The use of supported liquid membrane extraction for recovery and separation of rare-earth elements (REEs) has been investigated. Experiments have been carried out using the different configurations: (1) standard hollow fiber supported liquid membrane operation (HFSLM), (2) renewal liquid membrane operation (HFRLM), and (3) emulsion pertraction technology (EPT). The experiments were performed in pilot scale using a hollow fiber module with a mass transfer surface area of 8 m2. Synthetic feed solution was used with compositions based on a process for recovery of REE from an apatite concentrate. The total concentration of REE in the feed was varied from 1 to 22 mM REE and the pH was varied in the range 1.5–3.2. Di(2-ethylhexyl) phosphoric acid (D2HEPA) diluted in kerosene, 10% (v/v), was used as the organic membrane solution, and 3 M HCl was used as stripping solution. In supported liquid membrane extraction, the extraction performance is governed by both the kinetics of REE transport through the membrane and by thermodynamics. The effect of feed composition on the selectivity and transport of REE through the liquid membrane have been investigated. The results show that the liquid membrane is more selective toward the heavy REE at lower pH values and higher REE concentration. HFRLM shows a higher transport rate than HFSLM, while the HFSLM configuration gives a higher selectivity toward individual REE. The membrane performance in HFSLM configuration rapidly decays with time, while in the HFRLM and EPT configurations, the performance is much more stable. Possible mechanisms for decaying membrane performance are discussed, and gel formation is identified as being of significant importance. Gel formation is observed at an organic loading above ∼46% for Nd, 38% for Y, 46% for Dy, and 65% for Er. The work performed in this study serves as an initial step to demonstrate that HFRLM and EPT can provide stable operation and be feasible options for processing of REE liquors. A process flow diagram for the recovery of the REE, present in the apatite concentrate, in three fractions is proposed based on the results from this study.

Rare earth elements (REE) have been selectively recovered from NiMH battery leach liquors by antisolvent precipitation. The active anode material was leached using sulfuric acid. The REE were then separated from the other elements by precipitation as sulfates after addition of either ethanol or 2-propanol (antisolvent). In a second step, Ni and Co are separated as sulfates by the same technique. The concentration of elements in different acid alcohol mixtures at 25 degrees C and -10 degrees C respectively are presented as a function of time after addition of the alcohol, and the optimum conditions for separation of the REE in pure form are presented. Under optimum conditions, 5.6 mol/L (Organic/Aqueous (O/A) volumetric ratio = 0.7) of 2-propanol at 25 degrees C, 82% of the REE have precipitated 3 h after addition of the antisolvent and the purity is 99.9%.

In this study, different processes have been developed and applied to treat a rare earth phosphate concentrate obtained within the nitrophosphate process of fertilizer production. Methods to remove impurities such as Fe and Ca have been investigated as well as to separate the phosphorous and thereby facilitate dissolution of the rare earth elements (REE). These methods include thermal treatment with sodium hydroxide and sodium double sulphate precipitation with and without alkaline conversion, followed by selective dissolution in different acids. The proposed processes were compared and analyzed from the perspective of introducing an appropriate intermediate product for further individual REE separation. The results have shown that after thermal treatment with NaOH at 400 °C, the phosphorous can be removed from the rare earth phosphate concentrate by water leaching. Investigation of different REE phosphate concentrates demonstrated that mixed Ca and REE phases, e.g. REE_mCa_n(PO₄)_3m+2n/3 and CaHPO₄ are less likely to dephosphorize than REE(PO₄).nH₂O and FePO₄.H₂O under these conditions. The recovery of REE to a mild acidic solution is limited by the presence of remaining phosphate ions and by the formation of REE oxide phases during the thermal treatment. The results also show that a solution containing 40 g/L REE; free of phosphorous, calcium and iron can be obtained after reprecipitation of the rare earth phosphate concentrate as sodium rare earth double sulphates followed by alkaline conversion with sodium hydroxide and dissolution in nitric acid.

The recoveries of rare earth elements (REEs), nickel, and cobalt from hybrid electric vehicle batteries by sulfation, selective roasting, and water leaching have been studied. The cathode and anode materials of a Panasonic Prismatic Module nickel metal hydride (NiMH) battery were used in the study. The optimal conditions for each step of the process were determined by performing lab-scale experiments. It was found that 8 mol/L of sulfuric acid was sufficient for the sulfation with a solid-to-liquid ratio of 1/5. The optimal roasting conditions was determined to be 850 °C for 2 h. Under optimal conditions, 96% of the REEs could be obtained in the aqueous phase with negligible contamination of Ni and Co. The Ni and Co remained in solid phase as oxides together with traces of aluminum, zinc, and iron oxides. This method provides a way for the separation of the REEs from nickel, cobalt, and other elements present in the NiMH battery, into a leachate suitable for further processing.

Rare earth elements (REE) are a group of 17 elements including lanthanides, yttrium and scandium; which are found in a variety of classes of minerals worldwide. The criticality of the application, lack of high grade and economically feasible REE resources and a monopolistic supply situation has raised significant attention in recovery of these metals from low grade ores and waste materials. In this thesis, the recovery of REE from an apatite concentrate, containing 0.5 mass% of REE, within the nitrophosphate route of fertilizer production has been investigated. Most of the REE (≥ 95%) content can be recovered into a phosphate precipitate with almost 30 mass% REE. Different processes have been developed to convert the REE phosphate precipitate into a more soluble form to obtain a solution suitable for further REE purification and individual separation. It has been shown that after reprecipitation of the REE phosphate concentrate as REE sodium double sulphate and then transformation into a REE hydroxide concentrate, a solution containing 45g/L REE free of Ca, Fe and P can be obtained. The results suggest that the apatite waste after processing of iron ore have the potential to be a very important source for REE in Europe and that the economy is strongly supported by the simultaneous extraction of phosphorous.

The potential of using hollow fiber supported liquid membrane (HFSLM) extraction in individual and group separation of REE has been investigated. A hollow fiber supported liquid membrane plant in pilot scale has been operated according to the three main configurations: standard hollow fiber supported liquid membrane technology (HFSLM); hollow fiber renewal liquid membrane technology (HFRSLM) and emulsion pertraction technology (EPT). The standard HFSLM operation is more selective than HFRSLM and EPT, while higher metal transport rate is observed in EPT followed by HFRSLM and HFSLM. The HFRLM configuration helps to maintain the performance of the liquid membrane.

In the present study, the recovery of valuable metals from a Panasonic Prismatic Module 6.5 Ah NiMH 7.2 V plastic casing hybrid electric vehicle (HEV) battery has been investigated, processing the anode and cathode electrodes separately. The study focuses on the recovery of the most valuable compounds, i.e., nickel, cobalt and rare earth elements (REE). Most of the REE (La, Ce, Nd, Pr and Y) were found in the anode active material (33% by mass), whereas only a small amount of Y was found in the cathode material. The electrodes were leached in sulfuric acid and in hydrochloric acid, respectively, under different conditions. The results indicated that the dissolution kinetics of nickel could be slow as a result of slow dissolution kinetics of nickel oxide. At leaching in sulfuric acid, light rare earths were found to reprecipitate increasingly with increasing temperature and sulfuric acid concentration. Following the leaching, the separation of REE from the sulfuric acid leach liquor by precipitation as NaREE (SO4)(2)center dot H2O and from the hydrochloric acid leach solution as REE2 (C2O4)(3)center dot xH(2)O were investigated. By adding sodium ions, the REE could be precipitated as NaREE (SO4)2 center dot H2O with little loss of Co and Ni. By using a stoichiometric oxalic acid excess of 300%, the REE could be precipitated as oxalates while avoiding nickel and cobalt co-precipitation. By using nanofiltration it was possible to recover hydrochloric acid after leaching the anode material.

In the nitrophosphate process of fertilizer production, rare earth elements (REE) can be recovered as a REE phosphate concentrate. In this process, after digestion of apatite in concentrated nitric acid, Ca(NO₃)₂.4H₂O is first separated by cooling crystallization and then the REE are precipitated in phosphate form by a partial neutralization step using ammonia. The obtained REE phosphate concentrate is contaminated by mainly calcium and iron, and the main solid phases are CaHPO₄.2H₂O, FePO₄.2H₂O and REEPO₄.nH₂O.

In this study, a process to obtain a concentrate more enriched with REE with low concentration of calcium and iron and free of phosphorous is developed. In the developed process, enrichment and dephosphorization of the rare earth phosphate concentrate has been achieved by selective dissolution and re-precipitation of the REE as a sodium REE double sulfate salt. It is shown that by selective dissolution of the REE concentrate in nitric acid at a pH of 2.4, most of the calcium and phosphorus are dissolved, and a solid phase more enriched in REE is obtained. Thereafter, the REE phosphate concentrate is first dissolved in a mixture of sulfuric-phosphoric acid and then the REE are reprecipitated as NaREE(SO₄)₂.H₂O by addition of a sodium salt. More than 95% of the Ca, Fe and P are removed and a REE concentrate containing almost 30 mass% total REE is obtained.

In the present study, the recovery of rare earth elements (REEs) from an apatite concentrate in the nitrophosphate process of fertilizer production has been studied. The apatite concentrate has been recovered from iron ore tailings in Sweden by flotation. In the first step, the apatite is digested in concentrated nitric acid, after which Ca(NO3)2.4H2O is separated by cooling crystallization. The solution is then neutralized using ammonia whereby the REEs precipitate mainly as phosphates (REEPO4.nH2O) and together with calcium as REEn Cam (PO4)(3n + 2m) / 3. In this work, the degree of rare earth coprecipitation during seeded cooling crystallization of Ca(NO3)2.4H2O has been studied. The solubility of calcium nitrate tetrahydrate (Ca(NO3)2.4H2O) in acidic nitrophosphoric acid solutions in the temperature range of − 2 °C to 20 °C has been determined. For the neutralization step, it is shown that the calcium concentration and the final pH play an important role in determining the concentration of REEs in the precipitate. It is found that reaching maximum recovery of REE with minimum simultaneous precipitation of calcium requires careful control of the final pH to about 1.8. It is further observed that the precipitation yield of REEs and iron is favored by a longer residence time and higher temperature. Finally, the effect of seeding with synthesized REE phosphate crystals as well as a mixture of REE and Ca phosphates on the precipitation rate and the composition of the precipitate was studied.