CN111420563B - Hybrid composite reverse osmosis/nanofiltration membrane, preparation method and application thereof - Google Patents

Hybrid composite reverse osmosis/nanofiltration membrane, preparation method and application thereof Download PDF

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CN111420563B
CN111420563B CN202010135374.XA CN202010135374A CN111420563B CN 111420563 B CN111420563 B CN 111420563B CN 202010135374 A CN202010135374 A CN 202010135374A CN 111420563 B CN111420563 B CN 111420563B
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reverse osmosis
gqds
membrane
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composite reverse
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CN111420563A (en
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苏保卫
谭晓倩
程晓杰
韩力挥
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Ocean University of China
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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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/001—Runoff or storm water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a preparation method of a hybrid composite reverse osmosis/nanofiltration membrane and application of the prepared hybrid composite reverse osmosis/nanofiltration membrane; the preparation method of the hybrid composite reverse osmosis/nanofiltration membrane comprises a phase inversion step and an interfacial polymerization step; according to the invention, the amination quantum dot intermediate layer is deposited on the polysulfone (polyether sulfone) and polyimide mixed base membrane, and then the interface polymerization is carried out on the amination quantum dot intermediate layer, so that the stability of the membrane is remarkably improved, and the flux of the membrane is improved; the amination quantum dot intermediate layer has a large number of amino groups, so that the amination quantum dot intermediate layer can be connected with polyimide in a base film and a separation skin layer in a covalent bond manner, the dispersibility and stability of nano particles can be improved, and the separation performance of the film is improved; the preparation method is simple in preparation process and has good application prospect in water treatment aspects such as sea water/brackish water desalination and the like.

Description

Hybrid composite reverse osmosis/nanofiltration membrane, preparation method and application thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a hybrid composite reverse osmosis/nanofiltration membrane, a preparation method and application thereof.
Background
In recent years, sea water desalination and brackish water desalination technologies have attracted general attention. In the surface water resource, about 97% of the surface water resource is seawater, and the surface water resource cannot be directly used due to high salt content. But the seawater resources are abundant, so people begin to pay attention to developing the seawater desalination technology, enlarge the acquisition channel of fresh water resources and relieve the dilemma of water resource deficiency.
The membrane separation process has been developed rapidly in the past decades due to its low energy consumption, high efficiency, environmental friendliness, etc., and has become an important separation process in chemical engineering, food processing, water treatment, pharmaceutical technology, etc. Among them, reverse Osmosis (RO) and Nanofiltration (NF) technologies are used to obtain fresh water resources, which have become the most important application directions of membrane separation processes. Current membranes for water treatment market size is $ 60 billion dollars and grow at a rate of 10-15% per year. However, there is a Trade-off relationship between the flux and rejection of the current reverse osmosis membrane, and RO membranes with higher rejection tend to have lower flux.
In order to further improve the flux of reverse osmosis membranes, mixed Matrix Membranes (MMMs) prepared by doping nano materials and thin-layer nano composite membranes (TFNs) have appeared in recent years, wherein the mixed matrix membranes are prepared by adding nano materials into a casting solution based on a phase inversion method, and the nano materials exist in a skin layer and a supporting layer in the film forming process; the latter is to add the nano material into the aqueous phase or oil phase monomer solution in the interfacial polymerization process, and form a thin layer nano material composite film through interfacial polymerization. However, the nanomaterial is poor in dispersibility and easy to agglomerate, and the poor stability of the membrane is caused by the inevitable problems of loss of nanoparticles and the like in the use process because the poor intermolecular interaction force such as van der Waals force and hydrogen bond exists in the membrane matrix.
In recent years, the introduction of nanomaterial interlayers has begun to be of interest to researchers. Depositing a layer of nano material on the base film by vacuum suction filtration or filtration, and obtaining a layer of thin layer composite film by interfacial polymerization. The intermediate layer can accurately regulate and control the aperture, the porosity, the hydrophilicity and the surface morphology of the 'base film', so that the aqueous phase monomer solution is distributed more uniformly, the release of the aqueous phase monomer in the interfacial polymerization process is effectively controlled, and the formation of the separation layer is controlled.
From the research in recent years at home and abroad, the process of depositing a layer of nano material intermediate layer and then performing interfacial polymerization is a research hot spot in recent years. Researchers successfully prepare COFs, CNTs, MOFs, GO and other nano materials into an intermediate layer, so that the separation performance of the composite membrane is improved.
The Graphene Quantum Dots (GQDs) are novel quasi-zero-dimensional nano materials, are single-layer or multi-layer graphene sheets, have strong quantum effects, boundary effects and fluorescence properties, and have good thermal stability, chemical stability, biocompatibility and low toxicity. The functionalized graphene quantum dots are hot spots in recent research, and different functionalized quantum dots have different sizes, shapes and edge groups, so that the application range of the nano material is greatly widened. The aminated graphene quantum dots (af-GQDs) not only have the general performances of quantum dots and graphene, but also can participate in the reaction in the interfacial polymerization process due to the good water solubility and the existence of-NH 2, so that the problem that the nano particles exist in the film material stably for a long time can be solved.
In recent years, graphene quantum dots are beginning to be applied to the preparation process of nanofiltration membranes and reverse osmosis membranes; most of the researches at present take graphene quantum dots as water phase additives, but it is difficult to ensure good dispersion of the graphene quantum dots and stability of the quantum dots.
Polysulfone or polyethersulfone is widely used as a base membrane in the preparation of reverse osmosis membranes and nanofiltration membranes, and then an ultrathin skin layer is prepared through interfacial polymerization. However, since the polysulfone and polyethersulfone have no active groups on the polymer chains, covalent interactions with the nanomaterials cannot be formed, and most of the intermolecular weak interaction forces between the nanomaterial intermediate layer and the base membrane and between the nanomaterial intermediate layer and the skin layer are still combined through van der Waals force, hydrogen bond and the like, the nanomaterial intermediate layer is inevitably unstable, and the problems of nanoparticle loss and the like exist in the use process, so that the stability of the membrane is poor, and the flux and the rejection rate of the membrane are low.
Disclosure of Invention
Aiming at the technical problems of incapability of uniformly dispersing nano particles in a membrane material, poor stability of the nano particles, low flux and retention rate of the membrane and the like in the prior art, the invention provides a hybrid composite reverse osmosis/nanofiltration membrane, a preparation method and application thereof, and the prepared hybrid composite reverse osmosis/nanofiltration membrane has good nano particle dispersibility and stability.
In order to achieve the above object, the technical scheme of the present invention is as follows.
The first aspect of the invention discloses a hybrid composite reverse osmosis/nanofiltration membrane, which is prepared by depositing a nano material intermediate layer on the surface of a base membrane and forming a separation skin layer on the nano material intermediate layer through interfacial polymerization, wherein,
the base film is prepared by scraping a layer of casting film liquid prepared from polysulfone (or polyether sulfone) and polyimide according to a certain proportion on the surface of a non-woven fabric and performing phase inversion, wherein the mass percentage content of polyimide in the casting film liquid is 0.5% -2%;
the nano material intermediate layer is composed of amino graphene quantum dots (af-GQDs);
the separation skin layer is made of polyamide.
Preferably, the af-GQDs nanomaterial interlayer is connected with the base film through a covalent bond.
Preferably, the af-GQDs nanomaterial intermediate layer and the separation layer are connected through a covalent bond.
Preferably, the average sheet diameter of the af-GQDs is less than or equal to 50nm; more preferably, the af-GQDs have an average sheet diameter of 10nm or less.
Preferably, the af-GQDs have an average thickness of less than or equal to 5nm; more preferably, the af-GQDs have an average thickness of less than or equal to 2nm.
The invention discloses a preparation method of a multifunctional hybrid composite reverse osmosis/nanofiltration membrane, which comprises the following steps:
step one: preparing casting membrane solutions containing polysulfone (or polyether sulfone), polyimide, an additive and a first organic solvent with different concentrations, stirring after complete dissolution, standing for defoaming, and preparing a blending base membrane by a phase inversion method;
step two: after the surface of the blended basement membrane prepared in the step one is fully contacted with a certain amount of af-GQDs aqueous solution for a certain time, removing superfluous af-GQDs aqueous solution on the surface, washing with deionized water, and airing to obtain a modified basement membrane containing a nanomaterial intermediate layer;
step three: and (3) carrying out interfacial polymerization on the modified base film obtained in the step (II), an aqueous phase monomer solution containing a diamine or polyamine compound and a solution (organic phase monomer solution) containing a second organic solvent containing polybasic acyl chloride, and carrying out aftertreatment to obtain the hybrid composite film containing the af-GQDs interlayer.
Preferably, the total mass percentage concentration range of polysulfone (or polyether sulfone) and polyimide in the casting film liquid is 16-22%.
Preferably, the mass percentage content of polyimide in the film casting solution is 0.2% -2%; more preferably, the mass percentage content of polyimide in the film casting solution is 0.2% -1%.
Preferably, the content of the af-GQDs in the af-GQDs aqueous solution is 0.1 mg/L-50 mg/L; preferably, the content of the af-GQDs in the af-GQDs aqueous solution is 5mg/L to 20mg/L.
The third aspect of the invention discloses application of the hybrid composite reverse osmosis/nanofiltration membrane, which can be used for desalination of sea water and brackish water, treatment of industrial/municipal wastewater, and preparation of pure water and ultrapure water.
The technical scheme of the invention has obvious technical effects and progress and has substantial characteristics.
According to the preparation method of the hybrid composite membrane, the stability of the membrane is improved by preparing the af-GQDs intermediate layer on the polysulfone (polyethersulfone)/polyimide ultrafiltration or microfiltration base membrane and then performing interfacial polymerization.
The invention has the remarkable technical advantages that the af-GQDs nano material is deposited on the blending base film of polysulfone (polyethersulfone)/polyimide, and because a large amount of amino groups are arranged on the surface of the af-GQDs, the af-GQDs nano material and polyimide in the base film can be connected through covalent bonds, so that the af-GQDs intermediate layer is more firmly combined with the base film, and meanwhile, the dispersibility of the af-GQDs is improved; in the process of interfacial polymerization, af-GQDs can participate in interfacial polymerization reaction, so that nano materials are embedded into a cortical film material in a covalent bond mode, the stability of af-GQDs in the film is greatly improved, and the af-GQDs are used as connecting bands, so that the firmness between the cortex and a basal film layer is greatly improved, and due to the existence of-NH 2 on the surface of the af-GQDs, the hydrophilicity of the basal film is improved, the process of interfacial polymerization is controlled, and the separation performance of the film is improved.
Through the technical innovation, the invention solves the problem that the nano material is not tightly combined between an intermediate layer and a base film and a skin layer in the preparation process of the reverse osmosis/nanofiltration membrane taking polysulfone (polyether sulfone) as the base film, obtains remarkable technical progress, and has excellent application prospect in the desalination of sea water and brackish water and the municipal and industrial treatment fields.
Detailed Description
The invention is further illustrated by the following specific comparative examples and examples:
the diamine or polyamine compound used is m-phenylenediamine (MPD);
the polybasic acyl chloride is 1,3, 5-trimesoyl chloride (TMC);
the first organic solvent is N, N-dimethylacetamide (DMAc);
the additive used is polyethylene glycol (PEG-400);
the second organic solvent is n-hexane;
the rejection rate of the prepared membrane to sodium chloride and the corresponding water flux were measured with 2000mg/L aqueous sodium chloride solution at 25℃and a transmembrane pressure difference of 1.5 MPa.
Comparative example:
dissolving MPD in deionized water to prepare 2.0% (mass percent concentration, the same applies below) aqueous monomer solution;
TMC was dissolved in n-hexane to prepare a 0.15% organic phase monomer solution.
The preparation steps and conditions of the polyamide composite reverse osmosis membrane are as follows:
preparing a casting solution with polysulfone content of 18%, wherein the concentration of PEG-400 is 4% and the concentration of DMAc is 78%, dissolving the prepared casting solution for 24 hours, and standing and defoaming for 24 hours; sticking non-woven fabrics on the plate glass, scraping a film by using a film scraping machine, wherein the gap between a scraper and the plate glass is 230 mu m; after the film is scraped, evaporating for 10s in air, then immediately putting the scraped liquid film, the non-woven fabrics and the plate glass into deionized water at 25 ℃ for phase separation, taking out the prepared base film after 10min, repeatedly cleaning with the deionized water, and preserving in the deionized water for standby.
Taking out the base film from deionized water, airing, removing the aqueous phase monomer solution on the surface of the base film after the surface is fully contacted with the aqueous phase monomer solution for 8 seconds, naturally airing in the air at room temperature, then fully contacted with the organic phase monomer solution for 6 seconds, removing the redundant organic phase monomer solution on the surface of the film, and rapidly putting the film into deionized water to obtain the polyamide composite reverse osmosis membrane.
The prepared polyamide composite reverse osmosis membrane has a retention rate of 99.03 percent for 2000mg/L sodium chloride solution and a water permeability of 16.97L/(m) at 25 ℃ and a transmembrane pressure difference of 1.5MPa 2 .h.MPa)。
Example 1
The composition and concentration of the aqueous phase monomer solution and the organic phase monomer solution are the same as those of the comparative example;
ultrasonic treatment is carried out on an af-GQDs aqueous solution with the concentration of 10mg/L for 60min for standby; the average sheet diameter of the af-GQDs is 7.2nm; the average lamellar thickness of the af-GQDs is 1.6nm.
The film preparation steps are as follows:
step one: preparing a casting solution containing 17.5% of polysulfone and 0.5% of P84, wherein the concentration of PEG-400 is 4% and the concentration of DMAc is 78%, dissolving the prepared casting solution for 24 hours, standing for deaeration for 24 hours, and then scraping the membrane, wherein the steps of scraping the membrane are the same as those of the comparative example, so as to prepare the P84/polysulfone mixed ultrafiltration membrane;
step two: flatly attaching the P84/polysulfone mixed ultrafiltration membrane prepared in the first step on flat glass, flushing with deionized water, quickly pouring 30mL of af-GQDs aqueous solution on the surface of an ultrafiltration base membrane and keeping for 10min after no water drops are on the surface, removing superfluous af-GQDs aqueous solution on the surface, flushing with deionized water, and airing to obtain an af-GQDs modified base membrane;
step three: and (3) fully contacting the af-GQDs modified base film obtained in the step (II) with a water phase monomer solution for 8 seconds, removing the redundant water phase monomer solution on the surface of the film, airing, fully contacting the membrane with an organic phase monomer solution for 6 seconds, removing the organic phase monomer solution on the surface of the film, and placing the film in deionized water for hydrolysis to obtain the polyamide composite reverse osmosis film containing the af-GQDs intermediate layer.
The test conditions were the same as those of the comparative example.
The prepared polyamide composite reverse osmosis membrane has the retention rate of 99.13 percent of sodium chloride in 2000mg/L sodium chloride solution and the water permeability of 20.75L/(m) at 25 ℃ and a transmembrane pressure difference of 1.5MPa 2 h.MPa). The water permeability is improved by 22%, the retention rate is slightly increased, and the introduction of the middle layer is greatly shownThe separation performance of the membrane is improved.
Example 2
The difference from example 1 is that: the concentration of af-GQDs used in the second step is 15mg/L;
all other steps were the same as in example 1; the test conditions were the same as in example 1.
The prepared polyamide composite reverse osmosis membrane has the retention rate of 97.76 percent of sodium chloride in 2000mg/L sodium chloride solution and the water permeability of 23.28L/(m) at 25 ℃ and a transmembrane pressure difference of 1.5MPa 2 h.MPa). The introduction of the intermediate layer greatly increases the water permeability of the membrane.
Example 3
The difference from example 1 is that: the concentration of af-GQDs used in the second step is 20mg/L;
all other steps were the same as in example 1; the test conditions were the same as in example 1.
The prepared polyamide composite reverse osmosis membrane has the retention rate of 96.72 percent of sodium chloride in 2000mg/L sodium chloride solution and the water permeability of 24.68L/(m) at 25 ℃ and a transmembrane pressure difference of 1.5MPa 2 h.MPa). The introduction of the intermediate layer greatly increases the water permeability of the membrane.
Because the amino group of the intermediate layer and polyimide in the base film are subjected to crosslinking reaction, covalent bonds are formed, so that the intermediate layer of the nano material and the base film are tightly combined, and the intermediate layer is prevented from falling off from the base film; in addition, the amino group on the intermediate layer participates in interfacial polymerization reaction, and forms covalent bond with the cortex, so that the intermediate layer and the cortex are tightly combined, and the intermediate layer is prevented from falling off from the cortex. Therefore, the base film and the skin layer are tightly combined through the intermediate layer, the skin layer is prevented from falling off from the base film, the stability of the composite film is greatly improved, and the introduction of the intermediate layer is proved to greatly improve the stability and the separation performance of the film. The above examples illustrate that the addition of the af-GQDs interlayer has a great improvement on the membrane performance, and the prepared hybrid composite reverse osmosis/nanofiltration membrane has excellent performance, and achieves remarkable technical effects and progress.
It is noted that the above-mentioned examples are only preferred specific embodiments of the present invention and do not limit the present invention, and any embodiment falling within the scope of the present invention defined by the features of the claims or the equivalents thereof constitute patent rights infringing the present invention.

Claims (10)

1. A hybrid composite reverse osmosis/nanofiltration membrane is prepared by depositing a nano material intermediate layer on the surface of an ultrafiltration or microfiltration base membrane and forming a separation skin layer on the nano material intermediate layer through interfacial polymerization,
(1) The base film is prepared by scraping a layer of casting film liquid prepared by polysulfone or polyether sulfone and polyimide according to a certain proportion on the surface of non-woven fabric and carrying out phase inversion, wherein the mass percentage content of polyimide in the casting film liquid is 0.5% -2%;
(2) The nano material intermediate layer is composed of amino graphene quantum dots (af-GQDs);
(3) The separation skin layer is made of polyamide.
2. A hybrid composite reverse osmosis/nanofiltration membrane as defined in claim 1, wherein,
(1) The af-GQDs nano material intermediate layer is connected with the base film through a covalent bond;
(2) The af-GQDs nanometer material intermediate layer is connected with the separation cortex through covalent bonds.
3. A hybrid composite reverse osmosis/nanofiltration membrane as defined in claim 1, wherein,
(1) The average sheet diameter of the af-GQDs is less than or equal to 50nm;
(2) The average thickness of the af-GQDs is less than or equal to 5nm.
4. A hybrid composite reverse osmosis/nanofiltration membrane as defined in claim 1, wherein,
(1) The average sheet diameter of the af-GQDs is less than or equal to 10nm;
(2) The average thickness of the af-GQDs is less than or equal to 2nm.
5. The preparation method of the hybrid composite reverse osmosis/nanofiltration membrane is characterized by comprising the following steps of:
step one: preparing casting membrane solutions containing polysulfone or polyether sulfone, polyimide, additives and a first organic solvent with different concentrations, stirring after complete dissolution, standing for defoaming, and preparing a blending base membrane by a phase inversion method;
step two: after the surface of the blended basement membrane prepared in the step one is fully contacted with a certain amount of af-GQDs aqueous solution for a certain time, removing superfluous af-GQDs aqueous solution on the surface, washing with deionized water, and airing to obtain a basement membrane modified by the middle layer containing the nano material;
step three: and (3) carrying out interfacial polymerization on the modified base film obtained in the step (II), an aqueous monomer solution containing a diamine or polyamine compound and a solution containing a second organic solvent containing polybasic acyl chloride, and carrying out aftertreatment to obtain the hybrid composite film containing the af-GQDs intermediate layer.
6. The preparation method of the hybrid composite reverse osmosis/nanofiltration membrane as claimed in claim 5, wherein the total mass percentage concentration range of polysulfone or polyethersulfone and polyimide in the casting membrane solution is 16% -22%.
7. The preparation method of the hybrid composite reverse osmosis/nanofiltration membrane as claimed in claim 5, wherein the mass percentage of polyimide in the casting solution is 0.2% -2%.
8. The method for preparing a hybrid composite reverse osmosis/nanofiltration membrane according to claim 5, wherein the af-GQDs content in the af-GQDs aqueous solution is 0.1mg/L to 50mg/L.
9. The method for preparing a hybrid composite reverse osmosis/nanofiltration membrane according to claim 5, wherein the af-GQDs content in the af-GQDs aqueous solution is 5mg/L to 20mg/L.
10. The application of the hybrid composite reverse osmosis/nanofiltration membrane is characterized by being used for desalination of seawater and brackish water, treatment of industrial/municipal wastewater, and preparation of pure water and ultrapure water; wherein the hybrid composite reverse osmosis/nanofiltration membrane is a hybrid composite reverse osmosis/nanofiltration membrane according to any one of claims 1 to 4, or a hybrid composite reverse osmosis/nanofiltration membrane produced by the production method according to any one of claims 5 to 9.
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