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Adsorption of HMF from Water/DMSO Solutions onto Hydrophobic Zeolites: Experiment and Simulation
Author(s) -
Xiong Ruichang,
León Marta,
Nikolakis Vladimiros,
Sandler Stanley I.,
Vlachos Dionisios G.
Publication year - 2014
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201300408
Subject(s) - adsorption , chemistry , ternary operation , solvation , nanoporous , zeolite , chemical engineering , hydrophobic effect , thermodynamics , solvent , catalysis , organic chemistry , physics , computer science , engineering , programming language
The adsorption of 5‐hydroxymethylfurfural (HMF), DMSO, and water from binary and ternary mixtures in hydrophobic silicalite‐1 and dealuminated Y (DAY) zeolites at ambient conditions was studied by experiments and molecular modeling. HMF and DMSO adsorption isotherms were measured and compared to those calculated using a combination of grand canonical Monte Carlo and expanded ensemble (GCMC–EE) simulations. A method based on GCMC–EE simulations for dilute solutions combined with the Redlich–Kister (RK) expansion (GCMC–EE–RK) is introduced to calculate the isotherms over a wide range of concentrations. The simulations, using literature force fields, are in reasonable agreement with experimental data. In HMF/water binary mixtures, large‐pore hydrophobic zeolites are much more effective for HMF adsorption but less selective because large pores allow water adsorption because of H 2 O–HMF attraction. In ternary HMF/DMSO/water mixtures, HMF loading decreases with increasing DMSO fraction, rendering the separation of HMF from water/DMSO mixtures by adsorption difficult. The ratio of the energetic interaction in the zeolite to the solvation free energy is a key factor in controlling separation from liquid mixtures. Overall, our findings could have an impact on the separation and catalytic conversion of HMF and the rational design of nanoporous adsorbents for liquid‐phase separations in biomass processing.