Selective hydrogen reduction of binary iron-cobalt chlorides

Abstract

Global demand for cobalt is proliferating with the booming usage and consumption of Li-ion batteries in energy storage applications. With high cobalt content, cobalt white alloy has been an important intermediate product for cobalt production. In this paper, a method of hydrochlorination roasting-hydrogen reduction of cobalt white alloy is proposed to separate the valuable metals in cobalt white alloy. The hydrochlorination roasting process achieves the separation of copper and silicon from the cobalt white alloy and produces iron-cobalt binary chloride. This paper focuses on the effects of reduction temperature, reduction time, and hydrogen concentration during the hydrogen reduction of iron-cobalt binary chloride, with the aim of separating the two metals. The Co/Fe mass ratio in the reduction product is 10.71, with the cobalt content usually above 90 wt% under optimal conditions. The reduction product is a micro-fibrous Co-rich alloy exhibiting a significant specific surface area, which may have promising applications in catalysis. A mechanism based on chemical vapor deposition has been proposed to explain the formation of micro-fibrous products.

Keywords

cobalt white alloy / hydrogen reduction / selective separation / fibrous cobalt

References

[1] ZengX, LiJ. On the sustainability of cobalt utilization in China [J]. Resources, Conservation and Recycling, 2015, 104: 12-18

[2] ChandraM, YuD, TianQ, et al. . Recovery of cobalt from secondary resources: A comprehensive review [J]. Mineral Processing and Extractive Metallurgy Review, 2021, 43: 679-700

[3] TianL, LiuQ, WuJ, et al. . Template-free hydrothermal synthesis and gas-sensitivity of hollow-structured Cu_0.3Co_2.7O₄ microspheres [J]. Journal of Central South University, 2021, 28: 1946-1954

[4] GuoX, LiH, YuD, et al. . Molten salt electrolysis of spent nickel-based superalloys with liquid cathode for the selective separation of nickel [J]. Separation and Purification Technology, 2022, 302: 122168

[5] KhallafA, BhlolM, DawoodO, et al. . Wear resistance, hardness, and microstructure of carbide dispersion strengthened high-entropy alloys [J]. Journal of Central South University, 2022, 293529-3543

[6] LaiX, HuG, PengZ, et al. . Li_1.4Al_0.4Ti_1.6(PO₄)₃ coated Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ for enhancing electrochemical performance of lithium-ion batteries [J]. Journal of Central South University, 2022, 29: 1463-1478

[7] ChenX, KangD, CaoL, et al. . Separation and recovery of valuable metals from spent lithium ion batteries: Simultaneous recovery of Li and Co in a single step [J]. Separation and Purification Technology, 2019, 210: 690-697

[8] NortheyS, MohrS, MuddG, et al. . Modelling future copper ore grade decline based on a detailed assessment of copper resources and mining [J]. Resources, Conservation and Recycling, 2014, 83: 190-201

[9] FarjanaS, HudaN, MahmudM. Life cycle assessment of cobalt extraction process [J]. Journal of Sustainable Mining, 2019, 18: 150-161

[10] ZhaiX, LiN, ZhangX. Recovery of cobalt from converter slag of Chambishi Copper Smelter using reduction smelting process [J]. Transactions of Nonferrous Metals Society of China, 2011, 21: 2117-2121

[11] ZhanJ, HeY, ZhouD, et al. . Thermodynamic analysis on synthesis of fibrous Ni-Co alloys precursor and Ni/Co ratio control [J]. Transactions of Nonferrous Metals Society of China, 2011, 21: 1141-1148

[12] CrundwellF, PreezN, KnightsB. Production of cobalt from copper-cobalt ores on the African Copperbelt–An overview [J]. Minerals Engineering, 2020, 156: 106450

[13] GuoX, ZhangC, TianQ. Liquid metals dealloying as a general approach for the selective extraction of metals and the fabrication of nanoporous metals: A review [J]. Materials Today Communications, 2021, 26102007

[14] MakuzaB, TianQ, GuoX, et al. . Pyrometallurgical options for recycling spent lithium-ion batteries: A comprehensive review [J]. Journal of Power Sources, 2021, 491229622

[15] LiG, RaoM, LiQ, et al. . Extraction of cobalt from laterite ores by citric acid in presence of ammonium bifluoride [J]. Transactions of Nonferrous Metals Society of China, 2010, 201517-1520

[16] XuP, WangQ, LiC, et al. . Relationship between process mineralogical characterization and beneficiability of low-grade laterite nickel ore [J]. Journal of Central South University, 2021, 28: 3061-3073

[17] ZhaoH, MaB, HongS, et al. . Recovery of Copper and Cobalt from Converter Slags via Reduction - Sulfurization Smelting Using Spent Pot Lining as the Reductant [J]. ACS Sustainable Chemistry & Engineering, 2021, 9: 4234-4246

[18] ZhangD, SunF, ZhaoZ, et al. . Enhancing the leaching performance of molybdenite and Co-white alloy simultaneously: A structure conversion process [J]. Minerals Engineering, 2022, 181: 107543

[19] XuZ, YueR, YanK, et al. . Alkali-roasting and desilication pretreatment of refractory high-silicon cobalt white alloy [J]. The Chinese Journal of Nonferrous Metals, 2012, 222916-2923

[20] UsgsMineral commodity summaries 2023 [M], 2023, United States, USGS: 6061

[21] QinH, MakuzaB, ZhaoJ, et al. . Hydrochlorination of copper-cobalt alloy for efficient separation of valuable metals [J]. Journal of Sustainable Metallurgy, 2022, 8: 795-805

[22] BurzyńskaL, GumowskaW, RudnikE. Influence of the composition of Cu-Co-Fe alloys on their dissolution in ammoniacal solutions [J]. Hydrometallurgy, 2004, 71: 447-455

[23] XiaoL, ChenB, ZhongH, et al. . Bioleaching of cobalt white alloy in the presence of acidithiobacillus ferrooxidans [J]. Applied Mechanics and Materials, 2013, 373–375: 2042-2045

[24] TianL, WuX, GongA, et al. . Process and kinetics of extracting cobalt from complex high-silicon white alloy by sulfuric acid oxidation leaching [J]. JOM, 2021, 73: 1279-1289

[25] BurzynskaL, GumowskaW, RudnikE, et al. . Mechanism of the anodic dissolution of Cu₇₀-Co₄-Fe₁₄-Pb₇ alloy originated from reduced copper converter slag in an ammoniacal solution [J]. Hydrometallurgy, 2008, 92: 34-41

[26] FengR, XuS, LiuJ, et al. . The influence of Cl⁻ on the electrochemical dissolution of cobalt white alloy containing high silicon in a sulfuric acid solution [J]. Hydrometallurgy, 2014, 142: 12-22

[27] XiaW, ChenX, ShiH. Extracting Cu, Co and Fe from white alloy with HCl by adding H₂O₂ [J]. JOM, 2010, 62: 49-52

[28] LiuW, RaoS, WangW, et al. . Selective leaching of cobalt and iron from cobalt white alloy in sulfuric acid solution with catalyst [J]. International Journal of Mineral Processing, 2015, 141: 8-14

[29] YinF, XingP, LiQ, et al. . Magnetic separation-sulphuric acid leaching of Cu-Co-Fe matte obtained from copper converter slag for recovering Cu and Co [J]. Hydrometallurgy, 2014, 149: 189-194

[30] RenG, LiuZ, PanB, et al. . A novel process for cobalt and copper recovery from cobalt white alloy with high silicon [J]. Metallurgical Research & Technology, 2020, 117: 404

[31] ZhangC, GuoX, YuD, et al. . Treatment of copper-cobalt alloy with molten magnesium for metal extraction [J]. Journal of Alloys and Compounds, 2021, 874159933

[32] BaleC, BélisleE, ChartrandP. FactSage thermochemical software and databases, 2010–2016 [J]. Calphad, 2016, 5435-53

[33] DugleuxP, de Almeida MarquesS. Preparation of metal powders of groups VI and VIII (Fe, Co, Ni) by the vapor phase reduction of their chlorides pure or in binary mixtures [J]. Powder Technology, 1980, 27: 45-52

[34] GaoC, WangH, LiS, et al. . Enhanced cobalt-based catalysts through alloying ruthenium to cobalt lattice matrix as an efficient catalyst for overall water splitting [J]. Electrochimica Acta, 2019, 327: 134958

[35] KimK, LeeH, NohW, et al. . Cobalt ferrite nanoparticles to form a catalytic Co-Fe alloy carbide phase for selective CO₂ hydrogenation to light olefins [J]. ACS Catalysis, 2020, 108660-8671

[36] LourieO, JonesC, BartlettB, et al. . CVD growth of boron nitride nanotubes [J]. Chemistry of Materials, 2000, 12: 1808-1810

[37] MaxwellJ, BlackM, ChavezC, et al. . Growth of normally-immiscible materials (NIMs), binary alloys, and metallic fibers by hyperbaric laser chemical vapor deposition [J]. Applied Physics A, 2008, 91: 507-514

[38] TianC, ZhaoS, FengY, et al. . Research progress and prospect of silicon nanotubes in new energy field [J]. Journal of Central South University, 2023, 30(7): 2133-2148

[39] WangH, SohnH. Effects of firing and reduction conditions on swelling and iron whisker formation during the reduction of iron oxide compact [J]. ISIJ International, 2011, 51: 906-912