京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21964号 / 工博第4619号 / 新制||工||1720(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 高岡 昌輝, 准教授 福谷 哲 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The mining industry is a significant contributor to the Canadian economy. However, the mining activities can be detrimental to the environment due to the release of pollutants. Ammonia is one of the noxious and toxic contaminants associated with mining, ammonia contamination is created by the oxidizing agent in explosives. The explosives impacted mining wastewater (EIMWW) usually contains ammonia and other metal ions. The ammonia in EIMWW could harm the aquatic environment by the depletion of oxygen and its lethal toxicity to aquatic organisms. Before release to environment, EIMWW needs to be treated with an easy-to-operate method for ammonia removal at the remote mining sites. Ion-exchange (IE) with zeolite is an effective method for ammonia removal that is easy-to-operate, is not significantly impacted by cold temperature or toxicity effects. However, the traditional IE regeneration approach of using high concentration NaCl solutions creates a secondary polluting stream. Chlorine regeneration of ammonia-loaded zeolite appears to be a promising option, an evaluation of this option is the main topic of this thesis. This thesis includes three initiatives. The first is a set of multi-cycle batch loading-regeneration tests to assess the viability of ammonia removal with a commercial zeolite (SIR-600) for the treatment of a synthetic EIMWW (containing total ammonia nitrogen (TAN), K, and Ca) and to examine the performance of different ion-exchange regeneration solutions. The long-term TAN uptake of SIR-600 regenerated using a NaOCl (100 mg free Cl2/L) solution was 0.24 meq/g, which was approximately 20% lower than that after a NaCl regeneration. However, chlorine regeneration is promising because the selectivity of SIR-600 for TAN over Ca and K increased after the chlorine regeneration. To simulate recycling of the NaOCl regenerants, K and Ca were added to the NaOCl solution, it did not substantially affect the subsequent SIR-600’s ion uptake. This initiative represents a significant contribution since the earlier studies into chlorine regeneration did not investigate the impact of competing ions. The second initiative addressed concerns regarding the long-term integrity of SIR-600 arising from its exposure to high chlorine concentrations during the regeneration. The five-week long chlorine batch exposure tests with solutions of up to 1000 mg free Cl2/L showed that chlorine exposure did not significantly affect the SIR-600’s characteristics in terms of particle size distribution, surface area, FTIR spectra and ion uptake. Thus, SIR-600 has the potential for long-term use in field applications. The final initiative evaluated the feasibility of chlorine regeneration for continuous flow IE column systems used for ammonia removal from a synthetic EIMWW. Continuous flow column systems are important because these are the standard IE units used in full-scale applications. Multi-cycle column loading-regeneration tests were performed to compare the zeolite performance using a NaOCl (1000 ppm as free Cl2) solution with that using a 5% NaCl regeneration. The influence of loading duration was also assessed. The use of 6-hr loading cycles were shown to be preferable to 23-hr loading cycles because it had lower effluent concentrations and they could achieve higher overall TAN mass removals per unit time. After three operational cycles, the SIR-600 had similar TAN uptake performances (0.21 meq/g Vs. 0.21 meq/g) after NaOCl regeneration and after salt (NaCl) regeneration. This is in contrast to the lower TAN uptakes for the NaOCl regeneration in the batch tests, this indicates that batch tests are not always representative of full-scale applications. Compared to NaCl regenerated SIR-600, SIR-600 after NaOCl regeneration had a higher preference for TAN over Ca and K, which makes this type of regeneration very promising. Its only apparent limitation is that the NaOCl regeneration required a longer duration. During the NaOCl regeneration, the main mechanism appears to be the oxidation of ammonia to nitrogen gas and hydrogen ions, however the Na in the NaOCl solution also seems to have a role in the regeneration.

Polyelektrolyte (PEs) bilden eine große Klasse von Materialien, die in der wissenschaftlichen Forschung immer mehr Beachtung findet. Aufgrund der Lange-Bereich Elektrostatic ist das theoretische Verständnis von PE-Lösungen im Vergleich zu ihren neutralen Gegenstücken noch relativ schlecht gewesen, dadurch die Rationalisierung der Gegenionskondensation auf hochgeladenen PEs herausfordern. Die Komplexität des Problems wird noch zusätzlich durch die gleichzeitige Anwesenheit monovalenter und divalenter Gegenionen in der Lösung, was vielen biologische Umgebungen entspricht, erhöht. Dies beeinflusst die PE-Protein Komplexierungen, damit ihren Funktionen und Anwendungen in der Biomedizin und Biotechnologie. In dieser Arbeit führen wir eine umfassende Analyse der Ladungs- und Hydratationsstruktur von dendritischen PEs in einem monovalenten Salz unter Verwendung von atomistischen Molekulardynamik (MD) Computersimulationen mit explizitem Wasser durch. Darüber hinaus untersuchen der kompetitiven Adsorption der monovalenten und divalenten Gegenionen am globulären PE mit Hilfe theoretischer Mean-Field-Modelle, vergröberter und atomistischer (expliziter) Wasser-Simulationen und Kalorimetrie-Experimenten. Wir befassen uns mit der Herausforderung, eine genau definierte effektive Ladung und ein Oberflächenpotential der PEs für praktische Anwendungen zu finden, und präsentieren ein neuartiges kompetitives Ionenbindungsmodell, das einen aussagekräftigen Vergleich zwischen Theorie, Simulationen und Experimenten gewährleistet. Diese Arbeit stellt eine systematische elektrostatischen Beschreibung von PE vor, untersucht die thermodynamische PE-Wasser Signatur und analysiert die kompetitiven Bindung von monovalenten und divalenten Gegenionen an PEs. Es wird ein tieferer Einblick in die physikochemischen Aspekte von PE-Gegenionen- und PE-Wasser-Wechselwirkungen erhalten, was für das rationale Design von PEs auf einer gezielten Anwendungsbasis von entscheidender Bedeutung ist. / Polyelectrolytes (PEs) represent a broad class of materials that are getting an increasing attention in the scientific community. However, due to the long-range electrostatics, the theoretical understanding of PE solutions has been relatively poor compared to their neutral counterparts, thereby challenging the rationalization of the counterion condensation on highly charged PEs. Moreover, the counter-intuitive footprint of PE-water thermodynamics, and the simultaneous presence of the divalent and the monovalent counterions in the solution, as is reminiscent of many biological environments, escalates the complexity and richness of the problem. This affects the PE-proteins complexations, and thus their functions, applications in biomedicine and biotechnology. In this thesis, we conduct a comprehensive analysis of the charge and hydration structure of dendritic PEs in a monovalent salt using all-atom explicit-water molecular dynamics computer simulations, and investigate a competitive sorption of mono- versus divalent ions on globular PEs using mean-field theoretical models, all-atom and coarse-grained simulations and calorimetry experiments. We address the challenges of obtaining a well-defined effective charge and surface potential of the PE for practical applications and present a novel competitive ion binding model, ensuring a meaningful comparison between theory, simulations and experiments. This thesis lays out a systematic PE electrostatic characterization, explores PE-water thermodynamics, and analyses the competitive binding of divalent and monovalent counterions on the PE. A deeper insight into the physicochemical aspects of PE-counterion and PE-water interactions is achieved, which is vital towards the rational design of PEs on a targeted application basis.