Purification process and purification equipment for electrolytic titanium rod

Abstract

The invention belongs to the related technical field of high-purity titanium production, and particularly discloses a purification process and purification equipment for an electrolytic titanium rod. The purification process comprises first acid leaching, crushing, second acid leaching, filtering and washing, high-purity titanium is obtained, the electrolytic titanium rod subjected to first acid leaching is crushed in second acid liquor, and stirring and ultrasonic treatment are carried out in the second acid leaching process. The titanium rod can be preferentially permeated through the first acid leaching, so that the structure of the electrolytic titanium rod is loosened, follow-up crushing is facilitated, the impurity removal effect can be greatly improved in cooperation with follow-up crushing and second acid leaching, and the purity of the obtained high-purity titanium reaches 4-5 N.

Description

Technical Field

[0001] This invention belongs to the technical field of high-purity titanium production, and relates to a method for processing electrolytic titanium rods, specifically a purification process and purification equipment for electrolytic titanium rods. Background Technology

[0002] Molten salt electrolysis is one of the commonly used methods for preparing high-purity titanium metal materials. It involves dissolving crude titanium as the anode in a molten salt electrolyte containing one or more alkali metal halides, and then depositing the dissolved titanium in a pure titanium metal cathode to obtain high-purity electrolytic titanium. However, the resulting high-purity electrolytic titanium rod is prone to contain impurities such as alkali metal halide molten salt electrolytes or titanium halides, affecting the purity of the product.

[0003] In existing technologies, the titanium rods obtained by electrolysis are usually purified by crushing, hydrolysis, and acid leaching. During the preparation of high-purity titanium by molten salt electrolysis, low-valence titanium halides, such as TiCl3, may be mixed in with the electrolyzed titanium. TiCl3 is prone to hydrolysis to generate inert hydrated titanium dioxide (TiO2·xH2O), etc. Inert hydrated titanium dioxide does not react with acid and cannot be removed by acid leaching, thus affecting the purity of the finished high-purity titanium. Summary of the Invention

[0004] In view of the defects and deficiencies of the existing technology, the present invention provides, firstly, a purification process for electrolytic titanium rods; and secondly, a purification system for electrolytic titanium rods.

[0005] In a first aspect, the present invention provides a purification process for electrolytic titanium rods, comprising the following steps: Step 1: Immerse the electrolytic titanium rod completely in the first acid solution, and then wash the titanium rod with pure water to obtain the pretreated titanium rod. Step 2: Mix the pretreated titanium rod and the second acid solution, crush them to obtain slurry A; add the second acid solution to slurry A again for acid leaching, while stirring and sonicating, to obtain slurry B; Step 3: Filter slurry B, wash the obtained solid particles with pure water to obtain high-purity titanium.

[0006] Preferably, the first acid solution and the second acid solution are either dilute sulfuric acid solution or dilute hydrochloric acid solution, or both.

[0007] Preferably, in step 1, the concentration of the first acid solution is 1.5wt% to 5wt%, and the acid leaching time is 0.5 to 1h.

[0008] Preferably, in step 1, the solid-liquid ratio of the electrolytic titanium rod and the first acid solution is 1:2~8 kg / L.

[0009] Preferably, in step 2, the concentration of the second acid solution is 0.1 wt% to 1 wt%.

[0010] Preferably, in step 2, the solid-liquid ratio of slurry A is 1~6:1 kg / L; and the solid-liquid ratio of slurry B is 1:2~6 kg / L.

[0011] Preferably, in step 2, the crushing speed is 80~200 r / min and the crushing time is 10~30 min.

[0012] Preferably, in step 2, during acid leaching, the stirring speed is 60~180 r / min, the ultrasonic frequency is 20~40 kHz, and the time for simultaneous stirring and ultrasonic treatment of the material is 20~40 min.

[0013] Secondly, the present invention provides a purification system for electrolytic titanium rods, including a first acid leaching device and a second acid leaching device. The second acid leaching device includes a tank body, a first stirring shaft, and a second stirring shaft. The first stirring shaft and the second stirring shaft are rotatably connected to the tank body. The first stirring shaft and the second stirring shaft rotate in opposite directions. Multiple stirring blades are spaced apart on the first stirring shaft and the second stirring shaft. The stirring blades on the first stirring shaft and the second stirring shaft are staggered. An ultrasonic generator is provided at the bottom of the tank body.

[0014] Preferably, a spray pipe for spraying acid solution is provided above the barrel, and multiple nozzles are spaced apart on the water pipe.

[0015] Preferably, a discharge pipe is provided at the bottom of the barrel, and a spiral blade is rotatably arranged inside the discharge pipe, with the spiral blade and the discharge pipe being coaxially arranged.

[0016] Preferably, the discharge end of the discharge pipe is provided with a receiving bucket, and a screen is provided in the receiving bucket.

[0017] Preferably, the screen is inclined downward along the flow direction of the material.

[0018] Preferably, the first acid leaching device is an acid leaching tank.

[0019] Compared with the prior art, the present invention has the following significant advantages: (1) In the purification process provided by the present invention, the titanium rod can be preferentially penetrated by the first acid leaching, thereby loosening the structure of the electrolytic titanium rod, which is convenient for subsequent crushing. Combined with subsequent crushing and second acid leaching, the impurity removal effect can be greatly improved, and the purity of the high-purity titanium obtained reaches 4~5N.

[0020] (2) This invention solves the problem of uneven macro-mixing through double reverse stirring, further optimizes the problem of slow micro-interface reaction through ultrasonic generator, and reduces ineffective reaction consumption through pretreatment and crushing. The combination of these three features enables the acid leaching reaction to be completed under low concentration, room temperature and short time conditions, thereby reducing the energy consumption of acid preparation, heating and long-term equipment operation from the source, and ultimately achieving a reduction in production energy consumption and an increase in product purity. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the overall structure of the purification system for the electrolytic titanium rod provided in Example 1.

[0022] Figure descriptions: 1. Barrel body; 2. Stirring shaft one; 3. Stirring shaft two; 4. Spray pipe; 5. Discharge pipe; 6. Receiving barrel; 7. Stirring blades; 8. First drive; 9. Second drive; 10. Spray head; 11. Ultrasonic generator; 12. Ultrasonic transducer; 13. Rotating shaft; 14. Spiral blades; 15. Third drive; 16. Screen. Detailed Implementation

[0023] The present invention provides the following specific technical solutions.

[0024] In a first aspect, the present invention provides a purification process for electrolytic titanium rods, comprising the following steps: Step 1: Immerse the electrolytic titanium rod completely in the first acid solution, and then wash the titanium rod with pure water to obtain the pretreated titanium rod. Step 2: Mix the pretreated titanium rod and the second acid solution, crush them to obtain slurry A; add the second acid solution to slurry A again for acid leaching, while stirring and sonicating, to obtain slurry B; Step 3: Filter slurry B, wash the obtained solid particles with pure water to obtain high-purity titanium.

[0025] Through research, the inventors discovered that the internal structure of electrolytic titanium rods obtained by molten salt electrolysis is mostly dendritic or acicular, and the surface structure of the electrolytic titanium rod is denser than its internal structure. During the electrolytic deposition process, alkali metal halide molten salt electrolytes or titanium halides are easily trapped in the gaps between the titanium rods, affecting the purity of the final high-purity titanium product. Based on this, the inventors first immerse the electrolytic titanium rod entirely in a first acid solution when processing it. This first acid immersion removes most of the impurities from the electrolytic titanium rod. Firstly, this avoids further contamination of the electrolytic titanium rod by impurities; secondly, because the internal structure of the electrolytic titanium rod is mostly dendritic and acicular, the first acid immersion allows for preferential penetration, thereby loosening the structure of the electrolytic titanium rod and facilitating subsequent crushing. Combined with subsequent crushing and a second acid immersion, the impurity removal effect is significantly improved, and the purity of the obtained high-purity titanium reaches 4-5N.

[0026] Preferably, the first acid solution and the second acid solution are either dilute sulfuric acid solution or dilute hydrochloric acid solution, or both.

[0027] Preferably, in step 1, the concentration of the first acid solution is 1.5wt% to 5wt%, and the acid leaching time is 0.5 to 1h.

[0028] Preferably, in step 1, the solid-liquid ratio of the electrolytic titanium rod and the first acid solution is 1:2~8 kg / L.

[0029] In practical applications, the electrolytic titanium rod is immersed entirely in the first acid solution for the first acid leaching. Preferably, the ratio of the first acid solution to the electrolytic titanium rod is 1:2 to 8 kg / L, ensuring a superior acid leaching effect on the titanium rod. The solid-liquid ratio of the first acid solution to the electrolytic titanium rod can be 1:2 kg / L, 1:3 kg / L, 1:4 kg / L, 1:5 kg / L, 1:6 kg / L, 1:7 kg / L, or 1:8 kg / L.

[0030] Preferably, in step 2, the concentration of the second acid solution is 0.1 wt% to 1 wt%.

[0031] Through research, the inventors discovered that the first acid solution has a higher concentration. A high-concentration acid solution has a stronger dissolving ability and can quickly react with easily soluble impurities on the surface, shortening the acid leaching time and improving the pretreatment efficiency. The titanium matrix of the entire titanium rod dissolves more slowly at this concentration, which can avoid excessive loss of the titanium matrix due to excessive acid concentration, while achieving surface impurity removal. The second acid solution has a lower concentration. During the second acid leaching, the titanium rod has been crushed, significantly increasing the surface area of ​​the particles. Additionally, trace impurities embedded inside the titanium rod are released. The low-concentration acid solution has a weaker dissolving power, allowing it to slowly and selectively dissolve the trace impurities remaining inside the particles. This avoids excessive corrosion of the titanium particle matrix by the high-concentration acid solution. Combined with stirring and ultrasound, the low-concentration acid solution can fully penetrate into the gaps between the crushed particles, achieving deep purification with low loss and ensuring the purity of the final product.

[0032] If both steps use high-concentration acid, the crushed titanium particles will be over-dissolved due to their increased surface area, reducing the recovery rate of high-purity titanium. If both steps use low-concentration acid, the surface impurities of the entire titanium rod cannot be removed quickly in the first step, prolonging the process time and resulting in incomplete impurity removal. The concentration gradient design precisely avoids these two problems, achieving a seamless transition between efficient impurity removal and low-loss purification. It first efficiently removes large surface impurities, then performs fine purification to reduce titanium matrix loss, achieving a balance between purification efficiency and product recovery rate through gradient acid leaching.

[0033] In practical applications, the concentration of the second acid solution can be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, or 1.0wt%.

[0034] Preferably, in step 2, the solid-liquid ratio of slurry A is 1~6:1 kg / L; and the solid-liquid ratio of slurry B is 1:2~6 kg / L.

[0035] In practical applications, the solid-liquid ratio of slurry A can be 1:1 kg / L, 2:1 kg / L, 3:1 kg / L, 4:1 kg / L, 5:1 kg / L, or 6:1 kg / L; the solid-liquid ratio of slurry B can be 1:2 kg / L, 1:3 kg / L, 1:4 kg / L, 1:5 kg / L, or 1:6 kg / L.

[0036] Preferably, in step 2, the crushing speed is 80~200 r / min and the crushing time is 10~30 min.

[0037] Preferably, in step 2, during acid leaching, the stirring speed is 60~180 r / min, the ultrasonic frequency is 20~40 kHz, and the time for simultaneous stirring and ultrasonic treatment of the material is 20~40 min.

[0038] Secondly, the present invention provides a purification system for electrolytic titanium rods, including a first acid leaching device and a second acid leaching device. The second acid leaching device includes a tank body, a first stirring shaft, and a second stirring shaft. The first stirring shaft and the second stirring shaft are rotatably connected to the tank body. The first stirring shaft and the second stirring shaft rotate in opposite directions. Multiple stirring blades are spaced apart on the first stirring shaft and the second stirring shaft. The stirring blades on the first stirring shaft and the second stirring shaft are staggered. An ultrasonic generator is provided at the bottom of the tank body.

[0039] Through research, the inventors discovered that traditional titanium purification processes rely on high acid concentrations, high temperatures, and prolonged stirring to drive the reaction, essentially compensating for low mass transfer efficiency with high energy consumption. In this invention, however, the problem of macroscopic uneven mixing is solved through double-reverse stirring in the second acid leaching process, the ultrasonic generator further optimizes the slow reaction at the microscopic interface, and the step-by-step process reduces ineffective reaction consumption through pretreatment and crushing. The combination of these three elements allows the acid leaching reaction to be completed under low concentration, room temperature, and short time conditions, reducing energy consumption from acid preparation, heating, and prolonged equipment operation at the source, ultimately achieving reduced production energy consumption and improved product purity.

[0040] Preferably, a spray pipe for spraying acid solution is provided above the barrel, and multiple nozzles are spaced apart on the water pipe.

[0041] Preferably, a discharge pipe is provided at the bottom of the barrel, and a spiral blade is rotatably arranged inside the discharge pipe, with the spiral blade and the discharge pipe being coaxially arranged.

[0042] Preferably, the discharge end of the discharge pipe is provided with a receiving bucket, and a screen is provided in the receiving bucket.

[0043] Preferably, the screen is inclined downward along the flow direction of the material.

[0044] Preferably, the first acid leaching device is an acid leaching tank.

[0045] To make the technical problems, technical solutions and technical advantages of the present invention clearer, a detailed description will be given below with reference to specific examples. However, the scope of protection of the present invention is not limited to the following specific embodiments.

[0046] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0047] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0048] Example 1: This invention provides a purification system for electrolytic titanium rods, including a first acid leaching device and a second acid leaching device. The first acid leaching device is an acid leaching tank (not shown in the figure). The second acid leaching device includes a tank body 1, a first stirring shaft 2, a second stirring shaft 3, a spray pipe 4, a discharge pipe 5, and a receiving tank 6. The tank body 1 is a hollow cylindrical shape, with an acid solution receiving port at the top. The first stirring shaft 2 and the second stirring shaft 3 are arranged along the height direction of the tank body 1, and both are rotatably connected to the tank body 1. The stirring shafts 2 and 3 rotate in opposite directions. Multiple stirring blades 7 are spaced apart on both the first stirring shaft 2 and the second stirring shaft 3. The stirring blades 7 on the first stirring shaft 2 and the second stirring shaft 3 are staggered. A first drive 8 for driving the first stirring shaft 2 to rotate is provided at the top of the tank body 1, and a second drive 9 for driving the second stirring shaft 3 to rotate is also provided at the top of the tank body 1. Both the first drive 8 and the second drive 9 are located outside the tank body 1. In a specific embodiment of the present invention, both the first drive 8 and the second drive 9 are motors, and the first drive 8 and the second drive 9 are fixedly connected to the top of the barrel 1.

[0049] The spray pipe 4 is located in the upper part of the tank body 1, and multiple spray heads 10 are arranged at intervals on the spray pipe 4. The multiple spray heads 10 are evenly distributed.

[0050] An ultrasonic component is also provided at the lower part of the barrel body 1. In a specific embodiment of the present invention, the ultrasonic component includes an ultrasonic generator 11 and an ultrasonic transducer 12. The ultrasonic generator 11 and the ultrasonic transducer 12 are electrically connected. The ultrasonic transducer 12 is located outside the barrel body 1. When the stirring shaft 1 2 and the stirring shaft 2 3 are started, the ultrasonic transducer 12 is started at the same time to perform ultrasonic vibration on the material inside the barrel body 1.

[0051] A discharge pipe 5 is located at the bottom of the barrel 1, and is fixedly connected to and communicates with the bottom of the barrel 1. A rotating shaft 13 is rotatably connected to the discharge pipe 5, and the rotating shaft 13 and the discharge pipe 5 are coaxially arranged. A spiral blade 14 is fixedly connected to the rotating shaft 13. One end of the discharge pipe 5 is closed and fixedly connected to a third drive 15 for driving the rotating shaft 13 to rotate. In a specific embodiment of the present invention, the third drive 15 is a motor. The other end of the discharge pipe 5 is connected to a receiving barrel 6, and a screen 16 is provided inside the receiving barrel 6. The screen 16 is inclined, and the inclination direction is downward along the conveying direction.

[0052] A discharge valve is provided between the discharge pipe 5 and the barrel 1 to control the discharge of material from the barrel 1. In a specific embodiment of the present invention, the discharge pipe 5 is arranged horizontally. In other specific embodiments, the discharge pipe 5 may also be arranged at an angle, with the high end of the discharge pipe 5 close to the barrel 1 and the low end of the discharge pipe 5 close to the receiving barrel 6.

[0053] The working process of the above-mentioned purification system for electrolytic titanium rods is as follows: First, place the electrolytic titanium rod in the acid leaching tank for the first acid leaching. Then, open the top cover of the tank 1 of the second acid leaching device, add the electrolytic titanium rod after the first acid leaching into the tank 1, and open the spray pipe 4 to add a certain amount of second dilute acid through the acid solution inlet. Then, the first drive 8 and the second drive 9 are turned on, and the first stirring shaft 2 and the second stirring shaft 3 rotate. Under the action of the stirring blade 7, the electrolytic titanium rod after the first acid leaching is crushed. Then, the spray pipe 4 is opened, and the second acid solution is added again through the acid solution inlet. When the second acid solution in the tank 1 reaches a certain amount, the ultrasonic component is started. After the first stirring shaft 2, the second stirring shaft 3 and the ultrasonic component continue to work for a certain period of time, the discharge valve is opened, and the material in the tank 1 enters the discharge pipe 5. Then, the third drive 15 is started, driving the spiral blade 14 to rotate and transporting the material in the discharge pipe 5 to the receiving tank 6. The screen 16 in the receiving tank 6 achieves solid-liquid separation. The second acid solution enters the receiving tank 6, and the high-purity titanium solid is located above the screen 16. The screen 16 is removed, and the high-purity titanium is cleaned to obtain high-purity titanium with a purity higher than 4N.

[0054] Example 2: A purification process for electrolytic titanium rods includes the following steps: Step 1: Place the electrolytic titanium rod in an acid pickling tank, then add the first acid solution to the acid pickling tank to completely immerse the electrolytic titanium rod. The solid-liquid ratio of the electrolytic titanium rod to the first acid solution is 1:5 kg / L. After standing for 1 hour, wash with water to obtain the acid-impregnated electrolytic titanium rod. The first acid solution is dilute sulfuric acid with a concentration of 1.5 wt%.

[0055] Step 2: Transfer the acid-leached electrolytic titanium rod to the tank. Add the second acid solution (dilute sulfuric acid, 0.1 wt%) through the spray pipe. When the solid-liquid ratio of the titanium slag and the second acid solution is 6:1 kg / L, stop adding the second acid solution. Then start stirring shaft one and stirring shaft two at 80 r / min for 15 min (stirring shaft one and stirring shaft two rotate in opposite directions) to break the acid-leached electrolytic titanium rod and obtain titanium slag. Then spray the second acid solution (dilute sulfuric acid, 0.1 wt%) into the tank again. When the solid-liquid ratio of the titanium slag and the second acid solution is 1:2 kg / L, stop adding the second acid solution. Turn on the ultrasonic component and continuously stir (stirring shaft one and stirring shaft two rotate continuously) and ultrasonically vibrate at 20 kHz for 30 min to obtain a slurry.

[0056] Step 3: Screen the slurry and wash the obtained solid particles with pure water multiple times to obtain high-purity titanium.

[0057] Comparative Example 1: A purification process for electrolytic titanium rods includes the following steps: Step 1: Transfer the electrolytic titanium rod to the tank. Add the first acid solution (dilute sulfuric acid, 1.5 wt%) through the spray pipe. When the solid-liquid ratio of the electrolytic titanium rod to the first acid solution is 6:1 kg / L, stop adding the first acid solution. Then start stirring shaft one and stirring shaft two at 80 r / min for 30 min (stirring shaft one and stirring shaft two rotate in opposite directions) to break up the acid-leached electrolytic titanium rod and obtain titanium slag. Then spray the first acid solution (dilute sulfuric acid, 1.5 wt%) into the tank through the spray pipe. When the solid-liquid ratio of the titanium slag to the first acid solution is 1:2 kg / L, stop adding the first acid solution. Turn on the ultrasonic component and continuously stir (stirring shaft one and stirring shaft two rotate continuously) and ultrasonically vibrate at 20 kHz for 30 min to obtain a slurry.

[0058] Step 2: Screen the slurry and wash the resulting solid particles with pure water multiple times to obtain high-purity titanium.

[0059] Comparative Example 2: A purification process for electrolytic titanium rods includes the following steps: Step 1: Transfer the electrolytic titanium rod to the tank. Add the second acid solution (dilute sulfuric acid, 0.1 wt%) through the spray pipe. When the solid-liquid ratio of the electrolytic titanium rod to the second acid solution is 6:1 kg / L, stop adding the second acid solution. Then start stirring shaft one and stirring shaft two at 80 r / min for 30 min (stirring shaft one and stirring shaft two rotate in opposite directions) to break up the acid-leached electrolytic titanium rod and obtain titanium slag. Then spray the second acid solution (dilute sulfuric acid, 0.1 wt%) into the tank through the spray pipe. When the solid-liquid ratio of the titanium slag to the second acid solution is 1:2 kg / L, stop adding the second acid solution. Turn on the ultrasonic component and continuously stir (stirring shaft one and stirring shaft two rotate continuously) and ultrasonically vibrate at 20 kHz for 30 min to obtain a slurry.

[0060] Step 2: Screen the slurry and wash the resulting solid particles with pure water multiple times to obtain high-purity titanium.

[0061] Comparative Example 3: A purification process for electrolytic titanium rods includes the following steps: Step 1: Place the electrolytic titanium rod in an acid pickling tank, then add the first acid solution to the acid pickling tank to completely immerse the electrolytic titanium rod. The solid-liquid ratio of the electrolytic titanium rod to the first acid solution is 1:5 kg / L. After standing for 1 hour, wash with water to obtain the acid-impregnated electrolytic titanium rod. The first acid solution is dilute sulfuric acid with a concentration of 1.5 wt%.

[0062] Step 2: Transfer the acid-leached electrolytic titanium rod to the tank. Add the first acid solution through the spray pipe. When the solid-liquid ratio of titanium slag to the first acid solution is 6:1 kg / L, stop adding the first acid solution. Then start stirring shaft one and stirring shaft two at 80 r / min for 10 min to crush the acid-leached electrolytic titanium rod and obtain titanium slag. Then spray the first acid solution into the tank through the spray pipe. When the solid-liquid ratio of titanium slag to the first acid solution is 1:2 kg / L, stop adding the first acid solution. Turn on the ultrasonic component and continuously stir (stirring shaft one and stirring shaft two rotate continuously) and ultrasonically vibrate at 20 kHz for 30 min to obtain a slurry.

[0063] Step 3: Screen the slurry and wash the obtained solid particles with clean water multiple times to obtain high-purity titanium.

[0064] Comparative Example 4: A purification process for electrolytic titanium rods includes the following steps: Step 1: Place the electrolytic titanium rod in an acid pickling tank, then add the first acid solution to the acid pickling tank to completely immerse the electrolytic titanium rod. The solid-liquid ratio of the electrolytic titanium rod to the first acid solution is 1:5 kg / L. After standing for 1 hour, wash with water to obtain the acid-impregnated electrolytic titanium rod. The second acid solution is dilute sulfuric acid with a concentration of 0.1 wt%.

[0065] Step 2: Transfer the acid-leached electrolytic titanium rod to the tank. Add the second acid solution through the spray pipe. When the solid-liquid ratio of the titanium slag and the second acid solution is 6:1 kg / L, stop adding the second acid solution. Then start stirring shaft one and stirring shaft two at 80 r / min for 20 min to crush the acid-leached electrolytic titanium rod and obtain titanium slag. Then spray the second acid solution into the tank through the spray pipe. When the solid-liquid ratio of the titanium slag and the second acid solution is 1:2 kg / L, stop adding the second acid solution. Turn on the ultrasonic component and continuously stir (stirring shaft one and stirring shaft two rotate continuously) and ultrasonically vibrate at 20 kHz for 30 min to obtain a slurry.

[0066] Step 3: Screen the slurry and wash the obtained solid particles with clean water multiple times to obtain high-purity titanium.

[0067] The titanium slag obtained by controlling the stirring shaft one and stirring shaft two to rotate at 80 r / min in Comparative Examples 1 to 4 and Example 2 is basically the same.

[0068] Comparative Example 5: The difference from Example 2 is that in the electrolytic titanium rod device used in step 2, the first stirring shaft and the second stirring shaft rotate in the same direction.

[0069] Example 3: A purification process for electrolytic titanium rods includes the following steps: Step 1: Place the electrolytic titanium rod in an acid pickling tank, then add the first acid solution to the pickling tank to completely immerse the electrolytic titanium rod. The solid-liquid ratio of the electrolytic titanium rod to the first acid solution is 1:2 kg / L. After standing for 1 hour, wash with water to obtain the acid-impregnated electrolytic titanium rod. The first acid solution is dilute sulfuric acid with a concentration of 2 wt%.

[0070] Step 2: Transfer the acid-leached electrolytic titanium rod to the tank. Add the second acid solution through the spray pipe. When the solid-liquid ratio of the titanium slag and the second acid solution is 6:1 kg / L, stop adding the second acid solution. Then start stirring shaft one and stirring shaft two at 80 r / min for 15 min to crush the acid-leached electrolytic titanium rod and obtain titanium slag. Then spray the second acid solution into the tank through the spray pipe. The second acid solution is dilute sulfuric acid with a concentration of 0.1 wt%. When the solid-liquid ratio of the titanium slag and the second acid solution is 1:2 kg / L, stop adding the second acid solution. Turn on the ultrasonic component and continuously stir (stirring shaft one and stirring shaft two rotate continuously) and ultrasonically vibrate at 20 kHz for 30 min to obtain a slurry.

[0071] Step 3: Screen the slurry and wash the obtained solid particles with clean water multiple times to obtain high-purity titanium.

[0072] Example 4: A purification process for electrolytic titanium rods includes the following steps: Step 1: Place the electrolytic titanium rod in an acid pickling tank, then add the first acid solution to the acid pickling tank to completely immerse the electrolytic titanium rod. The solid-liquid ratio of the electrolytic titanium rod to the first acid solution is 1:8 kg / L. After standing for 1 hour, wash with water to obtain the acid-impregnated electrolytic titanium rod. The first acid solution is dilute sulfuric acid with a concentration of 1.5 wt%.

[0073] Step 2: Transfer the acid-leached electrolytic titanium rod to the tank. Add the second acid solution through the spray pipe. When the solid-liquid ratio of the titanium slag and the second acid solution is 6:1 kg / L, stop adding the second acid solution. Then start stirring shaft one and stirring shaft two at 80 r / min for 15 min to break the acid-leached electrolytic titanium rod and obtain titanium slag. Then spray the second acid solution into the tank through the spray pipe. The second acid solution is dilute sulfuric acid with a concentration of 0.2 wt%. When the solid-liquid ratio of the titanium slag and the second acid solution is 1:2 kg / L, stop adding the second acid solution. Turn on the ultrasonic component and continuously stir (stirring shaft one and stirring shaft two rotate continuously) and ultrasonically vibrate at 20 kHz for 30 min to obtain a slurry.

[0074] Step 3: Screen the slurry and wash the obtained solid particles with pure water multiple times to obtain high-purity titanium.

[0075] The purity and yield of the high-purity titanium prepared in Examples 2-4 and Comparative Examples 1-4 were tested. The test data are shown in the table below: Table 1. Purity and yield of high-purity titanium obtained in Examples 2-4 and Comparative Examples 1-4 As shown in Table 1, when comparing Example 2 with Comparative Examples 1 and 2, the purity of the product after a first acid leaching followed by crushing and a second acid leaching was significantly improved. Furthermore, the pretreatment of the electrolytic titanium rod with the first acid solution loosened and separated the internal electrolyte, making the electrolytic titanium more flexible and creating conditions for the subsequent crushing process, thus reducing energy consumption.

[0076] Comparing Example 2 with Comparative Examples 3 and 4, the product purity remained unchanged, and the energy consumption was similar. However, Comparative Example 3 used only the first acid solution, which had a high concentration and resulted in resource waste. In Comparative Example 4, the second acid solution was used, which had a lower concentration, leading to incomplete cleaning of impurities and reduced product purity.

[0077] Comparing Example 2 and Comparative Example 5, in Comparative Example 5, because the first and second stirring shafts rotate in the same direction, the electrolytic titanium was not sufficiently crushed and stirred and cleaned, resulting in a decrease in product purity and an increase in energy consumption.

[0078] Based on Examples 2-4, it can be seen that the technical solution provided by the present invention can reduce the overall acid usage and energy consumption, and the purity of the product obtained is improved, with the product purity remaining stable above 4N.

[0079] The above-described embodiments are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the technical scope of the present invention, based on the technical solution and concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A purification process for electrolytic titanium rods, characterized in that, Includes the following steps: Step 1: Immerse the electrolytic titanium rod completely in the first acid solution, and then wash the titanium rod with pure water to obtain the pretreated titanium rod. Step 2: Mix the pretreated titanium rod and the second acid solution, crush them to obtain slurry A; add the second acid solution to slurry A again for acid leaching, while stirring and sonicating, to obtain slurry B; Step 3: Filter slurry B, wash the obtained solid particles with pure water to obtain high-purity titanium.

2. The purification process for electrolytic titanium rods as described in claim 1, characterized in that, The first acid solution and the second acid solution are either dilute sulfuric acid solution or dilute hydrochloric acid solution, or both.

3. The purification process for electrolytic titanium rods as described in claim 1 or 2, characterized in that, In step 1, the concentration of the first acid solution is 1.5wt%~5wt%, and the acid leaching time is 0.5~1h.

4. The purification process for electrolytic titanium rods as described in claim 1, characterized in that, In step 1, the solid-liquid ratio of the electrolytic titanium rod and the first acid solution is 1:2~8 kg / L.

5. The purification process for electrolytic titanium rods as described in claim 1 or 2, characterized in that, In step 2, the concentration of the second acid solution is 0.1 wt% to 1 wt%.

6. The purification process for electrolytic titanium rods as described in claim 1, characterized in that, In step 2, the solid-liquid ratio of slurry A is 1~6:1 kg / L; the solid-liquid ratio of slurry B is 1:2~6 kg / L.

7. The purification process for electrolytic titanium rods as described in claim 1 or 6, characterized in that, In step 2, the crushing process is agitation crushing, with a crushing speed of 80~200 r / min and a crushing time of 10~30 min; during acid leaching, the agitation speed is 60~180 r / min and the ultrasonic frequency is 20~40 kHz; the time for simultaneous agitation and ultrasonic treatment of the material is 20~40 min.

8. A purification system for electrolytic titanium rods, characterized in that, The apparatus includes a first acid leaching device and a second acid leaching device. The second acid leaching device includes a tank body, a first stirring shaft, and a second stirring shaft. Both the first stirring shaft and the second stirring shaft are rotatably connected to the tank body. The first stirring shaft and the second stirring shaft rotate in opposite directions. Multiple stirring blades are spaced apart on the first stirring shaft and the second stirring shaft. The stirring blades on the first stirring shaft and the second stirring shaft are staggered. An ultrasonic generator is provided at the bottom of the tank body.

9. The purification system for electrolytic titanium rods as described in claim 8, characterized in that, A spray pipe for spraying acid solution is provided above the barrel, and multiple nozzles are spaced apart on the water pipe; a discharge pipe is provided at the bottom of the barrel, and a spiral blade is rotatably installed inside the discharge pipe, with the spiral blade and the discharge pipe being coaxially arranged.

10. The purification system for electrolytic titanium rods as described in claim 8 or 9, characterized in that, The discharge end of the discharge pipe is equipped with a receiving bucket, and a screen is installed in the receiving bucket. The screen is inclined downward along the flow direction of the material.

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