Crystallization is a key unit operation in the fine chemical and pharmaceutical industries, many of which employ batch stirred vessels for crystallization. Although using stirred vessels for crystallization has advantages such as better mixing and faster cooling, one of the disadvantages is that due to the presence of mechanical parts in the vessel such as baffles, impeller etc., crystals break up while stirring and generate unwanted secondary nucleation. This process contributes to a wide crystal size distribution with a smaller than desired mean crystal size. For studying crystal breakage phenomenon, experimentalists choose to use nonsolvents for crystal breakage experiments to isolate breakage from simultaneously occurring phenomena such as Ostwald-ripening, aging and agglomeration. Although performing experiments in non-solvents eliminates other phenomena and helps isolate breakage, the results can not always be correlated to saturated solutions due to density and viscosity differences between the two conditions. In this research, the effects of Ostwald ripening, aging and agglomeration on the crystal size and shape distributions are quantitatively measured. Micro and macro scale experiments were performed in both non-solvents and saturated solutions and the results were compared to determine the effects. Both in situ focused beam reflectance method (FBRM) and off-line analyses were performed to characterize the crystal size distributions. Results from experiments show that there is significant difference between the breakage behavior of crystals in non-solvents and in saturated solutions, mplying significant impacts of Ostwald ripening, aging, agglomeration and dissolution in saturated solutions. Calculations using Zwietering correlation also show that the difference between the viscosities and densities in the two systems may also be a contributing factor to the difference in the breakage profiles. It was also found that growth rates of crystals can differ when they are subjected to stress and strain. In macroscale experiments, dissolution was found to have a significant impact on the crystal size distribution. Abrasion was found to be the dominating fracture mechanism for most systems. Extent of breakage and morphological changes were found to be dependent on stirring rates, suspension density, shape and hardness of crystals and the type of system.

O crescimento acelerado da população mundial e o consequente aumento da produção de bens de consumo tem impulsionado uma crise na disponibilidade de recursos naturais, principalmente os hídricos. Diante da escassez de recursos hídricos, processos de tratamento de efluentes industriais e domésticos que visam o descarte zero de líquido (ZLD - Zero Liquid Discharge) vêm sendo cada vez mais estudados. Atualmente, diversos processos têm sido empregados com este propósito. No entanto, ainda há a geração, juntamente com a água recuperada, de uma corrente composta por uma solução salina concentrada, cuja composição normalmente é constituída por diferentes tipos de sais inorgânicos. Uma das formas de alcançar o descarte zero de líquidos é por meio da implementação de um processo adicional de separação, sendo a cristalização evaporativa considerada viável para essa finalidade. O emprego deste processo é limitado ao controle das características morfológicas das partículas obtidas, visto que estas influenciam diretamente na efetividade de separação dos processos subsequentes à cristalização (filtração, centrifugação). Além disso, efluentes industriais são soluções complexas, e a utilização da cristalização envolve a presença de mais de um sal em solução (co-cristalização). Este processo é pouco investigado na literatura científica, logo, a determinação de condições de processos visando controlar a características destas partículas não é trivial. Neste trabalho, foram estudados o efeito da taxa de evaporação e da presença de sementes na morfologia, composição, tamanho e hábito de partículas de cloreto de sódio e sulfato de cálcio obtidas por co-cristalização evaporativa em bateladas. Os resultados serviram para a determinação de parâmetros de operação para a co-cristalização visando a obtenção de partículas com elevado tamanho médio e baixa dispersão de tamanhos. Taxas de evaporação elevadas favoreceram a obtenção de aglomerados de partículas. A presença de sulfato de cálcio em solução resultou em partículas maiores, menos polidispersas e com menor grau de aglomeração. Tal resultado foi considerado positivo, visto que, estas características são desejáveis para a separação dos cristais da solução mãe. Foi também observado que as sementes de hemihidrato atuam inibindo a aglomeração dos cristais de NaCl. O aumento da quantidade de sementes destes sais culminou na obtenção de partículas menos aglomeradas, porém houve um alargamento das distribuições de tamanho de partículas. Nos experimentos em que foram utilizadas sementes de ambos os sais, o mesmo efeito na aglomeração foi observado. Em todos os experimentos com semeadura de hemihidrato, foi observada a aglomeração deste sal com o NaCl, que foi intensificada com o aumento da taxa de evaporação e com o aumento da concentração de sementes. Foi identificada a possibilidade de recuperação de ambos os sais e obtenção - em determinadas condições - de mais de 90% do NaCl com até 99,50% de pureza. / The accelerated growth of the world population and the consequent increase in the production of consumer goods, has driven to a crisis in the availability of natural resources, especially water. Due to the scarcity of water resources, industrial and domestic wastewater treatment processes that aim the Zero Liquid Discharge (ZLD) have been increasingly studied. Nowadays, several processes have been used for this purpose. However, in all of them, there is still the generation of a brine composed of a concentrated salt solution, concomitantly with the recovered water, whose composition is normally constituted by different types of inorganic salts. One way to achieve the ZLD is through the implementation of an additional separation process, for which the evaporative crystallization is considered technically viable for this purpose. The use of this process is limited to the control of the morphological characteristics of the particles obtained, since this influences directly the separation effectiveness of the downstream processes to crystallization (filtration, centrifugation). Besides, industrial effluents are complex solutions and its crystallization involves the presence of more than one salt in solution (cocrystallization). This process is still not well investigated on scientific literature, thus, the determination of process conditions aiming to control the characteristics of these particles is not trivial. In this work, the effect of the evaporation rate and the presence of seeds on the morphology, composition, size and habit of sodium chloride and calcium sulfate particles obtained by batch evaporative co-crystallization were studied. The results were used to determine the operating parameters for the cocrystallization in order to obtain particles with high average size and narrow dispersion of sizes. High evaporation rates favored the obtaining of agglomerated particles. The presence of calcium sulfate in solution resulted in larger particles, less polydisperse and with less degree of agglomeration. Such result was considered positive, since, these characteristics are desirable for the separation of the crystals from the solution. Seeds of hemihydrate inhibited the agglomeration of the NaCl crystals. The increase in seed load of hemihydrate culminated in obtaining less agglomerated particles, but there was an increase in particle size distributions. In the experiments in which seeds of both salts were used, the same effect in the agglomeration was observed. In all experiments with seeds of hemihydrate, agglomeration of this salt with NaCl was observed, which was intensified with increasing evaporation rate and increasing seed amount. It was identified the possibility of recovery of both salts and, for certain conditions, obtaining more than 90% of NaCl with up to 99.50% purity.

O crescimento acelerado da população mundial e o consequente aumento da produção de bens de consumo tem impulsionado uma crise na disponibilidade de recursos naturais, principalmente os hídricos. Diante da escassez de recursos hídricos, processos de tratamento de efluentes industriais e domésticos que visam o descarte zero de líquido (ZLD - Zero Liquid Discharge) vêm sendo cada vez mais estudados. Atualmente, diversos processos têm sido empregados com este propósito. No entanto, ainda há a geração, juntamente com a água recuperada, de uma corrente composta por uma solução salina concentrada, cuja composição normalmente é constituída por diferentes tipos de sais inorgânicos. Uma das formas de alcançar o descarte zero de líquidos é por meio da implementação de um processo adicional de separação, sendo a cristalização evaporativa considerada viável para essa finalidade. O emprego deste processo é limitado ao controle das características morfológicas das partículas obtidas, visto que estas influenciam diretamente na efetividade de separação dos processos subsequentes à cristalização (filtração, centrifugação). Além disso, efluentes industriais são soluções complexas, e a utilização da cristalização envolve a presença de mais de um sal em solução (co-cristalização). Este processo é pouco investigado na literatura científica, logo, a determinação de condições de processos visando controlar a características destas partículas não é trivial. Neste trabalho, foram estudados o efeito da taxa de evaporação e da presença de sementes na morfologia, composição, tamanho e hábito de partículas de cloreto de sódio e sulfato de cálcio obtidas por co-cristalização evaporativa em bateladas. Os resultados serviram para a determinação de parâmetros de operação para a co-cristalização visando a obtenção de partículas com elevado tamanho médio e baixa dispersão de tamanhos. Taxas de evaporação elevadas favoreceram a obtenção de aglomerados de partículas. A presença de sulfato de cálcio em solução resultou em partículas maiores, menos polidispersas e com menor grau de aglomeração. Tal resultado foi considerado positivo, visto que, estas características são desejáveis para a separação dos cristais da solução mãe. Foi também observado que as sementes de hemihidrato atuam inibindo a aglomeração dos cristais de NaCl. O aumento da quantidade de sementes destes sais culminou na obtenção de partículas menos aglomeradas, porém houve um alargamento das distribuições de tamanho de partículas. Nos experimentos em que foram utilizadas sementes de ambos os sais, o mesmo efeito na aglomeração foi observado. Em todos os experimentos com semeadura de hemihidrato, foi observada a aglomeração deste sal com o NaCl, que foi intensificada com o aumento da taxa de evaporação e com o aumento da concentração de sementes. Foi identificada a possibilidade de recuperação de ambos os sais e obtenção - em determinadas condições - de mais de 90% do NaCl com até 99,50% de pureza. / The accelerated growth of the world population and the consequent increase in the production of consumer goods, has driven to a crisis in the availability of natural resources, especially water. Due to the scarcity of water resources, industrial and domestic wastewater treatment processes that aim the Zero Liquid Discharge (ZLD) have been increasingly studied. Nowadays, several processes have been used for this purpose. However, in all of them, there is still the generation of a brine composed of a concentrated salt solution, concomitantly with the recovered water, whose composition is normally constituted by different types of inorganic salts. One way to achieve the ZLD is through the implementation of an additional separation process, for which the evaporative crystallization is considered technically viable for this purpose. The use of this process is limited to the control of the morphological characteristics of the particles obtained, since this influences directly the separation effectiveness of the downstream processes to crystallization (filtration, centrifugation). Besides, industrial effluents are complex solutions and its crystallization involves the presence of more than one salt in solution (cocrystallization). This process is still not well investigated on scientific literature, thus, the determination of process conditions aiming to control the characteristics of these particles is not trivial. In this work, the effect of the evaporation rate and the presence of seeds on the morphology, composition, size and habit of sodium chloride and calcium sulfate particles obtained by batch evaporative co-crystallization were studied. The results were used to determine the operating parameters for the cocrystallization in order to obtain particles with high average size and narrow dispersion of sizes. High evaporation rates favored the obtaining of agglomerated particles. The presence of calcium sulfate in solution resulted in larger particles, less polydisperse and with less degree of agglomeration. Such result was considered positive, since, these characteristics are desirable for the separation of the crystals from the solution. Seeds of hemihydrate inhibited the agglomeration of the NaCl crystals. The increase in seed load of hemihydrate culminated in obtaining less agglomerated particles, but there was an increase in particle size distributions. In the experiments in which seeds of both salts were used, the same effect in the agglomeration was observed. In all experiments with seeds of hemihydrate, agglomeration of this salt with NaCl was observed, which was intensified with increasing evaporation rate and increasing seed amount. It was identified the possibility of recovery of both salts and, for certain conditions, obtaining more than 90% of NaCl with up to 99.50% purity.

This thesis focuses on data-driven modeling and control of batch and batch-like processes. These processes are highly nonlinear and time-varying which, unlike continuous operations, are characterized by the finite duration of operation and absence of equilibrium conditions. This makes the modeling and control approaches available for continuous processes not readily applicable and requires appropriate adaptations of the available approaches to handle a) batch data structure for modeling and b) a control objective different than that of maintaining a steady-state operation as often encountered in a continuous process. With these considerations, this work adapted the batch subspace identification for modeling and control of a variety of batch and batch-like processes. A particular focus of this work was on the application of the proposed ideas on real engineering systems along with simulated case studies. The applications considered in this work are batch crystallization, a hydrogen plant startup dynamics in a collaboration with Praxair Inc. and a rotational molding process in collaboration with the polymer research group at McMaster University. For the seeded batch crystallization process, subspace identification techniques are adapted to identify a linear time invariant model for the, otherwise, infinite dimensional process. The identified model is then deployed in a linear model predictive control (MPC) strategy to achieve crystal size distribution (CSD) with desired characteristics subject to both manipulated input and product quality constraints. The proposed MPC is shown to achieve superior performance and the ability to respect tighter product quality constraints as well as robustness to uncertainty in comparison to an open loop policy as well as a traditional trajectory tracking policy using classical control. In another contribution, merits of handling data variety in a subspace identification framework was demonstrated on the crystallization process. The proposed approach facilitates the specification of a desired shape of the particle size distribution required at the termination of the batch process. Further, novel model validity constraints are proposed for the subspace identification based control framework. In the collaborative work on hydrogen plant startup, it is recognized as a batch-like process due to its similarity to batch processes. Firstly, in this work a high fidelity model of the Hydrogen unit was developed with relevant startup and shutdown mechanisms. This setup is used to mimic the trends in the key process variables during the startup/shutdown operation. The simulated data is used to identify a state-space model of the process and validated on new simulated startup. Further, the approach was demonstrated on real plant data from one of the Praxair's plants. The predictive capabilities of the model provide ample handle for the plant operator for averting failures and abrupt shutdown of the entire plant. This is expected to have immense economic advantages. Finally, the subspace identification based modeling and control approach was applied to a lab-scale rotational modeling (RM) process. It is a polymer processing technique that is characterized by the placement of a polymer resin inside a mold, subsequent closure of the mold, followed by the simultaneous application of uni-axial (as is the case in the present work) or bi-axial rotation and heat. The resin is deposited on the mold wall where it forms a dense unified layer following which, the mold is cooled while still rotating the mold. Once demolding temperatures are achieved, the finished part is removed from the mold. Its potential as a manufacturing process for polymeric components is limited by a number of concerns including difficulties in process control, in particular, determining efficiently the process operation to yield the desired product consistently, and produce new products. This work has contributed by developing optimal control strategies for the process to achieve user-specified product quality and reject variability across batches. The results obtained demonstrate the merits of the proposed approach. / Thesis / Doctor of Philosophy (PhD)

L'objectif principal de ce travail de recherche est de contrôler l'évolution de la distribution des tailles de cristaux (DTC) dans un procédé de cristallisation en batch. Nous avons été amenés à chercher une résolution numérique du bilan de population et à proposer un algorithme rapide et précis. La méthode numérique a été étendue au cas de la taille des cristaux multidimensionnels en utilisant un maillage mouvant. Nous avons étudié le problème de la commandabilité du système à partir de son modèle discrétisé et puis à partir du modèle continu. Nous avons conçu une loi de commande en boucle fermée pour atteindre la DTC désirée à partir de la condition initiale. Pour compenser l'incertitude des paramètres du modèle, nous avons ajouté un second contrôle par retour d'état afin d'assurer la poursuite de la DTC désirée en présence de l'incertitude des paramètres. Nous avons construit un observateur qui nous permet d'avoir en ligne l'estimation des variables d'états. Ces variables d'état estimées sont utilisées dans la synthèse de la loi du contrôle / The main objective of this research is to control the evolution of the Crystal Size Distribution (CSD) in a batch crystallization process. We are led to study a numerical resolution of the population balance and propose an algorithm for fast and accurate simulation. This method was extended to the case of the two-dimensional crystal by using a moving mesh. We studied the problem of controllability of the system from its discretized model and then from the continuous model. To compensate the uncertainty of the model parameters, we added the second state feedback control to ensure the tracking of the desired CSD in presence of parameter uncertainty. We constructed an observer who provides us with on-line estimation of state variables. These state variables estimated are used in the control law synthesis