Skip to main content

Advertisement

SpringerLink
Log in

Oxidative Leaching of Low-Grade Pyrolusite in Alkaline Solutions to Produce Potassium Manganate

  • Review
  • Published:
Mining, Metallurgy & Exploration Aims and scope Submit manuscript

Abstract 

In this study, the oxidation of low-grade pyrolusite to potassium manganate in alkaline solutions under O2 pressure has been investigated. The effects of different conditions on the high-grade and low-grade pyrolusite leaching process were investigated based on thermodynamic calculation, as well as the reaction mechanisms and kinetics of the low-grade pyrolusite during the leaching process. The results showed that the manganese conversion rates of the two types of pyrolusite were almost the same, and reaching 99% for high-grade pyrolusite and 96% for low-grade pyrolusite under optimal conditions. The optimum condition for low-grade pyrolusite sample JM-2 was achieved as 0.5 MPa of the oxygen partial pressure, 55% of KOH, 14 of the initial alkali-manganese ratio, and ≤ 48 μm of the mineral granularity at 260 °C within 150 min of leaching time and 500 rpm. In alkaline leaching of low-grade pyrolusite, Mn(IV) was oxidized into Mn(VI). The particles changed from large particles to flakes and finally formed crystals. Finally, the shrinking core model was used to fully describe the leaching kinetics of the manganese. It was demonstrated that the leaching of manganese was controlled by the chemical surface reactions and the activation energy which equals 115.9121 kJ/mol.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14
Fig. 15

Similar content being viewed by others

Data Availability

Not applicable.

References 

  1. Jadhav SV, Bringas E, Yadav GD, Rathod VK, Ortiz I, Marathe KV (2015) Arsenic and fluoride contaminated groundwaters: a review of current technologies for contaminants removal. J Environ Manage 162:306–325. https://doi.org/10.1016/j.jen-vman.2015.07.020

    Article  Google Scholar 

  2. Zhang WS, Cheng CY (2007) Manganese metallurgy review. Part I: leaching of ores/secondary materials and recovery of electrolytic/chemical manganese dioxide. Hydrometallurgy 89(3):137–159. https://doi.org/10.1016/j.hydromet.2007.08.010

    Article  Google Scholar 

  3. Li Y, Li YH, Zhang ZT, He XH, Chen JL (2021) Preparation of Mn3O4 by precipitation conversion-roasting method and its morphological evolution. Ceram Int 47(15):21570–21575. https://doi.org/10.1016/j.ceramint.2021.04.168

    Article  Google Scholar 

  4. Luo SL, Guo HJ, Zhang SK, Wang ZX, Li XH, Yan GC, Wang JX (2019) Comprehensive utilization of metallurgic waste in manganese electrowinning: towards high performance LiMn2O4. Ceram Int 45(7):8607–8615. https://doi.org/10.1016/j.cer-amint.2019.01.180

    Article  Google Scholar 

  5. Zawrah MF, Fadaly EA, Khattab RM, Aly MH, Shafei EH (2020) Synthesis and characterization of nano Mn3O4 and LiMn2O4 spinel from manganese ore and pure materials. Ceram Int 46(11):17514–17522. https://doi.org/10.1016/j.ceramint.2020.04.049

    Article  Google Scholar 

  6. Ma MY, Du YG, Bao SX, Li J, Wei H, Lv Y, Song XL, Zhang TC, Du DY (2020) Removal of cadmium and lead from aqueous solutions by thermal activated electrolytic manganese residues. Sci Total Environ 748:141490. https://doi.org/10.1016/j.sci-totenv.2020.141490

    Article  Google Scholar 

  7. Panimalar S, Chandrasekar M, Logambal S, Uthrakumar R, nmozhi C (2021) Europium-doped MnO2 nanostructures for controlling optical properties and visible light photocatalytic activity. Mater Today: Proc. https://doi.org/10.1016/j.ma-tpr.2021.10.335

    Article  Google Scholar 

  8. IMnI (2015) Overview of global manganese market-June 2015. Annual Conference Presentation[IMnI]

  9. Luo ZG, Shu JC, Chen MJ, Wang R, Zeng X, Yang Y, Wang R, Chen S, Liu R, Liu Z, Sun Z, Yu K, Deng Y (2021) Enhanced leaching of manganese from low-grade pyrolusite using ball milling and electric field. Ecotoxicol Environ Saf 211:111893. https://doi.org/10.1016/j.ecoenv.2021.111893

    Article  Google Scholar 

  10. Chen G, Ling YQ, Li QN, Zheng HW, Qi J, Li KQ, Chen J, Peng J, Gao L, Omran M, He F (2020) Investigation on microwave carbothermal reduction behavior of low-grade pyrolusite. J Mater Res Technol 9(4):7862–7869. https://doi.org/10.1016/j.j-mrt.2020.05.097

    Article  Google Scholar 

  11. Singh V, Gurulaxmi SN (2022) Development of low-cost smelting reduction process using cupola furnace for efficient use of inferior grade manganese ores and rejects, mining. Metall Explor 39(3):1233–1243. https://doi.org/10.1016/j.solidstatesciences.2014.02.015

    Article  Google Scholar 

  12. Kallam VKR, Pandey N, Tripathy SK, Biswas A (2022) Selective recovery of manganese from low-grade ferruginous manganese ores through SO2 leaching, mining. Metall Explor 39(3):1285–1295. https://doi.org/10.1007/s42461-022-00642-9

    Article  Google Scholar 

  13. Dou SQ, Liu JY, Xiao JZ, Pan W (2020) Economic feasibility valuing of deep mineral resources based on risk analysis: Songtao manganese ore - China case study. Resour Policy 66:101612. https://doi.org/10.1016/j.resourpol.2020.101612

    Article  Google Scholar 

  14. Lv X, Chen S, Chen C, Liu L, Liu F, Qiu G (2014) One-step hydrothermal synthesis of LiMn2O4 cathode materials for rechargeable lithium batteries. Solid State Sci 31:16–23. https://doi.org/10.1007/s42461-022-00590-4

    Article  Google Scholar 

  15. Zhang Y, Xie H, Jin H, Li X, Zhang Q, Li Y, Li K, Luo F, Li W, Li C (2021) Enhancing the electrochemical properties of Ti-doped LiMn2O4 spinel cathode materials using a one-step hydrothermal method. ACS Omega 6(33):21304–21315. https://doi.org/10.1016/j.ceramint.2020.04.049

    Article  Google Scholar 

  16. Peng D, Wang JK (2012) Reaction kinetics of potassium manganate prepared by three-phase compression oxidation process, Journal of Portland. J. Chin. Chem. Soc 40:1767–1772+1778

    Google Scholar 

  17. Tao CY, Ding LF, Liu ZH, Du J, Fang X (2012) Study on the preparation of potassium permanganate by electrolysis. Hydrometallurgy [in Chinese] 31:57–60

    Google Scholar 

  18. Li B, Fen YL, Li HR (2015) Gas-solid fluidized two-stage roasting of pyrolusite for preparation of potassium manganate. J Central South Univ (Natural Science Edition) 46:379–385

    Google Scholar 

  19. Peng D, Wang JK, Ma J, Yang SC, Li TJ, Na JX, Wang CH (2011) Potassium manganate was prepared by three-phase compression of the low-grade pyrolusite. Hydrometallurgy [in Chinese] 30:281–283

    Google Scholar 

  20. Lin SD, Li KQ, Yang Y, Gao L, Omran M, Guo SH, Chen J, Chen G (2021) Microwave-assisted method investigation for the selective and enhanced leaching of manganese from low-grade pyrolusite using pyrite as the reducing agent. Chem Eng Process-process Int 159:108209. https://doi.org/10.1016/j.cep.2020.108209

    Article  Google Scholar 

  21. Deng XY, Feng YL, Li HR, Du ZW, Kang JX, Guo CL (2018) Preparation of sodium manganate from low-grade pyrolusite by alkaline predesilication–fluidized roasting technique. T Nonferr Metal Soc 28(5):1045–1052. https://doi.org/10.1016/S1003-6326(18)64742-9

    Article  Google Scholar 

  22. Yang ZC, Feng YL, Li HR, Wang WD, Teng Q (2014) Effect of biological pretreatment on flotation recovery of pyrolusite. T Nonferr Metal Soc 24(5):1571–1577. https://doi.org/10.1016/S1003-6326(14)63227-1

    Article  Google Scholar 

  23. Li SC, Kang CS, Kim SC, Kim CJ, Kang CJ (2021) The extraction of Ta, Nb and rare earths from fergusonite by using KOH sub-molten salt leaching. Hydrometallurgy 201:105358. https://doi.org/10.1016/j.hydromet.2020.105358

    Article  Google Scholar 

  24. Yu MM, Mei GG, Chen XD (2018) Recovering rare earths and aluminum from waste BaMgAl10O17: Eu2+ and CeMgAl11O19: Tb3+ phosphors using NaOH sub-molten salt method. Miner Eng 117:1–7. https://doi.org/10.1016/j.mineng.2017.12.001

    Article  Google Scholar 

  25. Sahoo DK, Anitha M, Mondal S, Singh DK, Mishra R, Kain V (2016) Taguchi optimisation of process parameters for electrowinning of praseodymium metal in molten salt electrolysis. Miner Process Extr Metall 126(4):231–237. https://doi.org/10.1080/03719553.2016.1234813

    Article  Google Scholar 

  26. Peng XY, Liu WG, Liu WB, Zhao L, Zhang NX, Gu XW, Zhou SJ (2021) Fluorite enhanced magnesium recovery from serpentine tailings: kinetics and reaction mechanisms. Hydrometallurgy 201:105571. https://doi.org/10.1016/j.hydromet.202-1.105571

    Article  Google Scholar 

  27. Rogozhnikov D, Karimov K, Shoppert A, Dizer O, Naboichenko S (2021) Kinetics and mechanism of arsenopyrite leaching in nitric acid solutions in the presence of pyrite and Fe(III) ions. Hydrometallurgy 199:105525. https://doi.org/10.1016/j.hydrome-t.2020.105525

    Article  Google Scholar 

  28. Luo MJ, Liu CL, Xue J, Li P, Yu JG (2017) Leaching kinetics and mechanism of alunite from alunite tailings in highly concentrated KOH solution. Hydrometallurgy 174:10–20. https://doi.org/10.1016/j.hydromet.2017.09.008

    Article  Google Scholar 

  29. Chen G, Wang JJ, Wang XH, Zheng SL, Du H, Zhang Y (2013) An investigation on the kinetics of chromium dissolution from Philippine chromite ore at high oxygen pressure in KOH sub-molten salt solution. Hydrometallurgy 139:46–53. https://doi.org/10.1016/j.hydromet.2013.07.004

    Article  Google Scholar 

  30. Zhang KF, Liu ZQ, Qiu XY, Rao S, Zhu W (2020) Hydrometallurgical recovery of manganese, gold and silver from refractory Au-Ag ore by two-stage reductive acid and cyanidation leaching. Hydrometallurgy 196:105406. https://doi.org/10.1016/j.hydro-met.2020.105406

    Article  Google Scholar 

  31. Liu W, Huang C, Han JW, Qin WQ (2021) Removal and reuse of arsenic from arsenic-bearing purified residue by alkaline pressure oxidative leaching and reduction of As (V). Hydrometallurgy 199:105541. https://doi.org/10.1016/j.hydromet.20-20.105541

    Article  Google Scholar 

  32. Gu KH, Liu W, Han JW, Ou ZY, Wu DX, Qin WQ (2019) Arsenic and antimony extraction from high arsenic smelter ash with alkaline pressure oxidative leaching followed by Na2S leaching. Sep Purif Technol 222:53–59. https://doi.org/10.1016/j.seppur.2019.04.028

    Article  Google Scholar 

  33. Liu HB, Du H, Wang DW, Wang SN, Zheng SL, Zhang Y (2013) Kinetics analysis of decomposition of vanadium slag by KOH sub-molten salt method. T Nonferr Metal Soc 23:1489–1500. https://doi.org/10.1016/S1003-6326(13)62621-7

    Article  Google Scholar 

  34. Tao E, Xing ZQ, Yang SY (2020) Efficient removal of VOCl3 from crude TiCl4 by organic reagent: reaction mechanism, kinetics and thermodynamics. Hydrometallurgy 196:105424. https://doi.org/10.1016/j.hydromet.2020.105424

    Article  Google Scholar 

  35. Santos FMF, Pina PS, Porcaro R, Oliveira VA, Silva CA, Leão VA (2010) The kinetics of zinc silicate leaching in sodium hydroxide. Hydrometallurgy 102(1):43–49. https://doi.org/10.1016/j.hydromet.2010.01.010

    Article  Google Scholar 

  36. Chen G, Jiang CL, Liu RL, Xie ZM, Liu ZH, Cen SD, Tao C, Guo SH (2021) Leaching kinetics of manganese from pyrolusite using pyrite as a reductant under microwave heating. Sep Purif Technol 277:119472. https://doi.org/10.1016/j.sep-pur.2021.119472

    Article  Google Scholar 

  37. Lv YJ, Su J, Wen YX, Su HF, Yang KD, Lv XY (2011) Leaching kinetics of pyrolusite by macromolecular melanoidins of molasses alcohol wastewater in H2SO4. Procedia Eng 18:107–115. https://doi.org/10.1016/j.proeng.2011.11.017

    Article  Google Scholar 

  38. Levien KL, Levenspiel O (1999) Optimal product distribution from laminar flow reactors: Newtonian and other power-law fluids. Chem Eng Sci 54(13):2453–2458. https://doi.org/10.1016/S0009-2509(98)00484-9

    Article  Google Scholar 

  39. Ait Brahim J, Ait Hak S, Achiou B, Boulif R, Beniazza R, Benhida R (2022) Kinetics and mechanisms of leaching of rare earth elements from secondary resources. Miner Eng 177:107351. https://doi.org/10.1016/j.mineng.2021.107351

    Article  Google Scholar 

  40. Zhou LS, Peng TJ, Sun HJ, Hui T (2021) Mechanism and kinetics of iron removal in Fe-Al-H2SO4 system by coordination precipitation. J Environ Chem Eng 9(4):105241. https://doi.org/10.1016/j.jece.2021.105241

    Article  Google Scholar 

  41. Shoghian-Alanaghi A, Zamharir AJ, Aghajani H, Tabrizi AT (2022) Improving the leaching rate of molybdenite concentrate using oxidants by adding ethylene glycol and oxygen: kinetic study. Mining Metall Explor 39(4):1753–1761. https://doi.org/10.1021/acsomega.1c01521

    Article  Google Scholar 

  42. Wu JJ, Ahn F, Lee J (2020) Kinetic and mechanism studies using shrinking Ccore model for copper leaching from chalcopyrite in methanesulfonic acid with hydrogen peroxide. Min Proc Ext Met Rev 42(1):38–45. https://doi.org/10.1080/08827508.2020.1795850

    Article  Google Scholar 

Download references

Acknowledgements

We thank LetPub (www.letpub.com) for its linguistic assistance during the preparation of this manuscript.

Funding

This research was supported by the National Nature Science Foundation of China (grant no. 51764007) and the Guizhou Province Graduate Research Fund (YJSCXJH[2020]033).

Author information

Authors and Affiliations

  1. College of Material and Metallurgy, Guizhou University, Guiyang, 550025, China

    Fenglan Luo, Hongyan Xie, Huixin Jin, Chenzhe Li, Ma Lianren & Wang Duolun

Authors
  1. Fenglan Luo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hongyan Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Huixin Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Chenzhe Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ma Lianren
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Wang Duolun
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hongyan Xie.

Ethics declarations

Conflict of Interest

The authors declare no competing interests.

Disclaimer

The authors alone are responsible for the content and writing of the article.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Luo, F., Xie, H., Jin, H. et al. Oxidative Leaching of Low-Grade Pyrolusite in Alkaline Solutions to Produce Potassium Manganate. Mining, Metallurgy & Exploration 40, 81–94 (2023). https://doi.org/10.1007/s42461-022-00694-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s42461-022-00694-x

Keywords

Search

Navigation