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Overevaluation of Electro-oxidation for Chemical Oxygen Demand Removal Using a Boron-Doped Diamond Anode - The Roles of Various Electrogenerated Oxychlorides and Countermeasure

MetadataDetails
Publication Date2023-01-09
JournalACS ES&T Engineering
AuthorsHuiji Xiao, Yongjie Hao, Jinghua Chen, Fei Feng, Yijie Liu
InstitutionsQingdao University of Technology, Shandong Academy of Environmental Science
Citations12

Electrochemical oxidation using a boron-doped diamond (BDD) anode has been extensively investigated in various wastewater treatments, where the electrogenerated oxychlorides (ClOx-, x = 1 to 4) from Cl- oxidation have been well illustrated. However, the false chemical oxygen demand (COD) reduction induced by ClOx- adulteration has been almost completely overlooked when evaluating the electrochemical wastewater treatment performance. In this study, it was revealed that all the ClOx- species except ClO4- served as strong oxidants in lieu of dichromate to degrade organic matter under digestion conditions during the COD test procedure. To eliminate the interference of ClOx- mixtures on the assessment of electrochemical COD removal performance, the modified sulfite-based reduction method was developed for the electrochemical case to remove ClOx- mixtures from the BDD-treated water samples before the COD test. It was demonstrated that the unadulterated COD removal performance of the BDD-based electrochemical system used for both synthetic and real wastewater treatments could be obtained after sulfite-based reduction of the electrogenerated ClOx- mixtures within 30 min in a sealed reaction chamber with the molar [sulfite]ini/[ClOx-]ini ratio of 1-3, where the reactants were isochronously depleted without producing oxidative radicals (SO4•- and •OH). Due to extreme lack of oxygen in the sealed ClOx—sulfite system, radical propagation reactions were terminated and ClOx- constituents (ClO3-, ClO2-, and ClO-) were reduced by sulfite stoichiometrically via the oxygen transfer process with Cl- and SO42- as the final products. This new sulfite-based protocol could be regarded as a robust and adulteration-proof countermeasure for evaluating the real COD removal performance of an electrochemical system.

  1. 1996 - PRC (MEEC) Integrated wastewater discharge standard (GB 8978-1996)