Preparation device and preparation method of metal Ti

Abstract

The invention relates to the field of inorganic chemistry, electrochemistry and powder metallurgy science, in particular to a preparation device and a preparation method of metal Ti. The preparation device of the metal Ti comprises the reactor, the anode device and at least one group of cathode devices, preferably, the number of the cathode devices is multiple, so that cathode reactions can be carried out at the same time to improve the yield, different cathodes can also be carried out in turn to carry out the cathode reactions, continuous production is realized, and the production efficiency is improved. According to the preparation method of the metal Ti, the yield and quality of titanium are improved by improving the electrochemical performance of an electrolyte and the mass transfer rate of titanium tetrachloride, molten salt MgCl2 is used as the electrolyte, and the depth of a metal cathode immersed in the molten salt MgCl2 is continuously changed in the reaction process, so that the metal Ti is uniformly deposited on the surface of the metal cathode; and meanwhile, the cathode current density is controlled to be 0.1-10A / cm < 2 >, and the feeding rate of TiCl4 is 130-200g / A.h, so that the yield and the quality of a metallic titanium product are improved.

Description

Technical Field

[0001] The invention relates to the fields of inorganic chemistry, electrochemistry and powder metallurgy, and in particular to a preparation device and a preparation method of metal Ti. Background Art

[0002] Titanium is a structural material developed in the 1950s. It has excellent properties such as low density, high specific strength, easy processing, high temperature resistance and strong corrosion resistance. It is widely used in many fields such as aerospace, marine engineering, biomedicine and civil use, and is known as the "modern metal".

[0003] In the prior art, EP05799311A (Hori M., Ogasawara T., Yamaquchi M., etc., published on August 8, 2007) discloses a method and device for preparing Ti by calcium reduction. Figure 1 As shown, it includes an electrolytic cell and a reaction tank, and the electrolytic cell and the reaction tank are connected by a continuum. The molten salt CaCl in the electrolytic cell is electrolyzed, and Ca is generated on the cathode side (the continuum 5 constitutes the cathode). Ca is deposited and attached to the continuum and transported to the reaction tank to react with TiCl4 to form Ti. In this invention, the electrolysis of CaCl2 can replenish the Ca consumed in the reduction reaction of TiCl4, and the continuous production of Ti can be formed by increasing the feed rate of the raw material TiCl4, which has economic advantages. The disadvantages of this method are: below 900°C, the continuum in the device is difficult to move, resulting in a low output of Ti, and because the high conductivity of the CaCl melt determines the high solubility of calcium in the electrolyte, the quality of the output Ti is poor.

[0004] "Reduction of TiCl4 Gas by Ca Dissolved in Molten Calcium Chloride" (Takayuki Naito, Ryosuke O.Suzuki, Yoichi Tomii.) proposed a method for preparing titanium metal by reducing TiCl4 gas with calcium dissolved in molten calcium chloride. The principle of this method is as follows Figure 2As shown, it mainly includes two steps. ① Electrolyze molten calcium chloride at a temperature of about 1173K, release chlorine gas at the anode, and reduce metallic calcium to dissolve in the molten calcium chloride near the cathode; ② Inject TiCl4 gas into the cathode chamber, and use Ca to reduce TiCl4 to produce metallic titanium (2Ca(in CaCl2)+TiCl4(gas)=Ti(solid)+2CaCl2(liquid)). Part of the prepared metallic titanium accumulates on the metal cathode, and the other part is deposited at the bottom of the electrolytic cell. The disadvantage of this method is that when the concentration of Ca used to reduce TiCl4 is low, the yield of metallic titanium will be low, and the quality of the prepared metallic titanium is poor, containing impurities such as titanium oxide and titanium trioxide. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a preparation device and a preparation method of metal Ti, and the present invention specifically includes the following contents:

[0006] A device for preparing metal Ti, comprising a reactor, an anode device, and at least one cathode device.

[0007] An electrolyte is arranged inside the reactor, and a sealing cover is covered on the reactor, wherein the sealing cover is provided with an anode reserved opening and at least one cathode reserved opening;

[0008] The anode device comprises an anode diaphragm, an anode fixing cover and an anode, wherein the anode diaphragm encloses an anode chamber, wherein the lower end of the anode chamber is arranged in the electrolyte in the reactor, and the upper end thereof is arranged above the sealing cover through the anode reserved opening, an anode cover is arranged at the upper end of the anode chamber, and an anode gas outlet is also arranged at the upper part of the anode chamber; the upper end of the anode is arranged above the anode cover, and the lower end thereof is arranged in the anode chamber through the anode cover and immersed in the electrolyte;

[0009] The cathode device includes a cathode tower and a cathode. The cathode tower is arranged above the cathode reserved port. The cathode tower is provided with a first cathode air inlet, a second cathode air inlet, a second cathode air outlet, and a vacuum port. The air outlet is provided with a vacuum valve. The upper end of the cathode tower is provided with a cathode cover. The upper end of the cathode is arranged above the cathode cover, and the lower end passes through the cathode cover and the cathode reserved port in sequence and is immersed in the electrolyte. During the preparation process, the first cathode air inlet is used to transport TiCl4 gas to the cathode, the second cathode air inlet is used to transport argon gas, and the second cathode air outlet is used to output argon gas and TiCl4 gas remaining on the cathode surface. The part surrounded by the anode diaphragm in the reactor is the anode chamber, and the rest forms the cathode chamber. In this device, the number of the cathode devices is at least one group, preferably multiple groups, so that the cathode reaction can be carried out simultaneously to increase the output, and different cathodes can be made to take turns to carry out the cathode reaction to achieve continuous production and improve production efficiency.

[0010] Preferably, an anode chamber seal is provided at the intersection of the anode diaphragm and the anode reserved opening; an anode seal is provided at the intersection of the anode and the anode cover; a cathode tower seal is provided at the position where the bottom of the cathode tower contacts the sealing cover; and a cathode seal is provided at the intersection of the cathode and the cathode cover.

[0011] Preferably, it also includes a power supply device, a valve system, a detection system and an automatic control system which are respectively connected to the cathode and the anode through circuits, wherein the valve system is used to control the feeding and discharging of the entire device; the detection system is used to detect the internal information of the device; the automatic control system is connected to the power supply device, the valve system and the detection system, and is used to control the automatic operation of the entire device, realize automatic control of temperature, pressure, vacuum, current and voltage, and TiCl4 feeding rate, and display all working states.

[0012] Preferably, the valve system includes an anode outlet valve arranged outside the anode outlet, a first cathode inlet valve arranged outside the first cathode inlet, a second cathode inlet valve arranged outside the second cathode inlet, a second cathode outlet valve arranged outside the second cathode outlet, a vacuum valve arranged outside the gas extraction port, a third cathode inlet valve arranged outside the third cathode inlet, and a third cathode outlet valve arranged outside the third cathode outlet;

[0013] The detection system includes a current detection device and a voltage detection device arranged on the circuit, an electrolyte temperature detection device arranged in the reactor, an anode pressure detection device arranged at the anode gas outlet, a vacuum detection device and a cathode temperature detection device arranged in the cathode tower;

[0014] The automatic control system includes a receiving module, a computing module, a display module, and a control module. The computing module and the display module are connected to the receiving module and the control module respectively; the receiving module is connected to the current detection device, the voltage detection device, the electrolyte temperature detection device, the anode pressure detection device, the vacuum detection device, and the cathode temperature detection device respectively; the control module is connected to the power supply device, the anode outlet valve, the first cathode inlet valve, the second cathode inlet valve, the second cathode outlet valve, the vacuum valve, the third cathode inlet valve, and the third cathode outlet valve respectively. In the actual working project, the control program can be input into the computing module in advance. During the preparation process, the computing module will generate control instructions according to the real-time detection data and the preset program, and transmit them to the specified device through the control module to realize the automatic control of the entire device.

[0015] Preferably, the cathode tower is further provided with a third cathode air inlet and a third cathode air outlet, a third cathode air inlet valve is provided outside the third cathode air inlet, and a third cathode air outlet valve is provided outside the third cathode air outlet; the third cathode air inlet valve and the third cathode air outlet valve are respectively connected to a control module in an automatic control system. The third cathode air inlet and the third cathode air outlet can be used to transport and output condensed water to and from the cathode tower.

[0016] Preferably, it also includes a cathode lifting device, which includes a motor, a transmission device and a lifting mechanism, one end of the lifting mechanism is detachably connected to the upper end of the cathode, and the other end is linked to the motor through the transmission device; the motor is connected to the control module in the automatic control system. The cathode lifting device can realize the lifting and lowering control of the cathode, and can automatically control the lifting and lowering of the cathode during the working process, which can save the cost of manual operation and make the operation more accurate and efficient.

[0017] A method for preparing metal Ti using the device described above, using molten salt MgCl2 as an electrolyte for electrolytic reaction, generating metal magnesium and chlorine, causing chlorine to be discharged from the anode chamber, and metal magnesium to dissolve in the molten salt MgCl2; at the same time, TiCl4 gas is continuously introduced into the cathode, so that TiCl4 and metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-cathode-gaseous TiCl4 to generate metal Ti, and deposit on the cathode surface; during the reaction, the depth of the cathode immersed in the molten salt MgCl2 is continuously adjusted, so that metal Ti is uniformly deposited on the cathode surface. The method described in the present invention uses molten salt magnesium chloride as an electrolyte, and the titanium content of the obtained product metal Ti is relatively high, wherein the residual magnesium and the electrolyte molten salt MgCl2 can be simply removed by vacuum distillation or hydrometallurgy, and the product quality is high; and the metal magnesium and the molten salt MgCl2 can be reused after condensation and recovery, and the production cost is controllable. In order to make the metal Ti deposited uniformly and stably on the metal cathode, the present invention continuously changes the depth of the cathode immersed in the melt during the electrolysis process (making the metal cathode reciprocate in the direction perpendicular to the electrolyte). During the reaction, if the depth of the metal cathode immersed in the molten salt MgCl2 remains unchanged, metallic titanium is deposited on the three-phase interface of electrolyte-metal cathode-gaseous TiCl4. The Ti deposition layer on the surface of the metal cathode is unevenly distributed, which will make it difficult to remove the metal cathode from the reactor and make the metal Ti easily collapse into the molten salt electrolyte.

[0018] Preferably, the reaction temperature is controlled to be 750-800°C; and / or the cathode current density is 0.1-10A / cm 2 If the cathode current density is less than 0.1A / cm 2 , a small amount of TiCl2 and TiCl3 will appear near the metal cathode, resulting in a decrease in the yield and quality of metal Ti; if the cathode current density is greater than 10A / cm2 , the metal magnesium dissolved in the molten salt MgCl2 will react with TiCl4 on the electrolyte surface, rather than at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4, which will also lead to a decrease in the yield and quality of metal Ti. In addition, the TiCl2 and TiCl3 in the electrolyte will cause serious contamination of metal Ti.

[0019] Preferably, the rate of introduction of TiCl4 gas is controlled to be 130-200 g / A·h. If the feed rate of TiCl4 is less than 130 g / A·h, the density of the metal magnesium dissolved in the molten salt MgCl2 increases, which will cause TiCl4 to react with the metal magnesium on the electrolyte surface of the cathode space, and the metal Ti is deposited at the bottom of the cathode space, resulting in a high content of molten salt MgCl2 in the product and poor quality; if the feed rate of TiCl4 is greater than 200 g / A·h, the metal magnesium content is relatively insufficient, and low-valent chlorides of titanium are easily generated, resulting in incomplete reaction, titanium loss and low chloride pollution, affecting the output and quality of the product.

[0020] Preferably, the method further includes taking the lower end of the cathode out of the molten salt MgCl2 and placing it in a cathode tower after the deposition of metal Ti on the cathode surface is completed, introducing argon gas into the cathode tower to cool and remove the TiCl4 remaining on the cathode surface, then taking out the cathode, separating the surface deposits, and obtaining metal titanium after post-treatment.

[0021] Beneficial effects of the present invention:

[0022] (1) The present invention provides a device for preparing metal Ti, comprising a reactor, an anode device, and at least one group of cathode devices. The number of the cathode devices is preferably multiple groups, so that cathode reactions can be carried out simultaneously to increase production, or different cathodes can be allowed to take turns to carry out cathode reactions to achieve continuous production and improve production efficiency.

[0023] (2) The present invention provides a method for preparing metal Ti, which improves the yield and quality of titanium by improving the electrochemical properties of the electrolyte and the mass transfer rate of titanium tetrachloride. The present invention uses molten salt MgCl2 as the electrolyte, and continuously changes the depth of the metal cathode immersed in the molten salt MgCl2 during the reaction process, so that the metal Ti is uniformly deposited on the surface of the metal cathode; and at the same time, the cathode current density is controlled to be 0.1-10A / cm 2 , the feed rate of TiCl4 is 130-200g / A·h, which improves the output and quality of metal titanium products. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a diagram of a device for preparing Ti by calcium reduction as described in the background technology;

[0025] Figure 2The schematic diagram of the preparation of titanium metal by the calcium reduction TiCl4 method described in the background technology;

[0026] Figure 3 A schematic diagram of the structure of a device for preparing metal Ti provided by the present invention;

[0027] Figure 4 A schematic diagram of the electrolyte-cathode-gaseous TiCl4 three-phase interface in the method of the present invention;

[0028] Figure 5 The conversion rate of Ti under different process indicators for preparing metallic Ti by molten salt electrolysis.

[0029] Figure 3 The reference numerals in the drawings are:

[0030] 1-reactor; 2-molten salt MgCl2; 3-ceramic diaphragm; 4-anode chamber; 5-steel cover; 6-graphite anode; 7-rubber seal; 8-cathode tower; 9-vacuum valve; 10-cathode chamber; 11-product metal Ti; 12-metal cathode. DETAILED DESCRIPTION

[0031] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. The embodiments shown below do not limit the invention content described in the claims. In addition, the entire contents of the structures represented by the following embodiments are not limited to those necessary as solutions to the invention described in the claims.

[0032] Reference Figure 3, a preparation device of metal Ti, comprising a reactor 1, an anode device, and at least one group of cathode devices, wherein an electrolyte 2 is arranged inside the reactor 1, and a sealing cover 5 is covered above the reactor 1, and an anode reserved opening and at least one cathode 12 reserved opening are arranged on the sealing cover 5; the anode device comprises an anode diaphragm 3, an anode fixing cover and an anode 6, and the anode diaphragm 3 encloses an anode chamber 4, and the lower end of the anode chamber 4 is arranged in the electrolyte 2 in the reactor 1, and the upper end passes through the anode reserved opening and is arranged above the sealing cover 5, and an anode cover is arranged at the upper end of the anode chamber 4, and the upper part of the anode chamber 4 is also provided with a An anode gas outlet is provided; the upper end of the anode 6 is arranged above the anode cover, and the lower end passes through the anode cover and is arranged in the anode chamber 4 and immersed in the electrolyte 2; the cathode device includes a cathode tower 8 and a cathode 12, the cathode tower 8 is arranged above the cathode 12 reserved port, the cathode tower 8 is provided with a first cathode gas inlet, a second cathode gas inlet, a second cathode gas outlet, and a vacuum port, and the gas outlet is externally provided with a vacuum valve 9, and the upper end of the cathode tower 8 is provided with a cathode cover; the upper end of the cathode 12 is arranged above the cathode cover, and the lower end passes through the cathode cover and the cathode 12 reserved port in sequence and is immersed in the electrolyte 2. During the preparation process, the first cathode gas inlet is used to transport TiCl4 gas to the cathode 12, the second cathode gas inlet is used to transport argon gas, and the second cathode gas outlet is used to output argon gas and the residual TiCl4 gas on the surface of the cathode 12. The part surrounded by the anode diaphragm 3 in the reactor 1 is the anode chamber 4, and the rest forms the cathode chamber 10. In the present device, the number of the cathode devices is at least one group, preferably multiple groups, so that the cathode reaction can be carried out simultaneously to increase the output, and different cathodes 12 can also be made to carry out cathode reaction in turn to achieve continuous production and improve production efficiency. The anode diaphragm 3 is preferably a ceramic diaphragm, and the cathode 12 is a metal cathode.

[0033] In some embodiments of the present invention, an anode chamber 4 seal is provided at the intersection of the anode diaphragm 3 and the anode reserved opening; an anode 6 seal is provided at the intersection of the anode 6 and the anode cover; a cathode tower 8 seal is provided at the position where the bottom of the cathode tower 8 contacts the sealing cover 5; and a cathode seal 7 is provided at the intersection of the cathode 12 and the cathode cover.

[0034] In some embodiments of the present invention, a power supply device, a valve system, a detection system and an automatic control system are also included, which are respectively connected to the cathode 12 and the anode 6 through circuits. The valve system is used to control the feeding and discharging of the entire device; the detection system is used to detect the internal information of the device; the automatic control system is connected to the power supply device, the valve system and the detection system, and is used to control the automatic operation of the entire device, realize automatic control of temperature, pressure, vacuum, current and voltage, and TiCl4 feeding rate, and display all working states.

[0035] In some embodiments of the present invention, the valve system includes an anode outlet valve arranged outside the anode outlet, a first cathode inlet valve arranged outside the first cathode inlet, a second cathode inlet valve arranged outside the second cathode inlet, a second cathode outlet valve arranged outside the second cathode outlet, a vacuum valve 9 arranged outside the vacuum port, a third cathode inlet valve arranged outside the third cathode inlet, and a third cathode outlet valve arranged outside the third cathode outlet; the detection system includes a current detection device and a voltage detection device arranged on the circuit, an electrolyte temperature detection device arranged in the reactor 1, and an anode pressure detection device arranged at the anode outlet. The vacuum detection device and cathode temperature detection device are arranged in the cathode tower 8; the automatic control system includes a receiving module, a calculation module, a display module, and a control module, and the calculation module and the display module are respectively connected to the receiving module and the control module; the receiving module is respectively connected to the current detection device, the voltage detection device, the electrolyte temperature detection device, the anode pressure detection device, the vacuum detection device, and the cathode temperature detection device; the control module is respectively connected to the power supply device, the anode outlet valve, the first cathode inlet valve, the second cathode inlet valve, the second cathode outlet valve, the vacuum valve 9, the third cathode inlet valve, and the third cathode outlet valve. In the actual working project, the control program can be input in advance in the calculation module. During the preparation process, the calculation module will generate control instructions according to the real-time detection data and the preset program, and transmit them to the specified device through the control module to realize the automatic control of the entire device.

[0036] In some embodiments of the present invention, the cathode tower 8 is further provided with a third cathode gas inlet and a third cathode gas outlet, a third cathode gas inlet valve is provided outside the third cathode gas inlet, and a third cathode gas outlet valve is provided outside the third cathode gas outlet; the third cathode gas inlet valve and the third cathode gas outlet valve are respectively connected to a control module in an automatic control system. The third cathode gas inlet and the third cathode gas outlet can be used to transport and output H2O to the cathode tower 8.

[0037] In some embodiments of the present invention, a cathode lifting device is also included, and the cathode lifting device includes a motor, a transmission device and a lifting mechanism, one end of the lifting mechanism is detachably connected to the upper end of the cathode 12, and the other end is linked to the motor through the transmission device; the motor is connected to the control module in the automatic control system. The cathode lifting device can realize the lifting and lowering control of the cathode 12, and can automatically control the lifting and lowering of the cathode 12 during the working process, which can not only save the cost of manual operation, but also make the operation more accurate and efficient.

[0038] A method for preparing metal Ti using the device, using molten salt MgCl2 as electrolyte for electrolysis reaction, controlling the cathode current density to 0.1-10A / cm 2 (e.g. 0.15A / cm2 , 0.2A / cm 2 , 0.5A / cm 2 , 1A / cm 2 , 2A / cm 2 , 4A / cm 2 、6A / cm 2 , 8A / cm 2 At the same time, TiCl4 gas is continuously introduced into the cathode, and the introduction rate of TiCl4 gas is controlled to be 130-200 g / A·h (e.g., 135 g / A·h, 140 g / A·h, 150 g / A·h, 160 g / A·h, 170 g / A·h, 180 g / A·h, 190 g / A·h, etc.), so that TiCl4 and the metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-cathode-gaseous TiCl4 to generate metal Ti (reference Figure 4 ) and deposited on the cathode surface, controlling the reaction temperature to 750-800°C (e.g. 755°C, 760°C, 765°C, 770°C, 780°C, 790°C, 795°C, etc.); during the reaction process, the depth of the cathode immersed in the molten salt MgCl2 is continuously adjusted to allow the metal Ti to be uniformly deposited on the cathode surface. After the deposition of metal Ti on the cathode surface is completed, the lower end of the cathode is taken out of the molten salt MgCl2 and placed in the cathode tower, and argon gas is introduced into the cathode tower to cool and remove the TiCl4 remaining on the cathode surface, then the cathode is taken out, the surface sediment is separated, and metal titanium is obtained after post-treatment. Then, the cathode is reinstalled in the reactor, and the next batch of metal Ti can be produced.

[0039] First, it should be noted that the method of the present invention uses molten salt magnesium chloride as an electrolyte, and the titanium content in the obtained product metal Ti is relatively high, wherein the residual magnesium and electrolyte molten salt MgCl2 can be simply removed by vacuum distillation or hydrometallurgy, and the product quality is high; and the metal magnesium and molten salt MgCl2 can be reused after condensation recovery, and the production cost is controllable. The present invention is to make the metal Ti uniformly and stably deposited on the metal cathode, and the depth of the cathode immersion in the melt is continuously changed during the electrolysis process (making the metal cathode reciprocate in the vertical electrolyte direction). In the reaction process, if the metal cathode is immersed in the molten salt MgCl2, the depth remains unchanged, and the metal titanium is deposited on the three-phase interface of the electrolyte-metal cathode-gaseous TiCl4, and the Ti deposition layer on the surface of the metal cathode is unevenly distributed, which will cause the metal cathode to be difficult to remove from the reactor, so that the metal Ti is easily collapsed into the molten salt electrolyte.

[0040] Secondly, in the method described in the present invention, if the cathode current density is too small, a small amount of TiCl2 and TiCl3 will appear near the metal cathode, resulting in a decrease in the yield and quality of metal Ti; if the cathode current density is too large, the metal magnesium dissolved in the molten salt MgCl2 will react with TiCl4 on the electrolyte surface, rather than at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4, which will also result in a decrease in the yield and quality of metal Ti. In addition, the TiCl2 and TiCl3 appearing in the electrolyte will cause serious contamination of metal Ti.

[0041] In addition, in the method described in the present invention, if the feed rate of TiCl4 is too small, the density of the metallic magnesium dissolved in the molten salt MgCl2 increases, which will cause TiCl4 to react with the metallic magnesium on the electrolyte surface of the cathode space, and the metallic Ti is deposited at the bottom of the cathode space, resulting in a high content of molten salt MgCl2 in the product and poor quality; if the feed rate of TiCl4 is too large, the metallic magnesium content is relatively insufficient, and low-valent chlorides of titanium are easily generated, resulting in incomplete reaction, titanium loss and low chloride pollution, affecting the output and quality of the product.

[0042] Example 1

[0043] A method and device for preparing metal Ti, wherein the electrolyte molten salt MgCl2 is added into a reactor, the temperature of the reactor is controlled to be 780°C, the reactor is divided into an anode chamber and a cathode chamber by a ceramic diaphragm, and the cathode current density is 0.1A / cm 2 . The molten salt MgCl2 is electrolyzed to generate metal magnesium and chlorine (2MgCl2→2Mg+Cl2↑). The chlorine is discharged from the anode chamber, and the metal magnesium is dissolved in the molten salt MgCl2 in the cathode chamber. TiCl4 is introduced into the cathode chamber at a rate of 200g / A·h. TiCl4 and the metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4. The generated metal Ti is deposited on the metal cathode. By continuously changing the depth of the metal cathode immersed in the molten salt MgCl2, the metal Ti is uniformly deposited on the surface of the metal cathode. When a sufficient amount of metal Ti is deposited on the surface of the metal cathode, the vacuum valve is opened, the metal cathode is raised into the cathode tower, argon gas is introduced to cool and remove the TiCl4 residue, and the metal cathode is taken out after cooling. The metal Ti is sliced ​​and the molten salt MgCl2 is removed by vacuum distillation or hydrometallurgical treatment. Then, the metal cathode is reinstalled in the reactor to produce the next batch of metal Ti.

[0044] Example 2

[0045] A method and device for preparing metal Ti, wherein the electrolyte molten salt MgCl2 is added into a reactor, the temperature of the reactor is controlled to be 780°C, the reactor is divided into an anode chamber and a cathode chamber by a ceramic diaphragm, and the cathode current density is 1.0A / cm2 . The molten salt MgCl2 is electrolyzed to generate metal magnesium and chlorine (2MgCl2→2Mg+Cl2↑). The chlorine is discharged from the anode chamber, and the metal magnesium is dissolved in the molten salt MgCl2 in the cathode chamber. TiCl4 is introduced into the cathode chamber at a rate of 160g / A·h. TiCl4 and the metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4. The generated metal Ti is deposited on the metal cathode. By continuously changing the depth of the metal cathode immersed in the molten salt MgCl2, the metal Ti is uniformly deposited on the surface of the metal cathode. When a sufficient amount of metal Ti is deposited on the surface of the metal cathode, the vacuum valve is opened, the metal cathode is raised into the cathode tower, argon gas is introduced to cool and remove the TiCl4 residue, and the metal cathode is taken out after cooling. The metal Ti is sliced ​​and the molten salt MgCl2 is removed by vacuum distillation or hydrometallurgical treatment. Then, the metal cathode is reinstalled in the reactor to produce the next batch of metal Ti.

[0046] Example 3

[0047] A method and device for preparing metal Ti, wherein the electrolyte molten salt MgCl2 is added into a reactor, the temperature of the reactor is controlled to be 780°C, the reactor is divided into an anode chamber and a cathode chamber by a ceramic diaphragm, and the cathode current density is 10A / cm 2 Molten salt MgCl2 is electrolyzed to generate metallic magnesium and chlorine (2MgCl2→2Mg+Cl2↑), and chlorine is discharged from the anode chamber. The metallic magnesium is dissolved in the molten salt MgCl2 in the cathode chamber. TiCl4 is introduced into the cathode chamber at a rate of 130g / A·h. TiCl4 and the metallic magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4. The generated metallic Ti is deposited on the metallic cathode. By continuously changing the depth of the metallic cathode immersed in the molten salt MgCl2, the metallic Ti is uniformly deposited on the surface of the metallic cathode. When a sufficient amount of metallic Ti is deposited on the surface of the metallic cathode, the vacuum valve is opened, the metallic cathode is raised into the cathode tower, and argon is introduced to cool and remove the TiCl4 residue. After cooling, the metallic cathode is taken out, and the metallic Ti is sliced ​​and the molten salt MgCl2 is removed by vacuum distillation or hydrometallurgical treatment. Then, the metallic cathode is reinstalled in the reactor to produce the next batch of metallic Ti.

[0048] Comparative Example 1

[0049] A method and device for preparing metal Ti, wherein an electrolyte molten salt MgCl2 is added into a reactor, the temperature of the reactor is controlled to be 780°C, the reactor is divided into an anode chamber and a cathode chamber by a ceramic diaphragm, and the cathode current density is 0.05A / cm2. The molten salt MgCl2 is electrolyzed to generate metal magnesium and chlorine (2MgCl2→2Mg+Cl2↑), the chlorine is discharged from the anode chamber, the metal magnesium is dissolved in the molten salt MgCl2 in the cathode chamber, TiCl4 is introduced into the cathode chamber at a rate of 160g / A·h, TiCl4 and the metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4, the generated metal Ti is deposited on the metal cathode, and the metal Ti is uniformly deposited on the surface of the metal cathode by continuously changing the depth of the metal cathode immersed in the molten salt MgCl2. When a sufficient amount of metal Ti is deposited on the surface of the metal cathode, open the vacuum valve, lift the metal cathode into the cathode tower, pass argon gas to cool and remove the TiCl4 residue, take out the metal cathode after cooling, slice the metal Ti and remove the molten salt MgCl2 through vacuum distillation or hydrometallurgical treatment. Then, reinstall the metal cathode in the reactor to produce the next batch of metal Ti.

[0050] Comparative Example 2

[0051] A method and device for preparing metal Ti, wherein the electrolyte molten salt MgCl2 is added into a reactor, the temperature of the reactor is controlled to be 780°C, the reactor is divided into an anode chamber and a cathode chamber by a ceramic diaphragm, and the cathode current density is 15A / cm 2 . The molten salt MgCl2 is electrolyzed to generate metal magnesium and chlorine (2MgCl2→2Mg+Cl2↑). The chlorine is discharged from the anode chamber, and the metal magnesium is dissolved in the molten salt MgCl2 in the cathode chamber. TiCl4 is introduced into the cathode chamber at a rate of 160g / A·h. TiCl4 and the metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4. The generated metal Ti is deposited on the metal cathode. By continuously changing the depth of the metal cathode immersed in the molten salt MgCl2, the metal Ti is uniformly deposited on the surface of the metal cathode. When a sufficient amount of metal Ti is deposited on the surface of the metal cathode, the vacuum valve is opened, the metal cathode is raised into the cathode tower, argon gas is introduced to cool and remove the TiCl4 residue, and the metal cathode is taken out after cooling. The metal Ti is sliced ​​and the molten salt MgCl2 is removed by vacuum distillation or hydrometallurgical treatment. Then, the metal cathode is reinstalled in the reactor to produce the next batch of metal Ti.

[0052] Comparative Example 3

[0053] A method and device for preparing metal Ti, wherein the electrolyte molten salt MgCl2 is added into a reactor, the temperature of the reactor is controlled to be 780°C, the reactor is divided into an anode chamber and a cathode chamber by a ceramic diaphragm, and the cathode current density is 1.0A / cm 2 . The molten salt MgCl2 is electrolyzed to generate metal magnesium and chlorine (2MgCl2→2Mg+Cl2↑). The chlorine is discharged from the anode chamber, and the metal magnesium is dissolved in the molten salt MgCl2 in the cathode chamber. TiCl4 is introduced into the cathode chamber at a rate of 100g / A·h. TiCl4 and the metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4. The generated metal Ti is deposited on the metal cathode. By continuously changing the depth of the metal cathode immersed in the molten salt MgCl2, the metal Ti is uniformly deposited on the surface of the metal cathode. When a sufficient amount of metal Ti is deposited on the surface of the metal cathode, the vacuum valve is opened, the metal cathode is raised into the cathode tower, argon gas is introduced to cool and remove the TiCl4 residue, and the metal cathode is taken out after cooling. The metal Ti is sliced ​​and the molten salt MgCl2 is removed by vacuum distillation or hydrometallurgical treatment. Then, the metal cathode is reinstalled in the reactor to produce the next batch of metal Ti.

[0054] Comparative Example 4

[0055] A method and device for preparing metal Ti, wherein the electrolyte molten salt MgCl2 is added into a reactor, the temperature of the reactor is controlled to be 780°C, the reactor is divided into an anode chamber and a cathode chamber by a ceramic diaphragm, and the cathode current density is 1.0A / cm 2 . The molten salt MgCl2 is electrolyzed to generate metal magnesium and chlorine (2MgCl2→2Mg+Cl2↑). The chlorine is discharged from the anode chamber, and the metal magnesium is dissolved in the molten salt MgCl2 in the cathode chamber. TiCl4 is introduced into the cathode chamber at a rate of 230g / A·h. TiCl4 and the metal magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-metal cathode-gaseous TiCl4. The generated metal Ti is deposited on the metal cathode. By continuously changing the depth of the metal cathode immersed in the molten salt MgCl2, the metal Ti is uniformly deposited on the surface of the metal cathode. When a sufficient amount of metal Ti is deposited on the surface of the metal cathode, the vacuum valve is opened, the metal cathode is raised into the cathode tower, argon gas is introduced to cool and remove the TiCl4 residue, and the metal cathode is taken out after cooling. The metal Ti is sliced ​​and the molten salt MgCl2 is removed by vacuum distillation or hydrometallurgical treatment. Then, the metal cathode is reinstalled in the reactor to produce the next batch of metal Ti.

[0056] Comparative Example 5

[0057] The experiment was conducted according to the background technology "A method and device for preparing Ti by calcium reduction disclosed in EP05799311A (Hori M., Ogasawara T., Yamaquchi M., etc., published on August 8, 2007)". The cathode current density in the electrolytic cell was 1.0 A / cm 2 , the feed rate of TiCl4 is 160g / A·h.

[0058] Comparative Example 6

[0059] The experiment was conducted according to the background technology "Reduction of TiCl4 Gas by CaDissolved in Molten Calcium Chloride" (Takayuki Naito, Ryosuke O.Suzuki, Yoichi Tomii.) A method for preparing titanium metal by reducing TiCl4 gas with calcium dissolved in molten calcium chloride. The cathode current density in the electrolytic cell was 1.0 A / cm 2 , the feed rate of TiCl4 is 160g / A·h.

[0060] As shown in Table 1, Figure 5 The conversion rates of Ti in Examples 1-3 and Comparative Examples 1-4 at different cathode current densities and different TiCl4 feed rates are shown in Tables 1 and 4. Comparative Examples 5 and 6 are two methods for preparing metal Ti involved in the background technology. The conversion rates of Ti are obtained by conducting experiments according to the methods shown. Figure 5 It can be seen that the yield of metal Ti obtained in Examples 1 to 3 is relatively high, and the conversion rate of Ti is above 80%. Compared with Comparative Examples 1 to 4, the cathode current density in the present invention is limited to 0.1-10 A / cm 2 , the feed rate of TiCl4 is 130-200 g / A·h, which is feasible; compared with comparative examples 5-6, the present invention has obvious advantages over the existing methods for preparing metallic Ti by molten salt electrolysis.

[0061] Table 1 Conversion rate of Ti under different process indicators for preparing metallic Ti by molten salt electrolysis

[0062]

[0063] As shown in Table 2, the element content of metallic Ti prepared by the method adopted in this patent and the method adopted in Background Technology 2 is shown. The quality of metallic Ti prepared by different methods is different. The Ti content in metallic Ti prepared by the method of the present invention is as high as 99.70%, while the Ti content in metallic Ti prepared by Background Technology 2 is only 90.08%.

[0064] Table 2 Element contents of products prepared by different methods of molten salt electrolysis for metal Ti

[0065]

[0066] In summary, the method of the present invention is used to prepare metal Ti, and its output and quality are higher than other methods, which has great advantages and can be realized in industrial production.

[0067] In the description of the present application, it should be noted that the terms "upper", "lower", "inner", "outer", etc., indicating the orientation or positional relationship, are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present application. In addition, the terms "first", "second", "third", etc., are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0068] Unless otherwise clearly specified and limited, the terms "disposed" and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be the internal communication of two elements. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0069] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A device for preparing metal Ti, characterized in that: It comprises a reactor, an anode device, and at least one cathode device. An electrolyte is arranged inside the reactor, and a sealing cover is covered on the reactor, wherein the sealing cover is provided with an anode reserved opening and at least one cathode reserved opening; The anode device comprises an anode diaphragm, an anode fixing cover and an anode, wherein the anode diaphragm encloses an anode chamber, wherein the lower end of the anode chamber is arranged in the electrolyte in the reactor, and the upper end thereof is arranged above the sealing cover through the anode reserved opening, an anode cover is arranged at the upper end of the anode chamber, and an anode gas outlet is also arranged at the upper part of the anode chamber; the upper end of the anode is arranged above the anode cover, and the lower end thereof is arranged in the anode chamber through the anode cover and immersed in the electrolyte; The cathode device includes a cathode tower and a cathode, wherein the cathode tower is arranged above the cathode reserved opening, and is provided with a first cathode air inlet, a second cathode air inlet, a second cathode air outlet, and a vacuum port. The vacuum port is externally provided with a vacuum valve, and a cathode cover is arranged at the upper end of the cathode tower; the upper end of the cathode is arranged above the cathode cover, and the lower end passes through the cathode cover and the cathode reserved opening in sequence and is immersed in the electrolyte.

2. A preparation device for metal Ti according to claim 1, characterized in that: An anode chamber seal is provided at the intersection of the anode diaphragm and the anode reserved opening; an anode seal is provided at the intersection of the anode and the anode cover; a cathode tower seal is provided at the position where the bottom of the cathode tower contacts the sealing cover; and a cathode seal is provided at the intersection of the cathode and the cathode cover.

3. The device for preparing metal Ti according to any one of claims 1 to 2, characterized in that: It also includes a power supply device, a valve system, a detection system and an automatic control system which are respectively connected to the cathode and the anode through circuits. The valve system is used to control the feeding and discharging of the entire device; the detection system is used to detect the internal information of the device; the automatic control system is connected to the power supply device, the valve system and the detection system to control the automatic of the entire device.

4. A preparation device for metal Ti according to claim 3, characterized in that: The valve system includes an anode outlet valve disposed outside the anode outlet, a first cathode inlet valve disposed outside the first cathode inlet, a second cathode inlet valve disposed outside the second cathode inlet, a second cathode outlet valve disposed outside the second cathode outlet, a vacuum valve disposed outside the gas extraction port, a third cathode inlet valve disposed outside the third cathode inlet, and a third cathode outlet valve disposed outside the third cathode outlet; The detection system includes a current detection device and a voltage detection device arranged on the circuit, an electrolyte temperature detection device arranged in the reactor, an anode pressure detection device arranged at the anode gas outlet, a vacuum detection device and a cathode temperature detection device arranged in the cathode tower; The automatic control system includes a receiving module, a computing module, a display module, and a control module. The computing module and the display module are respectively connected to the receiving module and the control module; the receiving module is respectively connected to a current detection device, a voltage detection device, an electrolyte temperature detection device, an anode pressure detection device, a vacuum detection device, and a cathode temperature detection device; the control module is respectively connected to a power supply device, an anode outlet valve, a first cathode inlet valve, a second cathode inlet valve, a second cathode outlet valve, a vacuum valve, a third cathode inlet valve, and a third cathode outlet valve.

5. A preparation device for metal Ti according to claim 4, characterized in that: The cathode tower is also provided with a third cathode air inlet and a third cathode air outlet, a third cathode air inlet valve is arranged outside the third cathode air inlet, and a third cathode air outlet valve is arranged outside the third cathode air outlet; the third cathode air inlet valve and the third cathode air outlet valve are respectively connected to the control module in the automatic control system.

6. The device for preparing metal Ti according to claim 4, characterized in that: It also includes a cathode lifting device, which includes a motor, a transmission device and a lifting mechanism. One end of the lifting mechanism is detachably connected to the upper end of the cathode, and the other end is linked to the motor through the transmission device; the motor is connected to the control module in the automatic control system.

7. A method for preparing metal Ti using the device according to any one of claims 1 to 6, characterized in that: An electrolytic reaction is carried out using molten salt MgCl2 as an electrolyte to generate metallic magnesium and chlorine gas, and the chlorine gas is discharged from the anode chamber, and the metallic magnesium is dissolved in the molten salt MgCl2; at the same time, TiCl4 gas is continuously introduced into the cathode, so that TiCl4 and the metallic magnesium dissolved in the molten salt MgCl2 undergo a reduction reaction at the three-phase interface of electrolyte-cathode-gaseous TiCl4 to generate metallic Ti, which is deposited on the cathode surface; during the reaction, the depth of the cathode immersed in the molten salt MgCl2 is continuously adjusted to allow the metallic Ti to be uniformly deposited on the cathode surface.

8. A method for preparing metal Ti according to claim 7, characterized in that: The reaction temperature is controlled to be 750-800°C; and / or the cathode current density is 0.1-10A / cm 2 .

9. The method for preparing metal Ti according to any one of claims 7 to 8, characterized in that: The introduction rate of TiCl4 gas was controlled to be 130-200 g / A·h.

10. A method for preparing metal Ti according to claim 7, characterized in that: The method also includes taking the lower end of the cathode out of the molten salt MgCl2 and putting it into a cathode tower after the deposition of metal Ti on the cathode surface is completed, introducing argon gas into the cathode tower to cool and remove the TiCl4 remaining on the cathode surface, then taking out the cathode, separating the surface deposits, and obtaining metal titanium after post-treatment.

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