RESUMO
Ferromanganese oxide (MFOx) was first utilized to functionalize TiO2 and an MFOx@TiO2 catalyst was developed for catalytic ozonation for rapid attack of pharmaceutical and personal care products (PPCPs) with adjusted reactive oxygen species (ROSs) composition and strengthened ROSs generation. Unlike Al2O3, which strongly relied on adsorption and was significantly influenced by MFOx loading, synergistic catalytical effects of MFOx and TiO2 were observed, and optimal MFOx doping of 2 wt% and MFOx@TiO2 dosage of 500 ppm were obtained for catalyzing ozonation. In ibuprofen (IBP) degradation, MFOx@TiO2-catalyzed ozonation (MFOx@TiO2/O3) obtained 2.0-, 4.7- and 6.9-folds the kobs of TiO2/O3, MFOx/O3 and bare ozonation (B/O3). Stronger O3 decomposition was observed by MFOx@TiO2 over bare TiO2 with the participation of redox pairs Fe(II)/Fe(III) and Mn(II)/Mn(III)/Mn(IV) and increased surface oxygen vacancies (SOVs) from 9.8 % to 33.7 % was detected. The results revealed that Fe(II), Mn(II) and Mn(III) with low valance accelerated Ti(III) generation from Ti(VI), obtaining an unprecedented high Ti(III) composition occupying 35.3 % of the total Ti atoms. Ti(III) catalyzed the direct reduction of SOVs-O2 to â¢O2-, and it accelerated the formation of Ti(VI)-OH and Ti(VI)-O which catalyzed O3 decomposition into â¢O2-. â¢O2- was found to primarily initiate IBP degradation with nucleophilic addition and dominated over 66 % IBP removal. The enhanced â¢O2- generation further strengthened â¢OH and 1O2 production. MFOx@TiO2/O3 obtained 17 %, 21 % and 30 % higher TOC removal over TiO2/O3, MFOx/O3 and B/O3, respectively. Acute toxicity tests confirmed the effective toxicity control of organics by MFOx@TiO2/O3 process (inhibition rate: 10.9 %). Degradation test of atenolol and sulfamethoxazole confirmed the catalytic effects of MFOx@TiO2. MFOx@TiO2 performed strong resistance to water matrix in application test and showed good stability and reusability. The study proposed an effective catalyst for strengthening the ozonation process on PPCPs degradation and provided an in-depth understanding of the mechanisms and characteristics of the MFOx@TiO2 catalyst and MFOx@TiO2/O3 process.
Assuntos
Oxirredução , Ozônio , Espécies Reativas de Oxigênio , Titânio , Poluentes Químicos da Água , Ozônio/química , Catálise , Titânio/química , Espécies Reativas de Oxigênio/química , Poluentes Químicos da Água/química , Óxidos/químicaRESUMO
Petrochemical wastewater contains inhibitory compounds such as aromatics that are toxic to microorganisms during biological treatment. The compact and layered structure and the high amount of extracellular polymeric substances (EPS) in aerobic granular sludge (AGS) can contribute to protecting microorganisms from the harsh environment. This study evaluated the changes in the granule properties, pollutants removal, microbial metabolic potential and molecular microbial characteristics of the AGS process for petrochemical wastewater treatment. Granules treating petrochemical wastewater had a higher SVI30/SVI5 value (0.94) than that treating synthetic wastewater. An increase in bioactivity and EPS secretion with higher bio-polymer composition, specifically the functional groups such as hydroxyl, alkoxy and amino in protein, was observed, which promoted biomass aggregation. The granules also had more than 2-fold higher specific oxygen utilization rate. The AGS-SBR process obtained an average COD removal of 93% during petrochemical wastewater treatment and an effluent bCOD of below 1 mg L-1. No obvious inhibition of nitrification and denitrification activity was observed in the processes attributed to the layered structure of AGS. The average effluent NH4+-N of 5.0 mg L-1 was obtained and TN removal efficiencies of over 80.0% was achieved. Molecular microbial analysis showed that abundant functional genera Stenotrophomonas and Pseudoxanthomonas contributed to the degradation of aromatics and other petroleum organic pollutants. They were enriched with the variation of group behavior while metabolisms of amino acids and carboxylic acids by the relevant functional genera (e.g., Cytophagia) were significantly inhibited. The enrichment of Flavobacterium and Thermomonas promoted nitrification and denitrification, respectively. This research revealed the rapid start-up, enhanced granule structural strength, high inhibition resistance and considerable performance of AGS-SBR for petrochemical wastewater treatment.