CN112827373A - Preparation method of graphene oxide composite membrane with adjustable interlamellar spacing - Google Patents
Preparation method of graphene oxide composite membrane with adjustable interlamellar spacing Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 147
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000011229 interlayer Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 26
- 229960003638 dopamine Drugs 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 48
- 230000004907 flux Effects 0.000 abstract description 17
- 150000003839 salts Chemical class 0.000 abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 238000001728 nano-filtration Methods 0.000 description 53
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 30
- 229910052593 corundum Inorganic materials 0.000 description 30
- 229910001845 yogo sapphire Inorganic materials 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000012266 salt solution Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 230000035699 permeability Effects 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 238000009295 crossflow filtration Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- -1 salts sodium sulfate Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a Graphene Oxide (GO) composite membrane with adjustable interlamellar spacing, which comprises the following specific steps: carrying out interface modification on the membrane carrier to obtain a modified carrier; then adding an amine monomer into the GO dispersion liquid subjected to ultrasonic dispersion, fully reacting to obtain a coating liquid, and allowing the coating liquid to pass through N2Loading the modified carrier under pressure; and drying to obtain the GO composite membranes with different interlayer spacings. The method utilizes a simple thermodynamic means to influence the number of oxygen-containing functional groups (hydroxyl) on GO nano-sheets by changing the drying temperature so as to regulate and control the interlayer structure of GOThe purpose is to influence pure water permeation flux and salt rejection performance of the GO composite membrane. The method can provide reference for the influence rule of the number of the hydroxyl functional groups of different graphene oxide composite films on the performance of the graphene oxide composite films, and has high application potential.
Description
Technical Field
The invention relates to a preparation method of a graphene oxide composite membrane with adjustable interlamellar spacing, and belongs to the technical field of preparation of graphene oxide membranes and pollutant filtration.
Background
In recent years, the demand for clean water has rapidly increased with the rapid growth of the population, which is a serious challenge. To address the water resource crisis, low cost and efficient nanofiltration may be the most promising solution. Nanofiltration technology is widely used in drinking water and wastewater treatment due to its low energy cost and environmentally friendly simple operation process, where the performance of the nanofiltration membrane is of paramount importance. Two-dimensional materials have been widely used in recent years as separation membranes due to their internal mass transfer channels. The novel two-dimensional Graphene Oxide (GO) base film has a nanopore and an adjustable lamellar structure, is simple in preparation method, contains a large number of oxygen-containing functional groups, has the advantages of excellent mechanical stability, good antibacterial and antifouling properties and the like, and is one of ideal new materials. Experimental research shows that the GO composite membrane is easy to swell in water environment, so that the performance is unstable, and the application of the GO membrane is limited. Research shows that the interlayer stability of the GO composite membrane can be improved by crosslinking of amine monomers. Therefore, the interfacial and interlayer stability of the GO membrane is respectively improved by adopting dopamine pretreatment and Ethylenediamine (EDA) crosslinking modes. There are still application limitations with low throughput. On the breakthrough of realizing high flux of the graphene oxide composite membrane, researchers adopt various methods to regulate and control the interlayer spacing of the GO composite membrane so as to improve the membrane performance. The third phase of 2018, Febri Baskoro et al, Journal of Membrane Science, reported that interlayer spacing was adjusted by physically or chemically inserting ions, molecules or nanomaterials into the layer to adjust the interlayer nanochannels. In addition, the degree of reduction of GO nanoplates can be adjusted by methods such as exposure to hydroiodic acid (HI) steam, reported by Euntae Yang in Journal of Membrane Science 2017, stage 10, to change the interlayer spacing. However, most of the process steps of these methods are complicated, and are not easy to realize in an environment-friendly and simple manner.
Disclosure of Invention
The invention provides a preparation method of a graphene oxide composite membrane capable of regulating and controlling interlamellar spacing aiming at the application limit of low flux of the existing GO composite membrane, the method can be realized by utilizing a simple thermodynamic means and changing the drying temperature, and the operation is convenient and simple.
The technical scheme of the invention is as follows: a preparation method of a graphene oxide composite membrane with adjustable interlamellar spacing comprises the following specific steps:
step one, carrying out interface modification on a membrane carrier to obtain a modified carrier;
step two, adding the GO dispersion liquid subjected to ultrasonic dispersion into an amine monomer, fully reacting to obtain a coating liquid, and passing the coating liquid through N2Loading the modified carrier under pressure;
and step three, drying to obtain GO composite membranes with different interlayer spacings.
Preferably, the membrane carrier in the first step is tubular, and the pore diameter of the membrane tube is 20-200 nm.
Preferably, the interfacial modification is dopamine graft modification, silane graft modification or O ═ CS long-chain molecular bridge modification.
Preferably, the ultrasonic frequency of the ultrasonic dispersion in the step two is 20-50kHz, and the ultrasonic time is 5-30 min.
Preferably, in the second step, the amine monomer is ethylenediamine, p-phenylenediamine, dopamine, butanediamine, polyethyleneimine, polyimide or polyamide.
The preferable concentration of GO in the coating liquid is 0.3-0.5 mg.L-1(ii) a The concentration of the amine monomer is 0.3-1 mM.
Preferably N2The pressurizing pressure is 1-3bar, and the pressurizing time is 5-120 min.
Preferably, the drying temperature in the third step is 40-100 ℃, and the drying time is 12-14 h.
The thickness of the GO film prepared by the method is 20-60 nm.
The dopamine modification adopts a method reported in fifth stage 2019 by Wangcai Red (chemical industry, academic Press); the silane grafting modification adopts a method disclosed by Yueyun Lou in Applied Surface Science 2014 in the fourth stage; the modification of the long-chain molecular bridge of O-CS adopts a method disclosed by Zhang Meng in the 10 th stage of Angewandte Chemie 2019.
The application system of the GO composite membrane prepared by the invention is one of nanofiltration, reverse osmosis, pervaporation and gas separation.
According to the invention, a thermodynamic means is innovatively adopted, and the number of oxygen-containing functional groups (hydroxyl groups) on the GO nano-sheets is influenced by changing the drying temperature, so that the pure water permeation flux and the salt rejection performance of the GO composite membrane are influenced.
Has the advantages that:
the GO interlayer spacing can be regulated and controlled at different drying temperatures, the method is simpler and more convenient than the existing method for regulating and controlling the interlayer spacing, the influence of the temperature on the performance of the GO composite membrane is large, and the law is obvious.
Drawings
FIG. 1 GO-EDA/Al prepared in examples 1, 2, 4 and 62O3Optical photo of the composite nanofiltration membrane;
FIG. 2 GO-EDA/Al prepared in examples 1, 2, 4 and 62O3Flux contrast plot of composite nanofiltration membrane;
FIG. 3 GO-EDA/Al prepared in examples 1, 2, 4 and 62O3The composite nanofiltration membrane has the interception performance on four single-component salt solutions.
Detailed Description
For a better understanding of the present invention, the following examples are given to further illustrate the present invention, but the present invention is not limited to the examples.
Example 1:
1.GO-EDA/Al2O3preparation of composite nanofiltration membrane
1) 50mL of 5mM Tris-HCl buffer was prepared, the pH was adjusted to 8.50 with hydrochloric acid, and 20mL of 1 mg/mL Tris-HCl buffer was added-1The dopamine (PDA) solution was magnetically stirred at room temperature for 10 min. Then Al with a pore diameter of 200nm2O3And immersing the inner surface of the membrane tube into the solution, standing for 20h in the dark, taking out, and washing residual PDA solution on the inner surface of the membrane tube by deionized water. And finally, drying the membrane tube in an oven at 60 ℃ for 2h to obtain the PDA modified ceramic membrane tube.
2) Taking 67 mu L of the solution with the concentration of 1 mg/mL-1Adding deionized water into the GO dispersion liquid in a conical flask to dilute to 200mL, and ultrasonically dispersing for 5min at 35kHz to form 0.3 mg.L-1GO dispersion of (1). Then, 4.50 μ L of EDA was added to the dispersion (final concentration: 0.3mM), and the mixture was magnetically stirred in a water bath at 80 ℃ for 1 hour to allow sufficient reaction, thereby obtaining a GO-EDA coating solution. By usingPressure-driven coating device at 1bar N2Loading it under pressure to PDA-Al2O3The inner surface of the membrane was maintained at a pressure of 1bar N2And purging for 2h under the condition to make the surface of the film layer more uniform. Finally drying in an oven at 40 ℃ for 12h to obtain GO-EDA/Al2O3A composite nanofiltration membrane.
2.GO-EDA/Al2O3Performance testing of composite nanofiltration membranes
Adopting a tubular membrane cross-flow filtration device, at the temperature of 20 ℃, the pressure of 5bar and the membrane surface flow rate of 1.3 m.s-1Determination of GO/Al2O3Pure water permeability coefficient of composite nanofiltration membrane and 1mM Na pair2SO4、NaCl、MgSO4And MgCl2Retention properties of the four mono-component salt solutions. And comparing the pure water permeability coefficients of the composite nanofiltration membrane before and after the composite nanofiltration membrane is soaked in pure water for 170h, 340h, 510h and 680h and the retention rates of the composite nanofiltration membrane on the four salt solutions, thereby representing the stability of the membrane. The pure water flux of the composite membrane obtained by calculation is 39.59 L.m-2·h-1·bar-1The retention for the four salts was: 82.86%, 17.55%, 54.52%, 12.23%. The composite membrane has the advantages of thickness of about 38nm, large interlayer spacing, higher flux and higher interception of four salts.
Example 2:
1.GO-EDA/Al2O3preparation of composite nanofiltration membrane
1) 50mL of 5mM Tris-HCl buffer was prepared, the pH was adjusted to 8.5 with hydrochloric acid, and 20mL of 1 mg/mL Tris-HCl buffer was added-1The dopamine (PDA) solution was magnetically stirred at room temperature for 10 min. Then Al with a pore diameter of 200nm2O3And immersing the inner surface of the membrane tube into the solution, standing for 20h in the dark, taking out, and washing residual PDA solution on the inner surface of the membrane tube by deionized water. And finally, drying the membrane tube in an oven at 60 ℃ for 2h to obtain the PDA modified ceramic membrane tube.
2) Taking 67 mu L of the solution with the concentration of 1 mg/mL-1Adding deionized water into the GO dispersion liquid in a conical flask to dilute to 200mL, and ultrasonically dispersing for 5min at 35kHz to form 0.3 mg.L-1GO dispersion of (1). Then, 4.5. mu.L of EDA was added to the above dispersion(final concentration is 0.3mM), and magnetically stirring the mixed solution in a water bath at 80 ℃ for 1h to allow the mixed solution to react fully to obtain the GO-EDA membrane coating solution. Using a pressure-driven coating device at 1bar N2Loading it under pressure to PDA-Al2O3The inner surface of the membrane was maintained at a pressure of 1bar N2And purging for 2h under the condition to make the surface of the film layer more uniform. Finally drying in a drying oven at 60 ℃ for 12h to obtain GO-EDA/Al2O3A composite nanofiltration membrane.
2.GO-EDA/Al2O3Performance testing of composite nanofiltration membranes
Adopting a tubular membrane cross-flow filtration device, at the temperature of 20 ℃, the pressure of 5bar and the membrane surface flow rate of 1.3 m.s-1Determination of GO/Al2O3Pure water permeability coefficient of composite nanofiltration membrane and 1mM Na pair2SO4、NaCl、MgSO4And MgCl2Retention properties of the four mono-component salt solutions. And comparing the pure water permeability coefficients of the composite nanofiltration membrane before and after the composite nanofiltration membrane is soaked in pure water for 170h, 340h, 510h and 680h and the retention rates of the composite nanofiltration membrane on the four salt solutions, thereby representing the stability of the membrane. The pure water flux of the composite membrane obtained by calculation is 28.50 L.m-2·h-1·bar-1The retention for the four salts was: 85.41%, 23.44%, 63.59%, 29.70%. The composite membrane has the advantages of thickness of about 32nm, larger interlayer spacing, higher flux and higher interception of four salts.
Example 3:
1.GO-PDA/Al2O3preparation of composite nanofiltration membrane
1) 50mL of 5mM Tris-HCl buffer was prepared, the pH was adjusted to 8.50 with hydrochloric acid, and 20mL of 1 mg/mL Tris-HCl buffer was added-1The dopamine (PDA) solution was magnetically stirred at room temperature for 10 min. Then Al with a pore diameter of 50nm2O3And immersing the inner surface of the membrane tube into the solution, standing for 20h in the dark, taking out, and washing residual PDA solution on the inner surface of the membrane tube by deionized water. And finally, drying the membrane tube in an oven at 60 ℃ for 2h to obtain the PDA modified ceramic membrane tube.
2) Taking 100 μ L of 1 mg/mL-1Adding deionized water to dilute the GO dispersion in a conical flaskReleasing to 200ml, ultrasonic dispersing at 50kHz for 10min to form 0.5 mg.L-1GO dispersion of (1). Then, after the pH value is adjusted to 8.50, 0.0125g of dopamine (PDA) is added into the dispersion liquid (the final concentration is 0.3mM), and the mixed liquid is magnetically stirred for 1h in a water bath at the temperature of 80 ℃ to fully react to obtain the GO-PDA coating liquid. Using 2bar of N2Loading it under pressure to PDA-Al2O3The inner surface of the membrane was maintained at a pressure of 2bar N2And purging for 2h under the condition to make the surface of the film layer more uniform. Finally drying in an oven at 40 ℃ for 14h to obtain GO-PDA/Al2O3A composite nanofiltration membrane.
2.GO-PDA/Al2O3Performance testing of composite nanofiltration membranes
Adopting a tubular membrane cross-flow filtration device, at the temperature of 20 ℃, the pressure of 5bar and the membrane surface flow rate of 1.3 m.s-1Determination of GO/Al2O3Pure water permeability coefficient of composite nanofiltration membrane and 1mM Na pair2SO4、NaCl、MgSO4And MgCl2Retention properties of the four mono-component salt solutions. And comparing the pure water permeability coefficients of the composite nanofiltration membrane before and after the composite nanofiltration membrane is soaked in pure water for 170h, 340h, 510h and 680h and the retention rates of the composite nanofiltration membrane on the four salt solutions, thereby representing the stability of the membrane. The pure water flux of the composite membrane obtained by calculation is 29.59 L.m-2·h-1·bar-1The retention for the four salts was: 80.58%, 19.42%, 56.89%, 15.46%. The composite membrane has the advantages of about 55nm of membrane thickness, larger interlayer spacing, higher flux and higher interception of four salts.
Example 4:
1.GO-EDA/Al2O3preparation of composite nanofiltration membrane
1) 50mL of 5mM Tris-HCl buffer was prepared, the pH was adjusted to 8.5 with hydrochloric acid, and 20mL of 1 mg/mL solution was added-1The dopamine (PDA) solution was magnetically stirred at room temperature for 10 min. Then Al with a pore diameter of 200nm2O3And immersing the inner surface of the membrane tube into the solution, standing for 20h in the dark, taking out, and washing residual PDA solution on the inner surface of the membrane tube by deionized water. Finally, drying the membrane tube in a drying oven at 60 ℃ for 2h to obtain the PDA modified ceramic membraneA tube.
2) Taking 67 mu L of the solution with the concentration of 1 mg/mL-1Adding deionized water into the GO dispersion liquid in a conical flask to dilute to 200mL, and performing ultrasonic dispersion at 35kHz for 5min to form 0.3 mg.L-1The uniformly dispersed GO dispersion of (a). Then, 13.5 μ L of EDA was added to the dispersion (final concentration: 0.3mM), and the mixture was magnetically stirred in a water bath at 80 ℃ for 1 hour to allow sufficient reaction, thereby obtaining a GO-EDA coating solution. Using a pressure-driven coating device at 1bar N2Loading it under pressure to PDA-Al2O3The inner surface of the membrane was maintained at a pressure of 1bar N2And purging for 2h under the condition to make the surface of the film layer more uniform. Finally drying in an oven at 80 ℃ for 12h to obtain GO-EDA/Al2O3A composite nanofiltration membrane.
2.GO-EDA/Al2O3Performance testing of composite nanofiltration membranes
Adopting a tubular membrane cross-flow filtration device, at the temperature of 20 ℃, the pressure of 5bar and the membrane surface flow rate of 1.3 m.s-1Determination of GO/Al2O3Pure water permeability coefficient of composite nanofiltration membrane and 1mM Na pair2SO4、NaCl、MgSO4And MgCl2Retention properties of the four mono-component salt solutions. And comparing the pure water permeability coefficients of the composite nanofiltration membrane before and after the composite nanofiltration membrane is soaked in pure water for 170h, 340h, 510h and 680h and the retention rates of the composite nanofiltration membrane on the four salt solutions, thereby representing the stability of the membrane. The pure water flux of the composite membrane obtained by calculation is 19.79 L.m-2·h-1·bar-1The retention for the four salts was: 86.20%, 40.56%, 53.55%, 30.74%. The composite membrane was about 28nm thick with somewhat smaller interlayer spacing than the composite membranes of examples 1-3, so that flux was reduced, but higher rejection was achieved for the four salts.
Example 5:
1.GO-PDA/Al2O3preparation of composite nanofiltration membrane
1) A CS solution was prepared by dissolving 0.05g of CS in 50mL of a 0.5 wt% aqueous acetic acid solution. Excess GA (25% aqueous solution) was added to the CS solution and reacted for 2min with stirring. The final O ═ CS solution was dip coated onto the inner surface of the ceramic membrane tube and allowed to stand for 5min before pouring out. The resulting ceramic membrane tubes were rinsed with deionized water and dried at room temperature.
2) Taking 100 μ L of 1 mg/mL-1Adding deionized water into the GO dispersion liquid in a conical flask to dilute to 200mL, and ultrasonically dispersing for 10min at 50kHz to form 0.5 mg.L-1The uniformly dispersed GO dispersion of (a). Then, after the pH value is adjusted to 8.50, 0.019g of dopamine is added into the dispersion liquid (the final concentration is 0.5mM), and the mixed liquid is magnetically stirred for 1 hour in a water bath at the temperature of 80 ℃ to fully react to obtain the GO-PDA coating liquid. Using 2bar of N2Loading it under pressure to PDA-Al2O3The inner surface of the membrane was maintained at a pressure of 2bar N2And purging for 5min under the condition to make the surface of the film layer more uniform. Finally drying in an oven at 40 ℃ for 14h to obtain GO-PDA/Al2O3A composite nanofiltration membrane.
2.GO-PDA/Al2O3Performance testing of composite nanofiltration membranes
Adopting a tubular membrane cross-flow filtration device, at the temperature of 20 ℃, the pressure of 5bar and the membrane surface flow rate of 1.3 m.s-1Determination of GO/Al2O3Pure water permeability coefficient of composite nanofiltration membrane and 1mM Na pair2SO4、NaCl、MgSO4And MgCl2Retention properties of the four mono-component salt solutions. And comparing the pure water permeability coefficients of the composite nanofiltration membrane before and after the composite nanofiltration membrane is soaked in pure water for 170h, 340h, 510h and 680h and the retention rates of the composite nanofiltration membrane on the four salt solutions, thereby representing the stability of the membrane. The pure water flux of the composite membrane obtained by calculation is 20.36 L.m-2·h-1·bar-1The retention for the four salts was: 80.14%, 18.32%, 50.92% and 14.35%. The thickness of the composite membrane is about 53nm, the interlayer spacing of the composite membrane is reduced compared with that of the composite membrane with the interlayer spacing of 1-3, the flux is slightly reduced, and high interception of four salts is realized.
Example 6:
1.GO-EDA/Al2O3preparation of composite nanofiltration membrane
1) 50mL of 5mM Tris-HCl buffer was prepared, the pH was adjusted to 8.5 with hydrochloric acid, and 20mL of 1 mg/mL Tris-HCl buffer was added-1The dopamine (PDA) solution was magnetically stirred at room temperature for 10 min. Then the aperture is measuredAl of 200nm2O3And immersing the inner surface of the membrane tube into the solution, standing for 20h in the dark, taking out, and washing residual PDA solution on the inner surface of the membrane tube by deionized water. And finally, drying the membrane tube in an oven at 60 ℃ for 2h to obtain the PDA modified ceramic membrane tube.
2) Taking 67 mu L of the solution with the concentration of 1 mg/mL-1Adding deionized water into the GO dispersion liquid in a conical flask to dilute to 200mL, and ultrasonically dispersing for 5min at 35kHz to form 0.3 mg.L-1The uniformly dispersed GO dispersion of (a). Then, 19.79 μ L of EDA was added to the dispersion (final concentration: 0.3mM), and the mixture was magnetically stirred in a water bath at 80 ℃ for 1 hour to allow sufficient reaction, thereby obtaining a GO-EDA coating solution. Using a pressure-driven coating device at 1bar N2Loading it under pressure to PDA-Al2O3The inner surface of the membrane was maintained at a pressure of 1bar N2And purging for 2h to make the surface of the film layer more uniform. Finally drying in a drying oven at 100 ℃ for 12h to obtain GO-EDA/Al2O3A composite nanofiltration membrane.
2.GO-EDA/Al2O3Performance testing of composite nanofiltration membranes
Adopting a tubular membrane cross-flow filtration device, at the temperature of 20 ℃, the pressure of 5bar and the membrane surface flow rate of 1.3 m.s-1Determination of GO/Al2O3Pure water permeability coefficient of composite nanofiltration membrane and 1mM Na pair2SO4、NaCl、MgSO4And MgCl2Retention properties of the four mono-component salt solutions. And comparing the pure water permeability coefficients of the composite nanofiltration membrane before and after the composite nanofiltration membrane is soaked in pure water for 170h, 340h, 510h and 680h and the retention rates of the composite nanofiltration membrane on the four salt solutions, thereby representing the stability of the membrane. The pure water flux of the composite membrane obtained by calculation is 10.30 L.m-2·h-1·bar-1The retention for the four salts was: 76.87%, 42.09%, 59.75%, 40.86%. The composite membrane is about 25nm thick, has small interlayer spacing and realizes high interception of four salts.
a1-a4 are GO-EDA/Al prepared in examples 1, 2, 4 and 6, respectively2O3The optical photograph of the composite nanofiltration membrane is shown in FIG. 1, wherein a1-a4 are GO-EDA/Al prepared in examples 1, 2, 4 and 6 respectively2O3The optical photo of the composite nanofiltration membrane can be seen from the graph, the film tube prepared in example 1 has the lowest drying temperature and the lightest color, and the film tube prepared in example 4 has the highest drying temperature and the darkest color.
GO-EDA/Al prepared in examples 1, 2, 4 and 62O3The flux comparison graph of the composite nanofiltration membrane is shown in fig. 2, and it can be seen from the graph that the higher the drying temperature of the prepared GO composite membrane is, the fewer the number of hydroxyl groups between layers is, the smaller the interlayer spacing is, and the pure water flux is correspondingly reduced.
GO-EDA/Al prepared in examples 1, 2, 4 and 62O3The diagram of the interception performance of the composite nanofiltration membrane on four single-component salt solutions is shown in fig. 3, and it can be seen from the diagram that the higher the drying temperature is, the fewer the hydroxyl groups are, the smaller the interlayer spacing is, but the interception on monovalent anion salts sodium chloride and magnesium chloride is correspondingly increased, and the interception on divalent salts sodium sulfate and magnesium sulfate is higher.
The preparation of the composite membrane can be realized by adjusting the process parameters recorded in the content of the invention, and the performance rule basically consistent with the examples can be shown by simply changing the drying temperature.
Claims (9)
1. A preparation method of a graphene oxide composite membrane with adjustable interlamellar spacing comprises the following specific steps:
step one, carrying out interface modification on a membrane carrier to obtain a modified carrier;
step two, adding the GO dispersion liquid subjected to ultrasonic dispersion into an amine monomer, fully reacting to obtain a coating liquid, and passing the coating liquid through N2Loading the modified carrier under pressure;
and step three, drying to obtain GO composite membranes with different interlayer spacings.
2. The method according to claim 1, wherein the membrane carrier in the first step is tubular, and the pore diameter of the membrane tube is 20 to 200 nm.
3. The method according to claim 1, wherein the interfacial modification is dopamine graft modification, silane graft modification or O ═ CS long-chain molecular bridge modification.
4. The method according to claim 1, wherein the ultrasonic frequency of the ultrasonic dispersion in the step two is 20 to 50kHz, and the ultrasonic time is 5 to 30 min.
5. The method according to claim 1, wherein the amine monomer in step two is ethylenediamine, p-phenylenediamine, dopamine, butanediamine, polyethyleneimine, polyimide, or polyamide.
6. The production method according to claim 1, characterized in that the concentration of GO in the coating solution is 0.3-0.5 mg-L-1(ii) a The concentration of the amine monomer is 0.3-1 mM.
7. The method according to claim 1, wherein N is N2The pressurizing pressure is 1-3bar, and the pressurizing time is 5-120 min.
8. The method according to claim 1, wherein the drying temperature in step three is 40-100 ℃ and the drying time is 12-14 hours.
9. The preparation method according to claim 1, characterized in that the prepared GO has a film thickness of 20-60 nm.
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| CN104232108A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of pure inorganic composite membrane based on graphene |
| CN105664738A (en) * | 2016-04-11 | 2016-06-15 | 江西师范大学 | Graphene oxide-based composite membrane for treating radioactive wastewater |
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| CN104232108A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of pure inorganic composite membrane based on graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114984757A (en) * | 2022-06-21 | 2022-09-02 | 青岛大学 | Graphene oxide/chitosan composite nanofiltration membrane with controllable water flux or rejection rate and application thereof |
| CN114984757B (en) * | 2022-06-21 | 2023-09-22 | 青岛大学 | Graphene oxide/chitosan composite nanofiltration membrane with controllable water flux or retention rate and application thereof |
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