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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Tensioactif carboxylique polyéthoxylé pour la flottation ionique : étude fondamentale de la solution à la mousse / Polyethoxylated carboxylic surfactant for ion flotation

Micheau, Cyril 13 November 2013 (has links)
La flottation ionique est un procédé de séparation permettant d'extraire et de concentrer des ions dans une mousse formée à l'aide d'un tensioactif. Pour les systèmes classiques, la forte interaction entre les ions et le tensioactif collecteur entraîne généralement la formation de précipités. Une fois la mousse collapsée, le résidu solide récupéré nécessite un traitement particulier pour permettre sa valorisation ou son conditionnement. Afin de remédier à cet inconvénient, ce travail propose d'utiliser comme collecteur un tensioactif carboxylique polyéthoxylé, l'AKYPO® RO 90 VG, ayant la particularité de former des complexes ion-tensioactifs solubles, et ce également avec des ions multichargés. Ce travail présente une étude poussée des mécanismes fondamentaux qui régissent l'extraction d'ions par formation de mousses. Dans une première partie, les propriétés tensioactives et acide base du collecteur en solution sont étudiées en combinant nombre de techniques indépendantes que sont le dosage pHmétrique, la tensiométrie et la diffusion aux petits angles. L'évolution de ces propriétés en présence de différents sels de nitrates (Nd, Eu, Ca, Sr, Cu, Li, Na, Cs) couplée à des mesures électrophorétiques donneront une première approche de la sélectivité. Enfin, l'ensemble de ces données associées à une étude de la formation des complexes tensioactif/ion permettra d'établir la spéciation du système Nd/AKYPO® en fonction du pH. Dans une seconde partie, l'analyse de la conductimétrie et de la diffusion de neutron aux petits angles permettront d'établir les paramètres régissant la formation et stabilité des mousses de flottation. Le pH et la nature des ions ajoutés, leur nombre de charge ainsi que leur nature chimique, apparaissent ainsi comme les paramètres majeurs gérant l'humidité et l'épaisseur de film des mousses. La dernière partie est dédiée à la compréhension des expériences d'extraction/séparation ionique par flottation en s'appuyant sur l'ensemble des résultats obtenus précédemment. Il est montré que la flottation du néodyme est fortement liée à sa spéciation, pouvant conduire à sa dés-extraction ou sa flottation sous forme particulaire. Il est également montré que le néodyme induit un phénomène de déplétion des ions monovalents dans la mousse. Cette spécificité ionique permet d'envisager le système étudié pour la séparation d'ions par le procédé de flottation. / Ion foam flotation allows to concentrate ions in a foam phase formed by a soap. For classical systems, the strong interaction between ions and surfactant generally leads to the formation of precipitates and of froth. When the froth collapses, the solid residue thus recovered requires a recycling or conversion. In order to remedy this, the present work uses as collector a polyethoxylated carboxylic surfactant, AKYPO® RO 90 VG, which forms soluble ion/surfactant complexes, even with multi-charge ions. This work presents a detailed study of the fundamental mechanisms that govern the extraction of ions by foaming. In the first part, surface activity and acid/base properties of the surfactant in solution are determined by combining numerous independant techniques which are pHmetric dosage, tensiometry and small angle scattering. The evolution of these properties in the presence of different nitrate salts (Nd, Eu, Ca, Sr, Cu, Li, Na, Cs) coupled with electrophoretic measurements give a first approach to selectivity. Finally, all of these data combined with a study of the formation of surfactant/ion complexes allow us to determine the speciation of Nd/AKYPO® system as a function of pH. In the second part, the analysis of the foam by conductivity and neutron scattering provides information on the wetness and foam film thickness, parameters governing foam stability. The pH and the nature of the added ions, their number of charge and also their chemical nature thus appear to be major parameters that governed wetness and foam film thickness. The last part is devoted to the understanding of the ion extraction/separation experiments by flotation based on all previous results. It is shown that the flotation of neodymium is strongly related to its speciation, which could lead to its re-extraction or its flotation in precipitated form. It is shown that, neodymium induces a phenomenon of mono-charge ion depletion in the foam. This ionic specificity allows to consider the studied system for ion separation by the flotation process.
2

Fundamental Characterization and Technical Aspects of a Chelating Surfactant

Svanedal, Ida January 2014 (has links)
The purpose of this study was to investigate the fundamental characteristics of a chelating surfactant in terms of solution behaviour, chelation of divalent metal ions, and interaction in mixtures with different foaming agents and divalent metal ion, as well as examining its prospects in some practical applications. Chelating surfactants are functional molecules, with both surface active and chelating properties, which are water soluble and therefore suitable for chelation in many aqueous environments. The dual functionality offers the possibility to recover the chelating surfactant as well as the metals. The DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 4-C12-DTPA (2-dodecyldiethylenetriaminepentaacetic acid) was synthesized at Mid Sweden University. In the absence of metal ions, all eight donor atoms in the headgroup of 4-C12-DTPA are titrating and the headgroup charge can be tuned from +3 to -5 by altering the pH. The solution properties, studied by surface tension measurements and NMR diffusometry, were consequently found strongly pH dependent. pH measurements of chelating surfactant solutions as a function of concentration was used to extract information regarding the interaction between surfactants in the aggregation process. Small differences in the conditional stability constants (log K) between coordination complexes of DTPA and 4-C12-DTPA, determined by competition measurements utilizing electrospray ionization mass spectrometry (ESI-MS), indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. This was further confirmed in hydrogen peroxide bleaching of thermomechanical pulp (TMP) treated with 4-C12-DTPA. Interaction parameters for mixed systems of 4-C12-DTPA and different foaming agents were calculated following the approach of Rubingh’s regular solution theory. The mixtures were also examined with addition of divalent metal ions in equimolar ratio to the chelating surfactant. Strong correlation was found between the interaction parameter and the phase transfer efficiency of Ni2+ ions during flotations. Furthermore, a significant difference in log K between different metal complexes with 4-C12-DTPA enabled selective recovery of the metal ion with the highest log K. The findings in this study contribute to the understanding of the fundamental characteristics of chelating surfactants, which can be further utilized in practical applications.

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