Recovery of yttrium and europium from spent fluorescent lamps using pure levulinic acid and the deep eutectic solvent levulinic acid–choline chloride

Abstract

A solvometallurgical approach for the recovery of rare-earth elements from lamp phosphor waste was developed. The solubility of individual phosphors in different deep-eutectic solvents (DESs) was measured. The DES levulinic acid–choline chloride (x_ChCl = 0.33) showed high solubility of the YOX phosphor (Y₂O₃:Eu³⁺) and low solubility of the HALO phosphor (Sr,Ca)₁₀(PO₄)(Cl,F)₂:Sb³⁺,Mn²⁺, which does not contain any rare-earth element. This DES was selected for further investigation. When the DES was compared to pure levulinic acid, very similar leaching behaviour was observed, showing that the proton activity is more important than the chloride as a metal ligand. The leaching of YOX and HALO using levulinic acid–choline chloride (x_ChCl = 0.33) or pure levulinic acid was optimised in terms of water content, temperature and leaching time. The optimised parameters were validated in a synthetic mixture of phosphors and in real lamp phosphor waste. The co-dissolution of HALO is higher in the real waste than in the synthetic mixture. The real waste was also leached with an aqueous solution of hydrochloric acid, which was non-selective against dissolution of YOX, and with the functionalised ionic liquid betainium bis(trifluoromethylsulfonyl)imide. The ionic liquid gave a similar selectivity as levulinic acid, but is much more expensive. The recovery of the metals from the pregnant leach solution was tested via precipitation with oxalic acid and solvent extraction. Oxalic acid precipitation was not suitable for the DES system. The metals could be extracted via solvent extraction with the acidic extractant bis(2-ethylhexyl)phosphoric acid (D2EHPA) and stripped by an aqueous hydrochloric acid solution. Pure levulinic acid was found to be more suitable than the corresponding ChCl-based DES for the selective recovery of YOX.