Plant-based water filtration material and method of making same

Abstract

The application discloses a plant-based water body filtering material and a preparation method thereof, and relates to the technical field of filtering materials. In the preparation of the plant-based water body filtering material, 4-(10, 15, 20-triphenylporphyrin-5-yl) aniline is sequentially reacted with 2, 3-epoxypropyl acrylate and zinc acetate to obtain an alkenyl porphyrin zinc complex; chitosan and the alkenyl porphyrin zinc complex are reacted to obtain modified chitosan; reed carbon and butyl trimethyl ammonium chloride are reacted to obtain modified reed carbon; polybutylene terephthalate, the modified chitosan and the modified reed carbon are prepared into a spinning solution, and a fiber membrane is prepared through electrostatic spinning; itaconic acid and alkenyl benzisothiazolinone are prepared into a finishing liquid; and the fiber membrane is finished with the finishing liquid to obtain the plant-based water body filtering material. The plant-based water body filtering material prepared by the application can adsorb and catalytically degrade organic dyes in wastewater, adsorb heavy metals, and also has the effect of inhibiting bacteria.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of filter materials, in particular to a plant-based water filter material and a preparation method thereof. BACKGROUND

[0002] Water resource recycling is an important way to solve the contradiction between supply and demand. With the change of environmental protection concept from "wastewater treatment" to "recycling", membrane water treatment will become an inevitable condition to realize water resource utilization. At present, in the field of filter materials, mainly knitted fabrics, woven fabrics and some non-woven fabrics, etc. Compared with these traditional methods, electrospun fibers have the advantages of high specific surface area, large porosity and high permeability, and therefore can be used as high-performance water treatment filter materials, and have a very wide application prospect.

[0003] Sewage, especially industrial wastewater, usually contains a large amount of heavy metal ions, microorganisms and organic dyes. Traditional filter materials have single function and only have physical adsorption effect on pollutants, which is difficult to efficiently intercept these pollution components, increases the process of water purification and occupies a large amount of manpower and material resources. The present application uses PBT with high temperature resistance and acid and alkali corrosion resistance as a base resin, and uses chitosan and reed carbon as plant-based components, and an electrospun water filter material is prepared. Through modification of chitosan and reed carbon and post-treatment process, the water filter material has excellent adsorption capacity, catalytic degradation capacity and antibacterial capacity, so that the sewage purification efficiency is greatly improved. SUMMARY

[0004] The purpose of the present application is to provide a plant-based water filter material and a preparation method thereof to solve the problems in the prior art.

[0005] In order to solve the above technical problems, the present application provides the following technical scheme:

[0006] A preparation method of a plant-based water filter material, the preparation method of the plant-based water filter material comprising the following steps:

[0007] (1) reacting 4-(10,15,20-triphenylporphyrin-5-yl) aniline and 2,3-epoxypropyl acrylate to obtain an alkenyl porphyrin monomer; and reacting the alkenyl porphyrin monomer and zinc acetate to obtain an alkenyl porphyrin zinc complex;

[0008] (2) reacting chitosan and the alkenyl porphyrin zinc complex to obtain modified chitosan;

[0009] (3) carbonizing reed straw at high temperature to obtain reed carbon; oxidizing the reed carbon with nitric acid to obtain oxidized reed carbon; and loading butyl trimethyl ammonium chloride onto the oxidized reed carbon to obtain modified reed carbon;

[0010] (4) Polybutylene terephthalate, modified chitosan and modified reed charcoal were prepared into a spinning solution and electrospinned to obtain a fiber membrane.

[0011] (5) Benzisothiazolinone and 3-bromoprop-1-ene are reacted to obtain alkenylbenzisothiazolinone;

[0012] (6) Prepare finishing solution by mixing itaconic acid and alkenylbenzisothiazolinone; finish the fiber membrane with finishing solution to obtain plant-based water filtration material.

[0013] Further, the preparation method of the alkenyl porphyrin monomer in step (1) is as follows: 4-(10,15,20-triphenylporphyrin-5-yl)aniline and dichloromethane are mixed evenly at a mass ratio of 1:(30~40), stirred at room temperature for 20~30 min under nitrogen protection, 2,3-epoxypropyl acrylate with a molar amount of 1.1~1.2 times that of 4-(10,15,20-triphenylporphyrin-5-yl)aniline is added, the temperature is raised to 40~50℃, and the reaction is continued to be stirred and refluxed for 7~8 h. The alkenyl porphyrin monomer is then dried under vacuum at 60~70℃ for 8~10 h.

[0014] Further, the preparation method of the alkenyl porphyrin zinc complex in step (1) is as follows: alkenyl porphyrin monomer and dichloromethane are mixed at a mass ratio of 1:(30~40), stirred at room temperature for 20~30 min, zinc acetate with a mass of 2~3 times that of alkenyl porphyrin monomer is added, stirred and refluxed at 40~50℃ for 2~3 h, extracted with deionized water, the organic phase is taken, and vacuum dried at 60~70℃ for 8~10 h to obtain the alkenyl porphyrin zinc complex.

[0015] Furthermore, the chemical reaction formula of the alkenylporphyrin zinc complex in step (1) is as follows:

[0016] .

[0017] Further, the preparation method of the modified chitosan in step (2) is as follows: chitosan and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:(30~40), stirred at 40~50℃ for 10~20min, and then an alkenyl porphyrin zinc complex of 1.4~1.6 times the mass of chitosan is added. The mixture is stirred and reacted at 70~80℃ for 20~24h. The N,N-dimethylformamide is removed by rotary evaporation under reduced pressure, and the mixture is washed 3~5 times with methanol. The mixture is then vacuum dried at 70~80℃ for 16~20h to obtain the modified chitosan.

[0018] Further, the preparation method of the modified reed carbon in step (3) is as follows: the reed straws are dried at 60-80℃ for 20-24h, crushed in a crusher, and sieved through a 100-mesh screen to obtain straw powder; the straw powder is placed in a crucible, heated to 400-500℃ at a speed of 10℃ / min under nitrogen protection, kept for 60-80min, heated to 600-700℃, and kept for 2-3h, cooled to room temperature, ball-milled, and sieved through an 800-mesh screen to obtain reed carbon; the reed carbon and 10% nitric acid aqueous solution by mass fraction are uniformly mixed at a mass ratio of 1:(12-16), stirred at 75-85℃ for 10-14h, filtered, washed with deionized water for 3-5 times, and dried in an oven at 105-115℃ to constant weight to obtain oxidized reed carbon; the oxidized reed carbon, butyl trimethyl ammonium chloride, and methanol are uniformly mixed at a mass ratio of 1:(2-3):(10-20), ultrasonically treated at room temperature for 3-4h, filtered, and dried at 70-80℃ to constant weight to obtain modified reed carbon.

[0019] Further, the preparation method of the fiber membrane in step (4) is as follows: trifluoroacetic acid and dichloromethane are uniformly mixed at a mass ratio of 4:1 to prepare a mixed solvent; 30-40 parts of polybutylene terephthalate, 4-5 parts of modified chitosan, 3-4 parts of modified reed carbon, and 150-200 parts of the mixed solvent are weighed; the polybutylene terephthalate, the modified chitosan, the modified reed carbon, and the mixed solvent are uniformly mixed to prepare a spinning solution; and the spinning solution is electrospun on an electrospinning instrument to obtain a fiber membrane.

[0020] Further, the parameters of electrospinning are set as follows: the pushing rate of the spinning solution is 0.002-0.004mm / s, the spinning voltage is 22-26kV, and the receiving distance is 8-10cm.

[0021] Further, the preparation method of the alkenyl benzisothiazolinone in step (5) is as follows: benzisothiazolinone, 3-bromoprop-1-ene, and potassium carbonate are added into acetonitrile in a volume of 20-30 times the mass of the benzisothiazolinone at a molar ratio of 1:1:(1.1-1.3), stirred at 55-65℃ for 3-4h, mixed uniformly with deionized water in a volume of 2-3 times the volume of acetonitrile after the reaction is completed, extracted with ethyl acetate, and dried at 70-80℃ under vacuum for 10-12h to obtain alkenyl benzisothiazolinone.

[0022] Further, the chemical reaction formula of the alkenyl benzisothiazolinone is as follows:

[0023] .

[0024] Further, the preparation method of the plant-based water filtering material in step (6) is as follows: uniformly mixing itaconic acid, alkenyl benzisothiazolinone and acetone at a mass ratio of 1:(0.4-0.6):(13-15), stirring at room temperature for 10-20 min, adding 0.05-0.07 times the mass of itaconic acid of benzoyl peroxide to prepare a finishing liquid; immersing the fiber membrane in the finishing liquid with a bath ratio of 1:(20-30), and keeping at 65-75 DEG C for 60-80 min, taking out and drying at 70-80 DEG C to constant weight to obtain the plant-based water filtering material.

[0025] The application also provides the plant-based water filtering material prepared by the preparation method.

[0026] Compared with the prior art, the application has the following beneficial effects:

[0027] First, 4-(10,15,20-triphenylporphyrin-5-yl) aniline and 2,3-epoxypropyl acrylate are reacted to obtain an alkenyl porphyrin monomer; the alkenyl porphyrin monomer is reacted with zinc acetate to obtain an alkenyl porphyrin zinc complex; the alkenyl porphyrin zinc complex introduces an α,β-unsaturated double bond; the alkenyl porphyrin zinc complex is reacted with the amino group on the chitosan through a Michael addition reaction to graft the porphyrin zinc complex on the chitosan, and the porphyrin zinc complex enables the filtering membrane to have the performance of photocatalytic degradation of organic dyes.

[0028] Second, reed straw is carbonized at high temperature to obtain reed carbon; nitric acid is used as an oxidizing agent to oxidize the reed carbon to increase the content of carboxylic acid groups in the reed carbon; butyl trimethyl ammonium chloride is loaded on the oxidized reed carbon through electrostatic interaction to obtain modified reed carbon; the reed carbon is a biomass carbon material and contains a large number of oxygen-containing functional groups on the surface, which can adsorb heavy metals and organic dyes; the content of carboxylic acid groups in the reed carbon can be increased after the reed carbon is oxidized, so that the adsorption effect of the reed carbon is further improved; and the cationic bacteriostatic agent can be loaded in the reed carbon through electrostatic interaction, so that the bacteriostatic function of the filtering membrane material can be further improved.

[0029] Third, benzisothiazolinone and 3-bromo-prop-1-ene are reacted to obtain alkenyl benzisothiazolinone; itaconic acid and alkenyl benzisothiazolinone are prepared into a finishing liquid; the fiber membrane is finished with the finishing liquid to obtain a plant-based water filtering material; grafting reaction is carried out on the surface of the filtering membrane material to introduce carboxylic acid groups and benzisothiazolinone groups on the surface of the fiber membrane; the benzisothiazolinone groups have bacteriostatic activity, so that the bacteriostatic capacity of the filtering membrane material can be further improved; and a large number of carboxyl groups grafted on the surface can further improve the adsorption effect of the filtering membrane material. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0031] In the following examples and comparative examples, the polybutylene terephthalate used is purchased from Liaoyang Petrochemical Company.

[0032] Example 1

[0033] A preparation method of a plant-based water filtering material, comprising the following preparation steps:

[0034] (1) 4-(10,15,20-triphenylporphyrin-5-yl) aniline and dichloromethane are uniformly mixed at a mass ratio of 1:30, stirred at room temperature for 20 min under nitrogen protection, 1.1 times the molar amount of 4-(10,15,20-triphenylporphyrin-5-yl) aniline is added, the temperature is raised to 40℃, and the stirring reflux reaction is continued for 8 h, vacuum drying is performed at 60℃ for 10 h, and an alkenyl porphyrin monomer is prepared; the alkenyl porphyrin monomer and dichloromethane are mixed at a mass ratio of 1:30, stirred at room temperature for 20 min, 2 times the mass of the alkenyl porphyrin monomer is added as zinc acetate, stirring reflux is performed at 40℃ for 3 h, deionized water is used for extraction, the organic phase is taken, vacuum drying is performed at 60℃ for 10 h, and an alkenyl porphyrin zinc complex is prepared;

[0035] (2) chitosan and N,N-dimethylformamide are uniformly mixed at a mass ratio of 1:30, stirred at 40℃ for 20 min, 1.4 times the mass of the chitosan is added as the alkenyl porphyrin zinc complex, stirring reaction is performed at 70℃ for 24 h, N,N-dimethylformamide is removed by rotary evaporation under reduced pressure, washing is performed with methanol for 3 times, vacuum drying is performed at 70℃ for 20 h, and modified chitosan is prepared;

[0036] (3) reed straw is dried at 60℃ for 24 h, crushed in a crusher, and sieved through a 100-mesh screen to prepare straw powder; the straw powder is placed in a crucible, heated to 400℃ at a rate of 10℃ / min under nitrogen protection, kept at 400℃ for 80 min, heated to 600℃, and kept at 600℃ for 3 h, cooled to room temperature, ball milled, and sieved through an 800-mesh screen to prepare reed carbon; the reed carbon and 10% nitric acid aqueous solution are uniformly mixed at a mass ratio of 1:12, stirring reaction is performed at 75℃ for 14 h, filtered, washed with deionized water for 3 times, and dried in an oven at 105℃ to constant weight to prepare oxidized reed carbon; the oxidized reed carbon, butyl trimethyl ammonium chloride, and methanol are uniformly mixed at a mass ratio of 1:2:10, ultrasonic treatment is performed at room temperature for 3 h, filtered, and dried at 70℃ to constant weight to prepare modified reed carbon;

[0037] (4) trifluoroacetic acid, dichloromethane are mixed uniformly in a mass ratio of 4:1 to prepare a mixed solvent; 30 parts of polybutylene terephthalate, 4 parts of modified chitosan, 3 parts of modified reed carbon, and 150 parts of the mixed solvent are weighed according to the mass fraction; the polybutylene terephthalate, the modified chitosan, the modified reed carbon, and the mixed solvent are mixed uniformly to prepare a spinning solution; the spinning solution is electrospun on an electrospinning instrument to obtain a fiber membrane; the pushing rate of the electrospinning spinning solution is 0.003 mm / s, the spinning voltage is 24 kV, and the receiving distance is 10 cm;

[0038] (5) benzisothiazolinone, 3-bromoprop-1-ene, and potassium carbonate are added to acetonitrile in a molar ratio of 1:1:1.1, and stirred at 55°C for 4h; after the reaction is completed, deionized water is added to the acetonitrile in a volume of 2 times the volume of the acetonitrile, and then mixed uniformly; then, ethyl acetate is used for extraction, and the organic phase is taken and dried at 70°C under vacuum for 12h to obtain an alkenyl benzisothiazolinone;

[0039] (6) itaconic acid, alkenyl benzisothiazolinone, and acetone are mixed uniformly in a mass ratio of 1:0.4:13, stirred at room temperature for 10min, and then 0.05 times the mass of the itaconic acid is added to the benzoyl peroxide to prepare a finishing liquid; the fiber membrane is immersed in the finishing liquid, the bath ratio is 1:20, and the temperature is kept at 65°C for 80min; then, the fiber membrane is taken out and dried at 70°C until the weight is constant to obtain a plant-based water filtration material.

[0040] Example 2:

[0041] A method for preparing a plant-based water filtration material, comprising the following preparation steps:

[0042] (1) 4-(10,15,20-triphenylporphyrin-5-yl) aniline and dichloromethane are mixed uniformly in a mass ratio of 1:35, stirred at room temperature for 25min under nitrogen protection, and then 1.15 times the molar amount of the 4-(10,15,20-triphenylporphyrin-5-yl) aniline is added to the acrylic acid-2,3-epoxypropyl ester, and the temperature is increased to 45°C; the stirring is continued to reflux for 7.5h, and then dried at 65°C under vacuum for 9h to obtain an alkenyl porphyrin monomer; the alkenyl porphyrin monomer and dichloromethane are mixed in a mass ratio of 1:35, stirred at room temperature for 25min, and then 2.5 times the mass of the alkenyl porphyrin monomer is added to the zinc acetate, and the stirring is continued to reflux at 45°C for 2.5h; then, the mixture is extracted with deionized water, and the organic phase is taken and dried at 65°C under vacuum for 9h to obtain an alkenyl porphyrin zinc complex;

[0043] (2) The chitosan and N,N-dimethylformamide are mixed uniformly at a mass ratio of 1:35, stirred at 45℃ for 15 min, 1.5 times the mass of the chitosan of the zinc allyl porphyrin complex is added, stirred at 75℃ for 22 h, N,N-dimethylformamide is removed by rotary evaporation under reduced pressure, washed with methanol 4 times, and dried at 75℃ under vacuum for 18 h to prepare the modified chitosan;

[0044] (3) The reed straw is dried at 70℃ for 22 h, crushed in a crusher, and sieved through a 100-mesh screen to prepare straw powder; the straw powder is placed in a crucible, heated to 450℃ at a rate of 10℃ / min under nitrogen protection, kept at 450℃ for 70 min, heated to 650℃, and kept at 650℃ for 2.5 h, cooled to room temperature, ball-milled, and sieved through an 800-mesh screen to prepare reed carbon; the reed carbon and 10% nitric acid aqueous solution are mixed uniformly at a mass ratio of 1:14, stirred at 80℃ for 12 h, filtered, washed with deionized water 4 times, and dried in an oven at 110℃ to constant weight to prepare oxidized reed carbon; the oxidized reed carbon, butyl trimethyl ammonium chloride, and methanol are mixed uniformly at a mass ratio of 1:2.5:15, ultrasonically treated at room temperature for 3.5 h, filtered, and dried at 75℃ to constant weight to prepare modified reed carbon;

[0045] (4) The trifluoroacetic acid and dichloromethane are mixed uniformly at a mass ratio of 4:1 to prepare a mixed solvent; 35 parts of polybutylene terephthalate, 4.5 parts of modified chitosan, 3.5 parts of modified reed carbon, and 175 parts of the mixed solvent are weighed according to the mass fraction; the polybutylene terephthalate, modified chitosan, modified reed carbon, and mixed solvent are mixed uniformly to prepare a spinning solution; the spinning solution is electrospun on an electrospinning instrument to prepare a fiber membrane; the pushing rate of the electrospinning spinning solution is 0.003 mm / s, the spinning voltage is 24 kV, and the receiving distance is 10 cm;

[0046] (5) The benzisothiazolinone, 3-bromoprop-1-ene, and potassium carbonate are added to acetonitrile in an amount of 25 times the mass of the benzisothiazolinone at a molar ratio of 1:1:1.2, stirred at 60℃ for 3.5 h, mixed uniformly with deionized water in an amount of 2.5 times the volume of the acetonitrile after the reaction is completed, extracted with ethyl acetate, and the organic phase is dried under vacuum at 75℃ for 11 h to prepare an allyl benzisothiazolinone;

[0047] (6) The itaconic acid, allyl benzisothiazolinone, and acetone are mixed uniformly at a mass ratio of 1:0.5:14, stirred at room temperature for 15 min, and 0.06 times the mass of the itaconic acid of benzoyl peroxide is added to prepare a finishing liquid; the fiber membrane is immersed in the finishing liquid, the bath ratio is 1:25, kept at 70℃ for 70 min, taken out, and dried at 75℃ to constant weight to prepare a plant-based water filtration material.

[0048] Example 3:

[0049] A method for preparing a plant-based water filtering material, comprising the following preparation steps:

[0050] (1) 4-(10,15,20-triphenylporphyrin-5-yl) aniline and dichloromethane are mixed uniformly at a mass ratio of 1:40, stirred at room temperature for 30 min under nitrogen protection, 1.2 times the molar amount of 4-(10,15,20-triphenylporphyrin-5-yl) aniline is added, the temperature is raised to 50°C, and the stirring reflux reaction is continued for 7 h, and vacuum drying is performed at 70°C for 8 h to prepare an alkenyl porphyrin monomer; the alkenyl porphyrin monomer and dichloromethane are mixed at a mass ratio of 1:40, stirred at room temperature for 30 min, 3 times the mass of the alkenyl porphyrin monomer of zinc acetate is added, stirred at 50°C for 2 h, extracted with deionized water, the organic phase is taken, vacuum dried at 70°C for 8 h, and a zinc alkenyl porphyrin complex is prepared;

[0051] (2) chitosan and N,N-dimethylformamide are mixed uniformly at a mass ratio of 1:40, stirred at 50°C for 20 min, 1.6 times the mass of the chitosan of the zinc alkenyl porphyrin complex is added, stirred at 80°C for 20 h, N,N-dimethylformamide is removed by rotary evaporation under reduced pressure, washed with methanol 5 times, and vacuum dried at 80°C for 16 h to prepare modified chitosan;

[0052] (3) reed straw is dried at 80°C for 20 h, crushed in a crusher, and passed through a 100-mesh screen to prepare straw powder; the straw powder is placed in a crucible, heated to 500°C at a rate of 10°C / min under nitrogen protection, kept at 500°C for 60 min, heated to 700°C, and kept at 700°C for 2 h, cooled to room temperature, ball milled, and passed through an 800-mesh screen to prepare reed carbon; the reed carbon and 10% nitric acid aqueous solution are mixed uniformly at a mass ratio of 1:16, stirred at 85°C for 10 h, filtered, washed with deionized water 5 times, and dried in an oven at 115°C to constant weight to prepare oxidized reed carbon; the oxidized reed carbon, butyl trimethyl ammonium chloride, and methanol are mixed uniformly at a mass ratio of 1:3:20, ultrasonically treated at room temperature for 4 h, filtered, and dried at 80°C to constant weight to prepare modified reed carbon;

[0053] (4) trifluoroacetic acid and dichloromethane are mixed uniformly at a mass ratio of 4:1 to prepare a mixed solvent; polybutylene terephthalate 40 parts, modified chitosan 5 parts, modified reed carbon 4 parts, and the mixed solvent 200 parts are weighed according to the mass fraction; the polybutylene terephthalate, modified chitosan, modified reed carbon, and mixed solvent are mixed uniformly to prepare a spinning solution; the spinning solution is electrospun on an electrospinning instrument to prepare a fiber membrane; the pushing rate of the electrospun spinning solution is 0.003 mm / s, the spinning voltage is 24 kV, and the receiving distance is 10 cm;

[0054] (5) benzisothiazolinone, 3-bromoprop-1-ene, potassium carbonate were added into acetonitrile with a mass of 30 times of benzisothiazolinone at a molar ratio of 1:1:1.3, and stirred at 65°C for 3h. After the reaction was completed, deionized water with a volume of 3 times of acetonitrile was added and mixed uniformly, and then extracted with ethyl acetate. The organic phase was dried at 80°C under vacuum for 10h to obtain an alkenyl benzisothiazolinone;

[0055] (6) itaconic acid, alkenyl benzisothiazolinone, and acetone were mixed uniformly at a mass ratio of 1:0.6:15, and stirred at room temperature for 20min. Itaconic acid with a mass of 0.07 times was added into benzoyl peroxide to prepare a finishing liquid. The fiber membrane was immersed in the finishing liquid with a bath ratio of 1:30, and was kept at 75°C for 60min. After being taken out, it was dried at 80°C to constant weight to obtain a plant-based water body filtration material.

[0056] Comparative Example 1

[0057] The difference between the preparation method of the plant-based water body filtration material of Comparative Example 1 and Example 2 is that steps (1) and (2) are not performed in Comparative Example 1, that is, the chitosan is not modified, and chitosan is used instead of modified chitosan in step (4).

[0058] Comparative Example 2

[0059] The difference between the preparation method of the plant-based water body filtration material of Comparative Example 2 and Example 2 is that the reed carbon in step (3) of Comparative Example 2 is not subsequently modified, and the modified reed carbon is replaced by reed carbon in step (4).

[0060] Comparative Example 3

[0061] The difference between the preparation method of the plant-based water body filtration material of Comparative Example 3 and Example 2 is that step (5) is not performed in Comparative Example 3, and no alkenyl benzisothiazolinone is added when preparing the finishing liquid in step (6).

[0062] Comparative Example 4

[0063] The difference between the preparation method of the plant-based water body filtration material of Comparative Example 4 and Example 2 is that itaconic acid is not added when preparing the finishing liquid in step (6) of Comparative Example 4.

[0064] Test Example 1

[0065] Test of adsorbing heavy metal ions:

[0066] Preparation of standard curve: 0.50 g of copper nitrate was weighed and diluted to 500 mL. Then 1.25 mL, 5 mL, 10 mL, 12.5 mL, 20 mL and 25 mL were respectively taken and diluted to 25 mL to prepare copper solutions with different concentrations. The same volume of 25 mM ethylenediaminetetraacetic acid disodium salt was added to complex with the copper solution. The UV-vis absorption spectrum of the complexed solution was determined with distilled water as the reference solution. The scanning speed was 2 nm / min and the scanning range was 190-1100 nm. The absorbance of the solution with different copper ion concentrations was determined to draw the absorbance-concentration curve.

[0067] The examples and comparative examples were cut into circular samples with a diameter of 50 mm and fixed with a filter membrane fixing device. Copper nitrate was mixed with deionized water to prepare a copper solution with a concentration of 100 mg / L. 200 mL of the copper solution was taken. The copper solution was controlled to pass through the filter membrane by a peristaltic pump. The flow rate was controlled to be 2 ml / min, and the filtration was recycled for 3 h. 20 ml of the filtered filtrate was taken, and the same volume of 25 mM ethylenediaminetetraacetic acid disodium salt was added to complex with it. The absorbance at the maximum absorption wavelength was determined by a UV-visible spectrophotometer, and the copper ion concentration before and after filtration was calculated according to the standard curve. The copper ion adsorption efficiency was calculated, and the copper ion adsorption efficiency = (copper ion concentration before filtration-copper ion concentration after filtration) / copper ion concentration before filtration x 100%. The test results are shown in Table 1.

[0068] Table 1

[0069] Copper ion adsorption efficiency Copper ion adsorption efficiency Example 1 85.5% Comparative Example 1 84.9% Example 2 85.7% Comparative Example 2 70.6% Example 3 86.2% Comparative Example 3 83.6% Comparative Example 4 63.7%

[0070] Analyzing the test data in Table 1, it can be found that the copper ion adsorption rates of examples 1-3 are all greater than 80%, which shows good adsorption effect. The copper ion adsorption rate of comparative example 2 is obviously less than that of example 2, because reed carbon is a biomass carbon material, and the surface contains a large amount of oxygen-containing functional groups that can adsorb heavy metals. Oxidizing reed carbon with nitric acid can increase the content of carboxylic acid groups in reed carbon, further improving the adsorption effect of reed carbon. The copper ion adsorption rate of comparative example 4 is also obviously less than that of example 2, because itaconic acid is prepared into a finishing solution; the fiber membrane is finished with the finishing solution to obtain a plant-based water filtration material; and a grafting reaction is carried out on the surface of the filtration membrane material to introduce a large number of carboxylic acid groups on the surface of the fiber membrane, further improving the adsorption effect of the filtration membrane material.

[0071] Test Example 2

[0072] Test of adsorbing and degrading dyes:

[0073] The examples and comparative examples were cut into 3 cm x 3 cm samples; methylene blue was dissolved in deionized water to prepare a dye solution with a concentration of 15 mg / L; 100 mL of the dye solution was taken, the sample was added, stirred at 500 r / min for 10 h, then irradiated under a xenon lamp for 2 h, sampled, centrifuged, and the dye absorbance in the solution before and after the test was measured using a UV-visible spectrophotometer to obtain the dye concentration and calculate the dye removal rate. Dye removal rate = (dye concentration before test - dye concentration after test) / dye concentration before test x 100%. The test results are shown in Table 2.

[0074] Table 2

[0075] Dye removal efficiency Dye removal efficiency Example 1 93.7% Comparative Example 1 77.2% Example 2 95.5% Comparative Example 2 84.6% Example 3 95.2% Comparative Example 3 94.6% Comparative Example 4 73.5%

[0076] Analyzing the test data in Table 2, the dye removal rates of Examples 1-3 are significantly greater than that of Comparative Example 1, because the 4-(10,15,20-triphenylporphyrin-5-yl) aniline, acrylic acid-2,3-epoxypropyl ester were reacted to obtain an alkenyl porphyrin monomer; the alkenyl porphyrin monomer, zinc acetate were reacted to obtain an alkenyl porphyrin zinc complex; the alkenyl porphyrin zinc complex introduced an α,β-unsaturated double bond; the alkenyl porphyrin zinc complex was reacted with the amino group on the chitosan through a Michael addition reaction to graft the porphyrin zinc complex on the chitosan, and the porphyrin zinc complex enabled the filtration membrane to have the performance of photocatalytic degradation of organic dyes. The dye removal rates of Examples 1-3 are significantly greater than that of Comparative Example 2, because nitric acid was used as an oxidant to oxidize the reed carbon to increase the content of carboxylic acid groups in the reed carbon, and further improve the adsorption effect of the reed carbon on dyes. The dye removal rates of Examples 1-3 are significantly greater than that of Comparative Example 4, because itaconic acid was prepared into a finishing solution; the fiber membrane was finished with the finishing solution to obtain a plant-based water filtration material; and a grafting reaction was performed on the surface of the filtration membrane material to introduce carboxylic acid groups on the surface of the fiber membrane, which can further improve the adsorption effect of the filtration membrane material.

[0077] Test Example 3

[0078] Test of antibacterial performance:

[0079] The antibacterial test was carried out according to the oscillation method in the reference standard GB / T 20944.3-2008, and the antibacterial rate was calculated; the test bacteria was Escherichia coli. The test results are shown in Table 3.

[0080] Table 3

[0081] Bacteriostatic rate Bacteriostatic rate Example 1 ＞99% Comparative Example 1 98.92% Example 2 ＞99% Comparative Example 2 86.42% Example 3 ＞99% Comparative Example 3 81.57% Comparative Example 4 98.16%

[0082] The experimental data in Table 3 is analyzed, and the bacteriostatic rates of Examples 1-3 are obviously greater than those of Comparative Example 2, because the reed straw is high-temperature carbonized to obtain reed carbon; nitric acid is used as an oxidizing agent to oxidize the reed carbon, thereby increasing the content of carboxylic acid groups in the reed carbon; butyl trimethyl ammonium chloride is loaded on the oxidized reed carbon through electrostatic interaction to obtain modified reed carbon; butyl trimethyl ammonium chloride is a cationic bacteriostatic agent, which can further improve the bacteriostatic function of the filter membrane material. The bacteriostatic rates of Examples 1-3 are obviously greater than those of Comparative Example 3, because the enyl benzisothiazolinone is obtained by reacting benzisothiazolinone and 3-bromo-prop-1-ene; the enyl benzisothiazolinone is formulated into a finishing liquid; the fiber membrane is finished with the finishing liquid to obtain a plant-based water body filter material; the grafting reaction is carried out on the surface of the filter membrane material to introduce the benzisothiazolinone group on the surface of the fiber membrane, and the benzisothiazolinone group has bacteriostatic activity, which can further improve the bacteriostatic capacity of the filter membrane material.

[0083] The above specific embodiments further illustrate the purpose, technical solutions and advantages of the present application, and it should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method of making a plant-based water filtration material, characterized by, The preparation method of the plant-based water filtering material comprises the following steps: (1) reacting 4-(10,15,20-triphenylporphyrin-5-yl) aniline and acrylic-2,3-epoxy propyl ester to obtain an alkenyl porphyrin monomer; and reacting the alkenyl porphyrin monomer and zinc acetate to obtain an alkenyl porphyrin zinc complex; (2) reacting chitosan and the alkenyl porphyrin zinc complex to obtain modified chitosan; (3) carbonizing reed straw at high temperature to obtain reed carbon; oxidizing the reed carbon with nitric acid to obtain oxidized reed carbon; and loading butyl trimethyl ammonium chloride onto the oxidized reed carbon to obtain modified reed carbon; (4) preparing polybutylene terephthalate, modified chitosan and modified reed carbon into a spinning solution, and electrospinning to obtain a fiber membrane; (5) reacting benzisothiazolinone and 3-bromoprop-1-ene to obtain an alkenyl benzisothiazolinone; (6) preparing itaconic acid and the alkenyl benzisothiazolinone into a finishing liquid; and finishing the fiber membrane with the finishing liquid to obtain the plant-based water filtering material.

2. The method of making a plant-based water filtration material of claim 1, wherein, In step (1), the preparation method of the alkenyl porphyrin monomer is as follows: uniformly mixing 4-(10,15,20-triphenylporphyrin-5-yl) aniline and dichloromethane, stirring at room temperature for 20-30 min under nitrogen protection, adding acrylic-2,3-epoxy propyl ester, heating to 40-50 DEG C, continuing to stir and refluxing for 7-8 h, and drying to obtain the alkenyl porphyrin monomer.

3. The method of making a plant-based water filtration material of claim 1, wherein, In step (1), the preparation method of the alkenyl porphyrin zinc complex is as follows: mixing the alkenyl porphyrin monomer and dichloromethane, stirring at room temperature for 20-30 min, adding zinc acetate, stirring at 40-50 DEG C for 2-3 h, extracting with deionized water, taking the organic phase, and drying to obtain the alkenyl porphyrin zinc complex.

4. The method of making a plant-based water filtration material of claim 1, wherein, In step (2), the preparation method of the modified chitosan is as follows: uniformly mixing chitosan and N,N-dimethylformamide, stirring at 40-50 DEG C for 10-20 min, adding the alkenyl porphyrin zinc complex, stirring at 70-80 DEG C for 20-24 h, rotary evaporation under reduced pressure, washing, and drying to obtain the modified chitosan.

5. The method of making a plant-based water filtration material of claim 1, wherein, In step (3), the preparation method of the modified reed carbon is as follows: drying reed straw for 20-24 h, crushing the reed straw in a crusher, sieving to obtain straw powder; placing the straw powder in a crucible, heating to 400-500 DEG C under nitrogen protection, keeping the temperature for 60-80 min, heating to 600-700 DEG C, keeping the temperature for 2-3 h, cooling to room temperature, ball milling, and sieving to obtain reed carbon; uniformly mixing the reed carbon and 10% nitric acid aqueous solution according to a mass ratio of 1:(12-16), stirring at 75-85 DEG C for 10-14 h, filtering, washing, and drying to obtain oxidized reed carbon; uniformly mixing the oxidized reed carbon, butyl trimethyl ammonium chloride and methanol, ultrasonicating at room temperature for 3-4 h, filtering, and drying to obtain the modified reed carbon.

6. The method of making a plant-based water filtration material of claim 1, wherein, The preparation method of the fiber membrane in step (4) is as follows: uniformly mixing trifluoroacetic acid and dichloromethane to prepare a mixed solvent; taking 30-40 parts of polybutylene terephthalate, 4-5 parts of modified chitosan and 3-4 parts of modified reed carbon, and 150-200 parts of the mixed solvent; uniformly mixing the polybutylene terephthalate, the modified chitosan, the modified reed carbon and the mixed solvent to prepare a spinning solution; and electrospinning the spinning solution on an electrospinning instrument to obtain the fiber membrane.

7. The method of making a plant-based water filtration material of claim 1, wherein, The preparation method of the alkenyl benzisothiazolinone in step (5) is as follows: adding benzisothiazolinone, 3-bromoprop-1-ene and potassium carbonate into acetonitrile, stirring at 55-65℃ for 3-4h, uniformly mixing with deionized water after the reaction is completed, extracting with ethyl acetate, taking the organic phase, drying, and obtaining the alkenyl benzisothiazolinone.

8. A method of making a plant-based water filtration material according to claim 7, wherein, The chemical reaction formula of the alkenyl benzisothiazolinone is as follows: 。 9. The method of making a plant-based water filtration material of claim 1, wherein, The preparation method of the plant-based water body filtering material in step (6) is as follows: uniformly mixing itaconic acid, alkenyl benzisothiazolinone and acetone, stirring at room temperature for 10-20min, adding benzoyl peroxide to prepare a finishing liquid; immersing the fiber membrane in the finishing liquid, with a bath ratio of 1:(20-30), and keeping at 65-75℃ for 60-80min, taking out, drying, and obtaining the plant-based water body filtering material.

10. A plant-based water body filtering material prepared by the preparation method of the plant-based water body filtering material according to any one of claims 1-9.

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