The green reductive leaching of manganiferous iron ore and Mn3O4 nanoparticles production: Kinetic modeling and comparison of various reductants

Karimi M., Karimi S., YAZICI E. Y.

Journal of the Taiwan Institute of Chemical Engineers, vol.159, 2024 (SCI-Expanded) identifier

  • Publication Type: Article / Article
  • Volume: 159
  • Publication Date: 2024
  • Doi Number: 10.1016/j.jtice.2024.105479
  • Journal Name: Journal of the Taiwan Institute of Chemical Engineers
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Applied Science & Technology Source, Chemical Abstracts Core, Compendex, Computer & Applied Sciences, INSPEC
  • Keywords: Co-precipitation method, DL-malic acid, Kinetics study, Low-Grade pyrolusite ore, Mn3O4 nanoparticles, Reductive leaching
  • Karadeniz Technical University Affiliated: Yes


Background: Securing critical metals is crucial for the transition from fossil fuels to renewable energies. In this regard, extracting metals from various sources and low-grade ores can lead to the sustainable production of metals. Manganese, as a strategic metal, can play a significant role in achieving this goal. Methods: In this study, various reductants such as oxalic acid, citric acid, ascorbic acid, acetic acid, tannic acid, hydrogen peroxide, iron (II) sulfate, sodium thiosulfate, and DL-malic acid were used to evaluate the feasibility and comparison on the manganiferous iron ore leaching. Significant findings: DL-malic acid was chosen as the main reductant to investigate other factors because it is novel (as a reductant), eco-friendly, cost-effective, accessible, and easily storable. Therefore, more detailed studies on the dissolution of manganiferous iron ore in the presence of DL-malic acid as the reductant were carried out considering different levels of temperature, particle size, acid concentrations, and leaching time. Increasing the temperature from 298 K to 348 K notably boosted the leaching recovery from 27.00 % to 70.11 %. It was observed that decreasing the ore particle size from -212 μm to -38 μm resulted in an enhancement of leaching recovery from 57.74 % to 70.11 %. Also, adding only 250 % stoichiometry of DL-malic acid notably increased the leaching recovery to 70.11 %, compared to just 5.32 % in a reductant-free medium. It should be noted that the concentration of sulfuric acid had a direct impact on leaching recovery, increasing by 28.28 % with a concentration of 0.5 M and by 93.08 % with a concentration of 4 M. In this research work, the kinetic of the leaching process was modeled using the modified shrinking core model (MSCM). The calculated activation energy was about 33 kJ/mole, which confirmed that the mixed mechanism controlled the reaction. Mn3O4 nanoparticles were synthesized using a pregnant leach solution (PLS) and through a multi-stage co-precipitation method. In this method, hydrogen peroxide was used to modify the manganese hydroxide phase as a more eco-friendly method than other heat treatment methods. The SEM and EDX analyses revealed an average particle size of 80 nm with spherical shapes and no impurities. The XRD pattern of the synthesized nanoparticles confirmed the Mn3O4 phase composition.