CN110548414A - Separation membrane based on zwitterion functionalized graphene oxide and preparation method thereof - Google Patents
Separation membrane based on zwitterion functionalized graphene oxide and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 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 72
- 238000000926 separation method Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 28
- 239000002135 nanosheet Substances 0.000 claims description 27
- -1 amine compounds Chemical class 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000004528 spin coating Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 7
- 229930188620 butyrolactone Natural products 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D71/50—Polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a separation membrane based on zwitterion functionalized graphene oxide and a preparation method thereof. The separation membrane utilizes the layered structure of the graphene oxide modified by zwitterions and the affinity to water, so that water molecules are rapidly transmitted, and meanwhile, a stable membrane structure is constructed by utilizing the synergistic effect of the graphene oxide and a polymer, and finally, good water selective separation is shown in an alcohol-water separation system. The method disclosed by the invention is simple and economic in process, realizes high flux and high separation selectivity, ensures the stability of the membrane structure, improves the separation efficiency of the membrane, and has universality and good application prospect.
Description
Technical Field
The invention relates to a separation membrane based on zwitterion functionalized graphene oxide and a preparation method thereof, and the prepared membrane can be used for selective rapid permeation of water in an alcohol-water system.
Background
Material separation (purification, recovery and recycling) is a crucial component in various chemical industries, which accounts for a large part of the energy consumption, operation and capital costs in industrial production. Therefore, the development of a novel efficient and energy-saving separation process is a main direction for realizing energy conservation and emission reduction in the chemical industry, and has important significance for sustainable development of the chemical industry. Compared with the traditional separation technologies such as rectification, evaporation, drying and the like, the membrane separation technology is an energy-saving and environment-friendly separation technology and has the characteristics of high separation efficiency and low carbon emission.
Graphene oxide is a representative two-dimensional membrane material, has the thickness of a monoatomic layer, is easy to chemically modify, is easy to assemble to form a regular and adjustable nano mass transfer channel, and shows great prospect in the development of high-performance membrane materials. However, in aqueous environments, the swelling phenomenon of graphene oxide membranes and the restrictive relationship between membrane permeation flux and selectivity remain key challenges for achieving high efficiency separation processes. To address this problem, researchers have developed various regulatory approaches such as partial reduction, covalent crosslinking, and external pressure regulation. However, most of these studies have focused on modulating the physical size of the mass transfer channels between graphene oxide membrane layers, which typically results in increased separation factors and stability, but with a concomitant decrease in flux, also results in lower separation efficiency. Therefore, there is an urgent need to develop an efficient method while achieving high flux, separation selectivity and membrane structure stability.
Disclosure of Invention
The invention aims to provide a separation membrane based on zwitterion functionalized graphene oxide, and the invention also aims to provide a preparation method of the separation membrane. The composite membrane prepared by the method shows good permeation flux, separation selectivity and stability in the separation of an alcohol-water system. The preparation method is simple and easy to implement, and is green and environment-friendly.
The technical scheme of the invention is as follows: a separation membrane based on zwitterion functionalized graphene oxide is characterized in that: the graphene oxide membrane is composed of a separation layer and a support layer, wherein the membrane layer formed by alternately spin-coating a polymer solution and a functionalized graphene oxide solution is used as the separation layer, and the polymer ultrafiltration membrane is used as the support layer.
Preferably, the thickness of the separation layer is 15-55 nm.
The invention also provides a method for preparing the separation membrane, which comprises the following steps:
(1) Zwitterionic functionalized graphene oxide: respectively dispersing graphene oxide nanosheets, amine compounds and ester compounds in the same organic solvent, adding the amine compound solution into the graphene oxide solution, reacting for 1-2h at 40-60 ℃, then adding the ester compound solution, and reacting for 3-5h at 40-60 ℃; centrifuging to prepare a precipitate, washing by an alcohol solvent, and drying in vacuum to obtain a zwitterion functionalized graphene oxide nanosheet;
(2) Preparing a membrane preparation liquid: uniformly dispersing the prepared zwitterion functionalized graphene oxide nanosheets in a solvent to prepare a graphene oxide membrane preparation solution with the concentration of 0.1-0.4mg/ml for later use; uniformly dispersing the polymer in a solvent to prepare a polymer solution with the concentration of 0.2-0.6mg/ml for later use;
(3) Preparation of the film: placing a support body in a spin coater, alternately spin-coating the polymer solution prepared in the step (2) and the graphene oxide membrane-making solution on the polymer ultrafiltration membrane support body, after a layer of polymer solution is spin-coated, spin-coating and washing with deionized water once, then spin-coating a layer of graphene oxide membrane-making solution, and spin-coating and washing with deionized water once;
(4) And (4) circularly operating the step (3) to the required number of layers, and finally placing the prepared membrane in a vacuum drying oven for drying.
Preferably, the material of the polymer ultrafiltration membrane support is at least one of polyacrylonitrile, polycarbonate or polyvinylidene fluoride.
Preferably, the organic solvent is one of 1-methyl-2-pyrrolidone, N-N-2-methylformamide, acetone or dimethyl sulfoxide; the alcohol solvent is one of methanol or ethanol.
Preferably, the amine compound in the step (1) is one of ethanolamine or ethylenediamine; the ester compound is one of propane sultone or butane lactone.
Preferably, the concentration of the graphene oxide nanosheet solution in the step (1) is 0.2-0.5mg/ml, and the concentrations of the amine compound and the ester compound are both 1-5 mg/ml; the mass of the amine compound is 2-6 times that of the graphene oxide; the mass of the ester compound is 1-2 times of that of the compound A.
Preferably, the rotation speed of the centrifugation in the step (1) is 8000-12000rpm, and the centrifugation time is 10-30 min; the drying temperature is 25-50 ℃.
Preferably, the solvent in the step (2) is one of water, ethanol water solution or methanol water solution; the polymer is one of polydiallyldimethylammonium, polyethyleneimine or polyallylamine hydrochloride.
The spin coating conditions described in step (3) are preferred: the rotation speed is 1000-2000rpm, and the time is 30-60 s.
Preferably, the required number of layers in the step (4) is 5-20; the drying temperature is 25-50 ℃.
The separation membrane obtained by the vegetation of the invention has excellent separation performance on ethanol/water systems, when the temperature is 70 ℃, and the water content on the raw material side is 10%, the flux of the membrane is 2277-3995 g/m 2 h, and the separation factor is 42-1958.
Has the advantages that:
According to the method disclosed by the invention, zwitterion modification is carried out on graphene oxide, the affinity of graphene oxide to water molecules is enhanced, the construction of a rapid water transmission channel is promoted under the synergistic effect of graphene oxide and polymers, high flux, high separation selectivity and high membrane structure stability are obtained, and the efficiency of a membrane separation process is improved. The thickness and the structure of the membrane are controlled by adjusting the relevant preparation conditions of the membrane, and the separation performance of the membrane is effectively regulated and controlled to adapt to different separation requirements. The method has simple and economic process and wide application range.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of the film obtained in example 5.
Detailed Description
Comparative example 1
(1) And dispersing the graphene oxide nanosheets in a deionized water solution with the concentration of 0.2mg/ml, and dispersing polyethyleneimine in the deionized water solution with the concentration of 0.2 mg/ml.
(2) And (3) alternately spin-coating 5 layers of the solution in the step (1) on a polyacrylonitrile support body at 2000rpm for 60 s.
(3) The prepared membrane is dried in vacuum at 25 ℃ to obtain a separation membrane, the thickness of the separation layer is 15nm, the separation performance of the membrane prepared in the example on an ethanol/water system is measured, when the temperature is 70 ℃ and the water content on the raw material side is 10%, the flux of the membrane is 6800g/m 2 h, and the separation factor is 16.
Example 1
(1) Uniformly dispersing graphene oxide nano sheets in N-N-2-methylformamide with the concentration of 0.2mg/ml, and respectively dispersing ethanolamine and propane sultone in the N-N-2-methylformamide with the concentrations of 1 mg/ml.
(2) Taking 30ml of graphene oxide solution, adding 12ml of ethanolamine solution with 2 times of graphene oxide content, reacting for 1h at 40 ℃, then adding 12ml of propane sultone solution with 1 time of ethanolamine content, and reacting for 3h at 40 ℃. Centrifuging for 10min at the rotation speed of 8000rpm to obtain precipitate, washing with methanol, and vacuum drying at 25 deg.C to obtain zwitterion functionalized graphene oxide nanosheet.
(3) Dispersing the zwitterion functionalized graphene oxide nanosheet prepared in the step (2) in a deionized water solution, wherein the concentration is 0.2mg/ml, and dispersing polyethyleneimine in the deionized water solution, wherein the concentration is 0.2 mg/ml.
(4) And (4) alternately spin-coating 5 layers of the solution in the step (3) on a polyacrylonitrile support body at 1000rpm for 30 s.
(5) the prepared membrane is dried in vacuum at 25 ℃ to obtain a separation membrane, the thickness of the separation layer is 15nm, the separation performance of the membrane prepared in the example on an ethanol/water system is measured, when the temperature is 70 ℃ and the water content on the raw material side is 10%, the flux of the membrane is 3995g/m 2 h, and the separation factor is 42.
Example 2
(1) Uniformly dispersing graphene oxide nano sheets in N-N-2-methylformamide with the concentration of 0.5mg/ml, and respectively dispersing ethylenediamine and propane sultone in the N-N-2-methylformamide with the concentrations of 5 mg/ml.
(2) Taking 30ml of graphene oxide solution, adding 6ml of ethylenediamine solution with the content of 2 times that of graphene oxide, reacting for 2 hours at 60 ℃, then adding 12ml of propane sultone solution with the content of 2 times that of ethylenediamine, and reacting for 5 hours at 60 ℃. Centrifuging for 30min at the rotating speed of 12000rpm to obtain a precipitate, washing with ethanol, and vacuum-drying at 50 ℃ to obtain the zwitterion functionalized graphene oxide nanosheet.
(3) Dispersing the zwitterion functionalized graphene oxide nanosheet prepared in the step (2) in a deionized water solution, wherein the concentration is 0.2mg/ml, and dispersing polyethyleneimine in the deionized water solution, wherein the concentration is 0.2 mg/ml.
(4) And (3) alternately spin-coating 15 layers of the solution in the step (3) on a polyvinylidene fluoride support at 2000rpm for 60 s.
(5) The membrane obtained in this example was dried under vacuum at 50 ℃ to obtain a separation membrane, the thickness of the separation layer was 45nm, and the separation performance of the membrane obtained in this example was measured for an ethanol/water system, and when the temperature was 70 ℃ and the water content on the raw material side was 10%, the flux of the membrane was 2277g/m 2. h, and the separation factor was 324.
Example 3
(1) Uniformly dispersing graphene oxide nanosheets in 1-methyl-2-pyrrolidone to a concentration of 0.2mg/ml, and respectively dispersing ethanolamine and butyrolactone in 1-methyl-2-pyrrolidone to concentrations of 2 mg/ml.
(2) Taking 30ml of graphene oxide solution, adding 12ml of ethanolamine solution with the content of 4 times that of graphene oxide, reacting for 1h at 50 ℃, then adding 24ml of butyrolactone solution with the content of 2 times that of ethanolamine, and reacting for 4h at 50 ℃. Centrifuging for 20min at the rotation speed of 10000rpm to prepare a precipitate, washing with methanol, and drying in vacuum at 40 ℃ to obtain the zwitterion functionalized graphene oxide nanosheet.
(3) Dispersing the zwitterion functionalized graphene oxide nanosheet prepared in the step (2) in a methanol water solution, wherein the concentration is 0.3mg/ml, and dispersing polydiallyldimethylammonium in the methanol water solution, wherein the concentration is 0.4 mg/ml.
(4) And (3) alternately spin-coating 15 layers of the solution in the step (3) on the polycarbonate support at 2000rpm for 60 s.
(5) The prepared membrane is dried in vacuum at 40 ℃ to obtain a separation membrane, the thickness of the separation layer is 48nm, the separation performance of the membrane prepared in the example on an ethanol/water system is measured, when the temperature is 70 ℃ and the water content on the raw material side is 10%, the flux of the membrane is 3152g/m 2 h, and the separation factor is 439.
Example 4
(1) Uniformly dispersing graphene oxide nanosheets in dimethyl sulfoxide, wherein the concentration is 0.5mg/ml, and respectively dispersing ethylenediamine and butyrolactone in the dimethyl sulfoxide, wherein the concentrations are 5 mg/ml.
(2) Taking 30ml of graphene oxide solution, adding 18ml of ethylenediamine solution with the graphene oxide content being 6 times that of the graphene oxide solution, reacting for 2 hours at 50 ℃, then adding 36ml of butyrolactone solution with the ethylenediamine content being 2 times that of the graphene oxide solution, and reacting for 5 hours at 50 ℃. Centrifuging for 20min at the rotation speed of 8000rpm to obtain precipitate, washing with ethanol, and vacuum drying at 40 deg.C to obtain zwitterion functionalized graphene oxide nanosheet.
(3) Dispersing the zwitterion functionalized graphene oxide nanosheet prepared in the step (2) in an ethanol water solution, wherein the concentration is 0.1mg/ml, and dispersing polydiallyldimethylammonium in the ethanol water solution, wherein the concentration is 0.5 mg/ml.
(4) And (4) alternately spin-coating 15 layers of the solution in the step (3) on a polyacrylonitrile support body at 1500rpm for 45 s.
(5) The membrane obtained in the example was dried under vacuum at 40 ℃ to obtain a separation membrane, the thickness of the separation layer was 45nm, the separation performance of the membrane obtained in this example with respect to an ethanol/water system was determined, and when the temperature was 70 ℃ and the water content on the raw material side was 10%, the flux of the membrane was 2966g/m 2. h, and the separation factor was 781.
Example 5
(1) Uniformly dispersing graphene oxide nano sheets in N-N-2-methylformamide with the concentration of 0.5mg/ml, and respectively dispersing ethanolamine and butyrolactone in the N-N-2-methylformamide with the concentrations of 5 mg/ml.
(2) Taking 30ml of graphene oxide solution, adding 18ml of ethanolamine solution with the content of 6 times that of graphene oxide, reacting for 1h at 60 ℃, then adding 36ml of butyrolactone solution with the content of 2 times that of ethanolamine, and reacting for 4h at 60 ℃. Centrifuging for 30min at the rotation speed of 10000rpm to prepare a precipitate, washing with methanol, and drying in vacuum at 40 ℃ to obtain the zwitterion functionalized graphene oxide nanosheet.
(3) Dispersing the zwitterion functionalized graphene oxide nanosheet prepared in the step (2) in a deionized water solution, wherein the concentration is 0.4mg/ml, and dispersing polyallylamine hydrochloride in the deionized water solution, wherein the concentration is 0.6 mg/ml. .
(4) and (4) alternately spin-coating 15 layers of the solution in the step (3) on a polyacrylonitrile support body at 2000rpm for 60 s.
(5) And (3) drying the prepared membrane at 25 ℃ in vacuum to obtain the separation membrane.
the separation performance of the membrane prepared in this example was measured for an ethanol/water system, and when the temperature was 70 ℃ and the water content on the feed side was 10%, the flux of the membrane was 3100g/m 2. multidot.h, and the separation factor was 1958. the membrane prepared in this example was approximately 46nm thick as shown in FIG. 1.
Example 6
(1) Uniformly dispersing graphene oxide nano sheets in dimethyl sulfoxide, wherein the concentration is 0.5mg/ml, and respectively dispersing ethanolamine and propane sultone in dimethyl sulfoxide, wherein the concentrations are 5 mg/ml.
(2) Taking 30ml of graphene oxide solution, adding 18ml of ethanolamine solution with the content of 6 times that of graphene oxide, reacting for 1h at 60 ℃, then adding 36ml of propane sultone solution with the content of 2 times that of ethanolamine, and reacting for 4h at 60 ℃. Centrifuging for 30min at the rotation speed of 10000rpm to prepare a precipitate, washing with methanol, and drying in vacuum at 40 ℃ to obtain the zwitterion functionalized graphene oxide nanosheet.
(3) Dispersing the zwitterion functionalized graphene oxide nanosheet prepared in the step (2) in a deionized water solution, wherein the concentration is 0.2mg/ml, and dispersing polyethyleneimine in the deionized water solution, wherein the concentration is 0.2 mg/ml. .
(4) And (4) alternately spin-coating 20 layers of the solution in the step (3) on a polyacrylonitrile support body at 1500rpm for 45 s.
(5) The prepared membrane is dried in vacuum at 25 ℃ to obtain a separation membrane, the thickness of the separation layer is 55nm, the separation performance of the membrane prepared in the example on an ethanol/water system is measured, when the temperature is 70 ℃, the water content on the raw material side is 10%, the flux of the membrane is 2487g/m 2 h, and the separation factor is 759.
Claims (10)
1. A separation membrane based on zwitterion functionalized graphene oxide is characterized in that: the graphene oxide membrane is composed of a separation layer and a support layer, wherein the membrane layer formed by alternately spin-coating a polymer solution and a functionalized graphene oxide solution is used as the separation layer, and the polymer ultrafiltration membrane is used as the support layer.
2. A method for preparing the separation membrane of claim 1, comprising the following steps:
(1) zwitterionic functionalized graphene oxide: respectively dispersing graphene oxide nanosheets, amine compounds and ester compounds in the same organic solvent, adding the amine compound solution into the graphene oxide solution, reacting for 1-2h at 40-60 ℃, then adding the ester compound solution, and reacting for 3-5h at 40-60 ℃; centrifuging to prepare a precipitate, washing by an alcohol solvent, and drying in vacuum to obtain a zwitterion functionalized graphene oxide nanosheet;
(2) Preparing a membrane preparation liquid: uniformly dispersing the prepared zwitterion functionalized graphene oxide nanosheets in a solvent to prepare a graphene oxide membrane preparation solution with the concentration of 0.1-0.4mg/ml for later use; uniformly dispersing the polymer in a solvent to prepare a polymer solution with the concentration of 0.2-0.6mg/ml for later use;
(3) Preparation of the film: placing a support body in a spin coater, alternately spin-coating the polymer solution prepared in the step (2) and the graphene oxide membrane-making solution on the polymer ultrafiltration membrane support body, after a layer of polymer solution is spin-coated, spin-coating and washing with deionized water once, then spin-coating a layer of graphene oxide membrane-making solution, and spin-coating and washing with deionized water once;
(4) and (4) circularly operating the step (3) to the required number of layers, and finally placing the prepared membrane in a vacuum drying oven for drying.
3. The method according to claim 2, wherein the polymeric ultrafiltration membrane support is made of at least one of polyacrylonitrile, polycarbonate or polyvinylidene fluoride.
4. The method according to claim 2, wherein the organic solvent in the step (1) is one of 1-methyl-2-pyrrolidone, N-2-methylformamide, acetone, or dimethylsulfoxide; the alcohol solvent is one of methanol or ethanol.
5. The method according to claim 2, wherein the amine compound in the step (1) is one of ethanolamine or ethylenediamine; the ester compound is one of propane sultone or butane lactone.
6. The preparation method according to claim 2, characterized in that the concentration of the graphene oxide nanosheet solution in step (1) is 0.2-0.5mg/ml, and the concentrations of the amine compound and the ester compound are both 1-5 mg/ml; the mass of the amine compound is 2-6 times that of the graphene oxide; the mass of the ester compound is 1-2 times of that of the compound A.
7. The method according to claim 2, wherein the rotation speed of the centrifugation in step (1) is 8000-12000rpm, and the time of the centrifugation is 10-30 min; the drying temperature is 25-50 ℃.
8. the method according to claim 2, wherein the solvent in step (2) is one of water, an aqueous ethanol solution or an aqueous methanol solution; the polymer is one of polydiallyldimethylammonium, polyethyleneimine or polyallylamine hydrochloride.
9. The production method according to claim 2, characterized in that the spin-coating conditions described in step (3): the rotation speed is 1000-2000rpm, and the time is 30-60 s.
10. the method according to claim 1, wherein the required number of layers in the step (4) is 5 to 20; the drying temperature is 25-50 ℃.
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