In Taiwan, more than 25% of all water uses comes from groundwater, and thus groundwater is a very valuable water resource for both domestic and industrial uses. However, groundwater at many existing former industrial sites and disposal areas was contaminated by halogenated organic compounds that were released into the environment. The chlorinated solvent trichloroethene (TCE) is one of the most ubiquitous of these compounds. In this laboratory-scale feasibility study, a hybrid two-stage process combining fiber filtration (FF) and nanofiltration (NF) was applied to remove to suspended solids (SS) and TCE from contaminated groundwater for water purification. In this study, a man-made kaolin solution was used to simulate groundwater purification using FF system. Then, microfiltration (MF), ultrafiltration (UF), and NF systems were applied for TCE removal. The hybrid membrane process using FF and NF units was used to evaluate the feasibility on TCE removal. The scanning electron microscope (SEM) and energy dispersive spectroscope (EDS) were used to investigate membrane morphology and structure after use. A 3-D excitation emission fluorescence matrix (EEFM) was used to evaluate the potential of membrane organic fouling. Results show that the optimization filtration velocity of FF was 15.3 m/hr, and the observed TCE and SS removal efficiencies were 80% and 60%, respectively. Removal mechanisms for MF and UF were mainly sieving, and the removal mechanism for NF was mainly electrostatic repulsion. Results indicate that NF had the highest TCE removal efficiency (98.2%). When initial TCE concentration was 1 mg/L, NF membrane pore might shrink caused increased TCE removal (rejection). When TCE concentration was higher 1 mg/L, membrane damage and pore enlargement was observed with decreased TCE removal efficiency. The observed SS, sulfate, and hardness removal efficiencies were 99.8%, 98.7%, and 98.7% respectively, when FF and NF hybrid process was used. Higher TCE concentration might enlarge membrane pore, which caused decreased membrane separation and increased flux. Approximately 46% of flux drop was observed when NF was used alone compared to the hybrid membrane process using FF as the first treatment stage. Membrane analyses show that residual TCE was adsorbed on the membrane. Low zeta potential of groundwater was observed due to the compressed electric double layer, which caused aggregation of particle. High zeta potential of permeate was due to the particle dispersive through hybrid process. Results from SEM analysis show that membrane morphology was damaged by TCE, and heavy metal in groundwater deposited on membrane. Results of EEFM analysis indicate that groundwater contained humic acid (HA) and soluble microbial by-product (SMP). HA and SMP might be adsorbed on fiber filter, and extracellular polymeric substances (EPS) that attached on fiber filter might be washed out. The organic powders on the surface of the fiber filter might be washed out causing the increased in NPDOC concentrations. Humic acid could be removed through NF process, and SMP might be adsorbed in membrane pore caused organic fouling, and SMP might be washed out after treatment by the FF+NF hybrid process. Results indicate that FF as pre-treatment can maintain higher flux. Higher TCE concentration caused membrane destruction and decreased membrane separation. TCE contaminated groundwater can be affectively treated by the hybrid membrane system to meet the groundwater standard and reclaimed water standard. Reclaimed water could be used for industrial cooling water and irrigation purposes.

O presente trabalho aborda a aplicação de processos combinados de estampagem, processo convencional e incremental em uma mesma chapa metálica. Essa combinação é denominada de processo de estampagem híbrido. Tal processo é realizado através da fabricação de uma pré-forma pelo processo convencional de estampagem, seguido da manufatura pelo processo incremental. O objetivo principal é analisar o comportamento das deformações ocorridas na geratriz, o que até então só havia sido analisado separadamente, sem um aprofundamento aplicado ao processo híbrido. As deformações ocorridas no processo convencional determinam os caminhos de deformações nos elementos da geratriz, influenciando diretamente as deformações geradas pela estampagem incremental. Para alcançar os objetivos, experimentos foram realizados com o material aço DC04, sendo divididos em duas etapas: a estampagem incremental em linha reta e após o processo de estampagem híbrido. A estampagem incremental em linha reta foi realizada para avaliação do material em relação a diferentes estratégias incrementais e às máximas deformações. No processo híbrido, as deformações da estampagem convencional foram realizadas em três direções com graus de deformações diferentes. Na etapa incremental do processo híbrido foi adotada a estratégia de pirâmide com diferentes inclinações de parede nas amostras. Nos experimentos, foram analisadas as deformações verdadeiras, geometrias finais e redução de espessura das amostras. A simulação numérica é uma ferramenta computacional que foi utilizada para comparação e correlação com os dados dos experimentos físicos. Os critérios de falha ou parada das simulações são dependentes dos dados do material (curva limite de conformação) e/ou dos experimentos físicos realizados (profundidade de ruptura). No desenvolvimento da estampagem incremental em linha reta, o punção de ponta hemisférica com diâmetro de 30mm e 1mm de incremento por etapa apresentou as maiores deformações máximas (1,03). No processo de estampagem híbrido, as amostras com pré-deformações de embutimento profundo tenderam a não influenciar as deformações incrementais finais. As amostras com pré-deformações planas foram diretamente proporcionais às deformações máximas incrementais. Já as com pré-deformações de estiramento biaxial influenciaram as deformações incrementais conforme o grau da pré-deformação. / The present work approaches the application of combined forming processes, and conventional and incremental sheet forming processes in the same metal sheet. This combination is denominated hybrid forming processe. This process is done through the manufacture of a pre form by conventional forming process, followed by incremental sheet forming. The main objective is to analyze the behavior of strains occurred in the blank, which until now was only studied separately, without a deepening study applied to hybrid process. The pre strains occurred in the conventional process determine the strain paths in the blank elements, directly influencing the strains produced by the incremental process. To reach these objectives, experiments with DC4 steel were done, and were separated into two stages: first, a test of incremental sheet forming in a straight line, and, after, the hybrid forming process. The incremental sheet forming in straight line was done to evaluate the material in relation to different incremental strategies in this process and to maximum deformations. In the hybrid process, the conventional process deformations were done in three directions with distinct strain rate. In the incremental stage, the pyramid strategy was adopted with different wall inclinations of samples. In the experiments, the true strains, the final geometries and the samples thickness reduction was analyzed. The numerical simulation is a computational tool that was used for the comparison and correlation with the data of the physical experiments. The failure criterion or stopped simulations depend of the material data (Forming Limit Curve) and/or on the physical experiments done (depth of rupture). In the development of the incremental forming in straight line, the hemispherical-headed punch with diameter of 30 mm and 1 mm of increment per step presented the higher maximum strains (1,03). In the hybrid process, the deep drawing samples with pre-strain did not tend to influence the final incremental strains. The samples with plane pre-strain were directly proportional to the maximum incremental strains. Tthe samples with pre-strain biaxial, on the other hand, influenced the incremental strains according to the degree of pre-strain.

O presente trabalho aborda a aplicação de processos combinados de estampagem, processo convencional e incremental em uma mesma chapa metálica. Essa combinação é denominada de processo de estampagem híbrido. Tal processo é realizado através da fabricação de uma pré-forma pelo processo convencional de estampagem, seguido da manufatura pelo processo incremental. O objetivo principal é analisar o comportamento das deformações ocorridas na geratriz, o que até então só havia sido analisado separadamente, sem um aprofundamento aplicado ao processo híbrido. As deformações ocorridas no processo convencional determinam os caminhos de deformações nos elementos da geratriz, influenciando diretamente as deformações geradas pela estampagem incremental. Para alcançar os objetivos, experimentos foram realizados com o material aço DC04, sendo divididos em duas etapas: a estampagem incremental em linha reta e após o processo de estampagem híbrido. A estampagem incremental em linha reta foi realizada para avaliação do material em relação a diferentes estratégias incrementais e às máximas deformações. No processo híbrido, as deformações da estampagem convencional foram realizadas em três direções com graus de deformações diferentes. Na etapa incremental do processo híbrido foi adotada a estratégia de pirâmide com diferentes inclinações de parede nas amostras. Nos experimentos, foram analisadas as deformações verdadeiras, geometrias finais e redução de espessura das amostras. A simulação numérica é uma ferramenta computacional que foi utilizada para comparação e correlação com os dados dos experimentos físicos. Os critérios de falha ou parada das simulações são dependentes dos dados do material (curva limite de conformação) e/ou dos experimentos físicos realizados (profundidade de ruptura). No desenvolvimento da estampagem incremental em linha reta, o punção de ponta hemisférica com diâmetro de 30mm e 1mm de incremento por etapa apresentou as maiores deformações máximas (1,03). No processo de estampagem híbrido, as amostras com pré-deformações de embutimento profundo tenderam a não influenciar as deformações incrementais finais. As amostras com pré-deformações planas foram diretamente proporcionais às deformações máximas incrementais. Já as com pré-deformações de estiramento biaxial influenciaram as deformações incrementais conforme o grau da pré-deformação. / The present work approaches the application of combined forming processes, and conventional and incremental sheet forming processes in the same metal sheet. This combination is denominated hybrid forming processe. This process is done through the manufacture of a pre form by conventional forming process, followed by incremental sheet forming. The main objective is to analyze the behavior of strains occurred in the blank, which until now was only studied separately, without a deepening study applied to hybrid process. The pre strains occurred in the conventional process determine the strain paths in the blank elements, directly influencing the strains produced by the incremental process. To reach these objectives, experiments with DC4 steel were done, and were separated into two stages: first, a test of incremental sheet forming in a straight line, and, after, the hybrid forming process. The incremental sheet forming in straight line was done to evaluate the material in relation to different incremental strategies in this process and to maximum deformations. In the hybrid process, the conventional process deformations were done in three directions with distinct strain rate. In the incremental stage, the pyramid strategy was adopted with different wall inclinations of samples. In the experiments, the true strains, the final geometries and the samples thickness reduction was analyzed. The numerical simulation is a computational tool that was used for the comparison and correlation with the data of the physical experiments. The failure criterion or stopped simulations depend of the material data (Forming Limit Curve) and/or on the physical experiments done (depth of rupture). In the development of the incremental forming in straight line, the hemispherical-headed punch with diameter of 30 mm and 1 mm of increment per step presented the higher maximum strains (1,03). In the hybrid process, the deep drawing samples with pre-strain did not tend to influence the final incremental strains. The samples with plane pre-strain were directly proportional to the maximum incremental strains. Tthe samples with pre-strain biaxial, on the other hand, influenced the incremental strains according to the degree of pre-strain.

O presente trabalho aborda a aplicação de processos combinados de estampagem, processo convencional e incremental em uma mesma chapa metálica. Essa combinação é denominada de processo de estampagem híbrido. Tal processo é realizado através da fabricação de uma pré-forma pelo processo convencional de estampagem, seguido da manufatura pelo processo incremental. O objetivo principal é analisar o comportamento das deformações ocorridas na geratriz, o que até então só havia sido analisado separadamente, sem um aprofundamento aplicado ao processo híbrido. As deformações ocorridas no processo convencional determinam os caminhos de deformações nos elementos da geratriz, influenciando diretamente as deformações geradas pela estampagem incremental. Para alcançar os objetivos, experimentos foram realizados com o material aço DC04, sendo divididos em duas etapas: a estampagem incremental em linha reta e após o processo de estampagem híbrido. A estampagem incremental em linha reta foi realizada para avaliação do material em relação a diferentes estratégias incrementais e às máximas deformações. No processo híbrido, as deformações da estampagem convencional foram realizadas em três direções com graus de deformações diferentes. Na etapa incremental do processo híbrido foi adotada a estratégia de pirâmide com diferentes inclinações de parede nas amostras. Nos experimentos, foram analisadas as deformações verdadeiras, geometrias finais e redução de espessura das amostras. A simulação numérica é uma ferramenta computacional que foi utilizada para comparação e correlação com os dados dos experimentos físicos. Os critérios de falha ou parada das simulações são dependentes dos dados do material (curva limite de conformação) e/ou dos experimentos físicos realizados (profundidade de ruptura). No desenvolvimento da estampagem incremental em linha reta, o punção de ponta hemisférica com diâmetro de 30mm e 1mm de incremento por etapa apresentou as maiores deformações máximas (1,03). No processo de estampagem híbrido, as amostras com pré-deformações de embutimento profundo tenderam a não influenciar as deformações incrementais finais. As amostras com pré-deformações planas foram diretamente proporcionais às deformações máximas incrementais. Já as com pré-deformações de estiramento biaxial influenciaram as deformações incrementais conforme o grau da pré-deformação. / The present work approaches the application of combined forming processes, and conventional and incremental sheet forming processes in the same metal sheet. This combination is denominated hybrid forming processe. This process is done through the manufacture of a pre form by conventional forming process, followed by incremental sheet forming. The main objective is to analyze the behavior of strains occurred in the blank, which until now was only studied separately, without a deepening study applied to hybrid process. The pre strains occurred in the conventional process determine the strain paths in the blank elements, directly influencing the strains produced by the incremental process. To reach these objectives, experiments with DC4 steel were done, and were separated into two stages: first, a test of incremental sheet forming in a straight line, and, after, the hybrid forming process. The incremental sheet forming in straight line was done to evaluate the material in relation to different incremental strategies in this process and to maximum deformations. In the hybrid process, the conventional process deformations were done in three directions with distinct strain rate. In the incremental stage, the pyramid strategy was adopted with different wall inclinations of samples. In the experiments, the true strains, the final geometries and the samples thickness reduction was analyzed. The numerical simulation is a computational tool that was used for the comparison and correlation with the data of the physical experiments. The failure criterion or stopped simulations depend of the material data (Forming Limit Curve) and/or on the physical experiments done (depth of rupture). In the development of the incremental forming in straight line, the hemispherical-headed punch with diameter of 30 mm and 1 mm of increment per step presented the higher maximum strains (1,03). In the hybrid process, the deep drawing samples with pre-strain did not tend to influence the final incremental strains. The samples with plane pre-strain were directly proportional to the maximum incremental strains. Tthe samples with pre-strain biaxial, on the other hand, influenced the incremental strains according to the degree of pre-strain.

Biomass to Liquids via Fischer-Tropsch synthesis (BTL-FT) is regarded as one of the most promising routes for providing alternative solution to growing demand for energy and environmental protection. In Chapter I, the development and key issues of BTL-FT process (especially Fischer-Tropsch synthesis) were reviewed and identified. In Chapter II, Mo/HZSM-5 catalyst was synthesized using Incipient Wetness Impregnation method and tested in nitrogen rich model bio-syngas. Different operation parameters (temperature, pressure, and GHSV) were tested to investigate their influence on the catalytic performance. Those parameters were found to affect the performance significantly. Liquid samples from conversion were mainly composed of C8 to C10 range hydrocarbons. The catalyst characterization revealed that molybdenum species were well distributed on the catalyst support, while dealumination, agglomeration and coke deposition were observed in spent catalyst. The top layer of the spent catalyst had the most coke deposition. A Three-Dimensionally Ordered Macro-porous (3DOM) Fe based Fischer-Tropsch catalyst was developed using a facile in-situ Nitrate Oxidation-PMMA templating technique in Chapter III. Several techniques (including SEM, BET, TPR, HRTEM, XRD, XPS, and DRIFTS) were combined to characterize the morphology, textural properties and microstructures of 3DOM Fe catalysts at different stages. The effects of bio-syngas composition on carbonaceous species formation, iron phase transformation and catalytic performance were investigated and correlated. A novel hybrid bio-refinery process co-converting biomass and natural gas into liquid fuels via FTS with a CO2 recycle loop was developed, modeled and simulated by using Aspen Plus in Chapter IV. The Aspen Plus model utilized experimental data from the 3DOM Fe catalyst. Economic analysis was performed on different scenarios based on the simulation results to determine profitability of the process. Results indicated that 102.65 t/h gasoline and 22.93 t/h diesel can be produced with the co-processing of 100.00 t/h biomass and 112.3 t/h natural gas using 307.78 t/h of recycled CO2 in the process simulation. The carbon conversion rate was estimated to be 81.23% for the hybrid process. Economic analysis revealed that the process can be profitable when using at least 10.00 t/h biomass and 11.23 t/h natural gas.

This thesis deals with chemical plants constituted by parallel batch-continuous production lines with shared resources. For such plants, it is highly desirable to have optimal operation schedules which determine the starting times of the various batch processes and the flow rates of the continuous processes in order to maximize the average plant productivity and to have a continuous production without interruptions. This optimization problem is constrained by the limitation of the resources that are shared by the reactors and by the capacities of the various devices that constitute the plant. Such plants are "hybrid" by nature because they combine both continuous-time dynamics and discrete-event dynamics. The formalism of "Hybrid Automata" is there fore well suited for the design of plant models. The first contribution of this thesis is the development of a hybrid automaton model of the chemical plant in the Matlab-Simulink-Stateflow environment and its use for the design of an optimal periodic schedule that maximises the plant productivity. Using a sensitivity analysis and the concept of Poincaré; map, it is shown that the optimal schedule is a stable limit cycle of the hybrid system that attracts the system trajectories starting in a wide set of initial conditions. The optimal periodic schedule is valid under the assumption that the hybrid model is an exact description of the plant. Under perturbations on the plant parameters, it is shown that two types of problems may arise. The first problem is a drift of the hybrid system trajectory which can either lead to a convergence to a new stable sub-optimal schedule or to a resource conflict. The second problem is a risk of overflow or underflow of the output buffer tank. The second contribution of the thesis is the analysis of feedback control strategies to avoid these problems. For the first problem, a control policy based on a model predictive control (MPC) approach is proposed to avoid resource conflicts. The feedback control is run on - line with the hybrid Simulink-Stateflow simulator used as an internal model. For the solution of the second problem, a classical PI control is used. The goal is not only to avoid over- or under-filling of the tank but also to reduce the amplitude of outflow rate variations as much as possible. A methodological analysis for the PI controller tuning is presented in order to achieve an acceptable trade-off between these conflicting objectives.

Ce travail s’intéresse à la synthèse de films minces composites Zn-Si-O et Ti-Si-O à l’aide d’un procédé hybride combinant le dépôt de silice par PECVD (Plasma Enhanced Chemical Vapour Deposition) à partir du précurseur organométallique hexaméthyldisiloxane (HMDSO-Si2C6H180), et la pulvérisation réactive de zinc ou de titane. L’élaboration de revêtements dont la composition s’échelonne d’un oxyde métallique ZnOx ou TiOx à la silice est rendue possible en agissant sur le débit du précurseur. L’ajout de silicium dans le revêtement fait évoluer sa morphologie de colonnaire à dense. De plus un phénomène de compétition entre les composantes PECVD et pulvérisation du procédé est mis en évidence. Ainsi la mesure des vitesses de dépôt en fonction du débit d’HMDSO permet de déterminer les valeurs de débits critiques de précurseurs à partir desquelles le dépôt de silice par PECVD est initié, et pour lesquelles le recouvrement de la cible par le dépôt de silice se produit. Les caractérisations des revêtements montrent que ceux-ci sont constitués, dans une zone proche de l’interface avec l’acier d’un mélange d’oxydes non stoechiométriques qui diffère de manière importante d’un mélange ZnO+SiO2 ou TiO2+SiO2. Pour les revêtements de type Ti-Si-O le titane est en excès dans la zone proche de l’interface tandis que dans les revêtements de type Zn-Si-O le silicium est en excès. On observe alors une décroissance progressive de la concentration atomique respectivement de titane et de silicium lorsqu’on approche de la surface du revêtement. Ces évolutions peuvent être reliées à un effet de l’augmentation de la température dans la première phase de l’élaboration, qui agit sur la cinétique de dépôt par PECVD et conditionne l’état de contamination de la cible / The present work deals with the synthesis of Zn-Si-O and Ti-Si-O composite thin films by a hybrid process. The coatings are prepared by combining PECVD (Plasma Enhanced Chemical Vapour Deposition) of silicon oxide from hexamethyldisiloxane (HMDSO-Si2C6H180) and reactive sputtering of a zinc or a titanium target. Any composition of the deposited layer can be obtained from zinc oxide or titanium oxide to silicon oxide, by controlling the HMDSO flow rate in the reactor. The morphologies evolve from columnar to dense by adding silicon in the coating. Moreover, a competitive deposition process takes place between PECVD and sputtering. The critical flow rates above which the PECVD silicon oxide deposition takes place on the substrate and on the target can be described from measurements of the thin film deposition rates as a function of the HMDSO flow rate. The coating caracterisations show that they are, near the coating-substrate interface, made of a mixture of non-stoechiometric oxides whose composition is different from a ZnO+SiO2 or a TiO2+SiO2 mixing. Titanium and silicon are in excess near the coating-substrate interface, respectively in the Ti-Si-O and Zn-Si-O thin films. Then the atomic concentrations of titanium and silicon progressively decrease when reaching the surface of the thin film. These behaviours are correlated with an increase of the temperature during the first phase of deposition that increases the PECVD deposition kinetics and determines the contamination state of the target

Ces travaux ont porté sur l’intérêt de l’utilisation d’une membrane composite zéolite (CHA SSZ-13) accessible à l’échelle commerciale au travers de la technologie membranaire de perméation de gaz et de vapeurs. L’applicabilité de cette technologie séparative s’est principalement focalisée sur la récupération du méthane, propane et d’isobutène issus de flux produits à des échelles industrielles par des procédés durables. La mise au point d’un banc expérimental pour la mesure de données de perméation de gaz et de vapeur a été réalisé. En se basant sur des mesures expérimentales de perméation menées avec la membrane zéolite de l’étude, un premier cas d’application pratique a été de simuler les performances séparatives d’un procédé hybride associant un module membranaire zéolite avec une condensation cryogénique à partir d’un cahier des charges industriel pour la récupération d’isobutène. Le procédé hybride étudié est toujours plus performant que le procédé de condensation cryogénique seul de référence en termes de pureté du produit condensé obtenu et de consommation énergétique. Des cartographies ont été dressées afin de situer les performances de séparation simulées en fonction de l’objectif de récupération d’isobutène souhaité. Un second cas théorique de récupération du propane à partir d’évents de purge à l’azote avec un procédé hybride de séparation cryogénique couplée à une membrane permsélective a été étudié. Une cartographie des performances de séparation membranaire relative au couple propane/diazote selon les données de la littérature ouverte actuelles a été présentée. La membrane la plus permsélective au diazote et au propane (respectivement CHA SSZ-13 et PEBAX 2533) a été sélectionné afin de simuler des procédés hybrides dont les performances séparatives ont été comparées à celles de la condensation cryogénique seule de référence. Pour de faibles teneurs en propane, il a été constaté que le procédé le plus performant (besoin énergétique et qualité du produit condensé) impliquait un module membranaire polymère de type PEBAX 2533 avec un système de mise sous vide du perméat. / This work focused on the interest of using a zeolite composite membrane (CHA SSZ-13) accessible on a commercial scale through the membrane technology of gas and vapor permeation. The applicability of this separation technology has mainly focused on the recovery of methane, propane and isobutene from fluxes produced at industrial scales by sustainable processes. The development of an experimental lab scale pilot for gas and vapor permeation data measurements is detailed. Based on experimental permeation measurements carried out with the zeolite membrane of the study, a first case of practical application was to simulate the separation performance of a hybrid process associating a zeolite membrane module with a cryogenic condensation from an industrial specification for the recovery of isobutene. The hybrid process studied is always more efficient than the only cryogenic condensation process taken as reference in terms of purity of the condensed product obtained and energy consumption. A chart was generated to locate the simulated separation performance based on the desired isobutene recovery objective. A second theoretical case of propane recovery from nitrogen purging vents with hybrid membrane cryogenic separation process was studied. This study presented a chart of the membrane separation performance of propane over nitrogen according to data from the open literature. The most nitrogen- and propane-selective membrane (CHA SSZ-13 and PEBAX 2533 respectively) was then selected and used in order to simulate hybrid processes where separation performances were compared to a baseline cryogenic standalone process. For low propane contents in the nitrogen feed mixture, it was found that the most efficient process (energy need and quality of the condensed product) involved a PEBAX 2533 polymer membrane module with a vacuum system for the permeate.

Motivées par des normes de rejets en azote toujours plus sévères et par les besoins d'extension de certaines stations d'épuration, les agglomérations sont à la recherche de nouvelles technologies de traitement plus compactes et plus performantes. Dans ce sens, le procédé hybride, à lit fluidisé placé dans un réacteur de type boues activées (IFAS), est une nouvelle technologie de traitement du carbone et de l'azote très attractive. L'objectif de cette thèse est d'optimiser le dimensionnement du procédé IFAS en configuration trois bassins (anoxie/aérobie BA/aérobie IFAS) et d'apporter des recommandations sur la conduite du procédé (charge massique appliquée, température.). Pour cela, une double démarche expérimentale et numérique a été mise en place. Un pilote de 3 m3 alimenté en eau usée brute a été conçu, instrumenté et étudié pendant 2 ans au cours de 7 périodes stabilisées (entre 0,15 et 0,30 kgDBO5/kgMVSLM/j, température entre 10 et 22°C, et le séquençage de l'aération dans les bassins). La concentration en MES dans la liqueur mixte a été maintenue à 2,3 gMES/L et la concentration en oxygène entre 2 à 6 mgO2/L. Les capacités de nitrification du biofilm et de la liqueur mixte (NPRmax) ont été mesurées tous les 15 jours. Les performances d'élimination de l'azote (nitrification et dénitrification) et du carbone observées sont restées supérieur à 90% d'élimination pour une charge massique maximale de 0,30 kgDBO5/kgMVSLM/j entre 16 à 24°C. Le biofilm dispose d'une capacité de nitrification maximale de 0,90 gN/m2/j et tributaire des concentrations en oxygène dans la liqueur mixte (contraintes diffusionnelle). Le biofilm contribue en moyenne à hauteur de 60% du flux total nitrifié dans le réacteur IFAS pour des âges de boues < 5 jours à 16°C. La diminution du MLSRT en dessous de 4 jours a permis de limiter le développement des bactéries autotrophes dans la liqueur mixte (minimum 10% du flux total nitrifié par la liqueur mixte) mais pas de les supprimer totalement (apport de nitrifiante par détachement de biofilm) / Motivated by the increasingly demanding discharge consents and by the need to improve overall treatment capacity, water authorities are uninterruptedly examining better performing and more compact wastewater treatment technologies. Thanks to its compactness and to its capacity to treat both organic matter and nitrogen at an affordable cost, the IFAS process represents an attractive addition to improve retrofitting-activated sludge plants performance. The main objective of this thesis is to optimize IFAS process with regards to key operation parameters such as dimensioning, F/M ratio by combining experimental and mathematical modelling approaches. A 3 m3 pilot IFAS fed with raw wastewater was operated at the experimental hall of La Feyssine wastewater treatment plant, Villeurbanne, for a period of 2 years. The IFAS process was separated in 3 tanks to treat organic matter and total nitrogen separately (anoxic/aerobic, suspended/aerobic IFAS). The experimental study was divided in 7 periods with different steady state operation conditions each. The feasibility of nitrification at steady F/M ratios (between 0,1S to 0,30 kgBODS/kgMLVSS/d), at constant temperatures (between 10 - 22°C) and at different oxygen supply rates was investigated. TSS in mixed liquor were maintained at 2,3 gMLTSS/L and oxygen concentration between 2 to 6 mgO2/L. Biofilm mass and combined nitrification capacity of biofilm and mixed liquor (NPRmax) were measured on a weekly basis. The removal performance was up to 90% for nitrogen and carbon treatment with a maximal F/M ratio of 0,30 kgBODS/kgMLVSS/d between 16°C to 24 °C. The biofilm was able to nitrify 0,90 gN/m2/d (NPRmax) depending on the oxygen concentration in the mixed liquor (diffusional limitation). Under the operating conditions tested in this study, biofilm was responsible for 40 to 70% of NOx-N production in IFAS reactor during nitrification. Decreasing the MLSRT to less than 4 days limits the growth of autotrophic bacteria in the mixed liquor but does not halt it completely

Les cellules solaires en couches minces à base d'absorbeurs de type Cu(In,Ga)Se2 (CIGS) représentent une technologie d'avenir à haut rendement de conversion d'énergie. Plusieurs techniques sont utilisées pour synthétiser le CIGS. La pulvérisation cathodique réactive est une technique de dépôt adaptée aux grandes surfaces offrant la possibilité d'effectuer un scale-up industriel. L'objectif de ce travail est de développer et d'optimiser un procédé alternatif hybride de co-pulvérisation/évaporation pour la synthèse du composé CIGS. Pour répondre à cet objectif, différentes études ont été réalisées afin d'assurer le contrôle des différents paramètres de dépôt. Dans un premier temps, la phase plasma a été étudiée à l'aide de la spectroscopie d'émission optique pour pouvoir établir des corrélations entre la composition des couches déposées et les espèces présentes dans le plasma. Ceci a permis d'établir des courbes d'étalonnage et de suivi in-situ de la composition et l'homogénéité de l'épaisseur des couches déposées, ainsi que de déterminer l'existence de différentes modes de pulvérisation, reliés à la température appliquée pour l'évaporation du sélénium. Dans un deuxième temps, différents absorbeurs de CIGS ont été synthétisés à partir du procédé hybride développé. Ces absorbeurs ont été déposés en une et en trois étapes pour analyser l'influence des gradients de composition sur leurs propriétés morphologiques, structurales et optoélectroniques. Un absorbeur de CIGS avec un rendement de conversion maximum de 10,4 % a été fabriqué à partir d'une séquence de dépôt en une étape. Un rendement de 9,4 % a été obtenu avec une séquence dépôt en trois étapes. / Cu(In,Ga)Se2 (CIGS) thin film solar cells are a very promising technology for high efficiency energy conversion. Several techniques are used to synthesize CIGS absorbers. Magnetron reactive sputtering is an attractive deposition technique for depositing CIGS absorbers because of its potential for providing uniform coatings over large areas, thus offering the possibility for more competitive industrial scale-up. The objective of this work is to develop and optimize a hybrid alternative co-sputtering/evaporation CIGS deposition process. To meet this goal, various studies have been conducted to ensure control of the various deposition parameters. Initially, plasma was studied with Optical Emission Spectroscopy in order to establish correlations between plasma species and thin film composition, structure and morphology. This has allowed to establish in-situ calibration curves for monitoring the deposited layers composition and their homogeneity, and to determine the existence of different sputtering modes, linked to the selenium evaporation temperature. Then, different CIGS absorbers were synthesized with the stabilized hybrid process. These absorbers were deposited in one and three stages to analyze the influence of composition gradients on their morphological, structural and optoelectronic properties. A CIGS absorber giving a maximum conversion efficiency of 10.4 % was fabricated with a one step process. A 9.3 % efficiency solar cell was obtained with a three-stage deposition process.