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One of heavy oils upgrading processes is hydroconversion. As it is a complex process involving many chemical reactions, the mathematical model of hydroconversion process often has more kinetic parameters than can be estimated from the data. In this thesis, a model for hydroconversion processing of vacuum residue is proposed. It is proved that the model is structurally identifiable, but shown that it is inestimable and good parameter estimates may be impossible to obtain even if the model fit is good. As a proof to the model inestimability, it is shown that literature data can be fitted using a subset of only three (of seven) parameters. To improve parameter estimability, a method is proposed for designing additional experiments. The method is based on designing experiments that provide data that is complementary (in an appropriate sense) to existing data. The approach is illustrated using the hydroconversion model. For the hydroconversion model, using two additional experiments provides a good balance between parameter estimation and experimental effort. / Process Control

The objective of this work is to develop mathematical models to predict molecular weight distributions (MWDs) of ethylene copolymers produced in an industrial gas-phase reactor using a Ziegler-Natta (Z-N) catalyst. Because of the multi-site nature of Z-N catalysts, models of Z-N catalyzed copolymerization tend to be very large and have many parameters that need to be estimated. It is important that the data that are available for parameter estimation be used effectively, and that a suitable balance is achieved between modeling rigour and simplification. In the thesis, deconvolution analysis is used to gain an understanding of how the polymer produced by various types of active sites on the Z-N catalyst responds to changes in the reactor operating conditions. This analysis reveals which reactions are important in determining the MWD and also shows that some types of active sites share similar behavior and can therefore share some kinetic parameters. With this knowledge, a simplified model is developed to predict MWDs of ethylene/hexene copolymers produced at 90 °C. Estimates of the parameters in this isothermal model provide good initial guesses for parameter estimation in a subsequent more complex model. The isothermal model is extended to account for the effects of butene and temperature. Estimability analysis and cross-validation are used to determine which parameters should be estimated from the available industrial data set. Twenty model parameters are estimated so that the model provides good predictions of MWD and comonomer incorporation. Finally, D-, A-,and V-optimal experimental designs for improving the quality of the model predictions are determined. Difficulties with local minima are addressed and a comparison of the optimality criteria is presented. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2009-05-28 20:43:58.37

Engineers who develop fundamental models for chemical processes are often unable to estimate all of the model parameters due to problems with parameter identifiability and estimability. The literature concerning these two concepts is reviewed and techniques for assessing parameter identifiability and estimability in nonlinear dynamic models are summarized. Modellers often face estimability problems when the available data are limited or noisy. In this situation, modellers must decide whether to conduct new experiments, change the model structure, or to estimate only a subset of the parameters and leave others at fixed values. Estimating only a subset of important model parameters is a technique often used by modellers who face estimability problems and it may lead to better model predictions with lower mean squared error (MSE) than the full model with all parameters estimated. Different methods in the literature for parameter subset selection are discussed and compared. An orthogonalization algorithm combined with a recent MSE-based criterion has been used successfully to rank parameters from most to least estimable and to determine the parameter subset that should be estimated to obtain the best predictions. In this work, this strategy is applied to a batch reactor model using additional data and results are compared with computationally-expensive leave-one-out cross-validation. A new simultaneous ranking and selection technique based on this MSE criterion is also described. Unfortunately, results from these parameter selection techniques are sensitive to the initial parameter values and the uncertainty factors used to calculate sensitivity coefficients. A robustness test is proposed and applied to assess the sensitivity of the selected parameter subset to the initial parameter guesses. The selected parameter subsets are compared with those selected using another MSE-based method proposed by Chu et al. (2009). The computational efforts of these methods are compared and recommendations are provided to modellers. / Thesis (Master, Chemical Engineering) -- Queen's University, 2011-09-27 10:52:31.588

This thesis examined the biological treatment of gas streams containing benzene, toluene, ethylbenzene and o-xylene (BTEX) using solid-liquid two-phase partitioning bioscrubbers (SL-TPPBs). SL-TPPBs consist of a cell containing aqueous phase and a polymeric solid phase that sequesters poorly water soluble and/or toxic substrates, mitigating substrate toxicity in the aqueous phase and improving the gas mass transfer during treatment of VOC contaminated gases. An initial investigation of oxygen transport determined that the polymers in a stirred-tank SL-TPPB enhance gas-liquid mass transfer. In addition, a study on biodegradation kinetics of BTEX by a bacterial consortium identified and quantified substrate interactions such as inhibition, enhancement and cometabolism. The stirred-tank SL-TPPB was then experimentally investigated for treatment of BTEX gas streams during steady-state and dynamic step-change operation to determine performance of the system relative to other biotreatment methods. A mathematical model was developed to predict system performance, which included the microbial kinetic model structure and parameters estimated during kinetic and oxygen mass transfer studies. As a less energy intensive alternative, an airlift SL-TPPB was operated and characterized. The airlift SL-TPPB was compared to an airlift liquid-liquid TPPB (silicone oil as sequestering phase) and a single phase airlift over dynamic step-change loadings, which showed that the airlift SL-TPPB outperformed the single phase airlift by >30% and had similar performance to the liquid-liquid airlift. However, the airlift SL-TPPB performance was lower relative to the stirred-tank SL-TPPB by >15%. Steady-state operation of the airlift SL-TPPB identified a range of operating conditions that provided maximum performance and conditions that were not oxygen limited. This prompted a study of oxygen mass transfer and hydrodynamics in the airlift system, which identified that the addition of polymers to an airlift does not cause physical enhancement of the gas-liquid mass transfer coefficient, but improves aqueous phase mixing and enhances overall oxygen transfer rate. A tanks-in-series mathematical model was formulated to predict performance of the airlift SL-TPPB, wherein the number of tanks-in-series to describe mixing in the airlift was obtained from a residence time distribution analysis of the airlift system completed during the hydrodynamic investigation. This thesis contributes a low-energy solution for the effective treatment of gases contaminated with BTEX. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2009-08-18 16:16:22.598

Les objectifs de la thèse sont de (i) modéliser le transport de l’eau, d’un traceur et des polluants dans les sols contaminés, (ii) étudier l’estimabilité des paramètres et les corrélations entre les paramètres, (iii) optimiser les paramètres. Les différents modèles implantés dans le logiciel HYDRUS qui permettent de rendre compte ou pas de l’écoulement préférentiel et du transport hors équilibre physique et chimique sont choisis. Les études concernant le transport d’eau dans un lysimètre de terrain ont montré que les données quotidiennes de pressions et de teneurs en eau volumique contiennent plus d’information que les données horaires, que les pressions ont plus d’information que les teneurs en eau volumique, et que les corrélations des paramètres ont fait perturber les résultats de l’optimisation. Sur le même lysimètre, l’étude d’estimabilité des paramètres caractéristiques pour le transport du traceur (bromure) a montré que les concentrations dans les solutions de percolation ne sont pas suffisantes pour estimer le paramètre de transfert de l’eau entre les zones mobile et immobile car ce paramètre est fortement corrélé avec le paramètre de transfert de soluté. Pour le transport des hydrocarbures aromatiques polycycliques (HAP) dans les colonnes de laboratoire sous différentes conditions de saturation en eau, quand le degré de transport hors équilibre chimique des HAP est élevé, les concentrations en HAP dans les solutions de percolation de la colonne non saturée contiennent plus d’information que celles dans la colonne saturée / Preferential flow and nonequilibrium transport are probably the most frustrating in terms of hampering accurate predictions of contaminant transport through the vadose zone. The mathematical description of preferential flow and nonequilibrium transport needs many parameters that are not measurable. Therefore, the inverse method is a promising way to estimate model parameters. The main objectives of this work are to (i) study the water flow using the uniform flow and dual-porosity models, tracer and contaminant transport using the uniform transport model and/or physical and chemical nonequilibrium transport models, (ii) investigate parameter estimability and correlations between different parameters, and (iii) optimize the hydraulic properties and solute transport parameters. The results concerning the water flow in the bare field lysimeter show that daily data contained much more information than hourly data, daily pressure heads contained more information than daily water contents; the correlations between different parameters hamper the optimization results strongly. Basing on the tracer concentrations in the leaching solution of the lysimeter, the first-order rate water transfer coefficient was not estimable since this parameter was highly correlated with the solute transfer coefficient. PAH concentrations in the leaching solution of the contaminated soil column under saturated and nonsaturated flow conditions show that when the degree of chemical nonequilibirum transport is high, the solute leaching of the nonsaturated column contained more information than those of the saturated column. In addition, the fraction of sites with instantaneous sorption and the linear adsorption distribution coefficient always showed a very strong correlation, they were impossible to optimize simultaneously

L'objectif de cette étude est de développer une méthodologie permettant de déterminer et de mettre en \oe{}uvre les conditions opératoires optimales du procédé fed-batch de copolymérisation en émulsion du styrène et de l'acrylate de butyle en présence d'un agent de transfert de chaîne (CTA). Elle vise particulièrement à optimiser la production et les caractéristiques physico-chimiques de particules de latex à propriétés d'usage ciblées. Après une étude expérimentale de l'impact des différents facteurs, le modèle mathématique du procédé a été développé traduisant l'effet particulier de l'agent de transfert de chaîne sur la cinétique de polymérisation et mettant l'accent sur une les bilans de population. Une approche basée sur l'analyse de l'estimabilité des paramètres a ensuite permis de sélectionner 21 paramètres parmi les 49 paramètres du modèle mathématique dont les valeurs ont été identifiées grâce à un algorithme génétique. Le modèle mathématique validé en modes batch et fed-batch a ensuite été exploité pour l'optimisation multicritère du procédé orientée vers la maximisation de la production de particules de latex possédant une morphologie de type coeur-écorce avec un profil de température de transition vitreuse prédéfini. L'ensemble des solutions du front de Pareto a été obtenu grâce à un algorithme évolutionnaire développé et testé à cet effet. La meilleure alternative obtenue grâce à un outil d'aide à la décision a été implémentée expérimentalement et comparée avec succès aux prédictions du modèle mathématique / The objective of this study is to develop a methodology in order to determine and implement the optimal operating conditions of the emulsion fed-batch copolymerization process of styrene and butyl acrylate in the presence of a chain transfer agent. It particularly aims to optimize the production and the physico-chemical characteristics of latex particles with targeted end-use properties. After an experimental study, the process model has been developed taking into account the particular effect of the chain transfer agent on the polymerization kinetic and highlights the population balance. Thanks to an estimability analysis approach, 21 parameters among the 49 parameters of the model have been selected whose values have been identified by using a genetic algorithm. The mathematical model validated in both batch and fed-batch modes was then exploited for the multicriteria optimization of the process oriented towards the maximization of the production of latex particles having a core-shell type morphology with a given glass transition temperature profile. The Pareto's front solutions were obtained thanks to an evolutionary algorithm developed and tested for this purpose. The best alternative obtained by a decision-making aid tool was finally experimentally implemented and successfully compared with the predictions of the mathematical model