L’objectif de ce travail est d’adapter une formulation dispersante mise au point par la société Mäder à la dispersion de carbonate de calcium (CaCO3) dans une résine polyester insaturée (UP). Le carbonate de calcium est utilisé en tant que charge dans les matériaux composites à matrice thermodurcissable et en particulier dans les SMC (Sheet Molding Compound). Le rôle de cette formulation est de diminuer les viscosités de résines UP fortement chargées tout en conservant voire en améliorant les propriétés mécaniques des composites formés par un renforcement de l’interface charge / matrice. Trois grands axes ont été développés au cours de ce travail : - le comportement rhéologique d’un mélange CaCO3/résine UP a été déterminé et la formulation dispersante a été optimisée ; - la nature des interactions entre les différents constituants de la formulation dispersante et la surface du CaCO3 a été mise en évidence ; - de nouveaux polymères permettant une dispersion plus efficace de la charge dans la résine ont été synthétisés. Le mélange CaCO3 / résine UP présente un comportement rhéologique complexe. L’optimisation de la formulation dispersante a permis d’augmenter de plusieurs pourcents le taux de charge tout en conservant des viscosités inférieures à celle autorisée par le procédé industriel. L’étude des interactions des constituants de la formulation avec le carbonate de calcium a permis de déterminer les fonctions les plus réactives et de comprendre leur interaction avec la surface de la charge. La synthèse de nouveaux dispersants a également été effectuée. Ces derniers ont ensuite été testés dans l’application et ont montré une efficacité à disperser le CaCO3 dans la résine UP. / The aim of this study is to adapt a dispersive formulation developed by the Mäder group to the dispersion of calcium carbonate (CaCO3) in an unsaturated polyester resin (UP). The CaCO3 is commonly used as filler in the domain of composites especially for Sheet Molding Compound (SMC). This dispersive formulation is able to decrease the viscosity of UP resin containing a high amount of filler. In addition, the mechanical properties of composites could be increased by reinforcing the filler / matrix interface. Three main ways have been studied: - characterization of the rheological behavior of CaCO3 / polyester blends and optimization of the dispersive formulation ; - determination of the interactions between the dispersive formulation components and the CaCO3 surface ; - synthesis of new polymers in order to improve the CaCO3 dispersion in an organic matrix. A complex rheological behavior has been observed for CaCO3 / polyester blends. The dispersive formulation improvement led to an increasing of the filler percentage by keeping the viscosity under the industrial limit. The most reactive functions with the CaCO3 surface have been identified by studying the interactions between the dispersive formulation components and the CaCO3 surface. New dispersing agents have been synthesized. Their efficiency has been demonstrated for the dispersion of CaCO3 in a UP resin.

Massive sulfide deposits in the Noranda mining camp, northwestern Québec, are mainly associated with extensive footwall alteration defined by intense chloritization and sericitization. However, Fe-carbonate alteration also occurs in proximity to some deposits. To test the exploration significance of carbonate alteration in the camp, two areas of intense carbonate alteration were examined, around the small Delbridge deposit and near the new Pinkos occurrence in the Cyprus Rhyolite. Between 1969 and 1971, the Delbridge deposit produced 370,000 t of ore grading 9.6% Zn, 0.61% Cu, 110 g/t Ag, and 2.1 g/t Au. Recent drilling at the new Pinkos occurrence intersected 2.64 m of massive to semi-massive sulfides grading 8.1% Zn and 18.2 g/t Ag. Alteration mapping has shown that the distribution of Fe-carbonates can be used to identify vertically extensive zones of hydrothermal upflow at both properties. At Delbridge, intense Fe-carbonate alteration in brecciated rhyolite defines a pipe-like upflow zone that extends vertically for up to 300 m within the stratigraphic footwall of the massive sulfides and 100 m into the hanging wall. The location of known massive sulfide mineralization coincides with the intersection of the alteration pipe and a favorable horizon marked by the occurrence of fine-grained volcaniclastic rocks. At Pinkos, a similar zone of Fe-carbonate alteration occurs in outcrops of coherent rhyolite. Fe-carbonate alteration is most intensely developed along polygonal cooling fractures in massive rhyolite and decreases in intensity towards the centers of the columns. Fe-carbonate stringers and locally abundant matrix carbonate occur in fragmental rocks at the stratigraphic top of the coherent rhyolite flows and are most intense at the location of sulfide-bearing outcrops that mark the known mineralized horizon. Whereas Fe-carbonate alteration defines the central part of the hydrothermal upflow zones at both properties, disseminated pyrite occurs at the margins and is widespread outside the main upflow zones. This may indicate that Fe-carbonate in the main upflow zones formed at the expense of earlier disseminated sulfides. Replacement of pyrite by synvolcanic Fe-carbonate alteration at Delbridge and Pinkos can probably be attributed to a relatively high concentration of dissolved CO2, possibly of magmatic origin, in the main-stage ore-forming fluids.

The impact of particle size, size distribution, and particle shape on the rheology of precipitated calcium carbonate (PCC) based coatings was studied. Evaluating the interactions between different particle sizes and shapes leads to a better understanding of the packing fraction of PCC. HIgh packing fraction is desirable because of the positive impact on the fluidity of suspensions. Suspension with higher levels of fluidity can potentially load larger amounts of solids while keeping low viscosities. High solids suspensions are key factors to improve the efficiency of coating processes. To address this issue, PCC of different sizes and shapes where mixed in different ratiosto find mixtures with higher packing fractions that could result in coatings with lower viscosities. When coatings containing 90% of large particles and 10% by weight of small particles of different shape, viscosity decreases by 50% for one combination. The effect is caused by the higher packing fraction achieved. Future research is also described here.

The Pennsylvanian Marble Falls Formation in the Llano Uplift region of the southern Fort Worth Basin (Central Texas) is a Morrowan-Atokan mixed carbonate-siliciclastic unit whose deposition was influenced by icehouse glacioeustatic sea-level fluctuations and foreland basin tectonics. Previous interpretations of the Marble Falls Formation focused on outcrop data at the fringes of the Llano Uplift. This study uses a series of 21 cores to create a facies architectural model, depositional environmental interpretation, and regional sequence stratigraphic framework. On the basis of core data, the study area is interpreted to have been deposited in a ramp setting with a shallower water upper ramp area to the south and a deeper water basin setting to the north. Analysis of cores and thin sections identified 14 inner ramp to basin facies. Dominant facies are: (1) burrowed sponge spicule packstone, (2) algal grain-dominated packstone to grainstone, (3) skeletal foraminiferal wackestone, and (4) argillaceous mudstone to clay shale. Facies stacking patterns were correlated and combined with chemostratigraphic data to improve interpretations of the unit’s depositional history and form an integrated regional model. The Marble Falls section was deposited during Pennsylvanian icehouse times in a part of the Fort Worth Basin with active horst and graben structures developing in response to the Ouachita Orogeny. The resulting depositional cycles reflect high-frequency sea-level fluctuations and are divided into 3 sequences. Sequence 1 represents aggradational ramp deposition truncated by a major glacioeustatic sea-level fall near the Morrowan-Atokan boundary (SB1). This fall shifted accommodation basinward and previously distal areas were sites of carbonate HST in Sequence 2 deposition following a short TST phase. Sequence 3 represents the final phase of carbonate accumulation that was diachronously drowned by Smithwick siliciclastics enhanced by horst and graben faulting. These findings contribute to our understanding of the depositional response to glacioeustatic sea-level changes during the Pennsylvanian and can also form the basis for constructing a sedimentological and facies analog for Morrowan to Atokan shallow- to deepwater carbonates in the Permian Basin and the northern Fort Worth Basin. / text

L'implantation de matériaux pour reconstruction osseuse par des techniques chirurgicales peu invasives nécessite des substituts osseux synthétiques, résorbables, injectables et radioopaques. C'est pourquoi le contrôle des propriétés de ces matériaux est primordial. Dans ce contexte, ce travail s'intéresse à la formulation de deux ciments, l'un uniquement à base de carbonate de calcium, le second composé d'un mélange de carbonate de calcium et de phosphate de calcium en quantités égales. Le traitement des phases solides pulvérulentes de ces deux ciments par les procédés de broyage et de co-broyage a été étudié. Ces procédés permettent entre autres de diminuer la taille moyenne des particules. Un mélange intime et homogène entre les constituants de la phase solide est obtenu grâce au co-broyage et les propriétés des ciments sont très significativement améliorées. Le temps de prise est diminué et l'injectabilité de la pâte est fortement augmentée (facteur 100). Cette dernière propriété a pu être évaluée grâce à la mise au point d'un dispositif et d'un protocole de mesure adaptés à un analyseur de texture. Dans le but de visualiser par radiographie aux rayons X l'introduction du ciment injectable dans le site osseux à réparer, du strontium a été introduit en tant qu'agent de contraste radio-opacifiant. Deux voies d'ajout à la formulation du ciment ont été étudiées : la première sous forme de SrCO3 dans la phase solide, la seconde sous forme de SrCl2 dans la phase liquide. Les études réalisées montrent que le co-broyage de la phase solide contenant du SrCO3 est intéressant pour homogénéiser la dispersion de l'agent de contraste et ainsi optimiser la quantité de strontium à incorporer pour atteindre le niveau de radio-opacité requis par la norme en vigueur. De plus, il a été observé que l'ajout de SrCl2 dans la phase liquide rend la pâte plus visqueuse et diminue son injectabilité. Par ailleurs, l'étude de la dissolution de ces ciments à pH physiologique a révélé une libération lente et prolongée du strontium. Enfin, des tests cellulaires in-vitro ont été réalisés sur ces ciments ; ils mettent en évidence l'excellent comportement de cellules ostéoprogénitrices vis-à-vis de ces formulations de ciment ainsi que l'intérêt d'utiliser le sel de SrCO3 plutôt que de SrCl2. La dernière partie de ce travail concerne l'étude de la cristallisation de l'aragonite, variété polymorphe du carbonate de calcium, en présence d'ions phosphate, connus pour inhiber la cristallisation du CaCO3. Grâce à une modélisation à l'aide de la technique de croissance cristalline à composition constante permettant de se placer dans des conditions proches de celles de la prise du ciment uniquement à base de carbonate de calcium in-vivo, il a été montré que la présence d'ions phosphate, même en très faible quantité (concentration < 0,5 µM) diminue à la fois la vitesse de germination et la vitesse de croissance cristalline de l'aragonite. L'ensemble de ces travaux contribue à l'optimisation des propriétés de ces ciments biomédicaux et à mieux appréhender leur comportement que ce soit au moment de leur implantation in-vivo ou de leur évolution et suivi post-opératoires. D'un point de vue fondamental, ces travaux pluridisciplinaires menés dans des conditions modèles in-vitro mais également dans le cadre d'une expérimentation in-vivo ont mis en évidence l'intérêt de confronter ces deux approches pour identifier et comprendre les phénomènes et les réactions impliqués lors de la prise des ciments à base de carbonate de calcium in-vitro et in-vivo. / Implantation of bone substitute materials using minimally invasive surgical techniques requires specific properties for the material including resorbability, injectability and adequate radio-opacity. The control of such properties of the material is of prime importance to meet a surgeon's requirements. In this context, this study deals with two different mineral cements: the first one is only composed of calcium carbonate phases and the second one is a mixture of equal amount of calcium phosphate and calcium carbonate phases. An original methodology involving complementary analytical techniques was implemented to thoroughly investigate the grinding mechanism of separated or mixed reactive powders constituting the solid phase and its effects on cement reactivity and properties. We show that co-grinding the solid phase decreases the mean size of the particles and favours both a homogeneous mixing and good contact between the components, leading to a decrease in the setting time. We also set two original protocols designed to evaluate paste injectability and phase separation during paste extrusion. Co-grinding leads to synergistic positive effects on cement injectability and radio-opacity. It allows maintaining a low and constant load during the extrusion of paste, which composition remains constant. Moreover, the cement's mechanical properties can be enhanced by lowering the L/S ratio because of the lower plastic limit. To be able to follow in situ the injection of the bone cement using X-ray radiography, strontium has been introduced as a contrast agent in the cement composition. Two different routes have been investigated: SrCO3 has been added to the solid phase or SrCl2 has been dissolved in the liquid phase. We show that co-grinding process permits to homogenise strontium distribution in the cement allowing us to optimise the minimum amount of strontium to add into the cement paste to reach the radio-opacity required by ISO 9917-1 standard. Moreover, adding SrCl2 in the liquid phase makes the cement paste more viscous and diminishes its injectability. Release tests performed on Sr-loaded cements show a sustained release of strontium at 37°C and pH 7.4. Finally, in-vitro cell tests have shown the excellent behaviour of osteoprogenitor cells, especially on cements including SrCO3. The last part of this work deals with the study of the crystallization of aragonite CaCO3 in the presence of phosphate ions, naturally present in biological fluids, to better understand the setting ability of calcium carbonate cements in-vivo. Using the constant composition crystal growth technique, we show that the presence of phosphate ions, even in very low amount (concentration < 0.5 µM) diminishes both the nucleation and the crystal growth rates of aragonite. This work contributes to the optimization of the properties of calcium carbonate-based cements and a better understanding and control of their behaviours during implantation and their evolution in-vivo. From a fundamental point of view, this multidisciplinary work performed in model conditions in-vitro and completed by preliminary in-vivo experiments have underlined the interest in combining these two approaches to identify and understand the phenomena and the chemical reactions involved during the setting of biomedical cements.

Molten Carbonate Fuel cells are high temperature fuel cells suitable for distributed generation and combined heat and power, and are today being installed on commercial basis in sizes from 100kW to several MW. Novel applications for MCFC which have attracted interest lately are MCFC used for CO2 separation from combustion flue gas, and high temperature electrolysis with reversible fuel cells. In the first application, the intrinsic capability of the MCFC to concentrate CO2 from the cathode to the anode side through the cell reaction is utilized. In the second application, the high operating temperature and relatively simple design of the MCFC is utilized in electrolysis, with the aim to produce a syngas mix which can be further processed into hydrogen of synthetic fuels. In this thesis, the effect on fuel cell performance of operating a small lab-scale molten carbonate fuel cell in conditions which simulate those that would apply if the fuel cell was used for CO2 separation in combustion flue gas was studied. Such operating conditions are characterized especially by a low CO2 concentration at the cathode compared to normal operating conditions. Sulfur contaminants in fuel gas, especially H2S, are known poisoning agents which cause premature degradation of the MCFC. Furthermore, combustion flue gas often contains sulfur dioxide which, if entering the cathode, causes performance degradation by corrosion and by poisoning of the fuel cell. This makes poisoning by sulfur contaminants of great concern for MCFC development. In this thesis, the effect of sulfur contaminants at both anode and cathode on fuel cell degradation was evaluated in both normal and in low CO2 simulated flue gas conditions.      The results suggested that the poisoning effect of SO2 at the cathode is similar to that of H2S at the anode, and that it is possibly due to a transfer of sulfur from cathode to anode. Furthermore, in combination with low CO2 conditions at the cathode, SO2 contaminants cause fuel cell poisoning and electrolyte degradation, causing high internal resistance. By using a small lab-scale MCFC with commercial materials and standard fuel cell operating conditions, the reversible MCFC was demonstrated to be feasible. The electrochemical performance was investigated in both fuel cell (MCFC) and electrolysis cell (MCEC) modes. The separate electrodes were studied in fuel cell and electrolysis modes under different operating conditions. It was shown that the fuel cell exhibited lower polarization in MCEC mode than in MCFC mode, and a high CO2 concentration at the fuel cell anode reduced the polarization in electrolysis mode, which suggested that CO2 is reduced to produce CO or carbonate. / Smältkarbonatbränsleceller (MCFC) är en typ av högtemperaturbränsleceller som är anpassade för kombinerad el- och värmeproduktion i mellan-till stor skala. Idag installeras MCFC på kommersiell basis i storlekar mellan 100kW och flera MW. En ny typ av tillämpning för MCFC som har väckt intresse på senare tid är användandet av MCFC för CO2-avskiljning i kombination med konventionell elproduktion genom förbränning. En annan ny tillämpning är högtemperaturelektrolys genom användandet av reversibla bränsleceller. I det första fallet utnyttjas att CO2 kan koncentreras från katod- till anodsidan, vilket sker genom cellreaktionen för MCFC. I det andra fallet utnyttjas den höga arbetstemperaturen och den relativt enkla cell-designen för att använda reversibla MCFC till elektrolys, med syfte att producera en syngas-blandning som kan förädlas till vätgas eller till syntetiskt bränsle. I denna avhandling studeras effekten på bränslecellens prestanda genom att operera en MCFC i lab-skala med driftförhållanden som simulerar de som förväntas uppkomma om bränslecellen användes för CO2-avskiljning ur rökgaser från förbränning. Dessa driftförhållanden karaktäriseras av låg CO2-koncentration på katodsidan jämfört med normal drift. Svavelföroreningar i bränsle, speciellt H2S, är kända för att orsaka förgiftning av anoden, vilket i sin tur försämrar bränslecellens prestanda. Dessutom innehåller rökgaser ofta SO2, vilket antas orsaka korrosion och förgiftning av katoden. Detta gör effekten av svavelföroreningar till ett prioriterat ämne för utvecklingen av MCFC. I denna avhandling undersöks effekten av svavelföroreningar på både anod- och katodsidan, i normala driftförhållanden och i förhållanden med låg CO2 som simulerar användandet av rökgaser för CO2-avskiljning. Resultaten tyder på att effekten av förgiftning med SO2 på katoden liknar den med H2S på anoden, och att detta kan vara orsakat av en transport av svavel från katod till anod. Vidare, i kombination med låg CO2 koncentration på katoden så orsakar SO2-föroreningar elektrolytdegradering, vilket orsakar hög inre resistans. Genom att använda en liten MCFC i lab-skala med kommersiella material och standardförhållanden för MCFC påvisades att reversibla smältkarbonatbränsleceller kan vara ett lovande koncept. Den elektrokemiska prestandan av både cell och separata elektroder undersöktes både som bränslecell (MCFC)och vid elektrolys (MCEC). Resultaten visade att cellen uppvisade lägre polarisation vid elektrolys än som bränslecell, och att ten hög CO2-koncentration på det som är bränslecellens anodsida gav upphov till en minskad elektrodpolarisation, vilket indikerar att CO2 reduceras för att producera CO eller karbonat. / <p>QC 20141028</p>

Massive sulfide deposits in the Noranda mining camp, northwestern Québec, are mainly associated with extensive footwall alteration defined by intense chloritization and sericitization. However, Fe-carbonate alteration also occurs in proximity to some deposits. To test the exploration significance of carbonate alteration in the camp, two areas of intense carbonate alteration were examined, around the small Delbridge deposit and near the new Pinkos occurrence in the Cyprus Rhyolite. Between 1969 and 1971, the Delbridge deposit produced 370,000 t of ore grading 9.6% Zn, 0.61% Cu, 110 g/t Ag, and 2.1 g/t Au. Recent drilling at the new Pinkos occurrence intersected 2.64 m of massive to semi-massive sulfides grading 8.1% Zn and 18.2 g/t Ag. Alteration mapping has shown that the distribution of Fe-carbonates can be used to identify vertically extensive zones of hydrothermal upflow at both properties. At Delbridge, intense Fe-carbonate alteration in brecciated rhyolite defines a pipe-like upflow zone that extends vertically for up to 300 m within the stratigraphic footwall of the massive sulfides and 100 m into the hanging wall. The location of known massive sulfide mineralization coincides with the intersection of the alteration pipe and a favorable horizon marked by the occurrence of fine-grained volcaniclastic rocks. At Pinkos, a similar zone of Fe-carbonate alteration occurs in outcrops of coherent rhyolite. Fe-carbonate alteration is most intensely developed along polygonal cooling fractures in massive rhyolite and decreases in intensity towards the centers of the columns. Fe-carbonate stringers and locally abundant matrix carbonate occur in fragmental rocks at the stratigraphic top of the coherent rhyolite flows and are most intense at the location of sulfide-bearing outcrops that mark the known mineralized horizon. Whereas Fe-carbonate alteration defines the central part of the hydrothermal upflow zones at both properties, disseminated pyrite occurs at the margins and is widespread outside the main upflow zones. This may indicate that Fe-carbonate in the main upflow zones formed at the expense of earlier disseminated sulfides. Replacement of pyrite by synvolcanic Fe-carbonate alteration at Delbridge and Pinkos can probably be attributed to a relatively high concentration of dissolved CO2, possibly of magmatic origin, in the main-stage ore-forming fluids.

La demande actuelle croissante d’excipients multifonctionnels par les laboratoires pharmaceutiques, amène les fabricants de matières premières à développer de nouveaux matériaux pouvant répondre à ces critères de performance. Parmi les différents procédés disponibles pour de telles productions, les techniques de co-traitement sont les plus sollicitées. Considérant l’évaluation de la fonctionnalité de différents excipients désintégrants, l’objectif de cette thèse a été de développer un tel excipient, original, économiquement intéressant et pouvant être utilisé dans la fabrication de comprimés par compression directe.Dans ce travail, nous nous sommes tout d’abord intéressés à étudier et à comparer la fonctionnalité de différents désintégrants commerciaux, en évaluant notamment l’influence des milieux réactionnels sur cette fonctionnalité.La chitine, deuxième polysaccharide naturel le plus abondant au monde, et présentant des propriétés physico-chimiques et pharmacotechniques pertinentes, a retenu notre intérêt. Un mélange co-processé, de chitine et de carbonate de calcium (CC) a été développée, et sa préparation optimisée afin de pouvoir disposer d’un matériau aux propriétés maîtrisées. Par des études conduites sur simulateur de compression, nous avons pu, d’une part, établir un profil complet de compression du CC, d’autre part, évaluer ses performances en compression directe en le formulant avec des proportions variables de composants actifs pharmaceutiques retenus comme traceurs modèles. Des études de stabilité ont enfin été réalisées, afin de déterminer ses meilleures conditions d’utilisation.Les résultats les plus marquants ont montré que la chitine présente une comprimabilité satisfaisante et des propriétés de désintégration qui ne sont pas influencées par l’environnement physico-chimique de la formulation. L’excipient co-processé CC a révélé des propriétés très intéressantes et notamment, une densité vraie et une coulabilité améliorées, par rapport à la chitine seule. Ses propriétés désintégrantes sont également particulièrement notables (comprises entre 2 et 5 s.). Son comportement en compression est par ailleurs très satisfaisant avec, une comprimabilité, une compressibilité et une compactibilité performantes; il est également à noter, que dans nos conditions de formulations, il n’a pas nécessité l'addition de lubrifiant. Les comprimés élaborés avec les composants actifs modèles ont fourni des profils de compression également performants et des aptitudes à la désintégration très satisfaisantes. Quant aux profils de dissolution pharmaceutique, ils ont révélé que, avec une teneur en CC égale à 30% m/m, la libération des actifs était rapide. Les études de stabilité conduites afin de définir les conditions optimales de conservation, ont montré que des précautions de température et d'humidité doivent être prises pour les produits formulés avec CC.L’excipient CC co-traité développé dans cette Etude présente toutes les caractéristiques d’un excellent excipient multifonctionnel (diluant, désintégrant, liant). Valorisant l’usage d’une matière première de base naturelle et très abondante (la chitine), facile à produire et économiquement rentable, il devrait pouvoir trouver un intérêt dans la formulation et la production de comprimés à dissolution rapide par compression directe. / Nowadays, there is an increasing demand for multifunctional excipients that replaces the need and use of multiple excipients. Pharmaceutical excipients coprocessing techniques represent important methods for new excipients development with enhanced functionalities. The objective of this thesis is to develop a cost-effective multifunctional excipient (filler-disintegrant-binder) used in tablet manufacturing by direct compression.In this thesis, we’ve studied and compared disintegrants functionality for different materials and evaluated the effect of media on their disintegrant’s functionality. In addition, chitin was chosen as a base to develop a multifunctional excipient used in direct compression as it showed a good and promising physicochemical and pharmaceutical properties. Chitin-Calcium carbonate (CC) coprocessed excipient was developed and its production was further optimized to ensure better powder properties and functionality. In addition, CC compression profile was established by studying its compression behavior under different conditions and formulating with active pharmaceutical ingredients to determine how it affects the formulation at different percentages. Finally, stability study was carried out to determine best conditions for the excipient handling.Results showed that chitin has good tabletability and disintegration properties that were not influenced by the physicochemical environment of the formulation. CC showed an enhancement in true density and flowability (that are considered as drawbacks for raw chitin use as an excipient) and fast disintegration (2-5s). The excipient had good tabletability, compressibility, compactibility, and it doesn’t need the use of a lubricant. CC showed a good compression profile at different manufacturing conditions (multiple lubrication levels, compression speeds and dwell times) while maintaining fast disintegration. It causes rapid disintegration and dissolution when formulated with active pharmaceutical ingredients starting from 30% w/w, and its inclusion was reflected positively on tablets strength. Stability studies showed that precautions on temperature and humidity conditions would need to be taken on CC formulated products. The results showed that the excipient serves as an excellent multifunctional excipient (filler, disintegrant, binder) used for fast disintegrating tablets produced by direct compression. It represents a cost-effective product that is efficient and easily produced at pilot plant and upon scale-up.

Le glycérol est un coproduit de la filière des biocarburants obtenu par transestérification destriglycérides. Avec le développement des biocarburants, la production de glycérol est en pleine croissance.La consommation de glycérol comme additif dans les industries cosmétique, pharmaceutique et agroalimentairen’augmentant pas de manière aussi significative, l’excédent doit être valorisé. L’une des voies devalorisation est la synthèse du carbonate de glycérol qui est un intermédiaire intéressant pour la chimie fine.La méthode de synthèse utilisée au sein de l’industrie Novance est la carbonylation du glycérol par l’urée enprocédé discontinu. Cette réaction produit, en plus du carbonate de glycérol, une grande quantitéd’ammoniac gazeux extrait du milieu réactionnel par dépression. L’ampleur de ce dégagement gazeux ainsique son irrégularité au cours du temps représente la limitation de production du procédé discontinu. Le sujetde cette étude est de développer le procédé continu de cette synthèse afin de pallier ce problème. Pourréaliser le suivi de la réaction, des méthodes analytiques ont été développées dans un premier temps. Avecces outils, les connaissances du système discontinu ont été approfondies pour déterminer les critères dechoix du procédé continu. Une unité de désorption réactive a été ensuite conçue pour créer un systèmebiphasique gaz-liquide à contre-courant. Une série d’essais préliminaires a permis le développement duprocédé qui a été optimisé par un plan de Doehlert. / Glycerol is a by-product of biofuels obtained by transesterification of triglycerides. With developmentof biofuel, glycerol production is growing. The use of glycerol in cosmetic, pharmaceutical and food industriesis not increasing in the same way, so the surplus should be preferable to market. One way of development isthe synthesis of glycerol carbonate which is an interesting intermediate for fine chemistry. The synthesisused by Novance is carbonylation of glycerol by urea with a batch process. This reaction produces, as wellas glycerol carbonate, a high quantity of gaseous ammonia extracted from reactive mixture in a vacuum. Thescale of this gaseous emission and its irregularity during synthesis show the limits of production using abatch process. The aim of this study is to develop the continuous process of the synthesis to solve thisproblem. To carry out the monitoring of the reaction, at first, analytical methods were used. With suchmethods, knowledge of the batch process was improved in order to determine the best criteria for acontinuous process. A unit of reactive desorption was then elaborated to create a liquid-gas biphasic systemin a counter-flow configuration. A series of preliminary experiments were performed to develop the processwhich was optimised by a Doehlert plan.

Made available in DSpace on 2014-12-17T14:08:55Z (GMT). No. of bitstreams: 1 AndersonLSL_DISSERT.pdf: 3992478 bytes, checksum: f60081eb3b7bc8ce8a8b75327bfcf669 (MD5) Previous issue date: 2014-02-28 / As rochas carbon?ticas ocupam, numa vis?o global, um expressivo volume da crosta terrestre. De maneira geral, pode-se dizer que essas rochas est?o presentes nas diversas unidades litoestatigr?ficas da Terra. Os reservat?rios carbon?ticos s?o reservas naturalmente fraturadas que exigem uma abordagem diferenciada na modelagem em programas de simula??o num?rica. Os modelos de dupla porosidade s?o descritos por fun??es de tranfer?ncias que modelam o fluxo de ?leo entre matriz e fraturas. Em um reservat?rio carbon?tico naturalmente fraturado o sistema de fraturas ? determinante no escoamento de fluidos dentro da reserva. Os maiores reservat?rios carbon?ticos do mundo est?o situados no Oriente M?dio e na Am?rica do Norte. As maiores reservas de ?leo brasileiras encontradas neste tipo de reservat?rio est?o localizadas nos campos do Pr?-Sal. No Pr?-Sal, um volume significativo de di?xido de carbono ? produzido juntamente com o ?leo. A disponibilidade de um volume considerav?l de di?xido de carbono derivado da produ??o de ?leo no Pr?-Sal favorece a utiliza??o dos processos de EOR (Enhanced Oil Recovery) por inje??o de g?s. O processo de inje??o de di?xido de carbono vem sendo utilizado em uma grande quantidade de projetos pelo mundo. A afinidade existente entre o ?leo e o di?xido de carbono causa uma frente misc?vel entre as duas fases causando inchamento e vaporiza??o do ?leo dentro do reservat?rio. Para o estudo, foi utilizado um modelo base de reservat?rio de dupla-porosidade, desenvolvido pela CMG para o 6? Projeto de Solu??es Comparativas da SPE, que modela sistemas de fraturas e de matriz e a tranfer?ncia de massa fluida entre elas, caracter?sticas de reservat?rios naturalmente fraturados. Foi feita uma an?lise da inje??o de diferentes vaz?es de di?xido de carbono no modelo base e em modelos semelhantes, com aumento e redu??o de 5 e 0.5 pontos nas propriedades de porosidade e permeabilidade da matriz, respectivamente, tendo a produ??o de ?leo como resultado. A inje??o de 25 milh?es de p?s c?bicos por dia de CO2 foi a vaz?o que obteve a melhor fator de recupera??o