Vol. 337 No. 8 (2026)
DOI https://doi.org/10.18799/24131830/2026/8/5052
Stability of hydrochloric acid titanium-containing solutions for processing quartz-leucoxene concentrate by selective chlorination
Abstract. Relevance. The titanium industry is a strategically important area of development for any modern country. Aerospace, medical, food and other material-intensive industries are just a short list of consumers of titanium compounds. Most of the titanium reserves in the Russian Federation are presented in the form of quartz-leucoxene sandstones, the processing of which allows obtaining titanium tetrachloride, a precursor for the synthesis of titanium dioxide. Objective. To study the stability of aqueous solutions of titanium tetrachloride and to assess the effect of silicon tetrachloride impurity on the rate of hydrolytic decomposition of TiCl4. Methods. To study the hydrolysis processes, spectrophotometry and magnetic plasma atomic emission spectroscopy were used. Results and conclusions. The hydrolysis process of aqueous hydrochloric acid solutions of TiCl4 was studied. It was proven that the hydrolysis process accelerates as the concentration of TiCl4 in the solution decreases, while TiCl4 solutions with concentrations of 2.5 - 10.0 wt. % are actively hydrolyzed during the first day and are not suitable for transportation or storage. It has been proven that heating a TiCl4 solution increases the rate of titanium tetrachloride hydrolysis by 3 orders of magnitude. Changing the intensity and temperature of heating will allow regulating the rate of hydrochloric acid release (the rate of hydrolytic decomposition). It has been established that the admixture of silicon tetrachloride in an amount greater than 0.4% by weight of SiCl4 leads not only to the acceleration of the hydrolytic decomposition of titanium tetrachloride, but also to the polycondensation/polymerization of the resulting active silicic acid with the formation of gel-like structures. The drop in the concentrations of titanium compounds during the hydrolysis of silicon-containing solutions was up to 10% TiCl4 for every 0.5% SiCl4. The data obtained in the work can be used to obtain industrial titanium dioxide or in the production of complex titanium-containing coagulants.
Relevance. The titanium industry is a strategically important area of development for any modern country. Aerospace, medical, food and other material-intensive industries are just a short list of consumers of titanium compounds. Most of the titanium reserves in the Russian Federation are presented in the form of quartz-leucoxene sandstones, the processing of which allows obtaining titanium tetrachloride, a precursor for the synthesis of titanium dioxide. Aim. To study the stability of aqueous solutions of titanium tetrachloride and to assess the effect of silicon tetrachloride impurity on the rate of hydrolytic decomposition of TiCl4. Methods. To study hydrolysis, spectrophotometry and magnetic plasma atomic emission spectroscopy were used. Results and conclusions. The author has studied hydrolysis of aqueous hydrochloric acid solutions of TiCl4. It was proven that hydrolysis accelerates as the concentration of TiCl4 in the solution decreases, while TiCl4 solutions with concentrations of 2.5–10.0 wt % are actively hydrolyzed during the first day and are not suitable for transportation or storage. Defined that heating a TiCl4 solution increases the rate of titanium tetrachloride hydrolysis by three orders of magnitude. Changing the intensity and temperature of heating will allow regulating the rate of hydrochloric acid release (the rate of hydrolytic decomposition). It was established that the admixture of silicon tetrachloride in an amount greater than 0.4 wt % of SiCl4 leads not only to the acceleration of the hydrolytic decomposition of titanium tetrachloride, but also to the polycondensation/polymerization of the resulting active silicic acid with the formation of gel-like structures. The drop in the concentrations of titanium compounds during the hydrolysis of silicon-containing solutions was up to 10% TiCl4 for every 0.5% SiCl4. The data obtained in the work can be used to produce industrial titanium dioxide or in the production of complex titanium-containing coagulants.
For citation: Kuzin E.N. Stability of hydrochloric acid titanium-containing solutions for processing quartz-leucoxene concentrate by selective chlorination. Bulletin of the Tomsk Polytechnic University. Geo Assets Engineering, 2026, vol. 337, no. 8, pp. 7–15. https://doi.org/10.18799/24131830/2026/8/5052
Keywords:
quartz-leucoxene concentrate, chlorination, hydrolysis, polymerization, polycondensation, titanium and silicon tetrachloride
References:
1. Aleksandrov A.V., Lednov S.V., Davydkina E.A. State of affairs in the titanium industry and development prospects. Technology of light alloys, 2021, no. 2, pp. 77–82. (In Russ.) DOI: https://doi.org/10.24412/0321-4664-2021-2-76-81.
2. Mathur R., Emproto C., Simon A.C. Chemical separation and measuring technique for titanium isotopes for titanium ores and iron-rich minerals. Minerals, 2022, vol. 12, no. 644. DOI: https://doi.org/10.3390/min12050644
3. Neto F.C., Giaretton M.V., Neves G.O. An overview of highly porous titanium processed via metal injection molding in combination with the space holder method. Metals, 2022, vol. 12, no. 783. DOI: https://doi.org/10.3390/met12050783
4. Petrova L.G., Lysak V.V., Malkova E.V. Assessment of the state of the titanium market in the context of the current geopolitical situation. Problems of expertise in the automobile and road industry, 2022, vol. 4 (5), pp. 18–30. (In Russ.)
5. Sadykhov G.B. Fundamental problems and prospects for the use of titanium raw materials in Russia. News of higher educational institutions. Chernye metally, 2020, vol. 63, no. 3–4, pp. 178–194. (In Russ.) DOI: https://doi.org/10.17073/0368-0797-2020-3-4-178-194.
6. Sadykhov G.B., Zablotskaya Y.V., Anisonyan K.G. Extraction of high-quality titanium raw materials from leucoxene concentrates of the Yarega Deposit. Russian Metallurgy (Metally), 2018, no. 11, pp. 1015–1019. DOI: https://doi.org/10.1134/S0036029518110101.
7. Anisonyan K.G., Sadyhov G.B., Olyunina T.V. Magnetizing roasting of leucoxene concentrate. Russian metallurgy (Metally), 2011, no. 7, pp. 656–659. DOI: https://doi.org/10.1134/S0036029511070020.
8. Istomina E.I., Istomin P.V., Nadutkin A.V., Grass V.E. Desiliconization of leucoxene concentrate during vacuum silicothermal treatment. New refractories, 2020, vol. 3, pp. 5–9. (In Russ.) DOI: https://doi.org/10.17073/1683-4518-2020-3-5-9
9. Nikolaev A.A. Thermophysical parameters of the anode region of plasma arc under the reduction smelting of quartz-leucoxene concentrate in a metal-graphite reactor. Inorganic Materials: Applied Research, 2020, vol. 11, pp. 563–567. DOI: https://doi.org/10.1134/S207511332003034X
10. Nikolaev A.A., Kirpichev D.E., Nikolaev A.V. Separation of titanium and silicon oxides during plasma-arc melting of quartz-leucoxene concentrate. Inorganic Materials: Applied Research, 2022, vol. 13, pp. 716–720. DOI: https://doi.org/10.1134/S2075113322030273
11. Perovskiy I.А., Burtsev I.N., Ponaryadov A.V. Ammonium fluoride roasting and water leaching of leucoxene concentrates to produce a high grade titanium dioxide resource (of the Yaregskoye deposit, Timan, Russia). Hydrometallurgy, 2022, vol. 210, no. 105858. DOI: https://doi.org/10.1016/j.hydromet.2022.105858.
12. Smorokov A.A., Kantaev A.S., Bryankin D.V., Miklashevich A.A. Development of a method for low-temperature desiliconization of leucoxene concentrate of the Yaregskoye deposit with a solution of ammonium hydrodifluoride. Izvestiya universities Chemistry and chemistry. Technology, 2022, vol. 65, Iss. 2, pp. 127133 (In Russ.) DOI: 10.6060/ivkkt.20226502.6551.
13. Zanaveskin K.L., Zanaveskina S.M., Maslennikov A.N. Activation of quartz-leucoxene concentrate for processing into titanium tetrachloride. Russian Journal of Applied Chemistry, 2016, vol. 89, no. 11.pp. 1733–1739. DOI: https://doi.org/10.1134/S107042721611001X.
14. Zanaveskin K.L., Meshalkin V.P. Chlorination of quartz-leucoxene concentrate of Yarega Field. Metall Mater Trans B, 2020, vol. 51, pp. 906–915. DOI: https://doi.org/10.1007/s11663-020-01810-2.
15. Shon H., Vigneswaran S., Kandasamy J., Zareie M. Preparation and characterization of titanium dioxide (TiO2) from sludge produced by TiCl4 flocculation with FeCl3, Al2(SO4)3 and Ca(OH)2 coagulantaids in wastewater. Separation Science and Technology, 2009, vol. 44, pp. 1525–1543. DOI: 10.1080/01496390902775810.
16. Navarrete-López A.M., Li S., Dixon D.A., Gole J.L. Hydrolysis of TiCl4: initial steps in the production of TiO2. The Journal of Physical Chemistry A, 2010, vol. 114 (28), pp. 7561–7570. DOI: 10.1021/jp102020h.
17. Thomas M., Bąk J., Królikowska J. Efficiency of titanium salts as alternative coagulants in water and wastewater treatment: short review. Desalination and Water Treatment, 2020, vol. 208, pp. 261–272.
18. Izmailova N.L., Lorentson A.V., Chernoberezhskii Y.N. Composite coagulant based on titanyl sulfate and aluminum sulfate. Russian Journal of Applied Chemistry, 2015, vol. 88, pp. 458–462.
19. Gan Y., Li J., Zhang L., Wu B. Potential of titanium coagulants for water and wastewater treatment: current status and future perspectives. Chemical Engineering Journal, 2020, no. 126837. DOI: 10.1016/j.cej.2020.126837
20. Wern T.Y., Ardani M.R., Ramli S.F. Coagulation performance of titanium tetrachloride for Alor Pongsuwastewater treatment. AIP Conference Proceeding, 2020, vol. 2267, no. 020073. DOI: https://doi.org/10.1063/5.0016162
21. Zhao Y., Lian H., Tian C. Surface water treatment benefits from the presence of algae: Influence of algae on the coagulation behavior of polytitanium chloride. Frontiers of Environmental Science & Engineering, 2021, vol. 15, no. 58. DOI: https://doi.org/10.1007/s11783-020-1350-x
22. Kuzin E. Synthesis and use of complex titanium-containing coagulant in water purification processes. Inorganics, 2025, vol. 13 (1), no. 9. DOI: https://doi.org/10.3390/inorganics13010009
23. Shabanova N.A., Popov V.V., Sarkisov P.D. Chemistry and technology of nanodispersed oxides. Moscow, Akademkniga Publ., 2007. 309 p. (In Russ.)
24. Kuzin E.N. Application of the method of atomic emission spectroscopy with microwave (magnetic) plasma in the processes of identifying the chemical composition of steelmaking waste. Chernye metally, 2022, vol. 10, pp. 79–82. (In Russ.) DOI: 10.17580/chm.2022.10.13
25. Kuzin E.N., Kruchinina N.E., Chernyshev P.I., Vizen N.S. Synthesis of titanium trichloride. Inorganic Materials, 2020, vol. 56, no. 5, pp. 507–511. DOI: 10.1134/S002016852005009X
26. Zhu F., Ma S., Ma Z. Preparation of TiCl4 from panzhihua ilmenite concentrate by boiling chlorination. Journal of Materials Research and Technology, 2023, vol. 23, pp. 2703–2718. DOI: https://doi.org/10.1016/j.jmrt.2023.01.190
27. Mao H., Fan C., Du G. Chemical and morphological transformation of ilmenite during modification roasting with chlorine in fluidized bed. Journal of Materials Research and Technology, 2021, vol. 12, pp. 2285–2297. DOI: https://doi.org/10.1016/j.jmrt.2021.04.024.
