CN109267100A - A kind of device and method of electrolysis-pure titanium of chlorination-electrolytic preparation - Google Patents
A kind of device and method of electrolysis-pure titanium of chlorination-electrolytic preparation Download PDFInfo
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- CN109267100A CN109267100A CN201811408695.1A CN201811408695A CN109267100A CN 109267100 A CN109267100 A CN 109267100A CN 201811408695 A CN201811408695 A CN 201811408695A CN 109267100 A CN109267100 A CN 109267100A
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- 239000010936 titanium Substances 0.000 title claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 43
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 7
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 7
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000010962 carbon steel Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 210000004027 cell Anatomy 0.000 description 46
- 239000000460 chlorine Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 2
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- 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
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
-
- 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
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon
-
- 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
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
Landscapes
- 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
A kind of device and method of electrolysis-pure titanium of chlorination-electrolytic preparation belongs to electrolysis method production Titanium field.First electrolytic cell is using molten alkali metal chloride, alkaline earth metal chloride, aluminium chloride or their mixture as electrolyte, and the second electrolytic cell is using molten alkali metal chloride, alkaline earth metal chloride or their mixture as electrolyte；The Cl generated at first anode electrolytic cell2Entered by conduit and contains TiCxOyOr TiCxOyNzIn the chlorination reactor of raw material, chlorination goes out TiCl at a temperature of 200 DEG C~600 DEG C4Gas；The gas is passed through in the second electrolytic cell at cathode by conduit, utilizes TiCl4Dissolubility in the second electrolytic cell, and then it is electrolysed out high-purity titanium；The Cl that anode generates simultaneously2It is recycled in the first electrolytic cell chlorination reactor again and continues to participate in TiCxOyOr TiCxOyNzChlorination.Present invention process is simple, clean and effective；Simultaneously can be accurate to customize by-product obtained by the first electrolytic cell according to demand, further promote economic benefit.
Description
Technical field
The present invention relates to a kind of electrolysis-chlorination-electrolytic preparation pure titanium device and methods, belong to electrolysis method production Titanium
Field.
Background technique
Titanium has many excellent physical and chemical performances, the low (4.5g/cm of density3), it is fusing point high (1660 DEG C), anti-
It is burn into resistance to oxidation, nontoxic, there is good biocompatibility, referred to as " the following metal ".It is in aerospace, chemistry
The fields such as chemical industry, ship naval vessels, biologic medical, civilian building materials and sports equipment have a wide range of applications.On this basis, people
Titanium by Ti content higher than 99.95% or 99.99% (i.e. 3N5 or 4N) is known as high-purity titanium.High-purity titanium is not only
Possess excellent performance possessed by common titanium, meanwhile, excellent elongation percentage (50-60%), the contraction percentage of area (70-
80%) and the objectionable impurities elements of super low loading are that common titanium can not be reached.Therefore, high purity titanium is in high-end microelectronics, point
Hold space technology, accurate super large-scale integration and display screen etc. high-end fields by favor.
Currently, there are mainly two types of methods for the industrialized production of high purity titanium, one is Kroll method, another kind is molten-salt electrolysis
Method.The former is with TiO2By obtaining TiCl with carbon, chlorination4, TiCl4Titanium is obtained using magnesiothermic reduction, and by-product
MgCl2It then needs to be decomposed using fused salt electrolysis process, be recycled to realize.Whole flow process it is many and diverse it is tediously long, yield is limited.
In addition, high-purity titanium in order to obtain, raw materials used (TiCl4And magnesium metal) higher purity is generally required, this adds increased
The preparation cost of high purity titanium.The latter is using titanium sponge as anode, using fused salt containing titanium halide as electrolyte, electrolytic process Anodic sea
Continuous titanium dissolution, cathode titanium ion deposition obtain high-purity titanium.This method can be controlled effectively relative to Kroll method short flow
Oxygen content in product processed obtains the high-purity titanium of hypoxemia.However, the preparation of titanium sponge be unable to do without Kroll method, therefore its eventually
Upstream process is complicated, inefficient, ultimately causes the fused-salt electrolytic refining higher cost using titanium sponge as anode.
In view of the above-mentioned problems, the invention proposes a kind of electrolysis-chlorination-electrolytic preparation pure titanium device and methods.With two
Titanium oxide and carbonaceous material powder mix according to a certain percentage, briquetting, TiC obtained by carbon thermal reductionxOyOr TiCxOyNzFor raw material.?
Electrolyzing fused alkali metal chloride, alkaline earth metal chloride, aluminium chloride or their mixture in one electrolytic cell, anode gained chlorine
Gas, which is passed through, contains TiCxOyOr TiCxOyNzIn the chlorination reactor of raw material, and then chlorination goes out TiCl4Gas；The gas passes through conduit
It is passed through in the second electrolytic cell at cathode, utilizes TiCl4Dissolubility in the second electrolytic cell, and then it is electrolysed out high-purity titanium；
The Cl that anode generates simultaneously2It is recycled in the first electrolytic cell chlorination reactor again and continues to participate in TiCxOyOr TiCxOyNzChlorination.
Prepare high-purity titanium relative to Kroll method or conventional fused salt electrolysis process, the electrolysis-chlorination-electrolytic preparation pure titanium device and
Method avoids the batch productive prospecting of the tediously long complexity of Kroll method from source, simplifies entire process flow, and reduce
Kroll method or conventional fused salt electrolysis process prepare the production cost of high purity titanium.In addition, the selection of the first electrolytic cell components of molten salt can be with
Depending on the requirement of the alkali metal of turn of the market or customer demand, alkaline-earth metal, aluminum metal or alloy, to improve byproduct
Effective value.
Summary of the invention
The present invention provides a kind of device and method of electrolysis-pure titanium of chlorination-electrolytic preparation.Relative to Kroll method or with sea
Continuous titanium is that the molten-salt electrolysis of raw material prepares high-purity titanium, and this method has process succinct, low in cost, and can prepare high value
The characteristics of by-product.
Attached drawing 1 is electrolysis of the invention-chlorination-electrolytic preparation pure titanium schematic device, and device is by the first electrolytic cell, the
Two electrolytic cells, chlorination reactor and gas-guide tube composition, appliance arrangement feature are as follows:
First electrolytic cell and the second electrolytic cell are horizontally disposed, and the first electrolytic cell has with the second bottom of electrolytic tank and surrounding
Heating and temperature control system, for controlling the temperature of electrolyte in electrolytic cell.
The chlorination reactor is located at the upper position of the first anode electrolytic cell, and porous ceramics partition is arranged in bottom；Chlorination
Reactor shell material is steel, is lined with ceramic material；There are independent heating and temperature control system outside chlorination reactor, is used for
Control chlorination reactor internal material temperature.
First gas-guide tube is located at the anode position in the first electrolytic cell, and connect with chlorination reactor bottom；Second
Gas-guide tube one end connects at the top of chlorination reactor, and the other end is located at the cathode site in the second electrolytic cell；Third gas-guide tube one end
Anode position in the second electrolytic cell, the other end are connect with the first gas-guide tube in the first electrolytic cell；Gas-guide tube material is
Steel are lined with ceramics or polytetrafluoroethylene material.
Included the following steps: using apparatus of the present invention electrolysis-chlorination-electrolytic preparation pure titanium method
1) according to chemical reaction metering than by titanium dioxide and carbonaceous material powder mixing it is uniform after, compression moulding, 900~
TiC is made in 1600 DEG C of temperature ranges in vacuum conditionxOyOr TiC is made in a nitrogen atmospherexOyNz, it is packed into chlorination reactor
In；
2) the first electrolytic cell is with molten alkali metal chloride, alkaline earth metal chloride, aluminium chloride or their mixture
Supporting electrolyte, anode are carbon material, and cathode is metal material, and electrolyzer temperature control is at 150~1000 DEG C, chlorination reactor
Temperature is controlled at 200~600 DEG C；After electrolysis starts, Cl-Anode is moved to, reacts and generates Cl2；Anodic product Cl2Via
First gas-guide tube pass through porous barrier enter in chlorination reactor, and with the TiC in chlorination reactorxOyOr TiCxOyNzOccur anti-
TiCl should be generated4Gas；The gas enters the second electric tank cathode region via the second gas-guide tube；
It 3) is to support electricity with molten alkali metal chloride, alkaline earth metal chloride or their mixture in the second electrolytic cell
Xie Zhi, anode are carbon material, and cathode is metal material, and electrolyzer temperature is controlled at 500~1000 DEG C；After electrolysis starts, by the
The TiCl of two gas-guide tubes conveying4Gas enters fused salt, Ti at the second electric tank cathode4+Generation is reacted at cathode at a low price
Titanium ion, the reaction was continued deposits to obtain pure titanium in cathode for low valence titanium ion, reacts as follows:
Ti4++ e=Ti3+
Ti3++ e=Ti2+
Ti2++ 2e=Ti
Cl-Anode is moved to, Cl is generated at anode2, it is delivered in the first gas-guide tube via third gas-guide tube, with first
The Cl generated at anode electrolytic cell2Mixing, into participating in TiC in chlorination reactorxOyOr TiCxOyNzChlorination；
4) after an electrolysing period, cathode product in two electrolytic cells is removed, and through overpickling, washing, drying
Etc. processing steps, the high-purity titanium of product is collected from the cathode of the second electrolytic cell, is collected from the cathode of the first electrolytic cell secondary
Product alkali metal, alkaline-earth metal, aluminum metal or alloy.
5) after the completion of step 4), cathode is reloaded into two electrolytic cells, and by new TiCxOyOr TiCxOyNzRaw material
It is fitted into chlorination reactor, then carries out the operation of the electrolysis production high purity titanium of a new round.
In the step 1), carbonaceous material powder is the group of one or more of graphite, petroleum coke, carbon black, coal, charcoal
It closes.
In the step 1), in titanium dioxide in oxygen atom and carbonaceous material powder the number ratio of carbon atom be 1.2:1~
0.5:1, preferably 1:1~0.667:1.
The step 2) and 3) in, in the first electrolytic cell and the second electrolytic cell cathodic metal material be titanium, carbon steel or nickel.
The step 2) and 3) in, in the first electrolytic cell and the second electrolytic cell be electrolysed when current density be respectively as follows: anode,
0.01A/cm2~2.00A/cm2；Cathode, 0.01A/cm2~2.00A/cm2。
Compared with the existing technology, the present invention has the advantages that
1) chlorine preparation, oxidation of coal titanium or carbon titanium oxynitrides low temperature chlorination and titanium tetrachloride, are electrolysed three parts in same
One device is completed, the concise in technology, cleaning, efficient；
2) magnesiothermic reduction and MgCl involved in Kroll method production process, are avoided2The processes such as electrolytic decomposition, thus
Greatly shorten the preparation flow of high purity titanium；
3), the application of double electrolytic cells, by oxidation of coal titanium or carbon titanium oxynitrides low temperature chlorination and TiCl4Electroreduction separates,
The preparation for not only improving high purity titanium guarantees the purity of titanium, and the Cl that two anodes are generated2Realization recycles, and further drops
Low pollution and energy consumption；
4), can be accurate to customize by-product obtained by the first electrolytic cell according to turn of the market or customer demand, to improve by-product
Object utility value.
Detailed description of the invention
Fig. 1 is electrolysis of the invention-chlorination-electrolytic preparation pure titanium schematic device；
Figure grade: 1. first electrolytic cells, 2. second electrolytic cells, 3. chlorination reactors, 4. porous ceramics partitions, 5. first lead
Tracheae, 6. second gas-guide tubes, 7. third gas-guide tubes.
Embodiment 1
By titanium dioxide and graphite powder according to mass ratio 40:12 mixing it is uniform after, compression moulding, in 1400 DEG C of vacuum-sinterings
3 hours obtained TiC0.5O0.5And it is fitted into chlorination reactor.First electrolytic cell is with NaCl-AlCl3Eutectic salts are electrolyte, second
It is electrolyte that electrolytic cell, which selects NaCl-KCl eutectic salts, and two electrolytic cells are all made of inert gas shielding.When electrolysis, the first electrolysis
The temperature of slot is controlled at 150 DEG C, and cathode and anode is all made of graphite as electrode, and current density is respectively 0.5 and 1A/cm2；Second
At 750 DEG C, anode uses graphite for electrolyzer temperature control, and cathode uses metal nickel plate, and cathode and anode current density is respectively 1 He
2A/cm2.After one electrolysing period, collect high-purity titanium from the cathode nickel plate of the second electrolytic cell, and through overpickling,
Washing, drying, encapsulation etc. obtain high-purity titanium powder or crystal, collect metallic aluminium from the cathode of the first electrolytic cell.
Embodiment 2
By titanium dioxide and graphite powder according to mass ratio 40:15 mixing it is uniform after, compression moulding, in 1600 DEG C of vacuum-sinterings
2 hours obtained TiC0.25O0.75And it is fitted into chlorination reactor.First electrolytic cell is with NaCl-MgCl2-AlCl3Eutectic salts are electrolysis
Matter, it is electrolyte that the second electrolytic cell, which selects NaCl-LiCl-KCl eutectic salts,, two electrolytic cells are all made of inert gas shielding.Electricity
The temperature of Xie Shi, the first electrolytic cell are controlled at 550 DEG C, and cathode and anode is all made of graphite as electrode, and current density is respectively 0.5
And 1.5A/cm2；For the control of second electrolyzer temperature at 600 DEG C, anode uses graphite, and cathode uses metallic titanium plate, cathode and anode electricity
Current density is respectively 0.5 and 1A/cm2.After one electrolysing period, high purity titanium is collected from the cathode nickel plate of the second electrolytic cell
Metal, and high-purity titanium powder or crystal are obtained through overpickling, washing, drying, encapsulation etc., from the cathode collector of the first electrolytic cell
Magnesium-aluminum alloy.
Embodiment 3
By titanium dioxide and graphite powder according to mass ratio 40:12 mixing it is uniform after, compression moulding, in 1300 DEG C of nitrogen atmospheres
3 hours obtained TiC of lower sintering0.2O0.2N0.6And it is fitted into chlorination reactor.First electrolytic cell is electrolysis with LiCl-KCl eutectic salts
Matter, it is electrolyte that the second electrolytic cell, which selects NaCl-CaCl eutectic salts, and two electrolytic cells are all made of inert gas shielding.When electrolysis,
The temperature of first electrolytic cell is controlled at 750 DEG C, and cathode and anode is all made of graphite as electrode, and current density is respectively 0.2 He
1.5A/cm2；For the control of second electrolyzer temperature at 800 DEG C, anode uses graphite, and cathode uses metal nickel plate, cathode and anode electric current
Density is respectively 0.5 and 1.5A/cm2.After one electrolysing period, high purity titanium is collected from the cathode nickel plate of the second electrolytic cell
Metal, and high-purity titanium powder or crystal are obtained through overpickling, washing, drying, encapsulation etc., from the cathode collector gold of the first electrolytic cell
Belong to potassium.
Certainly, the present invention can also be familiar with ability without departing substantially from the technology of the present invention essence there are many embodiment
The technical staff in domain can disclosure according to the present invention make various corresponding changes and modification, but these corresponding changes and modifications
All it should fall within the scope of protection of the appended claims of the present invention.
Claims (7)
1. a kind of electrolysis-chlorination-electrolytic preparation pure titanium device, which is characterized in that including the first electrolytic cell, the second electrolytic cell,
Chlorination reactor and gas-guide tube；
Wherein, the first electrolytic cell (1) and the second electrolytic cell (2) are horizontally disposed, the first electrolytic cell (1) and the second electrolytic cell (2) bottom
Portion and surrounding have heating and temperature control system, for controlling the temperature of electrolyte in electrolytic cell；Chlorination reactor (3) is located at the first electricity
The upper position of slot (1) anode is solved, porous ceramics partition (4) are arranged in bottom；
Chlorination reactor (3) shell material is steel, is lined with ceramic material；There is independent heating outside chlorination reactor (3)
With temperature control system, for controlling chlorination reactor (3) internal material temperature；
First gas-guide tube (5) is located at the anode position in the first electrolytic cell (1), and connect with chlorination reactor (3) bottom；Second
Gas-guide tube (6) one end connects at the top of chlorination reactor (3), and the other end is located at the cathode site in the second electrolytic cell (2)；Third is led
Tracheae (7) one end is located at the anode position in the second electrolytic cell (2), the first gas-guide tube in the other end and the first electrolytic cell (1)
(5) it connects；Gas-guide tube material is steel, is lined with ceramics or polytetrafluoroethylene material.
2. a kind of method for preparing pure titanium using device as described in claim 1, which is characterized in that mainly include following step
It is rapid:
1) according to chemical reaction metering than by titanium dioxide and carbonaceous material powder mixing it is uniform after, compression moulding, 900~1600
TiC is made in DEG C temperature range in vacuum conditionxOyOr TiC is made in a nitrogen atmospherexOyNz, it is fitted into chlorination reactor；
2) the first electrolytic cell is to support with molten alkali metal chloride, alkaline earth metal chloride, aluminium chloride or their mixture
Electrolyte, anode are carbon material, and cathode is metal material, and electrolyzer temperature control is at 150~1000 DEG C, chlorination reactor temperature
Control is at 200~600 DEG C；After electrolysis starts, Cl-Anode is moved to, reacts and generates Cl2；Anodic product Cl2Via first
Gas-guide tube pass through porous barrier enter in chlorination reactor, and with the TiC in chlorination reactorxOyOr TiCxOyNzReact production
Raw TiCl4Gas；The gas enters the second electric tank cathode region via the second gas-guide tube；
It 3) is to support electrolysis with molten alkali metal chloride, alkaline earth metal chloride or their mixture in the second electrolytic cell
Matter, anode are carbon material, and cathode is metal material, and electrolyzer temperature is controlled at 500~1000 DEG C；After electrolysis starts, by second
The TiCl of gas-guide tube conveying4Gas enters fused salt, Ti at the second electric tank cathode4+It reacts at cathode and generates Low-valent Titanium
Ion, the reaction was continued deposits to obtain pure titanium in cathode for low valence titanium ion, reacts as follows:
Ti4++ e=Ti3+
Ti3++ e=Ti2+
Ti2++ 2e=Ti
Cl-Anode is moved to, Cl is generated at anode2, it is delivered in the first gas-guide tube via third gas-guide tube, with the first electrolysis
The Cl generated at slot anode2Mixing, into participating in TiC in chlorination reactorxOyOr TiCxOyNzChlorination；
4) after an electrolysing period, cathode product in two electrolytic cells is removed, and through overpickling, washing, drying and processing
Step collects the high-purity titanium of product from the cathode of the second electrolytic cell, and byproduct alkali is collected from the cathode of the first electrolytic cell
Metal, alkaline-earth metal, aluminum metal or alloy；
5) after the completion of step 4), cathode is reloaded into two electrolytic cells, and by new TiCxOyOr TiCxOyNzRaw material is packed into
In chlorination reactor, then carry out the operation of the electrolysis production high purity titanium of a new round.
3. preparing the method for pure titanium according to claim 2, which is characterized in that the carbonaceous material powder be graphite, petroleum coke,
The combination of one or more of carbon black, coal, charcoal.
4. preparing the method for pure titanium according to claim 2, which is characterized in that oxygen atom and carbonaceous material in the titanium dioxide
The number ratio of carbon atom is 1.2:1~0.5:1 in feed powder.
5. according to the method for preparing pure titanium of claim 2 or 4, which is characterized in that oxygen atom and carbon in the titanium dioxide
The number ratio of carbon atom is 1:1~0.667:1 in material feed powder.
6. preparing the method for pure titanium according to claim 2, which is characterized in that first electrolytic cell and the second electrolytic cell
In, cathodic metal material is titanium, carbon steel or nickel.
7. preparing the method for pure titanium according to claim 2, which is characterized in that in first electrolytic cell and the second electrolytic cell
Current density when electrolysis is respectively as follows: anode, 0.01A/cm2~2.00A/cm2；Cathode, 0.01A/cm2~2.00A/cm2。
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| CN201811408695.1A CN109267100B (en) | 2018-11-23 | 2018-11-23 | Device and method for preparing pure titanium through electrolysis-chlorination-electrolysis |
| US16/612,739 US11180863B2 (en) | 2018-11-23 | 2019-03-27 | Device and method for preparing pure titanium by electrolysis-chlorination-electrolysis |
| PCT/CN2019/079833 WO2020103366A1 (en) | 2018-11-23 | 2019-03-27 | Device and method for preparing pure titanium by means of electrolysis-chlorination-electrolysis |
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