Made available in DSpace on 2016-06-02T19:56:55Z (GMT). No. of bitstreams: 1 6081.pdf: 3692615 bytes, checksum: c275b7cf71f1d4575f5deeff0b9c56cc (MD5) Previous issue date: 2014-03-18 / Universidade Federal de Sao Carlos / Ethanol is a renewable fuel produced from biomass. Starting in 1975, Brazil began a national program to promote ethanol production in large scale, the ProAlcool Programme. In the harvest 2012/13 it was produced 23.64 billion of litters of ethanol, from that 9.85 billion was in anhydrous form. The anhydrous ethanol is mainly used as a gasoline additive. This mix reduces the dependence on fossil fuels, improves the engine performance and reduces the emission of toxic gases. Anydrous ethanol can be produced by azeotropic distillation (cyclohexane), by extractive distillation (mono ethylene glycol) or by molecular sieves technology (zeolytes). The objective of this work was the construction and operation of a distillation apparatus (in a bench scale) with the purpose of evaluating the extractive distillation of hydroalcoholic solutions of ethanol employing glycerol as solvent, in substitution of mono ethylene glycol. The substitution is motivated by several factors indicated by the literature like the biodiesel production growth, whose glycerol is a byproduct; the low toxicity; the superior capacity to promote the relative volatility increase of water-ethanol solution; and the inferior energetic consumption. The column was composed by three glass modules with five perforated plates each module. On the top it was used a glass coil condenser. As reboiler it was used a two litters round bottom boiling flask linked to a heating mantle. The feed of ethanol, solvent (glycerol) and the bottom product withdraw was made with pumps. The distillation system was modelled and simulated in the Aspen Plus software using the RadFrac distillation model and NRTL (non-random two-liquid model) thermodynamic model. Four simulations were made for different ethanol feed compositions (25, 35 and 45 wt %). Three simulations were made without the glycerine feed and one with solvent feed and 35% ethanol feed. The distillation column was operated in total reflux with 0.599 L/h ethanol feed flow and 0.341L/h glycerine feed flow. The systems without the solvent reached a mass purity of ethanol of 94.1% in distillate (45% of ethanol feed). The process with the solvent reached a purity of 99.8% in distillate. The four simulated conditions were experimentally evaluated. The experimental results confirmed that the use of glycerine feed promoted an improvement in separation, reaching distillate purity over 99%. Experiments without the glycerine reached compositions around 90%. Murphree efficiencies were determined in all experiments carried out. For the systems without the solvent the obtained efficiencies were: 45% (25% ethanol feed), 30% (35% ethanol feed), 35% (45% ethanol feed). The system with glycerine feed reached 70% efficiency. / O etanol é um combustível renovável que teve sua produção incentivada no Brasil a partir da implantação do Programa Nacional do Álcool em 1975. Na safra 2012/13 foram produzidos 23,64 bilhões de litros, destes 9,85 bilhões em sua forma anidra. Nesta composição é utilizado como aditivo na gasolina (25% em volume) o que contribui para redução da dependência dos combustíveis fósseis, melhora do desempenho dos motores e diminuição na emissão de gases tóxicos. A produção de etanol anidro pode ser realizada pela destilação azeotrópica (cicloexano), extrativa (monoetilenoglicol) ou por meio do emprego da tecnologia das peneiras moleculares (zeólitas). Este trabalho teve como objetivo a construção e operação de um aparelho de destilação (em escala de bancada) com o objetivo de avaliar a destilação extrativa de soluções hidroalcoólicas de etanol empregando glicerol como solvente em substituição ao monoetilenoglicol. Essa substituição é motivada por diversos fatores apontados pela literatura como o crescimento da produção de biodiesel, que possui como subproduto o glicerol; a menor toxicidade do glicerol em relação ao monoetilenoglicol; a maior capacidade em promover o aumento da volatilidade relativa da solução água-etanol; e o menor consumo energético. A coluna de destilação era composta de três módulos de vidro com cinco pratos perfurados em cada módulo. No topo foi utilizado um condensador de vidro tipo serpentina. Como refervedor foi utilizado balão de fundo redondo de dois litros acoplado a uma manta de aquecimento. A alimentação das correntes de etanol, solvente e a retirada do produto de fundo da coluna foram realizadas por bombas. O sistema de destilação foi simulado no aplicativo Aspen Plus utilizando o bloco RadFrac e o modelo termodinâmico NRTL (Non-random two-liquid model). Foram realizadas quatro simulações variando-se a composição de etanol na corrente de alimentação (25%, 35% e 45% m/m). Três simulações foram feitas sem a alimentação de glicerina e uma simulação com alimentação do solvente e alimentação de etanol de 35%. A simulação representou o processo em refluxo total com vazão de alimentação de etanol de 0,599 L/h e alimentação de glicerina com vazão de 0,341 L/h. As simulações mostraram que para os sistemas sem alimentação de glicerina a máxima pureza mássica de etanol obtida no destilado foi de 94,1% (alimentação com 45% de etanol). Para a operação com alimentação do solvente a pureza obtida no destilado atingiu 99,8%. As quatro condições simuladas foram avaliadas experimentalmente. Os resultados experimentais confirmaram que o uso da alimentação de glicerina promoveu uma melhora na separação, obtendo um destilado com pureza mássica de etanol superior a 99%. Os experimentos sem a presença do solvente atingiram concentrações próximas de 90% no destilado. A eficiência de Murphree foi determinada em cada uma das operações. Para os sistemas sem a presença de solvente, as eficiências obtidas foram de 45% (25% de etanol na alimentação), 30% (35% de etanol na alimentação) e 35% (45% de etanol na alimentação). Para o sistema com alimentação de glicerina a eficiência foi de 70%.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-16T18:20:30Z No. of bitstreams: 1 ANGELA LUCÍNIA URTIGA VASCONCELOS - TESE PPGEQ 2015..pdf: 3505212 bytes, checksum: 24fcdf4a2acef884f73f1502723a100d (MD5) / Made available in DSpace on 2018-03-16T18:20:30Z (GMT). No. of bitstreams: 1 ANGELA LUCÍNIA URTIGA VASCONCELOS - TESE PPGEQ 2015..pdf: 3505212 bytes, checksum: 24fcdf4a2acef884f73f1502723a100d (MD5) Previous issue date: 2015-08 / Capes / As operações de processos químicos periodicamente são interrompidas para realização de procedimentos de manutenção preventiva e/ou corretiva nos equipamentos que fazem parte do processo. Após a parada e as etapas do comissionamento dos equipamentos, dá-se início a operação de partida. A operação de partida dos processos químicos, em especial das colunas de destilação, é uma das etapas mais complexas observadas na prática industrial. O procedimento de partida de uma coluna de destilação pode levar desde algumas horas até dias para atingir o estado estacionário. Quanto maior o tempo necessário para que a operação da coluna alcance o regime estacionário, maior será a quantidade de produtos fora de especificação e maior será o consumo de energia, o que eleva os custos da operação. Embora a operação de partida seja uma etapa de extrema importância nas plantas químicas, ainda é pouco o número de pesquisas realizadas com relação a esse tema. Além disso, não foi encontrado na literatura consultada nenhum trabalho sobre a operação de partida dos sistemas de colunas de destilação termicamente acopladas. O sistema estudado consiste de duas colunas de destilação interconectadas por duas correntes, uma corrente no estado vapor e outra no estado líquido, onde uma das colunas é do tipo extrativa, utilizada para a separação da mistura azeotrópica etanol-água, e a outra é uma coluna de recuperação do solvente etilenoglicol. O presente trabalho teve por objetivo o desenvolvimento de procedimento de partida para o sistema de destilação extrativa termicamente acoplado estudado. Foi avaliado o comportamento dinâmico do sistema durante a operação de partida, bem como o efeito da variação do perfil da vazão do vapor de aquecimento no refervedor sobre o tempo total da partida, do efeito da composição da corrente de alimentação da coluna de recuperação sobre o tempo total da partida e do efeito do instante de alimentação do solvente na coluna extrativa sobre o tempo total da partida. A partir dos resultados e das análises realizadas, foi observado que a coluna de recuperação é quem demanda mais tempo para que a operação de partida do sistema seja concluída, logo quanto menor a quantidade de etanol que é alimentada na coluna de recuperação, menor o tempo total da partida do sistema. Foi observado também, que o solvente deve ser alimentado desde o início da operação de partida, pois quanto mais tardia a alimentação do solvente na coluna extrativa, maior é o tempo total da partida. / Preventive and/or corrective maintenance procedures in equipment’s process operations provoke periodically shut down in the plants. After the maintenance and commissioning step conclusions, initiate the equipment’s startup operation. The start-up operation of chemical processes, in particular distillation columns, is one of the most complex operations in industrial practice. The start-up procedure of a distillation column occurs in few hours or can to wait days to reach steady state. The longer the time required for the operation of the column reaches the steady state, the greater the amount of off-spec product and greater energy consumption. Therefore, the starting operation has a significant impact on operating costs. Although the startup operation is a step of great importance in chemical plants, still is little the number of researches performed with respect to this subject. Moreover, the literature focuses on startup conventional distillation columns. To fill this gap, this work focused startup distillation column thermally coupled. The system studied consists of two distillation columns. One of the columns is extractive distillation type used for separating the azeotropic mixture ethanol-water. The other is a solvent recovery column. The two column is interconnected by two streams. A stream is in vapor phase, and the another stream is in liquid phase. The dynamic behavior of the system was evaluated during the startup operation in a reference configuration. Then was studied the effect of varying the heating steam flow profile in the reboiler, the effect of the feed stream composition of the recovery column and the effect of the start solvent feed extraction column in the total startup time. From the results obtained, it was observed that the recovery column is responsible for most of the time required for completion of the starting. The smaller the amount of ethanol fed to the recovery column, the lower the total time of system startup. It was also observed that the solvent should be fed since the beginning of the start-up operation, because the later the feed of the solvent in the extractive column, the greater the total start-up time.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T19:16:15Z No. of bitstreams: 2 GARDÊNIA MARINHO CORDEIRO - TESE PPGEQ 2016..pdf: 4354292 bytes, checksum: 1f9e0bf89dc6a2e1c64d5fa7f2e58a85 (MD5) ANEXO_TESE.pdf: 3069265 bytes, checksum: da63715d85442ba1e5c536dc5ebe121f (MD5) / Made available in DSpace on 2018-03-23T19:16:15Z (GMT). No. of bitstreams: 2 GARDÊNIA MARINHO CORDEIRO - TESE PPGEQ 2016..pdf: 4354292 bytes, checksum: 1f9e0bf89dc6a2e1c64d5fa7f2e58a85 (MD5) ANEXO_TESE.pdf: 3069265 bytes, checksum: da63715d85442ba1e5c536dc5ebe121f (MD5) Previous issue date: 2016-08-29 / Capes / A intensificação de processos através de colunas de parede dividida (DWC) e acoplamento térmico de duas colunas (TCS) são apontadas na literatura consultada como uma das alternativas mais promissoras para redução do consumo energético do processo de destilação. Especificamente ao processo de destilação extrativa, o uso destas configurações ainda é questionável e não consensual quanto ao seu potencial de redução de custos totais. Neste trabalho, a fim de avaliar rigorosamente a viabilidade de configurações TCS, três abordagens de redução de energia (otimização, integração térmica e acoplamento térmico) são analisadas e concatenadas de modo a reduzir o custo anual total (TAC) e consumo específico de energia (SEC). O uso de um procedimento de otimização baseado no teor de solvente, com garantia de solução ótima global foi eficiente na redução desses custos, uma vez que apresentou menores resultados (de SEC e TAC) em comparação com todos os fluxogramas da literatura analisados. A inclusão de uma integração térmica para pré-aquecer a alimentação do azeótropo com a corrente de reciclo mostrou-se competitiva com o uso do acoplamento térmico. Para estender a avaliação em configurações DWC, considerando a equivalência em termos de estágio de equilíbrio com TCS, é proposto uma estratégia sistemática para obtenção de uma configuração DWC otimizada, em termos operacionais e de design. Um comparativo rigoroso entre DWC e CS (também otimizada) foi realizado e demonstrou a influência do número de estágios das colunas no desempenho dessas configurações. Em relação aos custos energéticos, todas as DWC’s mostraram-se favoráveis, entretanto, o percentual de redução de carga térmica depende de qual CS tomou-se como referencial. Os melhores resultados de TAC foram obtidos para colunas com o número de estágios bem distintos em cada lado da parede, entretanto, essas colunas não superaram os sistemas convencionais otimizados. Economicamente, a decisão sobre o tipo de configuração mais viável para uma aplicação industrial pode ser tomada como base nas estratégias apresentadas, observando o trade-off entre a capacidade de redução energética das DWC’s e os custos do processo das configurações otimizadas. / The process intensification through dividing wall column (DWC) and thermal coupling of two columns (TCS) are noted in the literature consulted as one of the most promising alternatives to reduce energy consumption of the distillation process. Specifically by extractive distillation process, the use of these settings is still questionable and nonconsensual as to its potential to reduce total costs. In this work, in order to assess accurately the feasibility of TCS, three approaches of energy reduction (optimization, thermal and thermal coupling integration) are analysed and concatenated in order to reduce the total annual cost (TAC) and specific energy consumption (SEC). The use of an optimization procedure based on the solvent content, with guaranteed global optimal solution was effective in reducing these costs, since presented smaller results (SEC and TAC) compared to all studies of the literature examined. The inclusion of a thermal integration to preheat the azeotrope with the recycle proved to be competitive with the use of thermal coupling. To extend the assessment in DWC, considering the equivalence in terms of stage of equilibrium with TCS, proposed a systematic strategy for obtaining a DWC configuration optimized in terms of design and operational. A strict comparison between DWC and CS (optimized too) was performed and showed the influence of the number of stages of the columns in the performance of these configurations. In relation to energy costs, all the DWC's were favorable, however, the percentage of reduction of thermal load depends on which CS took as a reference. The best TAC’s results were obtained for columns with distinctive number of stages on each side of the wall, however, these columns do not have overcome the conventional systems optimized. Economically, the decision about the type of configuration more viable for an industrial application can be taken as the basis of the presented strategies, noting the trade-off between the ability of energy reduction of DWC's and the costs of the process of the optimized configurations.

La distillation est le procédé de séparation le plus répandu dans l'industrie chimique. Pour la séparation des mélanges azéotropiques, une méthode spéciale de distillation doit être appliquée. Le but de mon travail était d'améliorer la séparation des mélanges azéotropiques par distillation discontinue (DD). Un nouvel algorithme a été présenté pour la détermination de la séquence des produits de DD pour des mélanges multicomposants azéotropiques. Contrairement aux méthodes publiées précédemment, cet algorithme n'a pas besoin des paramètres d'équilibre. Configurations non-conventionnelles de DD ont été étudiées par simulation rigoureuse avec un accent sur l'opération fermée. Nombreux modes d'opération fermés étaient proposés, lesquelles diffèrent en l'opération de réservoir supérieur. Les effets du recyclage des fractions sur un procédé de séparation existant de 6 lots d'un mélange déchet azéotropique ont été étudiés. Les études ont été étendues pour un procédé de distillation extractive discontinue (DED). Un volume minimal de pré-fraction doit être incinéré. Le cas optimal de DED a donné un profit plus grand que celui de DD. DED a été étudié pour la séparation des deux mélanges azéotropiques. La séparation a été infaisable ou le rendement a été bas par DD, mais DED et le procédé hybride ont donné des rendements élevés. Une nouvelle politique de DED a été aussi proposée. Un modèle généralisé de la distillation hétéroazéotropique discontinue avec une rétention variable de décanteur a été développé. Dans une analyse de faisabilité, toutes les politiques opérationnelles possibles ont été identifiées. Ce modèle a été étendu pour la distillation extractive hétérogène discontinue. / Distillation is the most widespread method for separating liquid mixtures. The separation of azeotropic mixtures requires a special distillation method. My aim was to improve the batch distillation separation of azeotropic mixtures. A new algorithm was presented for the determination of product sequences of batch distillation of multicomponent azeotropic mixtures. Non-conventional configurations were studied by simulation with emphasis on closed operation. The effects of off-cut recycle on a six-batch separation process of a waste solvent mixture were also investigated. Batch extractive distillation was studied for the separation of two azeotropic mixtures. A new extractive policy was also proposed. A generalised model of batch heteroazeotropic distillation with variable decanter hold-up was developed. This model was extended for batch heterogeneous extractive distillation.

Nous étudions la distillation extractive continue de mélanges azéotropiques à temperature de bulle minimale avec un entraineur lourd (classe 1.0-1a) avec comme exemples les mélanges acétone-méthanol avec l’eau et DIPE-IPA avec le 2-méthoxyethanol. Le procédé inclut les colonnes de distillation extractive et de régénération de l’entraineur en boucle ouverte et en boucle fermée. Une première stratégie d’optimisation consiste à minimiser la fonction objectif OF en cherchant les valeurs optimales du débit d’entraineur FE, les positions des alimentations en entraineur et en mélange NFE, NFAB, NFReg, les taux de reflux R1, R2 et les débits de distillat de chaque colonne D1, D2. OF décrit la demande en énergie par quantité de distillat et tient compte des différences de prix entre les utilités chaudes et froides et entre les deux produits. La deuxième stratégie est une optimisation multiobjectif qui minimise OF, le coût total annualisé (TAC) et maximise deux nouveaux indicateurs thermodynamiques d’efficacité de séparation extractive totale Eext et par plateau eext. Ils décrivent la capacité de la section extractive à séparer le produit entre le haut et le bas de la section extractive. L’analyse thermodynamique des réseaux de courbes de résidu ternaires RCM et des courbes d’isovolatilité montre l’intérêt de réduire la pression opératoire dans la colonne extractive pour les séparations de mélanges 1.0-1a. Une pression réduite diminue la quantité minimale d’entraineur et accroît la volatilité relative du mélange binaire azéotropique dans la région d’opération de la colonne extractive. Cela permet d’utiliser un taux de reflux plus faible et diminue la demande énergétique. La première stratégie d’optimisation est conduite avec des contraintes sur la pureté des produits avec les algorithmes SQP dans les simulateurs Aspen Plus ou Prosim Plus en boucle ouverte. Les variables continues optimisées sont : R1, R2 et FE (étape 1). Une étude de sensibilité permet de trouver les valeurs de D1, D2 (étape 2) et NFE, NFAB, NFReg (étape 3), tandis l’étape 1 est faite pour chaque jeu de variables discrètes. Enfin le procédé est resimulé en boucle fermée et TAC, Eext et eext sont calculés (étape 4). Les bilans matières expliquent l’interdépendance des débits de distillats et des puretés des produits. Cette optimisation permet de concevoir des procédés avec des gains proches de 20% en énergie et en coût. Les nouveaux procédés montrent une amélioration des indicateurs Eext et eext. Afin d’évaluer l’influence de Eext et eext sur la solution optimale, la seconde optimisation multiobjectif est conduite. L’algorithme génétique est peu sensible à l’initialisation, permet d’optimiser les variables discrètes N1, N2 et utilise directement le shéma de procédé en boucle fermée. L’analyse du front de Pareto des solutions met en évidence l’effet de FE/F et R1 sur TAC et Eext. Il existe un Eext maximum (resp. R1 minimum) pour un R1 donné (resp. Eext). Il existe aussi un indicateur optimal Eext,opt pour le procédé optimal avec le plus faible TAC. Eext,opt ne peut pas être utilisé comme seule fonction objectif d’optimisation mais en complément des autres fonctions OF et TAC. L’analyse des réseaux de profils de composition extractive explique la frontière du front de Pareto et pourquoi Eext augmente lorsque FE diminue et R1 augmente, le tout en lien avec le nombre d’étage. Visant à réduire encore TAC et la demande énergétique nous étudions des procédés avec intégration énergétique double effet (TEHI) ou avec des pompes à chaleur (MHP). En TEHI, un nouveau schéma avec une intégration énergétique partielle PHI réduit le plus la demande énergétique. En MHP, la recompression partielle des vapeurs VRC et bottom flash partiel BF améliorent les performances de 60% et 40% respectivement. Au final, le procédé PHI est le moins coûteux tandis que la recompression totale des vapeurs est la moins énergivore. / We study the continuous extractive distillation of minimum boiling azeotropic mixtures with a heavy entrainer (class 1.0-1a) for the acetone-methanol with water and DIPE-IPA with 2-methoxyethanol systems. The process includes both the extractive and the regeneration columns in open loop flowsheet and closed loop flowsheet where the solvent is recycled to the first column. The first optimization strategy minimizes OF and seeks suitable values of the entrainer flowrate FE, entrainer and azeotrope feed locations NFE, NFAB, NFReg, reflux ratios R1, R2 and both distillates D1, D2. OF describes the energy demand at the reboiler and condenser in both columns per product flow rate. It accounts for the price differences in heating and cooling energy and in product sales. The second strategy relies upon the use of a multi-objective genetic algorithm that minimizes OF, total annualized cost (TAC) and maximizes two novel extractive thermodynamic efficiency indicators: total Eext and per tray eext. They describe the ability of the extractive section to discriminate the product between the top and to bottom of the extractive section. Thermodynamic insight from the analysis of the ternary RCM and isovolatility curves shows the benefit of lowering the operating pressure of the extractive column for 1.0-1a class separations. A lower pressure reduces the minimal amount of entrainer and increases the relative volatility of original azeotropic mixture for the composition in the distillation region where the extractive column operates, leading to the decrease of the minimal reflux ratio and energy consumption. The first optimization strategy is conducted in four steps under distillation purity specifications: Aspen Plus or Prosim Plus simulator built-in SQP method is used for the optimization of the continuous variables: R1, R2 and FE by minimizing OF in open loop flowsheet (step 1). Then, a sensitivity analysis is performed to find optimal values of D1, D2 (step 2) and NFE, NFAB, NFReg (step 3), while step 1 is done for each set of discrete variables. Finally the design is simulated in closed loop flowsheet, and we calculate TAC and Eext and eext (step 4). We also derive from mass balance the non-linear relationships between the two distillates and how they relate product purities and recoveries. The results show that double digit savings can be achieved over designs published in the literature thanks to the improving of Eext and eext. Then, we study the influence of the Eext and eext on the optimal solution, and we run the second multiobjective optimization strategy. The genetic algorithm is usually not sensitive to initialization. It allows finding optimal total tray numbers N1, N2 values and is directly used with the closed loop flow sheet. Within Pareto front, the effects of main variables FE/F and R1 on TAC and Eext are shown. There is a maximum Eext (resp. minimum R1) for a given R1 (resp. Eext). There exists an optimal efficiency indicator Eext,opt which corresponds to the optimal design with the lowest TAC. Eext,opt can be used as a complementary criterion for the evaluation of different designs. Through the analysis of extractive profile map, we explain why Eext increases following the decrease of FE and the increase of R1 and we relate them to the tray numbers. With the sake of further savings of TAC and increase of the environmental performance, double-effect heat integration (TEHI) and mechanical heat pump (MHP) techniques are studied. In TEHI, we propose a novel optimal partial HI process aiming at the most energy saving. In MHP, we propose the partial VRC and partial BF heat pump processes for which the coefficients of performance increase by 60% and 40%. Overall, optimal partial HI process is preferred from the economical view while full VRC is the choice from the environmental perspective.

Made available in DSpace on 2016-06-02T19:56:50Z (GMT). No. of bitstreams: 1 4994.pdf: 4218201 bytes, checksum: 2533718bb0a463f333c6c34f4b0357b9 (MD5) Previous issue date: 2013-02-15 / Universidade Federal de Sao Carlos / An alternative of renewable fuel is the anhydrous ethanol from biomass. Its production has to aim the minimum consumption of hydric and energetic resources. The bottleneck of the process is located in the downstream that requires technological development with thermodynamics reasoning. This master s degree seeks to address this aspect by studying the dehydration of ethanol by extractive distillation making use of liquid solvent glycerol, salts of potassium acetate and calcium chloride, or both kinds of resources. These resources, called separation agents, can "break" the barrier of azeotropy and have advantages such as no top product contamination and lower energy consumption. The rectification column plus the conventional dehydration system are replaced by a single extractive distillation column which is itself the rectification column, adding the separating agents in the reflux stream. The simulation is performed in steady state using a rigorous model for calculating the column. For non-electrolytic systems UNIFAC model was used, and for systems involving electrolytes UNIFAC model with the addition of the Debye-Hückel term and UNIFAC-Dortmund model. Maximum values for the mean of absolute deviations of temperature and of ethanol molar fraction in vapor phase were 5,51 K and 0,0646 respectively. Though, it was observed that the deviations were higher in the region of least ethanol concentration. The simulation of extractive column with glycerol converged generating anhydrous ethanol following the specification, being a proof of the concept that the application of the proposed process was successful. The simulation of the saline extractive distillation presented difficulties of convergence which will need to be studied in future works. / Uma alternativa de combustível renovável é o etanol anidro a partir da biomassa. Sua produção deve visar o consumo mínimo de recursos hídricos e energéticos. O gargalo do processo está localizado no downstream que necessita de desenvolvimento tecnológico com fundamentação da termodinâmica. Este mestrado busca trabalhar neste aspecto estudando a desidratação do etanol pela destilação extrativa fazendo uso do solvente líquido glicerol, dos sais acetato de potássio e cloreto de cálcio, ou de ambos os tipos de recursos. Esses recursos, chamados de agentes de separação, conseguem quebrar a barreira da azeotropia e possuem vantagens como não contaminação do produto de topo e menor consumo de energia. A coluna de retificação mais o sistema de desidratação convencional são substituídos por uma única coluna de destilação extrativa que é a própria coluna de retificação, adicionando os agentes de separação na corrente de refluxo. A simulação é realizada no estado estacionário utilizando modelo rigoroso de cálculo da coluna. Para sistemas não eletrolíticos foi utilizado o modelo UNIFAC, e para sistemas envolvendo eletrólitos os modelos UNIFAC com adição do termo de Debye-Hückel e UNIFAC-Dortmund. Valores máximos para os desvios absolutos médios de temperatura e de fração molar de etanol na fase vapor foram de 5,51 K e 0,0646, respectivamente. Apesar disso, observou-se que os desvios foram maiores na região de menor concentração de etanol. A simulação da coluna extrativa com glicerol convergiu gerando etanol anidro conforme a especificação, mostrando ser uma prova do conceito de que a aplicação do processo proposto foi bem sucedida. A simulação da destilação extrativa salina apresentou dificuldades de convergência que deverão ser estudadas em futuros trabalhos.

Nous étudions la faisabilité du procédé de distillation extractive continue pour séparer des mélanges azéotropiques A-B à température de bulle minimale ou maximale, avec un tiers corps E lourd ou léger. Les mélanges ternaires A-B-E appartiennent aux classes 1.0-1-a et 1.0-2 qui se subdivisent chacune en deux souscas selon la position de la courbe d'univolatilité. La colonne de distillation a trois sections, rectification, extractive, épuisement. Nous établissons les équations décrivant les profiles de composition liquide dans chaque section en fonction des paramètres opératoires: pureté et taux de récupération du distillat, taux de reflux ratio R et rapport des débits d'alimentation FE/F dans le cas d'un tiers corps lourd ; pureté et taux de récupération du produit de pied, taux de rebouillage S et rapport des débits d'alimentation FE/F dans le cas d'un tiers corps léger. Avec un tiers corps lourd alimenté comme liquide bouillant au dessus de l'étage d'alimentation du mélange A-B, nous identifions le distillat atteignable et les plages de valeurs faisables des paramètres R et FE/F à partir du critère général de faisabilité énoncé par Rodriguez-Donis et al. (Ind. Eng. Chem. Res, 2009, 48(7), 3544–3559). Pour la classe 1.0-1a, il existe des rapport FE/F et reflux ratio minimum. Le rapport FE/F est plus important pour le procédé continu que pour le procédé discontinu parce que la faisabilité du procédé continu nécessite que les profils d'épuisement et extractifs s'intersectent. Pour la classe 1.0-2, les deux constituants A et B sont des distillats potentiels, l'un sous réserve que le rapport FE/F reste inférieur à une valeur limite maximale. Le procédé continu exhibe également une valeur minimale de FE/F à un taux de reflux ratio donné, contrairement au procédé discontinu. Avec un tiers corps léger alimenté comme vapeur saturante sous l'étage d'alimentation du mélange A-B, nous identifions le produit de pied atteignable et les plages de valeurs faisables des paramètres S et FE/F à partir du critère général de faisabilité énoncé par Rodriguez-Donis et al. (Ind. Eng. Chem. Res, 2012, 51, 4643–4660). Comparé au cas des tiers corps lourds, le produit principal est obtenu en pied. Autrement, les comportements des classes 1.0-1a et 1.0-2 sont analogues entre les tiers corps léger et lourd. Avec un tiers corps léger, le procédé continu ajoute la contrainte que les profils de rectification et extractifs s'intersectent. La contrainte d'intersection des profils d'épuisement et extractif est partagée par les deux modes opératoires continu et discontinu. Ce travail valide la méthodologie proposée pour évaluer la faisabilité du procédé de distillation extractive continue et permet de comparer les tiers entre eux en termes de taux de reflux ratio minimum et de rapport de débit d'alimentation minimal / We study the continuous extractive distillation of minimum and maximum boiling azeotropic mixtures A-B with a heavy or a light entrainer E, intending to assess its feasibility based on thermodynamic insights. The ternary mixtures belong to the common 1.0-1a and 1.0-2 class ternary diagrams, each with two sub-cases depending on the univolatility line location. The column has three sections, rectifying, extractive and stripping. Differential equations are derived for each section composition, depending on operating parameters: distillate product purity and recovery, reflux ratio R and entrainer – feed flow rate ratio FE/F for the heavy case; bottom product purity and recovery, reboil ratio and entrainer – feed flow rate ratio for the light entrainer case. For the case with a heavy entrainer fed as a boiling liquid above the main feed, the feasible product and operating parameters R and FE/F ranges are assessed under infinite reflux ratio conditions by using the general feasibility criterion enounced by Rodriguez-Donis et al. (Ind. Eng. Chem. Res, 2009, 48(7), 3544–3559). For the 1.0-1a class, there exists a minimum entrainer - feed flow rate ratio to recover the product, and also a minimum reflux ratio. The minimum entrainer - feed flow rate ratio is higher for the continuous process than for the batch because of the additional requirement in continuous mode that the stripping profile intersects with the extractive profile. For the 1.0-2 class both A and B can be distillated. For one of them there exists a maximum entrainer - feed flow rate ratio. The continuous process also has a minimum entrainer - feed flow rate ratio limit for a given feasible reflux ratio. For the case with a light entrainer fed as saturated vapor below the main feed, the feasible product and operating parameters S and FE/F ranges are assessed under infinite reflux ratio conditions by using the general feasibility criterion enounced by Rodriguez-Donis et al. (Ind. Eng. Chem. Res, 2012, 51, 4643–4660), Compared to the heavy entrainer case, the main product is removed from the column bottom. Similar results are obtained for the 1.0-1a and 1.0-2 class mixtures whether the entrainer is light or heavy. With a light entrainer, the batch insight about the process feasibility holds for the stripping and extractive sections. Now, an additional constraint in continuous mode comes from the necessary intersection between the rectifying and the extractive sections. This work validates the proposed methodology for assessing the feasibility of continuous extractive distillation processes and enables to compare entrainers in terms of minimum reflux ratio and minimum entrainer feed flow rate ratio

Made available in DSpace on 2014-12-17T15:01:30Z (GMT). No. of bitstreams: 1 JessicaCSLM_DISSERT.pdf: 2011571 bytes, checksum: 8e087d35d6e4c83d4f7eda24cd8d3e57 (MD5) Previous issue date: 2012-09-21 / Anhydrous ethanol is used in chemical, pharmaceutical and fuel industries. However, current processes for obtaining it involve high cost, high energy demand and use of toxic and pollutant solvents. This problem occurs due to the formation of an azeotropic mixture of ethanol + water, which does not allow the complete separation by conventional methods such as simple distillation. As an alternative to currently used processes, this study proposes the use of ionic liquids as solvents in extractive distillation. These are organic salts which are liquids at low temperatures (under 373,15 K). They exhibit characteristics such as low volatility (almost zero/ low vapor ), thermal stability and low corrosiveness, which make them interesting for applications such as catalysts and as entrainers. In this work, experimental data for the vapor pressure of pure ethanol and water in the pressure range of 20 to 101 kPa were obtained as well as for vapor-liquid equilibrium (VLE) of the system ethanol + water at atmospheric pressure; and equilibrium data of ethanol + water + 2-HDEAA (2- hydroxydiethanolamine acetate) at strategic points in the diagram. The device used for these experiments was the Fischer ebulliometer, together with density measurements to determine phase compositions. The experimental data were consistent with literature data and presented thermodynamic consistency, thus the methodology was properly validated. The results were favorable, with the increase of ethanol concentration in the vapor phase, but the increase was not shown to be pronounced. The predictive model COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient) proposed by Lin & Sandler (2002) was studied for calculations to predict vapor-liquid equilibrium of systems ethanol + water + ionic liquids at atmospheric pressure. This is an alternative for predicting phase equilibrium, especially for substances of recent interest, such as ionic liquids. This is so because no experimental data nor any parameters of functional groups (as in the UNIFAC method) are needed / O etanol anidro tem ampla aplica??o em ind?strias qu?mica, farmac?utica e de combust?veis. No entanto, os processos atuais para a sua obten??o envolvem custo elevado, alta demanda de energia e a utiliza??o de solventes t?xicos e poluentes. Esse problema ocorre devido ? forma??o de aze?tropo na mistura etanol + ?gua, n?o permitindo a separa??o completa por m?todos convencionais tais como destila??o simples. Como uma alternativa aos processos atualmente utilizados, este estudo prop?e a utiliza??o de l?quidos i?nicos como agentes na destila??o extrativa. Trata-se de sais org?nicos l?quidos a baixas temperaturas (abaixo de 373,15 K). Suas caracter?sticas, tais como baixa volatilidade (press?o de vapor muito baixa), estabilidade t?rmica e baixa corrosividade os tornam interessantes para aplica??es como catalisadores e solventes. Neste trabalho, dados experimentais de press?o de vapor de etanol e ?gua puros na faixa de press?o de 20 a 101 kPa, assim como dados de equil?brio l?quido-vapor(ELV) do sistema etanol + ?gua a press?o atmosf?rica, e dados de equil?brio do sistema etanol + ?gua + 2-HDEAA (acetato de 2-hidrodietanolamina) foram obtidos em pontos estrat?gicos do diagrama. O dispositivo usado para esses experimentos foi o ebuliometro de Fischer, juntamente com medidas de densidade para determinar a composi??o das fases. Os dados obtidos apresentaram coer?ncia com dados da literatura e consist?ncia termodin?mica, desta forma, a metodologia foi devidamente validada. Os resultados foram favor?veis, com o aumento da concentra??o de etanol na fase vapor, por?m o aumento n?o demonstrou ser elevado. O modelo preditivo COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient), desenvolvido por Lin e Sandler (2002), foi aplicado para os c?lculos de predi??o de Equil?brio L?quido-Vapor do sistema etanol + ?gua com l?quido i?nico a press?o atmosf?rica. Essa ? uma alternativa para a previs?o do equil?brio de fases, especialmente para subst?ncias de interesse recente, tais como l?quidos i?nicos, uma vez que nem dados experimentais, nem par?metros de grupos funcionais (como no m?todo UNIFAC) s?o necess?rios