A biocarbon composite sewage treatment agent and its preparation method

Abstract

The invention discloses a biocarbon composite sewage treatment agent and a preparation method thereof. The agent is prepared by polymerizing acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, a modified biocarbon carrier and a modified monomer. The sewage treatment agent contains molybdenum disulfide, which can adsorb heavy metal ions through electrostatic adsorption and form metal-sulfur bonds with metal ions to achieve the effect of adsorbing heavy metal ions. The condensed phenol hydroxyl groups on the surface can chelate metal ions. The polymer chain segments on the surface of the sewage treatment agent contain positively charged groups, hydrophobic groups and hydrophilic groups. Under the interaction of the hydrophobic groups, intramolecular and intermolecular associations can be caused, thereby causing the polymer chain segments on the carrier surface to cross-link to form a grid structure. At the same time, the grid surface contains a large number of active amino groups and imidazole structures that can chelate heavy metal ions in sewage. The modified monomer can increase the grid density, thereby improving the capture effect of particles in water.

Description

Technical Field

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

[0002] Water is vital to life and is a fundamental condition for human survival. With the rapid development of human society and industry, a large amount of complex industrial wastewater has been generated, such as coking wastewater, printing and dyeing wastewater, and pharmaceutical wastewater. These wastewaters contain a wide variety of pollutants at high concentrations and with complex structures. Some organic matter is poorly biodegradable and has carcinogenic, mutagenic, and teratogenic effects, posing serious risks to humans and other organisms. Therefore, strengthening the comprehensive management of complex industrial wastewater is urgent. Over the years, various processes have been developed for wastewater treatment. Among them, coagulation is a key and often necessary operation in the water treatment field due to its advantages such as simple equipment, ease of operation, good treatment effects, and economic feasibility. It can be used for pretreatment, advanced treatment, or even as the primary treatment method for wastewater, playing an indispensable role in water treatment. The type and properties of the wastewater treatment agents used in the coagulation process are key factors affecting pollutant removal efficiency and water treatment costs. Summary of the Invention

[0003] The purpose of the present invention is to provide a biocarbon composite sewage treatment agent and a preparation method thereof, which solves the problem that the current sewage treatment agents have poor treatment effects.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing a biocarbon composite sewage treatment agent comprises the following steps:

[0006] Step S1: Tannic acid, monochloroacetic acid, and deionized water are uniformly mixed, stirred at a speed of 150-200 r / min and a temperature of 50-60° C., and a sodium carbonate aqueous solution is added while maintaining the pH at a neutral value. The mixture is reacted for 3-5 hours and the pH is adjusted to 3-5 to obtain carboxylated tannic acid.

[0007] Step S2: The biocarbon support, epoxybutene, and DMF are uniformly mixed, reacted for 4-6 hours at a speed of 150-200 r / min, a temperature of 30-40° C., and a pH of 11-12, the filtrate is filtered and removed, the substrate is dispersed in toluene, carboxylated tannic acid and p-toluenesulfonic acid are added, and the reaction is carried out at a speed of 60-80 r / min and a temperature of 110-112° C. for 8-10 hours to obtain a modified biocarbon support;

[0008] Step S2: acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, modified biocarbon carrier, modified monomer and DMF are mixed evenly, stirred and potassium persulfate solution is added at a speed of 200-300 r / min, a temperature of 60-65°C and nitrogen protection, and the reaction is carried out for 4-6 hours. The filtrate is filtered to remove the filtrate and dried to obtain a bio-based porous carbon composite wastewater treatment agent.

[0009] Furthermore, the molar ratio of tannic acid to monochloroacetic acid in step S1 is 1:4, and the mass fraction of the sodium carbonate aqueous solution is 30%.

[0010] Furthermore, the molar ratio of amino groups to epoxybutene on the bio-carbon support in step S2 is 1:2, the amount of carboxylated tannic acid is 3% of the mass of the bio-carbon support, and the amount of p-toluenesulfonic acid is 1% of the mass of the carboxylated tannic acid.

[0011] Furthermore, the mass ratio of acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, biocarbon carrier and modified monomer in step S3 is 8.5:0.8:5:1.5, the amount of potassium persulfate used is 1-2% of the mass of acrylamide, and the mass fraction of potassium persulfate solution is 10%.

[0012] Furthermore, the biocarbon carrier is prepared by the following steps:

[0013] Step A1: Dissolve urea and sodium lignin sulfonate in deionized water, stir at a speed of 200-300 r / min and a temperature of 20-30° C., add calcium acetate and pectin, stir for 1-2 hours, and freeze-dry to obtain a precursor;

[0014] Step A2: The precursor is calcined at a temperature of 600-650° C. under nitrogen protection for 2-3 hours, dispersed in deionized water, and hydrochloric acid solution is added to a pH value of 6.5. The substrate is centrifuged and washed with deionized water until neutral, and then soaked in potassium hydroxide solution for 5-7 hours. After filtration, the precursor is kept at a temperature of 600-650° C. under nitrogen protection for 2-3 hours to obtain porous carbon;

[0015] Step A3: The porous carbon, sodium molybdate dihydrate, thioacetamide and deionized water are mixed evenly, and the mixture is hydrothermally reacted at a temperature of 220-230°C for 20-24 hours. The supernatant is removed by centrifugation, and the substrate is dried to obtain pretreated porous carbon. The pretreated porous carbon is dispersed in deionized water, stirred at a speed of 150-200 r / min and a temperature of 60-70°C, and KH550 is added. After stirring for 1-1.5 hours, the mixture is filtered and dried to obtain a biocarbon carrier.

[0016] Furthermore, the usage ratio of urea, sodium lignin sulfonate, deionized water, calcium acetate and pectin in step A1 is 0.5 g:1.4 g:30 mL:3.15 g:1 g.

[0017] Furthermore, the mass fraction of the hydrochloric acid solution in step A2 is 3.65%, and the mass fraction of the sodium hydroxide solution is 15%.

[0018] Furthermore, the amount ratio of the porous carbon, sodium molybdate dihydrate and thioacetamide in step A3 is 1 g:2 mmol:6 mmol, and the amount of KH550 is 1-1.5% of the mass of the pretreated porous carbon.

[0019] Furthermore, the modified monomer is prepared by the following steps:

[0020] 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol, potassium carbonate and anhydrous ethanol are mixed evenly, and refluxed for 10-15 hours at a speed of 120-150 r / min and a temperature of 80-82°C. The pH value is adjusted to 5-5.5 to obtain intermediate 1. Intermediate 1, potassium hydroxide, tetrabutylammonium bromide and DMF are mixed evenly, and 3-chloropropylene is added dropwise at a speed of 60-80 r / min and a temperature of 20-25°C with stirring. The mixture is reacted for 2-3 hours to obtain a modified monomer.

[0021] Furthermore, the molar ratio of 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol and potassium carbonate is 1:2:2.5, the molar ratio of intermediate 1, potassium hydroxide and 3-chloropropylene is 1:3.5:2, and the amount of tetrabutylammonium bromide is 2% by mass of 3-chloropropylene.

[0022] The beneficial effects of the present invention are as follows: a biocarbon composite sewage treatment agent prepared by the present invention uses tannic acid and monochloroacetic acid as raw materials, so that the hydroxyl group on the tannic acid reacts with the chlorine atom site on the monochloroacetic acid to prepare carboxylated tannic acid, and the biocarbon carrier and epoxybutene react under alkaline conditions, so that the amino group on the biocarbon carrier reacts with the epoxy group on the epoxybutene to produce a hydroxyl group, and then esterifies with the carboxylated tannic acid so that the carboxyl group on the carboxylated tannic acid reacts with the hydroxyl group to prepare a modified biocarbon carrier, and acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, and modified The biocarbon carrier and the modified monomer are polymerized on the surface to form an organic polymer to prepare a biocarbon composite wastewater treatment agent. The biocarbon carrier is prepared by pyrolyzing pectin and sodium lignin sulfonate to provide carbonic acid and sulfur sources, decomposing urea to provide nitrogen source, and calcium ions are in situ formed into a uniformly dispersed nano-calcium carbonate template. After carbonization treatment, the nano-calcium carbonate template is removed to form a three-dimensional hierarchical porous carbon. The porous carbon, sodium molybdate dihydrate and thioacetamide are hydrothermally reacted to load molybdenum disulfide on the pores of the porous carbon, and then treated with KH550. The siloxane water on the KH550 The decapsulated product is coated on the porous carbon surface, so that the surface is grafted with amino groups to obtain a biocarbon carrier. The modified monomer reacts with 4,4'-biphenyldicarboxaldehyde and 3,4-diaminobenzenethiol as raw materials to form a benzimidazole structure to obtain an intermediate 1. The intermediate 1 is reacted with 3-chloropropylene to make the thiol group on the intermediate 1 react with the chlorine atom site on the 3-chloropropylene to obtain a modified monomer. The sewage treatment agent contains molybdenum disulfide, which can adsorb heavy metal ions by electrostatic adsorption. During the surface polymer diffusion process, molybdenum disulfide contacts the metal ions and forms The surface of the sewage treatment agent forms a metal-sulfur bond to achieve the effect of adsorbing heavy metal ions, and the condensed phenol hydroxyl groups on the surface can chelate metal ions. The polymer segments on the surface of the sewage treatment agent contain positively charged groups, hydrophobic groups and hydrophilic groups. Under the interaction of the hydrophobic groups, intramolecular and intermolecular associations can be caused, thereby making the polymer segments between the carrier surface cross-linked to form a grid structure. At the same time, the grid surface contains a large number of active amino and imidazole structures that can chelate heavy metal ions in sewage. The modified monomer can increase the grid density, thereby improving the capture effect of particles in water. DETAILED DESCRIPTION

[0023] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0024] Example 1

[0025] A method for preparing a biocarbon composite sewage treatment agent comprises the following steps:

[0026] Step S1: Tannic acid, monochloroacetic acid, and deionized water were mixed uniformly, stirred at a speed of 150 r / min and a temperature of 50° C., and a sodium carbonate aqueous solution was added while maintaining the pH at a neutral pH. The mixture was reacted for 3 h and the pH was adjusted to 3 to obtain carboxylated tannic acid.

[0027] Step S2: The biocarbon support, epoxybutene, and DMF were uniformly mixed, and reacted at a speed of 150 r / min, a temperature of 30° C., and a pH of 11 for 4 hours. The filtrate was filtered to remove the substrate, and the substrate was dispersed in toluene. Carboxylated tannic acid and p-toluenesulfonic acid were added, and the reaction was carried out at a speed of 60 r / min and a temperature of 110° C. for 8 hours to obtain a modified biocarbon support.

[0028] Step S2: acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, modified biocarbon carrier, modified monomer and DMF are mixed evenly, stirred and potassium persulfate solution is added at a speed of 200 r / min, a temperature of 60°C and nitrogen protection, and the reaction is carried out for 4 hours. The filtrate is filtered to remove the filtrate and dried to obtain a bio-based porous carbon composite wastewater treatment agent.

[0029] The molar ratio of tannic acid to monochloroacetic acid in step S1 is 1:4, and the mass fraction of the sodium carbonate aqueous solution is 30%.

[0030] The molar ratio of amino groups to epoxybutene on the bio-carbon support in step S2 is 1:2, the amount of carboxylated tannic acid is 3% of the mass of the bio-carbon support, and the amount of p-toluenesulfonic acid is 1% of the mass of the carboxylated tannic acid.

[0031] The mass ratio of acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, biocarbon carrier and modified monomer in step S3 is 8.5:0.8:5:1.5, the amount of potassium persulfate used is 1% of the mass of acrylamide, and the mass fraction of potassium persulfate solution is 10%.

[0032] The biocarbon carrier is prepared by the following steps:

[0033] Step A1: Dissolve urea and sodium lignin sulfonate in deionized water, stir at a speed of 200 r / min and a temperature of 20° C., add calcium acetate and pectin, stir for 1 hour, and freeze-dry to obtain a precursor;

[0034] Step A2: The precursor was calcined at 600°C under nitrogen protection for 2 hours, dispersed in deionized water, and hydrochloric acid solution was added to a pH value of 6.5. The substrate was centrifuged and washed with deionized water until neutral. The substrate was then soaked in potassium hydroxide solution for 5 hours, filtered, and kept warm at 600°C under nitrogen protection for 2 hours to obtain porous carbon.

[0035] Step A3: The porous carbon, sodium molybdate dihydrate, thioacetamide and deionized water were mixed evenly, and the mixture was hydrothermally reacted at a temperature of 220°C for 20 hours. The supernatant was removed by centrifugation, and the substrate was dried to obtain pretreated porous carbon. The pretreated porous carbon was dispersed in deionized water, stirred at a speed of 150 r / min and a temperature of 60°C, and KH550 was added. After stirring for 1 hour, the mixture was filtered and dried to obtain a biocarbon carrier.

[0036] The usage ratio of urea, sodium lignin sulfonate, deionized water, calcium acetate and pectin described in step A1 is 0.5g:1.4g:30mL:3.15g:1g.

[0037] The mass fraction of the hydrochloric acid solution described in step A2 is 3.65%, and the mass fraction of the sodium hydroxide solution is 15%.

[0038] The amount ratio of the porous carbon, sodium molybdate dihydrate and thioacetamide in step A3 is 1 g:2 mmol:6 mmol, and the amount of KH550 is 1% of the mass of the pretreated porous carbon.

[0039] The modified monomer is prepared by the following steps:

[0040] 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol, potassium carbonate and anhydrous ethanol were mixed uniformly, refluxed at a speed of 120 r / min and a temperature of 80°C for 10 hours, and the pH value was adjusted to 5 to obtain intermediate 1. Intermediate 1, potassium hydroxide, tetrabutylammonium bromide and DMF were mixed uniformly, stirred at a speed of 60 r / min and a temperature of 20°C, and 3-chloropropylene was added dropwise, and the reaction was carried out for 2 hours to obtain a modified monomer.

[0041] The molar ratio of 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol and potassium carbonate is 1:2:2.5, the molar ratio of intermediate 1, potassium hydroxide and 3-chloropropylene is 1:3.5:2, and the amount of tetrabutylammonium bromide is 2% of the mass of 3-chloropropylene.

[0042] Example 2

[0043] A method for preparing a biocarbon composite sewage treatment agent comprises the following steps:

[0044] Step S1: Tannic acid, monochloroacetic acid, and deionized water were mixed uniformly, stirred at a speed of 150 r / min and a temperature of 55° C., and a sodium carbonate aqueous solution was added while maintaining the pH at a neutral pH. The mixture was reacted for 4 hours and the pH was adjusted to 4 to obtain carboxylated tannic acid.

[0045] Step S2: The biocarbon support, epoxybutene, and DMF were uniformly mixed, and reacted at a speed of 150 r / min, a temperature of 35° C., and a pH of 12 for 5 h. The filtrate was filtered to remove the substrate, and the substrate was dispersed in toluene. Carboxylated tannic acid and p-toluenesulfonic acid were added, and the reaction was carried out at a speed of 80 r / min and a temperature of 112° C. for 9 h to obtain a modified biocarbon support.

[0046] Step S2: acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, modified biocarbon carrier, modified monomer and DMF are mixed evenly, stirred and added with potassium persulfate solution at a speed of 200 r / min, a temperature of 65°C and nitrogen protection, and reacted for 5 hours. The filtrate is filtered to remove the filtrate and dried to obtain a bio-based porous carbon composite wastewater treatment agent.

[0047] The molar ratio of tannic acid to monochloroacetic acid in step S1 is 1:4, and the mass fraction of the sodium carbonate aqueous solution is 30%.

[0048] The molar ratio of amino groups to epoxybutene on the bio-carbon support in step S2 is 1:2, the amount of carboxylated tannic acid is 3% of the mass of the bio-carbon support, and the amount of p-toluenesulfonic acid is 1% of the mass of the carboxylated tannic acid.

[0049] The mass ratio of acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, biocarbon carrier and modified monomer described in step S3 is 8.5:0.8:5:1.5, the amount of potassium persulfate used is 1.5% of the mass of acrylamide, and the mass fraction of potassium persulfate solution is 10%.

[0050] The biocarbon carrier is prepared by the following steps:

[0051] Step A1: Dissolve urea and sodium lignin sulfonate in deionized water, stir at a speed of 200 r / min and a temperature of 25°C, add calcium acetate and pectin, stir for 1.5 hours, and freeze-dry to obtain a precursor;

[0052] Step A2: The precursor was calcined at 630° C. under nitrogen protection for 2.5 hours, dispersed in deionized water, and hydrochloric acid solution was added to a pH value of 6.5. The substrate was centrifuged and washed with deionized water until neutral. The substrate was then soaked in potassium hydroxide solution for 6 hours, filtered, and kept warm at 630° C. under nitrogen protection for 2.5 hours to obtain porous carbon.

[0053] Step A3: The porous carbon, sodium molybdate dihydrate, thioacetamide and deionized water were mixed evenly, and the mixture was hydrothermally reacted at a temperature of 225°C for 22 hours. The supernatant was removed by centrifugation, and the substrate was dried to obtain pretreated porous carbon. The pretreated porous carbon was dispersed in deionized water, stirred at a speed of 150 r / min and a temperature of 65°C, and KH550 was added. After stirring for 1.5 hours, the mixture was filtered and dried to obtain a biocarbon carrier.

[0054] The usage ratio of urea, sodium lignin sulfonate, deionized water, calcium acetate and pectin described in step A1 is 0.5g:1.4g:30mL:3.15g:1g.

[0055] The mass fraction of the hydrochloric acid solution described in step A2 is 3.65%, and the mass fraction of the sodium hydroxide solution is 15%.

[0056] The amount ratio of the porous carbon, sodium molybdate dihydrate and thioacetamide in step A3 is 1 g:2 mmol:6 mmol, and the amount of KH550 is 1.5% of the mass of the pretreated porous carbon.

[0057] The modified monomer is prepared by the following steps:

[0058] 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol, potassium carbonate and anhydrous ethanol were mixed evenly, refluxed at a speed of 120 r / min and a temperature of 81°C for 13 h, and the pH value was adjusted to 5.5 to obtain intermediate 1. Intermediate 1, potassium hydroxide, tetrabutylammonium bromide and DMF were mixed evenly, stirred at a speed of 60 r / min and a temperature of 23°C, and 3-chloropropylene was added dropwise, and the reaction was carried out for 3 h to obtain a modified monomer.

[0059] The molar ratio of 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol and potassium carbonate is 1:2:2.5, the molar ratio of intermediate 1, potassium hydroxide and 3-chloropropylene is 1:3.5:2, and the amount of tetrabutylammonium bromide is 2% of the mass of 3-chloropropylene.

[0060] Example 3

[0061] A method for preparing a biocarbon composite sewage treatment agent comprises the following steps:

[0062] Step S1: Tannic acid, monochloroacetic acid, and deionized water were mixed uniformly, stirred at a speed of 200 r / min and a temperature of 60° C., and a sodium carbonate aqueous solution was added while maintaining the pH at a neutral pH. The mixture was reacted for 5 hours and the pH was adjusted to 5 to obtain carboxylated tannic acid.

[0063] Step S2: The biocarbon support, epoxybutene, and DMF were uniformly mixed, and reacted at a speed of 200 r / min, a temperature of 40° C., and a pH of 12 for 6 h. The filtrate was filtered to remove the filtrate, and the substrate was dispersed in toluene. Carboxylated tannic acid and p-toluenesulfonic acid were added, and the reaction was carried out at a speed of 80 r / min and a temperature of 112° C. for 10 h to obtain a modified biocarbon support.

[0064] Step S2: acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, modified biocarbon carrier, modified monomer and DMF are mixed evenly, stirred and potassium persulfate solution is added at a speed of 300 r / min, a temperature of 65°C and nitrogen protection, and the reaction is carried out for 6 hours. The filtrate is filtered to remove the filtrate and dried to obtain a bio-based porous carbon composite wastewater treatment agent.

[0065] The molar ratio of tannic acid to monochloroacetic acid in step S1 is 1:4, and the mass fraction of the sodium carbonate aqueous solution is 30%.

[0066] The molar ratio of amino groups to epoxybutene on the bio-carbon support in step S2 is 1:2, the amount of carboxylated tannic acid is 3% of the mass of the bio-carbon support, and the amount of p-toluenesulfonic acid is 1% of the mass of the carboxylated tannic acid.

[0067] The mass ratio of acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, biocarbon carrier and modified monomer in step S3 is 8.5:0.8:5:1.5, the amount of potassium persulfate used is 2% of the mass of acrylamide, and the mass fraction of potassium persulfate solution is 10%.

[0068] The biocarbon carrier is prepared by the following steps:

[0069] Step A1: Dissolve urea and sodium lignin sulfonate in deionized water, stir at a speed of 300 r / min and a temperature of 30° C., add calcium acetate and pectin, stir for 2 h, and freeze-dry to obtain a precursor;

[0070] Step A2: The precursor was calcined at 650°C under nitrogen protection for 3 hours, dispersed in deionized water, and hydrochloric acid solution was added to a pH of 6.5. The substrate was centrifuged and washed with deionized water until neutral. The substrate was then soaked in potassium hydroxide solution for 7 hours, filtered, and kept warm at 650°C under nitrogen protection for 3 hours to obtain porous carbon.

[0071] Step A3: The porous carbon, sodium molybdate dihydrate, thioacetamide and deionized water were mixed evenly, and the mixture was hydrothermally reacted at a temperature of 230°C for 24 hours. The supernatant was removed by centrifugation, and the substrate was dried to obtain pretreated porous carbon. The pretreated porous carbon was dispersed in deionized water, stirred at a speed of 200 r / min and a temperature of 70°C, and KH550 was added. After stirring for 1.5 hours, the mixture was filtered and dried to obtain a biocarbon carrier.

[0072] The usage ratio of urea, sodium lignin sulfonate, deionized water, calcium acetate and pectin described in step A1 is 0.5g:1.4g:30mL:3.15g:1g.

[0073] The mass fraction of the hydrochloric acid solution described in step A2 is 3.65%, and the mass fraction of the sodium hydroxide solution is 15%.

[0074] The amount ratio of the porous carbon, sodium molybdate dihydrate and thioacetamide in step A3 is 1 g:2 mmol:6 mmol, and the amount of KH550 is 1.5% of the mass of the pretreated porous carbon.

[0075] The modified monomer is prepared by the following steps:

[0076] 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol, potassium carbonate and anhydrous ethanol were mixed uniformly, refluxed at a speed of 150 r / min and a temperature of 82°C for 15 hours, and the pH value was adjusted to 5.5 to obtain intermediate 1. Intermediate 1, potassium hydroxide, tetrabutylammonium bromide and DMF were mixed uniformly, stirred at a speed of 80 r / min and a temperature of 25°C, and 3-chloropropylene was added dropwise, and the reaction was carried out for 3 hours to obtain a modified monomer.

[0077] The molar ratio of 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol and potassium carbonate is 1:2:2.5, the molar ratio of intermediate 1, potassium hydroxide and 3-chloropropylene is 1:3.5:2, and the amount of tetrabutylammonium bromide is 2% of the mass of 3-chloropropylene.

[0078] Comparative Example 1

[0079] Compared with Example 1, this comparative example uses porous carbon instead of pretreated porous carbon, and the other steps are the same.

[0080] Comparative Example 2

[0081] Compared with Example 1, this comparative example uses the product obtained by treating the pretreated porous carbon with KH570 instead of the modified biocarbon carrier, and the remaining steps are the same.

[0082] Comparative Example 3

[0083] Compared with Example 1, this comparative example did not add the modified monomer, and the remaining steps were the same.

[0084] Take 200mL of wastewater from a certain place, turbidity 175, UV 254 21.33, COD3820mg / L, DOC1428mg / L, Cu 2+ =78.2mg / L, Pb 2+ =85.6 mg / L, under the condition of a rotation speed of 200 r / min, 30 mg of the sewage treatment agent prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were added respectively with stirring, stirred for 15 minutes, allowed to settle, and water samples were taken 2 cm below the liquid surface for analysis. Turbidity: measured using a HACH2100AN turbidimeter, UV 254 : After the water sample passed through a 0.45μm filter membrane, it was measured using a UV-1601 ultraviolet spectrophotometer from Beijing Rayleigh Analytical Instrument Co., Ltd. DOC: After the water sample passed through a 0.45μm filter membrane, it was measured using an Aurora1030W TOC total organic carbon analyzer from Aurora, USA. COD: Measured in accordance with GB / T11914-1989. Metal ions: AVIO500 inductively coupled plasma emission spectrometer. The removal rate calculation results are shown in the following table.

[0085] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Turbidity 98.87％ 98.94％ 99.22％ 94.63 84.37 92.38 <![CDATA[UV 254 ]]> 95.54％ 95.63％ 95.64％ 90.82 82.33 90.31 DOC 92.38％ 93.44％ 94.11％ 87.63 81.22 89.24 COD 89.75％ 90.08％ 90.12％ 83.88 80.34 88.33 <![CDATA[Cu 2+ ]]> 99.32％ 99.37％ 99.51％ 94.16 85.52 93.51 <![CDATA[Pb 2+ ]]> 98.13％ 98.34％ 98.49％ 93.24 84.66 92.66

[0086] It can be seen from the above table that this application has a very good sewage treatment effect.

[0087] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a biocarbon composite sewage treatment agent, characterized in that: The specific steps include: Step S1: mixing tannic acid, monochloroacetic acid and deionized water, adding a sodium carbonate aqueous solution, maintaining the pH at a neutral pH, reacting, and adjusting the pH to an acidic state to obtain carboxylated tannic acid; Step S2: mixing the biocarbon support, epoxybutene, and DMF for reaction, filtering and removing the filtrate, dispersing the substrate in toluene, adding carboxylated tannic acid and p-toluenesulfonic acid, and reacting to obtain a modified biocarbon support; Step S3: uniformly mixing acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, a modified biocarbon support, a modified monomer, and DMF, stirring under nitrogen protection, adding a potassium persulfate solution, reacting, filtering and removing the filtrate, and drying to obtain a bio-based porous carbon composite wastewater treatment agent; The biocarbon carrier is prepared by the following steps: Step A1: dissolving urea and sodium lignin sulfonate in deionized water, stirring, adding calcium acetate and pectin, stirring, and freeze-drying to obtain a precursor; Step A2: After calcining the precursor, the precursor is dispersed in deionized water, a hydrochloric acid solution is added, and the substrate is centrifuged and washed with deionized water until neutral, and then immersed in a potassium hydroxide solution. After the immersion treatment, the substrate is filtered and kept warm to obtain porous carbon; Step A3: porous carbon, sodium molybdate dihydrate, thioacetamide, and deionized water are mixed for reaction, the supernatant is removed by centrifugation, and the substrate is dried to obtain pretreated porous carbon. The pretreated porous carbon is dispersed in deionized water, stirred, and KH550 is added. After stirring, the mixture is filtered and dried to obtain a biocarbon support. The modified monomer is prepared by the following steps: 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol, potassium carbonate and anhydrous ethanol were mixed and refluxed for reaction, and the pH was adjusted to be acidic to obtain intermediate 1. Intermediate 1, potassium hydroxide, tetrabutylammonium bromide and DMF were mixed and stirred, and 3-chloropropylene was added dropwise to react to obtain a modified monomer.

2. The method for preparing a biocarbon composite sewage treatment agent according to claim 1, characterized in that: The molar ratio of tannic acid to monochloroacetic acid in step S1 is 1:

4.

3. The method for preparing a biocarbon composite sewage treatment agent according to claim 1, characterized in that: The molar ratio of amino groups to epoxybutene on the bio-carbon support in step S2 is 1:2, and the amount of carboxylated tannic acid used is 3% of the mass of the bio-carbon support.

4. The method for preparing a biocarbon composite sewage treatment agent according to claim 1, characterized in that: The mass ratio of acrylamide, acryloyloxyethyl dimethylbenzyl ammonium chloride, biocarbon carrier and modified monomer described in step S3 is 8.5:0.8:5:1.

5.

5. The method for preparing a biocarbon composite sewage treatment agent according to claim 1, characterized in that: The usage ratio of urea, sodium lignin sulfonate, deionized water, calcium acetate and pectin described in step A1 is 0.5g:1.4g:30mL:3.15g:1g.

6. The method for preparing a biocarbon composite sewage treatment agent according to claim 1, characterized in that: The porous carbon, sodium molybdate dihydrate and thioacetamide described in step A3 are used in a ratio of 1 g: 2 mmol: 6 mmol, and the amount of KH550 used is 1-1.5% of the mass of the pretreated porous carbon.

7. The method for preparing a biocarbon composite sewage treatment agent according to claim 1, characterized in that: The molar ratio of 4,4'-biphenyldicarboxaldehyde, 3,4-diaminobenzenethiol and potassium carbonate is 1:2:2.5, and the molar ratio of intermediate 1, potassium hydroxide and 3-chloropropylene is 1:3.5:

2.

8. A biocarbon composite sewage treatment agent, characterized by: Prepared according to any one of claims 1 to 7.