CN209024654U - A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation - Google Patents
A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation Download PDFInfo
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Abstract
A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation, 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, and chlorination reactor (3) is located at the upper position of the first electrolytic cell (1) anode, and porous ceramics partition (4) are arranged in bottom；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 gas-guide tube (7) one end is located at the anode position in the second electrolytic cell (2), and the other end is connect with the first gas-guide tube (5) in the first electrolytic cell (1).The utility model simple process, 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 utility model relates to a kind of electrolysis-chlorination-electrolytic preparation pure titanium device and methods, belong to electrolysis method production gold
Belong to 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.
Summary of the invention
In response to the above problems, the present invention proposes a kind of electrolysis-chlorination-electrolytic preparation pure titanium device and methods.
It is mixed according to a certain percentage with titanium dioxide and carbonaceous material powder, briquetting, carbon thermal reduction gained TiCxOyOr TiCxOyNzFor raw material.
Electrolyzing fused alkali metal chloride, alkaline earth metal chloride, aluminium chloride or their mixture in the first electrolytic cell, anode institute
Chlorine is passed through and contains TiCxOyOr TiCxOyNzIn the chlorination reactor of raw material, and then chlorination goes out TiCl4Gas；The gas passes through
Conduit 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
Belong to；The Cl that anode generates simultaneously2It is recycled in the first electrolytic cell chlorination reactor again and continues to participate in TiCxOyOr TiCxOyNzChlorine
Change.High-purity titanium is prepared 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.
The utility model provides a kind of device and method of electrolysis-pure titanium of chlorination-electrolytic preparation.Relative to Kroll method or
High-purity titanium is prepared by the molten-salt electrolysis of raw material of titanium sponge, this method has process succinct, low in cost, and can prepare height
The characteristics of being worth by-product.
Attached drawing 1 be the utility model electrolysis-chlorination-electrolytic preparation pure titanium schematic device, including the first electrolytic cell,
Second electrolytic cell, chlorination reactor and gas-guide tube；
Wherein, the first electrolytic cell and the second electrolytic cell are horizontally disposed, and chlorination reactor is located at the upper of the first anode electrolytic cell
Porous ceramics partition is arranged in portion position, bottom；
First gas-guide tube is located at the anode position in the first electrolytic cell, and connect with chlorination reactor bottom；Second air guide
Pipe 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 is located at
Anode position in second electrolytic cell, the other end are connect with the first gas-guide tube in the first electrolytic cell.
Further, the first electrolytic cell and the second bottom of electrolytic tank and surrounding have heating and temperature control system, for controlling chlorine
Change inside reactor temperature of charge.
Further, chlorination reactor shell material is steel, is lined with ceramic material；There is independence outside chlorination reactor
Heating and temperature control system, for controlling chlorination reactor internal material temperature.
Further, gas-guide tube material is steel, is lined with ceramics or polytetrafluoroethylene material.
Included the following steps: using utility model device 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 reaction
In device；
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
Reaction generates TiCl4Gas；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, utility model 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-chlorination-electrolytic preparation pure titanium schematic device of the utility model；
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.
Specific embodiment
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 utility model can also there are many embodiments, without departing substantially from the utility model technical spirit,
Those skilled in the art can disclosure according to the present utility model make various corresponding changes and modification, but these are corresponding
Change and modification all should belong to the protection scopes of the utility model the attached claims.
Claims (4)
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, and chlorination reactor (3) is located at the first electrolytic cell (1)
Porous ceramics partition (4) are arranged in the upper position of anode, bottom；
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.
2. electrolysis as described in claim 1-chlorination-electrolytic preparation pure titanium device, which is characterized in that the first electrolytic cell (1)
There are heating and temperature control system with the second electrolytic cell (2) bottom and surrounding, for controlling chlorination reactor (3) internal material temperature.
3. electrolysis as described in claim 1-chlorination-electrolytic preparation pure titanium device, which is characterized in that chlorination reactor (3)
Shell material is steel, is lined with ceramic material；There are independent heating and temperature control system outside chlorination reactor (3), for controlling
Chlorination reactor (3) internal material temperature processed.
4. electrolysis as described in claim 1-chlorination-electrolytic preparation pure titanium device, which is characterized in that gas-guide tube material is steel
Material is lined with ceramics or polytetrafluoroethylene material.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821942940.2U CN209024654U (en) | 2018-11-23 | 2018-11-23 | A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation |
| PCT/CN2019/079833 WO2020103366A1 (en) | 2018-11-23 | 2019-03-27 | Device and method for preparing pure titanium by means of 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 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821942940.2U CN209024654U (en) | 2018-11-23 | 2018-11-23 | A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation |
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| Publication Number | Publication Date |
|---|---|
| CN209024654U true CN209024654U (en) | 2019-06-25 |
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| CN201821942940.2U Active CN209024654U (en) | 2018-11-23 | 2018-11-23 | A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110983378A (en) * | 2019-11-15 | 2020-04-10 | 北京理工大学 | Device and method for preparing metal aluminum and titanium tetrachloride in molten salt by soluble anode |
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2018
- 2018-11-23 CN CN201821942940.2U patent/CN209024654U/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110983378A (en) * | 2019-11-15 | 2020-04-10 | 北京理工大学 | Device and method for preparing metal aluminum and titanium tetrachloride in molten salt by soluble anode |
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