chemicallytechFine Chemical TechnologiesТонкие химические технологии2410-65932686-7575MIREA – Russian Technological University (RTU MIREA).10.32362/2410-6593-2024-19-1-17-27chemicallytech-2029Research ArticleCHEMISTRY AND TECHNOLOGY OF ORGANIC SUBSTANCESХИМИЯ И ТЕХНОЛОГИЯ ОРГАНИЧЕСКИХ ВЕЩЕСТВEffect of glucose–citric acid deep eutectic solvent on the vapor–liquid equilibrium of an aqueous ethanol solutionВлияние глубоко эвтектического растворителя глюкоза–лимонная кислота на парожидкостное равновесие водного раствора этанолаhttps://orcid.org/0000-0002-7833-8330КлиновА. В.KlinovA. V.

Клинов Александр Вячеславович - д.т.н., зав. кафедрой процессов и аппаратов химической технологии, Scopus Author ID 36907475500, ResearcherID K-8270-2017.

420015, Казань, ул. Карла Маркса, д. 68

Alexander V. Klinov - Dr. Sci. (Eng.), Professor, Head of the Chemical Process Engineering Department. Scopus Author ID 36907475500, ResearcherID K-8270-2017.

68, Karla Marksa ul., Kazan, 420015

alklin@kstu.ruhttps://orcid.org/0000-0003-3789-5904ХайруллинаА. Р.KhairullinaA. R.

Хайруллина Алина Ришатовна - к.т.н., ассистент кафедры процессов и аппаратов химической технологии. Scopus Author ID 57278592000.

420015, Казань, ул. Карла Маркса, д. 68

Alina R. Khairullina - Cand. Sci. (Eng.), Assistant, Chemical Process Engineering Department.

68, Karla Marksa ul., Kazan, 420015

khalina@kstu.ruКазанский национальный исследовательский технологический университетРоссияKazan National Research Technological UniversityRussian Federation2024020320241911727Copyright © Klinov A.V., Khairullina A.R., 20242024Клинов А.В., Хайруллина А.Р.Klinov A.V., Khairullina A.R.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.finechem-mirea.ru/jour/article/view/2029Objectives

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

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

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

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.

Цели

Цели. Исследовать влияние глубоко эвтектического растворителя (ГЭР) на основе глюкозы и лимонной кислоты на парожидкостное равновесие водного раствора этанола.

Методы

Методы. Для качественного и количественного анализа условий парожидкостного равновесия в трехкомпонентной смеси этанол–вода–ГЭР использовались метод открытого испарения и измерение TPxy данных в эбулиометре Свентославского. Так как летучесть ГЭР пренебрежимо мала по сравнению с летучестью воды и этанола, состав паровой фазы измерялся титрованием по методу Карла Фишера. Моделирование условий фазового парожидкостного равновесия проводилось на основе модели UNIFAC.

Результаты

Результаты. Методом открытого испарения получены линии остаточных концентраций в смеси этанол–вода–ГЭР при разных концентрациях ГЭР и различном составе ГЭР (глюкоза–лимонная кислота). Получены TPxy данные при добавлении 30 мас. % ГЭР к водному раствору этанола при атмосферном давлении. Проведенные исследования показали, что ГЭР на основе глюкозы и лимонной кислоты оказывает существенное влияние на относительную летучесть этанола в водном растворе, что приводит к исчезновению азеотропной точки. Это влияние связано только с наличием глюкозы. Лимонная кислота не изменяет состава равновесных фаз, но позволяет увеличить растворимость глюкозы в водных растворах этанола. Это особенно важно при высоких концентрациях этанола, так как глюкоза плохо растворима в этаноле.

Выводы

Выводы. Добавление ГЭР на основе глюкозы и лимонной кислоты к водному раствору этанола приводит к исчезновению азеотропной точки. Это позволяет рассматривать данный ГЭР в качестве перспективного экстрактивного агента для извлечения этанола из водных растворов с помощью экстрактивной ректификации. Моделирование условий парожидкостного равновесия в системе этанол–вода–ГЭР с использованием модели UNIFAC показали удовлетворительную точность. Ошибка расчетных данных возрастает с увеличением концентрации глюкозы, однако остается приемлемой для практического использования.

парожидкостное равновесиеглюкозалимонная кислотаэтанол-водарастворимость глюкозыvapor–liquid equilibriumglucosecitric acidethanol–water mixtureglucose solubilityReferencesXu K.X. Handbook of Fine Organic Chemical Raw Materials and Intermediates, 2nd ed. Beijing, China: Chemical Industry Press; 2002.Xu K.X. Handbook of Fine Organic Chemical Raw Materials and Intermediates, 2nd ed. Beijing, China: Chemical Industry Press; 2002.Mahdi T., Ahmad A., Nasef M.M., Ripin A. State-of-the-Art Technologies for Separation of Azeotropic Mixtures. Sep. Purif. Rev. 2014;44(4):308–330. https://doi.org/10.1080/15422119.2014.963607Mahdi T., Ahmad A., Nasef M.M., Ripin A. State-of-the-Art Technologies for Separation of Azeotropic Mixtures. Sep. Purif. Rev. 2014;44(4):308–330. https://doi.org/10.1080/15422119.2014.963607Bajpai P. Developments in Bioethanol. Green Energy and Technology. Springer; 2021. 222 p. https://doi.org/10.1007/978981-15-8779-5Bajpai P. Developments in Bioethanol. Green Energy and Technology. Springer; 2021. 222 p. https://doi.org/10.1007/978981-15-8779-5Lei Z., Chen B., Ding Z. Special Distillation Processes. Elsevier; 2005. 370 p.Lei Z., Chen B., Ding Z. Special Distillation Processes. Elsevier; 2005. 370 p.Laroche L., Andersen H.W., Morari M., Bekiaris N. Homogeneous azeotropic distillation: Comparing entrainers. The Canadian J. Chem. Eng. 1991;69(6):1302–1319. https://doi.org/10.1002/cjce.5450690611Laroche L., Andersen H.W., Morari M., Bekiaris N. Homogeneous azeotropic distillation: Comparing entrainers. The Canadian J. Chem. Eng. 1991;69(6):1302–1319. https://doi.org/10.1002/cjce.5450690611Pereiro A.B., Araújo J.M.M., Esperança J.M.S.S., Marrucho I.M., Rebelo L.P.N. Ionic liquids in separations of azeotropic systems – A review. J. Chem. Thermodyn. 2012;46:2–28. https://doi.org/10.1016/j.jct.2011.05.026Pereiro A.B., Araújo J.M.M., Esperança J.M.S.S., Marrucho I.M., Rebelo L.P.N. Ionic liquids in separations of azeotropic systems – A review. J. Chem. Thermodyn. 2012;46:2–28. https://doi.org/10.1016/j.jct.2011.05.026Abbott A.P., Capper G., Davies D.L., Rasheed R.K., Tambyrajah V. Novel solvent properties of choline chloride/urea mixtures. Chem. Commun. 2002;(1):70–71. https://doi.org/10.1039/B210714GAbbott A.P., Capper G., Davies D.L., Rasheed R.K., Tambyrajah V. Novel solvent properties of choline chloride/urea mixtures. Chem. Commun. 2002;(1):70–71. https://doi.org/10.1039/B210714GAbbott A.P., Boothby D., Capper G., Davies D.L., Rasheed R.K. Deep Eutectic Solvents Formed between Choline Chloride and Carboxylic Acids: Versatile Alternatives to Ionic Liquids. J. Am. Chem. Soc. 2004;126(29):9142–9147. https://doi.org/10.1021/ja048266jAbbott A.P., Boothby D., Capper G., Davies D.L., Rasheed R.K. Deep Eutectic Solvents Formed between Choline Chloride and Carboxylic Acids: Versatile Alternatives to Ionic Liquids. J. Am. Chem. Soc. 2004;126(29):9142–9147. https://doi.org/10.1021/ja048266jNeubauer M., Wallek N., Lux S. Deep eutectic solvents as entrainers in extractive distillation – A review. Chem. Eng. Res. Des. 2022;184:402–418. https://doi.org/10.1016/j.cherd.2022.06.019Neubauer M., Wallek N., Lux S. Deep eutectic solvents as entrainers in extractive distillation – A review. Chem. Eng. Res. Des. 2022;184:402–418. https://doi.org/10.1016/j.cherd.2022.06.019Hansen B.B., Spittle S., Chen B., Poe D., Zhang Y., Klein J.M., et al. Deep Eutectic Solvents: A Review of Fundamentals and Applications. Chem. Rev. 2021;121(3):1232–1285. https://doi.org/10.1021/acs.chemrev.0c00385Hansen B.B., Spittle S., Chen B., Poe D., Zhang Y., Klein J.M., et al. Deep Eutectic Solvents: A Review of Fundamentals and Applications. Chem. Rev. 2021;121(3):1232–1285. https://doi.org/10.1021/acs.chemrev.0c00385Smith E.L., Abbott A.P., Ryder K.S. Deep Eutectic Solvents (DESs) and Their Applications. Chem. Rev. 2014;114(21): 11060–11082. https://doi.org/10.1021/cr300162pSmith E.L., Abbott A.P., Ryder K.S. Deep Eutectic Solvents (DESs) and Their Applications. Chem. Rev. 2014;114(21): 11060–11082. https://doi.org/10.1021/cr300162pPaiva A., Craveiro R., Aroso I., Martins M., Reis R.L., Duarte A.R.C. Natural deep eutectic solvents – solvents for the 21st century. ACS Sustain. Chem. Eng. 2014;2(5):1063–1071. https://doi.org/10.1021/sc500096jPaiva A., Craveiro R., Aroso I., Martins M., Reis R.L., Duarte A.R.C. Natural deep eutectic solvents – solvents for the 21st century. ACS Sustain. Chem. Eng. 2014;2(5):1063–1071. https://doi.org/10.1021/sc500096jСтепаненко Б.Н., Городецкий В.К., Ковалев П.В. (фарм.). Глюкоза. В кн.: Большая медицинская энциклопедия; гл. ред. Акад. Б.В. Петровский: в 30 т. Т. 6. М.: Сов. Энциклопедия; 1977.Stepanenko B.N., Gorodetsky V.K., Kovalev G.V. (farm.). Glucose. In: Petrovsky B.V. (Ed.). Bol’shaya meditsinskaya entsiklopediya (Big Medical Encyclopedia): in 30 v. V. 6. Moscow: Sov. Entsiklopediya; 1977.]Troter D.Z., Zlatkovic M., Đokić-Stojanović D.R. Konstantinović S.S., Todorović Z.B. Citric acid-based deep eutectic solvents: Physical properties and their use as cosolvents in sulphuric acidcatalysed ethanolysis of oleic acid. Adv. Technol. 2016;5(1): 53–65. https://doi.org/10.5937/savteh1601053TTroter D.Z., Zlatkovic M., Đokić-Stojanović D.R. Konstantinović S.S., Todorović Z.B. Citric acid-based deep eutectic solvents: Physical properties and their use as cosolvents in sulphuric acidcatalysed ethanolysis of oleic acid. Adv. Technol. 2016;5(1): 53–65. https://doi.org/10.5937/savteh1601053TŚwietoslawski W. Azeotropy and Polyazeotropy. NY, USA: Macmillan Company; 1963. 226 p.Świetoslawski W. Azeotropy and Polyazeotropy. NY, USA: Macmillan Company; 1963. 226 p.Gmehling J., Kleiber M., Kolbe B., Rarey J. Chemical Thermodynamics for Process Simulation. WILEY-VCH; 2019. 808 p.Gmehling J., Kleiber M., Kolbe B., Rarey J. Chemical Thermodynamics for Process Simulation. WILEY-VCH; 2019. 808 p.Davletbaeva I.M., Klinov A.V., Khairullina A.R., et al. Organoboron ionic liquids as extractants for distillation process of binary ethanol+ water mixtures. Processes. 2020;8(5):628. https://doi.org/10.3390/pr8050628Davletbaeva I.M., Klinov A.V., Khairullina A.R., et al. Organoboron ionic liquids as extractants for distillation process of binary ethanol+ water mixtures. Processes. 2020;8(5):628. https://doi.org/10.3390/pr8050628Klinov A.V., Malygin A.V., Khairullina A.R., et al. Alcohol Dehydration by Extractive Distillation with Use of Aminoethers of Boric Acid. Processes. 2020;8(11):1466. https://doi.org/10.3390/pr8111466Klinov A.V., Malygin A.V., Khairullina A.R., et al. Alcohol Dehydration by Extractive Distillation with Use of Aminoethers of Boric Acid. Processes. 2020;8(11):1466. https://doi.org/10.3390/pr8111466Davletbaeva I.M., Klinov A.V., Khairullina A.R., et al. Vapor– Liquid Equilibrium in Binary and Ternary Azeotropic Solutions Acetonitrile-Ethanol-Water with the Addition of Amino Esters of Boric Acid. Processes. 2022;10(10):2125. https://doi.org/10.3390/pr10102125Davletbaeva I.M., Klinov A.V., Khairullina A.R., et al. Vapor– Liquid Equilibrium in Binary and Ternary Azeotropic Solutions Acetonitrile-Ethanol-Water with the Addition of Amino Esters of Boric Acid. Processes. 2022;10(10):2125. https://doi.org/10.3390/pr10102125Reid R.С., Prausnitz J.M., Poling B.E. The Properties of Gases and Liquids. McGraw-Hill Publisher; 1987. 753 p.Reid R.С., Prausnitz J.M., Poling B.E. The Properties of Gases and Liquids. McGraw-Hill Publisher; 1987. 753 p.Abrams D.S., Prausnitz J.M. Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems. AIChE J. 1975;21(1):116–128. https://doi.org/10.1002/aic.690210115Abrams D.S., Prausnitz J.M. Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems. AIChE J. 1975;21(1):116–128. https://doi.org/10.1002/aic.690210115Maximo G.J., Meirelles A.J.A., Batista E.A.C. Boiling point of aqueous D-glucose and D-fructose solutions: Experimental determination and modeling with group-contribution method. Fluid Phase Equilib. 2010;299(1):32–41. https://doi.org/10.1016/j.fluid.2010.08.018Maximo G.J., Meirelles A.J.A., Batista E.A.C. Boiling point of aqueous D-glucose and D-fructose solutions: Experimental determination and modeling with group-contribution method. Fluid Phase Equilib. 2010;299(1):32–41. https://doi.org/10.1016/j.fluid.2010.08.018Timmermans J. The Physico-Chemical Constants of Binary Systems in Concentrated Solutions. V. IV. Systems with Inorganic + Organic or Inorganic Compounds (Excepting Metallic Derivatives). NY: Interscience Publishers.; 1960. 1347 p.Timmermans J. The Physico-Chemical Constants of Binary Systems in Concentrated Solutions. V. IV. Systems with Inorganic + Organic or Inorganic Compounds (Excepting Metallic Derivatives). NY: Interscience Publishers.; 1960. 1347 p.Hall R.E., Sherill M.S. Freezing point lowering of aqueous solutions. In: Washburn E.W. (Ed.). International Critical Tables of Numerical Data Physics. Chemistry and Technology. V. IV. NY: McGraw-Hill; 1926.Hall R.E., Sherill M.S. Freezing point lowering of aqueous solutions. In: Washburn E.W. (Ed.). International Critical Tables of Numerical Data Physics. Chemistry and Technology. V. IV. NY: McGraw-Hill; 1926.Alves L.A., Almeida e Silva J.B., Giulietti M. Solubility of d-Glucose in Water and Ethanol/Water Mixtures. J. Chem. Eng. Data. 2007;52(6):2166–2170. https://doi.org/10.1021/je700177nAlves L.A., Almeida e Silva J.B., Giulietti M. Solubility of d-Glucose in Water and Ethanol/Water Mixtures. J. Chem. Eng. Data. 2007;52(6):2166–2170. https://doi.org/10.1021/je700177nBockstanz J.G.L., Buffa M., Lira C.T. Solubility of anhydrousglucose in ethanol/water mixture. J. Chem. Eng. Data. 1989;34(4):426–429. https://doi.org/10.1021/je00058a016Bockstanz J.G.L., Buffa M., Lira C.T. Solubility of anhydrousglucose in ethanol/water mixture. J. Chem. Eng. Data. 1989;34(4):426–429. https://doi.org/10.1021/je00058a016

The authors declare that there are no conflicts of interest present.