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• Experimentally-validated model to predict size and distribution of nanoparticles. • Model couples time-resolved fluid dynamic simulations with population balance. • Increasing mixing rate, increases overall nanoparticle synthesis but not local rate. • Combination of fast mixing and high rate leads to a burst of nuclei formation. Achieving size control during nanomaterial synthesis is critical for their deployment in numerous applications due to their strong size-properties relationships. However, it remains a challenge in the field due to multi-step mechanisms in nanoparticle synthesis. In this paper, we present an experimentally-validated model able to predict the particle size and distribution of silver nanoparticles synthesised in flow reactors by coupling time-resolved fluid dynamic simulations with population balance. The model reveals fundamental correlations between reactor design and the corresponding size of the nanoparticles. It shows that increasing mixing rate, increases the overall rate of nanoparticle formation, where nanoparticle synthesis takes place homogeneously in the whole of the reaction volume. In contrast, when there is a distinguishable interface between reactant streams (i.e. low mixing rate), nucleation and growth take place in a small fraction of the reaction volume in the interface between the inlet streams. The combination of fast mixing and high average nucleation rate can lead to a burst of nuclei formation translated in small size and narrow size distribution. This work presents a new approach for the use of computational-guided design of reactors for the synthesis of nanomaterials to move the field away from current trial-and-error strategies. [ABSTRACT FROM AUTHOR]

This work describes the procedure for the simulation of the operation of a photocatalytic reactor by using a multiphysics computational fluid dynamics (CFD) model based on the determination of the intrinsic kinetics parameters in an optically differential photoreactor. The model includes the rigorous description of the hydrodynamics, radiation transfer, mass transport and chemical reaction rate based on a mechanistic kinetic model. Possible existence of dead and recirculation zones has been identified from the flow field, showing a non-uniform flow through the reactor domain. The theoretical laminar profile is not reached due to the short length of the annular core and the departure from the ideal models has been quantified. The predicted velocity field has been experimentally validated with good agreement by injecting a tracer. The radiation field was simulated for slurry TiO 2 suspensions with concentrations between 0.005 and 5 g·L −1 , showing an optimum catalyst loading around 0.1–0.2 g·L −1 . Above this value, the increase in the absorption of radiation is negligible, whereas a more non-uniform radiation profile develops, keeping the most external regions of the reactor in the dark. The results of photocatalytic activity, using methanol oxidation as test reaction, showed good agreement between model predictions and experimental data, with errors between 2% and 10% depending on the catalyst concentration. The successful validation confirms not only the scientific background of the model, but also supports its applicability for engineering purposes in the design and optimization of large scale photocatalytic reactor to overcome some of limitations hindering the industrial development of this technology. [ABSTRACT FROM AUTHOR]

• Mechanistic modelling of E. coli inactivation by photo-Fenton at circumneutral pH. • Radiation transport considering optical properties of iron hydroxide precipitates. • Reversible serial n-event kinetic model successfully describes solar inactivation. • Photo-Fenton cycle mediated by precipitated iron reproduces photosaturation effect. • Multiple target – multiple hit model reproduces synergy of photons and radicals. This work focuses, for the first time, on the mechanistic modelling of wastewater disinfection by the solar photo-Fenton process using controlled solar simulated radiation. At circumneutral pH, iron precipitates forming hydroxides and significantly affecting the optical properties of the water. In this regard, radiation transfer in the reactor has been taken into account. The proposed model considers that the solar inactivation of bacteria follows a serial n-event mechanism with n reversible steps of photonic attacks leading to the bacterial inactivation. Dark Fenton cyclic process of hydroxyl radical formation from hydrogen peroxide is considered to be mediated mainly by precipitated iron species, prevailing at circumneutral pH. Finally, the photo-Fenton process was modelled using a multiple target – multiple hit mechanistic approach that accounts for the synergistic effect between the photonic and the hydroxyl radical attacks to the bacteria. Model predictions successfully reproduce experimental data of solar disinfection, hydrogen peroxide consumption, and photo-Fenton disinfection at circumneutral pH. [ABSTRACT FROM AUTHOR]

• Enhanced radiation transport model validated in commonly used photoreactors. • Isotropic, parallel and cone-shaped emission tested, representing common UV sources. • Increase of precision reached for sun direct light simulations. • Great improvement in LEDs simulations, from finer cone radiation and power cosine. This work presents the enhanced numerical simulation of the radiation transport in three different types of photocatalytic reactor using a novel Discrete Ordinate Method model recently developed for the open-source Computational Fluid Dynamics (CFD) platform OpenFOAM. The photoreactors represent commonly used geometries and illumination sources in the field of heterogeneous photocatalysis: an annular reactor illuminated by a mercury fluorescent lamp, a tubular reactor coupled to a compound parabolic collector illuminated by sunlight, and a tubular reactor illuminated by LEDs. Simulations were carried out for different photocatalyst concentrations, considering absorption and anisotropic scattering, showing differences smaller than 2.4% with respect to the results obtained by commercial CFD software for systems with isotropic emission, such as fluorescent lamps. Moreover, the model was able to improve the simulation of solar reactors and dramatically outperformed the simulation of LED sources, due to the combined effect of quadrature rotation and cone-limit fitting for cone-shaped sources, as well as a LED-specific power-cosine light distribution. The developed model has been thoroughly validated and is now available to the open-source CFD community. It allows a comprehensive numerical simulation of radiation transport using any type of light source, with applications in numerous engineering fields where optical phenomena affect the performance of the process. [ABSTRACT FROM AUTHOR]

• Development of a numerical simulation model for SODIS processes in flow reactors. • Coupling of solar vector calculation with radiation field resolution. • Application of mechanistic kinetic model with explicit radiation absorption effect. • Validation of the model in a tubular photoreactor coupled with a CPC reflector. • Good prediction of experimental data under both simulated and natural sunlight. A novel procedure for the simulation of solar water disinfection (SODIS) processes in flow reactors is presented. The modeling approach includes the rigorous description of hydrodynamics, radiation transfer, mass transport and bacterial inactivation phenomena within the reactor by means of a computational fluid dynamics (CFD) software. The methodology has been evaluated in a tubular reactor coupled with a compound parabolic collector (CPC). Velocity profiles have been validated versus theoretical fully developed flow, and radiation fields versus both ray tracing and experimental actinometrical measurements. Incorporation of the solar vector calculation significantly improves the model capabilities for prediction of the potential performance of the SODIS process at different geographical coordinates and operation time. A mechanistic kinetic model was used for the description of the bacterial inactivation rate with explicit radiation absorption effects, coupling the radiation field with the mass balances of viable bacterial species. Model predictions successfully reproduce the experimental data of E. coli inactivation under different irradiances of both simulated and natural solar light with a normalized root mean squared logarithmic error (NRMSLE) of 6.65% and 9.72%, respectively. Therefore, this novel methodology is confirmed as a useful tool for the scaling-up of the SODIS process to large volume systems to be installed in remote communities where safe drinking water is not available. [ABSTRACT FROM AUTHOR]

[Display omitted] • DCF degradation was investigated via UV, UV/H 2 O 2 , and UV/FC at 265, 285 and 310 nm. • The degradation depends upon the absorption of the contaminant and the oxidant. • The main reaction mechanisms for UV/H 2 O 2 and UV/FC were proposed. • The electricity demand is similar for all treatments due to the oxidants' cost. • No significant synergy was found for the dual-wavelength system (265 + 285 nm). In this study, the degradation of diclofenac (DCF), a frequently detected non-steroidal pharmaceutical, was evaluated by using UV-B and UV-C (265, 285, and 310 nm) light-emitting diodes (LEDs) alone and in combination with hydrogen peroxide (UV/H 2 O 2) and free chlorine (UV/FC). The degradation of DCF followed a pseudo first-order kinetic, and their trend reflected the pattern of the molar absorption coefficients of the DCF and the oxidants. A positive synergistic factor was found for the UV-LED driven advanced oxidation processes in almost all cases, but despite the higher degradation rates, the overall electricity demand is similar to UV alone due to the oxidants' energy cost. The rigorous kinetic degradation mechanisms at different wavelengths were proposed for the two processes, UV/H 2 O 2 and UV/FC, where the predicted values were respectively k HO = 9.12 · 109 M−1 s−1 and k Cl = 1.30 · 1010 M−1 s−1. No significant synergy (p > 0.05) was found for the dual-wavelength system (265 + 285 nm), and the time-based constants in all cases changed linearly with lamp intensity. Finally, dissolved organic carbon and phytotoxicity analysis revealed low mineralisation (around 20–30%) associated with the formation of stable dimers and a decrease in toxicity towards tomato and radish seeds. In the main, this work shows the great potential of implementing wavelength-specific LEDs in water treatments and effectively designing the reactor playing with adjustable intensities and kinetic degradation rates. [ABSTRACT FROM AUTHOR]