Four Australian coals, Blair Athol, Ebenezer, Newlands and Warkworth coals, were demineralized by Ca(OH)(2) digestion at 300 degrees C, followed by washing with dilute HCl. Ash contents decreased from 8.8-15.4% to I% for Blair Athol, Newlands and Warkworth coals, and from 14.9% to 2.8% for Ebenezer coal. The CaO/ash ratio is an important factor affecting coal demineralization; the maximum ash removals were achieved at CaO/ash ratios in the range 0.61 g/g for all the coals. The major minerals in the original coals were kaolinite and quartz, with some montmorillonite and carbonates. Kaolinite and quartz hydrothermally reacted with Ca(OH)(2) form calcium-bearing hydrated silicates and aluminosilicates, such as tobermorite and hibschites, that could be dissolved in acid. With increasing CaO/ash ratio in excess of the optimum value, the removal of quartz significantly decreased; there also remains some calcium in treated coal, depending on digestion conditions and coal type. A lower ash removal from Ebenezer is due to a lower quartz removal and more remaining calcium.