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Abstract: Calibration of kinetic models of wet air oxidation (WAO) is usually performed through minimisation algorithms with respect to total organic carbon (TOC) experimental data. However, the reliability of the estimated value of the kinetic parameters is frequently not reported. Moreover, the influence of data quantity/quality in the kinetic parameters identifiability is not properly assessed. The objective of this study is to compare the calibration goodness of a proposed kinetic model when using one set of data (total effluent TOC [TOCeff]) or two sets of independent experimental measurements (total effluent TOC [TOCeff] and residual TOC of target pollutant [TOC[A]]). The systematic comparison was made using identifiability analysis with contour plots of both objective functions and the confidence intervals were calculated through the Fisher information matrix (FIM). The experimental data used in this study comes from a previous one, where WAO was investigated as a suitable precursor for the biological treatment of industrial wastewater containing high concentrations of o-cresol or 2-chlorophenol [M.E. Suárez-Ojeda, J. Carrera, I.S. Metcalfe, J. Font, Wet air oxidation (WAO) as a precursor to biological treatment of substituted phenols: refractory nature of the WAO intermediates, Chem. Eng. J. 144 (2008) 205–212.]. The results show that the model correctly fitted the experimental [TOCeff] in all cases with less than 6% as averaged relative deviation, either using one set of data ([TOCeff]) or two sets of independent experimental measures ([TOCeff] and [TOC[A]]) in the objective function. However, when using only [TOCeff], the model was not capable of fitting the proportion between [TOC[A]] and intermediates TOC. The obtained E ACT for the calibration made with [TOCeff] and [TOC[A]] were 71±20kJmol−1 (R 2 =0.92) and 47±9kJmol−1 (R 2 =0.96) for o-cresol and 2-chlorophenol, respectively. However, when using just [TOCeff], the obtained E ACT values were not in the range of the values reported in the literature and had smaller regression coefficients. Moreover, the calibration with just [TOCeff] presented a high correlation between the obtained rate constants, whereas the calibration with [TOCeff] and [TOC[A]] was statistically more reliable. As example, the D-criterion values are three to six times larger for the calibration made with ([TOCeff] and [TOC[A]] than for the calibration made only with [TOCeff], in the framework of OED/PE criteria, this is related to minimisation of the geometric mean of the identification errors. [Copyright &y& Elsevier]

Abstract: Wet air oxidation (WAO) was investigated as a suitable precursor for the biological treatment of industrial wastewaters that contained high concentrations of phenol, o-cresol or 2-chlorophenol. Two hours WAO semi-batch experiments were conducted at 2 and 9bar of oxygen partial pressure () and at 215, 240 and 265°C with total organic carbon (TOC) abatement up to 86%. The influence of hydroxyl-, methyl- and chloride ring substitution on the oxidation mechanism of aromatic compounds was established. Also, the readily biodegradable COD fraction (%CODRB) of the WAO effluents was found by respirometric techniques. The maximum %CODRB was 24% for phenol WAO at 265°C and 9bar of , 10% for o-cresol WAO at 265°C and 9bar of and 19% for 2-chlorophenol WAO at 215°C and 2bar of . These results allow comparison of whether or not the WAO effluents were suitable for a conventional activated sludge plant with non-acclimated biomass. Also, the results were compared to those obtained from a previous study for the same model compounds but using catalytic WAO (CWAO) with activated carbon (AC) as a catalyst [1]. This comparison allows us to establish whether or not the WAO effluents were less biodegradable or had more refractory intermediates than CWAO effluents. [Copyright &y& Elsevier]

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure () and at 180, 200 and 220°C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and were 140–160°C and 2–9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160°C and 2 bar of , which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (CODRB) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture. [Copyright &y& Elsevier]