Determining the kinetic constants leading to mineralization of dilute carbamazepine and estradiol-containing solutions under continuous supercritical water oxidation conditions

J Hazard Mater. 2022 Jan 15:422:126797. doi: 10.1016/j.jhazmat.2021.126797. Epub 2021 Aug 2.

Abstract

Continuous subcritical and supercritical water oxidation experiments were conducted on dilute carbamazepine- and estradiol-containing synthetic solutions used to simulate the removal of model emerging pollutants from secondary municipal effluents. The operating conditions comprised 340-500 °C, retention time of 24-453 s and a stoichiometric oxidant ratio (O.C.) between 4 and 64. The transformation of the various species was determined at the outlet and by modeling a segmented non-isothermal reaction system. Four empirical power law kinetic models were established to represent both the pollutants' degradation and TOC removal efficiencies, using nonlinear multiple regression coupled with bootstrapping and K-fold cross-validation. The mineralization and degradation models for both pollutants yielded a R2 of 67-80.5% vs. the experimental results. Discussion on the various model assumptions revealed that attributing full model deviations to the constant oxygen concentration or to the laminar reactor flow, yielded a deviation of 6% and 15% in the removal efficiencies, respectively. However, the expected deviation of the models was lower than 0.32% at conditions leading to (almost) full mineralization (45-60 s, 480-500 °C and O.C.s of 5-10). The methodologies developed in the study are useful for interpreting future results obtained from SCWO of actual secondary effluent solutions.

Keywords: 17β-Estradiol; Carbamazepine; Effluent RO retentate; SCWO.

MeSH terms

  • Carbamazepine
  • Estradiol
  • Kinetics
  • Oxidation-Reduction
  • Water
  • Water Pollutants, Chemical* / analysis
  • Water Purification*

Substances

  • Water Pollutants, Chemical
  • Water
  • Carbamazepine
  • Estradiol