With its long cycle life and scalable design, the vanadium redox flow battery (VRB) is a promising technology for grid energy storage. However, high materials costs have impeded its commercialization. An essential but costly component of the VRB is the ion-exchange membrane. The ideal VRB membrane provides a highly conductive path for protons, prevents crossover of reactive species, and is tolerant of the acidic and oxidizing chemical environment of the cell. In order to study membrane performance and optimize cell design, mathematical models of the separator membrane have been developed. Where previous VRB membrane models considered minimal details of membrane transport, generally focusing on conductivity or self-discharge at zero current, the model presented here considers coupled interactions between each of the major species by way of rigorous material balances and concentrated solution theory. The model describes uptake and transport of sulfuric acid, water, and vanadium ions in Nafion membranes, focusing on operation at high current density. Governing equations for membrane transport are solved in finite difference form using the Newton-Raphson method. Model capabilities were explored, leading to predictions of Ohmic losses, vanadium crossover, and electro-osmotic drag. Experimental methods were presented for validating the model and for further improving estimates of uptake parameters and transport coefficients. / text

It is known that when water is a product in reactions catalysed by cation exchange resins, it inhibits the reaction rate much more than predicted by the reverse reaction or dilution effects. In this work the inhibiting effect is ascribed to the preferential association of the catalytically active sites with water. In the derivation of the kinetic model, a Freundlich type adsorption isotherm was used to quantify the number of sites occupied by water. This is combined with a power law expression for the reaction rate. The resultant expression can accurately predict the reaction rate for various initial concentrations of water and mesityl oxide. Even when water was initially added to the reaction mixture, this model still gave an absolute average error of 6.5% compared to a 54.6% error when the same approach was followed but with the more popular Langmuir isotherm to describe site deactivation. The kinetic expression previously proposed for this reaction system by Klein and Banchero also failed when water was added to the reaction mixture and gave an average error of 71.1%. The procedure used to derive the model is therefore suggested for all cation exchange catalysed reactions where water is one of the products. / Dissertation (MSc)--University of Pretoria, 2005. / Chemical Engineering / unrestricted

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京都大学 / 新制・課程博士 / 博士(薬科学) / 甲第23135号 / 薬科博第134号 / 新制||薬科||15(附属図書館) / 京都大学大学院薬学研究科薬科学専攻 / (主査)教授 石濱 泰, 教授 松﨑 勝巳, 教授 加藤 博章 / 学位規則第4条第1項該当 / Doctor of Pharmaceutical Sciences / Kyoto University / DFAM

Landfilling is the most common approach to dispose of municipal solid wastes but inevitably leads to leachate formation. Persistent UV quenching substances (UVQS) in landfill leachate can affect the effectiveness of UV disinfection in municipal wastewater treatment systems when leachate co-treatment is applied. Membrane electrochemical reactor (MER) treatment was investigated to reduce the UV quenching capability and simultaneously recover resources in the leachate as an effective onsite pre-treatment. Ion-selective membranes were used in this MER to create two different conditions: a low-pH anolyte for organic oxidation and a high-pH catholyte for ammonia recovery. The MER achieved significantly higher removals of both dissolved organic carbon and UV254nm absorbance than membrane-less electrochemical treatment. The MER was able to remove a large percentage of total nitrogen from the leachate while recovering about half of the influent ammonia in the catholyte with less specific energy consumption. The second study coupled MER with Fenton oxidation through providing synergistic benefits with the low solution pH, reduced organics, and ammonia removal. This two-stage coupled system reduced the more leachate COD than the standalone Fenton process treating raw leachate. Also, the usage of chemicals as Fenton reagents has been greatly reduced: FeSO4 and H2O2 by 39%, H2SO4 by 100%, and NaOH by 55%. Consequently, the sludge production was reduced by 51% in weight and 12% in volume. Despite electricity consumption by the MER, the coupled system cost $4.76 per m3 leachate less than the standalone Fenton treatment. More notably, direct Fenton oxidation removed only 21% of ammonia; in comparison, the MER-Fenton system removed ammonia by 98% with the possibility for recovery at a rate of 30.6 -55.2 kg N m-3 reactor d-1. Those results demonstrated that coupling MER with the Fenton process could mitigate some inherent drawbacks of Fenton oxidation such as ineffective ammonia removal, high acid and chemical reagents dose requirements, and a large amount of sludge generation. The third study investigated the formation of total halogenated organics (DBP) and the associated toxicity as the side effect of leachate treatment in the MER. Compared to the 4538±100 µg L-1 from the control membrane-less electrochemical oxidation reactor, the amount of DBP generated in the MER only accounted for 19.1±4.5 % after the same treatment period. The total toxicity value (26.6 ×10-3 ) was low for MER effluent, only 15.1% of that in the control group. Both high pH and high ammonia concentration introduced more DBP mass and toxicity production after MER treatment. DBP concentrations were shown to increase with applied current density and possible temperature raise. With 67.5% of DBP mass concentration and 74.4% of the additive toxicity removal, the granular activated carbon (GAC) electrode system was shown more effective than GAC adsorption alone in remediating DBP harmful effects. This dissertation introduced MER as a promising technology for the treatment of leachate through performance demonstration, process integration and by-product remediation. / Doctor of Philosophy / Municipal solid waste is often disposed of in landfills because of the most economics and convenience. However, one of the most challenging problems is the leachate formation and treatment. In the US, leachate is currently often diluted in domestic wastewater treatment systems; meanwhile, the persistent contaminants in landfill leachate can lower the effectiveness of UV disinfection and result in high cost and permit violation. In this study, the membrane electrochemical reactor (MER) using electricity as the driving force was applied to solve the issue and simultaneously recover valuable resources in the leachate. Membranes as a barrier for selective ions were used in this MER to create two different conditions with different purposes: a low-pH anolyte for organic oxidation and a high-pH catholyte for ammonia recovery. The MER achieved significantly higher contaminants removals than membrane-less electrochemical treatment. The second study coupled MER with one of the established advanced oxidation processes, also known as Fenton oxidation through providing mutual benefits with the low solution pH, reduced organics, and ammonia removal/recovery. This two-stage coupled system reduced the leachate contaminants effectively towards the direct discharge standard. In addition, the usage of chemical reagents, as well as the amount of process residual, has significantly been reduced. The third study investigated the formation of by-products as the side effect of leachate treatment in the MER. Compared to the membrane-less reactor, the undesirable by-products generated in the MER only accounted for one fifth after the same treatment period. A granular activated carbon electrode system was shown effective in remediating the harmful effects. This dissertation introduced MER as a promising technology for the treatment of leachate as one of the toughest wastewaters.

Extracellular vesicles (EV) originate from various cell types and reflect the contents of the originating cells. EVs are ubiquitous in nearly all body fluids, including blood plasma, and exhibit significant potential as biomarkers in disease diagnostics. However, isolating EVs from blood plasma remains challenging due to the lack of a standardised method. This study aimed to compare and optimize a density gradient ultracentrifugation workflow (DUC) against size exclusion chromatography-cation exchange chromatography (SEC-CEC) and evaluate SEC versus SEC-CEC. Common contaminants during isolation include lipoproteins (LP); previous studies have shown that lowering the pH of blood plasma can precipitate LP, enhancing isolation efficiency. Acidified blood plasma was compared with neutral plasma for EV isolation using all above mentioned methods. To assess the ability of the isolation methods to purify contaminants while retaining maximal EV yield, samples were analysed using multiple techniques, including particle quantity, free proteins, LP-associated apolipoprotein B, purity index (μg protein/particle), and EV-associated surface markers. The results indicate potential for DUC, but further optimization is necessary to improve the method and its isolation of EV. SEC-CEC emerged as an effective method, reducing contaminants by 71% (SEC) to 99% (SEC-CEC), increasing purity by 80%, and yielding positive signals from EV markers (SEC-CEC). The effect of acidification was ambiguous, it reduced apolipoprotein-B levels in plasma pre-isolation. However, post- isolation, neutral plasma exhibited significantly lower contaminations, albeit at the expense of total particle content and risking EV loss. The study underscored several advantages of SEC-CEC but indicated that acidification did not optimise isolation efficiency.

Mechanisms of adsorption of alkaline copper quat (ACQ) components in wood were investigated with emphasis on: copper chemisorption, copper physisorption, and quat adsorption. Various factors were investigated that could affect the adsorption of individual ACQ components in red pine wood. Copper chemisorption in wood was affected by ligand types coordinating with Cu and the stability of the Cu-ligand complexes in solution. For Cu-monoethanolamine (Cu-Mea) system, the prevailing active solvent species at the solution pH, [Cu(Mea)2-H]+ complexes with wood acid sites and loses one Mea molecule through a ligand exchange reaction. The amount of adsorbed Cu was closely related to the cation exchange capacity of wood. An increase in Mea/Cu ratio increased the proportion of the uncharged Cu-Mea complex and resulted in decreased Cu chemisorption in wood. Copper precipitation is also an important Cu fixation mechanisms of Cu-amine treated wood. X-ray diffraction analysis revealed that in vitro precipitated Cu was a mixture of copper carbonates (azurite and malachite) and possibly Cu2O. Higher concentration Cu-amine solutions retarded the Cu precipitation to a lower pH because of higher free amine in the preservative-wood system. The changes in zeta potential of wood in relationship to the quaternary ammonium (alkyldimethylbenzylammonium chloride: ADBAC) adsorption isotherm showed two different adsorption mechanisms for quat in wood: ion exchange reaction at low concentration and additional aggregation form of adsorption by hydrophobic interaction at high concentration. Because of the aggregation effect, when wood was treated with ACQ, high amounts of ADBAC were concentrated near the surface creating a steep gradient with depth. This aggregated ADBAC was easily leached out while the ion exchanged ADBAC had high leaching resistance. Free Mea and Cu of ACQ components appeared to compete with ADBAC for the same bonding sites in wood.

This study focuses on the development of novel two-stage esterification-transesterification synthesis of biodiesel from used cooking oil (UCO) using novel heterogeneous catalysts. The esterification of the UCO was investigated using three types of ion exchange resins catalysts including Purolite D5081, Purolite D5082 and Amberlyst 15. Of all the catalysts investigated, Purolite D5081 resin showed the best catalytic performance and was selected for further optimisation studies. From the optimisation study, it was found that the external and internal mass transfer resistance has negligible effect on the esterification reaction. At the optimum reaction conditions, Purolite D5081 achieved 92% conversion of FFA. During reusability study, the conversion of FFA dropped by 10% after each cycle and it was found that progressive pore blockage and sulphur leaching were dominant factors that decreased the catalytic performance of the Purolite D5081 catalyst. A kinetic modelling for FFA esterification was carried out using Purolite D5081 as a catalyst. Three types of kinetic models were investigated i.e. pseudo homogeneous (PH), Eley-Rideal (ER) and Langmuir-Hinshelwood-Hougen-Watson (LHHW). Experimental data obtained from the batch kinetic studies was successfully represented by the PH model and a good agreement between experimental and calculated values was obtained. The activation energy for esterification and hydrolysis reaction was found to be 53 and 107 kJ/moL. The transesterification of pre-treated cooking oil (P-UCO) was investigated using various types of heterogeneous catalysts including Purolite CT-122, Purolite CT-169, Purolite CT-175, Purolite CT-275, Purolite D5081, Diaion PA306s and Cs-supported heteropolyacids catalysts. Of all the catalysts investigated, Diaion PA306s catalyst showed the highest conversion of triglycerides and was selected for further optimisation studies. At the optimum reaction conditions, Diaion PA306s achieved ca. 75% of triglycerides conversion. During the reusability study, Diaion PA306s catalyst gave a similar conversion of triglycerides after being reused once. Therefore, it was concluded that the resin can be used several times without losing catalytic activity. Several purification methods have been investigated and dry washing method was chosen as the best alternative for biodiesel purification.

The explosive 2,4,6-trinitrotoluene (TNT) is currently a main ingredient in munitions; however the compound has failed to meet the new sensitivity requirements. The replacement compound being tested is 2,4-dinitroanisole (DNAN). DNAN is less sensitive to shock, high temperatures, and has good detonation characteristics. However, DNAN is more soluble than TNT, which can influence transport and fate behavior and thus bio-availability and human exposure potential. The objective of this study was to investigate the environmental fate and transport of DNAN in soil, with specific focus on sorption processes. Batch and column experiments were conducted using soils collected from military installations located across the United States. The soils were characterized for pH, electrical conductivity, specific surface area, cation exchange capacity, and organic carbon content. In the batch rate studies, change in DNAN concentration with time was evaluated using the first order equation, while adsorption isotherms were fitted using linear and Freundlich equations. Solution mass-loss rate coefficients ranged between 0.0002 h(-1) and 0.0068 h(-1). DNAN was strongly adsorbed by soils with linear adsorption coefficients ranging between 0.6 and 6.3 L g(-1), and Freundlich coefficients between 1.3 and 34 mg(1-n) L-n kg(-1). Both linear and Freundlich adsorption coefficients were positively correlated with the amount of organic carbon and cation exchange capacity of the soil, indicating that similar to TNT, organic matter and clay minerals may influence adsorption of DNAN. The results of the miscible-displacement column experiments confirmed the impact of sorption on retardation of DNAN during transport. It was also shown that under flow conditions DNAN transforms readily with formation of amino transformation products, 2-ANAN and 4-ANAN. The magnitudes of retardation and transformation observed in this study result in significant attenuation potential for DNAN, which would be anticipated to contribute to a reduced risk for contamination of ground water from soil residues.