Polyhydroxyalkanoate recovery overview: properties, characterizations, and extraction strategies.

Due to their excellent properties, polyhydroxyalkanoates are gaining increasing recognition in the biodegradable polymer market. These biogenic polyesters are characterized by high biodegradability in multiple environments, overcoming the limitation of composting plants only and their versatility in production. The most consolidated techniques in the literature or the reference legislation for the physical, chemical and mechanical characterisation of the final product are reported since its usability on the market is still linked to its quality, including the biodegradability certificate. This versatility makes polyhydroxyalkanoates a promising prospect with the potential to replace fossil-based thermoplastics sustainably. This review analyses and compares the physical, chemical and mechanical properties of poly-ß-hydroxybutyrate and poly-ß-hydroxybutyrate-co-ß-hydroxyvalerate, indicating their current limitations and strengths. In particular, the copolymer is characterised by better performance in terms of crystallinity, hardness and workability. However, the knowledge in this area is still in its infancy, and the selling prices are too high (9-18 $ kg-1). An analysis of the main extraction techniques, established and in development, is also included. Solvent extraction is currently the most widely used method due to its efficiency and final product quality. In this context, the extraction phase of the biopolymer production process remains a major challenge due to its high costs and the need to use non-halogenated toxic solvents to improve the production of good-quality bioplastics. The review also discusses all fundamental parameters for optimising the process, such as solubility and temperature.

Production of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from methane and volatile fatty acids: properties, metabolic routes and current trend.

Polyhydroxyalkanoates (PHAs) are biobased and biodegradable polymers that could effectively replace fossil-based and non-biodegradable plastics. However, their production is currently limited by the high production costs, mainly due to the costly carbon sources used, low productivity and quality of the materials produced. A potential solution lies in utilizing cheap and renewable carbon sources as the primary feedstock during the biological production of PHAs, paving the way for a completely sustainable and economically viable process. In this review, the opportunities and challenges related to the production of polyhydroxyalkanoates using methane and volatile fatty acids (VFAs) as substrates were explored, with a focus on poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate). The discussion reports the current knowledge about promising Type II methanotrophs, the impact of process parameters such as limiting nutrients, CH4:O2 ratio and temperature, the type of co-substrate and its concentration. Additionally, the strategies developed until now to enhance PHA production yields were also discussed.

Techno-economic assessment of biopolymer production from methane and volatile fatty acids: effect of the reactor size and biomass concentration on the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) selling price.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) is a biobased and biodegradable polymer that could efficiently replace fossil-based plastics. However, its widespread deployment is slowed down by the high production cost. In this work, the techno-economic assessment of the process for producing poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from low-cost substrates, such as methane and valeric acid derived from the anaerobic digestion of organic wastes, is proposed. Several strategies for cost abatement, such as the use of a mixed consortium and a line for reagent recycling during downstream, were adopted. Different scenarios in terms of production, from 100 to 100,000 t/y, were analysed, and, for each case, the effect of the reactor volume (small, medium and large size) on the selling price was assessed. In addition, the effect of biomass concentration was also considered. Results show that the selling price of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) is minimum for a production plant with 100,000 t/y capacity, accounting for 18.4 €/kg, and highly influenced by the biomass concentration since it can be reduced up to 8.6 €/kg by increasing the total suspended solids from 5 to 30 g/L, This adjustment aligns the breakeven point of PHBV with the reported average commercial price.

Exploring New Strategies for Optimizing the Production of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from Methane and VFAs in Synthetic Cocultures and Mixed Methanotrophic Consortia.

In this work, the potential of a synthetic coculture and a mixed methanotrophic consortium to synthesize poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) from renewable and waste-based feedstocks was assessed batchwise. Methylocystis parvuscocultivated with Rhodococcus opacus and a Methylocystis-enriched culture previously grown on methane were subjected to nutrient starvation in a medium enriched with valeric acid (30% w w-1 of Ctot) or with a VFAs mixture containing acetic, propionic, butyric, and valeric acids (15% w w-1 of Ctot) under a CH4:O2 or air atmosphere. For all test series, pH was adjusted to 7 after adding the cosubstrates, and a negligible substrate consumption or polymer production was considered the end point of the trial. Results showed that valeric acid promoted PHBV accumulation in both cultures regardless of the atmosphere. Interestingly, the mixture of VFAs supported PHBV accumulation only in the presence of methane. The highest PHBV contents for the coculture and the mixed consortium, equal to 73.7 ± 2.5% w w-1 and 49.6 ± 13% w w-1, respectively, were obtained with methane and the VFAs mixture. This study demonstrates the suitability of cocultures and biobased cosubstrates for the sustainable production of the biodegradable polymer PHBV.

The co-conversion of methane and mixtures of volatile fatty acids into poly(3-hydroxybutyrate-co-3-hydroxyvalerate) expands the potential of an integrated biorefinery.

In this work, the potential of Methylocystis hirsuta to simultaneously use methane and volatile fatty acids mixtures for triggering PHBV accumulation was assessed for the first time batchwise. Biotic controls carried out with CH4 alone confirmed the inability of Methylocystis hirsuta to produce PHBV and achieved 71.2 ± 7 g m-3d-1 of PHB. Pure valeric acid and two synthetic mixtures simulating VFAs effluents from the anaerobic digestion of food waste at 35 °C (M1) and 55 °C (M2) were supplied to promote 3-HV inclusion. Results showed that pure valeric acid supported the highest polymer yields of 105.8 ± 9 g m-3d-1 (3-HB:3-HV=70:30). M1 mixtures led to a maximum of 103 ± 4 g m-3d-1 of PHBV (3-HB:3-HV=85:15), while M2 mixtures, which did not include valeric acid, showed no PHV synthesis. This suggested that the synthesis of PHBV from VFAs effluents depends on the composition of the mixtures, which can be tuned during the anaerobic digestion process.

Sustainable Process for the Production of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from Renewable Resources: A Simulation Study.

Bacterially produced polyhydroxyalkanoates are valuable substitutes for petrochemical plastics, but their current production capacities are very scarce. Producing poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-co-HV) from methane and odd-chain carbon fatty acids could make the production of this biodegradable polymer cost-effective. This study analyzes the main factors affecting methanotrophic growth and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) accumulation, simulating a pilot-scale process based on a double-stage approach. The effects of the nitrogen source and the oxygen partial pressure during a 20 day growth phase were studied; the cosubstrate concentration, the culture selected, and the methane partial pressure were investigated during the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) production stage performed within 15 days under nutrient starvation. Methylocystis parvus OBBP and Methylosinus thricosporum OB3b reached the maximum growth productivities with ammonium as the nitrogen source and oxygen at high partial pressure. The simulation of the PHB-co-HV accumulation revealed that methanotrophs could better accumulate the polymer with low valeric acid concentrations. A methane-abundant gas stream (0.5 atm of methane) could increase process yields up to 0.32 kg m-3 d-1.

Poly(3-hydroxybutyrate) production from methane in bubble column bioreactors: Process simulation and design optimization.

The pressing problem posed by plastic pollution has led to other, environmentally friendly alternatives, such as polyhydroxyalkanoates. This work proposes an innovative process to produce poly(3-hydroxybutyrate) by replacing expensive substrates, such as sugars, with methane. A two-step process was simulated: a first fermentation is performed in a continuous mode for 20 days to grow a strain belonging to the genus Methylocystis, while a second semi-continuous and nitrogen-limited fermentation is employed to induce the poly(3-hydroxybutyrate) accumulation within 12 days. The effects of the superficial gas velocity on the mass transfer and the poly(3-hydroxybutyrate) production yields were evaluated. Several scenarios were analyzed to optimize the geometry of the reactors and the methane utilization. The working volume of the reactors, as well as the presence of gas recycling stream, were shown to affect the global yields positively, while improving the aspect ratio from 8 to 19, with equal volume, lowered the fraction of poly(3-hydroxybutyrate) into the biomass by up to 37.5%.