Bleaching of kaolins and clays by chlorination of iron and titanium

The quality of the clays and over all kaolin is measured in function of iron content, since this element gives an undesirable reddish color to this type of minerals. The use of chlorination for iron and titanium removal from different clay and kaolin minerals, used in Argentinian ceramic industry, has been investigated to establish reaction mechanisms, precautions and optimal conditions to bleach the clays. The method consists of the calcinations of the pellets in a flow of chlorine gas at temperatures between 700 and 950 °C, to remove the iron and the titanium by volatilization of the respective chlorides. Isothermal and non-isothermal chlorination assays were made and the effects of the temperature, reaction time, and carbon content in the sample over the bleach of the minerals and the phase transformations suffered by these minerals during the chlorination step were investigated. The removed amounts of iron and titanium were determined by X-ray fluorescence, the phase transformations were followed by X-ray diffraction and the samples' bleaching was established making an analysis of the space of the color by the spectrophofotometric method CIELAB. Also, a thermodynamic analysis of the system using HSC Chemistry for Windows software was made. The experimental results show that for red clay with high colloidal iron content, the optimum working temperature for the iron quantitative removal, without aluminium loss, is close to 850 °C, in controlled atmosphere free of O2 and H2O; lower temperatures require long reaction times. The extraction of titanium is not quantitatively achieved, as that of iron, even for long reaction times, because this element is present in different structures, with the consequent variation of its reactivity. The content of carbon and organic matter in the clays, in the case of the San Luis red clay, is enough for extraction improvement. However, the optimum concentration of carbon can vary depending on the type of clay and the amount of Fe2O3 in the mineral. The formation of phases such as α-Al2O3, a product of chlorination, increases the piece hardness. The methodology used in this work allows for obtaining a great improvement in the color of the final product of the firing, achieving ceramic materials with notable whiteness, even with red clays. © 2006 Elsevier B.V. All rights reserved.