Isobaric (vapor + liquid) equilibrium data for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + 2-butyl acetate at P = 101.33 kPa

doi:10.1016/j.jct.2013.12.021

The Journal of Chemical Thermodynamics

Volume 74, July 2014, Pages 85-90

https://doi.org/10.1016/j.jct.2013.12.021 Get rights and content

Highlights

•
VLE data for methanol + 2-butyl alcohol were determined.
•
VLE data for methyl acetate + methanol + 2-butyl alcohol + SBAC were determined.
•
The binary interaction parameters were obtained based on the binary VLE data.
•
The data of quaternary system have been predicted.
•
Both Wilson and NRTL models are suitable to describe the VLE of quaternary system.

Abstract

In this paper, isobaric (vapor + liquid) equilibrium (VLE) data for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + 2-butyl acetate were determined at P = 101.33 kPa in a modified Rose still. The binary VLE data were found to be thermodynamic consistency by the Herrington method. The VLE data for the binary system were correlated by the Wilson and NRTL equations respectively, which were used to predict the VLE data of the quaternary system. The results showed that the Wilson and NRTL models matched well with the (vapor + liquid) phase equilibrium data. The deviations for the vapor-phase compositions and the equilibrium temperatures are reasonably small and the models are both suitable for these systems.

Introduction

2-Butyl alcohol is a vital organic raw material which is produced on a large scale, primarily as a precursor to the industrial solvent methyl ethyl ketone. It also can be used in the production of pesticide, pharmaceutical intermediates, spices, dyes and wetting agents. 2-Butyl alcohol is manufactured industrially by the hydration of 1-butene or 2-butene including the indirect and direct hydration [1], [2]. However, there are some drawbacks among these methods. It is necessary and appropriate to present a new process transesterification, to synthesize 2-butyl alcohol. Transesterification is a reaction that ester and alcohol react under the acid or alkali catalyst and generate the new ester and alcohol, known as the alcoholysis reaction. It is a reversible reaction [3], [4], [5]. The transesterification of 2-butyl acetate (SBAC) and methanol form methyl acetate and 2-butyl alcohol. One of the equilibrium reactions suitable for reactive distillation is transesterification. In general, the transesterification reactions are the equilibrium-limited reactions and could not reach complete conversion. The reactive distillation can lead to the higher conversion and selectivity [5], [6], so it can raise the utilization ratio of the raw materials and decrease the operating costs significantly.

The reactive distillation has received the increasing attention over the past several years as a promising alternative to conventional processes. Modeling of the reactive distillation is quite complex, since it involves both the multicomponent (vapor + liquid) equilibrium and the chemical reaction simultaneously. The VLE data is vital basic data for the study of reactive distillation. In the open literature, there are the VLE data for the binary system methanol + 2-butyl alcohol [7], [8], but these data are all in the low pressure condition, the measuring pressure is under 22 kPa. The transesterification reaction which SBAC and methanol form methyl acetate and 2-butyl alcohol can proceed at normal pressure, so the measurement of isobaric VLE data for the binary system methanol + 2-butyl alcohol is necessary. However, the (vapor + liquid) equilibrium data for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + 2-butyl acetate at P = 101.33 kPa have not been found in the literature. The reactive distillation process which is used to carry on the transesterification reaction producing 2-butyl alcohol is controlled at the ordinary pressure, so the VLE data were measured at P =101.33 kPa in this work. The experimental data of the binary system were correlated by Wilson and NRTL models and the binary interaction parameters of the other five binary systems had been obtained [9], [10], [11], [12], [13]. These binary interaction parameters were applied to predict the VLE data of the quaternary system. The purpose of this paper is to investigate the behavior of the (vapor + liquid) phase equilibrium of these systems and to provide the basic data for the simulation and design of the reactive distillation process.

Section snippets

Chemicals

The chemicals methyl acetate, methanol, 2-butyl alcohol and SBAC used in this work were supplied by Guangzhou Jinhuada Chemistry. Among them, SBAC had been purified by the distillation in order to eliminate the organic impurities, the others were all high-purity grade, so these products were used without the further purification. Table 1 shows the purification methods, final mass fraction and analysis method of the pure substances.

Apparatus and procedure

The experimental equilibrium still was a modified Rose still in

Experimental data

In this paper, the experimental data were determined in a modified Rose still. With the method mentioned in 2.2, the isobaric VLE data at P = 101.33 kPa for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + SBAC were determined. The experimental data for these systems are showed in TABLE 2, TABLE 3 respectively.

(Vapor + liquid) equilibrium model

The activity coefficients of the substances, listed in table 2, were calculated according to the following equation [15]: $γ_{i} = [\overset{\land}{ϕ_{i}^{v}} y_{i} p]$

Conclusions

In this paper, the isobaric VLE data for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + SBAC have been determined at P = 101.33 kPa. The VLE data satisfy the requirements of thermodynamic consistency test. The experimental binary VLE data have been correlated by Wilson and NRTL models. Based on the binary interaction parameters, the VLE data of the quaternary system methyl acetate + methanol + 2-butyl alcohol + SBAC have been predicted and

Acknowledgments

The authors are grateful to the National Science Council of Republic of China for financial support under Project NSC21176049, the Nature Science Foundation of Fujian Province for financial support under Project 2012J01040.

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Isobaric (vapor + liquid) equilibrium data for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + 2-butyl acetate at P = 101.33 kPa

Highlights

Abstract

Introduction

Section snippets

Chemicals

Apparatus and procedure

Experimental data

(Vapor + liquid) equilibrium model

Conclusions

Acknowledgments

Fluid Phase Equilib.

Fluid Phase Equilib.

Energy Proc.

Fluid Phase Equilib.

Fluid Phase Equilib.

Hydrocarbon Process.

Mod. Chem. Ind.

J. Am. Oil Chem. Soc.

Ind. Eng. Chem.

Chem. Eng. Process.

Ind. Eng. Chem. Res.

J. Chem. Eng. Data

Can. J. Chem.