Lepidolite tailing rubidium and cesium extraction device, efficient rubidium and cesium extraction agent and preparation method thereof

Abstract

The invention provides a lepidolite tailing rubidium and cesium extraction device, a rubidium and cesium efficient extraction agent and a preparation method of the rubidium and cesium efficient extraction agent, and relates to the technical field of metal material recycling. The driving mechanism comprises a mounting seat fixedly arranged at the bottom of the front surface of the treatment tank, the inner side of the mounting seat is rotationally connected with a rotating rod, and a surface key groove of the rotating rod is connected with a driving gear. According to the scheme, the pH value of the lepidolite leachate is finally and rapidly adjusted in a targeted mode, the problem that local pH value fluctuation is large due to the fact that excessive pH adjusting liquid is put at a time is solved, the problem that the pH adjusting efficiency of the lepidolite leachate is low due to the fact that the pH adjusting liquid is put intermittently can be solved, gas is injected into the lepidolite leachate at the same time, and the efficiency of adjusting the pH value of the lepidolite leachate is improved. While the pH adjusting liquid and the lepidolite leaching liquid are helped to be fused, the liquid turbulence is enhanced, the concentration gradient is reduced, the pH value of the lepidolite leaching liquid is rapidly adjusted, and the extraction efficiency of rubidium and cesium metal is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of metal material recovery, in particular to a lepidolite tailings rubidium-cesium extraction device, a rubidium-cesium high-efficiency extraction agent and a preparation method thereof. Background Art

[0002] Rubidium and cesium are rare alkali metals widely used in high-tech fields, but their recycling is crucial due to their scarcity and high environmental risks. When lithium is extracted from lepidolite, rubidium and cesium often occur as associated metals in the tailings, with concentrations reaching hundreds of ppm. Cesium is highly soluble in water and difficult to degrade once it seeps into groundwater. This can disrupt soil microbial communities, cause plant poisoning, and significantly pollute water and soil. Recycling rubidium and cesium from lepidolite tailings can not only prevent ecological disasters, but also reduce the overall cost of lithium extraction from lepidolite and promote sustainable resource utilization.

[0003] In the prior art, when using an extractant to recover rubidium and cesium from lepidolite tailings, the pH of the lepidolite leachate must be adjusted and the lepidolite leachate flocculated. However, existing lepidolite tailings rubidium and cesium extraction equipment is not convenient for quickly adjusting the pH of the lepidolite leachate, resulting in low extraction efficiency of the rubidium and cesium metals.

[0004] Therefore, it is necessary to provide a lepidolite tailings rubidium-cesium extraction device to solve the above technical problems. Summary of the Invention

[0005] The present invention provides a lepidolite tailings rubidium-cesium extraction device, which solves the technical problem in the related art that the existing lepidolite tailings rubidium-cesium extraction device is inconvenient to quickly adjust the pH value of the lepidolite leachate during use, resulting in low rubidium-cesium metal extraction efficiency.

[0006] In order to solve the above technical problems, the present invention provides a lepidolite tailings rubidium-cesium extraction device comprising: a treatment tank, a driving mechanism, an air intake mechanism and a liquid intake mechanism;

[0007] The driving mechanism includes a mounting base fixedly arranged at the bottom of the front surface of the treatment tank, a rotating rod is rotatably connected to the inner side of the mounting base, a driving gear is connected to the keyway on the surface of the rotating rod, a rotating shaft is rotatably connected to the inner side of the mounting base and located on the left side of the rotating rod, a passive gear is fixed on the surface of the rotating shaft, the passive gear is meshed with the active gear, and a driving motor for driving the rotating rod to rotate is provided at the bottom of the mounting base;

[0008] The air intake mechanism includes a cam fixedly mounted on the top end of the rotating rod, an air intake cylinder fixedly mounted on the inner side of the treatment tank, a first piston slidably connected to the inner side of the air intake cylinder, a first spring sleeved on the surface of the first piston and located on the outer side of the air intake cylinder, a first rotating seat fixedly mounted on the front side of the first piston, an air outlet pipe connected to the back side of the air intake cylinder, and an air intake pipe connected to the right side of the air intake cylinder;

[0009] The liquid inlet mechanism includes a disc fixedly mounted on the top of the rotating shaft, a convex disc provided on the top of the disc, connecting bolts provided on the inner sides of the disc and the convex disc, a liquid inlet cylinder provided on the inner side of the treatment pool, a second piston slidably connected to the inner side of the liquid inlet cylinder, a second spring provided on the surface of the second piston and located on the outer side of the liquid inlet cylinder, a second rotating seat fixedly provided on the front side of the second piston, a liquid outlet pipe connected to the back side of the liquid inlet cylinder, and a liquid inlet pipe connected to the left side of the liquid inlet cylinder.

[0010] Preferably, the air intake mechanism and the liquid intake mechanism are respectively vertically arranged in three groups on the surface of the rotating rod and the rotating shaft, and the air intake cylinder is located at the bottom of the liquid intake cylinder, and a through groove is opened on the inner side of the disc for use with the connecting bolt.

[0011] Preferably, the front end of the air inlet pipe is connected to the air inlet main pipe, and the front end of the liquid inlet pipe is connected to the liquid inlet main pipe.

[0012] Preferably, a mixing mechanism is fixedly provided on the inner wall of the treatment tank, and the mixing mechanism includes a mounting frame fixedly provided on the inner side of the treatment tank, the inner side of the mounting frame is vertically connected to a rotating shaft, two sets of stirring frames are fixedly provided on the surface of the rotating shaft, a stirring paddle is fixedly provided at the bottom end of the rotating shaft, and a mixing motor for driving the rotating shaft to rotate is provided on the top of the mounting frame.

[0013] Preferably, the inner side of the mounting frame is slidably connected to a feeding mechanism, and the feeding mechanism includes a tooth plate slidably connected to the inner side of the mounting frame, the bottom of the tooth plate is slidably connected to a slide rail, the bottom of the slide rail is fixedly connected to the top of the mounting frame, a discharge box is fixedly provided on the top of the tooth plate, a guide rod is fixedly provided on the front side of the tooth plate, a return spring is sleeved on the surface of the guide rod, a bracket is slidably connected to the surface of the guide rod, the left side of the bracket is fixedly connected to the right side of the mounting frame, a half gear is fixedly provided on the top of the rotating shaft, and the half gear is meshed with the tooth plate.

[0014] Preferably, the right side of the treatment tank is connected to a water inlet pipe, a sieve plate is fixedly provided on the right side of the inner wall of the treatment tank, and a supporting leg is fixedly provided on the bottom of the treatment tank.

[0015] Preferably, two collecting tanks are fixedly provided at the bottom of the treatment pool, and the bottoms of the two collecting tanks are connected to a sewage pipe.

[0016] Rubidium and cesium high-efficiency extractants, including:

[0017] Main carrier: acrylic skeleton macroporous white balls with pore size of 50-200nm, providing high specific surface area and acid and alkali resistance;

[0018] Auxiliary carrier: pyridine functionalized polystyrene microspheres to enhance the coordination adsorption capacity of rubidium and cesium;

[0019] Active ingredient: ammonium phosphomolybdate (NH4) PM O12 O 40 , loaded on the surface of the dual carrier through chemical bonding to form a stable porous composite structure;

[0020] Cross-linking agent: Epoxy resin-silane coupling agent composite system, which improves mechanical strength and prevents the loss of active components.

[0021] The preparation method of a rubidium-cesium efficient extractant comprises the following steps:

[0022] Step S1, dual-carrier pretreatment:

[0023] Acrylic macroporous white spheres and pyridyl polystyrene microspheres were mixed in a mass ratio of 3:1, washed with 0.5 mol / L NaOH solution, and then washed with water until neutral;

[0024] Step S2, active component loading:

[0025] Prepare a 20% ammonium phosphomolybdate solution, mix it with the pretreated dual carrier at a volume ratio of 5:1, and stir at 60°C for 12 hours to form a preliminary supported structure;

[0026] Step S3, composite cross-linking:

[0027] The loaded support was immersed in an ethanol solution containing 10% epoxy resin and 2% silane coupling agent, and cross-linked at 60°C for eight hours to obtain a composite extractant with high mechanical strength after curing;

[0028] Step S4, post-processing:

[0029] The product was washed three times with 3 mol / L hydrochloric acid to remove unreacted impurities, dried and sieved to obtain a particle size of 0.5-1 mm to obtain the finished product.

[0030] Compared with related technologies, the lepidolite tailings rubidium-cesium extraction device, rubidium-cesium high-efficiency extraction agent and preparation method thereof provided by the present invention have the following beneficial effects:

[0031] When adjusting the pH value of the lepidolite leachate, the overlapping position of the disc and the convex disc is adjusted by connecting bolts in view of the different pH values of the lepidolite at different depths, thereby adding different amounts of pH adjusting liquid to different depths of the lepidolite leachate, thereby achieving targeted and rapid adjustment of the pH value of the lepidolite leachate. This avoids the problem of large local pH value fluctuations caused by excessive one-time addition of pH adjusting liquid, and solves the problem of low pH adjustment efficiency of the lepidolite leachate caused by intermittent addition of pH adjusting liquid. At the same time, gas is injected into the lepidolite leachate to help the pH adjusting liquid and the lepidolite leachate merge, thereby enhancing liquid turbulence, reducing concentration gradients, and rapidly adjusting the pH value of the lepidolite leachate, thereby improving the extraction efficiency of rubidium and cesium metals. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0033] Figure 1 The best structural diagram provided by the present invention;

[0034] Figure 2 A schematic diagram of the rear view of the treatment pool is provided for the present invention;

[0035] Figure 3 A schematic structural diagram of the driving mechanism, air intake mechanism and liquid intake mechanism provided by the present invention;

[0036] Figure 4 for Figure 3 A schematic structural diagram of a cross-sectional view of an air intake cylinder is shown;

[0037] Figure 5 for Figure 4 The cam shown rotates, causing the piston to move forward under the action of the first spring;

[0038] Figure 6 for Figure 3 The structural diagram of the cross-sectional view of the liquid inlet cylinder shown;

[0039] Figure 7 for Figure 6 The enlarged structural diagram of point A is shown;

[0040] Figure 8 for Figure 6 Schematic diagram of the state in which the disc and the cam rotate and the second piston moves forward under the action of the second spring;

[0041] Figure 9 A schematic structural diagram of the mixing mechanism provided by the present invention;

[0042] Figure 10 A schematic structural diagram of the feeding mechanism provided by the present invention;

[0043] Figure 11 for Figure 10 The schematic diagram shows a state in which the rotating shaft drives the half gear to rotate, causing the two tooth plates to move;

[0044] Figure 12 A schematic structural diagram of a cross-sectional view of a treatment pool provided by the present invention;

[0045] Figure 13 A schematic diagram of the steps of the preparation method provided by the present invention;

[0046] Figure 14 This is a preliminary load structure overview diagram provided by the present invention.

[0047] Description of Figure Numbers:

[0048] 1. Treatment pool;

[0049] 2. Driving mechanism; 21. Mounting seat; 22. Rotating rod; 23. Driving gear; 24. Rotating shaft; 25. Driven gear; 26. Driving motor;

[0050] 3. Intake mechanism; 31. Cam; 32. Intake cylinder; 33. First piston; 34. First spring; 35. First rotating seat; 36. Exhaust pipe; 37. Intake pipe;

[0051] 4. Liquid inlet mechanism; 41. Disc; 42. Convex disc; 43. Connecting bolt; 44. Liquid inlet cylinder; 45. Second piston; 46. Second spring; 47. Second rotating seat; 48. Liquid outlet pipe; 49. Liquid inlet pipe;

[0052] 5. Air inlet pipe; 6. Liquid inlet pipe;

[0053] 7. Mixing mechanism; 71. Mounting frame; 72. Rotating shaft; 73. Stirring frame; 74. Stirring paddle; 75. Mixing motor;

[0054] 8. Feeding mechanism; 81. Tooth plate; 82. Slide rail; 83. Feeding box; 84. Guide rod; 85. Return spring; 86. Bracket; 87. Half gear;

[0055] 9. Water inlet pipe; 10. Sieve plate; 11. Support legs; 12. Collection trough; 13. Sewage pipe.

[0056] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0057] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0058] The present invention provides a lepidolite tailings rubidium-cesium extraction device, a rubidium-cesium high-efficiency extraction agent and a preparation method thereof.

[0059] First embodiment:

[0060] See also Figures 1 to 8 , a lepidolite tailings rubidium-cesium extraction device, comprising a treatment pool 1, a driving mechanism 2, an air intake mechanism 3 and a liquid intake mechanism 4;

[0061] The driving mechanism 2 includes a mounting base 21 fixed to the bottom of the front side of the treatment tank 1, a rotating rod 22 is rotatably connected to the inner side of the mounting base 21, a driving gear 23 is connected to the keyway on the surface of the rotating rod 22, a rotating shaft 24 is rotatably connected to the inner side of the mounting base 21 and located on the left side of the rotating rod 22, a passive gear 25 is fixed on the surface of the rotating shaft 24, and the passive gear 25 is meshed with the active gear 23, and a driving motor 26 for driving the rotating rod 22 to rotate is provided at the bottom of the mounting base 21;

[0062] Please combine Figure 3 : Start the drive motor 26, the drive motor 26 rotates to drive the rotating rod 22 to rotate, the rotating rod 22 rotates to drive the driving gear 23 to rotate, the driving gear 23 rotates to drive the driven gear 25 to rotate, the driven gear 25 rotates to drive the rotating shaft 24 to rotate;

[0063] Furthermore, when the driving gear 23 is adjusted downward and the keyway connection relationship with the rotating rod 22 is broken, the rotation of the driving motor 26 will only drive the rotating rod 22 to rotate;

[0064] The air intake mechanism 3 includes a cam 31 fixed to the top of the rotating rod 22, an air intake cylinder 32 fixed to the inner side of the treatment tank 1, a first piston 33 slidably connected to the inner side of the air intake cylinder 32, a first spring 34 is sleeved on the surface of the first piston 33 and located on the outer side of the air intake cylinder 32, a first rotating seat 35 is fixed to the front side of the first piston 33, an air outlet pipe 36 is connected to the back side of the air intake cylinder 32, and an air intake pipe 37 is connected to the right side of the air intake cylinder 32;

[0065] Please combine Figure 3 and Figure 5When the rotating rod 22 rotates, the cam 31 is simultaneously driven to rotate. When the raised position of the cam 31 moves away from the first rotating seat 35, the first spring 34 causes the first piston 33 to slide forward inside the air intake cylinder 32. As the first piston 33 slides forward, the gas in the air intake pipe 37 is pumped into the air intake cylinder 32.

[0066] Furthermore, when the rotating rod 22 drives the cam 31 to rotate, so that the raised position of the cam 31 contacts the first rotating seat 35, the first piston 33 slides backward inside the air inlet pipe 37, and the first spring 34 contracts. The first piston 33 moves backward, thereby discharging the air in the air inlet cylinder 32 into the treatment tank 1 through the air outlet pipe 36, causing bubbles to appear in the lepidolite leachate in the treatment tank 1.

[0067] Preferably, the surfaces of the air outlet pipe 36 and the air inlet pipe 37 are both provided with a one-way valve, and the surface of the air outlet pipe 36 is provided with a plurality of small holes at equal intervals;

[0068] The liquid inlet mechanism 4 includes a disc 41 fixed to the top of the rotating shaft 24, a convex disc 42 is provided on the top of the disc 41, and connecting bolts 43 are provided on the inner sides of the disc 41 and the convex disc 42. A liquid inlet cylinder 44 is provided on the inner side of the treatment pool 1, and a second piston 45 is slidably connected to the inner side of the liquid inlet cylinder 44. A second spring 46 is sleeved on the surface of the second piston 45 and located on the outer side of the liquid inlet cylinder 44. A second rotating seat 47 is fixed on the front side of the second piston 45. The back side of the liquid inlet cylinder 44 is connected to a liquid outlet pipe 48, and the left side of the liquid inlet cylinder 44 is connected to a liquid inlet pipe 49;

[0069] Please combine Figure 3 and Figure 8 When the rotating shaft 24 rotates, the disc 41 and the convex disc 42 are simultaneously driven to rotate. When the convex disc 42 is out of contact with the second rotating seat 47, the second piston 45 slides forward inside the liquid inlet cylinder 44 under the action of the second spring 46, thereby pumping the pH regulating liquid in the liquid inlet tube 49 into the liquid inlet cylinder 44;

[0070] Furthermore, when the rotating shaft 24 drives the disc 41 and the convex disc 42 to rotate, causing the convex disc 42 to contact the second rotating seat 47, the second piston 45 will slide backward on the inner side of the liquid inlet cylinder 44, and the second spring 46 will be contracted. The second piston 45 moves backward, and the pH regulating liquid in the liquid inlet cylinder 44 is discharged into the lepidolite leachate in the treatment tank 1 through the liquid outlet pipe 48;

[0071] Furthermore, the connection position between the disc 41 and the convex disc 42 is adjusted by the connecting bolt 43. When the overlap between the disc 41 and the convex disc 42 increases, the rotating shaft 24 drives the disc 41 and the convex disc 42 to rotate and squeeze the second rotating seat 47. The backward movement position of the second piston 45 will become smaller, and the pH regulating liquid discharged through the liquid inlet cylinder 44 will also decrease accordingly. Therefore, the pH regulating liquid can be discharged in a targeted manner according to the pH value of the lepidolite leachate at different depths.

[0072] Preferably, one-way valves are provided on the surfaces of the liquid outlet pipe 48 and the liquid inlet pipe 49, and a plurality of small holes are evenly opened on the surface of the liquid outlet pipe 48 for discharging the pH regulating liquid.

[0073] The air inlet mechanism 3 and the liquid inlet mechanism 4 are respectively provided in three groups vertically on the surfaces of the rotating rod 22 and the rotating shaft 24, and the air inlet cylinder 32 is located at the bottom of the liquid inlet cylinder 44. The inner side of the disc 41 is provided with a through groove for use with the connecting bolt 43.

[0074] Preferably, by arranging an air inlet cylinder 32 at the bottom of the liquid inlet cylinder 44, when the pH regulating liquid enters the lepidolite leachate, the bubbles can enhance the mixing effect of the pH regulating liquid and the lepidolite leachate, thereby avoiding large fluctuations in local pH values.

[0075] The front end of the air inlet pipe 37 is connected to the air inlet main pipe 5 , and the front end of the liquid inlet pipe 49 is connected to the liquid inlet main pipe 6 .

[0076] In this embodiment, unlike the existing pH adjustment equipment for lepidolite leachate, when adjusting the pH value of the lepidolite leachate, the present case adjusts the overlapping position of the disc 41 and the convex disc 42 by the connecting bolt 43, taking into account the different pH values at different depths of the lepidolite, thereby adding different amounts of pH adjustment liquid to different depths of the lepidolite leachate, thereby achieving targeted and rapid adjustment of the pH value of the lepidolite leachate. While avoiding the problem of large local pH fluctuations caused by excessive one-time addition of pH adjustment liquid, it can also solve the problem of low pH adjustment efficiency of the lepidolite leachate caused by intermittent addition of pH adjustment liquid. At the same time, gas is injected into the lepidolite leachate to help the pH adjustment liquid and the lepidolite leachate merge, while enhancing liquid turbulence and reducing concentration gradients, thereby rapidly adjusting the pH value of the lepidolite leachate and improving the extraction efficiency of rubidium and cesium metals.

[0077] Second embodiment:

[0078] See also Figures 9 to 12The inner wall of the treatment tank 1 is fixedly provided with a mixing mechanism 7, and the mixing mechanism 7 includes a mounting frame 71 fixedly provided on the inner side of the treatment tank 1, and a rotating shaft 72 is vertically connected to the inner side of the mounting frame 71. Two sets of stirring frames 73 are fixedly provided on the surface of the rotating shaft 72, and a stirring paddle 74 is fixedly provided at the bottom end of the rotating shaft 72. A mixing motor 75 for driving the rotating shaft 72 to rotate is provided on the top of the mounting frame 71;

[0079] Please combine Figure 9 : Start the mixing motor 75, and the rotation of the mixing motor 75 drives the rotating shaft 72 to rotate. The rotation of the rotating shaft 72 drives the two sets of stirring frames 73 to rotate, and at the same time drives the bottom stirring paddle 74 to rotate, thereby promoting the mixing effect of the pH regulating solution and the lepidolite leachate.

[0080] The inner side of the mounting frame 71 is slidably connected to a feeding mechanism 8, and the feeding mechanism 8 includes a toothed plate 81 slidably connected to the inner side of the mounting frame 71, and the bottom of the toothed plate 81 is slidably connected to a slide rail 82, and the bottom of the slide rail 82 is fixedly connected to the top of the mounting frame 71, and a discharge box 83 is fixedly provided on the top of the toothed plate 81, and a guide rod 84 is fixedly provided on the front side of the toothed plate 81, and a return spring 85 is sleeved on the surface of the guide rod 84, and a bracket 86 is slidably connected to the surface of the guide rod 84, and the left side of the bracket 86 is fixedly connected to the right side of the mounting frame 71, and a half gear 87 is fixed on the top of the rotating shaft 72, and the half gear 87 is meshed with the toothed plate 81;

[0081] Please combine Figure 11 When the rotating shaft 72 rotates, it will simultaneously drive the top half gear 87 to rotate. The rotation of the half gear 87 drives the tooth plate 81 to move forward. The forward movement of the tooth plate 81 drives the discharge box 83 and the guide rod 84 to move forward. The movement of the discharge box 83 adjusts the feeding position of the flocculant. The movement of the tooth plate 81 and the guide rod 84 causes the return spring 85 to contract.

[0082] Furthermore, when the rotating shaft 72 drives the half gear 87 to rotate and disengages from the tooth plate 81, the tooth plate 81 moves backward on the surface of the slide rail 82 through the expansion of the reset spring 85, thereby resetting the tooth plate 81 and the discharge box 83, and the rotating shaft 72 continuously drives the half gear 87 to rotate, thereby reciprocatingly adjusting the discharge position of the discharge box 83;

[0083] Preferably, there are two groups of feeding mechanisms 8, which are respectively arranged on both sides of the mounting frame 71, so that the flocculant is fed at two different positions to promote rapid mixing of the flocculant and the lepidolite leachate.

[0084] The right side of the treatment tank 1 is connected to a water inlet pipe 9 , a sieve plate 10 is fixedly provided on the right side of the inner wall of the treatment tank 1 , and a supporting leg 11 is fixedly provided on the bottom of the treatment tank 1 .

[0085] Two collecting tanks 12 are fixedly provided at the bottom of the treatment pool 1 , and the bottoms of the two collecting tanks 12 are connected to a sewage pipe 13 .

[0086] In this embodiment, the rotation of the mixing motor 75 drives the rotating shaft 72, the stirring frame 73 and the stirring paddle 74 to rotate, thereby promoting the mixing effect of the pH adjusting liquid or flocculant and the lithium mica leachate. When the rotating shaft 72 rotates, it will also drive the half gear 87 to rotate. Through the rotation of the half gear 87, with the cooperation of the reset spring 85, the tooth plate 81 drives the discharge box 83 to move back and forth, thereby adjusting the placement position of the flocculant and allowing the flocculant to quickly contact the lithium mica leachate.

[0087] Third embodiment:

[0088] See also Figure 13 and Figure 14 , rubidium and cesium high-efficiency extraction agents, including:

[0089] Main carrier: acrylic skeleton macroporous white balls with pore size of 50-200nm, providing high specific surface area and acid and alkali resistance;

[0090] Auxiliary carrier: pyridine functionalized polystyrene microspheres to enhance the coordination adsorption capacity of rubidium and cesium;

[0091] Active ingredient: ammonium phosphomolybdate (NH4) PM O12 O 40 , loaded on the surface of the dual carrier through chemical bonding to form a stable porous composite structure;

[0092] Cross-linking agent: epoxy resin-silane coupling agent composite system, which improves mechanical strength and prevents loss of active components;

[0093] Furthermore, rubidium and cesium were separated from the lepidolite leachate: the pH of the leachate was adjusted to 3, and after dynamic adsorption, 0.5 mol / L HCl (for rubidium removal) and 2 mol / L HNO3 (for cesium removal) were used for staged elution, and the separation coefficient between rubidium and cesium reached 180.

[0094] The preparation method of a rubidium-cesium efficient extractant comprises the following steps:

[0095] Step S1, dual-carrier pretreatment:

[0096] Acrylic macroporous white spheres and pyridyl polystyrene microspheres were mixed in a mass ratio of 3:1, washed with 0.5 mol / L NaOH solution, and then washed with water until neutral;

[0097] Physical state after mixing:

[0098] When acrylic macroporous white spheres (hydrophilic) are mixed with pyridyl polystyrene microspheres (hydrophobic), a heterogeneous suspension system is formed. Due to the difference in the surface properties of the two carriers (acrylic acid contains carboxylic acid groups, and polystyrene contains pyridine groups), a physical blend is formed by mechanical stirring or ultrasonic dispersion during mixing without obvious chemical reaction. The mixture is a milky white turbid liquid, and slight stratification may occur after standing (continuous stirring is required to maintain uniformity);

[0099] Mixing purpose:

[0100] Synergistic effect: acrylic macroporous white balls provide high specific surface area (500-800m 2 / g) and ion exchange sites (carboxylic acid groups);

[0101] Suitable for physical adsorption: Pyridine-based polystyrene microspheres enhance the chemical selectivity for rubidium and cesium through N coordination (the lone pair electrons of the pyridine ring and Rb + / Cs + empty d orbital coordination).

[0102] Optimize pore structure:

[0103] After the dual carriers are combined, hierarchical pores (macroporous + mesoporous) are formed to improve mass transfer efficiency;

[0104] The role of NaOH cleaning:

[0105] Cleaning objects:

[0106] Unpolymerized monomers (acrylic acid) and initiator fragments (such as ammonium persulfate decomposition products) remaining on the surface of acrylic white balls, and organic solvent residues adsorbed on the surface of pyridyl microspheres (such as toluene and dichloroethane used in the preparation of microspheres);

[0107] Chemical reaction:

[0108] NaOH reacts with the carboxylic acid groups on the surface of the acrylic acid sphere to neutralize and form sodium carboxylate (increasing hydrophilicity): CH2CH(COOH)+NaOH→CH2CH(COO-Na+)+H2OCH2CH(COOH)+NaOH→CH2CH(COO-Na+)+H2O;

[0109] At the same time, NaOH cleaning can partially open the π-π stacking structure of the pyridine group, exposing more active sites;

[0110] Step S2, active component loading:

[0111] Prepare a 20% ammonium phosphomolybdate solution, mix it with the pretreated dual support at a volume ratio of 5:1, and react with stirring at 60°C for 12 hours to form a preliminary supported structure;

[0112] Specific reactions involved:

[0113] Ammonium phosphomolybdate is combined with the dual carrier in the following ways:

[0114] Ion exchange: sodium carboxylate of acrylic acid white spheres (COO - Na + ) and NH4 in ammonium phosphomolybdate + Exchange to form a stable bond: COO-Na++NH4+→COO-NH4++Na+

[0115] Coordination: [PM O12 O 40 ] 3- It coordinates with the nitrogen atom of the pyridyl group through Lewis acid-base interaction.

[0116] Preliminary load structure status:

[0117] Microscopic morphology: Ammonium phosphomolybdate is uniformly distributed on the surface and within the pores of the dual carrier in the form of nanoclusters (10-20nm), forming an "island" structure. The carboxylic acid groups of the acrylic acid white spheres are anchored to the ammonium phosphomolybdate through ionic bonds, and the pyridine groups fix the molybdenum oxygen clusters through coordination bonds.

[0118] Chemical state: After loading, the surface of the carrier appears Acidic (due to NH 4+ dissociation), favoring cesium ions (Cs + ) electrostatic adsorption;

[0119] Step S3, composite cross-linking:

[0120] The loaded support was immersed in an ethanol solution containing 10% epoxy resin and 2% silane coupling agent, and cross-linked at 60°C for 8 hours to obtain a composite extractant with high mechanical strength after curing;

[0121] Cross-linking reaction mechanism:

[0122] Epoxy resin cross-linking: Epoxy groups (—CH(O)CH2—) open the ring under alkaline conditions and react with hydroxyl groups (—OH) or amino groups (—NH2) on the surface of the carrier: Epoxy group + —OH → 60℃—O—CH2CH(OH)—;

[0123] Silane coupling agent bridging: Silane (such as KH-550, NH2(CH2)3Si(OC2H5)3) hydrolyzes to form silanol (-Si(OH)3), which condenses with the hydroxyl group on the carrier surface to form a Si-O-Si bond. At the same time, the amino group reacts with the epoxy resin: Si(OC2H5)3+3H2O→Si(OH)3+3C2H5OHSi(OC2H5)3+-OH(carrier)→-O-Si-O-(covalent bond);

[0124] Cross-linked network structure:

[0125] After cross-linking, a three-dimensional interpenetrating network is formed: the epoxy resin fills the gaps between the carriers to enhance the mechanical strength (compressive strength ≥ 50MPa), and the silane coupling agent builds a "flexible bridge" between the carrier and the epoxy resin to prevent stress cracking;

[0126] Step S4, post-processing:

[0127] The product was washed three times with 3 mol / L hydrochloric acid to remove unreacted impurities, dried and sieved to obtain a particle size of 0.5-1 mm to obtain the finished product.

[0128] Compared with existing rubidium and cesium extractants, this embodiment pioneered a dual-carrier composite structure, combining the physical adsorption of macroporous white spheres with the chemical coordination of pyridine groups, breaking through the limitations of a single carrier. The cross-linking agent can be recycled, and the production process does not emit toxic solvents, making it green and low-cost.

[0129] The pyridyl group and ammonium phosphomolybdate work synergistically to achieve a separation coefficient (Cs / Rb) of over 200 for rubidium and cesium, demonstrating high selectivity. The cross-linked structure allows the extractant to remain intact within the pH range of 1-13. Even after 50 cycles, the adsorption capacity remains >90%, demonstrating strong stability. A single dynamic adsorption step can increase the purity of cesium to 99.95%, eliminating the need for multi-stage extraction or high-temperature treatment. This simplifies the production process and improves the recovery efficiency of rubidium and cesium metals.

[0130] Please refer to the Figures 1 to 14 The working principles of the lepidolite tailings rubidium-cesium extraction device, rubidium-cesium high-efficiency extraction agent and preparation method thereof provided by the present invention are as follows:

[0131] Step S1, before extracting the lepidolite leachate with the rubidium-cesium high-efficiency extractant of the present application, the lepidolite leachate is discharged into a treatment tank 1, the pH value of the lepidolite leachate is first adjusted to 3, and then flocculated to prevent impurities in the lepidolite leachate from clogging the adsorption column when the rubidium-cesium metal is extracted through the extractant adsorption column, thereby reducing the number of backwashing treatments of the extractant adsorption column, thereby improving the recovery efficiency of the rubidium-cesium metal extracted from the lepidolite leachate by the extractant;

[0132] Step S2, when adjusting the pH value of the lepidolite leachate, first start the drive motor 26, the drive motor 26 rotates to drive the rotating rod 22 to rotate, the rotating rod 22 rotates to drive the driving gear 23 to rotate, the driving gear 23 rotates to drive the driven gear 25 to rotate, the driven gear 25 rotates to drive the rotating shaft 24 to rotate;

[0133] When the rotating rod 22 rotates, it will drive the cam 31 to rotate at the same time. When the raised position of the cam 31 is away from the first rotating seat 35, the first piston 33 is caused to slide forward on the inner side of the air inlet cylinder 32 under the action of the first spring 34. The gas in the air inlet pipe 37 is pumped into the air inlet cylinder 32 by the forward sliding of the first piston 33. When the raised position of the cam 31 contacts the first rotating seat 35, the first piston 33 is caused to slide backward on the inner side of the air inlet pipe 37, and the first spring 34 is contracted. The first piston 33 moves backward, thereby discharging the air in the air inlet cylinder 32 into the treatment tank 1 through the air outlet pipe 36, so that bubbles appear in the lepidolite leachate in the treatment tank 1. The continuous rotation of the cam 31 continuously injects gas into the treatment tank 1.

[0134] In step S3, when the rotating shaft 24 rotates, the disc 41 and the convex disc 42 are driven to rotate at the same time. When the convex disc 42 is out of contact with the second rotating seat 47, the second piston 45 is caused to slide forward on the inner side of the liquid inlet cylinder 44 under the action of the second spring 46, thereby pumping the pH regulating liquid in the liquid inlet pipe 49 into the liquid inlet cylinder 44. When the convex disc 42 is in contact with the second rotating seat 47, the second piston 45 is caused to slide backward on the inner side of the liquid inlet cylinder 44, and the second spring 46 is contracted. The second piston 45 moves backward, and the pH regulating liquid in the liquid inlet cylinder 44 is discharged into the lepidolite leachate in the treatment tank 1 through the liquid outlet pipe 48. The disc 41 and the convex disc 42 continue to rotate, thereby continuously injecting the pH regulating liquid into the treatment tank 1.

[0135] The connection position between the disc 41 and the convex disc 42 is adjusted by the connecting bolt 43. When the overlap between the disc 41 and the convex disc 42 increases, the rotating shaft 24 drives the disc 41 and the convex disc 42 to rotate and squeeze the second rotating seat 47. The backward movement position of the second piston 45 will become smaller, and the pH regulating liquid discharged through the liquid inlet cylinder 44 will also decrease accordingly. Therefore, the pH regulating liquid can be discharged in a targeted manner according to the pH value of the lepidolite leachate at different depths.

[0136] Step S4, when the pH regulating liquid is injected into the treatment tank 1, the mixing motor 75 is started at the same time, and the rotating shaft 72 is rotated by the rotating motor 75, and the rotating shaft 72 rotates to drive the two sets of stirring frames 73 to rotate, and at the same time drives the bottom stirring paddle 74 to rotate, thereby promoting the mixing effect of the pH regulating liquid and the lepidolite leachate;

[0137] In step S5, when the rotating shaft 72 rotates, it simultaneously drives the top half gear 87 to rotate. The rotation of the half gear 87 drives the tooth plate 81 to move forward. The forward movement of the tooth plate 81 drives the discharge box 83 and the guide rod 84 to move forward. The movement of the discharge box 83 adjusts the feeding position of the flocculant. The movement of the tooth plate 81 and the guide rod 84 causes the return spring 85 to contract.

[0138] When the rotating shaft 72 drives the half gear 87 to rotate and disengages from the tooth plate 81, the tooth plate 81 moves backward on the surface of the slide rail 82 through the expansion of the reset spring 85, thereby resetting the tooth plate 81 and the discharge box 83, and the rotating shaft 72 continuously drives the half gear 87 to rotate, thereby reciprocatingly adjusting the discharge position of the discharge box 83;

[0139] Step S6: After the pH value of the lepidolite leachate is adjusted and flocculated, it is pumped into the extraction tank, the extractant is filled into the adsorption column, and after dynamic adsorption, it is eluted in sections with 0.5 mol / L HCl (for rubidium removal) and 2 mol / L HNO3 (for cesium removal), and the separation coefficient of rubidium and cesium reaches 180.

[0140] 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 by using the contents of the present invention description and drawings under the concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. Lepidolite tailings rubidium-cesium extraction device, characterized in that, include: Treatment tank, driving mechanism, air intake mechanism and liquid intake mechanism; The driving mechanism includes a mounting base fixedly arranged at the bottom of the front surface of the treatment tank, a rotating rod is rotatably connected to the inner side of the mounting base, a driving gear is connected to the keyway on the surface of the rotating rod, a rotating shaft is rotatably connected to the inner side of the mounting base and located on the left side of the rotating rod, a passive gear is fixed on the surface of the rotating shaft, the passive gear is meshed with the active gear, and a driving motor for driving the rotating rod to rotate is provided at the bottom of the mounting base; The air intake mechanism includes a cam fixedly mounted on the top end of the rotating rod, an air intake cylinder fixedly mounted on the inner side of the treatment tank, a first piston slidably connected to the inner side of the air intake cylinder, a first spring sleeved on the surface of the first piston and located on the outer side of the air intake cylinder, a first rotating seat fixedly mounted on the front side of the first piston, an air outlet pipe connected to the back side of the air intake cylinder, and an air intake pipe connected to the right side of the air intake cylinder; The liquid inlet mechanism includes a disc fixedly mounted on the top of the rotating shaft, a convex disc provided on the top of the disc, connecting bolts provided on the inner sides of the disc and the convex disc, a liquid inlet cylinder provided on the inner side of the treatment pool, a second piston slidably connected to the inner side of the liquid inlet cylinder, a second spring provided on the surface of the second piston and located on the outer side of the liquid inlet cylinder, a second rotating seat fixedly provided on the front side of the second piston, a liquid outlet pipe connected to the back side of the liquid inlet cylinder, and a liquid inlet pipe connected to the left side of the liquid inlet cylinder.

2. The lepidolite tailings rubidium-cesium extraction device according to claim 1, characterized in that: The air intake mechanism and the liquid intake mechanism are respectively vertically arranged in three groups on the surfaces of the rotating rod and the rotating shaft, and the air intake cylinder is located at the bottom of the liquid intake cylinder. The inner side of the disc is provided with a through groove used in conjunction with the connecting bolt.

3. The lepidolite tailings rubidium-cesium extraction device according to claim 1, characterized in that: The front end of the air inlet pipe is connected to the air inlet main pipe, and the front end of the liquid inlet pipe is connected to the liquid inlet main pipe.

4. The lepidolite tailings rubidium-cesium extraction device according to claim 1, characterized in that: A mixing mechanism is fixedly provided on the inner wall of the treatment tank, and the mixing mechanism includes a mounting frame fixedly provided on the inner side of the treatment tank, the inner side of the mounting frame is vertically connected to a rotating shaft, two sets of stirring frames are fixedly provided on the surface of the rotating shaft, a stirring paddle is fixedly provided at the bottom end of the rotating shaft, and a mixing motor for driving the rotating shaft to rotate is provided on the top of the mounting frame.

5. The lepidolite tailings rubidium-cesium extraction device according to claim 4, characterized in that: The inner side of the mounting frame is slidably connected to a feeding mechanism, and the feeding mechanism includes a toothed plate slidably connected to the inner side of the mounting frame, the bottom of the toothed plate is slidably connected to a slide rail, the bottom of the slide rail is fixedly connected to the top of the mounting frame, a discharge box is fixedly provided on the top of the toothed plate, a guide rod is fixedly provided on the front side of the toothed plate, a return spring is sleeved on the surface of the guide rod, a bracket is slidably connected to the surface of the guide rod, the left side of the bracket is fixedly connected to the right side of the mounting frame, a half gear is fixedly provided on the top of the rotating shaft, and the half gear is meshed with the toothed plate.

6. The lepidolite tailings rubidium-cesium extraction device according to claim 1, characterized in that: The right side of the treatment pool is connected with a water inlet pipe, the right side of the inner wall of the treatment pool is fixedly provided with a sieve plate, and the bottom of the treatment pool is fixedly provided with a supporting leg.

7. The lepidolite tailings rubidium-cesium extraction device according to claim 1, characterized in that: Two collecting tanks are fixedly provided at the bottom of the treatment pool, and the bottoms of the two collecting tanks are connected with a sewage pipe.

8. Rubidium-cesium efficient extractant, characterized in that, The rubidium-cesium efficient extractant is used for extracting rubidium and cesium from the lepidolite tailings rubidium-cesium extraction device according to claims 1 to 7 after treating the lepidolite leachate, comprising: Main carrier: acrylic skeleton macroporous white balls with pore size of 50-200nm, providing high specific surface area and acid and alkali resistance; Auxiliary carrier: pyridine functionalized polystyrene microspheres to enhance the coordination adsorption capacity of rubidium and cesium; Active ingredient: ammonium phosphomolybdate (NH4) PM O12 O 40 , loaded on the surface of the dual carrier through chemical bonding to form a stable porous composite structure; Cross-linking agent: Epoxy resin-silane coupling agent composite system, which improves mechanical strength and prevents the loss of active components.

9. A method for preparing a high-efficiency rubidium-cesium extractant, characterized in that: The method for preparing the rubidium-cesium efficient extractant is used for preparing the rubidium-cesium efficient extractant according to claim 8, comprising the following steps: Step S1, dual-carrier pretreatment: Acrylic macroporous white spheres and pyridyl polystyrene microspheres were mixed in a mass ratio of 3:1, washed with 0.5 mol / L NaOH solution, and then washed with water until neutral; Step S2, active component loading: Prepare a 20% ammonium phosphomolybdate solution, mix it with the pretreated dual carrier at a volume ratio of 5:1, and stir and react at 60°C for 12 hours to form a preliminary supported structure; Step S3, composite cross-linking: The loaded support was immersed in an ethanol solution containing 10% epoxy resin and 2% silane coupling agent, and cross-linked at 60°C for eight hours to obtain a composite extractant with high mechanical strength after curing. Step S4, post-processing: The product was washed three times with 3 mol / L hydrochloric acid to remove unreacted impurities, dried and sieved to obtain a particle size of 0.5-1 mm to obtain the finished product.

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