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Recovery of platinum and palladium from chloride solutions by a thiodiglycolamide derivative

Publication . Paiva, Ana Paula; Carvalho, Gonçalo Ivo; Costa, Maria Clara; Costa, Ana M. Rosa da; Nogueira, Carlos

The liquid-liquid extraction of platinum(IV) and palladium(II) from hydrochloric acid media was carried out using N,N’-dimethyl-N,N’-dicyclohexylthiodiglycolamide (DMDCHTDGA) in 1,2-dichloroethane (1,2-DCE). Pt(IV) is efficiently extracted from 5 M HCl onwards (%E ≥ 97%), whereas Pd(II) is quantitatively recovered from 1 to 8 M HCl solutions. Both Pt(IV) and Pd(II) can be successfully stripped from the loaded organic phases, the former with a 1 M HCl solution, the latter with 0.1 M thiourea in 1 M HCl. The maximum loading capacity of DMDCHTDGA for Pt(IV) could not be determined but it is high, since molar ratios extractant:Pt(IV) within 2 and 3 have been achieved. Data obtained from successive extraction-stripping cycles suggest a good stability profile of DMDCHTDGA towards Pt(IV) recovery. Attempts to replace 1,2-DCE by more environmentally-friendly diluents showed, in general, comparable %E for Pt(IV). The study of the influence of acidity, as well as chloride ion and DMDCHTDGA concentrations, allows a proposal for the composition of the Pt(IV) species formed upon extraction. Results obtained with binary metal ion solutions point out that Pt(IV) and Pd(II) can be efficiently separated from DMDCHTDGA loaded organic phases through sequential selective stripping.

2013Journal article

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The solvent extraction performance of N,N’-dimethyl-N,N’-dibutylmalonamide towards platinum and palladium in chloride media

Publication . Paiva, Ana Paula; Carvalho, Gonçalo Ivo; Costa, Maria Clara; Costa, Ana M. Rosa da; Nogueira, Carlos

The solvent extraction performance of N,N’-dimethyl-N,N’- dibutylmalonamide (DMDBMA) in 1,2-dichloroethane (1,2-DCE) towards platinum(IV) and palladium(II) in hydrochloric acid media was systematically evaluated. Pt(IV) extraction (%E) increases with the HCl concentration in the aqueous phases, being always higher than 72%, whereas Pd(II) extraction decreases from 65% at 1 M HCl to 22% at 8 M HCl. Several stripping agents for the two metals were tested: Pt(IV) is successfully recovered by a 1 M sodium thiosulfate solution, whereas the best result for Pd(II) was achieved with 0.1Mthiourea in 1MHCl. The loading capacity of DMDBMA for Pt(IV) is high, and data obtained from successive extraction-stripping cycles suggest a good DMDBMA stability pattern. Attempts to replace 1,2-DCE by more environmentally- friendly diluents showed, in general, worse %E for Pt(IV). The dependence of Pt(IV) distribution coefficients on DMDBMA and chloride ion concentrations, as well as on acidity, are the basis of a proposal for the composition of Pt(IV) extracted species.

2014Journal article

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Leaching efficiency and kinetics of the recovery of palladium and rhodium from a spent auto-catalyst in HCl/CuCl2 media

Publication . Nogueira, Carlos A.; Paiva, Ana Paula; Costa, Maria Clara; Rosa Da Costa, Ana

The recycling of scarce elements such as platinum-group metals is becoming crucial due to their growing importance in current and emerging applications. In this sense, the recovery of palladium and rhodium from a spent auto-catalyst by leaching in HCl/CuCl2 media was studied, aiming at assessing the kinetic performance as well as the influence of some processing factors, and the behaviour of contaminant metals. Based on a kinetic model developed for the present case, the influence of temperature was evaluated and the corresponding values of activation energy were estimated as 60.1 ± 4.1 kJ mol-1 for Pd and 44.3 ± 7.3 kJ mol-1 for Rh, indicating the relevance of the chemical step rather than diffusion. This finding was corroborated by the non-significant influence of the stirring velocity. The reaction orders were estimated for each leaching reagent: for HCl, values of 2.1 ± 0.1 for Pd and 1.0 ± 0.3 for Rh were obtained; for Cu2+, the obtained values were 0.42 ± 0.04 for Pd and 0.36 ± 0.06 for Rh. Without any significant loss of efficiency, solutions with higher metal concentrations were obtained using lower liquid/solid ratios, such as 5 L/kg. The main contaminant in solution was aluminum, and its leaching was found to be very dependent on the temperature and acid concentration.

2019Journal article

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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).

2013Journal article

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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.

2016Journal article

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