Made available in DSpace on 2014-12-17T15:01:48Z (GMT). No. of bitstreams: 1 LedaMOL_TESE.pdf: 3658937 bytes, checksum: 6ad7dbe6b2ec8a6f89d9264905ef89b6 (MD5) Previous issue date: 2009-12-21 / Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1? order / Tecnologias inovadoras que usam materiais tensoativos t?m aplicabilidade em v?rios campos industriais, dentre eles petr?leo e g?s natural. Este estudo busca investigar o uso de um tensoativo, derivado de ?leo de coco (OCS - ?leo de coco saponificado), no processo de recupera??o de compostos org?nicos presentes em efluentes oleosos da ind?stria de petr?leo. Para este fim, foram realizados experimentos em uma coluna de bancada objetivando verificar a influ?ncia do tensoativo OCS na efici?ncia de remo??o de ?leo. Desta forma, foram preparadas emuls?es com quantidades fixas de ?leo (50, 100, 200 e 400 ppm), determinandose a concentra??o ?tima de tensoativo para cada uma delas. Foram, tamb?m, realizados alguns ensaios com ?gua de produ??o da ind?stria de petr?leo, visando comparar o resultado com o das emuls?es. O processo de separa??o consiste no uso de bolhas gasosas formadas quando um fluxo de g?s passa em uma coluna l?quida, com concentra??es de tensoativo, ocorrendo a coalesc?ncia das gotas de ?leo dispersas e, consequentemente, o transporte delas ao topo da coluna, formando uma nova fase oleosa cont?nua. O processo fundamenta-se na satura??o de tensoativo na interface g?s-l?quido, dependendo da concentra??o de tensoativo usada, resultando na flota??o da fase ?leo dispersa. Um filtro de prato poroso, com tamanho de poro que varia de 40 a 250 μm, foi colocado ? base da coluna para permitir uma opera??o hidrodin?mica est?vel. Durante os procedimentos experimentais, o volume operacional da fase l?quida foi mantido constante e a taxa de fluxo de ar variada em cada experimento. Os resultados experimentais do estudo hidrodin?mico demonstraram que a captura do ?leo foi influenciada pelos di?metros das bolhas e vaz?es de ar. Com o aumento da vaz?o de 300 para 900 cm3.min-1, ocorreu um aumento de remo??o da fase ?leo de 44% para 66% e a cin?tica de remo??o do ?leo foi definida como uma rea??o de 1? ordem

Nous présentons dans cette thèse une utilisation de la structure dite de stries huileuses présente lors de la compétition entre deux ancrages antagonistes de part et d’autre d’un film sub-micrométrique de cristal liquide en phase smectique pour réaliser le contrôle à l’échelle individuelle de l’orientation d’émetteurs de photons unique ainsi que de l’auto-organisation ultérieure lorsque la concentration est augmentée. La morphologie interne de cette structure est étudiée à l’aide d’observations en microscopie optique polarisée, d’ellipsométrie et de diffraction de rayons X. L’analyse de ces résultats mène au modèle présenté en fin de chapitre 2 caractérisé par la formation d’un réseau de défauts topologiques orientés. Ces stries huileuses sont ensuite utilisées pour permettre l’alignement à l’échelle individuelle de particules semi-conductrices, des dots-in-rods de CdSe:CdS, suivant l’axe principal des défauts. Le chapitre 3 présente l’insertion des particules et la mesure de l’orientation de leur dipôle associé ainsi que celle du degré de polarisation. Le chapitre 4 discute du comportement des particules pour une concentration élevée, avec outre leur orientation leur auto-organisation au sein des stries huileuses. Nous faisons une analyse statistique de la densité des amas formés à la surface d’un échantillon et des informations résultant de la structure des amas sur l’organisation des défauts dans différentes situations. On observe un alignement des nanoparticules à l’échelle unique et en amas, ainsi qu’un maintien ou un renforcement du degré de polarisation mesuré, montrant une auto-organisation des amas favorisant l’interaction entre les dipôles des particules. / This thesis discusses the use of a liquid crystal structure, called oily streaks, formed by the competition of two antagonist anchoring on each side of a submicrometric liquid crystal layer, to achieve the self-alignment and, for higher concentration, the organization, of single photon emitters on an individual scale. We discuss the internal layout of these oily streaks through measurements done in polarized optical microscopy, ellipsometry and X-ray diffraction analysis. These data sets are correlated in chapter 2 into a description of the internal structure of the oily streaks, characterized by the formation of a pattern of oriented topological defects, and an analysis of their behaviour. These streaks are then used as a template to align single photon emitters, CdSe:CdS dot-in-rods, on an individual scale alongside the main axis of the defects. We measure the alignment of their dipoles as well as their degree of polarization in order to discuss the behaviour of the particles in the topological defects of the oily streaks. The last chapter presents a statistical analysis of the behaviour of nanoparticles in oily streaks once their concentration is increased, depending on their size in number of particles as well as the characteristics of the structure in which the single particles or the clusters are trapped. We use these elements to further our understanding of the layout of oily streaks in different thicknesses and configurations as we observe the alignment phenomenon both with single particles and clusters, as well as, for the clusters, a similar or superior degree of polarization compared to single particles, indicating an interaction between the particles’ dipoles.

Yes / Cocrystals consist of two molecules bonded together in a single crystal lattice giving rise to wide applications including improving solubility of poorly soluble pharmaceuticals. Cocrystallization reaction occurs in the oily phase of liquid–liquid phase separation (LLPS) after it is mixed with coformers. Indomethacin–saccharin cocrystal formation was monitored in situ, and the kinetics of crystallization were determined. The crystallization rates show that the process can be proposed to prevent unwanted oily phase formation during LLPS. / Research Development Fund Publication Prize Award winner, Sep 2022.

[pt] Métodos de análise para determinação de elementos-traço em amostras oleosas e pastosas são necessários, por exemplo, no caso do petróleo e em suas frações mais pesadas, para os quais os elementos-traço indicam características do tipo do petróleo, correlacionando-o com a localização geográfica da jazida. Além disso, a quantificação destes elementos tem utilidade nas interpretações geoquímicas relacionadas com maturidade térmica, correlação óleo-óleo e migração primária e secundária do óleo e na obtenção de informações que permitem a criação de estratégias para realizar o refino do óleo, prevenindo contaminação dos catalisadores, corrosão de equipamento e potencial dano ambiental. No caso de óleos e gorduras vegetais, a presença destes elementos, mesmo em baixas concentrações ((mi)g g-1), pode acelerar processos oxidativos que geram peróxidos, aldeídos, cetonas, ácidos e epóxidos, que além de causarem a rancidez prematura dos óleos produzem efeitos patológicos no sistema digestivo e potencializam a ação de alguns carcinogênicos. As técnicas espectrométricas baseadas no uso do plasma (ICP OES e ICP-MS) estão entre as mais utilizadas na determinação de elementos- traço nesses tipos de amostra. Porém, os procedimentos de preparação de amostra mais tradicionalmente usados são os que destroem a matriz das amostras, solubilizando-as em ácidos inorgânicos fortes. Neste trabalho, novas estratégias de preparação de amostras de petróleo, óleo diesel, asfaltenos, óleos comestíveis, manteiga e margarina foram desenvolvidas visando à utilização do tradicional procedimento de nebulização de solução para introdução de amostra no plasma. No caso do óleo diesel, a estratégia avaliada foi a de preparação de amostras na forma de emulsão com n-propanol. Nesse caso, um planejamento fatorial indicou que fatores importantes para a determinação de elementos refratários foram tanto a massa de amostra na composição da emulsão (até 25% em massa) quanto a acidificação da emulsão. As amostras de óleo cru, óleos vegetais e gorduras vegetais foram preparadas como microemulsão em n-propanol. Alternativamente, um procedimento de extração assistida por ultra-som foi desenvolvido. A emulsão de óleo cru com n-propanol mostrou ser um bom meio de estabilização dos analitos em solução. No caso da extração ácida assistida por ultra-som para óleo cru, um planejamento fatorial mostrou que os fatores importantes para a determinação de elementos-traço foram, o tempo de aquecimento da amostra, a concentração do ácido nítrico e a exposição ao ultra-som. Para as amostras de óleos e gorduras vegetais, a otimização das proporções de componentes na emulsão com n- propanol proporcionou boa estabilidade e homogeneidade das amostras de óleo de oliva e óleo de soja (6 % em massa de óleo) e para margarina e manteiga (5 % m/m de óleo). Para o método da extração ácida assistida por ultra-som, as condições otimizadas para a preparação da amostra permitiram também a análise por ICP-MS, cujos resultados são discutidos e comparados com os resultados obtidos por ICP OES. Para as amostras de asfaltenos, o procedimento proposto foi o de extração em HNO3 concentrado assistida por ultrasom. Nesse caso, os mesmos parâmetros otimizados para o óleo cru foram usados. Os parâmetros operacionais foram otimizados para obtenção dos parâmetros de mérito, sendo a aplicação dos métodos propostos confirmada por testes de recuperação além de comparação com resultados obtidos com procedimentos tradicionais para esse tipo de amostra. Assim, nessa tese, foram desenvolvidos métodos para a determinação de Cr, Mo, V e Ti em óleo diesel e em óleo combustível, Cd, Co, Cr, Fe, Mn, Mo, Ni, Ti, V e Zn em óleo cru, Fe, Ni e V em asfaltenos. Cd, Co, Cr, Cu, Mn e Ni foram determinados em óleos e gorduras comestíveis utilizando preparação de amostra como microemulsão em n-propanol. Já Al, Ca, Cd, Cu, Fe, Mg, Mn, Ni, V e Zn foram determinados após extração ácida assistida por / [en] Analytical methods for the determination of trace elements in oily and viscous samples are necessary, for example, in the case of crude oil and its heavy fractions, where trace elements indicate specific oil characteristics and the geographic location of the natural deposit. Moreover, the quantification of these elements is relevant for geochemical interpretations concerning thermal maturity, oil-oil correlations and primary and secondary oil migration. Knowledge on trace element characteristics of crude oil is also important in oil refining strategies to prevent contamination of catalysts as well as equipment corrosion, and to minimize environmental pollution. In the case of vegetal oils and fats, the presence of certain elements, even in low concentrations ((mi)g g-1); can speed up oxidative processes and premature rancidity of oils, which may cause pathological effects in the digestive system, including cancer. Spectrometric techniques based on inductively coupled plasma (ICP OES and ICPMS) are extensively used for determination of trace elements in such type of samples due to their sensitivities and multielemental features. In the case of oils and fats, the samples have to be generally decomposed by wet-ashing procedures with mineral acids, prior to the elemental determinations. In this work, new strategies for sample preparation of crude oil, diesel, asphaltenes, edible oils, butter and margarine have been developed, which allow the use of the traditional procedure for sample introduction into the ICP by solution nebulization. In the case of diesel oil, the proposed strategy was the preparation of samples as emulsions with n-propanol. Factorial design studies showed that the important factors for the quantitative determination of refractory metals were the sample amount in the emulsion (up to 25% in weight) and the acidification of the emulsion. Crude oil samples, vegetable oils and fats have been prepared as n-propanol microemulsions. Alternatively, an ultrasound-assisted trace metal extraction procedure was developed. The crude oil emulsions with n-propanol were found to be a good environment to keep the analytes in solution. In the case of the ultrasound-assisted acid extraction for crude oil, a factorial design indicated that the important factors for the determination of trace elements have been the sample heating time, the nitric acid concentration and the ultrasound exposure time. For vegetable oils and fats, the optimization of the npropanol emulsion components provided good stability and homogeneity olive and soy oils (6 % of oil in weight) and for margarine and butter (5 % of oil in weight). For the ultrasound-assisted acid extraction, the optimized conditions for sample preparation also allowed the analysis of the extracts by ICP-MS, which results were compared with the ones obtained by ICP OES. For asphaltene samples, the proposed procedure was the ultrasound- assisted acid extraction in concentrated HNO3 using similar conditions employed for crude oil. The figures of merit for the proposed methods were achieved under optimized experimental and instrumental conditions and validations were performed by analysis of certified reference materials (when available), recovery tests, and by comparison of results obtained using traditional sample preparation procedures for this type of sample. Methods for the determination of Cr, Mo, V and Ti in fuel and diesel oils, for Cd, Co, Cr, Fe, Mn, Mg, Ni, Ti, V and Zn in crude oil and for Fe, Ni and V in asphaltenes have been developed. Cd, Co, Cr, Cu, Mn and Ni in edible oils and fats have been determined using the microemulsification in n-propanol, while Al, Ca, Cd, Cu, Fe, Mg, Mn, Ni, V and Zn have been determined after acid extraction in HNO3. The analyses were carried out by using the external calibration method with internal standardization by Sc (in the case of ICP OES). The ultrasound-assisted acid extraction method for t

Made available in DSpace on 2014-12-17T15:42:07Z (GMT). No. of bitstreams: 1 LedaMOL_TESE.pdf: 3658937 bytes, checksum: 6ad7dbe6b2ec8a6f89d9264905ef89b6 (MD5) Previous issue date: 2010-12-21 / Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1? order. / Tecnologias inovadoras que usam materiais tensoativos t?m aplicabilidade em v?rios campos industriais, dentre eles petr?leo e g?s natural. Este estudo busca investigar o uso de um tensoativo, derivado de ?leo de coco (OCS - ?leo de coco saponificado), no processo de recupera??o de compostos org?nicos presentes em efluentes oleosos da ind?stria de petr?leo. Para este fim, foram realizados experimentos em uma coluna de bancada objetivando verificar a influ?ncia do tensoativo OCS na efici?ncia de remo??o de ?leo. Desta forma, foram preparadas emuls?es com quantidades fixas de ?leo (50, 100, 200 e 400 ppm), determinandose a concentra??o ?tima de tensoativo para cada uma delas. Foram, tamb?m, realizados alguns ensaios com ?gua de produ??o da ind?stria de petr?leo, visando comparar o resultado com o das emuls?es. O processo de separa??o consiste no uso de bolhas gasosas formadas quando um fluxo de g?s passa em uma coluna l?quida, com concentra??es de tensoativo, ocorrendo a coalesc?ncia das gotas de ?leo dispersas e, consequentemente, o transporte delas ao topo da coluna, formando uma nova fase oleosa cont?nua. O processo fundamenta-se na satura??o de tensoativo na interface g?s-l?quido, dependendo da concentra??o de tensoativo usada, resultando na flota??o da fase ?leo dispersa. Um filtro de prato poroso, com tamanho de poro que varia de 40 a 250 μm, foi colocado ? base da coluna para permitir uma opera??o hidrodin?mica est?vel. Durante os procedimentos experimentais, o volume operacional da fase l?quida foi mantido constante e a taxa de fluxo de ar variada em cada experimento. Os resultados experimentais do estudo hidrodin?mico demonstraram que a captura do ?leo foi influenciada pelos di?metros das bolhas e vaz?es de ar. Com o aumento da vaz?o de 300 para 900 cm3.min-1, ocorreu um aumento de remo??o da fase ?leo de 44% para 66% e a cin?tica de remo??o do ?leo foi definida como uma rea??o de 1? ordem

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T22:05:09Z No. of bitstreams: 1 VALDETE CAMPOS SILVA - DISSERTAÇÃO PPGEQ 2015..pdf: 1742009 bytes, checksum: d14a2b9103828a1effe17c04bc86fe09 (MD5) / Made available in DSpace on 2018-03-23T22:05:09Z (GMT). No. of bitstreams: 1 VALDETE CAMPOS SILVA - DISSERTAÇÃO PPGEQ 2015..pdf: 1742009 bytes, checksum: d14a2b9103828a1effe17c04bc86fe09 (MD5) Previous issue date: 2015-04-13 / Capes / As águas oleosas provenientes de descartes de algumas indústrias representam um sério problema para o ecossistema marinho e terrestre, sendo necessário um tratamento prévio para reutilização ou descarte dessas águas. O uso de materiais adsorventes vem sendo bastante estudado pelo fato de minimizar os problemas causadores no sistema ambiental. A busca por materiais de baixos custos, alta capacidade de remoção e fácil disponibilidade são fatores importantes para a sua escolha. Sendo assim, este trabalho teve como objetivo a avaliação da capacidade de remoção de óleo utilizando argila vermiculita modificada com sal quaternário de amônio e cera de carnaúba líquida em soluções emulsionadas óleo/água. Para tal finalidade, o planejamento fatorial 2² com três pontos centrais foi realizado para determinar as condições dos ensaios de banho finito. Para o processo de expansão a argila vermiculita in natura foi aferida, antes e depois da expansão, em uma proveta graduada. Foi levada ao forno mufla frio até atingir as temperaturas de 700, 800, e 900 ºC e, após atingir estas temperaturas permaneceu por mais 15 minutos no forno. A argila vermiculita expandida foi modificada com o sal quaternário de amônio CTABr e a cera de carnaúba líquida durante 2 minutos, sob agitação constante. Após as modificações, foram preparadas as emulsões óleo/água nas concentrações de 50, 75 e 100 ppm, utilizando o cloreto de sódio, óleo lubrificante Petrobras e água deionizada, sob agitação mecânica por 20 minutos. Para o banho finito, foram utilizadas as amostras da argila modificada, água deionizada, e as emulsões óleo/água, seguindo o planejamento fatorial 2². Após todos os procedimentos, as emulsões óleo/água e as amostras do banho finito, foram avaliadas através do analisador de óleo Horiba OCMA-350. Por meio do tratamento térmico, verificou-se que o processo de expansão das lamelas da vermiculita foi favorecido a temperatura de 700 oC. Nos difratogramas ficou evidenciado a intercalação do sal quaternário de amônio devido aumento da distância interlamelar do pico característico da argila vermiculita expandida. Com os espectros de infravermelhos observou-se a ausência da água adsorvida, ocasionada pelo processo de expansão, e a intercalação do material orgânico. A partir das micrografias verificou-se que a intercalação do sal quaternário de amônio e a cera de carnaúba gerou o preenchimento dos espaços vazios entre as camadas decorrentes da argila expandida que resultaram em aglomerados mais compactos. A argila vermiculita modificada com sal quaternário de amônio apresentou maior potencial na capacidade de remoção, nos tempos de 1h e 3h, e concentração de 100 ppm, em relação à argila modificada com cera de carnaúba. Para a argila vermiculita modificada com sal quaternário de amônio os ensaios 1 (50 ppm/1 hora) e 2 (100 ppm /1 hora) tiveram a melhor porcentagem de remoção de óleo, com 89,72% e 90,80%, respectivamente, e para a argila vermiculita modificada com cera de carnaúba os ensaios 2 (100 ppm/1 hora) e 4 (100 ppm/3 horas) tiveram a melhor remoção de óleo, com 84,21% e 86,90%, respectivamente. / Oily water from discharges of some industries represent a serious problem for the marine and terrestrial ecosystem, requiring pretreatment for reuse or disposal of these waters. The use of adsorbent materials has been widely studied because of minimizing the problems causing the environmental system. The search for low-cost materials, high capacity removal and easy availability are important factors in their choice. Thus, this study aimed to evaluate the oil removal capacity using vermiculite modified clay with quaternary ammonium salt and wax liquid carnauba in emulsified oil / water solutions. For this purpose, the factorial design 2² with three central points was conducted to determine the conditions of finite bath trials. For the process of expansion in nature vermiculite clay was measured before and after expansion, in a graduated cylinder. It was brought to the cold muffle furnace until it reaches temperatures of 700, 800, and 900 ° C and, after reached these temperatures remained for 15 more minutes in the oven. The expanded vermiculite clay was modified with the quaternary ammonium salt, the liquid CTABr and carnauba wax, for 2 minutes under constant stirring. After the modifications, the oil/water emulsions were prepared at concentrations of 50, 75 and 100 ppm, using sodium chloride, Petrobrás lubricating oil and deionized water, under mechanical stirring for 20 minutes. For the finite bath, the samples modified clay, the deionized water, and the oil/water emulsions were used, according to the 2² factorial design. Após todos os procedimentos, as emulsões óleo/água e as amostras do banho finito, foram avaliadas através do analisador de óleo Horiba OCMA-350. Through the heat treatment, it was found that the process of expansion of the vermiculite lamellae was favored of 700 ° C temperature. In diffractogram, was evidence the intercalation of quaternary ammonium salt, due to increased interlayer distance from the characteristic peak of the expanded vermiculite clay. With the infrared spectra, were observe the absence of adsorbed water, caused by the expansion process, and intercalation of the organic material. From the micrographs it was found that the intercalation of quaternary ammonium salt and carnauba wax generated filled the voids between layers of the resulting expanded clay which have resulted in more compact aggregation. The vermiculite modified clay with quaternary ammonium salt has the greatest potential removability, the times of 1h and 3h, and 100 ppm concentration, in relation to the clay modified with carnauba wax. For the vermiculite modified clay with quaternary ammonium salt, the tests 1 (50 ppm / 1 hour) and 2 (100 ppm / 1 hour) had the best percentage of oil removal, with 89.72% and 90.80%, respectively, and vermiculite modified

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-30T17:51:31Z No. of bitstreams: 1 TELLYS LINS DE ALMEIDA BARBOSA - DISSERTAÇÃO PPGEQ 2014..pdf: 2340446 bytes, checksum: 3a2ea16e16c4359a82b431379410d16c (MD5) / Made available in DSpace on 2018-04-30T17:51:31Z (GMT). No. of bitstreams: 1 TELLYS LINS DE ALMEIDA BARBOSA - DISSERTAÇÃO PPGEQ 2014..pdf: 2340446 bytes, checksum: 3a2ea16e16c4359a82b431379410d16c (MD5) Previous issue date: 2014-09-26 / O presente trabalho visa estudar o desempenho e validação de um sistema com automação para processos de separação de águas oleosas com membranas cerâmicas. O trabalho foi dividido em duas partes: testes em escala de bancada e no sistema com automação. Nos ensaios em escala de bancada foram realizados experimentos de caracterização da membrana cerâmica com água deionizada e com efluente sintético, com intuito de estimar o comportamento das membranas para auxiliar no desenvolvimento do sistema com automação. Para avaliar o desempenho dos sistemas de separação água/óleo com membranas cerâmicas os seguintes parâmetros foram analisados: fluxo do permeado (J, em L/h.m2) e taxa de rejeição de óleo. Nos experimentos no sistema com automação foi avaliado o desempenho no processo de separação água/óleo com membranas cerâmicas, o efluente sintético utilizado obedeceu às mesmas condições do sistema de bancada. Os experimentos com efluente sintético foram simulados com concentração de óleo fixada em 20 mg/L. Observou-se que a redução do fluxo de permeado com o tempo de operação é fortemente dependente da pressão e do teor de óleo emulsionado, podendo ser relacionada aos fenômenos de polarização por concentração, inerentes aos PSM. Contudo, a redução do fluxo no permeado foi atenuada no sistema com automação que possui processos de limpeza backpulse e backwash. Quanto à taxa de rejeição da fase dispersa, para todas as condições analisadas, apresentou-se maior que 97%. A utilização do backwash tendo como agente de limpeza uma solução de hidróxido de sódio não foi eficaz na recuperação do fluxo do permeado, porém o comportamento do processo de limpeza foi extremamente satisfatório o que indica com a mudança do agente de limpeza no processo terá uma melhor recuperação do fluxo do permeado. A partir dos experimentos realizados no sistema com automação os resultados obtidos demostram potencial para separação com membranas cerâmica, para o tratamento de águas oleosas. / This work aims to study the performance and validation of system with automation to oily water separation processes with ceramic membranes. It was divided into two phases: laboratory-scale tests and tests with the system with automation. In the laboratory-scale tests, experiments to characterize the ceramic membrane were carried out with deionized water and synthetic effluent, aiming to estimate the behavior of membranes to assist the developing of the system with automation. To evaluate the performance of the water-oil separation systems with ceramic membranes the following parameters were analyzed: permeate flow (J, L/h.m2) and oil rejection rate. In the experiments with the automatic system the performance was evaluated in oil-water separating process with ceramic membrane, the synthetic effluent used followed the same conditions as the benchtop system. The experiments with synthetic effluent were simulated with oil concentration set at 20 mg/L. It was observed that the reduction of the permeate flux with the operation time is strongly dependent of the pressure and emulsified oil content, may be related to concentration polarization, inherent to membrane separation processes. However, the reduction of permeate flow was attenuated in the system with automation where backpulse and blackwash cleaning processes were used. The dispersed phase rejection rate, for all conditions analyzed, was greater than 97%. The backwash cleaning system having sodium hydroxide as cleaning agent was not effective to increase the permeate flow, but the cleaning agent performance was extremely satisfactory which indicates that the change of the cleaning agent in the process will increase the flow in the permeate stream. From the experiments carried out with the system with automation results demonstrate the potential for separation with ceramic membranes, for oily water treatment.

Made available in DSpace on 2014-12-17T14:09:17Z (GMT). No. of bitstreams: 1 CiceroSL_TESE.pdf: 5334902 bytes, checksum: 41714ced8f45a82dbc84b8d2449a7bee (MD5) Previous issue date: 2014-03-21 / The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery / A borra oleosa (BO) de petr?leo ? uma mistura complexa de hidrocarbonetos, impurezas org?nicas, inorg?nicas e ?gua. Um dos grandes problemas encontrados atualmente na ind?stria de petr?leo ? o gerenciamento (acondicionamento, armazenamento, transporte e destino) de res?duos. Os nanomateriais (catalisadores) mesoporosos e microporosos s?o considerados promissores em processos de refino de petr?leo e como adsorventes para prote??o ambiental. O objetivo deste trabalho foi estudar a BO de petr?leo oriunda do processamento prim?rio (bruta e tratada) e res?duo de v?cuo, com aplica??o de an?lise termogravim?trica, t?cnica de pir?lise t?rmica e catal?tica com nanomateriais, visando a produ??o de derivado de petr?leo. As borras extra?das em um equipamento soxhlet foram analisadas por an?lise elementar, cromatografia em camada fina, termogravimetria (TG) e pir?lise acoplado a um cromatogr?fico gasoso/espectro de massa (Py-GC/MS). Os catalisadores AlMCM-41 e AlSBA-15 foram sintetizados com uma raz?o molar de s?licio/alum?nio de 50 (Si/Al = 50), usando tetraetilortossilicato (TEOS) como fonte de sil?cio e pseudobuhemita (AlOOH) como a fonte de alum?nio. Os catalisadores indicam que os materiais apresentaram estrutura hexagonal, ?rea espec?fica de 783,6 m2/g para o AlMCM-41, 600 m2/g para o AlSBA-15.1 e 377 m2/g para o AlSBA-15.2). A BO extra?da apresentou de 65 a 95% de componentes org?nicos (?leo), de 5 a 35% de componentes inorg?nicos (sais e ?xidos) e diferentes composi??es dos derivados. Os catalisadores tipo AlSBA-15 apresentaram melhor desempenho na obten??o dos derivados de petr?leo, aumentando em 20% a produ??o de querosene e gas?leo leve. O potencial energ?tico da BO foi elevado, pois ela pode ser utilizada como combust?vel e processada com outras cargas pesadas do petr?leo para a produ??o de diferentes derivados de petr?leo

Made available in DSpace on 2014-12-17T15:01:13Z (GMT). No. of bitstreams: 1 PaulaKLS.pdf: 655947 bytes, checksum: 42dfa97fce97ed099a5660c9d396a0eb (MD5) Previous issue date: 2008-02-29 / In the petroleum industry, water is always present in the reservoir formation together with petroleum and natural gas and this fact provokes the production of water with petroleum, resulting in a great environmental impact. Several methods can be applied for treatment of oily waters, such as: gravitational vases, granulated media filtration systems, flotation process, centrifugation process and the use of hydrocyclones, which can also be used in a combined way. However, the flotation process has showed a great efficiency as compared with other methods, because these methods do not remove great part of the emulsified oil. In this work was investigated the use of surfactants derived from vegetable oils, OSS and OGS, as collectors, using the flotation process in a glass column with a porous plate filter in its base for the input of the gaseous steam. For this purpose, oil/water emulsions were prepared using mechanical stirring, with concentrations around 300 ppm. The air flow rate was set at 700 cm3/min and the porous plate filter used for the generation of the air bubbles has pore size varying from 16 to 40 Pm. The column operated at constant volume (1500mL). A new methodology has been developed to collect the samples, where, instead of collecting the water phase, it was collected the oil phase removed by the process in the top of the flotation column. It has been observed that it is necessary to find an optimum surfactant concentration to achieve enhanced removal efficiency. Being for OSS 1.275 mmol/L and for OGS 0.840 mmol/L, with removal efficiencies of 93% and 99%, respectively, using synthetic solutions. For the produced water, the removal in these concentrations was 75% for OSS and 65% for OGS. It is possible to remove oil from water in a flotation process using surfactants of high HLB, fact that is against the own definition of HLB (Hydrophile-Lipophile Balance). The interfacial tension is an important factor in the oil removal process using a flotation process, because it has direct interference in the coalescence of the oil drops. The spreading of the oil of the air bubble should be considered in the process, and for the optimum surfactant concentrations it reached a maximum value. The removal kinetics for the flotation process using surfactants in the optimum concentration has been adjusted according to a first order model, for synthetic water as for the produced water. / Na ind?stria petrol?fera, a ?gua est? associada ao petr?leo e ao g?s natural, formando a ?gua de produ??o e gerando um grande impacto ambiental. Existem diversos m?todos de tratamento para as ?guas oleosas, tais como: vasos gravitacionais, sistemas de filtra??o em meio granular, flota??o, centrifuga??o e utiliza??o de hidrociclones, podendo ser utilizados de forma combinada. Entretanto, a flota??o tem mostrado maior efici?ncia com rela??o aos outros m?todos, pois eles n?o conseguem remover grande parte do ?leo emulsionado. O presente trabalho estuda a utiliza??o de tensoativos de origem vegetal, OSS (?leo de Soja Saponificado) e OGS (?leo de Girassol Saponificado), como coletores, atrav?s da flota??o em uma coluna com aera??o da suspens?o atrav?s de uma placa porosa. Para este fim, foram preparadas emuls?es ?leo/?gua por agita??o mec?nica, com concentra??es m?dias de 300 ppm. A vaz?o de ar utilizada foi de 700 cm3/min e o filtro de placa porosa utilizado para a gera??o das bolhas de ar foi de porosidade de (16-40) Pm. A coluna trabalhou a um volume constante de 1500mL. Desenvolveu-se uma nova metodologia para coletar as amostras, onde, ao inv?s de coletar a ?gua, coletou-se o ?leo removido na parte superior da c?lula de flota??o. Observou-se que ? necess?rio encontrar uma concentra??o ?tima de tensoativo para que haja uma maior efici?ncia de remo??o. S?o elas 1,275 mmol/L para o OSS e 0,840 mmol/L para o OGS, com efici?ncias de remo??o de 93 % e 99 %, respectivamente, em ?guas sint?ticas. Para a ?gua de produ??o, a remo??o nestas concentra??es foi de 75% para o OSS e 65% para o OGS. ? poss?vel remover ?leo de ?gua em um processo de flota??o utilizando tensoativos de BHL alto, fato que contraria a pr?pria defini??o de BHL (Balan?o Hidrof?lico-Lipof?lico). A tens?o interfacial ? um fator importante no processo de remo??o do ?leo na flota??o, pois interfere diretamente na coalesc?ncia das gotas de ?leo. O espalhamento do ?leo da bolha de ar deve ser considerado no processo, e para as concentra??es ?timas de tensoativo atingiu um valor m?ximo. A cin?tica da remo??o se ajustou para o modelo de primeira ordem na flota??o utilizando tensoativos na concentra??o ?tima, tanto para ?gua sint?tica como para a ?gua de produ??o.

Made available in DSpace on 2014-12-17T15:01:50Z (GMT). No. of bitstreams: 1 CarlosEMJ_TESE.pdf: 1404904 bytes, checksum: 3029c558b265d6dfdac69a6fac1ef20c (MD5) Previous issue date: 2010-05-24 / An evaluation project was conducted on the technique of treatment for effluent oil which is the deriving process to improve cashews. During the evaluation the following techniques were developed: advanced processes of humid oxidation, oxidative processes, processes of biological treatment and processes of adsorption. The assays had been carried through in kinetic models, with an evaluation of the quality of the process by means of determining the chemical demand of oxygen (defined as a technique of control by means of comparative study between the available techniques). The results demonstrated that the natural biodegradation of the effluent ones is limited, as result using the present natural flora in the effluent one revealed impracticable for an application in the industrial systems, independent of the evaluation environment (with or without the oxygen presence). The job of specific microorganisms for the oily composite degradation developed the viability technique of this route, the acceptable levels of inclusion in effluent system of treatment of the improvement of the cashew being highly good with reasonable levels of removal of CDO. However, the use combined with other techniques of daily pay-treatment for these effluent ones revealed to still be more efficient for the context of the treatment of effluent and discarding in receiving bodies in acceptable standards for resolution CONAMA 357/2005. While the significant generation of solid residues the process of adsorption with agroindustrial residues (in special the chitosan) is a technical viable alternative, however, when applied only for the treatment of the effluent ones for discarding in bodies of water, the economic viability is harmed and minimized ambient profits. Though, it was proven that if used for ends of I reuse, the viability is equalized and justifies the investments. There was a study of the photochemistry process which have are applicable to the treatment of the effluent ones, having resulted more satisfactory than those gotten for the UV-Peroxide techniques. There was different result on the one waited for the use of catalyses used in the process of Photo. The catalyses contained the mixing oxide base of Cerium and Manganese, incorporated of Potassium promoters this had presented the best results in the decomposition of the involved pollutants. Having itself an agreed form the gotten photochemistry daily paytreatment resulted, then after disinfection with chlorine the characteristics next the portability to the water were guarantee. The job of the humid oxidation presented significant results in the removal of pollutants; however, its high cost alone is made possible for job in projects of reuses, areas of low scarcity and of raised costs with the capitation/acquisition of the water, in special, for use for industrial and potable use. The route with better economic conditions and techniques for the job in the treatment of the effluent ones of the improvement of the cashew possesses the sequence to follow: conventional process of separation water-oil, photochemistry process and finally, the complementary biological treatment / Neste trabalho foram avaliadas t?cnicas de tratamento para os efluentes oleosos oriundos do processo de beneficiamento da castanha de caju. As t?cnicas avaliadas foram: processos de oxida??o ?mida, processos oxidativos avan?ados, processos de tratamento biol?gico e processos de adsor??o. Os ensaios foram realizados com propostas de modelos cin?ticos, com monitoramento da qualidade dos processos por meio da determina??o da demanda qu?mica de oxig?nio (definida como t?cnica de controle por meio de estudo comparativo entre as t?cnicas dispon?veis). Os resultados demonstram que a biodegrada??o natural dos efluentes ? limitada, e os resultados utilizando da flora natural presente no efluente mostrou-se invi?vel para aplica??o em sistemas industriais, independente do ambiente de avalia??o (com ou sem a presen?a de oxig?nio). O emprego de microorganismos espec?ficos para a degrada??o de compostos oleosos incrementou a viabilidade t?cnica dessa rota,em n?veis adequados para aplica??o em sistemas de tratamento de efluentes do beneficiamento da castanha, tendo-se uma boa expressividade, com remo??o da DQO. Por?m, o uso combinado com outras t?cnicas de pr?-tratamento para esses efluentes mostrou-se ainda mais eficiente para o contexto do tratamento de efluentes e descarte em corpos receptores dentro dos padr?es preconizados pela resolu??o CONAMA 357/2005. Apesar da gera??o significativa de res?duos s?lidos, o emprego do processo de adsor??o com res?duos agroindustriais (em especial a quitosana) ? uma alternativa tecnicamente vi?vel, por?m, quando aplicada apenas para o tratamento dos efluentes para o descarte em corpos d ?gua, a viabilidade econ?mica ? prejudicada e os ganhos ambientais minimizados. Por?m, foi comprovado que se utilizado para fins de reuso, a viabilidade ? equiparada e justifica os investimentos. Os processos fotoqu?micos s?o aplic?veis ao tratamento dos efluentes estudados, tendo-se como resultados mais satisfat?rios aqueles obtidos para as t?cnicas de UV-Per?xido. Sendo o resultado diferente do esperado pela utiliza??o de catalisadores usados no processo de Foto-Fenton. Os catalisadores a base de ?xido misto de C?rio e Mangan?s, incorporado de promotores de Pot?ssio, apresentaram os melhores resultados na decomposi??o dos poluentes envolvidos. Os resultados obtidos de forma combinada ao pr?-tratamento fotoqu?mico, ap?s desinfec??o com cloro, garantem caracter?sticas pr?ximas a potabilidade da ?gua. O emprego da oxida??o ?mida apresenta resultados muito significativos na remo??o de poluentes, entretanto, o seu alto custo s? ? viabilizado para emprego em projetos de reuso, em ?reas de baixa escassez e de elevados custos com a capta??o/aquisi??o da ?gua, em especial, para utiliza??o para uso industrial e pot?vel. A rota com melhores condi??es econ?micas e t?cnicas para o emprego no tratamento dos efluentes do beneficiamento da castanha de caju, possui a seq??ncia a seguir: processo convencional de separa??o ?gua-?leo, processo fotoqu?mico e por fim, o tratamento biol?gico complementar