Lithium brine thallium removal equipment and magnetic MOFs thallium removal agent preparation process thereof

Abstract

The invention provides lithium brine thallium removal equipment and a magnetic MOFs thallium removal agent preparation process thereof. The water pollution treatment device comprises a bottom plate, a tank body, a top cover, a mounting plate, a positioning frame, a driving mechanism and a discharging mechanism, the tank body is mounted on the upper surface of the bottom plate, the top cover is mounted on the upper surface of the tank body through bolts, 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. In the rotating process of the rotating drum, the rotating drum is automatically driven by the guide wheel to automatically ascend along with the thickness of the auxiliary plate, and when the guide wheel rotates to the vertical plane of the auxiliary plate, the guide wheel automatically falls to control the rotating drum to reset, so that the rotating drum can vertically move in the rotating process; in addition, small-amplitude vibration can be formed, so that the Fe3O4-coated UiO-66-NH2 nanoparticles are firstly treated into a liquid state and then are injected into the lithium leaching solution, and the concentration in the leaching solution can be ensured to be more uniform.

Description

Technical Field

[0001] The present invention relates to the technical field of water pollution control, and in particular to a lithium brine thallium removal device and a preparation process of a magnetic MOFs thallium removal agent. Background Art

[0002] Battery-grade lithium carbonate, an essential lithium salt for lithium-ion battery manufacturing, begins with the critical steps of lepidolite leaching, concentration, and synthesis. However, during the lepidolite leaching stage, thallium, a highly toxic heavy metal, enters the subsequent process flow along with numerous other elements. Thallium, present in the leachate as Tl+, is carried into the mother liquor during the subsequent concentration and enrichment processes, ultimately being incorporated into the battery-grade lithium carbonate product during the lithium precipitation step. This not only poses a potential threat to the environment but also affects product quality.

[0003] As the lithium precipitation process progresses, the thallium content in the wastewater generated during lithium precipitation often exceeds the permitted level, causing serious environmental pollution. Therefore, from the perspective of environmental protection and improving product quality, in-depth 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, the thallium isotope Tl-201 is widely used in the diagnosis and treatment of liver, heart, thyroid, melanoma, and tumor diseases due to its crucial role in detecting these conditions. Currently, thallium and its compounds are commonly used in industries such as chemical pharmaceutical manufacturing, advanced physics, aerospace technology, optical electronics, and superconducting materials. Existing thallium removal technologies, both domestically and internationally, include sulfidation precipitation, adsorption, ion exchange, biological preparation, and electrochemical methods.

[0005] In the prior art, Fe3O4@UiO-66-NH2 nanoparticles are directly added to the lithium leachate as a thallium removal agent to ensure that the metallic thallium forms flocculation and produces aggregates. Therefore, the Fe3O4@UiO-66-NH2 nanoparticles, as a solid material, are not convenient to fully mix with the leachate, which easily affects the concentration of Fe3O4@UiO-66-NH2 nanoparticles at different liquid levels, thereby affecting the thallium removal effect.

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

[0007] The present invention provides a lithium brine thallium removal device, comprising a bottom plate, a tank body, a top cover, a mounting plate, a positioning frame, a driving mechanism and a feeding mechanism; The tank body is mounted on the upper surface of the bottom plate, the top cover is mounted on the upper surface of the tank body by bolts, 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; The driving mechanism includes a motor, a driving gear and a driven gear, the bottom of the motor is mounted on the upper surface of the mounting plate by bolts, the axis of the driving gear is connected to the keyway of the motor output shaft, the driven gear is rotatably connected to the upper surface of the mounting plate and is located inside the positioning frame, the axis of the driven gear is connected to a rotating rod with a keyway, the top keyway of the rotating rod is connected to a first ratchet, the outer wall of the first ratchet is meshed with a first ratchet disk, and the outer wall keyway of the first ratchet disk is connected to a driving pulley; The top of the key rod is connected to the driven pulley by the key slot, and the outer wall of the driving pulley and the driven pulley are sleeved with a belt. The interior of the discharge tank is located below the key rod and is slidably connected to the outer wall of the drum. Both sides of the drum are rotatably connected to the guide wheel. The inner wall of the discharge tank and one side of the guide wheel are fixed with an auxiliary plate. The outer wall of the drum is provided with an auxiliary groove, and the outer wall of the drum is opened and closed with multiple slots below the auxiliary groove. A feeding pipe is installed inside the end cover and just above the auxiliary groove, and a baffle is fixed on the outer wall of the key rod and located below the end cover.

[0008] Preferably, the driving gear and the driven gear are engaged with each other, and the outer wall of the first ratchet plate is rotatably connected to the top of the positioning frame through a bearing.

[0009] Preferably, the upper and lower ends of the return spring are fixedly connected to the bottom of the baffle and the top of the drum, the auxiliary groove is designed in a circular arc shape, and the multiple slots are equidistantly distributed in a ring about the axis of the drum. The cross-section of the drum is a conical structure that is narrow at the top and wide at the bottom. One side of the auxiliary plate is a sloped structure, and the other side of the auxiliary plate is a vertical surface structure. The bottom of the discharge tank and the tank body are interconnected.

[0010] Preferably, it also includes a vibration mechanism; The bottom keyway of the rotating rod is connected to a second ratchet wheel, and the outer wall of the second ratchet wheel is meshedly connected to a second ratchet disk; The vibration mechanism includes a telescopic universal joint, four vertical rods, a top frame and a bottom frame, the top keyway of the telescopic universal joint is connected to the bottom of the second ratchet disk, the tops of the four vertical rods are fixedly mounted on the bottom of the top cover, the top frame is mounted on the outside of the four vertical rods, and the bottom of the four vertical rods and below the top frame is mounted with a bottom frame, two first springs are fixedly provided inside the top frame, a first slider is fixedly provided on the opposite side of the two first springs, two second springs are fixedly provided inside the bottom frame, a second slider is fixedly provided on the opposite side of the two second springs, a vibration cylinder is fixedly provided on the top of the second slider, the bottom end keyway of the telescopic universal joint is connected to a rotating shaft, and an eccentric disk is mounted on the outer wall of the rotating shaft through bolts; An injection pipe is installed on the upper surface of the top cover and on one side of the discharge mechanism, and a discharge pipe is installed at the bottom end of the tank body.

[0011] Preferably, the top of the rotating shaft is rotatably connected to the first slider via a bolt, the bottom of the rotating shaft is rotatably connected to the bottom of the vibration cylinder via a bearing, and the axis of the second ratchet disk is rotatably connected to the mounting plate via a bearing.

[0012] Preferably, the first slider and the second slider slide in the horizontal direction of the top frame and the bottom frame, and the top of the vibration cylinder is fixedly connected to the bottom of the first slider.

[0013] Preferably, it also includes a magnetic attraction mechanism and an air jet mechanism; The magnetic attraction mechanism includes a slide rod frame mounted on the upper surface of the base plate, a first slide sleeve and a second slide sleeve being slidably connected to the interior of the slide rod frame, a nebulium magnetic plate being fixedly mounted on the inner walls of the first slide sleeve and the second slide sleeve, and a driven plate being fixedly mounted on the top of the first slide sleeve; The jet mechanism includes an annular tube and a nozzle, the annular tube is installed on the upper surface of the top cover, the nozzle is installed on the bottom of the annular tube, a sleeve is installed through the upper surface of the annular tube, a piston is slidably connected to the inside of the sleeve, a push plate is slidably connected to the outside of the sleeve, a connecting spring is sleeved on the outer wall of the push plate, a through hole is opened in the interior of the piston, and an air intake pipe is installed through the top of the sleeve.

[0014] Preferably, the driven plate and the push plate are in the same horizontal direction, the through holes are interconnected between the nozzle, the annular pipe and the air intake pipe, and the piston and the push plate are fixedly connected.

[0015] The preparation process of the magnetic MOFs thallium removal agent includes the following preparation steps: S1: Synthesis of wet UiO-66-NH2; Mix the zirconium metal salt and the aminoterephthalic acid NH2-BDC organic ligand in a glass container, add DMF and glacial acetic acid to the mixture, and stir to fully dissolve the reactants; In the above steps, the zirconium source is zirconium tetrachloride, and the ratio of the amount of the zirconium salt to the amount of NH2-BDC is between 1:1 and 2; S2: The glass container containing the mixed solution in S1 is kept at a certain temperature for several hours, the temperature is 100 to 140 ° C, and the time is 10 to 16 hours. The reactant is naturally cooled and then centrifuged and washed with DMF and methanol three times each. The obtained material is centrifuged to obtain a wet UiO-66-NH2 gel; S3: synthesis of Fe3O4 nanoparticles; Weigh ferric chloride hexahydrate FeCl3·6H2O and place it in a polytetrafluoroethylene liner, add ethylene glycol solution into the polytetrafluoroethylene liner, and add sodium acetate NaAc and polyethylene glycol into the polytetrafluoroethylene liner; S4: stirring the mixture with a magnetic stirrer to fully dissolve it, sealing the polytetrafluoroethylene-lined stainless steel autoclave containing the reactants and placing it in an oven, transferring the solution in the autoclave to a centrifuge tube, magnetically separating the material with a magnet, and washing it thoroughly with deionized water and ethanol and drying it to obtain Fe3O4 nanoparticles; S4: Preparation method of magnetic Fe3O4@UiO-66-NH2; The Fe3O4 nanoparticles were mixed with the wet UiO-66-NH2 gel material and stirred until evenly mixed, and then dried. The resulting material was placed in a centrifuge tube and washed three times with acetone and methanol respectively. The washed material was dried. It should be noted that each washing time with acetone and methanol should be 10 to 14 hours at a temperature of 25 to 45°C. The prepared Fe3O4@UiO-66-NH2 nanoparticles can be injected into the tank through a feeding mechanism, and adsorbed with the lithium brine in the tank, thereby removing metallic thallium.

[0016] Compared with related technologies, the lithium brine thallium removal equipment and the magnetic MOFs thallium removal agent preparation process provided by the present invention have the following beneficial effects: In this case, Fe3O4@UiO-66-NH2 nanoparticles and pure water are added to the feeding tank. When 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 adaptively changes the falling trajectory, changing the straight line feeding into a parabolic arc feeding, thereby automatically dispersing the particles. Secondly, when the drum rotates clockwise, the Fe3O4@UiO-66-NH2 nanoparticles can be dispersed for the second time. Therefore, this design adopts active dispersion and passive dispersion to mix and dissolve the Fe3O4@UiO-66-NH2 nanoparticles and pure water medium. When the drum rotates, the guide wheel automatically drives the drum to automatically rise according to the thickness of the auxiliary plate. When the guide wheel rotates to the vertical surface of the auxiliary plate, it automatically falls to control the drum to reset. This design allows the drum to move vertically during rotation and also forms a small vibration, so that the sticky Fe3O4@UiO-66-NH2 nanoparticles can be mixed and dissolved again, so that the Fe3O4@UiO-66-NH2 nanoparticles are first processed into liquid and then added to the lithium leachate, so as to ensure a more uniform concentration in the leachate. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] 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.

[0018] Figure 1 A schematic diagram of the best structure provided by the present invention; Figure 2 for Figure 1 The schematic diagram of the cross-sectional structure of the tank body and the top cover shown; Figure 3 for Figure 2 The schematic diagram of the structure viewed from above is shown; Figure 4 for Figure 1 Schematic diagram of the driving mechanism structure shown; Figure 5 for Figure 4 The schematic diagram of the drive mechanism split structure shown; Figure 6 for Figure 5 The schematic cross-sectional structure diagram of the first ratchet disc shown; Figure 7 A schematic cross-sectional view of the blanking mechanism provided by the present invention; Figure 8 for Figure 7 The drum is shown in front plan view; Figure 9 for Figure 7 Schematic diagram of the initial working state of the drum shown; Figure 10 for Figure 9The diagram shows the working state of the drum rising when the drum rotates onto the auxiliary plate; Figure 11 for Figure 10 The schematic diagram of the structure viewed from above is shown; Figure 12 A schematic cross-sectional view of the vibration mechanism provided by the present invention; Figure 13 A schematic diagram of the structure of the magnetic attraction mechanism provided by the present invention; Figure 14 A schematic diagram of the structure of the jet mechanism provided by the present invention; Figure 15 for Figure 14 The enlarged structural diagram of point A is shown.

[0019] Description of Figure Numbers: 1. Bottom plate, 2. Tank body, 3. Top cover, 4. Mounting plate, 5. Positioning frame; 6. Driving mechanism, 61. Motor, 62. Driving gear, 63. Driven gear, 64. Rotating rod, 65. First ratchet, 66. First ratchet plate, 67. Driving pulley, 68. Second ratchet, 69. Second ratchet plate; 7. Discharging mechanism, 71. Discharging tank, 72. End cover, 73. Driven pulley, 74. Belt, 75. Auxiliary plate, 76. Rotating drum, 77. Guide wheel, 78. Notch, 79. Auxiliary groove, 710. Key rod, 711. Return spring, 712. Discharging pipe, 713. Baffle; 8. Vibration mechanism, 81. Telescopic universal joint, 82. Top frame, 83. Bottom frame, 84. First spring, 85. First slider, 86. Second spring, 87. Second slider, 88. Vertical rod, 89. Rotating shaft, 810. Eccentric disk, 811. Vibration cylinder; 9. Jet mechanism, 91. Ring pipe, 92. Nozzle, 93. Inlet pipe, 94. Sleeve, 95. Piston, 96. Push plate, 97. Connecting spring, 98. Through hole; 10. Magnetic attraction mechanism, 101. Sliding rod frame, 102. First sliding sleeve, 103. Second sliding sleeve, 104. Neodymium magnetic plate, 105. Driven plate; 11. Discharge pipe, 12. Injection pipe. DETAILED DESCRIPTION

[0020] 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.

[0021] The invention provides a lithium brine thallium removal device and a preparation process of a magnetic MOFs thallium removal agent.

[0022] First embodiment: See also Figures 1 to 11 , a lithium brine thallium removal device, comprising a bottom plate 1, a tank body 2, a top cover 3, a mounting plate 4, a positioning frame 5, a driving mechanism 6 and a feeding mechanism 7; The tank body 2 is mounted on the upper surface of the bottom plate 1 , the top cover 3 is mounted on the upper surface of the tank body 2 by bolts, the mounting plate 4 is mounted on the upper surface of the top cover 3 , and the positioning frame 5 is mounted on the upper surface of the mounting plate 4 ; The driving mechanism 6 includes a motor 61, a driving gear 62 and a driven gear 63. The bottom of the motor 61 is mounted on the upper surface of the mounting plate 4 by bolts. The axis of the driving gear 62 is connected to the keyway of the output shaft of the motor 61. The driven gear 63 is rotatably connected to the upper surface of the mounting plate 4 and is located inside the positioning frame 5. The axis of the driven gear 63 is connected to a rotating rod 64 with a keyway. The top keyway of the rotating rod 64 is connected to a first ratchet 65. The outer wall of the first ratchet 65 is meshed with a first ratchet disk 66. The outer wall keyway of the first ratchet disk 66 is connected to a driving pulley 67. Preferably, the motor 61 can be preferably a three-phase asynchronous motor.

[0023] See also Figure 4 and Figure 5 : When the user starts the motor 61, the driving gear 62 can be driven to engage with the driven gear 63 to rotate, so the motor 61 can freely control the forward and reverse rotation of the driven gear 63; The driven gear 63 has two rotation modes, one is a clockwise rotation mode of the driven gear 63 , and the other is a counterclockwise rotation mode of the driven gear 63 ; When the driven gear 63 rotates clockwise, the driven gear 63 drives the rotating rod 64 to drive the first ratchet 65 above the positioning frame 5 to rotate clockwise.

[0024] See also Figure 6 : When the first ratchet wheel 65 rotates clockwise, the peripheral teeth of the first ratchet wheel 65 will control the teeth in the first ratchet plate 66 clockwise, thereby realizing the synchronous transmission of the first ratchet plate 66 to rotate clockwise during the clockwise rotation of the first ratchet wheel 65.

[0025] The unloading mechanism 7 includes an unloading tank 71, an end cover 72, a key rod 710 and a return spring 711. The bottom of the unloading tank 71 is mounted on the top of the top cover 3, and the end cover 72 is mounted on the top of the unloading tank 71. The outer wall of the key rod 710 is rotatably mounted on the axis of the end cover 72 through a bearing. The return spring 711 is sleeved on the outer wall of the key rod 710. The top key groove of the key rod 710 is connected to the driven pulley 73. The outer walls of the driving pulley 67 and the driven pulley 73 are sleeved with a belt 74. The interior of the unloading tank 71 A rotating drum 76 is slidably connected to the outer wall below the key rod 710, and guide wheels 77 are rotatably connected to both sides of the rotating drum 76. An auxiliary plate 75 is fixed to the inner wall of the discharge tank 71 and on one side of the guide wheel 77. An auxiliary groove 79 is opened on the outer wall of the rotating drum 76, and a plurality of slots 78 are opened and closed on the outer wall of the rotating drum 76 and located below the auxiliary groove 79. A discharge pipe 712 is installed inside the end cover 72 and directly above the auxiliary groove 79. A baffle 713 is fixed to the outer wall of the key rod 710 and located below the end cover 72.

[0026] See also Figure 5 and Figure 7 : The clockwise rotating first ratchet plate 66 synchronously drives the driving pulley 67 and the transmission belt 74 controls the clockwise rotation of the driven pulley 73, and the driven pulley 73 rotates above the end cover 72.

[0027] See also Figure 7 and Figure 11 : When the driven pulley 73 rotates clockwise, it will synchronously drive the key rod 710 to rotate. When the key rod 710 rotates, the baffle 713, the return spring 711 and the rotating drum 76 will rotate in conjunction with the key rod 710.

[0028] See also Figure 7 : The user adds Fe3O4@UiO-66-NH2 nanoparticles and pure water into the discharge tank 71 through the discharge pipe 712; See also Figure 9 : When the key rod 710 controls the normal rotation of the rotating drum 76, 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 an extended state.

[0029] The driving gear 62 and the driven gear 63 are meshed with each other, and the outer wall of the first ratchet plate 66 is rotatably connected to the top of the positioning frame 5 through a bearing.

[0030] 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 drum 76. The auxiliary groove 79 is designed in an arc shape, and the multiple notches 78 are equidistantly distributed in a ring shape about the axis of the rotating drum 76. The cross-section of the rotating drum 76 is a conical structure that is narrow at the top and wide at the bottom. One side of the auxiliary plate 75 is an inclined structure, and the other side of the auxiliary plate 75 is a vertical surface structure. The bottom of the discharge tank 71 and the tank body 2 are interconnected.

[0031] It can be understood that: since the rotation of the 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 process; 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. Secondly, the rotating drum 76 and the key rod 710 slide, which can ensure that the rotating drum 76 can rotate and can also ensure that the rotating drum 76 can be lifted and lowered. This embodiment

[0032] Compared with the traditional direct feeding design, this case adds Fe3O4@UiO-66-NH2 nanoparticles and pure water into the feeding tank 71. When the Fe3O4@UiO-66-NH2 nanoparticles fall, they will enter the interior of the auxiliary groove 79. When the particles pass through the arc surface, the shape of the arc surface will adaptively change the falling trajectory, changing the straight line feeding into a parabolic arc feeding, so that the particles can be automatically dispersed. Secondly, when the drum 76 rotates clockwise, the Fe3O4@UiO-66-NH2 nanoparticles can be dispersed for the second time. Therefore, this design adopts active dispersion and passive dispersion to mix and dissolve the Fe3O4@UiO-66-NH2 nanoparticles and pure water medium, and when the drum 76 rotates, the guide wheel 77 automatically drives the drum 76 to automatically rise following the thickness of the auxiliary plate 75. When the guide wheel 77 rotates to the vertical plane of the auxiliary plate 75, it automatically falls to control the drum 76 to reset. This design allows the drum 76 to achieve vertical movement during rotation and also form a small amplitude vibration, so that the sticky Fe3O4@UiO-66-NH2 nanoparticles can be mixed and dissolved again, thereby realizing that the Fe3O4@UiO-66-NH2 nanoparticles are first processed into a liquid state and then added to the lithium leachate, thereby ensuring that the concentration in the leachate is more uniform.

[0033] Second embodiment: See also Figure 2 、 Figures 4 to 6 and Figure 12 , further comprising a vibration mechanism 8; 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 meshedly connected to a second ratchet disc 69 ; The vibration mechanism 8 includes a telescopic universal joint 81, four vertical rods 88, a top frame 82 and a bottom frame 83. The top keyway of the telescopic universal joint 81 is connected to the bottom of the second ratchet disk 69. The tops of the four vertical rods 88 are fixedly mounted on the bottom of the top cover 3. The top frame 82 is mounted on the outside of the four vertical rods 88. The bottom of the four vertical rods 88 and the bottom frame 83 is mounted 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 bottom 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 the rotating shaft 89. The outer wall of the rotating shaft 89 is mounted with an eccentric disk 810 by bolts. An injection pipe 12 is installed on the upper surface of the top cover 3 and on one side of the discharge mechanism 7 , and a discharge pipe 11 is installed at the bottom end of the tank body 2 .

[0034] See also Figure 4 and Figure 5 As can be seen from the first embodiment, the driven gear 63 has two working modes. When rotating clockwise in the first embodiment, the rotating rod 64 only affects the first ratchet 65 and does not drive the second ratchet 68 to rotate. When the rotating rod 64 rotates counterclockwise, the first ratchet 65 will avoid the first ratchet plate 66 when it rotates counterclockwise, so that the first ratchet plate 66 will not rotate. At this time, the counterclockwise rotating rotating rod 64 will drive the second ratchet 68 to control the second ratchet plate 69 to rotate counterclockwise. When the second ratchet plate 69 rotates, it will drive the telescopic universal joint 81 to rotate.

[0035] See also Figure 12 : During the rotation of the telescopic universal joint 81, the rotating shaft 89 will be driven to rotate inside the vibration 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, the left and right eccentric vibration forces will be generated during the rotation of the eccentric disk 810. The vibration force will further affect the vibration cylinder 811 to form vibration.

[0036] The top of the rotating shaft 89 is rotatably connected to the first slider 85 through a bolt, the bottom of the rotating shaft 89 is rotatably connected to the bottom of the vibration cylinder 811 through a bearing, and the axis of the second ratchet plate 69 is rotatably connected to the mounting plate 4 through a bearing.

[0037] The first slider 85 and the second slider 87 slide in the horizontal direction along the top frame 82 and the bottom frame 83 , and the top of the vibration cylinder 811 is fixedly connected to the bottom of the first slider 85 .

[0038] It can be understood that when the vibration cylinder 811 vibrates, it drives the first slider 85 and the second slider 87 at the upper and lower positions to generate a 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. Secondly, the vibration trajectory of the first slider 85 is biaxial vibration. The use of the telescopic universal joint 81 to connect the rotating shaft 89 and the second ratchet plate 69 can eliminate the interference caused by the vibration displacement of the rotating shaft 89 and ensure that the rotating shaft 89 can achieve universal rotation. This embodiment

[0039] Compared with the traditional design, this embodiment uses the forward and reverse rotation of the motor 61 to achieve two functions. When the material feeding function in the first embodiment is switched to the thallium removal function in this embodiment, the material feeding function is automatically disabled. Secondly, compared with the traditional thallium removal method, this embodiment is provided with a vibrating cylinder 811 in the middle of the tank body 2 to vibrate and affect the leachate inside the tank body 2. Compared with the traditional design, the vibration effect mode can achieve full mixing of Fe3O4@UiO-66-NH2 nanoparticles and leachate, while avoiding the destruction of the magnetic aggregates produced by the adsorption of metallic thallium by Fe3O4@UiO-66-NH2 nanoparticles, thereby achieving high efficiency in thallium removal. At the same time, the eccentric disk 810 is designed in a modular manner, and the user can adjust it freely. When the eccentric disks 810 overlap, the vibration force is the largest. Conversely, the smaller the overlapping part 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.

[0040] Third embodiment: See also Figure 2 、 Figures 13 to 15 , further comprising a magnetic attraction mechanism 10 and an air jet mechanism 9; The magnetic attraction mechanism 10 includes a slide rod frame 101 mounted on the upper surface of the base plate 1. A first sliding sleeve 102 and a second sliding sleeve 103 are slidably connected to the interior of the slide rod frame 101. The inner walls of the first sliding sleeve 102 and the second sliding sleeve 103 are fixedly mounted with a nebulium magnetic plate 104. A driven plate 105 is fixedly mounted on the top of the first sliding sleeve 102. The jet mechanism 9 includes an annular tube 91 and a nozzle 92. The annular tube 91 is installed on the upper surface of the top cover 3, and the nozzle 92 is installed at the bottom of the annular tube 91. A sleeve 94 is installed through the upper surface of the annular tube 91. A piston 95 is slidably connected to the inside of the sleeve 94. A push plate 96 is slidably connected to the outside of 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. An air intake pipe 93 is installed through the top of the sleeve 94.

[0041] 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 annular pipe 91 and the intake pipe 93, and the piston 95 and the push plate 96 are fixedly connected.

[0042] See also Figure 2 and Figure 13 : The user can freely slide the first sleeve 102 and the second sleeve 103 along the horizontal direction of the slide rod frame 101 until the two nebulium magnetic plates 104 are wrapped around the tank body 2. The nebulium magnetic plates 104 generate magnetism to adsorb the magnetic metal thallium aggregates on the inner wall of the tank body 2. When the first sleeve 102 is sliding, the driven plate 105 will also follow the driven movement.

[0043] See also Figure 14 and Figure 15 : When the nepheline magnetic plate 104 is wrapped around the outer wall of the tank body 2, the driven plate 105 will move and resist the force-bearing push plate 96 to push the internal piston 95 so that its through hole 98 moves into between the air intake pipe 93 and the annular tube 91. Then, when the air intake pipe 93 takes in air, it will enter the annular tube 91 through the through hole 98 and be sprayed out along the inner wall of the tank body 2 through the nozzle 92. This embodiment

[0044] Compared with the traditional design, this case is designed with two relatively movable rubidium magnetic plates 104 wrapped around the outer wall of the tank 2, so that the magnetic metal thallium aggregates can be adsorbed on the inner wall of the tank 2, thereby easily achieving the separation of the metal thallium aggregates and the pure leachate; At the same time, when the rubidium magnetic plate 104 is in the process of closing, the driven plate 105 drives the push plate 96 to control the piston 95 to connect the through hole 98 to the intake pipe 93 and the nozzle 92, thereby automatically opening the intake pipe 93 to generate high-pressure jet gas sprayed on the inner wall of the tank body 2, which can assist the rubidium magnetic plate 104 to separately separate the metal thallium aggregates, thereby achieving efficient removal and treatment of the metal thallium aggregates.

[0045] Working principle of the present invention: S1: input of Fe3O4@UiO-66-NH2 nanoparticles; Add Fe3O4@UiO-66-NH2 nanoparticles and pure water into the feeding tank 71, start the motor 61 to control the driving gear 62 to control the driven gear 63 so that the first ratchet plate 66 controls the driving pulley 67 to affect the belt 74 to control the driven pulley 73 to rotate clockwise; The driven pulley 73 controls the key rod 710 to drive the drum 76 to achieve mixed dissolution of Fe3O4@UiO-66-NH2 nanoparticles and pure water, and the drum 76 can also achieve lifting vibration to assist the mixed dissolution during the rotation process; S2: leaching solution to remove thallium; The pretreated Fe3O4@UiO-66-NH2 nanoparticles enter the tank body 2, and the injection pipe 12 is responsible for adding the leachate. The rotating rod 64 is started to rotate counterclockwise. The counterclockwise rotating rotating rod 64 drives the second ratchet wheel 68 to drive and control the second ratchet disk 69 to rotate counterclockwise. When the second ratchet disk 69 rotates, it drives the telescopic universal joint 81 to rotate. During the rotation of the telescopic universal joint 81, the rotating shaft 89 is driven to rotate inside the vibration 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, the left and right eccentric vibration forces are generated during the rotation of the eccentric disk 810. The vibration force further affects the vibration cylinder 811 to vibrate, vibrating the leachate inside the tank body 2, so that the metal thallium is adsorbed and flocculated to form magnetic metal thallium aggregates. S3: separation of magnetic metal thallium aggregates and pure liquid; The first sliding sleeve 102 and the second sliding sleeve 103 are freely slid along the horizontal direction of the slide 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 adsorb the magnetic metal thallium aggregates on the inner wall of the tank body 2, and the treated pure leachate is discharged through the discharge pipe 11. After that, the magnetic metal thallium aggregates remain on the inner wall of the tank body 2. After that, the rubidium magnetic plates 104 are powered on and lose their magnetism, and the nozzle 92 sprays gas to help the metal thallium aggregates slide down for collection.

[0046] Fourth embodiment: The preparation process of the magnetic MOFs thallium removal agent includes the following preparation steps: S1: Synthesis of wet UiO-66-NH2; Mix the zirconium metal salt and the aminoterephthalic acid NH2-BDC organic ligand in a glass container, add DMF and glacial acetic acid to the mixture, and stir to fully dissolve the reactants; In the above steps, the zirconium source is zirconium tetrachloride, and the ratio of the amount of the zirconium salt to the amount of NH2-BDC is between 1:1 and 2; S2: The glass container containing the mixed solution in S1 is kept at a certain temperature for several hours, the temperature is 100 to 140 ° C, and the time is 10 to 16 hours. The reactant is naturally cooled and then centrifuged and washed with DMF and methanol three times each. The obtained material is centrifuged to obtain a wet UiO-66-NH2 gel; S3: synthesis of Fe3O4 nanoparticles; Weigh ferric chloride hexahydrate FeCl3·6H2O and place it in a polytetrafluoroethylene liner, add ethylene glycol solution into the polytetrafluoroethylene liner, and add sodium acetate NaAc and polyethylene glycol into the polytetrafluoroethylene liner; S4: stirring the mixture with a magnetic stirrer to fully dissolve it, sealing the polytetrafluoroethylene-lined stainless steel autoclave containing the reactants and placing it in an oven, transferring the solution in the autoclave to a centrifuge tube, magnetically separating the material with a magnet, and washing it thoroughly with deionized water and ethanol and drying it to obtain Fe3O4 nanoparticles; S4: Preparation method of magnetic Fe3O4@UiO-66-NH2; The Fe3O4 nanoparticles were mixed with the wet UiO-66-NH2 gel material and stirred until evenly mixed, and then dried. The resulting material was placed in a centrifuge tube and washed three times with acetone and methanol respectively. The washed material was dried. It should be noted that each washing time with acetone and methanol should be 10 to 14 hours at a temperature of 25 to 45°C. The prepared Fe3O4@UiO-66-NH2 nanoparticles can be injected into the tank body 2 through the feeding mechanism 7, and adsorbed by the lithium brine in the tank body 2, thereby removing the metallic thallium. This embodiment

[0047] It is formed by combining zirconium tetrachloride (ZrCl4) or zirconium oxychloride octahydrate with aminoterephthalic acid organic ligand to form a three-dimensional porous structure, and then introducing Fe3O4 to form a magnetic load through compounding at high temperature. After passing through acid analysis solution, it is regenerated to achieve the purpose of recycling. The reason why UiO-66 has such outstanding stability is that under ideal conditions, the UiO-66-NH2 building block is composed of [Zr6O4(OH)4] metal clusters connected by 12 H2BDC-NH2 coordination groups, which is the highest possible coordination number between organic ligands and metal clusters in MOFs. The MOFs material exhibits smaller crystal size, shorter mass transfer path, higher adsorption capacity and more unsaturated active sites from a microscopic perspective. The synthesized adsorption material is placed in a lithium mica leachate with a thallium content of 4000 to 5000 ppb. The adsorption in the adsorption reaction is through π-π bond stacking, hydrogen bond interaction, metal and ligand coordination interaction and van der Waals interaction. Its efficient adsorption driving force comes from the electrostatic interaction between UiO-66-NH2 and Tl+, which enables the thallium in the brine to combine with the exposed active sites in the MOFs material, thereby achieving the effect of efficient removal.

[0048] 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. A lithium brine thallium removal device, characterized in that: It includes a bottom plate, a tank body, a top cover, a mounting plate, a positioning frame, a driving mechanism and a feeding mechanism; The tank body is mounted on the upper surface of the bottom plate, the top cover is mounted on the upper surface of the tank body by bolts, 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; The driving mechanism includes a motor, a driving gear and a driven gear, the bottom of the motor is mounted on the upper surface of the mounting plate by bolts, the axis of the driving gear is connected to the keyway of the motor output shaft, the driven gear is rotatably connected to the upper surface of the mounting plate and is located inside the positioning frame, the axis of the driven gear is connected to a rotating rod with a keyway, the top keyway of the rotating rod is connected to a first ratchet, the outer wall of the first ratchet is meshed with a first ratchet disk, and the outer wall keyway of the first ratchet disk is connected to a driving pulley; The top of the key rod is connected to the driven pulley by the key slot, and the outer wall of the driving pulley and the driven pulley are sleeved with a belt. The interior of the discharge tank is located below the key rod and is slidably connected to the outer wall of the drum. Both sides of the drum are rotatably connected to the guide wheel. The inner wall of the discharge tank and one side of the guide wheel are fixed with an auxiliary plate. The outer wall of the drum is provided with an auxiliary groove, and the outer wall of the drum is opened and closed with multiple slots below the auxiliary groove. A feeding pipe is installed inside the end cover and just above the auxiliary groove, and a baffle is fixed on the outer wall of the key rod and located below the end cover.

2. The lithium brine thallium removal equipment according to claim 1, characterized in that: The driving gear and the driven gear are meshed with each other, and the outer wall of the first ratchet plate is rotatably connected to the top of the positioning frame through a bearing.

3. The lithium brine thallium removal equipment according to claim 1, characterized in that: The upper and lower ends of the return spring are fixedly connected to the bottom of the baffle and the top of the drum. The auxiliary groove is designed in an arc shape, and multiple notches are equidistantly distributed in a ring about the axis of the drum. The cross-section of the drum is a conical structure that is narrow at the top and wide at the bottom. One side of the auxiliary plate is an inclined structure, and the other side of the auxiliary plate is a vertical structure. The bottom of the discharge tank and the tank body are interconnected.

4. The lithium brine thallium removal equipment according to claim 1, characterized in that: Also included is a vibration mechanism; The bottom keyway of the rotating rod is connected to a second ratchet wheel, and the outer wall of the second ratchet wheel is meshedly connected to a second ratchet disk; The vibration mechanism includes a telescopic universal joint, four vertical rods, a top frame and a bottom frame, the top keyway of the telescopic universal joint is connected to the bottom of the second ratchet disk, the tops of the four vertical rods are fixedly mounted on the bottom of the top cover, the top frame is mounted on the outside of the four vertical rods, and the bottom of the four vertical rods and below the top frame is mounted with a bottom frame, two first springs are fixedly provided inside the top frame, a first slider is fixedly provided on the opposite side of the two first springs, two second springs are fixedly provided inside the bottom frame, a second slider is fixedly provided on the opposite side of the two second springs, a vibration cylinder is fixedly provided on the top of the second slider, the bottom end keyway of the telescopic universal joint is connected to a rotating shaft, and an eccentric disk is mounted on the outer wall of the rotating shaft through bolts; An injection pipe is installed on the upper surface of the top cover and on one side of the discharge mechanism, and a discharge pipe is installed at the bottom end of the tank body.

5. The lithium brine thallium removal equipment according to claim 4, characterized in that: The top of the rotating shaft is rotatably connected to the first slider through a bolt, the bottom of the rotating shaft is rotatably connected to the bottom of the vibration cylinder through a bearing, and the axis of the second ratchet disk is rotatably connected to the mounting plate through a bearing.

6. The lithium brine thallium removal equipment according to claim 4, characterized in that: The first slider and the second slider slide in the horizontal direction of the top frame and the bottom frame, and the top of the vibration cylinder is fixedly connected to the bottom of the first slider.

7. The lithium brine thallium removal equipment according to claim 1, characterized in that: It also includes a magnetic attraction mechanism and an air jet mechanism; The magnetic attraction mechanism includes a slide rod frame mounted on the upper surface of the base plate, a first slide sleeve and a second slide sleeve being slidably connected to the interior of the slide rod frame, a nebulium magnetic plate being fixedly mounted on the inner walls of the first slide sleeve and the second slide sleeve, and a driven plate being fixedly mounted on the top of the first slide sleeve; The jet mechanism includes an annular tube and a nozzle, the annular tube is installed on the upper surface of the top cover, the nozzle is installed on the bottom of the annular tube, a sleeve is installed through the upper surface of the annular tube, a piston is slidably connected to the inside of the sleeve, a push plate is slidably connected to the outside of the sleeve, a connecting spring is sleeved on the outer wall of the push plate, a through hole is opened in the interior of the piston, and an air intake pipe is installed through the top of the sleeve.

8. The lithium brine thallium removal equipment according to claim 7, characterized in that: The driven plate and the push plate are in the same horizontal direction, the through holes are interconnected among the nozzle, the annular pipe and the air intake pipe, and the piston and the push plate are fixedly connected.

9. A process for preparing a magnetic MOFs thallium remover, characterized in that: The magnetic MOFs thallium removal agent is used in the lithium brine thallium removal equipment according to any one of claims 1 to 8, comprising the following preparation steps: S1: Synthesis of wet UiO-66-NH2; Mix the zirconium metal salt and the aminoterephthalic acid NH2-BDC organic ligand in a glass container, add DMF and glacial acetic acid to the mixture, and stir to fully dissolve the reactants; In the above steps, the zirconium source is zirconium tetrachloride, and the ratio of the amount of the zirconium salt to the amount of NH2-BDC is between 1:1 and 2; S2: The glass container containing the mixed solution in S1 is kept at a certain temperature for several hours, the temperature is 100 to 140 ° C, and the time is 10 to 16 hours. The reactant is naturally cooled and then centrifuged and washed with DMF and methanol three times each. The obtained material is centrifuged to obtain a wet UiO-66-NH2 gel; S3: synthesis of Fe3O4 nanoparticles; Weigh ferric chloride hexahydrate FeCl3·6H2O and place it in a polytetrafluoroethylene liner, add ethylene glycol solution into the polytetrafluoroethylene liner, and add sodium acetate NaAc and polyethylene glycol into the polytetrafluoroethylene liner; S4: stirring the mixture with a magnetic stirrer to fully dissolve it, sealing the polytetrafluoroethylene-lined stainless steel autoclave containing the reactants and placing it in an oven, transferring the solution in the autoclave to a centrifuge tube, magnetically separating the material with a magnet, and washing it thoroughly with deionized water and ethanol and drying it to obtain Fe3O4 nanoparticles; S4: Preparation method of magnetic Fe3O4@UiO-66-NH2; The Fe3O4 nanoparticles were mixed with the wet UiO-66-NH2 gel material and stirred until evenly mixed, and then dried. The resulting material was placed in a centrifuge tube and washed three times with acetone and methanol respectively. The washed material was dried. It should be noted that each washing time with acetone and methanol should be 10 to 14 hours at a temperature of 25 to 45°C. The prepared Fe3O4@UiO-66-NH2 nanoparticles can be injected into the tank through a feeding mechanism, and adsorbed with the lithium brine in the tank, thereby removing metallic thallium.

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