Heterogeneous photocatalysis using TiO2 modified with hydrotalcite and iron oxide under UV–visible irradiation for color and toxicity reduction in secondary textile mill effluent

Abstract

The objective of this study was to evaluate ADMI color removal from a biologically treated textile mill effluent by heterogeneous photocatalysis with UV–visible irradiation (UV–vis) using a novel catalyst composed of TiO2 supported on hydrotalcite and doped with iron oxide (HT/Fe/TiO2). Simulated biological treatment of solutions of the dyes (50 mg/L) used in the greatest amounts at the mill where the textile effluent was collected resulted in no color removal in reactive dye solutions and about 50% color removal in vat dye solutions, after 96 h, indicating that the secondary effluent still contained a large proportion of anionic reactive dyes. Photocatalytic treatments were carried out with TiO2 and HT/Fe/TiO2 of Fe:Ti molar ratios of 0.25, 0.5, 0.75 and 1, with varying catalyst doses (0–3 mg/L), initial pH values (4–10) and UV–vis times (0–6 h). The highest ADMI color removal with unmodified TiO2 was found at a dose of 2 g/L and pH 4, an impractical pH value for industrial application. The most efficient composite was HT/Fe/TiO2 1 at pH 10, also at a dose of 2 g/L, which provided more complete ADMI color removal, from 303 to 9 ADMI color units (96%), than unmodified TiO2, from 303 to 37 ADMI color units (88%), under the same conditions. Hydroxyl radicals were responsible for the color reduction, since when 2-propanol, an OH scavenger, was added color removal was very low. For this reason, the HT/Fe/TiO2 1 composite performed better at pH 10, because the higher concentration of hydroxide ions present at higher pH favored hydroxyl radical formation. COD reductions were relatively low and similar, approximately 20% for both catalysts after 6 h under UV–vis, because of the low initial COD (78 mg/L). Secondary effluent toxicity to Daphnia similis (EC50 = 70.7%) was reduced by photocatalysis with TiO2 (EC50 = 95.0%) and the HT/Fe/TiO2 1 composite (EC50 = 78.6%). HT/Fe/TiO2 1 was reused five times and still lowered secondary effluent ADMI color below local discharge limits. Benefits of the HT/Fe/TiO2 1 catalyst compared to TiO2 include its lower bandgap energy (2.34 eV vs 3.25 eV), higher ADMI color removal and its magnetic nature that facilitated its recovery and would reduce treatment costs.