Recovery of valuable metals from manganese purification sludge (SPS) containing Mn-Ni-Co sulfide and preparation of battery-grade Ni-Co-Mn sulfate solution

Abstract

The manganese production industry produces a large amount of sulfide purification sludge (SPS) every year, representing a hazardous solid waste but also a valuable secondary resource for Ni, Co, and Mn. In this paper, the recovery of Ni, Co, and Mn from the SPS was achieved by (i) leaching with a solution of hydrogen peroxide, (ii) selectively extracting nickel, cobalt and manganese, (iii) solvent extraction for zinc removal, and finally obtained the battery-grade Ni-Co-Mn sulfate solution. During the hydrogen peroxide solution leaching stage, the leaching efficiency of Co, Mn, and Ni reached 98.5%, 98.6%, and 95.6%, respectively. A synergistic extraction system (SES) consisting of decyl 4-picolinate and dinonylnaphthalene sulfonic acid was used to selectively extract Ni, Co, and part of Mn, and the extraction of Ni and Co was >99.8% and 95.5%, respectively. The loaded organic was subjected to four-stage countercurrent scrubbing using a 5 g/L H₂SO₄ solution, resulting in nearly 100% removal of Ca and Mg. After that, 150 g/L H₂SO₄ was used to strip Ni, Co, and Mn from the loaded organic to obtain a crude Ni-Co-Mn sulfate solution. Finally, D2EHPA was utilized for the extraction of impurity Zn from the stripping solution to obtain a battery-grade Ni-Co-Mn sulfate solution with <5 × 10⁻⁴ g/L of Zn. Compared to traditional technology, the novel process not only enables the recovery of valuable Ni, Co, and Mn in SPS but also facilitates their direct preparation into battery-grade nickel‑cobalt‑manganese sulfate solution, which has the advantages of a short process and high added value.