Fouling of heat treatment equipment in the dairy processing industry is an expensive and persistent problem. The objective of this work was to develop a better understanding of the mechanisms of dairy fouling in heat exchangers and identify methods to control this build-up. This was part of a larger project investigating the interaction between spore-forming thermophilic bacilli (thermophiles) contamination and fouling deposits on internal surfaces of equipment. Two systems were developed to monitor the onset and build-up of fouling on the internal surfaces of two research heat exchangers. The first used a commercial sensor to measure the local heat flux and the temperature on the hot side of a plate type heat exchanger. The heat transfer coefficient was calculated and normalised with its value at the start of the run to reflect the contribution of fouling deposits to the thermal resistance, thus giving a real-time estimate of the rate of fouling. The second system used an energy balance over a tubular type heat exchanger and measured inlet and outlet temperatures to estimate the overall heat transfer coefficient thus giving a global measurement of fouling over the tubular heat exchanger. In both systems the plot of normalised heat transfer coefficient over time often stayed constant over an induction period, which was followed by a falling period indicative of growth in the fouling layer thickness and/or mass. Each system was validated by comparing the final value of the normalised heat transfer coefficient with direct measurements of fouling made at the end of a run namely: fouling deposit height for the local measurement and fouling deposit mass for the global measurement. The normalised heat transfer coefficient reported by each system correlated well with the corresponding direct measurement of the fouling layer. An important factor identified in this study was the effect of air bubble nucleation on fouling deposits. It was shown that bubbles that formed on the heated surface greatly reduced the length of the induction period to a matter of seconds rather than hours, as found in previous studies of fouling in the absence of surface bubbles. The rate of fouling was also enhanced while the bubbles remained at the surface. The structure of bubble type fouling layers was linked to the behaviour of the bubbles at the heated surface. Visual observations of these bubbles showed evidence of growth, vibration and coalescence during their period of attachment to the heated surface. Deposits from bubble type fouling consisted of all solid components found in the original milk solution, except lactose, in approximately the same ratio. By contrast fouling deposits reported in the literature with systems operating under the traditional protein denaturation mechanism were reported to consist mainly of whey proteins. Bubble induced fouling can be limited in a number of ways, the most effective being to maintain a high operating pressure in the equipment to ensure nucleation does not occur. Experiments conducted in this study showed that a pressure of 130 kPa.g was sufficient to suppress all bubble nucleation at the heated surface at a temperature of 90°C. Another method identified was the use of high linear fluid velocities to entrain any surface bubbles into the processing stream immediately upon nucleation. Linear velocities above 1.0 m/s were shown to achieve this goal in the miniature plate heat exchanger tested. However, this method is only partially successful because the local linear velocity varies with position in heat exchange equipment of complex geometries and can drop below the mainstream average velocity causing surface bubbles to form, especially in recirculation regions behind flow obstacles. A more reliable method, in situations where high operating pressures could not be used, involved conditioning the heated surface with a thin protein layer during the first few minutes of a run. Conditioning the surface resulted in bubble suppression even at high temperatures and low pressures, thus greatly extending the length of the induction period. Trials performed in this study showed that the addition of a proteolytic enzyme produced by psychrotrophic microbes greatly increased fouling. The enzyme destabilised the caseins which could attach directly to the heat exchange surface independently from the bubble fouling mechanism. Thus the quality of the milk is another important factor to consider. However, the addition of enzymes produced by thermophilic bacilli isolated from milk powder plants did not increase fouling. A theory describing the air bubble induced fouling mechanism is presented along with recommendations on how to reduce this fouling contamination in processing equipment.

Lors de ce travail de thèse nous avons étudié le comportement à long terme de différentes membranes échangeuses d'anions et membranes échangeuses de cations utilisées en électrodialyse conventionnelle pour l'industrie agroalimentaire. Certaines de ces membranes sont du type homogène et d'autres du type hétérogène. La méthodologie suivie tout au long de ce travail est basée sur la comparaison de nombreuses propriétés physico-chimiques, structurales et mécaniques d'échantillons neufs et d'autres vieillis dans un module d'électrodialyse industriel (in-situ) ou selon des protocoles que nous avons mis au point en laboratoire (ex-situ).L'étude du vieillissement in-situ des différentes membranes échangeuses d'ions utilisées dans le traitement des acides organiques et dans la déminéralisation du lactosérum nous a permis de confirmer que les membranes échangeuses d'anions sont beaucoup plus sensibles au vieillissement que les membranes échangeuses de cations. Par ailleurs, nous avons démontré que les changements dans les propriétés de transport, et donc dans les performances des membranes, dépendent en grande partie des modifications survenues sur leur microstructure. Nous avons apporté des améliorations au modèle micro-hétérogène pour permettre d'interpréter et de quantifier les conséquences du vieillissement des membranes échangeuses d'ions. L'effet des opérations de nettoyage sur le comportement à long terme des membranes échangeuse d'ions utilisées dans les opérations d'électrodialyse en agroalimentaire a fait l'objet de notre étude ex-situ. Ce vieillissement est effectué par des solutions acides, alcalines ou par cycles alternant les deux solutions, ou également par des solutions oxydantes de type eau de Javel. Nous avons démontré, entre autres, que les cycles de nettoyage acide-base effectués lors des opérations d'électrodialyse en agroalimentaire engendrent d'importantes dégradations sur les membranes échangeuses d'anions et que ce nettoyage est la cause essentielle du vieillissement des membranes échangeuses d'anions homogènes utilisées en électrodialyse pour la déminéralisation du lactosérum. Une confrontation entre les résultats obtenus par les vieillissements ex-situ et in-situ nous permet de confirmer leur similarité. Ainsi, nous pouvons proposer que, sous des conditions opératoires bien choisies, les études ex-situ sont bien adaptées pour la réalisation d'un vieillissement artificiel contrôlé / The long term behavior of anion and cation-exchange membranes used in conventional electrodialysis for food industry applications was investigated. Some of these membranes were homogeneous and some others were heterogeneous. The approach of this thesis is based upon the analysis of several physico-chemical, structural and mechanical properties of new samples and aged ones in electrodialysis stacks (in-situ) or under artificial ageing protocols at laboratory scale (ex-situ).The in-situ investigation of different ion-exchange membranes used in the purification of organic acids and in whey demineralization confirmed that anion-exchange membranes are more prone to degradation than the cation-exchange membranes. It was observed, as well, that changes in the transport properties, and subsequently in the membrane performance, are dependant of the modifications of the membrane microstructure. The microheterogeneous model was improved and applied for the interpretation and quantification of the ageing consequences on ion-exchange membranes. Assessment of the cleaning process effect on the long term behavior of ion-exchange membranes used in electrodialysis for the food industry applications was the objective of the ex-situ investigation. The ageing protocols were performed using acidic or alkaline solutions or by alternating both of them, as well as in oxidant bleach solutions. Among other findings, it was proven that the damage caused by the acid-base cleaning cycles provoked severe degradation to anion-exchange membranes. Furthermore this cleaning process was the main cause of ageing of homogeneous anion-exchange membranes in electrodialysis for whey demineralization. Comparisons between results obtained by in-situ and ex-situ ageing protocols confirmed their similarity. Therefore, it may be considered that under well-chosen operation conditions, ex-situ investigation is a well adapted method for the artificial ageing

La pénurie d'eau est devenue un des problèmes clés à résoudre, et pour y faire face, il est nécessaire de disposer d'unités de traitement de l'eau efficaces. Au cours des dernières décennies la technologie des membranes est devenue l'une des techniques les plus prometteuses pour le traitement de l'eau. Néanmoins, les membranes ont une durée de vie limitée et sont, par ailleurs, sujettes à des phénomènes de colmatage - le dépôt, l'adsorption et l'absorption de particules dans la structure de la membrane -, ce qui réduit leur productivité, et augmente les coûts opérationnels. Une approche pour minimiser ce problème consiste à modifier des membranes hydrophobes, mécaniquement et chimiquement stables, en y greffant des matériaux amphiphiles afin de réduire le colmatage. L'objectif principal de ce travail est de caractériser les propriétés anti-colmatage des membranes de PVDF (Polyvinylidene fluoride) modifiées avec différents types de copolymères PS-PEGMA (Polystyrene - Poly(ethylene glycol) methacrylate), tout d'abord par l'utilisation de techniques classiques, puis, par le développement et / ou l'adaptation de techniques microfluidiques couplés à la microscopie à fluorescence et l'utilisation de la cartographie par microspectroscopie infrarouge à transformée de Fourier (IRTF). La cartographie IRTF a permis de quantifier localement le greffage et de mettre en évidence l'hétérogénéité du greffage sur la membrane. Ces cartes, représentant l'importance du greffage sur la membrane, ont par ailleurs été corrélées au dépôt de protéines sur la surface. Des systèmes microfluidiques ont également été développés pour caractériser sous microscope à fluorescence l'adsorption de protéines fluorescentes sur une membrane en présence d'un débit. Cette étude permet de suivre in situ et en dynamique l'adsorption (lors de cycles de filtration) et la désorption (lors de cycles de rinçage) de protéines sur la membrane. Ces mesures locales ont été mises en regard avec des mesures de permeabilité lors de cycles filtrations/rinçage mettant en évidence un rôle anti-fouling en particulier pour les copolymères tri-blocs ou pour les copolymères à enchaînement aléatoire. / Water scarcity has become one of the key issues to solve, and efficient water treatment is paramount to treat water sources. In recent decades membrane technology has become one of the promising solutions for water treatment. Nevertheless, membranes are prone to fouling phenomena - the deposition, adsorption, and absorption of particles in the membrane structure -, which hinders their life-span and productivity, and raise operative costs. One approach to minimize this issue is to modify the already mechanically and chemically stable hydrophobic membranes with amphiphilic materials. The main aim of this work is to characterise the anti-fouling properties of PVDF (Polyvinylidene fluoride) membranes modified with different types of PS-PEGMA (Polystyrene - Poly(ethylene glycol) methacrylate) copolymers, firstly by using classical techniques, and then, by developing and/or adapting new ones: microfluidic devices coupled with fluorescence microscopy, and the use of Fourier Transform Infrared microspectroscopy (FTIR mapping). FTIR mapping allowed the local detection of the coating layer and showed its heterogeneous distribution on the surface of the membrane. These maps, that represent the importance of the coating on the membrane, were correlated with the deposit of proteins on the surface. Microfluidic systems were also developed to characterise the adsorption of fluorescent proteins on the membrane under a fluorescent microscope in the presence of a flow. This study allowed the in-situ and dynamic follow-up of the adsorption - during filtration cycles - and of the desorption - during rinsing cycles - of the proteins on the membrane. These local measurements were compared against permeability measurements during the filtration/rinsing cycles evidencing the anti-fouling role of the copolymers used for the modification of the membranes, particularly for the triblock and random copolymers.

Malgré une longue histoire de développement, l'hémodialyse (rein artificiel) possède encore quelques limitations, telles que la perte des propriétés initiales de la membrane en cours de traitement à cause du colmatage et la mauvaise élimination des toxines urémiques de taille moyenne. La présente étude fait partie d'un projet européen nommé BioArt dont le but est d'apporter des solutions à ces limites. Dans cet objectif, l'un des partenaires du projet a proposé le développement d'un nouveau concept de membrane double couche au sein de laquelle sont incorporées des particules adsorbantes. Une caractérisation complète de cette nouvelle membrane était alors nécessaire, plus précisément l'impact de la matrice mixte sur l'élimination des toxines urémiques de divers groupes devait être évalué, ainsi que la propension du matériau membranaire à se colmater. Les études des phénomènes de colmatage sont classiquement menées à l'échelle macroscopique (faisceau de fibres creuses) sans analyse à l'échelle d'une fibre isolée. Le but premier de la présente thèse a alors été de proposer un dispositif permettant une étude du colmatage membranaire induit par la protéine à l'échelle microscopique. Un dispositif microfluidique transparent dans lequel la membrane polymère est insérée a été élaboré et mis en œuvre pour la filtration des protéines modèles : l'albumine de sérum bovin (BSA) et l'a-lactalbumine. Grâce au couplage avec la microscopie de fluorescence, différents modes d'adsorption des protéines sur la surface de la membrane ont été observés et liés aux variations des conditions hydrodynamiques à l'intérieur de la puce. Il a été constaté, sous certaines conditions, une différence dans l'accumulation de protéines entre l'entrée, le centre et la sortie du canal tandis que dans d'autres conditions cet effet s'annule. En outre, un phénomène inattendu, l'agrégation de l'a-lactalbumine, a été observé au cours de la filtration. La localisation dans le canal et la forme des agrégats dépendent également des conditions hydrodynamiques et de la pression transmembranaire appliquée. Dans le but d'optimiser la conception de la membrane vis à vis de son aptitude à éliminer des molécules de taille moyenne de la circulation sanguine, un modèle mathématique a été proposé. L'objectif du modèle était, en prenant en compte la présence de particules adsorbantes à l'intérieur de la membrane double couche, de rendre compte de la combinaison des trois mécanismes d'élimination du soluté : la convection, la diffusion et l'adsorption. Le modèle permet de prédire l'influence de divers paramètres tels que la diffusivité de la molécule, l'épaisseur de la membrane, la présence de la convection, la charge en particules adsorbantes, sur l'intensification des flux à travers la membrane. Le modèle semble être un outil utile pouvant être appliqué à l'optimisation de membranes pour l'élimination des toxines. / Despite a long history of development, the hemodialysis procedure (artificial kidney) still possesses some limitations, such as loss of the initial properties of the membrane due to fouling and poor removal of the middle sized uremic toxins. The present study is part of an European project named BioArt the aim of which was to overcome these limitations. In that objective, one of the partners of BioArt project reported on the development of the novel promising concept of double layer membrane with embedded adsorptive particles. A thorough characterization of the new membrane was then necessary, more precisely the extent to which mixed matrix layer can improve the removal of the uremic toxins from various groups needed to be evaluated, as well as the propensity of the membrane material to become fouled. The studies of the fouling phenomena are conventionally performed at the macro scale (bundle of hollow fibers) without insights of what is happening at the scale of an isolated fiber. Therefore, the primary aim of the present Thesis was to transfer the research of the protein-induced membrane fouling from the macro to the micro scale. A novel transparent microfluidics device with the polymeric membrane inside has been developed and applied for the filtration of model proteins: bovine serum albumin (BSA) and a-lactalbumin. Thanks to the coupling of the microchip with the fluorescent microscopy, different patterns of protein deposition on the membrane surface were observed and related to the variations in the hydrodynamic conditions inside the microchip. It was found that at certain conditions one may observe the difference in protein accumulation in the inlet, the middle, and the outlet of the channel while at other conditions this effect vanishes. Additionally, the unexpected phenomena of a-lactalbumin aggregation was observed over the course of filtration. The location and shape of the aggregates were also dependent on the hydrodynamic conditions and the applied transmembrane pressure. Aiming to address the problem of membrane design optimization for the enhancement of the middle molecules elimination from the bloodstream, a mathematical model, which accounts for the presence of adsorptive particles inside the complex double-layer membrane, has been proposed. The objective of the model was to understand the interplay of three solute removal mechanisms: convection, diffusion, and adsorption. The model allows predicting the influence of various parameters such as molecule diffusivity, membrane thickness, the presence of convection, content of adsorptive particles on the flux intensification across the membrane. The developed model seems to be a useful tool, which may be applied to design optimized membranes for the removal of toxins.

Les bioréacteurs à membranes (BRM), combinant l’épuration biologique des eaux usées à une étape de séparation membranaire, ont montré de très bonnes performances en matière d’élimination de la pollution organique et azotée. Cependant, cette technologie présente des surcoûts de fonctionnement liés essentiellement à l’énergie dépensée pour fournir l’aération nécessaire à l’activité biologique mais utilisée aussi pour lutter contre les phénomènes de colmatage membranaire. Afin de réduire ces besoins énergétiques, un BRM dit autotrophe a été mis en place. Il est caractérisé par une alimentation à une charge organique faible, dont plus de 60% est éliminé par un traitement physico-chimique préalable. De ce fait, le BRM autotrophe assure principalement le traitement d’azote, qui peut être affecté par la limitation en carbone organique nécessaire à la réaction de dénitrification. Ce travail a pour objectif d’étudier le comportement d’un tel système et d’identifier les paramètres déterminants. L’étude a été conduite expérimentalement et par modélisation. Deux campagnes expérimentales ont été réalisées en régime permanent à des charges organiques et des âges de boues différents, suivies d’une expérimentation en régime transitoire provoqué par une montée de la charge en azote ammoniacal. Les résultats des campagnes ont montré qu’il est possible de baisser le rapport de DCO/N jusqu’à 4,5 et l’âge des boues à 40j sans pour autant perturber la dénitrification. Ces résultats ont été appuyés par une modélisation dynamique s’appuyant sur un modèle ASM3s-SMP qui a été développé ensuite calibré sur l’ensemble des résultats expérimentaux. L’analyse du phénomène du colmatage de la membrane au cours de l’expérimentation a montré une tendance au colmatage relativement faible par rapport aux BRM opérant dans des conditions usuelles (DCO/N>10). L’effet du nettoyage mécanique induit par l’ajout d’un matériau granulaire dans le module membranaire s’est avéré peu important dans les conditions étudiées. Une modélisation en régime permanent a permis de développer les expressions des grandeurs caractéristiques du fonctionnement du BRM. Après avoir été validées par des simulations conduites en utilisant le logiciel GPS-X®Hydromantis, ces équations ont permis, au moyen d’approches de modélisation différentes (modèle simple, ASM1 et ASM3), de repérer les paramètres opératoires et cinétiques les plus influents et de déterminer par des expressions analytiques le rapport DCO/N minimal requis pour une réaction de dénitrification complète. / Membrane Bioreactors (MBR) as a combination of biological wastewater treatment and a membrane separation step, showed high performances for organic and nitrogen compounds removal. However, this technology has high running costs linked to energy consumption for aeration. The latter has to be provided for the biological activity and for the membrane scouring that reduces membrane fouling phenomena. In order to decrease these expenses, an MBR called autotrophic was set. It is marked by low organic loading rates due to a physicochemical treatment removing more than 60% of the initial organic matter amount. Mainly, the autotrophic MBR is dedicated to nitrogen removal that can be influenced by the shortage of the organic substrate, needed to achieve the denitrification process. The aim of this work is the investigation of the behavior of such system and the identification of most determining parameters. Experimental and modeling studies were carried out. Two steady state experimental campaigns were performed at different organic loading rates and solid retention times. They were followed by an experiment at transient state induced by the nitrogen loading rate rise. Obtained results proved that operation at a COD/N ratio as low as 4.5 did not hamper the denitrification efficiency. Those results were reinforced by a dynamic modeling study based on a model called ASM3s-SMP that was developed and calibrated using the experimental results. Membrane fouling analysis during experimental campaigns showed low fouling propensities compared to MBR operating at more common conditions (COD/N>10). The mechanical cleaning effect due to the addition of a granular material to the membrane module was found insignificant in the case of these operating conditions.A steady state modeling study helped determining mathematical expressions of different variables, yields and rates describing the system operation. After a validation step based on simulations with the use of the GPS-X®Hydromantis software, these expressions associated to different modeling approaches (simple model, ASM1 and ASM3) allowed pointing out the critical operating and kinetic criteria in addition to the minimum COD/N ratio required for a complete denitrification reaction.

Deposição é um fenômeno indesejável que ocorre na superfície dos trocadores de calor ao longo de sua operação, ocasionando redução na efetividade térmica e aumento da resistência ao escoamento nestes equipamentos. Estes efeitos trazem grandes consequências econômicas e ambientais, devido ao aumento dos custos operacionais (energia adicional é requerida), aumento dos custos de projeto (demanda por equipamentos de maior área de troca térmica), limitações hidráulicas (que pode levar a uma diminuição da carga processada) e aumento das emissões (aumento da queima de combustíveis fósseis para suprir a energia adicional requerida). Neste contexto, o presente trabalho tem por objetivo fornecer ferramentas computacionais robustas que apliquem técnicas de otimização para o gerenciamento da deposição em redes de trocadores de calor, visando minimizar os seus efeitos negativos. Estas ferramentas foram desenvolvidas utilizando programação matemática no ambiente computacional GAMS, e três abordagens distintas para a resolução do problema da deposição foram pesquisadas. Uma delas consiste na identificação do conjunto ótimo de trocadores de calor a serem limpos durante uma parada para manutenção da planta, visando restaurar a carga térmica nesses equipamentos através da remoção dos depósitos existentes. Já as duas outras abordagens consistem em otimizar a distribuição das vazões das correntes ao longo de ramais paralelos, uma de forma estacionária e a outra de forma dinâmica, visando maximizar a recuperação de energia ao longo da rede. O desempenho destas três abordagens é ilustrado através de um conjunto de exemplos de redes de trocadores de calor, onde os ganhos reais obtidos com estas ferramentas de otimização desenvolvidas são demonstrados / Fouling is an undesirable phenomenon that occurs over the surface of heat exchangers during its operation, causing reduction of thermal effectiveness and increase of flow resistance along these equipment. These effects bring large economics and environmental consequences, due to the increase of operational costs (additional energy is required), increase of project costs (demand of equipment with larger thermal exchange areas), hydraulic limitations (that can diminish the process throughput) and increase of emissions (increase of fossil fuel firing to supply the additional energy required). In this context, the objective of this work is to provide robust computational tools that apply optimization techniques for fouling management on heat exchanger networks, aiming to reduce its negative effects. These tools were developed using mathematical programming on GAMS software, and three distinct approaches for the resolution of the fouling problem were investigated. One of them consists in the identification of the optimal set of heat exchangers that have to be cleaned during a plant maintenance shutdown, aiming to restore the thermal load in these equipment through the removal of the existent deposits. The other approaches consist in to optimize the distribution of flow rates of the streams along parallel branches, using stationary and dynamic models, in order to maximize the energy recovery in the network. The performance of these three approaches is illustrated through examples of heat exchanger networks, where the real gains obtained with these optimization tools are demonstrated

A pasteurização é um processo térmico para inativar micro-organismos patogênicos e deterioradores em alimentos líquidos. O controle do processo é fundamental para a manutenção da temperatura de pasteurização, de forma que a modelagem dinâmica se torna útil no desenvolvimento, nos testes de controladores e nos procedimentos de operação. O objetivo deste trabalho foi o desenvolvimento e a validação experimental da modelagem dinâmica de um pasteurizador a placas com três seções de troca térmica para estudar sua operação em regime transiente. A modelagem consiste em balanços diferenciais de energia entre canais e placas do trocador, perda de calor para o ambiente do tubo de retenção e conexões e as respectivas condições iniciais e de contorno. Os coeficientes de troca térmica do equipamento foram determinados experimentalmente. Na simulação foram adotados métodos de diferenças finitas e a resolução matemática foi realizada através do software gPROMS. O modelo foi aplicado para representar o comportamento de um pasteurizador a placas de escala laboratorial (Armfield FT43A), operando em duas condições: sem e com a influência da incrustação na seção de aquecimento do trocador. Para a validação do modelo foram realizados ensaios experimentais da partida e de perturbação das vazões de alimentação do processo. Foram inseridos termopares em diversos pontos do equipamento e as temperaturas foram registradas com um sistema de aquisição de dados. Para estudar a influência da incrustação na pasteurização, foram realizados ensaios experimentais com dois tipos de leite para se ter alta e baixa incrustação. As placas do trocador foram pesadas e fotografadas antes e depois dos ensaios de incrustação para avaliar o depósito formado. Foram utilizados modelos genéricos de incrustação para a simulação desse efeito sobre o processo de pasteurização. Através da comparação dos resultados experimentais e simulados foi verificada que a modelagem matemática para a operação transiente do processo de pasteurização analisado foi muito satisfatória. / Pasteurization is a thermal process used to inactivate pathogenic and deteriorative microorganisms in liquid foods. Process control is essential for the temperature maintenance of pasteurization, so that the dynamic model is an important tool in the development, controller tests, and also in the procedure of operation. The aim of this work was the development and experimental validation of the dynamic model of a plate pasteurizer with three sections of heat exchange studying the transient state operation. The model consists of differential equations of thermal energy balance between channels and plates of heat exchanger, heat loss to the environment of the holding tube and connections and their respective initial and boundary conditions. The heat transfer coefficients of plate heat exchanger and tubes were determined experimentally. In the simulation, finite difference methods were adopted and the math solving was performed using the gPROMS software. The model was applied to represent the behavior of a plate pasteurizer in laboratory scale (Armfield FT43A), operating in two conditions: free of fouling and with fouling influence on the heating section of the heat exchanger. Experimental tests of the start-up and of disturbances in flow rates of the process were performed for the model validation. Thermocouples were inserted at various points of the equipment and the temperatures were recorded with a data acquisition system. In order to study the influence of the fouling, experimental tests were performed with two kinds of milk to obtain high and low fouling. Plates of the heat exchanger were weighed and photographed before and after of the fouling tests for evaluate the deposit formed. Generic models of fouling were used to simulate the effect of fouling on the pasteurization process. Through the comparison of experimental and simulated results, it was verified that the mathematical modeling for the transient operation of the pasteurization process was very satisfactory.

Nesse trabalho, foram caracterizadas 238 amostras de Ãgua produzida, oriundos de quatro campos de produÃÃo diferentes, todos provenientes de campos marÃtimos da bacia do CearÃ, denominados campo de produÃÃo A, campo de produÃÃo B, campo de produÃÃo C e campo de produÃÃo D. Foram determinados, os Ãnions (Acetato, Cloreto, Formiato, Sulfato) utilizando-se a cromatografia de Ãons; exceto, para o Ãnion Bicarbonato que foi determinado utilizando-se a titulaÃÃo potenciomÃtrica. E, os cÃtions (BÃrio, CÃlcio, EstrÃncio, Ferro Total, LÃtio, MagnÃsio, PotÃssio, SÃdio) utilizando-se a espectrometria de emissÃo Ãptica com plasma acoplado indutivamente. Para tratamento estatÃstico, utilizou-se como ferramenta, a PCA (anÃlise de componentes principais) e a HCA (anÃlise de agrupamento hierÃrquico). Na avaliaÃÃo da qualidade dos dados, utilizou-se o balanÃo iÃnico. Para visualizaÃÃo dos resultados, utilizou-se o grÃfico boxplot, onde se pode observar que o campo de produÃÃo A, seguido do campo de produÃÃo B, possuem tendÃncia à corrosÃo e à incrustaÃÃo, respectivamente. Como tambÃm, o campo de produÃÃo D que apresentou propensÃo à corrosÃo, mas em menor escala. Vale salientar a necessidade de uma caracterizaÃÃo individual das amostras, para conhecimento dos principais constituintes existentes. Pois, esses constituintes podem acarretar elevados custos na manutenÃÃo do processo produtivo da indÃstria petrolÃfera; devido, a corrosÃo do tipo pite, que promove a modificaÃÃo da aparÃncia e estrutura dos aÃos inoxidÃveis, muito utilizados na indÃstria petrolÃfera; e, as incrustaÃÃes, que tendem a se depositar nas paredes das tubulaÃÃes, que podem causar problemas como perda de pressÃo, diminuiÃÃo do escoamento da produÃÃo e aumento no consumo de energia. / In this study, we characterized 238 samples of water produced from four different production fields, all from offshore fields of the Cearà basin, called The field of production, production field B, C production and field production field D. were determined anions (acetate, chloride, formate, sulfate) using ion chromatography; except for the bicarbonate anion was determined using potentiometric titration. And, cations (Barium, Calcium, Strontium, total iron, lithium, magnesium, potassium, sodium) using the optical emission spectrometry with inductively coupled plasma. For statistical analysis, we used as a tool, the PCA (principal component analysis) and HCA (hierarchical cluster analysis). In evaluating the quality of the data, we used the ionic balance. To visualize the results, we used the box plot graph where one can observe that the production field, followed by the production field B, are prone to corrosion and fouling, respectively. As well, the D production field that showed propensity to corrosion, but on a smaller scale. It is worth stressing the need for individual characterization of the samples, to knowledge of the main existing constituents. For these constituents can incur high costs in maintaining the productive process of the oil industry; due to corrosion pitting type, which promotes change the look and structure of stainless steel, widely used in the oil industry; and incrustations which tend to deposit on the walls of pipes, which may cause problems such as pressure loss, decreased production flow and an increase in power consumption.

Une des solutions alternatives les plus fiables contre la raréfaction des ressources en eau et la dégradation de leur qualité est la réutilisation des eaux usées. Aujourd'hui la technologie membranaire basse et haute pression s'impose comme la technologie de choix pour la production directe et indirecte d'eau potable du fait de la très haute qualité de l'eau produite. Néanmoins, le colmatage des membranes, affectant techniquement et économiquement les filières de traitement, reste aujourd'hui l'un des principaux défis. Les objectifs de cette thèse sont d'améliorer la compréhension du colmatage membranaire dans le recyclage des eaux usées en étudiant le rôle de la qualité de l'effluent secondaire sur le développement du colmatage et l'impact du colmatage sur la qualité de l'eau produite. Afin d'atteindre ces objectifs, une meilleure connaissance de la qualité des effluents secondaires et de leur impact sur les procédés membranaires s'avère indispensable. Les différentes fractions organiques des effluents ont été caractérisées à l'aide de techniques innovantes telles que la spectroscopie de fluorescence à 3 dimensions (EEM) et la chromatographie liquide couplée à une détection carbone (LC-OCD). Une unité à échelle pilote, composée d'ultrafiltration suivie d'une osmose inverse à deux étages, a été mise en place sur deux sites distincts. Plusieurs doses de monochloramine ont été testées (0 à 2 mg/L NH2Cl) afin de donner des recommandations d'optimisation de traitement. / One of the most reliable alternative solutions to water shortage and scarcity in urban areas is potable reuse of what would otherwise be considered "waste" water. The combination of low and high-pressure membrane processes is the favoured technology for direct and indirect potable water recycling due to the very high water quality produced. Despite the fact that membrane technology is well established, membrane fouling remains a major challenge affecting plant operation technically and economically. This thesis aims to contribute to the understanding of membrane fouling in water reuse by investigating the importance of the feed water quality on fouling development and the impact of the fouling on the treated water quality. In order to achieve these objectives, it was important to develop better knowledge of the impact of feed water quality on the membrane process. The organic composition of the effluents was successfully differentiated with the use of advanced analytical tools such as fluorescence excitation emission matrix (EEM) and liquid chromatography-organic carbon detection (LC-OCD). To evaluate water quality impact on membrane fouling, a membrane pilot unit consisting of ultrafiltration and a two stage reverse osmosis train was operated on two different sites. Different monochloramine dosages (0 to 2 mg/L NH2Cl) were applied and their impact on RO membrane performance was studied in order to provide recommendations for plant design.

La microfiltration est un procédé baro-membranaire largement utilisé pour stabiliser et clarifier les jus de fruits ou pour concentrer leur fraction pulpeuse. Toutefois le colmatage membranaire limite la productivité économique du procédé. Même si de nombreuses études ont été menées pour comprendre et limiter le colmatage, aucun véritable outil n'est aujourd'hui disponible pour prévoir la filtrabilité d'un jus de fruits. Le développement de ce type d'outils prévisionnels est pourtant essentiel pour faciliter l'optimisation des conditions de filtration et pour une meilleure maitrise du colmatage membranaire. Dans ce contexte, l'étude a été axée sur l'identification de nouveaux critères de filtrabilité des jus de fruits au travers de la compréhension et de la caractérisation des mécanismes de colmatage qui interviennent.En choisissant le jus d'orange comme modèle, une approche statistique a permis, dans un premier temps, une sélection rapide et pertinente des caractéristiques physico-chimiques des jus de fruits directement corrélées à leur filtrabilité, à savoir la matière sèche totale, l'extrait sec soluble, le pH, la conductivité et la granulométrie. Ensuite, des stratégies expérimentales complémentaires basées sur des filtrations à l'échelle du laboratoire ont été proposées pour identifier les différentes fractions colmatantes en fonction de leur taille ainsi que les mécanismes de colmatage associés. Ces stratégies novatrices ont permis d'étudier le pouvoir colmatant du jus d'orange en prenant en compte toute sa complexité et de proposer par la suite des cartographies de composés colmatants. Ces cartographies s'avèrent particulièrement intéressantes pour anticiper le comportement colmatant des jus de fruits sans avoir recours à des filtrations longues et coûteuses à grande échelle. Les résultats ont montré que le phénomène le plus important qui régit le colmatage membranaire global au cours de la filtration du jus d'orange semble être le colmatage externe par dépôt. Les objectifs de la dernière partie du travail, ont été de considérer plus fortement le caractère complexe et hétérogène des jus de fruits, pouvant les conduire à des changements brutaux de comportement lors de leur filtration. Pour cela des mesures rhéologiques en mode dynamique couplées à une stratégie d'isolement spécifique des différentes fractions colmatantes du jus d'orange ont été menées pour déterminer le comportement viscoélastique de la fraction insoluble du jus d'orange au cours de sa concentration. Les observations ont montré que les énergies des interactions entre les particules insolubles sont des fonctions croissantes de la concentration de la fraction insoluble et dépendent de la taille des particules. De plus, la transition vers un comportement « solide » du jus d'orange semble être favorisée par la présence des fractions particulaire et supra-colloïdale. Ces observations sont cohérentes avec le mécanisme de colmatage prédominant dû à l'accumulation de ces fractions à la surface de la membrane. La confrontation de nouvelles études de filtrabilité à l'échelle du laboratoire avec la performance de la filtration à grande échelle permettra de généraliser les stratégies proposées pour prédire la performance de la filtration de nouveaux jus de fruits. / Microfiltration is a pressure driven process successfully used to clarify and stabilize fruit juices or to concentrate their pulpy fraction. However, membrane fouling remains the critical factor governing the overall economic productivity of this process. Even if, many studies have been made to understand and limit membrane fouling, to date, there stills a lack of predicting tools to evaluate the filterability of fruit juices. However, it is interesting to develop practical and efficient tools for the prediction of fruit juices filterability in order to adapt and optimize filtration conditions to the fouling behavior of the filtered juice. In this respect, this study focused on the identification of new criteria of fruit juices filterability through the comprehension and the characterization of the potential fouling mechanisms.First, orange juice was chosen as test matrix and a statistical approach was used to select simple and relevant physico-chemical characteristics of this juice in relation with its filterability, namely dry matter, TSS, pH, conductivity, and particles size. Later, additional experimental strategies based on filtration tests at lab-scale were developed to identify the relevant size-classes of foulant compounds and related fouling mechanisms. These innovative strategies allowed studying the fouling potential of orange juice with the consideration of its complexity and proposing cartographies of foulant compounds. These cartographies are particularly interesting to anticipate the fouling behavior of fruit juices without any costly filtration operation at large scale. Moreover, results showed that external fouling seems to be the predominant fouling mechanism governing the overall membrane fouling during orange juice filtration. Finally, the aim of the last part of the work was to highlight the role of the complex and heterogeneous nature of fruit juices in their unexpected behavior during their filtration. For this purpose, the viscoelastic behavior of orange juice suspended solids during their concentration was obtained from rheological measurements in dynamic mode coupled with specific isolation of orange juice foulant fractions. Results showed that the energy of the interactions between juice particles increased as the suspended solids concentration increased and depends on the particles size. Furthermore, the solid-like behavior of the juice was enhanced by the presence of supra-colloids and large particles. These observations are in accordance with the predominant fouling mechanism that is due to the accumulation of these fruit fractions on the membrane surface. The confrontation of new filterability studies at laboratory scale with the performance of large-scale filtration will enable to generalize the proposed strategies to predict the performance of filtration of new fruit juices.