Massive amounts of plastic waste have been generated over the past several decades, and growing demand will only exacerbate that issue. In particular, polyethylene variants (e.g., LDPE, HDPE) account for over 50% of single-use packaging production and over 30% of all plastic production, but the current, widely-used mechanical recycling methods are insufficient and incapable of handling this volume of waste. Alternatively, a plastic circular economy can be promoted via pyrolysis, a technique in which polymers can be cracked back to their constituent monomers. Using the method of “Pulse-Heated Analysis of Solid Reactions” (PHASR), polyethylene samples were pyrolyzed under isothermal, reaction-controlled conditions, so intrinsic kinetics were measured directly in the absence of secondary reactions and transport limitations. Here, the application of PHASR to LDPE pyrolysis is validated, intrinsic kinetics of LDPE pyrolysis are described via lumped kinetic models, and comparisons are made between these intrinsic kinetics and the apparent kinetics that have been reported in the literature thus far. The fundamental kinetics described herein provide the quantitative basis for developing effective control of the LDPE unzipping process and designing industrially-relevant polyolefin pyrolysis reactors.

Promoting a plastic circular economy via pulse-heated analysis of solid reactions (PHASR): Intrinsic kinetic insights from polyethylene pyrolysis

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ACS Fall 2022

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