CN112957929A - Modified graphene oxide membrane based on anion and cation regulation and control, preparation method and application - Google Patents
Modified graphene oxide membrane based on anion and cation regulation and control, preparation method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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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 invention provides a modified graphene oxide membrane based on anion and cation regulation and control, a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing graphene oxide sol; preparing a graphene oxide film on the surface of the porous carrier; preparing an anion/cation solution; and immersing the graphene oxide film in an anion/cation solution for modification treatment to obtain the modified graphene oxide film. According to the invention, the graphene oxide film is obtained, and the film material taking the graphene oxide film as a selective layer is prepared and applied to the pervaporation desalination technology in a simple manner of regulating and controlling the distance between graphene oxide layers based on anions and cations. The method utilizes a simple method to regulate and control the distance between graphene oxide layers, and the prepared graphene oxide membrane has higher water permeation selectivity and permeation flux, can effectively desalt seawater, thereby providing a high-efficiency, environment-friendly and economic technical means for seawater desalination, and has important practical significance.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and particularly relates to a modified graphene oxide membrane based on anion and cation regulation and control, a preparation method and application.
Background
Water is one of the basic necessities of life on earth, but as the population of the world increases and the climate changes, the shortage of fresh water resources has become a serious problem, and seawater desalination has become an important method for increasing the supply of fresh water. Currently, many purification techniques have been applied to the desalination of water, including distillation, ion exchange and membrane separation.
Traditional water purification methods such as distillation are effective means for removing bacteria, minerals, water hardness etc. substances such as calcium, magnesium and harmful metals. Distillation, however, can remove drinking water contaminants but cannot remove chlorine and some volatile organic compounds. The produced mineral-free water is acidic and has certain influence on human health, and more importantly, the energy consumption is very high. Among them, the membrane separation technology is the most promising alternative technology in the separation field because of its advantages of high efficiency, low energy consumption, easy operation and low investment. The membrane separation technology utilizes the difference of chemical potential of certain components on two sides of the membrane as a driving force, and the membrane realizes selective separation on the difference of affinity and mass transfer resistance of different components in feed liquid.
In addition, graphene is a two-dimensional monoatomic layer material arranged by an sp2 hybridized carbon six-membered ring array, and has received extensive attention and research due to its superior mechanical, electronic and optical properties. Partially oxidized, stacked graphene can provide ultra-thin, high-throughput and energy-efficient thin films for precise ion and molecular sieving in aqueous solutions. Although the thickness of the monoatomic layer of the graphene film is the goal of film material preparation, the ideal regular graphene film is a dense film layer and cannot permeate any gas and liquid. For example, some progress has been made in desalting brine using graphene-based desalting membranes. Han et al prepared an ultrathin graphene nanofiltration membrane on a microporous substrate with a rejection of 40% for 20mM NaCl and a flux of 3.3kg·m-2·h-1(Adv.Funct.Mater.,2013,23,3693-3700)。
Therefore, how to provide a modified graphene oxide film with graphene oxide based on anion and cation regulation, a preparation method and an application thereof are necessary to solve the above problems in the prior art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a modified graphene oxide membrane based on anion and cation modulation, a preparation method and an application thereof, which are used for solving the problems in the prior art that it is difficult to prepare an effective separation membrane based on a membrane separation technology, especially a separation membrane for seawater desalination.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a modified graphene oxide membrane based on anion and cation modulation, the method comprising the steps of:
providing graphene oxide, and dissolving the graphene oxide in water to obtain graphene oxide sol;
providing a porous carrier, and forming a graphene oxide film on the surface of the porous carrier based on the graphene oxide sol;
providing an anionic/cationic solution;
and immersing the graphene oxide film in the anion/cation solution for modification treatment to obtain a modified graphene oxide film.
Optionally, the concentration of the graphene oxide sol is between 0.08-0.12 mg/mL.
Optionally, the modified graphene oxide film has an interlayer spacing between 0.5-0.56 nm.
Optionally, the preparation method comprises at least one of the following conditions: A1) the configuration of the porous support comprises a tubular shape; A2) the porous support comprises a porous ceramic support; A3) the average pore diameter of the porous carrier is between 90 and 110 nm.
Optionally, the graphene oxide film is formed using a pressure assisted deposition method.
Optionally, in the process of forming the graphene oxide membrane, the porous carrier is loaded into a permeation assembly, the graphene oxide sol is introduced from the inner side of the membrane tube, and auxiliary gas is used as a driving force to pressurize and assist deposition on the inner surface of the porous carrier, wherein the pressure is between 1 and 10bar, and the total mass of the graphene oxide sol is between 0.25 and 0.75 mg.
Optionally, the process of obtaining the modified graphene oxide film further comprises a step of drying after dipping, wherein the drying mode comprises vacuum drying, the drying temperature is between 40 and 50 ℃, and the drying time is between 10 and 15 hours.
Optionally, in the anion/cation solution, the anion comprises any one of methyl blue, methyl orange, congo red and ponceau red; the cation comprises any one of methylene blue, 1-vinyl-3-ethylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole chloride salt, 1-allyl-3-vinylimidazole chloride salt and 1-benzyl-3-methylimidazole chloride salt.
Alternatively, the solution molar concentration of said anion is between 0.5-1.5 mM; when the cation is methylene blue, the molar concentration of the solution is between 0.5 and 1.5 mM; the molar concentration of the rest of the cation solution is between 2.5 and 3.5 mM.
In addition, the invention also provides a modified graphene oxide membrane based on anion and cation regulation, and the modified graphene oxide membrane is prepared by adopting the preparation method in any one of the schemes.
In addition, the invention also provides an application of the modified graphene oxide membrane in any one of the schemes, and the modified graphene oxide membrane is used for seawater desalination.
Optionally, a seawater desalination simulation step is included, wherein the simulated seawater comprises at least one of sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate, and calcium sulfate.
Optionally, when the modified graphene oxide membrane is used for seawater desalination, a pervaporation process is adopted, the temperature of pervaporation is between 30 and 90 ℃, the pressure of a permeation side is between 85 and 95Pa, and the feed flow is between 10 and 15 mL/min.
As described above, according to the modified graphene oxide membrane based on anion and cation regulation and the preparation method of the modified graphene oxide membrane based on anion and cation regulation, the membrane material with the graphene oxide membrane as a selection layer is prepared and applied to the pervaporation desalination technology in a simple manner of obtaining the graphene oxide membrane and regulating the distance between graphene oxide layers based on anion and cation. The method utilizes a simple method to regulate and control the distance between graphene oxide layers, and the prepared graphene oxide membrane has higher water permeation selectivity and permeation flux, can effectively desalt seawater, thereby providing a high-efficiency, environment-friendly and economic technical means for seawater desalination, and has important practical significance.
Drawings
Fig. 1 shows a flow chart of the preparation of the modified graphene oxide membrane based on anion and cation modulation according to the present invention.
FIG. 2 is a schematic diagram of a pervaporation separation process according to the present invention.
FIG. 3 shows a scanning electron microscope image of the surface morphology of the modified graphene oxide film supported by the porous alumina tube of the present invention.
Fig. 4 shows a scanning electron microscope image of the interface morphology of the modified graphene oxide film supported by the porous alumina tube of the present invention.
FIG. 5 shows a transmission electron microscope image of the interface morphology of a modified graphene oxide film supported by the porous alumina tube of the present invention.
Description of the element reference numerals
1 feeding liquid
2 peristaltic pump
3 membrane module and heat source
4 stop valve
5 Cold trap
6 vacuum meter
7 vacuum pump
S1-S4
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
As in the detailed description of the embodiments of the present invention, the cross-sectional views illustrating the device structures are not partially enlarged in general scale for convenience of illustration, and the schematic views are only examples, which should not limit the scope of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
For convenience in description, spatial relational terms such as "below," "beneath," "below," "under," "over," "upper," and the like may be used herein to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that these terms of spatial relationship are intended to encompass other orientations of the device in use or operation in addition to the orientation depicted in the figures. Further, when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. In addition, "between … …" as used herein includes both endpoints.
In the context of this application, a structure described as having a first feature "on" a second feature may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features are formed in between the first and second features, such that the first and second features may not be in direct contact.
It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed freely, and the layout of the components may be more complicated.
As shown in fig. 1, the present invention provides a method for preparing a modified graphene oxide membrane based on anion and cation modulation, the method comprising the steps of:
s1, providing graphene oxide, and dissolving the graphene oxide in water to obtain graphene oxide sol;
s2, providing a porous carrier, and forming a graphene oxide film on the surface of the porous carrier based on the graphene oxide sol;
s3, providing an anion/cation solution;
and S4, dipping the graphene oxide film in the anion/cation solution for modification treatment to obtain the modified graphene oxide film.
The following will describe in detail a method for preparing a modified graphene oxide membrane based on anion and cation modulation according to the present invention with reference to the accompanying drawings, where it should be noted that the above sequence does not strictly represent the preparation sequence of the method for preparing a modified graphene oxide membrane based on anion and cation modulation according to the present invention, and those skilled in the art may change the sequence according to actual process steps, and fig. 1 only shows the preparation steps of the modified graphene oxide membrane based on anion and cation modulation in one example of the present invention.
First, as shown in S1 in fig. 1, graphene oxide is provided and dissolved in water to obtain a graphene oxide sol. In this step, graphene oxide is dissolved in water to form a clear graphene oxide sol.
In one example, the obtained graphene oxide sol has a concentration of 0.08-0.12mg/ml, and is a graphene oxide hydrosol. For example, the concentration may be 0.09mg/ml, 0.1mg/ml, 0.11 mg/ml.
In one example, the graphene oxide is prepared by a Hummers method.
The graphene is oxidized to obtain oxidized graphene, various oxygen-containing groups are formed on the carbon ring and the edge of the oxidized graphene, the material is changed from hydrophobicity to hydrophilicity, the distance between layers is increased from 0.34nm to about 0.45nm, and the graphene has great separation application potential. Different from the fixed size of the carbon nanotube film hole, the size of the graphene oxide film hole (namely, the interlayer spacing between graphene oxide sheets) is variable, and the graphene oxide sol is obtained and the modified graphene oxide is obtained based on the subsequent process.
Next, as shown in S2 in fig. 1, providing a porous support, and forming a graphene oxide film on the surface of the porous support based on the graphene oxide sol;
in one example, the porous support comprises a porous ceramic support. In a further alternative example, the porous ceramic support may be any one of an alumina porous support, a titania porous support, and a zirconia porous support.
In one example, the porous support has an average pore size between 90-110nm, which may be, for example, 92nm, 95nm, 100nm, 102nm, 105 nm.
In one example, the porous ceramic support is tubular with an inner diameter of between 6-8mm and an outer diameter of between 9-11mm, for example, in one specific example, an inner diameter of 7mm and an outer diameter of 10 mm. In addition, in another example, the carrier is sealed at both ends, and the effective film length is between 15-25mm, for example, 16mm, 20mm, and 22 mm.
As an example, the method further comprises the step of cleaning and surface treating the porous ceramic support before forming the graphene oxide film, wherein optionally, the porous ceramic support is sequentially cleaned by ethanol, a 4% KOH aqueous solution and ultrapure water, and boiled by ultrapure water to remove impurities and dust on the surface of the porous ceramic support.
As an example, the graphene oxide film is formed on the surface of the porous support by a pressure-assisted deposition method.
In a further example, during the formation of the graphene oxide membrane, the porous support is loaded into a permeation module, the graphene oxide sol is introduced from the inner side of a membrane tube, and the deposition is assisted by pressurizing the inner surface of the porous support with an auxiliary gas (for example, nitrogen) as a driving force, wherein the pressure is between 1 and 10 bar. In a further alternative example, the total mass of the graphene oxide sol is selected to be between 0.25-0.75 mg.
For example, in a specific example, the porous support is a tubular ceramic support, the ceramic tube is installed in the infiltration assembly, graphene oxide hydrosol is introduced from the inner side of the membrane tube, and the pressure is applied to the inner surface of the support to assist deposition by using nitrogen gas with a certain pressure as a driving force, wherein the pressure is 1-10bar, and may be 2bar, 5bar, or 8bar, and the total amount of graphene oxide is 0.5 mg. For example, the concentration of the graphene oxide sol is 0.1mg/mL, and 5mL of the above graphene oxide hydrosol is diluted to 200mL, that is, the total amount of graphene oxide is 0.5 mg.
Next, as shown by S3 in fig. 1, an anion/cation solution is provided. This step prepares the anion into a clear solution.
As an example, in the anion/cation solution, the anion includes any one of methyl blue, methyl orange, congo red and ponceau red; the cation comprises any one of methylene blue, 1-vinyl-3-ethylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole chloride salt, 1-allyl-3-vinylimidazole chloride salt and 1-benzyl-3-methylimidazole chloride salt.
Illustratively, the solution molar concentration of the anion is between 0.5-1.5 mM; for example, it may be 0.8mM, 1mM, 1.2 mM; in addition, when the cation is methylene blue, the solution molar concentration is between 0.5 and 1.5mM, for example, it may be 0.8mM, 1mM, 1.2 mM; when other cations are present, the molarity of the other cation solution is between 2.5-3.5mM, and may be 2.8mM, 3mM, 3.2 mM.
By way of example, the anions used include methyl blue, methyl orange, congo red, ponceau red, in a molarity of 1 mM; the anions mentioned here were each tested individually for modification, and the concentration in each impregnation was 1 mM. The following cations work in the same way. The cation used comprises methylene blue with a molar concentration of 1 mM; 1-vinyl-3-ethylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole chloride salt, 1-allyl-3-vinylimidazole chloride salt and 1-benzyl-3-methylimidazole chloride salt, wherein the molar concentration is 3 mM.
In an alternative example, the concentration of the anion/cation solution and the concentration of the graphene oxide sol have a one-to-one correspondence relationship, such as the correspondence manner in the embodiment.
Finally, as shown in S4 in fig. 1, the graphene oxide film is immersed in the anion/cation solution to be modified, so that a modified graphene oxide film is obtained. Based on the scheme of the invention, ions are mainly inserted between graphene oxide layers by utilizing the ion-pi bond effect, the interlayer spacing of the graphene oxide is effectively controlled and cannot be expanded randomly in a liquid phase, and the interlayer spacing is smaller than the hydration size of separated ions and larger than the size of water molecules, so that accurate size screening is realized, and the desalination rate is ensured. Based on the impregnation process, namely the ion-pi bond effect, the impregnation effect is changed by adjusting the concentration of the impregnation ions and the impregnation time.
By way of example, the graphene oxide membrane is immersed in the anion and cation solution for 0.3-2.5h, such as 0.5h, 1h, and 2 h.
As an example, the process of obtaining the modified graphene oxide film further includes a step of drying after dipping, wherein the drying manner includes vacuum drying, the drying temperature is between 30 ℃ and 45 ℃, and the drying time is longer than 8h, for example, between 10 hours and 15 hours. For example, the drying temperature may be 32 ℃, 35 ℃, 40 ℃; the drying time can be 9h, 11h, 12h and 13 h. For example, in one example, the drying is vacuum drying at 45 ℃ for 12 hours.
As an example, the interlayer spacing of the graphene oxide film after modulation is about 0.5 to 0.56nm, for example, 0.52nm, 0.53nm, 0.54nm, 0.55 nm; before regulation, the particle size is about 0.45 nm.
Specifically, in the technical scheme of the invention, a simple and convenient way for regulating and controlling the distance between graphene oxide layers is found, the distance between the graphene oxide layers is regulated and controlled by a simple method based on the regulation and control of anions and cations, and the prepared graphene oxide membrane has higher water permeation selectivity and permeation flux, can effectively desalt seawater, thereby providing a high-efficiency, environment-friendly and economic technical means for seawater desalination and having important practical significance. The design of the present invention solves many problems in the potential ion filtration application of graphene oxide membranes, and based on the design of the present invention, the interlayer spacing can be reduced to a degree sufficient to repel small ions, and further such spacing is maintained to prevent the tendency of graphene oxide membranes to swell when immersed in aqueous solutions.
Fig. 3 is a scanning electron microscope image of the surface topography of the modified graphene oxide film supported by the porous alumina tube in an example of the present invention, and it can be seen that the surface of the modified graphene oxide film is relatively flat and has relatively typical graphene wrinkles; FIG. 4 shows a scanning electron microscope image of the interface morphology of a modified graphene oxide film supported by a porous alumina tube according to an example of the present invention, wherein the thickness of the modified graphene oxide film is about 100-150 nm, and FIG. 4 shows an example of 120 nm. In addition, fig. 5 shows a transmission electron microscope image of the cross-sectional morphology of the modified graphene oxide film supported by the porous alumina tube in an example of the present invention, in which the interlayer spacing after modification is increased to 0.53nm compared to the common graphene oxide layer spacing before modification (about 0.45 nm). The interlayer spacing is increased after modification, and ions are effectively inserted between the layers.
In addition, the invention also provides a modified graphene oxide membrane based on anion and cation regulation, and the modified graphene oxide membrane is prepared by adopting the preparation method in any one of the schemes. The characteristics and the like of the relevant constituent materials can be referred to the description in the preparation method, and are not described again.
In addition, the invention also provides an application of the modified graphene oxide membrane in any one of the schemes, and the modified graphene oxide membrane is used for seawater desalination. The characteristics of the modified graphene oxide composite film and the like can be referred to the description in the preparation method, and are not described herein again.
As an example, the method comprises a step of performing seawater desalination simulation, wherein the simulated seawater comprises inorganic salt components such as sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate and calcium sulfate. One or more of the above components may be used. For example, all of the components described above are included. In one example, the content of the above components is 0.1M to 3.5 wt%.
As an example, when seawater is desalinated by using the modified graphene oxide membrane, a pervaporation process is adopted.
Furthermore, based on the obtained modified graphene oxide, desalination separation is carried out by adopting a pervaporation process, and compared with other membrane desalination technologies, the modified graphene oxide film has higher water permeation selectivity and permeation flux, the interlayer spacing can be reduced to a degree enough to reject small ions, and the interlayer spacing is further maintained to prevent the expansion tendency of the graphene oxide film when the graphene oxide film is immersed in an aqueous solution, so that the modified graphene oxide film is particularly suitable for a pervaporation process, and has high retention rate of pervaporation salts and lower pretreatment requirement.
In one example, in a pervaporation process, the temperature of pervaporation is between 30-90 ℃, can be 45 ℃, 80 ℃, the permeate side pressure is between 85-95Pa, can be 88Pa, 92Pa, and the feed flow is between 10-15mL/min, can be 11mL/min, 13 mL/min. For example, in a specific example, the temperature of pervaporation is between 60 ℃, the permeate side pressure is between 90Pa, and the feed flow is between 12 mL/min.
In addition, as shown in fig. 2, a system for separation based on pervaporation is provided, which includes a feed liquid containing device for containing a feed liquid 1, a peristaltic pump 2, a membrane module and a heat source 3, a stop valve 4, a cold trap 5, a vacuum meter 6 and a vacuum pump 7, wherein the above devices are connected through a pipeline, and the modified graphene oxide membrane of the present invention is disposed between the membrane module and the heat source 3 to realize separation of the feed liquid 1. Of course, the modified graphene oxide membrane obtained based on the present invention may also be applied to other existing separation systems to realize separation of a feed liquid, and is not limited thereto.
The effects of the present invention will be further described with reference to specific examples.
Example 1 preparation of graphene oxide membranes on tubular ceramic supports for separation of mixtures of water and sodium chloride
Step 1: 10mg of graphene oxide is dissolved in 100mL of deionized water, and ultrasonic treatment is carried out for 30min to form 0.1mg/mL of graphene oxide hydrosol.
Step 2: porous alumina ceramic tubes are selected as carriers, the inner diameters and the outer diameters of the porous alumina ceramic tubes are respectively 7mm and 10mm, the average pore diameter of the inner surface is 100nm, the two ends of the carriers are sealed with glaze, and the effective membrane length is 20 mm. Cleaning and drying for later use.
And step 3: and (3) diluting 5mL of the graphene oxide hydrosol to 200mL, and depositing the sol on the inner surface of the carrier by a pressure-assisted deposition method, wherein the adopted pressure is 2-10 bar.
And 4, step 4: and placing the graphene oxide membrane supported by the porous alumina tube into the anion and cation solution with corresponding concentration, soaking for 1h, taking out, and drying in a vacuum oven at 45 ℃ for 12 h.
And 5: the mixture of pure water and sodium chloride is separated by adopting an pervaporation separation process, the operating temperature is 70 ℃, the system pressure is 0.1MPa, and the feeding molar concentration is 0.05M, 0.1M, 0.2M, 0.5M and 0.67M (approximately equal to 3.5 wt%).
Salt rejection calculation formula:
in the formula, C1And C2The salt concentrations were feed side and permeate side, respectively. Therefore, the salt rejection r can be calculated accordingly.
Permeate flux calculation formula: j ═ M/(a × t).
Wherein M (kg) is the amount of water collected on the permeate side, and A (m)2) For the effective membrane area, t (h) is the permeation duration. The permeation flux J (kg/m) can be calculated therefrom2·h)。
The pervaporation test results are shown in table 1:
table 1 results of the seawater desalination pervaporation test of example 1
Example 2 preparation of graphene oxide membranes on tubular ceramic supports for separation of water and mixtures of inorganic salts of different ionic valences
The difference from example 1 is that: and 5, separating the mixture of pure water and sodium chloride, sodium sulfate, magnesium chloride and magnesium sulfate by adopting a pervaporation separation process, wherein the operation temperature is 70 ℃, the system pressure is 0.1MPa, and the feeding molar concentration is 0.1M. The rest of the procedure was the same as in example 1.
The pervaporation test results are shown in table 2:
table 2 results of the seawater desalination pervaporation test of example 2
Example 3 preparation of graphene oxide membranes on tubular ceramic supports for separation of mixtures of pure water and sodium chloride at different temperatures
The difference from example 1 is that: in step 5, the operation temperature is 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃, the system pressure is 0.1MPa, and the feeding molar concentration is 0.1M. The rest of the procedure was the same as in example 1. The pervaporation test results are shown in table 3:
table 3 results of the seawater desalination pervaporation test of example 3
It can be seen from the results in tables 1-3 that the flux decreased from 12.9kg/m with temperature in the range of 50-90 deg.C2h is reduced to 1.14kg/m2h, flux of original GO membrane (1 kg/m)2h or so) is significantly improved; the desalination rate is kept above 99% in the temperature range, and compared with the original GO membrane desalination rate (30-40%), the desalination rate is also greatly increased.
In summary, according to the modified graphene oxide membrane based on anion and cation regulation and the preparation method thereof, the membrane material with the graphene oxide membrane as the selection layer is prepared and applied to the pervaporation desalination technology by obtaining the graphene oxide membrane and regulating the distance between graphene oxide layers based on the anion and cation. The method utilizes a simple method to regulate and control the distance between graphene oxide layers, and the prepared graphene oxide membrane has higher water permeation selectivity and permeation flux, can effectively desalt seawater, thereby providing a high-efficiency, environment-friendly and economic technical means for seawater desalination, and has important practical significance. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (12)
1. A preparation method of a modified graphene oxide membrane based on anion and cation regulation is characterized by comprising the following steps:
providing graphene oxide, and dissolving the graphene oxide in water to obtain graphene oxide sol;
providing a porous carrier, and forming a graphene oxide film on the surface of the porous carrier based on the graphene oxide sol;
providing an anionic/cationic solution;
and dipping the graphene oxide film in the anion/cation solution for modification treatment to obtain a modified graphene oxide film.
2. The method for preparing a modified graphene oxide membrane based on anion-cation modulation according to claim 1, wherein the concentration of the graphene oxide sol is between 0.08-0.12 mg/mL; and/or the interlayer spacing of the modified graphene oxide film is between 0.5 and 0.56 nm.
3. The method of claim 1, wherein the method comprises one or more of the following conditions:
A1) the configuration of the porous support comprises a tubular shape;
A2) the porous support comprises a porous ceramic support;
A3) the average pore diameter of the porous carrier is between 90 and 110 nm.
4. The method of claim 1, wherein the graphene oxide film is formed by a pressure-assisted deposition method.
5. The method for preparing the modified graphene oxide membrane based on anion-cation regulation and control according to claim 4, wherein in the process of forming the graphene oxide membrane, the porous carrier is loaded into a permeation assembly, the graphene oxide sol is introduced from the inner side of a porous carrier membrane tube, and auxiliary gas is used as driving force to pressurize and assist deposition on the inner surface of the porous carrier, wherein the pressure is between 1 and 10bar, and the total mass of the graphene oxide sol is between 0.25 and 0.75 mg.
6. The method for preparing a modified graphene oxide membrane based on anion-cation regulation and control according to claim 1, wherein the modified graphene oxide membrane is obtained by a process further comprising a step of drying after impregnation, wherein the drying manner comprises vacuum drying, the drying temperature is between 40 ℃ and 50 ℃, and the drying time is between 10 hours and 15 hours.
7. The method for preparing the modified graphene oxide membrane based on anion-cation modulation according to any one of claims 1 to 6, wherein in the anion/cation solution, anions comprise any one of methyl blue, methyl orange, congo red and ponceau red; the cation comprises any one of methylene blue, 1-vinyl-3-ethylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole chloride salt, 1-allyl-3-vinylimidazole chloride salt and 1-benzyl-3-methylimidazole chloride salt.
8. The method for preparing a modified graphene oxide membrane based on anion-cation modulation of claim 7, wherein the solution molar concentration of the anion is between 0.5-1.5 mM; when the cation is methylene blue, the molar concentration of the solution is between 0.5 and 1.5 mM; the molar concentration of the rest of the cation solution is between 2.5 and 3.5 mM.
9. A modified graphene oxide membrane based on anion and cation regulation, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the modified graphene oxide membrane of claim 9, wherein the modified graphene oxide membrane is used for desalination of sea water.
11. The use of the modified graphene oxide membrane of claim 10, comprising the step of performing a seawater desalination simulation, wherein the components simulating seawater comprise at least one of sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate, and calcium sulfate.
12. The use of the modified graphene oxide membrane according to any one of claims 10 to 11, wherein a pervaporation process is used for desalinating seawater by using the modified graphene oxide membrane, wherein the temperature of pervaporation is between 30 and 90 ℃, the pressure of a permeate side is between 85 and 95Pa, and the feed flow rate is between 10 and 15 mL/min.
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