Fe-Mn doped powdered activated carbon pellet as ozone catalyst for cost-effective phenolic wastewater treatment: Mechanism studies and phenol by-products elimination.

A novel bimetallic doped PAC (Fe-Mn/PAC) pellet was prepared with a facile sol-gel method and used as an ozone catalyst for phenolic wastewater (PWW) treatment. Adoption of Fe-Mn/PAC pellet in microbubble ozonation enhanced the 1-h chemical oxygen demand (COD) and phenol removal in PWW to 79% and 95%, respectively. With ozone dosage of 10 mg/L, 1 g/L Fe-Mn/PAC pellet exhibited ozone conversion of 92%. In comparison to microbubble ozonation process, Fe-Mn/PAC induced microbubble-catalytic ozonation process promoted ozone decomposition rate by 1.9 times. In terms of •OH production, Fe-Mn/PAC pellet enhanced •OH exposure by 10 times, with a Rct value of 2.92 × 10 -8. Rct kinetic model also suggested that Fe-Mn/PAC pellet obtained higher kinetic rate constants for initiating and promoting •OH generation. Usage of Fe-Mn/PAC pellet in microbubble ozonation for phenolic wastewater treatment also reduced the total ozone consumption by 70%. In Fe-Mn/PAC induced microbubble-catalytic ozonation process, the ratio between ozone consumption and COD removal (ΔO3/ΔCOD) was 0.91. Fe-Mn/PAC pellet characterization with X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) and X-ray powder diffraction (XRD) analysis revealed successful doping of Fe-Mn on PAC substrate and larger numbers of carbon-oxygen/hydroxyl surface groups, which played key roles in ozone decomposition and •OH production.

Organics removal in high strength petrochemical wastewater with combined microbubble-catalytic ozonation process.

Ozonation is a well-known and widely applied advanced oxidation process (AOP) for industrial wastewater treatment, while the ozonation efficiency might be limited by low mass transfer, poor solubility, and rapid decomposition rate of ozone molecules in the aqueous phase. The present study aims to investigate the feasibility of combined microbubble-catalytic ozonation process (M-O3/Fe/GAC) for improving the ozonation efficiency during treatment of petrochemical wastewater (PCW). M-O3/Fe/GAC process optimization was carried out with different pH conditions, ozone dosages and catalyst loadings. The optimum operating conditions were identified as 50 mg L-1 ozone dosage, real PCW pH (7.0-7.5) and 4 g L-1 catalyst loading. Among different ozonation processes, M-O3/Fe/GAC process achieved the highest chemical oxidation demand (COD) removal efficiency of 88%, which is 18% and 43% higher than those achieved by the microbubble and macrobubble ozonation processes, respectively. Phenolic compounds presented in PCW could be reduced by 63% within 15 min in M-O3/Fe/GAC treatment process. Long-term continuous flow studies suggested M-O3/Fe/GAC process to be the most cost-effective technology for PCW treatment with an operating cost of S$0.18 kg-1 COD and S$0.4 m-3 with good catalyst stability. Liquid size exclusion chromatography with organic carbon detection (LC-OCD) data suggested humic substances to be the dominant organic species in PCW, M-O3/Fe/GAC could achieve significant humic substances removal and biodegradability enhancement in PCW. Kinetics and mechanism studies revealed that organics removal in M-O3/Fe/GAC was 1.8 times higher than that in microbubble ozonation process, and hydroxyl radical (●OH) was the dominant oxidant specie for organics removal in M-O3/Fe/GAC process.

Reverse osmosis concentrate treatment by microbubble ozonation-biological activated carbon process: Organics removal performance and environmental impact assessment.

Reverse osmosis (RO) is being used in many water reclamation facilities to produce high quality water that can be reused for different purposes. As a part of the RO process, a reject stream is produced as the reverse osmosis concentrate (ROC), which contains elevated levels of contaminants compared to the source water. Effective treatment and safe disposal of ROC via cost-effective means is very challenging. This study aims to develop a robust microbubble ozonation-biological process for industrial ROC treatment with a target effluent chemical oxygen demand (COD) lower than 60 mg/L. As compared to macrobubble ozonation, microbubble ozonation exhibited better ozone dissolution and 29% higher COD removal efficiency with the same ozone dosage. Under the optimum operating conditions with ozone dosage of 30 mg/L, ROC natural pH of 8.67 and ozonation duration of 1 h, microbubble ozonation achieved 42% COD removal efficiency while increasing the BOD5/COD ratio (ratio of biological oxygen demand over 5 days to the corresponding chemical oxygen demand) in ROC from 0.042 to 0.216. A biological activated carbon (BAC) column with an empty bed contact time (EBCT) of 120 min was combined with microbubble ozonation for continuous ROC treatment. Over the 100-day operation, the combined system performed consistent organics removal with an average effluent COD of 45 mg/L. Both LC-OCD data and fluorescence EEM spectra confirmed humic substances were the dominant organic species in ROC. Ozone pre-treatment could achieve significant removal of humic substances in raw ROC. ATP analysis found that ozone pre-treatment enhanced BAC biofilm activity by around 5 folds. 5 min acute toxicity assessment with Aliivibrio fischeri showed 4 times reduction of bioluminescence inhibition in ozone treated ROC. From the environmental point of view, Life cycle assessment (LCA) results demonstrated that Ozone-BAC system had significant environmental burdens on climate change and human toxicity due to the electricity production process. These environmental impacts can be mitigated by optimizing the ozonation process with reduced ozone dosage or utilizing renewable energy sources for electricity generation.