Carbonized sludge-based defluorination filter material, preparation method and application

Abstract

The present invention relates to the field of wastewater treatment technology, specifically disclosing a carbonized sludge-based defluoridation filter material, a preparation method, and applications. The filter material comprises, by weight, 50-70 parts of modified carbonized sludge, 15-35 parts of anionic resin, 5-10 parts of clay, 1-5 parts of a binder, and 1-5 parts of a pore-forming agent. The filter material is used for removing fluoride ions, treating wastewater from semiconductor chip silicon etching, glass etching wastewater, fluoride-containing groundwater, or mine water. The filter material has good resource utilization, low cost, and excellent defluoridation performance.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and in particular to a carbonized sludge-based defluorination filter material, a preparation method and an application thereof. Background Art

[0002] The disposal of excess sludge is a pressing challenge facing wastewater treatment plants. Several disposal options are currently available: The first involves landfill after decontamination, but as the sludge volume increases, landfill becomes increasingly difficult and presents the risk of secondary contamination. The second involves high- and low-temperature composting, but pathogens and heavy metals in the compost pose a risk. The third involves high-temperature incineration, which, while the calorific value of sludge incineration is relatively low and the treatment cost relatively high, is highly safe. Sludge incineration avoids environmental risks while minimizing land use, and the resulting waste residue can be recycled as a building material. Currently, sludge slag is a viable option for sintering mud bricks and expanded clay, but the product performance is difficult to meet building material requirements, and the complex preparation process limits its effectiveness. Therefore, we are exploring new pathways for recycling waste sludge.

[0003] Excessive fluoride content in surface water and groundwater seriously affects human health and causes skeletal fluorosis and dental fluorosis.

[0004] Current fluoride removal technologies include coagulation and sedimentation, chemical precipitation, membrane separation, ion exchange, and adsorption. Adsorption is the most economical and commonly used method. Conventional fluoride adsorbents include activated carbon, zeolite, fly ash, zirconium oxide, carbon bone, and hydroxyapatite. However, most fluoride adsorbents suffer from drawbacks such as poor adsorption capacity, easy hardening, and low efficiency. Consequently, there are reports in the prior art on modifying hydroxyapatite in fluoride adsorbents. Patent document with publication number "CN115193394A" discloses a method for preparing fluorine removal separation column filler from dual solid waste sludge. First, electroplating sludge and tap water flocculation sludge are dried, ground, and sieved at a constant temperature, and calcined at 400-800°C for 4-8 hours to obtain pretreated electroplating sludge and tap water flocculation sludge; then, nickel in the pretreated electroplating sludge and aluminum in the tap water flocculation sludge are mixed at a molar ratio of 3:1-1:3, and the mixture is added to a 0.1-0.35 mol / L crystal structure directing agent solution. The mixture is hydrothermally reacted at 120-220°C for 10-35 hours to obtain a sludge-based composite material. Finally, the temperature is programmed to 200-350°C for sintering for 4-8 hours, and then the temperature is increased to 450-550°C and maintained for 2-8 hours to obtain a fluorine removal separation column filler. The defluorination separation column filler is used to remove excess fluoride ions in wastewater to solve the problems of high energy consumption and environmental pollution, and is suitable for industrial applications. However, this method requires secondary calcination, which is a complex process and increases the cost of preparation. In addition, the adsorption capacity of the obtained fluorine removal material is not high enough. Summary of the Invention

[0005] In order to solve the above-mentioned technical problems existing in the existing removal of fluoride content in water, the present invention provides a carbonized sludge-based defluoridation filter material, a preparation method and an application thereof, which has the characteristics of good resource utilization effect, low cost and good defluoridation function.

[0006] The first technical solution of the present invention: Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0007] 50-70 parts of modified carbonized sludge, 15-35 parts of anion resin, 5-10 parts of clay, 1-5 parts of binder, and 1-5 parts of pore-forming agent. The present invention prepares a carbonized sludge-based fluoride removal filter material by selecting modified carbonized sludge, anion resin, clay, binder and pore-forming agent in appropriate proportions and processing and mixing them. The modified carbonized sludge is prepared by modifying carbonized sludge as a base material. In addition to calcium salt, the carbonized sludge is also rich in iron and aluminum salts, which has the components of concrete and has the stability of building materials. Moreover, the content of carbonized sludge components in the entire filter material is also very high, and the mass ratio reaches more than half, thereby realizing a good resource application of carbonized sludge. After the carbonized sludge is modified, hydroxyapatite will be generated in situ on its outer surface. Hydroxyapatite has a good function of adsorbing fluoride ions and replacing hydroxyl groups. The content of the modified carbonized sludge component in the entire filter material is also the highest, and the content of hydroxyapatite will also be very high, which will enable the entire filter material to have a high adsorption capacity for fluoride ions in wastewater. The aluminum ions in the carbonized sludge can react with fluoride ions to generate AlF6 3- , which makes the filter material have an enhanced adsorption capacity for fluoride ions in wastewater; the anion resin also has a fluoride ion exchange function, and the addition of the anion resin can also greatly enhance the adsorption and removal function of the entire filter material for fluoride ions in wastewater; the addition of an appropriate amount of clay can enhance the hardness and stability of the entire filter material, play a supporting role, and effectively slow down the collapse problem of the filter material when it is immersed in water for a long time; the addition of an appropriate amount of binder can uniformly and stably form the filter material as a whole after mixing the various components, so as to facilitate direct use in wastewater for fluoride removal; the addition of an appropriate amount of pore-forming agent can make the entire filter material have a suitable porosity, increase the specific surface area of wastewater fluoride removal, and improve fluoride removal efficiency; by using the filter material of the present invention, the removal rate of fluoride ions in wastewater can reach more than 80%, and it has high adsorption fluoride removal performance; the fluoride removal function of the present invention is mainly achieved through the adsorption of hydroxyapatite, the flocculation of iron salts and aluminum salts and the ion exchange of anion resin, so it has a very high wastewater fluoride removal efficiency.

[0008] As preferred, the following components are included by weight:

[0009] 55-65 parts of modified carbonized sludge, 20-30 parts of anion resin, 6-9 parts of clay, 1.5-4.5 parts of binder, and 1.5-4.5 parts of pore-forming agent.

[0010] As preferred, the following components are included by weight:

[0011] 58-62 parts of modified carbonized sludge, 22-28 parts of anion resin, 6.5-8.5 parts of clay, 2-4 parts of binder, and 2-4 parts of pore-forming agent.

[0012] As preferred, the following components are included by weight:

[0013] 60 parts of modified carbonized sludge, 25 parts of anion resin, 7-8 parts of clay, 3 parts of binder, and 3 parts of pore-forming agent.

[0014] As preferred, the following components are included by weight:

[0015] 60 parts of modified carbonized sludge, 25 parts of anion resin, 7.5 parts of clay, 3 parts of binder, and 3 parts of pore-forming agent.

[0016] The second technical solution of the present invention: a method for preparing a carbonized sludge-based defluorination filter material, comprising the following steps:

[0017] (S01) Weighing an appropriate amount of carbonized sludge, soaking it in dilute hydrochloric acid, washing it with anhydrous ethanol, and then drying it;

[0018] (S02) adding ammonia water to the carbonized sludge dried in step (S01), stirring and mixing, and washing with anhydrous ethanol and then drying;

[0019] (S03) taking an appropriate amount of the carbonized sludge dried in step (S02) and an appropriate amount of calcium hydroxide and grinding them together in a ball mill;

[0020] (S04) preparing a phosphoric acid solution, and placing the ground mixture from step (S03) in the phosphoric acid solution for soaking and reaction;

[0021] (S05) stirring and vibrating the reactants in step (S04) until they are in a paste-like state, drying and dehydrating the mixture, and grinding the mixture into a powder in a ball mill;

[0022] (S06) taking appropriate amounts of anionic resin, clay, binder and pore-forming agent, adding water and stirring together with the powder in step (S05);

[0023] (S07) granulating the stirred mixture in step (S06) and placing the granules into a calcination container for calcination;

[0024] (S08) After the calcination in step (S07) is completed and cooled, a carbonized sludge-based defluorination filter material is obtained.

[0025] The present invention prepares hydroxyapatite in situ generated on the outer surface of modified carbonized sludge, and then mixes it with anion resin in a certain proportion. The anion resin has a fluoride ion exchange function, and the hydroxyapatite has the function of adsorbing fluoride ions and replacing hydroxyl groups. In addition to calcium salts, the carbonized sludge is also rich in iron and aluminum salts, which have the function of coagulation. Clay, binder and pore-forming agent are added, and the mixture is uniformly mixed in a mixer and then solidified into a shape. The filter material finally prepared has stable performance and high fluoride removal efficiency, solves the problems of low fluoride removal and difficult recovery and separation of powder materials, and is suitable for fluoride removal in groundwater and various fluoride-containing industrial wastewater. The present invention adopts high oxygen isolation conditions. The warm calcination method can avoid the risk of environmental damage caused by landfill or ordinary incineration, and does not occupy land resources. The waste residue produced can also be used as a building material for resource utilization. In addition to calcium salts, the waste residue is also rich in iron and aluminum salts, and the building materials made from it can also meet performance requirements; the entire preparation process adopts a process of cooling and molding after one calcination. The entire process steps are simple and reduce manufacturing costs; the use of dilute hydrochloric acid to soak the carbonized sludge can effectively remove useless carbonate ions, and the cleaning standard is to remove the carbonate content in the carbonized sludge; further treatment with ammonia water, The purpose is to remove the weak acid impurities and make the surface of the carbonized sludge hydroxylated, which is convenient for further modification. The use of anhydrous ethanol for cleaning can effectively remove impurities. It is necessary to ensure that the cleaning is repeated several times through anhydrous ethanol to remove impurities as completely as possible. The addition of calcium hydroxide is to increase the calcium content in the carbonized sludge, so as to make full preparations for the subsequent modification to make hydroxyapatite adsorption material, and make full use of the calcium in the carbonized sludge to generate the effective ingredient hydroxyapatite. The immersion reaction after the phosphoric acid solution is prepared is to make the hydroxyapatite we need well. The present invention is to process the residual sludge in the wastewater to prepare a defluorination filter material. The defluorination filter material is based on the carbonized sludge, generates hydroxyapatite in situ, and is mixed with anion resin, clay, binder and pore-forming agent. The mass proportion of the carbonized sludge is nearly half, realizing the resource application of the carbonized sludge. The whole preparation method of the present invention is to first modify the carbonized sludge to become hydroxyapatite, and then mix it with anion resin, clay, binder, pore-forming agent and appropriate amount of water, and then form it through granulation and calcination. The whole preparation process is simple and the cost is low.

[0026] Preferably, the mass concentration of the dilute hydrochloric acid in step (S01) is 5% to 15%. More preferably, the mass concentration of the dilute hydrochloric acid in step (S01) is 8% to 12%. More preferably, the mass concentration of the dilute hydrochloric acid in step (S01) is 10%. Dilute hydrochloric acid of a defined concentration can more effectively remove useless carbonate ions.

[0027] Preferably, the soaking time in step (S01) is 0.5 h to 1.5 h. More preferably, the soaking time in step (S01) is 0.8 h to 1.2 h. More preferably, the soaking time in step (S01) is 1 h. The soaking time is limited to ensure that useless carbonate ions are effectively removed while taking into account timeliness.

[0028] Preferably, the drying temperature in the step (S01) is 85°C to 200°C. More preferably, the drying temperature in the step (S01) is 90°C to 180°C. More preferably, the drying temperature in the step (S01) is 100°C to 160°C. More preferably, the drying temperature in the step (S01) is 120°C to 140°C. More preferably, the drying temperature in the step (S01) is 130°C. The drying temperature is limited here to effectively dry the substance as quickly as possible without affecting the stability of the substance therein due to excessively high temperature.

[0029] Preferably, the mass concentration of the ammonia water in step (S02) is 10% to 30%. More preferably, the mass concentration of the ammonia water in step (S02) is 12% to 28%. More preferably, the mass concentration of the ammonia water in step (S02) is 15% to 25%. More preferably, the mass concentration of the ammonia water in step (S02) is 18% to 22%. More preferably, the mass concentration of the ammonia water in step (S02) is 20%. The limitation on the mass concentration of the ammonia water is to ensure effective removal of weakly acidic impurities therein while also enabling better hydroxylation of the carbonized sludge surface.

[0030] Preferably, the mixing time in step (S02) is 0.5 h to 1.5 h. More preferably, the mixing time in step (S02) is 0.8 h to 1.2 h. More preferably, the mixing time in step (S02) is 1 h. The mixing time is limited to ensure effective removal of weakly acidic impurities and better hydroxylation of the carbonized sludge surface while taking into account timeliness.

[0031] Preferably, the drying temperature in the step (S02) is 85°C to 200°C. More preferably, the drying temperature in the step (S02) is 90°C to 180°C. More preferably, the drying temperature in the step (S02) is 100°C to 160°C. More preferably, the drying temperature in the step (S02) is 120°C to 140°C. More preferably, the drying temperature in the step (S02) is 130°C. The drying temperature is limited here to effectively dry the substance as quickly as possible without affecting the stability of the substance therein due to excessively high temperature.

[0032] Preferably, the mass ratio of carbonized sludge to calcium hydroxide in step (S03) is 1:1 to 3:1. More preferably, the mass ratio of carbonized sludge to calcium hydroxide in step (S03) is 1.5:1 to 2.5:1. More preferably, the mass ratio of carbonized sludge to calcium hydroxide in step (S03) is 2:1. The limitation on the mass ratio of carbonized sludge to calcium hydroxide is to fully utilize the calcium in the carbonized sludge to generate the effective ingredient hydroxyapatite while making up for the insufficient calcium content, thereby fully preparing for the subsequent further modification to produce hydroxyapatite adsorption material.

[0033] Preferably, the mass concentration of the phosphoric acid solution in step (S04) is 45% to 55%. More preferably, the mass concentration of the phosphoric acid solution in step (S04) is 48% to 52%. More preferably, the mass concentration of the phosphoric acid solution in step (S04) is 50%. Limiting the concentration of the phosphoric acid solution allows for more efficient modification of the carbonized sludge to produce the desired hydroxyapatite.

[0034] Preferably, the phosphoric acid solution in step (S04) is prepared such that the ratio of phosphate ion concentration to calcium ion concentration is 0.5 to 0.8. More preferably, the phosphoric acid solution in step (S04) is prepared such that the ratio of phosphate ion concentration to calcium ion concentration is 0.6 to 0.7. The limitation on the ratio of phosphate ion concentration to calcium ion concentration is intended to ensure a more complete reaction of phosphate ions and calcium ions to form hydroxyapatite, thereby preventing excessive ion waste.

[0035] Preferably, the calcination in step (S07) is carried out under oxygen-blocking conditions. Calcination under oxygen-blocking conditions can effectively prevent oxidation reactions produced under high temperature conditions, avoid the generation of additional impurities, and ensure the quality of the final filter material.

[0036] Preferably, the calcination temperature in step (S07) is 300°C to 350°C. More preferably, the calcination temperature in step (S07) is 310°C to 340°C. More preferably, the calcination temperature in step (S07) is 320°C to 330°C. The calcination temperature is limited here to ensure that the mixed material can be well converted into a high-quality defluorination filter material.

[0037] Preferably, the calcination time in step (S07) is 1 to 2 hours. More preferably, the calcination time in step (S07) is 1.2 to 1.8 hours. More preferably, the calcination time in step (S07) is 1.5 hours. The calcination time is limited here to ensure that the finished fluorine removal filter material is well formed while taking into account the timeliness.

[0038] Preferably, the shape of the particles after granulation in step (S07) is spherical. The purpose of granulation is to ensure that the particles can be well combined after calcination, so that the final filter material has good bulk density and porosity, thereby having better fluorine removal effect.

[0039] Preferably, the particle size of the particles after granulation in the step (S07) is 0.3 cm to 0.8 cm. More preferably, the particle size of the particles after granulation in the step (S07) is 0.4 cm to 0.7 cm. More preferably, the particle size of the particles after granulation in the step (S07) is 0.5 cm to 0.6 cm. The limitation on the particle size after granulation here is also to ensure that the particles can be well combined after calcination, so that the final filter material has a more uniform texture, good bulk density and porosity, and thus has a better defluorination effect.

[0040] Preferably, the cooling in step (S08) is natural cooling to room temperature. Natural cooling can ensure that the connections between the particles in the final filter material and the internal molecules of the particles form more stable and natural connections, thereby better ensuring the quality and stability of the filter material.

[0041] Preferably, the bulk density of the carbonized sludge-based defluorination filter material in step (S08) is 0.2 g / cm 3 ~0.8g / cm 3 More preferably, the bulk density of the carbonized sludge-based defluorination filter material in step (S08) is 0.3 g / cm 3 ~0.7g / cm 3 More preferably, the bulk density of the carbonized sludge-based defluorination filter material in step (S08) is 0.4 g / cm 3 ~0.6g / cm 3 More preferably, the bulk density of the carbonized sludge-based defluorination filter material in step (S08) is 0.5 g / cm 3 . This makes the filter material have a better adsorption effect on fluoride ions in wastewater.

[0042] Preferably, the porosity of the carbonized sludge-based defluoridation filter material in step (S08) is 30% to 50%. More preferably, the porosity of the carbonized sludge-based defluoridation filter material in step (S08) is 35% to 45%. More preferably, the porosity of the carbonized sludge-based defluoridation filter material in step (S08) is 40%. This provides the filter material with a suitable specific surface area, thereby achieving a better adsorption effect on fluoride ions in wastewater.

[0043] Preferably, the anion resin is a strongly basic anion exchange resin or a weakly basic anion exchange resin. More preferably, the anion resin is a CH-87 anion exchange resin. The type of anion resin can be flexibly selected as needed, as long as it is alkaline.

[0044] Preferably, the clay is at least one of kaolin, bentonite or montmorillonite. The type of clay can be flexibly selected according to needs and has a certain degree of selectivity.

[0045] Preferably, the bentonite is sodium bentonite with a mesh size of 200-400. More preferably, the bentonite is sodium bentonite with a mesh size of 250-350. More preferably, the bentonite is sodium bentonite with a mesh size of 300. This specific type of bentonite can better enhance the hardness and stability of the entire filter material.

[0046] Preferably, the binder is carboxymethyl cellulose, polyvinyl alcohol or hydroxypropyl methyl cellulose. The type of binder can be flexibly selected according to needs and has a certain degree of selectivity.

[0047] Preferably, the pore-forming agent is perlite, diatomaceous earth, rice husk, zeolite or sodium bicarbonate. The type of pore-forming agent can be flexibly selected according to needs and has a certain selectivity.

[0048] Preferably, the ball mill includes a processing base, support plates are provided on both sides of the processing base, and a ball mill cover is provided between the two support plates; a drive shaft is connected to the support plate on one side through a reduction transmission assembly, and the drive shaft is fixedly connected to a ball mill chamber, and the ball mill chamber is densely arranged with grinding balls, a material extraction port is provided on one side of the ball mill chamber, and an isolation ring and a switching ring are connected to the outer wall of the ball mill chamber through a rotating connector, and a plurality of ball outlets are provided on the top of the ball mill cover, and a magnetic storage member is provided on the ball mill cover at the ball outlet. The present invention can flexibly adjust the number of grinding balls in the ball mill in a controllable manner, so as to achieve the purpose of reasonably adding grinding balls according to the change in precision during the grinding process, and can significantly improve the grinding process efficiency compared with the existing technology; the present invention uses magnetic force to adsorb the grinding balls, and uses the driving magnetic ball to drive the grinding balls to rotate, so as to scrape the powder on the grinding balls, facilitate the full collection of the grinding powder, and facilitate the cleaning and collection of the grinding balls.

[0049] Preferably, the isolation ring is provided with a cleaning ball port corresponding to the ball outlet, the switching ring is provided with a ball outlet channel corresponding to the ball outlet, the switching ring is provided with a linkage ball port corresponding to the cleaning ball port, a driving magnetic ball is provided in the linkage ball port, a horizontal adjustment shaft is connected to the switching ring through an elastic linkage component, the horizontal adjustment shaft is fixedly connected to multiple driving magnetic balls, and control rotating parts are provided at the ends of the switching ring and the isolation ring.

[0050] Preferably, the isolation ring is sleeved on the outer wall of the ball mill chamber, the switching ring is sleeved on the outer wall of the isolation ring, the ball mill cover is sleeved on the outer wall of the switching ring, and the inner diameters of the ball outlet, cleaning ball outlet and ball outlet channel are consistent.

[0051] Preferably, the reduction transmission assembly includes a reducer arranged on a support plate, an output end of the reducer is connected to a drive shaft, a drive motor is fixedly provided on the reducer, and an output end of the drive motor is connected to an input end of the reducer.

[0052] Preferably, a support end cap is fixedly connected to the support plate located on one side of the feed outlet. A discharge port is formed on the support plate and extends through the side wall of the support end cap. A sealing plug is provided within the discharge port, and the discharge port is sized to correspond to the feed outlet. The provision of the sealing plug enables the discharge port to be closed. In this case, the feed outlet is sealed at its location due to the obstruction of the support end cap and the side wall of the sealing plug.

[0053] Preferably, the rotating connecting member includes an inner rotating ring connected to the support end cover through a first bearing, the inner rotating ring is fixedly arranged at the end of the ball mill chamber, the inner rotating ring is rotatably connected to the end of the isolation ring through a second bearing, the isolation ring is rotatably connected to the switching ring through a third bearing, and the switching ring is rotatably connected to the inner wall of the ball mill cover through a fourth bearing.

[0054] Preferably, the magnetic storage member includes a storage arc plate and a magnetic arc plate connected by a fastening adjustment member, a grid plate for storing grinding balls is provided at the bottom of the storage arc plate, and a magnetic attraction plate is provided above the magnetic arc plate.

[0055] Preferably, the tightening adjustment member includes a fan-shaped support member connected to the storage arc plate and the magnetic arc plate, respectively. The fan-shaped support member has an arc-shaped opening, and a tightening knob column is threadedly connected to the support plate and the storage arc plate. The tightening knob column extends outward through the arc-shaped opening. This allows the storage arc plate and the magnetic arc plate to rotate, and the position between adjacent plates can be changed during the rotation, thereby achieving flexible adjustment of the storage arc plate and the magnetic arc plate according to the magnetic force requirements for placement and storage, and the adjustment process only requires loosening the tightening knob column.

[0056] Preferably, the elastic linkage component includes a vertical elastic port opened in the switching ring, the vertical elastic port is connected to an elastic block through a resistance spring, the elastic block is rotatably connected to the horizontal adjustment shaft, and the switching ring located at the linkage ball port is provided with an adjustment through port for the horizontal adjustment shaft to move.

[0057] Preferably, one end of the horizontal adjustment shaft extends outward through the side wall of the switching ring and is fixedly connected to a linkage gear, and a fixed gear ring compatible with the linkage gear is fixedly connected to the support plate. The driving magnetic ball in the linkage ball port partially moves into the cleaning ball port under the action of the elastic force applied to the elastic block by the resistance spring. When the driving magnetic ball is not in the linkage ball port, it retracts into the linkage ball port under the resistance force of the inner wall of the isolation ring, and in this process, the fixed gear ring and the linkage gear are engaged and disengaged.

[0058] Preferably, the control rotary member includes an external threaded layer arranged on the outer side wall of the drive shaft, the external threaded layer is threadedly connected to an adjusting nut ring, a knob ring for rotating is provided on the adjusting nut ring, the outer side wall of the adjusting nut ring is connected to a sleeve ring through a keyway connector, and the outer side walls of the two sleeve rings are respectively connected to the switching ring and the isolation ring through a plurality of connecting rods.

[0059] Preferably, the keyway connector includes a plurality of torque key strips evenly distributed on the outer side wall of the adjusting nut ring, and the inner side wall of the sleeve ring is provided with a keyway adapted to the torque key strips.

[0060] The third technical solution of the present invention: application of carbonized sludge-based defluorination filter material in the removal of fluoride ions, treatment of semiconductor chip silicon etching wastewater, treatment of glass etching wastewater, treatment of fluorine-containing groundwater or treatment of mine water.

[0061] The present invention has the following beneficial effects:

[0062] (1) Carbonized sludge-based fluoride removal filter material is prepared by selecting and mixing modified carbonized sludge, anion resin, clay, binder and pore-forming agent in appropriate proportions. The modified carbonized sludge is prepared by modifying carbonized sludge as the base material. In addition to calcium salt, the carbonized sludge is also rich in iron and aluminum salts, which has the components of concrete and has the stability of building materials. In addition, the content of carbonized sludge components in the entire filter material is also very high, and the mass ratio reaches more than half, which realizes a good resource application of carbonized sludge. After the carbonized sludge is modified, hydroxyapatite will be generated in situ on its outer surface. Hydroxyapatite has a good adsorption effect on fluoride ions and also has the effect of replacing hydroxyl groups. The content of modified carbonized sludge components in the entire filter material is also the highest, and the content of hydroxyapatite will also be very high, which will enable the entire filter material to have a high adsorption capacity for fluoride ions in wastewater. The aluminum ions in the carbonized sludge can react with fluoride ions to generate AlF6 3-, which makes the filter material have an enhanced adsorption capacity for fluoride ions in wastewater; the anion resin also has a fluoride ion exchange function, and the addition of the anion resin can also greatly enhance the adsorption and removal function of the entire filter material for fluoride ions in wastewater; the addition of an appropriate amount of clay can enhance the hardness and stability of the entire filter material, play a supporting role, and effectively slow down the collapse problem of the filter material when it is immersed in water for a long time; the addition of an appropriate amount of binder can uniformly and stably form the filter material as a whole after mixing the various components, so as to facilitate direct use in the removal of fluoride in wastewater; the addition of an appropriate amount of pore-forming agent can make the entire filter material have a suitable porosity, increase the specific surface area of wastewater fluoride removal, and improve the fluoride removal efficiency; by using the filter material of the present invention, the removal rate of fluoride ions in wastewater can reach more than 80%, and it has high adsorption and fluoride removal performance;

[0063] (2) The fluoride removal function is mainly achieved through adsorption on hydroxyapatite, flocculation of iron salts and aluminum salts, and ion exchange of anion resins, which has a high efficiency in removing fluoride from wastewater;

[0064] (3) The hydroxyapatite generated in situ on the outer surface of the modified carbonized sludge is then mixed with an anion resin in a certain proportion. The anion resin has a fluoride ion exchange function, and the hydroxyapatite has the function of adsorbing fluoride ions and replacing hydroxyl groups. In addition to calcium salts, the carbonized sludge is also rich in iron and aluminum salts, which have a coagulation function. Clay, binder and pore-forming agent are added to the sludge, and the mixture is uniformly mixed in a mixer and then solidified into a shape. The final filter material has stable performance and high fluoride removal efficiency, which solves the problems of low fluoride removal and difficult recovery and separation of powder materials. It is suitable for fluoride removal in groundwater and various fluoride-containing industrial wastewaters.

[0065] (4) The high-temperature calcination method under oxygen-isolation conditions can avoid the risk of environmental damage caused by landfill or ordinary incineration, and does not occupy land resources. The waste residue produced can also be used as a building material for resource utilization. In addition to calcium salts, the waste residue is also rich in iron and aluminum salts, and the building materials made can also meet performance requirements; the entire preparation process adopts a process of cooling and molding after calcination once, the entire process steps are simple, and the manufacturing cost is reduced; the carbonized sludge is soaked in dilute hydrochloric acid, which can effectively remove useless carbonate ions therein, and the cleaning standard is to remove the carbonate content in the carbonized sludge; further treatment with ammonia water, The purpose is to remove weak acidic impurities and enable the surface of the carbonized sludge to be hydroxylated, which is convenient for further modification. The use of anhydrous ethanol for cleaning can effectively remove impurities. It is necessary to ensure that the cleaning is repeated several times through anhydrous ethanol to remove impurities as completely as possible. The addition of calcium hydroxide is to increase the calcium content in the carbonized sludge, making full preparations for the subsequent modification to produce hydroxyapatite adsorption material, and making full use of the calcium in the carbonized sludge to generate the effective ingredient hydroxyapatite. The immersion reaction after the phosphoric acid solution is prepared is to produce the hydroxyapatite we need, that is, the modified carbonized sludge.

[0066] (5) The residual sludge in the wastewater is treated to make a defluorination filter material. The defluorination filter material is based on carbonized sludge, and hydroxyapatite is generated in situ. It is mixed with anion resin, clay, binder and pore-forming agent, and the mass proportion of carbonized sludge reaches nearly half, realizing the resource application of carbonized sludge.

[0067] (6) The entire preparation method is to first modify the carbonized sludge into hydroxyapatite, then mix it with anionic resin, clay, binder, pore-forming agent and appropriate amount of water, and then form it after granulation and calcination. The entire preparation process is simple and low in cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 It is a structural schematic diagram of the ball mill in the present invention;

[0069] Figure 2 1. It is the internal structure diagram of the ball mill in the present invention;

[0070] Figure 3 for Figure 2 A magnified view of point A in the figure;

[0071] Figure 4 This is a first structural schematic diagram of the end face of the ball mill in the present invention;

[0072] Figure 5 This is a second structural schematic diagram of the end face of the ball mill in the present invention;

[0073] Figure 6 for Figure 5 Enlarged view of point B in .

[0074] The markings in the attached figure are: 1-processing base; 2-support plate; 3-ball mill cover; 4-drive shaft; 5-ball mill chamber; 6-grinding balls; 7-feeding port; 8-isolating ring; 9-switching ring; 10-ball outlet; 11-cleaning ball outlet; 12-ball outlet channel; 13-linked ball outlet; 14-driving magnetic ball; 15-horizontal adjustment shaft; 16-speed reducer; 17-drive motor; 18-support end cover; 19-sealing Plug; 20-inner rotating ring; 21-storage arc plate; 22-magnetic arc plate; 23-grid plate; 24-magnetic plate; 25-fan-shaped support; 26-arc-shaped opening; 27-fastening knob column; 28-elastic block; 29-adjustment through-opening; 30-linkage gear; 31-fixed gear ring; 32-adjusting nut ring; 33-sleeve ring; 34-connecting support rod; 35-knob ring; 36-keyway connector. DETAILED DESCRIPTION

[0075] The present invention will be further described below with reference to the accompanying drawings and examples, but they are not intended to limit the present invention.

[0076] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0077] 50-70 parts of modified carbonized sludge, 15-35 parts of anion resin, 5-10 parts of clay, 1-5 parts of binder, and 1-5 parts of pore-forming agent.

[0078] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0079] 55-65 parts of modified carbonized sludge, 20-30 parts of anion resin, 6-9 parts of clay, 1.5-4.5 parts of binder, and 1.5-4.5 parts of pore-forming agent.

[0080] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0081] 58-62 parts of modified carbonized sludge, 22-28 parts of anion resin, 6.5-8.5 parts of clay, 2-4 parts of binder, and 2-4 parts of pore-forming agent.

[0082] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0083] 60 parts of modified carbonized sludge, 25 parts of anion resin, 7-8 parts of clay, 3 parts of binder, and 3 parts of pore-forming agent.

[0084] The preparation method of carbonized sludge-based defluorination filter material comprises the following steps:

[0085] (S01) Weighing an appropriate amount of carbonized sludge, soaking it in dilute hydrochloric acid, washing it with anhydrous ethanol, and then drying it; the mass concentration of the dilute hydrochloric acid in step (S01) is 5% to 15%; the soaking time in step (S01) is 0.5h to 1.5h; the drying temperature in step (S01) is 85°C to 200°C;

[0086] (S02) adding ammonia water to the carbonized sludge dried in step (S01), stirring and mixing, and washing with anhydrous ethanol and then drying; the drying temperature in step (S02) is 85° C. to 200° C.;

[0087] (S03) taking an appropriate amount of the carbonized sludge dried in step (S02) and an appropriate amount of calcium hydroxide and grinding them together in a ball mill; the mass ratio of the carbonized sludge to the calcium hydroxide in step (S03) is 1:1 to 3:1; the mass ratio of the carbonized sludge to the calcium hydroxide in step (S03) is 1.5:1 to 2.5:1; the mass ratio of the carbonized sludge to the calcium hydroxide in step (S03) is 2:1;

[0088] (S04) preparing a phosphoric acid solution, and placing the ground mixture in step (S03) in the phosphoric acid solution for soaking and reaction; the mass concentration of the phosphoric acid solution in step (S04) is 45% to 55%; the preparation requirement of the phosphoric acid solution in step (S04) is that the concentration ratio of phosphate ion concentration to calcium ion concentration is 0.5 to 0.8;

[0089] (S05) stirring and vibrating the reactants in step (S04) until they are in a paste-like state, drying and dehydrating the mixture, and grinding the mixture into a powder in a ball mill;

[0090] (S06) taking appropriate amounts of anion resin, clay, binder and pore-forming agent, adding water and stirring together with the powder in step (S05); the anion resin is selected from a strong alkaline anion exchange resin or a weak alkaline anion exchange resin; the anion resin is selected from CH-87 anion exchange resin; the clay is selected from at least one of kaolin, bentonite or montmorillonite; the bentonite is sodium bentonite with a mesh size of 200 to 400; the binder is selected from carboxymethyl cellulose, polyvinyl alcohol or hydroxypropyl methylcellulose;

[0091] (S07) granulating the stirred mixture in step (S06) into a granulated shape, and placing the granulated particles into a calcination container for calcination; the calcination in step (S07) is carried out under oxygen-blocking conditions; the calcination temperature in step (S07) is 300° C. to 350° C.; the calcination time in step (S07) is 1 hour to 2 hours; the shape of the particles granulated in step (S07) is spherical; the particle size of the particles granulated in step (S07) is 0.3 cm to 0.8 cm;

[0092] (S08) After the calcination in step (S07) is completed and cooled, the carbonized sludge-based defluorination filter material is obtained; the cooling in step (S08) is naturally cooled to room temperature; the bulk density of the carbonized sludge-based defluorination filter material in step (S08) is 0.2 g / cm 3 ~0.8g / cm 3 ; The porosity of the carbonized sludge-based defluorination filter material in the step (S08) is 30% to 50%.

[0093] like Figure 1 and Figure 2 The ball mill shown in the figure comprises a processing base 1, a support plate 2 is provided on both sides of the processing base 1, a ball mill cover 3 is provided between the two support plates 2; a support plate 2 on one side is connected to the support plate 2 through a reduction transmission component. Figure 4 The drive shaft 4 shown in the figure is fixedly connected to a ball mill chamber 5, in which there are densely arranged balls such as Figure 5 The grinding balls 6 shown in the figure have a material taking port 7 extending through the side wall of the ball mill chamber 5. The outer wall of the ball mill chamber 5 is connected to an isolation ring 8 and a switching ring 9 via a rotating connector. The top of the ball mill housing 3 is provided with multiple ball outlets 10. The ball mill housing 3 at the ball outlets 10 is provided with a magnetic storage component. The isolation ring 8 is provided with a cleaning ball port 11 corresponding to the ball outlet 10. The switching ring 9 is provided with a ball outlet channel 12 corresponding to the ball outlet 10. The switching ring 9 is provided with a linkage ball port 13 corresponding to the cleaning ball port 11. A driving magnetic ball 14 is provided in the linkage ball port 13. The switching ring 9 is connected to the magnetic storage component via an elastic linkage component. Figure 6 The horizontal adjustment shaft 15 shown is fixedly connected to multiple driving magnetic balls 14, and the ends of the switching ring 9 and the isolation ring 8 are both provided with control rotating parts.

[0094] The isolation ring 8 is mounted on the outer wall of the ball mill chamber 5, the switching ring 9 is mounted on the outer wall of the isolation ring 8, and the ball mill cover 3 is mounted on the outer wall of the switching ring 9. The inner diameters of the ball outlet 10, the cleaning ball outlet 11, and the ball outlet channel 12 are all the same size. The reduction transmission assembly includes a reducer 16 mounted on the support plate 2. The output end of the reducer 16 is connected to the drive shaft 4. A drive motor 17 is fixedly mounted on the reducer 16, and the output end of the drive motor 17 is connected to the input end of the reducer 16. A support end cap 18 is fixedly connected to the support plate 2 located on one side of the material discharging port 7. A material discharging port is formed on the support plate 2 and passes through the side wall of the support end cap 18. A sealing plug 19 is provided in the material discharging port. The material discharging port corresponds in size to the material discharging port 7.

[0095] The rotating connection member includes an inner rotating ring 20 connected to the support end cap 18 via a first bearing. The inner rotating ring 20 is fixedly mounted at the end of the ball mill chamber 5. The inner rotating ring 20 is rotatably connected to the end of the isolation ring 8 via a second bearing. The isolation ring 8 is rotatably connected to the switching ring 9 via a third bearing. The switching ring 9 is rotatably connected to the inner sidewall of the ball mill housing 3 via a fourth bearing. The magnetic storage member includes a storage arc plate 21 and a magnetic arc plate 22 connected by a fastening adjustment member. A grid plate 23 for storing the grinding balls 6 is provided at the bottom of the storage arc plate 21, and a magnetic attraction plate 24 is provided above the magnetic arc plate 22.

[0096] The fastening adjustment member includes a fan-shaped support member 25 connected to the storage arc plate 21 and the magnetic arc plate 22 respectively, and an arc-shaped opening 26 is provided on the fan-shaped support member 25. A fastening knob column 27 is threadedly connected to the support plate 2 and the storage arc plate 21, and the fastening knob column 27 extends outward through the arc-shaped opening 26. The elastic linkage component includes a vertical elastic opening provided in the switching ring 9, and an elastic block 28 is connected to the inside of the vertical elastic opening through a resistance spring. The elastic block 28 is rotatably connected to the horizontal adjustment shaft 15, and an adjustment through-opening 29 for the horizontal adjustment shaft 15 to move is provided on the switching ring 9 located at the linkage ball opening 13. One end of the horizontal adjustment shaft 15 extends outward through the side wall of the switching ring 9 and is fixedly connected as shown. Figure 3 As shown in the linkage gear 30 , a fixed gear ring 31 adapted to the linkage gear 30 is fixedly connected to the support plate 2 .

[0097] The control rotary element includes an externally threaded layer disposed on the outer wall of the drive shaft 4. The externally threaded layer is threadedly connected to an adjusting nut ring 32. The adjusting nut ring 32 is provided with a rotating knob ring 35. The outer wall of the adjusting nut ring 32 is connected to a sleeve ring 33 via a keyway connector 36. The outer walls of the two sleeve rings 33 are respectively connected to the switching ring 9 and the isolation ring 8 via multiple connecting rods 34. The keyway connector 36 includes multiple torque key strips evenly distributed on the outer wall of the adjusting nut ring 32. The inner wall of the sleeve ring 33 is provided with a keyway that matches the torque key strips.

[0098] The application of carbonized sludge-based fluoride removal filter media in the removal of fluoride ions, semiconductor chip silicon etching wastewater treatment, glass etching wastewater treatment, fluoride-containing groundwater treatment or mine water treatment.

[0099] Example 1:

[0100] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0101] 50 parts of modified carbonized sludge, 15 parts of anion resin, 5 parts of clay, 1 part of binder, and 1 part of pore-forming agent.

[0102] Example 2:

[0103] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0104] 70 parts of modified carbonized sludge, 35 parts of anion resin, 10 parts of clay, 5 parts of binder, and 5 parts of pore-forming agent.

[0105] Example 3:

[0106] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0107] 55 parts of modified carbonized sludge, 20 parts of anion resin, 6 parts of clay, 1.5 parts of binder, and 1.5 parts of pore-forming agent.

[0108] Example 4:

[0109] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0110] 65 parts of modified carbonized sludge, 30 parts of anion resin, 9 parts of clay, 4.5 parts of binder, and 4.5 parts of pore-forming agent.

[0111] Example 5:

[0112] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0113] 58 parts of modified carbonized sludge, 22 parts of anion resin, 6.5 parts of clay, 2 parts of binder, and 2 parts of pore-forming agent.

[0114] Example 6:

[0115] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0116] 62 parts of modified carbonized sludge, 28 parts of anion resin, 8.5 parts of clay, 4 parts of binder, and 4 parts of pore-forming agent.

[0117] Example 7:

[0118] Carbonized sludge-based defluorination filter material comprises the following components in parts by weight:

[0119] 60 parts of modified carbonized sludge, 25 parts of anion resin, 7.5 parts of clay, 3 parts of binder, and 3 parts of pore-forming agent.

[0120] Example 8:

[0121] The preparation method of carbonized sludge-based defluorination filter material comprises the following steps:

[0122] (S01) Weighing an appropriate amount of carbonized sludge, soaking it in 5% dilute hydrochloric acid for 0.5 h, washing it with anhydrous ethanol, and then drying it at 85°C;

[0123] (S02) adding ammonia water to the carbonized sludge dried in step (S01), stirring and mixing, washing with anhydrous ethanol, and drying at a temperature of 85° C.;

[0124] (S03) taking an appropriate amount of the carbonized sludge dried in step (S02) and an appropriate amount of calcium hydroxide and grinding them together in a ball mill; wherein the mass ratio of the carbonized sludge to the calcium hydroxide is 1:1;

[0125] (S04) preparing a phosphoric acid solution with a mass concentration of 45%, and placing the ground mixture in step (S03) into the phosphoric acid solution for soaking reaction; ensuring that the concentration ratio of phosphate ion concentration to calcium ion concentration is 0.5;

[0126] (S05) stirring and vibrating the reactants in step (S04) until they are in a paste-like state, drying and dehydrating the mixture, and grinding the mixture into a powder in a ball mill;

[0127] (S06) taking appropriate amounts of anion resin, clay, binder and pore-forming agent, adding water and stirring together with the powder in step (S05); the anion resin is a strong alkaline anion exchange resin; the clay is kaolin; and the binder is carboxymethyl cellulose;

[0128] (S07) granulating the stirred mixture in step (S06) into spherical particles with a particle size of 0.3 cm, and placing the formed particles in a calcination container at a temperature of 300° C. and blocking oxygen for calcination for 1 hour;

[0129] (S08) After the calcination in step (S07) is completed and naturally cooled to room temperature, a carbonized sludge-based defluorination filter material is obtained; wherein the bulk density of the carbonized sludge-based defluorination filter material is 0.2 g / cm 3 ; Porosity 30%.

[0130] Example 9:

[0131] The preparation method of carbonized sludge-based defluorination filter material comprises the following steps:

[0132] (S01) Weighing an appropriate amount of carbonized sludge, soaking it in 15% dilute hydrochloric acid for 1.5 h, washing it with anhydrous ethanol, and then drying it at 200°C;

[0133] (S02) adding ammonia water to the carbonized sludge dried in step (S01), stirring and mixing, washing with anhydrous ethanol, and drying at a temperature of 200° C.;

[0134] (S03) taking an appropriate amount of the carbonized sludge dried in step (S02) and an appropriate amount of calcium hydroxide and grinding them together in a ball mill; wherein the mass ratio of the carbonized sludge to the calcium hydroxide is 3:1;

[0135] (S04) preparing a phosphoric acid solution with a mass concentration of 55%, and placing the ground mixture in step (S03) into the phosphoric acid solution for soaking reaction; ensuring that the concentration ratio of phosphate ion concentration to calcium ion concentration is 0.8;

[0136] (S05) stirring and vibrating the reactants in step (S04) until they are in a paste-like state, drying and dehydrating the mixture, and grinding the mixture into a powder in a ball mill;

[0137] (S06) taking appropriate amounts of anion resin, clay, binder and pore-forming agent, adding water and stirring together with the powder in step (S05); the anion resin is a weakly basic anion exchange resin; the clay is 200 mesh sodium bentonite; and the binder is polyvinyl alcohol;

[0138] (S07) granulating the stirred mixture in step (S06) into spherical particles with a particle size of 0.8 cm, and placing the formed particles in a calcination container at a temperature of 350° C. and blocking oxygen for calcination for 2 hours;

[0139] (S08) After the calcination in step (S07) is completed and naturally cooled to room temperature, a carbonized sludge-based defluorination filter material is obtained; wherein the bulk density of the carbonized sludge-based defluorination filter material is 0.8 g / cm 3 ; Porosity 50%.

[0140] Example 10:

[0141] The preparation method of carbonized sludge-based defluorination filter material comprises the following steps:

[0142] (S01) Weighing an appropriate amount of carbonized sludge, soaking it in 10% dilute hydrochloric acid for 1 hour, washing it with anhydrous ethanol, and then drying it at 150°C;

[0143] (S02) adding ammonia water to the carbonized sludge dried in step (S01), stirring and mixing, washing with anhydrous ethanol, and drying at a temperature of 150° C.;

[0144] (S03) taking an appropriate amount of the carbonized sludge dried in step (S02) and an appropriate amount of calcium hydroxide and grinding them together in a ball mill; wherein the mass ratio of the carbonized sludge to the calcium hydroxide is 2:1;

[0145] (S04) preparing a phosphoric acid solution with a mass concentration of 50%, and placing the ground mixture in step (S03) into the phosphoric acid solution for soaking reaction; ensuring that the concentration ratio of phosphate ion concentration to calcium ion concentration is 0.65;

[0146] (S05) stirring and vibrating the reactants in step (S04) until they are in a paste-like state, drying and dehydrating the mixture, and grinding the mixture into a powder in a ball mill;

[0147] (S06) taking appropriate amounts of anion resin, clay, binder and pore-forming agent, adding water and stirring together with the powder in step (S05); the anion resin is CH-87 anion exchange resin; the clay is montmorillonite; and the binder is hydroxypropyl methylcellulose;

[0148] (S07) granulating the stirred mixture in step (S06) into spherical particles with a particle size of 0.5 cm, and placing the formed particles in a calcination container at a temperature of 330° C. and blocking oxygen for calcination for 1.5 hours;

[0149] (S08) After the calcination in step (S07) is completed and naturally cooled to room temperature, a carbonized sludge-based defluorination filter material is obtained; wherein the bulk density of the carbonized sludge-based defluorination filter material is 0.5 g / cm 3 ; Porosity 40%.

[0150] Application Example 1:

[0151] First, take 50 kg of carbonized sludge residue and soak it in a prepared 10% dilute hydrochloric acid solution for 1 hour. Then, rinse it with clean water and dry it for later use. Then, mix it with 50 ml of ammonia solution to hydroxylate the surface, obtaining a modified carbonized sludge powder. The powder is mixed with 100 kg of calcium hydroxide and pounded into a paste with 300 ml of 50% phosphoric acid solution to produce a surface-coated hydroxyapatite. The main raw materials are hydroxyapatite, 5 kg of bentonite, 15 kg of CH-87 anion exchange resin, 1 kg of hydroxypropyl methylcellulose, and 1 kg of sodium bicarbonate. The bentonite particle size is selected to be 200 mesh. The proportion of water added is 8% of the total mass of the filler. After mixing, the filler is granulated and formed into small balls with a size of 0.3 cm. The filler is placed in a muffle furnace and heated for 2 hours at 320°C. The resulting material has a bulk density of 0.5 g / cm 3 , porosity 35%; the filler is placed in the fluidized bed reactor with a filling ratio of 50%; the effective volume of the cylindrical fluidized bed reactor is 10L; the influent is a fluorine-containing electronic wastewater, the hydraulic retention time is 30min, the average fluoride ion concentration of the raw water is 35.5mg / L, the average produced water is 1.5mg / L, and the removal rate is 95.8%.

[0152] Application Example 2:

[0153] First, 70 kg of carbonized sludge residue was soaked in a prepared 10% dilute hydrochloric acid solution for 1 hour, washed with clean water, and dried for later use; then, the mixture was mixed with 50 ml of ammonia solution to hydroxylate the surface and obtain a modified carbonized sludge powder; the powder was mixed with 150 kg of calcium hydroxide and mixed with 450 ml of 50% phosphoric acid solution to form a paste to produce surface-coated hydroxyapatite; hydroxyapatite, 10 kg of kaolin, 35 kg of CH-87 anion exchange resin, 5 kg of sodium carboxymethyl cellulose, and 5 kg of sodium bicarbonate were used as the main raw materials, the particle size of the bentonite was selected to be 400 mesh, and the proportion of water added was 10% of the total mass of the filler. After mixing, the filler was granulated and formed into small balls with a filler size of 0.5 cm; the filler was placed in a muffle furnace and heated for 2 hours at 320°C. The resulting material had a bulk density of 0.8 g / cm 3 , porosity 40%; the filler is placed in the fluidized bed reactor with a filling ratio of 50%; the effective volume of the cylindrical fluidized bed reactor is 10L; the influent is a fluorine-containing groundwater, the hydraulic retention time is 30min, the average fluoride ion concentration of the raw water is 5.5mg / L, the average produced water concentration is 0.6mg / L, the removal rate is 89.1%, and it meets the discharge standards.

[0154] Application Example 3:

[0155] First, 60 kg of carbonized sludge residue is soaked in a prepared 10% dilute hydrochloric acid solution for one hour, then rinsed with clean water, dried, and set aside. The mixture is then mixed with 50 ml of ammonia solution to hydroxylate the surface, yielding a modified carbonized sludge powder. The powder is then mixed with 50 kg of calcium hydroxide and pounded into a paste with 250 ml of a 50% phosphoric acid solution to form a surface-coated hydroxyapatite. The main raw materials are hydroxyapatite, 8 kg of sodium bentonite, 20 kg of CH-87 anion exchange resin, 3 kg of sodium carboxymethyl cellulose, and 3 kg of sodium bicarbonate. The bentonite particle size is 300 mesh, and the water content is 10% of the total filler mass. After mixing, the mixture is granulated into 0.8 cm balls. The filler is heated in a muffle furnace at 330°C for one hour. The resulting material has a bulk density of 0.6 g / cm 3 , porosity 50%; the filler is placed in the fluidized bed reactor with a filling ratio of 50%; the effective volume of the columnar fluidized bed reactor is 10L; the influent is a fluorine-containing coal chemical wastewater, the hydraulic retention time is 30min, the average fluoride ion concentration of the raw water is 18.5mg / L, the average produced water is 1.2mg / L, the removal rate is 93.5%, and it meets the emission standards.

[0156] Example 11:

[0157] A ball mill used for preparing carbonized sludge-based defluorination filter material includes a processing base 1, support plates 2 are provided on both sides of the processing base 1, and a ball mill cover 3 is provided between the two support plates 2, wherein one end of the ball mill cover 3 is fixedly connected to the support plate 2, and the other end is fixedly connected to the support plate 2 through a plurality of pillars. Through the setting of multiple pillars, the knob ring 35 can be conveniently rotated externally. The support plate 2 located on one side is connected to a drive shaft 4 through a reduction transmission assembly. Furthermore, the reduction transmission assembly includes a reducer 16 arranged on the support plate 2, and the output end of the reducer 16 is connected to the drive shaft 4. A drive motor 17 is fixedly provided on the reducer 16, and the output end of the drive motor 17 is connected to the input end of the reducer 16. The reducer 16 and the drive motor 17 are both existing technologies and will not be described in detail here.

[0158] The driving shaft 4 is fixedly connected to the ball mill 5, and the ball mill 5 is densely provided with grinding balls 6. In this solution, the grinding balls 6 are made of iron metal and can be adsorbed by magnetic force. A feeding port 7 is provided on one side of the ball mill 5 and passes through the side wall. Furthermore, a support end cover 18 is fixedly connected to the support plate 2 located on the side of the feeding port 7. A discharge port is provided on the support plate 2 and passes through the side wall of the support end cover 18. A sealing plug 19 is provided in the discharge port, and the discharge port corresponds to the size of the feeding port 7.

[0159] It is worth noting that the setting of the sealing plug 19 can achieve the closure of the discharge port. At this time, the position of the material outlet 7 will achieve a sealing effect due to the obstruction of the supporting end cover 18 and the side wall of the sealing plug 19.

[0160] The outer wall of the ball mill chamber 5 is connected to the isolation ring 8 and the switching ring 9 through a rotating connection. Furthermore, the rotating connection includes an inner rotating ring 20 connected to the support end cover 18 through a first bearing. The inner rotating ring 20 is fixedly set at the end of the ball mill chamber 5. The inner rotating ring 20 is rotatably connected to the end of the isolation ring 8 through a second bearing. The isolation ring 8 is rotatably connected to the switching ring 9 through a third bearing. The switching ring 9 is rotatably connected to the inner wall of the ball mill cover 3 through a fourth bearing.

[0161] The top of the ball mill cover 3 is provided with a ball outlet 10 which is evenly distributed along the axis. A magnetic storage component is provided on the ball mill cover 3 at the ball outlet 10. The magnetic storage component includes a storage arc plate 21 and a magnetic arc plate 22 connected by a fastening adjustment component. A grid plate 23 for storing the grinding balls 6 is provided at the bottom of the storage arc plate 21, and a magnetic attraction plate 24 is provided above the magnetic arc plate 22.

[0162] Furthermore, the fastening adjustment part includes a fan-shaped support part 25 connected to the storage arc plate 21 and the magnetic arc plate 22 respectively, and an arc-shaped opening 26 is opened on the fan-shaped support part 25. The support plate 2 and the storage arc plate 21 are both threadedly connected with a fastening knob column 27, and the fastening knob column 27 extends outward through the arc-shaped opening 26.

[0163] A further advantage of adopting the above method is that the storage arc plate 21 and the magnetic arc plate 22 can rotate, and the adjacent positions can be changed during the rotation, so that the storage arc plate 21 and the magnetic arc plate 22 can be flexibly adjusted according to the magnetic requirements of taking and placing and the storage process. During the adjustment process, it is only necessary to loosen the fastening knob column 27.

[0164] The isolation ring 8 is provided with a cleaning ball port 11 corresponding to the ball outlet 10, the switching ring 9 is provided with a ball outlet channel 12 corresponding to the ball outlet 10, and the switching ring 9 is provided with a linkage ball port 13 corresponding to the cleaning ball port 11. Furthermore, the isolation ring 8 is sleeved on the outer wall of the ball mill chamber 5, the switching ring 9 is sleeved on the outer wall of the isolation ring 8, and the ball mill cover 3 is sleeved on the outer wall of the switching ring 9. The inner diameters of the ball outlet 10, the cleaning ball port 11 and the ball outlet channel 12 are consistent and meet the requirements for the movement of the grinding balls 6.

[0165] A driving magnetic ball 14 is provided in the linkage ball mouth 13, and a horizontal adjustment shaft 15 is connected to the switching ring 9 through an elastic linkage component. Furthermore, the elastic linkage component includes a vertical elastic mouth opened in the switching ring 9, and an elastic block 28 is connected to the inside of the vertical elastic mouth through a resistance spring. The elastic block 28 is rotatably connected to the horizontal adjustment shaft 15. An adjustment through-hole 29 for moving the horizontal adjustment shaft 15 is provided on the switching ring 9 located at the linkage ball mouth 13. One end of the horizontal adjustment shaft 15 extends outward through the side wall of the switching ring 9 and is fixedly connected to a linkage gear 30. A fixed gear ring 31 adapted to the linkage gear 30 is fixedly connected to the support plate 2.

[0166] It should be noted that the driving magnetic ball 14 in the linkage ball port 13 will partially move into the cleaning ball port 11 under the action of the elastic force applied to the elastic block 28 by the resistance spring. When the driving magnetic ball 14 is not in the linkage ball port 13, it will retract into the linkage ball port 13 under the action of the resistance force of the inner wall of the isolation ring 8. In this process, the fixed gear ring 31 and the linkage gear 30 will be engaged and disengaged.

[0167] The horizontal adjustment shaft 15 is fixedly connected to the multiple driving magnetic balls 14. The ends of the switching ring 9 and the isolation ring 8 are both provided with control rotary members. The control rotary members include an external thread layer provided on the outer wall of the driving shaft 4. The external thread layer is threadedly connected to the adjusting nut ring 32. The adjusting nut ring 32 is provided with a rotating knob ring 35. The outer wall of the adjusting nut ring 32 is connected to the sleeve ring 33 through a keyway connector 36. The outer walls of the two sleeve rings 33 are respectively connected to the switching ring 9 and the isolation ring 8 through multiple connecting rods 34.

[0168] The keyway connector 36 includes a plurality of torque key strips evenly distributed on the outer wall of the adjusting nut ring 32, and a keyway adapted to the torque key strip is provided on the inner wall of the sleeve ring 33. The keyway connector 36 is provided to compensate for the movement of the threaded adjusting nut ring 32 after rotation, so as to avoid the movement affecting the switching ring 9 and the isolation ring 8.

[0169] The working principle of ball mill is:

[0170] When the present invention is used, the modified carbonized sludge and a certain amount of calcium hydroxide are placed in the ball mill, and the corresponding grinding balls 6 are added according to the progress and accuracy of the grinding. The magnetic arc plate 22 is rotated so that the magnetic arc plate 22 is not at the top. At this time, the receiving arc plate 21 is rotated so that the grinding balls 6 stored in the grid plate 23 on the receiving arc plate 21 are moved to the ball outlet 10. At this time, there is no magnetic attraction of the magnetic suction plate 24 on the magnetic arc plate 22, and the grinding balls 6 will fall from the ball outlet 10 into the ball mill bin 5. At this time, the control knob ring 35 is controlled to make the switching ring 9 and the isolation ring 8 misaligned. The side wall of the switching ring 9 will seal the cleaning ball port 11 on the isolation ring 8. The ball mill bin 5 will rotate under the action of the drive motor 17 and the reducer 16. During the rotation, the grinding balls 6 will grind the material during the rolling process. When the number of grinding balls 6 needs to be adjusted according to the grinding accuracy during the material grinding process, the above action is repeated to achieve batch addition of grinding balls 6.

[0171] After the grinding is completed, the knob ring 35 is turned to drive the switching ring 9 and the isolation ring 8 to rotate relative to each other, so that the cleaning ball port 11 on the isolation ring 8 is in the same position as the linkage ball port 13. During this process, the driving magnetic ball 14 set in the linkage ball port 13 will move outward and extend into the cleaning ball port 11. At this time, during the rotation process, the grinding balls 6 will move into the cleaning ball port 11 one by one under the action of the magnetic attraction and contact with the driving magnetic balls 14. The elastic block 28 connected to the resistance spring will make the linkage gear 30 at the end of the horizontal adjustment shaft 15 approach and mesh with the fixed gear ring 31. During the rotation process, the fixed gear ring 31 will make the linkage gear 30 drive multiple driving magnetic balls 14 to rotate. The friction force of the driving magnetic balls 14 will cause the grinding balls 6 in contact with them to rotate, and the dust adsorbed on the surface of the grinding balls 6 will be scraped off by the cleaning ball port 11 during the rotation process, which is convenient for the subsequent effective cleaning of the dust.

[0172] After cleaning is completed, the cleaning ball port 11 on the switching ring 9 is placed at the top position connected to the ball outlet 10. It is only necessary to rotate the switching ring 9 so that the ball outlet channel 12 on the switching ring 9 corresponds to the cleaning ball port 11 and the ball outlet 10. During the rotation process, the grinding ball 6 will be adsorbed on the cleaning ball port 11 under the action of the magnetic force on the magnetic arc plate 22 until the grinding ball 6 is absorbed into the grid plate 23 in the receiving arc plate 21, thereby realizing the storage of the cleaned grinding ball 6.

[0173] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes based on the technical solutions and improved concepts of the present invention within the technical scope disclosed by the present invention, and these changes should be covered by the scope of protection of the present invention.

Claims

1. Carbonized sludge-based defluorination filter material, characterized by: The following components are included in parts by weight: 50-70 parts of modified carbonized sludge, 15-35 parts of anion resin, 5-10 parts of clay, 1-5 parts of binder, and 1-5 parts of pore-forming agent; The modified carbonized sludge is obtained by the following modification method: Take the carbonized sludge, soak it in dilute hydrochloric acid, wash it with anhydrous ethanol and then dry it; Add ammonia water to the dried carbonized sludge and stir to mix, then wash with anhydrous ethanol and dry; The dried carbonized sludge and calcium hydroxide are ball-milled together; preparing a phosphoric acid solution, and placing the ball-milled mixture in the phosphoric acid solution for soaking and reaction; The reactants are stirred and vibrated to a paste, dried, dehydrated and ball-milled into powder to obtain the modified carbonized sludge.

2. The carbonized sludge-based defluorination filter material according to claim 1, characterized in that: The following components are included in parts by weight: 55-65 parts of modified carbonized sludge, 20-30 parts of anion resin, 6-9 parts of clay, 1.5-4.5 parts of binder, and 1.5-4.5 parts of pore-forming agent.

3. A method for preparing a carbonized sludge-based defluorination filter material, characterized by: Including the following step, (S01) Weigh an appropriate amount of carbonized sludge, soak it in dilute hydrochloric acid, wash it with anhydrous ethanol, and then dry it; (S02) adding ammonia water to the carbonized sludge dried in step (S01), stirring and mixing, and washing with anhydrous ethanol and then drying; (S03) taking an appropriate amount of the carbonized sludge dried in step (S02) and an appropriate amount of calcium hydroxide and grinding them together in a ball mill; (S04) preparing a phosphoric acid solution, and placing the ground mixture in step (S03) into the phosphoric acid solution for soaking and reaction; (S05) stirring and vibrating the reactants in step (S04) until they are in a paste-like state, drying and dehydrating the reactants, and grinding the mixture into a powder in a ball mill; (S06) taking appropriate amounts of anionic resin, clay, binder and pore-forming agent, adding water and stirring together with the powder in step (S05); (S07) granulating the stirred mixture in step (S06) and placing the granules into a calcination container for calcination; (S08) After the calcination in step (S07) is completed and cooled, a carbonized sludge-based defluorination filter material is obtained.

4. The method for preparing the carbonized sludge-based defluorination filter material according to claim 3, wherein: The mass concentration of the dilute hydrochloric acid in the step (S01) is 5% to 15%; the soaking time in the step (S01) is 0.5h to 1.5h; the drying temperature in the step (S01) is 85°C to 200°C; the drying temperature in the step (S02) is 85°C to 200°C; the mass ratio of the carbonized sludge to calcium hydroxide in the step (S03) is 1:1 to 3:1; the mass concentration of the phosphoric acid solution in the step (S04) is 45% to 55%; the preparation requirement of the phosphoric acid solution in the step (S04) is that the concentration ratio of phosphate ion concentration to calcium ion concentration is 0.5 to 0.

8.

5. The method for preparing the carbonized sludge-based defluorination filter material according to claim 3, wherein: The calcination in step (S07) is carried out under oxygen-blocking conditions; the calcination temperature in step (S07) is 300°C to 350°C; the calcination time in step (S07) is 1 hour to 2 hours; the shape of the particles after granulation in step (S07) is spherical; the particle size of the particles after granulation in step (S07) is 0.3 cm to 0.8 cm; the cooling in step (S08) is natural cooling to room temperature; the bulk density of the carbonized sludge-based defluorination filter material in step (S08) is 0.2 g / cm 3 ~0.8g / cm 3 ; The porosity of the carbonized sludge-based defluorination filter material in the step (S08) is 30% to 50%.

6. The method for preparing the carbonized sludge-based defluorination filter material according to claim 3, wherein: The anion resin is selected from a strong alkaline anion exchange resin or a weak alkaline anion exchange resin; the clay is selected from at least one of kaolin, bentonite or montmorillonite; and the binder is selected from carboxymethyl cellulose, polyvinyl alcohol or hydroxypropyl methylcellulose.

7. The method for preparing the carbonized sludge-based defluorination filter material according to claim 3, wherein: The ball mill comprises a processing base (1), support plates (2) are provided on both sides of the processing base (1), and a ball mill cover (3) is provided between the two support plates (2); a driving shaft (4) is connected to the support plate (2) on one side through a reduction transmission assembly, and the driving shaft (4) is fixedly connected to a ball mill chamber (5), and grinding balls (6) are densely arranged in the ball mill chamber (5), a material taking port (7) penetrating the side wall of the ball mill chamber (5) is provided on one side, and an isolation ring (8) and a switching ring (9) are connected to the outer wall of the ball mill chamber (5) through a rotating connecting piece, and a plurality of ball outlets (10) are provided on the top of the ball mill cover (3), and a magnetic storage member is provided on the ball mill cover (3) at the ball outlet (10).

8. The method for preparing the carbonized sludge-based defluorination filter material according to claim 7, wherein: The isolation ring (8) is provided with a cleaning ball port (11) corresponding to the ball outlet port (10), the switching ring (9) is provided with a ball outlet channel (12) corresponding to the ball outlet port (10), the switching ring (9) is provided with a linkage ball port (13) corresponding to the cleaning ball port (11), a driving magnetic ball (14) is arranged in the linkage ball port (13), a horizontal adjustment shaft (15) is connected to the switching ring (9) through an elastic linkage component, the horizontal adjustment shaft (15) is fixedly connected to the plurality of driving magnetic balls (14), and control rotating parts are provided at the ends of the switching ring (9) and the isolation ring (8); the isolation ring (8) is sleeved on the outer wall of the ball mill chamber (5), the switching ring (9) is sleeved on the outer wall of the isolation ring (8), and the ball mill cover (3) is sleeved on the outer wall of the switching ring (9), and the inner diameters of the ball outlet port (10), the cleaning ball port (11) and the ball outlet channel (12) are consistent.

9. The method for preparing the carbonized sludge-based defluorination filter material according to claim 7, wherein: The reduction transmission assembly includes a reducer (16) arranged on a support plate (2), an output end of the reducer (16) is connected to a drive shaft (4), a drive motor (17) is fixedly arranged on the reducer (16), and the output end of the drive motor (17) is connected to the input end of the reducer (16); a support end cover (18) is fixedly connected to the support plate (2) located on one side of the material taking port (7), a discharge port penetrating the side wall of the support end cover (18) is opened on the support plate (2), a sealing plug (19) is arranged in the discharge port, and the size of the discharge port corresponds to that of the material taking port (7).

10. Use of the carbonized sludge-based defluoridation filter material according to any one of claims 1 to 2 in the removal of fluoride ions, treatment of semiconductor chip silicon etching wastewater, treatment of glass etching wastewater, treatment of fluoride-containing groundwater or treatment of mine water.

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