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.

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.

Submitted by Morgana Andrade (morgana.andrade@ufes.br) on 2016-04-20T22:14:13Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) tese_2452_Mariana Frizera.pdf: 7628756 bytes, checksum: 7fb4daf0933cfd2f18906ac0d2c39ebd (MD5) / Approved for entry into archive by Patricia Barros (patricia.barros@ufes.br) on 2016-04-25T16:11:53Z (GMT) No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) tese_2452_Mariana Frizera.pdf: 7628756 bytes, checksum: 7fb4daf0933cfd2f18906ac0d2c39ebd (MD5) / Made available in DSpace on 2016-04-25T16:11:53Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) tese_2452_Mariana Frizera.pdf: 7628756 bytes, checksum: 7fb4daf0933cfd2f18906ac0d2c39ebd (MD5) / LabPetro - Fundação Ceciliano Abel de Almeida

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

La qualité des eaux-de-vie est un paramètre associé à la composition en composés volatils d’arôme. Cette composition résulte de la combinaison de différents facteurs dont la nature et le traitement des matières premières, mais surtout des transformations ayant lieu lors des phases de fermentation, distillation et, dans la plupart de cas, vieillissement.La distillation est une opération de séparation pratiquée depuis des millénaires, avec une technologie assez mature. Cependant, dans le domaine des eaux-de-vie, elle s’appuie essentiellement sur des connaissances empiriques. L’objectif de ce doctorat fut de contribuer à une meilleure compréhension du comportement des composés volatils d’arôme au cours de différents modes de distillation et de fournir des bases scientifiques à la conduite des unités par le biais de modules de simulation. L’attention a été portée sur la distillation d’Armagnac et de Calvados dans des colonnes multiétagées en régime stationnaire.Les modules de simulation ont été construits avec le logiciel ProSimPlus®. La première partie des travaux a été consacrée à l’acquisition de données d’équilibre liquide-vapeur des composés volatils d’arôme en milieu hydroalcoolique pour l’identification du modèle NRTL, en suivant trois approches complémentaires : recherche dans la littérature, détermination expérimentale et prédiction théorique avec les modèles UNIFAC et COSMO. Grâce à la connaissance acquise sur les volatilités relatives par rapport à l’éthanol et à l’eau, les composés volatils d’arôme ont pu être classés en trois groupes : composés légers, composés intermédiaires et composés lourds. La deuxième partie des travaux a porté sur la construction et la validation des modules de simulation, après réconciliation des données issues de la caractérisation expérimentale des unités de distillation. Cette investigation démontre que la simulation est un outil d’ingénierie performant dans le domaine des eaux-de-vie. Les résultats de la simulation ont permis d’affiner la classification des composés intermédiaires en trois catégories supplémentaires selon leur profil de concentration dans la colonne et leur taux de récupération dans le distillat. Enfin, cet outil a mis en évidence que certains paramètres opératoires, notamment l’augmentation de la teneur en éthanol du distillat ainsi que l’extraction de queues, favorisent la séparation préférentielle de certaines espèces de volatilité faible ou intermédiaire par rapport à l’éthanol. / The quality of spirits is a parameter related to the composition of volatile aroma compounds. This composition results from the combined production process of raw material extraction, subsequent fermentation, distillation and, in many cases, ageing.Distillation is a very old and the most important industrial separation technology. However, in spirits production, this operation relies essentially on empirical knowledge. The aim of this PhD was to contribute to a better understanding of the volatile aroma compounds behaviour in spirits distillation and to provide a scientific basis for the process through computer simulation. The study was focused on Armagnac and Calvados production by continuous multistage distillation.The simulation modules were built using the software ProSimPlus®. The first part of this research was dedicated to the acquisition of vapor-liquid equilibrium data of the volatile aroma compounds in ethanol-water solutions, in order to estimate the binary interaction parameters of the NRTL model.Three complementary approaches of data acquisition were used: literature compilation, experimental measurements and predictions with UNIFAC and COSMO models.According to their relative volatilities with respect to ethanol and water, the volatile aroma compounds can be classified in three groups: light compounds, intermediary compounds and heavy compounds. The second part of this research dealt with the creation and validation of simulation modules, by using reconciled experimental data from the distillation units. The results prove that simulation is a powerful tool in spirits distillation. The simulation data enables a more precise classification of the intermediary compounds in three categories, by considering their composition profiles in the distillation column and their recovery ratios from feed to distillate. Finally, the analysis of some operating parameters, including ethanol concentration in the distillate as well as tails extractions, demonstrates that the distillate composition can be modified by virtue of a selective separation of intermediary and heavy compounds with respect to ethanol.

This thesis deals with the batch controlling of a distillation column model. The thesis is divided into several parts. The first part, which is more theoretical, summarizes the description of the batch controlling, the distillation process and the equipment used, including the model of the distillation column itself. The second part is focused on the practical implementation. The beginning of this part displays different types of the models produced by the Standard 88. This section is followed by a description of a device database in the environment of FactoryTalk Batch Equipment Editor, creation of a logical phase codes using functions of the PhaseManager in the environment of RSLogix5000 and a creation of a recipe in the environment of FactoryTalk Batch Recipe Editor. The last part of this thesis deals with the visualization created in the FactoryTalk View Studio SE and final testing of the entire process.

Le procédé de distillation est largement utilisé dans de nombreuses applications telles que la production pétrochimique, le traitement du gaz naturel, les raffineries de pétrole, etc. Généralement, la maintenance des réacteurs chimiques est très coûteuse et perturbe la production pendant de longues périodes. Tous ces facteurs démontrent réellement la nécessité de stratégies efficaces de diagnostic et de pronostic des défauts pour pouvoir réduire et éviter le plus grand nombre de ces problèmes catastrophiques. La première partie de nos travaux vise à proposer une méthode de diagnostic fiable pouvant être utilisée dans le régime permanent d’une procédure non linéaire. De plus, nous proposons une procédure modifiée de la méthode MFCM permettant de calculer la variation en pourcentage entre deux classes. L’utilisation de MFCM a pour objectif de réduire le temps de calcul et d’accroître les performances du classifieur. Les résultats de la méthode proposée confirment la capacité de classifier entre les différentes classes de défaillances considérées. Le calcul de la durée de vie du système est extrêmement important pour éviter les pannes catastrophiques. Notre deuxième objectif est de proposer une méthode fiable de pronostic permettant d’estimer le chemin de dégradation d’une colonne de distillation et de calculer le pourcentage de durée de vie de ce système. Le travail présente une approche basée sur le système d’inférence neuro-fuzzy adaptatif (ANFIS) combiné avec (FCM) pour prédire la trajectoire future et calculer le pourcentage de durée de vie du système. Les résultats obtenus démontrent la validité de la technique proposée pour atteindre les objectifs requis avec une précision de haut niveau. Pour améliorer les performances d’ANFIS, nous proposons la distribution de Parzen comme nouvelle fonction d’appartenance de l’algorithme ANFIS. Les résultats ont démontré l’importance de la technique proposée car elle s’est avérée efficace pour réduire le temps de calcul. En outre, la distribution de Parzen présentait la plus petite erreur quadratique moyenne (RMSE). La dernière partie de cette thèse se concentrait sur la proposition d’un nouvel algorithme pouvant être appliqué pour obtenir un système de surveillance en temps réel s’appuyant sur la prédiction de défauts ; cela signifie que cette méthode permet de prédire l’état futur du système, puis de diagnostiquer quelle est la source d’erreur probable. Elle permet d’évaluer la dégradation d’une colonne de distillation et de diagnostiquer par la suite les défauts ou accidents pouvant survenir à la suite de la dégradation estimée. Cette nouvelle approche combine les avantages d’ANFIS à ceux de RNA permettant d’atteindre un haut niveau de précision. / The distillation process is largely used in many applications such a petrochemical production, natural gas processing, and petroleum refineries, etc. Usually, maintenance of the chemical reactors is very costly and it disrupts production for long periods of time. All these factors really demonstrate the fundamental need for effective fault diagnosis and prognostic strategies that they are able to reduce and avoid the greatest number of thes problems and disasters. The first part of our work aims to propose a reliable diagnostic method that can be used in the steady-state regime of a nonlinear procedure. Moreover, we propose a modified procedure of the fuzzy c-means clustering method (MFCM) where MFCM calculates the percentage variation between the two clustered classes. The purpose of using MFCM is to reduce the computing time and increase the performance of the classifier. The results of the proposed method confirm the ability to classify between normal mode and eight abnormal modes of faults. Our second goal aims to propose a prognosis reliable method used to estimate the degradation path of a distillation column and calculate the lifetime percentage of this system. The work presents an approach based on adaptive neuro-fuzzy inference system (ANFIS) combined with (FCM) to predict the future path and calculate the lifetime percentage of the system. The results obtained demonstrate the validity of the proposed technique to achieve the needed objectives with a high-level accuracy. To improve ANFIS performance we propose Parzen windows distribution as a new membership function for ANFIS algorithm. Results demonstrated the importance of the proposed technique since it proved to be highly successful in terms of reducing the time consumed. Additionally, Parzen windows had the smallest Root Mean Square Error (RMSE). The last part of this thesis was focusing on the proposing of new algorithm which can be applied to obtain real-time monitoring system which relies on the fault production module to reach the diagnosis module in contrast to the previous strategies ; this means this method predict the future state of the system then diagnosis what is the probable fault source. This proposed method has proven to be a reliable process that can evaluate the degradation of a distillation column and subsequently diagnose the possible faults or accidents that can emerge as a result of the estimated degradation. This new approach combines the benefits of ANFIS with the benefits of feedforward ANN. The results were demonstrated that the technique achieved with a high level of accuracy, the objective of prediction and diagnosis especially when applied to the data obtained from automated distillation process in the chemical industry.

Solvents play a crucial role in the Active Pharmaceutical Ingredient (API) manufacturing and are used in large quantities. Most of the industries incinerate the waste solvents or send it to waste management companies for destruction to avoid waste handling and cross-contamination. It is not a cost effective method and also hazardous to the environment. This study has been performed at AstraZeneca’s API manufacturing plant at Sodertalje, Sweden. In order to find a solution, a solvent recovery system is modeled and simulated using ASPEN plus and ASPEN batch modeler. The waste streams were selected based on the quantity and cost of the solvents present in them. The solvent mixture in the first waste stream was toluene-methanol in which toluene was the key-solvent whereas in the second waste stream, isooctane-ethyl acetate was the solvent mixture in which isooctane was the key-solvent. The solvents in the waste stream were making an azeotrope and hence it was difficult to separate them using conventional distillation techniques. Liquid-Liquid Extraction with water as a solvent followed by batch distillation was used for the first waste stream and Pressure Swing Distillation was used for the second waste stream. The design was optimized based on cost analysis and was successful to deliver 96.1% toluene recovery with 99.5% purity and 83.6% isooctane recovery with 99% purity. The purity of the solvents was decided based on the quality conventions used at AstraZeneca so that it can be recovered and recycled in the same system. The results were favorable with a benefit of €335,000 per year and preventing nearly one ton per year carbon dioxide emissions to the environment. A theoretical study for the recovery system of toluene-methanol mixture was performed. The proposed design was an integration of pervaporation to the batch distillation. A blend of polyurethane / poly(dimethylsiloxane) (PU / PDMS) membrane was selected for the separation of methanol and toluene mixture. The results of preliminary calculations show 91.4% toluene recovery and 72% methanol recovery with desired purity.

In the reservoir conditions, a petroleum fluid is defined by its thermodynamic and volumetric properties and by its physicochemical properties. Their behaviors are modeled from experimental data in order to properly simulate the processing of these fluids during the production.   With the advent of new regulations and rigidity that exist at the custom regulations today, research centers have great difficulty in obtaining large amounts of samples. For these reason, although there are several methods to characterize the different components of crude oil, the laboratories are turning increasingly to techniques that requires lower amounts of samples: micro-distillation, gas chromatography (GC).   The micro-distillation is a fast and completely computerized technique made to substitute the standard distillation for analysis of liquid petroleum products. Advantages of the method compared to the standard distillation are the reduction of working time by at least a factor of 4, the small sample volumes required for distillation (few micro liters). [24]   This report is aimed to create a simple model that can predict yield curves of physical distillation, without using the micro-distillation technique. The results obtained through gas chromatography (GC) analysis by laboratory technicians enable the modeling of the fluid behavior. Having identified and treated practically all aspects of micro-distillation through simulations with PRO/II, I found out that, regardless of the setting and the thermodynamic method used, there are always significant differences between simulation results and those of the micro-distillation.   The result shows that it’s still difficult to create a model which can replace micro-distillation and gas chromatography (GC) because of the huge gap between the simulation results and micro-distillation. Furthermore, the dynamics revealed that the micro distillation is not accurate. I had hoped to get additional results by studies the correlations with more samples, but that did not turn out to be the case. Regardless of that, I think that it would be interesting to study more samples and use another simulator to properly represent micro distillation. This could be an interesting topic for further studies. / Under de föhållanden som reservoarens miljö erbjuder, definieras en petroleumvätska av dess termodynamiska och volymetriska egenskaper och av dess fysikalisk-kemiska egenskaper. För att korrekt simulera bearbetningen av dessa vätskor under produktion, deras beteende modelleras från experimentella data Med tillkomsten av nya regler och oflexibilitet som finns på tullbestämmelser vid gränserna idag, har forskningscenter stora svårigheter att få större mängder prover levererade. Av den anledningen, trots att det finns flera metoder för att karakterisera de olika komponenterna av råolja, tvingas laboratorier att vända sig mer och mer till alternativa analysmetoder som kräver mindre provvolymer: mikrodestillation, gaskromatografi, etc.   Mikrodestillation, som är en snabb och helt datoriserad teknik, visar sig kunna ersätta standarddestillation för analys av flytande petroleumprodukter. Fördelar med metoden jämfört med standarddestillering är minskad arbetstidsåtgång med minst en faktor 4. Därtill krävs endast en begränsad provvolym (några mikroliter) i jämförelse med standarddestillation.  [24]   Denna rapport syftar till att skapa en enkel modell som kan förutsäga avkastningskurvan av fysisk destillation, utan att använda mikrodestillationsteknik. De resultat som erhölls genom gaskromatografiska analyser möjliggjorde modelleringen av det vätskebeteendet hos det analyserade provet. Efter att ha identifierat och behandlat praktiskt taget alla viktiga aspekter av mikro destillation genom simuleringar med PRO/II, fann jag att, oberoende av inställningen och den termodynamiska metod som används,  det alltid finns stora skillnader mellan simulering och mikro destillation.   Resultatet visar att det fortfarande är svårt att skapa en modell som kan ersätta mikrodestillering och gaskromatografi på grund av differensen mellan simuleringsresultaten å ena sidan, och resultaten från mikrodestillering å andra sidan. Dessutom visade resultaten att mikrodestillation som analysmetod inte ger tillförlitliga resultat. Min förhoppning var att få ytterligare användbara resultat genom att studerar potentiella korrelationer emellan fler prover, men detta visade sig inte vara fallet. Jag anser att det skulle vara intressant att studera fler prover och använda en annan simulator för att bättre representera mikrodestillation. Detta skulle kunna vara ett intressant ämne för vidare studier.

The synthesis of a number of alkyl esters such as methyl lactate, methyl decanoate, and ethyl benzoate via esterification in a reactive distillation is quite challenging. It is due to the complexity in the thermodynamic behaviour of the chemical species in the reaction mixture in addition to the difficulty of keeping the reactants together in the reaction section. One of the reactants (in these esterification reactions) having the lowest boiling point can separate from the other reactant as the distillation continues. This can result in a significant drop in the reaction conversion in a conventional reactive distillation whether it is a batch or a continuous column. To overcome this challenge, new different types of batch reactive distillation column configurations: (1) integrated conventional (2) semi-batch (3) integrated semi-batch (4) integrated dividing-wall batch distillation columns have been proposed here. Four esterification reaction schemes such as (a) esterification of lactic acid (b) esterification of decanoic acid (c) esterification of benzoic acid (d) esterification of acetic acid are investigated here. A detailed dynamic model based on mass, energy balances, chemical reaction, and rigorous thermodynamic (chemical and physical) properties is considered and incorporated in the optimisation framework within gPROMS (general PROcess Modelling System) software. It is found that for the methyl lactate system, the i-SBD operation outperforms the classical batch operations (CBD or SBD columns) to satisfy the product constraints. While, for the methyl decanoate system, the i-DWCBD operation outperforms all CBD, DWBD and sr-DWBD configurations by achieving the higher reaction conversion and the maximum product purity. For the ethyl benzoate system, the performance of i-CBD column is superior to the CBD process in terms of product quality, and conversion rate of acid. The CBD process is found to be a more attractive in terms of operating time saving, and annual profit improvement compared to the IBD, and MVD processes for the benzyl acetate system. / The Higher Committee for Education Development in Iraq (HCED)