Nitrogen-removing sewage treatment agent and preparation method thereof

Abstract

The invention relates to the technical field of sewage treatment, and discloses a nitrogen-removal sewage treatment agent and a preparation method thereof.The nitrogen-removal sewage treatment agent is obtained by adding polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon and a sulfonic polymer into a stirrer and stirring. The graphene oxide has a relatively large specific surface area and rich functional groups, and can effectively adsorb nitrogen in sewage; wherein the boric acid group can also remove nitrogen in water so as to play a role in purifying water, and the quaternary ammonium salt contained in the water can also remove nitrogen in sewage and has a synergistic effect with siloxane, so that the nitrogen in the sewage is adsorbed, and the effect of purifying water is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, in particular to a sewage treatment agent for removing nitrogen and a preparation method thereof. Background Art

[0002] Nitrogen in water exists in four forms: organic nitrogen, ammonia nitrogen, nitrite nitrogen and nitrate nitrogen. Nitrogen is widely present in nature and is of great significance to organisms. It is the main element for amino acid synthesis in cells. In recent years, due to the development of industry and agriculture, excessive discharge of organic nitrogen and inorganic nitrogen has broken the balance of nitrogen cycle and brought serious environmental problems. Nitrogen pollution mainly comes from: excessive use of nitrogen fertilizers; disorderly discharge of animal manure and septic tank systems; discharge of sewage containing nitrate nitrogen and ammonia nitrogen in industrial processes. With the expansion of coal chemical industry and animal husbandry, and the increase in demand for domestic water and landfill, a large amount of nitrogen-containing pollutants are generated and discharged into natural water bodies through surface runoff, infiltration, etc., resulting in the accumulation of nitrogen-containing compounds and causing various hazards. Inorganic nitrogen can cause eutrophication of water bodies; nitrate nitrogen can be converted into nitrite nitrogen, which may cause bladder cancer, ovarian cancer or gastric cancer after human ingestion. At the same time, high concentrations of nitrate nitrogen and nitrite nitrogen will affect the use of groundwater.

[0003] The nitrogen in the wastewater of refineries is mainly ammonia nitrogen and nitrate nitrogen. At present, most of them are removed by biological nitrification and denitrification. Due to the poor biodegradability of refinery wastewater, a large amount of carbon sources, such as glucose, acetic acid, sodium acetate, etc., are often required. Adding carbon sources will increase operating costs on the one hand, and cause secondary pollution to the water body on the other hand. With the improvement of sewage discharge standards, the existing sewage treatment facilities can no longer meet the requirements of deep treatment and are facing the problem of upgrading and transformation; how to avoid this phenomenon is the key to solving the problem. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies of the prior art, the present invention provides a sewage treatment agent for removing nitrogen and a preparation method thereof, which has a good nitrogen removal effect.

[0006] (II) Technical solution

[0007] To achieve the above objectives, the present invention provides the following technical solution: a sewage treatment agent for nitrogen removal, comprising the following components by weight: 8-12 parts by weight of polyethylene glycol, 7-15 parts by weight of modified siloxane, 6-10 parts by weight of modified graphene oxide, 10-12 parts by weight of urea, 5-10 parts by weight of activated carbon, and 6-8 parts by weight of sulfonic acid polymer.

[0008] Preferably, the preparation method of the modified siloxane is:

[0009] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring to dissolve, adding platinum black catalyst, heating to 75-95° C. for activation for 0.6-1.2 h, then heating to 100-120° C., adding heptamethyl trisiloxane dropwise at constant pressure, reacting at 105-115° C. for 4-8 h after the addition, and removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0010] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 90-105° C. for 5-12 hours, and then removing the solvent by distillation under reduced pressure, filtering and drying to obtain intermediate 1;

[0011] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate 1, raise the temperature to 110-125° C. and react for 8-15 hours. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0012] Preferably, the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyl trisiloxane in (1) is 1:0.01-0.03:1.1-1.3.

[0013] Preferably, the mass ratio of the polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride in (2) is 1.4-1.6:1.

[0014] Preferably, the mass ratio of boric acid to intermediate 1 in (3) is 1:1.2-1.5.

[0015] Preferably, the preparation method of the modified graphene oxide is:

[0016] S1. adding graphene oxide to thionyl chloride, uniformly dispersing by ultrasonication, reacting at 70-85° C. for 20-28 h, filtering after completion, washing and drying to obtain graphene chloride;

[0017] S2. Add intermediate 1 and graphene chloride to N,N-dimethylformamide solvent, stir to dissolve, continue to add p-toluenesulfonic acid catalyst, react at 95-105°C for 8-15h, and then distill under reduced pressure, filter and dry to obtain modified graphene oxide.

[0018] Preferably, in S1, the ratio of graphene oxide to thionyl chloride is 1:1.6-1.8.

[0019] Preferably, the mass ratio of the intermediate 1, the chlorinated graphene, and the p-toluenesulfonic acid catalyst in S2 is 1.2-1.4:1:0.02-0.04.

[0020] Preferably, the preparation method of the sulfonic acid polymer is:

[0021] a. Add 5-10 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve, stir evenly in an ice-water bath under nitrogen protection, then add 6-12 parts by weight of methyl acrylate dropwise within 2-4 hours, react at 20-30°C for 20-36 hours, and then distill under reduced pressure to obtain intermediate 1;

[0022] b. Add 15-20 parts by weight of intermediate 1 to a reactor containing methanol solvent, stir well, then add 2-5 parts by weight of ethylenediamine dropwise within 2-4 hours to react, and then perform rotary distillation at 70-100°C and 260-320Pa to obtain intermediate 2;

[0023] c. Add 7-15 parts by weight of intermediate 2 and 14-20 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1-5 parts by weight of triethylamine catalyst thereto, stir and react at 60-100 ° C for 8-12h, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0024] d. 3-6 parts by weight of olefinic polyamide, 5-10 parts by weight of sodium methyl propylene sulfonate, and 3-5 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5-1 parts by weight of ammonium persulfate initiator are added, and the temperature is raised to 100-150°C for reaction for 3-6h. After the reaction, the solvent is removed by distillation under reduced pressure, filtered, washed and dried to obtain a sulfonic acid polymer.

[0025] Preferably, the preparation method of the nitrogen-removing sewage treatment agent is: adding polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon, and sulfonic acid polymer into a stirrer, stirring at 30-40° C. for 10-14 minutes, and obtaining the nitrogen-removing sewage treatment agent after completion.

[0026] (III) Beneficial technical effects

[0027] The invention adds polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon and sulfonic acid polymer into a stirrer, and stirs to obtain a sewage treatment agent for removing nitrogen.

[0028] Graphene oxide itself has a large specific surface area and rich functional groups, which can effectively adsorb nitrogen in sewage; the boric acid groups in it can also remove nitrogen from water and play a role in water purification. The quaternary ammonium salts it contains can also remove nitrogen from sewage and work synergistically with siloxanes to adsorb nitrogen in sewage and achieve the effect of purifying water quality. DETAILED DESCRIPTION

[0029] Example 1

[0030] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 75°C for activation for 0.6h, then continuously heating to 100°C, and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.01:1.1, reacting at 105°C for 4h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0031] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.4:1, stirring and dissolving, reacting at 90° C. for 5 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 1;

[0032] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.2, heating to 110° C. to react for 8 h, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0033] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.6, and after being uniformly dispersed by ultrasonication, reacting at 70°C for 20 hours, filtering after the reaction, washing and drying to obtain chlorinated graphene;

[0034] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.2:1:0.02, reacting at 95° C. for 8 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0035] (6) Add 5 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise within 2 hours, react at 20° C. for 20 hours, and then distill under reduced pressure to obtain intermediate 1;

[0036] Add 15 parts by weight of intermediate 1 to a reactor filled with methanol solvent, stir thoroughly, then dropwise add 2 parts by weight of ethylenediamine within 2 hours to react, and then perform rotary vacuum distillation at 70° C. and 260 Pa to obtain intermediate 2;

[0037] Add 7 parts by weight of the intermediate 2 and 14 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1 part by weight of triethylamine catalyst, stir and react at 60° C. for 8 hours, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0038] 3 parts by weight of olefinic polyamide, 5 parts by weight of sodium methyl propylene sulfonate, and 3 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5 parts by weight of ammonium persulfate initiator is added, and the temperature is raised to 100° C. to react for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0039] (7) 8 parts by weight of polyethylene glycol, 7 parts by weight of modified siloxane, 6 parts by weight of modified graphene oxide, 10 parts by weight of urea, 5 parts by weight of activated carbon, and 6 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 30° C. for 10 minutes to obtain a nitrogen-removing sewage treatment agent.

[0040] Example 2

[0041] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 95° C. for activation for 1.2 h, then continuously heating to 120° C., and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.03:1.3, reacting at 115° C. for 8 h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0042] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.6:1, stirring and dissolving, reacting at 105° C. for 12 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 1;

[0043] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.5, heating to 125° C. to react for 15 h, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0044] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.8, and after being uniformly dispersed by ultrasonication, reacting at 85° C. for 28 h, and then filtering, washing and drying to obtain graphene chloride;

[0045] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.4:1:0.04, reacting at 105° C. for 15 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0046] (6) Add 8 parts by weight of ethylenediamine to a reactor filled with methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 10 parts by weight of methyl acrylate dropwise within 3 hours, react at 25° C. for 30 hours, and then distill under reduced pressure to obtain intermediate 1;

[0047] 18 parts by weight of intermediate 1 was added to a reactor filled with methanol solvent, and after being fully stirred, 3 parts by weight of ethylenediamine was added dropwise within 3 hours to carry out the reaction. After the reaction was completed, rotary vacuum distillation was carried out at 90° C. and 300 Pa to obtain intermediate 2;

[0048] Add 10 parts by weight of the intermediate 2 and 18 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 3 parts by weight of triethylamine catalyst, stir to react at 80° C. for 10 hours, and then perform vacuum distillation after reaction, filter and dry to obtain olefinated polyamide;

[0049] 5 parts by weight of olefinic polyamide, 8 parts by weight of sodium methyl propylene sulfonate, and 4 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.8 parts by weight of ammonium persulfate initiator is added, and the temperature is raised to 120° C. to react for 5 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0050] (7) 12 parts by weight of polyethylene glycol, 15 parts by weight of modified siloxane, 10 parts by weight of modified graphene oxide, 12 parts by weight of urea, 10 parts by weight of activated carbon, and 8 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 40° C. for 14 minutes to obtain a wastewater treatment agent for nitrogen removal.

[0051] Example 3

[0052] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 85°C for activation for 0.9h, then continuously heating to 110°C, and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.02:1.2, reacting at 110°C for 6h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0053] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.5:1, stirring to dissolve, reacting at 97.5° C. for 8.5 h, and then removing the solvent by distillation under reduced pressure, filtering and drying to obtain intermediate 1;

[0054] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.35, heating to 117.5° C. to react for 11.5 hours, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0055] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.7, and after being uniformly dispersed by ultrasonication, reacting at 77.5°C for 24 hours, and then filtering, washing and drying to obtain chlorinated graphene;

[0056] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.3:1:0.03, reacting at 97.5° C. for 11.5 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0057] (6) Add 10 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 12 parts by weight of methyl acrylate dropwise within 4 hours, react at 30° C. for 36 hours, and then distill under reduced pressure to obtain intermediate 1;

[0058] Add 20 parts by weight of intermediate 1 to a reactor filled with methanol solvent, stir thoroughly, then dropwise add 5 parts by weight of ethylenediamine within 4 hours to react, and then perform rotary vacuum distillation at 100° C. and 320 Pa to obtain intermediate 2;

[0059] Add 15 parts by weight of the intermediate 2 and 20 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 5 parts by weight of triethylamine catalyst, stir and react at 100° C. for 12 hours, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0060] 6 parts by weight of olefinic polyamide, 10 parts by weight of sodium methyl propylene sulfonate, and 5 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 1 part by weight of ammonium persulfate initiator is added, and the temperature is raised to 150° C. to react for 6 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0061] (7) 10 parts by weight of polyethylene glycol, 11 parts by weight of modified siloxane, 8 parts by weight of modified graphene oxide, 11 parts by weight of urea, 7.5 parts by weight of activated carbon, and 7 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 35° C. for 12 minutes to obtain a wastewater treatment agent for nitrogen removal.

[0062] Example 4

[0063] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 75°C for activation for 0.6h, then continuously heating to 100°C, and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.01:1.1, reacting at 105°C for 4h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0064] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.4:1, stirring and dissolving, reacting at 90° C. for 5 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 1;

[0065] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.5, heating to 125° C. to react for 15 h, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0066] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.8, and after being uniformly dispersed by ultrasonication, reacting at 85° C. for 28 h, and then filtering, washing and drying to obtain graphene chloride;

[0067] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.3:1:0.03, reacting at 97.5° C. for 11.5 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0068] (6) Add 5 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise within 2 hours, react at 20° C. for 20 hours, and then distill under reduced pressure to obtain intermediate 1;

[0069] Add 15 parts by weight of intermediate 1 to a reactor filled with methanol solvent, stir thoroughly, then dropwise add 2 parts by weight of ethylenediamine within 2 hours to react, and then perform rotary vacuum distillation at 70° C. and 260 Pa to obtain intermediate 2;

[0070] Add 7 parts by weight of the intermediate 2 and 14 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1 part by weight of triethylamine catalyst, stir and react at 60° C. for 8 hours, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0071] 3 parts by weight of olefinic polyamide, 5 parts by weight of sodium methyl propylene sulfonate, and 3 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5 parts by weight of ammonium persulfate initiator is added, and the temperature is raised to 100° C. to react for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0072] (7) 10 parts by weight of polyethylene glycol, 11 parts by weight of modified siloxane, 8 parts by weight of modified graphene oxide, 11 parts by weight of urea, 7.5 parts by weight of activated carbon, and 8 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 35° C. for 12 minutes to obtain a nitrogen-removing sewage treatment agent.

[0073] Example 5

[0074] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 95° C. for activation for 1.2 h, then continuously heating to 120° C., and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.03:1.3, reacting at 115° C. for 8 h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0075] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.6:1, stirring and dissolving, reacting at 105° C. for 12 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 1;

[0076] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.35, heating to 117.5° C. to react for 11.5 hours, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0077] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.7, and after being uniformly dispersed by ultrasonication, reacting at 77.5°C for 24 hours, and then filtering, washing and drying to obtain chlorinated graphene;

[0078] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.2:1:0.02, reacting at 95° C. for 8 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0079] (6) Add 5 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise within 2 hours, react at 20° C. for 20 hours, and then distill under reduced pressure to obtain intermediate 1;

[0080] Add 15 parts by weight of intermediate 1 to a reactor filled with methanol solvent, stir thoroughly, then dropwise add 2 parts by weight of ethylenediamine within 2 hours to react, and then perform rotary vacuum distillation at 70° C. and 260 Pa to obtain intermediate 2;

[0081] Add 7 parts by weight of the intermediate 2 and 14 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1 part by weight of triethylamine catalyst, stir and react at 60° C. for 8 hours, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0082] 3 parts by weight of olefinic polyamide, 5 parts by weight of sodium methyl propylene sulfonate, and 3 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5 parts by weight of ammonium persulfate initiator is added, and the temperature is raised to 100° C. to react for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0083] (7) 8 parts by weight of polyethylene glycol, 7 parts by weight of modified siloxane, 6 parts by weight of modified graphene oxide, 10 parts by weight of urea, 5 parts by weight of activated carbon, and 6 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 30° C. for 10 minutes to obtain a nitrogen-removing sewage treatment agent.

[0084] Example 6

[0085] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 85°C for activation for 0.9h, then continuously heating to 110°C, and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.02:1.2, reacting at 110°C for 6h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0086] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.5:1, stirring to dissolve, reacting at 97.5° C. for 8.5 h, and then removing the solvent by distillation under reduced pressure, filtering and drying to obtain intermediate 1;

[0087] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.2, heating to 110° C. to react for 8 h, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0088] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.6, and after being uniformly dispersed by ultrasonication, reacting at 70°C for 20 hours, filtering after the reaction, washing and drying to obtain chlorinated graphene;

[0089] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.4:1:0.04, reacting at 105° C. for 15 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0090] (6) 12 parts by weight of polyethylene glycol, 15 parts by weight of modified siloxane, 10 parts by weight of modified graphene oxide, 12 parts by weight of urea, 10 parts by weight of activated carbon, and 7 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 40° C. for 14 minutes to obtain a wastewater treatment agent for nitrogen removal.

[0091] Example 7

[0092] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 75°C for activation for 0.6h, then continuously heating to 100°C, and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.01:1.1, reacting at 105°C for 4h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0093] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.6:1, stirring and dissolving, reacting at 105° C. for 12 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 1;

[0094] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.35, heating to 117.5° C. to react for 11.5 hours, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0095] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.7, and after being uniformly dispersed by ultrasonication, reacting at 77.5°C for 24 hours, and then filtering, washing and drying to obtain chlorinated graphene;

[0096] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.3:1:0.03, reacting at 97.5° C. for 11.5 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0097] (6) Add 5 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise within 2 hours, react at 20° C. for 20 hours, and then distill under reduced pressure to obtain intermediate 1;

[0098] Add 15 parts by weight of intermediate 1 to a reactor filled with methanol solvent, stir thoroughly, then dropwise add 2 parts by weight of ethylenediamine within 2 hours to react, and then perform rotary vacuum distillation at 70° C. and 260 Pa to obtain intermediate 2;

[0099] Add 7 parts by weight of the intermediate 2 and 14 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1 part by weight of triethylamine catalyst, stir and react at 60° C. for 8 hours, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0100] 3 parts by weight of olefinic polyamide, 5 parts by weight of sodium methyl propylene sulfonate, and 3 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5 parts by weight of ammonium persulfate initiator is added, and the temperature is raised to 100° C. to react for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0101] (7) 10 parts by weight of polyethylene glycol, 11 parts by weight of modified siloxane, 8 parts by weight of modified graphene oxide, 11 parts by weight of urea, 7.5 parts by weight of activated carbon, and 6 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 35° C. for 12 minutes to obtain a nitrogen-removing sewage treatment agent.

[0102] Example 8

[0103] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 95° C. for activation for 1.2 h, then continuously heating to 120° C., and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.03:1.3, reacting at 115° C. for 8 h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0104] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.5:1, stirring to dissolve, reacting at 97.5° C. for 8.5 h, and then removing the solvent by distillation under reduced pressure, filtering and drying to obtain intermediate 1;

[0105] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.2, heating to 110° C. to react for 8 h, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0106] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.6, and after being uniformly dispersed by ultrasonication, reacting at 70°C for 20 hours, filtering after the reaction, washing and drying to obtain chlorinated graphene;

[0107] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.2:1:0.02, reacting at 95° C. for 8 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0108] (6) Add 5 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise within 2 hours, react at 20° C. for 20 hours, and then distill under reduced pressure to obtain intermediate 1;

[0109] Add 15 parts by weight of intermediate 1 to a reactor filled with methanol solvent, stir thoroughly, then dropwise add 2 parts by weight of ethylenediamine within 2 hours to react, and then perform rotary vacuum distillation at 70° C. and 260 Pa to obtain intermediate 2;

[0110] Add 7 parts by weight of the intermediate 2 and 14 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1 part by weight of triethylamine catalyst, stir and react at 60° C. for 8 hours, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0111] 3 parts by weight of olefinic polyamide, 5 parts by weight of sodium methyl propylene sulfonate, and 3 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5 parts by weight of ammonium persulfate initiator is added, and the temperature is raised to 100° C. to react for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0112] (7) 8 parts by weight of polyethylene glycol, 7 parts by weight of modified siloxane, 6 parts by weight of modified graphene oxide, 10 parts by weight of urea, 5 parts by weight of activated carbon, and 8 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 30° C. for 10 minutes to obtain a wastewater treatment agent for nitrogen removal.

[0113] Example 9

[0114] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 75°C for activation for 0.6h, then continuously heating to 100°C, and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.01:1.1, reacting at 105°C for 4h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0115] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.4:1, stirring and dissolving, reacting at 90° C. for 5 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 1;

[0116] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.2, heating to 110° C. to react for 8 h, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0117] (4) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.6, and after being uniformly dispersed by ultrasonication, reacting at 70°C for 20 hours, filtering after the reaction, washing and drying to obtain chlorinated graphene;

[0118] (5) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.4:1:0.04, reacting at 105° C. for 15 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0119] (6) Add 5 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve it, stir it evenly in an ice-water bath under nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise within 2 hours, react at 20° C. for 20 hours, and then distill under reduced pressure to obtain intermediate 1;

[0120] Add 15 parts by weight of intermediate 1 to a reactor filled with methanol solvent, stir thoroughly, then dropwise add 2 parts by weight of ethylenediamine within 2 hours to react, and then perform rotary vacuum distillation at 70° C. and 260 Pa to obtain intermediate 2;

[0121] Add 7 parts by weight of the intermediate 2 and 14 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1 part by weight of triethylamine catalyst, stir and react at 60° C. for 8 hours, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide;

[0122] 3 parts by weight of olefinic polyamide, 5 parts by weight of sodium methyl propylene sulfonate, and 3 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5 parts by weight of ammonium persulfate initiator is added, and the temperature is raised to 100° C. to react for 3 hours. After the reaction, the solvent is removed by distillation under reduced pressure, and the mixture is filtered, washed, and dried to obtain a sulfonic acid polymer;

[0123] (7) 10 parts by weight of polyethylene glycol, 11 parts by weight of modified siloxane, 8 parts by weight of modified graphene oxide, 11 parts by weight of urea, 7.5 parts by weight of activated carbon, and 6 parts by weight of sulfonic acid polymer are added into a stirrer and stirred at 35° C. for 12 minutes to obtain a nitrogen-removing sewage treatment agent.

[0124] Comparative Example 1

[0125] (1) adding graphene oxide to thionyl chloride, wherein the ratio of graphene oxide to thionyl chloride is 1:1.7, and after being uniformly dispersed by ultrasonication, reacting at 77.5° C. for 24 hours, and then filtering, washing and drying to obtain chlorinated graphene;

[0126] (2) adding intermediate 1 and chlorinated graphene to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 1, chlorinated graphene, and p-toluenesulfonic acid catalyst is 1.2:1:0.02, reacting at 95° C. for 8 h, and then distilling under reduced pressure, filtering and drying to obtain modified graphene oxide;

[0127] (3) 8 parts by weight of polyethylene glycol, 6 parts by weight of modified graphene oxide, 10 parts by weight of urea, and 5 parts by weight of activated carbon were added into a stirrer and stirred at 30° C. for 10 min. After the stirring, a wastewater treatment agent for removing nitrogen was obtained.

[0128] Comparative Example 2

[0129] (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring and dissolving, continuously adding platinum black catalyst thereto, heating to 95° C. for activation for 1.2 h, then continuously heating to 120° C., and adding heptamethyl trisiloxane thereto dropwise at a constant pressure, wherein the mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyl trisiloxane is 1:0.03:1.3, reacting at 115° C. for 8 h after the addition is completed, and then removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane;

[0130] (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride is 1.6:1, stirring and dissolving, reacting at 105° C. for 12 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain intermediate 1;

[0131] (3) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 1 thereto, wherein the mass ratio of boric acid to intermediate 1 is 1:1.35, heating to 117.5° C. to react for 11.5 hours, and after the reaction is completed, distilling under reduced pressure, filtering and drying to obtain modified siloxane;

[0132] (4) 8 parts by weight of polyethylene glycol, 7 parts by weight of modified siloxane, 10 parts by weight of urea, and 5 parts by weight of activated carbon are added into a stirrer and stirred at 30° C. for 10 minutes to obtain a nitrogen-removing sewage treatment agent.

[0133] The nitrogen removal performance of the sewage treatment agents obtained in Examples 1-5 and Comparative Examples 1-2 was tested. The test method is as follows: the sewage treatment agents obtained in the examples and comparative examples are filled in a sewage treatment device, sewage is introduced into the sewage device, and the nitrogen content in the liquid discharged from the outlet of the sewage treatment device is measured at a temperature of 25°C. The test results are shown in Table 1.

[0134] Table 1: Nitrogen content tested.

[0135] project Nitrogen content mg / L Example 1 1.43 Example 2 1.31 Example 3 1.41 Example 4 1.36 Example 5 1.42 Example 6 1.43 Example 7 1.38 Example 8 1.41 Example 9 1.42 Comparative Example 1 4.35 Comparative Example 2 4.57

[0136] It can be seen from Table 1 that Examples 1-9 of the present invention have better nitrogen removal effects than Comparative Examples 1-2.

[0137] 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 sewage treatment agent for removing nitrogen, characterized in that: The invention comprises the following components by weight: 8-12 parts by weight of polyethylene glycol, 7-15 parts by weight of modified siloxane, 6-10 parts by weight of modified graphene oxide, 10-12 parts by weight of urea, 5-10 parts by weight of activated carbon and 6-8 parts by weight of sulfonic acid polymer.

2. The sewage treatment agent for removing nitrogen according to claim 1, characterized in that: The preparation method of the modified siloxane is: (1) adding allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stirring to dissolve, adding platinum black catalyst, heating to 75-95° C. for activation for 0.6-1.2 h, then heating to 100-120° C., adding heptamethyl trisiloxane dropwise at constant pressure, reacting at 105-115° C. for 4-8 h after the addition, and removing low-boiling substances by reduced pressure distillation to obtain polyether-modified trisiloxane; (2) adding polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 90-105° C. for 5-12 hours, and then removing the solvent by distillation under reduced pressure, filtering and drying to obtain intermediate 1; (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate 1, raise the temperature to 110-125° C. and react for 8-15 hours. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

3. The sewage treatment agent for nitrogen removal according to claim 2, characterized in that: The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyl trisiloxane in (1) is 1:0.01-0.03:1.1-1.

3.

4. The sewage treatment agent for removing nitrogen according to claim 2, characterized in that: The mass ratio of polyether-modified trisiloxane to 2,3-epoxypropyltrimethylammonium chloride in (2) is 1.4-1.6:

1.

5. The sewage treatment agent for removing nitrogen according to claim 2, characterized in that: The mass ratio of boric acid to intermediate 1 in (3) is 1:1.2-1.

5.

6. The sewage treatment agent for removing nitrogen according to claim 1, characterized in that: The preparation method of the modified graphene oxide is: S1. adding graphene oxide to thionyl chloride, uniformly dispersing by ultrasonication, reacting at 70-85° C. for 20-28 h, filtering after completion, washing and drying to obtain graphene chloride; S2. Add intermediate 1 and graphene chloride to N,N-dimethylformamide solvent, stir to dissolve, continue to add p-toluenesulfonic acid catalyst, react at 95-105°C for 8-15h, and then distill under reduced pressure, filter and dry to obtain modified graphene oxide.

7. The sewage treatment agent for removing nitrogen according to claim 6, characterized in that: In the S1, the ratio of graphene oxide to thionyl chloride is 1:1.6-1.

8.

8. The sewage treatment agent for removing nitrogen according to claim 6, characterized in that: The mass ratio of the intermediate 1, the chlorinated graphene, and the p-toluenesulfonic acid catalyst in S2 is 1.2-1.4:1:0.02-0.

04.

9. The sewage treatment agent for removing nitrogen according to claim 1, characterized in that: The preparation method of the sulfonic acid polymer is: a. Add 5-10 parts by weight of ethylenediamine to a reactor containing methanol solvent to dissolve, stir evenly in an ice-water bath under nitrogen protection, then add 6-12 parts by weight of methyl acrylate dropwise within 2-4 hours, react at 20-30°C for 20-36 hours, and then distill under reduced pressure to obtain intermediate 1; b. Add 15-20 parts by weight of intermediate 1 to a reactor containing methanol solvent, stir well, then add 2-5 parts by weight of ethylenediamine dropwise within 2-4 hours to react, and then perform rotary distillation at 70-100°C and 260-320Pa to obtain intermediate 2; c. Add 7-15 parts by weight of intermediate 2 and 14-20 parts by weight of acryloyl chloride to N,N-dimethylformamide solvent, stir to dissolve, then add 1-5 parts by weight of triethylamine catalyst thereto, stir and react at 60-100 ° C for 8-12h, and then distill under reduced pressure, filter and dry to obtain olefinated polyamide; d. 3-6 parts by weight of olefinic polyamide, 5-10 parts by weight of sodium methyl propylene sulfonate, and 3-5 parts by weight of olefinic chitosan are added to N,N-dimethylformamide solvent, and after dissolution, 0.5-1 parts by weight of ammonium persulfate initiator are added, and the temperature is raised to 100-150°C for reaction for 3-6h. After the reaction, the solvent is removed by distillation under reduced pressure, filtered, washed and dried to obtain a sulfonic acid polymer.

10. A method for preparing a sewage treatment agent for removing nitrogen according to any one of claims 1 to 9, characterized in that: The preparation method of the nitrogen-removing sewage treatment agent is as follows: polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon, and sulfonic acid polymer are added into a stirrer, and stirred at 30-40° C. for 10-14 minutes, and then the nitrogen-removing sewage treatment agent is obtained.