Separation of azeotrope (allyl alcohol + water): Isobaric vapour-liquid phase equilibrium measurements and extractive distillation

doi:10.1016/j.jct.2017.11.009

The Journal of Chemical Thermodynamics

Volume 118, March 2018, Pages 139-146

https://doi.org/10.1016/j.jct.2017.11.009 Get rights and content

Highlights

•
The isobaric VLE data for the binary systems of allyl alcohol + NMP/NMF/EG were determined.
•
The thermodynamic consistency of the experimental data was checked by four methods.
•
The experimental data were correlated by the NRTL, UNIQUAC and Wilson activity coefficient models.
•
The extractive distillation processes were presented to separate the azeotrope of allyl alcohol + water.

Abstract

To separate the azeotrope of (allyl alcohol + water) by extractive distillation, N-methyl-2-pyrrolidone, N-methyl formamide and ethylene glycol were selected as extractive agents, and the isobaric VLE data for the binary systems of (allyl alcohol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide) and (allyl alcohol + ethylene glycol) were determined at 101.3 kPa by a modified Rose type recirculating still. The thermodynamic consistency of the experimental data was checked by the Herington, van Ness, infinite dilution, and pure component consistency method. Meanwhile, the experimental data were correlated by the NRTL, UNIQUAC and Wilson activity coefficient models, and the binary interaction parameters of the three models were regressed. All the correlated results by the NRTL, UNIQUAC, and Wilson models agreed well with the experimental data. Furthermore, the extractive distillation processes with the extractive agents were presented to separate the azeotrope of (allyl alcohol + water).

Introduction

Allyl alcohol is widely used in the production of medicine, spices, agricultural chemicals and other engineering applications because of its excellent physical and chemical properties [1], [2], [3], [4]. For example, allyl alcohol can be used as a reaction solvent during the synthesis of trimethylolpropane diallyl ether. After the reaction, the mixture of allyl alcohol and water is generated [5], [6]. To recover allyl alcohol, it is necessary to separate allyl alcohol from its aqueous solution, which is also beneficial for environmental protection and resource reutilization. However, allyl alcohol and water can form an azeotrope at atmospheric pressure. For the separation of such an azeotrope, special distillations are needed, such as extractive distillation, pressure-swing distillation, azeotropic distillation, reactive distillation and so on [7].

In this work, extractive distillation was adopted to separate the azeotrope of allyl alcohol and water. For design of the extractive distillation process, a reliable knowledge of vapour–liquid equilibrium (VLE) data for the system of allyl alcohol and water is required. Particularly, the selection of the entraniners is important, which can enhance the separation factor for the azeotropic mixture allyl (alcohol + water) [8]. Therefore, based on the criteria for the selection of entrainers for extractive distillation by Gmehling and Möllmann [9], N-methyl-2-pyrrolidone, N-methyl formamide and ethylene glycol were selected as the entrainer candidates for the separation of the azeotropic mixture allyl alcohol + water. In recent years, some investigators have reported the VLE data for the system allyl alcohol + water. Grabner [10] and Zhang [2] determined the isobaric VLE data for the system allyl alcohol + water at 101.3 kPa. Aucejo [11], Harper [12] and Lesteva [13] determined the isothermal VLE data of allyl alcohol + water at different pressures and salt effect to the VLE of allyl alcohol + water system was determined by Zhang [14]. However, the isobaric VLE data for the systems of allyl alcohol with N-methyl-2-pyrrolidone, N-methyl formamide and ethylene glycol have not been found in the NIST [15] and Dortmund Data Bank (DDB) [16].

In this work, the isobaric VLE data for the systems allyl alcohol + N-methyl-2-pyrrolidone, allyl alcohol + N-methyl formamide, and allyl alcohol + ethylene glycol at 101.3 kPa were measured by a recirculating type equilibrium still. The thermodynamic consistency of the VLE data was checked by the method of Herington test [17], van Ness test [18], infinite dilution test [19], and pure component consistency test [20]. Furthermore, the NRTL [21], UNIQUAC [22] and Wilson [23] activity coefficient models were used to correlate the VLE data, and the interaction parameters of the three models were obtained. Meanwhile the values of excess Gibbs energy, $G_{m}^{E}$ , were calculated by fitting the VLE data. Also, the extractive distillation process was presented to separate allyl alcohol from its aqueous solution in this work.

Section snippets

Chemicals

All chemicals were supplied by Shandong Xiya Chemical Co, Ltd. The CAS and mass fraction confirmed by GC (SP6890, Shandong Lunan Rui Hong Chemical Instrument Co., Ltd.) are listed in Table 1. All the chemicals were used without further purification.

All chemicals were analytical pure reagents. The water content of the reagents was checked and confirmed by GC. The pure-component boiling temperatures were compared with literature data and the detailed information is presented in Table S1 in the

Experimental results

In this work, the VLE data for three binary mixtures (allyl alcohol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide), and (allyl alcohol + ethylene glycol), were measured at pressure of 101.3 kPa. The experimental VLE data with the values of the activity coefficients and excess Gibbs energy G^E for the three systems are summarized in Table 2, Table 3, Table 4. Also, the T-x-y phase diagrams for the systems are presented in Fig. 1, Fig. 2, Fig. 3.

VLE calculation

The VLE relationship is usually

Solvent effects of entrainers

The solvent effects of the three entrainers N-methyl-2-pyrrolidone, N-methyl formamide and ethylene glycol were examined by calculation of the separation factor. The relative volatility is another criterion used for solvent selection, which is the ratio of volatilities between the light and heavy components after the addition of a solvent. The relative volatility was calculated using the UNIQUAC model with the binary parameters listed in Table 12. The x-y diagram of allyl alcohol and water was

Conclusions

The isobaric VLE values for the binary systems of (allyl alcohol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide) and (allyl alcohol + ethylene glycol) were determined at 101.3 kPa by a modified Rose type recirculating still. The thermodynamic consistency of the experimental results was validated by the Herington, van Ness, infinite dilution, and pure component consistency methods. The results show that the VLE data for the three binary mixtures are thermodynamically consistent.

Acknowledgement

This work was supported by the National Scientific Research Found of China (NSC 21306106).

References (38)

X.L. Wang et al.
A novel and efficient procedure for the preparation of allylic alcohols from α, β-unsaturated carboxylic esters using LiAlH₄/BnCl
Tetrahedron Lett.
(2009)
H. Matsuda et al.
Selection of entrainers for the separation of the binary azeotropic system methanol + dimethyl carbonate by extractive distillation
Fluid Phase Equilib.
(2011)
K. Kojima et al.
Thermodynamic consistency test of vapour-liquid equilibrium data: methanol, water, benzene, cyclohexane and ethyl methyl ketone, water
Fluid Phase Equilib.
(1990)
P.Y. Shi et al.
Separation of azeotrope (2,2,3,3-tetrafluoro-1-propanol + water): isobaric vapour-liquid phase equilibrium measurements and azeotropic distillation
J. Chem. Thermodyn.
(2017)
O. Eric et al.
A new stereoselective method for the preparation of allylic alcohols
J. Am. Chem. Soc.
(1997)
M. Bandini et al.
π-Activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions
Org. Biomol. Chem.
(2009)
Y.K. Wu et al.
An efficient procedure for the 1,3-transposition of allylic alcohols based on lithium naphthalenide induced reductive elimination of epoxy mesylates
Synlett
(2008)
J.J. Zhang, Y.F. Yang, G.Z. Song, A preparation method of trimethylolpropane allyl ether. CN. Patent No. 1301687 A,...
L.Z. Zhang et al.
Isobaric vapour–liquid equilibrium for binary systems of allyl alcohol with water, methanol, and ethanol at 101.3 kPa
J. Chem. Eng. Data
(2016)
Z. Lei et al.
Special Distillation Processes
(2005)

J. Gmehling et al.

Synthesis of distillation processes using thermodynamic models and the Dortmund data bank

Ind. Eng. Chem. Res.

(1998)

W. Roy et al.

Liquid-vapour equilibrium and heats of vapourization of allyl alcohol-water mixtures

J. Chem. Eng. Data

(1965)

A. Aucejo et al.

Isobaric vapour-liquid equilibria of prop-2-en-1-ol (allyl alcohol) + water system at 30, 60, and 100 kPa

ELDATA Int. Electron. J. Physico-Chem. Data

(1996)

B.G. Harper et al.

Vapour-liquid equilibrium new still and method for determining vapour-liquid equilibrium

Ind. Eng. Chem.

(1957)

T.M. Lesteva et al.

Duhen – margules equation used to check isothermic data on liquid-vapour equilibrium in binary and ternary system

Zh. Fiz. Khim.

(1972)

Y. Zhang et al.

Salt effect of 2-propenol-water vapour-liquid equilibrium

Chem. Eng. (China)

(1983)

The NIST Bank, the National Institute of Standards and Technology, NIST....

J. Gmehling, U. Onken. Dortmund Data Bank (DDB), The University of Dortmund....

E.F.G. Herington

Tests for the consistency of experimental isobaric vapour-liquid equilibrium data

J. Inst. Petrol.

(1951)

Cited by (50)

Measurement and correlation of the vapor-liquid equilibria related to the extraction of phenols from tar with mono-ethanolamine
2022, Fluid Phase Equilibria
Extracting phenol from coal tar has great economic significance. In this paper, a process for separating phenol from coal tar using mono-ethanolamine (MEA) as extractant was proposed, the conceptual design and optimized of the process was carried out by using Aspen Plus software. To ensure the accuracy of simulation, the vapor-liquid equilibrium data of MEA + phenol binary system were measured under different pressures. The binary interaction parameters of NRTL model, Wilson model and UNIQUAC model were fitted with the experimental data by data regression system. The results show that the deviation of NRTL model is less than that of Wilson model and UNIQUAC model. Considering that the boiling point difference between MEA and phenol is only 10°, two energy-saving schemes of double effect distillation are introduced into the conceptual process proposed in this paper, which can save 20% and 44.8% respectively compared with the traditional single tower distillation process. This paper provides reference for the industrial application of MEA in the extraction of phenol from coal tar.
Densities and excess volumes of binary and ternary mixtures of N, N-dimethyl sulfoxide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone at T = (293.15, 313.15)K and atmospheric pressure
2022, Chemical Data Collections
Citation Excerpt :
DMSO is recommended for separation of azeotropic mixtures [6–11]. NMP is more commonly used for separation of hydrocarbon mixtures [12–14]. DMA is considered as potential extractive agent, since it selectively increases the relative volatility of the substances [15–17].
Densities of binary liquid mixtures of N,N-dimethyl acetamide (DMA) + dimethyl sulfoxide (DMSO), DMSO + N-methyl-2-pyrrolidone (NMP), and DMA + NMP were measured over the entire composition range in the temperatures of 293.15 K and 313.15 K at atmospheric pressure. Based on this measurements, density deviations, Δρ, and excess molar volumes, V^E, of binary mixtures were calculated and the same were fitted by Redlich-Kister equation. Binary adjustable parameters were obtained using Linear Least Squares Regression (Microsoft Excel 2016). The variations of derivative properties with temperature and composition were discussed. The densities of ternary mixtures DMSO + DMA + NMP were measured at 293.15 K and 313.15 K. According to experimental data, diagrams of density isolines at both temperature, density changes and excess molar volume at 293.15 K are constructed.
Liquid-liquid phase behavior for water + 2,2-difluoroethanol with three imidazole-based ionic liquids
2022, Journal of Molecular Liquids
2,2-difluoroethanol (DFE) is a significant fine chemical in chemical industry. During its applications, an aqueous solution is often observed. Because DFE and water will form azeotropic mixture, it is infeasible to regenerate DFE from the mixture (DFE + water) by general distillation. In this research, for regenerating 2,2-difluoroethanol from its aqueous mixture by extraction, three hydrophobic imidazole-based ionic liquids (ILs), 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Hmim][NTf₂]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][NTf₂]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf₂]) were picked as the extraction agents. The liquid–liquid phase behavior of the systems (water + DFE + ILs) were explored at 298.15 K and 101.3 kPa. The NRTL model was applied to regress the determined tie-line data. To assess the separating power of the three ionic liquids, selectivity (S) and distribution coefficient (D) for ILs were computed and compared. In addition, the σ-profiles, interaction energy, hydrogen bond length between the ionic liquids and (DFE/water) were computed to ascertain the interactions between the ILs and (DFE/water).
Extraction of allyl alcohol from its aqueous solution using two different ionic liquids: Intermolecular interaction and liquid-liquid phase equilibrium explorations
2021, Journal of Molecular Liquids
Allyl alcohol is a remarkable chemical intermediate. During its preparation by allyl acetate hydrolysis, an aqueous mixture is usually obtained. Because allyl alcohol can form a minimum boiling point azeotropic mixture with water, it is impossible to separate such a mixture by conventional distillation. In this work, for recovering allyl alcohol by extraction, the ionic liquid extractants (ILs) were adopted by the model of COSMO-SAC and two ILs 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP][Tf₂N]) and 1-octyl-3-methylimidazolium trifluoromethanesulfonate ([OMIM][OTf]) were selected. The length of the hydrogen bond and the energy of the interaction between the ILs and (allyl alcohol/water) were calculated by quantum chemical calculations. The experimental liquid–liquid phase equilibrium (LLE) data for the ternary systems (water + allyl alcohol + [OMIM][OTf]/[BMP][Tf₂N]) were explored at 298.15 K. The [OMIM][OTf] and [BMP][Tf₂N] extraction capability was assessed with selectivity and partition ratio. In addition, the NRTL model was used to fit the measured tie-line values.
Separation of azeotropic mixture (acetone + n-heptane) by extractive distillation with intermediate and heavy boiling entrainers: Vapour-liquid equilibrium measurements and correlation
2021, Journal of Chemical Thermodynamics
Acetone and n-heptane are widely applied in pharmaceutical industry as benign solvents and are observed in the wastewater. Because acetone and n-hexane can form an azeotropic mixture, it is impossible to recover acetone and n-heptane with high purity from the wastewater using conventional distillation. In this research, for separating the azeotrope (acetone + n-heptane) by homogeneous extractive distillation, 1-chlorobutane and butyl propanoate were chosen as the intermediate and heavy boiling entrainers. The isobaric vapour-liquid equilibrium (VLE) behaviour for the three binary systems (acetone + 1-chlorobutane), (butyl propanoate + acetone) and (n-heptane + butyl propanoate) were reported at 101.3 kPa. The values of the excess Gibbs energy ( $G^{E}$ ) were calculated to explore the nonideal of the systems. The thermodynamic consistency of the determined VLE values was checked by the van Ness and Herington tests. In addition, the determined VLE data were fitted by the UNIQUAC, Wilson, and NRTL models. The parameters of those models were regressed, which are helpful for simulating the separation process with the intermediate and heavy boiling entrainers by extractive distillation.
Modeling vapour-liquid phase equilibrium for the aqueous solutions of formaldehyde and electrolyte
2020, Journal of Chemical Thermodynamics
Modeling of vapor-liquid equilibrium for the aqueous solutions of formaldehyde and electrolyte is required for the extractive distillation of formaldehyde-containing multicomponent mixtures using salt as entrainers. Here a revised physicochemical model, which integrates the advantages of the physicochemical model for the vapor-liquid and the chemical equilibria in aqueous formaldehyde solution and the LIFAC model for the phase behavior in mixed-solvent electrolyte systems, has been proposed. The new vapor-liquid equilibrium data in (HCHO–H₂O–salt) were systematically measured and utilized to determine newly-introduced model parameters. Comparisons of model calculated and experimental measured values proved that the model presented here provides a reliable method for correlating the vapor-liquid equilibria data in (HCHO–H₂O–salt) system. Furthermore, the model established in this work was used to study salts effect on vapor-liquid equilibria. Both the model calculations and the VLE experiments uncover that Zn(NO₃)₂ is the most promising among all of the entrainers investigated.

View all citing articles on Scopus

¹: Jingyu Wu and Dongmei Xu contributed equally.

View full text

Separation of azeotrope (allyl alcohol + water): Isobaric vapour-liquid phase equilibrium measurements and extractive distillation

Highlights

Abstract

Introduction

Section snippets

Chemicals

Experimental results

VLE calculation

Solvent effects of entrainers

Conclusions

Acknowledgement

Tetrahedron Lett.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Thermodyn.

A new stereoselective method for the preparation of allylic alcohols

J. Am. Chem. Soc.

π-Activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions

Org. Biomol. Chem.

An efficient procedure for the 1,3-transposition of allylic alcohols based on lithium naphthalenide induced reductive elimination of epoxy mesylates

Synlett

Isobaric vapour–liquid equilibrium for binary systems of allyl alcohol with water, methanol, and ethanol at 101.3 kPa

J. Chem. Eng. Data

Special Distillation Processes

Synthesis of distillation processes using thermodynamic models and the Dortmund data bank

Ind. Eng. Chem. Res.

Liquid-vapour equilibrium and heats of vapourization of allyl alcohol-water mixtures

J. Chem. Eng. Data

Isobaric vapour-liquid equilibria of prop-2-en-1-ol (allyl alcohol) + water system at 30, 60, and 100 kPa

ELDATA Int. Electron. J. Physico-Chem. Data

Vapour-liquid equilibrium new still and method for determining vapour-liquid equilibrium

Ind. Eng. Chem.

Duhen – margules equation used to check isothermic data on liquid-vapour equilibrium in binary and ternary system

Zh. Fiz. Khim.

Salt effect of 2-propenol-water vapour-liquid equilibrium

Chem. Eng. (China)

Tests for the consistency of experimental isobaric vapour-liquid equilibrium data

J. Inst. Petrol.

Separation of azeotrope (allyl alcohol + water): Isobaric vapour-liquid phase equilibrium measurements and extractive distillation