Mechanisms of Electrochemical Degradation of Low-Concentration Azo Dye Wastewater by a Typical Binary Anion System

The secondary effluent from printing and dyeing wastewater contains recalcitrant organic pollutants, such as azo dye derivatives. Their persistence in aquatic environments not only creates ecological risks but also hampers the high-value reuse of reclaimed water. This study investigated the influence of typical binary anions on the degradation performance of low-concentration azo dye wastewater using a Ti/RuO2-IrO2 anode electrochemical oxidation system. The results demonstrated that maximum COD removal efficiency could reach 50.22%, and the controlling factors synergistically regulated the contribution and competition between Reactive Chlorine Species and free radicals. This led to a characteristic “rapid rise–decline–slow rebound” phenomenon in the COD removal rate, with the inflection points co-influenced by the current density, conductivity, and binary anion ratio of the electrochemical process. Furthermore, it alters the degradation pathway of the azo dye to “azo bond cleavage → demethylation/desulfonation → dehydroxylation/deamination oxidation → benzene ring opening”. Within a fixed duration of 60 min, the Response Surface Methodology model identified the optimal COD degradation conditions as follows: current density of 19.72 mA/cm2, Cl−/SO42− ratio of 5.40, and conductivity of 8.30 mS/cm. This research elucidates the differences between the electrochemical oxidation degradation pathway of low-concentration azo dye wastewater under the regulation of typical binary anions and the conventional pathway. It also reveals the regulatory effects of current density, conductivity, and binary anion ratio on the degradation patterns.