An organic wastewater treatment agent and its preparation method

Abstract

The present invention discloses an organic wastewater treatment agent and a preparation method thereof, relating to the field of water treatment materials. When preparing the organic wastewater treatment agent of the present invention, nano-silica is successively reacted with silane coupling agent 4140, sodium periodate, p-phenylenediamine and dimethyl phosphite to obtain modified nano-silica; the modified nano-silica is reacted with 2,4,6-triformylphloroglucinol and 2,4-diamino-6-methoxypyrimidine to obtain functionalized nano-silica; microcrystalline cellulose is successively reacted with thionyl chloride, N-(glycidyl)-N-phenyl-epoxyethanemethylamine and thiourea to obtain modified cellulose; the modified cellulose is reacted with the functionalized nano-silica to obtain the organic wastewater treatment agent. The organic wastewater treatment agent prepared by the present invention has the abilities of antibacterial, anion pollutant adsorption, cation pollutant adsorption and photocatalytic degradation of organic pollutants.

Description

Technical Field

[0001] The present invention relates to the field of water treatment materials, and specifically to an organic wastewater treatment agent and a preparation method thereof. Background Art

[0002] Water treatment agents are a general term for a class of chemical agents used in water treatment, mainly used to remove harmful substances in water, such as corrosives, metal ions, dirt, and microorganisms, etc., in order to obtain civil or industrial water that meets the requirements. Water treatment agents are an important category in fine chemical products and have strong specificity. Different usage purposes and treatment objects require different water treatment agents.

[0003] The rapid development of industrialization has enabled the economic development level to enter the fast lane. In industrial production, chemical wastewater will be generated, and this type of wastewater contains a large amount of refractory organic matter. Refractory organic pollutants have the characteristics of complex composition, high toxicity, stable chemical structure, and being difficult to be degraded by microorganisms. Therefore, the degradation of refractory organic wastewater has become an urgent problem to be solved in the field of contemporary environmental protection. Therefore, this article introduces an organic wastewater treatment agent that can degrade organic wastewater. Summary of the Invention

[0004] The purpose of the present invention is to provide an organic wastewater treatment agent and a preparation method thereof to solve the problems existing in the prior art.

[0005] An organic wastewater treatment agent, wherein the organic wastewater treatment agent is prepared by reacting modified cellulose with functionalized nano-silica;

[0006] The modified cellulose is prepared by reacting microcrystalline cellulose with thionyl chloride, N-(glycidyl)-N-phenyl-epoxyethanemethylamine, and thiourea in sequence;

[0007] The functionalized nano-silica is prepared by reacting modified nano-silica with 2,4,6-triformylphloroglucinol and 2,4-diamino-6-methoxypyrimidine;

[0008] The modified nano-silica is prepared by reacting nano-silica with silane coupling agent 4140, sodium periodate, p-phenylenediamine, and dimethyl phosphite in sequence.

[0009] A preparation method of an organic wastewater treatment agent, the preparation method of the organic wastewater treatment agent mainly includes the following preparation steps:

[0010] (1) Mix nano-silica, silane coupling agent 4140 and isopropanol according to a mass ratio of 8 - 12:1:30 - 50, stir at 85 - 95 °C and 200 - 300 r / min for 5 - 7 h, centrifuge to separate and take the solid, wash it with deionized water 3 - 5 times, and dry it at 90 - 100 °C for 2 - 4 h to obtain hydroxylated nano-silica; Mix hydroxylated nano-silica, sodium periodate and deionized water according to a mass ratio of 1 - 2:1.9 - 2.1:95 - 105, stir at 50 - 60 r / min for 6 - 8 min, store it in the dark at 20 - 30 °C for 70 - 74 h, centrifuge, wash it with deionized water 3 - 5 times, and vacuum dry it at -10 - 0 °C for 22 - 26 h to obtain aldehyde-functionalized nano-silica; Mix aldehyde-functionalized nano-silica, ethanol and glacial acetic acid according to a mass ratio of 1:20 - 30:0.4 - 0.5, stir at 70 - 76 °C and 200 - 300 r / min under nitrogen protection for 10 - 14 min, add p-phenylenediamine which is 2 - 3 times the mass of aldehyde-functionalized nano-silica evenly within 8 - 10 min, continue to stir for 5 - 7 h, filter, wash it with deionized water 3 - 5 times, and vacuum dry it at 70 - 90 °C for 10 - 14 h to obtain pre-modified nano-silica; Mix pre-modified nano-silica and methanol according to a mass ratio of 1:20 - 30, stir at 200 - 300 r / min under nitrogen protection for 10 - 14 min, add a dimethyl phosphite mixture which is 2 - 3 times the mass of pre-modified nano-silica evenly within 8 - 10 min, raise the temperature to 60 - 64 °C, continue to stir for 6 - 8 h, filter, wash it with methanol 3 - 5 times, and vacuum dry it at 60 - 80 °C for 10 - 14 h to obtain modified nano-silica; Mix 2,4,6-triformylphloroglucinol, 2,4-diamino-6-methoxypyrimidine, modified nano-silica and a solvent according to a mass ratio of 1.2 - 1.4:

[0011] 1.6 - 1.8:2 - 3:10 - 20, add an acetic acid solution which is 0.16 - 0.17 times the volume of the solvent, ultrasonicate for 15 - 25 min, place it in the inner liner of a polytetrafluoroethylene reactor, stand at 110 - 130 °C for 70 - 74 h, centrifuge, wash it with ethanol 5 - 7 times, and dry it at 50 - 70 °C for 10 - 14 h to obtain functionalized nano-silica;

[0012] (2) Mix cellulose and N,N-dimethylformamide at a mass ratio of 1:18 - 20, stir at 85 - 95 °C and 250 - 350 r / min for 3 - 5 min, add thionyl chloride which is 5.6 - 6 times the mass of microcrystalline cellulose within 8 - 10 min, continue stirring for 2 - 3 h, pour it into deionized water, stir at 200 - 300 r / min for 10 - 16 min, filter, wash alternately with ammonia water with a mass fraction of 2.8 - 3.2% and deionized water until neutral, and vacuum dry at 45 - 55 °C for 11 - 13 h to obtain chlorinated cellulose; Mix chlorinated cellulose and N-(glycidyl)-N-phenyl-oxiranemethanamine at a mass ratio of 5 - 7:1 - 2, immerse it in N-methylpyrrolidone, react at 200 - 300 r / min and 70 - 90 °C for 10 - 14 h, vacuum dry at -10 - 0 °C for 20 - 24 h, wash with ether 3 - 5 times, and vacuum dry at -10 - 0 °C for 22 - 24 h to obtain pre-modified cellulose; Mix pre-modified cellulose, N,N-dimethylformamide and thiourea at a mass ratio of 1:20 - 30:0.4 - 0.6, stir at 60 - 80 °C and 200 - 300 r / min for 46 - 50 h, filter, wash with deionized water 5 - 7 times, and vacuum dry at 50 - 70 °C for 22 - 24 h to obtain modified cellulose;

[0013] (3) Mix modified cellulose, TEMPO, laccase, mixed solution, citrate buffer solution, and functionalized nano-silica at a mass ratio of 4 - 6:1:4 - 6:0.4 - 0.6:18 - 20:2 - 4, stir at 20 - 40 °C and 200 - 300 r / min for 12 - 16 h, add a catalyst which is 2 - 4 times the mass of TEMPO, continue to react for 12 - 16 h, filter, wash with deionized water 3 - 5 times, and vacuum dry at -10 - 0 °C for 22 - 24 h to obtain an organic wastewater treatment agent.

[0014] As an optimization, the solvent described in step (1) is prepared by mixing mesitylene and 1,4-dioxane evenly at a volume ratio of 1:1.

[0015] As an optimization, the concentration of the acetic acid solution described in step (1) is 3M.

[0016] As an optimization, the specific operation of the centrifugation described in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0017] As an optimization, the cellulose described in step (2) is microcrystalline cellulose.

[0018] As an optimization, the mixed solution described in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether at a molar ratio of 1:1, stirring at 50 - 70 °C, 200 - 300 r / min under argon protection for 10 - 14 h.

[0019] As an optimization, the citric acid buffer solution described in step (3) is prepared by mixing a 50 mM citric acid solution and a 50 mM sodium citrate solution to a pH of 5.

[0020] As an optimization, the catalyst described in step (3) is prepared by uniformly mixing L-proline, a mixed solution, and deionized water in a mass ratio of 11 - 12:46 - 47:0.017 - 0.019.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0022] When preparing the organic wastewater treatment agent of the present invention, nano-silica is successively reacted with silane coupling agent 4140, sodium periodate, p-phenylenediamine, and dimethyl phosphite to obtain modified nano-silica; the modified nano-silica is reacted with 2,4,6-triformylphloroglucinol and 2,4-diamino-6-methoxypyrimidine to obtain functionalized nano-silica; microcrystalline cellulose is successively reacted with thionyl chloride, N-(epoxypropyl)-N-phenyl-oxiranemethanamine, and thiourea to obtain modified cellulose; the modified cellulose is reacted with the functionalized nano-silica to obtain the organic wastewater treatment agent.

[0023] First, nano-silica is successively reacted with silane coupling agent 4140, sodium periodate, p-phenylenediamine, and dimethyl phosphite to obtain modified nano-silica; the modified nano-silica is reacted with 2,4,6-triformylphloroglucinol and 2,4-diamino-6-methoxypyrimidine to obtain functionalized nano-silica; nano-silica is reacted with silane coupling agent 4140 and then oxidized by sodium periodate to obtain aldehyde-functionalized nano-silica, and the aldehyde-functionalized nano-silica reacts with p-phenylenediamine to form Schiff base. The Schiff base can react with dimethyl phosphite. Under acidic conditions, phosphite will hydrolyze to generate phosphate anions, which can well adsorb cationic pollutants, and the reaction of the modified nano-silica with 2,4,6-triformylphloroglucinol and 2,4-diamino-6-methoxypyrimidine can form an organic framework to degrade organic pollutants under photocatalysis.

[0024] Secondly, microcrystalline cellulose is reacted with thionyl chloride, N-(glycidyl)-N-phenyl-epoxyethanemethylamine, and thiourea in sequence to obtain modified cellulose; the modified cellulose is reacted with functionalized nano-silica to obtain an organic wastewater treatment agent. Microcrystalline cellulose reacts with thionyl chloride to form chloro-cellulose, and chloro-cellulose reacts with N-(glycidyl)-N-phenyl-epoxyethanemethylamine to form a quaternary ammonium salt. The quaternary ammonium salt can adsorb anionic pollutants well, and the epoxy group on N-(glycidyl)-N-phenyl-epoxyethanemethylamine can react with thiourea. Thiourea can destroy the cell wall and cell membrane of pathogens, making them lose their viability, and can also inhibit the metabolic process of pathogens, thus achieving the effect of sterilization. Detailed implementation mode

[0025] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0026] Example 1:

[0027] A preparation method of an organic wastewater treatment agent mainly includes the following preparation steps:

[0028] (1) Mix nano-silica, silane coupling agent 4140 and isopropanol in a mass ratio of 8:1:30, stir at 85 °C and 200 r / min for 5 h, centrifuge to separate the solid, wash it with deionized water 3 times, and dry it at 90 °C for 2 h to obtain hydroxylated nano-silica; Mix hydroxylated nano-silica, sodium periodate and deionized water in a mass ratio of 1:1.9:95, stir at 50 r / min for 6 min, store it in the dark at 20 °C for 70 h, centrifuge, wash it with deionized water 3 times, and vacuum dry it at -10 °C for 22 h to obtain aldehyde-functionalized nano-silica; Mix aldehyde-functionalized nano-silica, ethanol and glacial acetic acid in a mass ratio of 1:20:0.4, stir at 70 °C and 200 r / min under nitrogen protection for 10 min, add p-phenylenediamine which is 2 times the mass of aldehyde-functionalized nano-silica uniformly within 8 min, continue to stir for 5 h, filter, wash it with deionized water 3 times, and vacuum dry it at 70 °C for 10 h to obtain pre-modified nano-silica; Mix pre-modified nano-silica and methanol in a mass ratio of 1:20, stir at 200 r / min under nitrogen protection for 10 min, add a dimethyl phosphite mixture which is 2 times the mass of pre-modified nano-silica uniformly within 8 min, raise the temperature to 60 °C, continue to stir for 6 h, filter, wash it with methanol 3 times, and vacuum dry it at 60 °C for 10 h to obtain modified nano-silica; Mix 2,4,6-triformylphloroglucinol, 2,4-diamino-6-methoxypyrimidine, modified nano-silica and a solvent in a mass ratio of 1.2:1.6:2:10, add an acetic acid solution which is 0.16 times the volume of the solvent, ultrasonicate for 15 min, place it in the inner liner of a polytetrafluoroethylene reactor, stand at 110 °C for 70 h, centrifuge, wash it with ethanol 5 times, and dry it at 50 °C for 10 h to obtain functionalized nano-silica;

[0029] (2) Mix cellulose and N,N-dimethylformamide in a mass ratio of 1:18, stir at 85 °C and 250 r / min for 3 min, add thionyl chloride which is 5.6 times the mass of microcrystalline cellulose within 8 min, continue to stir for 2 h, pour it into deionized water, stir at 200 r / min for 10 min, filter, wash it alternately with 2.8% ammonia water and deionized water until neutral, and vacuum dry it at 45 °C for 11 h to obtain chlorinated cellulose; Mix chlorinated cellulose and N-(epoxypropyl)-N-phenyl-oxiranemethanamine in a mass ratio of 5:1, immerse it in N-methylpyrrolidone, react at 200 r / min and 70 °C for 10 h, vacuum dry it at -10 °C for 20 h, wash it with ether 3 times, and vacuum dry it at -10 °C for 22 h to obtain pre-modified cellulose; Mix pre-modified cellulose, N,N-dimethylformamide and thiourea in a mass ratio of 1:20:0.4, stir at 60 °C and 200 r / min for 46 h, filter, wash it with deionized water 5 times, and vacuum dry it at 50 °C for 22 h to obtain modified cellulose;

[0030] (3) Mix the modified cellulose, TEMPO, laccase, the mixed solution, citric acid buffer solution, and functionalized nano-silica in a mass ratio of 4:1:4:0.4:18:2, stir at 20 °C and 200 r / min for 12 h, add a catalyst that is 2 times the mass of TEMPO, continue the reaction for 12 h, filter, wash 3 times with deionized water, and vacuum dry at -10 °C for 22 h to obtain the organic wastewater treatment agent.

[0031] As an optimization, the solvent described in step (1) is prepared by mixing mesitylene and 1,4-dioxane evenly in a volume ratio of 1:1.

[0032] As an optimization, the concentration of the acetic acid solution described in step (1) is 3 M.

[0033] As an optimization, the specific operation of the centrifugation described in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0034] As an optimization, the cellulose described in step (2) is microcrystalline cellulose.

[0035] As an optimization, the mixed solution described in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether in a molar ratio of 1:1, and stirring at 50 °C, 200 r / min under argon protection for 10 h.

[0036] As an optimization, the citric acid buffer solution described in step (3) is prepared by mixing a 50 mM citric acid solution and a 50 mM sodium citrate solution until the pH is 5.

[0037] As an optimization, the catalyst described in step (3) is prepared by mixing L-proline, the mixed solution, and deionized water evenly in a mass ratio of 11:46:0.017.

[0038] Example 2:

[0039] A preparation method of an organic wastewater treatment agent mainly includes the following preparation steps:

[0040] (1) Mix nano-silica, silane coupling agent 4140 and isopropanol in a mass ratio of 10:1:40, stir at 90 °C and 250 r / min for 6 h, centrifuge to separate and take the solid, wash it 4 times with deionized water, and dry it at 95 °C for 3 h to obtain hydroxylated nano-silica; Mix hydroxylated nano-silica, sodium periodate and deionized water in a mass ratio of 1.5:2:100, stir at 55 r / min for 7 min, store it in the dark at 25 °C for 72 h, centrifuge, wash it 4 times with deionized water, and vacuum dry it at -5 °C for 24 h to obtain aldehyde-functionalized nano-silica; Mix aldehyde-functionalized nano-silica, ethanol and glacial acetic acid in a mass ratio of 1:25:0.45, stir at 73 °C and 250 r / min under nitrogen protection for 12 min, add p-phenylenediamine which is 2.5 times the mass of aldehyde-functionalized nano-silica uniformly within 9 min, continue to stir for 6 h, filter, wash it 4 times with deionized water, and vacuum dry it at 80 °C for 12 h to obtain pre-modified nano-silica; Mix pre-modified nano-silica and methanol in a mass ratio of 1:25, stir at 250 r / min under nitrogen protection for 12 min, add a dimethyl phosphite mixture which is 2.5 times the mass of pre-modified nano-silica uniformly within 9 min, raise the temperature to 62 °C, continue to stir for 7 h, filter, wash it 4 times with methanol, and vacuum dry it at 70 °C for 12 h to obtain modified nano-silica; Mix 2,4,6-triformylphloroglucinol, 2,4-diamino-6-methoxypyrimidine, modified nano-silica and a solvent in a mass ratio of 1.3:1.7:2.5:15, add an acetic acid solution which is 0.165 times the volume of the solvent, ultrasonicate for 20 min, place it in the inner liner of a polytetrafluoroethylene reactor, let it stand at 120 °C for 72 h, centrifuge, wash it 6 times with ethanol, and dry it at 60 °C for 12 h to obtain functionalized nano-silica;

[0041] (2) Mix cellulose and N,N-dimethylformamide at a mass ratio of 1:19, stir at 90 °C and 300 r / min for 4 min, add thionyl chloride 5.8 times the mass of microcrystalline cellulose within 9 min, continue stirring for 2.5 h, pour into deionized water, stir at 250 r / min for 13 min, filter, wash alternately with 3% ammonia water and deionized water until neutral, and vacuum dry at 50 °C for 12 h to obtain chlorinated cellulose; Mix chlorinated cellulose and N-(glycidyl)-N-phenyl-oxiranemethanamine at a mass ratio of 6:1.5, immerse in N-methylpyrrolidone, react at 250 r / min and 80 °C for 12 h, vacuum dry at -5 °C for 22 h, wash with ether 4 times, and vacuum dry at -5 °C for 23 h to obtain pre-modified cellulose; Mix pre-modified cellulose, N,N-dimethylformamide and thiourea at a mass ratio of 1:25:0.5, stir at 70 °C and 250 r / min for 48 h, filter, wash with deionized water 6 times, and vacuum dry at 60 °C for 23 h to obtain modified cellulose;

[0042] (3) Mix modified cellulose, TEMPO, laccase, the mixed solution, citrate buffer solution, and functionalized nano-silica at a mass ratio of 5:1:5:0.5:19:3, stir at 30 °C and 250 r / min for 14 h, add a catalyst 3 times the mass of TEMPO, continue reacting for 14 h, filter, wash with deionized water 4 times, and vacuum dry at -5 °C for 23 h to obtain the organic wastewater treatment agent.

[0043] As an optimization, the solvent described in step (1) is prepared by mixing mesitylene and 1,4-dioxane evenly at a volume ratio of 1:1.

[0044] As an optimization, the concentration of the acetic acid solution described in step (1) is 3M.

[0045] As an optimization, the specific operation of the centrifugation described in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0046] As an optimization, the cellulose described in step (2) is microcrystalline cellulose.

[0047] As an optimization, the mixed solution described in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether at a molar ratio of 1:1, stirring at 60 °C, 250 r / min, and under argon protection for 12 h.

[0048] As an optimization, the citrate buffer solution described in step (3) is prepared by mixing a 50 mM citric acid solution and a 50 mM sodium citrate solution until the pH is 5.

[0049] As an optimization, the catalyst described in step (3) is prepared by uniformly mixing L-proline, a mixed solution, and deionized water in a mass ratio of 11.5:46.5:0.018.

[0050] Example 3:

[0051] A preparation method of an organic wastewater treatment agent mainly includes the following preparation steps:

[0052] (1) Mix nano-silica, silane coupling agent 4140, and isopropanol in a mass ratio of 12:1:50, stir at 95 °C and 300 r / min for 7 h, centrifuge to separate the solid, wash it 5 times with deionized water, and dry it at 100 °C for 4 h to obtain hydroxylated nano-silica; Mix hydroxylated nano-silica, sodium periodate, and deionized water in a mass ratio of 2:2.1:105, stir at 60 r / min for 8 min, store it in the dark at 30 °C for 74 h, centrifuge, wash it 5 times with deionized water, and vacuum dry it at 0 °C for 26 h to obtain aldehyde-functionalized nano-silica; Mix aldehyde-functionalized nano-silica, ethanol, and glacial acetic acid in a mass ratio of 1:30:0.5, stir at 76 °C and 300 r / min under nitrogen protection for 14 min, uniformly add p-phenylenediamine, which is 3 times the mass of aldehyde-functionalized nano-silica, within 10 min, continue to stir for 7 h, filter, wash it 5 times with deionized water, and vacuum dry it at 90 °C for 14 h to obtain pre-modified nano-silica; Mix pre-modified nano-silica and methanol in a mass ratio of 1:30, stir at 300 r / min under nitrogen protection for 14 min, uniformly add a dimethyl phosphite mixed solution, which is 3 times the mass of pre-modified nano-silica, within 10 min, raise the temperature to 64 °C, continue to stir for 8 h, filter, wash it 5 times with methanol, and vacuum dry it at 80 °C for 14 h to obtain modified nano-silica; Mix 2,4,6-triformylphloroglucinol, 2,4-diamino-6-methoxypyrimidine, modified nano-silica, and a solvent in a mass ratio of 1.4:1.8:3:20, add an acetic acid solution that is 0.17 times the volume of the solvent, ultrasonicate for 25 min, place it in the inner liner of a polytetrafluoroethylene reactor, stand at 130 °C for 74 h, centrifuge, wash it 7 times with ethanol, and dry it at 70 °C for 14 h to obtain functionalized nano-silica;

[0053] (2) Mix cellulose and N,N-dimethylformamide at a mass ratio of 1:20, stir at 95 °C and 350 r / min for 5 min, add thionyl chloride 6 times the mass of microcrystalline cellulose within 10 min, continue stirring for 3 h, pour into deionized water, stir at 300 r / min for 16 min, filter, wash alternately with ammonia water with a mass fraction of 3.2% and deionized water until neutral, and vacuum dry at 55 °C for 13 h to obtain chlorinated cellulose; Mix chlorinated cellulose and N-(epoxypropyl)-N-phenyl-oxiranemethanamine at a mass ratio of 7:2, immerse in N-methylpyrrolidone, react at 300 r / min and 90 °C for 14 h, vacuum dry at 0 °C for 24 h, wash with ether 5 times, and vacuum dry at 0 °C for 24 h to obtain pre-modified cellulose; Mix pre-modified cellulose, N,N-dimethylformamide and thiourea at a mass ratio of 1:30:0.6, stir at 80 °C and 300 r / min for 50 h, filter, wash with deionized water 7 times, and vacuum dry at 70 °C for 24 h to obtain modified cellulose;

[0054] (3) Mix modified cellulose, TEMPO, laccase, mixed solution, citrate buffer solution, and functionalized nano-silica at a mass ratio of 6:1:6:0.6:20:4, stir at 40 °C and 300 r / min for 16 h, add a catalyst 4 times the mass of TEMPO, continue reacting for 16 h, filter, wash with deionized water 5 times, and vacuum dry at 0 °C for 24 h to obtain an organic wastewater treatment agent.

[0055] As an optimization, the solvent described in step (1) is prepared by mixing mesitylene and 1,4-dioxane evenly at a volume ratio of 1:1.

[0056] As an optimization, the concentration of the acetic acid solution described in step (1) is 3 M.

[0057] As an optimization, the specific operation of the centrifugation described in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0058] As an optimization, the cellulose described in step (2) is microcrystalline cellulose.

[0059] As an optimization, the mixed solution described in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether at a molar ratio of 1:1, stirring at 70 °C, 300 r / min under argon protection for 14 h.

[0060] As an optimization, the citrate buffer solution described in step (3) is prepared by mixing a 50 mM citric acid solution and a 50 mM sodium citrate solution until the pH is 5.

[0061] As an optimization, the catalyst described in step (3) is prepared by uniformly mixing L-proline, a mixed solution, and deionized water in a mass ratio of 12:47:0.019.

[0062] Comparative Example 1:

[0063] A preparation method of an organic wastewater treatment agent mainly includes the following preparation steps:

[0064] (1) Mix nano-silica, silane coupling agent 4140, and isopropanol in a mass ratio of 10:1:40, stir at 90 °C and 250 r / min for 6 h, centrifuge to separate the solid, wash it 4 times with deionized water, and dry it at 95 °C for 3 h to obtain hydroxylated nano-silica; Mix hydroxylated nano-silica, sodium periodate, and deionized water in a mass ratio of 1.5:2:100, stir at 55 r / min for 7 min, store it in the dark at 25 °C for 72 h, centrifuge, wash it 4 times with deionized water, and vacuum dry it at -5 °C for 24 h to obtain aldehyde-functionalized nano-silica; Mix aldehyde-functionalized nano-silica, ethanol, and glacial acetic acid in a mass ratio of 1:25:0.45, stir at 73 °C, 250 r / min, under nitrogen protection for 12 min, uniformly add p-phenylenediamine 2.5 times the mass of aldehyde-functionalized nano-silica within 9 min, continue to stir for 6 h, filter, wash it 4 times with deionized water, and vacuum dry it at 80 °C for 12 h to obtain pre-modified nano-silica; Mix 2,4,6-triformylphloroglucinol, 2,4-diamino-6-methoxypyrimidine, pre-modified nano-silica, and a solvent in a mass ratio of 1.3:1.7:2.5:15, add an acetic acid solution 0.165 times the volume of the solvent, ultrasonicate for 20 min, place it in the inner liner of a polytetrafluoroethylene reactor, stand at 120 °C for 72 h, centrifuge, wash it 6 times with ethanol, and dry it at 60 °C for 12 h to obtain functionalized nano-silica;

[0065] (2) Mix cellulose and N,N-dimethylformamide at a mass ratio of 1:19, stir at 90 °C and 300 r / min for 4 min, add thionyl chloride 5.8 times the mass of microcrystalline cellulose within 9 min, continue stirring for 2.5 h, pour into deionized water, stir at 250 r / min for 13 min, filter, wash alternately with 3% ammonia water and deionized water until neutral, and vacuum dry at 50 °C for 12 h to obtain chlorinated cellulose; Mix chlorinated cellulose and N-(glycidyl)-N-phenyl-oxiranemethanamine at a mass ratio of 6:1.5, immerse in N-methylpyrrolidone, react at 250 r / min and 80 °C for 12 h, vacuum dry at -5 °C for 22 h, wash with ether 4 times, and vacuum dry at -5 °C for 23 h to obtain pre-modified cellulose; Mix pre-modified cellulose, N,N-dimethylformamide and thiourea at a mass ratio of 1:25:0.5, stir at 70 °C and 250 r / min for 48 h, filter, wash with deionized water 6 times, and vacuum dry at 60 °C for 23 h to obtain modified cellulose;

[0066] (3) Mix modified cellulose, TEMPO, laccase, mixed solution, citrate buffer solution, and functionalized nano-silica at a mass ratio of 5:1:5:0.5:19:3, stir at 30 °C and 250 r / min for 14 h, add a catalyst 3 times the mass of TEMPO, continue reacting for 14 h, filter, wash with deionized water 4 times, and vacuum dry at -5 °C for 23 h to obtain an organic wastewater treatment agent.

[0067] As an optimization, the solvent described in step (1) is prepared by mixing mesitylene and 1,4-dioxane evenly at a volume ratio of 1:1.

[0068] As an optimization, the concentration of the acetic acid solution described in step (1) is 3 M.

[0069] As an optimization, the specific operation of centrifugation in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0070] As an optimization, the cellulose described in step (2) is microcrystalline cellulose.

[0071] As an optimization, the mixed solution described in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether at a molar ratio of 1:1, stirring at 60 °C, 250 r / min under argon protection for 12 h.

[0072] As an optimization, the citrate buffer solution described in step (3) is prepared by mixing a 50 mM citric acid solution and a 50 mM sodium citrate solution until the pH is 5.

[0073] As an optimization, the catalyst described in step (3) is prepared by uniformly mixing L-proline, a mixed solution, and deionized water in a mass ratio of 11.5:46.5:0.018.

[0074] Comparative Example 2

[0075] A preparation method of an organic wastewater treatment agent mainly includes the following preparation steps:

[0076] (1) Mix nano-silica, silane coupling agent 4140, and isopropanol in a mass ratio of 10:1:40, stir at 90 °C and 250 r / min for 6 h, centrifuge to separate the solid, wash it 4 times with deionized water, and dry it at 95 °C for 3 h to obtain hydroxylated nano-silica; mix hydroxylated nano-silica, sodium periodate, and deionized water in a mass ratio of 1.5:2:100, stir at 55 r / min for 7 min, store it in the dark at 25 °C for 72 h, centrifuge, wash it 4 times with deionized water, and vacuum dry it at -5 °C for 24 h to obtain aldehyde-functionalized nano-silica; mix aldehyde-functionalized nano-silica, ethanol, and glacial acetic acid in a mass ratio of 1:25:0.45, stir at 73 °C, 250 r / min, under nitrogen protection for 12 min, uniformly add p-phenylenediamine, which is 2.5 times the mass of aldehyde-functionalized nano-silica, within 9 min, continue to stir for 6 h, filter, wash it 4 times with deionized water, and vacuum dry it at 80 °C for 12 h to obtain pre-modified nano-silica; mix pre-modified nano-silica and methanol in a mass ratio of 1:25, stir at 250 r / min, under nitrogen protection for 12 min, uniformly add a mixed solution of dimethyl phosphite, which is 2.5 times the mass of pre-modified nano-silica, within 9 min, raise the temperature to 62 °C, continue to stir for 7 h, filter, wash it 4 times with methanol, and vacuum dry it at 70 °C for 12 h to obtain modified nano-silica;

[0077] (2) Mix cellulose and N,N-dimethylformamide at a mass ratio of 1:19, stir at 90 °C and 300 r / min for 4 min, add thionyl chloride 5.8 times the mass of microcrystalline cellulose within 9 min, continue stirring for 2.5 h, pour into deionized water, stir at 250 r / min for 13 min, filter, wash alternately with 3% ammonia water and deionized water until neutral, and vacuum dry at 50 °C for 12 h to obtain chlorinated cellulose; mix chlorinated cellulose and N-(glycidyl)-N-phenyl-oxiranemethanamine at a mass ratio of 6:1.5, immerse in N-methylpyrrolidone, react at 250 r / min and 80 °C for 12 h, vacuum dry at -5 °C for 22 h, wash with ether 4 times, and vacuum dry at -5 °C for 23 h to obtain pre-modified cellulose; mix pre-modified cellulose, N,N-dimethylformamide and thiourea at a mass ratio of 1:25:0.5, stir at 70 °C and 250 r / min for 48 h, filter, wash with deionized water 6 times, and vacuum dry at 60 °C for 23 h to obtain modified cellulose;

[0078] (3) Mix modified cellulose, TEMPO, laccase, mixed solution, citrate buffer solution, and modified nano-silica at a mass ratio of 5:1:5:0.5:19:3, stir at 30 °C and 250 r / min for 14 h, add a catalyst 3 times the mass of TEMPO, continue reacting for 14 h, filter, wash with deionized water 4 times, and vacuum dry at -5 °C for 23 h to obtain an organic wastewater treatment agent.

[0079] As an optimization, the specific operation of the centrifugation in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0080] As an optimization, the cellulose in step (2) is microcrystalline cellulose.

[0081] As an optimization, the mixed solution in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether at a molar ratio of 1:1, stirring at 60 °C, 250 r / min under argon protection for 12 h.

[0082] As an optimization, the citrate buffer solution in step (3) is prepared by mixing 50 mM citric acid solution and 50 mM sodium citrate solution to a pH of 5.

[0083] As an optimization, the catalyst in step (3) is prepared by uniformly mixing L-proline, mixed solution and deionized water at a mass ratio of 11.5:46.5:0.018.

[0084] Comparative Example 3

[0085] A preparation method of an organic wastewater treatment agent mainly includes the following preparation steps:

[0086] (1) Mix nano-silica, silane coupling agent 4140 and isopropanol according to a mass ratio of 10:1:40, stir at 90 °C and 250 r / min for 6 h, centrifuge to separate the solid, wash it 4 times with deionized water, and dry it at 95 °C for 3 h to obtain hydroxylated nano-silica; Mix hydroxylated nano-silica, sodium periodate and deionized water according to a mass ratio of 1.5:2:100, stir at 55 r / min for 7 min, store it in the dark at 25 °C for 72 h, centrifuge, wash it 4 times with deionized water, and vacuum dry it at -5 °C for 24 h to obtain aldehyde-functionalized nano-silica; Mix aldehyde-functionalized nano-silica, ethanol and glacial acetic acid according to a mass ratio of 1:25:0.45, stir at 73 °C and 250 r / min under nitrogen protection for 12 min, add p-phenylenediamine which is 2.5 times the mass of aldehyde-functionalized nano-silica uniformly within 9 min, continue to stir for 6 h, filter, wash it 4 times with deionized water, and vacuum dry it at 80 °C for 12 h to obtain pre-modified nano-silica; Mix pre-modified nano-silica and methanol according to a mass ratio of 1:25, stir at 250 r / min under nitrogen protection for 12 min, add a dimethyl phosphite mixture which is 2.5 times the mass of pre-modified nano-silica uniformly within 9 min, raise the temperature to 62 °C, continue to stir for 7 h, filter, wash it 4 times with methanol, and vacuum dry it at 70 °C for 12 h to obtain modified nano-silica; Mix 2,4,6-triformylphloroglucinol, 2,4-diamino-6-methoxypyrimidine, modified nano-silica and a solvent according to a mass ratio of 1.3:1.7:2.5:15, add an acetic acid solution which is 0.165 times the volume of the solvent, ultrasonicate for 20 min, place it in the inner liner of a polytetrafluoroethylene reactor, stand at 120 °C for 72 h, centrifuge, wash it 6 times with ethanol, and dry it at 60 °C for 12 h to obtain functionalized nano-silica;

[0087] (2) Mix cellulose and N,N-dimethylformamide according to a mass ratio of 1:19, stir at 90 °C and 300 r / min for 4 min, add thionyl chloride which is 5.8 times the mass of microcrystalline cellulose within 9 min, continue to stir for 2.5 h, pour it into deionized water, stir at 250 r / min for 13 min, filter, wash it alternately with 3% ammonia water and deionized water until neutral, and vacuum dry it at 50 °C for 12 h to obtain chlorinated cellulose; Mix chlorinated cellulose and N-(epoxypropyl)-N-phenyl-oxiranemethanamine according to a mass ratio of 6:1.5, immerse it in N-methylpyrrolidone, react at 250 r / min and 80 °C for 12 h, vacuum dry it at -5 °C for 22 h, wash it 4 times with ether, and vacuum dry it at -5 °C for 23 h to obtain pre-modified cellulose;

[0088] (3) Mix pre-modified cellulose, TEMPO, laccase, the mixed solution, citric acid buffer solution, and functionalized nano-silica in a mass ratio of 5:1:5:0.5:19:3, stir at 30 °C and 250 r / min for 14 h, add a catalyst 3 times the mass of TEMPO, continue the reaction for 14 h, filter, wash 4 times with deionized water, and vacuum dry at -5 °C for 23 h to obtain the organic wastewater treatment agent.

[0089] As an optimization, the solvent described in step (1) is prepared by mixing mesitylene and 1,4-dioxane evenly in a volume ratio of 1:1.

[0090] As an optimization, the concentration of the acetic acid solution described in step (1) is 3 M.

[0091] As an optimization, the specific operation of the centrifugation described in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0092] As an optimization, the cellulose described in step (2) is microcrystalline cellulose.

[0093] As an optimization, the mixed solution described in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether in a molar ratio of 1:1, stirring at 60 °C, 250 r / min under argon protection for 12 h.

[0094] As an optimization, the citric acid buffer solution described in step (3) is prepared by mixing a 50 mM citric acid solution and a 50 mM sodium citrate solution until the pH is 5.

[0095] As an optimization, the catalyst described in step (3) is prepared by mixing L-proline, the mixed solution, and deionized water evenly in a mass ratio of 11.5:46.5:0.018.

[0096] Comparative Example 4

[0097] A preparation method of an organic wastewater treatment agent mainly includes the following preparation steps:

[0098] (1) Mix nano-silica, silane coupling agent 4140 and isopropanol in a mass ratio of 10:1:40, stir at 90 °C and 250 r / min for 6 h, centrifuge to separate the solid, wash it 4 times with deionized water, and dry it at 95 °C for 3 h to obtain hydroxylated nano-silica; Mix hydroxylated nano-silica, sodium periodate and deionized water in a mass ratio of 1.5:2:100, stir at 55 r / min for 7 min, store it in the dark at 25 °C for 72 h, centrifuge, wash it 4 times with deionized water, and vacuum dry it at -5 °C for 24 h to obtain aldehyde-functionalized nano-silica; Mix aldehyde-functionalized nano-silica, ethanol and glacial acetic acid in a mass ratio of 1:25:0.45, stir at 73 °C and 250 r / min under nitrogen protection for 12 min, add p-phenylenediamine which is 2.5 times the mass of aldehyde-functionalized nano-silica uniformly within 9 min, continue to stir for 6 h, filter, wash it 4 times with deionized water, and vacuum dry it at 80 °C for 12 h to obtain pre-modified nano-silica; Mix pre-modified nano-silica and methanol in a mass ratio of 1:25, stir at 250 r / min under nitrogen protection for 12 min, add a dimethyl phosphite mixture which is 2.5 times the mass of pre-modified nano-silica uniformly within 9 min, raise the temperature to 62 °C, continue to stir for 7 h, filter, wash it 4 times with methanol, and vacuum dry it at 70 °C for 12 h to obtain modified nano-silica; Mix 2,4,6-triformylphloroglucinol, 2,4-diamino-6-methoxypyrimidine, modified nano-silica and a solvent in a mass ratio of 1.3:1.7:2.5:15, add an acetic acid solution which is 0.165 times the volume of the solvent, ultrasonicate for 20 min, place it in the inner liner of a polytetrafluoroethylene reactor, stand at 120 °C for 72 h, centrifuge, wash it 6 times with ethanol, and dry it at 60 °C for 12 h to obtain functionalized nano-silica;

[0099] (2) Mix cellulose, TEMPO, laccase, a mixed solution, citrate buffer solution, and functionalized nano-silica in a mass ratio of 5:1:5:0.5:19:3, stir at 30 °C and 250 r / min for 14 h, add a catalyst which is 3 times the mass of TEMPO, continue to react for 14 h, filter, wash it 4 times with deionized water, and vacuum dry it at -5 °C for 23 h to obtain an organic wastewater treatment agent.

[0100] As an optimization, the solvent described in step (1) is prepared by mixing mesitylene and 1,4-dioxane evenly in a volume ratio of 1:1.

[0101] As an optimization, the concentration of the acetic acid solution described in step (1) is 3 M.

[0102] As an optimization, the specific operation of the centrifugation described in step (1) is to centrifuge at a speed of 10000 rmp for 3 min.

[0103] As an optimization, the cellulose described in step (2) is microcrystalline cellulose.

[0104] As an optimization, the mixed solution described in step (2) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether in a molar ratio of 1:1, stirring at 60 °C, 250 r / min under argon protection for 12 h.

[0105] As an optimization, the citrate buffer solution described in step (2) is prepared by mixing a 50 mM citric acid solution and a 50 mM sodium citrate solution to a pH of 5.

[0106] As an optimization, the catalyst described in step (3) is prepared by uniformly mixing L-proline, the mixed solution and deionized water in a mass ratio of 11.5:46.5:0.018.

[0107] Test Example 1:

[0108] Antibacterial property test

[0109] The test was carried out according to the shaking method of GB / T20944, and the selected bacterial strains were Staphylococcus aureus and Escherichia coli. The results are shown in Table 1.

[0110] Table 1

[0111]

[0112] It can be found from the comparison of the experimental data in Table 1 that the organic wastewater treatment agent prepared by the present invention has good antibacterial ability.

[0113] It can be found from the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3 in Table 1 that the antibacterial rates of Examples 1, 2, 3 are higher than that of Comparative Example 3, indicating that the epoxy group on N-(glycidyl)-N-phenyl-oxiranemethanamine can react with thiourea. Thiourea can destroy the cell wall and cell membrane of pathogens, making them lose their viability, and can also inhibit the metabolic process of pathogens, thus achieving the bactericidal effect;

[0114] It can be found from the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4 in Table 1 that the antibacterial rates of Examples 1, 2, 3 are higher than that of Comparative Example 4, indicating that the quaternary ammonium salt can change the cell permeability, causing the bacterial cells to rupture; it can denature proteins; it can inhibit certain enzymes in bacteria, making them lose their activity; and due to its good surface activity, it can aggregate at a high concentration on the surface of bacterial cells, affecting the metabolism of bacteria, thus achieving the bactericidal effect.

[0115] Test Example 2:

[0116] Anionic pollutants, anionic pollutant adsorption test

[0117] Test method: The measuring device is a Shimadzu UV-2700 ultraviolet spectrophotometer produced by Shimadzu Corporation of Japan. The process is as follows: Prepare 10 mg / L Congo red solution and Rhodamine B solution respectively; put the sewage treatment agent into a sandwich beaker, and pour in Congo red solution 20 times the mass of the sewage treatment agent, and let it stand in the dark for 120 min. Calculate the adsorption rates of Congo red and Rhodamine B. Among them, the Congo red adsorption rate = (initial absorbance value of Congo red - absorbance value of Congo red after 120 min) / initial absorbance value of Congo red * 100%, and the same applies to Rhodamine B. The results are shown in Table 2.

[0118] Table 2

[0119] Congo Red Rhodamine B Example 1 65.3％ 64.7％ Example 2 64.9％ 65.1％ Example 3 65.4％ 65.2％ Comparative Example 1 65.2％ 13.5％ Comparative Example 2 64.8％ 64.9％ Comparative Example 3 65.0％ 65.3％ Comparative Example 4 12.7％ 64.6％

[0120] From the comparison of the experimental data in Table 2, it can be found that the organic wastewater treatment agent prepared by the present invention has good adsorption capacity for anionic pollutants and cationic pollutants.

[0121] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4 in Table 2, it can be found that the Congo red adsorption rates of Examples 1, 2, 3 are higher than those of Comparative Example 4, indicating that microcrystalline cellulose reacts with thionyl chloride to form chlorinated cellulose, and chlorinated cellulose reacts with N-(epoxypropyl)-N-phenyl-epoxyethanemethylamine to form a quaternary ammonium salt, and the quaternary ammonium salt can adsorb anionic pollutants well;

[0122] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1, it can be found that the Rhodamine B adsorption rates of Examples 1, 2, 3 are higher than those of Comparative Example 1, indicating that nano-silica reacts with silane coupling agent 4140 and is then oxidized by sodium periodate to obtain aldehyde-functionalized nano-silica. Aldehyde-functionalized nano-silica reacts with p-phenylenediamine to form Schiff base. Schiff base can react with dimethyl phosphite. Under acidic conditions, phosphite will hydrolyze to form phosphate anions, which can adsorb cationic pollutants well.

[0123] Test Example 3

[0124] Organic pollutant degradation test

[0125] Test method: The measuring device is a Shimadzu UV-2700 ultraviolet spectrophotometer produced by Shimadzu Corporation of Japan. The process is as follows: Prepare 10 mg / L Congo red solution and Rhodamine B solution respectively; put the sewage treatment agent into a sandwich beaker, and pour in Congo red solution 20 times the mass of the sewage treatment agent, and let it stand in natural light for 120 min. Calculate the degradation rates of Congo red and Rhodamine B. Among them, the Congo red degradation rate = (initial absorbance value of Congo red - absorbance value of Congo red after 120 min) / initial absorbance value of Congo red * 100%, and the same applies to Rhodamine B. The results are shown in Table 3.

[0126] Table 3

[0127] Congo Red Rhodamine B Example 1 99.5％ 99.4％ Example 2 99.2％ 99.6％ Example 3 99.3％ 99.3％ Comparative Example 1 99.1％ 92.9％ Comparative Example 2 64.5％ 64.7％ Comparative Example 3 99.4％ 99.4％ Comparative Example 4 93.1％ 99.1％

[0128] From the comparison of the experimental data in Table 3, it can be found that the organic wastewater treatment agent prepared by the present invention has good pollutant degradation ability.

[0129] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2 in Table 3, it can be found that the Congo red degradation rate and rhodamine B degradation rate of Examples 1, 2, 3 are higher than those of Comparative Example 2, indicating that the functionalized nano-silica generates an organic framework and can degrade organic pollutants under photocatalysis;

[0130] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1, it can be found that the rhodamine B degradation rate of Examples 1, 2, 3 is higher than that of Comparative Example 1, indicating that nano-silica reacts with silane coupling agent 4140 and is then oxidized by sodium periodate to obtain aldehyde-functionalized nano-silica. The aldehyde-functionalized nano-silica reacts with p-phenylenediamine to form a Schiff base. The Schiff base can react with dimethyl phosphite. Under acidic conditions, phosphite will hydrolyze to generate phosphate anions, which can well adsorb cationic pollutants, thereby better degrading organic pollutants;

[0131] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4, it can be found that the Congo red degradation rate of Examples 1, 2, 3 is higher than that of Comparative Example 4, indicating that microcrystalline cellulose reacts with thionyl chloride to generate chloro-cellulose, and the chloro-cellulose reacts with N-(epoxypropyl)-N-phenyl-oxiranemethylamine to generate a quaternary ammonium salt. The quaternary ammonium salt can well adsorb anionic pollutants, thereby better degrading organic pollutants.

[0132] The specific embodiments described above further elaborate on the purpose, technical solution and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing an organic wastewater treatment agent, characterized in that: The preparation method of the organic wastewater treatment agent mainly includes the following preparation steps: (1) Nano-silica, silane coupling agent 4140 and isopropanol were mixed in a mass ratio of 8-12:1:30-50, stirred at 85-95°C and 200-300 r / min for 5-7 h, centrifuged to obtain a solid, washed with deionized water for 3-5 times, and dried at 90-100°C for 2-4 h to obtain hydroxylated nano-silica; hydroxylated nano-silica, sodium periodate and deionized water were mixed in a mass ratio of 1-2:1.9-2.1:95-105, stirred at 50-60 r / min for 6-8 min, and dried at 20- The mixture was stored at 30°C in the dark for 70-74 hours, centrifuged, washed with deionized water for 3-5 times, and vacuum dried at -10-0°C for 22-26 hours to obtain formaldehyde-modified nano-silica; the formaldehyde-modified nano-silica, ethanol and glacial acetic acid were mixed in a mass ratio of 1:20-30:0.4-0.5, stirred for 10-14 minutes at 70-76°C, 200-300 r / min, and nitrogen protection, and p-phenylenediamine in an amount of 2-3 times the mass of the formaldehyde-modified nano-silica was added at a uniform speed within 8-10 minutes, the mixture was stirred for 5-7 hours, filtered, and washed with deionized water. The pre-modified nano-silica was prepared by washing 3 to 5 times and vacuum drying at 70 to 90°C for 10 to 14 hours. The pre-modified nano-silica was mixed with methanol at a mass ratio of 1:20 to 30, stirred at 200 to 300 r / min for 10 to 14 minutes under nitrogen protection, and a dimethyl phosphite mixture of 2 to 3 times the mass of the pre-modified nano-silica was uniformly added within 8 to 10 minutes, the temperature was raised to 60 to 64°C, stirring was continued for 6 to 8 hours, filtered, washed with methanol 3 to 5 times, and vacuum dried at 60 to 80°C for 10 to 14 hours to obtain the modified nano-silica. Functionalized nano-silica; 2,4,6-triformylpyrogallol, 2,4-diamino-6-methoxypyrimidine, modified nano-silica and solvent are mixed in a mass ratio of 1.2-1.4:1.6-1.8:2-3:10-20, an acetic acid solution of 0.16-0.17 times the volume of the solvent is added, ultrasonicated for 15-25 minutes, placed in a polytetrafluoroethylene reactor liner, allowed to stand at 110-130°C for 70-74 hours, centrifuged, washed with ethanol for 5-7 times, and dried at 50-70°C for 10-14 hours to obtain functionalized nano-silica; (2) Mix cellulose and N,N-dimethylformamide in a mass ratio of 1:18-20, stir at 85-95°C and 250-350 r / min for 3-5 min, add 5.6-6 times the mass of microcrystalline cellulose of thionyl chloride within 8-10 min, continue stirring for 2-3 h, pour into deionized water, stir at 200-300 r / min for 10-16 min, filter, and wash alternately with 2.8-3.2% ammonia water and deionized water until neutral. Vacuum drying at 45-55°C for 11-13h to obtain chlorocellulose; mixing chlorocellulose and N-(epoxypropyl)-N-phenyl-oxirane methylamine at a mass ratio of 5-7:1-2, immersing in N-methylpyrrolidone, reacting at 200-300r / min and 70-90°C for 10-14h, vacuum drying at -10-0°C for 20-24h, washing with ether for 3-5 times, and vacuum drying at -10-0°C for 22-24h to obtain pre-modified cellulose; Pre-modified cellulose, N,N-dimethylformamide and thiourea are mixed in a mass ratio of 1:20-30:0.4-0.6, stirred at 60-80°C and 200-300 r / min for 46-50 hours, filtered, washed with deionized water for 5-7 times, and vacuum dried at 50-70°C for 22-24 hours to obtain modified cellulose; (3) Modified cellulose, TEMPO, laccase, mixed solution, citric acid buffer, and functionalized nano-silica were mixed in a mass ratio of 4-6:1:4-6:0.4-0.6:18-20:2-4, stirred at 20-40°C and 200-300 r / min for 12-16 h, added with a catalyst 2-4 times the mass of TEMPO, continued to react for 12-16 h, filtered, washed with deionized water 3-5 times, and vacuum dried at -10-0°C for 22-24 h to obtain an organic wastewater treatment agent.

2. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The solvent in step (1) is prepared by uniformly mixing mesitylene and 1,4-dioxane in a volume ratio of 1:

1.

3. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The concentration of the acetic acid solution in step (1) is 3M.

4. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The specific operation of the centrifugation in step (1) is to centrifuge at a speed of 10000 rpm for 3 minutes.

5. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The cellulose in step (2) is microcrystalline cellulose.

6. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The mixed solution in step (3) is prepared by mixing lithium bis(trifluoromethanesulfonyl)imide and triethylene glycol dimethyl ether in a molar ratio of 1:1, and stirring at 50-70° C., 200-300 r / min, under argon protection, for 10-14 hours.

7. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The citric acid buffer in step (3) is prepared by mixing 50 mM citric acid solution and 50 mM sodium citrate solution to a pH of 5.

8. The method for preparing an organic wastewater treating agent according to claim 1, characterized in that: The catalyst in step (3) is prepared by uniformly mixing L-proline, the mixed solution and deionized water in a mass ratio of 11-12:46-47:0.017-0.019.

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