CN1958859A - Method for extracting titanium from electrolyzed molten salt - Google Patents
Method for extracting titanium from electrolyzed molten salt Download PDFInfo
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- CN1958859A CN1958859A CN 200610137990 CN200610137990A CN1958859A CN 1958859 A CN1958859 A CN 1958859A CN 200610137990 CN200610137990 CN 200610137990 CN 200610137990 A CN200610137990 A CN 200610137990A CN 1958859 A CN1958859 A CN 1958859A
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Abstract
This invention relates to a method for producing Ti by molten salt electrolysis. The method utilizes TiO2 electrode added with CaCO3 or CaO and Ti powder as the cathode for molten salt electrolysis. The method can increase the electrolysis efficiency by more than 20%.
Description
Technical field
The method of titanium is produced in a kind of fused salt electrolysis, relates to a kind of method of method, particularly extracting titanium from electrolyzed molten salt of fused salt electrolysis metallurgical production metal.
Background technology
Titanium belongs to important Rare Metals Materials, and since 1948 realized suitability for industrialized production, tempo was very fast.Titanium is little because of its proportion, specific tenacity is high, heat-resisting, no magnetic, numerous advantages such as can weld, be widely used at civil areas such as military fields such as Aeronautics and Astronautics, naval vessel, electronics, weapons and oil, chemical industry, metallurgy, medical treatment, titanium or titanium alloy has become a kind of important rare metal structured material of the development of the national economy.The commercial production of metals titanium mainly adopts metal chloride slag or metal oxide to obtain the tetravalent metal muriate at present, adopts magnesium reduction process or sodium thermoreduction legal system to be equipped with metal then, also claims Kroll method.This processing method exists complex process, cost height, energy consumption is big and contaminate environment, has caused the price of titanium or titanium alloy higher simultaneously, has limited its Application Areas.、
For seeking the production technique of new low cost titanium, all done number of research projects both at home and abroad, the novel process of research has methods such as fused salt electrolysis process, plasma method, metal hydride reduction method, gas phase reduction process.Wherein people are imagining employing electrolytic process production metal titanium always, the electrolysis process of research has two kinds at present, a kind of is electrolytic reduction titanium in the titanium tetrachloride fused salt, mainly is to adopt dissolving titanium in fused salt (as sodium-chlor), generates titanium metal at the cathodic reduction titanium ion.Another kind method is that univ cambridge uk's Materials science in 1997 and metallurgy are that D.J.Fray leader's materials chemistry research group at first proposes, be that the direct reducing metal oxide of electric method of deoxidation prepares metal titanium (being called as the FFC method) in the employing fused salt, but up to the present all do not realize suitability for industrialized production.The specific embodiment of FFC method is after titania powder is mixed with binding agent, to be pressed into electrolytic negative plate, graphite is done anode, fused calcium chloride is as ionogen, and logical an amount of electric current is during electrolysis, titanium dioxide disassociation on the negative electrode, oxygen is emitted oxygen from the migration of negative electrode anode on anode, metal titanium is stayed on the negative plate, be stable solid, can be not oxidized.The working temperature of electrolyzer is at 800-1000 ℃, and operating voltage is 2.8-3.2V.Wherein to face maximum problem be that current efficiency is low to FFC, and this is owing to relate to the diffusion of ionic in solid during electrolysis, so the conductivity of ionic velocity of diffusion and electrode has limited the raising of electrolytic reaction speed and electrolytic efficiency.
Summary of the invention
The objective of the invention is the deficiency that exists at above-mentioned prior art, improves a kind of method of extracting titanium from electrolyzed molten salt of the current efficiency problem that can effectively solve the electrolytic process existence.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method of extracting titanium from electrolyzed molten salt is characterized in that its electrolytic process is to adopt to have added CaCO
3Or the TiO of CaO and Ti powder
2Electrode carries out fused salt electrolysis as negative electrode.
The method of a kind of extracting titanium from electrolyzed molten salt of the present invention is characterized in that it has added CaCO
3TiO with the Ti powder
2The weight percent of electrode consists of: CaCO
3Be 5%-15%; The Ti powder is 0%-10%, and surplus is TiO
2And unavoidable impurities.
The method of a kind of extracting titanium from electrolyzed molten salt of the present invention is characterized in that it has added the TiO of CaO and Ti powder
2The weight percent of electrode consists of: the content of CaO is 5%-15%; The Ti powder is 0%-10%, and surplus is TiO
2And unavoidable impurities.
The method of a kind of extracting titanium from electrolyzed molten salt of the present invention is characterized in that its TiO
2The preparation of electrode is to adopt TiO
2, CaCO
3Or CaO, Ti powder be raw material, and powder size is below 50 μ m, and behind mixing, compression moulding is prepared into electrode under the pressure of 100-200MPa; Under 600--1000 ℃ of vacuum or inert gas conditions sintering 1-2 hour.
The method of a kind of extracting titanium from electrolyzed molten salt of the present invention is characterized in that its electrolytic process is the TiO that will be suspended on the contact conductor
2Negative electrode inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield, temperature is 900-950 ℃, electrolysis voltage be carry out under the 3-3.2V condition electrolytic.
Method of the present invention adopts and added CaCO in preparation
3TiO with the Ti powder
2Powder, the electrode that sintering forms under repressed moulding, vacuum or the inert gas conditions are as negative electrode, and the deoxidation of switching in fused salt at last obtains metal titanium.
CaCO in the electrode
3Generation CO can take place to decompose in the time of 900 ℃
2Gas and CaO.And CaO is at 900 ℃ CaCl
2In very high solubleness is arranged is 19.4%mol, CaO is at CaCl
2In be dissolved with the infiltration that is beneficial to fused salt, increase the area of electrode reaction, improve electrolytic efficiency.Calculate as can be known under 900 ℃ according to thermodynamic data in addition, CaO is decomposed into Ca and O
2Theoretical decomposition voltage be 2.7V, so CaO also can resolve into Ca and O under the electrolytic condition of 3V
2
At TiO
2Add appropriate C aCO in the electrode preparation
3, CaCO when sintering and electrolysis
3Decomposition can increase hole on the cathode sheets.
At TiO
2Add a small amount of Ti powder in the electrode preparation, and under vacuum or argon gas sintering, cathodic conductivity is increased, reduce electrolytic energy consumption, improve electrolytic efficiency.Experiment shows, adopts method of the present invention, and electrolytic efficiency can improve more than 20%.
Embodiment
A kind of method of extracting titanium from electrolyzed molten salt, its electrolytic process are to adopt to have added CaCO
3Or the TiO of CaO and Ti powder
2Electrode carries out fused salt electrolysis as negative electrode.The weight percent of its electrode consists of: CaCO
3For the content of 5%-15% or CaO is 5%-15%; The Ti powder is 0%-10%, and surplus is TiO
2And unavoidable impurities.Its TiO
2The preparation of electrode is to adopt TiO
2, CaCO
3, the Ti powder is raw material, powder size is below 50 μ m, behind mixing, compression moulding is prepared into electrode under the pressure of 100-200MPa; Under 600--1000 ℃ of vacuum or inert gas conditions sintering 1-2 hour.Electrolytic process is the TiO that will be suspended on the contact conductor
2Negative electrode inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield, temperature is 900-950 ℃, electrolysis voltage be carry out under the 3-3.2V condition electrolytic.
Embodiment 1
Adopt 95%TiO
2, 5%CaCO
3Powder is a raw material, and powder size is below 50 μ m, and behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 20.6%.
Embodiment 2
Adopt 85%TiO
2, 15%CaCO
3Powder is a raw material, and powder size is below 50 μ m, and behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 25.9%.
Embodiment 3
Adopt 90%TiO
2, 5%CaCO
3, the 5%Ti powder is raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 21%.
Embodiment 4
Adopt 80%TiO
2, 15%CaCO
3, the 5%Ti powder is raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 27%.
Embodiment 5
Adopt 85%TiO
2, 5%CaCO
3, the 10%Ti powder is raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 24%.
Embodiment 6
Adopt 75%TiO
2, 15%CaCO
3, the 10%Ti powder is raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 33%.
Embodiment 7
Adopt 75%TiO
2, 15%CaO, 10%Ti powder be raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 30%.
Embodiment 8
Adopt 85%TiO
2, the 15%CaO powder is raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 23.3%.
Embodiment 9
Adopt 95%TiO
2, the 5%CaO powder is raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 20.4%.
Embodiment 10
Adopt 85%TiO
2, 5%CaO, 10%Ti powder be raw material, powder size is below 50 μ m, behind mixing, compression moulding under the pressure of 100MPa prepares sample through 900 ℃ of sintering again.With fused salt CaCl
2Be ionogen, the TiO behind the sintering
2Sheet is a negative electrode, and graphite rod is an anode.To be suspended on the TiO on the contact conductor during experiment
2Sintered sample inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield is when electrolysis temperature is 900 ℃.Electrolysis voltage is 3-3.2V, and electrolysis time is 4h.Electrolytic efficiency has improved 23%.
Claims (5)
1. the method for an extracting titanium from electrolyzed molten salt is characterized in that its electrolytic process is to adopt to have added CaCO
3Or the TiO of CaO and Ti powder
2Electrode carries out fused salt electrolysis as negative electrode.
2. the method for a kind of extracting titanium from electrolyzed molten salt according to claim 1 is characterized in that it has added CaCO
3TiO with the Ti powder
2The weight percent of electrode consists of: CaCO
3Be 5%-15%; The Ti powder is 0%-10%, and surplus is TiO
2And unavoidable impurities.
3. the method for a kind of extracting titanium from electrolyzed molten salt according to claim 1 is characterized in that it has added the TiO of CaO and Ti powder
2The weight percent of electrode consists of: the content of CaO is 5%-15%; The Ti powder is 0%-10%, and surplus is TiO
2And unavoidable impurities.
4. the method for a kind of extracting titanium from electrolyzed molten salt according to claim 1 is characterized in that its TiO
2The preparation of electrode is to adopt TiO
2, CaCO
3Or CaO, Ti powder be raw material, and powder size is below 50 μ m, and behind mixing, compression moulding is prepared into electrode under the pressure of 100-200MPa; Under 600--1000 ℃ of vacuum or inert gas conditions sintering 1-2 hour.
5. the method for a kind of extracting titanium from electrolyzed molten salt according to claim 1 is characterized in that its electrolytic process is the TiO that will be suspended on the contact conductor
2Negative electrode inserts fused salt CaCl is housed
2Plumbago crucible in, electrolysis under argon shield, temperature is 900-950 ℃, electrolysis voltage be carry out under the 3-3.2V condition electrolytic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101379909A CN100532653C (en) | 2006-11-03 | 2006-11-03 | Method for extracting titanium from electrolyzed molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101379909A CN100532653C (en) | 2006-11-03 | 2006-11-03 | Method for extracting titanium from electrolyzed molten salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1958859A true CN1958859A (en) | 2007-05-09 |
| CN100532653C CN100532653C (en) | 2009-08-26 |
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|---|---|---|---|
| CNB2006101379909A Expired - Fee Related CN100532653C (en) | 2006-11-03 | 2006-11-03 | Method for extracting titanium from electrolyzed molten salt |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545111B (en) * | 2008-03-26 | 2011-01-26 | 比亚迪股份有限公司 | Method for preparing simple substance of silicon |
| CN102409363A (en) * | 2011-11-24 | 2012-04-11 | 中国船舶重工集团公司第七二五研究所 | Method for preparing titanium with fused salt electrolysis process |
| CN102925929A (en) * | 2012-10-25 | 2013-02-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing metal titanium by molten salt electrolysis |
| CN105463515A (en) * | 2015-12-25 | 2016-04-06 | 东北大学 | Method for preparing V-4Cr-4Ti alloy through fused salt electro-deoxidation method |
| CN107587168A (en) * | 2017-10-31 | 2018-01-16 | 成都先进金属材料产业技术研究院有限公司 | The method that molten-salt electrolysis prepares Titanium |
| CN115142096A (en) * | 2021-03-30 | 2022-10-04 | 中国科学院过程工程研究所 | Method for improving electrolysis efficiency of refractory metal prepared by molten salt electrolysis and purifying molten salt |
| CN115821332A (en) * | 2022-11-28 | 2023-03-21 | 西北有色金属研究院 | Titanium current collector for proton exchange membrane electrolyzed water hydrogen production device and preparation method thereof |
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| KR20110025237A (en) * | 2002-03-13 | 2011-03-09 | 비에이치피 빌리튼 이노베이션 피티와이 리미티드 | Reduction of metal oxides in an elecrolytic cell |
| JP4198439B2 (en) * | 2002-10-25 | 2008-12-17 | 日本軽金属株式会社 | Consumable carbon anode for smelting titanium metal |
| CN1664173A (en) * | 2004-12-24 | 2005-09-07 | 北京科技大学 | Process of preparing titanium sponge by fusion electrolysis of titanium dioxide |
| CN1803938B (en) * | 2005-01-10 | 2011-06-29 | 北京化工大学 | TiO2/CaCO3 nano composite particle, hollow TiO2 nano material and method for preparing the same |
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2006
- 2006-11-03 CN CNB2006101379909A patent/CN100532653C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545111B (en) * | 2008-03-26 | 2011-01-26 | 比亚迪股份有限公司 | Method for preparing simple substance of silicon |
| CN102409363A (en) * | 2011-11-24 | 2012-04-11 | 中国船舶重工集团公司第七二五研究所 | Method for preparing titanium with fused salt electrolysis process |
| CN102925929A (en) * | 2012-10-25 | 2013-02-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing metal titanium by molten salt electrolysis |
| CN102925929B (en) * | 2012-10-25 | 2015-04-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing metal titanium by molten salt electrolysis |
| CN105463515A (en) * | 2015-12-25 | 2016-04-06 | 东北大学 | Method for preparing V-4Cr-4Ti alloy through fused salt electro-deoxidation method |
| CN107587168A (en) * | 2017-10-31 | 2018-01-16 | 成都先进金属材料产业技术研究院有限公司 | The method that molten-salt electrolysis prepares Titanium |
| CN115142096A (en) * | 2021-03-30 | 2022-10-04 | 中国科学院过程工程研究所 | Method for improving electrolysis efficiency of refractory metal prepared by molten salt electrolysis and purifying molten salt |
| CN115821332A (en) * | 2022-11-28 | 2023-03-21 | 西北有色金属研究院 | Titanium current collector for proton exchange membrane electrolyzed water hydrogen production device and preparation method thereof |
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|---|---|
| CN100532653C (en) | 2009-08-26 |
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