Kinetic study on methylene blue removal from aqueous solution using UV/chlorine process and its combination with...

This study investigated the kinetic degradation of methylene blue (MB) by a UV/chlorine process and its combination with other advanced oxidation processes. The ∙OH and reactive chlorine species (RCS: Cl∙, ClO∙, etc.) were the primary reactive species, which accounted for 56.7% and 37.6% of MB degradation at pH 7, respectively. The second-order rate constant of Cl∙ towards MB was calculated to be 2.8 × 10⁹ M^-1 s^-1. When the pH increased from 3 to 7, k_MB by ∙OH increased from 0.15 to 0.21 min^-1 before being reduced to 0.11 min^-1 at pH 11. k_MB by RCS continuously reduced from 0.16 to 0.13 min^-1 when the pH was increased to 11. Humic acid (HA), Br^-, and Cl^- inhibited the degradation with k_MB in the order: k_MB (in HA) < k_MB (in Br^-) < k_MB (in Cl^-). HCO₃^- increased k_MB from 0.37 to 0.48 min^-1. The experimental and modeling methods fit well, indicating the effectiveness of using Kintecus® in predicting concentrations of free radicals in complex water matrices. TOC removal was achieved at 60% after 30 min in a control process and it was strongly inhibited by the presence of HA, with 22% removal achieved at 5 mg_c L^-1 HA. UV/chlorine/electrochemical oxidation (UV/chlorine/EO) significantly improves k_MB from 0.37 to 0.94 min^-1 at a high current (240 mA), while UV/chlorine/H₂O₂ decreased k_MB at a low concentration of 0.01 mM H₂O₂ (k_MB decreased by 6.1%). The results indicate that the energy cost for UV irradiation was the main cost in MB treatment in both UV/chlorine and UV/persulfate (UV/PS) processes, accounting for 91% and 84%, respectively.