A fluorine removal adsorbent preparation method and a fluorine removal adsorbent preparation sampling device

Abstract

The application provides a kind of fluorine removal adsorbent preparation detection sampling equipment and fluorine removal adsorbent preparation method, relating to sampling and detection technical field, including sampling box, drive mechanism and sampling mechanism;The drive mechanism includes two slide rails, drive frame and two mounting brackets, the inner side of two The mounting bracket is vertically slidably connected with jacking frame, and the top of two The jacking frame is fixed with mounting plate. This scheme ultimately realizes the use of multiple sampling tubes, by switching the working position of the drive disc and the extruding wheel, multiple sampling of the filtrate is realized, the sampling efficiency of the filtrate is improved, and during the switching process, the working state of the sampling tube is switched, the sampling tube is switched from the sampling state to the cleaning state, to avoid the contamination of the new sample by the residual filtrate in the sampling tube during the secondary sampling, thereby improving the accuracy of the detection value, and avoiding the problem of product purity reduction caused by inaccurate detection data.

Description

Technical Field

[0001] This invention relates to the field of sampling and detection technology, and in particular to a sampling and detection device for the preparation of a defluorination adsorbent and a method for preparing the defluorination adsorbent. Background Technology

[0002] Fluorides are widely present in industrial wastewater, such as in industries like electroplating, aluminum electrolysis, photovoltaics, and phosphate fertilizer production, as well as in groundwater environments. Their concentration often exceeds national emission standards. Long-term consumption of high-fluoride water can lead to health problems such as dental fluorosis and skeletal fluorosis. If fluorides in industrial wastewater are discharged directly without treatment, they will cause irreversible damage to the ecosystem. Currently, adsorbents are commonly used to adsorb fluoride ions in wastewater.

[0003] In related technologies, some existing defluorination adsorbents require rinsing the filter cake with distilled water during preparation, aiming to achieve a neutral pH in the filtrate. Improper operation of this process can lead to a decrease in product purity and even equipment corrosion. Therefore, sampling equipment is needed to sample the filtrate, and intelligent detection equipment is required to monitor the pH value of the filtrate. However, existing sampling equipment for adsorbent preparation is not convenient for multiple sampling of the filtrate. To achieve a neutral pH in the filtrate, the filter cake needs to be rinsed multiple times, requiring sampling after each rinse. Existing sampling equipment leaves residue from the previous sample in the tube after each sampling, causing contamination during secondary sampling and resulting in measured values ​​that are often lower than the actual values.

[0004] Therefore, it is necessary to provide a detection and sampling device for the preparation of defluorination adsorbents and a method for preparing defluorination adsorbents to solve the above-mentioned technical problems. Summary of the Invention

[0005] This invention provides a detection and sampling device for the preparation of defluorination adsorbents and a method for preparing defluorination adsorbents, which solves the technical problem that some existing adsorbent sampling devices in the related technology are not convenient for multiple sampling of the filtrate, and that multiple sampling will cause pollution.

[0006] To solve the above-mentioned technical problems, the detection and sampling device for the preparation of fluoride adsorbents provided by the present invention includes a sampling box, a driving mechanism, and a sampling mechanism;

[0007] The drive mechanism includes two slide rails, a drive frame, and two mounting brackets. A lifting frame is vertically slidably connected to the inner side of each of the two mounting brackets. A mounting plate is fixed to the top of each of the two lifting frames. A spring is sleeved on the surface of each of the two lifting frames and at the bottom of the mounting bracket. A rotating wheel is rotatably connected to the inner side of the bottom of each of the two lifting frames. The bottom of each of the two rotating wheels is in contact with the top of the drive frame.

[0008] The sampling mechanism includes a mounting plate and two drive plates. Three mounting pads are fixed to the inner wall of the mounting plate, and sampling tubes are provided on the inner side of each of the three mounting pads. Extrusion rollers are rotatably connected to the surfaces of the two drive plates. Rotating shafts are vertically fixed to the inner sides of the two drive plates. The bottom end of the rotating shafts is rotatably connected to the mounting plate. A drive motor for driving the rotating shafts to rotate is provided at the bottom of the mounting plate.

[0009] Preferably, each of the two slide rails has a sliding seat slidably connected to its surface, the top of the two sliding seats is fixedly connected to the bottom of the drive frame, an electric telescopic rod is fixedly provided at the bottom of the inner wall of the sampling box, the output end of the electric telescopic rod is fixedly connected to the drive frame, and the bottom of the two slide rails and the mounting bracket is fixedly connected to the bottom of the inner wall of the sampling box.

[0010] Preferably, the three mounting pads and sampling tubes are equidistantly distributed, the distance between the two drive discs is the same as the distance between the mounting pads, the sampling tube located inside the mounting disc is a flexible tube, the output end is a pipe, the output end is a freely bendable corrugated tube, and the top and bottom of the extrusion wheel are both designed at bevel angles.

[0011] Preferably, a detection mechanism is rotatably connected to the inner wall of the sampling box. The detection mechanism includes a ball screw rotatably connected to the inner wall of the sampling box. A movable block is provided on the surface of the ball screw. A movable seat is fixed at the bottom of the movable block. A bracket is fixed on the right side of the top of the movable seat. A pH meter is rotatably connected to the inner side of the bracket. A detection motor for driving the ball screw to rotate is provided on the front of the sampling box.

[0012] Preferably, a sample retention mechanism is fixedly provided on the right side of the bottom of the inner wall of the sampling box. The sample retention mechanism includes two guide rails fixedly provided on the right side of the bottom of the inner wall of the sampling box. A moving platform is slidably connected to the surfaces of the two guide rails. A sample retention cup is provided on the right side of the top of the moving platform. A drive wheel is rotatably connected to the left side of the top of the moving platform. A total of three sets of sample retention mechanisms are provided.

[0013] Preferably, both the bottom of the moving platform and the inner wall of the sampling box are provided with through holes. When the moving platform moves to the far right, the through hole in the moving platform coincides with the through hole at the bottom of the inner wall of the sampling box. The bottom of the moving base is provided with a wedge-shaped protrusion that works in conjunction with the drive wheel.

[0014] Preferably, a wiping mechanism is fixedly provided on the top of the sampling box. The wiping mechanism includes two gear plates fixedly provided on the top of the sampling box. A connecting shaft is provided on the inner side of the top of the sampling box. A gear is fixedly provided on the top of the connecting shaft. During the movement of the gear, it meshes with the two gear plates in sequence. The bottom end of the connecting shaft is fixedly connected to the top of the pH meter. Two sets of cleaning racks are fixedly provided on the bottom of the inner wall of the sampling box.

[0015] Preferably, a cleaning tube is fixed to the back of the inner wall of the sampling box, and three cleaning nozzles are connected to the surface of the cleaning tube. Three drain pipes are connected to the right side of the bottom of the sampling box.

[0016] Preferably, a display controller is provided on the top of the sampling box, and a buzzer is provided on the rear side of the top of the sampling box. The display controller is electrically connected to the pH meter and the buzzer via wires, and multiple support legs are fixed at the bottom of the sampling box.

[0017] A method for preparing a fluoride removal adsorbent includes the following steps:

[0018] Step S1: Preparation of polycarboxylic acids 1,3,5-BTC:

[0019] S11. Place aromatic hydrocarbons and sulfuric acid in a three-necked flask and place in an ice bath. Add concentrated sulfuric acid dropwise to the solution after the ice bath. After the addition is complete, remove the ice bath, heat and stir. After the solution changes color, heat again and reflux the reaction.

[0020] S12. After cooling the reaction solution, add ice and wait for the precipitate to precipitate. Let it stand and filter to obtain the crude product. Wash the crude product with distilled water until the pH of the filtrate is 7. During the washing process, use a detection and sampling device to detect the pH value of the filtrate.

[0021] S13. Dissolve the crude product in water, filter, cool the filtrate, let it stand to crystallize, put the crystals into a vacuum drying oven, and dry to obtain the product;

[0022] Step S2, Preparation of MIL-96 (AL):

[0023] S21. Dissolve a certain amount of aluminum salt in deionized water and stir until the solid is completely dissolved. Add the prepared 1,3,5-BTC to the solution and stir until the solid is completely dissolved.

[0024] S22. The mixed solution is loaded into a polytetrafluoroethylene-lined reactor and subjected to hydrothermal reaction in a forced-air drying oven.

[0025] S23. Wash the product and dry it in an oven to obtain the final product.

[0026] Compared with related technologies, the detection and sampling equipment for preparing defluorination adsorbents and the method for preparing defluorination adsorbents provided by the present invention have the following beneficial effects:

[0027] During operation, this equipment extends via an electric telescopic rod, driving the drive frame to move backward. Under the action of the rotating wheel, lifting frame, and mounting plate, the working positions of the drive disc and squeezing wheel are switched. The squeezing wheel continuously squeezes and releases the sampling tube, drawing the filtrate into the sampling box for testing. Utilizing multiple sampling tubes, and by switching the working positions of the drive disc and squeezing wheel, multiple samples of the filtrate can be taken, improving sampling efficiency. During the switching process, the working state of the sampling tube is also switched, transitioning it from sampling mode to a clean mode. This prevents residual filtrate in the sampling tube from contaminating the new sample during secondary sampling, thereby improving the accuracy of the test values ​​and avoiding the problem of decreased product purity due to inaccurate test data. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0029] Figure 1 The optimal structural schematic diagram provided for this invention;

[0030] Figure 2 for Figure 1 The diagram shows a cross-sectional view of the sampling box.

[0031] Figure 3 A schematic diagram of the driving mechanism and sampling mechanism provided by the present invention;

[0032] Figure 4 A schematic diagram showing the state in which the electric telescopic rod, provided by the present invention, drives the drive frame to move backward, causing the rotating wheel and the lifting frame to drive the mounting plate to move upward;

[0033] Figure 5 for Figure 3 The enlarged structural diagram at point A is shown below;

[0034] Figure 6 for Figure 3 The diagram shows a structural schematic of the cross-sectional view of the mounting plate.

[0035] Figure 7 This is a schematic diagram of the detection mechanism provided by the present invention;

[0036] Figure 8This is a schematic diagram of the sample retention mechanism provided by the present invention;

[0037] Figure 9 for Figure 7 The diagram shows the structure of the movable base;

[0038] Figure 10 The diagram shows the state in which the ball screw rotation drives the moving seat to move backward, and the moving platform drives the sample cup to move to the right under the action of the drive wheel.

[0039] Figure 11 A schematic diagram of the wiping mechanism provided by the present invention;

[0040] Figure 12 The diagram shows the state provided by the present invention, in which the ball screw rotates to drive the moving seat to move backward, and after the gear contacts the gear plate, it drives the pH meter to rotate through the connecting shaft.

[0041] Explanation of icon numbers:

[0042] 1. Sampling box;

[0043] 2. Drive mechanism; 21. Slide rail; 22. Drive frame; 23. Mounting bracket; 24. Lifting frame; 25. Mounting plate; 26. Spring; 27. Rotating wheel; 28. Sliding seat; 29. ​​Electric telescopic rod;

[0044] 3. Sampling mechanism; 31. Mounting plate; 32. Drive plate; 33. Mounting pad; 34. Sampling tube; 35. Extrusion roller; 36. Rotating shaft; 37. Drive motor;

[0045] 4. Testing mechanism; 41. Ball screw; 42. Moving block; 43. Moving base; 44. Bracket; 45. pH meter; 46. Testing motor;

[0046] 5. Sample retention mechanism; 51. Guide rail; 52. Moving platform; 53. Sample cup; 54. Drive wheel;

[0047] 6. Wiping mechanism; 61. Gear plate; 62. Connecting shaft; 63. Gear; 64. Cleaning rack;

[0048] 7. Cleaning pipe; 8. Cleaning nozzle; 9. Drain pipe;

[0049] 10. Display controller; 11. Buzzer; 12. Support leg.

[0050] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0051] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0052] This invention provides a detection and sampling device for the preparation of a fluoride-removing adsorbent and a method for preparing the fluoride-removing adsorbent.

[0053] First embodiment:

[0054] Please see Figures 1 to 6 A detection and sampling device for the preparation of fluoride adsorbent, comprising a sampling box 1, a driving mechanism 2 and a sampling mechanism 3;

[0055] The drive mechanism 2 includes two slide rails 21, a drive frame 22, and two mounting brackets 23. The inner sides of the two mounting brackets 23 are vertically slidably connected to lifting frames 24. The tops of the two lifting frames 24 are fixed with mounting plates 25. The surfaces of the two lifting frames 24 and the bottoms of the mounting brackets 23 are fitted with springs 26. The inner sides of the bottoms of the two lifting frames 24 are rotatably connected to rotating wheels 27. The bottoms of the two rotating wheels 27 are in contact with the tops of the drive frame 22.

[0056] Sliding seats 28 are slidably connected to the surfaces of the two slide rails 21. The tops of the two sliding seats 28 are fixedly connected to the bottom of the drive frame 22. An electric telescopic rod 29 is fixedly provided at the bottom of the inner wall of the sampling box 1. The output end of the electric telescopic rod 29 is fixedly connected to the drive frame 22. The bottoms of the two slide rails 21 and the mounting bracket 23 are fixedly connected to the bottom of the inner wall of the sampling box 1.

[0057] Please combine Figure 4 and Figure 5 : Start the electric telescopic rod 29. The electric telescopic rod 29 extends and drives the drive frame 22 to move backward, so that the two sliding seats 28 slide backward on the surface of the slide rail 21. The drive frame 22 moves backward and drives the two rotating wheels 27 to move upward. The two rotating wheels 27 drive the mounting plate 25 to move upward through the lifting frame 24, so that the spring 26 retracts.

[0058] Furthermore, when the electric telescopic rod 29 retracts, it will simultaneously drive the drive frame 22 to move forward, causing the two sliding seats 28 to slide forward on the surface of the slide rail 21. The forward movement of the drive frame 22 cancels the compression on the rotating wheel 27, and under the action of the spring 26, the two lifting frames 24 will drive the mounting plate 25 to move downward.

[0059] The sampling mechanism 3 includes a mounting plate 31 and two drive plates 32. Three mounting pads 33 are fixedly provided on the inner wall of the mounting plate 31. Sampling tubes 34 are provided on the inner side of each of the three mounting pads 33. Extrusion rollers 35 are rotatably connected to the surfaces of the two drive plates 32. Rotation shafts 36 are vertically fixed on the inner side of the two drive plates 32. The bottom end of the rotation shafts 36 is rotatably connected to the mounting plate 25. A drive motor 37 for driving the rotation shafts 36 to rotate is provided at the bottom of the mounting plate 25.

[0060] Please combine Figure 3 and Figure 6 : Start the drive motor 37. The drive motor 37 rotates and drives the two drive disks 32 to rotate through the rotating shaft 36. The top drive disk 32 rotates and drives the two extrusion rollers 35 to extrude the bottom sampling tube 34. By rotating the two extrusion rollers 35 and continuously extruding and releasing the bottom sampling tube 34, a negative pressure is formed in the bottom sampling tube 34, and then the filtrate is pumped into the sampling box 1.

[0061] Furthermore, when the electric telescopic rod 29 extends and drives the drive frame 22 to move backward, the drive frame 22 lifts the mounting plate 25 upward through the rotating wheel 27 and the lifting frame 24, which in turn drives the drive motor 37 to move upward. The drive motor 37 then drives the two drive discs 32 and multiple squeezing wheels 35 to move upward through the rotating shaft 36, thereby adjusting the two top squeezing wheels 35 to the middle working position. During operation, the middle sampling tube 34 can be squeezed and released. At the same time, the bottom squeezing wheel 35 is adjusted to the bottom working position, and the bottom sampling tube 34 can be squeezed and released during operation. When the middle sampling tube 34 is used to sample the filtrate, the bottom sampling tube 34 extracts distilled water under the squeezing and releasing of the bottom squeezing wheel 35, thereby cleaning the inside of the pipe. Similarly, when the top sampling tube 34 is used to extract the filtrate, the middle sampling tube 34 is in a clean state.

[0062] Preferably, in order to ensure the accuracy of the test values, hot air can be introduced into the cleaned sampling tube 34 to dry the residual distilled water inside the sampling tube 34.

[0063] The three mounting pads 33 and sampling tubes 34 are equidistantly distributed. The distance between the two drive discs 32 is the same as the distance between the mounting pads 33. The sampling tube 34 located inside the mounting disc 31 is a flexible tube with a pipe at the output end. The output end is a freely bendable corrugated tube. The top and bottom of the extrusion wheel 35 are both designed at bevel angles.

[0064] In this embodiment, unlike existing sampling equipment for adsorbent preparation, this equipment extends via an electric telescopic rod 29, driving the drive frame 22 to move backward. Under the action of the rotating wheel 27, the lifting frame 24, and the mounting plate 25, the working positions of the drive disk 32 and the squeezing wheel 35 are switched. The squeezing wheel 35 continuously squeezes and releases the sampling tube 34, drawing the filtrate into the sampling box 1 for testing. By using multiple sampling tubes 34 and switching the working positions of the drive disk 32 and the squeezing wheel 35, multiple sampling of the filtrate can be achieved, improving the sampling efficiency. During the switching process, the working state of the sampling tube 34 is switched, changing the sampling tube 34 from the sampling state to the clean state. This avoids contamination of the new sample by residual filtrate in the sampling tube 34 during secondary sampling, thereby improving the accuracy of the detection values ​​and avoiding the problem of decreased product purity due to inaccurate detection data.

[0065] Second embodiment:

[0066] Please see Figures 7 to 10 The sampling box 1 is rotatably connected to the inner wall of the sampling box 1. The detection mechanism 4 includes a ball screw 41 rotatably connected to the inner wall of the sampling box 1. A moving block 42 is provided on the surface of the ball screw 41. A moving seat 43 is fixed at the bottom of the moving block 42. A bracket 44 is fixed on the right side of the top of the moving seat 43. A pH meter 45 is rotatably connected to the inner side of the bracket 44. A detection motor 46 for driving the ball screw 41 to rotate is provided on the front of the sampling box 1.

[0067] Please combine Figure 7 : Start the detection motor 46. The rotation of the detection motor 46 drives the ball screw 41 to rotate. The rotation of the ball screw 41 can then drive the moving seat 43, the bracket 44 and the pH meter 45 to move back and forth through the moving block 42, thereby flexibly adjusting the working position of the pH meter 45.

[0068] A sample retention mechanism 5 is fixedly provided on the right side of the bottom of the inner wall of the sampling box 1. The sample retention mechanism 5 includes two guide rails 51 fixedly provided on the right side of the bottom of the inner wall of the sampling box 1. A moving platform 52 is slidably connected to the surface of the two guide rails 51. A sample retention cup 53 is provided on the right side of the top of the moving platform 52. A drive wheel 54 is rotatably connected to the left side of the top of the moving platform 52. The sample retention mechanism 5 is provided in three sets.

[0069] Please combine Figures 8 to 10When sampling and testing are performed through the bottom sampling tube 34, the working positions of the moving seat 43, the bracket 44 and the pH meter 45 are switched backward by rotating the ball screw 41. During the backward movement of the moving seat 43, the driving wheel 54 will push the moving platform 52 to the right. The rightward movement of the moving platform 52 will drive the sample retention cup 53 to move to the right, thereby switching the sample retention cup 53 from the working position to the sample retention position.

[0070] Furthermore, when the sample cup 53 is switched to the sample retention position, the through hole in the moving platform 52 will coincide with the through hole at the bottom of the inner wall of the sampling box 1. At this time, the detection mechanism 4 has switched to the second detection position, and the bottom drive plate 32 and the squeezing wheel 35 are switched to the cleaning state to clean the bottom sampling tube 34. The clean distilled water is discharged through the output end of the bottom sampling tube 34 and then discharged from the sampling box 1 through the through hole and the drain pipe 9.

[0071] Both the mobile platform 52 and the sampling box 1 have through holes at their bottom. When the mobile platform 52 moves to the far right, the through hole in the mobile platform 52 coincides with the through hole at the bottom of the sampling box 1. The bottom of the mobile base 43 is provided with a wedge-shaped protrusion that works in conjunction with the drive wheel 54.

[0072] In this embodiment, when the detection motor 46 drives the ball screw 41 to rotate and switch the working positions of the moving seat 43, the bracket 44 and the pH meter 45 backward, the moving seat 43 moves through the drive wheel 54, causing the moving platform 52 to slide to the right on the surface of the guide rail 51, switching the sample cup 53 from the working position to the sample retention position. By setting the sample cup 53, the filtrate can be retained, which is convenient for tracing problems. At the same time, the filtrate can be centrally processed to avoid environmental pollution. After the sample cup 53 is switched to the sample retention position, the through hole in the moving platform 52 will coincide with the through hole at the bottom of the inner wall of the sampling box 1. When the bottom squeezing wheel 35 cleans the bottom sampling tube 34, distilled water can be discharged through the through hole and the drain pipe 9.

[0073] Third embodiment:

[0074] Please see Figure 1 , Figure 11 and Figure 12 The top of the sampling box 1 is fixedly provided with a wiping mechanism 6. The wiping mechanism 6 includes two gear plates 61 fixedly provided on the top of the sampling box 1. A connecting shaft 62 is provided on the inner side of the top of the sampling box 1. A gear 63 is fixedly provided at the top of the connecting shaft 62. During the movement of the gear 63, it meshes with the two gear plates 61 in sequence. The bottom end of the connecting shaft 62 is fixedly connected to the top of the pH meter 45. Two sets of cleaning racks 64 are fixedly provided at the bottom of the inner wall of the sampling box 1.

[0075] Please combine Figure 12When the detection motor 46 drives the ball screw 41 to rotate and switch the working positions of the moving seat 43, bracket 44 and pH meter 45 backward, the pH meter 45 will simultaneously drive the connecting shaft 62 and gear 63 to move backward. When the gear 63 contacts the gear plate 61, the gear 63 will drive the pH meter 45 to rotate through the connecting shaft 62. When the pH meter 45 moves to the inside of the cleaning rack 64, the gear 63 will drive the pH meter 45 to rotate, thus avoiding dead corners during the wiping process.

[0076] Preferably, when gear 63 contacts the front gear plate 61, gear 63 will drive pH meter 45 to rotate clockwise through connecting shaft 62; when gear 63 contacts the rear gear plate 61, gear 63 will drive pH meter 45 to rotate counterclockwise through connecting shaft 62.

[0077] A cleaning pipe 7 is fixedly installed on the back of the inner wall of the sampling box 1. Three cleaning nozzles 8 are connected to the surface of the cleaning pipe 7. Three drain pipes 9 are connected to the right side of the bottom of the sampling box 1.

[0078] The top of the sampling box 1 is provided with a display controller 10, and the rear side of the top of the sampling box 1 is provided with a buzzer 11. The display controller 10 is electrically connected to the pH meter 45 and the buzzer 11 through wires. The bottom of the sampling box 1 is fixed with multiple support legs 12.

[0079] Preferably, after the pH meter 45 detects the pH value of the filtrate, it transmits the data to the display controller 10, allowing the user to see the numerical result intuitively. The display controller 10 stores and records the data. The display controller 10 has a calculation function, which can not only display the numerical result but also process the data and calculate based on past data to determine approximately how many times the pH value of the filtrate reached neutral. When the pH value of the filtrate reaches neutral, the buzzer 11 will sound to remind the user.

[0080] In this embodiment, when the detection motor 46 drives the ball screw 41 to rotate and switch the working positions of the moving seat 43, the bracket 44 and the pH meter 45 backward, the pH meter 45 will simultaneously drive the connecting shaft 62 and the gear 63 to move backward. When the gear 63 contacts the gear plate 61, the gear 63 will drive the pH meter 45 to rotate through the connecting shaft 62. When the pH meter 45 moves to the inside of the cleaning rack 64, the gear 63 drives the pH meter 45 to rotate, avoiding dead corners during the wiping process, thereby ensuring detection accuracy and reducing the risk of cross-contamination of the filtrate.

[0081] Fourth embodiment:

[0082] A method for preparing a fluoride removal adsorbent includes the following steps:

[0083] Step S1: Preparation of polycarboxylic acids 1,3,5-BTC:

[0084] S11. Place aromatic hydrocarbons and sulfuric acid in a three-necked flask and place in an ice bath. Add concentrated sulfuric acid dropwise to the solution after the ice bath. After the addition is complete, remove the ice bath, heat and stir. After the solution changes color, heat again and reflux the reaction.

[0085] Preferably, the aromatic hydrocarbon can be m-trimethylbenzene. The solution is cooled to 0-5°C in an ice-water bath. When adding concentrated sulfuric acid, the dropping rate is controlled so that the reaction temperature does not exceed 10°C. The temperature is raised to 80°C and stirred for 4 hours. The solution color gradually turns orange-red. The temperature is raised again to 120°C and the reaction is refluxed for 6 hours.

[0086] S12. After cooling the reaction solution, add ice and wait for the precipitate to precipitate. Let it stand and filter to obtain the crude product. Wash the crude product with distilled water until the pH of the filtrate is 7. During the washing process, use a detection and sampling device to detect the pH value of the filtrate.

[0087] Preferably, the settling time is 1 hour;

[0088] S13. Dissolve the crude product in water, filter, cool the filtrate, let it stand to crystallize, put the crystals into a vacuum drying oven, and dry to obtain the product;

[0089] Preferably, the crude product is boiled in water for 5 minutes, filtered while hot, the filtrate is cooled to 4°C, left to stand for 12 hours, and then dried in a vacuum drying oven at 80°C for 12 hours.

[0090] Step S2, Preparation of MIL-96 (AL):

[0091] S21. Dissolve a certain amount of aluminum salt in deionized water and stir until the solid is completely dissolved. Add the prepared 1,3,5-BTC to the solution and stir until the solid is completely dissolved.

[0092] S22. The mixed solution is loaded into a polytetrafluoroethylene-lined reactor and subjected to hydrothermal reaction in a forced-air drying oven.

[0093] Preferably, the temperature of the forced-air drying oven is 210℃, and the hydrothermal reaction time is 4 hours;

[0094] S23. Wash the product and dry it in an oven to obtain the final product.

[0095] Preferably, the product is washed three times with deionized water and the oven temperature is 60℃.

[0096] In this embodiment, during the defluorination process, there is a synergistic effect between aluminum ions and organic ligands within the metal-organic framework structure of MIL-96(Al). This unique structural feature alters the electron cloud distribution on the material surface, significantly enhancing the adsorption affinity of MIL-96(Al) for fluoride ions and greatly strengthening its adsorption and activation capabilities for fluoride ions.

[0097] Meanwhile, MIL-96(Al) was loaded onto a specific porous carbon material. This carbon material possesses highly efficient electronic conductivity, and its abundant porous structure and ultra-large specific surface area allow for the firm attachment of MIL-96(Al) nanoclusters. This not only effectively reduces the mass transfer resistance of fluoride ions during adsorption but also allows more previously obscured adsorption active sites to be fully exposed, thereby greatly improving the fluoride removal activity of the MIL-96(Al) adsorbent and enhancing its stability.

[0098] Please refer to the reference again. Figures 1 to 12 The working principle of the detection and sampling device for the preparation of fluoride adsorbents provided by the present invention is as follows:

[0099] Step S1: Start the drive motor 37. The drive motor 37 rotates and drives the two drive disks 32 to rotate through the rotating shaft 36. The top drive disk 32 rotates and drives the two squeezing rollers 35 to squeeze the bottom sampling tube 34. By rotating the two squeezing rollers 35 and continuously squeezing and releasing the bottom sampling tube 34, a negative pressure is formed in the bottom sampling tube 34, which then draws the filtrate to the top of the front sample cup 53 and flows into the front sample cup 53 along the pH meter 45. When it flows over the surface of the pH meter 45, the filtrate is detected by the pH meter 45.

[0100] Step S2: Start the electric telescopic rod 29. The electric telescopic rod 29 extends and drives the drive frame 22 to move backward, so that the two sliding seats 28 slide backward on the surface of the slide rail 21. The drive frame 22 moves backward and drives the two rotating wheels 27 to move upward. The two rotating wheels 27 drive the mounting plate 25 to move upward through the lifting frame 24, and cause the spring 26 to retract.

[0101] The upward movement of the mounting plate 25 simultaneously drives the drive motor 37 to move upward. The drive motor 37 drives the two drive discs 32 and multiple extrusion rollers 35 to move upward via the rotating shaft 36, thereby adjusting the two top extrusion rollers 35 to the middle working position. During operation, they extrude and release the middle sampling tube 34. At the same time, the bottom extrusion rollers 35 are adjusted to the bottom working position, extruding and releasing the bottom sampling tube 34. When the middle sampling tube 34 is used to sample the filtrate, the bottom sampling tube 34 extracts distilled water under the extrusion and release of the bottom extrusion rollers 35, thereby cleaning the inside of the pipe. Similarly, when the top sampling tube 34 is used to extract the filtrate, the middle sampling tube 34 is in a clean state.

[0102] Step S3: Start the detection motor 46. The rotation of the detection motor 46 drives the ball screw 41 to rotate. The rotation of the ball screw 41 drives the moving seat 43, the bracket 44 and the pH meter 45 to move backward through the moving block 42, thereby adjusting the pH meter 45 to the top of the middle sample cup 53, ready for the next sampling.

[0103] In step S4, when the working positions of the movable seat 43, the bracket 44 and the pH meter 45 are switched backward by rotating the ball screw 41, the movable seat 43 will push the movable platform 52 to the right through the drive wheel 54 during the backward movement. The rightward movement of the movable platform 52 will drive the sample cup 53 to move to the right, thereby switching the sample cup 53 from the working position to the sample retention position.

[0104] When the sample cup 53 is switched to the sample retention position, the through hole in the moving platform 52 will coincide with the through hole at the bottom of the inner wall of the sampling box 1. At this time, the detection mechanism 4 has switched to the second detection position. The bottom drive plate 32 and the squeezing wheel 35 are switched to the cleaning state to clean the bottom sampling tube 34. The clean distilled water is discharged through the output end of the bottom sampling tube 34 and then discharged from the sampling box 1 through the through hole and the drain pipe 9. The top drive plate 32 and the squeezing wheel 35 are switched to the position of the middle sampling tube 34 for secondary sampling.

[0105] In step S5, when the detection motor 46 drives the ball screw 41 to rotate and switch the working positions of the moving seat 43, bracket 44 and pH meter 45 backward, the pH meter 45 will simultaneously drive the connecting shaft 62 and gear 63 to move backward. When the gear 63 contacts the gear plate 61, the gear 63 will drive the pH meter 45 to rotate through the connecting shaft 62. When the pH meter 45 moves to the inside of the cleaning rack 64, the gear 63 drives the pH meter 45 to rotate, thus avoiding dead corners during the wiping process.

[0106] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made under the concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A sampling and detection device for the preparation of a fluoride removal adsorbent, characterized in that, Includes sampling box, drive mechanism and sampling mechanism; The drive mechanism includes two slide rails, a drive frame, and two mounting brackets. A lifting frame is vertically slidably connected to the inner side of each of the two mounting brackets. A mounting plate is fixed to the top of each of the two lifting frames. A spring is sleeved on the surface of each of the two lifting frames located at the bottom of the mounting bracket. A rotating wheel is rotatably connected to the inner side of the bottom of each of the two lifting frames. The bottom of each of the two rotating wheels contacts the top of the drive frame. The drive frame has a trapezoidal structure. The sampling mechanism includes a mounting plate and two drive plates. Three mounting pads are fixedly provided on the inner wall of the mounting plate. A sampling tube, which is a flexible tube, is provided on the inner side of each of the three mounting pads. Extrusion rollers are rotatably connected to the surfaces of the two drive plates. A rotating shaft is vertically fixed on the inner side of the two drive plates. The bottom end of the rotating shaft is rotatably connected to the mounting plate. A drive motor for driving the rotating shaft to rotate is provided at the bottom of the mounting plate. Both slide rails are slidably connected to sliding seats, the tops of the two sliding seats are fixedly connected to the bottom of the drive frame, an electric telescopic rod is fixedly provided at the bottom of the inner wall of the sampling box, the output end of the electric telescopic rod is fixedly connected to the drive frame, and the bottoms of the two slide rails and the mounting bracket are fixedly connected to the bottom of the inner wall of the sampling box. The sampling box has a detection mechanism rotatably connected to its inner wall. The detection mechanism includes a ball screw rotatably connected to the inner wall of the sampling box. A moving block is provided on the surface of the ball screw. A moving seat is fixed at the bottom of the moving block. A bracket is fixed on the right side of the top of the moving seat. A pH meter is rotatably connected to the inner side of the bracket. A detection motor for driving the ball screw to rotate is provided on the front of the sampling box. A sample retention mechanism is fixedly provided on the right side of the bottom of the inner wall of the sampling box. The sample retention mechanism includes two guide rails fixedly provided on the right side of the bottom of the inner wall of the sampling box. A moving platform is slidably connected to the surfaces of the two guide rails. A sample retention cup is provided on the right side of the top of the moving platform. A drive wheel is rotatably connected to the left side of the top of the moving platform. The sample retention mechanism is provided in three sets. Both the mobile platform and the bottom of the inner wall of the sampling box have through holes. When the mobile platform moves to the far right, the through hole in the mobile platform coincides with the through hole at the bottom of the inner wall of the sampling box. The bottom of the mobile base is provided with a wedge-shaped protrusion that works with the drive wheel.

2. The detection and sampling device for preparing defluorination adsorbent according to claim 1, characterized in that, The three mounting pads are equidistantly distributed, the spacing between the two drive discs is the same as the spacing between the three mounting pads, and the top and bottom of the extrusion wheel are both designed at bevels.

3. The detection and sampling device for preparing defluorination adsorbent according to claim 1, characterized in that, The top of the sampling box is fixedly equipped with a wiping mechanism, which includes two gear plates fixedly mounted on the top of the sampling box. A connecting shaft is provided on the inner side of the top of the sampling box. A gear is fixedly mounted on the top of the connecting shaft. During the movement of the gear, it meshes with the two gear plates in sequence. The bottom end of the connecting shaft is fixedly connected to the top of the pH meter. Two sets of cleaning racks are fixedly mounted on the bottom of the inner wall of the sampling box.

4. The detection and sampling device for preparing defluorination adsorbent according to claim 1, characterized in that, A cleaning tube is fixed to the back of the inner wall of the sampling box, and three cleaning nozzles are connected to the surface of the cleaning tube. Three drain pipes are connected to the right side of the bottom of the sampling box.

5. The detection and sampling device for preparing defluorination adsorbent according to claim 1, characterized in that, The top of the sampling box is equipped with a display controller, and the rear side of the top of the sampling box is equipped with a buzzer. The display controller is electrically connected to the pH meter and the buzzer via wires, and multiple support legs are fixed at the bottom of the sampling box.

6. A method for preparing a fluoride removal adsorbent, characterized in that, The method for preparing the defluorination adsorbent includes the detection and sampling equipment as described in any one of claims 1-5, and includes the following steps: Step S1: Preparation of polycarboxylic acids 1,3,5-BTC: S11. Place aromatic hydrocarbons and sulfuric acid in a three-necked flask and place in an ice bath. Add concentrated sulfuric acid dropwise to the solution after the ice bath. After the addition is complete, remove the ice bath, heat and stir. After the solution changes color, heat again and reflux the reaction. S12. After cooling the reaction solution, add ice and wait for the precipitate to precipitate. Let it stand and filter to obtain the crude product. Wash the crude product with distilled water until the pH of the filtrate is 7. During the washing process, use a detection and sampling device to detect the pH value of the filtrate. S13. Boil the crude product in water to dissolve it, filter it while it is hot, cool the filtrate, let it stand to crystallize, put the crystals into a vacuum drying oven and dry them to obtain the product. Step S2, Preparation of MIL-96 (AL): S21. Dissolve a certain amount of aluminum salt in deionized water and stir until the solid is completely dissolved. Add the prepared 1,3,5-BTC to the solution and stir until the solid is completely dissolved. S22. The mixed solution is loaded into a polytetrafluoroethylene-lined reactor and subjected to hydrothermal reaction in a forced-air drying oven. S23. Wash the product and dry it in an oven to obtain the final product.

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