CA2698025C - Method for preparing metallic titanium by electrolyzing molten salt with titanium circulation - Google Patents
Method for preparing metallic titanium by electrolyzing molten salt with titanium circulation Download PDFInfo
- Publication number
- CA2698025C CA2698025C CA2698025A CA2698025A CA2698025C CA 2698025 C CA2698025 C CA 2698025C CA 2698025 A CA2698025 A CA 2698025A CA 2698025 A CA2698025 A CA 2698025A CA 2698025 C CA2698025 C CA 2698025C
- Authority
- CA
- Canada
- Prior art keywords
- titanium
- molten salt
- electrolyzing
- ticl2
- ticl3
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a method for preparing metallic titanium by electrolyzing molten salt with titanium circulation. The method mainly comprises reducing titanium tetrachloride (TiCl4) to at least one of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) in chloride molten salt by metallic titanium (Ti), and electrolyzing the at least one of TiCl3 and TiCl2 in the chloride molten salt to form metallic titanium. According to the method for preparing metallic titanium of the present invention, TiCl2, and/or TiCl3 are prepared and electrolyzed continuously without changing the surrounding medium, thereby simplifying process flow, reducing power consumption, and realizing industrialization.
Description
METHOD FOR PREPARING METALLIC TITANIUM BY ELECTROLYZING
MOLTEN SALT WITH TITANIUM CIRCULATION
FIELD OF THE INVENTION
The present invention relates to a technical filed of non-ferrous metal metallurgy, more particularly, to a method for preparing metallic titanium by electrolyzing molten salt.
DESCRIPTION OF RELATED ART
Titanium (Ti) is a metal with superior performances, and has many advantages such as low specific gravity, high specific strength, good corrosion resistance and the like.
Titanium alloy also has various excellent properties, for example, good high/low temperature resistance, nonmagnetic, shape memory characteristics, hydrogen absorption characteristics, superconductivity, and low damping characteristics and the like, thus it is an excellent constructional and/or functional material.
Because of numerous advantages of titanium, titanium is called "Metal for outer space", "Marine Metal", "Metal of 21s' century", etc. Consequently, in modem society, metallic titanium and its alloy are increasingly applied to national defense, chemical industry, metallurgy, medical treatment, industrial and agriculture production and other fields, especially to high and new technology industries.
However, it is pretty difficult to extract titanium. Currently, Kroll process is mainly used to produce sponge titanium in the world, and sponge titanium obtained by this process is generally purified by using a method of vacuum arc remelting. In particular, the process of producing sponge titanium by using the Kroll method comprises:
firstly preparing titanium tetrachloride (TiCl4) by chloridizing titanium dioxide (Ti02) with addition of carbon (C) (see the following reaction equation (1)), obtaining sponge titanium by thermally reducing metallic magnesium (see the following reaction equation (2)), and then vacuum distilling the obtained sponge titanium to obtain commercial sponge titanium.
Ti02 + 2C12 + 2C 4 TiC14 + 2CO (1) 2Mg + TiC14 4 2MgC12 +Ti (2) During producing sponge titanium through the Kroll method, metallic Mg is obtained by electrolyzing MgCl2, and chlorine gas (C12) obtained through electrolysis is used to prepare titanium chloride in turn, thus the whole production process comprises four main steps, i.e. chloridization of TiO2, thermal reduction with magnesium, vacuum distillation and electrolysis of MgC12. The method is advantageous in high productivity, is capable of producing sponge titanium with good quality, and facilitates commercialization, thus it seems that this method is irreplaceable so far. On the other hand, the method has disadvantages such as long process flow, excessive steps, high power consumption, and difficulty in achievement of continuous processes, resulting in high manufacturing cost of sponge titanium. For example, the sponge titanium produced by the Kroll method has a price much higher than steel, and has a price per unit weight three times higher than that of metal aluminum. Furthermore, Kroll process has already been a considerably mature process at present, and little improvement in it can be made.
In this case, it is expected that a method for producing metallic titanium with a lower cost can be developed. At present, representative methods comprise: OS
method, FFC process, QIT process, USTB method, PRP method, electrolysis of TiC14, Hunter method, Armstrong method (reduction with Na), SOM technique, producing Ti in vacuum, etc., but the industrialization has not been realized so far due to various disadvantages thereof.
Since TiC14 is used as a raw material in Kroll method, people all conceive of such a method of obtaining metallic titanium by directly electrolyzing TiC14. As a result, the disadvantage existing in reduction and distillation of Kroll method can be avoided.
However, studies have shown that TiCl4, the most common in titanium chlorides, has a pretty high vapor pressure at a temperature of molten salt electrolysis, and has a pretty small solubility (<1%) in melt, thus it is not feasible to use TiC14 as a raw material for directly electrolysis.
Studies on electrolysis of titanium chlorides mostly focus on a method of electrolyzing TiC13. Cordner and Warner from Australia reported their research results at the earliest; in particular, they obtained titanium crystals having a purity of 99% by electrolyzing a mixed molten salt of LiCl-KC1 having TiC13 dissolved therein at a temperature of 550 C. However, it was difficult to realize industrialization of this method due to the following problems: on one hand, there is no available method of preparing TiC13; on the other hand, there is no proper method to supply TiC13 to an electrolytic bath. Additionally, TiC13 is decomposed due to easily absorbing moisture in air, causing pollution to the product.
In addition, there were other research results reported that metallic titanium was prepared by electrolyzing TiC12. However, it could not be industrialized yet, since there was not an available method for preparing TiC12, and it was difficult to add TiC12 to an electrolytic bath and to store it.
SUMMARY OF THE INVENTION
In one aspect, the present invention overcomes the disadvantages such as long process flow; high power consumption or impossibility in realizing industrialization in the conventional method for preparing metallic titanium.
Thus, one aspect of the present invention provides a method for preparing metallic titanium having simple process, low power consumption and being capable of realizing industrialization, by using Ti as a reducing agent to reduce titanium tetrachloride (TiCl4) to titanium trichloride (TiCl3) and/or titanium dichloride (TiCI2).
The present invention provides, in another aspect, a method for preparing metallic titanium by electrolyzing molten salt with titanium circulation comprising: i) reducing titanium tetrachloride (TiCl4) to at least one of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) in chloride molten salt by metallic titanium (Ti); and ii) electrolyzing the at least one of TiC13 and TiC12 in the chloride molten salt to form metallic titanium.
According to another aspect of the present invention, the metallic titanium used in the step i) is a portion of metallic titanium obtained by electrolyzing the at least one of TiC13 and TiC12. A mole ratio of the metallic titanium for reducing to TiC14 is 1:1 to 1:3. The chloride molten salt is at a temperature higher than the eutectic temperature of the molten salt and lower than vaporization temperatures and decomposition temperatures of salts for forming the molten salt. According to preferable embodiments of the present invention, the chloride molten salt is formed by melting two or more of LiCI, NaCl, KCI, MgC12, CaC12, SrC12 and BaC12. The chloride molten salt is at a temperature of 400 C to 850 C.
According to another aspect of the present invention, a small amount of sponge titanium, titanium powder or titanium scrap is added as a titanium source before electrolyzing so as to react with TiCI4, thereby obtaining TiC12, TiC13, or a mixture of TiC12 and TiC13 used as electrolyte to induce electrolysis.
According to another aspect of the present invention, the method further comprises enclosing an anode with a ceramic material article, and collecting liberated at the anode in the step ii).
According to another aspect of the present invention, the method further comprises sequentially washing the generated titanium using hydrochloric acid aqueous solution having a concentration of 0.5 wt%-5 wt% and water after obtaining titanium by electrolyzing the at least one of TiC12 and TiC13, and drying the acid-washed and water-washed titanium in a vacuum oven.
According to another aspect of the method for preparing metallic titanium of the present invention, TiC12, TiC13 or a mixture thereof is prepared and electrolyzed continuously without changing the surrounding medium, thus the problems in the preparation and feeding of TiC12 and/or TiC13 can be solved, no additional foreign substance is introduced in the electrolysis and the operation can be simplified. In addition, C12 generated at the anode can be recovered and reused as a byproduct.
According to still another aspect of the present invention, there is provided a method for preparing metallic titanium by electrolyzing molten salt with titanium circulation, comprising: i) reducing titanium tetrachloride (TiCI4) to at least one of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) in chloride molten salt by metallic titanium (Ti); and ii) electrolyzing the at least one of TiC13 and TiC12 in the chloride molten salt to form metallic titanium, wherein a small amount of sponge titanium, titanium powder or titanium scrap is added as a titanium source before electrolyzing so as to react with TiCI4, thereby obtaining TiC12, TiCI3, or a mixture of TiC12 and TiCI3 as electrolyte to induce electrolysis, and wherein the metallic titanium used in the step i) is a portion of metallic titanium obtained by electrolyzing at least one of TiCI3 and TiC12.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides a method for preparing metallic titanium (Ti). In particular, the present invention provides a method for preparing metallic titanium by electrolyzing titanium trichloride (TiCI3) and/or titanium dichloride (TiCl2) in a molten salt with titanium circulation.
According to the present invention, the method for preparing metallic titanium comprises the following steps:
1) A suitable molten salt system of chloride is selected as an electrolyte, and in the system, TiCI3, TiC12 or a combination thereof with a certain concentration is prepared by using Ti and TiCI4. In particular, TiCI4 is reduced to TiCI3 and/or TiC12 by metallic Ti in the molten salt system (see the following reaction equations (3) and (4)).
Ti + TiCI4 - 2TiCI2 (3) Ti + 3TiCI4 - 4TiCI3 (4) 4a In this step, the chloride molten salt system is required to be dried to sufficiently remove various forms of moisture from the electrolyte.
In the present invention, titanium used at the early stage of electrolysis is the added metallic titanium such as sponge titanium, titanium powder, titanium scrap and the like, so that TiC14 is reduced to TiC12, TiCl3 or a combination thereof. Titanium obtained by electrolyzing is used after the electrolysis process is recycled.
2) TiC12, TiC13 or a combination thereof in the molten salt system is electrolyzed to generate metallic titanium and C12 (see the following reaction equations (5) and (6)).
TiCl2 ->Ti + C12 (5) 2TiCI3 -32Ti + 3C12 (6) According to the present invention, in the step of electrolyzing TiC12, TiC13 or a combination thereof, an anode of the electrolytic bath is made of graphite, and a cathode thereof is made of low carbon steel which is spaced apart from the anode by porous material. Herein, a porous material commonly used in the art can be used to enclose the anode so as to collect chlorine gas liberated from the anode, and can further prevent Tie}, Ti3+ in the molten salt from being oxidized to TiC14 by Cl2 at an anode region. It is preferable to enclose the anode using a ceramic material. The conditions of electrolyzing TiCl2 and/or TiC13 to Ti include a voltage of 2-5V, an anode current density of 0.05-0.6A/cm2, and a cathode current density of 0.1-5 A/cm2.
3) The product obtained at the metal cathode is washed by hydrochloric acid having a concentration of 0.5-5wt%, subsequently by distilled water so that the filtrate contains no chloride ion (Cl - ), and then acid-washed and water-washed titanium is dried in a vacuum oven, thereby obtaining metallic titanium having a relatively high purity.
In addition, it should be noted that TiC14 is continuously or discontinuously introduced to the cathode during the electrolysis so that TiC14 contacts with the titanium at the cathode region. TiC14 may react with Ti to generate low valence-Ti chloride at a certain electrolysis temperature (i.e. the temperature of chloride molten salt, 400-850 C), and the amount and velocity of the introduced TiCl4 are controlled to ensure the electrolysis to proceed smoothly.
The chloride molten salt used in the present invention is a molten salt formed by melting two or more of alkali metal chlorides and alkali-earth metal chlorides, which has a temperature (i.e. electrolysis temperature) higher than the eutectic temperature of the molten salt and lower than vaporization temperatures and decomposition temperatures of the salts for forming the molten salt. In particular, alkali metal chlorides may be one or more of lithium chloride (LiCI), sodium chloride (NaCI) and potassium chloride (KC1), and alkali-earth metal chlorides may be one or more of magnesium chloride (MgC12), calcium chloride (CaC12), strontium chloride (SrC12) and barium chloride (BaC12). According to the present invention, the temperature of chloride molten salt is preferably in a range of 400 C to 850 C. For example, in the present invention, KCl-LiCl system may be selected with a mole ratio of 41%:59%, which has an electrolysis temperature of 400 C to 600 C; NaCI-CaC12 system may also be selected with a mole ratio of 47.1 %:52.9%, which has an electrolysis temperature of 550 C to 750 C; or NaCI-KCI system may also be selected with a mole ratio of 50%:50%, which has an electrolysis temperature of 700 C to 850 C.
According to the present invention, TiC13 and TiC12 in the molten salt system are electrolyzed to generate metallic titanium at the cathode, a portion of which is used as a reducing agent, and to liberate Cl2 at the anode, which is used as a byproduct to be recovered and reused.
In addition, according to the present invention, the concentration of low valence-Ti ion in the electrolyte will be reduced continuously as the electrolysis proceeds, and the concentration of low valence-Ti ion in the electrolyte is required to be controlled within a certain concentration range in order to carry out the electrolysis process more smoothly, thus a predetermined amount of TiCl4 may be introduced into the chloride molten salt periodically so that it reacts with a portion of titanium generated by electrolyzing to generate TiC13, TiC12 or a combination thereof Low valence-Ti to be consumed by electrolyzing in the electrolyte may be added in time, titanium trichloride and/or titanium dichloride generated in the molten salt continue to be electrolyzed, and the above procedures are repeated, thereby building up a complete process of preparing metallic titanium by electrolyzing molten salt with titanium circulation.
MOLTEN SALT WITH TITANIUM CIRCULATION
FIELD OF THE INVENTION
The present invention relates to a technical filed of non-ferrous metal metallurgy, more particularly, to a method for preparing metallic titanium by electrolyzing molten salt.
DESCRIPTION OF RELATED ART
Titanium (Ti) is a metal with superior performances, and has many advantages such as low specific gravity, high specific strength, good corrosion resistance and the like.
Titanium alloy also has various excellent properties, for example, good high/low temperature resistance, nonmagnetic, shape memory characteristics, hydrogen absorption characteristics, superconductivity, and low damping characteristics and the like, thus it is an excellent constructional and/or functional material.
Because of numerous advantages of titanium, titanium is called "Metal for outer space", "Marine Metal", "Metal of 21s' century", etc. Consequently, in modem society, metallic titanium and its alloy are increasingly applied to national defense, chemical industry, metallurgy, medical treatment, industrial and agriculture production and other fields, especially to high and new technology industries.
However, it is pretty difficult to extract titanium. Currently, Kroll process is mainly used to produce sponge titanium in the world, and sponge titanium obtained by this process is generally purified by using a method of vacuum arc remelting. In particular, the process of producing sponge titanium by using the Kroll method comprises:
firstly preparing titanium tetrachloride (TiCl4) by chloridizing titanium dioxide (Ti02) with addition of carbon (C) (see the following reaction equation (1)), obtaining sponge titanium by thermally reducing metallic magnesium (see the following reaction equation (2)), and then vacuum distilling the obtained sponge titanium to obtain commercial sponge titanium.
Ti02 + 2C12 + 2C 4 TiC14 + 2CO (1) 2Mg + TiC14 4 2MgC12 +Ti (2) During producing sponge titanium through the Kroll method, metallic Mg is obtained by electrolyzing MgCl2, and chlorine gas (C12) obtained through electrolysis is used to prepare titanium chloride in turn, thus the whole production process comprises four main steps, i.e. chloridization of TiO2, thermal reduction with magnesium, vacuum distillation and electrolysis of MgC12. The method is advantageous in high productivity, is capable of producing sponge titanium with good quality, and facilitates commercialization, thus it seems that this method is irreplaceable so far. On the other hand, the method has disadvantages such as long process flow, excessive steps, high power consumption, and difficulty in achievement of continuous processes, resulting in high manufacturing cost of sponge titanium. For example, the sponge titanium produced by the Kroll method has a price much higher than steel, and has a price per unit weight three times higher than that of metal aluminum. Furthermore, Kroll process has already been a considerably mature process at present, and little improvement in it can be made.
In this case, it is expected that a method for producing metallic titanium with a lower cost can be developed. At present, representative methods comprise: OS
method, FFC process, QIT process, USTB method, PRP method, electrolysis of TiC14, Hunter method, Armstrong method (reduction with Na), SOM technique, producing Ti in vacuum, etc., but the industrialization has not been realized so far due to various disadvantages thereof.
Since TiC14 is used as a raw material in Kroll method, people all conceive of such a method of obtaining metallic titanium by directly electrolyzing TiC14. As a result, the disadvantage existing in reduction and distillation of Kroll method can be avoided.
However, studies have shown that TiCl4, the most common in titanium chlorides, has a pretty high vapor pressure at a temperature of molten salt electrolysis, and has a pretty small solubility (<1%) in melt, thus it is not feasible to use TiC14 as a raw material for directly electrolysis.
Studies on electrolysis of titanium chlorides mostly focus on a method of electrolyzing TiC13. Cordner and Warner from Australia reported their research results at the earliest; in particular, they obtained titanium crystals having a purity of 99% by electrolyzing a mixed molten salt of LiCl-KC1 having TiC13 dissolved therein at a temperature of 550 C. However, it was difficult to realize industrialization of this method due to the following problems: on one hand, there is no available method of preparing TiC13; on the other hand, there is no proper method to supply TiC13 to an electrolytic bath. Additionally, TiC13 is decomposed due to easily absorbing moisture in air, causing pollution to the product.
In addition, there were other research results reported that metallic titanium was prepared by electrolyzing TiC12. However, it could not be industrialized yet, since there was not an available method for preparing TiC12, and it was difficult to add TiC12 to an electrolytic bath and to store it.
SUMMARY OF THE INVENTION
In one aspect, the present invention overcomes the disadvantages such as long process flow; high power consumption or impossibility in realizing industrialization in the conventional method for preparing metallic titanium.
Thus, one aspect of the present invention provides a method for preparing metallic titanium having simple process, low power consumption and being capable of realizing industrialization, by using Ti as a reducing agent to reduce titanium tetrachloride (TiCl4) to titanium trichloride (TiCl3) and/or titanium dichloride (TiCI2).
The present invention provides, in another aspect, a method for preparing metallic titanium by electrolyzing molten salt with titanium circulation comprising: i) reducing titanium tetrachloride (TiCl4) to at least one of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) in chloride molten salt by metallic titanium (Ti); and ii) electrolyzing the at least one of TiC13 and TiC12 in the chloride molten salt to form metallic titanium.
According to another aspect of the present invention, the metallic titanium used in the step i) is a portion of metallic titanium obtained by electrolyzing the at least one of TiC13 and TiC12. A mole ratio of the metallic titanium for reducing to TiC14 is 1:1 to 1:3. The chloride molten salt is at a temperature higher than the eutectic temperature of the molten salt and lower than vaporization temperatures and decomposition temperatures of salts for forming the molten salt. According to preferable embodiments of the present invention, the chloride molten salt is formed by melting two or more of LiCI, NaCl, KCI, MgC12, CaC12, SrC12 and BaC12. The chloride molten salt is at a temperature of 400 C to 850 C.
According to another aspect of the present invention, a small amount of sponge titanium, titanium powder or titanium scrap is added as a titanium source before electrolyzing so as to react with TiCI4, thereby obtaining TiC12, TiC13, or a mixture of TiC12 and TiC13 used as electrolyte to induce electrolysis.
According to another aspect of the present invention, the method further comprises enclosing an anode with a ceramic material article, and collecting liberated at the anode in the step ii).
According to another aspect of the present invention, the method further comprises sequentially washing the generated titanium using hydrochloric acid aqueous solution having a concentration of 0.5 wt%-5 wt% and water after obtaining titanium by electrolyzing the at least one of TiC12 and TiC13, and drying the acid-washed and water-washed titanium in a vacuum oven.
According to another aspect of the method for preparing metallic titanium of the present invention, TiC12, TiC13 or a mixture thereof is prepared and electrolyzed continuously without changing the surrounding medium, thus the problems in the preparation and feeding of TiC12 and/or TiC13 can be solved, no additional foreign substance is introduced in the electrolysis and the operation can be simplified. In addition, C12 generated at the anode can be recovered and reused as a byproduct.
According to still another aspect of the present invention, there is provided a method for preparing metallic titanium by electrolyzing molten salt with titanium circulation, comprising: i) reducing titanium tetrachloride (TiCI4) to at least one of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) in chloride molten salt by metallic titanium (Ti); and ii) electrolyzing the at least one of TiC13 and TiC12 in the chloride molten salt to form metallic titanium, wherein a small amount of sponge titanium, titanium powder or titanium scrap is added as a titanium source before electrolyzing so as to react with TiCI4, thereby obtaining TiC12, TiCI3, or a mixture of TiC12 and TiCI3 as electrolyte to induce electrolysis, and wherein the metallic titanium used in the step i) is a portion of metallic titanium obtained by electrolyzing at least one of TiCI3 and TiC12.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides a method for preparing metallic titanium (Ti). In particular, the present invention provides a method for preparing metallic titanium by electrolyzing titanium trichloride (TiCI3) and/or titanium dichloride (TiCl2) in a molten salt with titanium circulation.
According to the present invention, the method for preparing metallic titanium comprises the following steps:
1) A suitable molten salt system of chloride is selected as an electrolyte, and in the system, TiCI3, TiC12 or a combination thereof with a certain concentration is prepared by using Ti and TiCI4. In particular, TiCI4 is reduced to TiCI3 and/or TiC12 by metallic Ti in the molten salt system (see the following reaction equations (3) and (4)).
Ti + TiCI4 - 2TiCI2 (3) Ti + 3TiCI4 - 4TiCI3 (4) 4a In this step, the chloride molten salt system is required to be dried to sufficiently remove various forms of moisture from the electrolyte.
In the present invention, titanium used at the early stage of electrolysis is the added metallic titanium such as sponge titanium, titanium powder, titanium scrap and the like, so that TiC14 is reduced to TiC12, TiCl3 or a combination thereof. Titanium obtained by electrolyzing is used after the electrolysis process is recycled.
2) TiC12, TiC13 or a combination thereof in the molten salt system is electrolyzed to generate metallic titanium and C12 (see the following reaction equations (5) and (6)).
TiCl2 ->Ti + C12 (5) 2TiCI3 -32Ti + 3C12 (6) According to the present invention, in the step of electrolyzing TiC12, TiC13 or a combination thereof, an anode of the electrolytic bath is made of graphite, and a cathode thereof is made of low carbon steel which is spaced apart from the anode by porous material. Herein, a porous material commonly used in the art can be used to enclose the anode so as to collect chlorine gas liberated from the anode, and can further prevent Tie}, Ti3+ in the molten salt from being oxidized to TiC14 by Cl2 at an anode region. It is preferable to enclose the anode using a ceramic material. The conditions of electrolyzing TiCl2 and/or TiC13 to Ti include a voltage of 2-5V, an anode current density of 0.05-0.6A/cm2, and a cathode current density of 0.1-5 A/cm2.
3) The product obtained at the metal cathode is washed by hydrochloric acid having a concentration of 0.5-5wt%, subsequently by distilled water so that the filtrate contains no chloride ion (Cl - ), and then acid-washed and water-washed titanium is dried in a vacuum oven, thereby obtaining metallic titanium having a relatively high purity.
In addition, it should be noted that TiC14 is continuously or discontinuously introduced to the cathode during the electrolysis so that TiC14 contacts with the titanium at the cathode region. TiC14 may react with Ti to generate low valence-Ti chloride at a certain electrolysis temperature (i.e. the temperature of chloride molten salt, 400-850 C), and the amount and velocity of the introduced TiCl4 are controlled to ensure the electrolysis to proceed smoothly.
The chloride molten salt used in the present invention is a molten salt formed by melting two or more of alkali metal chlorides and alkali-earth metal chlorides, which has a temperature (i.e. electrolysis temperature) higher than the eutectic temperature of the molten salt and lower than vaporization temperatures and decomposition temperatures of the salts for forming the molten salt. In particular, alkali metal chlorides may be one or more of lithium chloride (LiCI), sodium chloride (NaCI) and potassium chloride (KC1), and alkali-earth metal chlorides may be one or more of magnesium chloride (MgC12), calcium chloride (CaC12), strontium chloride (SrC12) and barium chloride (BaC12). According to the present invention, the temperature of chloride molten salt is preferably in a range of 400 C to 850 C. For example, in the present invention, KCl-LiCl system may be selected with a mole ratio of 41%:59%, which has an electrolysis temperature of 400 C to 600 C; NaCI-CaC12 system may also be selected with a mole ratio of 47.1 %:52.9%, which has an electrolysis temperature of 550 C to 750 C; or NaCI-KCI system may also be selected with a mole ratio of 50%:50%, which has an electrolysis temperature of 700 C to 850 C.
According to the present invention, TiC13 and TiC12 in the molten salt system are electrolyzed to generate metallic titanium at the cathode, a portion of which is used as a reducing agent, and to liberate Cl2 at the anode, which is used as a byproduct to be recovered and reused.
In addition, according to the present invention, the concentration of low valence-Ti ion in the electrolyte will be reduced continuously as the electrolysis proceeds, and the concentration of low valence-Ti ion in the electrolyte is required to be controlled within a certain concentration range in order to carry out the electrolysis process more smoothly, thus a predetermined amount of TiCl4 may be introduced into the chloride molten salt periodically so that it reacts with a portion of titanium generated by electrolyzing to generate TiC13, TiC12 or a combination thereof Low valence-Ti to be consumed by electrolyzing in the electrolyte may be added in time, titanium trichloride and/or titanium dichloride generated in the molten salt continue to be electrolyzed, and the above procedures are repeated, thereby building up a complete process of preparing metallic titanium by electrolyzing molten salt with titanium circulation.
Furthermore, it should be noted that there is only one molten salt system formed in the whole electrolysis, i.e. the molten salt system of chlorides of alkali metal and/or alkali earth-metal with TiC12/TiCl3, such as NaCI-KC1-TiC12/TiC13 or CaC12-KCI-TiC12/TiC13, since titanium (Ti) is directly used as the reducing agent in the present invention. Therefore, no additional foreign substance is introduced in the electrolysis processes for preparing metallic titanium according to the present invention, and the operation parameters are kept the same in the whole electrolysis, thereby reducing cost and facilitating operation.
Hereinafter, the present invention will be further explained in connection with embodiments.
Embodiment 1 A chloride molten salt system was prepared. 117g of NaCl (analytical reagent) and 149g of KCI (analytical reagent) were mixed uniformly and dried in an oven at for 24 hours, followed by dried in a reactor made of stainless steel under vacuum at 35011-4500 for 48 hours so that various forms of moisture contained in the electrolyte was sufficiently removed.
In this system, an electrolyte having a Ti2+ concentration of 5% was prepared using sponge titanium and TiC14. The temperature was then increased to 70011 in an Ar atmosphere to perform constant-current electrolysis. The anode was made of graphite and was spaced apart from the cathode by a porous material (preferably ceramic material) so as to facilitate collecting C12 liberated from the anode, while avoiding the possibility of oxidizing Ti2+, Ti3+ in the molten salt to TiC14 by C12 liberated at the anode region. The cathode was made of low carbon steel. The electrolysis system had an anode current density of 0.3A/cm2, a cathode current density of 1.2A/cm2, an anode-cathode distance of 6cm, a current intensity of 1OA, and 7g of metallic titanium was obtained based on 80% of current efficiency after lhr of electrolysis time. At this time, 25g of TiC14 was introduced to the cathode region in the molten salt to generate TiCl2, and the generated TiC14 was electrolyzed for I hr under the conditions of a current intensity of 15A and other parameters (i.e. the anode current density, the cathode current density, and the anode-cathode distance) the same as above.
After electrolysis, the cathode product was firstly washed by 1 wt% of hydrochloric acid to be colorless, and then washed by distilled water to have no chloride ion, followed by dried in a vacuum oven, thereby obtaining 12.08g of titanium powder. The results obtained by analyzing a sample were as follows: a Ti content of 99.83%, an oxygen content of 0.085%, a carbon content less than 0.02%, and an iron content less than 0.045% by weight of the product. The current efficiency of TiCl2 electrolysis was calculated as 89.98%.
Embodiment 2 After 40g of LiCI, 46g of NaCl and 22g of KC1 were weighed and mixed uniformly, a chloride molten salt system was prepared through dehydrating process in the same manner as that in Embodiment 1.
In this system, an electrolyte having a Ti3+ concentration of 6% was prepared using sponge titanium and TiC14. The temperature was then increased to 6000 in an Ar atmosphere to perform constant-current electrolysis. By using the same anode and cathode devices as those in Embodiment 1, the electrolysis system had an anode current density of 0.5A/cm2, a cathode current density of 3A/cm2, an anode-cathode distance of 5cm, and a current intensity of 6A, and 4.6g of metallic titanium was obtained based on 85% of current efficiency after lhr of electrolysis time. At this time, 55g of TiC14 was introduced to the cathode region in the molten salt to generate TiC13, and the generated TiC13 was electrolyzed for 2hr under the conditions of a current intensity of 8A and other parameters the same as above.
After electrolysis, the cathode product was firstly washed by 5wt%
hydrochloric acid to be colorless, and then washed by distilled water to have no chloride ion, followed by dried in a vacuum oven, thereby obtaining 12.65g of titanium powder. The results obtained by analyzing a sample were as follows: a Ti content of 99.72%, an oxygen content of 0.072%, a carbon content less than 0.02%, and an iron content less than 0.060% by weight of the product. The current efficiency of TiCl3 electrolysis was calculated as 88.37%.
Embodiment 3 After 70g of CaCl2 and 80g of KCl were weighed and mixed uniformly, a chloride molten salt system was prepared through dehydrating process in the same manner as that in Embodiment 1.
In this system, an electrolyte having a combined concentration of Ti2+ and Ti3+ of 10% was prepared using sponge titanium and TiC14. The temperature was then increased to 8000 in an Ar atmosphere to perform constant-current electrolysis. By using the same anode and cathode devices as those in Embodiment 1, the electrolysis system had an anode current density of 0.1 A/cm2, a cathode current density of 0.5A/em2, an anode-cathode distance of 5cm, and a current intensity of 12A, and 8g of metallic titanium was liberated based on 85% of current efficiency after lhr of electrolysis time.
At this time, 65g of TiC14 was introduced to the cathode region in the molten salt to generate a mixture of TiC12 and TiC13, and the generated TiC12 and TiC13 were electrolyzed for 2hr under the conditions of a current intensity of 8A and other parameters the same as above.
After electrolysis, the cathode product was firstly washed by 0.5wt%
hydrochloric acid to be colorless, and then washed by distilled water to have no chloride ion, followed by dried in a vacuum oven, thereby obtaining 10.20g of titanium powder. The results obtained by analyzing a sample were as follows: a Ti content of 99.67%, an oxygen content of 0.09%, a carbon content less than 0.03%, and an iron content less than 0.05% by weight of the product. The current efficiency of TiC12 and TiC13 electrolysis in combination was calculated as 78.07%.
It can be known from the experiment results of Embodiments 1-3 that the contents of Ti in the products were all above 99.6%, which showed that the generated titanium powders have high purity and can be directly cast, and that the current efficiencies in electrolyzing were all above 87%, which showed that the method for preparing metallic titanium according to the present invention can produce metallic titanium with high yield and low power consumption.
It can be known from the above embodiments that TiC12, TiC13 or a mixture thereof is prepared and electrolyzed continuously in the method for preparing metallic titanium according to the present invention, without changing the surrounding medium, thereby solving the problems in the preparation and feeding of TiC12 and/or TiC13. In addition, C12 generated at the anode can be recovered and reused as a byproduct.
Therefore, compared with the conventional method for preparing metallic titanium by electrolyzing, the method for preparing metallic titanium by electrolyzing molten salt with titanium circulation according to the present invention can simplify preparation process, reduce power consumption, and realize industrialization.
Hereinafter, the present invention will be further explained in connection with embodiments.
Embodiment 1 A chloride molten salt system was prepared. 117g of NaCl (analytical reagent) and 149g of KCI (analytical reagent) were mixed uniformly and dried in an oven at for 24 hours, followed by dried in a reactor made of stainless steel under vacuum at 35011-4500 for 48 hours so that various forms of moisture contained in the electrolyte was sufficiently removed.
In this system, an electrolyte having a Ti2+ concentration of 5% was prepared using sponge titanium and TiC14. The temperature was then increased to 70011 in an Ar atmosphere to perform constant-current electrolysis. The anode was made of graphite and was spaced apart from the cathode by a porous material (preferably ceramic material) so as to facilitate collecting C12 liberated from the anode, while avoiding the possibility of oxidizing Ti2+, Ti3+ in the molten salt to TiC14 by C12 liberated at the anode region. The cathode was made of low carbon steel. The electrolysis system had an anode current density of 0.3A/cm2, a cathode current density of 1.2A/cm2, an anode-cathode distance of 6cm, a current intensity of 1OA, and 7g of metallic titanium was obtained based on 80% of current efficiency after lhr of electrolysis time. At this time, 25g of TiC14 was introduced to the cathode region in the molten salt to generate TiCl2, and the generated TiC14 was electrolyzed for I hr under the conditions of a current intensity of 15A and other parameters (i.e. the anode current density, the cathode current density, and the anode-cathode distance) the same as above.
After electrolysis, the cathode product was firstly washed by 1 wt% of hydrochloric acid to be colorless, and then washed by distilled water to have no chloride ion, followed by dried in a vacuum oven, thereby obtaining 12.08g of titanium powder. The results obtained by analyzing a sample were as follows: a Ti content of 99.83%, an oxygen content of 0.085%, a carbon content less than 0.02%, and an iron content less than 0.045% by weight of the product. The current efficiency of TiCl2 electrolysis was calculated as 89.98%.
Embodiment 2 After 40g of LiCI, 46g of NaCl and 22g of KC1 were weighed and mixed uniformly, a chloride molten salt system was prepared through dehydrating process in the same manner as that in Embodiment 1.
In this system, an electrolyte having a Ti3+ concentration of 6% was prepared using sponge titanium and TiC14. The temperature was then increased to 6000 in an Ar atmosphere to perform constant-current electrolysis. By using the same anode and cathode devices as those in Embodiment 1, the electrolysis system had an anode current density of 0.5A/cm2, a cathode current density of 3A/cm2, an anode-cathode distance of 5cm, and a current intensity of 6A, and 4.6g of metallic titanium was obtained based on 85% of current efficiency after lhr of electrolysis time. At this time, 55g of TiC14 was introduced to the cathode region in the molten salt to generate TiC13, and the generated TiC13 was electrolyzed for 2hr under the conditions of a current intensity of 8A and other parameters the same as above.
After electrolysis, the cathode product was firstly washed by 5wt%
hydrochloric acid to be colorless, and then washed by distilled water to have no chloride ion, followed by dried in a vacuum oven, thereby obtaining 12.65g of titanium powder. The results obtained by analyzing a sample were as follows: a Ti content of 99.72%, an oxygen content of 0.072%, a carbon content less than 0.02%, and an iron content less than 0.060% by weight of the product. The current efficiency of TiCl3 electrolysis was calculated as 88.37%.
Embodiment 3 After 70g of CaCl2 and 80g of KCl were weighed and mixed uniformly, a chloride molten salt system was prepared through dehydrating process in the same manner as that in Embodiment 1.
In this system, an electrolyte having a combined concentration of Ti2+ and Ti3+ of 10% was prepared using sponge titanium and TiC14. The temperature was then increased to 8000 in an Ar atmosphere to perform constant-current electrolysis. By using the same anode and cathode devices as those in Embodiment 1, the electrolysis system had an anode current density of 0.1 A/cm2, a cathode current density of 0.5A/em2, an anode-cathode distance of 5cm, and a current intensity of 12A, and 8g of metallic titanium was liberated based on 85% of current efficiency after lhr of electrolysis time.
At this time, 65g of TiC14 was introduced to the cathode region in the molten salt to generate a mixture of TiC12 and TiC13, and the generated TiC12 and TiC13 were electrolyzed for 2hr under the conditions of a current intensity of 8A and other parameters the same as above.
After electrolysis, the cathode product was firstly washed by 0.5wt%
hydrochloric acid to be colorless, and then washed by distilled water to have no chloride ion, followed by dried in a vacuum oven, thereby obtaining 10.20g of titanium powder. The results obtained by analyzing a sample were as follows: a Ti content of 99.67%, an oxygen content of 0.09%, a carbon content less than 0.03%, and an iron content less than 0.05% by weight of the product. The current efficiency of TiC12 and TiC13 electrolysis in combination was calculated as 78.07%.
It can be known from the experiment results of Embodiments 1-3 that the contents of Ti in the products were all above 99.6%, which showed that the generated titanium powders have high purity and can be directly cast, and that the current efficiencies in electrolyzing were all above 87%, which showed that the method for preparing metallic titanium according to the present invention can produce metallic titanium with high yield and low power consumption.
It can be known from the above embodiments that TiC12, TiC13 or a mixture thereof is prepared and electrolyzed continuously in the method for preparing metallic titanium according to the present invention, without changing the surrounding medium, thereby solving the problems in the preparation and feeding of TiC12 and/or TiC13. In addition, C12 generated at the anode can be recovered and reused as a byproduct.
Therefore, compared with the conventional method for preparing metallic titanium by electrolyzing, the method for preparing metallic titanium by electrolyzing molten salt with titanium circulation according to the present invention can simplify preparation process, reduce power consumption, and realize industrialization.
The above description is only to illustrate some principles of the present invention, and does not limit the present invention to the scope as described above.
Therefore, all available corresponding modifications and equivalents fall into the scope claimed in the present invention, without departing from the spirit and scope of the present invention as defined in the claims and their equivalents.
Therefore, all available corresponding modifications and equivalents fall into the scope claimed in the present invention, without departing from the spirit and scope of the present invention as defined in the claims and their equivalents.
Claims (6)
1. A method for preparing metallic titanium by electrolyzing molten salt with titanium circulation, comprising:
i) reducing titanium tetrachloride (TiCl4) to at least one of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) in chloride molten salt by metallic titanium (Ti); and ii) electrolyzing the at least one of TiCl3 and TiCl2 in the chloride molten salt to form metallic titanium, wherein a small amount of sponge titanium, titanium powder or titanium scrap is added as a titanium source before electrolyzing so as to react with TiCl4, thereby obtaining TiCl2, TiCl3, or a mixture of TiCl2 and TiCl3 as electrolyte to induce electrolysis, and wherein the metallic titanium used in the step i) is a portion of metallic titanium obtained by electrolyzing at least one of TiCl3 and TiCl2.
i) reducing titanium tetrachloride (TiCl4) to at least one of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) in chloride molten salt by metallic titanium (Ti); and ii) electrolyzing the at least one of TiCl3 and TiCl2 in the chloride molten salt to form metallic titanium, wherein a small amount of sponge titanium, titanium powder or titanium scrap is added as a titanium source before electrolyzing so as to react with TiCl4, thereby obtaining TiCl2, TiCl3, or a mixture of TiCl2 and TiCl3 as electrolyte to induce electrolysis, and wherein the metallic titanium used in the step i) is a portion of metallic titanium obtained by electrolyzing at least one of TiCl3 and TiCl2.
2. The method of claim 1, wherein a mole ratio of the metallic titanium for reducing to TiCl4 is 1:1 to 1:3.
3. The method of claim 1, wherein the chloride molten salt is formed by melting two or more of LiCl, NaCl, KCl, MgCl2, CaCl2, SrCl2 and BaCl2.
4. The method of claim 1, wherein the chloride molten salt is at a temperature higher than the eutectic temperature of the chloride molten salt and lower than vaporization temperatures and decomposition temperatures of salts for forming the chloride molten salt.
5. The method of claim 4, wherein the chloride molten salt is at a temperature of 400°C to 850°C.
6. The method of claim 1, further comprising: collecting Cl2 liberated from an anode in the step ii).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910128311A CN101519789A (en) | 2009-03-30 | 2009-03-30 | Method for preparing metallic titanium by electrolyzing titanium-circulated molten salt |
| CN200910128311.5 | 2009-03-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2698025A1 CA2698025A1 (en) | 2010-09-30 |
| CA2698025C true CA2698025C (en) | 2012-10-09 |
Family
ID=41080580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2698025A Active CA2698025C (en) | 2009-03-30 | 2010-03-29 | Method for preparing metallic titanium by electrolyzing molten salt with titanium circulation |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20100243468A1 (en) |
| CN (1) | CN101519789A (en) |
| CA (1) | CA2698025C (en) |
| IT (1) | IT1399969B1 (en) |
| UA (1) | UA95025C2 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA024674B1 (en) * | 2010-11-02 | 2016-10-31 | Кеки Хормусджи Гхарда | Process for manufacturing lower chlorides of titanium |
| CN102115831B (en) * | 2011-03-02 | 2012-12-26 | 朝阳金达钛业有限责任公司 | Method for preparing titanium sponge |
| KR101135159B1 (en) * | 2011-11-18 | 2012-04-16 | 한국지질자원연구원 | Method for manufacturing titanium powder with low oxygen concentration |
| JP6228550B2 (en) | 2011-12-22 | 2017-11-08 | ユニヴァーサル テクニカル リソース サービシーズ インコーポレイテッド | Apparatus and method for titanium extraction and refining |
| CN102534261B (en) * | 2012-01-18 | 2013-04-10 | 深圳市新星轻合金材料股份有限公司 | Process method for preparing titanium sponge |
| CN102912379A (en) * | 2012-10-25 | 2013-02-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metal titanium |
| CN103898555A (en) * | 2012-12-25 | 2014-07-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal titanium production method |
| CN103147096B (en) * | 2013-03-28 | 2015-07-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing molten-salt electrolyte containing low-valent titanium chloride and method for extracting titanium |
| CN103451682B (en) | 2013-09-16 | 2017-06-06 | 北京科技大学 | A kind of method of titaniferous soluble anode electroextraction by molten salt electrolysis titanium |
| CN105780058A (en) * | 2014-12-23 | 2016-07-20 | 宁波创润新材料有限公司 | Cleaning method of cathode electrolytic products |
| CN105220182B (en) * | 2015-10-29 | 2017-10-31 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for preparing porous titanium valve |
| CN105350028B (en) * | 2015-11-24 | 2017-12-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Molten-salt electrolysis prepares Nitinol powder and preparation method thereof |
| US10550489B2 (en) * | 2016-07-11 | 2020-02-04 | Uchicago Argonne, Llc | Actinide and rare earth drawdown system for molten salt recycle |
| WO2018125322A1 (en) | 2016-09-14 | 2018-07-05 | Universal Technical Resource Services, Inc. | A method for producing titanium-aluminum-vanadium alloy |
| AU2018249909B2 (en) | 2017-01-13 | 2023-04-06 | Universal Achemetal Titanium, Llc | Titanium master alloy for titanium-aluminum based alloys |
| CN107475539B (en) * | 2017-08-18 | 2019-05-17 | 中南大学 | A kind of method that gaseous state electrochemistry prepares Titanium |
| CN107758731A (en) * | 2017-11-24 | 2018-03-06 | 郑州大学 | A kind of method and apparatus for preparing titanium trichloride powder |
| CN109280941B (en) | 2018-11-16 | 2020-02-28 | 北京科技大学 | A method for preparing titanium metal from ilmenite composite ore, carbon sulfide-electrolysis |
| CN113881972B (en) * | 2021-11-15 | 2023-07-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Molten salt electrolytic refining method and method for separating cathode precipitates thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3054735A (en) * | 1960-03-29 | 1962-09-18 | New Jersey Zinc Co | Production of titanium |
| FR2494726A1 (en) * | 1980-11-27 | 1982-05-28 | Armand Marcel | IMPROVED PROCESS FOR THE PREPARATION OF TITANIUM BY ELECTROLYSIS |
| CA2582039A1 (en) * | 2004-10-12 | 2006-04-20 | Toho Titanium Co., Ltd. | Method for producing metal by molten salt electrolysis and method for producing metal titanium |
-
2009
- 2009-03-30 CN CN200910128311A patent/CN101519789A/en active Pending
-
2010
- 2010-03-26 UA UAA201003507A patent/UA95025C2/en unknown
- 2010-03-26 US US12/732,362 patent/US20100243468A1/en not_active Abandoned
- 2010-03-29 IT ITTO2010A000243A patent/IT1399969B1/en active
- 2010-03-29 CA CA2698025A patent/CA2698025C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| UA95025C2 (en) | 2011-06-25 |
| US20100243468A1 (en) | 2010-09-30 |
| IT1399969B1 (en) | 2013-05-09 |
| CA2698025A1 (en) | 2010-09-30 |
| ITTO20100243A1 (en) | 2010-10-01 |
| CN101519789A (en) | 2009-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2698025C (en) | Method for preparing metallic titanium by electrolyzing molten salt with titanium circulation | |
| CN103298742B (en) | Process for preparing titanium chloride | |
| Kipouros et al. | A thermochemical analysis of the production of anhydrous MgCl2 | |
| CN103451682B (en) | A kind of method of titaniferous soluble anode electroextraction by molten salt electrolysis titanium | |
| CN108251866B (en) | A kind of preparation method of metallic titanium powder | |
| Zhang et al. | A perspective on thermochemical and electrochemical processes for titanium metal production | |
| CN101914788A (en) | A kind of method for preparing metal titanium | |
| CN101649472A (en) | Method for preparing metallic titanium | |
| PT2177636E (en) | A method of producing titanium powder | |
| CN101949038B (en) | Method for preparing TiCxOy composite anode with electrolysis method | |
| CN104947152A (en) | Method for preparing high-purity titanium by fused-salt electrolytic refining | |
| CN114672850B (en) | Method for preparing metallic titanium by separating titanium-aluminum alloy through molten salt electrolytic deoxidation | |
| CN109811370B (en) | Method for preparing metal titanium by electrolyzing-titanium carbon sulfur anode | |
| CN102586629B (en) | Cyclic preparation method for producing titanium sponge and synchronously producing elpasolite by using potassium fluotitanate as intermediate raw material | |
| Seki et al. | Reduction of titanium dioxide to metallic titanium by nitridization and thermal decomposition | |
| CN110983378A (en) | Device and method for preparing metal aluminum and titanium tetrachloride from soluble anode in molten salt | |
| CN103882476B (en) | Preparation methods for low valence state titanium chloride-containing electrolyte and metal titanium | |
| GB2513931A (en) | Method for cyclically preparing titanium sponge and simultaneously producing sodium cryolite using sodium fluorotitanate as an intermediate material | |
| CN107587168A (en) | The method that molten-salt electrolysis prepares Titanium | |
| CN104671270A (en) | Anhydrous aluminum chloride preparation method | |
| CN110079837A (en) | The method that water-soluble fluorine salt system molten-salt electrolysis soluble titanium hydrochlorate prepares Titanium | |
| Kero et al. | Technologies with potential for climate neutral silicon production | |
| CN104611727B (en) | A kind of preparation method of molten-salt electrolysis with chloride composite electrolyte | |
| CN105088283B (en) | A kind of method for extracting Titanium | |
| CN115707798A (en) | Method for preparing metal Ti based on low-temperature molten salt electrolysis dealumination of titanium-aluminum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |