Two-Step Solvent Extraction of Radioactive Elements and Rare Earths from Estonian Phosphorite Ore Using Nitrated Aliquat 336 and Bis(2-ethylhexyl) Phosphate
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Abstract:
Estonian phosphorite ore contains trace amounts of rare earth elements (REEs), many other d-metals, and some radioactive elements. Rare earth elements, Mo, V, etc. might be economically exploitable, while some radioactive and toxic elements should be removed before any other downstream processing for environmental and nutritional safety reasons. All untreated hazardous elements remain in landfilled waste in much higher concentration than they occur naturally. To resolve this problem U, Th, and Tl were removed from phosphorite ore at first using liquid extraction. In the next step, REE were isolated from raffinate. Nitrated Aliquat 336 (A336[NO3]) and Bis(2-ethylhexyl) Phosphate (D2EHPA) were used in liquid extraction for comparison. An improved method for exclusive separation of radioactive elements and REEs from phosphorite ore in 2-steps has been developed, exploiting liquid extraction at different pH values.Keywords:
Raffinate
Phosphorite
Aliquat 336
Aliquat 336
Raffinate
Stripping (fiber)
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Aliquat 336
Raffinate
Stripping (fiber)
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Hydrochloric acid
Hydrometallurgy
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The extraction behavior of americium(III), curium(III) (minor actinides, MA), fission products (lanthanides (Ln(III)), Mo, Ru, Pd, and Rh), and corrosion products (Zr and Fe) was studied in batch solvent extraction experiments using the room-temperature ionic liquid (IL) Aliquat-336 nitrate ([A336][NO3]) and a solvent composed of 0.05 M TODGA in [A336][NO3]. From acidic, dilute Ln(III) feed solutions, [A336][NO3] extracts nitric acid (D ≈ 0.5) and partially An(III) as well as Ln(III) (DAm = 0.02–0.1, DEu, and DCm = 0.01–0.04). The influence of the acid concentrations and kinetics on extraction and back-extraction of Ln(III) and An(III) by 0.05 M TODGA in [A336][NO3] was investigated using radiotracer-spiked dilute Ln(III) feed solutions. With the solvent composed of 0.05 M TODGA in [A336][NO3], DAn and DLn increase as a function of aqueous feed acidity. In the case of a spiked, simulated highly active raffinate (HAR) feed solution, [A336][NO3] extracts La(III) (DLa = 1.36), Ru (DRu = 1.64), and Pd (DPd = 38), while the distribution ratios of other Ln(III) and An(III) were lower than unity. The solvent composed of 0.05 M TODGA in [A336][NO3] co-extracted from HAR Zr(IV) (DZr> 300), Pd (DPd = 206), and Ln(III) (DLn> 1, except for Nd(III)), but An(III) were retained in the aqueous phase. The interference caused by the co-extraction of several fission (Zr, Pd, Ru, and Mo) and corrosion (Zr) products, which are present in the HAR at relatively high concentrations, was suppressed using masking agents (oxalic acid and trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, CDTA). In the case of the actual HAR solution, the kinetics were found to be faster compared with the extraction from dilute Ln(III) feed solutions, possibly due to the different aqueous speciation of the Ln(III) and An(III).
Aliquat 336
Raffinate
Nitric acid
Curium
Aqueous two-phase system
Liquid–liquid extraction
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Aiming at the content of the valuable components in the tailings of copper mine, we have chose and synthesized a sort of new phosphorite capture reagent (ZP-02).When the pH value of the flotation solution is 10 and the temperature is 30℃, be one roughing, two scavenging, and the rough concentrate were concentrated five times, the flotation result isβ P 2O 5 =25.32%, and e P 2O 5 =69.87%. Realize the recovery of Phosphorite from the tailings of copper mine.
Phosphorite
Copper mine
Copper ore
Recovery rate
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The smelting reduction of spent LIBs produces metallic alloys containing Co, Cu, Fe, Mn, and Ni. These metallic alloys can be completely dissolved by 2 M HCl solution containing H2O2 as an oxidizing agent. Extraction of the leaching solution with D2EHPA results in a Fe(III) free raffinate. In this work, solvent extraction experiments were performed with a mixture of Aliquat 336 and LIX 63 to separate Cu(II) from the Fe(III) free raffinate. This mixture showed selectivity for Cu(II) over Co(II), Mn(II), Ni(II), and Si(IV). The mixture of 0.3 M Aliquat 336 and 0.2 M LIX 63 had the highest synergistic coefficient for the extraction of Cu(II) from the solution. The Cu(II) in the loaded mixture was easily stripped by weak sulfuric acid solution, which facilitates the recovery of copper sulfate from the stripping solution. McCabe-Thiele diagrams for the extraction of Cu(II) by the mixture and for the stripping with sulfuric acid solution were constructed. Three stages of counter-current extraction and stripping experiments verified that only Cu(II) was completely extracted, and the purity of Cu(II) in the stripping solution was higher than 99.9%. Considering the selectivity and easy stripping of Cu(II) from the loaded organic, this mixture can be employed in real operation for the recovery of valuable metals from the leaching solutions of spent LIBs.
Aliquat 336
Raffinate
Stripping (fiber)
Hydrochloric acid
Hydrometallurgy
Oxidizing agent
Electrowinning
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The recovery of valuable metals such as Co, Cu, and Ni from spent lithium-ion batteries has attracted much attention due to environmental issues and economic values. Separation of these metals from the synthetic metallic mixtures was investigated by employing nonaqeous solvent. In this work, the mixture of HCl in ethylene glycol (EG) and Aliquat 336 in kerosene was employed as nonaqeous solvents and the leaching conditions were optimized. Under the optimum condition, Ni was completely leached and remained in the EG phase with 99.8% purity. Meanwhile, the leaching percentage of Co(II) and Cu(II) was 62.3% and 18.3% and most of the two dissolved metal ions were extracted into Aliquat 336 phase. After complete stripping of Co(II) and Cu(II) from the loaded Aliquat 336 phase with 2.0 mol L−1 H2SO4, Cu(II) was selectively extracted over Co(II) by 0.1 mol L−1 Cynanex301 and then stripped by 50% aqua regia solution with >99.9% purity. The purity of Co(II) in the raffinate was 99.6%. Besides, Co from the leaching residue was selectively dissolved over Cu by 5.0 mol L−1 H2SO4 with 99.6% purity. A process was proposed for the separation of Co, Cu and Ni from metallic mixtures. The process showed some advantages in terms of the high purity of the metal solutions recovered and a decrease in the number of steps for the metal recovery. Thus, the application of this process to real operation can be considered.
Aliquat 336
Raffinate
Hydrometallurgy
Kerosene
Aqua regia
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M. R. Shivade and V. M. Shinde, Analyst, 1983, 108, 1155 DOI: 10.1039/AN9830801155
Aliquat 336
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Abstract The liquid–liquid extraction of Ir(IV), Ru(III), and Rh(III) from chloride solution was studied under different conditions of aqueous‐ and organic‐phase component concentrations using Alamine 336 (A336) as an extractant. The differences obtained in the extraction of individual metals at different concentrations of A336 and HCl in the organic and aqueous phases respectively were used to mutually separate the three metals. A two‐step separation scheme was proposed. In the first step, Ir(IV) was selectively extracted using a solvent comprised of 0.1% A336 and 10% TBP in kerosene. In the second step, Ru(III) was quantitatively extracted using a solvent comprised of 5% A336 and 10% TBP in kerosene (all % v/v). Rh(III) was selectively left behind in the raffinate. Under controlled experimental conditions, we were able to eliminate the base metal ions commonly associated with Ir, Ru, and Rh during the extraction and the stripping process.
Raffinate
Kerosene
Stripping (fiber)
Aliquat 336
Hydrometallurgy
Aqueous two-phase system
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Abstract Aliquat 336 has been employed as an effective anionic extractant for the radiochemical separation of niobium, zirconium, and hafnium in mixtures using solvent extraction and reversed phase extraction chromatography (RPEC). In solvent extraction, niobium and zirconium are extracted with reagent solutions in the respective concentration ranges <0.001–0.04 mol dm−3 and 0.5 mol dm−3 leaving hafnium in the aqueous phase. In RPEC, niobium and zirconium are extracted by the reagent impregnated column and hafnium is completely eluted with water. Zirconium and niobium subsequently are eluted successively with 0.5 mol dm−3 HNO3 and 1 mol dm−3 HF solutions. Distribution studies indicate that the extracted species for niobium and zirconium are respectively mono- and dinegative in charge. The extent of separation and the purity of the separated species were verified by means of gamma-ray spectrometry.
Aliquat 336
Hafnium
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