Green Solvent-Based Approaches for Volatile Fatty Acid Production and Recovery from Organic Waste

Volatile fatty acids (VFAs) are essential precursors in chemical synthesis for various chemicals, polymers, pharmaceuticals, and fragrance compounds. Acidogenic anaerobic digestion (or arrested methanogenesis) is a promising method to stabilize organic wastes and convert them to value-added products such as VFAs. However, the VFAs’ accumulation could in turn suppress the fermentation process through product inhibition and limit the titer of VFA in the digestate. Therefore, in situ separation and recovery of VFAs from the fermentate is crucial to constructing an effective continuous VFA-producing system. Recent research has been dedicated to addressing these issues and advancing the utilization of biobased VFAs, particularly through process-intensified strategies employing novel green solvents such as natural deep eutectic solvents. Furthermore, in situ conversion of VFAs into esters is another potential strategy for VFA removal. However, VFA esterification in an aqueous medium is challenging due to the abundant water driving the reaction toward hydrolysis. Recent advances in free or immobilized enzyme catalysis in solvents have demonstrated improved ester yield by providing a hydrophobic space for the esterification reaction in aqueous solution. In this review, we present an overview of critical aspects on the state-of-the-art of green solvent-based process intensification strategies, including feedstock selection and pretreatment, operating condition optimization, advances in membrane- and solvent-based recovery methods, and biocatalytic in situ esterification. Lastly, we provide perspectives toward cost-effective, continuous, high-solid, environmental-benign, and industrial-relevant VFA production applications.