published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

D.Phil. (Chemistry) / Please refer to full text to view abstract

Thesis (PhD)--Stellenbosch University, 2001. / ENGLISH ABSTRACT: The photo-mineralization of organic compounds (in the combined presence of a Ti02 based semiconductor catalyst, UV radiation and molecular oxygen) represents an advanced oxidation technology with significant potential for environmental pollution abatement. This oxidation process (generally known as photocatalytic oxidation - PCO) is currently the subject of extensive global research, with the main objective being the oxidative removal of organic and inorganic pollutants from water, air and soil. Presently, many barriers still block the way to commercial implementation of this technology, hence a unique (and effective) configuration of catalyst, light source and reactor design needs to identified. In terms of the water treatment scenario (which is the emphasis of this work) the need exists to develop a practical and affordable PCO reactor for water treatment on a large scale. The two laboratory-scale PCO reactors investigated in this work were based on a "falling film" flow reactor design and were constructed with commercially available materials and components. Degussa P-25 Ti02 was used as semiconductor catalyst and two types of low-pressure mercury lamps as the UV light source. Three modes of operation were investigated in order to determine the practical feasibility of the reactors. These included the recirculation, single pass and sequential single pass modes. The reactors were operated either as a Ti02 slurry-phase reactor (Reactor 1), or with Ti02 immobilized on stationary fiber glass and fibrous activated carbon sheet modules (Reactors 2A and 28 respectively). Extensive parametric evaluations were done using conventional one-factor variation and statistical methods according to optimal experimental design principles. The PCO treatment of two model organic pollutants (para-Chlorophenol and cyanobacterial microcystin YA, YR, LR and RR) were investigated. These pollutants were spiked into various water matrices to the desired concentration level. The combined photocatalyticcarbon adsorption treatment of these two pollutants was also investigated in Reactor 28. The experimental results obtained through this work showed that both model pollutants were successfully degraded in several water matrices by means of treatment in the respective PCO reactors. Moreover, this research was the first ever demonstration of the Ti02 photocatalytic degradation of microcystin toxins in the aqueous phase. The large number of parametric and optimization studies yielded the relative contributions of the various process parameters (in terms of the defined photocatalytic efficiency parameters as responses) very effectively. Furthermore, statistical evaluation of the experimental data provided valuable insight into the scientific phenomena associated with Ti02 mediated PCO processes. / AFRIKAANSE OPSOMMING: Die foto-mineralisasie van organiese verbindings (in die gekombineerde teenwoordigheid van 'n Ti02 gebaseerde halfgeleier katalisator, UV straling en molekulêre suurstof) verteenwoordig 'n gevorderde oksidasie-tegnologie met beduidende potensiaal vir bekamping van omgewingsbesoedeling. Hierdie oksidasie-proses (algemeen bekend as fotokatalitiese oksidasie - FKO) is tans wêreldwyd die onderwerp van ekstensiewe navorsing, met hoofdoel die oksidatiewe verwydering van organiese en anorganiese besoedelingstowwe uit water, lug en grond. Huidiglik bestaan daar nog vele struikelblokke wat die weg na kommersiële implementering van hierdie tegnologie blokkeer, gevolglik moet 'n unieke (en effektiewe) konfigurasie van katalisator, ligbron en reaktor-ontwerp nog identifiseer word. In terme van die waterbehandeling situasie (wat die klem van hierdie werk is) bestaan die nodigheid om 'n praktiese en bekostigbare FKO reaktor te ontwikkel vir watersuiwering op 'n groot skaal. Die twee laboratorium-skaal FKO reaktore in hierdie studie was gebaseer op 'n "vallende film" vloeireaktor ontwerp en is gekonstrueer met kommersieël beskikbare materiale en komponente. Degussa P-25 Ti02 is aangewend as halfgeleier katalisator en twee tipes lae-druk kwik lampe as die UV ligbron. Drie bedryfsmodes is ondersoek met die doel om die praktiese haalbaarheid van die reaktore te bepaal. Hierdie het ingesluit die resirkulasie, enkeldeurvloei en enkeldeurvloei-sekwensie modes. Die reaktore is bedryf as óf 'n Ti02 flodder-fase reaktor (Reaktor 1) óf met Ti02 ge-immobiliseer op 'n stasionêre veselglas en veselagtige ge-aktiveerde koolstof blad-modules (Reaktor 2A en 28 onderskeidelik). Omvattende parametriese evaluasies is gedoen deur gebruik te maak van konvensionele een-faktor variasie en statistiese metodes na aanleiding van optimale eksperimentele ontwerp beginsels. Die FKO behandeling van twee modelorganiese besoedelingstowwe (para-Chlorofenol en siano-bakteriese mikrosistien YA, YR, LR en RR) is ondersoek. Hierdie besoedelingstowwe is ge-ent in verskeie watermatrikse tot die verlangde konsentrasievlak. Die gekombineerde fotokatalitiese - aktiveerde koolstof behandeling van die twee besoedelingstowwe is ook ondersoek in Reaktor 28. Die eksperimentele resultate verkry deur hierdie werk het getoon dat beide die modelbesoedelingstowwe suksesvol gedegradeer is in verskeie watermatrikse deur behandeling in die onderskeie FKO reaktore. Trouens, hierdie navorsing was die eerste demonstrasie ooit van die Ti02 fotokatalitiese degradasie van mikrosistien toksiene in die waterige fase. Die groot aantal parametriese en optimiseringstudies het die bydraes van die verskeie proses-parameters (in terme van die gedefinieerde fotokatalitiese effektiwiteitsparameters as response) baie effektief verskaf. Verder, statistiese evaluasie van die eksperimentele data het waardevolle insig verskaf tot die wetenskaplike verskynsels te assosieer met Ti02 gemedieërde FKO prosesse.

水資源缺乏引起的一系列問題在世界上已建得到廣泛關注，因此，確保提供潔淨衛生的水在保護人類健康和環境方面起著重要作用。近來，光催化作為頗有前景的替代方法被廣泛應用殺菌除污。二氧化鈦是目前研究最多應用最廣的光催化劑。基於紫外光譜照射，催化劑表面產生活性氧化物種，這些物種具有強氧化性能殺滅細胞。 / 本文首次研究了母體菌種大腸桿菌BW25113和它的同源單基因缺陷變異體對光催化殺菌的靈敏度差異。母體菌種和變異菌種表現出不同的耐受性。基於此，能幫助發掘出重要的變種。通過生物化學方法，可以檢測出不同菌種的生理性特徵。結合其他方法，可以進一步揭示光催化殺菌的生理性機理。 / 首先，我們篩選出了兩種重要的變異體。一種是大腸桿菌JW1081，即脂肪酸變異體，該菌種缺乏脂肪酸合成調節的關鍵基因。一種是大腸桿菌JW3942，即乙酰輔酶A變異體，該菌種缺乏乙酰輔酶A合成調控得到關鍵激酶。我們發現脂肪酸變異體對光催化處理的耐受性稍低，而乙酰輔酶A變異體則耐受性較高。 同時發現，溫度可以調節細胞膜的不飽和酸和飽和酸的比例。因此，我們提出脂肪酸和乙酰輔酶A是光催化殺菌中的重要影響因子。 / 更進一步研究發掘了細胞內酶和光催化產生的活性氧物種間的關係。大腸桿菌JW3914，即過氧化氫酶變異體，是發現的另一個重要的變異體。通過對母體和變異體的淬滅劑實驗，主要的殺菌活性氧物種是光催化產生的雙氧水，而不是羥基自由基。細胞體內的過氧化氫酶誘導在母體菌體內發現，而未在變異體內檢測到。 / 本課題採用母體/單基因變異體的研究方法，為全面深刻理解光催化殺菌的深層機理提供一種全新的研究思路。 / Many problems associated with the lack of clean, fresh water worldwide are well known. Developing countries will particularly be affected by water availability problems and there will be further pressure on water demand resulting from economic development and population growth. Therefore, the provision of safe and clean water plays a key role in protecting human health and the environment. Recently, photocatalytic oxidation (PCO) has been widely accepted as a promising alternative method of water disinfection. Titanium dioxide (TiO₂) has been investigated extensively and is the most widely used photocatalyst. Upon the irradiation of UVA lamp, reactive charged and oxidative species are generated on TiO₂ surface and can inactive the bacterial cells. / In this study, the photocatalytic performances of a parental strain (E.coli BW25113) and its isogenic single-gene deletion mutant strains have been investigated for the first time. These bacterial strains exhibited different sensitivies towards photocalytic inactivation. Based on this, it can help reveal some important mechanism from the mutations. Biotic factors were confirmed by physiological biochemical measurement. / Firstly, we screened out the potential mutation fabF⁻ mutant (E. coli JW1081, carrying the mutation of fabF759(del)::kan) and coaA⁻ mutant (E. coli JW3942, carrying the mutation of coaA755(del)::kan). The isogenic fabF⁻ mutant is slightly more susceptible, and coaA⁻ mutant is less susceptible to photocatalytic inactivation. Through conditioning temperature, it adjusts the ratio of unsaturated to saturated fatty acid (FA) of cell membrane. We propose that FA profile and coenzyme A level significantly affect photocatalytic inactivation of bacteria. Moreover, we show photogenerated electrons (e⁻) can directly inactivate the cells of E. coli. / Furthermore, we report the relationship between the bacterial intracellular enzyme and the reactive charged and oxidative species (ROSs) generated during photocataltic inactivation. The katG⁻ mutant, E. coli JW3914, carrying the mutation of katG729(del)::kan is another important mutation. The parental and katG⁻ mutant strains reveal that photogenerated H₂O₂ but not OH[subscript free] is another important reactive oxygen species to inactivate bacteria. The inducible catalase (CAT) corresponding to H₂O₂can be detected in parental strain but not in katG⁻ mutant. / The research methodology using parental/single-gene deletion mutant strains is expected to shed light on fully understanding of the fundamental mechanism of photocatalytic inactivation of E. coli. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Gao, Minghui. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 130-177). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Acknowledgements --- p.i / Abstract --- p.v / Table of contents --- p.ix / List of Figures --- p.xiii / List of Plates --- p.xvii / List of Tables --- p.xviii / List of Equations --- p.xix / Abbreviations --- p.xxi / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Water crisis --- p.1 / Chapter 1.2 --- Traditional disinfection methods --- p.3 / Chapter 1.2.1 --- Chlorination --- p.4 / Chapter 1.2.2 --- Ozonation --- p.6 / Chapter 1.2.3 --- Ultraviolet irradiation --- p.8 / Chapter 1.2.4 --- Multiple disinfectants --- p.10 / Chapter 1.3 --- Advanced oxidation process (AOPs) --- p.10 / Chapter 1.3.1 --- Hydrogen Peroxide/Ozone (H₂O₂/O₃) --- p.11 / Chapter 1.3.2 --- Ozone/Ultraviolet Irradiation (O₃/UV) --- p.12 / Chapter 1.3.3 --- Hydrogen Peroxide/ Ultraviolet Irradiation (H₂O₂/UV) --- p.12 / Chapter 1.3.4 --- Fenton's --- p.Reaction / Chapter 1.4 --- Solar photocatalytic disinfection (SPC-DIS) --- p.14 / Chapter 1.4.1 --- Photocatalyst-TiO₂ --- p.31 / Chapter 1.4.2 --- Irradiation sources --- p.35 / Chapter 1.4.3 --- TiO₂ photocatalytic process --- p.35 / Chapter 1.4.4 --- The role of photogenerated reactive charged and oxidative species (ROSs) --- p.38 / Chapter 1.5 --- Bacteria --- p.40 / Chapter 1.5.1 --- E. coli BW25113 --- p.40 / Chapter 1.5.2 --- E. coli Keio Collection --- p.41 / Chapter 1.5.3 --- Bacterial defense mechanism towards oxidative stresses --- p.44 / Chapter 1.6 --- Photocalytic applications --- p.53 / Chapter 1.7 --- Significance of the project --- p.55 / Chapter 2. --- Objectives --- p.58 / Chapter 3. --- Genetic studies of the roles of fatty acid and coenzyme A in photocatalytic inactivation of Escherichia coli --- p.61 / Chapter 3.1 --- Introduction --- p.61 / Chapter 3.2 --- Materials and methods --- p.65 / Chapter 3.2.1 --- Photocatalyst --- p.65 / Chapter 3.2.2 --- Bacterial nutrient --- p.66 / Chapter 3.2.3 --- Bacterial strains --- p.67 / Chapter 3.2.4 --- Photocatalytic inactivation --- p.69 / Chapter 3.2.5 --- Fatty acid profile --- p.72 / Chapter 3.2.6 --- Fluorescent measurement of bacterial coenzyme A content --- p.74 / Chapter 3.2.7 --- The role of photogenerated electrons (e⁻) to bacterial inactivation --- p.74 / Chapter 3.2.8 --- Transmission Electron Microscopic (TEM) --- p.75 / Chapter 3.2.9 --- Photoelectrochemical measurement --- p.77 / Chapter 3.3 --- Results --- p.77 / Chapter 3.3.1 --- Photocatalytic inactivation --- p.77 / Chapter 3.3.2 --- Effects of pre-incubation at different temperatures --- p.80 / Chapter 3.3.3 --- Fatty acid profile --- p.83 / Chapter 3.3.4 --- Fluorescent measurement of bacterial coenzyme A content --- p.84 / Chapter 3.3.5 --- The role of electron (e⁻) in photocataytic inactivation --- p.84 / Chapter 3.3.6 --- Transmission electron microscopy (TEM) --- p.89 / Chapter 3.3.7 --- Photocurrent measurement --- p.90 / Chapter 3.4 --- Discussion --- p.90 / Chapter 3.5 --- Conclusions --- p.96 / Chapter 4 --- Genetic and physiological studies of the role of Catalase and H₂O₂ in photocatalytic inactivation of E. coli --- p.98 / Chapter 4.1 --- Introduction --- p.98 / Chapter 4.2 --- Materials and methods --- p.101 / Chapter 4.2.1 --- Bacterial strains --- p.101 / Chapter 4.2.2 --- Photocatalytic performance --- p.102 / Chapter 4.2.3 --- Scavenger studies --- p.103 / Chapter 4.2.4 --- Effects of different pHs on photocatalytic inactivation --- p.104 / Chapter 4.2.5 --- Measurement of bacterial catalase activity and H₂O₂ --- p.104 / Chapter 4.2.6 --- Transmission electron microscopy (TEM) --- p.105 / Chapter 4.2.7 --- Atomic absorption spectrophotometer (AAS) --- p.105 / Chapter 4.3 --- Results and discussion --- p.106 / Chapter 4.3.1 --- Photocatalytic performance --- p.106 / Chapter 4.3.2 --- Scavenger studies --- p.108 / Chapter 4.3.3 --- Contribution of hydrogen peroxide (H₂O₂) --- p.111 / Chapter 4.3.4 --- Effects of different pHs on photocatalytic inactivation --- p.114 / Chapter 4.3.5 --- Bacterial catalase (CAT) activity --- p.116 / Chapter 4.3.6 --- Destruction model of bacterial cells --- p.118 / Chapter 4.4 --- Conclusions --- p.120 / Chapter 5. --- General conclusions --- p.122 / Chapter 6. --- Prospectives --- p.125 / Chapter 7. --- Appendix --- p.127 / Chapter 8. --- References --- p.130

This dissertation presents a method for enhancement of the efficiency and scalability of photocatalytic water purification systems, along with an experimental validation of the concept. A 3-dimensional photocatalyst structure, made from a TiO2-SiO2 composite, has been designed and fabricated for use in a custom designed LED-source illumination chamber of rotational symmetry that corresponds with the symmetry of the photocatalyst material. The design of the photocatalyst material has two defining characteristics: geometrical form and material composition. The design of the material was developed through the creation of a theoretical model for consideration of the system's photonic efficiency. Fabrication of the material was accomplished using a Ti alkoxide solution to coat a novel 3D support structure. The coatings were then heat treated to form a semiconducting thin-film. The resulting films were evaluated by SEM, TEM, UV-vis spectroscopy and Raman spectroscopy. The surface of the material was then modified by implantation of TiO2 and SiO2 nanoparticles in order to increase catalytic surface area and improve the photoactivity of the material, resulting in increased degradation performance by more than 500%. Finally, the efficiency of the photocatalytic reactor was considered with respect to energy usage as defined by the Electrical Energy per Order (EEO) characterization model. The effects of catalyst surface modification and UV-illumination intensity on the EEO value were measured and analyzed. The result of the modifications was an 81.9% reduction in energy usage. The lowest EEO achieved was 54 kWh per cubic meter of water for each order of magnitude reduction in pollutant concentration -- an improvement in EEO over previously reported thin-film based photoreactors.

Three studies were performed to obtain fundamental mechanistic information on the TiO2 catalyzed photooxidations of organic substrates irradiated at 350 nm in dilute aqueous solutions under oxygenated conditions: (a) The photodecomposition of three haloethers, 2-chloroethyl ether, 4-chlorophenyl phenyl ether, and 4-bromophenyl phenyl ether, was investigated in an aqueous media at pH 7.0. (b) A comparative study of structure-reactivity was conducted on para-substituted phenols whose substituents range from electron-withdrawing to electron-donating in an aqueous media at pH 3.0. (c) The initial rates of the TiO2 catalyzed photodegratation of phenol were studied in an aqueous media at pH 1.0, 3.0, 5.0, 7.0, 9.0, 11.0, and 13.7 and a pH effect profile was obtained and compared to the removal efficiency after four hours of irradiation. Controls were carried out throughout the three studies in the absence of light and under anoxic conditions, as well as without the semiconductor to evaluate the role of photolysis. The Langmuir-Hinshelwood model was employed in an attempt to characterize and evaluate differences in reactivity.

Monodisperse titanium dioxide (TiO2) nanoparticles were synthesized by a novel freeze-drying process herein called lyophilization. The process of lyophilization is described in detail. The materials were characterized by scanning electron microscopy SEM) including energy dispersive x-ray spectroscopy (EDXS), high resolution transmission electron microscopy (HRTEM), x-ray diffraction (XRD), Raman spectroscopy and UV-Vis-IR spectrophotometry. The TiO2 nanoparticles have narrow size distribution, mono-disperse, strained with most of the characteristics showing presence of the four phases of TiO2 thus: anatase, brookite, rutile with each lyophilization process producing its own phase mostly controlled by pH and precursor concentration and anneal/calcining temperatures. With specific reference to HRTEM, Raman spectroscopy results and XRD, it was found that the Scherrer equation, the Williamson-Hall method and others of similar nature were not enough to explain the strain and the grain sizes of these particles. Therefore the Williamson-Hall method was revised to properly explain the new results. The obtained TiO2 nanoparticles were used in three applications: (1) gas sensing (2) degradation of organic water-borne pollutants using methylene blue as an indicator (3) anti-bacterial activity. / Physics / D. Phil. Physics)

Cheng Yee Wan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 95-112). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Table of Contents --- p.vi / List of Figures --- p.xi / List of Plates --- p.xiv / List of Tables --- p.xvi / Abbreviations --- p.xviii / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Legionella pneumophila --- p.1 / Chapter 1.1.1 --- Bacterial morphology and ultrastructure --- p.2 / Chapter 1.1.2 --- Microbial ecology and natural habitats --- p.4 / Chapter 1.1.2.1 --- Association with amoeba --- p.5 / Chapter 1.1.2.2 --- Association with biofilm --- p.5 / Chapter 1.2 --- Legionnaires' disease and clinical significance --- p.6 / Chapter 1.2.1 --- Epidemiology --- p.6 / Chapter 1.2.1.1 --- Worldwide distribution --- p.6 / Chapter 1.2.1.2 --- Local situation --- p.7 / Chapter 1.2.2 --- Clinical presentation --- p.7 / Chapter 1.2.3 --- Route of infection and pathogenesis --- p.8 / Chapter 1.2.4 --- Diagnosis --- p.10 / Chapter 1.2.4.1 --- Culture of Legionella --- p.10 / Chapter 1.2.4.2 --- Direct fluorescent antibody (DFA) staining --- p.13 / Chapter 1.2.4.3 --- Serologic tests --- p.13 / Chapter 1.2.4.4 --- Urine antigen testing --- p.14 / Chapter 1.2.4.5 --- Detection of Legionella nucleic acid --- p.15 / Chapter 1.2.5 --- Risk factors --- p.15 / Chapter 1.2.6 --- Treatment for Legionella infection --- p.16 / Chapter 1.3 --- Detection of Legionella in environment --- p.16 / Chapter 1.4 --- Disinfection methods --- p.17 / Chapter 1.4.1 --- Physical methods --- p.19 / Chapter 1.4.1.1 --- Filtration --- p.19 / Chapter 1.4.1.2 --- UV-C irradiation --- p.20 / Chapter 1.4.1.3 --- Thermal eradication (superheat-and-flush) --- p.21 / Chapter 1.4.2 --- Chemical methods --- p.21 / Chapter 1.4.2.1 --- Chlorination --- p.21 / Chapter 1.4.2.2 --- Copper-silver ionization --- p.22 / Chapter 1.4.3 --- Effect of biofilm and other factors on disinfection --- p.23 / Chapter 1.5 --- Photocatalytic oxidation (PCO) --- p.24 / Chapter 1.5.1 --- Generation of strong oxidants --- p.24 / Chapter 1.5.2 --- Disinfection mechanism(s) --- p.27 / Chapter 1.5.3 --- Major factors affecting the process --- p.28 / Chapter 2. --- Objectives --- p.30 / Chapter 3. --- Materials and Methods --- p.31 / Chapter 3.1 --- Chemicals --- p.31 / Chapter 3.2 --- Bacterial strains and culture --- p.31 / Chapter 3.3 --- Photocatalytic reactor --- p.33 / Chapter 3.4 --- PCO efficacy tests --- p.33 / Chapter 3.5 --- PCO sensitivity tests --- p.35 / Chapter 3.6 --- Optimisation of PCO conditions --- p.35 / Chapter 3.6.1 --- Optimization of TiO2 concentration --- p.36 / Chapter 3.6.2 --- Optimization of UV intensity --- p.36 / Chapter 3.6.3 --- Optimization of depth of reaction mixture --- p.36 / Chapter 3.6.4 --- Optimization of stirring rate --- p.37 / Chapter 3.6.5 --- Optimization of initial pH --- p.37 / Chapter 3.6.6 --- Optimization of treatment time and initial cell concentration --- p.37 / Chapter 3.6.7 --- Combinational optimization --- p.37 / Chapter 3.7 --- Transmission electron microscopy (TEM) --- p.38 / Chapter 3.8 --- Fatty acid profile analysis --- p.40 / Chapter 3.9 --- Total organic carbon (TOC) analysis --- p.42 / Chapter 3.10 --- UV-C irradiation --- p.44 / Chapter 3.11 --- Hyperchlorination --- p.44 / Chapter 3.12 --- Statistical analysis and replication --- p.45 / Chapter 3.13 --- Safety precautions --- p.45 / Chapter 4. --- Results --- p.46 / Chapter 4.1 --- Efficacy test --- p.46 / Chapter 4.2 --- PCO sensitivity --- p.47 / Chapter 4.3 --- Optimization of PCO conditions --- p.48 / Chapter 4.3.1 --- TiO2 concentration --- p.48 / Chapter 4.3.2 --- UV intensity --- p.48 / Chapter 4.3.3 --- Depth of reaction mixture --- p.51 / Chapter 4.3.4 --- Stirring rate --- p.56 / Chapter 4.3.5 --- Effect of initial pH --- p.56 / Chapter 4.3.6 --- Effect of treatment time and initial concentrations --- p.56 / Chapter 4.3.7 --- Combinational effects --- p.63 / Chapter 4.4 --- Transmission electron microscopy (TEM) --- p.66 / Chapter 4.4.1 --- Morphological changes induced by PCO --- p.66 / Chapter 4.4.2 --- Comparisons with changes caused by UV-C irradiation and chlorination --- p.67 / Chapter 4.5 --- Fatty acid profile analysis --- p.71 / Chapter 4.6 --- Total organic carbon (TOC) analysis --- p.73 / Chapter 4.7 --- UV-C irradiation --- p.74 / Chapter 4.8 --- Hyperchlorination --- p.74 / Chapter 5. --- Discussion --- p.76 / Chapter 5.1 --- Efficacy test --- p.76 / Chapter 5.2 --- PCO sensitivity --- p.76 / Chapter 5.3 --- Optimization of PCO conditions --- p.77 / Chapter 5.3.1 --- Effect of TiO2 concentration --- p.77 / Chapter 5.3.2 --- Effect of UV intensity --- p.78 / Chapter 5.3.3 --- Effect of depth of reaction mixture --- p.79 / Chapter 5.3.4 --- Effect of stirring rate --- p.79 / Chapter 5.3.5 --- Effect of initial pH --- p.80 / Chapter 5.3.6 --- Effect of treatment time and initial concentrations --- p.81 / Chapter 5.3.7 --- Combinational effect --- p.82 / Chapter 5.4 --- Transmission electron microscopy (TEM) --- p.83 / Chapter 5.4.1 --- Morphological changes induced by PCO --- p.83 / Chapter 5.4.2 --- Comparisons with changes caused by UV-C irradiation and chlorination --- p.85 / Chapter 5.5 --- Fatty acid profile analysis --- p.85 / Chapter 5.6 --- Total organic carbon (TOC) analysis --- p.86 / Chapter 5.7 --- Comparisons of the three disinfection methods --- p.88 / Chapter 6. --- Conclusion --- p.91 / Chapter 7. --- References --- p.95 / Chapter 8. --- Appendix --- p.113

PhD (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Anaerobic digestion (AD) is usually applied in the treatment of distillery effluent due to the fact that it is effective in chemical oxygen demand (COD) reduction and bioenergy recovery. However, due to the presence of biorecalcitrant melanoidins present in distillery effluent, AD is ineffective in colour reduction. For this reason, ultraviolet (UV) photodegradation, which is effective in melanoidins’ degradation, can be integrated with AD to achieve high efficiency in colour and COD reduction. However, the UV process is energy intensive, majorly due to the electricity requirement of the UV lamp. In contrast, the AD process has high potential of renewable energy production in the form of biomethane, which can be transformed into electrical energy and applied to supplement the energy requirement of the UV process. The aim of this study was to evaluate the efficiency of a combined AD-UV system in colour and COD reduction for the treatment of distillery effluent in fluidised bed reactors. The potential of the application of the bioenergy produced by the AD process to supplement the energy intensive UV process was evaluated and modelled using response surface methodology. In the first place, the optimal hydrodynamic conditions of the fluidised bed reactors were determined using optical attenuation technique. The best homogeneity in the bioreactor, in which zeolite was used as microbial support, was found to be at a superficial liquid velocity of 0.6 cm/s while the best catalyst and gas hold up in the photoreactor were found to be 0.077 and 0.003, respectively. At these conditions, it was found that the initial biological step removed about 90% of COD and only about 50% of the colour while photodegradation post-treatment removed 98% of the remaining colour. Kinetic analysis of the bioreactor showed that ~ 9% of the feed total organic carbon (TOC) was non-biodegradable and this was attributed to the biorecalcitrant melanoidins. Photodegradation post-treatment mineralized the biorecalcitrant melanoidins via a reductive pathway as was indicated by the formation of NH4+ in large quantity compared to NO3-. Kinetic analysis further showed that the rate of substrate utilization in the bioreactor increased with an increase in organic loading rate and it was inversely proportional to the rate of photodegradation post-treatment. Modeling using response surface methodology (RSM) was applied to predict the effects of the operating parameters of the initial AD step on the performance of the photodegradation post-treatment process and the energy efficiency. Energy analysis of the integrated system showed that the AD process could produce 59 kWh/m3 of electricity which could supplement the electricity demand of the UV lamp by 30% leading to operation cost reduction of about USD 4.8/m3. This led to a presumed carbon dioxide emission reduction (CER) of 28.8 kg CO2e/m3.

Wong Man Yung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (leaves 106-120). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Table of Contents --- p.vi / List of Figures --- p.xi / List of Plates --- p.xiii / List of Tables --- p.xv / Abbreviations --- p.xvi / Equations --- p.xviii / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Water disinfection --- p.1 / Chapter 1.2 --- Bacterial species --- p.2 / Chapter 1.2.1 --- Staphylococcus saprophyticus --- p.2 / Chapter 1.2.2 --- Enterobacter cloacae --- p.3 / Chapter 1.3 --- Disinfection methods --- p.4 / Chapter 1.3.1 --- Physical methods --- p.4 / Chapter 1.3.1.1 --- UV-C irradiation --- p.4 / Chapter 1.3.1.2 --- Solar disinfection --- p.5 / Chapter 1.3.2 --- Chemical methods --- p.6 / Chapter 1.3.2.1 --- Chlorination --- p.6 / Chapter 1.3.2.2 --- Ozonation --- p.7 / Chapter 1.3.2.3 --- Mixed disinfectants --- p.8 / Chapter 1.3.3 --- Other disinfection methods --- p.8 / Chapter 1.4 --- Advanced oxidation processes (AOPs) --- p.9 / Chapter 1.5 --- Photocatalytic oxidation (PCO) --- p.10 / Chapter 1.5.1 --- PCO process --- p.12 / Chapter 1.5.2 --- Photocatalysts --- p.14 / Chapter 1.5.2.1 --- Titanium dioxide (P25) --- p.15 / Chapter 1.5.2.2 --- Silver sensitized P25 (Ag/P25) --- p.16 / Chapter 1.5.2.3 --- Silicon dioxide doped titanium dioxide (SiO2-TiO2) --- p.17 / Chapter 1.5.2.4 --- Copper(I) oxide sensitized P25 (Cu2O/P25) --- p.18 / Chapter 1.5.3 --- Irradiation sources --- p.19 / Chapter 1.5.4 --- PCO disinfection mechanisms --- p.20 / Chapter 1.6 --- Bacterial defense mechanisms against oxidative stress --- p.22 / Chapter 2. --- Objectives --- p.25 / Chapter 3. --- Materials and Methods --- p.26 / Chapter 3.1 --- Chemicals --- p.26 / Chapter 3.2 --- Bacterial culture --- p.26 / Chapter 3.3 --- Photocatalytic reactor --- p.27 / Chapter 3.4 --- PCO efficacy test --- p.30 / Chapter 3.5 --- Optimization of PCO conditions --- p.31 / Chapter 3.5.1 --- Effect of P25 concentrations --- p.31 / Chapter 3.5.2 --- Effect of UV intensities --- p.32 / Chapter 3.5.3 --- Combinational study of P25 concentrations and UV intensities --- p.32 / Chapter 3.5.4 --- Effect of stirring rates --- p.32 / Chapter 3.5.5 --- Effect of initial cell concentrations --- p.33 / Chapter 3.6 --- PCO disinfection using different photocatalysts --- p.33 / Chapter 3.6.1 --- Effect of CU2O/P25 concentrations --- p.33 / Chapter 3.6.2 --- Effect of CU2O powder on the two bacterial species --- p.33 / Chapter 3.7 --- Transmission electron microscopy (TEM) --- p.34 / Chapter 3.8 --- Catalase (CAT) test --- p.37 / Chapter 3.9 --- Superoxide dismutase (SOD) activity assay --- p.39 / Chapter 4. --- Results --- p.40 / Chapter 4.1 --- Efficacy test --- p.40 / Chapter 4.2 --- PCO disinfection under UV irradiation --- p.40 / Chapter 4.2.1 --- Control experiments --- p.40 / Chapter 4.2.2 --- Optimization of PCO conditions using P25 as a photocatalyst --- p.42 / Chapter 4.2.2.1 --- Effect of P25 concentrations --- p.42 / Chapter 4.2.2.2 --- Effect of UV intensities --- p.45 / Chapter 4.2.2.3 --- Combinational study of P25 concentrations and UV intensities --- p.48 / Chapter 4.2.2.4 --- Effect of stirring rates --- p.54 / Chapter 4.2.2.5 --- Effect of initial cell concentrations --- p.57 / Chapter 4.2.3 --- Comparison of PCO inactivation efficiency between S. saprophyticus and E. cloacae --- p.60 / Chapter 4.2.4 --- PCO disinfection using different photocatalysts --- p.62 / Chapter 4.2.4.1 --- Control experiments --- p.62 / Chapter 4.2.4.2 --- Ag/P25 --- p.62 / Chapter 4.2.4.3 --- SiO2-TiO2 --- p.64 / Chapter 4.2.4.4 --- Cu2O/P25 --- p.64 / Chapter 4.3 --- PCO disinfection under visible light irradiation --- p.66 / Chapter 4.3.1 --- Effect of Cu2O/P25 concentrations --- p.67 / Chapter 4.3.2 --- Effect of CU2O powder on the two bacterial species --- p.70 / Chapter 4.4 --- Feasibility use of indoor light (fluorescent lamps) for PCO disinfection --- p.71 / Chapter 4.5 --- Transmission electron microscopy (TEM) --- p.74 / Chapter 4.5.1 --- Morphological changes induced by PCO using P25 as a photocatalyst --- p.74 / Chapter 4.5.2 --- Morphological changes induced by PCO using Cu2O/P25 as a photocatalyst --- p.77 / Chapter 4.6 --- Catalase (CAT) test --- p.80 / Chapter 4.7 --- Superoxide dismutase (SOD) activity assay --- p.82 / Chapter 5. --- Discussion --- p.83 / Chapter 5.1 --- Efficacy test --- p.83 / Chapter 5.2 --- PCO disinfection under UV irradiation --- p.83 / Chapter 5.2.1 --- Optimization study --- p.84 / Chapter 5.2.1.1 --- Effect of P25 concentrations --- p.84 / Chapter 5.2.1.2 --- Effect of UV intensities --- p.85 / Chapter 5.2.1.3 --- Combinational study of P25 concentrations and UV intensities --- p.86 / Chapter 5.2.1.4 --- Effect of stirring rates --- p.86 / Chapter 5.2.1.5 --- Effect of initial cell concentrations --- p.87 / Chapter 5.2.2 --- Comparison of PCO inactivation efficiency between S. saprophyticus and E. cloacae --- p.88 / Chapter 5.2.3 --- PCO disinfection using different photocatalysts --- p.89 / Chapter 5.2.3.1 --- Ag/P25 --- p.89 / Chapter 5.2.3.2 --- SiO2-TiO2 and Cu2O/P25 --- p.90 / Chapter 5.3 --- PCO disinfection under visible light irradiation --- p.90 / Chapter 5.3.1 --- Effect of Cu20/P25 concentrations --- p.91 / Chapter 5.3.2 --- Effect of CU2O powder on the two bacterial species --- p.92 / Chapter 5.4 --- Feasibility use of fluorescent lamps for PCO disinfection --- p.93 / Chapter 5.5 --- Transmission electron microscopy (TEM) --- p.95 / Chapter 5.5.1 --- Morphological changes induced by PCO using P25 as a photocatalyst --- p.95 / Chapter 5.5.2 --- Morphological changes induced by PCO using CU2O/P25 as a photocatalyst --- p.96 / Chapter 5.6 --- Catalase (CAT) test --- p.98 / Chapter 5.7 --- Superoxide dismutase (SOD) activity assay --- p.99 / Chapter 6. --- Conclusion --- p.101 / Chapter 7. --- References --- p.106 / Chapter 8. --- Appendix --- p.121