This PhD project studied the caesium and strontium removal capacities of six nanoporous materials. Indeed, it was linked in with the SIXEP plant present at Sellafield site, UK, which is currently using natural clinoptilolite, originally mined from the Mojave Desert, to remove radioactive caesium and strontium ions from wastewater effluents. At the moment the feeds entering the SIXEP plant correspond to the best working conditions for clinoptilolite. As the feeds are moving toward more acidic pH and complex solutions and as clinoptilolite works at neutral pH, new nanoporous materials are required. This project had been divided into sub-projects, which all had the same purpose of finding the best material for caesium and strontium removal under complex solutions. The first part of the PhD focused on the synthesis of CST, SNT, ETS-4 and ETS-10 materials following literature reviews. The two last materials studied were provided by Fortum Power and Heat Oy for CsTreat material and by Sellafield Ltd for clinoptilolite material. The second part of the PhD consisted in studying the exchange capacities for caesium and strontium ions for each material studied under batch conditions using several water compositions relevant to Sellafield Ltd. Each water composition had different competing ions or pH and were used to classify the materials between them. From that it was found that Clinoptilolite stays the best materials for caesium and strontium removal. The third part of the project was the gamma irradiation of the materials. This irradiation had an aim to check the stability of the structure of the studied materials under gamma irradiation. The materials were exposed to four different gamma doses which were 0.5; 1; 3 and 6 MGy, the last one corresponding to the maximum dose were structural changes could happen. This revealed that all the materials, except ETS-4 material, were stable under gamma irradiation and that no structural changes were observable. The fourth part of the project was an extension of the third part in which the materials were Cs exchanged before being gamma irradiated to a dose of 6 MGy. This showed that the caesium exchange process is not affected by radiation. Finally, the unexchanged materials were alpha irradiated using a 15 MeV He2+ beam at the Dalton Cumbria Facility. Two irradiations were performed on CsTreat, CST, ETS-4, ETS-10 and clinoptilolite material. It was found that all the materials were damaged by alpha irradiation and displayed amorphous framework To resume, it appeared that clinoptilolite still stays one of the best materials for the removal of caesium and strontium ions in a wide range of wastewater composition. Additionally, it was discovered that ETS-10 material could be a good alternative to clinoptilolite material as its structure is stable under gamma irradiation and it displayed good exchange capacities when competing ions were present in the feeds. CST could also be a substitute as it shows good ion exchange properties under a broad range of pH. SNT material was great for strontium removal while CsTreat was working well for caesium removal. Even though ETS- 4 revealed good ion exchange capacities they were lower than clinoptilolite, ETS- 10 or CST materials.

Made available in DSpace on 2014-12-17T15:42:26Z (GMT). No. of bitstreams: 1 ValdeliceRS.pdf: 981957 bytes, checksum: cedb4f2ae440069c889ba97e29744a20 (MD5) Previous issue date: 2007-07-11 / The natural gas (NG) is a clean energy source and found in the underground of porous rocks, associated or not to oil. Its basic composition includes methane, ethane, propane and other components, like carbon dioxide, nitrogen, hydrogen sulphide and water. H2S is one of the natural pollutants of the natural gas. It is considered critical concerning corrosion. Its presence depends on origin, as well as of the process used in the gas treatment. It can cause problems in the tubing materials and final applications of the NG. The Ag?ncia Nacional do Petr?leo sets out that the maximum concentration of H2S in the natural gas, originally national or imported, commercialized in Brazil must contain 10 -15 mg/cm3. In the Processing Units of Natural Gas, there are used different methods in the removal of H2S, for instance, adsorption towers filled with activated coal, zeolites and sulfatreat (solid, dry, granular and based on iron oxide). In this work, ion exchange resins were used as adsorbing materials. The resins were characterized by thermo gravimetric analysis, infrared spectroscopy and sweeping electronic microscopy. The adsorption tests were performed in a system linked to a gas-powered chromatograph. The present H2S in the exit of this system was monitored by a photometrical detector of pulsing flame. The electronic microscopy analyzes showed that the topography and morphology of the resins favor the adsorption process. Some characteristics were found such as, macro behavior, particles of variable sizes, spherical geometries, without the visualization of any pores in the surface. The infrared specters presented the main frequencies of vibration associated to the functional group of the amines and polymeric matrixes. When the resins are compared with sulfatreat, under the same experimental conditions, they showed a similar performance in retention times and adsorption capacities, making them competitive ones for the desulphurization process of the natural gas / O g?s natural (GN) ? uma fonte de energia limpa encontrada no subsolo de rochas porosas, associado ou n?o ao petr?leo. Sua composi??o b?sica inclui metano, etano, propano e outros componentes, como di?xido de carbono, nitrog?nio, ?cido sulf?drico e ?gua. H2S ? um dos poluentes naturais do g?s natural. ? considerado cr?tico no que se refere ? corros?o. Sua presen?a depende da origem, bem como do processo usado no tratamento do g?s. Ele pode acarretar problemas nas tubula??es e aplica??es finais do GN. A Ag?ncia Nacional de Petr?leo estabelece que a concentra??o m?xima de H2S no g?s natural, de origem nacional ou importado, comercializado no Brasil contenha no m?ximo 10 15 mg/m3. Nas Unidades de Processamento do G?s Natutal, diferentes m?todos s?o usados na remo??o de H2S, por exemplo, em torres de adsor??o recheadas com carv?o ativo, ze?litas e Sulfatreat (s?lido, seco, granular e baseado em ?xido de ferro). Neste trabalho, resinas de troca-i?nica foram usadas como material adsorvente. As resinas foram caracterizadas por an?lise termogravim?trica, espectroscopia de infravermelho e microscopia eletr?nica de varredura. Os ensaios de adsor??o foram realizados em um sistema acoplado a um cromat?grafo a g?s. O H2S presente na sa?da do sistema foi monitorado por um detector fotom?trico de chama pulsante. As an?lises de microscopia eletr?nica demonstraram que a topografia e morfologia das resinas favorecem o processo de adsor??o. Caracter?sticas como comportamento macro, part?culas de tamanhos variados, geometrias esf?ricas, sem a visualiza??o de poros na superf?cie, foram encontrados. Os espectros de infravermelho apresentaram as principais freq??ncias de vibra??o associadas aos grupos funcionais das aminas e matrizes polim?ricas. Quando comparadas ao sulfatreat, sob as mesmas condi??es experimentais, as resinas demonstraram semelhante desempenho em tempos de reten??o e capacidade de adsor??o, tornando-se competitiva para o processo de dessulfuriza??o do g?s natural

Made available in DSpace on 2014-12-17T15:42:27Z (GMT). No. of bitstreams: 1 ValdeliceRS.pdf: 629576 bytes, checksum: 6bcf4a0b805ce82618289068cfb23b77 (MD5) Previous issue date: 2006-07-11 / The natural gas (NG) is a clean energy source and found in the underground of porous rocks, associated or not to oil. Its basic composition includes methane, ethane, propane and other components, like carbon dioxide, nitrogen, hydrogen sulphide and water. H2S is one of the natural pollutants of the natural gas. It is considered critical concerning corrosion. Its presence depends on origin, as well as of the process used in the gas treatment. It can cause problems in the tubing materials and final applications of the NG. The Ag?ncia Nacional do Petr?leo sets out that the maximum concentration of H2S in the natural gas, originally national or imported, commercialized in Brazil must contain 10 -15 mg/cm3. In the Processing Units of Natural Gas, there are used different methods in the removal of H2S, for instance, adsorption towers filled with activated coal, zeolites and sulfatreat (solid, dry, granular and based on iron oxide). In this work, ion exchange resins were used as adsorbing materials. The resins were characterized by thermo gravimetric analysis, infrared spectroscopy and sweeping electronic microscopy. The adsorption tests were performed in a system linked to a gas-powered chromatograph. The present H2S in the exit of this system was monitored by a photometrical detector of pulsing flame. The electronic microscopy analyzes showed that the topography and morphology of the resins favor the adsorption process. Some characteristics were found such as, macro behavior, particles of variable sizes, spherical geometries, without the visualization of any pores in the surface. The infrared specters presented the main frequencies of vibration associated to the functional group of the amines and polymeric matrixes. When the resins are compared with sulfatreat, under the same experimental conditions, they showed a similar performance in retention times and adsorption capacities, making them competitive ones for the desulphurization process of the natural gas / O g?s natural (GN) ? uma fonte de energia limpa encontrada no subsolo de rochas porosas, associado ou n?o ao petr?leo. Sua composi??o b?sica inclui metano, etano, propano e outros componentes, como di?xido de carbono, nitrog?nio, ?cido sulf?drico e ?gua. H2S ? um dos poluentes naturais do g?s natural. ? considerado cr?tico no que se refere ? corros?o. Sua presen?a depende da origem, bem como do processo usado no tratamento do g?s. Ele pode acarretar problemas nas tubula??es e aplica??es finais do GN. A Ag?ncia Nacional de Petr?leo estabelece que a concentra??o m?xima de H2S no g?s natural, de origem nacional ou importado, comercializado no Brasil contenha no m?ximo 10 15 mg/m3. Nas Unidades de Processamento do G?s Natutal, diferentes m?todos s?o usados na remo??o de H2S, por exemplo, em torres de adsor??o recheadas com carv?o ativo, ze?litas e Sulfatreat (s?lido, seco, granular e baseado em ?xido de ferro). Neste trabalho, resinas de troca-i?nica foram usadas como material adsorvente. As resinas foram caracterizadas por an?lise termogravim?trica, espectroscopia de infravermelho e microscopia eletr?nica de varredura. Os ensaios de adsor??o foram realizados em um sistema acoplado a um cromat?grafo a g?s. O H2S presente na sa?da do sistema foi monitorado por um detector fotom?trico de chama pulsante. As an?lises de microscopia eletr?nica demonstraram que a topografia e morfologia das resinas favorecem o processo de adsor??o. Caracter?sticas como comportamento macro, part?culas de tamanhos variados, geometrias esf?ricas, sem a visualiza??o de poros na superf?cie, foram encontrados. Os espectros de infravermelho apresentaram as principais freq??ncias de vibra??o associadas aos grupos funcionais das aminas e matrizes polim?ricas. Quando comparadas ao sulfatreat, sob as mesmas condi??es experimentais, as resinas demonstraram semelhante desempenho em tempos de reten??o e capacidade de adsor??o, tornando-se competitiva para o processo de dessulfuriza??o do g?s natural

Le présent travail vise à étudier le couplage de l’échange d’ions et de l’électrodialyse. Cette étude est appliquée à la séparation de biomolécules. Un des objectifs est de diminuer la génération d’effluents salins produits par les étapes d’échange d’ions utilisées de façon classique dans les bioséparations. Une première approche a conduit à la conception d’une architecture avec un mode de fonctionnement cyclique en 3 étapes qui permet de purifier certaines familles de peptides sans utiliser de tampon de pH ni générer d’effluents. Le dispositif expérimental est constitué d’une cellule d’électrodialyse dans laquelle sont introduites des résines échangeuses d’anions. Les trois étapes sont les suivantes : fixation des biomolécules sur la résine initialement sous forme carbonate, élution par une solution de dioxyde de carbone dissous dans l’eau, électrorégénération de la résine sous sa forme initiale, conduisant simultanément à la régénération de la solution d’acide carbonique. L’étape d’électrorégénération a été modélisée et les simulations permettent d’améliorer la compréhension des processus couplés mis en jeu comme les équilibres d’échange d’ions, les équilibres en solution, l’électromigration. Une deuxième approche a ensuite consisté à étudier les possibilités de contrôle du pH par voie électrochimique, afin de limiter l’utilisation de solutions tampons. La dissociation de l’eau, conduisant à la formation de protons et d’ions hydroxyles, a été plus particulièrement étudiée en mettant à profit les propriétés des contacts dits « bipolaires » sous l’effet d’un champ électrique. Il s’est alors avéré que les choix du type de résine et de la densité de courant permettent de jouer sur le pH Toutefois ce travail doit être poursuivi par la recherche d’architectures et de modes opératoires qui permettent d’obtenir un pouvoir tampon adéquat / The present work aims to study the coupling of ion exchange and electrodialysis. This study is applied to the separation of biomolecules. One objective is to reduce the generation of saline wastewater produced by the ion exchange steps used conventionally in bioseparations. One approach has led to the design of architecture with a cyclic mode in 3 steps to purify some families of peptides without using a buffer pH or generate wastes. The experimental device consists of an electrodialysis cell in which are introduced anion exchange resins. The three steps are: loading of biomolecules on the resin initially in the carbonate form, elution with a solution of carbon dioxide dissolved in water, electroregeneration of the resin in its original form leading simultaneously to the regeneration of the carbonic acid solution. Using a modelling of the electroregeneration step, simulations can improve the understanding of coupled processes as the ion exchange equilibria, the equilibria in solution, the electromigration. A second approach has then been to study the possibilities of controlling the pH by electrochemical means to limit the use of buffers. The dissociation of water, leading to the formation of protons and hydroxyl ions, has been particularly studied by accounting the properties of contacts called « bipolar » as a result of an electric field. It was established that the choice of resin type and the current density can modify the pH. However this work must be pursued through research of architectures and operating procedures that deliver appropriate buffer capacity

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / A cajucultura à considerada uma das atividades sÃcio-econÃmicas mais importantes da regiÃo Nordeste do Brasil. Apesar de ser empregado industrialmente para fabricaÃÃo de polpa, bebidas e doces, o pedÃnculo do caju apresenta altÃssimos nÃveis de desperdÃcio. Pouco mais de 10% da produÃÃo agrÃcola à explorada comercialmente. Neste contexto, a obtenÃÃo de produtos de valor agregado a partir do pedÃnculo do caju â como xaropes de frutose e glicose â pode indicar rotas econÃmicas alternativas para as regiÃes produtoras, aproveitando a produÃÃo excedentÃria nÃo absorvida pelo mercado de sucos e doces industrializados. O leito mÃvel simulado constitui uma das mais inovadoras tecnologias cromatogrÃficas que realiza separaÃÃo de isÃmeros de forma contÃnua. Um dos pontoschave desta tecnologia à a escolha adequada das condiÃÃes de operaÃÃo (vazÃes e tempos de troca) que propiciem uma separaÃÃo adequada. Este trabalho apresenta estudos de equilÃbrio de adsorÃÃo de soluÃÃes sintÃticas de frutose e glicose, em condiÃÃes de sobrecarga de concentraÃÃo, visando à separaÃÃo destes aÃÃcares em leito mÃvel simulado para a produÃÃo de xaropes de caju enriquecidos em frutose e glicose. As isotermas de adsorÃÃo foram obtidas por cromatografia frontal, utilizando soluÃÃes sintÃticas de frutose e glicose com concentraÃÃo variando de 10 a 120g/L, nas temperaturas de 30, 40 e 60 ÂC, utilizando as resinas de troca iÃnica Dowex MTO 99Ca e Diaion UBK 555. As curvas de ruptura (breakthrough) das soluÃÃes sintÃticas foram confrontadas com curvas de breakthrough obtidas a partir do xarope de caju para validaÃÃo do modelo. A partir das mesmas, foram obtidas isotermas nÃo-lineares bem descritas pelo modelo de Langmuir. O modelo do transporte dispersivo foi empregado para reproduzir o comportamento das curvas de breakthrough e para estimar parÃmetros de transferÃncia de massa, utilizando o solver comercial gPROMS. Os dados de equilÃbrio de adsorÃÃo foram utilizados para gerar a regiÃo de completa separaÃÃo (razÃes de vazÃo nas zonas 2 e 3) em uma unidade de leito mÃvel simulado (LMS), com base na Teoria do EquilÃbrio (mÃtodo do triÃngulo) para prediÃÃo das condiÃÃes de operaÃÃo numa unidade piloto. / The cashew crop is considered one of the most important socio-economic activity in Northeastern Brazil. Despite being used industrially for the production of pulp, drinks and sweets, the cashew apple shows high levels of waste. A little more than 10% of crop is exploited commercially. In this context, adding value to products derived from the cashew apple - such as fructose and glucose syrups - may indicate alternative economical routes for producing regions, by consuming the surplus not absorbed by the market of juices and sweets. The simulated moving bed is one of the most innovative technologies that performs continuous chromatographic separation of isomers. One of the key points of this technology is the choice of operating conditions (flows and switching times) that provides adequate separation. This work presents studies of adsorption equilibrium of synthetic solutions of fructose and glucose, under overloaded conditions of concentration, aiming at the separation of these sugars in simulated moving bed for the production of high-fructose and high-glicose syrups. The adsorption isotherms were obtained by frontal analysis, using synthetic solutions with fructose and glucose concentrations ranging from 10 to 120g / L, at temperatures of 30, 40 and 60  C, using the ion exchange resins Dowex MTO 99Ca and Diaion UBK 555. The breakthrough curves of synthetic solutions were compared with those obtained from the cashew syrup for validation of data, tha sake of model validation. Tha measured isotherms were non-linear and well described by the Langmuir model. The dispersive transport model was used to reproduce the behavior of breakthrough curves and to estimate mass transfer parameters, using the gPROMS commercial solver. Adsorption data were used to generate the region of complete separation (flowrate ratios in sections 2 and 3) of a simulated moving bed (SMB unit), based on the equilibrium theory (the triangle method), in order to predict operating conditions in a pilot unit.

A presença de compostos inibidores ao metabolismo de microrganismos é a principal dificuldade encontrada para utilização dos hidrolisados hemicelulósicos para produção de etanol e xilitol. Compostos derivados das degradações da lignina, da celulose e hemicelulose são liberados durante a hidrólise ácida da biomassa. O presente trabalho teve como objetivo avaliar a utilização de diferentes tratamentos de destoxificação de forma combinada, visando a purificação do hidrolisado hemicelulósico de bagaço de cana-de-açúcar para obtenção de etanol e xilitol. Os tratamentos utilizados foram: coagulação/floculação de impurezas coloidais, separação por membranas de microfiltração e ultrafiltração e resinas de troca iônica, sendo o material de partida foi um hidrolisado de bagaço recém-obtido. O tratamento de coagulação/floculação foi otimizado utilizando planejamento de experimentos do tipo fatorial e na melhor condição promoveu reduções de 53,3% em compostos fenólicos, 34,8% de furfural, 3,7% de HMF, 4,2% de ácido acético e 67,6% da área espectral. Na sequência, o hidrolisado tratado na etapa anterior foi submetido a testes de microfiltração e ultrafiltração. Para esta etapa os melhores resultados foram obtidos utilizando membranas de 100 kDa em polietersulfona. Com este tratamento foi possível reduzir em 11,9% os compostos fenólicos, 23,8% de furfural, 21,5% de HMF e 21,4% de área espectral. Após o tratamento com membranas o hidrolisado foi percolado em resinas de caráter catiônico e aniônico utilizadas em série possibilitando a eliminação de 34,8% de compostos fenólicos, 38,5% de furfural, 74,7% de HMF, 55% de ácido acético e 10,3% da área espectral. Ao final, a combinação de todas as tecnologias de separação estudadas possibilitou remoções maiores que 97% para compostos fenólicos, furfural e HMF o que resultou numa redução da área espectral em 99,3%. O hidrolisado purificado foi concentrado e submetido a testes fermentativos preliminares para produção de etanol e xilitol. Estas bioconversões apresentaram rendimentos de 0,58 g/g em xilitol e 0,29 g/g em etanol por D-xilose consumida, que equivalem a 86% e 83% dos rendimentos obtidos a partir dos meios sintéticos, respectivamente. Estes resultados indicaram que a purificação obtida através do uso combinado da coagulação/floculação, separação por membranas e resinas de troca iônica foram bastante satisfatórios principalmente considerando a fermentabilidade obtida a partir deste substrato em comparação ao meio sintético. / The presence of inhibitory compounds in the metabolism of microorganisms is the main difficulty for the use of hemicellulosic hydrolyzate for ethanol and xylitol production. Compounds derived from lignin, cellulose and hemicellulose degradation are released during the biomass acid hydrolysis. This study aimed to evaluate the use of different detoxification treatments in combination, aimed at purifying the hydrolyzed hemicellulosic sugarcane bagasse. The treatments were: coagulation / flocculation of colloidal impurities, separation by microfiltration and ultrafiltration membrane and ion exchange resins, and the starting material was a newly obtained hydrolyzed bagasse. The treatment of coagulation / flocculation was optimized using factorial experiments design of the kind that in the best condition promoted reductions of 53.3%, 34.8%, 3.7%, 4.2% and 67.6% in phenolic compounds, furfural, hydroxymethylfurfural, acid acetic acid and spectral area, respectively. Next, the hydrolyzate treated in the previous step was tested for microfiltration and ultrafiltration. For this step the best results were obtained using a 100 kDa membrane in polyethersulfone. With this treatment were obtaneid reduction of 11.9%, 23.8%, 21.5%, 21.4% in phenolic compunds, furfural, hydroxymethylfurfural and spectral area, respectively. After membrane treatment the hydrolyzate was percolated through resins with anionic and cationic character used in series enabling the elimination of 34.8%, 38.5%, 74.7%, 55% and 10.3% of phenolic compounds, furfural, hydroxymethylfurfural, acetic acid and spectral area, respectively. At the end, the combination of all separation technologies studied was able to remove greater than 97% of phenolic compounds, furfural and hydroxymethylfurfural which resulted in a reduction of 99.3% in spectral area. The purified hydrolyzate was concentrated and subjected to preliminary fermentative testing for the ethanol and xylitol production. These bioconversions had income of 0.58 g/g in xylitol and 0.29 g/g in ethanol by D-xylose consumed, equivalent to 86% and 83% of ethanol and xylitol yield obtained from the synthetic medium, respectively. These results indicated that the purification achieved through the combined use of coagulation/flocculation, membrane separation and íon exchange resins were very satisfactory, especially considering the fermentability obtained from this substrate compared to the synthetic medium.

<p>The interactions between anionic, crosslinked gels and cationic surfactants have been investigated. When exposed to oppositely charged surfactant, the gel collapses into a dense complex of polyion and micelles. During deswelling, the gel phase separates into a micelle-rich, collapsed surface phase, and a swollen, micelle-free core, both still part of the same network. As more surfactant is absorbed, the surface phase grows at the expense of the core, until the entire gel has collapsed. Polyacrylate (PA) gels with dodecyl- (C₁₂TAB), and cetyltrimethylammonium bromide (C₁₆TAB), as well as hyaluronate gels with cetylpyridinium chloride, have been studied. </p><p>Kinetic experiments have been performed on macro- as well as microgels, using micromanipulator assisted light microscopy for the latter. A surfactant diffusion controlled deswelling model has been employed to describe the deswelling. The deswelling kinetics of PA microgels have been shown to be controlled by surfactant diffusion through the stagnant layer surrounding the gel, as the surface phase is relatively thin for the major part of the deswelling. For macroscopic PA gels the surface phase is thicker, and the kinetics with C₁₂TAB were therefore also influenced by diffusion through the surface phase, while for C₁₆TAB they were dominated by it. </p><p>Relevant parameters have also been determined using equilibrium experiments. An irregular, balloon-forming deswelling pattern, mainly found for macrogels, as well as unexpectedly long lag times and slow deswelling for microgels, are reported and discussed. </p><p>The microstructure of fully collapsed PA/C₁₂TAB complexes has been studied using small-angle X-ray scattering. A cubic <i>Pm3n</i> structure was found at low salt concentration, which melted into a disordered micellar phase as the salt concentration was increased. Further increasing the salt concentration dissolved the micelles, resulting in no ordering.</p>

Zur selektiven Entfernung von Schwermetallen aus industriellen Abwässern und Prozesslösungen der metallverarbeitenden Industrie werden synthetische metallkomplexierende funktionelle Polymere – mit Iminodiessigsäure (IDE) als aktive Spezies – seit Jahren erfolgreich zur Eliminierung störender Kationen eingesetzt. Ständig steigende Anforderungen an die Qualität der aufzubereitenden Wässer verlangen nach leistungsfähigen Selektivaustauschern, die den Erhalt der Eigenschaften von Prozesslösungen (z. B. pH-Wert, Salzgehalt) ermöglichen. Ziel der Untersuchungen war es, die strukturellen Matrixeinflüsse auf Beladung, Kapazität, Selektivität und Kinetik durch Variation der Matrix und der experimentellen Bedingungen näher zu untersuchen. Auf Basis einer monodispersen Erstsubstitution eines Styren-Divinylbenzen-Copolymerisates wurde durch gezielten Einbau funktioneller Gruppen – Synthese mit differenziertem Substitutionsgrad (TK/N 1-2) – versucht, systematisch den Einfluss des Substitutionsgrades der Matrix auf die Eigenschaften der Ionenaustauscher zu analysieren. Methodisch geordnet wurden zunächst die Versuche nach dem Batch- und anschließend nach dem Säulenverfahren durchgeführt und parallel dazu die Matrix charakterisiert. Das Verhalten der funktionellen Ankergruppen in Abhängigkeit vom pH-Wert der Lösung (pH-Bereich 2 - 5) wurde untersucht, der optimale Anreicherungs-pH-Wert, die maximale Beladung (Kapazität) und Selektivität der unterschiedlich substituierten Proben für die Schwermetall-Ionen Cu, Zn, Ni, Cd, Pb und Co ermittelt. Den statischen Versuchen folgten dynamische Untersuchungen im Säulenverfahren. Ziel war die Ermittlung des Durchbruchverhaltens und der Durchbruchkapazität bei optimalem pH-Wert in Abhängigkeit vom Substitutionsgrad gegenüber den Einzelmetallionen (Cu, Ni, Zn) und ausgewählten Paaren (Cu/Ni, Cu/Zn, Ni/Zn). Alle Ionenaustauscher wurden ausschließlich in der Ca-Form eingesetzt. / Selective ion exchange offers a good solution for cleaning many waste streams. The aim of this study was to develop selective ion exchange materials for effective and economical applications in waste water treatment. The investigation of chelate resins is based on iminodiacetate with different secondary substitution (degree of substitution TK/N 1 - 2, from aminoacetic acid to iminodiacetate as functional group). As comparison the weak acid resin Lewatit TP 207 was used. The research focused on the application of selective ion exchange resins for waste effluents to ascertain the feasibility of a selective ion exchange process employing chelating cation exchangers for heavy metal removal. The metals of interest were copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), lead (Pb) and cadmium (Cd) and the resins appointed in the Ca-form. The batch operation was conducted to determine the equilibrium data and the operating resin capacity, one of the most important properties. The main equilibrium parameter affecting the ion exchange was the pH value (array 2-5). The best accumulation pH value was obtained using pH 5 for all metals. The only exception was lead with pH 3. After determining the viability of the different resins with batch systems, this study has focused on the column mode experiments. They were generated for the selected resins in the continuous ion exchange process which are essentially reserved for industrial applications. A practical application of the breakthrough curves is the determination of the breakthrough time which helps to find the best operating conditions.

The interactions between anionic, crosslinked gels and cationic surfactants have been investigated. When exposed to oppositely charged surfactant, the gel collapses into a dense complex of polyion and micelles. During deswelling, the gel phase separates into a micelle-rich, collapsed surface phase, and a swollen, micelle-free core, both still part of the same network. As more surfactant is absorbed, the surface phase grows at the expense of the core, until the entire gel has collapsed. Polyacrylate (PA) gels with dodecyl- (C12TAB), and cetyltrimethylammonium bromide (C16TAB), as well as hyaluronate gels with cetylpyridinium chloride, have been studied. Kinetic experiments have been performed on macro- as well as microgels, using micromanipulator assisted light microscopy for the latter. A surfactant diffusion controlled deswelling model has been employed to describe the deswelling. The deswelling kinetics of PA microgels have been shown to be controlled by surfactant diffusion through the stagnant layer surrounding the gel, as the surface phase is relatively thin for the major part of the deswelling. For macroscopic PA gels the surface phase is thicker, and the kinetics with C12TAB were therefore also influenced by diffusion through the surface phase, while for C16TAB they were dominated by it. Relevant parameters have also been determined using equilibrium experiments. An irregular, balloon-forming deswelling pattern, mainly found for macrogels, as well as unexpectedly long lag times and slow deswelling for microgels, are reported and discussed. The microstructure of fully collapsed PA/C12TAB complexes has been studied using small-angle X-ray scattering. A cubic Pm3n structure was found at low salt concentration, which melted into a disordered micellar phase as the salt concentration was increased. Further increasing the salt concentration dissolved the micelles, resulting in no ordering.

The successful genomic era has resulted in a great demand for efficient production and purification of proteins. The main objective of the work described in this thesis was to develop methods to facilitate recovery of target proteins after recombinant production in Escherichia coli. A positively charged purification tag, Zbasic, has previously been constructed by protein design of a compact three-helix bundle domain, Z. The charged domain was investigated for general use as a fusion partner. All target proteins investigated could be selectively captured by ion-exchange chromatography under conditions excluding adsorption of the majority of Escherichia coli host proteins. A single cation-exchange chromatography step at physiological pH was sufficient to provide Zbasic fusion proteins of high purity close to homogeneity. Moreover, efficient isolation directly from unclarified Escherichia coli homogenates could also be accomplished using an expanded bed mode. Since the intended use of a recombinant protein sometimes requires removal of the purification tag, a strategy for efficient release of the Zbasic moiety using an immobilised protease was developed. The protease columns were reusable without any measurable decrease in activity. Moreover, subsequent removal of the released tag, Zbasic, was effected by adsorption to a second cation-exchanger. Using a similar strategy, a purification tag with a negatively charged surface, denoted Zacid, was constructed and thoroughly characterised. Contrary to Zbasic, the negatively charged Zacid was highly unstructured in a low conductivity environment. Despite this, all Zacid fusion proteins investigated could be efficiently purified from whole cell lysates using anion-exchange chromatography Synthesis of polypeptides occurs readily in Escherichia coli providing large amounts of protein in cells of this type, albeit often one finds the recombinant proteins sequestered in inclusion bodies. Therefore, a high throughput method for screening of protein expression was developed. Levels of both soluble and precipitated protein could simultaneously be assessed in vivo by the use of a flow cytometer. The positively charged domain, Zbasic, was shown also to be selective under denaturing conditions, providing the possibility to purify proteins solubilised from inclusion bodies. Finally, a flexible process for solid-phase refolding was developed, using Zbasic as a reversible linker to the cation-exchanger resin. / QC 20101020