Experimental Study and Mechanism Analysis on the Separation of 2-Methylfuran/Methanol from Biofuel Assisted by Ethylene Glycol

Abstract

The formation of azeotropic mixtures between 2-methylfuran (2-MF) and methanol (MeOH) during catalytic hydrogenation of furfural poses a significant challenge for their separation. To address this issue, ethylene glycol (EG) was systematically evaluated as a sustainable extractant for liquid-liquid extraction of the 2-MF-MeOH azeotrope. The σ-profiles of five candidate solvents, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), and EG were analyzed. EG was identified as the optimal extractant due to its superior hydrogen-bonding capability. Key operational parameters including equilibrium temperature and azeotropic composition were experimentally optimized. Then, ternary liquidliquid phase equilibrium (LLE) data of 2-MF(1)+MeOH(2)+EG(3) were measured. The non-random two-liquid (NRTL) model demonstrated excellent correlation with LLE data (RMSD<2%), validating its reliability for process simulation. Multi-scale analysis methods for separation mechanism, such as electrostatic potential (ESP) mapping, independent gradient model based on Hirshfeld partition (IGMH), and molecular dynamics simulation were used to confirm the sites and types of interaction. This fundamental understanding of molecular interactions provides critical insights for designing sustainable separation processes in biomass-derived chemical production.

Keywords

Azeotropic separation / Liquid-liquid equilibrium / Molecular interaction

References

[1] Gandarias I, García-Fernández S, Obregón I, Agirrezabal-Telleria I, Arias P L. Fuel Process. Technol., 2018, 178: 336

[2] Kulkarni B B, Maradur S P. Bioresour. Technol., 2024, 402: 130805

[3] Giorgianni G, Perathoner S, Centi G, Soo-Tang S H, de Jong E, van der Waal J C, Abate S. Chem. Eng. Res. Des., 2023, 197: 968

[4] Li B, Li L, Sun H, Zhao C. ACS Sustainable Chem. Eng., 2018, 6: 12096

[5] Gilkey M J, Panagiotopoulou P, Mironenko A V, Jenness G R, Vlachos D G, Xu B. ACS Catal., 2015, 5: 3988

[6] Wang C, Wei L, Cheng Z, Xu H, Daniel R, Shuai S. Combust. Sci. Technol., 2015, 188: 329

[7] Banerjee D, Sahu A K, Clegg J K, Upadhyayula S. Chem. Eng. J., 2024, 493: 152552

[8] Yao C, Hou Y, Wu W, Ren S, Liu H. Green Chemistry, 2018, 20: 3101

[9] Aghel B, Mohadesi M, Gouran A. Sep. Sci. Technol., 2019, 55: 3402

[10] Warrag S E E, Darwish A S, Adeyemi I A, Hadj-Kali M K, Kroon M C, AlNashef I M. Fluid Phase Equilib., 2020, 517: 112622

[11] Yu Y, Zhang L, Zhu C, Huang X, Liao Z, Li Q. J. Solution Chem., 2020, 49: 1

[12] Zhu Z, Xu Y, Feng T, Wang N, Liu K, Fan H, Reyes-Labarta J A, Wang Y, Gao J, Wang L. J. Mol. Liq., 2020, 298: 111947

[13] Casás L M, Orge B, Ferreira O. J. Chem. Eng. Data, 2008, 53: 89

[14] da Silva J L, Aznar M. Fuel, 2014, 136: 316

[15] Dai F, He G, Xin K, Shi M, Li J, Li Q. J. Chem. Thermodyn., 2017, 115: 91

[16] Li C, Wang X, Li H, Duan C, An L, Liu Q. J. Chem. Eng. Data., 2019, 64: 1780

[17] Yu Y, Zhang X, Yi L, Li M, Zhang F, Wei J. J. Chem. Eng. Data., 2022, 67: 1195

[18] Renon H, Prausnitz J M. AlChE J., 1968, 14: 135

[19] Zhang Y, Li H, Li H, Shan R, Zhu Z, Wang Y, Gao J. J. Chem. Thermodyn., 2022, 167: 106715

[20] Ding Y, Guo Y, Sun Y, Sun T, Ye Q, Li J, Paricaud P, Peng C. Ind. Eng. Chem. Res., 2022, 61: 16193

[21] Boys S F, Bernardi F. Mol. Phys., 1970, 19: 553

[22] Lu T, Chen F. J. Comput. Chem., 2011, 33: 580

[23] Humphrey W A D, Schulten K. J. Mol. Graph., 1996, 14: 33

[24] Fu Y, Song X, Pang Y, Zheng Y, Gao L. J. Mol. Struct., 2023, 1290: 136000

[25] Martínez L, Andrade R, Birgin E G, Martínez J M. J. Comput. Chem., 2009, 30: 2157

[26] Berendsen H J C, van der Spoel D, van Drunen R. Comput. Phys. Commun., 1995, 91: 43

[27] Fan W, Ge C, Ding D, Deng L, Gao J, Xu D. J. Chem. Thermodyn., 2023, 182: 107036

[28] Zhang A, Yan H, Niu X, Han M, Wang W, Zhang Z, Lu W, Li T, Li Q. J. Chem. Eng. Data., 2023, 68: 2645

[29] Araya-López C, Contreras J, Merlet G, Cabezas R, Olea F, Villarroel E, Salazar R, Romero J, Quijada-Maldonado E. Fluid Phase Equilib., 2022, 561: 113518

[30] Chen X, Gao X, Zheng H, Zhao S, Wang L E. Fluid Phase Equilib., 2012, 313: 102

[31] Sun C, Xing J, Qu Y, Zhang Y, Cui P, Wang Y, Gao J. Ind. Eng. Chem. Res., 2023, 62: 9302

[32] Wang W, Wang Y, Lu W, Zhao W, Zhu Z, Cui P, Li X, Song X. Sep. Purif. Technol., 2025, 359: 130587

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Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH