Electrocoagulation (EC) is one of the most effective processes for highly emulsified oily wastewater (HEOW) treatment. However, the demulsification efficiency depends on the amount of aluminum or iron ions released from the conventional sacrificial metal anode, leading to challenges such as rapid anode dissolution and short lifespan. To address these issues, this study presents a novel electrolysis-enhanced coagulation (EEC) process, replacing conventional Al electrodes with dimensionally stable titanium anodes coated with ruthenium-iridium oxide and supplementing the electrochemically released Al³+ with externally added AlCl3.This process was assessed using the Turbiscan LAB Expert to measure the variation in floc diameter under various electrolysis times, AlCl3 concentrations, and current densities. At a current density of 5 mA/cm2 and AlCl3 dosage of 50 mg/L, the mean floc diameter increased from 32.4 ± 1.7 µm to 630.3 ± 76.9 µm as the electrolysis time extended from 0 to 4 min. Under optimal conditions, the oil removal efficiency of 96.7%±0.2% and residual oil concentration in the effluent of 66.3 ± 3.5 mg/L were achieved. The energy consumption of this process was 0.17 kWh/m³, which was a relatively low value compared with conventional EC techniques. Moreover, as electrolysis time increased, a greater proportion of dissolved and suspended Al transformed into species incorporated within the floating oil. These findings demonstrate the potential of the EEC process to replace EC in treating HEOW, providing an effective and durable solution.
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