CN109939571A - A kind of graphene oxide frame composite membrane and its preparation method and application - Google Patents
A kind of graphene oxide frame composite membrane and its preparation method and application Download PDFInfo
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- CN109939571A CN109939571A CN201910259283.4A CN201910259283A CN109939571A CN 109939571 A CN109939571 A CN 109939571A CN 201910259283 A CN201910259283 A CN 201910259283A CN 109939571 A CN109939571 A CN 109939571A
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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
Abstract
The present invention relates to a kind of graphene oxide frame composite membranes and preparation method thereof for sea water desalting processing.This method is reacted by being stirred by ultrasonic to crosslink graphene oxide with the diamines small molecule of ether-containing oxygen groups to form the graphene oxide frame compound with stable covalent structure, prepares high stability, high desalination performance graphene oxide frame composite membrane on inorganic porous supporter using vacuum filtration method.By regulating and controlling the ratio and structure of ether-containing oxygen groups diamines small molecule, the size of energy accuracy controlling graphene oxide frame composite film nanometer aquaporin, to improve film to the rejection of salt ion.Preparation process of the invention is simple, easy to operate, has repeatability well, significantly improves the water flux and salt rejection rate of film, and the separating property of long time running film is stablized, is with a wide range of applications in the fields such as Membrane seawater desalination or high-salt wastewater desalting processing.
Description
Technical field
The present invention relates to the graphene oxide frame composite membranes and its system of a kind of high water flux, equipment with high desalinization and high stability
Preparation Method and the application in infiltration evaporation desalination, belong to technical field of membrane separation.
Background technique
Water is Source of life, is the lifeblood of socio-economic development, is mankind's preciousness without alternative natural resources.With
Industrialized production and expanding economy, industrial wastewater pollution are got worse, and freshwater resources are increasingly deficient, to human lives and its life
State system constitutes serious threat.The seawater for accounting for 99% or more world water resources total amount desalination (sea water desalination) has been subjected to
As one of the important channel for solving water resources crisis.As a kind of membrane material of New Two Dimensional, graphene oxide (GO) has
The features such as containing a variety of oxygen-containing functional groups, large specific surface area, strong adsorption capacity, gas separation, liquid separation, wastewater treatment and
The fields such as sea water desalting have application prospect.Pure zirconia graphene film is that GO lamella passes through the weak effects such as pi-pi bond and hydrogen bond
The mutual stacking of power and form two-dimentional interlayer nanochannel, for molecule screening.But, in practice it has proved that the machinery of pure GO film
Intensity is low, and guest molecule can expand interlamellar spacing in separation easily, to influence its separating effect and stability, cause
It is unable to scale application.Therefore, active force (or stability of GO composite membrane), the control accurate film between GO lamella how to be improved
Nanochannel size become the major issue that is faced of GO group compound film industrial applications to separate different guest molecules.
It is " anchor point " by covalently handing over that the most directly effective method of active force between enhancing GO carbon-coating, which is with GO oxygen-containing group,
Joining agent molecule, (such as phenylboronate divides the linear structures units such as phenyl isocyanate cyanic acid ester group, glutaraldehyde, ethylenediamine
Son) it is modified with GO lamella progress covalent modification, to form uniform graphene oxide frame (the Graphene Oxide of interlamellar spacing
Frameworks, GOF) composite membrane.Hung etc. (Chemistry of Materials, 2014,26:2983-2990) selection second
Three kinds of diamine monomer small molecules such as diamines, butanediamine, p-phenylenediamine form GOF composite membrane with the modification of GO covalent cross-linking respectively,
The interlamellar spacing of these films is respectively 0.91,0.97 and 1.01nm under drying regime, is respectively 0.93,0.99 and under wetting state
1.09nm, and pure GO film interlamellar spacing in wet processes from dry 0.85nm increases to 1.31nm.GOF composite membrane is from dry shape
The interlamellar spacing variation of state to moisture state is less attributed to piece interlayer and forms stable C-N covalent bond, inhibits film significantly
The stretching of interlamellar spacing is to improve the stability of film.
Polyethyleneoxide diamine (the poly that it is 500~5000 with molecular weight that nearest patent CN106064023A, which is reported,
(ethylene glycol) diamine, PEGDA) it is covalent crosslinking agent, graphene is prepared on organic micro-filtration film support
Lamella GOF composite membrane adjustable in pitch has excellent comprehensive performance for gas separation.Especially with molecular weight 500
The GOF composite membrane of polyethyleneoxide diamine preparation has highest CO2Permeation flux and selectivity (Angew.Chem.Int.Ed.,
2017,56:14246-14251).Nearest Zhao etc. (Journal ofMembrane Science, 2018,567:311-320)
The polymer P EGDA for being 600 using molecular weight synthesizes PEGDA-GO composite membrane on PAN sheet supporter as covalent crosslinking agent,
Ethanol/water for infiltration evaporation separates, and obtains higher water flux and selectivity.Amino and GO in polymer P EGDA
In epoxy group covalent cross-linking reaction occur form stable GOF covalent structure, and the ehter bond in polymer P EGDA can mention
The hydrophily and water absorbing properties of high film.
Nevertheless, above-mentioned report is all the laminar film synthesized using organic film as supporter and is used only for gas, liquid
Separation etc., currently based on high concentration salt water (such as the NaCl solution of >=3.5wt%) being at room temperature that feeding liquid carries out sea water desalination
The research report of the GO group compound film material of desalination is less, especially high water flux, equipment with high desalinization and high stability at room temperature
GOF membrane material is urgently researched and developed.
Summary of the invention
It is multiple that the purpose of the present invention is to provide the graphene oxide frames of a kind of high water flux, equipment with high desalinization and high stability
Close film and preparation method thereof.This method, which is crosslinked by graphene oxide with the diamines small molecule of ether-containing oxygen groups, reacts formation
Stable GOF covalent structure, so that it is multiple to prepare the graphene oxide frame with high water flux, equipment with high desalinization and high stability
Film is closed, by regulating and controlling the ratio and structure of ether-containing oxygen groups diamines small molecule, the ruler of energy accuracy controlling GOF film layer nanometer aquaporin
Very little size, to improve film to the selectivity and rejection of salt ion.
Another object of the present invention is to provide a kind of above-mentioned graphene oxide frame composite membranes in water body desalting processing
Using.The film has many advantages, such as high separating property (water flux and salt rejection rate) and long-time stability at room temperature, especially suitable
It is handled for sea water desalination or high-concentration salt-containing wastewater.
The present invention provides a kind of graphene oxide frame composite membrane, which is containing ether oxygen
Group diamines small molecule is covalent crosslinking agent, modified with graphene oxide layer progress covalent cross-linking, using vacuum filtration method
It is prepared on inorganic porous supporter.
Above-mentioned graphene oxide frame composite membrane has the characteristics that interlamellar spacing is uniform, stable.
The present invention also provides the preparation methods of the graphene oxide frame composite membrane, comprise the following specific steps that:
(1) graphene oxide is stirred to ultrasonic disperse in water into 0.01~0.30g L-1Graphene oxide aqueous dispersions；
(2) ether-containing oxygen groups diamines small molecule is added in above-mentioned graphene oxide aqueous dispersions, is stirred at room temperature
It mixes 2~4h of ultrasonic reaction and obtains solution A；
(3) use vacuum filtration method by solution A dip-coating in forming composite membrane on inorganic porous supporter, then by composite membrane
Dry 2~6h is placed in 30~50 DEG C of vacuum drying oven to get graphene oxide frame composite membrane.
Further, the covalent crosslinking agent is selected from one or more of ether-containing oxygen groups diamines small molecule, this contains
The molecular structure skeleton symbol of ether oxygen group diamines small molecule is NH2(CH2CH2O)nCH2CH2NH2、NH2CH2(CH2CH2O)nCH2CH2CH2NH2, n=1~3.
Further, the mass ratio of the covalent crosslinking agent and graphene oxide is 5~20.
Further, the inorganic porous supporter is the Al of sheet, tubulose or hollow fiber2O3、SiO2、ZrO2、
TiO2, mullite material, average pore size be 10~200nm.
The present invention also provides the applications of above-mentioned graphene oxide frame composite membrane, i.e., the graphene oxide frame is compound
Film is handled for sea water desalination or high-concentration salt-containing wastewater.
At room temperature, above-mentioned graphene oxide frame composite membrane is placed in the membrane module of infiltration evaporation test, the side of film
For feeding liquid side, the NaCl solution simulated seawater of the optional 3.5wt% solubility of feeding liquid, the other side of film is per-meate side, per-meate side
It is evacuated to and is less than 80Pa, per-meate side steam is using liquid nitrogen condensation to glass cold-trap.
The separating property of film by per-meate side water flux J (kgm-2h-1) and salt rejection rate Rej% two parameters evaluated
:
Water flux J is the quality in unit time t through the measured penetrating fluid of per membrane area A, m:J=m/At；
Salt rejection rate Rej% can pass through test feed side concentration CfWith per-meate side concentration CpTo calculate: Rej%=(1-Cp/Cf)
× 100%.Penetrating fluid intermediate ion concentration uses conductivity meter and ion chromatography.
Particularly, using the double 2- amino-ethyl ethers of ethylene glycol as crosslinking agent, with graphene oxide covalent cross-linking it is modified
Tubulose Al2O3There is the graphene oxide frame composite membrane prepared on porous supporting body high water flux and salt rejection rate (to be higher than
99.99%), and in the operating condition desalting performance is stablized in long time running 100h.
The present invention compared to the prior art, the beneficial effect is that:
Graphene oxide ultrasonic agitation is carried out with ether-containing oxygen groups diamines small molecule covalent crosslinking agent at room temperature to react,
Dip-coating is filtered by vacuum on inorganic porous supporter and forms the composite membrane with GOF structure through oven drying.By regulating and controlling altogether
The ratio and structure of valence crosslinking agent, can accuracy controlling graphene oxide frame composite film nanometer water channel size size and mention
Selectivity and rejection of the height to salt ion.The preparation process of this method is simple, easy to operate, has repeatability well, made
Standby graphene oxide frame composite membrane has high-throughput, high rejection, the infiltration evaporation of high stability salt at room temperature
Energy.
Specific embodiment
In order to further describe the present invention, several specific implementation cases are shown below, but patent claim is not limited to
These examples.
Embodiment 1
(1) graphene oxide Yu Shuizhong is dispersed with stirring, it is 0.08g L that ultrasonic disperse 30min, which is prepared into mass fraction,-1
Graphene oxide dispersion.
(2) the double 2- amino-ethyl ethers of ethylene glycol are added in above-mentioned graphene oxide aqueous dispersions, and (also referred to as 2,2 '-is (sub-
Ethyl dioxy) bis- (ethamine), skeleton symbol NH2(CH2CH2O)2CH2CH2NH2) ultrasonic reaction 2h is stirred at room temperature, it obtains molten
Liquid A.Wherein the mass ratio of the double 2- amino-ethyl ethers of ethylene glycol and graphene oxide is 10: 1.
(3) use vacuum filtration method by solution A dip-coating in average pore size for the tubular type Al of 10nm2O3Shape on porous supporting body
At composite membrane, then composite membrane is placed in in 30 DEG C of vacuum drying oven dry 6h to get graphene oxide frame composite membrane.
(4) the above-mentioned graphene oxide frame composite membrane prepared is investigated to the infiltration evaporation of film using infiltration evaporation experiment
Desalting performance.Using initial concentration for 3.5wt% NaCl solution simulated seawater as feeding liquid, test the desalination of the film at room temperature
Performance.The result shows that: the osmotic water flux of the film is 18.07kg m-2h-1, salt rejection rate be higher than 99.99%, continuously run test
Water flux and the salt rejection rate holding of 100h, film are basically unchanged.
Comparative example 1
During preparing solution A, double 2- amino-ethyl ethers of ethylene glycol etc. are added without as covalent crosslinking agent, other preparations
Condition is same as Example 1, and pure graphene oxide membrane can be obtained.Infiltration evaporation desalting performance test condition and embodiment 1
Identical, the water flux of the film is only 4.82kg m-2h-1, salt rejection rate 99.95%.After continuously running test 6h, the film table is found
There is obvious peeling in the GO of layer, and the water flux of film rises, and salt rejection rate declines rapidly (lower than 30%).
Embodiment 2-4
During preparing solution A, change the matter of covalent crosslinking agent ethylene glycol double 2- amino-ethyl ethers and graphene oxide
Ratio is measured, other preparation conditions are same as Example 1, and a series of GOF that different crosslinking agents and graphene oxide ratio can be obtained is multiple
It closes film (i.e. embodiment 2~4).Infiltration evaporation desalting performance test condition is same as Example 1, the desalination of these GOF composite membranes
Performance is shown in Table 1.
The desalting performance of GOF composite membrane in 1. embodiment 2-4 of table
Embodiment 5-7
During preparing solution A, change the type of covalent crosslinking agent, it may be assumed that with other ether-containing oxygen groups diamines small molecules
Instead of the double 2- amino-ethyl ethers of ethylene glycol, other preparation conditions are same as Example 1, and a series of different covalent cross-linkings can be obtained
The GOF composite membrane (respectively corresponding embodiment 5~7) of agent crosslinking.The covalent crosslinking agent of other ether-containing oxygen groups diamines small molecules point
Not are as follows: bis- (2- aminoethyl) ether (the double ethamine of also referred to as 2,2- oxo, skeleton symbol NH2CH2CH2OCH2CH2NH2), bis- [2- (2-
Amino ethoxy) ethyl] ether (also referred to as 3,6,9- trioxaundecane -1,11- diamines, skeleton symbol NH2(CH2CH2O)3CH2CH2NH2), diethylene glycol two (3- aminopropyl) ether (also referred to as 4,7,10- tri- oxygen -1,13- tridecane diamines, structure letter
Formula NH2CH2(CH2CH2O)3CH2CH2CH2NH2).Infiltration evaporation desalting performance test condition is same as Example 1, these GOF are multiple
The desalting performance for closing film is shown in Table 2.
The desalting performance of GOF film in 2. embodiment 5-7 of table
Embodiment 8
(1) graphene oxide Yu Shuizhong is dispersed with stirring, it is 0.30g L that mass fraction is prepared into after ultrasonic disperse 2h-1's
Graphene oxide dispersion.
(2) the double 2- amino-ethyl ethers of ethylene glycol are added in above-mentioned graphene oxide dispersion, after ultrasonic disperse 15min in
Ultrasonic reaction 4h is stirred at room temperature, obtains solution A.Wherein the mass ratio of the double 2- amino-ethyl ethers of ethylene glycol and graphene oxide is
10∶1。
(3) use vacuum filtration method by solution A dip-coating in top layer average pore size for the ZrO of 50nm2-Al2O3It is asymmetric porous
Composite membrane is formed on supporter, then composite membrane is placed in in 50 DEG C of vacuum drying oven dry 2h to get graphene oxide frame
Frame composite membrane.
(4) the above-mentioned graphene oxide frame composite membrane prepared is investigated to the infiltration evaporation of film using infiltration evaporation experiment
Desalting performance.Using the NaCl solution of 3.5~4.2wt% concentration as feeding liquid, the desalting performance and not of the film is tested at room temperature
With the stable circulation performance of salinity seawater.Test result shows: continuously running test 120h, the desalting performance of the film is protected substantially
Hold it is constant, water flux be higher than 10.00kg m-2h-1, salt rejection rate is greater than 99.99%.
Claims (6)
1. a kind of graphene oxide frame composite membrane, which is characterized in that the graphene oxide frame composite membrane is with ether-containing oxygroup
Group's diamines small molecule is covalent crosslinking agent, carries out that covalent cross-linking is modified is prepared with graphene oxide layer.
2. a kind of preparation method of graphene oxide frame composite membrane, which is characterized in that comprise the following steps that
(1) graphene oxide is stirred to ultrasonic disperse in water into 0.01~0.30g L-1Graphene oxide aqueous dispersions；
(2) ether-containing oxygen groups diamines small molecule is added in above-mentioned graphene oxide aqueous dispersions, is stirred at room temperature super
2~4h of phonoresponse obtains solution A；
(3) use vacuum filtration method that composite membrane in forming composite membrane on inorganic porous supporter, is then placed to solution A dip-coating
Dry 2~6h is in 30~50 DEG C of vacuum drying oven to get graphene oxide frame composite membrane.
3. the preparation method of graphene oxide frame composite membrane as claimed in claim 2, which is characterized in that the covalent cross-linking
Agent is selected from one or more of ether-containing oxygen groups diamines small molecule, and the molecular structure skeleton symbol of ether-containing oxygen groups diamines small molecule is
NH2(CH2CH2O)nCH2CH2NH2、NH2CH2(CH2CH2O)nCH2CH2CH2NH2, n=1~3.
4. the preparation method of graphene oxide frame composite membrane as claimed in claim 2, which is characterized in that the covalent cross-linking
The mass ratio of agent and graphene oxide is 5~20.
5. the preparation method of graphene oxide frame composite membrane as claimed in claim 2, which is characterized in that described is inorganic porous
Supporter is the Al of sheet, tubulose or hollow fiber2O3、SiO2、ZrO2、TiO2, mullite material, average pore size be 10~
200nm。
6. a kind of application of graphene oxide frame composite membrane, which is characterized in that will be if claim 1-5 is as described in any one
Graphene oxide frame composite membrane is handled for sea water desalination or high-salt wastewater.
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Cited By (7)
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|---|---|---|---|---|
| CN110394070A (en) * | 2019-08-09 | 2019-11-01 | 中国海洋大学 | A kind of multilayer crosslinking-oxidization graphene, preparation method and application |
| 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 |
| CN110841487A (en) * | 2019-12-05 | 2020-02-28 | 中国石油大学(华东) | Preparation method of seawater desalination membrane |
| CN111804160A (en) * | 2020-06-04 | 2020-10-23 | 五邑大学 | Ionic liquid modified graphene oxide membrane with water and ion selective transmission performance and preparation method thereof |
| CN113318597A (en) * | 2020-02-28 | 2021-08-31 | 天津大学 | Method for preparing graphene oxide membrane through covalent crosslinking of layer |
| 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 |
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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 |
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| CN111804160A (en) * | 2020-06-04 | 2020-10-23 | 五邑大学 | Ionic liquid modified graphene oxide membrane with water and ion selective transmission performance and preparation method thereof |
| 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 |
| CN115651578A (en) * | 2022-10-28 | 2023-01-31 | 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 |
| 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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