A green preparation of Mn-based product with high purity from low-grade rhodochrosite

Abstract

The low-grade rhodochrosite, the main resources for exploitation and applications in China, contains multiple elements such as iron, silicon, calcium and magnesium. So the conventional preparation of manganese sulphate and manganese oxide with high purity from electrolytic product is characterized by long production-cycle, high-resource input and high-pollution discharge. In our work, a sustainable preparation approach of high pure MnSO4 solution and Mn3O4 was studied by employing low-grade rhodochrosite (13.86%) as raw material. The repeated leaching of rhodochrosite with sulphuric acid was proposed in view of the same ion effect, in order to improve the solubility of Mn2+ and inhibit the dissolution of the impurities Ca2+ and Mg2+. With the aid of theoretical calculation, BaF2 was chosen to remove Ca2+ and Mg2+ completely in the process of purifying. The results showed that the impurities such as Ca2+, Mg2+, Na+ were decreased to less than 20ppm, and the Ni- and Fe- impurities were decreased to less than 1ppm, which meets the standards of high pure reagent for energy and electronic materials. The extraction ratio and the recovery ratio of manganese reached 94.3% and 92.7%, respectively. Moreover, the high pure Mn3O4 was one-step synthesized via the oxidation of MnSO4 solution with the ratios of OH-/Mn2+=2 and Mn2+/H2O2=1.03, and the recovery rate of manganese reaches 99%.