<p>This licentiate study was initiated by copper, zinc and galvanized steel producers in Europe, who felt a need to assess runoff rates of copper and zinc from the pure metals and commercial products at marine exposure conditions. Their motive was the increasing concern in various European countries and the on-going risk assessments of copper and zinc within the European commission. Also the circumstance that available runoff rates so far, had been reported for mainly urban exposure conditions, rather than marine. A collaboration was therefore established with the French Corrosion Institute, which runs a marine test site in Brest, and a set of vital questions were formulated. Their answers are the essence of this licentiate study.</p><p>Based on the ISO corrosivity classification and one-year exposures, the marine atmosphere of Brest is fairly corrosive for zinc (class C3) and highly corrosive for copper (C4). Despite higher corrosivity classifications for both metals in Brest compared to the urban site of Stockholm, used as a reference site, nearly all runoff rates assessed for copper, zinc and their commercial products were lower in Brest compared to Stockholm. This was attributed to a higher surface wetting in Brest and concomitant higher removal rate of deposited chloride and sulphate species from the marine-exposed surfaces. The comparison shows that measured corrosion rates cannot be used to predict runoff rates, since different physicochemical processes govern corrosion and runoff respectively.</p><p>For copper, the runoff rate in Brest was approximately 1.1 g m^-2 yr^-1 with cuprite (Cu2O) as main patina constituent. During periods of very high chloride and sulphate deposition, paratacamite (Cu₂Cl(OH)₃) formed which increased the runoff rate to 1.5 g m^-2 yr^-1. For zinc, with hydrozincite (Zn₅(CO₃)2(OH)₆) as the main patina constituent, the runoff rate was relatively stable at 2.6 g m^-2 yr^-1 throughout the year, despite episodes of heavy chloride and sulphate deposition.</p><p>The application of organic coatings of varying thickness on artificially patinated copper or on different zinc-based products resulted in improved barrier properties and reduced runoff rates that seem highly dependent on thickness. The thickest organic coating (150 µm thick), applied on hot dipped galvanized steel, reduced the runoff rate by a factor of 100. No deterioration of organic coatings was observed during the one-year exposures. Alloying zinc-based products with aluminium resulted in surface areas enriched in aluminium and concomitant reduced zinc runoff rates.</p><p>The release rate and bioavailability of copper from different anti-fouling paints into artificial seawater was also investigated. It turned out that the release rate not only depends on the copper concentration in the paint, but also on paint matrix properties and other released metal constituents detected. Far from all copper was bioavailabe at the immediate release situation. In all, the results suggest the importance of assessing the ecotoxic response of anti-fouling paints not only by regarding the copper release, but rather through an integrated effect of all matrix constituents.</p>

Ceramic membrane processes are a rapidly emerging technology for water treatment, yet virtually no information on the performance and fouling mechanisms is available to the industry. Ceramic microfiltration of model feed solutions and a synthetic river water was examined, and a systematic comparison with polymeric counterpart was performed. The results suggested that the models which have been applied to polymeric membranes agreed well with the ceramic membrane filtration data. The fouling was characterized by the initial pore blocking mechanism and transition to the cake filtration mechanism at a later phase. Cake resistance was dominant and readily removable by physical cleaning. The effects of solution chemistry including ionic strength, divalent ion concentration and pH on the flux behavior were comparatively evaluated for ceramic and polymeric ultrafiltration of synthetic water containing model natural organic matter. Experimental evaluations further included resistance-in-series model analysis, organic matter fouling visualization using quantum dots, batch adsorption test, and contact angle measurement, and provided a quantitative a quantitative comparison of fouling characteristics between ceramic and polymeric membranes. The results collectively suggested that the effects of solution chemistry on the fouling behavior with ceramic membranes were mostly similar with polymeric membranes in terms of trends, while the extents varied depending on water quality parameters. Less fouling tendency and better cleaning efficiency were observed with the ceramic membranes, which was a promising finding for ceramic membrane application to surface water treatment. The study further examined a coagulation-ceramic membrane process as a robust option for surface water treatment. The performance of the hybrid system was evaluated using selected surface waters by varying coagulation conditions and types of coagulants. Results suggested that ceramic membranes experienced relatively less fouling and had better cleaning efficiency than polymeric counterpart. The results of this study provide critical information to guide the industry practitioners, consultants, and regulatory agents considering early adoption of this new technology as well as fundamental knowledge upon which further in-depth studies can be built.

No description available.

Modification of the surface chemistry of materials used as implants in biomedical applications affords the ability to control cell adhesion, prevent inflammation and enhance integration with the host. Titanium and its alloys are strong and lightweight thereby making them desirable for applications such as hip and knee replacements, dental implants, and cardiac pacemaker implants. However, the lifetime of these implants is often limited by poor incorporation into the surrounding bone which results in loosening and wear. In order to overcome these limitations we have studied the modification of titanium substrates with a self-assembled monolayer that can be used to perform surface-initiated atom transfer radical polymerization (SI-ATRP) of a monomer to afford polymer brushes that effectively prevent the adhesion of cells. In addition, the polymer brushes afford the ability to tether a peptide sequence. Specific peptides containing adhesion sequences have been tethered to the polymer brushes. The resulting surfaces promote cell adhesion and osteoblast differentiation, thereby increasing bone tissue formation around the implant resulting in better incorporation of the implant.

Les procédés de séparation membranaire, utilisés couramment dans de nombreux domaines industriels, comme l’agro-alimentaire, le traitement des eaux ou les biotechnologies, sont de plus en plus mis en œuvre dans le domaine des bioraffineries. L’ultrafiltration tangentielle, par exemple, montre un fort potentiel dans l’étape de séparation des matières premières comme les nanocristaux de cellulose pour les transformer en biomasse. Cependant, l’augmentation de la concentration en particules à la surface de la membrane limite ce procédé, entrainant la formation des phénomènes de polarisation de concentration et de colmatage, réduisant les performances de filtration. Ces travaux de thèse ont pour objectif d’améliorer la compréhension des mécanismes de formation de ces phénomènes. Deux méthodes de caractérisation couvrant les échelles nanométriques à micrométiques ont été mises au point, grâce au développement de cellules de filtration couplant l’ultrafiltration à la diffusion de rayons X aux petits angles d’une part, et à la micro vélocimétrie par images de particules d’autre part. Ces mesures effectuées in-situ lors de la filtration tangentielle de suspensions de nanocristaux de cellulose et d’argile de Laponite, ont permis de caractériser l’organisation structurale et le champ hydrodynamique au sein des couches de polarisation. La corrélation de ces résultats avec les lois de comportement rhéologique des suspensions ont permis d’accéder pour la première fois aux champs de contraintes dans les couches de polarisation de concentration et de colmatage lors du procédé. / Membrane separation processes commonly used in several industrial applications, like bio and agro industries, waste water and clean water treatments, are more and more exploited in biorefinery. As an example, cross-flow ultrafiltration process shows a high potential in separation protocol of raw feed components like cellulose nanocrystals to produce biomass. This process is limited by the increase of particles concentration at the membrane surface, which conducts to phenomena named concentration polarization and fouling, which decrease the filtration performance. The PhD work objective is to bring a better understanding of the mechanisms involved in the formation of these phenomena. Two characterization methods covering length scales from nanometer to micrometer have been developed thanks to new designed tangential ultrafiltration cells allowing to link the ultrafiltration process to small angle X rays scattering and to micro particle image velocimetry. These measurement performed in-situ during ultrafiltration of nanocrystal celluloses and Laponite clay suspensions have allowed characterizing the structural organization and the velocity field within the concentration polarization layers. The correlation of these results with the rheological behavior properties of the suspensions, have permitted to access for the first time to the stress field within the concentration polarization and fouling layer during the tangential ultrafiltration process.

O cultivo de moluscos marinhos tornou-se, nos últimos dez anos, uma importante fonte de renda das comunidades litorâneas de Santa Catarina, no sul do Brasil, sendo este estado o maior produtor nacional de moluscos cultivados e o segundo maior da América do Sul. A vieira Pata-de-Leão (Nodipecten nodosus Linnaeus, 1758) é uma espécie com grande potencial para a aqüicultura, e seu cultivo em escala experimental e piloto vem sendo realizado em Santa Catarina, com excelentes perspectivas. Entretanto, a incidência de organismos epibiontes sobre as valvas das vieiras cultivadas em Santa Catarina, por períodos superiores a quatros meses, pode acarretar problemas no desenvolvimento dos moluscos, uma vez que há interferência no crescimento em altura da N. nodosus (RUPP, 2007). O presente trabalho teve como objetivos registrar a ocorrência dos principais organismos que compõem o fouling da vieira N. nodosus e se este assentamento acarreta efeitos negativos no seu desenvolvimento; identificar e descrever as espécies de esponjas presentes no fouling e avaliar de forma preliminar a capacidade de colonização das espécies de esponjas através da competição por espaço com outros organismos da epifauna. As coletas foram realizadas no cultivo de vieiras N. nodosus, situado no estado de Santa Catarina, município de Bombinhas, praia do Canto Grande (27o13’S/48o30’W), nos meses de junho de 2006 a julho de 2007. Foi detectada a presença de 31 espécies pertencentes a sete grandes grupos de organismos epibiontes. Dessas, apenas dez espécies representaram mais de 98% da abundância total. Apesar de haver aumento da riqueza de espécies, diferenças na abundância e na diversidade ao longo das coletas, não houve evidências concretas de processos sucessionais. Após 467 dias sem limpeza, as vieiras do cultivo de Canto Grande não apresentaram efeitos negativos pela presença do fouling. Foram registradas oito espécies de esponjas, sendo Arenosclera brasiliensis a mais abundante, e Prosuberites sp. a espécie que apresentou a maior área de cobertura das valvas das vieiras. Entretanto, nenhuma espécie foi dominante na comunidade de epibiontes, não evitando a presença de outros organismos incrustantes. Foram identificadas pela primeira vez, esponjas associadas às vieiras de cultivo, descrevendose oito espécies: Arenosclera brasiliensis Muricy & Ribeiro 1999, Tedania ignis (Duhassaing & Micheloti, 1864), Lissodendoryx (Lissodendoryx) isodictyalis (Carter 1882), Hymeniacidon heliophila Parker 1910, Mycale (Carmia) microsigmatosa Arndt 1927, Halichondria (Halichondria) sp., Mycale (Carmia) sp. e Prosuberites sp. Ampliam-se os limites meridionais de A. brasiliensis e L. isodictyalis. Mycale sp. e Prosuberites sp. são possíveis espécies novas para a ciência. / The cultivation of marine mollusks became, in the last ten years, a major source of income to the coastal communities of Santa Catarina in southern Brazil. This state is the greatest domestic producer of shellfish cultivation and the second largest in South America. The scallop Pata-de-Leon (Nodipecten nodosus Linnaeus, 1758) is a species with great potential for aquaculture, and its cultivation in experimental and pilot scale is being held in Santa Catarina, with excellent prospects. However, the incidence of epibionts on the valves of scallops can cause problems in the development of bivalves. This study aimed to identify the occurrence of the main organisms that make up the fouling of the scallop N. nodosus and whether this settlement would impose negative effects on their development; to record and describe the occurrence of eight species of marine sponges associated with cultured scallops and evaluate on a preliminary form the ability of colonization of sponges species by the space competition with others epifaunal organisms. The samples were collected in the cultivation of scallops N. nodosus, located in the state of Santa Catarina, municipality of Bombinhas, the beach Canto Grande (27°13'S / 48°30'W), in the months of June 2006 to July 2007. It detected the presence of 31 species belonging to seven major groups of organisms epibionts. Of these, only ten species represented more than 98% of the total abundance. Although there was an increase in species richness, differences in the abundance and diversity throughout the study period, there was no concrete evidence of successional processes. After 467 days without cleaning, the scallops of the culture of Canto Grande showed no negative effects by the presence of fouling. Eight sponge species have been recorded being the most abundant Arenosclera brasiliensis, and Prosuberites sp. the species that showed the largest area of coverage valve of the scallops. However, no species was dominant in the community of epibionts, not avoiding the presence of other organisms incrustants. All sponge species have been described: Arenosclera brasiliensis Muricy & Ribeiro 1999, Tedania ignis (Duhassaing & Micheloti, 1864), Lissodendoryx (Lissodendoryx) isodictyalis (Carter 1882), Hymeniacidon heliophila Parker 1910, Mycale (Carmia) microsigmatosa Arndt 1927, Mycale (Carmia) sp., Halichondria (Halichondria) sp. e Prosuberites sp. The southern boundaries of A. brasiliensis and L. isodictyaliz were enlarged and the latter is a new record for Brazilian coast. Mycale sp., Halichondria sp. and Prosuberites sp. are possible new species.

Les procédés de réutilisation des eaux usées doivent être robustes, fiables et rentables pour que leur utilisation se démocratise et devienne complémentaire des traitements des eaux de surface. Le couplage d’un procédé biologique et de procédés membranaires représente une solution prometteuse pour répondre à ces challenges. Cette étude se focalise sur l’impact des conditions de fonctionnement du procédé secondaire (en particulier par bioréacteur à membrane BAM) sur le colmatage du procédé tertiaire de nanofiltration (NF) ou d’osmose inverse (OI) ainsi que sur le devenir des micropolluants et microorganismes tout au long de la chaine de traitement. Dans un premier temps, des expériences à court terme de filtration avec différentes membrane NF et d’OI ont été réalisées afin de caractériser les interactions entre effluents secondaires et membranes. Il a ainsi été observé de très fortes rétentions de tous les micropolluants ciblés par la Directive Cadre Européenne. En termes de colmatage, la chute de flux de l’OI, essentiellement liée pour ces essais de courte durée à une augmentation de pression osmotique puis à un dépôt de cristaux minéraux, peut être maîtrisée en contrôlant le pH et la concentration en carbonate et phosphate de l’effluent secondaire. Par ailleurs, des chutes de flux plus importantes sont observées lors des filtrations réalisées avec les membranes de NF qui sont plus sensibles au colmatage irréversible. Dans un second temps, l’optimisation de la filière de traitement des eaux usées urbaines couplant un bioréacteur à membranes à un procédé d’OI a été réalisée à partir d’une unité pilote fonctionnant en continu. La sélection de conditions opératoires adéquates a permis de faire fonctionner le procédé d’OI pendant plus de quatre mois sans qu’aucune maintenance ne soit réalisée. Une faible chute de flux de l’OI, linéaire sur toute la période de filtration, essentiellement dû à l’adsorption de molécules organiques à la surface de la membrane, a été observée. Sur l’ensemble de la période d’essais, la filière BAM/OI permet d’obtenir un abattement optimal en micropolluants présents. Lorsque des micropolluants sont injectés à des concentrations plus élevées (simulation d’une brusque dégradation de la qualité des eaux en entrée de filière) dans le bioréacteur, une chute de l’activité de la biomasse couplée à un relargage de produits microbiens solubles peut être observée. Néanmoins, ces pics de pollution n’ont eu aucun impact sur le colmatage de la membrane du BAM ni sur celle de l’OI. La filière BAM-OI permet donc de garantir un taux de rejet élevé et une productivité d’environ 15 L.h-1.m2 quelles que soient les fluctuations de la composition de l’eau usée urbaine à traiter. / In order to be competitive compare to surface water treatments, wastewater reuse needs robust, reliable and profitable combination of technologies. The combination of bioreactors and membrane processes seems to be a promising solution to these challenges. This study focus on the impact of the operating conditions of the secondary treatment (particularly the membrane bioreactor (MBR)) on the nanofiltration (NF) and reverse osmosis (RO) tertiary treatments as well as the fate of micropollutants and microorganisms along the treatment line. Firstly, short term filtration experiments with various NF and RO membranes were performed in order to characterize the interactions between secondary treatment effluents (STE) and membranes. High retentions of micropollutants listed by the European water framework directive were observed. During these short term experiments, RO flux decline is mainly due to an increase of osmotic pressure and then a precipitation of salts that can be solved by controlling the pH and thus the carbonate and phosphate concentration of the STE. In addition, higher flux declines are observed with NF because of a higher irreversible fouling behavior. Secondly, continuous long term tests were performed on a pilot unit combining a MBR and a RO processes. The appropriate selection of operating conditions allowed treating wastewater during more than four months without any maintenance. A linear low flux decline, mainly due to adsorption of organic molecules at the membrane surface was observed. During this filtration period, the MBR/RO process presented very high micropollutant retentions. When micropollutants are injected at higher concentration (simulation of sudden fluctuation of feed composition) into the MBR, a drop of biomass activity combined with soluble microbial products release can be observed. Nevertheless, these peaks of pollution did not cause any additional fouling of MBR as well as RO membranes. MBR/RO process is then a reliable technology that can guaranty high retention and productivity (around 15 L.h-1.m-2) whatever the fluctuations of the feed composition.

Le colmatage membranaire demeure l’un des verrous majeurs des bioréacteurs à membrane (BAM). Ces travaux visent à apporter une contribution à la compréhension de la dynamique de structuration de dépôts complexes formés lors de la filtration frontale de (bio)fluides et son impact sur les performances de filtration. Pour cela, différents outils permettant la mesure in-situ des propriétés structurelles locales des dépôts ont été utilisés de manière à pouvoir relier ces propriétés aux performances globales de filtration. Les propriétés électrocinétiques des dépôts ont également été étudiées. Deux méthodes, l’une optique et l’autre acoustique, ont été utilisées pour caractériser les propriétés structurelles locales des dépôts (épaisseur, cinétique de croissance). Dans un premier temps, les épaisseurs obtenues par les méthodes optiques et acoustiques ont été comparées. Il a été montré que, dans le cas de dépôts peu poreux, les deux méthodes conduisent aux mêmes épaisseurs de dépôts. Dans le cas de dépôts plus poreux, ces deux méthodes permettent l’obtention de données complémentaires à deux niveaux de profondeur différents au sein du dépôt. L’influence des conditions opératoires sur la structuration de dépôts de particules modèles a ensuite été étudiée. Grâce à la méthode optique il a été montré que, quelles que soient les conditions opératoires, il existe une variation temporelle des propriétés du dépôt. De plus, une répartition non homogène du dépôt à la surface de la membrane peut également exister, favorisée par de faibles répulsions entre particules. Enfin, l’applicabilité des différentes méthodes au cas des biofluides issus de BAM a été évaluée. La structure de dépôts complexes constitués lors de la filtration de ces biofluides a ensuite été étudiée. La compressibilité des dépôts, mise en évidence à l’échelle globale par suivi des performances de filtration, a également été observée à l’échelle locale : l’épaisseur du dépôt décroît avec une augmentation de la PTM. De plus, à l’échelle locale, une variabilité spatiale des propriétés du dépôt a été mise en évidence. Afin de contrôler la compressibilité des dépôts l’impact de l’ajout de particules au sein du biofluide a été évalué / Membrane fouling is one of the major drawbacks of membrane bioreactors. This study is thus a contribution to the understanding of the dynamic structuring of complex deposits build-up during dead-end filtration of complex biofluids. Several tools were used to perform in-situ characterization of cake layer structural properties at local scale and to link them to global filtration performances. The electrokinetics properties of the deposit were also investigated. An optical and an acoustic method were used to measure local cake thickness and growth kinetics. The thicknesses given by the two methods were first compared. It was shown that for compact deposits the two different methods lead to the same thickness of the deposit. For more porous deposits, these two methods allow to obtain complementary data at two different depths of the deposits. The influence of operating conditions on cake layer structuring during filtration of modelled particles was evaluated. Using the optical method it was shown that, whatever the operating conditions, the cake structure is not constant in time. Furthermore, a spatial variability of the cake layer thickness might exist especially in the case of weak particle-particle repulsion. Finally, it has been investigated whether the different methods could be applied or not to the case of biofluid filtration. The structural properties of the complex deposits built up during diluted activated sludge filtration were investigated. Cake compressibility was observed at global scale by a monitoring of process performances and was also observed at local scale: cake thickness decreases as TMP increases. Furthermore, at local scale, a spatial variability of deposit structure was found. Particle addition into the biofluid was assessed in order to mitigate compressibility effects

La filtration membranaire est une technique séparative utilisée fréquemment comme procédé permettant de retenir et d'extraire les microorganismes présents dans un fluide. Le mécanisme de sélectivité classiquement admis dans ce procédé est l'exclusion par la taille. Cependant, nos travaux ont permis de mettre en évidence un transfert de microorganismes à travers la structure poreuse des membranes au cours d'opérations de filtration, alors que les dimensions des cellules vivantes en suspension sont supérieures au diamètre moyen des pores de la membrane, entrainant une diminution du taux de récolte des microorganismes et une contamination de la phase perméat. Les caractéristiques morphologiques et nanomécaniques des cellules bactériennes sélectionnées pour nos travaux ont été observées et les propriétés du matériau membranaire modèle ont été mesurées. Grâce à ces informations, le transfert des bactéries aux premiers instants d'une filtration frontale a pu être évalué et le rôle de différents paramètres opératoires appliqués (type de souche bactérienne, composition physico-chimique de fluide filtré, PTM) a pu être commenté. Ainsi, nos résultats ont permis de préciser les mécanismes de sélectivités appliqués aux bactéries à Gram positif et à Gram négatif qui différent du fait des caractéristiques structurales de la paroi bactérienne (épaisseur et élasticité de la couche de peptidoglycane). Enfin, l'évolution du transfert de cellules vers la phase perméat a également été suivie et la mise en place du dépôt bactérien colmatant à la surface de la membrane a été observée. Le rôle de ce dépôt structuré sur les variations de débit et de transfert a donc pu être mis en évidence pour les trois modèles bactériens sélectionnés. Nos résultats ont permis de définir des conditions critiques (physiques, chimiques et biologiques) pour lesquelles le transfert de cellules bactériennes par déformation est amplifié au cours d'une filtration membranaire frontale. / Membrane filtration is a separation technique commonly used as a method for removing and extracting microorganisms present in a fluid. The selectivity mechanism is size exclusion. However, our work has highlighted transfer of microorganisms through the porous membrane structure during filtration operations, even if the size of the living cell in suspension is greater than the average pore size of the membrane, resulting in lowering of the accumulation rate of the microorganisms and thus contamination of the permeate phase. Morphological and nanomechanical characterization of selected bacteria cells used for our work were performed and the properties of the model membrane were analyzed. With this information, the transfer of bacteria dunring the first moments of the dead-end filtration has been evaluated and the role of operating parameters (type of bacteria strains, physicochemical composition of filtered fluid, TMP) has been studied. Thus, our results have clarified the selectivity mechanisms applied to Gram-positive and Gram-negative bacteria strains because of different structural characteristics of the bacterial cell wall (thickness and elasticity of the peptidoglycan layer). Finally, evolution of cells transfer to the permeate phase has also been followed, and the bacterial deposit clogging the membrane was observed. The role of the structured deposit on the variations in flow and transfer has been demonstrated for the three selected bacterial models. Our results have defined critical conditions (physical, chemical and biological) where the transfer of bacterial cells is amplified by deformation during a frontal membrane filtration.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Trocadores de calor são equipamentos muito utilizados na indústria de processos com o objetivo de modificar a temperatura e/ou o estado físico de correntes materiais. Uma rede de trocadores de calor pode ser definida como um grupo de trocadores de calor interligados, a fim de reduzir as necessidades de energia de um sistema. No entanto, durante a operação de uma rede, a eficiência térmica dos trocadores de calor diminui devido à deposição. Esse efeito promove o aumento dos custos de combustível e das emissões de carbono. Uma alternativa para mitigar este problema baseia-se no estabelecimento de uma programação das limpezas dos trocadores de calor durante a operação de rede. Este tipo de abordagem ocasiona uma situação na qual ocorre um conflito de escolha: a limpeza de um trocador de calor pode recuperar a sua eficiência térmica, mas implica custos adicionais, tais como, mão-de-obra, produtos químicos, etc. Além disso, durante a limpeza, o trocador de calor tem de ser contornado por uma corrente de by-pass, o que aumenta temporariamente o consumo de energia. Neste contexto, o presente trabalho tem como objetivo explorar diferentes técnicas de otimização envolvendo métodos estocásticos e heurísticos. Com este objetivo foi desenvolvido um conjunto de códigos computacionais integrados que envolvem a simulação pseudo-estacionária do comportamento da rede relacionado com incrustações e a otimização da programação das limpezas deste tipo de sistema. A solução do problema indica os períodos de tempo para a limpeza de cada trocador de calor. Na abordagem estocástica empregada, os parâmetros do algoritmo genético, como probabilidade de crossover e probabilidade de mutação, foram calibrados para o presente problema. A abordagem heurística desenvolvida se deu através da sequência do conjunto de movimentos zero, um e dois. De forma alternativa, desenvolveu-se a metodologia heurística recursiva na qual os conjuntos de movimentos um e dois foram empregados recursivamente. Também foi desenvolvida a abordagem híbrida que consistiu em diferentes combinações da metodologia estocástica e heurística. A análise comparativa entre as metodologias empregadas teve como objetivo avaliar a abordagem mais adequada para o presente problema da programação das limpezas em termos de função objetivo e esforço computacional. O desempenho da abordagem proposta foi explorado através de uma série de exemplos, incluindo uma refinaria real brasileira. Os resultados foram promissores, indicando que as técnicas de otimização analisadas neste trabalho podem ser abordagens interessantes para operações que envolvam redes de trocadores de calor. Dentre as abordagens de otimização analisadas, a metodologia heurística desenvolvida no presente trabalho apresentou os melhores resultados se mostrando competitiva frente às abordagens comparadas da literatura / Heat exchangers are devices widely used in many processes with the goal of changing the temperature and/or the physical state of the streams. A heat exchanger network (HEN) can be defined as a group of interconnected heat exchangers in order to reduce the energy requirements of a system and is widely used in process industries. However, during the operation of a HEN, the thermal effectiveness of the heat exchangers decreases due to fouling. This effect brings an increase of the fuel costs and carbon emissions. A possible approach to mitigate this problem is based on the establishment of a heat exchanger cleaning schedule during the refinery operation. This kind of intervention brings a tradeoff: the cleaning of a heat exchanger can restore its thermal effectiveness, but implies in additional costs, such as, manpower, chemicals, etc. Additionally, during the cleaning, the heat exchanger must be bypassed which temporally increases the energy consumption. In this context, the present work aims to explore different optimization techniques involving stochastic and heuristic methods. For this purpose, it was developed a set of integrated computational codes involving a pseudo-stationary simulation of HEN behavior related to fouling and schedule optimization of cleaning this type of system. The solution of the problem indicates for the operating staff the time periods for the cleaning of each heat exchanger in the crude preheat train. In the stochastic approach used, the parameters of the genetic algorithm, as the probability of crossover and mutation, have been calibrated to the present problem. The developed heuristic approach was made through the sequence of motions set of zero, one and two. Alternatively, the methodology developed in which the recursive heuristic move sets one and two were used recursively. The hybrid approach consisting of different combinations of stochastic and heuristic methodology was also developed. A comparative analysis of methodologies aimed at assessing the most appropriate approach to this problem of scheduling the cleaning in terms of computational effort and objective function. The performance of the proposed approach was explored by a series of examples including a real Brazilian refinery. The results were promising, suggesting that the optimization techniques of this work may be interesting approaches to operations involving HENs. Among the analyzed optimization approaches, the heuristic methodology developed in this work showed the best results showing competitive front approaches compared to the literature