Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants
Co-pyrolysis of brominated flame retardants (BFRs) with polymeric materials prevails in scenarios pertinent to thermal recycling of bromine-laden objects; most notably the non-metallic fraction in e-waste. Hydro-dehalogenation of aromatic compounds in a hydrogen-donating medium constitutes a key ste...
| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2020
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| Online Access: | http://psasir.upm.edu.my/id/eprint/88271/ http://psasir.upm.edu.my/id/eprint/88271/1/ABSTRACT.pdf |
| _version_ | 1848860589496991744 |
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| author | Altarawneh, Mohammednoor Ahmed, Oday H. Al-Harahsheh, Mohammad Jiang, Zhong Tao Nay, Ming Huang Lim, Hong Ngee Dlugogorski, Bogdan Z. |
| author_facet | Altarawneh, Mohammednoor Ahmed, Oday H. Al-Harahsheh, Mohammad Jiang, Zhong Tao Nay, Ming Huang Lim, Hong Ngee Dlugogorski, Bogdan Z. |
| author_sort | Altarawneh, Mohammednoor |
| building | UPM Institutional Repository |
| collection | Online Access |
| description | Co-pyrolysis of brominated flame retardants (BFRs) with polymeric materials prevails in scenarios pertinent to thermal recycling of bromine-laden objects; most notably the non-metallic fraction in e-waste. Hydro-dehalogenation of aromatic compounds in a hydrogen-donating medium constitutes a key step in refining pyrolysis oil of BFRs. Chemical reactions underpinning this process are poorly understood. Herein, we utilize accurate density functional theory (DFT) calculations to report thermo-kinetic parameters for the reaction of solid polyethylene, PE, (as a surrogate model for aliphatic polymers) with prime products sourced from thermal decomposition of BFRs, namely, HBr, bromophenols; benzene, and phenyl radical. Facile abstraction of an ethylenic H by Br atoms is expected to contribute to the formation of abundant HBr concentrations in practical systems. Likewise, a relatively low energy barrier for aromatic Br atom abstraction from a 2-bromophenol molecule by an alkyl radical site, concurs with the reported noticeable hydro-debromination capacity of PE. Pathways entailing a PE-induced bromination of a phenoxy radical should be hindered in view of high energy barrier for a Br transfer into the para position of the phenoxy radical. Adsorption of a phenoxy radical onto a Cu(Br) site substituted at the PE chain affords the commonly discussed PBDD/Fs precursor of a surface-bounded bromophenolate adduct. Such scenario arises due to the heterogeneous integration of metals into the bromine-rich carbon matrix in primitive recycling of e-waste and their open burning. |
| first_indexed | 2025-11-15T12:47:38Z |
| format | Article |
| id | upm-88271 |
| institution | Universiti Putra Malaysia |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-15T12:47:38Z |
| publishDate | 2020 |
| publisher | Elsevier |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | upm-882712022-11-24T04:40:18Z http://psasir.upm.edu.my/id/eprint/88271/ Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants Altarawneh, Mohammednoor Ahmed, Oday H. Al-Harahsheh, Mohammad Jiang, Zhong Tao Nay, Ming Huang Lim, Hong Ngee Dlugogorski, Bogdan Z. Co-pyrolysis of brominated flame retardants (BFRs) with polymeric materials prevails in scenarios pertinent to thermal recycling of bromine-laden objects; most notably the non-metallic fraction in e-waste. Hydro-dehalogenation of aromatic compounds in a hydrogen-donating medium constitutes a key step in refining pyrolysis oil of BFRs. Chemical reactions underpinning this process are poorly understood. Herein, we utilize accurate density functional theory (DFT) calculations to report thermo-kinetic parameters for the reaction of solid polyethylene, PE, (as a surrogate model for aliphatic polymers) with prime products sourced from thermal decomposition of BFRs, namely, HBr, bromophenols; benzene, and phenyl radical. Facile abstraction of an ethylenic H by Br atoms is expected to contribute to the formation of abundant HBr concentrations in practical systems. Likewise, a relatively low energy barrier for aromatic Br atom abstraction from a 2-bromophenol molecule by an alkyl radical site, concurs with the reported noticeable hydro-debromination capacity of PE. Pathways entailing a PE-induced bromination of a phenoxy radical should be hindered in view of high energy barrier for a Br transfer into the para position of the phenoxy radical. Adsorption of a phenoxy radical onto a Cu(Br) site substituted at the PE chain affords the commonly discussed PBDD/Fs precursor of a surface-bounded bromophenolate adduct. Such scenario arises due to the heterogeneous integration of metals into the bromine-rich carbon matrix in primitive recycling of e-waste and their open burning. Elsevier 2020 Article PeerReviewed text en http://psasir.upm.edu.my/id/eprint/88271/1/ABSTRACT.pdf Altarawneh, Mohammednoor and Ahmed, Oday H. and Al-Harahsheh, Mohammad and Jiang, Zhong Tao and Nay, Ming Huang and Lim, Hong Ngee and Dlugogorski, Bogdan Z. (2020) Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants. Chemosphere, 254. art. no. 126766. pp. 1-9. ISSN 0045-6535; ESSN: 1879-1298 https://www.sciencedirect.com/science/article/pii/S0045653520309590 10.1016/j.chemosphere.2020.126766 |
| spellingShingle | Altarawneh, Mohammednoor Ahmed, Oday H. Al-Harahsheh, Mohammad Jiang, Zhong Tao Nay, Ming Huang Lim, Hong Ngee Dlugogorski, Bogdan Z. Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants |
| title | Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants |
| title_full | Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants |
| title_fullStr | Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants |
| title_full_unstemmed | Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants |
| title_short | Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants |
| title_sort | co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants |
| url | http://psasir.upm.edu.my/id/eprint/88271/ http://psasir.upm.edu.my/id/eprint/88271/ http://psasir.upm.edu.my/id/eprint/88271/ http://psasir.upm.edu.my/id/eprint/88271/1/ABSTRACT.pdf |