Mechanistic modeling of vacuum UV advanced oxidation process in an annular photoreactor.

A novel mechanistic model that describes the vacuum UV advanced oxidation process in an annular photoreactor initiated by 172 nm and 185 nm (in combination with 253.7 nm, with and without exogenous H2O2) is presented in this paper. The model was developed from first principles by incorporating the vacuum UV-AOP kinetics into the theoretical framework of in-series continuous flow stirred tank reactors. After conducting a sensitivity analysis, model predictions were compared against experiments conducted under a variety of conditions: (a) photo-induced formation of hydrogen peroxide by water photolysis at 172 nm (for both air- and oxygen-saturated conditions); (b) photo-induced formation of hydrogen peroxide by water photolysis at 185 + 253.7 nm (in the presence of formic acid, with and without the initial addition of hydrogen peroxide); (c) direct photolysis of hydrogen peroxide by 253.7 nm; (d) degradation of formic acid by 185 + 253.7 nm (with and without initial addition of hydrogen peroxide); and (e) degradation of formic acid by 253.7 nm (with the addition of exogenous hydrogen peroxide). In all cases, the model was able to accurately predict the time-dependent profiles of hydrogen peroxide and formic acid concentrations. Two newly recognized aspects associated with water photolysis were identified through the use of the validated model. Firstly, unlike the 185 nm and 253.7 nm cases, water photolysis by the 172 nm wavelength revealed a depth of photoactive water layer an order of magnitude greater (∼230-390 µm, depending on the specific operating conditions) than the 1-log photon penetration layer (∼18 µm). To further investigate this potentially very important finding, a computational fluid dynamics model was set up to assess the role of transport mechanisms and species distributions within the photoreactor annulus. The model confirmed that short-lived hydroxyl radicals were present at a radial distance far beyond the ∼18 µm photon penetration layer. Secondly, kinetic simulations showed that the higher penetration depth of hydroxyl radicals was not caused by diffusive or convective transport phenomena but rather the effect of non-linear behavior of the complex reaction kinetics involved in the process.

Combined physico-chemical treatment of secondary settled municipal wastewater in a multifunctional reactor.

In this paper, the physico-chemical treatment of municipal wastewater for the simultaneous removal of pollutant indicators (chemical oxygen demand (COD) and total coliforms) and organic contaminants (total phenols) was investigated and assessed. A secondary settled effluent was subjected to coagulation, disinfection and absorption in a multifunctional reactor by dosing, simultaneously, aluminum polychloride (dose range: 0-150 µL/L), natural zeolites (dose range: 0-150 mg/L), sodium hypochlorite (dose range: 0-7.5 mg/L) and powder activated carbon (dose range: 0-30 mg/L). The treatment process was optimized using computational fluid dynamics (CFD) and response surface methodology. Specifically, a Latin square technique was employed to generate 16 combinations of treating agent types and concentrations which were pilot tested on an 8 m(3)/h multifunctional reactor fed by a secondary effluent with COD and total coliform concentrations ranging from ≈20 to 120 mg/L and from 10(5) to 10(6) CFU/100 mL, respectively. Results were promising, indicating that removal yields up to 71% in COD and 5.4 log in total coliforms were obtained using an optimal combination of aluminum polychloride (dose range ≈ 84-106 µL/L), powder activated carbon ≈ 5 mg/L, natural zeolite (dose range ≈ 34-70 mg/L) and sodium hypochlorite (dose range ≈ 3.4-5.6 mg/L), with all treating agents playing a statistically significant role in determining the overall treatment performance. Remarkably, the combined process was also able to remove ≈ 50% of total phenols, a micropollutant known to be recalcitrant to conventional wastewater treatments.