Modeling and inferential control studies are carried out on a reactive batch distillation system for the esterification reaction of ethanol with acetic acid to produce ethyl acetate. A dynamic model is developed based on a previous study done on a batch distillation column. The column is modified for a reactive system where Artificial Neural Network Estimator is used instead of Extended Kalman Filter for the estimation of compositions of polar compounds for control purposes. The results of the developed dynamic model of the column is verified theoretically with the results of a similar study. Also, in order to check the model experimentally, a lab scale column (40 cm height, 5 cm inner diameter with 8 trays) is used and it is found that experimental data is not in good agreement with the models&rsquo / . Therefore, the model developed is improved by using different rate expressions and thermodynamic models (fi-fi, combination of equations of state (EOS) and excess Gibbs free energy (EOS-Gex), gama-fi) with different equations of states (Peng Robinson (PR) / Peng Robinson - Stryjek-Vera (PRSV)), mixing rules (van der Waals / Huron Vidal (HV) / Huron Vidal Original (HVO) / Orbey Sandler Modification of HVO (HVOS)) and activity coefficient models (NRTL / Wilson / UNIQUAC). The gama-fi method with PR-EOS together with van der Waals mixing rule and NRTL activity coefficient model is selected as the best relationships which fits the experimental data. The thermodynamic models / EOS, mixing rules and activity coefficient models, all are found to have very crucial roles in modeling studies. A nonlinear optimization problem is also carried out to find the optimal operation of the distillation column for an optimal reflux ratio profile where the maximization of the capacity factor is selected as the objective function. In control studies, to operate the distillation system with the optimal reflux ratio profile, a control system is designed with an Artificial Neural Network (ANN) Estimator which is used to predict the product composition values of the system from temperature measurements. The network used is an Elman network with two hidden layers. The performance of the designed network is tested first in open-loop and then in closed-loop in a feedback inferential control algorithm. It is found that, the control of the product compositions with the help of an ANN estimator with error refinement can be done considering optimal reflux ratio profile.

La distillation réactive est l’un des procédés chimiques intensifiés les plus reconnus, qui intègre la séparation et la réaction au sein d’un même appareil. Les principaux avantages de la distillation réactive concerne l’amélioration de la conversion de la réaction, la diminution significative des investissements, des coûts de fonctionnement, de la consommation énergétique, et de la production de sous produits. Une méthodologie de conception systématique, générale et hiérarchisée de la distillation réactive discontinue avec des réactions consécutives est présentée dans ce manuscrit. La méthode élaborée est présentée sur la transestérification du carbonate de diméthyle par le procédé de distillation réactive discontinue dans une colonne avec un bac intermédiaire. Après l’acquisition de données phisicochimiques de base nécessaire à notre méthode, une nouvelle méthode de l’analyse de faisabilité pour les systèmes multiréactifs et multiconstituant a été développée. L’étape suivante est l’analyse de sensibilité afin d’explorer les effets des paramètres du procédé. Une configuration faisable, qui est entièrement réactive avec une alimentation dans la partie supérieure et inférieure de la colonne et avec un bac intermédiaire a été choisie et étudiée au cours de l’analyse de sensibilité par des simulations rigoureuses effectuées en utilisant le logiciel ProSIM Batch. / Reactive distillation, a process integrating separation and reaction in a single unit, is one of the best known intensified chemical processes. Major advantages of reactive distillation include higher conversion, reduced investment, operating costs, energy consumption, and quantity of secondary products. A systematic and hierarchic general methodology for conceptual design of multireactive batch reactive distillation (BRD) is presented in this manuscript. The elaborated method is presented on the transesterification of dimethyl carbonate by the process of batch reactive distillation in a middle vessel column.After collecting the physico-chemical basic data necessary for our method, the new method of feasibility analysis for multicomponent and multireactive systems has been developed. The next step is the sensibility analysis, when the effects of the process parameters are analysed. As a configuration feasible a fully reactive configuration of middle vessel column with entrainer feeding to the upper and lower column sections is studied by simulations using ProSIM Batch.

With ever-growing environmental concerns, petrochemical and fine chemical industries face an omnipresent issue in recovering acetic acid from its aqueous solutions. The recovery of acetic acid through the esterification process is a very viable option. However, esterification reactions are typically restricted by equilibrium limitations, and face challenges with product purification. Reactive distillation is an emerging technology that has an extremely attractive potential as a process alternative for carrying out equilibrium limited chemical reactions. Although the reactive distillation process has been successfully commercialised for the manufacture of hIgh commodity chemicals e.g. methyl tertiary butyl ether (MTBE) and methyl acetate, its potential as a separation tool for the recovery of acetic acid using iso-amyl alcohol has not been exploited.

Batch distillation with chemical reaction when takes place in the same unit is referred to as batch reactive distillation process. The combination reduces the capital and operating costs considerably. Among many different types of batch reactive distillation column configurations, (a) conventional (b) inverted (c) semi-batch columns are considered here. Three reaction schemes such as (a) esterification of methanol (b) esterification of ethanol (c) hydrolysis of methyl lactate are studied here. Four different types of dynamic optimisation problems such as (a) maximum conversion (b) maximum productivity (c) maximum profit and (d) minimum time are formulated in this work. Optimal design and or operation policies are obtained for all the reaction schemes. A detailed rigorous dynamic model consisting of mass, energy balances, chemical reaction and thermodynamic properties is considered for the process. The model was incorporated within the dynamic optimisation problems. Control Vector Parameterisation (CVP) technique was used to convert the dynamic optimisation problem into a nonlinear programming problem which was solved using efficient SQP (Successive Quadratic Programming) method available within the gPROMS (general PROcess Modelling System) software. It is observed that multi-reflux ratio or linear reflux operation always led to better performance in terms of conversion, productivity for all reaction schemes compared to that obtained using single reflux operation. Feed dilution (in the case of ethanol esterification) led to more profit even though productivity was found to be lower. This was due to reduction in feed price because of feed dilution. Semi-batch reactive distillation opertation (for ethanol esterification) led to better conversion compared to conventional batch distillation, however, the total amount of acetic acid (reactant) was greater in semi-batch operation. Optimisation of design and operation (for ethanol esterification) clearly showed that a single cloumn will not lead to profitable operation for all possible product demand profile. Also change in feed and /or product price may lead to adjust the production target to maximise the profitability. In batch distillation, total reflux operation is recommended or observed at the begining of the operation (as is the case for methnaol or ethanol esterification). However, in the case of hydrolysis, total reflux operation was obseved at the end of the operation. This was due to lactic acid (being the heaviest) was withrawn as the final bottom product.

Ces travaux de thèse abordent la problématique du développement d'internes destinés à la distillation réactive. La méthodologie à suivre est appliquée dans le cas des mousses céramiques en Carbure de Silicium. Le comportement hydrodynamique a été étudié ainsi que la capacité en transfert de matière validant la possible application des mousses en tant que garnissage destiné à la distillation. L'activation catalytique du support a ensuite été développée afin de dégager la méthode la plus intéressante permettant d'approcher le garnissage de référence, le KATAPAK, en termes d'activité catalytique. Le greffage d'Amberlyst 15 est alors apparu comme la voie la plus intéressante pour la possible application des mousses greffées comme interne catalytique destiné à la distillation réactive. / This work of thesis approaches the problems of the development of packings intended for reactive distillation. Methodology to be followed is so applied in the case of ceramic foam in Silicon Carbide. The hydrodynamic behaviour was studied as well as the mass transfer efficiency demonstrating the possible application of ceramic foam as a packing for distillation. The aspect of the catalytic activation of the support was then developed in order to determine the most efficiency method in terms of catalytic activity making it possible to approach reference packing, the KATAPAK. The coating of Amberlyst 15 then appeared as the most interesting way for the possible application of coating foam as catalytic packing for reactive distillation.

La distillation réactive est un exemple emblématique de l’intensification de procédés. Cependant, le couplage réaction/séparation génère des complexités importantes en termes de dynamique, de contrôle et de supervision qui constituent une barrière pour leur mise en œuvre industrielle. Ces aspects doivent être considérés dès la phase de conception sous peine de concevoir une colonne difficilement contrôlable. Une méthodologie existante est étendue afin d’y intégrer les aspects de contrôlabilité et de diagnosticabilité. L’étape de conception étudie les courbes de résidu et extractives réactives, identifie les paramètres opérationnels et propose des configurations de colonne respectant les spécifications. La meilleure configuration est choisie sur des critères de contrôlabilité par l’analyse de différents indicateurs quantitatifs et qualitatifs identifiés à l’aide de simulations en régime permanent et dynamique. La méthodologie est appliquée à la production industrielle d’acétate d’éthyle. Deux campagnes expérimentales ont permis de fiabiliser le modèle de simulation de la colonne. La méthodologie permet d’identifier les sensibilités et montre que il est possible d’agir sur les trois degrés de liberté de la colonne double alimentation pour atteindre les spécifications industrielles ; les variables contrôlées sont sélectionnées dans des sections spécifiques, similaires pour différentes configurations de colonne. Concernant le diagnostic, l’utilisation de capteurs de composition semble la plus pertinente mais la complexité de leur utilisation industrielle (cout) peut être contournée par la sélection d’un nombre plus important de capteurs de température judicieusement positionnés. Les résultats de contrôlabilité et de diagnosticabilité sont en cohérence et bien intégrés dans la conception des colonnes réactives. / Reactive distillation involves complexities on process dynamics, control and supervision. This work proposes a methodology integrating controllability and diagnosability as from conceptual design. The choice of the most appropriate feasible configuration is conducted though an indices-based method, regarding steady-state and dynamic simulations, for the ethyl acetate production. Experimental campaigns were performed to acquire reliable models. The methodology highlights the process sensitivities and shows that three degrees of freedom of the double-feed column can be manipulated to ensure the industrial specifications; the controlled variables are selected at similar specific locations for all column configurations. Concerning diagnosis, the use of composition sensors seems to be the most appropriate solution, but the same performances can be reached with more temperature sensors judiciously placed.

Orientador: Maria Regina Wolf Maciel / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T04:13:19Z (GMT). No. of bitstreams: 1 Afonso_AdilsonPires_D.pdf: 2963967 bytes, checksum: 74c2f52074d8664fff323f72dc8f5730 (MD5) Previous issue date: 2005 / Resumo: O processo de separação de misturas homogêneas e não ideais é um problema comum nas indústrias. A separação de misturas complexas pode ser realizada a baixa pressão, para evitar a degradação de componentes sensíveis ou ainda, com a utilização de destilação com reação química para eliminar azeótropos e/ou aumentar a volatilidade relativa dos componentes a serem separados. A destilação reativa é uma técnica utilizada há muitos anos na indústria, porém, somente, recentemente, é que a modelagem matemática do problema permitiu que se desenvolvessem algorítmos para calcular e simular o processo de destilação onde ocorre simultaneamente o equilíbrio líquido-vapor- e o equilíbrio químico. Neste contexto, a destilação reat!va é uma das aplicações industriais mais efetivas para separar misturas complexas, uma vez que é baseada no conceito de reatores multifuncionais, isto é, na combinação de reações químicas com a destilação fracionada em um mesmo equipamento. Neste trabalho de tese, foram estudados os processos de destilação a baixas pressões para separar mono e diglicerídeos de glicerol, ácidos graxos e água, e o de destilação reativa para eliminar o fenol da mistura azeotrópica com água. Neste último, o reagente utilizado foi o anidrido acético com a formação de ácido acético e acetato de fenila. O esquema proposto demonstrou ser uma eficiente alternativa para a descontam inação de águas residuais. O simulador de processo HysysPlant@ foi utilizado para simular as destilações em estado estacionário e os resultados obtidos são inéditos na literatura publicada, contribuindo, portanto, com os desenvolvimentos na área de separação de misturas complexas. Para permitir a simulação da destilação reativa para separação do azeótropo água- fenol com anidrido acéticoé necessário se ter a cinética da reação. Como não existem na literatura dados experimentais deste sistema, neste trabalho foram apresentados alguns métodos para permitir a estimativa da cinética. Além disso, uma análise das misturas azeotrópicas formadas foi também realizada, para permitir a caracterização termodinâmica do sistema e, com isto, propor a separação física dos vários componentes. Este trabalho foi desenvolvido no I:aboratório de Desenvolvimento de Processos de Separação /DPQ/FEQ/UNICAMP / Abstract: The separation process of homogeneous and non ideal mixtures is a common problem in chemical industries. The complex mixture separations may happen at low pressure to prevent thermal degradation or using reactive distillation to eliminate existing azeotropes and/or in order to increase the rei ative volatility of the components to be separated. Reactive distillation has been used in industrial applications for many years ago, but only recently, with the availability of mathematical models, it is possible to develop algorithms in order to calculate and to simulate the distillation process where the vapor-liquid and the chemical equilibria occur simultaneously. So, in this way, reactive distillation is one. of the most effective industrial applications in order to separate complex mixtures, since it is based on the concept of multifunction reactors or, in other words, on the combination of chemical reactors with fractionating distillation in a single equipment. In this work, two important processes were studied. The first one was the separation of mono and diglycerides from glycerol, fatty acids and water using low pressure distillation. The second one was the proposition of a new reaction scheme to carry out the separation of the diluted system composed by phenol and water, using acetic anhydride as reactant forming acetic acid and phenyl acetate as product. The scheme seems to be a simple and efficient alternative to the decontamination of wastewaters. It was necessary, also, to develop methodologies to calculate the reaction kinetic and characterization of the mixtures being studied in the second case. Computational steady state simulations were performed using Hysys.Plant@ commercial simulator. The results obtained are inedit in the published literature, contributing, so, with the developments in co.mplex mixture separations. This work was developed in the Separation Process Development Laboratory, at the School of Chemical Engineering, at UNICAMP / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Made available in DSpace on 2017-07-10T18:08:13Z (GMT). No. of bitstreams: 1 Vilmar Steffen.pdf: 1051925 bytes, checksum: 9d709f48cee722e3da025481c9af852b (MD5) Previous issue date: 2010-02-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Reactive distillation is the combination of chemical reaction and separation by distillation in only one equipment (these processes generally take place separately and in sequence in the industries of chemical processes). The integration of these two operations can increase the global performance of the production line. Thus, becomes necessary a previous study of the possibility to join these processes in a single equipment. The tool to start the study on a new process or the optimization of a process in operation is the modeling and simulation. The mathematical models for reactive distillation columns are constituted of a system of non linear equations. Several algorithms for simulation of distillation columns in steady state with different degrees of precision and consequently of difficulties were developed in the last decades. However, these algorithms don't supply a procedure to obtain the initial guesses, that are fundamental for the convergence of the method used to solve the system of non linear equations. In this work was developed an algorithm for the solution of mathematical model that describes the reactive distillation process in columns that operates in steady state. In the developed algorithm was defined a procedure to obtain reasonable initial guesses that facilitates the convergence of the method. The great majority of methods for simulation of distillation column in stead-state solve all the equations simultaneously by a system of non linear equations solution s method. In this work was developed an algorithm step-by-step, to facilitate it s understanding, where the system of non linear equations solution s method is necessary just for the group of equations that models the chemical reactions, so that, two system of non linear equations solution s methods were used, the method of Broyden (a variation of the Newton-Raphson s method) and the homotopy continuation method (or homotopy). The mathematical model was obtained from mass balances, energy balances, sum equations, phase equilibrium and chemical equilibrium or chemical kinetics. The modeling of phase equilibrium is rigorous by means of the calculation of activity and fugacity coefficients, the modeling of the thermal effects is also rigorous by means of the calculation of the residual and excess enthalpies. The developed algorithm was evaluated from examples of the literature and in all cases the obtained results were similar to those found in the literature. / Destilação reativa é a combinação de reação química e separação por destilação em um único equipamento (geralmente estes processos acontecem separadamente e em seqüência nas indústrias de processos químicos). A integração destas duas operações pode aumentar o desempenho global da linha de produção. Desta forma, torna-se necessário um estudo prévio da possibilidade de se reunir estes processos em um só equipamento. A ferramenta para se iniciar o estudo sobre um novo processo ou a otimização de um processo em operação é a modelagem e simulação. Os modelos matemáticos para a coluna de destilação reativa são constituídos de um sistema de equações não lineares. Vários algoritmos para simulação de colunas de destilação em regime permanente com diferentes graus de precisão e consequentemente de dificuldades foram desenvolvidos nas últimas décadas. Entretanto, estes algoritmos não fornecem um procedimento para a obtenção de estimativas iniciais, que são fundamentais para convergência do método utilizado para resolver o sistema de equações não lineares. Neste trabalho foi desenvolvido um algoritmo para resolução do modelo matemático que descreve o processo de destilação reativa em colunas que operam em regime permanente. No algoritmo desenvolvido definiu-se um procedimento de obtenção de estimativas iniciais razoáveis que facilitem a convergência do método. A grande maioria dos métodos para simulação de coluna de destilação em estado estacionário resolve todas as equações simultaneamente com um método de solução de sistema de equações não lineares. Neste trabalho foi desenvolvido um algoritmo passo-a-passo, para facilitar a compreensão do mesmo, onde o método de solução de sistemas de equações não lineares é necessário apenas para o conjunto de equações que modelam as reações químicas, para tal, foram utilizados dois métodos de solução de sistemas de equações não lineares, o método de Broyden (uma variação do método de Newton-Raphson) e o método da continuação homotópica (ou homotopia). O modelo matemático utilizado foi obtido a partir de balanços de massa, balanços de energia, equações de somatória, equilíbrio de fases e equilíbrio químico ou cinética química. A modelagem do equilíbrio de fases é rigorosa por meio do cálculo de coeficientes de atividade e fugacidade, a modelagem dos efeitos térmicos também é rigorosa por meio do cálculo das entalpias residual e de excesso. O algoritmo desenvolvido foi avaliado a partir de exemplos da literatura e em todos os casos os resultados obtidos foram semelhantes àqueles encontrados na literatura.

Batch distillation with chemical reaction when takes place in the same unit is referred to as batch reactive distillation process. The combination reduces the capital and operating costs considerably. Among many different types of batch reactive distillation column configurations, (a) conventional (b) inverted (c) semi-batch columns are considered here. Three reaction schemes such as (a) esterification of methanol (b) esterification of ethanol (c) hydrolysis of methyl lactate are studied here. Four different types of dynamic optimisation problems such as (a) maximum conversion (b) maximum productivity (c) maximum profit and (d) minimum time are formulated in this work. Optimal design and or operation policies are obtained for all the reaction schemes. A detailed rigorous dynamic model consisting of mass, energy balances, chemical reaction and thermodynamic properties is considered for the process. The model was incorporated within the dynamic optimisation problems. Control Vector Parameterisation (CVP) technique was used to convert the dynamic optimisation problem into a nonlinear programming problem which was solved using efficient SQP (Successive Quadratic Programming) method available within the gPROMS (general PROcess Modelling System) software. It is observed that multi-reflux ratio or linear reflux operation always led to better performance in terms of conversion, productivity for all reaction schemes compared to that obtained using single reflux operation. Feed dilution (in the case of ethanol esterification) led to more profit even though productivity was found to be lower. This was due to reduction in feed price because of feed dilution. Semi-batch reactive distillation opertation (for ethanol esterification) led to better conversion compared to conventional batch distillation, however, the total amount of acetic acid (reactant) was greater in semi-batch operation. Optimisation of design and operation (for ethanol esterification) clearly showed that a single cloumn will not lead to profitable operation for all possible product demand profile. Also change in feed and /or product price may lead to adjust the production target to maximise the profitability. In batch distillation, total reflux operation is recommended or observed at the begining of the operation (as is the case for methnaol or ethanol esterification). However, in the case of hydrolysis, total reflux operation was obseved at the end of the operation. This was due to lactic acid (being the heaviest) was withrawn as the final bottom product. / Libyan Petroleum Institute