Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose

Abstract

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC–Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC–Zr was 83.6 mg P/g. Furthermore, the QC–Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl−, NO3−, SO42−, SO44−) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC–Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both –N+(CH3)3 groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between –N+(CH3)3 and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO4)x). The 31P nuclear magnetic resonance (NMR) study implied that P surface–precipitated and inner–sphere complexed with zirconium hydroxide at a ratio of 3:1.