Die vorliegende Arbeit beschreibt zwei Verfahren zur Herstellung von submikronen Ionenaustauscherpartikeln. Im ersten Verfahren, der Miniemulsionspolymerisation, liegt der Schwerpunkt auf dem energetisch sehr aufwendigen Schritt der Herstellung einer stabilen Miniemulsion. Dabei werden Prozessparameter optimiert und Destabilisierungsmechanismen analysiert. Im zweiten Teil der Arbeit wird ein neues kostengünstiges und ressourcenschonendes Herstellungsverfahren vorgestellt. Dabei werden kommerziell erhältliche Ionenaustauscherpartikel auf Polymerbasis in Kugelmühlen zerkleinert.

L’industrie du nucléaire produit de grandes quantités d’effluents radioactifs de sources diverses nécessitant des traitements spécifiques en fonction de leur composition chimique. Le césium 137 fait partie, avec le strontium 90, des radioéléments majoritairement présents dans ces effluents qui doivent être extraits le plus efficacement possible en produisant un minimum de déchets secondaires. Le traitement en colonne est parmi les procédés les plus adaptés pour ce type d’extraction sur support solide. Son principe repose sur la capacité de sorption du radioélément par des hexacyanoferrates (HCF) de cuivre, des échangeurs ioniques minéraux très sélectifs du césium. Des investigations sur les HCF ont permis de mettre en avant les modifications structurales intervenant lors de l’échange avec le césium, à l’origine de leur forte affinité pour cet ion. La fonctionnalisation des HCF sur des monolithes de silice à porosité hiérarchique a mis à profit les propriétés remarquables de ces supports pour une utilisation en colonne. Les cinétiques de sorption évaluées jusqu’aux concentrations traces ont montré une capture rapide du césium qui justifie l’intérêt de ce matériau pour un emploi en colonne. Par ailleurs, la compétitivité des monolithes fonctionnalisés par rapport à des lits particulaires a été démontrée. Ces matériaux ont enfin été mis en œuvre pour la décontamination simultanée du césium et du strontium par des mécanismes couplés d’échange d’ions et de coprécipitation du sulfate de baryum, rendue possible par la grande perméabilité des monolithes. Un modèle simplifié du transport réactif basé sur la morphologie du monolithe a été développé avec le code HYTEC en supposant un écoulement dispersif dans les canaux du squelette et la diffusion dans les parois du squelette et les agrégats de HCF. / The nuclear industry produces high amounts of contaminated water from various sources that require specific treatments depending on their chemical composition. Cesium-137 and strontium-90 are among the most abundant radionuclides in those effluents, which have to be removed as efficiently as possible in order to generate the lowest amount of waste. The column process is one of the most suitable processes to achieve this solid-phase extraction. Its principle is based on the sorption capacity of the radionuclide by copper hexacyanoferrates (HCF), highly cesium-selective mineral ion-exchangers. Investigations on HCF pointed out the structural effects of the cesium insertion within the crystal, which were linked to the high affinity of HCF for this ion. The functionalization of HCF on silica monolith with hierarchical pore structure was carried out in order to benefit the remarkable properties of these supports used as a column. Sorption kinetics evaluated down to trace concentrations have shown a fast capture of the cesium, which proves the interest of this material for a column process purpose. In addition, the performances of functionalized silica monolith have been highlighted in comparison with those made of particulate fixed beds. Finally, those materials were implemented for a simultaneous decontamination of cesium and strontium by a double extraction mechanism of ion exchange and coprecipitation of barium sulfate, allowed by the high permeability of the monolith. A simplified model of reactive transport was built with the HYTEC code, based on the actual morphology of the monolith. To do so, a dispersive flow in the macroporous intraskeletal channels and a diffusive flow inside the walls of the structure and the HCF aggregates were assumed.

Previously, selenium was known as an element with negative properties. However, in the last century, the significant positive effects on human health were detected. Currently, the function, behavior and toxicity of selenium are still not well known. The key to understand it is to do speciation analysis. The aim of this diploma thesis is to develop method for determination inorganic (sodium selenite and selenate) and organic (selenourea, selenocystine, selenomethionine) selenium compounds. Parameters of apparatus for electrochemical hydride generation with atomic absorption spectrometry detector were optimized, final conditions were set and optimal conditions for separation process using HPLC were investigated. Calibration dependences for selenium compounds were measured and analytical figures of merit were investigated. In conclusion, a coupled method HPLC- EcHG- QFAAS for determination of individual selenium compounds was proposed, and it was tested on urea samples. Calibrations for these measurements were investigated and analytic characteristics were calculated. Based on these comparisons it can be said that proposed method allows the determination of selected selenium compounds in both aqueous and urea matrices. Subject words: Spectroscopy, analytical chemistry Key words: Atomic absorption...

<div>Metal-zeolites are promising materials for passive adsorber technologies for the abatement of nitrogen oxides (NOx, x = 1,2) and aldehydes during low-temperature operation in automotive exhaust aftertreatment systems. The aqueous-phase exchange processes used commonly to prepare metal-zeolites typically require mononuclear, transition metal complexes to diffuse within intrazeolite pore networks with their solvation shells and replace extra framework cations of higher chemical potential. When metal complexes are larger than the zeolite pore-limiting diameter, this imposes intracrystalline transport restrictions; thus, complexes and agglomerates tend to preferentially deposit near the surfaces of crystallites, requiring post-synthetic treatments to disperse metal species more uniformly throughout zeolite crystallites via solid-state ion-exchange processes. Here, we address the influence of post-synthetic gas treatments and zeolite material properties on the structural interconversion and exchange of extra framework Pd in CHA zeolites with a focus on the thermodynamic, kinetic, and mechanistic factors that dictate the Pd site structures and spatial distributions that form.<br></div><div><br></div><div>Pd-amine complexes introduced via incipient wetness impregnation on CHA zeolites were found to preferentially site near crystallite surfaces. Post-synthetic treatments in flowing air results in Pd-amine decomposition and agglomeration to metallic Pd0and supersequent oxidation to PdO, before converting to mononuclear Pd²⁺cations through an Ostwald ripening mechanism at high temperatures (>550 K). Progressively higher air treatment temperatures (up to 1023 K) were found to (1) thermodynamically favor the formation of mononu-clear Pd²⁺cations relative to agglomerated PdO particles, (2) increase the apparent rate of structural interconversion to mononuclear Pd²⁺, and (3) facilitate longer-range mobility of molecular intermediates involved in Ostwald ripening processes that allow Pd cations to form deeper within zeolite crystallites to form more uniformly dispersed Pd-zeolite materials. Additionally, the controlled synthetic variation of the atomic arrangement of 1 or 2Al sites in the 6-membered ring of CHA was used to show a thermodynamic preference to form mononuclear Pd2+cations charge-compensated by 2 Al sites over [PdOH]⁺complexes at 1 Al site. Colloidal Pd nanoparticle syntheses and deposition methods were used to prepare monodisperse Pd-CHA materials to isolate the effects of Pd particle size on structuralinterconversion to mononuclear Pd²⁺under a range of external environments. Consistent with computational thermodynamic predictions, smaller Pd particle sizes favor structural interconversion to mononuclear Pd²⁺under high-temperature air treatments (598–973 K),while adding H2O to the air stream inhibits the thermodynamics but not the kinetics of mononuclear Pd²⁺formation, demonstrating that water vapor in exhaust streams may be deleterious to the long-term stability of Pd-zeolite materials for passive NOx adsorption.<br></div><div><br></div><div>The influence of metal-zeolite material properties on the adsorption, desorption, and conversion of formaldehyde, a government-regulated automotive pollutant, under realistic conditions was investigated to identify beneficial material properties for this emerging application in mobile engine pollution abatement. A suite of Beta zeolite materials was synthesized with varied adsorption site identity (Brønsted acid, Lewis acid, silanol groups, and extra framework metal oxide) and bulk site densities. All materials stored formaldehyde and converted a large fraction of formaldehyde to more environmentally benign CO and CO₂, demonstrating the efficacy of silanol defects and zeolitic supports for the storage of formaldehyde. Sn-containing zeotypes, containing either Lewis acidic framework Sn sites or extra framework SnO_x particles, resulted in the greatest selectivity to CO and CO₂ formed during formaldehyde desorption, suggests that Sn species are a beneficial component in metal-zeolite formulations for the abatement of formaldehyde in automotive exhaust streams.<br></div><div><br></div><div>This work demonstrates how combining precise synthesis of metal-zeolites of varied bulk and atomic properties with site-specific characterization and titration methods enables systematically disentangling the influence of separate material properties (e.g., Pd particle size, zeolite framework Al arrangement, silanol density, heteroatom identify) and external environment on changes to metal structure, speciation, and oxidation state. This approach provides thermodynamic, kinetic, and mechanistic insights into the factors that influence metal re-structuring under the practical conditions encountered in automotive exhaust after treatment applications and guidance for materials design and treatment strategies to form desired metal structures during synthesis and after regeneration protocols.<br></div>

The majority of the nutrients in household wastewater are found in the urine and in order to facilitate the use the nutrients in the urine as fertilizer, the urine can be can be concentrated. To extract the nutrients from the urine, various technologies for urine concentration are being developed today. As the technologies are relatively new, urine concentration systems have not been installed on a larger scale. In this study, sustainability of three different urine concentration technologies was evaluated through a fictional case study for 2100 people that took inspiration from a planned residential area in Malmö, Sweden, where technology for urine concentration will be implemented in at least one of the buildings. The technologies were evaluated through a multi-criteria assessment (MCA), where different criteria within sustainability categories environment, technical, economic and health were determined based on the Sustainable Development Goals (SDGs). The technologies examined were alkaline dehydration, nitrification-distillation and ion-exchange using a pre-step of struvite precipitation. For the alkaline dehydration technology, fresh urine is added to an alkaline medium, in order to prevent nitrogen losses, and then dried. In the nitrification-distillation technology, stored urine is treated by first being stabilized by a partial nitrification and then distilled in order to reduce the volume. For the ion-exchange and struvite precipitation system, phosphorus is first precipitated from stored urine and nitrogen is then extracted through ion-exchange. The urine concentration technologies were assumed to be installed in semi-centralized treatment plants in basements in the residential area. The other household wastewater was assumed to be treated in the local wastewater treatment plant (WWTP). The results showed that all three urine concentration technologies may contribute to a significant increase in nitrogen recovery from the household sewer. However, this may come at the expense of increased annual costs for the population. Before it is possible to determine whether urine concentration can be an alternative as a complement to the existing wastewater treatment, further studies of the urine concentration technologies and their sustainability are required. However, this study indicated that urine concentration technologies perform well in many of the sustainability criteria examined and therefore have potential to contribute to the SDGs, especially regarding nitrogen recovery. This study can therefore be an incentive for further studies, where the sustainability of an implementation of urine concentration in Sweden is addressed. / Majoriteten av näringen i hushållsavloppsvattnet finns i urinen och för att underlätta användningen av växtnäringsämnena i urinen som gödningsmedel kan den koncentreras. För att utvinna näringen ur urinen utvecklas idag olika tekniker för urinkoncentrering. Då teknikerna är relativt nya har system för urinkoncentrering inte installerats i en större skala. Därför utvärderades hållbarheten för tre olika urinkoncentreringsmetoder genom en fiktiv fallstudie som innefattade 2100 personer. Fallstudien fick inspiration från ett planerat bostadsområde i Malmö, Sverige, där teknik för urinkoncentrering ska implementeras i minst en av byggnaderna. Teknikerna utvärderades genom en multikriterieanalys (MKA), där kriterier inom hållbarhetskategorierna miljö, teknik, ekonomi och hälsa valdes utifrån de Globala målen. De tekniker som utvärderades var alkalisk urintorkning, nitrifikations-destillering och jonbyte där struvitutfällning tillämpades som förbehandling. För den alkaliska urintorkningen tillförs färsk urin till ett alkaliskt medium, för att förhindra kväveförluster, och torkas sedan. I nitrifikations-destillerings tekniken behandlas lagrat urin genom att det först stabiliseras genom en partiell nitrifikation för att sedan destilleras för att reducera volymen. För systemet med jonbyte och struvitfällning, fälls först fosfor från lagrat urin ut och sedan utvinns kvävet genom jonbyte. Urinkoncentreringsteknikerna antogs anläggas i semi-centraliserade reningsverk i källare i bostadsområdet. Övrigt hushållsvatten antogs renas i det lokala avloppsreningsverket. Resultatet visade att samtliga av de tre teknikerna för urinkoncentrering kan bidra till en betydande ökning kväveåtervinning från hushållsavloppet. Dock kan detta komma på bekostnad av ökade årliga kostnader för de boende i området. Innan det är möjligt att avgöra om urinkoncentrering kan vara ett alternativ som ett komplement till den befintliga avloppsreningen i Sege Park krävs vidare studier av urinkoncentreringsteknikerna och deras hållbarhet. Däremot visade denna studie att urinkoncentreringsteknikerna presterar bra i många av de undersökta hållbarhetskriterierna och har därför potential att bidra till de Globala målen, främst när det gäller kväveåtervinning. Denna studie kan därför vara ett incitament för vidare studier som behandlar hållbarheten av en implementering av urinkoncentrering i Sverige.

Les dioxines/furanes sont des polluants organiques persistants générés principalement par l’activité anthropique et spécifiquement par l’industrie lors des procédés de combustion mettant en jeux des matières organochlorées. Etant donné leur transport à large échelle dans l'environnement et leur impact sur la santé de l’homme, il est nécessaire de contrôler en temps réel, les traces de dioxines à l'émission des sources fixes. Un tel contrôle est plus particulièrement requis lors de l’incinération de déchets hétérogènes non préalablement triés. Deux types de matériaux microporeux ont été sélectionnés pour l'adsorption des dioxines au vu de leurs propriétés physico-chimiques. Il s’agit des zéolithes et les Metal-Organic Frameworks (MOF). Deux types de test d’adsorption ont été conduits, d’une part, en laboratoire en phase liquide avec la dioxine dans de l’isooctane comme solvant, et d’autre part, en phase gazeuse lors des campagnes de prélèvement sur un site d'incinération de déchets avec une matrice réelle très complexe. L'adsorption en phase liquide nous a permis de conclure sur l’efficacité des matériaux étudiés pour l’adsorption de trois congénères de dioxine de différentes tailles. Elle a ensuite été caractérisée par des techniques d'analyses spécifiques afin de remonter aux mécanismes d'adsorption. L’efficacité d’adsorption a été testée en phase gaz sur un site d'incinération de déchets ménagers avec les mêmes matériaux testés en phase liquide au laboratoire. Finalement, en se basant sur les résultats d'adsorption en phases liquide et gaz, deux pistes ont été proposées pour la conception d’un dispositif de mesure de dioxines en ligne commercialisable. / Dioxins and furans are persistent organic pollutants generated mainly by human activity and industry during combustion processes using organochlorine substances. Due to their long-range air transport and impact on human health, it is necessary to have on-line dioxin emission monitoring at stationary source. Such a control is tipically required for incineration of no pre-sorted heterogeneous wastes.Two types of microporous materials have been selected for dioxin adsorption due to their physicochemical properties: zeolites and Metal -Organic Frameworks (MOF). Two types of adsorption tests have been established. On the one hand, dioxin adsorption tests in liquid phase in laboratory with isooctane as solvent, and on the other hand, dioxin adsorption tests in dynamic gas phase during sampling campaigns on waste incineration site with a very complex matrix.Liquid phase adsorption allowed us to conclude on the effectiveness of materials studied for dioxin adsorption. Adsorption has been after characterized by specific analysis techniques to trace adsorption mechanisms. Adsorption efficiencies were tested in gas phase on a household waste incinerator with the same materials tested in liquid phase in laboratory. Finally, taking into account liquid and gas phase results, two solutions have been proposed for a future commercialized device for on-line dioxin monitoring.

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Arbetet studerade skillnaderna mellan en användning av kalciumhydroxid samtnatriumhydroxid som pH-reglerande kemikalie i en kemisk vattenreningsanläggning.Samt dess påverkan på filtreringssteg som sandfilter, aktivkol filtrering samt jonbytarfiltrering. Det behandlade hur reningsgraden påverkas sett till metallreduktion av;krom, nickel, koppar och zink. Hur slammängderna är i förhållande tillvarandramellan de olika pH-reglernade kemikalierna och slutligen hur filtreringsstegenpåverkas beroende på vilken pH-reglerande kemikalie som doserats. Resultatet förarbetet har visat på att reningsgraden minskar vid användning av natriumhydroxidsom pH-reglerande kemikalie vilket besvarar en del av syftet samt frågeställningenmed arbetet. Ytterligare har resultatet påvisat att de efterkommande filtreringsstegensom i en eventuell framtid kan implementeras leder till en reducering avmetallhalterna i vattnet, vanligen gick reduceringen inte att statistiskt säkerställa mentendenser på en reducering påvisades. Även de erhållna slammängdernareducerades vid användning av natriumhydroxid som pH-reglerande kemikalie vilketvar ett förväntat resultat sett till hypotes och litteratur. Ytterligare minskadeturbiditeten för klarfasproverna vid en natriumhydroxiddosering i förhållande till enkalciumhydroxiddosering. Arbetets resultat har således påvisat den goda möjlighetenatt ersätta den manuella doseringen av solid kalciumhydroxid som pH-reglerandekemikalie emot en automatisk dosering av natriumhydroxid erhållen i vätskeform. / This work studied the differences between the use of calcium hydroxide and sodiumhydroxide as a pH-regulating chemical in a chemical water treatment plant. As wellas its impact on filtration steps such as sand filter, activated carbon filtration and ionexchange filtration. It dealt with how the degree of purification is affected in terms ofmetal reduction of; chromium, nickel, copper and zinc. How the sludge amounts arein relation to each other between the different pH-regulated chemicals and finallyhow the filtration steps are affected depending on which pH-regulating chemical hasbeen dosed. The results for the work have shown that the degree of purificationdecreases when using sodium hydroxide as a pH-regulating chemical, whichanswers part of the purpose and the question of the work. Furthermore, the resultshave shown that the subsequent filtration steps that can be implemented in thepossible future lead to a reduction of the metal contents in the water, usually thereduction could not be statistically confirmed but tendencies of a reduction wereshown. The amounts of sludge obtained were also reduced by using sodiumhydroxide as a pH-regulating chemical, which was an expected result in terms ofhypothesis and literature. Furthermore, the turbidity of the clear phase samplesdecreased at a sodium hydroxide dosage relative to a calcium hydroxide dosage.The results of the work have thus demonstrated the good possibility of replacing themanual dosing of solid calcium hydroxide as a pH-regulating chemical with anautomatic dosing of sodium hydroxide obtained in liquid form.

The degradation of wool keratin under conditions relevant to those of wool dyeing was investigated using the techniques of gel permeation chromatography (GPC), ion exchange gel chromatography, and amino acid analysis. Physical testing of the treated and untreated wool was also carried out to determine the physical changes occurring, parameters used being percentage elongation at the break, and the breaking strain of the fibre. Samples of wool keratin were immersed in various aqueous solutions at 1000C for 24 hours and the filtered, aqueous, oxidised extracts were analysed* The solutions used varied only in the dye, or dye intermediate present in the treatment solution. All treatment baths contained 10% owf 1.02 x 10 -2 MSulphuric VI acid; 10%owf 7.04x 10 -3 MSodium sulphate VI ; A 100 :1 liquor ratio was used in each case. Some of the dye intermediates showed a marked catalytic effect, particularly in their effect on breaking strain, a decrease of 40% in some cases. The GPC profiles of the extracted proteins were examined in detail and compared against previous workers' results. An explanation of the behaviour of the dyes and intermediates was proposed. The amino acid composition data of the extracted and fractionated proteins were compared against various morphological components extracted by other workers, as was the total gelatin obtained from each treatment. / Science Research Council