The purpose of this report is to present the results of the study and analysis of loss-of-coolant and loss-of-flow simulations performed on the Modular Helium Reactor developed by General Atomics using the thermal-hydraulics code RELAP5-3D/ATHENA. The MHR is a high temperature gas cooled reactor. It is a prismatic core concept for New Generation Nuclear Plant (NGNP). Very few reactors of that kind have been designed in the past. Furthermore, the MHR is supposed to be a highly passively safe concept. So there are high needs for numerical simulations in order to confirm the design. The project is dedicated to the assessment of the passive decay heat capabilities of the reactor under abnormal transient conditions. To comply with the requirements of the NGNP, fuel and structural temperatures must be kept under design safety limits under any circumstances. During the project, the MHR has been investigated: first under steady-state conditions and then under transient settings. The project confirms that satisfying passive decay heat removal by means of natural heat transfer mechanisms (convection, conduction and radiation) occurs.

The purpose of this report is to present the results of the study and analysis of loss-of-coolant and loss-of-flow simulations performed on the Modular Helium Reactor developed by General Atomics using the thermal-hydraulics code RELAP5-3D/ATHENA. The MHR is a high temperature gas cooled reactor. It is a prismatic core concept for New Generation Nuclear Plant (NGNP). Very few reactors of that kind have been designed in the past. Furthermore, the MHR is supposed to be a highly passively safe concept. So there are high needs for numerical simulations in order to confirm the design. The project is dedicated to the assessment of the passive decay heat capabilities of the reactor under abnormal transient conditions. To comply with the requirements of the NGNP, fuel and structural temperatures must be kept under design safety limits under any circumstances. During the project, the MHR has been investigated: first under steady-state conditions and then under transient settings. The project confirms that satisfying passive decay heat removal by means of natural heat transfer mechanisms (convection, conduction and radiation) occurs.

L’objectif de cette thèse était de mieux comprendre les paramètres structuraux et environnementaux gouvernant l’énantiosélectivité de la lipase B de Candida antarctica (CALB), lors de la résolution des alcools secondaires linéaires chiraux. Ces composés sont notamment utilisés comme synthons chiraux dans l’industrie pharmaceutique. Dans un premier temps, une étude systématique des orientations du butan-2-ol et du pentan-2-ol au sein du site actif a été réalisée par modélisation moléculaire. Les résultats suggèrent l’existence de modes d’arrimages supplémentaires à ceux mentionnés dans la littérature. La comparaison selon l’énergie potentielle du substrat des structures les plus stables, combinée à la prise en compte de modes de fixation non productifs, nous a permis d’expliquer qualitativement l’énantiopréférence de la CALB pour la forme R. A l’aide du réacteur solide/gaz, nous avons montré que les résidus hydrophobes formant le canal d’accès du substrat au site actif (Ile189, Leu278 et Ala282), jouaient un rôle significatif dans l’énantiosélectivité de la CALB vis-à-vis des alcools secondaires. L’influence de la partie alkoxy du donneur d’acyle sur le ratio énantiomérique a également pu être mise en évidence. Par ailleurs, nous avons montré que des mutations isostériques de la poche stéréosélective conduisaient à des variations des paramètres thermodynamiques d’activation de l’acylation du pentan-2-ol, probablement suite à des modifications du réseau de liaisons hydrogène formé entre les résidus de la poche. Les études d’adsorption de l'eau et des substrats sur l’enzyme immobilisée nous ont permis de relier l'état d'hydratation de la CALB avec les effets particuliers de l'eau sur l’activité et la sélectivité de l’enzyme. / The aim of this thesis was to understand more precisely the structural and environmental parameters governing the enantioselectivity of lipase B from Candida antarctica (CALB), involved in the discrimination of chiral secondary alcohols enantiomers. These compounds are used in particular for the synthesis of enantiomerically pure pharmaceutical molecules. Initially a systematic study of the orientation of butan-2-ol and pentan-2-ol in the active site was performed by molecular modeling. The results suggest the existence of additional binding modes to those mentioned in the literature. The potential energy comparison of the most stable conformations of the substrate, combined with the existence of non productive binding modes, allowed us to explain qualitatively the enantiopreference of CALB for the R form. Using the solid/gas reactor, we have shown that hydrophobic residues forming the access channel of substrate to the active site (Ile189, Leu278 and Ala282), played a significant role in the enantioselectivity of CALB towards secondary alcohols. The influence of the alkoxy part of the acyl donor on the enatiomeric ratio E has also been highlighted. Furthermore, we showed that isosteric mutations of the stereoselective pocket led to changes in pentan-2-ol activation thermodynamic parameters of acylation, probably due to changes in the hydrogen bonds network formed between residues of the pocket. Studies of water and substrates adsorption on the immobilized enzyme allowed us to relate the hydration status of CALB with specific effects of water on the enzyme activity and selectivity.

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.