Process for producing titanium-zirconium-hafnium series metal through continuous reduction

Abstract

The invention discloses a process for producing titanium-zirconium-hafnium series metal through continuous reduction, which comprises the following steps: in an inert atmosphere, heating a reactor to a reaction temperature, adding metal magnesium, and then continuously adding tetrachloride at a constant high speed to carry out reduction reaction. In the reaction process, magnesium chloride melt is continuously or intermittently discharged, and metal magnesium is supplemented to maintain the reaction; meanwhile, the generated sponge titanium is continuously moved out and conveyed to a collector through a conveying device directly communicated with the reactor. The whole process of feeding, reacting, discharging and product moving-out is continuous, a traditional sequencing batch production mode is subverted, the titanium tetrachloride feeding speed can be stably kept at a high level (for example, the titanium tetrachloride feeding speed is larger than or equal to 1600 kg / h), the production efficiency is remarkably improved compared with a traditional process, meanwhile, stability and excellent product quality are guaranteed, the automation degree is high, and the production cost is low. And centralized recycling of reaction waste heat can be realized.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metal metallurgy, and more specifically, to a process for the continuous reduction production of titanium-zirconium-hafnium metals. Background Technology

[0002] Titanium-zirconium-hafnium (TiZZH) metals (mainly including sponge titanium, sponge zirconium, and sponge hafnium) are important strategic metal materials. Their industrial production currently widely employs the magnesium reduction-vacuum distillation method, also known as the Kroll Process. This process uses tetrachlorides (titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride) as raw materials and metallic magnesium (Mg) as a reducing agent. The reduction reaction takes place under an inert atmosphere to produce titanium-zirconium-hafnium metals and magnesium chloride (MgCl2). Subsequently, high-temperature vacuum distillation removes residual magnesium and magnesium chloride from the pores of the titanium-zirconium-hafnium metals, ultimately yielding a pure, sponge-like product.

[0003] Taking the existing production process of sponge titanium as an example, the steps are as follows: First, the assembled reactor is placed in a heating furnace and preheated to the set temperature; refined metallic magnesium is added in one go; then, liquid titanium tetrachloride is slowly added to the reactor at a controlled rate. The reduction reaction (TiCl4 + 2Mg → Ti + 2MgCl2) is a strongly exothermic process, so the feeding rate of titanium tetrachloride must be strictly controlled. Too fast a rate may lead to local overheating, damaging the equipment and affecting the subsequent distillation effect. The liquid magnesium chloride produced during the reaction needs to be periodically discharged from the reactor to maintain an effective reaction space. After reaching the predetermined yield, feeding is stopped, and the reduction stage ends. Then, the process transitions to the vacuum distillation stage, where the residual magnesium and magnesium chloride are evaporated and separated under high temperature and high vacuum conditions to obtain porous sponge titanium lumps. After cooling, removal, crushing, and grading, the sponge titanium lumps become commercial sponge titanium.

[0004] However, this mature process has a fundamental limitation: it is essentially a batch (intermittent) operation, meaning that the second batch is produced only after the first batch is completed. Each batch must independently and sequentially complete the entire process of "charging → heating → adding magnesium → secondary heating → adding titanium tetrachloride (reduction) → multiple magnesium chloride discharges → stopping feeding → ignition → vacuum distillation → cooling → unloading" (the reduction process and reactor are as follows...). Figure 1 (As shown). This single-furnace interval production mode leads to the following significant technical drawbacks and industry bottlenecks: (1) Low production efficiency: The reduction cycle of a single furnace is long and the effective reaction time is low. Taking a furnace with a single furnace capacity of 7 tons as an example, the reduction time in the furnace is about 100 hours, the reduction reaction time is about 70 hours, and 30 hours are in the preparation or waiting state (i.e. non-feeding time). The titanium production per unit time is only 70 kg / h.

[0005] (2) Low average feeding rate: In the initial stage of the magnesium reduction process, due to the lack of crystal nuclei for rapid reaction, the feeding rate of titanium tetrachloride can only be gradually increased from small to large. In the middle and later stages, due to insufficient magnesium, the feeding rate has to be gradually reduced until feeding stops. The current titanium tetrachloride feeding rate is as follows: Figure 2 As shown in the figure. According to statistics, the maximum addition rate of titanium tetrachloride during the reduction process can reach about 600 kg / h, but the average addition rate is between 400 and 480 kg / h, which limits the release of production capacity.

[0006] (3) The product quality is not high and unstable: On the one hand, since the magnesium has not undergone deep impurity removal, Fe, Mn and other elements in the magnesium have entered the sponge titanium and are distributed discretely, which has a significant impact on the stability of product quality. On the other hand, due to the continuous changes in the feeding rate and the long reduction time, the relationship between the feeding rate and product quality is difficult to determine.

[0007] Therefore, developing a new technology that enables continuous, stable, and efficient production of titanium, zirconium, and hafnium metals is of great significance for improving the industry's technological level, reducing production costs, and enhancing product quality. Summary of the Invention

[0008] To overcome the aforementioned defects of the batch (intermittent) process used in the existing magnesium reduction method for producing sponge titanium, the present invention aims to provide a continuous reduction process for producing titanium-zirconium-hafnium metals. This process enables continuous reduction, removal, and purification throughout the entire process, thereby significantly improving production efficiency, stabilizing product quality, and reducing energy consumption and labor intensity.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A continuous reduction process for producing titanium-zirconium-hafnium metals includes the following steps: heating a reactor to the reaction temperature under an inert atmosphere and adding metallic magnesium; continuously adding tetrachloride to the reactor at a constant rate for reduction; continuously or intermittently discharging molten magnesium chloride and replenishing metallic magnesium multiple times to ensure the reduction reaction continues; continuously removing the generated sponge titanium from the reactor via a conveyor directly connected to the reactor and transporting it to a collector for collection, thus ensuring the reduction reaction continues. The metallic magnesium is refined or crude magnesium. The inert atmosphere is argon. The addition rate of tetrachloride (such as titanium tetrachloride) is not less than 1600 kg / h.

[0010] Furthermore, the tetrachloride is any one of titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride. This process can produce any one of sponge titanium, sponge zirconium, and sponge hafnium. When the tetrachloride is titanium tetrachloride, it is used to produce sponge titanium; when the tetrachloride is zirconium tetrachloride, it is used to produce sponge zirconium; and when the tetrachloride is hafnium tetrachloride, it is used to produce sponge hafnium.

[0011] Furthermore, a heating furnace is installed outside the reactor; a sealing cover is provided on the top of the reactor; and a feeding and discharging system connected to the reactor is installed on the sealing cover.

[0012] Furthermore, when the continuous reduction process for producing titanium-zirconium-hafnium metals is used only to produce titanium-zirconium-hafnium metals, the magnesium metal used is refined magnesium, and the feeding and discharging system includes a magnesium replenishment pipeline, a tetrachloride feeding pipeline, and a magnesium chloride discharge system, all connected to the reactor.

[0013] Furthermore, in addition to producing titanium-zirconium-hafnium metals, the continuous reduction process for producing titanium-zirconium-hafnium metals is also used for the deep purification of metallic magnesium. The metallic magnesium used is crude magnesium. The feeding and discharging system includes crude magnesium and tetrachloride feeding pipes connected to the reactor, a refined magnesium discharge pipe, and a magnesium chloride discharge system.

[0014] Furthermore, the magnesium chloride discharge system includes a liquid level detection device (such as a radar level gauge) installed on the reactor, a magnesium chloride discharge pipe connected to the bottom of the reactor, an electric discharge valve installed on the magnesium chloride discharge pipe, and a discharge device installed outside the reactor and connected to the magnesium chloride discharge pipe (the discharge device is a vacuum pump, a high-temperature pump, or the addition of inert gas to assist in discharging the magnesium chloride melt from the bottom of the reactor, achieving stable and controllable continuous or intermittent discharge). The magnesium chloride melt is discharged through the discharge device and the magnesium chloride discharge pipe. A pipe heating device can be installed on the magnesium chloride discharge pipe to prevent magnesium chloride from solidifying and clogging.

[0015] Furthermore, a heat dissipation device is installed inside the reactor, which extends into the reactor from the top through a heat dissipation pipe mounted on a sealed cover. The heat dissipation device is a similar mechanism, such as a circulating water channel or circulating air channel spirally arranged inside the heat dissipation pipe, for circulating heat dissipation.

[0016] Furthermore, the conveying device includes a conveying pipe and a high-temperature resistant conveying mechanism disposed within the conveying pipe. The conveying pipe is inclined, with one end (lower end) connected to the interior of the reactor (usually the bottom area), and the other end (upper end) connected to a collector (the bottom of the other end of the conveying pipe is connected to the collector via a discharge pipe). An insulation layer is provided outside the conveying pipe to reduce heat loss and maintain the required conveying temperature. The high-temperature resistant conveying mechanism is a chain conveyor with baffles on its chain plate to form a hopper for catching materials. The chain plate body is covered with perforations to allow most of the magnesium and magnesium chloride melt entrained during conveying to drain out. The high-temperature resistant conveying mechanism continuously conveys the titanium-zirconium-hafnium metal particles deposited at the bottom of the reactor and falling onto the high-temperature resistant conveying mechanism upwards. When conveyed to the other end of the conveying pipe, they fall into the collector from the discharge pipe of the conveying pipe.

[0017] When the continuous reduction process for producing titanium-zirconium-hafnium metals is used not only for producing titanium-zirconium-hafnium metals but also for the deep purification of metallic magnesium, the specific steps include: placing the metallic magnesium to be purified in a reactor, introducing tetrachloride under an inert atmosphere and at an appropriate temperature, and using the titanium-zirconium-hafnium metals and magnesium chloride generated by the reaction to adsorb and replace impurities in the magnesium, thereby physically adsorbing and chemically replacing non-metallic impurities (such as oxides and nitrides) and metallic impurities (such as Fe, Mn, Al, etc.) in the crude magnesium, thus achieving the purpose of deep purification of magnesium.

[0018] The beneficial effects of this invention are: (1) Achieving full-process continuous production: Transforming intermittent production into continuous production, with almost no idle time for equipment. This overturns the traditional batch production model, achieving full-process continuous production from feeding, reaction, slag discharge to product removal, significantly improving equipment utilization and increasing production efficiency several times compared to traditional processes. The feeding rate of titanium tetrachloride can be stably maintained at over 1600 kg / h, and the titanium production per unit time can reach 400 kg / h, which is more than 5 times that of the traditional process (70 kg / h).

[0019] (2) Stable and excellent product quality: constant high-speed feeding, stable liquid level control, and deeply purified magnesium source together ensure the high purity and excellent uniformity of the product.

[0020] (3) High degree of automation and stable operation: Through liquid level interlock control of discharge and automatic operation of vacuum system, a high degree of automation control is achieved, reducing labor intensity and making the production process safer, more stable and controllable. (4) Multi-purpose: By adjusting the feeding and discharging configuration, the same set of equipment can be used to efficiently and continuously produce sponge titanium, and can also be used for deep purification of crude magnesium, thus expanding the application range of the equipment.

[0021] (5) Waste heat utilization: Based on the addition rate of tetrachloride of 1600 kg / h, the system needs to exhaust about 800 kW / h of heat. Using this invention, concentrated and stable waste heat can be provided. If it is collected and recycled, the apparent energy consumption of the reduction process can be zero or negative, and the energy saving effect is very obvious. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the structure of a conventional batch magnesium reduction method sponge titanium production device.

[0023] Figure 2 This is a typical curve showing the change of titanium tetrachloride feeding rate over time in the existing technology.

[0024] Figure 3 This is a schematic diagram illustrating a constant high-speed titanium tetrachloride feeding rate achievable in an embodiment of the present invention.

[0025] Figure 4 This is a schematic diagram of the overall structure of the continuous reduction sponge titanium production device described in this invention.

[0026] Figure 5 This is a schematic diagram of the device of the present invention applied to the deep purification of metallic magnesium.

[0027] The diagram shows: 1-reactor, 2-heating furnace, 3-conveyor, 31-conveyor pipe, 32-high temperature resistant conveying mechanism, 33-insulation layer, 34-draining chamber (formed by the high position of the pipe), 4-magnesium replenishment pipe, 5-magnesium chloride discharge pipe, 6-tetrachloride feeding pipe, 7-sealing cover, 8-heat dissipation device, 9-collector, 10-crude magnesium and tetrachloride feeding pipe, 11-refined magnesium discharge pipe. Detailed Implementation

[0028] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] It should be understood that the structures, proportions, sizes, etc., depicted in the accompanying drawings of this specification are merely for illustrative purposes to aid those skilled in the art in understanding and reading the content disclosed herein, and are not intended to limit the conditions under which the invention can be implemented. Therefore, they have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to the size, without affecting the effects and objectives achieved by the invention, should still fall within the scope of the technical content disclosed herein. Furthermore, the terms such as "upper," "lower," "left," "right," and "middle" used in this specification are merely for clarity and are not intended to limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention's implementation.

[0030] In the description of this invention, it should be noted that, unless otherwise expressly specified and limited, the terms "connected" or "linked" should be interpreted broadly. For example, it can refer to a fixed connection, a detachable connection, or an integral connection; it can refer to a mechanical connection or an electrical connection; it can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances. It should be noted that the terms "comprising," "including," or any other variations are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0031] The following uses the formation process of sponge titanium as an example to specifically illustrate the production process and principle of the present invention. The production processes and principles of other sponge zirconium and sponge hafnium are basically the same as those of the present invention, and will not be described in detail here. Example 1: Continuous Reduction Sponge Titanium Production Apparatus

[0032] like Figure 4 As shown, this embodiment provides a continuous reduction sponge titanium production apparatus, including a reactor 1, a heating furnace 2, a feeding and discharging system, a conveying device 3, a heat dissipation device 8, and a collector 9.

[0033] The reactor 1 is a cylindrical body with a diameter greater than 2 meters and a cylindrical shape (it can also be rectangular, square, or other shapes), made of a material that is resistant to high temperature and chloride salt corrosion (such as nickel-based alloys). The top of the reactor 1 is equipped with a sealing cover 7, which has multiple functional interfaces. A sealing ring is provided between the sealing cover 7 and the reactor 1, and a flange with bolts is used to achieve a tight connection.

[0034] The heating furnace 2 is installed outside the reactor 1. The heating furnace 2 is a resistance heating furnace. The furnace body is made of composite insulation material, which can stably maintain the temperature of the reaction zone at 800-900℃.

[0035] The feeding and discharging system is connected to the reactor 1 through the functional interface of the sealing cover 7. The feeding and discharging system includes a magnesium replenishment pipe 4, a tetrachloride feeding pipe 6, and a magnesium chloride discharge system, which are respectively connected to the reactor 1.

[0036] One end of the magnesium replenishment pipe 4 is inserted from the sealing cover 7 of the reactor 1 into the middle of the reactor 1 (inside the magnesium layer), and the other end is connected to an external magnesium refining and purification furnace, which can pump deeply purified liquid magnesium (impurity Fe content <0.01%) into the reactor 1 as needed.

[0037] The tetrachloride feeding pipe 6 consists of three feeding pipes evenly distributed on the sealing cover 7 of the reactor 1. Controlled by a high-precision mass flow meter, it can inject liquid titanium tetrachloride into the reactor 1 at a constant total speed of not less than 1600 kg / h.

[0038] The magnesium chloride discharge system includes a liquid level detection device on the sealing cover 7 of reactor 1, a magnesium chloride discharge pipe 5 connected to the bottom of reactor 1, an electric discharge valve on the magnesium chloride discharge pipe 5, and a discharge device located outside reactor 1 and connected to the magnesium chloride discharge pipe 5. The discharge device can be any one of a vacuum pump, a high-temperature pump, or an inert gas injection device (a vacuum pump draws out magnesium chloride through negative pressure, a high-temperature pump or high-temperature centrifugal pump directly extracts magnesium chloride, and an inert gas injection device fills the reactor with argon gas, forcing magnesium chloride out of reactor 1 along the magnesium chloride discharge pipe 5). This assists in discharging the magnesium chloride melt from the bottom of reactor 1, achieving stable and controllable continuous or intermittent discharge. The liquid level detection device is a radar level gauge that monitors the melt level in real time. One end of the magnesium chloride discharge pipe 5 passes through the sealing cover 7 of the reactor 1 and extends into the bottom of the inner side of the reactor 1. A high-temperature resistant electric disc valve with a temperature of 720℃ is connected in series on the pipe outside the reactor 1 as an electric discharge valve. The pipe after the electric discharge valve is wrapped with an electric heating belt for heat preservation. The end of the magnesium chloride discharge pipe 5 outside the reactor 1 is connected to an intermediate storage tank. The liquid level in the reactor 1 is set with a high limit and a low limit. When the liquid level reaches the high limit, the electric discharge valve is opened and the discharge device is started to quickly discharge the magnesium chloride melt into the intermediate storage tank.

[0039] The conveying device 3 includes a conveying pipe 31 and a high-temperature resistant conveying mechanism 32 disposed within the conveying pipe 31.

[0040] The conveying pipe 31 is a high-temperature resistant alloy pipe, which is inclined and installed on the side of the reactor 1. One end (lower end) of the conveying pipe 31 is inserted into the lower half of the side wall of the reactor 1 at an angle of about 30° (the angle can be adjusted as needed, not limited to 30°, and can be adjusted arbitrarily between 5° and 90°, such as 45°, 60°, 75°, etc.), and its interior is connected to the bottom sedimentation area inside the reactor 1. The other end (upper end) extends upward, and its top end (i.e., the discharge port) is about 2 meters higher than the top of the reactor 1 (i.e., the top of the upper end of the conveying pipe 31 is higher than the top of the reactor 1), and finally connects to a water-cooled jacketed collector 9. The conveying pipe 31 is completely wrapped with an aluminum silicate fiber insulation layer 33, and the inside of the conveying pipe 31 is protected by argon gas.

[0041] The high-temperature resistant conveying mechanism 32 employs a chain conveyor (or other conveying equipment capable of similar conveying functions). The chain plates of the chain conveyor are made of heat-resistant steel, with 50mm high guardrails vertically welded onto the chain plates to form hoppers. The chain plate body is covered with φ8mm perforated holes. The drive motor of the chain conveyor uses frequency conversion control, enabling stepless adjustment of the conveying speed within the range of 0.1-1.0 m / min.

[0042] The heat dissipation device 8 extends from the top of the reactor 1 into the reactor 1 through a heat dissipation pipe installed on the sealing cover 7 (the heat dissipation device 8 is installed inside the heat dissipation pipe). The heat dissipation device 8 includes one or more water-cooled coils (or similar circulating water or circulating air heat dissipation mechanisms) spirally arranged inside the heat dissipation pipe. It passes through the sealing cover 7 and is inserted into the reactor 1 (extending into the magnesium layer together with the heat dissipation pipe). Excess reaction heat is removed by adjusting the cooling water flow rate. Example 2: Method for continuous production of sponge titanium using the apparatus described in Example 1

[0043] This embodiment details a specific method for the industrial continuous production of sponge titanium using the equipment described in Embodiment 1, including the following production steps: S1. System Initialization and Startup

[0044] S11. After the equipment is assembled, close all valves, start the vacuum system to evacuate reactor 1 and conveying pipeline 31 to below 50 Pa, and then fill with high-purity argon to a slightly positive pressure. Repeat this three times to ensure that the oxygen content in the system is below 10 ppm and to form an inert atmosphere.

[0045] S12. Pre-melted and deeply purified liquid magnesium is pumped into reactor 1 through magnesium replenishment pipe 4 as the initial reaction material.

[0046] S13. Start heating furnace 2 and slowly raise the temperature inside reactor 1 to 850℃ at a heating rate of ≤50℃ / h, and keep it stable.

[0047] S14. Start the circulating cooling water of the heat dissipation device 8 and set the inlet and outlet water temperatures.

[0048] S2. Continuous reduction and stability control S21. Titanium tetrachloride is added to reactor 1 through tetrachloride feeding pipe 6. The addition rate of titanium tetrachloride linearly increases from 0 to a preset 1600 kg / h within 2 hours, and then maintains a constant addition rate. Figure 3 As shown, the feeding rate of titanium tetrachloride can be stably maintained at over 1600 kg / h, which is about 4 times that of the traditional process.

[0049] S22. The reduction reaction begins immediately. The radar level gauge starts working. The magnesium chloride discharge system continuously or intermittently discharges magnesium chloride based on the data measured by the radar level gauge (a high level and a low level are preset; discharge begins when the high level is exceeded and stops when the low level is exceeded). When the liquid level reaches the high level, the electric disc valve opens and the discharge device starts discharging; when the liquid level drops to the low level, the valve closes and discharge stops.

[0050] S23. The heat of reaction is discharged in real time by the heat dissipation device 8. By adjusting the cooling water flow rate, the temperature fluctuation of key temperature measuring points in reactor 1 is controlled within ±5℃.

[0051] S3. Continuous removal of sponge titanium S31. Start the high-temperature resistant conveying mechanism 32 and run it at a low speed (0.2 m / min).

[0052] S32. The sponge titanium generated by the reduction reaction gradually forms and deposits at the bottom of reactor 1. The continuously operating high-temperature resistant conveying mechanism 32 retrieves the sponge titanium through its perforated chain plate, while the entrained liquid magnesium and magnesium chloride are drained back into reactor 1 through the holes.

[0053] S33. The sponge titanium is conveyed to collector 9, where it undergoes further purification to obtain a high-purity sponge titanium product, which can then be crushed and packaged. The conveying speed of the high-temperature resistant conveying mechanism 32 is adjustable to match the titanium production rate (approximately 400 kg / h), enabling continuous discharge.

[0054] S4. Continuous Operation and Material Replenishment S41. Based on the reaction consumption, periodically pump deeply purified magnesium into reactor 1 through magnesium replenishment pipe 4 to maintain sufficient reducing agent required for the reaction.

[0055] S42. The entire system can be planned to operate continuously for more than 3,000 hours (approximately 4 months) under fault-free conditions. During operation, key parameters such as titanium tetrachloride feeding rate, reaction temperature, and liquid level remain highly stable.

[0056] S43. When planning a shutdown, first stop adding titanium tetrachloride. After the material in reactor 1 has basically reacted, empty the system and carry out maintenance. Example 3: Sponge Titanium Asphalt Zone

[0057] The difference between this embodiment and Embodiment 1 is that the top of the upper end of the conveying pipe 31 is higher than the top of the reactor 1, thus forming a closed space (forming a draining chamber 34) at the upper end of the conveying pipe 31 that is higher than the upper surface of the magnesium layer inside the reactor. During the conveying process, the high-temperature conveying mechanism 32 passes through the draining chamber 34 (the draining chamber 34 is filled with argon gas). The magnesium chloride on the sponge titanium slides from the sponge titanium to the high-temperature conveying mechanism 32, and finally slides from the hollow hole of the high-temperature conveying mechanism 32 to the conveying pipe 31, and slides down along the conveying pipe 31 to achieve the initial draining of the sponge titanium. Example 4: Deep purification device for metallic magnesium

[0058] The difference between this embodiment and embodiments 1-3 is that this embodiment adjusts the position and purpose of some connecting pipes between the feeding and discharging system and the functional interface on the sealing cover 7. In this embodiment, as shown... Figure 5 As shown, the feeding and discharging system includes crude magnesium and tetrachloride feeding pipes 10, refined magnesium discharge pipe 11, and magnesium chloride discharge system, which are respectively connected to reactor 1.

[0059] The crude magnesium and titanium tetrachloride feeding pipe 10 is used to sequentially add crude magnesium and titanium tetrachloride into reactor 1; the refined magnesium discharge pipe 11 extends through the sealing cover 7 into the middle of reactor 1. The magnesium chloride discharge system is consistent with the structure of Examples 1-3. Example 5: Deep purification of metallic magnesium

[0060] This embodiment utilizes the characteristic that magnesium chloride and sponge titanium produced by magnesium reduction of titanium tetrachloride both have strong physical or chemical adsorption properties. Using the device described in Example 4, non-metallic and metallic impurities in magnesium are replaced and adsorbed to achieve deep purification of magnesium. Moreover, the magnesium chloride and sponge titanium produced by purification can be reused without generating waste residue, thus achieving deep purification of magnesium.

[0061] The magnesium metal to be purified (crude magnesium) is placed in reactor 1 through crude magnesium and tetrachloride feeding pipe 10. Under an inert atmosphere and at a temperature of 850-900℃, titanium tetrachloride is introduced through crude magnesium and tetrachloride feeding pipe 10 at a controlled rate. The sponge titanium and magnesium chloride generated by the reaction adsorb and replace the metallic and non-metallic impurities in the magnesium. The purified refined magnesium is discharged through refined magnesium discharge pipe, and the generated sponge titanium is removed through conveying device 3.

[0062] Other aspects of this invention that are not detailed herein are all conventional techniques known to those skilled in the art.

[0063] It should be noted that the terms “comprising,” “including,” or any other variations are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0064] The scope of protection of this invention is not limited to the technical solutions disclosed in the specific embodiments. Any modifications, equivalent substitutions, improvements, etc., made to the above embodiments based on the technical essence of this invention shall fall within the scope of protection of this invention.

Claims

1. A process for the continuous reduction production of titanium-zirconium-hafnium metals, characterized in that, Includes the following steps: Under an inert atmosphere, reactor (1) is heated to the reaction temperature and metallic magnesium is added thereto; Tetrachloride was continuously added to reactor (1) at a constant rate to carry out a reduction reaction; During the reaction, magnesium chloride melt is continuously or intermittently discharged, and metallic magnesium is replenished multiple times; The generated sponge titanium is continuously removed from the reactor (1) by a conveying device (3) that is directly connected to the reactor (1) and transported to a collector (9) for collection.

2. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 1, characterized in that: The tetrachloride is any one of titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride.

3. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 1, characterized in that: A heating furnace (2) is installed outside the reactor (1); a sealing cover (7) is provided on the top of the reactor (1); and a feeding and discharging system connected to the reactor (1) is installed on the sealing cover (7).

4. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 3, characterized in that: The feeding and discharging system includes a magnesium replenishment pipe (4), a tetrachloride feeding pipe (6), and a magnesium chloride discharge system, which are respectively connected to the reactor (1).

5. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 3, characterized in that: The feeding and discharging system includes crude magnesium and tetrachloride feeding pipes (10) connected to the reactor (1), refined magnesium discharge pipes (11), and magnesium chloride discharge system.

6. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 4 or 5, characterized in that: The magnesium chloride discharge system includes a liquid level detection device on the reactor (1), a magnesium chloride discharge pipe (5) connected to the bottom of the reactor (1), an electric discharge valve on the magnesium chloride discharge pipe (5), and a discharge device located outside the reactor (1) and connected to the magnesium chloride discharge pipe (5). The magnesium chloride melt is discharged through the discharge device and the magnesium chloride discharge pipe (5).

7. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 3, characterized in that: A heat dissipation device (8) is installed inside the reactor (1), which extends from the top of the reactor (1) into the reactor (1) through a heat dissipation pipe installed on the sealing cover (7).

8. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 1, characterized in that: The conveying device (3) includes a conveying pipe (31) and a high-temperature resistant conveying mechanism (32) disposed in the conveying pipe (31); one end of the conveying pipe (31) is connected to the inside of the reactor (1), and the other end is connected to the collector (9).

9. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 8, characterized in that: The high-temperature resistant conveying mechanism (32) is a chain plate conveyor, and a guard plate is provided on the chain plate of the high-temperature resistant conveying mechanism (32).

10. The process for continuous reduction production of titanium-zirconium-hafnium metals according to claim 1, characterized in that: The magnesium metal is refined magnesium or crude magnesium.

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