O Escândio é um elemento terra rara, utilizado principalmente em ligas de alumínio, células combustíveis de óxido sólido e na produção de lâmpadas de haletos metálicos. Apesar de ser o 31° elemento mais abundante na crosta terrestre, raramente é encontrado concentrado na crosta terrestre, e sua produção é sempre associada ao processamento de outros minerais na forma de um subproduto, ou a recuperação de sucata. Minérios de Níquel podem conter teores de Sc variando de 50 a 350ppm e resíduos gerados durante seu processamento pode concentrar o Sc acima de 1000ppm. A recuperação do Escândio de um resíduo da cadeia de produção do Níquel foi estudada, de modo a obter um óxido com pureza acima de 99,0% para aplicações industriais. O resíduo utilizado é um precipitado, na forma de hidróxido, e contém principalmente Fe, Cu, Ni e Co, sendo o teor de Escândio em base seca aproximadamente 1000ppm. O processo de recuperação proposto consiste na lixiviação atmosférica do resíduo, precipitação seletiva para concentração do escândio e extração por solventes. A lixiviação atmosférica em meio sulfúrico 2,0mol.L-1 a 70°C permitiu a recuperação de 92,5% do Escândio contido no resíduo. Entretanto, não foi seletiva, lixiviando também parte dos demais metais presentes. Após a lixiviação para concentrar o Escândio, antes da extração por solventes, foi realizada uma precipitação com NaOH. O intuito foi precipitar o Fe, principal contaminante presente no lixiviado, entretanto ocorreu a co-precipitação de 95,5% do Sc junto a 65,6% Fe em pH 2,0. O precipitado representou uma concentração do Escândio do resíduo em 5,6 vezes. Esse concentrado de Escândio obtido foi dissolvido em solução de H2SO4 para recuperação do Escândio por extração por solventes. O extrante escolhido foi o Cyanex 923, uma mistura de óxidos alquil-fósfinicos. O mecanismo de extração do Sc pelo Cyanex 923 observado foi a solvatação e a estequiometria da reação 1:2. Foi observado um aumento na extração do Sc com o aumento da concentração de H+. O processo de extração do Sc com o Cyanex 923 é exotérmico, sendo favorecido a temperatura ambiente. O teor de Fe na solução aquosa antes da extração é 35 vezes maior que o Escândio, e apesar do Cyanex 923 ser mais seletivo para o Sc do que para o Fe, parte do Fe é co-extraído. O Fe co-extraído foi removido da fase orgânica por meio de uma lavagem com H2SO4 3mol.L-1 com uma perda de Sc de 1,3%. A reextração do Sc na fase orgânica não foi efetiva utilizando ácidos fortes devido a formação de um complexo estável. Foi utilizado ácido oxálico, técnica consolidada para reextração de terras raras, para recuperação do Sc da solução orgânica e a recuperação do Sc foi de 84,3% para uma solução com 4,0% de ácido oxálico. O oxalato de Sc precipitado foi recuperado por filtração e calcinado a 600°C. O óxido obtido apresentou pureza mínima de 99,0%. / Scandium is a rare earth element, used mainly in special aluminum alloys, SOFC\'s and metal halide lamps production. Despite of being the 31st element more abundant in Earth\'s Crust, it is rarely found concentrated in ores, and its production is always related to other minerals processing as a by-product or scrap recovering. Scandium content in Nickel ore may vary between 50 and 350ppm and residues produced during its processing can concentrate Sc above 1000ppm. Scandium recovery from a residue of Nickel processing was studied in order to obtain an oxide with purity higher than 99,0% for industrial applications. The residue used is a hydroxide precipitate, which contains mainly Fe, Cu, Ni and Co, Sc content is around 1000ppm (dry basis). The recovery process proposed consists in atmospheric leaching of the residue, selective precipitation to concentrate the Scandium and solvent extraction. The atmospheric leaching in sulfuric acid 2,0mol.L-1 at 70°C allowed the recovery of 92,5% of the Scandium present in the residue. However it was not selective and part of the other metals present in the residue were also leached. After leaching, in order to concentrate the Sc before solvent extraction, a precipitation with NaOH was performed. The initial aim was to precipitate the Iron - main contaminant present in the leach liquor - nevertheless it occurred the co-precipitation of 95,5% of the Sc besides 65,6% of Fe in pH 2,0. The precipitantion represented a concentration of the Sc in the residue of 5,6 times. The Scandium concentrate obtained was dissolved in a sulfuric acid solution to Sc recovery by solvent extraction. The extractant selected was Cyanex 923, a mixture of alkyl-phosphinic oxides. The mechanism of extraction of Scandium observed was solvation and reaction stechiometry was 1:2. It was observed an increase in Sc extraction rates by increasing the concentration of H+. The extraction of Scandium with Cyanex 923 is exothermic, and favorable at room temperature. The Iron content in aqueous solution before extraction is 35 times higher than that of Scandium, and even though Cyanex 923 being more selective for Sc than Fe, part of the Fe is co-extracted. The Fe co-extracted was removed of the organic phase by H2SO4 3mol.L-1 scrubbing with a Sc loss of 1,3%. The stripping of Scandium from organic phase was not accomplished by using strong acids due to formation of a stable complex. Afterwards, it was used oxalic acid - a technique consolidated for rare earths stripping - and the Sc recovery of organic phase was 84,3% with a solution of 4,0% oxalic acid. The Scandium oxalate precipitated was recovered by filtration and calcinated at 600°C. The Scandium oxide obtained presented 99,0% minimum purity.

Le but de cette thèse était de créer des modèles pour deux applications qui apparaissent couramment en chimie séparative, à savoir la séparation solide-liquide et la séparation liquide-liquide. L'avantage de la modélisation est manifeste dans les deux cas. L'étude fondamentale des propriétés des ions et de leur solvatation dans les milieux complexes, en tenant compte de façon simplifié des différents effets mis en jeu, nous a permis de construire un cadre qui utile aussi bien aux chimistes en laboratoire qu’aux ingénieurs lors de la conception des procédés. Nous avons adapté cette stratégie sur deux systèmes différents, qui peuvent tous deux être considérés comme complexes. Le premier système modèle pour étudier la séparation solide-liquide était des nanotubes de TiO2 dispersés dans une solution aqueuse. Ce système a été étudié au moyen de la Théorie de la Fonctionnelle de la Densité Classique couplée à une méthode de régulation de charge, au sein de l'ensemble Grand-Canonique. La méthode s'est avérée efficace pour établir la description complète des propriétés de charge des nanotubes de TiO2. Dans ce cas, nous nous sommes intéressés à obtenir la description de l'ion à l'intérieur des nanotubes chargés sous l'influence du champ électrique (créé par les nanotubes). Les calculs ont prédit des effets tels que la différence de charge de surface entre la surface externe et la surface interne, ou la violation de l'électroneutralité à l'intérieur des nanotubes. Il a été démontré que le modèle était en accord avec les données expérimentales. De plus, la méthode peut être utilisée directement pour prédire diverses techniques de titrage. Une simple généralisation de l'approche proposée permettra d'étudier l'efficacité d'adsorption réelle du procédé de séparation solide-liquide. Le second système modèle concerne l'étude du procédé d'extraction liquide-liquide et il comprend trois parties distinctes. Les trois parties ont été consacrées aux cas des extractants non ioniques, puis acides (échangeurs d'ions), et enfin aux mélanges synergiques d'extractants. Un modèle simple de thermodynamique statistique, dans lequel nous avons incorporé certains des concepts bien établis en chimie colloïdale, a fourni une approche de type matière molle pour calculer le processus à l'échelle de l'ingénieur. Nous avons développé une approche classique d'équilibres simples pour une compréhension plus large et plus intuitive de la formation des agrégats polydisperses dans l'extraction liquide-liquide. La principale conclusion présentée est que l’on doit proposer un nouveau paradigme pour la chimie : à l'équilibre, de nombreux agrégats de composition très différente mais similaires en énergie libre, coexistent. Avec la polydispersité obtenue, nous avons ainsi proposé un outil pour étudier un comportement plus "global" de l'extraction liquide-liquide. Cela nous a poussés à passer des considérations classiques d'isothermes d'extraction à celles plus précises des " cartes " d’extraction. Un grand soin a été apporté à l'étude de la synergie puisqu'il s'agit d'une important question depuis 60 ans dans la communauté scientifique et industrielle de la séparation. A notre connaissance, la première rationalisation quantitative de la synergie d’extraction a été proposée dans le cadre de cette thèse. Les effets sous-jacents des contrôles enthalpique et entropique sur la structuration des phases organiques ont été découplés et étudiés en détail. Nous espérons que cette thèse a démontré l'importance de la modélisation mésoscopique sur des exemples pratiques utilisés à la fois par les chimistes et les ingénieurs. / The object of this thesis was to create models for two applications which readily appear in separation chemistry, namely the solid-liquid and the liquid-liquid extractions. The benefit of modelling in both cases is twofold. Studying the fundamental properties of ions and their solvation properties in the complex media, and simplifying the expression for important effects, enables us to construct the framework which can be used by both chemists in the laboratory, as well as the chemical engineers in the process design. For two applications we adapted two different systems, both of which can be considered as complex. The model system to study the solid-liquid separation were TiO$_{mathrm{2}}$ nanotubes dispersed in the aqueous solution. This system was studied by the means of Classical Density Functional Theory coupled with the charge regulation method, within the Grand-canonical ensemble. Indeed, the method proved to be successful in establishing the full description of the charge properties of TiO$_{mathrm{2}}$ nanotubes. In this case, we were interested in obtaining the description of ion inside the charged nanotubes under influence by the electric field (exhibited by nanotubes). Calculations predicted effects such as the difference in surface charge between the outer and the inner surface, or the violation of electroneutrality inside the nanotubes. It was demonstrated that the model was in the agreement with the experimental data. Moreover, the method can be directly used to predict titration for various techniques. A simple generalization of the proposed approach can be used to study the actual adsorption efficiency of the solid-liquid separation process. The model system to study the liquid-liquid extraction process included three distinct parts. The three parts were devoted to the cases on non-ionic, acidic ion exchangers, and finally the synergistic mixtures of extractants. Simple bulk statistical thermodynamics model, in which we incorporated some of the well-established concepts in colloidal chemistry provided a soft-matter approach for the calculation of actual engineering-scale processes. Were have expanded a classical simple equilibria approach to broader, more intuitive polydisperse aggregates formation that underlines the liquid-liquid extraction. The key finding can be presented as a current opinion or newly-proposed paradigm: at equilibrium, many aggregates completely different in composition but similar in free energy coexist. With obtained polydispersity, we were equipped with a tool to study a more 'global' behavior of liquid-liquid extraction. This urged us to pass our considerations of historical extraction isotherms to extraction 'maps'. Great care was devoted to the study of synergy since it is a 60-year old ongoing question in the separation industrial and science community. To our best knowledge, the first quantitative rationalization total synergistic extraction was proposed within this thesis. Underlying effects of enthalpy and entropy control on the organic phase structuring were decoupled and studied in detail. Hopefully, this thesis demonstrated the importance of mesoscopic modelling to assist both chemists and chemical engineers in practical examples.

Currently, 74% of cotton acres in the United States are planted with glyphosatetolerant varieties. The average glyphosate-tolerant cotton crop is treated with glyphosate 2.1 times each year in addition to other herbicides, insecticides, and fungicides. The primary objectives of this research were to: 1) describe the influence of glyphosate and pesticides commonly applied at or near the time of cotton planting on soil microbial activity and biomass; 2) study the effect of glyphosate on fluometuron degradation; 3) evaluate the response of Rhizoctonia solani to glyphosate and fluometuron; 4) study changes in glyphosate metabolism that occur as a result of repeated glyphosate applications; and 5) define shifts in the soil microbial community. Additionally, methods for accelerated solvent extraction (ASE) of fluometuron from soils were developed. In one experiment, the addition of glyphosate reduced C-mineralization in soils treated with fluometuron, aldicarb, or mefenoxam + PCNB formulations. However, in a second experiment, C-mineralization increased when glyphosate was applied with fluometuron relative to fluometuron applied alone. Accelerated solvent extraction was used in experiments which demonstrated that application of glyphosate with fluometuron increased the rate of fluometuron degradation in soil relative to fluometuron alone. When glyphosate was added to minimal medium, degradation of fluometuron by R. solani was reduced and less fungal biomass was produced. The total amount of 14C-glyphosate mineralized was reduced when glyphosate was applied 5 times relative to 1, 2, 3, or 4 times. Incorporation of 14Cglyphosate residues into soil microbial biomass was greater following five glyphosate applications than one application 3 and 7 days after application (DAA). Soil fatty acid methyl ester (FAME) profiles were altered by five glyphosate applications relative to one application. Additionally, FAMEs common to gram-negative bacteria were present in higher concentrations following five applications relative to 1, 2, 3, or 4 applications both 7 and 14 DAA. These studies indicated that: 1) glyphosate altered the soil microbial response to other pesticides; 2) fluometuron-degrading microorganisms in soil responded differently to glyphosate; 3) changes in the dissipation or distribution of glyphosate following repeated glyphosate applications were associated with changes in the structural diversity of the soil microbial community.

Made available in DSpace on 2014-06-11T19:26:16Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-07-23Bitstream added on 2014-06-13T20:07:34Z : No. of bitstreams: 1 canizella_r_me_bauru.pdf: 668494 bytes, checksum: ab160da0c27972ddf4f1aa98cece12c9 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As atividades de uma indústria com o sistema de produção contínua possuem características próprias dependendo do processo a que se dispõe a transformar uma matéria-prima, por isso este trabalho trata de analisar as perdas na produção contínua de extração de óleo de soja por solvente, apresentando a descrição do processo e as principais indicadores de desempenho, propondo sugetões de monitoramento para melhoria dos resultados. Essa abordagem é feita comparando-se resultados propiciados por alguns autores da área com dados da área com dados levantados de uma empresa no Brasil em dois períodos distintos, incluindo análise de evolução da planta, onde a alta gerência monitora a produtividade e a qualidade dos produtos, e trata as perdas no ambiente de transformação como consumo de solvente utilizado para extração do óleo de soja e consumo de combustível para a geração de energia térmica. Conclui-se que a indústria de extração de óleo vegetal, possui diversas variáveis de controle pelo conjunto de operações necessárias à transformação, ressaltando neste caso a perda de energia térmica como prioridade de atitudes de melhorias. Dado que a tendência de aumento da capacidade de processamento de soja é evidente, pela perspectiva de crescimento da produção de soja no Brasil, deve ser considerado neste contexto, o investimento em conhecimento para as pessoas exercerem as atividades operacionais em perfeita sincronia com as informações que ocorrem no processo, garantindo o objetivo da organização de minimização das perdas, e consequente aumento do lucro e crescimento / The activities of the industry with a continuous production system have their own characteristics depending on the process that is willing to turn a raw material, so this work is to analyzed the losses in the continuous production of soybean oil extraction solvent, presenting the description of the process and key performance indicators and propose suggestions for the improvement of monitoring results. This approach is made comparing the results obtained by some authors in the field with data collected from a company in Brazil in two distinct periods, including examination of the plant, where top management monitors productivity and product quality, and treats losses the environment of use as processing solvent used to extract the soybean oil and fuel to generate heat energy. It is concluded that the industry of oil extraction plant has several control variables the operations required for processing, emphasizing in this case the loss of thermal energy as priority actions for improvements. Since the trend of increased processing capacity of soybean is evident from the perspective of growth of soybean production in Brazil, should be considered in this context, investment in knowledge for people to exercise operational activities in perfect synchrony with the information occur in the process, ensuring the organization's goal of minimizind losses, and consequent increase in profit and growth

Made available in DSpace on 2014-10-09T12:26:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:32Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:30:15Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:31Z (GMT). No. of bitstreams: 1 01388.pdf: 3542311 bytes, checksum: a396a9d45f52da7b048a936d0107064a (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2014-12-19T17:05:43Z No. of bitstreams: 0 / Made available in DSpace on 2014-12-19T17:05:43Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:26:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:32Z (GMT). No. of bitstreams: 0 / Este trabalho apresenta um estudo sobre a síntese e caracterização de novos agentes extratores da família dos calixarenos, utilizados com a técnica de membranas líquido suportadas para recuperar íons Eu(III) e U(VI) de efluentes aquosos. Os novos agentes extratores, os n-acetatocalix[n]arenos ( n= 4, 6 e 8), foram obtidos a partir da reação de acetilação dos p-terc-butilcalix[n]arenos (n = 4, 6 e 8) com anidrido acético e caracterizados por: análise elementar de CHN, espectroscopia vibracional na região do infravermelho, espectroscopia de absorção na região do UV-Vis, ressonância magnética nuclear RMN 1H, análise termogravimétrica e testes de solubilidade. Os compostos obtidos foram usados em estudos de distribuição líquido-líquido e também na técnica de membranas líquido suportadas (MLS), utilizando suportes poliméricos de 0,45, 1,2 e 5 m. A partir dos resultados da análise de caracterização verificou-se a funcionalização dos calixarenos. Tanto os calixarenos não funcionalizados quanto os funcionalizados mostraram-se bastante efetivos para extração de íons Eu(III) e U(VI). Da análise dos resultados concluiu-se que: a eficiência de extração é dependente do pH. Para íons Eu(III) a máxima eficiência de extração foi alcançada em pH 4 e 5 e para o U(VI) em pH 7. Os solventes utilizados, tolueno e clorofórmio, mostraram-se bastante eficazes no processo de extração já que os dois tiveram eficiência de extração bastante próxima. Nos estudos de extração utilizando a técnica de membranas líquido suportadas (MLS) os resultados mostraram que a permeação dos íons Eu(III) e U(VI) é dependente do pH, da concentração dos metais e da concentração de NaNO3 na solução de alimentação, da porosidade da membrana e da concentração do HNO3 na solução de reversão. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:30:15Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:31Z (GMT). No. of bitstreams: 1 01388.pdf: 3542311 bytes, checksum: a396a9d45f52da7b048a936d0107064a (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2014-12-19T17:05:43Z No. of bitstreams: 0 / Made available in DSpace on 2014-12-19T17:05:43Z (GMT). No. of bitstreams: 0 / A contaminação das águas subterrâneas e recursos hídricos superficiais nas últimas décadas representam uma ameaça para a saúde pública. No Brasil, as águas subterrâneas desempenham importante papel no abastecimento público e privado, suprindo as mais variadas necessidades de água em diversas cidades e comunidades. Com a finalidade de garantir a qualidade da água consumida, o ser humano vem desenvolvendo desde a década de 70 diversas técnicas analíticas para monitorar a presença de contaminantes. No entanto, algumas dessas técnicas podem gerar resíduos piores ao meio ambiente do que as já existentes. Desta maneira a partir da década de 90, surge uma nova tendência na forma como conduzir as análises químicas, com o intuito de reduzir o impacto ambiental. No presente trabalho, foi explorada uma técnica de extração que atende tais objetivos, denominada como microextração líquido-líquido dispersivo DLLME, desenvolvida por M.Rezaee e colaboradores. Onde foram validados os hidrocarbonetos policíclicos aromáticos, atingindo limites entre 0,04 a 1,56 μgL-1, também foram analisadas amostras de águas subterrâneas coletadas aleatoriamente, em 4 postos de gasolina localizados na cidade de São Paulo. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP