CN111203114A - Multilayer bio-based hollow nanofiber water treatment membrane, preparation method and application thereof - Google Patents
Multilayer bio-based hollow nanofiber water treatment membrane, preparation method and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
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- 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
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
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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
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Abstract
The invention provides a multilayer bio-based hollow nanofiber water treatment membrane, a preparation method and application thereof, wherein the method comprises the steps of preparing a nanofiber membrane with a multilayer core-shell structure by using mineral oil as a core layer solution and using a mixed solution of a water-soluble biological macromolecule mixed with a cross-linking agent and a water-soluble synthetic macromolecule as a shell layer solution and adopting a coaxial electrostatic spinning technology, dissolving a core layer substance by using an organic solvent, and drying to obtain the multilayer hollow nanofiber membrane; the fiber in the water treatment membrane is of a hollow structure in the core part. The preparation method disclosed by the invention is simple to operate, low in cost, green and environment-friendly, and easy for industrial production, and the prepared multilayer hollow nanofiber has high heavy metal filtration efficiency, excellent mechanical property and flexibility, good biodegradability and a wide market application prospect.
Description
Technical Field
The invention relates to a multilayer bio-based hollow nanofiber water treatment membrane, a preparation method and application thereof, and belongs to the field of nano functional materials and environmental water treatment.
Background
Heavy metals cannot be biodegraded in nature, are biologically enriched after entering organisms, are converted into compounds which are more difficult to biodegrade and have stronger toxicity, and finally enter human bodies through the biological amplification effect of food chains, so that even trace concentrations of heavy metals can generate remarkable toxic effects.
The membrane separation method utilizes a porous semipermeable membrane, applies a certain pressure to heavy metal wastewater, so that water molecules in the wastewater pass through the semipermeable membrane, and heavy metal ions are difficult to pass through and are concentrated, thereby achieving the purification effect on the heavy metal wastewater. The membrane separation method has the characteristics of high efficiency, easiness in operation, space saving, good effluent quality and the like, and has a huge application prospect in the aspect of heavy metal wastewater treatment.
The micro-nano hollow structure material has the characteristics of ultrahigh specific surface area, hollow property and light weight, and has huge application prospect in the fields of food, environment, medicine and energy. The coaxial electrostatic spinning method is a technology capable of preparing hollow fibers with continuous micro-nano structures, the micro-nano fibers with core-shell structures are prepared by adopting coaxial needles on the basis of the traditional electrostatic spinning technology, and then the core materials are removed by utilizing solvent or high-temperature calcination, so that the nano materials with the hollow structures are obtained.
The biomass-based polymer has wide sources and low cost, can be fully biodegraded after being used, has no pollution to the environment, can be widely used for adsorbing and separating heavy metals and radioactive nuclides in wastewater of industries such as mining industry, metallurgy, chemical industry, electroplating, machinery, medicine, national defense and military industry and the like, and simultaneously, the renewable biomass resource is developed, so that the use of petrochemical raw materials can be greatly reduced, and the national sustainable development strategy is met. At present, the bio-based nanofiber filtering membrane prepared by an electrostatic spinning method has low mechanical strength, poor severe environment resistance, low single-layer adsorption capacity and small separation flux, and limits the industrial application of the bio-based nanofiber filtering membrane in the field of adsorption and separation.
Disclosure of Invention
The invention provides a hollow nanofiber water treatment membrane with stable multilayer and structure, a preparation method and application thereof, aiming at the defects of the existing bio-based nanofiber filtration membrane in the aspects of adsorption separation performance and mechanical property. The method is simple, convenient and efficient, energy-saving and environment-friendly, and the obtained hollow nanofiber membrane has the characteristics of large separation flux and high interception rate, and has wide application prospect in the field of environmental water treatment.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a multilayer bio-based hollow nanofiber water treatment membrane is characterized by comprising the following steps:
(1) preparation of core layer solution
Putting the mineral oil A into a beaker, standing, putting the beaker into an ultrasonic environment, and removing air mixed in the beaker to obtain a spinning core layer solution;
(2) preparation of Shell solution
Firstly, preparing a water-soluble biopolymer B into a high polymer B solution with the mass fraction of 1-5%, then preparing a water-soluble synthetic polymer C into a high polymer C solution with the mass fraction of 1-10%, then mixing the high polymer B solution and the high polymer C solution at normal temperature, and finally adding a cross-linking agent into the mixed solution to be used as a shell solution for spinning;
(3) preparation of multilayer core-shell nanofibers
Injecting the core layer solution prepared in the step (1) into a core layer injector by adopting a coaxial electrostatic spinning device, injecting the shell layer solution prepared in the step (2) into a shell layer injector, installing a coaxial needle side pipe on the core layer injector, connecting the shell layer injector with a side pipe of the coaxial needle by using a polytetrafluoroethylene pipe, pushing the core layer injector and the shell layer injector by using an automatic liquid supply pump, and preparing a first layer core-shell nanofiber layer by coaxial electrostatic spinning; on the basis of forming the first core-shell nanofiber layer, a second core-shell nanofiber layer, a third core-shell nanofiber layer and a multi-layer core-shell nanofiber membrane are sequentially prepared by stacking in the same method;
(4) preparation of multilayer hollow nanofiber membranes
And (4) placing the multilayer core-shell nanofiber membrane prepared in the step (3) in a solvent D, dissolving out the mineral oil A, taking out and drying to obtain the continuous and uniform multilayer hollow nanofiber membrane.
Further, in the step (1), the mineral oil A is one of paraffin oil and simethicone.
Further, the water-soluble biopolymer B in the step (2) is one or more of chitosan, carboxymethyl cellulose, starch, sodium alginate and gelatin.
Further, the water-soluble synthetic polymer C in the step (2) is one of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polymaleic anhydride, epoxy resin, phenol resin, amino resin, alkyd resin, and polyamino resin.
Further, the mass ratio of the high polymer B solution to the high polymer C solution in the step (2) is 1: 1-1: 10.
Further, in the step (2), the cross-linking agent is one of N, N' -methylene bisacrylamide, glutaraldehyde and sodium tripolyphosphate.
Further, the electrostatic spinning process parameters in the step (3) are as follows: the voltage of a high-voltage electrostatic electric field applied between the receiving roller and the coaxial needle head is 20-25 kV, the distance between the coaxial spray head and the receiving device is 4-8 cm, the spraying speed of the core layer solution is 1-3 mu L/min, and the spraying speed of the shell layer solution is 15-30 mu L/min.
Further, the solvent D in the step (4) is one of petroleum ether and n-hexane.
The multilayer bio-based hollow nanofiber water treatment membrane prepared by the preparation method is characterized in that the membrane is formed by stacking a plurality of layers of nanofiber membranes, pores are formed between fibers in the nanofiber membranes, the core parts of the fibers are of hollow structures, and the fibers are made of water-soluble biological polymers and water-soluble synthetic polymers through crosslinking.
The multilayer bio-based hollow nanofiber water treatment membrane is used for filtering and separating heavy metals in water.
The preparation method of the multilayer bio-based hollow nanofiber water treatment membrane adopts a coaxial electrospinning technology, takes mineral oil as a core layer solution, takes a mixed solution of a water-soluble biopolymer containing a cross-linking agent and a water-soluble synthetic polymer as a shell layer solution, and is prepared by multilayer superposition spinning. After the mineral oil in the core layer is dissolved out by the organic solvent, hollow pores are formed in the core part of the fiber, so that the porosity of the water treatment membrane is increased, and the flux of the membrane can be obviously improved.
The fiber shell material is formed by crosslinking a water-soluble biopolymer and a water-soluble synthetic polymer, so that on one hand, the use of an organic solvent in the preparation process can be avoided, and the zero pollution in the preparation process can be achieved. On the other hand, the prepared fiber has more functional groups, the chelation effect of the water treatment membrane on heavy metal substances in the heavy metal filtering process is improved, and the interception rate of heavy metals is improved. Meanwhile, the core part of the fiber is of a hollow structure, so that the contact area between water and the water treatment membrane is increased, and the filtering effect on heavy metals can be improved.
In addition, the water treatment membrane prepared by the method is of a multilayer structure, so that on one hand, the mechanical strength and flexibility of the membrane can be effectively improved; on the other hand, the filter also contributes to the improvement of the filtering effect.
In conclusion, the beneficial effects of the invention are as follows:
1) the invention adopts a coaxial electrostatic spinning method to prepare the multilayer hollow nanofiber membrane, adopts water as a solvent in the whole production process, does not produce secondary pollution, is green and environment-friendly, has low energy consumption, convenient operation and low cost, and is easy for large-scale production.
2) The hollow nanofiber membrane prepared by the invention has a multilayer hollow structure, is excellent in mechanical property, large in specific surface area, high in porosity, uniform in pore size distribution and good in adsorption property, has a heavy metal ion retention rate of over 96 percent, and can be applied to adsorption separation of heavy metal ions in a complex water environment.
3) Is made of biological materials, has good biodegradability and larger market application prospect.
Drawings
Fig. 1 is an optical microscope picture of the hollow nanofiber prepared in example 1.
Fig. 2 is an SEM picture of the hollow nanofiber prepared in example 1.
FIG. 3 shows the UV absorption spectrum (a) and the standard curve (b) of copper ions of different concentrations.
Fig. 4 is a graph of the filtration efficiency of the hollow nanofiber membrane of example 1 against copper ions.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
5mL of paraffin oil was measured, and after ultrasonic treatment for 30 seconds, air mixed therein was removed to obtain an electrospinning core layer solution. Weighing 20g of polyvinyl alcohol, dissolving in 180g of water, magnetically stirring for 4h at 90 ℃, and cooling to obtain a polyvinyl alcohol solution with the mass fraction of 10%. Weighing 5g of carboxymethyl chitosan, dissolving the carboxymethyl chitosan in 95g of water, magnetically stirring for 2 hours, and obtaining a carboxymethyl chitosan solution with the mass fraction of 5% after complete dissolution. Mixing a polyvinyl alcohol solution and a carboxymethyl chitosan solution in a ratio of 4: 1, adding 1% by mass of sodium tripolyphosphate into the mixed solution for crosslinking, and uniformly mixing by using a vortex mixer to obtain an electrostatic spinning shell solution; injecting the core layer solution into a core layer injector and injecting the shell layer solution into a shell layer injector by adopting a coaxial electrostatic spinning device, conveying the shell layer solution to a coaxial needle side tube through a polytetrafluoroethylene tube, controlling the propelling speeds of the core layer injector and the shell layer injector by an automatic liquid supply pump, setting the electrostatic voltage to be 23kV, the core layer spraying speed to be 3 mu L/min, the shell layer spraying speed to be 30 mu L/min and the receiving distance to be 4cm, and carrying out coaxial electrostatic spinning to prepare the first layer of core-shell nanofiber layer. On the first layer of core-shell nanofiber layer substrate, adopting the same steps to superpose and prepare a second layer of core-shell nanofiber layer, a third layer of core-shell nanofiber layer and a multilayer core-shell nanofiber membrane; and placing the prepared multilayer core-shell nanofiber membrane in petroleum ether, dissolving out paraffin oil, taking out and drying to obtain the multilayer hollow nanofiber membrane. Fig. 1 shows an optical microscope image of the hollow nanofiber prepared in this example 1, and it can be seen from the image in fig. 1 that the coaxial electrospinning process in combination with the method of dissolving the core substance by the organic solvent successfully prepares the fiber with a hollow core. An SEM picture of the multilayer hollow nanofiber membrane prepared in the embodiment is shown in FIG. 2, the diameter of the nanofiber is 100-300nm, a network communication structure is formed, a multilayer fishing net-shaped structure is formed after the nanofiber membrane is laminated layer by layer, and the structural strength and the toughness of the fiber membrane are greatly improved. The meshes between each layer are distributed densely, so that the porosity is greatly increased, and the separation flux of the fiber membrane is improved. And correspondingly, the filter of heavy metals is supported. As shown in FIG. 3, it can be seen from the ultraviolet absorption peak and the linear fitting graph that the absorbance and the concentration of the copper ions show an obvious linear positive correlation, and the correlation coefficient reaches more than 0.99. As shown in fig. 4, the four-layer nanofiber membrane has a metal copper ion filtration efficiency of 96.11%, and realizes high-efficiency adsorption filtration of copper ions.
Example 2
Measuring 5mL of paraffin oil, carrying out ultrasonic treatment for 30s, and removing air mixed in the paraffin oil to obtain an electrostatic spinning core layer solution; weighing 20g of polyacrylic acid, dissolving in 180g of water, magnetically stirring for 4h at 90 ℃, and cooling to obtain a polyacrylic acid solution with the mass fraction of 10%. Weighing 5g of carboxymethyl chitosan, dissolving the carboxymethyl chitosan in 95g of water, magnetically stirring for 2 hours, and obtaining a carboxymethyl chitosan solution with the mass fraction of 5% after complete dissolution. Mixing a polyacrylic acid solution and a carboxymethyl chitosan solution in a ratio of 3: 1, adding 1% glutaraldehyde for crosslinking, and uniformly mixing by using a vortex mixer to obtain an electrostatic spinning shell solution; and (2) injecting the core layer solution into a core layer injector and injecting the shell layer solution into a shell layer injector by adopting a coaxial electrostatic spinning device, connecting the shell layer solution with a coaxial needle side pipe by using a polytetrafluoroethylene pipe, controlling the core layer injector and the shell layer injection propulsion speed by using an automatic liquid supply pump, setting the electrostatic voltage to be 23kV, controlling the core layer injection speed to be 3 mu L/min, controlling the shell layer injection speed to be 30 mu L/min, and carrying out coaxial electrostatic spinning at a receiving distance of 4cm to prepare the first core-shell nanofiber layer. On the first layer of core-shell nanofiber layer substrate, adopting the same steps to superpose and prepare a second layer of core-shell nanofiber layer, a third layer of core-shell nanofiber layer and a multilayer core-shell nanofiber membrane; and placing the prepared multilayer core-shell nanofiber membrane in petroleum ether, dissolving out paraffin oil, taking out and drying to obtain the multilayer hollow nanofiber membrane.
Example 3
Measuring 5mL of dimethyl silicone oil, carrying out ultrasonic treatment for 30s, and removing air mixed in the dimethyl silicone oil to obtain an electrostatic spinning core layer solution; weighing 20g of polyvinyl alcohol, dissolving in 180g of water, magnetically stirring for 4h at 90 ℃, and cooling to obtain a polyvinyl alcohol solution with the mass fraction of 10%. Weighing 5g of carboxymethyl cellulose, dissolving the carboxymethyl cellulose in 95g of water, magnetically stirring for 2 hours, and obtaining a carboxymethyl cellulose solution with the mass fraction of 5% after complete dissolution. Mixing the polyvinyl alcohol solution and the carboxymethyl cellulose solution in a ratio of 2: 1, adding 1% by mass of sodium tripolyphosphate into the mixed solution for crosslinking, and uniformly mixing by using a vortex mixer to obtain an electrostatic spinning shell solution; and (2) injecting the core layer solution into a core layer injector and injecting the shell layer solution into a shell layer injector by adopting a coaxial electrostatic spinning device, connecting the shell layer solution with a coaxial needle side pipe by using a polytetrafluoroethylene pipe, controlling the core layer injector and the shell layer injection propulsion speed by using an automatic liquid supply pump, setting the electrostatic voltage to be 23kV, controlling the core layer injection speed to be 3 mu L/min, controlling the shell layer injection speed to be 30 mu L/min, and carrying out coaxial electrostatic spinning at a receiving distance of 4cm to prepare the first core-shell nanofiber layer. On the first layer of core-shell nanofiber layer substrate, adopting the same steps to superpose and prepare a second layer of core-shell nanofiber layer, a third layer of core-shell nanofiber layer and a multilayer core-shell nanofiber membrane; and (3) placing the prepared multilayer core-shell nanofiber membrane in n-hexane, dissolving out dimethyl silicone oil, taking out and drying to obtain the multilayer hollow nanofiber membrane.
Example 4
Measuring 5mL of dimethyl silicone oil, carrying out ultrasonic treatment for 30s, and removing air mixed in the dimethyl silicone oil to obtain an electrostatic spinning core layer solution; weighing 20g of polyvinylpyrrolidone, dissolving in 180g of water, magnetically stirring for 4h at 90 ℃, and cooling to obtain a polyvinylpyrrolidone solution with the mass fraction of 10%. Weighing 5g of sodium alginate, dissolving the sodium alginate in 95g of water, and stirring the mixture for 2 hours by magnetic force to obtain a sodium alginate solution with the mass fraction of 5 percent after the sodium alginate solution is completely dissolved. Mixing a polyvinyl pyrrolidone solution and a sodium alginate solution in a ratio of 1:1, adding 1 mass percent of N, N' -methylene bisacrylamide into the mixed solution for crosslinking, and uniformly mixing by using a vortex mixer to obtain an electrostatic spinning shell solution; and (2) injecting the core layer solution into a core layer injector and injecting the shell layer solution into a shell layer injector by adopting a coaxial electrostatic spinning device, connecting the shell layer solution with a coaxial needle side pipe by using a polytetrafluoroethylene pipe, controlling the core layer injector and the shell layer injection propulsion speed by using an automatic liquid supply pump, setting the electrostatic voltage to be 23kV, controlling the core layer injection speed to be 3 mu L/min, controlling the shell layer injection speed to be 30 mu L/min, and carrying out coaxial electrostatic spinning at a receiving distance of 4cm to prepare the first core-shell nanofiber layer. On the first layer of core-shell nanofiber layer substrate, adopting the same steps to superpose and prepare a second layer of core-shell nanofiber layer, a third layer of core-shell nanofiber layer and a multilayer core-shell nanofiber membrane; and placing the prepared multilayer core-shell nanofiber membrane in petroleum ether, dissolving out dimethyl silicone oil, taking out and drying to obtain the multilayer hollow nanofiber membrane.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a multilayer bio-based hollow nanofiber water treatment membrane is characterized by comprising the following steps:
(1) preparation of core layer solution
Putting the mineral oil A into a beaker, standing, putting the beaker into an ultrasonic environment, and removing air mixed in the beaker to obtain a spinning core layer solution;
(2) preparation of Shell solution
Preparing a water-soluble biopolymer B into a polymer B solution with the mass fraction of 1-5%;
preparing a water-soluble synthetic polymer C into a polymer C solution with the mass fraction of 1-10%;
then mixing the high polymer B solution and the high polymer C solution at normal temperature, and finally adding a cross-linking agent into the mixed solution to be used as a shell solution for spinning;
(3) preparation of multilayer core-shell nanofibers
Injecting the core layer solution prepared in the step (1) into a core layer injector by adopting a coaxial electrostatic spinning device, injecting the shell layer solution prepared in the step (2) into a shell layer injector, installing a coaxial needle side pipe on the core layer injector, connecting the shell layer injector with a side pipe of the coaxial needle by using a polytetrafluoroethylene pipe, pushing the core layer injector and the shell layer injector by using an automatic liquid supply pump, and preparing a first layer core-shell nanofiber layer by coaxial electrostatic spinning; on the basis of forming the first core-shell nanofiber layer, a second core-shell nanofiber layer, a third core-shell nanofiber layer and a multi-layer core-shell nanofiber membrane are sequentially prepared by stacking in the same method;
(4) preparation of multilayer hollow nanofiber membranes
And (4) placing the multilayer core-shell nanofiber membrane prepared in the step (3) in a solvent D, dissolving out the mineral oil A, taking out and drying to obtain the continuous and uniform multilayer hollow nanofiber membrane.
2. The method according to claim 1, wherein the mineral oil A in step (1) is one of paraffin oil and dimethicone.
3. The preparation method according to claim 1, wherein the water-soluble biopolymer B in step (2) is one or more of chitosan, carboxymethyl cellulose, starch, sodium alginate and gelatin.
4. The production method according to claim 1, wherein the water-soluble synthetic polymer C in the step (2) is one of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, polymaleic anhydride, epoxy resin, phenol resin, amino resin, alkyd resin, and polyamino resin.
5. The method according to claim 1, wherein the mass ratio of the polymer B solution to the polymer C solution in the step (2) is 1:1 to 1: 10.
6. The method according to claim 1, wherein the crosslinking agent in step (2) is one of N, N' -methylenebisacrylamide, glutaraldehyde, and sodium tripolyphosphate.
7. The preparation method according to claim 1, wherein the electrostatic spinning process parameters in the step (3) are as follows: the voltage of a high-voltage electrostatic electric field applied between the receiving roller and the coaxial needle head is 20-25 kV, the distance between the coaxial spray head and the receiving device is 4-8 cm, the spraying speed of the core layer solution is 1-3 mu L/min, and the spraying speed of the shell layer solution is 15-30 mu L/min.
8. The method according to claim 1, wherein the solvent D in the step (4) is one of petroleum ether and n-hexane.
9. The multi-layer bio-based hollow nanofiber water treatment membrane prepared by the preparation method of claim 1, wherein the multi-layer bio-based hollow nanofiber water treatment membrane is formed by stacking a plurality of layers of nanofiber membranes, pores are formed among fibers in the nanofiber membranes, the core parts of the fibers are of a hollow structure, and the fibers are made of water-soluble biological polymers and water-soluble synthetic polymers through crosslinking.
10. The multilayer bio-based hollow nanofiber water treatment membrane of claim 9 is used for filtration separation of heavy metals in water.
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| CN111644084A (en) * | 2020-06-15 | 2020-09-11 | 齐松松 | Modified carboxymethyl chitosan polytetrafluoroethylene nanofiltration membrane and preparation method thereof |
| CN113413774A (en) * | 2021-06-23 | 2021-09-21 | 江苏大学 | Multilayer bio-based nanofiber heavy metal filtering membrane, preparation method and application thereof |
| CN117771413A (en) * | 2023-12-27 | 2024-03-29 | 海南医学院 | Medicine-carrying double-layer nanofiber membrane and preparation method thereof |
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