Fluorine-containing wastewater recovery device and recovery method

Abstract

The present invention discloses a fluorine-containing wastewater recovery device and recovery method, and relates to the technical field of wastewater recovery, the fluorine-containing wastewater recovery device comprises: a support unit comprising a fixing frame; and the reaction unit comprises a reaction assembly arranged on the fixed frame. According to the method, calcium salts such as industrial calcium carbonate, industrial calcium chloride and industrial calcium hydroxide are added into a reaction tank, the adding amount, the reaction time and the initial fluorine ion concentration are adjusted, heating and stirring are conducted at the same time, fluorine ions in the wastewater fully react with the calcium salts to generate calcium fluoride, and therefore fluorine resources are efficiently recycled. The problems that a large amount of fluorine-containing sludge generated by a chemical precipitation method and a coagulation precipitation method easily causes secondary pollution, an adsorption method is only suitable for small-scale low-concentration wastewater and is high in cost and the like are effectively solved, fluorine crystals and a reaction solution are separated through the guiding assembly and conveyed to the recycling assembly to be collected in a unified mode, and the recycling efficiency is improved. The damage of the fluorine crystal secondary reaction to the equipment is avoided, so that the service life of the equipment is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment and resource recovery, and particularly to a fluoride-containing wastewater recovery device and a recovery method. Background Art

[0002] Fluoride-containing wastewater is widely generated in industrial fields such as semiconductor manufacturing, lithium battery recycling, photovoltaic etching, and coal chemical industry, and its fluoride ion (F - ) concentration can reach several hundred mg / L. Excessive discharge of fluorine elements not only causes ecological toxicity of water bodies, but also poses health risks such as skeletal fluorosis and thyroid dysfunction in humans through food chain enrichment. Therefore, strict fluoride-containing wastewater discharge standards have been introduced at home and abroad. For example, the "Integrated Wastewater Discharge Standard" (GB 8978-1996) in China requires that the fluoride discharge limit ≤ 10 mg / L, and some provinces (such as Jiangsu and Zhejiang) have raised the standard to ≤ 5 mg / L, putting higher and higher requirements on fluoride wastewater treatment technologies.

[0003] Fluorite (CaF2) is the core raw material of the fluorochemical industry chain, but China's fluorite resource reserves only account for 13% of the global total, and it faces over-exploitation and environmental protection restrictions. In recent years, the government has restricted the mining volume through the "Total Control Policy for the Mining of Refractory Clays and Fluorite", resulting in a tight supply of raw materials. The fluoride ion concentration in fluoride-containing wastewater (such as semiconductor etching wastewater and fluorochemical production wastewater) can reach several hundred mg / L. Direct discharge or landfill after traditional treatment both lead to the loss of fluorine resources. By using recovery technologies to extract fluorides, it can replace part of the demand for primary fluorite, relieve the supply tension, reduce the sludge production, and lower the risk of secondary pollution. The recovered fluorides (such as high-purity calcium fluoride) can be reused in fluorochemical production or used as raw materials for high-value-added products.

[0004] Existing methods for the resource recovery of fluoride-containing wastewater generally have problems such as low efficiency, high cost, and insufficient resource utilization. Although the chemical precipitation method can treat high-concentration fluoride-containing wastewater, the generated calcium fluoride sludge has a high water content (60%-80%) and low purity (30%-60%), with limited recovery value, and the residual fluoride concentration is still difficult to meet strict emission standards. Although the aluminum salt flocculation method can reduce the fluoride concentration, it has a large dosage, a high risk of residual dissolved aluminum, limited treatment depth, and poor economy. Adsorption methods (such as activated alumina and resins) are suitable for advanced treatment, but have a low adsorption capacity and frequent regeneration. Although new rare-earth-based materials (such as zirconia) have an increased adsorption capacity (up to 30 mg / g), they are costly and lack large-scale application. The membrane separation technology has high energy consumption and serious membrane fouling, and cannot achieve high-value recovery of fluorine resources. Although the nuclear crystallization granulation technology can improve the purity of calcium fluoride (>90%), the problems of seed loss and reactor scaling still limit its stability. In addition, the traditional process has low integration, a complex multi-stage treatment system, and insufficient automation, resulting in low resource recovery rate and high risk of secondary pollution; and during the fluorine recovery process, calcium fluoride residues are likely to occur, which will react and dissolve again with the newly entering wastewater, leading to repeated reactions that damage the equipment and reduce the service life of the equipment. Summary of the Invention

[0005] In view of the problems existing in the above-mentioned existing fluoride-containing wastewater recovery devices and methods, the present invention is proposed.

[0006] Therefore, the present invention provides a fluoride-containing wastewater recovery device and a recovery method, and the purpose is to solve the problems that the chemical precipitation method and the coagulation precipitation method are prone to cause secondary pollution, the adsorption method has high cost and limited application scope, these methods are difficult to meet the standards in terms of treatment efficiency, cost control and environmental protection performance, and residues are likely to cause repeated reactions of the equipment during recovery, damaging the equipment and reducing the service life.

[0007] To solve the above technical problems, the present invention provides the following technical solutions: a support unit, including a fixing frame; A reaction unit, including a reaction component arranged on the fixing frame; A recovery unit, including a guiding component arranged on the fixing frame, a heating component arranged inside the guiding component, a recovery component arranged inside the guiding component, and a collecting member arranged at the bottom of the guiding component, and the guiding component is connected to the reaction component in a penetrating manner.

[0008] As a preferred solution of the fluoride-containing wastewater recovery device of the present invention, among them: the reaction component includes a reaction tank arranged on the fixing frame, a stirring member arranged inside the reaction tank, stirring blades arranged on the stirring member, a heating rod arranged inside the stirring member, a transfer ring arranged on the outer diameter of the heating rod, and a first heating member arranged on the transfer ring, and the first heating member is fixedly connected to the stirring member.

[0009] As a preferred embodiment of the fluorine-containing wastewater recovery device of the present invention, the following is provided: a feeding port is arranged at the top of the reaction tank, a connecting pipe is arranged on one side of the reaction tank, a conveying pipe is arranged on the other side of the reaction tank, and the conveying pipe penetrates and is connected to the guiding assembly.

[0010] As a preferred embodiment of the fluorine-containing wastewater recovery device of the present invention, the following is provided: the guiding assembly includes a recovery tank arranged on the conveying pipe, an electric push rod arranged at the top of the recovery tank, an extension member arranged at the output end of the electric push rod, an L-shaped connecting member arranged on the outer diameter of the bottom of the extension member, a petal-shaped member arranged at the bottom of the L-shaped connecting member, a rotating member arranged on the petal-shaped member, and a heating box rotatably arranged on the outer diameter of the rotating member, and the heating box is fixedly connected to the recovery tank.

[0011] As a preferred embodiment of the fluorine-containing wastewater recovery device of the present invention, the following is provided: a sealing ring is arranged at the top of the petal-shaped member, and the sealing ring is fixedly connected to the heating box.

[0012] As a preferred embodiment of the fluorine-containing wastewater recovery device of the present invention, the following is provided: the heating assembly includes a second heating member arranged at the top of the heating box, a transfer member arranged inside the second heating member, and a conveying rod arranged on the transfer member, and the conveying rod is slidably connected inside the extension member.

[0013] As a preferred embodiment of the fluorine-containing wastewater recovery device of the present invention, the following is provided: a receiving ring is arranged at the bottom of the conveying rod, a heating pipe coil is arranged on the outer diameter of the receiving ring, and the receiving ring is slidably connected to the petal-shaped member.

[0014] As a preferred embodiment of the fluorine-containing wastewater recovery device of the present invention, the following is provided: the recovery assembly includes a recovery member arranged inside the recovery tank, a moving rod slidably arranged inside the recovery member, a receiving plate arranged on the moving rod, a return spring arranged inside the recovery member, and a connecting plate arranged at the top of the return spring, and the connecting plate is rotatably connected to the moving rod.

[0015] As a preferred embodiment of the fluorine-containing wastewater recovery device of the present invention, the following is provided: a first moving groove is arranged inside the recovery member, a second moving groove is arranged inside the recovery member, a rotating member is arranged on the outer diameter of the moving rod, and the rotating member is slidably connected to the first moving groove and the second moving groove.

[0016] In view of the fact that the chemical precipitation method and the coagulation precipitation method in the above-mentioned or existing technologies are prone to secondary pollution, the adsorption method has a high cost and a limited scope of application, and these methods are difficult to meet the standards not only in terms of treatment efficiency, cost control and environmental protection performance, but also prone to repeated reaction damage to the equipment due to residues during recovery, reducing the service life. Therefore, this detection method is proposed: a connecting pipe is connected to the wastewater discharge port, and the wastewater enters the interior of the reaction tank. Then, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are respectively added into the reaction tank through the feeding port as raw materials. By adjusting the amount of calcium salt added, the reaction time, and the initial fluoride ion concentration, the reaction is carried out. At the same time, the stirring blade and the heating element start to work to heat and stir the wastewater, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide inside the reaction tank. The reaction is carried out at a rotational speed of 200 r / min. After the reaction is completed, the slurry is centrifuged at a rotational speed of 4000 r / min for 5 minutes.

[0017] Then it is transported to the inside of the guiding component, and the heating component starts to continuously dry at 105 °C for 8 h. After complete dehydration, the calcium fluoride content is measured, and the remaining fluorine crystals after dehydration are transported to the recovery component through the guiding component for unified collection. The fluorine crystals are separated from the reaction solution that needs to be heated next time to avoid secondary reaction of the fluorine crystals. As more and more fluorine crystals accumulate on the top of the recovery component, the weight of the fluorine crystals causes the recovery component to move down and rotate. Finally, all the collected fluorine crystals fall on the top of the collecting component and are uniformly recovered through the collecting component. And the results of the fluorine recovery experiments of the three calcium salts are compared and analyzed, and the orthogonal experiment is designed by selecting the better experimental conditions to further optimize the process, so as to complete the maximum recovery of fluorine while ensuring the high quality of the product.

[0018] The beneficial effects of the present invention: By adding calcium salts such as industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide into the reaction tank, adjusting the addition amount, reaction time, and initial fluoride ion concentration, and simultaneously heating and stirring, the fluoride ions in the wastewater react fully with the calcium salts to generate calcium fluoride, thus efficiently recovering fluorine resources. Compared with the traditional methods, the present invention effectively solves the problems that the chemical precipitation method and the coagulation precipitation method produce a large amount of fluorine-containing sludge, which is easy to cause secondary pollution, and the adsorption method is only applicable to small-scale low-concentration wastewater and has a high cost. It can meet the requirements in terms of treatment efficiency, cost control, and environmental protection performance. At the same time, the fluorine crystals are separated from the reaction solution through the guiding component and transported to the recovery component for unified collection, avoiding the damage of the secondary reaction of the fluorine crystals to the equipment, thereby improving the service life of the equipment. By comparing and analyzing the results of the fluorine recovery experiments of the three calcium salts, the orthogonal experiment is designed by selecting the better experimental conditions to further optimize the process, and the maximum recovery of fluorine is achieved while ensuring the high quality of the product. Brief Description of the Drawings

[0019] To more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0020] Figure 1 It is a schematic diagram of the overall structure of the fluorine-containing wastewater recovery device of the present invention.

[0021] Figure 2 It is a schematic side view structure diagram of the fluorine-containing wastewater recovery device of the present invention.

[0022] Figure 3 It is a schematic sectional structure diagram of the reaction component of the fluorine-containing wastewater recovery device of the present invention.

[0023] Figure 4 For the fluorine-containing wastewater recovery device of the present invention Figure 3 The enlarged structure diagram at position A.

[0024] Figure 5 It is a schematic internal structure diagram of the recovery component of the fluorine-containing wastewater recovery device of the present invention.

[0025] Figure 6 For the fluorine-containing wastewater recovery device of the present invention Figure 5 The enlarged structure diagram at position B.

[0026] Figure 7 It is a schematic sectional structure diagram of the recovery component of the fluorine-containing wastewater recovery device of the present invention.

[0027] Figure 8 For the fluorine-containing wastewater recovery device of the present invention Figure 7 The enlarged structure diagram at position C.

[0028] Figure 9 For the fluorine-containing wastewater recovery device of the present invention Figure 7 The enlarged structure diagram at position D.

[0029] Figure 10 It is a schematic sectional structure diagram of the collection component of the fluorine-containing wastewater recovery device of the present invention.

[0030] Description of reference numerals in the drawings: 100, support unit; 101, fixing frame; 200, reaction unit; 201, reaction assembly; 2011, reaction tank; 2012, connecting pipe; 2013, feed inlet; 2014, stirring member; 2015, stirring blade; 2016, heating rod; 2017, transfer ring; 2018, first heating member; 2019, conveying pipe; 300, recovery unit; 301, guiding assembly; 3011, recovery tank; 3012, electric push rod; 3013, extension member; 3014, L-shaped connecting member; 3015, petal-shaped member; 3016, sealing ring; 3017, heating box; 3018, rotating member; 302, heating assembly; 3021, second heating member; 3022, transfer member; 3023, conveying rod; 3024, heating pipe coil; 3025, receiving ring; 303, recovery assembly; 3031, recovery member; 3032, first moving groove; 3033, second moving groove; 3034, return spring; 3035, connecting plate; 3036, moving rod; 3037, rotating member; 3038, receiving plate; 304, collecting member. Detailed implementation manners

[0031] In order to make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the specific implementation manners of the present invention will be given with reference to the drawings in the specification.

[0032] Example 1, referring to Figure 1 - Figure 4 , which is the first embodiment of the present invention, provides a fluorine-containing wastewater recovery device and a recovery method. This device includes: a support unit 100, a reaction unit 200, and a recovery unit 300.

[0033] Among them, the support unit 100 includes a fixing frame 101; The reaction unit 200 includes a reaction assembly 201 arranged on the fixing frame 101; Recovery unit 300, including a guiding component 301 arranged on a fixed frame 101, a heating component 302 arranged inside the guiding component 301, a recovery component 303 arranged inside the guiding component 301, and a collecting piece 304 arranged at the bottom of the guiding component 301. The guiding component 301 is connected to the reaction component 201 in a penetrating manner. When treating and recovering wastewater containing fluorine, the wastewater is connected to the reaction component 201, so that the wastewater enters the inside of the reaction component 201. At the same time, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are respectively added into the inside of the reaction component 201 as raw materials. By adjusting the addition amount of calcium salt, reaction time, and initial fluoride ion concentration, a reaction is carried out. And the reaction component 201 heats and stirs the reaction wastewater inside to increase the reaction time and speed. After the wastewater reaction inside the reaction component 201 is completed, the reaction component 201 transports the reaction wastewater to the inside of the guiding component 301. When the wastewater enters the inside of the guiding component 301, the heating component 302 starts to heat and dry the wastewater inside the guiding component 301, continuously drying at 105°C for 8 hours. Then, under the action of the guiding component 301, the fluorine crystals generated after dehydration are uniformly collected inside the recovery component 303, avoiding the fluorine crystals from reacting with the wastewater again, resulting in equipment damage. And the fluorine crystals uniformly collected inside the recovery component 303, as more and more are collected, the recovery component 303 uniformly recovers and processes the fluorine crystals through the collecting piece 304.

[0034] During use, when treating and recycling wastewater containing fluorine, the wastewater is connected to the reaction component 201, so that the wastewater enters the interior of the reaction component 201. At the same time, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are respectively added into the interior of the reaction component 201 as raw materials. By adjusting the addition amount of calcium salts, reaction time, and initial fluoride ion concentration, a reaction is carried out. The reaction component 201 heats and stirs the reaction wastewater inside to increase the reaction time and speed. After the wastewater reaction inside the reaction component 201 is completed, the reaction component 201 transports the reaction wastewater to the interior of the guiding component 301. When the wastewater enters the interior of the guiding component 301, the heating component 302 starts to heat and dry the wastewater inside the guiding component 301, continuously drying it at 105°C for 8 hours. Then, under the action of the guiding component 301, the fluorine crystals produced after dehydration are uniformly collected inside the recovery component 303, preventing the fluorine crystals from reacting with the wastewater again and causing damage to the equipment. And the fluorine crystals uniformly collected inside the recovery component 303, as more and more are collected, the recovery component 303 uniformly recovers and processes the fluorine crystals through the collection part 304, thereby efficiently recovering fluorine resources. Compared with traditional methods, the present invention effectively solves the problems that chemical precipitation method and coagulation precipitation method produce a large amount of fluorine-containing sludge and are prone to secondary pollution, and the adsorption method is only applicable to small-scale low-concentration wastewater and has high costs, etc. It can meet the requirements in terms of treatment efficiency, cost control, and environmental protection performance. At the same time, the fluorine crystals are separated from the reaction solution through the guiding component and transported to the recovery component for unified collection, avoiding damage to the equipment caused by the secondary reaction of the fluorine crystals, thereby improving the service life of the equipment.

[0035] Example 2, refer to Figure 1 - Figure 8, which is the second embodiment of the present invention. The difference between this embodiment and the first embodiment is that the reaction assembly 201 includes a reaction tank 2011 disposed on the fixing frame 101, a stirring member 2014 disposed inside the reaction tank 2011, stirring blades 2015 disposed on the stirring member 2014, a heating rod 2016 disposed inside the stirring member 2014, a transfer ring 2017 disposed on the outer diameter of the heating rod 2016, and a first heating member 2018 disposed on the transfer ring 2017. The first heating member 2018 is fixedly connected to the stirring member 2014. An inlet 2013 is provided at the top of the reaction tank 2011, a connecting pipe 2012 is provided on one side of the reaction tank 2011, and a conveying pipe 2019 is provided on the other side of the reaction tank 2011. The conveying pipe 2019 penetrates and is connected to the guiding assembly 301. When recovering fluorine-containing wastewater, the connecting pipe 2012 is connected to the wastewater discharge port to discharge the fluorine-containing wastewater from the inside of the reaction tank 2011. At the same time, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are added into the reaction tank 2011 through the opened inlet 2013 as raw materials, and the reaction is carried out by adjusting the addition amount of calcium salt, reaction time, and initial fluoride ion concentration. At the same time, while the fluorine-containing wastewater is reacting, the stirring member 2014 drives the stirring blades 2015 to start stirring the wastewater, and the heating rod 2016 also starts to generate heat, and the heat is transported to the transfer ring 2017. The heat is transported to the first heating member 2018 through the transfer ring 2017 to start heating and reacting the wastewater inside the reaction tank 2011. With the cooperation of the stirring blades 2015 and the first heating member 2018, the reaction time of the wastewater is accelerated.

[0036] During use, when recovering fluorine-containing wastewater, the connecting pipe 2012 is connected to the wastewater discharge port to discharge the fluorine-containing wastewater from the inside of the reaction tank 2011. At the same time, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are added to the inside of the reaction tank 2011 through the opening of the feeding port 2013. By adjusting the addition amount of calcium salts, reaction time, and initial fluoride ion concentration, the reaction is carried out. Meanwhile, while the fluorine-containing wastewater is reacting, the stirring member 2014 drives the stirring blade 2015 to start stirring the wastewater, and the heating rod 2016 also starts to generate heat, and the heat is transmitted to the transfer ring 2017. Through the transfer ring 2017, the heat is transmitted to the first heating member 2018 to start heating and reacting the wastewater inside the reaction tank 2011. With the cooperation of the stirring blade 2015 and the first heating member 2018, the reaction time of the wastewater is accelerated. After the reaction is completed, the slurry is centrifuged at a speed of 4000 r / min for 5 minutes, and then transported to the inside of the guiding assembly 301 for the next step of drying and recovery. By adding calcium salts such as industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide to the reaction tank 2011, adjusting the addition amount, reaction time, and initial fluoride ion concentration, and simultaneously performing heating and stirring, the fluoride ions in the wastewater fully react with the calcium salts to form calcium fluoride, thus efficiently recovering fluorine resources.

[0037] The rest of the structure is the same as that of Embodiment 1.

[0038] Embodiment 3, referring to Figure 1 - Figure 9, which is the third embodiment of the present invention. The difference between this embodiment and the second embodiment is as follows: The guiding component 301 includes a recovery tank 3011 arranged on the conveying pipe 2019, an electric push rod 3012 arranged on the top of the recovery tank 3011, an extension member 3013 arranged at the output end of the electric push rod 3012, an L-shaped connecting member 3014 arranged on the outer diameter of the bottom of the extension member 3013, a petal-shaped member 3015 arranged at the bottom of the L-shaped connecting member 3014, a rotating member 3018 arranged on the petal-shaped member 3015, and a heating box 3017 rotatably arranged on the outer diameter of the rotating member 3018, and the heating box 3017 is fixedly connected to the recovery tank 3011. A sealing ring 3016 is arranged on the top of the petal-shaped member 3015, and the sealing ring 3016 is fixedly connected to the heating box 3017. The heating component 302 includes a second heating member 3021 arranged on the top of the heating box 3017, a transfer member 3022 arranged inside the second heating member 3021, and a conveying rod 3023 arranged on the transfer member 3022. The conveying rod 3023 is slidably connected inside the extension member 3013. A receiving ring 3025 is arranged at the bottom of the conveying rod 3023, a heating tube coil 3024 is arranged on the outer diameter of the receiving ring 3025, and the receiving ring 3025 is slidably connected to the petal-shaped member 3015. After the wastewater reaction in the reaction tank 2011 is completed, the wastewater solution is conveyed into the interior of the recovery tank 3011 through the reaction component 201 and falls inside the heating box 3017 to carry out the drying and recovery work. The second heating member 3021 heats up, and the heat is conveyed to the heating tube coil 3024 at the bottom of the heating box 3017 through the transfer member 3022 and the conveying rod 3023, and the heating range starts to expand through the heating tube coil 3024 to carry out the heating and drying work on the wastewater solution inside the heating box 3017. It is continuously dried at 105 °C for 8 hours, so that the wastewater solution becomes fluorine crystals. After the wastewater solution inside the heating box 3017 is dried and becomes fluorine crystals, the electric push rod 3012 starts to extend downward, causing the extension member 3013 to drive the L-shaped connecting member 3014 and the petal-shaped member 3015 on the outer diameter of the extension member 3013 to start moving downward. At the same time, the rotating member 3018 at the other end of the petal-shaped member 3015 rotates and adjusts inside the heating box 3017, making the petal-shaped member 3015 become conical and open, so that all the fluorine crystals on the surface of the petal-shaped member 3015 fall into the bottom recovery component 303 for unified collection. And with the cooperation of the sealing ring 3016 at the top of the petal-shaped member 3015 and the receiving ring 3025, the sealing performance inside the heating box 3017 is ensured.

[0039] Compared with Embodiment 2, further, the recovery component 303 includes a recovery member 3031 disposed inside the recovery tank 3011, a moving rod 3036 slidably disposed inside the recovery member 3031, a receiving plate 3038 disposed on the moving rod 3036, a return spring 3034 disposed inside the recovery member 3031, and a connecting plate 3035 disposed at the top of the return spring 3034. The connecting plate 3035 is rotatably connected to the moving rod 3036. A first moving groove 3032 is provided inside the recovery member 3031, and a second moving groove 3033 is provided inside the recovery member 3031. A rotating member 3037 is provided on the outer diameter of the moving rod 3036, and the rotating member 3037 is slidably connected to the first moving groove 3032 and the second moving groove 3033. When the fluorine crystals inside the heating box 3017 fall onto the top of the receiving plate 3038, the receiving plate 3038 initially collects the fluorine crystals, preventing the fluorine crystals from reacting repeatedly with the waste water solution. Moreover, when more and more of the dried fluorine crystals that have fallen inside the heating box 3017 accumulate, the receiving plate 3038 begins to move downward along the first moving groove 3032 and the second moving groove 3033 inside the recovery member 3031 under the influence of the fluorine crystals and gravity. During the process of the moving rod 3036 squeezing the return spring 3034 and moving, due to the different lengths of the first moving groove 3032 and the second moving groove 3033 on both sides of the moving rod 3036, the moving rod 3036 contracts and flips, causing the fluorine crystals on the top of the receiving plate 3038 to roll to one side. As a result, the rotating member 3037 and the connecting plate 3035 flip, causing all the fluorine crystals on the top of the receiving plate 3038 to fall into the collection member 304 at the bottom for unified recovery processing. After the fluorine crystals on the top of the receiving plate 3038 have fallen, the weight of the receiving plate 3038 decreases, the return spring 3034 is released from the extrusion, and the moving rod 3036 drives the receiving plate 3038 to flip back to the upright position and move upward to return to the original position to continue separating and collecting the fluorine crystals.

[0040] During use, after the wastewater reaction inside the reaction tank 2011 is completed, the wastewater solution is transported into the interior of the recovery tank 3011 through the reaction assembly 201 and falls inside the heating box 3017 for drying and recovery work. It is heated by the second heating element 3021, and the heat is transported to the heating tube coil 3024 at the bottom of the heating box 3017 through the transfer piece 3022 and the conveying rod 3023. Then, the heating range starts to expand through the heating tube coil 3024 to heat and dry the wastewater solution inside the heating box 3017. It is continuously dried at 105 °C for 8 hours, causing the wastewater solution to turn into fluorine crystals. After the wastewater solution inside the heating box 3017 is dried into fluorine crystals, the electric push rod 3012 starts to extend downward, causing the extension piece 3013 to drive the L-shaped connecting piece 3014 and the petal-shaped piece 3015 on the outer diameter of the extension piece 3013 to start moving downward. At the same time, the rotating piece 3018 at the other end of the petal-shaped piece 3015 rotates and adjusts inside the heating box 3017, making the petal-shaped piece 3015 become conical and open, so that all the fluorine crystals on the surface of the petal-shaped piece 3015 fall onto the bottom recovery assembly 303 for unified collection. With the cooperation of the sealing ring 3016 and the receiving ring 3025 at the top of the petal-shaped piece 3015, the airtightness inside the heating box 3017 is ensured.

[0041] When the fluorine crystals inside the heating box 3017 fall onto the top of the receiving plate 3038, the receiving plate 3038 preliminarily collects the fluorine crystals to prevent the fluorine crystals from reacting repeatedly with the wastewater solution. And when more and more dried fluorine crystals fall inside the heating box 3017, the receiving plate 3038 starts to move downward along the moving groove one 3032 and the moving groove two 3033 inside the recovery piece 3031 under the influence of the fluorine crystals and gravity. During the process of the moving rod 3036 squeezing the return spring 3034 to move, because the lengths of the moving groove one 3032 and the moving groove two 3033 on both sides of the moving rod 3036 are different, the moving rod 3036 shrinks and flips, causing the fluorine crystals on the top of the receiving plate 3038 to all roll to one side, so that the rotating piece 3037 and the connecting plate 3035 flip, and all the fluorine crystals on the top of the receiving plate 3038 fall into the bottom collecting piece 304 for unified recovery treatment. And after the fluorine crystals on the top of the receiving plate 3038 fall, the weight of the receiving plate 3038 decreases, the return spring 3034 is released from extrusion, causing the moving rod 3036 to drive the receiving plate 3038 to flip back to the correct position and move upward to return to the original position to continue separating and collecting the fluorine crystals. By separating the fluorine crystals from the reaction solution and collecting them uniformly, the damage to the equipment caused by the secondary reaction of the fluorine crystals is avoided, thus improving the service life of the equipment. Through comparative analysis of the results of the fluorine recovery experiments on three calcium salts, the optimal experimental conditions are selected to design an orthogonal experiment to further optimize the process, achieving the maximum recovery of fluorine while ensuring the high quality of the product.

[0042] Example 4, referring to Figure 1 - Figure 10 , which is the fourth embodiment of the present invention. The difference between this embodiment and the third embodiment is that the connecting pipe 2012 is connected to the wastewater discharge port, and the wastewater enters the inside of the reaction tank 2011. Then, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are respectively added to the inside of the reaction tank 2011 through the feeding port 2013. By adjusting the calcium salt addition amount, reaction time, and initial fluoride ion concentration, a reaction is carried out. At the same time, the stirring blade 2015 and the heating element 1 2018 start to work to heat and stir the wastewater, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide inside the reaction tank 2011. The reaction is carried out at a rotation speed of 200 r / min. After the reaction is completed, the slurry is centrifuged at a speed of 4000 r / min for 5 minutes, and then transported to the inside of the guiding component 301. The heating component 302 starts to continuously dry at 105 °C for 8 h. After complete dehydration, the calcium fluoride content is measured, and fluorine crystals remain after dehydration is completed. They are transported to the recycling component 303 through the guiding component 301 for unified collection, separating the fluorine crystals from the reaction solution that needs to be heated next time to avoid secondary reaction of the fluorine crystals. As more and more fluorine crystals accumulate on the top of the recycling component 303, the weight of the fluorine crystals causes the recycling component 303 to move downward and rotate. Finally, all the collected fluorine crystals fall on the top of the collecting part 304 and are uniformly recycled through the collecting part 304. And the results of the fluorine recovery experiments of the three calcium salts are compared and analyzed, and orthogonal experiments are designed under relatively optimal experimental conditions to further optimize the process, achieving the maximum fluorine recovery while ensuring the high quality of the product.

[0043] During the use process, when recovering fluorine crystals, the connecting pipe 2012 is connected to the waste water discharge port, and the waste water enters the inside of the reaction tank 2011. Then, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are respectively added into the reaction tank 2011 through the feeding port 2013 as raw materials. By adjusting the calcium salt addition amount, reaction time, and initial fluoride ion concentration, a reaction is carried out. At the same time, the stirring blade 2015 and the heating element 1 2018 start to work to heat and stir the waste water, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide inside the reaction tank 2011. The reaction is carried out at a rotation speed of 200 r / min. After the reaction is completed, the slurry is centrifuged at a rotation speed of 4000 r / min for 5 minutes, and then transported to the inside of the guiding component 301. The heating component 302 starts to continuously dry at 105 °C for 8 h. After complete dehydration, the calcium fluoride content is measured, and the remaining fluorine crystals after dehydration are transported to the recovery component 303 through the guiding component 301 for unified collection, separating the fluorine crystals from the reaction solution that needs to be heated next time to avoid secondary reaction of the fluorine crystals. As more and more fluorine crystals accumulate on the top of the recovery component 303, the weight of the fluorine crystals causes the recovery component 303 to move downward and rotate. Finally, all the collected fluorine crystals fall on the top of the collection piece 304 and are uniformly recovered through the collection piece 304. By comparing and analyzing the results of the fluorine recovery experiments on the three calcium salts, the optimal experimental conditions are selected to design an orthogonal experiment to further optimize the process, achieving the maximum recovery of fluorine while ensuring the high quality of the product.

[0044] The remaining structure is the same as that of Embodiment 3.

[0045] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not restrictive. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A fluorine-containing wastewater recovery device, characterized in that: Comprising: A support unit (100), including a fixing frame (101); A reaction unit (200), including a reaction component (201) arranged on the fixing frame (101) for controlling the reaction rate; A recovery unit (300), including a guiding component (301) arranged on the fixing frame (101) for conveying reaction materials, a heating component (302) arranged inside the guiding component (301) for increasing the reaction rate, a recovery component (303) arranged inside the guiding component (301) for uniformly collecting fluorine crystals, and a collecting piece (304) arranged at the bottom of the guiding component (301) for discharging fluorine crystals, and the guiding component (301) is connected to the reaction component (201) in a penetrating manner.

2. The fluorine-containing wastewater recovery device according to claim 1, wherein: The reaction component (201) includes a reaction tank (2011) arranged on the fixing frame (101), a stirring piece (2014) arranged inside the reaction tank (2011), stirring blades (2015) arranged on the stirring piece (2014), a heating rod (2016) arranged inside the stirring piece (2014), a transfer ring (2017) arranged on the outer diameter of the heating rod (2016), and a first heating piece (2018) arranged on the transfer ring (2017), and the first heating piece (2018) is fixedly connected to the stirring piece (2014).

3. The fluorine-containing wastewater recovery device according to claim 2, wherein: A feed inlet (2013) is arranged at the top of the reaction tank (2011), a connecting pipe (2012) is arranged on one side of the reaction tank (2011), a conveying pipe (2019) is arranged on the other side of the reaction tank (2011), and the conveying pipe (2019) is connected to the guiding component (301) in a penetrating manner.

4. The fluorine-containing wastewater recovery device according to claim 3, characterized in that: The guiding component (301) includes a recovery tank (3011) arranged on the conveying pipe (2019), an electric push rod (3012) arranged at the top of the recovery tank (3011), an extension piece (3013) arranged at the output end of the electric push rod (3012), an L-shaped connecting piece (3014) arranged on the outer diameter of the bottom of the extension piece (3013), a petal-shaped piece (3015) arranged at the bottom of the L-shaped connecting piece (3014), a rotating piece (3018) arranged on the petal-shaped piece (3015), and a heating box (3017) rotatably arranged on the outer diameter of the rotating piece (3018), and the heating box (3017) is fixedly connected to the recovery tank (3011).

5. The fluorine-containing wastewater recovery device according to claim 4, characterized in that: A sealing ring (3016) is arranged at the top of the petal-shaped piece (3015), and the sealing ring (3016) is fixedly connected to the heating box (3017).

6. The fluorine-containing wastewater recovery device according to claim 5, characterized in that: The heating component (302) includes a second heating piece (3021) arranged at the top of the heating box (3017), a transfer piece (3022) arranged inside the second heating piece (3021), and a conveying rod (3023) arranged on the transfer piece (3022), and the conveying rod (3023) is slidably connected inside the extension piece (3013).

7. The fluorine-containing wastewater recovery device according to claim 6, characterized in that: A receiving ring (3025) is arranged at the bottom of the conveying rod (3023), a heating tube coil (3024) is arranged on the outer diameter of the receiving ring (3025), and the receiving ring (3025) is slidably connected to the petal-shaped piece (3015).

8. The fluorine-containing wastewater recovery device according to claim 7, wherein: Recovery component (303), including a recovery part (3031) disposed inside the recovery tank (3011), a moving rod (3036) slidably disposed inside the recovery part (3031), a receiving plate (3038) disposed on the moving rod (3036), a return spring (3034) disposed inside the recovery part (3031), and a connecting plate (3035) disposed at the top of the return spring (3034), and the connecting plate (3035) is rotatably connected to the moving rod (3036).

9. The fluorine-containing wastewater recovery device according to claim 8, wherein: A first moving groove (3032) is provided inside the recovery part (3031), a second moving groove (3033) is provided inside the recovery part (3031), a rotating part (3037) is provided on the outer diameter of the moving rod (3036), and the rotating part (3037) is slidably connected to the first moving groove (3032) and the second moving groove (3033).

10. A method for recovering fluorine-containing wastewater, which is applied to the fluorine-containing wastewater recovery device according to any one of claims 1-9, and is characterized in that: The recovery method further includes: connecting the connecting pipe (2012) to the wastewater discharge port, the wastewater enters the inside of the reaction tank (2011), and then industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide are respectively added into the reaction tank (2011) through the feeding port (2013). By adjusting the addition amount of calcium salt, reaction time, and initial fluoride ion concentration, a reaction is carried out. At the same time, the stirring blade (2015) and the first heating part (2018) start to work to heat and stir the wastewater, industrial calcium carbonate, industrial calcium chloride, and industrial calcium hydroxide inside the reaction tank (2011). The reaction is carried out at a rotation speed of 200 r / min. After the reaction is completed, the slurry is centrifuged at a rotation speed of 4000 r / min for 5 minutes, and then conveyed to the inside of the guiding component (301). The heating component (302) starts to continuously dry at 105 °C for 8 h. And for the fluorine crystals remaining after dehydration, they are conveyed to the recovery component (303) through the guiding component (301) for unified collection, separating the fluorine crystals from the reaction solution that needs to be heated next time to avoid secondary reaction of the fluorine crystals. As more and more fluorine crystals accumulate on the top of the recovery component (303), the weight of the fluorine crystals causes the recovery component (303) to move downward and rotate. Finally, all the collected fluorine crystals fall on the top of the collecting part (304), and are uniformly recovered through the collecting part (304). And the results of the fluorine recovery experiments of the three calcium salts are compared and analyzed, and the orthogonal experiment is designed by selecting the better experimental conditions to further optimize the process, and the maximum recovery of fluorine is completed while ensuring the high quality of the product.

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