A wastewater treatment agent for removing nitrogen and a preparation method thereof

Abstract

This invention relates to the field of wastewater treatment technology and discloses a nitrogen-removing wastewater treatment agent and its preparation method. The invention involves adding polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon, and a sulfonic acid polymer to a stirrer, stirring, and then obtaining the nitrogen-removing wastewater treatment agent. Graphene oxide itself has a large specific surface area and abundant functional groups, which can effectively adsorb nitrogen from wastewater; the boric acid groups can also remove nitrogen from water, playing a role in water purification; the quaternary ammonium salt contained therein can also remove nitrogen from wastewater, and the synergistic effect of the siloxane and graphene oxides adsorbs nitrogen from wastewater, achieving the effect of water purification.

Description

Technical Field

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

[0002] Nitrogen in water exists in four forms: organic nitrogen, ammonia nitrogen, nitrite nitrogen, and nitrate nitrogen. Nitrogen is widely distributed in nature and plays a vital role in organisms, being a major element in the synthesis of amino acids in cells. In recent years, due to industrial and agricultural development, the excessive discharge of organic and inorganic nitrogen has disrupted the nitrogen cycle balance, leading to serious environmental problems. Nitrogen pollution mainly comes from: the overuse of nitrogen fertilizers; the disorderly discharge of animal manure and septic tank systems; and the discharge of wastewater containing nitrate and ammonia nitrogen from industrial processes. With the expansion of coal chemical industry and animal husbandry, and the increased demand for domestic water and landfill, large amounts of nitrogenous pollutants are generated and discharged into natural water bodies through surface runoff and infiltration, leading to the accumulation of nitrogen compounds and causing various hazards. Inorganic nitrogen causes eutrophication of water bodies; nitrate nitrogen can be converted into nitrite nitrogen, which, when ingested by humans, may cause diseases such as bladder cancer, ovarian cancer, or stomach cancer. High concentrations of nitrate and nitrite nitrogen also affect the use of groundwater.

[0003] The nitrogen in wastewater from refining and chemical enterprises is mainly ammonia nitrogen and nitrate nitrogen. Currently, most of these are removed using biological nitrification and denitrification methods. However, due to the poor biodegradability of refining and chemical wastewater, large amounts of carbon sources, such as glucose, acetic acid, and sodium acetate, are often required. Adding carbon sources increases operating costs and also causes secondary pollution to the water body. With the increasing stringency of wastewater discharge standards, existing wastewater treatment facilities are no longer sufficient for advanced treatment and face the need for upgrades and renovations. Avoiding this situation is key to solving the problem. Summary of the Invention

[0004] (a) Technical problems to be solved

[0005] To address the shortcomings of existing technologies, this invention provides a nitrogen-removing wastewater treatment agent and its preparation method, 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 nitrogen removal wastewater treatment agent comprising the following weight components: 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 modified siloxane is prepared by:

[0009] (1) Add allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stir to dissolve, continue to add platinum black catalyst, heat to 75-95℃ to activate for 0.6-1.2h, then continue to heat to 100-120℃, add heptamethyltrisiloxane dropwise under constant pressure, after the dropwise addition is completed, react at 105-115℃ for 4-8h, after the reaction is completed, remove low-boiling substances by vacuum distillation to obtain polyether modified trisiloxane;

[0010] (2) Add polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, stir to dissolve, react at 90-105℃ for 5-12h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0011] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, heat to 110-125℃ and react for 8-15 h. 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 heptamethyltrisiloxane in (1) is 1:0.01-0.03:1.1-1.3.

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

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

[0015] Preferably, the modified graphene oxide is prepared by:

[0016] S1. Add graphene oxide to thionyl chloride, disperse it evenly by ultrasonication, and react it at 70-85℃ for 20-28h. After the reaction is completed, filter, wash and dry to obtain acyl-chromium graphene.

[0017] S2. Add intermediate A and acyl-chlorographene to N,N-dimethylformamide solvent, stir to dissolve, continue to add p-toluenesulfonic acid catalyst, react at 95-105℃ for 8-15h, after which distill under reduced pressure, filter and dry to obtain modified graphene oxide.

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

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

[0020] Preferably, the sulfonic acid polymer is prepared by:

[0021] a. Add 5-10 parts by weight of ethylenediamine to a reactor containing methanol solvent for dissolution, stir evenly under ice-water bath and nitrogen protection, then add 6-12 parts by weight of methyl acrylate dropwise over 2-4 hours, react at 20-30℃ for 20-36 hours, and distill under reduced pressure after the reaction to obtain intermediate B.

[0022] b. Add 15-20 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2-5 parts by weight of ethylenediamine dropwise over 2-4 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70-100℃ and 260-320Pa to obtain intermediate C.

[0023] c. Add 7-15 parts by weight of intermediate C 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, stir to react at 60-100℃ for 8-12 hours, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide.

[0024] d. Add 3-6 parts by weight of alkenylated polyamide, 5-10 parts by weight of sodium methacrylate sulfonate, and 3-5 parts by weight of alkenylated chitosan to N,N-dimethylformamide solvent. After dissolving, add 0.5-1 parts by weight of ammonium persulfate initiator, heat to 100-150℃ and react for 3-6 hours. After the reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain sulfonic acid polymer.

[0025] Preferably, the method for preparing the denitrifying wastewater treatment agent is as follows: polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon, and sulfonic acid polymer are added to a stirrer and stirred at 30-40°C for 10-14 minutes. After stirring, the denitrifying wastewater treatment agent is obtained.

[0026] (iii) Beneficial technical effects

[0027] This invention involves adding polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon, and sulfonic acid polymer to a stirrer, stirring, and then obtaining a denitrifying wastewater treatment agent.

[0028] Graphene oxide itself has a large specific surface area and abundant functional groups, which can effectively adsorb nitrogen in wastewater; the boric acid groups can also remove nitrogen from water, playing a role in water purification; the quaternary ammonium salts it contains can also remove nitrogen from wastewater, and the synergistic effect of siloxanes can adsorb nitrogen in wastewater, achieving the effect of purifying water quality. Detailed Implementation

[0029] Example 1

[0030] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 75°C for 0.6 h. Then the temperature was raised to 100°C and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.01:1.1. After the dropwise addition was completed, the reaction was carried out at 105°C for 4 h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0031] (2) Add 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, stir to dissolve, react at 90°C for 5 h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0032] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.2, heat to 110℃ and react for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0033] (4) Add graphene oxide to sulfoxide, wherein the mass ratio of graphene oxide to sulfoxide is 1:1.6. After ultrasonic dispersion, react at 70°C for 20 h. After the reaction, filter, wash and dry to obtain acyl-chlorographene.

[0034] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.2:1:0.02. React at 95℃ for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry 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 under ice-water bath and nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise over 2 hours, react at 20°C for 20 hours, and then distill under reduced pressure to obtain intermediate B.

[0036] Add 15 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2 parts by weight of ethylenediamine dropwise over 2 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70°C and 260 Pa to obtain intermediate C.

[0037] Add 7 parts by weight of intermediate C 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 to react for 8 hours at 60°C, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide.

[0038] Three parts by weight of alkenylated polyamide, five parts by weight of sodium methacrylate sulfonate, and three parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 0.5 parts by weight of ammonium persulfate initiator were added, and the mixture was heated to 100°C and reacted for 3 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0039] (7) Add 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 to a stirrer and stir at 30°C for 10 min. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0040] Example 2

[0041] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 95℃ for 1.2h. Then the temperature was raised to 120℃ and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.03:1.3. After the dropwise addition was completed, the reaction was carried out at 115℃ for 8h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0042] (2) Add 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. Stir to dissolve, react at 105℃ for 12h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0043] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.5, heat to 125℃ and react for 15h. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0044] (4) Graphene oxide was added to sulfoxide, wherein the mass ratio of graphene oxide to sulfoxide was 1:1.8. After ultrasonic dispersion, the mixture was reacted at 85°C for 28 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain acyl-chromium graphene.

[0045] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.4:1:0.04. React at 105℃ for 15h, and after the reaction is completed, distill under reduced pressure, filter and dry to obtain modified graphene oxide.

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

[0047] 18 parts by weight of intermediate B were added to a reactor containing methanol solvent. After stirring thoroughly, 3 parts by weight of ethylenediamine were added dropwise over 3 hours to carry out the reaction. After the reaction was completed, the intermediate C was obtained by rotary vacuum distillation at 90°C and 300 Pa.

[0048] 10 parts by weight of intermediate C and 18 parts by weight of acryloyl chloride were added to N,N-dimethylformamide solvent and stirred to dissolve. Then, 3 parts by weight of triethylamine catalyst were added and stirred at 80°C for 10 h. After the reaction was completed, the mixture was distilled under reduced pressure, filtered and dried to obtain alkenylated polyamide.

[0049] Five parts by weight of alkenylated polyamide, eight parts by weight of sodium methacrylate sulfonate, and four parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 0.8 parts by weight of ammonium persulfate initiator were added, and the mixture was heated to 120°C and reacted for 5 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0050] (7) Add 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 to a stirrer and stir at 40°C for 14 minutes. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0051] Example 3

[0052] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 85℃ for 0.9h. Then the temperature was raised to 110℃ and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.02:1.2. After the dropwise addition was completed, the reaction was carried out at 110℃ for 6h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0053] (2) Add polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride is 1.5:1, stir to dissolve, react at 97.5℃ for 8.5h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0054] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.35, heat to 117.5℃ and react for 11.5h. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0055] (4) Graphene oxide was added to thionyl chloride, wherein the mass ratio of graphene oxide to thionyl chloride was 1:1.7. After ultrasonic dispersion, the mixture was reacted at 77.5℃ for 24h. After the reaction was completed, the mixture was filtered, washed and dried to obtain acyl-chromium graphene.

[0056] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.3:1:0.03. React at 97.5℃ for 11.5h, and after the reaction is completed, distill under reduced pressure, filter and dry 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 under ice-water bath and nitrogen protection, then add 12 parts by weight of methyl acrylate dropwise over 4 hours, react at 30°C for 36 hours, and then distill under reduced pressure to obtain intermediate B.

[0058] 20 parts by weight of intermediate B were added to a reactor containing methanol solvent. After thorough stirring, 5 parts by weight of ethylenediamine were added dropwise over 4 hours to carry out the reaction. After the reaction was completed, the intermediate C was obtained by rotary vacuum distillation at 100℃ and 320Pa.

[0059] 15 parts by weight of intermediate C and 20 parts by weight of acryloyl chloride were added to N,N-dimethylformamide solvent and stirred to dissolve. Then, 5 parts by weight of triethylamine catalyst were added and stirred at 100°C for 12 h. After the reaction was completed, the mixture was distilled under reduced pressure, filtered and dried to obtain alkenylated polyamide.

[0060] Six parts by weight of alkenylated polyamide, 10 parts by weight of sodium methacrylate sulfonate, and 5 parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 1 part by weight of ammonium persulfate initiator was added, and the mixture was heated to 150°C and reacted for 6 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0061] (7) Add 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 to a stirrer and stir at 35°C for 12 minutes. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0062] Example 4

[0063] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 75°C for 0.6 h. Then the temperature was raised to 100°C and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.01:1.1. After the dropwise addition was completed, the reaction was carried out at 105°C for 4 h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0064] (2) Add 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, stir to dissolve, react at 90°C for 5 h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0065] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.5, heat to 125℃ and react for 15h. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0066] (4) Graphene oxide was added to sulfoxide, wherein the mass ratio of graphene oxide to sulfoxide was 1:1.8. After ultrasonic dispersion, the mixture was reacted at 85°C for 28 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain acyl-chromium graphene.

[0067] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.3:1:0.03. React at 97.5℃ for 11.5h, and after the reaction is completed, distill under reduced pressure, filter and dry 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 under ice-water bath and nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise over 2 hours, react at 20°C for 20 hours, and then distill under reduced pressure to obtain intermediate B.

[0069] Add 15 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2 parts by weight of ethylenediamine dropwise over 2 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70°C and 260 Pa to obtain intermediate C.

[0070] Add 7 parts by weight of intermediate C 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 to react for 8 hours at 60°C, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide.

[0071] Three parts by weight of alkenylated polyamide, five parts by weight of sodium methacrylate sulfonate, and three parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 0.5 parts by weight of ammonium persulfate initiator were added, and the mixture was heated to 100°C and reacted for 3 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0072] (7) Add 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 to a stirrer and stir at 35°C for 12 minutes. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0073] Example 5

[0074] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 95℃ for 1.2h. Then the temperature was raised to 120℃ and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.03:1.3. After the dropwise addition was completed, the reaction was carried out at 115℃ for 8h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0075] (2) Add 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. Stir to dissolve, react at 105℃ for 12h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0076] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.35, heat to 117.5℃ and react for 11.5h. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0077] (4) Graphene oxide was added to thionyl chloride, wherein the mass ratio of graphene oxide to thionyl chloride was 1:1.7. After ultrasonic dispersion, the mixture was reacted at 77.5℃ for 24h. After the reaction was completed, the mixture was filtered, washed and dried to obtain acyl-chromium graphene.

[0078] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.2:1:0.02. React at 95℃ for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry 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 under ice-water bath and nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise over 2 hours, react at 20°C for 20 hours, and then distill under reduced pressure to obtain intermediate B.

[0080] Add 15 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2 parts by weight of ethylenediamine dropwise over 2 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70°C and 260 Pa to obtain intermediate C.

[0081] Add 7 parts by weight of intermediate C 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 to react for 8 hours at 60°C, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide.

[0082] Three parts by weight of alkenylated polyamide, five parts by weight of sodium methacrylate sulfonate, and three parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 0.5 parts by weight of ammonium persulfate initiator were added, and the mixture was heated to 100°C and reacted for 3 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0083] (7) Add 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 to a stirrer and stir at 30°C for 10 min. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0084] Example 6

[0085] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 85℃ for 0.9h. Then the temperature was raised to 110℃ and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.02:1.2. After the dropwise addition was completed, the reaction was carried out at 110℃ for 6h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0086] (2) Add polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride is 1.5:1, stir to dissolve, react at 97.5℃ for 8.5h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0087] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.2, heat to 110℃ and react for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0088] (4) Add graphene oxide to sulfoxide, wherein the mass ratio of graphene oxide to sulfoxide is 1:1.6. After ultrasonic dispersion, react at 70°C for 20 h. After the reaction, filter, wash and dry to obtain acyl-chlorographene.

[0089] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.4:1:0.04. React at 105℃ for 15h, and after the reaction is completed, distill under reduced pressure, filter and dry to obtain modified graphene oxide.

[0090] (6) Add 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 to a stirrer and stir at 40°C for 14 min. After the stirring is completed, a denitrifying wastewater treatment agent is obtained.

[0091] Example 7

[0092] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 75°C for 0.6 h. Then the temperature was raised to 100°C and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.01:1.1. After the dropwise addition was completed, the reaction was carried out at 105°C for 4 h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0093] (2) Add 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. Stir to dissolve, react at 105℃ for 12h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0094] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.35, heat to 117.5℃ and react for 11.5h. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0095] (4) Graphene oxide was added to thionyl chloride, wherein the mass ratio of graphene oxide to thionyl chloride was 1:1.7. After ultrasonic dispersion, the mixture was reacted at 77.5℃ for 24h. After the reaction was completed, the mixture was filtered, washed and dried to obtain acyl-chromium graphene.

[0096] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.3:1:0.03. React at 97.5℃ for 11.5h, and after the reaction is completed, distill under reduced pressure, filter and dry 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 under ice-water bath and nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise over 2 hours, react at 20°C for 20 hours, and then distill under reduced pressure to obtain intermediate B.

[0098] Add 15 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2 parts by weight of ethylenediamine dropwise over 2 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70°C and 260 Pa to obtain intermediate C.

[0099] Add 7 parts by weight of intermediate C 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 to react for 8 hours at 60°C, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide.

[0100] Three parts by weight of alkenylated polyamide, five parts by weight of sodium methacrylate sulfonate, and three parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 0.5 parts by weight of ammonium persulfate initiator were added, and the mixture was heated to 100°C and reacted for 3 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0101] (7) Add 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 to a stirrer and stir at 35°C for 12 minutes. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0102] Example 8

[0103] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 95℃ for 1.2h. Then the temperature was raised to 120℃ and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.03:1.3. After the dropwise addition was completed, the reaction was carried out at 115℃ for 8h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0104] (2) Add polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride is 1.5:1, stir to dissolve, react at 97.5℃ for 8.5h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0105] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.2, heat to 110℃ and react for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0106] (4) Add graphene oxide to sulfoxide, wherein the mass ratio of graphene oxide to sulfoxide is 1:1.6. After ultrasonic dispersion, react at 70°C for 20 h. After the reaction, filter, wash and dry to obtain acyl-chlorographene.

[0107] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.2:1:0.02. React at 95℃ for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry 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 under ice-water bath and nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise over 2 hours, react at 20°C for 20 hours, and then distill under reduced pressure to obtain intermediate B.

[0109] Add 15 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2 parts by weight of ethylenediamine dropwise over 2 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70°C and 260 Pa to obtain intermediate C.

[0110] Add 7 parts by weight of intermediate C 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 to react for 8 hours at 60°C, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide.

[0111] Three parts by weight of alkenylated polyamide, five parts by weight of sodium methacrylate sulfonate, and three parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 0.5 parts by weight of ammonium persulfate initiator were added, and the mixture was heated to 100°C and reacted for 3 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0112] (7) Add 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 to a stirrer and stir at 30°C for 10 min. After the stirring is completed, a denitrifying wastewater treatment agent is obtained.

[0113] Example 9

[0114] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 75°C for 0.6 h. Then the temperature was raised to 100°C and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.01:1.1. After the dropwise addition was completed, the reaction was carried out at 105°C for 4 h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0115] (2) Add 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, stir to dissolve, react at 90°C for 5 h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0116] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.2, heat to 110℃ and react for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0117] (4) Add graphene oxide to sulfoxide, wherein the mass ratio of graphene oxide to sulfoxide is 1:1.6. After ultrasonic dispersion, react at 70°C for 20 h. After the reaction, filter, wash and dry to obtain acyl-chlorographene.

[0118] (5) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.4:1:0.04. React at 105℃ for 15h, and after the reaction is completed, distill under reduced pressure, filter and dry 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 under ice-water bath and nitrogen protection, then add 6 parts by weight of methyl acrylate dropwise over 2 hours, react at 20°C for 20 hours, and then distill under reduced pressure to obtain intermediate B.

[0120] Add 15 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2 parts by weight of ethylenediamine dropwise over 2 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70°C and 260 Pa to obtain intermediate C.

[0121] Add 7 parts by weight of intermediate C 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 to react for 8 hours at 60°C, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide.

[0122] Three parts by weight of alkenylated polyamide, five parts by weight of sodium methacrylate sulfonate, and three parts by weight of alkenylated chitosan were added to N,N-dimethylformamide solvent. After dissolution, 0.5 parts by weight of ammonium persulfate initiator were added, and the mixture was heated to 100°C and reacted for 3 hours. After the reaction, the solvent was removed by vacuum distillation, and the mixture was filtered, washed, and dried to obtain the sulfonic acid polymer.

[0123] (7) Add 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 to a stirrer and stir at 35°C for 12 minutes. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0124] Comparative Example 1

[0125] (1) Graphene oxide was added to thionyl chloride, wherein the mass ratio of graphene oxide to thionyl chloride was 1:1.7. After ultrasonic dispersion, the mixture was reacted at 77.5℃ for 24h. After the reaction was completed, the mixture was filtered, washed and dried to obtain acyl-chromium graphene.

[0126] (2) Add intermediate A and acyl chloride graphene to N,N-dimethylformamide solvent, stir to dissolve, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate A, acyl chloride graphene and p-toluenesulfonic acid catalyst is 1.2:1:0.02. React at 95℃ for 8 hours. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified graphene oxide.

[0127] (3) Add 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 to a stirrer and stir at 30°C for 10 minutes. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

[0128] Comparative Example 2

[0129] (1) Allyloxy polyoxyethylene ether was added to N,N-dimethylformamide solvent and stirred to dissolve. Platinum black catalyst was added to it, and the temperature was raised to 95℃ for 1.2h. Then the temperature was raised to 120℃ and heptamethyltrisiloxane was added dropwise under constant pressure. The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst and heptamethyltrisiloxane was 1:0.03:1.3. After the dropwise addition was completed, the reaction was carried out at 115℃ for 8h. After the reaction was completed, the low-boiling substances were removed by vacuum distillation to obtain polyether modified trisiloxane.

[0130] (2) Add 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. Stir to dissolve, react at 105℃ for 12h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A;

[0131] (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, wherein the mass ratio of boric acid to intermediate A is 1:1.35, heat to 117.5℃ and react for 11.5h. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane.

[0132] (4) Add 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 to a stirrer and stir at 30°C for 10 minutes. After the stirrer is set, a denitrifying wastewater treatment agent is obtained.

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

[0134] Table 1: Nitrogen content test.

[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] As shown in Table 1, Examples 1-9 of the present invention have better nitrogen removal effects compared with Comparative Examples 1-2.

[0137] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A nitrogen-removing wastewater treatment agent, characterized in that, It 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; the method for preparing the modified siloxane is as follows: (1) Add allyloxy polyoxyethylene ether to N,N-dimethylformamide solvent, stir to dissolve, continue to add platinum black catalyst, heat to 75-95℃ to activate for 0.6-1.2h, then continue to heat to 100-120℃, add heptamethyltrisiloxane dropwise under constant pressure, after the dropwise addition is completed, react at 105-115℃ for 4-8h, after the reaction is completed, remove low-boiling substances by vacuum distillation to obtain polyether modified trisiloxane; (2) Add polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, stir to dissolve, react at 90-105℃ for 5-12h, remove the solvent by vacuum distillation after the reaction, filter and dry to obtain intermediate A; (3) Add boric acid to toluene solvent, stir and disperse, then add intermediate A, heat to 110-125℃ and react for 8-15 h. After the reaction is completed, distill under reduced pressure, filter and dry to obtain modified siloxane; The method for preparing the modified graphene oxide is as follows: S1, graphene oxide is added to thionyl chloride, ultrasonically dispersed, and reacted at 70-85℃ for 20-28h. After the reaction is completed, the mixture is filtered, washed, and dried to obtain acyl-chromium graphene. S2, add the intermediate A and acyl-chlorographene to N,N-dimethylformamide solvent, stir to dissolve, continue to add p-toluenesulfonic acid catalyst, react at 95-105℃ for 8-15h, after which distill under reduced pressure, filter and dry to obtain modified graphene oxide.

2. The denitrified sewage treatment agent according to claim 1, characterized by, The mass ratio of allyloxy polyoxyethylene ether, platinum black catalyst, and heptamethyltrisiloxane in (1) is 1:0.01-0.03:1.1-1.

3.

3. The denitrified sewage treatment agent according to claim 1, characterized by, The mass ratio of polyether-modified trisiloxane and 2,3-epoxypropyltrimethylammonium chloride in (2) is 1.4-1.6:

1.

4. The denitrified sewage treatment agent according to claim 1, characterized by The mass ratio of boric acid and intermediate A in (3) is 1:1.2-1.

5.

5. The denitrified sewage treatment agent according to claim 1, characterized by The mass ratio of graphene oxide to sulfoxide in S1 is 1:1.6-1.

8.

6. The denitrified sewage treatment agent according to claim 1, characterized by The mass ratio of intermediate A, acyl-chlorographene, and p-toluenesulfonic acid catalyst in S2 is 1.2-1.4:1:0.02-0.

04.

7. The denitrified sewage treatment agent according to claim 1, characterized by The preparation method of the sulfonic acid polymer is as follows: a. Add 5-10 parts by weight of ethylenediamine to a reactor containing methanol solvent for dissolution, stir evenly under ice-water bath and nitrogen protection, then add 6-12 parts by weight of methyl acrylate dropwise over 2-4 hours, react at 20-30℃ for 20-36 hours, and distill under reduced pressure after the reaction to obtain intermediate B. b. Add 15-20 parts by weight of intermediate B to a reactor containing methanol solvent, stir thoroughly, and then add 2-5 parts by weight of ethylenediamine dropwise over 2-4 hours to carry out the reaction. After the reaction is completed, perform rotary vacuum distillation at 70-100℃ and 260-320Pa to obtain intermediate C. c. Add 7-15 parts by weight of intermediate C 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, stir to react at 60-100℃ for 8-12 hours, after which distill under reduced pressure, filter and dry to obtain alkenylated polyamide. d. Add 3-6 parts by weight of alkenylated polyamide, 5-10 parts by weight of sodium methacrylate sulfonate, and 3-5 parts by weight of alkenylated chitosan to N,N-dimethylformamide solvent. After dissolving, add 0.5-1 parts by weight of ammonium persulfate initiator, heat to 100-150℃ and react for 3-6 hours. After the reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain sulfonic acid polymer.

8. A process for the preparation of a denitrified sewage treatment agent as claimed in any one of claims 1 to 7, characterized in that, The method for preparing the denitrifying wastewater treatment agent is as follows: polyethylene glycol, modified siloxane, modified graphene oxide, urea, activated carbon, and sulfonic acid polymer are added to a stirrer and stirred at 30-40℃ for 10-14 minutes. After stirring, the denitrifying wastewater treatment agent is obtained.