Crotonic Acid Production by Pyrolysis and Vapor Fractionation of Mixed Microbial Culture-Based Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Crotonic acid (CA) and trans-2-pentenoic acid (2-PA) can be obtained from renewable resources by pyrolysis of the bio-based poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) copolymer. In this study, direct pyrolysis of the PHBV-enriched biomass into CA and 2-PA was studied under an inert atmosphere and N₂ carrier gas flow, aiming at obtaining high acid yields from mixed microbial cultures (MMCs). The highest yields of 80 ± 2% for CA and 67 ± 1% for 2-PA were obtained at conditions of 240 °C, 1 h, and 0.15 L/min nitrogen flow rate, corresponding to a mean hot vapor residence time of 20 s. A similar acid yield was achieved when the pyrolysis was performed under reduced pressure (150 mbar) instead of using nitrogen gas. The combined pyrolysis of extracted PHBV at 220 °C and 90 min with vapor fractionation by distillation resulted in yields of 81 and 92% for CA and 2-PA, respectively.