[pt] O potássio é um íon essencial para a nutrição de plantas, geralmente fornecido sob a forma de cloretos e sulfatos. De acordo com a disponibilidade e demanda brasileira de fertilizantes agrícolas, a importação de compostos portadores desse elemento químico é mandatória para atender a enorme demanda por esse nutriente. Assim, iniciativas que buscam fontes alternativas de potássio tornam-se cada vez mais interessantes e economicamente atraentes. Uma rota potencial está associada com a digestão com ácido sulfúrico de minerais portadores de glauconita e operações unitárias sequenciais para recuperar compostos de alumínio, ferro, magnésio e potássio. No contexto deste processo químico, o alúmen de potássio dodecahidrato aparece como um produto intermediário relevante que permite a recuperação seletiva de potássio e alumínio através de decomposição térmica seguida de solubilização em água e filtração. Com base no que foi dito, o presente trabalho investiga a cinética da decomposição do alúmen de potássio dodecahidratado sob condições não-redutoras e redutoras, e um novo modelo matemático é proposto para descrever a perda de massa ao longo do tempo. Uma abordagem estocástica, com o uso do método de otimização enxame de partículas, é empregada para estimar os parâmetros desconhecidos do modelo. As previsões do modelo são validadas por dados experimentais obtidos via análise termogravimétrica dinâmica em diferentes atmosferas de reação (inerte e oxidante), e com a presença ou não de agente redutor (finos de coque metalúrgico). Com os parâmetros do modelo validado, é possível usar o mesmo para monitorar as composições mássicas de todos os compostos presentes no meio assim como empregar o modelo futuramente para monitoramento online uma vez que sua simulação leva menos do que 1 s para simular 20 min de decomposição térmica. / [en] Potassium is an essential ion for plant nutrition, usually supplied in the form of chlorides and sulfates. According to Brazilian availability and demand of agriculture fertilizers, the importation of compounds carrying this chemical element is mandatory in order to fulfill the huge demand for this nutrient. So initiatives looking for alternative sources of potassium become increasingly interesting and economically attractive. A potential route is associated with the sulfuric digestion of glauconite-bearing greensands and sequential unit operations in order to recover aluminum, iron, magnesium and potassium compounds. In the context of this chemical process, the potassium alum dodecahydrate appears as a relevant intermediate product that allows the selective recovery of potassium and aluminum through thermal decomposition followed by solubilization in water and filtration. Based on what was said, the present work investigates the kinetics of potassium alum dodecahydrate decomposition under nonreductive and reductive conditions, and a novel mathematical model is proposed to describe the weight loss during time. A stochastic approach approach, using particle swarm optimization method, is employed to estimate the unknown model parameters. The model predictions are validated by experimental data obtained through dynamic thermogravimetric analysis at different reaction atmospheres (inert and oxidant), and with the presence or not of reducing agent (metallurgical coke breeze). With the validated model parameters, it is possible to use them to monitor the mass compositions of all compounds present in the process as well as to use the model for future online monitoring since its simulation takes less than 1 s to simulate 20 min of decomposition thermal.

Les pathologies vésicales sont nombreuses et nécessitent la plupart du temps un traitement médicamenteux. Il peut alors être administré par voie intravésicale, augmentant son efficience et limitant les effets indésirables systémiques. Nous nous sommes intéressés à quatre thérapeutiques : l’alun de potassium, le chlorhydrate de lidocaïne, l’hemisuccinate de méthylprednisolone, la mitomycine C et le bacille de Calmette et Guérin (BCG) en application locale directement dans la vessie. La perméabilité de l’aluminium à travers la vessie a été étudiée au travers d’un cas clinique et des expériences ex vivo ont été réalisées pour définir les paramètres de perméabilité et proposer un algorithme de prédiction de la quantité d’aluminium absorbée dans l’organisme après irrigation intravésicale à l’alun de potassium. Cet algorithme dépend du poids du patient, de la durée de l’irrigation et du volume de la solution utilisée en irrigation vésicale. Des études de perméation ont aussi été réalisées pour le chlorhydrate de lidocaïne, l’hemisuccinate de méthylprednisolone, la mitomycine C et le BCG afin de sécuriser l’emploi de ces thérapeutiques par voie intravésicale. Les études réalisées permettent de prédire, selon les caractères physico-chimiques des molécules, la pénétration dans la membrane vésicale. Une nouvelle formulation galénique réalisée à base d’un gel thermosensible a été étudiée pour optimiser les thérapeutiques intravésicales. Des études de perméation ont été faites avec la nouvelle formulation galénique. Pour finir, une culture de cellules cancéreuses urothéliales a été mise au point et un test de viabilité a été réalisé pour la mitomycine C et le BCG / Bladder diseases are numerous and mostly require medication. Drugs can be administered by intravesical route, thereby increasing efficiency and reducing systemic side effects. We are interested in four drugs: potassium alum, lidocaine hydrochloride, methylprednisolone hemisuccinate, mitomycin C and bacillus Calmette- Guérin (BCG). Mathematical modelling of drug transport through bladder wall is proposed considering scarce literature on this route of administration. The permeability of aluminum through bladder wall was studied through a clinical case and ex vivo experiments were performed to propose a simplified algorithm for the calculation of aluminium dose absorbed in patient with impaired renal function as function of volume of 1% alum solution in the bladder, duration of intravesical irrigation and patient body weight. Permeation studies were also conducted for lidocaine hydrochloride, methylprednisolone hemisuccinate, mitomycin C and BCG to secure intravesical administration of these drugs. Practical outcome of this study could drive compounding optimisation towards improvement of safety and efficacy in patient undergoing intravesical administration. A new pharmaceutical formulation including hrydrogel has been studied in an attempt to improve treatment administered by intravesical route. Permeation studies were made with the new formulation. Finally, an urothelial cancer cells culture has been developed and a viability test was performed with mitomycin C and BCG

Les travaux présentés dans ce manuscrit de doctorat s'inscrivent dans la thématique du stockage inter-saisonnier de l'énergie solaire thermique pour l'habitat et le tertiaire (eau chaude sanitaire et chauffage). Le stockage thermochimique en air humide est une des solutions les plus prometteuses, en particulier avec un réacteur à lit fixe. Le bromure de strontium et l'alun de potassium ont été sélectionnés comme réactifs pour leurs caractéristiques énergétiques lors de réactions d'hydratation et de déshydratation. L'étude est constituée d'avancées théoriques, de nombreuses expérimentations et d'un modèle numérique détaillé. Une étude thermodynamique a démontré l'existence d'une droite de charge qui relie les conditions d'entrée et de sortie de l'air humide au passage du réactif. Les équations régissant les réactions chimiques, les transferts massiques et thermiques et la conservation de la quantité de mouvement ont été établies et un modèle numérique monodimensionnel couplant ces phénomènes a été développé. Des essais sur différents échantillons des deux sels et pour divers conditions opératoires ont été effectués dans le but de comprendre les phénomènes physico-chimiques ainsi que pour valider l'étude théorique et le modèle numérique. / This PhD thesis focuses on seasonal solar thermal energy storage for household applications such as production of heat and domestic hot water. Thermochemical storage was chosen for that purpose. The specific solid/gas reactions with water vapor, also called hydration/dehydration reactions, were used with a multi-scale global approach. The level of the reactor was identified as the critical level of that multi-scale approach. As a consequence, the integrated fixed-bed reactor technology in a moist air open loop system was adopted. A theoretical, experimental and numerical methodology was used for the study where strontium bromide and potassium alum salts were chosen as reactive materials. The corresponding reactions are: + 5 (H2O) ↔ (with Δhr=67.4 kJ/molwater and Δsr=175 J/K.molwater) + 9 (H2O) ↔ < KAl(SO4)2.12H2O > (with Δhr=44.2 kJ/molwater and Δsr=109.8 J/K.molwater) The first salt exhibits very good thermochemical properties. On the other hand, the main advantages of potassium alum are its low cost and the fact that it presents no sanitary risk. More than 30 cycles with 3 different samples of potassium alum and more than 25 cycles with 4 samples of strontium bromide under various stationary and dynamic operating conditions were carried out in order to understand the phenomena. The main experimental results were the following ones: • A very good stability and reproducibility of physical and chemical phenomena was observed for both materials. • A thermal reaction front was also observed. • A thermal hysteresis for both salts was found. • Based on that last observation a theoretical equation named charge-discharge line was developed. Experimental results with both salts validate the charge-discharge line theory. • A correlation between reaction kinetics, temperature rise due to the reaction, power of the reaction and the operating conditions was observed. The criterion for that correlation is the affinity of the reaction. A proportional correlation between affinity and reaction kinetics, temperature rise and power of the reaction was observed. • Spontaneous hydration and over-hydration reactions do not produce any particular difficulties or problems. • Pressure drop through the reactor and evolution of salts volume were also measured. Experimental energy density was measured in the range of 350 kWh/m3 for strontium bromide and 240 kWh/m3 for the potassium alum. • In general, strontium bromide is a very good candidate material for seasonal storage, while potassium alum cannot provide satisfying temperature rise and power. The equations governing those phenomena were also established and used to develop a 1D numerical model with partial differential equations coupling chemical phenomena, mass and thermal transfer phenomena and momentum conservation. Verification, validation and confirmation of this model under a very large range of operating conditions were carried out based on the experimental results of strontium bromide. A total of 19 different test cases were studied in order to validate the numerical model. The effect of humidity, temperature, quantity of reactive material and air flow were studied both for stationary and dynamic conditions. The numerical model was able to provide very satisfying results.