Boron is an element, which is necessary as essential nutrient for living organisms, especially for plants where it is involved in cell wall composition. But boron excess can cause some problems on the development of plants (defoliation, decay and fall unripe fruits), of humans and animals such as nausea, diarrhoea, dermatitis, lethargy. Boron toxicity also changes blood composition, caused disorder in neurological, physical, intellectual development. Nowadays, due to the shortage of fresh water sources, seawater desalination has been becoming an alternative fresh water supply. However, the presence of boron in seawater is quite high (4.5 mg L–1, around 4.5 mM). Moreover, the increasing use of boron in industries and its discharge to the environment has led to the contamination of surface and ground waters. As the result, boron removal, in production of drinking water becomes very important. Therefore, the World health organization has recommended a guideline of 0.5 mg L–1 B in drinking water and a maximum limit of 0.3 mg L–1 B in fresh water used for irrigation. The objective of this thesis is to study the mechanisms of boron surface exchange on different materials versus time and at equilibrium depending on some physicochemical parameters such as pH, initial boron concentration, reaction time in order to find a new exchanger for boron removal. Boron removal was carried out by ion exchange process using 2 types of resins: Amberlite IRA 743, Diaion CRB 03 as boron selective resins with methylglucamine functions, and Ambersep 900-OH and Amberlite IRA 402 Cl as anionic exchange resins with ammonium functions. From batch studies, fast exchange between resin surface and liquid phase was observed with boron removal up to at least 96 % within 30 min for Amberlite IRA 743, Diaion CRB 03 and Ambersep 900- OH. The reaction between resin surface and boron solution reached equilibrium after 2 h for all the resins. The pseudo-second order kinetic model was used to well describe the sorption kinetic process of the resins. At equilibrium, the experimental results showed that the maximum adsorption was observed to be achieved at pH 8 for Ambersep 900- OH, pH 10 for Amberlite IRA 402 Cl and independent on pH range from 6 to 12 for the 2 boron selective resins Amberlite IRA 743 and Diaion CRB 03. At pH 8 and for boron concentrations < 20 mM, the Langmuir-type relationship was used to fit the experimental data for Amberlite IRA 743, Ambersep 900- OH and resin Diaion CRB 03. In the range of studied boron concentration, the boron sorption onto Amberlite IRA 402 Cl followed linear-type behaviour. At pH 8 and for boron concentrations < 20 mM, the sorption capacities are: 1, 0,7, 0,3 et 0,05 mmol g–1 for Diaion CRB 03, Amberlite IRA 743, Ambersep 900- OH and Amberlite IRA 402 Cl, respectively. Column experiments were performed with the anionic resin Ambersep 900-OH and the selective one Amberlite IRA 743 by studying both the influence of boron concentration and the residence time. For the selective resin, if the residence time decreases, the boron breakthrough is fast followed by a long tail. For larger residence time, local equilibrium seems to be assumed. Results are thus consistent with batch experimental data. For the anionic resin, the nonlinear behaviour is also confirmed. Moreover, column experiments showed a strong difference during desorption. To regenerate resins, acid and basic treatments are necessary for the selective resin although a basic solution is enough for the anionic resin. A more detailed study of mechanisms is in progress in order to build a exchange model for predicting boron fate. Finally, characterization of pectins was also performed. Its composition (sugar and boron content) and the viscosity of pectin solutions were quantified. Filtration experiments allowed testing the efficiency of such material to remove boron too

O Brasil tem uma longa tradição na tecnologia do tório, desde a abertura do principal mineral, a monazita, até compostos de pureza grau nuclear, com reservas minerais estimados em 1.200.000 ton – ThO2. Como conseqüência desta produção, foi acumulado um resíduo produzido na unidade piloto de purificação de nitrato de tório, do Instituto de Pesquisas Energéticas e Nucleares- CNEN/SP, mais de 25 toneladas ao longo das últimas três décadas, proveniente dos rafinados e soluções de lavagem do processo de extração por solventes, conhecido como RETOTER. Sua composição, um hidróxido, contendo tório, terras raras e impurezas menores, incluindo o chumbo-208 do decaimento do 232 Th, com abundância isotópica em 88,34 %, enriquecido naturalmente ao longo das eras geológicas. Neste trabalho são discutidos os estudos dos principais parâmetros do processo de recuperação deste chumbo, 0,42 % em massa no RETOTER seco, utilizando-se a técnica de troca iônica com resinas aniônicas em meio clorídrico. A abundância isotópica do chumbo foi analisada por espectrometria de massa termoiônica (TIMS) e de alta resolução (ICPMS), e com os dados calculou-se a secção de choque de captura para nêutrons térmicos. O valor resultante foi de s? o = 14,6 +/- 0,7 mb diferentemente do chumbo natural de s? o = 174,2 +/- 7,0 mb. Estudos preliminares de recuperação do tório e terras raras neste resíduo também foram apresentados. / Brazil has a long tradition in thorium technology, from mineral dressing (monazite) to the nuclear grade thorium compounds. The estimate reserves are 1200,000. ton of ThO2. As a consequence from the work of thorium purification pilot plant at Instituto de Pesquisas Energéticas e Nucleares-CNEN/SP, about 25 ton of a sludge containing thorium and rare earths was accumulated. It comes as a raffinate and washing solutions from thorium solvent extraction. This sludge, a crude hydroxide named RETOTER contains thorium, rare earths and minor impurities including the radiogenic lead-208, with abundance 88.34 %. This work discusses the results of the studies and main parameters for its recovery by anionic ion exchange technique in the hydrochloric system. The isotope abundance of this lead was analyzed by high resolution mass spectrometer (ICPMS) and thermoionic mass spectrometer (TIMS) and the data was used to calculate the thermal neutron capture cross section. The value of s? o = 14.6 +/- 0.7 mb was found, quite different from the s? o = 174.2 +/- 7.0 mb measure cross section for the natural lead. Preliminary study for the thorium and rare earths separation and recovery was discussed as well.

O Brasil tem uma longa tradição na tecnologia do tório, desde a abertura do principal mineral, a monazita, até compostos de pureza grau nuclear, com reservas minerais estimados em 1.200.000 ton – ThO2. Como conseqüência desta produção, foi acumulado um resíduo produzido na unidade piloto de purificação de nitrato de tório, do Instituto de Pesquisas Energéticas e Nucleares- CNEN/SP, mais de 25 toneladas ao longo das últimas três décadas, proveniente dos rafinados e soluções de lavagem do processo de extração por solventes, conhecido como RETOTER. Sua composição, um hidróxido, contendo tório, terras raras e impurezas menores, incluindo o chumbo-208 do decaimento do 232 Th, com abundância isotópica em 88,34 %, enriquecido naturalmente ao longo das eras geológicas. Neste trabalho são discutidos os estudos dos principais parâmetros do processo de recuperação deste chumbo, 0,42 % em massa no RETOTER seco, utilizando-se a técnica de troca iônica com resinas aniônicas em meio clorídrico. A abundância isotópica do chumbo foi analisada por espectrometria de massa termoiônica (TIMS) e de alta resolução (ICPMS), e com os dados calculou-se a secção de choque de captura para nêutrons térmicos. O valor resultante foi de s? o = 14,6 +/- 0,7 mb diferentemente do chumbo natural de s? o = 174,2 +/- 7,0 mb. Estudos preliminares de recuperação do tório e terras raras neste resíduo também foram apresentados. / Brazil has a long tradition in thorium technology, from mineral dressing (monazite) to the nuclear grade thorium compounds. The estimate reserves are 1200,000. ton of ThO2. As a consequence from the work of thorium purification pilot plant at Instituto de Pesquisas Energéticas e Nucleares-CNEN/SP, about 25 ton of a sludge containing thorium and rare earths was accumulated. It comes as a raffinate and washing solutions from thorium solvent extraction. This sludge, a crude hydroxide named RETOTER contains thorium, rare earths and minor impurities including the radiogenic lead-208, with abundance 88.34 %. This work discusses the results of the studies and main parameters for its recovery by anionic ion exchange technique in the hydrochloric system. The isotope abundance of this lead was analyzed by high resolution mass spectrometer (ICPMS) and thermoionic mass spectrometer (TIMS) and the data was used to calculate the thermal neutron capture cross section. The value of s? o = 14.6 +/- 0.7 mb was found, quite different from the s? o = 174.2 +/- 7.0 mb measure cross section for the natural lead. Preliminary study for the thorium and rare earths separation and recovery was discussed as well.

O presente trabalho teve como objetivo principal avaliar as relações entre a composição mineralógica de solos representativos do Estado de São Paulo e alguns de seus atributos eletroquímicos como o ponto de efeito salino nulo (PESN) e a capacidade de troca aniônica (CTA). Especial atenção foi dada também à quantificação de cargas negativas de caráter permanente e à contrastação dos resultados com a composição mineralógica da fração argila, a qual foi avaliada de forma qualitativa e semiquantitativa. Além dos atributos eletroquímicos supracitados, a adsorção e a dessorção de sulfato, principal forma inorgânica de enxofre presente nos solos sob condições aeróbicas, foram estudadas visando-se à determinação de índices representativos desses fenômenos e à associação dos mesmos com atributos mineralógicos, químicos e eletroquímicos dos solos. Em uma primeira etapa, amostras coletadas em camadas subsuperficiais de quinze solos localizados em diferentes regiões do Estado de São Paulo foram submetidas à uma intensa caracterização mineralógica, química e eletroquímica. Além dessas avaliações, as amostras foram utilizadas como adsorvedores em estudos de adsorção e dessorção de sulfato. Em um momento posterior e por meio do tratamento estatístico dos dados, procurou-se analisar as relações individuais dos diversos atributos avaliados com o ponto de efeito salino nulo, capacidade de troca aniônica, adsorção e dessorção de sulfato. Os resultados experimentais obtidos durante a avaliação do ponto de efeito salino nulo das amostras permitiram o desenvolvimento de um programa computacional para o tratamento matemático dos referidos dados visando-se à determinação analítica do valor desse atributo eletroquímico. Testes realizados com dados obtidos por outros autores demonstraram a adequação do programa para a determinação rápida e não-subjetiva do PESN. Em relação às cargas elétricas negativas de superfície, pôde-se verificar uma significativa presença de cargas de caráter permanente, fato que apresentou razoável concordância com a composição mineralógica das amostras. Contudo, faz-se necessária a contrastação de resultados obtidos com o método da adsorção de césio com quantidades de cargas permanentes determinadas por meio do uso de outros procedimentos metodológicos. Ao avaliar-se a capacidade de troca catiônica (CTC) das amostras, utilizando-se diferentes métodos, pôde-se observar que os solos com caráter ácrico estiveram dentre aqueles em que as maiores discrepâncias foram verificadas, fato que sugere a necessidade da reavaliação dos métodos empregados para a determinação da CTC efetiva nesses solos. Os procedimentos adotados permitiram verificar que os óxidos de alumínio mal cristalizados, pres entes na fração argila, são os componentes mais diretamente associados ao ponto de efeito salino nulo e à capacidade de troca aniônica das amostras estudadas. Em relação à adsorção de sulfato, novamente observou-se acentuada relação direta entre o teor dos óxidos de alumínio mal cristalizados e a capacidade adsortiva das amostras bem como com a afinidade apresentada pela fase sólida em relação ao referido ânion. A gibbsita e os óxidos de alumínio mal cristalizados são os constituintes inorgânicos da fase sólida mais diretamente associados à restrição à dessorção de sulfato nas amostras avaliadas, ao passo que a liberação do sulfato retido apresentou relação direta com o teor de caulinita. Esses dados indicam que as aplicações de gesso agrícola devem ser feitas com maior cautela em solos cauliníticos. Em relação aos atributos de fácil e rápida determinação, o pH das amostras medido em solução de fluoreto de sódio (pH NaF) apresentou estreita relação com a presença de óxidos de alumínio nas amostras estudadas e, por essa razão, mostrou-se como um índice bastante promissor para a avaliação indireta da capacidade de retenção aniônica de amostras de camadas subsuperficiais de solos das regiões tropicais. Finalmente, um grande número de correlações não significativas obsevadas entre os teores de óxidos de ferro cristalinos (hematita e goethita) tanto para com atributos eletroquímicos quanto para com a adsorção e dessorção de sulfato parece indicar a existência de acentuada variabilidade comportamental para esses minerais nas amostras estudadas. Desse modo, novos estudos devem ser realizados com os referidos óxidos de ferro visando-se analisar a influência da morfologia, tamanho de cristais e grau de cristalinidade sobre os atributos eletroquímicos e propriedades adsortivas desses minerais. Igualmente, o desenvolvimento de trabalhos de pesquisa de natureza similar envolvendo a gibbsita são também necessários, haja vista a completa ausência de informações relacionadas à variabilidade comportamental desse óxido de alumínio. / The present research aimed at studying the relationships between the mineralogical composition of representative soils from São Paulo State and some of their electrochemical properties, particularly the point of zero salt effect (PZSE) and the anion exchange capacity (AEC). Additionally, it was given special attention to the presence of permanent negative charges in those soils, whose magnitudes were also associated with the mineralogical composition of their clay fractions, which was evaluated by using qualitative and semiquantitative approaches. Besides the above mentioned electrochemical properties, the adsorption and desorption of sulfate, the main inorganic form of sulfur found in soils under aerobic conditions, were studied in order to associate the representative indexes of these phenomena with mineralogical, chemical and electrochemical soil properties. Initially, samples collected in subsurface layers of fifteen soils situated in different regions of São Paulo State were highly characterized as for their mineralogical, chemical and electrochemical properties Besides these evaluations, the soil samples were used as adsorbents in studies of sulfate adsorption and desorption reactions. After this, and through the statistical analyses of data, it was aimed at verifying the individual relationships of the evaluated properties with the PZSE, AEC, sulfate adsorption and desorption indexes. The experimental results obtained during the evaluation of the PZSE values of samples, gave us the possibility of the development of one software for mathematical manipulation of them in order to allow the analytical determination of the above mentioned electrochemical property. The software was evaluated through the analyses of potentiometric titration data from experiments of other authors. The results showed very good agreement between PZSE values calculated by the software and those determined by the authors. By this reason, this approach can be considered very useful for this determination. In relation to surface charges, it was possible to verify reasonable amounts of permanent negative charges in evaluated soil samples and good correspondence of them with soil mineralogical properties. However, more studies are necessary in order to compare the results of cesium adsorption method, employed for this determination in the present research, with ones from other methodologies. The determination of cation exchange capacity (CEC) values through different approaches have shown that the soil samples with acric character were among the ones that present the biggest discrepancies. These results suggest the necessity of reevaluation for the usual methods employed to measurements of CEC values in soils with acric character. The methods used in this research allowed us to verify that the contents of amorphous aluminum oxides in the clay fraction present direct associations with PZSE and AEC values determined in soil samples. In relation to sulfate adsorption, it was also observed the positive effect of amorphous aluminum oxides on the sulfate adsorptive capacities of the studied soils. In the same way, the content of above mentioned oxides present significative and direct correlation with the affinity of surfaces by sulfate ions. The gibbsite and amorphous aluminum oxides are the clay fraction constituents associated with the restriction to sulfate desorption in evaluated soil samples; on the other hand, the transference of sulfate ions from solid surfaces to soil solutions was favored by the high kaolinite contents. These data suggest that the use of gypsum in kaolinitic soils with low contents of oxides must be done with more criteria.Considering the soil properties whose determinations are not time consuming, the pH values evaluated in suspensions of soil-NaF 1 mol L -1 solution (pH NaF) presented very good associations with the aluminum oxides contents of soil samples and, by this reason, it showed also significative correlations with soil sulfate adsorption capacity. These founds indicate that the pH NaF is a very promising index for the indirect evaluation of the anion retention capacity of samples from subsurface layers of tropical soils. Finally, the great number of non-significative correlations verified in this research between crystalline iron oxides (hematite and goethite) contents and electrochemical properties or sulfate adsorption/desorption indexes suggest the existence of non-systematic variations in their intrinsic properties. So, it is very important the establishment of new researches with the objective of acquiring more information about the influence of morphology and crystals size and crystallinity of these adsorbents on their electrochemical properties and adsorptive capacities. These considerations are also applied to gibbsite, since there is no information about this topic associated to this mineral.

Orientadores: João Alexandre Ferreira da Rocha Pereira, Cesar Augusto Moraes de Abreu / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T05:19:09Z (GMT). No. of bitstreams: 1 Barauna_OsmarSouto_D.pdf: 2829115 bytes, checksum: bf2e35aadb3829156a0b6febbd04582f (MD5) Previous issue date: 2006 / Resumo: A utilização de argilas do tipo esmectita como agente descorante de óleo de soja, satisfazendo as exigências comerciais e se equivalendo à capacidade adsortiva da argila-padrão importada (Tonsil Supreme 180 FF), foi praticada através do desenvolvimento do processo adsortivo de pigmentos clorofila e carotenóides. A argila esmectítica adsorvente de origem da bacia sedimentar do Araripe/PE é constituída por argilomine rais (predominantes) e uma fração detrítica grosseira composta essencialmente por quartzo, calcita e gipsita. Procedeu-se à ativação ácida (HCl), previamente à aplicação no descoramento, favorecendo-se o desenvolvimento de atividades adsortivas da argila. Os parâmetros com base no desenvolvimento do processo de adsorção de pigmentos com a argila esmectítica ácido-ativada comprovaram a sua aptidão para produzir a despigmentação do óleo vegetal em teor da clorofila-a, repre sentando uma capacidade adsortiva de qAm = 144,93 mg.g-1, significan do ordem de grandeza próxima àquela determinada para a argila Tonsil de qAm = 166,67 mg.g-1. Equilíbrios de isotermas favoráveis nos dois ca sos foram quantificados segundo os parâmetros de adsorção de KAargila = 23,00 cm3.g-1 e KAtonsil = 20,00 cm3.g-1. Resultantes de avalia ções cinéticas experimentais, fundamentados em um modelo do tipo Langmuir-Freundlich, foram estimadas as constantes cinéticas de adsorção da argila (kaAargila = 0,2488 ± 0,0913) e do adsorvente Tonsil (kaAtonsil = 0,0839 ± 0,0219). Caracterizadas as atividades adsortivas das argilas em razão de suas acidez superficiais, traduzidas em números de sítios ácidos, foram identificadas características de sítios fortes (183,90 x 1020 sítios/g de argila), responsáveis pela adsorção dos pigmentos. A argila esmectítica acidificada demonstrou possuir propriedades adsortivas similares a do adsorvente importado, tendo servido à aplicação no processo de descoramento de óleo de soja / Abstract: Smectite clays from the Araripe sedimentary basin were employed as bleaching agents of soy bean oil and compared with adsorption capacity of the imported reference-clay (Tonsil Supreme 180 FF). The system was tested with chlorophyllous pigments and carotenoids. The smectite was mainly composed by a coarse detrital fraction of quartz, calcite and gypsum. To develop its adsorption capacity it was previously activated with acid (HCl). The parameters of the process indicated that the bleaching property of the activated clay in terms of chlorophyll-a representing an adsorption capacity of qm = 144.93 mg.g-1, which had an order magnitude near to that of Tonsil, qm = 166.67 mg.g-1. The adsorption parameters of the equilibrium isotherms for the two cases were KAclay = 23.00 cm3.g-1 KAtonsil = 20.00 cm3.g-1. From the experimental kinetic evaluations, based on a Langmuir-Freundlich model, the estimated kinetic adsorption constants for the clay and the Tonsil were kaAclay = 0.2488 ± 0.0913 kaAtonsil = 0.0839 ± 0.0219 respectively. The number of sites responsible for the pigments adsorption identified on the clay surface, were of the order of 183.90 x 1020 sites/g of clay. The acidified clay presented similar adsorptive properties to the imported product, showing that it may be employed to bleaching soy bean oil / Doutorado / Sistemas de Processos Quimicos e Informatica / Doutor em Engenharia Química

Orientador: Cesar Costapinto Santana / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-27T02:38:10Z (GMT). No. of bitstreams: 1 Veredas_Vinicius_M.pdf: 4752847 bytes, checksum: f01c509a2798835914e0489d2f75baac (MD5) Previous issue date: 2000 / Resumo: O crescente interesse e aplicações dos produtos biotecnológicos vem aumentando o desenvolvimento de novos processos de recuperação e purificação de proteínas. O soro de leite bovino, obtido da manufatura da caseína para a produção de queijo, é em sua maioria descartado em mananciais de água, causando sérios problemas ambientais devido a sua alta demanda biológica de oxigênio (DBO). As proteínas presentes no lactosoro apresentam um excelente valor nutritivo e farmacológico, porém, o seu uso no enriquecimento de produtos alimentícios é limitado devido a baixa concentração destas proteínas. As principais proteínas do lactosoro são: ~-Iactoglobulinas, a-Iactalbumina, albuminas de soro bovino, imunoglobulinas, lactoperoxidase, lactoferrina, lisozima e outras proteínas de menor proporção, que apresentam um alto valor agregado. A a-Iactalbumina atua no organismo estimulando os agentes do sistema imunológico por proporcionar a elevação de glutationa em vários órgãos e no sangue, resultando em benefícios para pacientes portadores de doenças degenerativas como os males de Parkinson e Alzheimer, câncer e AIDS. Neste trabalho foi estudado o processo de separação da a-Iactalbumina, através de técnicas cromatográficas empregando a metodologia de leito fixo e expandido. O leito expandido possibilita a redução nos custos do processo de purificação, eliminando etapas de separação necessárias quando o extrato apresenta material em suspensão, que é o caso dos lactosoros. Nos ensaios realizados foram estudados as melhores condições de adsorção da a-Iactalbumina visando a sua purificação empregando adsorventes de troca iônica e de interação hidrofóbica. Também foram realizados ensaios em sistemas de tanque agitados para a determinação das isotermas e cinéticas de adsorção. Neste trabalho obteve-se a a-Iactalbumina com uma pureza acima de 80% e apresentando um fator de purificação de 5 vezes utilizando as resinas de interação hidrofóbica com única etapa de purificação / Abstract: The interest and applications of biotechnology products has been increasing the development of new recovery and purification processes for proteins. The bovine milk serum, obtained from casein manufacture for cheese production, is mostly rejected into watercourse, causing problems to the environment due to its high biological oxygen demand (BOD). The proteins of milk serum have excellent nutritious and pharmaceutical value, h oweve r, its application for protein enrichment of food products is limited due to its low content in the milk serum. The main proteins of milk serum are: ~-Iactoglobulins, a-Iactalbumine, bovine serum albumine, immunoglobulins, lactoperoxidase, lactoferrin, lisozime and other lower content proteins which have a high aggregate value. The a-Iactalbumine acts in the human organism by stimulating the agents of the immunologycal system due to increasing on glutathione levei in several organs and blood, resulting in benefits for patients of some diseases like Parkinson and Alzheimer's iII, cancer and AIDS. It was studied in this work the separation processes of a-Iactalbumine, by chromatographic techniques making use of fixed and expanded bed methods. The expanded bed enables cost reduction on purification process by reducing separation steps used for removing suspended solids, as in case of milk serum extracts. In our experiments were studied the adsorption conditions of alactalbumine aiming at its purification by using ionic exchange and hydrophobic interaction adsorbents. Other experiments were accomplished at stirred tank systems for the determination of isotherms and adsorption kinetics. It was obtained, in this work, an a-Iactalbumine purity higher than 80%, with a five fold purification factor by using the hydrophobic interaction resins in a single purification ste / Mestrado / Desenvolvimento de Processos Biotecnologicos / Mestre em Engenharia Química

O presente trabalho teve como objetivo principal avaliar as relações entre a composição mineralógica de solos representativos do Estado de São Paulo e alguns de seus atributos eletroquímicos como o ponto de efeito salino nulo (PESN) e a capacidade de troca aniônica (CTA). Especial atenção foi dada também à quantificação de cargas negativas de caráter permanente e à contrastação dos resultados com a composição mineralógica da fração argila, a qual foi avaliada de forma qualitativa e semiquantitativa. Além dos atributos eletroquímicos supracitados, a adsorção e a dessorção de sulfato, principal forma inorgânica de enxofre presente nos solos sob condições aeróbicas, foram estudadas visando-se à determinação de índices representativos desses fenômenos e à associação dos mesmos com atributos mineralógicos, químicos e eletroquímicos dos solos. Em uma primeira etapa, amostras coletadas em camadas subsuperficiais de quinze solos localizados em diferentes regiões do Estado de São Paulo foram submetidas à uma intensa caracterização mineralógica, química e eletroquímica. Além dessas avaliações, as amostras foram utilizadas como adsorvedores em estudos de adsorção e dessorção de sulfato. Em um momento posterior e por meio do tratamento estatístico dos dados, procurou-se analisar as relações individuais dos diversos atributos avaliados com o ponto de efeito salino nulo, capacidade de troca aniônica, adsorção e dessorção de sulfato. Os resultados experimentais obtidos durante a avaliação do ponto de efeito salino nulo das amostras permitiram o desenvolvimento de um programa computacional para o tratamento matemático dos referidos dados visando-se à determinação analítica do valor desse atributo eletroquímico. Testes realizados com dados obtidos por outros autores demonstraram a adequação do programa para a determinação rápida e não-subjetiva do PESN. Em relação às cargas elétricas negativas de superfície, pôde-se verificar uma significativa presença de cargas de caráter permanente, fato que apresentou razoável concordância com a composição mineralógica das amostras. Contudo, faz-se necessária a contrastação de resultados obtidos com o método da adsorção de césio com quantidades de cargas permanentes determinadas por meio do uso de outros procedimentos metodológicos. Ao avaliar-se a capacidade de troca catiônica (CTC) das amostras, utilizando-se diferentes métodos, pôde-se observar que os solos com caráter ácrico estiveram dentre aqueles em que as maiores discrepâncias foram verificadas, fato que sugere a necessidade da reavaliação dos métodos empregados para a determinação da CTC efetiva nesses solos. Os procedimentos adotados permitiram verificar que os óxidos de alumínio mal cristalizados, pres entes na fração argila, são os componentes mais diretamente associados ao ponto de efeito salino nulo e à capacidade de troca aniônica das amostras estudadas. Em relação à adsorção de sulfato, novamente observou-se acentuada relação direta entre o teor dos óxidos de alumínio mal cristalizados e a capacidade adsortiva das amostras bem como com a afinidade apresentada pela fase sólida em relação ao referido ânion. A gibbsita e os óxidos de alumínio mal cristalizados são os constituintes inorgânicos da fase sólida mais diretamente associados à restrição à dessorção de sulfato nas amostras avaliadas, ao passo que a liberação do sulfato retido apresentou relação direta com o teor de caulinita. Esses dados indicam que as aplicações de gesso agrícola devem ser feitas com maior cautela em solos cauliníticos. Em relação aos atributos de fácil e rápida determinação, o pH das amostras medido em solução de fluoreto de sódio (pH NaF) apresentou estreita relação com a presença de óxidos de alumínio nas amostras estudadas e, por essa razão, mostrou-se como um índice bastante promissor para a avaliação indireta da capacidade de retenção aniônica de amostras de camadas subsuperficiais de solos das regiões tropicais. Finalmente, um grande número de correlações não significativas obsevadas entre os teores de óxidos de ferro cristalinos (hematita e goethita) tanto para com atributos eletroquímicos quanto para com a adsorção e dessorção de sulfato parece indicar a existência de acentuada variabilidade comportamental para esses minerais nas amostras estudadas. Desse modo, novos estudos devem ser realizados com os referidos óxidos de ferro visando-se analisar a influência da morfologia, tamanho de cristais e grau de cristalinidade sobre os atributos eletroquímicos e propriedades adsortivas desses minerais. Igualmente, o desenvolvimento de trabalhos de pesquisa de natureza similar envolvendo a gibbsita são também necessários, haja vista a completa ausência de informações relacionadas à variabilidade comportamental desse óxido de alumínio. / The present research aimed at studying the relationships between the mineralogical composition of representative soils from São Paulo State and some of their electrochemical properties, particularly the point of zero salt effect (PZSE) and the anion exchange capacity (AEC). Additionally, it was given special attention to the presence of permanent negative charges in those soils, whose magnitudes were also associated with the mineralogical composition of their clay fractions, which was evaluated by using qualitative and semiquantitative approaches. Besides the above mentioned electrochemical properties, the adsorption and desorption of sulfate, the main inorganic form of sulfur found in soils under aerobic conditions, were studied in order to associate the representative indexes of these phenomena with mineralogical, chemical and electrochemical soil properties. Initially, samples collected in subsurface layers of fifteen soils situated in different regions of São Paulo State were highly characterized as for their mineralogical, chemical and electrochemical properties Besides these evaluations, the soil samples were used as adsorbents in studies of sulfate adsorption and desorption reactions. After this, and through the statistical analyses of data, it was aimed at verifying the individual relationships of the evaluated properties with the PZSE, AEC, sulfate adsorption and desorption indexes. The experimental results obtained during the evaluation of the PZSE values of samples, gave us the possibility of the development of one software for mathematical manipulation of them in order to allow the analytical determination of the above mentioned electrochemical property. The software was evaluated through the analyses of potentiometric titration data from experiments of other authors. The results showed very good agreement between PZSE values calculated by the software and those determined by the authors. By this reason, this approach can be considered very useful for this determination. In relation to surface charges, it was possible to verify reasonable amounts of permanent negative charges in evaluated soil samples and good correspondence of them with soil mineralogical properties. However, more studies are necessary in order to compare the results of cesium adsorption method, employed for this determination in the present research, with ones from other methodologies. The determination of cation exchange capacity (CEC) values through different approaches have shown that the soil samples with acric character were among the ones that present the biggest discrepancies. These results suggest the necessity of reevaluation for the usual methods employed to measurements of CEC values in soils with acric character. The methods used in this research allowed us to verify that the contents of amorphous aluminum oxides in the clay fraction present direct associations with PZSE and AEC values determined in soil samples. In relation to sulfate adsorption, it was also observed the positive effect of amorphous aluminum oxides on the sulfate adsorptive capacities of the studied soils. In the same way, the content of above mentioned oxides present significative and direct correlation with the affinity of surfaces by sulfate ions. The gibbsite and amorphous aluminum oxides are the clay fraction constituents associated with the restriction to sulfate desorption in evaluated soil samples; on the other hand, the transference of sulfate ions from solid surfaces to soil solutions was favored by the high kaolinite contents. These data suggest that the use of gypsum in kaolinitic soils with low contents of oxides must be done with more criteria.Considering the soil properties whose determinations are not time consuming, the pH values evaluated in suspensions of soil-NaF 1 mol L -1 solution (pH NaF) presented very good associations with the aluminum oxides contents of soil samples and, by this reason, it showed also significative correlations with soil sulfate adsorption capacity. These founds indicate that the pH NaF is a very promising index for the indirect evaluation of the anion retention capacity of samples from subsurface layers of tropical soils. Finally, the great number of non-significative correlations verified in this research between crystalline iron oxides (hematite and goethite) contents and electrochemical properties or sulfate adsorption/desorption indexes suggest the existence of non-systematic variations in their intrinsic properties. So, it is very important the establishment of new researches with the objective of acquiring more information about the influence of morphology and crystals size and crystallinity of these adsorbents on their electrochemical properties and adsorptive capacities. These considerations are also applied to gibbsite, since there is no information about this topic associated to this mineral.

Le bore est nécessaire pour le développement des plantes supérieures (structuration de la paroi végétale). Il pose cependant des problèmes (défoliation, pourriture et chute des fruits mûrs). Pour l’homme, sa toxicité se traduit par des nausées, des diarrhées, des troubles du développement intellectuel, neurologique et physique. La pénurie en eau douce conduit à dessaler l’eau de mer pour augmenter la quantité en eau destinée à la consommation humaine, l’industrie et l’agriculture. Lors de ce procédé, il faut éliminer les ions majeurs mais aussi le bore présent à des concentrations élevées (> 4,5 mg L–1, environ 0,45 mM). Son usage dans l’industrie et son rejet dans l’environnement conduisent à la pollution des eaux souterraines et de surface. Son élimination est donc indispensable, sachant que l’Organisation Mondiale de la Santé recommande une valeur guide de 0,5 mg L–1 dans l’eau potable et une valeur maximale de 0,3 mg L–1 dans l’eau utilisée pour l’irrigation. Cette thèse porte sur l’étude cinétique et thermodynamique des échanges du bore à la surface de différents matériaux en fonction de paramètres physico-chimiques (pH, concentration initiale …) à l’aide d’essais en réacteurs fermés et en colonnes. Deux types de résines commerciales ont été choisies : (i) les résines échangeuses d’anions Ambersep 900-OH et Amberlite IRA 402 Cl avec des fonctions ammonium, (ii) les résines spécifiques Amberlite IRA 743 et Diaion CRB 03 ayant des fonctions méthylglucamine. Les premières essais en réacteurs fermés montrent que les échanges liquide-solide sont rapides avec une élimination du bore > 96 % pour t < 30 min pour Amberlite IRA 743, Diaion CRB 03 et Ambersep 900-OH. Pour t > 2 h, un équilibre est observé pour toutes les résines. Le modèle du pseudosecond ordre permet de décrire la cinétique de sorption pour les 4 résines. A l’équilibre, l’adsorption est maximum d’une part dans une gamme de pH compris entre 6 et 12 pour les 2 résines sélectives Amb IRA 743 et CRB 03, et d’autre part pour un pH de 8 pour la résine Ambersep 900-OH et un pH 10 pour la résine Amberlite IRA 402 Cl. A pH 8 et pour les concentrations en bore < 20 mM, la sorption du bore est représentée par le modèle de type Langmuir pour Amberlite IRA 743, Ambersep 900-OH et Diaion CRB 03. Par contre, la rétention du bore sur Amberlite IRA 402 Cl suit une isotherme de type linéaire. A pH 8 et pour des concentrations en bore < 20 mM, les capacités de sorption sont : 1, 0,7, 0,3 et 0,05 mmol g–1 pour Diaion CRB 03, Amberlite IRA 743, Ambersep 900-OH et Amberlite IRA 402 Cl, respectivement. Les résines Ambersep 900-OH, échangeuse d’anions, et Amberlite IRA 743, sélective, ont été utilisées pour les essais en colonnes en fonction de la concentration en bore et du temps de séjour. Pour la résine spécifique, le temps de séjour dans la colonne affecte fortement le comportement du bore : lorsqu’il diminue, son élution est rapide suivie d’une longue traînée ; lorsqu’il augmente, la courbe de percée correspond à un système à l’équilibre. Pour un temps de séjour élevé, les résultats confirment la non-linéarité observée lors des essais en réacteurs fermés. Pour la résine échangeuse d’anions, la non-linéarité est aussi confirmée. Ces essais permettent de différencier le comportement du bore lors de sa désorption. La régénération est obtenue après des traitements acides et basiques pour la résine spécifique alors qu’un traitement alcalin est suffisant pour la résine anionique. Une étude plus détaillée des mécanismes est en cours et permettra de les intégrer dans un même modèle. La fixation du bore sur des pectines et sa rétention par des membranes d’ultrafiltration (membranes de seuil de coupure différent) a aussi été étudiée. Les pectines ont été caractérisées (composition en sucre et en bore présent initialement) et la viscosité des solutions pectiques mesurée. Des essais de filtration ont permis de déterminer l’efficacité de production et de rétention du bore sur ces matériaux. / Boron is an element, which is necessary as essential nutrient for living organisms, especially for plants where it is involved in cell wall composition. But boron excess can cause some problems on the development of plants (defoliation, decay and fall unripe fruits), of humans and animals such as nausea, diarrhoea, dermatitis, lethargy. Boron toxicity also changes blood composition, caused disorder in neurological, physical, intellectual development. Nowadays, due to the shortage of fresh water sources, seawater desalination has been becoming an alternative fresh water supply. However, the presence of boron in seawater is quite high (4.5 mg L–1, around 4.5 mM). Moreover, the increasing use of boron in industries and its discharge to the environment has led to the contamination of surface and ground waters. As the result, boron removal, in production of drinking water becomes very important. Therefore, the World health organization has recommended a guideline of 0.5 mg L–1 B in drinking water and a maximum limit of 0.3 mg L–1 B in fresh water used for irrigation. The objective of this thesis is to study the mechanisms of boron surface exchange on different materials versus time and at equilibrium depending on some physicochemical parameters such as pH, initial boron concentration, reaction time in order to find a new exchanger for boron removal. Boron removal was carried out by ion exchange process using 2 types of resins: Amberlite IRA 743, Diaion CRB 03 as boron selective resins with methylglucamine functions, and Ambersep 900-OH and Amberlite IRA 402 Cl as anionic exchange resins with ammonium functions. From batch studies, fast exchange between resin surface and liquid phase was observed with boron removal up to at least 96 % within 30 min for Amberlite IRA 743, Diaion CRB 03 and Ambersep 900- OH. The reaction between resin surface and boron solution reached equilibrium after 2 h for all the resins. The pseudo-second order kinetic model was used to well describe the sorption kinetic process of the resins. At equilibrium, the experimental results showed that the maximum adsorption was observed to be achieved at pH 8 for Ambersep 900- OH, pH 10 for Amberlite IRA 402 Cl and independent on pH range from 6 to 12 for the 2 boron selective resins Amberlite IRA 743 and Diaion CRB 03. At pH 8 and for boron concentrations < 20 mM, the Langmuir-type relationship was used to fit the experimental data for Amberlite IRA 743, Ambersep 900- OH and resin Diaion CRB 03. In the range of studied boron concentration, the boron sorption onto Amberlite IRA 402 Cl followed linear-type behaviour. At pH 8 and for boron concentrations < 20 mM, the sorption capacities are: 1, 0,7, 0,3 et 0,05 mmol g–1 for Diaion CRB 03, Amberlite IRA 743, Ambersep 900- OH and Amberlite IRA 402 Cl, respectively. Column experiments were performed with the anionic resin Ambersep 900-OH and the selective one Amberlite IRA 743 by studying both the influence of boron concentration and the residence time. For the selective resin, if the residence time decreases, the boron breakthrough is fast followed by a long tail. For larger residence time, local equilibrium seems to be assumed. Results are thus consistent with batch experimental data. For the anionic resin, the nonlinear behaviour is also confirmed. Moreover, column experiments showed a strong difference during desorption. To regenerate resins, acid and basic treatments are necessary for the selective resin although a basic solution is enough for the anionic resin. A more detailed study of mechanisms is in progress in order to build a exchange model for predicting boron fate. Finally, characterization of pectins was also performed. Its composition (sugar and boron content) and the viscosity of pectin solutions were quantified. Filtration experiments allowed testing the efficiency of such material to remove boron too

Le domaine émergeant de l’électronique imprimée nécessite de nouveaux matériaux peu coûteux et non toxiques pour réaliser de nombreux systèmes tels que des circuits logiques, des capteurs, des affichages, des thermoélectriques ou même du photovoltaïque sur substrat souple. Il s’agit aussi d’optimiser le fonctionnement de couches granulaires de semiconducteurs de type n et p.BiCuOS a été identifié comme un semiconducteur de type p possédant des propriétés intéressantes. Cependant, sa forte sous stoechiométrie en cuivre induit un dopage de type p trop élevé qui nuit à ses propriétés semiconductrices. De plus, comme la plupart des composés à base de chalcogénures, BiCuOS se décompose lors d’un frittage, et ne peut être densifié thermiquement. Dans le but d’optimiser des couches minces de BiCuOS, des solutions doivent ainsi être trouvées pour i) réduire le taux de dopage ; ii) obtenir de bonnes mobilités dans des couche peu denses. De nombreuses substitutions chimiques ont été essayées telles que celle du soufre par l’iode et celle du cuivre par l’argent. Ces substitutions ont permis de réduire fortement le taux de porteurs de charge. D’autre part, nous avons étudié l’effet du greffage de molécules à la surface des grains de semiconducteurs sur la conduction électronique. Des molécules conjuguées (acides téréphtaliques substitués) et des polymères dérivés des polythiophènes ont été adsorbés à la surface d’un semiconducteur modèle de type n, ZnO. L’amélioration du transfert électronique intergranulaire a été expliquée par le saut des électrons au travers de la LUMO de ces molécules.L’élaboration d’encres de particules semiconductrices stabilisées par de telles molécules a permis la fabrication par voie liquide de jonctions diodes p-n ZnO/BiCuOS avec de bonnes performances malgré l’absence de propriétés photovoltaïques. Plus largement, ce travail est une contribution à la mise en forme de nouveaux systèmes d’électronique hybride par voie de chimie douce, dont le développement permettrait la commercialisation de technologies plus respectueuses de l’environnement. / The emerging domain of printed electronics requires new cheap and non-toxic materials for applications such as logic devices, sensors, displays, thermoelectric and photovoltaic devices. It also requires optimizing the conduction in granular semiconductors. BiCuOS has been identified as a promising p-type semiconductor for such applications. However, its high copper under-stoichiometry, induces an important p-type doping, which is detrimental for its use as a photovoltaic absorber. Moreover, like all chalcogenide based materials, it shows a poor chemical stability during sintering, thermal treatment necessary to enhance transport properties. In order to optimize its properties, solutions must be found i) to control the doping content, ii) to obtain good charge carrier mobilities in thin films. On the one hand, we have explored different kinds of substitutions such as iodine for sulfur or silver for copper, which successfully enabled to strongly reduce the charge carrier density. On the other hand, we have studied the effect of grafting conjugated molecules (terephthalic acid and polythiophene derivatives) onto the surface of a model n-type semiconductor (ZnO) to study their effect on the intergranular transport. Electronic transfer improvement occurs by transfer though a lowered energy barrier formed by the LUMO of the molecules. The formulation of optimized inks using these molecules as additives allowed the thin film deposition of p-n diodes formed with ZnO/BiCuOS. Although no photovoltaic effect has been detected yet, the p-n junctions showed high nonlinear properties and are strongly photosensitive. With this work, we have participated to the elaboration of new sulfides and hybrid interfaces systems for the improvement of semiconductor devices. The development of such hybrid electronic devices through soft chemistry method is a valuable step towards the commercialization of sustainable technologies.

L'EU-1 et la MCM-22 sont deux zéolithes à taille de pores intermédiaire, utilisées respectivement pour l'isomérisation de la coupe C8 aromatique et l'alkylation du benzène par des oléfines légères. Leurs propriétés catalytiques originales sont dues à une contribution très importante des sites acides localisés sur leur surface externe. Au cours de ce travail, différentes approches ont été envisagées pour augmenter la quantité ou la proportion de ces sites aux dépends des sites internes. Tout d'abord, une série de zéolithes H-EU-1 partiellement échangées par du sodium a été préparée et caractérisée par voie physicochimique et par des réactions modèles. Comme attendu, l'échange s'accompagne d'une diminution de la concentration en sites acides de Brönsted. Toutefois, une augmentation importante de la quantité de sites acides très forts a été observée pour des taux d'échange de 26 à 35 % et corrélée à l'augmentation de l'activité en craquage du méthylcyclohexane. Par ailleurs, les conversions du m-xylène et du 1,3,5-triméthylbenzène diminuent rapidement pour de faibles taux d'échange, ce qui pourrait s'expliquer par un échange préférentiel des sites acides externes, également mis en évidence dans le cas de zéolithes MCM-22. Enfin, une nouvelle zéolithe de la famille MWW a été synthétisée et caractérisée. Cette zéolithe possède une acidité totale similaire à celle de la MCM-22, mais une proportion de sites acides externes beaucoup plus importante, conduisant à une activité beaucoup plus grande en transformation du m-xylène et du 1,3,5-triméthylbenzène. Cette nouvelle zéolithe pourrait donc constituer une alternative intéressante à la zéolithe MCM-22 en alkylation du benzène. / EU-1 and MCM-22 are two 10-ring zeolites used in petrochemical applications such as C8-aromatic cut isomerization and benzene alkylation with short olefins. In all these processes, the original catalytic behaviors of both zeolites are characterized by an important contribution of the acid sites located over the external surface of their crystals. In this work, different methods were investigated in order to increase the amount or the proportion of these acid sites at the expense of those located inside the pores. Firstly, a series of partially Na-exchanged H-EU-1 was prepared and fully characterized through physicochemical techniques and model reactions. As expected, the exchange led to a gradual decrease in the total Brönsted site concentration. Nevertheless, an increase of the concentration in very strong acid sites was obtained for exchange ratio between 26 and 35%, leading to a significant increase of the activity in methylcyclohexane transformation. On the other hand, m-xylene and 1,3,5-trimethylbenzene (135-TMB) conversions decreased rapidly at low exchange ratio, which was attributed to a preferential exchange of the external acid sites. This latter phenomenon was also observed over Na-exchanged H-MCM-22 zeolites. Secondly, a new zeolite belonging to the MWW family was synthesized and characterized. This zeolite was shown to possess the same acid site concentration than MCM-22 zeolite but with a much higher proportion of external sites. In consequence, it exhibited a very high catalytic activity in both m-xylene and 135-TMB transformations. This material could therefore be considered as an alternative to MCM-22 in the benzene alkylation process. / EU-1 e MCM-22 são dois zeólitos de poros intermédios utilizados, respetivamente, na isomerização do corte C8 aromático e na alquilação do benzeno com olefinas leves. As suas propriedades catalíticas originais devem-se a uma importante contribuição dos centros ácidos localizados nas superfície externa. Nesta tese, diferentes abordagens foram investigadas com o objetivo de aumentar a quantidade ou a proporção destes centros ácidos em detrimento dos centros internos. Primeiramente, uma série de zeólitos H-EU-1 parcialmente permutados com sódio foi preparada e caracterizada por via físico-química e por reações modelo. Como esperado, a permuta é acompanhada por uma diminuição da concentração em centros ácidos de Brönsted. Contudo, um importante aumento da quantidade de centros ácidos muito fortes foi obtido para taxas de permuta entre 26 e 35% e correlacionado com um aumento da atividade no cracking do metilciclohexano. Por outro lado, as conversões do m-xileno e do 1,3,5-trimetilbenzeno diminuem rapidamente para baixas taxas de permuta, o que pode ser explicado por uma permuta preferencial dos centros ácidos externos. Este último fenómeno foi igualmente observado no caso do zeólito H-MCM-22 permutado com sódio. Por fim, um novo zeólito pertencente à família MWW foi sintetizado e caracterizado. Este zeólito demonstrou possuir uma acidez total semelhante à do zeólito MCM-22, porém com uma muito maior proporção de centros ácidos externos, conduzindo a uma bastante superior atividade nas transformações do m-xileno e do 1,3,5-trimetilbenzeno. Este novozeólito poderá, portanto, representar uma alternativa interessante ao zeólito MCM-22 na alquilação do benzeno.