A lithium brine thallium removal device and a preparation process of a magnetic MOF thallium removal agent thereof

Abstract

This invention provides a lithium brine thallium removal device and its magnetic MOF thallium removal agent preparation process. It relates to the field of water pollution control technology and includes a base plate, a tank, a top cover, a mounting plate, a positioning frame, a drive mechanism, and a feeding mechanism. The tank is mounted on the upper surface of the base plate, the top cover is bolted to the upper surface of the tank, the mounting plate is mounted on the upper surface of the top cover, and the positioning frame is mounted on the upper surface of the mounting plate. This invention employs active and passive dispersion to mix and dissolve Fe3O4@UiO-66-NH2 nanoparticles with pure water. During the rotation of the drum, a guide wheel automatically drives the drum to rise automatically following the thickness of the auxiliary plate. When the guide wheel reaches the vertical plane of the auxiliary plate, it automatically falls to control the drum's reset, allowing for vertical movement during rotation and generating small-amplitude vibrations. This process first treats the Fe3O4@UiO-66-NH2 nanoparticles into a liquid state before adding them to the lithium leaching solution, thus ensuring a more uniform concentration within the leaching solution.

Description

Technical Field

[0001] This invention relates to the field of water pollution control technology, and in particular to a lithium brine thallium removal device and its magnetic MOF thallium removal agent preparation process. Background Technology

[0002] Battery-grade lithium carbonate is an indispensable lithium salt in the manufacture of lithium-ion batteries, and its production process begins with key steps such as the leaching, concentration, and synthesis of lepidolite. However, during the leaching stage of lepidolite, thallium, a highly toxic heavy metal, enters the subsequent process along with many other elements. Thallium exists in the leachate as Tl+ and is carried into the mother liquor during subsequent concentration and enrichment processes. Ultimately, it is incorporated into the battery-grade lithium carbonate product during the lithium precipitation step, posing a potential threat to the environment and affecting product quality.

[0003] As the lithium precipitation process progresses, the thallium content in the wastewater often exceeds safe levels, causing serious environmental pollution. Therefore, from the perspective of environmental protection and improving product quality, thorough thallium removal is particularly urgent. This not only reduces environmental damage but also ensures the purity and safety of battery-grade lithium carbonate products.

[0004] In modern medicine, thallium isotope Tl-201 is widely used in the diagnosis and treatment of diseases such as liver, heart, thyroid, melanoma, and tumors due to its important role in detection. In current industries, thallium and its compounds are commonly used in chemical manufacturing, advanced physics, aerospace technology, and optoelectronics and superconducting materials manufacturing. Existing domestic and international thallium removal technologies include sulfide precipitation, adsorption, ion exchange, biological agents, and electrochemical methods.

[0005] In existing technologies, Fe3O4@UiO-66-NH2 nanoparticles are directly added to lithium leaching solutions as thallium removal agents to ensure that metallic thallium forms flocculations and aggregates. As a result, Fe3O4@UiO-66-NH2 nanoparticles, being solid materials, are not easy to mix fully with the leaching solution, which can easily affect the concentration of Fe3O4@UiO-66-NH2 nanoparticles at different liquid levels, thus affecting the thallium removal effect.

[0006] Therefore, it is necessary to provide a lithium brine thallium removal device and a process for preparing a magnetic MOF thallium removal agent to solve the above-mentioned technical problems. Summary of the Invention

[0007] This invention provides a lithium brine thallium removal device, including a bottom plate, a tank, a top cover, a mounting plate, a positioning frame, a drive mechanism, and a feeding mechanism;

[0008] The tank body is installed on the upper surface of the base plate, the top cover is installed on the upper surface of the tank body by bolts, the mounting plate is installed on the upper surface of the top cover, and the positioning frame is installed on the upper surface of the mounting plate;

[0009] The drive mechanism includes a motor, a drive gear, and a driven gear. The bottom of the motor is bolted to the upper surface of the mounting plate. The shaft of the drive gear is keyway connected to the output shaft of the motor. The driven gear is rotatably connected to the upper surface of the mounting plate and located inside the positioning frame. A rotating rod is keyway connected to the shaft of the driven gear. A first ratchet is keyway connected to the top of the rotating rod. A first ratchet disc is meshed with the outer wall of the first ratchet disc. A drive pulley is keyway connected to the outer wall of the first ratchet disc.

[0010] The feeding mechanism includes a feeding tank, an end cover, a key rod, and a return spring. The bottom of the feeding tank is mounted on the top of the top cover, and the end cover is installed on the top of the feeding tank. The outer wall of the key rod is rotatably mounted on the axis of the end cover via a bearing. The return spring is sleeved on the outer wall of the key rod. A driven pulley is connected to the keyway at the top of the key rod. A belt is sleeved on the outer wall of the drive pulley and the driven pulley. A rotating cylinder is slidably connected to the inner wall of the feeding tank below the key rod. Guide wheels are rotatably connected to both sides of the rotating cylinder. An auxiliary plate is fixed to the inner wall of the feeding tank on one side of the guide wheels. An auxiliary groove is opened on the outer wall of the rotating cylinder. Multiple slots are opened and closed on the outer wall of the rotating cylinder below the auxiliary groove. A feeding pipe is installed inside the end cover directly above the auxiliary groove. A baffle is fixed to the outer wall of the key rod below the end cover.

[0011] Preferably, the drive gear and the driven gear mesh with each other, and the outer wall of the first ratchet disc is rotatably connected to the top of the positioning frame via a bearing.

[0012] Preferably, the upper and lower ends of the reset spring are fixedly connected to the bottom of the baffle and the top of the rotating cylinder. The auxiliary groove is designed in an arc shape, and multiple grooves are distributed equidistantly in a ring about the axis of the rotating cylinder. The cross-section of the rotating cylinder is a tapered structure that is narrow at the top and wide at the bottom. One side of the auxiliary plate is a sloping structure, and the other side of the auxiliary plate is a vertical structure. The bottom of the feeding tank is connected to the tank body.

[0013] Preferably, it also includes a vibration mechanism;

[0014] The bottom keyway of the rotating rod is connected to a second ratchet, and the outer wall of the second ratchet is engaged with a second ratchet disc;

[0015] The vibration mechanism includes a telescopic universal joint, four uprights, a top frame, and a base frame. The top keyway of the telescopic universal joint is connected to the bottom of the second ratchet disc. The tops of the four uprights are fixedly installed on the bottom of the top cover. The top frame is installed on the outside of the four uprights. The base frame is installed at the bottom of the four uprights and below the top frame. Two first springs are fixed inside the top frame, and a first slider is fixed on one side of the two first springs. Two second springs are fixed inside the base frame, and a second slider is fixed on one side of the two second springs. A vibration cylinder is fixed on the top of the second slider. The bottom keyway of the telescopic universal joint is connected to a rotating shaft, and an eccentric disc is bolted to the outer wall of the rotating shaft.

[0016] An injection pipe is installed on the upper surface of the top cover and on one side of the feeding mechanism, and a discharge pipe is installed at the bottom of the tank.

[0017] Preferably, the top of the rotating shaft is rotatably connected to the first slider by bolts, the bottom of the rotating shaft is rotatably connected to the bottom of the vibrating cylinder by bearings, and the axis of the second ratchet disc is rotatably connected to the mounting plate by bearings.

[0018] Preferably, the first slider and the second slider slide along the horizontal direction of the top frame and the bottom frame, and the top of the vibrating cylinder is fixedly connected to the bottom of the first slider.

[0019] Preferably, it also includes a magnetic suction mechanism and a jet mechanism;

[0020] The magnetic attraction mechanism includes a slide bar frame mounted on the upper surface of the base plate. The slide bar frame has a first sliding sleeve and a second sliding sleeve slidably connected inside. The inner walls of the first sliding sleeve and the second sliding sleeve are both fixedly mounted with rubidium magnetic plates. The top of the first sliding sleeve is fixedly provided with a driven plate.

[0021] The jet mechanism includes a ring pipe and a nozzle. The ring pipe is installed on the upper surface of the top cover, and the nozzle is installed at the bottom of the ring pipe. A sleeve is installed through the upper surface of the ring pipe. A piston is slidably connected inside the sleeve, and a push plate is slidably connected outside the sleeve. A connecting spring is sleeved on the outer wall of the push plate. A through hole is opened inside the piston, and an air intake pipe is installed through the top of the sleeve.

[0022] Preferably, the driven plate and the push plate are in the same horizontal direction, the through hole is interconnected between the nozzle, the ring pipe and the air intake pipe, and the piston and the push plate are fixedly connected.

[0023] The preparation process of thallium removal agent for magnetic MOFs includes the following steps:

[0024] S1: Synthesis of wet UiO-66-NH2;

[0025] Zirconium metal salt and aminoterephthalic acid NH2-BDC organic ligand were mixed and placed in a glass container. DMF and glacial acetic acid were added to the mixture and stirred to fully dissolve the reactants.

[0026] In the above steps, the zirconium source is zirconium tetrachloride, and the molar ratio of the zirconium salt to NH2-BDC is between 1:1 and 2.

[0027] S2: Keep the glass container of the mixed solution in S1 at a certain temperature for several hours, the temperature is 100 to 140°C and the time is 10 to 16 hours. After the reactants are naturally cooled, they are centrifuged and washed three times each with DMF and methanol. The resulting material is centrifuged to obtain wet UiO-66-NH2 gel.

[0028] S3: Synthesis of Fe3O4 nanoparticles;

[0029] Weigh out ferric chloride hexahydrate FeCl3·6H2O and place it in a polytetrafluoroethylene (PTFE) liner. Add ethylene glycol solution to the PTFE liner. Add sodium acetate (NaAc) and polyethylene glycol to the PTFE liner.

[0030] S4: Stir the above mixture with a magnetic stirrer to dissolve it completely. Seal the polytetrafluoroethylene liner containing the reactants in a stainless steel autoclave and place it in an oven. Transfer the solution in the autoclave to a centrifuge tube and perform magnetic separation of the material using a magnet. Wash thoroughly with deionized water and ethanol and dry to obtain Fe3O4 nanoparticles.

[0031] S4: Preparation method of magnetic Fe3O4@UiO-66-NH2;

[0032] Fe3O4 nanoparticles were mixed with wet UiO-66-NH2 gel material and stirred evenly before drying. The resulting material was placed in a centrifuge tube and washed three times with acetone and methanol respectively. The washed material was then dried. Note that each washing with acetone and methanol should last for 10 to 14 hours at a temperature of 25 to 45°C.

[0033] The prepared Fe3O4@UiO-66-NH2 nanoparticles can be injected into the tank through a feeding mechanism, where they adsorb with the lithium brine in the tank, thereby removing the metallic thallium.

[0034] Compared with related technologies, the lithium brine thallium removal equipment and its magnetic MOF thallium removal agent preparation process provided by the present invention have the following beneficial effects:

[0035] In this case, Fe3O4@UiO-66-NH2 nanoparticles and pure water are added into the feeding tank. As the Fe3O4@UiO-66-NH2 nanoparticles fall, they enter the interior of the auxiliary tank. When the particles pass through the arc surface, the shape of the arc surface will adaptively change the falling trajectory, changing the straight feeding to the parabolic arc feeding, thereby automatically dispersing the particles.

[0036] Secondly, the clockwise rotation of the drum allows for secondary rotational dispersion of the Fe3O4@UiO-66-NH2 nanoparticles. This design employs both active and passive dispersion methods to mix and dissolve the Fe3O4@UiO-66-NH2 nanoparticles with pure water. Furthermore, during the drum's rotation, guide wheels automatically drive the drum to rise along with the thickness of the auxiliary plate. When the guide wheels reach the vertical plane of the auxiliary plate, they automatically drop, resetting the drum. This design enables vertical movement and small-amplitude vibrations during drum rotation, further mixing and dissolving the adhered Fe3O4@UiO-66-NH2 nanoparticles. This process first liquefies the Fe3O4@UiO-66-NH2 nanoparticles before adding them to the lithium leaching solution, ensuring a more uniform concentration within the leaching solution. Attached Figure Description

[0037] 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.

[0038] Figure 1 This is a schematic diagram of the optimal structure for the present invention;

[0039] Figure 2 for Figure 1 The diagram shows a cross-sectional view of the tank body and top cover.

[0040] Figure 3 for Figure 2 The diagram shows the structure viewed from below.

[0041] Figure 4 for Figure 1 The diagram shows the structure of the drive mechanism.

[0042] Figure 5 for Figure 4 The diagram shows the disassembled structure of the drive mechanism;

[0043] Figure 6 for Figure 5 The diagram shows a cross-sectional view of the first ratchet disc.

[0044] Figure 7 This is a cross-sectional view of the feeding mechanism provided by the present invention;

[0045] Figure 8 for Figure 7 The diagram shown is a front view of the rotating drum.

[0046] Figure 9 for Figure 7 The diagram shows the initial working state of the rotating drum.

[0047] Figure 10 for Figure 9 The diagram shows the working state of the rotating drum as it rotates onto the auxiliary plate, with the drum rising upwards.

[0048] Figure 11 for Figure 10 The diagram shows the structure viewed from below.

[0049] Figure 12 This is a cross-sectional structural diagram of the vibration mechanism provided by the present invention;

[0050] Figure 13 This is a schematic diagram of the magnetic attraction mechanism provided by the present invention;

[0051] Figure 14 A schematic diagram of the jet mechanism provided by the present invention;

[0052] Figure 15 for Figure 14 The enlarged structural diagram at point A is shown.

[0053] Explanation of icon numbers:

[0054] 1. Base plate; 2. Tank body; 3. Top cover; 4. Mounting plate; 5. Positioning frame;

[0055] 6. Drive mechanism; 61. Motor; 62. Drive gear; 63. Driven gear; 64. Rotating rod; 65. First ratchet; 66. First ratchet disc; 67. Drive pulley; 68. Second ratchet; 69. Second ratchet disc.

[0056] 7. Feeding mechanism; 71. Feeding tank; 72. End cover; 73. Driven pulley; 74. Belt; 75. Auxiliary plate; 76. Rotary drum; 77. Guide wheel; 78. Groove; 79. Auxiliary groove; 710. Key rod; 711. Return spring; 712. Feeding pipe; 713. Baffle.

[0057] 8. Vibration mechanism; 81. Telescopic universal joint; 82. Top frame; 83. Base frame; 84. First spring; 85. First slider; 86. Second spring; 87. Second slider; 88. Vertical rod; 89. Rotating shaft; 810. Eccentric plate; 811. Vibration cylinder.

[0058] 9. Jet mechanism; 91. Ring pipe; 92. Nozzle; 93. Inlet pipe; 94. Sleeve; 95. Piston; 96. Push plate; 97. Connecting spring; 98. Through hole;

[0059] 10. Magnetic attraction mechanism; 101. Slide bar frame; 102. First sliding sleeve; 103. Second sliding sleeve; 104. Rubidium magnet plate; 105. Driven plate;

[0060] 11. Discharge tube; 12. Injection tube. Detailed Implementation

[0061] 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.

[0062] This invention provides a lithium brine thallium removal device and a process for preparing a magnetic MOF thallium removal agent.

[0063] First embodiment:

[0064] Please see Figures 1 to 11 A lithium brine thallium removal device includes a bottom plate 1, a tank body 2, a top cover 3, a mounting plate 4, a positioning frame 5, a drive mechanism 6, and a feeding mechanism 7;

[0065] The tank body 2 is installed on the upper surface of the base plate 1, the top cover 3 is installed on the upper surface of the tank body 2 by bolts, the mounting plate 4 is installed on the upper surface of the top cover 3, and the positioning frame 5 is installed on the upper surface of the mounting plate 4.

[0066] The drive mechanism 6 includes a motor 61, a drive gear 62, and a driven gear 63. The bottom of the motor 61 is bolted to the upper surface of the mounting plate 4. The shaft of the drive gear 62 is keyway connected to the output shaft of the motor 61. The driven gear 63 is rotatably connected to the upper surface of the mounting plate 4 and located inside the positioning frame 5. A rotating rod 64 is keyway connected to the shaft of the driven gear 63. A first ratchet 65 is keyway connected to the top of the rotating rod 64. A first ratchet disc 66 is meshed with the outer wall of the first ratchet disc 65. A drive pulley 67 is keyway connected to the outer wall of the first ratchet disc 66.

[0067] Preferably, motor 61 can be a three-phase asynchronous motor.

[0068] Please see Figure 4 and Figure 5 When the user starts the motor 61, it can drive the drive gear 62 to mesh with the driven gear 63 to rotate. Therefore, the motor 61 can freely control the forward and reverse rotation of the driven gear 63.

[0069] The driven gear 63 has two rotation modes: one is clockwise rotation mode and the other is counterclockwise rotation mode.

[0070] When the driven gear 63 rotates clockwise, it will drive the rotating rod 64 to drive the first ratchet 65 above the positioning frame 5 to rotate clockwise.

[0071] Please see Figure 6 When the first ratchet 65 rotates clockwise, the peripheral teeth of the first ratchet 65 will control the teeth in the first ratchet disc 66 clockwise, thereby realizing the synchronous transmission of the first ratchet disc 66 to rotate clockwise during the clockwise rotation of the first ratchet 65.

[0072] The feeding mechanism 7 includes a feeding tank 71, an end cover 72, a key rod 710, and a return spring 711. The bottom of the feeding tank 71 is mounted on the top of the top cover 3. The end cover 72 is installed on the top of the feeding tank 71. The outer wall of the key rod 710 is rotatably mounted on the axis of the end cover 72 via a bearing. The return spring 711 is sleeved on the outer wall of the key rod 710. The keyway at the top of the key rod 710 is connected to a driven pulley 73. A belt 74 is sleeved on the outer wall of the drive pulley 67 and the driven pulley 73. The interior of the feeding tank 71... A rotating cylinder 76 is slidably connected to the outer wall below the key rod 710. Guide wheels 77 are rotatably connected to both sides of the rotating cylinder 76. An auxiliary plate 75 is fixedly provided on the inner wall of the feed tank 71 and on one side of the guide wheel 77. An auxiliary groove 79 is opened on the outer wall of the rotating cylinder 76. Multiple slots 78 are opened on the outer wall of the rotating cylinder 76 and below the auxiliary groove 79. A feed pipe 712 is installed inside the end cover 72 and directly above the auxiliary groove 79. A baffle 713 is fixedly provided on the outer wall of the key rod 710 and below the end cover 72.

[0073] Please see Figure 5 and Figure 7 The first ratchet disc 66 rotates clockwise, synchronously driving the pulley 67 and the drive belt 74 to control the driven pulley 73 to rotate clockwise. The driven pulley 73 rotates above the end cover 72.

[0074] Please see Figure 7 and Figure 11During the clockwise rotation of the driven pulley 73, the key lever 710 will be driven to rotate synchronously. When the key lever 710 rotates, the baffle 713, the return spring 711 and the rotating cylinder 76 will rotate in conjunction with the key lever 710.

[0075] Please see Figure 7 The user adds Fe3O4@UiO-66-NH2 nanoparticles and pure water into the feed tank 71 through the feed pipe 712;

[0076] Please see Figure 9 When the key lever 710 controls the rotating drum 76 to rotate normally, the guide wheels 77 on both sides of the rotating drum 76 and the bottom surface of the auxiliary plate 75 are level, and the return spring 711 is in the extended state.

[0077] The drive gear 62 and the driven gear 63 mesh with each other, and the outer wall of the first ratchet disc 66 is rotatably connected to the top of the positioning frame 5 via a bearing.

[0078] The upper and lower ends of the return spring 711 are fixedly connected to the bottom of the baffle 713 and the top of the rotating cylinder 76. The auxiliary groove 79 has an arc-shaped design. Multiple grooves 78 are equidistantly distributed in a ring about the axis of the rotating cylinder 76. The cross-section of the rotating cylinder 76 has a tapered structure that is narrow at the top and wide at the bottom. One side of the auxiliary plate 75 has a sloping structure, and the other side of the auxiliary plate 75 has a vertical structure. The bottom of the feeding tank 71 is connected to the tank body 2.

[0079] Understandably: Since the rotation of the rotating drum 76 is a continuous clockwise rotation mode, and the inclined surface of the auxiliary plate 75 is always set in the rotation direction of the guide wheel 77, the guide wheel 77 will not interfere with the inclined surface of the auxiliary plate 75 during the clockwise rotation.

[0080] Secondly, the bottom of the return spring 711 is fixedly connected to the top of the rotating drum 76, which can prevent the rotating drum 76 from falling. Furthermore, the rotating drum 76 and the key rod 710 slide, which can ensure that the rotating drum 76 can rotate and can also be raised and lowered.

[0081] This embodiment

[0082] Compared to the traditional direct feeding design, this design adds Fe3O4@UiO-66-NH2 nanoparticles and pure water into the feeding tank 71. As the Fe3O4@UiO-66-NH2 nanoparticles fall, they enter the auxiliary tank 79. When the particles pass through the arc surface, the shape of the arc surface will adaptively change the falling trajectory, changing the straight feeding to a parabolic arc feeding, thereby automatically dispersing the particles.

[0083] Secondly, the clockwise rotation of the drum 76 enables secondary rotational dispersion of the Fe3O4@UiO-66-NH2 nanoparticles. Therefore, this design employs both active and passive dispersion methods to mix and dissolve the Fe3O4@UiO-66-NH2 nanoparticles with pure water. Furthermore, during the rotation, the guide wheel 77 automatically drives the drum 76 to rise along with the thickness of the auxiliary plate 75. When the guide wheel 77 reaches the vertical plane of the auxiliary plate 75, it automatically falls, controlling the drum 76 to reset. This design allows the drum 76 to move vertically and generate small-amplitude vibrations during rotation, thereby further mixing and dissolving the adhered Fe3O4@UiO-66-NH2 nanoparticles. This process first treats the Fe3O4@UiO-66-NH2 nanoparticles into a liquid state before adding them to the lithium leaching solution, ensuring a more uniform concentration within the leaching solution.

[0084] Second embodiment:

[0085] Please see Figure 2 , Figures 4 to 6 and Figure 12 It also includes a vibration mechanism 8;

[0086] The bottom keyway of the rotating rod 64 is connected to a second ratchet 68, and the outer wall of the second ratchet 68 is engaged with a second ratchet disc 69.

[0087] The vibration mechanism 8 includes a telescopic universal joint 81, four uprights 88, a top frame 82, and a base frame 83. The top keyway of the telescopic universal joint 81 is connected to the bottom of the second ratchet disc 69. The tops of the four uprights 88 are fixedly installed on the bottom of the top cover 3. The top frame 82 is installed on the outside of the four uprights 88. The base frame 83 is installed at the bottom of the four uprights 88 and below the top frame 82. Two first springs 84 are fixed inside the top frame 82. A first slider 85 is fixed on the opposite side of the two first springs 84. Two second springs 86 are fixed inside the base frame 83. A second slider 87 is fixed on the opposite side of the two second springs 86. A vibration cylinder 811 is fixed on the top of the second slider 87. The bottom keyway of the telescopic universal joint 81 is connected to a rotating shaft 89. An eccentric disc 810 is bolted to the outer wall of the rotating shaft 89.

[0088] An injection pipe 12 is installed on the upper surface of the top cover 3 and on one side of the feeding mechanism 7, and a discharge pipe 11 is installed at the bottom of the tank body 2.

[0089] Please see Figure 4 and Figure 5As can be seen from the first embodiment, the driven gear 63 has two working modes. When it rotates clockwise in the first embodiment, the rotating rod 64 will only affect the first ratchet 65 and will not drive the second ratchet 68 to rotate.

[0090] When the lever 64 rotates counterclockwise, the first ratchet 65 will avoid the first ratchet disc 66 when it rotates counterclockwise, so the first ratchet disc 66 will not rotate. At this time, the counterclockwise rotating lever 64 will drive the second ratchet 68 to control the second ratchet disc 69 to rotate counterclockwise. When the second ratchet disc 69 rotates, it will drive the telescopic universal joint 81 to rotate.

[0091] Please see Figure 12 During the rotation of the telescopic universal joint 81, the shaft 89 will rotate inside the vibrating cylinder 811. At this time, the shaft 89 will synchronously drive the eccentric disk 810 to rotate. Since the left and right ends of the eccentric disk 810 have different weights, when the eccentric disk 810 rotates, it will generate left and right eccentric vibration force, which will further affect the vibrating cylinder 811 to generate vibration.

[0092] The top of the rotating shaft 89 is rotatably connected to the first slider 85 by bolts, the bottom of the rotating shaft 89 is rotatably connected to the bottom of the vibrating cylinder 811 by bearings, and the axis of the second ratchet disc 69 is rotatably connected to the mounting plate 4 by bearings.

[0093] The first slider 85 and the second slider 87 slide along the horizontal direction of the top frame 82 and the bottom frame 83, and the top of the vibrating cylinder 811 is fixedly connected to the bottom of the first slider 85.

[0094] Understandably: when the vibrating cylinder 811 vibrates, it will drive the first slider 85 and the second slider 87 in the upper and lower positions to generate vibration force. Therefore, the first spring 84 and the second spring 86 are used to limit the first slider 85 and the second slider 87 to ensure stable vibration.

[0095] Secondly, the vibration trajectory of the first slider 85 is bilateral vibration. By using a telescopic universal joint 81 to connect the rotating shaft 89 and the second ratchet disk 69, the interference generated when the rotating shaft 89 vibrates and displaces can be eliminated, ensuring that the rotating shaft 89 can achieve universal rotation.

[0096] This embodiment

[0097] Compared to traditional designs, this invention uses the forward and reverse rotation of motor 61 to achieve two functions. When switching from the feeding function in the first embodiment to the thallium removal function in this embodiment, the feeding function will automatically stop working. Secondly, compared to traditional thallium removal methods, this invention has a vibrating cylinder 811 that can vibrate and move in the middle of the tank 2 to vibrate and affect the leachate inside the tank 2.

[0098] Compared to traditional designs, the vibration-induced mode can achieve thorough mixing of Fe3O4@UiO-66-NH2 nanoparticles and leachate while avoiding the destruction of magnetic aggregates formed by the adsorption of thallium by Fe3O4@UiO-66-NH2 nanoparticles, thereby achieving high efficiency in thallium removal.

[0099] Meanwhile, the eccentric disk 810 is designed in a modular way, which users can adjust freely. When the eccentric disks 810 overlap, the vibration force is the greatest. Conversely, the smaller the overlap of the eccentric disks 810, the smaller the vibration force. It can also be used with an external vibration shaker to assist in vibration processing.

[0100] Third embodiment:

[0101] Please see Figure 2 , Figures 13 to 15 It also includes a magnetic suction mechanism 10 and a jet mechanism 9;

[0102] The magnetic attraction mechanism 10 includes a slide bar frame 101 mounted on the upper surface of the base plate 1. The slide bar frame 101 is slidably connected to a first slide sleeve 102 and a second slide sleeve 103. Rubidium magnetic plates 104 are fixedly mounted on the inner walls of the first slide sleeve 102 and the second slide sleeve 103. A driven plate 105 is fixedly mounted on the top of the first slide sleeve 102.

[0103] The jet mechanism 9 includes an annular pipe 91 and a nozzle 92. The annular pipe 91 is installed on the upper surface of the top cover 3, and the nozzle 92 is installed at the bottom of the annular pipe 91. A sleeve 94 is installed through the upper surface of the annular pipe 91. A piston 95 is slidably connected inside the sleeve 94, and a push plate 96 is slidably connected outside the sleeve 94. A connecting spring 97 is sleeved on the outer wall of the push plate 96. A through hole 98 is opened inside the piston 95, and an air intake pipe 93 is installed through the top of the sleeve 94.

[0104] The driven plate 105 and the push plate 96 are in the same horizontal direction. The through hole 98 is interconnected with the nozzle 92, the ring pipe 91 and the air intake pipe 93. The piston 95 and the push plate 96 are fixedly connected.

[0105] Please see Figure 2 and Figure 13 The user can freely slide the first sliding sleeve 102 and the second sliding sleeve 103 along the horizontal direction of the sliding rod frame 101 until the two rubidium magnetic plates 104 are wrapped around the tank body 2. The rubidium magnetic plates 104 generate magnetism to attract the magnetic metal thallium aggregates to the inner wall of the tank body 2. When the first sliding sleeve 102 is sliding, the driven plate 105 will also follow the movement.

[0106] Please see Figure 14 and Figure 15When the rubidium magnetic plate 104 is wrapped around the outer wall of the tank 2, the driven plate 105 will move and abut against the force-bearing push plate 96 to push and drive the internal piston 95 so that its through hole 98 moves into the space between the air intake pipe 93 and the ring pipe 91. Then, when the air intake pipe 93 takes in air, it will enter the ring pipe 91 through the through hole 98 and be sprayed out along the inner wall of the tank 2 through the nozzle 92.

[0107] This embodiment

[0108] Compared to traditional designs, this design features two relatively movable rubidium magnetic plates 104 wrapped around the outer wall of the tank 2, which allows magnetic thallium aggregates to be adsorbed onto the inner wall of the tank 2, thus easily achieving the separation of thallium aggregates from the leachate.

[0109] Simultaneously, during the closing process of the rubidium magnetic plate 104, the driven plate 105 drives the push plate 96 to control the piston 95 to connect the through hole 98 to the air inlet pipe 93 and the nozzle 92, thereby realizing the automatic connection of the air inlet pipe 93 to generate high-pressure jet gas that is sprayed onto the inner wall of the tank 2. This can assist the rubidium magnetic plate 104 in separating the metal thallium aggregates, thereby achieving efficient removal and treatment of metal thallium aggregates.

[0110] Working principle of the invention:

[0111] S1: The addition of Fe3O4@UiO-66-NH2 nanoparticles;

[0112] Fe3O4@UiO-66-NH2 nanoparticles and pure water are added into the feeding tank 71. The motor 61 is started to control the drive gear 62 to control the driven gear 63, so that the first ratchet disc 66 controls the drive pulley 67 and affects the belt 74 to control the driven pulley 73 to rotate clockwise.

[0113] Driven pulley 73 controls key rod 710 to drive rotating drum 76 to achieve mixing and dissolution of Fe3O4@UiO-66-NH2 nanoparticles and pure water. During the rotation of rotating drum 76, lifting vibration can also be used to assist mixing and dissolution.

[0114] S2: Leachate for thallium removal;

[0115] The pretreated Fe3O4@UiO-66-NH2 nanoparticles are introduced into the tank 2. The injection pipe 12 is responsible for adding the leachate. The starter rod 64 rotates counterclockwise. The counterclockwise rotating rod 64 will drive the second ratchet 68 to control the second ratchet disc 69 to rotate counterclockwise. When the second ratchet disc 69 rotates, it will drive the telescopic universal joint 81 to rotate.

[0116] During the rotation of the telescopic universal joint 81, the rotating shaft 89 will rotate inside the vibrating cylinder 811. At this time, the rotating shaft 89 will synchronously drive the eccentric disk 810 to rotate. Since the left and right ends of the eccentric disk 810 have different weights, when the eccentric disk 810 rotates, it will generate left and right eccentric vibration force. The vibration force will further affect the vibrating cylinder 811 to generate vibration, vibrating the leachate inside the vibrating tank 2, so that the metal thallium can be adsorbed and flocculated to form magnetic metal thallium agglomerates.

[0117] S3: Separation of magnetic thallium aggregates and pure liquid;

[0118] The first sliding sleeve 102 and the second sliding sleeve 103 can be freely slid along the horizontal direction of the sliding rod frame 101 until the two rubidium magnetic plates 104 are wrapped around the tank body 2. The rubidium magnetic plates 104 generate magnetism and adsorb the magnetic metal thallium aggregates onto the inner wall of the tank body 2. The treated leachate pure liquid is discharged through the discharge pipe 11. After that, the magnetic metal thallium aggregates remain on the inner wall of the tank 2. Then, the rubidium magnetic plates 104 lose magnetism when the power is turned off, and the nozzle 92 sprays gas to help the metal thallium aggregates slide down for collection.

[0119] Fourth embodiment:

[0120] The preparation process of thallium removal agent for magnetic MOFs includes the following steps:

[0121] S1: Synthesis of wet UiO-66-NH2;

[0122] Zirconium metal salt and aminoterephthalic acid NH2-BDC organic ligand were mixed and placed in a glass container. DMF and glacial acetic acid were added to the mixture and stirred to fully dissolve the reactants.

[0123] In the above steps, the zirconium source is zirconium tetrachloride, and the molar ratio of the zirconium salt to NH2-BDC is between 1:1 and 2.

[0124] S2: Keep the glass container of the mixed solution in S1 at a certain temperature for several hours, the temperature is 100 to 140°C and the time is 10 to 16 hours. After the reactants are naturally cooled, they are centrifuged and washed three times each with DMF and methanol. The resulting material is centrifuged to obtain wet UiO-66-NH2 gel.

[0125] S3: Synthesis of Fe3O4 nanoparticles;

[0126] Weigh out ferric chloride hexahydrate FeCl3·6H2O and place it in a polytetrafluoroethylene (PTFE) liner. Add ethylene glycol solution to the PTFE liner. Add sodium acetate (NaAc) and polyethylene glycol to the PTFE liner.

[0127] S4: Stir the above mixture with a magnetic stirrer to dissolve it completely. Seal the polytetrafluoroethylene liner containing the reactants in a stainless steel autoclave and place it in an oven. Transfer the solution in the autoclave to a centrifuge tube and perform magnetic separation of the material using a magnet. Wash thoroughly with deionized water and ethanol and dry to obtain Fe3O4 nanoparticles.

[0128] S4: Preparation method of magnetic Fe3O4@UiO-66-NH2;

[0129] Fe3O4 nanoparticles were mixed with wet UiO-66-NH2 gel material and stirred evenly before drying. The resulting material was placed in a centrifuge tube and washed three times with acetone and methanol respectively. The washed material was then dried. Note that each washing with acetone and methanol should last for 10 to 14 hours at a temperature of 25 to 45°C.

[0130] The prepared Fe3O4@UiO-66-NH2 nanoparticles can be injected into the tank 2 through the feeding mechanism 7, where they are adsorbed by the lithium brine in the tank 2, thereby removing the metallic thallium.

[0131] This embodiment

[0132] It is made by forming a three-dimensional porous structure by combining zirconium tetrachloride (ZrCl4) or zirconium oxychloride octahydrate with amino terephthalic acid organic ligand, and then introducing Fe3O4 to form a magnetic load at high temperature through composite, and then regenerating it after acid desorption solution to achieve the purpose of recycling.

[0133] The reason why UiO-66 has such outstanding stability is that, under ideal conditions, the UiO-66-NH2 building unit is formed by the coordination of [Zr6O4(OH)4] metal clusters with 12 H2BDC-NH2 groups, which is the highest coordination number of organic ligands and metal clusters that MOFs can have.

[0134] This MOF material exhibits smaller crystal size, shorter mass transfer path, higher adsorption capacity, and more unsaturated active sites at the microscopic level. The synthesized adsorbent material was placed in a lepidolite leachate with a thallium content of 4000 to 5000 ppb. The adsorption in this reaction is achieved through π-π bond stacking, hydrogen bonding interactions, metal-ligand coordination interactions, and van der Waals interactions. The efficient adsorption driving force comes from the electrostatic interaction between UiO-66-NH2 and Tl+, which allows thallium in the brine to combine with the exposed active sites in the MOF material, thereby achieving a highly efficient removal effect.

[0135] 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 lithium brine thallium removal device, characterized in that, Includes bottom plate, tank body, top cover, mounting plate, positioning frame, drive mechanism and unloading mechanism; The tank body is installed on the upper surface of the base plate, the top cover is installed on the upper surface of the tank body by bolts, the mounting plate is installed on the upper surface of the top cover, and the positioning frame is installed on the upper surface of the mounting plate; The drive mechanism includes a motor, a drive gear, and a driven gear. The bottom of the motor is bolted to the upper surface of the mounting plate. The shaft of the drive gear is keyway connected to the output shaft of the motor. The driven gear is rotatably connected to the upper surface of the mounting plate and located inside the positioning frame. A rotating rod is keyway connected to the shaft of the driven gear. A first ratchet is keyway connected to the top of the rotating rod. A first ratchet disc is meshed with the outer wall of the first ratchet disc. A drive pulley is keyway connected to the outer wall of the first ratchet disc. The feeding mechanism includes a feeding tank, an end cover, a key rod, and a return spring. The bottom of the feeding tank is mounted on the top of the top cover, and the end cover is installed on the top of the feeding tank. The outer wall of the key rod is rotatably mounted on the axis of the end cover via a bearing. The return spring is sleeved on the outer wall of the key rod. A driven pulley is connected to the keyway at the top of the key rod. A belt is sleeved on the outer wall of the drive pulley and the driven pulley. A rotating cylinder is slidably connected to the inner wall of the feeding tank below the key rod. Guide wheels are rotatably connected to both sides of the rotating cylinder. An auxiliary plate is fixed to the inner wall of the feeding tank on one side of the guide wheel. An auxiliary groove is opened on the outer wall of the rotating cylinder. Multiple slots are opened and closed on the outer wall of the rotating cylinder below the auxiliary groove. A feeding pipe is installed inside the end cover and directly above the auxiliary groove. A baffle is fixed to the outer wall of the key rod below the end cover. The upper and lower ends of the reset spring are fixedly connected to the bottom of the baffle and the top of the rotating drum. The auxiliary groove is designed in an arc shape. Multiple grooves are distributed in a ring at equal intervals about the axis of the rotating drum. The cross-section of the rotating drum is a tapered structure that is narrow at the top and wide at the bottom. One side of the auxiliary plate is a sloping structure, and the other side of the auxiliary plate is a vertical structure. The bottom of the feeding tank is connected to the tank body.

2. The lithium brine thallium removal equipment according to claim 1, characterized in that, The drive gear and the driven gear mesh with each other, and the outer wall of the first ratchet disc is rotatably connected to the top of the positioning frame via a bearing.

3. The lithium brine thallium removal equipment according to claim 1, characterized in that, It also includes vibration mechanisms; The bottom keyway of the rotating rod is connected to a second ratchet, and the outer wall of the second ratchet is engaged with a second ratchet disc; The vibration mechanism includes a telescopic universal joint, four uprights, a top frame, and a base frame. The top keyway of the telescopic universal joint is connected to the bottom of the second ratchet disc. The tops of the four uprights are fixedly installed on the bottom of the top cover. The top frame is installed on the outside of the four uprights. The base frame is installed at the bottom of the four uprights and below the top frame. Two first springs are fixed inside the top frame, and a first slider is fixed on one side of the two first springs. Two second springs are fixed inside the base frame, and a second slider is fixed on one side of the two second springs. A vibration cylinder is fixed on the top of the second slider. The bottom keyway of the telescopic universal joint is connected to a rotating shaft, and an eccentric disc is bolted to the outer wall of the rotating shaft. An injection pipe is installed on the upper surface of the top cover and on one side of the feeding mechanism, and a discharge pipe is installed at the bottom of the tank.

4. The lithium brine thallium removal equipment according to claim 3, characterized in that, The top of the rotating shaft is rotatably connected to the first slider by bolts, the bottom of the rotating shaft is rotatably connected to the bottom of the vibrating cylinder by bearings, and the axis of the second ratchet disc is rotatably connected to the mounting plate by bearings.

5. The lithium brine thallium removal equipment according to claim 3, characterized in that, The first and second sliders slide along the horizontal direction of the top and bottom frames, and the top of the vibrating cylinder is fixedly connected to the bottom of the first slider.

6. The lithium brine thallium removal equipment according to claim 1, characterized in that, It also includes a magnetic suction mechanism and a jet injection mechanism; The magnetic attraction mechanism includes a slide bar frame mounted on the upper surface of the base plate. The slide bar frame has a first sliding sleeve and a second sliding sleeve slidably connected inside. The inner walls of the first sliding sleeve and the second sliding sleeve are both fixedly mounted with rubidium magnetic plates. The top of the first sliding sleeve is fixedly provided with a driven plate. The jet mechanism includes a ring pipe and a nozzle. The ring pipe is installed on the upper surface of the top cover, and the nozzle is installed at the bottom of the ring pipe. A sleeve is installed through the upper surface of the ring pipe. A piston is slidably connected inside the sleeve, and a push plate is slidably connected outside the sleeve. A connecting spring is sleeved on the outer wall of the push plate. A through hole is opened inside the piston, and an air intake pipe is installed through the top of the sleeve.

7. The lithium brine thallium removal equipment according to claim 6, characterized in that, The driven plate and the push plate are in the same horizontal direction, the through hole is interconnected between the nozzle, the ring pipe and the air intake pipe, and the piston and the push plate are fixedly connected.

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