Petrik, Leslie F.Perold, Willem J.Fatoba, Ojo.O.Tijani, Jimoh Oladejo2016-06-082024-05-132016-06-082024-05-132015https://hdl.handle.net/10566/14681Philosophiae Doctor - PhDEmerging micropollutants such as bisphenol-A and 2-nitrophenol present a great threat in drinking water due to their adverse effects. Most conventional technologies in water and wastewater treatment are not designed to eliminate these xenobiotics; instead pollutants are merely transferred from one phase to another. Advanced oxidation technologies (AOTs) however, have been identified as suitable routes for the degradation of these potential damaging substances based on free radical mechanisms and use of less expensive chemicals. Moreover, due to the structural complexity of wastewater and the existence of pollutants as mixtures, no single advanced oxidation technology can convincingly remove all forms of contaminants and then most often than not, a combination of treatment processes is required for an effective purification process. Besides, the problem of adequate degradation of emerging contaminants in the environment, when AOT(s) are used individually, they present inherent problems. For instance, powder TiO₂ photocatalysts obstruct light penetration, thus prevent effective interaction of UV light with the target pollutants, and particulates present problems of post-filtration and recovery of catalyst particles after treatment. Additionally, TiO₂ has a high band gap energy, high electron-hole recombination rate, and is prone to aggregation of the suspended particles. Similarly, the dielectric barrier discharge (DBD) system produces ultra violet light and hydrogen peroxide within the plasma zone which is not fully maximised for the mineralization of persistent organic pollutants. Rapid oxidation and aggregation of nano zero valent iron particles in photo-Fentons process reduce the particles mobility and affect its performance. In the same vein, the jet loop reactor (JLR) system is characterised by low impingement yield, which is responsible for low mineralization rate. In light of this background, this research investigated the degradation of bisphenol-A and 2- nitrophenol in aqueous solution using the following combined advanced oxidation methods: DBD/supported TiO₂ or Ag doped TiO₂ photocatalysts, DBD/photo-Fenton induced process and JLR/UV/H₂O₂. The target was to assess the performance of each single system and then identify the best combined AOTs capable of significantly mineralizing the target compounds. Firstly, two materials were developed namely supported TiO₂ and stabilized nano zero valent Fe. The TiO₂ photocatalyst supported on a stainless steel mesh was synthesised using sol-gel solution of 8 % PAN/DMF/TiCl₄. The influence of calcination temperature and holding time on the formation of nanocrystals was investigated. Afterwards, various amounts of metallic silver were deposited on the (optimum) supported TiO₂ photocatalyst using thermal evaporation. The catalysts were characterized by several analytical methods; HRSEM, HRTEM, EDS, SAED, FTIR, TGA-DSC, UV-vis/diffuse reflectance spectroscopy, XRD, BET, and XPS. The photocatalytic activity of the prepared catalysts was determined using methylene blue as a model pollutant under ultra-violet light irradiation. Secondly, the TiO2 photocatalyst and 2.4 % Ag doped TiO₂ nanocomposites obtained as optimums (in section 1) were combined with the DBD to decompose BPA or 2-NP in aqueous solution. Moreover, the photo-Fenton process was applied for degradation of the model pollutants, and different dosages of stabilized nZVI (in the range of 0.02 -1.00 g) were added to the DBD system to induce the photo-Fenton process and improve BPA or 2-NP degradation efficiency. Finally, a jet loop reactor (JLR) presenting advanced mixing by the “impinging effect” was explored to decompose BPA or 2-NP in aqueous solution as a function of inlet applied pressure, solution pH, and initial concentration of BPA or 2-NP. Subsequently, different concentrations of hydrogen peroxide (H₂O₂) were added to the JLR to enhance the mineralization process. Furthermore, a combination of JLR with in-line UV light and H₂O₂ were further utilised to decompose BPA or 2-NP in aqueous solution. The residual concentration of the model compounds and intermediates were analysed using high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LCMS). The concentration of the ozone, hydrogen peroxide and hydroxyl radicals generated by the DBD in the presence or absence of a catalyst was monitored using Ultraviolet-visible spectroscopy and Photoluminescence spectroscopy. The results revealed that the optimal thermal conditions to obtain well supported uniformly grown, highly active crystalline TiO₂ catalysts with high specific surface area was 350 ºC at a 3 h holding time in N2 atmosphere with a flow rate of 20 mL/min. Pyrolysis temperature and holding time played an important role on the crystalline nature and photocatalytic activity of the catalyst. Moreover, 2.4 % Ag doped TiO₂ nanocomposites exhibited higher photocatalytic activity for methylene blue degradation than the undoped supported TiO₂ nanocrystals. The results indicated that combining DBD with 2.4 % Ag doped TiO₂ nanocomposites achieved 89 % and 81 % removal efficiency for BPA or 2-NP compared to 67.22 % or 56.8 % obtain when using the DBD system alone. The 2.4 % Ag doped TiO₂ nanocomposites demonstrated excellent activity and offered photochemical stability after four repeated applications.In the case of the photo-Fenton induced process, nano zero valent iron particles (nZVI) stabilized with polyethylene glycol were synthesised using a modified borohydride reduction method. The HRSEM, BET, XRD, and XPS analysis confirmed the formation of filamentous, high surface area iron nanoparticles in the zero valent state. Unlike combined DBD/Ag doped TiO2 nanocomposites, 100 % or complete removal of BPA or 2-NP in aqueous solution was achieved with DBD/nZVI system within 30 minutes compared to 67.9 % (BPA) or 56.8 % (2-NP) with DBD alone after 80 minutes. The removal efficiency was attributable to the production of an increased concentration of OH radicals as well as existence of a synergetic effect in the combined DBD/nZVI system. Five new transformation products namely: 4-nitrophenol (C₆H₅NO₃), 4-nitrosophenolate (C₆H₄NO₂), 4-(prop-1-en-2-yl) cyclohexa-3,5-diene-1,2-dione, (C₉H₈O₂), 4-(2- hydroxylpropan-2-yl)cyclohexane-3,5-diene-1,2-dione (C₉H₁₀O₃), and 1,2-dimethyl-4-(2- nitropropan-2-yl)benzene (C₉H₁₀NO₄) were identified during the degradation of BPA. While, three aromatic intermediate compounds such as 2-nitro-1,3,5-benzenetriolate (C₆H₂NO₅), 2- nitro-1,4-benzoquinone (C₆H₃NO₄), and 2,5-dihydroxyl-1,4-benzoquinone (C₆H₄O₄) respectively were identified during the degradation of 2-NP for the first time in the DBD with JT14 or JT17 using LC-MS. These intermediate compounds have never been reported in the literature, thereby expanding the number of BPA or 2-NP intermediates in the data base in the DBD/JT14 or DBD/nZVI system. BPA degradation proceeded via ozonation, hydroxylation, dimerization, and decarboxylation and nitration step, while 2-NP proceeded via hydroxylation, nitration and denitration respectively. Furthermore, maximum removal efficiency of BPA or 2-NP in aqueous solution using JLR alone under the optimum solution pH (3), inlet pressure (4 bar), flow rate (0.0007 m3/s) was 14.0 % and 13.2 % respectively after 80 minutes. A removal efficiency of 34.9 % was recorded for BPA while 33.2 % was achieved for 2-NP using combined JLR/UV under the same conditions as JLR alone. For the combined JLR/H₂O₂ under optimum conditions of inlet pressure (4 bar), solution pH (3) and peroxide dosage (0.34 g/L), a 51.3 % and 50.1 % removal efficiency was achieved for BPA and 2-NP respectively under same conditions relative to JLR alone. Combination of JLR/UV/H₂O₂ achieved 77.7 % (BPA) or 76.6 % (2- NP) removal efficiency under the same conditions. The combined JLR/UV/H₂O₂ process was found to be most effective combination under the optimized operating parameters due to existence of a synergetic index value of 6.42 or 6.84. This implies that JLR should be coupled with UV and H₂O₂ to achieve greater mineralization efficiency instead of using the system individually. The obtained experimental data of these combined treatment processes fitted the pseudo-first order kinetic models. The combination of the JLR/UV/H₂O₂ was found to be energy efficient and could effectively degrade BPA or 2-NP in aqueous solution to a greater extent than the JLR, JLR/UV or JLR/H₂O₂ system. However, the total organic carbon (TOC) reduction value by all combined DBD and JLR system recorded was not completely achieved due to the formation of recalcitrant intermediate compounds under the applied conditions. In conclusion, this study is reporting for the first time a combination of supported 2.4 % Ag doped TiO₂ nanocomposites with dielectric barrier discharge system for BPA/2-NP degradation in aqueous solution; a combination jet loop reactor based on impingement with in-line UV lamp and H2O2 for successfully decomposing BPA or 2-NP in aqueous solution; as well as a combination of dielectric barrier discharge system and stabilised nano zero valent iron particles, which induced a photo-Fenton process for highly effective removal of BPA or 2-NP in aqueous solution. This study conclusively supports the hypothesis that combined advanced oxidation technologies offer a sustainable and highly efficient means of achieving partial or complete removal of BPA or 2-NP in aqueous solutions. Considering all the combinations of AOTs investigated in this study, the novel DBD/photo-Fenton-induced process under optimised operating parameters was found to be the most efficient in the elimination of BPA or 2-NP in aqueous solutions. The combination of DBD with photo- Fenton like process offers a promising advanced waste water purification technology in the immediate future. Based on these findings, it is recommended that DBD should be redesigned to prevent loss of ozone and JLR system reconfigured to increase impingement and cavitational yield in order to have an effective combination treatment strategy for waste water purification especially in large scale waste water management.enBisphenol-ASupported Ag doped photocatalystPhoto-Fenton induced processDielectric barrier discharge systemJet loop reactorMicropollutantsUniversity of the Western Cape