Industrial steel waste recovery pathway: Production of innovative supported catalyst and its application on hexavalent chromium reduction studies

Abstract

Mill scale is the metallurgical waste produced by the rolling mill in the steel hot rolling process. This hazardous waste is mainly composed of oxide iron, such as hematite, magnetite and wustite. It may have a different and alternative final destination by becoming a catalyst for wastewater treatment. In this work, the catalytic potential of mill scale (MS) from a steel plant was evaluated for hexavalent chromium reduction from synthetic and real matrices under slurry conditions (MS particles dispersed in the solution) or immobilized in Raschig rings. Experiments were conducted in an annular photoreactor irradiated by UVA light. Raschig rings were coated with MS by electrostatic link with polyethylene-grafted-maleic anhydride copolymer (PEGMA) film, and further packed in the annular zone of the UV photoreactor. SEM, XRD and FTIR analysis showed a homogeneous film of MS firmly attached on Raschig rings surface. In this way, the iron-rich industrial steel waste acted as both source of iron and photocatalyst, allowing the reduction of Cr(VI) to Cr(III) in the bulk solution and MS surface, respectively, in the presence of tartaric acid as hole and hydroxyl scavenger and Fe-complexing agent. The Raschig rings (248 g) coated with MS (23 g) achieved total Cr(VI) reduction (below detection limit) after 45 min of reaction (k = 2.0 × 10^-2 mg L^-1 min^{- 1}) under UVA radiation, considering the following initial conditions: [Cr(VI)]₀ = 10 mg L^-1, [tartaric acid]₀/[Cr(VI)]₀ molar ratio = 6:1, pH = 3.0, T = 25 °C. The same system was tested for the treatment of a real effluent from a galvanic industry containing 6 mg L^-1 of Cr(VI). Using the same tartaric acid/Cr(VI) molar ratio (6:1) and pH 3.0, the Cr(VI) present in the effluent was totally reduced (below detection limit) in 360 min (k = 1.93 × 10^-2 mg L^{- 1} min^{- 1}), showing similar kinetic behavior as the process with the synthetic matrix. In all experiments, the concentrations of dissolved iron (Fe(II) and Fe_(total)) were below the disposal limit established by Brazilian legislation, and total chromium removal was achieved by Cr(III) precipitation after the photocatalytic reaction.

Keywords: Heterogeneous photocatalysis; Hexavalent chromium; Iron based process; Mill scale; Raschig rings.