The Reduction Behavior of Ocean Manganese Nodules by Pyrolysis Technology Using Sawdust as the Reductant

Abstract

Ocean manganese nodules, which contain abundant Cu, Co, Ni and Mn resources, were reduced using biomass (sawdust) pyrolysis technology. Valuable metals were further extracted by acid leaching after the reduction process with high efficiency. The effects of sawdust dosage, reduction temperature, and time were investigated to obtain optimal operating parameters. The extraction rates of Mn, Cu, Co, and Ni reached as high as 96.1%, 91.7%, 92.5%, and 94.4%, respectively. Results from TGA show that the main pyrolysis process of sawdust occurs at temperature range of 250–375 °C with a mass loss of 59%, releasing a large amount of volatile substances to reduce the ocean manganese nodules. The pyrolysis activation energy of sawdust was calculated to be 52.68 kJ∙mol−1 by the non-isothermal kinetic model. Additionally, the main reduction reaction behind the main sawdust pyrolysis process was identified by the comparison of the assumed and actual TG curve. The thermodynamic analysis showed that the high valence manganese minerals were gradually reduced to Mn2O3, Mn3O4, and MnO by CO generated from sawdust pyrolysis. The shrinking core model showed that the reduction process is controlled by the surface chemical reaction with activation energy of 45.5 kJ∙mol−1. The surface of reduced ore and acid leached residue exhibited a structure composed of relatively finer pores and rougher morphology than the raw ore.