CN108325399B - Preparation method of graphene polyamide reverse osmosis membrane - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 146
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 40
- 239000004952 Polyamide Substances 0.000 title claims abstract description 24
- 229920002647 polyamide Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 78
- 239000012071 phase Substances 0.000 claims description 65
- 229920002492 poly(sulfone) Polymers 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 238000005266 casting Methods 0.000 claims description 34
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 26
- 238000007664 blowing Methods 0.000 claims description 22
- 238000002791 soaking Methods 0.000 claims description 22
- 238000007790 scraping Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000008346 aqueous phase Substances 0.000 claims description 15
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims description 13
- 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 13
- 238000004140 cleaning Methods 0.000 claims description 13
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 12
- 229940082004 sodium laurate Drugs 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- -1 acyl chlorinated graphene Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 104
- 230000004907 flux Effects 0.000 description 11
- 238000001728 nano-filtration Methods 0.000 description 6
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of reverse osmosis membrane modification, in particular to a preparation method of a graphene polyamide reverse osmosis membrane.
Description
Technical Field
The invention relates to the technical field of semipermeable membrane modification, in particular to a preparation method of a graphene polyamide reverse osmosis membrane.
Background
The reverse osmosis membrane filtration technology has the advantages of high efficiency, low energy consumption, easy operation and the like, is widely applied to the fields of seawater desalination, wastewater treatment and the like, and is always a hotspot in the field of domestic outer membrane separation. The reverse osmosis membrane uses static pressure difference at two sides of the membrane as driving force, overcomes osmotic pressure of the solvent, selectively intercepts ionic substances and only permeates the solvent, thereby realizing separation of liquid mixture. In contrast to other membrane separation techniques, reverse osmosis is the most complex process, and its separation behavior, in addition to being related to the pore size, also depends to a great extent on the dissolution, adsorption and diffusion of the permeate components in the membrane, which are closely related to the chemical and physical properties of the reverse osmosis membrane.
Graphene is a polymer made of carbon atoms in sp2The thickness of the graphene formed by single-layer carbon atoms of the honeycomb-shaped planar thin film formed by the hybridization mode is only 0.34nm, and the graphene is the thinnest and hardest nano material at present. Graphene oxide is one of graphene derivatives, and has a structure substantially the same as that of graphene, except that a large number of oxygen-containing groups are connected to a base plane formed by a single carbon atom and extending infinitely in a two-dimensional space, and the insertion of the oxygen-containing groups breaks pi bonds in the planes of the carbon layers of graphene, thereby losing the ability to conduct electrons, but endows graphene oxide with some new properties, such as dispersibility, hydrophilicity, and compatibility with polymers. Meanwhile, the oxygen-containing groups in the graphene oxide can be modified to obtain different types of functionalized graphene.
With the rapid development and popularization of graphene oxide materials, polymers and graphene oxide, especially polymers and modified graphene oxide, have become the main direction of reverse osmosis membrane development. For example, CN102989331B discloses a polymeric membrane/graphene hybrid nanofiltration membrane and a preparation method thereof, in which graphene is introduced into a functional layer of the nanofiltration membrane, so as to improve the water flux and rejection rate of the nanofiltration membrane. However, the nanofiltration membrane has the defects of short service life and reduced membrane performance after being washed for many times.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a graphene polyamide reverse osmosis membrane.
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding carboxylated graphene and polysulfone into N, N-dimethylformamide, heating and ultrasonically treating, and performing vacuum defoaming to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, and immersing the membrane casting solution in deionized water for curing to obtain a polysulfone base membrane;
(3) adding aminated graphene, 4-dimethylaminopyridine and m-phenylenediamine into deionized water to prepare an aqueous phase solution;
(4) adding acyl chloride graphene and trimesoyl chloride into cyclohexane to prepare an oil phase solution;
(5) soaking polysulfone base membrane in the water phase solution, taking out, blowing off the redundant water phase solution on the surface by using an air knife, soaking in the oil phase solution again, carrying out interfacial polymerization reaction, taking out, blowing off the redundant oil phase solution on the surface by using the air knife, drying, and cleaning by using deionized water to obtain the polysulfone base membrane.
In the step (1), the amount of the carboxylated graphene is 0.05-0.3 g, the mass percentage of the polysulfone is 15-25 g, and the amount of the N, N-dimethylformamide is 250 ml.
In the step (1), heating and ultrasonic treatment are carried out for 2-4 hours, the heating temperature is 95-100 ℃, and the vacuum defoaming time is 14-20 hours.
In the step (2), the thickness of the scraped film is 10-15 μm, the temperature of the deionized water is 10-20 ℃, and the curing time is 15-20 min.
In the step (3), 0.5-2 g of aminated graphene, 0.1-0.2 g of 4-dimethylaminopyridine, 3-5 g of sodium laurate, 150-350 g of m-phenylenediamine and 5L of deionized water.
In the step (4), 0.1-1 g of acyl chloride graphene, 5-10 ml of diethyl ether, 20-100 g of trimesoyl chloride and 2L of cyclohexane are added.
In the step (5), the temperature of the aqueous phase solution is 10-15 ℃, the time for immersing the aqueous phase solution is 40-60 min, the temperature of the oil phase solution is 30-40 ℃, the interfacial polymerization time is 1-3 min, the drying temperature is 70 ℃, the drying time is 10-20 min, and the cleaning time is 10 min.
Compared with the prior art, the method has the following advantages:
1. the preparation method comprises the steps of selecting proper modified graphene, doping the modified graphene in a membrane casting solution, a water phase solution and an oil phase solution for preparing the reverse osmosis membrane, connecting the modified graphene with a compound of the reverse osmosis membrane and the modified graphene through chemical amide bonds, increasing the structural stability inside the reverse osmosis membrane, and prolonging the service life of the reverse osmosis membrane.
2. The polyamide layer and the base membrane layer of the reverse osmosis membrane are both doped with the modified graphene, so that the hydrophilicity of the polyamide layer on the surface is enhanced, the water flux of a water delivery channel in the base membrane is improved, and the integral water flux of the reverse osmosis membrane is increased.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments and test examples, but the scope of protection is not limited to the description.
Example 1
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.05g of carboxylated graphene and 15g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 2 hours at the temperature of 95 ℃, and carrying out vacuum defoaming for 14 hours to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 10 microns, immersing the membrane casting solution in deionized water at 10 ℃, and curing for 15min to obtain a polysulfone-based membrane;
(3) adding 0.5g of aminated graphene, 0.1g of 4-dimethylaminopyridine, 3g of sodium laurate and 150g of m-phenylenediamine into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 0.1g of acyl chlorinated graphene, 5ml of diethyl ether and 20g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking the polysulfone basal membrane into 10 ℃ water phase solution, keeping the water phase solution for 40min, taking out, blowing off redundant water phase solution on the surface by using an air knife, soaking into 30 ℃ oil phase solution, carrying out interfacial polymerization reaction for 1min, taking out, blowing off redundant oil phase solution on the surface by using an air knife, drying for 10min at 70 ℃, and cleaning for 10min by using deionized water to obtain the polysulfone basal membrane.
Example 2
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.15g of carboxylated graphene and 20g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 3 hours at the temperature of 97 ℃, and carrying out vacuum defoaming for 17 hours to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 13 microns, immersing the membrane casting solution in deionized water at 15 ℃, and curing for 18min to obtain a polysulfone base membrane;
(3) 1g of aminated graphene, 0.15g of 4-dimethylaminopyridine, 4g of sodium laurate and 250g of m-phenylenediamine are added into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 0.5g of acyl chlorinated graphene, 7.5ml of diethyl ether and 60g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking polysulfone base membrane in 13 deg.C water phase solution, maintaining for 50min, taking out, blowing off excessive water phase solution on surface with air knife, soaking in 35 deg.C oil phase solution, performing interfacial polymerization for 2min, taking out, blowing off excessive oil phase solution on surface with air knife, oven drying at 70 deg.C for 15min, and washing with deionized water for 10 min.
Example 3
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.3g of carboxylated graphene and 25g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 4 hours at the temperature of 100 ℃, and carrying out vacuum defoaming for 20 hours to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 15 microns, immersing the membrane casting solution in deionized water at the temperature of 20 ℃, and curing for 20min to obtain a polysulfone-based membrane;
(3) adding 2g of aminated graphene, 0.2g of 4-dimethylaminopyridine, 5g of sodium laurate and 350g of m-phenylenediamine into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 1g of acyl chlorinated graphene, 10ml of diethyl ether and 100g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking the polysulfone basal membrane into a 15 ℃ water phase solution, keeping the water phase solution for 60min, taking out, blowing off the redundant water phase solution on the surface by using an air knife, soaking into a 40 ℃ oil phase solution, carrying out interfacial polymerization reaction for 3min, taking out, blowing off the redundant oil phase solution on the surface by using the air knife, drying for 20min at 70 ℃, and cleaning for 10min by using deionized water to obtain the polysulfone basal membrane.
Example 4
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 21g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 2h at the heating temperature of 98 ℃, and carrying out vacuum defoaming for 16h to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 12 microns, immersing the membrane casting solution in deionized water at 10 ℃, and curing for 18min to obtain a polysulfone base membrane;
(3) adding 1.2g of aminated graphene, 0.12g of 4-dimethylaminopyridine, 3.5g of sodium laurate and 180g of m-phenylenediamine into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 0.4g of acyl chlorinated graphene, 6ml of diethyl ether and 35g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking a polysulfone base membrane into a 11 ℃ water phase solution, keeping the temperature in the water phase solution for 55min, taking out, blowing off redundant water phase solution on the surface by using an air knife, soaking into a 32 ℃ oil phase solution, carrying out interfacial polymerization reaction for 2min, taking out, blowing off redundant oil phase solution on the surface by using an air knife, drying for 18min at 70 ℃, and cleaning for 10min by using deionized water to obtain the polysulfone base membrane.
Example 5
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.24g of carboxylated graphene and 22g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 4 hours at the temperature of 97 ℃, and carrying out vacuum defoaming for 18 hours to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 14 microns, immersing the membrane casting solution in deionized water at 13 ℃, and curing for 16min to obtain a polysulfone base membrane;
(3) 0.18g of 4-dimethylaminopyridine, 4.2g of sodium laurate and 320g of m-phenylenediamine are added into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 0.7g of acyl chlorinated graphene, 8ml of diethyl ether and 90g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking a polysulfone base membrane into a 13 ℃ water phase solution, keeping the temperature in the water phase solution for 45min, taking out, blowing off redundant water phase solution on the surface by using an air knife, soaking into a 32 ℃ oil phase solution, carrying out interfacial polymerization reaction for 1min, taking out, blowing off redundant oil phase solution on the surface by using an air knife, drying for 14min at 70 ℃, and cleaning for 10min by using deionized water to obtain the polysulfone base membrane.
Example 6
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.21g of carboxylated graphene and 18g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 3 hours at the temperature of 95 ℃, and carrying out vacuum defoaming for 15 hours to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 12 microns, immersing the membrane casting solution in deionized water at the temperature of 11 ℃, and curing for 19min to obtain a polysulfone base membrane;
(3) 1.8g of aminated graphene, 0.16g of 4-dimethylaminopyridine, 4.5g of sodium laurate and 290g of m-phenylenediamine are added into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 9ml of diethyl ether and 75g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking polysulfone base membrane in 15 deg.C water phase solution, maintaining for 53min, taking out, blowing off excessive water phase solution on surface with air knife, soaking in 38 deg.C oil phase solution, performing interfacial polymerization for 2min, taking out, blowing off excessive oil phase solution on surface with air knife, oven drying at 70 deg.C for 17min, and washing with deionized water for 10 min.
Example 7
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.19g of carboxylated graphene and 16g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 2.5h at the temperature of 95 ℃, and carrying out vacuum defoaming for 18h to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 12 microns, immersing the membrane casting solution in deionized water at 13 ℃, and curing for 19min to obtain a polysulfone base membrane;
(3) adding 2.5g of acyl chloride graphene, 0.13g of 4-dimethylaminopyridine, 4.4g of sodium laurate and 245g of m-phenylenediamine into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 1.2g of aminated graphene, 8.5ml of diethyl ether and 50g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking polysulfone base membrane in 12 deg.C water phase solution, maintaining for 53min, taking out, blowing off excessive water phase solution on surface with air knife, soaking in 35 deg.C oil phase solution, performing interfacial polymerization for 3min, taking out, blowing off excessive oil phase solution on surface with air knife, oven drying at 70 deg.C for 17min, and washing with deionized water for 10 min.
Example 8
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.25g of aminated graphene and 25g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 4 hours at the temperature of 96 ℃, and carrying out vacuum defoaming for 14 hours to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 11 microns, immersing the membrane casting solution in deionized water at 16 ℃, and curing for 16min to obtain a polysulfone base membrane;
(3) adding 1.5g of carboxylated graphene, 0.14g of 4-dimethylaminopyridine, 3.8g of sodium laurate and 280g of m-phenylenediamine into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 0.35g of acyl chlorinated graphene, 6.5ml of diethyl ether and 70g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking a polysulfone base membrane in a 13 ℃ water phase solution, keeping the temperature in the water phase solution for 47min, taking out, blowing off the redundant water phase solution on the surface by using an air knife, soaking in a 34 ℃ oil phase solution, carrying out interfacial polymerization reaction for 1min, taking out, blowing off the redundant oil phase solution on the surface by using an air knife, drying for 16min at 70 ℃, and cleaning for 10min by using deionized water to obtain the polysulfone base membrane.
Example 9
A preparation method of a graphene polyamide reverse osmosis membrane comprises the following steps:
(1) adding 0.75g of acyl chloride graphene and 19g of polysulfone into 250ml of N, N-dimethylformamide, heating and ultrasonically treating for 2h at the temperature of 98 ℃, and carrying out vacuum defoaming for 15h to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, wherein the membrane scraping thickness is 15 microns, immersing the membrane casting solution in deionized water at 13 ℃, and curing for 15min to obtain a polysulfone base membrane;
(3) 1.7g of aminated graphene, 0.13g of 4-dimethylaminopyridine, 5g of sodium laurate and 300g of m-phenylenediamine are added into 5L of deionized water to prepare an aqueous phase solution;
(4) adding 1.5g of carboxylated graphene, 8ml of diethyl ether and 85g of trimesoyl chloride into 2L of cyclohexane to prepare an oil phase solution;
(5) soaking the polysulfone basal membrane into 10 ℃ water phase solution, keeping the water phase solution for 40min, taking out, blowing off redundant water phase solution on the surface by using an air knife, soaking into 40 ℃ oil phase solution, carrying out interfacial polymerization reaction for 2min, taking out, blowing off redundant oil phase solution on the surface by using an air knife, drying for 17min at 70 ℃, and cleaning for 10min by using deionized water to obtain the polysulfone basal membrane.
Test examples
Sample groups 1-9 were reverse osmosis membranes prepared in examples 1-9, and a nanofiltration membrane as disclosed in CN102989331B was used as a control group.
The filtration effect of the sample groups 1 to 9 and the control group was tested. The test solution was 2000ppm NaCl solution, the operating pressure was 150psi, the pH was 7.3, and the water flux and rejection of the membrane after the first 48h was tested. Next, the membranes of the experimental group were subjected to regenerative cleaning for 30min, and the water flux and rejection rate of the membranes after the second 48h were tested. Thereafter, the membrane water flux and rejection after 48h were tested for the third to tenth test runs with the "wash regeneration" and "test" being alternated for 8 times, and the results are reported in table 1:
TABLE 1
Table 1 (continuation watch)
Table 1 (continuation watch)
As can be seen from the above table, the reverse osmosis membranes prepared in sample groups 1 to 3 have high water flux and good rejection rate, and the water flux is about 5% polluted after 10 times of cleaning. When the reverse osmosis membrane of the sample group 4 is tested for the 8 th time, the trends of water flux and rejection rate are abnormal, and the phenomenon of membrane structure damage exists. The reverse osmosis membranes of the sample groups 5 and 6 are lack of modified graphene in part of the preparation process, so that the filtering effect is obviously reduced, and particularly, the membrane pollution degree of the reverse osmosis membrane of the sample group 6 is increased. The reverse osmosis membranes of sample groups 7-9 have good performance in the initial test, but have membrane damage phenomenon after regeneration and cleaning, increased water flux, reduced rejection rate and poor stability. And the nanofiltration membrane of the comparison group is tested at the 7 th time, the water flux begins to increase, the interception rate is reduced, and the membrane structure is damaged.
Claims (7)
1. The preparation method of the graphene polyamide reverse osmosis membrane is characterized by comprising the following steps:
(1) adding carboxylated graphene and polysulfone into N, N-dimethylformamide, heating and ultrasonically treating, and performing vacuum defoaming to obtain a membrane casting solution;
(2) pouring the membrane casting solution on a glass plate for membrane scraping treatment, and immersing the membrane casting solution in deionized water for curing to obtain a polysulfone base membrane;
(3) adding aminated graphene, 4-dimethylaminopyridine, sodium laurate and m-phenylenediamine into deionized water to prepare an aqueous phase solution;
(4) adding acyl chlorinated graphene, diethyl ether and trimesoyl chloride into cyclohexane to prepare an oil phase solution;
(5) soaking polysulfone base membrane in the water phase solution, taking out, blowing off the redundant water phase solution on the surface by using an air knife, soaking in the oil phase solution again, carrying out interfacial polymerization reaction, taking out, blowing off the redundant oil phase solution on the surface by using the air knife, drying, and cleaning by using deionized water to obtain the polysulfone base membrane.
2. The method for preparing a graphene polyamide reverse osmosis membrane according to claim 1, wherein in the step (1), the amount of carboxylated graphene is 0.05-0.3 g, the amount of polysulfone is 15-25 g, and the amount of N, N-dimethylformamide is 250 ml.
3. The preparation method of the graphene polyamide reverse osmosis membrane according to claim 1, wherein in the step (1), the heating ultrasound is performed for 2-4 hours at a heating temperature of 95-100 ℃ for 14-20 hours of vacuum defoaming.
4. The preparation method of the graphene polyamide reverse osmosis membrane according to claim 1, wherein in the step (2), the thickness of the scraped membrane is 10-15 μm, the temperature of deionized water is 10-20 ℃, and the curing time is 15-20 min.
5. The method for preparing the graphene polyamide reverse osmosis membrane according to claim 1, wherein in the step (3), 0.5-2 g of aminated graphene, 0.1-0.2 g of 4-dimethylaminopyridine, 3-5 g of sodium laurate, 150-350 g of m-phenylenediamine and 5L of deionized water are added.
6. The method for preparing the graphene polyamide reverse osmosis membrane according to claim 1, wherein in the step (4), the amount of the acylchlorinated graphene is 0.1-1 g, the amount of the diethyl ether is 5-10 ml, the amount of the trimesoyl chloride is 20-100 g, and the amount of the cyclohexane is 2L.
7. The preparation method of the graphene polyamide reverse osmosis membrane according to claim 1, wherein in the step (5), the temperature of the aqueous phase solution is 10-15 ℃, the time for immersing the aqueous phase solution is 40-60 min, the temperature of the oil phase solution is 30-40 ℃, the interfacial polymerization time is 1-3 min, the drying temperature is 70 ℃, the drying time is 10-20 min, and the cleaning time is 10 min.
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