Effect of glucose–citric acid deep eutectic solvent on the vapor–liquid equilibrium of an aqueous ethanol solution

A. Klinov, A. Khairullina
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Abstract

Objectives. To study the effect of a deep eutectic solvent (DES) based on glucose and citric acid on the vapor–liquid equilibrium of an aqueous solution of ethanol.Methods. A qualitative and quantitative analysis of the conditions of vapor–liquid equilibrium in an ethanol–water–DES ternary mixture was performed based on the open evaporation method and the measurement of TPxy data using a Świętosławski ebulliometer. Since the volatility of the DES is negligible in comparison with that of water and ethanol, the composition of the vapor phase was measured by means of Karl Fischer titration. The conditions of vapor–liquid phase equilibrium were modeled using the UNIFAC model.Results. The open evaporation method was used to determine the curves of residual concentrations for the ethanol–water–DES mixture at various DES concentrations and compositions (glucose–citric acid ratios). TPxy data was obtained for the mixture produced by adding 30 wt % DES to an aqueous solution of ethanol at atmospheric pressure. Studies show that DES based on glucose and citric acid has a significant effect on the relative volatility of ethanol in aqueous solution, leading to the disappearance of the azeotropic point. This effect is due to only the presence of glucose. Citric acid does not change the composition of the equilibrium phases, but rather increases the solubility of glucose in aqueous ethanol solutions. This is especially important at high ethanol concentrations, since glucose is poorly soluble in ethanol.Conclusions. Addition of DES based on glucose and citric acid to an aqueous solution of ethanol leads to the disappearance of the azeotropic point. DES can thus be considered as a promising entrainer for extracting ethanol from aqueous solutions using extractive distillation. Modeling of the conditions of vapor–liquid equilibrium in the ethanol–water–DES system using the UNIFAC model showed a satisfactory level of accuracy. The error in the calculated data increases with increasing the glucose concentration, while remaining acceptable for practical use.
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葡萄糖-柠檬酸深共晶溶剂对乙醇水溶液气液平衡的影响
研究目的研究基于葡萄糖和柠檬酸的深共晶溶剂(DES)对乙醇水溶液气液平衡的影响。根据开放式蒸发法和使用Świętosławski ebulliometer测量TPxy数据,对乙醇-水-DES三元混合物中的汽液平衡条件进行了定性和定量分析。由于 DES 的挥发性与水和乙醇相比可以忽略不计,因此气相的组成是通过卡尔费休滴定法测量的。气相-液相平衡条件使用 UNIFAC 模型进行模拟。采用开放式蒸发法确定了乙醇-水-DES 混合物在不同 DES 浓度和组成(葡萄糖-柠檬酸比率)下的残留浓度曲线。在常压下将 30 wt % DES 加入乙醇水溶液所产生的混合物获得了 TPxy 数据。研究表明,基于葡萄糖和柠檬酸的 DES 对水溶液中乙醇的相对挥发性有显著影响,导致共沸点消失。这种影响仅仅是由于葡萄糖的存在。柠檬酸不会改变平衡相的组成,反而会增加葡萄糖在乙醇水溶液中的溶解度。这一点在乙醇浓度较高时尤为重要,因为葡萄糖在乙醇中的溶解度很低。在乙醇水溶液中加入基于葡萄糖和柠檬酸的 DES 会导致共沸点消失。因此,DES 可被视为使用萃取蒸馏法从水溶液中萃取乙醇的理想夹带剂。使用 UNIFAC 模型对乙醇-水-DES 系统中的汽液平衡条件进行建模,结果显示精确度令人满意。计算数据的误差随着葡萄糖浓度的增加而增大,但在实际使用中仍是可以接受的。
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