Palladium (Pd) and platinum (Pt) are extensively used as catalysts in the petrochemical and automotive industries, and due to high demand for them on the market, their recycling from spent supported catalysts is clearly needed. To assess the content of Pd and Pt in catalysts in order to establish their commercial value or to evaluate the recovery efficiency of technologies used for recycling, reliable analytical methods for determination of these elements are required. Spectrometric methods, such as inductively coupled plasma optical emission spectrometry (ICP-OES) and graphite furnace atomic absorption spectrometry (GFAAS) are powerful tools that can be employed for the determination of Pd and Pt in various sample matrices. However, these methods allow only the injection of liquid samples. In this regard, the digestion of solid sample by microwave-assisted acid extraction procedures at high pressures and temperatures is often used. In this study, a microwave acid digestion method was optimized for the extraction of Pd and Pt from spent catalysts, using a four-step program, at a maximum 200 °C. The resulting solutions were analyzed using ICP-OES, at two different wavelengths for each metal (Pd at 340.458 and 363.470 nm, and Pt at 265.945 and 214.423 nm, respectively) and using GFAAS (Pd at 247.64 nm, Pt at 265.94 nm). Five types of spent catalyst were analyzed and the standard deviations of repeatability for five parallel samples were less than predicted relative standard deviations (PRSD%) calculated using Horvitz’s equation for all the analyzed samples.

Precious metals such as palladium (Pd) have many applications, ranging from automotive catalysts to fine chemistry. Platinum group metals are, thus, in massive demand for industrial applications, even though they are relatively rare and belong to the list of critical materials for many countries. The result is an explosion of their price. The recovery of Pd from spent catalysts and, more generally, the development of a circular economy process around Pd, becomes essential for both economic and environmental reasons. To this aim, we propose a sustainable process based on the use of supercritical CO₂ (i.e., a green solvent) operated in mild conditions of pressure and temperature (p = 25 MPa, T = 313 K). Note that the range of CO₂ pressures commonly used for extraction is going from 15 to 100 MPa, while temperatures typically vary from 308 to 423 K. A pressure of 25 MPa and a temperature of 313 K can, therefore, be viewed as mild conditions. CO₂-soluble copolymers bearing complexing groups, such as pyridine, triphenylphosphine, or acetylacetate, were added to the supercritical fluid to extract the Pd from the catalyst. Two supported catalysts were tested: a pristine aluminosilicate-supported catalyst (Cat D) and a spent alumina supported-catalyst (Cat A). An extraction conversion of up to more than 70% was achieved in the presence of the pyridine-containing copolymer. The recovery of the Pd from the polymer was possible after extraction, and the technological and economical assessment of the process was considered.

Precious metals, in particular Pd, have a wide range of applications in industry. Due to their scarcity, precious metals have to be recycled, preferably with green and energy-saving recycling processes. In this article, palladium extraction from an aluminosilicate-supported catalyst, containing about 2 wt% (weight%) of Pd (100% PdO), with supercritical CO₂ (scCO₂) assisted by complexing polymers is described. Two polymers, p(FDA)SH homopolymer and p(FDA-co-DPPS) copolymer (FDA: 1,1,2,2-tetrahydroperfluorodecyl acrylate; DPPS: 4-(diphenylphosphino)styrene), were tested with regards to their ability to extract palladium. Both polymers showed relatively low extraction conversions of approximately 18% and 30%, respectively. However, the addition of piperidine as activator for p(FDA-co-DPPS) allowed for an increase in the extraction conversion of up to 60%.

The synthesis and characterization of a platform of novel functional fluorinated gradient copolymers soluble in liquid and supercritical CO₂ is reported. These functional copolymers are bearing different types of complexing units (pyridine, triphenylphosphine, acetylacetate, thioacetate, and thiol) which are well-known ligands for various metals. They have been prepared by reversible addition–fragmentation chain-transfer (RAFT) polymerization in order to obtain well-defined gradient copolymers. The copolymers have been characterized by proton nuclear magnetic resonance (¹H-NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, thermal gravimetric analysis (TGA), dynamical scanning calorimetry (DSC) and cloud point measurements in dense CO₂. All the investigated metal-complexing copolymers are soluble in dense CO₂ under mild conditions (pressure lower than 30 MPa up to 65 °C), confirming their potential applications in processes such as metal-catalyzed reactions in dense CO₂, metal impregnation, (e.g., preparation of supported catalysts) or metal extraction from various substrates (solid or liquid effluents). Particularly, it opens the door to greener and less energy-demanding processes for the recovery of metals from spent catalysts compared to more conventional pyro- and hydro-metallurgical methods.