Porous metakaolin geopolymer as a reactive binder for hydroxyapatite adsorbent granules in dye removal

In this study, porous hydroxyapatite-metakaolin geopolymer (HAP-MK-GP) granules were prepared with a novel method for adsorption of organic pollutants from aqueous solutions, using brilliant green dye as a model compound. The preparation involved combining finely powdered hydroxyapatite, metakaolin, and solid sodium metasilicate in a high-shear granulator. Then, hydrogen peroxide (H2O2) was added at different concentrations (0.0, 5.0, 7.5, or 10.0%) as a combined granulation fluid and blowing agent. In the resulting granules, metakaolin geopolymer bound the powdered hydroxyapatite as granules and contributed to the adsorption capacity. To determine their structural, morphological, and mechanical properties, the granules were characterized with infrared spectroscopy, X-ray fluorescence, scanning electron microscopy, specific surface area and porosity analysis, and compressive strength tests. The granules had a high porosity and promising compressive strength and Young's modulus of 0.8 and 10 MPa, respectively, potentially enabling their use in large-scale adsorption columns. The monolayer adsorption mechanism of brilliant green dye onto HAP-MK-GP granules was confirmed by fitting the obtained batch adsorption data to the Langmuir isotherm model which showed that the adsorption capacity was approximately 41 mg/g. The optimum conditions were: pH of 7, initial dye concentration of 100 mg/L, adsorbent dose of 3 g/L, agitation speed of 250 rpm, contact time of 30 min, and temperature of 298 K. The adsorption kinetic data indicated that the adsorption followed the pseudo-second-order kinetic model. The thermodynamic parameters, including Gibbs free energy, enthalpy, entropy, and activation energy, indicated that adsorption was spontaneous, endothermic, and was based on physisorption. The rate-limiting step was film diffusion. Based on the results, HAP-MK-GP granules could be a feasible adsorbent for the removal of dyes from industrial wastewater. Moreover, the facile granulation method presented here could be applied to other powdered adsorbents as well to prepare adsorbent granules.