Elsevier

Fluid Phase Equilibria

Volume 317, 15 March 2012, Pages 89-95
Fluid Phase Equilibria

Measurements and correlation of liquid–liquid equilibria of 4-methyl-2-pentanone + ethanol + water and 4-methyl-2-pentanone + n-butanol + water ternary systems between 283.2 and 323.2 K

https://doi.org/10.1016/j.fluid.2012.01.009Get rights and content

Abstract

In this work, experimental liquid–liquid equilibria data of the systems 4-methyl-2-pentanone + ethanol + water and 4-methyl-2-pentanone + n-butanol + water are presented. The liquid–liquid equilibria of both systems have been measured between 283.2 and 323.2 K. The NRTL and UNIQUAC models were applied to fit the data for both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. The binodal lines were compared to the values predicted by the UNIFAC-LLE and UNIFAC models. Moreover, the solvent capability of 4-methyl-2-pentanone was checked in order to separate these azeotropic mixtures alcohol + water.

Highlights

► 4-Methyl-2-pentanone + ethanol/n-butanol + water liquid–liquid equilibria data are shown. ► The temperature influence on both systems was studied. ► The NRTL and UNIQUAC models were applied to fit the data for both ternary systems. ► The binodal lines were compared to the prediction due by UNIFAC-LLE and UNIFAC models ► The capability of 4-methyl-2-pentanone as solvent was studied.

Introduction

Short chain alcohols (ethanol, propanol and butanol) are commonly used solvents in many chemical and pharmaceutical syntheses and therefore their recovery is frequently sought. However, many of these alcohols are known to form azeotropes with water [1], [2], [3], [4]. In addition, these mixtures are usually present on the chemical process industry (CPI) because alcohols, such as ethanol and n-butanol, are also produce from hydration of alkenes.

In any case, final purification or separation of the alcohol–water mixture is a relative complex procedure due to the existence of a minimum boiling azeotrope. Its separation by simple distillation is impossible. This can be overcome by several techniques including azeotropic and extractive distillation [5], [6], liquid–liquid extraction [7], [8], membrane separation [9] and salt addition [10]. Nevertheless, because of the lower energy cost of the process, liquid–liquid extraction is an alternative method to distillation. At the same time, liquid–liquid extraction is a technique knows to separate the ethanol from aqueous solutions and many solvents have been tried for this purpose [11], [12], [13], [14].

Therefore, this work presents useful liquid–liquid equilibrium (LLE) data for the extraction of ethanol and n-butanol from aqueous solution, respectively.

In the present paper, 4-methyl-2-pentanone is used as an organic solvent, which has low cost and very low solubility in water, and could be, therefore, a good solvent with a high ability for extraction of ethanol or n-butanol from aqueous solution. The 4-methyl-2-pentanone (well known as methyl isobutyl ketone or MIBK) is a ketone widely used as solvent on chemical industry [15], both pure and mixed with other solvents such alcohols.

This work is focused on the study of 4-methyl-2-pentanone (1) + ethanol (2) + water (3) and 4-methyl-2-pentanone (1) + n-butanol (4) + water (3) ternary systems between 283.2 and 323.2 K, in order to check the viability of this ketone as extraction solvent and the temperature influence on the systems. In future studies, we will also analyze the effect of this ketone in the separation of the propanols + water azeotropic mixture.

In a recent literature review, only LLE data for the 4-methyl-2-pentanone (1) + ethanol (2) + water (3) system at 298.2 K has been found [16], which results were compared with our experimental data.

The LLE data were correlated using the UNIQUAC [17] and NRTL [18] activity coefficient models and compared to the values predicted by the UNIFAC method [19] and UNIFAC-LLE method [20]. Finally, the solvent capability has been compared for both azeotropic binary mixtures.

Section snippets

Chemicals

4-Methyl-2-pentanone (>0.995 mass fraction, assay GC) was purchased from Aldrich Ltd, n-butanol (=0.99 mass fraction, assay GC) was supplied from Fluka, ethanol (=0.998 mass fraction, assay GC) was delivered by Merck, n-propanol (0.9997 mass fraction, assay GC) was purchased from Across Organics and water was bidistilled. The reagents were used without further purification after chromatography failed to show any significant impurities. All chemicals used in the experiments are listed in Table 1

Experimental data

The determination of composition of the equilibrium liquid phases for the system 4-methyl-2-pentanone (1) + ethanol (2) + water (3) was carried out at 283.2, 298.2 and 323.2 K and for the system 4-methyl-2-pentanone (1) + n-butanol (4) + water (3) was carried out at 283.2 and 323.2 K at atmospheric pressure and are presented in Table 3, Table 4, respectively. All concentrations are expressed in mole fractions.

As can be observed in Fig. 1, Fig. 2, Fig. 3 the liquid–liquid phase diagrams for

Conclusions

The determination of composition of the equilibrium liquid phases for the systems 4-methyl-2-pentanone (1) + ethanol (2) + water (3) and 4-methyl-2-pentanone (1) + n-butanol (4) + water (3) was carried out between 283.2 and 323.2 K.

The UNIQUAC [17] and NRTL [18] models were used to correlate the experimental data. Both models were found to properly correlate the data for the two systems studied, but the parameters determined have no relation between them. Therefore, for each system, a simultaneous

Acknowledgements

Financial support from the Ministerio de Ciencia y Tecnología of Spain, through project No. CTQ2010-18848/PPQ and the FEDER European Program are gratefully acknowledged. The authors are grateful to Prof. Mª Cruz Burguet for her continuous dedication in our research group and valuable discussions.

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