Isobaric vapor–liquid equilibrium for binary system of N, N-dimethyl formamide + N, N-dimethyl acetamide and quaternary system of sec-butyl alcohol + sec-butyl acetate + N, N-dimethyl formamide + N, N-dimethyl acetamide at 101.3 kPa

doi:10.1016/j.fluid.2015.12.052

Fluid Phase Equilibria

Volume 417, 15 June 2016, Pages 115-119

https://doi.org/10.1016/j.fluid.2015.12.052 Get rights and content

Abstract

Isobaric vapor–liquid equilibrium (VLE) for the binary system N, N-dimethyl formamide (DMF) + N, N-dimethyl acetamide (DMAC) and the quaternary system sec-butyl alcohol (SBA) + sec-butyl acetate (SBAC) + DMF + DMAC were determined at 101.3 kPa using a vapor–liquid equilibrium still. The thermodynamic consistency test for the experimental data was checked by Van Ness point test. The binary VLE data were correlated with the NRTL, UNIQUAC and Wilson activity coefficient models respectively. And the VLE data of the quaternary system predicted by the correlated binary interaction parameters agree well with the experimental data. And the mixture of DMF (3) and DMAC (4) can eliminate the pseudo-azeotrope of sec-butyl alcohol (1) + sec-butyl acetate (2). Thus, the mixture of DMF and DMAC is appropriate for separation of the pseudo-azotrope of SBA and SBAC by extractive distillation.

Introduction

sec-Butyl alcohol (SBA) is an important intermediate for production of methyl ethyl ketone. It is also used as pesticides mineral-dressing agent, emulsifiers, plasticizers and the co-solvent of methanol for improving the octane number of gasoline [1], [2], [3]. SBA is traditionally produced by hydration of n-butene with water. The indirect hydration process uses sulfuric acid as catalyst and causes serious equipment corrosion and low selectivity [4], [5]. Direct hydration process avoids the drawback of corrosion to equipment by replacing sulfuric acid with acidic catalyst, such as heteropolyacid, resin and molecular sieve. But it requires high reaction temperature and pressure, more energy consumption and high purity of n-butene and has low conversion of n-butene [5], [6]. To develop an efficient, stable, environment-friendly process for SBA, the transesterification of sec-butyl acetate (SBAC) with alcohols was presented by researchers [7], which has high conversion, low energy-consumption and no corrosion to equipment.

In the process of transesterification of SBAC with alcohols, SBA and SBAC can form a pseudo-azotrope [8]. Extractive distillation is effective in separation of close-boiling, azeotropic and pseudo-azeotropic systems, in which solvent selection is essential. Berg indicted that the mixture of N, N-dimethyl formamide (DMF) and N, N-dimethyl acetamide (DMAC) is effective in separation SBA from SBAC [9]. However, the VLE data of DMF (3) + DMAC (4) and SBA (1) + SBAC (2) + DMF (3) + DMAC (4) have not been found in the opened literature so far. The VLE data is very important for the simulation and design of the extractive distillation column [10]. Thus, isobaric VLE data at 101.3 kPa of the two systems were measured in this work to provide fundamental data for the separation of SBA and SBAC by extractive distillation.

Section snippets

Chemicals

Analytical reagents (AR), SBA, SBAC, DMF and DMAC were used in this work, whose information is listed in Table 1. Purity of all these chemicals were checked by a gas chromatograph (GC) equipped with a flame ionization detector (FID), and no appreciable peak of impurity was detected. The water contents determined by Karl Fischer titration were less than 0.003 (mass fraction). Therefore, all of the chemicals were used without further purification.

Apparatus and procedure

The VLE data were determined in a circulation

Experimental data

In this work, the isobaric VLE data of the binary system DMF (3) + DMAC (4) and the quaternary system SBA (1) + SBAC (2) + DMF (3) + DMAC (4) were measured by the modified Othmer still at 101.3 kPa. The experimental data are listed in Table 2 and Table 3, respectively.

Vapor–liquid equilibrium model

The activity coefficient can be calculated by the following equation [13]. $y_{i} = [{\hat{ϕ}}_{i}^{v} y_{i} P / (x_{i} ϕ_{i}^{v} P_{i}^{s})] exp [(P - P_{i}^{s}) V_{i}^{L} / R T], (i = 1,2 \dots, N)$ where y_i and x_i are the mole fractions of component i in the vapor and liquid phases, respectively; P

Conclusions

The isobaric VLE data for the binary system DMF (3) + DMAC (4) and the quaternary system SBA + SBAC + DMF + DMAC at 101.3 kPa was measured in a circulation vapor–liquid equilibrium still. The binary VLE experimental data were checked with the Herington area method and the Van Ness test and confirmed to be thermodynamic consistent. The NRTL, UNIQUAC and Wilson models were used to correlate the VLE data of the binary system DMF (3) + DMAC (4). And the VLE behaviors of the quaternary system SBA

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Isobaric vapor–liquid equilibrium of the binary system sec-butyl acetate + para-xylene and the quaternary system methyl acetate + para-xylene + sec-butyl acetate + acetic acid at 101.3 kPa
Fluid Phase Equilib.
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Experimental isobaric vapor–liquid equilibrium for ternary system of sec-butyl alcohol + sec-butyl acetate + N,N-dimethyl formamide at 101.3 kPa
Fluid Phase Equilib.
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Isobaric vapor–liquid equilibrium for binary system of methyl myristate + methyl palmitate at 0.5, 1.0 and 1.4 kPa
Fluid Phase Equilib.
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Isobaric vapor–liquid equilibrium for ternary system of sec-butyl alcohol + sec-butyl acetate +N,N-dimethyl acetamide at 101.3 kPa
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Liquid-liquid equilibrium for sec-butanol – water – KF and sec-butanol – water – K₂CO₃ systems
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There are more references available in the full text version of this article.

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Citation Excerpt :
DMA is considered as potential extractive agent, since it selectively increases the relative volatility of the substances [15–17]. The use of mixed extractive agents containing one of discussed solvents can provide a number of advantages [18–25]. The purpose of using mixed extractive agents is to selectively influence molecular interactions in the separated mixtures.
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.
Experimental isobaric vapour-liquid equilibrium data for binary systems of {sec-butyl acetate (SBAC) + acetamide} and {sec-butyl alcohol (SBA) + acetamide} and the ternary system of (SBAC + SBA + acetamide) at 101.3 kPa
2020, Journal of Chemical Thermodynamics
Citation Excerpt :
Vapour-liquid equilibrium (VLE) data are fundamental in simulation and design of the extractive distillation column. Our previous work has presented the VLE data in separating SBAC and SBA by extractive distillation using N, N-dimethyl acetamide (DMAC) [22], N, N-dimethyl formamide (DMF) [23], dimethyl sulfoxide (DMSO) [24] and their binary mixture as extractive agents [25–27]. Up to now, the VLE data of the system SBAC + SBA + acetamide have not been found in the literature.
Isobaric vapour - liquid equilibrium (VLE) data for the binary systems of sec-butyl acetate (SBAC) + acetamide and sec-butyl alcohol (SBA) + acetamide and the ternary system of SBAC + SBA + acetamide were measured at 101.3 kPa using a modified Othmer still. The thermodynamic consistency tests for the experimental data were checked by Van Ness point test and Wisniak’s L-W method. The experimental VLE data of the binary systems were correlated with NRTL, Wilson and UNIQUAC activity coefficient models. The results indicate that the binary and ternary VLE data predicted by the three models agree well with the experimental data. And the ‘pseudo-azeotropic’ phenomenon of sec-butyl acetate + sec-butyl alcohol mixture can be eliminated by acetamide.
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Isopropyl alcohol and ethyl acetate can be used to produce degradable and renewable fuel. Since isopropyl alcohol + ethyl acetate can form an azeotropic mixture, it is a tough task to separate the binary mixture by general distillation. In this work, extractive distillation process with N, N-dimethylformamide and dimethyl sulfoxide as entrainers was adopted to separate this azeotrope. The binary and ternary vapor-liquid equilibrium data for (isopropyl alcohol + N, N-dimethylformamide), (ethyl acetate + dimethyl sulfoxide), (isopropyl alcohol + ethyl acetate + N, N-dimethylformamide) and (isopropyl alcohol + ethyl acetate + dimethyl sulfoxide) were determined under 101.3 kPa. Meanwhile, the interaction energies between the molecules were calculated to provide the theoretical insight into the separation of the azeotrope of (EA + IPA) by the entrainers. In addition, the NRTL, UNIQUAC and Wilson models were used to fit the determined binary VLE data. The ternary VLE data for (isopropyl alcohol + ethyl acetate + N, N-dimethylformamide) and (isopropyl alcohol + ethyl acetate + dimethyl sulfoxide) were predicted using the NRTL, UNIQUAC and Wilson models with the parameters regressed from the experimental data.
Experimental isobaric vapour-liquid equilibrium data for the binary system (N, N-dimethyl acetamide + dimethyl sulfoxide) and the quaternary system (sec-butyl acetate + sec-butyl alcohol + N, N-dimethyl acetamide + dimethyl sulfoxide) at 101.3 kPa
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Citation Excerpt :
The vapour-liquid equilibrium (VLE) data are indispensable for the simulation and design of the extractive distillation column. Our previous work has investigated the VLE of using N, N-dimethyl acetamide (DMAC) [4], N, N-dimethyl formamide (DMF) [21], dimethyl sulfoxide (DMSO) [22] and the mixture of DMAC and DMF [23] as extractive solvents in separation of SBAC and SBA. However, the VLE data of the system of (SBAC + SBA + DMAC + DMSO) have not been found in the literature.
Isobaric vapour-liquid equilibrium (VLE) data for the binary system of {N, N-dimethyl acetamide (DMAC) + dimethyl sulfoxide (DMSO)} and the quaternary system of {sec-butyl acetate (SBAC) + sec-butyl alcohol (SBA) + DMAC + DMSO} were measured at 101.3 kPa using a modified Othmer still. The thermodynamic consistency test for the binary experimental data was checked by Van Ness point test. The experimental VLE data of the binary system were correlated with Wilson, NRTL and UNIQUAC activity coefficient models. The binary and quaternary VLE data predicted by the binary interaction parameters agreed well with the experimental data. And the mixed solvent (DMAC + DMSO) can eliminate the pseudo-azeotrope of SBAC and SBA. Thus the mixture of (DMAC + DMSO) is a potential extractive solvent in the separation of the pseudo-azeotrope of SBAC and SBA by extractive distillation.
Isobaric Vapor–Liquid Equilibrium Data for the Quaternary System of sec-Butyl Acetate + sec-Butyl Alcohol + Dimethyl Sulfoxide + 1-Ethyl-3-methylimidazolium Acetate at 101.3 kPa
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Fluid Phase Equilibria

Abstract

Introduction

Section snippets

Chemicals

Apparatus and procedure

Experimental data

Vapor–liquid equilibrium model

Conclusions

References (18)

Isobaric vapor–liquid equilibrium of the binary system sec-butyl acetate + para-xylene and the quaternary system methyl acetate + para-xylene + sec-butyl acetate + acetic acid at 101.3 kPa

Fluid Phase Equilib.

Experimental isobaric vapor–liquid equilibrium for ternary system of sec-butyl alcohol + sec-butyl acetate + N,N-dimethyl formamide at 101.3 kPa

Fluid Phase Equilib.

Isobaric vapor–liquid equilibrium for binary system of methyl myristate + methyl palmitate at 0.5, 1.0 and 1.4 kPa

Fluid Phase Equilib.

Isobaric vapor–liquid equilibrium for ternary system of sec-butyl alcohol + sec-butyl acetate +N,N-dimethyl acetamide at 101.3 kPa

Fluid Phase Equilib.

Liquid-liquid equilibrium for sec-butanol – water – KF and sec-butanol – water – K₂CO₃ systems

J. South China Univ. Technol. Nat. Sci. Ed.

Techno-economic analysis of sec-butanol production processes

Mod. Chem. Ind.

Dynamical simulation for production of 2-butyl alcohol by transesterification in a reactive distillation column

Comput. Appl. Chem.

Technogy analysis of n-butene hydration for sec-butanol

Chem. Intermed.

Processes of sec-butanol produced by catalytic hydration of n-butene

Petchem. Technol. Appl.

Cited by (6)

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

Experimental isobaric vapour-liquid equilibrium data for binary systems of {sec-butyl acetate (SBAC) + acetamide} and {sec-butyl alcohol (SBA) + acetamide} and the ternary system of (SBAC + SBA + acetamide) at 101.3 kPa

Separation of azeotropic mixture isopropyl alcohol + ethyl acetate by extractive distillation: Vapor-liquid equilibrium measurements and interaction exploration

Experimental isobaric vapour-liquid equilibrium data for the binary system (N, N-dimethyl acetamide + dimethyl sulfoxide) and the quaternary system (sec-butyl acetate + sec-butyl alcohol + N, N-dimethyl acetamide + dimethyl sulfoxide) at 101.3 kPa

Isobaric Vapor–Liquid Equilibrium Data for the Quaternary System of sec-Butyl Acetate + sec-Butyl Alcohol + Dimethyl Sulfoxide + 1-Ethyl-3-methylimidazolium Acetate at 101.3 kPa

Isobaric Vapor-Liquid Equilibrium Data at 101.3 kPa for the Binary System Acetamide + N,N-Dimethyl Formamide and the Quaternary System sec-Butyl Alcohol + sec-Butyl Acetate + Acetamide + N,N-Dimethyl Formamide

Isobaric vapor–liquid equilibrium for binary system of N, N-dimethyl formamide + N, N-dimethyl acetamide and quaternary system of sec-butyl alcohol + sec-butyl acetate + N, N-dimethyl formamide + N, N-dimethyl acetamide at 101.3 kPa

Abstract

Introduction

Section snippets

Chemicals

Apparatus and procedure

Experimental data

Vapor–liquid equilibrium model

Conclusions

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Liquid-liquid equilibrium for sec-butanol – water – KF and sec-butanol – water – K2CO3 systems

J. South China Univ. Technol. Nat. Sci. Ed.

Techno-economic analysis of sec-butanol production processes

Mod. Chem. Ind.

Dynamical simulation for production of 2-butyl alcohol by transesterification in a reactive distillation column

Comput. Appl. Chem.

Technogy analysis of n-butene hydration for sec-butanol

Chem. Intermed.

Processes of sec-butanol produced by catalytic hydration of n-butene

Petchem. Technol. Appl.

Liquid-liquid equilibrium for sec-butanol – water – KF and sec-butanol – water – K₂CO₃ systems