Thesis (PhD)--University of South Australia, 1999

Thesis (PhD)--University of South Australia, 1999

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

Although the precipitation of aluminium trihydroxide as gibbsite, via the Bayer process has been widely studied, the mechanism of crystal growth is poorly understood. This work focus on the morphology of gibbsite and the relative growth rates of individual crystal faces.Initial work was carried out to characterize aluminium trihydroxide and it was found that bayerite, another polymorph, precipitated at temperatures below 50 [degrees] C and its morphology depended on the method of precipitation. Gibbsite however, precipitated above this temperature and its morphology depended on the type of alkali aluminate solutions used. The method of precipitation does not affect the morphology, only the size of the precipitate formed. The morphology of gibbsite can be altered by the addition of organic compounds which are known to inhibit gibbsite precipitation. Some of these compounds were found to selectively inhibit the growth of individual crystal faces, thus altering the overall morphology of gibbsite. Boehmite, a polymorph of aluminium hydroxide, can be produced by partial dehydration of gibbsite at 300T. The morphology of boehmite consisted of diamond shaped crystals.The influence of cation incorporation on the morphology of gibbsite was studied experimentally and computationally (molecular modelling). These studies showed that there is a linear relationship between the amount of cation incorporated and atomic radii and between the amount of cation incorporated and the defect energy calculated. The equilibrium morphology of gibbsite predicted in the absence of media matched the morphology of gibbsite grown slowly from sodium aluminate, implying that the amount of sodium incorporation is low in these crystals.The growth rates of individual crystal faces were measured in situ, and found to be a function of supersaturation squared for the prismatic faces, possibly indicating ++ / that E growth occurs by spiral growth mechanism. The growth of the basal face was found to follow the spiral growth mechanism below a relative supersaturation of 0.815 and the birth and spread mechanism above this level. The activation energies and kinetic coefficients for the individual prismatic faces were also determined.Growth rate dispersion was observed in these microscopic studies, but the question of size dependency remains unanswered.The overall growth rates of gibbsite crystal, determined using rapid dynamic light scattering, was found to be an exponential function of supersaturation indicative of a birth and spread growth mechanism.

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.

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

Thèse (M.Eng.) -- Université du Québec à Chicoutimi, 2003. / Bibliogr.: f. 130-134. Document électronique également accessible en format PDF. CaQCU

Thèse (M.Eng.) -- Université du Québec à Chicoutimi, 2003. / Bibliogr.: f. [184]-191. Document électronique également accessible en format PDF. CaQCU

Sodium oxalate is one of the many organics present in Bayer liquor. Due to its limited solubility, sodium oxalate can co-precipitate with alumina trihydrate during precipitation. This can have detrimental effects on the final product quality, especially if it occurs in the initial stages of precipitation.Quaternary amine type cationic surfactants can prevent sodium oxalate co-precipitation and increase the tolerable concentration of sodium oxalate in Bayer liquor. Their action is via the inhibition of nucleation or/and the inhibition of crystal growth. This study presents work detailing the effect of quaternary amines on sodium oxalate crystal growth in Bayer liquor.A series of quaternary amines were tested and classified as strong, medium or weak crystal growth inhibitors in plant liquor. The octadecyltrimethylammonium bromide was found to be the most effective under plant conditions.Results will show that while quaternary amines inhibit crystal growth in Bayer liquor, they have no effect on crystallization in synthetic liquor. It has been postulated that the presence of certain organic molecules is required for quaternary amines to crystallization and therefore stabilize the liquor. The inhibition of oxalate crystal growth in Bayer process liquors is due to the plant organics present, and the stabilizing effect of quaternary amines is the result of an interaction between quaternary amines and plant humic material on the oxalate surface. A series of organics, anionic macromolecules and anionic surfactants, have been tested to simulate the behaviour of plant humates, and their inhibitory effect on sodium oxalate crystal growth has been measured.A method for the analysis of the strongest quaternary amine has been adopted, improved and modified in order to fulfil experimental conditions.The CMC of quaternary amines has been determined in liquor. Surface tension ++ / measurements revealed relationships between certain liquor components and quaternary amines.Adsorption isotherms of quaternary amines have been successfully generated in Bayer liquor. Investigations with quaternary amines and plant humics reveal a synergy between the two. Co-adsorption of quaternary amines and plant humates onto the oxalate surface has been found, and the effect of the components on the adsorption behaviour will be discussed. The inhibitory effect and the adsorbed amount of components have been compared. Results revealed a relationship between the amount of plant humates on the surface and the crystal growth inhibition.The nature of the adsorption has been investigated with confocal laser scanning microscopy. These results will show that humic material adsorbs at the edges and in the corners of the crystals. In the presence of quaternary amines, the humic material occupies the main crystal faces as well. The nucleation of sodium oxalate from humic solution and from a mixture of humates and quaternary amine resulted in crystals with different morphology.Fourier Transform Infrared Attenuated Total Reflection Spectroscopy investigations will present the adsorption of quaternary amine on oxalate, and will indicate that the adsorption is pH dependent.

Thèse (M.Eng.) -- Université du Québec à Chicoutimi, 2005. / La p. de t. porte en outre: Mémoire présenté à l'Université du Québec à Chicoutimi comme exigence partielle de la maîtrise en ingénierie. CaQQUQ Bibliogr.: f. 128-131. Document électronique également accessible en format PDF. CaQQUQ