Search Results (6)

The increasing demand for critical metals has intensified efforts to recover valuable metals from various sources, including secondary waste. Zn-Pb tailings contain both major and trace metals with economic and environmental significance. This study examined the extraction of transition metals from Zn-Pb tailings using inductively coupled plasma mass spectrometry (ICP-MS) at a constant time of 30 min. Metal extraction efficiencies were evaluated using N-Methyl-N,N,N-trioctylammonium chloride (Aliquat 336), methyl salicylate (MS), di(2-ethylhexyl) phosphoric acid (D2EHPA), tributyl phosphate (TBP),2,4,6-tris(allyloxy)-1,3,5-triazine (TAOT), and triethyl phosphate (TEP). Increasing mixing rates improved mass transfer, enhancing recoveries, with Hf⁴⁺, Ti⁴⁺, and Fe³⁺ reaching 88, 56, and 50%, respectively, at 1000 rpm (mixing rate; rotation per minute) using D2EHPA. At a mixing rate of 1000 rpm, 10% TEP recovered 25% of Cu²⁺ and 34% of Mn²⁺, while 150 g/L extracted 48% of Hf⁴⁺ and 46% of V⁴⁺. Additionally, 10% TBP extracted 33% of Mn²⁺ and 35% of V⁴⁺, 10% MS recovered 41% of Mn²⁺ and 39% of V⁴⁺, while TAOT extracted 35% of V⁴⁺. At room temperature (22.5 °C) and 1400 rpm, 10% of D2EHPA recovered 80% of Hf⁴⁺, 73% of Ti⁴⁺, and 61% of Fe²⁺. However, 10% TAOT selectively recovered 50% of V⁴⁺, while 10% MS, under the same conditions, recovered 50% of V⁴⁺ with co-extraction of Mn²⁺ and Cu²⁺ (<10%). A total of 150 g/L Aliquat 336 effectively extracted Hf⁴⁺ (66%), Zn²⁺ (19%), and V⁴⁺ (56%). A total of 10% TBP recovered 53% and 47% of Mn²⁺ and V⁴⁺, respectively. A total of 10% TEP recovered Cu²⁺ (45%), Mn²⁺ (55%), Zn²⁺ (29%), V (40%), and 26% of Ni²⁺. At room temperature (22.5 °C) and 1400 rpm, pH changes significantly affected extraction, with D2EHPA (10%) demonstrating 89% efficiency for Hf⁴⁺ at pH 1.3, while other metals showed lower recoveries. TEP (10%) increased Cu²⁺ and Hf⁴⁺ recovery to 52% and 80%, respectively, at pH 1.3, while 150 g/L Aliquat 336 favored Cu²⁺ (58%), with co-extraction of 16% of Zn²⁺ at pH 1.3. TBP (10%) extracted 60% and 61% of Cu²⁺ and Fe, respectively, at pH 1.3, while 10% of MS recovered 55% and 50% of V, respectively. A concentration of 10% D2EHPA favored the recovery of 90% of Hf⁴⁺ at pH 1.3, with less than 35% co-extraction of Cu²⁺, Mn²⁺, Zn²⁺, and Fe²⁺. At 1400 rpm, temperature also influenced extraction, with D2EHPA recovering 84% of Hf⁴⁺ at 35 °C, 77% of Ti (55 °C), and 79% of Fe (55 °C) and TBP extracting 73% of Cu²⁺, 67% of Mn²⁺, 68% of Zn, 60% of V⁴⁺, and 47% of Ni²⁺ at 55 °C. A concentration of 10% MS extracted 61% of V⁴⁺and 54% of Fe²⁺, while 150 g/L recovered 61% of V⁴⁺ at 55 °C. TAOT extracted 46% of Mn and 41% of V⁴⁺, while 10% TEP recovered 60% of Mn and 32% of V⁴⁺ at 55 °C. These outcomes contribute to an improved understanding of the solvent extraction mechanisms of different ligands. Full article

The application of a bidentate aromatic N,N’-donor ligand, 2,2′-biimidazole (BIIMH₂), as an extractant in the form of 1-octyl-2,2′-biimidazole (OBIIMH) and related derivatives in the solvent extraction of base metal ions (Mg²⁺, Mn²⁺, Fe³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) from an acidic sulfonate medium using dinonylnaphthalene disulfonic acid (DNNDSA) as a synergist was investigated. OBIIMH with DNNDSA as a co-extractant showed a lack of selectivity for base metals ions (Mg²⁺, Mn²⁺, Fe³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) despite its similarity with a related bidentate aromatic ligand, 2,2′-pyridylimidazole, which showed preference for Ni(II) ions. The nickel(II) specificity, through stereochemical “tailor-making”, was not achieved as expected and the extracted species were isolated to study the underlying chemistry. The homemade metal sulfonate salts, M(RSO₃)₂·6H₂O (R = Toluene and M²⁺ = Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺), were used as precursors of the metal complexes of BIIMH₂ using toluene-4-sulfonic acid as the representative sulfonate. Spectroscopic analysis and single-crystal X-ray analysis supported the formation of similar neutral distorted octahedral sulfonato complexes through the bis coordination of BIIMH₂ and two sulfonate ions rather than the formation of cationic complex species with anion coordination of sulfonates. We attributed the observation of similar complex species and the similar stability constants of the bis-complexes in solution as the cause for the lack of pH-metric separation of the later 3d metal ions. Full article

The matrix effect refers to the change in the analytical signal caused by the matrix in which the sample is contained, as well as the impurities that are co-eluted with the target analyte. In crop sample analysis using LC–MS/MS, the matrix effect can affect the quantification results. Chinese chives are likely to exhibit a strong matrix effect when co-extracted with bifenthrin and butachlor due to the presence of phytochemicals and chlorophyll. A novel analytical method was developed to reduce the matrix effects of bifenthrin and butachlor to a negligible level in Chinese chives. The established method had a limit of quantitation of 0.005 mg/kg and correlation coefficients greater than 0.999 within the range of 0.005–0.5 mg/kg. Matrix effects were found to be negligible, with values ranging from −18.8% to 7.2% in four different sources of chives and two leafy vegetables. Compared to conventional analytical methods for the LOQ and matrix effect, the established method demonstrated improved performances. The analytical method was further applied in a residual study in chive fields. The active ingredient of butachlor 5 granule (GR) was not detected after soil admixture application, while that of bifenthrin 1 emulsifiable concentrate (EC) showed a range from 1.002 to 0.087 mg/kg after foliar spraying. The dissipation rate constant (k) of bifenthrin was determined to be 0.115, thus its half-life was calculated to be 6.0 days. From the results, PHI and safety use standards of both pesticides were suggested. The developed analytical method can be applied to accurately determine bifenthrin and butachlor residues in Chinese chives and provides a foundation for further research on the fate and behavior of these pesticides in the environment. Full article

An experimentally simple method for the direct determination of single-ion partition coefficients between water and a PVC membrane plasticized with o-NPOE is suggested. The method uses the traditional assumption of equal single-ion partition coefficients for some reference cation and anion, in this case tetraphenylphosphonium (TPP⁺) and tetraphenylborate (TPB⁻). The method is based on an integrated approach, including direct study of some salts’ distribution between water and membrane phases, estimation of ion association constants, and measurements of unbiased selectivity coefficients for ions of interest, including the reference ones. The knowledge of distribution coefficients together with ion association constants allows for direct calculation of the multiple of the single-ion partition coefficients for the corresponding cation and anion, while the knowledge of unbiased selectivity coefficients together with ion association constants allows for immediate estimation of the single-ion partition coefficients for any ion under study, if the corresponding value for the reference ion is known. Both potentiometric and extraction studies are inherently equilibrium-based techniques, while traditionally accepted methods such as voltammetry and diffusion are kinetical. The inner coherent scale of single-ion partition coefficients between water and membrane phases was constructed. Full article

We prepared acetic acid derivatives using three different frameworks, calix[4]arene, alkenyltrimethylol, and trihydroxytriphenylmethane, which differ in the number and size of their coordination sites. We further investigated the extraction properties for aluminum group metal ions. All three extraction reagents exhibited increased extraction compared with the corresponding monomeric compounds, owing to structural effects. The extraction reaction and extraction equilibrium constants were determined using a slope analysis. Their extraction abilities, separation efficiencies, and potential coordination modes are discussed using the extraction equilibrium constants, half-pH values, and spectroscopic data. The calix[4]arene and trihydroxytriphenylmethane derivatives demonstrated allosteric co-extraction of indium ions (In³⁺) with an unexpected stoichiometry of 1:2. Full article

Selective solvent extraction of molybdenum over rhenium from molybdenite (MoS₂) flue dust leaching solution was studied. In the present work, thermodynamic calculations of the chemical equilibria in aqueous solution were first performed, and the potential–pH diagram for the Mo–Re–${\mathrm{SO}}_4^{2-}$–H₂O system was constructed. With the gained insight on the system, 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl)-ester (PC88A) diluted in kerosene was used as the extractant agent. Keeping constant the reaction temperature and aqueous-to-organic phase ratio (1:1), organic phase concentration and pH were the studied experimental variables. It was observed that by increasing the acidity of the solution and extractant concentration, selectivity towards Mo extraction increased, while the opposite was true for Re extraction. Selective Mo removal (+95%) from leach solution containing ca. 9 g/L Mo and 0.5 g/L Re was achieved when using an organic phase of 5% PC88A at pH = 0. No rhenium was coextracted during 10 min of extraction time at room temperature. Density functional theory (DFT) calculations were performed in order to study the interactions of organic extractants with Mo and Re ions, permitting a direct comparison of calculation results with the experimental data to estimate selectivity factors in Mo–Re separation. For this aim, PC88A and D2EHPA (di-(2-ethylhexyl) phosphoric acid) were simulated. The interaction energies of D2EHPA were shown to be higher than those of PC88A, which could be due to its stronger capability for complex formation. Besides, it was found that the interaction energies of both extractants follow this trend considering Mo species: ${\mathrm{MoO}}_2^{2+}$ > ${\mathrm{MoO}}_4^{2-}$. It was also demonstrated through DFT calculations that the interaction energies of D2EHPA and PC88A with species are based on these trends, respectively: ${\mathrm{MoO}}_2^{2+}$ > ${\mathrm{MoO}}_4^{2-}$ > ${\mathrm{ReO}}_4^{-}$ and ${\mathrm{MoO}}_2^{2+}$ > ${\mathrm{ReO}}_4^{-}$ > ${\mathrm{MoO}}_4^{2-}$, in qualitative agreement with the experimental findings. Full article