From Nickel Ore to Ni Nanoparticles in the Extraction Process: Properties and Application

F. Bahfie$^1$, A. Manaf$^2$, W. Astuti$^1$, F. Nurjaman$^1$, E. Prasetyo$^{1,3}$, Ye. Triapriani$^1$, and D. Susanti$^4$

$^1$Research Centre of Mining Technology, National Research and Innovation Agency of Indonesia, South Lampung, 35361 Lampung, Indonesia
$^2$Physics Department, Faculty of Mathematics and Science, University of Indonesia, 16424 Depok, West Java, Indonesia
$^3$Department of Chemical Engineering, Norwegian University of Science and Technology, 7491 Trondheim, Norway
$^4$Department of Metallurgical and Material Engineering, Faculty of Industrial Technology and Systems Engineering, Institut Teknologi Sepuluh Nopember, 60111 Surabaya, East Java, Indonesia

Received 31.05.2022; final version — 31.01.2023 Download PDF logo PDF

Laterite nickel ore is a mineral rock, which contains iron–nickel oxide compounds. One processing technology proposed to treat the ore is the Caron process. In general, the Caron process combines pyrometallurgical and hydrometallurgical stages. In the pyrometallurgical step, the ore mixed with reductant is heated up to 1800 °C in a rotary kiln-electric furnace to transform iron–nickel oxide into iron–nickel alloy. In the hydrometallurgical stage, nickel has to be dissolved selectively using ammonia solution (alkaline). The further process is aimed to separate and purify the nickel in ammonia solution using solvent extraction and precipitation. The disadvantages of the pyrometallurgical stage in the Caron process include high-energy consumption, low economic value, and technical problems such as partially melted material, which hinders the further process. While in the hydrometallurgical stage, the extensive use of ammonia causes an environmental impact. Selective reduction is proposed to solve problems in the pyrometallurgical stage. Selective reduction is a process favouring the formation of iron oxide to obtain high nickel content in an intermediate product with less energy consumption. An additive is added to the ore to reduce selectively the nickel and decrease the reaction temperature. To solve the environmental impact of ammonia, a novel and safer chemical is proposed as a substitute — the monosodium glutamate (MSG). Selective reduction combined with alkaline leaching using MSG is proposed as an alternative to the Caron method. Precipitation is employed further to purify the nickel that results in nickel nanoparticles with 90–95 wt.% purity.

Keywords: laterite, Caron method, purification, synthesis, nickel nanoparticles.


Citation: F. Bahfie, A. Manaf, W. Astuti, F. Nurjaman, E. Prasetyo, Ye. Triapriani, and D. Susanti, From Nickel Ore to Ni Nanoparticles in the Extraction Process: Properties and Application, Progress in Physics of Metals, 24, No. 1: 173–196 (2023)

  1. X. Ma, Z. Cui, and B. Zhao, Efficient utilization of nickel laterite to produce master alloy, JOM, 68: 3006–3014 (2016);
  2. J. Li, D. Xiong, H. Chen, R. Wang, and Y. Liang, Physicochemical factors affecting leaching of laterite ore in hydrochloric acid, Hydrometallurgy, 129: 14–18 (2012);
  3. X. Lv, C. Bai, S. He, and Q. Huang, Mineral change of Philippine and Indonesia nickel lateritic ore during sintering and mineralogy of their sinter, ISIJ Int., 50: 380–385 (2010);
  4. S. Pournaderi, E. Keskinkılıç, A. Geveci, and Y. A. Topkaya, Reducibility of nickeliferous limonitic laterite ore from Central Anatolia, Can. Metall. Quart., 53: 26–37 (2014);
  5. J. Kim, G. Dodbiba, H. Tanno, K. Okaya, S. Matsuo, and T. Fujita, Calcination of low-grade laterite for concentration of Ni by magnetic separation, Miner. Eng., 23: 282–288 (2010);
  6. C.A. Pickles, C.T. Harris, J. Peacey, and J. Forster, Thermodynamic analysis of the Fe–Ni–Co–Mg–Si–O–H–S–C–Cl system for selective sulphidation of a nickeliferous limonitic laterite ore, Miner. Eng., 54: 52–62 (2013);
  7. C.A. Pickles, J. Forster, and R. Elliott, Thermodynamic analysis of the carbothermic reduction roasting of a nickeliferous limonitic laterite ore, Miner Eng., 65: 33–40 (2014);
  8. S. Al-Khirbash, Genesis and mineralogical classification of Ni-laterites, Oman Mountains, Ore Geol. Rev., 65: 199–212 (2015);
  9. N.M. Rice, A hydrochloric acid process for nickeliferous laterites, Miner. Eng., 88: 28–52 (2016);
  10. T. Agacayak, V. Zedef, and A. Aras, Kinetic study on leaching of nickel from Turkish lateritic ore in nitric acid solution, J. Cent. South Univ., 23: 39–43 (2016);
  11. E.N. Zevgolis, C. Zografidis, T. Perraki, and E. Devlin, Phase transformations of nickeliferous laterites during preheating and reduction with carbon monoxide, J. Therm. Anal. Calorim., 100: 133–139 (2010);
  12. A. Bunjaku, M. Kekkonen, K. Pietilä, and P. Taskinen, Effect of mineralogy and reducing agent on reduction of saprolitic nickel ores, Trans. Inst. Min. Metall. C, 121: 156–165 (2012);
  13. C.A. Pickles and R. Elliott, Thermodynamic analysis of selective reduction of nickeliferous limonitic laterite ore by carbon monoxide, Trans. Inst. Min. Metall. C, 124: 208–2160 (2015);
  14. R. Elliott, F. Rodrigues, C.A. Pickles, and J. Peacey, A two-stage thermal upgrading process for nickeliferous limonitic laterite ores, Can. Metall. Quart., 54: 395–405 (2015);
  15. K. Quast, J.N. Connor, W. Skinner, D.J. Robinson, and J. Addai-Mensah, Preconcentration strategies in the processing of nickel laterite ores Part 1: Literature review, Miner. Eng., 79: 261–268 (2015);
  16. S.L. Chen, X.Y. Guo, W.T. Shi, and N. Li, Extraction of valuable metals from low-grade nickeliferous laterite ore by reduction roasting-ammonia leaching method, Journal of Central South University of Technology, 17: 765–769 (2010);
  17. J. Kyle, Nickel laterite processing technologies – where to next? ALTA 2010 Nickel/Cobalt/Copper Conf. (24–27 May 2010, Perth, Western Australia).
  18. A.D. Dalvi, W.G. Bacon, and R.C. Osborne, The past and the future of nickel laterites, PDAC 2004 International Convention (Trade Show & Investors Exchange, March 7–10, 2004).
  19. M. Valix and W.H. Cheung, Effect of sulfur on the mineral phases of laterite ores at high temperature reduction, Miner. Eng., 15: 523–530 (2002);
  20. B. Ma, C. Wang, W. Yang, F. Yin, and Y. Chen, Screening and reduction roasting of limonitic laterite and ammonia-carbonate leaching of nickel–cobalt to produce a high-grade iron concentrate, Miner. Eng., 50: 106–113 (2013);
  21. M.A.R. Önal and Y.A. Topkaya, Pressure acid leaching of Çaldaǧ lateritic nickel ore: an alternative to heap leaching, Hydrometallurgy, 142: 98–107 (2014);
  22. J.A. Johnson, R.G. McDonald, D.M. Muir, and J. Tranne, Pressure acid leaching of arid-region nickel laterite ore Part IV: Effect of acid loading and additives with nontronite ores, Hydrometallurgy, 78: 264–270 (2005);
  23. D.H. Rubisov, J.M. Krowinkel, and V.G. Papangelakis, Sulphuric acid pressure leaching of laterites-universal kinetics of nickel dissolution for limonites and limonitic/saprolitic blends, Hydrometallurgy, 58: 1–11 (2000);
  24. K. Liu, Q. Chen, Z. Yin, H. Hu, and Z. Ding, Leaching kinetics of rare-earth elements from complex ores by acidic solutions, Hydrometallurgy, 125: 125–136 (2012);
  25. Z. Liu, T. Sun, X. Wang, and E. Gao, Generation process of FeS and its inhibition mechanism on iron mineral reduction in selective direct reduction of laterite nickel ore, Int. J. Miner. Metall. Mater., 22: 901–906 (2015);
  26. F. Bahfie, A. Manaf, W. Astuti, F. Nurjaman, and U. Herlina, Tinjauan teknologi proses ekstraksi bijih nikel laterit, Jurnal Teknologi Mineral dan Batubara, 17, No. 3: 135–152 (2021);
  27. J. MacCarthy, J. Addai-Mensah, and A. Nosrati, Atmospheric acid leaching of siliceous goethitic Ni laterite ore: effect of solid loading and temperature, Miner. Eng., 69: 154–164 (2014);
  28. B. Ma, W. Yang, B. Yang, C. Wang, Y. Chen, and Y. Zhang, Pilot-scale plant study on the innovative nitric acid pressure leaching technology for laterite ores, Hydrometallurgy, 155: 88–94 (2015);
  29. P. Zhang, Q. Guo, G. Wei, L. Meng, L. Han, J. Qu, and T. Qi, Extraction of metals from saprolitic laterite ore through pressure hydrochloric-acid selective leaching, Hydrometallurgy, 157: 149–158 (2015);
  30. Q. Guo, J. Qu, B. Han, P. Zhang, Y. Song, and T. Qi, Innovative technology for processing saprolitic laterite ores by hydrochloric acid atmospheric pressure leaching, Miner. Eng., 71: 1–6 (2015);
  31. W. Astuti, T. Hirajima, K. Sasaki, and N. Okibe, Kinetics of nickel extraction from Indonesian saprolitic ore by citric acid leaching under atmospheric pressure, Miner. Metall. Proc., 32: 176–185 (2015);
  32. B. Wang, Q. Guo, G. Wei, P. Zhang, J. Qu, and T. Qi, Characterization, and atmospheric hydrochloric acid leaching of a limonitic laterite from Indonesia, Hydrometallurgy, 129: 7–13 (2012);
  33. E. Prasetyo, F. Bahfie, and A.S. Handoko, Alkaline leaching of nickel from electric arc furnace dust using ammonia-ammonium glutamate as lixiviant, Ni–Co 2021: The 5th Int. Symp. on Nickel and Cobalt, The Minerals, Metals & Materials Series (2021);
  34. J.A.B. Botelho, D.C.R. Espinosa, D. Dreisinger, and J.A.S. Tenório, Effect of iron oxidation state for copper recovery from nickel laterite leach solution using chelating resin, Separation Science and Technology, 55, No. 4: 1–11 (2020);
  35. Q. Shi, Y. Zhang, J. Huang, T. Liu, H. Liu, and L. Wang, Synergistic solvent extraction of vanadium from leaching solution of stone coal using D2EHPA and PC88A, Separation and Purification Technology, 181: 1–7 (2017);
  36. G.F.R. de Oliveira, J.A.B. Botelho, and J.A.S. Tenório, Separation of cobalt from the nickel-rich solution from HPAL process by synergism using organic extracts cyanex 272 and ionquest 290, Tecnol. Metal. Mater. Miner., 16, No. 4: 464–469 (2019);
  37. V. Miettinen, J. Mäkinen, E. Kolehmainen, T. Kravtsov, and L. Rintala, Iron control in atmospheric acid laterite leaching, Minerals, 9: 404 (2019);
  38. K. Komnitsas, E. Petrakis, O. Pantelaki, and A. Kritikaki, Column leaching of greek low-grade limonitic laterites, Minerals, 8: 377 (2018);
  39. C. Mystrioti, N. Papassiopi, A. Xenidis, and E. Komnitsas, Counter-current leaching of low-grade laterites with hydrochloric acid and proposed purification options of pregnant solution, Minerals, 8: 599 (2018);
  40. P. Vanýsek, CRC Handbook of Chemistry and Physics; Electrochemical Series (Eds. W.M. Haynes, D.R. Lide, and T.J. Bruno) (Taylor & Francis Group: 2017).
  41. M.Z. Mubarok, K. Sukamto, Z.T. Ichlas, and A.T. Sugiarto, Direct sulfuric acid leaching of zinc sulphide concentrate using ozone as oxidant under atmospheric pressure, Miner. Metall. Process., 35: 133–140, (2018);
  42. Z.T. Ichlas, M.Z. Mubarok, A. Magnalita, J. Vaughan, and A.T. Sugiarto, Processing mixed nickel‑cobalt hydroxide precipitate by sulfuric acid leaching followed by selective oxidative precipitation of cobalt and manganese, Hydrometallurgy, 191: 105185 (2020);
  43. M.A. Rhamdhani, E. Jak, and P.C. Hayes, BNC. Part I Microstructure and phase changes during oxidation and reduction processes, Metallurgical and Materials Transactions B, 39: 218–233 (2008);
  44. E. Keskinkilic, S. Pournaderi, A. Geveci, and Y.A. Topkaya, Calcination characteristics of laterite ores from the central region of Anatolia, J. S. Afr. I. Min. Metall., 112: 877–882 (2012).
  45. M.A. Rhamdhani, J. Chen, T. Hidayat, E. Jak, and P. Hayes, Advances in research on nickel production through the Caron process, Proc. EMC 2009 (2009).
  46. M. Jiang, T. Sun, Z. Liu, J. Kou, N. Liu, and S. Zhang, Mechanism of sodium sulphate in promoting selective reduction of nickel laterite ore during reduction roasting process, Int. J. Miner. Process., 123: 32–38 (2013);
  47. X. Tang, R. Liu, L. Yao, Z. Ji, Y. Zhang, and S. Li, Ferronickel enrichment by fine particle reduction and magnetic separation from nickel laterite ore, Int. J. Minerals, Metall. Mater., 21: 955–961 (2014);
  48. D.Q. Zhu, Y. Cui, K. Vining, S. Hapugoda, J. Douglas, J. Pan, and G.L. Zheng, Upgrading low nickel content laterite ores using selective reduction followed by magnetic separation, Int. J. Miner. Process., 106: 1–7 (2012);
  49. J. Lu, S. Liu, J. Shangguan, W. Du, F. Pan, and S. Yang, The effect of sodium sulphate on the hydrogen reduction process of nickel laterite ore, Miner. Eng., 49: 154–164 (2013);
  50. M. Rao, G. Li, X. Zhang, J. Luo, Z. Peng, and T. Jiang, Reductive roasting of nickel laterite ore with sodium sulphate for Fe–Ni production. Part I: Reduction/sulfidation characteristics, Sep. Sci. Technol., 51: 1408–1420 (2016);
  51. M. Rao, G. Li, X. Zhang, J. Luo, Z. Peng, and T. Jiang, Reductive roasting of nickel laterite ore with sodium sulphate for Fe-Ni production. Part II: Phase transformation and grain growth, Sep. Sci. Technol., 51: 1727-1735 (2016b);
  52. S. Zhou, B. Li, Y. Wei, H. Wang, C. Wang, and B. Ma, Effect of additives on phase transformation of nickel laterite ore during low‐temperature reduction roasting process using carbon monoxide, Drying, Roasting, and Calcining of Minerals: 177–184, (2015);
  53. F. Nurjaman, A. Rahmawaty, M.F. Karimy, B. Suharno, and D. Ferdian, The role of sodium-based additives on reduction process of nickel ore, IOP Conf. Ser.: Mater. Sci. Eng., 478: 012001 (2018);
  54. F. Nurjaman, A. Sa’adah, and B. Suharno, Optimal conditions for selective reduction process of nickel laterite ore, IOP Conf. Series: Mater. Sci. Eng., 523: (2019);
  55. A. Bunjaku, M. Kekkonen, P. Taskinen, and L. Holappa, Thermal behaviour of hydrous nickel–magnesium silicates when heating up to 750 °C, Mineral Processing and Extractive Metallurgy, 120, No. 3: 139–146 (2011);
  56. G. Li, T. Shi, M. Rao, T. Jiang, and Y. Zhang, Beneficiation of nickeliferrous laterite by reduction roasting in the presence of sodium sulphate, Minerals Engineering, 32: 19–26 (2012);
  57. G.-J. Chen, J.-S. Shiau, S.-H. Liu, and W.-S. Hwang, Optimal combination of calcination and reduction conditions as well as Na2SO4 additive for carbothermic reduction of limonite ore, Materials Transection, 57: 1560–1566 (2016);
  58. I. Setiawan, S. Harjanto, A. Rustandi, and R. Subagja, Reducibility of low nickel lateritic ores with presence of calcium sulphate, Int. J. Eng. Technol., 14: 56–66 (2014).
  59. S. Yang, W. Du, P. Shi, J. Shangguan, S. Liu, C. Zhou, P. Chen, Q. Zhan, and H. Fan, Mechanistic and kinetic analysis of Na2SO4-modified laterite decomposition by thermogravimetry coupled with mass spectrometry, PLoS ONE, 11, No. 6: 1–21 (2016);
  60. L.A. Paramo, A.A. Feregrino-Perez, R. Guevara, S. Mendoza, and K. Esquivel, Nanoparticles in agroindustry: applications, toxicity, challenges, and trends, Nanomaterials, 10, No. 9: 654–86 (2020);
  61. R. Magaye and J. Zhao, Recent progress in studies of metallic nickel and nickel-based nanoparticles’ genotoxicity and carcinogenicity, Environ. Toxicol. Pharmacol., 34, No. 3: 644–650 (2012);
  62. I. Bibi, S. Kamal, A. Ahmed, M. Iqbal, S. Nouren, and K. Jilani, Nickel nanoparticle synthesis using camellia sinensis as reducing and capping agent: growth mechanism and photocatalytic activity evaluation, Int. J. Biol. Macromol., 103: 783–790 (2017);
  63. Y. Cheng, M. Guo, M. Zhai, Y. Yu, and J. Hu, Nickel nanoparticles anchored onto Ni foam for supercapacitors with high specific capacitance, J. Nanosc. Nanotechnol., 20, No. 4: 2402–2407 (2020);
  64. A.R. Abdel Fattah, T. Majdi, A.M. Abdalla, S. Ghosh, and I.K. Puri, Nickel nanoparticles entangled in carbon nanotubes: novel ink for nanotube printing, ACS Appl. Mater. Interfaces, 8, No. 3: 1589–1593 (2016);
  65. M.M. Barsan, T.A. Enache, N. Preda, G. Stan, N.G. Apostol, and E. Matei, Direct immobilization of biomolecules through magnetic forces on Ni electrodes via Ni nanoparticles: applications in electrochemical biosensors, ACS Appl. Mater. Interfaces, 11, No. 22: 19867–19877 (2019);
  66. D. Hill, A. R. Barron, and S. Alexander, Comparison of hydrophobicity and durability of functionalized aluminium oxide nanoparticle coatings with magnetite nanoparticles-links between morphology and wettability, J. Colloid Interface Sci., 555: 323–30 (2019);
  67. Z. Bian, S. Das, M.H. Wai, P. Hongmanorom, and S. Kawi, A review on bimetallic nickel-based catalysts for CO2 reforming of methane, ChemPhysChem. 18, No. 22: 3117–3134 (2017);
  68. A. Sagasti, V. Palomares, J. M. Porro, I. Orue, M. B. Sanchez-Ilarduya, and A. C. Lopes, Magnetic, magnetoelastic and corrosion resistant properties of (Fe-Ni)-based metallic glasses for structural health monitoring applications, Materials, 13, No. 1: 57–70 (2019);
  69. D. Wang, Y. Jia, Y. He, L. Wang, J. Fan, and H. Xie, Enhanced photothermal conversion properties of magnetic nanofluids through rotating magnetic field for direct absorption solar collector, J. Colloid Interface Sci., 557: 266–75 (2019);
  70. N.D. Jaji, H.L. Lee, M.H. Hussin, H.M. Akil, M.R. Zakaria, and M.B.H. Othman, Advanced nickel nanoparticles technology: from synthesis to applications, Nanotechnol. Rev., 9: 1456–1480 (2020);
  71. A.M. Ealias and M. Saravanakumar, A review on the classification, characterisation, synthesis of nanoparticles and their application, IOP Conf. Ser. Mater. Sci. Eng., 263: 32019 (2017);
  72. O. Molnarova, P. Malek, J. Vesely, P. Minarik, F. Lukac, T. Chraska, The influence of milling and spark plasma sintering on the microstructure and properties of the Al7075 alloy, Materials, 11, No. 4: 547–64 (2018);
  73. S. Ida, D. Shiga, M. Koinuma, and Y. Matsumoto, Synthesis of hexagonal nickel hydroxide nanosheets by exfoliation of layered nickel hydroxide intercalated with dodecyl sulfate ions, J. Am. Chem. Soc., 130, No. 43: 14038–14039 (2008);
  74. G. Li, X. Wang, H. Ding, and T. Zhang, A facile synthesis method for Ni(OH)2 ultrathin nanosheets and their conversion to porous NiO nanosheets used for formaldehyde sensing, RSC Adv., 2: 13018–13023 (2012);
  75. A.G. Solomenko, R.M. Balabai, T.M. Radchenko, and V.A. Tatarenko, Functionalization of quasi-two-dimensional materials: chemical and strain-induced modifications, Prog. Phys. Met., 23, No. 2: 147–238 (2022);
  76. T.M. Radchenko, I.Yu. Sahalianov, V.A. Tatarenko, Yu.I. Prylutskyy, P. Szroeder, M. Kempiński, and W. Kempiński, The impact of uniaxial strain and defect pattern on magnetoelectronic and transport properties of graphene, Handbook of Graphene: Growth, Synthesis, and Functionalization (Eds. E. Celasco and A. Chaika) (Beverly, MA: Scrivener Publishing LLC: 2019), Vol. 1, Ch. 14, p. 451;
  77. P. Szroeder, I.Yu. Sagalianov, T.M. Radchenko, V.A. Tatarenko, Yu.I. Prylutskyy, and W. Strupiński, Effect of uniaxial stress on the electrochemical properties of graphene with point defects, Appl. Surf. Sci., 442: 185–188 (2018);
  78. P. Szroeder, I. Sahalianov, T. Radchenko, V. Tatarenko, and Yu. Prylutskyy, The strain- and impurity-dependent electron states and catalytic activity of graphene in a static magnetic field, Optical Mater., 96: 109284-1–5 (2019);
  79. T.M. Radchenko and V.A. Tatarenko, Statistical thermodynamics and kinetics of long-range order in metal-doped graphene, Solid State Phenomena, 150: 43–72 (2009);
  80. T.M. Radchenko and V.A. Tatarenko, Kinetics of atomic ordering in metal-doped graphene, Solid State Sciences, 12, No. 2: 204–209 (2010);
  81. T.M. Radchenko and V.A. Tatarenko, A statistical-thermodynamic analysis of stably ordered substitutional structures in graphene, Physica E: Low-Dimensional Systems and Nanostructures, 42, No. 8: 2047–2054 (2010);
  82. T.M. Radchenko, A.A. Shylau, and I.V. Zozoulenko, Conductivity of epitaxial and CVD graphene with correlated line defects, Solid State Communications, 195: 88–94 (2014);
  83. I.Yu. Sahalianov, T.M. Radchenko, V.A. Tatarenko, and Yu.I. Prylutskyy, Magnetic field-, strain-, and disorder-induced responses in an energy spectrum of graphene, Annals of Physics, 398: 80–93 (2018);
  84. T.M. Radchenko, I.Yu. Sahalianov, V.A. Tatarenko, Yu.I. Prylutskyy, P. Szroeder, M. Kempiński, and W. Kempiński, Strain- and adsorption-dependent electronic states and transport or localization in graphene, Springer Proceedings in Physics: Nanooptics, Nanophotonics, Nanostructures, and Their Applications (Eds. O. Fesenko and L. Yatsenko) (Cham, Switzerland: Springer: 2018), Vol. 210, Ch. 3, p. 25;
  85. T.M. Radchenko, V.A. Tatarenko, and G. Cuniberti, Effects of external mechanical or magnetic fields and defects on electronic and transport properties of graphene, Materials Today: Proceedings, 35, Pt. 4: 523 (2021);
  86. I.Yu. Sagalianov, T.M. Radchenko, V.A. Tatarenko, and G. Cuniberti, Sensitivity to strains and defects for manipulating the conductivity of graphene, EPL, 132: 48002 (2020);
  87. X.-L. Wei, Z.-K. Tang, G.-C. Guo, S. Ma, and L.-M. Liu, Electronic and magnetism properties of two-dimensional stacked nickel hydroxides and nitrides, Sci. Rep., 5: 11656-1–9 (2015);