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Advanced Analytical Framework for Pyrolysis Product Characterization and Emission Profiling in Mixed Plastic Waste: Implications for Recycling Strategy
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Analytical pyrolysis combined with comprehensive 2D gas chromatography–mass spectrometry of six polyolefin-rich plastic waste streams reveals aliphatic hydrocarbon-dominated pyrolysates with trace antioxidant-derived non-intentionally added substances (NIAS) but no detectable heavy polycyclic aromatics. This characterization framework is critical for assessing chemical contaminant risks in chemically recycled plastics, directly informing the safety of circular plastic management strategies.
Chemical recycling of mixed plastic waste can return polymers to fuel- and feedstock-range hydrocarbons, but legacy additives and non-intentionally added substances (NIAS) may persist in the products or leach during use. We investigated six polyolefin-rich wastes (P1–P6) by analytical pyrolysis coupled to comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (Py-GC×GC-TOF-MS) and profiled potential emissions from three consumer-grade plastics (P7–P9) via headspace/solvent-extraction GC–MS and water-migration tests. When the plastics were polysized at 650°C, the resulting pyrolysates are dominated by aliphatic hydrocarbons (C₅–C₃₀): n-paraffins and α-olefins for PE-rich feeds, and branched olefins with modest mono-aromatics for PP. Oxygenates are negligible in non-oxidized feeds but persist at low levels in weather-aged HDPE, consistent with carry-through of pre-existing carbonyls; one aged film (P5) shows an epoxide spike (~5–6 area %). Across oils we identify hallmark NIAS from antioxidant packages (e.g., 2,4-di-tert-butylphenol; Irganox®-1010 spiro-dione) at trace to sub-percent levels, while heavy polycyclic aromatics are not detected above method limits. A 3D GC×GC visualization highlights the dense, resolved hydrocarbon envelope and the minor heteroatom features that guide upgrading targets. VOC/SVOC and leachate analyses (P7–P9) reveal mainly low-intensity hydrocarbons, esters, and fragrance/cosmetic residues; no phthalates were detected in the tested samples, although caprolactam and other additive-related NIAS occur sporadically. Collectively, the results indicate that well-sorted polyolefins yield oils suitable for refining to fuels or monomers, but quality assurance should address oxygenate tails in oxidized PE and antioxidant-derived NIAS.
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