Caproate Production from Yellow Water Fermentation: The Decisive Roles of Electron Donors

Caproate is a valuable medium-chain fatty acid (MCFA) that is found to be extensively used in biofuel production, food preservation, and the pharmaceutical industries. Short-chain fatty acids (SCFAs) from waste streams can be upgraded sustainably through their biological synthesis via anaerobic chain elongation. However, caproate production is frequently limited in real-world systems due to low carbon conversion efficiency and a lack of electron donors. In this study, we developed a two-stage fermentation strategy employing yellow water—a high-strength organic wastewater from liquor manufacturing—as a novel substrate. During primary fermentation, Lactobacillus provided endogenous electron donors by converting the residual carbohydrates in the yellow water into lactic acid. Nano zero-valent iron (NZVI) was introduced to the secondary fermentation to enhance power reduction and electron flow, further promoting caproate biosynthesis. The caproate production increased significantly due to the synergistic action of lactic acid and NZVI, reaching a maximum concentration of 20.41 g·L−1 and a conversion efficiency of 69.50%. This strategy enhances carbon recovery and electron transport kinetics while lowering dependency on expensive external donors like hydrogen or ethanol. Microbial community analysis using 16S rRNA sequencing revealed enrichment of chain-elongating bacteria such as Clostridium kluyveri. These findings demonstrate the feasibility of employing an integrated fermentation–electron management technique to valorize industrial yellow water into compounds with added value. This study offers a scalable and environmentally sound pathway for MCFA production from waste-derived resources.