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  • Hydrometallurgical recovery of platinum-group metals from spent auto-catalysts: Focus on leaching and solvent extraction
    Publication . Paiva, A. P.; Piedras, Francisco Vega; Rodrigues, Pedro G.; Nogueira, Carlos
    ABSTRACT: To ensure the supply of raw materials for products of extreme importance in strategic sectors, the recovery of critical metals from secondary sources becomes increasingly urgent. Platinum group metals (PGMs), being rare and very valuable, fall into this demand, and the catalytic converters that contain them are recognized as one of the main sources. Hydrometallurgical processes have been proposed as an alternative to pyrometallurgical ones, with leaching and separation by solvent extraction being core operations in this type of processing. This article investigates these two operations, seeking to optimize conditions and propose new arrangements to improve them. Two different catalyst samples were considered in the experimental work. Leaching was carried out involving concentrated HCl solutions (with H2O2 as oxidant) and low liquid/solid ratios, seeking to maximize PGMs recovery, guaranteeing their high concentration in leachates and minimizing aluminum co-dissolution. Cerium leaching was also followed since this is a rare-earth metal with potential interest. Temperature, HCl concentration, liquid/solid ratio (L/S), time and particle size factors were evaluated, and the optimized conditions found were 11.6 mol L-1 HCl, 1%vol H2O2, 60 C, L/S = 2 L kg(-1) and 3 h, leading to PGM yields of 90-98% Pt, 99% Pd and 70-96% Rh, and leachate compositions of 0.41-0.78 g L-1 Pt, 1.6 g L-1 Pd, 0.062-0.066 g L-1 Rh, depending on the catalyst sample.& nbsp;For solvent extraction (SX), several commercial extractants dissolved/diluted in toluene were checked, firstly with a model solution, and then applied to the real spent auto-catalyst (SAC) leachates produced in-situ. The overall results showed that the most promising SX systems among those tested were Cyanex (R) 471X and Cyphos (R) IL 101. Cyanex (R) 471X allowed the quantitative extraction of Pd(II) and Fe(III), but the latter was conveniently scrubbed by water prior to Pd(II) stripping by an acidic thiourea solution. Pt(IV) and Pd(II) extraction values by Cyphos (R) IL 101 were very encouraging, as only Fe(III) and Zn(II) were appreciably co-extracted, however, scrubbing of the contaminating metals, and Pd(II) and Pt(IV) stripping, did not work. Hence, investigation to find proper scrubbing/stripping agents for Cyphos (R) IL 101 SX system, to recover PGMs from recycled SACs, is further needed.
  • Recovery of platinum from a spent automotive catalyst through chloride leaching and solvent extraction
    Publication . Méndez, Ana; Nogueira, Carlos; Paiva, A. P.
    ABSTRACT: Considering economics and environmental sustainability, recycling of critical metals from end-of-life devices should be a priority. In this work the hydrometallurgical treatment of a spent automotive catalytic converter (SACC) using HCl with CaCl2 as a leaching medium, and solvent extraction (SX) with a thiodiglycolamide derivative, is reported. The aim was to develop a leaching scheme allowing high Pt recoveries and minimizing Al dissolution, facilitating the application of SX. The replacement of part of HCl by CaCl2 in the leaching step is viable, without compromising Pt recovery (in the range 75-85%), as found for the mixture 2 M CaCl2 + 8 M HCl when compared to 11.6 M HCl. All leaching media showed good potential to recover Ce, particularly for higher reaction times and temperatures. Regarding SX, results achieved with a model solution were promising, but SX for Pt separation from the real SACC solution did not work as expected. For the adopted experimental conditions, the tested thiodiglycolamide derivative in toluene revealed a very good loading performance for both Pt and Fe, but Fe removal and Pt stripping from the organic phases after contact with the SACC solution were not successfully accomplished. Hence, the reutilization of the organic solvent needs improvement.
  • Ionic Liquids in the Extraction and Recycling of Critical Metals from Urban Mines
    Publication . Paiva, A. P.; Nogueira, Carlos
    ABSTRACT: Ionic liquids (ILs), salts with a melting temperature below the boiling point of water, are one of the most recent fashion trends in modern chemistry. Nowadays, and taking into account the extensive research found in literature, it seems hard to imagine a sustainable world in the near future without the involvement of ILs, since they have low vapor pressure, are non-flammable, and display excellent chemical/electrochemical/thermal stabilities. Accordingly, ILs are considered to be advantageous replacers of the traditional organic solvents, therefore, much more environmentally-friendly. ILs can be easily produced to tune their physicochemical properties to specific applications, and that is the case currently occurring for several separation processes. This review aims to highlight and discuss some of the most relevant key-achievements, developed at laboratory scale, focusing on the use of ILs for the hydrometallurgical extraction of critical metals from urban mines, particularly the platinum-group metals (PGMs): ruthenium, rhodium, palladium, osmium, iridium, and platinum. A few decades of investigation brought a well-recognized scientific knowledge, still with a wide space to go, but work has yet to be conducted on testing the most promising ILs for the recycling of metals from real urban mines, and at a scaled-up level. Nevertheless, based on the most significant case-studies, the upcoming of ILs to recover critical metals from end-of-life devices for further valorization is assessed.