CN116459686B - Porous graphene oxide pervaporation membrane and preparation method and application thereof - Google Patents
Porous graphene oxide pervaporation membrane and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 211
- 239000012528 membrane Substances 0.000 title claims abstract description 74
- 238000005373 pervaporation Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 55
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims description 75
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 64
- 239000007788 liquid Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 18
- 239000002135 nanosheet Substances 0.000 description 76
- 239000007864 aqueous solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229920002239 polyacrylonitrile Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
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- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000001553 co-assembly Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005549 size reduction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a porous graphene oxide pervaporation membrane, which comprises a base membrane and a porous graphene oxide separation layer covered on the base membrane, wherein the porous graphene oxide separation layer comprises graphene oxide, porous graphene oxide and Congo red molecules. The invention also provides a preparation method and application of the porous graphene oxide pervaporation membrane. Compared with the graphene oxide pure membrane and the porous graphene oxide pure membrane, the graphene oxide pervaporation membrane has higher permeation flux and water/butanol separation factor.
Description
Technical Field
The invention relates to the technical field of preparation of pervaporation membranes, in particular to a porous graphene oxide pervaporation membrane, and a preparation method and application thereof.
Background
The energy crisis and environmental pollution caused by the combustion of fossil fuels are significant challenges facing the world's energy and environmental world. Development of environment-friendly alternative energy is a main strategy for solving the current energy and environmental problems. Butanol is a novel biofuel with great potential, and has the advantages of high energy content, high mixing ratio with gasoline, capability of using the existing pipeline for transportation, low corrosiveness and the like. Butanol is typically prepared by biological fermentation, and high purity butanol is obtained from the fermentation broth and is subject to moisture removal. In addition, butanol is widely used as an important bulk chemical in various industrial processes such as chemical industry, medicine, printing and dyeing, and the recovery and purification process thereof involve alcohol-water separation. The separation process is difficult to achieve by conventional rectification techniques due to the formation of butanol/water azeotropes. The special rectification method has high energy consumption, and the introduction of third components such as entrainers and the like has serious environmental pollution; the energy consumption required by the regeneration of the molecular sieve adsorption method adsorbent is relatively high; the pervaporation membrane technology is favored because of the advantages of simple operation, high product purity, low raw material loss, no pollution, low energy consumption and the like, and is particularly suitable for removing water under low water content.
The core of the membrane separation technology is a membrane material, and the performance of the membrane material is a key factor for determining the core competitiveness of the membrane separation technology, such as efficiency, service life and the like. The ideal film material should meet the following two conditions: (1) Ultra-thin thickness, in order to shorten the mass transfer route to the maximum extent, reduce the mass transfer resistance, raise the membrane permeation flux; (2) The channel size is orderly and controllable, so that efficient molecular screening is realized, and the membrane selectivity is improved.
The performance of a main stream product, namely a polymer membrane, in the market at present is generally limited by the trade-off relation between permeability and selectivity; the separation performance of the inorganic membrane material is greatly improved compared with that of a high polymer membrane, but the preparation difficulty and the cost are relatively high. In recent years, two-dimensional (2D) materials with atomic layer thickness, such as graphene and its derivative Graphene Oxide (GO), have become extremely potential next-generation high-performance separation membrane materials because of being capable of being assembled to form ultrathin films with controllable and ordered nanochannels, thereby realizing high permeability and high selectivity, and having better film forming property.
The pure GO laminated film formed by assembling the GO nano sheets has low flux due to the fact that slit holes among the nano sheets and in-plane defect holes are fewer and mass transfer paths in the film are tortuous. In order to solve the problem, researchers prepare a porous graphene oxide membrane, flux is improved by introducing large-size in-plane defect holes, and a good separation effect is obtained in the membrane processes of ultrafiltration, nanofiltration and the like. However, in molecular scale liquid separation systems (such as water and alcohol molecular separation during pervaporation), porous graphene oxide membranes have not yet been applied, and the challenge is that the porous graphene oxide membranes are assembled into membranes to form defects easily, so that the separation selectivity is reduced while the permeation flux is improved. In order to realize the application of the porous graphene oxide membrane in the pervaporation process, the problems need to be solved, and the porous graphene oxide pervaporation membrane with high separation performance is prepared.
Disclosure of Invention
Aiming at the prior art, the invention provides a porous graphene oxide pervaporation membrane and a preparation method thereof, so as to realize the efficient separation of a water/butanol mixture. The preparation method has simple and convenient process and easy operation, and the obtained graphene oxide pervaporation membrane has higher permeation flux and water/butanol separation factor compared with a pure graphene oxide membrane and a pure porous graphene oxide membrane.
The porous graphene oxide pervaporation membrane comprises a base membrane and a porous graphene oxide separation layer covered on the base membrane, wherein the porous graphene oxide separation layer comprises graphene oxide, porous graphene oxide and Congo red molecules.
Preferably, the thickness of the graphene oxide is 1nm, and the transverse dimension is 400-600 nm; the pore diameter of the porous graphene oxide is 3-5 nm, the thickness is 0.6nm, and the transverse dimension is 50-100 nm;
Preferably, in the porous graphene oxide separation layer, the mass ratio of graphene oxide to porous graphene oxide is 1:1 to 1:3, the mass ratio of Congo red to graphene oxide to porous graphene oxide is 0.11: 1-0.19:1; the thickness of the porous graphene oxide separation layer is 50-160 nm; the size of the channels between the inner layers of the porous graphene oxide separation layer is 0.383-0.474 nm.
The invention also provides a preparation method of the porous graphene oxide pervaporation membrane, which comprises the following steps:
step 1, mixing graphene oxide dispersion liquid with hydrogen peroxide at a high temperature for reacting for a period of time to obtain porous graphene oxide;
step 2, preparing porous graphene oxide obtained in the step 1 into porous graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid, congo red solution and the porous graphene oxide dispersion liquid, diluting, and uniformly stirring to obtain mixed liquid;
and 3, carrying out suction filtration on the mixed solution obtained in the step 2 on the base film by a vacuum auxiliary filtration method, and carrying out thermal crosslinking on the base film assembled with the mixed solution to obtain the porous graphene oxide pervaporation film.
Preferably, in the step 1, the concentration of the graphene oxide dispersion liquid is 2-5 mg/ml, and the concentration of the hydrogen peroxide is 30%; the volume ratio of the graphene oxide dispersion liquid to the hydrogen peroxide is 10: 1-2: 1.
Preferably, in the step1, the temperature of the mixing reaction of the graphene oxide dispersion liquid and the hydrogen peroxide is 100 ℃ and the time is 2-8 hours.
Preferably, in the step 2, the concentrations of the graphene oxide dispersion liquid, the congo red solution and the porous graphene oxide dispersion liquid are all 0.2mg/ml.
Preferably, in step 2, the volume ratio of the graphene oxide dispersion liquid to the porous graphene oxide dispersion liquid is 1:1 to 1:3, and the sum of the volumes of the two is 2ml; the volume ratio of Congo red solution to graphene oxide dispersion liquid to porous graphene oxide dispersion liquid is 0.2:1 to 1:1.
Preferably, in step 3, the temperature at which the base film is thermally crosslinked is 60 ℃ for 3 hours.
The invention also provides application of the porous graphene oxide pervaporation membrane in separating a water/butanol mixture.
Compared with the prior art, the invention has the beneficial effects that:
1. The method realizes in-plane pore-forming and transverse size reduction of the graphene oxide nano-sheets by high-temperature oxidation etching of the graphene oxide nano-sheets by hydrogen peroxide, and comprises the following specific processes: taking hydrogen peroxide and graphene oxide as base materials, under the high temperature condition, the hydrogen peroxide can react with oxygen-containing functional groups on the graphene oxide nano-sheets to cause part of carbon atoms to escape in the form of carbon monoxide and carbon dioxide, so that in-plane pore-forming of the graphene oxide nano-sheets is realized, and meanwhile, the nano-sheets are broken to reduce the transverse size of the graphene oxide nano-sheets; on the basis, porous graphene oxide, graphene oxide and Congo red are co-assembled on the surface of a base film by a vacuum auxiliary filtering method to prepare a porous graphene oxide base pervaporation film; the graphene oxide provides good film forming property, and defects in the film are avoided; the porous graphene oxide nano-sheets provide surface inner holes, and meanwhile, more slit holes are formed by smaller transverse dimensions, so that a molecular mass transfer path is increased, and the permeation flux is improved; the pi-pi action, the hydrogen bond action and the like between the porous graphene oxide and the graphene oxide enable the graphene oxide nano sheets to be stacked more tightly, the size of an interlayer channel is reduced, and the water/butanol separation factor is improved; congo red molecules regulate the size of an interlayer channel, hydrophilic sulfonic acid groups are introduced into the channel, and the simultaneous promotion of flux and separation factors is realized.
2. Compared with a graphene oxide pure membrane, the preparation method provided by the invention is simple, convenient and controllable, compared with the graphene oxide pure membrane, the porous graphene oxide pervaporation membrane has the advantages that the permeation flux of pervaporation separation of a 10wt%/90wt% water/butanol mixture is increased from 2.72 kg/(m 2 h) to 4.81 kg/(m 2 h), the separation factor of butanol is increased from 288 to 5705, and butanol molecules can be effectively intercepted. Compared with the porous graphene oxide pure film, the preparation of a defect-free high-selectivity film layer can be realized. The invention can be used for the separation of pervaporation water/butanol and has wide application prospect of solvent separation and purification.
Drawings
Fig. 1 is a surface electron microscopic view of a porous graphene oxide pervaporation membrane obtained in example 1 of the present invention.
Fig. 2 is a surface electron microscopic image of the graphene oxide pure film obtained in comparative example 1 of the present invention.
Fig. 3 is a surface electron microscopic image of the porous graphene oxide pure film obtained in comparative example 2 of the present invention.
Detailed Description
According to the invention, graphene oxide is used as a material, in-plane pore-forming and transverse size reduction of graphene oxide nano-sheets are realized by hydrogen peroxide at high temperature, and the porous graphene oxide pervaporation membrane with different structures and separation performances is prepared by changing the proportion of graphene oxide, porous graphene oxide and Congo red during co-assembly. The porous graphene oxide membrane prepared by the method can be widely used for alcohol-water separation, and the preparation method is convenient and simple. The invention is further described with reference to the following detailed drawings in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
Example 1
The preparation method of the porous graphene oxide pervaporation membrane comprises the following steps of:
Step 1, mixing graphene oxide nano sheet aqueous dispersion liquid with hydrogen peroxide at 100 ℃ for reaction for 4 hours, and removing the hydrogen peroxide and redundant aqueous solution in the reaction liquid in a centrifugal separation mode to obtain porous graphene oxide nano sheets; wherein the concentration of the graphene oxide nano sheet water dispersion liquid is 5mg/ml, and the concentration of the hydrogen peroxide is 30%; the volume ratio of the graphene oxide nano sheet aqueous dispersion liquid to the hydrogen peroxide is 10:1.
Step 2, preparing porous graphene oxide nano-sheets obtained in the step 1 into porous graphene oxide nano-sheet aqueous dispersion, mixing the graphene oxide nano-sheet aqueous dispersion, congo red aqueous solution and the porous graphene oxide nano-sheet aqueous dispersion, diluting to 200ml, and uniformly stirring to obtain a mixed solution; wherein, the concentration of the graphene oxide nano-sheet aqueous dispersion liquid, congo red aqueous solution and porous graphene oxide nano-sheet aqueous dispersion liquid is 0.2mg/ml; the volume ratio of the graphene oxide nano sheet aqueous dispersion to the porous graphene oxide nano sheet aqueous dispersion is 1:1, the sum of the volumes of the two is 2ml; the volume ratio of Congo red aqueous solution to (graphene oxide nano-sheet aqueous dispersion + porous graphene oxide nano-sheet aqueous dispersion) is 0.2:1.
And 3, carrying out vacuum suction filtration on the mixed solution obtained in the step 2 to a polyacrylonitrile support body through a vacuum auxiliary self-assembly process, placing the polyacrylonitrile support body assembled with the mixed solution in a 60 ℃ oven for thermal crosslinking for 3 hours, cleaning uncrosslinked congo red deposited on the surface of the base film, and carrying out vacuum drying for 12 hours to obtain the porous graphene oxide pervaporation membrane.
The porous graphene oxide pervaporation membrane prepared in example 1 has smaller surface fold size, as shown in fig. 1, and shows that the nano-sheets are assembled more regularly, the pervaporation separation permeation flux of the membrane for 10wt%/90wt% of water/butanol mixture is 4.56 kg/(m 2 h) at 70 ℃, and the water/butanol separation factor is 3954.
Example 2
The preparation method of the porous graphene oxide pervaporation membrane comprises the following steps of:
Step 1, mixing graphene oxide nano sheet aqueous dispersion liquid with hydrogen peroxide at 100 ℃ for reaction for 2 hours, and removing the hydrogen peroxide and redundant aqueous solution in the reaction liquid in a centrifugal separation mode to obtain porous graphene oxide nano sheets; wherein the concentration of the graphene oxide nano sheet water dispersion liquid is 2mg/ml, and the concentration of the hydrogen peroxide is 30%; the volume ratio of the graphene oxide nano sheet aqueous dispersion liquid to the hydrogen peroxide is 5:1.
Step 2, preparing porous graphene oxide nano-sheets obtained in the step 1 into porous graphene oxide nano-sheet aqueous dispersion, mixing the graphene oxide nano-sheet aqueous dispersion, congo red aqueous solution and the porous graphene oxide nano-sheet aqueous dispersion, diluting to 200ml, and uniformly stirring to obtain a mixed solution; wherein, the concentration of the graphene oxide nano-sheet aqueous dispersion liquid, congo red aqueous solution and porous graphene oxide nano-sheet aqueous dispersion liquid is 0.2mg/ml; the volume ratio of the graphene oxide nano sheet aqueous dispersion to the porous graphene oxide nano sheet aqueous dispersion is 1:3, the sum of the volumes of the two is 2ml; the volume ratio of Congo red aqueous solution to (graphene oxide nano-sheet aqueous dispersion + porous graphene oxide nano-sheet aqueous dispersion) is 0.5:1.
And 3, carrying out vacuum suction filtration on the mixed solution obtained in the step 2 to a polyacrylonitrile support body through a vacuum auxiliary self-assembly process, placing a base film assembled with the polyacrylonitrile support body in a 60 ℃ oven for thermal crosslinking for 3 hours, cleaning uncrosslinked congo red deposited on the surface of the base film, and carrying out vacuum drying for 12 hours to obtain the porous graphene oxide pervaporation membrane.
The porous graphene oxide pervaporation membrane prepared in example 2 had a pervaporation separation permeation flux of 4.70 kg/(m 2 h) for a 10wt%/90wt% water/butanol mixture at 70 ℃, and a water/butanol separation factor of 5072.
Example 3
The preparation method of the porous graphene oxide pervaporation membrane comprises the following steps of:
Step 1, mixing graphene oxide nano sheet aqueous dispersion liquid with hydrogen peroxide at 100 ℃ for reaction for 8 hours, and removing the hydrogen peroxide and redundant aqueous solution in the reaction liquid in a centrifugal separation mode to obtain porous graphene oxide nano sheets; wherein the concentration of the graphene oxide nano sheet water dispersion liquid is 2mg/ml, and the concentration of the hydrogen peroxide is 30%; the volume ratio of the graphene oxide nano sheet aqueous dispersion liquid to the hydrogen peroxide is 2:1.
Step 2, preparing porous graphene oxide nano-sheets obtained in the step 1 into porous graphene oxide nano-sheet aqueous dispersion, mixing the graphene oxide nano-sheet aqueous dispersion, congo red aqueous solution and the porous graphene oxide nano-sheet aqueous dispersion, diluting to 200ml, and uniformly stirring to obtain a mixed solution; wherein, the concentration of the graphene oxide nano-sheet aqueous dispersion liquid, congo red aqueous solution and porous graphene oxide nano-sheet aqueous dispersion liquid is 0.2mg/ml; the volume ratio of the graphene oxide nano sheet aqueous dispersion to the porous graphene oxide nano sheet aqueous dispersion is 1:1, the sum of the volumes of the two is 2ml; the volume ratio of Congo red aqueous solution to (graphene oxide nano-sheet aqueous dispersion and porous graphene oxide nano-sheet aqueous dispersion) is 1:1.
And 3, carrying out vacuum suction filtration on the mixed solution obtained in the step 2 to a polyacrylonitrile support body through a vacuum auxiliary self-assembly process, placing the polyacrylonitrile support body assembled with the mixed solution in a 60 ℃ oven for thermal crosslinking for 3 hours, cleaning uncrosslinked congo red deposited on the surface of the base film, and carrying out vacuum drying for 12 hours to obtain the porous graphene oxide pervaporation membrane.
The porous graphene oxide pervaporation membrane prepared in example 3 had a pervaporation separation permeation flux of 4.81 kg/(m 2 h) for a 10wt%/90wt% water/butanol mixture at 70 ℃, and a water/butanol separation factor of 5705.
Comparative example 1
The preparation method of the graphene oxide pure film comprises the following steps:
Preparing graphene oxide nano-sheets into an aqueous solution with the concentration of 0.2mg/ml, diluting 2ml of graphene oxide nano-sheet solution to 200ml, carrying out vacuum-assisted self-assembly, carrying out vacuum suction filtration on a polyacrylonitrile support, and then placing the support in a drying pot for drying for 12 hours to prepare the graphene oxide pure film.
The graphene oxide pure membrane obtained in comparative example 1 has a large wrinkles on the surface, and as shown in fig. 2, the membrane has a permeation flux of 2.72 kg/(m 2 h) for permeation vaporization separation of 10wt%/90wt% water/butanol mixture at 70 ℃ and a water/butanol separation factor of 288.
Comparative example 2
The preparation method of the porous graphene oxide pure film comprises the following steps:
Step 1, by a high-temperature oxidation etching method of hydrogen peroxide, mixing the hydrogen peroxide with graphene oxide nanosheet aqueous dispersion with the concentration of 2mg/ml according to the volume ratio of 10:1, mixing under stirring, reacting the mixture at 100 ℃ for 2 hours, and removing hydrogen peroxide and redundant aqueous solution in the mixture by a centrifugal separation mode to obtain the porous graphene oxide nano-sheet for later use.
Step 2, preparing the porous graphene oxide nano-sheets obtained in the step 1 into porous graphene oxide nano-sheet aqueous dispersion liquid with the concentration of 0.2 mg/ml; 2ml of porous graphene oxide nano sheet aqueous dispersion is diluted to 200ml, and is subjected to vacuum filtration on a polyacrylonitrile support body through a vacuum-assisted self-assembly process, and then is placed in a drying pot to be dried for 12 hours, so that the porous graphene oxide pure film is prepared.
The surface of the porous graphene oxide pure film prepared in comparative example 2 has a large number of defects, and is not selective to water/butanol separation as shown in fig. 3.
Comparative example 3
The preparation method of the porous graphene oxide pervaporation membrane comprises the following steps of:
Step 1, mixing graphene oxide nano sheet aqueous dispersion liquid with hydrogen peroxide at 100 ℃ for reaction for 4 hours, and removing the hydrogen peroxide and redundant aqueous solution in the reaction liquid in a centrifugal separation mode to obtain porous graphene oxide nano sheets; wherein the concentration of the graphene oxide nano sheet water dispersion liquid is 5mg/ml, and the concentration of the hydrogen peroxide is 30%; the volume ratio of the graphene oxide nano sheet aqueous dispersion liquid to the hydrogen peroxide is 10:1.
Step 2, preparing porous graphene oxide nano-sheets obtained in the step 1 into porous graphene oxide nano-sheet aqueous dispersion liquid, mixing the graphene oxide nano-sheet aqueous dispersion liquid with the porous graphene oxide nano-sheet aqueous dispersion liquid, diluting to 200ml, and uniformly stirring to obtain a mixed solution; wherein, the concentration of the graphene oxide nano sheet aqueous dispersion liquid and the concentration of the porous graphene oxide nano sheet aqueous dispersion liquid are both 0.2mg/ml; the volume ratio of the graphene oxide nano sheet aqueous dispersion to the porous graphene oxide nano sheet aqueous dispersion is 1:1, the sum of the volumes of the two is 2ml.
And 3, carrying out vacuum-assisted self-assembly on the mixed solution obtained in the step 2, carrying out vacuum suction filtration on a polyacrylonitrile support, and then placing the polyacrylonitrile support in a drying pot for drying for 12 hours to obtain the porous graphene oxide pervaporation membrane.
The porous graphene oxide pervaporation membrane prepared in comparative example 3 has a pervaporation separation permeation flux of 4.32 kg/(m 2 h) for a 10wt%/90wt% water/butanol mixture at 70 ℃, and a water/butanol separation factor of 1397.
The permeation flux and separation performance of the membranes prepared in each example of the present invention and comparative example are shown in table 1:
TABLE 1
| Project | Membrane permeation flux (kg/(m 2 h)) | Membrane separation factor |
| Example 1 | 4.56 | 3954 |
| Example 2 | 4.70 | 5072 |
| Example 3 | 4.81 | 5705 |
| Comparative example 1 | 2.72 | 288 |
| Comparative example 2 | - | Non-selectivity |
| Comparative example 3 | 4.32 | 1397 |
In summary, the preparation conditions are mild, the preparation process is simple and easy to implement, the small-size porous graphene oxide nanosheets are prepared by utilizing a hydrogen peroxide oxidizing etching mode under a high temperature condition, graphene oxide, porous graphene oxide and Congo red molecules are mixed in a certain proportion, and then the mixed solution is subjected to suction filtration on a support body through a vacuum auxiliary co-assembly process to obtain the porous graphene oxide pervaporation membrane. The graphene oxide provides good film forming property, and defects in the film are avoided; the porous graphene oxide nano-sheets provide surface inner holes, and meanwhile, more slit holes are formed by smaller transverse dimensions, so that a molecular mass transfer path is increased, and the permeation flux is improved; the pi-pi action, the hydrogen bond action and the like between the porous graphene oxide and the graphene oxide enable the graphene oxide nano sheets to be stacked more tightly, the size of an interlayer channel is reduced, and the water/butanol separation factor is improved; congo red molecules regulate the size of an interlayer channel, hydrophilic sulfonic acid groups are introduced into the channel, and the simultaneous promotion of flux and separation factors is realized; the synergistic effect of the graphene oxide, the porous graphene oxide and the Congo red optimizes the porous graphene oxide pervaporation membrane structure, and remarkably improves the permeation and separation performance.
The foregoing is only the embodiments of the present invention, and therefore, the patent scope of the invention is not limited thereto, and all equivalent structures made by the description of the invention and the accompanying drawings are directly or indirectly applied to other related technical fields, which are all within the scope of the invention.
Claims (8)
1. The porous graphene oxide pervaporation membrane is characterized in that the porous graphene oxide pervaporation membrane comprises a base membrane and a porous graphene oxide separation layer covered on the base membrane, wherein the porous graphene oxide separation layer comprises graphene oxide, porous graphene oxide and Congo red molecules; the thickness of the graphene oxide is 1nm, and the transverse dimension is 400-600 nm; the pore diameter of the porous graphene oxide is 3-5 nm, the thickness is 0.6nm, and the transverse dimension is 50-100 nm; in the porous graphene oxide separation layer, the mass ratio of graphene oxide to porous graphene oxide is 1:1 to 1:3, the mass ratio of Congo red to graphene oxide to porous graphene oxide is 0.11: 1-0.19:1; the thickness of the porous graphene oxide separation layer is 50-160 nm; the interlayer channel size of the porous graphene oxide separation layer is 0.383-0.474 nm.
2. The porous graphene oxide pervaporation membrane according to claim 1, wherein the method of preparing the same comprises the steps of:
step 1, mixing graphene oxide dispersion liquid with hydrogen peroxide at a high temperature for reacting for a period of time to obtain porous graphene oxide;
step 2, preparing porous graphene oxide obtained in the step 1 into porous graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid, congo red solution and the porous graphene oxide dispersion liquid, diluting, and uniformly stirring to obtain mixed liquid;
and 3, carrying out suction filtration on the mixed solution obtained in the step 2 on the base film by a vacuum auxiliary filtration method, and carrying out thermal crosslinking on the base film assembled with the mixed solution to obtain the porous graphene oxide pervaporation film.
3. The porous graphene oxide pervaporation membrane according to claim 2, wherein in step 1, the concentration of the graphene oxide dispersion liquid is 2-5 mg/ml, and the concentration of the hydrogen peroxide is 30%; the volume ratio of the graphene oxide dispersion liquid to the hydrogen peroxide is 10: 1-2: 1.
4. The porous graphene oxide pervaporation membrane according to claim 2 or 3, wherein in step 1, the temperature of the mixing reaction of the graphene oxide dispersion liquid and hydrogen peroxide is 100 ℃ and the time is 2-8 hours.
5. The porous graphene oxide pervaporation membrane according to claim 2 or 3, wherein in step 2, the concentration of each of the graphene oxide dispersion, congo red solution and porous graphene oxide dispersion is 0.2mg/ml.
6. The porous graphene oxide pervaporation membrane according to claim 2 or 3, wherein in step 2, the volume ratio of the graphene oxide dispersion liquid to the porous graphene oxide dispersion liquid is 1:1 to 1:3, and the sum of the volumes of the two is 2ml; the volume ratio of Congo red solution to graphene oxide dispersion liquid to porous graphene oxide dispersion liquid is 0.2:1 to 1:1.
7. A porous graphene oxide pervaporation membrane according to claim 2 or 3, wherein in step 3, the base membrane is thermally cross-linked at a temperature of 60 ℃ for a period of 3 hours.
8. Use of the porous graphene oxide pervaporation membrane according to claim 1, for separating a water/butanol mixture.
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