Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathway

In this study, the supercritical water oxidation (SCWO) processes of monochlorophenols (ortho-, meta-, and para-chlorophenol, 2-, 3-, and 4-CP), dichlorophenol (2,4-DCP), and trichlorophenol (2,4,6-TCP) were investigated on the basis of experimental data combined with density functional theory (DFT)...

Full description

Saved in:
Bibliographic Details
Main Authors: Xin Peng, Huiyin Luo, Li Zeng, Zhiwen Cheng, Qingyuan Wang, Bowen Yang
Format: Article
Language:English
Published: Elsevier 2025-04-01
Series:Desalination and Water Treatment
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S1944398625002498
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849734126970601472
author Xin Peng
Huiyin Luo
Li Zeng
Zhiwen Cheng
Qingyuan Wang
Bowen Yang
author_facet Xin Peng
Huiyin Luo
Li Zeng
Zhiwen Cheng
Qingyuan Wang
Bowen Yang
author_sort Xin Peng
collection DOAJ
description In this study, the supercritical water oxidation (SCWO) processes of monochlorophenols (ortho-, meta-, and para-chlorophenol, 2-, 3-, and 4-CP), dichlorophenol (2,4-DCP), and trichlorophenol (2,4,6-TCP) were investigated on the basis of experimental data combined with density functional theory (DFT). SCWO experiments were performed in a coiled tubular reactor at 650–800 K, 24 MPa, and 300 % excess oxygen within 5 min with or without catalysts and/or auxiliary fuels. The results indicated that i) the removal efficiency for trichlorophenol was better than those for dichlorophenol and the monochlorophenols; ii) for the three monochlorophenols, the removal efficiencies were in the order of 4-CP > 2-CP > 3-CP; and iii) the chlorophenol removal efficiency increased in the presence of Cu(II) and isopropyl alcohol (IPA). The Fukui index data supported the experimental findings, which showed that i) Cl atoms in the para-position were more susceptible to radical attack than those in the ortho- and meta-positions; ii) the Fukui values of Cl atom(s) were greater than those of carbon, hydrogen, and oxygen atoms; and iii) 2,4-DCP and 2,4,6-TCP could provide more active sites than the monochlorophenols because they possessed more Cl atoms. On the basis of these results, a pathway for the degradation of chlorophenols involving dechlorination, ring opening, and mineralization was proposed.
format Article
id doaj-art-670d3522a88d4ec0b2796eaff0d1e1b9
institution DOAJ
issn 1944-3986
language English
publishDate 2025-04-01
publisher Elsevier
record_format Article
series Desalination and Water Treatment
spelling doaj-art-670d3522a88d4ec0b2796eaff0d1e1b92025-08-20T03:07:51ZengElsevierDesalination and Water Treatment1944-39862025-04-0132210123310.1016/j.dwt.2025.101233Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathwayXin Peng0Huiyin Luo1Li Zeng2Zhiwen Cheng3Qingyuan Wang4Bowen Yang5Sichuan Provincial Engineering Research Center of City Solid Waste Energy and Building Materials Conversion and Utilization Technology, Chengdu University, Chengdu 610106, China; State Key Laboratory of Subtropical Silviculture, Zhejiang A&F University, Hangzhou, Zhejiang 311300, China; College of Architecture & Environment, Sichuan University, Chengdu 61000, ChinaSichuan Provincial Engineering Research Center of City Solid Waste Energy and Building Materials Conversion and Utilization Technology, Chengdu University, Chengdu 610106, ChinaSichuan Provincial Engineering Research Center of City Solid Waste Energy and Building Materials Conversion and Utilization Technology, Chengdu University, Chengdu 610106, ChinaSchool of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418, ChinaSichuan Provincial Engineering Research Center of City Solid Waste Energy and Building Materials Conversion and Utilization Technology, Chengdu University, Chengdu 610106, China; College of Architecture & Environment, Sichuan University, Chengdu 61000, China; Correspondence to: Chengdu University, 2025 Chengluo Road, Chengdu 610106, China.Sichuan Provincial Engineering Research Center of City Solid Waste Energy and Building Materials Conversion and Utilization Technology, Chengdu University, Chengdu 610106, China; Guangxi Key Laboratory of Environmental Pollution Control Theory and Technology, Guilin University of Technology, Guilin 541004, China; Correspondence to: School of Architecture and Civil Engineering, Chengdu University, 2025 Chengluo Road, Chengdu 610106, China.In this study, the supercritical water oxidation (SCWO) processes of monochlorophenols (ortho-, meta-, and para-chlorophenol, 2-, 3-, and 4-CP), dichlorophenol (2,4-DCP), and trichlorophenol (2,4,6-TCP) were investigated on the basis of experimental data combined with density functional theory (DFT). SCWO experiments were performed in a coiled tubular reactor at 650–800 K, 24 MPa, and 300 % excess oxygen within 5 min with or without catalysts and/or auxiliary fuels. The results indicated that i) the removal efficiency for trichlorophenol was better than those for dichlorophenol and the monochlorophenols; ii) for the three monochlorophenols, the removal efficiencies were in the order of 4-CP > 2-CP > 3-CP; and iii) the chlorophenol removal efficiency increased in the presence of Cu(II) and isopropyl alcohol (IPA). The Fukui index data supported the experimental findings, which showed that i) Cl atoms in the para-position were more susceptible to radical attack than those in the ortho- and meta-positions; ii) the Fukui values of Cl atom(s) were greater than those of carbon, hydrogen, and oxygen atoms; and iii) 2,4-DCP and 2,4,6-TCP could provide more active sites than the monochlorophenols because they possessed more Cl atoms. On the basis of these results, a pathway for the degradation of chlorophenols involving dechlorination, ring opening, and mineralization was proposed.http://www.sciencedirect.com/science/article/pii/S1944398625002498ChlorophenolsSupercritical water oxidationCationsIsopropyl alcoholDensity functional theory
spellingShingle Xin Peng
Huiyin Luo
Li Zeng
Zhiwen Cheng
Qingyuan Wang
Bowen Yang
Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathway
Desalination and Water Treatment
Chlorophenols
Supercritical water oxidation
Cations
Isopropyl alcohol
Density functional theory
title Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathway
title_full Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathway
title_fullStr Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathway
title_full_unstemmed Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathway
title_short Supercritical water oxidation of chlorophenols: Catalytic effect, auxiliary fuels, reaction mechanism, and degradation pathway
title_sort supercritical water oxidation of chlorophenols catalytic effect auxiliary fuels reaction mechanism and degradation pathway
topic Chlorophenols
Supercritical water oxidation
Cations
Isopropyl alcohol
Density functional theory
url http://www.sciencedirect.com/science/article/pii/S1944398625002498
work_keys_str_mv AT xinpeng supercriticalwateroxidationofchlorophenolscatalyticeffectauxiliaryfuelsreactionmechanismanddegradationpathway
AT huiyinluo supercriticalwateroxidationofchlorophenolscatalyticeffectauxiliaryfuelsreactionmechanismanddegradationpathway
AT lizeng supercriticalwateroxidationofchlorophenolscatalyticeffectauxiliaryfuelsreactionmechanismanddegradationpathway
AT zhiwencheng supercriticalwateroxidationofchlorophenolscatalyticeffectauxiliaryfuelsreactionmechanismanddegradationpathway
AT qingyuanwang supercriticalwateroxidationofchlorophenolscatalyticeffectauxiliaryfuelsreactionmechanismanddegradationpathway
AT bowenyang supercriticalwateroxidationofchlorophenolscatalyticeffectauxiliaryfuelsreactionmechanismanddegradationpathway