Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC

Wu, Jiayang; Papanikolaou, Konstantinos G.; Cheng, Feng; Addison, Bennett; Cuthbertson, Amy A.; Mavrikakis, Manos; Huber, George W.

doi:10.1021/acssuschemeng.4c00564

Title: Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC

Journal Article · 29 April 2024 · ACS Sustainable Chemistry & Engineering

DOI: https://doi.org/10.1021/acssuschemeng.4c00564 · OSTI ID:2352421

Wu, Jiayang ^[1];

^[1]; Cheng, Feng ^[1]; Addison, Bennett ^[2]; Cuthbertson, Amy A. ^[2];

^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)

In this paper, we study the kinetics of polyvinyl chloride (PVC) decomposition using a combination of experimental and computational approaches. Here, we develop a simplified kinetic model that contains only two steps: dehydrochlorination of PVC and further decomposition of the PVC residue. The model is consistent with density functional theory (DFT) calculations and experimental data. Dehydrochlorination is an autocatalytic reaction that starts with a tertiary chloride (Cl) and generates hydrogen chloride (HCl) and benzene as the main products. Benzene and HCl formation rates showed similar trends, indicating that HCl likely catalyzes a homolytic carbon-carbon (C-C) bond cleavage, which gives rise to benzene and an aliphatic fragment. We characterized the structure of dehydrochlorinated PVC (PVC residue) by using thermal gravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). FTIR and NMR results indicate that the PVC residue contains 20% quaternary carbon content, indicating a high concentration of cross-linked molecules. We predict that the most probable structure in the cross-linked centers of the PVC residue is cyclohexadiene, which is supported by DFT calculations, FTIR, and NMR.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; AC36-08GO28308; EE0009285

OSTI ID:: 2352421

Report Number(s):: NREL/JA--2800-89924; MainId:90703; UUID:6b56b290-bf5e-4e88-9e3a-833131d62eb8; MainAdminId:72619

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 19 Vol. 12; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC

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