Water pollution treatment equipment and method suitable for industrial high-fluorine wastewater

Abstract

The invention provides water pollution treatment equipment and method suitable for industrial high-fluorine wastewater, and relates to the technical field of water pollution treatment, the water pollution treatment equipment comprises a flocculation basin, a reciprocating frame, a flocculation mechanism and a flocculation auxiliary mechanism; the flocculation mechanism comprises a medicine box and a medicine outlet pipe, the medicine box is arranged at the top of the reciprocating frame, the medicine outlet pipe is rotatably connected to the inner side of the reciprocating frame, and the bottom of the medicine outlet pipe is communicated with an atomizing nozzle. According to the scheme, forward and reverse rotation of the chemical outlet pipe is finally achieved, the swing arm, the connecting rod and the bolt can drive the swing support and the flapping plate to swing back and forth on the surface of fluorine-containing raw water, waves are generated on the water surface, the laminar flow state of the water body is broken, and atomized and sprayed flocculants are rapidly diffused and pushed to the deep water body; the problem that the flocculating agent only floats on the water surface or is locally accumulated is avoided, for fluorine removal, the reaction of fluorine ions and the flocculating agent needs to depend on sufficient mass transfer, wave disturbance can shorten the agent diffusion time, the flocculating agent can be combined with free fluorine ions in water more quickly, and the settling separation efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the field of water pollution control, and in particular to a water pollution control device and method suitable for industrial high-fluorine wastewater. Background Art

[0002] Fluoride ion pollution in water bodies is a major environmental problem that threatens global drinking water safety and industrial sustainable development. Long-term intake of water with excessive fluoride can lead to diseases such as dental fluorosis and skeletal fluorosis. The high fluoride discharge in industrial wastewater further exacerbates the ecological risks. Therefore, it is necessary to reduce the fluoride ion concentration in water to a regulatory level through physical, chemical, biological or combined processes to reduce the potential harm of wastewater to water ecology, soil and human health.

[0003] The widespread use of fluoride in industry results in wastewater containing high levels of fluoride, necessitating the use of treatment equipment to treat this high-fluoride industrial wastewater. However, some existing water pollution control equipment struggles with uniformly dispensing flocculants during flocculation of high-fluoride wastewater. This prevents the flocculant from fully reacting with the fluoride ions in the wastewater, resulting in abnormal floc morphology and reduced sedimentation and separation efficiency.

[0004] Therefore, it is necessary to provide a water pollution control device and method suitable for industrial high-fluorine wastewater to solve the above technical problems. Summary of the Invention

[0005] The present invention provides a water pollution control device and method suitable for industrial high-fluorine wastewater, which solves the problem that some existing water pollution control devices are not convenient for uniformly adding flocculants when flocculating high-fluorine wastewater.

[0006] In order to solve the above technical problems, the present invention provides a water pollution control device suitable for industrial high-fluorine wastewater, which includes a flocculation tank, a reciprocating frame, a flocculation mechanism and a flocculation auxiliary mechanism; The flocculation mechanism includes a medicine box and a medicine outlet pipe, the medicine box is arranged on the top of the reciprocating frame, the medicine outlet pipe is rotatably connected to the inner side of the reciprocating frame, the bottom of the medicine outlet pipe is connected to the atomizing nozzle, the bottom of the reciprocating frame is fixed with two brackets, the inner sides of the two brackets are respectively provided with electric telescopic rods, the output ends of the two electric telescopic rods are respectively provided with gear plates, the surface of the medicine outlet pipe is fixed with two swing gears, and the two swing gears are respectively engaged with the two gear plates; The flocculation auxiliary mechanism includes two rotating seats and two swing arms. The tops of the two rotating seats are fixedly connected to the bottom of the reciprocating frame. The inner sides of the two rotating seats are rotatably connected to the swing brackets. The opposite sides of the two swing brackets are fixedly provided with a flapping plate. The two swing arms are fixedly connected to the two ends of the medicine outlet pipe. The opposite sides of the two swing arms are rotatably connected to the connecting rods. Bolts are provided on the left sides of the two connecting rods. The two connecting rods are respectively connected to the two swing brackets by bolts. Adjustment slots are provided on the inner sides of the two swing brackets.

[0007] Preferably, a delivery pump is provided on the top of the reciprocating frame and at the rear side of the medicine box, and is used to deliver the medicine in the medicine box to the medicine outlet pipe, and spray the medicine into the fluorine-containing raw water using an atomizing nozzle.

[0008] Preferably, by loosening the bolt, the position of the left side of the connecting rod in the swing bracket can be adjusted. When the position of the left side of the swing bracket changes, the swing amplitude of the swing bracket driven by the connecting rod when the swing arm swings will also change.

[0009] Preferably, the inner side of the reciprocating frame is rotatably connected to a scraping mechanism, and the scraping mechanism includes two rotating shafts rotatably connected to the inner side of the reciprocating frame, and the surfaces of the two rotating shafts are fixedly provided with a driving gear and a passive gear. The inner side of the reciprocating frame is vertically slidably connected to a scraper, and two passive tooth plates are fixedly provided on the right side of the scraper, and the two passive tooth plates are respectively engaged with the two passive gears, and two slide rails are fixedly provided on the left side of the scraper, and the two slide rails are slidably connected to the reciprocating frame.

[0010] Preferably, the inner wall of the flocculation tank is laterally rotatably connected to a reciprocating mechanism, and the reciprocating mechanism includes a threaded screw laterally rotatably connected to the inner wall of the flocculation tank, the surface of the threaded screw is threadedly connected to a threaded seat, the bottom of the threaded seat is fixedly connected to the top of the reciprocating frame, the front and rear sides of the inner wall of the flocculation tank are fixed with guide rails, the surfaces of the two guide rails are slidably connected to two sliding seats, the opposite sides of the four sliding seats are fixedly connected to the surface of the reciprocating frame, and a reciprocating motor for driving the threaded screw to rotate is provided on the left side of the flocculation tank.

[0011] Preferably, a bubble generating mechanism is fixedly provided on the left side of the flocculation tank, and the bubble generating mechanism includes an air cylinder fixedly provided on the left side of the flocculation tank, a push rod is slidably connected to the inside of the flocculation tank, a piston is fixedly provided on the left end of the push rod, the surface of the piston is slidably connected to the inner wall of the air cylinder, a spring is provided on the surface of the push rod and located inside the flocculation tank, an air outlet pipe is longitudinally provided inside the flocculation tank, a plurality of bubble nozzles are connected to the top of the air outlet pipe, and the air cylinder is connected to the air outlet pipe through a hose.

[0012] Preferably, the inner wall of the flocculation tank is laterally rotatably connected to a stirring mechanism, and the stirring mechanism includes a stirring shaft laterally rotatably connected to the inner wall of the flocculation tank, and a plurality of groups of stirring brackets are fixedly provided on the surface of the stirring shaft, and a mixing plate is fixedly provided on the surface of the plurality of groups of stirring brackets, and a driving motor for driving the stirring shaft to rotate is provided on the left side of the flocculation tank.

[0013] Preferably, the bottom of the flocculation tank is connected to two discharge pipes, the left side of the flocculation tank is connected to two discharge pipes, and the front side of the flocculation tank is connected to a feed pipe.

[0014] A water pollution control method applicable to industrial high-fluorine wastewater comprises the following steps: Step S1, raw material reaction: zirconium nitrate and trimesic acid are dissolved in a mixed solvent of DMF (N,N-dimethylformamide) and acetic acid, stirred until completely dissolved, and then transferred to a reactor. The pH of the reaction system is adjusted to generate MOF-808 crystals through a solvothermal reaction; Step S2, purification: After the reaction is completed, the product is separated by centrifugation, washed with DMF and methanol in sequence to remove unreacted ligand and solvent, and finally vacuum dried to obtain white MOF-808 powder; Step S3, nitrogen doping modification: MOF-808 powder is mixed with melamine and carbonized at high temperature under an inert gas atmosphere to form nitrogen-doped MOF-808 (N-MOF-808), thereby improving the conductivity of the material; Step S4, hydroxyl modification: N-MOF-808 is immersed in a citric acid solution, and the citric acid molecules are coordinated with the zirconium clusters by stirring, anchoring the hydroxyl groups (-OH) on the pore surface to enhance the fluoride ion adsorption selectivity; Step S5, slurry preparation: the modified MOF-808 powder is mixed with carbon nanotubes (CNTs) and polyvinylidene fluoride (PVDF) binder, and the mixture is added to N-methylpyrrolidone (NMP) solvent for ball milling to form a uniform slurry; Step S6, coating and molding: coating the slurry on the surface of the porous carbon paper current collector, drying and pressing to obtain a MOF-808 based composite electrode; Step S7, electrode configuration: constructing an asymmetric CDI device using the MOF-808 composite electrode as the anode, the activated carbon electrode as the cathode, and the titanium mesh as the current collector; Step S8, adsorption-regeneration cycle: In the adsorption phase, voltage is applied to drive fluoride ions to migrate to the surface of the MOF-808 electrode, where they are captured by microporous screening and coordination with zirconium clusters. In the regeneration phase, the voltage is reversed and the electrode is flushed to release the adsorbed fluoride ions and restore electrode activity. Step S9, fluorine resource recovery: reacting the regeneration waste liquid with calcium salt to generate calcium fluoride precipitate, thereby realizing resource recovery of fluoride ions.

[0015] Compared with related technologies, the water pollution control equipment and method for industrial high-fluoride wastewater provided by the present invention have the following beneficial effects: The gear plate drives the swing gear and the medicine outlet pipe to rotate forward and backward, so that the atomizing nozzle can swing to dispense the flocculant. The swing coverage of the atomizing nozzle is wider, and the flocculant can be evenly sprayed to the entire surface of the fluoride-containing raw water, avoiding the dosing gaps in the edges and corners of the pool, ensuring that the fluoride ions in every area can fully contact with the flocculant, laying the foundation for the subsequent formation of floc complexes. In addition, the drug outlet pipe rotates forward and backward, and the swinging bracket and the flapping plate will swing back and forth on the surface of the fluorine-containing raw water through the swing arm, connecting rod and bolts, causing waves on the water surface, breaking the laminar flow state of the water body, and quickly spreading the atomized flocculant and pushing it to the deep water body, avoiding the problem of the flocculant only floating on the water surface or local accumulation. For fluoride removal, the reaction between fluoride ions and flocculants depends on sufficient mass transfer. Wave disturbance can shorten the diffusion time of the agent, allowing the flocculant to combine with the free fluoride ions in the water more quickly, and improve the sedimentation separation efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] 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.

[0017] Figure 1 The best structural diagram provided by the present invention; Figure 2 A schematic structural diagram of a right view of a flocculation tank provided by the present invention; Figure 3 A schematic diagram of the structures of the flocculation mechanism, flocculation auxiliary mechanism and scraping mechanism provided by the present invention; Figure 4 for Figure 3 The schematic diagram of the structure of the enlarged area A shown; Figure 5 This is a schematic diagram of the state in which the electric telescopic rod provided by the present invention drives the gear plate to move leftward, and the flapping plate swings under the action of the swing gear, swing arm, etc.; Figure 6 A schematic diagram of a state in which the electric telescopic rod provided by the present invention drives the gear plate to continuously move to the left, and the driving gear and the driven gear drive the swinging gear plate and the scraper to move downward; Figure 7 A schematic structural diagram of the reciprocating mechanism provided by the present invention; Figure 8A schematic structural diagram of the bubble generating mechanism provided by the present invention; Figure 9 for Figure 8 A schematic structural diagram of a cross-sectional view of the gas cylinder shown; Figure 10 A schematic diagram of the state in which the reciprocating frame provided by the present invention continuously drives the scraper to move leftward, and utilizes the scraper to squeeze the push rod; Figure 11 A schematic structural diagram of the stirring mechanism provided by the present invention; Figure 12 The present invention provides a flow chart of the method.

[0018] Description of Figure Numbers: 1. Flocculation tank; 2. Reciprocating frame; 3. Flocculation mechanism; 31. Medicine box; 32. Medicine outlet pipe; 33. Atomizing nozzle; 34. Bracket; 35. Electric telescopic rod; 36. Gear plate; 37. Swing gear; 4. Flocculation auxiliary mechanism; 41. Rotating seat; 42. Swinging bracket; 43. Beating plate; 44. Connecting rod; 45. Bolt; 46. Adjusting slot; 47. Swing arm; 5. Scraping mechanism; 51. Rotating shaft; 52. Driving gear; 53. Passive gear; 54. Scraper; 55. Passive gear plate; 56. Slide rail; 6. Reciprocating mechanism; 61. Threaded screw; 62. Threaded seat; 63. Guide rail; 64. Sliding seat; 65. Reciprocating motor; 7. Bubble generating mechanism; 71. Air cylinder; 72. Push rod; 73. Piston; 74. Spring; 75. Air outlet pipe; 76. Bubble nozzle; 8. Stirring mechanism; 81. Stirring shaft; 82. Stirring bracket; 83. Mixing plate; 84. Driving motor; 9. Discharge pipe; 10. Discharge pipe; 11. Feed pipe. DETAILED DESCRIPTION

[0019] 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.

[0020] The present invention provides a water pollution control device and method applicable to industrial high-fluorine wastewater.

[0021] First embodiment: See also Figures 1 to 5, a water pollution control device suitable for industrial high-fluorine wastewater, comprising a flocculation tank 1, a reciprocating frame 2, a flocculation mechanism 3 and a flocculation auxiliary mechanism 4; The flocculation mechanism 3 includes a medicine box 31 and a medicine outlet pipe 32. The medicine box 31 is arranged on the top of the reciprocating frame 2. The medicine outlet pipe 32 is rotatably connected to the inner side of the reciprocating frame 2. The bottom of the medicine outlet pipe 32 is connected to an atomizing nozzle 33. Two brackets 34 are fixedly provided at the bottom of the reciprocating frame 2. The inner sides of the two brackets 34 are each provided with an electric telescopic rod 35. The output ends of the two electric telescopic rods 35 are each fixed with a gear plate 36. Two swing gears 37 are fixedly provided on the surface of the medicine outlet pipe 32. The two swing gears 37 are respectively engaged with the two gear plates 36. Please combine Figure 3 : Start the electric telescopic rod 35, the electric telescopic rod 35 extends and drives the gear plate 36 to move to the left, the gear plate 36 moves to the left and drives the swing gear 37 to rotate counterclockwise, the swing gear 37 rotates counterclockwise and drives the medicine dispensing tube 32 and the atomizing nozzle 33 to rotate counterclockwise, so that the atomizing nozzle 33 adds flocculant to the right; Furthermore, the electric telescopic rod 35 is activated, and the electric telescopic rod 35 retracts, driving the gear plate 36 to move rightward. The rightward movement of the gear plate 36 drives the swing gear 37 to rotate clockwise. The clockwise rotation of the swing gear 37 drives the medicine outlet pipe 32 and the atomizing nozzle 33 to rotate clockwise, causing the atomizing nozzle 33 to add flocculant to the left. The flocculation auxiliary mechanism 4 includes two rotating seats 41 and two swing arms 47. The tops of the two rotating seats 41 are fixedly connected to the bottom of the reciprocating frame 2. The inner sides of the two rotating seats 41 are rotatably connected to the swing brackets 42. The two opposite sides of the swing brackets 42 are fixedly provided with a flapping plate 43. The two swing arms 47 are fixedly connected to the two ends of the medicine discharge pipe 32. The opposite sides of the two swing arms 47 are rotatably connected to the connecting rods 44. The left sides of the two connecting rods 44 are provided with bolts 45. The two connecting rods 44 are respectively connected to the two swing brackets 42 by the bolts 45. The inner sides of the two swing brackets 42 are provided with adjustment slots 46. Please combine Figure 3 and Figure 5 : When the swing gear 37 drives the medicine dispensing tube 32 to rotate counterclockwise, the medicine dispensing tube 32 further drives the two swing arms 47 to rotate counterclockwise. The two swing arms 47 drive the swing bracket 42 and the flapping plate 43 to rotate to the right through the connecting rod 44 and the bolt 45; Furthermore, when the swing gear 37 drives the medicine dispensing tube 32 to rotate clockwise, the medicine dispensing tube 32 in turn drives the two swing arms 47 to rotate clockwise. The two swing arms 47 drive the swing bracket 42 and the flapping plate 43 to move to the left through the connecting rod 44 and the bolt 45. Furthermore, the electric telescopic rod 35 is reciprocated and extended, and the gear plate 36 is used to drive the swing gear 37 to rotate forward and reverse. The swing gear 37 then drives the medicine outlet pipe 32 to rotate forward and reverse. The forward and reverse rotation of the medicine outlet pipe 32 causes the atomizing nozzle 33 to swing and dispense the flocculant. In addition, the forward and reverse rotation of the medicine outlet pipe 32 drives the swing bracket 42 and the flapping plate 43 to swing back and forth on the surface of the fluorine-containing raw water through the swing arm 47, the connecting rod 44 and the bolt 45, thereby generating waves on the water surface. The flocculant is diffused by the waves, which can avoid dead corners when the flocculant is dispensed. A delivery pump is provided on the top of the reciprocating frame 2 and at the rear side of the medicine box 31 . The delivery pump is used to deliver the medicine in the medicine box 31 to the medicine outlet pipe 32 , and spray the medicine onto the fluorine-containing raw water using the atomizing nozzle 33 .

[0022] By loosening the bolt 45, the position of the left side of the connecting rod 44 in the swing bracket 42 can be adjusted. When the position of the left side of the swing bracket 42 changes, the swing amplitude of the swing bracket 42 driven by the connecting rod 44 when the swing arm 47 swings will also change.

[0023] In this embodiment, the gear plate 36 drives the swing gear 37 and the drug outlet pipe 32 to rotate forward and reverse, so that the atomizing nozzle 33 performs a swinging dispensing of the flocculant. The swinging coverage of the atomizing nozzle 33 is wider, and the flocculant can be evenly sprayed onto the entire surface of the fluorine-containing raw water, avoiding drug dispensing gaps in areas such as the edges and corners of the tank body, ensuring that fluoride ions are fully contacted with the flocculant at every location, laying the foundation for the subsequent formation of floc complexes. In addition, the medicine outlet pipe 32 rotates forward and backward, and the swinging bracket 42 and the flapping plate 43 are driven to swing back and forth on the surface of the fluorine-containing raw water through the swing arm 47, the connecting rod 44 and the bolt 45, thereby generating waves on the water surface, breaking the laminar flow state of the water body, and quickly spreading the atomized sprayed flocculant and pushing it to the deep water body, avoiding the problem of the flocculant only floating on the water surface or local accumulation. For fluoride removal, the reaction between fluoride ions and flocculants requires sufficient mass transfer. Wave disturbance can shorten the diffusion time of the agent, allowing the flocculant to combine with the free fluoride ions in the water more quickly, thereby improving the sedimentation separation efficiency.

[0024] Second embodiment: See also Figure 3 、 Figure 6 and Figure 7The inner side of the reciprocating frame 2 is rotatably connected to a scraping mechanism 5, and the scraping mechanism 5 includes two rotating shafts 51 rotatably connected to the inner side of the reciprocating frame 2. The surfaces of the two rotating shafts 51 are fixedly provided with a driving gear 52 and a passive gear 53. The inner side of the reciprocating frame 2 is vertically slidably connected to a scraper 54, and two passive tooth plates 55 are fixedly provided on the right side of the scraper 54. The two passive tooth plates 55 are respectively engaged with the two passive gears 53. The left side of the scraper 54 is fixedly provided with two slide rails 56, and the two slide rails 56 are slidably connected to the reciprocating frame 2. Please combine Figure 3 and Figure 6 : When the gear plate 36 continues to move to the left, disengages from the swing gear 37, and contacts the driving gear 52, it drives the driving gear 52 to rotate counterclockwise. The driving gear 52 drives the driven gear 53 to rotate counterclockwise through the rotating shaft 51. The counterclockwise rotation of the driven gear 53 drives the scraper 54 to move downward, so that the bottom of the scraper 54 is inserted into the water. Preferably, the friction coefficient between the rotating shaft 51 and the reciprocating frame 2 is large, and when not driven by the driving gear 52, it will not rotate on its own. The bottom of the scraper 54 is provided with a scraping groove, and a collecting tank is provided on the left side of the flocculation tank 1. The inner wall of the flocculation tank 1 is laterally rotatably connected to a reciprocating mechanism 6, and the reciprocating mechanism 6 includes a threaded screw 61 that is laterally rotatably connected to the inner wall of the flocculation tank 1, and a threaded seat 62 is threadedly connected to the surface of the threaded screw 61, and the bottom of the threaded seat 62 is fixedly connected to the top of the reciprocating frame 2. The front and rear sides of the inner wall of the flocculation tank 1 are fixed with guide rails 63, and the surfaces of the two guide rails 63 are slidably connected to two sliding seats 64, and the opposite sides of the four sliding seats 64 are fixedly connected to the surface of the reciprocating frame 2. A reciprocating motor 65 for driving the threaded screw 61 to rotate is provided on the left side of the flocculation tank 1; Please combine Figure 7 : Start the reciprocating motor 65, and the reciprocating motor 65 rotates to drive the threaded screw 61 to rotate. The threaded screw 61 rotates and then drives the threaded seat 62 and the reciprocating frame 2 to move to the right, so that the sliding seat 64 slides to the right on the surface of the guide rail 63. By reversing the reciprocating motor 65, the reciprocating frame 2 can be driven to move to the left. The reciprocating frame 2 moves left and right, so that the working position of the atomizing nozzle 33 and the scraper 54 can be adjusted. By driving the scraper 54 to move to the left by the reciprocating frame 2, the suspended matter on the top of the fluorine-containing raw water can be scraped into the collection tank.

[0025] In this embodiment, when the gear plate 36 contacts the driving gear 52, it drives the bottom of the scraper 54 to be inserted into the water body. In the fluorine-containing raw water, flocs generated by the reaction of fluoride ions and flocculants, such as aluminum-fluoride complexes or calcium fluoride complexes, mostly float or suspend in the upper layer of the water body. The scraper 54 is driven to move to the left by the reciprocating frame 2. When the scraper 54 moves to the left, the fluorine-containing suspended matter on the water surface can be scraped directionally into the left collection tank to remove the flocs accumulated in various areas of the pool body, thereby preventing them from being redispersed or sinking to the bottom of the pool due to water flow disturbance, resulting in subsequent difficulty in removal and even the problem of fluoride ions being re-dissolved.

[0026] Third embodiment: See also Figure 1 、 Figures 8 to 11 A bubble generating mechanism 7 is fixedly provided on the left side of the flocculation tank 1. The bubble generating mechanism 7 includes an air cylinder 71 fixedly provided on the left side of the flocculation tank 1. A push rod 72 is slidably connected to the inside of the flocculation tank 1. A piston 73 is fixedly provided on the left end of the push rod 72. The surface of the piston 73 is slidably connected to the inner wall of the air cylinder 71. A spring 74 is sleeved on the surface of the push rod 72 and located inside the flocculation tank 1. An air outlet pipe 75 is longitudinally provided inside the flocculation tank 1. A plurality of bubble nozzles 76 are connected to the top of the air outlet pipe 75. The air cylinder 71 is connected to the air outlet pipe 75 through a hose. Please combine Figures 8 to 10 When the reciprocating frame 2 continuously drives the scraper 54 to move leftward, the scraper 54 will squeeze the push rod 72 to the left, causing the push rod 72 to drive the piston 73 to slide leftward on the inner wall of the cylinder 71, and the gas in the cylinder 71 is transported to the outlet pipe 75 through the hose. The gas is then transported into the fluorine-containing raw water in the form of tiny bubbles by the bubble nozzle 76. The bubbles are adsorbed on the surface of the negatively charged fluorine-containing flocs, causing the fluorine-containing flocs to float to the water surface, forming a scum layer of uniform thickness. The scraper 54 can push the scum layer into the collection tank, and the discharge pipe 10 can discharge it out of the flocculation tank. Preferably, an air extraction pipe is provided at the top of the air cylinder 71, and both the air extraction pipe and the hose are provided with a one-way valve; The inner wall of the flocculation tank 1 is laterally rotatably connected to a stirring mechanism 8, and the stirring mechanism 8 includes a stirring shaft 81 that is laterally rotatably connected to the inner wall of the flocculation tank 1. The surface of the stirring shaft 81 is fixed with multiple groups of stirring brackets 82, and the surfaces of the multiple groups of stirring brackets 82 are fixed with mixing plates 83. A driving motor 84 for driving the stirring shaft 81 to rotate is provided on the left side of the flocculation tank 1; Please combine Figure 11 : Start the drive motor 84, the drive motor 84 rotates to drive the stirring shaft 81 to rotate, the stirring shaft 81 rotates through the multiple sets of stirring brackets 82 to drive the mixing plate 83 to rotate, thereby mixing the fluorine-containing raw water and the flocculant; The bottom of the flocculation tank 1 is connected to two discharge pipes 9 , the left side of the flocculation tank 1 is connected to two discharge pipes 10 , and the front side of the flocculation tank 1 is connected to a feed pipe 11 .

[0027] In this embodiment, when the scraper 54 moves to the left to squeeze the push rod 72, the gas generated by the air cylinder 71 is released in the form of tiny bubbles in the fluorine-containing raw water. The surface of the bubble is positively charged and can be combined with the negatively charged fluorine-containing flocs through charge adsorption. The buoyancy of the bubble can overcome the gravity of the flocs and quickly lift them to the water surface, forming a scum layer with uniform thickness, which can avoid the desorption of fluoride ions caused by the flocs staying in the water body for too long. At the same time, after the flocs float up, the scum layer structure will be relatively tight, which can effectively reduce the risk of breakage when the scraper 54 is scraping, ensure that the fluorine-containing flocs are efficiently collected in the collection tank, reduce the possibility of rebound of fluorine concentration in the effluent, and thus improve the fluorine removal effect on high-fluorine wastewater.

[0028] Fourth embodiment: See also Figure 12 , a water pollution control method suitable for industrial high-fluorine wastewater, comprising the following steps: Step S1, raw material reaction: zirconium nitrate and trimesic acid are dissolved in a mixed solvent of DMF (N,N-dimethylformamide) and acetic acid, stirred until completely dissolved, and then transferred to a reactor. The pH of the reaction system is adjusted to generate MOF-808 crystals through a solvothermal reaction; Preferably, zirconium nitrate and trimesic acid are dissolved in a molar ratio of 1:2.5, the pH is adjusted to 2.5, and a solvothermal reaction is carried out at 135° C. for 36 hours; Step S2, purification: After the reaction is completed, the product is separated by centrifugation, washed with DMF and methanol in sequence to remove unreacted ligand and solvent, and finally vacuum dried to obtain white MOF-808 powder; Preferably, vacuum drying at 80°C for 12h; Step S3, nitrogen doping modification: MOF-808 powder is mixed with melamine and carbonized at high temperature under an inert gas atmosphere to form nitrogen-doped MOF-808 (N-MOF-808), thereby improving the conductivity of the material; Preferably, the inert gas is argon, and the temperature is increased to 600°C at 5°C / min and kept constant for 2h; Step S4, hydroxyl modification: N-MOF-808 is immersed in a citric acid solution, and the citric acid molecules are coordinated with the zirconium clusters by stirring, anchoring the hydroxyl groups (-OH) on the pore surface to enhance the fluoride ion adsorption selectivity; Preferably, 100 ml of citric acid solution with a pH of 3.0 is prepared, stirred at 80°C for 12 h, filtered, and washed with deionized water until neutral; Step S5, slurry preparation: the modified MOF-808 powder is mixed with carbon nanotubes (CNTs) and polyvinylidene fluoride (PVDF) binder, and the mixture is added to N-methylpyrrolidone (NMP) solvent for ball milling to form a uniform slurry; Preferably, ball milling is performed for 4 hours at a rotation speed of 300 rpm; Step S6, coating and molding: coating the slurry on the surface of the porous carbon paper current collector, drying and pressing to obtain a MOF-808 based composite electrode; Preferably, the carbon paper current collector has a thickness of 0.3 mm and a porosity of 85%, is vacuum dried at 80° C. for 12 h, and is pressed at a pressure of 10 MPa for 5 min; Step S7, electrode configuration: constructing an asymmetric CDI device using the MOF-808 composite electrode as the anode, the activated carbon electrode as the cathode, and the titanium mesh as the current collector; Preferably, the MOF-808 composite electrode and the activated carbon electrode were placed in parallel with a spacing of 3 mm, and a titanium mesh was used as a current collector to assemble an asymmetric CDI module; Step S8, adsorption-regeneration cycle: In the adsorption phase, voltage is applied to drive fluoride ions to migrate to the surface of the MOF-808 electrode, where they are captured by microporous screening and coordination with zirconium clusters. In the regeneration phase, the voltage is reversed and the electrode is flushed to release the adsorbed fluoride ions and restore electrode activity. Preferably, the voltage is 1.0V, the flow rate is 10ml / min, the inlet pH is 6.0, and the adsorption is carried out for 30min; after saturation of adsorption, the electrodes are short-circuited and a voltage of -0.5V is applied for 10min, while the electrodes are flushed with NaCl solution at a flow rate of 20ml / min; Step S9, fluorine resource recovery: reacting the regeneration waste liquid with calcium salt to generate calcium fluoride precipitate, thereby realizing resource recovery of fluoride ions; Preferably, the regeneration wastewater is mixed with 10% CaCl2 solution (calculated by Ca 2+ :F-=1.2:1 molar ratio), adjust the pH to 7.0, and stir for 30 minutes to generate CaF2 precipitate, which is then centrifuged to recover fluorine resources.

[0029] In this embodiment, by combining MOF material modification with capacitive deionization technology, in terms of anti-interference and adaptation to complex water quality, industrial wastewater often contains a large number of coexisting ions and impurities. The process anchors hydroxyl groups on the surface of MOF-808 channels through hydroxyl modification, relying on the strong coordination effect between specific metal clusters and fluoride ions to preferentially capture fluorine, and then combined with the microporous screening effect of MOF materials to eliminate interference from large molecular impurities. Even if the concentration of coexisting ions far exceeds that of fluoride ions, the fluorine adsorption selectivity can still remain very high. It can be adapted to high-salt and high-impurity wastewater in coal chemical, fluorine chemical and other industries, and realizes efficient, stable and repeatable fluoride ion removal and resource utilization.

[0030] Please refer to the Figures 1 to 12 The working principle of the water pollution control equipment for industrial high-fluorine wastewater provided by the present invention is as follows: Step S1: Fluorine-containing raw water is introduced into the flocculation tank 1 through the feed pipe 11, and the drive motor 84 is started. The drive motor 84 rotates to drive the stirring shaft 81 to rotate. The stirring shaft 81 rotates through the multiple sets of stirring brackets 82 to drive the mixing plate 83 to rotate, thereby premixing the fluorine-containing raw water; The reciprocating motor 65 is started, and the reciprocating motor 65 rotates to drive the threaded screw 61 to rotate. The threaded screw 61 rotates and drives the threaded seat 62 and the reciprocating frame 2 to move rightward, causing the sliding seat 64 to slide rightward on the surface of the guide rail 63. The reciprocating motor 65 is reversed, thereby driving the reciprocating frame 2 to move leftward. Step S2: Start the electric telescopic rod 35. The electric telescopic rod 35 is used to extend and retract to drive the gear plate 36 to reciprocate. The reciprocating movement of the gear plate 36 drives the swing gear 37 to rotate forward and reverse. The forward and reverse rotation of the swing gear 37 drives the medicine outlet pipe 32 and the atomizing nozzle 33 to rotate forward and reverse. The delivery pump is started to deliver the medicine in the medicine box 31 to the medicine outlet pipe 32. The atomizing nozzle 33 is used to swing and spray the medicine into the fluorine-containing raw water. The reciprocating frame 2 moves back and forth, driving the atomizing nozzle 33 to reciprocate and swing to spray the medicine. The drug dispensing pipe 32 rotates forward and backward, and drives the swing bracket 42 and the flapping plate 43 to swing back and forth on the surface of the fluorine-containing raw water through the swing arm 47, the connecting rod 44 and the bolt 45, thereby generating waves on the water surface. The waves are used to diffuse the flocculant, which can avoid dead corners when the flocculant is dispensed; Step S3: After the reagent is added, it is allowed to stand for fifteen minutes. When the reagent fully reacts with the fluorine-containing raw water, the gear plate 36 continues to move to the left, disengaging from the swing gear 37 and contacting the driving gear 52. This drives the driving gear 52 to rotate counterclockwise. The driving gear 52 drives the driven gear 53 to rotate counterclockwise via the rotating shaft 51. The counterclockwise rotation of the driven gear 53 drives the scraper 54 downward, so that the bottom of the scraper 54 is inserted into the water. In step S4, the reciprocating mechanism 6 drives the reciprocating frame 2 and the scraper 54 to continuously move leftward. The scraper 54 presses the push rod 72 to the left, causing the push rod 72 to drive the piston 73 to slide leftward on the inner wall of the cylinder 71. The gas in the cylinder 71 is transported to the outlet pipe 75 through the hose. The gas is then transported into the fluorine-containing raw water in the form of tiny bubbles using the bubble nozzle 76. The bubbles are adsorbed on the surface of the negatively charged fluorine-containing flocs, causing the fluorine-containing flocs to float to the water surface, forming a scum layer of uniform thickness. In step S5, the scraper 54 is adjusted to the right working position through the reciprocating mechanism 6, and then the bottom of the scraper 54 is adjusted to the water. The reciprocating mechanism 6 is used to drive the scraper 54 to move to the left, thereby pushing the scum layer to the left and pushing the scum into the collection tank on the left. The scum is discharged using the discharge pipe 10. After the scraping work is completed, the equipment can be reset.

[0031] 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 water pollution control device suitable for industrial high-fluorine wastewater, characterized in that: It includes a flocculation tank, a reciprocating frame, a flocculation mechanism and a flocculation auxiliary mechanism; The flocculation mechanism includes a medicine box and a medicine outlet pipe, the medicine box is arranged on the top of the reciprocating frame, the medicine outlet pipe is rotatably connected to the inner side of the reciprocating frame, the bottom of the medicine outlet pipe is connected to the atomizing nozzle, the bottom of the reciprocating frame is fixed with two brackets, the inner sides of the two brackets are respectively provided with electric telescopic rods, the output ends of the two electric telescopic rods are respectively provided with gear plates, the surface of the medicine outlet pipe is fixed with two swing gears, and the two swing gears are respectively engaged with the two gear plates; The flocculation auxiliary mechanism includes two rotating seats and two swing arms. The tops of the two rotating seats are fixedly connected to the bottom of the reciprocating frame. The inner sides of the two rotating seats are rotatably connected to the swing brackets. The opposite sides of the two swing brackets are fixedly provided with a flapping plate. The two swing arms are fixedly connected to the two ends of the medicine outlet pipe. The opposite sides of the two swing arms are rotatably connected to the connecting rods. Bolts are provided on the left sides of the two connecting rods. The two connecting rods are respectively connected to the two swing brackets by bolts. Adjustment slots are provided on the inner sides of the two swing brackets.

2. The water pollution control equipment suitable for industrial high-fluorine wastewater according to claim 1, characterized in that: A delivery pump is provided on the top of the reciprocating frame and at the rear side of the medicine box. The delivery pump is used to deliver the medicine in the medicine box to the medicine outlet pipe, and spray the medicine onto the fluorine-containing raw water using an atomizing nozzle.

3. The water pollution control equipment suitable for industrial high-fluorine wastewater according to claim 1, characterized in that: By loosening the bolt, the position of the left side of the connecting rod in the swing bracket can be adjusted. When the position of the left side of the swing bracket changes, the swing amplitude of the swing bracket driven by the connecting rod when the swing arm swings will also change.

4. The water pollution control equipment suitable for industrial high-fluorine wastewater according to claim 1, characterized in that: The inner side of the reciprocating frame is rotatably connected to a scraping mechanism, and the scraping mechanism includes two rotating shafts rotatably connected to the inner side of the reciprocating frame, and the surfaces of the two rotating shafts are fixedly provided with a driving gear and a passive gear. The inner side of the reciprocating frame is vertically slidably connected to a scraper, and two passive tooth plates are fixedly provided on the right side of the scraper, and the two passive tooth plates are respectively engaged with the two passive gears, and two slide rails are fixedly provided on the left side of the scraper, and the two slide rails are slidably connected to the reciprocating frame.

5. The water pollution control equipment suitable for industrial high-fluorine wastewater according to claim 1, characterized in that: The inner wall of the flocculation tank is laterally rotatably connected to a reciprocating mechanism, and the reciprocating mechanism includes a threaded screw that is laterally rotatably connected to the inner wall of the flocculation tank, the surface of the threaded screw is threadedly connected to a threaded seat, and the bottom of the threaded seat is fixedly connected to the top of the reciprocating frame. The front and rear sides of the inner wall of the flocculation tank are fixed with guide rails, and the surfaces of the two guide rails are slidably connected to two sliding seats, and the opposite sides of the four sliding seats are fixedly connected to the surface of the reciprocating frame. A reciprocating motor for driving the threaded screw to rotate is provided on the left side of the flocculation tank.

6. The water pollution control equipment suitable for industrial high-fluorine wastewater according to claim 1, characterized in that: A bubble generating mechanism is fixedly provided on the left side of the flocculation tank, and the bubble generating mechanism includes an air cylinder fixedly provided on the left side of the flocculation tank, a push rod is slidably connected to the interior of the flocculation tank, a piston is fixedly provided on the left end of the push rod, the surface of the piston is slidably connected to the inner wall of the air cylinder, a spring is provided on the surface of the push rod and located inside the flocculation tank, an air outlet pipe is longitudinally provided inside the flocculation tank, a plurality of bubble nozzles are connected to the top of the air outlet pipe, and the air cylinder is connected to the air outlet pipe through a hose.

7. The water pollution control equipment suitable for industrial high-fluorine wastewater according to claim 1, characterized in that: The inner wall of the flocculation tank is laterally rotatably connected to a stirring mechanism, and the stirring mechanism includes a stirring shaft laterally rotatably connected to the inner wall of the flocculation tank. A plurality of stirring brackets are fixedly provided on the surface of the stirring shaft, and a mixing plate is fixedly provided on the surface of the plurality of stirring brackets. A driving motor for driving the stirring shaft to rotate is provided on the left side of the flocculation tank.

8. The water pollution control equipment suitable for industrial high-fluorine wastewater according to claim 1, characterized in that: The bottom of the flocculation tank is connected to two discharge pipes, the left side of the flocculation tank is connected to two discharge pipes, and the front side of the flocculation tank is connected to a feed pipe.

9. A water pollution control method suitable for industrial high-fluorine wastewater, characterized in that: The treatment method comprises the treatment device according to any one of claims 1 to 8 and the following steps: Step S1, raw material reaction: zirconium nitrate and trimesic acid are dissolved in a mixed solvent of DMF (N,N-dimethylformamide) and acetic acid, stirred until completely dissolved, and then transferred to a reactor. The pH of the reaction system is adjusted to generate MOF-808 crystals through a solvothermal reaction; Step S2, purification: After the reaction is completed, the product is separated by centrifugation, washed with DMF and methanol in sequence to remove unreacted ligand and solvent, and finally vacuum dried to obtain white MOF-808 powder; Step S3, nitrogen doping modification: MOF-808 powder is mixed with melamine and carbonized at high temperature under an inert gas atmosphere to form nitrogen-doped MOF-808 (N-MOF-808), thereby improving the conductivity of the material; Step S4, hydroxyl modification: N-MOF-808 is immersed in a citric acid solution, and the citric acid molecules are coordinated with the zirconium clusters by stirring, anchoring the hydroxyl groups (-OH) on the pore surface to enhance the fluoride ion adsorption selectivity; Step S5, slurry preparation: the modified MOF-808 powder is mixed with carbon nanotubes (CNTs) and polyvinylidene fluoride (PVDF) binder, and the mixture is added to N-methylpyrrolidone (NMP) solvent for ball milling to form a uniform slurry; Step S6, coating and molding: coating the slurry on the surface of the porous carbon paper current collector, drying and pressing to obtain a MOF-808 based composite electrode; Step S7, electrode configuration: constructing an asymmetric CDI device using the MOF-808 composite electrode as the anode, the activated carbon electrode as the cathode, and the titanium mesh as the current collector; Step S8, adsorption-regeneration cycle: In the adsorption stage, voltage is applied to drive fluoride ions to migrate to the surface of the MOF-808 electrode, and the fluoride ions are captured by microporous screening and coordination with the zirconium clusters; The regeneration stage is to reverse the voltage and flush the electrode to release the adsorbed fluoride ions and restore the electrode activity; Step S9, fluorine resource recovery: reacting the regeneration waste liquid with calcium salt to generate calcium fluoride precipitate, thereby realizing resource recovery of fluoride ions.

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