Modélisation des transferts de masse et de chaleur dans une cellule d'électrolyse de production de fluor. La production de fluor par électrolyse est une étape clé de la conversion de l’uranium dans l’industrie nucléaire. Afin d’optimiser ce procédé, les travaux de thèse décrits dans ce manuscrit se sont concentrés sur deux axes : le développement d’un modèle numérique de l’électrolyseur et l’étude du phénomène d’hyperpolarisation cathodique néfaste pour le bon fonctionnement de la cellule. Un modèle couplant plusieurs physiques (thermique avec solidification, diphasique, électrocinétique) a été développé et des essais expérimentaux ont été menés afin d’acquérir, d’une part, certaines propriétés physiques de l’électrolyte nécessaires aux simulations (conductivité thermique et capacité thermique à pression constante) et, d’autre part, des données expérimentales permettant de qualifier le modèle obtenu. Ce travail de modélisation a abouti à l’obtention d’un modèle 3D fiable couplant les physiques citées précédemment, ceci à l’échelle d’un pilote R&D semi-industriel. L’impact de la solidification de l’électrolyte sur le transfert de chaleur a également pu être simulé pour la première fois. Ces essais ont également permis de fournir des premières explications sur le phénomène d’hyperpolarisation cathodique en dressant des tendances claires quant à l’influence de certains paramètres de contrôle de l’électrolyseur comme le titre HF et la température de consigne. / Computer modeling of heat transfer and mass transfer in an electrolytic cell for production of fluorineElectrolytic production of fluorine is a key step in uranium conversion for the nuclear industry. In order to improve this process, the work described in this dissertation aims at two main objectives: to build a numerical simulation of the electrolysis cell and to understand the cathodic hyperpolarization effect which lowers the productivity of the cell. A model coupling several physics (heat transfer with solidification, two-phase flow, electrokinetics) has been developed and experiments were made in order to evaluate unknown physical properties of the electrolyte (thermal conductivity and heat capacity at constant pressure). Experimental data were also acquired in order to assess the capacity of the model to simulate various phenomena occurring inside the cell. Eventually, a reliable 3D model of a semi-industrial R&D cell coupling the physics above mentioned has been obtained. The negative impact of the solidification of the electrolyte on the cooling system was simulated for the first time. Thanks to these experiments, it was also possible to determine the major trends which drive the cathodic hyperpolarization effect. The influence of HF mass fraction and temperature on this phenomenon was clearly shown.

L’économie actuelle repose sur l’utilisation d’énergies fossiles dont les réserves sont limitées. En plus, l’utilisation de ces ressources a un impact négatif sur l’environnement dû à l’émission des gaz polluants et du CO2. Il est donc nécessaire de remplacer les ressources fossiles par les énergies renouvelables. Les énergies renouvelables peuvent être facilement converties en électricité pour une utilisation directe, mais l’électricité ne peut pas être stockée en grande quantité. Dans ce contexte, l’hydrogène pourrait servir de vecteur énergétique. Il est possible de produire de l’hydrogène par électrolyse de l’eau. L’hydrogène sera ensuite utilisé via une pile à combustible pour fournir de l’électricité et de la chaleur. Ce procédé ne produit que de l’eau qui va être re-consommé ensuite par l’électrolyse.Ce travail de thèse est axé sur la production d’hydrogène par électrolyse de l’eau en milieu acide par la technologie PEM (proton exchange membrane). L’objectif est de remplacer le platine, catalyseur de la réduction à la cathode par des complexes de cobalt de type cobalt-oxime.Le premier chapitre traite différents aspects de l’électrolyse de l’eau et différents catalyseurs étudiés dans la littérature.Le second chapitre décrit différentes techniques expérimentales utilisées pour caractériser les complexes étudiés.Le chapitre trois décrit la synthèse et l’activité catalytique des complexes de cobalt-oxime en solution dans l’acétonitrile vis-à-vis de la réduction des protons en hydrogène.Le chapitre quatre présente les premiers travaux obtenus en utilisant les complexes de cobalt-oxime à la place du platine dans les électrolyseurs PEM. / Today's economy is base on the use of fossil fuels, whose reserves are limited. In addition, the use of these resources has a negative impact on the environment due to the emission of polluting gases and CO2. Therefore it is necessary to replace fossil fuels by renewable energy. Renewable energy can be easily converted to electricity to direct use, but electricity can not be stored in large quantities. In this context, hydrogen could be used as an energy carrier. It is possible to produce hydrogen by electrolysis of water. Hydrogen is then used via a fuel cell to supply electricity and heat. This process produces only water which will then be re-used by the electrolysis.This thesis focuses on hydrogen production by water electrolysis in acidic medium by the PEM (proton exchange membrane) technology. The goal is to replace the platinum, catalyst for proton reduction at the cathode by cobalt-oxime complexes.The first chapter describes various aspects of water electrolysis and different catalyst studied in the literature.The second chapter describes different characterization techniquesChapter three describes the synthesis and catalytic activity of the complexes of cobalt-oxime in solution in acetonitrile towards proton reduction into hydrogen.Chapter four presents the early work obtained using cobalt complexes oxime instead of platinum in PEM electrolyzers.

La production d’hydrogène et de dioxygène par électrolyse PEM (PEM « Proton Exchange Membrane ») de l’eau s’effectue grâce à la présence de métaux nobles dans les couches catalytiques: à la cathode, le platine supporté sur du carbone est généralement utilisé (les chargements en métaux nobles sont faibles de l’ordre de 0,5 mg/cm²) ; à l’anode, la production d’oxygène s’effectue à des potentiels élevés (> 1,6 V vs. ESH). Les oxydes de métaux nobles sont utilisés seuls dans la couche active anodique et servent à la fois de catalyseurs et de conducteurs électroniques. Comme ils sont parmi les métaux les plus denses, pour obtenir une continuité électrique de la couche anodique, les chargements doivent être très élevés, de l’ordre de 2-3 mg/cm².Cette thèse propose ainsi de développer de nouveaux matériaux supports stables électrochimiquement et bons conducteurs électroniques pour séparer les fonctions de catalyse et de conduction électronique. Pour cela, des assemblages membrane électrodes intégrant des particules de titane comme support de catalyseur anodique ont été préparés dans notre laboratoire. Testés en mono-cellule de 25 cm², leurs principales caractéristiques ont été déterminées par voltampérométrie cyclique, spectroscopie d’impédance et grâce à des courbes de polarisations à différentes températures. La comparaison des résultats obtenus entre ces anodes « innovantes » et celles à base de catalyseur seul a permis de mettre en évidence la présence d’un chargement anodique seuil de 0,5 mg/cm² en dessous duquel la présence d’un support de catalyseur est nécessaire pour assurer la percolation électrique. Grâce à l’utilisation de ce support de catalyseur bon marché, les chargements anodiques ont pu être réduits jusqu’à des valeurs aussi faibles que 0,1 mg/cm² IrO2, soit une réduction de dix fois au minimum par rapport aux taux généralement employés dans la littérature, tout en maintenant des performances identiques. / It is expected that PEM water electrolysis will play a significant role in the hydrogen society as a key process for producing hydrogen from renewable energy sources but before this, substantial cost reductions are still required. Because of the high acidity of membrane materials used in PEM water electrolysers, expensive noble-metals or their oxides are required as electrocatalysts (platinum for hydrogen evolution and iridium for oxygen evolution). As the oxygen evolution reaction takes place with a large overpotential (anodic potential > 1.6 V) only few materials can be used to avoid corrosion. In state-of-the-art, noble metal oxides are generally used alone in the active layer with typical loadings of 2-3 mg/cm² and act as both catalyst and electronic conductor.In order to reduce the noble metal loadings and keep a good electronic conductivity of the catalytic layer, iridium can be supported onto a conductive and electrochemical stable material support. To gain more insights, several MEAs with anodes made of pure iridium oxide or 50 wt % IrO2/Ti anodes have been prepared and characterized using cyclic voltammetry and impedance spectroscopy, and by measuring polarization curves at different operating temperatures. Without the catalyst support, anodic loadings can be reduced down to 0,5 mg/cm² without any degradation in the electrochemical performances. By using anodes made of iridium oxide and titanium particles, further reductions of anodic loading can be made down to 0.1 mg/cm² with performances similar to those obtained with conventional loadings of several mg cm-2.

Orientador: Keizo Yukimitu / Banca: Victor Ciro Solano Reynoso / Banca: Sandro Márcio Lima / Resumo: No presente trabalho, investigaram-se os efeitos dos íons alcalinos Na+, Li+ substituídos pelo íon H+ e Na+ nos centros relacionados ao alumínio que é uma impureza encontrada naturalmente nas matrizes de quartzo natural. Foram realizadas medidas de absorção óptica na região do visível e do ultravioleta, assim como medidas no infravermelho de amostras de quartzo natural que passaram ou não pelo processo de eletrodifusão. Foi investigado um efeito de escurecimento no quartzo citrino quando este é exposto ao sol, correlacionando com os centros estudados no presente trabalho, [AlO4/H], [Li-OH] e [Na-OH], identificáveis na região do infravermelho e os centros [AlO4]0 e E' identificáveis no espectro de absorção óptica. A existência desses centros, chamados de centros de impurezas, é facilitada pela presença de um canal estrutural no quartzo, o qual permite a entrada de íons substitucionais como Al3+ e intersticiais Na+, Li+ e H+ junto a cadeia cristalina do quartzo. As amostras foram submetidas à radiação gama de dose aproximada a 20kGy, o resultado foi analisado com base nos centros estudados e os efeitos da eletrodifusão foram analisados por espectroscopia na região do UV-Vis e Infravermelho. A análise infravermelha indicou que a eletrodifusão de hidrogênio no quartzo citrino e hialino foi bem sucedida, uma vez que observa-se um incremento no centro [AlO4/H]0 e um decréscimo no centro [Li-OH], localizado na banda em 3484cm-1. A interação entre a radiação gama e o quartzo faz com que os centros relacionados à presença de hidrogênio com o alumínio aumentem, pois, a radiação ao excitar os átomos da rede do quartzo acaba por afetar diretamente os centros cujo compensador de carga são os átomos alcalinos Li+,Na+ e K+ do centro [AlO4/M]0, havendo então a compensação por átomos de hidrogênio, formando então mais centros [AlO4/H]0. O aparecimento das bandas em 430 ... / Abstract: In the present study, we investigated the effects of alkali ions Na+ , Li+ replaced by ion H+ and Na+ in the center related to the aluminum that is a found naturally in motrices natural quartz. Measurements of optical absorption in the visible and ultraviolet region and measures infrared samples of natural quartz that have passed or not by electrodiffusion process were performed. An effect of browning in citrine quartz was investigated when exposed to the sun , correlating with the centers studied in this work, [ AlO4/H]0 , [ Li-OH ] and [Na-OH] , identifiable in the infrared region in the centers [AlO4]0 and E' that are identifiable in the optical absorption spectrum. The existence of such centers, centers called impurities is facilitated by the presence of a structural channel quartz, which allows the entry of ions such as substitutional Al3+ substitutional and interstitial as Na+, Li+ and H+ along the crystal quartz chain . The samples were submitted to gamma radiation dose of approximately 20kGy , the outcome was analyzed based on the centers and the effects of electrodiffusion were analyzed by spectroscopy, UV- Vis and IR region. Infrared analysis indicated that the hydrogen electrodiffusion in citrine and hyaline quartz was successful , since there is an increase in the center [AlO4/H]0 and a decrease in the [Li-OH] , located in the band at 3484cm -1. The interaction between gamma radiation and quartz causes the centers related to the presence of hydrogen with aluminum increase , because the radiation to excite the atoms of the quartz network ultimately directly affect the centers whose compesator load are the alkali atoms Li+ , Na+ and K+ center [AlO4/M]0 , then there is compensation for hydrogen atoms , thus forming more centers [AlO4/H]0 . The appearance of bands at 430 and 620 nm associated to the center [AlO4]0 in the citrine and hyaline quatz after irradiation, enables us to state that ... / Mestre

Made available in DSpace on 2017-07-10T15:14:46Z (GMT). No. of bitstreams: 1 Vander Silveira.pdf: 1631323 bytes, checksum: 98ee5edf851d1f5877f2bfc766c109ab (MD5) Previous issue date: 2012-02-17 / This study aimed to develop and evaluate an electrolytic reaction system for the production of HHO gas. The HHO gas, also known as Brown s gas or hydroxyl gas, can be used together with liquid fuel in Otto and Diesel cycle engines, to reduce their consumption. To conduct the study was built an electrolytic reactor with 360L steel plates in an acrylic vat. It was evaluated the performance of the electrolytic reactor, using the electrolytes of sodium hydroxide and potassium hydroxide. The findings allowed to conclude that the reactor showed better energy performance in the production of HHO gas when using sodium hydroxide as electrolyte / Este trabalho teve o objetivo de desenvolver e avaliar um sistema de reação eletrolítica para a produção de gás HHO. O gás HHO, também conhecido como gás de Brown ou gás hidróxi, pode ser utilizado concomitantemente com combustíveis líquidos em motores ciclo Otto e ciclo Diesel, visando à redução do consumo destes últimos. Para a realização do trabalho foi construído um reator eletrolítico com placas de aço 316L em uma cuba de acrílico. Avaliou-se o desempenho do reator eletrolítico, utilizando-se os eletrólitos hidróxido de sódio e hidróxido de potássio. Os resultados encontrados permitiram concluir que o reator apresentou melhor desempenho energético na produção de gás HHO quando se utilizou o hidróxido de sódio como eletrólito.

京都大学 / 新制・課程博士 / 博士(人間・環境学) / 甲第23996号 / 人博第1048号 / 新制||人||246(附属図書館) / 2022||人博||1048(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 高木 紀明, 教授 白井 理, 教授 光島 重徳 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Microbial electrochemical systems (MESs) have attracted much research attention in recent years due to their promising applications in renewable energy generation, bioremediation, and wastewater treatment. In a MES, microorganisms interact with electrodes via electrons, catalyzing oxidation and reduction reactions at the anode and the cathode. The bacterial community of a high power mixed consortium MESs (maximum power density is 6.5W/m��) was analyzed by using denature gradient gel electrophoresis (DGGE) and 16S DNA clone library methods. The bacterial DGGE profiles were relatively complex (more than 10 bands) but only three brightly dominant bands in DGGE results. These results indicated there are three dominant bacterial species in mixed consortium MFCs. The 16S DNA clone library method results revealed that the predominant bacterial species in mixed culture is Geobacter sp (66%), Arcobacter sp and Citrobacter sp. These three bacterial species reached to 88% of total bacterial species. This result is consistent with the DGGE result which showed that three bright bands represented three dominant bacterial species. Exoelectrogenic bacterial strain SX-1 was isolated from a mediator-less microbial fuel cell by conventional plating techniques with ferric citrate as electron acceptor under anaerobic conditions. Phylogenetic analysis of the 16S rDNA sequence revealed that it was related to the members of Citrobacter genus with Citrobacter sp. sdy-48 being the most closely related species. The bacterial strain SX-1 produced electricity from citrate, acetate, glucose, sucrose, glycerol, and lactose in MFCs with the highest current density of 205 mA/m�� generated from citrate. Cyclic voltammetry analysis indicated that membrane associated proteins may play an important role in facilitating electron transfer from the bacteria to the electrode. This is the first study that demonstrates that Citrobacter species can transfer electrons to extracellular electron acceptors. Citrobacter strain SX-1 is capable of generating electricity from a wide range of substrates in MFCs. This finding increases the known diversity of power generating exoelectrogens and provids a new strain to explore the mechanisms of extracellular electron transfer from bacteria to electrode. The wide range of substrate utilization by SX-1 increases the application potential of MFCs in renewable energy generation and waste treatment. Anode properties are critical for the performance of microbial electrolysis cells (MECs). Inexpensive Fe nanoparticle modified graphite disks were used as anodes to preliminarily investigate the effects of nanoparticles on the performance of Shewanella oneidensis MR-1 in MECs. Results demonstrated that average current densities produced with Fe nanoparticle decorated anodes were up to 5.9-fold higher than plain graphite anodes. Whole genome microarray analysis of the gene expression showed that genes encoding biofilm formation were significantly up-regulated as a response to nanoparticle decorated anodes. Increased expression of genes related to nanowires, flavins and c-type cytochromes indicate that enhanced mechanisms of electron transfer to the anode may also have contributed to the observed increases in current density. The majority of the remaining differentially expressed genes were associated with electron transport and anaerobic metabolism demonstrating a systemic response to increased power loads. The carbon nanotube (CNT) is another form of nano materials. Carbon nanotube (CNT) modified graphite disks were used as anodes to investigate the effects of nanostructures on the performance S. oneidensis MR-1 in microbial electrolysis cells (MECs). The current densities produced with CNT decorated anodes were up to 5.6-fold higher than plain graphite anodes. Global transcriptome analysis showed that cytochrome c genes associated with extracellular electron transfer are up-expressed by CNT decorated anodes, which is the leading factor to contribute current increase in CNT decorated anode MECs. The up regulated genes encoded to flavin also contribute to current enhancement in CNT decorated anode MECs. / Graduation date: 2013

The production of chlorate, chlorine and sodium hydroxiderelies heavily on electrical energy, so that savings in thisarea are always a pertinent issue. This can be brought aboutthrough increased mass transfer of reacting species to therespective electrodes, and through increased catalytic activityand uniformity of current density distribution at theseelectrodes. This thesis will present studies involvingmathematical modelling and experimental investigations of theseprocesses. They will show the effect that hydrodynamicbehaviour has on the total current density and cell voltages,along with the effects on current density distributions andindividual overpotentials atthe respective electrodes. Primary, secondary and psuedo-tertiary current densitydistribution models of a chlor-alkali anode are presented anddiscussed. It is shown that the secondary model presentsresults rather similar to the pseudo-tertiary model, when thecurrent density distribution is investigated, although thepotential distribution differs rather markedly. Furthermore, itis seen that an adequate description of the hydrodynamicsaround the anode is required if the potential distribution, andthereby the prevalence of side-reactions, is to be reasonablepredicted. A rigorous tertiary current density distribution model ofthe chlorate cell is also presented, which takes into accountthe developing hydrodynamic behaviour along the height of thecell. This shows that an increased flowrate gives more uniformcurrent density distributions. This is due to the fact that theincreased vertical flowrate of electrolyte replenishes ioncontent at the electrode surfaces, thus reducing concentrationoverpotentials. Furthermore, results from the model lead to theconclusion that it is the hypochlorite ion that partakes in themajor oxygen producing side-reaction. A real-scale cross-section of a segmented anode-cathode pairfrom a chlorate cell was designed and built in order to studythe current density distribution in industrial conditions.These experiments showed that increased flowrate brought aboutmore even current density distributions, reduced cell voltageand increased the total current density. An investigation ofthe hydrodynamic effects on the respective electrodeoverpotentials shows the anode reactions being more favoured byincreased flowrate. This leads to the conclusion that theuniform current density distribution, caused by increasedflowrate, occurs primarily through decreasing the concentrationoverpotential at the anode rather than by decreasing thebubble-induced ohmic drop at the cathode. Finally, results from experiments investigating thebubble-induced free convection from a small electrochemicalcell are presented. These experiments show that Laser DopplerVelocimetry is the most effective instrument for investigatingthe velocity profiles in bubble-containing electrochemicalsystems. The results also show that the flow can transform fromlaminar to turbulent behaviour on both the vertical andhorizontal planes, in electrochemical systems where bubbles areevolved.

The ultimate goal of this study is to examine the feasibility of extracting silicon from silica through electrolysis. The objective of the thesis was to evaluate the physico-chemical properties of a cryolite-lithium fluoride mixture as an electrolyte for the electrolysis process. A study of 86.2wt%Cryolite and13.8wt%Lithium fluoride melt with silica concentration varying from 0-4wt% and temperature range of 900-1000°C was done. Three properties were measured using two sets of experiments: 1) Dissolution Behaviour Determination, to obtain a) solubility limit, b) dissolution rate (mass transfer coefficient) and 2) density using Archimedes’ Principle. The study concluded that solubility and dissolution rate increases with temperature and the addition of LiF to cryolite decreases the solubility limit but increases the rate at which silica dissolves into the melt. With addition of silica, the apparent density of electrolyte first increases up to 2-3wt% and the drops.

The present study was undertaken to elucidate the electrochemical reduction mechanisms of benzil derivatives using the techniques of polarography and controlled potential electrolysis. Another objective of this study was to determine a quantitative relationship between reactivity and structure. The electrochemical experiments have been conducted in a 50% ethanol-water solvent over the pH range of 1.5 to 13.5. Potentiometric titrations and ultraviolet spectra were obtained to help understand the ionization of hydroxy-substituted benzil derivatives and how the ionization affects the polarographic reductions. Benzoin and two benzoin derivatives were studied to help determine the reduction products.