Detection sampling equipment for preparing defluorination adsorbent and preparation method of defluorination adsorbent

Abstract

The invention provides detection sampling equipment for preparing a defluorination adsorbent and a preparation method of the defluorination adsorbent, and relates to the technical field of sampling and detection, the detection sampling equipment comprises a sampling box, a driving mechanism and a sampling mechanism; the driving mechanism comprises two sliding rails, a driving frame and two mounting supports, jacking frames are vertically and slidably connected to the inner sides of the two mounting supports, and mounting plates are fixedly arranged at the tops of the two jacking frames. According to the scheme, multiple sampling of filtrate is finally realized by switching the working positions of a driving disc and an extrusion wheel by utilizing a plurality of arranged sampling pipes, the sampling efficiency of the filtrate is improved, switching of the working states of the sampling pipes is realized in the switching process, the sampling pipes are switched to a clean state from a sampling state, and the phenomenon that during secondary sampling, the sampling efficiency is greatly improved is avoided. Residual filtrate in the sampling tube pollutes a new sample, so that the accuracy of a detection value is improved, and the problem that the purity of a product is reduced due to inaccurate detection data is avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of sampling and detection, and in particular to a detection sampling device for preparing a defluorination adsorbent and a method for preparing the defluorination adsorbent. Background Art

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

[0003] In the related art, during the preparation process of some existing defluorination adsorbents, the filter cake needs to be rinsed with distilled water. The goal is to wash until the pH value of the filtrate reaches neutral. Improper operation of this process will lead to a decrease in product purity and even corrosion of the equipment. Therefore, it is necessary to use sampling equipment to sample the filtrate and use intelligent detection equipment to detect the pH value of the filtrate. During the sampling process, some existing adsorbent preparation sampling equipment is not convenient for multiple sampling of the filtrate. In order to achieve a neutral pH value of the filtrate, the filter cake needs to be rinsed multiple times, and sampling is required for each rinse. After sampling, the existing sampling equipment will have residual samples from the previous sample in the tube, which will cause contamination during the second sampling, resulting in the detection value being often smaller than the actual value.

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

[0005] The present invention provides a detection sampling device for preparing a defluorination adsorbent and a method for preparing a defluorination adsorbent, which solves the technical problem in the related art that some existing adsorbent sampling devices are inconvenient for multiple sampling of filtrate and multiple sampling may cause pollution.

[0006] In order to solve the above technical problems, the present invention provides a detection and sampling device for preparing a defluorination adsorbent, comprising a sampling box, a driving mechanism and a sampling mechanism; The driving mechanism includes two slide rails, a driving frame and two mounting brackets. The inner sides of the two mounting brackets are vertically slidably connected to the lifting frame. The tops of the two lifting frames are fixed with mounting plates. The surfaces of the two lifting frames and the bottoms of the mounting brackets are sleeved with springs. The inner sides of the bottoms of the two lifting frames are rotatably connected to rotating wheels. The bottoms of the two rotating wheels are in contact with the top of the driving frame. The sampling mechanism includes a mounting plate and two driving plates. Three mounting pads are fixedly provided on the inner wall of the mounting plate. Sampling tubes are provided on the inner sides of the three mounting pads. Extrusion wheels are rotatably connected to the surfaces of the two driving plates. A rotating shaft is vertically fixed on the inner sides of the two driving plates. The bottom end of the rotating shaft is rotatably connected to the mounting plate. A driving motor for driving the rotating shaft is provided at the bottom of the mounting plate.

[0007] Preferably, the surfaces of the two slide rails are slidably connected to sliding seats, the tops of the two sliding seats are fixedly connected to the bottom of the driving 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 driving 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.

[0008] Preferably, the three mounting pads and sampling tubes are equidistantly distributed, the spacing between the two driving disks is the same as the spacing between the mounting pads, the sampling tube located on the inner side of the mounting disk is a hose, 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 angled designs.

[0009] Preferably, the inner wall of the sampling box is longitudinally rotatably connected to a detection mechanism, and the detection mechanism includes a ball screw longitudinally 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 fixedly provided at the bottom of the moving block, a bracket is fixedly provided on the right side of the top of the moving seat, a pH meter is rotatably connected to the inner side of the bracket, and a detection motor for driving the ball screw to rotate is provided on the front of the sampling box.

[0010] Preferably, a sample retention mechanism is fixedly provided on the right side of the bottom of the inner wall of the sampling box, and 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, and the surfaces of the two guide rails are slidably connected to a moving platform, a sample retention cup is provided on the right side of the top of the moving platform, and a driving wheel is rotatably connected to the left side of the top of the moving platform. There are three groups of sample retention mechanisms in total.

[0011] Preferably, the bottom of the mobile platform and the inner wall of the sampling box are both provided with 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 seat is provided with a wedge-shaped protrusion for use with the driving wheel.

[0012] Preferably, a wiping mechanism is fixedly provided on the top of the sampling box, and 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, and a gear is fixedly provided on the top of the connecting shaft. During the movement of the gear, the gear engages with the two gear plates in turn, and 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 at the bottom of the inner wall of the sampling box.

[0013] Preferably, a cleaning pipe is fixedly provided on the back of the inner wall of the sampling box, the surface of the cleaning pipe is connected to three cleaning nozzles, and the right side of the bottom of the sampling box is connected to three drainage pipes.

[0014] Preferably, a display controller is provided on the top of the sampling box, 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 through wires, and a plurality of supporting legs are fixedly provided on the bottom of the sampling box.

[0015] A method for preparing a defluorination adsorbent comprises the following steps: Step S1, preparation of polycarboxylic acid 1,3,5-BTC: S11, placing aromatic hydrocarbons and sulfuric acid in a three-necked flask, placing an ice bath, and adding concentrated sulfuric acid dropwise to the ice bath solution. After the addition is complete, removing the ice bath, heating and stirring, and after the solution changes color, heating again and reflux reaction; S12, after cooling the reaction solution, add ice, wait for precipitation, let it stand and filter to obtain a crude product, wash the crude product with distilled water until the filtrate pH = 7, and use a detection sampling device to detect the pH value of the filtrate during the washing process; S13, dissolving the crude product in water, filtering, cooling the obtained filtrate, standing for crystallization, placing the crystals in a vacuum drying oven, and drying 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, placing the mixed solution into a polytetrafluoroethylene-lined reactor, and performing a hydrothermal reaction in a blast drying oven; S23, washing the product, and placing the washed product in an oven for drying to obtain the final product.

[0016] Compared with related technologies, the detection and sampling equipment for preparing defluorination adsorbent and the method for preparing defluorination adsorbent provided by the present invention have the following beneficial effects: When the device is working, the electric telescopic rod is extended to drive the drive frame to move backward. Under the action of the rotating wheel, the lifting frame and the mounting plate, the working positions of the drive disc and the extrusion wheel are switched. The sampling tube is continuously squeezed and released by the extrusion wheel to pump the filtrate into the sampling box for detection. By utilizing the multiple sampling tubes, the working positions of the drive disc and the extrusion wheel are switched to realize multiple sampling of the filtrate, thereby improving the sampling efficiency of the filtrate. In the switching process, the working state of the sampling tube is switched from the sampling state to the cleaning state, thereby avoiding 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 reduced product purity due to inaccurate detection data. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0018] Figure 1 The best structural diagram provided by the present invention; Figure 2 for Figure 1 A schematic structural diagram of a cross-sectional view of the sampling box shown; Figure 3 A schematic structural diagram of the driving mechanism and sampling mechanism provided by the present invention; Figure 4 A schematic diagram of a state in which the electric telescopic rod provided by the present invention drives the driving frame to move backward, causing the rotating wheel and the lifting frame to drive the mounting plate to move upward; Figure 5 for Figure 3 The enlarged structural diagram of point A is shown; Figure 6 for Figure 3 A schematic structural diagram of a cross-sectional view of the mounting plate shown; Figure 7 A schematic structural diagram of the detection mechanism provided by the present invention; Figure 8 A schematic structural diagram of the sample retention mechanism provided by the present invention; Figure 9 for Figure 7 The structural diagram of the mobile seat shown; Figure 10 This is a schematic diagram of the state in which the ball screw provided by the present invention rotates to drive the movable seat to move backward, and the driving wheel causes the movable platform to drive the sample cup to move to the right; Figure 11A schematic structural diagram of the wiping mechanism provided by the present invention; Figure 12 This is a schematic diagram of the state in which the ball screw provided by the present invention rotates to drive the movable seat to move backward, and after the gear contacts the gear plate, the pH meter is driven to rotate through the connecting shaft.

[0019] Description of Figure Numbers: 1. Sampling box; 2. Driving mechanism; 21. Slide rail; 22. Driving frame; 23. Mounting bracket; 24. Lifting frame; 25. Mounting plate; 26. Spring; 27. Rotating wheel; 28. Sliding seat; 29. ​​Electric telescopic rod; 3. Sampling mechanism; 31. Mounting plate; 32. Driving plate; 33. Mounting pad; 34. Sampling tube; 35. Extrusion wheel; 36. Rotating shaft; 37. Driving motor; 4. Detection mechanism; 41. Ball screw; 42. Moving block; 43. Moving seat; 44. Bracket; 45. pH meter; 46. Detection motor; 5. Sample retention mechanism; 51. Guide rail; 52. Moving platform; 53. Sample retention cup; 54. Driving wheel; 6. Wiping mechanism; 61. Gear plate; 62. Connecting shaft; 63. Gear; 64. Cleaning rack; 7. Cleaning pipe; 8. Cleaning nozzle; 9. Drain pipe; 10. Display controller; 11. Buzzer; 12. Support legs.

[0020] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0021] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0022] The invention provides a detection sampling device for preparing a defluorination adsorbent and a method for preparing the defluorination adsorbent.

[0023] First embodiment: See also Figures 1 to 6 , a detection sampling device for preparing a defluorination adsorbent, comprising a sampling box 1, a driving mechanism 2 and a sampling mechanism 3; The driving mechanism 2 includes two slide rails 21, a driving frame 22 and two mounting brackets 23. The inner sides of the two mounting brackets 23 are vertically slidably connected to a lifting frame 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 sleeved 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 driving frames 22. The surfaces of the two slide rails 21 are slidably connected to a sliding seat 28, the tops of the two sliding seats 28 are fixedly connected to the bottom of the driving 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 driving frame 22, and 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; Please combine Figure 4 and Figure 5 : Start the electric telescopic rod 29, which extends and drives the driving frame 22 to move backward, causing the two sliding seats 28 to slide backward on the surface of the slide rail 21. The driving 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 jacking frame 24, causing the spring 26 to contract; Furthermore, when the electric telescopic rod 29 retracts, it simultaneously drives the driving frame 22 forward, causing the two sliding seats 28 to slide forward on the surface of the slide rail 21. The forward movement of the driving frame 22 cancels the squeezing of the rotating wheel 27. Under the action of the spring 26, the two lifting frames 24 drive the mounting plate 25 to move downward. The sampling mechanism 3 includes a mounting plate 31 and two drive plates 32. Three mounting pads 33 are fixed to the inner wall of the mounting plate 31. The inner sides of the three mounting pads 33 are each provided with a sampling tube 34. The surfaces of the two drive plates 32 are rotatably connected to an extrusion wheel 35. A rotating shaft 36 is vertically fixed to the inner sides of the two drive plates 32. The bottom end of the rotating shaft 36 is rotatably connected to the mounting plate 25. A driving motor 37 for driving the rotating shaft 36 is provided at the bottom of the mounting plate 25. 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 squeezing wheels 35 to squeeze the bottom sampling tube 34, and the two squeezing wheels 35 rotate and continuously squeeze and release the bottom sampling tube 34, thereby forming a negative pressure in the bottom sampling tube 34, and then pumping the filtrate into the sampling box 1; Furthermore, when the electric telescopic rod 29 is extended and drives the driving frame 22 to move backward, the driving frame 22 pushes the mounting plate 25 upward through the rotating wheel 27 and the lifting frame 24, which will simultaneously drive the driving motor 37 to move upward. The driving motor 37 drives the two driving discs 32 and the multiple squeezing wheels 35 upward through the rotating shaft 36, thereby adjusting the two squeezing wheels 35 on the top to the middle working position, and the middle sampling tube 34 can be squeezed and released during operation. At the same time, the bottom squeezing wheel 35 is adjusted to the bottom working position accordingly, 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 is squeezed and released by the bottom squeezing wheel 35 to extract distilled water, thereby cleaning the inside of the pipeline. Similarly, when the top sampling tube 34 is used to extract the filtrate, the middle sampling tube 34 is in a cleaning state. Preferably, in order to ensure the accuracy of the detection value, hot air can be passed through the cleaned sampling tube 34 to dry the distilled water remaining inside the sampling tube 34; The three mounting pads 33 and the sampling tube 34 are equidistantly distributed. The spacing between the two driving disks 32 is the same as the spacing between the mounting pads 33. The sampling tube 34 located on the inner side of the mounting disk 31 is a hose, the output end is a pipe, and the output end is a freely bendable corrugated tube. The top and bottom of the extrusion wheel 35 are both angled.

[0024] In this embodiment, unlike the existing sampling equipment for adsorbent preparation, when the present equipment is working, the electric telescopic rod 29 is extended to drive the driving 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 driving disk 32 and the squeezing wheel 35 are switched. The squeezing wheel 35 continuously squeezes and releases the sampling tube 34 to pump the filtrate into the sampling box 1 for detection. By utilizing the multiple sampling tubes 34, by switching the working positions of the driving disk 32 and the squeezing wheel 35, multiple sampling of the filtrate is achieved, thereby improving the sampling efficiency of the filtrate. In the switching process, the working state of the sampling tube 34 is switched, and the sampling tube 34 is switched from the sampling state to the cleaning state, thereby avoiding the residual filtrate in the sampling tube 34 from contaminating the new sample during the secondary sampling, thereby improving the accuracy of the detection value and avoiding the problem of reduced product purity due to inaccurate detection data.

[0025] Second embodiment: See also Figures 7 to 10The inner wall of the sampling box 1 is longitudinally rotatably connected to a detection mechanism 4, and the detection mechanism 4 includes a ball screw 41 longitudinally rotatably connected to the inner wall of the sampling box 1, and a moving block 42 is provided on the surface of the ball screw 41. A moving seat 43 is fixedly provided at the bottom of the moving block 42, and a bracket 44 is fixedly provided 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; Please combine Figure 7 : Start the detection motor 46, the detection motor 46 rotates to drive the ball screw 41 to rotate, and the rotation of the ball screw 41 can drive the moving seat 43, the bracket 44 and the pH meter 45 to move forward and backward through the moving block 42, thereby flexibly adjusting the working position of the pH meter 45; 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 mobile 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 mobile platform 52. A driving wheel 54 is rotatably connected to the left side of the top of the mobile platform 52. There are three groups of sample retention mechanisms 5 in total. Please combine Figures 8 to 10 : After sampling and testing through the bottom sampling tube 34, the ball screw 41 rotates backward to switch the working positions of the movable seat 43, the bracket 44 and the pH meter 45. During the backward movement of the movable seat 43, the driving wheel 54 pushes the movable platform 52 to the right. The rightward movement of the movable platform 52 drives the sample cup 53 to move to the right, thereby switching the sample cup 53 from the working position to the sample retention position; Furthermore, when the sample cup 53 is switched to the sample retention position, the through hole in the movable 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 been switched backward to the second detection position, and the driving disk 32 and the extrusion wheel 35 at the bottom are switched to the cleaning state, cleaning the bottom sampling tube 34. After the clean distilled water is discharged through the output end of the bottom sampling tube 34, it will be discharged from the sampling box 1 through the through hole and the drain pipe 9. The bottom of the movable platform 52 and the inner wall of the sampling box 1 are both provided with through holes. When the movable platform 52 moves to the rightmost side, the through hole in the movable platform 52 coincides with the through hole at the bottom of the inner wall of the sampling box 1. The bottom of the movable seat 43 is provided with a wedge-shaped protrusion for use with the driving wheel 54.

[0026] In this embodiment, the detection motor 46 drives the ball screw 41 to rotate, and when the working position of the movable seat 43, the bracket 44 and the pH meter 45 is switched backward, the movable seat 43 moves through the driving wheel 54 to cause the movable platform 52 to slide to the right on the surface of the guide rail 51, and the sample cup 53 is switched from the working position to the sample position. Through the setting of the sample cup 53, the filtrate can be retained, which is convenient for tracing the problem. At the same time, the filtrate can be centrally processed to avoid polluting the environment. After the sample cup 53 is switched to the sample position, the through hole in the movable platform 52 will coincide with the through hole at the bottom of the inner wall of the sampling box 1. When the bottom extrusion wheel 35 cleans the bottom sampling tube 34, the distilled water can be discharged through the through hole and the drain pipe 9.

[0027] Third embodiment: See also Figure 1 、 Figure 11 and Figure 12 , a wiping mechanism 6 is fixedly provided on the top of the sampling box 1, and the wiping mechanism 6 includes two gear plates 61 fixedly provided on the top of the sampling box 1, and a connecting shaft 62 is provided on the inner side of the top of the sampling box 1. The top of the connecting shaft 62 is fixedly provided with a gear 63, and the gear 63 is respectively engaged with the two gear plates 61 in sequence during the movement process. The bottom end of the connecting shaft 62 is fixedly connected to the top of the pH meter 45, and two sets of cleaning racks 64 are fixedly provided at the bottom of the inner wall of the sampling box 1; Please combine Figure 12 : When the detection motor 46 drives the ball screw 41 to rotate and switches the working positions of the movable 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 drives the pH meter 45 to rotate through the connecting shaft 62. When the pH meter 45 moves to the inner side of the cleaning rack 64, the pH meter 45 is driven to rotate through the gear 63 to avoid dead angles during the wiping process. Preferably, when the gear 63 contacts the front gear plate 61, the gear 63 drives the pH meter 45 to rotate clockwise through the connecting shaft 62; when the gear 63 contacts the rear gear plate 61, the gear 63 drives the pH meter 45 to rotate counterclockwise through the connecting shaft 62; A cleaning pipe 7 is fixedly provided on the back of the inner wall of the sampling box 1 , and three cleaning nozzles 8 are connected to the surface of the cleaning pipe 7 . Three drainage pipes 9 are connected to the right side of the bottom of the sampling box 1 .

[0028] A display controller 10 is provided on the top of the sampling box 1, and a buzzer 11 is provided on the rear side of the top of the sampling box 1. The display controller 10 is electrically connected to the pH meter 45 and the buzzer 11 through a wire. A plurality of supporting legs 12 are fixed on the bottom of the sampling box 1. Preferably, after the pH meter 45 detects the pH value of the filtrate, it will transmit the data to the display controller 10, and the user can intuitively see the digital result. The display controller 10 will retain and record the data. The display controller 10 has a calculation function, which can not only display the digital result, but also process the data and make calculations based on past data, and calculate the approximate pH value of the filtrate at which sampling it reaches neutral. When the pH value of the filtrate reaches neutral, the buzzer 11 will make a sound to remind the user.

[0029] In this embodiment, when the detection motor 46 drives the ball screw 41 to rotate and switches the working positions of the movable 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 inner side of the cleaning rack 64, the pH meter 45 is driven to rotate through the gear 63 to avoid dead corners during the wiping process, thereby ensuring the detection accuracy and reducing the risk of cross-contamination of the filtrate.

[0030] Fourth embodiment: A method for preparing a defluorination adsorbent comprises the following steps: Step S1, preparation of polycarboxylic acid 1,3,5-BTC: S11, placing aromatic hydrocarbons and sulfuric acid in a three-necked flask, placing an ice bath, and adding concentrated sulfuric acid dropwise to the ice bath solution. After the addition is complete, removing the ice bath, heating and stirring, and after the solution changes color, heating again and reflux reaction; Preferably, the aromatic hydrocarbon can be m-trimethylbenzene, cooled to 0-5°C in an ice-water bath, and the dripping rate of concentrated sulfuric acid was controlled so that the reaction temperature did not exceed 10°C. The temperature was raised to 80°C and stirred for 4 hours. The color of the solution gradually changed to orange-red. The temperature was raised to 120°C for the second time and refluxed for 6 hours. S12, after cooling the reaction solution, add ice, wait for precipitation, let it stand and filter to obtain a crude product, wash the crude product with distilled water until the filtrate pH = 7, and use a detection sampling device to detect the pH value of the filtrate during the washing process; Preferably, the standing time is 1 hour; S13, dissolving the crude product in water, filtering, cooling the obtained filtrate, standing for crystallization, placing the crystals in a vacuum drying oven, and drying to obtain the product; Preferably, the crude product is boiled with water for 5 minutes, filtered while hot, the filtrate is cooled to 4°C, allowed to stand for 12 hours, and dried in a vacuum oven at 80°C for 12 hours; 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, placing the mixed solution into a polytetrafluoroethylene-lined reactor, and performing a hydrothermal reaction in a blast drying oven; Preferably, the temperature of the blast drying oven is 210° C., and the hydrothermal reaction time is 4 hours; S23, washing the product, and drying the washed product in an oven to obtain a final product; Preferably, the product is washed three times with deionized water, and the oven temperature is 60°C.

[0031] In this embodiment, during the defluorination process, a synergistic effect exists between aluminum ions and organic ligands within the metal-organic framework structure of MIL-96 (Al). This unique structural feature changes the electron cloud distribution on the surface of the material, greatly improving the adsorption affinity of MIL-96 (Al) for fluoride ions and significantly enhancing its adsorption and activation capabilities for fluoride ions. At the same time, MIL-96 (Al) is loaded onto a specific porous carbon material. This carbon material has efficient electronic conductivity. Its rich porous structure and large specific surface area can firmly attach MIL-96 (Al) nanoclusters. This not only effectively reduces the mass transfer resistance of fluoride ions during the adsorption process, but also allows more previously shielded adsorption active sites to be fully exposed, thereby greatly improving the defluorination activity of the MIL-96 (Al) adsorbent and enhancing the adsorbent's stability.

[0032] Please refer to the Figures 1 to 12 The working principle of the detection and sampling equipment for preparing the defluorination adsorbent provided by the present invention is as follows: Step S1: Start the drive motor 37. The drive motor 37 rotates to drive the two drive disks 32 to rotate via the rotating shaft 36. The top drive disk 32 rotates to drive the two squeezing wheels 35 to squeeze the bottom sampling tube 34. The two squeezing wheels 35 rotate and continuously squeeze and release the bottom sampling tube 34, thereby forming a negative pressure in the bottom sampling tube 34. The filtrate is then pumped to the top of the front sample cup 53 and flows into the front sample cup 53 along the pH meter 45. When the filtrate flows through the surface of the pH meter 45, the pH meter 45 detects the filtrate. Step S2: activating the electric telescopic rod 29. The electric telescopic rod 29 extends to drive the driving frame 22 to move backward, causing the two sliding seats 28 to slide backward on the surface of the slide rail 21. The backward movement of the driving frame 22 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 the spring 26 to contract. The upward movement of the mounting plate 25 simultaneously drives the driving motor 37 to move upward, and the driving motor 37 drives the two driving discs 32 and the multiple squeezing wheels 35 to move upward via the rotating shaft 36, thereby adjusting the two squeezing wheels 35 at the top to the middle working position, squeezing and releasing the middle sampling tube 34 during operation. At the same time, the bottom squeezing wheel 35 is correspondingly adjusted to the bottom working position, squeezing and releasing the bottom sampling tube 34 during operation. When the middle sampling tube 34 is used to sample the filtrate, the bottom sampling tube 34 is squeezed and released by 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 cleaning state. Step S3, starting the detection motor 46, the detection motor 46 rotates to drive the ball screw 41 to rotate, the ball screw 41 rotates through the moving block 42 to drive the moving seat 43, the bracket 44 and the pH meter 45 to move backward, thereby adjusting the pH meter 45 to the top of the middle sample cup 53, ready for the next sampling; Step S4: When the ball screw 41 rotates backward to switch the working positions of the movable base 43, the bracket 44, and the pH meter 45, the movable base 43 moves backward, and the driving wheel 54 pushes the movable platform 52 to the right. The rightward movement of the movable platform 52 drives the sample cup 53 to move to the right, thereby switching the sample cup 53 from the working position to the sample retention position. When the sample cup 53 is switched to the sample retention position, the through hole in the movable 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 been switched backward to the second detection position, and the driving disk 32 and the squeezing wheel 35 at the bottom are switched to the cleaning state to clean the bottom sampling tube 34. After the clean distilled water is discharged through the output end of the bottom sampling tube 34, it will be discharged from the sampling box 1 through the through hole and the drain pipe 9. The driving disk 32 and the squeezing wheel 35 at the top are switched to the position of the middle sampling tube 34 for secondary sampling. Step S5, when the detection motor 46 drives the ball screw 41 to rotate and switches the working position 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 inner side of the cleaning rack 64, the pH meter 45 is driven to rotate through the gear 63 to avoid dead angles during the wiping process.

[0033] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention description and drawings under the concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A detection and sampling device for preparing a defluorination adsorbent, characterized in that: It includes a sampling box, a driving mechanism and a sampling mechanism; The driving mechanism includes two slide rails, a driving frame and two mounting brackets. The inner sides of the two mounting brackets are vertically slidably connected to the lifting frame. The tops of the two lifting frames are fixed with mounting plates. The surfaces of the two lifting frames and the bottoms of the mounting brackets are sleeved with springs. The inner sides of the bottoms of the two lifting frames are rotatably connected to rotating wheels. The bottoms of the two rotating wheels are in contact with the top of the driving frame. The sampling mechanism includes a mounting plate and two driving plates. Three mounting pads are fixedly provided on the inner wall of the mounting plate. Sampling tubes are provided on the inner sides of the three mounting pads. Extrusion wheels are rotatably connected to the surfaces of the two driving plates. A rotating shaft is vertically fixed on the inner sides of the two driving plates. The bottom end of the rotating shaft is rotatably connected to the mounting plate. A driving motor for driving the rotating shaft is provided at the bottom of the mounting plate.

2. The detection and sampling equipment for preparing a defluorination adsorbent according to claim 1, characterized in that: The surfaces of the two slide rails are slidably connected to sliding seats, the tops of the two sliding seats are fixedly connected to the bottom of the driving 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 driving 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.

3. The detection and sampling equipment for preparing a defluorination adsorbent according to claim 1, characterized in that: The three mounting pads and sampling tubes are equidistantly distributed, the spacing between the two driving disks is the same as the spacing between the mounting pads, the sampling tube located on the inner side of the mounting disk is a hose, the output end is a pipe, and the output end is a freely bendable corrugated tube. The top and bottom of the extrusion wheel are both angled designs.

4. The sampling device for preparing a defluorination adsorbent according to claim 1, characterized in that: The inner wall of the sampling box is longitudinally rotatably connected to a detection mechanism, and the detection mechanism includes a ball screw longitudinally 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 fixedly provided at the bottom of the moving block, a bracket is fixedly provided on the right side of the top of the moving seat, a pH meter is rotatably connected to the inner side of the bracket, and a detection motor for driving the ball screw to rotate is provided on the front of the sampling box.

5. The sampling device for preparing a defluorination adsorbent according to claim 4, characterized in that: 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. The surfaces of the two guide rails are slidably connected with a moving platform. A sample retention cup is provided on the right side of the top of the moving platform. The left side of the top of the moving platform is rotatably connected with a driving wheel. There are three groups of sample retention mechanisms in total.

6. The sampling device for preparing a defluorination adsorbent according to claim 5, characterized in that: The bottom of the mobile platform and the inner wall of the sampling box are both provided with 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 seat is provided with a wedge-shaped protrusion for use with the driving wheel.

7. The sampling device for preparing a defluorination adsorbent according to claim 4, characterized in that: A wiping mechanism is fixedly provided on the top of the sampling box, and 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, and a gear is fixedly provided on the top of the connecting shaft. During the movement of the gear, the gear engages with the two gear plates in turn. The bottom end of the connecting shaft is fixedly connected to the top of the pH meter, and two sets of cleaning racks are fixedly provided at the bottom of the inner wall of the sampling box.

8. The sampling device for preparing a defluorination adsorbent according to claim 1, characterized in that: A cleaning pipe is fixedly provided on the back of the inner wall of the sampling box. The surface of the cleaning pipe is connected to three cleaning nozzles. The right side of the bottom of the sampling box is connected to three drainage pipes.

9. The sampling device for preparing a defluorination adsorbent according to claim 4, characterized in that: A display controller is provided on the top of the sampling box, 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 through wires, and a plurality of supporting legs are fixedly provided on the bottom of the sampling box.

10. A method for preparing a defluorination adsorbent, characterized in that: The method for preparing a defluorination adsorbent comprises the detection and sampling device according to any one of claims 1 to 9, comprising the following steps: Step S1, preparation of polycarboxylic acid 1,3,5-BTC: S11, placing aromatic hydrocarbons and sulfuric acid in a three-necked flask, placing an ice bath, and adding concentrated sulfuric acid dropwise to the ice bath solution. After the addition is complete, removing the ice bath, heating and stirring, and after the solution changes color, heating again and reflux reaction; S12, after cooling the reaction solution, add ice, wait for precipitation, let it stand and filter to obtain a crude product, wash the crude product with distilled water until the filtrate pH = 7, and use a detection sampling device to detect the pH value of the filtrate during the washing process; S13, dissolving the crude product in water, filtering, cooling the obtained filtrate, standing for crystallization, placing the crystals in a vacuum drying oven, and drying 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, placing the mixed solution into a polytetrafluoroethylene-lined reactor, and performing a hydrothermal reaction in a blast drying oven; S23, washing the product, and placing the washed product in an oven for drying to obtain the final product.

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