Salts effect on isobaric vapor−liquid equilibrium for separation of the azeotropic mixture allyl alcohol + water
Introduction
Allyl alcohol is an important chemical intermediate. Due to its excellent physical and chemical properties, allyl alcohol is widely applied in the production of medicine, spices, and agricultural chemicals [1], [2], [3], [4]. Generally, allyl acetate hydrolysis method is adopted to produce allyl alcohol in industry, from which the production mixture consisted of allyl alcohol, water and a small amount of allyl aldehyde and acetic acid can be obtained [5]. To separate allyl alcohol from the mixture, the distillation technology is needed. However, since allyl alcohol and water can form a minimum azeotrope, the special distillation is necessary.
Usually, for the separation of the azeotropic mixtures, special distillations are applied, such as extractive distillation, azeotropic distillation, salt distillation, pressure-swing distillation and reactive distillation [6]. Considering the salts effect on isobaric vapor-liquid equilibrium of the azeotropic mixtures, which can affect the relative volatility of the components in the mixtures [7], [8], [9], [10], in this work, the salt distillation technology was adopted for its high-efficiency separation capacity for the azeotropic mixture of allyl alcohol and water.
In the previous works, some researchers reported the VLE for the system of allyl alcohol + water [11], [12], [13], [14], [15]. Grabner [11] and Zhang [12] determined the isobaric VLE data for the system allyl alcohol + water at 101.3 kPa. Aucejo [13] measured the isobaric VLE data for allyl alcohol + water at pressures of 30, 60 and 100 kPa. And the isobaric VLE data of allyl alcohol + water at 100.26 kPa were determined by Harper [14]. Meanwhile, Lesteva reported the isothermic VLE data for allyl alcohol + water at 313.14 K [15]. To separate azeotropic systems contain alcohols, calcium chloride, calcium nitrate and magnesium nitrate were selected as azeotrope destroyers [9], [16], [17], [18], [19], which have a strong salting out effect and lead to the elimination of the azeotropic points. Since calcium chloride, calcium nitrate and magnesium nitrate are well dissolved in water and allyl alcohol, and the solubilities of the salts in allyl alcohol are different than water, the three salts were adopted in this work to break the azeotrope of allyl alcohol and water. According to the retrieve results from the NIST, the salts (calcium chloride, calcium nitrate and magnesium nitrate) effect on isobaric VLE for the system of allyl alcohol + water has not been reported.
In this work, the isobaric vapor-liquid equilibrium data for the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate were determined at 101.3 kPa and the thermodynamic consistency of the measured VLE data were checked by the van Ness test [20], [21]. Meantime, the VLE data were correlated by the nonrandom two-liquid model (NRTL) [22], [23].
Section snippets
Chemicals
Allyl alcohol was purchased from Shandong Xiya Chemical Co., Ltd. with the mass fraction of 0.99. The purity of allyl alcohol was checked and confirmed by gas chromatography (SP6890, Shandong Rui Hong Chemical Co., Ltd.). The salts, calcium nitrate, calcium chloride, and magnesium nitrate were provided by Chengdu Kelong Chemical Reagents Co., Ltd. The water content of the salts was checked by Karl Fisher titration. Allyl alcohol and calcium chloride were used without further purification.
Validation of the apparatus
The isobaric VLE data for the binary system allyl alcohol and water at pressure of 101.3 kPa were determined to verify the reliability of the equilibrium still, which are listed in Table 3. For comparison, the references data reported by Grabner [11] and Zhang [12] are plotted in Fig. 1. As shown in Fig. 1, the measured VLE data agree well with literature data, which indicate that the apparatus is reliable. Moreover, the system of allyl alcohol and water formed an azeotrope at x1 ≈ 0.451 and
Conclusions
The isobaric vapor-liquid equilibrium data for the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate were determined at pressure of 101.3 kPa. The consistency of the measured VLE data were checked by the van Ness test. With addition of the salts, the azeotropic point of the system allyl alcohol and water moved and was eliminated. The salting-out effect of the salts follow the order:
Acknowledgement
Financial support from the National Natural Science Foundation of China (Project 21306093) is gratefully acknowledged.
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Li Xu and Dongmei Xu contributed equally.