CN117160246A - Method for stabilizing graphene oxide cortex and ultrafiltration base membrane - Google Patents
Method for stabilizing graphene oxide cortex and ultrafiltration base membrane Download PDFInfo
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application discloses a method for stabilizing a graphene oxide cortex and an ultrafiltration base membrane, and belongs to the technical field of membrane separation. A method of stabilizing a graphene oxide skin layer and an ultrafiltration membrane comprising the steps of: and carrying out functionalization treatment on the PAN film to obtain a functionalized PAN film, then coating graphene oxide on the functionalized PAN film, and carrying out heat treatment to obtain the graphene oxide composite film. According to the preparation method, through optimizing membrane preparation parameters (EDA adsorption time, post-adsorption heat treatment temperature, GO thickness and the like), the graphene oxide composite membrane (GO composite membrane) with improved screening performance and more stable pore channel structure is obtained.
Description
Technical Field
The application relates to the technical field of membrane separation, in particular to a method for stabilizing a graphene oxide cortex and an ultrafiltration base membrane.
Background
Graphene Oxide (GO) is used as a novel two-dimensional material, has the advantages of strong mechanical property, good dispersion property, capability of macro preparation and the like, has the characteristics of good hydrophilicity, antibacterial property, chlorine resistance and the like, is an excellent water treatment surface material, and is expected to be applied to separation processes such as ultrafiltration, nanofiltration, reverse osmosis, pervaporation and the like.
There are various methods for constructing the graphene oxide separation layer, mainly forming a two-dimensional stacking structure through a self-assembly process, and specific assembly driving types include pressure driving, dispersion liquid volatilization driving and the like. The pressure driving is a pressure-assisted self-assembly method, and the method can be particularly divided into two types of 'pressurized filtration' and 'negative pressure filtration', and is characterized in that GO dispersion liquid with a certain concentration is selected, and under the action of pressure assistance, the GO skin layer in the dispersion liquid is deposited on a base film to obtain the GO composite film. The method has the advantages of convenience, rapidness, controllable thickness of the separation layer, and adjustable film forming speed and microstructure of the GO layer.
Stable interaction is constructed between the functional layer and the cortex of the GO composite membrane, so that the problem that the separation layer falls off due to operations such as fluid convection and the like in the actual use process of the membrane can be avoided. In constructing this stable interaction, the surface of the base film is often functionalized to carry functional groups that can form strong interactions with the GO sheets. In the construction of the GO composite membrane, the applied basic membrane modification method mostly selects polydopamine surface modification with broad-spectrum compatibility to the material surface. However, this method itself has a certain limitation. The polydopamine surface modification method is to realize surface functionalization in a mode that polydopamine small particles are deposited on a modified surface, and the surface modification method is faced with a plurality of pore channels with high surface appearance requirements, especially pore channels with the surface of only 10nm level, such as ultrafiltration base membranes, and the pore blocking possibly occurs in the modification process, so that the flux of membrane separation is reduced. How to effectively functionalize the surface of the base film with easily blocked holes on the surface while maintaining the pore channel structure of the surface is the direction of the force.
Disclosure of Invention
The application aims to provide a method for stabilizing a graphene oxide skin layer and an ultrafiltration base membrane, so as to solve the problems in the prior art, the PAN membrane adopted by the application is a common microfiltration membrane construction material, carboxylation of a surface structure can be realized by controlling hydrolysis of PAN on the membrane surface, covalent bonding is formed with oxygen-containing groups on the GO surface, or secondary functionalization is carried out with a diamine cross-linking agent first, and then the reaction is carried out with a GO separation layer, so that the interception performance can be improved under the condition that the microstructure of a small pore canal is effectively maintained (as can be proved by a Surface Electron Microscope (SEM) photo, particularly, the PAN membrane after hydrolysis carboxylation and amino secondary functionalization has a similar surface morphology as PAN, and still maintains obvious surface gaps).
In order to achieve the above object, the present application provides the following solutions:
one of the technical schemes of the application is as follows: a method of stabilizing a graphene oxide skin layer and an ultrafiltration membrane comprising the steps of:
and performing functionalization treatment on the PAN film (PAN base film) to obtain a functionalized PAN film, then coating graphene oxide on the functionalized PAN film, and performing heat treatment to obtain the graphene oxide composite film.
Further, the functionalized PAN membrane comprises a carboxyl-functionalized PAN membrane or an amino-functionalized PAN membrane; the temperature of the heat treatment is 25-100 ℃ and the time is 0.5h.
Further, the heat treatment is a forced air drying oven heat treatment, a vacuum drying oven heat treatment, an electric heat treatment, a microwave heat treatment, an optical radiation heat treatment or a wind heat treatment.
Further, the temperature of the heat treatment was 80℃for 0.5h.
Further, the graphene oxide is coated in the form of a dispersion; the concentration of the dispersion liquid is 0.4mg/mL, and the volume is 20-40 mu L.
Further, the preparation method of the carboxyl functional PAN membrane (functional and hydrolytic at molecular level) comprises the following steps:
and placing the PAN film in an alkaline solution, oscillating in a water bath, and then placing the PAN film in an acidic solution for soaking to obtain the carboxyl functional PAN film.
PAN membranes are a necessary choice, which provides a material basis for hydrolysis.
Further, the alkaline solution is NaOH solution, and the concentration is 1.5mol/L; the temperature of the water bath oscillation is 50 ℃ and the time is 1h; the acid solution is hydrochloric acid solution, and the concentration is 1mol/L; the soaking time is 24 hours.
Further, the preparation method of the amino-functionalized PAN membrane (functionalization, hydrolysis and EDA functionalization at molecular level) comprises the following steps:
and placing the carboxyl functional PAN film in an ethylenediamine solution (EDA solution), oscillating in a water bath, and drying to obtain the amino functional PAN film.
Further, the concentration of the ethylenediamine solution is 10mg/mL; the temperature of the water bath oscillation is 25 ℃ and the time is 1-30 min; the temperature of the drying is 80 ℃ and the time is 0.5h.
The PAN film is functionalized at the molecular level, and a guarantee is provided for the maintenance of a micro-pore structure (the surface of the micro-filtration film always has a gap of about 10 nm).
Further, the preparation method of the graphene oxide specifically comprises the following steps: and mixing the acid liquor, the graphene and the potassium permanganate, heating for reaction, pouring the reacted solution into ice, uniformly mixing, dropwise adding hydrogen peroxide, centrifuging after the dropwise adding is finished, and precipitating to obtain the graphene oxide.
Further, the acid liquor is a mixed solution of concentrated sulfuric acid (18.4 mol/L) and concentrated phosphoric acid (14.6 mol/L) in a volume ratio of 5:1; the temperature of the heating reaction is 40 ℃ and the time is 6 hours.
Still further, the coating method comprises vacuum filtration, spin coating, pressurized assembly or gas-liquid interface assembly.
The second technical scheme of the application is as follows: the graphene oxide composite membrane prepared by the method.
The third technical scheme of the application: the application of the graphene oxide composite membrane in nanofiltration interception, reverse osmosis, forward osmosis, ultrafiltration, pervaporation or oil-water separation.
Further, the nanofiltration trapped object comprises inorganic divalent anions, inorganic trivalent anions, negatively charged small organic molecules or small neutral molecules with a molecular weight above 200.
The application discloses the following technical effects:
(1) The method solves the problem of unstable interaction between the functional layer and the cortex of the GO composite membrane, can enable the graphene oxide composite membrane to be tightly connected with the substrate, avoids the cortex from falling off, and realizes the improvement of interception performance.
(2) The graphene oxide composite membrane prepared by the method has excellent nanofiltration performance.
(3) According to the preparation method, through optimizing membrane preparation parameters (EDA adsorption time, post-adsorption heat treatment temperature, GO thickness and the like), the graphene oxide composite membrane (GO composite membrane) with improved screening performance and more stable pore channel structure is obtained.
(4) According to the application, PAN film is subjected to hydrolysis carboxylation and ethylenediamine two times of functionalization treatment, and the prepared GO composite film has more excellent interception performance (in the process of base film treatment, the second ethylenediamine functionalization parameter, the composite film heat treatment parameter and the like are very critical in the process of preparing composite film performance).
(5) The application selects common PAN microfiltration membrane as a substrate, respectively researches the influence of a single carboxyl functional base membrane and a secondary functional base membrane on the performance of the composite membrane, and specifically comprises the following steps: (1) Hydrolyzing the surface of the PAN base film to realize carboxyl functionalization, and then directly connecting with a GO skin layer to prepare a stable GO composite film (PAN-COOH-GO composite film); (2) Hydrolyzing the surface of a PAN base film to realize carboxyl functionalization, performing secondary functionalization on the carboxylated base film by using ethylenediamine to prepare an ultrafiltration film which performs amino functionalization at a molecular level, stabilizing a GO separation layer on the upper surface of the base film by covalent bonding with the secondary functionalized ultrafiltration film serving as a substrate, and preparing a GO composite film (PAN-COOH-EDA-GO composite film) with the stabilizing effect of a cortex and the base film. The ion interception performance of the composite membrane is tested by a laboratory cross-flow membrane performance evaluation instrument, and the result shows that the interception performance of the GO composite membrane (PAN-COOH-EDA-GO) prepared by taking the secondary functionalized PAN ultrafiltration membrane as a substrate is improved compared with that of the GO composite membrane (PAN-COOH-GO) bonded by the carboxyl of the substrate and the GO composite membrane (PAN-GO) without strong interaction of the substrate.
(6) In a general surface deposition method, particles having diameters of several nanometers to several tens nanometers are deposited on the surface of a microporous membrane, so that pores are easily blocked. The application uses the functionalization of molecular level, the size is within 1nm, and the hole can not be blocked. The ultrafiltration membrane treated by the method has little pore channel and PAN change (almost does not influence the morphology of pore channels on the surface of the membrane and can not cause the ultrafiltration base membrane to block pores), which can be proved by SEM photo comparison. If a GO separation layer is added, the pore canal is changed from ultrafiltration to nanofiltration, and the pore canal is changed from the 10nm level to the 1nm level (GO compact layer).
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of PAN, PAN-COOH-EDA films;
FIG. 2 is a surface infrared spectrum of PAN, PAN-COOH-EDA films;
FIG. 3 is a graph showing the nanofiltration performance of PAN-COOH-EDA-GO membranes prepared in examples 5-6 of the present application using different adsorption times;
FIG. 4 is a graph showing nanofiltration performance results of PAN-COOH-EDA-GO composite membranes prepared using different heat treatment temperatures in examples 5 and 7 of the present application;
FIG. 5 is a graph showing the nanofiltration performance results of PAN-COOH-EDA-GO composite membranes prepared using different volumes of graphene oxide standard dispersions in examples 5 and 8 of the present application;
FIG. 6 is a graph showing the results of pure water flux test of the PAN-GO composite membrane prepared in comparative example 2 of the present application;
FIG. 7 is a graph showing the results of pure water flux test of PAN-COOH-EDA-GO composite membrane prepared in example 5 of the present application;
FIG. 8 is a graph showing nanofiltration performance results for different retentate objects of the PAN-COOH-EDA-GO composite membrane prepared in example 5 of the present application;
FIG. 9 is a graph showing the nanofiltration performance results of PAN-COOH-EDA-GO composite membrane prepared in example 5 according to the present application and PAN-COOH-diamine-GO composite membrane prepared in comparative example 1 according to the present application under different diamines;
FIG. 10 is a graph showing nanofiltration performance results of the PAN-GO composite membrane prepared in comparative example 2 of the present application at different bubble times;
FIG. 11 is a graph showing nanofiltration performance results at various bubble times for the PAN-COOH-EDA-GO composite membrane prepared in example 5 of the present application.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
The preparation of Graphene Oxide (GO) refers to the classical hummers method, and comprises the following specific steps:
(1) Adding 240mL of mixed solution of concentrated sulfuric acid (18.4 mol/L) and concentrated phosphoric acid (14.6 mol/L) with the volume ratio of 5:1, 5.0g of graphene solid and 25.0g of potassium permanganate solid into a 500mL round bottom flask, reacting for 6 hours at 40 ℃, stopping heating, cooling to room temperature, pouring the solution on about 400g of ice, uniformly mixing, slowly dropwise adding 20mL of hydrogen peroxide, separating for 4 hours by using a centrifuge after the dropwise adding is finished, and discarding the supernatant, wherein the solid is the GO crude product.
(2) The resulting crude GO was washed 8 times with 1mol/L HCl solution and the solid was collected, and then washed 5 times with RO water (reverse osmosis water) (the last supernatant was measured for conductivity, if 0ms/cm, indicating that the ions attached to its surface had been washed clean) and the resulting solid was collected. Dispersing the cleaned solid in 200mL of RO water, carrying out suction filtration by taking a PVDF film with the aperture of 0.45 mu m as a substrate, and carrying out vacuum drying on the obtained filter cake at room temperature to obtain the graphene oxide paper.
(3) Dispersing graphene oxide paper with a certain mass into deionized water, and performing ultrasonic treatment at room temperature for 5min to promote uniform dispersion, so as to obtain graphene oxide standard dispersion liquid (GO-ss) with the concentration of 0.4 mg/mL.
Example 2
The preparation of PAN-COOH films (carboxyl-functionalized PAN films) comprises the following specific steps:
200mL of ethanol is added into a 500mL beaker, then the PAN membrane is placed into ethanol, the beaker is placed into a water bath oscillation instrument for oscillation for 1h (the temperature is 25 ℃), 300mL of new ethanol is replaced, the beaker is placed for soaking for 12h, RO water is used for washing for 2 times, the diaphragm is taken out, the diaphragm is placed into 300mL of RO water for soaking for 24h, residual ethanol is fully replaced, the surface RO water is removed from the cleaned diaphragm, the beaker is placed into a beaker containing 400mL of NaOH solution (the concentration is 1.5 mol/L), the beaker is placed into a 50 ℃ constant temperature water bath oscillation instrument for reaction for 1h (the temperature is 50 ℃), the diaphragm is taken out, the beaker is washed 3 times with RO water, the beaker is soaked into 200mL of HCl solution with the concentration of 1mol/L, the diaphragm is taken out and is washed with RO water for 30min (the temperature is 25 ℃) repeatedly, the diaphragm is soaked into 300mL of RO water after 3 times of washing, the diaphragm is oscillated for 24h, the diaphragm is taken out, the diaphragm is obtained, and the PAN-COOH membrane is immersed into cold storage RO water for standby.
Example 3
The PAN-COOH-EDA film is prepared under different adsorption time, and the specific steps are as follows:
transferring 20mL of ethylenediamine solution with the concentration of 10mg/mL into 5 clean weighing bottles respectively, taking out 5 PAN-COOH membranes prepared in example 2, airing surface moisture, placing in the weighing bottles, placing in a water bath oscillator for respectively adsorbing for 1min, 3min, 5min, 15min and 30min (the temperature is 25 ℃), taking out the membrane after the adsorption is finished, airing the ethylenediamine solution on the surface, then placing in an oven with the temperature of 80 ℃ for heating for 0.5h, taking out the membrane, cooling to room temperature, soaking in ethanol, placing in the water bath oscillator for cleaning for 0.5h (the temperature is 25 ℃), repeating for 4 times, taking out the membrane, airing, immersing in RO water, placing in the water bath oscillator for cleaning (the temperature is 25 ℃), preparing the PAN-COOH-EDA membrane, and placing in the RO water for standby.
Example 4
The preparation of the PAN-COOH-GO composite film comprises the following specific steps:
(1) In a beaker, 30 μl of the graphene oxide standard dispersion prepared in example 1 (GO standard dispersion) was mixed in 15mL of deionized water to obtain a film-forming liquid; covering the beaker cover by using a preservative film, sealing by using an elastic band, and placing the film-making liquid into an ultrasonic cleaner for ultrasonic treatment for 5min to obtain film-making liquid G.
(2) Taking out the glass sand core filtering device, cleaning the device for 3 times by tap water and RO water respectively, cleaning the glass sand core by RO water, placing the PAN-COOH film prepared in the embodiment 2 on the glass sand core, sucking bubbles between the film and the sand core by paper, and assembling the device; taking out the film-making liquid G, pouring the film-making liquid G into a glass sand core filtering device, and connecting a vacuum circulating water pump after the liquid level is stable and motionless; and (3) coating GO on the PAN-COOH film by using a vacuum assisted suction filtration assembly method, drying at room temperature, and performing heat treatment for 1h in an oven at 80 ℃ to obtain a PAN-COOH-GO film (PAN-COOH-GO composite film or graphene oxide composite film) with carboxyl-linked skin layers, and taking out for use.
Example 5
The preparation of the PAN-COOH-EDA-GO composite film comprises the following specific steps:
(1) In a beaker, 30 μl of the graphene oxide standard dispersion prepared in example 1 (GO standard dispersion) was mixed in 15mL of deionized water to obtain a film-forming liquid; covering the beaker cover by using a preservative film, sealing by using an elastic band, and placing the film-making liquid into an ultrasonic cleaner for ultrasonic treatment for 5min to obtain film-making liquid G.
(2) Taking out the glass sand core filtering device, cleaning the device for 3 times by tap water and RO water respectively, cleaning the glass sand core by RO water, placing the PAN-COOH-EDA film with the adsorption time of 3min in the embodiment 3 on the glass sand core, sucking bubbles between the film and the sand core by paper, and assembling the device; taking out the film-making liquid G, pouring the film-making liquid G into a glass sand core filtering device, and connecting a vacuum circulating water pump after the liquid level is stable and motionless; and (3) coating GO on the PAN-COOH-EDA film by using a vacuum assisted suction filtration assembly method (a vacuum suction filtration method), drying at room temperature, and performing heat treatment for 1h in an oven (a blast drying oven) at 80 ℃ to prepare an amino-linked cortical PAN-COOH-EDA-GO film (a PAN-COOH-EDA-GO composite film or a graphene oxide composite film), and taking out for use.
Example 6
The difference from example 5 was that the PAN-COOH-EDA film in step (1) was replaced with the PAN-COOH-EDA film having adsorption times of 1min, 5min, 15min, and 30min in example 3, respectively, to obtain 4 different PAN-COOH-EDA-GO composite films (graphene oxide composite films).
Example 7
The difference from example 5 was only that the temperature of the heat treatment in step (2) was replaced with 25 ℃, 60 ℃ and 100 ℃ respectively, to obtain 3 different PAN-COOH-EDA-GO composite films (graphene oxide composite films).
Example 8
The difference from example 5 was that the volumes of the standard dispersion of graphene oxide in step (1) were replaced with 20. Mu.L, 25. Mu.L, 35. Mu.L and 40. Mu.L, respectively, to prepare 4 different PAN-COOH-EDA-GO composite films (graphene oxide composite films).
Comparative example 1
Preparation of GO composite membranes crosslinked with different diamines the preparation of each composite membrane was the same as in example 5, except that the ethylenediamine crosslinking agent of the PAN-COOH-EDA-GO composite membrane in step (2) was replaced with other diamines, respectively: and preparing 2 different PAN-COOH-diamine-GO composite films (graphene oxide composite films) by using tri (2-aminoethyl) amine and diethylenetriamine.
Comparative example 2
The difference with example 4 is that the PAN-COOH based membrane in the step (2) is changed into a PAN ultrafiltration membrane to prepare a PAN-GO composite membrane.
Effect example 1
The surface morphology of PAN film, PAN-COOH film and PAN-COOH-EDA film was characterized by using a field emission Scanning Electron Microscope (SEM) method, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the pore structure of the upper surface of the membrane prepared by hydrolysis (PAN-COOH membrane) and subsequent hydrolysis and EDA functionalization (PAN-COOH-EDA membrane) is clear, and no obvious pore blocking phenomenon occurs.
Effect example 2
The surface chemistry of PAN films, PAN-COOH-EDA films (adsorption time 3 min) was characterized (surface ATR-IR), and the results are shown in FIG. 2.
As can be seen from FIG. 2, the PAN-COOH film was 1696cm compared to the PAN film -1 A new peak appears at the position, which corresponds to the peak of carbonyl in carboxylate radical, and verifies the hydrolysis result of the PAN film surface; PAN-COOH-EDA film was then at 1682cm -1 New peaks appear at positions 1566 and correspond to carbonyl groups in the carboxyl and amide bonds, respectively, indicating that part of the carboxyl groups are converted to amide groups, confirming that EDA is covalently functionalized to the PAN-COOH surface.
Characterization of Membrane separation Performance (nanofiltration Performance)
The nanofiltration performance of the composite membrane is tested by using a laboratory cross-flow filtration device, each membrane is controlled to be pre-pressed for 2 hours under 0.7MPa, and the membrane data are obtained under the parallel test of three membranes. The test solution was 1 g/L1800 mL Na 2 SO 4 A solution. The liquid was connected by a weighed plastic centrifuge tube (the mass of which was denoted as m 1 ) And recording time from the time when the first drop of liquid falls down to about 3mL, stopping timing, and recording time as t 2 And finally, connecting 3mL of stock solution by using a plastic centrifugal tube, and placing the plastic centrifugal tubes on a centrifugal tube rack to be tested. Plastic centrifuge for weighingTotal mass m of tube and liquid received 2 . The conductivity of the solution in each plastic centrifuge tube was measured.
Permeate flux and solute rejection were calculated from equations 1 and 2:
flux (Flux) = 84.87 × (m) 2 -m 1 )/Δt(L·m -2 ·h -1 ) Equation 1
Rej (retention) = (1-C) p /C f ) X 100% equation 2
C p : osmotic solubility; c (C) f : feed solution solubility.
The nanofiltration performance of the PAN-COOH-EDA-GO composite membrane prepared under different membrane preparation parameters is compared, and the specific membrane preparation parameters comprise: EDA adsorption time, EDA processing temperature, volume of graphene oxide standard dispersion.
Effect example 3
Nanofiltration properties of PAN-COOH-EDA-GO composite membranes prepared using PAN-COOH-EDA membranes prepared at different adsorption times in examples 5 to 6 were measured and the results are shown in fig. 3.
Test conditions: na (Na) 2 SO 4 Salt concentration: 1g/L,0.7MPa, cross flow: 30LPH.
As can be seen from FIG. 3, the PAN-COOH-GO composite membrane (adsorption time is 0 min) without EDA adsorption, while keeping good retention rate, the flux is very small, and the possibility of practical application is almost low. After EDA is adsorbed, the flux is obviously improved, and the flux is improved to 14 L.m in a PAN-COOH-EDA-GO composite membrane prepared by adopting a PAN-COOH-EDA membrane with the adsorption time of 3min 2- ·h -1 The rejection rate of sodium sulfate is also slightly improved (reaching 91%). Compared with the PAN-COOH-GO membrane, the flux is obviously increased, and the retention rate is increased by 3%.
Effect example 4
Nanofiltration properties of PAN-COOH-EDA-GO composite membranes prepared in examples 5, 7 using different heat treatment temperatures were determined and the results are shown in fig. 4.
Test conditions: na (Na) 2 SO 4 Salt concentration: 1g/L,0.7MPa, cross flow: 30LPH.
As can be seen from FIG. 4, the effect of heat treatment at 80℃is optimal, indicating that the effect is remarkable after the temperature reaches 80℃by dehydration condensation of carboxyl groups and amino groups.
Effect example 5
Nanofiltration properties of PAN-COOH-EDA-GO composite membranes prepared in examples 5, 8 using different volumes of graphene oxide standard dispersion were measured, and the results are shown in fig. 5.
Test conditions: na (Na) 2 SO 4 Salt concentration: 1g/L,0.7MPa, cross flow: 30LPH.
As can be seen from fig. 5, the entrapment of sodium sulfate by PAN-COOH-EDA-GO composite membrane was gradually improved with the increase of the Graphene Oxide (GO) loading, and the loading of the PAN-COOH-EDA-GO composite membrane was 0.96 μg cm when the amount of the graphene oxide standard dispersion was 30 μl -2 ) The rejection rate reaches the maximum value. As the amount of graphene oxide standard dispersion increases, the water flux gradually decreases. Taking the retention rate and flux into comprehensive consideration, selecting 30 mu L of membrane preparation volume (GO load capacity is 0.96 mu g cm) of the optimal GO standard dispersion -2 )。
Membrane pure water flux-pressure relationship test
The nanofiltration performance of the composite membrane is tested by using a laboratory cross-flow filtration device, and the operation pressure of each membrane is controlled to be changed gradually at 0.1-0.7-0.1 MPa, and the membrane is modulated once every 10 min. The membrane data were obtained under a parallel test of three membranes, and the test solution was pure water. The liquid was connected by a weighed plastic centrifuge tube (the mass of which was denoted as m 1 ) Recording time from the moment of falling of the first drop of liquid, receiving for 10min, stopping receiving liquid, and recording total liquid-containing mass m of the centrifuge tube 2 And adjusting the operation pressure, and immediately starting the next liquid receiving cycle after stabilizing.
The permeate flux was calculated from equation 3:
flux (Flux) = 84.87 ×6× (m 2 -m 1 )(L·m- 2 ·h -1 ·bar -1 ) Equation 3
Effect example 5
(1) The pure water flux of the PAN-GO composite membrane prepared in comparative example 2 was measured, and the result is shown in fig. 6.
Test conditions: RO water, 0.1- & gt 0.7- & gt 0.1MPa, cross-flow 30LPH.
(2) The pure water flux of the PAN-COOH-EDA-GO composite membrane prepared in example 5 was measured, and the result is shown in FIG. 7.
Test conditions: RO water, 0.1- & gt 0.7- & gt 0.1MPa, cross-flow 30LPH.
As can be seen from fig. 6 and 7, the flux-pressure curve changes of the two composite membranes are similar, and both have two stages: (1) In the initial stage of pressurization, the water flux is obviously reduced along with the increase of the operation pressure, which indicates that the GO interlayer channel structure is obviously reduced along with the increase of the pressure; (2) When the pressure reaches 0.7MPa and then drops, the water flux is not changed along with the change of the operation pressure, which indicates that the membrane structure can be stabilized after high-pressure compaction. The PAN-GO membrane and the PAN-COOH-EDA-GO membrane have certain difference, the PAN-COOH-EDA-GO membrane is lower than the PAN-GO membrane in the initial stage of pressurization, and the water flux is higher than the PAN-GO membrane when the PAN-COOH-EDA-GO membrane enters the flux stabilization period after depressurization, so that the addition of the PAN-GO membrane indicates that the addition of the PAN-COOH-EDA-membrane has a stabilization effect on the channels of the GO cortex and has no obvious oversized holes; on the other hand, the maintenance of GO cortex pore channels is facilitated. This test was not done because the PAN-COOH-GO membrane flux was too low and no change was detected under the existing conditions.
Effect example 6
Nanofiltration properties of the PAN-COOH-EDA-GO composite membrane of example 5 were measured for different subjects trapped, and the results are shown in fig. 8.
Test conditions: trapped object concentration: 1g/L,0.7MPa, cross flow: 30LPH, the trapped objects are respectively: sodium sulfate, C 6 H 12 O 6 (glucose), magnesium sulfate, magnesium chloride, and sodium chloride.
As can be seen from FIG. 8, the composite membrane has the best trapping effect on sodium sulfate, and on sodium sulfate and C 6 H 12 O 6 The retention rates of magnesium sulfate, magnesium chloride and sodium chloride are sequentially reduced, and the method is similar to the rule of a GO separation layer, which shows that the treatment of the cross-linked ultrafiltration base membrane and the separation layer is mainly to stabilize the action of the separation layer and the base membrane, and has no influence on the structure and the surface property of the separation layer.
Effect example 7
The nanofiltration properties of the PAN-COOH-EDA-GO composite membrane prepared in example 5 of the present application (adsorption for 3 min) and the PAN-COOH-diamine-GO composite membrane prepared in comparative example 1 using different diamine cross-linking agents were measured, and the results are shown in fig. 9.
Test conditions: sodium sulfate concentration: 1g/L,0.7MPa, cross flow: 30LPH.
As can be seen from fig. 9, among the different diamine cross-linking agents, the ethylenediamine cross-linked composite membrane has the best effect of intercepting sodium sulfate, the other two longer chain diamines have significantly reduced effects, and the reduction degree is increased with the increase of chain length, which indicates that the short chain diamines are more suitable for linking the PAN-COOH based membrane with the GO separation layer.
Effect example 8
Stability test with ultrafiltration base membrane and separation layer cross-linked or not. The PAN-COOH-EDA-GO composite membrane (adsorbed for 3min in example 5) and the PAN-GO composite membrane (prepared in comparative example 2) were soaked in RO water for a certain period of time for the subsequent experiments on sodium sulfate entrapment, the soaking times were respectively: 0h, 0.5h, 1h, 24h. Wherein 0h represents the composite film without soaking. The PAN-GO composite membrane and PAN-COOH-EDA-GO composite membrane of comparative example 2 were tested for membrane nanofiltration performance after soaking in water, and the results are shown in fig. 10-11.
Test conditions: sodium sulfate concentration: 1g/L,0.7MPa, cross flow: 30LPH.
From fig. 10, it can be seen that the rejection effect of the PAN-GO composite membrane on sodium sulfate is significantly reduced after soaking, while the PAN-COOH-EDA-GO composite membrane is almost unchanged (the rejection rate of fig. 11 is reduced within 2%), which indicates that after the PAN-COOH-based membrane and the GO separation layer are crosslinked by a-COO-EDA-chain, the underwater structure of the membrane is stable, and the PAN-COOH-EDA-GO composite membrane is expected to be applied to complex actual nanofiltration separation.
According to the application, a mode of covalently linking the PAN ultrafiltration base membrane and the GO separation layer is designed, and parameters such as EDA adsorption time, post-adsorption heat treatment temperature, GO cortex thickness (the dosage of graphene oxide standard dispersion liquid) and the like are optimized, so that the PAN-COOH-EDA-GO composite membrane with improved retention performance is prepared. From the experiments of the composite membrane on sodium sulfate interception, pure water flux-operating pressure and membrane soaking performance, the PAN-COOH-EDA-GO composite membrane has a more stable membrane structure than the PAN-GO composite membrane, and maintains rich water channels (avoids the rapid decrease of flux) than the PAN-COOH-GO composite membrane. According to the application, a new treatment process is carried out on the PAN film, and the composite film with stable structure and improved sieving performance is prepared, so that the GO composite film is expected to be oriented to practical application.
The above embodiments are only illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solutions of the present application should fall within the protection scope defined by the claims of the present application without departing from the design spirit of the present application.
Claims (10)
1. The method for stabilizing the graphene oxide skin layer and the ultrafiltration base membrane is characterized by comprising the following steps of:
and carrying out functionalization treatment on the PAN film to obtain a functionalized PAN film, then coating graphene oxide on the functionalized PAN film, and carrying out heat treatment to obtain the graphene oxide composite film.
2. The method of stabilizing a graphene oxide skin layer and ultrafiltration membrane of claim 1, wherein the functionalized PAN membrane comprises a carboxyl-functionalized PAN membrane or an amino-functionalized PAN membrane; the temperature of the heat treatment is 25-100 ℃ and the time is 0.5h.
3. The method for stabilizing a graphene oxide skin layer and an ultrafiltration membrane according to claim 2, wherein the preparation method of the carboxyl-functionalized PAN membrane comprises the following steps:
and placing the PAN film in an alkaline solution, oscillating in a water bath, and then placing the PAN film in an acidic solution for soaking to obtain the carboxyl functional PAN film.
4. The method for stabilizing a graphene oxide skin layer and an ultrafiltration membrane according to claim 3, wherein the alkaline solution is a NaOH solution with a concentration of 1.5mol/L; the temperature of the water bath oscillation is 50 ℃ and the time is 1h; the acid solution is hydrochloric acid solution, and the concentration is 1mol/L; the soaking time is 24 hours.
5. The method for stabilizing graphene oxide skin and ultrafiltration membrane according to claim 2, wherein the preparation method of the amino-functionalized PAN membrane comprises the following steps:
and placing the carboxyl functional PAN film in an ethylenediamine solution, oscillating in a water bath, and drying to obtain the amino functional PAN film.
6. The method of stabilizing a graphene oxide skin layer and ultrafiltration membrane according to claim 5, wherein the concentration of the ethylenediamine solution is 10mg/mL; the temperature of the water bath oscillation is 25 ℃ and the time is 1-30 min; the temperature of the drying is 80 ℃ and the time is 0.5h.
7. The method for stabilizing a graphene oxide skin layer and an ultrafiltration membrane according to claim 1, wherein the preparation method of graphene oxide specifically comprises: and mixing the acid liquor, the graphene and the potassium permanganate, heating for reaction, pouring the reacted solution into ice, uniformly mixing, dropwise adding hydrogen peroxide, centrifuging after the dropwise adding is finished, and precipitating to obtain the graphene oxide.
8. The method for stabilizing a graphene oxide skin layer and an ultrafiltration membrane according to claim 7, wherein the acid solution is a mixed solution of 18.4mol/L concentrated sulfuric acid and 14.6mol/L concentrated phosphoric acid in a volume ratio of 5:1; the temperature of the heating reaction is 40 ℃ and the time is 6 hours.
9. A graphene oxide composite membrane prepared by the method of any one of claims 1 to 8.
10. Use of the graphene oxide composite membrane of claim 9 in nanofiltration rejection, reverse osmosis, forward osmosis, ultrafiltration, pervaporation or oil-water separation.
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