Detoxification of oil refining effluents by oxidation of naphthenic acids using TAML catalysts

The environmental problem stemming from toxic and recalcitrant naphthenic acids (NAs) present in effluents from the oil industry is well characterized. However, despite the numerous technologies evaluated for their destruction, their up-scaling potential remains low due to high implementation and running costs. Catalysts can help cutting costs by achieving more efficient reactions with shorter operating times and lower reagent requirements. Therefore, we have performed a laboratory investigation to assess iron-TAML (tetra-amido macrocyclic ligand) activators to catalyze the oxidation of NAs by activating hydrogen peroxide - considered environmentally friendly because it releases only water as by-product - under ultra-dilute conditions. We tested Fe-TAML/H₂O₂ systems on (i) model NAs and (ii) a complex mixture of NAs in oil refining wastewater (RWW) obtained from a refining site in Colombia. Given the need for cost-effective solutions, this preliminary study explores sub-stoichiometric H₂O₂ concentrations for NA mineralization in batch mode and, remarkably, delivers substantial removal of the starting NAs. Additionally, a 72-h semi-batch process in which Fe-TAML activators and hydrogen peroxide were added every 8 h achieved 90-95% removal when applied to model NAs (50 mg L^-1) and a 4-fold reduction in toxicity towards Aliivibrio fischeri when applied to RWW. Chemical characterization of treated RWW showed that Fe-TAML/H₂O₂ treatment (i) reduced the concentration of the highly toxic O₂ NAs, (ii) decreased cyclized constituents in the mixture, and (iii) preferentially degraded higher molecular weight species that are typically resistant to biodegradation. The experimental findings, together with the recent development of new TAML catalysts that are far more effective than the TAML catalysts deployed herein, constitute a foundation for cost-effective treatment of NA-contaminated wastewater.