Rapid and selective recovery of palladium from platinum group metals and base metals using a thioamide-modified calix[4]arene extractant in environmentally friendly hydrocarbon fluids

A novel macrocyclic calix[4]arene extractant having a long alkyl chain thioamide, 25,26,27,28-tetrakis(N-n-octylthiocarbamoyl)methoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (1), was synthesized from 25,26,27,28-tetrakis(N-n-octylcarbamoyl)methoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (2) using Lawesson’s reagent. Extractant 1 was characterized using 1H NMR, 13C NMR, FT-IR spectroscopy, and elemental analysis. The Pd(II) extraction abilities of 1 and 2 were studied in high-boiling-point and environmentally friendly hydrocarbon diluents. Pd(II) extraction experiments were conducted using single-metal Pd(II) solutions, simulated mixed palladium group metal (PGM) solutions, and acid-leached automotive catalyst residue solutions. Different experimental conditions, including the shaking time, HCl/HNO3 concentration, Pd(II) concentration, extractant concentration, and the organic/aqueous phase ratio, were studied systematically. Extractant 1 showed very selective (> 99.9%) Pd(II) extraction from the mixed PGM/base metal solutions and the acid-leached automotive catalyst residue solution. Conversely, the Pd(II) extraction ability of extractant 2 was found to be negligible. Extractant 1 showed very fast extraction kinetics and a high extraction capacity as compared to those of the commercial extractant di-n-octyl sulfide. Effective stripping of Pd(II) from 1 was performed using HCI, HNO3, NH3, and HCl-thiourea solutions. Furthermore, 1 was successfully recycled over five extraction/stripping cycles. The Pd(II) extraction mechanism of 1 was studied using FT-IR spectroscopy. Extractant 1 exhibited very selective Pd(II) extraction and high acid stability, demonstrating its industrial applicability for the extraction of Pd(II) from leached automotive catalyst liquors containing PGMs and base metals.