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Improving methane production using hydrodynamic cavitation as pre-treatment / Förbättrad methanproduktion med hydrodynamisk kavitation som förbehandlingAbrahamsson, Louise January 2016 (has links)
To develop anaerobic digestion (AD), innovative solutions to increase methane yields in existing AD processes are needed. In particular, the adoption of low energy pre-treatments to enhance biomass biodegradability is needed to provide efficient digestion processes increasing profitability. To obtain these features, hydrodynamic cavitation has been evaluated as an innovative solutions for AD of waste activated sludge (WAS), food waste (FW), macro algae and grass, in comparison with steam explosion (high energy pre-treatment). The effect of these two pre-treatments on the substrates, e.g. particle size distribution, soluble chemical oxygen demand (sCOD), biochemical methane potential (BMP) and biodegradability rate, have been evaluated. After two minutes of hydrodynamic cavitation (8 bar), the mean fine particle size decreased from 489- 1344 nm to 277- 381 nm (≤77% reduction) depending of the biomasses. Similar impacts were observed after ten minutes of steam explosion (210 °C, 30 bar) with a reduction in particle size between 40% and 70% for all the substrates treated. In terms of BMP value, hydrodynamic cavitation caused significant increment only within the A. nodosum showing a post treatment increment of 44% compared to the untreated value, while similar values were obtained before and after treatment within the other tested substrates. In contrast, steam explosion allowed an increment for all treated samples, A. nodosum (+86%), grass (14%) and S. latissima (4%). However, greater impacts where observed with hydrodynamic cavitation than steam explosion when comparing the kinetic constant K. Overall, hydrodynamic cavitation appeared an efficient pre-treatment for AD capable to compete with the traditional steam explosion in terms om kinetics and providing a more efficient energy balance (+14%) as well as methane yield for A. nodosum. / Det behövs innovativa lösningar för att utveckla anaerob rötning i syfte att öka metangasutbytet från biogassubstrat. Beroende på substratets egenskaper, kan förbehandling möjliggöra sönderdelning av bakterieflockar, uppbrytning av cellväggar, elimination av inhiberande ämnen och frigörelse av intracellulära organiska ämnen, som alla kan leda till en förbättring av den biologiska nedbrytningen i rötningen. För att uppnå detta har den lågenergikrävande förebehandlingsmetoden hydrodynamisk kavitation prövats på biologiskt slam, matavfall, makroalger respektive gräs, i jämförelse med ångexplosion. Effekten på substraten av dessa två förbehandlingar har uppmäts genom att undersöka distribution av partikelstorlek, löst organiskt kol (sCOD), biometan potential (BMP) och nedbrytningshastigheten. Efter 2 minuters hydrodynamisk kavitation (8 bar) minskade partikelstorleken från 489- 1344 nm till 277- 281 nm (≤77 % reduktion) för de olika biomassorna. Liknande påverkan observerades efter tio minuters ångexplosion (210 °C, 30 bar) med en partikelstorlekreducering mellan 40 och 70 % för alla behandlade substrat. Efter behandling med hydrodynamisk kavitation, i jämförelse med obehandlad biomassa, ökade metanproduktionens hastighetskonstant (K) för matavfall (+65%), makroalgen S. latissima (+3%), gräs (+16 %) samtidigt som den minskade för A. nodosum (-17 %). Förbehandlingen med ångexplosion ökade hastighetskonstanten för S. latissima (+50 %) och A. nodosum (+65 %) medan den minskade för gräs (-37 %), i jämförelse med obehandlad biomassa. Vad gäller BMP värden, orsakade hydrodynamisk kavitation små variationer där endast A. nodosum visade en ökning efter behandling (+44 %) i jämförelse med obehandlad biomassa. Biomassa förbehandlade med ångexplosion visade en ökning för A .nodosum (+86 %), gräs (14 %) och S. latissima (4 %). Sammantaget visar hydrodynamisk kavitation potential som en effektiv behandling före rötning och kapabel att konkurrera med den traditionella ångexplosionen gällande kinetik och energibalans (+14%) samt metanutbytet för A. nodosum.
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Concepção e estudo de uma unidade compacta para tratamento preliminar de esgoto sanitário composta por separador hidrodinâmico por vórtice e grade fina de fluxo tangencial / Designing and study of a compact unit for sewage preliminary treatment made up of a hydrodynamic vortex separator and a tangential flux fine screenPrado, Gustavo Silva do 15 September 2006 (has links)
Atualmente, existe uma tendência entre os projetistas brasileiros de valorizar a etapa de tratamento preliminar em projetos de novas estações de tratamento de esgoto (ETE). Neste ensejo foi concebido, construído e estudado um protótipo, em escala plena, de uma unidade composta de separador hidrodinâmico por vórtice (SHV) empregado como desarenador e grade fina cilíndrica de fluxo tangencial. Estudos acerca da hidrodinâmica da unidade, fundamentados em ensaios de estímulo-resposta com traçador (sal de cozinha) e simulações computacionais do padrão de escoamento em software de dinâmica dos fluidos computacional, demonstrou que ao se operar a unidade com taxas de aplicação superficial (TAS) de 764 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd e 1.528 'M POT.3'/'M POT.2'd o regime de macro-mistura do padrão de escoamento que se desenvolve no SHV aproximou-se do plug-flow, porém com certo grau de mistura que diminuiu com o aumento da TAS. Nesta pesquisa, foram desenvolvidos dois métodos um para determinação da concentração de areia no esgoto sanitário e outro para determinação da distribuição granulométrica dos grãos dessa areia. Ambos foram empregados na avaliação de desempenho da unidade de tratamento preliminar desenvolvida, que foi realizada na estação elevatória de ETE Jardim das Flores do município de Rio Claro, SP. Durante esta fase da pesquisa, o SHV demonstrou enorme potencialidade na remoção de areia para as TAS de 764 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd e 1.528 'M POT.3'/'M POT.2'd, porquanto, além de não remover significativamente matéria orgânica particulada (medida em termos de concentração de sólidos suspensos voláteis) presentes no esgoto sanitário, a unidade atingiu eficiências de remoção de grãos de areia de tamanho maior ou igual a 200 'mü'm entre 85% e 95%. Entretanto, a grade fina cilíndrica de fluxo tangencial (auto-limpante) revelou-se inviável. / Currently, there is a trend among the brazilian designers of valorizing the preliminary treatment in recently designed wastewater treatment plants (WWTP). In this context, a full scale prototype of a unit made up of a hydrodynamic vortex separator (HVS) applied as a degritter and a tangential flux fine screening was designed, built and evaluated. Research about the hydrodynamic of the prototype, based on stimulus-response essays with a salt tracer (sodium chloride) and computational simulations of the flow pattern using the computational fluid dynamic (CFD) software, showed that the macro mixture regime of the flow was similar to a plug-flow when the unit was operated with superficial loading rates (SLR) of 746 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd and 1.528 'M POT.3'/'M POT.2'd, however, the flow presented a certain mixture degree that reduced with the SLR increase. In this research, two methods were developed: one for the determination of grit concentration in sewage and another one for the assessment of grit grading. Both methods were used on the evaluation of the HVS prototype efficiency, which was carried out at Jardim das Flores WWT, in the city of Rio Claro, SP. During this phase of the research, the HVS presented a great potential for grit removal when the SLR of 746 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd and 1.528 'M POT.3'/'M POT.2'd were applied; for the reason that, besides not significantly removing the particulate organic matter present in sewage (measured as volatile suspended solids), the unit achieved grit removal efficiencies in the range of 85% to 95% for grit equal to or large than 200 'mü'm. However, the tangential flux cylindrical fine screening (self cleaning) did not reveal feasibility.
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Comparison of geoenvironmental properties of caustic and noncaustic oil sand fine tailingsMiller, Warren Gregory 11 1900 (has links)
A study was conducted to evaluate the properties and processes influencing the rate and magnitude of volume decrease and strength gain for oil sand fine tailings resulting from a change in bitumen extraction process (caustic versus non-caustic) and the effect of adding a coagulant to caustic fine tailings.
Laboratory flume deposition tests were carried out with the objective to hydraulically deposit oil sand tailings and compare the effects of extraction processes on the nature of beach deposits in terms of geometry, particle size distribution, and density. A good correlation exists between flume deposition tests results using oil sand tailings and the various other tailings materials. These comparisons show the reliability and effectiveness of flume deposition tests in terms of establishing general relationships and can serve as a guide to predict beach slopes.
Fine tailings were collected from the various flume tests and a comprehensive description of physical and chemical characteristics of the different fine tailings was carried out. The characteristics of the fine tailings is presented in terms of index properties, mineralogy, specific surface area, water chemistry, liquid limits, particle size distribution and structure. The influence of these fundamental properties on the compressibility, hydraulic conductivity and shear strength properties of the fine tailings was assessed. Fourteen two meter and one meter high standpipe tests were instrumented to monitor the rate and magnitude of self-weight consolidation of the different fine tailings materials. Consolidation tests using slurry consolidometers were carried out to determine consolidation properties, namely compressibility and hydraulic conductivity, as well as the effect of adding a coagulant (calcium sulphate [CaSO4]) to caustic fine tailings. The thixotropic strength of the fine tailings was examined by measuring shear strength over time using a vane shear apparatus.
A difference in water chemistry during bitumen extraction was concluded to be the cause of substantial differences in particle size distributions and degree of dispersion of the comparable caustic and non-caustic fine tailings. The degree of dispersion was consistent with predictions for dispersed clays established by the sodium adsorption ratio (SAR) values for these materials. The biggest advantage of non-caustic fine tailings and treating caustic fine tailings with coagulant is an increased initial settlement rate and slightly increased hydraulic conductivity at higher void ratios. Thereafter, compressibility and hydraulic conductivity are governed by effective stress. The chemical characteristics of fine tailings (water chemistry, degree of dispersion) do not have a significant impact on their compressibility behaviour and have only a small influence at high void ratio (low effective stress). Fine tailings from a caustic based extraction process had relatively higher shear strengths than comparable non-caustic fine tailings at equivalent void ratios. However, shear strength differences were small and the overall impact on consolidation behaviour, which also depends on compressibility and hydraulic conductivity, is not expected to be significant.
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Wheat Straw-Clay-Polypropylene Hybrid CompositesSardashti, Amirpouyan 23 September 2009 (has links)
The preparation of polymeric hybrid composite consisting of organic and inorganic fillers is of interest for industries like automotive, construction and packaging. In order to understand and predict the physical and chemical properties of these hybrid composites, it is necessary to fully understand the nature and properties of the employed fillers. In this study, the preparation of polypropylene hybrid composite consisting of wheat straw and clay was investigated. A detailed study was performed on wheat straw from South Western Ontario region. The effect of grinding the straw and compounding it with polypropylene was investigated. Experiments were carried out to identify the thermal stability of the ground wheat straw with respect to their size and composition. It was important to identify a correlation between these properties in order to minimize the straw degradation by processing and also to improve the final properties of the hybrid composite. The composite samples were prepared through melt blending method using a co-rotating twin-screw extruder. Sample test bars were prepared by injection moulding. The composition of the constituents of the hybrid composite; percentages of wheat straw, clay and coupling agent, were varied in order to investigate their influence on thermal stability, water resistance and mechanical properties.
The results of the study indicated that grinding the wheat straw with a hammer mill produced particles with different sizes and shapes. It was found that through the grinding system all particles, regardless of their size, had a multi-layered structure similar to the plant structure. Further hammer milling did not produce plant particles with long aspect ratios that would be expected in a defibrillation process. Analysis of the chemical composition of wheat straw particles of different sizes and shapes was used to measure the ratio of hemicelluloses: lignin and the ash content. It was found that the large particles contained more amount of lignin whereas smaller particles had larger amount of ash content. The thermal stability of the particles was found to be a function of particle size rather than the lignin content. Particle size analysis on the wheat straw particles after the extrusion process indicated a reduction in the particle length and aspect ratio.
The thermal stability of the composites was found to be enhanced by the addition of clay particles at higher temperature and the addition of coupling agent at lower temperatures. Increasing the amount of wheat straw and clay content increased the flexural modulus and reduced the resistance for water absorption. Increasing the amount of coupling agent also increased the flexural modulus and resistance for water absorption. The morphological study by scanning electron microscopy revealed that coupling agent increased the interfacial interaction between the particles and the polymer matrix.
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Wheat Straw-Clay-Polypropylene Hybrid CompositesSardashti, Amirpouyan 23 September 2009 (has links)
The preparation of polymeric hybrid composite consisting of organic and inorganic fillers is of interest for industries like automotive, construction and packaging. In order to understand and predict the physical and chemical properties of these hybrid composites, it is necessary to fully understand the nature and properties of the employed fillers. In this study, the preparation of polypropylene hybrid composite consisting of wheat straw and clay was investigated. A detailed study was performed on wheat straw from South Western Ontario region. The effect of grinding the straw and compounding it with polypropylene was investigated. Experiments were carried out to identify the thermal stability of the ground wheat straw with respect to their size and composition. It was important to identify a correlation between these properties in order to minimize the straw degradation by processing and also to improve the final properties of the hybrid composite. The composite samples were prepared through melt blending method using a co-rotating twin-screw extruder. Sample test bars were prepared by injection moulding. The composition of the constituents of the hybrid composite; percentages of wheat straw, clay and coupling agent, were varied in order to investigate their influence on thermal stability, water resistance and mechanical properties.
The results of the study indicated that grinding the wheat straw with a hammer mill produced particles with different sizes and shapes. It was found that through the grinding system all particles, regardless of their size, had a multi-layered structure similar to the plant structure. Further hammer milling did not produce plant particles with long aspect ratios that would be expected in a defibrillation process. Analysis of the chemical composition of wheat straw particles of different sizes and shapes was used to measure the ratio of hemicelluloses: lignin and the ash content. It was found that the large particles contained more amount of lignin whereas smaller particles had larger amount of ash content. The thermal stability of the particles was found to be a function of particle size rather than the lignin content. Particle size analysis on the wheat straw particles after the extrusion process indicated a reduction in the particle length and aspect ratio.
The thermal stability of the composites was found to be enhanced by the addition of clay particles at higher temperature and the addition of coupling agent at lower temperatures. Increasing the amount of wheat straw and clay content increased the flexural modulus and reduced the resistance for water absorption. Increasing the amount of coupling agent also increased the flexural modulus and resistance for water absorption. The morphological study by scanning electron microscopy revealed that coupling agent increased the interfacial interaction between the particles and the polymer matrix.
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Comparison of geoenvironmental properties of caustic and noncaustic oil sand fine tailingsMiller, Warren Gregory Unknown Date
No description available.
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Investigation into submicrometer particle and gaseous emissions from airport ground running proceduresMazaheri, Mandana January 2009 (has links)
Emissions from airport operations are of significant concern because of their potential impact on local air quality and human health. The currently limited scientific knowledge of aircraft emissions is an important issue worldwide, when considering air pollution associated with airport operation, and this is especially so for ultrafine particles. This limited knowledge is due to scientific complexities associated with measuring aircraft emissions during normal operations on the ground. In particular this type of research has required the development of novel sampling techniques which must take into account aircraft plume dispersion and dilution as well as the various particle dynamics that can affect the measurements of the aircraft engine plume from an operational aircraft.
In order to address this scientific problem, a novel mobile emission measurement method called the Plume Capture and Analysis System (PCAS), was developed and tested. The PCAS permits the capture and analysis of aircraft exhaust during ground level operations including landing, taxiing, takeoff and idle. The PCAS uses a sampling bag to temporarily store a sample, providing sufficient time to utilize sensitive but slow instrumental techniques to be employed to measure gas and particle emissions simultaneously and to record detailed particle size distributions. The challenges in relation to the development of the technique include complexities associated with the assessment of the various particle loss and deposition mechanisms which are active during storage in the PCAS. Laboratory based assessment of the method showed that the bag sampling technique can be used to accurately measure particle emissions (e.g. particle number, mass and size distribution) from a moving aircraft or vehicle.
Further assessment of the sensitivity of PCAS results to distance from the source and plume concentration was conducted in the airfield with taxiing aircraft. The results showed that the PCAS is a robust method capable of capturing the plume in only 10 seconds. The PCAS is able to account for aircraft plume dispersion and dilution at distances of 60 to 180 meters downwind of moving a aircraft along with particle deposition loss mechanisms during the measurements. Characterization of the plume in terms of particle number, mass (PM2.5), gaseous emissions and particle size distribution takes only 5 minutes allowing large numbers of tests to be completed in a short time. The results were broadly consistent and compared well with the available data.
Comprehensive measurements and analyses of the aircraft plumes during various modes of the landing and takeoff (LTO) cycle (e.g. idle, taxi, landing and takeoff) were conducted at Brisbane Airport (BNE). Gaseous (NOx, CO2) emission factors, particle number and mass (PM2.5) emission factors and size distributions were determined for a range of Boeing and Airbus aircraft, as a function of aircraft type and engine thrust level. The scientific complexities including the analysis of the often multimodal particle size distributions to describe the contributions of different particle source processes during the various stages of aircraft operation were addressed through comprehensive data analysis and interpretation.
The measurement results were used to develop an inventory of aircraft emissions at BNE, including all modes of the aircraft LTO cycle and ground running procedures (GRP). Measurements of the actual duration of aircraft activity in each mode of operation (time-in-mode) and compiling a comprehensive matrix of gas and particle emission rates as a function of aircraft type and engine thrust level for real world situations was crucial for developing the inventory. The significance of the resulting matrix of emission rates in this study lies in the estimate it provides of the annual particle emissions due to aircraft operations, especially in terms of particle number.
In summary, this PhD thesis presents for the first time a comprehensive study of the particle and NOx emission factors and rates along with the particle size distributions from aircraft operations and provides a basis for estimating such emissions at other airports. This is a significant addition to the scientific knowledge in terms of particle emissions from aircraft operations, since the standard particle number emissions rates are not currently available for aircraft activities.
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Caractérisation et stabilité de la matière organique du sol en contexte montagnard calcaire : proposition d'indicateurs pour le suivi de la qualité des sols à l'échelle du paysage / Characterization and stability of soil organic matter in calcareous mountain : proposal of indicators for soil quality monitoring at the landscape scaleSaenger, Anaïs 16 April 2013 (has links)
Les sols de montagne représentent d'importants réservoirs de carbone (C) potentiellement vulnérables aux changements climatiques et changements d'usage qui les affectent de manière amplifiée. Or la grande variabilité de ces milieux, leur faible accessibilité ainsi que le manque d'outils de mesure appropriés limitent nos connaissances qui restent aujourd'hui très fragmentaires en ce qui concerne les stocks, la chimie et la réactivité du carbone organique des sols (COS). Ces informations sont pourtant nécessaires pour appréhender l'évolution de ces sols et de leur C dans ce contexte de changements globaux. Les objectifs de ce travail de thèse étaient (i) d'accéder à une meilleure compréhension de la nature, de la stabilité et de la vulnérabilité du COS dans une mosaïque d'écosystèmes des Préalpes calcaires (massif du Vercors), (ii) de rechercher des outils de caractérisation rapides et fiables adaptés à l'étude et au suivi du COS à l'échelle du paysage, et enfin (iii) de proposer des indices pour l'évaluation et le suivi de la qualité des sols en milieu de montagne. Dans un premier temps, nous avons testé l'application de la pyrolyse Rock-Eval pour l'étude du COS à grande échelle sur un ensemble d'unités écosystémiques. Nous avons ensuite comparé la pyrolyse Rock-Eval à deux techniques classiques d'étude de la matière organique du sol (MOS) : le fractionnement granulodensimétrique de la MOS et la spectroscopie moyen infrarouge. Ces approches analytiques couplées nous ont permis de quantifier les stocks de C à l'échelle de la zone d'étude et d'expliquer la stabilité et la vulnérabilité du COS sous des angles variés. Les facteurs responsables des patrons observés dans les différentes unités écosystémiques sont discutés. Ce travail a également confirmé la pertinence de l'outil Rock-Eval pour répondre aux objectifs fixés. Parallèlement, des approches biologiques nous ont permis d'évaluer l'importance de la composante microbienne dans ces sols. Enfin, des indices évaluant le statut organique des sols (stockage de COS, fertilité des sols, vulnérabilité du COS) sont proposés pour constituer des outils de gestion et d'aide à la décision. / Mountain soils are major reservoirs of carbon (C), potentially vulnerable to climate and land use changes that affect them significantly. However, the great variability of these soils, their limited accessibility and the lack of appropriate measurement tools restrict our knowledge. Today, our comprehension of the biogeochemistry of mountain soils remains very incomplete regarding stocks, chemistry and reactivity of soil organic carbon (SOC). Yet this information is necessary to understand the evolution of soil carbon in the current context of global change. The objectives of this work were (i) to gain a better understanding of the nature, stability and vulnerability of SOC in a mosaic of ecosystems in a calcareous massif in the Alps (Vercors massif), (ii) to search for fast and reliable characterization tools, suitable for the study and monitoring of COS at the landscape scale, and (iii) to propose indicators for the assessment and monitoring of soil quality in mountain regions. As a first step, we tested the application of Rock-Eval pyrolysis for the study of COS at large-scale on a set of ecosystem units. Then, we compared the Rock-Eval approach to two conventional techniques for soil organic matter (SOM) study: the particle-size fractionation of SOM, and the mid-infrared spectroscopy. These coupled analytical approaches allowed us to quantify C stocks across the study area, and explain the stability and the vulnerability of COS at various angles. Factors responsible for the patterns observed in the different eco-units are discussed. This work also confirmed the relevance of the Rock-Eval tool to achieve our previous objectives. Biological approaches allowed us to assess the significance of microbial pool in these soils. Finally, indices assessing the status of SOM (SOC storage, soil fertility, vulnerability COS) were proposed and constituted interesting management tools for decision-makers.
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Etude et modélisation de l'interface graphite/électrolyte dans les batteries lithium-ion / Study and establishment of a model of the graphite/electrolyte interface in lithium-ion batteriesChhor, Sarine 19 December 2014 (has links)
Cette thèse se positionne dans le domaine des batteries lithium-ion. Elle a pourobjectif de mieux comprendre le fonctionnement de l’électrode négative de graphiteen étudiant le processus de formation du film de passivation, couramment appeléSEI (Solid Electrolyte Interface) créé à l’interface avec l’électrolyte. Ce travail nousa conduit à proposer des modèles pouvant expliquer comment se forme la SEI et àidentifier les phénomènes qui entrent en jeu dans le fonctionnement de la batterie.La SEI résulte de la réaction entre l’électrode de graphite, les ions lithium et les moléculesorganiques de l’électrolyte qui survient lors du premier processus d’insertion.Elle est principalement composée des produits de décomposition de l’électrolyte etles ions lithium consommés ne sont plus échangeables. Elle est donc responsable dela capacité irréversible observée lors du premier cycle de formation, correspondantà la différence de capacité entre le processus d’insertion et le processus de désinsertion.Il est donc essentiel de mieux comprendre les paramètres qui l’influencentpour pouvoir ainsi la contrôler et limiter la perte irréversible de capacité. Les performancesen capacité de l’élément lithium-ion sont directement liées à cette valeurde capacité irréversible, elle doit être limitée afin de maximiser la quantité d’ionslithium échangée entre l’électrode négative et l’électrode positive. La stabilité dela SEI conditionne ensuite le comportement en cyclage de l’électrode au cours dutemps.Dans ce mémoire de thèse, nous avons choisi de caractériser le comportement del’électrode de graphite en faisant varier la nature de l’électrolyte et la taille desparticules de graphite tout en restant le plus proche possible du fonctionnementd’une vraie batterie. Au travers des techniques de caractérisations électrochimiques(cyclage galvanostatique, spectroscopie d’impédance) associées à des techniques decaractérisation de surface (spectroscopie de photoélectrons X, microscopie électroniqueà balayage), les résultats obtenus ont permis de proposer un nouveau modèlede formation de la SEI.Pour l’électrolyte, nous avons choisi de ne regarder que l’effet du solvant (le carbonatede propylène) et de l’additif (le carbonate de vinylène). Ces deux composésentrent dans la composition des électrolytes utilisés dans les éléments lithium-ioncommerciaux. Pour l’électrode de graphite, le choix des particules s’avère primordialpuisque chaque type de particules possède une chimie de surface spécifique (plans223basaux ou plans prismatiques) susceptible de réagir différemment vis-à-vis de l’électrolyte.Deux particules de graphite, de taille et de morphologie différentes, ont étéétudiées. Elles sont utilisées séparément en tant que matière active dans les électrodesnégatives des batteries lithium-ion. Notre spécificité est d’avoir préparé desélectrodes constituées par un mélange de ces deux particules et de les avoir ensuitecaractérisées en formation. L’application de conditions de fonctionnement différentescomme le régime de cyclage et la température d’essai ont mis en évidence les valeursidéales conduisant à minimiser la dégradation de l’électrolyte et à optimiser laqualité du film.Nous avons abouti, au travers de l’ensemble des méthodes de caractérisations misesen oeuvre, à une meilleure compréhension des mécanismes de formation du film depassivation permettant ainsi d’améliorer cette étape essentielle à la pérennité desperformances de l’électrode dans le temps. Ce travail a donc un réel impact auniveau industriel. Le modèle de formation proposé apporte un éclairage nouveau auprocessus de formation et peut permettre également d’aider en amont à la fabricationdes particules de graphite. / This work relates to the lithium ion battery field. The purpose of this study is tobetter understand the behavior of graphite electrodes by focusing on the formationof a passive layer named Solid Electolyte Interface (SEI) which is formed at thegraphite/electrolyte interface. This work has led us to put forward models whichcan explain the SEI formation and identify the reactions which take place in alithium ion battery.The SEI results from reactions between graphite electrode, lithium ions and organicmolecules from the electrolyte during the first charge of the lithium ion battery. It ismainly composed of decomposition products from the electrolyte. Consumed lithiumions can no longer be used in the next cycle. The SEI is therefore responsible for theirreversible capacity during the first formation cycle which is the charge loss betweenthe intercalation process and the deintercalation process. It is necessary to betterunderstand the impact of the formation conditions and other parameters in orderto control and limit the irreversible charge loss. Lithium ion battery performancesdepend on this irreversible capacity, this value has to be reduced in order to maximizethe amount of exchanged lithium ions between negative and positive electrodes. TheSEI stability will determine the electrode behavior upon cycling.In this thesis, we chose to study the graphite behavior by testing several electrolytecompositions and graphite particle sizes in electrochemical cells similar to areal battery. Electrochemical techniques (galvanostatic cycling and electrochemicalimpedance spectroscopy) and surface analyses (X-ray photoelectron spectroscopy,scanning electron microscopy) will be combined. These results helped us to developa new model of the SEI formation.For the electrolyte, we chose to study the effect of the solvent (propylene carbonate)and the additive (vinylene carbonate). Both components are commonly used inthe electrolyte for commercial lithium ion batteries. For the graphite electrode, thechoice of graphite particles is essential because each graphite family has its ownsurface chemistry (basal and prismatic surfaces) which can react in many wayswith the electrolyte. Two graphite particles, with specific sizes and morphologiesare studied. They are separately used as active materials for negative electrodes inlithium ion batteries. Our unique approach is to prepare graphite electrodes basedon a mix of both particles with various compositions and then test the electrode225performances. After testing several formation conditions such as the cycling rateand the temperature, we found the ideal formation conditions for minimizing theelectrolyte decomposition and optimizing the film quality.Finally, based on all the characterization methods, we came to a better understandingof the film formation process. In this way, we have improved this essentialpreliminary step which can now lead to more durable cycling performances overtime. This study can have a major impact on the industrial level. The formationmodel cast a new light on the formation process and can therefore help to makeefficient graphite electrodes.
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Concepção e estudo de uma unidade compacta para tratamento preliminar de esgoto sanitário composta por separador hidrodinâmico por vórtice e grade fina de fluxo tangencial / Designing and study of a compact unit for sewage preliminary treatment made up of a hydrodynamic vortex separator and a tangential flux fine screenGustavo Silva do Prado 15 September 2006 (has links)
Atualmente, existe uma tendência entre os projetistas brasileiros de valorizar a etapa de tratamento preliminar em projetos de novas estações de tratamento de esgoto (ETE). Neste ensejo foi concebido, construído e estudado um protótipo, em escala plena, de uma unidade composta de separador hidrodinâmico por vórtice (SHV) empregado como desarenador e grade fina cilíndrica de fluxo tangencial. Estudos acerca da hidrodinâmica da unidade, fundamentados em ensaios de estímulo-resposta com traçador (sal de cozinha) e simulações computacionais do padrão de escoamento em software de dinâmica dos fluidos computacional, demonstrou que ao se operar a unidade com taxas de aplicação superficial (TAS) de 764 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd e 1.528 'M POT.3'/'M POT.2'd o regime de macro-mistura do padrão de escoamento que se desenvolve no SHV aproximou-se do plug-flow, porém com certo grau de mistura que diminuiu com o aumento da TAS. Nesta pesquisa, foram desenvolvidos dois métodos um para determinação da concentração de areia no esgoto sanitário e outro para determinação da distribuição granulométrica dos grãos dessa areia. Ambos foram empregados na avaliação de desempenho da unidade de tratamento preliminar desenvolvida, que foi realizada na estação elevatória de ETE Jardim das Flores do município de Rio Claro, SP. Durante esta fase da pesquisa, o SHV demonstrou enorme potencialidade na remoção de areia para as TAS de 764 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd e 1.528 'M POT.3'/'M POT.2'd, porquanto, além de não remover significativamente matéria orgânica particulada (medida em termos de concentração de sólidos suspensos voláteis) presentes no esgoto sanitário, a unidade atingiu eficiências de remoção de grãos de areia de tamanho maior ou igual a 200 'mü'm entre 85% e 95%. Entretanto, a grade fina cilíndrica de fluxo tangencial (auto-limpante) revelou-se inviável. / Currently, there is a trend among the brazilian designers of valorizing the preliminary treatment in recently designed wastewater treatment plants (WWTP). In this context, a full scale prototype of a unit made up of a hydrodynamic vortex separator (HVS) applied as a degritter and a tangential flux fine screening was designed, built and evaluated. Research about the hydrodynamic of the prototype, based on stimulus-response essays with a salt tracer (sodium chloride) and computational simulations of the flow pattern using the computational fluid dynamic (CFD) software, showed that the macro mixture regime of the flow was similar to a plug-flow when the unit was operated with superficial loading rates (SLR) of 746 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd and 1.528 'M POT.3'/'M POT.2'd, however, the flow presented a certain mixture degree that reduced with the SLR increase. In this research, two methods were developed: one for the determination of grit concentration in sewage and another one for the assessment of grit grading. Both methods were used on the evaluation of the HVS prototype efficiency, which was carried out at Jardim das Flores WWT, in the city of Rio Claro, SP. During this phase of the research, the HVS presented a great potential for grit removal when the SLR of 746 'M POT.3'/'M POT.2'd; 1.146 'M POT.3'/'M POT.2'd and 1.528 'M POT.3'/'M POT.2'd were applied; for the reason that, besides not significantly removing the particulate organic matter present in sewage (measured as volatile suspended solids), the unit achieved grit removal efficiencies in the range of 85% to 95% for grit equal to or large than 200 'mü'm. However, the tangential flux cylindrical fine screening (self cleaning) did not reveal feasibility.
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