Defluorination reactor device

Abstract

The invention discloses a defluorination reactor device, and aims to solve the problems that precipitates generated by a medicament method in the prior art are light in specific gravity, slow in sedimentation and poor in solid-liquid separation effect; enough sedimentation time is needed, and a huge sedimentation tank body causes large occupied area of process equipment. According to the technical scheme, the system comprises a reaction system, the reaction system comprises a defluorination reaction tank and a flocculation reaction tank which are communicated with each other, a defluorination agent adding device is arranged in the defluorination reaction tank, and a flocculating agent adding device is arranged in the flocculation reaction tank; the concentration system comprises a concentration tank communicated with the flocculation reaction tank and a membrane tank arranged in the concentration tank, and an ultrafiltration membrane device is arranged in the membrane tank; the ultrafiltration membrane device comprises a plurality of water collecting cavities, one side of each water collecting cavity is provided with a yin-yang ultrafiltration membrane, and the interiors of the water collecting cavities are communicated with the outside through water collecting pipes; the clean water system comprises a clean water tank, and the water outlet of the water collecting pipe is communicated with the clean water tank.

Description

Technical Field

[0001] The present invention relates to the technical field of defluorination, and more particularly to a defluorination reactor device. Background Art

[0002] With the tightening of national environmental protection policies, the requirements for the treatment of fluoride-containing wastewater are becoming increasingly stringent. Environmental protection bureaus in many places even require that the fluoride content in the company's external drainage water meet the requirements of Class III water quality in the "Surface Water Environmental Quality Standards", that is, 1.0 mg / L, such as some coal mines in the Huaibei area.

[0003] At present, the pharmaceutical method has been accepted by many corporate customers because of its remarkable effect in treating fluoride-containing wastewater and its more economical effect compared with resin adsorption method, reverse osmosis membrane method, etc. However, because the precipitate generated by the pharmaceutical method has a too light specific gravity and is not easy to settle, a large amount of defluoridation agent needs to be added to ensure that the fluoride in the effluent is less than 1.0 mg / L, and sufficient precipitation time is required. Therefore, at this stage, the pharmaceutical method for defluoridation still has problems such as large area of ​​process equipment, large amount of agent addition, and high operating cost, which also seriously restricts the development of enterprises. Summary of the invention

[0004] The present invention overcomes the following deficiencies in the prior art: (1) the precipitate generated by the reagent method has a light specific gravity, slow sedimentation, and poor solid-liquid separation effect; (2) sufficient sedimentation time is required, and the huge sedimentation tank body causes the process equipment to occupy a large area; (3) in order to ensure the water quality of the effluent, the amount of reagent added is large, and the operating cost is high; (4) the degree of automation is low, and professional personnel are required to operate, otherwise it is easy to add too much or too little reagent, causing the effluent water quality to fluctuate; a defluorination reactor device is provided, which mainly uses membrane filtration to remove the suspended turbidity formed after the addition of the reagent. The liquid is used for solid-liquid separation, and the surface has both a positive charge layer and a negative charge layer, which can effectively reduce the adhesion of aluminum-based agents and realize the physical and chemical separation of high-concentration precipitation flocs and water; the equipment of the present invention adopts a concentration tank to replace the original sedimentation tank, and cooperates with submerged membrane water head pressure filtration to realize the enrichment of precipitation flocs, improve the defluorination efficiency, and solve the problems of large footprint and large dosage of agents in the original equipment; at the same time, remote control technology and automatic control technology are adopted to realize on-site management with few or no people, solving the problems of low degree of automation of the existing technology that most of the on-site operations require professionals.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solution: a defluorination reactor device, comprising: The reaction system comprises a defluorination reaction tank and a flocculation reaction tank which are interconnected, wherein the defluorination reaction tank is provided with a defluorination agent dosing device, and the flocculation reaction tank is provided with a flocculant dosing device; The concentration system includes a concentration tank connected to the flocculation reaction tank, and a membrane tank arranged in the concentration tank, wherein an ultrafiltration membrane device is arranged in the membrane tank; the ultrafiltration membrane device includes a plurality of water collection chambers, and a positive and negative ultrafiltration membranes are arranged on one side of the plurality of water collection chambers, and the water collection chambers are connected to the outside through a water collection pipe; The clean water system includes a clean water tank, and the water outlet of the water collecting pipe is connected with the clean water tank.

[0006] In this application, fluorine-containing wastewater enters the defluorination reaction tank through the water inlet, and the defluorination agent is added through the defluorination dosing device; then the treated water enters the flocculation reaction tank, and the flocculation agent is added through the flocculation dosing device, and the flocculation agent reacts with the treated water to produce floccules; then the treated water enters the concentration tank for concentration, and the clearer liquid in the upper part of the concentration tank overflows from the top of the membrane tank into the membrane tank. During this period, the floccules produced in the concentration tank enter the concentration mud bucket and are then discharged through the first row of waste pipes; the floccules in the membrane tank enter the membrane pool mud bucket and are then discharged through the second row of waste pipes; then the treated water is treated by the yin and yang ultrafiltration membrane device, and after the treated water passes through the yin and yang ultrafiltration membrane, it enters the clear water tank through the water collecting pipe, and the clear water tank is provided with a water outlet, and the clear water of the clear water tank is discharged through the water outlet. Remote control or automatic control is adopted, and no personnel management is required on site.

[0007] Preferably, the cation-cation ultrafiltration membrane comprises a support layer, a negative charge layer and a positive charge layer which are sequentially away from the water collection chamber.

[0008] The surface of fluoride ions is negatively charged and will be captured by the positive charge layer. The fluoride ions that pass through the positive charge layer will be repelled by the negative charge layer and then return to the positive charge layer. The surface of the defluoridation agent is positively charged and will be repelled by the positive charge on the surface of the positive charge layer when it contacts the outer layer of the anion and cation ultrafiltration membrane, thereby improving the efficiency of fluoride removal.

[0009] Preferably, it also includes a cleaning device for cleaning the ultrafiltration membrane device; the cleaning device includes a cleaning frame arranged on the outside of the ultrafiltration membrane device and a spray head arranged on the inner wall of the cleaning frame.

[0010] A cleaning device is provided to clean the positive and negative ultrafiltration membranes. A spray head is provided on the cleaning frame, and a plurality of spray heads can be conveniently installed on the cleaning frame.

[0011] Preferably, the spray head is connected to the clean water tank through a spray water pipe, and a flushing device is provided on the spray water pipe.

[0012] The water in the clean water tank is used to clean the yin and yang ultrafiltration membranes, which can reduce the waste of water resources and realize the recycling of treated water.

[0013] Preferably, a stirring device is provided in the defluorination reaction tank and the flocculation reaction tank, and the stirring device comprises a stirring motor and a stirring paddle provided on an output shaft of the stirring motor.

[0014] The stirring devices in the defluorination reaction tank and the flocculation reaction tank can stir the flocculation agent or the defluorination agent evenly, so that the defluorination agent and the flocculation agent can fully react with the treated water in the defluorination reaction tank and the flocculation reaction tank respectively.

[0015] Preferably, a concentrated mud hopper is provided at the bottom of the concentration tank, and the horizontal cross-sectional area of ​​the concentrated mud hopper gradually decreases in the vertical downward direction; a first row of waste pipes is provided at the bottom of the concentrated mud hopper.

[0016] The thickening mud hopper forms a funnel shape with an opening that gradually narrows downward, so that the flocs in the thickening tank can settle at the bottom of the thickening mud hopper. A first row of waste pipes is provided at the bottom of the thickening mud hopper, and finally the flocs in the thickening mud hopper are precipitated and discharged from the first row of waste pipes.

[0017] Preferably, a membrane pool mud hopper is provided at the bottom of the membrane pool, and the horizontal cross-sectional area of ​​the membrane pool mud hopper gradually decreases along the vertical downward direction; a second row of waste pipes is provided at the bottom of the membrane pool mud hopper.

[0018] The membrane pool mud hopper forms a funnel shape with an opening that gradually shrinks downward, so that the flocs in the membrane pool mud hopper can settle at the bottom of the membrane pool mud hopper. A second row of waste pipes is provided at the bottom of the membrane pool mud hopper. Finally, the flocs in the membrane pool are precipitated and finally discharged from the second row of waste pipes.

[0019] Preferably, a plurality of water collecting chambers are arranged in parallel, and two spray heads are correspondingly arranged on both sides of the plurality of water collecting chambers.

[0020] The water collecting chambers are arranged in parallel, and two spray heads are correspondingly arranged on both sides of each water collecting chamber. After the yin and yang ultrafiltration membranes react for a period of time, the tiny holes on the yin and yang ultrafiltration membranes will be blocked. Therefore, the yin and yang ultrafiltration membranes can be cleaned by the spray heads on both sides to keep the yin and yang ultrafiltration membranes clean.

[0021] Preferably, a separation device for preventing clean water from being discharged is arranged in the first waste pipe, and the separation device comprises a positioning plate arranged in the first waste pipe, and a plurality of first holes are arranged through the positioning plate; A second hole is provided through the center of the positioning plate; a sleeve is provided in the second hole, and an opening is provided at the top of the sleeve; a connecting rod is slidably provided in the sleeve, and a first spring is provided in the sleeve to push the connecting rod to move downward; A blocking plate is connected to the outer side of the opening where the connecting rod extends, and the projection of the blocking plate toward the positioning plate covers all the first holes; An air bag is connected to the top of the baffle plate through a drawstring, and the air bag is located in the concentration tank.

[0022] The separation device can prevent clean water from being discharged from the first waste pipe, thereby reducing the discharge of sewage and improving the efficiency of fluorine removal.

[0023] Preferably, a side wall outlet is provided on the side wall of the first row of waste pipes, a sliding piston is provided at the bottom of the first row of waste pipes, and a second spring is provided at the bottom of the sliding piston to push it to move upward.

[0024] When the first hole is opened, the pressure of the liquid in the first row of waste pipes acts on the sliding piston, and the sliding piston overcomes the elastic force of the second spring and moves downward. At this time, the side wall outlet is opened, and the flocculent sediment is discharged from the side wall outlet; when the first hole is closed, the liquid pressure acting on the sliding piston is reduced, and the second spring pushes the sliding piston to move upward to block the side wall outlet, thereby preventing the liquid from being discharged from the side wall outlet, and at the same time ensuring that liquid remains in the first row of waste pipes to maintain the balance of the hydraulic pressure in the first row of waste pipes.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: the present application mainly adopts the form of membrane filtration to separate the suspension formed after adding the medicine into solid and liquid, and the surface has both a positive charge layer and a negative charge layer, which can effectively reduce the adhesion of aluminum-based agents and realize the physical and chemical separation of high-concentration precipitation flocs and water; the equipment of the present invention adopts a concentration tank to replace the original sedimentation tank, and cooperates with submerged membrane water head pressure filtration to realize the enrichment of precipitation flocs, improve the fluorine removal efficiency, and solve the problems of large footprint and large dosage of agents in the original equipment; at the same time, remote control technology and automatic control technology are adopted to realize on-site management with few or no people, solving the problems of the prior art that most of the on-site operations require professionals and the low degree of automation. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of the overall structure of the present invention.

[0027] Figure 2 It is a schematic structural diagram of the flushing device of the present invention.

[0028] Figure 3 It is a schematic structural diagram of the cation and cation ultrafiltration membrane of the present invention.

[0029] Figure 4 It is a three-dimensional structural diagram of the cation and cation ultrafiltration membranes of the present invention when assembled.

[0030] Figure 5 It is a schematic diagram of the overall structure of the second embodiment of the present invention.

[0031] Figure 6 It is a schematic structural diagram of the separation device of the present invention.

[0032] Figure 7 It is a schematic diagram of the principle of the cation and yang ultrafiltration membrane of the present invention.

[0033] Figure 8 It is a statistical diagram of the fluoride content of the inlet and outlet water under the actual operating state of the present invention.

[0034] In the figure: 1, reaction system, 11, water inlet, 12, defluorination reaction tank, 13, stirring device in defluorination reaction tank, 14, flocculation reaction tank, 15, stirring device in flocculation reaction tank, 16, defluorination agent dosing device, 17, flocculant dosing device; 2. Concentration system, 21. Membrane pool, 22. Ultrafiltration membrane device, 221. Water collecting pipe, 222. Yin-yang ultrafiltration membrane, 2221. Basic support layer, 2222. Negative charge layer, 2223. Positive charge layer, 223. Spray head, 23. Concentration pool, 24. Membrane pool mud hopper, 25. Concentration barrier wall, 26. Concentration mud hopper, 261. First row of waste pipe, 262. Side wall outlet; 3. Clean water system, 31. Water outlet monitoring device, 32. Flushing device, 33. Clean water tank, 34. Water outlet; 4. sliding piston, 41. second spring, 42. limiting ring; 5. Separation device, 51. Positioning plate, 511. First hole, 512. Second hole, 52. Sleeve, 53. Connecting rod, 54. First spring, 55. Blocking plate, 56. Airbag, 57. Pull rope; DETAILED DESCRIPTION

[0035] The technical solution of the present invention is further described in detail below through specific embodiments and in conjunction with the accompanying drawings: Example 1: Reference Figures 1 to 8 As shown, a defluorination reactor device includes: a reaction system 1, a concentration system 2 and a clean water system 3.

[0036] The reaction system 1 includes a defluorination reaction tank 12 and a flocculation reaction tank 14 which are interconnected. A defluorination agent dosing device 16 is provided in the defluorination reaction tank 12, and a flocculant dosing device 17 is provided in the flocculation reaction tank 14. The defluorination agent dosing device 16 can automatically add defluorination agent to the defluorination reaction tank 12, and the flocculant dosing device 17 can automatically add flocculant to the flocculation reaction tank 14, thereby realizing the function of automatically adding defluorination agent and flocculant. A water inlet 11 is provided on the side wall of the defluorination reaction tank 12.

[0037] The concentration system 2 includes a concentration tank 23 connected to the flocculation reaction tank 14, and a membrane tank arranged in the concentration tank 23, wherein an ultrafiltration membrane device 22 is arranged in the membrane tank; when the wastewater in the concentration tank 23 exceeds the edge of the top of the membrane tank 21, the wastewater in the concentration tank 23 overflows from the edge of the top of the membrane tank 21 into the membrane tank 21, and the side wall of the membrane tank 21 is composed of a concentration barrier wall 25, which can prevent the treated water from passing through the side wall of the membrane tank 21 and entering the membrane tank 21. The ultrafiltration membrane device 22 includes a plurality of water collection chambers, and a positive and negative ultrafiltration membrane 222 is arranged on one side of the plurality of water collection chambers, and the water collection chamber is connected to the outside through a water collection pipe 221.

[0038] The clean water system 3 includes a clean water tank 33 , and a water outlet 34 of the water collecting pipe 221 is connected to the clean water tank 33 .

[0039] In the present application, fluorine-containing wastewater enters the defluorination reaction tank 12 through the water inlet 11, and the defluorination agent is added through the defluorination agent dosing device 16; then the treated water enters the flocculation reaction tank 14, and the flocculation agent is added through the flocculation agent dosing device 17, and the flocculation agent reacts with the treated water to produce floccules; then the treated water enters the concentration tank 23 for concentration, and the clearer liquid in the upper part of the concentration tank 23 overflows from the top of the membrane tank 21 into the membrane tank 21. During this period, the floccules produced in the concentration tank 23 enter the concentration mud hopper 26, and then are discharged through the first row of waste pipes 261; the floccules in the membrane tank 21 enter the membrane tank mud hopper 24, and then are discharged through the second row of waste pipes; then the treated water is treated by the ultrafiltration membrane device 22, and after the treated water passes through the yin and yang ultrafiltration membranes 222, it enters the clear water tank 33 through the water collecting pipe 221, and the clear water tank 33 is provided with a water outlet 34, and the clear water of the clear water tank 33 is discharged through the water outlet 34. Remote control or automatic control is adopted, and no personnel management is required on site.

[0040] In one embodiment, a stirring device is provided in the defluorination reaction tank 12 and the flocculation reaction tank 14, and the stirring device includes a stirring motor and a stirring paddle provided on the output shaft of the stirring motor. The stirring device in the defluorination reaction tank 12 and the flocculation reaction tank 14 can stir the flocculation agent or the defluorination agent evenly, so that the defluorination agent and the flocculation agent can fully react with the treated water in the defluorination reaction tank 12 and the flocculation reaction tank 14, respectively.

[0041] In one embodiment, a thickening mud hopper 26 is provided at the bottom of the thickening tank 23. The horizontal cross-sectional area of ​​the thickening mud hopper 26 gradually decreases in the vertical downward direction, so that the thickening mud hopper 26 can form a funnel shape with an opening that gradually decreases downward, so that the flocs in the thickening tank 23 can settle at the bottom of the thickening mud hopper 26. A first row of waste pipes 261 is provided at the bottom of the thickening mud hopper 26, and finally the flocs in the thickening mud hopper 26 are precipitated and discharged from the first row of waste pipes 261.

[0042] In one of the embodiments, a membrane pool mud hopper 24 is provided at the bottom of the membrane pool 21. The horizontal cross-sectional area of ​​the membrane pool mud hopper 24 gradually decreases along the vertical downward direction, so that the membrane pool mud hopper 24 forms a funnel shape with an opening gradually decreasing downward, so that the flocs in the membrane pool mud hopper 24 can settle at the bottom of the membrane pool mud hopper 24. A second row of waste pipes is provided at the bottom of the membrane pool mud hopper 24, and finally the flocs in the membrane pool 21 are precipitated and discharged from the second row of waste pipes.

[0043] In one embodiment, a cleaning device for cleaning the ultrafiltration membrane device 22 is included; the cleaning device includes a cleaning frame arranged outside the ultrafiltration membrane device 22 and a spray head 223 arranged on the inner wall of the cleaning frame. After the positive and negative ultrafiltration membranes 222 react for a period of time, the tiny holes on the positive and negative ultrafiltration membranes 222 will be blocked, so a cleaning device is provided to clean the positive and negative ultrafiltration membranes 222. The spray head 223 is arranged on the cleaning frame, and a plurality of spray heads 223 can be installed on the cleaning frame.

[0044] In one embodiment, a plurality of water collecting chambers are arranged in parallel, and two spray heads 223 are correspondingly arranged on both sides of the plurality of water collecting chambers. Each water collecting chamber is provided with a water collecting pipe 221, and the water collecting pipes 221 of each water collecting chamber are finally converged into a total water collecting pipe 221. The water collecting chambers in this embodiment are arranged in parallel, and two spray heads 223 are correspondingly arranged on both sides of each water collecting chamber. After the yin and yang ultrafiltration membranes 222 react for a period of time, the tiny holes on the yin and yang ultrafiltration membranes 222 will be blocked. Therefore, spray heads 223 are arranged to clean the yin and yang ultrafiltration membranes 222.

[0045] Since the impact force of the water sprayed from the spray head 223 will be reduced by the treated water in the membrane pool 21 when the yin and yang ultrafiltration membranes 222 are directly cleaned in the membrane pool 21, the ultrafiltration membrane device 22 and the cleaning frame are connected to the lifting device, and the lifting device can be a crane, a gantry truck and other equipment. When it is necessary to spray the yin and yang ultrafiltration membranes 222, the lifting device directly lifts the ultrafiltration membrane device 22 and the lifting device out of the membrane pool 21 to clean the yin and yang ultrafiltration membranes 222. Of course, the cleaning frame can also directly rinse the yin and yang ultrafiltration membranes 222 in the membrane pool 21.

[0046] In addition, a water outlet monitoring device 31 is provided on the water collecting pipe 221. The water outlet monitoring device 31 is a flow meter provided on the water collecting pipe 221. When the yin and yang ultrafiltration membranes 222 are blocked, the flow rate of water in the water collecting pipe 221 is reduced, and the water outlet monitoring device 31 will sound an alarm to remind the operator to clean the yin and yang ultrafiltration membranes 222.

[0047] In one embodiment, the spray head 223 is connected to the clean water tank 33 through spraying, and a flushing device 32 is provided on the spray water pipe. The flushing device 32 is a flushing pump, which can pump out the water in the clean water tank 33, and then spray it out from the spray head 223 to clean the yin and yang ultrafiltration membranes 222. That is, in this embodiment, the water in the clean water tank 33 is used to clean the yin and yang ultrafiltration membranes 222, thereby reducing the waste of water resources and realizing the recycling of treated water.

[0048] In one embodiment, the anionic ultrafiltration membrane 222 includes a base support layer 2221, a negative charge layer 2222, and a positive charge layer 2223, which are sequentially away from the water collection chamber. The negative charge layer 2222 is on the inside, and the positive charge layer 2223 is on the outside. The negative charge layer 2222 in this embodiment is polydopamine with a thickness of 5-20 nm, and the positive charge layer 2223 is polyethyleneimine or other positively charged polymers with a thickness of 20-50 nm. The base support layer 2221 can be a polymer organic membrane, an inorganic membrane, or a composite membrane. Figure 7 As shown, the surface of fluorine ions is negatively charged and will be captured by the positive charge layer 2223. The fluorine ions that pass through the positive charge layer 2223 will be repelled by the negative charge layer 2222 and then return to the positive charge layer 2223. The surface of the defluorinating agent is positively charged and will be repelled by the positive charge on the surface of the positive charge layer 2223 when it contacts the outer layer of the positive and negative ultrafiltration membranes 222, and then return to the membrane pool 21 to further react with the fluorine ions. The defluorinating agent that has reacted completely will be adsorbed by the fluorine ions and accumulated on the surface of the positive charge layer 2223. After a certain period of time, the effluent monitoring device 31 of the ultrafiltration membrane device 22 will give feedback, and the ultrafiltration membrane device 22 will be lifted. The ultrafiltration membrane device 22 is provided with a movable high-pressure spray head 223, which can move up and down to clean the surface of the positive and negative ultrafiltration membranes 222. At this time, the fluorine ions and defluorinating agent on the membrane surface will be taken away by the water flow.

[0049] The working principle of this embodiment is as follows: fluorine-containing wastewater enters the defluorination reaction tank 12 through the water inlet 11, and the defluorination agent is added through the defluorination agent dosing device, and fully reacts under the stirring of the stirring device of the defluorination reaction tank 12; then the treated water enters the flocculation reaction tank 14, and the flocculation agent is added through the flocculant dosing device 17, and fully reacts under the stirring of the stirring device of the flocculation reaction tank 14; then the treated water enters the concentration tank 23 for concentration, and the clearer liquid in the upper part of the concentration tank 23 overflows from the top of the membrane tank 21 into the membrane tank 21. During this period, the floccules in the concentration tank 23 are precipitated into the concentration mud bucket 26, and then discharged from the first waste pipe 261; the flocculent precipitate in the membrane tank 21 enters the membrane tank mud bucket 24, and then discharged from the second waste pipe; the treated water is treated by the ultrafiltration membrane device 22, and the treated water enters the clear water tank 33 by gravity using the siphon effect (the height difference between the membrane tank 21 and the clear water tank 33 is 5-10 m), the clean water in the clean water tank 33 is discharged or reused through the outlet 34, and part of the clean water can be used for cleaning the device to flush the yin and yang ultrafiltration membranes 222.

[0050] In a specific practice, a coal mine used the process and equipment of this patent to defluorinate fluorine-containing mine water. The equipment was in operation for 2 months, and the clean water produced was directly discharged to the nearby watershed. The fluorine-containing mine water is transferred to the defluorination reactor device in this application through a water pump, and 50~150 mg / L of defluorination agent and 1~10 mg / L of flocculant are added. The treated water then enters the concentration tank 23, and the concentrated effluent enters the membrane tank 21, and is treated by the ultrafiltration membrane device 22. The effluent uses gravity to directly enter the clean water tank 33. The height difference between the membrane tank 21 and the clean water tank 33 is 8 m, and finally the clean water is directly discharged. During operation, the surface of the yin and yang ultrafiltration membrane 222 is flushed with a clean water flushing device 32 every 1 hour to remove the fouling layer. The overall area of ​​the on-site equipment is 50 m 2 In actual operation, one pump group is used and the other is reserved, and the water treatment capacity is 100 t / h.

[0051] Fluoride content in and out of mine water during operation Figure 8 As shown in Figure 1, the online selective electrode method is used for fluoride detection. Figure 8 It can be seen that after the equipment was put into operation, the fluoride in the mine water was stably reduced to below the standard of 1.0 mg / L. Compared with the common coagulation defluorination process, this equipment reduces the dosage by 20%, reduces the land area by 40%, and the effluent water quality is more stable.

[0052] Therefore, compared with the prior art, the present application mainly adopts membrane filtration to separate the solid-liquid suspension formed after adding drugs, and the surface has both a positive charge layer 2223 and a negative charge layer 2222, which can effectively reduce the adhesion of aluminum-based agents and realize the physical and chemical separation of high-concentration precipitation flocs and water; the equipment of the present invention adopts a concentration tank 23 to replace the original sedimentation tank, and cooperates with submerged membrane water head pressure filtration to realize the enrichment of precipitation flocs, improve the fluorine removal efficiency, and solve the problems of large footprint and large dosage of agents in the original equipment; at the same time, remote control technology and automatic control technology are adopted to realize on-site management with few or no people, solving the problems of the prior art that most of the on-site operations require professionals and the low degree of automation.

[0053] Example 2: Reference Figures 1 to 8 As shown, a defluorination reactor device includes: a reaction system 1, a concentration system 2 and a clean water system 3.

[0054] The reaction system 1 includes a defluorination reaction tank 12 and a flocculation reaction tank 14 which are interconnected. A defluorination agent dosing device 16 is provided in the defluorination reaction tank 12, and a flocculant dosing device 17 is provided in the flocculation reaction tank 14. The defluorination agent dosing device 16 can automatically add defluorination agent to the defluorination reaction tank 12, and the flocculant dosing device 17 can automatically add flocculant to the flocculation reaction tank 14, thereby realizing the function of automatically adding defluorination agent and flocculant. A water inlet 11 is provided on the side wall of the defluorination reaction tank 12.

[0055] The concentration system 2 includes a concentration tank 23 connected to the flocculation reaction tank 14, and a membrane tank arranged in the concentration tank 23, wherein an ultrafiltration membrane device 22 is arranged in the membrane tank; when the wastewater in the concentration tank 23 exceeds the edge of the top of the membrane tank 21, the wastewater in the concentration tank 23 overflows from the edge of the top of the membrane tank 21 into the membrane tank 21, and the side wall of the membrane tank 21 is composed of a concentration barrier wall 25, which can prevent the treated water from passing through the side wall of the membrane tank 21 and entering the membrane tank 21. The ultrafiltration membrane device 22 includes a plurality of water collection chambers, and a positive and negative ultrafiltration membrane 222 is arranged on one side of the plurality of water collection chambers, and the water collection chamber is connected to the outside through a water collection pipe 221.

[0056] The clean water system 3 includes a clean water tank 33 , and a water outlet 34 of the water collecting pipe 221 is connected to the clean water tank 33 .

[0057] In the present application, fluorine-containing wastewater enters the defluorination reaction tank 12 through the water inlet 11, and the defluorination agent is added through the defluorination agent dosing device 16; then the treated water enters the flocculation reaction tank 14, and the flocculation agent is added through the flocculation agent dosing device 17, and the flocculation agent reacts with the treated water to produce floccules; then the treated water enters the concentration tank 23 for concentration, and the clearer liquid in the upper part of the concentration tank 23 overflows from the top of the membrane tank 21 into the membrane tank 21. During this period, the floccules produced in the concentration tank 23 enter the concentration mud hopper 26, and then are discharged through the first row of waste pipes 261; the floccules in the membrane tank 21 enter the membrane tank mud hopper 24, and then are discharged through the second row of waste pipes; then the treated water is treated by the ultrafiltration membrane device 22, and after the treated water passes through the yin and yang ultrafiltration membranes 222, it enters the clear water tank 33 through the water collecting pipe 221, and the clear water tank 33 is provided with a water outlet 34, and the clear water of the clear water tank 33 is discharged through the water outlet 34. Remote control or automatic control is adopted, and no personnel management is required on site.

[0058] In one embodiment, a stirring device is provided in the defluorination reaction tank 12 and the flocculation reaction tank 14, and the stirring device includes a stirring motor and a stirring paddle provided on the output shaft of the stirring motor. The stirring device in the defluorination reaction tank 12 and the flocculation reaction tank 14 can stir the flocculation agent or the defluorination agent evenly, so that the defluorination agent and the flocculation agent can fully react with the treated water in the defluorination reaction tank 12 and the flocculation reaction tank 14, respectively.

[0059] In one embodiment, a thickening mud hopper 26 is provided at the bottom of the thickening tank 23. The horizontal cross-sectional area of ​​the thickening mud hopper 26 gradually decreases in the vertical downward direction, so that the thickening mud hopper 26 can form a funnel shape with an opening that gradually decreases downward, so that the flocs in the thickening tank 23 can settle at the bottom of the thickening mud hopper 26. A first row of waste pipes 261 is provided at the bottom of the thickening mud hopper 26, and finally the flocs in the thickening mud hopper 26 are precipitated and discharged from the first row of waste pipes 261.

[0060] In one of the embodiments, a membrane pool mud hopper 24 is provided at the bottom of the membrane pool 21. The horizontal cross-sectional area of ​​the membrane pool mud hopper 24 gradually decreases along the vertical downward direction, so that the membrane pool mud hopper 24 forms a funnel shape with an opening gradually decreasing downward, so that the flocs in the membrane pool mud hopper 24 can settle at the bottom of the membrane pool mud hopper 24. A second row of waste pipes is provided at the bottom of the membrane pool mud hopper 24, and finally the flocs in the membrane pool 21 are precipitated and discharged from the second row of waste pipes.

[0061] In one embodiment, a cleaning device for cleaning the ultrafiltration membrane device 22 is included; the cleaning device includes a cleaning frame arranged outside the ultrafiltration membrane device 22 and a spray head 223 arranged on the inner wall of the cleaning frame. After the positive and negative ultrafiltration membranes 222 react for a period of time, the tiny holes on the positive and negative ultrafiltration membranes 222 will be blocked, so a cleaning device is provided to clean the positive and negative ultrafiltration membranes 222. The spray head 223 is arranged on the cleaning frame, and a plurality of spray heads 223 can be installed on the cleaning frame.

[0062] In one embodiment, a plurality of water collecting chambers are arranged in parallel, and two spray heads 223 are correspondingly arranged on both sides of the plurality of water collecting chambers. Each water collecting chamber is provided with a water collecting pipe 221, and the water collecting pipes 221 of each water collecting chamber are finally converged into a total water collecting pipe 221. The water collecting chambers in this embodiment are arranged in parallel, and two spray heads 223 are correspondingly arranged on both sides of each water collecting chamber. After the yin and yang ultrafiltration membranes 222 react for a period of time, the tiny holes on the yin and yang ultrafiltration membranes 222 will be blocked. Therefore, spray heads 223 are arranged to clean the yin and yang ultrafiltration membranes 222.

[0063] Since the impact force of the water sprayed from the spray head 223 will be reduced by the treated water in the membrane pool 21 when the yin and yang ultrafiltration membranes 222 are directly cleaned in the membrane pool 21, the ultrafiltration membrane device 22 and the cleaning frame are connected to the lifting device, and the lifting device can be a crane, a gantry truck and other equipment. When it is necessary to spray the yin and yang ultrafiltration membranes 222, the lifting device directly lifts the ultrafiltration membrane device 22 and the lifting device out of the membrane pool 21 to clean the yin and yang ultrafiltration membranes 222. Of course, the cleaning frame can also directly rinse the yin and yang ultrafiltration membranes 222 in the membrane pool 21.

[0064] In addition, a water outlet monitoring device 31 is provided on the water collecting pipe 221. The water outlet monitoring device 31 is a flow meter provided on the water collecting pipe 221. When the yin and yang ultrafiltration membranes 222 are blocked, the flow rate of water in the water collecting pipe 221 is reduced, and the water outlet monitoring device 31 will sound an alarm to remind the operator to clean the yin and yang ultrafiltration membranes 222.

[0065] In one embodiment, the spray head 223 is connected to the clean water tank 33 through spraying, and a flushing device 32 is provided on the spray water pipe. The flushing device 32 is a flushing pump, which can pump out the water in the clean water tank 33, and then spray it out from the spray head 223 to clean the yin and yang ultrafiltration membranes 222. That is, in this embodiment, the water in the clean water tank 33 is used to clean the yin and yang ultrafiltration membranes 222, thereby reducing the waste of water resources and realizing the recycling of treated water.

[0066] In one embodiment, the anionic ultrafiltration membrane 222 includes a base support layer 2221, a negative charge layer 2222, and a positive charge layer 2223, which are sequentially away from the water collection chamber. The negative charge layer 2222 is on the inside, and the positive charge layer 2223 is on the outside. The negative charge layer 2222 in this embodiment is polydopamine with a thickness of 5-20 nm, and the positive charge layer 2223 is polyethyleneimine or other positively charged polymers with a thickness of 20-50 nm. The base support layer 2221 can be a polymer organic membrane, an inorganic membrane, or a composite membrane. Figure 7 As shown, the surface of fluorine ions is negatively charged and will be captured by the positive charge layer 2223. The fluorine ions that pass through the positive charge layer 2223 will be repelled by the negative charge layer 2222 and then return to the positive charge layer 2223. The surface of the defluorinating agent is positively charged and will be repelled by the positive charge on the surface of the positive charge layer 2223 when it contacts the outer layer of the positive and negative ultrafiltration membranes 222, and then return to the membrane pool 21 to further react with the fluorine ions. The defluorinating agent that has reacted completely will be adsorbed by the fluorine ions and accumulated on the surface of the positive charge layer 2223. After a certain period of time, the effluent monitoring device 31 of the ultrafiltration membrane device 22 will give feedback, and the ultrafiltration membrane device 22 will be lifted. The ultrafiltration membrane device 22 is provided with a movable high-pressure spray head 223, which can move up and down to clean the surface of the positive and negative ultrafiltration membranes 222. At this time, the fluorine ions and defluorinating agent on the membrane surface will be taken away by the water flow.

[0067] Reference Figure 5 and Figure 6 As shown, the structure of this embodiment is similar to that of the embodiment 1, except that a separation device 5 for preventing the discharge of clean water is provided in the first waste pipe 261, and the separation device 5 includes a positioning hole 51 provided in the first waste pipe 261, and a plurality of first holes 511 are provided through the positioning hole 51; A second hole 512 is provided through the center of the positioning hole 51; a sleeve 52 is provided in the second hole 512, and an opening is provided at the top of the sleeve 52; a connecting rod 53 is slidably provided in the sleeve 52, and a first spring 54 is provided in the sleeve 52 to push the connecting rod 53 to move downward; A blocking plate 55 is connected to the outer side of the opening where the connecting rod 53 extends, and the projection of the blocking plate 55 toward the positioning hole 51 covers all the first holes 511; An air bag 56 is connected to the top of the baffle plate 55 via a pull rope 57 , and the air bag 56 is located in the concentration tank 23 .

[0068] In this embodiment, through the above structure, under normal use, when the airbag 56 is in the flocculent sediment, the airbag 56 is subjected to a large buoyancy at this time, and the airbag 56 pulls the connecting rod 53 upward through the pull rope 57, so that the baffle plate 55 is separated from the positioning hole 51. At this time, the flocculent sediment at the bottom of the concentration tank 23 passes through the first hole 511 and is discharged from the bottom of the first waste pipe 261; as the flocculent sediment at the bottom of the concentration tank 23 is discharged, the airbag 56 is covered with clean water at this time. Since the density of clean water is lower than that of the flocculent sediment, the buoyancy of the airbag 56 is reduced at this time. At this time, the first spring 54 pushes the connecting rod 53 to move downward, and the baffle plate 55 moves downward to block the first hole 511 on the positioning hole 51, thereby preventing clean water from flowing out of the first hole 511.

[0069] Therefore, through the above arrangement, it is possible to automatically prevent clean water from being discharged from the first waste pipe 261, thereby reducing the discharge of sewage and improving the efficiency of fluorine removal. In addition, although flocculent precipitates are also produced in the membrane pool 21, since the density of the flocculent precipitates in the membrane pool 21 is relatively low, and there are more flocculent precipitates in the concentration tank 23, the separation device 5 in this embodiment is arranged in the concentration tank 23 for better effect.

[0070] In one embodiment, a side wall outlet 262 is provided on the side wall of the first waste pipe 261 , a sliding piston 4 is provided at the bottom of the first waste pipe 261 , and a second spring 41 is provided at the bottom of the sliding piston 4 to push it to move upward.

[0071] In this embodiment, when the first hole 511 is opened, the pressure of the liquid in the first row of waste pipes 261 acts on the sliding piston 4, and the sliding piston 4 overcomes the elastic force of the second spring 41 and moves downward. At this time, the side wall outlet 262 is opened, and the flocculent sediment is discharged from the side wall outlet 262; when the first hole 511 is closed, the liquid pressure acting on the sliding piston 4 is reduced, and the second spring 41 pushes the sliding piston 4 to move upward to block the side wall outlet 262, thereby preventing the liquid from being discharged from the side wall outlet 262, and at the same time ensuring that liquid remains in the first row of waste pipes 261 to maintain the balance of the hydraulic pressure in the first row of waste pipes 261.

[0072] In addition, a limit ring 42 is provided on the inner wall of the first row of waste pipes 261, and the limit ring 42 is close to the top of the side wall outlet 262. The elastic force of the second spring 41 is relatively large, and the second spring 41 can be compressed only when the first hole 511 is opened. This makes it possible for the second spring 41 to immediately push the sliding piston 4 to move upward to close the side wall outlet 262 when the first hole 511 is closed. At the same time, the sliding piston 4 abuts against the limit ring 42, so that the second spring 41 maintains a relatively large clamping force, thereby ensuring that liquid is retained in the first row of waste pipes 261 and maintaining the balance of the hydraulic pressure in the first row of waste pipes 261.

[0073] The working principle of this embodiment is as follows: fluorine-containing wastewater enters the defluorination reaction tank 12 through the water inlet 11, and the defluorination agent is added through the defluorination agent dosing device, and fully reacts under the stirring of the stirring device of the defluorination reaction tank 12; then the treated water enters the flocculation reaction tank 14, and the flocculation agent is added through the flocculant dosing device 17, and fully reacts under the stirring of the stirring device of the flocculation reaction tank 14; then the treated water enters the concentration tank 23 for concentration, and the clearer liquid in the upper part of the concentration tank 23 overflows from the top of the membrane tank 21 into the membrane tank 21. During this period, the floccules in the concentration tank 23 are precipitated into the concentration mud bucket 26, and then discharged from the first waste pipe 261; the flocculent precipitate in the membrane tank 21 enters the membrane tank mud bucket 24, and then discharged from the second waste pipe; the treated water is treated by the ultrafiltration membrane device 22, and the treated water enters the clear water tank 33 by gravity using the siphon effect (the height difference between the membrane tank 21 and the clear water tank 33 is 5-10 m), the clean water in the clean water tank 33 is discharged or reused through the outlet 34, and part of the clean water can be used for cleaning the device to flush the yin and yang ultrafiltration membranes 222.

[0074] In a specific practice, a coal mine used the process and equipment of this patent to defluorinate fluorine-containing mine water. The equipment was in operation for 2 months, and the clean water produced was directly discharged to the nearby watershed. The fluorine-containing mine water is transferred to the defluorination reactor device in this application through a water pump, and 50~150 mg / L of defluorination agent and 1~10 mg / L of flocculant are added. The treated water then enters the concentration tank 23, and the concentrated effluent enters the membrane tank 21, and is treated by the ultrafiltration membrane device 22. The effluent uses gravity to directly enter the clean water tank 33. The height difference between the membrane tank 21 and the clean water tank 33 is 8 m, and finally the clean water is directly discharged. During operation, the surface of the yin and yang ultrafiltration membrane 222 is flushed with a clean water flushing device 32 every 1 hour to remove the fouling layer. The overall area of ​​the on-site equipment is 50 m 2 In actual operation, one pump group is used and the other is reserved, and the water treatment capacity is 100 t / h.

[0075] Fluoride content in and out of mine water during operation Figure 8 As shown in Figure 1, the online selective electrode method is used for fluoride detection. Figure 8It can be seen that after the equipment was put into operation, the fluoride in the mine water was stably reduced to below the standard of 1.0 mg / L. Compared with the common coagulation defluorination process, this equipment reduces the dosage by 20%, reduces the land area by 40%, and the effluent water quality is more stable.

[0076] Therefore, compared with the prior art, the present application mainly adopts membrane filtration to separate the solid-liquid suspension formed after adding drugs, and the surface has both a positive charge layer 2223 and a negative charge layer 2222, which can effectively reduce the adhesion of aluminum-based agents and realize the physical and chemical separation of high-concentration precipitation flocs and water; the equipment of the present invention adopts a concentration tank 23 to replace the original sedimentation tank, and cooperates with submerged membrane water head pressure filtration to realize the enrichment of precipitation flocs, improve the fluorine removal efficiency, and solve the problems of large footprint and large dosage of agents in the original equipment; at the same time, remote control technology and automatic control technology are adopted to realize on-site management with few or no people, solving the problems of the prior art that most of the on-site operations require professionals and the low degree of automation.

[0077] The above-described embodiments are only preferred solutions of the present invention and are not intended to limit the present invention in any form. Other variations and modifications are possible without exceeding the technical solutions described in the claims.

Claims

1. A defluorination reactor device, characterized in that: include: The reaction system comprises a defluorination reaction tank and a flocculation reaction tank which are interconnected, wherein the defluorination reaction tank is provided with a defluorination agent dosing device, and the flocculation reaction tank is provided with a flocculant dosing device; The concentration system includes a concentration tank connected to the flocculation reaction tank, and a membrane tank arranged in the concentration tank, wherein an ultrafiltration membrane device is arranged in the membrane tank; the ultrafiltration membrane device includes a plurality of water collection chambers, and a positive and negative ultrafiltration membranes are arranged on one side of the plurality of water collection chambers, and the water collection chambers are connected to the outside through a water collection pipe; The clean water system includes a clean water tank, and the water outlet of the water collecting pipe is connected with the clean water tank.

2. The defluorination reactor device according to claim 1, characterized in that: The cation-cation ultrafiltration membrane comprises a base support layer, a negative charge layer and a positive charge layer which are sequentially away from the water collection chamber.

3. The defluorination reactor device according to claim 1 or 2, characterized in that: It also includes a cleaning device for cleaning the ultrafiltration membrane device; the cleaning device includes a cleaning frame arranged outside the ultrafiltration membrane device and a spray head arranged on the inner side wall of the cleaning frame.

4. The defluorination reactor device according to claim 3, characterized in that: The spray head is connected to the clean water tank through a spray water pipe, and a flushing device is arranged on the spray water pipe.

5. The defluorination reactor device according to claim 1, characterized in that: A stirring device is arranged in the defluorination reaction tank and the flocculation reaction tank. The stirring device comprises a stirring motor and a stirring paddle arranged on the output shaft of the stirring motor.

6. The defluorination reactor device according to claim 1, 2 or 5, characterized in that: A concentrated mud hopper is arranged at the bottom of the concentration tank, and the horizontal cross-sectional area of ​​the concentrated mud hopper gradually decreases along the vertical downward direction; a first row of waste pipes is arranged at the bottom of the concentrated mud hopper.

7. The defluorination reactor device according to claim 1, 2 or 5, characterized in that: A membrane pool mud hopper is arranged at the bottom of the membrane pool, and the horizontal cross-sectional area of ​​the membrane pool mud hopper gradually decreases along the vertical downward direction; a second row of waste pipes is arranged at the bottom of the membrane pool mud hopper.

8. The defluorination reactor device according to claim 3, characterized in that: A plurality of water collecting chambers are arranged in parallel, and two spray heads are correspondingly arranged on both sides of the plurality of water collecting chambers.

9. The defluorination reactor device according to claim 6, characterized in that: A separation device for preventing clean water from being discharged is arranged in the first waste pipe, and the separation device comprises a positioning plate arranged in the first waste pipe, and a plurality of first holes are arranged through the positioning plate; A second hole is provided through the center of the positioning plate; a sleeve is provided in the second hole, and an opening is provided at the top of the sleeve; a connecting rod is slidably provided in the sleeve, and a first spring is provided in the sleeve to push the connecting rod to move downward; A blocking plate is connected to the outer side of the opening where the connecting rod extends, and the projection of the blocking plate toward the positioning plate covers all the first holes; An air bag is connected to the top of the baffle plate through a drawstring, and the air bag is located in the concentration tank.

10. The defluorination reactor device according to claim 9, characterized in that: A side wall outlet is arranged on the side wall of the first row of waste pipes, a sliding piston is arranged at the bottom of the first row of waste pipes, and a second spring is arranged at the bottom of the sliding piston to push it to move upward.

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