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

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.

Facile fabrication of hybrid titanium(IV) isopropoxide/pozzolan nanosheets (TnS-Pz) of high photocatalytic activity: characterization and application for Cr(VI) reduction in an aqueous solution.

This paper presents the synthesis of a hybrid material through the use of natural pozzolan and titanium(IV) isopropoxide using the sol-gel method and its application in the photocatalytic hexavalent chromium reduction. The characterization data indicated a mesoporous material possessing a surface area of 271.7 m2 g-1. The morphology studies (SEM and TEM) showed nanosheet hybrid structures. The analysis of DRUV, FTIR, XRD, and Mössbauer spectroscopy provides a different electronic structure of the synthetized material when compared with the originals, proving the hybridization process between pozzolan and titanium(IV) isopropoxide. The photocatalytic reduction of Cr(VI) to Cr(III) using the hybrid material showed a better performance than conventional photocatalysts (precursor and TiO2-P25). Operational conditions such as chromium initial concentration (0.02-0.20 mM), solution pH (3-6), and type of scavenger (citric or tartaric acid) were evaluated in order to determine the best experimental conditions for the Cr(VI) photoreduction. At their optimum (catalyst load of 15 mg L-1, tartaric acid as scavenger, [scavenger]0/[Cr(VI)]0 M ratio = 3:1, pH 3, and 25 °C), the total photoreduction of 0.20 mM Cr(VI) was achieved in 180 min. The novel hybrid materials synthesized from pozzolan and titanium(IV) isopropoxide showed to be a potential catalyst for the Cr(VI) reduction in aqueous solution. Graphical abstract.

As(III) and Cr(VI) oxyanion removal from water by advanced oxidation/reduction processes-a review.

Water pollution by human activities is a global environmental problem that requires innovative solutions. Arsenic and chromium oxyanions are toxic compounds, introduced in the environment by both natural and anthropogenic activities. In this review, the speciation diagrams of arsenic and chromium oxyanions in aqueous solutions and the analytical methods used for their detection and quantification are presented. Current and potential treatment methods for As and Cr removal, such as adsorption, coagulation/flocculation, electrochemical, ion exchange, membrane separation, phyto- and bioremediation, biosorption, biofiltration, and oxidative/reductive processes, are presented with discussion of their advantages, drawbacks, and the main recent achievements. In the last years, advanced oxidation processes (AOPs) have been acquiring high relevance for the treatment of water contaminated with organic compounds. However, these processes are also able to deal with inorganic contaminants, mainly by changing metal/metalloid oxidation state, turning these compounds less toxic or soluble. An overview of advanced oxidation/reduction processes (AO/RPs) used for As and Cr removal was carried out, focusing mainly on H2O2/UVC, iron-based and heterogeneous photocatalytic processes. Some aspects related to AO/RP experimental conditions, comparison criteria, redox mechanisms, catalyst immobilization, and process intensification through implementation of innovative reactors designs are also discussed. Nevertheless, further research is needed to assess the effectiveness of those processes in order to improve some existing limitations. On the other hand, the validation of those treatment methods needs to be deepened, namely with the use of real wastewaters for their future full-scale application. Graphical abstract ᅟ.

Application of a micro-meso-structured reactor (NETmix) to promote photochemical UVC/H2O2 processes - oxidation of As(iii) to As(v).

A micro-meso-structured reactor (NETmix) was used for the first time to promote photochemical UVC/H2O2 processes. The NETmix photoreactor consists of a network of chambers and channels, where the liquid flows, sealed with a quartz slab with high UVC transparency. Due to the small size of channels and chambers, the NETmix presents a uniform irradiance through the entire reactor depth, short molecular diffusion distances and large specific interfacial areas, maximizing the pollutant/oxidant contact. In this study, the NETmix photoreactor was evaluated for As(iii) oxidation to As(v) using a photochemical UVC/H2O2 system. The effect of the UVC lamp power (4, 6 or 11 W), the number of UVC lamps (2 or 3 lamps) and the UVC lamp layout (parallel or perpendicular to the flow direction) was evaluated, in order to ensure uniform irradiation of the entire reaction mixture. The optimum H2O2 concentration for each light distribution system was also evaluated. At the best configuration, 3 lamps of 11 W positioned parallel to the flow direction, total As(iii) oxidation ([As(iii)]0 = 1.33 × 10-2 mM) was achieved in 15 min with an absorbed photon flux density of 1.9 × 10-1 einstein per m3 per s. Significant differences were highlighted between the photon flux actually received in the photoreactor and the radiant power emitted by the lamp. A kinetic model able to represent the As(iii) oxidation employing UVC radiation and H2O2 in a micro-meso-structured reactor was presented. The photochemical space time yield (PSTY) values obtained for the micro-meso-structured reactor are higher than for conventional batch reactors, showing that the NETmix technology can be a good solution for application in photochemical processes.

Strategies to reduce mass and photons transfer limitations in heterogeneous photocatalytic processes: Hexavalent chromium reduction studies.

The current work presents different approaches to overcome mass and photon transfer limitations in heterogeneous photocatalytic processes applied to the reduction of hexavalent chromium to its trivalent form in the presence of a sacrificial agent. Two reactor designs were tested, a monolithic tubular photoreactor (MTP) and a micro-meso-structured photoreactor (NETmix), both presenting a high catalyst surface area per reaction liquid volume. In order to reduce photon transfer limitations, the tubular photoreactor was packed with transparent cellulose acetate monolithic structures (CAM) coated with the catalyst by a dip-coating method. For the NETmix reactor, a thin film of photocatalyst was uniformly deposited on the front glass slab (GS) or on the network of channels and chambers imprinted in the back stainless steel slab (SSS) using a spray system. The reaction rate for the NETmix photoreactor was evaluated for two illumination sources, solar light or UVA-LEDs, using the NETmix with the front glass slab or/and back stainless steel slab coated with TiO2-P25. The reusability of the photocatalytic films on the NETmix walls was also evaluated for three consecutive cycles using fresh Cr(VI) solutions. The catalyst reactivity in combination with the NETmix-SSS photoreactor is almost 70 times superior to one obtained with the MTP.

Photo-Fenton oxidation of 3-amino-5-methylisoxazole: a by-product from biological breakdown of some pharmaceutical compounds.

The present study aims to assess the removal of 3-amino-5-methylisoxazole (AMI), a recalcitrant by-product resulting from the biological breakdown of some pharmaceuticals, applying a solar photo-Fenton process assisted by ferrioxalate complexes (SPFF) (Fe3+/H2O2/oxalic acid/UVA-Vis) and classical solar photo-Fenton process (SPF) (Fe2+/H2O2/UVA-Vis). The oxidation ability of SPFF was evaluated at different iron/oxalate molar ratios (1:3, 1:6, and 1:9, with [total iron] = 3.58 × 10-2 mM and [oxalic acid] = 1.07 × 10-1, 2.14 × 10-1 and 3.22 × 10-1 mM, respectively) and pH values (3.5-6.5), using low iron contents (2.0 mg Fe3+ L-1). Additionally, the use of other organic ligands such as citrate and ethylenediamine-N,N'-disuccinic acid (EDDS) was tested. The oxidation power of the classical SPF was assessed at different pH values (2.8-4.0) using 2.0 mg Fe2+ per liter. Furthermore, the effect of AMI concentration (2-20 mg L-1), presence of inorganic ions (Cl-, SO42-, NO3-, HCO3-, NH4+), and radical scavengers (sodium azide and D-mannitol) on the SPF method at pH 3.5 was also assessed. Experiments were done using a lab-scale photoreactor with a compound parabolic collector (CPC) under simulated solar radiation. A pilot-scale assay was conducted using the best operation conditions. While at near neutral pH, an iron/oxalate molar ratio of 1:9 led to the removal of 72 % of AMI after 90 min of SPFF, at pH 3.5, an iron/oxalate molar ratio of 1:3 was enough to achieve complete AMI degradation (below the detection limit) after 30 min of reaction. The SPF process at pH 3.5 underwent a slower AMI degradation, reaching total AMI degradation after 40 min of reaction. The scale up of SPF process showed a good reproducibility. Oxalic and oxamic acids were identified as the main low-molecular-weight carboxylic acids detected during the pilot-scale SPF reaction. Graphical abstract ᅟ.