Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-06-25T13:24:34Z No. of bitstreams: 1 Dissserta??o final_Lucas Weber Dias.pdf: 2263503 bytes, checksum: ea9c29b6b538c56ea795610f7bc5a808 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-06-29T13:30:33Z (GMT) No. of bitstreams: 1 Dissserta??o final_Lucas Weber Dias.pdf: 2263503 bytes, checksum: ea9c29b6b538c56ea795610f7bc5a808 (MD5) / Made available in DSpace on 2018-06-29T13:38:08Z (GMT). No. of bitstreams: 1 Dissserta??o final_Lucas Weber Dias.pdf: 2263503 bytes, checksum: ea9c29b6b538c56ea795610f7bc5a808 (MD5) Previous issue date: 2017-08-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The main function of the packaging is to protect the cosmetic from the external environment, avoiding undesirable changes in the product that is contained inside, and thus indispensable for its storage and transpotation. However, its disposal improperly generates a large volume of solid waste, which is directly related to the environmental impact. One of the alternatives to minimize this impact is the use of packages made from biodegradable polymeric films based on polyacrylic acid (PLA), poly (lactic acid ? co- glycolic acid) (PLGA) and polycaprolactone (PCL), blends of theses polymers and incorporation of Zeolites 13x. The thermal, mechanical optical, water vapor barrier and degradation time in saline solution of polymeric systems are evaluated for application as cosmetic packaging. The technique used for the preparation of the polymer films was that of Solvent Casting. The polymer films were characterized by the techniques of UV-Vis Spectrophotometry, Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Scsannig Electron Microscopy (SEM), transparency, water vapor permeability, mechanical assay and absorption spectroscopy atomic. The transmittance results showed that the PCL and PLA blends showed greater blockage to the passage of radiation (190 - 1100nm) and water vapor permeability. The incorporation of PLA or PLGA to the pure PCL resulted in material with batter thermal properties, but more rigid and brittle, not modifying the degradation process until 120 days of incubation. The incorporation of 15% Zeolite 13x into the PCL/PLA blends did not significantly modify the properties evaluated. / As embalagens t?m como principal fun??o, proteger o cosm?tico do meio externo, evitando que ocorram altera??es indesej?veis no produto que est? contido no seu interior, sendo assim indispens?vel para o seu armazenamento e transporte. Por?m, o seu descarte de forma inadequada gera um grande volume de res?duos s?lidos, que est? diretamente relacionado com o impacto ambiental. Uma das alternativas para minimizar este impacto ? a utiliza??o de embalagens confeccionadas a partir de pol?meros biodegrad?veis. Desta maneira, o presente trabalho tem como objetivo a prepara??o e caracteriza??o de filmes polim?ricos biodegrad?veis baseados em Poli ? ?cido l?ctico (PLA), Poli (?cido l?ctico ? co- ?cido glic?lico) (PLGA) e Policaprolactona (PCL), blendas destes pol?meros e incorpora??o de Ze?litas 13x. S?o avaliadas as propriedades t?rmicas, mec?nicas, ?pticas, de barreira a vapor de ?gua e o tempo de degrada??o em solu??o salina dos sistemas polim?ricos, visando aplica??o como embalagem para cosm?ticos. A t?cnica utilizada para a prepara??o dos filmes polim?ricos foi a de Solvent Casting. Os filmes polim?ricos foram caracterizados pelas t?cnicas de Espectrofotometria UV-Vis, Calorimetria Explorat?ria Diferencial (DSC), An?lise Termogravim?trica (TGA), Microscopia Eletr?nica de Varredura (MEV-FEG), transpar?ncia, permeabilidade a vapor de ?gua, ensaio mec?nico e Espectroscopia de absor??o at?mica. Os resultados de transmit?ncia mostraram que a blenda de PCL e PLA apresentou maior bloqueio ? passagem de radia??o (190 nm ? 1100 nm) e ? permeabilidade de vapor de ?gua. A incorpora??o de PLA ou PLGA ao PCL puro resultou num material com melhores propriedades t?rmicas, por?m mais r?gido e quebradi?o, n?o modificando o processo de degrada??o at? 120 dias de incuba??o. A incorpora??o de 15% Ze?lita 13x ? blenda de PCL/PLA n?o modificou significativamente as propriedades avaliadas.

The industrial sector is one of the largest emitters of CO2 and a great potential for retrofitting with carbon capture systems. In this work the performance of a palladium-based membrane reactor at 400°C and operating pressures between 100-400 kPa have been studied in terms of methane conversion, hydrogen recovery, hydrogen purity, and CO2 emission. It is found that the MR has the potential to produce high purity hydrogen while the methane conversion values could be as high as 40% at very moderate operating conditions and without using any sweep gases. The H2 permeation and separation properties of two Pd-based composite membranes were evaluated and compared at 400 °C and at a pressure range of 150 kPa to 600 kPa. One membrane was characterized by an approximately 8 μm-thick palladium (Pd)-gold (Au) layer deposited on an asymmetric microporous Al2O3 substrate; the other membrane consisted of an approximately 11 μm-thick pure palladium layer deposited on a yttria-stabilized zirconia (YSZ) support. At 400 °C and with a trans-membrane pressure of 50 kPa, the membranes showed a H2 permeance of 8.42 × 10−4 mol/m2·s·Pa0.5 and 2.54 × 10−5 mol/m2·s·Pa0.7 for Pd-Au and Pd membranes, respectively. Pd-Au membrane showed infinite ideal selectivity to H2 with respect to He and Ar at 400 °C and a trans-membrane pressure of 50 kPa, while the ideal selectivities for the Pd membrane under the same operating conditions were much lower. Furthermore, the permeation tests for ternary and quaternary mixtures of H2, CO, CO2, CH4, and H2O were conducted on the Pd/YSZ membrane. The H2 permeating flux decreased at the conclusion of the permeation tests for all mixtures. This decline however, was not permanent, i.e., H2 permeation was restored to its initial value after treating the membrane with H2 for a maximum of 7 h. The effects of gas hourly space velocity (GHSV) and the steam-to-carbon (S/C) ratio on H2 permeation were also investigated using simulated steam methane reforming mixtures. It was found that H2 permeation is highest at the greatest GHSV, due to a decline in the concentration polarization effect. Variations in S/C ratio however, showed no significant effect on the H2 permeation. The permeation characteristics for the Pd/YSZ membrane were also investigated at temperatures ranging from 350 to 400 °C. The pre-exponential factor and apparent activation energy were found to be 5.66 × 10−4 mol/m2·s·Pa0.7 and 12.8 kJ/mol, respectively. Scanning Electron Microscope (SEM) and X-ray diffraction (XRD) analyses were performed on both pristine and used membranes, and no strong evidence of the formation of Pd-O or any other undesirable phases was observed. The permeation tests with pure hydrogen and inert gases indicate that the MR is highly selective toward hydrogen and the produced hydrogen is an ultrahigh purity grade. The carbon capture experiments in the work consists of dehydrating the retentate stream and redirecting it to a 13X packed bed before analyzing the stream via mass spectrometry. The carbon capture studies reveal that approximately 5.96 mmole CO2 (or 262.25 mg of CO2)can be captured per g of 13X. In this study, SEM-EDS, and XRD technics have been used to characterize the crystallography and morphology of the membrane surface. These material characterization techniques reveal that the surface of the membrane has gone through significant oxidation during the steam methane reforming reaction, although this oxidation is only limited to the few nanometers of depth through the surface of the palladium membrane.

The overall objective of this thesis is to evaluate the fundamentals of current low concentration CO2 separation technologies and to provide an alternate method using adsorption technology with existing as well as new adsorbents. Two different applications for the adsorption of CO2 are explored; Direct Air Capture (DAC) and excimer gas purification. The investigation of aerogels as possible adsorbent for these applications was also explored. The first application, DAC of CO2 using adsorbents, addresses climate change by reducing the amount of atmospheric CO2 levels that are directly correlated to global warming. Because of DAC being carbon negative, this field has gained significant attention in the literature. DAC as a CO2 reduction strategy was approached in two ways: 1. Chapter 2 investigates capturing and concentrating CO2 from 0.04% in the air to 95% to be able to sequester it into the ground. This research began by doing an adsorbent selection using pure gas gravimetric measurements on seven different commercially available type X zeolites that were determined to have potential for this separation. Breakthrough experiments were then carried out with the most promising zeolite by perturbing the bed with compressed ambient air. In the process studied, a basic four step temperature vacuum swing adsorption (TVSA) cycle was investigated comprising the following steps: pressurization, adsorption, blowdown, and desorption. Four different regeneration temperatures were tested along with four different gas space velocities. With this cycle configuration, CO2 was concentrated to 95% from 0.04% with total capture fractions as high as 81%. This study highlighted methods to reduce the energy consumption per ton of CO2 captured in the system as well as the potential of using low Si/Al ratio faujasite structured zeolites in DAC of CO2 for greenhouse gas reduction. 2. Chapter 3 expands on the research of Chapter 2 by capturing CO2 from 0.04% in the air and concentrating it to high purity CO2 levels where the cost for operating the process will be reimbursed through the value of the produced CO2. The goal of this research was to increase the CO2 to as high as possible because the purer the CO2, the more valuable it is. This research started by conducting an in-depth investigation into the pure gas adsorption of CO2, N2, O2, and Ar on the most promising zeolite from Chapter 2. The data was then fitted to the TD-Toth model which allowed for the evaluation of the TVSA cycle and showed the potential of reducing the pressure and/or elevating the temperature during the blowdown step in order to produce high purity CO2. To confirm this, the TVSA cycle was run on a fixed bed breakthrough experiment where high purity CO2 was produced between a concentration of 99.5% and 99.96% by lowering the blowdown pressure. By controlling the blowdown temperature, the concentration of the product was increased from 99.8% to 99.95%, however with a significant loss of CO2. This effect of N2, O2, and Ar desorbing during the blowdown step with CO2 desorbing during the evacuation step is shown graphically by measuring the concentration and flow rate of the exiting gas species. The results from this study show the potential for producing a valuable product of high purity CO2 from atmospheric concentrations. The second application in this thesis that is explored in Chapter 4 is the purification of trace impurities of CO2, CF4, COF2, and O2 from F2, Kr, and Ne for applications in excimer lasers. Due to the incompatibility of many adsorbents to F2 and HF, aluminas and polymeric adsorbents were selected as potentially compatible materials. To increase the compatibility of these adsorbents, the use of a cryo-cooler was determined to be feasible to precool the feed stream before separation, which increases the adsorption capacity and compatibility of the material to F2 and HF. To determine the adsorption potential in the low concentration of these adsorbents, the concentration pulse chromatographic technique was chosen to determine the Henry’s Law constants of CO2, CF4, and O2. This data was then plotted on the van’t Hoff plot and extrapolated to colder temperatures to determine the benefit of using a cryo-cooler. From this study, it was determined that HayeSep Q was the best polymeric adsorbent with significant adsorption of CO2 at temperatures below -50˚C while being the best performing CF4 adsorbent. AA-300 was the best performing alumina in this study while having significant adsorption of CF4 at temperatures below -135˚C. However, from a compatibility standpoint, both of these materials need to be tested to determine their robustness in the presence of F2 and HF at room and reduced temperatures. Chapters 5 & 6 in this thesis explore the fundamentals of adsorption on aerogels as a prelude to using aerogels as possible adsorbents for DAC of CO2. This investigation into aerogels looks at silica aerogels and carbon aerogels, which are both industrially produced and explores their adsorption with relation to like materials such as silica gel and activated carbons. Both of these Chapters utilize experimentally determined adsorption isotherms of CO2, N2, O2, and Ar as well as characterization to determine adsorption trends in the materials. Some major conclusions for silica aerogels were that common surface modifications to make the material more resilient against water adsorption impacts the adsorption of CO2 significantly with roughly 4 fold difference in adsorption capacity. For carbon aerogels some major conclusions were that the adsorption was increasingly dominated by the heterogeneous nature of the surface at lower pressures and increasingly dominated by the pore size at the higher pressures. Both chapters discuss the adsorption of air along with ideas such as the influence of gas thermal conductivity in the pores with respects to adsorption. L'objectif général de cette thèse est d'évaluer les principes fondamentaux des technologies actuelles de séparation du CO2 à faible concentration et de fournir une méthode alternative utilisant la technologie d’adsorption avec des adsorbants actuels ainsi que d'en découvrir de nouveaux. Deux applications différentes pour l'adsorption du CO2 ont été explorées; la capture directe dans l’air ambient (CAD) et la purification des gaz excimères, ainsi que la recherche d'aérogels comme adsorbant possible pour ces applications. La première application, le CAD du CO2 utilisant des adsorbants, pourrait répondre aux changements climatiques puisque les niveaux de CO2 atmosphérique sont directement corrélés au réchauffement climatique. Dernièrement, le CAD a fait l'objet d'une attention particulière en tant que stratégie de réduction du CO2, par conséquent, deux voies différentes ont été explorées dans cette thèse: 1. Le chapitre 2 étudie la capture et la concentration du CO2 de 0,04% dans l'air à 95% afin de pouvoir l’enfermer dans la terre. Pour ce faire, une sélection d'adsorbant a été effectué en utilisant des mesures gravimétriques à gaz pur sur sept zéolithes de type X disponibles dans le commerce qui ont été déterminés comme ayant un potentiel pour cette séparation. Des expériences révolutionnaires ont ensuite été réalisées avec la zéolite la plus prometteuse en perturbant le lit avec de l'air ambiant comprimé. Dans le processus étudié, un cycle basique à quatre étapes d’adsorption modulée en température et pression (AMTP) a été étudié, comprenant les étapes suivantes: pressurisation, adsorption, purge et désorption. Quatre températures de régénération différentes ont été testées ainsi que quatre vitesses spatiales de gaz différents. Avec cette configuration de cycle, le CO2 était concentré à 95% de 0,04% avec des fractions de capture totales aussi élevées que 81%. Cette étude a mis en évidence des méthodes pour réduire la consommation d'énergie par tonne de CO2 captée dans le système ainsi que le potentiel d'utilisation de zéolithes structurées à base de faujasite à faible rapport Si/Al dans le CAD du CO2 pour la réduction des gaz à effet de serre. 2. Le chapitre 3 approfondit les recherches du chapitre 2 en capturant le CO2 de 0,04% dans l'air et en le concentrant à des niveaux de très haute pureté où le processus sera remboursé par la valeur du CO2 produit. L'objectif de cette partie était d'augmenter la pureté du CO2 le plus possible car plus le CO2 est pur, plus il est précieux. Une enquête approfondie sur l'adsorption de gaz pur de CO2, N2, O2 et Ar sur la zéolite la plus prometteuse du chapitre 2. Les données ont ensuite été ajustées au modèle TD-Toth qui a permis d'évaluer le cycle AMTP et a montré le potentiel de réduire la pression et/ou d'élever la température pendant l'étape de purge afin de produire du CO2 de haute pureté. Pour confirmer cela, le cycle AMTP a été fait par le biais d’une expérience dans un lit fixe où du CO2 de haute pureté a été produit entre une concentration de 99,5% et 99,96% en abaissant la pression de purge. En contrôlant la température de purge, la concentration du produit est passée de 99,8% à 99,95%, mais avec une perte importante de CO2. Cet effet de la désorption de N2, O2 et Ar pendant l'étape de purge avec la désorption du CO2 pendant l'étape d'évacuation est illustré graphiquement en mesurant la concentration et le débit des espèces de gaz sortant. Les résultats de cette étude montrent le potentiel de production d'un produit précieux de CO2 de haute pureté à partir des concentrations atmosphériques. La deuxième application de cette thèse qui est explorée au Chapitre 4 est la purification des traces d'impuretés de CO2, CF4, COF2 et O2 de F2, Kr et Ne pour des applications dans les lasers à excimère. En raison de l'incompatibilité de nombreux adsorbants avec le F2 et le HF, les alumines et les adsorbants polymères ont été sélectionnés comme matériaux potentiellement compatibles. Pour augmenter la compatibilité de ces adsorbants, l'utilisation d'un cryoréfrigérant a été jugée possible pour pré-refroidir le flux d'alimentation avant la séparation, ce qui augmente la capacité d'adsorption et la compatibilité du matériau en F2 et HF. Pour déterminer le potentiel d'adsorption dans la faible concentration de ces adsorbants, la technique de chromatographie pulsée de concentration a été choisie pour déterminer les constantes de la loi de Henry de CO2, CF4 et O2. Ces données ont ensuite été tracées sur le graphique van’t Hoff et extrapolées à des températures plus froides pour déterminer les avantages de l’utilisation d’un cryoréfrigérant. À partir de cette étude, il a été déterminé que HayeSep Q était le meilleur adsorbant polymère avec une adsorption significative de CO2 à des températures inférieures à -50 ° C tout en étant l'adsorbant CF4 le plus performant. L'AA-300 était l'alumine la plus performante de cette étude tout en ayant une adsorption significative de CF4 à des températures inférieures à -135 °C. Cependant, du point de vue de la compatibilité, ces deux matériaux doivent être testés pour déterminer leur robustesse en présence de F2 et de HF à température ambiante et réduite. Les chapitres 5 et 6 explorent les principes fondamentaux de l'adsorption sur les aérogels en prélude à l'utilisation d'aérogels comme adsorbants possibles pour le CAD du CO2. Cette enquête sur les aérogels examine les aérogels de silice et les aérogels de carbone, qui sont tous les deux fabriqués industriellement et explore leur adsorption par rapport à des matériaux similaires tels que le gel de silice et les charbons actifs. Ces deux chapitres utilisent des isothermes d'adsorption déterminés expérimentalement de CO2, N2, O2 et Ar ainsi que la caractérisation pour déterminer les tendances d'adsorption dans les matériaux. Certaines conclusions majeures pour les aérogels de silice étaient que les modifications de surface courantes pour rendre le matériau plus résistant à l'adsorption d'eau ont un impact significatif sur l'adsorption de CO2 avec une différence d'environ 4 fois dans la capacité d'adsorption. Pour les aérogels de carbone, certaines conclusions majeures étaient que l'adsorption était de plus en plus dominée par la nature hétérogène de la surface à des pressions plus faibles et de plus en plus dominée par la taille des pores aux pressions plus élevées. Les deux chapitres discutent de l'adsorption d'air ainsi que des idées telles que l'influence de la conductivité thermique du gaz dans les pores en ce qui concerne l'adsorption.

Made available in DSpace on 2014-12-17T15:01:31Z (GMT). No. of bitstreams: 1 MayaraOL_DISSERT.pdf: 2406797 bytes, checksum: e542f1e52029a933cac4b8af8d311ef3 (MD5) Previous issue date: 2012-12-27 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / This work depicts a study of the adsorption of carbon dioxide on zeolite 13X. The activities were divided into four stages: study batch adsorption capacity of the adsorbent with synthetic CO2 (4%), fixed bed dynamic evaluation with the commercial mixture of gases (4% CO2, 1.11% CO, 1 2% H2, 0.233% CH4, 0.1% C3, 0.0233% C4 argon as inert closing balance), fixed bed dynamic modeling and evaluation of the breakthrough curve of CO2 originated from the pyrolysis of sewage sludge. The sewage sludge and the adsorbent were characterized by analysis TG / DTA, SEM, XRF and BET. Adsorption studies were carried out under the following operating conditions: temperature 40 ?C (for the pyrolysis of the sludge T = 600 ?C), pressures of 0.55 to 5.05 bar (batch process), flow rate of the gaseous mixture between 50 - 72 ml/min and the adsorbent masses of 10, 15 and 20 g (fixed bed process). The time for the adsorption batch was 7 h and on the fixed bed was around 180 min. The results of this study showed that in batch adsorption process step with zeolite 13X is efficient and the mass of adsorbed CO2 increases with the increases pressure, decreases with temperature increases and rises due the increase of activation temperature adsorbent. In the batch process were evaluated the breakthrough curves, which were compared with adsorption isotherms represented by the models of Langmuir, Fre?ndlich and Toth. All models well adjusted to the experimental points, but the Langmuir model was chosen in view of its use in the dynamic model does not have implications for adsorption (indeterminacy and larger number of parameters such as occurred with others) in solving the equation. In the fixed bed dynamic study with the synthetic gas mixture, 20 g of mass adsorbent showed the maximum adsorption percentage 46.7% at 40 ?C temperature and 50 mL/min of flow rate. The model was satisfactorily fitted to the three breakthrough curves and the parameters were: axial dispersion coefficient (0.0165 dm2/min), effective diffusivity inside the particle (dm2/min 0.0884) and external transfer coefficient mass (0.45 dm/min). The breakthrough curve for CO2 in the process of pyrolysis of the sludge showed a fast saturation with traces of aerosols presents in the gas phase into the fixed bed under the reaction process / O presente trabalho retrata um estudo da adsor??o de di?xido de carbono em ze?lita comercial do tipo 13X. As atividades desenvolvidas foram divididas em quatro etapas: estudo em batelada da capacidade de adsor??o do adsorvente com o CO2 sint?tico (4%), avalia??o din?mica em leito fixo com a mistura sint?tica de gases (4% CO2, 1,11% CO, 1,2% H2, 0,233% CH4, 0,1% C3, 0,0233% C4 e arg?nio como inerte fechando o balan?o), modelagem din?mica em leito fixo e avalia??o em leito fixo da curva de ruptura do CO2 com o g?s de pir?lise do lodo de esgoto. O lodo e o adsorvente foram caraterizados por an?lises TG/DTA, MEV, FRX e BET. Os estudos de adsor??o foram realizados nas seguintes condi??es operat?rias: temperatura de 40 ?C (para a pir?lise do lodo T = 600 ?C), press?o de 0,55 5,05 bar (processo batelada), vaz?o da mistura gasosa entre 50 72 mL/min e massa de adsorvente igual a 10, 15 e 20 g (processo em leito fixo). O tempo do processo de adsor??o em batelada foi de 7h e em leito fixo foi em torno de 180 min. Os resultados obtidos nesta etapa mostraram que no estudo batelada o processo de adsor??o com a ze?lita 13X ? eficiente e que a massa adsorvida do CO2 aumenta com o crescimento da press?o, diminui com o aumento da temperatura e se eleva com a temperatura de ativa??o do adsorvente. No processo din?mico foram avaliadas as curvas de rupturas, as quais foram comparadas ?s isotermas de adsor??o representadas pelos modelos de Langmuir, Fre?ndlich e Toth. Todos os modelos se ajustaram bem aos pontos experimentais, por?m o modelo de Langmuir foi o escolhido tendo em vista sua utiliza??o no modelo din?mico de adsor??o n?o apresentar implica??es (indetermina??o e maior n?mero de par?metros como ocorreu com os demais) na resolu??o da equa??o. No estudo din?mico em leito fixo com a mistura de gases sint?ticos e diferentes massas de adsorvente, a massa de 20 g apresentou maior percentual de adsor??o 46,7% na temperatura de 40 oC e vaz?o da mistura gasosa de 50 mL/min. O modelo se ajustou satisfatoriamente para as tr?s curvas de ruptura e os par?metros avaliados foram: coeficiente de dispers?o axial (0,0165 dm2/min), difusividade efetiva no interior da part?cula (0,0884 dm2/min) e coeficiente externo de transfer?ncia de massa (0,45 dm/min). A curva de ruptura para o CO2 constru?da no processo de pir?lise do lodo mostrou uma r?pida satura??o do leito proveniente de tra?os de aeross?is, presentes na fase gasosa, decorrentes do processo reacional

Les systèmes de stockage de chaleur par sorption (SSCS) ouvrent de nouvelles perspectives dans l'exploitation de l'énergie solaire pour le chauffage des bâtiments résidentiels. En effet, ces systèmes sont très prometteurs dans la mesure où ils permettent un stockage de chaleur sur de longues périodes (le stockage est réalisé sous forme de potentiel chimique) et offrent des densités énergétiques importantes (jusqu'à 230 kWh/m3 de matériau en moyenne) en comparaison aux systèmes classiques comme le stockage par chaleur sensible (qui, pour le cas de l'eau, dispose d'une densité énergétique moyenne d'environ 81 kWh/m3 de matériau pour une variation de 70°C) et le stockage par chaleur latente (qui atteint des densités énergétiques de 90 kWh/m3 de matériau).La présente thèse vise à étudier les performances d'un système de stockage de chaleur par sorption à base de zéolithe 13X intégré à un bâtiment type basse consommation. Des modèles mathématiques de transferts couplés de masse et de chaleur des différents composants du système sont développés et validés par le biais de l'expérimentation. La simulation numérique dynamique, comme outil de dimensionnement, permet, à partir des résultats d'analyses de sensibilité paramétrique sur les différents composants du système, l'étude de son fonctionnement et les critères de sa faisabilité. / Sorption heat storage systems (SHSS) open new perspectives for solar heating of residential buildings. These systems allow long term heat storage (storage is done in the form of chemical potential) and offer high energy densities (up to 230 kWh/m3 of material on average) compared to conventional heat storage systems such as sensible heat storage (which, for the case of water, has an average energy density of approximately 81 kWh/m3 of material for a temperature change of 70 °C) and latent heat storage (nearly reaching energy densities of 90 kWh/m3 of material on average).This thesis aims to study the performance of a sorption solar heat storage system on zeolite 13X, integrated to low-energy building. Mathematical models of coupled heat and mass transfer of various components of the system are developed and validated through experimentation. Numerical dynamic simulations allow to study the functioning of the SHSS in specific conditions, and its design with the results from the parametric sensitivity analysis on its components.

Les sources d’énergies renouvelables représentent un gisement intéressant mais l’intermittence de leur production impose une meilleure anticipation des besoins et la mise en place d’un système de stockage d’énergie. Le stockage thermochimique par adsorption dans un système intégrant le couple zéolithe 13X/eau semble être une solution adaptée à un stockage de l’énergie à basse température pour une application aux bâtiments. Notre objectif consiste à reproduire le comportement de ce type de problèmes thermiques non-linéaires. En effet, une simulation précise et rapide du comportement du système sélectionné permettrait une régulation lors de son utilisation. Un modèle bidimensionnel de stockage d’énergie dans un adsorbeur cylindrique a été développé. La résolution numérique de ce modèle, dit d’ordre élevé, implique l’intégration d’un système de quelques centaines à quelques milliers d’équations fortement non-linéaires et couplés. Les coûts de calculs générés pouvant être prohibitifs, l’application d’une méthode de réduction a ainsi été envisagée afin de conserver les caractéristiques, le couplage des transferts de chaleur et de masse ainsi que les non-linéarités de ce modèle tout en limitant le temps de calculs. La projection de Galerkin des équations de ce dernier sur la base, obtenue grâce à une décomposition orthogonale aux valeurs propres, permet de construire un système dynamique d’ordre faible. Sa résolution est moins coûteuse que celle du modèle d’ordre élevé et reproduit correctement la dynamique de l’adsorbeur. / Renewable energy sources will play a key role in meeting future energy demand. One major criticism of those sources stands in their intermittency requiring both a more effective management of demand and efficient storage systems. We focus on thermo-chemical storage by adsorption-desorption mechanism. Eco friendly, economically viable and suitable with solar energy temperature range made the zeolite 13X - water pair ideal for buildings applications. We built an energy storage model in a cylindrical adsorber which contains the mentioned zeolite13X - water pair. Energy storage has been modeled to present coupled heat and mass transfers thanks to a bi-dimensional model. The numerical simulations lead to the time-space evolution of the heating fluid and adsorbent temperatures and pressure. These knowledge models include typically a great amount of coupled differential equations to solve and strong non linearities. The originality of this study is to build a knowledge model of coupled heat and mass transfer in an adsorber and use the Proper Orthogonal Decomposition (POD) and Galerkin projection to build a minimal model of lower dimension without significant loose of accuracy.