The mechanisms of action of sodium oxalate seed stabiliser molecules under Bayer conditions.

Abstract

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.