Les colonnes à cloison et la distillation réactive présentent de nombreux avantages. Si ces deux concepts sont couplés, cela conduit à un procédé intensifié appelé : colonne à cloison réactive. Ce nouveau procédé intensifié constitue le principal objet d’étude de cette thèse. Dans une première partie, une procédure de design d’une colonne à cloison basée sur le modèle FUGK a été proposée. Dans cette procédure les aspects technologiques et hydrodynamiques sont abordés. Ces paramètres de design obtenus sont ensuite utilisés pour réaliser une simulation rigoureuse et une optimisation de cette colonne en utilisant le logiciel ProSim. Afin de tester cette procédure, des mélanges idéaux et non idéaux ont été utilisés. Il a été montré que cette procédure de design aboutit rapidement aux paramètres de pré design qui permettent d’initialiser de manière satisfaisante la simulation rigoureuse. Dans un second temps, un pilote d’une hauteur de 4m a été conçu, monté et testé au laboratoire. Des résultats expérimentaux ont été obtenus qui valident la procédure sur des mélanges non réactifs en termes de profils de composition et de température ainsi que sur les compositions et les débits de sortie du procédé. Enfin, dans une dernière partie, cette procédure a été adaptée à des mélanges réactifs en combinant les approches de R. Thery et al (2005) et celle de Triantafyllou et al (1992). Ces ultimes développements ont été testés sur la production d’acétate de méthyl par estérification du méthanol par l’acide acétique à la fois d’un de vue expérimental et théorique. / Divided wall column and reactive distillation have many advantages. If a divided wall column and a reactive distillation are integrated, they leads to a higher integrated process is a reactive divided wall column. However reactive divided wall column has still a new research area. First of all, the thesis proposed a procedure for design of divided wall column, which based on the FUGK model. Both technological and hydrodynamic aspects in the divided wall column are considered in the procedure. Design parameters are then provided to the rigorous simulation and optimization in the ProSimplus software. In order to test this procedure, both ideal and non-ideal ternary mixtures are chosen to be separated in a divided wall column. The results show that the procedure can determine parameters quickly in the case studies and can give a good initialization for rigorous simulation. Secondly, a pilot plant has been design, built and operated in our laboratory (LGC, Toulouse, France, 2013). The pilot plant will provide necessary experimental evidence to validate the previous procedure. Ternary mixture and four-component mixture of alcohols have been used in our pilot plant in steady state conditions. The results show that the composition of products, composition and temperature profile along the column are in very good agreement with simulation results. Finally, a conceptual design method for reactive divided wall column is presented. The pre-design method of R. Thery et al., (2005) and a modified shortcut method for reactive divided wall column that is based on the classical shortcut adapted to a non-reactive divided wall column by C. Triantafyllou and R. Smith (1992) are applied. To verify, simulation and experiment are considered. The methodology has been illustrated for the synthesis of Methyl Acetate from Methanol and Acetic Acid.

Implantées depuis plus de dix ans dans l’industrie, l’intérêt des colonnes à cloison n’est aujourd’hui plus à démontrer. Suivant les applications envisagées, elles peuvent permettre d’important gain tant énergétique qu’économique. Cependant leur design est toujours complexe et les méthodes de conception développées ne s’adressent qu’à des applications avec des mélanges proches de l’idéalité. Le développement d’une nouvelle méthode de design d’une colonne à distillation de mélanges non-idéaux applicable aux colonnes à cloison constitue l’objet d’étude de cette thèse. Dans un premier temps, une procédure de faisabilité et de design d’une colonne classique basée sur les feuilles opératoires a été proposée. Les paramètres de design obtenus sont ensuite utilisés comme initialisation d’une simulation rigoureuse conduite au sein du logiciel Prosim Plus. Afin de tester cette procédure, des mélanges idéaux, non-idéaux et azéotropiques ont été utilisés. Il a pu être montré que les paramètres de design obtenus permettent d’accéder à un design plus fiable et plus efficient, aussi bien d’un point de vue énergétique qu’économique, que ceux obtenus par la bien connue méthode shortcut FUGK. Dans un second temps, la procédure a été adaptée aux colonnes à cloison. Les paramètres obtenus ont également servi à initialiser une simulation rigoureuse et la procédure a été testée avec les mêmes mélanges. Il a été mis en évidence que les paramètres de design obtenus permettaient d’obtenir une bonne initialisation de la colonne. Comparée avec une autre méthode développée précédemment par le laboratoire, la procédure développée s’est révélée plus fiable et a permis l’obtention de design plus économique tant du point de vue énergétique qu’en termes d’investissement. Enfin, une phase de validation expérimentale a également été réalisée sur une installation pilote. Dans un premier temps, l’instrumentation et le contrôle de la colonne ont été fortement améliorés. Dans un second temps, des résultats expérimentaux réalisés sur avec un mélange hétéro-azéotropique ont pu valider des simulations en terme de profils de composition et de température interne ainsi que les compositions et les débits de sortie de la colonne. / The constant increase of divided wall columns usage in the industry for more than ten years shows that its benefits are no longer to be demonstrated. Depending on the applications, it can provide significant energy and economic savings. However their design is still complicated and existing design methods are only applicable to ideal mixtures. The development of a new design method for divided wall distillation column for non-ideal and azeotropic mixtures is the subject of this thesis. Firstly, a feasibility and design procedure for classic distillation column based on the operation leaves was proposed. Calculated design parameters are then used to initialize a rigorous simulation run in ProSimPlus© software. The procedure was tested with ideal, non-ideal and azeotropic mixtures. Results show that calculated design parameters provide a more reliable and efficient column design, from an energetic and economic point of view, than those calculated with the well-known FUGK shortcut method. Secondly the procedure was adapted for divided wall column. Compared with a method developed previously in the laboratory, this new methodology is more reliable and provides more energy and cost efficient designs. Finally, an experimental validation work was made on a pilot plant. Firstly, both instrumentation and control was strongly improved. Secondly, experimental results with a hetero-azeotropic mixture were able to validate rigorous simulation in terms of compositions and temperature profiles inside the column as well as outlet compositions and flowrates of the column.

A destilação é um processo de separação com uma alta demanda de energia, razão pela qual, através de diferentes épocas tem sido estudadas diferentes configurações. O problema da separação de misturas multicomponente pode envolver sequências de colunas de destilação convencionais. Neste caso, surge um problema combinatório a fim de projetar a sequência mais econômica de separação. Por outro lado, em anos recentes têm sido proposto o uso de equipamentos alternativos, sendo as colunas com paredes divididas uma opção bastante estudada que se caracterizam pela integração de 2 seções de colunas compartilhando um único condensador e um único refervedor. Estes equipamentos propõem diminuir o custo total de processo de separação de misturas multicomponentes. Neste trabalho apresenta-se um estudo econômico da separação de três misturas ternárias de Benzeno, Tolueno, P-xileno, comparando os projetos ótimos de sequências convencionais e de colunas de paredes divididas. Inicialmente, são definidas as variáveis de projeto para cada configuração por meio de uma análise de graus de liberdade. O dimensionamento é realizado inicialmente com o método não rigoroso de valor de fronteira. Finalmente, as sequências diretas e indiretas e as colunas de parede divididas são projetadas usando modelos rigorosos, baseados no método de ponto de bolha, programação matemática para resolver os problemas de otimização do Custo Total Anualizado TAC com variáveis contínuas e enumeração exaustiva para tratar o problema combinatório. São obtidos projetos ótimos para uma alimentação com três composições diferentes. A sequência indireta forneceu o melhor resultado para a alimentação rica no componente mais pesado (-58,35%) e no componente intermediário (-45,98%). Já a sequência direta foi a melhor quando a alimentação é rica em componente leve (-33,36%). A coluna com parede dividida teve o pior desempenho em todos os três casos estudados. / Distillation is a high-energy demand separation process, for that reason, alternative configurations have been studied through the ages. The separation problem of multicomponent mixtures may involve a sequence of conventional distillation columns. In this case, a combinatorial problem arises in order to design the most economical separation sequence. On the other hand, in recent years the use of alternative devices has been proposed. One of those options is the divided wall column, which is extensively studied, and is characterized by the integration of two column sections sharing a single condenser and a single reboiler. This equipment is sought to decrease the total cost of the separation process for multicomponent mixtures. This work presents an economic study for the separation of three ternary mixtures of benzene, toluene and p-xylene, comparing the optimum design of conventional sequences and divided wall columns. Initially, the design variables are defined for each configuration through a degrees of freedom analysis. The sizing is initially performed with the boundary value shortcut method. Then, the direct and indirect sequences, and divided wall columns are designed using rigorous models based on the bubble point method. Mathematical programming is used for solving the optimization problems of minimization of the total annualized cost (TAC) with continuous variables and exhaustive enumeration to handle the combinatorial issue. Optimal designs for three feeds with different compositions are obtained. The indirect sequence provided the best result for the feed rich in the heaviest component (-58.35 %) and in the intermediate component (-45.98 %). The direct sequence result was the best when the feed composition is rich in lighter component (-33.36 %). The divided wall column had the worst performance in all three cases studied.

A destilação é um processo de separação com uma alta demanda de energia, razão pela qual, através de diferentes épocas tem sido estudadas diferentes configurações. O problema da separação de misturas multicomponente pode envolver sequências de colunas de destilação convencionais. Neste caso, surge um problema combinatório a fim de projetar a sequência mais econômica de separação. Por outro lado, em anos recentes têm sido proposto o uso de equipamentos alternativos, sendo as colunas com paredes divididas uma opção bastante estudada que se caracterizam pela integração de 2 seções de colunas compartilhando um único condensador e um único refervedor. Estes equipamentos propõem diminuir o custo total de processo de separação de misturas multicomponentes. Neste trabalho apresenta-se um estudo econômico da separação de três misturas ternárias de Benzeno, Tolueno, P-xileno, comparando os projetos ótimos de sequências convencionais e de colunas de paredes divididas. Inicialmente, são definidas as variáveis de projeto para cada configuração por meio de uma análise de graus de liberdade. O dimensionamento é realizado inicialmente com o método não rigoroso de valor de fronteira. Finalmente, as sequências diretas e indiretas e as colunas de parede divididas são projetadas usando modelos rigorosos, baseados no método de ponto de bolha, programação matemática para resolver os problemas de otimização do Custo Total Anualizado TAC com variáveis contínuas e enumeração exaustiva para tratar o problema combinatório. São obtidos projetos ótimos para uma alimentação com três composições diferentes. A sequência indireta forneceu o melhor resultado para a alimentação rica no componente mais pesado (-58,35%) e no componente intermediário (-45,98%). Já a sequência direta foi a melhor quando a alimentação é rica em componente leve (-33,36%). A coluna com parede dividida teve o pior desempenho em todos os três casos estudados. / Distillation is a high-energy demand separation process, for that reason, alternative configurations have been studied through the ages. The separation problem of multicomponent mixtures may involve a sequence of conventional distillation columns. In this case, a combinatorial problem arises in order to design the most economical separation sequence. On the other hand, in recent years the use of alternative devices has been proposed. One of those options is the divided wall column, which is extensively studied, and is characterized by the integration of two column sections sharing a single condenser and a single reboiler. This equipment is sought to decrease the total cost of the separation process for multicomponent mixtures. This work presents an economic study for the separation of three ternary mixtures of benzene, toluene and p-xylene, comparing the optimum design of conventional sequences and divided wall columns. Initially, the design variables are defined for each configuration through a degrees of freedom analysis. The sizing is initially performed with the boundary value shortcut method. Then, the direct and indirect sequences, and divided wall columns are designed using rigorous models based on the bubble point method. Mathematical programming is used for solving the optimization problems of minimization of the total annualized cost (TAC) with continuous variables and exhaustive enumeration to handle the combinatorial issue. Optimal designs for three feeds with different compositions are obtained. The indirect sequence provided the best result for the feed rich in the heaviest component (-58.35 %) and in the intermediate component (-45.98 %). The direct sequence result was the best when the feed composition is rich in lighter component (-33.36 %). The divided wall column had the worst performance in all three cases studied.