Intragruppentrennung Seltener Erden mittels neuer phosphororganischer Liganden

Rare earth elements (REE) have unique magnetic, photophysical, and chemical properties and they are therefore used in numerous high-technology applications. However, to this day, the isolation of pure rare earths from primary and secondary raw materials is very challenging. In this work, the hydrometallurgical separation of neighboring rare earths (e.g., praseodymium/neodymium) was optimized with novel selective extraction agents.The separation of rare earths (yttrium and all lanthanides except promethium) was investigated with fourteen new organophosphorus compounds. Oxygen-bearing phosphinic acids yielded good separation results for heavy rare earths (dysprosium to lutetium). For light rare earths (lanthanum to neodymium), particularly high separation factors were realized with synergistic systems containing an aromatic dithiophosphinic acid and a co-extractant, such as tris (2-ethylhexyl) phosphate (TEHP). Optimization studies of the latter extraction system revealed an extremely high separation factor (SF) of 4.21 between praseodymium and neodymium.Another focus of this work was to understand the extraction mechanism. With the aid of nuclear magnetic resonance spectroscopy (1H-NMR) and time-resolved laser fluorescence spectroscopy (TRLFS), the complex stoichiometry of promising extraction systems was examined. Studies revealed a dependency between the selectivity for rare earths and the coordination number of the formed complexes. In addition, temperature-dependent extraction experiments were performed and thermodynamic data (ΔG, ΔH, and ΔS) determined. These data provided additional information about the origin of selectivity for neighboring rare earths.With regard to the industrial capability of the investigated extraction systems, the chemical durability of ligands was studied under process-relevant conditions. Qualitative and quantitative analytical methods (e.g., GC-MS) were used in long-term experiments to determine the ligand degradation. After the decomposition products had been identified, reaction paths were proposed. The impact of this decomposition on the separation of rare earths was followed, in single extraction experiments, over a period of up to several months