[Adsorption of Phosphate from Aqueous Solution on Hydrous Zirconium Oxides Precipitated at Different pH Values]

Abstract

In this study, hydrous zirconium oxide (HZO) samples precipitated at different pH values were prepared, characterized and used as adsorbents to remove phosphate from aqueous solution. The adsorption characteristics and mechanisms of phosphate on these HZO samples were investigated. The results showed that the presence of Na⁺ slightly enhanced the adsorption of phosphate on HZO samples prepared at precipitation pH of 4.8 and 8.0, but it greatly enhanced the adsorption of phosphate on HZO prepared at precipitation pH of 10.6. The presence of Ca²⁺ slightly enhanced the adsorption of phosphate on HZO prepared at precipitation pH of 4.8, but it significantly enhanced the adsorption of phosphate on HZO samples prepared at precipitation pH of 8.0 and 10.6. The presence of HCO₃^- or SO₄^2- inhibited phosphate adsorption onto HZO, and the inhibitory effect of these anions on phosphate adsorption onto HZO precipitated at pH 4.8 was much higher than that on phosphate adsorption onto HZO samples precipitated at pH 8.0 and 10.6. The phosphate adsorption was dependent upon solution pH, and it decreased with increasing solution pH. The Langmuir, Freundlich and Dubinin-Redushckevich (D-R) isotherm models fitted well to the adsorption equilibrium data of phosphate on HZO samples precipitated at pH 4.8, 8.0 and 10.6. In the presence of Na⁺ but in the absence of Ca²⁺, there was no significant difference of the maximum phosphate monolayer adsorption capacity derived from the Langmuir isotherm model among HZO samples prepared at precipitation pH of 4.8, 8.0 and 10.6. In the presence of Ca²⁺, the maximum phosphate monolayer adsorption capacity derived from the Langmuir isotherm model for HZO precipitated at pH 8.0 or 10.6 was much higher than that for HZO precipitated at pH 4.8. The mechanism for phosphate adsorption onto HZO mainly obeyed the inner-sphere complexing mechanism. The surface chloride and hydroxyl groups played the key role in the adsorption of phosphate on HZO precipitated at pH 4.8 or 8.0, while only the surface hydroxyl groups played the key role in the adsorption of phosphate on HZO precipitated at pH 10.6. Results of this work demonstrated that the HZO precipitated at pH 8.0 or 10.6 was a more promising adsorbent for removing phosphate from wastewater than the HZO precipitated at pH 4.8.

Keywords: adsorption; hydrous zirconium oxide; ligand exchange; phosphate; precipitated pH values.