Simulated moving bed chromatography process (SMBCP) is the technical realisation of a countercurrent adsorption process through the cyclic port switching. SMB technology reduces the cost of packing material with high loading capacity and provides high purity and high recovery in a very short time. Major commodity applications have been found in the petroleum, food, biotechnology, pharmaceutical and fine chemical industries. The industrial applications bring an emergent demand to improve the SMBCP operation for higher product quality, productivity, efficiency and robustness. However, for this particular process, we encounter several challenges. Firstly, the interplay of the effects of strong nonlinearities, competition of solutes, mass transfer resistance and fluid dynamic dispersion produces steep concentration fronts. Mathematical model accounted for this particular property constitutes a serious difficulty for the solution procedure. Secondly, a dynamic SMB model consists of a set of partial differential, ordinary differential and algebraic equations, which are highly coupled. The large size is a problem due to its intensive computation when on-line optimisation and real-time control are necessary. Thirdly, the SMB unit operation exhibits complex dynamics. Process metrics for design and operation can be determined only when a cyclic steady state is reached after a certain number of switching. Achieving this steady state by solving the PDE models cycle after cycle involves expensive calculation. Studies have been carried out to solve these problems through process analysis, investigation on spatial discretisation techniques, and development of an accelerated integration scheme. / Through a systematic study on the advances of SMB modelling, design and control, a set of functionally equivalent models for SMBCP are identified and summarized for their practical applications. The limitations of the existing modelling techniques in industrial applications are also identified. Furthermore, structural analysis of the existing models is conducted for a better understanding of the functionality and suitability of each model. Suggestions are given on how to choose an appropriate model with sufficient accuracy while keeping the computational demand reasonably low for real time control. / Effort is made on to the systematic investigation of different numerical methods for the solution of PDEs to circumvent the steep gradients encountered in chromatographic separation. Comprehensive studies are conducted on a single column chromatographic process represented by a transport-dispersive-equilibrium linear model. Numerical solutions from the upwind-1 finite difference, wavelet-collocation, and high resolution methods are evaluated by quantitative comparisons with the analytical solution for a range of Peclet numbers. It reveals that for a PDE system with a low Peclet number, all existing numerical methods work well, but the upwind finite difference method consumes the most time for the same degree of accuracy of the numerical solution. The high resolution method provides an accurate numerical solution for a PDE system with a medium Peclet number. The wavelet collocation method is capable of catching up steep changes in the solution, and thus can be used for solving PDE models with high singularity. / The advantages and disadvantages of the wavelet based approaches are further investigated through several case studies on real SMBCP system. A glucose-fructose separation process is firstly chosen with its relatively simple isotherm representations. Simulations are conducted using both wavelet collocation and upwind finite difference methods. For more complicated applications, an enantiomers separation process is selected. As the PDEs model exhibit a certain degree of singularity, wavelet collocation and high resolution methods are adopted for spatial discretisation. It is revealed that both the wavelet based approaches and high resolution methods are good candidates in terms of computation demand and prediction accuracy on the steep front. This is the first time that these two frontier numerical methods are used for such a complex SMB system models and our results are encouraging for the development of model-based online control scheme. / In developing a new scheme to rapidly obtain the solution at steady state for any arbitrary initial condition, the concept of Quasi-Envelope (QE) is adopted under the consideration that a SMBCP can be treated as a pseudo-oscillatory process because of a large number of continuous switching. The scheme allows larger steps to be taken to predict the slow change of starting state within each switching. Combined with previously developed wavelet-based technique, this method is successfully applied to the simulation of a SMB sugar separation process. Investigations are also carried out on the location of proper starting point for the algorithm and on the effect of changing stepsize to the convergence of iteration method. It is found that if the starting state of Quasi-Envelope is chosen to be the same as the original function, the multivalue algorithm would require similar computational effort to achieve the steady state prediction, regardless of the integration stepsize. If using constant stepsize, launching QE later is helpful when quasi-envelope displays steep change at the start-up period. A changing stepsize produces slow convergence compared to the constant stepsize strategy, thus increasing the work load where the stepsize change is occurring. Other iteration method is required to be imposed to achieve faster convergence right from the beginning. Potential applications can be seen for other chemical engineering processes with inherent cyclic behaviour.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O Leito Móvel Simulado (LMS) é um processo de separação de compostos por adsorção muito eficiente, por trabalhar em um regime contínuo e também possuir fluxo contracorrente da fase sólida. Dentre as diversas aplicações, este processo tem se destacado na resolução de petroquímicos e principalmente na atualidade na separação de misturas racêmicas que são separações de um grau elevado de dificuldade. Neste trabalho foram propostas duas novas abordagens na modelagem do LMS, a abordagem Stepwise e a abordagem Front Velocity. Na modelagem Stepwise as colunas cromatográficas do LMS foram modeladas com uma abordagem discreta, onde cada uma delas teve seu domínio dividido em N células de mistura interligadas em série, e as concentrações dos compostos nas fases líquida e sólida foram simuladas usando duas cinéticas de transferência de massa distintas. Essa abordagem pressupõe que as interações decorrentes da transferência de massa entre as moléculas do composto nas suas fases líquida e sólida ocorram somente na superfície, de forma que com essa suposição pode-se admitir que o volume ocupado por cada molécula nas fases sólida e líquida é o mesmo, o que implica que o fator de residência pode ser considerado igual a constante de equilíbrio. Para descrever a transferência de massa que ocorre no processo cromatográfico a abordagem Front Velocity estabelece que a convecção é a fase dominante no transporte de soluto ao longo da coluna cromatográfica. O Front Velocity é um modelo discreto (etapas) em que a vazão determina o avanço da fase líquida ao longo da coluna. As etapas são: avanço da fase líquida e posterior transporte de massa entre as fases líquida e sólida, este último no mesmo intervalo de tempo. Desta forma, o fluxo volumétrico experimental é utilizado para a discretização dos volumes de controle que se deslocam ao longo da coluna porosa com a mesma velocidade da fase líquida. A transferência de massa foi representada por dois mecanismos cinéticos distintos, sem (tipo linear) e com capacidade máxima de adsorção (tipo Langmuir). Ambas as abordagens propostas foram estudadas e avaliadas mediante a comparação com dados experimentais de separação em LMS do anestésico cetamina e, posteriormente, com o fármaco Verapamil. Também foram comparados com as simulações do modelo de equilíbrio dispersivo para o caso da Cetamina, usado por Santos (2004), e para o caso do Verapamil (Perna 2013). Na etapa de caracterização da coluna cromatográfica as novas abordagens foram associadas à ferramenta inversa R2W de forma a determinar os parâmetros globais de transferência de massa apenas usando os tempos experimentais de residência de cada enantiômero na coluna de cromatografia líquida de alta eficiência (CLAE). Na segunda etapa os modelos cinéticos desenvolvidos nas abordagens foram aplicados nas colunas do LMS com os valores determinados na caracterização da coluna cromatográfica, para a simulação do processo de separação contínua. Os resultados das simulações mostram boa concordância entre as duas abordagens propostas e os experimentos de pulso para a caracterização da coluna na separação enantiomérica da cetamina ao longo do tempo. As simulações da separação em LMS, tanto do Verapamil quando da Cetamina apresentam uma discrepância com os dados experimentais nos primeiros ciclos, entretanto após esses ciclos iniciais a correlação entre os dados experimentais e as simulações. Para o caso da separação da cetamina (Santos, 2004), a qual a concentração da alimentação era relativamente baixa, os modelos foram capazes de predizer o processo de separação com as cinéticas Linear e Langmuir. No caso da separação do Verapamil (Perna, 2013), onde a concentração da alimentação é relativamente alta, somente a cinética de Langmuir representou o processo, devido a cinética Linear não representar a saturação das colunas cromatográficas. De acordo como o estudo conduzido ambas as abordagens propostas mostraram-se ferramentas com potencial na predição do comportamento cromatográfico de uma amostra em um experimento de pulso, assim como na simulação da separação de um composto no LMS, apesar das pequenas discrepâncias apresentadas nos primeiros ciclos de trabalho do LMS. Além disso, podem ser facilmente implementadas e aplicadas na análise do processo, pois requer um baixo número de parâmetros e são constituídas de equações diferenciais ordinárias. / Simulated Moving Bed (SMB) is a very efficient process in the compounds separation by adsorption, because works in a continuous regime, and with countercurrent flow of the solid phase. Among different applications, SMB has stood out in the petrochemical products separation and mainly in the separation of racemic compounds, which are separations of a high degree of difficulty. In this work, two new approaches to modeling the LMS process have been proposed, stepwise approach and Front Velocity approach. In the Stepwise approach, each chromatographic column of the SMB, is divided in to N cells connected in series, and the concentrations of compounds in liquid and solid phases were simulated using two different kinetics of mass transfer. This approach assumes that the interactions resulting from the mass transfer between the molecules of the compound in its liquid and solid phases occur only on the surface. So that with this assumption the volume occupied by each molecule in the solid and liquid phases is the same, implying that the factor of residence is equal to the equilibrium constant. To describe the mass transfer that occurs in the Chromatographic process, the Front Velocity approach considers that the convection is the dominant phase in the solute transport along the chromatographic column. The "Front Velocity" is a discrete model (steps) where the flow rate determines the liquid phase advance along the column. The steps are: advancing liquid phase and subsequent mass transfer between the liquid and solid phases, the latter in the same time interval. Thus, the experimental volumetric flow is used for the discretization of the control volume moving along the porous column with the same velocity of the liquid phase. The mass transfer was represented by two distinct kinetic mechanisms without (linear type) and with maximum adsorption capacity (Langmuir type). Both proposed approaches were studied and evaluated by comparison with experimental data separation LMS of the anesthetic ketamine and subsequently with the drug Verapamil. Were also compared with the simulations of dispersive equilibrium model for the case of ketamine used by Santos (2004) and the simulations of the software Help for the case of Verapamil (Perna 2013). In the chromatographic column characterization step, the new approaches have been associated with inverse R2W tool to determine the global mass transfer parameters using only the experimental residence times of each enantiomer in the high performance liquid chromatography (HPLC) column. In the second step, the kinetic models developed in both approaches were applied to the columns of the LMS with the values determined in the characterization of the chromatographic column step, for the simulation of continuous separation process. The simulation results show good agreement between the two proposed approaches and pulse experiments to characterize the column in the enantiomeric separation of ketamine over time. In the simulation of the SMB process, when the approaches admit one kinetic mechanism of the Langmuir type showed good agreement with the results obtained from the dispersive equilibrium model, it is a classical tool for the simulation of this process. While using a kinetic linear mechanism the results is more similar to the experimental data. According to the study conducted, both the proposed approaches were shown to be potential tools to predict the chromatographic behavior of a sample in a test pulse, as well as the simulation of separation of a compound in SMB process despite minor discrepancies presented in the first work cycles of the SMB. Moreover, the approaches can be easily programed and applied in the analysis of the process, because it requires a low number of parameters and consist of ordinary differential equations.

As atividades industriais petroquímicas, incluindo as refinarias de petróleo, são grandes consumidoras de água e, consequentemente, grandes geradoras de efluentes industriais contendo uma infinidade de contaminantes. No caso das refinarias de petróleo brasileiras, o nitrogênio amoniacal tem se tornado um componente crítico a ser tratado, o que tem sido feito através de processos de tratamento biológicos que utilizam a nitrificação como base. Neste trabalho, foi avaliada a operação de um reator de leito móvel (MBBR), em escala de bancada, utilizando suportes de polietileno com área específica de 820 m2.m-3, para tratar um efluente proveniente de uma refinaria brasileira com alta concentração de nitrogênio amoniacal. O efluente bruto apresentou demanda química de oxigênio entre 100 e 300 mg.L-1, teores de nitrogênio amoniacal entre 60 e 90 mg.L-1 e condutividade elétrica entre 1 e 2 mS.cm-1. Mesmo com variações da qualidade da alimentação da planta ao longo do estudo, como o aumento das concentrações de contaminantes, incluindo inibidores da nitrificação típicos dos efluentes de refinaria, a planta atendeu à Resolução CONAMA 430/2011 (BRASIL, 2011), que limita a concentração de descarte em 20 mg.L-1 para o contaminante nitrogênio amoniacal, em 93% das medições. Para o caso de uma fictícia legislação mais restritiva, que exigisse limite de 5 mg.L-1 desse contaminante, houve sucesso no tratamento em 83% do tempo, com eficiência média de nitrificação de 93,1%, evidenciando que há uma possibilidade real de utilização do processo MBBR em refinarias brasileiras. / Petrochemical industrial activities, including oil refineries, are major consumers of water and thus generating large industrial wastewater containing a multitude of contaminants. In the case of Brazilian oil refineries, ammonia nitrogen has become a critical component to be treated, what has been done through biological treatment processes using nitrification as a basis. In this work, the operation of a bench scale moving bed reactor was evaluated (MBBR), using polyethylene biomedia with specific area of 820 m2.m-3, to treat an effluent from a Brazilian petroleum refinery containing high concentrations of ammonia nitrogen, was evaluated. The raw effluent contained between 100 and 300 mg.L-1 of Chemical Oxygen Demand, ammonia nitrogen content between 60 and 90 mg.L-1 and electrical conductivity between 1 and 2 mS.cm-1. Even with the variation of feed quality throughout the study, such as the increasing of concentrations of contaminants, including of typical refinery wastewater nitrification inhibitors compounds, the plant has met the legislation CONAMA 430/2011 (BRASIL, 2011), which limits the discarding concentration of ammonia nitrogen in 20 mg.L-1, in 93% of measurements. In the case of a fictitious more restrictive legislation, requiring a discharge concentration limit of 5 mg.L-1 for this contaminant, the treatment was successful in 83% of the time, with an average efficiency of 93.1% nitrification, showing that there is a real possibility to use the MBBR process in Brazilian refineries.

Made available in DSpace on 2015-03-26T13:28:03Z (GMT). No. of bitstreams: 1 texto completo.pdf: 921341 bytes, checksum: 446b365083b78b0c2838f6e14f0457d3 (MD5) Previous issue date: 2011-05-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Bleached kraft pulp production generates large volumes of wastewater. During the process, wood components such as lignin, extractives and fibers are removed and contribute to the organic load of these effluents. Pulp mill wastewater treatment is usually performed by biological processes but part of the organic load has low biodegradability (or high recalcitrance) and is not removed by the treatment. Moreover, some of these compounds be toxic and decrease survival and, or reproduction in aquatic organisms. Pulp mill effluents are commonly treated in activated sludge plants. This system consists of an aeration tank, where organic matter is removed by biomass (biological sludge), and a sedimentation tank (secondary sedimentation), where effluent clarification occurs through settling of the biological sludge, which is recycled to the aeration tank, which allows increasing the biomass concentration and contributes to greater treatment efficiency. The moving bed biofilm reactor (MBBR) has emerged as a new activated sludge system configuration aimed at greater organic matter removal efficiency combined with greater stability, lower solids production and less need for nutrients. In this system, the aeration tank is filled with plastic biofilm carriers that are suspended and in continuous movement within the aeration tank, permitting growth of biomass in both dispersed and biofilm forms. This configuration allows greater biomass retention and may result in better recalcitrant organic matter or toxicity removal from industrial effluent. This study compared activated sludge and MBBR systems in parallel with the MBBR with hydraulic retention times of 12 and 24 hours, and the reactors in series (with MBBR after the activated sludge system), with regard to removal of organic matter, extractives, lignin, phenolic compounds and toxicity of bleached kraft pulp mill effluent, as well as EPS production by biological sludge. Both systems showed high organic matter removal efficiency with no statistically significant differences between reactor configurations. In relation to recalcitrant compounds, the MBBR was more efficient than the activated sludge system in extractives removal, but there was no difference in removal of lignin or phenolic compounds. Protein contents were higher in EPS produced by biological sludge in the reactors operated in series than in parallel. In general, the chronic toxicity to Ceriodaphnia dubia was eliminated through biological treatment, independently of the system or hydraulic retention time. In general, theMBBR and activated sludge systems behaved similarly for most of the parameters analyzed and configurations evaluated. / O processo de produção de polpa celulósica kraft branqueada é conhecido pela geração de grande volume de efluentes. Durante o processo, componentes da madeira, como lignina, extrativos e fibras, são removidos e contribuem para o aumento da carga orgânica destes efluentes. O tratamento destas águas residuárias normalmente é realizado por processos biológicos e parte destes compostos orgânicos possui baixa biodegradabilidade (ou alta recalcitrância) e não são removidos durante o tratamento. Além disso, alguns desses compostos apresentam efeitos tóxicos e podem causar problemas em relação à sobrevivência e, ou reprodução de organismos aquáticos. Um dos processos biológicos mais utilizados por indústrias de polpa celulósica é o sistema de lodos ativados. Este sistema é composto por um tanque de aeração, no qual ocorre a remoção da matéria orgânica através de sua utilização por uma biomassa (lodo biológico), e um decantador (decantador secundário), no qual ocorre a clarificação do efluente através da sedimentação dos sólidos em suspensão. O fornecimento do oxigênio é realizado por aeradores superficiais, sopradores de ar ou injeção de oxigênio puro. O sistema apresenta ainda uma linha de recirculação de lodo, responsável pelo retorno da biomassa decantada ao tanque de aeração, o que permite o aumento da concentração da biomassa e contribui para uma maior eficiência do tratamento. O reator de biofilme e leito móvel (MBBR) surgiu como uma nova configuração do sistema de lodos ativados visando maior eficiência de remoção de matéria orgânica combinada com maior estabilidade, menor produção de sólidos e menor necessidade de nutrientes. Neste sistema, o tanque de aeração é preenchido com meios suportes que possibilitam o crescimento aderido juntamente com o crescimento disperso no meio líquido. Esta configuração permite maior retenção da biomassa e pode implicar em uma maior remoção de matéria orgânica recalcitrante ou tóxica de efluentes industriais. O presente estudo comparou o sistema de lodos ativados e reator MBBR operados em paralelo com tempos de detenção hidráulica de 12 e 24 horas, além dos reatores em série (com o MBBR após o sistema de lodos ativados). Foram avaliadas as eficiências dos sistemas em relação à remoção de matéria orgânica, extrativos, lignina, compostos fenólicos e toxicidade do efluente de uma fábrica de polpa kraft branqueada de eucalipto, além de produção de EPS pelo lodo biológico. Os resultados indicaram grande eficiência de remoção de matéria orgânica de ambos os sistemas nas diferentes configurações testadas, e não foram observadas diferenças significativas entre os tratamentos. Em relação aos compostos recalcitrantes, o MBBR apresentou-se mais eficiente na remoção de extrativos do que o sistema de lodos ativados, mas não houve diferença significativa para a remoção de compostos fenólicos. Em geral, o tratamento biológico foi capaz de eliminar a toxicidade a Ceriodaphnia dubia, independentemente do reator ou tempo de detenção hidráulico. De maneira geral, o reator MBBR comportou-se de maneira semelhante ao sistema de lodos ativados, para a maioria dos parâmetros analisados e para as configurações testadas.

As atividades industriais petroquímicas, incluindo as refinarias de petróleo, são grandes consumidoras de água e, consequentemente, grandes geradoras de efluentes industriais contendo uma infinidade de contaminantes. No caso das refinarias de petróleo brasileiras, o nitrogênio amoniacal tem se tornado um componente crítico a ser tratado, o que tem sido feito através de processos de tratamento biológicos que utilizam a nitrificação como base. Neste trabalho, foi avaliada a operação de um reator de leito móvel (MBBR), em escala de bancada, utilizando suportes de polietileno com área específica de 820 m2.m-3, para tratar um efluente proveniente de uma refinaria brasileira com alta concentração de nitrogênio amoniacal. O efluente bruto apresentou demanda química de oxigênio entre 100 e 300 mg.L-1, teores de nitrogênio amoniacal entre 60 e 90 mg.L-1 e condutividade elétrica entre 1 e 2 mS.cm-1. Mesmo com variações da qualidade da alimentação da planta ao longo do estudo, como o aumento das concentrações de contaminantes, incluindo inibidores da nitrificação típicos dos efluentes de refinaria, a planta atendeu à Resolução CONAMA 430/2011 (BRASIL, 2011), que limita a concentração de descarte em 20 mg.L-1 para o contaminante nitrogênio amoniacal, em 93% das medições. Para o caso de uma fictícia legislação mais restritiva, que exigisse limite de 5 mg.L-1 desse contaminante, houve sucesso no tratamento em 83% do tempo, com eficiência média de nitrificação de 93,1%, evidenciando que há uma possibilidade real de utilização do processo MBBR em refinarias brasileiras. / Petrochemical industrial activities, including oil refineries, are major consumers of water and thus generating large industrial wastewater containing a multitude of contaminants. In the case of Brazilian oil refineries, ammonia nitrogen has become a critical component to be treated, what has been done through biological treatment processes using nitrification as a basis. In this work, the operation of a bench scale moving bed reactor was evaluated (MBBR), using polyethylene biomedia with specific area of 820 m2.m-3, to treat an effluent from a Brazilian petroleum refinery containing high concentrations of ammonia nitrogen, was evaluated. The raw effluent contained between 100 and 300 mg.L-1 of Chemical Oxygen Demand, ammonia nitrogen content between 60 and 90 mg.L-1 and electrical conductivity between 1 and 2 mS.cm-1. Even with the variation of feed quality throughout the study, such as the increasing of concentrations of contaminants, including of typical refinery wastewater nitrification inhibitors compounds, the plant has met the legislation CONAMA 430/2011 (BRASIL, 2011), which limits the discarding concentration of ammonia nitrogen in 20 mg.L-1, in 93% of measurements. In the case of a fictitious more restrictive legislation, requiring a discharge concentration limit of 5 mg.L-1 for this contaminant, the treatment was successful in 83% of the time, with an average efficiency of 93.1% nitrification, showing that there is a real possibility to use the MBBR process in Brazilian refineries.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O Leito Móvel Simulado (LMS) é um processo de separação de compostos por adsorção muito eficiente, por trabalhar em um regime contínuo e também possuir fluxo contracorrente da fase sólida. Dentre as diversas aplicações, este processo tem se destacado na resolução de petroquímicos e principalmente na atualidade na separação de misturas racêmicas que são separações de um grau elevado de dificuldade. Neste trabalho foram propostas duas novas abordagens na modelagem do LMS, a abordagem Stepwise e a abordagem Front Velocity. Na modelagem Stepwise as colunas cromatográficas do LMS foram modeladas com uma abordagem discreta, onde cada uma delas teve seu domínio dividido em N células de mistura interligadas em série, e as concentrações dos compostos nas fases líquida e sólida foram simuladas usando duas cinéticas de transferência de massa distintas. Essa abordagem pressupõe que as interações decorrentes da transferência de massa entre as moléculas do composto nas suas fases líquida e sólida ocorram somente na superfície, de forma que com essa suposição pode-se admitir que o volume ocupado por cada molécula nas fases sólida e líquida é o mesmo, o que implica que o fator de residência pode ser considerado igual a constante de equilíbrio. Para descrever a transferência de massa que ocorre no processo cromatográfico a abordagem Front Velocity estabelece que a convecção é a fase dominante no transporte de soluto ao longo da coluna cromatográfica. O Front Velocity é um modelo discreto (etapas) em que a vazão determina o avanço da fase líquida ao longo da coluna. As etapas são: avanço da fase líquida e posterior transporte de massa entre as fases líquida e sólida, este último no mesmo intervalo de tempo. Desta forma, o fluxo volumétrico experimental é utilizado para a discretização dos volumes de controle que se deslocam ao longo da coluna porosa com a mesma velocidade da fase líquida. A transferência de massa foi representada por dois mecanismos cinéticos distintos, sem (tipo linear) e com capacidade máxima de adsorção (tipo Langmuir). Ambas as abordagens propostas foram estudadas e avaliadas mediante a comparação com dados experimentais de separação em LMS do anestésico cetamina e, posteriormente, com o fármaco Verapamil. Também foram comparados com as simulações do modelo de equilíbrio dispersivo para o caso da Cetamina, usado por Santos (2004), e para o caso do Verapamil (Perna 2013). Na etapa de caracterização da coluna cromatográfica as novas abordagens foram associadas à ferramenta inversa R2W de forma a determinar os parâmetros globais de transferência de massa apenas usando os tempos experimentais de residência de cada enantiômero na coluna de cromatografia líquida de alta eficiência (CLAE). Na segunda etapa os modelos cinéticos desenvolvidos nas abordagens foram aplicados nas colunas do LMS com os valores determinados na caracterização da coluna cromatográfica, para a simulação do processo de separação contínua. Os resultados das simulações mostram boa concordância entre as duas abordagens propostas e os experimentos de pulso para a caracterização da coluna na separação enantiomérica da cetamina ao longo do tempo. As simulações da separação em LMS, tanto do Verapamil quando da Cetamina apresentam uma discrepância com os dados experimentais nos primeiros ciclos, entretanto após esses ciclos iniciais a correlação entre os dados experimentais e as simulações. Para o caso da separação da cetamina (Santos, 2004), a qual a concentração da alimentação era relativamente baixa, os modelos foram capazes de predizer o processo de separação com as cinéticas Linear e Langmuir. No caso da separação do Verapamil (Perna, 2013), onde a concentração da alimentação é relativamente alta, somente a cinética de Langmuir representou o processo, devido a cinética Linear não representar a saturação das colunas cromatográficas. De acordo como o estudo conduzido ambas as abordagens propostas mostraram-se ferramentas com potencial na predição do comportamento cromatográfico de uma amostra em um experimento de pulso, assim como na simulação da separação de um composto no LMS, apesar das pequenas discrepâncias apresentadas nos primeiros ciclos de trabalho do LMS. Além disso, podem ser facilmente implementadas e aplicadas na análise do processo, pois requer um baixo número de parâmetros e são constituídas de equações diferenciais ordinárias. / Simulated Moving Bed (SMB) is a very efficient process in the compounds separation by adsorption, because works in a continuous regime, and with countercurrent flow of the solid phase. Among different applications, SMB has stood out in the petrochemical products separation and mainly in the separation of racemic compounds, which are separations of a high degree of difficulty. In this work, two new approaches to modeling the LMS process have been proposed, stepwise approach and Front Velocity approach. In the Stepwise approach, each chromatographic column of the SMB, is divided in to N cells connected in series, and the concentrations of compounds in liquid and solid phases were simulated using two different kinetics of mass transfer. This approach assumes that the interactions resulting from the mass transfer between the molecules of the compound in its liquid and solid phases occur only on the surface. So that with this assumption the volume occupied by each molecule in the solid and liquid phases is the same, implying that the factor of residence is equal to the equilibrium constant. To describe the mass transfer that occurs in the Chromatographic process, the Front Velocity approach considers that the convection is the dominant phase in the solute transport along the chromatographic column. The "Front Velocity" is a discrete model (steps) where the flow rate determines the liquid phase advance along the column. The steps are: advancing liquid phase and subsequent mass transfer between the liquid and solid phases, the latter in the same time interval. Thus, the experimental volumetric flow is used for the discretization of the control volume moving along the porous column with the same velocity of the liquid phase. The mass transfer was represented by two distinct kinetic mechanisms without (linear type) and with maximum adsorption capacity (Langmuir type). Both proposed approaches were studied and evaluated by comparison with experimental data separation LMS of the anesthetic ketamine and subsequently with the drug Verapamil. Were also compared with the simulations of dispersive equilibrium model for the case of ketamine used by Santos (2004) and the simulations of the software Help for the case of Verapamil (Perna 2013). In the chromatographic column characterization step, the new approaches have been associated with inverse R2W tool to determine the global mass transfer parameters using only the experimental residence times of each enantiomer in the high performance liquid chromatography (HPLC) column. In the second step, the kinetic models developed in both approaches were applied to the columns of the LMS with the values determined in the characterization of the chromatographic column step, for the simulation of continuous separation process. The simulation results show good agreement between the two proposed approaches and pulse experiments to characterize the column in the enantiomeric separation of ketamine over time. In the simulation of the SMB process, when the approaches admit one kinetic mechanism of the Langmuir type showed good agreement with the results obtained from the dispersive equilibrium model, it is a classical tool for the simulation of this process. While using a kinetic linear mechanism the results is more similar to the experimental data. According to the study conducted, both the proposed approaches were shown to be potential tools to predict the chromatographic behavior of a sample in a test pulse, as well as the simulation of separation of a compound in SMB process despite minor discrepancies presented in the first work cycles of the SMB. Moreover, the approaches can be easily programed and applied in the analysis of the process, because it requires a low number of parameters and consist of ordinary differential equations.

O lançamento de águas residuárias contendo compostos nitrogenados tem um importante impacto sobre a saúde e o meio ambiente, tornando necessária a incorporação de processos de remoção desses compostos nos sistemas de tratamento de águas residuárias. Neste trabalho, foram estudadas as condições de operação para promover a remoção conjunta de nitrogênio e matéria orgânica em reator biológico de leito móvel, contínuo, operado sob aeração intermitente, alimentado com água residuária sintética contendo nitrogênio amoniacal (90 a 110 mg/L) e melaço como matéria orgânica (DQO de 450 a 550 mg/L). Foram utilizados dois reatores em escala de bancada, cada um com dois litros de volume útil, contendo diferentes meios suportes para a imobilização da biomassa: matrizes de espuma de poliuretano e anéis plásticos. Na primeira etapa experimental, o reator contendo anéis plásticos apresentou eficiências de remoção de nitrogênio muito baixas. Na segunda etapa, trocou-se o material suporte por matrizes de espuma de poliuretano inoculadas com lodo aeróbio de estação de tratamento de águas residuárias. A partir de então, trabalhou-se com dois reatores de mesma configuração, exceto pelas origens, idades e características dos lodos de inóculo. Inicialmente, a alimentação foi realizada utilizando-se apenas os micronutrientes contidos no melaço. Posteriormente, a composição da água residuária foi alterada, introduzindo-se solução de micronutrientes, pois se concluiu que a instabilidade no processo de nitrificação devia-se ao fato de o melaço comercial apresentar deficiências nutricionais. Como resultado, em condições de estabilidade operacional, foram obtidas eficiências de remoção de DQO superiores a 85%, oxidação total do nitrogênio amoniacal e eficiências de remoção de nitrogênio de aproximadamente 55%. Variações posteriores nas condições de operação, como o aumento do período anóxico (de 1h para 1h15min) e redução do tempo de detenção hidráulica (para valores inferiores a 12 horas), resultaram em melhora no desempenho dos reatores. Os resultados obtidos permitem admitir que as melhores condições de operação não foram atingidas durante o experimento, abrindo a possibilidade para a otimização do processo em pesquisas futuras. Constatou-se que o desenvolvimento das populações microbianas imobilizadas no meio suporte foi diferente do observado na biomassa em suspensão. Verificou-se, também, que a biomassa responsável pela nitrificação e desnitrificação ocorreu predominantemente no meio suporte, enquanto que a biomassa heterotrófica predominou no lodo em suspensão. / The operating conditions for the combined removal of nitrogen and organic matter in moving- bed biological reactor were investigated. Two bench-scale reactors, two liters each, were operated under intermittent aeration and continuously fed with synthetic wastewater containing ammonia nitrogen (90 to 110 mg/L) and molasses as organic carbon source (COD of 450 to 550 mg/L). Each reactor received different moving-bed materials: polyurethane foam matrices and plastic rings, respectively. During the first experimental period, the reactor containing plastic rings maintained very low nitrogen removal efficiencies during large period. For this reason, the moving-bed was replaced by polyurethane foam matrices and the reactor was re-inoculated with aerobic wastewater plant sludge. Thereafter, the two reactors were similar except for the origin, age and characteristics of the inoculum sludge. First, the wastewater micronutrients were just those contained in the carbon source (molasses). After, the synthetic wastewater composition was changed by adding a solution of micronutrients. This procedure was adopted to achieve a stable nitrification process, because commercial molasses is a very poor regarding its micronutrient composition. As a result of the stable conditions prevalence just after adding micronutrients, organic matter (as COD) removal efficiencies were higher than 85% and complete nitrogen ammonia oxidation was achieved. In nitrogen removal efficiencies were approximately 55%. The performance of the reactors improved after the increase of the anoxic period from1h to 1h15min, and reduction of the hydraulic detention time to less than 12 h. The results obtained in the last operating period indicated the optimum operating conditions was not achieved in this experiment, thus opening the possibility of process improvement in further researches. Microbial populations with different characteristics were developed in suspended growth and attached biomass. Nitrification and denitrification bacteria predominated as attached biomass whereas heterotrophic bacteria predominated as suspended growth biomass.

Continuous chromatography is an attractive alternative to traditional batch chromatography because it can have higher productivity, solvent efficiency, and product concentrations. However, several barriers prevent further use of continuous chromatography. There are many operating parameters that must be determined when designing continuous systems making it difficult to achieve high purity, yield, and productivity. Through the identification and strategic combination of the key dimensionless groups that control a continuous separation, it is possible to design highly productive systems that produce products with high yield and high purity. In this dissertation, three examples were selected to demonstrate the significance of a model-based method when designing continuous chromatography systems. (1) The Speedy Standing Wave Design and simulated moving bed splitting strategies for the separation of ternary mixtures with linear isotherms. (2) The Standing-wave Design of Three-Zone open-loop non-isocratic SMB for purification. (3) The Continuous Ligand-Assisted Displacement for the separation of Rare Earth Elements.<div>In the first example, the Speedy Standing Wave Design equations were developed for multicomponent separations with linear isotherms and a systematic splitting strategy was developed for the design of multiple sequential Simulated Moving Beds (SMBs). By performing the easiest split first, the overall productivity and solvent efficiency can be significantly improved. Rate model simulations were used to verify that the SSWD equations achieved target yields and purities. In systems where only one component is desired, the sorbent should be selected such that this component is the most or least retained so that it can be separated in a single SMB.</div><div>In the second example, the Standing Wave Design method was extended to non-isocratic three zone open loop SMBs. The standing wave design equations were derived and then verified using rate model simulations. In two case studies it was shown that non-isocratic SMBs designed using the standing wave design method show an order of magnitude higher productivity than a comparable batch system when the impurities are weakly adsorbing. When the impurities are competitive, the SWD method produces SMB systems with 2 orders of magnitude higher productivity than comparable batch systems. Because the design is based on dimensionless groups, the resulting designs are easily scalable and no rate model simulations are required to design high yield, high purity, and high productivity SMBs.</div><div>In the third example, the constant pattern design method was extended to continuous LAD systems. A continuous operation mode was developed that reduced the cycle time of LAD systems to further increase the productivity. In cases where the feed was equimolar, the continuous configuration increased the productivity between 20-50%. A multizone continuous LAD configuration was developed for the separation of a complex mixture of Dy, ND, and Pr that simulated a crude magnet feed. The resulting overall productivity for this system was 190 kg/m³day which was two orders of magnitude higher than a single column batch system and 70% higher than a multizone batch system. The robustness of the constant pattern design method was demonstrated through a simulated case study and it was determined that adding a safety factor through the reduction of the flowrate was more effective than reducing the design length.</div><div>Using a model-based design allows for the consistent design of continuous chromatography systems. The effects of a change in a feed or operating condition can be more easily understood through the lens of the model. This means that adjustments can be made pre-emptively when necessary and the new designs can be tested with virtual experiments before being implemented. The understanding of key dimensionless groups allows for designs that meet key design criteria at all scales of operation and thus allows for the easy transition from one scale to another.</div>

This master thesis is based on own studies. A four-month study was performed at Hammarby Sjostad Research Station, which is located in Stockholm. One-stage deammonification process was evaluated in two different system configurations in pilot plant scale. The theoretical background for this thesis works is presented in the first part and where is presented negative impacts of nitrogen compounds in environment and requirements for purified wastewater in European Union (Sweden and Poland). In the next part of the thesis the nitrogen cycle is described and with focus on biological reactions for nitrogen removal. Especially, nitrification/denitrification and anammox processes are described with special focus on parameters affecting the anammox process performance and its advantages and disadvantages of using this process. Experimental results from the four-month study and evaluation of the microbial activity are described in the last part.

The aim of the present work about experimental and mathematical modelling of moving-bed-gasification was to increase the transparency of the process. At Dresden University of Technology a gasifier with a high number of measuring points was used. Two-dimensional profiles of temperature and gas-concentrations were analysed. Samples of particles taken out of the reactor gave information about drying, pyrolysis and char-reactions. A commercial CFD-software was modified for the special application of fixed-bedgasifiers by subroutines. Comparisons of the results of experiment and simulation showed the constitutive process with its significant reaction-behaviour. By variation of different parameters, important influences were discussed. / Das Ziel der Arbeit war die Erhöhung der Prozeßtransparenz der Festbettvergasung im kleinen Leistungsbereich. Es besteht einerseits eine große Wissenslücke, welche einen durchschlagenden Erfolg für den Brennstoff Holz bisher verhinderte. Andererseits besitzt die Technologie ein energiewirtschaftlich bedeutendes und unter den gegenwärtigen politischen Rahmenbedingungen betriebswirtschaftlich hohes Potential. Ein Modellvergaser war mit umfangreichen Meßmöglichkeiten ausgerüstet. Mittels daran angepaßter Probenahmevorrichtungen konnten in den Untersuchungen auf der Basis von 16 Stützstellen zweidimensionale Profile der Temperatur und der Gaszusammensetzung ermittelt werden. Die Partikelproben aus drei Meßebenen gaben Auskunft über den Trocknungs- und Pyrolysefortschritt sowie über den Koksumsatz. Parallel erfolgte die Erarbeitung einer Mathematischen Modellierung. Hier wurde eine kommerzielle Strömungssimulations-Software mittels Unterprogramme an die Anforderungen der Festbettvergasung angepaßt. Im Vergleich der Ergebnisse aus Experiment und Simulation konnte der Reaktionsablauf dargestellt, sowie Einflüsse verschiedener Parameter auf den Prozeß diskutiert werden.