The effect of isotopic substitution of deuterium for hydrogen on the morphology of products precipitated from synthetic Bayer solutions

Abstract

In the production of alumina (Al 2O 3), the precipitation of gibbsite (Al(OH) 3) is the slowest step in the Bayer process. Gibbsite growth rates are generally in the vicinity of microns per hour. Thus, research is focussed on increasing productivity (gibbsite precipitation rates) without compromising product quality. Fundamental to this is an improved understanding of gibbsite growth mechanisms. Isotopic substitution of deuterium for hydrogen in synthetic Bayer (sodium aluminate) solutions was used primarily to investigate deprotonation and reprotonation of the surface hydroxyl groups. Gibbsite precipitates in a highly alkaline solution. The hydroxyl groups situated on the surfaces of the growing crystals are likely to be deprotonated because the pH of the Bayer liquor is >14 and the pK a for the surface protons is in the range of 9–10. The rate of gibbsite growth may therefore depend on the deprotonation and reprotonation of the hydroxyl groups, as the gibbsite crystal lattice consists of hydrogen bonded layers of Al(OH) 3. However, the gibbsite precipitation rates from equivalent sodium aluminate solutions (NaAl(OH) 3 and NaAl(OD) 3) were very similar, indicating that the deprotonation and reprotonation of the hydroxyl groups are not rate-limiting. Nonetheless, the isotopic substitution of deuterium for hydrogen in synthetic Bayer solutions did have effects on the gibbsite solubility, crystallization growth process, product phase and morphology. This paper focuses on the changes in product morphology. Isotopic substitution resulted in changes in the orientation of nuclei formed on seed surfaces as well as the nuclei morphology. This is the first time that isotopic substitution has been used to investigate gibbsite precipitation in synthetic Bayer solutions.