Extraction of 5-Hydroxymethylfurfural and Furfural in Aqueous Biphasic Systems: A COSMO-RS Guided Approach to Greener Solvent Selection

Author(s)

Soukup-Carne, Dominik ; Lopez-Porfiri, Pablo ; Bragagnolo, Felipe Sanchez ; Funari, Cristiano Soleo ; Fan, Xiaolei ; Gonzalez-Miquel, Maria ; Esteban, Jesus

• Document type: Journal article
• Source: ACS SUSTAINABLE CHEMISTRY & ENGINEERING; v. 12, n. 9, p. 14-pg., 2024-02-20.

Abstract

5-Hydroxymethylfurfural (HMF) and furfural (Fur) are promising biobased platform chemicals, derived from the dehydration of carbohydrate feedstocks, normally conducted in an aqueous phase. Plagued by side-reactions in such phase, such as the rehydration to levulinic acid (LA) and formic acid (FA) or self-condensation to humins, HMF and Fur necessitates diversification from monophasic aqueous reaction systems toward biphasic systems to mitigate undesired side-reactions. Here, a methodology based on the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) method was used to screen solvent candidates based on the predicted partition coefficients (K-i). Hansen solubility parameters in conjunction with excess thermodynamic quantities determined by COSMO-RS were employed to assess solvent compatibility. Experimental validation of the COSMO-RS values highlighted only minor deviations from the predictions with root-mean-square-error (RMSE) values of HMF and Fur at 0.76 and 5.32, respectively, at 298 K. The combined effort suggested cyclohexanone, isophorone, and methyl isobutyl ketone (MIBK) as the best candidates. Finally, extraction solvent reuse demonstrated cyclohexanone suitability for HMF extraction with K-HMF of 3.66 and MIBK for Fur with K-Fur 7.80 with consistent partitioning across four total runs. Both solvents are classified as recommended by the CHEM21 solvent selection guide, hence adding to the sustainability of the process. (AU)

• FAPESP's process: 22/00645-0 - Integral valorization of soya and wheat by-products generated in Brazil and United Kingdom: a cascading value-adding approach
• Grantee: Cristiano Soleo de Funari
• Support Opportunities: Regular Research Grants
• FAPESP's process: 17/06216-6 - Development of green analytical methodologies in the search for high-added value organic compounds in agricultural waste
• Grantee: Cristiano Soleo de Funari
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 22/10469-5 - Application of in silico tools for the extraction of bioactive compounds from agro by-products by gas-expanded liquids and green switchable solvents
• Grantee: Felipe Sanchez Bragagnolo
• Support Opportunities: Scholarships in Brazil - Post-Doctoral