Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-03-31T23:01:39Z No. of bitstreams: 1 GislanePinhoDeOliveira_DISSERT.pdf: 2585969 bytes, checksum: 5a2ec44dfa4024c61a2f9bad2b0cc474 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-04-04T22:09:35Z (GMT) No. of bitstreams: 1 GislanePinhoDeOliveira_DISSERT.pdf: 2585969 bytes, checksum: 5a2ec44dfa4024c61a2f9bad2b0cc474 (MD5) / Made available in DSpace on 2016-04-04T22:09:35Z (GMT). No. of bitstreams: 1 GislanePinhoDeOliveira_DISSERT.pdf: 2585969 bytes, checksum: 5a2ec44dfa4024c61a2f9bad2b0cc474 (MD5) Previous issue date: 2015-06-25 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / O progresso industrial moderno vem incorporando compostos fen?licos entre as impurezas encontradas na ?gua. Por se tratar de uma subst?ncia t?xica e cancer?gena, ? imprescind?vel que a mesma seja reduzida ? concentra??es toler?veis, determinadas pelo CONAMA. Neste contexto, este trabalho tem como objetivo o tratamento e caracteriza??o de catalisadores oriundos do biocarv?o, subproduto da pir?lise de biomassa (avel?s e p? de madeira), assim como sua avalia??o na degrada??o fotocatal?tica do fenol. Os ensaios foram realizados em um reator leito de lama, com medi??es instant?neas da temperatura, pH e oxig?nio dissolvido. Os experimentos foram realizados nas seguintes condi??es operacionais: temperatura igual a 50 ?C, vaz?o de oxig?nio igual a 410 mL min-1 , volume de solu??o reagente igual a 3,2 L, l?mpada UV de 400 W, press?o de 1 atm e tempo de rea??o de 2 horas. Os par?metros avaliados foram o pH do meio reacional (3,0; 6,9 e 10,7), concentra??o inicial de fenol comercial (250, 500 e 1000 ppm), concentra??o de catalisador (0, 1, 2 e 3 g L-1 ) e natureza do catalisador (carv?o do aveloz ativado e lavado com diclorometano, CAADCM, e carv?o da madeira ativado e lavado com diclorometano, CMADCM). Os resultados de FRX, DRX e BET comprovaram a presen?a de ferro e pot?ssio em quantidades satisfat?rias para o catalisador CAADCM e em quantidades reduzidas no catalisador CMADCM, e o aumento da ?rea superficial dos materiais ap?s a ativa??o qu?mica e f?sica. As curvas de degrada??o do fenol indicam que o pH tem uma influ?ncia significativa na convers?o do fenol, apresentando melhores resultados para os valores de pH mais reduzidos. A concentra??o ?tima de catalisador observada foi de 1 g L-1 e o aumento da concentra??o inicial de fenol exerce uma influ?ncia negativa na condu??o da rea??o. Tamb?m foi observado o efeito positivo da presen?a de ferro e pot?ssio na estrutura do catalisador: obteve-se convers?es melhores para os ensaios realizados com o catalisador CAADCM, quando comparado com o catalisador CMADCM nas mesmas condi??es. A maior convers?o foi obtida para o ensaio realizado em pH ?cido (3,0), com uma concentra??o inicial de fenol igual a 250 ppm na presen?a do catalisador CAADCM a 1 g L-1 . As amostras l?quidas retiradas a cada 15 minutos foram analisadas por cromatografia l?quida identificando e quantificando a hidroquinona, p-benzoquinona, catecol e ?cido maleico. Finalmente um mecanismo do processo reacional foi proposto, considerando que o fenol ? transformado em fase homog?nea e os demais reagem na superf?cie do catalisador. Aplicandose o modelo de Langmuir-Hinshelwood juntamente com um balan?o de massa, obteve-se um sistema de equa??es diferenciais que foi resolvido utilizando o m?todo de Runge-Kutta de 4? ordem associado a uma rotina de otimiza??o SWARM (enxame de part?culas), visando minimizar a fun??o objetivo de m?nimos quadrados para estima??o dos par?metros cin?ticos e de adsor??o. Obteve-se constantes cin?ticas da ordem de grandeza de 10-3 para a degrada??o do fenol, 10-4 ? 10-2 para a forma??o de ?cidos, 10-6 ? 10-9 para a mineraliza??o dos quin?nicos (hidroquinona, p-benzoquinona e catecol), 10-3 ? 102 para a mineraliza??o dos ?cidos. / The modern industrial progress has been contaminating water with phenolic compounds. These are toxic and carcinogenic substances and it is essential to reduce its concentration in water to a tolerable one, determined by CONAMA, in order to protect the living organisms. In this context, this work focuses on the treatment and characterization of catalysts derived from the bio-coal, by-product of biomass pyrolysis (avel?s and wood dust) as well as its evaluation in the phenol photocatalytic degradation reaction. Assays were carried out in a slurry bed reactor, which enables instantaneous measurements of temperature, pH and dissolved oxygen. The experiments were performed in the following operating conditions: temperature of 50 ?C, oxygen flow equals to 410 mL min-1 , volume of reagent solution equals to 3.2 L, 400 W UV lamp, at 1 atm pressure, with a 2 hours run. The parameters evaluated were the pH (3.0, 6.9 and 10.7), initial concentration of commercial phenol (250, 500 and 1000 ppm), catalyst concentration (0, 1, 2, and 3 g L-1 ), nature of the catalyst (activated avel?s carbon washed with dichloromethane, CAADCM, and CMADCM, activated dust wood carbon washed with dichloromethane). The results of XRF, XRD and BET confirmed the presence of iron and potassium in satisfactory amounts to the CAADCM catalyst and on a reduced amount to CMADCM catalyst, and also the surface area increase of the materials after a chemical and physical activation. The phenol degradation curves indicate that pH has a significant effect on the phenol conversion, showing better results for lowers pH. The optimum concentration of catalyst is observed equals to 1 g L-1 , and the increase of the initial phenol concentration exerts a negative influence in the reaction execution. It was also observed positive effect of the presence of iron and potassium in the catalyst structure: betters conversions were observed for tests conducted with the catalyst CAADCM compared to CMADCM catalyst under the same conditions. The higher conversion was achieved for the test carried out at acid pH (3.0) with an initial concentration of phenol at 250 ppm catalyst in the presence of CAADCM at 1 g L-1 . The liquid samples taken every 15 minutes were analyzed by liquid chromatography identifying and quantifying hydroquinone, p-benzoquinone, catechol and maleic acid. Finally, a reaction mechanism is proposed, cogitating the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. Applying the model of Langmuir-Hinshelwood along with a mass balance it was obtained a system of differential equations that were solved using the Runge-Kutta 4th order method associated with a optimization routine called SWARM (particle swarm) aiming to minimize the least square objective function for obtaining the kinetic and adsorption parameters. Related to the kinetic rate constant, it was obtained a magnitude of 10-3 for the phenol degradation, 10-4 to 10-2 for forming the acids, 10-6 to 10-9 for the mineralization of quinones (hydroquinone, p-benzoquinone and catechol), 10-3 to 10-2 for the mineralization of acids.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-12-12T18:27:28Z No. of bitstreams: 1 AngelinneCostaAlexandrino_TESE.pdf: 3367753 bytes, checksum: c56321a7ee935dea3023d07d501a15bd (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-12-13T20:12:54Z (GMT) No. of bitstreams: 1 AngelinneCostaAlexandrino_TESE.pdf: 3367753 bytes, checksum: c56321a7ee935dea3023d07d501a15bd (MD5) / Made available in DSpace on 2017-12-13T20:12:54Z (GMT). No. of bitstreams: 1 AngelinneCostaAlexandrino_TESE.pdf: 3367753 bytes, checksum: c56321a7ee935dea3023d07d501a15bd (MD5) Previous issue date: 2017-09-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / H? d?cadas que a produ??o de combust?veis alternativos visando ? substitui??o do petr?leo e de seus derivados tem despertado o interesse de muitos pesquisadores em todo o planeta. Biodiesel ? uma alternativa renov?vel, o qual pode ser produzido a partir de ?leos residuais, gorduras animais e ?leos vegetais atrav?s do processo de transesterifica??o heterog?nea utilizando ?lcoois. Nesse contexto, catalisadores heterog?neos t?m se apresentado como potencial na produ??o de biodiesel em raz?o da possibilidade do seu reuso e por ser um processo mais limpo e eficiente. No presente trabalho, carv?o ativado obtido da pir?lise do lodo de esgoto (C.A), Mo2C, Mo2C/C.A e Ni (20%)-Mo2C/C.A foram avaliados no processo de transesterifica??o met?lica do ?leo de soja refinado visando ? produ??o de biodiesel. O carv?o do lodo foi tratado com o KOH no sentido de abrir os poros e promover maior ?rea especifica de contato, seguido de ativa??o f?sica. Os catalisadores a base de molibd?nio foram sintetizados a partir da rea??o g?s-s?lido utilizando como precursor heptamolibdato de am?nio e uma mistura de CH4/H2. Todos os materiais foram caracterizados utilizando as an?lises de TG, DRX, FRX, MEV, B.E.T e granulometria a laser. O processo de transesterifica??o foi avaliado em um reator de mistura constitu?do de um sistema de aquecimento e refluxo da fase alco?lica. Em temperatura constante de 65 oC, as condi??es operacionais estudadas para a rea??o foram: a natureza e concentra??o m?ssica (1 a 5%) do catalisador em rela??o ? massa do ?leo, a raz?o molar ?leo/?lcool (1/6 a 1/18), o pH do meio reacional (2,0 a 8,5), o tempo de rea??o (3 e 5 h) e a velocidade de agita??o da fase l?quida (450 e 600 rpm). Para todas as condi??es e demais catalisadores, o biodiesel foi produzido. A convers?o m?xima do ?leo de soja encontrada foi de 27,34%, no estudo cin?tico, para o catalisador Mo2C/C.A nas condi??es operacionais de 1% de catalisador, 6 h de rea??o, raz?o molar ?leo/?lcool de 1/12 e pH = 5. Na an?lise de caracteriza??o de uma amostra de biodiesel produzido o ponto de fulgor apresentou valor de 141 ?C, o qual est? acima do m?nimo especificado pela ANP. Um modelo cin?tico pseudo homog?neo foi utilizado, para o catalisador Mo2C/C.A atrav?s do qual foi mostrado que os resultados experimentais se ajustaram satisfatoriamente a uma cin?tica de 1? ordem, cuja constante cin?tica de velocidade teve como valor 0,0009 min-1. / For decades, the production of environment-friendly fuels, as alternative power sources for oil, has gained attention and interest of researchers worldwide. Biodiesel is a renewable alternative fuel that can be obtained from residual oils, animal fat and vegetable oils through heterogeneous transesterification reaction using alcohol. In this context, heterogeneous catalyst present potential for biodiesel production as they can be regenerated and provide a cleaner and more efficient process. In this work, several molybdenum carbide catalysts were tested for the transesterification reaction of soybean oil with methanol towards producing biodiesel. These catalysts were pure Mo2C, Mo2C supported over activated carbon (A.C), pure A.C and bimetallic Ni (20%)-Mo2C/A.C being this support produced from sewage sludge pyrolysis. The pyrolysis product was treated with KOH, in order to increase its porosity and promote a larger specific surface area, and later physically activated. Gas solid reaction with CH4 and H2 atmosphere was used to produce the studied molybdenum derived catalysts, and ammonium molybdate was used as molybdenum source in all cases. All catalysts were characterized in a TG, XDR, XFR, SEM, B.E.T and laser particle size analysis basis. Their activity towards transesterification reaction was evaluated by using a mixing reactor with temperature control and alcohol reflux at 65 ?C. The parameters that were manipulated for this experimental evaluation were: type and mass concentration of the catalyst (1 to 5%), oil/alcohol ratio (1/6 to 1/18), pH (2.0 to 8.5), reaction time (3 and 5h) and liquid phase agitation speed (450 and 600 rpm). For all conditions and other catalysts, biodiesel was produced. The maximum conversion found was 27.34% for the Mo2C/A.C catalyst under the operating conditions of 1% catalyst, 6 h reaction, oil/alcohol ration of 1/12 and pH = 5. In the characterization analysis of a sample of biodiesel produced the flash point presented a value of 141 ?C, which is above the minimum specified by the ANP. A pseudo homogeneous kinetics model was used, and experimental data presented agreement with a 1st order reaction with speed rate constant of 0,0009 min-1.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-07-08T21:11:24Z No. of bitstreams: 1 EmersonAlencarDeMedeiros_DISSERT.pdf: 2911970 bytes, checksum: f1aed4ff1b910b2a9a0ab98f785583a7 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-07-12T21:29:33Z (GMT) No. of bitstreams: 1 EmersonAlencarDeMedeiros_DISSERT.pdf: 2911970 bytes, checksum: f1aed4ff1b910b2a9a0ab98f785583a7 (MD5) / Made available in DSpace on 2016-07-12T21:29:33Z (GMT). No. of bitstreams: 1 EmersonAlencarDeMedeiros_DISSERT.pdf: 2911970 bytes, checksum: f1aed4ff1b910b2a9a0ab98f785583a7 (MD5) Previous issue date: 2015-10-02 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / ? preocupante o descontrole por parte das ind?strias que produzem insumos relacionados aos compostos fen?licos, promovendo a emiss?o ou descarte desse poluente no meio ambiente, trazendo danos irrevers?veis ? natureza bem como ao ser humano. Diante disso, ? imprescind?vel a realiza??o de um tratamento desses efluentes antes de serem descartados no meio ambiente, reduzindo a concentra??o do contaminante ? valores determinados pela legisla??o. Procura-se, portanto, o tratamento desses efluentes utilizando novos materiais catal?ticos que viabilizem o processo como um todo. Nesse contexto, o presente trabalho tem como objetivo o tratamento, caracteriza??o e avalia??o de novos catalisadores na rea??o de degrada??o fotocatal?tica do fenol. Os ensaios foram realizados em um reator fotocatal?tico, em condi??es constantes de temperatura (50 ?C), pot?ncia da l?mpada (400 W), volume da fase l?quida (3,4 L), concentra??o do catalisador (1 g L-1), concentra??o inicial do fenol (500 ppm) e tempo de rea??o 3 horas. Preliminarmente ? rea??o foi realizado um estudo com a vaz?o de oxig?nio (410, 515, 650 e 750 mL min-1) a fim de identificar o valor ?timo (650 ml min-1) a ser utilizado no processo de degrada??o do fenol. Os demais par?metros foram variados: pH do meio reacional (3, 5,5 e 10) e a natureza do catalisador (paligorsquita acidificada calcinada, paligorsquita impregnada com 3,8% de ferro e carv?o originado da pir?lise do lodo de esgoto dom?stico). Os materiais catal?ticos foram caracterizados por DRX, FRX, BET e distribui??o granulom?trica. No processo de degrada??o fotocatal?tica do fenol, os resultados mostraram que o pH tem influ?ncia significativa na convers?o do fenol, apresentando melhores resultados para o pH igual a 5,5. Os valores da convers?o do fenol variaram entre 58% (para a paligorsquita acidificada calcinada) e 52% para o carv?o do lodo de esgoto. As amostras l?quidas analisadas por cromatografia l?quida identificaram e quantificaram os seguintes produtos da degrada??o: hidroquinona, catecol e o ?cido mal?ico. Por fim, foi proposto um mecanismo do processo reacional, considerando que o fenol ? transformado em fase homog?nea e os demais reagem na superf?cie do catalisador. Para este ?ltimo, foi aplicado o modelo Langmuir-Hinshelwood, cujos balan?os de massas conduziram a um sistema de equa??es diferenciais que foram resolvidas utilizando o m?todo num?rico associado a uma minimiza??o da fun??o objetivo para obten??o e otimiza??o dos par?metros cin?ticos e de adsor??o. O modelo se ajustou satisfatoriamente aos resultados experimentais. A partir do mecanismo proposto e com as condi??es operat?rias utilizadas no presente trabalho, a etapa mais favorecida, independente do catalisador, foi a do grupo ?cidos (originada dos compostos quin?nicos), sendo transformado em CO2 e ?gua, cuja constante de velocidade k4 apresentou valor 0,578 mol L-1 min-1 para a paligorsquita acidificada calcinada, 0,472 mol L-1 min-1 para o Fe2O3/paligorsquita e 1,276 mol L-1 min-1 para o carv?o do lodo, sendo este ?ltimo o melhor catalisador para mineraliza??o dos ?cidos em CO2 e ?gua. Os quin?nicos foram mais fortemente adsorvidos nos s?tios dos catalisadores paligorsquita acidificada calcinada e Fe2O3/paligorsquita, cujas constantes de adsor??o foram semelhantes (~4,45 L mol-1) e superior ao carv?o do lodo (3,77 L mol-1). / The uncontrolled disposal of wastewaters containing phenolic compounds by the industry has caused irreversible damage to the environment. Because of this, it is now mandatory to develop new methods to treat these effluents before they are disposed of. One of the most promising and low cost approaches is the degradation of phenolic compounds via photocatalysis. This work, in particular, has as the main goal, the customization of a bench scale photoreactor and the preparation of catalysts via utilization of char originated from the fast pyrolysis of sewage sludge. The experiments were carried out at constant temperature (50?C) under oxygen (410, 515, 650 and 750 ml min-1). The reaction took place in the liquid phase (3.4 liters), where the catalyst concentration was 1g L-1 and the initial concentration of phenol was 500 mg L-1 and the reaction time was set to 3 hours. A 400 W lamp was adapted to the reactor. The flow of oxygen was optimized to 650 ml min-1. The pH of the liquid and the nature of the catalyst (acidified and calcined palygorskite, palygorskite impregnated with 3.8% Fe and the pyrolysis char) were investigated. The catalytic materials were characterized by XRD, XRF, and BET. In the process of photocatalytic degradation of phenol, the results showed that the pH has a significant influence on the phenol conversion, with best results for pH equal to 5.5. The phenol conversion ranged from 51.78% for the char sewage sludge to 58.02% (for palygorskite acidified calcined). Liquid samples analyzed by liquid chromatography and the following compounds were identified: hydroquinone, catechol and maleic acid. A mechanism of the reaction was proposed, whereas the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. For the latter, the Langmuir-Hinshelwood model was applied, whose mass balances led to a system of differential equations and these were solved using numerical methods in order to get estimates for the kinetic and adsorption parameters. The model was adjusted satisfactorily to the experimental results. From the proposed mechanism and the operating conditions used in this study, the most favored step, regardless of the catalyst, was the acid group (originated from quinone compounds), being transformed into CO2 and water, whose rate constant k4 presented value of 0.578 mol L-1 min-1 for acidified calcined palygorskite, 0.472 mol L-1 min-1 for Fe2O3/palygorskite and 1.276 mol L-1 min-1 for the sludge to char, the latter being the best catalyst for mineralization of acid to CO2 and water. The quinones were adsorbed to the acidic sites of the calcined palygorskite and Fe2O3/palygorskite whose adsorption constants were similar (~ 4.45 L mol-1) and higher than that of the sewage sludge char (3.77 L mol-1).

Made available in DSpace on 2014-12-17T15:01:51Z (GMT). No. of bitstreams: 1 AristidesFSJ_TESE.pdf: 1616188 bytes, checksum: 162e291640cf71e1607267c17f431e17 (MD5) Previous issue date: 2010-10-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ? C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved. / A oxida??o ?mida de compostos org?nicos a CO2 e H2O tem demonstrado ser uma t?cnica interessante no tratamento de efluentes. Este trabalho tem como objetivo a s?ntese e caracteriza??o dos catalisadores Fe-MnO2/CeO2, K-MnO2/CeO2/paligorsquita e Fe/paligorsquita, assim como, a avalia??o na degrada??o oxidativa do fenol. Os experimentos foram realizados em um reator de leito de lama, com controle de temperatura, de press?o e de velocidade de agita??o e com coleta de amostras da fase l?quida. Os Experimentos foram executados nas seguintes condi??es operacionais: temperatura de 130 oC, press?o de 20,4 atm, concentra??o m?ssica do catalisador de 5 g/L e concentra??o inicial do fenol de 0,5 g/L. Os par?metros avaliados foram: teor de ferro impregnado (0,3; 7 e 10% em massa) e o pH do meio reacional (3,1; 6,8 e 8,7). Os resultados da caracteriza??o por DRX, MEV e FRX mostraram a dispers?o do ferro na paligorsquita, a pureza das fases e, finalmente, a composi??o dos elementos que constituem o catalisador. O uso da paligorsquita como suporte eleva a ?rea especifica superficial do catalisador que foi confirmada por an?lise BET. As curvas de degrada??o do fenol indicam que o catalisador Fe3+ suportado em paligorsquita tem um papel preponderante na convers?o de Carbono Org?nico Total (COT) quando comparado aos demais catalisadores. A diminui??o da alcalinidade do meio reacional favorece tamb?m a convers?o de COT. A convers?o m?xima de COT obtida com o catalisador 3% Fe/paligorsquita, foi em torno de 95 % para um tempo de rea??o de 60 minutos, reduzindo ao mesmo tempo a forma??o de ?cidos, em especial o ?cido ac?tico. Com os produtos obtidos da oxida??o ?mida do fenol, hidroquinona, p-benzoquinona, catecol e ?cido ox?lico, identificados e quantificados por Cromatografia L?quida de Alta Efici?ncia, foi poss?vel propor um mecanismo do processo reacional onde o fenol ? transformado em fase homog?nea e os demais em fase heterog?nea. Aplicou-se um modelo cin?tico, tipo Langmuir- Hinshelwood, com avalia??o das constantes cin?ticas das diferentes rea??es envolvidas

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