CN102719857B - Method and electrolytic tank for producing metal titanium through directive electrolysis of titanium dioxide - Google Patents
Method and electrolytic tank for producing metal titanium through directive electrolysis of titanium dioxide Download PDFInfo
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Abstract
The invention belongs to the non-ferrous metallurgy field and discloses a method and an electrolytic tank for producing metal titanium through directive electrolysis of titanium dioxide. According to the method, titanium dioxide powder serves as a raw material, liquid metal sodium serves as a cathode reduction medium, the titanium dioxide powder enters the cathode of the metal sodium continuously for a reduction reaction under a joint action of a spirally feeding mode and argon flow serving as a carrier gas, and an electrolytic product is highly purified sponge titanium powder; and oxygen ions are released during the electrolytic process, enter KC1-NaC1 binary mixed molten salt through a stable zirconia solid oxygen permeable membrane of yttrium oxide under the effect of an electric field, transfer to a graphite anode for an electrochemical reaction, and then are discharged. The producing process is capable of producing the metal titanium through direct and rapid reduction of the titanium dioxide powder and producing continuously, high in current efficiency and deoxidation efficiency, strong in regeneration capacity of a reducing agent, simple and suitable for industrial applications.
Description
Technical field
The invention belongs to Non-ferrous Metallurgy field, relate in particular to a kind of novel fused salt electrolysis technology taking titanium dioxide as the processing method of raw material direct Preparation of Titanium simple substance and involved electrolyzer.
Background technology
The method generally using in world's titanium sponge industrial production is Kroll (Kroll) technique.Kroll method mainly adopts metal M g reduction TiCl
4operation, vacuum separation operation are manufactured metal titanium.This technique is made up of three parts: the one, produce smart TiCl by titaniferous ore matter
4; The 2nd, magnesium reduction TiCl
4produce the reduction operation of titanium sponge; The 3rd, the regeneration of vacuum distilling, purification and magnesium.In reduction operation, liquid TiCl
4add from reactor top and the melting Mg that flows through reduces, deposit and obtain sponge Ti at reactor bottom; Vacuum separation operation is mainly to remove the Mg simple substance and the reduzate MgCl that are wherein mingled with
2.This technique can make highly purified metal titanium, but this technique due to thermal reduction process length, complex procedures, the reason such as can not produce continuously and make titanium production cost high, the environmental pollution in production process in addition, has restricted the widespread use of titanium greatly.Improve although a lot of researchists attempt that Kroll technique is carried out to some, the improvement of some technical elements of presentation of results can not change the expensive defect of this method.Therefore, adopting novel titanium extractive technique to replace Kroll traditional technology is an important developing direction of titanium industry.
At present, exploitation around Novel Titanium smelting technology has become worldwide study hotspot, the new technology of or having developed reaches hundreds of, wherein representative technique mainly contains electrolysis of chloride method, mechanical alloying method, low temperature metal hydrides reduction method, gas phase reduction process, Ono and Suzuki have proposed calciothermic reduction technique (OS), premolding reducing process (PRP), electrical conductor is got involved reduction method (EMR), composite anode technique (MER), titanium slag direct-reduction technique (QIT), fluidized-bed direct-reduction technique (SRI), University of Science & Technology, Beijing's technique (USTB method) and Cambridge fused salt electrolysis process (FFC) etc.Wherein most of technique still need be with TiCl
4or titanium suboxide etc. is as reduction raw material, therefore in work simplification, does not have advantage.FFC electro-deoxiedation directly adopts TiO
2as raw material, its operational path is relatively simple, but FFC exists that side reaction ratio is bigger than normal, current efficiency is low and electrolysis speed is crossed the defects such as slow, is difficult to realize scale operation, and it need to be to TiO simultaneously
2raw material carries out premolding and sintering process, thereby has increased process complexity and process energy consumption.OS method utilizes the reductive agent Ca of electrolytic process generation directly to TiO
2powder reduces, but the equal Shortcomings of the regenerative power of electrolytic process Ca and utilization ratio aspect, electrolytic process is slow and current efficiency is low, and the oxygen level of electrolysate is difficult to reduce.
So, realize titanium novel process for smelting exploitation cheaply, its most economical raw material is TiO
2thereby, to realize adding continuously with the continuous derivation of product of raw material simultaneously and realize serialization production.The mode of production is to adopt conventional electrolysis production in nonferrous metallurgy to be advisable, to adapt to green metallurgical demand for development.
The reason that FFC method current efficiency is low is mainly coming from wherein serious side reaction.The Ca simple substance producing in cathodic area in electrolytic process has strong reducing property, and it can promote the titanium reduction process in cathodic area, but its also can due to fused salt flow and diffusive migration to positive column and with anodic product CO/CO
2react, produce a large amount of carbon simple substance and sneak into molten salt system and be enriched in fused salt surface.Meanwhile, the oxygen that anode removes is introduced in again in fused salt and circulation participates in the discharge process on anode, causes the waste of electric power.It is mainly the restriction due to deoxidation link that FFC method electrolysis speed is crossed slowly: oxygen removal process will be passed through migration and four steps of anodic reaction in liberalization, negative electrode migration of solid phases, ion fused salt, its restriction due to oxide cathode cause oxygen ionized process and migration of solid phases process slow, and then delay overall electrolytic process.OS method reduction interface is TiO
2particle and fused salt contact interface, it has some superiority aspect kinetics, but the regenerative power of its reductive agent Ca is not enough to support long-time, successional reduction process.
Summary of the invention
The object of the invention is to, improve a kind of method and electrolyzer thereof of novel Direct Electrolysis titanium dioxide production metal titanium, this production technique can be directly reduced TiO 2 powder preparation metal titanium fast, process current efficiency is high, deoxidation rate is high, regenerative power reductive agent is strong, technique is simple, can produce continuously, is suitable for industrial application.
The electrolyzer of a kind of Direct Electrolysis titanium dioxide production of the present invention metal titanium, electrolyzer is upper and lower two portions, upper cover comprises anode and cathode interface, thermopair interface, cooling water system, adjustable argon gas import and outlet, and TiO2 powder feeding screw is connected with argon gas import; Bottom adopts well formula stainless steel electrolytic groove, electrolyzer using high purity graphite crucible as fused salt, between plumbago crucible and stainless steel trough body, carry out insulation processing with high temperature material, wherein said electrolyzer comprises a liquid metal sodium cathode, the zirconia solid oxygen permeable film pipe of stabilized with yttrium oxide that comprises sodium Metal 99.5, an end closure as negative electrode outer wall, high-purity filamentary silver as cathode wire, liquid metal sodium cathode is positioned in electrolysis fused salt, is provided with inlet mouth and the air outlet of argon gas above the liquid level of its sodium Metal 99.5 solution; High purity graphite crucible or graphite rod are as anode; In fused salt, be provided with ferrum-chromium-aluminum preelectrolysis negative electrode and thermopair.
Preferred version of the present invention, zirconia solid oxygen permeable film (YSZ) the pipe inside and outside wall of described stabilized with yttrium oxide sprays titanium processing through high temperature, thereby has increased the erosion resistance of YSZ film, has ensured stability in use and the work-ing life of electrolyzer; The bottom of described electrolyzer and negative electrode outer wall is provided with continuous discharging device, and this scheme has realized serialization production prepared by metal titanium, has improved output, is applicable to produce in enormous quantities; The degree of depth of described stainless steel electrolytic groove is 600mm, and diameter is 300mm; The internal diameter of described negative electrode outer wall is that 150mm, thickness are 3mm, also can according to produce actual needs all the size of electrolyzer make corresponding amendment; Negative electrode top has sealed interface, opening for feed and argon gas gangway, can realize TiO
2adding continuously and the inner inert protective atmosphere of sodium Metal 99.5 negative electrode of powder.Adopt high-purity filamentary silver as cathode wire by external stabilized power and liquid metal sodium UNICOM.
The method of a kind of Direct Electrolysis titanium dioxide production of the present invention metal titanium, taking titanium dioxide powder as raw material, using liquid metal sodium as cathodic reduction medium, titanium dioxide powder enters continuously sodium Metal 99.5 negative electrode under using spiral charging and argon gas stream as the mode of application of carrier gas and carries out reduction reaction, and electrolysate is highly purified spongy titanium powder; The process of electrolysis discharges oxonium ion, enters KCl-NaCl binary fused salt mixt and migrate to graphite anode generation electrochemical reaction to discharge under electric field action by the zirconia solid oxygen permeable film of stabilized with yttrium oxide.
The preferred version of present method, the process of described sodium Metal 99.5 reduction titanium dioxide is to carry out under the effect of applying electrical potential.Sodium Metal 99.5 can not be directly reduces TiO by chemical process
2, but next for TiO in the effect of certain applying electrical potential
2have very strong reducing power, the na oxide generating after reduction dissolves in sodium Metal 99.5 liquid, thereby makes oxygen be free ion state.Said process can be realized oxygen ionized process fast, makes TiO
2oxygen in raw material more easily carries out oxygen migration under electric field action in sodium Metal 99.5 negative electrode.
The method of a kind of Direct Electrolysis titanium dioxide production of the present invention metal titanium, comprises following following steps:
(1) the KCl-LiCl binary fused salt mixt that KCl mole of proportioning of preparation is 40.8% ~ 47% is as molten salt electrolyte, at 300 DEG C of temperature, carry out 12h processed, and transfer to rapidly in plumbago crucible, in reactor, be warming up to rapidly and at 450 DEG C, carry out melting treatment, heating-up time is less than 30 minutes, taking preelectrolysis electrode as negative electrode, plumbago crucible carries out electrode voltage as 2.0V preelectrolysis process as anode;
(2) in the zirconia solid oxygen permeable film pipe of stabilized with yttrium oxide, incorporate after 600ml/min high-purity argon gas 0.5h, add solid metal sodium, add-on is as the criterion with pipe inner height 1/2, to after upper cover sealing, install high purity silver cathode wire additional and continue to pass into high-purity argon gas, negative electrode is slowly down in fused salt and is made sodium Metal 99.5 fusing form liquid state;
(3) by analytical pure TiO
2powder is in the mode of spiral charging, be added to continuously in sodium Metal 99.5 negative electrode using argon gas as carrier gas, adding speed is 100g/h, carry out constant-potential electrolysis to adding 2.8V ~ 4.0V electrode voltage between cathode wire and positive wire, electrolysis continues to maintain 1.5h～4h after reinforced end;
(4) electrolysis finish after by negative electrode entirety rise on fused salt liquid level, carry out cooling, after being down to room temperature, temperature takes out internal solids, upper metal sodium carries out after physical sepn for subsequent use, and enrichment electrolysate in bottom carries out cryodrying after washing, supersound process, obtains titanium sponge powder.
The method of a kind of Direct Electrolysis titanium dioxide production of the present invention metal titanium, in wherein said step (3), the charging of TiO2 powder can be taked the mode repeatedly in batches entering.
Gordian technique of the present invention is: 1. adopt the sodium Metal 99.5 of low melting point as the reducing medium of electrolytic process, it can reduce TiO
2reduction potential and can with TiO
2form good reaction interface (solid particulate-molten metal interface), under certain cathode electrode potential, realize TiO
2the fast restore of powder, Ti powder after reduction is deposited on sodium Metal 99.5 liquid bottom, thereby oxonium ion is free ion, under electric field action, is discharged and realized reduction process by electric deoxidation by sodium Metal 99.5 liquid, in electrolytic process, can form intermediate sodium oxide components, thereby it can obtain electrolysis and realize the regenerative process of sodium Metal 99.5 under catholyte voltage; 2. adopt the sleeve pipe as sodium Metal 99.5 negative electrode through the YSZ oxonium ion selectivity solid oxygen-ion membrane (som) pipe of titanizing processing, realizing under high electrode voltage, the electrolytic process of long-time continuous, can eliminate the side reaction between anodic product and cathode product simultaneously; 3. adopt KCl-LiCl fused salt mixt (mole proportioning: 40:59.2) as electrolysis molten salt system to realize the production process of (450 DEG C) under cold condition; 4. TiO
2adopt powdery continuous sample introduction mode, be carried into liquid metal sodium cathode inside carry out continuous electrolysis using argon gas stream as carrier gas, argon gas serves as sodium Metal 99.5 galvanic protection gas simultaneously.
The present invention directly adopts TiO
2powder as raw material not only technological process more simplify, be also favourable for realizing reduction process fast.Meanwhile, metallothermic reduction can effectively reduce the reduction potential of metal titanium, more easily realizes higher deoxidation rate compared to electric deoxidation process.Therefore, the invention discloses a kind of taking low melting point metal sodium as reducing medium, with the strong reducing property negative electrode with ion selectivity of YSZ solid oxygen-ion membrane (som) composition to realize fast restore TiO
2process.Said process can be realized oxygen ionized process fast, makes TiO
2oxygen in raw material more easily carries out oxygen migration under electric field action in sodium Metal 99.5 negative electrode.Oxygen transition process adopts electric deoxidation mode, and the YSZ solid oxygen-ion membrane (som) of introducing is owing to having the selection trafficability characteristic of oxonium ion, thereby can effectively avoid, between cathodic reduction product and anodic product, side reaction occurs.Meanwhile, adopt low-temperature molten salt system fused salt ionic channel is provided for oxonium ion removes and realizes the smelting process under lesser temps.
Electrolytic reduction process is taking oxygen migration as principal mode, TiO
2powder discharges oxonium ion realize fast restore process under the strong reducing action of cathodic metal sodium liquid in, and under electric field action, enter fused salt by YSZ oxygen permeable film and migrate to graphite anode generation electrochemical reaction and discharge, deoxidation process have rapidly, continuously change, without features such as side reaction interference.Raw material directly adopts TiO
2powder can reduce production costs and simplify reducing process route, can realize serialization production process.Reduction interface has obvious kinetic advantage, make that reduction process is fast, electrolysing period is short and electrolysate in metal Ti content high.
Brief description of the drawings
Fig. 1 is Direct Electrolysis TiO of the present invention
2powder is prepared the electrolyzer schematic diagram of metal Ti;
1.TiO in figure
2powder feeding screw; 2. be adjustable argon gas admission port; 3. be argon gas export; 4. be cathode wire, using high-purity filamentary silver (99.9999%) as electrical conductor; 5. be fused salt preelectrolysis negative electrode and interface thereof; 6. be K type temperature-control heat couple; 7. be CO/CO
2exhaust port; 8. be positive wire and interface thereof; 9. be stainless steel reactor top recirculated cooling water interface; 10. be molten metals in liquid state sodium; 11. is the fixing zirconium white of yttrium oxide (YSZ) solid oxygen-ion membrane (som) pipe; 12. is reactor lower part and external heating device; 13. melt salt for KCl-LiCl.
Fig. 2 is Direct Electrolysis TiO of the present invention
2powder is prepared the process flow sheet of metal Ti.
Embodiment
As shown in Figure 1, the electrolyzer of a kind of Direct Electrolysis titanium dioxide production of the present invention metal titanium, electrolyzer is upper and lower two portions, and upper cover comprises anode and cathode interface (4,8), thermopair interface (6), cooling water system (9), adjustable argon gas import and outlet (2,3), TiO
2powder feeding screw (1) is connected with argon gas import, can realize TiO
2adding continuously and the inner inert protective atmosphere of sodium Metal 99.5 negative electrode of powder; Bottom adopts well formula stainless steel electrolytic groove, electrolyzer using high purity graphite crucible as fused salt, between plumbago crucible and stainless steel trough body, carry out insulation processing with high temperature material, wherein said electrolyzer comprises a liquid metal sodium cathode, zirconia solid oxygen permeable film pipe by the stabilized with yttrium oxide of sodium Metal 99.5 (10), an end closure forms as cathode wire (4) as negative electrode outer wall (11), high-purity filamentary silver, and wherein sodium Metal 99.5 (10) is as the renewable negative electrode liquid state of high reductibility in the design.Sodium Metal 99.5 negative electrode is positioned in electrolysis fused salt (13), is provided with inlet mouth (2) and air outlet (3) of argon gas, wherein argon gas air outlet band filter screen above the liquid level of its sodium Metal 99.5 solution; High purity graphite crucible or graphite rod are as anode (8); In fused salt, be provided with ferrum-chromium-aluminum preelectrolysis negative electrode (5) and thermopair (6), wherein thermopair (6) is with high-purity Al
2o
3protective tube.Zirconia solid oxygen permeable film (YSZ) the pipe inside and outside wall of described stabilized with yttrium oxide is through the processing of high temperature spray titanium; The bottom of described electrolyzer and negative electrode outer wall is provided with continuous discharging device; The degree of depth of described stainless steel electrolytic groove is 600mm, and diameter is 300mm; The internal diameter of described negative electrode outer wall is that 150mm, thickness are 3mm; Negative electrode top has sealed interface and tail gas outlet (7); And reactor lower part and outside are provided with heating unit (12) and temperature-control heat couple (6) and temperature controller composition electrolysis temperature regulating device.
Embodiment 1
The KCl-LiCl fused salt that is 47.0:53.0 by mole proportioning carries out 12h processed and shifts while hot in plumbago crucible at 300 DEG C, in reactor, be warming up to rapidly and at 450 DEG C, carry out melting (upper cover passes into recirculated cooling water), fused salt severity control is height for reactor 1/2 to 2/3, and intensification melting process required time is no more than 30 minutes.Using the high temperature resistant conductor of ferrum-chromium-aluminum as preelectrolysis negative electrode, plumbago crucible carries out the preelectrolysis process of 2.0V, 0.5h as anode.After passing into 600ml/min high-purity argon gas 0.5h in YSZ pipe, add 300g solid metal sodium, upper cover and YSZ pipe are carried out installing cathode wire additional and continuing to pass into high-purity argon gas after encapsulation process.By negative electrode good aforesaid combination and electrolyzer top cap connects and negative electrode is slowly down to and is made interior metal sodium melt in fused salt to form liquid, according to the structure of Fig. 1, electrolyzer various piece is installed.By 500g analytical pure TiO
2powder is in the mode of spiral charging, be added to continuously in sodium Metal 99.5 negative electrode as carrier gas using argon gas, and adding speed is 100g/h, carries out constant-potential electrolysis to additional 2.8V electrode voltage between cathode wire and positive wire, and electrolysis continues to maintain 4h after reinforced end.After electrolysis finishes, negative electrode entirety is risen to and on fused salt liquid level, carry out coolingly, after temperature is down to room temperature, take out internal solids.Upper metal sodium carries out after physical sepn for subsequent use, and it is dry that enrichment electrolysate in bottom carries out low temperature (60 DEG C) after washing, supersound process.
As main, color is black to product taking Powdered, obtains titanium sponge powder 301g after ultrasonic dispersion, and titanium content is 99.46%, reaches national level Four titanium standard, can directly apply to industrial melted ingot processing.Electrolytic process current efficiency 75.6%.After electrolysis, the sodium Metal 99.5 rate of recovery is 83%, can directly recycle.
Embodiment 2
The KCl-LiCl fused salt that is 40.8:59.2 by a certain amount of mole of proportioning carries out 12h processed and shifts while hot in plumbago crucible at 300 DEG C, in reactor, be warming up to rapidly and at 450 DEG C, carry out melting (upper cover passes into recirculated cooling water), fused salt severity control is height for reactor 1/2 to 2/3, and intensification melting process required time is no more than 30 minutes.Using the high temperature resistant conductor of ferrum-chromium-aluminum as preelectrolysis negative electrode, plumbago crucible carries out the preelectrolysis process of 2.0V, 0.5h as anode.After passing into 600ml/min high-purity argon gas 0.5h in YSZ pipe, add 300g solid metal sodium, upper cover and YSZ pipe are carried out installing cathode wire additional and continuing to pass into high-purity argon gas after encapsulation process.By negative electrode good aforesaid combination and electrolyzer top cap connects and negative electrode is slowly down to and is made interior metal sodium melt in fused salt to form liquid, according to the structure of Fig. 1, electrolyzer various piece is installed.By 500g analytical pure TiO
2powder is in the mode of spiral charging, be added to continuously in sodium Metal 99.5 negative electrode as carrier gas using argon gas, and adding speed is 200g/h, carries out constant-potential electrolysis to additional 3.4V electrode voltage between cathode wire and positive wire, and electrolysis continues to maintain 3h after reinforced end.After electrolysis finishes, negative electrode entirety is risen to and on fused salt liquid level, carry out coolingly, after temperature is down to room temperature, take out internal solids.Upper metal sodium carries out after physical sepn for subsequent use, and it is dry that enrichment electrolysate in bottom carries out low temperature (60 DEG C) after washing, supersound process.
As main, color is black to product taking Powdered, obtains titanium sponge powder 300g after ultrasonic dispersion, and titanium content is 99.86%, reaches national level Four titanium standard, can directly apply to industrial melted ingot processing.Electrolytic process current efficiency 87.7%.After electrolysis, the sodium Metal 99.5 rate of recovery is 87%, can directly recycle.
Embodiment 3
The KCl-LiCl fused salt that is 40.8:59.2 by a certain amount of mole of proportioning carries out 12h processed and shifts while hot in plumbago crucible at 300 DEG C, in reactor, be warming up to rapidly and at 450 DEG C, carry out melting (upper cover passes into recirculated cooling water), fused salt severity control is height for reactor 1/2 to 2/3, and intensification melting process required time is no more than 30 minutes.Using the high temperature resistant conductor of ferrum-chromium-aluminum as preelectrolysis negative electrode, plumbago crucible carries out the preelectrolysis process of 2.0V, 0.5h as anode.After passing into 600ml/min high-purity argon gas 0.5h in YSZ pipe, add 400g solid metal sodium, upper cover and YSZ pipe are carried out installing cathode wire additional and continuing to pass into high-purity argon gas after encapsulation process.By negative electrode good aforesaid combination and electrolyzer top cap connects and negative electrode is slowly down to and is made interior metal sodium melt in fused salt to form liquid, according to the structure of Fig. 1, electrolyzer various piece is installed.By 500g analytical pure TiO
2powder is in the mode of spiral charging, be added to continuously in sodium Metal 99.5 negative electrode as carrier gas using argon gas, and adding speed is 300g/h, carries out constant-potential electrolysis to additional 4.0V electrode voltage between cathode wire and positive wire, and electrolysis continues to maintain 2h after reinforced end.After electrolysis finishes, negative electrode entirety is risen to and on fused salt liquid level, carry out coolingly, after temperature is down to room temperature, take out internal solids.Upper metal sodium carries out after physical sepn for subsequent use, and it is dry that enrichment electrolysate in bottom carries out low temperature (60 DEG C) after washing, supersound process.
As main, color is black to product taking Powdered, obtains titanium sponge powder 298g after ultrasonic dispersion, and titanium content is 99.90%, reaches national level Four titanium standard, can directly apply to industrial melted ingot processing.Electrolytic process current efficiency 90.7%.After electrolysis, the sodium Metal 99.5 rate of recovery is 88%, can directly recycle.
Embodiment 4
The KCl-LiCl fused salt that is 41.0:59.0 by a certain amount of mole of proportioning carries out 12h processed and shifts while hot in plumbago crucible at 300 DEG C, in reactor, be warming up to rapidly and at 450 DEG C, carry out melting (upper cover passes into recirculated cooling water), fused salt severity control is height for reactor 1/2 to 2/3, and intensification melting process required time is no more than 30 minutes.Using the high temperature resistant conductor of ferrum-chromium-aluminum as preelectrolysis negative electrode, plumbago crucible carries out the preelectrolysis process of 2.0V, 0.5h as anode.After passing into 600ml/min high-purity argon gas 0.5h in YSZ pipe, add 500g solid metal sodium, upper cover and YSZ pipe are carried out installing cathode wire additional and continuing to pass into high-purity argon gas after encapsulation process.By negative electrode good aforesaid combination and electrolyzer top cap connects and negative electrode is slowly down to and is made interior metal sodium melt in fused salt to form liquid, according to the structure of Fig. 1, electrolyzer various piece is installed.By 500g analytical pure TiO
2powder is in the mode of spiral charging, be added to continuously in sodium Metal 99.5 negative electrode using argon gas as carrier gas, adding speed is 300g/h, carry out constant-potential electrolysis to additional 4.0V electrode voltage between cathode wire and positive wire, electrolysis continues to maintain after 1.5h after reinforced end, continues to add TiO in negative electrode
2powder 500g, feed rate is 300g/h, continues negative electrode entirety to be risen to after electrolysis 1.5h on fused salt liquid level, to carry out coolingly after reinforced end, takes out internal solids after temperature is down to room temperature.Upper metal sodium carries out after physical sepn for subsequent use, and it is dry that enrichment electrolysate in bottom carries out low temperature (60 DEG C) after washing, supersound process.
Product, taking black powder shape as main, obtains titanium sponge powder 589g after ultrasonic dispersion, washing, and titanium content is 99.78%, reaches national level Four titanium standard, can directly apply to industrial melted ingot processing.Electrolytic process current efficiency 90.1%.After electrolysis, the sodium Metal 99.5 rate of recovery is 84%, can directly recycle.
Claims (6)
1. an electrolyzer for Direct Electrolysis titanium dioxide production metal titanium, electrolyzer is upper and lower two portions, upper cover comprises anode and cathode interface, thermopair interface, cooling water system, adjustable argon gas import and outlet, TiO
2powder feeding screw is connected with argon gas import; Bottom adopts well formula stainless steel electrolytic groove, electrolyzer using high purity graphite crucible as fused salt, between plumbago crucible and stainless steel trough body, carry out insulation processing with high temperature material, it is characterized in that, described electrolyzer comprises a liquid metal sodium cathode, the zirconia solid oxygen permeable film pipe of stabilized with yttrium oxide that comprises sodium Metal 99.5, an end closure as negative electrode outer wall, high-purity filamentary silver as cathode wire, liquid metal sodium cathode is positioned in electrolysis fused salt, is provided with inlet mouth and the air outlet of argon gas above the liquid level of its sodium Metal 99.5 solution; High purity graphite crucible or graphite rod are as anode; In fused salt, be provided with preelectrolysis negative electrode and thermopair.
2. the electrolyzer of a kind of Direct Electrolysis titanium dioxide production metal titanium according to claim 1, is characterized in that, the zirconia solid oxygen permeable film pipe inside and outside wall of described stabilized with yttrium oxide is through the processing of high temperature spray titanium.
3. the electrolyzer of a kind of Direct Electrolysis titanium dioxide production metal titanium according to claim 1 and 2, is characterized in that, the bottom of described electrolyzer and negative electrode outer wall is provided with continuous discharging device.
4. the electrolyzer of a kind of Direct Electrolysis titanium dioxide production metal titanium according to claim 1 and 2, is characterized in that, the degree of depth of described stainless steel electrolytic groove is 600mm, and diameter is 300mm; The internal diameter of described negative electrode outer wall is that 150mm, thickness are 3mm.
5. a method for Direct Electrolysis titanium dioxide production metal titanium, is characterized in that, comprises the following steps:
(1) the KCl-LiCl binary fused salt mixt that KCl mole of proportioning of preparation is 40.8% ~ 47% is as molten salt electrolyte, at 300 DEG C of temperature, carry out 12h processed, and transfer to rapidly in plumbago crucible, in reactor, be warming up to rapidly and at 450 DEG C, carry out melting treatment, heating-up time is less than 30 minutes, taking preelectrolysis electrode as negative electrode, plumbago crucible carries out electrode voltage as 2.0V preelectrolysis process as anode;
(2) in the zirconia solid oxygen permeable film pipe of stabilized with yttrium oxide, incorporate after 600ml/min high-purity argon gas 0.5h, add solid metal sodium, add-on is as the criterion with pipe inner height 1/2, to after upper cover sealing, install high purity silver cathode wire additional and continue to pass into high-purity argon gas, negative electrode is slowly down in fused salt and is made sodium Metal 99.5 fusing form liquid state;
(3) by analytical pure TiO
2powder is in the mode of spiral charging, be added to continuously in sodium Metal 99.5 negative electrode using argon gas as carrier gas, adding speed is 100g/h ~ 300g/h, carry out constant-potential electrolysis to adding 2.8V ~ 4.0V electrode voltage between cathode wire and positive wire, electrolysis continues to maintain 1.5h ~ 4h after reinforced end;
(4) electrolysis finish after by sodium Metal 99.5 negative electrode entirety rise on fused salt liquid level, carry out cooling, after being down to room temperature, temperature takes out internal solids, upper metal sodium carries out recycling after physical sepn, and enrichment electrolysate in bottom carries out cryodrying after washing, supersound process, obtains titanium sponge powder.
6. the method for a kind of Direct Electrolysis titanium dioxide production metal titanium according to claim 5, is characterized in that, TiO in described step (3)
2the charging of powder is to take repeatedly batch charging or repeat reinforced technique.
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| CN108203835B (en) * | 2016-12-20 | 2019-12-31 | 有研稀土新材料股份有限公司 | Blowing protection device and method and rare earth fluoride salt electrolysis device |
| CN107560919A (en) * | 2017-10-27 | 2018-01-09 | 山东裕航特种合金装备有限公司 | A kind of aluminum alloy extrusion section bar microscopic structure method of inspection and its prepare metallographic specimen electrode |
| CN109023432A (en) * | 2018-10-09 | 2018-12-18 | 龙蟒佰利联集团股份有限公司 | A kind of electrolyzing fused titanium dioxide prepares the method and electrolysis unit of titanium-aluminium alloy |
| CN112030008B (en) * | 2020-07-13 | 2021-06-08 | 昆明理工大学 | Method for preparing metallic titanium by reducing titanium dioxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450205A (en) * | 2003-04-22 | 2003-10-22 | 上海大学 | Process for preparing titanium sponge from titanium oxide composite ore |
| 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 |
| CN101245418A (en) * | 2008-01-08 | 2008-08-20 | 上海大学 | Method for producing type AB hydrogen occluding alloy with titanium white as base |
| CN101260547A (en) * | 2008-02-29 | 2008-09-10 | 上海大学 | Method for preparing AB5 type hydrogen-storage alloy directly from metal oxide mixture |
| CN101457372A (en) * | 2008-12-04 | 2009-06-17 | 上海大学 | Method for directly preparing titanium and titanium alloy by titanium-containing waste residue |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6849104B2 (en) * | 2000-10-10 | 2005-02-01 | H. C. Starck Inc. | Metalothermic reduction of refractory metal oxides |
| US7504017B2 (en) * | 2001-11-22 | 2009-03-17 | Qit-Fer Et Titane Inc. | Method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state |
-
2012
- 2012-07-03 CN CN201210229485.2A patent/CN102719857B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450205A (en) * | 2003-04-22 | 2003-10-22 | 上海大学 | Process for preparing titanium sponge from titanium oxide composite ore |
| 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 |
| CN101245418A (en) * | 2008-01-08 | 2008-08-20 | 上海大学 | Method for producing type AB hydrogen occluding alloy with titanium white as base |
| CN101260547A (en) * | 2008-02-29 | 2008-09-10 | 上海大学 | Method for preparing AB5 type hydrogen-storage alloy directly from metal oxide mixture |
| CN101457372A (en) * | 2008-12-04 | 2009-06-17 | 上海大学 | Method for directly preparing titanium and titanium alloy by titanium-containing waste residue |
Non-Patent Citations (9)
| Title |
|---|
| Direct electrochemical reduction of solid vanadium oxide to metal vanadium;Zhuo-fei Cai, etal.;《International Journal of Minerals, Metallurgy and Materials》;20120630;第19卷(第6期);第499-505页 * |
| TiO2直接电解还原过程的研究;刘美凤 等;《中国有色金属学报》;20041031;第14卷(第10期);第1752-1757页 * |
| TiO2直接还原法提取金属钛研究进展;吴晓松 等;《钢铁钒钛》;20070531;第28卷(第2期);第67-71页 * |
| Zhuo-fei Cai, etal..Direct electrochemical reduction of solid vanadium oxide to metal vanadium.《International Journal of Minerals, Metallurgy and Materials》.2012,第19卷(第6期), |
| 何季麟 等.氧化钽（铌）还原制取钽（铌）粉的新方法.《中国有色金属学会第五届学术年会论文集》.2003, * |
| 刘美凤 等.TiO2直接电解还原过程的研究.《中国有色金属学报》.2004,第14卷(第10期), |
| 吴晓松 等.TiO2直接还原法提取金属钛研究进展.《钢铁钒钛》.2007,第28卷(第2期), |
| 固体透氧膜法用于制备金属钦的研究;陈朝轶 等;《中国稀土学报》;20080830;第26卷;第370-373页 * |
| 陈朝轶 等.固体透氧膜法用于制备金属钦的研究.《中国稀土学报》.2008,第26卷 |
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