CN112844074A - Graphene composite polyacrylonitrile hollow fiber membrane and preparation method thereof - Google Patents
Graphene composite polyacrylonitrile hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN112844074A CN112844074A CN202110055856.9A CN202110055856A CN112844074A CN 112844074 A CN112844074 A CN 112844074A CN 202110055856 A CN202110055856 A CN 202110055856A CN 112844074 A CN112844074 A CN 112844074A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 146
- 239000012528 membrane Substances 0.000 title claims abstract description 115
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 78
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910001868 water Inorganic materials 0.000 claims abstract description 40
- 239000003607 modifier Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940053009 ethyl cyanoacrylate Drugs 0.000 claims abstract description 10
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 29
- 238000005266 casting Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000003809 water extraction Methods 0.000 claims description 11
- 230000001112 coagulating effect Effects 0.000 claims description 10
- 238000001891 gel spinning Methods 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- 230000015271 coagulation Effects 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 244000052769 pathogen Species 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 53
- -1 bubbles Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a graphene composite polyacrylonitrile hollow fiber membrane and a preparation method thereof, wherein the graphene composite polyacrylonitrile hollow fiber membrane comprises the following raw materials: 20-50% of polyacrylonitrile powder, 0.1-15% of graphene oxide solution, 0.1-1% of modifier, 10-20% of pore-foaming agent and 30-60% of solvent; the pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1 (2-4) to (1-2). The modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinyl pyrrolidone and a silane coupling agent, and the mass ratio of the modifier to the silane coupling agent is 1 (2-4) to (3-5) to (1-2). The invention also provides a preparation method of the graphene composite polyacrylonitrile hollow fiber membrane. The fiber membrane prepared by the method has high strength and high filtering efficiency, and can remove suspended particles, heavy metals, colloids and the like in water and also remove bacteria and pathogens in the water.
Description
Technical Field
The invention relates to a graphene fiber membrane and a preparation method thereof, in particular to a graphene composite 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 and prevent secondary pollution.
Disclosure of Invention
The invention aims to provide a graphene fiber membrane and a preparation method thereof, wherein modified graphene is fused, so that suspended particles, colloid and heavy metal particles in water can be filtered, bacteria and pathogens can be blocked, the graphene has the functions of antibiosis and bacteriostasis, secondary pollution of water quality is avoided, the quality of drinking water is ensured to be in a high-quality state all the time, and the health of people is protected.
In order to achieve the purpose, the invention provides a graphene composite polyacrylonitrile hollow fiber membrane, wherein the hollow fiber membrane comprises the following raw materials in percentage by mass: 20-50% of Polyacrylonitrile (PAN) powder, 0.1-15% of graphene oxide solution, 0.1-1% of modifier, 10-20% of pore-foaming agent and 30-60% of solvent; the pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1 (2-4) to (1-2).
The graphene composite 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 methods such as a mechanical stripping method, a liquid-phase stripping method, a chemical vapor deposition method and a redox method.
The graphene composite polyacrylonitrile hollow fiber membrane is characterized in that the modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinylpyrrolidone (PVP) and a silane coupling agent in a mass ratio of (2) - (4) - (3-5) - (1-2).
The graphene composite polyacrylonitrile hollow fiber membrane is characterized in that the solvent is DMF (dimethyl formamide).
The invention also provides a preparation method of the graphene composite 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 DMF solvent, stirring, performing ultrasonic treatment, adding polyacrylonitrile powder and a pore-forming agent, swelling, heating, and stirring 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 composite polyacrylonitrile hollow fiber membrane.
In the preparation method of the graphene composite 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 a DMF solvent, fully stirred for 15-30 min, subjected to ultrasonic treatment for 20-40 min, added with polyacrylonitrile powder and a pore-forming agent, swelled at 40-60 ℃ for 30-50 min, heated to 70-80 ℃ and stirred for 1-2 h to prepare the casting solution.
The preparation method of the graphene composite polyacrylonitrile hollow fiber membrane comprises the following steps of (4) adding the membrane casting solution into a reaction kettle at the temperature of 60-80 ℃, filtering and defoaming, removing insoluble substances, bubbles and impurities, starting to discharge materials, spinning by adopting a dry-wet method, passing the spun membrane filaments through an air channel with the length of 5-10 cm, and then entering a coagulating bath; the membrane wire holes are circular, and DMF/H2O gradient coagulation bath is adopted, and the gradient mass ratio is (50-60): 35-40), (50-55): 60-70 respectively; and (3) washing the product with water, and soaking the product in a deionized water extraction bath for 2-5 hours at room temperature.
In the step 5, the product is stretched twice in a water bath at 50-60 ℃ and 85-95 ℃, and the stretching times are 3-4 times and 2-3 times respectively.
In the preparation method of the graphene composite polyacrylonitrile hollow fiber membrane, in the step 5, the obtained membrane filaments are dried, and the inner diameter of the membrane filaments is 0.8-1.5 mm, and the outer diameter of the membrane filaments is 2.1-2.5 mm.
The graphene composite polyacrylonitrile hollow fiber membrane and the preparation method thereof provided by the invention have the following advantages:
the graphene functional hollow fiber membrane prepared by the method has high strength and high filtration efficiency, wherein the pore diameter of the membrane is less than 0.01 micron, so that not only can suspended particles, heavy metals, colloids and the like in water be removed, but also bacteria and pathogens in the water can be removed, the removal rate reaches 99.9%, and the water quality after treatment is completely combined with 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 composite 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, 0.1-1% of modifier, 10-20% of pore-foaming agent and 30-60% of solvent.
Preferably, the pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1 (2-4) to (1-2).
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.
The modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinylpyrrolidone (PVP) and a silane coupling agent, and the mass ratio of the modifier to the silane coupling agent is 1 (2-4) to (3-5) to (1-2).
The solvent was DMF (dimethylformamide).
The invention also provides a preparation method of the graphene composite 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 DMF solvent, stirring, performing ultrasonic treatment, adding polyacrylonitrile powder and a pore-forming agent, swelling, heating, and stirring 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 composite polyacrylonitrile hollow fiber membrane.
Preferably, 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%.
And 3, adding the functional graphene slurry and the modifier into a DMF (dimethyl formamide) solvent, fully stirring for 15-30 min, performing ultrasonic treatment for 20-40 min, adding polyacrylonitrile powder and a pore-forming agent, swelling for 30-50 min at 40-60 ℃, heating to 70-80 ℃, stirring for 1-2 h, and preparing the membrane casting solution.
Adding the membrane casting solution into a reaction kettle at the temperature of 60-80 ℃, 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 5-10 cm and then enter a coagulating bath; the membrane wire holes are circular, and DMF/H2O gradient coagulation bath is adopted, and the gradient mass ratio is (50-60): 35-40), (50-55): 60-70 respectively; and (3) washing the product with water, and soaking the product in a deionized water extraction bath for 2-5 hours at room temperature.
And step 5, respectively stretching the product twice in water baths at 50-60 ℃ and 85-95 ℃, wherein the stretching times are respectively 3-4 times and 2-3 times.
The graphene composite 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 composite polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 49.8% of Polyacrylonitrile (PAN) powder, 0.1% of graphene oxide solution, 0.1% of modifier, 20% of pore-forming agent and 30% of solvent.
The pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1:2: 1.
The modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinylpyrrolidone (PVP) and a silane coupling agent in a mass ratio of 1:2:3: 1.
The graphene oxide solution is prepared from graphene oxide and deionized water; the graphene of the graphene oxide is prepared by a mechanical stripping method.
The solvent was DMF (dimethylformamide).
The embodiment also provides a preparation method of the graphene composite 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.
Weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 20-40 min at a normal temperature, and then carrying out ultrasonic treatment for 30-60 min 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 DMF solvent, fully stirring for 15-30 min, performing ultrasonic treatment for 20-40 min, adding polyacrylonitrile powder and a pore-forming agent, swelling for 30-50 min at 40-60 ℃, heating to 70-80 ℃, and stirring for 1-2 h to prepare a casting solution.
Step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle at the temperature of 60-80 ℃, 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 5-10 cm and then enter a coagulating bath; the membrane wire holes are circular, and DMF/H2O gradient coagulation bath is adopted, and the gradient mass ratio is (50-60): 35-40), (50-55): 60-70 respectively; washing the product with water, and soaking the product in a deionized water extraction bath at room temperature for 2-5 h;
and 5, stretching the product obtained in the step 4 twice in a water bath at the temperature of 50-60 ℃ and 85-95 ℃, wherein the stretching times are 3-4 times and 2-3 times respectively. And drying the obtained membrane filaments to obtain the graphene composite polyacrylonitrile hollow fiber membrane. The inner diameter of the membrane wire is 0.8-1.5 mm, and the outer diameter is 2.1-2.5 mm.
Example 2
A graphene composite polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 50% of Polyacrylonitrile (PAN) powder, 1% of graphene oxide solution, 0.8% of a modifier, 11% of a pore-forming agent and 37.2% of a solvent.
The pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1:2.5: 1.
The modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinylpyrrolidone (PVP) and a silane coupling agent in a mass ratio of 1:2.5:3.5: 1.
The graphene oxide solution is prepared from graphene oxide and deionized water; the graphene of the graphene oxide is prepared by a liquid phase stripping method.
The solvent was DMF (dimethylformamide).
The embodiment also provides a preparation method of the graphene composite 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.
Weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 20-40 min at a normal temperature, and then carrying out ultrasonic treatment for 30-60 min to obtain functional graphene slurry; the mass concentration of the graphene oxide powder in deionized water is 3%.
And 3, adding the functional graphene slurry and the modifier obtained in the step 2 into a DMF solvent, fully stirring for 15-30 min, performing ultrasonic treatment for 20-40 min, adding polyacrylonitrile powder and a pore-forming agent, swelling for 30-50 min at 40-60 ℃, heating to 70-80 ℃, and stirring for 1-2 h to prepare a casting solution.
Step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle at the temperature of 60-80 ℃, 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 5-10 cm and then enter a coagulating bath; the membrane wire holes are circular, and DMF/H2O gradient coagulation bath is adopted, and the gradient mass ratio is (50-60): 35-40), (50-55): 60-70 respectively; washing the product with water, and soaking the product in a deionized water extraction bath at room temperature for 2-5 h;
and 5, stretching the product obtained in the step 4 twice in a water bath at the temperature of 50-60 ℃ and 85-95 ℃, wherein the stretching times are 3-4 times and 2-3 times respectively. And drying the obtained membrane filaments to obtain the graphene composite polyacrylonitrile hollow fiber membrane. The inner diameter of the membrane wire is 0.8-1.5 mm, and the outer diameter is 2.1-2.5 mm.
Example 3
A graphene composite polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 24.7% of Polyacrylonitrile (PAN) powder, 3% of graphene oxide solution, 0.3% of a modifier, 12% of a pore-foaming agent and 60% of a solvent.
The pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1:3: 1.5.
The modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinylpyrrolidone (PVP) and a silane coupling agent in a mass ratio of 1:3:4: 1.5.
The graphene oxide solution is prepared from graphene oxide and deionized water; the graphene of the graphene oxide is prepared by a chemical vapor deposition method.
The solvent was DMF (dimethylformamide).
The embodiment also provides a preparation method of the graphene composite 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.
Weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 20-40 min at a normal temperature, and then carrying out ultrasonic treatment for 30-60 min 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 DMF solvent, fully stirring for 15-30 min, performing ultrasonic treatment for 20-40 min, adding polyacrylonitrile powder and a pore-forming agent, swelling for 30-50 min at 40-60 ℃, heating to 70-80 ℃, and stirring for 1-2 h to prepare a casting solution.
Step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle at the temperature of 60-80 ℃, 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 5-10 cm and then enter a coagulating bath; the membrane wire holes are circular, and DMF/H2O gradient coagulation bath is adopted, and the gradient mass ratio is (50-60): 35-40), (50-55): 60-70 respectively; washing the product with water, and soaking the product in a deionized water extraction bath at room temperature for 2-5 h;
and 5, stretching the product obtained in the step 4 twice in a water bath at the temperature of 50-60 ℃ and 85-95 ℃, wherein the stretching times are 3-4 times and 2-3 times respectively. And drying the obtained membrane filaments to obtain the graphene composite polyacrylonitrile hollow fiber membrane. The inner diameter of the membrane wire is 0.8-1.5 mm, and the outer diameter is 2.1-2.5 mm.
Example 4
A graphene composite polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 30% of Polyacrylonitrile (PAN) powder, 7% of graphene oxide solution, 0.5% of a modifier, 15% of a pore-forming agent and 47.5% of a solvent.
The pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1:3.5: 2.
The modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinylpyrrolidone (PVP) and a silane coupling agent in a mass ratio of 1:3.5:4.5: 2.
The graphene oxide solution is prepared from graphene oxide and deionized water; the graphene of the graphene oxide is prepared by adopting a redox method.
The solvent was DMF (dimethylformamide).
The embodiment also provides a preparation method of the graphene composite 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.
Weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 20-40 min at a normal temperature, and then carrying out ultrasonic treatment for 30-60 min 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 DMF solvent, fully stirring for 15-30 min, performing ultrasonic treatment for 20-40 min, adding polyacrylonitrile powder and a pore-forming agent, swelling for 30-50 min at 40-60 ℃, heating to 70-80 ℃, and stirring for 1-2 h to prepare a casting solution.
Step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle at the temperature of 60-80 ℃, 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 5-10 cm and then enter a coagulating bath; the membrane wire holes are circular, and DMF/H2O gradient coagulation bath is adopted, and the gradient mass ratio is (50-60): 35-40), (50-55): 60-70 respectively; washing the product with water, and soaking the product in a deionized water extraction bath at room temperature for 2-5 h;
and 5, stretching the product obtained in the step 4 twice in a water bath at the temperature of 50-60 ℃ and 85-95 ℃, wherein the stretching times are 3-4 times and 2-3 times respectively. And drying the obtained membrane filaments to obtain the graphene composite polyacrylonitrile hollow fiber membrane. The inner diameter of the membrane wire is 0.8-1.5 mm, and the outer diameter is 2.1-2.5 mm.
Example 5
A graphene composite polyacrylonitrile hollow fiber membrane comprises the following raw materials in percentage by mass: 20% of Polyacrylonitrile (PAN) powder, 15% of graphene oxide solution, 1% of modifier, 10% of pore-forming agent and 54% of solvent.
The pore-foaming agent is a mixture of inorganic salt, polyethylene glycol and ethyl cyanoacrylate according to a mass ratio of 1:4: 2.
The modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinylpyrrolidone (PVP) and a silane coupling agent in a mass ratio of 1:4:5: 2.
The graphene oxide solution is prepared from graphene oxide and deionized water; the graphene of the graphene oxide is prepared by a mechanical stripping method or a redox method.
The solvent was DMF (dimethylformamide).
The embodiment also provides a preparation method of the graphene composite 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.
Weighing graphene oxide powder, dispersing the graphene oxide powder in deionized water, stirring for 20-40 min at a normal temperature, and then carrying out ultrasonic treatment for 30-60 min 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 DMF solvent, fully stirring for 15-30 min, performing ultrasonic treatment for 20-40 min, adding polyacrylonitrile powder and a pore-forming agent, swelling for 30-50 min at 40-60 ℃, heating to 70-80 ℃, and stirring for 1-2 h to prepare a casting solution.
Step 4, adding the membrane casting solution prepared in the step 3 into a reaction kettle at the temperature of 60-80 ℃, 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 5-10 cm and then enter a coagulating bath; the membrane wire holes are circular, and DMF/H2O gradient coagulation bath is adopted, and the gradient mass ratio is (50-60): 35-40), (50-55): 60-70 respectively; washing the product with water, and soaking the product in a deionized water extraction bath at room temperature for 2-5 h;
and 5, stretching the product obtained in the step 4 twice in a water bath at the temperature of 50-60 ℃ and 85-95 ℃, wherein the stretching times are 3-4 times and 2-3 times respectively. And drying the obtained membrane filaments to obtain the graphene composite polyacrylonitrile hollow fiber membrane. The inner diameter of the membrane wire is 0.8-1.5 mm, and the outer diameter is 2.1-2.5 mm.
The invention provides a graphene composite polyacrylonitrile hollow fiber membrane and a preparation method thereof, which are characterized in that functional graphene slurry is added into a polyacrylonitrile membrane casting solution, the solution contains a pore-forming agent with a certain concentration, and the functional graphene slurry system can be well mixed with the polyacrylonitrile membrane casting solution. The invention aims to produce a graphene polyacrylonitrile hollow fiber membrane material by utilizing a graphene solution preparation and dispersion system and a polyacrylonitrile hollow fiber membrane production process, the graphene hollow fiber membrane is fused with modified graphene, not only can filter suspended particulate matters, colloids and heavy metal particles in water, but also can obstruct bacteria and pathogens, simultaneously plays a role in graphene antibiosis and bacteriostasis, 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. The graphene hollow fiber membrane can also greatly prolong the service life and reduce the use cost.
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 composite 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, 0.1-1% of modifier, 10-20% of pore-foaming agent and 30-60% of solvent; the pore-foaming agent is inorganic salt, polyethylene glycol and ethyl cyanoacrylate, and the mass ratio of the pore-foaming agent to the ethyl cyanoacrylate is 1 (2-4):
the mixture of (1-2).
2. The graphene composite 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 composite polyacrylonitrile hollow fiber membrane of claim 1, wherein the modifier is a mixture of polyethylene glycol, dodecyl pyrrolidone, polyvinyl pyrrolidone and a silane coupling agent, and the mass ratio of the modifier to the silane coupling agent is 1 (2-4) to (3-5) to (1-2).
4. The graphene composite polyacrylonitrile hollow fiber membrane according to claim 1, wherein the solvent is DMF.
5. A preparation method of the graphene composite polyacrylonitrile hollow fiber membrane as claimed in any one of claims 1 to 4, characterized by comprising 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 DMF solvent, stirring, performing ultrasonic treatment, adding polyacrylonitrile powder and a pore-forming agent, swelling, heating, and stirring 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 composite polyacrylonitrile hollow fiber membrane.
6. The preparation method of the graphene composite polyacrylonitrile hollow fiber membrane according to claim 5, 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%.
7. The preparation method of the graphene composite polyacrylonitrile hollow fiber membrane according to claim 5, wherein in the step 3, the functional graphene slurry and the modifier are added into a DMF solvent, fully stirred for 15-30 min, then subjected to ultrasonic treatment for 20-40 min, added with polyacrylonitrile powder and a pore-forming agent, swelled at 40-60 ℃ for 30-50 min, heated to 70-80 ℃ and stirred for 1-2 h, and a membrane casting solution is prepared.
8. The preparation method of the graphene composite polyacrylonitrile hollow fiber membrane according to claim 5, wherein in the step 4, the membrane casting solution is added into a reaction kettle at the temperature of 60-80 ℃, 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 the length of 5-10 cm and then enter a coagulation bath; the membrane filament hole is circular and adopts DMF/H2An O gradient coagulation bath, wherein the mass ratio of the gradient is (50-60): 35-40), (50-55): 60-70); and (3) washing the product with water, and soaking the product in a deionized water extraction bath for 2-5 hours at room temperature.
9. The preparation method of the graphene composite polyacrylonitrile hollow fiber membrane according to claim 5, wherein in the step 5, the product is stretched twice in a water bath at 50-60 ℃ and 85-95 ℃, and the stretching times are 3-4 times and 2-3 times respectively.
10. The preparation method of the graphene composite polyacrylonitrile hollow fiber membrane as claimed in claim 5, wherein in the step 5, the obtained membrane filaments are dried, and the inner diameter of the membrane filaments is 0.8-1.5 mm, and the outer diameter of the membrane filaments is 2.1-2.5 mm.
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