Rhodium (Rh) is the most expensive platinum group metal (PGM) and is of great industrial importance. Although the recycling of PGMs from secondary sources is in high demand, the preferential and selective separation of Rh from PGM mixtures remains a great challenge. Here, a selective Rh separation method involving the precipitation of Rh from an HCl solution containing palladium (Pd), platinum (Pt), and Rh is reported. 4-Butylaniline and 4-hexylaniline were used as precipitants for Rh, and selective Rh precipitation was achieved at high HCl concentrations. We revealed that Rh in HCl selectively forms a unique and highly stable ion-pair complex comprising [RhCl 6 ] 3– /anilinium/chloride ions in a 1:6:3 ratio. The formation and high stability of the Rh complex were found to play important roles in the selective recovery of Rh from PGM mixtures.

The selective recovery of platinum-group metals (PGMs) remains a huge challenge. Although solvent extraction processes are generally used for PGM separation, the use of organic solvents is problematic because of their toxicity and environmental concerns. Here, we have developed a new PGM recovery method by precipitation from hydrochloric acid (HCl) solutions containing Pd(II), Pt(IV), and Rh(III) using aliphatic primary amines as precipitants. Pt(IV) was precipitated using the amines with alkyl chains longer than hexyl independent of HCl concentration. The precipitation of Pd(II) required longer alkyl amines than octyl, regardless of the HCl concentration. Rh(III) was recovered by precipitation at high HCl concentrations using the amines longer than hexyl. The mutual separation of Pt(IV), Rh(III), and Pd(II), in this order, was successfully achieved by changing the HCl concentrations and alkyl chain lengths of the amines. X-ray photoelectron spectroscopy and thermogravimetric analysis evidently showed that the metal-containing precipitates were ion-pair complexes composed of metal chloro-complex anions and ammonium cations.

A new Rh(III) separation method using metal-containing hydrochloric acid (HCl) solutions has been developed. This method includes Rh(III) precipitation with high selectivity using aromatic primary diamines as precipitants. The compound p-phenylene diamine dihydrochloride (PPDA) successfully precipitates only Rh(III) from HCl solutions containing Pd(II), Pt(IV), and Rh(III). Furthermore, highly selective Rh(III) recovery from the simulated spent catalyst leach solution, comprising Pd, Pt, Rh, Ce, Al, Ba, Zr, La, and Y in 5 M HCl, was achieved using PPDA. Single-crystal X-ray analysis revealed that the Rh(III)-containing precipitate using PPDA forms three-dimensional ionic crystals comprising the [RhCl6]3–/ammonium form of PPDA/chloride anion/H2O at a 1:2:1:2 ratio. Formation of these unique ionic crystals plays a key role in the highly selective Rh(III) recovery. This Rh(III) recovery method will be promising for use in the purification process of Rh as well as the practical Rh recovery from spent catalysts.

The selective separation and recovery of specific platinum-group metals (PGMs) from metal mixtures is a significant challenge owing to the similarity of these metals in terms of chemical and physical properties. Among the typical PGMs (Pd, Pt, and Rh), the selective recovery of Pt prior to the recovery of Pd and Rh is in high demand. In this study, we attempted the selective precipitation of Pt(IV) from mixed-metal HCl solutions using 2-ethylhexylamine (2EHA) as a precipitant and achieved the selective precipitation of Pt(IV) from Pd(II) and Rh(III) over a wide range of HCl concentrations. Selective precipitation of Pt(IV) was also achieved from HCl solutions with high levels of base metals, such as Al, Cu, Fe, and Zn. High yields of undegraded 2EHA remaining in the HCl solution after Pt(IV) precipitation were recovered using hydrophobic porous resins. X-ray photoelectron spectroscopy and thermogravimetric measurements revealed that the Pt(IV)-containing precipitate was an ion-pair comprising one [PtCl6]2− and two ammonium cations of 2EHA. The steric hindrance and high hydrophilicity of 2EHA suppressed the formation of Rh(III)- and Pd(II)-containing precipitates, respectively, resulting in the selective precipitation of Pt(IV).

In this study, 4-butylaniline-impregnated resins (BuIRs) were prepared by soaking hydrophobic porous resins in aqueous solutions of 4-butylaniline hydrochloride. Rh(III) was successfully adsorbed by BuIRs from 10 ppm Rh(III) solutions (6 M HCl). The quantitative desorption of Rh(III) accompanied with 4-butylaniline hydrochloride from BuIRs was also achieved by Soxhlet extraction using methanol. UV-Vis absorption measurements of Rh(III)-containing solutions showed that the equilibrium shift of Rh(III)-based species in HCl solutions is slow, and heating of the solutions is effective for equilibrating. The BuIRs obtained in this study effectively recovered the Rh(III) chloro-complex anion ([RhCl 6 ] 3 ) from low Rh(III) concentration solutions, and can be useful in the Rh(III) recovery process.