Adsorption filtering membrane for treating heavy metal ion pollution of water body and preparation method of adsorption filtering membrane

Abstract

The invention discloses a water body heavy metal ion pollution treatment adsorption filtering membrane and a preparation method thereof, and relates to the technical field of water treatment. When the water body heavy metal ion pollution treatment adsorption filtering membrane is prepared, graphene oxide sequentially reacts with 3-diethylaminopropylamine, tetrabromophenyl porphyrin and N, N-diethyl allylamine, and functionalized graphene oxide is prepared; the preparation method comprises the following steps: reacting cellulose with 4 '-bromo-2, 2': 6 ', 2' '-terpyridyl and maleic anhydride in sequence to prepare modified cellulose; the preparation method comprises the following steps: reacting sodium alginate with propylene oxide to prepare modified sodium alginate; the modified sodium alginate, the modified cellulose, the functionalized graphene oxide, trans, trans-1, 3-butadiene-1, 4-dicarboxylic acid and a photoinitiator are subjected to a reaction, a membrane is prepared, and the water body heavy metal ion pollution treatment adsorption filtering membrane is prepared. The water body heavy metal ion pollution treatment adsorption filtering membrane prepared by the invention has good antibacterial and photocatalytic organic matter degradation capabilities.

Description

Technical Field

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

[0002] Providing clean and safe fresh water is one of the major challenges of the 21st century. The accelerated urbanization process, population growth and industrial development have caused serious pollution to fresh water resources. Coupled with climate change, natural disasters such as hurricanes and floods occur frequently, and various pollutants are mixed into water sources, exacerbating the global shortage of clean fresh water resources. Membrane filtration technology has the advantages of high phase separation efficiency, easy operation, easy production, low cost, high recovery rate and good economic benefits, and is considered to be a green separation method.

[0003] The rapid development of industry and agriculture and the efficient operation of society have caused serious pollution to water sources, such as heavy metal pollution, oil pollution, organic chemical pollution, micro-nano particle pollution and biological pollution. These pollutants can enter the human body through drinking water and accumulate in the body, causing acute or chronic diseases and threatening national health and safety. Therefore, there is an urgent need to develop new technologies and efficient strategies to alleviate water pollution problems at lower costs and with less energy consumption. In the face of the complexity and diversity of pollutants, this article introduces an adsorption filtration membrane for the treatment of heavy metal ion pollution in water bodies with the ability to resist bacteria and photocatalytically degrade organic pollutants. Summary of the invention

[0004] The object 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.

[0005] A water body heavy metal ion pollution treatment adsorption filtration membrane, the water body heavy metal ion pollution treatment adsorption filtration membrane is prepared by reacting sodium alginate with propylene oxide to obtain modified sodium alginate; and reacting modified sodium alginate, modified cellulose, functionalized graphene oxide, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and a photoinitiator to form a membrane;

[0006] The modified sodium alginate is prepared by reacting sodium alginate with propylene oxide;

[0007] The modified cellulose is prepared by reacting cellulose with 4'-bromo-2,2':6',2"-terpyridine and maleic anhydride in sequence;

[0008] The functionalized graphene oxide is prepared by sequentially reacting graphene oxide with 3-diethylaminopropylamine, tetrabromophenylporphyrin and N,N-diethylallylamine.

[0009] 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:

[0010] (1) adding a 3-diethylaminopropylamine aqueous solution to a graphene oxide aqueous solution of 4 to 6 times the mass of the 3-diethylaminopropylamine aqueous solution at a uniform rate within 8 to 10 minutes, stirring at 85 to 95° C. and 200 to 300 r / min for 25 to 35 minutes, filtering, washing with deionized water for 3 to 5 times, and drying at 55 to 65° C. for 22 to 26 hours to obtain pre-modified graphene oxide; mixing the pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin in a mass ratio of 1:3 to 5:0.6 to 0.8, and heating at 40 to 5 0°C, stirring at 200-300 r / min for 7-9h, filtering, washing with ether for 3-5 times, and vacuum drying at 40-50°C for 22-24h to obtain modified graphene oxide; modifying graphene oxide, ethanol and N,N-diethylallylamine are mixed in a mass ratio of 1:3-5:0.6-0.8, stirring at 40-50°C, 200-300 r / min for 7-9h, filtering, washing with ether for 3-5 times, and vacuum drying at 40-50°C for 22-24h to obtain functionalized graphene oxide;

[0011] (2) Mixing cellulose, ethanol and 4'-bromo-2,2':6',2"-terpyridine in a mass ratio of 1:3-5:0.1-0.2, stirring at 40-50°C and 200-300 r / min for 7-9 hours, filtering, washing with deionized water for 3-5 times, and vacuum drying at 40-50°C for 22-24 hours to obtain pre-modified cellulose; mixing pre-modified cellulose and maleic anhydride in a mass ratio of 1:5-7, stirring at 100-120°C and 200-300 r / min for 220-260 minutes, washing with deionized water until neutral, and vacuum drying at 105-115°C for 22-24 hours to obtain modified cellulose;

[0012] (3) Sodium alginate and deionized water are mixed in a mass ratio of 1:20-26, stirred at 200-300 r / min for 10-14 h, the pH is adjusted to 8.7-9.3 with a sodium hydroxide aqueous solution, 3,4-epoxy-1-butene in an amount of 0.2-0.3 times the mass of the sodium alginate is added, the temperature is raised to 70-80° C., stirring is continued for 7-9 h, the pH is adjusted to neutral with an acetic acid aqueous solution, poured into acetone, allowed to stand for 10-14 h, filtered, washed with acetone for 3-5 times, and vacuum dried at 45-55° C. for 22-24 h to obtain modified sodium alginate;

[0013] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.03-0.05 part of photoinitiator, 4-5 parts of modified sodium alginate, 0.6-0.8 part of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 3.5-4.5 parts of deionized water 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 stand for 11-13 hours, and evenly coat on a glass plate with a thickness of 0.08-0.12 mm. Let stand for 3-5 minutes under a 500 W ultraviolet lamp, scrape off, and obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0014] 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.

[0015] The method is optimized, 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.

[0016] As an optimization, it is characterized in that the cellulose in step (2) is microcrystalline cellulose.

[0017] As an optimization, it is characterized in that the maleic anhydride in step (2) is maleic anhydride heated to 100-120°C.

[0018] As an optimization, it is characterized in that the sodium hydroxide aqueous solution in step (3) is a 0.2M sodium hydroxide aqueous solution.

[0019] 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.

[0020] As an optimization, it is characterized in that the photoinitiator in step (4) is 1-hydroxycyclohexyl phenyl ketone.

[0021] As an optimization, it is characterized in that the manufacturer of the 500W ultraviolet lamp in step (4) is Beijing Newbit Technology Co., Ltd.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] When preparing the adsorption filtration 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 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 filtration membrane for treating heavy metal ion pollution in water bodies.

[0024] 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 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, ions are exchanged with 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 the porphyrins are chelated with heavy metals in the wastewater, a metal-organic framework is formed, which can degrade organic pollutants under photocatalytic conditions; and then reacted with N,N-diethylallylamine to form more quaternary ammonium salts, and the surface of graphene oxide is rich in double bonds, which is convenient for subsequent cross-linking with sodium alginate and cellulose.

[0025] 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 propylene oxide 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 prepare an adsorption filtration membrane for treating heavy metal ion pollution in water bodies; 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, and the presence of double bonds facilitates the subsequent reaction with alginate Cross-linking of sodium and functionalized graphene oxide; reacting sodium alginate with propylene oxide 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, so as to achieve 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, photoinitiator and deionized water, and polymerizing double bonds under the photoinitiator, and finally obtaining a membrane rich in carboxyl groups, and the negative charge of the carboxyl group can form a coordination bond with the heavy metal ions, thereby adsorbing the heavy metal ions, having high chemical reaction activity, 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

[0026] 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 described embodiments 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 work are within the scope of protection of the present invention.

[0027] Embodiment 1:

[0028] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0029] (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 uniformly added to a graphene oxide aqueous solution with a mass of 4 times that of the 3-diethylaminopropylamine aqueous solution 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 3 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 3 times, and vacuum dried at 40°C for 22 hours to obtain functionalized graphene oxide;

[0030] (2) Mix cellulose, ethanol and 4'-bromo-2,2':6',2"-terpyridine in a mass ratio of 1:3:0.1, stir at 40°C and 200 r / min for 7 h, filter, wash with deionized water for 3 times, and vacuum dry at 40°C for 22 h to obtain pre-modified cellulose; heat maleic anhydride to 100°C to obtain maleic anhydride; mix pre-modified cellulose and maleic anhydride in a mass ratio of 1:5, stir at 100°C and 200 r / min for 220 min, wash with deionized water until neutral, and vacuum dry at 105°C for 22 h to obtain modified cellulose;

[0031] (3) Mix acetic acid and deionized water in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; mix sodium alginate and deionized water in a mass ratio of 1:20, stir at 200 r / min for 10 hours, adjust the pH to 8.7 with a 0.2 m sodium hydroxide aqueous solution, add 3,4-epoxy-1-butene in an amount of 0.2 times the mass of sodium alginate, heat to 70°C, continue stirring for 7 hours, adjust the pH to neutral with an acetic acid aqueous solution, pour into acetone, let stand for 10, filter, wash with acetone 3 times, and vacuum dry at 45°C for 22 hours to obtain modified sodium alginate;

[0032] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.03 parts of 1-hydroxycyclohexyl phenyl 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-hydroxycyclohexyl phenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 4 hours, let stand for 11 hours, and evenly coat on a glass plate with a thickness of 0.08 mm. Let stand for 3 minutes under a 500 W ultraviolet lamp, and scrape off to obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0033] Embodiment 2:

[0034] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0035] (1) Graphene oxide and deionized water are mixed at a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water are mixed at a mass ratio of 1:200 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution is uniformly added to a graphene oxide aqueous solution with a mass of 5 times that 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 for 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 h, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 h 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 h, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 h to obtain functionalized graphene oxide;

[0036] (2) Mix cellulose, ethanol and 4'-bromo-2,2':6',2"-terpyridine in a mass ratio of 1:4:0.15, stir at 45°C and 250 r / min for 8 h, filter, wash with deionized water for 4 times, and vacuum dry at 45°C for 23 h to obtain pre-modified cellulose; heat maleic anhydride to 110°C to obtain maleic anhydride; mix pre-modified cellulose and maleic anhydride in a mass ratio of 1:6, stir at 110°C and 250 r / min for 240 min, wash with deionized water until neutral, and vacuum dry at 110°C for 23 h to obtain modified cellulose;

[0037] (3) Mix acetic acid and deionized water in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; mix sodium alginate and deionized water in a mass ratio of 1:23, stir at 250 r / min for 12 hours, adjust the pH to 9 with a 0.2 m sodium hydroxide aqueous solution, add 3,4-epoxy-1-butene in an amount of 0.25 times the mass of sodium alginate, heat to 75°C, continue stirring for 8 hours, adjust the pH to neutral with an acetic acid aqueous solution, pour into acetone, let stand for 12 hours, filter, wash with acetone 4 times, and vacuum dry at 50°C for 23 hours to obtain modified sodium alginate;

[0038] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexyl phenyl 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-hydroxycyclohexyl phenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let stand for 12 hours, and evenly coat on a glass plate with a thickness of 0.1 mm. Let stand for 4 minutes under a 500 W ultraviolet lamp, scrape off, and obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0039] Embodiment 3:

[0040] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0041] (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 uniformly added to a graphene oxide aqueous solution with a mass of 6 times that of the 3-diethylaminopropylamine aqueous solution within 10 minutes, 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 a 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;

[0042] (2) Mix cellulose, ethanol and 4'-bromo-2,2':6',2"-terpyridine in a mass ratio of 1:5:0.2, stir at 50°C and 300 r / min for 9 h, filter, wash with deionized water for 5 times, and vacuum dry at 50°C for 24 h to obtain pre-modified cellulose; heat maleic anhydride to 120°C to obtain maleic anhydride; mix pre-modified cellulose and maleic anhydride in a mass ratio of 1:7, stir at 120°C and 300 r / min for 260 min, wash with deionized water until neutral, and vacuum dry at 115°C for 24 h to obtain modified cellulose;

[0043] (3) Mix acetic acid and deionized water in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; mix sodium alginate and deionized water in a mass ratio of 1:26, stir at 300 r / min for 14 hours, adjust the pH to 9.3 with a 0.2 m sodium hydroxide aqueous solution, add 3,4-epoxy-1-butene in an amount of 0.3 times the mass of sodium alginate, heat to 80°C, continue stirring for 9 hours, adjust the pH to neutral with an acetic acid aqueous solution, pour into acetone, let stand for 14 hours, filter, wash with acetone 5 times, and vacuum dry at 55°C for 24 hours to obtain modified sodium alginate;

[0044] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.05 part of 1-hydroxycyclohexyl phenyl ketone, 5 parts of modified sodium alginate, 0.8 part 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-hydroxycyclohexyl phenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 6 hours, let stand for 13 hours, and evenly coat on a glass plate with a thickness of 0.12 mm. Let stand for 5 minutes under a 500 W ultraviolet lamp, and scrape off to obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0045] Comparative Example 1:

[0046] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0047] (1) Graphene oxide and deionized water were mixed in a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water were mixed in 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 with a mass of 5 times that 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 for 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 in a mass ratio of 1:4:0.7, stirred at 45°C and 250 r / min for 8 hours, filtered, washed with ether for 4 times, and vacuum dried at 45°C for 23 hours to obtain functionalized graphene oxide;

[0048] (2) Mix cellulose, ethanol and 4'-bromo-2,2':6',2"-terpyridine in a mass ratio of 1:4:0.15, stir at 45°C and 250 r / min for 8 h, filter, wash with deionized water for 4 times, and vacuum dry at 45°C for 23 h to obtain pre-modified cellulose; heat maleic anhydride to 110°C to obtain maleic anhydride; mix pre-modified cellulose and maleic anhydride in a mass ratio of 1:6, stir at 110°C and 250 r / min for 240 min, wash with deionized water until neutral, and vacuum dry at 110°C for 23 h to obtain modified cellulose;

[0049] (3) Mix acetic acid and deionized water in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; mix sodium alginate and deionized water in a mass ratio of 1:23, stir at 250 r / min for 12 hours, adjust the pH to 9 with a 0.2 m sodium hydroxide aqueous solution, add 3,4-epoxy-1-butene in an amount of 0.25 times the mass of sodium alginate, heat to 75°C, continue stirring for 8 hours, adjust the pH to neutral with an acetic acid aqueous solution, pour into acetone, let stand for 12 hours, filter, wash with acetone 4 times, and vacuum dry at 50°C for 23 hours to obtain modified sodium alginate;

[0050] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexyl phenyl 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-hydroxycyclohexyl phenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let stand for 12 hours, and evenly coat on a glass plate with a thickness of 0.1 mm. Let stand for 4 minutes under a 500 W ultraviolet lamp, scrape off, and obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0051] Comparative Example 2:

[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) 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 for 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;

[0054] (2) Mix acetic acid and deionized water in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; mix sodium alginate and deionized water in a mass ratio of 1:23, stir at 250 r / min for 12 hours, adjust the pH to 9 with a 0.2 m sodium hydroxide aqueous solution, add 3,4-epoxy-1-butene in an amount of 0.25 times the mass of sodium alginate, heat to 75°C, continue stirring for 8 hours, adjust the pH to neutral with an acetic acid aqueous solution, pour into acetone, let stand for 12 hours, filter, wash with acetone 4 times, and vacuum dry at 50°C for 23 hours to obtain modified sodium alginate;

[0055] (3) Take 1 part of graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexyl phenyl 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-hydroxycyclohexyl phenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let stand for 12 hours, and evenly coat on a glass plate with a thickness of 0.1 mm. Let stand for 4 minutes under a 500 W ultraviolet lamp, scrape off, and obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0056] Comparative Example 3

[0057] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0058] (1) Graphene oxide and deionized water are mixed at a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water are mixed at a mass ratio of 1:200 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution is uniformly added to a graphene oxide aqueous solution with a mass of 5 times that 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 for 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 h, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 h 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 h, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 h to obtain functionalized graphene oxide;

[0059] (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;

[0060] (3) Mix acetic acid and deionized water in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; mix sodium alginate and deionized water in a mass ratio of 1:23, stir at 250 r / min for 12 hours, adjust the pH to 9 with a 0.2 m sodium hydroxide aqueous solution, add 3,4-epoxy-1-butene in an amount of 0.25 times the mass of sodium alginate, heat to 75°C, continue stirring for 8 hours, adjust the pH to neutral with an acetic acid aqueous solution, pour into acetone, let stand for 12 hours, filter, wash with acetone 4 times, and vacuum dry at 50°C for 23 hours to obtain modified sodium alginate;

[0061] (4) Take 1 part of functionalized graphene oxide, 1 part of modified cellulose, 0.04 parts of 1-hydroxycyclohexyl phenyl 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-hydroxycyclohexyl phenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let stand for 12 hours, and evenly coat on a glass plate with a thickness of 0.1 mm. Let stand for 4 minutes under a 500 W ultraviolet lamp, scrape off, and obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0062] Comparative Example 4

[0063] A method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps:

[0064] (1) Graphene oxide and deionized water are mixed at a mass ratio of 1:200 to obtain a graphene oxide aqueous solution; 3-diethylaminopropylamine and deionized water are mixed at a mass ratio of 1:200 to obtain a 3-diethylaminopropylamine aqueous solution; the 3-diethylaminopropylamine aqueous solution is uniformly added to a graphene oxide aqueous solution with a mass of 5 times that 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 for 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 h, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 h 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 h, filtered, washed with ether 4 times, and vacuum dried at 45°C for 23 h to obtain functionalized graphene oxide;

[0065] (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 for 4 times, and vacuum dried at 45°C for 23 h to obtain pre-modified cellulose;

[0066] (3) Mix acetic acid and deionized water in a mass ratio of 1:1 to obtain an acetic acid aqueous solution; mix sodium alginate and deionized water in a mass ratio of 1:23, stir at 250 r / min for 12 hours, adjust the pH to 9 with a 0.2 m sodium hydroxide aqueous solution, add 3,4-epoxy-1-butene in an amount of 0.25 times the mass of sodium alginate, heat to 75°C, continue stirring for 8 hours, adjust the pH to neutral with an acetic acid aqueous solution, pour into acetone, let stand for 12 hours, filter, wash with acetone 4 times, and vacuum dry at 50°C for 23 hours to obtain modified sodium alginate;

[0067] (4) Take 1 part of functionalized graphene oxide, 1 part of pre-modified cellulose, 0.04 parts of 1-hydroxycyclohexyl phenyl 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-hydroxycyclohexyl phenyl ketone, modified sodium alginate and deionized water, ultrasonicate for 5 hours, let stand for 12 hours, and evenly coat on a glass plate with a thickness of 0.1 mm. Let stand for 4 minutes under a 500 W ultraviolet lamp, scrape off, and obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

[0068] Test Example 1:

[0069] Antimicrobial testing

[0070] According to QB / T2591, the selected bacteria were Staphylococcus aureus and Escherichia coli. The results are shown in Table 1.

[0071] Table 1

[0072]

[0073]

[0074] 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.

[0075] 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 indicates 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, ions are exchanged with amino groups and hydroxyls on the cell surface, thereby destroying the original structure of the cell membrane, accelerating membrane damage and cell death, thereby achieving an antibacterial effect.

[0076] Test Example 2:

[0077] Metal ion adsorption test

[0078] At room temperature, add 25 cm2 of copper ion solution to 50 mL of 25 mg / L copper ion solution. 2 The copper ion concentration was measured after 60 min for a film with a thickness of 0.2 cm. The results are shown in Table 2.

[0079] Table 2

[0080]

[0081]

[0082] From the comparison of the experimental data in Table 2, it can be found that the adsorption filtration membrane for treating heavy metal ion pollution in water prepared by the present invention has good metal ion adsorption capacity.

[0083] 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, 3 are lower than those of Comparative Example 1, which indicates that porphyrin can complex with metal ions to reduce the metal ion concentration in water;

[0084] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found 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 to enrich the cellulose with terpyridine structure, which can adsorb heavy metal substances and reduce the metal ion concentration in water.

[0085] 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, 3 is lower than that of Comparative Example 4, which shows that the pre-modified cellulose reacts with maleic anhydride to make 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 being able to efficiently adsorb heavy metal pollutants and reduce the metal ion concentration in water.

[0086] Test Example 3:

[0087] Organic matter degradation test

[0088] Add 25 cm2 iron ion solution to 50 mL of 20 mg / L iron ion solution. 2 The film with a thickness of 0.2 cm was taken out after 60 minutes, vacuum dried at -5℃ for 24 hours, prepared with 25mL of 10ppm methylene blue solution, and then placed the filter membrane in the methylene blue solution, ultrasonicated, turned on the power of the photocatalytic device for 60 minutes, and calculated the degradation efficiency by the change of absorbance at 665nm. The results are shown in Table 3.

[0089] Table 3

[0090] Degradation efficiency Example 1 98.7％ Example 2 99.1％ Example 3 99.0％ Comparative Example 1 13.5％ Comparative Example 2 14.1％ Comparative Example 3 98.9％ Comparative Example 4 98.6％

[0091] 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.

[0092] 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, 3 is higher than that of Comparative Example 1, which shows that porphyrin forms a metal-organic framework after metal chelation in wastewater, and can degrade organic pollutants under photocatalytic conditions.

[0093] 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. An adsorption filtration membrane for treating heavy metal ion pollution in water, characterized in that: The water body heavy metal ion pollution treatment adsorption filtration membrane is prepared by reacting sodium alginate with propylene oxide to obtain modified sodium alginate; and reacting modified sodium alginate, modified cellulose, functionalized graphene oxide, trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and a photoinitiator to form a membrane. The modified sodium alginate is prepared by reacting sodium alginate with propylene oxide; The modified cellulose is prepared by reacting cellulose with 4'-bromo-2,2':6',2"-terpyridine and maleic anhydride in sequence; The functionalized graphene oxide is prepared by sequentially reacting graphene oxide with 3-diethylaminopropylamine, tetrabromophenylporphyrin and N,N-diethylallylamine.

2. 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 filtration membrane for treating heavy metal ion pollution in water bodies mainly comprises the following preparation steps: (1) adding a 3-diethylaminopropylamine aqueous solution to a graphene oxide aqueous solution of 4 to 6 times the mass of the 3-diethylaminopropylamine aqueous solution at a uniform rate within 8 to 10 minutes, stirring at 85 to 95° C. and 200 to 300 r / min for 25 to 35 minutes, filtering, washing with deionized water for 3 to 5 times, and drying at 55 to 65° C. for 22 to 26 hours to obtain pre-modified graphene oxide; mixing the pre-modified graphene oxide, dichloromethane and tetrabromophenylporphyrin in a mass ratio of 1:3 to 5:0.6 to 0.8, and heating at 40 to 5 0°C, stirring at 200-300 r / min for 7-9h, filtering, washing with ether for 3-5 times, and vacuum drying at 40-50°C for 22-24h to obtain modified graphene oxide; modifying graphene oxide, ethanol and N,N-diethylallylamine are mixed in a mass ratio of 1:3-5:0.6-0.8, stirring at 40-50°C, 200-300 r / min for 7-9h, filtering, washing with ether for 3-5 times, and vacuum drying at 40-50°C for 22-24h to obtain functionalized graphene oxide; (2) mixing cellulose, ethanol and 4'-bromo-2,2':6',2"-terpyridine in a mass ratio of 1:3-5:0.1-0.2, stirring at 40-50°C and 200-300 r / min for 7-9 hours, filtering, washing with deionized water for 3-5 times, and vacuum drying at 40-50°C for 22-24 hours to obtain pre-modified cellulose; Pre-modified cellulose and maleic anhydride are 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 modified cellulose; (3) Sodium alginate and deionized water are mixed in a mass ratio of 1:20-26, stirred at 200-300 r / min for 10-14 h, the pH is adjusted to 8.7-9.3 with a sodium hydroxide aqueous solution, 3,4-epoxy-1-butene in an amount of 0.2-0.3 times the mass of the sodium alginate is added, the temperature is raised to 70-80° C., stirring is continued for 7-9 h, the pH is adjusted to neutral with an acetic acid aqueous solution, poured into acetone, allowed to stand for 10-14 h, filtered, washed with acetone for 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 part of photoinitiator, 4-5 parts of modified sodium alginate, 0.6-0.8 part of trans, trans-1,3-butadiene-1,4-dicarboxylic acid, and 3.5-4.5 parts of deionized water 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 stand for 11-13 hours, and evenly coat on a glass plate with a thickness of 0.08-0.12 mm. Let stand for 3-5 minutes under a 500 W ultraviolet lamp, scrape off, and obtain an adsorption filter membrane for treating heavy metal ion pollution in water bodies.

3. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 2, 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.

4. The method for preparing a water body heavy metal ion pollution treatment adsorption filtration membrane according to claim 2, 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.

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

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

7. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 2, characterized in that: The sodium hydroxide aqueous solution in step (3) is a 0.2M sodium hydroxide aqueous solution.

8. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 2, 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.

9. The method for preparing an adsorption filtration membrane for treating heavy metal ion pollution in water bodies according to claim 2, characterized in that: The photoinitiator in step (4) is 1-hydroxycyclohexyl phenyl ketone.

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