Made available in DSpace on 2014-12-17T15:01:17Z (GMT). No. of bitstreams: 1 NorbertoAM.pdf: 1190502 bytes, checksum: 15fc3890db7720ac4fcdf9c75747130a (MD5) Previous issue date: 2005-12-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / This work aims to use a different hydrodynamic condition applied to a new design of mixer-settler on treating wastewater produced by petroleum industry, called MDIF (Misturador-Decantador ? Invers?o de Fases/ Mixer-Settler based on Phase Inversion MSPI). The use of this different hydrodynamic behaviour is possible due to vertical disposition of the device and the principle of Phase Inversion that controls the MDIF, providing the generation (creation) of a cascade of drops, into an organic layer, that works as micro-decanters, thus making possible the formation of a bed of non-coalesced drops, called Bed Formation . The use of this new hydrodynamics condition allows to increase the residence time of the oil carrier drops, into an organic layer, and the device can treat a greater volume of wastewater. In view of to get this condition it is necessary to operate at high throughput (58,6 m3.m-2.h-1). By results, the condition of Bed Formation is the best one to be used when MSPI operates with throughput up to 58,6 m3.m-2.h-1. The results using the condition of Bed Formation show that increasing the height of the bed of non-coalesced drops and/or decreasing the volumetric ratio (O/A) an increase of the separation efficiency is detected / Este trabalho objetiva utilizar uma diferente condi??o hidrodin?mica aplicada a um novo design de misturador-decantador aplicado ao tratamento de ?guas produzidas da ind?stria do petr?leo, que vem sendo denominado de MDIF (Misturador-Decantador ? Invers?o de Fases). A utiliza??o do regime hidrodin?mico de Leito Denso ? poss?vel devido a disposi??o vertical do aparelho e ao princ?pio de invers?o de fases que rege o MDIF, proporcionando a gera??o de uma cascata de gotas, na regi?o de leito org?nico, que funcionam como micro-decantadores, possibilitando assim a forma??o de um leito de gotas n?o-coalescidas, denominado de Leito Denso. A utiliza??o desta nova condi??o hidrodin?mica permite o aumento do tempo de resid?ncia da gota transportadora de ?leo, na regi?o de leito org?nico, e o trata um maior volume de ?gua produzida, visto que para se atingir esta condi??o ? necess?rio se operar a altas vaz?es (58,6 m3/m2h). A partir dos resultados obtidos, a condi??o de regime de leito denso mostra-se como a melhor condi??o a ser utilizada quando se opera o misturador-decantador ? invers?o de fases com vaz?es espec?ficas acima de 58,6 m3.m-2.h-1. Os resultados utilizando o regime de leito denso mostram que elevando-se a altura do leito de gotas n?o-coalescidas e/ou diminuindo a raz?o volum?trica org?nico/aquoso aumenta a efici?ncia de separa??o do aparelho

Au-dessus d’une certaine température appelée température de trouble (Tc), les solutions aqueuses de la majorité des tensioactifs non ioniques polyéthoxylés se séparent en deux phases liquides en équilibre : la phase diluée et le coacervat. Grâce à la solubilisation micellaire de composés hydrophobes, amphiphiles ou même ioniques et à leur concentration dans le (faible) volume de coacervat, une extraction à deux phases aqueuses (extraction par point de trouble ou par coacervat)peut être réalisée et appliquée à des opérations de dépollution d'effluents industriels ou à la concentration ou encore à la séparation de substances à haute valeur ajoutée. L’extraction par point de trouble (CPE) est une technique relativement simple et écologique pour l'élimination des matières toxiques de l'environnement, qui s’est avérée efficace dans le traitement de divers contaminants (organiques et inorganiques dissous ou dispersés) de l’eau. Une première partie de cette thèse consiste à rappeler quelques notions sur la pollution industrielle des eaux et quelques généralités sur les tensioactifs (TA) et sur l’extraction liquide-liquide. Elle est suivie d’une description des réactifs, du matériel et des méthodes utilisées au cours de ce travail, comme préliminaire à la mise au point d'un procédé d'extraction par coacervat. Quelques propriétés thermodynamiques superficielles (adsorption) et d’association (micellisation) de deux tensioactifs non ioniques industriels (le Simulsol NW342 et le Tergitol 15-S-7) ont été déterminées. Les courbes de démixtion des systèmes binaires (eau/TA) ainsi que l’effet de divers additifs (sel, composés organiques, tensioactifs ioniques) sur le point de trouble sont étudiés. Le diagramme isotherme du système ternaire (eau/TA/ phénol) est tracé. Une application du modèle de Flory-Huggins-Rupert pour la prédiction des courbes de démixtion des tensioactifs non ioniques a été expérimentée. L’extraction à un seul contact, à partir de solutions modèles, utilise des alcools oxo éthoxylés biodégradables (Simulsol NW342 et Tergitol 15-S-7) pour des polluants organiques dissous (phénol, 1-phényléthanol et alcool benzylique) et un mélange de tensioactifs non ionique (Simulsol NW342) et ionique (SDS ou CTAB) pour des polluants métalliques solubles (plomb(II), molybdène(VI)). On cherche le meilleur compromis entre le pourcentage de soluté extrait (E%),la fraction volumique du coacervat (фv), et les pourcentages de soluté et de tensioactif restants dans la phase diluée (Xs,d et XTA, d), en utilisant un plan d'expériences de type Scheffé et un lissage empirique des courbes. Les résultats sont très prometteurs car les pourcentages d’extraction varient de 60 à 95% pour les solutés organiques et de 40 à 85% pour les solutés métalliques, les meilleures performances étant obtenues pour le phénol et le plomb. D’autre part, il est possible, en jouant sur le pH, d’améliorer les séparations et de recycler le tensioactif après désextraction des solutés. Les cinétiques d’extraction, de séparation et de clarification ont été aussi étudiées pour une meilleure compréhension de ces systèmes. Enfin, l’extraction continue du phénol à partir du mélange eau/4%Simulsol NW342/0,2%phénol (mass.) a été testée sur deux appareillages (extracteur centrifuge et mélangeurdécanteur)thermostatés. Dans un procédé multi-étagé à courants croisés sur un mélangeur-décanteur, on arrive à réduire la concentration du phénol à moins de 0,3ppm (concentration limite selon la législation) après six étages. / Above a certain temperature called cloud point (Tc), aqueous solutions of most nonionic polyethoxylated surfactants separate into two liquid phases in equilibrium: the dilute phase and the coacervate. Thanks to the micellar solubilization of hydrophobic, amphiphilic or even ionic compounds and their concentration in the low volume of coacervate, two-aqueous phase extraction (cloud-point or coacervate extraction) can be performed and applied to the removal of pollutants from aqueous industrial effluents or to the concentration or even separation of high added-value chemicals. Cloud point extraction (CPE) is a relatively simple and ecologically-safe technique for the removal of toxic materials from the environment; this process has proved efficient in treating water for various contaminants including dissolved or dispersed organic and inorganic chemicals. The first part of this thesis consists of recalling some notions on industrial wastewater, some generalities about surfactants (TA) and liquid-liquid extraction, followed by a description of all the reagents, materials and methods used in this work as a preliminary study of a coacervate extraction process. Some surface thermodynamic (adsorption) and association (micellization) properties of two industrial nonionic surfactants (Simulsol NW342 and Tergitol 15-S-7) were determined. The cloud point curves of water /TA binary systems are drawn and the effect of various additives (salt, organic compounds, ionic surfactants) on the cloud point is studied. The isothermal diagram of a water/TA/phenol ternary system is drawn. An application of the Flory-Huggins-Rupert model for the prediction of cloud point curves of nonionic surfactants is discussed. Single contact extraction, from model solutions, uses biodegradable polyethoxylated nonionic surfactants (Simulsol NW342 and Tergitol 15-S-7) for dissolved organic pollutants (phenol, 1-phenylethanol and benzyl alcohol) and mixed micelles of nonionic (Simulsol NW342) and ionic (SDS, CTAB) surfactants for soluble electolytes (lead (II), molybdenum (VI)). We search for the best compromise between the percentage of solute extracted (E%), the coacervate volume fraction (фc) and the percentages of solute and surfactant remaining in the dilute phase (Xs,d and XTA,d), These experimental results are subject to an empirical smoothing through a Scheffé-type experimental design, and an empirical curve fitting procedure. The results are very promising, due to the percentage of solute extracted, which varies between 60 and 95% for organic solutes and from 40 to 85% for electrolytes, the best performances being obtained for phenol and lead. On the other hand, it is possible, by adjusting pH, to improve the separation and recycle the surfactant after back-extraction. The kinetics of extraction yield and phase separation and clarification were also investigated for a better understanding of these systems. Finally, the continuous extraction of phenol from a model solution (water/4wt.% Simulsol NW342/0.2wt.% phenol) on two thermostated equipments (a centrifugal extractor and a mixer-settler) was attempted. In a multi-stage process on a cross-current mixer-settler, the concentration of residual phenol in the dilute phase could be reduced to less than 0.3 ppm (concentration allowed by standard European regulations) after six stages.

Made available in DSpace on 2014-12-17T15:01:42Z (GMT). No. of bitstreams: 1 WillaciEFJ.pdf: 1499759 bytes, checksum: 03aff567e782194c97d56cdcac63888c (MD5) Previous issue date: 2006-12-19 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The aim of this work is to use a new technology in the treatment of produced wastewaters from oil industry. An unit for treat produced waters called UTMDIF, was designed, installed and operated in an industrial plant for treatment of effluents from oil industry. This unit operates by means of the method of separation of phase inversion and can become a promising alternative to solve the problem of oil/water separation. This method constitutes the basis of the working of a new design of mixersettler of vertical configuration which occupies small surface area. The last characteristic becomes specially important when there is limitation on the lay-out of the plant, for example, over maritime platforms to explore oil. This equipment in a semi-industrial scale treats produced wastewaters contaminated with oil at low concentrations (ranging from 30 to 150 mg/L) and throughputs of 320 m3/d (47,4 m3 m-2 h-1). Good results were obtained in oil/water separation which leads to the necessary specification to discharge those wastewaters. Besides, the non dependence of the efficiency of separation in spite of the salinity of the medium becomes the equipment an attractive new technology to treat wastewaters containing oil at low concentrations / Este trabalho tem por objetivo utilizar uma nova tecnologia no tratamento de ?guas produzidas da ind?stria do petr?leo. Uma Unidade de Tratamento de ?guas Produzidas, denominada UT-MDIF, foi projetada, instalada e operou dentro de uma planta industrial de tratamento de efluentes de petr?leo. Esta Unidade de Tratamento piloto utiliza o m?todo de separa??o ? invers?o de fases e pode se tornar numa alternativa promissora para resolver o problema de separa??o ?leo/?gua. Este m?todo constitui a base do funcionamento de um novo modelo de misturador-decantador de configura??o vertical e que ocupa pequena ?rea superficial. Esta ?ltima caracter?stica se torna especialmente importante, quando existe limita??o de espa?o no lay-out da planta industrial, por exemplo, uma plataforma mar?tima para explora??o de petr?leo. Este equipamento em escala semi-industrial trata ?guas produzidas contaminadas com petr?leo em baixas concentra??es da ordem de 30 a 150 mg/L e vaz?es efetivas de 320 m3/d (47,4m3m-2h-1). Os bons resultados na separa??o ?leo/?gua, obtendo-se a especifica??o necess?ria para descarte, associado ? n?o depend?ncia da efici?ncia de separa??o face ? salinidade do meio, podem tornar o equipamento uma nova tecnologia no tratamento de ?guas contaminadas com ?leo a baixas concentra??es

Made available in DSpace on 2014-12-17T15:01:52Z (GMT). No. of bitstreams: 1 NorbertoAM_TESE.pdf: 2336588 bytes, checksum: 940ad1b0befe8c431d2e9fb731a885b6 (MD5) Previous issue date: 2011-09-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This work aims to determine a better methodology to help predicting some operational parameters to a new design of mixer-settler on treating wastewater produced by petroleum industry, called MDIF (Misturador-Decantador ? Invers?o de Fases/ Mixer-Settler based on Phase Inversion MSPI). The data from this research were obtained from the wastewater treatment unit, called MSPI-TU, installed on a wastewater treatment plant (WTP) of PETROBRAS/UO-RNCE. The importance in determining the better methodology to predict the results of separation and extraction efficiency of the equipment, contributes significantly to determine the optimum operating variables for the control of the unit. The study was based on a comparison among the experimental efficiency (E) obtained by operating MSPI-TU, the efficiency obtained by experimental design equation (Eplan) from the software Statistica Experimental Design? (version 7.0), and the other obtained from a modeling equation based on a dimensional analysis (Ecalc). The results shows that the experimental design equation gives a good prediction of the unit efficiencies with better data reliability, regarding to the condition before a run operation. The average deviation between the proposed by statistic planning model equation and experimental data was 0.13%. On the other hand, the efficiency calculated by the equation which represents the dimensional analysis, may result on important relative deviations (up 70%). Thus, the experimental design is confirmed as a reliable tool, with regard the experimental data processing of the MSPI-TU / Este trabalho objetiva determinar a melhor metodologia para auxiliar na predi??o de vari?veis operacionais de um novo design de misturador-decantador aplicado ao tratamento de ?guas produzidas da ind?stria do petr?leo, que vem sendo denominado de MDIF (Misturador-Decantador ? Invers?o de Fases). Os dados utilizados neste estudo foram obtidos da Unidade de Tratamento de ?guas produzidas, denominada de UT-MDIF, que se encontra instalada em uma das esta??es de tratamento de efluentes (ETE) da PETROBRAS/UORNCE. A import?ncia em determinar a melhor metodologia que permita a predi??o dos resultados das efici?ncias de separa??o e extra??o do equipamento, contribui de forma significativa para otimiza??o das vari?veis operacionais para o controle da unidade. O estudo se baseou na compara??o dos resultados das efici?ncias experimentais (E) obtidas pela UTMDIF, com os resultados das efici?ncias obtidas pela equa??o do modelo do planejamento estat?stico (Eplan), gerado pelo programa Statistica Experimental Design? (vers?o 7.0), e com a utiliza??o de uma equa??o utilizando modelagem com base em an?lise dimensional (Ecalc). Os resultados mostram que a equa??o decorrente do planejamento estat?stico ? capaz de predizer, com boa aproxima??o, os resultados de efici?ncia a serem obtidos com a unidade, possibilitando uma melhor confiabilidade dos dados, no que se refere ? condi??o que antecede uma corrida operacional. O desvio m?dio entre a equa??o proposta e os dados experimentais ? de 0,13%. Por outro lado, a efici?ncia calculada pela equa??o da an?lise dimensional pode apresentar desvios relativos importantes (at? 70%). Desta forma, o planejamento estat?stico experimental se confirma como sendo uma ferramenta confi?vel, no que se refere ao tratamento dos dados experimentais da UT-MDIF