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  • N,N '-dimethyl-N,N '-dicyclohexylsuccinamide: A novel molecule for the separation and recovery of Pd(II) by liquid-liquid extraction
    Publication . Costa, Maria Clara; Assunção, Ana; Almeida, Rúben; Rosa da Costa, Ana; Nogueira, Carlos; Paiva, Ana Paula
    N,N'-dimethyl-N,N'-dicyclohexylsuccinamide (DMDCHSA) is investigated as a potential molecule for the liquid-liquid extraction of Pd(II) from chloride solutions for the first time. The effect of several parameters on Pd(II) extraction, such as the contact period between both phases, hydrochloric acid, extractant and hydrogen ion concentrations, is evaluated. Pd(II) extraction equilibrium is very fast (30 s) and the extraction percentage (%E) increases with the HCI concentration in the aqueous phases, being higher than 60% for [HCl] > 5 M. The loading capacity of DMDCHSA for Pd(II) is reasonable (molar ratio extractant/metal higher than 16). Several stripping agents (e.g. distilled water, 1 M HCl, seawater and 20 g/L chloride solution as NaCl) were successfully used to transfer Pd(II) to a new aqueous phase, and data obtained from five successive extraction-stripping cycles suggest a good DMDCHSA stability pattern. Attempts to replace 1,2-dichloroethane (1,2-DCE) by commercial and more environmentally friendly diluents showed much worse %E for Pd(II). Selectivity tests with binary, ternary and more complex metal ion solutions were carried out to evaluate the performance of DMDCHSA towards Pd(II) recovery from 6 M HCl, when in presence of Pt(IV), Fe(III), Zn(II), Al(III) and Ce(III), metal ions usually present in solutions that may result from the hydrometallurgical treatment of spent automobile catalytic converters. It was generally observed that the additional metal ions do not affect the recovery of Pd(II) by DMDCHSA, although Fe(III) and Pt(IV) were co-extracted in a great extent. A solvent extraction (SX) scheme is proposed, based on a previous separation of Fe(III) with tributylphosphate (TBP) and on the selective and sequential stripping of Pt(IV) and Pd(II) from the loaded DMDCHSA with 0.01 M thiourea in 0.5 M HCI and seawater, respectively. The dependence of the Pd(II) distribution ratios on DMDCHSA and acidity, complemented with UV-Visible spectroscopy data, points out to DMDCHSA:Pd(II) extracted species with a 2:1 molar ratio and suggests the occurrence of an outer-sphere ion pair reaction, in which both [PdCl4](2-) and HCI are extracted.
  • N,N′-tetrasubstituted succinamides as new molecules for liquid–liquid extraction of Pt(IV) from chloride media
    Publication . Costa, Maria Clara; Almeida, Ruben; Assunção, Ana; Costa, Ana M. Rosa da; Nogueira, Carlos; Paiva, Ana Paula
    Due to the increasing demand of platinum group metals (PGM’s), among which platinum, the search for new alternatives aiming to their extraction and recovery is nowadays of great importance. Thus, two N, N0-tetrasubstituted succinamides, N,N0-dicyclohexyl-N,N0-dimethylsuccinamide (DMDCHSA) and N,N0- dimethyl-N,N0-diphenylsuccinamide (DMDPHSA) were synthesized and investigated, for the first time, as potential molecules for the liquid–liquid extraction of Pt(IV) from chloride solutions. According to the extraction and stripping results obtained in a single contact, these succinamides can be considered promising extractants for the recovery of platinum(IV) from hydrochloric acid media, since DMDCHSA is able to extract more than 95% Pt(IV) from 4 M HCl or higher concentrations, and DMDPHSA extracts 80% and 92% Pt(IV) from 6 M and 8 M HCl solutions, respectively. Furthermore, platinum(IV) can successfully be stripped through a simple contact with seawater: 93% Pt(IV) were recovered from DMDCHSA, while 60% stripping were obtained from DMDPHSA. For each compound, the time necessary to reach equilibrium, and the effects of the type of diluent and different extractant concentrations on the Pt(IV) extraction percentage were investigated. The loading capacity of DMDCHSA and DMDPHSA toward Pt (IV) was also evaluated, and the results show that both extractants present a very high loading capacity. In addition, data obtained from successive extraction-stripping cycles suggest a good stability pattern for both succinamides.
  • Liquid-Liquid Extraction of Platinum from Chloride Media byN,N′-Dimethyl-N,N′-Dicyclohexyltetradecylmalonamide
    Publication . Costa, Maria Clara; Assunção, Ana; Costa, Ana M. Rosa da; Nogueira, Carlos; Paiva, Ana Paula
    Liquid-liquid extraction of platinum(IV) from chloride media was carried out using N,N - dimethyl-N,N -dicyclohexyltetradecylmalonamide (DMDCHTDMA) in 1,2-dichloroethane. Platinum can be effectively extracted by DMDCHTDMA without addition of tin(II) chloride, since extraction percentages (%E) of 88% and 99% have been achieved from 6 M and 8 M HCl, respectively. Moreover, platinum can be successfully stripped through a simple contact with a 1 M HCl solution. The effect of some experimental parameters such as equilibration time, diluent, extractant and HCl concentrations was systematically investigated. The loading capacity of DMDCHTDMA was also evaluated. Data obtained from successive extraction-stripping cycles suggest a good stability pattern of DMDCHTDMA. Preliminary extraction data achieved with single metal ion solutions pointed out to a possible separation of platinum(IV) from palladium(II).