This work is focused on thermodynamic modelling of isobaric vapour-liquid-liquid equilibrium (VLLE) (homogeneous) and (heterogeneous) for binary, ternary and quaternary systems. This work uses data for organic/aqueous systems; historically these mixtures were used in the production of penicillin and were required to be separated by continuous fractional distillation. Modelling of the separation required phase equilibrium data to be available so that predictions could be made for equilibrium stage temperatures, vapour compositions, liquid compositions and any phase splitting occurring in the liquid phase. Relevant data became available in the literature and work has been carried out to use relevant theories in correlating and predicting as was originally required in the distillation equilibrium stage modelling. All the modelling carried out was at atmospheric pressure. The modelling has been done using an Equation of State, specifically Peng Robinson Styrjek Vera (PRSV), combined with the activity coefficient model UNIversal QUAsi Chemical (UNIQUAC) through Wong Sandler mixing rules (WSMR). The success of all correlations and predictions was justified by minimizing the value of the Absolute Average Deviation (AAD) as defined within the thesis. Initially the integral Area Method and a method called Tangent Plane Intersection (TPI) were used in the prediction of liquid-liquid equilibrium (LLE) binary systems. This work used a modified 2-point search, suggested a 3-point search and has successfully applied both of these methods to predict VLLE for binary systems. It was discovered through the application of the TPI on ternary VLLE systems that the method was strongly sensitive to initial values. This work suggested and tested a Systematic Initial Generator (SIG) to provide the TPI method with realistic initial values close to the real solution and has demonstrated the viability of the SIG on improving the accuracy of the TPI results for the ternary systems investigated. In parallel with the TPI another method the Tangent Plane Distance Function (TPDF) was also investigated. This method is based on the minimisation of Gibbs free energy function related to the Gibbs energy surface. This method consistently showed it was capable of predicting VLLE for both ternary and quaternary systems as demonstrated throughout this work. The TPDF method was found to be computationally faster and less sensitive to the initial values. Some of the methods investigated in this work were also found to be applicable as phase predictors and it was discovered that the TPDF and the SIG methods were successful in predicting the phase regions; however the TPI method failed in identifying the 2 phase region. Applying the techniques described to newly available quaternary data has identified the strengths and weaknesses of the methods. This work has expanded the existing knowledge and developed a reliable model for design, operation and optimisation of the phase equilibria required for prediction in many separation processes. Currently available modelling simulation packages are variable in their predictions and sometimes yield unsatisfactory predictions. Many of the current uses of VLLE models are particularly focused on Hydrocarbon/Water systems at high pressure. The work described in this thesis has demonstrated that an EOS with suitable mixing rules can model and predict data for polar organic liquids at atmospheric and below atmospheric pressure and offers the advantage of using the same modelling equations for both phases.

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No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_EquilibrioLiquidoLiquido.pdf: 2090840 bytes, checksum: 6f929fc002ac92d312bfb025305763e1 (MD5) Previous issue date: 2013 / O biodiesel é definido como sendo uma mistura de monoésteres de ácidos graxos derivados de gorduras animal ou óleos vegetais, obtido por meio do processo de transesterificação com alcoóis de cadeia curta. Durante a sua produção é utilizada uma quantidade em excesso de álcool e um catalisador para favorecer a reação de formação dos ésteres; desta forma a corrente de saída do reator contém o catalisador, o álcool que não reagiu e os produtos da transesterificação, biodiesel e glicerina, formando um sistema bifásico; dependendo do grau de solubilidade desses compostos, pode haver quantidades de biodiesel na fase rica em glicerina e quantidades de glicerina na fase rica em biodiesel. Durante o processo de purificação do biodiesel é necessário executar uma lavagem com água, para promover a retirada do catalisador e impurezas do produto de interesse. Devido à quantidade de compostos envolvidos na produção e purificação é essencial conhecer os dados de equilíbrio líquido-líquido para poder predizer as proporções em que os compostos coexistem e, posteriormente, proceder com a purificação sob condições adequadas para obtenção do biodiesel com maior rendimento e auxiliar no projeto do reator e sistemas de separação. Os objetivos desse trabalho foram produzir o biodiesel a partir de uma planta oleaginosa nativa da região, a castanha do Brasil (Bertholletia excelsa H. B. K.) e, determinar dados de equilíbrio líquido-líquido (ELL) para os sistemas ternários: biodiesel de castanha do Brasil + metanol + glicerina e biodiesel de castanha do Brasil + metanol + água nas temperaturas de 30°C e 50°C. O biodiesel produzido foi inicialmente caracterizado segundo as normas da Agência Nacional de Petróleo (ANP) utilizando métodos físico-químicos. Os dados obtidos foram posteriormente correlacionados com os modelos termodinâmicos NRTL e UNIQUAC para o calculo do coeficiente de atividade de cada componente na fase liquida, com estimativa de novos parâmetros de interação energética. Os resultados obtidos com a modelagem foram satisfatórios, e foi observado que o modelo NRTL representou melhor os dados experimentais. / Biodiesel is defined as being a mixture of fatty esters derived of animal fats or vegetable oils, obtained through the process of transesterification with short chain alcohols. During the production is used a quantity in excess of alcohol and a catalyst to propitiate the formation reaction of esters; in this way the output flow of the reactor contains the catalyst, the unreacted alcohol and products obtained by transesterification, biodiesel and glycerin, forming a biphasic system; depending on the solubility of these compounds, will may there be amounts of biodiesel and glycerin-rich phase and quantities of glycerin in biodiesel-rich phase. During the process of purification of biodiesel it is necessary to accomplish a washing with water, to promote removal of the catalyst and impurities of the product of interest. Due to the amount of compounds involved in the production and purification is essential to know the liquid-liquid equilibrium data in order to predict the proportions in which the compounds coexist and subsequently, to proceed with purification under suitable conditions for obtaining biodiesel with greatest efficiency and to assist in the design of the reactor and tanks. The objectives of this work were to produce biodiesel from oleaginous plants native to the region, the Brazil nut (Bertholletia excelsa H. B. K.) and to establish liquid-liquid equilibrium data (ELL) to ternary systems: biodiesel of Brazil nut + methanol + glycerin and biodiesel of Brazil nut + methanol + water at temperatures of 30° C and 50° C. The biodiesel produced was initially characterized in accordance with the standards of the National Petroleum Agency (ANP) using physicochemical methods. The data obtained were afterward correlated with NRTL and UNIQUAC thermodynamic models for the calculation of the coefficient of activity of each component in the liquid phase, with new energetic interaction parameters obtained. The results obtained from the modeling were satisfactory, and was observed that the NRTL model represented better the experimental data.

Orientador: Martin Aznar / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-05T17:10:49Z (GMT). No. of bitstreams: 1 Maduro_RaquelMoreira_M.pdf: 680083 bytes, checksum: 5d31fee10f51a9386d8fdf5c4d9bcff6 (MD5) Previous issue date: 2005 / Resumo: A principal fonte do alcalóide nicotina (C10H14N2) é o tabaco (Nicotiana Tabacum), matéria-prima fundamental na indústria do fumo para a fabricação de cigarros. Este processo produz como resíduo uma solução aquosa extremamente rica em nicotina e altamente tóxica, que pode ser tratada por meio da extração líquida da nicotina usando um agente extratante. Sendo assim, o principal objetivo desta dissertação foi determinar dados de equilíbrio líquido-líquido para sistemas ternários do tipo nicotina + água + extratante. Os extratantes utilizados foram ciclohexano e 1-butanol, e os dados foram coletados a três temperaturas, 25, 30 e 40 °C. Os experimentos foram realizados em células de equilíbrio, feitas de vidro, mantendo a temperatura do sistema constante. A nicotina foi analisada por espectrofotometria de ultravioleta-visível a 259 nm, a água por titulação potenciométrica de Karl Fischer, e o extratante por diferença. Primeiramente, através do planejamento fatorial 22, foi determinado o tempo ótimo de agitação (2:36 h) e de repouso (20 h), na faixa experimental estudada, para atingir o equilíbrio. Estes tempos foram utilizados para validação da metodologia e para determinação de novos dados para os sistemas em estudo. A validação da metodologia foi realizada reproduzindo seis linhas de amarração do sistema ternário nicotina + água + extratante reportados por García et al. (2000); os resultados indicaram que os dados reportados por estes autores não constituíam um verdadeiro equilíbrio termodinâmico. Analisando os novos dados, observou-se um aumento da região de miscibilidade parcial do 1-butanol para o ciclohexano, mostrando que este último era um melhor extratante. Além disso, pôde-se comprovar que, no caso do ciclohexano, à medida que aumenta a temperatura, a região bifásica também aumenta. Posteriormente, os dados experimentais foram correlacionados através dos modelos moleculares NRTL e UNIQUAC para o cálculo do coeficiente de atividade, com estimativa de novos parâmetros de interação energética. Os resultados foram considerados satisfatórios, observando-se que o modelo NRTL foi capaz de representar melhor os dados de equilíbrio dos sistemas estudados. Palavras-chave: Equilíbrio líquido-líquido, Nicotina, NRTL, UNIQUAC e Planejamento Fatorial / Abstract: The main source of alkaloid nicotine (C10H14N2) is the tobacco (Nicotiana Tabacum), basic raw material in tobacco industry for cigarette manufacture. This process yields, as a residue, an aqueous solution extremely rich in nicotine and highly toxic that can be treated by liquid extraction using an extratante. Therefore, the main objective of this work was to determine liquid-liquid equilibrium data for ternary systems of the type nicotine + water + solvents. The solvents were ciclohexane and 1-butanol, and the data were collected at three temperatures, 25, 30 and 40 °C. The experiments were carried out in glass equilibrium cells, at constant temperature. The nicotine was analyzed by UV-VIS spectrofotometry at 259 nm, the water by Karl Fischer titration, and the solvents by difference. Firstly, through factorial design 22, the optimum agitation time (2:36 h) and rest (20 h) were determined, in the experimental range studied, to reach the equilibrium. These times were used for validation of the methodology and determination of new data for the systems in study. The validation of the methodology was carried out reproducing six tie-lines of the ternary system nicotine + water + solvent, reported for García et al. (2000); the results indicate that the data reported for these authors do not constitute a true thermodynamic equilibrium. Analyzing the new data, an increasing of the region of partial miscibilidade from 1-butanol to ciclohexane was observed, showing that latter is a better solvent. Moreover, it can be proven that, in the case of ciclohexane, as the temperature increases, the two-phase region also increases. Later, the experimental data were correlated through molecular models NRTL and UNIQUAC for the calculation of the activity coefficient, with estimation of new parameters of interaction energy. The results were considered satisfactory, observing that NRTL was capable to represent better the equilibrium data of the studied systems / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Répondant à une forte demande de sécurité, d’économie de poids et d’optimisation du volume utile, les réservoirs pour carburants sont actuellement généralement constitués d’une paroi barrière polymère multicouche visant à limiter les émissions de vapeurs dans l’atmosphère. Etre capable de prédire les perméabilités est primordial pour l’optimisation de telles structures. Grâce à des automates conçus au laboratoire, les mesures de sorption et de perméabilité ont été réalisées pour trois polymères leaders du domaine (PEHD, Liant et EVOH) et des mélanges modèles de carburants composés d’éthanol, d’iso-octane et de toluène. Les propriétés de sorption ont été modélisées par UNIQUAC et un nouveau modèle inédit SORPFIT. Les paramètres des lois de diffusion, de type TSVF2 ou Long généralisé, ont aussi été optimisés pour chaque polymère malgré une difficulté particulière pour l’EVOH. Une méthodologie originale a été ensuite proposée pour la prédiction des flux partiels des multicouches à partir des paramètres caractéristiques des monocouches correspondantes. Selon la nature et la disposition de chaque couche, deux cas de figures ont été identifiés : la limitation cinétique et la limitation thermodynamique du transfert, cette dernière étant estimée à partir des modèles de sorption initialement optimisés. La confrontation des calculs avec les mesures expérimentales réalisées pour des films bicouches et tricouches d’Arkema montre des prédictions très satisfaisantes. Cette approche est finalement étendue à la simulation de la perméabilité de structures multicouches plus complexes et plus représentatives des réservoirs pour carburants industriels / Responding to a strong demand for security, weight reduction and volume optimization, the fuel tanks are currently usually made of polymer multi-layer barriers in order to limit vapour emissions into the atmosphere. The prediction of their permeability remains a world-wide critical challenge for the multi-layer optimization. Thanks to original semi-automated experimental set-ups, sorption and permeability measurements were carried out for three leading polymer materials (HDPE, EVOH and Binder) and model fuel mixtures of ethanol, iso-octane and toluene. The modelling of the sorption properties was successfully achieved by the UNIQUAC model and a new model called SORPFIT. The parameters of the diffusion laws according to the TSVF2 or the generalized Long models were also optimized for each polymer despite some difficulty with EVOH. An original methodology was then proposed for predicting the partial fluxes of polymer multi-layers from the characteristic parameters of the corresponding mono-layers. Depending on the nature and disposition of each layer, two scenarios were identified: the kinetics limitation and the thermodynamics limitation of mass transfer, the latter being estimated from the sorption models initially optimized. The comparison of the calculated fluxes with the experimental data obtained for bi-layer and tri-layer films provided by the world-wide industrial company Arkema showed that the predictions were very satisfying. This approach was then extended to the simulation of the permeability of more complex multi-layer structures which are more representative of commercial fuel tanks

Die experimentelle Charakterisierung von Phasengleichgewichten (Flüssigkeit-Dampf und Flüssigkeit-Flüssigkeit) erfolgte in binären und ternären Systemen aus aromatischen bzw. aliphatischen Kohlenwasserstoffen, Phenolen und Wasser. Die Trübungstitration diente der Bestimmung von Flüssigkeit-Flüssigkeit-Gleichgewichten, auftretende koexistierende flüssige Phasen wurden analytisch charakterisiert. Mit Hilfe der dynamischen Methode erfolgte die Bestimmung der Flüssigkeit-Dampf-Gleichgewichte. Die Modellierung der binären Systeme und die Vorausberechnung der ternären Systeme erfolgten mit den Aktivitätskoeffizientenmodellen NRTL und UNIQUAC. Weiterhin wurden die Berechnungen mit der von Elliott, Suresh und Donohue entwickelten Zustandsgleichung (ESD) durchgeführt, welche einen die assoziierenden Wechselwirkungen berücksichtigenden Term beinhaltet. Ferner wurden mit der Gruppenbeitragsmethode UNIFAC die untersuchten binären und ternären Systeme vorausberechnet. Beide Aktivitätskoeffizientenmodelle können bei der simultanen Modellierung der verfügbaren Phasengleichgewichtsdaten für nahezu alle betrachteten binären Systeme mit sehr guten Ergebnissen überzeugen. Bei der Modellierung mit der Zustandsgleichung ESD müssen deutlich höhere Abweichungen akzeptiert werden. Die Ergebnisse der Modellierung der binären Systeme lassen sich nicht adäquat auf die Vorausberechnung der ternären Systeme übertragen. UNIQUAC Modell und Zustandsgleichung ESD zeigen im Mittel die geringsten Unterschiede zwischen vorausberechneten und experimentellen Phasengleichgewichten. Deutlich höhere Abweichungen treten im Mittel bei Verwendung des NRTL Modells bzw. der Gruppenbeitragsmethode UNIFAC auf. Die Annahme, mit Hilfe der expliziten Berücksichtigung der Assoziation mit Zustandsgleichung ESD eine deutliche Verbesserung bei der Vorausberechnung entsprechender Phasengleichgewichten zu erzielen, konnte lediglich für Flüssigkeit-Flüssigkeit-Gleichgewichte in Systemen mit aliphatischen Kohlenwasserstoffen bestätigt werden. / The experimental characterizations of phase equilibria (vapor-liquid and liquid-liquid) were determined in binary and ternary systems containing aliphatic and aromatic hydrocarbons, phenols and water. Liquid-liquid equilibria were measured by turbidity titration. The compositions of coexisting phases were determined with analytic methods. The vapor-liquid equilibria were determined by the dynamic method. The correlation of the binary systems and the prediction of the ternary systems were performed with the activity coefficient models NRTL and UNIQUAC. Furthermore the calculations were realized with an equation of state (ESD) developed by Elliott, Suresh and Donohue, which contain a term for association. Additional predictions of investigated binary and ternary systems were performed with the group contribution method UNIFAC. Both activity coefficient models convinced with satisfactory results by the simultaneously correlation of the available equilibria data for almost all investigated binary systems. The correlations with the ESD equation of state were performed with higher deviations. A transfer of the results of the binary correlations into the ternary predictions is not possible. The UNIQUAC model and the ESD equation of state performed on average with minor deviations between predicted and experimental phase equilibria. Higher deviations were calculated using the NRTL model respectively the group contribution method UNIFAC. Only liquid-liquid equilibria in systems contain aliphatic hydrocarbons indicates improved prediction results based on the consideration of the association.

Made available in DSpace on 2014-12-17T15:01:56Z (GMT). No. of bitstreams: 1 AlessandroALA_TESE.pdf: 2166690 bytes, checksum: 87b921d322f56a3c11d668a0ad8d9341 (MD5) Previous issue date: 2013-11-11 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The nonionic surfactants when in aqueous solution, have the property of separating into two phases, one called diluted phase, with low concentration of surfactant, and the other one rich in surfactants called coacervate. The application of this kind of surfactant in extraction processes from aqueous solutions has been increasing over time, which implies the need for knowledge of the thermodynamic properties of these surfactants. In this study were determined the cloud point of polyethoxylated surfactants from nonilphenolpolietoxylated family (9,5 , 10 , 11, 12 and 13), the family from octilphenolpolietoxylated (10 e 11) and polyethoxylated lauryl alcohol (6 , 7, 8 and 9) varying the degree of ethoxylation. The method used to determine the cloud point was the observation of the turbidity of the solution heating to a ramp of 0.1 ? C / minute and for the pressure studies was used a cell high-pressure maximum ( 300 bar). Through the experimental data of the studied surfactants were used to the Flory - Huggins models, UNIQUAC and NRTL to describe the curves of cloud point, and it was studied the influence of NaCl concentration and pressure of the systems in the cloud point. This last parameter is important for the processes of oil recovery in which surfactant in solution are used in high pressures. While the effect of NaCl allows obtaining cloud points for temperatures closer to the room temperature, it is possible to use in processes without temperature control. The numerical method used to adjust the parameters was the Levenberg - Marquardt. For the model Flory- Huggins parameter settings were determined as enthalpy of the mixing, mixing entropy and the number of aggregations. For the UNIQUAC and NRTL models were adjusted interaction parameters aij using a quadratic dependence with temperature. The parameters obtained had good adjust to the experimental data RSMD < 0.3 %. The results showed that both, ethoxylation degree and pressure increase the cloudy points, whereas the NaCl decrease / Os tensoativos n?o i?nicos, quando em solu??o aquosa, apresentam a propriedade de separa??o em duas fases, sendo uma denominada de fase dilu?da, baixa concentra??o em tensoativo, e a outra rica em tensoativo denominada de coacervato. A aplica??o deste tipo de tensoativo nos processos de extra??o de solutos de meios aquosos vem aumentando o que implica na necessidade do conhecimento das propriedades termodin?micas desses tensoativos. Neste trabalho foram determinados os pontos de n?voa dos tensoativos polietoxilados, da fam?lia do nonilfenolpolietoxilado variando o grau de etoxila??o (9,5;10;11;12 e 13), da fam?lia do octilfenolpolietoxilado variando o grau de etoxila??o (10 e 11) e do ?lcool laur?lico polietoxilado nos graus de etoxila??o (6;7;8 e 9). O m?todo utilizado para determina??o do ponto de n?voa foi a observa??o do turvamento da solu??o ao aquecer o sistema a uma rampa de 0,1oC/minuto, e no estudo da press?o foi utilizada uma c?lula de alta press?o, m?ximo (300 bar). Atrav?s dos dados experimentais obtidos dos respectivos tensoativos, foram utilizados os modelos de Flory-Huggins, UNIQUAC e NRTL para descrever as curvas do ponto de n?voa dos referidos tensoativos. Foram tamb?m estudados a influ?ncia da concentra??o do NaCl e da press?o no ponto de n?voa. Este ?ltimo par?metro ? importante para os processos de recupera??o avan?ada de petr?leo nos quais os tensoativos em solu??o s?o submetidos a press?es elevadas. Enquanto que o efeito do NaCl permite obter pontos de n?voa a temperaturas mais pr?xima da temperatura ambiente viabilizando sua utiliza??o em processos sem controle de temperatura. O m?todo num?rico utilizado para ajustar os par?metros foi o Levenberg-Marquardt. Para o modelo de Flory-Huggins foram determinados par?metros de ajuste como a entalpia da mistura, entropia da mistura e o n?mero de agrega??o. Para os modelos UNIQUAC e NRTL foram ajustados par?metros de intera??o aij utilizando uma depend?ncia quadr?tica com a temperatura. Os par?metros obtidos tiveram bons ajustes aos dados experimentais com RMSD < 0,3%. Os resultados mostraram que tanto a etoxila??o quanto a press?o aumentam o ponto de n?voa do tensoativo, enquanto que o NaCl diminui

La gazéification de la biomasse par voie thermochimique constitue une ressource en énergie renouvelable ayant un grand potentiel de développement. Parmi les différentes techniques possibles, la voie cogénération Chaleur/bio-SNG (Substitute Natural Gaz) est proche de la maturité technologique. Un des verrous technologique de cette technologie est l’élimination des goudrons contenu dans le gaz issu du gazéifieur. Le présent travail de recherche constitue une contribution à la levée de ce verrou. La technique d’élimination des goudrons par lavage au moyen d’un solvant non miscible à l’eau ayant été sélectionnée pour un pilote de démonstration, le présent travail de recherche s’est principalement focalisé sur l’acquisition de données d’équilibre bi et triphasique des composés modèles des goudrons - eau – solvant de lavage. De telles données sont en effet indispensable pour la mise au point du modèle thermodynamique permettant la modélisation et l’optimisation du lavage. Les analyses des phases liquides en équilibre on été réalisées par CPG-FID ou CPG-SM. Dans certains cas les niveaux de concentration étaient particulièrement faibles. Les concentrations réciproque obtenues et les coefficients de partage qui s’en déduisent vérifie respectivement la corrélation empirique de Hands et la relation de Van’t Hoff. L’équilibre liquide-liquide-vapeur des binaires eau – solvant de lavage ont été étudiés par la méthode statique. Les concentrations des phases en équilibres ont été corrélées par les modèles NRTL et UNIQUAC au moyen du logiciel commercial ‘Simulis Thermodynamic’. Les paramètres d’interaction ainsi ajustés permettent une bonne restitution des données expérimentales. / Gasification of biomass is a promising thermochemical renewable energy resource. Among all biomass conversion processes, gasification by heat cogeneration / bio-SNG (Substitute Natural Gas) is the promising one. But still, one of the deadlocks to be raised is the reduction of the high level of tar present in the product gas. The objective of this work is to perform a data base which will be useful at the operation of tar removal from aqueous medium. The present work has mainly focused on the acquisition of bi and triphasic equilibrium data model molecules of tars - water - washing solvent. Such data are indeed essential for the development of the thermodynamic model for the modeling and the optimization of the washing process. Analyses of liquid phases in equilibrium have been performed by GC-FID or GC-MS. In some cases the concentration levels were particularly low (up to 10-10 mole fraction of anthracene in the aqueous phase). Reciprocal concentrations obtained and the partition coefficients which are deduced from the empirical correlation satisfy each of Hands and the Van't Hoff relationship. Liquid-liquid-vapor equilibrium of binary systems (water-extracting solvent) was studied with the static method. The concentrations of the phases in equilibrium were correlated by the NRTL and UNIQUAC models using the commercial software 'Thermodynamic Simulis'. The interaction parameters adjusted allow a good reproduction of experimental data.

Die experimentelle Charakterisierung von Phasengleichgewichten (Flüssigkeit-Dampf und Flüssigkeit-Flüssigkeit) erfolgte in binären und ternären Systemen aus aromatischen bzw. aliphatischen Kohlenwasserstoffen, Phenolen und Wasser. Die Trübungstitration diente der Bestimmung von Flüssigkeit-Flüssigkeit-Gleichgewichten, auftretende koexistierende flüssige Phasen wurden analytisch charakterisiert. Mit Hilfe der dynamischen Methode erfolgte die Bestimmung der Flüssigkeit-Dampf-Gleichgewichte. Die Modellierung der binären Systeme und die Vorausberechnung der ternären Systeme erfolgten mit den Aktivitätskoeffizientenmodellen NRTL und UNIQUAC. Weiterhin wurden die Berechnungen mit der von Elliott, Suresh und Donohue entwickelten Zustandsgleichung (ESD) durchgeführt, welche einen die assoziierenden Wechselwirkungen berücksichtigenden Term beinhaltet. Ferner wurden mit der Gruppenbeitragsmethode UNIFAC die untersuchten binären und ternären Systeme vorausberechnet. Beide Aktivitätskoeffizientenmodelle können bei der simultanen Modellierung der verfügbaren Phasengleichgewichtsdaten für nahezu alle betrachteten binären Systeme mit sehr guten Ergebnissen überzeugen. Bei der Modellierung mit der Zustandsgleichung ESD müssen deutlich höhere Abweichungen akzeptiert werden. Die Ergebnisse der Modellierung der binären Systeme lassen sich nicht adäquat auf die Vorausberechnung der ternären Systeme übertragen. UNIQUAC Modell und Zustandsgleichung ESD zeigen im Mittel die geringsten Unterschiede zwischen vorausberechneten und experimentellen Phasengleichgewichten. Deutlich höhere Abweichungen treten im Mittel bei Verwendung des NRTL Modells bzw. der Gruppenbeitragsmethode UNIFAC auf. Die Annahme, mit Hilfe der expliziten Berücksichtigung der Assoziation mit Zustandsgleichung ESD eine deutliche Verbesserung bei der Vorausberechnung entsprechender Phasengleichgewichten zu erzielen, konnte lediglich für Flüssigkeit-Flüssigkeit-Gleichgewichte in Systemen mit aliphatischen Kohlenwasserstoffen bestätigt werden. / The experimental characterizations of phase equilibria (vapor-liquid and liquid-liquid) were determined in binary and ternary systems containing aliphatic and aromatic hydrocarbons, phenols and water. Liquid-liquid equilibria were measured by turbidity titration. The compositions of coexisting phases were determined with analytic methods. The vapor-liquid equilibria were determined by the dynamic method. The correlation of the binary systems and the prediction of the ternary systems were performed with the activity coefficient models NRTL and UNIQUAC. Furthermore the calculations were realized with an equation of state (ESD) developed by Elliott, Suresh and Donohue, which contain a term for association. Additional predictions of investigated binary and ternary systems were performed with the group contribution method UNIFAC. Both activity coefficient models convinced with satisfactory results by the simultaneously correlation of the available equilibria data for almost all investigated binary systems. The correlations with the ESD equation of state were performed with higher deviations. A transfer of the results of the binary correlations into the ternary predictions is not possible. The UNIQUAC model and the ESD equation of state performed on average with minor deviations between predicted and experimental phase equilibria. Higher deviations were calculated using the NRTL model respectively the group contribution method UNIFAC. Only liquid-liquid equilibria in systems contain aliphatic hydrocarbons indicates improved prediction results based on the consideration of the association.

Die Phasengleichgewichte (Flüssigkeit-Dampf und Flüssigkeit-Flüssigkeit) der binären, ternären und quaternären Mischungen bestehend aus Wasser, Toluen, Anilin und Cyclohexylamin wurden experimentell bestimmt und modelliert bzw. vorausberechnet. Die Bestimmung der Flüssigkeit-Dampf-Gleichgewichte erfolgte mit Hilfe der dynamischen Methode, die dafür notwendige Mess- und Regeltechnik wurde erweitert und modernisiert. Die Flüssigkeit-Flüssigkeit-Gleichgewichte wurden durch Trübungstitration und Analyse der koexistierenden Phasen bestimmt. Die Beschreibung der binären Systeme und die Vorausberechnung der Mehrkomponentensysteme erfolgte mit den Aktivitätskoeffizientenmodellen UNIQUAC und NRTL und der Zustandsgleichung, entwickelt von Elliott, Suresh und Donohue (ESD). Die ESD-Zustandsgleichung enthält neben einem Attraktions- und einem Repulsionsterm auch einen Term, der assoziative Wechselwirkungen explizit berücksichtigt. Die Beschreibung der binären Systeme gelingt mit den getesteten Modellen sehr gut. Dabei werden mit den Aktivitätskoeffizientenmodellen bessere Ergebnisse erreicht als mit der ESD-Zustandsgleichung. Diese Bild kehrt sich bei der Vorausberechnung der Mehrkomponentensysteme um. Bei Verwendung der NRTL-Gleichung treten deutlich höhere Abweichungen auf als bei Berechnungen mit der ESD-Zustandsgleichung bzw. der UNIQUAC-Gleichung. Die Erwartung durch explizite Berücksichtigung der Assoziation mit der ESD-Zustandsgleichung einen deutlichen Vorteil in der Vorhersage von Phasengleichgewichten in Systemen mit assoziierenden Komponenten zu erhalten konnte in den untersuchten Mischungen nicht eindeutig bestätigt werden. / Phase equilibria (vapor-liquid and liquid-liquid) of binary, ternary and quaternary systems consisting of water, toluene, aniline and cyclohexylamine were determined experimentally and modeled resp. predicted. Vapor-liquid equilibria were determined by the dynamic method, the necessary measuring and control systems were extended and modernized. Liquid-liquid equilibria were investigated by turbidity titration and analyses of coexisting phases. The calculation of the binary systems and the prediction of the multicomponent systems were performed with the activity coefficient models UNIQUAC and NRTL and the equation of state developed by Elliott, Suresh and Donohue (ESD). The ESD equation of state includes beside an attractive and a repulsive term a term for explicit consideration of associative interaction. The description of the binary systems succeeded very well with the tested models. Better results were achieved with the activity coefficient models than with the ESD equation of state. These findings are inversed in the case of prediction of multicomponent phase equilibria. On application of the NRTL equation the deviations are notable greater than with the ESD equation of state or the UNIQUAC equation. The expectation to get a significant advantage in prediction of phase equilibria in systems with associating components with the ESD equation of state could not be answered definitely.

Orientadores: Maria Regina Wolf Maciel, Martin Aznar / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-11T22:03:29Z (GMT). No. of bitstreams: 1 Machado_AlexBarreto_M.pdf: 1251594 bytes, checksum: 12614335c44f56e98288ed9de32033db (MD5) Previous issue date: 2007 / Resumo: Observa-se que, nos últimos anos, a procura por novos processos de separação para a recuperação de ácidos orgânicos, dentre eles o ácido acrílico, a partir de seu caldo de fermentação, tem sido intensa. O processo de extração líquido-líquido apresenta-se como uma alternativa das mais viáveis para sistemas diluídos, quando se utiliza solventes apropriados e de baixa toxicidade. Na parte computacional do trabalho em questão, inicialmente, realizou-se um estudo do software Aspen Plus no que se refere à obtenção de dados termodinâmicos (parâmetros binários) e curvas binodais. Realizou-se, também, a validação do software obtendo regressões de dados experimentais envolvendo fenol e alguns solventes retirados da literatura. Algumas curvas de extração (curvas binodais), testando diferentes solventes para extração do ácido acrílico, foram construídas. As curvas binodais simuladas no Aspen também auxiliaram na escolha dos pontos experimentais, uma vez que, desta maneira, já se conhecia a região de formação de duas fases dos sistemas em estudo e pôde-se orientar a coleta destes dados laboratoriais sem o consumo excessivo de reagentes e de tempo. A parte experimental deste projeto envolve a obtenção de dados de ELL dos sistemas ternários ácido acrílico - água e os seguintes solventes: diisopropil éter, isopropil acetato, 2-etil 1-hexanol, 4- metil 2-pentanona; além do levantamento dos dados de ELL dos sistemas quaternários: ácido acrílico+água+diisopropil éter+sal, usando como sais MgCl2 e CaCl2 de concentrações de 5 e 10%, respectivamente, e ácido acrílico+água+isopropil acetato+sal, usando como sais MgCl2 e CaCl2 de concentrações de 5 e 10% respectivamente. Os resultados encontrados foram muito satisfatórios, permitindo-se construir curvas de solubilidades e realizar as regressões utilizando os modelos de coeficiente de atividade UNIQUAC e NRTL, determinando-se os parâmetros binários. Foram realizadas comparações entre os 4 solventes de extração e entre os sistemas quaternários envolvendo sais. / Abstract: It is observed that, in the last years, the search for new separation processes for recovering organic acids, such as acrylic acid produced from renewable sugar, has been intense. The liquid-liquid extraction process appears as the most viable alternative for diluted systems, since suitable solvents are used. Related to the computational part of this work, initially, a study using the software Aspen Plus for obtaining thermodynamic data (binary parameters) and binodal curves were carried out. Some extraction curves (binodal curves), testing different solvents for acrylic acid extraction, were obtained. Binodal curves simulated with Aspen Plus were very important in choosing experimental points, since, in this way, it was possible to know the region where there are immiscible two phases and, so, to facilitate the obtention of experimental data without excessive consumption of reagents and time. In the experimental section of this work, experimental data of liquid liquid equilibria (LLE) were obtained for the ternary systems acrylic acid + water + solvents (diisopropyl ether, isopropyl acetate, 2-ethyll 1-hexanol, 4 - methyl 2-pentanona), beyond obtain LLE data for the quaternary systems acrylic acid + water + diisopropyl ether + salt (using MgCl2 or CaCl2, with concentrations of 5 and 10%, respectively) and system acrylic acid + water + isopropyl acetate + salt (using MgCl2 and CaCl2 with concentrations of 5 and 10%, respectively). The results obtained were very satisfactory. Experimental solubility curves and regressed curves, using UNIQUAC and NRTL models for the activity coefficient calculations, through the binary parameters, were carried out. The results obtained with four solvents were compared and the ternary and quaternary systems (involving salts) also were compared among themselves. / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química