Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

Abstract

The refining of platinum group metals is based mainly on solvent extraction methods, whereas Ru is selectively recovered by distillation as RuO4. Replacement of distillation by extraction is expected to simplify the purification process. To develop an effective extraction system for Ru, we analyzed the Ru species in HCl with ultraviolet-visible (UV-Vis) and Ru K-edge extended X-ray absorption fine structure (EXAFS) spectroscopies, and we examined the properties of Ru extracted with N-2-ethylhexyl-bis(N-di-2-ethylhexyl-ethylamide) amine (EHBAA) and trioctylamine (TOA). EXAFS and UV-Vis spectra of Ru in HCl solutions revealed that the predominant Ru species in 0.5–10 M HCl solutions changed from [RuCl4(H2O)2]− to [RuCl6]3− with the HCl concentration. The extraction percentages (E%) of Ru in the EHBAA system increased with increasing HCl concentration, reached 80% at [HCl] = 5 M, and decreased at higher HCl concentrations; the corresponding E% for TOA were low. EXAFS analysis of the extracted complex indicated that the Ru3+ had 5 Cl− and 1 H2O in its inner coordination sphere. The similarity of the dependence on HCl concentrations of the E% in the EHBAA system and the distribution profile of [RuCl5(H2O)]2− on [RuCln(H2O)6−n]3−n suggested that the EHBAA extracted the pentachlorido species.