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- Catalisadores de automóvel: Caracterização, Reciclagem e Recuperação de Metais PreciososPublication . Paiva, A. P.; Nogueira, Carlos; Costa, Ana M. Rosa da; Costa, M. ClaraOs catalisadores de automóvel desempenham um papel importante no tratamento dos gases de escape dos veículos, minimizando as emissões de substâncias nocivas para o ambiente. No final do seu ciclo de vida constituem resíduos que devem ser reciclados, não só por razões ambientais, mas também económicas e de conservação de recursos. Os agentes catalíticos destes dispositivos são os metais nobres do grupo da platina (Pt, Pd e Rh) cuja recuperação é crucial pelo seu valor e raridade. Neste artigo apresenta-se uma descrição do funcionamento, composição e de processos para a reciclagem de catalisadores de automóvel, bem como alguns resultados de um projecto de investigação em curso que visa contribuir para o desenvolvimento de operações hidro-metalúrgicas, como a lixiviação e a extracção por solventes, aplicáveis aos metais nobres contidos nestes resíduos. Estudou-se a lixiviação em meio de HCl, na presença de um oxidante, demonstrando-se o efeito de variáveis processuais como a concentração dos reagentes e a temperatura nos rendimentos de lixiviação dos metais. Foram também desenvolvidos extractantes (diamidas), que extraem eficiente e selectivamente os metais nobres de meios cloretados, possibilitando a sua separação e recuperação.
- Liquid-Liquid Extraction of Platinum from Chloride Media by N,N'-Dimethyl-N,N'-DicyclohexyltetradecylmalonamidePublication . Costa, M. Clara; Assunção, Ana; Costa, Ana M. Rosa da; Nogueira, Carlos; Paiva, A. P.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).
- Recovery of platinum(IV) and palladium(II) from complex hydrochloric acid matrices by a thiodiglycolamide derivativePublication . Paiva, A. P.; Carvalho, G. I.; Costa, M. Clara; Costa, Ana M. Rosa da; Nogueira, CarlosThe solvent extraction performance of N,N’-dimethyl-N,N’-dicyclohexylthiodiglycolamide (DMDCHTDGA) towards Pt(IV) and Pd(II) in HCl solutions has recently been published. It was shown that these two platinum-group metals (PGMs) are efficiently extracted from 8 M HCl aqueous phases, being subsequently separated by sequential strippings: 1 M HCl allows Pt(IV) recovery, whereas Pd(II) is only back-extracted by thiourea in HCl. In this work, selectivity tests were carried out to evaluate the performance of DMDCHTDGA towards the recovery of both PGMs, from 8 M HCl aqueous phases, when in presence of Rh(III), Fe(III), Ni(II), Zn(II), Al(III), Ce(III) and Zr(IV), simulating the leaching 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) and Pt(IV) by DMDCHTDGA. Fe(III), Zn(II) and Zr(IV) are co-extracted with Pt(IV) and Pd(II); Fe(III) and Zn(II) were efficiently scrubbed with water, whereas Zr(IV) was removed by an acidified aqueous solution. Inversely, Ni(II) is not extracted, and Rh(III) and Ce(III) appear only traceably in the loaded organic phase. Al(III) is a concern, as it is appreciably extracted, and none of the tested backextraction solutions was able to strip it.
- Recovery of platinum and palladium from chloride solutions by a thiodiglycolamide derivativePublication . Paiva, A. P.; Carvalho, G. I.; Costa, M. Clara; Costa, Ana M. Rosa da; Nogueira, CarlosThe 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.
- N,N '-dimethyl-N,N '-dicyclohexylsuccinamide: a novel molecule for the separation and recovery of Pd(II) by liquid-liquid extractionPublication . Costa, M. Clara; Assunção, Ana; Almeida, Ruben; Costa, Ana M. Rosa da; Nogueira, Carlos; Paiva, A. P.ABSTRACT: 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.
- Oxidative leaching process with cupric ion in hydrochloric acid mediafor recovery of Pd and Rh from spent catalytic convertersPublication . Nogueira, Carlos; Paiva, A. P.; Oliveira, Paula; Costa, M. Clara; Costa, Ana M. Rosa daThe recycling of platinum-group metals from wastes such as autocatalytic converters is getting growing attention due to the scarcity of these precious metals and the market pressure originated by increase of demand in current and emerging applications. Hydrometallurgical treatment of such wastes is an alternative way to the most usual pyrometallurgical processes based on smelter operations. This paper focuses on the development of a leaching process using cupric chloride as oxidising agent, in HCl media, for recovery of palladium and rhodium from a spent catalyst. The chloride media allows the adequate conditions for oxidising and solubilising the metals, as demonstrated by equilibrium calculations based on thermodynamic data. The experimental study of the leaching process revealed that Pd solubilisation is clearly easier than that of Rh. The factors temperature, time, and HCl and Cu2+ concentrations were significant regarding Pd and Rh leaching, the latter requiring higher factor values to achieve the same results. Leaching yields of 95% Pd and 86% Rh were achieved under optimised conditions (T = 80.C, t = 4 h,[HCl] = 6 M, [Cu2+] = 0.3 M).
- Leaching efficiency and kinetics of the recovery of palladium and rhodium from a spent auto-catalyst in HCl/CuCl2 mediaPublication . Nogueira, Carlos; Paiva, A. P.; Costa, M. Clara; Costa, Ana M. Rosa daABSTRACT: 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 nonsignificant 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.
- Recovery of precious metals from exhausted automotive catalysts by leaching and solvent extractionPublication . Nogueira, Carlos; Carvalho, G. I.; Costa, M. Clara; Costa, Ana M. Rosa da; Paiva, A. P.Platinum group metals (PGM’s) are precious and rare metals used in many existing and emerging technologies such as electronics, catalysts, energy and medical appliances, among others. PGM’s applications and demand are growing rapidly, and their supply is short and considered critical. Recycling of residues containing PGM’s is therefore mandatory, in order to allow the continuity of supplying. The main market share of PGM´s are catalysts, specially automotive catalytic converters. When exhausted, these wastes constitute important secondary resources that cannot be neglected. Therefore, the recycling of autocatalysts has been taken growing attention. Although some refiners operating plants for PGM’s recovery from residues are already known, the processes are complex, involve many operations and are highly reagent-consuming. Research in this domain is increasing, trying to develop new technologies and processes, more efficient and selective, and less consuming. Hydrometallurgy, and specifically solvent extraction with new reagents, can play an important role in achieving those objectives. In this context, a research has been carried out aiming at developing hydrometallurgical technologies to recover PGM's from spent autocatalysts. This paper presents some results of this investigation, namely concerning the leaching and solvent extraction operations. A Pd-Rh bearing catalyst was mechanically treated by shredding with a cutting mill, allowing size reduction to average particle size of d50=0.61 mm. The leaching operation was tested using hydrochloric acid media (6 M) and several concentrations of nitric acid as oxidizer (0.5-2.4 M). The results attained showed that the dissolution of Pd and Rh was very efficient, with yields near 90%, whatever the nitric acid concentration used. The extraction and separation of PGM’s from synthetic aqueous solutions was studied with amide extractants, namely an N,N’-tetraalkyl substituted thiodiglycolamide. The results showed a good selectively of this extractant for palladium against rhodium, allowing 100% Pd extraction in a wide range of HCl concentrations (1-8 M), while Rh extraction was near 65%. The complete selectivity can be however attained in the subsequent stripping operations, given that Pd can be quantitatively stripped with thiourea/HCl solutions while Rh co-extracted is only stripped by a soda solution. Platinum, if present in the catalysts, can also be processed by this extractive system, since it is also extracted mainly for high HCl concentrations in leachates, and can be selectively stripped by diluted HCl solutions. The achieved results seem promising for developing a new process for efficient separation and recovery of PGM’s from catalysts, using acid leaching and highly selective solvent extraction technology.
- The solvent extraction performance of N,N’-dimethyl-N,N’-dibutylmalonamide towards platinum and palladium in chloride mediaPublication . Paiva, A. P.; Carvalho, G. I.; Costa, M. Clara; Costa, Ana M. Rosa da; Nogueira, CarlosThe 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.