NdFeB magnets currently dominate the magnet market. Supply risks of certain rare earth metals(REM), e.g. Nd and Dy, impose efficient recycling schemes that are applicable to different types and compositions of these...NdFeB magnets currently dominate the magnet market. Supply risks of certain rare earth metals(REM), e.g. Nd and Dy, impose efficient recycling schemes that are applicable to different types and compositions of these magnets with minimum use of chemicals and waste generation. In this study, a hydrometallurgical method was studied that could be adjusted to recover not only REM, but also other valuable metals(e.g.Co, Ni and Cu) that co-existed in the magnet. The magnet powders were completely dissolved in a dilute sulfuric acid solution giving more than 98% of dissolved iron in the ferrous state. Chemical oxidation of Fe-(2+) into Fe-(3+) by the addition of MnO 2 required only 1 h at ambient temperature. It was then possible to precipitate more than 99% of this ferric iron by adjusting the pH of the solution above 3 with either Ca(OH)2 or MnO additions. However, the addition of Ca(OH)2 resulted in the formation of gypsum and up to ca. 23% REM losses, possibly via co-precipitation into the gypsum. MnO elevated the Mn-(2+) concentration in the solution. However, it was found to be problematic that subsequent direct electrolysis removed Mn and Co. Low anodic current efficiencies(ACE) resulted in high energy consumption(EC), while incomplete Mn and Co removals and undesired REM losses were reported. Pre-electrolysis removals of REM and/or Co by oxalate and/or sulfide precipitation were proven to be successful and selective, but this enlarged the flowsheet considerably with only minor improvement of the Mn removal, ACE and EC.展开更多
Rare earth elements(REEs)play a crucial role in many technologies from daily appliances in cell phones to more advanced wind turbines and electric cars.Permanent magnets account for a quarter of total global REEs prod...Rare earth elements(REEs)play a crucial role in many technologies from daily appliances in cell phones to more advanced wind turbines and electric cars.Permanent magnets account for a quarter of total global REEs production and have high recycling value.In this study,smelting process was used to selectively oxidize REEs in the permanent magnets by adding Fe_(2)O_(3).This separates REEs into a slag phase from an iron-rich metallic phase.B_(2)O_(3) was also added to the system as a flux to lower the slag melting temperature.This minimizes REEs loss to the metallic phase and allows a more efficient phase separation.The effect of flux and oxidizing agent addition was investigated on both regular and cerium-rich NdFeB(NdCeFeB)magnets.At 1350℃and for 1 h,the slag phase was successfully separated from the metallic phase with the addition of 0.8 stoichiometric amount of Fe_(2)O_(3) and 40 wt%of B_(2)O_(3).Scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDX)analysis reveals that REEs in the magnet do not migrate to the metal phase while the REE-rich slag phase contains almost no iron.After the selective removal of iron into the metallic phase,REEs are recovered from the slag phase through an acid leaching process allowing>99%of REEs recovery.Boron in the magnet can also be recovered as useful boric acid by evaporation and crystallisation technique.The proposed process in this study is reagent and energy-efficient with almost complete valorisation of both NdCeFeB and NdFeB magnets.展开更多
基金Project supported by the European Community’s Seventh Framework Programme([FP7/2007-2013])under grant Agreement No.607411(MC-ITN EREAN:European Rare Earth Magnet Recycling Network)the Hercules Foundation(Project ZW09-09)
文摘NdFeB magnets currently dominate the magnet market. Supply risks of certain rare earth metals(REM), e.g. Nd and Dy, impose efficient recycling schemes that are applicable to different types and compositions of these magnets with minimum use of chemicals and waste generation. In this study, a hydrometallurgical method was studied that could be adjusted to recover not only REM, but also other valuable metals(e.g.Co, Ni and Cu) that co-existed in the magnet. The magnet powders were completely dissolved in a dilute sulfuric acid solution giving more than 98% of dissolved iron in the ferrous state. Chemical oxidation of Fe-(2+) into Fe-(3+) by the addition of MnO 2 required only 1 h at ambient temperature. It was then possible to precipitate more than 99% of this ferric iron by adjusting the pH of the solution above 3 with either Ca(OH)2 or MnO additions. However, the addition of Ca(OH)2 resulted in the formation of gypsum and up to ca. 23% REM losses, possibly via co-precipitation into the gypsum. MnO elevated the Mn-(2+) concentration in the solution. However, it was found to be problematic that subsequent direct electrolysis removed Mn and Co. Low anodic current efficiencies(ACE) resulted in high energy consumption(EC), while incomplete Mn and Co removals and undesired REM losses were reported. Pre-electrolysis removals of REM and/or Co by oxalate and/or sulfide precipitation were proven to be successful and selective, but this enlarged the flowsheet considerably with only minor improvement of the Mn removal, ACE and EC.
基金Project supported by the Science and Engineering Research Board of India(SRG/2020/002096)。
文摘Rare earth elements(REEs)play a crucial role in many technologies from daily appliances in cell phones to more advanced wind turbines and electric cars.Permanent magnets account for a quarter of total global REEs production and have high recycling value.In this study,smelting process was used to selectively oxidize REEs in the permanent magnets by adding Fe_(2)O_(3).This separates REEs into a slag phase from an iron-rich metallic phase.B_(2)O_(3) was also added to the system as a flux to lower the slag melting temperature.This minimizes REEs loss to the metallic phase and allows a more efficient phase separation.The effect of flux and oxidizing agent addition was investigated on both regular and cerium-rich NdFeB(NdCeFeB)magnets.At 1350℃and for 1 h,the slag phase was successfully separated from the metallic phase with the addition of 0.8 stoichiometric amount of Fe_(2)O_(3) and 40 wt%of B_(2)O_(3).Scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDX)analysis reveals that REEs in the magnet do not migrate to the metal phase while the REE-rich slag phase contains almost no iron.After the selective removal of iron into the metallic phase,REEs are recovered from the slag phase through an acid leaching process allowing>99%of REEs recovery.Boron in the magnet can also be recovered as useful boric acid by evaporation and crystallisation technique.The proposed process in this study is reagent and energy-efficient with almost complete valorisation of both NdCeFeB and NdFeB magnets.