Elsevier

Fluid Phase Equilibria

Volume 376, 25 August 2014, Pages 48-54
Fluid Phase Equilibria

Phase equilibria and excess properties for binary systems in reactive distillation processes. Part II. Ethyl acetate synthesis

https://doi.org/10.1016/j.fluid.2014.05.031Get rights and content

Abstract

In this investigation isothermal vapor–liquid equilibrium data (VLE) and excess enthalpy (HE) data were measured for the binary systems required for the design of reactive distillation processes for the ethyl acetate production. The isothermal Px data was measured with a static apparatus, the heat of mixing measurements were performed with a commercial isothermal flow calorimeter. To the experimental data from this work and mixture data from other authors temperature dependent UNIQUAC parameters were fitted.

Introduction

For the accurate design and optimization of separation processes like distillation columns the reliable knowledge of the phase equilibrium behavior is required. The ethyl acetate synthesis by esterification of acetic acid with methanol, and the back reaction, the hydrolysis of ethyl acetate, have received growing interest as a model for reactive distillation processes [1]. The synthesis and hydrolysis of methyl acetate, as first homologous of the row, was already published by Horstmann et al. [2].

While for most of the binary systems experimental data are available in literature (Dortmund Data Bank, DDB 2013) [3], there is a lack of experimental information for some systems. Therefore in this work, isothermal Px data measured with the static method are presented for the binary systems ethanol + acetic acid and ethyl acetate + acetic acid. Excess enthalpy (HE) data were measured for the binary systems ethyl acetate + ethanol, ethanol + acetic acid, ethanol + water, ethyl acetate + acetic acid, and ethyl acetate + water, which are important for a correct description of the temperature dependence of activity coefficients following the Gibbs–Helmholtz equation:lnγi1/TP,x=H¯iER

The experimental vapor–liquid equilibrium (VLE) and HE data of this work as well as VLE, HE, LLE, and azeotropic data from other authors are presented together with a UNIQUAC correlation which can be used in simulation software packages.

Section snippets

Materials

Ethanol, ethyl acetate and acetic acid were purchased from commercial sources. The substances were dried over molecular sieves and afterwards distilled and degassed as described by Fischer and Gmehling [4]. Deionized water was prepared in our laboratory. The final purity and water content were determined by gas chromatography and Karl-Fischer titration and are given in Table 1.

Apparatus and procedure

The VLE measurements (isothermal Px data) were carried out in a computer operated static device following the

Results

Since for the most binary systems many VLE data sets can be found in literature, only isothermal VLE data for the binary systems ethanol + acetic acid and ethyl acetate + acetic acid were measured in this work. Excess enthalpy (HE) data were measured for the binary systems ethyl acetate + ethanol, ethanol + acetic acid, ethanol + water, ethyl acetate + acetic acid, and ethyl acetate + water. For most of the systems moderate temperatures (323.15 to 363.15 K) were chosen. Since for the system ethanol + ethyl

Conclusions

Isothermal Px and HE data were measured for the binary systems containing ethanol, ethyl acetate, acetic acid, and water using the static technique and isothermal flow calorimetry. From these data and data taken from literature temperature dependent UNIQUAC parameters were fitted. The experimental data from this work and from literature data are in good agreement with the predicted values using the UNIQUAC model.

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