RESUMO
This work aims to integrate several hydrogen peroxide (H2O2) activation mechanisms, photolysis (UVC irradiation), chemical electron transfer (TiO2-P25 photocatalysis), and reaction with TiO2-P25 in dark conditions, for reactive oxygen species (ROS) generation towards the removal of contaminants of emerging concern (CECs), in a single unit operated in continuous-flow mode. An H2O2 stock solution is fed by the lumen side of a tubular ceramic membrane, delivering the oxidant to the (i) catalyst immobilized in the membrane shell-side and (ii) annular reaction zone (ARZ, space between membrane shell-side and outer quartz tube) where CECs contaminated water flows with a helix trajectory, being activated by UV light provided by four lamps placed symmetrically around the reactor. First, the effect of several parameters in the removal of a CEC target molecule, amoxicillin (AMX), was evaluated using a synthetic solution ([AMX]inlet = 2.0 mg L-1): (i) light source (UVA or UVC radiation), (ii) H2O2 dose, (iii) H2O2 injection method (radial permeation vs. upstream injection), and (iv) number of TiO2-P25 layers deposited on the membrane. The UVC/H2O2/TiO2 system with radial addition of H2O2 (20 mg L-1) and 9-TiO2-P25 layers provided the highest AMX removal efficiency (72.2 ± 0.5%) with a UV fluence of 45 mJ cm-2 (residence time of 4.6 s), due to the synergic effect of four mechanisms: (i) AMX photolysis, (ii) H2O2 photocleavage, (iii) TiO2-P25 photoactivation, and (iv) chemical reactions between H2O2 and TiO2-P25. The urban wastewater matrix showed a negative effect on AMX removal (~44%) due to the presence of ROS scavengers and light-filtering species.
Assuntos
Águas Residuárias , Poluentes Químicos da Água , Amoxicilina , Cerâmica , Peróxido de Hidrogênio/química , Oxirredução , Espécies Reativas de Oxigênio , Titânio/química , Raios Ultravioleta , Águas Residuárias/química , Poluentes Químicos da Água/análiseRESUMO
This work proposes a novel approach for the coupling of ozonation and Fenton processes using a new prototype of a high rotation bubble reactor (HRBR), which improves utilization of the ozone and hydrogen peroxide through bubble generation and axial and radial dispersion of the flow. The HRBR integrates the rotor and the diffuser in the same device facilitating the generation and dispersion of the ozone bubbles inside the reaction tank. Thus, the mass transfer to the liquid phase is enhanced. Most of the experiments were carried out under neutral pH and 1580 rpm of agitation during the 20 min of reaction. Total ibuprofen degradation was achieved within 20 min of operation for most of the couplings and individual processes evaluated. It was successfully demonstrated that the HRBR can be used as a reactive system for heterogeneous Fenton and ozonation coupling because it presents a high synergy. For the ozonation process, the reactor also displayed a good performance because the residual ozone in the gas is lower than 0.4 mg/L, which indicates that there is a suitable ozone utilization. Ibuprofen degradation by other processes like oxidation direct by H2O2 and heterogeneous Fenton was 28.0% and 73.1%, respectively. It was determined that the reaction rate, synergy, OUI (ozone utilized index), and consumption of electrical energy (EE/O) of the coupled processes could be improved by using the HRBR depending on the experimental conditions.
Assuntos
Poluentes Ambientais , Ozônio , Poluentes Químicos da Água , Peróxido de Hidrogênio , Compostos de Ferro , Minerais , Oxirredução , RotaçãoRESUMO
This work presents a disruptive approach to promote highly-efficient photo-Fenton process at neutral pH under continuous mode operation. The system consists of a tube-in-tube membrane reactor designed for continuous-flow titration of low iron doses to the annular reaction zone (ARZ). A concentrated acidic ferrous ion (Fe2+) solution is fed by the lumen-side of the membrane, permeating through the membrane pores (inside-out mode), being dosed and uniformly delivered to the membrane shell-side. Polluted water, containing amoxicillin (AMX) and oxidant (H2O2), flows continuously in the reactor annulus (space between the membrane shell-side and an outer quartz tube). The catalyst radial dispersion is enhanced by the helicoidal movement of water around the membrane shell-side, efficiently promoting its contact with H2O2 and UV light. The efficiency of photochemical and photocatalytic oxidation was evaluated as a function of catalyst dose, catalyst injection mode (radial permeation vs injection upstream from the reactor inlet), light source (UVA vs UVC) and aqueous solution matrix (synthetic vs real wastewater). At steady-state, photo-Fenton reaction with Fe2+ radial addition, driven by UVC light, showed the highest AMX removal for synthetic (â¼65%, removal rate of 44 µMAMX/min, using [Fe2+]ARZ = 2 mg/L and [H2O2]inlet = 10 mg/L) and real municipal wastewaters (â¼45%, removal rate of 31 µMAMX/min, with [Fe2+]ARZ = 5 mg/L and [H2O2]inlet = 40 mg/L), with a residence time of only 4.6 s.
Assuntos
Águas Residuárias , Poluentes Químicos da Água , Peróxido de Hidrogênio , Concentração de Íons de Hidrogênio , Ferro , Oxirredução , Poluentes Químicos da Água/análiseRESUMO
WO3/TiO2 is a composite photocatalyst that is being widely used in heterogeneous photocatalysis because it presents better photocatalytic properties than TiO2. For example, the probability of recombination of the electron/hole pairs is diminished and a more range of the solar spectrum is used for its excitation. However, this depend of variables such as tungsten oxide concentration, calcination temperature and synthesis method. This work is focused in establish the effect of WO3 on the morphological and structural characteristics of TiO2. WO3/TiO2 was synthesized by sol-gel method at different calcination temperatures and at different concentrations of tungsten oxide. The surface area, the possible transition between valence band and conduction band, particle size, elemental analysis and crystallography were examined through the BET, DRS, SEM-EDS and XRD analysis.