Photocatalytic Degradation of Dissolved Phenol by Immobilized Zinc Oxide Nanoparticles: Batch Studies, Continuous Flow Experiments, and Numerical Modeling.

In spite of the progress achieved on the photo-catalytic treatment of water streams, there is still a gap of knowledge on the optimization of the performance of continuous-flow photo-reactors. Zinc-oxide (ZnO) nanoparticles were immobilized on Duranit (80% silica + 20% alumina) inert balls with dip-coating and thermal annealing. The immobilized ZnO nanoparticles were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) spectroscopy, and Raman spectroscopy. To assess the stability and photocatalytic capacity of immobilized ZnO, degradation tests of phenol were performed in batch mode in a 22 W UV-oven with an emission peak at 375 nm by varying the temperature, the initial phenol concentration, and the ratio of photocatalyst mass to initial phenol mass. Continuous flow tests were conducted on two types of annular photo-reactors, made of poly(methyl)methacrylate (PMMA) and stainless steel (STST), equipped with a 6 W UV-lamp with emission at 375 nm, packed with ZnO-coated Duranit beads. Experiments were conducted by recirculating the phenol solution between the annular space of reactor and an external tank and varying the flow rate and the liquid volume in the tank. A one-dimensional dynamic mathematical model was developed by combining reactive with mass-transfer processes and used to estimate the overall reaction kinetic constant with inverse modeling. The results revealed that the ZnO losses might be discernible in batch mode due to the intense stirring caused by the bubbles of injected air, while an insignificant loss of ZnO mass occurs under continuous flow conditions, even after several cycles of reuse; the order of the overall phenol photodegradation reaction is lower than unity; the pseudo-1st order kinetic constant scales positively with the ratio of photocatalyst mass to the initial phenol mass and Peclet number.