CN111871232B - Double-layer composite reverse osmosis membrane - Google Patents
Double-layer composite reverse osmosis membrane Download PDFInfo
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- CN111871232B CN111871232B CN202010745857.1A CN202010745857A CN111871232B CN 111871232 B CN111871232 B CN 111871232B CN 202010745857 A CN202010745857 A CN 202010745857A CN 111871232 B CN111871232 B CN 111871232B
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The invention provides a double-layer composite reverse osmosis membrane, which comprises alumina hollow fibers serving as a supporting layer, a polyamide transition layer loaded on the supporting layer and a polyamide active layer loaded on the transition layer, wherein the polyamide active layer has a more compact polyamide structure than the polyamide transition layer. According to the invention, the polyamide transition layer is laid between the inorganic support body and the polyamide active layer, and the transition layer can make up for the defect of uneven surface pore diameter of the inorganic support body on one hand and can realize the purpose of coarse desalting on the other hand. According to the invention, unreacted acyl chloride in the polyamide transition layer is continuously combined with the water phase monomer in the active layer to form the polyamide active layer with a compact structure by a specific interfacial polymerization method, and the oil phase monomer flowing inside the hollow fiber can be subjected to interfacial polymerization with the water phase monomer solution in the active layer at the macroporous defect position so as to block the large defect hole (2-5 μm).
Description
Technical Field
The invention relates to a separation membrane, in particular to a polyamide reverse osmosis membrane with a double-layer structure.
Background
Membrane technology is becoming a new separation technology that finds increasing application in the production of water treatment and water purification industries. Compared with other separation technologies, the membrane separation technology has the characteristics of environmental protection, energy conservation, easy control and operation, and becomes one of important separation and purification means.
The composite membrane is a common membrane material and comprises a supporting layer and an active layer, wherein the supporting layer plays a role in supporting strength, the active layer plays a role in separation, and the supporting layer and the active layer play respective roles and are mutually synergistic. The common organic composite membrane and inorganic composite membrane are composite membranes, wherein a supporting layer and an active layer of the organic composite membrane are both organic materials, and a supporting layer and an active layer of the inorganic composite membrane are both inorganic materials. Compared with the organic composite membrane, the organic composite membrane has the advantages of low cost, good separation performance, weak solvent resistance and acid and alkali resistance, relatively high cost, high strength and good thermochemical stability. In order to achieve both advantages, many studies have been focused on using an inorganic material as a support and an organic material as an active layer. However, the compatibility between inorganic materials and organic materials is poor, the surface pore diameter of the inorganic support is not uniform, and some inorganic supports have the defect of macropores, so in order to overcome the problem of poor compatibility between the inorganic support and the organic active layer, documents such as CN106731884A and the like, a hydrophilic coating is coated on the inorganic support to be used as a transition layer.
Polyamide reverse osmosis membranes are a common type of composite membrane, and no literature has been available to date for attempting to prepare polyamide composite membranes using inorganic materials as support layers. The applicant has tried to prepare a polyamide composite membrane by coating an organic coating layer on an inorganic support, but found that separation of an active layer from a transition layer easily occurs due to the difference in the materials of the transition layer and the active layer in application, thereby decreasing the application stability of the membrane. Furthermore, the existing polyamide reverse osmosis membrane materials using organic materials as support layers have a trade-off effect, making it difficult to obtain reverse osmosis membrane materials having both good salt rejection and water flux.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a double-layer composite reverse osmosis membrane and a preparation method thereof.
The technical scheme adopted by the invention is specifically as follows:
a double-layer composite reverse osmosis membrane comprises alumina hollow fibers serving as a supporting layer, a polyamide transition layer loaded on the supporting layer and a polyamide active layer loaded on the transition layer, wherein the polyamide active layer has a more compact polyamide structure than the polyamide transition layer.
In the double-layer composite reverse osmosis membrane, the polyamide transition layer is prepared by interfacial polymerization and then placed in the water-phase monomer solution of the active layer, and the oil-phase monomer solution of the active layer continuously passes through the inside of the alumina hollow fiber.
The invention also provides a method for preparing the double-layer composite reverse osmosis membrane, which comprises the following steps:
(a) pretreatment of a carrier:
dipping the alumina hollow fiber in deionized water for ultrasonic treatment, dipping the alumina hollow fiber in the deionized water for 4 to 6 hours after the ultrasonic treatment, and drying for later use;
(b) a load transition layer:
mixing the aqueous phase monomer of the transition layer, sodium hydroxide, a surfactant and water to obtain an aqueous phase monomer solution of the transition layer; mixing a transition layer oil phase monomer with an organic solvent to obtain a transition layer oil phase monomer solution; sealing two ends of the alumina hollow fiber, immersing the alumina hollow fiber into the aqueous phase monomer solution of the transition layer for 30-120s, taking out and removing the redundant solution on the surface of the fiber; continuously immersing the alumina hollow fiber into the transition layer oil phase monomer solution for 30-120s, taking out the fiber after the immersion is finished, and obtaining the alumina hollow fiber loaded with the transition layer after the surface solvent is volatilized;
(c) loading an active layer:
mixing the active layer aqueous phase monomer, sodium hydroxide, a surfactant and water to obtain an active layer aqueous phase monomer solution; mixing an active layer oil phase monomer with an organic solvent to obtain an active layer oil phase monomer solution; and (c) opening the seals at the two ends of the hollow fiber treated in the step (b), connecting the hollow fiber with an active layer oil phase monomer solution source pipeline to continuously introduce the active layer oil phase monomer solution into the hollow fiber, immediately soaking the hollow fiber in the active layer oil phase monomer solution for 60-180s, and drying after the soaking is finished to obtain the double-layer composite reverse osmosis membrane.
In the method, the water phase monomer of the transition layer is piperazine, and the oil phase monomer of the transition layer is trimesoyl chloride.
In the method, the water phase monomer of the active layer is m-phenylenediamine, and the oil phase monomer of the active layer is trimesoyl chloride.
In the method, the concentrations of the transition layer aqueous phase monomer, the sodium hydroxide and the surfactant in the transition layer aqueous phase monomer solution are 1-2wt%, 0-1wt% and 0.1-1wt% in sequence; the concentration of the transition layer oil phase monomer in the transition layer oil phase monomer solution is 1-3 wt%.
In the method, the concentrations of the active layer aqueous phase monomer, the sodium hydroxide and the surfactant in the active layer aqueous phase monomer solution are 2-5wt%, 0-1wt% and 0.1-1wt% in sequence; the concentration of the active layer oil phase monomer in the active layer oil phase monomer solution is 1-3wt%, and preferably, the active layer oil phase monomer solution and the transition layer oil phase monomer solution have the same components and concentrations.
In the method, the surfactant is one selected from sodium dodecyl benzene sulfonate, N-methyl pyrrolidone or sodium lauryl sulfate, and the solvent is one selected from cyclohexane, N-hexane, N-heptane and octane.
In the method, the flow speed of the oil phase monomer solution of the active layer in the hollow fiber is 0.2-0.5 ml/min.
The invention has the technical characteristics and advantages that:
1. according to the invention, the polyamide transition layer is laid between the inorganic support body and the polyamide active layer, and the transition layer can make up for the defect of uneven surface pore diameter of the inorganic support body on one hand and can realize the purpose of coarse desalting on the other hand.
2. According to the invention, unreacted acyl chloride in the polyamide transition layer is continuously combined with the water phase monomer in the active layer to form the polyamide active layer with a compact structure by a specific interfacial polymerization method, and the oil phase monomer flowing inside the hollow fiber can be subjected to interfacial polymerization with the water phase monomer solution in the active layer at the macroporous defect position so as to block the large defect hole (2-5 μm).
3. According to the invention, the alumina is used as the support body, the surface hydroxyl can be combined with acyl chloride, the bonding force between the support layer and the transition layer is improved, and the hydrophilicity of the alumina can be beneficial to spreading of the water-phase monomer.
4. The double-layer polyamide layer is arranged, so that the thickness of the compact active layer can be reduced under the condition that the thickness of the membrane is kept to be certain, and the flux of reverse osmosis can be improved.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to examples.
The first embodiment is as follows:
the double-layer composite reverse osmosis membrane prepared in this example includes an alumina hollow fiber as a support layer, a transition layer supported on the support layer, and a polyamide active layer supported on the transition layer.
The method adopted by the embodiment comprises the following steps:
(a) pretreatment of a carrier:
soaking alpha-alumina hollow fiber (with average pore diameter of 0.9 μm) in deionized water for ultrasonic treatment, soaking in deionized water for 4h after ultrasonic treatment, and drying for later use;
(b) a load transition layer:
mixing piperazine, sodium hydroxide, sodium dodecyl sulfate and water to obtain a transition layer aqueous phase monomer solution, wherein the concentrations of the piperazine, the sodium hydroxide and the sodium dodecyl sulfate are 2wt%, 0.5 wt% and 1wt% in sequence; trimesoyl chloride and normal hexane are mixed to be used as a transition layer oil phase monomer solution, wherein the concentration of the trimesoyl chloride is 2 wt%.
The specific operation of the step is as follows: sealing two ends of the alumina hollow fiber, immersing the alumina hollow fiber into the aqueous phase monomer solution of the transition layer for 30s, taking out and removing the redundant solution on the surface of the fiber; continuously immersing the alumina hollow fiber into the transition layer oil phase monomer solution for 90s, taking out the fiber after the immersion is finished, and obtaining the alumina hollow fiber loaded with the transition layer after the surface solvent is volatilized;
(c) loading an active layer:
mixing m-phenylenediamine, sodium hydroxide, sodium dodecyl sulfate and water to obtain an active layer aqueous phase monomer solution, wherein the concentrations of the m-phenylenediamine, the sodium hydroxide and the sodium dodecyl sulfate are 3wt%, 1wt% and 1wt% in sequence; the transition layer oil phase monomer solution is used as the active layer oil phase monomer solution.
The step is specifically operated; and (c) opening the seals at the two ends of the hollow fiber treated in the step (b), connecting the hollow fiber with an active layer oil phase monomer solution source pipeline to enable the active layer oil phase monomer solution to be continuously introduced into the hollow fiber, enabling the flow rate to be 0.5ml/min, immediately soaking the hollow fiber in the active layer oil phase monomer solution for 120s, and drying after the soaking is finished to obtain the double-layer composite reverse osmosis membrane.
Comparative example 1
The double-layer composite reverse osmosis membrane prepared by the comparative example comprises alumina hollow fibers serving as a supporting layer, a transition layer supported on the supporting layer and a polyamide active layer supported on the transition layer.
The method adopted by the embodiment comprises the following steps:
(a) pretreatment of a carrier:
soaking alpha-alumina hollow fiber (with average pore diameter of 0.9 μm) in deionized water for ultrasonic treatment, soaking in deionized water for 4h after ultrasonic treatment, and drying for later use;
(b) a load transition layer:
mixing piperazine, sodium hydroxide, sodium dodecyl sulfate and water to obtain a transition layer aqueous phase monomer solution, wherein the concentrations of the piperazine, the sodium hydroxide and the sodium dodecyl sulfate are 2wt%, 0.5 wt% and 1wt% in sequence; trimesoyl chloride and normal hexane are mixed to be used as a transition layer oil phase monomer solution, wherein the concentration of the trimesoyl chloride is 2 wt%.
The specific operation of the step is as follows: sealing two ends of the alumina hollow fiber, immersing the alumina hollow fiber into the aqueous phase monomer solution of the transition layer for 30s, taking out and removing the redundant solution on the surface of the fiber; continuously immersing the alumina hollow fiber into the transition layer oil phase monomer solution for 90s, taking out the fiber after the immersion is finished, and obtaining the alumina hollow fiber loaded with the transition layer after the surface solvent is volatilized;
(c) loading an active layer:
mixing m-phenylenediamine, sodium hydroxide, sodium dodecyl sulfate and water to obtain an aqueous monomer solution of an active layer, wherein the concentrations of the m-phenylenediamine, the sodium hydroxide and the sodium dodecyl sulfate are 3wt%, 1wt% and 1wt% in sequence.
The step is specifically operated; and (c) continuously dipping the two ends of the hollow fiber treated in the step (b) into the water-phase monomer solution of the active layer for 120s, taking out the fiber after dipping is finished, and volatilizing the surface solvent to obtain the alumina hollow fiber loaded with the transition layer.
Comparative example 2
The double-layer composite reverse osmosis membrane prepared by the comparative example comprises alumina hollow fibers serving as a supporting layer, a transition layer supported on the supporting layer and a polyamide active layer supported on the transition layer.
The method adopted by the embodiment comprises the following steps:
(a) pretreatment of a carrier:
soaking alpha-alumina hollow fiber (with average pore diameter of 0.9 μm) in deionized water for ultrasonic treatment, soaking in deionized water for 4h after ultrasonic treatment, and drying for later use;
(b) a load transition layer:
mixing piperazine, sodium hydroxide, sodium dodecyl sulfate and water to obtain a transition layer aqueous phase monomer solution, wherein the concentrations of the piperazine, the sodium hydroxide and the sodium dodecyl sulfate are 2wt%, 0.5 wt% and 1wt% in sequence; trimesoyl chloride and normal hexane are mixed to be used as a transition layer oil phase monomer solution, wherein the concentration of the trimesoyl chloride is 2 wt%.
The specific operation of the step is as follows: sealing two ends of the alumina hollow fiber, immersing the alumina hollow fiber into the aqueous phase monomer solution of the transition layer for 30s, taking out and removing the redundant solution on the surface of the fiber; continuously immersing the alumina hollow fiber into the transition layer oil phase monomer solution for 90s, taking out the fiber after the immersion is finished, and obtaining the alumina hollow fiber loaded with the transition layer after the surface solvent is volatilized;
(c) loading an active layer:
mixing piperazine, sodium hydroxide, sodium dodecyl sulfate and water to obtain an active layer aqueous phase monomer solution, wherein the concentrations of the m-phenylenediamine, the sodium hydroxide and the sodium dodecyl sulfate are 3wt%, 1wt% and 1wt% in sequence; the transition layer oil phase monomer solution is used as the active layer oil phase monomer solution.
The step is specifically operated; and (c) opening the seals at the two ends of the hollow fiber treated in the step (b), connecting the hollow fiber with an active layer oil phase monomer solution source pipeline to enable the active layer oil phase monomer solution to be continuously introduced into the hollow fiber, enabling the flow rate to be 0.5ml/min, immediately soaking the hollow fiber in the active layer oil phase monomer solution for 120s, and drying after the soaking is finished to obtain the double-layer composite reverse osmosis membrane.
Comparative example No. three
The double-layer composite reverse osmosis membrane prepared by the comparative example comprises alumina hollow fibers serving as a supporting layer, a transition layer supported on the supporting layer and a polyamide active layer supported on the transition layer.
The method adopted by the embodiment comprises the following steps:
(a) pretreatment of a carrier:
soaking alpha-alumina hollow fiber (with average pore diameter of 0.9 μm) in deionized water for ultrasonic treatment, soaking in deionized water for 4h after ultrasonic treatment, and drying for later use;
(b) a load transition layer:
mixing m-phenylenediamine, sodium hydroxide, sodium dodecyl sulfate and water to obtain a transition layer aqueous phase monomer solution, wherein the concentrations of piperazine, sodium hydroxide and sodium dodecyl sulfate are 2wt%, 0.5 wt% and 1wt% in sequence; trimesoyl chloride and normal hexane are mixed to be used as a transition layer oil phase monomer solution, wherein the concentration of the trimesoyl chloride is 2 wt%.
The specific operation of the step is as follows: sealing two ends of the alumina hollow fiber, immersing the alumina hollow fiber into the aqueous phase monomer solution of the transition layer for 30s, taking out and removing the redundant solution on the surface of the fiber; continuously immersing the alumina hollow fiber into the transition layer oil phase monomer solution for 90s, taking out the fiber after the immersion is finished, and obtaining the alumina hollow fiber loaded with the transition layer after the surface solvent is volatilized;
(c) loading an active layer:
mixing m-phenylenediamine, sodium hydroxide, sodium dodecyl sulfate and water to obtain an active layer aqueous phase monomer solution, wherein the concentrations of the m-phenylenediamine, the sodium hydroxide and the sodium dodecyl sulfate are 3wt%, 1wt% and 1wt% in sequence; the transition layer oil phase monomer solution is used as the active layer oil phase monomer solution.
The step is specifically operated; and (c) opening the seals at the two ends of the hollow fiber treated in the step (b), connecting the hollow fiber with an active layer oil phase monomer solution source pipeline to enable the active layer oil phase monomer solution to be continuously introduced into the hollow fiber, enabling the flow rate to be 0.5ml/min, immediately soaking the hollow fiber in the active layer oil phase monomer solution for 120s, and drying after the soaking is finished to obtain the double-layer composite reverse osmosis membrane.
The results of NaCl salt rejection and water flux (unit GFD) and salt rejection (%) of 5 samples each of the polyamide composite membranes prepared in example 1 and comparative examples 1 to 3 were shown in the following table in a 2000ppm NaCl aqueous solution under test conditions of 225psi operating pressure, 25 ℃ temperature and 7 pH
TABLE 1 Properties of samples of examples and comparative examples
The data in the table show that the embodiment of the invention can well compensate the defects of the inorganic support and meet the requirements on the separation performance.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (7)
1. A double-layer composite reverse osmosis membrane is characterized by comprising alumina hollow fibers serving as a supporting layer, a polyamide transition layer loaded on the supporting layer and a polyamide active layer loaded on the transition layer, wherein the polyamide active layer has a more compact polyamide structure than the polyamide transition layer; the polyamide transition layer is prepared by interfacial polymerization and then is placed in the water-phase monomer solution of the active layer, and the oil-phase monomer solution of the active layer continuously passes through the inside of the alumina hollow fiber; the alumina hollow fiber has defect pores with the diameter of 2-5 mu m; the flow speed of the active layer oil phase monomer solution in the alumina hollow fiber is 0.2-0.5 ml/min; the oil phase monomer flowing inside the hollow alumina fiber is polymerized with the water phase monomer solution in the active layer at the defect hole to block the defect hole.
2. A method of making a two-layer composite reverse osmosis membrane of claim 1 comprising the steps of:
(a) pretreatment of a carrier:
dipping the alumina hollow fiber in deionized water for ultrasonic treatment, dipping the alumina hollow fiber in the deionized water for 4 to 6 hours after the ultrasonic treatment, and drying for later use;
(b) a load transition layer:
mixing the aqueous phase monomer of the transition layer, sodium hydroxide, a surfactant and water to obtain an aqueous phase monomer solution of the transition layer; mixing a transition layer oil phase monomer with an organic solvent to obtain a transition layer oil phase monomer solution; sealing two ends of the alumina hollow fiber, immersing the alumina hollow fiber into the aqueous phase monomer solution of the transition layer for 30-120s, taking out and removing the redundant solution on the surface of the fiber; continuously immersing the alumina hollow fiber into the transition layer oil phase monomer solution for 30-120s, taking out the fiber after the immersion is finished, and obtaining the alumina hollow fiber loaded with the transition layer after the surface solvent is volatilized;
(c) loading an active layer:
mixing the active layer aqueous phase monomer, sodium hydroxide, a surfactant and water to obtain an active layer aqueous phase monomer solution; mixing an active layer oil phase monomer with an organic solvent to obtain an active layer oil phase monomer solution; and (c) opening the seals at the two ends of the hollow fiber treated in the step (b), connecting the hollow fiber with an active layer oil phase monomer solution source pipeline to continuously introduce the active layer oil phase monomer solution into the hollow fiber, immediately soaking the polyamide composite membrane in the active layer water phase monomer solution for 60-180s, and drying after the soaking is finished to obtain the double-layer composite reverse osmosis membrane.
3. The method of claim 2, wherein the transition layer aqueous phase monomer is piperazine and the transition layer oil phase monomer is trimesoyl chloride.
4. The method of claim 2, wherein the active layer aqueous phase monomer is m-phenylenediamine and the active layer oil phase monomer is trimesoyl chloride.
5. The method according to claim 2, wherein the concentrations of the transition layer aqueous phase monomer, the sodium hydroxide and the surfactant in the transition layer aqueous phase monomer solution are 1-2wt%, 0-1wt% and 0.1-1wt% in sequence; the concentration of the transition layer oil phase monomer in the transition layer oil phase monomer solution is 1-3 wt%.
6. The method according to claim 2, wherein the concentrations of the aqueous monomer of the active layer, the sodium hydroxide and the surfactant in the aqueous monomer solution of the active layer are 2 to 5wt%, 0 to 1wt% and 0.1 to 1wt% in this order; the concentration of the active layer oil phase monomer in the active layer oil phase monomer solution is 1-3 wt%.
7. The method according to claim 2, wherein the surfactant is one selected from sodium dodecylbenzenesulfonate, N-methylpyrrolidone or sodium lauryl sulfate, and the solvent is one selected from cyclohexane, N-hexane, N-heptane and octane.
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| CN103071403A (en) * | 2013-01-31 | 2013-05-01 | 北京碧水源膜科技有限公司 | Double desalting layer composite reverse osmosis membrane and preparation method thereof |
| CN105169972A (en) * | 2015-09-30 | 2015-12-23 | 北京新源国能科技有限公司 | Hollow fiber nanofiltration membrane and preparation method for producing hollow fiber nanofiltration membrane |
| CN110559887A (en) * | 2019-08-29 | 2019-12-13 | 浙江工业大学 | Preparation method for preparing ultrathin composite membrane by interfacial microfluidization method |
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| CN105169972A (en) * | 2015-09-30 | 2015-12-23 | 北京新源国能科技有限公司 | Hollow fiber nanofiltration membrane and preparation method for producing hollow fiber nanofiltration membrane |
| CN110559887A (en) * | 2019-08-29 | 2019-12-13 | 浙江工业大学 | Preparation method for preparing ultrathin composite membrane by interfacial microfluidization method |
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