Thèse (Ph. D.)--Université Laval, 2004. / Titre de l'écran-titre (visionné le 29 novembre 2004). Bibliogr.

Thesis (Ph.D.)--Ohio University, November, 2004. / Title from PDF t.p. Includes bibliographical references (p. 161-171)

M.Sc. / Dissolved salts, mainly carbonates and sulphates such as those of calcium and magnesium, form hard water, which when heated produces an insoluble precipitate of scale forming crystals. Scale formation affects performance in industry and ouseholds. Besides the problem of energy costs, there are all the additional problems and maintenance costs of scale removal. Traditional methods of combatting scale build-up based on chemical water treatment do exist. These include: the addition of strong acid to remove the bicarbonate ion from the water, the use of chemicals to prevent or retard the formation of hard scale and, other techniques such as ion exchange process. A cost-effective alternative to these methods is Physical Water Treatment (PWT). Many different types of equipment claiming to treat water physically, for scale reduction are commercially available. These include magnetic, electric (high frequency or radio frequency) or electrostatic, catalytic and ultrasonic devices. In this work attempts have been made to unravel the mechanisms involved in PWT. For this it was necessary to develop experimental methods to determine the effect of electromagnetic fields and selected magnetic and radio frequency (rf) water treatment devices on precipitation reactions. The most significant finding of this study involves the effect of Zn on scale formation. When supersaturated Ca(HCO3 )2 solutions were tested in a glass heat exchanger, a 77% reduction in the formation of scale was found when the solutions were spiked with Zn.

M.Sc. / Calcium carbonate scale formation is a major problem in industrial water and cooling systems as well as in household systems. The resulting reduction in heat transfer and the removal of the scale are very costly processes. One of the methods used in the past 50 years and investigated for nearly a century, is the use of physical fields to reduce, remove and / or inhibit scale formation. These physical fields are usually magnetic fields, but RF electric and electrostatic fields are also used. These fields are claimed to reduce the cost involved in the removal of scale to a minimum. To investigate these claimed effects on scale formation, a pure calcium bicarbonate solution was exposed to some of the commercial available units: The exposed solution was then forced to precipitate by elevating the temperature. The pH was monitored against time, to investigate the nucleation process of CaCO 3 and the resulting precipitate analysed for changes in crystal morphology. The principle conclusions made from the results were, firstly that the nucleation of CaCO 3 was significantly delayed in one of the units tested and that the preferred morphology was changed from the thermodynamically more stable calcite to the more unstable aragonite in that unit. Secondly, that a direct correlation existed between the release of trace amounts of metals from the unit and the observed effects.

A incrustação causada pelo coque é um sério problema na indústria do petróleo, principalmente, nos equipamentos que operam em altas temperaturas. Neste trabalho apresenta-se um estudo para demonstrar a possibilidade do emprego da incrustação do coque como um elemento transdutor para compor um sensor tipo resistivo, para fornecer um sinal elétrico representativo do crescimento e do envelhecimento local da própria incrustração. Para a demonstração, procederam-se duas etapas de experimentos com óleos pesados do petróleo e amostras de incrustação de coque originadas por esses óleos na indústria. Os experimentos mostraram bons resultados, mas também indicaram que o sinal combina a condutividade do óleo e o da incrustação. O coque produzido nos experimentos apresentou-se como grânulos soltos não aderentes e eletricamente desconectados entre si. Verificou-se que o sinal obtido durante o craqueamento térmico em regime de batelada apresenta três regiões distintas: no início o material reage com uma cinética de primeira ordem; na região intermediária, ocorre separação do fluído em duas fases líquidas e finalmente, na terceira região, ocorre a deposição do coque sólido, porém imerso em óleo com elevada resistência elétrica, fornecendo um sinal muito mais alto que o valor inicial apresentado pelo óleo. Entretanto, craqueamentos térmicos sucessivos sobre o leito de coque inicial mostrou progressivas reduções nos valores das leituras, indicando a tendência a ser adquirida com o envelhecimento do coque, de se agregar em uma grande estrutura carbonácea de baixa resistividade elétrica. Alternativamente, para confirmar, mediu-se a resistência elétrica em amostras de incrustação verdadeiras usando-se as mesmas condições empregadas nos óleos. Os resultados mostraram uma resistividade aproximadamente 50 vezes menor que a dos óleos. Ensaios de craqueamento sucessivos de óleos sobre estas incrustações mantêm praticamente constante a resistência elétrica obtida como leitura, confirmando que o aumento da condutividade se deve mais ao envelhecimento e cimentação dos grânulos de coque do que o crescimento da incrustação. Os ensaios também mostraram que uma vez que a incrustação adquire uma resistividade elétrica menor que a do óleo, o sinal torna-se mais representativo da incrustação. O sinal então, se associado a um método de ajuste adequado, fornece a velocidade de crescimento da camada incrustada que pode ser usada como parâmetro de controle ao processo industrial para minimizar o problema da incrustação pelo coque. / The coke fouling is a serious problem in the oil industry, mainly in equipment operating at high temperatures. This work presents a study to demonstrate the possibility of using the inlay of the coke as a transducer element to form a resistive sensor type, to provide an electrical signal representative of the growth and aging of the local self inlay. In order to demonstrate this, two categories of experiments have been carried out with two heavy oils fractions and two samples of real fouling coke incrustation originated by these oils in the industry. The experiments show good results, but also indicate that the signal combines both oil and incrustations conductivity. The coke produced during the experiment haad non-adherent loose granules that were electrically disconnected between them. It was verified that the signal obtained during the batch controlled thermal cracking shows three distinct regions: at first, the material reacts within a first-order kinetic rate; at the intermediate region, fluid separation happens in two liquid phases and, finally, at the third region, solid coke deposition occurs, though immersed in a high electric resistivity oil, providing a much higher signal than the initial value presented by the oil. However, sucessive thermal cracking on the initial bed of coke showed progressive reductions in the values of the readings, indicating the tendency to be acquired by the aging of coke, to aggregate in a large structure of carbonaceous material with low electrical resistivity. Alternatively, to confirm, was measured the electrical resistance in samples of real inlay using the same conditions employed in the oils. These have showed a resistivity approximately 50 times smaller than the one for the oils. Testing of sucessive oil cracking on these inlays remain practically constant the electric resistance obtained as reading, confirming that the increase in conductivity is due more to the aging and cementation of grains of coke than the growth of the inlay itself. The tests also showed that once the encrustation acquires a resistivity lower than of the oil, the signal becomes more meaningful and representative of the inlay. The signal, if is associated with an appropriate adjustment method, give the rate of growth of the embedded layer that can be used as a control parameter for the industrial process to minimize the problem of fouling by coke.

Les réacteurs à lit fixe arrosé vers le bas en régime ruisselant se comportent comme des filtres en profondeur quand des liquides contaminés entrent en contact avec le lit. La rétention des solides de petite taille occasionne une augmentation progressive de la perte de charge. Éventuellement, l’opération du réacteur doit être interrompue et le lit colmaté est écarté, même si le matériel catalytique qui le constitue demeure encore actif occasionnant de la sorte des pertes économiques importantes. Cet ouvrage propose des méthodes et des modèles pour la simulation du colmatage du lit fixe avec des écoulements mono et biphasiques. Deux niveaux d’analyse sont présentés. Au niveau du lit complet, le modèle Eulérien-Eulérien, qui est une procédure de la mécanique des fluides numérique (CFD), permet l’inclusion des équations de fermeture pour le transfert de masse et de quantité de mouvement dans le contexte de la filtration en profondeur (deep bed filtration, DBF).. A l’échelle d’un seul élément de garnissage, l’analyse de trajectoire est couramment acceptée pour l’étude du taux de capture de particules dans le cadre de la filtration en profondeur dans le lit fixe. Dans le cas de l’écoulement monophasique, la capture de particules est calculée par l’expression de Rajagolapan & Tien (1976). L’insertion de cette expression dans le code CFD fourni des informations utiles à propos du comportement de la colonne en état transitoire. Dans le cas de l'écoulement biphasique en régime ruisselant, aucune procédure d’analyse de trajectoire n'est connue. En conséquence, une toute nouvelle adaptation de cette méthodologie est proposée. En utilisant un modèle de film pour représenter le réacteur à lit arrosé, l'analyse de TA est accomplie dans les cas suivants; monophasique et biphasique avec déposition monocouche et multicouche. Les tendances de TA concordent avec l'analyse de Rajagopalan et Tien (1976) démontrant que les mécanismes de capture sont du même type que ceux qui se présentent dans l'écoulement monophasique et qu’ils sont modifiés uniquement par la présence de la phase gazeuse. Les résultats ont été comparés aux données expérimentales de Gray et al. (2002). La rétention liquide statique (SLH) est un paramètre qui, selon des observations expérimentales, affecte sensiblement la capture en conditions multiphasiques. Une collection presque exhaustive des données de la SLH a été construite à partir de la littérature expérimentale disponible. Avec ces données de SLH et avec l'utilisation d'un algorithme considérant un minimum d'énergie de ménisque, des angles de contact moyennés pour une gamme de liquides et de garnissages ont été obtenus. En réinsérant les angles de contact calculés dans un logiciel de réseaux neuronaux, une corrélation qui surpasse toutes les corrélations disponibles a été obtenue. À l’avenir, il serait souhaitable que la rétention liquide statique soit incluse dans le modèle de colmatage, ou à tout le moins dans l’analyse des trajectoires. / Trickle bed reactors (TBR) behave as deep bed filtration (DBF) units when the liquid feedstock is contaminated with fine particles. Solid retention causes an ever increasing pressure drop in the bed that leads to eventual halting of the installation. Industry response has been so far to change the plugged, but still active, catalytic bed with a fresh catalyst packing causing important profit losses of the process. In this work two levels of analysis are proposed for the DBF in single and two phase trickle flow conditions. At bed scale, an Eulerian-Eulerian CFD approach is used that provides the framework for the insertion of closure equations for the mass transfer in DBF. At pore scale, Trajectory Analysis (TA) is used as is an accepted procedure for the analysis of Deep Bed Filtration (DBF) in single-phase aqueous systems. In single phase flow through packed beds, the known TA based expression of Rajagolapan and Tien (1976) is used. By inserting this expression in the CFD approach it becomes possible to obtain valuable information about the transient structure and development of plugging. Benchmarking was obtained with the work of Narayan et al. (1997). In two phase trickle flow, no TA approach is known so far and an all new extension of this methodology is proposed in this work. Using a film model to represent the trickle bed reactor, TA analysis is performed in single phase, one-layer and multilayer deposition in TBR conditions. TA tendencies were akin to the analysis of Rajagopalan and Tien (1976) demonstrating that deposition mechanisms are of the same kind as in the single phase flow only modified by the presence of the gas phase. Results were compared with the data of Gray et al. (2002). Static liquid hold-up (SLH) is a parameter that, according to experimental observations, affects significantly solid deposition in multiphase conditions. An almost exhaustive collection of SLH values was constructed from the available experimental literature. With the SLH data and with the use of a minimum energy algorithm, average contact angles for a wide range of liquids and packing were obtained. Reinserting the calculated contact angles in neural network software, a correlation was obtained which outperforms all the available correlations. It is hoped that in future work, this last parameter, the SLH, will be included in the plugging model or at least in the trajectory analysis at the collector scale.

This study shows how the composition of gases released from a single magmatic source may be modified during their ascending path. The main processes that influence the composition of the gases in these high temperature fumarolic environments, are: 1) interactions with wallrocks during gas ascent, which change the fugacities of the metal volatile species and affect the equilibrium between major species (fH2S/fSO2; fH2/fH2O); 2) mixing with meteoric water with consequent Cl adsorption, which may account for the Cl depletion of the gases; 3) remobilisation of previously formed sublimates and/or incrustation deposits. Comparison between the thermochemical models and the mineralogical composition of the silica tubes at Kudryavy and Satsuma-Iwojima volcanoes suggests that high fO2 due to the mixing of the gases with air during their injection into the atmosphere significantly reduces the volatility of several trace elements (As, Sb, Sn, Na, K, Tl, Te, Se and Cd). Comparisons between the enriched metals in aerosols and in the gases suggest that Mo, Pb, Bi, Na, K, Cu, Zn or Fe, which are enriched in the gases, are preferentially deposited in the gas conduits and vents whereas the highly volatile metals (Te, Tl, Sb, As and Se) and Cd condense in the plume. This study determines the reactions that may occur during the alteration of rocks in high temperature fumarolic environments. Three different processes of alteration prevail: (1) Acidic alteration which is characterized by the complete absence of clays, because the constant supply of gases to these systems allows for the pH values of the acidic fluids to be maintained low enough to prevent the precipitation of clay minerals. Complete leaching of all cations, except Si, from the primary silicates leads to important "silicification" of the wall rock. The primary mineral cations are leached in the following order: K, Na > Ca > Fe, Mg > Al > Si, Ti. The fluids enriched in these cations circulate in microcracks at different temperatures and different redox conditions and lead to the precipitation of secondary incrustations. At Kudryavy the incrustations are mainly sulfates. At Usu the lower sulfur/fluoride ratio of the gases allows the occurrence of aluminum fluoride incrustations. The order of primary minerals dissolution (olivine > plagioclase > pyroxene > matrix glass > Fe-Ti oxides) is established for both sites studied. (2) Alteration by an oxidized volcanic gas, resulting from mixing with the atmosphere (500 to 300°C). At Kudryavy, thermochemical modeling suggests that anhydrite and anhydrous sulfates, which occur at intermediate temperatures, are formed by interactions of the rock with oxidized gas. (3) The most important outcome of this work is the identification of the features of alteration by the volcanic gas that directly reacts with the rock at high temperatures (T > 500°C). The Kudryavy rocks show evidences for mineral transformations, which occur in the presence of the volcanic gas phase. Volcanic gas directly reacts with rocks at high temperatures (T > 500°C). The gas destabilizes the primary minerals, remobilizes the rock-bearing cations, and leads to the formation of second mineral assemblages. These transformations occur in situ, without significant mobility (gain or loss) of the cations. The high temperature secondary associations are characterized by the presence of andradite, hedenbergite, hercynite, tridymite/cristobalite. Anhydrite and anhydrous Al sulfate may occur within these mineral assemblages if the gas is oxidized.

Reproduction de : Thèse d'exercice : Chirurgie dentaire : Nantes : 2009. / Bibliogr.

Thesis (Ph.D.)--Ohio University, November, 2006. / Title from PDF t.p. Includes bibliographical references.

La nécessité de valoriser les co-produits laitiers, dans un souci de croissance économique dans ce secteur, a conduit à l'émergence de nouveaux ingrédients. Par exemple, les hydrolysats de protéines lactosériques constituent une source importante de peptides potentiellement bioactifs. Toutefois, l'isolation et la purification de telles molécules semblent nécessaires afin d'améliorer leur bioefficacité. Les peptides peuvent être dessalés par électrodialyse (ED) mais leur colmatage sur les membranes échangeuses d'anions (MEA) et de cations (MEC) diminue l'efficacité du procédé. Dans cette optique, la présente étude a pour objectifs (1) d'identifier, caractériser et quantifier les séquences peptidiques responsables du colmatage des MEA et MEC, (2) de mieux comprendre les mécanismes sous-jacents au colmatage et (3) d'évaluer l'impact des différents régimes de courant en ED quant-à l'éventuelle prévention du colmatage. Dans un premier temps, le colmatage a été généré en condition statiques sans application de courant puis caractérisé. Dans un second temps, les phénomènes de dissociation d'eau et d'électroconvection ont été étudiés afin d’optimiser le procédé in-situ avec courant. Ainsi, en conditions statiques, les MEA chargées positivement (N+(CH3)3), présentaient un colmatage plus élevé à pH 6 et 10 qu’à pH 2. Les analyses HPLC-MS ont révélé que les peptides VLVLDTDYK, TPEVDDEALEK et IDALNENK (chargés négativement à pH 6 et 10) constituaient 86% du colmatage à ces pH alors qu’aucun peptide n’a été détecté à pH 2. Par conséquent, des interactions électrostatiques entre les charges peptidiques (COO-) et les groupements des MEA se sont établies. Concernant les MEC chargées négativement (SO3-), le colmatage était plus important à pH 6 qu'à pH 2 et 10. En outre, les analyses HPLC-MS ont révélé qu'à pH 6, les séquences ALPMHIR et TKIPAVFK chargées positivement (NH3+) ont établit des interactions (1) électrostatiques peptide/MEC créant une première couche puis (2) hydrophobes peptide/peptide via leurs résidus hydrophobes respectifs générant une seconde couche. Néanmoins à pH 2, le colmatage était moindre alors que ces peptides portaient théoriquement davantage de charges positives. Il est possible qu'à pH acide, les charges membranaires des MEC aient été protonnées (HSO3) et donc non chargées contrecarrant ainsi l'établissement d'interactions électrostatiques. Dans la seconde partie avec application de courant, le colmatage respectif des MEA et MEC a été réduit de 62 et 36 % en conditions électroconvectives. Les résultats démontrent que travailler à pH acide ou en régime post-limite permettrait de limiter voire d'éviter totalement le colmatage des membranes augmentant ainsi leur durée de vie et l'efficacité du procédé. Cette thèse propose différents mécanismes de colmatage en fonction de la nature de la MEI et des caractéristiques physico-chimiques des peptides. L'utilisation future de séquences peptidiques modèles, connues et synthétiques permettrait d'améliorer davantage les connaissances de ces mécanismes. / In the dairy industry, the economical growth led to the necessity of creating high added-value products from low commercial value by-products. For example, whey proteins hydrolysates (WPH) are an important source of peptides potentially bioactive. However, bioactive peptides need to be isolated and purified in order to enhance their bioactivities. The WPH demineralization by conventional electrodialysis (ED) may lead to peptide fouling on anion (AEM) and cation-exchange membranes (CEM) and decrease the process efficiency. Therefore, this study aimed (1) to identify, characterize and quantify the peptide sequences responsible for membrane fouling, (2) to better understand the mechanisms involved in peptide fouling and (3) to evaluate the impact of non-conventional ED modes on fouling. In a first phase, peptide fouling was generated and characterized in static conditions and without applying current. In a second phase, fouling was carried-out in real hydrodynamic conditions using ohmic, limiting and overlimiting currents in order to optimize the demineralization process. Results showed that in static conditions for AEMs, fouling was important at pH 6 and 10 and absent at pH 2. Based on HPLC-MS results, the VLVLDTDYK, TPEVDDEALEK and IDALNENK sequences (negatively charged at pH 6 and 10) represented 86% of the total fouling at these pH values whereas no peptide was detected at pH 2. Consequently, electrostatic interactions were established between the negative peptide charges (COO-) and positive AEM charges (N+(CH3)3). Concerning the CEMs, fouling was more important at pH 6 than 2 and 10. At pH 6, ALPMHIR and TKIPAVFK sequences firstly established electrostatic interactions with the negative CEM charges (SO3-) through their positive residues (NH3+) creating a first layer. Secondly, peptide/peptide interactions occurred through their respective hydrophobic residues creating a second layer. Nonetheless at pH 2, fouling was twice lower whereas peptides carried more positive charges. It is possible that for acidic pH values, CEM charges were partially protonated (HSO3) and consequently neutralized and unable to establish electrostatic interactions. Finally during a demineralization step in hydrodynamic conditions, fouling of AEM and CEM was reduced using overlimiting current by 62 and 36 %, respectively. According to these results, working at acidic pH values or using overlimiting conditions would hamper nay avoid fouling on membranes which would increase their lifetime and effectiveness. Different fouling mechanism models depending on the nature of IEM and the physicochemical characteristics of peptides are suggested in this thesis. In the future, the use of synthetic and well-characterized peptide sequences would enable to improve the knowledge of these mechanisms.