Dissertations / Theses on the topic 'BET isotherm'

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This work has evaluated the adsorption capability of three coal produced in the Universidade Estadual do Oeste do Paraná (tilapia bone residual coal, soybean bark coal and chestnut from Pará) and other kind of coal commercially obtained (babaçu coconut pealing coal) to remove the metronidazole from aqueous solution. The coal which better absorbed the metranidazole was the babaçu coconut peal one (CCCB) with temperature from 40ºC, 150 rpm of stirring and with no pH adjustment. Thus, the kinetic tests were performed by using the SOTAX dissolution apparatus, with 1000 mL of metronidazole solution, varying the concentration (200, 400, 650 and 850 mg/ L) and the temperature (30, 40, 45ºC), 1 g of the coal and 150 rpm of stirring. The equilibrium time observed was around 20 hours and in the first 4 hours a bigger amount of metranidazole was adsorbed, this inicial amount corresponds to the metranidazole adsorption in the outer layer of the CCCB. The results obtained from the adsorption kinetics were described by the intraparticule diffusion in which were verified the appearing of four well defined regions corresponding to the adsorption in the outer layer, in the macropores, in the CCCB mesopores and the equilibrium, respectively. In the equilibrium studies, were presented two adsorption mechanisms: monolayer and multilayer with increasing concentration of the adsorbate, corresponding to the hybrid model of Langmuir + BET. The removing process of metranidazole by using CCCB became economically viable due to the low cost in the obtention or production of the adsorbent, the easily extracetion of the babaçu coconut biomass and the excellent capability of maximum adsorptive to the metranidazole.
Neste trabalho, avaliou-se a capacidade de adsorção de três carvões produzidos na Universidade Estadual do Oeste do Paraná (carvão do resíduo ósseo de tilápia, carvão da casca da soja e o carvão da casca da castanha do Pará) e um carvão obtido comercialmente (carvão da casca do coco babaçu) para remoção do antibiótico metronidazol de solução aquosa. O carvão que melhor adsorveu o metronidazol foi o carvão da casca do coco babaçu (CCCB) com temperatura de 40ºC, 150 rpm de agitação e sem ajuste de pH. Dessa forma, os testes cinéticos foram realizados com o auxílio de um dissolutor (Sotax), utilizando 1000 mL de solução de metronidazol, variando a concentração (200, 400, 650 e 850 mg L-1) e a temperatura (30, 40 e 45ºC), 1 g do carvão e 150 rpm de agitação. O tempo de equilíbrio observado foi de aproximadamente 20 horas e nas primeiras 4 horas uma maior quantidade de metronidazol foi adsorvida, essa quantidade inicial corresponde à adsorção do metronidazol na camada externa do CCCB. Os dados obtidos a partir da cinética de adsorção foram descritos pelo modelo de difusão intrapartícula, no qual verificou-se o aparecimento de quatro regiões bem definidas correspondendo respectivamente a adsorção na camada externa, nos macroporos, nos mesoporos do CCCB e por último o equilíbrio. No estudo de equilíbrio, apresentou dois mecanismos de adsorção: monocamada e multicamadas com o aumento da concentração do adsorvato, correspondendo ao modelo híbrido de Langmuir+ BET. O processo de remoção de metronidazol utilizando o CCCB é economicamente viável visto o baixo custo na obtenção ou fabricação do adsorvente por ser extraído da biomassa do coco babaçu, além de possuir uma excelente capacidade máxima adsortiva para o antibiótico estudado.

water sorption isotherms of destoned and ground saiadey Jaul type dates were obtained at 30,40.50 C.using the gravimetric methods.Data were analyzed by applying the GAB,BAT ,Smith,Iglesias and Chrife,Halsey ,Henderson and Oswin Models.Isosteric heat of sorption value was calculated using the Clausius-Clapeyron Equation and tried to be as afunction of moisture content of dates. It was found that the experimental data fitted well to ,smith ,I glesias and Chirife ,Halsey, Henderson and Oswin equation, which are suitable for high sugar foods.Isosteric heat of sorption for dates varied from 0,9 to - 1,84 KJ/mol as moisture content changed from 11,0 to 18,0%.

Les évolutions de microstructures du nouvel alliage chinois Ti B19 ont été étudiées au cours de divers traitements thermiques et des relations entre microstructures et propriétés mécaniques ont été établies. Les cinétiques de transformations isothermes ont été établies par des mesures de résistivité électrique. Les structures et microstructures ont été caractérisées par DRX synchroton, Microscopies Optiques et Electroniques (MEB, MET). Les cinétiques de transformation et les caractéristiques microstructurales. Les cinétiques de transformation isothermes ont été obtenues, analysées (loi JMAK), et cet ensemble de résultats a conduit à l'établissement du diagramme TTT de l'alliage TiB19. Enfin il a été montré que la vitesse de chauffage a une très forte influence sur les transformations mises en jeu, et qu'une pré déformation plastique accélère les cinétiques de transformation (introduction de nouveaux sites de germination). Enfin les cinétiques de transformation ont été caractérisées en refroidissement continu depuis le domaine monophasé bêta. Une première approche de la modélisation des cinétiques de transformation a été menée en utilisant le loi JMAK et le principe d'additivité de Scheil. Enfin les relations entre microstructures et propriétés sont discutés
The phase transformations and microstructure evolutions has been characterized for different thermal treatments, and the relationships between final microstrures and properties have been investigated in the new metastable Ti-B19 alloy. The isothermal phase transformation kinetics and the influence of different heat treatment phaths have been establisheb by using in-situ electrical Resistivity. The structures have been determined by synchrotron X-Ray Diffraction and the microstructures were observed by SEM and TEM. The results show that phase transformation kinetics and microstructure characteristics are strongly dependent on the aging temperature (ranging from 300 to 700°C). The global isothermal phase transformation phase transformation kinetics has been got and anallyzed with JMAK equation, and the TTT diagram of Ti-B19 alloy has been established. We have also shown that the heating rate has remarkable influence on the isothermal phase transformation behaviors and the pre-deformation accelerates the transformation kinetics. The microstructure evolutions during cooling are obviously dependent on the cooling rates. A first attempt has been made to calculate the transformation kinetics during cooling using JMAK law and Scheil principle. Finally, the relationship between mechanical properties and microstructure has been discussed

The Onsager heat of transport for p-tert-butyltoluene was measured, as part of a series of preliminary experiments towards the determination of the importance of temperature gradients on the air-sea flux of carbon dioxide. The results presented in this thesis imply that the temperature gradient is a major contributor to the magnitude of the air-sea flux. The heat of transport has been measured for the p-tert-butyltoluene system by measuring stationary-state pressure changes for known temperature differences on the vapour side of the interface. At the pressure ranges used the number of mean free paths was always outside the Knudsen zone, but the values of Q* were approximately 100 % of the latent heat of vaporisation. Departures from linearity of plots of P against ΔT are attributed to temperature jumps at the surface of the dry upper plate. Both the results taken for p-tert-butyltoluene and the earlier results for water from this laboratory fit to a Type III BET isotherm, where the c parameter is not constant. They also reveal the importance of the temperature gradient in determining the value of the thermal accommodation coefficient, and provide a new method of measuring thermal accommodation coefficients for a variety of surfaces and vapours

Energy use in buildings accounts for a large portion of global and regional energy demand and energy-related CO2 emissions. To steer the world towards a low carbon future, the development of new and more efficient technologies is required. In hot and humid climates, the high latent heat loads results in uncomfortable and unhealthy indoor environments, accounting for 30% to 50% of standard air conditioning energy requirements. Physical adsorption of water vapour on solid desiccants is found to offer an energy efficient alternative to conventional dehumidification process using standard air conditioning systems. However, the isosteric heat of adsorption released increases the surface vapour pressure of the solid desiccants resulting in a decreased adsorption capacity. In packed beds of solid desiccants, this heat of adsorption increases the bed temperature, exit air temperature and exit air humidity ratio subsequently imposing an increased cooling load requirement and high energy requirement in the regeneration of the solid desiccants. In literature, several approaches used in removing in situ the heat of adsorption released in packed bed systems were fraught with several limitations. To this end, an integrated packed bed-oscillating heat pipe (OHP) system was proposed. The concept was for the evaporator of the OHP to remove the heat of adsorption generated by the packed bed and reject at its condenser towards an energy efficient isothermal adsorption process. To achieve this, theoretical investigations of the individual systems and the integrated systems preceded experimental testing of a rig set up in the laboratory. For the theoretical studies, the OHP was helically coiled at both ends, filled with ethanol, methanol and water working fluids respectively at 50% volume fraction and numerically investigated using the Eulerian Volume of Fluid (VOF) model in ANSYS Fluent R15.0. The packed bed on the other hand was configured as a Heggs et al (1994) Z-type flow arrangement for enhanced radial flow using the Porous Media model in ANSYS Fluent R15.0 set up with the properties of Silica Gel. ANSYS Fluent R15.0 System Coupling limitations led to the development of mathematical models for the prediction of the integrated system performance. The experimental investigations were in line with the theoretical only in this case the optimum working fluid, deionized water, was used as the main working fluid in the helically coiled OHP (HCOHP). The results showed reasonable agreement between the performance of the numerical model and experimental prototype. The HCOHPs were capable of passively removing heat from the packed bed systems. Mean bed temperature reduction between the integrated packed bed-HCOHP system and corresponding individual packed bed configurations were about 5.61°C, 9.48°C and 10.14°C respectively for the large annulus (LAPB), medium annulus (MAPB) and small annulus (SAPB) packed bed configurations. Average packed bed outlet temperature reductions of about 6.61°C, 9.19°C and 6.29°C were also achieved for the respective configurations. A validation of the theoretical model showed average temperature difference of about 5.60°C between the experimental prototype of the integrated system and results predicted using experimental packed bed temperature data and HCOHP thermal resistance. Compared to other similar systems in literature, the integrated packed bed-HCOHP system showed capacity to passively remove significant amounts of the heat of adsorption released in silica gel packed beds towards isothermal adsorption.

El objetivo principal de este trabajo es predecir la dispersión de un flujo bifásico en el lecho de un reactor de hidrodesulfuración. Se consideran propiedades físicas constantes, sin incluir reacciones químicas ni procesos de transferencia de calor ni materia. Dos herramientas de simulación diferentes se han utilizado en este estudio. Una de ellas es el software comercial Fluent, ampliamente utilizado en el campo de la Computación en Dinámica de Fluidos, en el que se han introducido nuevos modelos de arrastre y capilaridad no incluidos en la versión comercial del software. La segunda herramienta utilizada es el código doméstico Multiphase Flow Solver, escrito en lenguaje de programación Fortran, que ha sido desarrollado durante esta tesis doctoral, constituyendo un importante objetivo de la misma. Este código incorpora los modelos necesarios para describir los procesos físicos que describen el comportamiento de este tipo de flujos multifásicos y su dispersión en medios porosos.
The main objective of this work is to predict the two-phase flow dispersion in the bed of a hydrodesulfurization reactor. Physical properties are considered to remain constant, without including chemical reactions nor heat and mass transfer processes. Two different simulation tools have been used in this study. One of them is the commercial software Fluent, widely used in the field of Computational Fluid Dynamics, in which new drag and capillarity models not included in the commercial version of the software have been implemented. The second tool used is the domestic code Multiphase Flow Solver, written in Fortran programming language, which has been developed during this doctoral thesis, being one important goal of it. This code includes the models needed to describe the physical processes which describe the behavior of this type of multiphase flows and their dispersion in porous media.

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A crescente necessidade da utilização de espécies forrageiras de estação fria na região sul do país vem determinando uma grande demanda por sementes de qualidade. Entre as leguminosas se destaca o cornichão (Lotus corniculatus L.), que é uma leguminosa forrageira oriundo da Europa e da região mediterrânea. Esta leguminosa forrageira tem na versatilidade a sua maior vantagem, visto que apresenta produção de forragem na primavera, no verão e no outono, possui resistência à seca e ao encharcamento temporário do solo e apresenta boa persistência da massa verde. Além disso, as sementes deste tipo de espécie podem ser misturadas com espécies de inverno, o que aumenta o rendimento da matéria seca, dá uma melhor distribuição da forragem ao longo do ano e agrega uma melhora na qualidade das pastagens. Apesar dessas vantagens, as sementes de cornichão comercializadas possuem ainda uma baixa qualidade. Esse fato é decorrente de um sistema de fiscalização ineficiente, associado à dificuldade de produção e beneficiamento do produto. Outro problema que o produtor de sementes desta espécie enfrenta é a dormência tegumentar, isto é, o revestimento da semente (tegumento) é impermeável e não permite que a água necessária para a germinação chegue ao interior da semente. Na literatura, diversos trabalhos têm relatado que cada vez mais há um aumento na demanda de sementes forrageiras em função do melhoramento do campo nativo e das pastagens cultivadas. Diante de um mercado tão promissor, a obtenção de sementes de melhor qualidade ainda apresenta dificuldades que vão desde a fase de produção no campo, onde as sementes são colhidas precocemente em relação ao ponto de maturidade fisiológica devido ao processo de perda natural, até seu beneficiamento, onde o processo de secagem apresenta-se como uma etapa limitante que necessita de uma atenção muito especial para evitar perdas fisiológicas no produto final. De um modo geral, a secagem é definida como a remoção, voluntária ou não, total ou parcial, de uma fase líquida ou gasosa de qualquer material através da transferência de calor e de massa. A secagem tem em sua essência a finalidade de assegurar a conservação de um produto por meio da redução do seu teor de água. No caso de materiais orgânicos, como é o caso de sementes, a redução no teor de água deve ser efetuada até o ponto em que a concentração de açúcares, ácidos, sais e outros componentes, sejam suficientemente elevados para reduzir a atividade de água e inibir, portanto, o desenvolvimento de micro-organismos. Na tecnologia de produção de sementes de alta qualidade a secagem é tida com uma das etapas de maior importância, pois permite a redução do teor de água em níveis adequados para o armazenamento e comercialização (12 a 15 % de umidade), preserva as sementes de alterações físicas e químicas induzidas pelo excesso de umidade, torna possível a manutenção da qualidade inicial durante o armazenamento e possibilita colheitas próximas da maturação fisiológica. Entretanto, o processo de secagem, seja ele qual for, deve acontecer de forma controlada e de maneira uniforme a fim de evitar elevados gradientes de umidade e temperatura no interior do material que podem provocar a perda da qualidade do produto final. De acordo com o que foi exposto, o presente trabalho de mestrado teve como objetivo realizar um estudo sobre o processo de secagem de sementes de cornichão (Lotus corniculatus L.) em um secador de leito fixo com fluxo de ar paralelo. Para alcançar tal objetivo, este trabalho foi dividido nas seguintes etapas: caracterização física e fisiológica das sementes, análise do processo de reumidificação das sementes, estudo das isotermas de dessorção das sementes reumidificadas e avaliação dos efeitos da variação da temperatura, da velocidade do ar e da altura da bandeja sobre a cinética de secagem e qualidade fisiológica do produto final. Os dados experimentais mostraram que os resultados obtidos para a umidade em base úmida das sementes secas ficaram na faixa de 5 % para as secagens realizadas a 60 °C e em aproximadamente 8 % para as secagens realizadas a 40 °C. No que se refere à germinação, os valores encontrados estão na ordem de 44 a 59 % para as secagens realizadas neste estudo. Dentre as secagens, a que obteve o maior valor de germinação, com valor de 59 %, foi a realizada na condição de T = 40 °C, v = 1,0 m/s e h = 1,0 cm.
The growing necessity for the use of cool-season forage species in the southern region of the country has indicated a high demand for quality seeds. Among the legumes, the birdsfoot trefoil (Lotus corniculatus L.) is a forage legume which is originated in Europe and in the Mediterranean region. This versatility in the forage legume has its biggest advantage, since it presents forage production in the spring, summer and autumn, is resistant to drought and temporary waterlogging and shows good persistence of green mass. Furthermore, seeds of such kind can be mixed with winter species, which increases the yield of dry matter, gives a better distribution of the material throughout the year and adds an improvement in the quality of pastures. Despite these advantages, the seeds of birdsfoot marketed still have a poor quality. This fact is a result of an inefficient system of monitoring and difficulties associated to production and processing of the product. Another problem is that the seed producer of this species is facing cutaneous numbness, that is, the seed coat (tegument) is impermeable and does not allow the water, necessary for germination to reache the interior of the seed. In the literature, several studies have reported that there is an increasing demand for an increase in forage seed due to the improvement of native grassland and cultivated pastures. Faced with such a promising market, obtaining better quality seed still presents difficulties ranging from the production phase of the field, where the seeds are harvested early in relation to physiological maturation due to the natural loss process until its processing where the drying process is presented as a limiting step that requires particular attention to avoid losses in physiological final product. In general, drying is defined as the removal voluntary or not, full or partial, of a liquid or gaseous phase of any material by the transfer of heat and mass. Drying has its essence in order to ensure the preservation of a product through reduction of water content. In the case of organic materials, such as seeds, reduction in water content must be performed to the extent that the concentration of sugars, acids, salts and other components are sufficiently high to reduce the water activity and inhibit, therefore, the growth of microorganisms. In the production of high quality seeds the drying technology is seen with one of the most important steps, since it allows reducing the water content suitable for storage and marketing levels (12 to 15% moisture), preserves the seeds from physical changing and chemical induced excess moisture, makes it possible to maintain the initial quality during storage and enables the next harvest physiological maturity. However, the drying process, whatever it may be, should occurs in a controlled and uniform manner in order to avoid high temperature and humidity gradients within the material that could result in loss of quality of the final product. Towards to it, this paper aimed to conduct a study on the drying of seeds of birdsfoot trefoil (Lotus corniculatus L.) in a fixed bed dryer with parallel air flow. To accomplish this goal, this study was divided into the following steps: physical and physiological seed characterization, analysis of rewetting seed process, study of desorption isotherms of the rewetted seeds and evaluation the effects of temperature, air velocity and the height of the tray on the drying kinetics and physiological quality of the final product. The experimental data showed that the results for the dry seeds of UBU were in the range of 5 % to drying carried out at 60 ° C and about 8% to drying carried out at 40 ° C. With regard to seed germination, the values are found in a range of 44 to 59% for the drying carried out in this study. The drying condition whom presented the highest germination value about 59 % was performed on T = 40 ° C, v = 1,0 m/s and h = 1,0 cm.

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O objetivo deste trabalho foi estudar a secagem de filés de anchoita in natura e modificados enzimaticamente, em secadores de leito fixo (camada delgada) e leito móvel (leito de jorro), sendo avaliadas as propriedades termodinâmicas e as características do produto final. Em relação às propriedades termodinâmicas, a modificação enzimática dos filés de anchoita promoveu aumento da umidade de monocamada e das constantes relacionadas às multicamadas. Isto levou a um aumento de até 170% na intensidade da ligação da água, mostrada através das entalpias diferencial e integral, e uma diminuição 193% no número de sítios ativos livres e 520% da mobilidade molecular, mostrada através das entropias diferencial e integral, respectivamente. Com a hidrólise também ocorreu aumento, em média, de 29% na área superficial de sorção e diminuição do tamanho dos poros. O processo de dessorção mostrou ser controlado pela entalpia, sendo espontâneo para o filé in natura e não espontâneo para o modificado. Com respeito à cinética de secagem, o aumento da intensidade da ligação da água e diminuição do tamanho dos poros, com a modificação enzimática, acarretou maior dificuldade remoção de água, o que foi comprovado pela diminuição da difusividade efetiva de umidade (Def) do material modificado (0,74×10-10 a 1,84×10-10 m2 /s) em relação aos filés in natura com pele voltada para baixo (3,3×10-10 a 8,6×10-10 m2 /s), nas temperaturas estudadas (50, 60 e 70ºC). Na secagem dos filés, a menor alteração ocorreu na condição de 60ºC para as amostras secas pelos dois lados. Nesta condição, a solubilidade, digestibilidade in vitro e atividade antioxidante específica (AAE) diminuiram 25%, 6% e 10%, respectivamente; os conteúdos de lisina e metionina disponíveis foram de 7,21 e 2,64 g/100gproteína, respectivamente; o índice de TBA de 1,16 mgMDA/kg; a atividade antioxidante específica de 1,91 µMDPPHseq/gptna solmin. Em relação à secagem da pasta modificada enzimaticamente, a melhor condição de operação foi a uma temperatura de 60 ºC e espessura de 2,5 mm. Nestas condições os produtos apresentaram baixa oxidação lipídica (0,93mgMDA/kg), redução na lisina disponível de 16%, estando dentro do limite recomendado para pescado, e perda de 20% na AAE. Na secagem em leito de jorro da suspensão protéica modificada enzimaticamente (SPME), a menor redução no conteúdo de lisina disponível (9%) e a menor perda na AAE (8%) ocorreram a temperatura do ar de entrada de 90ºC, concentração da suspensão de 6,5% e vazão de alimentação da suspensão de 200 mL/h. O produto desidratado em leito de jorro caracterizou-se como uma fonte protéica de elevado valor biológico, considerando o perfil de seus aminoácidos essenciais, pois foi capaz de atender às recomendações nutricionais recomendadas pela FAO/WHO.
The aims of this work was to study the drying of in natura anchovy fillets and enzymatic modified in fixed bed (thin layer) and moving bed (spouted bed) dryers, it was being evaluated the thermodynamic properties and the final product characteristics. In relation to the thermodynamic properties, the enzymatic modification of anchovy fillets showed an increase in monolayer moisture and in constant related to multilayer. Which led to an increase of 170% the intensity of water bound, shown through the differential and integral enthalpies, and a decrease of 193% in the number of free active sites and 520% of the molecular mobility, shown through the differential and integral entropies, respectively. With the enzymatic hydrolysis was also increased of 29% on sorption surface area and consequent reduction in pore size. The desorption process showed to be controlled by enthalpy, being spontaneous for the fillet and non-spontaneous for the modified. With respect to drying kinetics, the increased intensity of water bound and decreased pore size, with the enzymatic modification, resulted in a more difficult removal of water, which can be shown by decreased effective moisture diffusivity (Def) of the modified material (from 0.74×10-10 to 1.84×10-10 m2 /s) in relation to in natura fillet with skin side down (from 3.3×10-10 to 8.6×10-10 m2 /s) at studied temperatures (50, 60 and 70 ºC). In the drying anchovy fillets the lower change was in condition at 60 °C with air flow for two sides of the samples. In this condition, the solubility, in vitro digestibility and specific antioxidant activity decrease 25%, 6% and 10%, respectively; the contents of available lysine and methionine were 7.21 and 2.64 g/100protein, respectively; the TBA value was 1.16 mgMDA/kg. With respect the drying of enzymatic modified fillet (paste), the best drying condition was obtained at 60 ºC and thickness sample 2.5 mm, in which the TBA value was 0.93 mgMDA/kgsample, reduction in available lysine about 16% and specific antioxidant activity loss of 20.2%. Drying in spouted bed of paste, the lower reduction in available lysine (9%) and loss of specific antioxidant activity (8%) occurred at 90 °C, 6.5% and 200 mL/h. In these operation conditions, the dehydrated product was characterized as a high biological protein source value, taking into account the essential amino acids profile, it was able meet to recommended by FAO/WHO.

In this thesis, a numerical study of simulating and computing the magnetocaloric properties of magnetic materials is presented. The main objective was to deduce the optimal procedure to obtain the isothermal change in entropy of magnetic systems, by evaluating two different formulas of entropy extraction, one relying on the magnetization of the material and the other on the magnet's heat capacity. The magnetic systems were simulated using two different Monte Carlo algorithms, the Metropolis and Wang-Landau procedures. The two entropy methods proved to be comparably similar to one another. Both approaches produced reliable and consistent results, though finite size effects could occur if the simulated system became too small. Erroneous fluctuations that invalidated the results did not seem stem from discrepancies between the entropy methods but mainly from the computation of the heat capacity itself. Accurate determination of the heat capacity via an internal energy derivative generated excellent results, while a heat capacity obtained from a variance formula of the internal energy rendered the extracted entropy unusable. The results acquired from the Metropolis algorithm were consistent, accurate and dependable, while all of those produced via the Wang-Landau method exhibited intrinsic fluctuations of varying severity. The Wang-Landau method also proved to be computationally ineffective compared to the Metropolis algorithm, rendering the method not suitable for magnetic simulations of this type.

Remoções quase totais de clorofenóis, por processos anaeróbios, já foram atingidas mediante elevada concentração de matéria orgânica e um número considerável de fontes de carbono. Porém, é necessário que se investigue o desempenho dos reatores submetidos a condições menos idealizadas. Este trabalho apresenta o desenvolvimento de uma metodologia para avaliar um reator anaeróbio de leito fluidificado (RALF) como etapa de pré-tratamento de substrato sintético contendo pentaclorofenol (PCP). Para isso, foram adotadas as seguintes condições experimentais: fonte única de carbono; concentração reduzida de matéria orgânica; biomassa não previamente adaptada, e menores tempos de detenção hidráulica. Para cumprir o objetivo citado, foram desenvolvidos dois reatores, com 2,2 e 16 litros, respectivamente, e foram realizadas etapas de avaliação de materiais suporte, estudo de diversas interações (partícula/fluido, partículas fluido, biopartícula/fluido e biopartículas/fluido), e análise do desempenho do RALF sem PCP e com PCP. Os materiais suporte escolhidos foram a alumina, o basalto e o carvão ativado granular, todos com diâmetros próximos a 3 mm. Eles foram avaliados em ensaios de caracterização física, de microscopia eletrônica de varredura, de fluidodinâmica e de análise de imagens. O carvão apresentou os melhores resultados e foi escolhido para a continuidade do trabalho. As interações foram analisadas através de ensaios fluidodinâmicos, isotermas de adsorção, dentre outros. Nas condições experimentais utilizadas, a biomassa aumentou a densidade da partícula, fato que foi comprovado pelos ensaios para determinação da velocidade mínima de fluidificação, de expansão e porosidade do leito, e também de velocidade terminal da partícula isolada. As isotermas de adsorção demonstraram que a presença de matéria orgânica diminuiu em 9% a adsorção do PCP. O RALF apresentou um comportamento satisfatório no período de operação sem PCP. Nos 105 dias de operação, a eficiência média de remoção de DQO ficou quase sempre superior a 90%, e os outros parâmetros de monitoramento de desempenho apresentaram valores típicos, indicando estabilidade no processo. A presença de PCP no sistema, nas concentrações utilizadas, não alterou a qualidade da biomassa presente, e nem os parâmetros de monitoramento de desempenho, como DQO, alcalinidade, pH e ácidos voláteis. Mesmo sob condições menos idealizadas, foi observado um desempenho satisfatório do reator na remoção do PCP. Em concentrações variando de 1 a 6 mg/L, foram observadas eficiências médias de remoção de 93% e 70%, respectivamente, para os 80 dias de operação nessas condições. Diante dos resultados obtidos, foi possível concluir que a remoção de PCP em um RALF pode ser atingida mediante condições operacionais mais simples.
The almost total removal of chlorophenols by anaerobic processes has been achieved under high concentrations of organic matter and a considerably large number of carbon sources. However, it is necessary to investigate the performance of such reactors under less idealized conditions. The present work shows the development of a new methodology for evaluating the use of an anaerobic fluidized bed reactor (AFBR) in the pretreatment step of a synthetic substrate containing pentachlorophenol (PCP). In order to do that, the following experimental conditions were used: a single source of carbon; reduced concentrations of organic matter; non-previously adapted biomass, and smaller hydraulic retention times. To achieve the main objective, two reactors, one having a volume of 2.2 L and the other one, 16 L, were especially designed; evaluation steps of support material and the study of several interactions (particle/fluid, particles/fluid, bioparticle/fluid, bioparticles/fluid) were carried out, and the performance of the AFBR with and without PCP was analyzed. The three support materials employed were alumina, basalt and granular activated carbon, all having average diameters of 3 mm. These materials were evaluated through physical characterization methods, microscopy, hydrodynamic and image analyses. The activated coal showed the best results and was exclusively employed in the remainder of the work. The interactions were analyzed by hydrodynamics and adsorption isotherms, to name but a few. Under the experimental conditions employed, the biomass made the particle density increase, a fact that was verified in the determination of the minimum fluidization velocity, the bed porosity and expansion as well as the terminal velocity of isolated particles. The adsorption isotherms showed a decrease of 9% in PCP absorption due to the existence of organic matter. The AFBR showed satisfactory results during the operation without PCP. In the 105 days of operation, the average efficiency of COD removal remained almost always over 90%, while the other performance monitoring parameters remained at typical values, indicating the process stability. The presence of PCP under the concentrations used in the system did not seem to affect neither the quality of the biomass nor the performance monitoring parameters, like COD, alkalinity, pH and volatile acids. Even under less idealized conditions, the reactor showed good performance in removing PCP. The average efficiencies of removal attained around 93% and 70% for concentrations of 1 to 6 mg/L respectively. These concentration levels were kept during 80 days. In view of the results obtained, it is possible to conclude that reasonably good efficiency of PCP removal in AFBR can be attained under simpler operational conditions.

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Os metais pesados sÃo conhecidos por serem altamente tÃxicos em baixÃssimas concentraÃÃes na Ãgua. Sendo assim, numerosos estudos tem sido dedicados à sua remoÃÃo a limites aceitÃveis do ponto de vista ambiental. Tais pesquisas se concentram, principalmente, no desenvolvimento de uma remoÃÃo eficiente e de baixo custo. Muitos mÃtodos tÃm sido propostos para remoÃÃo de metais pesados, por exemplo, precipitaÃÃo, membranas filtrantes, troca iÃnica e adsorÃÃo. A precipitaÃÃo à um dos mÃtodos que mais vem sendo utilizado embora seja um mÃtodo inadequado no que se refere a impactos ambientais por gerar resÃduos. A casca de coco oferece facilidade natural de ser encontrado e manejado, por isso à um dos materiais mais estudados para fins de reaproveitamento. Este trabalho se propÃe a fazer um estudo de adsorÃÃo de Cu+2 utilizando casca de coco modificado como adsorbente. As modificaÃÃes empregadas foram (a) por polimerizaÃÃo do formaldeÃdo em meio sulfÃrico; b) Tratamento com lÃquido iÃnico e c) EsterificaÃÃo por Ãcido multicarboxÃlicos e multifenÃlicos. Os modelos aplicados para o estudo de isotermas foram de Langmuir, Freundlich, Temkin e Dubinin âRaduschevich. Aplicando o modelo de Langmuir no estudo de adsorÃÃo de Cu(II) no adsorbente modificado BCFB a capacidade mÃxima de adsorÃÃo qm e a constante KL foram 125 mg/g e 1,11x10-1 L.mg-1 para o Cu+2 . Para os adsorbentes BC/LI e BCTÃnico o valor de qm foram 64,5 e 99mg.g-1 , respectivamente enquanto o valor de KL foram 5,3x10-2 e 5,6x10-2 , respectivamente . O modelo cinÃtico que melhor se ajustou ao fenÃmeno foi o de segunda ordem. Os resultados obtidos mostraram que a casca de coco quimicamente modificado à um potencial adsorbente para remoÃÃo de Cu+2. O estudo de coluna foi empregado para verificar a desempenho do adsorbente quando se emprega efluente industrial. Nas condiÃÃes empregadas neste estudo a modificaÃÃo com Ãcido tÃnico foi a que teve melhor desempenho de remoÃÃo. Destaca-se tambÃm a capacidade de reutilizaÃÃo do adsorbente que promove uma diminuiÃÃo do custo operacional quando à considerada sua aplicabilidade numa escala industrial.
The heavy metals are known to be highly toxic at very low concentrations in water. At this point, numerous studies have been dedicated to their removal to acceptable limits of an environmental point of view. Such researches are focused mainly in developing an efficient removal and low cost. Many methods have been proposed for removing heavy metals, for example, precipitation, membrane filtration, ion exchange and adsorption. The precipitation is one method that has been used more although an inappropriate method regarding the environmental impact for generating residues. The bagasse, coconut offers natural facility to be found and handled, so it is one of the most studied materials for reuse. This paper aims to make a study of adsorption of Cu 2+ using bagasse as adsorbent modified coconut. The modifications were employed (a) by polymerization of formaldehyde in sulfuric acid medium, b) treatment with ionic lÃguido c) Esterification acid and multicarboxÃlicos multifenÃlicos. The models applied to the study of isotherms were Langmuir, Freundlich, Temkin and Dubinin-Raduschevich. Applying the model in the study of Langmuir Adsorption of Cu (II) adsorbent modified BCFB the maximum adsorption capacity qm and kL were contained 125 mg.g-1 and 1.11 x10-2L.mg for Cu +2. For adsorbentes BC / LI and BCTÃnico the qm value were 64.5 and 99mg.g-1 respectively as kL value were 5.3 x10-2 5.6 x10-2 respectively. The kinetic model that best fit the phenomenon was the second order. The results showed that the coconut coir chemically modified is a potential adsorbent for removing Cu2+. The study column was used to verify the performace of the adsorbent when employing industrial effluent. Under the conditions employed in this study was modified with tannic acid that had shown the best removal performance desempenho removal. Also the reusability of the adsorbent is remarkable since it promotes a lowering cost, considering its applicability on an industrial scale.

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The tururi and buriti fibers, and the castor bean stalks are extremely efficient to sorption of metal ions from aqueous solutions. In this study, the adsorbents were activated with different concentrations of alkali solutions (5, 7, 10 and 15% w/v). The materials were characterized by analytical techniques as infrared, X-ray Diffraction (XRD) and Thermogravimetry analysis. The infrared spectra revealed that associated groups to macromolecules of hemicellulose and lignin after alkaline activation have less intensity compared to the initial samples. The XRD revealed, that after castor bean stalks alkaline activation, the presence of the cellulose type II peaks, which did not occur with tururi and buriti fibers. The fluorescence X-ray data showed that the cations present in the initial adsorbents, K+ and Ca2 + are exchanged by Cu (II), Ni (II), Cd (II) and Pb (II) in the sorption process. Studies of the influences of variables: mass of adsorbent; agitation rate; the initial pH and concentration using a fractional factorial design 24-1 demonstrated that all variables affect the response (adsorption capacity mg g-1). As a result for a larger value of qtotal, conditions were observed while maintaining the pH at 5.5; mass of the adsorbent 50 mg; agitation at 200 rpm and the initial concentration: 500 mg L-1. The adsorption kinetics revealed fast adsorption process, about 30 minutes, and good fitting to pseudo-second-order theoretical model to all adsorption process studied. Intraparticle diffusion models as Weber-Morris and Boyd were testes in order to study the limiting steps of the process.The results showed that for tururi and buriti fibers (with the exception of nickel ions) the rate-limiting step is not the intraparticle diffusion, while for the castor bean stalks, it was found that the rate-limiting step of the process is the intraparticle diffusion. The study of monoelement and multielement systems were performed at pH 5.5, initial concentrations from 20-500 mg L-1, which the experimental data were fitted to the Langmuir, Freundlich and Sips theoretical models. The tururi fibers adsorption capacities (mg g-1) in monoelementar and multielement system follows the order Pb (188.79)> Cd (92.20)> Cu (32.82)> Ni (22.23) and Cd (77.53)> Pb (43.93)> Cu (24.99)> Ni (19.51), respectively. Buriti fibers adsorption capacities (g-1 mg) in monoelementar and multielement systems follows the order of Cu (143.1)> Pb (112.1)> Ni (103.7)> Cd (86.33) and Pb (69.12)> Cu (49.28)> Ni (45.10)> Cd (24.95), respectively. Castor bean stalks adsorption capacities (g-1 mg) in in monoelementar and multielement systems follows the order of Pb (175.1)> Cd (124.8)> Ni (111.1)> Cu (89.23) and Cu (56.78)> Pb (55.82)> Cd (44.72)> Ni (43.48), respectively. The results showed a better fit for the Sips model, relating to a heterogeneous adsorption. Fixed bed studies using castor bean stalks checking the influence of variables adsorbent flow (1, 2 and 3 mL min-1), the height of the column (5, 7 and 10 cm) and initial concentration (100 , 200, 300 mg L-1) by the Box-Behnken planning revealed that there were no influence between the variables in the studied. The breakthrough curves were well fitted to the Thomas model. The study in real effluent with Cu (II) (galvanoplastic sector) was carried out using the optimized condition: flow (1 ml min-1); bed height (10 cm) initial concentration: (245.5 mg L-1) and it was found adsorption capacity of 32.42 mg g-1. The mamoneira stalks adsorbent was used for five cycles to verify their potential reuse, and it was found no significant efficiency losses.
As fibras tururi, buriti e talos da mamoneira sÃo resÃduos lignocelulÃsicos extremamente eficientes na sorÃÃo de metais de soluÃÃes aquosas. Neste trabalho, eles foram ativados com diferentes concentraÃÃes de soluÃÃes alcalinas (5, 7, 10 e 15% m/v). Os materiais foram caracterizados pelas tÃcnicas analÃticas de Infravermelho, DifraÃÃo de Raios-X (DRX) e Termogravimetria. Os espectros de infravermelho revelaram que os grupos associados Ãs macromolÃculas de hemicelulose e lignina diminuem em intensidade ou desaparecem apÃs a ativaÃÃo alcalina. Os DRX revelaram que apÃs a ativaÃÃo alcalina, os talos da mamoneira apresentaram picos de celulose tipo II, o que nÃo ocorreu com as fibras de tururi e buriti. O dados de FluorescÃncia de Raios-X revelaram que os cÃtions presentes nos adsorventes como Na(I) e Ca(II) sÃo trocados pelos Ãons Cu(II), Ni(II), Cd(II) e Pb(II) no processo de sorÃÃo. Os estudos das influÃncias das variÃveis: massa do adsorvente; taxa de agitaÃÃo; pH e concentraÃÃo inicial utilizando planejamento experimental fracionÃrio 24-1 demostrou que todas as variÃveis afetaram a resposta (capacidade de adsorÃÃo mg g-1). Como resultado para um maior valor de qtotal, as condiÃÃes observadas foram mantendo o pH em 5,5; massa do adsorvente em 50 mg; taxa de agitaÃÃo em 200 rpm e concentraÃÃo inicial 500 mg L-1. A cinÃtica de adsorÃÃo revelou rÃpida adsorÃÃo, cerca de 30 minutos em geral, seguindo o modelo de pseudo-segunda ordem em todos os processos adsortivos. Modelos de difusÃo intrapartÃcula como de Webber-Morris e Boyd foram estudados a fim de determinar as etapas limitantes do processo. Os dados evidenciaram que para as fibras de tururi e buriti (com exceÃÃo dos Ãons nÃquel) a etapa limitante da velocidade nÃo à a difusÃo intraporo, enquanto para os talos de mamoneira foi verificado que a etapa limitante do processo à a difusÃo intrapartÃcula. O estudo com sistema monoelementar e multielementar foi realizado em pH 5,5, concentraÃÃes variando de 20-500 mg L-1, nos quais os dados foram aplicados aos modelos de Langmuir, Freundlich e Sips. As capacidades de adsorÃÃo (mg g-1) em sistema monoelementar e multielementar das fibras de tururi segue a ordem Pb(188,79)> Cd(92,20)> Cu(32,82)> Ni(22,23) e Cd(77,53)> Pb(43,93)> Cu(24,99)> Ni(19,51), respectivamente. As capacidades de adsorÃÃo (mg g-1) das fibras de buriti em sistema monoelementar e multielementar segue a ordem Cu(143,1)> Pb(112,1)> Ni(103,7) > Cd(86,33) e Pb(69,12)> Cu(49,28)> Ni(45,10)> Cd(24,95), respectivamente. As capacidades de adsorÃÃo (mg g-1) dos talos de mamoneira em sistema monoelementar e multielementar segue a ordem Pb(175,1)> Cd(124,8)> Ni(111,1)> Cu(89,23) e Cu(56,78)> Pb(55,82)> Cd(44,72)> Ni(43,48), respectivamente. Em geral, os resultados evidenciaram melhor aplicabilidade ao modelo de Sips, o qual prediz que os sÃtios disponÃveis para adsorÃÃo sÃo heterogÃneos. Em relaÃÃo ao estudo de adsorÃÃo em leito fixo utilizando talos de mamoneira, a verificaÃÃo da influÃncia das variÃveis: fluxo do adsorvente (1, 2 e 3mL min-1), altura da coluna (5, 7 e 10 cm) e concentraÃÃo inicial (100, 200, 300 mg L-1) pelo planejamento de Box-Behnken, revelou que nÃo hà influencia mutua entre as variÃveis no intervalo estudado. As curvas de ruptura experimentais foram bem aplicadas ao modelo teÃrico de Thomas. O estudo com efluente real de Ãons Cu (II) (setor galvanoplÃstico) utilizando a condiÃÃo otimizada: fluxo (1mL min-1); altura de leito (10 cm) e concentraÃÃo inicial: (245,5 mg L-1) obteve 32,42 mg g-1 de capacidade de adsorÃÃo O adsorvente talos de mamoneira foi utilizado por cinco ciclos para verificar seu potencial de uso, nÃo havendo perdas significativas de eficiÃncia.

Orientador: Vânia Regina Nicoletti Telis
Banca: Caciano Pelayo Zapata Noreña
Banca: Joel Fernando Nicoleti
Banca: José Francisco Lopes Filho
Banca: José Antônio Gomes Vieira
Resumo: Os objetivos deste trabalho foram analisar a influência do tipo e da quantidade de aditivos, além de diferentes métodos de secagem da polpa de maracujá em pó, nas isotermas, propriedades termodinâmicas de sorção e nos atributos de qualidade do produto obtido. No capítulo 1 descreve-se o efeito de diferentes aditivos - maltodextrina DE 10 e goma arábica - sobre as isotermas de sorção nas temperaturas de 20, 30, 40 e 50 ºC de polpa de maracujá em pó obtida por secagem a vácuo. O modelo de GAB se ajustou aos dados de sorção. As isotermas apresentaram comportamento da curva do tipo II, na classificação de Brunauer. Observou-se que a adição de maltodextrina DE 10 e de goma arábica à polpa de maracujá desidratada reduziu a umidade de equilíbrio em relação à umidade da polpa pura e não houve diferença considerável entre as umidades de equilíbrio das amostras da polpa com 18% de goma arábica e polpa com 18% ou 55% de maltodextrina. O aumento da concentração da maltodextrina não teve influência sobre os valores de umidade de equilíbrio. O calor isostérico de sorção da polpa em pó aumentou com o decréscimo da umidade, ao mesmo tempo em que apresentou menores valores para a polpa em pó com aditivos do que os observados para a polpa pura. Através da teoria da compensação isocinética, pode-se concluir que o processo de sorção de água pela polpa de maracujá em pó é um processo espontâneo e controlado pela entalpia para todas as amostras testadas. No capítulo 2 foi analisada a influência de três métodos de secagem: em estufa a vácuo (60 ºC), spray drying (140 ºC) e liofilização sobre as isotermas da polpa de maracujá em pó com 55% de maltodextrina DE 10. O pó produzido em spray dryer apresentou maior capacidade de sorção em relação aos pós desidratados em estufa a vácuo e em liofilizador. No capítulo 3 foi avaliada a influência... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The objectives of this work were to analyze the influence of type and quantity of additives, in addition to different drying methods, on the production of powdered passion fruit pulp, on its water sorption isotherms and on its themodynamical properties, as well as evaluating the quality attributes of the obtained product. Chapter 1 describes the effect of different additives - maltodextrin DE 10 and Arabic gum - on the sorption isotherms at temperatures of 20, 30, 40 e 50 ºC of passion fruit pulp powder obtained by vacuum drying. The sorption data were well adjusted by GAB model. The isotherms presented behavior of type II curves according to the Brunauer classification. The addition of maltodextrin DE 10 and Arabic gum to the passion fruit pulp powder decreased the equilibrium water content when compared to the pure powdered pulp and no considerable differences between the equilibrium moisture content of samples with 18% of arabic gum and with 18% or 55% of maltodextrin were observed. The increase in maltodextrin concentration did not affect the equilibrium water contents. The isosteric heat of sorption of the powdered pulp increased with decreasing water content, at the same time that lower values were obtained to powdered pulp with additives than to pure powdered pulp. Through the isokinetic compensation theory it could be concluded that the water sorption process by the powdered passion fruit pulp is an enthalpy controlled, spontaneous process for all tested samples. In chapter II, the influence of three drying methods: vacuum drying (60 ºC), spray drying (140 ºC) and freeze drying over the powdered passion fruit pulp isotherms with 55% of maltodextrin DE 10, was analyzed. The passion fruit pulp powder produced by spray drying presented higher sorption ability than vacuum dried and freeze dried pulp. In chapter 3, the influence of different concentrations and different dextrose... (Complete abstract click electronic access below)
Doutor

Atualmente, o tipo de propelente para produtos em aerossol mais usado no mundo é uma mistura de hidrocarbonetos leves (butano e propano - sendo o primeiro em maior proporção). Parte de seu processo de produção é a dessulfurização do butano líquido, através de adsorção em leito fixo usando peneiras moleculares 13X. A literatura científica não apresenta muitas publicações sobre o tema e considerando que a técnica de adsorção é fortemente dependente de dados experimentais para seu maior entendimento, é objetivo deste trabalho estudar este processo através do equilíbrio de adsorção, das curvas de ruptura e do desenvolvimento de um modelo matemático que represente o funcionamento de uma coluna de adsorção de leito fixo a temperatura constante. Obtiveram-se dados sobre o equilíbrio de adsorção por meio de ensaios em banho finito comparando-se a interação de diferentes compostos de enxofre com a peneira molecular 13X e o efeito da temperatura. Utilizou-se a técnica de cromatografia gasosa como método analítico para obtenção dos teores de compostos sulfurados e de hidrocarbonetos. O modelo de Langmuir apresentou bom ajuste aos dados experimentais. Avaliando-se a interação dos componentes sulfurados com a zeólita 13X, identificou-se diferenças significativas, sendo a maior em ordem decrescente: etil-mercaptana, n-propil-mercaptana e terc-butil-mercaptana, respectivamente. A dinâmica do processo de adsorção foi estudada através da obtenção das curvas de ruptura em leitos em escala laboratorial e piloto. Avaliaram-se as influências da variação da concentração de entrada da n-propil-mercaptana e da velocidade do fluido em leito fixo recheado com zeólitas 13X, mantendo os demais parâmetros constantes. Conforme esperado o aumento da concentração inicial reduz o tempo de ruptura, aumenta a quantidade total adsorvida pelo leito e não altera o comportamento da zona de transferência de massa (ZTM). Analisando-se a elevação da velocidade, nota-se também uma diminuição no tempo de ruptura e um aumento da ZTM. O modelo matemático apresentado considera os balanços de massa microscópicos aplicados ao leito, os fenômenos de transporte de massa com modelo de dispersão axial e transporte por convecção da fase líquida para a superfície da partícula e as isotermas de adsorção. As equações diferenciais parciais resultantes foram adimensionalizadas e resolvidas empregando-se o método de diferenças finitas, implementado por código Matlab®. A partir da simulação matemática das condições experimentais obtiveram-se os parâmetros de dispersão axial e de transferência de massa que possibilitaram uma boa reprodução do tempo de ruptura quanto do perfil da zona de transferência de massa para os experimentos em escala laboratorial e piloto.
Currently, the kind of propellant for aerosol products most widely used in the world is a blend of light hydrocarbons (butane and propane - the first in greater proportion). Part of the production of propellant is the desulfurization of liquid-phase butane by molecular sieves 13X in a fixed bed. The scientific literature concerning the adsorption of the mercaptans using zeolite are scarce and considering that the adsorption technique is strongly dependent on experimental data for its better knowlegde, the aim of this work was to study this process by adsorption equilibrium, the breakthrough curves and the development of a mathematic model, simulation and comparison with the operation of a fixed-bed pilot and laboratory-scale column. Adsorption equilibrium parameters were obtained using finite bath experiment and comparing the interaction of different sulfur compounds with molecular sieve 13X and the temperature effect. It was used the gas chromatography as an analytical method in order to obtain the levels of hydrocarbons and sulfur compounds. The Langmuir model well fit the experimental data. Significant differences were identified in the interaction of the sulfur components with zeolite 13X. The major interactions of the sulfur components are in decreasing order: ethyl-mercaptan, n-propyl-mercaptan and terc-butyl-mercaptan. The dynamic of the adsorption process was studied by obtaining the breakthrough curves in laboratory and pilot scale. It was investigated the influence of the initial concentration of n-propyl mercaptan and the fluid velocity in a fixed bed packed with zeolite 13X keeping the other parameters constant. As it was expected, as the inlet sulfur concentration increases the break point time decrease, and enhances the total amount adsorbed by the bed. Analyzing the increase in velocity on the breakthroug profile, it was noted that also decreases the break point time and causes a greater decline of the curve resulting in greater ZTM and anticipating the bed saturation time. The model equations account the mass balance applied in the flowing liquid phase in the column, transport phenomena as the effect of axial dispersion and convection from liquid phase to the adsorbent surface and adsorption isotherm. Finite difference method was used to solve the dimensionless general partial differential equations and it was implemented by Matlab® software. From mathematical simulation of experimental conditions it were obtained the axial dispersion parameters and mass transfer coefficient which allowed a fair agreement in predicting break point time and the mass transfer zone profile.

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Os objetivos deste trabalho foram analisar a influência do tipo e da quantidade de aditivos, além de diferentes métodos de secagem da polpa de maracujá em pó, nas isotermas, propriedades termodinâmicas de sorção e nos atributos de qualidade do produto obtido. No capítulo 1 descreve-se o efeito de diferentes aditivos - maltodextrina DE 10 e goma arábica - sobre as isotermas de sorção nas temperaturas de 20, 30, 40 e 50 ºC de polpa de maracujá em pó obtida por secagem a vácuo. O modelo de GAB se ajustou aos dados de sorção. As isotermas apresentaram comportamento da curva do tipo II, na classificação de Brunauer. Observou-se que a adição de maltodextrina DE 10 e de goma arábica à polpa de maracujá desidratada reduziu a umidade de equilíbrio em relação à umidade da polpa pura e não houve diferença considerável entre as umidades de equilíbrio das amostras da polpa com 18% de goma arábica e polpa com 18% ou 55% de maltodextrina. O aumento da concentração da maltodextrina não teve influência sobre os valores de umidade de equilíbrio. O calor isostérico de sorção da polpa em pó aumentou com o decréscimo da umidade, ao mesmo tempo em que apresentou menores valores para a polpa em pó com aditivos do que os observados para a polpa pura. Através da teoria da compensação isocinética, pode-se concluir que o processo de sorção de água pela polpa de maracujá em pó é um processo espontâneo e controlado pela entalpia para todas as amostras testadas. No capítulo 2 foi analisada a influência de três métodos de secagem: em estufa a vácuo (60 ºC), spray drying (140 ºC) e liofilização sobre as isotermas da polpa de maracujá em pó com 55% de maltodextrina DE 10. O pó produzido em spray dryer apresentou maior capacidade de sorção em relação aos pós desidratados em estufa a vácuo e em liofilizador. No capítulo 3 foi avaliada a influência...
The objectives of this work were to analyze the influence of type and quantity of additives, in addition to different drying methods, on the production of powdered passion fruit pulp, on its water sorption isotherms and on its themodynamical properties, as well as evaluating the quality attributes of the obtained product. Chapter 1 describes the effect of different additives - maltodextrin DE 10 and Arabic gum - on the sorption isotherms at temperatures of 20, 30, 40 e 50 ºC of passion fruit pulp powder obtained by vacuum drying. The sorption data were well adjusted by GAB model. The isotherms presented behavior of type II curves according to the Brunauer classification. The addition of maltodextrin DE 10 and Arabic gum to the passion fruit pulp powder decreased the equilibrium water content when compared to the pure powdered pulp and no considerable differences between the equilibrium moisture content of samples with 18% of arabic gum and with 18% or 55% of maltodextrin were observed. The increase in maltodextrin concentration did not affect the equilibrium water contents. The isosteric heat of sorption of the powdered pulp increased with decreasing water content, at the same time that lower values were obtained to powdered pulp with additives than to pure powdered pulp. Through the isokinetic compensation theory it could be concluded that the water sorption process by the powdered passion fruit pulp is an enthalpy controlled, spontaneous process for all tested samples. In chapter II, the influence of three drying methods: vacuum drying (60 ºC), spray drying (140 ºC) and freeze drying over the powdered passion fruit pulp isotherms with 55% of maltodextrin DE 10, was analyzed. The passion fruit pulp powder produced by spray drying presented higher sorption ability than vacuum dried and freeze dried pulp. In chapter 3, the influence of different concentrations and different dextrose... (Complete abstract click electronic access below)

The topic of this work is the monitoring of the effect of zinc on the hydration process in Portland mixed cement (specifically with the addition of finely ground granulated blast-furnace slag, high temperature fly ash and fluidized bed combustion filter ash). How much zinc and at what time it remains in the pore solution during hydration. Activation energy of a mixture of cement with zinc in the form of soluble salts (Zn(NO3)2.6H2O and ZnCl2) and insoluble oxide (ZnO) by isothermal calorimetry was also investigated. The XRF method has shown composition during hydration. The zinc retardation effect was investigated by isothermal calorimetry and activation energy was calculated using this method. The XRF and ICP-OES methods were used to measure the zinc content of the pore solution. And the amount of portlandite was monitored by the DTA and XRF method.

The theme of this work is to monitor the effect of zinc on the properties of blended Portland cements. Zinc was tested in the form of two-soluble salts: Zn(NO3)22 H2O and ZnCl2 and a very slightly soluble compound ZnO. Blended cements were prepared by partial replacement with finely ground granulated blast furnace slag, high-temperature and fluidized bed combustion filter fly ash. Flow properties were studied on the prepared pastes. Impact on hydration reactions was examined by using of isothermal and isoperibolic calorimetry. Flexural and compressive strength were measured as mechanical properties of the prepared test specimens. The phase composition of the prepared composites and incorporation of zinc ions in the cement matrix via leaching tests and FTIR analyzes were also studied. Microstructure development of cement samples was tested by SEM analysis with EDS. Influence on ecotoxicity was also measured.

The pharmaceutical industry is developing a growing interest in natural compounds with biological and nutritional properties. Betulinic and oleanolic acids are two naturally occurring triterpenic acids, which possess such characteristics. These two compounds can be extracted from natural resources, i.e., from the bark of Eucalyptus globulus. However, their separation is difficult because these compounds present similar structures (they are constitutional isomers). In this work, the chromatographic separation of betulinic and oleanolic acids from representative extracts of E. globulus was studied. High performance liquid chromatography (HPLC) assays were initially performed using an Acclaim C30 column as stationary phase. Through these tests it was found that the mobile phase methanol/acetonitrile 50/50 (%, v/v) is the most suitable for the separation of both triterpenic acids. In order to determine the equilibrium constants (𝐻𝑖) and the global linear driving force mass transfer coefficients (𝐾𝐿𝐷𝐹), several breakthrough experiments of pure acids (unary solutions) were carried out. The two parameters were correlated using experimental data and then validated by simulating the breakthrough curve of a binary mixture containing the same proportion of betulinic and oleanolic acids found in E. globulus extracts. The outcomes of all experiments were modeled using Carta’s analytical solution. In parallel, the method of moments was also used to obtain the transport parameters. The results were consistent. Lastly, the separation of betulinic and oleanolic acids by simulating moving bed (SMB) has been studied, carrying out simulations using the transport parameters obtained before from the breakthrough assays. Two different column configurations (1-1-1-1 and 2-2-2-2) and column lengths (from 10 to 25 cm) were adopted. It was concluded that using an SMB unit is able to separate betulinic and oleanolic acids with purity higher than 99 % both in extract and raffinate for all the scenarios presented. Posteriorly, the recovery of both triterpenic acids from the extract and raffinate streams of a future process was also investigated, taking advantage of their low solubility in water. Accordingly, the solubility of each triterpenic acid in solvent mixtures of increasing water concentration was experimentally measured and discussed.
A indústria farmacêutica tem manifestado um crescente interesse em compostos naturais com propriedades biológicas e nutricionais. Os ácidos betulínico e oleanólico são dois ácidos triterpénicos que ocorrem naturalmente na natureza e que possuem tais características. Estes dois compostos podem ser extraídos de recursos naturais, tais como da casca do Eucalyptus globulus. No entanto, a sua separação é difícil, pois os compostos apresentam estruturas muito semelhantes (são isómeros constitucionais). Neste trabalho estudou-se a separação cromatográfica de uma amostra representativa dos extratos de E. globulus dos ácidos betulínico e oleanólico. Inicialmente foram realizados testes cromatográficos em cromatografia líquida de alta eficiência, recorrendo à fase estacionária Acclaim C30. Através destes ensaios determinou-se que a fase móvel metanol/acetonitrilo 50/50 (%, v/v) é a mais adequada para a separação destes ácidos triterpénicos. De modo a averiguar as constantes de equilíbrio (𝐻𝑖) e os coeficientes globais de transferência de massa (𝐾𝐿𝐷𝐹), foram determinadas as curvas de rutura dos ácidos puros (soluções unárias). Estes parâmetros foram correlacionados recorrendo a dados experimentais e posteriormente validados pela simulação da curva de rutura de uma mistura binária contendo a mesma proporção de ácido betulínico e oleanólico encontrada no E. globulus. Os dados advindos deste ensaio foram modelados pela solução analítica de Carta. Paralelamente, foi também usado o método dos momentos para obter os parâmetros de transporte. Os resultados obtidos foram consistentes. Por fim, estudou-se a separação dos ácidos betulínico e oleanólico por leito móvel simulado (SMB), realizando simulações utilizando os parâmetros de transporte obtidos anteriormente pela modelação das curvas de rutura. Foram adotadas duas configurações diferentes (1-1-1-1 e 2-2-2-2) e diferentes comprimentos de coluna (variando dos 10 aos 25 cm), usando os parâmetros de transporte obtidos. Foi concluído que usando uma unidade SMB é possível separar os ácidos betulínico e oleanólico com purezas superiores a 99 % tanto no extrato como no rafinado para todos os cenários apresentados. Posteriormente, foi analisada a recuperação dos ácidos triterpénicos das correntes de extrato e rafinado de um futuro processo, tirando vantagem da sua baixa solubilidade em água. Por conseguinte, a solubilidade de cada ácido triterpénico em misturas de solventes com o aumento da concentração de água foi medida e discutida.
Mestrado em Engenharia Química

碩士
國立成功大學
化學工程研究所
82
Most of the researches in the hydrodesulfurization (HDS) of the residual oil were focused on a single catalyst pellet with an uniform activ ity , or on studing the optimal initial pore size under the isothermal conditions . However the operations of HDS in the industry in practice us- ually fix the reactor outlet con centration of the sulfur-contai- ning molecules and stop the operation when the upper limiting te- mperature is reached . In this study the non-uniform activity pr- ofile of the HDS catalysts was incorporated into the restricted diffusion model proposed by Rajagoplan and Luss to examine the t- emperature- rising profile of the fixed bed reactor , and to pred- ict the optimal design of the reactor from the total amount of desulf urization under the nonisothermal operating conditions . The optimal design of the reactor includes the optimal pore size the catalysts and their corresponding optimal design in one -stage and two-stage arrangement respectively . The reaction product of the metal sulfide will accumulate on the pore surface of the catalysts during the reaction , and ther- eby reduce the HDS reaction rate . Because of this , the hydrode- metallation (HDM) reaction the residual oil was considered simul- taneously with the HDS reaction . In this study , 1st- order reac- tion for HDM and 2nd-order reaction for HDS were adopted . The numerical results have shown that the life-time and the total mass of desulfarization with the nonuniform activity catal- ysts were higher than those of the uniform activity catalysts . Although the initial temperature of the former is greater th- an that of the uniform activity catalyst , but their temperature- rising prifile is flatter than that of the uniform activity cata- lyst , and their interior activity surface can be more efficient- ly utilized to improve the catalyst life and mass of desulfuriza- tion .

Natural products have been progressively forgotten by major pharmaceutical research companies as sources for new drugs in the last half century. Currently one observes a change of strategy, which is promoting a renewed interest on the integration of natural products into pharmaceuticals. Triterpenic acids are a promising group of plant secondary metabolites occurring in cuticular waxes covering fruits, owers, and leaves, providing a wide variety of bene cial biological activities. In this dissertation it was studied the oleanolic and ursolic acids isolation by chromatographic tecnique of simulated moving bed (SMB). The seperation of triterpenic acids is complex due their similar structure. EgiChem laboratory (CICECO, UA) has a SMB unit, but it is necessary to carry out preliminary experiments in order to select the best mobile phase and optimal operating conditions for separation of both acids. For that, it was analyzed the infuence of the solvent/mixture of solvents on the chromatographic separation by measuring selectivity, retention factor and resolution. It was tested a triacontyl column (Acclaim C30), and the best results were obtained with a mobile phase of methanol/ water 95/5 (%, v/v). Then, breakthrough curves have been measured in order to determine process parameters like the equilibrium isotherms (constants Hi) of both oleanolic and ursolic acids, and the global linear driving force (LDF) coe cients of mass transfer (KLDF,i). Data modeling was accomplished using Klinkenberg equation, which is specifcially applicable to linear systems. The equilibrium constants of oleanolic and ursolic acdis were HOA= 2.06 and HUA= 2.16, respectively, and global LDF coe cients were KLDF,OA= 30.48 min-1 and KLDF,UA= 101.45 min-1 with average deviaions of AADROA=18.29 % and AADRUA=26.88 %. Finally the simulation of a SMB unit for a oleanolic/ursolic acids mixture separation was accomplished, with a 2-2-2-2 con guration, using the packing of Acclaim C30 column and methanol/water 95/5 (%, v/v) as mobile phase and the equilibrium and kinetic parameters previously optimized. The obtained results for con guration showed that the separation of oleanolic and ursolic acids is viable, being possible to produce puri ed streams of each acid with concentrations above 99%.
No último meio século, os produtos naturais tem sido gradualmente esquecidos pelas maiores companhias de investigação farmacêuticas como fontes de novos medicamentos. Porém atualmente observou-se uma mudança de estratégia que promoveu um novo interesse na integração dos produtos naturais nestes. Os ácidos triterpénicos fazem parte de um grupo promissor de metabolitos secundários que podem ser encontrados em plantas, flores, folhas com grande variedade de benficios. Nesta dissertação estudou-se o isolamento dos ácidos oleanólico e ursólico por técnicas cromatográficas, recorrendo à tecnologia de leito móvel simulado (SMB). A separação dos ácidos triterpénicos é complexa dada à sua semelhança estrutural. No laboratório do grupo EgiChem (CICECO, UA) está a ser instalada uma unidade de SMB, porém é necessário realizar ensaios preliminares para selecionar a fase móvel mais adequada, bem como a otimização das condições de operação de ambos os ácidos. Posto isto, analisou-se a influência do solvente/mistura de solventes na separação cromatográfica recorrendo à medição de seletividades, factores de retenção e resolução. Foi testada uma coluna triacontyl (Acclaim C30), sendo que os melhores resultados foram obtidos com a fase móvel metanol/água 95/5 (%, v/v). Seguiu-se à medição das curvas de rutura de modo a determinar os parametros de processo como as isotérmicas de equilibrio (constantes Hi) do ácido oleanólico e do ácido ursólico, e os coeficientes globais de transferência de massa do modelo da força motriz linear (KLDF,i). Os dados obtidos foram modelados através da equação de Klinkenberg, que é aplicado especificamente para sistemas lineares. As constantes de equilíbrio linear dos ácidos oleanólico e ursólico foram HOA= 2.06 e HUA= 2.16, respetivamente, e os coeficientes globais de transferência de massa LDF de KLDF,OA= 30.48 min-1 e KLDF,UA= 101.45 min-1 com desvios médios de AADROA=18.29 % e AADRUA=26.88 %. Por fim foi realizada uma simulação de uma unidade SMB para a separação de uma mistura de ácidos oleanólico e ursólico, com uma configuração 2-2-2-2, usando o enchimento da coluna Acclaim C30 e a fase móvel metanol/água 95/5 (%, v/v) e os parâmetros de equilibrio e cinética otimizados anteriormente. Os resultados obtidos para esta configuração mostraram que é possível produzir correntes purificadas de cada ácido com concentrações acima dos 99%.
Mestrado em Engenharia Química

碩士
中原大學
生物醫學工程研究所
99
Abstract Chlorine/chloramine residues in water have a considerable threat to hemodialysis patients. According to relevant literature, chlorine/chloramine residues in water are related to the hemolysis phenomenon during the treatment of dialysis patients. In addition, among all the water treatment procedures of dialysis, only the activated carbon adsorption procedure can effectively eliminate chlorine/chloramine residues in water to reduce the hemolysis phenomenon of dialysis patients. The purpose of this study is to estimate the breakthrough time and filling height of the activated carbon adsorption bed by the mathematical models of the isotherm adsorption and fixed bed adsorption theories, in order to effectively remove the chlorine/chloramine residues in water and reduce the occurrence of hemolysis phenomenon of the dialysis patients during dialysis. This study conducted three types of tests using the clinically used activated carbon adsorbents. The first type test was the adsorption speed test using a fixed amount of activated carbon; the secondary test was the isotherm adsorption test of using different amounts of activated carbon in sodium hypochlorite solution of given volume, and conducted regression analysis and relevant analysis of the adsorption results to find the appropriate isotherm adsorption model; the third type of test was the fixed bed adsorption simulation test with carbon adsorption device of scaled dwon specifications for clinical use, and the adsorption results were analyzed using the fixed bed adsorption mathematical theoretical model. The results suggested that the clinically used activated adsorbents can effectively reduce the chlorine/chloramine residues in water in 5 min, and completely eliminate them in 15 min. The regression analysis of the isotherm adsorption testing results found that the clinically used activated carbon adsorbent can facilitate adsorption with the adsorption index (1/n) at 0.52. A comparison with the relevant analysis results of Langmuir and Freundlich found that the adsorbent can better fit the Freundlich isotherm adsorption model with correlation coefficient at 0.91. The fixed bed adsorption simulation results suggested that the breakthrough time of the column adsorption were 13 hr and the saturated adsorption time was 21 hr. By the mathematical model of the fixed bed adsorption theory, the column adsorption belt (δ) was 0.02 m, and the column adsorption belt moving speed (ν) was 3.04 x 10-3(m/hr), number of moving units (Nf) was 3.61 and the total capacity (Kfav) was 9925.23(1/hr). By inputting different theoretical solution concentrations into the theoretical mathematical model, it was confirmed by calculation that the theoretical adsorption time and testing time of the model have good correlation. The relevant parameters of the clinically used carbon adsorption device were input into the theoretical mathematical model to obtain the theoretical filling bed height (Z) of theoretical scaling up as 0.87 m, which was a gap of 0.13 m from the filling height bed height of 1 m, as provided by the manufacturer. The theoretical breakthrough time was 8760 hr, which was consistent with the manufacturer-suggested replacement time. By isotherm adsorption test and the fixed bed adsorption theoretical mathematical model, the breakthrough time and filling height of the activated carbon filling bed can be estimated to effectively eliminate the chlorine/chloramine residues in water to reduce the occurrence of hemolysis phenomenon of dialysis patients during dialysis.

4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...

Στην εργασία αυτή μελετήθηκε η ρόφηση και η εκρόφηση του παρασιτοκτόνου ατραζίνη (atrazine) σε πρότυπες εδαφικές ουσίες καθώς και σε ένα τυπικό δείγμα εδάφους, τόσο σε αντιδραστήρες διαλείποντος έργου (batch) όσο και σε πληρωμένες κλίνες (bed). Ως πρότυπες ουσίες επιλέχθηκαν η πυριτία (silica-gel, SiO2), η αλούμινα (γ-alumina, Al2O3), το ανθρακικό ασβέστιο (calcite, CaCO3) και το χουμικό οξύ (humic acid). Η ατραζίνη ροφείται σημαντικά στο χουμικό οξύ στην πυριτία και στο έδαφος, όμως βρέθηκε ότι έχει πολύ μεγαλύτερη συγγένεια για το χουμικό οξύ σε σύγκριση με την πυριτία. Η ατραζίνη δεν έδειξε να ροφείται στη γ-αλούμινα και το CaCO3, ανεξαρτήτως από τις πειραματικές συνθήκες που χρησιμοποιήθηκαν. Σε όλες τις περιπτώσεις, η κινητική μελέτη έδειξε δύο διακριτά στάδια: ένα πρώτο γρήγορο στάδιο ρόφησης της ατραζίνης, διαδεχόμενο από ένα δεύτερο πιο αργό στάδιο. Η κινητική της ρόφησης υπακούει ικανοποιητικά στο μοντέλο Elovich. Στα χρονικά πλαίσια που μελετήθηκε η ρόφηση και η εκρόφηση, η διεργασία είναι αντιστρεπτή και η ατραζίνη εκροφείται ποσοτικά. Οι ισόθερμοι ρόφησης της ατραζίνης λήφθηκαν σε διαφορετικές τιμές ιοντικής ισχύος, pH και θερμοκρασίας και υπακούουν στο μοντέλο Freundlich. Σε όλες τις περιπτώσεις που μελετήθηκαν, η αύξηση της ιοντικής ισχύος του διαλύματος προκάλεσε αύξηση της ροφημένης ποσότητας της ατραζίνης. Η ρόφηση της ατραζίνης μειώνεται καθώς το pH του διαλύματος αυξάνεται. Όσον αφορά στην πυριτία, η ρόφηση της ατραζίνης φαίνεται ότι γίνεται κυρίως μέσω δεσμών υδρογόνου με τις υδροξυλομάδες της επιφάνειας. Όσον αφορά στο χουμικό οξύ, το σημαντικότερο ρόλο στη ρόφηση παίζει η διάχυση της ατραζίνης προς το εσωτερικό του στερεού όπου η ρόφηση επιτυγχάνεται κυρίως μέσω υδρόφοβων αλληλεπιδράσεων. Η προσρόφηση της ατραζίνης στην πυριτία αυξάνεται σημαντικά καθώς αυξάνεται η θερμοκρασία του διαλύματος, μια τάση που δεν παρατηρείται κατά τη ρόφηση της ατραζίνης στο χουμικό οξύ. Η θερμοδυναμική ανάλυση έδειξε ότι η ρόφηση στα μοντέλα εδάφους είναι φυσική αφού παρατηρήθηκαν τιμές της ενθαλπίας ρόφησης στην περιοχή των 10 kJ mol-1. Οι λαμβανόμενες ισόθερμοι ρόφησης από τα πειράματα σε πληρωμένες κλίνες ήταν σε καλή συμφωνία με αυτές που λήφθηκαν από τα πειράματα στους αντιδραστήρες διαλείποντος έργου. Η παρουσία χουμικού οξέος στις κλίνες προκαλεί με το χρόνο δραστική μείωση της διαπερατότητας.
Adsorption and desorption of the herbicide atrazine was investigated on the principal inorganic constituents of soil, as well as on a typical Greek soil sample. The studies were conducted both in batch, stirred reactors and in packed beds. Silica-gel (SiO2), γ-alumina (Al2O3) and calcite (CaCO3), were selected as model inorganic substances. Humic acid was selected as a model substance representative of the organic part of soil. Significant adsorption of atrazine was measured on the humic acid, silica and on the soil suspensions in electrolyte solutions. Atrazine exhibited higher affinity for humic acid rather than for silica. Atrazine did not adsorb on γ-alumina and on CaCO3 regardless the experimental conditions (pH range or total solid available for adsorption). In all cases, kinetic results have shown two distinct features: a first, fast sorption step, followed by a second, slow step. The kinetics data of atrazine uptake on both substrates yielded satisfactory fit to the Elovich model. Atrazine was found to be completely desorbed from both the humic acid and the silica substrates. Adsorption isotherms for atrazine were obtained at different values of ionic strength, pH and temperature. The adsorption data gave the best fit to the Freundlich model. In all cases investigated, the amount of adsorbed atrazine increased upon increasing the ionic strength of the solution. The adsorption of atrazine decreased with increasing solution pH. The adsorption of atrazine on silica was primarily dominated by the formation of hydrogen bonds with the surface hydroxyl groups. In the case of humic acid, the diffusion of atrazine to the interior of the solid seemed to play the most significant role. Inside the organic substance particles, sorption took place mainly through hydrophobic interactions. The sorption of atrazine on silica surface increased considerably with increasing temperature, a trend not found in the case of humic acid. The thermodynamic analysis yielded adsorption energy values of the order of 10 kJ mol-1 suggesting physical adsorption. The isotherms obtained from the packed bed experiments were in a good agreement with those obtained from batch experiments. Finally, humic acid grains, mixed with silica in packed beds, were found to change morphology upon hydration which resulted to swelling. The humic substances clogged a large portion of the pores of the packed beds, decreasing drastically their permeability.