Nickel-lithium solution recovery device
The nickel-lithium solution recovery device solves the problems of impurity introduction and unrecoverable precipitates in nickel-lithium solution processing, achieving efficient separation and recovery of nickel-lithium solution and meeting the requirements of the next process.
Patent Information
- Application Number
- CN202520158236.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-23
- Publication Date
- 2026-01-02
- Estimated Expiration
- 2035-01-23
AI Technical Summary
Existing technologies introduce new impurities when processing nickel-lithium solutions, and the precipitated elements in the precipitate cannot be directly recovered and reused, resulting in the ineffective recycling of nickel-lithium solutions.
A nickel-lithium solution recovery device was designed, including a filtration and storage device, a nickel-lithium metal precipitation and separation device, an ammonia removal and weight removal device, a concentration and precipitation device, and a sodium sulfate crystallization and solution reuse device. The nickel-lithium solution is processed through multiple series units to achieve the separation and recovery of nickel and lithium.
The system achieves effective separation and recovery of nickel and lithium in nickel-lithium solution, with nickel concentration reaching 90 g/L, lithium concentration reaching 18 g/L, and sodium content less than 100 mg/L, meeting the requirements of the next process. The nickel-lithium solution product can be reused.
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Figure CN223747153U_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The utility model mainly relates to the technical field of solution treatment, especially relates to a set of nickel lithium solution recovery device. BACKGROUND
[0002] In the production process of lithium battery positive electrode material containing nickel, such as acid dissolution and water washing process of lithium nickelate and pure nickel product, a large amount of acidic solution containing nickel and lithium (referred to as nickel lithium solution) will be produced. The proportion of nickel and lithium in the nickel lithium solution is about 1.0-5.0%, which has high recycling value.
[0003] At present, the existing technology mainly adopts membrane system separation, precipitation and extraction and other ways to treat nickel lithium solution, but in the process of treating nickel lithium solution by the above technical means, the solution will be introduced into new impurities (such as potassium, sodium and sulfur), and the produced precipitate also cannot be directly recycled due to the precipitation elements containing precipitants. Therefore, it is necessary to design a new nickel lithium solution recovery device, so that the product of the treated nickel lithium solution can be reused or meet the discharge index. INVENTION CONTENTS
[0004] To solve the above technical problems, the utility model adopts the following technical scheme:
[0005] A set of nickel lithium solution recovery device is provided, which comprises filter storage devices, nickel lithium metal precipitation separation devices, ammonia removal and heavy metal removal devices, concentration precipitation devices, concentration precipitation devices and sodium sulfate crystallization and solution recycling devices connected in series. The filter storage device is used to remove solid impurities and temporarily store nickel lithium solution; the concentration device is used to concentrate nickel lithium solution; the nickel lithium metal precipitation separation device is used to make nickel metal crystallize and precipitate and separate from the solution, so as to obtain lithium solution; the ammonia removal and heavy metal removal device is used to remove ammonia and heavy metals; the concentration precipitation device is used to concentrate lithium solution and react with sodium carbonate to produce lithium carbonate separated from lithium solution; the sodium sulfate crystallization and solution recycling device is used to concentrate and produce meta alumina, and the remaining lithium-containing solution returns to the previous step to separate and precipitate to obtain lithium carbonate.
[0006] In the above nickel lithium solution recovery device, the filter storage device comprises plate and frame filter press, storage tank one, microporous filter one and storage tank two connected in series. The input end of the plate and frame filter press is connected with the external input mechanism in communication, and the nickel lithium solution enters the nickel lithium solution recovery device from here; the output end of the storage tank two is connected with the concentration device in communication.
[0007] The concentration device comprises a plate heat exchanger 1, a falling film evaporator 1 and a buffer tank 1 connected in series; the falling film evaporator 1 is further connected in series with a gas-liquid separator 1, a secondary separator 1, a compressor 1 and a distilled water tank; the secondary separator 1 and the distilled water tank are connected in communication, and the distilled water tank and the plate heat exchanger 1 are connected in communication. The input end of the plate heat exchanger 1 is connected in communication with the output end of the storage tank 2; and the output end of the buffer tank 1 is connected in communication with the nickel-lithium metal precipitation separation device.
[0008] The nickel-lithium metal precipitation separation device comprises a reaction kettle, a centrifuge 1, a drying machine 1 and a buffer tank 2 connected in series; the reaction kettle is further connected with an ammonia water tank 1 and a lye tank. The input end of the reaction kettle is connected in communication with the output end of the buffer tank 1; and the output end of the buffer tank 2 is connected in communication with the ammonia removal and heavy metal removal device.
[0009] The ammonia removal and heavy metal removal device comprises a deamination tower, an ammonia absorption tower, a precipitation tank, a filter press, a buffer tank 3, a microporous filter 2 and a buffer tank 4 connected in series; the deamination tower is further connected in series with an ammonia condenser and an ammonia water tank 2. The input end of the deamination tower is connected in communication with the output end of the buffer tank 2; and the output end of the buffer tank 4 is connected in communication with the concentration and precipitation device.
[0010] The concentration and precipitation device comprises a plate heat exchanger 2, a falling film evaporator 2, a buffer tank 5, a high-level tank 1, a lithium precipitation kettle, a buffer tank 6, a centrifuge 2, a pH adjusting tank 1, a decarbonization tower and a pH adjusting tank 2 connected in series; the falling film evaporator 2 is further connected in series with a gas-liquid separator 2, a secondary separator 2 and a condensed water tank; the secondary separator 2 is connected in communication with the falling film evaporator 2 and the condensed water tank through a compressor 2; and the concentration and precipitation device further comprises a high-level tank 2 connected in communication with the lithium precipitation kettle. The input end of the plate heat exchanger 2 is connected in communication with the output end of the buffer tank 4; and the output end of the pH adjusting tank 2 is connected in communication with the sodium sulfate crystallization and solution recycling device.
[0011] The sodium sulfate crystallization and solution recycling device comprises a storage tank 3, a heat exchanger 3, a gas-liquid separator 3, a thickener, a centrifuge 3 and a drying machine 2 connected in series. The input end of the storage tank 3 is connected in communication with the output end of the pH adjusting tank 2.
[0012] Compared with the prior art, the concentration and precipitation device has the advantages that:
[0013] The nickel lithium solution inputted from outside contains less than 60g / L of nickel, less than 15g / L of lithium and less than 100mg / L of sodium. The filter storage device is arranged to remove the solid impurities from the nickel lithium solution inputted from outside, and store the nickel lithium solution after removing the solid impurities. The filter storage device is connected to the concentration device, and when the nickel lithium solution enters the concentration device, the nickel lithium solution is concentrated to the critical saturation state, and the nickel concentration is greater than 90g / L, so as to be more suitable for the conditions of the precursor crystallization of the next process. The nickel lithium metal precipitation separation device is arranged, and the nickel lithium solution is subjected to precipitation reaction to crystallize the nickel metal into nickel hydroxide, i.e. Ni 2+ +2NaOH=Ni(OH)2⬇+2Na + , so as to separate the nickel metal and the lithium metal, and the remaining lithium solution contains ammonia and the lithium metal content is about 6g / L. The remaining lithium solution enters the ammonia removal and heavy metal removal device, and the ammonia and the heavy metal in the lithium solution are removed. Then, the lithium solution enters the concentration and precipitation device, and the lithium solution is further concentrated until the lithium metal content is about 18g / L. The concentrated lithium solution reacts with sodium carbonate to produce lithium carbonate precipitation, i.e. 2Li + +Na2CO3=Li2CO3⬇+2Na + , and the lithium is separated from the lithium solution. The remaining lithium solution is subjected to decarburization and pH adjustment, and the lithium metal content in the remaining lithium solution is less than 3g / L. Finally, the sodium sulfate crystallization and solution recycling device is arranged, the lithium solution is preheated and concentrated again until the solution concentration is saturated, and then the sodium sulfate is obtained by solid-liquid separation. Through the above arrangement, the nickel and the lithium metal in the nickel lithium solution can be recycled respectively. BRIEF DESCRIPTION OF DRAWINGS
[0014] Figure 1 is a structural schematic diagram of a nickel lithium solution recycling device;
[0015] Figure 2 is a structural schematic diagram of a filter storage device;
[0016] Figure 3 is a structural schematic diagram of a concentration device;
[0017] Figure 4 is a structural schematic diagram of a nickel lithium metal precipitation separation device;
[0018] Figure 5 is a structural schematic diagram of an ammonia removal and heavy metal removal device;
[0019] Figure 6 is a structural schematic diagram of a concentration and precipitation device;
[0020] Figure 7 is a structural schematic diagram of a sodium sulfate crystallization and solution recycling device.
[0021] The reference signs in the drawings represent:
[0022] 1. Filter storage device; 11. Plate and frame filter press; 12. Storage tank 1; 13. Microporous filter 1; 14. Storage tank 2;
[0023] 2. Concentration device; 21. Plate heat exchanger 1; 22. Falling film evaporator 1; 23. Buffer tank 1; 24. Gas-liquid separator 1; 25. Secondary separator 1; 26. Compressor 1; 27. Distilled water tank;
[0024] 3. Nickel-lithium metal precipitation separation device; 31. Reaction kettle; 32. Centrifuge 1; 33. Dryer 1; 34. Buffer tank 2; 35. Ammonia tank 1; 36. Alkali tank;
[0025] 4. Deamination and heavy metal removal device; 41. Deamination tower; 42. Ammonia absorption tower; 43. Sedimentation tank; 44. Filter press; 45. Buffer tank 3; 46. Microporous filter 2; 47. Buffer tank 4; 48. Ammonia condenser; 49. Ammonia tank 2;
[0026] 5. Concentration and precipitation device; 51. Plate heat exchanger 2; 52. Falling film evaporator 2; 53. Buffer tank 5; 54. High-level tank 1; 55. Lithium precipitation kettle; 56. Buffer tank 6; 57. Centrifuge 2; 58. pH adjusting tank 1; 59. Decarbonization tower; 510. pH adjusting tank 2; 511. Gas-liquid separator 2; 512. Secondary separator 2; 513. Condensate tank; 514. Compressor 2; 515. High-level tank 2;
[0027] 6. Sodium sulfate crystallization and solution recycling device; 61. Storage tank 3; 62. Heat exchanger 3; 63. Gas-liquid separator 3; 64. Thickener; 65. Centrifuge 3; 66. Dryer 2. DETAILED DESCRIPTION
[0028] The utility model will be further described in detail below in combination with the drawings and specific examples.
[0029] Examples
[0030] As Figures 1 to 7As shown, in the embodiment, the nickel-lithium solution input from outside is sequentially connected in series with the filtering storage device 1 for removing solid impurities and temporarily storing the nickel-lithium solution, the concentration device 2 for concentrating the nickel-lithium solution so that the nickel concentration is greater than 90 g / L, the nickel-lithium metal precipitation separation device 3 for precipitating and separating nickel metal from the solution to obtain a lithium solution, the ammonia and heavy metal removal device 4 for removing ammonia and heavy metals, the concentration and precipitation device 5 for concentrating the nickel-lithium solution and reacting with sodium carbonate to produce lithium carbonate separated from the nickel-lithium solution, and the sodium sulfate crystallization and solution recycling device 6 for concentrating to obtain sodium carbonate, and the remaining lithium-containing solution is returned to the previous step to be precipitated and separated to obtain lithium carbonate. The nickel-lithium solution input from outside has a nickel content less than 60 g / L, a lithium content less than 15 g / L, and a sodium content less than 100 mg / L. By providing the filtering storage device 1, the solid impurities in the nickel-lithium solution input from outside are removed, and the nickel-lithium solution after removing the solid impurities is stored therein. The filtering storage device 1 is in communication with the concentration device 2, and when the nickel-lithium solution enters the concentration device 2, the nickel-lithium solution is concentrated to a critical saturation state, at which time the nickel concentration is greater than 90 g / L, so as to be more suitable for the conditions of the precursor crystallization of the next process. By further providing the nickel-lithium metal precipitation separation device 3, in which the nickel-lithium solution is precipitated to crystallize nickel metal into nickel hydroxide, so as to separate the nickel metal from the lithium metal, and the remaining lithium solution contains ammonia and has a lithium metal content of about 6 g / L. The remaining lithium solution then enters the ammonia and heavy metal removal device 4, in which the ammonia and heavy metals in the lithium solution are discharged. Subsequently, the lithium solution enters the concentration and precipitation device 5, in which the lithium solution is further concentrated until the lithium metal content reaches about 18 g / L, the concentrated lithium solution reacts with sodium carbonate to produce lithium carbonate precipitate which is separated from the solution, and the remaining lithium solution is decarburized and adjusted in pH, and the lithium metal content in the lithium solution is less than 3 g / L. Finally, by providing the sodium sulfate crystallization and solution recycling device 6, the lithium solution is preheated and then concentrated again until the solution concentration is saturated, and sodium carbonate is obtained after solid-liquid separation. Through the above settings, the nickel and lithium metal in the nickel-lithium solution can be recycled and utilized respectively.
[0031] In the embodiment, the filter storage device 1 comprises a plate-and-frame filter press 11, a storage tank 1 2, a microporous filter 1 3 and a storage tank 2 14 connected in series. The nickel-lithium solution flowing into the filter storage device 1 from the outside contains solid impurities, and the plate-and-frame filter press 1 1 and the microporous filter 1 3 are arranged to perform primary filtration and fine filtration on the solid impurities in the nickel-lithium solution. First, the nickel-lithium solution enters the plate-and-frame filter press 1 1, and the solid impurities in the nickel-lithium solution are removed in the plate-and-frame filter press 1 1. In the embodiment, the mesh number of the plate-and-frame filter press 1 1 is selected to be 500-2000. Then, the nickel-lithium solution after the primary filtration is stored in the storage tank 1 2. The storage tank 1 2 arranged between the plate-and-frame filter press 1 1 and the microporous filter 1 3 can buffer the flow, and the storage capacity of the storage tank 1 2 is not less than 60 m³. Next, the nickel-lithium solution after the primary filtration in the storage tank 1 2 enters the microporous filter 1 3 for fine filtration, and the solid impurities in the nickel-lithium solution are further removed in the microporous filter 1 3. In the embodiment, the pore size of the microporous filter 1 3 is 0.5 μm. Then, the nickel-lithium solution after the fine filtration is stored in the storage tank 2 14. Of course, in other embodiments, the storage tank 2 14 can also be replaced by a solution pool.
[0032] In the embodiment, the concentration device 2 comprises a plate heat exchanger 1 21, a falling film evaporator 1 22 and a buffer tank 1 23 connected in series; the falling film evaporator 1 22 further comprises a gas-liquid separator 1 24, a secondary separator 1 25, a compressor 1 26 and a distilled water tank 27 connected in series; the secondary separator 1 25 and the distilled water tank 27, and the distilled water tank 27 and the plate heat exchanger 1 21 are connected in communication. The nickel-lithium solution filtered by the filter storage device 1 first enters the plate heat exchanger 1 21, and the temperature of the nickel-lithium solution is raised to 85-90°C in the plate heat exchanger 1 21, and the generated steam enters the distilled water tank 27 or is transported to the outside. Then, the nickel-lithium solution after the temperature rise enters the falling film evaporator 1 22 and is heated to about 95°C, at which time the generated steam enters the gas-liquid separator 1 24 and the secondary separator 1 25 in sequence and is flashed, the steam generated in the secondary separator 1 25 is stored in the distilled water tank 27, the remaining solution is heated by the compressor 1 26 and then transported to the falling film evaporator 1 22 for continuous heating, and the condensed water generated in the compressor 1 26 is stored in the distilled water tank 27; the distilled water tank 27 is connected in communication with the outside. The nickel-lithium solution after the concentration is discharged from the falling film evaporator 1 22 and stored in the buffer tank 1 23.
[0033] In this embodiment, the nickel-lithium metal precipitation separation device 3 comprises a reaction kettle 31, a centrifuge 32, a drying machine 33 and a buffer tank 34 connected in series. The reaction kettle 31 is also connected with an ammonia tank 35 and a lye tank 36. The nickel-lithium solution concentrated by the concentration device 2 first enters the reaction kettle 31. At this time, the ammonia tank 35 supplies ammonia water to the reaction kettle 31, and the lye tank 36 supplies lye to the reaction kettle 31. The solution is heated to 55±5℃ in the reaction kettle 31, and spherical nickel hydroxide particle slurry is obtained by reaction at a certain speed. The mixture is discharged from the reaction kettle 31 into the centrifuge 32, where solid-liquid separation and washing of solid substances are performed. Then, the solid substances enter the drying machine 33 for drying at a temperature lower than 55℃, and finally spherical nickel hydroxide powder is obtained and discharged. The solution is transported to the buffer tank 2 for storage. Specifically, the volume of the reaction kettle 31 is 6-20m³; the drying machine 33 can be a vacuum drying machine or a disc type drying machine. Of course, in other embodiments, the buffer tank 2 can be replaced by a water tank.
[0034] In this embodiment, the deamination and heavy metal removal device 4 comprises a deamination tower 41, an ammonia absorption tower 42, a sedimentation tank 43, a filter press 44, a buffer tank 3 45, a microporous filter 2 46 and a buffer tank 4 47 connected in series. The deamination tower 41 is also connected with an ammonia condenser 48 and an ammonia tank 2 49. The lithium solution treated by the nickel-lithium metal precipitation separation device 3 is sequentially introduced into the deamination tower 41 and the ammonia absorption tower 42. In this process, ammonia is separated from the solution in the form of ammonia gas. The separated ammonia gas is converted into ammonia water by the ammonia condenser 48 and stored in the ammonia tank 2 49. The ammonia tank 2 49 can be connected with the ammonia tank 1 35 to supplement the ammonia water of the ammonia tank 1 35. The solution after deamination by the deamination tower 41 and the ammonia absorption tower 42 is subjected to preliminary precipitation in the sedimentation tank 43. The clear liquid is sequentially transported to the filter press 44, the buffer tank 3 45 and the microporous filter 2 46. The obtained solution substantially free of heavy metals such as nickel, cobalt and manganese is stored in the buffer tank 4 47. Specifically, the sedimentation tank 43 can be replaced by a stirring tank. The mesh number of the filter press 44 is selected to be 500-1000 meshes. The filter pore size of the microporous filter 2 46 is selected to be 0.2-0.5μm.
[0035] In this embodiment, the concentration and precipitation device 5 comprises, in series, a plate heat exchanger two 51, a falling film evaporator two 52, a buffer tank five 53, a high tank one 54, a lithium precipitation kettle 55, a buffer tank six 56, a centrifuge two 57, a pH adjusting tank one 58, a decarburization tower 59, and a pH adjusting tank two 510; the falling film evaporator two 52 is further connected in series with a gas-liquid separator two 511, a secondary separator two 512, and a condensate tank 513; the secondary separator two 512 is connected in communication with the falling film evaporator two 52 and the condensate tank 513 through a compressor two 514; the concentration and precipitation device 5 further comprises a high tank two 515 connected in communication with the lithium precipitation kettle 55. The lithium solution treated by the deamination and heavy metal removal device 4 is sequentially introduced into the plate heat exchanger two 51 and the falling film evaporator two 52, and the solution is heated to 94°C in the falling film evaporator two 52, and then flashed into the gas-liquid separator two 511, at this time, 90°C steam and concentrated solution are generated; wherein the steam is separated into gas and liquid in the secondary separator two 512, and then sent back to the falling film evaporator two 52 through the compressor two 514 to be heated again, while the generated condensate is collected and stored in the condensate tank 513, and the condensate in the condensate tank 513 can be used for batching or sent to the outside. The solution discharged from the falling film evaporator two 52 is introduced into the buffer tank five 53, and then sent to the high tank one 54, and together with the sodium carbonate solution in the high tank two 515, sent to the lithium precipitation kettle 55, the temperature of the lithium precipitation kettle 55 is maintained above 90°C, and the product of the reaction is sent to the buffer tank six 56, and then subjected to solid-liquid separation by the centrifuge two 57, the obtained solid material is discharged, dried, and then the crude industrial-grade lithium carbonate is obtained; and the liquid is introduced into the pH adjusting tank one 58, in which 15-30% dilute sulfuric acid is added, and after the carbonate in the solution is removed, the solution is introduced into the decarburization tower 59, and the remaining carbon is blown off, so that the carbon content in the solution is less than 30 mg / L. The solution treated by the decarburization tower 59 is sent to the pH adjusting tank two 510, and in the pH adjusting tank two 510, 32% liquid caustic is added to adjust the pH to 6-9.
[0036] In this embodiment, the sodium sulfate crystallization and solution recycling device 6 comprises, in series, a storage tank three 61, a heat exchanger three 62, a gas-liquid separator three 63, a thickener 64, a centrifuge three 65, and a dryer two 66.
[0037] The solution treated by the concentration and precipitation device 5 is introduced into the storage tank three 61, and then sent to the heat exchanger three 62 for heating, and the heated solution is pumped into the gas-liquid separator three 63, when the sodium sulfate is saturated and crystals are precipitated, the crystals are transferred to the thickener 64 for thickening, the thickened material containing crystals is separated by the centrifuge 65, and then dried by the dryer two 66 to obtain sodium sulfate, and the remaining solution can be returned to the storage tank three 61 or the buffer tank five 53 for recycling.
[0038] Although the utility model has disclosed as above with preferable embodiments, however, not to limit the utility model. Any skilled person in the art, without departing from the utility model technical scheme range, can utilize the above disclosed technical content to make many possible changes and modifications to the utility model technical scheme, or modify as equivalent variation equivalent embodiment. Therefore, any simple modification, equivalent variation and modification made to the above embodiments according to the technical essence of the utility model, which does not depart from the content of the utility model technical scheme, should fall within the scope of the utility model technical scheme protection.
Claims
1. A set of nickel lithium solution recovery devices, characterized by, It comprises in series: filtration storage device (1) to remove solid impurities and temporarily store nickel lithium solution; concentration device (2) to concentrate nickel lithium solution; nickel lithium metal precipitation separation device (3) to make nickel metal crystallize and precipitate and separate from the solution, thereby obtaining lithium solution; deamination and heavy metal removal device (4) to remove ammonia and heavy metals; concentration and precipitation device (5) to concentrate lithium solution and react with sodium carbonate to produce lithium carbonate separated from lithium solution; sodium sulfate crystallization and solution recycling device (6) to concentrate and produce sodium sulfate and separate from lithium solution.
2. The nickel lithium solution recovery apparatus of claim 1, wherein: The filtration storage device (1) comprises in series: plate and frame filter press (11), storage tank one (12), microporous filter one (13) and storage tank two (14).
3. The nickel lithium solution recovery apparatus of claim 1, wherein: The concentration device (2) comprises in series: plate heat exchanger one (21), falling film evaporator one (22) and buffer tank one (23); The falling film evaporator one (22) is further connected in series with gas-liquid separator one (24), secondary separator one (25), compressor one (26) and distilled water tank (27); The secondary separator one (25) and the distilled water tank (27) are connected in communication.
4. The nickel lithium solution recovery apparatus of claim 1, wherein: The nickel lithium metal precipitation separation device (3) comprises in series: reaction kettle (31), centrifuge one (32), drying machine one (33) and buffer tank two (34); The reaction kettle (31) is further connected with ammonia water tank one (35) and lye tank (36).
5. The nickel lithium solution recovery apparatus of claim 1, wherein: The deamination and heavy metal removal device (4) comprises in series: deamination tower (41), ammonia absorption tower (42), sedimentation tank (43), filter press (44), buffer tank three (45), microporous filter two (46) and buffer tank four (47); The deamination tower (41) is further connected in series with ammonia condenser (48) and ammonia water tank two (49).
6. The nickel lithium solution recovery apparatus of claim 1, wherein: The concentration and precipitation device (5) comprises in series: plate heat exchanger two (51), falling film evaporator two (52), buffer tank five (53), high-level tank one (54), lithium precipitation kettle (55), buffer tank six (56), centrifuge two (57), pH adjusting tank one (58), decarburization tower (59) and pH adjusting tank two (510); The falling film evaporator two (52) is further connected in series with gas-liquid separator two (511), secondary separator two (512) and condensed water tank (513); The secondary separator two (512) is connected in communication with the falling film evaporator two (52) and the condensed water tank (513) through compressor two (514); The concentration and precipitation device (5) further comprises high-level tank two (515) connected in communication with lithium precipitation kettle (55).
7. The nickel lithium solution recovery apparatus of claim 1, wherein: The sodium sulfate crystallization and solution recycling device (6) comprises in series: storage tank three (61), heat exchanger three (62), gas-liquid separator three (63), thickener (64), centrifuge three (65) and drying machine two (66).