CN109939571B - Graphene oxide framework composite membrane and preparation method and application thereof - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010612 desalination reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 18
- 239000013535 sea water Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 7
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- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000003618 dip coating Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims 1
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- 238000000926 separation method Methods 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- -1 salt ions Chemical class 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 12
- 238000005373 pervaporation Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000011033 desalting Methods 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- NIQFAJBKEHPUAM-UHFFFAOYSA-N 2-[2-[2-(2-aminoethoxy)ethoxy]ethoxy]ethanamine Chemical compound NCCOCCOCCOCCN NIQFAJBKEHPUAM-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000012267 brine Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical group C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a graphene oxide framework composite membrane for seawater desalination and desalination treatment and a preparation method thereof. According to the method, graphene oxide and diamine micromolecules containing ether oxygen groups are subjected to a cross-linking reaction through ultrasonic stirring to form a graphene oxide framework compound with a stable covalent structure, and a high-stability and high-desalting-performance graphene oxide framework composite membrane is prepared on an inorganic porous support body by adopting a vacuum filtration method. The size of the nanometer water channel of the graphene oxide framework composite film layer can be accurately regulated and controlled by regulating and controlling the proportion and the structure of ether oxygen group-containing diamine micromolecules, so that the rejection rate of the film to salt ions is improved. The preparation process is simple and easy to operate, has good repeatability, remarkably improves the water flux and the desalination rate of the membrane, has stable separation performance after long-time operation, and has wide application prospect in the fields of membrane seawater desalination or high-salinity wastewater desalination treatment and the like.
Description
Technical Field
The invention relates to a graphene oxide framework composite membrane with high water flux, high desalination rate and high stability, a preparation method thereof and application thereof in pervaporation desalination, belonging to the technical field of membrane separation.
Background
Water is a source of life, is a life pulse for social and economic development, and is a precious and irreplaceable natural resource for human beings. With the development of industrial production and economy, industrial wastewater pollution is increasingly serious, fresh water resources are increasingly deficient, and the pollution poses serious threats to human life and ecological systems thereof. Desalination (sea water desalination) of sea water, which accounts for more than 99% of the total water resources in the world, has become one of the important ways to solve the water resource crisis. As a novel two-dimensional membrane material, Graphene Oxide (GO) has the characteristics of containing various oxygen-containing functional groups, large specific surface area, strong adsorption capacity and the like, and has application prospects in the fields of gas separation, liquid separation, wastewater treatment, seawater desalination and the like. The pure graphene oxide film is formed by stacking GO sheet layers mutually through weak acting forces such as pi-pi bonds, hydrogen bonds and the like to form a two-dimensional interlayer nano channel, so that the pure graphene oxide film is used for molecular sieving. However, practice has proved that the mechanical strength of pure GO membranes is low and the guest molecules can easily expand the interlayer spacing upon separation, thereby affecting the separation effect and stability thereof, resulting in non-scaleable applications. Therefore, how to improve the acting force between GO sheet layers (or the stability of the GO composite membrane) and accurately regulate and control the size of a nano-channel of the membrane to separate different guest molecules becomes an important problem for industrial application of the GO-based composite membrane.
The most direct and effective method for enhancing the acting force between GO carbon layers is to take GO oxygen-containing groups as anchor points to carry out covalent modification on GO sheet layers through covalent cross-linking agent molecules (such as cyanate ester groups such as phenyl borate and p-phenyl isocyanate, glutaraldehyde, ethylene diamine and other linear structural unit molecules), so as to form Graphene Oxide Framework (GOF) composite membranes with uniform layer spacing. Hung et al (Chemistry of Materials, 2014, 26: 2983-. The change of the interlayer spacing of the GOF composite membrane from a dry state to a wet state is not largely attributed to the formation of stable C-N covalent bonds between sheets, and the stretching of the interlayer spacing of the membrane layer is remarkably inhibited, so that the stability of the membrane is improved.
Recently, patent CN106064023A reports that a poly (ethylene glycol) diamine (PEGDA) with a molecular weight of 500-5000 is used as a covalent cross-linking agent to prepare a graphene interlayer distance-adjustable GOF composite membrane on an organic microfiltration membrane support, and the GOF composite membrane has excellent comprehensive performance for gas separation. Particularly, the GOF composite membrane prepared by using the polyoxyethylene diamine with the molecular weight of 500 has the highest CO2Permeate flux and selectivity (Angew. chem. int. Ed., 2017, 56: 14246-14251). Recently, ZHao et al (Journal of Membrane Science, 2018, 567: 311-320) synthesized PEGDA-GO composite membrane on PAN sheet support by using PEGDA with molecular weight of 600 as covalent cross-linking agent for ethanol/water separation of pervaporation to obtain higher water flux and selectivity. The amino group in polymer PEGDA and the epoxy group in GO are subjected to covalent cross-linking reaction to form a stable GOF covalent structure, and ether bond in polymer PEGDACan improve the hydrophilicity and water absorption performance of the membrane.
Nevertheless, the above reports are all sheet membranes synthesized by using organic membranes as a support and only used for gas and liquid separation, etc., at present, there are few research reports on GO-based composite membrane materials for desalination and desalination of sea water by using high-concentration brine (such as NaCl solution greater than or equal to 3.5 wt%) as a feed liquid at room temperature, and especially GOF membrane materials with high water flux, high desalination rate and high stability at room temperature are in urgent need of research and development.
Disclosure of Invention
The invention aims to provide a graphene oxide framework composite membrane with high water flux, high salt rejection rate and high stability and a preparation method thereof. According to the method, the graphene oxide and the diamine micromolecules containing the ether oxygen groups are subjected to a cross-linking reaction to form a stable GOF covalent structure, so that the graphene oxide framework composite membrane with high water flux, high salt rejection rate and high stability is prepared, and the size of a nanometer water channel of a GOF membrane layer can be accurately regulated and controlled by regulating and controlling the proportion and the structure of the diamine micromolecules containing the ether oxygen groups, so that the selectivity and the retention rate of the membrane to salt ions are improved.
The invention also aims to provide an application of the graphene oxide framework composite membrane in water desalination treatment. The membrane has the advantages of high separation performance (water flux and desalination rate) and long-term stability at room temperature, and is particularly suitable for seawater desalination or high-concentration salt-containing wastewater treatment.
The invention provides a graphene oxide framework composite membrane which is prepared on an inorganic porous support by adopting a vacuum filtration method after covalent crosslinking modification is carried out on a graphene oxide lamellar layer by taking ether-oxygen group-containing diamine micromolecules as a covalent crosslinking agent.
The graphene oxide frame composite membrane has the characteristics of uniform and stable interlayer spacing.
The invention also provides a preparation method of the graphene oxide framework composite membrane, which comprises the following specific steps:
(1) stirring graphene oxide in water and ultrasonically dispersing the graphene oxide into 0.01-0.30 g L-1A graphene oxide aqueous dispersion;
(2) adding ether oxygen group-containing diamine micromolecules into the graphene oxide aqueous dispersion, and stirring and carrying out ultrasonic reaction for 2-4 h at room temperature to obtain a solution A;
(3) and dip-coating the solution A on an inorganic porous support by adopting a vacuum filtration method to form a composite membrane, and then placing the composite membrane in a vacuum oven at the temperature of 30-50 ℃ for drying for 2-6 h to obtain the graphene oxide frame composite membrane.
Further, the covalent cross-linking agent is selected from one or more of ether oxygen group-containing diamine micromolecules, and the molecular structure of the ether oxygen group-containing diamine micromolecules is simple NH2(CH2CH2O)nCH2CH2NH2、NH2CH2(CH2CH2O)nCH2CH2CH2NH2，n＝1～3。
Further, the mass ratio of the covalent cross-linking agent to the graphene oxide is 5-20.
Further, the inorganic porous support is sheet-shaped, tubular or hollow fiber-shaped Al2O3、SiO2、ZrO2、TiO2And the average pore diameter of the mullite material is 10-200 nm.
The invention also provides application of the graphene oxide framework composite membrane, namely the graphene oxide framework composite membrane is used for seawater desalination or high-concentration salt-containing wastewater treatment.
At room temperature, the graphene oxide frame composite membrane is placed in a membrane component for pervaporation test, one side of the membrane is a feed liquid side, 3.5 wt% of NaCl solution can be selected as the feed liquid to simulate seawater, the other side of the membrane is a permeation side, the permeation side is vacuumized to be less than 80Pa, and vapor at the permeation side is condensed to a glass cold trap by adopting liquid nitrogen.
The separation performance of the membrane is determined by the water flux J (kgm) at the permeate side-2h-1) And the salt rejection, Rej%:
water flux J is the mass of permeate measured per unit membrane area a per unit time t, m: j ═ m/At;
the salt rejection Rej% can be measured by measuring the feed side concentration CfAnd a permeate side concentration CpTo calculate: rej ═ 1-Cp/Cf) X 100%. The ion concentration in the permeate was determined using a conductivity meter and ion chromatography.
In particular, ethylene glycol bis 2-aminoethyl ether is taken as a cross-linking agent, and is covalently cross-linked and modified with graphene oxide to form tubular Al2O3The graphene oxide framework composite membrane prepared on the porous support has high water flux and desalination rate (higher than 99.99%), and has stable desalination performance within 100 hours of long-time operation under operating conditions.
Compared with the prior art, the invention has the beneficial effects that:
and (2) carrying out ultrasonic stirring reaction on graphene oxide and ether oxygen group-containing diamine micromolecule covalent cross-linking agent at room temperature, carrying out vacuum filtration, dip-coating on an inorganic porous support, and drying by an oven to form the composite membrane with the GOF structure. By regulating and controlling the proportion and the structure of the covalent cross-linking agent, the size of a nano water channel of the graphene oxide framework composite film layer can be accurately regulated and controlled, and the selectivity and the rejection rate of salt ions are improved. The preparation method is simple in preparation process, easy to operate and good in repeatability, and the prepared graphene oxide framework composite membrane has pervaporation desalting performance with high flux, high rejection rate and high stability at room temperature.
Detailed Description
In order to further describe the present invention, several specific embodiments are given below, but the patent rights are not limited to these examples.
Example 1
(1) Stirring and dispersing graphene oxide in water, and performing ultrasonic dispersion for 30min to prepare graphene oxide with the mass fraction of 0.08g L-1The graphene oxide dispersion liquid of (1).
(2) Adding ethylene glycol bis 2-aminoethyl ether (also called 2, 2' - (ethylene dioxy) bis (ethylamine)) into the graphene oxide aqueous dispersion, wherein the structure is shown in a simplified formula NH2(CH2CH2O)2CH2CH2NH2) Stirring and carrying out ultrasonic reaction for 2h at room temperature to obtain a solution A. Wherein B isThe mass ratio of the alcohol bis 2-aminoethyl ether to the graphene oxide is 10: 1.
(3) Dip-coating the solution A in tubular Al with average pore diameter of 10nm by vacuum filtration2O3And forming a composite membrane on the porous support, and then placing the composite membrane in a vacuum oven at 30 ℃ for drying for 6 hours to obtain the graphene oxide framework composite membrane.
(4) And (3) inspecting the pervaporation desalination performance of the prepared graphene oxide frame composite membrane by adopting a pervaporation experiment. The desalting performance of the membrane was tested at room temperature using simulated seawater as a feed solution with an initial concentration of 3.5 wt% NaCl solution. The results show that: the membrane had a permeate flux of 18.07kg m-2h-1The salt rejection rate is higher than 99.99%, and the water flux and salt rejection rate of the membrane are kept basically unchanged after the continuous operation test for 100 h.
Comparative example 1
In the process of preparing the solution a, ethylene glycol bis 2-aminoethyl ether and the like are not added as a covalent crosslinking agent, and other preparation conditions are the same as those in example 1, so that a pure graphene oxide film can be obtained. The pervaporation desalination performance test conditions are the same as example 1, and the water flux of the membrane is only 4.82kg m-2h-1The salt rejection was 99.95%. After running continuously for 6h, the GO on the surface layer of the membrane is obviously peeled off, the water flux of the membrane is increased, and the salt rejection rate is rapidly reduced (less than 30%).
Examples 2 to 4
In the process of preparing the solution A, the mass ratio of the covalent cross-linking agent ethylene glycol bis 2-aminoethyl ether to the graphene oxide is changed, other preparation conditions are the same as those in the example 1, and a series of GOF composite membranes (namely, the examples 2 to 4) with different ratios of the cross-linking agent to the graphene oxide can be obtained. The conditions for testing the pervaporation desalination performance are the same as those in example 1, and the desalination performance of these GOF composite membranes is shown in Table 1.
TABLE 1 desalting Performance of GOF composite membranes in examples 2-4
Examples 5 to 7
During the preparation of solution a, the type of covalent cross-linker was changed, namely: other ether oxygen group-containing diamine micromolecules are used for replacing ethylene glycol bis (2-aminoethyl ether), other preparation conditions are the same as those in example 1, and a series of GOF composite membranes (respectively corresponding to examples 5-7) crosslinked by different covalent crosslinking agents can be obtained. Other covalent cross-linking agents containing ether oxygen group diamine small molecules are respectively: bis (2-aminoethyl) ether (also known as 2, 2-oxobisethylamine, structure formula NH2CH2CH2OCH2CH2NH2) Bis [2- (2-aminoethoxy) ethyl ester]Ether (also known as 3, 6, 9-trioxaundecane-1, 11-diamine, structure formula NH)2(CH2CH2O)3CH2CH2NH2) Diethylene glycol bis (3-aminopropyl) ether (also known as 4, 7, 10-trioxa-1, 13-tridecanediamine, structure formula NH)2CH2(CH2CH2O)3CH2CH2CH2NH2). The conditions for testing the pervaporation desalination performance are the same as those in example 1, and the desalination performance of these GOF composite membranes is shown in Table 2.
TABLE 2 desalting Performance of GOF membranes in examples 5-7
Example 8
(1) Stirring and dispersing graphene oxide in water, and preparing the graphene oxide with the mass fraction of 0.30g L after ultrasonic dispersion for 2 hours-1The graphene oxide dispersion liquid of (1).
(2) Adding ethylene glycol bis (2-aminoethyl) ether into the graphene oxide dispersion liquid, performing ultrasonic dispersion for 15min, and then stirring at room temperature for ultrasonic reaction for 4h to obtain a solution A. Wherein the mass ratio of the ethylene glycol bis 2-aminoethyl ether to the graphene oxide is 10: 1.
(3) The solution A is dipped and coated on the ZrO with the top layer average aperture of 50nm by adopting a vacuum filtration method2-Al2O3Forming a composite membrane on an asymmetric porous support, and then mixingAnd (3) drying the composite membrane in a vacuum oven at 50 ℃ for 2h to obtain the graphene oxide framework composite membrane.
(4) And (3) inspecting the pervaporation desalination performance of the prepared graphene oxide frame composite membrane by adopting a pervaporation experiment. And (3) taking a NaCl solution with the concentration of 3.5-4.2 wt% as a feed solution, and testing the desalting performance of the membrane and the circulating stability performance of seawater with different salt concentrations at room temperature. The test result shows that: the continuous operation test is carried out for 120h, the desalting performance of the membrane is basically kept unchanged, and the water flux is higher than 10.00kg m-2h-1The salt rejection rate is more than 99.99%.
Claims (2)
1. The graphene oxide framework composite membrane is characterized by being prepared by taking ether oxygen group-containing diamine micromolecules as a covalent cross-linking agent and carrying out covalent cross-linking modification on the ether oxygen group-containing diamine micromolecules and graphene oxide lamella, wherein the covalent cross-linking agent is selected from one or more of the ether oxygen group-containing diamine micromolecules, and the molecular structure of the ether oxygen group-containing diamine micromolecules is NH2(CH2CH2O)nCH2CH2NH2(n＝2)、NH2CH2(CH2CH2O)nCH2CH2CH2NH2(n＝1～3)；
The preparation method of the graphene oxide framework composite membrane comprises the following steps:
(1) stirring graphene oxide in water and ultrasonically dispersing the graphene oxide into 0.08-0.30 g L-1A graphene oxide aqueous dispersion;
(2) adding ether oxygen group-containing diamine micromolecules into the graphene oxide aqueous dispersion, and carrying out stirring ultrasonic reaction for 2-4 hours at room temperature to obtain a solution A, wherein the mass ratio of the ether oxygen group-containing diamine micromolecules to the graphene oxide is 5-15;
(3) and dip-coating the solution A on an inorganic porous support by adopting a vacuum filtration method to form a composite membrane, and then placing the composite membrane in a vacuum oven at the temperature of 30-50 ℃ for drying for 2-6 h to obtain the graphene oxide frame composite membrane.
2. The application of the graphene oxide framework composite membrane is characterized in that the graphene oxide framework composite membrane according to claim 1 is used for seawater desalination or high-salinity wastewater treatment.
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| CN110508164A (en) * | 2019-08-07 | 2019-11-29 | 大连理工大学 | A kind of preparation method of the graphene oxide composite membrane of stable structure |
| CN110394070B (en) * | 2019-08-09 | 2021-12-03 | 中国海洋大学 | Multilayer crosslinked graphene oxide, and preparation method and application thereof |
| CN110841487B (en) * | 2019-12-05 | 2022-04-15 | 中国石油大学(华东) | Preparation method of seawater desalination membrane |
| CN113318597A (en) * | 2020-02-28 | 2021-08-31 | 天津大学 | Method for preparing graphene oxide membrane through covalent crosslinking of layer |
| CN111804160B (en) * | 2020-06-04 | 2022-05-27 | 五邑大学 | Ionic liquid modified graphene oxide membrane with water and ion selective transmission performance and preparation method thereof |
| CN114432909A (en) * | 2022-01-30 | 2022-05-06 | 大连理工大学 | High-stability ceramic-based sub-nanopore graphene composite membrane and precise separation application |
| CN115651578B (en) * | 2022-10-28 | 2023-08-29 | 深圳市锦旺兴绝缘材料有限公司 | Preparation method and application of heat-resistant modified epoxy resin insulating adhesive |
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| CN103611431A (en) * | 2013-11-11 | 2014-03-05 | 南京工业大学 | Preparation method of graphene membrane supported by porous ceramic |
| CN106606931A (en) * | 2015-10-27 | 2017-05-03 | 中国科学院宁波材料技术与工程研究所 | High stability seawater desalination film, preparation method and application thereof |
| CN106064023A (en) * | 2016-04-13 | 2016-11-02 | 天津大学 | The preparation of a kind of functional graphene oxide composite membrane and application |
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