A fluorine-containing wastewater treatment device and method

Abstract

This invention provides a device and method for treating fluoride-containing wastewater. Relating to the field of wastewater treatment, the device includes a tank placed on the ground. The device and method treat wastewater by adjusting the pH of the fluoride-containing wastewater to 5 to improve the removal efficiency of fluoride ions. An adsorption motor drives a first and second adsorption box, arranged at different heights, to rotate within the tank, enabling dynamic, multi-angle contact between the MOF adsorbent and the wastewater. This significantly increases the mass transfer area and efficiency, avoiding dead zones that may exist in static adsorption. Simultaneously, the first and second adsorption boxes agitate the water within the tank, forming an internal circulation that ensures deep and uniform mixing of the wastewater and the MOF adsorbent, improving the overall treatment effect. The first and second adsorption boxes feature a pluggable design, facilitating rapid removal for regeneration after the MOF adsorbent becomes saturated, aligning with the concept of green environmental protection.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment, and more particularly to a device and method for treating fluoride-containing wastewater. Background Technology

[0002] Fluoride wastewater mainly originates from industrial processes such as semiconductor manufacturing, photovoltaic production, glass etching, metal smelting, electroplating, phosphate fertilizer chemical industry, fluoride production, and fluoride-containing pharmaceutical and pesticide synthesis. These industries use or produce fluoride-containing substances such as hydrofluoric acid and fluorosilicic acid during production, resulting in persistently high concentrations of fluoride ions in their wastewater discharge.

[0003] Existing fluoride-containing wastewater treatment devices are equipped with a dispersing mechanism. The rotation of the first screen plate generates shearing and pushing forces on the fluoride-containing wastewater, which disperses the clumps and promotes the contact between chemical reagents and the fluoride-containing wastewater.

[0004] However, in actual use, the mixing device only stirs in one dimension and cannot realize the overall wastewater circulation mechanism inside the device, resulting in uneven mixing of wastewater at different depths in the reactor.

[0005] Therefore, it is necessary to provide a device and method for treating fluoride-containing wastewater to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides a device and method for treating fluoride-containing wastewater, which solves the problem of uneven mixing of wastewater at different depths within the reactor.

[0007] To solve the above-mentioned technical problems, the present invention provides a fluoride-containing wastewater treatment device, comprising: a tank placed on the ground, a top cover movably installed on the top of the tank, a bottom cover fixedly installed on the bottom of the tank, an outlet opening on the surface of the bottom cover, vertical grooves opening on both sides of the tank, and a support box fixedly installed on both sides of the tank.

[0008] The regulating mechanism is used to pre-regulate the fluoride-containing wastewater;

[0009] An adsorption mechanism is fixedly installed at the bottom of the inner walls of the two carrying boxes. The adsorption mechanism includes telescopic columns, two of which are fixedly installed at the bottom of the inner walls of the two carrying boxes respectively. A support plate is fixedly installed at the top of each of the two telescopic columns. A first rotating shaft and a second rotating shaft are rotatably installed between the two support plates. Four first adsorption boxes are snapped onto the surface of the first rotating shaft inside the tank through a fixing component. Several first through holes are opened on the surface of the first adsorption box. Four second adsorption boxes are snapped onto the surface of the second rotating shaft inside the tank through a fixing component. Several second through holes are opened on the surface of the second adsorption box. Two baffles are fixedly installed on the surfaces of the first and second rotating shafts. The two baffles are adapted to the two vertical grooves. Fixing columns are fixedly installed on both sides of the four first adsorption boxes and the four second adsorption boxes. The fixing columns are adapted to the fixing component. An adsorption motor is fixedly installed at one end of each of the first and second rotating shafts through a bracket.

[0010] Water outlet mechanism, the water outlet mechanism being used to open the water outlet to release water:

[0011] A drainage mechanism for recycling treated water:

[0012] A water distribution mechanism is used to distribute water to the tank.

[0013] Preferably, the regulating mechanism is connected to the upper cover. The regulating mechanism includes an regulating pool and an inlet pipe. The outlet end of the inlet pipe is connected to the upper cover. The regulating pool is located on the ground. A wastewater pipe is connected to one side of the regulating pool. A medicine tank is connected to one side of the regulating pool through a medicine inlet pipe. The medicine tank is located on the ground. A water pump is connected to the bottom of the regulating pool through a water pipe. The outlet end of the water pump is connected to the inlet end of the inlet pipe.

[0014] Preferably, each end of the first rotating shaft and the second rotating shaft is provided with four placement slots. The placement slots are adapted to be installed with the fixing column and the fixing components. Thirty-two fixing components are respectively fixedly installed on both sides of the inner wall of the sixteen placement slots. Each fixing component includes a fixing plate, which is fixedly installed on one side of the inner wall of the placement slot. One side of the fixing plate is fixedly connected to a locking block by a spring, and the locking block is adapted to be installed with the fixing column.

[0015] Preferably, the water outlet mechanism is fixedly installed at the bottom of the bottom cover. The water outlet mechanism includes a motor, which is fixedly installed at the bottom of the bottom cover via a bracket. The output end of the motor is fixedly connected to a water outlet shaft. The water outlet shaft passes through the bottom of the bottom cover and extends into the interior of the tank. A water outlet plate is fixedly installed on the surface of the water outlet shaft inside the tank. The water outlet plate is adapted to the water outlet. The drainage mechanism is connected to the water outlet. The drainage mechanism includes a drain pipe, the inlet end of which is connected to the water outlet. A filter screen is installed inside the drain pipe. The drain pipe is connected to a drain bucket via a three-way valve.

[0016] Preferably, the water distribution mechanism is connected to the bottom of the bottom cover. The water distribution mechanism includes a connecting pipe, which is connected to the bottom of the bottom cover. The bottom end of the connecting pipe is connected to a water distribution tank. The outside of the water distribution tank is connected to six water distribution pipes, and the bottom of each of the six water distribution pipes is provided with several water distribution holes.

[0017] Preferably, a drive mechanism is fixedly installed on one side of the inner wall of each of the two carrier boxes. The drive mechanism includes a drive motor, which is fixedly installed on one side of the inner wall of the carrier box. A cam is fixedly installed on the output shaft of the drive motor.

[0018] Preferably, bearings are fixedly installed at both ends of the first and second rotating shafts, and the four bearings are respectively adapted to be installed with the two cams. A pH detector is installed inside the regulating tank.

[0019] Preferably, a backflushing mechanism is connected to one side of the three-way valve. The backflushing mechanism includes a backflushing pipe, one end of which is connected to one side of the three-way valve, and the other end of which is connected to a backflushing box. The backflushing box is located on the ground. A backflushing port is provided on the surface of the bottom cover. A thread is provided on the surface of the water outlet shaft. A lifting mechanism is threadedly connected to the surface of the water outlet shaft. The lifting mechanism includes a lifting plate. The interior of the lifting plate is threadedly connected to the surface of the water outlet shaft. Four limiting posts are fixedly installed on the top of the bottom cover. The surfaces of the four limiting posts are slidably connected to the interior of the lifting plate. The water outlet plate is adapted to the backflushing port. A recovery box is connected to the bottom of the backflushing port.

[0020] A method for treating fluoride-containing wastewater includes the following steps:

[0021] S1: Zirconium tetrachloride ( ) and 2-aminoterephthalic acid ( Add N,N-dimethylformamide ( In the solution, ultrasonic treatment is performed until complete dissolution is obtained;

[0022] S2: Add acetic acid to the dissolved solution and stir magnetically to form a homogeneous solution, thus obtaining a mixed solution;

[0023] S3: Transfer the mixed solution to a 50ml polytetrafluoroethylene-lined high-pressure reactor, seal it, and place it in an oven;

[0024] S4: After the reaction is complete, allow the mixture to cool to room temperature naturally, then centrifuge to collect the white precipitate.

[0025] S5: The white precipitate was washed successively with DMF and anhydrous ethanol, and then dried under vacuum to obtain... powder;

[0026] S6: Add MOF adsorbent ( Add to a fluoride-containing solution, maintain constant temperature and shake, centrifuge, collect the supernatant, and determine... concentration;

[0027] S7: Selective testing, in the presence of... , Repeat step S6 in the mixed solution to calculate the adsorption capacity and selectivity coefficient;

[0028] S8: Regeneration treatment, immersing the adsorbed MOF in... In the solution, after shaking, the solid is separated by centrifugation, washed with deionized water until neutral, and then placed in an oven to dry;

[0029] S9: Cyclic test, repeat the adsorption experiments of S6 and S7 5 times, and calculate the capacity retention rate.

[0030] Preferably, zirconium tetrachloride (S1) ) is 1 mmol, 2-aminoterephthalic acid ( In step S2, 1.2 mmol of MOF was added to 40 ml of DMF, and the mixture was sonicated for 10 min. In step S3, 3 ml of acetic acid was added, and the mixture was magnetically stirred for 30 min. In step S3, the reaction temperature was set at 120 °C, and the reaction time was 24 h. In step S4, the mixture was centrifuged for 10 min at 8000 rpm. In step S5, the mixture was washed three times each with DMF and anhydrous ethanol, and then vacuum dried at 60 °C for 12 h. In step S6, 0.1 g of MOF adsorbent was added to 100 ml of fluorine-containing solution and shaken at 25 °C for 12 h. Selectivity coefficient: Adsorption capacity: Wherein, C0 (initial concentration), Ce (equilibrium concentration), V (solution volume, L), and m (adsorbent mass, g); the MOF saturated in S8 is 0.1 g. The solution is 0.1 mol / L, 50 ml, shaken at 25℃ for 2 h, and dried at 60℃. The formula for calculating the volume retention rate in S9 is: Retention Rate ;in, This represents the initial adsorption capacity. Let n be the capacity of the nth iteration.

[0031] Compared with related technologies, the fluoride-containing wastewater treatment device provided by the present invention has the following beneficial effects:

[0032] This invention provides a fluoride-containing wastewater treatment device. By adjusting the pH value of the fluoride-containing wastewater to 5, a suitable reaction environment is provided for the MOF adsorbent, thereby improving the removal efficiency of fluoride ions and treating the wastewater. The device uses an adsorption motor to drive the first and second adsorption boxes, which are arranged at different heights, to rotate within the tank. This allows the MOF adsorbent to achieve dynamic and multi-angle contact with the wastewater, significantly increasing the mass transfer area and efficiency. It avoids the dead zone problem that may exist in static adsorption. At the same time, the first and second adsorption boxes can also agitate the water in the tank, forming an internal circulation to ensure deep and uniform mixing of wastewater and MOF adsorbent, thereby improving the overall treatment effect. The first and second adsorption boxes adopt a pluggable design, which facilitates quick removal and regeneration of the MOF adsorbent after it becomes saturated, in line with the concept of green environmental protection. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of a preferred embodiment of a fluoride-containing wastewater treatment device provided by the present invention;

[0034] Figure 2 Another structural schematic diagram of a preferred embodiment of a fluoride-containing wastewater treatment device;

[0035] Figure 3 for Figure 2 The diagram shows the installation of the vertical slot;

[0036] Figure 4 for Figure 2 The diagram shows the structure of the adjustment mechanism.

[0037] Figure 5 for Figure 2 Another schematic diagram of the adjustment mechanism shown;

[0038] Figure 6 for Figure 2 The diagram shows the structure of the adsorption mechanism.

[0039] Figure 7 for Figure 6 The diagram shows the structure of the fixing component.

[0040] Figure 8 for Figure 7 The diagram shows the installation of the fixing components;

[0041] Figure 9 for Figure 8 The enlarged schematic diagram of part A shown below;

[0042] Figure 10 for Figure 2 The diagram shows the installation of the water outlet mechanism;

[0043] Figure 11 for Figure 10 The diagram shows the structure of the water outlet mechanism;

[0044] Figure 12 for Figure 2 The diagram shows the structure of the drainage mechanism.

[0045] Figure 13 for Figure 2 The diagram shows the structure of the water distribution mechanism.

[0046] Figure 14 This is a schematic diagram of a second embodiment of a fluoride-containing wastewater treatment device;

[0047] Figure 15 for Figure 14 The diagram shows the structure of the drive mechanism.

[0048] Figure 16 for Figure 14 The diagram shown is a structural schematic of the recoil mechanism.

[0049] Figure 17 for Figure 14 The diagram shown is a structural schematic of the recoil mechanism.

[0050] Figure 18 for Figure 14 The diagram shows the installation of the recycling bin;

[0051] Figure 19 for Figure 14 The diagram shows the installation of the backflush port;

[0052] Figure 20 To prepare MOF adsorbents ( )flow chart.

[0053] Numbered in the diagram: 1. Tank; 2. Adjusting mechanism; 201. Adjusting tank; 202. Wastewater pipe; 203. Chemical tank; 204. Chemical inlet pipe; 205. Water pump; 206. Water inlet pipe; 3. Adsorption mechanism; 301. Telescopic column; 302. Support plate; 303. First rotating shaft; 304. First adsorption box; 305. First through hole; 306. Second rotating shaft; 307. Second adsorption box; 308. Second through hole; 309. Baffle; 310. Fixed column; 311. Adsorption motor; 31. Fixing assembly; 3101. Fixing plate; 3102. Spring; 3103. Locking block; 4. Water outlet mechanism; 401. Motor; 402. Water outlet shaft; 4 03. Water outlet plate; 5. Drainage mechanism; 501. Drainage pipe; 502. Filter screen; 503. Three-way valve; 504. Drainage bucket; 6. Water distribution mechanism; 601. Connecting pipe; 602. Water distribution tank; 603. Water distribution pipe; 604. Water distribution hole; 7. Backflush port; 8. Drive mechanism; 801. Drive motor; 802. Cam; 9. Backflush mechanism; 901. Backflush pipe; 902. Backflush box; 10. Lifting mechanism; 1001. Limiting post; 1002. Lifting plate; 11. Top cover; 12. Bottom cover; 13. pH meter; 14. Bearing; 15. Vertical trough; 16. Carrier box; 17. Water outlet; 18. Placement trough; 19. Recycling box. Detailed Implementation

[0054] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0055] First Embodiment

[0056] Please refer to the following: Figures 1-13 A fluoride-containing wastewater treatment device includes: a tank 1 placed on the ground, a top cover 11 movably installed on the top of the tank 1, a bottom cover 12 fixedly installed on the bottom of the tank 1, an outlet 17 opened on the surface of the bottom cover 12, vertical grooves 15 opened on both sides of the tank 1, and a support box 16 fixedly installed on both sides of the tank 1.

[0057] Adjustment mechanism 2, the adjustment mechanism 2 is used for pre-adjusting fluoride-containing wastewater;

[0058] An adsorption mechanism 3 is fixedly installed at the bottom of the inner walls of the two support boxes 16. The adsorption mechanism 3 includes telescopic columns 301, with two telescopic columns 301 respectively fixedly installed at the bottom of the inner walls of the two support boxes 16. A support plate 302 is fixedly installed at the top of each of the two telescopic columns 301. A first rotating shaft 303 and a second rotating shaft 306 are rotatably installed between the two support plates 302. Four first adsorption boxes 304 are snapped onto the surface of the first rotating shaft 303 inside the tank 1 via a fixing assembly 31. Several first through holes 305 are formed on the surface of each first adsorption box 304. The second rotating shaft 306 is located at... Four second adsorption boxes 307 are snapped onto the inner surface of the tank 1 by a fixing component 31. The surface of the second adsorption box 307 is provided with several second through holes 308. Two baffles 309 are fixedly installed on the surfaces of the first rotating shaft 303 and the second rotating shaft 306. The two baffles 309 are adapted to the two vertical grooves 15. Fixing posts 310 are fixedly installed on both sides of the four first adsorption boxes 304 and the four second adsorption boxes 307. The fixing posts 310 are adapted to the fixing component 31. An adsorption motor 311 is fixedly installed at one end of the first rotating shaft 303 and the second rotating shaft 306 by a bracket.

[0059] Water outlet mechanism 4, which is used to open the water outlet 17 to release water:

[0060] Drainage mechanism 5, which is used to recycle the treated water:

[0061] Water distribution mechanism 6, which is used to distribute water to the tank 1.

[0062] The regulating mechanism 2 is connected to the upper cover 11. The regulating mechanism 2 includes an regulating pool 201 and an inlet pipe 206. The outlet end of the inlet pipe 206 is connected to the upper cover 11. The regulating pool 201 is set on the ground. A wastewater pipe 202 is connected to one side of the regulating pool 201. A medicine tank 203 is connected to one side of the regulating pool 201 through a medicine inlet pipe 204. The medicine tank 203 is set on the ground. A water pump 205 is connected to the bottom of the regulating pool 201 through a water pipe. The outlet end of the water pump 205 is connected to the inlet end of the inlet pipe 206.

[0063] Four placement slots 18 are provided at both ends of the first rotating shaft 303 and the second rotating shaft 306. The placement slots 18 are adapted to be installed with the fixing post 310 and the fixing component 31. Thirty-two fixing components 31 are respectively fixedly installed on both sides of the inner wall of sixteen placement slots 18. Each fixing component 31 includes a fixing plate 3101. The fixing plate 3101 is fixedly installed on one side of the inner wall of the placement slot 18. A locking block 3103 is fixedly connected to one side of the fixing plate 3101 by a spring 3102. The locking block 3103 is adapted to be installed with the fixing post 310.

[0064] The water outlet mechanism 4 is fixedly installed at the bottom of the bottom cover 12. The water outlet mechanism 4 includes a motor 401, which is fixedly installed at the bottom of the bottom cover 12 via a bracket. The output end of the motor 401 is fixedly connected to a water outlet shaft 402. The water outlet shaft 402 passes through the bottom of the bottom cover 12 and extends into the interior of the tank 1. A water outlet plate 403 is fixedly installed on the surface of the water outlet shaft 402 located inside the tank 1. The water outlet plate 403 is adapted to the water outlet 17. The drainage mechanism 5 is connected to the water outlet 17. The drainage mechanism 5 includes a drain pipe 501, the inlet end of which is connected to the water outlet 17. A filter screen 502 is provided inside the drain pipe 501. The drain pipe 501 is connected to a drain bucket 504 via a three-way valve 503.

[0065] The water distribution mechanism 6 is connected to the bottom of the bottom cover 12. The water distribution mechanism 6 includes a connecting pipe 601, which is connected to the bottom of the bottom cover 12. The bottom end of the connecting pipe 601 is connected to a water distribution tank 602. The outside of the water distribution tank 602 is connected to six water distribution pipes 603. The bottom of each of the six water distribution pipes 603 is provided with several water distribution holes 604.

[0066] In actual use, the inside of the reagent box 203 is a sodium hydroxide solution; the top cover 11 is detachable; the first adsorption box 304 and the second adsorption box 307 contain MOF adsorbent, which can efficiently adsorb fluoride ions in water.

[0067] The working principle of the fluoride-containing wastewater treatment device provided by this invention is as follows:

[0068] First, the fluoride-containing wastewater is discharged into the equalization tank 201 through the wastewater pipe 202. After the pH value is measured manually, sodium hydroxide solution is provided through the reagent tank 203 to adjust it to 5. Then, the water pump 205 is started and discharged through the inlet pipe 206 to the connecting pipe 601. The wastewater flows into the distribution tank 602 and is discharged into the tank 1 through the distribution pipe 603.

[0069] Then, when the wastewater flows into the tank 1, the two adsorption motors 311 are activated to drive the first rotating shaft 303 and the second rotating shaft 306 to rotate respectively. The first rotating shaft 303 and the second rotating shaft 306 drive the first adsorption box 304 and the second adsorption box 307 to rotate respectively. At this time, the first adsorption box 304 and the second adsorption box 307 rotate, and the wastewater enters through the first through hole 305 and the second through hole 308 to be adsorbed by the MOF adsorbent. While the adsorption is working, the first adsorption box 304 and the second adsorption box 307, which are up and down, can better contact the wastewater during the rotation process. At the same time, they can also break the stability of the wastewater and carry out the overall circulation of wastewater inside the tank 1, deeply mixing the different states of wastewater treatment.

[0070] Then, after the treatment is completed, start the motor 401 to drive the water outlet shaft 402 to rotate. The water outlet shaft 402 drives the water outlet plate 403 to open the water outlet 17 to discharge the treated purified water. After passing through the drain pipe 501 and the filter screen 502, the water is discharged into the drain tank 504 for recycling. The filter screen 502 filters solid impurities and overflowing MOF adsorbent.

[0071] Finally, after the MOF adsorbent inside the first adsorption box 304 and the second adsorption box 307 has been used multiple times, after opening the top cover 11, the first adsorption box 304 and the second adsorption box 307 are pulled out for MOF adsorbent regeneration. When manually pulled out, the spring 3102 rebounds and enters the placement slot 18.

[0072] Compared with related technologies, the fluoride-containing wastewater treatment device provided by the present invention has the following beneficial effects:

[0073] By adjusting the pH of the fluoride-containing wastewater to 5, a suitable reaction environment is provided for the MOF adsorbent, thereby improving the removal efficiency of fluoride ions for wastewater treatment. The first adsorption box 304 and the second adsorption box 307, which are arranged at different heights, are driven by the adsorption motor 311 to rotate in the tank 1, so that the MOF adsorbent and the wastewater can achieve dynamic and multi-angle contact, which significantly increases the mass transfer area and efficiency and avoids the dead zone problem that may exist in static adsorption. At the same time, the first adsorption box 304 and the second adsorption box 307 can also stir the water in the tank to form an internal circulation, ensuring that the wastewater and the MOF adsorbent are deeply and uniformly mixed, thereby improving the overall treatment effect. The first adsorption box 304 and the second adsorption box 307 adopt a pluggable design, which makes it easy to quickly remove the MOF adsorbent for regeneration after it is saturated, in line with the concept of green environmental protection.

[0074] Second Embodiment

[0075] Please refer to the following: Figures 14-19Based on the fluoride-containing wastewater treatment device provided in the first embodiment of this application, the second embodiment of this application proposes another fluoride-containing wastewater treatment device. The second embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the separate implementation of the first embodiment.

[0076] Specifically, the difference in the fluoride-containing wastewater treatment device provided in the second embodiment of this application is that a drive mechanism 8 is fixedly installed on one side of the inner wall of each of the two carrier boxes 16. The drive mechanism 8 includes a drive motor 801, which is fixedly installed on one side of the inner wall of the carrier box 16. A cam 802 is fixedly installed on the output shaft of the drive motor 801.

[0077] Bearings 14 are fixedly installed at both ends of the first rotating shaft 303 and the second rotating shaft 306. The four bearings 14 are respectively adapted to be installed with the two cams 802. A pH detector 13 is installed inside the regulating tank 201.

[0078] One side of the three-way valve 503 is connected to a backflushing mechanism 9. The backflushing mechanism 9 includes a backflushing pipe 901. One end of the backflushing pipe 901 is connected to one side of the three-way valve 503, and the other end of the backflushing pipe 901 is connected to a backflushing box 902. The backflushing box 902 is located on the ground. A backflushing port 7 is provided on the surface of the bottom cover 12. The surface of the water outlet shaft 402 is threaded. A lifting mechanism 10 is threadedly connected to the surface of the water outlet shaft 402. The lifting mechanism 10 includes a lifting plate 1002. The interior of the lifting plate 1002 is threadedly connected to the surface of the water outlet shaft 402. Four limiting posts 1001 are fixedly installed on the top of the bottom cover 12. The surfaces of the four limiting posts 1001 are slidably connected to the interior of the lifting plate 1002. The water outlet plate 403 is adapted to the backflushing port 7. The bottom of the backflushing port 7 is connected to a recovery box 19.

[0079] In actual use, the backwash tank 902 is equipped with a submersible pump, and the internal solution is clean water; the reagent tank 203 is equipped with a submersible pump; and the pH meter 13 is connected to an external control system.

[0080] The working principle of the fluoride-containing wastewater treatment device provided in this embodiment is as follows:

[0081] First, the pH value of the fluoride-containing wastewater inside the equalization tank 201 is detected by the pH meter 13. The submersible pump in the reagent tank 203 is automatically started to supply sodium hydroxide solution. When the two adsorption motors 311 are started, the two drive motors 801 are also started. The two drive motors 801 drive the two cams 802 to rotate. The two cams 802 contact the four bearings 14, which drive the first rotating shaft 303 and the second rotating shaft 306 to move up and down. At this time, the wastewater can be better contacted. At the same time, the MOF adsorbent inside the first adsorption box 304 and the second adsorption box 307 is vibrated to avoid sticking and improve working efficiency. At the same time, the wastewater can be better mixed.

[0082] Then, after the purified water is discharged, the filter screen 502 is backwashed. The submersible pump in the backwash box 902 is started to supply clean water through the three-way valve 503 to backwash the filter screen 502. At this time, the lifting plate 1002, which is threadedly connected to the water outlet shaft 402, is raised. The motor 401 continues to work and drives the water outlet plate 403 to rotate while opening the backwash port 7. At this time, the lifting plate 1002 reaches the target height. The backwash water flows through the filter screen 502. The height raised by the lifting plate 1002 prevents the backwash contaminated water from contaminating the adsorption mechanism 3. After passing through the backwash port 7, the backwash water is discharged into the inside of the recovery box 19 for treatment.

[0083] Finally, after the process is completed, the motor 401 drives the water outlet plate 403 and the lifting plate 1002 to reset respectively.

[0084] Compared with related technologies, the fluoride-containing wastewater treatment device provided in this embodiment has the following beneficial effects:

[0085] The drive motor 801 drives the cam 802 to move the first adsorption box 304 and the second adsorption box 307 up and down and oscillate, respectively. This not only makes the contact between the MOF adsorbent and the wastewater more sufficient, but also effectively prevents the MOF adsorbent from caking and sticking, maintaining its loose and porous high-activity state. This significantly improves the adsorption rate and the removal efficiency of fluoride ions. By automatically raising the lifting plate 1002 and opening the backwash port 7 during backwashing, the backwash zone is physically separated from the core adsorption mechanism 3. This effectively prevents the backwash wastewater containing high concentrations of pollutants from flowing back into the adsorption mechanism 3, thus preventing secondary pollution of the adsorption mechanism 3 and damage to the MOF adsorbent. The system is designed to prevent damage and ensure continuous and stable operation. Wastewater generated by backwashing is collected in recycling tank 19 for specialized treatment, achieving graded treatment and resource utilization of wastewater. This avoids water waste and the environmental risks of direct discharge, aligning with the concept of green environmental protection. The backwashing function can promptly remove impurities trapped by filter screen 502, keeping it unobstructed and effectively preventing clogging. This extends the service life of the filter screen and the entire system. Fluoride-containing wastewater becomes purified water after treatment. When discharged, it is filtered by filter screen 502, which can trap detached solid impurities and any MOF adsorbent that may overflow. This ensures the quality of the effluent and achieves effective recovery of the adsorbent, avoiding material loss and secondary pollution.

[0086] A method for treating fluoride-containing wastewater

[0087] Please refer to the following: Figure 20 A method for treating fluoride-containing wastewater includes the following steps:

[0088] S1: Zirconium tetrachloride ( ) and 2-aminoterephthalic acid ( Add N,N-dimethylformamide ( In the solution, ultrasonic treatment is performed until complete dissolution is obtained;

[0089] S2: Add acetic acid to the dissolved solution and stir magnetically to form a homogeneous solution, thus obtaining a mixed solution;

[0090] S3: Transfer the mixed solution to a 50ml polytetrafluoroethylene-lined high-pressure reactor, seal it, and place it in an oven;

[0091] S4: After the reaction is complete, allow the mixture to cool to room temperature naturally, then centrifuge to collect the white precipitate.

[0092] S5: The white precipitate was washed successively with DMF and anhydrous ethanol, and then dried under vacuum to obtain... powder;

[0093] S6: Add MOF adsorbent ( Add to a fluoride-containing solution, maintain constant temperature and shake, centrifuge, collect the supernatant, and determine... concentration;

[0094] S7: Selective testing, in the presence of... , Repeat step S6 in the mixed solution to calculate the adsorption capacity and selectivity coefficient;

[0095] S8: Regeneration treatment, immersing the adsorbed MOF in... In the solution, after shaking, the solid is separated by centrifugation, washed with deionized water until neutral, and then placed in an oven to dry;

[0096] S9: Cyclic test, repeat the adsorption experiments of S6 and S7 5 times, and calculate the capacity retention rate.

[0097] Zirconium tetrachloride in S1 ( ) is 1 mmol, 2-aminoterephthalic acid ( In step S2, 1.2 mmol of MOF was added to 40 ml of DMF, and the mixture was sonicated for 10 min. In step S3, 3 ml of acetic acid was added, and the mixture was magnetically stirred for 30 min. In step S3, the reaction temperature was set at 120 °C, and the reaction time was 24 h. In step S4, the mixture was centrifuged for 10 min at 8000 rpm. In step S5, the mixture was washed three times each with DMF and anhydrous ethanol, and then vacuum dried at 60 °C for 12 h. In step S6, 0.1 g of MOF adsorbent was added to 100 ml of fluorine-containing solution and shaken at 25 °C for 12 h. Selectivity coefficient: Adsorption capacity: Wherein, C0 (initial concentration), Ce (equilibrium concentration), V (solution volume, L), and m (adsorbent mass, g); the MOF saturated in S8 is 0.1 g. The solution is 0.1 mol / L, 50 ml, shaken at 25℃ for 2 h, and dried at 60℃. The formula for calculating the volume retention rate in S9 is: Retention Rate ;in, This represents the initial adsorption capacity. Let n be the capacity of the nth iteration.

[0098] First Embodiment

[0099] amino functionalization Synthesis and conventional water fluoride removal.

[0100] 0.233g 1mmol With 0.242g 1.2mmol Place the solid in a 100ml beaker, add 40ml of DMF adsorbent, place the beaker in an ultrasonic cleaner, and sonicate for 10 minutes until the solid is completely dissolved to form a transparent solution.

[0101] Measure 3 ml of acetic acid using a graduated cylinder and slowly add it dropwise to the above solution. At the same time, stir continuously with a magnetic stirrer (500 rpm) for 30 minutes to ensure uniform mixing and obtain a mixed solution.

[0102] Transfer the mixed solution into a 50ml polytetrafluoroethylene liner, ensuring the liquid level does not exceed 80% of the liner's volume; install the liner into the stainless steel high-pressure reactor shell, and tighten the bolts to a torque of 15 N·m to ensure a tight seal.

[0103] Place the reactor in a preheated drying oven at 120°C and react for 24 hours, with a temperature fluctuation range of 2°C, to avoid local overheating that could lead to ligand decomposition.

[0104] After the reaction is complete, allow the reactor to cool naturally to room temperature (approximately 25°C), open the reactor, transfer the suspension in the liner to a 50ml centrifuge tube, centrifuge at 8000rpm for 10min, separate the supernatant, and take the white precipitate.

[0105] Add 40 ml of DMF to the precipitate, vortex for 5 min, centrifuge at 8000 rpm for 10 min, repeat 3 times to remove unreacted matter; then wash 3 times with 40 ml of anhydrous ethanol each time to remove residual DMF and byproducts. .

[0106] The washed white precipitate was spread evenly on a petri dish and placed in a vacuum drying oven at 60°C for 12 hours to obtain... Powder, yield approximately 0.18g, yield 85%.

[0107] Weigh 0.442 g of sodium fluoride, dissolve it in 1 L of deionized water, and prepare a solution with a concentration of 1000 mg / L. Stock solution. Dilute 20 ml of the stock solution to 1 L to obtain 20 mg / L. The working solution is 0.1 mol / L. / Adjust the pH to 5.

[0108] Weigh out 0.1g Add the powder to a 250ml Erlenmeyer flask and pour in 100ml of water. The working solution was placed in a constant temperature shaker (25℃, 200rpm) and shaken for 12 hours.

[0109] The supernatant was filtered through a 0.22 filter membrane, and the equilibrium concentration Ce was determined using a fluoride ion selective electrode.

[0110] Second Embodiment

[0111] Defect type Microwave synthesis and high-concentration fluorine adsorption.

[0112] Weigh according to the proportions in Example 1 and Dissolve in 40 ml DMF, add 5 ml acetic acid, and stir magnetically for 30 min. Transfer the mixture to a 100 ml microwave-safe reaction tube, seal it, and place it in a microwave cavity.

[0113] The reaction parameters are set as follows: power 300W, temperature 120℃, pressure limit 20 bar, and reaction time 2 hours. The microwave cavity has a built-in infrared temperature sensor for real-time monitoring to prevent localized overheating.

[0114] 1g microwave-synthesized The powder and 5 ml of acetic acid were added to a 50 ml round-bottom flask; a reflux apparatus was set up, and the mixture was heated under reflux in an oil bath at 80 °C for 4 h; the solid was collected by centrifugation, washed three times with ethanol, and dried under vacuum at 60 °C for 12 h to obtain the defective type. .

[0115] Prepare 100ml / L Adjust the pH of the solution to 3, and take 0.1g of the defective type. Add to 100 ml of high-fluoride solution and shake at 25 °C for 12 h.

[0116] Compared with related technologies, the fluoride-containing wastewater treatment method provided by the present invention has the following beneficial effects:

[0117] By introducing amino ligands and optimizing the synthesis process, this material combines high fluorine adsorption capacity, wide pH stability, and strong anti-interference ability, solving the problems of low adsorption capacity, inactivation under acidic conditions, and poor selectivity of traditional adsorbents (such as activated alumina).

[0118] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A fluoride-containing wastewater treatment device, characterized in that, include: A tank placed on the ground, with a top cover movably installed on the top of the tank, a bottom cover fixedly installed on the bottom of the tank, an outlet on the surface of the bottom cover, vertical grooves on both sides of the tank, and a carrying box fixedly installed on both sides of the tank. The regulating mechanism is used to pre-regulate the fluoride-containing wastewater; An adsorption mechanism is fixedly installed at the bottom of the inner walls of the two carrying boxes. The adsorption mechanism includes telescopic columns, two of which are fixedly installed at the bottom of the inner walls of the two carrying boxes respectively. A support plate is fixedly installed at the top of each of the two telescopic columns. A first rotating shaft and a second rotating shaft are rotatably installed between the two support plates. Four first adsorption boxes are snapped onto the surface of the first rotating shaft inside the tank through a fixing component. Several first through holes are opened on the surface of the first adsorption box. Four second adsorption boxes are snapped onto the surface of the second rotating shaft inside the tank through a fixing component. Several second through holes are opened on the surface of the second adsorption box. Two baffles are fixedly installed on the surfaces of the first and second rotating shafts. The two baffles are adapted to the two vertical grooves. Fixing columns are fixedly installed on both sides of the four first adsorption boxes and the four second adsorption boxes. The fixing columns are adapted to the fixing component. An adsorption motor is fixedly installed at one end of each of the first and second rotating shafts through a bracket. A water outlet mechanism, which is used to open the water outlet to allow water to flow out; A drainage mechanism for recycling treated water; A water distribution mechanism, used to distribute water to the tank; The water outlet mechanism is fixedly installed at the bottom of the bottom cover. The water outlet mechanism includes a motor, which is fixedly installed at the bottom of the bottom cover via a bracket. The output end of the motor is fixedly connected to a water outlet shaft, which passes through the bottom of the bottom cover and extends into the interior of the tank. A water outlet plate is fixedly installed on the surface of the water outlet shaft inside the tank. The water outlet plate is adapted to the water outlet. The drainage mechanism is connected to the water outlet and includes a drain pipe. The inlet end of the drain pipe is connected to the water outlet. A filter screen is installed inside the drain pipe. The drain pipe is connected to a drain bucket via a three-way valve. One side of the three-way valve is connected to a backflushing mechanism, which includes a backflushing pipe. One end of the backflushing pipe is connected to one side of the three-way valve, and the other end of the backflushing pipe is connected to a backflushing box. The backflushing box is located on the ground. A backflushing port is provided on the surface of the bottom cover. A thread is provided on the surface of the water outlet shaft. A lifting mechanism is threadedly connected to the surface of the water outlet shaft. The lifting mechanism includes a lifting plate. The interior of the lifting plate is threadedly connected to the surface of the water outlet shaft. Four limiting posts are fixedly installed on the top of the bottom cover. The surfaces of the four limiting posts are slidably connected to the interior of the lifting plate. The water outlet plate is adapted to the backflushing port. A recovery box is connected to the bottom of the backflushing port.

2. The fluoride-containing wastewater treatment device according to claim 1, characterized in that, The regulating mechanism is connected to the top cover. The regulating mechanism includes an regulating pool and an inlet pipe. The outlet end of the inlet pipe is connected to the top cover. The regulating pool is located on the ground. A wastewater pipe is connected to one side of the regulating pool. A medicine tank is connected to one side of the regulating pool through a medicine inlet pipe. The medicine tank is located on the ground. A water pump is connected to the bottom of the regulating pool through a water pipe. The outlet end of the water pump is connected to the inlet end of the inlet pipe.

3. The fluoride-containing wastewater treatment device according to claim 1, characterized in that, Both ends of the first and second rotating shafts are provided with four placement slots. The placement slots are adapted to be installed with the fixing posts and the fixing components. Thirty-two fixing components are respectively fixedly installed on both sides of the inner wall of the sixteen placement slots. Each fixing component includes a fixing plate, which is fixedly installed on one side of the inner wall of the placement slot. A locking block is fixedly connected to one side of the fixing plate by a spring. The locking block is adapted to be installed with the fixing posts.

4. The fluoride-containing wastewater treatment device according to claim 1, characterized in that, The water distribution mechanism is connected to the bottom of the upper cover. The water distribution mechanism includes a connecting pipe, which is connected to the bottom of the upper cover. The bottom end of the connecting pipe is connected to a water distribution tank. The outside of the water distribution tank is connected to six water distribution pipes, and the bottom of each of the six water distribution pipes is provided with several water distribution holes.

5. The fluoride-containing wastewater treatment device according to claim 2, characterized in that, A drive mechanism is fixedly installed on one side of the inner wall of each of the two carrier boxes. The drive mechanism includes a drive motor, which is fixedly installed on one side of the inner wall of the carrier box. A cam is fixedly installed on the output shaft of the drive motor.

6. The fluoride-containing wastewater treatment device according to claim 5, characterized in that, Bearings are fixedly installed at both ends of the first and second rotating shafts. The four bearings are respectively adapted to be installed with the two cams. A pH detector is installed inside the regulating tank.

7. A method for treating fluoride-containing wastewater, requiring the use of a fluoride-containing wastewater treatment device as described in any one of claims 1-6, characterized in that, Includes the following steps: S1: Zirconium tetrachloride ( ) and 2-aminoterephthalic acid ( Add N,N-dimethylformamide ( In the solution, ultrasonic treatment is performed until complete dissolution is obtained; S2: Add acetic acid to the dissolved solution and stir magnetically to form a homogeneous solution, thus obtaining a mixed solution; S3: Transfer the mixed solution to a 50ml polytetrafluoroethylene-lined high-pressure reactor, seal it, and place it in an oven; S4: After the reaction is complete, allow the mixture to cool to room temperature naturally, then centrifuge to collect the white precipitate. S5: The white precipitate was washed successively with DMF and anhydrous ethanol, and then dried under vacuum to obtain... powder; S6: Add MOF adsorbent Add to a fluoride-containing solution, maintain constant temperature and shake, centrifuge, collect the supernatant, and determine the concentration. concentration; S7: Selective testing, in the presence of... , Repeat step S6 in the mixed solution to calculate the adsorption capacity and selectivity coefficient; S8: Regeneration treatment, immersing the adsorbed MOF in... In the solution, after shaking, the solid is separated by centrifugation, washed with deionized water until neutral, and then placed in an oven to dry; S9: Cyclic test, repeat the adsorption experiments of S6 and S7 5 times, and calculate the capacity retention rate.

8. The method for treating fluoride-containing wastewater according to claim 7, characterized in that, Zirconium tetrachloride in S1 ( ) is 1 mmol, 2-aminoterephthalic acid ( In step S2, 1.2 mmol of MOF was added to 40 ml of DMF, and the mixture was sonicated for 10 min. In step S3, 3 ml of acetic acid was added, and the mixture was magnetically stirred for 30 min. In step S3, the reaction temperature was set at 120 °C, and the reaction time was 24 h. In step S4, the mixture was centrifuged for 10 min at 8000 rpm. In step S5, the mixture was washed three times each with DMF and anhydrous ethanol, and then vacuum dried at 60 °C for 12 h. In step S6, 0.1 g of MOF adsorbent was added to 100 ml of fluorine-containing solution and shaken at 25 °C for 12 h. Selectivity coefficient: Adsorption capacity: Wherein, C0 is the initial concentration, Ce is the equilibrium concentration, V is the solution volume in L, and m is the adsorbent mass in g; the MOF saturated in S8 is 0.1 g. The solution is 0.1 mol / L, 50 ml, shaken at 25℃ for 2 h, and dried at 60℃. The formula for calculating the volume retention rate in S9 is: Retention Rate ;in, This represents the initial adsorption capacity. Let n be the capacity of the nth iteration.

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