethylbenzene at 20 kPa , 2013 .

[17]  C. Poole,et al.  Extraction of organic compounds with room temperature ionic liquids. , 2010, Journal of chromatography. A.

[18]  José O. Valderrama,et al.  A simple and generalized model for predicting the density of ionic liquids , 2009 .

[19]  Zhigang Lei,et al.  Application of scaled particle theory in extractive distillation with salt , 2002 .

[20]  Á. Domínguez,et al.  Vapor–Liquid Equilibria for the Ternary System Ethanol + Water + 1-Ethyl-3-methylimidazolium Ethylsulfate and the Corresponding Binary Systems Containing the Ionic Liquid at 101.3 kPa , 2008 .

[21]  P. Miguel,et al.  Isobaric Vapor–Liquid Equilibria for the Extractive Distillation of Ethanol + Water Mixtures Using 1-Ethyl-3-methylimidazolium Dicyanamide , 2011 .

[22]  Ingo Krossing,et al.  In silico predictions of the temperature-dependent viscosities and electrical conductivities of functionalized and nonfunctionalized ionic liquids. , 2011, The journal of physical chemistry. B.

[23]  Iván D. Gil,et al.  Control of an extractive distillation process to dehydrate ethanol using glycerol as entrainer , 2012, Comput. Chem. Eng..

[24]  João A. P. Coutinho,et al.  A Group Contribution Method for Heat Capacity Estimation of Ionic Liquids , 2008 .

[25]  De Haan,et al.  Binary and Ternary Vapor-Liquid Equilibrium Data of the System (Ethylbenzene+Styrene+4-Methyl-N-butylpyridinium Tetrafluoroborate) at Vacuum Conditions and Liquid-Liquid Equilibrium Data of Their Binary Systems , 2012 .

[26]  Á. Domínguez,et al.  Study of the behaviour of the azeotropic mixture ethanol–water with imidazolium-based ionic liquids , 2007 .

[27]  Andreas Klamt,et al.  Prediction of the vapor pressure and vaporization enthalpy of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids. , 2007, Physical chemistry chemical physics : PCCP.

[28]  J. Torrecilla,et al.  Density and Molar Volume Predictions Using COSMO-RS for Ionic Liquids. An Approach to Solvent Design , 2007 .

[29]  Sheng Dai,et al.  Ionic liquids-based extraction: a promising strategy for the advanced nuclear fuel cycle. , 2012, Chemical reviews.

[30]  S. O. Momoh,et al.  Assessing the Accuracy of Selectivity as a Basis for Solvent Screening in Extractive Distillation Processes , 1991 .

[31]  Michael D. Frenkel,et al.  ILThermo: A Free-Access Web Database for Thermodynamic Properties of Ionic Liquids† , 2007 .

[32]  Ji-qin Zhu,et al.  Isobaric Vapor—Liquid Equilibrium for (Propan-2-ol + Water + 1-Butyl-3-methylimidazolium Tetrafluoroborate) , 2009 .

[33]  J. Torrecilla,et al.  Development of an a Priori Ionic Liquid Design Tool. 1. Integration of a Novel COSMO-RS Molecular Descriptor on Neural Networks , 2008 .

[34]  A. Arce,et al.  Physical properties and phase equilibria of the system isopropyl acetate + isopropanol + 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide , 2010 .

[35]  D. Armstrong,et al.  Ionic liquids in separations. , 2007, Accounts of chemical research.

[36]  A. Klamt,et al.  COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids , 2000 .

[37]  Wolfgang Arlt,et al.  Influence of Ionic Liquids on the Phase Behavior of Aqueous Azeotropic Systems , 2004 .

[38]  Diego Barba,et al.  Hyperazeotropic ethanol salted-out by extractive distillation. Theoretical evaluation and experimental check , 1985 .

[39]  Honglai Liu,et al.  Sifting Ionic Liquids as Additives for Separation of Acetonitrile and Water Azeotropic Mixture Using the COSMO-RS Method , 2012 .

[40]  J. Ortega,et al.  Experimental Thermodynamic Properties of 1-Butyl-2-methylpyridinium Tetrafluoroborate [b2mpy][BF4] with Water and with Alkan-1-ol and Their Interpretation with the COSMO-RS Methodology , 2009 .

[41]  Qunsheng Li,et al.  Selection of Ionic Liquids as Entrainers for the Separation of Ethyl Acetate and Ethanol , 2009 .

[42]  Victor R. Ferro,et al.  Introducing process simulation in ionic liquids design/selection for separation processes based on operational and economic criteria through the example of their regeneration , 2012 .

[43]  Tom Welton,et al.  Room-temperature ionic liquids: solvents for synthesis and catalysis. 2. , 1999, Chemical reviews.

[44]  A. Klamt,et al.  Fast solvent screening via quantum chemistry: COSMO‐RS approach , 2002 .

[45]  B. Younglove,et al.  Thermophysical properties of fluids , 1982 .

[46]  A. Klamt,et al.  COSMO-RS as a tool for property prediction of IL mixtures—A review , 2010 .

[47]  J. J. Rodríguez,et al.  Optimized ionic liquids for toluene absorption , 2013 .

[48]  Qunsheng Li,et al.  Isobaric Vapor–Liquid Equilibrium for Methanol + Dimethyl Carbonate + 1-Octyl-3-methylimidazolium Tetrafluoroborate , 2012 .

[49]  W. Arlt,et al.  Tailor-made ionic liquids , 2005 .

[50]  W. Arlt,et al.  Separation of 1-hexene and n-hexane with ionic liquids , 2006 .

[51]  G. W. Meindersma,et al.  Ionic liquids in extractive distillation of ethanol/water : from laboratory to pilot plant , 2012 .

[52]  J. Torrecilla,et al.  Development of an a Priori Ionic Liquid Design Tool. 2. Ionic Liquid Selection through the Prediction of COSMO-RS Molecular Descriptor by Inverse Neural Network , 2009 .

[53]  J. Trampé,et al.  Solute recovery from ionic liquids: a conceptual design study for recovery of styrene monomer from [4-mebupy][BF4] , 2013 .

[54]  Zhigang Lei,et al.  Influence of salt added to solvent on extractive distillation , 2002 .

[55]  W. Geng,et al.  Selection of ionic liquids as entrainers for separation of (water + ethanol) , 2008 .

[56]  V. K. Rattan,et al.  Experimental Isobaric Vapor−Liquid Equilibrium Data for Binary Mixtures of Cyclic Ethers with (1-Methylethyl)benzene , 2008 .

[57]  Guangren Yu,et al.  Isobaric vapor–liquid equilibrium for methanol + dimethyl carbonate + phosphoric-based ionic liquids , 2013 .

[58]  Luís M. N. B. F. Santos,et al.  Evaluation of COSMO-RS for the prediction of LLE and VLE of alcohols + ionic liquids , 2007 .

[59]  Zhigang Lei,et al.  COSMO-RS modeling on the extraction of stimulant drugs from urine sample by the double actions of supercritical carbon dioxide and ionic liquid , 2007 .

[60]  J. Ortega,et al.  Interactions of ionic liquids and acetone: thermodynamic properties, quantum-chemical calculations, and NMR analysis. , 2013, The journal of physical chemistry. B.

[61]  A. Klamt,et al.  Refinement and Parametrization of COSMO-RS , 1998 .

[62]  Peter Wasserscheid,et al.  Selection of entrainers in the 1-hexene/n-hexane system with a limited solubility , 2007 .

[63]  P. Miguel,et al.  Isobaric Vapor–Liquid Equilibria of 1-Propanol + Water + Trifluoromethanesulfonate-Based Ionic Liquid Ternary Systems at 100 kPa , 2011 .

[64]  Hsiao-Ping Huang,et al.  Design of a Complete Ethyl Acetate Reactive Distillation System , 2003 .

[65]  Andreas Klamt,et al.  Polarization charge densities provide a predictive quantification of hydrogen bond energies. , 2012, Physical chemistry chemical physics : PCCP.

[66]  Zhigang Lei,et al.  Isobaric Vapor−Liquid Equilibrium for Ethyl Acetate + Ethanol + 1-Ethyl-3-methylimidazolium Tetrafluoroborate† , 2009 .

[67]  W. F. Furter Production of Fuel-Grade Ethanol by Extractive Distillation Employing the Salt Effect , 1993 .

[68]  A. Marciniak Influence of cation and anion structure of the ionic liquid on extraction processes based on activity coefficients at infinite dilution. A review , 2010 .

[69]  Andreas Klamt,et al.  Erratum to “COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids” [Fluid Phase Equilib. 172 (2000) 43–72] , 2003 .

[70]  K. Marsh,et al.  Room temperature ionic liquids and their mixtures—a review , 2004 .

[71]  D. Deng,et al.  Selection of ionic liquids as entrainers for separation of water and 2-propanol , 2007 .

[72]  J. Valderrama,et al.  Critical Properties of Ionic Liquids. Revisited , 2009 .

[73]  Tamal Banerjee,et al.  Prediction of binary VLE for imidazolium based ionic liquid systems using COSMO-RS , 2006 .

[74]  Zhigang Lei,et al.  Solvent improvement for separating C4 with ACN , 2002 .

[75]  J. Brennecke,et al.  Ionic liquids: Innovative fluids for chemical processing , 2001 .

[76]  Á. Domínguez,et al.  Vapor−Liquid Equilibria for the Ternary System Ethanol + Water + 1-Butyl-3-methylimidazolium Chloride and the Corresponding Binary Systems at 101.3 kPa , 2006 .

[77]  A. B. Pereiro,et al.  Applications of Ionic Liquids in Azeotropic Mixtures Separations , 2011 .

[78]  Á. Domínguez,et al.  Experimental vapor-liquid equilibria for the ternary system ethanol + water + 1-ethyl-3-methylpyridinium ethylsulfate and the corresponding binary systems at 101.3 kPa: Study of the effect of the cation , 2010 .

[79]  Zhigang Lei,et al.  Process improvement on separating C4 by extractive distillation , 2002 .

[80]  Sheila N. Baker,et al.  An analytical view of ionic liquids. , 2005, The Analyst.

[81]  Biaohua Chen,et al.  Separation on Aromatics and Non-aromatics by Extractive Distillation with NMP , 2003 .

[82]  A. Klamt Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena , 1995 .

[83]  J. Andino,et al.  Computational and experimental study of the interactions between ionic liquids and volatile organic compounds. , 2010, Physical chemistry chemical physics : PCCP.

[84]  L. Berg Separation of benzene and toluene from close boiling nonaromatics by extractive distillation , 1983 .

[85]  J. Araújo,et al.  Ionic liquids in separations of azeotropic systems - A review , 2012 .

[86]  E. F. G Herington,et al.  Test for the consistency of experimental isbalic vapor-liquid equilibrium data , 1951 .

[87]  K. Tochigi,et al.  Isobaric Vapor–Liquid Equilibria for Ethanol + Water + Ethylene Glycol and Its Constituent Three Binary Systems , 2012 .