Recovering Valuable Chemicals from Polypropylene Waste via a Mild Catalyst-Free Hydrothermal Process.

Waste polypropylene (PP) presents a significant environmental challenge, owing to its refractory nature and inert C-C backbone. In this study, we introduce a practical chemical recovery strategy from PP waste using a mild catalyst-free hydrothermal treatment (HT). The treatment converts 64.1% of the processed PP into dissolved organic products within 2 h in an air atmosphere at 160 °C. Higher temperatures increase the PP conversion efficiency. Distinct electron absorption and emission characteristics of the products are identified by spectral analysis. Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) reveals the oxidative cracking of PP into shorter-chain homologues (10-50 carbon atoms) containing carboxylic and carbonyl groups. Density functional theory (DFT) calculations support a reaction pathway involving thermal C-H oxidation at the tertiary carbon sites in the polymer chain. The addition of 1% HO further enhances the oxidation reaction to produce valuable short-chain acetic acids, enabling gram-scale recycling of both pure PP and disposable surgical masks from the real world. Techno-economic analysis (TEA) and environmental life cycle costing (E-LCC) analysis suggest that this hydrothermal oxidation recovery technology is financially viable, which shows significant potential in tackling the ongoing plastic pollution crisis and advancing plastic treatment methodologies toward a circular economy paradigm.