Trickle bed reactors (TBRs) exhibit complex hydrodynamics and this study is aimed at giving insight into whether liquid-solid mass transfer and wetting are influenced by bed depth in a 5 m trickling column using 4 mm glass spheres as random packing. Measurements were made using the novel electrochemical technique developed by Joubert and Nicol (2013). Using this technique the wetting and mass transfer could be measured simultaneously. The study proves that the liquid-solid mass transfer and wetting efficiency do not stabilise at a minimum bed depth. The parameters were found to continue decreasing until the bottom of the bed. For the upper branch of the hydrodynamic envelope, the rate of decrease for the wetting efficiency was slow at the top of the bed and decreased rapidly closer to the bottom. However, only the wetting efficiency decreased significantly as a function of bed length; the liquid-solid mass transfer exhibited only a slight decrease of 14%. This compared well with the results of Du Toit et al. (2014), who found an 11% decrease in the liquid-solid mass transfer in a column with an x/D value of 29,4. The lower branch of the hydrodynamic envelope showed a linear decrease with respect to bed length for both wetting and mass transfer. The liquid-solid mass transfer decreased by 50% from the top of the bed to the bottom. These results are also in agreement with those of Du Toit et al. (2014)1 who found a decrease of 30% for a 1,6 m column. The wetting efficiency for the Levec mode decreased by 52%, whereas Du Toit et al. (2014)2 found a decrease of 20%. / Dissertation (MEng)--University of Pretoria, 2014. / lk2014 / Chemical Engineering / MEng / Unrestricted

The prewetting of a trickle-bed reactor has important implications in the design and operation of these reactors. This is because the prewetting changes the flow morphology (shape and texture) of the liquid flowing through the bed and leads to the existence of multiple hydrodynamic states. The extent of this change in flow morphology can be seen in the effect the prewetting of the reactor has on the pressure drop, liquid holdup and gas-liquid mass transfer. The following prewetting procedures were used: -- Levec-wetted: the bed is flooded and drained and after residual holdup stabilisation the gas and liquid flow is reintroduced -- Kan-wetted: the bed is operated in the pulse flow regime and liquid and gas flow rates are reduced to the desired set point -- Super-wetted: the bed is flooded and gas and liquid flow are introduced once draining commences For the pressure drop: -- The different prewetting procedures resulted in two distinct regions (Upper region Kan and Super-wetted, Lower region Dry and Levec-wetted) -- There was no significant difference between the Dry and Levec-wetted beds -- The pressure drop in the Kan and Super-wetted beds can be as much as seven times greater than the pressure drop in the Dry and Levec-wetted beds For the liquid holdup: -- The different prewetting procedures resulted in four distinct regions (Kan-wetted, Super-wetted, Levec-wetted, Dry bed) -- The liquid holdup in the Kan-wetted bed can be as much as four times greater than the liquid holdup in the Dry bed -- The liquid holdup in the Levec-wetted can be as much as thirty percent lower than the liquid holdup in the Kan-wetted bed For the gas-liquid mass transfer: -- The different prewetting procedures resulted in three distinct regions (Kan and Super-wetted, Levec-wetted, Dry bed) -- The volumetric gas-liquid mass transfer coefficient in the Kan and Super-wetted beds can be as much as six times greater than the mass transfer coefficient in the Dry bed -- The volumetric gas-liquid mass transfer coefficient in the Kan and Super-wetted beds can be as much as two and a half times greater than the mass transfer coefficient in the Levec-wetted bed While an increase in the liquid flow rate results in an increase in the pressure drop, liquid holdup and gas-liquid mass transfer for all of the experiments, the effect of increasing gas flow on the measured variables were more pronounced for the prewetted beds. In a prewetted bed (Kan, Super and Levec-wetted) an increase in the gas flow rate causes an increase in the volumetric gas-liquid mass transfer coefficient and a decrease in the liquid holdup. The decrease in the liquid holdup is due to the fact that the increased gas flow rate causes the films around the particles to thin and spread out. In the dry bed the flow is predominantly in the form of rivulets and the increase in gas flow rate does not affect the liquid holdup. In the case of the volumetric gas-liquid mass transfer coefficient the increased gas flow rate causes an increase in the mass transfer coefficient regardless of the prewetting procedure. This increase is due to the effect that the gas flow rate has on the liquid holdup as well as the increase in the gas-liquid interfacial area due to the increased gas-liquid interaction. If the pulsing in the Kan-wetted bed is induced by increasing the gas flow rate and keeping the liquid flow rate constant the results are significantly different. The pressure drop in the gas-pulsing experiments was lower than the pressure drop in the recorded in the Kan and Super-wetted beds, but higher than the pressure drop in the dry and Levec-wetted beds. However, the liquid holdup in the gas-pulsing experiments was higher than the liquid holdup in any of the other beds. The volumetric gas-liquid mass transfer coefficient in the gas-pulsing experiments was lower than the mass transfer coefficients of the Kan and Super-wetted beds, but higher than the mass transfer coefficients in the dry and Levec-wetted beds. The multiple operating points obtained from the different prewetting procedures are by no means the only possible operating points. By simply decreasing the draining time in the Levec-wetted bed steady state operating points can be found between those of the Super and Levec-wetted beds. This alludes to the fact that the operating conditions determined from the different prewetting modes are only boundaries and that the actual operating point can lie anywhere between these boundaries. The existence of these multiple hydrodynamic states complicates things further when a correlation is developed to determine the pressure drop, liquid holdup or the volumetric gas-liquid mass transfer coefficient. No correlation tested was able to accurately predict the pressure drop, liquid holdup or volumetric gas-liquid mass transfer coefficient in the dry or prewetted beds. / Dissertation (MEng (Chemical Engineering))--University of Pretoria, 2007. / Chemical Engineering / unrestricted

Le captage de polluants des effluents industriels, et plus particulièrement du CO2, est un défi majeur à relever. Le procédé de captage du CO2 basé sur l’absorption par des solutions aqueuses d’amines est la technique la plus maîtrisée pour le traitement des fumées en postcombustion. La substitution des colonnes à garnissage par des colonnes à pulvérisation présente un intérêt économique car la surface d’échange entre les phases gazeuse et liquide est très importante réduisant ainsi la taille de la colonne d’absorption. De plus, les pertes de charge côté gaz sont évitées et les coûts de maintenance réduits. L’objectif de ces travaux de thèse est de caractériser le transfert de matière dans un spray au cours d'une absorption du CO2 par une solution aqueuse de monoethanolamine (MEA) en utilisant une nouvelle méthode.Ainsi, l’étude s’intéresse à la caractérisation locale du transfert de matière entre un spray de MEA à 30% massique et une atmosphère de CO2. Pour cela, une technique optique non-intrusive est utilisée : la réfractométrie arc-en-ciel globale (GRT). Cette technique est une mesure de l’indice de réfraction d’un ensemble de gouttes localisé dans une partie du spray. C’est donc une mesure locale dans un volume de l’ordre de quelques millimètres cubes. L’indice de réfraction d’une solution dépend de sa température et de sa concentration. Ainsi, à l’aide d’un étalonnage préalable dans un réacteur agité, les indices de réfraction des solutions aqueuses de MEA chargées sont reliés à leurs températures et à leurs concentrations de CO2 absorbé. La mesure d’indice de réfraction permet donc de suivre l’avancement du transfert de matière à travers la concentration de CO2 absorbé à une température moyenne du volume de mesure. La GRT est donc utilisée pour la mesure d’indice de réfraction au cours de l’absorption avec réaction chimique et, la quantité de CO2 captée par unité de volume est mesurée à plusieurs hauteurs de chute. Les mesures sont ensuite comparées aux prédictions d’un modèle de transfert de matière dans une goutte résolu numériquement sous COMSOL Multiphysics. Dans un deuxième temps, l’étude s’intéresse à la caractérisation du transfert de matière côté gaz en mesurant par spectrométrie infra-rouge la quantité de CO2 présente dans la phase gaz lors de l’absorption de celui-ci par une solution aqueuse de MEA à 30 % massique. Les résultats sont présentés sous forme d’efficacité de captage et un coefficient de transfert de matière côté gaz est calculé, en fonction de paramètres opératoires tels que les débits gazeux et liquide.Ces travaux de thèse, appliqués au captage du CO2, traite principalement de la mesure de transfert de matière grâce à la GRT pour la première fois utilisée à une absorption avec réaction chimique. La méthode développée permettra son utilisation pour d’autres systèmes chimique. / Pollutant capture, especially of CO2, is still a major challenge nowadays.CO2 capture based on absorption with chemical reaction by aqueous solutions of amines is the most mature technique for post-combustion gas cleaning.The substitution of packed columns by spray columns presents an economical interest since the exchange area between both gas and liquid phases is very important, reducing the size of the absorption column. In addition, gas side pressure losses are avoided and maintenance costs are reduced.The aim of this thesis is to characterize mass transfer in a spray column during a CO2 absorption by an aqueous solution of monoethanolamine (MEA) by using a new optical technique.The study focuses on the characterization of the local mass transfer between MEA spray and a CO2 atmosphere. In order to achieve this, a non-intrusive optical technique is used: Global Rainbow Technique (GRT). This technique measures the refractive index of droplets in a local portion of the spray. Therefore, the measurement is local with a volume of few cubic millimeters.The refractive index of a solution depends on its temperature and its concentration. Thus, by using a prior calibration in a stirred reactor, the refractive indices of CO2 loaded MEA solutions are correlated with their temperatures and CO2 absorbed concentration. Therefore, measuring refractive index is a measurement of mass transfer extent.GRT is then used during CO2 absorption with chemical reaction, and the amount of CO2 captured per volume unit is measured at several column heights. The experimental results are then compared with mass transfer predictions in a droplet with a model numerically solved in COMSOL Multiphysics.In another hand, gas side mass transfer is characterized by measuring the amount of CO2 in the gas phase with infrared spectrometry during CO2 absorption in an aqueous solution of 30 % MEA. The results are presented in term of capture efficiency and a gas-side mass transfer coefficient is calculated as a function of operating parameters such as gas and liquid flow rates.This work, applied to CO2 capture, deals with mass transfer measurement with GRT through a first application to absorption with chemical reaction. The developed method in this thesis will allow its use for other chemical systems.

No description available.

The objective of this PhD project is to develop novel membranes and desiccants that would help develop a second generation vacuum desiccant cooling (VDC) garment that is efficient, robust, durable and wearer-friendly. It was found that properly chosen support material could improve both mechanical strength and vapor flux for flat sheet polyvinylidene fluoride (PVDF), due to improved membrane structure and structure integrity that enhanced vapour mass transfer. Super solid desiccants were developed using a super absorbent polymer (SAP), which are sodium polyacrylate granules, as the host matrices to harbour LiCl. Furthermore, a novel desiccant based on loading LiCl in to hydrophobic hollow fibre membranes and therefore called membrane based desiccant fiber (MDF), was developed and demonstrated to be suitable for VDC. Heat and mass transfer for vapor absorption in MDF were analyzed. These membranes and desiccants, although developed for application in VDC, may also found applications in other fields such as water treatment, air conditioning, and natural gas dehumidification. Finally, based on the newly developed membranes and desiccants, three conceptual designs of second generation VDC garments are proposed.

L'objectif de ce travail était d'étudier les trois fonctions d'une colonne airlift sous dépression qui sont le pompage, les transferts gaz-liquide et l'extraction de matières particulaires par moussage-écumage. Le champ d'application ciblé concernait principalement le traitement des eaux aquacoles incluant l'extraction et la concentration de microalgues naturelles ou de culture. Chacune des fonctions a été étudiée séparément afin d'évaluer les capacités de l'airlift dans différentes conditions. L'étude de la fonction pompage a montré l'importance de la nature de l'eau, du type de diffuseur d'air, du débit gazeux injecté et du niveau de dépression appliqué. En eau douce, une forte coalescence des bulles est observée. Elle a pour conséquence une rétention gazeuse plus faible qu'en eau de mer. Le débit d'eau fourni par la colonne apparaît ainsi supérieur en eau douce (30 à 35 m3.h-1 contre seulement 10 à 20 m3.h-1 en eau de mer pour 5 m3.h-1 d'air injecté). A l'inverse, la hauteur de refoulement disponible est plus élevée en eau de mer (jusqu'à 0.8 m) qu'en eau douce (0.6 m maximum). Pour des circuits d'aquaculture où la perte de charge est faible, l'airlift est un système de pompage économique qui permet de réduire d'environ 40 % la consommation d'énergie par rapport à celle de pompes centrifuges. La colonne airlift présente également des capacités de transferts de matière comparables à celles de systèmes conventionnels. Les valeurs de KLa calculées pour la désorption du CO2 et comprises entre 0.002 et 0.01 s-1, sont environ quatre fois inférieures à celles obtenues pour le transfert d'oxygène par aération dans des conditions comparables. Les efficacités de transfert sont comprises entre 0.02 et 0.023 Kg.KW.h-1 pour le CO2 et entre 1.52 et 1.8 Kg.KW.h-1 pour l'O2. Les vitesses de transfert dépendent significativement du débit d'air, de la température, de la taille moyenne des bulles et de la présence d'aliments dans le bassin d'élevage. Elles sont peu affectées par la salinité, le niveau de dépression, la longueur du tube interne d'échange et le débit d'eau. Enfin, les capacités de séparation par moussage-écumage évoluent de façon positive quand le débit d'air et la taille des bulles sont réduits. L'efficacité globale d'extraction diminue avec l'augmentation de la concentration des produits extraits qui peut atteindre 130 fois la concentration initiale. La colonne à dépression apparaît ainsi comme un système multifonctionnel performant, même si l'efficacité maximale, pour chacune des fonctions, correspond à des conditions opératoires différentes. Ce procédé ouvre des perspectives de développement intéressantes dans des secteurs variés (de l'aquaculture au traitement des eaux industrielles). / The aim of this work was to study the three functions of a vacuum airlift, which are water pumping, mass transfer and foam fractionation. The investigations mainly focused on the treatment of fish culture water and on phytoplancton harvesting. Each function was studied separately, in order to assess the performance of the vacuum airlift with specific operating conditions. By studying the airlift pump, the effects of water and diffuser types, air injection conditions and depression level were shown. In fresh water, bubble coalescence was observed, which reduced gas holdup compared to sea water. Consequently, the water flow of the vacuum airlift appeared higher in fresh water than in sea water (30 to 35 m3.h-1 against 10 to 20 m3.h-1) for the same air flow rate (5 m3.h-1). Conversely, the available lift height was higher in sea water (up to 0.8 m) than in fresh water (0.6 m maximum). For low head aquaculture systems, the vacuum airlift may be an economical pumping system which allows a 40 % energy saving compared to centrifugal pumps. The vacuum airlift had a mass transfer efficiency similar to other gas transfer systems. The KLa values calculated for CO2 desorption ranged between 0.002 and 0.01 s-1. They were four times lower than those obtained for oxygen transfer in similar conditions. Mass transfer efficiencies ranged between 0.02 and 0.023 Kg.KW.h-1 for CO2 and between 1.52 and 1.8 Kg.KW.h-1 for O2. Mass transfer velocities significantly depended on air flow rate, water temperature, average bubble size and the presence of feed in the rearing tank. They are weakly depending on salinity, depression level, inner tube length or water flow. At last, foam fractionation increased when air flow and bubble size were reduced. The extraction efficiency decreased when the concentration of the extracted product increased (maximal concentration factor around130). The vacuum airlift appeared to be as a high-performance multifunctional system, even if the maximal efficiency for each of the functions corresponds to different operating conditions. This process could be used in a large scope of fields ranging from aquaculture to industrial water treatment.

Le marinage et le saumurage améliorent la durée de conservation, la tendreté et la jutosité de la viande et du poisson. En complément, un malaxage ou « barattage » est souvent appliqué aux pièces de viande préalablement à la cuisson. Le but principal de cette étude était d’évaluer l’impact des conditions de traitement sur les modifications biochimiques et structurales du tissu musculaire ; une grande partie concerne le malaxage. Les essais relatifs au marinage ont permis de fixer le pH et la teneur en NaCl de petits échantillons de Semitendinosus de bœuf respectivement à 6,5, 5,4 ou 4,3 et à 0,9 ou 2 % en masse ; une ANOVA a révélé les effets de ces 2 paramètres sur la taille des cellules et des espaces extracellulaires, l’oxydation des lipides et des protéines et l’hydrophobie de surface de ces dernières. Un simulateur de saumurage-malaxage conçu par le laboratoire a permis d’imposer des successions de déformations contrôlées (nombre de 350 à 2500, taux de compression de 10 à 30%) à des muscles Semimembranosus (SM) ou Rectus femoris (RF) de porc. Des traitements mécaniques semblables à ceux existant dans des barattes industrielles de tailles différentes ont ainsi été reproduits. Les principales conclusions sont : (1) le malaxage augmente nettement la diffusivité apparente du NaCl, d’une part, en altérant la structure tissulaire (+ 20 %), et d’autre part, en induisant une convection s’ajoutant à la diffusion (+200 %) ; (2) le traitement mécanique entraine en lui-même une augmentation de la solubilité des protéines, connue pour moduler les qualités des viandes transformées, de 20 à 50% par rapport à des échantillons non malaxés, qu’ils soient salés ou non ; (3) il entraine aussi une augmentation modérée de l’hydrophobie des protéines ; (4) la dégradation de l’endomysium, servant d’indicateur des modifications structurales, est plus marquée au milieu qu’en périphérie du muscle malaxé et d’autant plus importante que le traitement mécanique est fort et long. / Marinating and brining improve shelf-life, tenderness and juiciness of meat and fish. As a supplement massaging or tumbling is often applied to meat pieces before cooking. The main aim of this study was to assess the impacts of the processing conditions on the biochemical and structural changes in the meat tissue; a great part is focused on massaging. In the marinating trials the pH and NaCl content of thin samples of beef Semimembranosus muscle were set at 6.5, 5.4 or 4.3 and at 0,9 or 2 % (w/w), respectively; an ANOVA have shown the effect of these two parameters on the cells and extra cellular space sizes, the oxidation of lipids and proteins and the protein surface hydrophobicity. A brining-massaging simulator built by the laboratory was used to apply controlled successions of deformations (number from 350 to 2500, compression ratio from 10 to 30 %) to Semimembranosus (SM) ou Rectus femoris (RF) pork muscles. Mechanical treatments similar to those existing in industrial tumblers of various diameters were so reproduced. The main conclusions are: (1) massaging clearly increases the NaCl apparent diffusivity, on the one hand, by a modifying the tissue structure (+20%) and, on the other hand, by adding convection to diffusion (+200%); (2) the mechanical treatment promotes by itself an increase in protein solubility, known to affect processed meat quality, from 20 to 50 % in comparison with salted or unsalted reference samples; (3) it also increases moderately protein hydrophobicity; (4) the endomysium degradation, used as an indicator of structural changes, was more pronounced in the muscle periphery than in the middle and all the more marked than massaging was strong and long.

Hydrodynamic multiplicity in the trickle flow, or low interaction, regime is a well documented phenomenon. Multiple hydrodynamic states are often presented in the form of hysteresis loops where the hydrodynamic parameter studied are shown as a function of the operating history of the bed, i.e. liquid and gas flow rates. In extreme cases the lower leg, representing an increase in liquid flow rate on a pre-wetted and drained bed, is commonly referred to as the Levec mode. The upper extreme, referred to as the Kan-liquid mode, represents a decrease in liquid flow rate after operation in the high interaction regime. The many reported studies investigating liquid-solid mass transfer in trickle beds have generally used either the dissolution or electrochemical techniques. Numerous researchers have used their data to develop correlations predicting solid-liquid mass transfer coefficients. Most of these studies do not specify the multiplicity mode of operation. Only two studies (Sims et al. (1993) and Van der Merwe, Nicol&Al-Dahhan (2008)) use both the Levec and Kan-liquid operating modes. Both of these studies suggest that solid-liquid mass transfer also exhibit multiplicity behaviour although the trends suggested or speculated differ from each other. Sims et al. (1993) found that a Kan-liquid operated bed will outperform a Levec operated bed; however in contrast to this Van der Merwe et al. (2008) speculated that a Levec operated bed is better suited for liquid limited reactions due to enhanced liquid-solid mass transfer in the Levec mode as a result of faster interstitial velocity. This study showed that solid-liquid mass transfer coefficients, measured with both the dissolution and electrochemical technique, show multiplicity behaviour. Two distinct operating regions were found, which corresponds to the Levec and Kan-liquid modes. Measurements taken using the electrochemical technique yielded solid-liquid mass transfer coefficients larger than those measured using the dissolution method. The experimental results agree with the trend found by Sims et al. (1993) but the mass transfer coefficients in this study were significantly lower. Additionally it was shown that the difference in mass transfer coefficients, in the two modes, cannot be explained by merely compensating for the differences in wetting efficiency and interstitial velocity, suggesting that the Levec mode has a larger percentage of stagnant or poorly irrigated zones. It was also shown that mass transfer coefficients measured at the top of the column is higher than those measured at the bottom, suggesting that the flow structure is changing as a function of axial length. Lastly, with regards to electrochemical measurements of liquid-solid mass transfer, it was shown that measurements using a single particle electrode compared well to that of a multiple packing electrode. / Dissertation (MEng)--University of Pretoria, 2009. / Chemical Engineering / unrestricted

Orientador: Maria Angela de Almeida Meireles / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-26T21:20:51Z (GMT). No. of bitstreams: 1 Jesus_SusanaPereirade_D.pdf: 19153904 bytes, checksum: e8d3e5239f2dbe5f9d61e1e553bad266 (MD5) Previous issue date: 2015 / Resumo: A extração supercrítica consiste em uma operação unitária de separação na qual o solvente é um fluido no estado supercrítico, sendo que o dióxido de carbono (CO2) é o mais utilizado. Destaca-se por ser reconhecida como uma tecnologia limpa, alternativa aos métodos convencionais que em geral utilizam solventes orgânicos prejudiciais à saúde e ao meio-ambiente. O processo de extração supercrítica tem sido extensivamente estudado pela comunidade científica há mais de três décadas, o que resultou na construção de um sólido conhecimento sobre os principais fundamentos envolvidos neste processo, além da formação de uma ampla base de dados para descrever o comportamento de diferentes sistemas (CO2 + matriz sólida). É uma técnica de extração a alta pressão que começou a ser utilizada em escala comercial na década de 1980 e, desde então, o número de plantas em operação é crescente em algumas regiões como Europa, Ásia e Estados Unidos. Apesar disso, continua a ser considerada uma tecnologia emergente e inovadora, visto que os métodos convencionais ainda são predominantes em diversas aplicações industriais e, em muitos países (como é o caso do Brasil), a técnica ainda não é utilizada em escala comercial. A viabilidade técnica do processo de extração supercrítica já está consolidada e a tecnologia encontra-se disponível comercialmente. Além disso, pesquisadores da área afirmam que a técnica pode ser economicamente competitiva, dependendo da área de aplicação e do produto de interesse. Entretanto, a questão econômica ainda é considerada como o principal empecilho à disseminação desta técnica, pois os custos de investimento associados a uma planta de alta pressão são altos quando comparados à instalação de plantas que operam em baixas pressões. Diante deste cenário, considera-se importante a investigação de métodos de cálculo (modelagem e simulação) que possam ser aplicados no sentido de estimar parâmetros para design de processo e aumento de escala, os quais são requeridos em estudos de viabilidade econômica. No presente trabalho, dados disponíveis na literatura foram utilizados para estudar a modelagem matemática da transferência de massa no processo de extração supercrítica. Para tanto, dados cinéticos de matérias-primas diversas foram ajustados por meio da aplicação de diferentes modelos, tendo como foco avaliar a versatilidade e aplicabilidade dos mesmos em termos de design de processo. Os resultados demonstraram que o modelo spline e o modelo de Sovová foram eficientes na descrição quantitativa da curva de extração, além de apresentarem versatilidade para ajustar curvas com formatos diferenciados. O modelo spline apresentou os melhores ajustes e também menores erros na descrição da etapa CER (Constant Extraction Rate), a qual é a mais importante em termos de design de processo / Abstract: Supercritical fluid extraction (SFE) is a solid-fluid separation technique in which the solvent is a fluid in the supercritical state, and the supercritical carbon dioxide (CO2) is the most used one. It is recognized as a green technology and a versatile alternative to conventional extraction methods, which generally use organic solvents that are harmful to human health and environment. The SFE process has been extensively studied by scientific community for more than three decades. As a consequence, a solid knowledge about the fundamental concepts has been developed, and there is a huge amount of data to describe the behavior of different systems (CO2 + solid matrix). It is a high-pressure extraction method that has been carried out on a commercial scale since the 1980s. From that point on, a growing number of industrial plants have been operating in Europe, Asia, and USA. However, SFE can still be considered an emerging technology since the conventional methods remain the most used in various applications. Besides, this technique has yet not been applied on a commercial scale in several countries, such as Brazil. The technical feasibility of SFE process is consolidated and the industrial-scale technology is commercially available. Researchers in this field claim that costs of SFE may be commercially competitive, depending on application area and target products. Nonetheless, the economic aspects are still considered an obstacle in SFE technology dissemination. This happens especially because a high pressure process requires higher investment costs than a conventional low pressure plant. In this scenario, it is important to investigate calculation methods (modeling and simulation) that may be applied to estimate parameters for process design and scale-up, which are key points in studies of economic viability. In this work, the mathematical modeling of SFE mass transfer was investigated by using experimental data from literature. Then, different models were applied to fit the kinetic data of SFE from various raw materials. The main purpose was to evaluate the models by considering their versatility and applicability in terms of process design. The results showed that spline and Sovová¿s models have been very effective in describing the quantitative behavior of the extraction curves. Moreover, these models presented versatility in fitting different curve shapes. The spline model provided the best fits as well as the lowest residual errors in the CER (Constant Extraction Rate) period, which is the most important region for process design purposes / Doutorado / Engenharia de Alimentos / Doutora em Engenharia de Alimentos

Orientador: Fernando Galembeck / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T09:01:49Z (GMT). No. of bitstreams: 1 Balestrin_LiaBeraldodaSilveira_M.pdf: 4255591 bytes, checksum: c4d0f9d5952dc35354bfb9f0d111643b (MD5) Previous issue date: 2015 / Resumo: Quando dois materiais isolantes são atritados, ocorre a triboeletrização de suas superfícies, isto é, a formação de cargas estáticas, distribuídas em padrões fractais. Uma das hipóteses para explicar a eletrização de isolantes é a ocorrência de reações mecanoquímicas seguidas da transferência mútua de massa. Esta dissertação apresenta mapas de potencial elétrico de superfícies atritadas, que também foram examinadas por microscopia eletrônica de varredura (SEI, BEI) e microanálise EDX. Os resultados verificam a hipótese mecanoquímica associada à transferência de fragmentos poliméricos iônicos, sendo as reações iniciadas pela quebra de cadeias seguida da formação de várias espécies de alta energia e produtos de oxidação. Microanálises também detectaram a fixação de N2 nestas superfícies, evidenciando a participação da atmosfera e a formação de triboplasma. As imagens BEI revelam uma distribuição fractal de composição química consistente com a distribuição de fragmentos limitada por difusão, mas superior à dimensão fractal de distribuição de cargas. Esta diferença é atribuída à supressão de cargas devido a microdescargas elétricas desencadeadas por gradientes superiores à rigidez dielétrica do sólido ou do ar. As microdescargas diminuem os gradientes elétricos, mas, ao mesmo tempo, geram novas espécies muito reativas, aumentando a heterogeneidade química das superfícies. Essa dissertação descreve também alguns experimentos acerca da eletrização produzida por simples contato, obtendo-se padrões bem definidos com tempo de contato de 1 h, porém não revelam a transferência de fragmentos poliméricos mutuamente, sugerindo que o cisalhamento desempenhe um papel importante na transferência de fragmentos poliméricos eletrizados. Em um menor grau de aprofundamento, esta dissertação contempla outras consequências de cargas estáticas, como alterações no coeficiente de atrito / Abstract: Triboelectrification occurs when two insulators are rubbed, i.e. static charges are formed on the surface with a fractal distribution pattern. One of the hypotheses raised by the literature indicates that the electrification is accompanied by mutual mass transfer. This dissertation presents electric potential maps of rubbed surfaces, which were also examined by scanning electron microscopy (SEI, BEI) and EDX microanalysis. The results verify the hypothesis that the electrification is due to mechanochemical reactions associated with transfer of charged polymeric fragments. The reaction is initiated by breaking the chains, generating reactive species and oxidation products. Microanalysis also detected N2 fixation on these surfaces, evidencing the contribution of the atmosphere and the formation of triboplasma. The BEI images show a fractal distribution of chemical composition consistent with a fragment distribution limited by diffusion, but higher than the fractal dimension of the charge distribution. This difference is attributed to the suppression of charges due to electrical micro discharge triggered by gradients higher than the dielectric strength of solid or air. The micro discharges decrease electrical gradients, but at the same time, generates very reactive species further increasing the chemical heterogeneity of surfaces. This dissertation also describes some experiments about the electrification produced by single contact, resulting in well-defined patterns with a contact time of 1 h, but do not show the mutual transfer of polymeric fragments, suggesting that the shearing plays an important role in transferring electrified fragments. This work also includes other consequences of static charges, such as changes in the friction coefficient / Mestrado / Físico-Química / Mestra em Química