Solubility Temperature Dependence of Bio-Based Levulinic Acid, Furfural, and Hydroxymethylfurfural in Water, Nonpolar, Polar Aprotic and Protic Solvents

Abstract

Bio-based levulinic acid (LA), furfural (FF), and hydroxymethylfurfural (HMF) represent key chemical intermediates when biorefining biomass resources, i.e., either cellulose, glucose, hexoses, etc. (HMF/LA), or hemicellulose, xylose, and pentose (FF). Despite their importance, their online in situ detection by process analytical technologies (PATs), solubility, and its temperature dependence are seldom available. Herein, we report their solubility and temperature dependence by examining n-hexane, cyclohexane, benzene, toluene, 1,4-dioxane, diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, formic acid, n-butanol, n-propanol, ethanol, methanol, and water. These solvents were selected as they are the most common nonpolar, polar aprotic, and polar protic solvents. Fourier-transform infrared (FTIR) spectroscopy was applied as a fast, accurate, and sensitive method to the examined solutions or mixtures. The latter also enables operando monitoring of the investigated compounds in pressurized reactors. Selected temperatures investigated were chosen, as they are within typical operating ranges. The calculated thermodynamic data are vital for designing biorefinery process intensification, e.g., reaction yield optimization by selective compound extraction. In addition to extracting, upstream or downstream unit operations that can benefit from the results include dissolution, crystallization, and precipitation.

Product selectivity and mass transport in levulinic acid transfer hydrogenation by monolithic MIL-100, MIL-88B and ZIF-8@Pd MOFs

“…Unexpectedly, from Figures 7C, D the large GVL molecule shows no diffusion limitation in any of the materials. Therefore, as GVL may have a slightly larger critical diameter than LA, it is likely that any LA diffusion limitations arise increasing surface diffusion effects, facilitated by the much stronger interactions between catalyst and substrate, compared to catalyst and product ( Yuta et al, 2009 ; Jakob et al, 2021 ). Again, for a reaction to be efficient the removal of products from the surface and tortuosity is important as it drives the reaction forward.…”

Electron Beam Etching of Cellulose Microgels for Absorptive Separation of DMSO from Reactions of 5‐Hydroxymethylfurfural Synthesis

“…The microgels were successfully synthesized according to the procedure described in the Experimental Section. Recent studies have shown that HMF differs in its solubility and temperature dependence in different solvents [27] . The swelling properties of the biomass microgels in different solvents obtained using cellulose and chitosan were tested, and the results are shown in Figure 1.…”

Process Design for Value-Added Products in a Biorefinery Platform from Agro and Forest Industrial Byproducts

“…This non-polar solvent allows the extraction of PHB. Since previous studies have demonstrated that LA is not solubilized in non-polar solvents [ 20 ], the solvent must be recovered by evaporation after solvent extraction of PHB. After PHB separation, LA was extracted using furfural.…”