The phase separation of mixed Langmuir-Blodgett (LB) monolayers was investigated using a combination of atomic force microscopy (AFM), X-ray photoelectron emission microscopy (X-PEEM) and confocal fluorescent microscopy measurements. Shapes of phase-separated domains that formed on solid substrate surfaces depended on a competition between line tension and dipole-dipole interactions. In the mixed LB film of arachidic acid (C19H39COOH) (C20) and perfluorotetradecanoic acid (C13F27COOH) (F14), the components phase separated into elevated hexagonal domains of C20 surrounded by a continuous domain primarily consisting of F14. The underlying molecular arrangement of C20 was found to be an oblique packing. The domains in this system grew via Ostwald ripening and the kinetics of their growth was modeled by twodimensional LifshitzSlyozov equation. In the stearic acid (C17H35COOH) (C18) and F14 mixed films, the C18 domains formed a linear pattern where the F14 molecules filled the areas in between the lines occupied by C18. For the mixed film of palmitic acid (C15H31COOH) (C16) and perfluorooctadecanoic acid (C17F35COOH) (F18), the surfactants phaseseparated into elevated hexagonal domains with hairy extensions radiating from them. These domains were composed of F18 and surrounded by C16. Ostwald ripening was found to be the mechanism of domain growth. Phase separation was controlled by different forces such as line tension and dipole interactions, as well as the diffusion of the molecules, solubility of the surfactant in the sub-phase, temperature and surface pressure. Simple mechanisms regarding phase separation and pattern formation were discussed in these mixed systems. It was observed that all fatty acid / F14 systems in this study were immiscible at all molar fractions examined. The fatty acid / F18 systems were immiscible at short chains of fatty acids (myristic acid (C13H27COOH) C14, C16, C18), whereas at longer fatty acid chains (C20, C22 behenic acid (C21H43COOH)) the components of the mixed system became miscible. When perfluorocarboxylic acid chain combined with fatty acids, the domains changed from large hexagonal domains into narrow lines as the fatty acid chain decreased in length.

The phase separation of mixed Langmuir-Blodgett (LB) monolayers was investigated using a combination of atomic force microscopy (AFM), X-ray photoelectron emission microscopy (X-PEEM) and confocal fluorescent microscopy measurements. Shapes of phase-separated domains that formed on solid substrate surfaces depended on a competition between line tension and dipole-dipole interactions. In the mixed LB film of arachidic acid (C19H39COOH) (C20) and perfluorotetradecanoic acid (C13F27COOH) (F14), the components phase separated into elevated hexagonal domains of C20 surrounded by a continuous domain primarily consisting of F14. The underlying molecular arrangement of C20 was found to be an oblique packing. The domains in this system grew via Ostwald ripening and the kinetics of their growth was modeled by twodimensional LifshitzSlyozov equation. In the stearic acid (C17H35COOH) (C18) and F14 mixed films, the C18 domains formed a linear pattern where the F14 molecules filled the areas in between the lines occupied by C18. For the mixed film of palmitic acid (C15H31COOH) (C16) and perfluorooctadecanoic acid (C17F35COOH) (F18), the surfactants phaseseparated into elevated hexagonal domains with hairy extensions radiating from them. These domains were composed of F18 and surrounded by C16. Ostwald ripening was found to be the mechanism of domain growth. Phase separation was controlled by different forces such as line tension and dipole interactions, as well as the diffusion of the molecules, solubility of the surfactant in the sub-phase, temperature and surface pressure. Simple mechanisms regarding phase separation and pattern formation were discussed in these mixed systems. It was observed that all fatty acid / F14 systems in this study were immiscible at all molar fractions examined. The fatty acid / F18 systems were immiscible at short chains of fatty acids (myristic acid (C13H27COOH) C14, C16, C18), whereas at longer fatty acid chains (C20, C22 behenic acid (C21H43COOH)) the components of the mixed system became miscible. When perfluorocarboxylic acid chain combined with fatty acids, the domains changed from large hexagonal domains into narrow lines as the fatty acid chain decreased in length.

Οι ζεόλιθοι είναι κρυσταλλικά αργιλοπυριτικά υλικά με πόρους μοριακών διαστάσεων και για το λόγο αυτό συχνά καλούνται και ως μοριακά κόσκινα. Χαρακτηρίζονται από την ικανότητα ρόφησης αερίων και ατμών, ανταλλαγής των κατιόντων της δομής τους, καθώς και κατάλυσης σημαντικού αριθμού χημικών αντιδράσεων. Λόγω των ιδιαίτερων φυσικοχημικών ιδιοτήτων τους, οι ζεόλιθοι αποτελούν ιδανικά υλικά για το διαχωρισμό μορίων με διαφορετικό σχήμα, μέγεθος ή πολικότητα γι’αυτό την τελευταία δεκαετία μέρος του ερευνητικού ενδιαφέροντος έχει επικεντρωθεί στην ανάπτυξη πολυκρυσταλλικών μεμβρανών από ζεόλιθους με σκοπό το διαχωρισμό αερίων και υγρών μιγμάτων. Στην παρούσα Διατριβή μελετήθηκε η κρυστάλλωση μεμβρανών φωγιασίτη πάνω σε πορώδη υποστρώματα από α-Al2O3 με επίπεδη και κυλινδρική γεωμετρία συναρτήσει διαφόρων παραμέτρων σύνθεσης όπως ήταν η σύσταση, η θερμοκρασία, ο χρόνος και η γήρανση των αιωρημάτων σύνθεσης των μεμβρανών Συνολικά εξετάστηκαν πέντε διαφορετικές συστάσεις. Η σύσταση 4.17Na2O : 1.0Al2O3 : 10TEA (τριαιθανολαμίνη) : 1.87SiO2 : 460H2O οδήγησε στην ανάπτυξη μεμβρανών φωγιασίτη με λιγότερες ατέλειες και για αυτό μελετήθηκε περισσότερο. Η ικανότητα των μεμβρανών να διαχωρίζουν μίγματα CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 και C3H6 / C3H8 / N2 εξετάστηκε συναρτήσει της θερμοκρασίας, της σύστασης και της πίεσης της τροφοδοσίας καθώς και της παρουσίας ή μη υγρασίας στο ρεύμα της τροφοδοσίας. Τα πειράματα διαπερατότητας απέδειξαν, ότι ευνοείται η εκλεκτική μεταφορά κυρίως του CO2 και του C3H6 μέσα από τις μεμβράνες. Η εκλεκτικότητα μπορεί να αποδοθεί στην ισχυρή αλληλεπίδραση των μορίων αυτών με τα κατιόντα Na+ που περιέχονται στη δομή του φωγιασίτη. Τέλος, μελετήθηκαν οι μηχανισμοί μεταφοράς μάζας των μιγμάτων CO2 / H2 και CO2 / H2 / N2 / CH4 με τη χρήση της θεωρίας Stefan-Maxwell. Επιπρόσθετα εξετάστηκαν διάφορες περιπτώσεις αργού σταδίου (διάχυση και εκρόφηση) καθώς και συνδυασμοί διαφορετικών μηχανισμών διάχυσης (επιφανειακή διάχυση και ενεργοποιημένη διάχυση αερίων). Οι συντελεστές διάχυσης υπολογίστηκαν από το συνδυασμό των πειραματικών δεδομένων ρόφησης και διαπερατότητας των καθαρών συστατικών. Η ανάλυση που πραγματοποιήθηκε οδήγησε στο συμπέρασμα ότι η μεταφορά των μιγμάτων μέσα από τις μεμβράνες μπορεί να προβλεφθεί κυρίως από το μηχανισμό της επιφανειακής διάχυσης. / Zeolites are crystalline aluminosilicate materials. They are frequently called molecular sieves because they have pores of molecular dimensions. They are able to adsorb gases or vapors, to exchange framework cations and to catalyze a large number of chemical reactions. Due to their physicochemical properties they are ideal materials for the discrimination of molecules based on their shape, size or polarity. The last decade part of the research attention has been focused on the synthesis of polycrystalline zeolite membranes for the separation of gas and vapor mixtures. In the present thesis the crystallization of faujasite membranes on porous flat or tubular α-Al2O3 substrates was studied as a function of several synthesis parameters such as composition, temperature, time and aging of sol mixtures. Five different compositions were examined. Membranes synthesized using sols with composition 4.17Na2O : 1.0Al2O3 : 10TEA (triethanolamine) : 1.87SiO2 : 460H2O, had the best separation performance. The ability of the membranes to separate CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 and C3H6 / C3H8 / N2 mixtures was examined as a function of temperature, feed mixture composition, total feed pressure and the presence or not of humidity in the feed side. In all cases the membranes were either CO2 or C3H6 selective. The separation ability can be attributed to the strong interaction between those molecules with the Na+ cations of the faujasite framework. The transport of CO2, H2, N2 and CH4 through the membranes was modeled using the Maxwell-Stefan theory. Two different cases of rate limiting step (diffusion and desorption) as well as several combinations of different diffusion mechanisms (surface diffusion and activated gaseous diffusion) were considered. The diffusion coefficients were calculated using the single-component permeation and adsorption data. It has been possible to predict the multicomponent permeation fluxes when surface diffusion was assumed the transport mechanism of all species.

Analytical chemistry is a field with a vast variety of applications. A robust companion in the field is liquid chromatography, the method used in this thesis, which is an established workhorse and a versatile tool in many different disciplines. It can be used for identification and quantification of interesting compounds generally present in low concentrations, called analytical scale chromatography. It can also be used for isolation and purification of high value compounds, called preparative chromatography. The latter is usually conducted in large scale with high concentrations. With high concentrations it is also possible to determine something called adsorption isotherms. Determination of adsorption isotherms is a useful tool for quite a wide variety of reasons. It can be used for characterisation of chromatographic separation systems, and then gives information on the retention mechanism as well as provides the possibility to study column-column and batch-batch reproducibility. If a protein is immobilised on a solid support, adsorption isotherms can be used for pharmacological characterisation of drug-protein interactions. Moreover, they can be used for the study of unexpected chromatographic phenomena. If the adsorption isotherm is known it is also possible to simulate chromatograms, and subsequently optimise the separation process numerically. The gain of a numerically optimised separation process is higher purity or yield of valuable compounds such as pharmaceuticals or antioxidants, as well as reducing the solvent usage. Taken all together, it saves time, money and the environment. However, the process of the adsorption isotherm determination requires a number of careful experimental considerations and preparations, and these are the main focus of the thesis. Important steps along the way include the choice of separation system and of suitable analytes, preparation of mobile phases and sample solutions, calibration, determination of injection profiles and column void, and of course the adsorption isotherm determination method itself. It is also important to keep track of parameters such as temperature and pH. These issues are discussed in this thesis. At the end, a description of useful methods for processing of the raw adsorption isotherm data is presented, as well as a brief passage on methods for numerical optimisation.

This thesis concerns the development and validation of methods for the industrially important area of adsorption isotherm parameter estimation in preparative, nonlinear high performance liquid chromatography (HPLC). Preparative chromatography is a powerful separation method to get pure compounds from more or less complex liquid mixtures, e.g., mixtures of mirror-image molecules. Computer simulations can be used to optimize preparative chromatography, but then competitive adsorption isotherm parameters are usually required. Here two methods to estimate adsorption isotherm parameters are treated: (i) the perturbation peak (PP) method and (ii) the inverse method (IM). A new theory for the PP method was derived and led to a new injection technique which was validated experimentally. This injection technique solved the severe problem with vanishing peaks and enabled us to use the PP method to estimate binary competitive adsorption isotherms valid over a broad concentration range. Also, the injection technique made it possible to estimate competitive adsorption isotherms for a quaternary mixture for the first time. Finally, an interesting perturbation peak phenomenon, known as the “Helfferich Paradox”, was experimentally verified for the first time. The IM is a relatively new method to determine adsorption isotherm parameters. It has the advantage of requiring very small samples, but also requires an advanced computer algorithm. An improved implementation of this computer algorithm was developed and tested experimentally. Also, a variant of the IM called “the inverse method on plateaus” was tested experimentally and the estimated adsorption isotherm parameters were shown to be valid over a broader concentration range than those estimated with the standard IM.

Shungite is a carbonaceous rock which is abundant in Karelia (Russian Federation). Large deposits of shungite with low levels of carbon (approx. 10% C) are also found in Kazakhstan, where it is mined under the trade name Taurit (Koksu Mining Company). Although Taurit has been reported to be used as an adsorbent for hazardous compounds in water treatment, there is very little precise data about its adsorption capacity or the compounds adsorbed. In this study, the ability of Taurit to adsorb Zn(II) was investigated and Freundlich isotherms were determined for both distilled water and tap water. Taurit was found to have a high buffer capacity leading to pH values > 7.0 in aqueous solution. Because dissolved zinc precipitates as Zn(OH)2 under alkaline conditions, the pH must be carefully controlled and kept ≤7.0. Despite the small inner surface area (BET) of Taurit (13.4 m2 g−1), Freundlich coefficients for distilled water (Kf = 2.4, n = 4.0) and tap water (Kf = 1.5, n = 2.5) were similar to other adsorbents. Our results indicate that Taurit could provide a cheap alternative to activated carbon since both substances have a similar adsorption capacity (at least for Zn(II)).

Le présent travail a pour objectif de comprendre l’influence des paramètres géométriques des éco-matériaux d’enveloppe, tels que le béton de chanvre, sur les mécanismes de transferts couplés de chaleur, d'air et d’humidité afin de prédire le comportement du bâtiment dans le but de le piloter et de l’améliorer dans sa durabilité. Pour cela, une approche multi-échelle est mise en place. Elle consiste à maîtriser les phénomènes physiques dominants et leurs interactions à l’échelle microscopique. S’ensuit, une modélisation à double échelle, microscopique–macroscopique, des transferts couplés de chaleur, d’air et d’humidité qui prend en compte les propriétés intrinsèques et la topologie microstructurale du matériau moyennant le recours à la tomographie rayon X conjuguée à la corrélation d’images 2D et 3D. Pour cela, une campagne de caractérisation fine des propriétés physiques et hygrothermiques du béton de chanvre confectionné au laboratoire a été réalisée. Elle s’est focalisée sur l’étude de l’impact du vieillissement, l’état thermique et hydrique du matériau sur ses propriétés intrinsèques. Les résultats montrent une excellente capacité d'isolation thermique et de régulation naturelle d’humidité du béton de chanvre. Puis, une caractérisation microscopique par différentes techniques d’imagerie a été effectuée. Les reconstructions 3D du matériau réel scanné au tomographe aux rayons X à différentes résolutions montrent que le béton de chanvre possède plusieurs échelles de porosité, allant de la microporosité au sein du liant et des chènevottes à la macroporosité inter-particulaire. Le comportement hygro-morphique sous sollicitations hydriques a été ensuite étudié. Les résultats de la corrélation d’image numérique 2D et de la tomographie aux rayons X couplés à la corrélation d’images volumiques, montrent la nature du comportement du béton de chanvre soumis à des hygrométries différentes. En effet, la chènevotte subit des déformations plus importantes que le liant, causant ainsi des modifications de la microstructure du matériau. Sur le volet de la modélisation, moyennant la technique d’homogénéisation périodique un modèle des transferts couplés de chaleur, d’air et d’humidité dans les matériaux poreux de construction a été développé. Les tenseurs de diffusion et de conductivité thermique homogénéisés ont été calculés numériquement. Ensuite, une confrontation entre les résultats du calcul des coefficients de diffusion macroscopique et ceux expérimentaux obtenus au LaSIE a été réalisée. Elle met en évidence la qualité de la prédiction. De plus, la conductivité thermique de la phase solide a été ainsi déduite. Les résultats obtenus dans le cadre de ce travail de thèse ont mis en exergue l’influence de l’état hydrique et thermique du béton de chanvre sur ces propriétés intrinsèques, et sa microstructure très hétérogène. Ils ont révélé aussi les limites des approches phénoménologiques basées sur l’établissement des bilans de masse, de quantité de mouvement et d’énergie. / The aim of this work is to understand the influence of the geometric parameters of envelope eco-materials, such as hemp concrete, on the mechanisms of coupled heat, air and moisture transfers, in order to predict behavior of the building to control and improving it in its durability. For this a multi-scale approach is implemented. It consists of mastering the dominant physical phenomena and their interactions on the microscopic scale. Followed by a dual-scale modeling, microscopic-macroscopic, of coupled heat, air and moisture transfers that takes into account the intrinsic properties and microstructural topology of the material using X-ray tomography combined with the correlation of 2D and 3D images. A characterization campaign of physical and hydrothermal properties of the hemp concrete manufactured in the laboratory was carried. It focused on studying the impact of aging, thermal and hydric state of the material on these intrinsic properties. The results show an excellent thermal insulation and natural moisture regulation capacity of hemp concrete. Then, a microscopic characterization by different imaging techniques was performed. The 3D reconstructions of the real material scanned with X-ray tomography at different resolutions show that hemp concrete has several scales of porosity, ranging from micro-porosity within the binder and hemp shiv to the inter-particle macro-porosity. The hydromorphic behavior under hydric solicitations was studied. The results of the 2D digital image correlation and X-ray tomography coupled with the volumetric image correlation show the nature of the behavior of hemp concrete subjected to different relative humidities. In fact, the hemp shiv undergoes greater deformations than the binder, thus causing changes in the microstructure of the material. On the modeling part, a model of coupled heat, air and moisture transfer in porous building materials was developed using the periodic homogenization technique. The homogenized tensors of diffusion and thermal conductivity were determined numerically. Then, a confrontation between the results of the calculation of the macroscopic diffusion coefficients and the experimental results obtained at the LaSIE was carried out. It highlights the quality of the prediction. In addition, the thermal conductivity of the solid phase was thus deduced. The results obtained in the framework of this PhD thesis have highlighted the influence of the hydric and thermal state of the hemp concrete on these intrinsic properties and its very heterogeneous microstructure. They also revealed the limitations of phenomenological approaches based on the establishment of the balances of mass, amount of motion and energy

A casca de pinhão manso é um resíduo abundante da indústria de biocombustível e foi usada em sua forma natural (PN) e tratada por plasma não térmico (PP) como biossorvente para a remoção do corante Vermelho reativo 120 (VR-120) de soluções aquosas. Os nanotubos de carbono de parede múltipla (NTCPM) e carvão ativo (CA) foram investigados como adsorventes na remoção do corante Azul direto 53 (AD-53) a partir de águas residuais. Os materiais adsorventes foram caracterizados por espectroscopia Raman, espectroscopia de infravermelho, isotermas de adsorção/dessorção de N2, microscopia eletrônica de varredura e transmissão. As melhores condições para adsorção dos corantes foram alcançadas em pH 2,0. O tempo de contato para obter o equilíbrio de isotermas, em 298-323 K, foi fixado em 10 horas para os biossorventes PN e PP. Para estes, o modelo cinético de ordem geral forneu o melhor ajuste aos dados experimentais em comparação com as cinéticas pseudo-primeira ordem e pseudo-segunda ordem. Para o corante VR-120, os dados de equilíbrio (298-323 K) foram ajustados para o modelo de isoterma de Liu. A capacidade máxima de adsorção do corante ocorreu a 323 K, atingindo valores de 40,94 e 65,63 mg g-1 para o PN e PP, respectivamente. Os resultados dos estudos de adsorção/dessorção mostraram que a maior porcentagem de remoção de PN e PP foram alcançadas quando a mistura de solventes (acetona a 50% + 50% de 0,050 mol L-1 de NaCl (v/v)) foi utilizada. Os efluentes simulados foram utilizados para verificar a aplicabilidade dos biossorventes propostos. A remoção ocorreu de 68,2 e 94,6%, para PN e PP, respectivamente, em meio com elevada concentração salina. Já para NTCPM e CA os tempos de contato foram fixados em 3 horas e 4 horas, respectivamente. O modelo da cinética de ordem geral forneceu o melhor ajuste aos dados experimentais, se comparado aos modelos de adsorção cinéticos de pseudoprimeira ordem e pseudo-segunda ordem. Para o corante AD-53, os dados no equilíbrio (298-323 K) foram ajustados pelo modelo de isoterma de Sips. A capacidade máxima de adsorção do corante ocorreu a 323 K, com os valores de 409,4 e 135,2 mg g-1 para NTCPM e CA, respectivamente. Os resultados dos estudos de adsorção/dessorção mostraram que os NTCPM carregados com AD-53 podem ser regenerados (97,85%) utilizando uma solução de acetona aquosa (50% de acetona + 50% NaOH 3 mol L-1 (v/v)). Em experimentos de simulação de efluentes têxteis para aplicação dos adsorventes no tratamento de efluentes industriais, foram obtidas as remoções de 99,87% e 97,00% para NTCPM e CA, respectivamente, num meio com alta salinidade e diversos corantes. / Jatropha curcas shell an abundant residue of the biocombustible industry, was used in its natural form (JN) and treated by non-thermal plasma (JP) as biosorbents for the removal of Reactive Red 120 (RR-120) dye from aqueous solutions. Multi-walled carbon nanotubes (MWCNT) and powder activated carbon (PAC) were used as adsorbents for adsorption of Direct Blue 53 dye (DB-53) from aqueous solutions. The adsorbents were characterised using Raman spectroscopy, infrared spectroscopy, N2 adsorption/desorption isotherms, and scanning and transmission electron microscopy. The best conditions to adsorption of the dye by adsorbent were achieved at pH 2.0. The contact time to obtain equilibrium isotherms at 298–323 K was fixed at 10 h for both biosorbents. The general order kinetic model provided the best fit to the experimental data compared with pseudo-first order and pseudo-second order kinetic adsorption models. For RR-120 dye, the equilibrium data (298–323 K) were best fitted to the Liu isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, attaining values of 40.94 and 65.63 mg g−1 for JN and JP, respectively. The results of adsorption/desorption studies showed that the highest percentage of removal of JN and JP were obtained when the mixture of solvents (acetone 50% + 50% 0.050 mol L-1 NaCl (v/v)) was used. Simulated dyehouse effluents were used to check the applicability of the proposed biosorbents for effluent treatment. The removal was 68.2 and 94.6% for JP and JN, respectively, in media with high salinity. As for NTCPM and CA the contact times were set at 3 h and 4 h, respectively. The general order kinetic model provided the best fit of the experimental data compared to pseudo-first order and pseudo-second order kinetic adsorption models. For DB- 53 dye, the equilibrium data (298 to 323 K) were best fitted to the Sips isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, with the values of 409.4 and 135.2 mg g-1 for MWCNT and PAC, respectively. The results of adsorption/desorption studies showed that MWCNT loaded DB-53 could be regenerated (97.85%) using mixture 50% acetone + 50% of 3 mol L-1 NaOH (v/v). Simulated dye house effluents were used to evaluate the application of the adsorbents for effluent treatment, with removal of 99.87% and 97.00% for MWCNT and PAC, respectively.

Made available in DSpace on 2014-06-11T19:24:45Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-21Bitstream added on 2014-06-13T20:12:59Z : No. of bitstreams: 1 villavelez_ha_me_sjrp.pdf: 807308 bytes, checksum: 262020576b600a66d35be63d82b014a7 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A banana é a fruta com maior produção mundial, sendo plantada em quase todos os continentes. Devido à grande oferta de banana no mercado, é notável a existência de problemas com a geração de resíduos causados por desperdícios (fruta sobremadura) e material celulósico gerado no cultivar. O presente trabalho tem como objetivo principal a aplicação do processo de secagem para resíduos do cultivar da banana nanica (Mussa spp. Haploide AAB ), visando seu possível aproveitamento na indústria. Resíduos de banana tipo nanica (casca, pedicelo, pedúnculo) e polpa foram caracterizados quimicamente, encontrando valores de cinza, umidade, matéria seca, proteína, lipídeos e carboidratos totais muito próximos à literatura. A relação entre o conteúdo de umidade e a atividade de água proporciona informações uteis para a armazenagem e processamento destes resíduos. Na pesquisa foram determinadas isotermas de desorção para casca, pedicelo e polpa de banana a seis temperaturas (20, 30, 40, 50, 60 e 70°C), na faixa de conteúdo de umidade entre 0,001-6,360 kg·kg -1 e atividades de água entre 0,02-0,907. O modelo teórico de GAB foi empregado para a modelagem das isotermas de desorção. Foi proposta a segunda derivada da solução analítica da equação de Clausius-Clapeyron para calcular o calor isostérico de sorção, a entropia diferencial e, a energia livre de Gibbs, através do modelo de GAB quando o efeito da temperatura em equilíbrio higroscópico é considerado. Experimentos de secagem para casca de banana foram realizados em um secador de leito fixo, a três diferentes velocidades de ar (2.5, 1.5 e 1.0 m·s -1 ), e quatro temperaturas (40, 50, 60 e 70°C). Os modelos de Peleg, Lewis, Henderson-Pabis e difusivo, foram empregados na modelagem das curvas de secagem. Na análise gráfica, encontrou-se que a velocidade de ar não influência no tempo final secagem... / Banana is the most produced fruit in the world, being planted in every continent. Due to the large supply bananas in the market, the existence of problems with waste generation caused for overripe fruit and cellulosic material is noteworthy. The objective of this paper is the drying process implementation for banana waste, variety nanica (Mussa spp. Haploid AAB), for a possible application in the industry. Waste (peel, pedicel and peduncle) and pulp of banana nanica were characterized chemically, where values of ash, protein, fat, carbohydrates, and water were quantified, showing similar results with literature. The relationship between moisture content and water activity provides useful information for processing and storage of banana waste. The desorption isotherms of peel, pedicel and pulp of overripe bananas were determined at six different temperatures (20, 30, 40, 50, 60 and 70ºC) over wide ranges of moisture content (0,001–6,360 kg kg-1 d.b.) and water activity (0,02– 0,907). The theoretical model of GAB was used for modeling the desorption isotherms. An analytical solution of the Clausius-Clapeyron equation was proposed to compute the isosteric heat of sorption, the differential entropy, and the Gibbs’ free energy, by means of the GAB model when the effect of temperature on hygroscopic equilibrium is considered. Drying kinetics for peel banana in convective hot air forced equipment were determined, at three air velocities (2.5, 1.5 and 1.0 m·s -1 ), and four temperatures (40, 50, 60 and 70 ° C). The models of Peleg, Lewis, Henderson-Pabis, and diffusive were used to the modeling of drying curves. In the graphical analysis, for all experiments, air velocity does not influence in the final time of drying, showed a decreasing rate period of drying. Finally, acid hydrolysis of dry peel banana was performed by using a central composite design experimental with three... (Complete abstract click electronic access below)

Made available in DSpace on 2014-12-17T15:01:28Z (GMT). No. of bitstreams: 1 RicardoPFM_DISSERT.pdf: 809568 bytes, checksum: 0179539902298813dbee39bd2859650c (MD5) Previous issue date: 2012-07-20 / The generation of effluent from the finishing process in textile industry is a serious environmental problem and turned into an object of study in several scientific papers. Contamination with dyes and the presences of substances that are toxic to the environment characterize this difficult treatment effluent. Several processes have already been evaluated to remove and even degrade such pollutants are examples: coagulation-flocculation, biological treatment and advanced oxidative processes, but not yet sufficient to enable the recovery of dye or at least of the recovery agent. An alternative to this problem is the cloud point extraction that involves the application of nonionic surfactants at temperatures above the cloud point, making the water a weak solvent to the surfactant, providing the agglomeration of those molecules around the dyes molecules by affinity with the organic phase. After that, the formation of two phases occurred: the diluted one, poor in dye and surfactant, and the other one, coacervate, with higher concentrations of dye and surfactants than the other one. The later use of the coacervate as a dye and surfactant recycle shows the technical and economic viability of this process. In this paper, the cloud point extraction is used to remove the dye Reactive Blue from the water, using nonionic surfactant nonyl phenol with 9,5 etoxilations. The aim is to solubilize the dye molecules in surfactant, varying the concentration and temperature to study its effects. Evaluating the dye concentration in dilute phase after extraction, it is possible to analyze thermodynamic variables, build Langmuir isotherms, determine the behavior of the coacervate volume for a surfactant concentration and temperature, the distribution coefficient and the dye removal efficiency. The concentration of surfactant proved itself to be crucial to the success of the treatment. The results of removal efficiency reached values of 91,38%, 90,69%, 89,58%, 87,22% and 84,18% to temperatures of 65,0, 67,5, 70,0, 72,5 and 75,0?C, respectively, showing that the cloud point extraction is an efficient alternative for the treatment of wastewater containing Reactive Blue / A gera??o de efluente proveniente do processo de acabamento na industria t?xtil ? um grave problema ambiental e se transformou em objeto de estudo em diversos trabalhos cient?ficos. A contamina??o por corantes e a presen?a de subst?ncias que s?o t?xicas ao meio ambiente caracterizam este efluente de dif?cil tratamento. V?rios processos j? foram avaliados para remover e at? degradar tais poluentes s?o exemplos: a coagula??o-flocula??o, tratamento biol?gico e processos oxidativos avan?ados, mas ainda n?o foram suficientes para possibilitar a recupera??o do corante ou pelo menos do agente separador. Uma alternativa para este problema ? a extra??o por ponto nuvem que envolve a aplica??o de tensoativos n?o i?nicos a temperaturas acima do ponto de nuvem, tornando a ?gua um solvente fraco para o tensoativo, proporcionando a aglomera??o destas mol?culas ao redor do corante por afinidade a fase org?nica. Depois disso ocorre a forma??o de duas fases: uma chamada de dilu?da pobre em corante e tensoativo e a coacervato com concentra??o de corante e tensoativo bem maior que a outra fase. A utiliza??o posterior do coacervato como reciclo de corante e tensoativo mostra a viabilidade t?cnica e econ?mica do processo. Neste trabalho a extra??o por ponto nuvem ? utilizada para remover o corante Reactive Blue da ?gua utilizando tensoativo n?o-i?nico nonil fenol com 9,5 etoxila??es. O objetivo ? solubilizar as mol?culas de corante no tensoativo, variando-se a concentra??o deste e a temperatura para estudar seus efeitos. Avaliando a concentra??o de corante na fase dilu?da ap?s a extra??o ? poss?vel analisar vari?veis termodin?micas, construir isotermas de Langmuir, determinar o comportamento do volume de coacervato para uma concentra??o de tensoativo e temperatura, o coeficiente de distribui??o e a efici?ncia de remo??o de corante. A concentra??o de tensoativo mostrou-se fundamental para o sucesso do tratamento. Os resultados de efici?ncia de remo??o alcan?aram valores de 91,38%, 90,69%, 89,58%, 87,22% e 84,18% para temperaturas de 65,0, 67,5, 70,0, 72,5 e 75,0?C, respectivamente, mostrando que a extra??o por ponto nuvem ? uma alternativa eficiente para o tratamento de efluentes contendo Reactive Blue