Pressure Dependent Changes in CO 2 ‐Concentrations Modulate the 3‐Hydroxyvalerate Fraction in Terpolymeric Polyhydroxyalkanoates

Polyhydroxyalkanoates (PHAs), especially their copolymeric forms, such as poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxyvalerate) (PHBVV), have promising properties for replacing petrochemical‐derived plastics. However, the research focuses mostly on producing PHA from a specific substrate or waste‐stream, while the reproducibility of a precise polymer composition is seldom targeted. This study systematically focuses on the influence of pressure conditions on the production of terpolymeric PHBVV by Cupriavidus necator NCIMB 11599 using levulinic acid (LA). Three different process setups were evaluated to assess the impact of hydrostatic pressure (Δ p Hydro ) and applied pressure (Δ p Vessel ) compared to the process at ambient pressure. Differences were detected regarding carbon utilization (Y X/Gluc & Y PHA/LA ) and polymer composition. The Y X/Gluc increased in the pilot scale compared to the technical scale from 0.31 ± 0.01 g X g Gluc −1 to 0.41 ± 0.01 g X g Gluc −1 . Conversely, as Δ p Vessel increased, the Y PHA/LA decreased from 0.35 ± 0.02 g PHA g LA −1 to 0.23 ± 0.02 g PHA g LA −1 , while the corresponding 3HV contents increased from 48 ± 1% (w/w) to 69 ± 2% (w/w) . These changes were consistent with pressure‐dependent variations in CO 2 concentration and a potentially increased carbon fixation via the energy‐intensive CBB cycle. This indicates that the polymer composition and cell vitality can be adjusted via the CO 2 concentration, a factor that should be taken into account when further scaling up of PHA production processes.