A method for extracting alkali metals from lithium-sinking waste material and an apparatus therefor

Abstract

The application provides a method and equipment for extracting alkali metal from lithium precipitation waste. In the field of alkali metal extraction, 0.0003 mol of ethidium bromide and 0.0002 mol of 1,3,5-triformylphloroglucinol are added in 7.5 mL of dimethyl sulfoxide, respectively, and ultrasonic treatment is carried out for 10 min to obtain an aldehyde monomer solution and an amine monomer solution; S2: the aldehyde monomer solution is slowly added to the amine monomer solution and stirred until it becomes dark red, and then it is left to stand for 24 h to obtain a porous organic framework nanosheet. The artificial cation-chloride co-transporter membrane has weak surface charge, a narrow-pore porous organic framework and high selectivity, can identify basic ions and halogen ions Cl- and reject other cations and anions, and has size-induced ion selectivity: Cl-≈K+>Na+>Li+>>Ca2+>Mg2+, has low permeability to Rb and Cs, uses the rich chloride ions in the lithium precipitation mother liquor to improve lithium ion permeability and lithium extraction performance, and is not prone to produce too much waste liquid, has good selectivity, a fast process and low cost.

Description

Technical Field

[0001] This invention relates to the field of alkali metal extraction technology, and in particular to a method and equipment for extracting alkali metals from lithium precipitate waste. Background Technology

[0002] With the transformation of the energy structure and the rapid development of the new energy industry, the demand for energy storage equipment such as lithium-ion batteries and supercapacitors has exploded. As a result, the strategic value and market price of rare metals such as lithium, rubidium, and cesium, which are the core raw materials for these devices, have also risen accordingly.

[0003] Especially in high-end fields such as new energy vehicles, renewable energy storage, and aerospace, the demand for high-purity lithium, rubidium, cesium and other metals is particularly urgent. As a by-product of lithium salt production, lithium precipitation mother liquor is a solid-liquid mixture containing abundant valuable elements such as rubidium, cesium, lithium, sodium, and magnesium. However, due to the similarity of these elements in chemical properties, the efficient separation and recovery of them from lithium precipitation mother liquor has become a technical challenge.

[0004] However, in the existing technology, the regeneration process of ion exchange resin used in the traditional ion exchange method is complicated, and problems such as poisoning and aging are prone to occur. It consumes a large amount of acid and alkali solutions, generates waste liquid, and has problems such as poor selectivity, long process and high cost.

[0005] Therefore, it is necessary to provide a method and apparatus for extracting alkali metals from lithium precipitate waste to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides a method and equipment for extracting alkali metals from lithium precipitated waste, which solves the technical problems of poor selectivity, long process and high cost of traditional ion exchange method in related technologies.

[0007] To solve the above-mentioned technical problems, the present invention provides a method for extracting alkali metals from lithium precipitate waste, characterized by comprising the following steps:

[0008] S1: Add 0.0003 mol of ethidium bromide and 0.0002 mol of 1,3,5-tricarboxymethyl phloroglucinol to 7.5 mL of dimethyl sulfoxide and sonicate for 10 min to obtain aldehyde monomer solution and amine monomer solution.

[0009] S2: Slowly add the aldehyde monomer solution to the amine monomer solution and stir until it turns dark red. Let it stand for 24 hours to obtain porous organic framework nanosheets.

[0010] S3: Cast the porous organic framework nanosheets obtained in step S2 onto a preheated glass substrate and dry them at 60°C to completely evaporate the solvent, thus obtaining an artificial cation-chloride ion cotransporter membrane.

[0011] S4: Peel the artificial cation-chloride cotransporter membrane from the glass substrate and immerse it in 50 mL of dimethyl sulfoxide for 1 h;

[0012] S5: Clean the artificial cation-chloride cotransporter membrane three times each with ethanol and deionized water and air dry;

[0013] S6: First, the lithium precipitation mother liquor is solidified and liquidified to obtain a liquid. The liquid is then permeated through a 6μm artificial cation-chloride cotransporter membrane for 3 hours to obtain a solution containing Li+, Na+, and Cl- and a rubidium-cesium enriched solution containing Rb+, Cs+, Mg2+, and SO42-.

[0014] S7: An adsorption column was constructed using a gas drying tube. Adsorbent bags filled with 50 mg of Prussian blue ionic liquid powder and 30 mg of ammonium phosphotungstate double cross-linked hydrogel spheres with a cation ratio of 2:1 were prepared. The flow rate was 0.56 mL / s, and rubidium and cesium were adsorbed and leached at room temperature for 7 h.

[0015] S8: Carbon dioxide is introduced into a solution containing Li+, Na+, and Cl- until saturation. The solution is then filtered and dried to obtain lithium carbonate. The lithium carbonate is then converted into an electrolytic lithium salt, and metallic lithium is obtained by electrolyzing the molten salt.

[0016] S9: The filtrate obtained in S8 is evaporated under reduced pressure at 80°C with the vacuum degree controlled at -0.08MPa to obtain sodium chloride.

[0017] S10: After adsorption of S7, the solution is transferred to a rotary evaporator, concentrated and crystallized at 60°C to obtain magnesium sulfate. The magnesium sulfate is converted into a magnesium salt suitable for electrolysis, and then metallic magnesium is obtained by electrolysis of the molten magnesium salt.

[0018] An apparatus for extracting alkali metals from lithium precipitate waste, characterized in that it comprises: a base plate, a mounting frame, a hose, an extraction tube, and a drive mechanism;

[0019] The mounting bracket is fixed to the upper surface of the base plate. Positioning tubes are fixed on both the left and right sides of the mounting bracket. A knob is threaded inside the positioning tube. The flexible tube is installed through the positioning tube and is located inside the mounting bracket. The extraction tube is installed on the upper surface of the base plate and is located on one side of the mounting bracket.

[0020] The driving mechanism includes an electric cylinder and a limiting rod. The electric cylinder and the limiting rod are installed in the middle of the mounting frame. A lifting frame is installed on the top of the electric cylinder. A limiting groove is opened inside the mounting frame. A bidirectional motor is installed inside the lifting frame. The output shafts at both ends of the bidirectional motor are keyway connected to a rotating plate and a lifting gear, respectively. A first slide rod, a second slide rod, and a third slide rod are slidably connected inside the rotating plate. A movable extrusion wheel is installed at the outer end of the first slide rod, the second slide rod, and the third slide rod. A return spring is sleeved on the outer wall of the first slide rod, the second slide rod, and the third slide rod. A slot is opened on the outer wall of the rotating plate on one side of the third slide rod. A trigger guide wheel is rotatably connected to the outside of the third slide rod. A fixed extrusion wheel is rotatably connected inside the rotating plate in the same horizontal direction as the movable extrusion wheel.

[0021] An arc-shaped plate is installed through the inside of the mounting frame and above the rotating plate, and a support plate is fixed on the back of the arc-shaped plate.

[0022] Preferably, the third slide bar has an "L" shape and can slide horizontally along the groove. The second slide bar is horizontally positioned. The outlet end of the hose is sealed to the top of the extraction tube. A discharge check valve is sealed to the bottom of the extraction tube, and a discharge pipe is sealed to the outlet end of the discharge check valve.

[0023] Preferably, the reset spring is fixedly connected to the movable extrusion wheel and the rotating plate on both sides, the receiving plate is installed with the mounting bracket by means of bolts, and the lifting frame can be raised and lowered vertically along the limiting rod and the limiting groove.

[0024] Preferably, a linkage mechanism is also included;

[0025] The top of the mounting frame is bolted to a top frame. A positioning seat is fixed on the upper surface of the mounting frame and on one side of the top frame. A mounting rod is rotatably connected inside the positioning seat. A first gear and a second gear are rotatably connected inside the top frame and at the upper and lower positions of the lifting gear, respectively.

[0026] The linkage mechanism includes a linkage plate and a cam. The cam keyway is connected to the first gear shaft. The linkage plate is rotatably mounted on the outer end of the mounting rod. Connecting wheels and rotating rods are rotatably connected to both sides of the linkage plate, and two baffles are fixed on the outer wall of the rotating rod.

[0027] Preferably, the outer wall of the connecting wheel is continuously in contact with the outer wall of the cam, the inlet end of the hose is located on the upper surface of the rotating rod and between the two baffles, and the first gear and the lifting gear are mutually adapted.

[0028] Preferably, it also includes a gas supply system;

[0029] The air supply mechanism includes a positioning plate and a positioning frame mounted on the upper surface of the base plate. A sleeve is installed inside the positioning frame. An eccentric plate is rotatably connected to the outer wall of the positioning plate. A slide rail is bolted to the outer wall of the positioning plate and located on one side of the eccentric plate. A slider is slidably connected to the outer wall of the slide rail. A connecting plate is rotatably connected to the outer wall of the eccentric plate. A moving rod is fixed to the side wall of the slider. A piston is slidably connected inside the sleeve. An air inlet check valve and an air supply pipe are respectively sealed and installed on the outer wall of the sleeve and located on one side of the piston.

[0030] Preferably, the eccentric plate and the second gear shaft are connected by a keyway, and one side of the connecting plate is rotatably connected to the outer wall of the slider.

[0031] Preferably, one end of the moving rod extends into the sleeve and is fixedly connected to the piston shaft; the air outlet end of the air supply pipe is sealed to the discharge pipe; and the air inlet end of the air supply pipe is sealed to the sleeve via a one-way valve.

[0032] Compared with related technologies, the method and equipment for extracting alkali metals from lithium precipitate waste provided by the present invention have the following advantages:

[0033] Artificial cation-chloride cotransporter membranes possess a weak surface charge, a narrow-pore porous organic framework, and high selectivity. They can recognize basic ions and halide ions (Cl-) while repelling other cations and anions. Their size-induced ion selectivity is: Cl-≈K+>Na+>Li+>>Ca2+>Mg2+. They exhibit low permeability to Rb and Cs. They utilize the abundant chloride ions in the lithium precipitation mother liquor to improve lithium ion permeability and lithium extraction performance. They do not generate excessive waste liquid and offer good selectivity, fast process, and low cost. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0035] Figure 1 This is a schematic diagram of the optimal structure for the present invention;

[0036] Figure 2 This is a schematic diagram of the overall device back structure provided by the present invention;

[0037] Figure 3 for Figure 1 The diagram shows the location distribution of the drive mechanism and mounting bracket;

[0038] Figure 4 for Figure 3The enlarged structural diagram at point A is shown below;

[0039] Figure 5 for Figure 3 and Figure 4 The diagram shows the installation structure of the curved plate, the receiving plate, and the mounting bracket.

[0040] Figure 6 This is a schematic diagram of the cross-sectional structure of the rotating plate provided by the present invention;

[0041] Figure 7 This is a front view schematic diagram of the rotating plate provided by the present invention;

[0042] Figure 8 A schematic diagram showing the positional distribution of the lifting gear, the first gear, and the second gear provided by the present invention;

[0043] Figure 9 A schematic diagram of the initial working state of the rotating plate when it is in a horizontal position, as provided by the present invention;

[0044] Figure 10 for Figure 9 The diagram shows the working state of media conveying when the guide wheel and the arc plate come into contact during the rotation of the rotating plate.

[0045] Figure 11 A schematic diagram of the linkage mechanism structure provided by the present invention;

[0046] Figure 12 This is a schematic diagram of the gas supply mechanism provided by the present invention.

[0047] Explanation of icon numbers:

[0048] 1. Base plate;

[0049] 2. Mounting bracket; 3. Top bracket;

[0050] 4. Extraction tube;

[0051] 5. Drive mechanism; 51. Electric cylinder; 52. Limiting rod; 53. Lifting frame; 54. Bidirectional motor; 55. Turning plate; 56. Lifting gear; 57. First slide rod; 58. Second slide rod; 59. Third slide rod; 510. Limiting groove; 511. Trigger guide wheel; 512. Moving extrusion wheel; 513. Fixed extrusion wheel; 514. Return spring.

[0052] 6. Hose; 7. Positioning tube;

[0053] 8. Linkage mechanism; 81. Linkage plate; 82. Connecting wheel; 83. Cam; 84. Rotating rod; 85. Baffle.

[0054] 9. Air supply mechanism; 91. Positioning plate; 92. Positioning frame; 93. Sleeve; 94. Eccentric plate; 95. Slide rail; 96. Connecting plate; 97. Slider; 98. Moving rod; 99. Piston; 910. Air inlet check valve; 911. Air supply pipe.

[0055] 10. Knob; 11. Positioning seat; 12. Mounting rod;

[0056] 13. Limiting groove; 14. Discharge check valve; 15. Discharge pipe;

[0057] 16. Curved plate, 17. Receiving plate, 18. First gear, 19. Second gear. Detailed Implementation

[0058] 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.

[0059] This invention provides a method and equipment for extracting alkali metals from lithium precipitate waste.

[0060] First embodiment:

[0061] A method for extracting alkali metals from lithium precipitate waste includes the following steps:

[0062] S1: Add 0.0003 mol of ethidium bromide and 0.0002 mol of 1,3,5-tricarboxymethyl phloroglucinol to 7.5 mL of dimethyl sulfoxide and sonicate for 10 min to obtain aldehyde monomer solution and amine monomer solution.

[0063] S2: Slowly add the aldehyde monomer solution to the amine monomer solution and stir until it turns dark red. Let it stand for 24 hours to obtain porous organic framework nanosheets.

[0064] S3: Cast the porous organic framework nanosheets obtained in step S2 onto a preheated glass substrate and dry them at 60°C to completely evaporate the solvent, thus obtaining an artificial cation-chloride ion cotransporter membrane.

[0065] S4: Peel the artificial cation-chloride cotransporter membrane from the glass substrate and immerse it in 50 mL of dimethyl sulfoxide for 1 h;

[0066] S5: Clean the artificial cation-chloride cotransporter membrane three times each with ethanol and deionized water and air dry;

[0067] S6: First, the lithium precipitation mother liquor is solidified and liquidified to obtain a liquid. The liquid is then permeated through a 6μm artificial cation-chloride cotransporter membrane for 3 hours to obtain a solution containing Li+, Na+, and Cl- and a rubidium-cesium enriched solution containing Rb+, Cs+, Mg2+, and SO42-.

[0068] S7: An adsorption column was constructed using a gas drying tube. Adsorbent bags filled with 50 mg of Prussian blue ionic liquid powder and 30 mg of ammonium phosphotungstate double cross-linked hydrogel spheres with a cation ratio of 2:1 were prepared. The flow rate was 0.56 mL / s, and rubidium and cesium were adsorbed and leached at room temperature for 7 h.

[0069] S8: Carbon dioxide is introduced into a solution containing Li+, Na+, and Cl- until saturation. The solution is then filtered and dried to obtain lithium carbonate. The lithium carbonate is then converted into an electrolytic lithium salt, and metallic lithium is obtained by electrolyzing the molten salt.

[0070] S9: The filtrate obtained in S8 is evaporated under reduced pressure at 80°C with the vacuum degree controlled at -0.08MPa to obtain sodium chloride.

[0071] S10: After adsorption of S7, the solution is transferred to a rotary evaporator, concentrated and crystallized at 60°C to obtain magnesium sulfate. The magnesium sulfate is converted into a magnesium salt suitable for electrolysis, and then metallic magnesium is obtained by electrolysis of the molten magnesium salt.

[0072] This embodiment

[0073] Artificial cation-chloride cotransporter membranes possess a weak surface charge, a narrow-pore porous organic framework, and high selectivity. They can recognize basic ions and halide ions Cl- while repelling other cations and anions. Their size-induced ion selectivity is: Cl-≈K+>Na+>Li+>>Ca2+>Mg2+. They exhibit low permeability to Rb and Cs. The abundant chloride ions in the lithium precipitation mother liquor can be used to improve lithium ion permeability and lithium extraction performance. Sodium chloride in the lithium precipitation mother liquor can promote faster lithium ion transport, and the Li+ / Mg2+ selectivity is significantly increased.

[0074] Basic ions and chloride ions are coupled and transported. Chloride ions promote the faster transport of basic ions, and basic ions promote the faster transport of chloride ions. The two promote each other and can achieve synchronous selective separation of chloride ions and basic ions.

[0075] Industrially, the process for extracting Li+ from lithium precipitation mother liquor involves removing NaCl before Li+ / Mg2+ separation to ensure better Li+ / Mg2+ separation performance. However, artificial cation-chloride cotransporter membranes can reverse this process, achieving high-throughput and high-selectivity Li+ sieving in NaCl-containing solutions, exceeding the performance of previously reported membranes.

[0076] Second embodiment:

[0077] Please see Figure 1 and Figure 10 An apparatus for extracting alkali metals from lithium precipitate waste includes: a base plate 1, a mounting frame 2, a hose 6, an extraction tube 4, and a drive mechanism 5;

[0078] The mounting bracket 2 is fixed to the upper surface of the base plate 1. Positioning tubes 7 are fixed on both the left and right sides of the mounting bracket 2. A knob 10 is threaded inside the positioning tube 7. The hose 6 is installed through the positioning tube 7 and is located inside the mounting bracket 2. The extraction tube 4 is installed on the upper surface of the base plate 1 and is located on one side of the mounting bracket 2.

[0079] The drive mechanism 5 includes an electric cylinder 51 and a limiting rod 52. The electric cylinder 51 and the limiting rod 52 are installed in the middle position inside the mounting frame 2. A lifting frame 53 is installed on the top of the electric cylinder 51. A limiting groove 13 is opened inside the mounting frame 2. A bidirectional motor 54 is installed inside the lifting frame 53. The output shafts at both ends of the bidirectional motor 54 are keyway connected to a rotating plate 55 and a lifting gear 56, respectively. A first sliding rod 57, a second sliding rod 58, and a third sliding rod 59 are slidably connected inside the rotating plate 55. The outer ends of the first slide rod 57, the second slide rod 58 and the third slide rod 59 are equipped with movable extrusion wheels 512. The outer walls of the first slide rod 57, the second slide rod 58 and the third slide rod 59 are respectively fitted with return springs 514. The outer wall of the rotating plate 55 and located on one side of the third slide rod 59 are provided with a slot 510. The outside of the third slide rod 59 is rotatably connected to a trigger guide wheel 511. The inside of the rotating plate 55 and rotatably connected to a fixed extrusion wheel 513 in the same horizontal direction as the movable extrusion wheel 512.

[0080] An arc-shaped plate 16 is installed through the inside of the mounting bracket 2 and above the rotating plate 55, and a receiving plate 17 is fixed on the back of the arc-shaped plate 16.

[0081] Please see Figure 3 , Figure 4 and Figure 6 When the user starts the bidirectional motor 54, the bidirectional motor 54 can drive the rotating plate 55 and the lifting gear 56 to rotate synchronously. During the rotation of the rotating plate 55, the fixed extrusion wheel 513 and the moving extrusion wheel 512 will be driven to rotate in linkage.

[0082] Please see Figure 3 and Figure 6 During adsorption and extraction, the rotating plate 55 needs to be controlled to rotate clockwise. During the rotation, the fixed extrusion wheel 513 and the moving extrusion wheel 512 rotate and extrude the surface of the contact hose 6, so that the medium in the hose 6 can be continuously transported from the mounting frame 2 to the inside of the extraction tube 4. The principle is similar to that of a peristaltic pump.

[0083] The extraction tube 4 uses a gas drying tube to construct an adsorption column. Adsorbent bags filled with 50 mg of Prussian blue ionic liquid powder and 30 mg of ammonium phosphotungstate double cross-linked hydrogel balls with a cation ratio of 2:1 are prepared respectively, which can adsorb and leach rubidium and cesium at room temperature.

[0084] The third slide bar 59 has an "L" shape and can slide horizontally along the slot 510. The second slide bar 58 is horizontally set. The outlet end of the hose 6 is sealed to the top of the extraction tube 4. The bottom of the extraction tube 4 is sealed with a discharge check valve 14, and the outlet end of the discharge check valve 14 is sealed with a discharge tube 15.

[0085] The reset spring 514 is fixedly connected to the movable extrusion wheel 512 and the rotating plate 55 on both sides. The receiving plate 17 is installed with the mounting bracket 2 by means of bolts. The lifting frame 53 can be raised and lowered vertically along the limiting rod 52 and the limiting groove 13.

[0086] Please see Figure 9 When the rotating plate 55 is in its initial working state, the rotating plate 55 is in a horizontal direction. At this time, the trigger guide wheel 511 and the arc plate 16 will not be in contact. In the initial state, the axis of the moving extrusion wheel 512 and the fixed extrusion wheel 513 are equidistant from the center of the rotating plate 55.

[0087] Please see Figure 10 As the rotating plate 55 rotates, the trigger guide wheel 511 rotates to the surface of the arc plate 16, and the trigger guide wheel 511 adaptively controls the extension of the moving extrusion wheel 512 according to the height of the arc plate 16. When the moving extrusion wheel 512 extends, the distance between the axis of the moving extrusion wheel 512 and the center of the rotating plate 55 becomes longer, and the depth of the moving extrusion wheel 512 extruding the hose 6 becomes greater, thereby achieving secondary assistance to push the medium inside the hose 6.

[0088] Understandable:

[0089] Please see Figure 7 The two circular dashed lines in this figure represent the central circles of the arc plate 16 and the trigger guide wheel 511 about the center of the rotating plate 55. As can be seen from the figure, the range of the arc plate 16 is larger than the range of motion of the trigger guide wheel 511. Therefore, when the trigger guide wheel 511 rotates to the position of the arc plate 16, it automatically rolls adaptively along the surface of the arc plate 16.

[0090] Please refer to it again. Figure 6 When the trigger guide wheel 511 is pushed by the arc plate 16, it will affect the third slide bar 59 to achieve the integrated linkage of the second slide bar 58 and the first slide bar 57 to slide and extend the moving extrusion wheel 512. At this time, the reset spring 514 extends. When the trigger guide wheel 511 continues to rotate and the arc plate 16 moves away, the moving extrusion wheel 512 will automatically reset.

[0091] The working principle of this embodiment:

[0092] S1: First, the user needs to install the hose 6. During the installation process, first pass the outlet end of the entire hose 6 through the positioning tube 7 on one side of the mounting frame 2, so that the hose 6 forms an arc shape inside the mounting frame 2. Then pull the outlet end out from the positioning tube 7 on the other side. Finally, seal the outlet end of the hose 6 and the extraction tube 4. Rotate the knob 10 to position the hose 6 in the two positioning tubes 7. After positioning, install the inlet of the hose 6 and the rubidium-cesium enrichment tank (the rubidium-cesium enrichment tank can be externally installed).

[0093] S2: The user starts the bidirectional motor 54 to drive the rotating plate 55 to rotate clockwise. The rotation of the rotating plate 55 continuously squeezes and pushes the surface of the arc-shaped hose 6 through the moving extrusion roller 512 and the fixed extrusion roller 513, thereby transporting the medium in the hose 6 to the extraction tube 4, and realizing the adsorption and extraction of rubidium and cesium through the extraction tube 4.

[0094] This embodiment

[0095] Compared to traditional alkali metal extraction designs, this invention employs a double-layered stationary column filled with different adsorbents. The upper layer adsorbs cesium ions, while the lower layer adsorbs rubidium ions. The two layers do not interfere with each other, achieving efficient adsorption and separation. The adsorbents are stable and have high adsorption efficiency. Cesium and rubidium ions can be recognized and selectively adsorbed by the adsorbents, and the cation membrane (adsorbent bag) can prevent anions from entering.

[0096] Furthermore, during the adsorption and extraction process, a fixed extrusion wheel 513 and a moving extrusion wheel 512 are used to extrude the hose 6 to deliver the medium into the extraction tube 4. The fluid only flows inside the hose 6 and does not come into contact with other components, which fundamentally avoids fluid contamination and prevents fluid corrosion or wear. This effectively ensures the stability of the rubidium-cesium enrichment solution, thereby further improving the extraction accuracy.

[0097] Secondly, a specially shaped arc plate 16 is provided, and the height of the arc plate 16 is higher than that of the trigger guide wheel 511. When the trigger guide wheel 511 rotates to the position of the arc plate 16, the moving extrusion wheel 512 can be controlled to form a secondary extension depth to extrude the medium in the hose 6. This design can maximize the driving force, ensure rapid delivery of the medium, and effectively improve the adsorption and extraction efficiency.

[0098] Third embodiment:

[0099] Please see Figure 3 , Figure 7 , Figure 8 and Figure 11 It also includes linkage mechanism 8;

[0100] The top of the mounting frame 2 is bolted to a top frame 3. A positioning seat 11 is fixed on the upper surface of the mounting frame 2 and on one side of the top frame 3. An installation rod 12 is rotatably connected inside the positioning seat 11. A first gear 18 and a second gear 19 are rotatably connected inside the top frame 3 and at the upper and lower positions of the lifting gear 56, respectively.

[0101] The linkage mechanism 8 includes a linkage plate 81 and a cam 83. The cam 83 is keyway connected to the shaft of the first gear 18. The linkage plate 81 is rotatably mounted on the outer end of the mounting rod 12. Connecting wheels 82 and rotating rods 84 are rotatably connected to both sides of the linkage plate 81. Two baffles 85 are fixed on the outer wall of the rotating rod 84.

[0102] The outer wall of the connecting wheel 82 is continuously in contact with the outer wall of the cam 83, the inlet end of the hose 6 is located on the upper surface of the rotating rod 84 and between the two baffles 85, and the first gear 18 and the lifting gear 56 are mutually adapted.

[0103] Please see Figure 8 In the second embodiment, the lifting gear 56 will rotate synchronously with the rotating plate 55. At this time, the lifting gear 56 is separated from the first gear 18 and the second gear 19. Therefore, in the second embodiment, the lifting gear 56 will not affect the first gear 18 and the second gear 19.

[0104] Please see Figure 3 and Figure 8 If, in the second embodiment, the conveying requirements cannot be met by the single extrusion of the moving extrusion wheel 512, or if the user needs to replace the hose 6 with a thinner hose, then the method of the first embodiment will not work, because the extrusion depth of the hose 6 is different.

[0105] At this time, the user can start the electric cylinder 51 to push the lifting frame 53 to rise vertically along the limit rod 52. During the rising process, the lifting gear 56 and the first gear 18 mesh, and the rotating plate 55 will also rise. When the rotating plate 55 rotates, it will automatically increase the squeezing depth of the moving extrusion wheel 512 and the fixed extrusion wheel 513 on the hose 6.

[0106] Understandable: Please combine Figure 7 When the rotating plate 55 rises, the trigger guide wheel 511 will also rise. When the trigger guide wheel 511 rotates, it will pass through the arc plate 16 and will not interfere with the arc plate 16. At this time, the moving extrusion wheel 512 and the fixed extrusion wheel 513 extrude the hose 6 to the same depth.

[0107] Please see Figure 11When the rotating plate 55 is squeezing the hose 6, the lifting gear 56 will rotate and mesh with the first gear 18 to drive the cam 83 to rotate. When the long end of the cam 83 rotates to the position of the connecting wheel 82, the connecting wheel 82 will control the linkage plate 81 to rotate counterclockwise along the hinge position of the mounting rod 12. During the counterclockwise rotation, the rotating rod 84 will be driven to rotate counterclockwise and move downward.

[0108] This embodiment

[0109] According to the density of the original rubidium-cesium enrichment solution and when a thinner hose 6 needs to be replaced, the lifting frame 53 can be driven to drive the rotating plate 55 to rise, thereby changing the squeezing depth of the moving squeezing wheel 512 and the fixed squeezing wheel 513 on the hose 6, thus further realizing the flexibility in the extraction process.

[0110] Secondly, as the rotating plate 55 rises, the lifting gear 56 and the first gear 18 mesh and rotate, influencing the linkage plate 81 to rotate counterclockwise, causing the rotating rod 84 to move downwards. As the rotating rod 84 moves downwards, it influences the upper hose 6 to move downwards. When moving downwards, the rubidium-cesium enriched liquid in the hose 6 will form a downward trend, thus automatically forming a downward attraction to assist in the conveying. As the linkage plate 81 rotates repeatedly, the hose 6 will return to its initial state. During the resetting process, the medium in the hose 6 changes from a downward trend to an upward trend, thus forming a secondary assist in the conveying of the rubidium-cesium enriched liquid from the hose 6.

[0111] Fourth embodiment:

[0112] Please see Figure 8 and Figure 12 It also includes gas supply facilities 9;

[0113] The air supply mechanism 9 includes a positioning plate 91 and a positioning frame 92 installed on the upper surface of the base plate 1. A sleeve 93 is installed inside the positioning frame 92. An eccentric plate 94 is rotatably connected to the outer wall of the positioning plate 91. A slide rail 95 is bolted to the outer wall of the positioning plate 91 and located on one side of the eccentric plate 94. A slider 97 is slidably connected to the outer wall of the slide rail 95. A connecting plate 96 is rotatably connected to the outer wall of the eccentric plate 94. A moving rod 98 is fixedly provided on the side wall of the slider 97. A piston 99 is slidably connected inside the sleeve 93. An air inlet check valve 910 and an air supply pipe 911 are respectively sealed and installed on the outer wall of the sleeve 93 and located on one side of the piston 99.

[0114] The eccentric plate 94 and the second gear 19 are connected by a keyway at their shafts, and one side of the connecting plate 96 is rotatably connected to the outer wall of the slider 97.

[0115] One end of the moving rod 98 extends into the inside of the sleeve 93 and is fixedly connected to the axis of the piston 99. The air outlet end of the air supply pipe 911 is sealed to the discharge pipe 15, and the air inlet end of the air supply pipe 911 is sealed to the sleeve 93 through a one-way valve.

[0116] Understandably, the gas supply pipe 911 and the sleeve 93 are equipped with one-way valves to prevent the medium in the discharge pipe 15 from being sucked into the sleeve 93.

[0117] Please see Figure 8 In the operation of the first and second embodiments, if it is necessary to replace the larger hose 6, the lifting frame 53 needs to be controlled to move downward, and during the downward movement of the lifting frame 53, the lifting gear 56 will mesh with the second gear 19.

[0118] Please see Figure 8 and Figure 12 When the rotating plate 55 rotates and squeezes the medium in the hose 6, the lifting gear 56 will mesh synchronously to control the rotation of the second gear 19. The second gear 19 drives the eccentric plate 94 to rotate. During the rotation of the eccentric plate 94, the connecting plate 96 pulls the slider 97 to move back and forth along the horizontal direction of the slide rail 95, thereby controlling the moving rod 98 to push the piston 99 to move inside the sleeve 93. When the piston 99 pushes, it can generate squeezed gas. The gas enters the discharge pipe 15 through the gas supply pipe 911. When the piston 99 is in the process of suction, it will draw the external gas into the sleeve 93 through the inlet one-way valve 910. The user can install an inert gas tank outside the inlet one-way valve 910.

[0119] This embodiment

[0120] By designing a follower-operated air supply mechanism 9, the lifting frame 53 can be driven to descend by controlling the electric cylinder 51, and the rotating plate 55 can be lowered in conjunction, so that the thicker hose 6 can be squeezed and conveyed.

[0121] If a thicker hose 6 is used for delivery, the amount of rubidium-cesium enriched liquid delivered will be greater. Therefore, when the lifting frame 53 is adjusted downwards, the lifting gear 56 will mesh with the second gear 19. At this time, when the second gear 19 rotates, it can control the piston 99 to form a reciprocating push-pull motion inside the sleeve 93. During the push-pull motion, gas can be delivered to the discharge pipe 15. The gas delivery can help push the liquid out. The gas can be dispersed in the medium inside the discharge pipe 15. Furthermore, the user can replace the gas in the sleeve 93 with inert gas for protective delivery according to the characteristics of the medium.

[0122] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made under the concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for extracting alkali metals from lithium precipitate waste, characterized in that, Includes the following steps: S1: Add 0.0003 mol of ethidium bromide and 0.0002 mol of 1,3,5-tricarboxymethyl phloroglucinol to 7.5 mL of dimethyl sulfoxide and sonicate for 10 min to obtain aldehyde monomer solution and amine monomer solution. S2: Slowly add the aldehyde monomer solution to the amine monomer solution and stir until it turns dark red. Let it stand for 24 hours to obtain porous organic framework nanosheets. S3: Cast the porous organic framework nanosheets obtained in step S2 onto a preheated glass substrate and dry them at 60°C to completely evaporate the solvent, thus obtaining an artificial cation-chloride ion cotransporter membrane. S4: Peel the artificial cation-chloride cotransporter membrane from the glass substrate and immerse it in 50 mL of dimethyl sulfoxide for 1 h; S5: Clean the artificial cation-chloride cotransporter membrane three times each with ethanol and deionized water and air dry; S6: First, the lithium precipitation mother liquor is processed into a liquid through solid-liquid treatment. The liquid is then permeated through a 6μm artificial cation-chloride ion cotransporter membrane for 3 hours to obtain a Li-containing solution. + Na + Cl - The solution and rubidium-cesium enrichment solution, the rubidium-cesium enrichment solution containing Rb + Cs + Mg 2+ SO4 2- ; S7: An adsorption column was constructed using a gas drying tube. Adsorbent bags filled with 50 mg of Prussian blue ionic liquid powder and 30 mg of ammonium phosphotungstate double cross-linked hydrogel spheres with a cation ratio of 2:1 were prepared. The flow rate was 0.56 mL / s, and rubidium and cesium were adsorbed and leached at room temperature for 7 h. S8: Towards Li + Na + Cl - The solution is filled with carbon dioxide until saturated, filtered, and dried to obtain lithium carbonate. The lithium carbonate is then converted into an electrolytic lithium salt, and metallic lithium is obtained by electrolyzing the molten salt. S9: The filtrate obtained in S8 is evaporated under reduced pressure at 80°C with the vacuum degree controlled at -0.08MPa to obtain sodium chloride. S10: After adsorption of S7, the solution is transferred to a rotary evaporator, concentrated and crystallized at 60°C to obtain magnesium sulfate. The magnesium sulfate is converted into a magnesium salt suitable for electrolysis, and then metallic magnesium is obtained by electrolysis of the molten magnesium salt.

2. An apparatus for extracting alkali metals from lithium precipitated waste, used in step S7 of the method for extracting alkali metals from lithium precipitated waste as described in claim 1, characterized in that, include: Base plate, mounting bracket, hose, extraction tube, and drive mechanism; The mounting bracket is fixed to the upper surface of the base plate. Positioning tubes are fixed on both the left and right sides of the mounting bracket. A knob is threaded inside the positioning tube. The flexible tube is installed through the positioning tube and is located inside the mounting bracket. The extraction tube is installed on the upper surface of the base plate and is located on one side of the mounting bracket. The driving mechanism includes an electric cylinder and a limiting rod. The electric cylinder and the limiting rod are installed in the middle of the mounting frame. A lifting frame is installed on the top of the electric cylinder. A limiting groove is opened inside the mounting frame. A bidirectional motor is installed inside the lifting frame. The output shafts at both ends of the bidirectional motor are keyway connected to a rotating plate and a lifting gear, respectively. A first slide rod, a second slide rod, and a third slide rod are slidably connected inside the rotating plate. A movable extrusion wheel is installed at the outer end of the first slide rod, the second slide rod, and the third slide rod. A return spring is sleeved on the outer wall of the first slide rod, the second slide rod, and the third slide rod. A slot is opened on the outer wall of the rotating plate on one side of the third slide rod. A trigger guide wheel is rotatably connected to the outside of the third slide rod. A fixed extrusion wheel is rotatably connected inside the rotating plate in the same horizontal direction as the movable extrusion wheel. An arc-shaped plate is installed through the inside of the mounting frame and above the rotating plate, and a support plate is fixed on the back of the arc-shaped plate.

3. The apparatus for extracting alkali metals from lithium precipitate waste according to claim 2, characterized in that, The third slide bar has an "L" shape and can slide horizontally along the groove. The second slide bar is horizontally positioned. The outlet end of the hose is sealed to the top of the extraction tube. The bottom of the extraction tube is sealed with a discharge check valve, and the outlet end of the discharge check valve is sealed with a discharge pipe.

4. The apparatus for extracting alkali metals from lithium precipitate waste according to claim 2, characterized in that, The reset spring is fixedly connected to the movable extrusion wheel and the rotating plate on both sides. The receiving plate is installed with the mounting bracket by means of bolts. The lifting frame can be raised and lowered vertically along the limit rod and the limit groove.

5. The apparatus for extracting alkali metals from lithium precipitate waste according to claim 2, characterized in that, It also includes linkage mechanisms; The top of the mounting frame is bolted to a top frame. A positioning seat is fixed on the upper surface of the mounting frame and on one side of the top frame. A mounting rod is rotatably connected inside the positioning seat. A first gear and a second gear are rotatably connected inside the top frame and at the upper and lower positions of the lifting gear, respectively. The linkage mechanism includes a linkage plate and a cam. The cam keyway is connected to the first gear shaft. The linkage plate is rotatably mounted on the outer end of the mounting rod. Connecting wheels and rotating rods are rotatably connected to both sides of the linkage plate, and two baffles are fixed on the outer wall of the rotating rod.

6. The apparatus for extracting alkali metals from lithium precipitate waste according to claim 5, characterized in that, The outer wall of the connecting wheel is continuously in contact with the outer wall of the cam, the inlet end of the hose is located on the upper surface of the rotating rod and between the two baffles, and the first gear and the lifting gear are adapted to each other.

7. The apparatus for extracting alkali metals from lithium precipitate waste according to claim 5, characterized in that, This also includes gas supply organizations; The air supply mechanism includes a positioning plate and a positioning frame mounted on the upper surface of the base plate. A sleeve is installed inside the positioning frame. An eccentric plate is rotatably connected to the outer wall of the positioning plate. A slide rail is bolted to the outer wall of the positioning plate and located on one side of the eccentric plate. A slider is slidably connected to the outer wall of the slide rail. A connecting plate is rotatably connected to the outer wall of the eccentric plate. A moving rod is fixed to the side wall of the slider. A piston is slidably connected inside the sleeve. An air inlet check valve and an air supply pipe are respectively sealed and installed on the outer wall of the sleeve and located on one side of the piston.

8. The apparatus for extracting alkali metals from lithium precipitate waste according to claim 7, characterized in that, The eccentric plate is connected to the second gear shaft via a keyway, and one side of the connecting plate is rotatably connected to the outer wall of the slider.

9. The apparatus for extracting alkali metals from lithium precipitate waste according to claim 7, characterized in that, One end of the moving rod extends into the inside of the sleeve and is fixedly connected to the piston shaft. The air outlet end of the air supply pipe is sealed to the discharge pipe, and the air inlet end of the air supply pipe is sealed to the sleeve through a one-way valve.

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