Removal of phenolic inhibitor compounds from hydrolysates and post-fermentation broths by using a Hydrophobic Magnetic Deep Eutectic Solvent

Hydroxymethylfurfural (HMF), furfural (FF), hydroquinone (HQ), and vanillin (VAN) are among the main inhibitors generated during most of biomass pre-treatments prior to fermentation processes. They are recognized as toxic to several fermentative microorganisms and therefore cause a decrease in biohydrogen or biofuel production (after hydrolysis). Moreover, if they are released into aqueous solutions (after fermentation), they can be detrimental to the ecosystem. In this research, a new method for removing these inhibitor compounds from the broth after hydrolysis and fermentation is proposed. A hydrophobic magnetic deep eutectic solvent (HMDES), based on menthol: nonanoic acid in a mole ratio of 2:1 was prepared and magnetized with Fe3O4 nanoparticles and applied for effective sorption and removal of these inhibitors from the broth after fermentation and for biomass hydrolysates. Parameters affecting sorption, such as pH, volume of the inhibitors, initial concentration of inhibitors, volume of HMDES, temperature, stirring speed, and contact time, were studied and optimized. Under optimum conditions, the removal efficiency for HQ, HMF, FF, and VAN was obtained as 92.97, 86.72, 82.86 and 95.12% for the model samples. In addition, the removal efficiency of real samples after hydrolysis and fermentation for HQ, HMF, FF and VAN were higher than 83.3, 71.42, 69.99 and 76.80%, respectively. The studies on HMDES regeneration revealed that the removal efficiency remained constant even after undergoing 13 cycles of regeneration. The mechanism of inhibitor removal suggests that hydrogen bonding or van der Waals interactions may serve as the predominant factor influencing the extraction process.