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

Abstract

The application provides a water pollution treatment equipment and method suitable for industrial high-fluorine wastewater, relates to the technical field of water pollution treatment, and comprises a flocculation tank, 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 rotationally connected to the inner side of the reciprocating frame. The bottom of the medicine outlet pipe is communicated with an atomizing nozzle. The scheme finally realizes the forward and reverse rotation of the medicine outlet pipe. Through the swing arm, connecting rod and bolt, the swing support and beating plate are driven to reciprocally swing on the surface of the fluorine-containing raw water, so that waves are generated on the water surface, the laminar flow state of the water body is broken, the flocculating agent sprayed by atomization is rapidly diffused and pushed to the deep water body, and the problem that the flocculating agent only floats on the water surface or is locally accumulated is avoided. For defluorination, the reaction of fluorine ions and the flocculating agent needs to rely on sufficient mass transfer. The wave disturbance can shorten the diffusion time of the medicine, so that the flocculating agent can be combined with the free fluorine ions in the water more quickly, and the sedimentation separation efficiency is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of water pollution treatment, and in particular to a water pollution treatment device and method suitable for industrial high-fluorine wastewater. BACKGROUND

[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 fluorine-exceeding water can cause diseases such as dental fluorosis and skeletal fluorosis, and the high-fluorine discharge of industrial wastewater further aggravates the ecological risk. Therefore, it is necessary to reduce the fluoride ion concentration in water to a compliant level through physical, chemical, biological or combined processes, and to reduce the potential harm of wastewater to water ecology, soil and human health.

[0003] In related technologies, the widespread use of fluorides in industry results in wastewater with high-fluorine characteristics, which requires treatment equipment to treat industrial high-fluorine wastewater. However, some existing water pollution treatment equipment is not convenient for uniform dosing of flocculants when flocculating high-fluorine wastewater, which causes the flocculants to not fully react with fluoride ions in the wastewater, resulting in abnormal flocculation body morphology and reduced sedimentation separation efficiency.

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

[0005] The present application provides a water pollution treatment device and method suitable for industrial high-fluorine wastewater, which solves the problem that some existing water pollution treatment equipment is not convenient for uniform dosing of flocculants when flocculating high-fluorine wastewater.

[0006] To solve the above technical problems, the water pollution treatment device suitable for industrial high-fluorine wastewater provided by the present application comprises a flocculation tank, a reciprocating frame, a flocculation mechanism and a flocculation auxiliary mechanism.

[0007] 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, the bottom of the medicine outlet pipe is communicated with an atomizing nozzle, the bottom of the reciprocating frame is fixedly provided with two brackets, the inner sides of the two brackets are both provided with an electric telescopic rod, the output ends of the two electric telescopic rods are both fixedly provided with a gear plate, the surface of the medicine outlet pipe is fixedly provided with two oscillating gears, and the two oscillating gears are respectively engaged with the two gear plates.

[0008] The flocculation auxiliary mechanism comprises two rotating seats, the top of the two rotating seats is fixedly connected with the bottom of the reciprocating frame, the inner side of the two rotating seats is rotationally connected with a swing support, the opposite side of the two swing supports is fixedly provided with a beating plate, the two ends of the two swing arms are fixedly connected with the two ends of the medicine outlet pipe, the opposite side of the two swing arms is rotationally connected with a connecting rod, the left side of the two connecting rods is provided with a bolt, and the two connecting rods are connected with the two swing supports through the bolts.

[0009] Preferably, the top of the reciprocating frame and the rear side of the medicine box are provided with a delivery pump, the delivery pump is used for delivering the medicament in the medicine box into the medicine outlet pipe, and the medicament is sprayed to the fluorine-containing raw water by the atomizing nozzle.

[0010] Preferably, the position of the left side of the connecting rod in the swing support can be adjusted by loosening the bolt, and when the position of the left side of the swing support changes, the swing range of the swing support driven by the connecting rod when the swing arm swings will also change.

[0011] Preferably, the inner side of the reciprocating frame is rotationally connected with a scraping mechanism, the scraping mechanism comprises two rotating shafts rotationally connected with the inner side of the reciprocating frame, the surface of the two rotating shafts is fixedly provided with a driving gear and a driven gear, the inner side of the reciprocating frame is vertically and slidingly connected with a scraper, the right side of the scraper is fixedly provided with two driven tooth plates, the two driven tooth plates are respectively engaged with the two driven gears, the left side of the scraper is fixedly provided with two sliding rails, and the two sliding rails are slidingly connected with the reciprocating frame.

[0012] Preferably, the inner wall of the flocculation tank is transversely and rotationally connected with a reciprocating mechanism, the reciprocating mechanism comprises a threaded screw rod transversely and rotationally connected with the inner wall of the flocculation tank, the surface of the threaded screw rod is threadedly connected with a threaded seat, the bottom of the threaded seat is fixedly connected with the top of the reciprocating frame, the front side and the rear side of the inner wall of the flocculation tank are fixedly provided with guide rails, the surface of the two guide rails is slidingly connected with two sliding seats, the opposite side of the four sliding seats is fixedly connected with the surface of the reciprocating frame, and the left side of the flocculation tank is provided with a reciprocating motor for driving the threaded screw rod to rotate.

[0013] Preferably, the left side of the flocculation tank is fixedly provided with a bubble generating mechanism, the bubble generating mechanism comprises an air cylinder fixedly provided on the left side of the flocculation tank, the inside of the flocculation tank is slidingly connected with a push rod, the left end of the push rod is fixedly provided with a piston, the surface of the piston is slidingly connected with the inner wall of the air cylinder, the surface of the push rod and the inside of the flocculation tank are sleeved with a spring, the inside of the flocculation tank is longitudinally provided with an air outlet pipe, the top of the air outlet pipe is communicated with a plurality of bubble nozzles, and the air cylinder is communicated with the air outlet pipe through a hose.

[0014] Preferably, the inner wall of the flocculation tank is transversely connected with a stirring mechanism, the stirring mechanism comprises a stirring shaft transversely connected with the inner wall of the flocculation tank, the surface of the stirring shaft is fixedly provided with a plurality of stirring supports, the surface of the plurality of stirring supports is fixedly provided with mixing plates, and the left side of the flocculation tank is provided with a driving motor for driving the stirring shaft to rotate.

[0015] Preferably, the bottom of the flocculation tank is communicated with two discharge pipes, the left side of the flocculation tank is communicated with two discharge pipes, and the front side of the flocculation tank is communicated with a feeding pipe.

[0016] A water pollution treatment method suitable for industrial high-fluorine wastewater, comprising the following steps:

[0017] Step S1, raw material reaction: dissolve zirconium nitrate and trimesic acid in a mixed solvent of DMF (N, N-dimethylformamide) and acetic acid, transfer to a reaction kettle after stirring to completely dissolve, adjust the PH of the reaction system, and generate MOF-808 crystals through solvothermal reaction;

[0018] Step S2, purification treatment: after the reaction is completed, the product is centrifuged and washed with DMF and methanol in sequence to remove unreacted ligands and solvents, and finally vacuum dried to obtain white MOF-808 powder;

[0019] Step S3, nitrogen-doped modification: mix the MOF-808 powder with melamine, carbonize at high temperature in an inert gas atmosphere to form nitrogen-doped MOF-808 (N-MOF-808), and improve the electrical conductivity of the material;

[0020] Step S4, hydroxyl modification: immerse N-MOF-808 in a citric acid solution, coordinate citric acid molecules with zirconium clusters through stirring, anchor hydroxyl groups (-OH) on the surface of the pores, and enhance the adsorption selectivity of fluoride ions;

[0021] Step S5, slurry preparation: mix the modified MOF-808 powder with carbon nanotubes (CNT) and polyvinylidene fluoride (PVDF) binder, add N-methyl pyrrolidone (NMP) solvent, and ball mill to form a uniform slurry;

[0022] Step S6, coating and molding: coat the slurry on the surface of a porous carbon paper current collector, dry and press to form a MOF-808-based composite electrode;

[0023] Step S7, electrode configuration: use the MOF-808 composite electrode as the anode, an activated carbon electrode as the cathode, and a titanium mesh as the current collector to construct an asymmetric CDI device;

[0024] Step S8, adsorption-regeneration cycle: the adsorption stage is to apply voltage to drive fluorine ion migration to the MOF-808 electrode surface, and capture fluorine ion through microporous screening and coordination with zirconium clusters; the regeneration stage is to reverse the voltage and flush the electrode to release the adsorbed fluorine ion and restore the electrode activity;

[0025] Step S9, fluorine resource recovery: the regenerated waste liquid is reacted with calcium salt to generate calcium fluoride precipitate, realizing the resource recovery of fluorine ion.

[0026] Compared with the related art, the water pollution treatment equipment and method suitable for industrial high-fluorine wastewater provided by the present application has the following beneficial effects:

[0027] The gear plate drives the swing gear and the medicine outlet pipe to rotate forward and backward, so that the atomizing nozzle swings to place the flocculant. The swinging coverage of the atomizing nozzle is wider, and the flocculant can be uniformly sprayed to the whole surface of the fluorine-containing raw water, avoiding the problem of blank medicine placement in the edge and corner areas of the pool body, and ensuring that the fluorine ion in every place can fully contact with the flocculant, laying a foundation for the generation of subsequent flocculation compound.

[0028] In addition, the forward and backward rotation of the medicine outlet pipe drives the swing bracket and the beating plate to reciprocally swing on the surface of the fluorine-containing raw water through the swing arm, connecting rod and bolt, so that waves are generated on the water surface, the laminar flow state of the water body is broken, and the flocculant sprayed by atomization is quickly diffused and pushed to the deep water body, avoiding the problem that the flocculant only floats on the water surface or is locally accumulated. For defluorination, the reaction between the fluorine ion and the flocculant needs to rely on sufficient mass transfer, and the wave disturbance can shorten the diffusion time of the medicine, so that the flocculant can combine with the free fluorine ion in the water faster, and the sedimentation separation efficiency is improved. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description only show some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor on the basis of the drawings shown.

[0030] Figure 1 The best structural schematic diagram provided by the present application is shown in the figure.

[0031] Figure 2 The structural schematic diagram of the right view of the flocculation tank provided by the present application is shown in the figure.

[0032] Figure 3 The structural schematic diagram of the flocculation mechanism, flocculation auxiliary mechanism and scraping mechanism provided by the present application is shown in the figure.

[0033] Figure 4 The structural schematic diagram of the flocculation mechanism, flocculation auxiliary mechanism and scraping mechanism provided by the present application is shown in the figure. Figure 3 The structural schematic diagram of the enlarged A area shown in the figure is shown in the figure.

[0034] Figure 5 The state diagram of the electric telescopic rod driving gear plate moving to the left, and the flapping plate swinging under the action of the swing gear, swing arm, etc. is provided for the present application;

[0035] Figure 6 The state diagram of the electric telescopic rod driving gear plate continuously moving to the left, and the swing gear plate and the scraper moving downward under the action of the driving gear and the driven gear is provided for the present application;

[0036] Figure 7 The structure diagram of the reciprocating mechanism is provided for the present application;

[0037] Figure 8 The structure diagram of the bubble generating mechanism is provided for the present application;

[0038] Figure 9 The structure diagram of the air cylinder cross-sectional view is provided for the present application; Figure 8

[0039] The state diagram of the reciprocating frame continuously driving the scraper moving to the left, and the scraper extruding the push rod is provided for the present application; Figure 10

[0040] The structure diagram of the stirring mechanism is provided for the present application; Figure 11

[0041] The method flow chart is provided for the present application. Figure 12

[0042] Explanation of the reference numerals:

[0043] 1, flocculation tank; 2, reciprocating frame;

[0044] 3, flocculation mechanism; 31, medicine box; 32, medicine outlet pipe; 33, atomizing nozzle; 34, support; 35, electric telescopic rod; 36, gear plate; 37, swing gear;

[0045] 4, flocculation auxiliary mechanism; 41, rotating seat; 42, swing support; 43, flapping plate; 44, connecting rod; 45, bolt; 46, adjusting groove; 47, swing arm;

[0046] 5, scraping mechanism; 51, rotating shaft; 52, driving gear; 53, driven gear; 54, scraper; 55, driven gear plate; 56, sliding rail;

[0047] 6, reciprocating mechanism; 61, threaded screw; 62, threaded seat; 63, guide rail; 64, sliding seat; 65, reciprocating motor;

[0048] ​7, bubble generating mechanism; 71, air cylinder; 72, push rod; 73, piston; 74, spring; 75, air outlet pipe; 76, bubble nozzle;

[0049] 8, stirring mechanism; 81, stirring shaft; 82, stirring support; 83, mixing plate; 84, driving motor;

[0050] 9, discharge pipe; 10, exhaust pipe; 11, feeding pipe. DETAILED DESCRIPTION

[0051] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0052] The present application provides a water pollution treatment equipment and method suitable for industrial high-fluorine wastewater.

[0053] First embodiment:

[0054] Please refer to Figures 1 to 5 A water pollution treatment equipment 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.

[0055] The flocculation mechanism 3 comprises a medicine box 31 and a medicine outlet pipe 32, the medicine box 31 is arranged at 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 communicated with an atomizing nozzle 33, the bottom of the reciprocating frame 2 is fixedly provided with two supports 34, the inner side of each of the two supports 34 is provided with an electric telescopic rod 35, the output end of each of the two electric telescopic rods 35 is fixedly provided with a gear plate 36, the surface of the medicine outlet pipe 32 is fixedly provided with two oscillating gears 37, and each of the two oscillating gears 37 is engaged with a gear plate 36.

[0056] Please refer to Figure 3 : Start the electric telescopic rod 35, the electric telescopic rod 35 is extended to drive the gear plate 36 to move to the left, the gear plate 36 moves to the left to drive the oscillating gear 37 to rotate counterclockwise, the oscillating gear 37 counterclockwise drives the medicine outlet pipe 32 and the atomizing nozzle 33 to rotate counterclockwise, so that the atomizing nozzle 33 adds flocculant to the right side;

[0057] Further, the electric telescopic rod 35 is started, the electric telescopic rod 35 retracts to drive the gear plate 36 to move to the right, the gear plate 36 moves to the right to drive the swing gear 37 to rotate clockwise, the swing gear 37 rotates clockwise to drive the medicine outlet pipe 32 and the atomizing nozzle 33 to rotate clockwise, so that the atomizing nozzle 33 adds flocculating agent to the left side;

[0058] The flocculation auxiliary mechanism 4 comprises two rotating seats 41 and two swing arms 47, the top of the two rotating seats 41 is fixedly connected with the bottom of the reciprocating frame 2, the inner side of the two rotating seats 41 is rotatably connected with a swing support 42, the opposite side of the two swing supports 42 is fixedly provided with a beating plate 43, the two swing arms 47 are fixedly connected with the two ends of the medicine outlet pipe 32, the opposite side of the two swing arms 47 is rotatably connected with a connecting rod 44, the left side of the two connecting rods 44 is provided with a bolt 45, and the two swing supports 42 are connected with the two connecting rods 44 through the bolts 45.

[0059] Please combine Figure 3 and Figure 5 : when the swing gear 37 drives the medicine outlet pipe 32 to rotate counterclockwise, the medicine outlet pipe 32 drives the two swing arms 47 to rotate counterclockwise, and the two swing arms 47 drive the swing supports 42 and the beating plates 43 to rotate to the right through the connecting rods 44 and the bolts 45.

[0060] Further, when the swing gear 37 drives the medicine outlet pipe 32 to rotate clockwise, the medicine outlet pipe 32 drives the two swing arms 47 to rotate clockwise, and the two swing arms 47 drive the swing supports 42 and the beating plates 43 to move to the left through the connecting rods 44 and the bolts 45.

[0061] Further, the electric telescopic rod 35 is reciprocated, the gear plate 36 drives the swing gear 37 to rotate forward and backward, the swing gear 37 drives the medicine outlet pipe 32 to rotate forward and backward, the medicine outlet pipe 32 rotates forward and backward to make the atomizing nozzle 33 swing to add flocculating agent, and the medicine outlet pipe 32 rotates forward and backward to drive the swing supports 42 and the beating plates 43 to reciprocate on the surface of the fluorine-containing raw water through the swing arms 47, the connecting rods 44 and the bolts 45, so that waves are generated on the water surface, the flocculating agent is diffused by the waves, and dead angles during the addition of the flocculating agent can be avoided.

[0062] The top of the reciprocating frame 2 and the rear side of the medicine box 31 are provided with a delivery pump, the delivery pump is used to deliver the medicament in the medicine box 31 to the medicine outlet pipe 32, and the medicament is sprayed to the fluorine-containing raw water by the atomizing nozzle 33.

[0063] 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 amplitude of the swing of the swing bracket 42 driven by the connecting rod 44 will also change when the swing arm 47 swings.

[0064] In this embodiment, the gear plate 36 drives the swing gear 37 and the medicine outlet pipe 32 to rotate forward and backward, so that the atomizing nozzle 33 performs swing type flocculant dispensing. The swing coverage of the atomizing nozzle 33 is wider, and the flocculant can be uniformly sprayed to the whole surface of the fluorine-containing raw water, avoiding the problem of dispensing blank in the edge and corner areas of the pool body, and ensuring that the fluorine ions can fully contact with the flocculant, laying a foundation for the generation of subsequent flocculation compound.

[0065] In addition, the forward and backward rotation of the medicine outlet pipe 32 drives the swing bracket 42 and the beating plate 43 to reciprocate on the surface of the fluorine-containing raw water through the swing arm 47, the connecting rod 44 and the bolt 45, so as to generate waves on the water surface, break the laminar flow state of the water body, quickly diffuse the flocculant sprayed by atomization and push it to the deep water body, and avoid the problem that the flocculant only floats on the water surface or accumulates locally. For defluorination, the reaction of fluorine ions and flocculant needs to rely on sufficient mass transfer, and wave disturbance can shorten the diffusion time of the reagent, so that the flocculant can combine with the free fluorine ions in the water faster, and the sedimentation separation efficiency is improved.

[0066] Second embodiment:

[0067] Please refer to Figure 3 , Figure 6 and Figure 7 , the inner side of the reciprocating frame 2 is rotationally connected with a scraping mechanism 5, the scraping mechanism 5 includes two rotating shafts 51 rotationally 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 driven gear 53, the inner side of the reciprocating frame 2 is vertically and slidingly connected with a scraper 54, the right side of the scraper 54 is fixedly provided with two driven tooth plates 55, the two driven tooth plates 55 are respectively engaged with the two driven gears 53, the left side of the scraper 54 is fixedly provided with two sliding rails 56, and the two sliding rails 56 are slidingly connected with the reciprocating frame 2.

[0068] Please refer to Figure 3 and Figure 6 : when the gear plate 36 continuously moves to the left and is out of contact with the swing gear 37 and is in contact with the driving gear 52, the driving gear 52 will be driven to rotate counterclockwise, the driving gear 52 drives the driven gear 53 to rotate counterclockwise through the rotating shaft 51, and the driven gear 53 drives the scraper 54 to move downward, so that the bottom of the scraper 54 is inserted into the water body.

[0069] 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, the rotating shaft 51 will not rotate alone, the bottom of the scraper 54 is provided with a scraping groove, and the left side of the flocculation tank 1 is provided with a collecting groove;

[0070] The inner wall of the flocculation tank 1 is transversely connected with a reciprocating mechanism 6, the reciprocating mechanism 6 includes a threaded rod 61 transversely connected to the inner wall of the flocculation tank 1, the surface of the threaded rod 61 is threadedly connected with a threaded seat 62, the bottom of the threaded seat 62 is fixedly connected with the top of the reciprocating frame 2, the front side and the rear side of the inner wall of the flocculation tank 1 are both fixedly provided with a guide rail 63, the surfaces of the two guide rails 63 are both slidably connected with two sliding seats 64, opposite sides of the four sliding seats 64 are fixedly connected with the surface of the reciprocating frame 2, and the left side of the flocculation tank 1 is provided with a reciprocating motor 65 for driving the threaded rod 61 to rotate;

[0071] Please refer to Figure 7 : start the reciprocating motor 65, the reciprocating motor 65 rotates to drive the threaded rod 61 to rotate, the threaded rod 61 rotates to drive the threaded seat 62 and the reciprocating frame 2 to move rightward, the sliding seat 64 slides rightward on the surface of the guide rail 63, and through the reverse rotation of the reciprocating motor 65, the reciprocating frame 2 can be driven to move leftward, the reciprocating frame 2 moves leftward and rightward, so as to adjust the working position of the atomizing nozzle 33 and the scraper 54, and through the reciprocating frame 2 driving the scraper 54 to move leftward, the suspended matter on the top of the fluorine-containing raw water can be scraped into the collecting groove.

[0072] In the embodiment, when the gear plate 36 contacts the driving gear 52, the bottom of the scraper 54 is inserted into the water body, and the flocculation of fluorine ions and flocculants in the fluorine-containing raw water, such as aluminum fluoride complex or calcium fluoride complex, is mostly floated or suspended on the upper layer of the water body, through the reciprocating frame 2 driving the scraper 54 to move leftward, the fluorine-containing suspended matter on the water surface can be scraped into the left collecting groove in a directional manner when the scraper 54 moves leftward, the flocculation of the fluorine-containing raw water is removed, and the problem that the flocculation is dispersed or sinks to the bottom of the tank due to water flow disturbance, which causes subsequent removal difficulty, or even fluorine ions are re-dissolved, is avoided.

[0073] Third embodiment:

[0074] Please refer to Figure 1 , Figures 8 to 11The left side of the flocculation tank 1 is fixedly provided with a bubble generating mechanism 7, the bubble generating mechanism 7 comprises a gas cylinder 71 fixedly arranged on the left side of the flocculation tank 1, a push rod 72 slidably connected in the flocculation tank 1, a piston 73 fixedly arranged on the left end of the push rod 72, the surface of the piston 73 is slidably connected with the inner wall of the gas cylinder 71, a spring 74 is sleeved on the surface of the push rod 72 and located in the flocculation tank 1, a gas outlet pipe 75 is longitudinally arranged in the flocculation tank 1, a plurality of bubble nozzles 76 are communicated with the top of the gas outlet pipe 75, and the gas cylinder 71 is communicated with the gas outlet pipe 75 through a hose;

[0075] Please refer to Figures 8 to 10 :When the reciprocating frame 2 continuously drives the scraper 54 to move to the left, the scraper 54 will extrude the push rod 72 to the left, so that the push rod 72 drives the piston 73 to slide to the left in the inner wall of the gas cylinder 71, the gas in the gas cylinder 71 is transported into the gas outlet pipe 75 through the hose, and the bubble nozzles 76 are used for transporting the gas into the fluorine-containing raw water in the form of micro-bubbles, the bubbles are adsorbed on the surface of the fluorine-containing flocculation body with negative electricity, so that the fluorine-containing flocculation body floats to the water surface, and a floating sludge layer with uniform thickness is formed, the scraper 54 can push the floating sludge layer into the collecting groove, and the discharge pipe 10 can discharge the floating sludge layer out of the flocculation tank;

[0076] Preferably, the top of the gas cylinder 71 is provided with an air extraction pipeline, and the air extraction pipeline and the hose are both provided with a one-way valve.

[0077] The inner wall of the flocculation tank 1 is transversely rotatably connected with a stirring mechanism 8, the stirring mechanism 8 comprises a stirring shaft 81 transversely rotatably connected with the inner wall of the flocculation tank 1, a plurality of groups of stirring supports 82 are fixedly arranged on the surface of the stirring shaft 81, and mixing plates 83 are fixedly arranged on the surfaces of the plurality of groups of stirring supports 82; a driving motor 84 is arranged on the left side of the flocculation tank 1 and used for driving the stirring shaft 81 to rotate.

[0078] Please refer to Figure 11 :Start the driving motor 84, the driving motor 84 drives the stirring shaft 81 to rotate, the stirring shaft 81 drives the mixing plates 83 to rotate through the plurality of groups of stirring supports 82, so that the fluorine-containing raw water and the flocculant are mixed.

[0079] The bottom of the flocculation tank 1 is communicated with two discharge pipes 9, the left side of the flocculation tank 1 is communicated with two discharge pipes 10, and the front side of the flocculation tank 1 is communicated with a feeding pipe 11.

[0080] In this embodiment, when the scraper 54 moves to the left to press the push rod 72, the air cylinder 71 generates gas in the form of tiny bubbles in the fluorine-containing raw water, the bubble surface is positively charged, and can be combined with the negatively charged fluorine-containing flocculation through the charge adsorption effect. The buoyancy of the bubble can overcome the gravity of the flocculation and quickly lift it to the water surface to form a thick and uniform scum layer. The fluorine ion desorption caused by the long retention of the flocculation in the water body can be avoided. At the same time, after the flocculation floats, the structure of the scum layer is relatively tight, which can effectively reduce the risk of breaking during the scraping of the scraper 54, ensure that the fluorine-containing flocculation is efficiently collected into the collection tank, reduce the possibility of fluorine concentration rebound of the effluent, and improve the defluorination effect on high-fluorine wastewater.

[0081] Fourth embodiment:

[0082] Please refer to Figure 12 A water pollution treatment method suitable for industrial high-fluorine wastewater, comprising the following steps:

[0083] Step S1, raw material reaction: dissolve zirconium nitrate and trimesic acid in a mixed solvent of DMF (N, N-dimethylformamide) and acetic acid, transfer to a reaction kettle after stirring to completely dissolve, adjust the PH of the reaction system, and generate MOF-808 crystals through solvothermal reaction;

[0084] Preferably, zirconium nitrate and trimesic acid are dissolved at a molar ratio of 1:2.5, the PH is adjusted to 2.5, and the solvothermal reaction is carried out at 135℃ for 36h;

[0085] Step S2, purification treatment: after the reaction is completed, the product is centrifuged and washed with DMF and methanol in sequence to remove unreacted ligands and solvents, and finally vacuum dried to obtain white MOF-808 powder;

[0086] Preferably, vacuum drying at 80℃ for 12h;

[0087] Step S3, nitrogen-doped modification: mix the MOF-808 powder with melamine, and carbonize under inert gas atmosphere at high temperature to form nitrogen-doped MOF-808 (N-MOF-808), which improves the electrical conductivity of the material;

[0088] Preferably, the inert gas is argon, and the temperature is raised to 600℃ at a rate of 5℃ / min and kept constant for 2h;

[0089] Step S4, hydroxyl modification: immerse N-MOF-808 in a citric acid solution, and through stirring, citric acid molecules are coordinated with zirconium clusters to anchor hydroxyl groups (-OH) on the surface of the pores, thereby enhancing the adsorption selectivity of fluorine ions;

[0090] Preferably, a 100ml citric acid solution with PH=3.0 is prepared, stirred at 80℃ for 12h, and then filtered and washed with deionized water until neutral;

[0091] Step S5, slurry preparation: mixing the modified MOF-808 powder with carbon nanotubes (CNT), polyvinylidene fluoride (PVDF) binder, adding N-methyl pyrrolidone (NMP) solvent and ball milling to form a uniform slurry;

[0092] Preferably, ball milling for 4 hours at a speed of 300 rpm;

[0093] Step S6, coating and forming: coating the slurry on the surface of the porous carbon paper current collector, drying and pressing to form a MOF-808-based composite electrode;

[0094] Preferably, the thickness of the carbon paper current collector is 0.3 mm, the porosity is 85%, and the carbon paper current collector is dried at 80°C under vacuum for 12 hours and pressed at a pressure of 10 MPa for 5 minutes;

[0095] Step S7, electrode configuration: using the MOF-808 composite electrode as the anode, the activated carbon electrode as the cathode, and the titanium mesh as the current collector to construct an asymmetric CDI device;

[0096] Preferably, the MOF-808 composite electrode and the activated carbon electrode are placed in parallel with a distance of 3 mm, and the titanium mesh is used as the current collector to assemble an asymmetric CDI module;

[0097] Step S8, adsorption-regeneration cycle: in the adsorption stage, a voltage is applied to drive the migration of fluoride ions to the surface of the MOF-808 electrode, and the fluoride ions are captured by the coordination action of the microporous sieve and the zirconium cluster; in the regeneration stage, the voltage is reversed and the electrode is flushed to release the adsorbed fluoride ions and restore the activity of the electrode;

[0098] Preferably, the voltage is 1.0 V, the flow rate is 10 ml / min, the water inlet pH is 6.0, and the adsorption time is 30 minutes; after adsorption saturation, the electrodes are short-circuited and a voltage of -0.5 V is applied for 10 minutes, and at the same time, the electrodes are flushed with a NaCl solution at a flow rate of 20 ml / min;

[0099] Step S9, fluoride resource recovery: reacting the regenerated waste liquid with a calcium salt to generate calcium fluoride precipitate to realize the resource recovery of fluoride ions;

[0100] Preferably, the regenerated waste liquid is mixed with a 10% CaCl2 solution (Ca 2+ :1.2:1 molar ratio), the pH is adjusted to 7.0, and the mixture is stirred for 30 minutes to generate CaF2 precipitate, and the fluoride resource is recovered after centrifugal separation.

[0101] In this embodiment, by combining MOF material modification and capacitive deionization technology, in terms of anti-interference and adaptation to complex water quality, industrial wastewater often contains a large amount of coexisting ions and impurities. The process anchors hydroxyl groups on the pore surface of MOF-808 through hydroxyl modification, relies on the strong coordination effect of specific metal clusters and fluorine ions to preferentially capture fluorine, and then combines the micropore sieving effect of MOF materials to exclude macromolecular impurities interference. Even if the concentration of coexisting ions is much higher than that of fluorine, the fluorine adsorption selectivity can still remain high. It can adapt to high-salt and high-impurity wastewater in coal chemical industry and fluorine chemical industry, and realize efficient, stable and repeatable fluorine ion removal and resource utilization.

[0102] Please refer to Figures 1 to 12 The working principle of the water pollution control equipment suitable for industrial high-fluorine wastewater provided by the application is as follows:

[0103] Step S1, the fluorine-containing raw water is introduced into the flocculation tank 1 through the feed pipe 11, the driving motor 84 is started, the driving motor 84 rotates to drive the stirring shaft 81 to rotate, the stirring shaft 81 rotates to drive the mixing plate 83 to rotate through the multiple groups of stirring supports 82, so that the fluorine-containing raw water is pre-mixed;

[0104] The reciprocating motor 65 is started, the reciprocating motor 65 rotates to drive the threaded lead screw 61 to rotate, the threaded lead screw 61 rotates to drive 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, and through the reverse rotation of the reciprocating motor 65, the reciprocating frame 2 can be driven to move to the left;

[0105] Step S2, the electric telescopic rod 35 is started, the electric telescopic rod 35 is telescoped to drive the gear plate 36 to reciprocate, the gear plate 36 reciprocates to drive the swing gear 37 to rotate forward and backward, the swing gear 37 rotates forward and backward to drive the medicine outlet pipe 32 and the atomizing nozzle 33 to rotate forward and backward, the conveying pump is started, the conveying pump conveys the medicament in the medicine box 31 to the medicine outlet pipe 32, the atomizing nozzle 33 is used to swing the medicament to spray to the fluorine-containing raw water, through the reciprocating movement of the reciprocating frame 2 left and right, the atomizing nozzle 33 is driven to move reciprocatingly to swing and spray the medicament;

[0106] The medicine outlet pipe 32 rotates forward and backward, the swing arm 47, the connecting rod 44 and the bolt 45 drive the swing support 42 and the beating plate 43 to reciprocate on the surface of the fluorine-containing raw water, so that waves are generated on the water surface, the flocculant is diffused out by using the waves, and the dead angle of the flocculant when it is put can be avoided;

[0107] Step S3: After the reagent is added, let it stand for 15 minutes. When the reagent has fully reacted with the fluoride-containing raw water, it will move to the left through the gear plate 36, disengage from the swing gear 37, and come into contact with the active gear 52. This will drive the active gear 52 to rotate counterclockwise. The active gear 52 will drive the passive gear 53 to rotate counterclockwise through the rotating shaft 51. The counterclockwise rotation of the passive gear 53 will drive the scraper 54 to move downward, so that the bottom of the scraper 54 is inserted into the water.

[0108] In step S4, the reciprocating mechanism 6 drives the reciprocating frame 2 and scraper 54 to move continuously to the left. The scraper 54 will squeeze the push rod 72 to the left, causing the push rod 72 to drive the piston 73 to slide to the left on the inner wall of the air cylinder 71. The gas in the air cylinder 71 is delivered to the air outlet pipe 75 through the hose. The gas is delivered to the fluoride-containing raw water in the form of tiny bubbles using the bubble nozzle 76. The bubbles will be adsorbed on the surface of the negatively charged fluoride-containing flocs, causing the fluoride-containing flocs to float to the water surface and form a scum layer of uniform thickness.

[0109] In step S5, the scraper 54 is adjusted to the right working position by the reciprocating mechanism 6, and then the bottom of the scraper 54 is adjusted into the water. The reciprocating mechanism 6 drives 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 side, and discharging it through the discharge pipe 10. After the scraping work is completed, the equipment can be reset.

[0110] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made under the concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A water pollution treatment device suitable for industrial high-fluoride wastewater, characterized in that, Includes flocculation tank, reciprocating frame, flocculation mechanism and flocculation auxiliary mechanism; The flocculation mechanism includes a medicine tank and a medicine outlet pipe. The medicine tank is located on the top of the reciprocating frame, and 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 an atomizing nozzle. Two supports are fixedly installed at the bottom of the reciprocating frame. Electric telescopic rods are installed on the inner side of the two supports. Gear plates are fixedly installed at the output ends of the two electric telescopic rods. Two swing gears are fixedly installed on the surface of the medicine outlet pipe, and the two swing gears mesh with the two gear plates respectively. 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. Swing brackets are rotatably connected to the inner sides of the two rotating seats. Beating plates are fixedly provided on the opposite sides of the two swing brackets. The two swing arms are fixedly connected to both ends of the drug outlet tube. Connecting rods are rotatably connected to the opposite sides of the two swing arms. Bolts are provided on the left side of the two connecting rods. The two connecting rods are respectively connected to the two swing brackets by bolts. Adjustment grooves are provided on the inner sides of the two swing brackets. A delivery pump is installed at the top of the reciprocating frame and at the rear of the medicine tank. The delivery pump is used to deliver the medicine in the medicine tank to the medicine outlet pipe and spray the medicine onto the fluoride-containing raw water using an atomizing nozzle. By loosening the bolts, the position of the left side of the connecting rod within the swing bracket can be adjusted. When the position of the left side of the swing bracket changes, the amplitude of the swing bracket swinging via the connecting rod will also change when the swing arm swings. A scraping mechanism is rotatably connected to the inner side of the reciprocating frame. The scraping mechanism includes two rotating shafts rotatably connected to the inner side of the reciprocating frame. A driving gear and a driven gear are fixed on the surface of each of the two rotating shafts. A scraper is vertically slidably connected to the inner side of the reciprocating frame. Two driven toothed plates are fixed on the right side of the scraper. The two driven toothed plates mesh with the two driven gears respectively. Two slide rails are fixed on the left side of the scraper. The two slide rails are slidably connected to the reciprocating frame. The inner wall of the flocculation tank is laterally rotatably connected to a reciprocating mechanism. 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. Guide rails are fixedly provided on the front and rear sides of the inner wall of the flocculation tank. Two sliding seats are slidably connected to the surfaces of the two guide rails. The opposite side of the four sliding seats is 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. A bubble generating mechanism is fixedly installed on the left side of the flocculation tank. The bubble generating mechanism includes an air cylinder fixedly installed on the left side of the flocculation tank. A push rod is slidably connected inside the flocculation tank. A piston is fixedly installed at 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 sleeved on the surface of the push rod inside the flocculation tank. An air outlet pipe is longitudinally arranged inside the flocculation tank. Multiple bubble nozzles are connected to the top of the air outlet pipe. The air cylinder is connected to the air outlet pipe through a hose.

2. The water pollution treatment equipment for industrial high-fluoride wastewater according to claim 1, characterized in that, The inner wall of the flocculation tank is rotatably connected to a stirring mechanism. The stirring mechanism includes a stirring shaft rotatably connected to the inner wall of the flocculation tank. Multiple sets of stirring supports are fixed on the surface of the stirring shaft, and mixing plates are fixed on the surface of the multiple sets of stirring supports. A drive motor for driving the stirring shaft to rotate is provided on the left side of the flocculation tank.

3. The water pollution treatment equipment for industrial high-fluoride 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.

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