CN114931863A - Conductive forward osmosis membrane and preparation method and application thereof - Google Patents
Conductive forward osmosis membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 131
- 238000009292 forward osmosis Methods 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001690 polydopamine Polymers 0.000 claims abstract description 55
- 239000002105 nanoparticle Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003245 coal Substances 0.000 claims abstract description 22
- 239000004952 Polyamide Substances 0.000 claims abstract description 17
- 229920002647 polyamide Polymers 0.000 claims abstract description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 10
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 73
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 20
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 12
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 11
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 11
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000000284 resting effect Effects 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 description 36
- 150000003839 salts Chemical class 0.000 description 12
- 230000008021 deposition Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000000691 measurement method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 239000000356 contaminant Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009285 membrane fouling Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- AMMWFYKTZVIRFN-UHFFFAOYSA-N sodium 3-hydroxy-4-[(1-hydroxynaphthalen-2-yl)diazenyl]-7-nitronaphthalene-1-sulfonic acid Chemical compound [Na+].C1=CC=CC2=C(O)C(N=NC3=C4C=CC(=CC4=C(C=C3O)S(O)(=O)=O)[N+]([O-])=O)=CC=C21 AMMWFYKTZVIRFN-UHFFFAOYSA-N 0.000 description 4
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 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
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- 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
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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Abstract
The invention belongs to the technical field of water treatment membranes, and discloses a conductive forward osmosis membrane and a preparation method and application thereof.A tubular coal-based carbon membrane is taken as a supporting layer, polydopamine nanoparticles are deposited on the inner surface of the tubular coal-based carbon membrane by a vacuum filtration method, and then a continuous polyamide layer is prepared on the surfaces of the polydopamine nanoparticles by interfacial polymerization to obtain the conductive forward osmosis membrane; electrically conductive forward osmosis membranes can be used in water treatment, for example as filtration membranes in water treatment devices or equipment. The conductive forward osmosis membrane prepared by the invention realizes good conductivity and chemical stability, and can solve the problems of poor conductivity or unstable conductivity of the composite conductive forward osmosis membrane; the method is applied to the field of sewage treatment, can relieve the pollution of the forward osmosis membrane by combining the electrochemical action, thereby improving the performance of the membrane, and has great theoretical significance and application value.
Description
Technical Field
The invention belongs to the technical field of water treatment membranes, and particularly relates to a conductive forward osmosis membrane and a preparation method and application thereof.
Background
Forward osmosis technology is identified as one of the best strategies to alleviate the problem of water resource shortage due to its advantages of low energy consumption, good effluent quality and the like. At present, forward osmosis technology is widely applied in the fields of seawater desalination, wastewater treatment and the like. However, membrane fouling prevents the maintenance of performance of forward osmosis technologies for long term use. Thus, mitigating membrane fouling is one of the primary ways to improve membrane performance. The electrochemical coupling membrane technology has the good characteristics of easy process control, stable performance, environmental friendliness and the like, and is concerned more and more in the aspect of controlling membrane pollution.
The conductive forward osmosis membrane is coupled with electrochemistry under the electrostatic action and the oxidation action, and has remarkable effect of relieving membrane pollution. Researchers have proposed that the membrane performance be enhanced by introducing conductive materials into the surface of a forward osmosis substrate or polyamide layer, but conductivity or conductivity stability may affect the enhancement of the membrane performance.
Disclosure of Invention
The invention aims to broaden the preparation method of a conductive forward osmosis membrane, and provides the conductive forward osmosis membrane, the preparation method and the application thereof.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the invention, a tubular coal-based carbon membrane is used as a supporting layer, polydopamine nanoparticles are deposited on the inner surface of the tubular coal-based carbon membrane through a vacuum filtration method, and then a continuous polyamide layer is prepared on the surfaces of the polydopamine nanoparticles through interfacial polymerization, so that the conductive forward osmosis membrane is obtained.
Further, the method comprises the following steps:
(1) preparing a polydopamine nanoparticle dispersion liquid;
(2) preparing a polydopamine nanoparticle middle layer: enabling the polydopamine nanoparticle dispersion liquid obtained in the step (1) to pass through the tubular coal-based carbon membrane, and depositing polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane through vacuum filtration;
(3) and preparing a continuous polyamide layer on the surface of the polydopamine nanoparticle through interfacial polymerization.
Further, in the step (1), the preparation method of the polydopamine nanoparticle dispersion liquid comprises the following steps: mixing dopamine hydrochloride powder with a Tris solution to obtain a dopamine hydrochloride solution; shaking the dopamine hydrochloride solution for 0.5-1.5 h to enable dopamine hydrochloride to undergo oxidative autopolymerization to obtain a polydopamine solution; and ultrasonically dispersing the polydopamine solution to obtain the polydopamine nanoparticle dispersion liquid.
Preferably, the dosage of the dopamine hydrochloride powder is 0.1-0.2 g based on 100mL of water; the concentration of the Tris solution is 0.05-0.2 g/L, and the pH value is 8-9.
Further, in the step (2), the deposition amount of the polydopamine nano-particles on the inner surface of the tubular coal-based carbon film is 0.4-1.3mg/cm 2 。
Further, in the step (3), the method for preparing the continuous polyamide layer on the surface of the polydopamine nanoparticle by interfacial polymerization comprises the following steps: vertically fixing the film obtained in the step (2), enabling a 1-7% m-phenylenediamine solution to pass through the inner surface of the film at a flow rate of 1-5 mL/min, and soaking for 1-10 min to remove redundant solution on the surface; enabling 0.1-0.3% of trimesoyl chloride solution to pass through the inner surface of the membrane at the same flow rate for reaction for 1-5 min; after standing for a certain time, placing the membrane in a hot water bath for crosslinking; taking out the film and sequentially soaking the film in a sodium hypochlorite solution and a sodium bisulfite solution; and then placing the film in a hot water bath again to obtain the conductive forward osmosis film.
Wherein preferably, the rest time is 3-5 min; the temperature for crosslinking in the hot water bath is 80-100 ℃, and the time is 1-3 min.
Preferably, the concentration of the sodium hypochlorite solution is 0.1-0.5 g/L, and the soaking time is 1-3 min; the concentration of the sodium bisulfite solution is 1-3 g/L, and the soaking time is 20-40 s; and placing the film in a hot water bath again at the temperature of 80-100 ℃ for 5-8 min.
According to another aspect of the present invention, there is provided a conductive forward osmosis membrane obtained by the above-mentioned production method.
According to another aspect of the present invention, there is provided a use of the above-described electrically conductive forward osmosis membrane in water treatment.
The invention has the beneficial effects that:
according to the conductive forward osmosis membrane prepared by the invention, polydopamine nanoparticles are deposited on the inner surface of the tubular coal-based carbon membrane through vacuum filtration, so that the inner surface of the carbon membrane which is rough, hydrophobic and has a macroporous defect is covered, and a hydrophilic intermediate layer with uniform pore size distribution is formed; and a complete and continuous polyamide layer is obtained through interfacial polymerization, and the polyamide layer has good permeability and excellent selectivity; the finally prepared conductive forward osmosis membrane realizes good conductivity and chemical stability, and solves the problems of poor conductivity or unstable conductivity of the composite conductive forward osmosis membrane.
The invention prepares the polyamide layer on the inner surface of the coal-based carbon membrane, when the conductive forward osmosis membrane treats the polluted water in a liquid-drawing mode on the polyamide layer, the membrane is used as an electrode under the condition of an external electric field, and the conductivity of the outer surface with large surface area can reduce the deposition of pollutants on the surface of the membrane through electrostatic repulsion and oxidation.
The conductive forward osmosis membrane is applied to the field of sewage treatment, and can relieve the pollution of the forward osmosis membrane by combining the electrochemical action, so that the performance of the membrane is improved, and the conductive forward osmosis membrane has great theoretical significance and application value.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a conductive forward osmosis membrane provided by the present invention;
FIG. 2 is a schematic diagram showing the effect of applied voltage on the flux and flux recovery rate of the rhodamine B solution processed by the conductive forward osmosis membrane prepared in example 2;
wherein, (a) is a flux decline curve of the rhodamine B solution processed by the conductive carbon-based forward osmosis membrane under different voltages;
wherein, (B) is the flux recovery rate and retention rate of the rhodamine B solution processed by the conductive carbon-based forward osmosis membrane under different voltages;
FIG. 3 is a graph showing the effect of applied voltage on the flux and flux recovery rate of the conductive forward osmosis membrane prepared in example 2 for treating a chrome black T solution;
wherein, (a) is a flux decline curve of the conductive carbon-based forward osmosis membrane for treating the chrome black T solution under different voltages;
wherein, (b) is flux recovery rate and retention rate of the conductive carbon-based forward osmosis membrane for treating the chrome black T solution under different voltages.
Detailed Description
As shown in fig. 1, the present invention provides a method for preparing a conductive forward osmosis membrane, comprising the steps of:
(1) preparing a polydopamine nanoparticle dispersion liquid;
as a preferred preparation method: firstly, mixing dopamine hydrochloride powder with a Tris solution to obtain a dopamine hydrochloride solution; then oscillating the dopamine hydrochloride solution for 0.5-1.5 h to enable dopamine hydrochloride to undergo oxidative autopolymerization to obtain a polydopamine solution; and then carrying out ultrasonic dispersion on the polydopamine solution to obtain a polydopamine nanoparticle dispersion solution.
Wherein preferably, the dosage of the dopamine hydrochloride powder based on 100mL of water is 0.1-0.2 g; the concentration of the Tris solution is 0.05-0.2 g/L, and the pH value is 8-9.
(2) Preparing a polydopamine nanoparticle middle layer: taking a certain volume of polydopamine nanoparticle dispersion liquid, passing the polydopamine nanoparticle dispersion liquid through a tubular coal-based carbon membrane, and depositing polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane through vacuum filtration; the deposition amount of the polydopamine nano-particles on the inner surface of the tubular coal-based carbon membrane is preferably 0.4-1.3mg/cm 2 。
(3) A continuous polyamide layer was prepared on the surface of the polydopamine nanoparticles by interfacial polymerization.
As a preferred preparation method: vertically fixing the film obtained in the step (2), enabling a m-phenylenediamine solution with the mass fraction of 1% -7% to pass through the inner surface of the film at the flow speed of 1-5 mL/min, and removing redundant solution on the surface after soaking for 1-10 min; enabling 0.1-0.3% of trimesoyl chloride solution to pass through the inner surface of the membrane at the same flow rate for reaction for 1-5 min; standing for 3-5 min, and then placing the membrane in a hot water bath at the temperature of 80-100 ℃ for crosslinking for 1-3 min; taking out the film, soaking the film in a sodium hypochlorite solution with the concentration of 0.1-0.5 g/L for 1-3 min, and then soaking the film in a sodium bisulfite solution with the concentration of 1-3 g/L for 20-40 s; and then placing the film in a hot water bath at 80-100 ℃ for 5-8 min again to obtain the conductive forward osmosis film.
The conductive forward osmosis membrane prepared by the invention can be used in water treatment, such as a filtration membrane in a water treatment device or equipment.
For a better understanding of the present invention, the following detailed description is given in conjunction with specific examples and comparative examples, but the specific examples described herein are merely illustrative and not restrictive.
The starting materials used in the examples and comparative examples of the present invention are either commercially available or may be synthesized by methods known in the art.
Example 1:
a conductive forward osmosis membrane is prepared by the following steps:
(1) preparing a polydopamine nanoparticle dispersion liquid: weighing 0.2g of dopamine hydrochloride, and dissolving the dopamine hydrochloride in 100mL of Tris solution with the pH value of 8.5 and the concentration of 50mM to obtain dopamine hydrochloride solution; shaking the dopamine hydrochloride solution for 1h to enable the dopamine hydrochloride to undergo oxidative autopolymerization to obtain a polydopamine solution; and (3) carrying out ultrasonic treatment on the polydopamine solution to obtain a polydopamine nanoparticle dispersion liquid.
(2) Preparing a polydopamine nanoparticle middle layer: and (2) taking 5mL of the polydopamine nanoparticle dispersion liquid obtained in the step (1), passing the polydopamine nanoparticle dispersion liquid through a tube of the tubular coal-based carbon membrane at a flow rate of 3mL/min by using a peristaltic pump, and depositing the polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane by vacuum filtration under the pressure of 0.2 Mpa. Finally, the deposition amount of the polydopamine nano-particles on the inner surface of the tubular coal-based carbon membrane is 0.4mg/cm 2 。
(3) Preparing a continuous polyamide layer on the surface of the polydopamine nanoparticles by interfacial polymerization: vertically fixing the film obtained in the step (2), enabling a 3.0 wt% m-phenylenediamine solution to pass through the inner surface of the film at a flow rate of 3mL/min, and removing redundant solution on the surface after soaking for 5 min; allowing 0.15 wt% trimesoyl chloride solution to pass through the inner surface of the membrane at the same flow rate for reaction for 1.5min, standing for 3min, crosslinking the membrane in a hot water bath at 90 ℃ for 2min, taking out, and soaking the membrane in 0.2g/L sodium hypochlorite for 2 min; then the membrane is soaked in 1g/L sodium bisulfite solution for 0.5min, and then the membrane is placed in a hot water bath at 90 ℃ for 6min again, thus obtaining the conductive forward osmosis membrane of the embodiment.
The water flux and the salt flux of the conductive forward osmosis membrane are respectively obtained by formula (1) and formula (2):
wherein, Δ V — volume change of draw solution, L; a-effective membrane area, m 2 (ii) a Δ t-Interval time, h.
Wherein, V t -the volume of draw solution at the end of the test, L; c t -the salt concentration of the draw solution at the end of the test, mol/L; v 0 -the initial volume of draw solution, L; c 0 -initial salt concentration of draw solution, mol/L.
The conductive forward osmosis membrane obtained in example 1 was found to have a water flux of 7.5L/(m) 2 H) reverse salt flux of 10.2 g/(m) 2 ·h)。
Example 2
A conductive forward osmosis membrane was prepared according to the procedure of example 1 except that, in step (2), the volume of the polydopamine nanoparticle dispersion was 10mL, and the deposition amount of the final polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane was 0.91mg/cm 2 。
According to the determination method of the example 1, the water flux of the conductive forward osmosis membrane obtained in the example 2 is 10.75L/(m) 2 H) reverse salt flux of 1.83 g/(m) 2 ·h)。
Example 3
A conductive forward osmosis membrane was prepared according to the procedure of example 1 except that, in step (2), the volume of the polydopamine nanoparticle dispersion was 15mL, and the final deposition amount of the polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane was 1.23mg/cm 2 。
According to the measurement method of the example 1, the water flux of the conductive forward osmosis membrane obtained in the example 3 is measured to be 7.17L/(m) 2 H) reverse salt flux of 1.65 g/(m) 2 ·h)。
Example 4
A conductive forward osmosis membrane was prepared by following the procedure of example 2 except that in the step (3), the concentration of the m-phenylenediamine solution was 1% by weight.
According to the measurement method of example 1, the water flux of the conductive forward osmosis membrane obtained in example 4 is 15.01L/(m) 2 H) reverse salt flux of 6.1 g/(m) 2 ·h)。
Example 5
A conductive forward osmosis membrane was prepared by following the procedure of example 2 except that in step (3), the concentration of the m-phenylenediamine solution was 5 wt%.
According to the measurement method of example 1, the water flux of the conductive forward osmosis membrane obtained in example 5 is 10.37L/(m) 2 H) reverse salt flux of 6.43 g/(m) 2 ·h)。
Example 6
A conductive forward osmosis membrane was prepared by following the procedure of example 2 except that in the step (3), the concentration of the m-phenylenediamine solution was 7% by weight.
According to the determination method of the example 1, the water flux of the conductive forward osmosis membrane obtained in the example 6 is 11.64L/(m) 2 H) reverse salt flux of 106.97 g/(m) 2 ·h)。
Example 7
A conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), a trimesoyl chloride solution was taken at a concentration of 0.1 wt%.
According to the measurement method of the example 1, the water flux of the conductive forward osmosis membrane obtained in the example 7 is measured to be 16.21L/(m) 2 H) reverse salt flux of 55.28 g/(m) 2 ·h)。
Example 8
A conductive forward osmosis membrane was prepared according to the procedure of example 2 except that in step (3), a trimesoyl chloride solution was taken at a concentration of 0.2 wt%.
According to the measurement method of example 1, the water flux of the conductive forward osmosis membrane obtained in example 8 is measured to be 8.39L/(m) 2 H) reverse salt flux of 1.78 g/(m) 2 ·h)。
Example 9
A conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), a trimesoyl chloride solution was taken at a concentration of 0.3 wt%.
The water flux of the conductive forward osmosis membrane obtained in example 9 was measured to be 7.08L/(m) according to the measurement method of example (1) 2 H) reverse salt flux of 11.16 g/(m) 2 ·h)。
The conductive forward osmosis membrane prepared in the above example for treating the dye with positive charge to alleviate membrane pollution is studied as follows:
an anti-contamination experiment was performed using the conductive forward osmosis membrane prepared in example 2 with rhodamine B solution having a concentration of 100ppm and a pH of 4 as a target contaminant. Fig. 2 shows the effect of applied voltage on the flux and flux recovery of the conductive forward osmosis membrane. When +1.5V was applied to the membrane, the flux increased by 21.57% and the flux recovery increased by 4.5% after 8h of operation compared to no voltage application.
The study on the conductive forward osmosis membrane prepared in the above example for treating the negatively charged dye to alleviate membrane contamination is as follows:
an anti-contamination experiment was performed using the conductive forward osmosis membrane prepared in example 2 with a chrome black T solution having a concentration of 100ppm and a pH of 6 as a target contaminant. Fig. 3 shows the effect of applied voltage on the flux and flux recovery of the conductive forward osmosis membrane. When a voltage of-1.5V was applied to the membrane, the flux increased by 14.47% and the flux recovery increased by 4.1% after 8h of operation compared to no voltage, compared to no voltage.
The research on the conductive forward osmosis membrane for treating the dye with positive and negative charges to relieve membrane pollution shows that the anti-pollution performance of the conductive membrane depends on the surface charge of pollutants. Membrane fouling is reduced when the contaminants and the membrane surface have the same charge; membrane fouling is exacerbated when the contaminants and the membrane surface have opposite charges.
The deposition amount is 0.4-1.3mg/cm through preparing the carbon film substrate 2 The conductive carbon-based forward osmosis membrane prepared by the poly-dopamine nanoparticle middle layer has good permeability. When the deposition amount of the polydopamine nano-particles is 0.91mg/cm 2 And the carbon membrane substrate is completely covered to form a hydrophilic intermediate layer with uniform pore size distribution, so that the prepared conductive carbon-based forward osmosis membrane has the best permeability.
On the basis, the influence of the concentration of the m-phenylenediamine solution and the concentration of the trimesoyl chloride solution on the positive permeability of the prepared conductive carbon-based forward osmosis membrane is respectively researched. The concentration range of the m-phenylenediamine solution is 1-5 wt%, the concentration range of the trimesoyl chloride solution is 0.15-0.3 wt%, and the prepared conductive carbon-based forward osmosis membrane has good forward osmosis performance, wherein when the concentration of the m-phenylenediamine solution is 3 w% and the concentration of the trimesoyl chloride solution is 0.15 wt%, the performance of the prepared conductive carbon-based forward osmosis membrane is optimal. And excessive m-phenylenediamine (concentration of 7 wt%) or trimesoyl chloride solution (concentration of 0.3 wt%) causes defects in the polyamide layer by interrupting the formation of the polyamide network, thereby deteriorating the front permeability of the polyamide layer.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (10)
1. The preparation method of the conductive forward osmosis membrane is characterized in that a tubular coal-based carbon membrane is used as a supporting layer, polydopamine nano-particles are deposited on the inner surface of the tubular coal-based carbon membrane by a vacuum filtration method, and then a continuous polyamide layer is prepared on the surfaces of the polydopamine nano-particles through interfacial polymerization to obtain the conductive forward osmosis membrane.
2. The method for preparing a conductive forward osmosis membrane according to claim 1, comprising the steps of:
(1) preparing a polydopamine nanoparticle dispersion liquid;
(2) preparing a middle layer of poly-dopamine nano-particles: enabling the polydopamine nanoparticle dispersion liquid obtained in the step (1) to pass through the tubular coal-based carbon membrane, and depositing polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane through vacuum filtration;
(3) and preparing a continuous polyamide layer on the surface of the polydopamine nano-particles through interfacial polymerization.
3. The method for preparing a conductive forward osmosis membrane according to claim 2, wherein in the step (1), the poly-dopamine nanoparticle dispersion liquid is prepared by: mixing dopamine hydrochloride powder with a Tris solution to obtain a dopamine hydrochloride solution; shaking the dopamine hydrochloride solution for 0.5-1.5 h to enable dopamine hydrochloride to undergo oxidative autopolymerization to obtain a polydopamine solution; and ultrasonically dispersing the polydopamine solution to obtain the polydopamine nanoparticle dispersion liquid.
4. The method for preparing a conductive forward osmosis membrane according to claim 3, wherein the dopamine hydrochloride powder is used in an amount of 0.1 to 0.2g based on 100mL of water; the concentration of the Tris solution is 0.05-0.2 g/L, and the pH value is 8-9.
5. The method for preparing a conductive forward osmosis membrane according to claim 2, wherein in step (2), the poly-dopamine nanoparticle is deposited on the inner surface of the tubular coal-based carbon membrane in an amount of 0.4 to 1.3mg/cm 2 。
6. The method for preparing a conductive forward osmosis membrane according to claim 2, wherein in the step (3), the method for preparing the continuous polyamide layer on the surface of the polydopamine nanoparticle by interfacial polymerization comprises the following steps: vertically fixing the film obtained in the step (2), enabling a 1-7% m-phenylenediamine solution to pass through the inner surface of the film at a flow rate of 1-5 mL/min, and soaking for 1-10 min to remove redundant solution on the surface; enabling 0.1-0.3% of trimesoyl chloride solution in mass fraction to pass through the inner surface of the membrane at the same flow rate to react for 1-5 min; after standing for a certain time, placing the membrane in a hot water bath for crosslinking; taking out the film and sequentially soaking the film in a sodium hypochlorite solution and a sodium bisulfite solution; and then placing the film in a hot water bath again to obtain the conductive forward osmosis film.
7. The method for preparing a conductive forward osmosis membrane according to claim 6, wherein the resting time is 3-5 min; the temperature for crosslinking in the hot water bath is 80-100 ℃, and the time is 1-3 min.
8. The method for preparing a conductive forward osmosis membrane according to claim 6, wherein the concentration of the sodium hypochlorite solution is 0.1-0.5 g/L, and the soaking time is 1-3 min; the concentration of the sodium bisulfite solution is 1-3 g/L, and the soaking time is 20-40 s; and placing the film in a hot water bath again at the temperature of 80-100 ℃ for 5-8 min.
9. An electrically conductive forward osmosis membrane, characterized by being obtained by the production method of any one of claims 1 to 8.
10. Use of a conductive forward osmosis membrane according to claim 9 in water treatment.
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| CN108654408A (en) * | 2018-05-16 | 2018-10-16 | 东华大学 | A kind of PDA is modified hot pressing nanofiber forward osmosis membrane and preparation method thereof |
| US20210060497A1 (en) * | 2019-08-28 | 2021-03-04 | Tongji University | Thin-film composite polyamide reverse osmosis membrane with anti-bacterial and anti-biofouling effects and preparation method thereof |
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