Revolutionizing titanium production: A comprehensive review of thermochemical and molten salt electrolysis processes
Haohang Ji , Shenghui Guo , Lei Gao , Li Yang , Hengwei Yan , Hongbo Zeng
International Journal of Minerals, Metallurgy, and Materials ›› 2026, Vol. 33 ›› Issue (1) : 15 -34.
Revolutionizing titanium production: A comprehensive review of thermochemical and molten salt electrolysis processes
Titanium exhibits outstanding properties, particularly, high specific strength and resistance to both high and low temperatures, earning it a reputation as the metal of the future. However, because of the highly reactive nature of titanium, metallic titanium production involves extensive procedures and high costs. Considering its advantages and limitations, the European Union has classified titanium metal as a critical raw material (CRM) of low category. The Kroll process is predominantly used to produce titanium; however, molten salt electrolysis (MSE) is currently being explored for producing metallic titanium at a low cost. Since 2000, electrolytic titanium production has undergone a wave of technological advancements. However, because of the intermediate and disproportionation reactions in the electrolytic titanium production process, the process efficiency and titanium purity according to industrial standards could not be achieved. Consequently, metallic titanium production has gradually diversified into employing technologies such as thermal reduction, MSE, and titanium alloy preparation. This study provides a comprehensive review of research advances in titanium metal preparation technologies over the past two decades, highlighting the challenges faced by the existing methods and proposing potential solutions. It offers useful insights into the development of low-cost titanium preparation technologies.
titanium preparation / titanium alloy / thermal reduction / molten salt electrolysis
| [1] |
|
| [2] |
|
| [3] |
|
| [4] |
|
| [5] |
J. Sure, D.S.M. Vishnu, R.V. Kumar, U.K. Mudali, and C. Schwandt, Corrosion performance of electrochemically prepared Ti–5Ta–2Nb alloy in concentrated nitric acid, Mater. Today Commun., 26(2021), art. No. 101786. |
| [6] |
|
| [7] |
|
| [8] |
|
| [9] |
Global Titanium Mining—Statistics & facts, [2025–04–25], https://www.statista.com/topics/11141/titanium-industry-worldwide/. |
| [10] |
|
| [11] |
|
| [12] |
|
| [13] |
|
| [14] |
|
| [15] |
|
| [16] |
|
| [17] |
|
| [18] |
N. Matsanga, M. Wa Kalenga, and W. Nheta, An overview of thermochemical reduction processes for titanium production, Minerals, 15(2025), No. 1, art. No. 17. |
| [19] |
V. Tebaldo, G. Gautier di Confiengo, D. Duraccio, and M.G. Faga, Sustainable recovery of titanium alloy: From waste to feedstock for additive manufacturing, Sustainability, 16(2024), No. 1, art. No. 330. |
| [20] |
R.G. Reddy, P.S. Shinde, and A.M. Liu, Review: The emerging technologies for producing low-cost titanium, J. Electrochem. Soc., 168(2021), No. 4, art. No. 042502. |
| [21] |
M. El Khalloufi, O. Drevelle, and G. Soucy, Titanium: An overview of resources and production methods, Minerals, 11(2021), No. 12, art. No. 1425. |
| [22] |
|
| [23] |
|
| [24] |
F.W. Hurd, Metal Reduction Process Employing Metal Subhalides, Google Patents, Appl. 4032329, 1977. |
| [25] |
F.W. Hurd, Metal or Alloy Forming Reduction Process and Apparatus, Google Patents, Appl. 4687632, 1987. |
| [26] |
|
| [27] |
|
| [28] |
|
| [29] |
|
| [30] |
|
| [31] |
|
| [32] |
|
| [33] |
|
| [34] |
|
| [35] |
|
| [36] |
|
| [37] |
|
| [38] |
L.I. Perez-Andrade, V.S. Bhattiprolu, W.M. Schuette, and L.N. Brewer, Influence of powder properties and processing gas on the microstructural evolution of Armstrong CP-titanium and Ti6Al4V powders processed by cold spray, Surf. Coat. Technol., 431(2022), art. No. 128011. |
| [39] |
|
| [40] |
|
| [41] |
|
| [42] |
|
| [43] |
|
| [44] |
|
| [45] |
|
| [46] |
|
| [47] |
|
| [48] |
|
| [49] |
|
| [50] |
|
| [51] |
|
| [52] |
B. Wang, C.Y. Chen, J.Q. Li, L.Z. Wang, Y.P. Lan, and S.Y. Wang, Production of Fe–Ti alloys from mixed slag containing titanium and Fe2O3 via direct electrochemical reduction in molten calcium chloride, Metals, 10(2020), No. 12, art. No. 1611. |
| [53] |
|
| [54] |
|
| [55] |
S.K. Nayak, C.J. Hung, V. Sharma, et al., Insight into point defects and impurities in titanium from first principles, NPJ Comput. Mater., 4(2018), art. No. 11. |
| [56] |
|
| [57] |
|
| [58] |
|
| [59] |
|
| [60] |
|
| [61] |
J.W. Yu, Y. Ou, Y.S. Sun, Y.J. Li, and Y.X. Han, Hydrogen reduction behaviors and mechanisms of vanadium titanomagnetite ore under fluidized bed conditions, Powder Technol., 402(2022), art. No. 117340. |
| [62] |
|
| [63] |
|
| [64] |
|
| [65] |
|
| [66] |
|
| [67] |
|
| [68] |
|
| [69] |
|
| [70] |
C.L. Yeh and C.Y. Ke, In situ formation of TiB2/Al2O3-reinforced Fe3Al by combustion synthesis with thermite reduction, Metals, 8(2018), No. 4, art. No. 288. |
| [71] |
|
| [72] |
|
| [73] |
|
| [74] |
|
| [75] |
|
| [76] |
|
| [77] |
|
| [78] |
|
| [79] |
|
| [80] |
J.Z. Yang, Y.W. Wang, J.P. Peng, and Y.Z. Di, Reaction mechanism and kinetics of ferrotitanium preparation by aluminothermic reduction of CaTiO3, Mater. Today Commun., 30(2022), art. No. 102995. |
| [81] |
Z.Y. Wang, J.L. Zhang, Z.J. Liu, et al., Production of ferrotitanium alloy from titania slag based on aluminothermic reduction, J. Alloy. Compd., 810(2019), art. No. 151969. |
| [82] |
|
| [83] |
B.L. Yan, J. Wang, T. Yang, et al., Synthesis of Ti powders with different morphologies via controlling the valence state of the titanium ion in KCl–NaCl molten salt, J. Electroanal. Chem., 876(2020), art. No. 114496. |
| [84] |
|
| [85] |
|
| [86] |
M.A. Steinberg, S.S. Carlton, M.E. Sibert, and E. Wainer, Preparation of titanium by fluoride electrolysis, J. Electrochem. Soc., 102(1955), No. 6, art. No. 332. |
| [87] |
|
| [88] |
D.J. Fray, Removal of Oxygen from Metal oxides and Solid solutions by Electrolysis in a Fused Salt, International Patent, WO 99/64638, 1999. |
| [89] |
|
| [90] |
|
| [91] |
|
| [92] |
|
| [93] |
|
| [94] |
|
| [95] |
|
| [96] |
|
| [97] |
|
| [98] |
|
| [99] |
S.C. Heck, M.F. de Oliveira, and E. Radovanovic, Ti production from natural rutile sand by the FFC process: Experimental and mathematical modelling study, J. Electroanal. Chem., 905(2022), art. No. 115996. |
| [100] |
|
| [101] |
|
| [102] |
|
| [103] |
S.C. Heck and E. Radovanovic, Determination of kinetic parameters for TiO2 and Nb2O5 molten salt FFC reduction by modelling experimental sweep voltammograms, J. Electroanal. Chem., 889(2021), art. No. 115233. |
| [104] |
|
| [105] |
|
| [106] |
K. Zhao and K.J. Liu, Investigation of the electrochemical reduction of porous CaTiO3 pellets in CaCl2%–0.5%CaO molten salt, J. Electrochem. Soc., 169(2022), No. 5, art. No. 052504. |
| [107] |
G.L. Zhao, Y. Xu, and Y.Q. Cai, Effect of sintering temperature and porosity on electro-deoxidation of calcium titanate in CaCl2–NaCl molten salt, Int. J. Electrochem. Sci., 17(2022), No. 2, art. No. 220245. |
| [108] |
|
| [109] |
|
| [110] |
|
| [111] |
|
| [112] |
J.J. Liu, S.L. Li, Z.P. Lv, Y. Fan, J.L. He, and J.X. Song, Electro-desulfurization of metal sulfides in molten salts, Sep. Purif. Technol., 310(2023), art. No. 123109. |
| [113] |
|
| [114] |
|
| [115] |
|
| [116] |
|
| [117] |
|
| [118] |
|
| [119] |
|
| [120] |
|
| [121] |
|
| [122] |
|
| [123] |
|
| [124] |
|
| [125] |
|
| [126] |
|
| [127] |
|
| [128] |
|
| [129] |
|
| [130] |
N. Kwon, J.S. Byeon, H.C. Kim, et al., Effective deoxidation process of titanium scrap using MgCl2 molten salt electrolytic, Metals, 11(2021), No. 12, art. No. 1981. |
| [131] |
L.X. Kong, T. Ouchi, and T.H. Okabe, Electrochemical deoxidation of titanium in molten MgCl2–HoCl3, MATEC Web Conf., 321(2020), art. No. 07006. |
| [132] |
|
| [133] |
|
| [134] |
F.X. Zhu, L. Li, X.Z. Cheng, S.R. Ma, L.W. Jiang, and K.H. Qiu, Direct electrochemical reduction of low titanium chlorides into titanium aluminide alloy powders from molten eutectic KCl–LiCl–MgCl2, Electrochim. Acta, 357(2020), art. No. 136867. |
| [135] |
|
| [136] |
M. Dayah, Ptable® is a registered trademark of Michael Dayah, (2022–10–12) [2025–04–25], https://ptable.com/lang=zh-hans#. |
| [137] |
|
| [138] |
|
| [139] |
|
| [140] |
|
| [141] |
|
| [142] |
|
| [143] |
|
| [144] |
J.J. Peng, G.M. Li, H.L. Chen, D.H. Wang, X.B. Jin, and G.Z. Chen, Cyclic voltammetry of ZrO2 powder in the metallic cavity electrode in molten CaCl2, J. Electrochem. Soc., 157(2010), No. 1, art. No. F1. |
| [145] |
|
| [146] |
|
| [147] |
|
| [148] |
|
| [149] |
R. Bhagat, M. Jackson, D. Inman, and R. Dashwood, Production of Ti–W alloys from mixed oxide precursors via the FFC Cambridge process, J. Electrochem. Soc., 156(2009), No. 1, art. No. E1. |
| [150] |
|
| [151] |
R. Bhagat, M. Jackson, D. Inman, and R. Dashwood, The production of Ti–Mo alloys from mixed oxide precursors via the FFC Cambridge process, J. Electrochem. Soc., 155(2008), No. 6, art. No. E63. |
| [152] |
Z.Y. Pang, X.L. Zou, S.S. Li, W. Tang, Q. Xu, and X.G. Lu, Molten salt electrochemical synthesis of ternary carbide Ti3AlC2 from titanium-rich slag, Adv. Eng. Mater., 22(2020), No. 5, art. No. 1901300. |
| [153] |
|
| [154] |
|
| [155] |
|
| [156] |
F. Cardarellir, Electrochemical Deoxidation of Titanium and its Alloy Process, US Patent, 7504017, 2009. |
| [157] |
J.C. Withers and R.O. Loutfy, Thermal and Electrochemical Process for Metal Production, US Patent, 7410562, 2008. |
| [158] |
|
| [159] |
|
| [160] |
|
| [161] |
|
| [162] |
|
| [163] |
|
| [164] |
|
| [165] |
|
| [166] |
J.X. Wang, Z. Wang, J.G. Tu, J. Zhu, M.Y. Wang, and S.Q. Jiao, Purification of titanium oxycarbonitride by leaching from titanium slag with carbothermal reduction, Hydrometallurgy, 215(2023), art. No. 105984. |
| [167] |
S. Jiao, T. Donghua, and J. Handongr, Preparing Process for Titanium of Ti–C–S Anode by Carbonized/sulfurized Ilmenite, US Patents, 11473207, 2022. |
| [168] |
|
| [169] |
|
| [170] |
H.D. Jiao, W.L. Song, H.S. Chen, M.Y. Wang, S.Q. Jiao, and D.N. Fang, Sustainable recycling of titanium scraps and purity titanium production via molten salt electrolysis, J. Cleaner Prod., 261(2020), art. No. 121314. |
| [171] |
J.X. Liu, J.C. Liu, D.W. Long, and K. Zhan, Electroplating titanium film on 316L stainless steel in LiCl–KCl–Tix+ (2 < x < 3) molten salts, Nucl. Sci. Tech., 31(2020), No. 5, art. No. 43. |
| [172] |
D.J. Fray and S. Jiaor, Treatment of Titanium Ores, US Patents, 9181604, 2015. |
| [173] |
|
| [174] |
C. Haixian and J. Caor, Device and Process for Preparing High-purity Titanium Powder by Continuous Electrolysis, US Patents, 17/422453, 2022. |
| [175] |
|
| [176] |
|
| [177] |
|
| [178] |
|
| [179] |
|
| [180] |
|
| [181] |
|
| [182] |
|
| [183] |
|
| [184] |
|
| [185] |
|
| [186] |
|
| [187] |
|
| [188] |
|
| [189] |
|
| [190] |
|
| [191] |
|
| [192] |
|
| [193] |
|
| [194] |
F.X. Zhua, K.H. Li, W.C. Song, L. Li, D.F. Zhang, and K.H. Qiu, Composition and structure of Ti–Al alloy powders formed by electrochemical co-deposition in KCl–LiCl–MgCl2–TiCl3–AlCl3 molten salt, Intermetallics, 139(2021), art. No. 107341. |
| [195] |
|
| [196] |
|
| [197] |
|
| [198] |
|
| [199] |
|
| [200] |
|
| [201] |
|
University of Science and Technology Beijing
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