Fluorine-containing wastewater adsorption treatment device, adsorption material and preparation method thereof

Abstract

The present invention provides a fluorine-containing wastewater adsorption treatment device, an adsorption material and a preparation method thereof. The fluorine-containing wastewater adsorption treatment device comprises: a shell; a treatment barrel is rotatably connected to the inside of the shell, a filter is installed on the treatment barrel, and a discharge chute is installed at the bottom of the treatment barrel. The fluorine-containing wastewater adsorption treatment device, the adsorption material and a preparation method thereof provided by the present invention, by putting the fluorine-containing wastewater and the adsorption material into the treatment barrel together for reaction, so that the fluorine element in the fluorine-containing wastewater is adsorbed into the adsorption material to produce a precipitate. After static sedimentation, the wastewater and the precipitate can be separated as the displacement member contracts, and the precipitate can be discharged again by contracting again. The reaction, precipitation and discharge functions are integrated into one, which greatly reduces the use cost, reduces the floor space, facilitates discharge, reduces the workload of the staff, and realizes the conversion between different states at the same time. The operation is simple and convenient, and has the effect of multifunctional use.

Description

Technical Field

[0001] The present invention relates to the field of brine treatment, and in particular to a fluorine-containing wastewater adsorption treatment device, an adsorption material and a preparation method thereof. Background Art

[0002] With the development of modern industry, the mining and metallurgical industries produce large amounts of fluorine-containing brines during production. These brines often contain a high concentration of fluorine in the form of fluoride ions. High concentrations of fluorine are harmful to the environment and human health, so they must be removed. Direct discharge of fluorine-containing wastewater pollutes the environment, causing poisoning in surrounding humans and animals and endemic fluorosis. Direct internal use can cause system disruption or even collapse, and evaporator corrosion.

[0003] The adsorption method is based on the principle that F- in water is adsorbed onto the surface of a solid adsorbent, bonded to the surface of the adsorbent or simply adsorbed on the surface through relatively weak intermolecular forces. The fluoride removal effect of this method is mainly restricted by the type of adsorbent.

[0004] In the existing technology, a large number of equipment are used for adsorption of fluorine-containing wastewater, generally including reaction tanks, sedimentation tanks and filtration devices, which have complex structures. More equipment not only increases the cost, but also requires a larger floor space. After the adsorption is completed, the sediment needs to be removed by workers, which is more troublesome to clean up.

[0005] Therefore, it is necessary to provide a fluorine-containing wastewater adsorption treatment device, an adsorption material and a preparation method thereof to solve the above technical problems. Summary of the Invention

[0006] The present invention provides a fluorine-containing wastewater adsorption treatment device, an adsorption material and a preparation method thereof, which solves the problem that more equipment not only increases the cost but also requires a larger floor space, and the sediment after adsorption needs to be removed by workers, which is troublesome to clean up.

[0007] In order to solve the above technical problems, the present invention provides a fluorine-containing wastewater adsorption treatment device comprising: a housing;

[0008] A treatment barrel is rotatably connected to the interior of the shell. The treatment barrel is used to contain fluorine-containing wastewater and to put adsorption material into it to cause adsorption reaction between the fluorine-containing wastewater and the adsorption material. A filter is installed on the treatment barrel. A discharge chute is installed at the bottom of the treatment barrel. A drainage chute and an open chute are provided on the left side of the shell. A partition is fixedly connected to the interior of the shell, and a sliding sleeve is slidably connected to the partition.

[0009] The bottom of the shell is fixedly connected to a displacement piece, the top of the displacement piece is fixedly connected to a connecting plate, the connecting plate is fixedly connected to a support sleeve, the bottom of the shell is installed with a cylinder, the interior of the cylinder is slidably connected to a sliding block, the bottom of the sliding block is installed with a first elastic piece, the top of the sliding block is installed with a connecting rod, the outer surface of the connecting rod is fixedly connected to a connecting block, the top of the connecting rod passes through the connecting plate and is installed with a sealing plate, the sealing plate abuts against the discharge trough for closing the discharge trough.

[0010] Preferably, the top of the shell is fixedly connected to a support frame, the bottom of the support frame is fixedly connected to a stirring rod, the stirring rod extends into the processing barrel, the outer surface of the stirring rod is provided with multiple groups of stirring blades, a driving motor is installed on the shell, a transmission assembly is installed between the driving motor and the processing barrel, the driving motor drives the processing barrel to rotate through the transmission assembly to achieve stirring; during stirring, the sliding sleeve covers the outer surface of the filter screen to seal the filter screen.

[0011] Preferably, the transmission assembly is two gears meshing with each other, wherein one of the gears is mounted on the output shaft of the driving motor, and the other gear is mounted on the outer surface of the processing barrel.

[0012] Preferably, a cavity is provided inside the stirring rod, and a group of stirring blades are slidably connected to the inside of a telescopic rod, the outer surface of the telescopic rod is sleeved with a second elastic member, one end of the telescopic rod extends to the inside of the cavity, and a scraper is installed at the other end of the telescopic rod, and the opposite ends of the two telescopic rods are provided with a first inclined surface, and the top of the sealing plate is fixedly connected to an auxiliary rod, and the auxiliary rod extends to the inside of the cavity, and a moving block is installed at the top of the auxiliary rod, and the bottom of the moving block is provided with two symmetrical second inclined surfaces.

[0013] Preferably, a water collecting tank and a suction pump are fixedly connected to the right side of the shell, a first connecting pipe is connected between the water collecting tank and the inlet of the suction pump, and a second connecting pipe is connected to the outlet of the suction pump. The second connecting pipe passes through the shell and extends to the interior of the shell, a nozzle is installed on the second connecting pipe, and a conduit is connected between the drainage trough and the water collecting tank.

[0014] An adsorption material is added into the fluorine-containing wastewater adsorption treatment device to achieve the treatment of fluorine-containing wastewater, and is prepared from carboxymethyl chitosan and amino magnetic nanoparticles.

[0015] A method for preparing an adsorption material, for preparing the adsorption material, comprising:

[0016] S1, prepare carboxymethyl chitosan, the steps are as follows:

[0017] S11, placing chitosan in a three-necked flask, adding an organic solvent to dissolve and stir;

[0018] S12. Slowly add sodium hydroxide solution using a dropping funnel and stir in a constant temperature water bath to alkalize;

[0019] S13, dissolving chloroacetic acid in an organic solvent, slowly adding the solution dropwise to the alkalized chitosan solution, heating and continuing stirring;

[0020] S14, adding glacial acetic acid to adjust the pH, pouring the reaction solution into anhydrous ethanol and stirring;

[0021] S15, centrifuging the precipitate, washing and drying to obtain carboxymethyl chitosan;

[0022] S2. Preparation of amino-modified magnetic nanoparticles, the steps are as follows:

[0023] S21, dissolving substances containing divalent iron ions and trivalent iron ions in deionized water to prepare solutions, and placing the solutions in a three-necked flask;

[0024] S22, introduce nitrogen to expel all air, and stir vigorously in a constant temperature water bath;

[0025] S23, rapidly adding ammonia water dropwise using a dropping funnel while continuing to stir to obtain black Fe3O4 nanoparticles;

[0026] S24, separating the Fe3O4 nanoparticles using a magnet and washing them with deionized water until they are neutral;

[0027] S25, dispersing the washed Fe3O4 nanoparticles in anhydrous ethanol, and adding a silane coupling agent or an amino acid substance;

[0028] S26, reflux and stir the reaction in a constant temperature water bath;

[0029] S27, separating the amino-modified magnetic nanoparticles using a magnet and washing them with anhydrous ethanol;

[0030] S3, prepare carboxymethylated chitosan-based magnetic adsorbent, the steps are as follows:

[0031] S31, dissolving the carboxymethyl chitosan prepared above in deionized water to prepare a solution, slowly adding it to the solution prepared by the aluminum source material, and stirring evenly;

[0032] S32, adding the amino-modified magnetic nanoparticles prepared above, and sonicating to obtain a uniform mixed solution;

[0033] S33, dissolving genipin in deionized water to prepare a solution, slowly adding it to the above mixed solution, and stirring in a constant temperature water bath;

[0034] S34, add alkaline solution to adjust the pH of the mixed solution and continue stirring;

[0035] S35, preparing a solution of polyethyleneimine with a mass fraction of 2%, adding the solution to the mixed solution and stirring;

[0036] S36, adding 25% by mass of glutaraldehyde to the mixed solution, and stirring at room temperature;

[0037] S37, repeatedly washing the reaction product with deionized water until the pH of the washing solution reaches neutral, and separating the product with a magnet after each washing;

[0038] S38. Drying the washed product to a constant weight to obtain a carboxymethylated chitosan-based magnetic adsorbent, i.e., the adsorption material.

[0039] Preferably, the organic solvent in S11 is one of isopropanol, methanol, ethanol, and acetone; the concentration of the sodium hydroxide solution in S12 is 40%-60%, the water bath temperature is 30-50°C, and the alkalization time is 1-2h; the organic solvent in S13 is consistent with that in S11, the temperature is raised to 60-80°C, and the stirring time is 4-6h; the pH in S14 is neutral; the centrifugal speed in S15 is 4000-6000r / min, the centrifugal time is 10-30min, and washing is performed 3 times with anhydrous ethanol.

[0040] Preferably, the divalent iron ion substance in S21 is FeSO4·7H2O, and the trivalent iron ion substance is FeCl3·6H2O; the temperature in S22 is 80-100°C, and the stirring time is 30-60 min; the stirring time in S23 is 30-60 min; the silane coupling agent in S25 is one of γ-aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-540), and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), and the amino acid substance is lysine; the temperature in S26 is 60-80°C, and the stirring time is 6-8 h; and the anhydrous ethanol washing in S27 is performed 3 times.

[0041] Preferably, the aluminum source material in S31 is one of aluminum nitrate nonahydrate and aluminum chloride; the ultrasonic time in S32 is 30-60 min; the constant temperature in S33 is 40-60°C, and the stirring time is 4-6 h; the alkaline solution in S34 is 1 mol / L sodium hydroxide solution, the pH is 8-9, and the stirring time is 6-8 h; the stirring time in S35 is 1-2 h; the stirring time in S36 is 6-8 h; and the drying in a vacuum environment in S38 is at a temperature of 60-80°C and a time of 60-90 min.

[0042] Compared with related technologies, the fluorine-containing wastewater adsorption treatment device, adsorption material and preparation method thereof provided by the present invention have the following beneficial effects:

[0043] The present invention provides a fluorine-containing wastewater adsorption treatment device, an adsorption material and a preparation method thereof. The fluorine-containing wastewater and the adsorption material are put into a treatment barrel together for reaction, so that the fluorine element in the fluorine-containing wastewater is adsorbed into the adsorption material to generate a precipitate. After static sedimentation, the wastewater and the precipitate can be separated as the displacement member contracts, and the precipitate can be discharged by contracting again. The device integrates the multiple functions of reaction, precipitation and discharge, greatly reduces the use cost, reduces the floor space, facilitates discharge, reduces the workload of staff, and realizes the conversion between different states. The operation is simple and convenient, and the device has the effect of multifunctional use. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 A schematic structural diagram of a first embodiment of a fluorine-containing wastewater adsorption treatment device provided by the present invention;

[0045] Figure 2 for Figure 1 A schematic cross-sectional view of the housing shown;

[0046] Figure 3 for Figure 2 An enlarged schematic diagram of part A is shown;

[0047] Figure 4 for Figure 2 A schematic cross-sectional view of the stirring rod shown;

[0048] Figure 5 The diagram of the fluorine-containing wastewater adsorption treatment device in use, wherein (5a) is a schematic diagram of the stirring state, (5b) is a schematic diagram of the solid-liquid separation state, (5c) is a schematic diagram of the discharge state, and (5d) is a schematic diagram of the filter screen cleaning state;

[0049] Figure 6 A schematic structural diagram of a second embodiment of the fluorine-containing wastewater adsorption treatment device provided by the present invention;

[0050] Figure 7 for Figure 6 A schematic cross-sectional view of the housing shown;

[0051] Figure 8 The present invention provides a flow chart of the method for preparing the adsorption material.

[0052] Numbers in the figure: 1. outer shell, 2. processing barrel, 3. filter screen, 4. discharge trough, 5. drainage trough, 6. opening trough, 7. partition, 8. sliding sleeve, 9. support frame, 10. stirring rod, 11. stirring blade, 12. drive motor, 13. transmission assembly, 14. displacement member, 15. connecting plate, 16. support sleeve, 17. cylinder, 18. sliding block, 19. first elastic member, 20. connecting rod, 21. connecting block, 22. sealing plate, 23. cavity, 24. telescopic rod, 25. second elastic member, 26. scraper, 27. first inclined plane, 28. auxiliary rod, 29. moving block, 30. second inclined plane, 31. water collecting tank, 32. suction pump, 33. first connecting pipe, 34. second connecting pipe, 35. nozzle, 36. conduit. DETAILED DESCRIPTION

[0053] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0054] First embodiment

[0055] Please refer to Figure 1-5 ,in, Figure 1 A schematic structural diagram of a first embodiment of a fluorine-containing wastewater adsorption treatment device provided by the present invention; Figure 2 for Figure 1 A schematic cross-sectional view of the housing shown; Figure 3 for Figure 2 An enlarged schematic diagram of part A is shown; Figure 4 for Figure 2 A schematic cross-sectional view of the stirring rod shown; Figure 5 The diagram of the fluorine-containing wastewater adsorption treatment device in use, wherein (5a) is a schematic diagram of the stirring state, (5b) is a schematic diagram of the solid-liquid separation state, (5c) is a schematic diagram of the discharge state, and (5d) is a schematic diagram of the filter screen cleaning state. The fluorine-containing wastewater adsorption treatment device includes: a housing 1;

[0056] A treatment barrel 2 is rotatably connected to the interior of the housing 1. The treatment barrel 2 is used to contain fluorine-containing wastewater and to put adsorption material into it to cause adsorption reaction between the fluorine-containing wastewater and the adsorption material. A filter screen 3 is installed on the treatment barrel 2, and a discharge chute 4 is installed at the bottom of the treatment barrel 2. A drainage chute 5 and an opening chute 6 are provided on the left side of the housing 1. A partition 7 is fixedly connected to the interior of the housing 1, and a sliding sleeve 8 is slidably connected to the partition 7.

[0057] The bottom of the shell 1 is fixedly connected to a displacement member 14, the top of the displacement member 14 is fixedly connected to a connecting plate 15, and the connecting plate 15 is fixedly connected to a support sleeve 16, and the support sleeve 16 is used to support the sliding sleeve 8 to achieve blocking of the filter screen 3; the bottom of the shell 1 is installed with a cylinder 17, and the interior of the cylinder 17 is slidably connected to a sliding block 18, and the bottom of the sliding block 18 is installed with a first elastic member 19, and the top of the sliding block 18 is installed with a connecting rod 20, and the outer surface of the connecting rod 20 is fixedly connected to a connecting block 21, and the top of the connecting rod 20 passes through the connecting plate 15 and is installed with a sealing plate 22, and the sealing plate 22 abuts on the discharge trough 4 to close the discharge trough 4.

[0058] In this embodiment, the first elastic member 19 includes but is not limited to a spring, a pneumatic piston cylinder, etc., and only needs to satisfy the reset of the sliding block 18 after displacement, and the elastic force of the first elastic member 19 is completely sufficient to support the gravity of the sliding block 18.

[0059] In this embodiment, the displacement member 14 includes but is not limited to an electric telescopic rod, a cylinder, a hydraulic rod, a linear motor, etc., and only needs to drive the connecting plate 15 to move linearly up and down.

[0060] In this embodiment, the bottom of the processing barrel 2 is a curved surface structure, and the bottom of the inner wall of the shell 1 is also inclined, tilted toward the opening groove 6, which can facilitate material discharge.

[0061] The top of the outer shell 1 is fixedly connected to a support frame 9, and the bottom of the support frame 9 is fixedly connected to a stirring rod 10, which extends into the processing barrel 2. The outer surface of the stirring rod 10 is provided with multiple groups of stirring blades 11, and a driving motor 12 is installed on the outer shell 1. A transmission assembly 13 is installed between the driving motor 12 and the processing barrel 2. The driving motor 12 drives the processing barrel 2 to rotate through the transmission assembly 13 to achieve stirring; during stirring, the sliding sleeve 8 covers the outer surface of the filter screen 3 to seal the filter screen 3.

[0062] In this embodiment, the transmission assembly 13 includes but is not limited to mechanical transmission mechanisms such as belt pulleys, chain sprockets, and gear sets, and only needs to realize the transmission between the drive motor 12 and the processing barrel 2.

[0063] The transmission assembly 13 is two gears meshing with each other, one of which is mounted on the output shaft of the driving motor 12 , and the other is mounted on the outer surface of the processing barrel 2 .

[0064] A cavity 23 is provided inside the stirring rod 10, and a group of stirring blades 11 are slidably connected to the inside of a telescopic rod 24, and the outer surface of the telescopic rod 24 is sleeved with a second elastic member 25. One end of the telescopic rod 24 extends to the inside of the cavity 23, and the other end of the telescopic rod 24 is equipped with a scraper 26. The opposite ends of the two telescopic rods 24 are each provided with a first inclined surface 27. The top of the sealing plate 22 is fixedly connected to an auxiliary rod 28, and the auxiliary rod 28 extends to the inside of the cavity 23. A moving block 29 is installed on the top of the auxiliary rod 28, and the bottom of the moving block 29 is provided with two symmetrical second inclined surfaces 30.

[0065] In this embodiment, the second elastic member 25 includes but is not limited to a spring, an elastic rib, a piston cylinder, etc., and is only required to ensure the restoration of the telescopic rod 24 after displacement.

[0066] As the auxiliary rod 28 moves downward, the moving block 29 moves downward, thereby squeezing the first inclined surface 27 through the second inclined surface 30, causing the two telescopic rods 24 to extend outward, thereby enabling the two scrapers 26 to move away from each other and cling to the filter 3.

[0067] In this embodiment, the device has four usage states, which are specifically as follows:

[0068] Stirring status (see Figure 5 a): introducing fluorine-containing wastewater into the interior of the treatment barrel 2, and adding a carboxymethylated chitosan-based magnetic adsorbent therein, and then driving the treatment barrel 2 to rotate by the driving motor 12, so that the stirring rod 10 stirs inside the treatment barrel 2, so that the fluorine-containing wastewater and the carboxymethylated chitosan-based magnetic adsorbent fully react, remove fluoride ions in the wastewater and generate precipitation;

[0069] Solid-liquid separation state (see Figure 5 b): After the fluorine-containing wastewater and the carboxymethylated chitosan-based magnetic adsorbent have fully reacted, the displacement member 14 contracts, causing the connecting plate 15 to drive the support sleeve 16 to move downward, thereby causing the sliding sleeve 8 to fall and no longer block the filter screen 3. At this time, as the driving motor 12 drives the treatment barrel 2 to rotate, the sediment and the purified water are centrifugally separated. The water is thrown out and discharged through the drain trough 5, while the sediment remains inside the treatment barrel 2;

[0070] Sediment discharge status (see Figure 5 c) The displacement member 14 contracts again, causing the connecting plate 15 to move downward. When it contacts the connecting block 21, it drives the connecting block 21 downward, thereby causing the connecting rod 20 to move downward, and then the sealing plate 22 to move downward, opening the discharge chute 4, so that the sediment is discharged from the processing barrel 2 and then cleaned out through the opening slot 6;

[0071] Filter cleaning status (see Figure 5 d): Through the further contraction of the displacement member 14, the connecting plate 15 continues to move downward, thereby driving the connecting block 21 to continue to move downward, and the sealing plate 22 to continue to move downward, so that the auxiliary rod 28 moves downward, driving the moving block 29 to slide downward inside the cavity 23, and pushing the two telescopic rods 24 outward, so that the two scrapers 26 move away from each other and come into contact with the filter 3. With the rotation of the processing barrel 2, the sediment attached to the surface of the filter 3 can be cleaned up to avoid affecting the use of the filter 3.

[0072] The working principle of the fluorine-containing wastewater adsorption treatment device provided by the present invention is as follows:

[0073] Fluorine-containing wastewater is introduced into the treatment barrel 2, and adsorption material is added thereto so that the fluorine-containing wastewater and the adsorption material react fully, fluoride ions in the wastewater are removed and precipitation is generated; then, the displacement member 14 contracts, so that the connecting plate 15 drives the support sleeve 16 to move downward, thereby causing the sliding sleeve 8 to fall, and the adsorbed wastewater and sediment are separated through the filter screen 3, and the water is discharged through the drainage groove 5, while the sediment remains in the treatment barrel 2, and then the displacement member 14 contracts again, so that the connecting plate 15 moves downward, and when it contacts the connecting block 21, it drives the connecting block 21 to move downward, thereby causing the connecting rod 20 to move downward, and then causing the sealing plate 22 to move downward, opening the discharge chute 4, so that the sediment is discharged from the treatment barrel 2 and then discharged through the opening groove 6.

[0074] Compared with related technologies, the fluorine-containing wastewater adsorption treatment device provided by the present invention has the following beneficial effects:

[0075] By putting fluorine-containing wastewater and adsorption material into the treatment barrel 2 together for reaction, the fluorine element in the fluorine-containing wastewater is adsorbed into the adsorption material to produce a precipitate. After static sedimentation, the wastewater and the precipitate can be separated as the displacement member 14 contracts, and the precipitate can be discharged again by contracting again. The reaction, precipitation and discharge functions are integrated into one, which greatly reduces the cost of use, reduces the floor space, facilitates discharge, reduces the workload of the staff, and realizes the conversion between different states. The operation is simple and convenient, and it has the effect of multi-functional use.

[0076] Second embodiment

[0077] Please refer to Figure 6-7 Based on the fluorine-containing wastewater adsorption treatment device provided in the first embodiment of this application, the second embodiment of this application provides another fluorine-containing wastewater adsorption treatment device. The second embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the independent implementation of the first embodiment.

[0078] Specifically, the difference of the fluorine-containing wastewater adsorption treatment device provided in the second embodiment of the present application is that a water collecting tank 31 and a suction pump 32 are fixedly connected to the right side of the shell 1, and a first connecting pipe 33 is connected between the water collecting tank 31 and the inlet of the suction pump 32, and a second connecting pipe 34 is connected to the outlet of the suction pump 32. The second connecting pipe 34 passes through the shell 1 and extends to the interior of the shell 1. A nozzle 35 is installed on the second connecting pipe 34, and a conduit 36 ​​is connected between the drainage trough 5 and the water collecting tank 31.

[0079] Compared with related technologies, the fluorine-containing wastewater adsorption treatment device provided by the present invention has the following beneficial effects:

[0080] The water discharged through the drainage trough 5 can be introduced into the interior of the water collecting tank 31 through the conduit 36, and is sucked by the suction pump 32 so that the water is sprayed out through the nozzle 35, and the nozzle 35 is aimed at the filter 3. As the treatment barrel 2 rotates, the filter 3 can be backwashed, thereby improving the cleaning effect of the filter 3.

[0081] The present invention also provides an adsorption material, which is added to the fluorine-containing wastewater adsorption treatment device to achieve the treatment of fluorine-containing wastewater, and is prepared from carboxymethyl chitosan and amino magnetic nanoparticles.

[0082] See also Figure 8 The present invention also provides a method for preparing an adsorption material, which comprises:

[0083] S1, prepare carboxymethyl chitosan, the steps are as follows:

[0084] S11, placing chitosan in a three-necked flask, adding an organic solvent to dissolve and stir;

[0085] S12. Slowly add sodium hydroxide solution using a dropping funnel and stir in a constant temperature water bath to alkalize;

[0086] S13, dissolving chloroacetic acid in an organic solvent, slowly adding the solution dropwise to the alkalized chitosan solution, heating and continuing stirring;

[0087] S14, adding glacial acetic acid to adjust the pH, pouring the reaction solution into anhydrous ethanol and stirring;

[0088] S15, centrifuging the precipitate, washing and drying to obtain carboxymethyl chitosan;

[0089] S2. Preparation of amino-modified magnetic nanoparticles, the steps are as follows:

[0090] S21, dissolving substances containing divalent iron ions and trivalent iron ions in deionized water to prepare solutions, and placing the solutions in a three-necked flask;

[0091] S22, introduce nitrogen to expel all air, and stir vigorously in a constant temperature water bath;

[0092] S23, rapidly adding ammonia water dropwise using a dropping funnel while continuing to stir to obtain black Fe3O4 nanoparticles;

[0093] S24, separating the Fe3O4 nanoparticles using a magnet and washing them with deionized water until they are neutral;

[0094] S25, dispersing the washed Fe3O4 nanoparticles in anhydrous ethanol, and adding a silane coupling agent or an amino acid substance;

[0095] S26, reflux and stir the reaction in a constant temperature water bath;

[0096] S27, separating the amino-modified magnetic nanoparticles using a magnet and washing them with anhydrous ethanol;

[0097] S3, prepare carboxymethylated chitosan-based magnetic adsorbent, the steps are as follows:

[0098] S31, dissolving the carboxymethyl chitosan prepared above in deionized water to prepare a solution, slowly adding it to the solution prepared by the aluminum source material, and stirring evenly;

[0099] S32, adding the amino-modified magnetic nanoparticles prepared above, and sonicating to obtain a uniform mixed solution;

[0100] S33, dissolving genipin in deionized water to prepare a solution, slowly adding it to the above mixed solution, and stirring in a constant temperature water bath;

[0101] S34, add alkaline solution to adjust the pH of the mixed solution and continue stirring;

[0102] S35, preparing a solution of polyethyleneimine with a mass fraction of 2%, adding the solution to the mixed solution and stirring;

[0103] S36, adding 25% by mass of glutaraldehyde to the mixed solution, and stirring at room temperature;

[0104] S37, repeatedly washing the reaction product with deionized water until the pH of the washing solution reaches neutral, and separating the product with a magnet after each washing;

[0105] S38. Drying the washed product to a constant weight to obtain a carboxymethylated chitosan-based magnetic adsorbent, i.e., the adsorption material.

[0106] The organic solvent in S11 is one of isopropanol, methanol, ethanol, and acetone; the concentration of the sodium hydroxide solution in S12 is 40%-60%, the water bath temperature is 30-50°C, and the alkalization time is 1-2h; the organic solvent in S13 is the same as that in S11, the temperature is raised to 60-80°C, and the stirring time is 4-6h; the pH in S14 is neutral; the centrifugal speed in S15 is 4000-6000r / min, the centrifugal time is 10-30min, and washing is performed 3 times with anhydrous ethanol.

[0107] In the S21, the divalent iron ion substance is FeSO4·7H2O, and the trivalent iron ion substance is FeCl3·6H2O; in the S22, the temperature is 80-100°C, and the stirring time is 30-60 min; in the S23, the stirring time is 30-60 min; in the S25, the silane coupling agent is one of γ-aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-540), and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), and the amino acid substance is lysine; in the S26, the temperature is 60-80°C, and the stirring time is 6-8 h; in the S27, washing is performed three times with anhydrous ethanol.

[0108] The aluminum source material in S31 is one of aluminum nitrate nonahydrate and aluminum chloride; the ultrasonic time in S32 is 30-60 min; the constant temperature in S33 is 40-60°C, and the stirring time is 4-6 h; the alkaline solution in S34 is 1 mol / L sodium hydroxide solution, the pH is 8-9, and the stirring time is 6-8 h; the stirring time in S35 is 1-2 h; the stirring time in S36 is 6-8 h; and the drying in vacuum environment in S38 is at a temperature of 60-80°C and a time of 60-90 min.

[0109] Furthermore, the adsorbent was subjected to adsorption experiments with fluorine-containing brine. The adsorbent was mixed with fluorine-containing brine for adsorption, and the fluorine in the actual fluorine-containing wastewater was adsorbed within 10 minutes. - The concentration decreased from 10.1 mg L−1 to 1.2 mg L−1. After 10 cycles, the adsorbent had a strong affinity for F - The adsorption capacity of the cellulose acetate solution decreased by only 15.5%.

[0110] In this reaction, chitosan as a carrier improves the structural stability of boehmite (AlOOH), while the hierarchical porous structure and polyethyleneimine group of the carboxymethylated chitosan-based magnetic adsorbent shorten the adsorption equilibrium time. Through alkalinization treatment, the hydroxyl groups (-OH) on the chitosan molecular chain are deprotonated to form negatively charged oxygen anions (-O -), this oxygen anion has a stronger nucleophilicity and can significantly enhance the activity of subsequent carboxymethylation reactions. After alkalinization, the oxygen anions on the chitosan attack the carbon atoms in the chloroacetic acid molecule, undergoing a nucleophilic substitution reaction and successfully introducing carboxymethyl groups (-CH2COOH) into the chitosan molecular chain. This increases the number of active groups on the chitosan molecule, providing more sites for subsequent reactions and interactions with other substances, and enhancing the reactivity of chitosan.

[0111] Through amino modification, the ethoxy groups of γ-aminopropyltriethoxysilane (KH-550) are hydrolyzed to form silanol groups (-SiOH). These silanol groups then react with hydroxyl groups on the surface of ferroferric oxide nanoparticles, introducing amino groups (-NH2) onto the particle surface. Genipin reacts with amino groups in carboxymethyl chitosan molecules and amino groups on the surface of amino-modified magnetic nanoparticles to form covalent bonds, crosslinking the carboxymethyl chitosan and amino-modified magnetic nanoparticles to form a stable structural framework. Aluminum oxyhydroxide (AlOOH) has a large surface area and abundant surface hydroxyl groups, which can interact with target adsorbents such as fluoride ions through coordination and hydrogen bonding, thereby enhancing the adsorption capacity of the adsorbent for fluoride ions. The addition of polyethyleneimine (PEI) increases the number of amino groups on the adsorbent surface, further enhancing the adsorption capacity for certain anions, such as fluoride, due to the electrostatic attraction of amino groups with anions.

[0112] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention's description and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A fluorine-containing wastewater adsorption treatment device, characterized in that: include: shell; A treatment barrel is rotatably connected to the interior of the shell. The treatment barrel is used to contain fluorine-containing wastewater and to put adsorption material into it to cause adsorption reaction between the fluorine-containing wastewater and the adsorption material. A filter is installed on the treatment barrel. A discharge chute is installed at the bottom of the treatment barrel. A drainage chute and an open chute are provided on the left side of the shell. A partition is fixedly connected to the interior of the shell, and a sliding sleeve is slidably connected to the partition. The bottom of the shell is fixedly connected with a displacement member, the top of the displacement member is fixedly connected with a connecting plate, the connecting plate is fixedly connected with a support sleeve, the support sleeve is used to support the sliding sleeve to achieve blocking of the filter screen, the bottom of the shell is installed with a cylinder, the interior of the cylinder is slidably connected with a sliding block, the bottom of the sliding block is installed with a first elastic member, a connecting rod is installed on the top of the sliding block, the outer surface of the connecting rod is fixedly connected with a connecting block, the top of the connecting rod passes through the connecting plate and is installed with a sealing plate, the sealing plate abuts on the discharge chute for closing the discharge chute; The top of the shell is fixedly connected to a support frame, the bottom of the support frame is fixedly connected to a stirring rod, the stirring rod extends into the processing barrel, the outer surface of the stirring rod is provided with multiple groups of stirring blades, a driving motor is installed on the shell, a transmission assembly is installed between the driving motor and the processing barrel, the driving motor drives the processing barrel to rotate through the transmission assembly to achieve stirring; during stirring, the sliding sleeve covers the outer surface of the filter screen to seal the filter screen.

2. The fluorine-containing wastewater adsorption treatment device according to claim 1, characterized in that: The transmission assembly is two gears meshing with each other, wherein one of the gears is mounted on the output shaft of the driving motor, and the other gear is mounted on the outer surface of the processing barrel.

3. The fluorine-containing wastewater adsorption treatment device according to claim 1, characterized in that: A cavity is provided inside the stirring rod, and a telescopic rod is slidably connected to the interior of one group of stirring blades, and a second elastic member is sleeved on the outer surface of the telescopic rod. One end of the telescopic rod extends to the interior of the cavity, and a scraper is installed at the other end of the telescopic rod. The opposite ends of the two telescopic rods are provided with a first inclined surface, and the top of the sealing plate is fixedly connected to an auxiliary rod, and the auxiliary rod extends to the interior of the cavity. A moving block is installed on the top of the auxiliary rod, and two symmetrical second inclined surfaces are provided at the bottom of the moving block.

4. The fluorine-containing wastewater adsorption treatment device according to claim 3, characterized in that: A water collecting tank and a suction pump are fixedly connected to the right side of the shell. A first connecting pipe is connected between the water collecting tank and the inlet of the suction pump. A second connecting pipe is connected to the outlet of the suction pump. The second connecting pipe passes through the shell and extends to the interior of the shell. A nozzle is installed on the second connecting pipe. A conduit is connected between the drainage trough and the water collecting tank.

5. An adsorption material added to the fluorine-containing wastewater adsorption treatment device according to any one of claims 1 to 4 to achieve the treatment of fluorine-containing wastewater, characterized in that: It is prepared from carboxymethyl chitosan and amino-modified magnetic nanoparticles; The preparation method of the adsorption material comprises the following steps: S1, prepare carboxymethyl chitosan, the steps are as follows: S11, placing chitosan in a three-necked flask, adding an organic solvent to dissolve and stir; S12. Slowly add sodium hydroxide solution using a dropping funnel and stir in a constant temperature water bath to alkalize; S13, dissolving chloroacetic acid in an organic solvent, slowly adding the solution dropwise to the alkalized chitosan solution, heating and continuing stirring; S14, adding glacial acetic acid to adjust the pH, pouring the reaction solution into anhydrous ethanol and stirring; S15, centrifuging the precipitate, washing and drying to obtain carboxymethyl chitosan; S2. Preparation of amino-modified magnetic nanoparticles, the steps are as follows: S21, dissolving substances containing divalent iron ions and trivalent iron ions in deionized water to prepare solutions, and placing the solutions in a three-necked flask; S22, introduce nitrogen to expel all air, and stir vigorously in a constant temperature water bath; S23, rapidly adding ammonia water dropwise using a dropping funnel while continuing to stir to obtain black Fe3O4 nanoparticles; S24, separating the Fe3O4 nanoparticles using a magnet and washing them with deionized water until they are neutral; S25, dispersing the washed Fe3O4 nanoparticles in anhydrous ethanol, and adding a silane coupling agent or an amino acid substance; S26, reflux and stir the reaction in a constant temperature water bath; S27, separating the amino-modified magnetic nanoparticles using a magnet and washing them with anhydrous ethanol; S3, prepare carboxymethylated chitosan-based magnetic adsorbent, the steps are as follows: S31, dissolving the carboxymethyl chitosan prepared above in deionized water to prepare a solution, slowly adding it to the solution prepared by the aluminum source material, and stirring evenly; S32, adding the amino-modified magnetic nanoparticles prepared above, and sonicating to obtain a uniform mixed solution; S33, dissolving genipin in deionized water to prepare a solution, slowly adding it to the above mixed solution, and stirring in a constant temperature water bath; S34, add alkaline solution to adjust the pH of the mixed solution and continue stirring; S35, preparing a solution of polyethyleneimine with a mass fraction of 2%, adding the solution to the mixed solution and stirring; S36, adding 25% by mass of glutaraldehyde to the mixed solution, and stirring at room temperature; S37, repeatedly washing the reaction product with deionized water until the pH of the washing solution reaches neutral, and separating the product with a magnet after each washing; S38. Drying the washed product to a constant weight to obtain a carboxymethylated chitosan-based magnetic adsorbent, i.e., the adsorption material.

6. The adsorption material according to claim 5, characterized in that The organic solvent in S11 is one of isopropanol, methanol, ethanol, and acetone; the concentration of the sodium hydroxide solution in S12 is 40%-60%, the water bath temperature is 30-50°C, and the alkalization time is 1-2h; the organic solvent in S13 is the same as that in S11, the temperature is raised to 60-80°C, and the stirring time is 4-6h; the pH in S14 is neutral; the centrifugal speed in S15 is 4000-6000r / min, the centrifugal time is 10-30min, and washing is performed 3 times with anhydrous ethanol.

7. The adsorption material according to claim 5, characterized in that The divalent iron ion substance in S21 is FeSO4·7H2O, and the trivalent iron ion substance is FeCl3·6H2O; the temperature in S22 is 80-100°C, and the stirring time is 30-60 min; the stirring time in S23 is 30-60 min; the silane coupling agent in S25 is one of γ-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and the amino acid substance is lysine; the temperature in S26 is 60-80°C, and the stirring time is 6-8 h; and the S27 is washed with anhydrous ethanol three times.

8. The adsorption material according to claim 5, characterized in that The aluminum source material in S31 is one of aluminum nitrate nonahydrate and aluminum chloride; the ultrasonic time in S32 is 30-60 min; the constant temperature in S33 is 40-60°C, and the stirring time is 4-6 h; the alkaline solution in S34 is 1 mol / L sodium hydroxide solution, the pH is 8-9, and the stirring time is 6-8 h; the stirring time in S35 is 1-2 h; the stirring time in S36 is 6-8 h; and the drying in vacuum environment in S38 is at a temperature of 60-80°C and a time of 60-90 min.

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