CN108970425B - Polymer membrane for high-salinity wastewater treatment and preparation method thereof - Google Patents

Polymer membrane for high-salinity wastewater treatment and preparation method thereof Download PDF

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CN108970425B
CN108970425B CN201810963700.9A CN201810963700A CN108970425B CN 108970425 B CN108970425 B CN 108970425B CN 201810963700 A CN201810963700 A CN 201810963700A CN 108970425 B CN108970425 B CN 108970425B
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不公告发明人
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Zhang Chunyun
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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Abstract

The invention provides a preparation method of a polymer film for treating high-salinity wastewater, which comprises the following steps: i, preparing a fluorine-containing piperazine amide polymer; II, modifying chitosan; III, modifying the surface of graphene oxide; and IV, preparing a film. The invention also discloses the polymer membrane for treating the high-salinity wastewater, which is prepared according to the preparation method. The preparation method of the polymer membrane for treating the high-salinity wastewater disclosed by the invention is simple and easy to implement, has low dependence on equipment, has low requirements on reaction conditions, is easy to obtain raw materials, is low in price and is suitable for large-scale production. The prepared polymer membrane for treating high-salinity wastewater has the advantages of stable performance, large water flux, high salt removal rate, excellent mechanical property and strong corrosion resistance and stain resistance.

Description

Polymer membrane for high-salinity wastewater treatment and preparation method thereof
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a polymer membrane for treating high-salinity wastewater and a preparation method thereof.
Background
With the progress of global industrialization, environmental problems and energy problems are still main factors restricting economic development and social progress, and especially in recent years, industrial wastewater represented by papermaking wastewater has large discharge amount, is rich in various toxic and harmful pollutants, has large harm to ecological environment and human health, and is difficult to treat and purify. The search for effective wastewater treatment technologies to treat industrial wastewater has become a problem that enterprises have to face.
At present, the treatment technology of industrial wastewater mainly comprises the following steps: biological treatment technology, chemical treatment technology, adsorption filtration and other physical treatment technologies. The technologies have a good treatment effect on organic pollutants in industrial wastewater, but the industrial wastewater contains a large amount of salt substances besides the organic pollutants, and the substances cause the salinity and the chloride ion content of the wastewater to be high, have strong corrosivity and are very difficult to treat.
At present, the treatment of the high-salt wastewater mainly adopts a thermal concentration process, such as multi-effect evaporation, and the principle of the process is to concentrate the high-salt wastewater by utilizing heat energy to obtain concentrated water and clear water. The process has high energy consumption, needs large-scale equipment with large occupied area, and simultaneously, salt ions in the wastewater easily cause equipment corrosion and scaling, thereby reducing the treatment efficiency of the equipment and increasing the later maintenance and maintenance cost of the equipment. The membrane separation technology effectively combines the effective filtration performance of the membrane with the traditional multiple-effect evaporation technology, makes up the defects of the traditional multiple-effect evaporation technology, has the characteristics of low energy consumption, good quality, less pollution, simple process, simple operation and the like, and gradually replaces the traditional multiple-effect evaporation to become the mainstream technology in the industry. However, the membrane material in the prior art has complex preparation process, high preparation cost, poor strength, poor corrosion resistance and poor anti-fouling performance, and the defects limit the application of the membrane material in the treatment of high-salinity wastewater.
The Chinese patent with application publication number CN107486031 discloses an organic silicon composite membrane for high-salinity wastewater treatment, which is prepared by the following steps: the method comprises the steps of coating silica sol on an organic material through high-speed spin coating, forming a very thin inorganic prefabricated layer after low-temperature heat treatment, then spin coating the silica sol on the prefabricated layer, and then performing low-temperature heat treatment.
Therefore, the development of a high-salt wastewater treatment membrane with stable performance, large water flux, high salt removal rate, excellent mechanical properties and strong corrosion resistance and pollution resistance is imperative.
Disclosure of Invention
The invention mainly aims to provide a polymer membrane for treating high-salinity wastewater and a preparation method of the polymer membrane for treating the high-salinity wastewater, aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a polymer membrane for treating high-salinity wastewater comprises the following steps:
i, preparation of a fluorine-containing piperazine amide polymer: dissolving piperazine-2-formamide and 1, 4-bis (2',3' -epoxypropyl) perfluorobutane in a high-boiling-point solvent to form a solution, adding a basic catalyst into the solution, stirring and reacting at 90-100 ℃ for 8-10 hours, then adding 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine into the solution, continuing stirring and reacting for 1-2 hours, then cooling to room temperature, precipitating in water, washing the precipitated polymer with water for 3-5 times, then washing with ethanol for 4-6 times, and drying in a vacuum drying oven at 70-80 ℃ for 12-18 hours to obtain the fluorine-containing piperazine amide polymer;
II, modification of chitosan: adding chitosan, chloromethyl triethoxysilane and potassium carbonate into an organic solvent, stirring and reacting for 4-6 hours at 50-60 ℃, removing the solvent by rotary evaporation to obtain a crude product, washing the crude product with deionized water for 3-5 times, and drying for 10-15 hours at 90-100 ℃ in a vacuum drying oven to obtain modified chitosan;
III, modifying the surface of graphene oxide: adding graphene oxide into chloroform, adding 1,3,5, 7-tetra (4-aminophenyl) adamantane into the chloroform, stirring the mixture to react for 4 to 6 hours at the temperature of between 70 and 80 ℃, carrying out centrifugal separation, washing the mixture for 3 to 5 times by using acetone, and centrifuging the mixture again to obtain surface modified graphene oxide;
IV, preparation of a film: mixing the fluorine-containing piperazine amide polymer prepared in the step I, the modified chitosan prepared in the step II, the surface modified graphene oxide prepared in the step III, a pore-forming agent and N-methyl pyrrolidone, stirring at 30-60 ℃ for 8-10 hours, standing for 6-8 hours, pouring the mixture on a polytetrafluoroethylene flat plate by adopting an immersion precipitation phase conversion method, scraping a membrane by using a membrane scraping knife, staying in the air for 1-2 hours, and then placing the mixture in a coagulating bath to obtain the polymer membrane for treating high-salinity wastewater.
Furthermore, in the step I, the mass ratio of the piperazine-2-formamide, the 1, 4-bis (2',3' -epoxypropyl) perfluorobutane, the high boiling point solvent, the basic catalyst and the 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine is 1:2.43 (10-15): 0.2-0.5: 0.1.
Preferably, the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the alkaline catalyst is selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide.
Furthermore, the mass ratio of the chitosan, the chloromethyl triethoxysilane, the potassium carbonate and the organic solvent in the step II is (3-5):0.5:0.5: (9-15).
Preferably, the organic solvent is selected from one or more of chloroform, acetonitrile and acetone.
Further, in the step III, the mass ratio of the graphene oxide to the chloroform to the 1,3,5, 7-tetra (4-aminophenyl) adamantane is (3-5): (9-15): 0.5.
Furthermore, in the step IV, the mass ratio of the fluorine-containing piperazine amide polymer to the modified chitosan to the surface-modified graphene oxide to the pore-forming agent to the N-methyl pyrrolidone is (40-60) to (5-10) to (7-15) to (1-5) to (120-180).
Preferably, the pore-forming agent is selected from one or more of amine chloride, lithium perchlorate, glycerol and polyvinylpyrrolidone.
Preferably, the coagulating bath adopts one or more solvents selected from water, ethanol and acetone.
The polymer membrane for treating the high-salinity wastewater is prepared by adopting the preparation method of the polymer membrane for treating the high-salinity wastewater.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the polymer membrane for treating high-salinity wastewater disclosed by the invention is simple and feasible in preparation method, low in equipment dependence, not harsh in requirements on reaction conditions, easy in obtaining of raw materials, low in price and suitable for large-scale production.
(2) The polymer membrane for treating high-salinity wastewater disclosed by the invention overcomes the technical problems of complex preparation process, higher preparation cost, poor strength, poor corrosion resistance, small water flux and poor anti-fouling performance of the polymer membrane for treating high-salinity wastewater in the prior art, and has the advantages of stable performance, large water flux, high salt removal rate, excellent mechanical property and strong corrosion resistance and anti-fouling capability.
(3) The polymer film for treating high-salinity wastewater disclosed by the invention combines the advantages of organic fluorine and polyamide film-forming polymers, and introduces the triazine structure end capping, so that the polymer film has good weather resistance, excellent mechanical property and good anti-fouling and salt-blocking properties; the modified chitosan is added, and the structure containing more active hydroxyl groups and side chain hydroxyl groups prepared by polycondensation act synergistically, so that the hydrophilicity of the polymer film is enhanced, and the water flux of the polymer film is remarkably improved. The chitosan is modified, so that the components are uniformly dispersed, and the compatibility is improved; the surface modified graphene oxide is added, so that the salt removal rate, the mechanical strength and the oxidation resistance are further improved, the dispersity and the compatibility of the graphene oxide can be improved through surface modification, and the weather resistance can also be improved; the components have synergistic effect, so that the polymer membrane for treating the high-salinity wastewater has excellent comprehensive performance.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The raw materials used in the examples of the present invention were purchased from Mobei (Shanghai) Biotech limited.
Example 1
A preparation method of a polymer membrane for treating high-salinity wastewater comprises the following steps:
i, preparation of a fluorine-containing piperazine amide polymer: dissolving 10g of piperazine-2-formamide and 24.3g of 1, 4-bis (2',3' -epoxypropyl) perfluorobutane in 100g of dimethyl sulfoxide to form a solution, adding 2g of potassium carbonate into the solution, stirring the solution at 90 ℃ for reaction for 8 hours, adding 1g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine into the solution, continuing to stir the solution for reaction for 1 hour, cooling the solution to room temperature, precipitating the solution in water, washing the precipitated polymer with water for 3 times, washing the polymer with ethanol for 4 to 6 times, and drying the polymer in a vacuum drying oven at 70 ℃ for 12 hours to obtain the fluorine-containing piperazine amide polymer;
II, modification of chitosan: adding 30g of chitosan, 5g of chloromethyltriethoxysilane and 5g of potassium carbonate into 90g of chloroform, stirring and reacting for 4 hours at 50 ℃, performing rotary evaporation to remove a solvent to obtain a crude product, washing the crude product for 3 times by using deionized water, and drying for 10 hours at 90 ℃ in a vacuum drying oven to obtain modified chitosan;
III, modifying the surface of graphene oxide: adding 30g of graphene oxide into 90g of chloroform, adding 5g of 1,3,5, 7-tetra (4-aminophenyl) adamantane, stirring and reacting for 4 hours at 70 ℃, carrying out centrifugal separation, washing for 3 times by using acetone, and centrifuging again to obtain surface modified graphene oxide;
IV, preparation of a film: mixing 20g of the fluorine-containing piperazine amide polymer prepared in the step I, 2.5g of the modified chitosan prepared in the step II, 3.5g of the surface-modified graphene oxide prepared in the step III, 0.5g of amine chloride and 60g of N-methyl pyrrolidone, stirring at 30 ℃ for 8 hours, standing for 6 hours, pouring the mixture on a polytetrafluoroethylene flat plate by adopting an immersion precipitation phase conversion method, scraping a membrane by using a membrane scraping knife, staying in the air for 1 hour, and then placing in a coagulating bath to obtain the polymer membrane for treating high-salinity wastewater; the coagulating bath adopts water as a solvent.
The polymer membrane for treating the high-salinity wastewater is prepared by adopting the preparation method of the polymer membrane for treating the high-salinity wastewater.
Example 2
A preparation method of a polymer membrane for treating high-salinity wastewater comprises the following steps:
i, preparation of a fluorine-containing piperazine amide polymer: dissolving 10g of piperazine-2-formamide and 24.3g of 1, 4-bis (2',3' -epoxypropyl) perfluorobutane in 110g of N, N-dimethylformamide to form a solution, adding 3g of sodium carbonate into the solution, stirring the solution at 93 ℃ for reaction for 8.5 hours, adding 1g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine into the solution, continuing to stir the solution for reaction for 1.2 hours, cooling the solution to room temperature, precipitating the solution in water, washing the precipitated polymer with water for 4 times, washing the polymer with ethanol for 5 times, and drying the polymer in a vacuum drying oven at 73 ℃ for 13 hours to obtain the fluorine-containing piperazine amide polymer;
II, modification of chitosan: adding 35g of chitosan, 5g of chloromethyltriethoxysilane and 5g of potassium carbonate into 100g of acetonitrile, stirring and reacting for 4.5 hours at 53 ℃, performing rotary evaporation to remove a solvent to obtain a crude product, washing the crude product for 4 times by using deionized water, and drying for 11 hours at 93 ℃ in a vacuum drying oven to obtain modified chitosan;
III, modifying the surface of graphene oxide: adding 35g of graphene oxide into 100g of chloroform, adding 5g of 1,3,5, 7-tetra (4-aminophenyl) adamantane, stirring and reacting at 73 ℃ for 4.5 hours, centrifugally separating, washing with acetone for 4 times, and centrifuging again to obtain surface-modified graphene oxide;
IV, preparation of a film: mixing 23g of the fluorine-containing piperazine amide polymer prepared in the step I, 3g of the modified chitosan prepared in the step II, 4g of the surface-modified graphene oxide prepared in the step III, 1g of lithium perchlorate and 70g of N-methylpyrrolidone, stirring at 35 ℃ for 8.5 hours, standing for 6.5 hours, pouring the mixture on a polytetrafluoroethylene flat plate by adopting an immersion precipitation phase conversion method, scraping a membrane by using a membrane scraping knife, staying in the air for 1.5 hours, and then placing the mixture in a coagulating bath to obtain the polymer membrane for treating the high-salt wastewater; the coagulating bath adopts ethanol as a solvent.
The polymer membrane for treating the high-salinity wastewater is prepared by adopting the preparation method of the polymer membrane for treating the high-salinity wastewater.
Example 3
A preparation method of a polymer membrane for treating high-salinity wastewater comprises the following steps:
i, preparation of a fluorine-containing piperazine amide polymer: dissolving 10g of piperazine-2-formamide and 24.3g of 1, 4-bis (2',3' -epoxypropyl) perfluorobutane in 125g of N-methylpyrrolidone to form a solution, adding 3.5g of potassium hydroxide into the solution, stirring the solution at 95 ℃ for reaction for 9 hours, adding 1g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine into the solution, continuing to stir the solution for reaction for 1.6 hours, cooling the solution to room temperature, precipitating the solution in water, washing the precipitated polymer with water for 5 times, washing the polymer with ethanol for 6 times, and drying the polymer in a vacuum drying oven at 75 ℃ for 15 hours to obtain the fluorine-containing piperazine amide polymer;
II, modification of chitosan: adding 40g of chitosan, 5g of chloromethyltriethoxysilane and 5g of potassium carbonate into 125g of acetone, stirring and reacting for 5 hours at 56 ℃, performing rotary evaporation to remove the solvent to obtain a crude product, washing the crude product for 4 times by using deionized water, and drying for 13.5 hours at 96 ℃ in a vacuum drying oven to obtain modified chitosan;
III, modifying the surface of graphene oxide: adding 40g of graphene oxide into 130g of chloroform, adding 5g of 1,3,5, 7-tetra (4-aminophenyl) adamantane, stirring and reacting at 76 ℃ for 5 hours, centrifugally separating, washing with acetone for 4 times, and centrifuging again to obtain surface-modified graphene oxide;
IV, preparation of a film: mixing 26g of the fluorine-containing piperazine amide polymer prepared in the step I, 4g of the modified chitosan prepared in the step II, 5g of the surface-modified graphene oxide prepared in the step III, 1.5g of glycerol and 78g of N-methyl pyrrolidone, stirring at 45 ℃ for 9.2 hours, standing for 7.3 hours, pouring the mixture on a polytetrafluoroethylene flat plate by adopting an immersion precipitation phase conversion method, scraping a membrane by using a membrane scraping knife, staying in the air for 1.7 hours, and then placing in a coagulating bath to obtain the polymer membrane for treating high-salinity wastewater; the coagulating bath adopts acetone as a solvent.
The polymer membrane for treating the high-salinity wastewater is prepared by adopting the preparation method of the polymer membrane for treating the high-salinity wastewater.
Example 4
A preparation method of a polymer membrane for treating high-salinity wastewater comprises the following steps:
i, preparation of a fluorine-containing piperazine amide polymer: dissolving 10g of piperazine-2-formamide and 24.3g of 1, 4-bis (2',3' -epoxypropyl) perfluorobutane in 140g of a high-boiling-point solvent to form a solution, adding 4.5g of a basic catalyst into the solution, stirring the solution at 98 ℃ for reaction for 9.5 hours, adding 1g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine into the solution, continuing to stir the solution for reaction for 1.8 hours, cooling the solution to room temperature, precipitating the solution in water, washing the precipitated polymer with water for 5 times, washing the polymer with ethanol for 5 times, and drying the polymer in a vacuum drying oven at 78 ℃ for 17 hours to obtain the fluorine-containing piperazine amide polymer; the high-boiling-point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to a mass ratio of 1:1: 2; the alkaline catalyst is a mixture formed by mixing potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide according to the mass ratio of 2:1:3: 1;
II, modification of chitosan: adding 45g of chitosan, 5g of chloromethyltriethoxysilane and 5g of potassium carbonate into 140g of an organic solvent, stirring and reacting for 5.5 hours at 58 ℃, performing rotary evaporation to remove the solvent to obtain a crude product, washing the crude product for 4 times by using deionized water, and drying for 14.5 hours at 97 ℃ in a vacuum drying oven to obtain modified chitosan; the organic solvent is a mixture formed by mixing chloroform, acetonitrile and acetone according to the mass ratio of 3:4: 2;
III, modifying the surface of graphene oxide: adding 45g of graphene oxide into 145g of chloroform, adding 5g of 1,3,5, 7-tetra (4-aminophenyl) adamantane, stirring and reacting at 78 ℃ for 5.5 hours, centrifugally separating, washing with acetone for 5 times, and centrifuging again to obtain surface-modified graphene oxide;
IV, preparation of a film: mixing 28g of the fluorine-containing piperazine amide polymer prepared in the step I, 4.5g of the modified chitosan prepared in the step II, 6.5g of the surface-modified graphene oxide prepared in the step III, 2g of a pore-forming agent and 85g of N-methyl pyrrolidone, stirring at 55 ℃ for 9.5 hours, standing for 7.5 hours, pouring the mixture on a polytetrafluoroethylene flat plate by adopting an immersion precipitation phase conversion method, scraping a membrane by using a membrane scraping knife, staying in the air for 1.9 hours, and then placing the mixture in a coagulating bath to obtain the polymer membrane for treating high-salt wastewater; the pore-foaming agent is a mixture formed by mixing amine chloride, lithium perchlorate, glycerol and polyvinylpyrrolidone according to the mass ratio of 2:1:1: 3; the coagulating bath adopts a mixture of water, ethanol and acetone in a mass ratio of 1:1: 5.
The polymer membrane for treating the high-salinity wastewater is prepared by adopting the preparation method of the polymer membrane for treating the high-salinity wastewater.
Example 5
A preparation method of a polymer membrane for treating high-salinity wastewater comprises the following steps:
i, preparation of a fluorine-containing piperazine amide polymer: dissolving piperazine-2-formamide 10g and 1, 4-bis (2',3' -epoxypropyl) perfluorobutane 24.3g in dimethyl sulfoxide 150g to form a solution, adding sodium hydroxide 5g into the solution, stirring at 100 ℃ for reaction for 10 hours, then adding 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine 1g, continuing to stir for reaction for 2 hours, then cooling to room temperature, precipitating in water, washing the precipitated polymer with water for 5 times, then washing with ethanol for 6 times, and then drying at 80 ℃ in a vacuum drying oven for 18 hours to obtain the fluorine-containing piperazine amide polymer;
II, modification of chitosan: adding 50g of chitosan, 5g of chloromethyltriethoxysilane and 5g of potassium carbonate into 150g of chloroform, stirring and reacting for 6 hours at 60 ℃, performing rotary evaporation to remove a solvent to obtain a crude product, washing the crude product for 5 times by using deionized water, and drying for 15 hours at 100 ℃ in a vacuum drying oven to obtain modified chitosan;
III, modifying the surface of graphene oxide: adding 50g of graphene oxide into 150g of chloroform, adding 5g of 1,3,5, 7-tetra (4-aminophenyl) adamantane, stirring and reacting at 80 ℃ for 6 hours, centrifugally separating, washing with acetone for 5 times, and centrifuging again to obtain surface modified graphene oxide;
IV, preparation of a film: mixing 30g of the fluorine-containing piperazine amide polymer prepared in the step I, 5g of the modified chitosan prepared in the step II, 7.5g of the surface-modified graphene oxide prepared in the step III, 2.5g of polyvinylpyrrolidone and 90g of N-methyl pyrrolidone, stirring at 60 ℃ for 10 hours, standing for 8 hours, pouring the mixture on a polytetrafluoroethylene flat plate by adopting an immersion precipitation phase conversion method, scraping a membrane by using a membrane scraping knife, staying in the air for 2 hours, and then placing in a coagulating bath to obtain the polymer membrane for treating high-salinity wastewater; the coagulating bath adopts water as a solvent.
The polymer membrane for treating the high-salinity wastewater is prepared by adopting the preparation method of the polymer membrane for treating the high-salinity wastewater.
Comparative example 1
This example provides a polymer membrane for treating high salinity wastewater, which is similar in formulation and preparation to example 1, except that modified chitosan is not added.
Comparative example 2
The present example provides a polymer membrane for treating high salinity wastewater, which has a formulation and a preparation method similar to those of example 1, except that surface-modified graphene oxide is not added.
Comparative example 3
The present invention provides a corrosion-resistant and stain-resistant membrane for treating high-salinity wastewater, and the formula and the preparation method thereof are the same as in embodiment 1 of the invention patent CN107715700A in China.
The polymer membranes for treating high-salinity wastewater prepared in the above examples 1 to 5 and comparative examples 1 to 2 and the corrosion-resistant and fouling-resistant membrane for treating high-salinity wastewater of comparative example 3 were subjected to performance tests, and the test results are shown in table 1. The test method is as follows:
(1) retention rate: the membrane performance evaluation instrument is adopted for determination (MPY-II type membrane performance evaluation instrument of Hangzhou water treatment center of national ocean office) The testing condition is 0.2Mpa, and the effective filtration area of the membrane is 22.22cm2. Magnesium chloride with a salt concentration of 3.5 wt% was used.
(2) And (3) testing tensile strength: the test is carried out according to GB/T1040-2006 method for testing the tensile property of plastics.
(3) COD removal rate: testing was performed according to GB 11914-89.
TABLE 1
Figure GDA0002496173570000081
As can be seen from table 1, the polymer membrane for treating high-salinity wastewater disclosed in the embodiment of the present invention has more excellent tensile properties, higher COD removal rate and higher magnesium chloride retention rate compared with the corrosion-resistant and stain-resistant membrane for treating high-salinity wastewater in the prior art; the addition of the modified chitosan and the modified graphene oxide is beneficial to improving the performances of the polymer film.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A preparation method of a polymer membrane for treating high-salinity wastewater is characterized by comprising the following steps:
i, preparation of a fluorine-containing piperazine amide polymer: dissolving piperazine-2-formamide and 1, 4-bis (2',3' -epoxypropyl) perfluorobutane in a high-boiling-point solvent to form a solution, adding a basic catalyst into the solution, stirring and reacting at 90-100 ℃ for 8-10 hours, then adding 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine into the solution, continuing stirring and reacting for 1-2 hours, then cooling to room temperature, precipitating in water, washing the precipitated polymer with water for 3-5 times, then washing with ethanol for 4-6 times, and drying in a vacuum drying oven at 70-80 ℃ for 12-18 hours to obtain the fluorine-containing piperazine amide polymer;
II, modification of chitosan: adding chitosan, chloromethyl triethoxysilane and potassium carbonate into an organic solvent, stirring and reacting for 4-6 hours at 50-60 ℃, removing the solvent by rotary evaporation to obtain a crude product, washing the crude product with deionized water for 3-5 times, and drying for 10-15 hours at 90-100 ℃ in a vacuum drying oven to obtain modified chitosan;
III, modifying the surface of graphene oxide: adding graphene oxide into chloroform, adding 1,3,5, 7-tetra (4-aminophenyl) adamantane into the chloroform, stirring the mixture to react for 4 to 6 hours at the temperature of between 70 and 80 ℃, carrying out centrifugal separation, washing the mixture for 3 to 5 times by using acetone, and centrifuging the mixture again to obtain surface modified graphene oxide;
IV, preparation of a film: mixing the fluorine-containing piperazine amide polymer prepared in the step I, the modified chitosan prepared in the step II, the surface modified graphene oxide prepared in the step III, a pore-forming agent and N-methyl pyrrolidone, stirring at 30-60 ℃ for 8-10 hours, standing for 6-8 hours, pouring the mixture on a polytetrafluoroethylene flat plate by adopting an immersion precipitation phase conversion method, scraping a membrane by using a membrane scraping knife, staying in the air for 1-2 hours, and then placing the mixture in a coagulating bath to obtain the polymer membrane for treating high-salinity wastewater.
2. The method for preparing a polymer membrane for treating high-salinity wastewater according to claim 1, characterized in that the mass ratio of the piperazine-2-carboxamide, 1, 4-bis (2',3' -epoxypropyl) perfluorobutane, the high-boiling solvent, the basic catalyst and the 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazin-2-amine in step I is 1:2.43 (10-15): 0.2-0.5): 0.1.
3. The method for preparing a polymer membrane for high-salinity wastewater treatment according to claim 1, wherein the high-boiling point solvent is one or more selected from dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the alkaline catalyst is selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide.
4. The preparation method of the polymer membrane for high-salinity wastewater treatment according to claim 1, characterized in that the mass ratio of the chitosan, the chloromethyltriethoxysilane, the potassium carbonate and the organic solvent in the step II is (3-5):0.5:0.5 (9-15).
5. The method for preparing a polymer membrane for high-salinity wastewater treatment according to claim 1, wherein the organic solvent is selected from one or more of chloroform, acetonitrile and acetone.
6. The method for preparing a polymer membrane for high-salinity wastewater treatment according to claim 1, wherein the mass ratio of the graphene oxide, the chloroform and the 1,3,5, 7-tetrakis (4-aminophenyl) adamantane in the step III is (3-5):0.5 (9-15).
7. The method for preparing a polymer membrane for treating high-salinity wastewater according to claim 1, wherein the mass ratio of the fluorine-containing piperazine amide polymer, the modified chitosan, the surface-modified graphene oxide, the pore-forming agent and the N-methylpyrrolidone in step IV is (40-60): 5-10): 7-15): 1-5: 120-.
8. The method for preparing a polymer membrane for treating high-salinity wastewater according to claim 1, wherein the pore-forming agent is one or more selected from ammonium chloride, lithium perchlorate, glycerol and polyvinylpyrrolidone.
9. The method for preparing a polymer membrane for treating high-salinity wastewater according to claim 1, wherein the solvent used in the coagulating bath is one or more of water, ethanol and acetone.
10. A polymer membrane for high-salinity wastewater treatment prepared by the method for preparing the polymer membrane for high-salinity wastewater treatment according to any one of claims 1 to 9.
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