An adsorption filter membrane for treating heavy metal ion pollution in water bodies and a preparation method thereof

Abstract

The present invention discloses an adsorption filter membrane for treating heavy metal ion pollution in water bodies and a preparation method thereof, and relates to the technical field of water treatment. When preparing the adsorption filter membrane for treating heavy metal ion pollution in water bodies, the present invention sequentially reacts graphene oxide with 3-diethylaminopropylamine, tetrabromophenylporphyrin and N,N-diethylallylamine to prepare functionalized graphene oxide; sequentially reacts cellulose with 4'-bromo-2,2':6',2"-terpyridine and maleic anhydride to prepare modified cellulose; reacts sodium alginate with propylene oxide to prepare modified sodium alginate; and reacts the modified sodium alginate, modified cellulose, functionalized graphene oxide, trans,trans-1,3-butadiene-1,4-dicarboxylic acid and a photoinitiator to prepare a membrane to prepare the adsorption filter membrane for treating heavy metal ion pollution in water bodies. The adsorption filter membrane for treating heavy metal ion pollution in water bodies prepared by the present invention has good antibacterial and photocatalytic degradation capabilities of organic matter.

Description

Technical Field

[0001] The present invention relates to the technical field of water treatment, in particular to an adsorption filter membrane for treating heavy metal ion pollution in water bodies and a preparation method thereof. Background Art

[0002] Membrane filtration technology has the advantages of high separation efficiency, easy operation, easy production, low cost, high recovery rate and good economic benefits. It is considered to be a green separation method. This article introduces an adsorption filtration membrane for treating heavy metal ion pollution in water bodies with antibacterial and photocatalytic degradation capabilities of organic pollutants. Summary of the Invention

[0003] The purpose of the present invention is to provide an adsorption filtration membrane for treating heavy metal ion pollution in water bodies and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies, the method mainly comprising the following preparation steps:

[0005] (1) Add the 3-diethylaminopropylamine aqueous solution to the graphene oxide aqueous solution which is 4 to 6 times the mass of the 3-diethylaminopropylamine aqueous solution at a uniform speed within 8 to 10 minutes, stir at 85 to 95 ° C and 200 to 300 r / min for 25 to 35 minutes, filter, wash with deionized water 3 to 5 times, and dry at 55 to 65 ° C for 22 to 26 hours to obtain pre-modified graphene oxide; mix the pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin in a mass ratio of 1:3 to 5:0.6 to 0.8, and stir at 40 to 5 0°C, stirring at 200-300 r / min for 7-9 hours, filtering, washing with diethyl ether 3-5 times, and vacuum drying at 40-50°C for 22-24 hours to obtain modified graphene oxide; modified graphene oxide, ethanol and N,N-diethylallylamine are mixed in a mass ratio of 1:3-5:0.6-0.8, stirred at 40-50°C, 200-300 r / min for 7-9 hours, filtering, washing with diethyl ether 3-5 times, and vacuum drying at 40-50°C for 22-24 hours to obtain functionalized graphene oxide;

[0006] (2) Cellulose, ethanol and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:3~5:0.1~0.2, stirred at 40~50℃ and 200~300r / min for 7~9h, filtered, washed with deionized water for 3~5 times, and vacuum dried at 40~50℃ for 22~24h to obtain pre-modified cellulose; pre-modified cellulose and maleic anhydride were mixed in a mass ratio of 1:5~7, stirred at 100~120℃ and 200~300r / min for 220~260min, washed with deionized water until neutral, and vacuum dried at 105~115℃ for 22~24h to obtain modified cellulose;

[0007] (3) Sodium alginate and deionized water were mixed in a mass ratio of 1:20~26, stirred at 200~300 r / min for 10~14 h, the pH was adjusted to 8.7~9.3 with sodium hydroxide aqueous solution, 0.2~0.3 times the mass of sodium alginate was added with 3,4-epoxy-1-butene, the temperature was raised to 70~80°C, the stirring was continued for 7~9 h, the pH was adjusted to neutral with acetic acid aqueous solution, the mixture was poured into acetone, and the mixture was allowed to stand for 10~14 h, filtered, washed with acetone 3~5 times, and vacuum dried at 45~55°C for 22~24 h to obtain modified sodium alginate;

[0008] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.03~0.05 parts of photoinitiator, 4~5 parts of modified sodium alginate, 0.6~0.8 parts of trans,trans-1,3-butadiene-1,4-dicarboxylic acid, and 3.5~4.5 parts of deionized water in parts by mass, mix the functionalized graphene oxide, modified cellulose, trans,trans-1,3-butadiene-1,4-dicarboxylic acid, photoinitiator, modified sodium alginate and deionized water, ultrasonicate for 4~6 hours, let it stand for 11~13 hours, and evenly coat it on a glass plate with a thickness of 0.08~0.12 mm. Let it stand for 3~5 minutes under a 500W ultraviolet lamp, scrape it off, and prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0009] As an optimization, it is characterized in that the graphene oxide aqueous solution in step (1) is prepared by uniformly mixing graphene oxide and deionized water in a mass ratio of 1:190-210.

[0010] The optimization method is characterized in that the 3-diethylaminopropylamine aqueous solution in step (1) is prepared by uniformly mixing 3-diethylaminopropylamine and deionized water in a mass ratio of 1:190-210.

[0011] As an optimization, it is characterized in that the cellulose in step (2) is microcrystalline cellulose.

[0012] As an optimization, it is characterized in that the maleic anhydride in step (2) is maleic anhydride heated to 100-120°C.

[0013] As an optimization, it is characterized in that the sodium hydroxide aqueous solution in step (3) is a 0.2M sodium hydroxide aqueous solution.

[0014] As an optimization, it is characterized in that the acetic acid aqueous solution in step (3) is prepared by uniformly mixing acetic acid and deionized water in a mass ratio of 1:1.

[0015] As an optimization, it is characterized in that the photoinitiator in step (4) is 1-hydroxycyclohexyl phenyl ketone.

[0016] As an optimization, it is characterized in that the manufacturer of the 500W ultraviolet lamp in step (4) is Beijing Newbit Technology Co., Ltd.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] When preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies, the present invention comprises the following steps: reacting graphene oxide with 3-diethylaminopropylamine, tetrabromophenylporphyrin and N,N-diethylallylamine in sequence to prepare functionalized graphene oxide; reacting cellulose with 4'-bromo-2,2':6',2''-terpyridine and maleic anhydride in sequence to prepare modified cellulose; reacting sodium alginate with 3,4-epoxy-1-butene to prepare modified sodium alginate; and reacting the modified sodium alginate, modified cellulose, functionalized graphene oxide, trans,trans-1,3-butadiene-1,4-dicarboxylic acid and a photoinitiator to prepare a membrane, thereby preparing the adsorption filtration membrane for treating heavy metal ion pollution in water bodies.

[0019] First, graphene oxide is reacted with 3-diethylaminopropylamine, tetrabromophenylporphyrin and N,N-diethylallylamine in sequence to obtain functionalized graphene oxide; graphene oxide is reacted with 3-diethylaminopropylamine and tetrabromophenylporphyrin in sequence to obtain graphene oxide rich in quaternary ammonium salts and porphyrins. After the quaternary ammonium salts come into contact with the cell surface, the alkyl chains can insert into the hydrophobic region of the cell membrane, destroying the membrane structure, causing the cell contents to leak and die. At the same time, ion exchange is carried out on the amino and hydroxyl groups on the cell surface, thereby destroying the original structure of the cell membrane, accelerating membrane damage and cell death, thereby achieving an antibacterial effect. After being chelated with heavy metals in the wastewater, porphyrin forms a metal-organic framework, which can degrade organic pollutants under photocatalytic conditions; it then reacts with N,N-diethylallylamine to form more quaternary ammonium salts, and the graphene oxide surface is rich in double bonds, which is convenient for subsequent cross-linking with sodium alginate and cellulose.

[0020] Secondly, cellulose is reacted with 4'-bromo-2,2':6',2''-terpyridine and maleic anhydride in sequence to obtain modified cellulose; sodium alginate is reacted with 3,4-epoxy-1-butene to obtain modified sodium alginate; modified sodium alginate, modified cellulose, functionalized graphene oxide, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and a photoinitiator are reacted to prepare a membrane to obtain an adsorption filtration membrane for treating heavy metal ion pollution in water; 4'-bromo-2,2':6',2''-terpyridine reacts with part of the hydroxyl groups of cellulose to make the cellulose rich in terpyridine structure, which can adsorb heavy metal substances, and then reacts with maleic anhydride to make the cellulose rich in both carboxyl groups and double bonds. The presence of double bonds facilitates subsequent reaction with seaweed. Cross-linking of sodium alginate and functionalized graphene oxide; reacting sodium alginate with 3,4-epoxy-1-butene to make it rich in double bonds, which is convenient for cross-linking, and the sodium in sodium alginate can be replaced by heavy metal ions in pollutants, thereby achieving the effect of removing heavy metal ions in pollutants; reacting modified sodium alginate, modified cellulose, functionalized graphene oxide, trans,trans-1,3-butadiene-1,4-dicarboxylic acid, a photoinitiator and deionized water, and polymerizing the double bonds under the photoinitiator, and finally obtaining a membrane rich in carboxyl groups. The negative charge of the carboxyl group can form a coordination bond with the heavy metal ions, thereby adsorbing heavy metal ions, having high chemical reactivity, and being able to efficiently adsorb heavy metal pollutants, and the carboxyl group is hydrophilic, so that the obtained membrane has good wetting ability. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0022] Example 1:

[0023] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0024] (1) Graphene oxide and deionized water were mixed at a mass ratio of 1:190 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water were mixed at a mass ratio of 1:190 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution was added to a graphene oxide aqueous solution with a mass 4 times that of the 3-diethylaminopropylamine aqueous solution at a uniform speed within 8 minutes, stirred at 85°C and 200 r / min for 25 minutes, filtered, washed with deionized water for 3 times, and dried at 55°C for 22 hours to obtain a pre-modified graphene oxide. Graphene; pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin were mixed in a mass ratio of 1:3:0.6, stirred at 40°C and 200 r / min for 7 hours, filtered, washed with ether three times, and vacuum dried at 40°C for 22 hours to obtain modified graphene oxide; modified graphene oxide, ethanol and N,N-diethylallylamine were mixed in a mass ratio of 1:3:0.6, stirred at 40°C and 200 r / min for 7 hours, filtered, washed with ether three times, and vacuum dried at 40°C for 22 hours to obtain functionalized graphene oxide;

[0025] (2) Cellulose, ethanol and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:3:0.1, stirred at 40°C and 200 r / min for 7 h, filtered, washed with deionized water three times, and vacuum dried at 40°C for 22 h to obtain pre-modified cellulose; maleic anhydride was heated to 100°C to obtain maleic anhydride; pre-modified cellulose and maleic anhydride were mixed in a mass ratio of 1:5, stirred at 100°C and 200 r / min for 220 min, washed with deionized water until neutral, and vacuum dried at 105°C for 22 h to obtain modified cellulose;

[0026] (3) Acetic acid and deionized water were mixed in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; sodium alginate and deionized water were mixed in a mass ratio of 1:20, stirred at 200 r / min for 10 h, the pH was adjusted to 8.7 with a 0.2 m sodium hydroxide aqueous solution, 3,4-epoxy-1-butene (0.2 times the mass of sodium alginate) was added, the temperature was raised to 70 ° C, the stirring was continued for 7 h, the pH was adjusted to neutral with an acetic acid aqueous solution, the solution was poured into acetone, allowed to stand for 10, filtered, washed with acetone 3 times, and vacuum dried at 45 ° C for 22 h to obtain modified sodium alginate;

[0027] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.03 parts of 1-hydroxycyclohexylphenyl ketone, 4 parts of modified sodium alginate, 0.6 parts of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 3.5 parts of deionized water by mass, mix the functionalized graphene oxide, modified cellulose, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, 1-hydroxycyclohexylphenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 4 hours, let it stand for 11 hours, and evenly coat it on a glass plate with a thickness of 0.08 mm. Then let it stand for 3 minutes under a 500W ultraviolet lamp, scrape it off, and prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0028] Example 2:

[0029] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0030] (1) Graphene oxide and deionized water were mixed at a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water were mixed at a mass ratio of 1:200 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution was added uniformly over 9 minutes to a graphene oxide aqueous solution 5 times the mass of the 3-diethylaminopropylamine aqueous solution, stirred at 90°C and 250 r / min for 30 minutes, filtered, washed with deionized water 4 times, and dried at 60°C for 24 hours to obtain a pre-modified graphene oxide. Graphene; pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin were mixed in a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 hours to obtain modified graphene oxide; modified graphene oxide, ethanol and N,N-diethylallylamine were mixed in a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 hours to obtain functionalized graphene oxide;

[0031] (2) Cellulose, ethanol and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:4:0.15, stirred at 45°C and 250 r / min for 8 h, filtered, washed with deionized water 4 times, and vacuum dried at 45°C for 23 h to obtain pre-modified cellulose; maleic anhydride was heated to 110°C to obtain maleic anhydride; pre-modified cellulose and maleic anhydride were mixed in a mass ratio of 1:6, stirred at 110°C and 250 r / min for 240 min, washed with deionized water until neutral, and vacuum dried at 110°C for 23 h to obtain modified cellulose;

[0032] (3) Acetic acid and deionized water were mixed in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; sodium alginate and deionized water were mixed in a mass ratio of 1:23, stirred at 250 r / min for 12 h, the pH was adjusted to 9 with a 0.2 m sodium hydroxide aqueous solution, 3,4-epoxy-1-butene (0.25 times the mass of sodium alginate) was added, the temperature was raised to 75 ° C, the stirring was continued for 8 h, the pH was adjusted to neutral with an acetic acid aqueous solution, the solution was poured into acetone, allowed to stand for 12 h, filtered, washed with acetone 4 times, and vacuum dried at 50 ° C for 23 h to obtain modified sodium alginate;

[0033] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexylphenyl ketone, 4.5 parts of modified sodium alginate, 0.7 parts of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 4 parts of deionized water by mass, mix the functionalized graphene oxide, modified cellulose, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, 1-hydroxycyclohexylphenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let it stand for 12 hours, and evenly coat it on a glass plate with a thickness of 0.1 mm. Then let it stand for 4 minutes under a 500W ultraviolet lamp and scrape it off to prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0034] Example 3:

[0035] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0036] (1) Graphene oxide and deionized water were mixed at a mass ratio of 1:210 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water were mixed at a mass ratio of 1:210 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution was added uniformly over 10 minutes to a graphene oxide aqueous solution with a mass 6 times that of the 3-diethylaminopropylamine aqueous solution, stirred at 95°C and 300 r / min for 35 minutes, filtered, washed with deionized water for 5 times, and dried at 65°C for 26 hours to obtain pre-modified graphene oxide. Modified graphene; pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin were mixed in a mass ratio of 1:5:0.8, stirred at 50°C and 300 r / min for 9 hours, filtered, washed with ether 5 times, and vacuum dried at 50°C for 24 hours to obtain modified graphene oxide; modified graphene oxide, ethanol and N,N-diethylallylamine were mixed in a mass ratio of 1:5:0.8, stirred at 50°C and 300 r / min for 9 hours, filtered, washed with ether 5 times, and vacuum dried at 50°C for 24 hours to obtain functionalized graphene oxide;

[0037] (2) Cellulose, ethanol and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:5:0.2, stirred at 50°C and 300 r / min for 9 h, filtered, washed with deionized water 5 times, and vacuum dried at 50°C for 24 h to obtain pre-modified cellulose; maleic anhydride was heated to 120°C to obtain maleic anhydride; pre-modified cellulose and maleic anhydride were mixed in a mass ratio of 1:7, stirred at 120°C and 300 r / min for 260 min, washed with deionized water until neutral, and vacuum dried at 115°C for 24 h to obtain modified cellulose;

[0038] (3) Acetic acid and deionized water were mixed in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; sodium alginate and deionized water were mixed in a mass ratio of 1:26, stirred at 300 r / min for 14 h, the pH was adjusted to 9.3 with a 0.2 m sodium hydroxide aqueous solution, 3,4-epoxy-1-butene (0.3 times the mass of sodium alginate) was added, the temperature was raised to 80 ° C, the stirring was continued for 9 h, the pH was adjusted to neutral with an acetic acid aqueous solution, the solution was poured into acetone, allowed to stand for 14 h, filtered, washed with acetone 5 times, and vacuum dried at 55 ° C for 24 h to obtain modified sodium alginate;

[0039] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.05 parts of 1-hydroxycyclohexylphenyl ketone, 5 parts of modified sodium alginate, 0.8 parts of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 4.5 parts of deionized water by mass, mix the functionalized graphene oxide, modified cellulose, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, 1-hydroxycyclohexylphenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 6 hours, let it stand for 13 hours, and evenly coat it on a glass plate with a thickness of 0.12 mm. Then let it stand for 5 minutes under a 500W ultraviolet lamp, scrape it off, and prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0040] Comparative Example 1:

[0041] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0042] (1) Graphene oxide and deionized water were mixed at a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water were mixed at a mass ratio of 1:200 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution was uniformly added to a graphene oxide aqueous solution 5 times the mass of the 3-diethylaminopropylamine aqueous solution within 9 minutes, stirred at 90°C and 250 r / min for 30 minutes, filtered, washed with deionized water 4 times, and dried at 60°C for 24 hours to obtain pre-modified graphene oxide; pre-modified graphene oxide, ethanol and N,N-diethylallylamine were mixed at a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 hours to obtain functionalized graphene oxide;

[0043] (2) Cellulose, ethanol and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:4:0.15, stirred at 45°C and 250 r / min for 8 h, filtered, washed with deionized water 4 times, and vacuum dried at 45°C for 23 h to obtain pre-modified cellulose; maleic anhydride was heated to 110°C to obtain maleic anhydride; pre-modified cellulose and maleic anhydride were mixed in a mass ratio of 1:6, stirred at 110°C and 250 r / min for 240 min, washed with deionized water until neutral, and vacuum dried at 110°C for 23 h to obtain modified cellulose;

[0044] (3) Acetic acid and deionized water were mixed in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; sodium alginate and deionized water were mixed in a mass ratio of 1:23, stirred at 250 r / min for 12 h, the pH was adjusted to 9 with a 0.2 m sodium hydroxide aqueous solution, 3,4-epoxy-1-butene (0.25 times the mass of sodium alginate) was added, the temperature was raised to 75 ° C, the stirring was continued for 8 h, the pH was adjusted to neutral with an acetic acid aqueous solution, the solution was poured into acetone, allowed to stand for 12 h, filtered, washed with acetone 4 times, and vacuum dried at 50 ° C for 23 h to obtain modified sodium alginate;

[0045] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexylphenyl ketone, 4.5 parts of modified sodium alginate, 0.7 parts of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 4 parts of deionized water by mass, mix the functionalized graphene oxide, modified cellulose, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, 1-hydroxycyclohexylphenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let it stand for 12 hours, and evenly coat it on a glass plate with a thickness of 0.1 mm. Then let it stand for 4 minutes under a 500W ultraviolet lamp and scrape it off to prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0046] Comparative Example 2:

[0047] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0048] (1) Cellulose, ethanol and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:4:0.15, stirred at 45°C and 250 r / min for 8 h, filtered, washed with deionized water 4 times, and vacuum dried at 45°C for 23 h to obtain pre-modified cellulose; maleic anhydride was heated to 110°C to obtain maleic anhydride; pre-modified cellulose and maleic anhydride were mixed in a mass ratio of 1:6, stirred at 110°C and 250 r / min for 240 min, washed with deionized water until neutral, and vacuum dried at 110°C for 23 h to obtain modified cellulose;

[0049] (2) Acetic acid and deionized water were mixed in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; sodium alginate and deionized water were mixed in a mass ratio of 1:23, stirred at 250 r / min for 12 h, the pH was adjusted to 9 with a 0.2 m sodium hydroxide aqueous solution, 3,4-epoxy-1-butene (0.25 times the mass of sodium alginate) was added, the temperature was raised to 75 ° C, the stirring was continued for 8 h, the pH was adjusted to neutral with an acetic acid aqueous solution, the solution was poured into acetone, allowed to stand for 12 h, filtered, washed with acetone 4 times, and vacuum dried at 50 ° C for 23 h to obtain modified sodium alginate;

[0050] (3) Take 1 part of graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexylphenyl ketone, 4.5 parts of modified sodium alginate, 0.7 parts of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 4 parts of deionized water by mass, mix the functionalized graphene oxide, modified cellulose, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, 1-hydroxycyclohexylphenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let it stand for 12 hours, and evenly coat it on a glass plate with a thickness of 0.1 mm. Then let it stand for 4 minutes under a 500W ultraviolet lamp and scrape it off to prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0051] Comparative Example 3

[0052] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0053] (1) Graphene oxide and deionized water were mixed at a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water were mixed at a mass ratio of 1:200 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution was added uniformly over 9 minutes to a graphene oxide aqueous solution 5 times the mass of the 3-diethylaminopropylamine aqueous solution, stirred at 90°C and 250 r / min for 30 minutes, filtered, washed with deionized water 4 times, and dried at 60°C for 24 hours to obtain a pre-modified graphene oxide. Graphene; pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin were mixed in a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 hours to obtain modified graphene oxide; modified graphene oxide, ethanol and N,N-diethylallylamine were mixed in a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 hours to obtain functionalized graphene oxide;

[0054] (2) Heating maleic anhydride to 110°C to obtain maleic anhydride; mixing modified cellulose and maleic anhydride in a mass ratio of 1:6, stirring at 110°C and 250 r / min for 240 min, washing with deionized water until neutral, and vacuum drying at 110°C for 23 h to obtain modified cellulose;

[0055] (3) Acetic acid and deionized water were mixed in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; sodium alginate and deionized water were mixed in a mass ratio of 1:23, stirred at 250 r / min for 12 h, the pH was adjusted to 9 with a 0.2 m sodium hydroxide aqueous solution, 3,4-epoxy-1-butene (0.25 times the mass of sodium alginate) was added, the temperature was raised to 75 ° C, the stirring was continued for 8 h, the pH was adjusted to neutral with an acetic acid aqueous solution, the solution was poured into acetone, allowed to stand for 12 h, filtered, washed with acetone 4 times, and vacuum dried at 50 ° C for 23 h to obtain modified sodium alginate;

[0056] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexylphenyl ketone, 4.5 parts of modified sodium alginate, 0.7 parts of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 4 parts of deionized water by mass, mix the functionalized graphene oxide, modified cellulose, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, 1-hydroxycyclohexylphenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let it stand for 12 hours, and evenly coat it on a glass plate with a thickness of 0.1 mm. Then let it stand for 4 minutes under a 500W ultraviolet lamp and scrape it off to prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0057] Comparative Example 4

[0058] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0059] (1) Graphene oxide and deionized water were mixed at a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water were mixed at a mass ratio of 1:200 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution was added uniformly over 9 minutes to a graphene oxide aqueous solution 5 times the mass of the 3-diethylaminopropylamine aqueous solution, stirred at 90°C and 250 r / min for 30 minutes, filtered, washed with deionized water 4 times, and dried at 60°C for 24 hours to obtain a pre-modified graphene oxide. Graphene; pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin were mixed in a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 hours to obtain modified graphene oxide; modified graphene oxide, ethanol and N,N-diethylallylamine were mixed in a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 hours to obtain functionalized graphene oxide;

[0060] (2) Cellulose, ethanol, and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:4:0.15, stirred at 45°C and 250 r / min for 8 h, filtered, washed with deionized water four times, and vacuum dried at 45°C for 23 h to obtain pre-modified cellulose;

[0061] (3) Acetic acid and deionized water were mixed in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; sodium alginate and deionized water were mixed in a mass ratio of 1:23, stirred at 250 r / min for 12 h, the pH was adjusted to 9 with a 0.2 m sodium hydroxide aqueous solution, 3,4-epoxy-1-butene (0.25 times the mass of sodium alginate) was added, the temperature was raised to 75 ° C, the stirring was continued for 8 h, the pH was adjusted to neutral with an acetic acid aqueous solution, the solution was poured into acetone, allowed to stand for 12 h, filtered, washed with acetone 4 times, and vacuum dried at 50 ° C for 23 h to obtain modified sodium alginate;

[0062] (4) Take 1 part of functionalized graphene oxide, 1 part of pre-modified cellulose, 0.04 parts of 1-hydroxycyclohexylphenyl ketone, 4.5 parts of modified sodium alginate, 0.7 parts of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 4 parts of deionized water by mass, mix the functionalized graphene oxide, modified cellulose, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, 1-hydroxycyclohexylphenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let it stand for 12 hours, and evenly coat it on a glass plate with a thickness of 0.1 mm. Then let it stand for 4 minutes under a 500W ultraviolet lamp and scrape it off to prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

[0063] Test Example 1:

[0064] Antibacterial testing

[0065] According to QB / T2591, the selected bacterial species were Staphylococcus aureus and Escherichia coli. The results are shown in Table 1.

[0066] Table 1

[0067]

[0068] From the comparison of the experimental data in Table 1, it can be found that the adsorption filtration membrane for treating heavy metal ion pollution in water prepared by the present invention has good antibacterial ability.

[0069] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2 in Table 1, it can be found that the antibacterial rates of Examples 1, 2, and 3 are higher than those of Comparative Example 2, which shows that graphene oxide is reacted with 3-diethylaminopropylamine and tetrabromophenylporphyrin in sequence to generate quaternary ammonium salts. After the quaternary ammonium salts come into contact with the cell surface, the alkyl chains can be inserted into the hydrophobic region of the cell membrane, destroying the membrane structure, causing the cell contents to leak and die. At the same time, ion exchange is performed on the amino and hydroxyl groups on the cell surface, thereby destroying the original structure of the cell membrane, accelerating membrane damage and cell death, and thus achieving an antibacterial effect.

[0070] Test Example 2:

[0071] Metal ion adsorption test

[0072] At room temperature, add 50 mL of 25 mg / L copper ion solution to a solution with an area of ​​25 cm 2 The copper ion concentration was measured after 60 minutes for a 0.2 cm thick film. The results are shown in Table 2.

[0073] Table 2

[0074]

[0075] From the comparison of the experimental data in Table 2, it can be found that the adsorption filter membrane for treating heavy metal ion pollution in water prepared by the present invention has good metal ion adsorption capacity.

[0076] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 2, it can be found that the copper ion concentrations of Examples 1, 2, and 3 are lower than those of Comparative Example 1, which shows that porphyrin can complex with metal ions and reduce the metal ion concentration in water;

[0077] Comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 3 shows that the copper ion concentrations of Examples 1, 2, and 3 are lower than those of Comparative Example 3. 4'-Bromo-2,2':6',2''-terpyridine reacts with some hydroxyl groups of cellulose, enriching the cellulose with a terpyridine structure, which can adsorb heavy metal substances and reduce the metal ion concentration in water.

[0078] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4, it can be found that the copper ion concentration of Examples 1, 2, and 3 is lower than that of Comparative Example 4, which shows that the reaction of the pre-modified cellulose with maleic anhydride makes the cellulose rich in carboxyl groups. The negative charge of the carboxyl groups can form coordination bonds with heavy metal ions, thereby adsorbing heavy metal ions, having high chemical reactivity, and can efficiently adsorb heavy metal pollutants and reduce the metal ion concentration in water.

[0079] Test Example 3:

[0080] Organic matter degradation test

[0081] Add 50mL of 20mg / L iron ion solution with an area of ​​25cm 2 The 0.2 cm thick membrane was removed after 60 minutes and vacuum dried at -5°C for 24 hours. 25 mL of a 10 ppm methylene blue solution was prepared, and the filter membrane was placed in the methylene blue solution. Ultrasonic treatment was performed, and the photocatalytic device was powered on for 60 minutes. The degradation efficiency was calculated based on the change in absorbance at 665 nm. The results are shown in Table 3.

[0082] Table 3

[0083]

[0084] From the comparison of the experimental data in Table 3, it can be found that the adsorption filtration membrane for treating heavy metal ion pollution in water prepared by the present invention has good antibacterial ability.

[0085] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 3, it can be found that the degradation efficiency of Examples 1, 2, and 3 is higher than that of Comparative Example 1, which shows that porphyrin forms a metal-organic framework after metal chelation in wastewater, which can degrade organic pollutants under photocatalytic conditions.

[0086] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies, characterized in that: The preparation method of the adsorption filter membrane for treating heavy metal ion pollution in water mainly comprises the following preparation steps: (1) Add the 3-diethylaminopropylamine aqueous solution to the graphene oxide aqueous solution which is 4 to 6 times the mass of the 3-diethylaminopropylamine aqueous solution at a uniform speed within 8 to 10 minutes, stir at 85 to 95 ° C and 200 to 300 r / min for 25 to 35 minutes, filter, wash with deionized water 3 to 5 times, and dry at 55 to 65 ° C for 22 to 26 hours to obtain pre-modified graphene oxide; mix the pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin in a mass ratio of 1:3 to 5:0.6 to 0.8, and stir at 40 to 5 0°C, stirring at 200-300 r / min for 7-9 hours, filtering, washing with diethyl ether 3-5 times, and vacuum drying at 40-50°C for 22-24 hours to obtain modified graphene oxide; modified graphene oxide, ethanol and N,N-diethylallylamine are mixed in a mass ratio of 1:3-5:0.6-0.8, stirred at 40-50°C, 200-300 r / min for 7-9 hours, filtering, washing with diethyl ether 3-5 times, and vacuum drying at 40-50°C for 22-24 hours to obtain functionalized graphene oxide; (2) Cellulose, ethanol, and 4'-bromo-2,2':6',2''-terpyridine were mixed in a mass ratio of 1:3-5:0.1-0.2, stirred at 40-50°C and 200-300 r / min for 7-9 h, filtered, washed with deionized water 3-5 times, and vacuum dried at 40-50°C for 22-24 h to obtain pre-modified cellulose; The pre-modified cellulose and maleic anhydride were mixed in a mass ratio of 1:5-7, stirred at 100-120°C and 200-300 r / min for 220-260 min, washed with deionized water until neutral, and vacuum dried at 105-115°C for 22-24 h to obtain the modified cellulose. (3) Sodium alginate and deionized water were mixed in a mass ratio of 1:20~26, stirred at 200~300 r / min for 10~14 h, the pH was adjusted to 8.7~9.3 with sodium hydroxide aqueous solution, 0.2~0.3 times the mass of sodium alginate was added with 3,4-epoxy-1-butene, the temperature was raised to 70~80°C, the stirring was continued for 7~9 h, the pH was adjusted to neutral with acetic acid aqueous solution, the mixture was poured into acetone, and the mixture was allowed to stand for 10~14 h, filtered, washed with acetone 3~5 times, and vacuum dried at 45~55°C for 22~24 h to obtain modified sodium alginate; (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.03~0.05 parts of photoinitiator, 4~5 parts of modified sodium alginate, 0.6~0.8 parts of trans,trans-1,3-butadiene-1,4-dicarboxylic acid, and 3.5~4.5 parts of deionized water in parts by mass, mix the functionalized graphene oxide, modified cellulose, trans,trans-1,3-butadiene-1,4-dicarboxylic acid, photoinitiator, modified sodium alginate and deionized water, ultrasonicate for 4~6 hours, let it stand for 11~13 hours, and evenly coat it on a glass plate with a thickness of 0.08~0.12 mm. Let it stand for 3~5 minutes under a 500W ultraviolet lamp, scrape it off, and prepare an adsorption filter membrane for treating heavy metal ion pollution in water.

2. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 1, characterized in that: The graphene oxide aqueous solution in step (1) is prepared by uniformly mixing graphene oxide and deionized water in a mass ratio of 1:190-210.

3. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 1, characterized in that: The 3-diethylaminopropylamine aqueous solution in step (1) is prepared by uniformly mixing 3-diethylaminopropylamine and deionized water in a mass ratio of 1:190-210.

4. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 1, characterized in that: The cellulose in step (2) is microcrystalline cellulose.

5. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 1, characterized in that: The maleic anhydride in step (2) is maleic anhydride heated to 100-120°C.

6. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 1, characterized in that: The sodium hydroxide aqueous solution in step (3) is a 0.2M sodium hydroxide aqueous solution.

7. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 1, characterized in that: The acetic acid aqueous solution in step (3) is prepared by uniformly mixing acetic acid and deionized water in a mass ratio of 1:

1.

8. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 1, characterized in that: The photoinitiator in step (4) is 1-hydroxycyclohexyl phenyl ketone.

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