Addition of organic acids to dilute hydrochloric acid solution can improve the extraction of rare earth elements by single cationic extractants. However, the correlation between the chemical structure of organic acids and the extraction of REEs as well as the variation in equilibrium pH has not been elucidated. In this study, we investigated the extraction of Tb(III) from dilute HCl solutions containing an organic acid like formic, lactic, fumaric, or maleic acid. As extractants, single Cyanex 272, a mixture of Cyanex 272 and Alamine 336 (Ala336-Cy272), and an ionic liquid (ALi-Cy272) synthesized by Cyanex 272 and Aliquat 336 were used. The speciation of Tb(III) in dilute HCl solutions containing organic acids was analyzed. In extraction of Tb(III), organic acids showed two roles as complexing and buffering agent, which depended on the chemical structure of the acids. There was some difference in the extraction of Tb(III) between single Cyanex 272 and ionic liquid, ALi-Cy272. During extraction with ALi-Cy272, formic and lactic acid negatively affected the extraction of Tb(III). The fact that the chemical structure of organic acids affected the extraction of Tb(III) from dilute HCl solution by the studied extractants can provide important information on the selection of suitable extraction systems.
Electroplating of palladium (Pd) is practiced in the manufacture of electronic materials. The increasing demand for Pd metal necessitates the recovery of Pd(II) from the spent electroplating solutions. In this work, the recovery of Pd compound was studied from the cemented Pd by zinc (Zn) metal from spent electroplating solutions. Initially, the selective extraction ability of ionic liquids synthesized from commercial extractants for Pd(II) over Zn(II) from the synthetic HCl solution was investigated. Pd(II) was selectively extracted over Zn(II) from 9 M HCl solution by ALi-CY301(Nmethyl-N,N,N-trioctylammonium bis(2,4,4-trimethylpentyl) dithiophosphinic) and by ALi-I (N-methylN,N,N-trioctylammonium iodide) from weak HCl solution (pH 1). Since 9 M HCl was needed to completely dissolve Pd from the cemented Pd, ALi-CY301 was employed for the separation of Pd(II) and Zn(II) from the real HCl leaching solution of the cemented Pd. Two-stages counter-current extraction of the real HCl solution with ALi-CY301 resulted in selective extraction of Pd(II). Pd(II) was effectively stripped from the loaded ALi-CY301 by a mixture of HCl and NaClO. After oxidizing Pd(II) in the stripping solution to Pd(IV) by adding NaClO, Pd(IV) compound was synthesized by adding NH4Cl as a precipitant. By comparing leaching and extraction efficiency between hydrochloric and sulfuric acid solutions, a hydrometallurgical process consisted of HCl leaching, extraction with ALiCY301 and precipitation with NH4Cl was recommended for the recovery of pure (NH4)2PdCl6 from the cemented Pd.
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