CN110917902A - Graphene polyacrylonitrile hollow fiber membrane and preparation method thereof - Google Patents
Graphene polyacrylonitrile hollow fiber membrane and preparation method thereof Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a graphene polyacrylonitrile hollow fiber membrane and a preparation method thereof, wherein the graphene polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 20-50% of polyacrylonitrile powder, 0.1-15% of graphene oxide solution, 1-5% of modifier, 1-10% of pore-foaming agent and 30-60% of solvent. The modifier is a mixture containing polyvinyl alcohol, sodium lignosulphonate and polyvinylpyrrolidone. The pore-foaming agent comprises potassium salt, sodium salt, polyethylene glycol and polyacrylic acid. The solvent is dimethyl sulfoxide and N-methyl pyrrolidone. The invention also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane. The hollow fiber membrane prepared by the invention is fused with graphene elements, can filter suspended particulate matters, colloids and heavy metal particles in water, can obstruct bacteria and pathogens, simultaneously exerts the graphene antibacterial and bacteriostatic functions, avoids secondary pollution of water quality, ensures that the water quality of drinking water is always in a high-quality state, and protects the health of people.
Description
Technical Field
The invention relates to a fiber membrane and a preparation method thereof, in particular to a graphene polyacrylonitrile hollow fiber membrane and a preparation method thereof.
Background
Graphene is a single-layer carbon atom material stripped from graphite, and a single-layer two-dimensional honeycomb lattice structure is formed by tightly packing carbon atoms, and is known to be the material with the thinnest thickness, the hardest texture and the best conductivity. Graphene has excellent mechanical, optical and electrical properties and a very stable structure, researchers have not found that graphene has a missing carbon atom, the linkage between carbon atoms is very flexible, and is harder than diamond, the strength is 100 times higher than that of the world's best steel, if graphene is used for making a packaging bag, the graphene can bear about two tons of articles, the graphene is almost completely transparent, but is very compact, waterproof and airtight, helium gas with the minimum atomic size cannot pass through the graphene, the graphene has good conductivity, the movement speed of electrons in graphene reaches 1/300 of the light speed, the conductivity exceeds that of any traditional conductive material, the chemical properties are similar to the surface of graphite, various atoms and molecules can be adsorbed and desorbed, and the graphene also has the capability of resisting strong acid and strong alkali. Meanwhile, the graphene also has an excellent antibacterial function, and can be applied to a water purification hollow fiber membrane to effectively avoid bacterial breeding, prevent secondary pollution and protect human health.
Disclosure of Invention
The invention aims to provide a fiber membrane and a preparation method thereof, the graphene hollow fiber membrane is fused with graphene elements, can filter suspended particulate matters, colloids and heavy metal particles in water, can obstruct bacteria and pathogens, simultaneously has the graphene antibacterial and bacteriostatic functions, avoids secondary pollution of water quality, ensures that the water quality of drinking water is always in a high-quality state, and protects the health of people.
In order to achieve the purpose, the invention provides a graphene polyacrylonitrile hollow fiber membrane, wherein the raw materials of the hollow fiber membrane comprise, by mass: 20-50% of Polyacrylonitrile (PAN) powder, 0.1-15% of graphene oxide solution, 1-5% of modifier, 1-10% of pore-foaming agent and 30-60% of solvent.
The graphene polyacrylonitrile hollow fiber membrane is characterized in that the graphene oxide solution is prepared from graphene oxide and deionized water; the graphene of the graphene oxide is prepared by any one of a mechanical stripping method, a liquid phase stripping method, a chemical vapor deposition method and a redox method.
The graphene polyacrylonitrile hollow fiber membrane is characterized in that the modifier is a mixture containing polyvinyl alcohol, sodium lignosulphonate and polyvinylpyrrolidone (PVP), and the mass ratio of the modifier to the PVP is 1 (2-5) to (3-5).
The graphene polyacrylonitrile hollow fiber membrane is characterized in that the pore-foaming agent contains any one or more of potassium salt, sodium salt, polyethylene glycol and polyacrylic acid.
The graphene polyacrylonitrile hollow fiber membrane is characterized in that the solvent is one or two of dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP).
The invention also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane, wherein the method comprises the following steps: step 1, weighing raw materials in proportion; step 2, preparing a graphene oxide solution to obtain functional graphene slurry; step 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, stirring and ultrasonically treating the mixture, adding polyacrylonitrile powder and a pore-forming agent, heating and stirring the mixture to prepare a membrane casting solution; step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle, filtering and defoaming, removing insoluble substances, bubbles and impurities, starting to discharge materials, adopting dry-wet spinning, spinning membrane filaments, passing through an air channel, then entering a coagulating bath, washing with water, and soaking in a deionized water extraction bath at room temperature; and 5, stretching the product obtained in the step 4 in a water bath twice, and drying the obtained membrane filaments to obtain the graphene polyacrylonitrile hollow fiber membrane.
In the preparation method of the graphene polyacrylonitrile hollow fiber membrane, in the step 2, graphene oxide powder is weighed and dispersed in deionized water, stirred at normal temperature for 20-40 min, and then subjected to ultrasonic treatment for 30-60 min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in deionized water is 1-15%.
In the step 3, the functional graphene slurry and the modifier are added into the solvent, fully stirred for 5-15 min, subjected to ultrasonic treatment for 10-30 min, added with the polyacrylonitrile powder and the pore-forming agent, heated to 40-70 ℃, and stirred for 2-3 h to prepare the membrane casting solution.
In the step 4, the casting solution is added into a reaction kettle at a temperature of 80-90 ℃, filtering and defoaming are carried out, insoluble substances, bubbles and impurities are removed, discharging is carried out, dry-wet spinning is adopted, and spun membrane filaments firstly pass through an air channel with the length of 10-15 cm and then enter a coagulating bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in deionized water extraction bath for 1-2 hours at room temperature.
In the step 5, the product is stretched twice in a water bath at 70-80 ℃ and 85-95 ℃, wherein the stretching times are 1-2 times and 2-3 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
The graphene polyacrylonitrile hollow fiber membrane and the preparation method thereof provided by the invention have the following advantages:
the graphene functional hollow fiber membrane provided by the invention has high strength and high filtration efficiency, wherein the pore diameter of the membrane is less than 0.01 micron, not only can remove suspended particles, heavy metals, colloids and the like in water, but also can remove bacteria and pathogens in water, the removal rate reaches 99.9%, and the water quality after treatment completely meets the national drinking standard.
The functional graphene hollow fiber membrane prepared by the method has the advantages of simple process, easy operation, low cost and high economic benefit, and is suitable for large-scale industrial production.
Detailed Description
The following further describes embodiments of the present invention.
The graphene polyacrylonitrile hollow fiber membrane provided by the invention comprises the following raw materials in percentage by mass: 20-50% of Polyacrylonitrile (PAN) powder, 0.1-15% of graphene oxide solution, 1-5% of modifier, 1-10% of pore-foaming agent and 30-60% of solvent.
Preparing a graphene oxide solution by using graphene oxide and deionized water; graphene of graphene oxide is prepared by any one of methods such as a mechanical exfoliation method, a liquid-phase exfoliation method, a chemical vapor deposition method, and a redox method.
Preferably, the modifier is a mixture containing polyvinyl alcohol, sodium lignosulphonate and polyvinylpyrrolidone (PVP) in a mass ratio of 1 (2-5) to (3-5).
The pore-foaming agent comprises any one or more of potassium salt, sodium salt, polyethylene glycol, polyacrylic acid and the like.
The solvent is one or two of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and the like.
The invention also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane, which comprises the following steps: step 1, weighing raw materials in proportion; step 2, preparing a graphene oxide solution to obtain functional graphene slurry; step 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, stirring and ultrasonically treating the mixture, adding polyacrylonitrile powder and a pore-forming agent, heating and stirring the mixture to prepare a membrane casting solution; step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle, filtering and defoaming, removing insoluble substances, bubbles, impurities and the like, starting to discharge materials, adopting dry-wet spinning, spinning membrane filaments, passing through an air channel, then entering a coagulating bath, washing with water, and soaking in a deionized water extraction bath at room temperature; and 5, stretching the product obtained in the step 4 in a water bath twice, and drying the obtained membrane filaments to obtain the graphene polyacrylonitrile hollow fiber membrane.
Preferably, the graphene oxide powder is weighed in the step 2 and dispersed in deionized water, and is stirred for 20-40 min at normal temperature, and then is subjected to ultrasonic treatment for 30-60 min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in deionized water is 1-15%.
And 3, adding the functional graphene slurry and the modifier into a solvent, fully stirring for 5-15 min, performing ultrasonic treatment for 10-30 min, adding polyacrylonitrile powder and a pore-forming agent, heating to 40-70 ℃, stirring for 2-3 h, and preparing a membrane casting solution.
Adding the membrane casting solution into a reaction kettle at the temperature of 80-90 ℃, filtering, defoaming, removing insoluble substances, bubbles and impurities, starting discharging, adopting dry-wet spinning, and spinning membrane filaments to pass through an air channel with the length of 10-15 cm and then enter a coagulating bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in deionized water extraction bath for 1-2 hours at room temperature.
In the step 5, the product is stretched twice in water bath at the temperature of 70-80 ℃ and 85-95 ℃ respectively, and the stretching times are 1-2 times and 2-3 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
The graphene polyacrylonitrile hollow fiber membrane and the preparation method thereof provided by the invention are further described below with reference to the embodiments.
Example 1
A graphene polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 20% of Polyacrylonitrile (PAN) powder, 15% of graphene oxide solution, 5% of a modifier, 10% of a pore-forming agent and 50% of a solvent.
Preparing a graphene oxide solution by using graphene oxide and deionized water; graphene of graphene oxide is prepared by a mechanical exfoliation method.
Preferably, the modifier is a mixture containing polyvinyl alcohol, sodium lignosulfonate and polyvinylpyrrolidone (PVP) in a mass ratio of 1:2: 3.
The porogen comprises a potassium salt. The solvent is dimethyl sulfoxide.
The embodiment also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing a graphene oxide solution to obtain the functional graphene slurry.
Preferably, weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 40min at a normal temperature, and then performing ultrasonic treatment for 60min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in the deionized water is 15%.
And 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, fully stirring for 15min, performing ultrasonic treatment for 30min, adding polyacrylonitrile powder and a pore-forming agent, heating to 40-70 ℃, stirring for 3h, and preparing a membrane casting solution.
Step 4, adding the casting solution prepared in the step 3 into a reaction kettle at the temperature of 80-90 ℃, filtering and defoaming, removing insoluble substances, bubbles, impurities and the like, starting discharging, adopting dry-wet spinning, and spinning membrane filaments to pass through an air channel with the length of 10-15 cm and then enter a coagulating bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in a deionized water extraction bath for 2 hours at room temperature.
Step 5, respectively stretching the product obtained in the step 4 twice in a water bath at the temperature of 70-80 ℃ and 85-95 ℃, wherein the stretching times are 2 times and 3 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
Example 2
A graphene polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 50% of Polyacrylonitrile (PAN) powder, 12% of graphene oxide solution, 3% of a modifier, 5% of a pore-foaming agent and 30% of a solvent.
Preparing a graphene oxide solution by using graphene oxide and deionized water; graphene of graphene oxide is prepared by a liquid phase exfoliation method.
Preferably, the modifier is a mixture containing polyvinyl alcohol, sodium lignosulfonate and polyvinylpyrrolidone (PVP) in a mass ratio of 1:3: 4.
The porogen comprises a sodium salt. The solvent is N-methylpyrrolidone (NMP).
The embodiment also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing a graphene oxide solution to obtain the functional graphene slurry.
Preferably, weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 25min at normal temperature, and performing ultrasonic treatment for 40min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in the deionized water is 5%.
And 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, fully stirring for 8min, performing ultrasonic treatment for 15min, adding polyacrylonitrile powder and a pore-forming agent, heating to 40-70 ℃, stirring for 2h, and preparing a membrane casting solution.
Step 4, adding the casting solution prepared in the step 3 into a reaction kettle at the temperature of 80-90 ℃, filtering and defoaming, removing insoluble substances, bubbles, impurities and the like, starting discharging, adopting dry-wet spinning, and spinning membrane filaments to pass through an air channel with the length of 10-15 cm and then enter a coagulating bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in a deionized water extraction bath for 1h at room temperature.
Step 5, respectively stretching the product obtained in the step 4 twice in a water bath at the temperature of 70-80 ℃ and 85-95 ℃, wherein the stretching times are 2 times and 2 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
Example 3
A graphene polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 28% of Polyacrylonitrile (PAN) powder, 10% of graphene oxide solution, 1% of modifier, 1% of pore-forming agent and 60% of solvent.
Preparing a graphene oxide solution by using graphene oxide and deionized water; graphene of graphene oxide is prepared by chemical vapor deposition.
Preferably, the modifier is a mixture containing polyvinyl alcohol, sodium lignosulfonate and polyvinylpyrrolidone (PVP) in a mass ratio of 1:4: 4.
The porogen comprises polyethylene glycol. The solvent is dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP).
The embodiment also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing a graphene oxide solution to obtain the functional graphene slurry.
Preferably, weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 30min at normal temperature, and performing ultrasonic treatment for 45min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in the deionized water is 8%.
And 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, fully stirring for 10min, performing ultrasonic treatment for 20min, adding polyacrylonitrile powder and a pore-forming agent, heating to 40-70 ℃, stirring for 2.5h, and preparing a membrane casting solution.
Step 4, adding the casting solution prepared in the step 3 into a reaction kettle at the temperature of 80-90 ℃, filtering and defoaming, removing insoluble substances, bubbles, impurities and the like, starting discharging, adopting dry-wet spinning, and spinning membrane filaments to pass through an air channel with the length of 10-15 cm and then enter a coagulating bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in a deionized water extraction bath for 1.5 hours at room temperature.
Step 5, respectively stretching the product obtained in the step 4 twice in a water bath at the temperature of 70-80 ℃ and 85-95 ℃, wherein the stretching times are 1.5 times and 2.5 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
Example 4
A graphene polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 30% of Polyacrylonitrile (PAN) powder, 5% of graphene oxide solution, 4% of a modifier, 6% of a pore-forming agent and 55% of a solvent.
Preparing a graphene oxide solution by using graphene oxide and deionized water; graphene of graphene oxide is prepared by a redox method.
Preferably, the modifier is a mixture containing polyvinyl alcohol, sodium lignosulfonate and polyvinylpyrrolidone (PVP) in a mass ratio of 1:3.5: 4.5.
The porogen comprises polyacrylic acid. The solvent is dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP).
The embodiment also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing a graphene oxide solution to obtain the functional graphene slurry.
Preferably, weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 35min at normal temperature, and performing ultrasonic treatment for 50min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in the deionized water is 12%.
And 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, fully stirring for 12min, performing ultrasonic treatment for 25min, adding polyacrylonitrile powder and a pore-forming agent, heating to 40-70 ℃, stirring for 3h, and preparing a membrane casting solution.
Step 4, adding the casting solution prepared in the step 3 into a reaction kettle at the temperature of 80-90 ℃, filtering and defoaming, removing insoluble substances, bubbles, impurities and the like, starting discharging, adopting dry-wet spinning, and spinning membrane filaments to pass through an air channel with the length of 10-15 cm and then enter a coagulating bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in a deionized water extraction bath for 2 hours at room temperature.
Step 5, respectively stretching the product obtained in the step 4 twice in a water bath at the temperature of 70-80 ℃ and 85-95 ℃, wherein the stretching times are 1 time and 3 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
Example 5
A graphene polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 45% of Polyacrylonitrile (PAN) powder, 0.1% of graphene oxide solution, 1.9% of a modifier, 8% of a pore-foaming agent and 45% of a solvent.
Preparing a graphene oxide solution by using graphene oxide and deionized water; graphene of graphene oxide is prepared by any one of methods such as a mechanical exfoliation method, a liquid-phase exfoliation method, a chemical vapor deposition method, and a redox method.
Preferably, the modifier is a mixture containing polyvinyl alcohol, sodium lignosulfonate and polyvinylpyrrolidone (PVP) in a mass ratio of 1:5: 5.
The pore-foaming agent comprises any one or more of potassium salt, sodium salt, polyethylene glycol, polyacrylic acid and the like.
The solvent is one or two of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and the like.
The embodiment also provides a preparation method of the graphene polyacrylonitrile hollow fiber membrane, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing a graphene oxide solution to obtain the functional graphene slurry.
Preferably, weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 20min at a normal temperature, and then performing ultrasonic treatment for 30min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in deionized water is 1%.
And 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, fully stirring for 5min, performing ultrasonic treatment for 10min, adding polyacrylonitrile powder and a pore-forming agent, heating to 40-70 ℃, stirring for 2h, and preparing a membrane casting solution.
Step 4, adding the casting solution prepared in the step 3 into a reaction kettle at the temperature of 80-90 ℃, filtering and defoaming, removing insoluble substances, bubbles, impurities and the like, starting discharging, adopting dry-wet spinning, and spinning membrane filaments to pass through an air channel with the length of 10-15 cm and then enter a coagulating bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in a deionized water extraction bath for 1h at room temperature.
Step 5, respectively stretching the product obtained in the step 4 twice in a water bath at the temperature of 70-80 ℃ and 85-95 ℃, wherein the stretching times are 1 time and 2 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
The invention provides a graphene polyacrylonitrile hollow fiber membrane and a preparation method thereof, and a graphene polyacrylonitrile hollow fiber membrane material is produced by utilizing a graphene solution preparation and dispersion system and a polyacrylonitrile hollow fiber membrane production process. Specifically, a functional graphene slurry is added into a polyacrylonitrile membrane casting solution, and the solution contains a pore-foaming agent with a certain concentration. This oxidation graphite alkene thick liquids system can be fine mix with polyacrylonitrile membrane casting liquid, and the graphite alkene hollow fiber membrane of preparation fuses graphite alkene element, not only can filter aquatic suspended particles thing, colloid, heavy metal particle, can also separation bacterium, pathogen, has played the antibiotic antibacterial function of graphite alkene simultaneously, avoids quality of water secondary pollution, guarantees that drinking water quality of water is in high-quality state all the time, protects people healthy.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. The graphene polyacrylonitrile hollow fiber membrane is characterized by comprising the following raw materials in percentage by mass: 20-50% of polyacrylonitrile powder, 0.1-15% of graphene oxide solution, 1-5% of modifier, 1-10% of pore-foaming agent and 30-60% of solvent.
2. The graphene polyacrylonitrile hollow fiber membrane according to claim 1, wherein the graphene oxide solution is prepared by graphene oxide and deionized water; the graphene of the graphene oxide is prepared by any one of a mechanical stripping method, a liquid phase stripping method, a chemical vapor deposition method and a redox method.
3. The graphene polyacrylonitrile hollow fiber membrane as claimed in claim 1, wherein the modifier is a mixture containing polyvinyl alcohol, sodium lignosulfonate and polyvinylpyrrolidone, and the mass ratio of the modifier to the polyvinylpyrrolidone is 1 (2-5) to (3-5).
4. The graphene polyacrylonitrile hollow fiber membrane as claimed in claim 1, wherein the pore-forming agent comprises any one or more of potassium salt, sodium salt, polyethylene glycol and polyacrylic acid.
5. The graphene polyacrylonitrile hollow fiber membrane according to claim 1, wherein the solvent is any one or two of dimethyl sulfoxide and N-methyl pyrrolidone.
6. A preparation method of the graphene polyacrylonitrile hollow fiber membrane as claimed in any one of claims 1 to 5, wherein the method comprises the following steps:
step 1, weighing raw materials in proportion;
step 2, preparing a graphene oxide solution to obtain functional graphene slurry;
step 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a solvent, stirring and ultrasonically treating the mixture, adding polyacrylonitrile powder and a pore-forming agent, heating and stirring the mixture to prepare a membrane casting solution;
step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle, filtering and defoaming, removing insoluble substances, bubbles and impurities, starting to discharge materials, adopting dry-wet spinning, spinning membrane filaments, passing through an air channel, then entering a coagulating bath, washing with water, and soaking in a deionized water extraction bath at room temperature;
and 5, stretching the product obtained in the step 4 in a water bath twice, and drying the obtained membrane filaments to obtain the graphene polyacrylonitrile hollow fiber membrane.
7. The preparation method of the graphene polyacrylonitrile hollow fiber membrane according to claim 6, wherein in the step 2, graphene oxide powder is weighed and dispersed in deionized water, stirred for 20-40 min at normal temperature, and then subjected to ultrasonic treatment for 30-60 min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in deionized water is 1-15%.
8. The preparation method of the graphene polyacrylonitrile hollow fiber membrane as claimed in claim 6, wherein in the step 3, the functional graphene slurry and the modifier are added into a solvent, fully stirred for 5-15 min, then subjected to ultrasonic treatment for 10-30 min, added with the polyacrylonitrile powder and the pore-forming agent, heated to 40-70 ℃, stirred for 2-3 h, and a membrane casting solution is prepared.
9. The preparation method of the graphene polyacrylonitrile hollow fiber membrane as claimed in claim 6, wherein in the step 4, the membrane casting solution is added into a reaction kettle at a temperature of 80-90 ℃, filtration and defoaming are carried out, insoluble substances, bubbles and impurities are removed, discharging is started, dry-wet spinning is adopted, and the spun membrane filaments firstly pass through an air channel with a length of 10-15 cm and then enter a coagulation bath; the membrane filament hole is circular and adopts H2And (4) performing O coagulation bath, washing the product with water, and soaking the product in deionized water extraction bath for 1-2 hours at room temperature.
10. The preparation method of the graphene polyacrylonitrile hollow fiber membrane as claimed in claim 6, wherein in the step 5, the product is stretched twice in a water bath at 70-80 ℃ and 85-95 ℃ respectively, and the stretching times are 1-2 times and 2-3 times respectively; and drying the obtained membrane yarn, wherein the inner diameter of the membrane yarn is 0.8-1.5 mm, and the outer diameter of the membrane yarn is 2.0-2.5 mm.
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| CN113402809A (en) * | 2021-05-27 | 2021-09-17 | 北京汽车研究总院有限公司 | Porous graphene honeycomb core material and preparation method and application thereof |
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