Rare earth elements recovery from secondary wastes by solid-state chlorination and selective organic leaching.

Processing of end-of-life products (EoL) containing rare earth elements (REE) has gained increasing importance in recent years with the aim of avoiding supply risks. In addition, circular economy renders complete recirculation of technology metals mandatory. Fluorescent lamp wastes are an important source for REE recovery since they contain significant amounts, up to 55 wt%, of Y and Eu in red phosphors. For these purposes, solid-state chlorination (SSC) is an economically attractive alternative to wet acid leaching treatment, which profits from a considerable reduction of chemicals consumption and process costs. Chlorination takes place with dry HCl(g) produced from thermal decomposition of NH4Cl(s), not only converting the REE content of the Hg-free phosphor waste into water soluble REE metal chlorides, but also avoiding the implications of aqueous complex chemistry of REE. To establish an industrial process viable on a commercial scale, the SSC process has been optimized by (i) using a design of experiment (DOE) varying temperature, residence time, and gNH4Cl/gsolid ratio and (ii) improved leaching of the chlorinated metals with an organic mixture selective for REE. As a result, 95.7% of the Y and 92.2% of the Eu were selectively recovered at 295.9 °C, 67 min and a ratio of 1.27 gNH4Cl/gsolid, followed by quantitative selective leaching of the REE. Owed to its low chemicals consumption and operation costs, the current process allows for valorizing lamp waste even when raw material prices are low.

Rare earths separation from fluorescent lamp wastes using ionic liquids as extractant agents.

Processing of end-of-life products has become essential in the rare earth elements (REEs) recovery field because the demand for these metals has increased over the last years due to their intensive use in advanced technologies. Fluorescent lamp wastes are considered one of the most interesting end-of-life products for investigation due to their high REEs content, mainly yttrium and europium. As a result, red phosphors (Y2O3:Eu3+ - YOX) have been chosen for evaluating their REEs' recovery potential. The REEs from a YOX reach liquor, coming from a soft leaching process have been precipitated adding oxalic acid and calcined to get the REEs in oxide form. Cyanex 572, D2EHPA and the ionic liquids, Primene 81R·Cyanex 572 IL and Primene 81R·D2EHPA IL, have been chosen to investigate the efficiency of REEs separation in chloride media. Yttrium, europium and cerium have been individually recovered by a four stages cross-flow solvent extraction process using the Primene 81R·D2EHPA IL and the Primene 81R·Cyanex 572 IL as extractants. Ce(III), Eu(III) and Y(III) have been obtained at high purities ≥ 99.9%. 4 mol/L HCl has been used to recover the yttrium and the europium from the organic phases.

Neodymium recovery from NdFeB magnet wastes using Primene 81R·Cyanex 572 IL by solvent extraction.

The necessity of Rare Earth Elements (REEs) recycling is crucial to minimizing their supply risk and provide an alternative to greener technologies. Hence, the REEs recovery from NdFeB magnet wastes using cationic extractants by solvent extraction technique has been investigated in this research. Due to the difficulty in maintaining the aqueous pH in the industrial counter-current devices when extractants like Cyanex 272 or Cyanex 572 are used, the Primene 81R·Cyanex 572 ionic liquid has been synthesised to overcome this. 99.99% Nd(III) recovery with a purity of 99.7% from an aqueous mixture of Nd/Tb/Dy in chloride medium, the three representative REEs present in the NdFeB magnets wastes, has been achieved after two stages counter-current extraction process using 0.30 M of Primene 81R·Cyanex 572 ionic liquid (1:4 A:O ratio) diluted in Solvesso 100, without any aqueous pH conditioning.

Mathematical modeling of cadmium(II) solvent extraction from neutral and acidic chloride media using Cyanex 923 extractant as a metal carrier.

This paper describes experimental work and the mathematical modeling of solvent extraction of cadmium(II) from neutral and acidic aqueous chloride media with a Cyanex 923 extractant in Exxol D-100. Solvent extraction experiments were carried out to analyze the influence of variations in the composition of the aqueous and organic phases on the efficiency of cadmium(II) extraction. In neutral and acidic chloride conditions, the extraction of cadmium(II) by the organophosphorous extractant Cyanex 923 (L) is based on the solvation mechanism of neutral H(n)CdCl((2+n)) species and the formation of H(n)CdCl((2+n))L(q) complexes in the organic phase, where n=0, 1, 2 and q=1, 2. The mathematical model of cadmium(II) extraction was derived from the mass balances and chemical equilibria involved in the separation system. The model was computed with the Matlab software. The equilibrium parameters for metal extraction, i.e. the stability constants of the aqueous Cd-Cl complexes, the formation constants of the acidic Cd-Cl species and the metal equilibrium extraction constants, were proposed. The optimized constants were appropriate, as there was good agreement when the model was fitted to the experimental data for each of the experiments.

Bismuth recovery from acidic solutions using Cyphos IL-101 immobilized in a composite biopolymer matrix.

Impregnated resins prepared by the immobilization of an ionic liquid (IL, Cyphos IL-101, tetradecyl(trihexyl)phosphonium chloride) into a composite biopolymer matrix (made of gelatin and alginate) have been tested for recovery of Bi(III) from acidic solutions. The concentration of HCl slightly influenced Bi(III) sorption capacity. Bismuth(III) sorption capacity increased with IL content in the resin but non-linearly. Maximum sorption capacity reached 110-130mgBig(-1) in 1M HCl solutions. The mechanism involved in Bi recovery was probably an ion exchange mechanism, though it was not possible to establish the stoichiometric exchange ratio between BiCl(4)(-) and IL. Sorption kinetics were investigated through the evaluation of a series of parameters: metal concentration, sorbent dosage, type and size of sorbent particles and agitation speed. In order to reinforce the stability of the resin particles, the IL-encapsulated gels were dried; this may cause a reduction in the porosity of the resin particle and then diffusion limitations. The intraparticle diffusion coefficients were evaluated using the Crank's equation. Additionally, the pseudo-first-order and pseudo-second-order equations were systematically tested on sorption kinetics. Metal can be desorbed from loaded resins using either citric acid or KI/HCl solutions. The sorbent could be recycled for at least three sorption/desorption cycles.

Recovery of zinc(II) from HCl spent pickling solutions by solvent extraction.

Recovery of zinc(II) from HCl spent pickling solutions by solvent extraction using CYANEX921, CYANEX923, CYANEX302, tributyl phosphate, and ALAMINE336 extractants was studied. Tributyl phosphate was selected as suitable extractant. It permitted both effective zinc(II) extraction and the stripping from loaded organic phase with water. The presence of iron(II) did not affect zinc extraction, and only negligible oxidation of iron(II) was observed during extraction experiments. CYANEX reagents and ALAMINE336 extracted zinc(II) strongly, but the stripping with water was ineffective. Moreover, a significant oxidation of iron(II) to iron(III) occurred during extraction. Each of three reagents (CYANEX923, ALAMINE336 and TBP) extracted iron(III) very well. Thus, if iron(III) was present in the spent pickling solution, prior to the extraction it had to be reduced to iron(II). The oxidation was low for tributyl phosphate and high for CYANEX923 and ALAMINE336. CYANEX302 was inactive both for zinc(II) and iron(III) and could not be used for extraction of zinc(II) from spent pickling hydrochloric acid solutions.