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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.
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.
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.
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).
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.
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Funding agency
Fundação para a Ciência e a Tecnologia
Funding programme
3599-PPCDT
Funding Award Number
PTDC/QUI-QUI/109970/2009