Submitted by Geandra Rodrigues (geandrar@gmail.com) on 2018-11-05T13:41:09Z No. of bitstreams: 1 deboraguimaraesdeoliveira.pdf: 3971933 bytes, checksum: 7b5a0ee6a3a033ca0149c8adc512aea2 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2018-11-23T11:16:07Z (GMT) No. of bitstreams: 1 deboraguimaraesdeoliveira.pdf: 3971933 bytes, checksum: 7b5a0ee6a3a033ca0149c8adc512aea2 (MD5) / Made available in DSpace on 2018-11-23T11:16:07Z (GMT). No. of bitstreams: 1 deboraguimaraesdeoliveira.pdf: 3971933 bytes, checksum: 7b5a0ee6a3a033ca0149c8adc512aea2 (MD5) Previous issue date: 2018-08-31 / A proteção superficial de nanoesferas de ouro (AuNEs) pode fornecer uma maior estabilidade coloidal, importante quando se trabalha com sistemas biológicos, por apresentarem situações diversas que podem levar à agregação das AuNEs. O biopolímero quitosana (Quit) é um material atóxico, apresenta baixo custo, e vem sendo muito utilizado em sistemas biológicos para diagnóstico de doenças. Sistemas sensíveis, como os biossensores utilizados na detecção de moléculas adsorvidas em AuNEs, podem ser monitorados por mudança na banda de ressonância de plasmon de superfície localizado (LSPR) e pela utilização da técnica de espalhamento Raman intensificado por superfície (SERS). Quando as moléculas são adsorvidas nas superfícies das AuNEs é possível observar a indução de agregação da suspensão coloidal pela mudança na banda LSPR. Devido à sensibilidade analítica, as superfícies das AuNEs são protegidas para evitar agregação e precipitação coloidal, e a obtenção de resultados falso-positivos. Esta tese teve como objetivo realizar vários estudos utilizando as AuNEs protegidas superficialmente por Quit para oferecer uma maior estabilidade e controlar a formação de hot spots na presença do analito. Para tal, sempre foram realizados experimentos comparando as AuNEs com e sem proteção superficial por Quit. Os estudos iniciais observaram a resistência à agregação das AuNEs com relação ao tempo de exposição em temperatura ambiente. Seguindo o raciocínio as AuNEs também foram expostas à diferentes concentrações dos agentes agregantes etanol (EtOH) e KCl. Os analitos utilizados como molécula prova para o SERS e também para observar possíveis mudanças na banda LSPR, foram os corantes: cristal violeta (CV), rodamina 6G (R6G) e IR-820, que apresentam cargas superficiais positiva ou negativa; a fim de identificar alguma preferência na adsorção por carga superficial do analito. Para os estudos em espectroscopia SERS, foram realizadas medidas variando concentração de Quit na presença dos corantes juntos ou separados, além de observar a interferência na ordem de adição do corante no sinal SERS. A Quit se mostrou promissora para aumentar a estabilidade das AuNEs e, portanto, experimentos para tentar modular e controlar a formação de hot spots foram realizados. O efeito SERS foi utilizado como uma ferramenta analítica em que foi estudada a relação direta do sinal SERS obtido dos corantes, com a sua concentração em solução. A partir destes resultados, foi possível construir isotermas de adsorção dos corantes estudados, que foram ajustadas ao modelo de Langmuir. / The surface protection of gold nanospheres (AuNEs) can provide greater colloidal stability, important when work with biological system, because the present diverse situations that can lead to the aggregation of AuNEs. The chitosan biopolymer (Quit) is a non-toxic material, presents low cost, and has been widely in biological systems for the diagnosis of diseases. Sensitive systems, such as biosensors used in detection of adsorbed molecules in AuNEs, can be monitored by changing in Localized Surface Plasmon Resonance´s band (LSPR) and by use of Surface-Enhanced Raman Spectroscopy technique (SERS). When the molecules are adsorbed on the AuNEs surfaces is possible to observe the induction of aggregation of the colloidal suspension by the change in the LSPR band. Due to the analytical sensitivity, the surfaces of the AuNES are protected to avoid aggregation and colloidal precipitation, and to obtain false positive results. This thesis aimed to perform several studies using the AuNEs surface protected by Quit to offer greater stability and to control the formation of hot spots in the presence of the analyte. For this, experiments were always done to compare the AuNEs with and without surface protection by Quit. The initial studies observed the resistance to AuNEs aggregation in relation to exposure time at room temperature. Following the reasoning, the AuNEs were also exposed to different concentrations of the aggregating agents ethanol (EtOH) and KCl. The analytes that were used as a test molecule for the SERS and also to observe possible changes in the LSPR band were the dyes: crystal violet (CV), rhodamine 6G (R6G) and IR-820, which have positive or negative surface charges; in order to identify some preference in surface adsorption of the analyte. For the SERS spectroscopy studies, measurements were performed varying the concentration of Quit in the presence of the dyes together or separated, besides observing the interference in the order of dye addition in the SERS signal. The Quit proved promising to increase the stability of AuNEs and, therefore, modification experiments, aiming at modulate and control the formation of hot spots, were performed. The SERS effect was used as an analytical tool in which the direct relationship of the SERS signal obtained from the dyes with their concentration in solution was studied. From these results, it was possible to construct adsorption isotherms of the studied dyes, which were adjusted to the Langmuir model.

Les activités humaines ont généré une augmentation importante de la concentration de gaz à effet de serre (GES) au cours des 150 dernières années, ce qui est relié à plusieurs problèmes environnementaux, tels que le réchauffement planétaire et les changements climatiques. Le secteur agricole contribue de 8 à 10% aux émissions totales de GES dans l'atmosphère, et les principaux GES émis sont le dioxyde de carbone (CO2), le méthane (CH4) et l'oxyde nitreux (N2O). Le contrôle et la quantification de ces émissions requièrent des technologies qui permettent de les capturer et ou les dégrader, par exemple par adsorption. L'objectif du présent projet est de caractériser des matériaux qui puissent être utilisés comme adsorbants des GES et de décrire leurs cinétiques d'adsorption afin d'avoir l'information qui permet de sélectionner des adsorbants pour capturer le CH4 et le N2O à des basses concentrations et à température et pression ambiantes. Pour adsorber le CH4, des adsorbants commerciaux et synthétiques ont été utilisés. Les adsorbants choisis ont été des zéolithes, un biocharbon conditionné au laboratoire et un ZIF (« Zeolitic imidazolate framework », ZIF-8) synthétisé au laboratoire. Ce dernier a été employé aussi pour adsorber du N2O. La capacité d'adsorption de CH4 et de N2O a été évaluée pour chaque adsorbant par de tests dynamiques d'adsorption du gaz sous conditions ambiantes. Ces matériaux ont été caractérisés physiquement et chimiquement afin de corréler leurs propriétés avec la capacité d'adsorption de CH4 et/ou de N2O. Des isothermes d'équilibre ont été utilises pour modéliser les donnés expérimentales. Parmi les différents matériaux utilisés lors de l'adsorption du CH4 à 30 ºC et à pressions partielles de CH4 inférieures à 0,40 kPa, les biocharbons présentent la capacité d'adsorption la plus élevée, suivis par le ZIF-8 et les zéolithes commerciales / Human activities contributed with a significant increase in GHG concentrations over the past 150 years and they are related to environmental issues, such as global warming and climate change. The agricultural sector contributes 8 to 10% of total GHG emissions to the atmosphere, being carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) the main GHGs emitted. The control and quantification of these emissions requires technologies which can capture and or degrade these GHG, for example by adsorption. The objective of this project is to characterize adsorbents and to describe their adsorption kinetics in order to select the most suitable for the adsorption of CH4 and N2O at low concentration and at ambient temperature. For CH4 adsorption, commercial and synthesized adsorbents were tested. The selected adsorbents were commercial zeolites, laboratory conditioned biochar and synthesized ZIF ("Zeolitic imidazolate framework"). ZIF was also used for N2O adsorption. The adsorption capacity of CH4 and N2O for each adsorbent was evaluated by dynamic adsorption tests of the gas under atmospheric conditions. These materials were physically and chemically characterized in order to correlate its properties with its CH4 and/or N2O adsorption capacity. The experimental data of gas adsorption were fitted by equilibrium isotherms. Among the different materials used for CH4 adsorption at 30 ºC and partial pressures lower than 0.40 kPa, biocharbons presented the highest adsorption capacity, followed by ZIF- 8 and commercial zeolites

The Diploma thesis deals with humic acids and their ability to adsorb metal ions on their surface. Humic acids are aromatic polycyclic compounds which contain carboxylic and fenolic functional groups on their sidechains. Thanks to these functional groups humic acids can form complexes with metal ions of different stability and assist the partial immobilization of pollutants in the nature. In this thesis, the sorption of Pb2+ and Zn2+ ions on humic acids was studied by relatively new electroanalytic method called galvanostatic stripping chronopotentiometry. Experimental data were described by Freundlich and Langmuir isotherms. The results show that the amount of examined metal ions increases with their increasing concentration. Furthermore it was determined that Pb2+ ions are adsorbed better on humic acids than Zn2+ ions. Both metals are adsorbed better from solution containing only one metal ion than in presence of four metals at the same time (Cd, Cu, Zn and Pb) where the sorption of these metals is not influenced by the presence of other metals.

No description available.

Arsenic (As) contamination is a worldwide problem, and millions of people are suffering from it. There are two major inorganic forms of As in waters: arsenate(V) and arsenite(III), and adsorption to a sorbent material may be an efficient method to handle them. In this study, we focused on As(III), the more toxic form, which predominates under reducing conditions. The As(III) removal properties of four sorbent materials: hydrotalcite, Mg−Al layered double hydroxide, amorphous aluminium hydroxide and amorphous titanium oxide, are examined from the following viewpoints: As(III) adsorption, the effects of pH, the effects of adsorbent concentration, adsorption as a function of dissolved As(III), and the effect of co-existing anions (HCO3− and PO43−). The maximum adsorption of As(III) to HT (0.1 mmol As(III)/g adsorbent), Mg-Al LDH (0.1 mmol As(III)/g adsorbent), am-Al(OH)3 (0.22 mmol As(III)/g adsorbent), and am-TiO2 (0.21 mmol As(III)/g adsorbent) occurred at pH 7.5, 7, 7, 8, respectively. At this pH, approximately 20%, 62%, 35%, and 98.3%, respectively, of the added As(III) was adsorbed. When the As(III) to sorbent ratio was increased, the adsorption was instead around 7% to am-Al(OH)3 (2.2 mmol As(III)/g adsorbent), and 46.3% to am-TiO2 (2.1 mmol As(III)/g adsorbent). These figures show that am-TiO2is the most efficient sorbent for As(III) adsorption of the four materials tested, Mg-Al LDH is second best, while HT and am-Al(OH)3 are not suitable for As(III) removal. The adsorption of As(III) to Mg-Al LDH as a function of dissolved As(III) could be adequately described by a linear equation, suggesting that As(III) adsorption to Mg-Al LDH was governed by anion exchange. As a result, the co-existing anions (HCO3- and PO43-) showed a significant influence on As(III) adsorption to Mg-Al LDH. Considering the interfering effects of co-existing anions on am-TiO2, HCO3− did not influence As(III) adsorption, while PO43- caused a slight but clear competition effect. Overall, am-TiO2 would be the best choice of these four materials in contact with As-contaminated groundwater due to its superior As(III) removal properties and the limited competition from co-existing anions on As(III) adsorption. / Alltför höga halter av arsenik (As) i vatten är ett världsomspännande problem som orsakar hälsoproblem för miljontals människor. Det finns två huvudsakliga oorganiska former av As i vatten: arsenat(V) och arsenit(III), och adsorption till ett material (s.k. ”sorbent”) kan vara eneffektiv metod för att avlägsna dem från vatten. I denna studie fokuserade vi på arsenit(III), den mer giftiga formen, vilken dominerar under reducerande förhållanden. Vi undersökte adsorptionsegenskaperna för arsenit(III) för fyra sorbentmaterial som kan vara tänkbara när det gäller arsenikrening av förorenade vatten: hydrotalkit, s.k. Mg-Al LDH (Mg-Al-skiktad dubbelhydroxid), am-Al(OH)3 (amorf aluminiumhydroxid), och am-TiO2 (amorf titandioxid). Dessa material undersöktes när det gäller följande: adsorption av arsenit(III) som funktion av pH,betydelsen av sorbentkoncentration, adsorption som funktion av löst arsenit(III) (”isoterm”), och konkurrens från samexisterande anjoner (HCO3− och PO43−). Den maximala adsorptionen av As (III) till HT (0,1 mmol As(III)/g sorbent), Mg-Al LDH (0,1 mmol As(III)/g sorbent), am-Al(OH)3 (0,22 mmol As(III)/g sorbent) och am-TiO2(0,21 mmol As(III)/g sorbent) inträffade vid pH 7,5, 7, 7, respektive 8. Vid dessa pH-värden adsorberades ungefär 20%, 62%, 35% respektive 98,3% tillsatt As(III). När kvoten mellan As(III) till sorbent ökades blev adsorptionen istället cirka 7% till am-Al(OH)3 (2,2 mmol As(III)/g sorbent) och 46,3% till am-Ti02(2,1mmol As(III)/g sorbent). Dock var adsorptionsmängden per viktsenhetsorbenthögre över hela pH-området. Dessa siffror visar att am-TiO2 är det mest effektiva av de fyra testade materialen för As(III)-adsorption, Mg-Al LDH det näst bästa, medan HT och am-Al(OH)3 är olämpliga för detta ändamål. Adsorptionen av As(III) till Mg-Al LDH som funktion av löst As(III) kunde beskrivas väl med en linjär ekvation, vilket antyder att adsorptionen av As(III) till Mg-Al LDH styrdes av anjonbyte. I konsekvens med detta hade de samexisterande anjonerna (HCO3- och PO43-) ett betydande inflytande på As(III)-adsorptionen till Mg-Al LDH. För am-TiO2 påverkade HCO3− inte As(III)-adsorptionen, medan PO43- orsakade en liten men tydlig konkurrenseffekt. Sammantaget är am-TiO2 det bästa valet av dessa fyra material i kontakt med As- kontaminerat grundvatten på grund av dess betydligt bättre förmåga att avskilja arsenit(III) och den förhållandevis blygsamma konkurrensen från andra anjoner.

Cette thèse s'inscrit dans le cadre de la recherche des moyens de réduction du bruit. Le but est d’analyser et de créer par une méthode passive, le confinement d’énergie acoustique dans les irrégularités géométriques via le phénomène de localisation pour ensuite la dissiper. En prélude à l'atténuation du bruit par les géométries irrégulières, les mécanismes de la dissipation acoustique sont rappelés et illustrés par quelques exemples de réseaux de résonateurs quart-d'onde. Le phénomène de localisation est ensuite étudié par une analyse modale. Le caractère localisé d'un mode est quantifié par son volume d'existence relatif (VER) qui donne, en fraction du volume total du domaine, le volume effectif concerné par l'énergie du mode. Il ressort de cette étude que seules les cavités irrégulières ayant des irrégularités en forme de sous-cavités couplées à une cavité principale sont « localisantes ». La fréquence d'un mode localisé est liée aux dimensions de la zone irrégulière de localisation. Le lien entre les irrégularités géométriques et la dissipation acoustique est ensuite analysé au moyen des indicateurs tels que le facteur de qualité, le coefficient d'absorption ou le taux d'amortissement de l'énergie. Cette étude montre que les cavités irrégulières amortissement mieux une onde acoustique comparativement aux cavités à géométrie régulière. Toutefois, la dissipation de l'énergie acoustique des cavités irrégulières n'est pas uniquement liée à la localisation. Elle dépend également d'autres paramètres (porosité, résistivité, etc.). Lorsque les irrégularités des parois rigides ne permettent pas de réaliser une dissipation suffisante, elles peuvent être réalisées dans les matériaux poroélastiques à performance acoustique moyenne pour augmenter leur capacité dissipative. Enfin, des études expérimentales menées ont permis de valider l'existence du phénomène de localisation et de confirmer la tendance plus dissipative des géométries irrégulières par rapport aux géométries régulières. De même, des mesures du coefficient d'absorption d'un échantillon de forme préfractale d'un béton de chanvre (matériau ayant une performance acoustique moyenne) montrent une augmentation de la dissipation de plus de 40% induite par la forme irrégulière. La contribution majeure de cette thèse est d’avoir répondu à un défi technologique important consistant à effectuer une mise en évidence expérimentale du phénomène de localisation jusque-là difficile à réaliser avec des microphones. Pour y parvenir, un outil optique peu conventionnel dans la métrologie acoustique est adopté; il s'agit de la réfracto-vibrométrie qui consiste à utiliser, sous certaines conditions, le vibromètre laser pour mesurer un champ acoustique (pression acoustique). Bien que contraignante, cette technique présente l'avantage d'être non intrusive et donc moins encombrante même pour de petites cavités comparativement aux microphones. / In this thesis, the acoustical behavior of irregular cavities leading to localization phenomenon is investigated for noise reduction applications. The aim of this work is to study and create by means of passive method, an accumulation of acoustical energy and dissipate it. Before addressing geometrical irregularities effects on the sound field, viscothermal dissipation mechanisms of sound are recalled and illustrated through few networks of quarter-wave resonators. In a second part, a study of the localization phenomenon is carried out by a modal analysis approach. The localization is quantified by the relative existence volume (VER), an indicator which gives a measure of the volume of the region in which a mode is localized as a fraction of the total cavity volume. The localization analysis is conducted using both regular and irregular cavities. It has been shown that only cavities with irregular geometry, such that sub-cavities are formed, can localize some acoustical modes. Moreover, the frequency of a localized mode is related to the dimensions of the localization region. Following the investigation of the localization phenomenon, the relation between cavities geometry and sound energy dissipation has been studied by the estimation of damping indicators, such as the quality factor, the sound absorption coefficient or the energy damping rate. According to this study, irregular cavities have higher capability to damp sound waves compared to regular cavities. However, for the case of irregular cavities only, the induced dissipation is not proportional to the localization. Nevertheless, when irregularities of rigid walls are not able to achieve sufficient dissipation, this can be obtained with slightly absorptive porous materials of irregular geometry. In fact, the dissipative properties of some porous materials can be optimized by giving them irregular interface. Finally, an experimental set-up has been designed to validate the localization phenomenon and to confirm the damping tendency of irregular geometries in comparison to regular ones. Moreover, measurements of the sound absorption coefficient of a hemp concrete reveal that the sample of irregular geometry achieves sound dissipation more than 40% higher than the one achieved by a regular plane sample. Finally, this thesis has addressed a technological challenge consisting of experimentally validating the localization phenomenon which is so far very difficult to obtain by the use of conventional pressure microphones. In the framework of this thesis, an optical non-conventional sound pressure measurement technique has been used. The used technique is the laser refracto-vibrometry which consists of using a laser vibrometer in some specific conditions to measure the acoustical field (sound pressure). This technique is difficult to conduct but it has the advantage of being contactless, thus less cumbersome for even very small cavities as compared to pressure microphones.

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.

Ethyl lactate (EL) plays a major role as green solvent and also a replacement for most petrochemical solvents. The esterification process of lactic acid and ethanol to produce EL is an equilibrium-limiting reaction and the selective removal of one of the reaction products can be improved using a membrane reactor and when coupled with a heterogeneous catalyst offers an opportunity for process intensification. This thesis investigates the batch process esterification reaction involving lactic acid (LA) and ethanol (EL) in the presence of a water selective membrane using different cation-exchange resin catalysts. The product was analysed using gas chromatograph coupled with mass spectrometry detector (GC-MS). The analytical methods used for the characterisation of the cation-exchange resins and membrane include Fourier transform infrared coupled with attenuated total reflectance (FTIR-ATR), scanning electron microscopy attached to energy dispersive analyser (SEM/EDAX), Liquid nitrogen physisorption and nuclear magnetic resonance (NMR) respectively. A novel method was developed for carrying out esterification reaction in a gaseous phase system using a flat sheet polymeric membrane. Prior to the esterification reaction, different carrier gases were tested with ceramic membrane to determine the suitable carrier gases for the analysis of esterification product. The four carrier gases used for the permeation test were argon (Ar), helium (He), carbon dioxide (CO2) and nitrogen (N2). A 15nm pore size commercially available tubular ceramic support, consisting of 77%Al2O3 and 23%TiO2 with the porosity of 45% was used for the carrier gas investigation. The support was modified with silica based on the sol-gel dip-coating techniques. The dip-coated membrane exhibited a higher molar flux with He (0.046mol m-2s-1) and Ar (0.037mol m-2s-1) with a much lower flux for N2 (0.037mol m-2s-1) and CO2 (0.035 mol m-2s-1) at 0.30 bar. Helium gas with the highest permeation rate were identified as the suitable carrier gas for the analysis of esterification product with GC-MS. The esterification reaction in the presence of four cation-exchange resins to produce ethyl lactate was carried out between 60-160 oC in a batch and membrane processes to determine the effectiveness resin catalysts for LA esterification. The effect of external mass transfer diffusion limitation between the liquid components and the resin catalysts was avoided by increasing the agitation time of the esterification reaction. The percentage conversion rate of the lactic acid feed from the batch process esterification was found to be in the range of 98.6 to 99.8%. The reaction kinetics of the esterification reaction was described based on two simplified mechanisms of Langmuir Hinshelwood model to describe the adsorption components on the surface of the catalysts. The lactic acid feed gave a conversion rate of up to 100 % confirming the effectiveness of the acetate membrane impregnated resin catalysts in the selective removal of water for the separation of ethyl lactate. The significance of producing ethyl lactate through batch process intensified by a water-selective membrane processes can be recommended for industrial LA production.

Made available in DSpace on 2014-12-17T15:42:04Z (GMT). No. of bitstreams: 1 CamilaRML_DISSERT.pdf: 3932876 bytes, checksum: 4cacf8f7fc64136e2ecb15a917a88b97 (MD5) Previous issue date: 2013-01-25 / Universidade Federal do Rio Grande do Norte / Among the polymers that stand out most in recent decades, chitosan, a biopolymer with physico-chemical and biological promising properties has been the subject of a broad field of research. Chitosan comes as a great choice in the field of adsorption, due to their adsorbents properties, low cost and abundance. The presence of amino groups in its chain govern the majority of their properties and define which application a sample of chitosan may be used, so it is essential to determine their average degree of deacetylation. In this work we developed kinetic and equilibrium studies to monitor and characterize the adsorption process of two drugs, tetracycline hydrochloride and sodium cromoglycate, in chitosan particles. Kinetic models and the adsorption isotherms were applied to the experimental data. For both studies, the zeta potential analyzes were also performed. The adsorption of each drug showed distinct aspects. Through the studies developed in this work was possible to describe a kinetic model for the adsorption of tetracycline on chitosan particles, thus demonstrating that it can be described by two kinetics of adsorption, one for protonated tetracycline and another one for unprotonated tetracycline. In the adsorption of sodium cromoglycate on chitosan particles, equilibrium studies were developed at different temperatures, allowing the determination of thermodynamic parameters / Dentre os pol?meros que mais se destacam nas ?ltimas d?cadas, a quitosana, um biopol?mero com propriedades f?sico-qu?micas e biol?gicas promissoras, tem sido alvo de um campo amplo de pesquisa. A quitosana se apresenta como uma ?tima escolha no campo de adsor??o, devido a suas propriedades adsorventes, baixo custo e abund?ncia. A presen?a de grupos aminos em sua cadeia governam a maioria das suas propriedades e definem em qual aplica??o dada amostra de quitosana poder? ser utilizada, assim torna-se imprescind?vel a determina??o do seu grau de desacetila??o m?dio. Neste trabalho foram desenvolvidos estudos cin?ticos e de equil?brio a fim de monitorar e caracterizar o processo de adsor??o de dois f?rmacos, o cloridrato de tetraciclina e o cromoglicato de s?dio, em part?culas de quitosana. Modelos cin?ticos e de isotermas de adsor??o foram aplicados nos dados experimentais. Para ambos os estudos, an?lises no potencial zeta tamb?m foram realizadas. A adsor??o de cada f?rmaco apresentou aspectos distintos. Atrav?s dos estudos desenvolvidos neste trabalho foi poss?vel descrever um modelo cin?tico para a adsor??o de tetraciclina em part?culas de quitosana, demonstrando que o mesmo pode ser descrito por duas cin?ticas de adsor??o, uma para a tetraciclina protonada e outra para a tetraciclina n?o protonada. Na adsor??o de cromoglicato de s?dio em part?culas de quitosana, estudos de equil?brio foram desenvolvidos a diferentes temperaturas, permitindo a determina??o de par?metros termodin?micos

Made available in DSpace on 2014-12-17T15:42:05Z (GMT). No. of bitstreams: 1 AnaLPFC.pdf: 1922699 bytes, checksum: c82e91dbc8eb0d49eecb97284bc06938 (MD5) Previous issue date: 2009-08-14 / Due to its physico-chemical and biological properties, related to the abundance and low cost of raw material, chitosan has been recognized as a material of wide application in various fields, such as in drug delivery systems. Many of these properties are associated with the presence of amino groups in its polymer chain. A proper determination of these amino groups is very important, in order to properly specify if a given chitosan sample can be used in a particular application. Thus, in this work, initially, a comparison between the determination of the deacetylation degree by conductometry and elemental analysis was carried out using a detailed analysis of error propagation. It was shown that the conductometric analysis resulted in a simple and safe method for the determining the degree of deacetylation of chitosan. Subsequently, experiments were performed to monitor and characterize the adsorption of tetracycline on chitosan particles through kinetic and equilibrium studies. The main models of kinetics and adsorption isotherms, widely used to describe the adsorption on wastewater treatment systems and the drug loading, were used to treat the experimental data. Firstly, it was shown that an apparent linear t/q(t) ? t relationship did not imply in a pseudo-second-order adsorption kinetics, differently of what has been repeatedly reported in the literature. It was found that this misinterpretation can be avoided by using non-linear regression. Finally, the adsorption of tetracycline on chitosan particles was analyzed using insights obtained from theoretical analysis, and the parameters generated were used to analyze the kinetics of adsorption, the isotherm of adsorption and to ropose a mechanism of adsorption / Devido ?s suas propriedades f?sico-qu?micas e biol?gicas, associadas ? abund?ncia e ao baixo custo da mat?ria-prima, a quitosana tem sido considerada um material de ampla aplica??o em diversos campos, tais como em sistemas de libera??o de f?rmacos. Muitas dessas propriedades est?o associadas ? presen?a de grupos amino em sua cadeia polim?rica. Uma determina??o apropriada desses grupos amino ? muito importante, com o objetivo de especificar adequadamente se uma dada amostra de quitosana pode ser usada em uma particular aplica??o. Dessa forma, neste trabalho, inicialmente, foi realizada uma compara??o entre a determina??o do grau m?dio de desacetila??o atrav?s de an?lises condutim?trica e elementar usando uma minuciosa an?lise de propaga??o erro. Foi mostrado que a an?lise condutim?trica resultou em um m?todo simples e seguro para determina??o do grau m?dio de desacetila??o da quitosana. Posteriormente, foram realizados experimentos a fim de monitorar e caracterizar o processo de adsor??o de tetraciclina em part?culas de quitosana, atrav?s de estudos cin?ticos e de equil?brio. Os principais modelos cin?ticos e de isotermas de adsor??o, amplamente usados para descrever a adsor??o em sistemas de tratamento de efluentes e de incorpora??o de f?rmacos, foram utilizados nos dados experimentais. Primeiramente, foi mostrado que uma aparente rela??o linear t/q(t) ? t n?o implica em um mecanismo de adsor??o de pseudo-segunda-ordem, diferentemente do que tem sido repetitivamente relatado na literatura. Foi encontrado que esta interpreta??o err?nea pode ser evitada atrav?s do uso de uma regress?o n?o-linear. Finalmente, a adsor??o de tetraciclina em part?culas de quitosana foi analisada, utilizando os conhecimentos obtidos de uma an?lise te?rica, e os par?metros gerados foram usados para analisar a cin?tica de adsor??o, a isoterma de adsor??o e para propor um mecanismo de adsor??o