Catalytic and non-catalytic degradation of acetaminophen in supercritical water

Pharmaceutical industrial wastewater is typical wastewater consisting of complex organic compounds with higher concentration, microbial toxicity, strenuous to deteriorate, and environmental threatening. The present work assesses the degradation of recalcitrant acetaminophen (ACM) by a green technology known as supercritical water oxidation (SCWO). Experiments were carried out in a continuous flow SCWO reactor by altering reaction conditions such as temperature 400-600 °C, oxidant coefficient (OC 0 to 3), and Fe(II) catalyst concentration (0.5 and 1 mg L^-1) to study the technical feasibility of highly concentrated ACM. Liquid product analysis indicated the total organic carbon (TOC) removal efficiency could reach up to 99.5% without catalyst at 600 °C and 99.9% with Fe(II) at 500 °C. The addition of Fe not only suppressed the intermediate ring components but also promoted the formation of permanent gases via decarboxylation and reforming reactions. The reaction between Fe(II) and H₂O₂ in supercritical water is extremely fast, which has a direct impact on the system's operating conditions. The high activity exhibited by Fe(II) catalyst degraded the ACM completely at an operating condition of 500 °C. Maximum H₂ fraction was attained without catalyst at 600 °C, OC 0.5, and with the catalyst at 500 °C, respectively, whereas, CO₂ tends to rise significantly with both temperature and oxidant concentration. The catalytic process is efficient in comparison to the non-catalytic process. A possible reaction pathway was proposed based on the intermediates generated during the degradation.