CN103898555A - Metal titanium production method - Google Patents
Metal titanium production method Download PDFInfo
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- CN103898555A CN103898555A CN201210570206.9A CN201210570206A CN103898555A CN 103898555 A CN103898555 A CN 103898555A CN 201210570206 A CN201210570206 A CN 201210570206A CN 103898555 A CN103898555 A CN 103898555A
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Abstract
The present invention provides a metal titanium production method, which comprises: carrying out electrolysis on MgCl2 in a molten salt containing MgCl2, and adding TiCl4 to the formed magnesium liquid layer for producing the metal magnesium during the electrolysis process, such that the TiCl4 is reduced into the metal titanium with the produced metal magnesium, wherein the metal magnesium consumption rate of the reduction reaction is less than or equal to the metal magnesium production rate of the electrolysis through the electrolysis conditions and the addition amount of the TiCl4. With the method, the metal titanium production period can be effectively shortened, the magnesium electrolysis process and the reduction process are combined so as to achieve the closed loop circulation of the magnesium and effectively reduce the energy consumption of the production process, the production period is short, the continuous operation production can be achieved, and the application prospects are bright.
Description
Technical field
The present invention relates to a kind of method of producing metal titanium.
Background technology
Titanium or titanium alloy has a series of good characteristics, is widely used in the numerous areas such as space flight, chemical industry, electric power, boats and ships, sea water desaltination and daily life.The main method of producing at present titanium sponge is both at home and abroad magnesiothermy (Kroll method), mainly comprises TiCl
4produce, Mg electrolysis and also steam three large techniques, production energy consumption is higher holds at high price it, although institutes of scientific research institution is devoted for years in researching and developing novel titanium extraction process technology, has formed FFC, MER, TiCl both at home and abroad
4the series of process such as electrolysis.But all in the experimental study stage, many technical barriers are also broken through.Therefore, reduce the most direct method of titanium sponge production cost and improve exactly the existing operational path of optimization, realize the internal recycling that logistics can flow as far as possible.
Cause the higher reason of magnesiothermy (Kroll method) energy consumption to be: going back long, the whole technical process of steaming process production cycle is that batch production and magnesium eletrolysis process energy consumption are higher.Except power consumption, also there is the thermosteresis of the processes such as transport, refining in wherein magnesium eletrolysis operation, is also subject to the pollution of transport pipe material iron simultaneously, affects quality product.
Summary of the invention
The object of the invention is to overcome the defect of prior art, a kind of method that can effectively shorten the production cycle and reduce energy consumption and produce continuously metal titanium is provided.
To achieve these goals, the invention provides a kind of method of producing metal titanium, wherein, the method comprises: electrolysis contains MgCl
2fused salt in MgCl
2, and add TiCl in the magnesium liquid layer forming to generation MAGNESIUM METAL in electrolytic process
4, make the MAGNESIUM METAL generating by TiCl
4be reduced to metal titanium, the condition of electrolysis and TiCl
4add-on make reduction reaction consume the speed that the speed of MAGNESIUM METAL is less than or equal to electrolytic production of metals magnesium.
Adopt method of the present invention, can effectively shorten the cycle of producing metal titanium, magnesium eletrolysis technique and reducing process are combined, realize the closed cycle of magnesium, effectively reduced the energy consumption of production technique, with short production cycle, and can realize the production of working continuously, application prospect light.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the device schematic diagram of a kind of embodiment of method provided by the invention.
Description of reference numerals
1 ionogen molten bath 2 cathode compartments
3 anolyte compartment's 4 discharging parts
21 negative electrode 22TiCl
4reinforced parts
31 anodes
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of method of producing metal titanium, the method comprises: electrolysis contains MgCl
2fused salt in MgCl
2, and add TiCl in the magnesium liquid layer forming to generation MAGNESIUM METAL in electrolytic process
4, make the MAGNESIUM METAL generating by TiCl
4be reduced to metal titanium, the condition of electrolysis and TiCl
4add-on make reduction reaction consume the speed that the speed of MAGNESIUM METAL is less than or equal to electrolytic production of metals magnesium.
MAGNESIUM METAL and TiCl in the present invention
4there is following reaction:
2Mg+TiCl
4→Ti↓+2MgCl
2
In order to realize goal of the invention, only need to control condition and the TiCl of electrolysis
4add-on make reduction reaction consume the speed that the speed of MAGNESIUM METAL is less than or equal to electrolytic production of metals magnesium, can realize TiCl
4can react with MAGNESIUM METAL continuously, produce continuously titanium sponge and realize, make the titanium sponge generating be deposited on the bottom of fused salt.For the better effects if, the reaction efficiency that react are higher, preferably, ensure TiCl in described fused salt
4be less than 1:2 with the mol ratio of MAGNESIUM METAL, more preferably 1:1-1.5.
According to method provided by the invention, described in contain MgCl
2fused salt can be by MgCl
2the fused salt that melting forms, also can be for will contain MgCl
2and be selected from the fused salt that one or more ionogen meltings in the fluorochemical of muriate, alkaline-earth metal of alkali-metal muriate, alkali-metal fluorochemical, alkaline-earth metal except Mg form, and taking the gross weight of described fused salt as benchmark, MgCl
2content be>=10 % by weight, be preferably 10-30 % by weight.Described alkali metal chloride can be one or more in lithium chloride, sodium-chlor, Repone K and rubidium chloride, described alkaline metal fluoride cpd can be one or more in lithium fluoride, Sodium Fluoride, Potassium monofluoride and rubidium fluoride, the muriate of described alkaline-earth metal except Mg can be one or more in beryllium chloride, calcium chloride, strontium chloride and bariumchloride, and the fluorochemical of described alkaline-earth metal can be one or more in beryllium fluoride, magnesium fluoride, Calcium Fluoride (Fluorspan), strontium fluoride and barium fluoride.
According to method of the present invention, can be by conventional methods by ionogen melting to form fused salt, under preferable case, the ionogen that is used to form fused salt was first dried before melting, to remove the moisture existing with various forms, described being dried can adopt this area usual manner, can be for example vacuum-drying, in order fully to take off contained various forms of moisture, preferably, to be used to form the first dry 20-30h under 100-150 DEG C of condition of normal pressure of ionogen of fused salt, then under 300-400 DEG C of vacuum (≤1000PaA) condition, be dried 4-6h.
According to method provided by the invention, due to magnesium metal reduction TiCl
4reaction in MAGNESIUM METAL liquid layer, carry out, liquid MAGNESIUM METAL has ensured the temperature that reduction reaction is required, in order to make the better effects if efficiency of reduction reaction higher, contains MgCl described in preferably
2the temperature of fused salt higher than the fusing point of MAGNESIUM METAL lower than MAGNESIUM METAL and described in contain MgCl
2the gasification temperature of fused salt, further preferred, described temperature of molten salt is 680-750 DEG C.Because the temperature of described fused salt is usually above 600 DEG C, and TiCl
4boiling point is 136.4 DEG C, no matter by the TiCl of liquid state or gaseous state
4after adding in fused salt, TiCl
4all will become gaseous state, therefore method provided by the invention is for added TiCl
4initial temperature and form do not limit.
According to method provided by the invention, the condition of described electrolysis can be selected according to this area conventional electrolysis condition, in order to make the better efficiency of reaction effect higher, the condition of preferred described electrolysis comprises that strength of current is 400-600A, and cathode current density is 0.3-0.6A/cm
2, anodic current density is 0.3-0.6A/cm
2.
According to method provided by the invention, in order to make reaction effect better, described electrolysis can be carried out under inert atmosphere, and described inert atmosphere is selected from one or more in rare gas, is preferably argon gas.
According to method provided by the invention, the method can also comprise the step of the metal titanium separation the fused salt from containing metal titanium, reaction being generated.The step that the described metal titanium from the fused salt that contains metal titanium, reaction being generated separates can adopt the mode of this area routine, and preferably, described separating step carries out in inert atmosphere, and described inert atmosphere is selected from one or more in rare gas.In isolated product mixture, contain metal titanium and be mingled with the unreacted MgCl of containing
2fused salt, therefore, can purify to metal titanium by the method for this area routine, for example can adopt the method for distillation known in those skilled in the art or the method for hydrometallurgical process.
According to method provided by the invention, can generate Cl at electrolytic process Anodic
2, for fear of the Cl generating
2disturb magnesium metal reduction TiCl
4reaction, preferably, collect the Cl generating at anode in electrolytic process
2, ensure the Cl generating
2the MAGNESIUM METAL can Contact cathod not generating.
Method provided by the invention can adopt in the high temperature resistant electrolyzer of this area routine carries out, under preferable case, described method is carried out in the device of production metal titanium as shown in Figure 1, this device comprises ionogen molten bath 1, in described ionogen molten bath, be provided with cathode compartment 2 and anolyte compartment 3, the bottom of described cathode compartment 2 and anolyte compartment 3 communicates with described ionogen molten bath 1 respectively, in described cathode compartment 2, is provided with negative electrode 21 and TiCl
4reinforced parts 22, are provided with anode 31 in described anolyte compartment 3, and discharging parts 4 are arranged at the bottom in described ionogen molten bath 1.Use this device can better realize the continuous production of metal titanium and shorten the production cycle.
According to method provided by the invention, in described ionogen molten bath 1, cathode compartment 2 and anolyte compartment 3 can arrange in a usual manner, and preferred described cathode compartment 2 and anolyte compartment 3 are the Cl that independently space generates with guarantee anolyte compartment 3 Anodics 31 separately
2can not enter cathode compartment 2.The material of described cathode compartment 2 and anolyte compartment 3 can be various high temperature materials, is preferably selected from the one in boron nitride, silicon nitride and graphite; The shape of described cathode compartment 2 and anolyte compartment 3 can be designed to various formation as required, as long as can hold respectively negative electrode 21, TiCl
4reinforced parts 22, and anode 31.
According to method provided by the invention, the described negative electrode 21 in described cathode compartment 2 can arrange according to conventional selection the in this area, and the material of described negative electrode 21 can be conventional resistant to elevated temperatures electrode materials, is preferably selected from the one in graphite, nickel and molybdenum.Described negative electrode 21 preferably also has the function of adding fused salt, for example, negative electrode 21 is made to hollow tubular parts.Described TiCl in described cathode compartment 2
4reinforced parts 22 can be conventional TiCl
4reinforced parts are for example hollow tubular parts.Described anode 31 in described anolyte compartment 3 can arrange according to conventional selection the in this area, and the material of described anode 31 can be conventional resistant to elevated temperatures electrode materials, is preferably selected from the one in graphite, nickel and molybdenum.Described anode 31 preferably also has discharge Cl
2function, for example anode 31 is made to hollow tubular parts.
According to method provided by the invention, in the device of described production metal titanium, described discharging parts 4 can be the discharging parts of this area routine, for example, can be star-like dumper or cup valve.
To the process of production metal titanium of this preferred implementation briefly be described below.
A, in ionogen molten bath 1, interior interpolation contains MgCl
2fused salt, connect electrolysis power, on the anode 31 in anolyte compartment 3, will constantly produce Cl
2.Meanwhile, also constantly produce MAGNESIUM METAL on the negative electrode 21 in cathode compartment 2, MAGNESIUM METAL floats on and contains MgCl
2fused salt on form MAGNESIUM METAL liquid layer, after electrolysis for some time, pass through TiCl
4reinforced parts 22 add TiCl in MAGNESIUM METAL liquid layer
4, control the speed that its speed that adds speed to make reduction reaction consume MAGNESIUM METAL is less than or equal to electrolytic production of metals magnesium.
The metal titanium grain that b, reduction reaction produce sinks to the bottom in ionogen molten bath 1, after for some time, open the discharging parts 4 of lower end, discharge product mixture, and sent into distillation process or directly carry out hydrometallurgical process to separate the MgCl that contains removing wherein
2fused salt, finally obtain resultant metal titanium, recycle the unreacted MgCl of containing simultaneously
2fused salt.
Method provided by the invention can be for producing metal titanium continuously, be particularly useful for producing continuously titanium sponge, compared with existing Kroll method (magnesiothermy), the titanium sponge uniform particles that the present invention produces, its granularity is 0.1-1cm, the utilization ratio of MAGNESIUM METAL reaches more than 70% (because magnesium eletrolysis current efficiency generally can maintain 85% left and right, actual metal magnesium utilization efficiency is about (0.7 ÷ 0.85) × 100%=82%), can realize the production of working continuously, can effectively shorten the cycle of subsequent products purification (distillation or hydrometallurgical process), the present invention combines magnesium eletrolysis technique and reducing process, realize the closed cycle of magnesium, thereby effectively reduce the calorific loss of magnesium in the processes such as transmission, existing Kroll method energy consumption is about 69000-70000kWh/t
ti, be about 56000-60000kWh/t and the present invention produces the energy consumption of metal titanium
ti, energy consumption obviously reduces, therefore application prospect light.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will describe the present invention by embodiment.
The measuring method of the quality product of metal titanium is as follows: adopt ICP spectroscopic analysis to measure metallic element (Fe, Mg, Mn, Ti) wherein; Spectrophotometer method is measured chlorine element wherein; Nitrogen hydrogen-oxygen determinator is measured N, H, O wherein; Aas determination Si wherein; Carbon and sulfur analytical instrument is measured carbon wherein.
The method of calculation of the ionogen rate of recovery are as shown in 1 formula:
Wherein, η is the ionogen rate of recovery (%), and m reclaims the electrolyte weight (g) obtaining; m
2for reclaiming front ionogen total mass (g); m
1for the product weight (g) obtaining after electrolytic recovery.
MAGNESIUM METAL utilization ratio method of calculation are as shown in 2 formulas:
Wherein: m=CIt; C is MAGNESIUM METAL electrochemical equivalent (0.453g/Ah); I strength of current (A); T, electrolysis time (h).M
1reaction finishes MAGNESIUM METAL weight (g) in rear ionogen;
When energy consumption calculation, select 20%TiO
2the ilmenite concentrate of content is smelted 90%TiO
2carry out, calculate and undertaken by 3 formulas:
W=UIt+W
former+ W
add+ W
after(3)
Wherein, U is that electrolyzer is pressed (V); I is Faradaic current intensity (A); T is electrolysis time (h);
W
formerenergy consumption (the kWh/t converting out for electrolysis is raw materials used
ti); W
addenergy consumption (the kWh/t that electrolytic furnace heats
ti); W
afterenergy consumption (the kWh/t consuming for aftertreatment
ti).
In the following example, produce the method for metal titanium carries out in device as shown in Figure 1.This device comprises ionogen molten bath 1, in described ionogen molten bath, be provided with cathode compartment 2 and anolyte compartment 3, the material of described cathode compartment 2 and anolyte compartment 3 is boron nitride, and the bottom of described cathode compartment 2 and anolyte compartment 3 communicates with described ionogen molten bath 1 respectively, in described cathode compartment 2, is provided with negative electrode 21 and TiCl
4reinforced parts 22, the material of described negative electrode 21 is graphite, its structure is bar-shaped, described TiCl
4the material of reinforced parts 22 is quartz, and its structure is tubulose, in described anolyte compartment 3, is provided with anode 31, and the material of described anode 31 is graphite, and its structure is bar-shaped, and discharging parts 4 are arranged at the bottom in described ionogen molten bath 1, and its structure is star-like dumper.
Embodiment mono-
The present embodiment is for illustrating the method for production metal titanium provided by the invention.
By MgCl
2at 120 DEG C after constant pressure and dry 24h, then under 300-400 DEG C of vacuum (≤1000PaA) condition dry 5h, by dried MgCl
2add in the ionogen molten bath 1 of device as shown in Figure 1, be filled with argon gas and be warming up to 800 DEG C and make MgCl
2melting, connects electrolysis power, and strength of current is controlled at 500A, and negative electrode 21 current densities are 0.5A/cm
2, anode 31 current densities are 0.4A/cm
2, after half an hour, by TiCl
4from TiCl
4in filling tube 22, add in the magnesium liquid layer that the MAGNESIUM METAL of cathode compartment 2 forms, flow control is at 10g/min, TiCl in fused salt
4with the mol ratio of MAGNESIUM METAL be 1:1, after 5h, open dumping device 4, product mixture is expelled in the heat insulation tank of argon shield, filter out the MgCl of melting
2, resultant metal titanium is distilled to 5h at 950-1000 DEG C, obtain finished product titanium sponge.Simultaneously by the unreacted melting MgCl obtaining
2join in ionogen molten bath 1 and recycle.Gained titanium sponge quality reaches MHT100 standard, and granularity is 0.1-1cm, MgCl
2the rate of recovery is 98%, and MAGNESIUM METAL utilization ratio is 70%, and energy consumption is: 56500kWh/t
ti, the production cycle is 12h/t
ti.
Embodiment bis-
The present embodiment is for illustrating the method for production metal titanium provided by the invention.
By MgCl
2-CaCl
2-NaCl-MgF
2(its massfraction proportioning is 20:20:58:2) at 120 DEG C after constant pressure and dry 24h, then under 300-400 DEG C of vacuum (≤1000PaA) condition dry 5h, by dried MgCl
2add in the ionogen molten bath 1 of device as shown in Figure 1, be filled with argon gas and be warming up to 680 DEG C and make MgCl
2melting, connects electrolysis power, and strength of current is controlled at 500A, and negative electrode 21 current densities are 0.3A/cm
2, anode 31 current densities are 0.3A/cm
2, after half an hour, by TiCl
4from TiCl
4in filling tube 22, add in the magnesium liquid layer that the MAGNESIUM METAL of cathode compartment 2 forms, flow control is at 10g/min, TiCl in fused salt
4with the mol ratio of MAGNESIUM METAL be 1:1.5, after 5h, open dumping device 4, product mixture is expelled in the heat insulation tank of argon shield, filter out the ionogen MgCl of melting
2-CaCl
2-NaCl-MgF
2, by cooling resultant metal titanium and carry out hydrometallurgical process, after washing and drying, obtain finished product titanium sponge.Simultaneously by the ionogen MgCl of the unreacted melting obtaining
2-CaCl
2-NaCl-MgF
2join in ionogen molten bath 1 and recycle.Gained titanium sponge quality reaches MHT100 standard, and granularity is 0.1-1cm, ionogen MgCl
2-CaCl
2-NaCl-MgF
2the rate of recovery is 97%, and MAGNESIUM METAL utilization ratio is 74%, and energy consumption is: 58500kWh/t
ti, production cycle 10h/t
ti.
Embodiment tri-
The present embodiment is for illustrating the method for production metal titanium provided by the invention.
By MgCl
2at 120 DEG C after constant pressure and dry 24h, then under 300-400 DEG C of vacuum (≤1000PaA) condition dry 5h, by dried MgCl
2add in the ionogen molten bath 1 of device as shown in Figure 1, be filled with argon gas and be warming up to 800 DEG C and make MgCl
2melting, connects electrolysis power, and strength of current is controlled at 400A, and negative electrode 21 current densities are 0.5A/cm
2, anode 31 current densities are 0.6A/cm
2, after half an hour, by TiCl
4from TiCl
4in filling tube 22, add in the magnesium liquid layer that the MAGNESIUM METAL of cathode compartment 2 forms, flow control is at 8g/min, TiCl in fused salt
4with the mol ratio of MAGNESIUM METAL be 1:1.2, after 5h, open dumping device 4, product mixture is expelled in the heat insulation tank of argon shield, filter out the MgCl of melting
2, more than resultant metal titanium is distilled to 5h at 950-1000 DEG C, obtain finished product titanium sponge.Simultaneously by the unreacted melting MgCl obtaining
2join in ionogen molten bath 1 and recycle.Gained titanium sponge quality reaches MHT100 standard, and granularity is 0.1-1cm, MgCl
2the rate of recovery is 98%, and MAGNESIUM METAL utilization ratio is 76%, and energy consumption is: 56700kWh/t
ti, production cycle 8h/t
ti.
Result by above-described embodiment 1-3 can be found out, the titanium sponge uniform particles that the present invention produces, and its granularity is 0.1-1cm, quality product reaches MHT100 standard.The utilization ratio of MAGNESIUM METAL reaches more than 70% (because magnesium eletrolysis current efficiency generally can maintain 85% left and right, actual metal magnesium utilization efficiency is about (0.7/0.85) * 100%=82%), can realize the production of working continuously, can effectively shorten the cycle of subsequent products purification (distillation or hydrometallurgical process), the present invention combines magnesium eletrolysis technique and reducing process, realize the closed cycle of magnesium, thereby effectively reducing the calorific loss of magnesium in the processes such as transmission, existing Kroll method energy consumption is about 69000-70000kWh/t
ti, be about 56000-60000kWh/t and the present invention produces the energy consumption of metal titanium
ti, energy consumption obviously reduces, therefore application prospect light.
Claims (10)
1. a method of producing metal titanium, is characterized in that, the method comprises: electrolysis contains MgCl
2fused salt in MgCl
2, and add TiCl in the magnesium liquid layer forming to generation MAGNESIUM METAL in electrolytic process
4, make the MAGNESIUM METAL generating by TiCl
4be reduced to metal titanium, the condition of electrolysis and TiCl
4add-on make reduction reaction consume the speed that the speed of MAGNESIUM METAL is less than or equal to electrolytic production of metals magnesium.
2. method according to claim 1, wherein, the condition of electrolysis and TiCl
4add-on make TiCl in described fused salt
4be less than 1:2 with the mol ratio of MAGNESIUM METAL, be preferably 1:1-1.5.
3. method according to claim 1 and 2, wherein, described in contain MgCl
2fused salt be by MgCl
2the fused salt that melting forms.
4. method according to claim 1 and 2, wherein, described in contain MgCl
2fused salt for will contain MgCl
2and be selected from the fused salt that one or more ionogen meltings in the fluorochemical of muriate, alkaline-earth metal of alkali-metal muriate, alkali-metal fluorochemical, alkaline-earth metal except Mg form, and taking the gross weight of described fused salt as benchmark, MgCl
2content be>=10 % by weight, be preferably 10-30 % by weight.
5. method according to claim 1 and 2, wherein, described in contain MgCl
2the temperature of fused salt higher than the fusing point of MAGNESIUM METAL lower than MAGNESIUM METAL and described in contain MgCl
2the gasification temperature of fused salt.
6. method according to claim 1 and 2, wherein, the condition of described electrolysis comprises that strength of current is 400-600A, cathode current density is 0.3-0.6A/cm
2, anodic current density is 0.3-0.6A/cm
2.
7. according to the method described in claim 1 or 6, wherein, described electrolysis is carried out under inert atmosphere, and described inert atmosphere is selected from one or more in periodic table of elements zero group gas.
8. method according to claim 1 and 2, wherein, the method also comprises the step the fused salt that contains metal titanium from obtaining, metal titanium being separated.
9. method according to claim 1, wherein, the method also comprises collects the Cl generating at anode in electrolytic process
2.
10. according to the method described in any one in claim 1-9, wherein, the method is carried out in the device of producing metal titanium, this device comprises ionogen molten bath (1), in described ionogen molten bath, be provided with cathode compartment (2) and anolyte compartment (3), the bottom of described cathode compartment (2) and anolyte compartment (3) communicates with described ionogen molten bath (1) respectively, is provided with negative electrode (21) and TiCl in described cathode compartment (2)
4reinforced parts (22), are provided with anode (31) in described anolyte compartment (3), the bottom in described ionogen molten bath (1) is also provided with discharging parts (4).
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| CN106894059A (en) * | 2017-04-12 | 2017-06-27 | 攀钢集团研究院有限公司 | Metallic titanium powder molten-salt electrolysis recovery method |
| CN108546964A (en) * | 2018-05-29 | 2018-09-18 | 钢研晟华科技股份有限公司 | A kind of preparation facilities and preparation method of Titanium |
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| CN105088283B (en) * | 2015-09-29 | 2018-05-11 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for extracting Titanium |
| CN106894059A (en) * | 2017-04-12 | 2017-06-27 | 攀钢集团研究院有限公司 | Metallic titanium powder molten-salt electrolysis recovery method |
| CN108546964A (en) * | 2018-05-29 | 2018-09-18 | 钢研晟华科技股份有限公司 | A kind of preparation facilities and preparation method of Titanium |
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