CN111715078B - Sandwich graphene oxide hollow fiber membrane with fixed interlayer spacing and preparation method and application thereof - Google Patents
Sandwich graphene oxide hollow fiber membrane with fixed interlayer spacing and preparation method and application thereof Download PDFInfo
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- CN111715078B CN111715078B CN201910211100.1A CN201910211100A CN111715078B CN 111715078 B CN111715078 B CN 111715078B CN 201910211100 A CN201910211100 A CN 201910211100A CN 111715078 B CN111715078 B CN 111715078B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
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- 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
- B01D69/08—Hollow fibre membranes
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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
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
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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
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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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
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing, and a preparation method and application thereof. The porous polymer layer is prepared by phase inversion on the surface of the GO membrane, swelling of the GO layer and increase of interlayer spacing are inhibited by utilizing the limiting effect of the internal hollow fiber substrate and the external porous polymer layer, so that the sandwich GO hollow fiber membrane with high desalting performance and high stability is obtained, and the prepared sandwich GO hollow fiber membrane is used for desalting application. The method provided by the invention can maintain the physicochemical property of the GO membrane and can be used for synthesizing a sandwich GO hollow fiber membrane with higher separation performance; the obtained sandwich GO hollow fiber membrane can effectively remove inorganic salt which can not be treated by a common GO membrane, and the rejection rate is up to more than 90%; has extremely high stability while maintaining high separation performance and even can resist ultrasonic treatment.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing, and a preparation method and application thereof.
Background
Graphene Oxide (GO) membranes are a novel high efficiency separation membrane. Due to its excellent hydrophilicity, abundant polar groups, high mechanical strength, ultra-thin structure and other properties, it is widely used in various aspects such as gas separation, water treatment, solvent recovery and the like. However, due to its excellent hydrophilicity, when used for water treatment, water molecules are adsorbed into the interlayer of the GO membrane, and the GO membrane interlayer is swollen, thereby causing a decrease in separation performance, particularly in separation efficiency of small molecular substances such as organic small molecules and inorganic salts. Further, unlimited swelling may even cause the GO membrane to re-disperse in the aqueous solution, thereby causing the GO membrane to lose separation performance on the feed liquid. The modification methods commonly used at present mainly include a chemical grafting method and a reduction method. Grafting is to crosslink the GO membrane by introducing the reaction of molecules and the oxygen-containing groups of GO, so that the stability of the GO membrane is improved. However, the reported performance rejection of chemically cross-linked modified GO membranes to date is more general for inorganic salts. The reduction method is to partially reduce the GO membrane through heat treatment or treatment of a reducing agent, so as to inhibit the increase of the distance between GO membrane layers. However, the method improves stability and inhibits increase of interlayer spacing, and simultaneously reduces the oxygen-containing group content of the GO membrane, so that the flux of the GO membrane is reduced. Therefore a new approach that can be used to improve GO membrane stability and separation performance is urgently needed to be established.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the first object of the present invention is to provide a method for preparing a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing.
The invention also aims to provide the sandwich graphene oxide hollow fiber membrane with the fixed interlayer spacing prepared by the method.
The invention further aims to provide an application of the sandwich graphene oxide hollow fiber membrane with the fixed interlayer spacing in desalination.
The purpose of the invention is realized by the following scheme:
a preparation method of a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing comprises the following steps:
(1) preparing a GO hollow fiber membrane: sealing one end of a hollow fiber substrate, soaking the hollow fiber substrate in GO suspension, and depositing a GO layer on the surface of the hollow fiber substrate by vacuumizing the other end of the hollow fiber substrate to obtain a GO hollow fiber membrane;
(2) preparation of a sandwich GO hollow fiber membrane: firstly, dissolving a polymer in an organic solvent to obtain a polymer solution, then removing bubbles in the solution, then soaking the GO hollow fiber membrane obtained in the step (1) in the polymer solution, taking out the GO hollow fiber membrane, soaking the GO hollow fiber membrane in water for phase conversion to obtain a sandwich membrane with a porous polymer layer, then placing the sandwich membrane in water, and finally drying the sandwich membrane to obtain the sandwich GO hollow fiber membrane.
The hollow fiber substrate in the step (1) is one of polymer or ceramic; wherein the polymer is at least one of polyvinylidene fluoride (PVDF), Polystyrene (PS), Polysulfone (PSF), Polyethersulfone (PES), Polyacrylonitrile (PAN) and the like; it is preferable from the economical point of view to use at least one of PVDF, PSF and PES.
The GO suspension in the step (1) is preferably prepared by the following method: firstly, preparing graphite oxide, then dispersing the graphite oxide in water, and preparing a GO suspension by adopting an ultrasonic stripping method.
More preferably, the graphite oxide is prepared by at least one of a hummer method, a modified hummer method, a staudenmier method and a Brodie method; most preferably by the hummer method.
Concentration of GO in GO suspension liquid in step (1)10 to 500. mu.g mL of the composition-1(ii) a In terms of preparation time, 50 to 100. mu.g mL is preferred-1。
The vacuum pumping time in the step (1) is 1-10 h, and the preferable time is 4-8 h in consideration of the GO film thickness and the pumping process.
The polymer in the step (2) is mainly at least one of polyvinylidene fluoride (PVDF), Polystyrene (PS), Polysulfone (PSF), Polyethersulfone (PES), Polyacrylonitrile (PAN) and the like. It is preferable from the economical point of view to use at least one of PVDF, PSF and PES.
The organic solvent in the step (2) is mainly at least one of N' N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), Tetrahydrofuran (THF) and the like, and preferably at least one of DMF and DMAc.
The concentration of the polymer in the polymer solution in the step (2) is 8-20 wt%, preferably 10-12 wt%.
Soaking the GO hollow fiber membrane in the polymer solution for 1-10 s in the step (2); preferably 5 to 8 seconds.
The time for soaking in water for phase transformation in the step (2) is 1-8 min; preferably for 3 min.
The drying temperature in the step (2) is 20-80 ℃, and preferably 50 ℃.
The sandwich graphene oxide hollow fiber membrane with the fixed interlayer spacing is prepared by the method.
The sandwich graphene oxide hollow fiber membrane with the fixed interlayer spacing is applied to desalination.
The mechanism of the invention is as follows:
the porous polymer layer is prepared by performing phase conversion on the surface of the GO membrane based on the special structure of the hollow fiber. The swelling of the GO layer and the increase of the interlayer distance are inhibited by utilizing the limiting effect of the internal hollow fiber substrate and the external porous polymer layer, so that the sandwich GO hollow fiber membrane with high desalting performance and high stability is obtained, and the prepared sandwich GO hollow fiber membrane is used for desalting.
Compared with the prior art, the invention has the following advantages and beneficial effects:
compared with the traditional method for improving the performance of the GO membrane, the method provided by the invention can maintain the physicochemical property of the GO membrane and can be used for synthesizing a sandwich GO hollow fiber membrane with higher separation performance; the obtained sandwich GO hollow fiber membrane can effectively remove inorganic salt which can not be treated by the common GO membrane, and the rejection rate is up to more than 90%; has extremely high stability while maintaining high separation performance and even can resist ultrasonic treatment.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1 Sandwich GO/PVDF hollow fiber Membrane preparation
(1) Preparation of GO suspension: graphite oxide was prepared by hummer. 2g of flake graphite and 1g of sodium nitrate were added to 46mL of concentrated sulfuric acid, and the process was carried out in a mixed bath of ice and water. Then 6g of potassium permanganate was slowly added to the above mixture and reacted at 25 ℃ for 30 min. And finally, diluting the solution by adopting 92mL of deionized water, keeping the solution at the temperature of 98 ℃ for 40min to obtain graphite oxide, adding 6mL of hydrogen peroxide, and cleaning and drying the obtained graphite oxide. 40mg of the obtained graphite oxide is weighed and dispersed in deionized water to prepare the concentration of 2mg mL-1GO suspension of (2). And (3) carrying out ultrasonic treatment on the suspension for 2h, and centrifuging at the rotating speed of 4000rpm for 5min to remove undispersed graphite oxide so as to obtain the uniformly dispersed GO suspension. The resulting GO suspension was diluted to 100. mu.g mL with deionized water-1。
(2) Preparing a GO hollow fiber membrane: GO membranes were prepared by vacuum filtration method. The PVDF hollow fiber substrate was cut to 4 cm. One end of the substrate is then sealed with epoxy glue, while the other end is sealed with a polyurethane tube using epoxy glue. PVDF hollow fiber membranes were soaked in GO suspension. And a vacuum pump is connected with the polyurethane pipe for suction. GO suspension will deposit on the surface of PVDF hollow fiber membrane. When the suction filtered solution reached 4mL (suction 5h), the suction was terminated to obtain GO hollow fiber membrane.
(3) Preparation of a sandwich GO hollow fiber membrane: and depositing a porous PSF layer on the surface of the GO hollow fiber membrane by adopting an immersion phase inversion method. First, a polymer solution was prepared, PSF was added to DMF to prepare a solution having a concentration of 10 wt%, and the PSF was sufficiently dissolved by stirring. The resulting PSF solution was sonicated for 10min and allowed to stand for 12h to remove air bubbles from the solution. For coating, the prepared GO hollow fiber membrane was soaked in the polymer solution for 5 s. And after soaking, soaking the GO hollow fiber membrane with the PSF solution in deionized water for 3min, and performing immersion phase conversion to form an outer porous polymer layer. The resulting sandwich film was then placed in a volume of deionized water for 3 h. Finally drying is carried out at 50 ℃.
And (3) carrying out desalting performance test on the prepared hollow fiber membrane by adopting dead-end filtration. The feed solution was a NaCl solution with a concentration of 500 ppm. The test result shows that the water flux of the prepared GO/PVDF sandwich hollow fiber membrane is 2.8L m-2h-1bar-1The retention rate was 47%.
Example 2 preparation of Sandwich GO/PES hollow fiber membranes
Example 2 differs from example 1 in that the hollow fiber substrate is PES; GO hollow fiber membranes were used as a control. GO hollow fiber membranes differ from sandwich GO/PES hollow fibers in that no porous polymer layer is made.
And (3) carrying out desalting performance test on the prepared hollow fiber membrane by adopting dead-end filtration. The feed solution was a NaCl solution with a concentration of 500 ppm. The water flux of the prepared sandwich GO/PES hollow fiber membrane is 7.1L m-2h-1bar-1The retention rate was 95%. The membrane flux is less than 14.5L m of GO hollow fiber membrane-2h-1bar-1But the rejection rate is greatly improved relative to 21% of the GO hollow fiber membrane. Ultrasonic treatment is carried out on the GO hollow fiber membrane and the sandwich GO/PES hollow fiber membrane for 30min for many times, and the water flux and the rejection rate of the GO hollow fiber membrane are respectively 13L m-2h-1bar-1And 20%, and sandwich GO-PES hollow fiber membraneThe flux and retention properties of (a) were almost constant, indicating that the membrane had very high stability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing is characterized by comprising the following steps:
(1) preparing a GO hollow fiber membrane: sealing one end of a hollow fiber substrate membrane, soaking the hollow fiber substrate membrane in GO suspension, and depositing a GO layer on the surface of the hollow fiber substrate through vacuum suction of the other end to obtain a GO hollow fiber membrane;
(2) preparation of a sandwich GO hollow fiber membrane: firstly, dissolving a polymer in an organic solvent to obtain a polymer solution, then removing bubbles in the solution, soaking the GO hollow fiber membrane obtained in the step (1) in the polymer solution, taking out the GO hollow fiber membrane, soaking the GO hollow fiber membrane in water for phase conversion to obtain a sandwich membrane with a porous polymer layer, then placing the sandwich membrane in water, and finally drying the sandwich membrane to obtain the sandwich GO hollow fiber membrane;
the hollow fiber basement membrane in the step (1) is a hollow fiber polyether sulfone basement membrane;
the polymer in the step (2) is polysulfone.
2. The method for preparing a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing according to claim 1, wherein:
the concentration of GO in the GO suspension liquid in the step (1) is 10-500 mu g mL < -1 >;
and (2) the vacuum pumping time in the step (1) is 1-10 h.
3. The method for preparing a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing according to claim 1, wherein:
the concentration of the polymer in the polymer solution in the step (2) is 8-20 wt%;
soaking the GO hollow fiber membrane in the polymer solution for 1-10 s in the step (2);
and (3) soaking the product in water for phase inversion for 1-8 min.
4. The method for preparing a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing according to claim 1, wherein:
the concentration of GO in the GO suspension liquid in the step (1) is 50-100 mu g mL < -1 >;
and (2) the vacuum pumping time in the step (1) is 4-8 h.
5. The method for preparing a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing according to claim 1, wherein:
the concentration of the polymer in the polymer solution in the step (2) is 10-12 wt%;
soaking the GO hollow fiber membrane in the polymer solution for 5-8 s in the step (2);
and (3) soaking in water for phase inversion for 3 min.
6. The method for preparing a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing according to any one of claims 1 to 5, wherein:
the GO suspension in the step (1) is prepared by the following method: firstly, preparing graphite oxide, then dispersing the graphite oxide in water, and preparing a GO suspension by adopting an ultrasonic stripping method;
wherein the graphite oxide is prepared by at least one of a hummer method, a modified hummer method, a Staudenmaier method and a Brodie method.
7. The method for preparing a sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing according to claim 1, wherein:
the organic solvent in the step (2) is at least one of N' N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and tetrahydrofuran;
the drying temperature in the step (2) is 20-80 ℃.
8. A sandwich graphene oxide hollow fiber membrane with a fixed interlayer spacing prepared by the method of any one of claims 1 to 7.
9. Use of the sandwich graphene oxide hollow fiber membrane with fixed interlayer spacing according to claim 8 in desalination.
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| CN113828167B (en) * | 2021-02-01 | 2023-02-28 | 南京工业大学 | Ceramic composite membrane for oil-water separation and preparation method thereof |
| CN114471155B (en) * | 2021-12-13 | 2023-05-26 | 南京工业大学 | Nanofiltration membrane based on graphene oxide and preparation method and application thereof |
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