Activation of peroxymonosulfate by biochar-supported Fe3O4 derived from oily sludge to enhance the oxidative degradation of tetracycline hydrochloride

Abstract

Carbon materials used for catalysis in advanced oxidation processes tend to be obtained from cheap and readily available raw materials. We constructed a carbon material, OSC@Fe₃O₄, by loading Fe₃O₄ onto the pyrolyzed hazardous waste oily sludge. OSC@Fe₃O₄ was then used to activate peroxymonosulfate (PMS) for the removal of tetracycline hydrochloride (TTCH) from water. At 298 K, 0.2 g⋅L^-1 of catalyst and 0.3 g⋅L^-1 of PMS, the reaction rate constant of the OSC@I-2/PMS system reached 0.079 min^-1, with a TTCH removal efficiency of 92.6%. The degradation efficiency of TTCH remained at 81% after five cycles. The specific surface area and pore volume of OSC@I-2 were 263.9 m²⋅g^-1 and 0.42 cm³⋅g^-1, respectively, which improved the porous structure of the carbon material and provided more active points, thus improving the catalytic performance. N and S were doped into the oily sludge carbon due to the presence of N- and S-containing compounds in the raw oily sludge. N and S doping led to more electron-rich sites with higher negative charges in OSC@I-2 and gave the oily sludge carbon a higher affinity to PMS, thereby promoting its ability to activate PMS. Sulfate radicals (SO₄^•‾) played a dominant role in the degradation of TTCH, with demethylation and the breaking of double bonds being a possible degradation pathway. A biotoxicity test showed that the microbial toxicity of the degradation intermediates was significantly reduced. This work provides a strategy for the application of PMS-based catalysts derived from waste carbon resources.

Keywords: Advanced oxidation processes; Carbon materials; Degradation; Oily sludge; Peroxymonosulfate; Tetracycline hydrochloride.