CN109939571B - Graphene oxide framework composite membrane and preparation method and application thereof - Google Patents
Graphene oxide framework composite membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN109939571B CN109939571B CN201910259283.4A CN201910259283A CN109939571B CN 109939571 B CN109939571 B CN 109939571B CN 201910259283 A CN201910259283 A CN 201910259283A CN 109939571 B CN109939571 B CN 109939571B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- composite membrane
- membrane
- desalination
- diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 81
- 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 52
- 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 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 12
- 239000013535 sea water Substances 0.000 claims abstract description 12
- -1 diamine small molecules Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000004907 flux Effects 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 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
- 238000001035 drying Methods 0.000 description 4
- 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
- 230000001276 controlling effect Effects 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002090 nanochannel Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 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
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 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
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000012827 research and development Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 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
-
- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明涉及一种用于海水淡化脱盐处理的氧化石墨烯框架复合膜及其制备方法。该方法通过超声搅拌将氧化石墨烯与含醚氧基团的二胺小分子发生交联反应从而形成具有稳定的共价结构的氧化石墨烯框架复合物，采用真空抽滤法在无机多孔支撑体上制备出高稳定性的、高脱盐性能的氧化石墨烯框架复合膜。通过调控含醚氧基团二胺小分子的比例和结构，能精确调控氧化石墨烯框架复合膜层纳米水通道的尺寸大小，从而提高膜对盐离子的截留率。本发明的制备过程简单、易操作，具有很好的重复性，显著提高了膜的水通量和脱盐率，长时间运转膜的分离性能稳定，在膜法海水淡化或高盐废水脱盐处理等领域具有广泛的应用前景。The invention relates to a graphene oxide frame composite membrane for desalination of seawater and a preparation method thereof. In the method, graphene oxide is cross-linked with small diamine molecules containing ether oxide groups through ultrasonic stirring to form a graphene oxide framework complex with a stable covalent structure. The graphene oxide framework composite membrane with high stability and high desalination performance was prepared on the above. By adjusting the proportion and structure of diamine small molecules containing ether oxygen groups, the size of the nano-water channels in the graphene oxide framework composite membrane layer can be precisely regulated, thereby improving the salt ion retention rate of the membrane. The preparation process of the invention is simple, easy to operate, has good repeatability, remarkably improves the water flux and desalination rate of the membrane, the separation performance of the membrane is stable in long-term operation, and can be used in the desalination of seawater by membrane method or desalination of high-salt wastewater, etc. The field has broad application prospects.
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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910259283.4A CN109939571B (en) | 2019-04-01 | 2019-04-01 | Graphene oxide framework composite membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910259283.4A CN109939571B (en) | 2019-04-01 | 2019-04-01 | Graphene oxide framework composite membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109939571A CN109939571A (en) | 2019-06-28 |
| CN109939571B true CN109939571B (en) | 2022-02-11 |
Family
ID=67013309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910259283.4A Active CN109939571B (en) | 2019-04-01 | 2019-04-01 | Graphene oxide framework composite membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109939571B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110508164A (en) * | 2019-08-07 | 2019-11-29 | 大连理工大学 | A kind of preparation method of graphene oxide composite film with 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 | A kind of highly stable ceramic-based sub-nanoporous graphene composite membrane and its application in precision separation |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103611431A (en) * | 2013-11-11 | 2014-03-05 | 南京工业大学 | Preparation method of graphene membrane supported by porous ceramic |
| CN104582819A (en) * | 2012-08-15 | 2015-04-29 | 曼彻斯特大学 | Using membranes to separate water |
| 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 |
| 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 |
| US10065155B2 (en) * | 2016-08-04 | 2018-09-04 | King Fahd University Of Petroleum And Minerals | Method for preparing a polygraphene membrane |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105014982B (en) * | 2015-07-30 | 2017-11-07 | 湖州森诺环境科技有限公司 | The preparation method of graphene polytetrafluoroethylene (PTFE) osmotic distillation film |
| CN105084355B (en) * | 2015-09-11 | 2017-12-19 | 四川大学 | Controllable stable graphene oxide membrane of interlamellar spacing and preparation method thereof |
| CN105833735B (en) * | 2016-05-06 | 2018-08-21 | 中国科学院宁波材料技术与工程研究所 | A kind of three-dimensional graphene oxide frame films and its preparation method and application |
| CN106731893B (en) * | 2017-02-28 | 2020-05-12 | 中国科学院上海高等研究院 | A kind of preparation method and application of graphene oxide framework material self-assembled film |
-
2019
- 2019-04-01 CN CN201910259283.4A patent/CN109939571B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104582819A (en) * | 2012-08-15 | 2015-04-29 | 曼彻斯特大学 | Using membranes to separate water |
| 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 |
| US10065155B2 (en) * | 2016-08-04 | 2018-09-04 | King Fahd University Of Petroleum And Minerals | Method for preparing a polygraphene membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109939571A (en) | 2019-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109939571B (en) | Graphene oxide framework composite membrane and preparation method and application thereof | |
| Liu et al. | Mixed-matrix hollow fiber composite membranes comprising of PEBA and MOF for pervaporation separation of ethanol/water mixtures | |
| Liu et al. | A review: the effect of the microporous support during interfacial polymerization on the morphology and performances of a thin film composite membrane for liquid purification | |
| Liu et al. | Hydrophobic-ZIF-71 filled PEBA mixed matrix membranes for recovery of biobutanol via pervaporation | |
| Li et al. | Preparation and characterization of SiO2/PDMS/PVDF composite membrane for phenols recovery from coal gasification wastewater in pervaporation | |
| WO2013130143A2 (en) | Polaniline based membranes for separation of carbon dioxide and methane | |
| CN108409981A (en) | A kind of preparation method of modified metal organic frame and composite nanometer filtering film | |
| Si et al. | Fluoroalkyl-grafted methacrylate-PDMS membranes using fluoromonomer as a diluent for enhancing biobutanol pervaporation | |
| CN103285739A (en) | Preparation method of hydrophobic porous separation membrane | |
| Rong et al. | Preparation and characterization of novel zwitterionic poly (arylene ether sulfone) ultrafiltration membrane with good thermostability and excellent antifouling properties | |
| Wang et al. | Reducing active layer thickness of polyamide composite membranes using a covalent organic framework interlayer in interfacial polymerization | |
| CN114028947A (en) | A reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials and preparation method thereof | |
| Miao et al. | Development of novel ionic covalent organic frameworks composite nanofiltration membranes for dye/salt separation | |
| Thakur et al. | Highly stable acid–base complex membrane for ethanol dehydration by pervaporation separation | |
| CN112657352B (en) | A kind of polyamide film layer composite reverse osmosis film and its preparation method and application | |
| Kamio et al. | Hollow fiber-type facilitated transport membrane composed of a polymerized ionic liquid-based gel layer with amino acidate as the CO2 carrier | |
| Riasat Harami et al. | Magnetic nanoFe2O3–incorporated PEBA membranes for CO2/CH4 and CO2/N2 separation: Experimental study and grand canonical Monte Carlo and molecular dynamics simulations | |
| Liu et al. | Fabrication of highly permeable PDMS@ ZIF‐8/PVDF hollow fiber composite membrane in module for ethanol‐water separation | |
| Wang et al. | A highly permeable mixed matrix membrane containing a vertically aligned metal–organic framework for CO2 separation | |
| CN109012243A (en) | The preparation and Separate Efficiency Study of macromolecule-covalent organic frame material (polyCOF) composite membrane | |
| CN109865501A (en) | A kind of compound membrane preparation method for organic dyestuff in Adsorption water | |
| CN105833735B (en) | A kind of three-dimensional graphene oxide frame films and its preparation method and application | |
| Shiue et al. | Using polyvinyl alcohol (PVA): poly (allylamine)(PAA) coated on reverse osmosis membrane for separating carbon dioxide from indoor air | |
| Zhao et al. | Macromolecule crosslinked composite PVA membranes for pervaporation desalination | |
| Ma et al. | Novel dopamine-modified cellulose acetate ultrafiltration membranes with improved separation and antifouling performances |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |