A thorough observation of an ozonation catalyst under long-term practical operation: Deactivation mechanism and regeneration

Heterogeneous catalytic oxidation, as an efficient advanced treatment technology, has been gradually applied in industrial wastewater treatment. The fixed bed technique is one of the most popular catalytic ozonation methods. However, few studies have concentrated on the long-term operation effects on catalysts. In this study, we conducted long-term (~5 years) observations of the operation of the largest petrochemical wastewater treatment plant (treatment capacity 120,000 m³/d) with catalytic ozonation technology in China. A commercial catalyst, which uses Al₂O₃ pellets supporting copper oxide was applied in this plant. The results showed that the catalytic efficiency gradually decreased from 60.65% to 25.98% since 2018, and the ozone dosage to COD removal ratio (ozone/COD) also increased from 0.82 to 1.93 mg/mg as the running time continued. By means of the comparison and characterization of fresh catalyst and used catalyst, a “mucus layer” was formed by the adsorption of negatively charged extracellular polymeric substances on the positively charged catalyst surface and the interception of the catalyst layer. The mucus layer significantly reduced the catalytic efficiency by isolating ozone with catalytic active sites and releasing extra organic contaminants during the catalytic process resulting in 53.97% TOC increase in the batch test. Meanwhile, regeneration experiments revealed that the TOC removal efficiency was 4.76% and 43.48% in presence of washed catalysts and calcinated catalysts, respectively. Compared with the fresh catalyst, 73% of the catalytic activity was recovered for calcinated catalyst. Consequently, this study provides much practical information, showing positive effects on the promotion of catalytic ozonation application in actual wastewater treatment.