Granular zirconium-aluminum hybrid adsorbent (GZAHA) was fabricated for efficient defluoridation of groundwater in filter application. GZAHA was formed through the aggregation of massive Zr/Al oxide nanoparticles with an amorphous pattern. This adsorbent has a satisfactory mechanical strength, a specific surface area of 29.55 m2/g, and numerous hydroxyl groups on the surface. F adsorption equilibrium could be achieved within 12 h, and the sorption process followed a pseudo-second-order reaction rate. The maximum adsorption capacity of F estimated from the Langmuir model was 65.07 mg/g at 25 °C, being greater than most of other granular adsorbents. The removal efficiency of F could be maintained in a wide pH range of 5~9. The presence of phosphate posed an adverse effect on F adsorption due to the competition mechanisms. The saturated adsorbents could be regenerated and reused for four times by using sodium hydroxide solution as an eluent, and the adsorption capacity remained around 80%. Besides electrostatic attraction and Al-F complex, surface complexation and anion exchange were also involved in the adsorption process. Continuous adsorption experiments illustrated that 808 bed volumes of F-contaminated water (F = 5 mg/L) were treated successfully by a GZAHA-packed column without second pollution.
Keywords: Adsorption; Aluminum oxide; Fluoride; Granular adsorbent; Zirconium oxide.