This work presents a case study of a wastewater treatment plant (WWTP), located in Biscay (Spain), in which the removal of high-occurrence contaminants of emerging concern (CEC) was studied. The existing biological treatment in the WWTP was complemented with a continuous ultrafiltration (c-UF) pilot plant, as a tertiary treatment. Thus, the effect on CEC removal of both treatments could be analyzed globally and after each operation. A total of 39 CEC were monitored, including pharmaceutical products, industrial additives, food additives, herbicides and personal care products. For evaluation of the efficiencies, the removal rates of the biological and of the c-UF treatments, including their variability over a day and a week in relation to the ammonium content, were examined in the influent of the WWTP. In the biological treatment, a wide range of different removal rates was obtained due to the different CEC’s biodegradability and concentration. In UF, lower, but more constant removal rates, were achieved. In addition, the reduction of the general toxicity by the UF treatment in terms of the Microtox® toxicity assay was also evaluated. After UF, all of the samples yielded values of TU50 lower than 1, confirming this result the UF effectiveness for toxicity removal.
In this work, a study of the main operating variables affecting TiO2/UV photocatalysis was carried out. The treatment of an industrial effluent containing aniline and benzothiazole from the manufacture of accelerants for vulcanization was performed in a TiO2-supported commercial photoreactor. The degradation of both contaminants was monitored by GC-MS analysis. The proposed experiments were able to properly identify the phenomenon of adsorption, as well as to improve the performance of the commercial photoreactor by adding small amounts of TiO2 in suspension. The removal performance, durability of the photocatalytic material, and energy costs were analysed. The results showed that the use of suspensions intensifies the degradation obtaining an improvement of 23.15% with respect to the use of the supported catalyst. For an aniline and benzothiazole solution, the best operating conditions were found at pH = 12.0, introducing 60.0 mg L−1 of suspended TiO2 together with the existing supported catalyst.
This work aims to study the sustainable catalytic ozonation of aniline promoted by granular active carbon (GAC) doped with TiO2. Aniline was selected as a model compound for the accelerator manufacturing industries used in the manufacture of rubber due to its environmental impact, low biodegradability, and harmful genotoxic effects on human health. Based on the evolution of total organic carbon (TOC), aniline concentration measured using high performance liquid chromatography (HPLC), pH and ozone concentration in liquid and gas phase, and catalyst loading, a three-phase reaction system has been modelled. The proposed three-phase model related the ozone transfer parameters and the pseudo-first order kinetic constants through three coefficients that involve the adsorption process, oxidation in the liquid, and the solid catalyst. The interpretation of the kinetic constants of the process allowed the predominance of the mechanism of Langmuir–Hinshelwood or modified Eley–Rideal to be elucidated. Seven intermediate aromatic reaction products, representative of the direct action of ozone and the radical pathway, were identified and quantified, as well as precursors of the appearance of turbidity, with which two possible routes of degradation of aniline being proposed.
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