Academic literature on the topic 'Simulated moving bed (SMB)'

Studies were carried out on the production of high-fructose syrup by Simulated Moving Bed (SMB) technology. A mathematical model and numerical methodology were used to predict the behavior and performance of the simulated moving bed reactors and to verify some important aspects for application of this technology in the isomerization process. The developed algorithm used the strategy that considered equivalences between simulated moving bed reactors and true moving bed reactors. The kinetic parameters of the enzymatic reaction were obtained experimentally using discontinuous reactors by the Lineweaver-Burk technique. Mass transfer effects in the reaction conversion using the immobilized enzyme glucose isomerase were investigated. In the SMB reactive system, the operational variable flow rate of feed stream was evaluated to determine its influence on system performance. Results showed that there were some flow rate values at which greater purities could be obtained.

Abstract Tartary buckwheat shell is an important by-product of Tartary buckwheat production. Previous studies shown that Tartary buckwheat shells are rich in flavonoids, which are responsible for their antioxidant properties. Due to lack of advanced separation technologies, the purification for Tartary buckwheat shell is still in the laboratory scale, and could not realize the industrialization production. According to the results of static adsorption experiment, AB-8 resin was selected for Tartary buckwheat shell flavonoids (TBSF) adsorption. The adsorption isotherm, resin adsorption thermodynamic and dynamic adsorption parameters were studied. And the adsorption of AB-8 resin for TBSF was determined as an endothermic process. Results of preparative chromatography experiment showed that TBSF could be efficiently purified by AB-8 resin. And the optimal parameters were: feed concentration 25 mg/mL, desorption flow rate 2.5 mL/min. Under these conditions, the TBSF were separated effectively. Results of liquid chromatography-mass spectrometer (LC-MS) indicated that there were seven kinds of flavonoids in Tartary buckwheat shell, which were mainly from the 40 and 60% of ethanol elution. Simulated moving bed (SMB) was applied for TBSF purification the first time in this study. The optimal conditions of SMB were as following: adsorption zone flow rate 7.0 mL/min, contaminant removal zone flow rate 17.9 mL/min, product elution zone flow rate 22.3 mL/min, regeneration zone flow rate 21.5 mL/min, water washing zone flow rate 27.5 mL/min, switching time 1260 S, and the purity and yield of TBSF was 90 ± 0.22% and 85 ± 0.28%, respectively. The IC50 values of α-glucosidase inhibition activities and DPPH scavenging activity of the purified TBSF were 57.09 ± 0.15 and 7.92 ± 0.23 μg/mL, respectively. The constituents of TBSF showed higher α-glucosidase inhibition activities and antioxidant than raw TBSF and rutin. The results suggest that SMB is a proper method for industrial production of TBSF, and SMB could be applied for other natural products purification.

Simulated moving bed (SMB) chromatographic separation is a new type of separation technology based on traditional fixed bed adsorption operation and true moving bed (TMB) chromatographic separation technology, which includes inlet-outlet liquid, liquid circulation, and feed liquid separation. The input-output data matrices were constructed based on SMB chromatographic separation process data. The SMB chromatographic separation process was modeled by utilizing two subspace system identification algorithms: multivariable output-error state-space (MOESP) identification algorithm and numerical algorithms for subspace state-space system identification (N4SID), so as to obtain the 3rd-order and 4th-order state-space yield models of the SMB chromatographic separation process, respectively. The model predictive control method based on the established state-space models is used in the SMB chromatographic separation process. The influence of different control indicators on the predictive control system response performance is discussed. The output response curves of the yield models were obtained by changing the related parameters so that the yield model parameters are optimized set meanwhile. Finally, the simulation results showed that the yield models are successfully controlled based on the each control period and given yield range.

Abstract A mixture of galacto-oligosaccharides and non-prebiotic sugars was separated using a simulated moving bed unit equipped with eight packed-bed columns of a cation exchanger. In order to determine operating conditions using triangle theory, equilibrium adsorption isotherms of galactose, glucose, lactose, tri- and tetragalacto-oligosaccharide were measured. It was found that each column of the SMB unit had a maximum separation efficiency of more than 3000 theoretical plates. The achieved purity of galacto-oligosaccharides in the raffinate stream was 99.9 %, similarly 99.9 % of extract was formed by non-prebiotic sugars lactose, glucose and galactose. The productivities in the raffinate and extract, were 0.6 g/(L h) and 2.4 g/(L h), respectively.

La chromatographie à lit mobile simulé (procédé SMB) est une technique de séparation bien maîtrisée dans certains secteurs traditionnels tels que la séparation de sucres et d’hydrocarbures. Cependant, son application à la séparation de composés à haute valeur ajoutée dans l’industrie pharmaceutique pose de nouveaux problèmes liés à la nature des produits à séparer ainsi qu'aux exigences plus strictes en matière de pureté et de quantités produites. Les principaux problèmes ouverts sont notamment la détermination des conditions de fonctionnement optimales, la conception de structures robustes de régulation, et le développement d’un système de supervision permettant la détection et la localisation de dégradations de fonctionnement. Ces tâches requièrent l’usage d’un modèle mathématique du procédé ainsi qu’une méthodologie d’estimation paramétrique. L’étude et le développement des modèles mathématiques pour ce type d’installation ainsi que l’estimation des paramètres des modèles sur base de mesures expérimentales constituent précisément l’objet de nos travaux de doctorat.

Les modèles mathématiques décrivant les procédés SMB consistent en les bilans massiques des composés à séparer. Ce sont des modèles à paramètres distribués (décrit par des équations aux dérivées partielles). Certains ont un comportement dynamique de type hybride (c'est-à-dire faisant intervenir des dynamiques à temps continu et des événements discrets). Quelques modèles ont été développés dans la littérature. Il s’agit de sélectionner ceux qui paraissent les plus intéressants au niveau de leur temps de calcul, de leur efficacité et du nombre de paramètres à déterminer. En outre, de nouvelles structures de modèles sont également proposées afin d’améliorer le compromis précision / temps de calcul.

Ces modèles comportent généralement certains paramètres inconnus. Ils consistent soit, en des grandeurs physiques mal définies au départ des données de base, soit, en des paramètres fictifs, introduits à la suite d'hypothèses simplificatrices et englobant à eux seuls un ensemble de phénomènes. Il s’agit de mettre au point une procédure systématique d’estimation de ces paramètres requérant le moins d’expériences possible et un faible temps de calcul. La valeur des paramètres est estimée, au départ de mesures réelles, à l'aide d'une procédure de minimisation d'une fonction de coût qui indique l’écart entre les grandeurs estimées par le modèle et les mesures. La sensibilité du modèle aux écarts sur les paramètres, ainsi que l’identifiabilité du modèle (possibilité de déterminer de manière univoque les paramètres du modèle) sur la base de mesures en fonctionnement normal sont étudiées. Ceci fournit un critère de comparaison supplémentaire entre les différents modèles et permet en outre de déterminer les conditions expérimentales optimales (choix du type d’expérience, choix des signaux d’entrée, choix du nombre et de la position des points de mesures…) dans lesquelles les mesures utilisées lors de l’estimation paramétrique doivent être relevées. De plus, les erreurs d’estimation sur les paramètres et les erreurs de simulation sont estimées. La procédure choisie est ensuite validée sur des données expérimentales recueillies sur un procédé pilote existant au Max-Planck-Institut für Dynamik komplexer technischer systeme (Magdebourg, Allemagne).

Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished

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.

S'han creat les eines necessàries per a estudiar la viabilitat de dur a terme la separació de mescles de dos i tres components basats en un mètode de separació en continu tipus SMB. Amb aquesta finalitat, s'ha creat un sistema per al disseny ràpid i econòmic de separadors SMB que permet simular el comportament d'una columna qualsevol integrada en un sistema SMB. Aquest sistema, està constituït per una sola columna cromatogràfica que pot treballar en qualsevol de les quatre zones en què es pot dividir un SMB.

El sistema de control de l'instrument permet simular cicles complets de separadors SMB. A més, el programa també permet treballar amb separacions formalment binàries o ternàries, en conformacions de SMB de 4, 6 i 8 columnes i combinació d'elles agrupades en 4 zones de treball. El sistema també integra un programa de simulació numèrica i optimització de separadors SMB.

La combinació del programa i el sistema de disseny de SMB permet establir la variació de la concentració de cada substància amb el temps podent així determinar: el nombre de columnes per zona, el temps de canvi de cada columna, el cabal d'operació a cada zona i la concentració de cada substància per cada sortida de l'SMB.

Per tal de verificar el correcte funcionament de l'equip complet s'ha dut a terme la separació de dos components, fenol i triclorofenol, determinant-ne les condicions òptimes de separació. Tot i que la retenció entre aquestes dues substàncies és molt similar, el prototipus ha permès estudiar el comportament de la unitat SMB complerta. També s'ha estudiat la separació del p-aminofenol i l'o-aminofenol com a part integrant del procés de fabricació del paracetamol i se n'han trobat les condicions òptimes d'operació. En treballar amb aquest procés s'ha buscat la màxima puresa del p-aminofenol en detriment de la puresa de l'o-aminofenol aconseguint una puresa de p-aminofenol a la sortida refinat del 97%.

Finalment, i des del punt de vista del canvi d'escala, s'han determinat els valors de la longitud no utilitzada de rebliment i del coeficient global de transferència de matèria per tal de poder extrapolar els resultats del prototipus a escala industrial.
Se han creado las herramientas necesarias para estudiar la viabilidad de desarrollar separaciones de mezclas de 2 y 3 componentes basados en un método de separación en continuo tipo SMB. Con esta finalidad se ha creado un sistema para el diseño rápido y económico de separadores SMB que permite simular el comportamiento de una columna cualquiera integrada en un sistema SMB. Este sistema está constituido por una única columna cromatográfica que puede trabajar en cualquiera de las cuatro zonas en que se puede dividir un SMB.

El sistema de control del instrumento permite simular ciclos completos de separadores SMB. Además, el programa también permite trabajar con separaciones formalmente binarias o ternarias, en conformaciones de SMB de 4, 6 y 8 columnas y combinación de ellas agrupadas en 4 zonas de trabajo. El sistema también integra un programa de simulación numérica y optimización de separadores SMB.

La combinación del programa y el sistema de diseño de SMB permite establecer la variación de la concentración de cada sustancia con el tiempo pudiendo así determinar: el número de columnas por zona, el tiempo de cambio de cada columna, el caudal de operación en cada zona y la concentración de cada sustancia por cada salida del SMB.

Para verificar el correcto funcionamiento del equipo completo se ha separado una mezcla de dos compuestos, fenol y triclorofenol, determinando las condiciones óptimas de separación. Aunque la retención entre estas dos sustancias es muy similar, el prototipo ha permitido estudiar el comportamiento de la unidad SMB completa. También se ha estudiado la separación del p-aminofenol y el o-aminofenol como parte integrante del proceso de fabricación del paracetamol y se han determinado las condiciones óptimas de operación. Al trabajar con este proceso se ha buscado la máxima pureza del p-aminofenol con menoscabo de la pureza del o-aminofenol consiguiendo una pureza de p-aminofenol a la salida de refinado del 97%.

Finalmente se han determinado los valores de la longitud de lecho no utilizada y del coeficiente global de transferencia de materia para extrapolar los resultados del prototipo a escala industrial.
The necessary tools to study the viability of developing separations of mixtures of 2 and 3 components using a continuous method like the SMB have been developed. A fast and non-expensive system to design such separations has been developed. This system can simulate the behaviour of a single column integrated in the SMB. This system is composed by a single column capable to work in every one of the four zones into which an SMB can be divided.

The control system gives the possibility of simulate complete cycles of an SMB separator. In addition the program also can work with binary or ternary separations, in SMB conformations of 4, 6 and 8 columns and its combinations grouped together in 4 working zones. The system also integrates a numerical simulation and optimization program of SMB separators.

The combination of program and SMB design system establishes the concentration of each substance within the time. It gives the following parameters: the number of columns per zone, the column switch time, the flow in each zone and the concentration at the SMB outlet.

In order to check the correct operation of the whole unit the separation of phenol and trichlorophenol have been done determining the best operation conditions. However the retention of this substances is very similar, the prototype has studied the complete separation. It also has been studied the separation of p-aminophenol and o-aminophenol as a part of the sysntesis process os paracetamole and the best separation condition have been stablished. While working with this process the maximum purity of p-aminophenol has been searched. The purity of p-aminophenol at the raffinate outlet is about 97%.

Finally the values of unused bed lenght and overall mass transfer coefficient have been calculated to extrapolate the results to the industrial scale.

La séparation des C8 aromatiques par Lit Mobile Simulé (LMS) permet d'obtenir du paraxylène (PX) pur. Les autres composés du mélange sont recyclés dans un réacteur afin d'être isomérisés puis séparés à nouveau. La charge du LMS est composée à environ 75% par ce flux de recyclage. L'intégration de la réaction dans le LMS, réalisée en intercalant des réacteurs d'isomérisation entre les lits d'adsorbant de la zone 3 (procédé LMS Réactif, LMSR), doit permettre une réduction de ce flux de recyclage.L'objectif de cette thèse est de développer une méthodologie d'étude des procédés de type Lit Mobile Simulé (LMS) et Lit Mobile Simulé Réactif (LMSR) basée sur :-un outil expérimental simplifié : le pilote One-column réactif (OCR)-des simulateurs One-column réactif ou non qui seront validés par les résultats expérimentaux du pilote-des simulateurs LMS et LMSR permettant d'accéder aux résultats des procédés industriels.Les simulations de One-column (OC) montrent une bonne sensibilité aux paramètres clés de la séparation des C8 aromatiques (sélectivité PX/EB et diffusion intracristalline). Les résultats expérimentaux font ressortir des difficultés importantes à mettre en œuvre le OC expérimentalement. Plusieurs hypothèses sont exposées pour expliquer les résultats obtenus mais les difficultés rencontrées limitent, en l'état, l'utilisation du pilote pour l'étude de la séparation (réactive ou non) des C8 aromatiques.L'étude du LMSR effectuée par simulation montre l'importance du nombre et de l'emplacement des réacteurs ainsi que de l'intégration du LMSR dans la boucle de production de PX. L'usage du LMSR pour la production de PX permet une réduction importante du débit de recyclage
Today, pure paraxylene (PX) is mainly obtained from a mix of C8 aromatics by a separation process based on adsorption: the Simulated Moving Bed (SMB). The other components of the blend are sent to an isomerisation reactor and are recycled to the SMB. 75% of the SMB feed flow rate come from this recycle flow. Coupling reaction and separation by inserting isomerisation reactors between the adsorption beds of the third zone (Simulated Moving Bed Reactor, SMBR) should allow a reduction of this recycling flow rate.The main objective of this thesis is to develop a new methodology for studying SMB and SMBR processes based on:- a simplify experimental tool : the One-column reactive (OCR) pilot unit- simulators of the OCR which will be validated by the experimental results obtain on the pilot unit- simulators of SMB and SMBR processes which give access to industrial processes results.Simulation results show that OC system seem to be sensitive to key parameters of C8 aromatics separation (PX/EB selectivity and micropore diffusivity). Results on the pilot unit highlight the difficulties to implement an experimental OC. Hypothesis are given to explain those results but, without modification, OCR pilot unit cannot be used to study xylene separation (with or without reaction).SMBR study done by simulation shows the impact of the placement and the number of reactors. Integration of SMBR in the global PX production scheme is also essential. SMBR allows an important reduction of recycling flow rate (up to 50%)

Doutoramento em Engenharia Química
A exploração de compostos, subprodutos e resíduos naturais é um passo chave para a obtenção de um futuro sustentável. A valorização e comercialização destes materiais dependem da aplicação de técnicas adequadas de conversão e separação/purificação que permitam obter os níveis desejados de pureza e produtividade. Os ácidos triterpénicos, particularmente os ácidos betulínico, oleanólico e ursólico, são compostos de elevado valor que têm atraído interesse devido às suas já reportadas propriedades nutraceuticas e farmacológicas. Estes triterpenoides estão presentes em diversas fontes vegetais mas podem ser encontrados com abundâncias consideráveis na casca do eucalipto (decídua e externa), um resíduo comum da indústria da pasta e papel. O isolamento dos ácidos triterpénicos é uma tarefa difícil devido às suas semelhantes estruturas moleculares, especialmente no caso dos ácidos oleanólico e ursólico, que são isómeros de posição. O leito móvel simulado (simulated moving bed, SMB) é uma técnica cromatográfica de separação contínua e em contracorrente que maximiza a força diretriz de transferência de massa permitindo a separação de moléculas mesmo quando as seletividades se aproximam de um. Por exemplo, é frequentemente utilizada no isolamento de enantiómeros. No SMB clássico a separação de dois componentes é efetuada em quatro zonas, os caudais e concentrações de alimentação são fixos e as portas de entrada/saída são comutadas simultaneamente. Recentemente, novas implementações tais como a modificação da concentração ou caudais da alimentação, a utilização de tempos de comutação variáveis e a introdução de novas zonas para separação multicomponente, têm permitido a obtenção de maior flexibilidade e melhor performance. Uma revisão profunda destes modos de operação foi feita durante esta tese. A modelação e otimização são passos essenciais no dimensionamento e desenvolvimento de qualquer processo e particularmente importantes no SMB. Como ponto de partida para o estudo do fracionamento de ácidos triterpénicos por leito móvel simulado, modelos fenomenológicos conhecidos foram aplicados para desenvolver de um simulador SMB. Durante este trabalho uma estratégia de otimização de unidades de SMB foi desenvolvida combinando as metodologias de desenho de experiências e respostas de superfície com simulações computacionais, com o objetivo de obter condições de operação ótimas com baixa complexidade e um esforço computacional reduzido. Esta técnica de otimização foi aplicada ao estudo da separação dos enantiómeros de óxido de trans-estilbeno, usando informação da literatura, e posteriormente comparada com outros procedimentos de determinação de condições de operação ótimas. Esta técnica permitiu purezas acima de 99.5 % para ambos enantiómeros, necessitando de um baixo número de simulações. A separação de ácidos triterpénicos foi inicialmente estudada à escala analítica, através de uma série de ensaios cromatográficos em diferentes condições para seleção de fase móvel e estacionária apropriada. Os melhores resultados foram obtidos com uma coluna Apollo C18 usando metanol/água 95/5 (%,v/v) e os parâmetros de equilíbrio e transporte foram determinados através de experiências de rutura com os compostos puros. Esta informação foi utilizada com sucesso na simulação da separação de uma mistura ternária, cujos resultados foram validados com experiências de rutura ternárias. A separação em SMB de uma mistura representativa de um extrato natural contendo os ácidos betulínico, oleanólico e ursólico foi desenhada utilizando um processo em dois passos: inicialmente o ácido betulínico foi isolado dos ácidos oleanólico e ursólico e, de seguida, os ácidos oleanólico e ursólico foram fracionados. Esta separação foi otimizada usando a metodologia de desenho de experiências e respostas de superfície combinada com simulações rigorosas e permitiu demonstrar que é possível produzir os ácidos betulínico, oleanólico e ursólico com purezas de 99.4 %, 99.1 %, e 99.4 %. Os polímeros molecularmente impressos (molecularly imprinted polymers, MIPs) são sintetizados para possuírem centros ativos altamente seletivos para moléculas alvo, tornando-os adsorventes muito promissores. Vários MIPs foram sintetizados por polimerização por precipitação usando diferentes formulações. Após a preparação, estes polímeros foram caracterizados por microscopia eletrónica de varrimento e os mais promissores, em termos de características morfológicas, foram diretamente testados através de experiências de adsorção. Os resultados revelam que o material “MIP1b” exibe selectividade infinita para o ácido oleanólico, a molécula alvo usada na sua síntese. Em conjunto com a sua capacidade de adsorção – superior à da previamente estudada fase C18 – estes resultados demonstram o elevado potencial do polímero “MIP1b” para aplicação na separação dos ácidos triterpénicos. Investigação adicional é necessária neste tópico onde diferentes técnicas de separação podem ser antecipadas. Este trabalho culminou com o dimensionamento e montagem de uma unidade laboratorial de leito móvel verdadeiro baseada num sistema de uma-válvula-ST por coluna recentemente patenteado, que permite à unidade operar sobre diferentes estratégias de operação e configurações.
The exploitation of natural compounds, by-products and residues is a key strategy for the pursuit of a sustainable future. The effective valorization and commercialization of these materials depends on the application of adequate conversion and separation/purification techniques that can provide desired levels of purity and productivity. Triterpenic acids, particularly betulinic, oleanolic, and ursolic acids, are high value molecules that have attracted considerable interest due to their reported nutraceutical and pharmacological properties. These triterpenoids are present in diverse vegetable sources but significant abundances are found in Eucalyptus bark (deciduous and external), a common residue from the paper and pulp industry. The isolation of triterpenic acids is a difficult task due to their similar molecular structures, particularly in the case of oleanolic and ursolic acids, which are positional isomers. The simulated moving bed (SMB) technology is a countercurrent continuous chromatographic technique that maximizes the mass transfer driving force, thus allowing the separation of compounds even when selectivities approach one. For instance, it is often used for enantiomers isolation. In a classic SMB, the separation of two components is accomplished across four zones, the flow rates and feed concentrations are fixed, and the inlet/outlet ports are switched synchronously. Recently, new implementations and modifications, such as the modulation of feed concentration or flow rates, variable switch times and additional zones for multicomponent separations, enabled better flexibility and performances to be achieved. A thorough review of these modes of operation was performed in this thesis. Modeling and optimization are necessary steps for the design and development of any process, being particularly important in SMB. As the starting point for the study of the fractionation of triterpenic acids by simulated moving bed, well know phenomenological models were applied to develop a SMB simulator. During this work, an optimization strategy of SMB units was developed combining the design of experiments and response surface methodologies (DoE-RSM) with computer simulations, aimed at providing good operating conditions with low complexity and reduced computational effort. This optimization technique was applied to the separation of trans-stilbene oxide (TSO) enantiomers using data from the literature and compared with other existing procedures for the determination of the best operation conditions. It allowed purities above 99.5 % for both TSO enantiomers while requiring a small number of simulations. The separation of triterpenic acids was initially studied at analytical scale, through a series of chromatographic assays under different conditions, to select appropriate mobile and stationary phases. Best results were obtained using an Apollo C18 column and methanol/water 95/5 (%, v/v), and equilibrium and mass transport parameters were determined through breakthrough experiments with pure compounds. This information was then successfully applied in the simulation of a ternary mixture separation, whose results were validated with ternary breakthrough measurements. The SMB separation of a representative natural extract containing betulinic, oleanolic and ursolic acids was designed using a two-step process: firstly, betulinic acid was isolated from oleanolic and ursolic acids, and secondly, oleanolic and ursolic acids were fractionated. This separation approach was optimized using DoE-RSM combined with rigorous simulations, and it was demonstrated that it is possible to produce betulinic, oleanolic and ursolic acids with purities of at least 99.4 %, 99.1 %, and 99.4 %. Molecularly imprinted polymers (MIPs) are synthesized to possess binding sites highly selective to specific molecules, making them very promising adsorbents. Several MIPs were synthetized by precipitation polymerization using different formulations. After preparation, these polymers were characterized by scanning electron microscopy and the most successful ones, in terms of morphological features, were directly tested carrying out batch adsorption experiments. The results disclosed that “MIP1b” material exhibits infinite selectivity for oleanolic acid, the template molecule used in its synthesis. Together with its adsorption capacity – even higher than that of the previously studied C18 phase – these results demonstrate the high potential of “MIP1b” polymer for application on the separation of triterpenic acids. Additional research is required in this topic, where distinct separation approaches may be anticipated. This PhD work culminated in the design and assembling of a laboratory simulated moving bed unit based on a recently patented system using a one- ST valve per column valve scheme, thus allowing the SMB to run under several operation strategies and configurations.

The solid-gas contacting for thermal storage and thermal recovery is generally carried out in fixed-bed regenerators. Compared to a fixed bed, higher thermal recovery can be achieved in a moving bed with countercurrent flow of gas and solids. However, the moving beds have not been widely used due to difficulties in solid handling. The relative movement of the bed to the gas flow can be simulated in a fixed bed by moving the inlet and outlet ports of the gas along the length of the bed. Similar simulated moving-beds are already in use for adsorptive separation of liquid mixtures in chemical industries. A Novel Moving-Port system is proposed to achieve simulated moving-bed operation in a fixed bed. We have carried out studies to evaluate the relative performance of the fixed and the simulated moving bed heat regenerators. We have examined the feasibility of replacing a set of three blast furnaces and thermal regeneration of an adsorption bed with the simulated moving-bed regenerator. It is found that high heat transfer intensification can be achieved. The results indicate that the volume of the Simulated Moving-Bed regenerator required is about 100 times smaller than the blast-furnace stoves. The heat transfer intensification is high enough to carry out thermal regeneration of the adsorption beds in a cycle time that is in the range of the pressure swing adsorption, which is favored for its faster rate of regeneration.