Adsorption and induced crystallization combined defluorination equipment and defluorination method

Abstract

The invention relates to the technical field of sewage treatment, in particular to adsorption and induced crystallization combined fluorine removal equipment and a fluorine removal method.The fluorine removal equipment comprises a pool body, an annular support, a rotating frame, a driving assembly, a quantitative feeding assembly, a fixed supporting piece, a waste discharge valve, a cylindrical shell, a suspension drainage assembly and a fluorine ion monitoring module and can be well applied to the fluorine removal method. The fluorine removal method comprises the following steps: firstly, putting Ca10 (PO4) 6 (OH) 2 into fluorine-containing wastewater to be treated so as to generate Ca10 (PO4) 6F2 of insoluble water through an ion exchange adsorption process; according to the method, the fluorine-containing wastewater is subjected to adsorption and induced crystallization, Ca < 2 + >, H2PO4 <-> and OH <-> are synchronously added into the fluorine-containing wastewater, and deep fluorine removal of the wastewater is realized through the coupling effect of adsorption and induced crystallization, so that the problem that deep fluorine removal is difficult to economically and efficiently carry out during water treatment is well solved.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, and in particular to an adsorption combined induced crystallization defluorination device and a defluorination method. Background Art

[0002] Fluoride is an essential trace element for the human body. Appropriate intake of fluoride can inhibit lactobacilli and thus prevent tooth decay, and promote the hardness of teeth and bone strength. However, long-term excessive intake of fluoride can cause dental fluorosis and skeletal fluorosis. In addition, fluoride also has certain irritating and corrosive effects on human skin and mucous membranes. Fluoride can also have an impact on plants. Excessive fluoride can damage the cell plasma membrane and chloroplasts, hinder the transmembrane transport of photosynthesis, affect the photosynthesis and respiration of plants, and inhibit metabolism by inhibiting the activity of maleate dehydrogenase. Therefore, excessive fluoride in water can affect the growth of aquatic plants and destroy the aquatic ecosystem.

[0003] Fluorine-containing compounds are essential raw materials for the production of many chemical industries, integrated circuits, and photovoltaic companies, and will inevitably lead to the discharge of a large amount of fluorine-containing wastewater. With the rapid development of integrated circuits and photovoltaic companies, fluorine pollution is becoming more and more serious.

[0004] At present, the commonly used fluoride removal technologies include chemical precipitation, coagulation, adsorption, ion exchange, membrane separation (electrodialysis, reverse osmosis, nanofiltration), etc. The treatment depth of chemical precipitation and coagulation is limited. They are suitable for treating high-concentration fluoride-containing wastewater, but it is difficult to reduce the fluoride to below 8 mg / L, and generally cannot meet higher emission standards. Adsorption and ion exchange face problems such as high treatment costs, while membrane separation technology has high energy consumption, and the treatment of concentrated water is also a problem. In general, the current fluoride removal equipment and methods in sewage often have problems such as complex structure, high investment cost and incomplete fluoride removal.

[0005] Therefore, there is an urgent need for an economical and efficient deep defluorination equipment and method to provide technical support for the deep defluorination of various types of water. Summary of the invention

[0006] The object of the present invention is to provide an adsorption combined induced crystallization defluorination device and a defluorination method, which are used to solve the problem in the prior art that it is difficult to carry out deep defluorination economically and efficiently during water treatment.

[0007] To achieve the above-mentioned purpose, the present invention provides the following technical solutions: an adsorption combined induced crystallization defluorination device, the pool body includes a cylinder, a truncated cone shell connected to the bottom end of the cylinder, a conical shell connected to the bottom end of the truncated cone shell and a support structure supported on the outer edge of the bottom end of the cylinder, the top of the cylinder side wall is provided with a water inlet pipe; the outer edge of the annular support is fixedly connected to the top of the inner circumferential wall of the cylinder; the rotating frame includes a ring body rotatably connected to the inner edge of the annular support, a sleeve ring arranged at the center of the ring body and a plurality of radially fixed rings on the ring body. The connecting rod is connected between the body and the sleeve ring; the driving assembly is used to drive the ring body to rotate; the quantitative feeding assembly includes a support fixed to the outer end of the top surface of the connecting rod, a horizontal cylinder fixed to the top of the support, a spiral blade shaft rotatably installed in the horizontal cylinder, a feeding motor fixed to one end surface of the horizontal cylinder and used to drive the spiral blade shaft to rotate, a hopper fixed at the bottom end to the top of the horizontal cylinder, a top cover covering the top of the hopper, a vertical cylinder fixed to the other end of the horizontal cylinder on one side of the top, and a vertical cylinder arranged in the inner cavity of the vertical cylinder and located in the horizontal cylinder The weighing support member on the lower side and the rotating material distribution member arranged at the center of the inner cavity of the vertical cylinder, the weighing support member includes a fan-shaped bottom plate whose outer edge is fixed to the inner peripheral wall of the vertical cylinder, a ring fixed to the inner edge of the fan-shaped bottom plate, a fan-shaped support plate arranged parallel to the fan-shaped bottom plate, and a weighing sensor connected between the bottom surface of the fan-shaped support plate and the top surface of the fan-shaped bottom plate, the rotating material distribution member includes a vertical shaft rotatably sleeved in the ring, a pair of partitions fixed to the outer peripheral wall of the vertical shaft in radial direction and with the bottom ends located at the two ends of the top surface of the fan-shaped support plate, and a and a blade fixed to the bottom end of the vertical axis, an open groove is provided on one side of the bottom end of the vertical cylinder close to the center of the cylinder; the waste valve is installed at the bottom end of the conical shell; the cylindrical shell is arranged on one side of the cylinder, and a through groove is vertically provided between the cylindrical shell and the cylinder; the suspended drainage assembly includes an annular float slidably mounted in the cylindrical shell and a water pump fixedly mounted inside the annular float; the fluoride ion monitoring module is installed on the bottom surface of the annular float; one end of the drainage hose is mounted on the output end of the water pump.

[0008] Preferably, a slewing bearing is fixed to the inner edge of the bottom surface of the annular support, the outer edge of the annular body is fixed to the top surface of the rotating inner ring of the slewing bearing, and an outer gear ring is fixed to the inner edge of the bottom surface of the annular body. The drive assembly includes a drive motor fixed to the top surface of the annular support and a gear fixedly mounted on the bottom end of the power output shaft of the drive motor and meshing with the outer gear ring.

[0009] Preferably, the inner circumferential wall of the cylindrical shell is provided with a plurality of slide grooves extending vertically respectively, the external fixed sleeve of the annular float is provided with a sleeve, the outer circumferential wall of the sleeve is provided with vertical grooves corresponding to the positions of the slide grooves, and rollers rolling along the slide grooves are rotatably installed in the vertical grooves.

[0010] Preferably, it also includes a fixed support member and a separator, the fixed support member includes a fixed circular plate, a vertical tube with a bottom end fixedly mounted in the center of the fixed circular plate and a top end rotatably mounted in the ring, and an outer ring member fixed to the periphery of the fixed circular plate and fixedly mounted with the bottom end of the frustum shell, a plurality of fan-shaped holes 1 are evenly arranged along the circumferential direction on the fixed circular plate, the separator includes a vertical rod rotatably mounted in the vertical tube, a rotating circular plate with a center fixedly mounted on the bottom end of the vertical rod and attached to the bottom surface of the fixed circular plate, and the rotating circular plate is provided with fan-shaped holes 2 corresponding to the fan-shaped holes one by one.

[0011] Preferably, a clamping head is provided at the top end of the vertical rod, and electric clamping claws with clamping hands located on both sides of the clamping head are fixed to the inner end of the top surface of the connecting rod.

[0012] Preferably, the angle between the two paired partitions is 90-150°.

[0013] A method for defluorination by adsorption combined with induced crystallization comprises the following steps:

[0014] S1, first use one of the quantitative feeding components to feed Ca 10 (PO4)6(OH)2 is added to the fluoride-containing wastewater to be treated to generate Ca2+, which is insoluble in water, through the ion exchange adsorption process. 10 (PO4)6F2; The chemical reaction equation is as follows:

[0015] Ca 10 (PO4)6(OH)2+2F - =Ca 10 (PO4)6F2+2OH - ①

[0016] S2, using another quantitative feeding component to simultaneously add Ca into the fluorine-containing wastewater in a certain proportion 2+ 、H2PO4 - OH - ;

[0017] Among them, the added Ca 2+ 、H2PO4 - OH - At this time, F - The ratio is Ca 2+ :H2PO4 - :OH - :F - =7:3:6:1; Ca 2+ 、H2PO4 - OH - Add in the form of Ca(OH)2, KH2PO4, CaSO4 and / or CaCL2.

[0018] The chemical reaction equation is as follows:

[0019] 10Ca 2+ +6H2PO4 - +2F - =Ca 10 (PO4)6F2+12H + ②

[0020] 12H + +12OH - =12H2O ③

[0021] Among them, the mutual coupling promotion effect between the adsorption process and the crystallization process is reflected in the following two aspects:

[0022] 1) In Ca 10 The calcium fluorophosphate product formed on the surface of (PO4)6(OH)2 can serve as a seed crystal, provide a structural template for the growth of new crystals, reduce the interfacial free energy of calcium fluorophosphate precipitation, form heterogeneous crystals, and further reduce the precipitation concentration of calcium fluorophosphate in water, thereby achieving the goal of reducing F - To lower the level.

[0023] 2) In Ca 2+ 、H2PO4 - OH - When the dosage is appropriate, the OH generated during the ion exchange adsorption process - With the added OH - Together, they neutralize the H released during the crystallization of calcium fluorophosphate + , synchronously accelerate the reaction processes of ① and ②.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. The present invention relates to an adsorption combined induced crystallization defluorination device and a defluorination method, in which the defluorination method is implemented by a defluorination device integrated with a quantitative feeding, mixing, monitoring, and waste discharge system, etc., and deep defluorination of sewage is achieved through the coupling effect of adsorption and induced crystallization, which effectively solves the problem of difficulty in economically and efficiently carrying out deep defluorination in water treatment.

[0026] 2. The adsorption combined induced crystallization defluorination equipment and defluorination method involved in the present invention have scientific and reasonable addition ratios of various reagents, which not only ensure the maximum depth of defluorination operation, but also avoid the addition of new residual components, such as phosphorus, in the water after defluorination. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic diagram of the overall three-dimensional structure of an adsorption combined with induced crystallization defluorination device of the present invention;

[0028] Figure 2 It is a schematic diagram of the three-dimensional structure of a rotating frame in an adsorption combined induced crystallization defluorination device of the present invention;

[0029] Figure 3 For the present invention Figure 4 A schematic diagram of the enlarged structure at A in the middle;

[0030] Figure 4 It is a schematic diagram of the three-dimensional structure of a quantitative feeding component in an adsorption combined induced crystallization defluorination device of the present invention;

[0031] Figure 5 It is a schematic diagram of the exploded structure of a weighing support in an adsorption combined induced crystallization defluorination device of the present invention;

[0032] Figure 6 It is a schematic diagram of the three-dimensional structure of a rotating cloth member in an adsorption combined induced crystallization defluorination device of the present invention;

[0033] Figure 7 It is a schematic diagram of the three-dimensional structure of a fixed support member in an adsorption combined induced crystallization defluorination device of the present invention;

[0034] Figure 8 It is a schematic diagram of the three-dimensional structure of a separator in an adsorption combined induced crystallization defluorination device of the present invention;

[0035] Fig. 9 It is a schematic diagram of the three-dimensional structure of a suspended drainage component in an adsorption combined induced crystallization defluorination device of the present invention;

[0036] Fig.10 This is a schematic diagram of a defluorination method by adsorption combined with induced crystallization according to the present invention;

[0037] Fig.11 It is a curve diagram of the experimental verification results of an adsorption combined with induced crystallization defluorination method in the present invention;

[0038] Fig.12 This is a curve diagram showing the results of verifying the effect of using an adsorption combined with induced crystallization defluorination method in the present invention for actual fluoride-containing wastewater treatment.

[0039] In the figure: 1-tank body; 1.1-cylinder body; 1.1.1-water inlet pipe; 1.2-truncated cone shell; 1.3-conical shell; 1.4-support structure;

[0040] 2-annular support; 2.1-slewing bearing;

[0041] 3- rotating frame; 3.1- ring body; 3.2- sleeve ring; 3.3- connecting rod; 3.4- outer gear ring;

[0042] 4-driving assembly; 4.1-driving motor; 4.2-gear;

[0043] 5-quantitative feeding assembly; 5.1-support; 5.2-horizontal cylinder; 5.3-spiral blade shaft; 5.4-feeding motor; 5.5-hopper; 5.6-top cover; 5.7-vertical cylinder; 5.7.1-opening slot; 5.8-weighing support; 5.8.1-fan ring bottom plate; 5.8.2-ring; 5.8.3-fan ring support plate; 5.8.4-weighing sensor; 5.9-rotating cloth member; 5.9.1-vertical axis; 5.9.2-partition plate; 5.9.3-blade;

[0044] 6-fixed support; 6.1-fixed circular plate; 6.1.1-sector hole 1; 6.2-vertical pipe; 6.3-outer ring;

[0045] 7-separator; 7.1-vertical rod; 7.1.1-clamp; 7.2-rotating circular plate; 7.2.1-sector-shaped hole 2;

[0046] 8-Electric gripper;

[0047] 9- Waste discharge valve;

[0048] 10- cylindrical housing; 10.1- slideway;

[0049] 11-suspended drainage assembly; 11.1-water pump; 11.2-annular float; 11.3-sleeve; 11.3.1-vertical groove; 11.4-roller;

[0050] 12-Fluoride ion monitoring module;

[0051] 13-Drain hose. DETAILED DESCRIPTION

[0052] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0053] See also Figure 1-10 The present invention provides a technical solution, an adsorption combined induced crystallization defluorination equipment, the pool body 1 includes a cylinder 1.1, a conical shell 1.2 connected to the bottom end of the cylinder 1.1, a conical shell 1.3 connected to the bottom end of the conical shell 1.2 and a supporting structure 1.4 supported on the outer edge of the bottom end of the cylinder 1.1, and a water inlet pipe 1.1.1 is provided on the top of the side wall of the cylinder 1.1; a waste valve 9 is installed at the bottom end of the conical shell 1.3.

[0054] The outer edge of the annular support 2 is fixedly connected to the top of the inner peripheral wall of the cylinder 1.1; the inner edge of the bottom surface of the annular support 2 is fixed with a slewing support 2.1. That is, the rotating outer ring of the slewing support 2.1 is fixed to the inner edge of the bottom surface of the annular support 2.

[0055] The rotating frame 3 includes a ring body 3.1 rotatably connected to the inner edge of the annular support 2, a collar 3.2 arranged at the center of the ring body 3.1, and a plurality of connecting rods 3.3 radially fixed between the ring body 3.1 and the collar 3.2; wherein the outer edge of the ring body 3.1 is fixed to the top surface of the rotating inner ring of the slewing bearing 2.1; and an outer gear ring 3.4 is fixed to the inner edge of the bottom surface of the ring body 3.1. The driving assembly 4 includes a driving motor 4.1 fixed to the top surface of the annular support 2 and a gear 4.2 fixedly mounted on the bottom end of the power output shaft of the driving motor 4.1 and meshing with the outer gear ring 3.4.

[0056] The quantitative feeding assembly 5 comprises a support 5.1 fixed to the outer end of the top surface of the connecting rod 3.3, a horizontal cylinder 5.2 fixed to the top of the support 5.1, a spiral blade shaft 5.3 rotatably installed in the horizontal cylinder 5.2, a feeding motor 5.4 fixed to one end surface of the horizontal cylinder 5.2 and used to drive the spiral blade shaft 5.3 to rotate, a hopper 5.5 with its bottom end fixed to the top of the horizontal cylinder 5.2, a top cover 5.6 covering the top of the hopper 5.5, a vertical cylinder 5.7 with one side of its top fixed to the other end of the horizontal cylinder 5.2, a weighing support 5.8 arranged in the inner cavity of the vertical cylinder 5.7 and located at the lower side of the horizontal cylinder 5.2, and a rotating material distribution member 5.9 arranged in the center of the inner cavity of the vertical cylinder 5.7, wherein the weighing support 5.8 comprises an outer edge fixed to the inner periphery of the vertical cylinder 5.7. The fan-shaped annular bottom plate 5.8.1 of the wall, the ring 5.8.2 fixed to the inner edge of the fan-shaped annular bottom plate 5.8.1, the fan-shaped support plate 5.8.3 arranged parallel to the fan-shaped annular bottom plate 5.8.1, and the weighing sensor 5.8.4 connected between the bottom surface of the fan-shaped support plate 5.8.3 and the top surface of the fan-shaped annular bottom plate 5.8.1. The rotating material distribution member 5.9 includes a vertical shaft 5.9.1 rotatably sleeved in the ring 5.8.2, partitions 5.9.2 fixed in pairs along the radial direction to the outer peripheral wall of the vertical shaft 5.9.1 and the bottom ends of which are located at the two ends of the top surface of the fan-shaped support plate 5.8.3, and blades 5.9.3 fixed to the bottom end of the vertical shaft 5.9.1. An open groove 5.7.1 is provided on one side of the bottom end of the vertical cylinder 5.7 near the center of the cylinder body 1.1. Among them, two sets of quantitative feeding components 5 are provided, and the hopper 5.5 of the No. 1 quantitative feeding component 5 contains C a10 (PO4)6(OH)2, used for C a10 (PO4)6(OH)2 is quantitatively fed. The hopper 5.5 of the quantitative feeding assembly 5 No. 2 is filled with Ca 2+ 、H2PO4 - OH - mixture, ensuring Ca 2+ :H2PO4 - :OH- =7:3:6. In addition, the angle between the two paired partitions 5.9.2 is 90-150°. When feeding quantitatively, the feeding motor 5.4 drives the spiral blade shaft 5.3 to rotate to push the medicine through the horizontal cylinder 5.2 to the vertical cylinder 5.7. The medicine falling into the vertical cylinder 5.7 falls on the top surface of the fan-shaped support plate 5.8.3 under the blocking effect of the two partitions 5.9.2. At this time, the weighing sensor 5.8.4 is convenient for weighing the medicine on the top surface of the fan-shaped support plate 5.8.3. When the preset weight is reached, the signal of the weighing sensor 5.8.4 stops the operation of the corresponding feeding motor 5.4 through the controller.

[0057] The cylindrical housing 10 is arranged on one side of the cylinder 1.1, and a through groove is arranged vertically between the cylindrical housing 10 and the cylinder 1.1. The inner peripheral wall of the cylindrical housing 10 is provided with a plurality of slide grooves 10.1 extending vertically.

[0058] The suspended drainage assembly 11 includes an annular float 11.2 that is slidably mounted in the cylindrical shell 10 and a water pump 11.1 that is fixedly mounted inside the annular float 11.2; one end of the drainage hose 13 is mounted on the output end of the water pump 11.1. The annular float 11.2 is fixedly mounted with a sleeve 11.3 on the outside, and the outer peripheral wall of the sleeve 11.3 is provided with vertical grooves 11.3.1 at positions corresponding to the chute 10.1, and rollers 11.4 that roll along the chute 10.1 are rotatably mounted in the vertical grooves 11.3.1. That is, under the buoyancy of the annular float 11.2, the water suction end of the water pump 11.1 is always just below the water surface. The rollers 11.4 roll along the chute 10.1, providing a good guiding effect to ensure the smooth lifting and lowering of the water pump 11.1.

[0059] The fixed support member 6 comprises a fixed circular plate 6.1, a vertical pipe 6.2 whose bottom end is fixedly sleeved in the center of the fixed circular plate 6.1 and whose top end is rotatably sleeved in the sleeve ring 3.2, and an outer ring member 6.3 fixed to the outer periphery of the fixed circular plate 6.1 and fixedly sleeved with the bottom end of the truncated cone shell 1.2. A plurality of fan-shaped holes 6.1.1 are evenly arranged along the circumference of the fixed circular plate 6.1.

[0060] The partition 7 comprises a vertical rod 7.1 which is rotatably mounted in the vertical tube 6.2, a rotating circular plate 7.2 which is fixedly mounted at the bottom of the vertical rod 7.1 and is attached to the bottom surface of the fixed circular plate 6.1, and a second sector hole 7.2.1 which corresponds to the first sector hole 6.1.1 is provided on the rotating circular plate 7.2. Among them, a clamping head 7.1.1 is provided at the top of the vertical rod 7.1, and electric clamping claws 8 with clamping hands located on both sides of the clamping head 7.1.1 are fixed at the inner end of the top surface of the connecting rod 3.3.

[0061] The fluoride ion monitoring module 12 is installed on the bottom surface of the annular float 11.2; the fluoride ion monitoring module 12 is used to monitor the fluoride ion content in the wastewater in the cylinder 1.1, and is used to provide a basis for the feeding amount of the quantitative feeding component 5; it also provides a basis for starting and stopping the water pump 11.1.

[0062] In summary, initially, the fan-shaped hole 1 6.1.1 and the fan-shaped hole 2 7.2.1 are in a mutually staggered state. Fluorine-containing wastewater is discharged into the cylinder 1.1 through the water inlet pipe 1.1.1. The driving motor 4.1 drives the rotating frame 3 to rotate through the meshing action of the gear 4.2 and the outer gear ring 3.4. The quantitative feeding component 5 No. 1 performs C a10 (PO4)6(OH)2 delivery process. As the rotating frame 3 rotates, the blades 5.9.3 are impacted by the water flow at the corresponding opening slot 5.7.1, driving the vertical shaft 5.9.1 to rotate, so that the partition 5.9.2 moves the corresponding reagent on the fan annular support plate 5.8.3 to fall down along the vertical cylinder 5.7. The rotating blades 5.9.3 will provide stirring in the process of mixing the reagent and wastewater, so as to facilitate the C a10 (PO4)6(OH)2 is evenly added to the wastewater in cylinder 1.1.

[0063] Then, the quantitative feeding component No. 2 feeds the Ca 2+ 、H2PO4 - OH - The amount of the mixture is quantitatively added. At this time, the amount of addition is determined according to the fluoride ion content monitored by the fluoride ion monitoring module 12 to ensure that Ca 2+ :H2PO4 - :OH - :F - =7:3:6:1.

[0064] After completing the two feeding processes, deep defluorination of wastewater is achieved through the coupling effect of adsorption and induced crystallization.

[0065] Then the electric clamp 8 fixes and clamps the chuck 7.1.1. At this time, the vertical rod 7.1 will lead the rotating circular plate 7.2 to rotate a certain angle relative to the fixed circular plate 6.1, so that the fan-shaped hole 1 6.1.1 corresponds to the fan-shaped hole 2 7.2.1 one by one. The formed crystalline insoluble matter will fall into the conical shell 1.3 through the fan-shaped hole 1 6.1.1 and the fan-shaped hole 2 7.2.1 in turn for collection.

[0066] The water pump 11.1 is turned on to gradually pump out the upper layer of clean water. The vertical rod 7.1 is driven to rotate by the rotating frame 3 again, so that the fan-shaped hole 1 6.1.1 and the fan-shaped hole 2 7.2.1 are staggered again, and the crystal insoluble matter can be discharged through the waste valve 9.

[0067] The experimental verification process of an adsorption combined with induced crystallization defluorination method is as follows:

[0068] Configure fluoride-containing wastewater.

[0069] The configuration method is: add NaF to deionized water to make the initial F - The concentration is 8mg / L.

[0070] Set up three pairs of experiments:

[0071] The first group only added C a10 (PO4)6(OH)2, it is believed that this group removes F only by ion exchange adsorption - (Reaction ①) The hydroxyapatite used in the experiment has a purity of 99%, is in powder form (particle size: 4.5 μm), and is added in an amount of 1.5 g / L.

[0072] The second group only added KH2PO4, CaCl2, and Ca(OH)2 (analytical grade) to make Ca 2+ :H2PO4 - :OH - :F - =7:3:6:1, this group only removes F by homogeneous crystallization - , the reaction equation is the same as ② and ③.

[0073] Group 3: Synchronous Ca addition 10 (PO4)6(OH)2, KH2PO4, CaCl2, Ca(OH)2, reagent purity, particle size, and dosage are the same as those of the first and second groups. This group removes F through the combined action of exchange adsorption and induced crystallization. - .

[0074] like Figure 1 As shown in the figure, the defluorination effect of the combined action of exchange adsorption and induced crystallization is significantly better than that of single adsorption and single crystallization. This proves that there is a mutual coupling promotion effect between exchange adsorption and induced crystallization. It can be seen that the Ca 10 At the dosage of (PO4)6(OH)2, it is difficult to - From 8mg / L to below 1mg / L. The single crystallization reaction rate is slow. According to the test results, under the test conditions, F - The reaction time required to reduce the concentration to below 1 mg / L is much longer than 3.5 hours. To increase the reaction rate and treatment effect, it may be necessary to increase the dosage of the agent. - The concentration dropped rapidly, reaching 0.1 mg / L in just 3 minutes, breaking through the lower limit of fluoride ion concentration in effluent from existing defluoridation methods, further confirming the occurrence of induced crystallization, and providing a new path for efficient defluoridation.

[0075] The verification process of the effect of an adsorption combined with induced crystallization defluorination method on the actual fluoride-containing wastewater treatment is as follows:

[0076] Actual fluoride-containing wastewater was taken as the test raw water. Among them, the fluoride-containing wastewater was taken from a photovoltaic enterprise. - The type and amount of reagent added are the same as the above test verification process.

[0077] like Figure 2 As shown in the figure, the method was used to treat the fluorine-containing wastewater and obtain a good treatment effect. When the cumulative treated water volume reached 2.7L / g, the treatment effect was still good. Within 3 minutes, F - Reduced to below 1 mg / L. Based on the test results, the estimated cost of the agent is shown in Table 1.

[0078] Table 1 Actual cost accounting of fluorine-containing wastewater treatment agents

[0079]

[0080]

[0081] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0082] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An adsorption combined with induced crystallization defluorination equipment, characterized in that: include: A pool body (1), the pool body (1) comprising a cylinder (1.1), a truncated cone shell (1.2) connected to the bottom end of the cylinder (1.1), a conical shell (1.3) connected to the bottom end of the truncated cone shell (1.2), and a support structure (1.4) supported on the outer edge of the bottom end of the cylinder (1.1), and a water inlet pipe (1.1.1) is provided at the top of the side wall of the cylinder (1.1); An annular support (2), the outer edge of which is fixedly connected to the top end of the inner peripheral wall of the cylinder (1.1); A rotating frame (3), the rotating frame (3) comprising a ring body (3.1) rotatably connected to the inner edge of the annular support (2), a collar (3.2) arranged at the center of the ring body (3.1), and a plurality of connecting rods (3.3) radially fixed between the ring body (3.1) and the collar (3.2); A driving assembly (4), the driving assembly (4) being used to drive the ring body (3.1) to rotate; The quantitative feeding assembly (5) comprises a support (5.1) fixed to the outer end of the top surface of the connecting rod (3.3), a horizontal cylinder (5.2) fixed to the top of the support (5.1), a spiral blade shaft (5.3) rotatably installed in the horizontal cylinder (5.2), a feeding motor (5.4) fixed to one end surface of the horizontal cylinder (5.2) and used to drive the spiral blade shaft (5.3) to rotate, and a bottom end of the horizontal cylinder (5.2) fixed to the water cylinder (5.3). A hopper (5.5) at the top of the horizontal cylinder (5.2), a top cover (5.6) covering the top of the hopper (5.5), a vertical cylinder (5.7) with one side of the top fixed to the other end of the horizontal cylinder (5.2), a weighing support (5.8) arranged in the inner cavity of the vertical cylinder (5.7) and located at the lower side of the horizontal cylinder (5.2), and a rotating material distribution member (5.9) arranged in the center of the inner cavity of the vertical cylinder (5.7), wherein the weighing support (5.8) includes an outer edge fixed a fan-shaped bottom plate (5.8.1) fixed on the inner peripheral wall of the vertical cylinder (5.7), a collar (5.8.2) fixed on the inner edge of the fan-shaped bottom plate (5.8.1), a fan-shaped support plate (5.8.3) arranged parallel to the fan-shaped bottom plate (5.8.1), and a weighing sensor (5.8.4) connected between the bottom surface of the fan-shaped support plate (5.8.3) and the top surface of the fan-shaped bottom plate (5.8.1), the rotating cloth member (5.9 ) comprises a vertical shaft (5.9.1) rotatably mounted in the sleeve (5.8.2), partitions (5.9.2) fixed in pairs along the radial direction to the outer peripheral wall of the vertical shaft (5.9.1) and with the bottom ends located at the two ends of the top surface of the fan annular support plate (5.8.3), and blades (5.9.3) fixed to the bottom end of the vertical shaft (5.9.1), and an open groove (5.7.1) is provided on one side of the bottom end of the vertical cylinder (5.7) close to the center of the cylinder body (1.1); A waste discharge valve (9), the waste discharge valve (9) being mounted at the bottom end of the conical housing (1.3); A cylindrical shell (10), the cylindrical shell (10) being arranged on one side of the cylinder (1.1), and a through groove being arranged vertically between the cylindrical shell (10) and the cylinder (1.1); A suspended drainage assembly (11), the suspended drainage assembly (11) comprising an annular float (11.2) slidably mounted in the cylindrical housing (10) and a water pump (11.1) fixedly mounted inside the annular float (11.2); A fluoride ion monitoring module (12), the fluoride ion monitoring module (12) being installed on the bottom surface of the annular floating body (11.2); A drainage hose (13), one end of which is sleeved on the output end of the water pump (11.1).

2. The defluorination equipment by adsorption combined with induced crystallization according to claim 1 is characterized in that: A slewing bearing (2.1) is fixed to the inner edge of the bottom surface of the annular support (2); the outer edge of the ring body (3.1) is fixed to the top surface of the rotating inner ring of the slewing bearing (2.1); an outer gear ring (3.4) is fixed to the inner edge of the bottom surface of the ring body (3.1); and the drive assembly (4) comprises a drive motor (4.1) fixed to the top surface of the annular support (2) and a gear (4.2) fixedly mounted on the bottom end of the power output shaft of the drive motor (4.1) and meshing with the outer gear ring (3.4).

3. The defluorination equipment by adsorption combined with induced crystallization according to claim 2 is characterized in that: The inner peripheral wall of the cylindrical shell (10) is provided with a plurality of slide grooves (10.1) extending in the vertical direction respectively; the outer fixing sleeve of the annular floating body (11.2) is provided with a sleeve (11.3); the outer peripheral wall of the sleeve (11.3) is provided with vertical grooves (11.3.1) at positions corresponding to the slide grooves (10.1); rollers (11.4) rolling along the slide grooves (10.1) are rotatably installed in the vertical grooves (11.3.1).

4. The adsorption combined induced crystallization defluorination equipment according to claim 3 is characterized in that: The invention also comprises a fixed support member (6) and a separator (7), wherein the fixed support member (6) comprises a fixed circular plate (6.1), a vertical pipe (6.2) whose bottom end is fixedly sleeved in the center of the fixed circular plate (6.1) and whose top end is rotatably sleeved in the sleeve ring (3.2), and an outer ring member (6.3) fixed to the periphery of the fixed circular plate (6.1) and fixedly sleeved with the bottom end of the truncated cone shell (1.2), and a plurality of fan-shaped holes (6.3) are evenly arranged on the fixed circular plate (6.1) along the circumferential direction. 6.1.1), the partition (7) comprises a vertical rod (7.1) rotatably mounted in the vertical tube (6.2), a rotating circular plate (7.2) centrally fixedly mounted on the bottom end of the vertical rod (7.1) and fitted to the bottom surface of the fixed circular plate (6.1), and the rotating circular plate (7.2) is provided with a second sector-shaped hole (7.2.1) corresponding one-to-one to the first sector-shaped hole (6.1.1).

5. The defluorination equipment by adsorption combined with induced crystallization according to claim 4 is characterized in that: The top end of the vertical rod (7.1) is provided with a clamping head (7.1.1), and the inner end of the top surface of the connecting rod (3.3) is fixed with electric clamping claws (8) with clamping hands located on both sides of the clamping head (7.1.1).

6. The defluorination equipment by adsorption combined with induced crystallization according to claim 5, characterized in that: The angle between the two paired partitions (5.9.2) is 90 to 150 degrees.

7. The defluorination method of the defluorination equipment using adsorption combined with induced crystallization according to claim 6, characterized in that: The following steps are involved: S1, first use a quantitative feeding component (5) to feed Ca 10 (PO4)6(OH)2 is added to the fluoride-containing wastewater to be treated to generate Ca2+, which is insoluble in water, through the ion exchange adsorption process. 10 (PO4)6F2; S2, using another quantitative feeding component (5) to simultaneously add Ca into the fluorine-containing wastewater 2+ 、H2PO4 - OH - ; Among them, the added Ca 2+ 、H2PO 4- OH - At this time, F - The ratio is Ca 2+ :H2PO 4- :OH - :F - =7:3:6:

1.

8. The defluorination method of claim 7, characterized in that: Ca 2+ 、H2PO4 - OH - Add in the form of Ca(OH)2, KH2PO4, CaCl2.

9. The method for defluorination by adsorption combined with induced crystallization according to claim 7, characterized in that: Ca 2+ 、H2PO4 - OH - Add in the form of Ca(OH)2, KH2PO4, CaSO4.

10. The method for defluorination by adsorption combined with induced crystallization according to claim 7, characterized in that: Ca 2+ 、H2PO4 - OH - Add in the form of Ca(OH)2, KH2PO4, CaSO4, CaCl2.

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