Long-Term Continuous Extraction of Medium-Chain Carboxylates by Pertraction With Submerged Hollow-Fiber Membranes

Medium-chain carboxylic acids (MCCAs), which can be generated from organic waste and agro-industrial side streams through microbial chain elongation, are valuable chemicals with numerous industrial applications. Membrane-based liquid-liquid extraction (pertraction) as a downstream separation process to extract MCCAs has been applied successfully. Here, a novel pertraction system with submerged hollow-fiber membranes in the fermentation bioreactor was applied to increase the MCCA extraction rate and reduce the footprint. The highest average surface-corrected MCCA extraction rate of 655.2 ± 86.4 mmol C m^-2 d^-1 was obtained, which was higher than any other previous reports, albeit the relatively small surface area removed only 11.6% of the introduced carbon via pertraction. This submerged extraction system was able to continuously extract MCCAs with a high extraction rate for more than 8 months. The average extraction rate of MCCA by internal membrane was 3.0- to 4.7-fold higher than the external pertraction (traditional pertraction) in the same bioreactor. A broth upflow velocity of 7.6 m h^-1 was more efficient to extract MCCAs when compared to periodic biogas recirculation operation as a means to prevent membrane fouling. An even higher broth upflow velocity of 40.5 m h^-1 resulted in a significant increase in methane production, losing more than 30% of carbon conversion to methane due to a loss of H₂, and a subsequent drop in the H₂ partial pressure. This resulted in the shift from a microbial community with chain elongators as the key functional group to methanogens, because the drop in H₂ partial pressure led to thermodynamic conditions that oxidizes ethanol and carboxylic acids to acetate and H₂ with methanogens as the syntrophic partner. Thus, operators of chain elongating systems should monitor the H₂ partial pressure when changes in operating conditions are made.