A Study on Direct Oxalate Precipitation for REE Recovery from a Low-Grade REE Pregnant Solution

"While oxalic acid precipitation practices are commonly applied on purified rare earth elements (REEs) pregnant leaching solutions (PLS), few efforts have been reported using oxalic acid (OXA) to recover REEs directly from untreated PLS. High oxalic acid demand is the most significant issue in all these direct oxalic precipitation (DOP) practices. Preliminary research on DOP of REE from a dilute PLS originating from an acid bake followed by water leaching was conducted. At 75°C, the oxalic acid demand was between 12 and 18 times the stoichiometric requirement for complete REE precipitation. Conducting DOP at 25°C had superior REE recovery but the product purity and filterability declined. Between 75°C and 100°C, REE recovery increased with increasing temperature. When sodium hydroxide was used to adjust the pH during DOP, in the range of 0.5 to 1.5, higher pH benefited REE recovery. Using ammonium hydroxide in place of sodium hydroxide, the REE recovery was reduced by close to 5%. Sodium chloride addition to the PLS was also investigated and the results showed that at both 75°C and 25°C, the REE recovery was enhanced substantially. At 25°C, when the oxalic acid addition was controlled at 4.7 times the stoichiometric requirement, the overall REE recovery reached 95% with the addition of 240 g/L NaCl. Other reagents such as KCl, NH4Cl also showed significant enhanced REE recovery at the same oxalic acid addition. The addition of sodium sulphate appeared to largely enhance the precipitation of LREE but inhibited the formation of HREE oxalate. All results indicate the formation of rare earth double salts may play an important role in REE DOP sulphate media.INTRODUCTIONThe conventional routes for recovering rare earth elements (REEs) from a sulphuric acid pregnant leaching solution (PLS) involves an initial purification step for removal of iron, aluminium for example by precipitation through neutralization, followed by precipitation of REEs as hydroxide, oxalate or carbonate salts, or by bulk solvent extraction for REE recovery (Xia, 2013). Another route was used by Bayan Obo in their historical flowsheet, where the PLS was first subjected to double sulphate precipitation, then the remaining REEs, mostly heavy rare earth elements (HREE), were recovered by oxalate precipitation (Li, 2011)."