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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.
- New extractants for separation of platinium-group metals from chloride solutions and their application to recycling processesPublication . Paiva, A. P.; Carvalho, G. I.; Schneider, A. L.; Costa, M. Clara; Costa, A. M.; Assunção, A. F.; Nogueira, CarlosIn this paper some results on the application of four N,N’-tetrasubstituted malonamide derivatives for the extraction and separation of platinum-group metals (PGMs) are presented. The above mentioned extractants were specifically synthesized in order to evaluate their efficiency for the extraction of a specific metal, or group of metals, from aqueous chloride matrices. Different behaviours were obtained towards platinum(IV) and/or palladium(II) extraction, all the N,N’-tetrasubstituted malonamide derivatives allowing the mutual separation of the two metal ions, depending on the HCl concentration. Generally, extraction experiments were carried out involving initial aqueous phases containing 100 mg/L of each metal isolate, in varying 1M to 8M HCl concentration ranges, and 0.05M extractant in 1,2- dichloroethane solutions. From the preliminary results obtained, one can conclude that HCl concentrations and the structure of the malonamide derivative play a crucial role on the efficiency shown for Pt(IV) and/or Pd(II) extraction. The efficiency of the stripping stage of the loaded organic phases is variable, depending on the N,N’-tetrasubstituted malonamide derivative, as well as on the metal ion involved; for Pt(IV), distilled water and 1M HCl were generally successful, whereas for Pd(II), thiourea in HCl gave better results. The overall data already achieved suggest that these extractants may be good candidates for further evaluation in PGMs separations from real solutions resulting from recycling processes.
- 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.
- Ionic liquids in the solvent extraction of platinum-group metals : how far can they go?Publication . Paiva, A. P.; Costa, M. Clara; Nogueira, CarlosABSTRACT: Ionic liquids (ILs) are molten salts that are liquid at room temperature. Although their existence has been known from the beginning of the 20th century, only at the end of the 80's - beginning of 90´s their characteristic properties and potential advantages began to be widely explored. Nowadays there is no doubt that ILs have become a major subject of research for modern chemistry, and the industry progressively starts to include ILs in chemical processes. This communication presents and discusses some relevant results found in literature concerning the application of ILs to recover platinum-group metals (PGMs) from complex leaching solutions by solvent extraction (SX). Based on the available data, an evaluation about the forthcoming of ILs to recover PGMs from real leaching solutions of spent catalysts will be assessed.
- Hydrometallurgical recovery of platinum-group metals from spent auto-catalysts: Focus on leaching and solvent extractionPublication . Paiva, A. P.; Piedras, Francisco Vega; Rodrigues, Pedro G.; Nogueira, CarlosABSTRACT: To ensure the supply of raw materials for products of extreme importance in strategic sectors, the recovery of critical metals from secondary sources becomes increasingly urgent. Platinum group metals (PGMs), being rare and very valuable, fall into this demand, and the catalytic converters that contain them are recognized as one of the main sources. Hydrometallurgical processes have been proposed as an alternative to pyrometallurgical ones, with leaching and separation by solvent extraction being core operations in this type of processing. This article investigates these two operations, seeking to optimize conditions and propose new arrangements to improve them. Two different catalyst samples were considered in the experimental work. Leaching was carried out involving concentrated HCl solutions (with H2O2 as oxidant) and low liquid/solid ratios, seeking to maximize PGMs recovery, guaranteeing their high concentration in leachates and minimizing aluminum co-dissolution. Cerium leaching was also followed since this is a rare-earth metal with potential interest. Temperature, HCl concentration, liquid/solid ratio (L/S), time and particle size factors were evaluated, and the optimized conditions found were 11.6 mol L-1 HCl, 1%vol H2O2, 60 C, L/S = 2 L kg(-1) and 3 h, leading to PGM yields of 90-98% Pt, 99% Pd and 70-96% Rh, and leachate compositions of 0.41-0.78 g L-1 Pt, 1.6 g L-1 Pd, 0.062-0.066 g L-1 Rh, depending on the catalyst sample.& nbsp;For solvent extraction (SX), several commercial extractants dissolved/diluted in toluene were checked, firstly with a model solution, and then applied to the real spent auto-catalyst (SAC) leachates produced in-situ. The overall results showed that the most promising SX systems among those tested were Cyanex (R) 471X and Cyphos (R) IL 101. Cyanex (R) 471X allowed the quantitative extraction of Pd(II) and Fe(III), but the latter was conveniently scrubbed by water prior to Pd(II) stripping by an acidic thiourea solution. Pt(IV) and Pd(II) extraction values by Cyphos (R) IL 101 were very encouraging, as only Fe(III) and Zn(II) were appreciably co-extracted, however, scrubbing of the contaminating metals, and Pd(II) and Pt(IV) stripping, did not work. Hence, investigation to find proper scrubbing/stripping agents for Cyphos (R) IL 101 SX system, to recover PGMs from recycled SACs, is further needed.