Circulation of Sodium Sulfate Solution Produced During NiMH Battery Waste Processing

Hydrometallurgical recovery of rare earth elements (REE) from NiMH battery waste can be performed using sulfuric acid leaching followed by selective precipitation as double salt (REENa(SO4)2•H2O) by adding Na2SO4 as a precipitating agent. The formed double salts can be treated further with NaOH solution to form REE hydroxides. This study focuses on metamodeling of a simulated flowsheet with design of experiments (DOE). Based on literature survey, a process flowsheet was developed using HSC Sim software. The created flowsheet focuses on circulation of solution containing Na+, K+, SO42- ions and impurities liberated in the NaOH treatment of double salt precipitate. The effect of seven parameters (P1-P7) on seven responses (R1-R7) were modeled using central composite design (CCD). INTRODUCTION Nickel metal hydride (NiMH) battery waste can be considered as an urban mineral due to the presence of valuable metals like: Ni, Co and rare earth elements (REE) (Larsson et al., 2013). In NiMH battery waste leaching experiments, sulfuric acid has often been employed as a lixiviant (Pietrelli et al., 2002,Zhang et al., 1999,Rodrigues and Mansur, 2010,Porvali et al., 2018). The key advantages of sulfuric acid are its stability and cost-effectiveness compared to other mineral acids such as HCl and HNO3. However, the usage of sulfuric acid in NiMH battery waste leaching poses simultaneous challenges and advantages. Limited REE solubility can be taken as benefit when recovering REEs double sulfates after solid-liquid separation. However, sodium and potassium hydroxide, present in electrolyte residues in the battery waste, can cause in-situ precipitation already during leaching due to limited solubility, thus decreasing the total REE recovery (Porvali et al., 2018). However, this problem can be circumvented by washing the electrolyte residues off the raw materials. Subsequently, the REEs may be precipitated in bulk as a mixed double salt out from the solution at very low pH with minimal co-precipitation of Ni and other metals. This relatively easy separation method can be extremely advantageous in the case of such a complex solution matrix with relatively high REE concentrations (conc.). Once REEs have been precipitated as double sulfates as per eq. (1) (Porvali et al., 2018), the resulting double salt precipitate lacks applications without further treatment. Direct thermal treatment would generate sulfur dioxide emissions and likely require high temperatures in order to transform double sulfates into REE oxides. Furthermore, the precipitate contains Na ions, which would need to be removed by chemical treatment from the calcined REE product. In the context of circularity of raw materials, it can be taken of a remarkable benefit if the sodium and sulfur present in the double salt could be reused instead of wasting them into the side streams. To that end, in this simulation study, the double salts are converted by dissolution and precipitation to hydroxides which are readily treatable, e.g. with total dissolution and solvent extraction, for further purification (Abreu and Morais, 2010):