Preparation method of activated carbon-containing adsorption material and application of activated carbon-containing adsorption material in wastewater treatment

Abstract

The invention relates to the technical field of wastewater treatment, and discloses a preparation method of an activated carbon-containing adsorption material and application of the activated carbon-containing adsorption material in wastewater treatment.The preparation method comprises the steps that modified phenolic resin, activated carbon and sulfo chitosan are added into a double-screw extruder, and melt extrusion is performed to obtain the activated carbon-containing adsorption material; the phenolic resin is high in phenolic hydroxyl content and strong in hydrophilicity, has a good adsorption effect on chromium ions, lead ions and other heavy metal ions in wastewater, and has good adsorption energy on the heavy metal ions due to the coordination and hydrogen-bond interaction of amido in the phenolic resin, and flocculation is achieved through synergism; a sulfonic acid group and chromium ions, lead ions and other heavy metal ions in the wastewater are subjected to a complexation reaction to form tiny flocs, the tiny flocs and quaternary ammonium salt groups are electrically neutralized to form precipitates, the heavy metal ions are effectively removed, and the flocculation effect is achieved; meanwhile, chitosan is a natural antibacterial agent, and forms an antibacterial system with a quaternary ammonium salt group and a sulfonic acid group to achieve a synergistic antibacterial effect.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment, in particular to a method for preparing an activated carbon-containing adsorption material and an application thereof in wastewater treatment. Background Art

[0002] Human activities will cause a large amount of domestic, agricultural and industrial waste to be discharged into clean water, which not only pollutes water resources but also endangers human health. Sewage contains a large amount of heavy metal ions such as chromium ions and lead ions. How to remove them is the key to solving the problem. Activated carbon can effectively deodorize and decolorize sewage and effectively remove harmful substances in water. Activated carbon has a developed pore structure, good adsorption properties, high mechanical strength, and is easy to regenerate repeatedly. It is compounded with modified phenolic resin, activated carbon, and sulfonic chitosan to prepare an activated carbon adsorption material that can not only treat sewage but also has a good bactericidal effect. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In view of the shortcomings of the prior art, the present invention provides a method for preparing an activated carbon adsorption material and its application in wastewater treatment, which has a good wastewater treatment effect, effectively reduces heavy metal ions in water, and has a good antibacterial effect.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a method for preparing an activated carbon-containing adsorption material, the method for preparing an activated carbon-containing adsorption material comprising the following steps:

[0007] (1) adding o-nitrophenylhydrazine, ammonia water, isopropanol and hexylene glycol to N,N-dimethylformamide solvent, stirring and mixing, reacting at a reaction pressure of 5-10 MPa and at 120-150° C. for 2-3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, filtered and dried to obtain intermediate 1;

[0008] (2) Under nitrogen atmosphere, the intermediate 1 and ε-caprolactone are stirred evenly, and then stannous octoate catalyst is added, and the reaction is carried out at 135-145° C. for 6-10 hours. After the reaction is completed, the crude product is first dissolved in chloroform and then precipitated with anhydrous ether. The dissolution and precipitation are repeated 2-4 times, and the product is vacuum dried for 20-30 hours to obtain modified caprolactone;

[0009] (3) adding 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid to thionyl chloride, reacting at 60-70° C. for 4-7 h, and then distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0010] (4) adding p-aminophenol, modified caprolactone and intermediate 2 to N,N-dimethylformamide solvent, stirring to dissolve, then adding triethylamine catalyst, reacting at 80-90° C. for 6-10 hours, and then distilling under reduced pressure after completion, washing the product with n-hexane to obtain modified phenol;

[0011] (5) adding modified phenol and formaldehyde into a stirrer, reacting at 85-100° C. for 40-60 min, then adding ethylenediamine dropwise, heating to 85-95° C., reflux dehydration, and cooling to room temperature to obtain a modified phenolic resin;

[0012] (6) Add 15-30 parts by weight of modified phenolic resin, 10-15 parts by weight of activated carbon, and 8-20 parts by weight of sulfonic acid chitosan into a twin-screw extruder, and melt extrude at 185-200° C. to obtain an activated carbon-containing adsorption material.

[0013] Preferably, the mass ratio of o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol in (1) is 1:1.1-1.3:0.8-1.2:2-4.

[0014] Preferably, the mass ratio of the intermediate 1, ε-caprolactone and stannous octoate catalyst in (2) is 1.2-1.5:1:0.01-0.03.

[0015] Preferably, the mass ratio of thionyl chloride to 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid in (3) is 1.2-1.6:1.

[0016] Preferably, the mass ratio of p-aminophenol, modified caprolactone, intermediate 2 and triethylamine catalyst in (4) is 1.1-1.4:1.6-1.8:1:0.03-0.04.

[0017] Preferably, the mass ratio of modified phenol, formaldehyde and ethylenediamine in (5) is 1:1.2-1.5:0.01-0.03.

[0018] Preferably, the preparation method of the sulfonic acid chitosan in (6) is:

[0019] S1. Add 5-10 parts by weight of chitosan to an ethanol solvent, heat in a water bath at 75-90°C, then add 8-12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at a constant pressure, react for 6-9h, wash with anhydrous ethanol, dry, and dialyze to obtain modified chitosan;

[0020] S2. Add 6-8 parts by weight of modified chitosan and 5-9 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir to dissolve, react at 75-90°C for 8-15h, and then distill under reduced pressure, filter and dry to obtain sulfonic chitosan.

[0021] Preferably, it is characterized by the application in wastewater treatment.

[0022] (III) Beneficial technical effects

[0023] The invention adds modified phenolic resin, activated carbon and sulfonic acid chitosan into a twin-screw extruder for melt extrusion to obtain an activated carbon-containing adsorption material.

[0024] o-Nitrophenylhydrazine, ammonia water, isopropanol and hexylene glycol are added to N,N-dimethylformamide solvent, stirred and mixed, and reacted to obtain intermediate 1; intermediate 1 and ε-caprolactone are reacted with stannous octoate catalyst to obtain modified caprolactone; p-aminophenol, modified caprolactone and intermediate 2 are reacted with triethylamine catalyst to obtain modified phenol; modified phenol and formaldehyde are added to a stirrer, and then ethylenediamine is added dropwise to react to obtain modified phenolic resin; chitosan is reacted with 2,3-epoxypropyltrimethylammonium chloride to obtain modified chitosan; modified chitosan is reacted with sodium 3-chloro-2-hydroxypropanesulfonate to obtain sulfonic chitosan.

[0025] The phenolic hydroxyl content of the formaldehyde resin is relatively high, and the hydrophilicity is strong. It has a good adsorption effect on heavy metal ions such as chromium ions and lead ions in wastewater, and the coordination and hydrogen bonding of the amino groups in the phenolic resin make it have good adsorption energy for heavy metal ions, and synergistically achieve flocculation; the sulfonic acid group and the heavy metal ions such as chromium ions and lead ions in the wastewater undergo a complex reaction to form tiny flocs, which are electrically neutralized with the quaternary ammonium salt group to form a precipitate, effectively removing the heavy metal ions and achieving the effect of flocculation; and the phenolic hydroxyl group in the modified phenolic resin and the sulfonic acid group, amino group, and hydroxyl group in the sulfonic chitosan form hydrogen bonds to form a cross-linked network, which can more effectively adsorb heavy metal ions in wastewater and achieve the effect of sewage treatment; at the same time, chitosan is a natural antibacterial agent, and constitutes an antibacterial system with the quaternary ammonium salt group and the sulfonic acid group, and has a synergistic antibacterial effect. DETAILED DESCRIPTION

[0026] Example 1

[0027] (1) adding o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol to N,N-dimethylformamide solvent, wherein the mass ratio of o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol is 1:1.1:0.8:2, stirring and mixing, reacting, the reaction pressure is 5 MPa, reacting at 120° C. for 2 h, and after the reaction, removing the solvent by reduced pressure distillation, filtering and drying to obtain intermediate 1;

[0028] (2) Under nitrogen atmosphere, the intermediate 1 and ε-caprolactone were stirred evenly, and then a stannous octoate catalyst was added, wherein the mass ratio of the intermediate 1, ε-caprolactone, and the stannous octoate catalyst was 1.2:1:0.01, and the reaction was carried out at 135° C. for 6 h. After the reaction was completed, the crude product was first dissolved with chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated twice. The product was vacuum dried for 20 h to obtain modified caprolactone;

[0029] (3) adding 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid to thionyl chloride, wherein the mass ratio of thionyl chloride to 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid is 1.2:1, reacting at 60° C. for 4 h, and then distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0030] (4) adding p-aminophenol, modified caprolactone, and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of p-aminophenol, modified caprolactone, intermediate 2, and triethylamine catalyst is 1.1:1.6:1:0.03, stirring to dissolve, and then continuing to add triethylamine catalyst, reacting at 80° C. for 6 hours, and then distilling under reduced pressure after completion, washing the product with n-hexane to obtain modified phenol;

[0031] (5) adding modified phenol and formaldehyde into a stirrer, reacting at 85° C. for 40 min, then adding ethylenediamine dropwise, wherein the mass ratio of modified phenol, formaldehyde, and ethylenediamine is 1:1.2:0.01, heating to 85° C., reflux dehydration, and cooling to room temperature to obtain a modified phenolic resin;

[0032] (6) adding 5 parts by weight of chitosan to an ethanol solvent, heating in a water bath at 75° C., then adding 8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, reacting for 6 hours, washing with anhydrous ethanol, drying, and dialyzing to obtain modified chitosan;

[0033] (7) adding 6 parts by weight of modified chitosan and 5 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 75° C. for 8 h, and then distilling under reduced pressure, filtering and drying to obtain sulfonic chitosan;

[0034] (8) 15 parts by weight of modified phenolic resin, 10 parts by weight of activated carbon, and 8 parts by weight of sulfonic acid chitosan were added to a twin-screw extruder and melt-extruded at 185° C. to obtain an activated carbon-containing adsorbent material.

[0035] Example 2

[0036] (1) adding o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol to N,N-dimethylformamide solvent, wherein the mass ratio of o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol is 1:1.3:1.2:4, stirring and mixing, reacting, the reaction pressure is 10 MPa, and the reaction is carried out at 150° C. for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, filtered and dried to obtain intermediate 1;

[0037] (2) Under nitrogen atmosphere, the intermediate 1 and ε-caprolactone were stirred evenly, and then a stannous octoate catalyst was added, wherein the mass ratio of the intermediate 1, ε-caprolactone, and the stannous octoate catalyst was 1.5:1:0.03, and the reaction was carried out at 145° C. for 10 h. After the reaction was completed, the crude product was first dissolved with chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated 4 times. The product was vacuum dried for 30 h to obtain modified caprolactone;

[0038] (3) adding 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid to thionyl chloride, wherein the mass ratio of thionyl chloride to 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid is 1.6:1, reacting at 70° C. for 7 h, and then distilling under reduced pressure after the reaction, filtering and drying to obtain intermediate 2;

[0039] (4) adding p-aminophenol, modified caprolactone, and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of p-aminophenol, modified caprolactone, intermediate 2, and triethylamine catalyst is 1.4:1.8:1:0.04, stirring to dissolve, and then continuing to add triethylamine catalyst, reacting at 90° C. for 10 hours, and then distilling under reduced pressure after completion, washing the product with n-hexane to obtain modified phenol;

[0040] (5) adding modified phenol and formaldehyde into a stirrer, reacting at 100° C. for 60 min, then adding ethylenediamine dropwise, wherein the mass ratio of modified phenol, formaldehyde, and ethylenediamine is 1:1.5:0.03, heating to 95° C., reflux dehydration, and cooling to room temperature to obtain a modified phenolic resin;

[0041] (6) adding 10 parts by weight of chitosan to an ethanol solvent, heating the mixture in a water bath at 90° C., then adding 12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, reacting the mixture for 9 hours, washing the mixture with anhydrous ethanol, drying the mixture, and dialyzing the mixture to obtain modified chitosan;

[0042] (7) adding 8 parts by weight of modified chitosan and 9 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 90° C. for 15 h, and then distilling under reduced pressure, filtering and drying to obtain sulfonic chitosan;

[0043] (8) 30 parts by weight of modified phenolic resin, 15 parts by weight of activated carbon, and 20 parts by weight of sulfonic acid chitosan were added into a twin-screw extruder and melt-extruded at 200° C. to obtain an activated carbon-containing adsorbent material.

[0044] Example 3

[0045] (1) adding o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol to N,N-dimethylformamide solvent, wherein the mass ratio of o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol is 1:1.2:1.0:3, stirring and mixing, reacting, the reaction pressure is 7.5 MPa, reacting at 135° C. for 2.5 hours, and after the reaction, removing the solvent by reduced pressure distillation, filtering and drying to obtain intermediate 1;

[0046] (2) Under nitrogen atmosphere, the intermediate 1 and ε-caprolactone were stirred evenly, and then a stannous octoate catalyst was added, wherein the mass ratio of the intermediate 1, ε-caprolactone, and the stannous octoate catalyst was 1.35:1:0.02, and the reaction was carried out at 140° C. for 8 h. After the reaction was completed, the crude product was first dissolved with chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated 3 times. The product was vacuum dried for 25 h to obtain modified caprolactone;

[0047] (3) adding 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid to thionyl chloride, wherein the mass ratio of thionyl chloride to 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid is 1.4:1, reacting at 65° C. for 5.5 h, and then distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0048] (4) adding p-aminophenol, modified caprolactone, and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of p-aminophenol, modified caprolactone, intermediate 2, and triethylamine catalyst is 1.25:1.7:1:0.035, stirring to dissolve, and then continuing to add triethylamine catalyst, reacting at 85° C. for 8 hours, and then distilling under reduced pressure after completion, washing the product with n-hexane to obtain modified phenol;

[0049] (5) adding modified phenol and formaldehyde into a stirrer, reacting at 92.5° C. for 50 min, then adding ethylenediamine dropwise, wherein the mass ratio of modified phenol, formaldehyde, and ethylenediamine is 1:1.35:0.02, heating to 90° C., reflux dehydration, and cooling to room temperature to obtain a modified phenolic resin;

[0050] (6) adding 7.5 parts by weight of chitosan to an ethanol solvent, heating in a water bath at 82.5° C., then adding 10 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, reacting for 7.5 hours, washing with anhydrous ethanol, drying, and dialyzing to obtain modified chitosan;

[0051] (7) adding 7 parts by weight of modified chitosan and 7 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 82.5° C. for 11.5 hours, and then distilling under reduced pressure, filtering and drying to obtain sulfonic chitosan;

[0052] (8) 22.5 parts by weight of modified phenolic resin, 12.5 parts by weight of activated carbon, and 14 parts by weight of sulfonic acid chitosan were added to a twin-screw extruder and melt-extruded at 192.5° C. to obtain an activated carbon-containing adsorbent material.

[0053] Example 4

[0054] (1) adding o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol to N,N-dimethylformamide solvent, wherein the mass ratio of o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol is 1:1.1:0.8:2, stirring and mixing, reacting, the reaction pressure is 5 MPa, reacting at 120° C. for 2 h, and after the reaction, removing the solvent by reduced pressure distillation, filtering and drying to obtain intermediate 1;

[0055] (2) Under nitrogen atmosphere, the intermediate 1 and ε-caprolactone were stirred evenly, and then a stannous octoate catalyst was added, wherein the mass ratio of the intermediate 1, ε-caprolactone, and the stannous octoate catalyst was 1.2:1:0.01, and the reaction was carried out at 135° C. for 6 h. After the reaction was completed, the crude product was first dissolved with chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated twice. The product was vacuum dried for 20 h to obtain modified caprolactone;

[0056] (3) adding 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid to thionyl chloride, wherein the mass ratio of thionyl chloride to 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid is 1.6:1, reacting at 70° C. for 7 h, and then distilling under reduced pressure after the reaction, filtering and drying to obtain intermediate 2;

[0057] (4) adding p-aminophenol, modified caprolactone, and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of p-aminophenol, modified caprolactone, intermediate 2, and triethylamine catalyst is 1.4:1.8:1:0.04, stirring to dissolve, and then continuing to add triethylamine catalyst, reacting at 90° C. for 10 hours, and then distilling under reduced pressure after completion, washing the product with n-hexane to obtain modified phenol;

[0058] (5) adding modified phenol and formaldehyde into a stirrer, reacting at 92.5° C. for 50 min, then adding ethylenediamine dropwise, wherein the mass ratio of modified phenol, formaldehyde, and ethylenediamine is 1:1.35:0.02, heating to 90° C., reflux dehydration, and cooling to room temperature to obtain a modified phenolic resin;

[0059] (6) adding 7.5 parts by weight of chitosan to an ethanol solvent, heating in a water bath at 82.5° C., then adding 10 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, reacting for 7.5 hours, washing with anhydrous ethanol, drying, and dialyzing to obtain modified chitosan;

[0060] (7) adding 7 parts by weight of modified chitosan and 7 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 82.5° C. for 11.5 hours, and then distilling under reduced pressure, filtering and drying to obtain sulfonic chitosan;

[0061] (8) 22.5 parts by weight of modified phenolic resin, 12.5 parts by weight of activated carbon, and 14 parts by weight of sulfonic acid chitosan were added to a twin-screw extruder and melt-extruded at 192.5° C. to obtain an activated carbon-containing adsorbent material.

[0062] Example 5

[0063] (1) adding o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol to N,N-dimethylformamide solvent, wherein the mass ratio of o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol is 1:1.3:1.2:4, stirring and mixing, reacting, the reaction pressure is 10 MPa, and the reaction is carried out at 150° C. for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, filtered and dried to obtain intermediate 1;

[0064] (2) Under nitrogen atmosphere, the intermediate 1 and ε-caprolactone were stirred evenly, and then a stannous octoate catalyst was added, wherein the mass ratio of the intermediate 1, ε-caprolactone, and the stannous octoate catalyst was 1.5:1:0.03, and the reaction was carried out at 145° C. for 10 h. After the reaction was completed, the crude product was first dissolved with chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated 4 times. The product was vacuum dried for 30 h to obtain modified caprolactone;

[0065] (3) adding 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid to thionyl chloride, wherein the mass ratio of thionyl chloride to 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid is 1.4:1, reacting at 65° C. for 5.5 h, and then distilling under reduced pressure, filtering and drying to obtain intermediate 2;

[0066] (4) adding p-aminophenol, modified caprolactone, and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of p-aminophenol, modified caprolactone, intermediate 2, and triethylamine catalyst is 1.25:1.7:1:0.035, stirring to dissolve, and then continuing to add triethylamine catalyst, reacting at 85° C. for 8 hours, and then distilling under reduced pressure after completion, washing the product with n-hexane to obtain modified phenol;

[0067] (5) adding modified phenol and formaldehyde into a stirrer, reacting at 85° C. for 40 min, then adding ethylenediamine dropwise, wherein the mass ratio of modified phenol, formaldehyde, and ethylenediamine is 1:1.2:0.01, heating to 85° C., reflux dehydration, and cooling to room temperature to obtain a modified phenolic resin;

[0068] (6) adding 5 parts by weight of chitosan to an ethanol solvent, heating in a water bath at 75° C., then adding 8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, reacting for 6 hours, washing with anhydrous ethanol, drying, and dialyzing to obtain modified chitosan;

[0069] (7) adding 6 parts by weight of modified chitosan and 5 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 75° C. for 8 h, and then distilling under reduced pressure, filtering and drying to obtain sulfonic chitosan;

[0070] (8) 15 parts by weight of modified phenolic resin, 10 parts by weight of activated carbon, and 8 parts by weight of sulfonic acid chitosan were added to a twin-screw extruder and melt-extruded at 185° C. to obtain an activated carbon-containing adsorbent material.

[0071] Comparative Example 1

[0072] (1) 10 parts by weight of activated carbon and 8 parts by weight of sulfonic acid chitosan were added into a twin-screw extruder and melt-extruded at 185° C. to obtain an activated carbon-containing adsorbent material.

[0073] Comparative Example 2

[0074] (1) 15 parts by weight of modified phenolic resin and 10 parts by weight of activated carbon were added to a twin-screw extruder and melt-extruded at 185° C. to obtain an activated carbon-containing adsorbent material.

[0075] Take 200mL of wastewater into a beaker. 2+ , and Pb 2+ The initial concentration of the wastewater was 100 mg / L. The wastewater adsorbent was added to the wastewater, and the wastewater was ultrasonically dispersed for 6 minutes and then placed on a shaker for 15 hours. The supernatant was taken and the Cd content in the supernatant was determined by ICP. 2+ and Pb 2+ The concentration after adsorption, the removal rate of heavy metal ions w = (initial concentration-concentration after adsorption) / initial concentration, the test results are shown in Table 1.

[0076] Table 1: Adsorption tests.

[0077] project <![CDATA[Cd 2+ Removal rate (%)]]> <![CDATA[Pb 2+ Removal rate (%)]]> Example 1 88.5 88.1 Example 2 91.6 92.6 Example 3 89.1 90.4 Example 4 88.9 88.7 Example 5 89.4 89.1 Comparative Example 1 52.6 53.8 Comparative Example 2 51.1 52.3

[0078] It can be seen from Table 1 that Examples 1-5 of the present invention have better heavy metal removal effects than Comparative Examples 1-2.

[0079] The activated carbon adsorbent material was dissolved and cast into a film to make a thin sheet with a radius of 1 cm; then the bacteria were transferred to a sterile culture medium using an inoculation loop to culture the bacteria at a concentration of 10 6 CFU / mL of bacterial suspension, then transfer 0.5mL of the bacterial suspension to a culture dish containing beef extract peptone medium, shake evenly and add the slice, and culture in a constant temperature incubator. After 48h of culture, measure the diameter of the inhibition zone.

[0080] Table 2: Antimicrobial testing.

[0081] sample Escherichia coli (mm) Staphylococcus aureus (mm) Example 1 18.6 18.8 Example 2 22.4 21.5 Example 3 21.5 19.3 Example 4 19.4 20.9 Example 5 18.5 18.2 Comparative Example 1 14.1 13.4 Comparative Example 2 14.3 13.6

[0082] It can be seen from Table 2 that Examples 1-5 of the present invention have better antibacterial effects than Comparative Examples 1-2.

[0083] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing an activated carbon adsorption material, characterized in that: The preparation method of the activated carbon-containing adsorption material comprises the following steps: (1) adding o-nitrophenylhydrazine, ammonia water, isopropanol and hexylene glycol to N,N-dimethylformamide solvent, stirring and mixing, reacting at a reaction pressure of 5-10 MPa and at 120-150° C. for 2-3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, filtered and dried to obtain intermediate 1; (2) Under nitrogen atmosphere, the intermediate 1 and ε-caprolactone are stirred evenly, and then stannous octoate catalyst is added, and the reaction is carried out at 135-145° C. for 6-10 hours. After the reaction is completed, the crude product is first dissolved in chloroform and then precipitated with anhydrous ether. The dissolution and precipitation are repeated 2-4 times, and the product is vacuum dried for 20-30 hours to obtain modified caprolactone; (3) adding 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid to thionyl chloride, reacting at 60-70° C. for 4-7 hours, and then distilling under reduced pressure, filtering and drying to obtain intermediate 2; (4) adding p-aminophenol, modified caprolactone and intermediate 2 to N,N-dimethylformamide solvent, stirring to dissolve, then adding triethylamine catalyst, reacting at 80-90° C. for 6-10 hours, and then distilling under reduced pressure after completion, washing the product with n-hexane to obtain modified phenol; (5) adding modified phenol and formaldehyde into a stirrer, reacting at 85-100° C. for 40-60 min, then adding ethylenediamine dropwise, heating to 85-95° C., reflux dehydration, and cooling to room temperature to obtain a modified phenolic resin; (6) Add 15-30 parts by weight of modified phenolic resin, 10-15 parts by weight of activated carbon, and 8-20 parts by weight of sulfonic acid chitosan into a twin-screw extruder, and melt extrude at 185-200° C. to obtain an activated carbon-containing adsorption material.

2. The method for preparing an activated carbon-containing adsorption material according to claim 1, characterized in that: The mass ratio of o-nitrophenylhydrazine, aqueous ammonia, isopropanol and hexylene glycol in (1) is 1:1.1-1.3:0.8-1.2:2-4.

3. The method for preparing an activated carbon-containing adsorption material according to claim 1, characterized in that: The mass ratio of the intermediate 1, ε-caprolactone and stannous octoate catalyst in (2) is 1.2-1.5:1:0.01-0.

03.

4. The method for preparing an activated carbon-containing adsorption material according to claim 1, characterized in that: The mass ratio of thionyl chloride to 3,6,9,12-tetraoxatetradecane-1,14-dicarboxylic acid in (3) is 1.2-1.6:

1.

5. The method for preparing an activated carbon-containing adsorption material according to claim 1, characterized in that: The mass ratio of p-aminophenol, modified caprolactone, intermediate 2 and triethylamine catalyst in (4) is 1.1-1.4:1.6-1.8:1:0.03-0.

04.

6. The method for preparing an activated carbon-containing adsorption material according to claim 1, characterized in that: The mass ratio of modified phenol, formaldehyde and ethylenediamine in (5) is 1:1.2-1.5:0.01-0.

03.

7. The method for preparing an activated carbon-containing adsorption material according to claim 1, characterized in that: The preparation method of the sulfonic acid chitosan in (6) is: S1. Add 5-10 parts by weight of chitosan to an ethanol solvent, heat in a water bath at 75-90°C, then add 8-12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at a constant pressure, react for 6-9h, wash with anhydrous ethanol, dry, and dialyze to obtain modified chitosan; S2. Add 6-8 parts by weight of modified chitosan and 5-9 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir to dissolve, react at 75-90°C for 8-15h, and then distill under reduced pressure, filter and dry to obtain sulfonic chitosan.

8. A method for preparing an activated carbon-containing adsorption material according to any one of claims 1 to 7, characterized in that: The application in wastewater treatment.