Journal of the Southern African Institute of Mining and Metallurgy
versión On-line ISSN 2411-9717
South Africa and Australia are the biggest suppliers of zircon sand to the international zirconium industry. However neither South Africa nor Australia is well known for zircon beneficiation. Geratech Zirconium Beneficiation Ltd (GZB) continued with additional research on sodium hydroxide (NaOH) cracking of zircon sand during 2002-2003. In 2003 GZB started extracting zirconium from zircon sand by means of NaOH cracking on a commercial scale. Experience has shown that temperature profile and atmospheric control inside the furnace is crucial for the beneficiation of zircon sand. Silica carryover to zirconium chemicals could result if a high temperature is used. Once the sodium silicate is extracted from the sodium zirconate and dissolved in hydrochloric acid, two distinct routes can be followed to precipitate various zirconium chemicals. The most common route is to precipitate zirconium oxychloride crystals (ZOC), with subsequent purification from all contaminants (crystal route). Less known is the process (liquid route) that involves the direct precipitation of zirconium basic sulphate (ZBS). This route will yield a less pure product, with contaminants such as silica and titanium. An important factor in this route is the prevention of silica gel formation, which could hamper final product filtration. For applications like paint drying (zirconium octoate) or antiperspirants (zirconium hydroxychloride) low levels of contaminants have no effect on the final product. The advantage of the liquid route is fewer production stages compared to the crystal route. The disadvantage of the liquid route is that the market for the products will be significantly smaller. The optimum solution could be a plant design that could cater for both routes. Another example of an application of zirconium chemicals is the use of ammonium zirconium carbonate (AZC) in the paper industry. Zirconium basic carbonate (ZBC) is dissolved in ammonium carbonate to produce AZC solution. AZC is used mainly in European countries in the paper industry. For example, carton boxes were initially produced with formaldehyde as the binder, however, it has now been replaced with AZC since formaldehyde is considered toxic. AZC reacts with the cellulose fibres in the paper to act as the binder. The resulting product is not toxic, and printing ink dries very quickly due to the porous paper structure. Other applications of zirconium chemicals involve the use of acid zirconium sulphate tetrahydrate (AZST), zirconium orthosulphate (ZOS), potassium zirconium carbonate (KZC), and zirconium hydrous oxide (ZHO). Fluoride-based zirconium chemicals like zirconium tetra-fluoride (ZrF4) and hexafluoro-zirconic acid (H2ZrF6) are used in the aluminium industry. Zirconium oxide (ZrO2) can be produced from any of the abovementioned precipitated chemicals via a high-temperature decomposition process. The physical properties of such oxides can differ tremendously, depending on the final application. The fired density of sanitaryware is typically 5.8 g/cm3, compared to milling media at >6.1 g/cm3. The required fired density is achieved by controlling the precipitation and decomposition conditions for these two oxides. The same applies to stabilized and mixed oxides, for example where zirconium oxide acts as an oxygen carrier in fuel cells.