Modeling Photolytic Advanced Oxidation Processes for the Removal of Trace Organic Contaminants
AdvisorSáez, Eduardo A.
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PublisherThe University of Arizona.
RightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
EmbargoRelease after 12-Mar-2018
AbstractAdvanced oxidation processes (AOPs) are commonly used for the destruction of persistent trace organic contaminants (TOrCs) that survive conventional wastewater treatment processes. Three types of AOPs, UV/H2O2, sunlight photolysis and photo-Fenton are experimentally investigated and mathematically quantified to anticipate the fate of TOrCs during oxidation processes, specifically addressing the significant effect of reaction by-products and water matrix on oxidation efficiencies. Hydrogen peroxide UV photolysis is among the most widely used AOPs for the destruction of TOrCs in waters destined for reuse. Previous kinetic models of UV/H2O2 focus on the dynamics of hydroxyl radical production and consumption, as well as the reaction of the target organic with hydroxyl radicals. In this work, we build a predictive kinetic model for the destruction of p-cresol by hydrogen peroxide photolysis based on a complete reaction mechanism that includes reactions of intermediates with hydroxyl radicals. The results show that development of a predictive kinetic model to evaluate process performance requires consideration of the complete reaction mechanism, including reactions of intermediates with hydroxyl radicals. Applying the model to an annular flow-through reactor with reflecting walls, the model mathematically demonstrates that the wall reflectivity significantly enhances the rate of conversion of the target, accounting for the UV light reflection from the reacting walls, as well as the hydrodynamics of the annular flow. Direct and indirect sunlight photolysis is critically important in the breakdown of contaminants in effluent wastewater. The fate of a suite of TOrCs and estrogenic activity were investigated in an effluent-dependent stream. Some TOrCs, which are not sufficiently attenuated through biodegradation and soil adsorption were destructed obviously with distance of travel in the stream. Independent experiments, conducted in batch reactor with 17α-ethinylestradiol (EE2) spiked in effluent showed that attenuation of estrogenic compounds maybe due in part to indirect photolysis caused by formation of reactive species from sunlight absorption. Further investigation was conducted using selective probe compounds to characterize reactive species. And results showed that singlet oxygen generated from excited state of effluent organic matter was responsible for essentially all observed transformations of targets in the effluent in Tucson. To mathematically quantify the photo-Fenton AOP, a kinetic model is proposed for the photolysis of Fe3+ hydroxo complexes at low pH (pH ≤ 3.0). The model incorporates elementary reactions of the Fenton-like and UV/H2O2 system. Iron speciation and photochemical parameters, including the molar absorptivities of light-absorbing species and the quantum yields of Fe3+ and FeOH2+ hydrolysis are experimentally validated. However, the predicted, time-dependent Fe2+ concentrations during Fe3+ photolysis are much lower than measured. The possible missing elements in the model could be (i) quenching of OH radicals by unknown species, or/and (ii) shielding of Fe2+ by unknown compounds at the beginning of the process.
Degree ProgramGraduate College