Fast degradation of diclofenac by catalytic hydrodechlorination.

Aqueous-phase catalytic hydrodechlorination (HDC) has been scarcely explored in the literature for the removal of chlorinated micropollutants. The aim of this work is to prove the feasibility of this technology for the fast and environmentally-friendly degradation of such kind of compounds. Diclofenac (DCF), a highly consumed anti-inflammatory drug, has been selected as the target pollutant given its toxicity and low biodegradability. The commercial Pd/Al2O3 (1% wt.) catalyst has been used due to its prominent role on this field. Complete degradation of DCF was achieved in a short reaction time (20 min) under ambient conditions (25 °C, 1 atm) at [DCF]0 = 68 μM; [Pd/Al2O3]0 = 0.5 g L-1 and H2 flow rate of 50 N mL min-1. Remarkably, the chlorinated intermediate (2-(2-chloroanilino)-phenylacetate (Cl-APA)) generated along reaction was completely removed at the same time, being the chlorine-free compound 2-anilinophenylacetate (APA) the only final product. A reaction scheme based on this consecutive pathway and a pseudo-first-order kinetic model have been proposed. An apparent activation energy of 43 kJ mol-1 was obtained, a comparable value to those previously reported for conventional organochlorinated pollutants. Remarkably, the catalyst exhibited a reasonable stability upon three successive uses, achieving the complete degradation of the drug and obtaining APA as the final product in 30 min. The evolution of ecotoxicity was intimately related to the disappearance of the chlorinated organic compounds and thus, the final HDC effluents were non-toxic. The versatility of the system was finally demonstrated in different environmentally-relevant matrices (wastewater treatment plant effluent and surface water).