Quasi Natural Approach for Crystallization of Zeolites from Different Fly Ashes and Their Application as Adsorbent Media for Malachite Green Removal from Polluted Waters

Worldwide disposal of multi-tonnage solid waste from coal-burning thermal power plants (TPPs) creates serious environmental and economic problems, which necessitate the recovery of industrial waste in large quantities and at commercial prices. Fly ashes (FAs) and slag from seven Bulgarian TPPs have been successfully converted into valuable zeolite-like composites with various applications, including as adsorbents for capturing CO2 from gases and for removal of contaminants from water. The starting materials generated from different types of coal are characterized by a wide range of SiO2/Al2O3 ratio, heterogeneous structure and a complex chemical composition. The applied synthesis procedure resembles the formation of natural zeolites, as the raw FAs undergo long-term self-crystallization in an alkaline aqueous solution at ambient temperature. The phase and chemical composition, morphology and N-2 adsorption of the final zeolite products were studied by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), X-Ray Diffraction (XRD) and Brunauer-Emmett-Teller (BET) analyses. The growth of faujasite (FAU) crystals as the main zeolite phase was established in all samples after 7 and 14 months of alkaline treatment. Phillipsite (PHI) crystals were also observed in several samples as an accompanying phase. The final products possess specific surface area over 400 m(2)/g. The relationships between the surface properties of the investigated samples and the characteristics of the raw FAs were discussed. All of the obtained zeolite-like composites were able to remove the highly toxic dye (malachite green, MG) from water solutions with efficiency over 96%. The experimental data were fitted with high correlation to the second-order kinetics.