CN115161714B - Method for preparing metallic titanium by molten salt solid-state deoxidization method - Google Patents
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- CN115161714B CN115161714B CN202210917210.1A CN202210917210A CN115161714B CN 115161714 B CN115161714 B CN 115161714B CN 202210917210 A CN202210917210 A CN 202210917210A CN 115161714 B CN115161714 B CN 115161714B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
- C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
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Abstract
The invention provides a method for preparing metallic titanium by a molten salt solid-state deoxidization method, which comprises the following steps: molding titanium dioxide and then sintering to obtain a sintering product; electrolyzing the sintered product in chloride to obtain metallic titanium; and dynamically adjusting the electrolysis voltage in the electrolysis process. The method provided by the invention omits the steps of secondary electrorefining or pre-generating titanium oxycarbide and the like in the prior art, and realizes the compactness of the process flow; by dynamically adjusting the electrolysis voltage between 3V and 9V, the applied electrolysis voltage can reach the voltage required by the electro-deoxidation of titanium dioxide, and simultaneously, the molten salt decomposition caused by the overhigh electrolysis voltage and the extra electrolysis electric quantity consumption caused by the decomposition of the molten salt can be avoided, thereby avoiding the generation of harmful gases such as chlorine, reducing the total energy consumption and realizing the efficient low-pollution preparation of the metal titanium by the electro-deoxidation of the molten salt; the electrolytic parameter setting can be flexibly adjusted according to the addition amount of raw materials and the electrode size, and the cost fluctuation caused by the too low or too high product yield is avoided.
Description
Technical Field
The invention belongs to the technical field of titanium, and particularly relates to a method for preparing metallic titanium by a molten salt solid-state deoxidization method.
Background
Titanium metal has unique physicochemical properties, and is not an alternative to the importance of the high-end manufacturing field. The prior art process for preparing metallic titanium (Kroll method) has long flow, high energy consumption and large pollution. The preparation from raw materials to final titanium sponge is carried out by mineral separation, enrichment, chlorination, refining, magnesium reduction (comprising magnesium chloride electrolysis and magnesium recovery), vacuum distillation and other process steps. The price of the metal titanium is far higher than that of most structural metal materials and alloy materials due to the complex process flow, and the application amount and market range of the metal titanium are greatly limited. Therefore, a short-flow, low-energy-consumption and low-pollution green metal titanium preparation technology process needs to be developed.
Disclosure of Invention
In view of the above, the invention aims to provide a method for preparing metallic titanium by a molten salt solid-state deoxidization method, which has the advantages of simple process, high efficiency and low pollution.
The invention provides a method for preparing metallic titanium by a molten salt solid-state deoxidization method, which comprises the following steps:
molding titanium dioxide and then sintering to obtain a sintering product;
electrolyzing the sintered product in chloride to obtain metallic titanium;
and dynamically adjusting the electrolysis voltage in the electrolysis process.
Preferably, the sintering temperature is 200-1000 ℃.
Preferably, the chloride salt is selected from CaCl 2 、LiCl、BaCl 2 One or more of NaCl and KCl.
Preferably, the cathode structure in the electrolysis process is a sintered product, and the anode structure is graphite.
Preferably, the temperature in the electrolysis process is 830-1200 ℃.
Preferably, the chlorine salt is first enriched after being melted in the electrolysis process; and dynamically adjusting enrichment voltage in the enrichment process to enable:
V enrichment voltage ≤V Enriching dynamic voltage <V Chlorine salt decomposition voltage 。
Preferably, the dynamic adjustment of the electrolytic voltage causes:
V electro-deoxidation voltage ≤V Dynamic electrolytic voltage <V Chlorine salt decomposition voltage 。
Preferably, the dynamically adjusted electrolytic voltage is in the range of 3 to 9V.
Preferably, the V Chlorine salt decomposition voltage 3.04-10.28V.
Preferably, the V Enrichment voltage 1.2 to 2.8V;
the V is Electro-deoxidation voltage 1.93 to 1.79V.
The invention provides a low-pollution and high-efficiency pure titanium production process method, which is a novel process for directly preparing metallic titanium from raw materials such as titanium dioxide (titanium white) by solid electrolysis based on a molten salt solid-state deoxidization method, and has better balance in the aspects of compact process flow, improved electrolysis efficiency, reduced pollution emission, flexibility of capacity adjustment and the like.
According to the method provided by the invention, after the raw material titanium dioxide is simply molded, the raw material titanium dioxide is directly placed in molten chlorine salt for electro-deoxidation, so that the metal titanium is directly prepared, the steps of secondary electro-refining or pre-generating titanium oxycarbide and the like in the prior art are omitted, and the process flow is compactified; by dynamically adjusting the electrolysis voltage between 3V and 9V (manually or automatically controlled by a computer program), the electrolysis voltage applied can be ensured to reach the voltage required by the electro-deoxidation of titanium dioxide, and simultaneously, the decomposition of molten salt and the consumption of extra electrolysis electric quantity caused by the excessively high electrolysis voltage are avoided, thereby avoiding the generation of harmful gas such as chlorine, reducing the total energy consumption and realizing the efficient low-pollution electro-deoxidation of molten salt to prepare the metallic titanium; by adopting the dynamic voltage adjustment method based on the resistance value of the electrode component and the real-time electrolysis current, the electrolysis parameter setting can be flexibly adjusted according to the addition amount of raw materials and the electrode size, and the flexible adjustment of the industrialized production energy can be realized under the condition that main production equipment and basic process parameters are not greatly changed, so that the cost fluctuation caused by the excessively low or excessively high product yield is avoided.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for preparing metallic titanium by a molten salt solid-state deoxidization method, which comprises the following steps:
molding titanium dioxide and then sintering to obtain a sintering product;
electrolyzing the sintered product in chloride to obtain metallic titanium;
and dynamically adjusting the electrolysis voltage in the electrolysis process.
In the invention, in the molding process, titanium dioxide raw materials and deionized water are mixed according to the mass ratio of 1:1 to 1:10 to prepare slurry, and then the slurry is prepared into a cylindrical or sheet-shaped mold by extrusion or slip casting.
In the present invention, the sintering temperature is preferably 200 to 1000 ℃, more preferably 500 to 800 ℃, and most preferably 600 to 700 ℃.
In the present invention, the sintered product is preferably used as a cathode structure in the electrolytic process; graphite is preferably used as the anode structure.
In the present invention, it is preferable that the electrode structure (cathode structure and anode structure) is put into a container containing chlorine salt for electrolysis in the electrolysis process; the chloride salt is preferably selected from CaCl 2 、LiCl、BaCl 2 Or a single, binary, ternary or multi-element eutectic mixture of NaCl, KCl and the three chlorine salts; preferably selected from calcium chloride and (sodium chloride or potassium chloride); the mass of the sodium chloride or potassium chloride is preferably 5 to 20% of the mass of the calcium chloride, more preferably 10 to 15%.
In the present invention, the temperature in the electrolytic process is preferably 830 to 1200 ℃, more preferably 850 to 1150 ℃, still more preferably 900 to 1100 ℃, and most preferably 900 ℃.
In the present invention, it is preferable that a specific voltage V is applied after the chlorine salt is melted in the electrolysis process Enrichment Enriching titanium dioxide and other valence titanium oxides in the raw materials; the V is Enrichment Preferably, the dynamic adjustment is performed according to the real-time current in the electrolysis process, and the dynamic adjustment method is performed according to the following formula:
V enriching dynamic voltage ＝V Enrichment voltage +(R Total (S) *I Real time )*K Chloride decomposition Voltage coefficient 1 ；
Wherein V is Enrichment voltage A voltage for oxidizing metal impurities contained in the titanium dioxide raw material into metal ions;
R total (S) The total resistance value of the electrode structure;
I real time Is the real-time current in the enrichment process;
K chloride decomposition Voltage coefficient 1 To set the voltage coefficient required for the decomposition of the chloride at the electrolysis temperature.
In the present invention, the V Enrichment voltage Preferably 1.2 to 2.8V, more preferably 1.5 to 2.5V, and most preferably 2V. In the present invention, the V Enrichment voltage Preferably by thermodynamic calculation, V at electrolysis temperature Enrichment voltage The calculation can be performed according to the following formula:
V enrichment voltage The gibbs free energy/faraday constant of ionization of the metal impurities/number of electron transfer at ionization was calculated by thermodynamics.
In the present invention, the R Total (S) The method for obtaining (a) preferably comprises:
connecting the electrode structural component A with a constant current power supply, applying A A1 The current, recorded at A A1 V generated under current A1 Voltage is applied A A2 The current, recorded at A A2 V generated under current A2 Voltage is applied A A3 The current, recorded at A A3 V generated under current A3 A voltage; repeating the steps until a predictable stable relationship between the current and the voltage is established. Obtaining an average current value R by repeating the test Average A In order to reduce systematic errors caused by contact resistance variations during the measurement; storing records and turning off a constant current power supply; the resistance value of the electrode structural member a was calculated by the following formula:
R A1 ＝V A1 /A A1 ；R A2 ＝V A2 /A A2 ；R A3 ＝V A3 /A A3 ；……R An ＝V An /A An
R average A ＝(R A1 +R A2 +R A3 +……R An )/n；
Repeating the steps to measure the resistance values of all the electrode parts to obtain R Average B 、R Average C 、R Average D ……R Average X 。
The calculation formula of the resistance value of the serial part is as follows:
R string ＝R Average A string +R Average B string +R Average C string +R Average D string ……+R Average X-string
And the calculation formula of the parallel connection part resistance value is as follows:
R and is combined with ＝1/(1/R Average A and +1/R average B and +1/R average C and +1/R average D and ……+R mean X and )
the calculation formula of the total resistance of the electrode structure is as follows:
R total (S) ＝(R String +R And is combined with )*K Temperature resistivity of
K Temperature resistivity of The resistance correction coefficient of the electrode material at different electrolysis temperatures is obtained.
In the present invention, the K Temperature resistivity of The method for obtaining (a) preferably comprises: available through a network or database.
In the present invention, I Real time Is the observed current: the electrolysis process only applies voltage, I Real time Is applied V Enrichment voltage Post-production, then observe I Real time Brought to formula V Enriching dynamic voltage ＝V Enrichment voltage +(R Total (S) *I Real time )*K Chloride decomposition Voltage coefficient 1 V can be obtained in Enriching dynamic voltage 。
In the present invention, the K Chloride decomposition Voltage coefficient 1 The method for obtaining (a) preferably comprises:
K chloride decomposition Voltage coefficient 1 ＝((V Chlorine salt decomposition voltage +(R Total (S) *I Real time ))*0.9-V Enrichment voltage )/(R Total (S) *I Real time )
In the present invention, K Chloride decomposition Voltage coefficient 1 Guarantee V Enriching dynamic voltage Does not cause molten salt decomposition.
In the present invention, the time for the enrichment is 2 to 12 hours, more preferably 5 to 10 hours, and most preferably 6 to 8 hours.
In the invention, the electrolysis voltage in the electrolysis process is preferably dynamically adjusted within the range of 3-9V; preferably, after enrichment is finished, the electrolytic voltage is dynamically adjusted according to the following formula:
V dynamic electrolytic voltage ＝V Electro-deoxidation voltage +(R Total (S) *I Real time )*K Chloride decomposition voltage coefficient 2 ；
Wherein V is Electro-deoxidation voltage Is V (V) Electro-deoxidation voltage The voltage required for deoxidizing the titanium dioxide at the electrolysis temperature;
R total (S) The total resistance value of the electrode structure;
I real time Is the real-time current in the electrolysis process;
K chloride decomposition voltage coefficient 2 To be a factor of the voltage required for decomposition of chlorine salt at a set electrolysis temperature.
In the present invention, the V Electro-deoxidation voltage Preferably 1.93 to 1.79V.
In the present invention, the V Electro-deoxidation voltage Preferably by thermodynamic calculation, V at electrolysis temperature Electro-deoxidation voltage The method comprises the steps of carrying out a first treatment on the surface of the The calculation can be performed according to the following formula:
V electro-deoxidation voltage The gibbs free energy per faraday constant per electron transfer number at deoxygenation of titania at electrolysis temperature was calculated by thermodynamics.
In the present invention, the R Total (S) The obtaining method is consistent with the technical scheme.
In the present invention, I Real time Is the observed current: the electrolysis process only applies voltage, I Real time Is applied V Electro-deoxidation voltage Post-production, then observe I Real time Brought to formula V Dynamic electrolytic voltage ＝V Electro-deoxidation voltage +(R Total (S) *I Real time )*K Chloride decomposition voltage coefficient 2 V can be obtained in Dynamic electrolytic voltage 。
In the present invention, the K Chloride decomposition voltage coefficient 2 The method for obtaining (a) preferably comprises:
K chloride decomposition voltage coefficient 2 ＝((V Chlorine saltSolution voltage +(R Total (S) *I Real time ))*0.9-V Electro-deoxidation voltage )/(R Total (S) *I Real time )
In the present invention, K Chloride decomposition voltage coefficient 2 Coefficient assurance V Dynamic electrolytic voltage Does not cause molten salt decomposition.
In the present invention, V Enriching dynamic voltage And V Dynamic electrolytic voltage The whole electrolysis process is controlled in the following steps:
V enrichment voltage ≤V Enriching dynamic voltage <V Chlorine salt decomposition voltage ；
V Electro-deoxidation voltage ≤V Dynamic electrolytic voltage <V Chlorine salt decomposition voltage Within the range.
In the present invention, the V Chlorine salt decomposition voltage Preferably 3.04 to 10.28V.
In the present invention, the V Chlorine salt decomposition voltage Preferably V at the electrolysis temperature is obtained by thermodynamic calculation Chlorine salt decomposition voltage The method comprises the steps of carrying out a first treatment on the surface of the Can be calculated according to the following formula:
V chlorine salt decomposition voltage The gibbs free energy of chloride decomposition/faraday constant/electron transfer number at chloride decomposition + electrolysis measured current at electrolysis temperature was calculated by thermodynamics.
In the present invention, the dynamic adjustment preferably dynamically adjusts V at a frequency of 5 minutes to 1 hour each time, based on the voltage drop change caused by the system resistance and the electrolysis current change Dynamic electrolytic voltage 。
The method provided by the invention can effectively improve the electrolysis efficiency and avoid pollutant emission caused by chlorine salt decomposition. Meanwhile, as different loading amounts can cause larger fluctuation on the resistance value of the electrode component and the electrolytic current value, the adoption of the real-time dynamic electrolytic voltage adjustment process can realize flexible adjustment of the productivity under the condition that main production equipment and basic process parameters are not changed greatly.
In the invention, the metallic titanium obtained by electrolysis is peeled off after the electrode is cooled after the electrolysis is finished; preferably, the stripped metallic titanium is washed by dilute acid and clean water to obtain clean metallic titanium.
In the present invention, the dilute acid is preferably selected from dilute sulfuric acid, dilute hydrochloric acid or dilute acetic acid.
The method provided by the invention has better balance in the aspects of compact process flow, pollutant generation control, electrolysis efficiency improvement, capacity dynamic adjustment capability and the like, and fills up the short plates in the aspects of complex process flow, heavy environmental pollution burden, low production efficiency, huge price fluctuation and the like in the field of metal titanium smelting.
Example 1
15g of titanium dioxide (TiO) 2 Not less than 96%) and 15g of deionized water are added and stirred uniformly, and the mixture is extruded into the diameter<10mm strips are dried and put into a sintering furnace for sintering at 800 ℃ for 5 hours, naturally cooled and then taken out and put into an alumina crucible to be connected with an iron rod to be used as an electrode, meanwhile, a carbon rod with the diameter of 15mm and the length of 300mm is put into a carbon rod to be used as a counter electrode, 1kg of anhydrous calcium chloride is added, and then the carbon rod and the counter electrode are put into an electrolytic electric furnace together, the carbon rod are vacuumized, filled with argon and sealed, and after the temperature is raised to 900 ℃, V at 900 ℃ is calculated and measured respectively Enrichment voltage And V Electro-deoxidation voltage Firstly using V Enrichment voltage (1.5V) oxidizing the metal impurities in the titanium dioxide so as to enable the metal impurities to be removed from the titanium dioxide in a metal ion form (lasting for 1 hour) to increase the purity of the titanium dioxide; thereafter adopt V Dynamic electrolytic voltage (based on observed electrolysis current (time-dependent) and measured system resistance (fixed value), by V Dynamic electrolytic voltage The formula is that the formula is adjusted at intervals of 30 minutes, and the adjustment range is 3.1-4.2V); stopping electrolysis for 21 hours, naturally cooling, opening a furnace cover after the furnace temperature is reduced to room temperature, and cleaning the metallic titanium obtained by electrolysis by using dilute hydrochloric acid and water respectively.
The metallic titanium prepared in the embodiment 1 of the invention has silver gray metallic luster and higher hardness, and is subjected to X-ray fluorescence spectrum detection analysis, wherein the oxygen content is 900ppm, and the titanium content is 99.10wt%.
Example 2
36g of titanium dioxide (TiO) 2 96% or more) was added 36g of deionized waterStirring water uniformly, extruding into diameter<10mm strips are dried and put into a sintering furnace for sintering at 900 ℃ for 5 hours, naturally cooled and then taken out and put into a graphite crucible to be connected with an iron rod to be used as an electrode, meanwhile, a carbon rod with the diameter of 20mm and the length of 300mm is put into a carbon rod to be used as a counter electrode, 1.5kg of anhydrous calcium chloride and 5 percent of anhydrous potassium chloride (the mass of the anhydrous potassium chloride is 5 percent of that of the anhydrous calcium chloride) are added, and then the mixture is put into an electrolytic furnace together, sealed after vacuumizing and argon filling, and V at 850 ℃ is calculated and measured respectively after heating to 850 DEG C Enrichment voltage And V Electro-deoxidation voltage Firstly using V Enrichment voltage (1.8V) oxidizing the metal impurities in the titanium dioxide so as to enable the metal impurities to be removed from the titanium dioxide in a metal ion form (lasting for 2 hours) to increase the purity of the titanium dioxide; thereafter adopt V Dynamic electrolytic voltage (based on observed electrolysis current (time-dependent) and measured system resistance (fixed value), by V Dynamic electrolytic voltage The formula is that the formula is adjusted at intervals of 1 hour, and the adjustment range is 3.3-4.8V); stopping electrolysis for 24 hours, naturally cooling, opening a furnace cover after the furnace temperature is reduced to room temperature, and cleaning the metallic titanium obtained by electrolysis by using dilute hydrochloric acid and water respectively.
The metallic titanium prepared in the embodiment 2 of the invention has silver gray metallic luster and higher hardness, and is subjected to X-ray fluorescence spectrum detection analysis, wherein the oxygen content is 1800ppm, and the titanium content is 98.91wt%.
Example 3
500g of titanium dioxide (TiO) 2 More than or equal to 96 percent) is added with 500g of deionized water and stirred uniformly, and is extruded into thickness<A plate with the length of 7mm and the width of 100mm and the width of 50mm is placed into a sintering furnace for sintering for 6 hours at 1000 ℃, is taken out after natural cooling, is placed into a carbon steel crucible and is connected with an iron rod to be used as an electrode, simultaneously a carbon rod with the diameter of 30mm and the length of 300mm is placed into a counter electrode, 20kg of anhydrous calcium chloride and 20 percent of anhydrous sodium chloride (the mass of the anhydrous sodium chloride is 20 percent of that of the anhydrous calcium chloride) are added, and then the plate is placed into an electrolytic furnace together, is sealed after vacuumizing and argon filling, and is heated to 1000 ℃, and V at 1000 ℃ is calculated and measured respectively Enrichment voltage And V Electro-deoxidation voltage Firstly using V Enrichment voltage (1.9V) oxidizing the metal impurities in the titanium dioxide so as to enable the metal impurities to be removed from the titanium dioxide in a metal ion form (3 hours) to increase the purity of the titanium dioxide; thereafter adopt V Dynamic electrolytic voltage (based on observed electrolysis current (time-dependent) and measured system resistance (fixed value), by V Dynamic electrolytic voltage The formula is that the formula is adjusted at intervals of 2 hours, and the adjustment range is 4.5V-6.1V); stopping electrolysis for 24 hours, naturally cooling, opening a furnace cover after the furnace temperature is reduced to room temperature, and cleaning the metallic titanium obtained by electrolysis by using dilute hydrochloric acid and water respectively.
The metallic titanium prepared in the embodiment 3 of the invention has silver gray metallic luster and higher hardness, and is subjected to X-ray fluorescence spectrum detection analysis, wherein the oxygen content is 1900ppm, and the titanium content is 98.71wt%.
The method adopts dynamic voltage adjustment in the process of preparing the metal titanium, and compared with constant voltage, the method has the advantages that the purity of the obtained metal titanium is higher, the hardness is better, the time for preparing the metal titanium is shorter, the production efficiency can be improved, the method is suitable for industrial mass production and preparation, and meanwhile, the overall quality stability of the metal titanium is higher when the metal titanium is prepared in a large quantity.
The method provided by the invention has better balance in the aspects of compact process flow, pollutant generation control, electrolysis efficiency improvement, capacity dynamic adjustment capability and the like, and fills up the short plates in the aspects of complex process flow, heavy environmental pollution burden, low production efficiency, huge price fluctuation and the like in the field of metal titanium smelting.
While the invention has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the invention. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the invention as defined by the following claims, so as to adapt the objective, spirit and scope of the present application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (10)
1. A method for preparing metallic titanium by a molten salt solid-state deoxidization method, which comprises the following steps:
molding titanium dioxide and then sintering to obtain a sintering product;
electrolyzing the sintered product in chloride to obtain metallic titanium;
in the electrolytic process, a specific voltage V is firstly applied after the chlorine salt is melted Enrichment voltage Enriching titanium dioxide and other valence titanium oxides in the raw materials; the V is Enrichment Voltage (V) The method for dynamically adjusting the current in the electrolysis process is carried out according to the following formula:
V enriching dynamic voltage = V Enrichment voltage + (R Total (S) *I Real time )*K Chloride decomposition Voltage coefficient 1 ；
Wherein V is Enrichment voltage A voltage for oxidizing metal impurities contained in the titanium dioxide raw material into metal ions;
R total (S) The total resistance value of the electrode structure;
I real time Is the real-time current in the enrichment process;
K chloride decomposition Voltage coefficient 1 Setting a voltage coefficient required by decomposing chlorine salt at an electrolysis temperature;
the K is Chlorine salt decomposition voltage coefficient 1 The obtaining method of (1) comprises the following steps:
K chloride decomposition Voltage coefficient 1 =((V Chlorine salt decomposition voltage + (R Total (S) *I Real time ))*0.9- V Enrichment voltage )/ (R Total (S) *I Real time )；
Dynamically adjusting electrolysis voltage in the electrolysis process;
the temperature in the electrolysis process is 830-1200 ℃;
after enrichment is finished, dynamically adjusting the electrolytic voltage according to the following formula:
V dynamic electrolytic voltage = V Electro-deoxidation voltage + (R Total (S) *I Real time )* K Chloride decomposition voltage coefficient 2 ；
Wherein V is Electro-deoxidation voltage The voltage required for deoxidizing the titanium dioxide at the electrolysis temperature;
R total (S) The total resistance value of the electrode structure;
I real time Is the real-time current in the electrolysis process;
K chloride decomposition voltage coefficient 2 A factor of a voltage required for decomposing chlorine salt at a set electrolysis temperature;
the K is Chloride decomposition voltage coefficient 2 The obtaining method of (1) comprises the following steps:
K chloride decomposition voltage coefficient 2 =((V Chlorine salt decomposition voltage + (R Total (S) *I Real time ))*0.9- V Electro-deoxidation voltage )/ (R Total (S) *I Real time )。
2. The method of claim 1, wherein the sintering temperature is 200-1000 ℃.
3. The method according to claim 1, wherein the chloride salt is selected from CaCl 2 、LiCl、BaCl 2 One or more of NaCl and KCl.
4. The method of claim 1, wherein the cathode structure in the electrolytic process is a sintered product and the anode structure is graphite.
5. The method of claim 1, wherein the chlorine salt is first enriched after melting during the electrolysis; and dynamically adjusting enrichment voltage in the enrichment process to enable:
V enrichment voltage ≤V Enriching dynamic voltage <V Chlorine salt decomposition voltage ；
V Enrichment voltage Is titanium dioxide raw materialThe voltage at which the metal impurities contained therein oxidize to metal ions;
V enriching dynamic voltage Is the voltage dynamically adjusted in the enrichment process;
V chlorine salt decomposition voltage The voltage required for the decomposition of the chloride salt.
6. The method of claim 1, wherein the dynamically adjusting the electrolysis voltage causes:
V electro-deoxidation voltage ≤V Dynamic electrolytic voltage <V Chlorine salt decomposition voltage ；
V Electro-deoxidation voltage The voltage required for deoxidizing the titanium dioxide at the electrolysis temperature;
V dynamic electrolytic voltage Dynamically adjusting the voltage in the electrolysis process;
V chlorine salt decomposition voltage The voltage required for the decomposition of the chloride salt.
7. The method of claim 1, wherein the dynamically adjusted electrolysis voltage is in the range of 3-9 v.
8. The method of claim 5 or 6, wherein V Chlorine salt decomposition voltage 3.04-10.28V.
9. The method of claim 5, wherein the V Enrichment voltage Is 1.2-2.8V.
10. The method of claim 6, wherein the V Electro-deoxidation voltage 1.93 to 1.79V.
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