A method for producing a battery material lithium carbonate and an apparatus for the production

Abstract

This invention provides a method and equipment for producing lithium carbonate for batteries. The method includes the following steps: S1, crushing and grinding lepidolite ore into fine particles with a particle size of less than 75 μm; S2, placing the ground lepidolite particles into a flotation device to obtain lepidolite concentrate using a flotation process. The lithium carbonate production method provided by this invention incorporates phosphate and carboxylic acid groups into the collector. The phosphate groups in the aminophosphate molecule can form stable chemical bonds or complexes with lithium ions on the surface of lepidolite, enhancing the binding force between the collector and lepidolite, increasing the collection ability of lithium minerals, and improving selectivity. The interaction with the surface of lepidolite is specific, while the interaction with the surface of gangue minerals is weaker, thus better enhancing its selectivity and improving the quality of the lepidolite concentrate, laying the foundation for the subsequent production of higher quality lithium carbonate.

Description

Technical Field

[0001] This invention relates to the field of battery material production, and in particular to a method and equipment for producing lithium carbonate, a battery material. Background Technology

[0002] Lithium carbonate (Li2CO3) is a crucial raw material in the lithium battery industry. It is a key lithium source for preparing cathode materials and electrolytes, and the raw materials for preparing lithium carbonate usually include lepidolite.

[0003] The current process for preparing lithium carbonate from lepidolite includes: crushing and grinding lepidolite ore; flotation of the lepidolite ore concentrate; adding the lepidolite concentrate to a sulfuric acid solution to obtain a lithium leachate; subsequently removing impurities from the lithium leachate and reacting it with carbonates to prepare lithium carbonate. In the flotation of lepidolite, the collector is the key reagent. The collector selectively acts on the surface of the lepidolite mineral, changing it from hydrophilic to hydrophobic, thus allowing it to adhere to bubbles and float, achieving separation from gangue minerals.

[0004] Among them, amines are the most commonly used lepidolite collectors on the market. They are positively charged in acidic slurry and can strongly electrostatically adsorb negatively charged lepidolite, thus having a good collection effect on lepidolite.

[0005] However, monoamine collectors are greatly affected by the properties of the slurry, resulting in high foam viscosity and thus relatively low concentrate grades. Furthermore, there is still room for improvement in the selectivity of monoamine collectors.

[0006] Therefore, it is necessary to provide a method for producing lithium carbonate battery material and equipment for producing it to solve the above-mentioned technical problems. Summary of the Invention

[0007] This invention provides a method and equipment for producing lithium carbonate, a battery material, which solves the problem that the selectivity of monoamine lepidolite collectors used in current lithium carbonate production processes still has room for improvement.

[0008] To solve the above-mentioned technical problems, the present invention provides a method for producing lithium carbonate, a battery material, comprising the following steps:

[0009] S1. The lepidolite ore is crushed and then ground into fine particles with a particle size of less than 75μm.

[0010] S2. The ground lepidolite particles are placed into a flotation device to obtain lepidolite concentrate using the flotation process; wherein, the lepidolite flotation reagents include aminophosphine surfactant, frother, modifier and solvent.

[0011] The chemical formula of the aminophosphophosphate surfactant is:

[0012] ;

[0013] S3. Lithium mica concentrate is added to a sulfuric acid solution with a mass fraction of 5% - 25% for leaching, and solid-liquid separation is achieved by filtration to obtain lithium-containing leachate and leaching residue;

[0014] S4. Add a preset amount of hydrogen peroxide to the lithium-containing leachate, then adjust the pH of the solution to 5-13, filter the precipitate, and finally use the ion exchange resin method to remove the residual impurity ions in the solution to obtain the purified lithium-containing solution.

[0015] S5. Preparation of lithium carbonate: Add sodium carbonate or ammonium carbonate solution to the purified lithium-containing solution, control the reaction pH value at 8-11, and generate lithium carbonate precipitate. Then, after filtration, washing and drying, lithium carbonate is obtained.

[0016] Preferably, in S2, the proportion of aminophosphophosphate surfactant is 40-60%, the proportion of foaming agent is 15-20%, the proportion of modifier is 15-30%, and the proportion of solvent is 20-30%.

[0017] Preferably, the preparation method of the aminophosphophosphate surfactant includes the following steps:

[0018] S21. Add glyoxylic acid monohydrate A, compound B, phosphorous acid and deionized water to the quartz photoreactor;

[0019] S22. Seal the quartz photoreactor with a sealing membrane and place it under a xenon lamp to irradiate the reaction.

[0020] S23. Stir the mixture under a 150W xenon lamp and use TLC to check whether the reactants have reacted completely.

[0021] S24. After the reaction is complete, filter the reaction solution and collect the precipitate, then rinse three times with 5g of deionized water.

[0022] The product is dried in a vacuum drying oven to obtain an aminophosphophosphate surfactant.

[0023] Preferably, the chemical formula of glyoxylic acid monohydrate A is as follows: .

[0024] The present invention also provides equipment for producing lithium carbonate battery material, characterized in that it is used in the lithium carbonate battery material production method and includes: a mounting frame, a lifting frame, a flotation tank, a stirring device, a liquid storage cylinder, an air inlet device, and a material feeding device;

[0025] The flotation cell is mounted on the mounting frame via a lifting frame;

[0026] The stirring device includes a driving device, a stirring tube, and a stirring blade. The stirring tube is installed through and rotatably on the top of the mounting frame, and the bottom end of the stirring tube extends into the interior of the flotation cell. The stirring blade is installed on the stirring tube and located inside the flotation cell. The stirring blade communicates with the interior of the stirring tube. A discharge hole is provided on the stirring blade. The driving device is used to drive the stirring tube to rotate.

[0027] The liquid storage cylinder includes a cylinder body and a valve. The cylinder body is mounted on the top of the mounting frame via a mounting cover, and the valve is mounted on the liquid outlet pipe of the cylinder body.

[0028] The top end of the stirring tube is detachably connected to the liquid outlet tube via a connecting fitting;

[0029] The material feeding device is used to push the flotation foam out of the flotation cell;

[0030] An air intake device is used to input gas into the flotation cell.

[0031] Preferably, the connecting pipe includes a rotary connector and a tee pipe. One end of the rotary connector is connected to the stirring tube, the bottom end of the tee pipe is connected to the other end of the rotary connector, the liquid outlet pipe is detachably connected to the top end of the tee pipe, and the output pipe of the air inlet device is connected to the side end of the tee pipe.

[0032] Preferably, the top end of the three-way pipe is fitted with a threaded connecting sleeve, which is slidably connected to the three-way pipe within a preset stroke, and the liquid outlet pipe is threadedly connected to the threaded connecting sleeve.

[0033] Preferably, the lifting frame includes a lifting cylinder, an L-shaped frame, and a connecting plate. The lifting cylinder is mounted on the mounting frame, the L-shaped frame is mounted on the output end of the lifting cylinder via the connecting plate, and the flotation cell is detachably mounted on the L-shaped frame.

[0034] Preferably, the driving device includes a drive motor, a drive shaft, a main gear, and a driven gear. The drive motor is mounted on the mounting cover, the drive shaft is connected to the output end of the drive motor, the main gear is mounted on the bottom end of the drive shaft, and the driven gear is mounted on the stirring tube. The main gear meshes with the driven gear.

[0035] Preferably, the drive shaft includes a square shaft and a sleeve. The square shaft is fixed to the output end of the drive motor. The sleeve is sleeved on the square shaft to form a sliding key connection. The main gear is connected to the bottom end of the sleeve. A drive gear is installed at the top end of the sleeve. A driving gear is installed on the threaded connection sleeve.

[0036] The equipment for producing lithium carbonate battery material also includes a support frame, which includes a support plate and a support rod. The bottom end of the support rod is supported on the connecting plate, and the top end of the support rod passes through the top end of the mounting frame and is connected to the support plate. The support plate is used to support the sleeve.

[0037] When the master gear meshes with the slave gear, the drive gear is located above the driving gear.

[0038] Compared with related technologies, the lithium carbonate production method for battery materials provided by this invention has the following beneficial effects:

[0039] This invention provides a method for producing lithium carbonate battery material. By incorporating phosphate and carboxylic acid groups into the collector, the phosphate groups in the aminophosphate molecule can form stable chemical bonds or complexes with lithium ions on the surface of lepidolite. This chemical bond formation is stronger than the adsorption by electrostatic interaction of a single amine collector, enhancing the binding force between the collector and lepidolite, improving the collection ability of lithium minerals, and increasing selectivity. The interaction with the surface of lepidolite is specific, while the interaction with the surface of gangue minerals is weaker, thus better enhancing its selectivity.

[0040] The amino and phosphate groups in the aminophosphoric acid molecule can work synergistically. The amino group can bind to the negatively charged sites on the surface of lepidolite through electrostatic attraction and hydrogen bonding, while the phosphate group can bind to metal ions through chemical adsorption. This synergistic effect increases the interaction sites and forces between the collector and the surface of lepidolite, making the adsorption more stable and efficient. This improves the quality of lepidolite concentrate and paves the way for the subsequent production of higher quality lithium carbonate. Attached Figure Description

[0041] Figure 1 A flowchart illustrating the steps of a method for producing lithium carbonate, a battery material, provided by the present invention.

[0042] Figure 2 This is a flowchart of the steps in the method for producing aminophosphophosphate surfactants provided by the present invention;

[0043] Figure 3 A schematic diagram of the chemical equation for the aminophosphophosphate surfactant of the present invention;

[0044] Figure 4 This is a schematic diagram of the experiment on the effect of pH on the flotation of mineral samples with different collectors according to the present invention;

[0045] Figure 5 A schematic diagram of the equipment for producing lithium carbonate battery materials provided by the present invention;

[0046] Figure 6 for Figure 5 A schematic diagram of equipment used for producing lithium carbonate, a battery material, from another perspective;

[0047] Figure 7 A partial cross-sectional view of the equipment for producing lithium carbonate battery materials provided by the present invention;

[0048] Figure 8 A schematic diagram showing the separation of the flotation cell and the stirring blades provided by the present invention;

[0049] Figure 9 A schematic diagram showing the installation positions of the drive gear and the driving gear provided by the present invention;

[0050] Figure 10 for Figure 9 A partial cross-sectional view of equipment used for producing lithium carbonate, a battery material, is shown.

[0051] Figure 11 This is a schematic diagram showing the meshing state of the drive gear and the driving gear provided by the present invention.

[0052] Numbering on the map:

[0053] 1. Mounting bracket; 11. Slide rod;

[0054] 2. Lifting frame; 21. Lifting cylinder; 22. L-shaped frame; 23. Connecting plate; 221. Insertion hole;

[0055] 3. Flotation cell; 301. Discharge channel; 302. Positioning shaft;

[0056] 4. Stirring device; 41. Drive motor; 42. Stirring tube; 43. Drive shaft; 44. Main gear; 45. Driven gear; 46. Stirring blade; 431. Square shaft; 432. Sleeve; 461. Discharge hole;

[0057] 5. Mounting cover; 51. Support;

[0058] 6. Liquid storage cylinder; 61. Cylinder body; 62. Valve; 611. Liquid outlet pipe; 612. Positioning block;

[0059] 7. Air intake equipment;

[0060] 8. Feeding device; 81. Feeding motor; 82. Actuating plate;

[0061] 9. Connecting pipe fittings; 91. Rotary connectors; 92. Tees; 921. Threaded connecting sleeves; 922. Retaining rings;

[0062] 10. Drive gear; 20. Bracket; 201. Support plate; 202. Support rod; 30. Drive gear. Detailed Implementation

[0063] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0064] This invention provides a method for producing lithium carbonate, a battery material.

[0065] Please refer to the following: Figure 1 and Figure 2 In one embodiment of the present invention, the method for producing lithium carbonate battery material includes the following steps:

[0066] S1. The lepidolite ore is crushed and then ground into fine particles with a particle size of less than 75μm.

[0067] S2. The ground lepidolite particles are placed into a flotation device to obtain lepidolite concentrate using the flotation process; wherein, the lepidolite flotation reagents include aminophosphine surfactant, frother, modifier and solvent.

[0068] The chemical formula of the aminophosphophosphate surfactant is:

[0069] ;

[0070] S3. Lithium mica concentrate is added to a sulfuric acid solution with a mass fraction of 5% - 25% for leaching, and solid-liquid separation is achieved by filtration to obtain lithium-containing leachate and leaching residue;

[0071] S4. Add a preset amount of hydrogen peroxide to the lithium-containing leachate, then adjust the pH of the solution to 5-13, filter the precipitate, and finally use the ion exchange resin method to remove the residual impurity ions in the solution to obtain the purified lithium-containing solution.

[0072] S5. Preparation of lithium carbonate: Add sodium carbonate or ammonium carbonate solution to the purified lithium-containing solution, control the reaction pH value at 8-11, and generate lithium carbonate precipitate. Then, after filtration, washing and drying, lithium carbonate is obtained.

[0073] By incorporating phosphate and carboxylic acid groups into the collector, the phosphate groups in the aminophosphate molecule can form stable chemical bonds or complexes with lithium ions on the surface of lepidolite. This chemical bond formation is stronger than the adsorption by electrostatic interaction of a single amine collector, enhancing the binding force between the collector and lepidolite, increasing the collection ability of lithium minerals, and improving selectivity. The interaction with the surface of lepidolite is specific, while the interaction with the surface of gangue minerals is weaker, which can better enhance its selectivity.

[0074] The amino and phosphate groups in the aminophosphoric acid molecule can work synergistically. The amino group can bind to the negatively charged sites on the surface of lepidolite through electrostatic attraction and hydrogen bonding, while the phosphate group can bind to metal ions through chemical adsorption. This synergistic effect increases the interaction sites and forces between the collector and the surface of lepidolite, making the adsorption more stable and efficient. This improves the quality of lepidolite concentrate and paves the way for the subsequent production of higher quality lithium carbonate.

[0075] In step S4, an appropriate amount of hydrogen peroxide is added to the lithium-containing leachate to oxidize ferrous ions to ferric ions. Then, the pH of the solution is adjusted to 5-13, causing impurities such as ferric, aluminum, and magnesium ions to precipitate as hydroxides, which are then removed by filtration. Next, an ion exchange resin method is used to remove residual trace impurity ions such as calcium and magnesium from the solution, resulting in a purified lithium-containing solution.

[0076] As a preferred embodiment of this example, in S2, the proportion of aminophosphophosphate surfactant is 40-60%, the proportion of foaming agent is 15-20%, the proportion of modifier is 15-30%, and the proportion of solvent is 20-30%.

[0077] Among them, foaming agents include one or more of alcohols, oils, ethers, and ether alcohols.

[0078] Modifiers include sodium carbonate, sodium hydroxide, water glass, and starch, among others.

[0079] The solvent includes water or alcohol.

[0080] The preparation method of the aminophosphophosphate surfactant includes the following steps:

[0081] S21. Add glyoxylic acid monohydrate A, compound B, phosphorous acid and deionized water to the quartz photoreactor;

[0082] S22. Seal the quartz photoreactor with a sealing membrane and place it under a xenon lamp to irradiate the reaction.

[0083] S23. Stir the mixture under a 150W xenon lamp and use TLC to check whether the reactants have reacted completely.

[0084] S24. After the reaction is complete, filter the reaction solution and collect the precipitate, then rinse three times with 5g of deionized water.

[0085] The product is dried in a vacuum drying oven to obtain an aminophosphophosphate surfactant.

[0086] The chemical formula of glyoxylic acid monohydrate A is: .

[0087] In one embodiment, compound B is L-tryptophan;

[0088] In another embodiment, compound B has the following chemical formula: ;like Figure 3 The chemical formula for generating an aminophosphophosphate surfactant using compound B and glyoxylic acid monohydrate A.

[0089] The specific steps of the synthesis are as follows:

[0090] Take a clean and dry 2000mL quartz photoreactor;

[0091] Add glyoxylic acid monohydrate A (0.1 mol, 9.2 g), L-tryptophan (0.1 mol, 20.4 g), phosphorous acid (0.1 mol, 8.2 g), and deionized water (500 mL). Seal the vial with a sealing film and place it under a xenon lamp to irradiate the reaction.

[0092] Use TLC (thin-layer chromatography) to check whether the reactants have reacted completely;

[0093] After reactant A has reacted completely, cool to room temperature;

[0094] Pour the reaction solution into a Buchner funnel, collect the precipitate, and rinse three times with 500 mL of deionized water; place in a vacuum drying oven overnight.

[0095] The following specific examples describe the effects of the aminophosphate surfactant of the present invention in the flotation process:

[0096] Example 1

[0097] Flotation experiments were conducted in the laboratory, and the pH of the solution was adjusted with acid and alkali to compare the pH adaptability of aminophosphoric acid surfactants and dodecylamine (DDA).

[0098] Step 1: Place the lithium mica ore in a ball mill and grind it until it reaches a density of 65%-75% at 200 mesh.

[0099] Step 2: Place the collected ground ore into flotation cell 3;

[0100] Step 3: After the ore has settled to the bottom, use a flexible tube to suck out the upper layer of muddy water. Repeat this process three times. Adjust the flotation equipment speed to 1350 r / min and stir the slurry in the flotation equipment for 4 min. Adjust the pH of the slurry by acid and alkali and test it with pH paper to finally obtain 6 flotation samples with pH ranges from 2 to 12.

[0101] Step 4: Slowly add 100-2000 g / t of one of the aminophosphoric acid surfactants and DDA flotation agents, stir for 8 min, then turn on the flotation equipment for roughing to obtain roughing concentrate and roughing tailings. Add 10-200 g / t of the flotation agent to the roughing tailings for scavenging to obtain scavenged ore and scavenged tailings.

[0102] Step 5: Add 10-250 g / t of the flotation agent to the rough concentrate obtained from the roughing process for the first cleaning process, to obtain the first cleaning middlings and the first cleaning concentrate. Add 10-500 g / t of the flotation agent to the first cleaning middlings to obtain the second cleaning concentrate and middlings.

[0103] Experimental results are as follows Figure 4 As shown, the concentrate recovery rate of DDA collector flotation increases with increasing pH, while the concentrate grade decreases with increasing pH. In contrast, the concentrate recovery rate and grade of the aminophosphate collector of this invention both increase first and then decrease with increasing pH. This is because DDA requires acidic conditions to complete the protonation of the amino groups, acquiring a positive charge, and then adsorbing lepidolite ore through electrostatic attraction, thereby completing the flotation of lepidolite ore.

[0104] When the pH is around 6, the charge properties and potential distribution of the mineral surface reach a suitable state, which is conducive to the interaction of the aminophosphate collector with the lepidolite surface through electrostatic adsorption and hydrogen bonding. This allows the collector to be better adsorbed onto the lepidolite particle surface, thereby improving the recovery rate and grade. However, as the pH continues to rise, the charge properties of the mineral surface change too much, leading to a decrease in the amount of collector adsorbed and a deterioration in the flotation effect. In a strongly acidic environment, aminophosphate exists in a protonated form, which is highly hydrophilic and not conducive to binding with the lepidolite surface. As the pH increases, aminophosphate gradually dissociates, forming an anionic form with suitable hydrophilicity and hydrophobicity. At pH 6, its degree of dissociation is moderate, allowing it to fully interact with the lepidolite surface and achieve a good collection effect. When the pH is too high, the collector over-dissociates, becoming too hydrophilic, which is actually detrimental to adsorption on the mineral surface, resulting in a decrease in recovery rate and grade.

[0105] Example 2

[0106] Using the lepidolite particles from the previous example, flotation tests were conducted at pH = 6 using aminophosphate collectors and DDA collectors at different dosages, following the same flotation procedure. With increasing reagent dosage, the grades of both aminophosphate and DDA decreased. This is because excessive aminophosphate collector increases the viscosity of the pulp. High-viscosity pulp hinders the collision and adhesion of bubbles to mineral particles, making it difficult for bubbles to effectively carry mineral particles to the surface, reducing flotation efficiency and consequently decreasing recovery. Since aminophosphate itself has a pH-regulating effect, excessive reagent can also alter the pH of the pulp, affecting the charge properties and chemical composition of the mineral surface. As mentioned earlier, pH changes affect the interaction mode and adsorption capacity between the collector and the mineral surface. When the pH deviates from the optimal range, the adsorption capacity of the collector on the lepidolite surface decreases or its adsorption stability weakens, leading to a decrease in concentrate grade and recovery.

[0107] The present invention also provides equipment for producing lithium carbonate, a battery material.

[0108] Please see Figures 5 to 7 A battery material lithium carbonate production equipment, used in the battery material lithium carbonate production method, includes: a mounting frame 1, a lifting frame 2, a flotation tank 3, a stirring device 4, a liquid storage cylinder 6, an air inlet device 7, and a material feeding device 8.

[0109] The flotation cell 3 is mounted on the mounting frame 1 via the lifting frame 2;

[0110] The stirring device 4 includes a driving device, a stirring tube 42, and a stirring blade 46. The stirring tube 42 passes through and is rotatably mounted on the top of the mounting frame 1. The bottom end of the stirring tube 42 extends into the interior of the flotation cell 3. The stirring blade 46 is mounted on the stirring tube 42 and located inside the flotation cell 3. The stirring blade 46 communicates with the interior of the stirring tube 42. The stirring blade 46 has a discharge hole 461. The driving device is used to drive the stirring tube 42 to rotate.

[0111] The liquid storage cylinder 6 includes a cylinder body 61 and a valve 62. The cylinder body 61 is mounted on the top of the mounting frame 1 through a mounting cover 5, and the valve 62 is mounted on the liquid outlet pipe 611 of the cylinder body 61.

[0112] The top end of the stirring tube 42 is detachably connected to the liquid outlet tube 611 via a connecting fitting 9;

[0113] The feeding device 8 is used to push the flotation foam out of the flotation cell 3;

[0114] The air intake device 7 is used to input gas into the flotation cell 3.

[0115] In this embodiment, the equipment for producing lithium carbonate battery material is mainly used for laboratory-level flotation of lepidolite. In laboratory flotation equipment for lepidolite, it is usually necessary for the experimenter to manually add the lepidolite flotation collector to the flotation cell 3 continuously, which is quite troublesome.

[0116] In this embodiment, the collector for flotation is loaded into the storage tank 6. During flotation, the lepidolite to be floated is added to the flotation cell 3, and water is added. The air inlet device 7 inputs gas into the flotation cell 3 to generate bubbles. The stirring device 4 stirs the mixture. At the same time, the valve 62 is opened, and the collector inside the storage tank 6 enters the stirring pipe 42 through the outlet pipe 611 and the connecting pipe 9, and then enters the stirring blade 46. It is discharged through the discharge hole 461. Since the stirring blade 46 is rotating, the collector is dispersed along the rotational trajectory. After being dispersed, it can be quickly mixed with the lepidolite liquid by the stirring blade 46. This allows for the automatic addition of lepidolite collector and rapid mixing of the collector with the lepidolite liquid.

[0117] Lithium mica ore is floated to the top of the entire solution along with the bubbles. The feeding device 8 continuously pushes the bubbles containing lithium mica ore out of the flotation cell 3 along the discharge channel 301 and into the pre-placed container.

[0118] Among them, valve 62 is a solenoid valve or electric valve, which can control the opening and closing of the liquid outlet pipe 611 and control the flow rate of the collector.

[0119] The number of stirring blades 46 can be one or more; in this embodiment, there are two. Each of the two stirring blades 46 has multiple discharge holes 461, and these discharge holes 461 are located on opposite sides of the two stirring blades 46. Figure 7 .

[0120] Please see Figure 5 In this embodiment, the feeding device 8 includes a feeding motor 81, a feeding plate 82, and a fixing frame. One end of the fixing frame is mounted on the mounting frame 1, and the other end is suspended on one side of the flotation cell 3 and located above the flotation cell 3. The feeding motor 81 is mounted on one end of the fixing frame, and the feeding plate 82 is mounted on the output shaft of the feeding motor 81. The feeding plate 82 is located at the inlet end of the discharge channel 301. The feeding motor 81 rotates the feeding plate 82 to push the foam out of the flotation cell 3.

[0121] In other embodiments, an electric pusher cylinder can also be used to push the actuating plate 82 to push out the foam in the flotation cell 3.

[0122] As an optional method in this embodiment, the connecting pipe 9 is only a rotary connector 91, which is used to connect the liquid outlet pipe 611 of the liquid storage cylinder 6 and the stirring pipe 42. By setting the rotary connector 91, when the driving device drives the stirring pipe 42 to rotate, it will not drive the liquid storage cylinder 6 to rotate accordingly.

[0123] As another optional method in this embodiment, please refer to Figure 6 The connecting pipe 9 includes a rotary connector 91 and a three-way pipe 92. One end of the rotary connector 91 is connected to the stirring pipe 42, and the bottom end of the three-way pipe 92 is connected to the other end of the rotary connector 91. The liquid outlet pipe 611 is detachably connected to the top end of the three-way pipe 92, and the output pipe of the air inlet device 7 is connected to the side end of the three-way pipe 92.

[0124] By connecting the output end of the air intake device 7 to the stirring pipe 42 through the three-way pipe 92, when the air intake device 7 is working, the gas can enter the stirring pipe 42 through the three-way pipe 92 and the rotary connector 91 in sequence, and finally be discharged through the discharge hole 461 on the stirring blade 46. The gas is discharged with the rotation of the stirring blade 46, so that the gas can quickly fill the entire lithium mica ore solution and be quickly and evenly distributed.

[0125] At the same time, the airflow can carry the incoming collector out quickly through the discharge hole 461, and avoid the discharge hole 461 being blocked by solid particles of lepidolite mineral, which would prevent the collector from being discharged.

[0126] In one embodiment, the air intake device 7 includes an air compressor or jet pump, valves, and pipes. The pipes connect the air compressor or jet pump to a three-way pipe 92. The valves are installed on the pipes. Gas is input through the air compressor or jet pump, and the gas is discharged through multiple discharge holes 461 to form bubbles.

[0127] In another embodiment, an air intake device 7 can also be provided separately, such as a bubble generator, with the output end of the bubble generator detachably installed in the flotation cell 3;

[0128] Please see Figure 7 As an optional embodiment, the top end of the three-way pipe 92 is fitted with a threaded connecting sleeve 921, the threaded connecting sleeve 921 is slidably connected to the three-way pipe 92 within a preset stroke, and the liquid outlet pipe 611 is threadedly connected to the threaded connecting sleeve 921.

[0129] Among them, the top end and surface of the tee pipe 92 are equipped with retaining rings 922 at intervals, and the threaded connecting sleeve 921 is sleeved on the tee pipe 92 and located between the two retaining rings 922, and can slide within the range between the two retaining rings 922, thereby forming a sliding connection within a preset stroke.

[0130] The surface of the corresponding outlet pipe 611 is provided with external threads;

[0131] During installation, make the bottom end of the outlet pipe 611 abut against the top end of the tee pipe 92, and then screw the threaded connecting sleeve 921 to connect with the threaded outlet pipe 611 to achieve a detachable connection.

[0132] The liquid storage cylinder 6 can be cleaned by disassembling it, thanks to the detachable connection.

[0133] Preferably, the diameter of the liquid storage cylinder 6 can be set to be larger than the rotation radius of the stirring blade 46. After the raw materials of the collector as described above are added into the liquid storage cylinder 6, the stirring blade 46 is inserted into the liquid storage cylinder 6 to stir the solutions evenly.

[0134] The bottom end of the outlet pipe 611 is bonded with a sealing ring to ensure the sealing of the connection between the outlet pipe 611 and the top end of the three-way pipe 92.

[0135] The top of the liquid storage cylinder 6 is threaded with a cap, which can be opened to add a collector or to clean the liquid storage cylinder 6.

[0136] The top of the mounting cover 5 has a circular hole, and the bottom end of the liquid storage cylinder 6 extends into the mounting cover 5 through the circular hole and is connected to the three-way pipe 92. Preferably, an annular support 51 is provided on the top of the mounting cover 5 at the position corresponding to the circular hole. The support 51 can stably support the bottom of the liquid storage cylinder 6.

[0137] Preferably, multiple limiting grooves are provided on the support 51, and a positioning block 612 is provided at the bottom of the corresponding cylinder 61. When the cylinder 61 is assembled with the three-way pipe 92, the cylinder 61 is located in the support 51, and the positioning block 612 is inserted into the limiting groove, thereby limiting the axial movement of the cylinder 61. Therefore, when the threaded connecting sleeve 921 is threadedly connected to the liquid outlet pipe 611, it is not necessary to manually limit the axial movement of the cylinder 61.

[0138] The mounting cover 5 is installed on the top of the mounting frame 1. The side plate of the mounting cover 5 is designed to be detachable or openable. In this embodiment, the three-way pipe 92 is connected to the liquid outlet pipe 611 by removing or opening the side plate.

[0139] As another optional method in this embodiment, the threaded connecting sleeve 921 can be fitted onto the liquid outlet pipe 611 within a preset stroke, and an external thread can be provided at the top of the tee pipe 92.

[0140] Please see Figure 6 and Figure 7In this embodiment, the lifting frame 2 includes a lifting cylinder 21, an L-shaped frame 22 and a connecting plate 23. The lifting cylinder 21 is installed on the mounting frame 1, and the L-shaped frame 22 is installed at the output end of the lifting cylinder 21 through the connecting plate 23. The flotation tank 3 is detachably installed on the L-shaped frame 22.

[0141] By setting up the lifting frame 2, after flotation is completed, the lifting cylinder 21 lowers the L-shaped frame 22, which in turn lowers the flotation tank 3, causing it to separate from the stirring blade 46. Figure 8 Subsequently, the flotation cell 3 can be removed, and the tailings inside the flotation cell 3 can be cleaned, making it easier to clean the flotation cell 3.

[0142] The L-shaped frame 22 has multiple insertion holes 221, and the bottom of the flotation cell 3 is equipped with multiple positioning shafts 302. When the flotation cell 3 is fitted onto the L-shaped frame 22, the corresponding positioning shafts 302 pass through the insertion holes 221 to achieve a detachable connection.

[0143] Alternatively, a thread can be provided on the positioning shaft 302, which can be tightened with a nut after passing through the insertion hole 221.

[0144] The lifting cylinder 21 can be a pneumatic cylinder, a hydraulic cylinder, or an electric push cylinder.

[0145] Preferably, multiple slide rods 11 are installed on the mounting frame 1, and the connecting plate 23 is sleeved on the slide rods 11 to form a sliding connection, which limits the position of the connecting plate 23 and improves the stability of the lifting of the connecting plate 23.

[0146] Please see Figure 8 In this embodiment, the driving device includes a drive motor 41, a drive shaft 43, a main gear 44, and a driven gear 45. The drive motor 41 is mounted on the mounting cover 5. The drive shaft 43 is connected to the output end of the drive motor 41. The main gear 44 is mounted on the bottom end of the drive shaft 43. The driven gear 45 is mounted on the stirring tube 42. The main gear 44 meshes with the driven gear 45.

[0147] When the driving stirring tube 42 rotates, the driving motor 41 drives the main gear 44 to rotate through the driving shaft 43. The main gear 44 drives the stirring tube 42 to rotate through the driven gear 45, thereby driving the stirring blade 46 to rotate for stirring operation.

[0148] Please see Figure 9 and Figure 10In other embodiments, the drive shaft 43 includes a square shaft 431 and a sleeve 432. The square shaft 431 is fixed to the output end of the drive motor 41. The sleeve 432 is sleeved on the square shaft 431 to form a sliding key connection. The main gear 44 is connected to the bottom end of the sleeve 432. The top end of the sleeve 432 is equipped with a drive gear 10. The threaded connection sleeve 921 is equipped with a driving gear 30.

[0149] The equipment for producing lithium carbonate battery material also includes a support 20, which includes a support plate 201 and a support rod 202. The bottom end of the support rod 202 is supported on the connecting plate 23, and the top end of the support rod 202 passes through the top end of the mounting frame 1 and is connected to the support plate 201. The support plate 201 is used to support the sleeve 432.

[0150] When the master gear 44 meshes with the slave gear 45, the drive gear 10 is located above the driving gear 30.

[0151] At the end of flotation, the lifting cylinder 21 first lowers the L-shaped frame 22 by a preset distance. At this time, the support 20 follows the L-shaped frame 22 downwards, and the sleeve 432 also descends. The sleeve 432 drives the main gear 44 to separate from the driven gear 45, and at this time, the drive gear 10 descends and meshes with the driving gear 30. Figure 11 At this time, the support plate 201 of the L-shaped bracket 20 is attached to the top of the mounting frame 1. The lifting cylinder 21 can then continue to lower the L-shaped frame 22. The flotation cell 3 can then be removed and the tailings cleaned out. The flotation cell 3 can then be reinstalled on the L-shaped frame 22. At the same time, the drive motor 41 drives the square shaft 431 to rotate the sleeve 432. The drive gear 10 drives the threaded connecting sleeve 921 to rotate through the gear 30, so that the threaded connecting sleeve 921 automatically separates from the liquid outlet pipe 611. Thus, the separation of the liquid outlet pipe 611 from the three-way pipe 92 can be achieved automatically without opening the side plate of the mounting cover 5. The operation is simple.

[0152] At this point, the liquid storage cylinder 6 can be removed and cleaned. After cleaning, the liquid storage cylinder 6 is filled with cleaning water and then put back in, so that the liquid outlet pipe 611 abuts against the top of the three-way pipe 92. The drive motor 41 drives the square shaft 431 to rotate in the opposite direction, so that the threaded connecting sleeve 921 is connected to the liquid outlet pipe 611 again.

[0153] Then, valve 62 is opened, and gas is introduced by air intake device 7. The gas carries the cleaning liquid into the stirring tube 42 and out through discharge hole 461, thereby cleaning the inside of stirring tube 42 and stirring blade 46. The cleaned water is discharged into empty flotation cell 3.

[0154] Subsequently, the L-shaped frame 22 can be lowered to remove the flotation cell 3 for cleaning;

[0155] In subsequent use, the lifting cylinder 21 raises the L-shaped frame 22 again, and the flotation tank 3 moves up to the preset height, so that the stirring blade 46 is located in the flotation tank 3, and at the same time the agitator 82 is located at the feed end of the discharge channel 301.

[0156] At this time, the connecting plate 23 lifts the support rod 202, which drives the support plate 201 to lift the sleeve 432, causing the drive gear 10 to separate from the drive gear 30, and the main gear 44 to mesh with the driven gear 45 again.

[0157] The thickness of the drive gear 10 and the driving gear 30 is not less than the length of the threaded connection between the threaded sleeve 921 and the outlet pipe 611.

[0158] Furthermore, the drive motor 41 drives the square shaft 431 to rotate an integer number of revolutions each time, thereby ensuring that the teeth of the drive gear 10 can be aligned with the tooth grooves of the drive gear 30, so that the teeth of the main gear 44 can be aligned with the tooth grooves of the gear 45.

[0159] As an optional method in this embodiment, the driving gear 30 and the driven gear 45 can be elastically connected to the corresponding positions. A spring can be connected between the threaded connecting sleeve 921 and the retaining ring 922 of the three-way pipe 92. A flange is correspondingly provided on the stirring tube 42, and a spring is connected between the flange and the driven gear 45. The spring is sleeved on the stirring tube 42.

[0160] Therefore, even if the driven gear 45 is displaced, when the main gear 44 and the driven gear 45 are meshed, the main gear 44 can drive the driven gear 45 to compress the spring. When the drive motor 41 drives the drive shaft 43 to rotate, the main gear 44 rotates accordingly. When the teeth and tooth grooves are aligned, the elasticity of the spring will push the driven gear 45 to mesh with the main gear 44. The meshing principle of the drive gear 10 and the drive gear 30 is the same.

[0161] The bottom end of the sleeve 432 is sealed and has embedded balls. The top of the support plate 201 is provided with an arc-shaped seat. The arc-shaped seat interacts with the bottom of the balls to reduce the friction between the sleeve 432 and the support plate 201 when the sleeve 432 rotates.

[0162] The working principle of the equipment for producing lithium carbonate battery materials provided by this invention is as follows:

[0163] In this embodiment, the collector for flotation is loaded into the storage tank 6. During flotation, the lepidolite to be floated is added to the flotation cell 3, and water is added. The air inlet device 7 inputs gas into the flotation cell 3 to generate bubbles. The stirring device 4 stirs the mixture. At the same time, the valve 62 is opened, and the collector inside the storage tank 6 enters the stirring pipe 42 through the outlet pipe 611 and the connecting pipe 9, and then enters the stirring blade 46. It is discharged through the discharge hole 461. Since the stirring blade 46 is rotating, the collector is dispersed along the rotational trajectory. After being dispersed, it can be quickly mixed with the lepidolite liquid by the stirring blade 46. This allows for the automatic addition of lepidolite collector and rapid mixing of the collector with the lepidolite liquid.

[0164] By connecting the output end of the air intake device 7 to the stirring pipe 42 through the three-way pipe 92, when the air intake device 7 is working, the gas can enter the stirring pipe 42 through the three-way pipe 92 and the rotary connector 91 in sequence, and finally be discharged through the discharge hole 461 on the stirring blade 46. The gas is discharged with the rotation of the stirring blade 46, so that the gas can quickly fill the entire lithium mica ore solution and be quickly and evenly distributed.

[0165] At the same time, the airflow can carry the incoming collector out quickly through the discharge hole 461, and avoid the discharge hole 461 being blocked by solid particles of lepidolite mineral, which would prevent the collector from being discharged.

[0166] At the end of flotation, the lifting cylinder 21 first lowers the L-shaped frame 22 by a preset distance. At this time, the support 20 follows the L-shaped frame 22 downwards, and the sleeve 432 also descends. The sleeve 432 drives the main gear 44 to separate from the driven gear 45, and at this time, the drive gear 10 descends and meshes with the driving gear 30. Figure 11 At this time, the support plate 201 of the L-shaped bracket 20 is attached to the top of the mounting frame 1. The lifting cylinder 21 can then continue to lower the L-shaped frame 22. The flotation cell 3 can then be removed and the tailings cleaned out. The flotation cell 3 can then be reinstalled on the L-shaped frame 22. At the same time, the drive motor 41 drives the square shaft 431 to rotate the sleeve 432. The drive gear 10 drives the threaded connecting sleeve 921 to rotate through the gear 30, so that the threaded connecting sleeve 921 automatically separates from the liquid outlet pipe 611. Thus, the separation of the liquid outlet pipe 611 from the three-way pipe 92 can be achieved automatically without opening the side plate of the mounting cover 5. The operation is simple.

[0167] At this point, the liquid storage cylinder 6 can be removed and cleaned. After cleaning, the liquid storage cylinder 6 is filled with cleaning water and then put back in, so that the liquid outlet pipe 611 abuts against the top of the three-way pipe 92. The drive motor 41 drives the square shaft 431 to rotate in the opposite direction, so that the threaded connecting sleeve 921 is connected to the liquid outlet pipe 611 again.

[0168] Then, valve 62 is opened, and gas is introduced by air intake device 7. The gas carries the cleaning liquid into the stirring tube 42 and out through discharge hole 461, thereby cleaning the inside of stirring tube 42 and stirring blade 46. The cleaned water is discharged into empty flotation cell 3.

[0169] Subsequently, the L-shaped frame 22 can be lowered to remove the flotation cell 3 for cleaning;

[0170] In subsequent use, the lifting cylinder 21 raises the L-shaped frame 22 again, and the flotation tank 3 moves up to the preset height, so that the stirring blade 46 is located in the flotation tank 3, and at the same time the agitator 82 is located at the feed end of the discharge channel 301.

[0171] At this time, the connecting plate 23 lifts the support rod 202, which drives the support plate 201 to lift the sleeve 432, causing the drive gear 10 to separate from the drive gear 30, and the main gear 44 to mesh with the driven gear 45 again.

[0172] Thus, the device can drive the stirring device 4 to work in one state, and can install and disassemble the liquid storage cylinder 6 in another state. The state can be switched by using the lifting flotation tank 3.

[0173] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A method for producing lithium carbonate, a battery material, characterized in that, Includes the following steps: S1. The lepidolite ore is crushed and then ground into fine particles with a particle size of less than 75μm. S2. The ground lepidolite particles are placed into a flotation device to obtain lepidolite concentrate using the flotation process; wherein, the lepidolite flotation reagents include aminophosphine surfactant, frother, modifier and solvent. The chemical formula of the aminophosphophosphate surfactant is: ； S3. Lithium mica concentrate is added to a sulfuric acid solution with a mass fraction of 5% - 25% for leaching, and solid-liquid separation is achieved by filtration to obtain lithium-containing leachate and leaching residue; S4. Add a preset amount of hydrogen peroxide to the lithium-containing leachate, then adjust the pH of the solution to 5-13, filter the precipitate, and finally use the ion exchange resin method to remove the residual impurity ions in the solution to obtain the purified lithium-containing solution. S5. Lithium carbonate preparation: Add sodium carbonate or ammonium carbonate solution to the purified lithium-containing solution, control the reaction pH value at 8-11, generate lithium carbonate precipitate, and then obtain lithium carbonate after filtration, washing and drying. The preparation method of the aminophosphophosphate surfactant includes the following steps: S21. Add glyoxylic acid monohydrate A, compound B, phosphorous acid and deionized water to the quartz photoreactor; S22. Seal the quartz photoreactor with a sealing membrane and place it under a xenon lamp to irradiate the reaction. S23. Stir the mixture under a 150W xenon lamp and use TLC to check whether the reactants have reacted completely. S24. After the reaction is complete, filter the reaction solution and collect the precipitate, then rinse three times with 5g of deionized water. The product is dried in a vacuum drying oven to obtain an aminophosphophosphate surfactant. Compound B is L-tryptophan or .

2. The method for producing lithium carbonate battery material according to claim 1, characterized in that, The proportion of aminophosphophosphate surfactant in S2 is 40-60%, foaming agent is 15-20%, modifier is 15-30%, and solvent is 20-30%.

3. The method for producing lithium carbonate battery material according to claim 1, characterized in that, The chemical formula of glyoxylic acid monohydrate A is: .

4. A device for producing lithium carbonate, a battery material, characterized in that, The method for producing lithium carbonate battery material as described in any one of claims 1-3 includes: a mounting frame, a lifting frame, a flotation tank, a stirring device, a liquid storage cylinder, an air inlet device, and a material feeding device; The flotation cell is mounted on the mounting frame via a lifting frame; The stirring device includes a driving device, a stirring tube, and a stirring blade. The stirring tube is installed through and rotatably on the top of the mounting frame, and the bottom end of the stirring tube extends into the interior of the flotation cell. The stirring blade is installed on the stirring tube and located inside the flotation cell. The stirring blade communicates with the interior of the stirring tube. A discharge hole is provided on the stirring blade. The driving device is used to drive the stirring tube to rotate. The liquid storage cylinder includes a cylinder body and a valve. The cylinder body is mounted on the top of the mounting frame via a mounting cover, and the valve is mounted on the liquid outlet pipe of the cylinder body. The top end of the stirring tube is detachably connected to the liquid outlet tube via a connecting fitting; The material feeding device is used to push the flotation foam out of the flotation cell; An air intake device is used to input gas into the flotation cell.

5. The equipment for producing lithium carbonate battery materials according to claim 4, characterized in that, The connecting pipe includes a rotary connector and a tee pipe. One end of the rotary connector is connected to the stirring tube, the bottom end of the tee pipe is connected to the other end of the rotary connector, the liquid outlet pipe is detachably connected to the top end of the tee pipe, and the output pipe of the air inlet device is connected to the side end of the tee pipe.

6. The equipment for producing lithium carbonate battery materials according to claim 5, characterized in that, The top end of the three-way pipe is fitted with a threaded connecting sleeve, which is slidably connected to the three-way pipe within a preset stroke, and the liquid outlet pipe is threadedly connected to the threaded connecting sleeve.

7. The equipment for producing lithium carbonate battery materials according to claim 6, characterized in that, The lifting frame includes a lifting cylinder, an L-shaped frame, and a connecting plate. The lifting cylinder is mounted on the mounting frame, and the L-shaped frame is mounted on the output end of the lifting cylinder via the connecting plate. The flotation cell is detachably mounted on the L-shaped frame.

8. The equipment for producing lithium carbonate battery materials according to claim 7, characterized in that, The driving device includes a drive motor, a drive shaft, a main gear, and a driven gear. The drive motor is mounted on the mounting cover, the drive shaft is connected to the output end of the drive motor, the main gear is mounted on the bottom end of the drive shaft, and the driven gear is mounted on the stirring tube. The main gear meshes with the driven gear.

9. The equipment for producing lithium carbonate battery materials according to claim 8, characterized in that, The drive shaft includes a square shaft and a sleeve. The square shaft is fixed to the output end of the drive motor. The sleeve is fitted onto the square shaft to form a sliding key connection. The main gear is connected to the bottom end of the sleeve. A drive gear is installed at the top end of the sleeve. A driving gear is installed on the threaded connection sleeve. The equipment for producing lithium carbonate battery material also includes a support frame, which includes a support plate and a support rod. The bottom end of the support rod is supported on the connecting plate, and the top end of the support rod passes through the top end of the mounting frame and is connected to the support plate. The support plate is used to support the sleeve. When the master gear meshes with the slave gear, the drive gear is located above the driving gear.

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