Statistical Approach to the Transformation of Fly Ash into Zeolites

The experimental conversion of F-class fly ash into zeolites is described. The ash, composed mainly of aluminosilicate glass, mullite and quartz, was collected in the Cracow power plant (southern Poland). The experiments involved the heating of fly ash samples in PTFE vessels. Time, temperature and solution composition were the reaction parameters considered in the experiments and in the subsequent modeling. A series of reactions with 0.5, 3 and 5M NaOH solutions (and some with additional 3M NaCl) were carried out at 70°, 100° and 150°C for 12-48 hours under autogenic pressure (not measured) and at a constant ash-to-solution ratio of 33.3 g/l. The following zeolite phases were synthesized: sodalite (SOD structure), hydroxysodalite (SOD), CAN type phases, Na-X (FAU), and NaP1 (GIS). Statistically calculated relationships based on the mineral- and chemical compositions of the reaction products support the conclusion that the type of zeolite phase that crystallizes depends on the concentration of OH- and Cl- in solution and on the temperature of the reaction. The duration of reaction, if on the order of tens of hours, is of less significance. The nature of the zeolite phase that crystalises is controlled by the intensity and selectivity of the substrate dissolution. That dissolution can favour, in sequence, one or other of the components in the substrate, resulting in Si/Al variation in the reaction solutions. Mullite dissolution (decreasing solution Si/Al) characterizes the most advanced reaction stages. The sequence of crystallization of the zeolite phases mirrors the sequential dissolution of substrate components, and the composition of the crystallizing zeolite crystals reflects the changes in the solution Si/Al.