CN115445439A - Pervaporation membrane and preparation method and application thereof - Google Patents

Pervaporation membrane and preparation method and application thereof Download PDF

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Publication number
CN115445439A
CN115445439A CN202110636406.9A CN202110636406A CN115445439A CN 115445439 A CN115445439 A CN 115445439A CN 202110636406 A CN202110636406 A CN 202110636406A CN 115445439 A CN115445439 A CN 115445439A
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graphene oxide
electric field
pervaporation membrane
pervaporation
polymer matrix
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杜润红
洋汉军
杜春良
闫伟
王晶晶
杜发鑫
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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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
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

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  • Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a pervaporation membrane and a preparation method and application thereof, and the pervaporation membrane comprises the following components: a polymer matrix; graphene oxide nanosheets doped in the polymer matrix and comprising hydrophilic functional groups; wherein the graphene oxide nanoplatelets are oriented in the thickness direction of the film. The pervaporation membrane is an organic-inorganic hybrid membrane prepared by doping Graphene Oxide (GO) nanosheets into a polymer matrix, and the Graphene nanosheets in the polymer matrix are arranged by applying an external alternating current electric field, so that the Graphene nanosheets are oriented in the membrane, and the permeation flux of the pervaporation membrane is improved.

Description

Pervaporation membrane and preparation method and application thereof
Technical Field
The invention belongs to the field of separation of constant-boiling residues and near-boiling residues, micro-water removal, brine desalination and the like, and particularly relates to a pervaporation membrane and a preparation method and application thereof.
Background
Pervaporation is a novel separation technology which takes the chemical potential gradient of a certain component in a liquid mixture on two sides of a membrane as a mass transfer driving force to enable the component to be adsorbed and dissolved on the surface of the membrane, to be diffused in the membrane and to be vaporized on the downstream side of the membrane, and the difference of different components in the dissolving and diffusing processes is utilized to realize separation. Pervaporation has the advantages of low energy consumption, small pollution, simple equipment, convenient operation and the like, can be applied to the fields of separation of azeotrope and near-boiling substance, removal of trace water, desalination of salt-containing water and the like, and becomes one of the research hotspots in the fields of chemical engineering, environmental protection and the like.
At present, the problem of insufficient flux exists in the pervaporation membrane, and the large-scale industrial application of the pervaporation technology is limited.
Disclosure of Invention
In view of the above, the present invention provides a pervaporation membrane with improved permeation flux, and a preparation method and application thereof.
According to one aspect of the invention, the pervaporation membrane comprises the following components: a polymer matrix; and graphene oxide nanoplatelets dispersed in the polymer matrix, the graphene oxide nanoplatelets comprising hydrophilic functional groups; wherein the graphene oxide nanoplatelets are oriented in the thickness direction of the film.
In the invention, graphene Oxide (hereinafter abbreviated as GO) nanosheets are doped into a polymer matrix, and an external alternating current electric field is applied to arrange the Graphene Oxide nanosheets in the polymer matrix so as to be oriented in the membrane, so that the prepared organic-inorganic hybrid membrane (namely, a pervaporation membrane) has higher permeation flux than a membrane prepared under the condition of no electric field.
According to some embodiments of the invention, the polymer matrix comprises: one or more of polyetheramide, polyvinyl alcohol, chitosan, cellulose triacetate, polyhydroxymethylene, sulfonated polyethylene, polyamide, polyethersulfone, sodium alginate, polyacrylonitrile, and polydimethylaminoethyl methacrylate; preferably, the polymer matrix comprises cellulose triacetate.
According to some embodiments of the present invention, the graphene oxide nanoplatelets have a sheet diameter of 0.05 to 5 μm, preferably 0.1 to 3 μm, more preferably 0.2 to 1.5 μm. In the present invention, the term "sheet diameter" refers to a linear distance between two points that are farthest from each other on the same plane of the graphene oxide nanosheet.
According to some embodiments of the invention, the hydrophilic functional groups of the graphene oxide nanoplatelets comprise one or more of carboxyl groups, hydroxyl groups and epoxy groups. For example, graphene oxide nanoplatelets available from Sigma-Aldrich under the trade designation 796034 are used.
According to some embodiments of the present invention, the mass fraction of the graphene oxide nanoplatelets relative to the pervaporation membrane is 0.05 to 25wt%, preferably 0.5 to 20wt%, and more preferably 2.5 to 15wt%.
According to a second aspect of the present invention, there is also provided a method of manufacturing a pervaporation membrane as described above, comprising the steps of:
step a), dispersing graphene oxide nanosheets in a solvent to form a graphene oxide nanosheet dispersion liquid, wherein the content of the graphene oxide nanosheets in the graphene oxide nanosheet dispersion liquid is 0.001-0.7 wt%, preferably 0.01-0.5 wt%, and more preferably 0.05-0.3 wt%;
step b) adding a polymer matrix into the graphene oxide nanosheet dispersion liquid obtained in the step a), and stirring and dissolving to form a membrane casting liquid;
and c) casting the casting solution in the step b) into a film, placing the film in an electric field, and drying to obtain the electric field oriented pervaporation film.
According to some embodiments of the present invention, the graphene oxide nanosheet dispersion liquid is prepared in the step a) by ultrasonic action, and the ultrasonic dispersion time is 30 to 60 minutes; and/or wherein the graphene oxide nanosheet has a platelet diameter of 0.05 to 5 μm, preferably 0.1 to 3 μm, and more preferably 0.2 to 1.5 μm; and/or the hydrophilic functional groups of the graphene oxide nanoplatelets comprise one or more of carboxyl groups, hydroxyl groups, and epoxy groups; and/or the solvent comprises one or more of 1, 4-dioxane, 1, 2-dichloroethane, isopropanol, o-xylene, cyclohexanone, m-xylene, anhydrous ethanol, petroleum ether, tetrahydrofuran, glacial acetic acid, preferably 1, 4-dioxane.
According to some embodiments of the present invention, in the step b), a casting solution with a polymer matrix concentration of 0.1 to 15wt%, preferably 0.5 to 10wt%, and more preferably 1 to 5wt% is prepared; and/or the stirring temperature is 40-80 ℃ and the stirring time is 8-15 hours; the polymer matrix comprises one or more of polyether amide, polyvinyl alcohol, chitosan, cellulose triacetate, polyhydroxymethylene, sulfonated polyethylene, polyamide, polyether sulfone, sodium alginate, polyacrylonitrile and polydimethylaminoethyl methacrylate, and is preferably cellulose triacetate.
According to some embodiments of the invention, the electric field strength in step c) is 400 to 5000V/cm, preferably 500 to 3000V/cm, more preferably 600 to 1000V/cm; and/or the frequency is 400-1000 Hz, and the action time of the electric field is 10-120 minutes; and/or the drying time is 2 to 24 hours.
According to the third aspect of the present invention, the pervaporation membrane as described above and the pervaporation membrane prepared by the method for preparing the pervaporation membrane as described above are provided, and the pervaporation membrane is applied to the fields of separation of azeotrope and near-boiling substance, micro-water removal, desalination of salt water and the like.
The invention has the beneficial effects that:
according to the invention, hydrophilic functional groups exist on the graphene oxide nanosheets, the graphene oxide nanosheets can be doped in a polymer to prepare an organic-inorganic hybrid membrane, and gaps among the graphene oxide nanosheets and an interface formed between an organic phase and an inorganic phase can be mass transfer channels of a permeant in the membrane.
Furthermore, the graphene oxide nanosheets in the polymer matrix are arranged by applying an external alternating current electric field, so that the GO nanosheets are oriented in the membrane, the mass transfer path of permeate molecules in the membrane is shortened, and the permeation flux of the pervaporation membrane is improved.
Drawings
Fig. 1A is a microscopic view of a dispersion of graphene oxide nanoplatelets prepared according to example 1 of the present invention in 1, 4-dioxane at 0 second, 60 seconds, 90 seconds, 120 seconds, and 150 seconds under an electric field.
Fig. 1B is a microscopic observation image of the dispersion liquid of graphene oxide nanoplatelets prepared according to example 2 of the present invention in 1, 2-dichloroethane under the effect of an electric field for 0 second and 150 seconds.
Fig. 1C is a microscopic observation view of the dispersion liquid of graphene oxide nanoplatelets prepared according to example 2 of the present invention in isopropanol at 0 second and 150 seconds under the effect of an electric field.
Fig. 1D is a microscopic image of the dispersion liquid of graphene oxide nanoplatelets prepared according to example 2 of the present invention in o-xylene under the influence of an electric field for 0 second and 150 seconds.
Fig. 1E is a microscopic observation view of the dispersion liquid of graphene oxide nanosheets in cyclohexanone prepared according to example 2 of the present invention under the action of an electric field for 0 second and 150 seconds.
Fig. 1F is a microscopic image of the dispersion liquid of graphene oxide nanoplatelets prepared according to example 2 of the present invention in m-xylene under the influence of an electric field for 0 second and 150 seconds.
Fig. 1G is a microscopic observation image of the dispersion liquid of graphene oxide nanoplatelets prepared according to embodiment 2 of the present invention in absolute ethanol under the effect of an electric field for 0 second and 150 seconds.
Fig. 1H is a microscopic observation view of the dispersion liquid of graphene oxide nanoplatelets prepared according to example 2 of the present invention in petroleum ether under the effect of an electric field for 0 second and 150 seconds.
Fig. 1I is a microscopic observation view of the dispersion liquid of graphene oxide nanosheets in tetrahydrofuran prepared according to example 2 of the present invention under the action of an electric field for 0 second and 150 seconds.
Fig. 1J is a microscopic view of the dispersion liquid of graphene oxide nanoplatelets prepared according to example 2 of the present invention in glacial acetic acid under the action of an electric field for 0 second and 150 seconds.
FIG. 1K is a schematic view of a microscope setup for observing pervaporation membranes in accordance with exemplary embodiments of the present invention.
Fig. 2 is a flowchart of a method of making a pervaporation membrane according to an exemplary embodiment of the present invention.
Fig. 3 is a schematic diagram of a pervaporation membrane implementing an electric field orientation effect according to an exemplary embodiment of the present invention.
FIG. 4 is a graph of pervaporation membrane performance versus electric field strength for electric field orientation according to an exemplary embodiment of the present invention.
Description of the reference numerals
101. Microscope
103. Electrode plate
105. High-voltage pulse power supply
107. Glass groove
109. Graphene oxide nanosheet dispersion liquid
301. Power supply
303. Dust-free box
305. Electrode plate
307. Backing board
309. Casting solution
311. Glass plate
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The graphene oxide nanosheet has anisotropic polarizability, and when the graphene oxide nanosheet is acted by an external electric field, the external electric field generates an induced dipole moment on the plane of the graphene oxide nanosheet. The interaction of the external electric field and the dipole moment generates a torque, which acts on the graphene oxide nanoplatelets to turn and align the dipoles with the direction of the external electric field, thereby making the graphene oxide nanoplatelets parallel to the direction of the electric field. Therefore, in the process of preparing the membrane by adopting the GO-containing polymer solution, an external electric field with the direction perpendicular to the membrane sheet is applied to the two sides of the membrane, so that the graphene oxide nanosheets in the polymer can be oriented along the thickness direction of the membrane.
[1]Besharat F,Manteghian M,Gallone G,et al.Electric field induced alignment of graphene oxide nanoplatelets in polyethersulfone matrix[J].Nanotechnology,2020,31(15):155701(16pp).
It should be noted that the reagents used in the examples of the present invention are all conventional products that can be obtained commercially, and all of the reagents are analytically pure or chemically pure.
Example 1
The procedure for preparing the graphene oxide nanosheet dispersion used in example 1 included adding graphene oxide nanosheets (trade name 796034; manufacturer Sigma-Aldrich; molecular weight 4239.48g/mol, average plate diameter 0.8 μm) to 1, 4-Dioxane (Dioxane, analytical pure, chemical reagents ltd., mikrom, ltd., tianjin, manufacturers) to prepare a graphene oxide nanosheet dispersion having a content of graphene oxide nanosheets of 0.02wt% in the dispersion, and ultrasonically dispersing the graphene oxide nanosheet dispersion for 1 hour.
Fig. 1A is a microscopic image of the 1, 4-dioxane dispersion of graphene oxide nanoplatelets prepared according to example 1 of the present invention at 0 seconds, 60 seconds, 90 seconds, 120 seconds, and 150 seconds under the influence of an electric field.
In this embodiment, the observation environment in fig. 1A is that the concentration of the graphene oxide nanosheet dispersion is 0.02wt%, the electric field strength is 1000V/cm, the frequency is 1000Hz, and the used observation device is shown in the schematic diagram of the microscope device in fig. 1K.
In this embodiment, under the condition of an electric field, as the time of the electric field is prolonged, the graphene oxide nanosheet is more obviously oriented in the solvent.
Example 2
Example 2 the procedure for preparing the graphene oxide nanoplatelet dispersion used comprised mixing graphene oxide nanoplatelets (trade name 796034; sigma-Aldrich, molecular weight 4239.48g/mol, average of plate diameter 0.8 μm, were added to 1, 2-dichloroethane (Asahu chemical reagent, inc., of Tianjin City, analyzer), isopropanol (Asahu chemical reagent, inc., of Tianjin City, analyzer), o-xylene (Asahu chemical reagent, inc., of Tianjin City, analyzer), m-xylene (Asahu chemical reagent, inc, of Tianjin City, analyzer), cyclohexanone (Asahu chemical reagent, of Tianjin City, analyzer), absolute ethanol (Asahu chemical reagent, inc, of Tianjin City, analyzer), petroleum ether (Asahu chemical reagent, inc, of Tianjin city, analyzer), tetrahydrofuran (Asahu chemical reagent, of Tianjin city, analyzer), glacial acetic acid (Asahu chemical reagent, of Tianjin city, nanohu chemical reagent, inc, manufacturer, analyzer), and the dispersion of graphene oxide was 0.02wt% of the dispersion of the graphene oxide nanoplatelets, and the graphene oxide dispersion was prepared.
Fig. 1B to 1J are microscope observation images of the graphene oxide nanosheet dispersion prepared according to example 2 of the present invention under the influence of an electric field for 0 second and 150 seconds.
In this embodiment, the observation environment shown in fig. 1B to 1J is 0.02wt% of the graphene oxide nanosheet dispersion, the electric field strength is 1000V/cm, the frequency is 1000Hz, and the observation apparatus used is as shown in the schematic view of the microscope apparatus shown in fig. 1K.
In this embodiment, under the condition of an electric field, as the time of the electric field is prolonged, the orientation of the graphene oxide nanosheet in the solvent is more obvious.
Example 3
Fig. 2 is a flowchart of a method of making a pervaporation membrane according to an exemplary embodiment of the present invention.
Referring to fig. 2, in step S201 of this embodiment, 0.05g of graphene oxide nanosheets (product number 796034; manufacturer Sigma-Aldrich; molecular weight 4239.48g/mol, average value of plate diameter 0.8 μm) and 97.95g of 1, 4-Dioxane (Dioxane, manufacturer Tianjin, department of mion chemical reagents, ltd., analytical purity) are blended to prepare a graphene oxide nanosheet dispersion liquid with a graphene oxide nanosheet content of 0.05wt% in the dispersion liquid, and the graphene oxide nanosheet dispersion liquid is ultrasonically dispersed for 1 hour. And then proceeds to S203.
In step S203, 2g of cellulose triacetate (analytically pure; manufacturer ACROS; molecular weight 966.845 g/mol) as a polymer matrix is added to the graphene oxide nanosheet dispersion, stirred and dissolved to form a casting solution, and stirred and dissolved in a water bath at 80 ℃ for 8 hours to obtain the casting solution with GO/CTA = 0.025. And then proceeds to S205.
In step S205, the casting solution is scraped into a film on a glass plate, and the film is placed in a high voltage AC electric field with an electric field strength of 1000V/cm and a frequency of 1000Hz, and the electric field action apparatus is shown in FIG. 3. The application of the electric field was stopped 50 minutes later and allowed to dry naturally for 24 hours to evaporate the solvent to form a cured film. The pervaporation membrane of the present example was obtained.
The conditions for carrying out the pervaporation experiment on the pervaporation membrane obtained in the present example include: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
The result of pervaporation experiment in this example is: the water flux is 8.10 kg/(m) 2 H), the salt rejection of NaCl was 99.9%.
Example 4
Similarly to example 3, referring to fig. 2, in step S201 of this embodiment, 0.1g of graphene oxide nanosheets (product number 796034; sigma-Aldrich manufacturer, with a molecular weight of 4239.48g/mol, a mean value of the plate diameter of 0.8 μm) and 97.9g of 1, 4-Dioxane (Dioxane, analytical pure, techniaki chemical reagent Co., ltd., manufacturer Tianjin) were blended to prepare a graphene oxide nanosheet dispersion with a content of 0.1wt% of graphene oxide nanosheets in the dispersion, and the graphene oxide nanosheet dispersion was ultrasonically dispersed for 1 hour. And then proceeds to S203.
In step S203, 2g of cellulose triacetate (analytically pure; manufacturer ACROS; molecular weight 966.845 g/mol) as a polymer matrix is added to the graphene oxide nanosheet dispersion, stirred and dissolved to form a casting solution, and stirred and dissolved in a water bath at 80 ℃ for 8 hours to obtain the casting solution with GO/CTA = 0.05. And then proceeds to S205.
In step S205, the casting solution is scraped into a film on a glass plate, and the film is placed in a high voltage AC electric field with an electric field strength of 600-1000V/cm (one sample is prepared at intervals of 100V/cm, so 5 samples are used in the present example) and a frequency of 1000Hz, and the electric field applying apparatus is shown in FIG. 3. The electric field was applied for 50 minutes and then stopped and dried for 24 hours. The pervaporation membrane of the present example was obtained.
The conditions for carrying out the pervaporation experiment on the pervaporation membrane obtained in the embodiment comprise that: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
The result of pervaporation experiment in this example is:
electric field intensity of 600V/cm sample: the water flux is 7.63 kg/(m) 2 H), the salt rejection of NaCl is 99.9%;
electric field strength of 700V/cm sample: the water flux is 7.76 kg/(m) 2 H), the salt rejection of NaCl is 99.9%;
electric field intensity of 800V/cm sample: the water flux is 7.93 kg/(m) 2 H), the salt rejection of NaCl is 99.9%;
the electric field intensity is 900V/cm of the sample: the water flux is 8.12 kg/(m) 2 H), the salt rejection of NaCl is 99.9%;
electric field strength 1000V/cm sample: the water flux is 8.59 kg/(m) 2 H), the salt rejection of NaCl was 99.9%.
This example demonstrates that the higher the electric field strength, the higher the degree of GO orientation, and the more the water flux is boosted, as shown in fig. 4.
Example 5
Similarly to the above example 3, referring to fig. 2, in step S201 of this example, 0.15g of graphene oxide nanosheet (product number 796034; manufacturer Sigma-Aldrich; molecular weight 4239.48g/mol, average value of the plate diameter is 0.8 μm) is blended with 97.85g of 1, 4-Dioxane (analytically pure, manufactured by seiko chemical reagents ltd., tianjin, inc.) to prepare a graphene oxide nanosheet dispersion liquid with the content of the graphene oxide nanosheet of 0.15wt% in the dispersion liquid, and the graphene oxide nanosheet dispersion liquid is ultrasonically dispersed for 1h. And then proceeds to S203.
In step S203, 2g of cellulose triacetate (analytical grade; manufacturer ACROS; molecular weight 966.845 g/mol) as a polymer matrix is added to the graphene oxide nanosheet dispersion, stirred and dissolved to form a casting solution, and stirred and dissolved in a water bath at 80 ℃ for 8 hours to obtain a casting solution with GO/CTA = 0.075. And then proceeds to S205.
In step S205, the casting solution is scraped into a film on a glass plate, and the film is placed in a high voltage AC electric field with an electric field strength of 1000V/cm and a frequency of 1000Hz, and the electric field action apparatus is shown in FIG. 3. The electric field was applied for 50 minutes and then stopped and dried for 24 hours. The pervaporation membrane of the present example was obtained.
The conditions for carrying out the pervaporation experiment on the pervaporation membrane obtained in the present example include: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of a permeation side is 0kPa.
The result of the pervaporation experiment in this example is: the water flux is 9.06 kg/(m) 2 H), the salt rejection of NaCl was 99.9%.
Example 6
Referring to fig. 2, in step S201 of this embodiment, 0.2g of graphene oxide nanosheets (product number 796034; manufacturer Sigma-Aldrich; molecular weight 4239.48g/mol, average value of plate diameter 0.8 μm) and 97.8g of 1, 4-Dioxane (Dioxane, manufacturer Tianjin, department of mion chemical reagents, ltd., analytical purity) are blended to prepare a graphene oxide nanosheet dispersion liquid with a graphene oxide nanosheet content of 0.2wt% in the dispersion liquid, and the graphene oxide nanosheet dispersion liquid is ultrasonically dispersed for 1 hour. And then proceeds to S203.
In step S203, 2g of cellulose triacetate (analytically pure; manufacturer ACROS; molecular weight 966.845 g/mol) as a polymer matrix is added to the graphene oxide nanosheet dispersion, stirred and dissolved to form a casting solution, and stirred and dissolved in a water bath at 80 ℃ for 8 hours to obtain the casting solution with GO/CTA = 0.1. And then proceeds to S205.
In step S205, the casting solution is scraped into a film on a glass plate, and the film is placed in a high voltage AC electric field with an electric field strength of 1000V/cm and a frequency of 1000Hz, and the electric field action apparatus is shown in FIG. 3. The field was applied for 50 minutes and then stopped and dried for 24 hours. The pervaporation membrane of the present example was obtained.
The conditions for carrying out the pervaporation experiment on the pervaporation membrane obtained in the present example include: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of a permeation side is 0kPa.
The result of pervaporation experiment in this example is: the water flux is 9.07 kg/(m) 2 H), salt rejection of NaCl 99.9%.
Example 7
Referring to fig. 2, in step S201 of this embodiment, 0.25g of graphene oxide nanosheets (trade name 796034; manufacturer Sigma-Aldrich; molecular weight 4239.48g/mol, average value of plate diameter 0.8 μm) and 97.75g of 1, 4-Dioxane (dioxyane, analytical pure, of tianjin, cromo chemical reagent ltd) are blended to prepare a graphene oxide nanosheet dispersion liquid with the content of graphene oxide nanosheets of 0.25wt% in the dispersion liquid, and the graphene oxide nanosheet dispersion liquid is ultrasonically dispersed for 1 hour. And then proceeds to S203.
In step S203, 2g of cellulose triacetate (analytically pure; manufacturer ACROS; molecular weight 966.845 g/mol) as a polymer matrix is added to the graphene oxide nanosheet dispersion, stirred and dissolved to form a casting solution, and stirred and dissolved in a water bath at 80 ℃ for 8 hours to obtain the casting solution with GO/CTA = 0.125. And then proceeds to S205.
In step S205, the casting solution is scraped into a film on a glass plate, and the film is placed in a high voltage AC electric field with an electric field strength of 1000V/cm and a frequency of 1000Hz, and the electric field action apparatus is shown in FIG. 3. The electric field was applied for 50 minutes and then stopped and dried for 24 hours. The pervaporation membrane of the present example was obtained.
The conditions for carrying out the pervaporation experiment on the pervaporation membrane obtained in the present example include: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of a permeation side is 0kPa.
The result of pervaporation experiment in this example is: the water flux is 9.11 kg/(m) 2 H), salt rejection of NaCl 99.9%.
Example 8
Referring to fig. 2, in step S201 of this embodiment, 0.3g of graphene oxide nanosheets (trade name 796034; manufacturer Sigma-Aldrich; molecular weight 4239.48g/mol, average value of plate diameter 0.8 μm) and 97.7g of 1, 4-Dioxane (dioxyane, analytical pure, of tianjin, cromo chemical reagent ltd) are blended to prepare a graphene oxide nanosheet dispersion liquid with the content of graphene oxide nanosheets of 0.3wt% in the dispersion liquid, and the graphene oxide nanosheet dispersion liquid is ultrasonically dispersed for 1 hour. And then proceeds to S203.
In step S203, 2g of cellulose triacetate (analytically pure; manufacturer ACROS; molecular weight 966.845 g/mol) as a polymer matrix is added to the graphene oxide nanosheet dispersion, stirred and dissolved to form a casting solution, and stirred and dissolved in a water bath at 80 ℃ for 8 hours to obtain the casting solution with GO/CTA = 0.15. And then proceeds to S205.
In step S205, the casting solution is scraped into a film on a glass plate, and the film is placed in a high voltage AC electric field with an electric field strength of 1000V/cm and a frequency of 1000Hz, and the electric field action apparatus is shown in FIG. 3. The electric field was applied for 50 minutes and then stopped and dried for 24 hours. The pervaporation membrane of the present example was obtained.
The conditions for carrying out the pervaporation experiment on the pervaporation membrane obtained in the present example include: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of a permeation side is 0kPa.
The result of the pervaporation experiment in this example is: the water flux is 9.23 kg/(m) 2 H), the salt rejection of NaCl was 99.9%.
Comparative example 1
Similarly to the casting solution prepared in example 3, it was dried for 24 hours in an electric field-free environment to obtain a pervaporation membrane that was not oriented by an electric field.
The conditions for carrying out the pervaporation test on the pervaporation membrane obtained in comparative example 1 included: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
Comparative example 1 the results of the pervaporation experiments were: the water flux is 7.07 kg/(m) 2 H), the salt rejection of NaCl was 99.9%.
Comparative example 2
Similarly to the casting solution prepared in example 4, the casting solution was dried in an electric field-free environment for 24 hours to obtain a pervaporation membrane that was not oriented by an electric field.
The conditions for conducting the pervaporation experiment on the pervaporation membrane obtained in comparative example 2 included: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
Comparative example 2 the results of the pervaporation experiments were: the water flux is 7.24 kg/(m) 2 H), salt rejection of NaCl 99.9%.
Comparative example 3
Similarly to the casting solution prepared in example 5, the same was dried in an electric field-free environment for 24 hours to obtain a pervaporation membrane that was not oriented by an electric field.
The conditions for carrying out the pervaporation test on the pervaporation membrane obtained in comparative example 3 included: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
Comparative example 3 the results of the pervaporation experiments were: the water flux is 7.36 kg/(m) 2 H), salt rejection of NaCl 99.9%.
Comparative example 4
Similarly to the casting solution prepared in example 6, it was dried for 24 hours in an electric field-free environment to obtain a pervaporation membrane that was not oriented by an electric field.
The conditions for conducting the pervaporation test on the pervaporation membrane obtained in comparative example 4 included: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
Comparative example 4 the results of the pervaporation experiment were: the water flux is 7.69 kg/(m) 2 H), salt rejection of NaCl 99.9%.
Comparative example 5
Similarly to the casting solution prepared in example 7, it was dried in an electric field-free environment for 24 hours to obtain a pervaporation membrane that was not oriented by an electric field.
The conditions for conducting the pervaporation test on the pervaporation membrane obtained in comparative example 5 included: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
Comparative example 5 the results of the pervaporation experiments were: the water flux is 7.95 kg/(m) 2 H), salt rejection of NaCl 99.9%.
Comparative example 6
Similarly to the casting solution prepared in example 8, it was dried for 24 hours in an electric field-free environment to obtain a pervaporation membrane that was not oriented by an electric field.
The conditions for conducting the pervaporation test on the pervaporation membrane obtained in comparative example 6 included: the raw material solution is 35g/L NaCl aqueous solution, the flow rate is 1000mL/min, the temperature is 50 ℃, and the absolute pressure of the permeation side is 0kPa.
Comparative example 6 the results of the pervaporation experiment were: the water flux is 8.53 kg/(m) 2 H), salt rejection of NaCl 99.9%.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art in light of the technical teaching provided by the present invention, and should be considered as the protection scope of the present invention.

Claims (8)

1. A pervaporation membrane, comprising the following components:
a polymer matrix; and
graphene oxide nanoplatelets dispersed in the polymer matrix, the graphene oxide nanoplatelets comprising hydrophilic functional groups;
wherein the graphene oxide nanoplatelets are oriented in the thickness direction of the film.
2. The pervaporation membrane according to claim 1, wherein said polymer matrix comprises: one or more of polyether amide, polyvinyl alcohol, chitosan, cellulose triacetate, polyhydroxymethylene, sulfonated polyethylene, polyamide, polyether sulfone, sodium alginate, polyacrylonitrile and polydimethylaminoethyl methacrylate;
preferably, the polymer matrix comprises cellulose triacetate.
3. Pervaporation membrane according to claim 1 or 2, characterised in that said graphene oxide nanoplatelets have a sheet diameter comprised between 0.05 and 5 μ ι η, preferably between 0.1 and 3 μ ι η, more preferably between 0.2 and 1.5 μ ι η; and/or
The hydrophilic functional group of the graphene oxide nanosheet comprises one or more of a carboxyl group, a hydroxyl group and an epoxy group; and/or
The mass fraction of the graphene oxide nanosheet relative to the pervaporation membrane is 0.05 to 25wt%, preferably 0.5 to 20wt%, and more preferably 2.5 to 15wt%.
4. A method of making a pervaporation membrane according to any of claims 1 to 3, comprising the steps of:
step a), dispersing graphene oxide nanosheets in a solvent to form a graphene oxide nanosheet dispersion liquid; wherein the content of the graphene oxide nanosheet in the graphene oxide nanosheet dispersion liquid is 0.001-0.7 wt%, preferably 0.01-0.5 wt%, and more preferably 0.05-0.3 wt%;
step b) adding a polymer matrix into the graphene oxide nanosheet dispersion liquid obtained in the step a), and stirring and dissolving to form a membrane casting liquid;
and c) casting the casting solution in the step b) into a film, placing the film in an electric field, and drying to obtain the electric field oriented pervaporation film.
5. The preparation method according to claim 4, wherein the graphene oxide nanosheet dispersion liquid is prepared in step a) by ultrasonic action for 30-60 minutes; and/or
Wherein the sheet diameter of the graphene oxide nanosheet is 0.05-5 μm; and/or
The hydrophilic functional groups of the graphene oxide nanoplatelets comprise carboxyl and/or hydroxyl and/or epoxy groups.
6. The method according to claim 4 or 5, wherein the concentration of the polymer matrix in the casting solution in step b) is 0.1 to 15wt%, preferably 0.5 to 10wt%, more preferably 1 to 5wt%; and/or
Stirring at 40-80 deg.c for 8-15 hr;
wherein the polymer matrix comprises one or more of polyether amide, polyvinyl alcohol, chitosan, cellulose triacetate, polyhydroxymethylene, sulfonated polyethylene, polyamide, polyether sulfone, sodium alginate, polyacrylonitrile and polydimethylaminoethyl methacrylate, and preferably the cellulose triacetate.
7. The method according to any one of claims 4 to 6, wherein the electric field strength in step c) is 400 to 5000V/cm, preferably 500 to 3000V/cm, more preferably 600 to 1000V/cm; and/or
The frequency of the electric field is 400-1000 Hz, and the time of the action of the electric field is 10-120 minutes; and/or
The drying time is 2-24 hours.
8. Use of a pervaporation membrane according to any of claims 1-3 and/or a pervaporation membrane prepared according to the method of manufacturing a pervaporation membrane according to any of claims 4-7 in the fields of azeotrope and near-boil separation, trace water removal, desalination of brine and the like.
CN202110636406.9A 2021-06-08 2021-06-08 Pervaporation membrane and preparation method and application thereof Pending CN115445439A (en)

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CN104998560A (en) * 2015-09-02 2015-10-28 中国海洋大学 Preparation method of composite membrane containing oxidized graphene
CN108404682A (en) * 2018-03-12 2018-08-17 黄启洋 A kind of graphene oxide film and preparation method thereof, preparation facilities and application
CN108479423A (en) * 2018-05-31 2018-09-04 大连理工大学 A kind of graphene oxide@polyvinyl alcohols matrix infiltrating and vaporizing membrane and preparation method thereof
CN112495195A (en) * 2020-11-06 2021-03-16 大连理工大学 Preparation method and application method of graphene oxide/carbon nanotube asymmetric separation membrane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101983758A (en) * 2010-10-21 2011-03-09 中国科学院苏州纳米技术与纳米仿生研究所 Polymer/inorganic nanometer composite separation membrane and preparation method thereof
CN104998560A (en) * 2015-09-02 2015-10-28 中国海洋大学 Preparation method of composite membrane containing oxidized graphene
CN108404682A (en) * 2018-03-12 2018-08-17 黄启洋 A kind of graphene oxide film and preparation method thereof, preparation facilities and application
CN108479423A (en) * 2018-05-31 2018-09-04 大连理工大学 A kind of graphene oxide@polyvinyl alcohols matrix infiltrating and vaporizing membrane and preparation method thereof
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