Efficient sewage treatment agent and preparation method thereof

Abstract

The invention discloses an efficient sewage treatment agent and a preparation method thereof, and relates to the field of sewage treatment agents. When the efficient sewage treatment agent is prepared, magnetic particles firstly react with aniline and then react with (dimethylamino) acetyl chloride to prepare modified magnetic particles, cellulose reacts with sodium periodate and zinc chloride to prepare dialdehyde cellulose, the dialdehyde cellulose reacts with dodecyl succinic anhydride to prepare modified cellulose, and the modified cellulose is prepared into the efficient sewage treatment agent. The modified magnetic particles, the modified cellulose and 2-chloroethylamine are subjected to a reaction, and the efficient sewage treatment agent is prepared. The high-efficiency sewage treatment agent prepared by the invention has good oil stain removal and heavy metal removal performance, antibacterial performance and reusability, and can be magnetically separated.

Description

Technical Field

[0001] The present invention relates to the field of sewage treatment agents, and specifically to a high-efficiency sewage treatment agent and a preparation method thereof. Background Art

[0002] Petroleum, as an important resource in modern industry, has played a crucial role in the global economic development and industrialization process. However, the oil extraction and processing processes inevitably have an impact on the ecological environment. For example, the waste gas produced during the production process is highly toxic and volatile, the waste liquid will seep into the soil, causing soil salinization and polluting groundwater. When crude oil accidentally lands on the ground and forms a mixture with sand, soil and water, it will induce soil compaction. Heavy metal ions and organic pollutant components will accumulate heavily in animals and humans through the food chain, causing irreversible damage to the natural environment and human health. Oil-containing sewage usually refers to the sewage formed due to accidental oil spills during exploration and exploitation, refining and processing, transportation and storage processes, mainly containing inorganic pollutants such as heavy metals and salts like copper, chromium, mercury, etc., and a large number of harmful microorganisms, mostly pathogenic bacteria, and has the characteristics of high oil content, high viscosity, poor fluidity, difficult dehydration, and difficult sedimentation. If not properly disposed of, it will pose a serious threat to the natural environment, ecological safety and human health.

[0003] The high-efficiency sewage treatment agent prepared by the present invention can effectively remove heavy metal ions and oil stains in oil-containing sewage, is easy to separate, and can be reused after desorption, having good market prospects. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-efficiency sewage treatment agent and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions: A high-efficiency sewage treatment agent, which is prepared by reacting magnetic particles with aniline first and then with (dimethylamino) acetyl chloride to obtain modified magnetic particles, reacting cellulose with sodium periodate and zinc chloride to obtain dialdehyde cellulose, reacting dialdehyde cellulose with dodecyl succinic anhydride to obtain modified cellulose, and reacting the modified magnetic particles, modified cellulose and 2-chloroethylamine.

[0006] A high-efficiency sewage treatment agent and a preparation method thereof, including the following preparation steps: (1)Mix fly ash magnetic beads, deionized water, and absolute ethanol at a mass ratio of 1:(5 - 15):(20 - 30), stir at 200 - 300 r / min for 10 - 20 min at room temperature, add ammonia water 4 - 6 times the mass of the magnetic particles, and drop tetraethyl orthosilicate 5 - 7 times the mass of the fly ash at a rate of 2 drops per second. Continue stirring for 5 - 7 h, separate the solids in the solution with a permanent magnet, wash with deionized water 3 - 5 times, and dry at 75 - 85 °C for 10 - 14 h to obtain magnetic particles. (2)Mix ammonium persulfate and deionized water at a mass ratio of 1:2 to prepare an aqueous solution of ammonium persulfate. Mix magnetic particles, aniline, and 1 mol / L hydrochloric acid solution, ultrasonicate for 15 min, and drop the aqueous solution of ammonium persulfate 30 - 40 times the mass of the magnetic particles at a rate of 3 - 5 drops per second. Stir at 300 - 400 r / min at room temperature for 7 - 9 h, separate the solids with a permanent magnet, wash the solids with deionized water and absolute ethanol 3 - 5 times respectively, and dry at 60 - 70 °C for 4 - 6 h to obtain pre-modified magnetic particles. Mix pre-modified magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide, stir at 300 - 400 r / min at room temperature for 5 - 6 h under an argon atmosphere, add (dimethylamino)acetyl chloride 0.2 - 0.4 times the mass of the magnetic particles, heat to 145 - 155 °C, continue stirring for 2 - 3 days, perform suction filtration, wash the filter cake with deionized water 3 - 5 times, perform Soxhlet extraction for 2 - 3 days with N,N-dimethylformamide as the solvent, and vacuum dry at 55 - 65 °C for 20 - 24 h to obtain modified magnetic particles. (3)Mix a 1% mass concentration nano-cellulose solution, sodium periodate, zinc chloride, and deionized water, adjust the pH to 4.0 with dilute hydrochloric acid, wrap with aluminum foil to avoid light, stir at 150 - 250 r / min at room temperature for 4 - 6 h, perform suction filtration with a filter membrane with a pore size of 0.45 μm, wash the filter cake with deionized water 3 - 5 times, and vacuum dry at 55 - 65 °C for 4 - 6 h to obtain dialdehyde cellulose. Mix urea and choline chloride at a molar ratio of 2:1, heat at 75 - 85 °C for 20 - 30 min to obtain a mixed solution. Mix dialdehyde cellulose, dodecyl succinic anhydride, and the mixed solution, react in a microwave reactor at 55 - 65 °C for 10 - 20 min, add absolute ethanol 1.5 - 2.5 times the mass of the mixed solution to precipitate, centrifuge to separate the precipitate, wash the precipitate with deionized water 3 - 5 times, and then dialyze the precipitate in distilled water for 72 h with a dialysis membrane with a molecular weight cut-off of 1000 Da, and freeze-dry to obtain modified cellulose. (4) Mix modified cellulose, 2-chloroethylamine, and absolute ethanol at a mass ratio of 1:(1 - 2):(40 - 60), stir at 300 - 400 r / min at 45 - 55 °C for 4 - 6 h, add modified magnetic particles in an amount 0.4 - 0.6 times the mass of the modified cellulose, continue stirring for 4 - 6 h, separate the solids in the solution with a permanent magnet, wash 3 - 5 times with deionized water, and freeze-dry to obtain a high-efficiency sewage treatment agent.

[0007] As an optimization, the method for preparing fly ash magnetic beads in step (1) is: subject 100-mesh fly ash to magnetic separation with a magnetic separation tube under a strong magnetic field of 100 mT, and then separate it through a weak magnetic field of 100 mT.

[0008] As an optimization, the mass ratio of the magnetic particles, aniline, and 1 mol / L hydrochloric acid solution in step (2) is 1:(4 - 5):(15 - 25).

[0009] As an optimization, the mass ratio of the pre-modified magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide in step (2) is 1:(1.5 - 2.5):(35 - 45).

[0010] As an optimization, the mass ratio of the 1% nano-cellulose solution by mass concentration, sodium periodate, zinc chloride, and deionized water in step (3) is 1:(1.5 - 2.5):(0.8 - 1.2):(200 - 300).

[0011] As an optimization, the mass ratio of the dialdehyde cellulose, dodecyl succinic anhydride, and mixed solution in step (3) is 1:(1.5 - 2.5):(80 - 120).

[0012] As an optimization, the mass ratio of the modified cellulose, 2-chloroethylamine, and absolute ethanol in step (4) is 1:(1 - 2):(40 - 60).

[0013] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing the high-efficiency sewage treatment agent of the present invention, the magnetic particles are first reacted with aniline and then with (dimethylamino)acetyl chloride to obtain modified magnetic particles, the cellulose is reacted with sodium periodate and zinc chloride to obtain dialdehyde cellulose, the dialdehyde cellulose is reacted with dodecyl succinic anhydride to obtain modified cellulose, and the modified magnetic particles, modified cellulose, and 2-chloroethylamine are reacted to obtain the high-efficiency sewage treatment agent.

[0014] First, the fly ash magnetic beads prepared by magnetic separation of fly ash have good magnetism and can be adsorbed by a permanent magnet. Therefore, the high-efficiency sewage treatment agent can be adsorbed by the permanent magnet after treating sewage, so as to achieve a separation effect and effectively improve the separation efficiency of the sewage treatment agent. The magnetic particles react with aniline first and then with (dimethylamino) acetyl chloride to prepare modified magnetic particles. Polyaniline polymerizes on the surface of the magnetic particles to form a polyaniline layer. The polyaniline structure contains a large number of amino and imine structures, which can complex with heavy metal ions, so as to achieve the effect of adsorbing heavy metals. Moreover, after the amino and imine structures complex with heavy metal ions, they can be desorbed under alkaline conditions, making the sewage treatment agent have good reusability. (Dimethylamino) acetyl chloride can react with 2-chloroethylamine to generate quaternary ammonium salt. As a cationic antibacterial agent, the quaternary ammonium salt has good antibacterial effect and can effectively improve the antibacterial performance of the high-efficiency sewage treatment agent.

[0015] Secondly, dialdehyde cellulose reacts with dodecyl succinic anhydride to prepare modified cellulose. The hydrophobic long chain of dodecyl is introduced onto the hydrophilic cellulose. The hydrophilic and hydrophobic groups can form an oriented surface layer on the surface of the solution or at the two-phase interface through hydrophilic interaction, reducing the surface tension of the interface, so as to achieve the effect of oil removal, effectively remove oil stains, and thus improve the oil removal performance of the high-efficiency sewage treatment agent. 2-Chloroethylamine reacts with the modified cellulose to form a Schiff base imine structure, which can complex with heavy metal ions, so as to achieve the effect of adsorbing heavy metals. Moreover, after the amino and imine structures complex with heavy metal ions, they can be desorbed under alkaline conditions, making the sewage treatment agent have good reusability. Specific embodiments

[0016] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative work shall fall within the protection scope of the present invention.

[0017] Example 1: A high-efficiency sewage treatment agent and its preparation method, including the following preparation steps: (1)The fly ash with a mesh size of 100 is subjected to magnetic separation using a magnetic separation tube under a strong magnetic field of 100 mT, and then separated by a weak magnetic field of 100 mT to obtain fly ash magnetic beads. The fly ash magnetic beads, deionized water, and absolute ethanol are mixed evenly at a mass ratio of 1:5:20, stirred at 200 r / min for 10 min at room temperature, ammonia water 4 times the mass of the fly ash magnetic beads is added, tetraethyl orthosilicate 5 times the mass of the fly ash is dropped at a rate of 2 drops / second, stirring is continued for 5 h, the solid in the solution is separated by a permanent magnet, washed 3 times with deionized water, and dried at 75 °C for 10 h to obtain magnetic particles. (2)Ammonium persulfate and deionized water are mixed evenly at a mass ratio of 1:2 to prepare an aqueous solution of ammonium persulfate. The magnetic particles, aniline, and 1 mol / L hydrochloric acid solution are mixed evenly at a mass ratio of 1:4:15, ultrasonicated for 15 min, and an aqueous solution of ammonium persulfate 30 times the mass of the magnetic particles is dropped at a rate of 3 drops / second, stirred at 300 r / min for 7 h at room temperature, the solid is separated by a permanent magnet, and the solid is washed 3 times with deionized water and absolute ethanol respectively, and dried at 60 °C for 4 h to obtain pre-modified magnetic particles. The pre-modified magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:1.5:35, stirred at 300 r / min for 5 h at room temperature under an argon atmosphere, (dimethylamino) acetyl chloride 0.2 times the mass of the magnetic particles is added, the temperature is raised to 145 °C, stirring is continued for 2 days, filtered by suction, the filter cake is washed 3 times with deionized water, extracted by Soxhlet for 2 days using N,N-dimethylformamide as the solvent, and vacuum dried at 55 °C for 20 h to obtain modified magnetic particles. (3)A nano-cellulose solution with a mass concentration of 1%, sodium periodate, zinc chloride, and deionized water are mixed evenly at a mass ratio of 1:1.5:0.8:200, the pH is adjusted to 4.0 with dilute hydrochloric acid, wrapped with aluminum foil to avoid light, stirred at 150 r / min for 4 h at room temperature, filtered by suction with a filter membrane with a pore size of 0.45 μm, the filter cake is washed 3 times with deionized water, and vacuum dried at 55 °C for 4 h to obtain dialdehyde cellulose. After urea and choline chloride are mixed evenly at an ammonia molar ratio of 2:1, the mixture is heated at 75 °C for 20 min to obtain a mixed solution. The dialdehyde cellulose, dodecyl succinic anhydride, and the mixed solution are mixed evenly at a mass ratio of 1:1.5:80, reacted in a microwave reactor at 55 °C for 10 min, anhydrous ethanol 1.5 times the mass of the mixed solution is added to precipitate, the precipitate is separated by centrifugation, the precipitate is washed 3 times with deionized water, and then the precipitate is dialyzed in distilled water for 72 h using a dialysis membrane with a molecular weight cut-off of 1000 Da, and freeze-dried to obtain modified cellulose. (4) Mix modified cellulose, 2-chloroethylamine, and absolute ethanol at a mass ratio of 1:1:40, stir at 300 r / min at 45 °C for 4 h, add modified magnetic particles 0.4 times the mass of the modified cellulose, continue stirring for 4 h, separate the solids in the solution with a permanent magnet, wash 3 times with deionized water, and freeze-dry to obtain a high-efficiency sewage treatment agent.

[0018] Example 2: A high-efficiency sewage treatment agent and its preparation method, including the following preparation steps: (1) Perform magnetic separation on 100-mesh fly ash with a magnetic separation tube under a strong magnetic field of 100 mT, and then separate it through a weak magnetic field of 100 mT to obtain fly ash magnetic beads; mix the fly ash magnetic beads, deionized water, and absolute ethanol at a mass ratio of 1:10:25, stir at 250 r / min at room temperature for 15 min, add ammonia water 5 times the mass of the fly ash magnetic beads, and drop tetraethyl orthosilicate 6 times the mass of the fly ash at a rate of 2 drops / second, continue stirring for 6 h, separate the solids in the solution with a permanent magnet, wash 4 times with deionized water, and dry at 80 °C for 12 h to obtain magnetic particles; (2) Mix ammonium persulfate and deionized water at a mass ratio of 1:2 to prepare an aqueous solution of ammonium persulfate; mix the magnetic particles, aniline, and 1 mol / L hydrochloric acid solution at a mass ratio of 1:4.5:20, ultrasonicate for 15 min, and drop the aqueous solution of ammonium persulfate 35 times the mass of the magnetic particles at a rate of 4 drops / second, stir at 350 r / min at room temperature for 8 h, separate the solids with a permanent magnet, wash the solids 4 times with deionized water and absolute ethanol respectively, and dry at 65 °C for 5 h to obtain pre-modified magnetic particles; mix the pre-modified magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide at a mass ratio of 1:2:40, stir at 350 r / min at room temperature for 5.5 h under an argon atmosphere, add (dimethylamino)acetyl chloride 0.3 times the mass of the magnetic particles, heat up to 150 °C, continue stirring for 2.5 days, perform suction filtration, wash the filter cake 4 times with deionized water, perform Soxhlet extraction for 2.5 days with N,N-dimethylformamide as the solvent, and vacuum dry at 60 °C for 22 h to obtain modified magnetic particles; (3) Mix a 1% nanocellulose solution, sodium periodate, zinc chloride, and deionized water in a mass ratio of 1:2:1:250. Adjust the pH to 4.0 with dilute hydrochloric acid, wrap it with aluminum foil to avoid light, stir at 200 r / min at room temperature for 5 h, filter it with a filter membrane with a pore size of 0.45 μm, wash the filter cake 4 times with deionized water, and dry it in vacuo at 60 °C for 5 h to obtain dialdehyde cellulose; after mixing urea and choline chloride in a molar ratio of 2:1, heat it at 80 °C for 25 min to obtain a mixed solution. Mix dialdehyde cellulose, dodecyl succinic anhydride, and the mixed solution in a mass ratio of 1:2:100, react at 60 °C in a microwave reactor for 15 min, add anhydrous ethanol twice the mass of the mixed solution to precipitate, centrifuge to separate the precipitate, wash the precipitate 4 times with deionized water, and then dialyze the precipitate in distilled water for 72 h with a dialysis membrane with a molecular weight cut-off of 1000 Da, and freeze-dry to obtain modified cellulose; (4) Mix modified cellulose, 2-chloroethylamine, and anhydrous ethanol in a mass ratio of 1:1.5:50, stir at 350 r / min at 50 °C for 5 h, add modified magnetic particles 0.5 times the mass of modified cellulose, continue to stir for 5 h, separate the solid in the solution with a permanent magnet, wash it 4 times with deionized water, and freeze-dry to obtain a high-efficiency sewage treatment agent.

[0019] Example 3: A high-efficiency sewage treatment agent and its preparation method, including the following preparation steps: (1) Separate fly ash with 100 mesh by magnetic separation using a magnetic separation tube under a strong magnetic field of 100 mT, and then separate it through a weak magnetic field of 100 mT to obtain fly ash magnetic beads; mix fly ash magnetic beads, deionized water, and anhydrous ethanol in a mass ratio of 1:15:30, stir at 300 r / min at room temperature for 20 min, add ammonia water 6 times the mass of fly ash magnetic beads, and drop tetraethyl orthosilicate 7 times the mass of fly ash at a rate of 2 drops / second, continue to stir for 7 h, separate the solid in the solution with a permanent magnet, wash it 5 times with deionized water, and dry it at 85 °C for 14 h to obtain magnetic particles; (2)Mix ammonium persulfate and deionized water in a mass ratio of 1:2 to obtain an aqueous solution of ammonium persulfate; mix magnetic particles, aniline, and 1 mol / L hydrochloric acid solution in a mass ratio of 1:5:25, ultrasonicate for 15 min, and dropwise add an aqueous solution of ammonium persulfate 40 times the mass of the magnetic particles at a rate of 5 drops / second. Stir at 400 r / min at room temperature for 9 h, separate the solid with a permanent magnet, wash the solid 5 times with deionized water and anhydrous ethanol respectively, and dry at 70 °C for 6 h to obtain pre-modified magnetic particles; mix pre-modified magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:2.5:45, stir at 400 r / min at room temperature for 6 h in an argon atmosphere, add (dimethylamino)acetyl chloride 0.4 times the mass of the magnetic particles, raise the temperature to 155 °C, continue to stir for 3 days, perform suction filtration, wash the filter cake 5 times with deionized water, perform Soxhlet extraction for 3 days using N,N-dimethylformamide as the solvent, and vacuum dry at 65 °C for 24 h to obtain modified magnetic particles; (3)Mix a 1% nano-cellulose solution, sodium periodate, zinc chloride, and deionized water in a mass ratio of 1:2.5:1.2:300, adjust the pH to 4.0 with dilute hydrochloric acid, wrap it with aluminum foil to avoid light, stir at 250 r / min at room temperature for 6 h, perform suction filtration with a filter membrane with a pore size of 0.45 μm, wash the filter cake 5 times with deionized water, and vacuum dry at 65 °C for 6 h to obtain dialdehyde cellulose; mix urea and choline chloride in a molar ratio of 2:1, heat at 85 °C for 30 min to obtain a mixed solution, mix dialdehyde cellulose, dodecyl succinic anhydride, and the mixed solution in a mass ratio of 1:2.5:120, react at 65 °C in a microwave reactor for 20 min, add anhydrous ethanol 2.5 times the mass of the mixed solution to precipitate, centrifuge to separate the precipitate, wash the precipitate 5 times with deionized water, and then dialyze the precipitate in distilled water for 72 h using a dialysis membrane with a molecular weight cut-off of 1000 Da, and freeze-dry to obtain modified cellulose; (4)Mix modified cellulose, 2-chloroethylamine, and anhydrous ethanol in a mass ratio of 1:2:60, stir at 400 r / min at 55 °C for 6 h, add modified magnetic particles 0.6 times the mass of the modified cellulose, continue to stir for 6 h, separate the solid in the solution with a permanent magnet, wash 5 times with deionized water, and freeze-dry to obtain a high-efficiency sewage treatment agent.

[0020] Comparative Example 1: A high-efficiency sewage treatment agent and its preparation method, including the following preparation steps: (1) Mix ammonium persulfate and deionized water in a mass ratio of 1:2 to obtain an aqueous solution of ammonium persulfate. Mix nano-silica, aniline, and 1 mol / L hydrochloric acid solution in a mass ratio of 1:4.5:20, ultrasonicate for 15 min, and dropwise add an aqueous solution of ammonium persulfate 35 times the mass of nano-silica at a rate of 4 drops per second. Stir at 350 r / min at room temperature for 8 h, centrifuge to separate the solid, wash the solid 4 times with deionized water and anhydrous ethanol respectively, and dry at 65 °C for 5 h to obtain pre-modified particles. Mix the pre-modified particles, anhydrous potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:2:40, stir at 350 r / min at room temperature for 5.5 h under an argon atmosphere, add (dimethylamino)acetyl chloride 0.3 times the mass of nano-silica, raise the temperature to 150 °C, continue to stir for 2.5 days, filter by suction, wash the filter cake 4 times with deionized water, perform Soxhlet extraction for 2.5 days using N,N-dimethylformamide as the solvent, and vacuum dry at 60 °C for 22 h to obtain modified particles. (2) Mix a 1% mass concentration nano-cellulose solution, sodium periodate, zinc chloride, and deionized water in a mass ratio of 1:2:1:250, adjust the pH to 4.0 with dilute hydrochloric acid, wrap with aluminum foil to avoid light, stir at 200 r / min at room temperature for 5 h, filter by suction through a filter membrane with a pore size of 0.45 μm, wash the filter cake 4 times with deionized water, and vacuum dry at 60 °C for 5 h to obtain dialdehyde cellulose. Mix urea and choline chloride in an ammonia molar ratio of 2:1 and heat at 80 °C for 25 min to obtain a mixed solution. Mix dialdehyde cellulose, dodecyl succinic anhydride, and the mixed solution in a mass ratio of 1:2:100, react in a microwave reactor at 60 °C for 15 min, add anhydrous ethanol 2 times the mass of the mixed solution to precipitate, centrifuge to separate the precipitate, wash the precipitate 4 times with deionized water, and then dialyze the precipitate in distilled water for 72 h using a dialysis membrane with a molecular weight cut-off of 1000 Da, and freeze-dry to obtain modified cellulose. (3) Mix modified cellulose, 2-chloroethylamine, and anhydrous ethanol in a mass ratio of 1:1.5:50, stir at 350 r / min at 50 °C for 5 h, add modified particles 0.5 times the mass of modified cellulose, continue to stir for 5 h, centrifuge to separate the solid, wash the solid 4 times with deionized water, and freeze-dry to obtain a high-efficiency sewage treatment agent.

[0021] Comparative Example 2: A high-efficiency sewage treatment agent and its preparation method, including the following preparation steps: (1)The fly ash with a mesh size of 100 is subjected to magnetic separation using a magnetic separation tube under a strong magnetic field of 100 mT, and then separated by a weak magnetic field of 100 mT to obtain fly ash magnetic beads; the fly ash magnetic beads, deionized water, and absolute ethanol are mixed evenly at a mass ratio of 1:10:25, stirred at 250 r / min for 15 min at room temperature, ammonia water 5 times the mass of the fly ash magnetic beads is added, tetraethyl orthosilicate 6 times the mass of the fly ash is dropped at a rate of 2 drops / second, stirring is continued for 6 h, the solid in the solution is separated by a permanent magnet, washed 4 times with deionized water, and dried at 80 °C for 12 h to obtain magnetic particles; (2)The magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:2:40, stirred at 350 r / min for 5.5 h at room temperature under an argon atmosphere, (dimethylamino) acetyl chloride 0.3 times the mass of the magnetic particles is added, the temperature is raised to 150 °C, stirring is continued for 2.5 days, filtered by suction, the filter cake is washed 4 times with deionized water, extracted with a Soxhlet extractor for 2.5 days using N,N-dimethylformamide as the solvent, and vacuum dried at 60 °C for 22 h to obtain modified magnetic particles; (3)A nano-cellulose solution with a mass concentration of 1%, sodium periodate, zinc chloride, and deionized water are mixed evenly at a mass ratio of 1:2:1:250, the pH is adjusted to 4.0 with dilute hydrochloric acid, wrapped with aluminum foil to avoid light, stirred at 200 r / min for 5 h at room temperature, filtered by suction using a filter membrane with a pore size of 0.45 μm, the filter cake is washed 4 times with deionized water, and vacuum dried at 60 °C for 5 h to obtain dialdehyde cellulose; after mixing urea and choline chloride in an ammonia molar ratio of 2:1 and heating at 80 °C for 25 min to obtain a mixed solution, the dialdehyde cellulose, dodecyl succinic anhydride, and the mixed solution are mixed evenly at a mass ratio of 1:2:100, reacted in a microwave reactor at 60 °C for 15 min, anhydrous ethanol 2 times the mass of the mixed solution is added to precipitate, the precipitate is separated by centrifugation, the precipitate is washed 4 times with deionized water, and then dialyzed in distilled water for 72 h using a dialysis membrane with a cut-off molecular weight of 1000 Da, and freeze-dried to obtain modified cellulose; (4)The modified cellulose, 2-chloroethylamine, and absolute ethanol are mixed evenly at a mass ratio of 1:1.5:50, stirred at 350 r / min for 5 h at 50 °C, modified magnetic particles 0.5 times the mass of the modified cellulose are added, stirring is continued for 5 h, the solid in the solution is separated by a permanent magnet, washed 4 times with deionized water, and freeze-dried to obtain a high-efficiency sewage treatment agent.

[0022] Comparative Example 3: A high-efficiency sewage treatment agent and its preparation method, including the following preparation steps: (1) The fly ash with a mesh size of 100 is subjected to magnetic separation using a magnetic separation tube under a strong magnetic field of 100 mT, and then separated by a weak magnetic field of 100 mT to obtain fly ash magnetic beads; the fly ash magnetic beads, deionized water, and absolute ethanol are mixed evenly at a mass ratio of 1:10:25, stirred at 250 r / min for 15 min at room temperature, ammonia water 5 times the mass of the fly ash magnetic beads is added, tetraethyl orthosilicate 6 times the mass of the fly ash is dropped at a rate of 2 drops per second, stirring is continued for 6 h, the solid in the solution is separated using a permanent magnet, washed 4 times with deionized water, and dried at 80 °C for 12 h to obtain magnetic particles; (2) Ammonium persulfate and deionized water are mixed evenly at a mass ratio of 1:2 to prepare an aqueous solution of ammonium persulfate; the magnetic particles, aniline, and 1 mol / L hydrochloric acid solution are mixed evenly at a mass ratio of 1:4.5:20, ultrasonicated for 15 min, and the aqueous solution of ammonium persulfate 35 times the mass of the magnetic particles is dropped at a rate of 4 drops per second, stirred at 350 r / min for 8 h at room temperature, the solid is separated using a permanent magnet, the solid is washed 4 times with deionized water and absolute ethanol respectively, and dried at 65 °C for 5 h to obtain pre-modified magnetic particles; the pre-modified magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:2:40, stirred at 350 r / min for 5.5 h at room temperature under an argon atmosphere, (dimethylamino) acetyl chloride 0.3 times the mass of the magnetic particles is added, the temperature is raised to 150 °C, stirring is continued for 2.5 days, filtered by suction, the filter cake is washed 4 times with deionized water, Soxhlet extracted for 2.5 days using N,N-dimethylformamide as the solvent, and vacuum dried at 60 °C for 22 h to obtain modified magnetic particles; (4) Cellulose, 2-chloroethylamine, and absolute ethanol are mixed evenly at a mass ratio of 1:1.5:50, stirred at 350 r / min for 5 h at 50 °C, modified magnetic particles 0.5 times the mass of cellulose are added, stirring is continued for 5 h, the solid in the solution is separated using a permanent magnet, washed 4 times with deionized water, and freeze-dried to obtain a high-efficiency sewage treatment agent.

[0023] Comparative Example 4: A high-efficiency sewage treatment agent and its preparation method, including the following preparation steps: (1) The fly ash with a mesh size of 100 is subjected to magnetic separation using a magnetic separation tube under a strong magnetic field of 100 mT, and then separated by a weak magnetic field of 100 mT to obtain fly ash magnetic beads; the fly ash magnetic beads, deionized water, and absolute ethanol are mixed evenly at a mass ratio of 1:10:25, stirred at 250 r / min for 15 min at room temperature, ammonia water 5 times the mass of the fly ash magnetic beads is added, tetraethyl orthosilicate 6 times the mass of the fly ash is dropped at a rate of 2 drops per second, stirring is continued for 6 h, the solid in the solution is separated using a permanent magnet, washed 4 times with deionized water, and dried at 80 °C for 12 h to obtain magnetic particles; (2) Ammonium persulfate and deionized water were mixed evenly at a mass ratio of 1:2 to prepare an aqueous solution of ammonium persulfate; magnetic particles, aniline, and 1 mol / L hydrochloric acid solution were mixed evenly at a mass ratio of 1:4.5:20, ultrasonically treated for 15 min, and an aqueous solution of ammonium persulfate 35 times the mass of the magnetic particles was dropped at a rate of 4 drops / second, stirred at 350 r / min at room temperature for 8 h, the solid was separated with a permanent magnet, the solid was washed 4 times with deionized water and anhydrous ethanol respectively, and dried at 65 °C for 5 h to obtain pre-modified magnetic particles; the pre-modified magnetic particles, anhydrous potassium carbonate, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:2:40, stirred at 350 r / min at room temperature for 5.5 h under an argon atmosphere, (dimethylamino) acetyl chloride 0.3 times the mass of the magnetic particles was added, the temperature was raised to 150 °C, and stirring was continued for 2.5 days, filtered by suction, the filter cake was washed 4 times with deionized water, Soxhlet extracted for 2.5 days with N,N-dimethylformamide as the solvent, and vacuum dried at 60 °C for 22 h to obtain modified magnetic particles; (3) A 1% nanocellulose solution by mass concentration, sodium periodate, zinc chloride, and deionized water were mixed evenly at a mass ratio of 1:2:1:250, the pH was adjusted to 4.0 with dilute hydrochloric acid, wrapped with aluminum foil to avoid light, stirred at 200 r / min at room temperature for 5 h, filtered by suction with a filter membrane with a pore size of 0.45 μm, the filter cake was washed 4 times with deionized water, and vacuum dried at 60 °C for 5 h to obtain dialdehyde cellulose; after urea and choline chloride were mixed evenly at a molar ratio of 2:1, a mixed solution was prepared by heating at 80 °C for 25 min. The dialdehyde cellulose, dodecyl succinic anhydride, and the mixed solution were mixed evenly at a mass ratio of 1:2:100, reacted at 60 °C in a microwave reactor for 15 min, anhydrous ethanol 2 times the mass of the mixed solution was added to precipitate, the precipitate was separated by centrifugation, the precipitate was washed 4 times with deionized water, and then the precipitate was dialyzed in distilled water for 72 h with a dialysis membrane with a molecular weight cut-off of 1000 Da, and freeze-dried to obtain modified cellulose; (4) The modified cellulose and anhydrous ethanol were mixed evenly at a mass ratio of 1:50, stirred at 350 r / min at 50 °C for 5 h, 0.5 times the mass of the modified magnetic particles of the modified cellulose was added, and stirring was continued for 5 h. The solid in the solution was separated with a permanent magnet, washed 4 times with deionized water, and freeze-dried to obtain a high-efficiency sewage treatment agent.

[0024] Test Example 1: Oil removal rate test: Weigh the oily sludge into a sample bottle. Prepare the high - efficiency sewage treatment agent prepared in each example and comparative example into an aqueous solution with a concentration of 2.5 g / L. Weigh the oily sludge into a sample bottle, add an aqueous solution of the sewage treatment agent 10 times the mass of the oily sludge, disperse it evenly, then place it in a constant - temperature water - bath shaker, and treat it at a speed of 200 r / min at 70 °C for 2 h. Let it stand for 4 h, recover the oil layer and emulsion layer, dry the sludge layer in an oven at 60 °C until constant weight, and finally use an automatic ash and moisture analyzer to measure the oil content of the remaining solid. Calculate the oil removal rate according to the formula: Oil removal rate = (oil content of oily sludge before treatment - oil content of oily sludge after treatment) / oil content of oily sludge before treatment * 100%. The results are shown in Table 1.

[0025] Oil removal rate (%) Oil removal rate (%) Example 1 64.88 Comparative Example 1 65.13 Example 2 65.21 Comparative Example 2 65.22 Example 3 65.17 Comparative Example 3 64.98 Comparative Example 4 21.36 From the comparison of the experimental data of Examples 1 - 3 and Comparative Examples 1 - 4 in Table 1, it can be found that the high - efficiency sewage treatment agent prepared by the present invention has good oil - removing performance.

[0026] By comparison, the oil removal rates of Examples 1 - 3 are significantly better than that of Comparative Example 3, indicating that the modified cellulose prepared by the reaction of dialdehyde cellulose and dodecyl succinic anhydride introduces a hydrophobic long chain of dodecyl on the hydrophilic cellulose. The hydrophilic - hydrophobic interaction between hydrophilic groups and hydrophobic groups can enable the sewage treatment agent to form an oriented surface layer on the surface of the solution or at the two - phase interface, reducing the surface tension of the interface, thereby achieving the oil - removal effect, effectively removing oil stains, and thus improving the oil - removing performance of the high - efficiency sewage treatment agent.

[0027] Test Example 2: 1. Heavy metal removal performance test: Put 0.1 g of adsorbent into a 100 - mL conical flask, add 50 mL of hexavalent Cr solution with a certain initial concentration, and place the conical flask in a constant - temperature shaker for an adsorption experiment at a speed of 200 r / min. After the reaction is completed, use a magnet to separate the adsorbent, then take the supernatant, filter it with a 0.45 - μm filter head, and then conduct a concentration test. The measurement of the hexavalent chromium Cr concentration is carried out using an ultraviolet spectrophotometer. Use 1 mol / L sodium hydroxide and 1 mol / L hydrochloric acid solutions to adjust the pH of the reaction system to 2.0, conduct 3 parallel experiments, and record the removal rate of hexavalent chromium. The results are shown in Table 2.

[0028] Adsorption and regeneration performance test: Use 1 mol / L sodium hydroxide solution as the eluent, treat the adsorbed high - efficiency sewage treatment agent and then conduct a cyclic adsorption test for 7 cycles, and record the removal rate of hexavalent chromium after 7 cycles. The results are shown in Table 2.

[0029] Hexavalent chromium removal rate (%) Removal rate after 7 cycles (%) Example 1 98.8 98.2 Example 2 99.2 97.9 Example 3 99.1 98.1 Comparative Example 1 99.1 97.8 Comparative Example 2 62.74 48.53 Comparative Example 3 78.49 56.24 Comparative Example 4 98.8 55.69 From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 2, it can be found that the high-efficiency sewage treatment agent prepared by the present invention has good heavy metal removal performance and reusability.

[0030] By comparison, the removal rate of hexavalent chromium in Examples 1-3 is greater than that in Comparative Example 2, indicating that polyaniline polymerizes on the surface of magnetic particles to form a polyaniline layer. The polyaniline structure contains a large number of amino and imine structures, which can complex with heavy metal ions, thereby achieving the effect of adsorbing heavy metals and effectively improving the heavy metal removal performance of the high-efficiency sewage treatment agent; the removal rate of hexavalent chromium in Examples 1-3 is greater than that in Comparative Example 3, indicating that 2-chloroethylamine reacts with dialdehyde cellulose to form a Schiff base, and the formed Schiff base is an imine structure, which can complex metal ions, thereby achieving the effect of removing heavy metals and improving the heavy metal removal performance of the sewage treatment agent.

[0031] By comparison, the removal rate of hexavalent chromium after 7 cycles in Examples 1-3 is greater than that in Comparative Example 2 after 7 cycles, indicating that the abundant amino and imine structures on the polyaniline structure on the surface of magnetic particles can desorb after complexing heavy metals in an alkaline environment, so it has good reusability; the removal rate of hexavalent chromium after 7 cycles in Examples 1-3 is greater than that in Comparative Example 3 after 7 cycles, indicating that 2-chloroethylamine reacts with dialdehyde cellulose to form a Schiff base imine structure, which can desorb under alkaline conditions after complexing metal ions, making the sewage treatment agent have good reusability; the removal rate of hexavalent chromium after 7 cycles in Examples 1-3 is greater than that in Comparative Example 4 after 7 cycles, indicating that 2-chloroethylamine can react with (dimethylamino) acetyl chloride to form a quaternary ammonium salt, making the modified magnetic particles and modified cellulose form a chemical crosslink. When using a permanent magnet to separate the sewage treatment agent, both the modified cellulose and the modified magnetic particles can be separated at the same time, giving full play to their reusability.

[0032] Test Example 3: Measurement of magnetic strength: Use an HH-20 type vibrating sample magnetometer to measure the magnetic properties of each example and comparative example. Magnetic field range: 0~±1T. The results are shown in Table 3.

[0033] Specific saturation magnetization (emu / g) Specific saturation magnetization (emu / g) Example 1 49.67 Comparative Example 1 0 Example 2 49.55 Comparative Example 2 49.75 Example 3 49.81 Comparative Example 3 49.46 Comparative Example 4 49.59 From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 1, it can be found that the specific saturation magnetization of Examples 1-3 is greater than that of Comparative Example 1, indicating that the sewage treatment agent prepared by the present invention is rich in magnetism. The fly ash magnetic beads prepared by magnetic separation of fly ash have good magnetism and can be adsorbed by a permanent magnet. Therefore, the high-efficiency sewage treatment agent can be adsorbed by a permanent magnet after treating sewage, so as to achieve a separation effect and effectively improve the separation efficiency of the sewage treatment agent.

[0034] Test Example 4: Antibacterial performance test: The sewage treated in each example and comparative example was subjected to bacterial culture, and the sewage untreated with the sewage treatment agent was used as the control group, and the sterilization rate was recorded. The results are shown in Table 4.

[0035] Bacteriostatic rate (%) Bacteriostatic rate (%) Example 1 99.9 Comparative Example 1 99.9 Example 2 99.8 Comparative Example 2 16.2 Example 3 99.9 Comparative Example 3 99.9 Comparative Example 4 14.5 From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 4, it can be found that the high-efficiency sewage treatment agent prepared by the present invention has good antibacterial performance.

[0036] By comparison, the antibacterial rates of Examples 1 to 3 are significantly greater than those of Comparative Examples 2 and 4, indicating that 2-chloroethylamine can react with (dimethylamino) acetyl chloride to form a quaternary ammonium salt. The quaternary ammonium salt is a cationic antibacterial agent with good antibacterial effects and can effectively improve the antibacterial performance of the high-efficiency sewage treatment agent.

[0037] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and do not limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high-efficiency sewage treatment agent, characterized in that: The high-efficiency sewage treatment agent is prepared by reacting modified magnetic particles, modified cellulose and 2-chloroethylamine; The modified magnetic particles are prepared by first reacting the magnetic particles with aniline and then with (dimethylamino)acetyl chloride; The modified cellulose is prepared by reacting cellulose with sodium periodate and zinc chloride to obtain dialdehyde cellulose, and reacting dialdehyde cellulose with dodecyl succinic anhydride to obtain the modified cellulose.

2. A high-efficiency sewage treatment agent and a preparation method thereof, characterized in that: The method comprises the following preparation steps: (1) Mix fly ash magnetic beads, deionized water, and anhydrous ethanol in a mass ratio of 1: (5-15): (20-30), stir at 200-300 r / min for 10-20 min at room temperature, add ammonia water 4-6 times the mass of the magnetic particles, and drip tetraethyl orthosilicate 5-7 times the mass of the fly ash at a rate of 2 seconds / drop, continue stirring for 5-7 hours, separate the solid in the solution with a permanent magnet, wash with deionized water 3-5 times, and dry at 75-85°C for 10-14 hours to obtain magnetic particles; (2) ammonium persulfate and deionized water were mixed in a mass ratio of 1:2 to obtain an aqueous solution of ammonium persulfate; magnetic particles, aniline, and 1 mol / L hydrochloric acid solution were mixed, ultrasonicated for 15 min, and an aqueous solution of ammonium persulfate 30 to 40 times the mass of the magnetic particles was added dropwise at a rate of 3 to 5 seconds per drop, stirred at 300 to 400 r / min for 7 to 9 hours at room temperature, and the solid was separated by a permanent magnet. The solid was washed with deionized water and anhydrous ethanol for 3 to 5 times, respectively, and dried at 60 to 70 °C for 4 to 6 hours to obtain a pre-modified magnetic particle. Pre-modified magnetic particles; pre-modified magnetic particles, anhydrous potassium carbonate and N,N-dimethylformamide are mixed, stirred at 300-400 r / min for 5-6 hours at room temperature under argon atmosphere, (dimethylamino)acetyl chloride is added in an amount of 0.2-0.4 times the mass of the magnetic particles, the temperature is raised to 145-155°C, stirring is continued for 2-3 days, filtered, the filter is washed with deionized water for 3-5 times, N,N-dimethylformamide is used as solvent, Soxhlet extraction is performed for 2-3 days, and vacuum drying is performed at 55-65°C for 20-24 hours to obtain modified magnetic particles; (3) Mix 1% nanocellulose solution, sodium periodate, zinc chloride and deionized water, adjust the pH to 4.0 with dilute hydrochloric acid, cover with aluminum foil to avoid light, stir at 150-250 r / min for 4-6 h at room temperature, filter with a filter membrane with a pore size of 0.45 μm, wash the filter cake with deionized water for 3-5 times, and vacuum dry at 55-65 °C for 4-6 h to obtain dialdehyde cellulose; mix urea and choline chloride in a molar ratio of 2:1, and heat at 75-8 The mixed solution is prepared by heating at 5°C for 20-30 minutes, the dialdehyde cellulose, dodecyl succinic anhydride and the mixed solution are mixed, reacted in a microwave reactor at 55-65°C for 10-20 minutes, anhydrous ethanol in an amount of 1.5-2.5 times the mass of the mixed solution is added to precipitate, the precipitate is separated by centrifugation, the precipitate is washed with deionized water for 3-5 times, and then the precipitate is dialyzed in distilled water for 72 hours using a dialysis membrane with a molecular weight cutoff of 1000Da, and freeze-dried to obtain modified cellulose; (4) Modified cellulose, 2-chloroethylamine and anhydrous ethanol are mixed in a mass ratio of 1: (1-2): (40-60), stirred at 300-400 r / min at 45-55°C for 4-6 h, modified magnetic particles in an amount of 0.4-0.6 times the mass of the modified cellulose are added, stirring is continued for 4-6 h, the solid in the solution is separated with a permanent magnet, washed with deionized water for 3-5 times, and freeze-dried to obtain a high-efficiency sewage treatment agent.

3. A high-efficiency sewage treatment agent and a preparation method thereof according to claim 2, characterized in that: The method for preparing fly ash magnetic beads in step (1) is as follows: 100-mesh fly ash is magnetically separated using a magnetic separation tube under a strong magnetic field of 100 mT, and then separated using a weak magnetic field of 100 mT to obtain the magnetic beads.

4. A high-efficiency sewage treatment agent and a preparation method thereof according to claim 2, characterized in that: In step (2), the mass ratio of the magnetic particles, aniline and 1 mol / L hydrochloric acid solution is 1:(4-5):(15-25).

5. A high-efficiency sewage treatment agent and a preparation method thereof according to claim 2, characterized in that: In step (2), the mass ratio of the pre-modified magnetic particles, anhydrous potassium carbonate and N,N-dimethylformamide is 1:(1.5-2.5):(35-45).

6. A high-efficiency sewage treatment agent and a preparation method thereof according to claim 2, characterized in that: In step (3), the mass ratio of the 1% nanocellulose solution, sodium periodate, zinc chloride and deionized water is 1: (1.5-2.5): (0.8-1.2): (200-300).

7. A high-efficiency sewage treatment agent and a preparation method thereof according to claim 2, characterized in that: In step (3), the mass ratio of dialdehyde cellulose, dodecyl succinic anhydride and mixed solution is 1: (1.5-2.5): (80-120).

8. A high-efficiency sewage treatment agent and a preparation method thereof according to claim 2, characterized in that: In step (4), the mass ratio of the modified cellulose, 2-chloroethylamine and anhydrous ethanol is 1:(1-2):(40-60).