High-efficiency treating agent, treating process and system for coal mine production sewage

Abstract

The application discloses a kind of coal mine production sewage with efficient treating agent, treating process and system, the treating agent includes modified flocculant and multifunctional adjuvant.The efficient treating agent for coal mine production sewage provided in the application is a two-component reagent that can well cope with the water quality characteristics of coal mine production sewage, achieving the removal of suspended solids, organic pollutants and heavy metal ions in the water body, and can efficiently kill bacteria in the water body, achieving excellent pollution treatment effect.The multifunctional adjuvant of the application forms a composite system with both sonosensitization and photosensitization catalysis, combining photocatalysis and ultrasonic catalysis to treat sewage, which can cooperate with each other, photocatalysis can efficiently produce reactive oxygen, and disperse to each area of the water body through ultrasonic effect, ultrasonic effect can penetrate to the blind area that light cannot irradiate, assisting photocatalysis to achieve deep purification of the whole area of the water body, the combination of photocatalysis and ultrasonic catalysis can achieve more efficient sewage treatment with relatively lower energy consumption.

Description

Technical Field

[0001] This invention relates to the field of mining technology, and in particular to a high-efficiency treatment agent, treatment process and system for coal mine production wastewater. Background Technology

[0002] Wastewater from coal mines mainly includes pollution generated during mining and coal washing. Besides suspended solids such as coal slag, gangue, sand, and coal ash that are difficult to settle, the wastewater also contains significant amounts of sulfur- and carbon-containing organic pollutants and heavy metal ions. For example, chemicals added during coal washing, such as oil collectors, and oils and petroleum substances produced during mining are major sources of organic pollutants. Heavy metal ions primarily originate from chemicals added during coal washing and the leaching of metal ions from the coal mine. Furthermore, the use of phosphonic acid collectors and pH adjusters (such as phosphoric acid and sodium hexametaphosphate) during coal washing can also cause phosphorus pollution in the water.

[0003] In summary, the characteristics of coal mine wastewater are: a wide variety of pollutants, including suspended solids (SS), organic matter, heavy metal ions, and phosphorus. Traditional coal mine wastewater treatment processes commonly use flocculants such as polyaluminum chloride for flocculation and sedimentation to remove pollutants. However, this method has drawbacks such as long flocculation and sedimentation times, loose flocs that easily disperse and reform as suspended solids when shaken, and poor treatment effectiveness for organic matter, heavy metal ions, and phosphorus. Therefore, additional subsequent processes are often required, such as multiple filtrations or sedimentation, or biological treatment.

[0004] Patent CN110577265A discloses a coal washing wastewater treatment agent and its preparation method. It uses a compound agent composed of polyacrylamide, magnesium polyacrylate polymer, magnesium chloride, and calcium chloride for flocculation and sedimentation, which can enhance floc stability and improve flocculation and sedimentation effects to a certain extent. However, it does not improve the removal capacity for organic matter and heavy metal ions.

[0005] Patent CN120288916A discloses a polyaluminum chloride composite water treatment agent and its preparation method. Through the synergistic effect of polyaluminum chloride and a natural polymer composite system, it can improve floc performance, enhance turbidity removal rate, COD removal rate, and heavy metal adsorption capacity, while also possessing broad-spectrum antibacterial and biodegradable properties. However, overall, its COD removal rate and antibacterial rate still need further improvement, and it does not specifically address the removal of phosphorus (P).

[0006] Patent CN109650639A discloses a coal mine wastewater treatment and recycling process, including sedimentation, aeration, filtration, secondary filtration, and high-temperature sterilization. However, it has drawbacks such as a long process flow and high energy consumption for high-temperature sterilization.

[0007] Therefore, it is now necessary to improve existing technologies to provide more reliable solutions. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to provide a high-efficiency treatment agent, treatment process and system for coal mine production wastewater, which addresses the shortcomings of the prior art.

[0009] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: In the first aspect of the present invention, a high-efficiency treatment agent for coal mine production wastewater is provided, including a modified flocculant and a multifunctional auxiliary agent. When using the agent, the modified flocculant and the multifunctional auxiliary agent are added to the wastewater in a mass ratio of 5:1 to 1:2, and the wastewater is treated under the simultaneous application of ultrasound and light. The modified flocculant is carbon nanotubes and lanthanum-doped polyaluminum chloride; The multifunctional excipient was prepared by the following method: S1. Mesoporous iron oxide is synthesized in situ on attapulgite to obtain magnetically modified adsorption particles. Then, cerium-doped titanium dioxide is loaded onto the magnetically modified adsorption particles to prepare acoustically functionalized adsorption particles. S2. Deposit manganese-doped carbon dots on MXene to prepare carbon dot-MXene composites; S3. Assemble carbon dot-MXene complex with acoustically functionalized adsorbent particles to prepare acoustic-optic dual-response adsorbent particles, i.e., multifunctional excipients.

[0010] Preferably, the multifunctional excipient is prepared by the following method: S1. Preparation of acoustically functionalized adsorption particles: S1-1. Add attapulgite to hydrochloric acid solution, heat and stir under reflux, filter, wash until neutral, dry, grind, and microwave to obtain activated attapulgite. S1-2. Disperse Fe(NO3)2, Fe(NO3)3, and activated attapulgite in deionized water, adjust the pH to 8-9 with ammonia, stir the reaction, transfer the resulting product to a reaction vessel, react at 170-190℃ for 3-12 hours, filter, wash, and dry to obtain magnetically modified adsorption particles. S1-3. Disperse the magnetically modified adsorption particles, tetrabutyl titanate, and cerium nitrate in methanol, then add sodium hydroxide aqueous solution, stir, transfer the resulting mixture into a reaction vessel, react at 120-150℃ for 3-10 h, filter, wash, and dry to obtain acoustically functionalized adsorption particles. S2. MXene powder, salicylic acid, and manganese acetate are dispersed in deionized water to obtain precursor solution 1; chitosan, L-arginine, p-phenylenediamine, and ethanol are added to deionized water and stirred to obtain precursor solution 2; precursor solution 2 is added to precursor solution 1 under stirring and ultrasonically dispersed; the resulting mixture is added to a reaction vessel and reacted at 180-225℃ for 4-10 h; centrifuged; and the solid product is freeze-dried to obtain carbon dot-MXene complex. S3. Add the acoustically functionalized adsorbent particles to a nitric acid solution, stir, filter, wash, and redisperse the resulting solid in deionized water to obtain dispersion 1; disperse the carbon dot-MXene complex in deionized water to obtain dispersion 2; add dispersion 2 dropwise to dispersion 1 while stirring, stir, let stand, filter, and freeze-dry the solid product to obtain acoustically and optically responsive adsorbent particles, i.e., multifunctional excipients.

[0011] Preferably, step S1 specifically includes: S1-1. Add attapulgite to a 0.2-5 mol / L hydrochloric acid solution, stir and reflux at 70-100℃ for 2-8 hours, filter, wash until neutral, dry, grind, place the acidified attapulgite in a crucible, and treat at 500-800W for 2-8 minutes to obtain activated attapulgite. S1-2. Add 0.005-0.02 mol Fe(NO3)2, 0.01-0.04 mol Fe(NO3)3, and 2.5-10 g activated attapulgite to 100-300 mL of deionized water and ultrasonically disperse for 0.5-2 h. Adjust the pH to 8-9 by adding ammonia dropwise while stirring, and stir the reaction for 30-90 min. Transfer the obtained product to a reaction vessel and react at 170-190℃ for 3-12 h. Cool to room temperature, filter, wash, and dry to obtain magnetically modified adsorption particles. S1-3. Add 1-4g of magnetically modified adsorption particles, 1.1-4.25mL of tetrabutyl titanate, and 0.24-0.96g of cerium nitrate to 50-200mL of methanol and ultrasonically disperse for 0.5-2h. Then add 15-60mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL and stir for 15-60min. Transfer the resulting mixture to a reaction vessel and react at 120-150℃ for 3-10h. Filter, wash, and dry to obtain acoustically functionalized adsorption particles.

[0012] Preferably, step S2 specifically includes: Add 0.5-2g MXene powder, 0.07-0.28g salicylic acid, and 0.175-0.7g manganese acetate to 25-100mL of deionized water and sonicate at 60-80℃ for 0.5-2h to obtain precursor solution 1. Add 0.35-1.5g chitosan, 0.26-1.04g L-arginine, 0.16-0.64g p-phenylenediamine, and 25-100mL ethanol to 25-100mL of deionized water and stir for 5-30min to obtain precursor solution 2. Add precursor solution 2 to precursor solution 1 with stirring and sonicate for 10-40min. Add the resulting mixture to a reaction vessel and react at 180-225℃ for 4-10h. Centrifuge and freeze-dry the solid product to obtain the carbon dot-MXene complex.

[0013] Preferably, step S3 specifically includes: Add 1-4g of acoustically functionalized adsorbent particles to 25-100mL of 1mol / L nitric acid solution, stir for 30-90min, filter, wash, and add the resulting solid to 25-100mL of deionized water. Sonicate for 15-60min to obtain dispersion 1. Add 0.75-3g of carbon dot-MXene complex to 25-100mL of deionized water and sonicate for 15-60min to obtain dispersion 2. Add dispersion 2 dropwise to dispersion 1 under stirring, completing the addition within 30-90min. Stir for 0.5-2h, let stand for 2-6h, filter, and freeze-dry the solid product to obtain acoustically and optically responsive adsorbent particles, i.e., the multifunctional excipient.

[0014] Preferably, the multifunctional excipient is prepared by the following method: S1. Preparation of acoustically functionalized adsorption particles: S1-1. Add 10g of 200-mesh attapulgite to 200mL of 1mol / L hydrochloric acid solution, stir and reflux at 90℃ for 4h, filter, wash with deionized water until neutral, dry at 100℃, grind, and treat the acidified attapulgite in a microwave oven at 700W for 4min to obtain activated attapulgite. S1-2. Add 0.01mol Fe(NO3)2, 0.02mol Fe(NO3)3, and 5g activated attapulgite to 150mL of deionized water and ultrasonically disperse for 1h. Adjust the pH to 8 by adding 20wt% ammonia water dropwise while stirring. Stir the reaction for 45min. Transfer the obtained product to a reaction vessel and react at 180℃ for 6h. Cool, filter, wash the solid product with deionized water, and vacuum dry at 100℃ for 8h to obtain magnetically modified adsorption particles. S1-3. Add 2g of magnetically modified adsorption particles, 2.125mL of tetrabutyl titanate, and 0.48g of cerium nitrate to 100mL of methanol and ultrasonically disperse for 1h. Then add 30mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL and stir for 30min. Transfer the resulting mixture to a reaction vessel and react at 140℃ for 5h. Cool to room temperature, filter, wash with deionized water, and vacuum dry at 80℃ for 12h to obtain acoustically functionalized adsorption particles. S2. Add 1g MXene powder, 0.14g salicylic acid, and 0.35g manganese acetate to 50mL of deionized water and sonicate at 70℃ for 1h to obtain precursor solution 1; add 0.75g chitosan, 0.522g L-arginine, 0.324g p-phenylenediamine, and 50mL ethanol to 50mL of deionized water and stir for 15min to obtain precursor solution 2; add precursor solution 2 to precursor solution 1 with stirring and sonicate for 20min. Add the resulting mixture to a reaction vessel and react at 200℃ for 7h. Cool, centrifuge, and freeze-dry the solid product to obtain carbon dot-MXene complex. Among them, MXene powder is T3C2T x MXene powder.

[0015] S3. Add 2g of acoustically functionalized adsorption particles to 50mL of 1mol / L nitric acid solution, stir for 45min, filter and wash, add the obtained solid to 50mL of deionized water, and sonicate for 30min to obtain dispersion 1; add 1.5g of carbon dot-MXene complex to 50mL of deionized water, and sonicate for 30min to obtain dispersion 2; add dispersion 2 dropwise to dispersion 1 under stirring, and complete the addition within 45min, stir for 1h, let stand for 4h, filter, and freeze-dry the solid product to obtain acoustically and optically responsive adsorption particles, i.e., the multifunctional excipient.

[0016] Preferably, the MXene powder is T3C2T. x MXene powder, prepared by the following method: 1 g of Ti3AlC2 was added to 70 mL of 30% hydrofluoric acid solution, and the mixture was stirred at 40 °C for 48 h. The product was washed with deionized water by centrifugation until the pH of the supernatant was 5-6. The precipitate was collected, dried under vacuum at 70 °C overnight, and ground to obtain T3C2T. x MXene powder.

[0017] Preferably, the modified flocculant is prepared by the following method: 1) After ultrasonic treatment of carbon nanotubes in hydrogen peroxide, they are placed in a mixed acid composed of sulfuric acid and nitric acid, heated and stirred, filtered, washed with deionized water until neutral, and dried to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixture; add acidified carbon nanotubes to the mixture and disperse by ultrasonication to obtain a base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixture to 2-2.5, react under heating, centrifuge, wash the solid product with deionized water, and dry to obtain the modified flocculant.

[0018] Preferably, the modified flocculant is prepared by the following method: 1) 0.5g of carbon nanotubes were ultrasonically treated in 100mL of 20%wt hydrogen peroxide for 1h, filtered, and then placed in 100mL of a mixed acid consisting of 95wt% sulfuric acid and 65wt% nitric acid in a volume ratio of 3:1. The mixture was stirred at 70℃ for 4h, filtered, washed with deionized water until neutral, and vacuum dried at 90℃ for 12h to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixed solution with aluminum chloride and lanthanum nitrate concentrations of 0.5 mol / L and 0.05 mol / L, respectively; add 2 g of acidified carbon nanotubes to 100 mL of the mixed solution and ultrasonically disperse for 1 h to obtain the base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixed solution to 2, react at 70 °C for 24 h, centrifuge, wash the solid product with deionized water, and vacuum dry at 80 °C for 12 h to obtain the modified flocculant.

[0019] A second aspect of the present invention provides a coal mine wastewater treatment process, which uses the high-efficiency coal mine wastewater treatment agent described above for treatment, and the process includes the following steps: Add the multifunctional auxiliary agent dispersion to the wastewater at a ratio of 2-10g / L wastewater, stir for 5-30 minutes, then treat with ultrasound and light simultaneously for 5-90 minutes. After that, add the modified flocculant to the wastewater at a ratio of 2.5-30g / L wastewater, remove the ultrasound, and carry out coagulation and sedimentation treatment for 0.5-2 hours.

[0020] In a third aspect, the present invention provides a coal mine wastewater treatment system that uses the process described above for wastewater treatment.

[0021] The beneficial effects of this invention are: This invention provides a high-efficiency treatment agent for coal mine wastewater and a wastewater treatment process based on the agent. The high-efficiency treatment agent for coal mine wastewater provided in this invention is a two-component reagent, including a modified flocculant and a multifunctional adjuvant that can work together. It can effectively address the water quality characteristics of coal mine wastewater, remove suspended solids, organic pollutants, and heavy metal ions from the water, and efficiently kill bacteria in the water, thus achieving excellent pollution treatment results.

[0022] The modified flocculant in this invention is carbon nanotubes and lanthanum-doped polyaluminum chloride. Through the modification of carbon nanotubes and cerium, the stability of polyaluminum chloride can be improved and the flocculation effect can be enhanced by promoting the formation of a network structure in the modified flocculant system. It can also enhance the adsorption effect to a certain extent and improve the removal rate of pollutants in water. The multifunctional adjuvant in this invention is an adsorbent particle with dual acoustic and optical response characteristics, obtained by sequentially modifying attapulgite as a matrix through magnetic modification, acoustic functionalization modification, and photosensitive functionalization modification. In addition to its excellent physical adsorption capacity, it also has the ability to generate active oxygen under ultrasound or light irradiation, thus endowing it with the characteristics of chemically removing organic pollutants through active oxygen generation and bactericidal properties, which can improve the purification effect of pollution. Simultaneously, the modified flocculant and the multifunctional adjuvant can interact during the process, intertwining and connecting to form a network structure, forming larger and more stable flocs, which can improve flocculation stability, accelerate sedimentation, and enhance the "net-trapping and sweeping effect" of the flocculant. This can improve the defects of polyaluminum chloride, such as loose floc structure, easy back-turbidity, and poor sedimentation performance.

[0023] The multifunctional adjuvant of this invention forms a composite system that combines acoustic and photocatalytic catalysis. It treats wastewater by combining the dual effects of photocatalysis and ultrasonic catalysis. The two systems work synergistically. Photocatalysis can efficiently generate active oxygen and disperse it to various areas of the water body through ultrasonic action. Ultrasonic action can penetrate into blind areas that cannot be reached by light. In conjunction with photocatalysis, it can achieve deep purification of the entire water body. The combination of photocatalysis and ultrasonic catalysis can achieve more efficient wastewater treatment with relatively lower energy consumption. Attached Figure Description

[0024] Figure 1 The results show the test results of the singlet oxygen generation capacity of the multifunctional adjuvant in Example 1 under different treatment conditions; Figure 2 The test results of the singlet oxygen generation capacity of the multifunctional excipients prepared in Examples 1-3 and Comparative Examples 4-8 under the combined action of ultrasound and light irradiation; Figure 3 The infrared spectrum of the modified flocculant prepared in Example 1; Figure 4 The infrared spectrum of the multifunctional excipient prepared in Example 1; Figure 5 The results of SS removal rate tests are for the examples and comparative examples; Figure 6 The COD removal rate test results are for the examples and comparative examples; Figure 7 The results of BOD removal rate tests are shown in the examples and comparative examples; Figure 8The results of metal ion removal rate tests are for the examples and comparative examples; Figure 9 The results of total phosphorus removal rate tests for the examples and comparative examples are shown below; Figure 10 The sterilization rate test results are for the examples and comparative examples. Detailed Implementation

[0025] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0026] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0027] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. For examples where specific conditions are not specified, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments whose manufacturers are not specified, they are all commercially available products.

[0028] This invention provides a high-efficiency treatment agent for coal mine production wastewater, comprising a modified flocculant and a multifunctional auxiliary agent. When using the agent, the modified flocculant and the multifunctional auxiliary agent are added to the wastewater in a mass ratio of 5:1 to 1:2, and the wastewater is treated under the simultaneous application of ultrasound and light.

[0029] In this invention, the modified flocculant is carbon nanotubes and lanthanum-doped polyaluminum chloride, prepared by the following method: 1) Sonicate 0.25-1g of carbon nanotubes in 50-200mL of 20%wt hydrogen peroxide for 0.5-2h, filter, and place in 50-200mL of a mixed acid consisting of 95wt% sulfuric acid and 65wt% nitric acid in a volume ratio of 3:1. Stir at 60-85℃ for 2-8h, filter, wash with deionized water until neutral, and vacuum dry at 70-100℃ for 6-24h to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixed solution with aluminum chloride concentration of 0.25-1 mol / L and lanthanum nitrate concentration of 0.025-0.1 mol / L. Add 1-4 g of acidified carbon nanotubes to 100 mL of the mixed solution and ultrasonically disperse for 0.5-2 h to obtain the base solution. Add Na2CO3 to the base solution to adjust the alkalinity of the mixed solution to 2-2.5. React at 60-80℃ for 12-48 h, centrifuge, wash the solid product with deionized water, and vacuum dry at 70-100℃ for 6-24 h to obtain the modified flocculant.

[0030] In this invention, the multifunctional adjuvant is an acousto-optic dual-response adsorption particle, which is prepared by the following method: S1. Mesoporous iron oxide was synthesized in situ on attapulgite to obtain magnetically modified adsorbent particles. Then, cerium-doped titanium dioxide was loaded onto the magnetically modified adsorbent particles to prepare acoustically functionalized adsorbent particles. S1-1, Attapulgite activation treatment: Add attapulgite to a 0.2-5 mol / L hydrochloric acid solution, stir and reflux at 70-100℃ for 2-8 hours, filter, wash until neutral, dry, grind, place the acidified attapulgite in a crucible, and treat at 500-800W for 2-8 minutes to obtain activated attapulgite. S1-2. In-situ synthesis of mesoporous iron oxide on attapulgite: Add 0.005-0.02 mol Fe(NO3)2, 0.01-0.04 mol Fe(NO3)3, and 2.5-10 g activated attapulgite to 100-300 mL of deionized water and ultrasonically disperse for 0.5-2 h. Adjust the pH to 8-9 by adding ammonia dropwise while stirring, and stir the reaction for 30-90 min. Transfer the obtained product to a reaction vessel and react at 170-190℃ for 3-12 h. Cool to room temperature, filter, wash, and dry to obtain magnetically modified adsorption particles. S1-3, Loading cerium-doped titanium dioxide onto magnetically modified adsorption particles: Add 1-4g of magnetically modified adsorption particles, 1.1-4.25mL of tetrabutyl titanate, and 0.24-0.96g of cerium nitrate to 50-200mL of methanol and ultrasonically disperse for 0.5-2h. Then add 15-60mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL and stir for 15-60min. Transfer the resulting mixture to a reaction vessel and react at 120-150℃ for 3-10h. Filter, wash, and dry to obtain acoustically functionalized adsorption particles.

[0031] S2. Deposit manganese-doped carbon dots on MXene to prepare carbon dot-MXene composites: Add 0.5-2g MXene powder, 0.07-0.28g salicylic acid, and 0.175-0.7g manganese acetate to 25-100mL of deionized water and sonicate at 60-80℃ for 0.5-2h to obtain precursor solution 1. Add 0.35-1.5g chitosan, 0.26-1.04g L-arginine, 0.16-0.64g p-phenylenediamine, and 25-100mL ethanol to 25-100mL of deionized water and stir for 5-30min to obtain precursor solution 2. Add precursor solution 2 to precursor solution 1 with stirring and sonicate for 10-40min. Add the resulting mixture to a reaction vessel and react at 180-225℃ for 4-10h. Centrifuge and freeze-dry the solid product to obtain the carbon dot-MXene complex.

[0032] S3. Assemble the carbon dot-MXene complex with acoustically functionalized adsorbent particles to prepare acousto-optically responsive adsorbent particles: Add 1-4g of acoustically functionalized adsorbent particles to 25-100mL of 1mol / L nitric acid solution, stir for 30-90min, filter, wash, and add the resulting solid to 25-100mL of deionized water. Sonicate for 15-60min to obtain dispersion 1. Add 0.75-3g of carbon dot-MXene complex to 25-100mL of deionized water and sonicate for 15-60min to obtain dispersion 2. Add dispersion 2 dropwise to dispersion 1 under stirring, completing the addition within 30-90min. Stir for 0.5-2h, let stand for 2-6h, filter, and freeze-dry the solid product to obtain acoustically and optically responsive adsorbent particles, i.e., the multifunctional excipient.

[0033] This invention also provides a coal mine wastewater treatment process, which uses the high-efficiency coal mine wastewater treatment agent described above for treatment. The process includes the following steps: Add the multifunctional auxiliary agent dispersion to the wastewater at a ratio of 5-50g / L wastewater, stir for 5-30 minutes, then treat with ultrasound and light simultaneously for 5-90 minutes. After that, add the modified flocculant to the wastewater at a ratio of 2.5-30g / L wastewater, remove the ultrasound, and carry out coagulation and sedimentation treatment for 0.5-2 hours.

[0034] This treatment agent is used in the flocculation and sedimentation process of pollution. The specific wastewater treatment process is implemented according to the actual conditions such as the water quality of coal mine wastewater, and is not limited in this invention.

[0035] For example, in one embodiment, the coal mine wastewater treatment process includes the following steps: Step 1: Transport the coal mine production wastewater to the sedimentation tank for initial sedimentation. The initial sedimentation time is 1-2 hours. If the suspended solids content of the coal mine production wastewater is too high, it is necessary to remove some of the suspended solids (especially large particles) through initial sedimentation before flocculation and sedimentation. However, if the suspended solids content of the wastewater is not too high, this step can be omitted. Step 2: Introduce the overflow wastewater from the grit chamber into the coagulation sedimentation tank. Prepare the multifunctional auxiliary agent and the modified flocculant with water to form a multifunctional auxiliary agent dispersion with a solid content of 10-50% (e.g., a solid content of 25%) and a modified flocculant dispersion with a solid content of 10-50% (e.g., a solid content of 25%), respectively. Add the multifunctional auxiliary agent dispersion to the coagulation sedimentation tank at a ratio of 15g multifunctional auxiliary agent / L wastewater, stir at 500rpm for 10min, then treat with ultrasound and light simultaneously for 20min, then add the modified flocculant to the coagulation sedimentation tank at a ratio of 10g modified flocculant / L wastewater, remove the ultrasound after 10min, and treat with coagulation sedimentation for 30-60min. The ultrasound is generated by setting up an ultrasonic generator; for example, in one example, the ultrasonic power is 0.2-2 kW / m. 3 The frequency is 50-250kHz, and more preferably, the ultrasonic power is 0.7kW / m. 3 The frequency is 120kHz; the ultrasonic generator setup density is 1 ultrasonic generator / m. 3 ; The light source for the illumination treatment is natural light. When natural light is insufficient, ultraviolet lamps are used as the light source. For example, in one example, an ultraviolet LED lamp with a wavelength of 365nm and a power of 100W is used for illumination. The ultraviolet LED lamp is placed 20cm above the sewage.

[0036] Step 3: Filter the overflow from the coagulation sedimentation tank to obtain treated clean water. Conventional filtration methods are acceptable, such as using a filter tank, filter, or membrane. The choice of this step depends on the intended use of the effluent. If a high concentration of suspended solids is required, further filtration can reduce its content. If the requirement for a low concentration of suspended solids is not high, this step can be omitted.

[0037] Invention Mechanism: The high-efficiency treatment agent for coal mine production wastewater provided in this invention is a two-component reagent, including a modified flocculant and a multifunctional adjuvant that can work together. It can effectively address the water quality characteristics of coal mine production wastewater, remove suspended solids, organic pollutants, and heavy metal ions from the water, and efficiently kill bacteria in the water, thus achieving excellent pollution treatment results. The modified flocculant is carbon nanotube and lanthanum-doped polyaluminum chloride. Modification with carbon nanotubes and cerium promotes the formation of a network structure in the modified flocculant system, enhancing the stability of polyaluminum chloride and improving flocculation. It also enhances adsorption to a certain extent, increasing the removal rate of pollutants from water. The multifunctional adjuvant is an adsorption particle with dual acoustic and optical response characteristics, obtained by sequentially modifying attapulgite as a matrix through magnetic, acoustic, and photosensitive functionalization. Besides excellent physical adsorption capacity, it also has the ability to generate active oxygen under ultrasound or light irradiation, thus endowing it with the characteristics of chemically removing organic pollutants through active oxygen generation and bactericidal properties, improving the purification effect of pollution. Simultaneously, the modified flocculant and multifunctional adjuvant interact during the process, intertwining and connecting to form a network structure, creating larger and more stable flocs. This improves flocculation stability, accelerates sedimentation, and enhances the "netting and sweeping effect" of the flocculant, improving the defects of polyaluminum chloride such as loose floc structure, easy turbidity, and poor sedimentation performance.

[0038] I. Specific preparation and mechanism of action of modified flocculants: This invention uses aluminum chloride as the raw material for preparing polyaluminum chloride, and modifies it by adding acidified carbon nanotubes and lanthanum nitrate to prepare a modified flocculant. Pre-treatment of the carbon nanotubes with hydrogen peroxide and strong acid introduces abundant oxygen-containing functional groups such as carboxyl and hydroxyl groups on their surface, improving their dispersibility. During the preparation process, Al... 3+ It can coordinate and electrostatically adsorb with carboxyl and hydroxyl groups on acidified carbon nanotubes, enabling a large amount of Al to be absorbed. 3+ A hydrolysis-polymerization reaction can occur on acidified carbon nanotubes to form an aluminum polymer system in which acidified carbon nanotubes are interwoven. The acidified carbon nanotubes act as a framework, which can improve the stability of the aluminum polymer system structure.

[0039] Lanthanum ions (La) added during the preparation process 3+Lanthanum ions can coordinate with the carboxyl and hydroxyl groups on acidified carbon nanotubes, and have multiple coordination capabilities, which can promote the formation of a network structure of acidified carbon nanotubes, thereby further improving the strength and stability of the aluminum polymer system. In addition, lanthanum carbonate formed by the reaction of some lanthanum ions with Na2CO3 has excellent adsorption effect on phosphorus, which can significantly improve the removal effect of modified flocculants on phosphorus in water, and can better adapt to the treatment of coal mine production wastewater (phosphonic acid collectors used in coal mine production, and pH adjusters such as phosphoric acid and sodium hexametaphosphate can easily cause a large amount of phosphorus pollutants in the water).

[0040] During the flocculation process, the adsorption effect generated by the tubular structure of acidified carbon nanotubes and the strong coordination and electrostatic adsorption between the oxygen-containing functional groups on the surface and the metal ions can enhance the removal capacity of pollutants in water. At the same time, acidified carbon nanotubes can also play an adsorption bridging role, which can increase the floc particle size and improve the floc stability, thereby improving the coagulation effect.

[0041] II. Specific preparation and mechanism of action of multifunctional excipients: 1. First, the purified natural attapulgite is soaked in hydrochloric acid to remove impurities and clear the pores. Then, it is activated by microwave heating to remove some of the crystal water and surface water in the attapulgite, making its structure loose and porous, increasing its specific surface area and adsorption capacity (Yao Ying, He Leping, Zhao Ping. Effect of microwave treatment on the adsorption performance of attapulgite [J]. Metal Mines, 2008, 000(010):135-137.DOI:10.3321 / j.issn:1001-1250.2008.10.038.). Attapulgite is a hydrous magnesium aluminum silicate clay mineral with a layered chain structure. It has a large specific surface area and excellent adsorption capacity, making it suitable as an adsorbent material for water treatment. Next, mesoporous iron(III) oxide was synthesized in situ on activated attapulgite to obtain magnetically modified adsorption particles. Mesoporous iron(III) oxide has a high specific surface area and high adsorption characteristics, which can significantly improve the adsorption capacity of heavy metal ions and organic pollutants in water, thereby improving the adsorption performance of attapulgite. At the same time, since mesoporous iron(III) oxide endows the system with good magnetic properties, it is conducive to the recovery and recycling of multifunctional auxiliary agents.

[0042] Then, cerium-doped titanium dioxide was loaded onto the magnetically modified adsorbent particles using a one-pot hydrothermal method, followed by acoustic hybridization treatment to obtain acoustically functionalized adsorbent particles. The layered structure, abundant pore structure, and specific surface area of ​​the magnetically modified adsorbent particles enable uniform loading of cerium-doped titanium dioxide. A large amount of cerium-doped titanium dioxide is confined within the interlayers and pores of the magnetically modified adsorbent particles, which can greatly improve the stability of cerium-doped titanium dioxide, maintain its long-term acoustic sensitivity performance, and facilitate the recycling of multifunctional excipients.

[0043] Titanium dioxide is an inorganic nanomaterial with acoustic sensitivity. Under ultrasonic action, it can excite reactive oxygen species (ROS). ROS has strong oxidizing properties and can efficiently decompose organic pollutants and odor substances in water, remove water color, and effectively kill bacteria, viruses, and fungi, achieving deep water purification. However, as an acoustic material, titanium dioxide suffers from problems such as easy recombination of electrons and holes after excitation of its band structure, low acoustic efficiency, and poor ROS yield (Liang Shuang. Development and Optimization of Several Novel Acoustic Agents and Their Application in Tumor Synergistic Therapy [D]. University of Science and Technology of China, 2021). In this invention, on the one hand, the layered structure and rich pore structure of the adsorbed particles are magnetically modified to achieve uniform dispersion and loading of titanium dioxide, which helps to increase the specific surface area of ​​titanium dioxide and increase the active sites, thereby improving its acoustic efficiency; on the other hand, by doping nano-cerium oxide (CeO2) into titanium dioxide, the acoustic catalytic activity of titanium dioxide can be improved, and the ROS yield can be increased; CeO2 has a variable valence state, and CeO2 contains Ce 3+ / Ce 4+ The rapid and reversible conversion of CeO2 endows it with excellent oxygen storage capacity, enabling it to dynamically release or capture oxygen, providing sufficient oxygen source for ROS generation; the surface oxygen vacancies generated by CeO2 can serve as reactive centers, promoting the adsorption and activation of oxygen species, and increasing the separation of electrons and holes, thus compensating for the deficiencies of titanium dioxide. Ultimately, this can significantly improve the acoustic properties of titanium dioxide and enhance the ROS yield.

[0044] 2. Then, it undergoes another hydrothermal reaction in a pot, through MXene (specifically T3C2T). x (Taking MXene as an example for illustration) Manganese-doped carbon dots were deposited on T3C2T to prepare a carbon dot-MXene composite; x MXene has a two-dimensional layered structure and contains hydroxyl groups on its surface. The electrostatic adsorption and coordination between manganese ions in the raw material and hydroxyl groups and other carbon dot raw materials facilitates the formation of T3C2T. x Manganese-doped carbon dots are formed by surface and interlayer deposition of MXene.

[0045] The manganese-doped carbon dots in the carbon dot-MXene composite can efficiently generate reactive oxygen species under light irradiation, exhibiting excellent photosensitivity and endowing the multifunctional auxiliaries with superior photocatalytic degradation capabilities for organic pollutants. The main mechanism is that, under light excitation, electrons from the carbon dots transition from the valence band to the conduction band, forming electrons (ek). - ) and holes (h + ) pair, separated electrons (e - ) and holes (h + ) react with oxygen and water molecules respectively to produce singlet oxygen ( 1O2) and hydroxyl radicals (·OH)). Manganese dioxide formed by doping carbon dots can change the surface states of carbon dots, increase electron cloud density, broaden the spectral response range, and reduce the recombination rate of photogenerated electrons and holes, thereby improving the photogenerated ROS performance of carbon dots.

[0046] T3C2T in carbon dot-MXene complex x MXene has at least the following functions: (1) T3C2T x MXene has a high specific surface area, abundant surface functional groups and a two-dimensional layered structure, and has good physical adsorption capacity for heavy metal ions and organic pollutants; (2) its two-dimensional layered structure can provide a larger specific surface area, promote the uniform dispersion of manganese-doped carbon dots, which is conducive to the contact and capture of pollutants, and creates favorable conditions for the treatment of pollutants by manganese-doped carbon dots; (3) T3C2T x MXene can act as an "electron acceptor" site, inhibiting the recombination of photogenerated electrons generated by manganese-doped carbon dots (Fang Yu. Preparation of silver tungstate / MXenes-based composite material and its study on photocatalytic degradation of antibiotics in water [D]. Guizhou University, 2020.), and can provide more active sites to improve the efficiency of photocatalytic ROS generation. Therefore, by forming a composite system of manganese-doped carbon dots and MXene, the photogenerated ROS performance of manganese-doped carbon dots can be significantly improved, and the adsorption capacity of multifunctional adjuvants can be enhanced.

[0047] 3. Finally, the carbon dot-MXene complex is assembled with acoustically functionalized adsorbent particles to prepare acoustic-optically responsive adsorbent particles, i.e., multifunctional excipients. In this process, the acoustically functionalized adsorbent particles are first soaked in dilute nitric acid to form positively charged metal ions (mainly Fe) on the surface. 3+ Then, through the electrostatic coupling and strong coordination between the hydroxyl and carboxyl functional groups on the carbon dot-MXene complex and the metal ions on the surface of the acoustically functionalized adsorbent particles, the carbon dot-MXene complex can be assembled into a large number of uniformly on the surface of the acoustically functionalized adsorbent particles to form a complex: acoustic-optic dual-response adsorbent particles; in this process, the adsorption between MXene and acoustically functionalized adsorbent particles also helps the assembly process.

[0048] In acoustically functionalized adsorption particles, cerium-doped titanium dioxide is largely confined within the interlayer and pores of magnetically modified adsorption particles. A large amount of carbon dot-MXene complex is assembled and coated on the surface of these particles, significantly enhancing the stability of the internal cerium-doped titanium dioxide, which acts as an acoustic sensitizer. This allows the cerium-doped titanium dioxide to exert its acoustic sensitizing properties within the multifunctional adjuvant system, efficiently generating ROS under the excitation of more penetrating ultrasound. The carbon dot-MXene complex on the surface acts as a photosensitizer, efficiently generating large amounts of photogenerated ROS under light excitation. By constructing acoustically and photosensitive dual-response adsorption particles with a core acoustic response and a shell photoresponse, the dual-mode response characteristics formed by the combination of internal and external components enable more efficient ROS generation. Combined with the physical adsorption provided by the magnetically modified adsorption particles as a carrier and the MXene in the carbon dot-MXene complex, this system can achieve efficient removal of pollutants such as organic matter and heavy metal ions from wastewater, as well as efficient killing of bacteria and pathogens in water bodies, achieving deep water purification.

[0049] III. The synergistic effect between modified flocculants and multifunctional adjuvants After the modified flocculant and multifunctional additive were added to the water, the acidified carbon nanotubes in the modified flocculant contained a large number of carboxyl and hydroxyl groups, and some of the remaining lanthanum ions still had coordination ability; the manganese-doped carbon dots on the surface of the multifunctional additive had abundant functional groups such as carboxyl and hydroxyl groups, T3C2T x MXene also contains a certain amount of hydroxyl groups. Through the coordination of lanthanum ions with the carboxyl and hydroxyl groups in the multifunctional adjuvant, the modified flocculant and the multifunctional adjuvant can intertwine to form a network structure through the linkage effect of lanthanum ions, forming a composite system with larger particle size and stronger stability.

[0050] In wastewater treatment, a multifunctional auxiliary agent is first added to the water body, and light and ultrasound are applied simultaneously. The multifunctional auxiliary agent efficiently generates active oxygen and adsorbs a large number of heavy metal ions in the water. Then, a modified flocculant is added for flocculation and deposition. At this time, the adsorbed heavy metal ions coordinate with the carboxyl and hydroxyl groups on the acidified carbon nanotubes and manganese-doped carbon dots, forming more "bridging sites." This promotes the interweaving and connection of more modified flocculants and multifunctional auxiliary agents into a larger network structure, forming highly stable, large-particle-size composite flocs. This further enhances the flocculation stability, deposition rate, and the "netting and sweeping effect" of the flocculant. The more heavy metal ions in the water, the more prominent this enhancing effect becomes, and the greater its contribution to water purification. This is well-suited to address situations where heavy metal pollution in the water is more severe. Therefore, this component system of modified flocculants and multifunctional auxiliary agents in this invention can effectively treat coal mine production wastewater containing both heavy metal ions and organic pollutants.

[0051] In this invention, the composite system of acoustic and photosensitive catalysis for wastewater treatment has the following advantages: This invention utilizes the photosensitive properties of a multifunctional auxiliary agent to efficiently degrade organic matter in wastewater through photocatalysis and the generation of active oxygen, while also killing bacteria. This avoids the need for strong oxidizing agents, making it more environmentally friendly and cost-effective. Furthermore, this invention can utilize artificial lighting or natural light (when natural light is sufficient), further reducing costs. However, a major problem with photocatalytic degradation of organic matter in wastewater is the limited light penetration, especially in water with high turbidity, which further hinders light transmission and affects the photocatalytic degradation effect. Ultrasound, on the other hand, has strong penetrating power in water and is not significantly affected by turbidity. Therefore, ultrasonic catalysis can overcome the poor penetration problem of photocatalysis. The effect of ultrasound can also promote the uniform dispersion of the multifunctional auxiliary agent and the generated active oxygen in the water, thus achieving more efficient and thorough treatment of pollutants. However, the efficiency of active oxygen generation by ultrasonic catalysis is limited, and the application of ultrasound increases costs to some extent. Based on this, the present invention employs a composite system that combines acoustic and photocatalytic catalysis, and uses both photocatalysis and ultrasonic catalysis to treat wastewater. These two systems work synergistically. Photocatalysis can efficiently generate active oxygen, which is then dispersed to various areas of the water body through ultrasonic action. Ultrasonic action can penetrate into blind areas that cannot be reached by light. In conjunction with photocatalysis, deep purification of the entire water body can be achieved. The combination of photocatalysis and ultrasonic catalysis can achieve more efficient wastewater treatment at a relatively lower cost.

[0052] The above is the general concept of the present invention. Based on this, detailed embodiments and comparative examples are provided below to further illustrate the present invention.

[0053] In the following examples and comparative examples, the attapulgite was all natural attapulgite, and it was purified in advance using the following conventional methods before use: Add 50g of 200-mesh natural attapulgite clay (Shijiazhuang Aokai Mineral Products Co., Ltd.) to 1000mL of deionized water, then add 2.5g of sodium hexametaphosphate, ultrasonically disperse for 1h, let stand for 90min, take the upper suspension and centrifuge at 2500rpm, dry the solid product at 100℃ for 6h, grind, and pass through a 200-mesh sieve to complete the purification process.

[0054] In the following examples and comparative examples, the MXene powder is T3C2T. x MXene powder was prepared as follows: 2g of Ti3AlC2 was added to 100mL of 30% hydrofluoric acid solution, and the mixture was stirred at 40℃ for 48h. The product was washed with deionized water by centrifugation until the pH of the supernatant reached 5. The precipitate was collected, dried under vacuum at 70℃ overnight, and ground to obtain T3C2T.x MXene powder.

[0055] Example 1

[0056] A high-efficiency treatment agent for coal mine wastewater includes a modified flocculant and a multifunctional adjuvant.

[0057] The modified flocculant was prepared by the following method: 1) 0.5g of carbon nanotubes (multi-walled carbon nanotubes, diameter 5-10nm, length 30μm) were ultrasonically treated in 100mL of 20%wt hydrogen peroxide for 1h, filtered, and then placed in 100mL of a mixed acid consisting of 95wt% sulfuric acid and 65wt% nitric acid in a volume ratio of 3:1. The mixture was stirred at 70℃ for 4h, filtered, washed with deionized water until neutral, and vacuum dried at 90℃ for 12h to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixed solution with aluminum chloride and lanthanum nitrate concentrations of 0.5 mol / L and 0.05 mol / L, respectively; add 2 g of acidified carbon nanotubes to 100 mL of the mixed solution and ultrasonically disperse for 1 h to obtain the base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixed solution to 2, react at 70 °C for 24 h, centrifuge, wash the solid product with deionized water, and vacuum dry at 80 °C for 12 h to obtain the modified flocculant.

[0058] The multifunctional excipients are prepared by the following methods: S1. Mesoporous iron oxide is synthesized in situ on attapulgite to obtain magnetically modified adsorption particles, which are then loaded with cerium-doped titanium dioxide to obtain acoustically functionalized adsorption particles. S1-1, Attapulgite activation treatment: 10g of attapulgite clay with a mesh size of less than 200 mesh was added to 200mL of 1mol / L hydrochloric acid solution, stirred and refluxed at 90℃ for 4h, filtered, washed with deionized water until neutral, dried at 100℃, ground, and the resulting acidified attapulgite clay was placed in a crucible and treated at 700W for 4min to obtain activated attapulgite clay. S1-2. In-situ synthesis of mesoporous iron oxide on attapulgite: 0.01 mol Fe(NO3)2, 0.02 mol Fe(NO3)3, and 5 g activated attapulgite were added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 20 wt% ammonia was added dropwise under stirring to adjust the pH to 8. The reaction was stirred for 45 min. The resulting product was transferred to a reaction vessel and reacted at 180 °C for 6 h. After cooling to room temperature, the product was filtered, washed with deionized water, and vacuum dried at 100 °C for 8 h to obtain magnetically modified adsorption particles. S1-3, Loading cerium-doped titanium dioxide onto magnetically modified adsorption particles: 2g of magnetically modified adsorption particles, 2.125mL of tetrabutyl titanate, and 0.48g of cerium nitrate were added to 100mL of methanol and ultrasonically dispersed for 1h. Then, 30mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL was added and stirred for 30min. The resulting mixture was transferred to a reaction vessel and reacted at 140℃ for 5h. After cooling to room temperature, the mixture was filtered, washed with deionized water, and vacuum dried at 80℃ for 12h to obtain acoustically functionalized adsorption particles. S2. Deposit manganese-doped carbon dots on MXene to prepare carbon dot-MXene composites: 1 g of MXene powder, 0.14 g of salicylic acid, and 0.35 g of manganese acetate were added to 50 mL of deionized water and ultrasonically dispersed at 70 °C for 1 h to obtain precursor solution 1. 0.75 g of chitosan (90% degree of deacetylation, Jiangsu Minglin Chemical Technology Co., Ltd.), 0.522 g of L-arginine, 0.324 g of p-phenylenediamine, and 50 mL of ethanol were added to 50 mL of deionized water and stirred for 15 min to obtain precursor solution 2. Precursor solution 2 was added to precursor solution 1 under stirring and ultrasonicated for 20 min. The resulting mixture was added to a reaction vessel and reacted at 200 °C for 7 h. After cooling to room temperature, the mixture was centrifuged, the solid product was collected, and freeze-dried to obtain the carbon dot-MXene complex. S3. Assemble carbon dot-MXene complexes with acoustically functionalized adsorbent particles to prepare acousto-optically responsive adsorbent particles: 2g of acoustically functionalized adsorbent particles were added to 50mL of 1mol / L nitric acid solution and stirred for 45min. After filtration and washing, the resulting solid was added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 1. 1.5g of carbon dot-MXene complex was added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 2. Dispersion 2 was added dropwise to dispersion 1 under stirring, and the addition was completed within 45min. After stirring for 1h, the mixture was allowed to stand for 4h, filtered, and the solid product was freeze-dried to obtain acoustically and optically responsive adsorbent particles, i.e., the multifunctional excipient.

[0059] Example 2

[0060] A high-efficiency treatment agent for coal mine wastewater includes a modified flocculant and a multifunctional adjuvant.

[0061] The modified flocculant was prepared by the following method: 1) 0.5g of carbon nanotubes (multi-walled carbon nanotubes, diameter 5-10nm, length 30μm) were ultrasonically treated in 100mL of 20%wt hydrogen peroxide for 1h, filtered, and then placed in 100mL of a mixed acid consisting of 95wt% sulfuric acid and 65wt% nitric acid in a volume ratio of 3:1. The mixture was stirred at 70℃ for 4h, filtered, washed with deionized water until neutral, and vacuum dried at 90℃ for 12h to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixed solution with aluminum chloride and lanthanum nitrate concentrations of 0.5 mol / L and 0.04 mol / L, respectively; add 2 g of acidified carbon nanotubes to 100 mL of the mixed solution and ultrasonically disperse for 1 h to obtain the base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixed solution to 2, react at 70 °C for 24 h, centrifuge, wash the solid product with deionized water, and vacuum dry at 80 °C for 12 h to obtain the modified flocculant.

[0062] The multifunctional excipients are prepared by the following methods: S1. Mesoporous iron oxide is synthesized in situ on attapulgite to obtain magnetically modified adsorption particles, which are then loaded with cerium-doped titanium dioxide to obtain acoustically functionalized adsorption particles. S1-1, Attapulgite activation treatment: 10g of attapulgite clay with a mesh size of less than 200 mesh was added to 200mL of 1mol / L hydrochloric acid solution, stirred and refluxed at 90℃ for 4h, filtered, washed with deionized water until neutral, dried at 100℃, ground, and the resulting acidified attapulgite clay was placed in a crucible and treated at 700W for 4min to obtain activated attapulgite clay. S1-2. In-situ synthesis of mesoporous iron oxide on attapulgite: 0.01 mol Fe(NO3)2, 0.02 mol Fe(NO3)3, and 5.5 g activated attapulgite were added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 20 wt% ammonia was added dropwise under stirring to adjust the pH to 8, and the reaction was stirred for 45 min. The resulting product was transferred to a reaction vessel and reacted at 180 °C for 6 h. After cooling to room temperature, the product was filtered, washed with deionized water, and vacuum dried at 100 °C for 8 h to obtain magnetically modified adsorption particles. S1-3, Loading cerium-doped titanium dioxide onto magnetically modified adsorption particles: 2g of magnetically modified adsorption particles, 2.125mL of tetrabutyl titanate, and 0.45g of cerium nitrate were added to 100mL of methanol and ultrasonically dispersed for 1h. Then, 30mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL was added and stirred for 30min. The resulting mixture was transferred to a reaction vessel and reacted at 140℃ for 5h. After cooling to room temperature, the mixture was filtered, washed with deionized water, and vacuum dried at 80℃ for 12h to obtain acoustically functionalized adsorption particles. S2. Deposit manganese-doped carbon dots on MXene to prepare carbon dot-MXene composites: 1 g of MXene powder, 0.14 g of salicylic acid, and 0.40 g of manganese acetate were added to 50 mL of deionized water and ultrasonically dispersed at 70 °C for 1 h to obtain precursor solution 1. 0.75 g of chitosan (90% degree of deacetylation, Jiangsu Minglin Chemical Technology Co., Ltd.), 0.522 g of L-arginine, 0.324 g of p-phenylenediamine, and 50 mL of ethanol were added to 50 mL of deionized water and stirred for 15 min to obtain precursor solution 2. Precursor solution 2 was added to precursor solution 1 under stirring and ultrasonicated for 20 min. The resulting mixture was added to a reaction vessel and reacted at 200 °C for 7 h. After cooling to room temperature, the mixture was centrifuged, the solid product was collected, and freeze-dried to obtain the carbon dot-MXene complex. S3. Assemble carbon dot-MXene complexes with acoustically functionalized adsorbent particles to prepare acousto-optically responsive adsorbent particles: 2g of acoustically functionalized adsorbent particles were added to 50mL of 1mol / L nitric acid solution and stirred for 45min. After filtration and washing, the resulting solid was added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 1. 1.5g of carbon dot-MXene complex was added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 2. Dispersion 2 was added dropwise to dispersion 1 under stirring, and the addition was completed within 45min. After stirring for 1h, the mixture was allowed to stand for 4h, filtered, and the solid product was freeze-dried to obtain acoustically and optically responsive adsorbent particles, i.e., the multifunctional excipient.

[0063] Example 3

[0064] A high-efficiency treatment agent for coal mine wastewater includes a modified flocculant and a multifunctional adjuvant.

[0065] The modified flocculant was prepared by the following method: 1) 0.5g of carbon nanotubes (multi-walled carbon nanotubes, diameter 5-10nm, length 30μm) were ultrasonically treated in 100mL of 20%wt hydrogen peroxide for 1h, filtered, and then placed in 100mL of a mixed acid consisting of 95wt% sulfuric acid and 65wt% nitric acid in a volume ratio of 3:1. The mixture was stirred at 70℃ for 4h, filtered, washed with deionized water until neutral, and vacuum dried at 90℃ for 12h to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixed solution with aluminum chloride and lanthanum nitrate concentrations of 0.55 mol / L and 0.05 mol / L, respectively; add 2 g of acidified carbon nanotubes to 100 mL of the mixed solution and ultrasonically disperse for 1 h to obtain the base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixed solution to 2, react at 70 °C for 24 h, centrifuge, wash the solid product with deionized water, and vacuum dry at 80 °C for 12 h to obtain the modified flocculant.

[0066] The multifunctional excipients are prepared by the following methods: S1. Mesoporous iron oxide is synthesized in situ on attapulgite to obtain magnetically modified adsorption particles, which are then loaded with cerium-doped titanium dioxide to obtain acoustically functionalized adsorption particles. S1-1, Attapulgite activation treatment: 10g of attapulgite clay with a mesh size of less than 200 mesh was added to 200mL of 1mol / L hydrochloric acid solution, stirred and refluxed at 90℃ for 4h, filtered, washed with deionized water until neutral, dried at 100℃, ground, and the resulting acidified attapulgite clay was placed in a crucible and treated at 700W for 4min to obtain activated attapulgite clay. S1-2. In-situ synthesis of mesoporous iron oxide on attapulgite: 0.01 mol Fe(NO3)2, 0.02 mol Fe(NO3)3, and 5 g activated attapulgite were added to 150 mL of deionized water and ultrasonically dispersed for 1 h. 20 wt% ammonia was added dropwise under stirring to adjust the pH to 8. The reaction was stirred for 45 min. The resulting product was transferred to a reaction vessel and reacted at 180 °C for 6 h. After cooling to room temperature, the product was filtered, washed with deionized water, and vacuum dried at 100 °C for 8 h to obtain magnetically modified adsorption particles. S1-3, Loading cerium-doped titanium dioxide onto magnetically modified adsorption particles: 2.3 g of magnetically modified adsorption particles, 2.125 mL of tetrabutyl titanate, and 0.5 g of cerium nitrate were added to 100 mL of methanol and ultrasonically dispersed for 1 h. Then, 30 mL of sodium hydroxide aqueous solution with a concentration of 0.025 g / mL was added and stirred for 30 min. The resulting mixture was transferred to a reaction vessel and reacted at 140 °C for 5 h. After cooling to room temperature, the mixture was filtered, washed with deionized water, and vacuum dried at 80 °C for 12 h to obtain acoustically functionalized adsorption particles. S2. Deposit manganese-doped carbon dots on MXene to prepare carbon dot-MXene composites: 1 g of MXene powder, 0.14 g of salicylic acid, and 0.30 g of manganese acetate were added to 50 mL of deionized water and ultrasonically dispersed at 70 °C for 1 h to obtain precursor solution 1. 0.75 g of chitosan (90% degree of deacetylation, Jiangsu Minglin Chemical Technology Co., Ltd.), 0.522 g of L-arginine, 0.324 g of p-phenylenediamine, and 50 mL of ethanol were added to 50 mL of deionized water and stirred for 15 min to obtain precursor solution 2. Precursor solution 2 was added to precursor solution 1 under stirring and ultrasonicated for 20 min. The resulting mixture was added to a reaction vessel and reacted at 200 °C for 7 h. After cooling to room temperature, the mixture was centrifuged, the solid product was collected, and freeze-dried to obtain the carbon dot-MXene complex. S3. Assemble carbon dot-MXene complexes with acoustically functionalized adsorbent particles to prepare acousto-optically responsive adsorbent particles: 2g of acoustically functionalized adsorbent particles were added to 50mL of 1mol / L nitric acid solution and stirred for 40min. After filtration and washing, the resulting solid was added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 1. 1.3g of carbon dot-MXene complex was added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 2. Dispersion 2 was added dropwise to dispersion 1 under stirring, and the addition was completed within 45min. After stirring for 1h, the mixture was allowed to stand for 4h, filtered, and the solid product was freeze-dried to obtain acoustically and optically responsive adsorbent particles, i.e., the multifunctional excipient.

[0067] Comparative Example 1 This example is basically the same as Example 1, except that the modified flocculant of Example 1 is used as a high-efficiency treatment agent for coal mine production wastewater, and multifunctional auxiliary agents are not included.

[0068] Comparative Example 2 This example is basically the same as Example 1, except that the modified flocculant in this example is prepared by the following method: 1) 0.5g of carbon nanotubes (multi-walled carbon nanotubes, diameter 5-10nm, length 30μm) were ultrasonically treated in 100mL of 20%wt hydrogen peroxide for 1h, filtered, and then placed in 100mL of a mixed acid consisting of 95wt% sulfuric acid and 65wt% nitric acid in a volume ratio of 3:1. The mixture was stirred at 70℃ for 4h, filtered, washed with deionized water until neutral, and vacuum dried at 90℃ for 12h to obtain acidified carbon nanotubes. 2) Add aluminum chloride to deionized water to prepare a solution with an aluminum chloride concentration of 0.5 mol / L; add 2 g of acidified carbon nanotubes to 100 mL of this solution and ultrasonically disperse for 1 h to obtain the base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixture to 2, react at 70℃ for 24 h, centrifuge, wash the solid product with deionized water, and vacuum dry at 80℃ for 12 h to obtain the modified flocculant.

[0069] Comparative Example 3 This example is basically the same as Example 1, except that the modified flocculant in this example is prepared by the following method: Aluminum chloride and lanthanum nitrate were added to deionized water to prepare a mixed solution with concentrations of 0.5 mol / L and 0.05 mol / L, respectively. Na2CO3 was added to the mixed solution to adjust the alkalinity to 2. The mixture was reacted at 70°C for 24 h, centrifuged, and the solid product was washed with deionized water and dried under vacuum at 80°C for 12 h to obtain the modified flocculant.

[0070] Comparative Example 4 This example is basically the same as Example 1, except that the acoustically functionalized adsorption particles of Example 1 are used as multifunctional adjuvants.

[0071] Comparative Example 5 This example is basically the same as Example 1, except that the carbon dot-MXene complex of Example 1 is used as a multifunctional excipient.

[0072] Comparative Example 6 This example is basically the same as Example 1, except that the multifunctional excipient in this example is prepared by the following method: S1. Mesoporous iron oxide is synthesized in situ on attapulgite to obtain magnetically modified adsorption particles. The specific steps are the same as in Example 1. S2. Add 0.14g salicylic acid and 0.35g manganese acetate to 50mL of deionized water and sonicate at 70℃ for 1h to obtain precursor solution 1; add 0.75g chitosan (90% deacetylation, Jiangsu Minglin Chemical Technology Co., Ltd.), 0.522g L-arginine, 0.324g p-phenylenediamine, and 50mL ethanol to 50mL of deionized water and stir for 15min to obtain precursor solution 2; add precursor solution 2 to precursor solution 1 with stirring and sonicate for 20min. Add the resulting mixture to a reaction vessel and react at 200℃ for 7h. Cool to room temperature, centrifuge, collect the solid product, freeze-dry, and obtain manganese-doped carbon dots. S3. Assemble manganese-doped carbon dots with acoustically functionalized adsorption particles to prepare acousto-optic dual-response adsorption particles: 2g of acoustically functionalized adsorbent particles were added to 50mL of 1mol / L nitric acid solution and stirred for 45min. After filtration and washing, the resulting solid was added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 1. 0.75g of manganese-doped carbon dots were added to 50mL of deionized water and ultrasonically dispersed for 30min to obtain dispersion 2. Dispersion 2 was added dropwise to dispersion 1 under stirring, and the addition was completed within 45min. After stirring for 1h, the mixture was allowed to stand for 4h, filtered, and the solid product was freeze-dried to obtain acoustically and optically responsive adsorbent particles, i.e., the multifunctional excipient.

[0073] Comparative Example 7 This example is basically the same as Example 1, except that steps S1-3 in this example are as follows: 2g of magnetically modified adsorption particles and 2.125mL of tetrabutyl titanate were added to 100mL of methanol and ultrasonically dispersed for 1h. Then, 30mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL was added and stirred for 30min. The resulting mixture was transferred to a reaction vessel and reacted at 140℃ for 5h. After cooling to room temperature, the mixture was filtered, washed with deionized water, and vacuum dried at 80℃ for 12h to obtain acoustically functionalized adsorption particles.

[0074] Comparative Example 8 This example is basically the same as Example 1, except that step S2 in this example is as follows: 1 g of MXene powder and 0.14 g of salicylic acid were added to 50 mL of deionized water and ultrasonically dispersed at 70 °C for 1 h to obtain precursor solution 1. 0.75 g of chitosan (90% degree of deacetylation, Jiangsu Minglin Chemical Technology Co., Ltd.), 0.522 g of L-arginine, 0.324 g of p-phenylenediamine, and 50 mL of ethanol were added to 50 mL of deionized water and stirred for 15 min to obtain precursor solution 2. Precursor solution 2 was added to precursor solution 1 under stirring and ultrasonicated for 20 min. The resulting mixture was added to a reaction vessel and reacted at 200 °C for 7 h. After cooling to room temperature, the mixture was centrifuged, the solid product was collected, and freeze-dried to obtain the carbon dot-MXene complex.

[0075] I. Testing of ROS performance 1-1. The multifunctional excipient from Example 1 was added to deionized water and stirred for 30 min in the dark to prepare a dispersion of the multifunctional excipient with a concentration of 0.5 mg / mL. The dispersion was then treated under different conditions and the singlet oxygen content was tested at different treatment times. 1 O2 content. The SOSG singlet oxygen fluorescent probe (Singlet Oxygen SensorGreen, Shanghai Jinpan Biotechnology Co., Ltd.) was used for testing. The fluorescence intensity (Ex / Em=488 / 525nm) was measured using a fluorescence spectrophotometer. The fluorescence intensity was positively correlated with the singlet oxygen content, so the singlet oxygen content could be characterized by the fluorescence intensity.

[0076] The processing conditions for each group are as follows: (1) US+Light: Simultaneous application of ultrasound and light, ultrasound parameters: ultrasound power is 0.7kW / m 3 The frequency is 120kHz; the illumination uses an ultraviolet LED lamp (wavelength 365nm, power 100W) at a height of 20cm above the multifunctional excipient dispersion.

[0077] (2) US: Processing under dark conditions, only ultrasound applied. Ultrasonic parameters: ultrasound power is 0.7kW / m 3 The frequency is 120kHz.

[0078] (3) Light: Only light is applied. The light source is an ultraviolet LED lamp (wavelength 365nm, power 100W), placed 20cm above the multifunctional excipient dispersion.

[0079] Fluorescence intensity test results at different treatment times are as follows Figure 1As shown, it can be seen that the multifunctional adjuvant of Example 1 can generate singlet oxygen under both ultrasound and light irradiation, and the singlet oxygen yield is the highest when ultrasound and light irradiation are applied simultaneously.

[0080] 1-2. The multifunctional excipients prepared in Examples 1-3 and Comparative Examples 4-8 were added to deionized water and stirred in the dark for 30 min to prepare a multifunctional excipient dispersion with a concentration of 0.5 mg / mL. The dispersion was then subjected to simultaneous ultrasound and light irradiation for 15 min. The singlet oxygen content in the dispersion was then tested using the same method as above. 1 O2 content; among which, ultrasonic parameters: ultrasonic power is 0.7kW / m 3 The frequency is 120kHz; the illumination uses an ultraviolet LED lamp (wavelength 365nm, power 100W) at a height of 20cm above the multifunctional excipient dispersion.

[0081] Test results are as follows Figure 2 As shown, the singlet oxygen production in Examples 1-3 is significantly higher than that in Comparative Examples 4-8. The reason for this is as follows: The multifunctional adjuvant in Comparative Example 4 did not contain carbon dot-MXene, and its ability to generate singlet oxygen through photocatalysis was significantly reduced. The multifunctional adjuvant in Comparative Example 5 did not contain acoustically functionalized adsorbent particles, and lost its ability to generate singlet oxygen under ultrasound. The multifunctional adjuvant in Comparative Example 6 did not contain hybridized MXene, which affected its ability to generate singlet oxygen through photocatalysis. The acoustically functionalized adsorbent particles in Comparative Example 7 did not contain cerium doping, which affected the acoustically catalytic activity. The carbon dot-MXene in Comparative Example 8 did not contain manganese doping, and its photocatalytic activity decreased.

[0082] II. Characterization of Modified Flocculants and Multifunctional Adjuvants Reference Figure 3 The infrared spectrum of the modified flocculant prepared in Example 1 is shown below. Figure 4 The infrared spectrum of the multifunctional excipient prepared in Example 1 illustrates the successful synthesis of the modified flocculant and the multifunctional excipient.

[0083] III. Wastewater Treatment Performance Testing The wastewater treatment performance of the treatment agents prepared in the examples and comparative examples was tested using the following methods. The water samples were overflow water from the combined wastewater of Shaanxi Yongming Coal Mine Co., Ltd., which was treated by primary sedimentation in a grit chamber (primary sedimentation time was 1 hour). The water quality is shown in Table 1 below: Table 1

[0084] Note: The metal ions included are Fe. 3+ Mn 4+ Co 3+Pb 2+ Cu 2+ Cd 2+ Total amount.

[0085] The testing process used is as follows: (1) Prepare a multifunctional auxiliary agent dispersion with a solid content of 25% and a modified flocculant dispersion with a solid content of 25% by using water respectively. Fill a 1m container with wastewater samples. 3 In the wastewater tank, the multifunctional auxiliary agent dispersion was added to the coagulation sedimentation tank at a ratio of 15g multifunctional auxiliary agent / L wastewater. The mixture was stirred at 500rpm for 10min, and then treated with ultrasound and light simultaneously for 20min. After that, the modified flocculant was added to the coagulation sedimentation tank at a ratio of 10g modified flocculant / L wastewater. After 10min, the ultrasound and light were removed, and the coagulation sedimentation treatment lasted for 45min. An ultrasonic generator with an ultrasonic power of 0.7 kW / m was installed in the center of the sewage tank. 3 The frequency is 120kHz; an ultraviolet LED light (wavelength 365nm, power 100W) is installed 20cm above the sewage tank as the light source.

[0086] To compare the effects of different wastewater treatment processes, comparative examples 9 and 10 were also set up.

[0087] Comparative Example 9 The testing process used is as follows: (1) The multifunctional adjuvant and modified flocculant prepared in Example 1 were respectively prepared with water to form a multifunctional adjuvant dispersion with a solid content of 25% and a modified flocculant dispersion with a solid content of 25%. Fill a 1m container with wastewater samples. 3 In the wastewater tank, the multifunctional auxiliary agent dispersion was added to the coagulation sedimentation tank at a ratio of 15g multifunctional auxiliary agent / L wastewater. The mixture was stirred at 500rpm for 10min, then treated under light for 20min. After that, the modified flocculant was added to the coagulation sedimentation tank at a ratio of 10g modified flocculant / L wastewater. The light was removed, and the mixture was stirred at 500rpm for 10min. The coagulation sedimentation treatment lasted for 45min. An ultraviolet LED light (wavelength 365nm, power 100W) is installed 20cm above the sewage tank as the light source.

[0088] Comparative Example 10 The testing process used is as follows: (1) The multifunctional adjuvant and modified flocculant prepared in Example 1 were respectively prepared with water to form a multifunctional adjuvant dispersion with a solid content of 25% and a modified flocculant dispersion with a solid content of 25%. Fill a 1m container with wastewater samples. 3 In the wastewater tank, a multifunctional auxiliary agent dispersion was added to the coagulation sedimentation tank at a ratio of 15g of multifunctional auxiliary agent / L of wastewater. The mixture was stirred at 500rpm for 10 minutes, followed by ultrasonic treatment for 20 minutes. Then, modified flocculant was added to the coagulation sedimentation tank at a ratio of 10g of modified flocculant / L of wastewater. After 10 minutes, the ultrasonic treatment was removed, and the coagulation sedimentation process lasted for 45 minutes. An ultrasonic generator with an ultrasonic power of 0.7kW / m was placed in the center of the wastewater tank. 3 The frequency is 120kHz.

[0089] After treatment, the supernatant was analyzed to calculate the removal rate of each component. The results are shown in Table 2 below. Figures 5-10 As shown: Table 2

[0090] The test results show that the treatment agents in Examples 1-3 can achieve efficient removal of SS (suspended solids), COD, BOD, heavy metal ions, and phosphorus, while also effectively killing bacteria in the water. The treatment agent in Comparative Example 1 does not contain multifunctional adjuvants and relies solely on the coagulation effect of the modified flocculant to remove pollutants, similar to traditional wastewater treatment methods. This results in a significant decrease in various indicators, necessitating further treatment measures (such as re-sedimentation, biological treatment, sterilization, etc.).

[0091] In Comparative Example 2, the removal efficiency of phosphorus decreased significantly, and other indicators also decreased to some extent, indicating that doping the modified flocculant with lanthanum can significantly improve the removal efficiency of phosphorus and also improve other indicators to some extent.

[0092] The modified flocculant in Comparative Example 3 did not contain acidified carbon nanotubes, which significantly affected the stability and flocculation effect of polyaluminum chloride, leading to a significant decrease in various indicators.

[0093] In Comparative Example 4, the unhybridized carbon dot-MXene significantly reduced its photogenerated ROS capacity and adsorption performance, resulting in a marked decrease in various indicators.

[0094] In Comparative Example 5, the unhybridized acoustic-sensitive functionalized adsorbent particles lacked the ability to generate ROS under ultrasound and also lacked the physical adsorption properties provided by the acoustic-sensitive functionalized adsorbent particles, resulting in a significant decrease in all indicators.

[0095] The COD and BOD removal rates in Comparative Example 6 decreased significantly, indicating that MXene has a significant effect on increasing the photogenerated ROS capacity of carbon dots.

[0096] The decrease in various indicators in Comparative Example 7 indicates that the doping of cerium in the acoustically functionalized adsorbent particles has a significant effect on improving the acoustically catalytic activity, and can also improve the removal capacity of suspended solids and heavy metal ions to a certain extent.

[0097] The decrease in COD and BOD removal rates in Comparative Example 8 indicates that manganese doping in carbon dots can improve the photogenerated ROS performance of carbon dots.

[0098] The significant decrease in various indicators in Comparative Examples 9 and 10 indicates that the composite system with dual acoustic and photosensitive catalysis constructed in this invention can effectively improve the removal rate of COD, BOD, and P and the sterilization performance by increasing the ROS yield. The decrease in the removal rate of SS and metal ions in Comparative Example 9 is mainly attributed to the fact that without the application of ultrasound, the uniform dispersion of the treatment agent and the sufficient contact with the pollutants cannot be promoted by ultrasound.

[0099] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A high-efficiency treatment agent for coal mine wastewater, characterized in that, It includes modified flocculants and multifunctional additives. When using it, the modified flocculants and multifunctional additives are added to the wastewater at a mass ratio of 5:1 to 1:2, and the wastewater is treated under the simultaneous application of ultrasound and light. The modified flocculant is carbon nanotubes and lanthanum-doped polyaluminum chloride; The multifunctional excipient was prepared by the following method: S1. Mesoporous iron oxide is synthesized in situ on attapulgite to obtain magnetically modified adsorption particles. Then, cerium-doped titanium dioxide is loaded onto the magnetically modified adsorption particles to prepare acoustically functionalized adsorption particles. S2. Deposit manganese-doped carbon dots on MXene to prepare carbon dot-MXene composites; S3. Assemble carbon dot-MXene complex with acoustically functionalized adsorbent particles to prepare acoustic-optic dual-response adsorbent particles, i.e., multifunctional excipients.

2. The high-efficiency treatment agent for coal mine production wastewater according to claim 1, characterized in that, The multifunctional excipient was prepared by the following method: S1. Preparation of acoustically functionalized adsorption particles: S1-1. Add attapulgite to hydrochloric acid solution, heat and stir under reflux, filter, wash until neutral, dry, grind, and microwave to obtain activated attapulgite. S1-2. Disperse Fe(NO3)2, Fe(NO3)3, and activated attapulgite in deionized water, adjust the pH to 8-9 with ammonia, stir the reaction, transfer the resulting product to a reaction vessel, react at 170-190℃ for 3-12 hours, filter, wash, and dry to obtain magnetically modified adsorption particles. S1-3. Disperse the magnetically modified adsorption particles, tetrabutyl titanate, and cerium nitrate in methanol, then add sodium hydroxide aqueous solution, stir, transfer the resulting mixture into a reaction vessel, react at 120-150℃ for 3-10 h, filter, wash, and dry to obtain acoustically functionalized adsorption particles. S2. MXene powder, salicylic acid, and manganese acetate are dispersed in deionized water to obtain precursor solution 1; chitosan, L-arginine, p-phenylenediamine, and ethanol are added to deionized water and stirred to obtain precursor solution 2; precursor solution 2 is added to precursor solution 1 under stirring and ultrasonically dispersed; the resulting mixture is added to a reaction vessel and reacted at 180-225℃ for 4-10 h; centrifuged; and the solid product is freeze-dried to obtain carbon dot-MXene complex. S3. Add the acoustically functionalized adsorbent particles to a nitric acid solution, stir, filter, wash, and redisperse the resulting solid in deionized water to obtain dispersion 1; disperse the carbon dot-MXene complex in deionized water to obtain dispersion 2; add dispersion 2 dropwise to dispersion 1 while stirring, stir, let stand, filter, and freeze-dry the solid product to obtain acoustically and optically responsive adsorbent particles, i.e., multifunctional excipients.

3. The high-efficiency treatment agent for coal mine wastewater according to claim 2, characterized in that, Step S1 specifically includes: S1-1. Add attapulgite to a 0.2-5 mol / L hydrochloric acid solution, stir and reflux at 70-100℃ for 2-8 hours, filter, wash until neutral, dry, grind, place the acidified attapulgite in a crucible, microwave at 500-800W for 2-8 minutes to obtain activated attapulgite. S1-2. Add 0.005-0.02 mol Fe(NO3)2, 0.01-0.04 mol Fe(NO3)3, and 2.5-10 g activated attapulgite to 100-300 mL of deionized water and ultrasonically disperse for 0.5-2 h. Adjust the pH to 8-9 by adding ammonia dropwise while stirring, and stir the reaction for 30-90 min. Transfer the obtained product to a reaction vessel and react at 170-190℃ for 3-12 h. Cool to room temperature, filter, wash, and dry to obtain magnetically modified adsorption particles. S1-3. Add 1-4g of magnetically modified adsorption particles, 1.1-4.25mL of tetrabutyl titanate, and 0.24-0.96g of cerium nitrate to 50-200mL of methanol and ultrasonically disperse for 0.5-2h. Then add 15-60mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL and stir for 15-60min. Transfer the resulting mixture to a reaction vessel and react at 120-150℃ for 3-10h. Filter, wash, and dry to obtain acoustically functionalized adsorption particles.

4. The high-efficiency treatment agent for coal mine production wastewater according to claim 3, characterized in that, Step S2 is as follows: Add 0.5-2g MXene powder, 0.07-0.28g salicylic acid, and 0.175-0.7g manganese acetate to 25-100mL of deionized water and sonicate at 60-80℃ for 0.5-2h to obtain precursor solution 1. Add 0.35-1.5g chitosan, 0.26-1.04g L-arginine, 0.16-0.64g p-phenylenediamine, and 25-100mL ethanol to 25-100mL of deionized water and stir for 5-30min to obtain precursor solution 2. Add precursor solution 2 to precursor solution 1 with stirring and sonicate for 10-40min. Add the resulting mixture to a reaction vessel and react at 180-225℃ for 4-10h. Centrifuge and freeze-dry the solid product to obtain the carbon dot-MXene complex.

5. The high-efficiency treatment agent for coal mine wastewater according to claim 3, characterized in that, Step S3 is as follows: Add 1-4g of acoustically functionalized adsorbent particles to 25-100mL of 1mol / L nitric acid solution, stir for 30-90min, filter, wash, and add the resulting solid to 25-100mL of deionized water. Sonicate for 15-60min to obtain dispersion 1. Add 0.75-3g of carbon dot-MXene complex to 25-100mL of deionized water and sonicate for 15-60min to obtain dispersion 2. Add dispersion 2 dropwise to dispersion 1 under stirring, completing the addition within 30-90min. Stir for 0.5-2h, let stand for 2-6h, filter, and freeze-dry the solid product to obtain acoustically and optically responsive adsorbent particles, i.e., the multifunctional excipient.

6. The high-efficiency treatment agent for coal mine wastewater according to claim 1, characterized in that, The multifunctional excipient was prepared by the following method: S1. Preparation of acoustically functionalized adsorption particles: S1-1. Add 10g of 200-mesh attapulgite to 200mL of 1mol / L hydrochloric acid solution, stir and reflux at 90℃ for 4h, filter, wash with deionized water until neutral, dry at 100℃, grind, and treat the acidified attapulgite in a microwave oven at 700W for 4min to obtain activated attapulgite. S1-2. Add 0.01mol Fe(NO3)2, 0.02mol Fe(NO3)3, and 5g activated attapulgite to 150mL of deionized water and ultrasonically disperse for 1h. Adjust the pH to 8 by adding 20wt% ammonia water dropwise while stirring. Stir the reaction for 45min. Transfer the obtained product to a reaction vessel and react at 180℃ for 6h. Cool, filter, wash the solid product with deionized water, and vacuum dry at 100℃ for 8h to obtain magnetically modified adsorption particles. S1-3. Add 2g of magnetically modified adsorption particles, 2.125mL of tetrabutyl titanate, and 0.48g of cerium nitrate to 100mL of methanol and ultrasonically disperse for 1h. Then add 30mL of sodium hydroxide aqueous solution with a concentration of 0.025g / mL and stir for 30min. Transfer the resulting mixture to a reaction vessel and react at 140℃ for 5h. Cool to room temperature, filter, wash with deionized water, and vacuum dry at 80℃ for 12h to obtain acoustically functionalized adsorption particles. S2. Add 1g MXene powder, 0.14g salicylic acid, and 0.35g manganese acetate to 50mL of deionized water and sonicate at 70℃ for 1h to obtain precursor solution 1; add 0.75g chitosan, 0.522g L-arginine, 0.324g p-phenylenediamine, and 50mL ethanol to 50mL of deionized water and stir for 15min to obtain precursor solution 2; add precursor solution 2 to precursor solution 1 with stirring and sonicate for 20min. Add the resulting mixture to a reaction vessel and react at 200℃ for 7h. Cool, centrifuge, and freeze-dry the solid product to obtain carbon dot-MXene complex. Among them, MXene powder is T3C2T x MXene powder; S3. Add 2g of acoustically functionalized adsorption particles to 50mL of 1mol / L nitric acid solution, stir for 45min, filter and wash, add the obtained solid to 50mL of deionized water, and sonicate for 30min to obtain dispersion 1; add 1.5g of carbon dot-MXene complex to 50mL of deionized water, and sonicate for 30min to obtain dispersion 2; add dispersion 2 dropwise to dispersion 1 under stirring, and complete the addition within 45min, stir for 1h, let stand for 4h, filter, and freeze-dry the solid product to obtain acoustically and optically responsive adsorption particles, i.e., the multifunctional excipient.

7. The high-efficiency treatment agent for coal mine wastewater according to claim 1, characterized in that, The modified flocculant was prepared by the following method: 1) After ultrasonic treatment of carbon nanotubes in hydrogen peroxide, they are placed in a mixed acid composed of sulfuric acid and nitric acid, heated and stirred, filtered, washed with deionized water until neutral, and dried to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixture; add acidified carbon nanotubes to the mixture and disperse by ultrasonication to obtain a base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixture to 2-2.5, react under heating, centrifuge, wash the solid product with deionized water, and dry to obtain the modified flocculant.

8. The high-efficiency treatment agent for coal mine wastewater according to claim 7, characterized in that, The modified flocculant was prepared by the following method: 1) 0.5g of carbon nanotubes were ultrasonically treated in 100mL of 20%wt hydrogen peroxide for 1h, filtered, and then placed in 100mL of a mixed acid consisting of 95wt% sulfuric acid and 65wt% nitric acid in a volume ratio of 3:

1. The mixture was stirred at 70℃ for 4h, filtered, washed with deionized water until neutral, and vacuum dried at 90℃ for 12h to obtain acidified carbon nanotubes. 2) Add aluminum chloride and lanthanum nitrate to deionized water to prepare a mixed solution with aluminum chloride and lanthanum nitrate concentrations of 0.5 mol / L and 0.05 mol / L, respectively; add 2 g of acidified carbon nanotubes to 100 mL of the mixed solution and ultrasonically disperse for 1 h to obtain the base solution; add Na2CO3 to the base solution to adjust the alkalinity of the mixed solution to 2, react at 70 °C for 24 h, centrifuge, wash the solid product with deionized water, and vacuum dry at 80 °C for 12 h to obtain the modified flocculant.

9. A coal mine wastewater treatment process, characterized in that, It employs the high-efficiency treatment agent for coal mine production wastewater as described in any one of claims 1-8, and the process includes the following steps: Add the multifunctional auxiliary agent dispersion to the wastewater at a ratio of 2-10g / L wastewater, stir for 5-30 minutes, then treat with ultrasound and light simultaneously for 5-90 minutes. After that, add the modified flocculant to the wastewater at a ratio of 2.5-30g / L wastewater, remove the ultrasound, and carry out coagulation and sedimentation treatment for 0.5-2 hours.

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