CN113699560B - Method for preparing metallic titanium by soluble anode electrolysis of fluorine-chlorine mixed molten salt system - Google Patents
Method for preparing metallic titanium by soluble anode electrolysis of fluorine-chlorine mixed molten salt system Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 98
- 239000010936 titanium Substances 0.000 title claims abstract description 95
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 68
- 150000003839 salts Chemical class 0.000 title claims abstract description 43
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 23
- 239000000919 ceramic Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 238000003825 pressing Methods 0.000 claims description 19
- 235000010215 titanium dioxide Nutrition 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 230000003068 static effect Effects 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- 238000010438 heat treatment Methods 0.000 description 21
- 238000000498 ball milling Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000010405 anode material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910020549 KCl—NaCl Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000009870 titanium metallurgy Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5603—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides with a well-defined oxygen content, e.g. oxycarbides
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- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
- C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
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- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
A method for preparing metallic titanium by soluble anode electrolysis of fluorine-chlorine mixed molten salt system. The invention relates to the field of metallurgy, in particular to a method for preparing metallic titanium by taking titanium dioxide as a raw material, which mainly comprises two steps of preparing a high-conductivity titanium oxycarbide anode and carrying out molten salt electrolysis on a fluorine-chlorine mixed system soluble anode. The high-purity metallic titanium product is prepared by adopting the characteristic process flows of secondary fine grinding, secondary briquetting, secondary roasting, pre-electrolysis, mixed molten salt and the like, and roasting and electrolysis are carried out in an argon environment. Besides adding some process steps, the technology inherits the advantages of other soluble anode electrolysis, such as low raw material cost, easy operation and continuous production, besides, the technology has lower requirements on equipment tightness, better electrolysis stability, higher current efficiency and product purity, and is convenient for realizing industrial application.
Description
Technical Field
The invention relates to a method for preparing metallic titanium, belonging to the field of nonferrous metal metallurgy.
Background
Titanium and its alloy have excellent physical and chemical properties, have the characteristics of small density, high strength, high temperature resistance, corrosion resistance and the like, are important light structural materials and novel functional materials, are widely applied to civil fields such as aerospace, military industry and chemical industry, ships, buildings, sports equipment, medical appliances, biomedicine and the like, and are known as future metals and third metals. The magnesium reduction method (Kroll method) is the only method for producing titanium sponge (titanium sponge) industrially internationally at present, however, as the Kroll process is discontinuous, intermittent loading and unloading and high-temperature heating operation are required in the production process, the energy consumption is high, the period is long, and the production cost is high. In addition, the chlorinating agent has strong corrosiveness, is easy to erode equipment, worsens labor conditions and pollutes the environment, thereby limiting the wider application of the metallic titanium. Therefore, the novel titanium metallurgy technology with low development cost, simple process and high cleanness and efficiency is a constantly focused problem and effort.
For the last 20 years, numerous universities and scientific research institutions at home and abroad including university of Norway science and technology, cambridge university and various titanium metallurgical enterprises including DuPont are striving to explore methods for producing metallic titanium by replacing magnesian reduction, and the cathode deoxidation process of titanium dioxide developed by Cambridge university utilizes a direct electroreduction process (also called FFC method) to remove oxygen from metallic oxide raw materials, which can directly take titanium dioxide as cathode raw material and directly precipitate titanium sponge on the cathode (Nature.2000, 407:361-364), and after the technological birth, a lot of technological achievements are invented successively (for example, CN101086074 discloses a vacuum electrolysis TiO) 2 Preparation of TiO in titanium sponge 2 Cathode preparation method; CN1664173 discloses a method for preparing titanium sponge by molten salt electrolysis of titanium dioxide; CN107587168A discloses "method for preparing metallic titanium by molten salt electrolysis". The method has the advantages that titanium dioxide with lower cost can be used as a raw material, the production flow is short, and no toxic chlorine is generated in the production process. However, this method has problems of low solid-phase diffusion rate of oxygen in the cathode region, low current efficiency, and high impurity content in the metallic titanium obtained by electrolysis. Electrochemical calcium thermal reduction process developed by university of Kyoto utilizes TiO 2 The calcic thermal reduction of metal titanium or its alloys (see Metallurgical and Materials Transactions B.2003, 34:287-295) is also advantageous in terms of low raw material costs and short process flows, but the process first requires electrolysis of CaCl 2 Liquid metal calcium is generated, and then TiO is reduced by caloricity 2 The preparation of the metallic titanium has low production efficiency, and the calcium-titanium alloy product is not easy to thoroughly separate to influence the purity of the metallic titanium. The Japanese research group uses CaF 2 Equal molten salt directDissolving TiO 2 And electrolytic treatment to obtain liquid metallic titanium (Electrochemistry, 1999, 67:661-668), but with higher impurity content. The full oxide melt electrolysis method proposed by Sadowy professor of university of Massachu works electrolyzes TiO-containing at high temperature 2 To produce liquid metallic titanium and at the same time produce O at the anode 2 (J Materials Research,1995 (10): 487-492), which is simple, can be continuously produced and is environmentally friendly, but requires expensive special metal anode materials for electrolysis at 1700 ℃ and has high production cost.
The new technology of "soluble anodic electrolysis of titanium oxycarbide" was originally proposed by e.wainer in the united states, which uses a mixture of TiC and TiO as raw materials, and deposits titanium sponge on the cathode by the high temperature method of arc melting (as disclosed in US,2868703, cell Feed Material for the Production of Titanium; US,2722509, thermal and Electrochemical Process for Metal Production), however, the raw materials cost of this method is too high. Subsequently, the American MER company is treated with TiO 2 Or uniformly mixing rutile powder with carbon and a binder, performing compression molding, performing heat treatment, and preparing a soluble anode, wherein ilmenite is used as a raw material to prepare the ferrotitanium alloy (see Warrendale, PA: TMS, 2007:117-126). A similar titanium preparation method is developed by Beijing university of science and technology research group, and is called as the "USTB process" (CN 1712571 discloses a method for producing pure titanium by anode electrolysis of a titanium monoxide/titanium carbide soluble solid solution; CN103451682A discloses a method for extracting metallic titanium by molten salt electrolysis of a titanium-containing soluble anode), and titanium white and graphite are adopted as raw materials to perform heat treatment under vacuum condition to prepare TiC with good conductivity x O y The solid solution is used as an anode material for electrolyzing the metallic titanium, the result shows that the electrolytic titanium has high purity and stable current, the whole process does not use chlorine, only carbon monoxide gas which can be used as fuel is generated, the environmental load is small, and the large-scale production is easy to realize, thus being an important method for preparing the metallic titanium. However, tiC prepared by this method x O y The method is carried out under high vacuum condition, the sealing performance of the equipment is too high, and the compactness and conductivity of the electrode are also realizedThere is still room for further improvement in terms of electrical rate, electrolysis current efficiency, and the like.
Disclosure of Invention
The invention provides a method for preparing metallic titanium by soluble anode electrolysis of a fluorine-chlorine mixed molten salt system, which aims at the defects of the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
method for preparing metallic titanium by soluble anodic electrolysis 2 The mixture of the materials and the C-containing materials is used as the raw material to prepare TiC through the main procedures of primary grinding, primary briquetting, primary roasting, secondary grinding, secondary briquetting and secondary roasting x O y The conductive ceramic adopts a fluorine-chlorine mixed molten salt system after pre-electrolysis and uses TiC x O y The conductive ceramic is used as an anode, and the high-purity metallic titanium product is prepared through the procedures of electrolysis, washing and drying.
Preferably, the steps are specifically as follows:
s1, grinding for the first time: will contain TiO 2 Grinding the materials and the C-containing materials to ensure TiO during mixing 2 And C, the uniformity of spatial distribution and the activity of reaction particles, and the primary grinding and the uniform mixing function are realized;
s2, primary briquetting: placing the materials obtained by primary grinding into a mould, and pressing and forming by a press to form a raw material block with good compactness, wherein the mould meets the geometric shape and size requirements of the baked raw material block;
s3, primary roasting: roasting the raw material block formed by pressing the primary briquetting at a high temperature to obtain a primary roasting product;
s4, secondary grinding: grinding the primary roasting product to form TiC with small granularity and good dispersivity x O y Ceramic fine particles;
s5, secondary briquetting: grinding the TiC obtained by the secondary grinding x O y Placing ceramic fine particles in a die to carry out secondary briquetting, wherein the die meets the requirements of the geometric shape and the size of an anode;
s6, secondary roasting: tiC obtained by secondary briquetting x O y The material block is subjected to secondary roasting to obtain soluble TiC required by electrolysis in the step S8 x O y A conductive ceramic anode;
s7, pre-electrolysis: placing fluorine-chlorine mixed molten salt electrolyte in a graphite crucible, pre-electrolyzing in argon atmosphere with graphite as anode and tungsten wire as cathode to remove impurity components inherent in the fluorine-chlorine mixed molten salt electrolyte,
s8, electrolysis: by TiC x O y The conductive ceramic is used as an anode, the high-temperature-resistant metal material is used as a cathode, and CO are generated at the anode during electrolysis 2 The gas generates metallic titanium at the cathode, and the product can be sponge titanium or titanium powder according to different preparation process conditions;
s9, washing: stripping the cathode electrolytic product, and washing with pure water or dilute acid solution to remove electrolyte in the titanium sponge;
s10, drying: the washed metallic titanium is required to be dried in vacuum at low temperature to remove the moisture and volatile acid in the sponge titanium or titanium powder.
Preferably, the particle size (d) of the solid phase particles after grinding should be such that d.ltoreq.75 μm (. Gtoreq.200 mesh) is satisfied, whether primary grinding or secondary grinding.
Preferably, the primary briquetting or the secondary briquetting can adopt various briquetting modes, and when a uniaxial static pressure mode is adopted, the axial pressure is more than or equal to 20Mpa.
Preferably, for primary roasting or secondary roasting, the roasting temperature T needs to meet the condition that T is not less than 1300 and not more than 1550 ℃, and the roasting time T is not less than 1h and not more than 6h.
Preferably, the primary roasting and the secondary roasting are carried out under an argon protection atmosphere without maintaining a vacuum environment.
Preferably, a mixed molten salt system of fluoride and chloride is adopted in electrolysis, and the chloride comprises NaCl, KCl, liCl, mgCl 2 And CaCl 2 One or more of the fluorides including NaF, KF, alF 3 、Na 3 AlF 6 、KF、K 2 Ti 4 F 6 And Na (Na) 2 Ti 4 F 6 One or more of them.
Preferably, in the step S7, during pre-electrolysis, the voltage of the two electrodes is controlled to be 2-2.7V; in the step S8, during electrolysis, the cell voltage is controlled to be 3.0-3.5V, and the anode current density is in the range of 0.1-1.5A/cm 2 The cathode current density ranges from 0.3 to 2A/cm 2 。
Preferably, the electrolytic product can be washed by pure water or dilute acid solution after being stripped, and the washing is carried out, and then vacuum drying is carried out, wherein the drying temperature is 40-80 ℃, so that the final metallic titanium product is prepared.
Preferably, the TiO-containing material 2 The material comprises titanium white, the C-containing material comprises graphite, and the high-temperature-resistant metal material serving as the cathode in the step S8 comprises titanium and stainless steel.
Preferably, the method comprises the steps of,
s1, grinding for the first time: the preferred molar ratio of titanium dioxide to graphite is 1:1.5 to 2.5.
S2, primary briquetting: during pressing, the axial static pressure is controlled to be 20-40 MPa/cm 2 。
S3, primary roasting: roasting at high temperature, heating to 1500-1600 ℃, and preserving heat for 1-6 h.
S5, secondary briquetting: the axial static pressure is controlled to be 20-40 MPa/cm 2 。
S6, secondary roasting: heating to 1500-1600 deg.c and maintaining for 1-6 hr.
Compared with the prior art, the invention has the following beneficial effects:
the method adopted by the invention belongs to a soluble anode electrolysis method, and is similar to the USTB technology, and titanium white (TiO) 2 ) And graphite (C) as raw materials, forming a soluble anode through high-temperature heat treatment, and then preparing metallic titanium through molten salt electrolysis, so that the method comprises the advantages of the USTB technology. However, the present invention makes a number of important improvements to the USTB process, which are mainly manifested in:
(1) The non-vacuum argon protective atmosphere reduces the requirement of the preparation condition on the tightness of equipment, reduces the investment of a vacuum system, and is convenient for realizing industrial production as soon as possible; the non-nitriding anode material and the non-nitrogen protective atmosphere are adopted, so that the reaction between N and Ti in the electrolysis process is avoided, and the purity of the metallic titanium product is reduced.
(2) The technology of sectional grinding, sectional briquetting and sectional roasting is adopted to ensure that the space distribution of reactants is more uniform, and TiC formed after primary roasting is reduced x O y Porosity in ceramics, tiC is enhanced x O y Fusion between ceramic particles to improve TiC x O y The density of the anode is further improved, thereby TiC in the anode x O y The purity and the conductivity of the anode improve the mechanical strength and corrosion resistance of the electrode under the high-temperature electrolysis condition;
(3) Compared with a pure chloride system, the fluorine-chlorine compound mixed system is adopted as electrolyte, so that volatilization of molten salt in the electrolysis process is reduced, stability of electrolysis is improved, and TiC is improved x O y Solubility in the electrolyte, thereby contributing to an improvement in current efficiency; compared with a simple fluoride system, the eutectic temperature of the electrolyte is reduced, the electrolysis temperature and the energy consumption are reduced, and the operation environment is improved.
(4) Impurities in molten salt are effectively removed through pre-electrolysis, consumption of impurity ions to current and precipitation at a cathode are reduced, and electrolysis current efficiency and quality of metallic titanium products are improved.
(5) TiC prepared by the technique provided by the invention x O y The anode room temperature conductivity is improved by an order of magnitude compared with the traditional technology, and still keeps high conductivity at high temperature, so that the electrolytic loop resistance is effectively reduced, and the current efficiency is obviously improved. Meanwhile, due to the enhancement of the compactness of the anode, the stability of electrolysis is improved, and the defects of poor stability, easy crack growth and even falling-off of the anode in the conventional electrolysis process are overcome.
Drawings
FIG. 1 is a flow chart of the process of the present invention, wherein TiC is prepared by stepwise grinding, briquetting and roasting x O y The anode material is subjected to pre-electrolysis, washing and low-temperature vacuum drying to obtain high-purity metallic titanium. Roasting, pre-electrolysis and electrolysis are all performed in argonUnder a gaseous atmosphere.
FIG. 2 shows TiC prepared under different carbon distribution conditions according to the present invention x O y The XRD pattern of the anode material, as can be seen from the figure, when TiO 2 The proportion of the C is 1:2, preparing single TiC x O y The phase has no generation of impurity phase and residual carbon, and the impurity phase exists in the products with insufficient carbon compounding amount or excessive carbon compounding amount. And (3) injection: tiC x O y The phase is a solid solution of TiC and TiO, and the diffraction peak position is basically consistent with TiC.
FIG. 3 shows TiC prepared under different carbon distribution conditions according to the present invention x O y As can be seen from the XRD pattern of the anode material, tiC starts to be generated when the temperature reaches 1400 ℃ x O y And (3) phase (C). When the temperature reaches 1500 ℃, the main phase component is TiC x O y Incomplete reaction, residual C and Ti 2 O 3 The impurity phase exists. When the temperature reaches 1550 ℃, single TiC is generated x O y And (3) phase (C).
FIG. 4 shows TiC prepared according to the present invention x O y SEM of anode material showing TiC x O y The anode material presents a branch porous coral reef microcosmic appearance. From SEM image, the compactness of the material and the thickness of the bridging neck between particles can be observed, which can be used as the current in TiC during electrolysis x O y A microstructural criterion for the network distribution and conductivity of the material.
FIG. 5 is an XRD pattern of metallic titanium prepared in accordance with the present invention, reflecting that under suitable electrolysis conditions the electrolysis product is a single metallic titanium phase, without any impurity phases present.
Fig. 6 is an SEM image of the metallic titanium prepared according to the present invention, reflecting that the metallic titanium prepared forms a dendritic structure from micron-sized grains, conforming to the basic microscopic morphological features of titanium sponge.
Detailed Description
The technical scheme of the invention is further described below through examples.
Example 1
The embodiment relates to a method for preparing metallic titanium by mixed molten salt soluble anode electrolysis, which specifically comprises the following steps (the experimental process flow is shown in figure 1):
s1, grinding for the first time: titanium dioxide and graphite are mixed according to a mole ratio of 1:2 is placed in an agate ball milling tank, ball milling is carried out on a planetary ball mill for 3 hours at 400rpm, so as to ensure TiO during mixing 2 And uniformity of the spatial distribution of C and activity of the reaction particles.
S2, primary briquetting: placing the material ground at one time into a mould, pressing into cylindrical raw material block by using a press, and controlling axial static pressure to be 25MPa/cm 2 The resulting geometry is aboutRaw material blocks of (a);
s3, primary roasting: placing the raw material block formed by pressing the primary pressing block in a resistance furnace for high-temperature roasting under the argon atmosphere, heating to 1550 ℃ at a heating rate of 10 ℃/min, preserving heat for 4 hours, and cooling to obtain a primary roasting product;
s4, secondary grinding: placing the primary roasting product in an agate ball milling tank, ball milling for 3 hours on a planetary ball mill at 400rpm to obtain TiC with small granularity and good dispersibility x O y Ceramic fine powder;
s5, secondary briquetting: grinding the TiC obtained by the secondary grinding x O y Placing the ceramic powder in a die, performing secondary briquetting, and controlling the axial static pressure to be 25MPa/cm 2 TiC having a geometry of about 50mm by 15mm by 5mm was obtained x O y And (3) a material block.
S6, secondary roasting: tiC obtained by secondary briquetting x O y Placing the material block in a resistance furnace for secondary roasting, wherein the heating rate is still 10 ℃/min, heating to 1550 ℃, and preserving heat for 4 hours to obtain the soluble TiC required by electrolysis x O y Anode block (XRD of its product is shown as G2 curve in fig. 2 and S7 (1823K) curve in fig. 3), microstructure of the product is shown as fig. 4);
s7, pre-electrolysis: the fluorine-chlorine mixed molten salt electrolyte is placed in a graphite crucible, graphite is used as an anode, and tungsten wire is used as a cathode to carry out pre-electrolysis under the argon atmosphere, so that inherent impurity components in the molten salt are removed. The voltage of the pre-electrolysis tank is controlled to be 2.6V.
S8, electrolysis: by TiC x O y The anode block is used as anode, titanium sheet is used as cathode, KCl-NaCl-K is used as anode 2 TiF 6 The mixed molten salt is used as electrolyte for electrolysis, the cell voltage is controlled at 3.0V, and the anode current density is about 0.2A/cm 2 The cathode current density range was 0.3A/cm 2 . CO and CO production at the anode during electrolysis 2 And (3) gas, and precipitating metallic titanium at the cathode.
S9, washing: the electrolytic product is peeled off and then washed with a dilute hydrochloric acid solution with a concentration of 3%, and then washed with pure water to remove the electrolyte in the titanium sponge.
S10, drying: after washing, the obtained metallic titanium was vacuum-dried in a vacuum drying oven at 40 ℃ for 6 hours to remove water in the sponge titanium and hydrochloric acid in the residual washing liquid, thereby preparing the final metallic titanium product (XRD thereof is shown in fig. 5, SEM is shown in fig. 6).
Through the above process steps, the TiC is prepared x O y The anode had an electrical conductivity of 1.06X10 at 768.21 DEG C 5 S·m -1 The current efficiency reaches 90.32%, the purity of the obtained metallic titanium product is 99.92%, and the specific chemical compositions are shown in table 1:
TABLE 1 chemical Components (mass%) of titanium sponge product prepared by example 1
Example 2
The embodiment relates to a method for preparing metallic titanium by mixed molten salt soluble anode electrolysis, which specifically comprises the following steps:
s1, grinding for the first time: titanium dioxide and graphite are mixed according to a mole ratio of 1:2 is placed in an agate ball milling tank, ball milling is carried out on a planetary ball mill for 6 hours at the rotating speed of 300rpm, so as to ensure TiO during mixing 2 And uniformity of the spatial distribution of C and activity of the reaction particles.
S2, onceAnd (3) briquetting: placing the material ground at one time into a mould, pressing into cylindrical raw material block by using a press, and controlling axial static pressure to be 30MPa/cm 2 The resulting geometry is aboutRaw material blocks of (a);
s3, primary roasting: placing the raw material block formed by pressing the primary pressing block in a resistance furnace for high-temperature roasting under the argon atmosphere, wherein the heating rate is 10 ℃/min, the temperature is increased to 1600 ℃, the temperature is kept for 2 hours, and the primary roasting product is obtained after cooling;
s4, secondary grinding: placing the primary roasting product in an agate ball milling tank, ball milling for 6 hours on a planetary ball mill at a rotating speed of 300rpm to obtain TiC with small granularity and good dispersibility x O y Ceramic fine powder;
s5, secondary briquetting: grinding the TiC obtained by the secondary grinding x O y Placing the ceramic powder in a die, performing secondary briquetting, and controlling the axial static pressure to be 30MPa/cm 2 TiC having a geometry of about 50mm by 15mm by 5mm was obtained x O y And (3) a material block.
S6, secondary roasting: tiC obtained by secondary briquetting x O y Placing the material block in a resistance furnace for secondary roasting, wherein the heating rate is still 10 ℃/min, the temperature is increased to 1600 ℃, and the temperature is kept for 4 hours to obtain the soluble TiC required by electrolysis x O y An anode block;
s7, pre-electrolysis: the fluorine-chlorine mixed molten salt electrolyte is placed in a graphite crucible, graphite is used as an anode, and tungsten wire is used as a cathode to carry out pre-electrolysis under the argon atmosphere, so that inherent impurity components in the molten salt are removed. The pre-electrolysis cell voltage was controlled at 2.7V.
S8, electrolysis: by TiC x O y The anode block is used as anode, titanium sheet is used as cathode, KCl-NaCl-K is used as anode 2 TiF 6 The mixed molten salt is used as electrolyte for electrolysis, the cell voltage is controlled at 3.0V, and the anode current density is about 0.3A/cm 2 The cathode current density range was 0.5A/cm 2 . CO and CO production at the anode during electrolysis 2 And (3) gas, and precipitating metallic titanium at the cathode.
S9, washing: the electrolytic product is peeled off and then washed with a dilute hydrochloric acid solution with a concentration of 3%, and then washed with pure water to remove the electrolyte in the titanium sponge.
S10, drying: and (3) placing the obtained metallic titanium in a vacuum drying oven for vacuum drying after washing, wherein the drying temperature is 50 ℃, and the drying time is 4 hours, so as to remove the moisture in the titanium sponge and the hydrochloric acid in the residual washing liquid, thereby preparing the final metallic titanium product.
Through the above process steps, the TiC is prepared x O y The anode had a conductivity of 1.24X10 at 768.21 DEG C 5 S·m -1 The current efficiency reaches 90.17%, and the purity of the obtained metallic titanium product is 99.90%.
Example 3
The embodiment relates to a method for preparing metallic titanium by mixed molten salt soluble anode electrolysis, which specifically comprises the following steps:
s1, grinding for the first time: titanium dioxide and graphite are mixed according to a mole ratio of 1:2 is placed in an agate ball milling tank, ball milling is carried out on a planetary ball mill for 5 hours at the rotating speed of 400rpm, so as to ensure TiO during mixing 2 And uniformity of the spatial distribution of C and activity of the reaction particles.
S2, primary briquetting: placing the material ground at one time into a mould, pressing into cylindrical raw material block by using a press, and controlling axial static pressure to be 40MPa/cm 2 The resulting geometry is aboutRaw material blocks of (a);
s3, primary roasting: placing the raw material block formed by pressing the primary pressing block in a resistance furnace for high-temperature roasting under the argon atmosphere, heating to 1550 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and cooling to obtain a primary roasting product;
s4, secondary grinding: placing the primary roasting product in an agate ball milling tank, ball milling for 6 hours on a planetary ball mill at a rotating speed of 300rpm to obtain TiC with small granularity and good dispersibility x O y Ceramic fine powder;
s5, secondary pressing block: grinding the TiC obtained by the secondary grinding x O y Placing the ceramic powder in a die, performing secondary briquetting, and controlling the axial static pressure to be 20MPa/cm 2 TiC having a geometry of about 50mm by 15mm by 5mm was obtained x O y And (3) a material block.
S6, secondary roasting: tiC obtained by secondary briquetting x O y Placing the material block in a resistance furnace for secondary roasting, wherein the heating rate is still 10 ℃/min, the temperature is increased to 1600 ℃, and the temperature is kept for 3 hours to obtain the soluble TiC required by electrolysis x O y An anode block;
s7, pre-electrolysis: the fluorine-chlorine mixed molten salt electrolyte is placed in a graphite crucible, graphite is used as an anode, and tungsten wire is used as a cathode to carry out pre-electrolysis under the argon atmosphere, so that inherent impurity components in the molten salt are removed. The voltage of the pre-electrolysis tank is controlled to be 2.5V.
S8, electrolysis: by TiC x O y The anode block is used as anode, titanium sheet is used as cathode, KCl-NaCl-K is used as anode 2 TiF 6 The mixed molten salt is used as electrolyte for electrolysis, the cell voltage is controlled at 3.3V, and the anode current density is about 0.4A/cm 2 The cathode current density range was 0.8A/cm 2 . CO and CO production at the anode during electrolysis 2 And (3) gas, and precipitating metallic titanium at the cathode.
S9, washing: the electrolytic product is peeled off and then washed with a dilute hydrochloric acid solution with a concentration of 1%, and then washed with pure water to remove the electrolyte in the titanium sponge.
S10, drying: and (3) placing the obtained metallic titanium in a vacuum drying oven for vacuum drying after washing, wherein the drying temperature is 70 ℃, and the drying time is 2 hours, so as to remove the moisture in the titanium sponge and the hydrochloric acid in the residual washing liquid, thereby preparing the final metallic titanium product.
Through the above process steps, the TiC is prepared x O y The anode had an electrical conductivity of 0.95X 10 at 768.21 DEG C 5 S·m -1 The current efficiency reaches 90.38%, and the purity of the obtained metallic titanium product is 99.91%.
Example 4
The embodiment relates to a method for preparing metallic titanium by mixed molten salt soluble anode electrolysis, which specifically comprises the following steps:
s1, grinding for the first time: titanium dioxide and graphite are mixed according to a mole ratio of 1:2 is placed in an agate ball milling tank, ball milling is carried out on a planetary ball mill for 8 hours at the rotating speed of 350rpm, so as to ensure TiO during mixing 2 And uniformity of the spatial distribution of C and activity of the reaction particles.
S2, primary briquetting: placing the material ground at one time into a mould, pressing into cylindrical raw material block by using a press, and controlling axial static pressure to be 35MPa/cm 2 The resulting geometry is aboutRaw material blocks of (a);
s3, primary roasting: placing the raw material block formed by pressing the primary pressing block in a resistance furnace for high-temperature roasting under the argon atmosphere, heating to 1525 ℃ at a heating rate of 10 ℃/min, preserving heat for 5 hours, and cooling to obtain a primary roasting product;
s4, secondary grinding: placing the primary roasting product in an agate ball milling tank, ball milling for 6 hours on a planetary ball mill at a rotating speed of 300rpm to obtain TiC with small granularity and good dispersibility x O y Ceramic fine powder;
s5, secondary briquetting: grinding the TiC obtained by the secondary grinding x O y Placing the ceramic powder in a die, performing secondary briquetting, and controlling the axial static pressure to be 20MPa/cm 2 TiC having a geometry of about 50mm by 15mm by 5mm was obtained x O y And (3) a material block.
S6, secondary roasting: tiC obtained by secondary briquetting x O y Placing the material block in a resistance furnace for secondary roasting, wherein the heating rate is still 10 ℃/min, heating to 1525 ℃, and preserving heat for 3 hours to obtain the soluble TiC required by electrolysis x O y An anode block;
s7, pre-electrolysis: the fluorine-chlorine mixed molten salt electrolyte is placed in a graphite crucible, graphite is used as an anode, and tungsten wire is used as a cathode to carry out pre-electrolysis under the argon atmosphere, so that inherent impurity components in the molten salt are removed. The voltage of the pre-electrolysis tank is controlled to be 2.5V.
S8, electrolysis: by TiC x O y The anode block is used as anode, titanium sheet is used as cathode, KCl-NaCl-K is used as anode 2 TiF 6 The mixed molten salt is used as electrolyte for electrolysis, the voltage of the electrolytic tank is controlled to be 3.1V, and the current density of the anode is about 0.3A/cm 2 The cathode current density range was 0.6A/cm 2 . CO and CO production at the anode during electrolysis 2 And (3) gas, and precipitating metallic titanium at the cathode.
S9, washing: the electrolytic product is peeled off and then washed with a dilute hydrochloric acid solution with a concentration of 2%, and then washed with pure water to remove the electrolyte in the titanium sponge.
S10, drying: and (3) placing the obtained metallic titanium in a vacuum drying oven for vacuum drying after washing, wherein the drying temperature is 70 ℃, and the drying time is 2 hours, so as to remove the moisture in the titanium sponge and the hydrochloric acid in the residual washing liquid, thereby preparing the final metallic titanium product.
Through the above process steps, the TiC is prepared x O y The anode had a conductivity of 1.67X 10 at 768.21 DEG C 5 S·m -1 The current efficiency reaches 89.23%, and the purity of the obtained metallic titanium product is 99.87%.
Comparative examples
The embodiment relates to a method for preparing metallic titanium by adopting traditional soluble anodic electrolysis, which comprises the following preparation process conditions: the method for preparing the metallic titanium by only one grinding, one briquetting and one roasting process is carried out in a vacuum environment, wherein the electrolyte is a KCl-NaCl chloride system, the pre-electrolysis is not carried out, and the rest preparation conditions are completely the same as those of the embodiment 1, and the specific steps are as follows:
s1, grinding: titanium dioxide and graphite are mixed according to a mole ratio of 1:2 is placed in an agate ball milling tank, ball milling is carried out on a planetary ball mill for 3 hours at 400rpm, so as to ensure TiO during mixing 2 And uniformity of the spatial distribution of C and activity of the reaction particles.
S2, briquetting: placing the material ground at one time into a mould, pressing into cylindrical raw material block by using a press, and controlling axial static pressure to be 25MPa/cm 2 The resulting geometry is aboutRaw material blocks of (a);
s3, roasting: under vacuum condition (vacuum pressure about 70 Pa), placing the pressed raw material block into a resistance furnace for high-temperature roasting, heating to 1550 ℃ at a heating rate of 10 ℃/min, preserving heat for 4h, and cooling to obtain TiC x O y An anode block;
s4, electrolysis: by TiC x O y The anode block is used as an anode, a titanium sheet is used as a cathode, KCl-NaCl chloride molten salt is used as electrolyte for electrolysis, and the anode current density is about 0.2A/cm 2 The cathode current density range was 0.3A/cm 2 . CO and CO production at the anode during electrolysis 2 And (3) gas, and precipitating metallic titanium at the cathode.
S5, washing: the electrolytic product is peeled off and then washed with a dilute hydrochloric acid solution with a concentration of 3%, and then washed with pure water to remove the electrolyte in the titanium sponge.
S6, drying: and (3) placing the obtained metallic titanium in a vacuum drying oven for vacuum drying after washing, wherein the drying temperature is 40 ℃, and the drying time is 6 hours, so as to remove the moisture in the titanium sponge and the hydrochloric acid in the residual washing liquid, thereby preparing the final metallic titanium product.
TiC prepared through the process steps x O y The anode had a conductivity of 0.72X10 at room temperature 4 S·m -1 The current efficiency reaches 84.46%, and the purity of the obtained metallic titanium product is 99.05%.
As can be seen from the comparative examples, although the process flow of the method adopted by the invention is longer than that of the conventional soluble anode electrolysis process for preparing metallic titanium, the test results show that TiC is obtained after the process improvement of the invention x O y The conductivity of the anode is improved by more than one order of magnitude, the current efficiency is improved by about 5-6%, the purity of the metal titanium product is improved from 2N level to 3N level, the method has a crucial effect on reducing the production energy consumption and improving the product level, and has a good promoting effect on the industrialized production of the metal titanium prepared by an electrolytic method in the early days.
Claims (5)
1. A method for preparing metallic titanium by fluorine-chlorine mixed molten salt system soluble anode electrolysis uses a mixture of titanium white and graphite as a raw material, and prepares TiC through main procedures of primary grinding, primary briquetting, primary roasting, secondary grinding, secondary briquetting and secondary roasting x O y The conductive ceramic is characterized in that a fluorine-chlorine mixed molten salt system after pre-electrolysis is adopted, and TiC is adopted x O y The conductive ceramic is used as an anode, and the high-purity metallic titanium product is prepared through the procedures of electrolysis, washing and drying,
s1, grinding for the first time: titanium white and graphite are mixed according to a mole ratio of 1:2, grinding to ensure TiO during mixing 2 And C, the uniformity of spatial distribution and the activity of reaction particles, and the primary grinding and the uniform mixing function are realized;
s2, primary briquetting: placing the materials obtained by primary grinding into a mould, and pressing and forming by a press to form a raw material block with good compactness, wherein the mould meets the geometric shape and size requirements of the baked raw material block;
s3, primary roasting: roasting the raw material block formed by pressing the primary briquetting at a high temperature to obtain a primary roasting product;
s4, secondary grinding: grinding the primary roasting product to form TiC with small granularity and good dispersivity x O y Ceramic fine particles;
s5, secondary briquetting: grinding the TiC obtained by the secondary grinding x O y Placing ceramic fine particles in a die to carry out secondary briquetting, wherein the die meets the requirements of the geometric shape and the size of an anode;
s6, secondary roasting: tiC obtained by secondary briquetting x O y The material block is subjected to secondary roasting to obtain soluble TiC required by electrolysis in the step S8 x O y A conductive ceramic anode;
s7, pre-electrolysis: placing the fluorine-chlorine mixed molten salt electrolyte in a graphite crucible, pre-electrolyzing in an argon atmosphere by taking graphite as an anode and tungsten wire as a cathode to remove inherent impurity components in the fluorine-chlorine mixed molten salt electrolyte, and controlling the voltage of two poles to be 2-2.7 and V;
s8, electrolysis: by TiC x O y The conductive ceramic is used as an anode, the high temperature resistant metal material is used as a cathode, and KCl-NaCl-K is used as a cathode 2 TiF 6 The mixed molten salt is used as electrolyte for electrolysis, and CO are generated at the anode during electrolysis 2 The gas generates metallic titanium at the cathode, and the product can be sponge titanium or titanium powder according to different preparation process conditions; during electrolysis, the cell voltage is controlled to be 3.0-3.5V, and the anode current density is in the range of 0.1-1.5A/cm 2 The cathode current density is in the range of 0.3-2A/cm 2 ；
S9, washing: stripping the cathode electrolytic product, and washing with pure water or dilute acid solution to remove electrolyte in the titanium sponge;
s10, drying: the washed metallic titanium is required to be dried in vacuum at low temperature to remove the moisture and volatile acid in the sponge titanium or titanium powder;
the firing temperature is either for the primary firing or the secondary firingTIs required to meet 1525 less than or equal toTFiring time at 1600℃ or lesstIs less than or equal to 1ht≤6 h；
The primary roasting and the secondary roasting are carried out under the protection of argon without maintaining a vacuum environment.
2. The method for preparing metallic titanium by soluble anode electrolysis of a fluorine-chlorine mixed molten salt system according to claim 1, wherein the particle size d of the solid phase particles after grinding is less than or equal to 75 μm whether the primary grinding or the secondary grinding is carried out.
3. The method for preparing metallic titanium by soluble anode electrolysis of a fluorine-chlorine mixed molten salt system according to claim 1, wherein a plurality of briquetting modes can be adopted, and when a uniaxial static pressure mode is adopted, the axial pressure is more than or equal to 20Mpa.
4. The method for preparing metallic titanium by soluble anode electrolysis of a fluorine-chlorine mixed molten salt system according to claim 1, wherein the electrolytic product can be washed by pure water or dilute acid solution after being stripped, and the washing is performed by vacuum drying at the drying temperature of 40-80 ℃ so as to prepare the final metallic titanium product.
5. The method for preparing metallic titanium by soluble anode electrolysis of a fluorine-chlorine mixed molten salt system according to claim 1, wherein the high temperature resistant metallic material used as the cathode in the step S8 comprises titanium and stainless steel.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712571A (en) * | 2005-05-08 | 2005-12-28 | 北京科技大学 | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis |
| CN101947652A (en) * | 2010-09-21 | 2011-01-19 | 攀钢集团有限公司 | Method for preparing C-O-T (carbon-oxygen-titanium) composite anode by microwave heating |
| CN102912379A (en) * | 2012-10-25 | 2013-02-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metal titanium |
| CN103451682A (en) * | 2013-09-16 | 2013-12-18 | 北京科技大学 | Method for extracting metal titanium through molten salt electrolysis of titanium-containing soluble anode |
| CN109763148A (en) * | 2019-01-14 | 2019-05-17 | 浙江海虹控股集团有限公司 | A kind of device and method that continuous electrolysis prepares high pure metal titanium valve |
| CN109811370A (en) * | 2019-03-15 | 2019-05-28 | 北京科技大学 | A kind of electrolysis-titanium carbon sulphur anode-method for preparing Titanium |
-
2021
- 2021-07-17 CN CN202110810003.1A patent/CN113699560B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712571A (en) * | 2005-05-08 | 2005-12-28 | 北京科技大学 | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis |
| CN101947652A (en) * | 2010-09-21 | 2011-01-19 | 攀钢集团有限公司 | Method for preparing C-O-T (carbon-oxygen-titanium) composite anode by microwave heating |
| CN102912379A (en) * | 2012-10-25 | 2013-02-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metal titanium |
| CN103451682A (en) * | 2013-09-16 | 2013-12-18 | 北京科技大学 | Method for extracting metal titanium through molten salt electrolysis of titanium-containing soluble anode |
| CN109763148A (en) * | 2019-01-14 | 2019-05-17 | 浙江海虹控股集团有限公司 | A kind of device and method that continuous electrolysis prepares high pure metal titanium valve |
| CN109811370A (en) * | 2019-03-15 | 2019-05-28 | 北京科技大学 | A kind of electrolysis-titanium carbon sulphur anode-method for preparing Titanium |
Non-Patent Citations (1)
| Title |
|---|
| "熔融盐电镀难熔金属钛的探讨";陈书荣等;《98’昆明理工大学研究生学术交流会 论文集》;第139-142页 * |
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