CN115418679A - Method for preparing metallic titanium by electrolyzing titanium dioxide in fluoride molten salt-electroactive oxide system - Google Patents
Method for preparing metallic titanium by electrolyzing titanium dioxide in fluoride molten salt-electroactive oxide system Download PDFInfo
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 100
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 91
- 239000010936 titanium Substances 0.000 title claims abstract description 91
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 107
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000007670 refining Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 6
- 239000007769 metal material Substances 0.000 claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 5
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 14
- 239000010937 tungsten Substances 0.000 claims description 14
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 229910000856 hastalloy Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000001568 sexual effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000001307 helium Substances 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000007770 graphite material Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- GEHLLHAUIUKKFH-UHFFFAOYSA-L [F-].[F-].[Na+].[K+] Chemical compound [F-].[F-].[Na+].[K+] GEHLLHAUIUKKFH-UHFFFAOYSA-L 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- GBPYGZIYERGMPX-UHFFFAOYSA-L [F-].[K+].[Li+].[F-] Chemical compound [F-].[K+].[Li+].[F-] GBPYGZIYERGMPX-UHFFFAOYSA-L 0.000 description 3
- MDIZCNDXLVFYLF-UHFFFAOYSA-L lithium;sodium;difluoride Chemical compound [Li+].[F-].[F-].[Na+] MDIZCNDXLVFYLF-UHFFFAOYSA-L 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- CKRNPRFOXFWMGH-UHFFFAOYSA-K calcium;potassium;trifluoride Chemical compound [F-].[F-].[F-].[K+].[Ca+2] CKRNPRFOXFWMGH-UHFFFAOYSA-K 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- FYAABNCYNWGSQX-UHFFFAOYSA-L disodium;difluoride Chemical compound [F-].[F-].[Na+].[Na+] FYAABNCYNWGSQX-UHFFFAOYSA-L 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FYLHIULETLYEFY-UHFFFAOYSA-N [C].[O].[Ti] Chemical compound [C].[O].[Ti] FYLHIULETLYEFY-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
- C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for preparing metal titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system, belonging to the technical field of metal titanium preparation. In the invention, tiO is mixed with 2 Directly adding the mixture into a fluoride molten salt-electroactive oxide system, heating the mixture at the temperature of between 300 and 400 ℃ in an inert atmosphere to remove water in the molten salt system, heating the mixture until the superheat degree is between 20 and 80 ℃, taking carbon or metal material as an anode of an electrolytic cell, taking metal or metal alloy as a cathode of the electrolytic cell, and carrying out constant current electrolysis to obtain a cathode product after electrolysis; taking a cathode product as an anode of an electrolytic cell, chloride fused salt as a fused salt electrolyte, taking metal or metal alloy as a cathode of the electrolytic cell, carrying out constant current electrolytic refining at the superheat degree of 20-80 ℃ in an inert atmosphere to remove fluoride and oxide electrolytes, and carrying out vacuum distillation or washing to remove impurities to obtain cathode metal titanium. In the invention, tiO is added 2 Dissolving in fluoride-electroactive oxide system for electrolysis, simple process, short process, low cost, and high product qualityThe purity reaches 99.7 percent.
Description
Technical Field
The invention relates to a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system, belonging to the technical field of metallic titanium preparation.
Background
Titanium and its alloy have the advantages of high strength, low density, strong resilience, corrosion resistance, good biocompatibility and the like, are important metal materials for modern industry and advanced scientific development, and are called as 'modern metals'. At present, the method for industrially preparing titanium is mainly a Kroll method, and has the characteristics of complex process flow, difficult continuous production, high production energy consumption and the like, so that the production cost of titanium is high, and the use and development of titanium and titanium alloy in the fields of middle-end and low-end industries and civil use are limited. If these resources can be reasonably used, the progress and development of global science and technology will be accelerated, so how to prepare high-quality titanium products and how to reduce production cost become a problem that researchers at home and abroad continuously explore and solve.
Currently, the only method for industrially producing metallic titanium is the magnesiothermic reduction method, also known as Kroll method. The process is to put magnesium metal into a reactor and fill argon for protection, heat to 800-900 ℃, and then add titanium tetrachloride and magnesium vapor at a certain speed to react to produce titanium sponge. The process has the defects of non-continuity, complex production process, high cost, high energy consumption, great environmental pollution and the like. The high cost of the smelting method causes the price of titanium and titanium alloy to be higher, and limits the wide application of the titanium and the titanium alloy materials.
In the prior art, tiO is adopted for preparing metal titanium by a molten salt electrolysis method 2 As raw material in CaCl 2 Deoxidizing the cathode in molten salt to produce titanium sponge, but the raw material utilization rate is low, the electrolytic deoxidation efficiency is low, and the oxygen content of the product is high; in CaCl 2 Method for preparing TiO from active calcium obtained by electrolysis in molten salt 2 Reduced into titanium metal, but has low current efficiency, incomplete reaction of raw materials, high impurity content of products and original materialThe purity requirement of the titanium dioxide is high; with TiO 2 And C are mixed according to the stoichiometric ratio and are thermally reduced at 1100-1300 ℃ to obtain a low-valence compound of titanium, and the low-valence compound is used as a composite anode to be electrolyzed in an alkali metal molten salt system to obtain the metallic titanium. The composite anode is a mixed material of a low-valence titanium compound of titanium and carbon, and residual carbon covers the surface of the anode in the electrochemical dissolution process to prevent the further dissolution of the anode, so that the problem of low anode dissolution rate exists;
titanium dioxide and graphite are used as raw materials, a titanium low-valent compound with good conductivity is produced by vacuum carbothermic reduction at 1500 ℃, the titanium low-valent compound is used as a soluble anode material to extract high-purity metal titanium in a NaCl-KCl molten salt system at 700 ℃, or a titanium-containing material and a carbon-containing reducing agent are mixed to be used as raw materials, the raw materials are uniformly mixed and pressed to be molded, and the mixture is roasted at 1000-2000 ℃ in a nitrogen-containing atmosphere to prepare a titanium-containing compound with good conductivity, and then the titanium-containing compound is used as an anode to extract metal titanium in halide molten salt of alkali metal or alkaline earth metal by electrolysis, however, the process also has the problem of low anode dissolution rate;
titanium tetrachloride is used as a raw material, metal titanium is used for reduction to obtain low-valence titanium chloride, and then the metal titanium is obtained through molten salt electrolysis, so that the problems of expensive raw material, low reaction rate, high cost and the like exist; liquid metal (bismuth, tin, lead and the like) is used as a cathode, and titanium sponge or soluble titanium-containing substances (titanium-carbon-oxygen solid solution and the like) are used as an anode for electrolysis. After the electrolysis is finished, distilling the cathode titanium alloy product at high temperature to finally obtain high-purity titanium metal; sintering titanium dioxide powder to obtain a sintered body, and then taking the sintered body and a metal molybdenum wire as cathodes, graphite as anodes and NaF and AlF as anodes 3 The mixture melt is used as electrolyte to be electrolyzed to obtain metal titanium powder;
a method for preparing metal titanium by dissolving and electrolyzing titanium dioxide in fluoride fused salt, which is to dissolve and electrolyze TiO 2 Directly adding into nNaF-K 2 TiF 6 Dissolving in fluoride molten salt system at 20-80 deg.C in inert atmosphere, performing cathode-anode current density differential electrolysis with carbon or metal material as the anode and metal material as the cathode of the electrolytic cell, and electrolyzing to obtain cathodeRemoving the attached electrolyte from the polar product by vacuum distillation or washing with dilute hydrochloric acid solution to obtain metal titanium; however, the electrolysis carried out by the method finds that the prepared metallic titanium has low purity, partial low-valence titanium oxide is generated, and the impurity content of the product is high; the electrolysis efficiency is low; in addition, after washing with dilute hydrochloric acid, the effect of removing impurities is not achieved, and the dissolution of metallic titanium is caused.
However, the molten salt electrolysis method in the prior art for preparing the metal titanium has the problems of expensive raw materials, complex flow, high cost and the like.
Disclosure of Invention
Aiming at the problems of high cost, low utilization rate of raw materials, high content of product impurities and the like in the production process of metal titanium in the prior art, the invention provides a method for preparing metal titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system, namely directly preparing TiO 2 Dissolving the product in a fluoride-electroactive oxide system for electrolysis, and then removing impurities by chloride molten salt electrolysis, wherein the method is simple, the flow is short, the cost is low, and the product purity reaches 99.7%.
A method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) Adding TiO into the mixture 2 Directly adding the mixture into a fluoride fused salt-electroactive oxide system, heating the mixture at the temperature of between 300 and 400 ℃ in an inert atmosphere to remove the moisture in the fused salt system, heating the mixture to the superheat degree of between 20 and 80 ℃, carrying out constant current electrolysis by taking carbon or metal materials as an anode of an electrolytic cell and metal or metal alloy as a cathode of the electrolytic cell, and obtaining a cathode product after electrolysis; the electrolytic cell is of a sealed structure, and the superheat degree is the difference between the electrolysis temperature and the molten salt primary crystal temperature, namely the superheat degree = the electrolysis temperature-the molten salt primary crystal temperature; the primary crystal temperature of fluoride fused salt is 630-880 ℃, the electrolysis temperature is 650-900 ℃, and TiO is added under the electrolysis temperature 2 The solubility in a fluoride molten salt system is not less than 4wt%, and the solubility of the electroactive oxide in the fluoride molten salt system is not less than 1wt%;
(2) And (2) taking the cathode product in the step (1) as an anode of an electrolytic cell, chloride molten salt as molten salt electrolyte, metal or metal alloy as a cathode of the electrolytic cell, carrying out constant-current electrolytic refining at the superheat degree of 20-80 ℃ in an inert atmosphere to remove fluoride and oxide electrolyte, and removing impurities by vacuum distillation or water washing to obtain cathode metal titanium, wherein the primary crystal temperature of the chloride molten salt is 400-830 ℃, and the electrolytic temperature is 450-900 ℃.
The fluoride molten salt in the step (1) is composed of a fluoride A and a fluoride B, the fluoride A and the fluoride B are different substances, the fluoride A is sodium fluoride, potassium fluoride, lithium fluoride or calcium fluoride, and the fluoride B is potassium fluotitanate, sodium fluotitanate, potassium fluoride or lithium fluoride.
The molar ratio of the fluoride A to the fluoride B is 1-4.
The electroactive oxide in the step (1) is CaO and Al 2 O 3 MgO or Na 2 O。
The cathode in the step (1) is titanium, tungsten, molybdenum, zinc, bismuth, tin, 310 stainless steel or hastelloy.
The current density of the constant current in the step (1) is 1-5A/cm 2 。
The chloride molten salt in the step (2) is NaCl, KCl and CaCl 2 One or more of (a).
The cathode in the step (2) is tungsten, titanium, hastelloy or 310S stainless steel.
The current density of the constant current in the step (2) is 1.5-3.5A/cm 2 。
Preferably, the inert gas is argon or helium.
In the electrolysis process, the electrolysis bath needs to be vacuumized and then argon is introduced for three times before electrolysis, and the temperature is raised after circulation for three times.
The mechanism of titanium dioxide direct electrolysis to prepare metallic titanium in a fluoride molten salt-electroactive oxide system is as follows: the method comprises the steps of utilizing fluoride molten salt electrolyte with high titanium dioxide solubility (more than 4 wt%), adding electroactive oxide of a fluoride system, and controlling proper electrolysis process conditions to further reduce insufficiently reduced low-valence titanium oxide by an electrolyzed cathode product; by directly adding the electroactive oxide into the fluoride molten salt, when the metal titanium is prepared by electrolysis, the metal titanium is not generated, but the electroactive metal is generated, and the generated electroactive metal can further reduce the low-valence titanium oxide to fully reduce the low-valence titanium oxide. And then taking the electrolytic cathode product as an anode, carrying out electrolytic refining through a chloride molten salt system to remove attached fluoride and oxide electrolyte, and washing with water to obtain the cathode metal titanium with higher purity (more than 99.7 wt%).
The invention has the beneficial effects that:
(1) The invention adds electroactive substances into fluoride fused salt, and makes the electroactive substances electrolyzed into electroactive metals in the electrolysis process, so that the electroactive metals promote the secondary reduction of the low-valence titanium oxide.
(2) The method directly uses titanium dioxide as a raw material, prepares high-purity titanium and low-valence titanium oxide by electrolysis in a fluoride molten salt-oxide system with high solubility to the titanium dioxide, carries out deep reduction by chloride molten salt electrolysis refining, and finally carries out vacuum distillation and washing to remove impurities, and is simple, short in process, low in cost and high in product purity of 99.7 percent
(3) The electrochemical window of the electrolyte in the fluoride molten salt-oxide system is wider, and fluorine gas is not generated at the anode during electrolysis.
Drawings
FIG. 1 is an XRD pattern of titanium metal of the cathode of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) 7.2g of TiO 2 180g of fluoride fused salt (sodium fluoride-potassium fluotitanate) and 5.4g of electroactive oxide (calcium oxide) are uniformly mixed, dried for 6 hours at the temperature of 100 ℃, kept warm for 3 hours at the temperature of 300 ℃ under the inert (argon) atmosphere to remove the moisture of a fused salt system, heated to 880 ℃ to the superheat degree of 80 ℃, graphite material is used as an anode of an electrolytic cell, a tungsten rod is used as a cathode of the electrolytic cell, and the cathode is applied to the cathode and the anodeThe current density is 1A/cm 2 Carrying out constant current electrolysis for 3h to obtain a cathode product after electrolysis; wherein the molar ratio of sodium fluoride to potassium fluotitanate in the fluoride molten salt is 1.5, the electrolytic cell is of a sealed structure, and the superheat degree is the difference between the electrolysis temperature and the primary crystal temperature of the molten salt, namely the superheat degree = the electrolysis temperature-the primary crystal temperature of the molten salt; the primary crystal temperature of fluoride fused salt (sodium fluoride-potassium fluotitanate) is 800 ℃, the electrolysis temperature is 880 ℃, and TiO is added under the electrolysis temperature 2 The solubility in a fluoride molten salt system is not less than 4wt%, and the solubility of an electroactive oxide (calcium oxide) in the fluoride molten salt system is not less than 1wt%;
(2) Taking the cathode product in the step (1) as an anode of an electrolytic cell, chloride fused salt (NaCl) as fused salt electrolyte, taking metal tungsten as a cathode of the electrolytic cell, and applying cathode current density of 2.5A/cm to the cathode and the anode under the condition of superheat degree of 50 ℃ and inert atmosphere (argon) 2 Performing constant current electrolytic refining for 180min to remove fluoride and oxide electrolytes, washing with water to remove impurities to obtain cathode metal titanium, wherein the primary crystal temperature of chloride molten salt (NaCl) is 801 ℃, and the electrolysis temperature is 851 ℃;
the XRD pattern of the cathode metallic titanium is shown in figure 1, and as can be seen from figure 1, the cathode product obtained by electrolyzing the metallic titanium in the method under the proper electrolysis condition can obtain a relatively pure metallic titanium phase without generating other impurity phases;
the cathode titanium metal of the embodiment is washed by water to obtain the titanium metal with the purity of 99.83 wt%.
Example 2: a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) 9g of TiO 2 180g of fluoride fused salt (sodium fluoride-sodium fluotitanate) and 6g of electroactive oxide (calcium oxide) are uniformly mixed, dried for 5 hours at the temperature of 200 ℃, kept at the temperature of 300 ℃ for 3 hours under the inert (helium) atmosphere to remove the moisture in a fused salt system, heated to 800 ℃ to the superheat degree of 72 ℃, graphite material is used as the anode of an electrolytic cell, a tungsten rod is used as the cathode of the electrolytic cell, and the cathode current density is applied to the cathode and the anode and is 2.5A/cm 2 Carrying out constant current electrolysis for 3.2h to obtain a cathode product after electrolysis; in which the fluoride is fluorinated in a molten salt of fluorideThe molar ratio of sodium to sodium fluotitanate is 1; the primary crystal temperature of the fluoride fused salt (sodium fluoride-sodium fluotitanate) is 728 ℃, the electrolysis temperature is 800 ℃, and TiO is added under the electrolysis temperature 2 The solubility in a fluoride molten salt system is not less than 4wt%, and the solubility of an electroactive oxide (calcium oxide) in the fluoride molten salt system is not less than 1wt%;
(2) Taking the cathode product in the step (1) as an anode of an electrolytic cell, chloride fused salt (KCl) as fused salt electrolyte, taking metal tungsten as a cathode of the electrolytic cell, and applying cathode current density of 3A/cm to the cathode and the anode under the conditions that the superheat degree is 20 ℃ and inert atmosphere (helium gas) 2 Performing constant current electrolytic refining for 120min to remove fluoride and oxide electrolytes, washing with water to remove impurities to obtain cathode metal titanium, wherein the primary crystal temperature of chloride molten salt (KCl) is 770 ℃ and the electrolysis temperature is 790 ℃;
in this example, the cathode titanium metal was washed with water to obtain titanium metal with a purity of 99.75 wt%.
Example 3: a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) 12g of TiO 2 180g of fluoride fused salt (sodium fluoride-potassium fluoride) and 9g of electroactive oxide (magnesium oxide) are uniformly mixed, dried for 7 hours at the temperature of 150 ℃, insulated for 3 hours at the temperature of 350 ℃ in the inert (helium) atmosphere to remove the moisture of a fused salt system, heated to 790 ℃ until the superheat degree is 34 ℃, tungsten is used as the anode of an electrolytic cell, hastelloy is used as the cathode of the electrolytic cell, and the cathode current density is 1A/cm applied to the cathode and the anode 2 Carrying out constant current electrolysis for 6h to obtain a cathode product after electrolysis; wherein the molar ratio of sodium fluoride to potassium fluoride in the fluoride molten salt is 3; the primary crystal temperature of fluoride fused salt (sodium fluoride-potassium fluoride) is 756 ℃, the electrolysis temperature is 790 ℃, and TiO is added under the electrolysis temperature 2 Solubility in molten fluoride salt system of not less than 4wt%, electroactive oxide (oxidizing)Magnesium) has a solubility in molten fluoride salt systems of not less than 1wt%;
(2) Taking the cathode product in the step (1) as an anode of the electrolytic cell, and using chloride molten salt (CaCl) 2 ) Taking tungsten as cathode of electrolytic cell, and applying cathode current density of 1.5A/cm at cathode and anode under inert atmosphere (helium) at 20 deg.C 2 Performing constant current electrorefining for 200min to remove fluoride and oxide electrolyte, washing with water to remove impurities to obtain cathode metal titanium, wherein chloride molten salt (CaCl) 2 ) The primary crystallization temperature is 772 ℃, and the electrolysis temperature is 792 ℃;
the cathode titanium metal of the embodiment is washed by water to obtain the titanium metal with the purity of 99.84 wt%.
Example 4: a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) 15g of TiO 2 180g of fluoride fused salt (sodium fluoride-lithium fluoride) and 10g of electroactive oxide (aluminum oxide) are uniformly mixed, dried for 8 hours at the temperature of 150 ℃, kept warm for 3 hours at the temperature of 400 ℃ under the inert (helium) atmosphere to remove the moisture of a fused salt system, heated to the superheat degree of 50 ℃, graphite material is used as the anode of an electrolytic cell, hastelloy is used as the cathode of the electrolytic cell, and the cathode current density is applied to the cathode and the anode and is 5A/cm 2 Carrying out constant current electrolysis for 6h to obtain a cathode product after electrolysis; wherein the molar ratio of sodium fluoride to lithium fluoride in the fluoride molten salt is 2; the primary crystal temperature of fluoride fused salt (sodium fluoride-lithium fluoride) is 700 ℃, the electrolysis temperature is 750 ℃, and TiO is added at the electrolysis temperature 2 The solubility in a fluoride molten salt system is not less than 4wt%, and the solubility of an electroactive oxide (aluminum oxide) in the fluoride molten salt system is not less than 1wt%;
(2) Taking the cathode product in the step (1) as the anode of the electrolytic cell, and using chloride molten salt (NaCl-CaCl) 2 ) The molten salt electrolyte is prepared by using molybdenum as cathode of electrolytic cell, and applying cathode current density of 2A/cm to cathode and anode at superheat degree of 50 deg.C under inert atmosphere (helium) 2 Performing constant current electrorefining for 180min to remove fluoride and oxide electrolyte, washing with water to remove impurities to obtain cathode metal titanium, wherein NaCl and CaCl are contained in chloride molten salt 2 Chloride fused salt (NaCl — CaCl) at a molar ratio of 4 2 ) The primary crystal temperature is 400 ℃, and the electrolysis temperature is 450 ℃;
the cathode titanium metal of the embodiment is washed by water to obtain the titanium metal with the purity of 99.76 wt%.
Example 5: a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) 6.8g of TiO 2 180g of fluoride fused salt (potassium fluoride-lithium fluoride) and 6g of electroactive oxide (sodium oxide) are uniformly mixed, dried for 5 hours at the temperature of 200 ℃, kept warm for 2 hours at the temperature of 350 ℃ in an inert (argon) atmosphere to remove the moisture of a fused salt system, heated to the superheat degree of 20 ℃, graphite material is used as an anode of an electrolytic cell, a titanium rod is used as a cathode of the electrolytic cell, and the cathode current density is 3.0A/cm applied to the cathode and the anode 2 Carrying out constant current electrolysis for 4h to obtain a cathode product after electrolysis; wherein the molar ratio of sodium fluoride to lithium fluoride in the fluoride molten salt is 1.8, the electrolytic cell is of a sealing structure, and the superheat degree is the difference between the electrolysis temperature and the molten salt primary crystal temperature, namely the superheat degree = the electrolysis temperature-the molten salt primary crystal temperature; the primary crystal temperature of fluoride fused salt (sodium fluoride-lithium fluoride) is 760 ℃, the electrolysis temperature is 780 ℃, and TiO is added at the electrolysis temperature 2 The solubility in a fluoride molten salt system is not less than 4wt%, and the solubility of an electroactive oxide (sodium oxide) in the fluoride molten salt system is not less than 1wt%;
(2) Taking the cathode product in the step (1) as an anode of an electrolytic cell, chloride fused salt (NaCl) as fused salt electrolyte, taking metal tungsten as a cathode of the electrolytic cell, and applying cathode current density of 2A/cm to the cathode and the anode under the condition that the superheat degree is 40 ℃ and the inert atmosphere (argon gas) 2 Performing constant current electrolytic refining for 240min to remove fluoride and oxide electrolytes, washing with water to remove impurities to obtain cathode metal titanium, wherein the primary crystallization temperature of chloride molten salt (NaCl) is 801 ℃, and the electrolysis temperature is 841 ℃;
the cathode titanium metal of the embodiment is washed by water to obtain the titanium metal with the purity of 99.78 wt%.
Example 6: a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) 9g of TiO 2 180g of fluoride fused salt (lithium fluoride-potassium fluotitanate) and 6g of electroactive oxide (sodium oxide) are uniformly mixed, dried for 5 hours at the temperature of 200 ℃, kept warm for 3 hours at the temperature of 300 ℃ in an inert (argon) atmosphere to remove the moisture of a fused salt system, heated to the superheat degree of 30 ℃, graphite material is used as an anode of an electrolytic cell, a titanium rod is used as a cathode of the electrolytic cell, and the cathode current density is applied to the cathode and the anode and is 5.0A/cm 2 Carrying out constant current electrolysis for 3h to obtain a cathode product after electrolysis; wherein the molar ratio of lithium fluoride to potassium fluotitanate in the fluoride molten salt is 4; the primary crystal temperature of fluoride fused salt (lithium fluoride-potassium fluotitanate) is 800 ℃, the electrolysis temperature is 830 ℃, and TiO is added under the electrolysis temperature 2 The solubility in a fluoride molten salt system is not less than 4wt%, and the solubility of an electroactive oxide (sodium oxide) in the fluoride molten salt system is not less than 1wt%;
(2) Taking the cathode product in the step (1) as an anode of an electrolytic cell, chloride fused salt (NaCl-KCl) as fused salt electrolyte, taking metal tungsten as a cathode of the electrolytic cell, and applying cathode current density of 1.5A/cm to the cathode and the anode under the conditions that the superheat degree is 28 ℃ and the inert atmosphere (argon gas) 2 Performing constant current electrolytic refining for 180min to remove fluoride and oxide electrolytes, washing with water to remove impurities to obtain cathode metal titanium, wherein the molar ratio of NaCl to KCl in the chloride molten salt is 1, the primary crystal temperature of the chloride molten salt (NaCl-KCl) is 782 ℃, and the electrolysis temperature is 810 ℃;
the cathode titanium metal of the embodiment is washed by water to obtain the titanium metal with the purity of 99.85 wt%.
Example 7: a method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system comprises the following specific steps:
(1) 20g of TiO 2 180g of fluoride molten salt (calcium fluoride-potassium fluotitanate), 10g of electroactive oxygenUniformly mixing the compounds (calcium oxide), drying at 200 deg.C for 6h, maintaining at 300 deg.C under inert (argon) atmosphere for 3h to remove water in molten salt system, heating to 40 deg.C, using graphite material as anode of electrolytic bath, tungsten rod as cathode of electrolytic bath, and applying cathode current density of 3A/cm to the cathode and anode 2 Carrying out constant current electrolysis for 5h to obtain a cathode product after electrolysis; wherein the molar ratio of calcium fluoride to potassium fluotitanate in the fluoride molten salt is 4, the electrolytic cell is of a sealed structure, and the superheat degree is the difference between the electrolysis temperature and the primary crystal temperature of the molten salt, namely the superheat degree = the electrolysis temperature-the primary crystal temperature of the molten salt; the primary crystal temperature of fluoride fused salt (calcium fluoride-potassium fluotitanate) is 820 ℃, the electrolysis temperature is 860 ℃, and TiO is added under the electrolysis temperature 2 The solubility in a fluoride molten salt system is not less than 4wt%, and the solubility of an electroactive oxide (calcium oxide) in the fluoride molten salt system is not less than 1wt%;
(2) Taking the cathode product in the step (1) as an anode of an electrolytic cell, chloride fused salt (KCl) as fused salt electrolyte, taking metal tungsten as a cathode of the electrolytic cell, and applying cathode current density of 2A/cm to the cathode and the anode under the conditions that the superheat degree is 40 ℃ and the inert atmosphere (argon gas) is adopted 2 Performing constant current electrolytic refining for 180min to remove fluoride and oxide electrolyte, washing with water to remove impurities to obtain cathode metal titanium, wherein the primary crystal temperature of chloride molten salt (KCl) is 770 ℃, and the electrolysis temperature is 810 ℃;
the cathode titanium metal of the embodiment is washed by water to obtain the titanium metal with the purity of 99.89 wt%.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (9)
1. A method for preparing metallic titanium by electrolyzing titanium dioxide in a fluoride molten salt-electroactive oxide system is characterized by comprising the following specific steps:
(1) Adding TiO into the mixture 2 Directly adding into a fluoride molten salt-electroactive oxide system, and inertly adding at the temperature of 300-400 DEG CHeating in a sexual atmosphere to remove water in a molten salt system, heating to the superheat degree of 20-80 ℃, carrying out constant current electrolysis by using carbon or metal materials as an anode of an electrolytic cell and metal or metal alloy as a cathode of the electrolytic cell, and electrolyzing to obtain a cathode product; the electrolytic cell is of a sealed structure, and the superheat degree is the difference between the electrolysis temperature and the molten salt primary crystal temperature, namely the superheat degree = the electrolysis temperature-the molten salt primary crystal temperature; the primary crystal temperature of the fluoride fused salt is 630-880 ℃, the electrolysis temperature is 650-900 ℃, and TiO is added at the electrolysis temperature 2 The solubility in a molten fluoride salt system is not less than 4wt%, and the solubility of the electroactive oxide in the molten fluoride salt system is not less than 1wt%;
(2) And (2) taking the cathode product in the step (1) as an anode of an electrolytic cell, chloride molten salt as molten salt electrolyte, metal or metal alloy as a cathode of the electrolytic cell, carrying out constant-current electrolytic refining at the superheat degree of 20-80 ℃ in an inert atmosphere to remove fluoride and oxide electrolyte, and removing impurities by vacuum distillation or water washing to obtain cathode metal titanium, wherein the primary crystal temperature of the chloride molten salt is 400-830 ℃, and the electrolytic temperature is 450-900 ℃.
2. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 1, characterized in that: the fluoride fused salt in the step (1) is composed of fluoride A and fluoride B, the fluoride A and the fluoride B are different substances, the fluoride A is sodium fluoride, potassium fluoride, lithium fluoride or calcium fluoride, and the fluoride B is potassium fluotitanate, sodium fluotitanate, potassium fluoride or lithium fluoride.
3. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 2, wherein: the molar ratio of fluoride A to fluoride B is 1-4.
4. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 1, wherein: the electroactive oxide in the step (1) is CaO and Al 2 O 3 MgO or Na 2 O。
5. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 1, characterized in that: the cathode is titanium, tungsten, molybdenum, zinc, bismuth, tin, 310 stainless steel or hastelloy.
6. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 1, wherein: the current density of the constant current in the step (1) is 1 to 5A/cm 2 。
7. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 1, characterized in that: the chloride molten salt in the step (2) is NaCl, KCl and CaCl 2 One or more of (a).
8. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 1, characterized in that: and (3) the cathode in the step (2) is tungsten, titanium, hastelloy or 310S stainless steel.
9. The method for preparing metallic titanium by electrolysis of titanium dioxide in a fluoride molten salt-electroactive oxide system according to claim 1, characterized in that: the current density of the constant current in the step (2) is 1.5-3.5A/cm 2 。
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