CN115364704A - Polyacrylonitrile-carbon nano tube electroactive film with selective oxidation function and application - Google Patents
Polyacrylonitrile-carbon nano tube electroactive film with selective oxidation function and application Download PDFInfo
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- CN115364704A CN115364704A CN202211306498.5A CN202211306498A CN115364704A CN 115364704 A CN115364704 A CN 115364704A CN 202211306498 A CN202211306498 A CN 202211306498A CN 115364704 A CN115364704 A CN 115364704A
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention provides a polyacrylonitrile-carbon nano tube electroactive membrane with a selective oxidation function and application thereof. The polyacrylonitrile-carbon nanotube electroactive membrane is used as an anode to be connected with a direct current power supply during filtration, macromolecular organic pollutants such as polysaccharide, protein and humus are physically intercepted by a polyacrylonitrile separating layer and pass through toxic and harmful micromolecular organic pollutants such as antibiotics, endocrine disruptors and persistent organic pollutants, the micromolecular organic pollutants reach the lower carbon nanotube electroactive layer and then undergo electrochemical oxidation reaction to be degraded, the macromolecular organic pollutants can be prevented from competing for electroactive membrane reaction sites, selective oxidative degradation of the toxic and harmful micromolecular organic pollutants in urban secondary effluent is realized, and the polyacrylonitrile-carbon nanotube electroactive membrane has important significance for guaranteeing the safety of secondary effluent recycling.
Description
Technical Field
The invention relates to the field of water treatment materials, in particular to a polyacrylonitrile-carbon nano tube electroactive film with a selective oxidation function and application thereof.
Background
The membrane separation technology is widely applied in the field of advanced sewage treatment. The micro-filtration, ultra-filtration, nano-filtration and reverse osmosis membrane can intercept various pollutants in biological treatment secondary effluent (urban secondary effluent for short) of the urban sewage plant according to the pore size of the micro-filtration, ultra-filtration, nano-filtration and reverse osmosis membrane, so that the sewage is deeply purified to meet the requirement of reuse water. When the advanced treatment is carried out on the secondary effluent of cities, the removal of toxic and harmful small-molecule organic pollutants such as antibiotics, endocrine disruptors, persistent organic pollutants and the like is the key for guaranteeing the recycling safety of sewage. However, since the molecular weight of the toxic and harmful small-molecule organic pollutants is usually 200 to 500 daltons, the toxic and harmful small-molecule organic pollutants can be removed only through a nanofiltration membrane and a reverse osmosis membrane, and the removal effect is only physical interception, namely, the toxic and harmful small-molecule organic pollutants are only transferred into a nanofiltration or reverse osmosis concentrated solution, are not chemically degraded and still have toxicity.
In recent years, the preparation of electroactive membranes by loading conductive and electrochemically reactive materials onto traditional membrane materials has become a hot point of research. The electroactive membrane is also connected with a power supply as an electrode when filtering sewage, so that pollutants in the sewage can be removed through physical interception, and the pollutants in the sewage can be degraded through electrochemical reaction. The characteristic of the electroactive film is very beneficial to removing toxic and harmful small-molecular organic pollutants, so that the removal effect can be improved, and the toxicity can be reduced.
It is worth noting that the urban secondary effluent contains a large amount of macromolecular organic pollutants such as polysaccharide, protein and humus besides toxic and harmful small molecular organic pollutants, and the currently reported electroactive membrane cannot realize selective oxidation of the toxic and harmful small molecular organic pollutants. Chinese patent CN112827366A discloses preparation and application of a nano zero-valent copper-based modified carbon nanotube filter membrane, and CN202010766254.X discloses preparation and application of a gold cluster-carbon nanotube electrocatalytic film. These two patents set up catalyst modification carbon nanotube electroactive layer in electroactive membrane upper surface and come to degrade organic pollutant in the sewage, but electroactive layer will contact with the macromolecule organic pollutant and the poisonous harmful micromolecule organic pollutant in the sewage simultaneously, and a large amount of reaction sites are occupied by macromolecule organic pollutant to do not do benefit to getting rid of poisonous harmful micromolecule organic pollutant. Chinese patent CN110496544A discloses a preparation method and application of an inorganic-organic composite carbon-based conductive ultrafiltration membrane, and CN110496543A discloses a preparation method of a silicon dioxide-polyether sulfone conductive ultrafiltration membrane, and the obtained ultrafiltration membrane and application thereof. In the two patents, the carbon cloth conducting layer is arranged on the lower surface of the electroactive film to carry out electrochemical degradation on the antibiotics, but the carbon cloth conducting layer does not have the function of removing macromolecular organic pollutants in secondary effluent in advance before oxidizing the antibiotics, and cannot realize selective oxidation on the antibiotics.
Disclosure of Invention
In view of this, the present invention provides a polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function, which utilizes a pore structure of a polyacrylonitrile separation layer on the upper portion of the electroactive membrane to physically trap macromolecular organic pollutants and permeate toxic and harmful small-molecule organic pollutants, and then utilizes a carbon nanotube electroactive layer on the lower portion of the electroactive membrane to oxidize the toxic and harmful small-molecule organic pollutants, thereby achieving the purpose of selectively oxidizing the toxic and harmful small-molecule organic pollutants.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a polyacrylonitrile-carbon nanotube electroactive membrane with a selective oxidation function comprises an upper polyacrylonitrile separation layer and a lower carbon nanotube electroactive layer, wherein the carbon nanotube electroactive layer is located on the back side of the polyacrylonitrile separation layer with large membrane pores, the aperture of the front side of the polyacrylonitrile separation layer is 2-8nm, the conductivity is 50-200S/m, and the polyacrylonitrile separation layer and the carbon nanotube electroactive layer are crosslinked through polyaniline.
Further, the polyacrylonitrile-carbon nanotube electroactive film is prepared by the following steps:
1) Preparation and hydrolysis of a polyacrylonitrile separation layer:
preparing a polyacrylonitrile membrane casting solution, preparing a polyacrylonitrile membrane by adopting a non-solvent phase inversion method, and contacting the back of the polyacrylonitrile membrane with a NaOH solution for hydrolysis;
2) Carbon nanotube electroactive layer loading:
preparing carbon nano tube dispersion liquid, wherein the polyacrylonitrile membrane has large membrane pores on the back and small membrane pores on the front, so that the carbon nano tube dispersion liquid is filtered by suction with the polyacrylonitrile membrane facing upwards on the back, and a carbon nano tube electroactive layer is formed on the back of the polyacrylonitrile membrane; thus, the front membrane pores can be used for filtering out macromolecules, and only small molecules can penetrate through the polyacrylonitrile membrane;
3) And (3) crosslinking:
dripping aniline solution with the thickness of 2-3 mm on the back of the polyacrylonitrile membrane loaded with the carbon nano tube electroactive layer, pouring the aniline solution after a period of time, and maintaining the back of the membrane in a wet state; dripping ammonium persulfate solution with the thickness of the liquid layer of 2-3 mm on the back of the membrane to react, and realizing crosslinking by utilizing aniline in-situ polymerization reaction; and pouring the ammonium persulfate solution and maintaining the wet state of the back of the membrane to continue the crosslinking reaction to obtain the polyacrylonitrile-carbon nano tube electroactive membrane.
Further, in the step 1), the mass fraction of polyacrylonitrile in the polyacrylonitrile membrane casting solution is 18-22%.
Further, the concentration of the NaOH solution in the step 1) is 1-2mol/L, the contact time of the NaOH solution and the NaOH solution is 2-8min, and the temperature of the NaOH solution is 40-60 ℃.
Further, the carbon nano tube adopted in the step 2) is a carboxylated carbon nano tube, the carboxyl content is 2% -4%, the conductivity of the electroactive layer is reduced due to too high carboxyl content, and the crosslinking effect is weakened due to too low carboxyl content; the mass fraction of the carbon nano tube dispersion liquid is 0.02-0.08%, the volume of the dispersion liquid is 50-100 mL, the carbon nano tube agglomeration is easy to occur in the dispersion or suction filtration process when the mass fraction or the volume of the dispersion liquid is too high, and a good conductive network cannot be formed when the mass fraction or the volume of the dispersion liquid is too low.
Further, the aniline solution in the step 3) is an aniline-dilute hydrochloric acid solution, wherein the aniline concentration is 0.1-0.5mol/L, and the hydrochloric acid concentration is 1-2mol/L; the ammonium persulfate solution is an ammonium persulfate-dilute hydrochloric acid solution, wherein the concentration of the ammonium persulfate is 0.1-0.5mol/L, and the concentration of the hydrochloric acid is 1-2 mol/L.
Further, the time for contacting the aniline solution in the step 3) is 4-6min, the time for contacting the ammonium persulfate solution is 4-6min, and the continuous reaction time is 4-6 h after the ammonium persulfate solution is poured out. Controlling the contact time of the aniline solution and the ammonium persulfate solution to be neither too long nor too short, and if the contact time is too short, the aniline solution and the ammonium persulfate solution cannot penetrate through the carbon nanotube electroactive layer to reach the back of the polyacrylonitrile separation layer, so that the crosslinking effect of the separation layer and the electroactive layer is influenced; too long may result in polyaniline formation in the polyacrylonitrile separation layer pore channels, affecting the water permeability of the membrane.
The invention also provides an application of the polyacrylonitrile-carbon nano tube electroactive membrane with the selective oxidation function, which is used for secondary effluent advanced treatment of biological treatment in urban sewage plants, wherein the polyacrylonitrile-carbon nano tube electroactive membrane is used as an anode for connecting a direct current power supply when filtering sewage, the oxidative degradation rate of toxic and harmful small-molecule organic pollutants is higher than 80%, and the oxidative degradation rate of macromolecular organic pollutants is lower than 10%.
Further, the voltage of the direct current power supply is 0.5-2.5V.
Further, the molecular weight of the toxic harmful small molecule organic pollutants is 200-500 daltons, including antibiotics, endocrine disruptors, persistent organic pollutants; the macromolecular organic pollutants are microbial extracellular polymers, including polysaccharides, proteins and humus.
Compared with the prior art, the polyacrylonitrile-carbon nanotube electroactive film with the selective oxidation function has the following advantages:
(1) When the polyacrylonitrile-carbon nano tube electroactive membrane with the selective oxidation function is used for filtering urban secondary effluent, macromolecular organic pollutants such as polysaccharide, protein and humus in the urban secondary effluent are physically intercepted by a polyacrylonitrile separation layer on the upper part of the electroactive membrane, and toxic and harmful small-molecular organic pollutants such as antibiotics, endocrine disruptors and persistent organic pollutants can smoothly penetrate through the polyacrylonitrile separation layer to reach a carbon nano tube electroactive layer on the lower part of the electroactive membrane, and are oxidized and degraded under the action of an external voltage, so that the selective oxidation of the electroactive membrane on the toxic and harmful small-molecular organic pollutants in the urban secondary effluent is realized.
(2) The invention utilizes carboxyl generated after hydrolysis of cyano-group in polyacrylonitrile molecule, carboxyl in carboxylated carbon nano-tube and amido in aniline, realizes chemical crosslinking of polyaniline separation layer and carbon nano-tube electroactive layer in the course of aniline in-situ polymerization reaction, and effectively avoids the carbon nano-tube electroactive layer from falling off from the back of the membrane. The aniline in-situ polymerization reaction is carried out under the acidic (hydrochloric acid) condition of an oxidant (ammonium persulfate), and the generated polyaniline can be ensured to have certain conductivity, thereby being beneficial to the electrochemical degradation of small molecular organic pollutants.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows the effect of polyacrylonitrile membrane of comparative example 1 of the present invention on the retention of humic acid and tetracycline;
FIG. 2 is a graph showing the change of humic acid concentration and removal rate with time in the polyacrylonitrile-carbon nanotube electroactive membrane of comparative example 2 of the present invention without voltage filtration;
FIG. 3 is a graph showing the change of tetracycline concentration and removal rate with time in the absence of applied voltage filtration of the polyacrylonitrile-carbon nanotube electroactive membrane of comparative example 2 of the present invention;
FIG. 4 shows the change of tetracycline concentration and removal rate with time when the polyacrylonitrile-carbon nanotube electroactive membrane of embodiment 3 of the present invention is filtered under an applied voltage of 2.5V;
fig. 5 shows the change of humic acid concentration and removal rate with time when the polyacrylonitrile-carbon nanotube electroactive membrane of embodiment 3 of the present invention is filtered under an external 2.5V voltage.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
A polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function is prepared by the following steps:
(1) Preparation and hydrolysis of polyacrylonitrile membrane: preparing a polyacrylonitrile membrane casting solution, wherein the mass fraction of polyacrylonitrile in the membrane casting solution is 22wt%, preparing a polyacrylonitrile membrane by adopting a non-solvent phase inversion method, and hydrolyzing the back of the polyacrylonitrile membrane in a 1.5 mol/L NaOH solution at 45 ℃ for 5 min;
(2) Carbon nanotube electroactive layer loading: preparing a carbon nano tube (carboxyl content is 3%) dispersion liquid with the mass fraction of 0.05 wt%, and performing suction filtration on 90ml of the carbon nano tube dispersion liquid with the back side of the polyacrylonitrile membrane facing upwards to form a carbon nano tube electroactive layer on the back side of the polyacrylonitrile membrane;
(3) And (3) crosslinking: dripping an aniline solution with the thickness of about 2mm on the back surface of the polyacrylonitrile membrane loaded with the carbon nano tube electroactive layer and contacting for 4min, wherein the concentration of aniline in the aniline solution is 0.1mol/L, and the concentration of hydrochloric acid is 1mol/L; pouring the aniline solution, maintaining the wet state of the back of the membrane, dripping an ammonium persulfate solution with the thickness of about 2mm on the back of the membrane, and contacting for 4min for reaction, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.1mol/L, and the concentration of hydrochloric acid is 1mol/L; and pouring the ammonium persulfate solution, and maintaining the wet state of the back of the membrane to continue reacting for 4 hours to obtain the polyacrylonitrile-carbon nanotube electroactive membrane.
The polyacrylonitrile-carbon nano tube electroactive membrane has a polyacrylonitrile separating layer at the upper part and an average aperture of 5nm at the front surface; the lower part of the membrane is a carbon nano tube electroactive layer with the conductivity of 50S/m.
Example 2
A polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function is prepared by the following steps:
(1) Preparation and hydrolysis of polyacrylonitrile membrane: preparing a polyacrylonitrile membrane casting solution, wherein the mass fraction of polyacrylonitrile in the membrane casting solution is 18wt%, preparing a polyacrylonitrile membrane by adopting a non-solvent phase inversion method, and hydrolyzing the back of the polyacrylonitrile membrane in a 2mol/L NaOH solution at 45 ℃ for 5 min;
(2) Carbon nanotube electroactive layer loading: preparing 0.02wt% of carbon nanotube dispersion liquid (carboxyl content is 2%), pumping and filtering 90ml of the carbon nanotube dispersion liquid with the back of the polyacrylonitrile membrane facing upwards, and forming a carbon nanotube electroactive layer on the back of the polyacrylonitrile membrane;
(3) And (3) crosslinking: dripping aniline solution with the thickness of about 3mm on the back surface of the polyacrylonitrile membrane loaded with the carbon nano tube electroactive layer and contacting for 5min, wherein the concentration of aniline in the aniline solution is 0.2mol/L, and the concentration of hydrochloric acid is 2mol/L; pouring the aniline solution, maintaining the wet state of the back of the membrane, dripping an ammonium persulfate solution with the thickness of about 3mm on the back of the membrane, and contacting for 5min for reaction, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.2mol/L, and the concentration of hydrochloric acid is 2mol/L; and pouring the ammonium persulfate solution, and maintaining the wet state of the back of the membrane to continue reacting for 6 hours to obtain the polyacrylonitrile-carbon nanotube electroactive membrane.
The polyacrylonitrile-carbon nano tube electroactive membrane is characterized in that a polyacrylonitrile separating layer is arranged at the upper part of the membrane, and the average aperture of the front side is 6nm; the lower part of the membrane is a carbon nano tube electroactive layer with the conductivity of 200S/m.
Example 3
The polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function in the embodiment 2 is adopted to filter simulated urban secondary effluent, and the simulated water comprises 20mg/L of humic acid (macromolecular organic pollutants with the average size of about 7 nm), 1mg/L of tetracycline (toxic and harmful micromolecular organic pollutants with the molecular weight of about 300 daltons), and 1 mM NaHCO 3 、10 mM Na2SO 4 The electroactive film was used as the anode and the dc voltage was 2.5V.
Comparative example 1
A polyacrylonitrile membrane was prepared in this comparative example in order to demonstrate that the polyacrylonitrile separation layer in the polyacrylonitrile-carbon nanotube electroactive membrane obtained in example 2 is capable of trapping humic acid and permeating tetracycline. The polyacrylonitrile membrane is prepared by the following steps: preparing a polyacrylonitrile membrane casting solution with the mass fraction of 18wt%, and preparing the polyacrylonitrile membrane by adopting a non-solvent phase inversion method. Then, the polyacrylonitrile membrane was used to filter a solution containing 20mg/L humic acid and 1mg/L tetracycline under a condition of no voltage.
Comparative example 2
The comparative example differs from example 3 in that no voltage is applied during the filtration of the simulated city secondary effluent.
The data for comparative example 1, comparative example 2 and example 3 are shown in figures 1-5. In comparative example 1, the rejection rate of the polyacrylonitrile membrane to humic acid is 94.2% + -1.3%, and the rejection rate to tetracycline is 31.4% + -8.4%, so that the polyacrylonitrile membrane has a good separation effect on humic acid and tetracycline, and can intercept humic acid and permeate tetracycline (fig. 1).
In comparative example 2, under the condition of no voltage, the humic acid rejection rate of the polyacrylonitrile-carbon nanotube electroactive membrane is stabilized between 94% and 96%, and is consistent with that of comparative example 1, so that the physical rejection effect of the polyacrylonitrile separation layer on the humic acid is further illustrated (fig. 2); the tetracycline retention was between 30% and 50%, which was substantially the same as that of comparative example 1, further indicating that the polyacrylonitrile separation layer was tetracycline permeable (fig. 3).
In example 3, under the voltage of 2.5V applied to the polyacrylonitrile-carbon nanotube electroactive film, the removal rate of tetracycline is significantly increased compared with that of comparative example 2 (no voltage applied), and the tetracycline is always maintained at more than 96% in the whole filtration process (the effluent concentration is lower than the detection limit), which indicates that tetracycline is electrochemically degraded in the carbon nanotube electroactive layer (fig. 4); the humic acid removal rate was maintained at about 95% (FIG. 5). The data show that the polyacrylonitrile-carbon nanotube electroactive membrane can firstly physically intercept humic acid and then electrochemically degrade tetracycline, and the aim of selectively oxidizing tetracycline is fulfilled.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A polyacrylonitrile-carbon nanotube electroactive film with selective oxidation function is characterized in that: the polyacrylonitrile-carbon nano tube composite membrane comprises a polyacrylonitrile separating layer on the upper layer and a carbon nano tube electroactive layer on the lower layer, wherein the carbon nano tube electroactive layer is positioned on the back side with large membrane pores of the polyacrylonitrile separating layer, the aperture of the front side of the polyacrylonitrile separating layer is 2-8nm, the electric conductivity is 50-200S/m, and the polyacrylonitrile separating layer and the carbon nano tube electroactive layer are crosslinked through conductive polymer polyaniline.
2. The polyacrylonitrile-carbon nanotube electroactive film with selective oxidation function of claim 1, characterized in that: the polyacrylonitrile-carbon nano tube electroactive film is prepared by the following steps:
1) Preparation and hydrolysis of a polyacrylonitrile separation layer:
preparing a polyacrylonitrile membrane casting solution, preparing a polyacrylonitrile membrane by adopting a non-solvent phase inversion method, and contacting the back of the polyacrylonitrile membrane with a NaOH solution for hydrolysis;
2) Loading the carbon nano tube electroactive layer:
preparing carbon nano tube dispersion liquid, and performing suction filtration on the carbon nano tube dispersion liquid with the back of the polyacrylonitrile membrane facing upwards to form a carbon nano tube electroactive layer on the back of the polyacrylonitrile membrane;
3) And (3) crosslinking:
dripping aniline solution with the thickness of 2-3 mm on the back of the polyacrylonitrile membrane loaded with the carbon nano tube electroactive layer, pouring the aniline solution after a period of time, and maintaining the back of the membrane in a wet state; dropping ammonium persulfate solution with the thickness of the liquid layer of 2-3 mm on the back of the membrane for reaction, and realizing crosslinking by utilizing aniline in-situ polymerization reaction; and pouring the ammonium persulfate solution and maintaining the wet state of the back of the membrane to continue the crosslinking reaction to obtain the polyacrylonitrile-carbon nano tube electroactive membrane.
3. The polyacrylonitrile-carbon nanotube electroactive film with selective oxidation function of claim 2, characterized in that: the mass fraction of polyacrylonitrile in the polyacrylonitrile membrane casting solution in the step 1) is 18-22%.
4. The polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function according to claim 2, characterized in that: in the step 1), the concentration of the NaOH solution is 1-2mol/L, the contact time with the NaOH solution is 2-8min, and the temperature of the NaOH solution is 40-60 ℃.
5. The polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function according to claim 2, characterized in that: the carbon nano tube adopted in the step 2) is a carboxylated carbon nano tube, and the carboxyl content is 2% -4%; the mass fraction of the carbon nano tube dispersion liquid is 0.02-0.08%, and the volume of the dispersion liquid is 50-100 mL.
6. The polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function according to claim 2, characterized in that: the aniline solution in the step 3) is an aniline-diluted hydrochloric acid solution, wherein the aniline concentration is 0.1-0.5mol/L, and the hydrochloric acid concentration is 1-2mol/L; the ammonium persulfate solution is an ammonium persulfate-dilute hydrochloric acid solution, wherein the concentration of ammonium persulfate is 0.1-0.5mol/L, and the concentration of hydrochloric acid is 1-2 mol/L.
7. The polyacrylonitrile-carbon nanotube electroactive film with selective oxidation function of claim 2, characterized in that: the time for contacting with the aniline solution in the step 3) is 4-6min, the time for contacting with the ammonium persulfate solution is 4-6min, and the continuous reaction time is 4-6 h after the ammonium persulfate solution is poured out.
8. Use of the polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function according to claim 1, characterized by comprising: the polyacrylonitrile-carbon nanotube electroactive membrane is used for secondary effluent advanced treatment of biological treatment in urban sewage plants, is used as an anode for connecting a direct current power supply when filtering sewage, and has the oxidative degradation rate of toxic and harmful small-molecule organic pollutants higher than 80 percent and the oxidative degradation rate of macromolecular organic pollutants lower than 10 percent.
9. Use of the polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function according to claim 8, characterized in that: the voltage of the direct current power supply is 0.5-2.5V.
10. Use of the polyacrylonitrile-carbon nanotube electroactive membrane with selective oxidation function according to claim 8, characterized in that: the molecular weight of the toxic harmful small-molecule organic pollutants is 200-500 daltons, and the toxic harmful small-molecule organic pollutants comprise antibiotics, endocrine disruptors and persistent organic pollutants; the macromolecular organic pollutants are microbial extracellular polymers, including polysaccharide, protein and humus.
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| CN113441013A (en) * | 2021-06-28 | 2021-09-28 | 哈尔滨工业大学 | Preparation method of conductive nanofiltration membrane for water treatment |
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| CN102977533A (en) * | 2012-11-28 | 2013-03-20 | 昆明理工大学 | Conductive high-polymer composite material and preparation method thereof |
| US20150224450A1 (en) * | 2014-02-13 | 2015-08-13 | The Regents Of The University Of California | Electrically conducting reverse osmosis membranes |
| CN104785075A (en) * | 2015-04-27 | 2015-07-22 | 南京九思高科技有限公司 | Gas membrane separation device capable of eliminating static electricity and method |
| CN208852693U (en) * | 2018-05-09 | 2019-05-14 | 北京吉泰亿阳科技有限公司 | A kind of heater capable of purifying air |
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