Thesis (Ph.D.) --Murdoch University, 2003. / Thesis submitted to the Division of Science and Engineering. Includes bibliographical references (leaves 172-181).

Thesis (M.A.)--University of Wisconsin--Madison, 1974. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Master-Arbeit Univ. St. Gallen, 2007.

Orientador: Marcia Miguel Castro Ferreira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T07:45:07Z (GMT). No. of bitstreams: 1 Escobar_EduardoMarchioni_M.pdf: 4616166 bytes, checksum: 408a53eb5fa36485cc72a600c9361d94 (MD5) Previous issue date: 2004 / Mestrado / Físico-Química / Mestre em Química

For the majority of tailings substrates, flocculant adsorption proceeds through hydrogen bonding of the amide functionalities with neutral surfaces. However, flocculation of Bayer process residue solids takes place in highly caustic liquors, typically using high molecular weight polyacrylates. This represents an almost unique situation, and implies a totally different adsorption mechanism. Direct examination of polyacrylate adsorption within the complex matrix of real liquors and a mixture of residue phases is difficult, making it necessary to focus on a model substrate (hematite) and synthetic liquors (pH 13 at high ionic strength). Previous spectral studies have used ex situ techniques, with sample drying potentially altering the adsorbed species, leading to inconclusive results. This study presents for the first time direct in situ evidence of polyacrylate adsorption onto hematite obtained by Fourier Transform Infrared-Attenuated Total Reflection (FTIR-ATR) Spectroscopy. Adsorption and hence concentration of dilute polyacrylate solutions onto hematite-coated zinc selenide optics has provided spectra of adsorbed polymer under a range of conditions, unbiased by any contribution from the bulk polymer solution. Analysis of the polyacrylate carbon-oxygen stretching frequencies established differing modes of adsorption at low and high pH conditions. At pH 2 adsorption proceeded through bidentate chelation of the carboxylate to a surface ferric ion, facilitated through deprotonation of a carboxylic acid group and removal of a hematite surface hydroxyl group, i.e. chemisorption. Unshifted carboxyl peaks in the spectrum enabled the unadsorbed 'loops' and 'tails' to be distinguished from the adsorbed polymer, and represented at least 70% of the total polymer chain length. / In contrast, at pH 13 adsorption of polyacrylate occurs via physisorption and was only possible with the addition of electrolyte. This adsorption was enhanced with increasing electrolyte concentrations up to 1 M NaCl. The hematite surface charge was negative at high pH, however with increasing ionic strength the specific adsorption of Na+ ions decreased the negative surface charge, and at very high salt concentrations the surface became positively charged. For electrolyte with different monovalent cations, polymer adsorption increased in the order Li+ > Na+ > Cs+. The identity of the monovalent cation had no effect on the polymer solution dimensions but the ability to reduce the magnitude of the hematite surface charge followed the same trend. This finding is consistent with the 'structure making - structure breaking' model proposed by Berube and de Bruyn. At both high and low pH, polyacrylate exhibited adsorption isotherms that are best described by the Langmuir expression. Surface coverage was greatest at low pH due to more available surface sites and the adsorbed polymer conformation (a greater fraction of loops and tails). Adsorbed conformation and hence maximum adsorption was independent of molecular weight at low pH, however at high pH maximum adsorption increased with increased molecular weight, indicating an adsorbed polymer configuration exhibiting a greater degree of loops and tails. While the individual carboxylate-surface interaction was stronger at low pH than high pH, both were relatively weak. Despite this, none of the polymers could be removed by washing, demonstrating the strength and irreversibility of the multi-attached polymer molecules. / The stronger individual carboxylate-surface interactions at low pH is indicative of a higher activation energy of formation, and may be a contributing factor to the slower rate of adsorption at low pH. The rate of polyacrylate adsorption was dominated by mass transport limitations in all cases. The initial rate of adsorption was greater at lower polymer molecular weight, consistent with the relative polymer diffusion coefficients. This rate of adsorption was much less dependent on polymer molecular weight at high pH than at low pH, suggesting significantly different polymer-solvent interactions. It was clearly demonstrated that the sodium ion concentration within the high ionic strength Bayer liquors is more than sufficient to facilitate polyacrylate adsorption on bauxite residue. There is no need to postulate calcium bridging between the polymer and surface, as has been suggested in previous studies. Improved settling and clarity associated with the presence of calcium on residue surfaces is more likely due to enhanced particle coagulation prior to flocculation. FTIR-ATR has been shown to be an excellent tool for the in situ examination of polyacrylate adsorption onto hematite, and will be a powerful technique for the characterisation and subsequent comparison of the adsorption behaviour of other systems.

Gibbsite scale growth in pipe fittings is a major problem for an alumina refinery. A recent investigation into the scale growth mechanism at an alumina refinery found almost 60 % more scale growth in a reducer when compared with the connecting straight pipe sections for similar flow conditions. Scale growth occurs where liquor (supersaturated solutions) come in contact with solid surfaces and it is affected by the liquor flow velocity besides other physical and chemical parameters. The present work is dedicated to study the hydro-dynamical aspects of the mechanism of scale growth. In particular, the role of the phenomenon of turbulent bursting, stream wise and cross stream fluctuating velocity components (Ux and Uy) was investigated as the flow moves through the reducer. Particle Image Velocimetry (PIV) technique was used to get a full view of the reducer and the readings close-to-the-wall of the reducer at Reynolds number of 27,000 and 44,000 upstream which corresponds to Reynolds number of 41,500 and 66,000 downstream of the reducer respectively. The results showed an increase in cross stream and a decrease in magnitude of stream wise fluctuating velocity components, whereby we presume that the increased cross stream fluctuating velocity component increases the frequency of impacts of the scaling particles on the wall thus initiating excessive scale growth in the reducer when compared with the connecting straight pipe sections, for similar flow conditions.

Univ., Diss.--Bonn, 2006.

Dissertation--Bamberg--Otto-Friedrich-Universität, 2006. / Bibliogr. p. 265-280.

Thesis (PhD)--University of South Australia, 1997

Low temperature (165°C) Wet Oxidation (WO) and Catalytic Wet Oxidation (CWO) of 12 organic compounds has been studied in highly alkaline, high ionic strength solution (simulating that encountered in the Bayer process used to refine alumina) for the first time. Most (11 out of 12) of the 12 organic compounds studied (formic, acetic, propionic, butyric, oxalic, malonic, succinic, glutaric, citric, lactic, malic and tartaric acids) have been identified in various worldwide Bayer liquors. The various aspects of WO and CWO studied for each of the above-mentioned compounds were as follows; -Extent of complete oxidation to carbonate (i.e. extent of removal of organic compound) -Extent of overall oxidation (i.e. extent of complete oxidation and partial oxidation to stable products) -The product(s) formed from partial (incomplete) oxidation -The reaction mechanism occurring -Why certain compounds undergo low temperature WO and/or CWO in highly alkaline, high ionic strength solution -The ability of various transition metal oxides to catalyse the WO of the selected organic compounds Of the 12 organic compounds studied only six (formic, malonic, citric, lactic, malic and tartaric acids) underwent appreciable (>2% overall oxidation) WO in isolation under the reaction conditions used (4.4 -7.0 M NaOH, 165°C, 500 kPa Po₂, 2 hours). Each of these six compounds underwent some complete oxidation and therefore can be partly removed from highly alkaline, high ionic strength solution using low temperature WO. The order of extent of complete oxidation determined was as follows tartaric> citric> malonic> formic> lactic> malic. All of these compounds also underwent some partial oxidation under the reaction conditions used, excluding formic acid, which only underwent complete oxidation. Oxalic acid was a major product of partial oxidation of all of the above-mentioned compounds (excluding formic acid), while acetic acid was a major product of partial oxidation of citric, lactic, malic and tartaric acids. The WO of formic, malonic, citric, lactic, malic and tartaric acids varied considerably with NaOH concentration over the NaOH concentration range studied (4.4 - 7.0 M). The extent of overall oxidation undergone by each of these compounds increased significantly with increasing NaOH concentration. All of the compounds that underwent appreciable WO under the reaction conditions studied contained hydrogen(s) significantly more acidic then the compounds that did not undergo appreciable WO, thus indicating that only organic compounds that contain acidic (albeit weakly acidic) hydrogens undergo low temperature (165°C) WO in highly alkaline, high ionic strength solution. Two different reaction mechanisms were identified to occur during low temperature WO in highly alkaline, high ionic strength solution. Malonic and formic acids underwent WO predominantly via a free radical based reaction mechanism, while citric, lactic, malic and tartaric acids underwent WO predominantly via an ionic based reaction mechanism. The six organic compounds that did not undergo appreciable WO in isolation (acetic, propionic, butyric, oxalic, succinic and glutaric acids) all underwent appreciable WO when in the presence of malonic acid undergoing low temperature WO. Hence, low temperature WO of all of the above-mentioned compounds can be initiated by free radical intermediates produced by malonic acid undergoing WO in highly alkaline, high ionic strength solution. The ability of several transition metal oxides to catalyse the WO of the chosen 12 organic compounds was investigated. Of the transition metal oxides studied CuO was clearly the most active. Five of the organic compounds studied (malonic, citric, lactic, malic and tartaric acids) were catalytically wet oxidised by CuO in highly alkaline, high ionic strength solution in isolation. The order of catalytic activity observed was malonic > tartaric> lactic> malic> citric. Two different catalytic reaction mechanisms were identified for CuO catalysed WO in highly alkaline solution for the organic compounds studied. CuO catalysed the WO of malonic acid predominantly by catalysing the formation of free radical intermediates. CuO catalysed the WO of citric, lactic, malic and tartaric acids predominantly via a complexation-based reaction mechanism.