High-efficiency adsorptive sewage treatment agent and preparation method thereof

Abstract

This invention relates to the field of wastewater treatment technology, specifically to a highly efficient adsorbent wastewater treatment agent and its preparation method, comprising the following raw materials in parts by weight: 50-70 parts activated carbon powder, 8-12 parts deionized water, 5-10 parts ammonium bicarbonate, 1-3 parts sodium dodecyl sulfate, 15-25 parts additive A, and 8-15 parts additive B. In this invention, the stably loaded cerium ions can effectively exert their specific coordination and capture effect on heavy metals. The chitosan introduced into the carrier can enhance the electrostatic and chelate adsorption of anionic pollutants and organic molecules. Simultaneously, the well-developed pores formed after shellac carbonization combine with the network structure of chitosan, further increasing the specific surface area of ​​the material and the adsorption capacity of organic pollutants, achieving highly efficient and stable adsorption of heavy metals, dyes, and organic pollutants.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically to a highly efficient adsorbent wastewater treatment agent and its preparation method. Background Technology

[0002] Commonly used wastewater treatment agents include activated carbon, bentonite, diatomaceous earth, synthetic resins, and some biomass materials. Among them, activated carbon is widely used due to its well-developed pore structure and huge specific surface area. With the rapid development of industrialization and urbanization, the discharge of various types of wastewater is increasing day by day, and its composition is becoming more and more complex. It often contains high concentrations of heavy metal ions such as lead, cadmium, chromium, and copper, as well as recalcitrant organic pollutants and various suspended solids. These pollutants pose a serious threat to the aquatic ecological environment and human health.

[0003] Existing wastewater treatment agents have some limitations. Traditional agents such as activated carbon mainly rely on physical adsorption, have weak chemical binding capacity for pollutants, insufficient adsorption capacity for pollutants existing in ionic form, and limited effectiveness against recalcitrant organic matter. Therefore, this invention provides a highly efficient adsorption wastewater treatment agent and its preparation method. Summary of the Invention

[0004] The purpose of this invention is to provide a highly efficient adsorption wastewater treatment agent and its preparation method. The wastewater treatment agent prepared by this invention not only has a good heavy metal ion capture ability, but also has good organic pollutant degradation performance, effectively improving wastewater treatment efficiency.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A highly efficient adsorption wastewater treatment agent comprises the following raw materials in parts by weight: 50-70 parts activated carbon powder, 8-12 parts deionized water, 5-10 parts ammonium bicarbonate, 1-3 parts sodium dodecyl sulfate, 15-25 parts additive A and 8-15 parts additive B. The raw materials for additive A include composite powder, anhydrous ethanol, carrier powder, KH-550 and glutaraldehyde solution; The raw materials for additive B include additives, anhydrous ethanol, curcumin, caffeic acid, chitosan, dilute acetic acid aqueous solution, KH550 and glutaraldehyde solution.

[0006] Further, the additive A is prepared by the following method: the composite powder is dispersed in anhydrous ethanol at 6-10 times its mass, and 1-3% KH550 by mass of the composite powder is added. The mixture is refluxed at 60-70°C for 4-6 hours. After the reaction, the product is centrifuged and the resulting solid is washed with ethanol 3-5 times and dried at 70-80°C for 4-6 hours to obtain a premixed powder for later use. The carrier powder and the premixed powder are mixed at a mass ratio of 1.5-2.5:1 to obtain a first mixture. 1-3% glutaraldehyde solution by mass is added to the first mixture, and the mixture is reacted for 2-4 hours. After the reaction, the product is filtered, and the filter residue is washed with deionized water until neutral. The residue is dried at 50-70°C for 6-8 hours and ground through a 200-mesh sieve to obtain additive A, wherein the mass concentration of the glutaraldehyde solution is 0.5-2%.

[0007] Further, the composite powder is prepared by the following method: 200-300 mesh pyrophyllite powder is taken, and the pyrophyllite powder is mixed with KH550 and anhydrous ethanol. The mass ratio of pyrophyllite powder, KH550 and anhydrous ethanol is 1:0.05-0.1:20-30. After mixing, the mixture is refluxed at 70-80℃ for 3-5 hours. The resulting product is filtered to obtain a solid. The solid is dried at 70-80℃ for 6-8 hours to obtain a coarse material. The coarse material is stirred with cerium citrate solution at 60-80℃ for 6-10 hours. The mixture is filtered to obtain a filter residue. The filter residue is dried at 100-120℃ for 3-5 hours, and then calcined at 400-500℃ for 2-3 hours. The resulting product is ground and sieved through a 400 mesh sieve to obtain the composite powder. The mass ratio of the coarse material to the cerium citrate solution is 100:10-12.

[0008] Further, the carrier powder is prepared by the following method: Shellac resin is crushed and placed in a tube furnace, pyrolyzed at 500-600℃ for 1-2 hours under nitrogen protection to obtain an intermediate product. The intermediate product is mixed with phosphoric acid solution at a solid-liquid ratio of 1g:(5-8)mL, soaked in a water bath at 60-80℃ for 6-10 hours, filtered, and the filter residue is washed with deionized water until neutral, dried, and pulverized to 200 mesh to obtain shellac resin carbon powder. The shellac resin carbon powder is mixed with deionized water at a mass ratio of 1:(8...)... -12) Mix to obtain a suspension. Add 0.5-1% of the volume of lysozyme solution to the suspension and react at 35-40℃ and pH 6.5-7.5 for 2-3 hours. Add 5-10% of the mass of the lysozyme solution of chitosan acetate solution and react for 1 hour. Centrifuge to separate the precipitate. Dry the precipitate and grind it through a 200-mesh sieve to obtain the carrier powder. The mass concentration of the phosphoric acid solution is 10-20%, and the concentration of the lysozyme solution is 10-20 mg / mL.

[0009] Further, the additive B is prepared by the following method: The additive is dispersed in anhydrous ethanol at 10-20 times its mass to obtain a dispersion, which is set aside. Curcumin and caffeic acid are mixed and dissolved in acetone at 20-30 times their mass to obtain a first premixed solution, which is set aside. Chitosan is dissolved in a 0.5-2% (w / w) dilute acetic acid aqueous solution, where the mass of chitosan is 1-2% of the mass of the dilute acetic acid aqueous solution, to obtain a second premixed solution. The first and second premixed solutions are mixed at a volume ratio of 1:(0.8-1.2), and then the first... The premixed solution and the second premixed solution contain 0.5-1.5% KH-550 by mass, and are stirred at 40-60℃ for 1-2 hours to obtain a loaded solution. The loaded solution is then added dropwise to the dispersion at a mass ratio of 1:0.8-1.5. The mixture is stirred and impregnated at 40-50℃ in the dark for 4-6 hours. Subsequently, 1-3% glutaraldehyde solution by volume of the impregnation system is added, and the crosslinking reaction continues for 1-2 hours. The mixture is then centrifuged, and the precipitate is washed 2-4 times with acetone and dried at 60-70℃ for 4-6 hours to obtain additive B. The mass concentration of the glutaraldehyde solution is 2%.

[0010] Further, the additive is prepared by the following method: praseodymium nitrate, neodymium nitrate, and cerium nitrate are mixed in a mass ratio of 1:1:(0.1-0.3), and 80-100 times the total mass of praseodymium nitrate, neodymium nitrate, and cerium nitrate are added to deionized water and stirred to dissolve. Then, 2.5-3.5% of the mass of deionized water is added to propyl gallate to obtain a first mixture. The reactant is mixed with the first mixture in a mass ratio of 1:(5-10), and the reaction is carried out for 12-24 hours. The mixture is filtered, and the filter residue is dried at 80-100℃ and calcined at 400-500℃ for 2-3 hours under nitrogen protection. After cooling, the additive is obtained.

[0011] Further, the reactant is prepared by the following method: sucrose and erythrina gum are mixed at a mass ratio of (7-9):2 to obtain a second mixture. 1.5-2.33 times the mass of the second mixture is added to deionized water to obtain a second liquid mixture. Ethyl silicate and hexadecyltrimethylammonium bromide are added to the second liquid mixture to obtain a reaction solution. The reaction solution is transferred to a hydrothermal reactor and reacted at 150-180℃ for 10-15 hours. After cooling, the mixture is filtered, and the filter residue is washed three times each with deionized water and anhydrous ethanol. The dried solid is then heated to 600-700℃ at a rate of 5℃ / min under a nitrogen atmosphere and carbonized for 2-3 hours. After cooling, it is soaked in a 2-4 mol / L sodium hydroxide solution for 12-24 hours, filtered, and the filter residue is washed with deionized water until neutral. The residue is then dried to obtain the reactant.

[0012] Furthermore, the mass of the ethyl silicate is 10-15% of the mass of sucrose, and the mass of the hexadecyltrimethylammonium bromide is 5-8% of the mass of sucrose.

[0013] Furthermore, the concentration of cerium ions in the cerium citrate solution is 0.05-0.1 mol / L.

[0014] Furthermore, the preparation method of the highly efficient adsorption wastewater treatment agent includes the following steps: Step 1: Place activated carbon powder, additive A and additive B in a high-speed mixer and stir at 300-500 rpm for 15-20 minutes to obtain a dry mixture; Step 2: Dissolve ammonium bicarbonate and sodium dodecyl sulfate in deionized water to obtain a third mixture. Spray the third mixture into the dry mixture and granulate to obtain wet granules. Step 3: Dry the wet granules at 100-110℃ for 3.5-4.5 hours, then cool them to obtain a highly efficient adsorbent wastewater treatment agent.

[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, additive A modifies the surface of pyrophyllite powder by introducing a silane coupling agent, thereby enhancing the binding force between cerium citrate and the carrier. After calcination, cerium exists in a relatively stable form, preventing cerium ions from falling off in wastewater. After being cross-linked and fixed on the modified shellac resin carbon carrier by glutaraldehyde, the stably loaded cerium ions can effectively exert their specific coordination and capture effect on heavy metals. The chitosan introduced into the carrier can enhance the electrostatic and chelate adsorption of anionic pollutants and organic molecules. At the same time, the well-developed pores formed after shellac carbonization combine with the network structure of chitosan, further improving the specific surface area of ​​the material and the adsorption capacity of organic pollutants, thus achieving efficient and stable adsorption of heavy metals, dyes and organic pollutants.

[0016] 2. In this invention, additive B, through the combination of chitosan and glutaraldehyde, effectively fixes curcumin and caffeic acid on the surface and inside of a rare earth-doped porous carbon matrix, avoiding direct covalent bonding between the silane coupling agent and the polyphenolic hydroxyl groups. This preserves the reducing properties and reactivity of the phenolic hydroxyl groups of curcumin and caffeic acid. The protected polyphenol system synergistically interacts with rare earth ions (praseodymium, neodymium, cerium), providing additional adsorption sites through its abundant phenolic hydroxyl groups. Its fully preserved reducing functional groups can further form a redox system with rare earth ions, continuously reducing high-valence toxic metal ions and catalytically degrading some organic pollutants during wastewater treatment, thus improving the purification depth of the treatment agent for complex pollutants.

[0017] 3. In this invention, by rationally combining additives A and B with the activated carbon matrix, complementary and synergistic effects of adsorption functions are achieved. Activated carbon provides basic adsorption capacity and rapid diffusion channels, additive A focuses on enhancing the broad-spectrum capture of conventional pollutants through ionic interactions and porous structures, and additive B provides selective adsorption and chemical transformation capabilities for difficult-to-treat pollutants. The three work synergistically to enable the final treatment agent to simultaneously and efficiently remove multiple types of pollutants from wastewater, exhibiting excellent comprehensive purification performance. Attached Figure Description

[0018] Figure 1 The present invention provides a flowchart of a highly efficient adsorption wastewater treatment agent and its preparation method. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] It should be noted that the raw materials used in the following embodiments are all commercially available. Example 1:

[0021] Raw material preparation: 50 parts activated carbon powder, 8 parts deionized water, 5 parts ammonium bicarbonate, 1 part sodium dodecyl sulfate, 15 parts additive A and 8 parts additive B; Additive A was prepared by the following method: The composite powder was dispersed in anhydrous ethanol at 6 times its mass, and 1% KH550 (by mass of the composite powder) was added. The mixture was refluxed at 60°C for 4 hours. After the reaction, the product was centrifuged, and the resulting solids were washed three times with ethanol and dried at 70°C for 4 hours to obtain a premixed powder. The carrier powder and the premixed powder were mixed at a mass ratio of 1.5:1 to obtain a first mixture. 1% glutaraldehyde solution (by mass of the first mixture) was added to the first mixture, and the mixture was reacted for 2 hours. After the reaction, the product was filtered, and the filter residue was washed with deionized water until neutral. The residue was dried at 50°C for 6 hours and ground through a 200-mesh sieve to obtain additive A. The mass concentration of the glutaraldehyde solution was 0.5%. The composite powder was prepared by the following method: 200-mesh pyrophyllite powder was taken, and pyrophyllite powder was mixed with KH550 and anhydrous ethanol. The mass ratio of pyrophyllite powder, KH550 and anhydrous ethanol was 1:0.05:20. After mixing, the mixture was refluxed at 70℃ for 3 hours. The resulting product was filtered to obtain a solid. The solid was dried at 70℃ for 6 hours to obtain a coarse material. The coarse material was stirred with cerium citrate solution at 60℃ for 6 hours. The mixture was filtered to obtain a filter residue. The filter residue was dried at 100℃ for 3 hours and then calcined at 400℃ for 2 hours. The resulting product was ground and sieved through a 400-mesh sieve to obtain the composite powder. The mass ratio of coarse material to cerium citrate solution was 100:10, and the cerium ion concentration in the cerium citrate solution was 0.05 mol / L. The carrier powder was prepared by the following method: after crushing the shellac resin, it was placed in a tube furnace and pyrolyzed at 500°C for 1 hour under nitrogen protection to obtain an intermediate product. The intermediate product was mixed with phosphoric acid solution at a solid-liquid ratio of 1 g: (5) mL and soaked in a water bath at 60°C for 6 hours. After filtration, the filter residue was washed with deionized water until neutral, dried, and pulverized to 200 mesh to obtain shellac resin carbon powder. The shellac resin carbon powder was mixed with deionized water at a mass ratio of 1: (8) to obtain a suspension. 0.5% of its volume of lysozyme solution was added to the suspension and reacted at 35°C and pH 6.5 for 2 hours. 5% of the mass of lysozyme solution of chitosan acetate solution was added and reacted for 1 hour. The mixture was centrifuged and the resulting precipitate was dried, ground through a 200-mesh sieve, and the carrier powder was obtained. The mass concentration of the phosphoric acid solution was 10%, and the concentration of the lysozyme solution was 10 mg / mL. Additive B is prepared by the following method: The additive is dispersed in anhydrous ethanol at 10 times its mass to obtain a dispersion, which is then set aside. Curcumin and caffeic acid are mixed and dissolved in acetone at 20 times their mass to obtain a first premixed solution, which is then set aside. Chitosan is dissolved in a 0.5% (w / w) dilute acetic acid aqueous solution, with the chitosan mass being 1% of the mass of the dilute acetic acid aqueous solution, to obtain a second premixed solution. The first and second premixed solutions are mixed at a volume ratio of 1:(0.8), and then... Add 0.5% KH-550 (total mass of the first and second premixed solutions) to the mixture and stir at 40°C for 1 hour to obtain a loaded solution. Add the loaded solution dropwise to the dispersion at a mass ratio of 1:0.8. Stir and impregnate at 40°C in the dark for 4 hours. Then add 1% glutaraldehyde solution (total volume of the impregnation system) and continue the crosslinking reaction for 1 hour. Perform centrifugation, wash the precipitate twice with acetone, and dry at 60°C for 4 hours to obtain additive B. The mass concentration of the glutaraldehyde solution is 2%. The additive was prepared by the following method: praseodymium nitrate, neodymium nitrate, and cerium nitrate were mixed in a mass ratio of 1:1:(0.1), and 80 times the total mass of praseodymium nitrate, neodymium nitrate, and cerium nitrate were added to deionized water and stirred to dissolve. Then, 2.5% of the mass of deionized water was added to propyl gallate to obtain the first mixture. The reactant was mixed with the first mixture in a mass ratio of 1:(5), and reacted for 12 hours. The mixture was filtered, and the filter residue was dried at 80°C. The residue was then calcined at 400°C for 2 hours under nitrogen protection and cooled to obtain the additive. The reactant was prepared by the following method: sucrose and erythrina gum were mixed at a mass ratio of (7):2 to obtain a second mixture. Deionized water with a mass of 1.5 times that of the second mixture was added to obtain a second liquid mixture. Ethyl silicate and hexadecyltrimethylammonium bromide were added to the second liquid mixture to obtain a reaction solution. The reaction solution was transferred to a hydrothermal reactor and reacted at 150°C for 10 hours. After cooling, the mixture was filtered. The filter residue was washed three times each with deionized water and anhydrous ethanol. The dried solid was heated to 600°C at a rate of 5°C / min under a nitrogen atmosphere and carbonized for 2 hours. After cooling, the solid was soaked in a 2 mol / L sodium hydroxide solution for 12 hours. After filtration, the filter residue was washed with deionized water until neutral and dried to obtain the reactant. The mass of ethyl silicate was 10% of the mass of sucrose, and the mass of hexadecyltrimethylammonium bromide was 5% of the mass of sucrose. Finished product preparation: Step 1: Place activated carbon powder, additive A and additive B in a high-speed mixer and stir at 300 rpm for 15 minutes to obtain a dry mixture. Step 2: Dissolve ammonium bicarbonate and sodium dodecyl sulfate in deionized water to obtain a third mixture. Spray the third mixture into the dry mixture and granulate to obtain wet granules. Step 3: Dry the wet granules at 100℃ for 3.5 hours, then cool them to obtain a highly efficient adsorbent wastewater treatment agent. Example 2:

[0022] Raw material preparation: 60 parts activated carbon powder, 10 parts deionized water, 7 parts ammonium bicarbonate, 2 parts sodium dodecyl sulfate, 20 parts additive A and 10 parts additive B; Additive A was prepared by the following method: The composite powder was dispersed in anhydrous ethanol at 8 times its mass, and 2% (by mass) of KH550 was added. The mixture was refluxed at 65°C for 5 hours. After the reaction, the product was centrifuged, and the resulting solids were washed four times with ethanol and dried at 75°C for 5 hours to obtain a premixed powder. The carrier powder and the premixed powder were mixed at a mass ratio of 2:1 to obtain a first mixture. 2% (by mass) of glutaraldehyde solution was added to the first mixture, and the mixture was reacted for 3 hours. After the reaction, the product was filtered, and the filter residue was washed with deionized water until neutral. The residue was dried at 60°C for 7 hours and ground through a 200-mesh sieve to obtain additive A. The mass concentration of the glutaraldehyde solution was 1.5%. The composite powder was prepared by the following method: 250-mesh pyrophyllite powder was taken, mixed with KH550 and anhydrous ethanol, and the mass ratio of pyrophyllite powder, KH550 and anhydrous ethanol was 1:0.07:25. After mixing, the mixture was refluxed at 75℃ for 4 hours. The resulting product was filtered to obtain a solid, which was dried at 75℃ for 7 hours to obtain a coarse material. The coarse material was stirred with cerium citrate solution at 70℃ for 8 hours, filtered to obtain a filter residue, which was dried at 110℃ for 4 hours and then calcined at 450℃ for 2.5 hours. The resulting product was ground and sieved through a 400-mesh sieve to obtain the composite powder. The mass ratio of the coarse material to the cerium citrate solution was 100:11, and the cerium ion concentration in the cerium citrate solution was 0.07 mol / L. The carrier powder was prepared by the following method: after crushing the shellac resin, it was placed in a tube furnace and pyrolyzed at 550°C for 1.5 h under nitrogen protection to obtain an intermediate product. The intermediate product was mixed with phosphoric acid solution at a solid-liquid ratio of 1 g: (7) mL and soaked in a water bath at 70°C for 8 h. After filtration, the filter residue was washed with deionized water until neutral, dried, and pulverized to 200 mesh to obtain shellac resin carbon powder. The shellac resin carbon powder was mixed with deionized water at a mass ratio of 1: (10) to obtain a suspension. 0.7% of its volume of lysozyme solution was added to the suspension and reacted at 37°C and pH 7 for 2.5 h. 7% of the mass of lysozyme solution of chitosan acetate solution was added and reacted for 1 h. The mixture was centrifuged and the resulting precipitate was dried, ground through a 200-mesh sieve, and the carrier powder was obtained. The mass concentration of the phosphoric acid solution was 15%, and the concentration of the lysozyme solution was 15 mg / mL. Additive B is prepared by the following method: the additive is dispersed in anhydrous ethanol at 15 times its mass to obtain a dispersion, which is set aside for later use. Curcumin and caffeic acid are mixed and dissolved in acetone at 25 times the mass of the mixture to obtain a first premixed solution, which is set aside for later use. Chitosan is dissolved in a 1.5% dilute acetic acid aqueous solution, where the mass of chitosan is 1.5% of the mass of the dilute acetic acid aqueous solution, to obtain a second premixed solution. The first premixed solution and the second premixed solution are mixed at a volume ratio of 1:(1), and then added... Add 1% KH-550 (total mass of the first and second premixed solutions) to the mixture and stir at 50°C for 1.5 h to obtain a loaded solution. Add the loaded solution dropwise to the dispersion at a mass ratio of 1:1.2. Stir and impregnate at 45°C in the dark for 5 h. Then add 2% glutaraldehyde solution (total volume of the impregnation system) and continue the crosslinking reaction for 1.5 h. Perform centrifugation, wash the precipitate three times with acetone, and dry at 65°C for 5 h to obtain additive B. The mass concentration of the glutaraldehyde solution is 2%. The additive was prepared by the following method: praseodymium nitrate, neodymium nitrate, and cerium nitrate were mixed in a mass ratio of 1:1:(0.2), and 90 times the total mass of praseodymium nitrate, neodymium nitrate, and cerium nitrate were added to deionized water and stirred to dissolve. Then, 3% of the mass of deionized water was added to propyl gallate to obtain the first mixture. The reactant was mixed with the first mixture in a mass ratio of 1:(7), and reacted for 18 hours. The mixture was filtered, and the filter residue was dried at 90°C. The residue was then calcined at 450°C for 2.5 hours under nitrogen protection and cooled to obtain the additive. The reactant was prepared by the following method: sucrose and erythrina gum were mixed at a mass ratio of (8):2 to obtain a second mixture. Deionized water with a mass of 2 times that of the second mixture was added to obtain a second liquid mixture. Ethyl silicate and hexadecyltrimethylammonium bromide were added to the second liquid mixture to obtain a reaction solution. The reaction solution was transferred to a hydrothermal reactor and reacted at 160°C for 12 hours. After cooling, the mixture was filtered. The filter residue was washed three times each with deionized water and anhydrous ethanol. The dried solid was heated to 650°C at a rate of 5°C / min under a nitrogen atmosphere and carbonized for 2.5 hours. After cooling, the solid was soaked in a 3 mol / L sodium hydroxide solution for 18 hours. After filtration, the filter residue was washed with deionized water until neutral and dried to obtain the reactant. The mass of ethyl silicate was 13% of the mass of sucrose, and the mass of hexadecyltrimethylammonium bromide was 6% of the mass of sucrose. Finished product preparation: Step 1: Place activated carbon powder, additive A and additive B in a high-speed mixer and stir at 500 rpm for 20 minutes to obtain a dry mixture. Step 2: Dissolve ammonium bicarbonate and sodium dodecyl sulfate in deionized water to obtain a third mixture. Spray the third mixture into the dry mixture and granulate to obtain wet granules. Step 3: Dry the wet granules at 105℃ for 4 hours, then cool them to obtain a highly efficient adsorbent wastewater treatment agent. Example 3:

[0023] Raw material preparation: 70 parts activated carbon powder, 12 parts deionized water, 10 parts ammonium bicarbonate, 3 parts sodium dodecyl sulfate, 25 parts additive A and 15 parts additive B; Additive A was prepared by the following method: The composite powder was dispersed in anhydrous ethanol at 10 times its mass, and 3% (by mass) of KH550 was added. The mixture was refluxed at 70°C for 6 hours. After the reaction, the product was centrifuged, and the resulting solids were washed five times with ethanol and dried at 80°C for 6 hours to obtain a premixed powder. The carrier powder and the premixed powder were mixed at a mass ratio of 2.5:1 to obtain a first mixture. 3% (by mass) of glutaraldehyde solution was added to the first mixture, and the mixture was reacted for 4 hours. After the reaction, the product was filtered, and the filter residue was washed with deionized water until neutral. The residue was dried at 70°C for 8 hours and ground through a 200-mesh sieve to obtain additive A. The mass concentration of the glutaraldehyde solution was 2%. The composite powder was prepared by the following method: 300-mesh pyrophyllite powder was taken, mixed with KH550 and anhydrous ethanol, and the mass ratio of pyrophyllite powder, KH550 and anhydrous ethanol was 1:0.1:30. After mixing, the mixture was refluxed at 80℃ for 5 hours. The resulting product was filtered to obtain a solid, which was dried at 80℃ for 8 hours to obtain a coarse material. The coarse material was stirred with cerium citrate solution at 80℃ for 10 hours, filtered to obtain a filter residue, which was dried at 120℃ for 5 hours and then calcined at 500℃ for 3 hours. The resulting product was ground and sieved through a 400-mesh sieve to obtain the composite powder. The mass ratio of the coarse material to the cerium citrate solution was 100:12, and the cerium ion concentration in the cerium citrate solution was 0.1 mol / L. The carrier powder was prepared by the following method: after crushing the shellac resin, it was placed in a tube furnace and pyrolyzed at 600°C for 2 hours under nitrogen protection to obtain an intermediate product. The intermediate product was mixed with phosphoric acid solution at a solid-liquid ratio of 1g:(8)mL and soaked in a water bath at 80°C for 10 hours. After filtration, the filter residue was washed with deionized water until neutral, dried, and pulverized to 200 mesh to obtain shellac resin carbon powder. The shellac resin carbon powder was mixed with deionized water at a mass ratio of 1:(12) to obtain a suspension. 1% of the volume of lysozyme solution was added to the suspension and reacted at 40°C and pH 7.5 for 3 hours. 10% of the mass of the lysozyme solution was added to chitosan acetate solution and reacted for 1 hour. The mixture was centrifuged and the resulting precipitate was dried, ground through a 200-mesh sieve, and the carrier powder was obtained. The mass concentration of the phosphoric acid solution was 20%, and the concentration of the lysozyme solution was 20mg / mL. Additive B is prepared by the following method: The additive is dispersed in anhydrous ethanol at 20 times its mass to obtain a dispersion, which is then set aside. Curcumin and caffeic acid are mixed and dissolved in acetone at 30 times their mass to obtain a first premixed solution, which is then set aside. Chitosan is dissolved in a 2% (w / w) dilute acetic acid aqueous solution, with the chitosan mass being 2% of the mass of the dilute acetic acid aqueous solution, to obtain a second premixed solution. The first and second premixed solutions are mixed at a volume ratio of 1:(1.2), and then... Add 1.5% KH-550 (total mass of the first and second premixed solutions) to the mixture and stir at 60°C for 2 hours to obtain a loaded solution. The loaded solution is then added dropwise to the dispersion at a mass ratio of 1:1.5. The mixture is stirred and impregnated at 50°C in the dark for 6 hours. Subsequently, 3% glutaraldehyde solution (total volume of the impregnation system) is added, and the crosslinking reaction continues for 2 hours. The mixture is then centrifuged, and the precipitate is washed four times with acetone and dried at 70°C for 6 hours to obtain additive B. The glutaraldehyde solution has a mass concentration of 2%. The additive was prepared by the following method: praseodymium nitrate, neodymium nitrate, and cerium nitrate were mixed in a mass ratio of 1:1:(0.3), and 100 times the total mass of praseodymium nitrate, neodymium nitrate, and cerium nitrate were added to deionized water and stirred to dissolve. Then, 3.5% of the mass of deionized water was added to propyl gallate to obtain the first mixture. The reactant was mixed with the first mixture in a mass ratio of 1:(10), and reacted for 24 hours. The mixture was filtered, and the filter residue was dried at 100°C. The residue was then calcined at 500°C for 3 hours under nitrogen protection and cooled to obtain the additive. The reactant was prepared by the following method: sucrose and erythrina gum were mixed at a mass ratio of (9):2 to obtain a second mixture. Deionized water with a mass of 2.33 times that of the second mixture was added to obtain a second liquid mixture. Ethyl silicate and hexadecyltrimethylammonium bromide were added to the second liquid mixture to obtain a reaction solution. The reaction solution was transferred to a hydrothermal reactor and reacted at 180°C for 15 hours. After cooling, the mixture was filtered. The filter residue was washed three times each with deionized water and anhydrous ethanol. The dried solid was heated to 700°C at a rate of 5°C / min under a nitrogen atmosphere and carbonized for 3 hours. After cooling, the solid was soaked in a 4 mol / L sodium hydroxide solution for 24 hours. After filtration, the filter residue was washed with deionized water until neutral and dried to obtain the reactant. The mass of ethyl silicate was 15% of the mass of sucrose, and the mass of hexadecyltrimethylammonium bromide was 8% of the mass of sucrose. Finished product preparation: Step 1: Place activated carbon powder, additive A and additive B in a high-speed mixer and stir at 500 rpm for 20 minutes to obtain a dry mixture. Step 2: Dissolve ammonium bicarbonate and sodium dodecyl sulfate in deionized water to obtain a third mixture. Spray the third mixture into the dry mixture and granulate to obtain wet granules. Step 3: Dry the wet granules at 110℃ for 4.5 hours, then cool them to obtain a highly efficient adsorbent wastewater treatment agent.

[0024] Comparative Example 1: The difference between this comparative example and Example 1 is that this comparative example does not contain additive A.

[0025] Comparative Example 2 differs from Example 1 in that it does not contain additive B.

[0026] Comparative Example 3 differs from Example 1 in that it contains neither additive A nor additive B.

[0027] Performance testing: The high-efficiency adsorption wastewater treatment agents prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance testing, and the test data are recorded in the table below: Table 1 In the performance test, the lead ion adsorption capacity was determined as follows: Following the similarity principle of GB / T 12496.8-2015, lead-containing simulated wastewater was prepared, and under specified adsorption conditions, the saturated adsorption capacity of the adsorbent per unit mass for lead ions was determined. The methylene blue adsorption value was determined as follows: Following the kinetic test approach of GB / T 12496.10-1999, methylene blue solution was selected as the model organic pollutant, and the removal rate of methylene blue by the adsorbent within a fixed time was determined. The phenol removal rate was determined as follows: Referring to HJ 676-2013, phenol-containing simulated wastewater was prepared, and after reacting for a certain time under simulated light conditions, the removal rate of phenol for each sample was calculated based on the initial and remaining concentrations of phenol.

[0028] The data obtained from the performance test table show that the wastewater treatment agents prepared in Examples 1-3 are superior to those in Comparative Examples 1-3 in terms of three key indicators: lead ion adsorption capacity, methylene blue adsorption value, and phenol removal rate. This proves the key role of additives A and B in the system of this invention and the necessity of their synergistic effect.

[0029] By comparing and analyzing the relevant data in the table, it can be seen that the highly efficient adsorption wastewater treatment agent prepared by this invention not only has a good heavy metal ion capture capacity, but also good organic pollutant degradation performance. This indicates that the highly efficient adsorption wastewater treatment agent provided by this invention has a broader market prospect and is more suitable for widespread application.

[0030] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0031] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A highly efficient adsorbent wastewater treatment agent, characterized in that, The ingredients include the following parts by weight: 50-70 parts activated carbon powder, 8-12 parts deionized water, 5-10 parts ammonium bicarbonate, 1-3 parts sodium dodecyl sulfate, 15-25 parts additive A and 8-15 parts additive B; The raw materials for additive A include composite powder, anhydrous ethanol, carrier powder, KH-550 and glutaraldehyde solution; The raw materials for additive B include additives, anhydrous ethanol, curcumin, caffeic acid, chitosan, dilute acetic acid aqueous solution, KH550, and glutaraldehyde solution.

2. The wastewater treatment agent with high-efficiency adsorption according to claim 1, characterized in that, Additive A is prepared by the following method: The composite powder is dispersed in anhydrous ethanol at 6-10 times its mass, and 1-3% (by mass) of KH550 is added. The mixture is refluxed at 60-70°C for 4-6 hours. After the reaction, the product is centrifuged, and the resulting solid is washed with ethanol 3-5 times and dried at 70-80°C for 4-6 hours to obtain a premixed powder. The carrier powder and the premixed powder are mixed at a mass ratio of 1.5-2.5:1 to obtain a first mixture. 1-3% (by mass) of glutaraldehyde solution is added to the first mixture, and the mixture is reacted for 2-4 hours. After the reaction, the product is filtered, and the filter residue is washed with deionized water until neutral. The residue is dried at 50-70°C for 6-8 hours and ground through a 200-mesh sieve to obtain additive A. The mass concentration of the glutaraldehyde solution is 0.5-2%.

3. The wastewater treatment agent with high-efficiency adsorption according to claim 2, characterized in that, The composite powder is prepared by the following method: 200-300 mesh pyrophyllite powder is taken, and pyrophyllite powder is mixed with KH550 and anhydrous ethanol. The mass ratio of pyrophyllite powder, KH550 and anhydrous ethanol is 1:0.05-0.1:20-30. After mixing, the mixture is refluxed at 70-80℃ for 3-5 hours. The resulting product is filtered to obtain a solid. The solid is dried at 70-80℃ for 6-8 hours to obtain a coarse material. The coarse material is stirred with cerium citrate solution at 60-80℃ for 6-10 hours. The mixture is filtered to obtain a filter residue. The filter residue is dried at 100-120℃ for 3-5 hours, and then calcined at 400-500℃ for 2-3 hours. The resulting product is ground and sieved through a 400 mesh sieve to obtain the composite powder. The mass ratio of the coarse material to the cerium citrate solution is 100:10-12.

4. The wastewater treatment agent with high-efficiency adsorption according to claim 2, characterized in that, The carrier powder is prepared by the following method: Shellac resin is crushed and placed in a tube furnace, pyrolyzed at 500-600℃ for 1-2 hours under nitrogen protection to obtain an intermediate product. The intermediate product is mixed with phosphoric acid solution at a solid-liquid ratio of 1g:(5-8)mL, soaked in a water bath at 60-80℃ for 6-10 hours, filtered, and the filter residue is washed with deionized water until neutral, dried, and pulverized to 200 mesh to obtain shellac resin carbon powder. The shellac resin carbon powder is mixed with deionized water at a mass ratio of 1:(8-1)mL. 2) Mix to obtain a suspension. Add 0.5-1% of the volume of lysozyme solution to the suspension and react at 35-40℃ and pH 6.5-7.5 for 2-3 hours. Add 5-10% of the mass of the lysozyme solution of chitosan acetate solution and react for 1 hour. Centrifuge to separate the precipitate, dry it, grind it through a 200-mesh sieve to obtain the carrier powder. The mass concentration of the phosphoric acid solution is 10-20%, and the concentration of the lysozyme solution is 10-20 mg / mL.

5. The wastewater treatment agent with high-efficiency adsorption according to claim 1, characterized in that, Additive B is prepared by the following method: The additive is dispersed in anhydrous ethanol at 10-20 times its mass to obtain a dispersion, which is then set aside. Curcumin and caffeic acid are mixed and dissolved in acetone at 20-30 times their mass to obtain a first premixed solution, which is then set aside. Chitosan is dissolved in a 0.5-2% (w / w) dilute acetic acid aqueous solution, where the mass of chitosan is 1-2% of the mass of the dilute acetic acid aqueous solution, to obtain a second premixed solution. The first and second premixed solutions are mixed at a volume ratio of 1:(0.8-1.2), and then the first premixed solution is added... The total mass of the liquid and the second premixed solution is 0.5-1.5% of KH-550. The mixture is stirred at 40-60℃ for 1-2 hours to obtain a loaded liquid. The loaded liquid is added dropwise to the dispersion at a mass ratio of 1:0.8-1.

5. The mixture is stirred and impregnated at 40-50℃ in the dark for 4-6 hours. Then, 1-3% of the total volume of the impregnation system is added to the glutaraldehyde solution. The crosslinking reaction is continued for 1-2 hours. The mixture is then centrifuged and the precipitate is washed 2-4 times with acetone and dried at 60-70℃ for 4-6 hours to obtain additive B. The mass concentration of the glutaraldehyde solution is 2%.

6. The wastewater treatment agent with high-efficiency adsorption according to claim 5, characterized in that, The additive is prepared by the following method: praseodymium nitrate, neodymium nitrate, and cerium nitrate are mixed in a mass ratio of 1:1:(0.1-0.3), and 80-100 times the total mass of praseodymium nitrate, neodymium nitrate, and cerium nitrate are added to deionized water and stirred to dissolve. Then, 2.5-3.5% of propyl gallate by mass of deionized water is added to obtain a first mixture. The reactant is mixed with the first mixture in a mass ratio of 1:(5-10), and the reaction is carried out for 12-24 hours. The mixture is filtered, and the filter residue is dried at 80-100℃ and calcined at 400-500℃ for 2-3 hours under nitrogen protection. After cooling, the additive is obtained.

7. The wastewater treatment agent with high-efficiency adsorption according to claim 6, characterized in that, The reactant is prepared by the following method: sucrose and erythrina gum are mixed at a mass ratio of (7-9):2 to obtain a second mixture. 1.5-2.33 times the mass of the second mixture is added to deionized water to obtain a second liquid mixture. Ethyl silicate and hexadecyltrimethylammonium bromide are added to the second liquid mixture to obtain a reaction solution. The reaction solution is transferred to a hydrothermal reactor and reacted at 150-180℃ for 10-15 hours. After cooling, the mixture is filtered, and the filter residue is washed three times each with deionized water and anhydrous ethanol. The dried solid is then heated to 600-700℃ at a rate of 5℃ / min under a nitrogen atmosphere and carbonized for 2-3 hours. After cooling, the solid is soaked in a 2-4 mol / L sodium hydroxide solution for 12-24 hours, filtered, and the filter residue is washed with deionized water until neutral. The residue is then dried to obtain the reactant.

8. The wastewater treatment agent with high-efficiency adsorption according to claim 7, characterized in that, The mass of the ethyl silicate is 10-15% of the mass of sucrose, and the mass of the hexadecyltrimethylammonium bromide is 5-8% of the mass of sucrose.

9. The wastewater treatment agent with high-efficiency adsorption according to claim 3, characterized in that, The concentration of cerium ions in the cerium citrate solution is 0.05-0.1 mol / L.

10. The method for preparing the highly efficient adsorbent wastewater treatment agent according to claims 1-9, characterized in that, Includes the following steps: Step 1: Place activated carbon powder, additive A and additive B in a high-speed mixer and stir at 300-500 rpm for 15-20 minutes to obtain a dry mixture. Step 2: Dissolve ammonium bicarbonate and sodium dodecyl sulfate in deionized water to obtain a third mixture. Spray the third mixture into the dry mixture and granulate to obtain wet granules. Step 3: Dry the wet granules at 100-110℃ for 3.5-4.5 hours, then cool them to obtain a highly efficient adsorbent wastewater treatment agent.

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