Journal
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 9, Issue 37, Pages 12575-12583Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.1c03299
Keywords
chemical recycle; recycling; polyhydroxybutyrate (PHB); polyhydroxyalkanoates (PHA); extraction; recovery; solvents; bio-based
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Funding
- Regione Emilia-Romagna (Bando Alte competenze per la ricerca e il trasferimento tecnologico) [2088]
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Two novel protocols were developed for the chemical valorization of polyhydroxybutyrate (PHB), producing methyl 3-hydroxybutyrate (MHB) and methyl 3-methoxybutyrate (MMB), with high purity and excellent molecular weights of extracted PHB.
Two novel protocols for the chemical valorization of polyhydroxybutyrate (PHB) were developed, aiming at the production of two bio-based molecules: methyl 3-hydroxybutyrate (MHB) and methyl 3-methoxybutyrate (MMB). Optimized reaction conditions were applied to pure PHB and PHB inclusions inside bacterial cells as starting materials. MHB was synthesized through a single-step catalytic methanolysis, while MMB was synthesized through a three-step process: thermolytic distillation to give crotonic acid (CA), esterification to give methyl crotonate (MC), and oxa-Michael addition of MeOH. The obtained MHB and MMB were tested as solvents for the recovery of PHB itself both from freeze-dried single strain cultures (SSC) and mixed microbial cultures (MMC) with low to medium contents of PHB (22-57 wt %). High PHB recovery was achieved: up to 96 +/- 1% through MHB and up to 98 +/- 1% through MMB. Extraction from MMC slurry (with a PHB content of 39% on dry weight) was also performed, recovering 77 +/- 2% using MHB and 92 +/- 2% using MMB. High purities and excellent molecular weights and polydispersity indexes of extracted PHB were obtained with both MHB and MMB. Solubility in water, octanol/water partition coefficients (log K-ow), and aerobic ready biodegradability of both solvents were also evaluated.
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