Thallium-containing sewage treatment method, thallium removal agent preparation method and preparation equipment

Abstract

The invention provides a thallium-containing sewage treatment method, a thallium removal agent preparation method and preparation equipment, and relates to the field of environment control and pollution treatment. The thallium-containing sewage treatment method comprises the following steps: S1, introducing thallium-containing sewage into a treatment box; s2, adding a thallium removal agent into the sewage treatment tank; and S3, stirring the thallium-containing wastewater at 20-40 DEG C, and adsorbing the thallium element in the wastewater by using the thallium removal agent. According to the thallium-containing sewage treatment method provided by the invention, five heteroatoms of nitrogen, phosphorus, sulfur, oxygen and chlorine are doped in a biochar matrix, the adsorption capacity and selectivity of the biochar material to thallium ions in water pollution are remarkably improved by utilizing the synergistic effect of the multiple heteroatoms, and the five heteroatoms form rich active sites on the surface of the biochar, so that the thallium-containing sewage treatment effect is improved. And complexing, ion exchange and the like can be carried out with thallium ions, so that the adsorption effect is enhanced, and the treatment effect on thallium-containing sewage in water pollution treatment and control is improved.

Description

Technical Field

[0001] This invention relates to the field of environmental control and pollution treatment, and in particular to a method for treating thallium-containing wastewater, a method for preparing thallium removal agents, and equipment for preparing such agents. Background Technology

[0002] Thallium is highly toxic, has strong accumulative properties, and is easily migrated, posing a serious threat to the ecological environment and human health. With continuous industrial development, the discharge of thallium-containing wastewater is increasing daily, and thallium pollution is becoming increasingly severe. Currently, commonly used thallium removal methods mainly include chemical precipitation, ion exchange, and adsorption, among which adsorption is widely used due to its advantages of simple operation, low cost, and high efficiency.

[0003] As a novel adsorbent material, biochar has the characteristics of large specific surface area, rich pore structure and diverse surface functional groups, showing good application potential in the treatment of heavy metal pollution. However, biochar materials doped with single heteroatoms still have shortcomings in thallium adsorption performance, such as limited adsorption capacity, low selectivity and poor stability, which make it difficult to meet the needs of actual water pollution treatment.

[0004] Therefore, it is necessary to provide a method for treating thallium-containing wastewater to solve the above-mentioned technical problems. Summary of the Invention

[0005] This invention provides a method for treating thallium-containing wastewater, which solves the problem that there is still room for improvement in the thallium adsorption performance of biochar materials with single heteroatom doping.

[0006] To solve the above-mentioned technical problems, the present invention provides a method for treating thallium-containing wastewater, comprising the following steps:

[0007] S1. The wastewater containing thallium is introduced into the treatment tank;

[0008] S2. Add the thallium removal agent to the wastewater treatment tank. The solid-liquid ratio of the thallium removal agent to the thallium-containing water is 1:(10-100)g / L.

[0009] The thallium removal agent includes biochar and five compounds containing nitrogen, phosphorus, sulfur, oxygen and chlorine. The mass ratio of biochar to the five compounds is 1:(0.5-2), and the molar ratio of nitrogen, phosphorus, sulfur, oxygen and chlorine is (1-5):(1-3):(1-4):(2-6):(1-2).

[0010] S3. Stir the thallium-containing wastewater at 20-40℃ and use the thallium removal agent to adsorb the thallium element in the wastewater for 1-12 hours.

[0011] S4. Discharge the wastewater after it has been treated with thallium removal agent.

[0012] Preferably, the biochar is prepared from agricultural waste, which is selected from at least one of straw, rice husks, and peanut shells.

[0013] Preferably, the five compounds containing nitrogen, phosphorus, sulfur, oxygen, and chlorine are urea, ammonium dihydrogen phosphate, thiourea, hydrogen peroxide, and ammonium chloride, respectively.

[0014] This invention also provides a method for preparing a thallium removal agent, used in the aforementioned thallium-containing wastewater treatment method; comprising the following steps:

[0015] S11. After washing and drying agricultural waste, crush it and sieve it to obtain biomass powder.

[0016] S12. Mix biomass powder and heteroatom dopant at a mass ratio of 1:(0.5-2) to obtain a mixture, wherein the heteroatom dopant is a nitrogen-containing compound, a phosphorus-containing compound, a sulfur-containing compound, an oxygen-containing compound, or a chlorine-containing compound.

[0017] S13. Place the mixture in an inert gas and calcine it at 500-900℃ for 2-6 hours, with a heating rate of 5-10℃ / min.

[0018] S14. After calcination, the product is naturally cooled to room temperature, removed, washed with deionized water until neutral, and dried to obtain a thallium removal agent for high-entropy heteroatom-doped biochar material.

[0019] Preferably, the inert gas in S13 is nitrogen or argon.

[0020] The present invention also provides an apparatus for preparing thallium removal agent, comprising a mixing drum, a stirring device and two mounting plates, characterized in that, for use in the aforementioned method for preparing thallium removal agent, it further comprises: a lifting device and a material holding structure;

[0021] The mixing cylinder includes a main cylinder body, a top cover, and a rotating structure. The main cylinder body is horizontally installed between two mounting plates. One side of the top cover is rotatably installed on the main cylinder body via the rotating structure, and two guide rollers are installed at intervals on the other side of the top cover.

[0022] The lifting device is used to drive the top cover to rotate along the rotating structure;

[0023] The material holding structure includes a material bag and two rope structures. The two rope structures are connected to both ends of the material bag. Each rope structure includes a main rope, a first branch rope, a second branch rope, and a buckle. The first branch rope and the second branch rope are respectively installed on both sides of the end of the material bag. One end of the main rope is connected to the first branch rope and the second branch rope, and the buckle is connected to the other end of the main rope.

[0024] When the material-filling structure is used to feed material into the mixing cylinder, the buckle is detachably connected to the guide roller.

[0025] Preferably, the lifting device includes a rotating base, a lifting cylinder, and a connecting arm. The lifting cylinder is rotatably mounted on the mounting plate via the rotating base. One end of the connecting arm is connected to the side of the top cover away from the rotating structure. The output end of the lifting cylinder is rotatably connected to the other end of the connecting arm.

[0026] Preferably, the thallium removal agent preparation equipment further includes a rope winding structure, which includes a rotating device, a rotating shaft, and a winding frame. The rotating shaft passes through and is rotatably mounted on the mounting plate. The winding frame is mounted at one end of the rotating shaft and is located below the guide roller. The rotating device is used to drive the rotating shaft to rotate.

[0027] When the material-filling structure is used to feed material into the mixing drum, the main rope passes through the guide roller, and the buckle is detachably connected to the winding frame.

[0028] Preferably, the rotating device includes a toothed plate and a gear, the gear is mounted on the rotating shaft, the toothed plate is vertically slidably mounted on the mounting plate, the toothed plate meshes with the gear, and the rope winding structure further includes a driving rope, the driving rope connecting the toothed plate to the output end of the lifting cylinder.

[0029] Preferably, the first branch rope includes a connecting rope, a sling and an L-shaped hook, one end of the connecting rope is connected to the filling bag, the sling is installed at the other end of the connecting rope, and the L-shaped hook is installed on the main rope;

[0030] An abutment plate is provided on the inner wall of the top cover at the position corresponding to the guide roller.

[0031] Compared with related technologies, the thallium-containing wastewater treatment method, thallium removal agent preparation method, and preparation equipment provided by the present invention have the following beneficial effects:

[0032] This invention provides a method for treating thallium-containing wastewater. By doping a biochar matrix with five heteroatoms—nitrogen, phosphorus, sulfur, oxygen, and chlorine—the synergistic effect between these heteroatoms significantly improves the adsorption capacity and selectivity of the biochar material for thallium ions in water pollution. The five heteroatoms form abundant active sites on the surface of the biochar, which can interact with thallium ions through complexation and ion exchange, thereby enhancing the adsorption effect and improving the treatment efficiency of thallium-containing wastewater in water pollution control. Attached Figure Description

[0033] Figure 1 A flowchart illustrating the steps of the thallium-containing wastewater treatment method provided by the present invention;

[0034] Figure 2 A flowchart illustrating the steps of the thallium removal agent preparation method provided by the present invention;

[0035] Figure 3 This is a schematic diagram of the equipment for preparing thallium removal agent provided by the present invention;

[0036] Figure 4 for Figure 3 The enlarged schematic diagram of part A shown below;

[0037] Figure 5 This is a partial cross-sectional view of the apparatus for preparing thallium removal agent provided by the present invention;

[0038] Figure 6 This is a schematic diagram of the material holding structure provided by the present invention;

[0039] Figure 7 This is a schematic diagram illustrating the feeding state of the material-holding structure provided by the present invention onto the main cylinder; wherein... Figure 7 (a) is a schematic diagram showing the filling bag located on the support platform with the buckle passing through the guide roller and connected to the winding frame. Figure 7 (b) is a schematic diagram of the lifting device lifting the top cover and driving the filling bag to the top opening of the main cylinder;

[0040] Figure 8 This is a schematic diagram of the lifting device for the present invention, showing how the lifting top cover causes the toothed plate to move upward.

[0041] Numbering on the map:

[0042] 1. Mounting plate; 101. Limit roller;

[0043] 2. Mixing cylinder; 21. Main cylinder body; 22. Top cover; 23. Rotating structure;

[0044] 211. Discharge pipe; 221. Guide roller; 222. Abutment plate;

[0045] 3. Agitator; 31. Drive unit; 32. Agitator shaft; 33. Plow blade agitator;

[0046] 4. Lifting device; 41. Rotating seat; 42. Lifting cylinder; 43. Connecting arm;

[0047] 5. Rope winding structure; 51. Rotating device; 52. Rotating shaft; 53. Winding frame; 54. Limiting plate; 55. Driving rope; 511. Toothed plate; 512. Gear;

[0048] 6. Support platform;

[0049] 7. Material holding structure; 71. Material bag; 72. Main rope; 73. First rope; 74. Second rope; 75. Buckle; 731. Connecting rope; 732. Loop; 733. L-shaped hook;

[0050] 8. Spraying components. Detailed Implementation

[0051] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0052] This invention provides a method for treating thallium-containing wastewater.

[0053] Please refer to the following: Figure 1 In one embodiment of the present invention, the thallium-containing wastewater treatment method is characterized by comprising the following steps:

[0054] S1. The wastewater containing thallium is introduced into the treatment tank;

[0055] S2. Add the thallium removal agent to the wastewater treatment tank. The solid-liquid ratio of the thallium removal agent to the thallium-containing water is 1:(10-100)g / L.

[0056] The thallium removal agent includes biochar and five compounds containing nitrogen, phosphorus, sulfur, oxygen and chlorine. The mass ratio of biochar to the five compounds is 1:(0.5-2), and the molar ratio of nitrogen, phosphorus, sulfur, oxygen and chlorine is (1-5):(1-3):(1-4):(2-6):(1-2).

[0057] S3. Stir the thallium-containing wastewater at 20-40℃ and use the thallium removal agent to adsorb the thallium element in the wastewater for 1-12 hours.

[0058] S4. Discharge the wastewater after it has been treated with thallium removal agent.

[0059] In this invention, before the thallium-containing wastewater is introduced into the treatment tank, larger impurities in the wastewater are removed by means of a screen and filter. An equalization tank is set up to adjust the water volume and pH of the wastewater. Subsequently, the wastewater is treated with a thallium removal agent before being introduced into the treatment tank. The water flowing out of the wastewater tank is then filtered through an activated carbon layer, a precision filter (or an ultrafiltration), and finally the pH is adjusted to the range specified by the national discharge standards (usually 6-9).

[0060] By doping the biochar matrix with five heteroatoms—nitrogen, phosphorus, sulfur, oxygen, and chlorine—the synergistic effect among these heteroatoms significantly improves the adsorption capacity and selectivity of biochar materials for thallium ions in water pollution. The five heteroatoms form abundant active sites on the surface of the biochar, which can interact with thallium ions through complexation and ion exchange, thereby enhancing the adsorption effect and improving the treatment efficiency of thallium-containing wastewater in water pollution control.

[0061] In a preferred embodiment, the biochar is prepared from agricultural waste, which is selected from at least one of straw, rice husks, and peanut shells.

[0062] Using agricultural waste as raw material for biochar is widely available and inexpensive, realizing the resource utilization of agricultural waste and reducing the preparation cost of thallium removal agents.

[0063] As an optional embodiment, the five compounds containing nitrogen, phosphorus, sulfur, oxygen, and chlorine are urea, ammonium dihydrogen phosphate, thiourea, hydrogen peroxide, and ammonium chloride, respectively.

[0064] The nitrogen-containing compound is selected from at least one of urea, melamine, and ammonium nitrate; the phosphorus-containing compound is selected from at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and sodium phosphate; the sulfur-containing compound is selected from at least one of thiourea, sodium sulfate, and sodium sulfide; the oxygen-containing compound is selected from at least one of hydrogen peroxide, potassium permanganate, and nitric acid; and the chlorine-containing compound is selected from at least one of ammonium chloride, sodium chloride, and potassium chloride.

[0065] The present invention also provides a method for preparing a thallium removal agent.

[0066] Please see Figure 2 A method for preparing a thallium removal agent, used in the aforementioned thallium-containing wastewater treatment method; comprising the following steps:

[0067] S11. After washing and drying agricultural waste, crush it and sieve it to obtain biomass powder.

[0068] S12. Mix biomass powder and heteroatom dopant at a mass ratio of 1:(0.5-2) to obtain a mixture, wherein the heteroatom dopant is a nitrogen-containing compound, a phosphorus-containing compound, a sulfur-containing compound, an oxygen-containing compound, or a chlorine-containing compound.

[0069] S13. Place the mixture in an inert gas and calcine it at 500-900℃ for 2-6 hours, with a heating rate of 5-10℃ / min.

[0070] S14. After calcination, the product is naturally cooled to room temperature, removed, washed with deionized water until neutral, and dried to obtain a thallium removal agent for high-entropy heteroatom-doped biochar material.

[0071] The inert gas in S13 is nitrogen or argon.

[0072] The preparation method of this invention is simple, the operating conditions are mild, it is easy to industrialize, and no toxic or harmful substances are generated during the preparation process, which is in line with the concept of green environmental protection.

[0073] The preparation method and effects of thallium removal agent are specifically illustrated through the following multiple examples.

[0074] Example 1

[0075] A method for preparing a thallium removal agent includes the following steps:

[0076] Step 1: Wash and dry the straw, then crush it and pass it through a 100-mesh sieve to obtain biomass powder;

[0077] Step 2: Mix the biomass powder and heteroatom dopant at a mass ratio of 1:1 to obtain a mixture. The heteroatom dopant consists of urea, ammonium dihydrogen phosphate, thiourea, hydrogen peroxide, and ammonium chloride, with a molar ratio of 3:2:2:4:1.

[0078] Step 3: Place the mixture under a nitrogen atmosphere and calcine it at 700℃ for 4 hours, with a heating rate of 8℃ / min;

[0079] Step 4: After calcination, allow the product to cool naturally to room temperature, remove it, wash it with deionized water until neutral, and dry it at 80°C for 12 hours to obtain a thallium removal agent for high-entropy heteroatom-doped biochar material.

[0080] The thallium removal agent prepared above was used to remove thallium ions from thallium-containing water. The specific operation was as follows: 100 mL of simulated wastewater with a thallium concentration of 10 mg / L was taken, and 0.2 g of the thallium removal agent was added. The mixture was stirred and adsorbed at 30°C for 6 hours. After adsorption, the concentration of thallium ions in the water was measured. The results showed that the removal rate of thallium ions was 98.5%, and the adsorption capacity was 4.925 mg / g.

[0081] Example 2

[0082] A method for preparing a thallium removal agent includes the following steps:

[0083] Step 1: Wash and dry the rice husks, then crush them and pass them through an 80-mesh sieve to obtain biomass powder;

[0084] Step 2: Mix the biomass powder and heteroatom dopant at a mass ratio of 1:0.5 to obtain a mixture. The heteroatom dopant consists of melamine, diammonium hydrogen phosphate, sodium sulfate, potassium permanganate, and sodium chloride, with a molar ratio of 1:1:1:2:1.

[0085] Step 3: Place the mixture under an argon atmosphere and calcine it at 500°C for 6 hours, with a heating rate of 5°C / min;

[0086] Step 4: After calcination, allow the product to cool naturally to room temperature, remove it, wash it with deionized water until neutral, and dry it at 70°C for 15 hours to obtain a high-entropy heteroatom-doped biochar material thallium removal agent.

[0087] The thallium removal agent prepared above was used to remove thallium ions from thallium-containing water. The specific operation was as follows: 200 mL of simulated wastewater with a thallium concentration of 5 mg / L was taken, and 0.4 g of the thallium removal agent was added. The mixture was stirred and adsorbed at 20°C for 12 hours. After adsorption, the concentration of thallium ions in the water was measured. The results showed that the removal rate of thallium ions was 96.2%, and the adsorption capacity was 2.405 mg / g.

[0088] Example 3

[0089] A method for preparing a thallium removal agent includes the following steps:

[0090] Step 1: Wash and dry the peanut shells, then crush them and pass them through a 120-mesh sieve to obtain biomass powder;

[0091] Step 2: Mix the biomass powder and heteroatom dopant at a mass ratio of 1:2 to obtain a mixture. The heteroatom dopant consists of ammonium nitrate, sodium phosphate, sodium sulfide, nitric acid, and potassium chloride, with a molar ratio of 5:3:4:6:2.

[0092] Step 3: Place the mixture in a nitrogen atmosphere and calcine it at 900℃ for 2 hours, with a heating rate of 10℃ / min;

[0093] Step 4: After calcination, allow the product to cool naturally to room temperature, remove it, wash it with deionized water until neutral, and dry it at 90°C for 10 hours to obtain a thallium removal agent for high-entropy heteroatom-doped biochar material.

[0094] The thallium removal agent prepared above was used to remove thallium ions from thallium-containing water. The specific operation was as follows: 50 mL of simulated wastewater with a thallium concentration of 20 mg / L was taken, and 0.1 g of the thallium removal agent was added. The mixture was stirred and adsorbed at 40 °C for 1 hour. After adsorption, the concentration of thallium ions in the water was measured. The results showed that the removal rate of thallium ions was 97.8%, and the adsorption capacity was 9.78 mg / g.

[0095] Example 4

[0096] Adsorption-desorption cycle experiment: The thallium removal agent used in Example 1 was desorbed with 0.1 mol / L hydrochloric acid solution for 2 hours. After desorption, it was washed with deionized water until neutral and dried for use in the next adsorption experiment. The above adsorption-desorption process was repeated 5 times, and the removal rate of thallium ions in each adsorption experiment was measured. The results showed that after 5 cycles, the removal rate of thallium ions remained above 90%, indicating that the thallium removal agent has good stability and reusability.

[0097] The present invention also provides an apparatus for preparing thallium removal agent.

[0098] Please see Figures 3 to 6 An apparatus for preparing thallium removal agent includes a mixing cylinder 2, a stirring device 3, and two mounting plates 1, used in the thallium removal agent preparation method to mix biomass powder with heteroatom dopants (i.e., nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds, and chlorine-containing compounds), and further includes a lifting device 4 and a material holding structure 7;

[0099] The mixing cylinder 2 includes a main cylinder 21, a top cover 22 and a rotating structure 23. The main cylinder 21 is horizontally installed between two mounting plates 1. One side of the top cover 22 is rotatably installed on the main cylinder 21 through the rotating structure 23. Two guide rollers 221 are installed at intervals on the other side of the top cover 22.

[0100] The lifting device 4 is used to drive the top cover 22 to rotate along the rotating structure 23;

[0101] The material holding structure 7 includes a material bag 71 and two rope structures. The two rope structures are connected to both ends of the material bag 71. Each rope structure includes a main rope 72, a first branch rope 73, a second branch rope 74, and a buckle 75. The first branch rope 73 and the second branch rope 74 are respectively installed on both sides of the end of the material bag 71. One end of the main rope 72 is connected to the first branch rope 73 and the second branch rope 74, and the buckle 75 is connected to the other end of the main rope 72.

[0102] When the material-filling structure 7 is used to feed material into the mixing cylinder 2, the buckle 75 is detachably connected to the guide roller 221.

[0103] Please see Figure 3 and Figure 5 In this embodiment, the stirring device 3 includes a driving device 31, a stirring shaft 32, and multiple plow blades 33. The driving device 31 is mounted on one side of the mounting plate 1 through a mounting box. The stirring shaft 32 passes through the mixing cylinder 2 and the two mounting plates 1, and is rotatably connected to the mounting plates 1 and mechanically sealed to the mixing cylinder 2. The output end of the driving device 31 is connected to the stirring shaft 32 to drive the stirring shaft 32 to rotate. Multiple plow blades 33 are spaced apart on the stirring shaft 32.

[0104] The bottom of the main cylinder 21 is provided with a discharge pipe 211, and a gate valve is provided on the discharge pipe 211. The gate valve is used to control the connection between the discharge pipe 211 and the main cylinder 21.

[0105] Currently, when mixing solid particles with solid particles or containing liquids, commonly used mixing equipment includes plow mixers. The mixing drum 2 of a plow mixer is usually horizontally set, and the feed inlet is located at the top of the mixing drum 2. When feeding materials, it is necessary to use feeding equipment such as screw conveyors or vacuum feeders. However, for laboratory equipment, or for private purchase or small workshop use, setting up the above-mentioned feeding equipment increases costs. Usually, manual feeding to the mixing drum 2 is required, which is cumbersome. In addition, the feed inlet at the top of the mixing drum 2 is high above the ground, making feeding inconvenient.

[0106] In this embodiment, the top of the main cylinder 21 is provided with an opening that is compatible with the top cover 22;

[0107] By setting the top cover 22, the lifting device 4 lifts the top cover 22 and opens it. The mixture is added through the opening at the top of the main cylinder 21. After the top cover 22 is fully opened, the internal condition of the mixing cylinder 2 can be viewed through the opening, and the internal condition of the mixing cylinder 2 can be easily cleaned and inspected in the future.

[0108] When solid materials need to be loaded into the mixing drum 2, the solid materials are first loaded into the loading bag 71. In this embodiment, the buckle 75 at the end of the main rope 72 is sleeved on the guide roller 221. When the lifting device 4 lifts the top cover 22 and makes it rotate upward along the rotating structure 23, the top cover 22 drives the loading bag 71 to move upward through the main rope 72, the first branch rope 73 and the second branch rope 74. Thus, the lifting device 4 can be used to rotate and open the top cover 22, driving the loading bag 71 to move upward, thereby achieving the auxiliary lifting of the material. In this embodiment, the subsequent manual assistance can be used to rotate the loading bag 71 to allow the material to enter the mixing drum 2, thereby simplifying the loading operation and making loading more convenient.

[0109] In this embodiment, the buckle 75 includes a buckle ring, a buckle arm, a connecting shaft, and a torsion spring. One side of the buckle ring has an opening, and one end of the buckle arm is rotatably mounted on the buckle ring via the connecting shaft. The buckle arm blocks the opening. The torsion spring is sleeved on the connecting shaft, and its two ends are respectively connected to the buckle ring and the buckle arm.

[0110] In other embodiments, the buckle 75 may also include two half-buckles connected by bolts.

[0111] Please see Figure 5The equipment for preparing thallium removal agent also includes a spraying assembly 8, which includes a connecting pipe, multiple nozzles, a hose, a water pump, and a storage cylinder. A mounting groove is provided in the center of the top cover 22, and the connecting pipe is installed inside the mounting groove, preventing it from interacting with the rotating plow blades 33. Multiple nozzles are connected and installed at the bottom of the connecting pipe, one end of which passes through the top cover 22. The hose connects the output end of the water pump to the end of the connecting pipe located outside the top cover 22. The input end of the water pump is connected to the output end of the storage cylinder via a pipe and valve. The hose is pre-lengthened to allow the top cover 22 to be opened by flipping it over. The hose, water pump, and storage cylinder are not shown in the diagram and can be housed in a mounting box or mounted on the mounting plate 1 using brackets or similar means.

[0112] By setting up the spraying component 8, liquid raw materials, such as the hydrogen peroxide solution mentioned above, can be sprayed evenly into the mixing cylinder 2, and the solution is added into the storage cylinder.

[0113] The rotating structure 23 includes a mounting shaft, a mounting sleeve, and two mounting blocks. The two ends of the mounting shaft are mounted on the main cylinder 21 via the mounting blocks, and the mounting sleeve is mounted on the top cover 22. The mounting sleeve is fitted onto the mounting shaft to form a rotating connection. There are at least two rotating structures 23; in this example, there are two, symmetrically arranged at both ends of the mixing cylinder 2.

[0114] The guide roller 221 includes a support roller and two support plates. The two ends of the support roller are mounted on the top cover 22 through the support plates. The support roller is rotatably mounted between the two support plates. An annular groove is provided on the support roller to limit the main rope 72. A gap is left between the support roller and the top cover 22.

[0115] Please see Figure 4 In this embodiment, the lifting device 4 includes a rotating seat 41, a lifting cylinder 42, and a connecting arm 43. The lifting cylinder 42 is rotatably mounted on the mounting plate 1 via the rotating seat 41. One end of the connecting arm 43 is connected to the side of the top cover 22 away from the rotating structure 23, and the output end of the lifting cylinder 42 is rotatably connected to the other end of the connecting arm 43.

[0116] When it is necessary to open the top cover 22, the lifting cylinder 42 drives the top cover 22 to open upwards via the connecting arm 43, such as Figure 7 During the opening of the top cover 22, the lifting cylinder 42 adapts to the angle change.

[0117] One end of the connecting arm 43 is connected to the top cover 22, and the other end is equipped with a connecting shaft. The top end of the lifting cylinder 42 is sleeved on the connecting shaft to form a rotatable connection.

[0118] The rotating seat 41 includes a U-shaped frame, a rotating shaft, and a T-shaped block. The U-shaped frame is mounted on the mounting plate 1, the rotating shaft is mounted inside the U-shaped frame, and one end of the T-shaped block is sleeved on the rotating shaft to form a rotating connection. The bottom end of the lifting cylinder 42 is mounted on the T-shaped block.

[0119] The lifting cylinder 42 can be a pneumatic cylinder, a hydraulic cylinder, or an electric push cylinder.

[0120] In this embodiment, there are two lifting devices 4, which are respectively installed on two mounting plates 1.

[0121] In other embodiments, the lifting device 4 includes a motor and a mounting bracket. The motor is mounted on the mounting plate 1 via the mounting bracket. The output end of the motor is connected to the mounting shaft in the rotating structure 23. By driving the mounting shaft to rotate, the top cover 22 is rotated and opened.

[0122] Please see Figure 3 Below the mixing drum 2, and on the side near the guide roller 221, there is a support 6. When feeding, the filling bag 71 can be placed on the support 6 to increase the starting height of the filling bag 71. By setting support 6 of different heights, the starting height of the filling bag 71 can be adjusted.

[0123] Please refer to it again. Figure 4 As a preferred embodiment, the thallium removal agent preparation equipment further includes a rope winding structure 5, which includes a rotating device 51, a rotating shaft 52, and a winding frame 53. The rotating shaft 52 passes through and is rotatably mounted on the mounting plate 1. The winding frame 53 is mounted on one end of the rotating shaft 52 and is located below the guide roller 221. The rotating device 51 is used to drive the rotating shaft 52 to rotate.

[0124] When the material holding structure 7 is used to feed material into the mixing cylinder 2, the main rope 72 passes through the guide roller 221 and the buckle 75 is detachably connected to the winding frame 53.

[0125] In this embodiment, the winding frame 53 includes an H-shaped frame and multiple winding shafts. The multiple winding shafts are installed at intervals inside the H-shaped frame, and the middle of the H-shaped frame is sleeved and fixed on the rotating shaft 52.

[0126] By setting the rope winding structure 5, when adding solid materials into the mixing drum 2, the buckle 75 and the main rope 72 are passed through the gap between the guide roller 221 and the top cover 22, and then the buckle 75 is sleeved on the winding shaft at the far end of the winding frame 53; when the lifting device 4 drives the side of the top cover 22 equipped with the guide roller 221 to rotate upward, the guide roller 221 pulls up the main rope 72, and pulls up the filling bag 71 through the first branch rope 73 and the second branch rope 74. At the same time, the rotating device 51 drives the rotating shaft 52 to rotate, driving the winding frame 53 to rotate, thereby winding the main rope 72, further increasing the height of the lifting of the filling bag 71, so that the filling bag 71 can be suspended at the opening of the main drum 21, such as Figure 7 (a) and Figure 7 In section (b), the material can be directly conveyed to the opening of the main cylinder 21 without manual lifting or the need to set the starting height of the filling bag 71 to be relatively high.

[0127] When feeding is complete, the lifting device 4 lowers the top cover 22, and at the same time the rotating device 51 drives the rotating shaft 52 to rotate the winding frame 53 in the opposite direction to release the main rope 72. Afterwards, the buckle 75 can be removed from the winding frame 53 and then passed through the guide roller 221. Afterwards, the filling bag 71 can be removed. When removing the bag, the remaining material in the filling bag 71 can be poured out.

[0128] The top cover 22 is opened to the center position of the guide roller 221 corresponding to the main cylinder 21.

[0129] Corresponding to the guide roller 221, there are two rope winding structures 5, with two winding frames 53 located outside the two guide rollers 221. That is, the distance between the two winding frames 53 is slightly larger than that between the two guide rollers 221, so that the winding frames 53 will not block the upward movement of the filling bag 71.

[0130] As an optional embodiment, the rotating device 51 includes a motor and a mounting bracket (not shown in the schematic diagram). The motor is mounted on the mounting plate 1 via the mounting bracket, and the output shaft of the motor is connected to the rotating shaft 52. The rotating shaft 52 is driven to rotate by the motor.

[0131] As another optional embodiment, the rotating device 51 includes a toothed plate 511 and a gear 512. The gear 512 is mounted on the rotating shaft 52, and the toothed plate 511 is vertically slidably mounted on the mounting plate 1. The toothed plate 511 meshes with the gear 512. The rope winding structure 5 also includes a driving rope 55, which connects the toothed plate 511 to the output end of the lifting cylinder 42.

[0132] When the lifting cylinder 42 lifts the top cover 22 to open, the output end of the lifting cylinder 42 simultaneously pulls the driving rope 55 to move upward, the driving rope 55 drives the toothed plate 511 to move upward, the toothed plate 511 drives the gear 512 to rotate, and the gear 512 drives the winding frame 53 to rotate through the rotating shaft 52, thereby realizing the winding of the main rope 72 and further raising the height of the filling bag 71.

[0133] Thus, by using the lifting cylinder 42 to open the top cover 22, the filling bag 71 is lifted and the winding frame 53 is driven to rotate, further increasing the height of the filling bag 71.

[0134] Please refer to Figure 4 A limit roller 101 is installed on the mounting plate 1 to limit the drive rope 55, so that the lower part of the drive rope 55 is kept vertical with the toothed plate 511, thereby keeping the force of the bottom end of the drive rope 55 lifting the toothed plate 511 vertical.

[0135] When the winding frame 53 releases the main rope 72, after the top cover 22 descends, the downward gravity of the toothed plate 511 can drive the gear 512 to rotate, thereby driving the winding frame 53 to rotate and release the main rope 72. During this process, depending on the situation, manual assistance can be provided to push the toothed plate 511 down or rotate the winding frame 53 to release the main rope 72.

[0136] Please see Figure 3 and Figure 8 A limiting plate 54 is installed on the mounting plate 1, and a toothed plate 511 is sleeved on the limiting plate 54 to form a vertical sliding connection; through the vertical sliding connection, the toothed plate 511 can be limited in the horizontal direction, so that the toothed plate 511 can only slide in the vertical direction.

[0137] Alternatively, a slide rail can be vertically installed on the mounting plate 1, and a slide groove can be opened on one side of the toothed plate 511. The slide rail and the toothed plate 511 can be slidably assembled through the slide groove to form a vertical sliding connection with the mounting plate 1.

[0138] Please see Figure 6 In a preferred embodiment, the first branch rope 73 includes a connecting rope 731, a collar 732 and an L-shaped hook 733. One end of the connecting rope 731 is connected to the filling bag 71, the collar 732 is installed at the other end of the connecting rope 731, and the L-shaped hook 733 is installed on the main rope 72.

[0139] An abutment plate 222 is provided on the inner wall of the top cover 22 at a position corresponding to the guide roller 221.

[0140] By making the first rope 73 detachable, see [link to relevant documentation]. Figure 7During the process of the main rope 72 driving the filling bag 71 upward through the first branch rope 73 and the second branch rope 74, the filling bag 71 initially moves along the side wall of the main cylinder 21. When the filling bag 71 moves to the point of separation from the main cylinder 21, the filling bag 71 is subjected to gravity and swings towards the center of the main cylinder 21. The abutment plate 222 limits the L-shaped hook 733. Since the L-shaped hook 733 cannot move towards the center of the main cylinder 21, the entire filling bag 71 drives the connecting rope 731 to continue moving towards the center of the main cylinder 21. As a result, the collar 732 on the connecting rope 731 separates from the L-shaped hook 733. At this time, the side of the filling bag 71 with the connecting rope 731 tilts downward, and the material enters the main cylinder 21, realizing automatic feeding.

[0141] If the collar 732 and the L-shaped hook 733 become detached during use, a tool can be used to push the connecting rope 731 to separate the collar 732 from the L-shaped hook 733. The tool can be a T-shaped rod, etc.

[0142] When placing the filling bag 71 onto the support 6, the first rope 73 should be oriented toward the mixing drum 2.

[0143] When removing the material bag 71, pour the remaining material into the mixing drum 2;

[0144] In other embodiments, the filling bag 71 can be divided into a side circumference and a bottom bag. One side of the top of the bottom bag is fixedly connected to the side circumference, and the other three sides of the top are detachably connected to the side circumference. The connection can be made by a zipper or a male and female buckle. When unloading, the worker opens the zipper or the male and female buckle to unload the material.

[0145] The working principle of the thallium removal agent preparation equipment provided by this invention is as follows:

[0146] When it is necessary to fill the inside of the mixing drum 2 with solid materials, place the filling bag 71 on the support 6, and fill the filling bag 71 with solid materials (biomass powder and nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds and chlorine-containing compounds). Depending on the situation, the material can be filled at once or multiple times.

[0147] The buckle 75 and the main rope 72 are passed through the gap between the guide roller 221 and the top cover 22, and then the buckle 75 is sleeved on the winding shaft at the far end of the winding frame 53; when the lifting device 4 drives the side of the top cover 22 equipped with the guide roller 221 to rotate upward, the guide roller 221 pulls up the main rope 72, and pulls up the filling bag 71 through the first branch rope 73 and the second branch rope 74.

[0148] At the same time, the output end of the lifting cylinder 42 pulls the driving rope 55 upward, which in turn drives the toothed plate 511 upward. The toothed plate 511 drives the gear 512 to rotate, and the gear 512 drives the winding frame 53 to rotate via the rotating shaft 52, thereby achieving winding of the main rope 72 and further raising the height of the filling bag 71 so that the filling bag 71 can be suspended on the opening of the main cylinder 21. Figure 7 (a) and Figure 7 In section (b), materials can be directly conveyed to the opening of the main cylinder 21.

[0149] During the process of the main rope 72 driving the filling bag 71 upward through the first branch rope 73 and the second branch rope 74, the filling bag 71 initially moves along the side wall of the main cylinder 21. When the filling bag 71 moves to the point of separation from the main cylinder 21, the filling bag 71 is subjected to gravity and swings towards the center of the main cylinder 21. The abutment plate 222 limits the L-shaped hook 733. Since the L-shaped hook 733 cannot move towards the center of the main cylinder 21, the entire filling bag 71 drives the connecting rope 731 to continue moving towards the center of the main cylinder 21. As a result, the collar 732 on the connecting rope 731 separates from the L-shaped hook 733. At this time, the side of the filling bag 71 with the connecting rope 731 tilts downward, and the material enters the main cylinder 21, realizing automatic feeding.

[0150] If the collar 732 and the L-shaped hook 733 become detached during use, a tool can be used to push the connecting rope 731 to separate the collar 732 and the L-shaped hook 733.

[0151] When feeding is complete, the lifting device 4 lowers the top cover 22, and at the same time the rotating device 51 drives the rotating shaft 52 to rotate the winding frame 53 in the opposite direction to release the main rope 72. Afterwards, the buckle 75 can be removed from the winding frame 53 and then passed through the guide roller 221. Afterwards, the filling bag 71 can be removed. When removing the bag, the remaining material in the filling bag 71 can be poured out.

[0152] Subsequently, hydrogen peroxide solution is added into the mixing cylinder 2 via the spraying component 8;

[0153] After the material is added, the drive device 31 drives the stirring shaft 32 to rotate the plow blade stirring blade 33 to carry out the stirring work.

[0154] After mixing is complete, the mixture is discharged through discharge pipe 211.

[0155] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A method for treating wastewater containing thallium, characterized by, The method comprises the following steps: S1, the wastewater containing thallium is introduced into the treatment tank; S2, a thallium removal agent is added into the wastewater treatment tank, and the solid-liquid ratio of the thallium removal agent to the wastewater containing thallium is 1:(10-100) g / L; The thallium removal agent comprises biochar and five compounds containing nitrogen, phosphorus, sulfur, oxygen and chlorine, the mass ratio of the biochar to the five compounds is 1:(0.5-2), and the molar ratio of nitrogen, phosphorus, sulfur, oxygen and chlorine is (1-5):(1-3):(1-4):(2-6):(1-2); S3, the wastewater containing thallium is stirred at 20-40℃, the thallium element in the wastewater is adsorbed by the thallium removal agent, and the adsorption time is 1-12 hours; S4, the wastewater treated by the thallium removal agent is discharged.

2. The method according to claim 1, wherein, The biochar is prepared from agricultural waste, and the agricultural waste is at least one of straw, rice husk and peanut shell.

3. The method according to claim 1, wherein the thallium-containing wastewater is a wastewater containing thallium (I) and thallium (III) ions. The five compounds containing nitrogen, phosphorus, sulfur, oxygen and chlorine are urea, ammonium dihydrogen phosphate, thiourea, hydrogen peroxide and ammonium chloride, respectively.

4. A method for preparing a thallium removing agent, characterized by, The method for preparing the thallium removal agent used in the method for treating wastewater containing thallium according to any one of claims 1-3 comprises the following steps: S11, the agricultural waste is washed, dried and then crushed to obtain biomass powder by sieving; S12, the biomass powder is uniformly mixed with a heteroatom dopant according to a mass ratio of 1:(0.5-2) to obtain a mixture, the heteroatom dopant being a nitrogen-containing compound, a phosphorus-containing compound, a sulfur-containing compound, an oxygen-containing compound and a chlorine-containing compound; S13, the mixture is placed in an inert gas and calcined at 500-900℃ for 2-6 hours, and the temperature rising rate is 5-10℃ / min; S14, after the calcination is completed, the product is naturally cooled to room temperature, washed with deionized water until neutral, and then dried to obtain the thallium removal agent of high-entropy heteroatom doped biochar material.

5. The method for preparing the thallium removal agent according to claim 4, characterized in that, The inert gas in S is nitrogen or argon.

6. A device for preparing a thallium removing agent, comprising a mixing cylinder, a stirring device, and two mounting plates, characterized in that, The method for preparing the thallium removal agent according to any one of claims 4-5 further comprises a cover lifting device and a material containing structure; The mixing cylinder comprises a main cylinder body, a top cover and a rotating structure, the main cylinder body is horizontally installed between the two mounting plates, one side of the top cover is rotatably installed on the main cylinder body through the rotating structure, and the other side of the top cover is spacedly installed with two guide rollers; The cover lifting device is used to drive the top cover to rotate along the rotating structure; The material containing structure comprises a material containing bag and two rope structures, the two rope structures are connected at two ends of the material containing bag, the rope structure comprises a main rope and a first branch rope, a second branch rope and a buckle, the first branch rope and the second branch rope are respectively installed on the two sides of the end portions of the material containing bag, one end of the main rope is connected with the first branch rope and the second branch rope, and the buckle is connected at the other end of the main rope; When the material containing structure is used to load materials into the interior of the mixing cylinder, the buckle is detachably connected with the guide rollers.

7. The apparatus for preparing a thallium removing agent according to claim 6, wherein The cover lifting device comprises a rotating seat, a lifting cylinder and a connecting arm, the lifting cylinder is rotatably installed on the mounting plate through the rotating seat, one end of the connecting arm is connected with the side of the top cover away from the rotating structure, and the output end of the lifting cylinder is rotatably connected with the other end of the connecting arm.

8. The apparatus for preparing a thallium removing agent according to claim 7, wherein The device for preparing the thallium removing agent further comprises a rope collecting structure, the rope collecting structure comprises a rotating device, a rotating shaft and a winding frame, the rotating shaft is installed through and rotates on the mounting plate, the winding frame is installed on one end of the rotating shaft and is located below the guide roller, and the rotating device is used to drive the rotating shaft to rotate. When the material loading structure is used to load the inside of the mixing cylinder, the buckle is detachably connected with the winding frame after the main rope passes through the guide roller.

9. The apparatus for preparing a thallium removing agent according to claim 8, wherein The rotating device comprises a gear plate and a gear, the gear is installed on the rotating shaft, the gear plate is vertically and slidingly installed on the mounting plate, the gear plate is engaged with the gear, and the rope collecting structure further comprises a driving rope, the driving rope is connected with the gear plate and the output end of the lifting cylinder.

10. The apparatus for preparing a thallium removing agent according to claim 6, wherein The first branch rope comprises a connecting rope, a thimble and an L-shaped hook, one end of the connecting rope is connected with the loading bag, the thimble is installed on the other end of the connecting rope, and the L-shaped hook is installed on the main rope. An abutting plate is arranged on the inner wall of the top cover and corresponds to the position of the guide roller.

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