CN1664173A - Process of preparing titanium sponge by fusion electrolysis of titanium dioxide - Google Patents
Process of preparing titanium sponge by fusion electrolysis of titanium dioxide Download PDFInfo
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- CN1664173A CN1664173A CN 200410101829 CN200410101829A CN1664173A CN 1664173 A CN1664173 A CN 1664173A CN 200410101829 CN200410101829 CN 200410101829 CN 200410101829 A CN200410101829 A CN 200410101829A CN 1664173 A CN1664173 A CN 1664173A
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- titanium dioxide
- titanium sponge
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Abstract
The invention relates to a method for preparing the titanium sponge through electrolyzing the titania by fused salt. The titania applied in the cathode is formed by roasting 1-3h in the carbon reducing atmosphere and 1200-1300 Deg.c. The cathode has two forms: one is plate-like titania, which is formed through roasting the shaped titania combined with PVA adhensive in high temperature and carbon reducing atmosphere; the second is titania particles, which is formed through roasting the rectangle mesh cathode made up of non-corrosive steel or metallic titanium netting in high temperature and carbon reducing atmosphere. The electrolyte is the mixing molten salt system of calcii chloridum and lithium chloride, and the anode uses carbite or inert materials. The cathode and anode are arranged vertically, and the electrode surfaces are parallel, and the electrolyser has at least one group of anode-cathode-anode electrode, and it can set many electrodes in one electrolyser. The voltage of the controlling electrolyzer is 2.8-3.2V, the electrolyzing temperature is 850-900 Deg.c. Cleaning the cathode with the dilute hydrochloric acid and drying it, and getting the titanium sponge, which contains oxygen below 600ppm and the current efficiency is between 70-80%.
Description
Technical field
The invention belongs to the nonferrous materials field, particularly a kind of method of preparing titanium sponge by fusion electrolysis of titanium dioxide.
Background technology
The method of generally using in world's titanium sponge industrial production is a Kroll technology, and it is by magnesium reduction TiCl
4The preparation titanium sponge.This technology has not had too big change always since setting up.This technology is made up of three parts: the one, produce thick TiCl by titaniferous ore
4The 2nd, thick TiCl
4Refining; The 3rd, magnesium reduction TiCl
4Produce titanium sponge and vacuum distilling.Kroll technology is discrete, must feed to reaction in process of production, heat and discharging operation, not only energy consumption height but also cycle long, the production cost height, environmental pollution is serious.Although it is possible that Kroll technology is carried out some improvement, facts have proved that some small technical renovation can not change expensive this present situation.Therefore, the new production technique of titanium sponge cheaply of exploitation is the target that the titanium industry member is pursued to substitute Kroll technology.Direct electrolysis TiO from fused salt
2The preparation titanium sponge, its technical process is short, simple fast, cost is low, saved the chlorination in the traditional technology, make with extra care TiCl
4, complicated procedures of forming such as magnesium reduction and vacuum distilling, can reduce the cost of titanium sponge greatly.Particularly not having emitting of chlorine, avoided the generation of polluting, is a kind of novel pollution-free green metallurgical technology.Application number is that 99808568.5 patents have proposed " fused salt electrolysis of oxygen is removed in metal oxide and the sosoloid " method, has wherein mentioned and has used TiO
2Do negative electrode, direct electrolysis TiO in fused salt
2The preparation titanium sponge.Because titanium dioxide is insulating material, and is non-conductive, directly uses TiO
2Current efficiency is low, generally about 15--25%, is difficult in industrial application.
Summary of the invention
The objective of the invention is at present fused salt electrolysis TiO
2Prepare the low shortcoming of titanium sponge current efficiency, propose a kind of method of preparing titanium sponge by fusion electrolysis of titanium dioxide, this method has high current efficiency.
A kind of preparing titanium sponge by fusion electrolysis of titanium dioxide method is characterized in that titanium dioxide that this method negative electrode adopts forms at roasting 1--3h under the carbon reduction atmosphere and in 1200--1300 ℃ of scope.Negative electrode titanium dioxide is divided into tabular and two kinds of forms of particulate state, if tabular, it is tabular for the 1--2%PVA binding agent is pressed into to add weight per-cent by titanium dioxide in the making, at roasting 2--3h under the carbon reduction atmosphere and in 1200--1300 ℃ of scope; If granular, then be earlier titanium dioxide powder to be added the pelletizing that water is made diameter 1-10mm, at roasting 1--2h under the carbon reduction atmosphere and in 1200--1300 ℃ of scope; Titanium dioxide granule after the roasting packed into make in the rectangle mesh cathode mesh 100--200 order by stainless steel or ti-alloy mesh.
The ionogen that uses is calcium chloride and lithium chloride fused salt mixt system, and wherein the lithium chloride weight percent content is 5-20%.Anode uses graphite or inert material, and when with the inert material anode, electrolytic process is emitted O
2Control flume voltage is at 2.8--3.2V; Electrolysis temperature in 850--900 ℃ of scope, electrolysis time 4--5h.Electric tank cathode and anode are arranged verticals, and electrode surface is parallel to each other, and are provided with one group of electrode that--the moon--positive mode is arranged with sun in the cell body at least, also multi-group electrode can be installed with this mode in same groove, i.e. sun--the moon--sun--the moon--sun.After electrolysis is finished, take out negative electrode, use the dilute hydrochloric acid cleaning, drying, what obtain is exactly titanium sponge.The titanium sponge that makes with this method contains oxygen and is lower than 600ppm, and current efficiency is at 70--80%.Compare with traditional Kroll technology, the electrolysis production cost reduces by 40%, and the current efficiency height has been realized cleaner production.
The characteristics of the inventive method:
Because titanium dioxide is insulating material, therefore, under carbon reduction atmosphere and high-temperature roasting, make the titania molecule deoxidation become semi-conductor, improve electrochemical deoxidising efficient in the electrolytic process; Negative electrode titanium dioxide adopts granular texture, and further fast reaction speed improves deoxidation efficient.In calcium chloride electrolyte, add lithium chloride, can improve electrolytical electric conductivity.The electrode vertical parallel is arranged, and pole span is little, accelerates deoxidation speed, and favourable current efficiency improves.
Embodiment
Embodiment one, and negative electrode is made by the titanium dioxide sintered plate, and it is added by titanium dioxide, and weight per-cent is tabular for the 2%PVA binding agent is pressed into to form under carbon reduction atmosphere and at 1250 ℃ of roasting 2h; Anode is made by inert material; Use calcium chloride and lithium chloride mixed electrolyte in the electrolytic process, wherein the lithium chloride weight percent content is 5%, and electrolysis temperature is at 850 ℃.In electrolysis, bath voltage is controlled at 2.9V, the oxonium ion of on negative electrode, overflowing, and oxonium ion moves towards anode direction under electric field action.Discharge generates oxygen on anode, electrolysis 4h, and negative electrode oxygen level 600ppm becomes titanium sponge.Negative electrode and anodic arranged vertical have increased the electrolysis area, have improved single groove productivity, and current efficiency is 70%.
Embodiment two, and electric tank cathode is made by the titanium net, interior dress titanium dioxide granule, and mesh 150 orders, interior dress titanium dioxide granule, diameter 2mm, titanium dioxide granule add water polo group by titanium dioxide powder and form, under carbon reduction atmosphere and at 1200 ℃ of roasting 1h; Anode is made by graphite; Use calcium chloride and lithium chloride mixed electrolyte in the electrolytic process, wherein the lithium chloride weight percent content is 15%, and electrolysis temperature is at 870 ℃.In electrolysis, bath voltage is controlled at 3.0V, and working process is with embodiment one, and just escaping gas is a carbonic acid gas on anode, and negative electrode oxygen level 500ppm becomes titanium sponge.Open the titanium net, take out titanium sponge, current efficiency is 80%.
Embodiment three, and electric tank cathode is made by stainless (steel) wire, interior dress titanium dioxide granule, and mesh 200 orders, interior dress titanium dioxide granule, diameter 5mm, titanium dioxide granule add water polo group by titanium dioxide powder and form, under carbon reduction atmosphere and at 1300 ℃ of roasting 2h; Anode is made by graphite; Use calcium chloride and lithium chloride mixed electrolyte in the electrolytic process, wherein the lithium chloride degree is 20%, and electrolysis temperature is at 900 ℃.In electrolysis, bath voltage is controlled at 2.8V, and working process is with embodiment one, and just escaping gas is a carbonic acid gas on anode, and negative electrode oxygen level 500ppm becomes titanium sponge.Open stainless (steel) wire, take out titanium sponge, current efficiency is 80%.
Embodiment four, and electric tank cathode is made by the titanium net, interior dress titanium dioxide granule, and mesh 100 orders, interior dress titanium dioxide granule, diameter 7mm, titanium dioxide granule add water polo group by titanium dioxide powder and form, under carbon reduction atmosphere and at 1200 ℃ of roasting 2h; Anode is made by inert material, uses calcium chloride and lithium chloride mixed electrolyte in the electrolytic process, and wherein the lithium chloride weight percent content is 15%, 870 ℃ of electrolysis temperatures.In electrolysis, bath voltage is controlled at 2.8V, and working process is with embodiment one, and escaping gas is an oxygen on anode, and negative electrode 3 oxygen level 400ppm become titanium sponge.Open the titanium net, take out titanium sponge, current efficiency is 75%.
Embodiment five, and electric tank cathode is made by the titanium dioxide sintered plate, and it is added by titanium dioxide, and weight per-cent is tabular for the 1%PVA binding agent is pressed into to form under carbon reduction atmosphere and at 1200 ℃ of roasting 3h; Anode is made by graphite; Use calcium chloride electrolyte in the electrolytic process, wherein the lithium chloride weight percent content is 10%, 870 ℃ of electrolysis temperatures.In electrolysis, bath voltage is controlled at 3.1V, and working process is with embodiment one, and just escaping gas is a carbonic acid gas on anode, and negative electrode 3 oxygen level 500ppm become titanium sponge, and current efficiency is 70%.
Claims (7)
1. the method for a preparing titanium sponge by fusion electrolysis of titanium dioxide is characterized in that titanium dioxide that this method negative electrode adopts forms at roasting 1-3h under the carbon reduction atmosphere and in 1200--1300 ℃ of scope.
2. preparation titanium sponge method as claimed in claim 1, it is characterized in that the titanium dioxide that negative electrode adopts is tabular, it is tabular for the 1--2%PVA binding agent is pressed into earlier to add weight per-cent by titanium dioxide in the making, forms at roasting 2-3h under the carbon reduction atmosphere and in 1200--1300 ℃ of scope.
3. preparation titanium sponge method as claimed in claim 1 is characterized in that negative electrode titanium dioxide is granular, earlier titanium dioxide powder is added the pelletizing that water is made diameter 1-10mm, at roasting 1-2h under the carbon reduction atmosphere and in 1200--1300 ℃ of scope; Titanium dioxide granule after the roasting packed into make in the rectangle mesh cathode mesh 100--200 order by stainless steel or ti-alloy mesh.
4. as claim 1 or 2 or 3 described preparation titanium sponge methods, it is characterized in that the ionogen that this method is used is calcium chloride and lithium chloride fused salt mixt system, wherein the lithium chloride weight percent content is 5-20%.
5. preparation titanium sponge method as claimed in claim 4 is characterized in that anode electrolytic cell made by graphite or inert material, and when with the inert material anode, electrolytic process is emitted O2.
6. preparation titanium sponge method as claimed in claim 5, it is characterized in that electric tank cathode and anode are arranged verticals, at least be provided with one group of electrode that--the moon--positive mode is arranged with sun in the mutual plain cloth cell body of electrode surface, in same groove, also multi-group electrode can be installed with this mode, i.e. sun--the moon--sun--the moon--sun.
7. preparation titanium sponge method as claimed in claim 6 is characterized in that the electrolytic tank electrolysis temperature is 850--900 ℃, and bath voltage is 2.8--3.2V, and electrolysis time is 4-5h; After electrolysis is finished, take out negative electrode, use the dilute hydrochloric acid cleaning, drying, what obtain is exactly titanium sponge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410101829 CN1664173A (en) | 2004-12-24 | 2004-12-24 | Process of preparing titanium sponge by fusion electrolysis of titanium dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410101829 CN1664173A (en) | 2004-12-24 | 2004-12-24 | Process of preparing titanium sponge by fusion electrolysis of titanium dioxide |
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| CN1664173A true CN1664173A (en) | 2005-09-07 |
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| CN 200410101829 Pending CN1664173A (en) | 2004-12-24 | 2004-12-24 | Process of preparing titanium sponge by fusion electrolysis of titanium dioxide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007092398A3 (en) * | 2006-02-06 | 2008-02-28 | Du Pont | Method for electrolytic production of titanium and other metal powders |
| CN100532653C (en) * | 2006-11-03 | 2009-08-26 | 西北有色金属研究院 | Method for extracting titanium from electrolyzed molten salt |
| CN1837411B (en) * | 2006-02-17 | 2010-09-08 | 武汉大学 | Method for preparing refractory active metal or alloy |
| CN102719857A (en) * | 2012-07-03 | 2012-10-10 | 北京科技大学 | Method and electrolytic tank for producing metal titanium through directive electrolysis of titanium dioxide |
| CN103334125A (en) * | 2013-06-14 | 2013-10-02 | 中国船舶重工集团公司第七二五研究所 | Method for preparing sponge titanium on special resistance furnace by molten salt electrolysis 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 |
-
2004
- 2004-12-24 CN CN 200410101829 patent/CN1664173A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007092398A3 (en) * | 2006-02-06 | 2008-02-28 | Du Pont | Method for electrolytic production of titanium and other metal powders |
| CN1837411B (en) * | 2006-02-17 | 2010-09-08 | 武汉大学 | Method for preparing refractory active metal or alloy |
| CN100532653C (en) * | 2006-11-03 | 2009-08-26 | 西北有色金属研究院 | Method for extracting titanium from electrolyzed molten salt |
| CN102719857A (en) * | 2012-07-03 | 2012-10-10 | 北京科技大学 | Method and electrolytic tank for producing metal titanium through directive electrolysis of titanium dioxide |
| CN102719857B (en) * | 2012-07-03 | 2014-08-13 | 北京科技大学 | Method and electrolytic tank for producing metal titanium through directive electrolysis of titanium dioxide |
| CN103334125A (en) * | 2013-06-14 | 2013-10-02 | 中国船舶重工集团公司第七二五研究所 | Method for preparing sponge titanium on special resistance furnace by molten salt electrolysis method |
| CN103334125B (en) * | 2013-06-14 | 2015-08-12 | 中国船舶重工集团公司第七二五研究所 | A kind of fused salt electrolysis process that adopts on special resistors stove prepares the method for titanium sponge |
| 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 |
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