Separation of cerium from solution by oxidative precipitation with hydrogen peroxide: The reaction mechanism

Abstract

Cerium removal from solution via oxidative precipitation with hydrogen peroxide was investigated in a batch reactor to identify optimum conditions for maximum Ce removal. Tests were performed under ambient temperature at pH 2, 3, 4 and 5, using the exact stoichiometric requirement and 30 % and 50 % excess, respectively. It was found that, unlike the usual direct Ce(OH)₄ formation presented in the literature for most oxidants, the reaction with hydrogen peroxide proceeded via a metastable ceric hydroxide, with conversion rates increased by increasing temperature. Standard free energies of reaction were calculated for both routes. To better understand the process, the oxidation of Ce(III) to Ce(IV) and the precipitation of Ce(OH)₄ were studied separately via a decoupled approach at low pH and reaction mechanisms for each process were proposed. The Ce(III) oxidation reaction was identified as the rate-limiting step, whereas Ce(IV) precipitation was fast and quantitative. In the pH range of 3–5, Ce removal extents varied between 80 and 95 %, depending on the hydrogen peroxide excess. Following the Ce removal step via oxidative precipitation, it was found that a 2 h ageing stage at 80 °C and pH 2.5 was required to complete the transition of cerium hydroxy-peroxide to the more stable ceric hydroxide and decompose any residual H₂O₂.