CN107587168A - The method that molten-salt electrolysis prepares Titanium - Google Patents
The method that molten-salt electrolysis prepares Titanium Download PDFInfo
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- CN107587168A CN107587168A CN201711050796.1A CN201711050796A CN107587168A CN 107587168 A CN107587168 A CN 107587168A CN 201711050796 A CN201711050796 A CN 201711050796A CN 107587168 A CN107587168 A CN 107587168A
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Abstract
The invention belongs to metallurgical technology field, method that more particularly to a kind of molten-salt electrolysis prepares Titanium.Cost is high when preparing Titanium for existing method, flow is complicated, is unable to the technical problem of continuous production, and the present invention provides a kind of method that molten-salt electrolysis prepares Titanium, comprised the following steps：A, titania powder is dried, after adding binding agent mixing, pours into compressing in mould, drying and processing again, sintered body is made after sintering；B, using above-mentioned sintered body and metal molybdenum filament as negative electrode, using graphite as anode, with NaF and AlF3Mixture melt be electrolyte, under 900~960 DEG C, 2.8~3.0V voltages be electrolysed 2~10h, obtain metallic titanium powder.The present invention is by selecting NaF and AlF3Mixture melt as electrolyte, production cost is reduced, compared to conventional CaCl2Fused salt, also have and be not easy the moisture absorption, be electrolysed the advantages that speed is fast, and product is not easy to pollute, electrolytic efficiency of the present invention is high, effectively reduces production cost.
Description
Technical field
The invention belongs to metallurgical technology field, method that more particularly to a kind of molten-salt electrolysis prepares Titanium.
Background technology
Titanium has a series of properties, such as low-density, high specific strength, wider work as a kind of silvery white non-ferrous metal
The excellent properties such as temperature range, good corrosion resistance and biocompatibility, all obtained in many fields and were widely applied.Aviation
Industry is development and application titanium and its earliest field of alloy, and in recent years, titanium alloy is in biomedicine, automobile, stationery sports goods etc.
Civil area has also obtained extensive research and application.
The production method of current titanium mainly uses metallothermic processes, i.e., is aoxidized using metallic reducing agent (R) and metal
The reaction of thing or chloride (MX) prepares metal M.The titanium metallurgical method for having been carried out industrialized production is magnesium reduction process and sodium
Thermal reduction.Sodium thermoreduction method is higher than magnesium reduction process production cost, and using being restricted, now widely used is that magnesium heat is gone back
Former method, it is by titanium-riched material chlorination, refined as TiCl4Steam, then with magnesium metal reduction be biscuit titanium.Magnesium reduction process
Also have production cost high, can bring environmental pollution in production, reduction efficiency is low, it is impossible to the shortcomings of realizing the serialization of production,
Its application is limited, at present, is badly in need of a kind of low cost, short route, environment-friendly Titanium preparation method.
The content of the invention
The technical problem to be solved in the present invention is：Cost is high when existing method prepares Titanium, flow is complicated, can not be continuous
The technical problem of metaplasia production.
The present invention solve technical problem technical scheme be：A kind of method that molten-salt electrolysis prepares Titanium is provided.The party
Method comprises the following steps：
A, cathode material is prepared
Titania powder is dried, after adding binding agent mixing, pours into compressing in mould, drying and processing again,
Sintered body is made after sintering；
B, it is electrolysed
Using the sintered body described in step a and metal molybdenum filament as negative electrode, using graphite as anode, with NaF and AlF3Mixing
Thing melt is electrolyte, and 2~10h is electrolysed under 900~960 DEG C, 2.8~3.0V voltages, obtains metallic titanium powder.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and the titanium dioxide described in step a is anatase titanium dioxide dioxy
Change titanium, purity >=99.0%.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and drying temperature described in step a is 100~200 DEG C,
Drying time is 2~4h.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and binding agent described in step a is polyvinyl alcohol.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and the addition of binding agent described in step a is titanium dioxide
The 6~8% of titanium powder weight.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and compressing pressure described in step a is 3~5Mpa,
The forming shape is column.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and sintering temperature described in step a is 900~1000 DEG C,
Soaking time is 6~8h.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, in the electrolyte described in step b, NaF and AlF3's
Mol ratio is 2.2~3 ︰ 1.
Further, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, in the electrolyte described in step b, is additionally added
Account for NaF and AlF3The CaF of mixture melt weight 5~8%2。
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, is protected when being electrolysed described in step b using inert gas
Shield.
Compared with prior art, beneficial effects of the present invention are：The invention provides a kind of molten-salt electrolysis to prepare Titanium
Method, pass through select special NaF and AlF3Mixture melt as electrolyte, not only reduce production cost, compare
Conventional CaCl2Fused salt, also have and be not easy the moisture absorption, be electrolysed the advantages that speed is fast, and product is not easy to pollute；It is cloudy using the inventive method
Electrode current efficiency can reach 80%, and electrolytic efficiency can reach 25%, compared to existing electrolytic efficiency, it is possible to increase 20% with
On.Therefore, the invention provides a kind of method that simple and effective electrolysis fused salt prepares Titanium, it is left that purity 99% can be obtained
Right biscuit titanium valve, has significant economic benefit.
Embodiment
The invention provides a kind of method that molten-salt electrolysis prepares Titanium, comprise the following steps：
A, cathode material is prepared
Titania powder is dried, after adding binding agent mixing, pours into compressing in mould, drying and processing again,
Sintered body is made after sintering；
B, it is electrolysed
Using the sintered body described in step a and metal molybdenum filament as negative electrode, using graphite as anode, with NaF and AlF3Mixing
Thing melt is electrolyte, and 2~10h is electrolysed under 900~960 DEG C, 2.8~3.0V voltages, obtains metallic titanium powder.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and the titanium dioxide described in step a is anatase titanium dioxide dioxy
Change titanium, purity >=99.0%.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and drying temperature described in step a is 100~200 DEG C,
Drying time is 2~4h.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and binding agent described in step a is polyvinyl alcohol.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and the addition of binding agent described in step a is titanium dioxide
The 6~8% of titanium powder weight.
It is readily volatilized in sintering process from polyvinyl alcohol as binding agent for the characteristic of sintered body of the present invention, no
Sintered body can be polluted.The addition of binding agent of the present invention is the 6~8% of titania powder weight, if binder amount
It is few, then it can not make powder bonding together, sintered body easily ftractures after sintering；If binding agent is excessive, powder can be into the shape of mud
Formula, lead to not be molded.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, and compressing pressure described in step a is 3~5Mpa,
The forming shape is column.The shape of sintered body of the present invention is not limited only to column, can also have it is square, oval etc., when
When being pressed into column, diameter with 10-50mm can, preferably a diameter of 30mm or 50mm, it is furthermore preferred that being compressed toColumn.
Wherein, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, in the electrolyte described in step b, NaF and AlF3's
Mol ratio is 2.2~3 ︰ 1.
Further, above-mentioned molten-salt electrolysis is prepared in the method for Titanium, in the electrolyte described in step b, is additionally added
Account for NaF and AlF3The CaF of mixture melt weight 5~8%2。
The key point of the present invention is the selection of electrolyte, in traditional electrolytic method, typically using CaCl2Fused salt electricity
Solution, but CaCl2The easy moisture absorption, metal solubility height in fused salt cause background current big, and current efficiency is low, and electrolysis speed is slow,
And electrolysate is also easy to be polluted by carbon, easily separates out chlorine.The invention have selected NaF and AlF3Mixing melt
Body is electrolyte, and defines NaF and AlF in electrolyte3Mol ratio be 2.2~3 ︰ 1, when both ratios be equal to 3 when, electrolysis
Plastidome can improve electrolyte performance, especially reduce fusing point in neutrality.In order to reach more preferable effect, the present invention is in acid
Appropriate AlF is added in the NaF of property3So that NaF and AlF3Mol ratio be 2.2~3 ︰ 1, obtain neutrality electrolyte, enhance
Electrolytic efficiency, being capable of more preferable electrolytic preparation Titanium.
The NaF and AIF3 too low reaction rate that can't increase electrolysis of mol ratio, and too low mol ratio can cause
AIF3 a large amount of volatilizations, very big adverse effect are caused to electrolysis process and experimental situation, and also do not meet technological design.Two
Person's mol ratio is too high, improves electrolysis temperature, adds cost, is not suitable for industrialization and carries out.
Using the electrolyte of the present invention, the ion of dissolving is transmitted in the form of fluorine oxygen calcium complex ion and occurred anti-
Answer, the electrolysis speed of electro-deoxidation can be significantly improved, so as to improve electrolytic efficiency.
The present invention needs first to carry out the assembling of electrolytic cell before electrolysis, and specific operating process is as follows：
Opening temperature controller, furnace temperature is risen to l20 DEG C, to remove moisture remaining in system.Anode is suspended on electrolysis
In groove, heated up with electrolyte with stove, anode material is relative with high purity graphite negative electrode, when the electrolyte in graphite crucible melts completely
Afterwards, decline instrument with spiral and anode sample is slowly immersed into fused salt.Anode is joined directly together with stainless steel guide rod, in stainless steel guide rod most
A hole is bored among upper end, is connected with the anode of dc source, stainless steel crucible is connected as negative electrode with the negative pole of power supply.No
Become rusty the built-in graphite crucible of steel crucible, in order to ensure that graphite crucible side wall is non-conductive in electrolytic process, in graphite crucible internal sleeve
Corundum sleeve pipe.In galvanization, the loop of a closure is formed, carries out electrolytic experiment, 900 DEG C of electrolysis temperature, electrolysis time
For 2~8h, in electrolytic process, every the height of half an hour measurement electrolyte solution, the electrolyte of supplement consumption in time, make electrolysis
Matter horizontal plane remains sustained height.
Explanation is further explained to the embodiment of the present invention below in conjunction with embodiment, but not indicated that this
The protection domain of invention is limited in described in embodiment in scope.
TiO described in embodiment2It is ordinary commercial products Deng raw material.
Embodiment 1 prepares Titanium with the inventive method
Pure TiO will be analyzed2It is put into Φ 30cm steel dies after being well mixed with binding agent, is pressurizeed with powder compressing machine
3Mpa is pressed into cylinder, is put into baking oven and dries, to remove moisture remaining in system.By cathode material and carbon anode material
Carry out electrolytic experiment after assembling, voltage stabilization is electrolysed 3 hours, 30min is first vacuumized in electrolytic process, is then led to again in 3.0V
Argon gas, with NaF and AlF3Blend melt be electrolyte, NaF and AlF in electrolyte3Mol ratio be 2.2.Electrolysis temperature controls
At 900 DEG C, voltage is controlled in 3.0V, electrolysis time 2h, after temperature is down to room temperature, takes out product and Ti powder is made, purity is made
95% titanium sponge, electrolytic efficiency 24.5%.
Embodiment 2 prepares Titanium with the inventive method
Pure TiO will be analyzed2It is put into Φ 30cm steel dies after being well mixed with binding agent, is pressurizeed with powder compressing machine
4Mpa is pressed into cylinder, is put into baking oven and dries, to remove moisture remaining in system.By cathode material and carbon anode material
Carry out electrolytic experiment after assembling, voltage stabilization is electrolysed 5 hours, 30min is first vacuumized in electrolytic process, then lead to argon again in 5V
Gas, with NaF and AlF3Blend melt be electrolyte, NaF and AlF in electrolyte3Mol ratio be 3.Electrolysis temperature control exists
960 DEG C, voltage is controlled in 3.0V, electrolysis time 6h, after temperature is down to room temperature, takes out product and Ti powder is made, purity is made
99% titanium sponge, electrolytic efficiency 24.1%.
Embodiment 3 prepares Titanium with the inventive method
Pure TiO will be analyzed2It is put into Φ 30cm steel dies after being well mixed with binding agent, is pressurizeed with powder compressing machine
5Mpa is pressed into cylinder, is put into baking oven and dries, to remove moisture remaining in system.By cathode material and carbon anode material
Carry out electrolytic experiment after assembling, voltage stabilization is electrolysed 8 hours, 30min is first vacuumized in electrolytic process, is then led to again in 3.0V
Argon gas, with NaF and AlF3Blend melt be electrolyte, NaF and AlF in electrolyte3Mol ratio be 2.8.Electrolysis temperature controls
At 960 DEG C, voltage is controlled in 3.5V, electrolysis time 8h, after temperature is down to room temperature, takes out product and Ti powder is made, purity is made
99% or so titanium sponge, electrolytic efficiency 25.3%.
Comparative example 1 does not use the present invention to prepare Titanium
In comparative example 1, except NaF and AlF in electrolyte3Mol ratio for outside 2.0, remaining operation is the same as embodiment 3, electrolysis effect
Rate 23.1%.
Comparative example 2 does not use the present invention to prepare Titanium
In comparative example 2, except NaF and AlF in electrolyte3Mol ratio for outside 3.5, remaining operation is the same as embodiment 3, electrolysis effect
Rate 22.7%.
Comparative example 3 does not use the present invention to prepare Titanium
In comparative example 3, except electrolyte uses CaCl2Outside, remaining operation is the same as embodiment 3, electrolytic efficiency 18.9%.
From embodiment and the experimental result of comparative example, using NaF of the present invention and AlF3It is electrolysed as electrolyte
Method, the titanium sponge of purity 99% or so can be prepared, moreover it is possible to electrolytic efficiency is significantly improved, compared to existing CaCl2
Electrolyte, electrolytic efficiency improve 25% or so, significantly reduce production cost.
Claims (10)
1. the method that molten-salt electrolysis prepares Titanium, it is characterised in that comprise the following steps：
A, cathode material is prepared
Titania powder is dried, after adding binding agent mixing, pours into compressing in mould, dries, made after sintering again
Obtain sintered body；
B, it is electrolysed
Using the sintered body described in step a and metal molybdenum filament as negative electrode, using graphite as anode, with NaF and AlF3Mixture melt
For electrolyte, 2~10h is electrolysed under 900~960 DEG C, 2.8~3.0V voltages, obtains metallic titanium powder.
2. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Two described in step a
Titanium oxide is anatase titanium dioxide, purity >=99.0%.
3. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Dried described in step a
Temperature is 100~200 DEG C, and drying time is 2~4h.
4. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Bonded described in step a
Agent is polyvinyl alcohol.
5. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Bonded described in step a
The addition of agent is the 6~8% of titania powder weight.
6. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Suppressed described in step a
Briquetting pressure is 3~5Mpa.
7. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Sintered described in step a
Temperature is 900~1000 DEG C, and soaking time is 6~8h.
8. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Electricity described in step b
Xie Zhizhong, NaF and AlF3Mol ratio be 2.2~3 ︰ 1.
9. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：Electricity described in step b
Xie Zhizhong, it is also added into accounting for NaF and AlF3The CaF of mixture melt weight 5~8%2。
10. the method that molten-salt electrolysis according to claim 1 prepares Titanium, it is characterised in that：It is electrolysed described in step b
Shi Caiyong inert gas shieldings.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108441893A (en) * | 2018-06-13 | 2018-08-24 | 重庆大学 | A kind of molten-salt electrolysis TiO2The method for preparing Titanium |
| CN115161714A (en) * | 2022-08-01 | 2022-10-11 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metal titanium by molten salt solid-state deoxidation method |
| CN115386917A (en) * | 2022-08-23 | 2022-11-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing porous titanium by using electrolytic titanium cathode precipitate as raw material |
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| CN102061489A (en) * | 2009-11-11 | 2011-05-18 | 北京科技大学 | Improved process for smelting metallic titanium by electro-deoxidation method |
| 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 |
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| 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 |
| CN1958859A (en) * | 2006-11-03 | 2007-05-09 | 西北有色金属研究院 | Method for extracting titanium from electrolyzed molten salt |
| CN101289754A (en) * | 2008-06-04 | 2008-10-22 | 曹大力 | Process for preparing metallic titanium and titanium master alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108441893A (en) * | 2018-06-13 | 2018-08-24 | 重庆大学 | A kind of molten-salt electrolysis TiO2The method for preparing Titanium |
| CN115161714A (en) * | 2022-08-01 | 2022-10-11 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metal titanium by molten salt solid-state deoxidation method |
| CN115386917A (en) * | 2022-08-23 | 2022-11-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing porous titanium by using electrolytic titanium cathode precipitate as raw material |
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Application publication date: 20180116 |