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Álcoois primários sulfatados de cadeia longa, usualmente na forma de sais de sódio, são tensoativos de grande interesse comercial utilizados em diversas formulações de higiene pessoal e limpeza doméstica. Eles são produzidos comercialmente através da reação de álcoois etoxilados com trióxido de enxofre seguida de imediata neutralização com hidróxido de sódio. O produto formado é uma solução neutra de álcool primário etoxilado sulfatado em água. Sabe-se que a armazenagem desse produto por longos períodos de tempo em temperaturas elevadas pode levar à hidrólise completa, mas, em condições normais de uso e temperatura ambiente é esperado que o produto seja resistente à hidrólise. No entanto observou-se que algumas amostras comerciais de lauril éter sulfato de sódio que foram estocadas por diferentes períodos de tempo em frascos fechados à temperatura ambiente sofreram hidrólise em intervalos de tempo relativamente curtos. Isso leva à hipótese de que o comportamento de hidrólise seria influenciado por outras variáveis além da temperatura e do tempo de estocagem. O presente trabalho consistiu em identificar as variáveis de maior impacto na reação de hidrólise por meio de experimentos planejados. O teor de ativos foi acompanhado ao longo da reação para avaliar o efeito da presença de eletrólitos, de material insulfatado, em diferentes temperaturas, variando-se o pH inicial por meio da adição de ácido clorídrico. O comportamento da reação de hidrólise observado foi compatível com aquele descrito na literatura para o dodecil sulfato de sódio. A hidrólise apresentou-se como sendo autocatalítica, com a aceleração da taxa de reação provavelmente causada pela presença de íons hidrogênio liberados na reação. Foi possível identificar que as variáveis de maior efeito na reação foram: pH inicial, o teor de cloreto de sódio e a temperatura. O modelo de troca iônica em pseudo-fase foi utilizado para o tratamento dos resultados experimentais e mostrou-se adequado tendo sido, portanto, utilizado para prever o comportamento de estabilidade do produto à temperatura ambiente e nas condições em que o produto é normalmente comercializado. Um modelo empírico de redes neurais foi desenvolvido com sucesso para prever o comportamento do pH ao longo do tempo para as condições estudadas. / Long-chain primary alkyl sulfuric acids, usually as their sodium salts, are important commercial surfactants used in a large number of household and personal care formulations. They are commercially produced by treatment of mixtures of ethoxylated fatty alcohols with sulfur trioxide followed by immediate neutralization with sodium hydroxide, a neutral aqueous mixture of sodium primary alkyl ether sulfate is obtained. It is known that prolonged storage of the material at elevated temperature can lead to complete hydrolysis but under normal use and typical environmental conditions the product is expected to be resistant to hydrolysis. In spite of that it has been observed that some commercial samples of sodium lauryl ether sulfate stored for different periods of time in sealed containers at room temperature have undergone hydrolysis in a relatively short period of time which leads to the hypothesis that the hydrolysis behavior would be strongly influenced by variables other than temperature and storage time. The present work consisted of identifying the process variables with the most significant effect on the acid hydrolysis by using experimental design. The rate of hydrolysis has been followed acidimetrically to evaluate the effect of electrolytes as well as the concentration of unsulfated matter at different temperatures, over a wide initial pH range, under the presence of added hydrochloric acid. The pattern of kinetic behaviour observed was broadly the same as previously described for the sodium dodecyl sulfate. The hydrolysis presented the characteristic autocatalytic form, the catalysis presumably arising from the production of hydrogen sulfate ions. It was possible to observe that the most significant effects on the rate of hydrolysis were the initial pH, the total amount of sodium chloride and the temperature. The results were also discussed in terms of the ion-exchange pseudophase model of the micelle reaction. Accordingly to the fitting of parameters that was carried out it is possible to conclude that the pseudo-phase ion-exchange theory is found to account satisfactorily for the results reported and it was used to predict the stability behavior of the product at room temperature and under normal commercial conditions. A neural network based model was also successfully developed in order to predict the pH behavior in the conditions studied.

Made available in DSpace on 2017-07-10T18:08:16Z (GMT). No. of bitstreams: 1 Thiago DArisbo.pdf: 2108504 bytes, checksum: 7b8aad29ec7d75a6fd370e54a95cd849 (MD5) Previous issue date: 2011-02-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Ion exchange is a process that is used in the treatment of aqueous industrial effluents containing organic compounds and heavy metals. The fixed bed columns are longer applied by allowing the process to occur continuously (cycles of regeneration). The design and process optimization of the ion exchange column requires the use of mathematical models. Phenomenological models of these systems involve the solution of partial differential and algebraic equations. The equilibrium data for ion exchange processes are usually described by the Mass Action Law (MAL), which can be considered non-ideality of aqueous and solid phases. Artificial Neural Networks (ANN) are being used successfully for the study of equilibrium data because they are empirical models and don t demand a mathematical rigor. This work aimed to evaluate the applicability of the hybrid model to describe the dynamics of ion exchange in fixed beds of binary systems. This system consists of partial differential equations obtained from mass balance in fluid phases in the ion exchanger and ANN to describe the balance. LAM was adjusted to experimental data of ion exchange equilibrium and then were generated 4200 data sets for each binary pair studied, which served as training for RNA. We tested networks with different structures, with one and two input layers. The 3-3-2 structure was used in the simulations of the hybrid model because it was the best represented the systems during the training phase. The differential equations were solved by the lines method. A computer program in FORTRAN language was developed for solving the model equations. DASSL subroutine was used to solve the equations. The performance of the hybrid model was evaluated from the results obtained with the phenomenological model, in which case the equilibrium description was made with the use of MAL. It also was the analysis of results from the comparison of experimental data. To evaluate the model we used data from the literature of ion exchange in Amberlite IR 120 resin on the systems Cu-Na and Zn-Na and in NaY zeolite on Fe-Na and Zn-Na. Both models were efficient to describe the dynamics of ion-exchange fixed bed columns, and the hybrid model had the advantage of the reduced computational time (82% reduction on average) as a result of not needing to solve a nonlinear equation. / A troca iônica é um processo muito utilizado no tratamento de efluentes industriais aquosos contendo compostos orgânicos e metais pesados. As colunas de leito fixo são mais aplicadas por permitir que o processo ocorra de maneira contínua (ciclos de regeneração). O projeto e a otimização de processos de troca iônica em coluna requer o uso de modelos matemáticos. Os modelos fenomenológicos destes sistemas envolvem a resolução de equações diferenciais parciais e algébricas. Os dados de equilíbrio de processos de troca iônica geralmente são descritos pela Lei da Ação das Massas (LAM), na qual podem ser consideradas as não idealidades das fases aquosa e sólida. As Redes Neurais Artificiais (RNA) estão sendo utilizadas com sucesso para o estudo destes dados de equilíbrio por serem modelos empíricos e não demandarem tal rigor matemático. Esta dissertação teve por objetivo avaliar a aplicabilidade do modelo híbrido para descrever a dinâmica do processo de troca iônica em leito fixo de sistemas binários. Este sistema é constituído de equações diferenciais parciais obtidas por meio de balanço de massa nas fases fluida e no trocador iônico e de RNA para descrever o equilíbrio. A LAM foi ajustada a dados experimentais de equilíbrio de troca iônica e, então, foram gerados conjuntos de 4200 dados para cada par binário estudado, os quais serviram como treinamento para a RNA. Foram testadas redes com diferentes estruturas, com uma e com duas camadas de entrada. A estrutura 3-3-2 foi utilizada nas simulações do modelo híbrido, pois foi a que melhor representou os sistemas na etapa de treinamento. As equações diferenciais foram resolvidas pelo método das linhas. Um programa computacional em linguagem FORTRAN foi desenvolvido para a resolução das equações do modelo. Foi utilizada a sub-rotina DASSL para resolver as equações. O desempenho do modelo híbrido foi avaliada a partir dos resultados obtidos com o modelo fenomenológico, sendo que neste caso a descrição do equilíbrio foi feita pelo uso da LAM. Também foi feita a análise dos resultados a partir da comparação dos dados experimentais. Para avaliar o modelo foram utilizados dados da literatura de troca iônica em resina Amberlite IR 120 dos sistemas Cu-Na e Zn-Na e na zeólita NaY dos sistemas Fe-Na e Zn-Na. Ambos os modelos foram eficientes para descrever a dinâmica de troca iônica de colunas de leito fixo, sendo que o modelo híbrido apresentou como vantagem o menor tempo computacional (82% de redução em média) em decorrência de não necessitar resolver a equação não-linear.

Ce travail porte sur l'amélioration de la sélectivité préférentielle d'une membrane cationique à base d’ETFE pour une utilisation en électrodialyse afin de traiter des effluents industriels contenant un mélange d’acides et de sels métalliques. Pour cela, nous avons fait appel à la méthode de la modification chimique de la surface d’une membrane cationique par la formation d’un film superficiel mince portant des charges positives afin de former une barrière de répulsion électrostatique pour des cations bivalents tout en permettant le passage de cations monovalents tels que les protons.<p>La synthèse de la membrane cationique de base a été réalisée en passant par différentes étapes à savoir :le greffage du styrène - divinylbenzène (DVB), la chlorosulfonation et l’hydrolyse. <p>Au cours de ce travail, nous avons mis au point un protocole de greffage du styrène-DVB dans le film d’ETFE qui permet l’obtention d’un film ayant un taux de greffage reproductible assurant à la membrane cationique finale une bonne conductivité électrique et une capacité d’échange acceptable pour une membrane d’électrodialyse. Une étude de la réaction de greffage en fonction de la concentration en réticulant a été réalisée. <p>Nous avons procédé par la suite à la modification de la surface du film d’ETFE greffé styrène-DVB par la formation d’une couche superficielle mince fixée par des liens covalents. Les membranes modifiées ont été obtenues par la réaction d’une seule face du film d’ETFE greffé chlorosulfoné avec la 3-diméthylaminopropylamine. La modification chimique de la surface du film ETFE greffé chlorosulfoné a été suivie par la technique FTIR-ATR. L’effet de la concentration de la diamine sur les propriétés électrochimiques des différentes membranes modifiées a été étudié. La résistance électrique des membranes modifiées équilibrées au contact de solutions de chlorure de sodium et d'acide sulfurique a été mesurée par la technique d’impédance. La détermination du nombre de transport du proton et de l’ion sodium a été réalisée à partir de mesures du potentiel de membrane. La densité de courant limite des membranes a été évaluée sur base des courbes courant-tension. Les mesures de chronopotentiométrie ont été également effectuées sur les différentes membranes synthétisées.<p>Les résultats de ces caractérisations montrent que la modification de la surface engendre des changements considérables au niveau des propriétés électrochimiques des membranes résultantes. La résistance électrique, la densité de courant limite ainsi que les propriétés de transport de la membrane dépendent d’une part de la concentration de la diamine utilisée et d’autre part de la solution dans laquelle la membrane modifiée est équilibrée. <p>La sélectivité préférentielle des différentes membranes vis-à-vis des protons par rapport aux ions bivalents a été testée en réalisant des électrodialyses d’un milieu mixte H2SO4-NiSO4. Nos résultats montrent que la modification chimique de la surface de la membrane affecte d’une manière significative le transport des ions nickel tout en respectant le passage des protons. Une meilleure séparation a été obtenue pour une membrane modifiée en utilisant la diamine pure.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

A S-metilcisteína (SMC) e o peptídeo &#947;-glutamil-S-metilcisteína (&#947;-Glu-SMC), presentes em algumas leguminosas comestíveis, principalmente no feijão comum (Phaseolus vulgaris L.), apresentam efeitos biológicos controversos após a sua ingestão por animais de laboratório e humanos. O presente trabalho teve por finalidade investigar a absorção intestinal da SMC e da &#947;-Glu-SMC, empregando ensaios com segmentos intestinais isolados de rato, comparando-se a assimilação destes com a de aminoácidos protéicos. Os segmentos de duodeno e jejuno foram evertidos e incubados em solução nutritiva contendo isoladamente os aminoácidos (SMC, Phe e Met) ou o peptídeo em estudo, . acompanhando-se a taxa de absorção de cada um, em intervalos regulares entre 10 e 60 min. A taxa de absorção foi determinada por cromatografia de troca iônica em autoanalisador de aminoácidos. A SMC apresentou valores superiores aos aminoácidos Met e Phe. As mesmas amostras foram analisadas também por cromatografia líquida de alta eficiência em fase reversa após derivatização com o-oftalaldeído (Gustine, 1985). Os resultados por esta metodologia não foram conclusivos pois ocorreu perda de eficiência da coluna cromatográfica, provavelmente devido à adsorção irreversível de subprodutos resultantes da reação de derivatização. Sugere-se que sejam estudadas modificações no protocolo analítico. Em relação à absorção do peptídeo-Glu-SMC, comprovou-se a sua hidrólise pelo aparecimento de pequenas quantidades de SMC livre no lado seroso dos segmentos intestinais, supondo-se que esta hidrólise tenha ocorrido pela enzima &#947;-glutamiltranspeptidase (&#947;-GT). A reduzida quantidade de SMC livre encontrada poderia ser atribuída a uma eventual perda de atividade desta enzima durante o preparo e manuseio do segmento intestinal. Contudo, em ensaios adicionais, não foi observada perda de atividade desta enzima durante a incubação dos segmentos intestinais em solução nutritiva por 40 minutos. A atividade da enzima &#947;-GT foi aproximadamente três vezes superior no duodeno do que no jejuno, sendo de relevância em estudos de absorção intestinal. Mais estudos são necessários para um melhor entendimento do processo absortivo do peptídeo. / The biological effects of S-methyl-cysteine (SMC) and the peptide &#947;-glutamyl-cysteine (&#947;-Glu-SMC), distributed in some edible legume seeds, mainly in common bean (Phaseolus vulgaris L.), are controversial when these compounds are ingested by laboratory animals and humans. In the present study it was investigated the rate of intestinal absorption of SMC and &#947;-Glu-SMC employing isolated segments of rat intestines and analyzing comparatively the absorption of protein amino acids. The everted segments of duodenum and jejunum were incubated in a nutritive solution and the aminoacids SMC, Phe and Met and the peptide &#947;-Glu-SMC were added individually in order to measure their absorption rates in intervals of 10 min until reaching 60 minutes of incubation. The absorption rate of each compound was measured by ion exchange chromatography (amino acid analyzer). The absorption rates observed for SMC were higher than those observed for Met and Phe. The same samples were also analyzed by reversed phase-HPLC after derivatization with o-phthalaldehyde (Gustine,.1985). Results did not succeed because the chromatographic column lost efficiency probably due to adsorption of byproducts of the derivatization reaction. We suggest that modifications on the analytical protocol should be developed. Results showed that the peptide &#947;-Glu-SMC seem to be hydrolyzed supported by the appearance of small amounts of free SMC on the serosal side of the intestines. The hydrolysis was probably catalyzed by the enzyme &#947;-glutamyltranspeptidase (&#947;-GT). The appearance of only small amounts of free SMC could be explained by an eventual loss of the activity of &#947;-GT during preparation and incubation of the intestinal segments. However, in additional assays, the enzyme did not show any loss of activity during incubation of the segments for 40 min. We observed also that the activity of the enzyme &#947;-GT was 3 times higher in duodenum than in jejunum. This observation could be relevant for absorption studies employing intestinal segments. Further studies are necessary for a better understanding of the absorption process of the peptide &#947;-Glu-SMC.

La presente Tesis Doctoral consiste en la determinación de las propiedades de transporte de diferentes especies catiónicas a través de membranas de intercambio catiónico. Las membranas de intercambio iónico son un componente clave de los reactores electroquímicos y de los sistemas de electrodiálisis, puesto que determinan el consumo energético y la eficiencia del proceso. La utilización de este tipo de membranas para el tratamiento de efluentes industriales no es muy extendida debido a los requisitos de elevada resistencia química y durabilidad que deben cumplir las membranas. Otro asunto importante radica en la eficiencia en el transporte de los iones que se quieren eliminar a través de la membrana. Normalmente, existe una competencia por el paso a través de las membranas entre diferentes especies debido al carácter multicomponente de los efluentes a tratar. Sin embargo, una mejora en las propiedades de las membranas de intercambio iónico permitiría la implantación del tratamiento mediante reactores electroquímicos de efluentes industriales con un contenido importante en compuestos metálicos, tales como los baños agotados de las industrias de cromado. La utilización de una tecnología limpia como la electrodiálisis conllevaría diferentes ventajas, entre las cuales destacan la recuperación de los efluentes para su reutilización en el proceso industrial, el ahorro en el consumo de agua y la disminución de la descarga de contaminantes al medio ambiente. La determinación de las condiciones de operación óptimas así como la mejora de las propiedades de transporte de las membranas constituye el principal tema de la presente investigación. Para ello, se emplearán diferentes tipos de membrana. En primer lugar, se estudiará el comportamiento de las membranas poliméricas comerciales que poseen unas propiedades de resistencia química elevadas, las cuales se tomarán como referencia. De forma paralela, se producirán membranas conductoras de iones a partir de materiales cerámicos económicos, ya que la resistencia de los materiales cerámicos a sustancias oxidantes y muy ácidas es mayor que la de los materiales poliméricos. Este punto constituye la parte más innovadora de la investigación, puesto que la mayoría de las membranas de intercambio iónico comerciales están basadas en materiales poliméricos que no pueden resistir las condiciones específicas de los efluentes industriales. Una vez determinadas las condiciones de operación óptimas, se realizarán ensayos en plantas piloto con el fin de confirmar los resultados obtenidos mediante las técnicas de caracterización y determinar el grado de recuperación y coste energético asociado a los procesos electrodialíticos de tratamiento de efluentes industriales. / Martí Calatayud, MC. (2014). STUDY OF THE TRANSPORT OF HEAVY METAL IONS THROUGH CATION-EXCHANGE MEMBRANES APPLIED TO THE TREATMENT OF INDUSTRIAL EFFLUENTS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/46004 / Premios Extraordinarios de tesis doctorales

Highly proton conducting polymers for operation in hydrogen/oxygen proton exchange membrane fuel cells (PEMFCs) provide often a poor mechanical strength due to high water contents. To strengthen the conducting polymers, blends with different ratios of partially fluorinated sulfonic acid graft and diblock copolymers with perfluorinated polymers were prepared. To analyze the effect of the different quantities of the compounds, with regard to water sorption and proton conducting properties, membranes were prepared by dissolving the components and drop casting. Partially sulfonated poly([vinylidene difluoride-co-chlorotrifluoroethylene]-g-styrene) (P(VDF-co-CTFE)-g-SPS) was blended with polyvinylidene difluoride (PVDF), decreasing the ion exchange capacity (IEC). The blended polymers absorbed less water. However, the by AC impedance spectroscopy determined proton conductivity stayed stable or increased slightly. The effective proton mobility remained constant. Partially sulfonated poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) (P(VDF-co-HFP)-b-SPS) with two different PS-block lengths were blended with different amounts of poly(vinylidene difluoride-co-hexafluoropropylene) (P(VDF-co-HFP)). In that case, the polymers absorbed less water and the proton conductivity decreased stepwise by adding more than 20 wt% P(VDF-co-HFP). The results indicate that a blending of P(VDF-co-CTFE)-g-SPS with PVDF inhibits swelling without having an effect on the proton conductivity, though water sorption and IEC are reduced.

The aim of this thesis was to introduce and apply the possibilities of using waste glycerol from biodiesel production and partly waste low-stiffen coolant from cars that could be applied in industry. At the beginning of the thesis is summarized biodiesel production and its world production. There is more developed biodiesel production in the Czech Republic and in the European Union and some European legal regulations and standards for biodiesel. Also described herein is a composition of biodiesel and the description of the technology of its production. In the theoretical section summarizes the physical and chemical properties of glycerol and there is also summarized the traditional use of glycerol as food, explosives, etc. There are also new procedures that were performed in the experimental part of the thesis. There are described the ion exchange mechanism, ion exchange resin properties and the properties of the acids and salts generated by neutralization with NaOH contained in the waste glycerol. Also is described herein the wood protection and properties of ethylene glycol coolants and properties of boroglycerol and boroglycol as protection for wood and mechanism of their preparation. Next is described the mechanism of dehydration of glycerol to acrolein and options which can perform the synthesis. In the experimental part, the pH of waste glycerol was measured, then was measured the exact amount of NaOH in the glycerol. There is also desribed cleaning of waste glycerol from NaOH using acidic cation exchange resins on columns, or by neutralization with oleic acid, lactic acid and CO2. Further syntheses were performed glycerol borate and ethylene glycol borate. Water amount in ethylene glycol and methanol with water amount in glycerol were found by distillation. Then were prepared boroglycol and boroglycerol. By the amount resulting from the amount of reaction water were observed reaction conditions H3BO3, Na2B4O7•10 H2O and glycerol. At the end was carried out experimental dilution resulting boroglycerol and boroglycol by ethanol, methanol, TMB. Finally, the diluted boroglycerol was deposited on wood. Dehydration of glycerol to acrolein under the catalytic action of KHSO4 was performed. The results are given all the results and discussed the possibility of using the knowledge gained in this work in the industry. In conclusion, there are listed the economic comparison using waste glycerol and crude oil as a raw material and also charts the development of oil prices in 40 years since 1970, and graph of the price of waste glycerol.

At the beginning of the thesis is summarized biodiesel production and its world production. There is more developed biodiesel production in the Czech Republic and in the European Union and some European legal regulations and standards for biodiesel. Also described herein is a composition of biodiesel and the description of the technology of its production. In the theoretical section summarizes the physical and chemical properties of glycerol and there is also summarized the traditional use of glycerol as food, explosives, etc. There are also new procedures that were performed in the experimental part of the thesis. Then, here are the proposed new procedures for processing waste glycerol and glycol, which were conducted in the experimental part of the thesis. There are described the ion exchange properties of the cation exchangers and also properties of salts generated by neutralization of NaOH in the waste glycerol with organic acids and CO2. There is also described wood protection, properties of ethylene glycol as coolant and properties of boroglycerols and boroglycols as protection for wood and mechanism of their preparation. Then there is described a mechanism of dehydration of glycerol to acrolein and options which can perform the synthesis. In the experimental part, the pH of waste glycerol was measured and then was measured the amount of NaOH in the waste glycerol. There is also desribed cleaning of waste glycerol from NaOH using acidic cation exchange resins on columns, or by neutralization with oleic acid, lactic acid and CO2. Further syntheses were performed glycerol borate and ethylene glycol borate. Water amount in ethylene glycol and methanol with water amount in glycerol were found by distillation. Then were prepared boroglycol and boroglycerol. By the amount resulting from the amount of reaction water were observed reaction conditions H3BO3, Na2B4O7•10 H2O and glycerol. At the end was carried out experimental dilution resulting boroglycerol and boroglycol by ethanol, methanol, TMB. Finally, the diluted boroglycerol was deposited on wood. Dehydration of glycerol to acrolein under the catalytic action of KHSO4 was performed. The results are given all the results and discussed the possibility of using the knowledge gained in this work in the industry. In conclusion, there are listed the economic comparison using waste glycerol and crude oil as a raw material and also charts the development of oil prices in 40 years since 1970, and graph of the price of waste glycerol. There is also discussed technological applicability of the methods used in practice.