CN112957930A - Metal ion doped graphene oxide composite membrane, preparation method and application - Google Patents
Metal ion doped graphene oxide composite membrane, preparation method and application Download PDFInfo
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
Abstract
The invention provides a metal ion doped graphene oxide composite membrane, a preparation method and application, wherein the preparation method comprises the following steps: preparing a graphene oxide dispersion liquid, preparing a graphene oxide film on a porous ceramic carrier based on the graphene oxide dispersion liquid, and dipping the graphene oxide film structure in a metal salt solution to obtain the metal ion doped graphene oxide composite film. According to the invention, the graphene oxide film is formed by controlling, the graphene oxide film is doped with metal ions in a corresponding metal salt solution by using an immersion method, an effective ion-pi effect can be formed by the technical scheme of the invention, and the metal ions are introduced into the graphene oxide film by using the ion-pi effect, so that the aim of separating olefin from alkane is fulfilled.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and particularly relates to a metal ion-doped graphene oxide composite membrane, a preparation method thereof, and application of the metal-doped graphene oxide composite membrane in olefin and alkane separation.
Background
Light olefins (ethylene and propylene) are important industrial feedstocks for the production of polyolefins, alcohols, ethers, and the like. The main source of olefins is petroleum cracking gas, usually olefins and paraffins are produced simultaneously, and need to be separated and purified to meet the needs of industrial production. Ethane and ethylene, propane and propylene, which have close molecular sizes and small differences in physical properties, are a major challenge to the separation of olefinic alkanes.
The traditional olefin/alkane separation technology such as rectification has poor selectivity, low separation coefficient and high energy consumption. In order to reduce energy consumption, it is of practical interest to develop new olefin/alkane separation technologies. Porous materials are used for adsorption separation (such as molecular sieve materials, zeolites, complexes and the like), and although olefin and alkane can be separated, the adsorption rate is slow, the adsorption capacity is weak, and the selectivity is poor.
In recent years, graphene materials have received much attention due to their excellent physicochemical properties. Graphene oxide is the most extensively studied graphene derivative in the graphene family. Compared with graphene, graphene oxide contains a large number of oxygen-containing groups, hydroxyl groups and carboxyl groups are distributed at the edge of the graphene oxide, and carbonyl groups and epoxy groups are distributed in the plane of the graphene oxide, so that the originally hydrophobic graphene is changed into a hydrophilic material.
Therefore, how to provide a metal ion doped graphene oxide composite membrane and a preparation method thereof are necessary to solve the above problems in the olefin and alkane separation process 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 metal ion-doped graphene oxide composite membrane, a preparation method thereof, and an application of the metal-doped graphene oxide composite membrane in olefin and alkane separation, which are used for solving the problems that the prior art is difficult to effectively realize olefin and alkane separation, etc.
In order to achieve the above and other related objects, the present invention provides a method for preparing a metal ion-doped graphene oxide composite film, the method comprising:
providing graphene oxide, and dispersing the graphene oxide in water to obtain a graphene oxide dispersion liquid;
providing a porous ceramic support;
preparing a graphene oxide film on the porous ceramic support based on the graphene oxide dispersion liquid;
providing a metal salt, and dissolving the metal salt in water to obtain a metal salt solution;
and dipping the graphene oxide film in the metal salt solution for a preset time to obtain the metal ion doped graphene oxide composite film.
Optionally, the pore size of the porous ceramic support is between 3-100 nm.
Optionally, the material of the porous ceramic support comprises any one of alumina, titania and zirconia.
Optionally, the method for preparing the graphene oxide film on the porous ceramic support is a filter-press deposition method, and the pressure in the deposition process is between 1 and 15 bar.
Optionally, the metal ion in the metal salt comprises Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Ag+、Zn2+、Na+At least one of (1).
Optionally, the metal salt comprises MnSO4、MnCl2、Mn(NO3)2、Mn(ClO4)2、Mn(CH3COO)2、FeSO4、FeCl2、Fe(NO3)2、Fe(CH3COO)2、Fe(BF4)2、CoSO4、CoCl2、Co(NO3)2、Co(CH3COO)2、NiSO4、NiCl2、Ni(NO3)2、Ni(CH3COO)2、CuSO4、CuCl2、Cu(NO3)2、Cu(CH3COO)2、Cu(BF4)2、AgBF4、AgCF3SO3、AgCF3CO2、AgNO3、CH3COOAg、ZnSO4、ZnCl2、Zn(NO3)2、Zn(CH3COO)2、Zn(BF4)2、NaCl、NaBF4、Na2SO4、NaNO3At least one of (1).
Optionally, the preset time for immersing the graphene oxide film structure in the metal salt solution is between 5 and 180 min.
Optionally, the step of drying the impregnated structure is further included after the impregnation, wherein the drying atmosphere includes at least one of argon and vacuum, and the drying temperature is between 25 ℃ and 60 ℃.
Optionally, the concentration of the graphene oxide dispersion is between 0.1-2 mg/ml.
Optionally, the concentration of the metal salt solution is between 0.01 and 5 mol/L.
In addition, the invention also provides a metal ion doped graphene oxide composite membrane, and the graphene composite membrane is prepared by adopting the preparation method of the metal ion doped graphene oxide composite membrane in any one of the schemes.
In addition, the invention also provides application of the metal ion doped graphene oxide composite membrane in any scheme, wherein the metal ion doped graphene oxide composite membrane is used for separating olefin and alkane.
Alternatively, the olefins include ethylene and propylene; the alkanes include ethane and propane.
As described above, according to the metal ion-doped graphene oxide composite membrane, the preparation method and the application of the metal ion-doped graphene oxide composite membrane, the graphene oxide thin film is formed by controlling, and the graphene oxide membrane is further doped with metal ions by an immersion method in a corresponding metal salt solution, an effective ion-pi effect can be formed by the technical scheme of the invention, and the metal ions are introduced into the graphene oxide membrane by the ion-pi effect, so that the purpose of separating olefin from alkane is achieved.
Drawings
Fig. 1 is a flowchart illustrating a method for preparing a metal ion-doped graphene oxide composite film according to the present invention.
FIG. 2 shows that the graphene oxide film is impregnated with 0.25mol/L Cu (BF) in example 1 of the present invention4)2Scanning electron micrograph of aqueous solution for 1h, wherein FIG. 2(a) is surface morphology and FIG. 2(b) is cross-sectional morphology
FIG. 3 shows AgBF in which graphene oxide film is impregnated at 0.25mol/L in example 4 of the present invention4Scanning electron micrographs in aqueous solution for 1h, FIG. 3(a) is the surface topography and FIG. 3(b) is the cross-sectional topography.
Description of the element reference numerals
S1-S5
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 metal ion-doped graphene oxide composite film, the method comprising:
s1, providing graphene oxide, and dispersing the graphene oxide in water to obtain a graphene oxide dispersion liquid;
s2, providing a porous ceramic carrier;
s3, preparing a graphene oxide film on the porous ceramic carrier based on the graphene oxide dispersion liquid;
s4, providing metal salt, and dissolving the metal salt in water to obtain metal salt solution;
and S5, dipping the graphene oxide film in the metal salt solution for a preset time to obtain the metal ion doped graphene oxide composite film.
The method for preparing the metal ion-doped graphene oxide composite membrane according to the present invention will be described in detail with reference to the accompanying drawings, wherein it should be noted that the above sequence does not strictly represent the preparation sequence of the method for preparing the metal ion-doped graphene oxide composite membrane according to the present invention, and those skilled in the art may change the sequence according to the actual process steps, and fig. 1 only shows the preparation steps of the metal ion-doped graphene oxide composite membrane according to an example of the present invention.
First, as shown in S1 in fig. 1, graphene oxide is provided and dispersed in water to obtain a graphene oxide dispersion liquid.
In one example, the obtained graphene oxide dispersion has a concentration of 0.1-2mg/ml, and is a graphene oxide hydrosol. For example, the concentration may be 0.12mg/ml, 0.15mg/ml, 0.16mg/ml, 0.18 mg/ml.
In one example, the graphene oxide is prepared by a Hummers method.
Next, as shown by S2 in fig. 1, a porous ceramic support is provided.
In one example, the pore size of the porous ceramic support is between 3-100nm, for example, 3nm, 5nm, 10nm, 20nm, 50nm, 100 nm. In another example, the porous ceramic support may be any one of an alumina porous support, a titania porous support, and a zirconia porous support.
In a further 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 a specific example, an inner diameter of 7mm and an outer diameter of 10 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.
Next, as shown in S3 in fig. 1, a graphene oxide thin film is prepared on the porous ceramic support based on the graphene oxide dispersion liquid.
As an example, the method for preparing the graphene oxide film on the porous ceramic support is a filter-press deposition method, and the pressure during the deposition process is between 1 and 15 bar. For example, 2bar, 5bar, 8bar, 10bar, 12bar are possible.
The graphene oxide thin film obtained based on the above method is advantageous for obtaining a layered structure and a suitable thickness, and the obtained interlayer distance is, for example, between 0.4 and 0.5nm, and may be, for example, 0.43nm, 0.45nm, and 0.48nm, where the gas molecules have approximate sizes: ethylene 0.39nm, ethane 0.39nm, propylene 0.43nm and propane 0.43nm, and in olefin and alkane separation, the interlayer spacing is equal to the size of gas molecules, so that a passage for the molecules to pass is provided; the thickness of the film is between 120-180nm, such as 150nm and 160nm, so as to further facilitate the subsequent ion-pi function, enhance the ion-pi interaction between the metal cation and the benzene ring, and thus the metal ion is attached to the graphene oxide.
Next, as shown by S4 in fig. 1, a metal salt is provided and dissolved in water to obtain a metal salt solution, thereby achieving gas separation based on metal ions.
Specifically, the graphene oxide film is doped with metal ions by using an immersion method, the graphene oxide contains a large number of oxygen-containing groups, hydroxyl groups and carboxyl groups are distributed at the edge of the graphene oxide, and carbonyl groups and epoxy groups are distributed in the plane of the graphene oxide, so that the originally hydrophobic graphene is changed into a hydrophilic material; and further, a graphene oxide film is prepared on the porous ceramic carrier through filter pressing deposition, the graphene oxide is a novel film separation material, the thickness of a graphene oxide monoatomic layer is thick, the flexibility is excellent, a regular two-dimensional nano channel is formed, the interlayer spacing can be controlled, the hydrophilicity is good, metal cations can be stably attached to oxygen-containing groups and aromatic rings of GO based on the effect of ion-pi based on the impregnation method, and the interaction between the ion-pi is stronger.
The graphene oxide composite membrane prepared based on the technical scheme of the invention has the characteristics of low energy consumption, low investment, environmental friendliness and the like, metal ions are introduced into the membrane as a carrier, and the separation of olefin and alkane is realized by utilizing the reaction that the metal ions and the olefin form a donor/acceptor complex and do not react with the alkane.
As an example, the metal ion in the metal salt includes Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Ag+、Zn2+、Na+At least one of them may be one of them, or a mixture of two or more of them.
Summarizing still further alternative examples, the metal salt comprises MnSO4、MnCl2、Mn(NO3)2、Mn(ClO4)2、Mn(CH3COO)2、FeSO4、FeCl2、Fe(NO3)2、Fe(CH3COO)2、Fe(BF4)2、CoSO4、CoCl2、Co(NO3)2、Co(CH3COO)2、NiSO4、NiCl2、Ni(NO3)2、Ni(CH3COO)2、CuSO4、CuCl2、Cu(NO3)2、Cu(CH3COO)2、Cu(BF4)2、AgBF4、AgCF3SO3、AgCF3CO2、AgNO3、CH3COOAg、ZnSO4、ZnCl2、Zn(NO3)2、Zn(CH3COO)2、Zn(BF4)2、NaCl、NaBF4、Na2SO4、NaNO3At least one of them may be one of them, or a mixture of two or more of them.
By way of example, the concentration of the metal salt solution is between 0.01 and 5mol/ml, and may be, for example, 0.05mol/ml, 0.1mol/ml, 0.5mol/ml, 1mol/ml, 2 mol/ml.
In addition, the concentration of the metal salt solution in the design scheme of the invention preferably has a corresponding relationship with the concentration of the graphene oxide dispersion solution, so that an effective ion-pi effect can be effectively formed between the graphene oxide film and the metal ions. In an alternative example, the concentration of the metal salt solution and the concentration of the graphene oxide dispersion have a one-to-one correspondence relationship, such as the correspondence manner in the embodiment. In addition, the thickness of the film can be controlled by the concentration or the use amount of the graphene oxide.
In an example, the immersion time of the graphene oxide thin film structure in the metal salt solution is between 5-180min, for example, 10min, 20min, 30min, 50min, 60 min.
In another alternative example, the step of drying the impregnated structure is further included after the impregnation in the metal salt solution, wherein the drying atmosphere includes at least one of argon and vacuum, and the drying temperature is between 25 ℃ and 60 ℃, for example, 30 ℃, 40 ℃, 45 ℃, and 50 ℃ may be selected.
Based on the technical scheme of the invention, metal ions are introduced into the graphene oxide membrane by utilizing the ion-pi action, so that the aim of separating olefin from alkane is fulfilled, and the preparation method of the process is simple to operate, low in energy consumption and low in investment. Wherein, based on ion-pi effect, metal ions are introduced into the membrane as carriers, and the separation of olefin and alkane is realized by utilizing the reaction that the metal ions and olefin form a donor/acceptor complex and do not react with alkane.
In addition, the invention also provides a metal ion doped graphene oxide composite membrane, and the graphene composite membrane is prepared by adopting the preparation method of the metal ion doped graphene oxide composite membrane 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 graphene oxide composite membrane in olefin and alkane separation, wherein the graphene oxide composite membrane doped with the metal ions is adopted to separate the olefin and the alkane. The characteristics and the like of the related metal ion doped graphene oxide composite film can be referred to the description in the preparation method, and are not described herein again.
In one example, the alkenes and alkanes include: ethylene, propylene, ethane, propane. In one example, the test format may be selected to be one of two: one is that single component gas is separated, permeation flux of ethylene, ethane, propylene and propane are respectively tested, and then separation selectivity of ethylene/ethane and propylene/propane is calculated; another is the separation of mixed gases, such as ethylene: ethane-1: 1 (volume ratio) of the mixed gas passes through a graphene oxide membrane, the gas composition after penetrating through the graphene oxide membrane is detected by chromatography for permeation detection, and then the separation selectivity is calculated.
In another example, the gas test pressure is 0.2-2bar, such as 1 bar; the test temperature is 25-100 deg.C, such as 30 deg.C, 35 deg.C, 40 deg.C, and 50 deg.C.
The effects of the present invention will be further described with reference to specific examples.
Example 1
Step 1: adding 25mg of graphene oxide into 100mL of ultrapure water, and ultrasonically crushing for 1h at normal temperature to form 0.4mg/mL of GO dispersion liquid;
step 2: selecting a porous titanium oxide ceramic tube as a carrier, wherein the outer diameter and the inner diameter of the porous titanium oxide ceramic tube are respectively 10mm and 7mm, the average pore diameter of the inner surface is 5nm, glaze is sealed at two ends of the carrier, the length of an effective membrane is 25mm, and the porous titanium oxide ceramic tube is cleaned, dried and roasted at 980 ℃ for 0.5 h;
and step 3: a filter pressing deposition method is adopted, a ceramic tube is arranged in a membrane assembly, graphene oxide hydrosol is introduced from the inner side of the membrane tube, nitrogen with a certain pressure is used as a driving force, the pressure range is 1-15bar, and the membrane tube is placed at normal temperature for 2 hours;
and 4, step 4: the membrane tube in step 3 was immersed in 0.25mol/L Cu (BF4)2Vacuum drying in water solution at 45 deg.C for 12 hr for 1 hr;
and 5: separating ethylene/ethane and propylene/propane by adopting a gas permeation device, wherein the gas test pressure is 0.2-1 bar, the test temperature is 25 ℃, and the permeation flux P (mol/m)2/s/Pa), separation selectivity α ═ P1/P2. The results of the isolation test are shown in table 1.
Wherein, fig. 2 is a scanning electron microscope image of the graphene oxide composite film prepared by the method of example 1, fig. 2(a) is a surface topography, fig. 2(b) is a cross-sectional topography, from the surface topography, it can be seen that the surface of the film is dense and uniform, and has obvious graphene oxide wrinkles, from the cross-sectional topography, it can be seen that the layered structure of the film, and the thickness of the film is about 150 nm.
Example 2
The difference from example 1 is that: in step 4, the membrane tube is immersed in 0.25mol/L CuCl2And (5) dissolving in the water solution for 1 h. The rest of the procedure was the same as in example 1. The results of the isolation test are shown in table 1.
Example 3
The difference from example 1 is that: in step 4, the membrane tube is immersed in 0.25mol/L Cu (NO)3)2And (5) dissolving in the water solution for 1 h. The rest of the procedure was the same as in example 1. The results of the isolation test are shown in table 1.
Example 4
The difference from example 1 is that: in step 4, the membrane tube is immersed in 0.25mol/L AgBF4The rest of the procedure was the same as in example 1, in aqueous solution for 1 h. The results of the isolation test are shown in table 1.
Wherein, fig. 3 is a scanning electron microscope image of the graphene oxide composite film prepared by the method of example 4, fig. 3(a) is a surface topography, fig. 3(b) is a cross-sectional topography, from the surface topography, it can be seen that the surface of the film is dense and uniform, and has obvious graphene oxide wrinkles, from the cross-sectional topography, it can be seen that the layered structure of the film, and the thickness of the film is about 150 nm.
Example 5
The difference from example 1 is that: in step 4, the membrane tube is immersed in 0.1mol/L AgBF4The rest of the procedure was the same as in example 1, in aqueous solution for 1 h. The results of the isolation test are shown in table 1.
Example 6
The difference from example 1 is that: in step 4, the membrane tube is immersed in 0.25mol/L AgBF4The procedure was the same as in example 1 except that the aqueous solution was maintained for 1 hour and the gas test temperature was 50 ℃. The results of the isolation test are shown in table 1.
TABLE 1 results of olefin/alkane gas separation tests
Note: the gas permeation flux unit is mol/m 2/s/Pa.
It can be seen from the results shown in table 1 that, compared with examples 1, 2 and 3, with the same metal cation, metal salt concentration and immersion time, only the graphene oxide membrane immersed by Cu (BF4)2 in example 1 has a better separation effect of olefin and alkane, wherein the separation effect of ethane/ethylene is more significant, and the graphene oxide membrane immersed by other copper salts in examples 2 and 3 has almost no separation effect; in the graphene oxide membrane immersed by 0.25mol/L AgBF4 in example 4, the separation selectivity of ethane and ethylene is about 60, and the separation selectivity of propane and propylene is also about 60; in example 5, the effect of separating alkene and alkane from 0.1mol/L AgBF 4-impregnated graphene oxide membrane is general, and the comparison between examples 4 and 5 shows that the concentration of metal salt solution is increased, which is beneficial to improving the effect of separating alkene and alkane; the preparation conditions in example 6 were the same as in example 4 except that the test temperature was increased to 50 ℃, but the separation effect was rather decreased, indicating that it was meaningless to increase the test temperature.
In summary, the metal ion-doped graphene oxide composite membrane, the preparation method and the application of the metal ion-doped graphene oxide composite membrane of the present invention form a graphene oxide thin film by controlling, and further dope the graphene oxide membrane with metal ions by using an immersion method in a corresponding metal salt solution, an effective ion-pi effect can be formed by the technical scheme of the present invention, and the metal ions are introduced into the graphene oxide membrane by using the ion-pi effect, so as to achieve the purpose of separating olefins from alkanes. 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 (10)
1. A preparation method of a metal ion doped graphene oxide composite film is characterized by comprising the following steps:
providing graphene oxide, and dispersing the graphene oxide in water to obtain a graphene oxide dispersion liquid;
providing a porous ceramic support;
preparing a graphene oxide film on the porous ceramic support based on the graphene oxide dispersion liquid;
providing a metal salt, and dissolving the metal salt in water to obtain a metal salt solution;
and dipping the graphene oxide film in the metal salt solution for a preset time to obtain the metal ion doped graphene oxide composite film.
2. The method of preparing a metal ion-doped graphene oxide composite membrane according to claim 1, wherein the characteristics of the porous ceramic support include at least one of the following conditions:
A1) the pore diameter of the porous ceramic carrier is between 3 and 100 nm;
A2) the material of the porous ceramic carrier comprises any one of alumina, titania and zirconia.
3. The method for preparing a metal ion-doped graphene oxide composite membrane according to claim 1, wherein the method for preparing the graphene oxide thin film on the porous ceramic support is a filter-press deposition method, wherein the pressure during deposition is between 1 and 15 bar.
4. The method according to claim 1, wherein the metal ions in the metal salt comprise Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Ag+、Zn2+、Na+At least one of; the metal salt comprises MnSO4、MnCl2、Mn(NO3)2、Mn(ClO4)2、Mn(CH3COO)2、FeSO4、FeCl2、Fe(NO3)2、Fe(CH3COO)2、Fe(BF4)2、CoSO4、CoCl2、Co(NO3)2、Co(CH3COO)2、NiSO4、NiCl2、Ni(NO3)2、Ni(CH3COO)2、CuSO4、CuCl2、Cu(NO3)2、Cu(CH3COO)2、Cu(BF4)2、AgBF4、AgCF3SO3、AgCF3CO2、AgNO3、CH3COOAg、ZnSO4、ZnCl2、Zn(NO3)2、Zn(CH3COO)2、Zn(BF4)2、NaCl、NaBF4、Na2SO4、NaNO3At least one of (1).
5. The method according to claim 1, wherein the predetermined time for immersing the graphene oxide thin film structure in the metal salt solution is between 5 and 180 min; and drying the impregnated structure after impregnation, wherein the drying atmosphere comprises at least one of argon and vacuum, and the drying temperature is between 25 and 60 ℃.
6. The method for preparing a metal ion-doped graphene oxide composite membrane according to any one of claims 1 to 5, wherein the concentration of the graphene oxide dispersion liquid is between 0.1 and 2 mg/ml.
7. The method according to claim 6, wherein the concentration of the metal salt solution is between 0.01 and 5 mol/L.
8. A metal ion doped graphene oxide composite film, which is characterized in that the graphene composite film is prepared by the preparation method of the metal ion doped graphene oxide composite film according to any one of claims 1 to 7.
9. Use of the metal ion-doped graphene oxide composite membrane according to claim 8, wherein the metal ion-doped graphene oxide composite membrane is used for separation of olefins and alkanes.
10. The use of the metal ion-doped graphene oxide composite membrane according to claim 9, wherein the olefin comprises ethylene and propylene; the alkanes include ethane and propane.
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| CN113457470A (en) * | 2021-06-21 | 2021-10-01 | 清华大学 | Graphene oxide nanofiltration membrane and preparation method thereof |
| CN115228307A (en) * | 2022-01-21 | 2022-10-25 | 南京工业大学 | Graphene oxide separation membrane, preparation method and application in ethylene/ethane separation |
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