CN116078177B - Hollow fiber forward osmosis membrane, preparation method and application - Google Patents
Hollow fiber forward osmosis membrane, preparation method and application Download PDFInfo
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- CN116078177B CN116078177B CN202310200036.3A CN202310200036A CN116078177B CN 116078177 B CN116078177 B CN 116078177B CN 202310200036 A CN202310200036 A CN 202310200036A CN 116078177 B CN116078177 B CN 116078177B
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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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
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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
- B01D67/0002—Organic membrane manufacture
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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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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- 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
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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Abstract
The invention provides a hollow fiber forward osmosis membrane, a preparation method and application thereof. According to the invention, the polyamide porous framework layer is directly formed on the inner wall of the reinforcing layer, so that the polyamide porous framework layer cannot be peeled off or fall off in the water treatment process, and when the membrane wires are washed, the polyamide porous framework layer can fall off from the reinforcing layer easily due to low composite strength of the polyamide and the reinforcing layer, so that pollutants are carried to fall off from the reinforcing layer, and then the polyamide porous framework layer carrying the pollutants to fall off flows out along with washing liquid, so that membrane pollution is removed. Then the porous framework layer can be formed again through simple chemical treatment, the water flux of the forward osmosis membrane is recovered, and the service life of the membrane is prolonged.
Description
Technical Field
The invention relates to the technical field of water treatment, and particularly discloses a hollow fiber forward osmosis membrane, a preparation method and application thereof.
Background
The forward osmosis technology is a spontaneous transmembrane transport process of water molecules by utilizing osmotic pressure difference at two sides of a solution, and is a naturally occurring osmosis process. FO refers to the process in which water flows from the low osmotic side to the high osmotic side through a membrane with selectivity, the driving force for the overall process being from the osmotic pressure differential across the membrane, so that the FO process is spontaneous. Advantages of FO technology include: (1) low pressure or even no pressure operation, thus lower energy consumption; (2) Almost completely entrapping a plurality of pollutants, and has good separation effect; (3) simple membrane process and equipment, etc.
Forward osmosis membranes are the core of forward osmosis technology, and are mainly used for trapping monovalent and divalent ions in water, and generally only allowing water molecules to pass through. The forward osmosis membrane material initially used cellulose acetate and derivatives of cellulose acetate. However, cellulose acetate membranes are not suitable for repeated cleaning, have poor oxidation resistance and chemical resistance, have low mechanical strength, and can accelerate the degradation of the membrane skeleton at too high a temperature or alkalinity, and the membrane skeleton can be biodegraded. Polybenzimidazole membranes are another forward osmosis membrane after the development of cellulose acetate membranes. However, the porous structure inside benzimidazole membranes causes severe concentration polarization effects inside the benzimidazole membranes and poor solubility of the membrane material itself. The most advanced forward osmosis membrane is a polyamide thin layer composite membrane at present, which has a better salt interception effect, can overcome lower water flux compared with an integral asymmetric membrane, and can be used in a wider temperature and pH range.
However, the pores inside the support layer of the polyamide thin layer composite membrane are reduced or even blocked due to deposition or propagation of particles, colloid particles, solute molecules or bacteria, viruses and the like, and form a bridge effect, so that the pores inside the support layer become small and even blocked, and the membrane passing resistance is increased, thereby reducing the water flux of the membrane, increasing the cost, increasing the instability in the operation process and the like. Moreover, membrane contamination is difficult to recover, severely affecting the useful life of the membrane.
Disclosure of Invention
In view of the above-described drawbacks or deficiencies of the prior art, the present application aims to provide a hollow fiber forward osmosis membrane capable of eliminating membrane fouling and effectively restoring water flux, to solve at least one of the above-described technical problems.
It is an object of the present invention to provide a hollow fiber forward osmosis membrane comprising an active layer, a porous support layer, a reinforcing layer and a porous architecture layer in this order from the outside to the inside.
The porous framework layer is a polyamide porous framework layer, and the thickness of the porous framework layer is 0.5-1.2 mu m.
Preferably, the porous architecture layer is preferably a polyamide porous architecture layer having a regular striped structure.
Preferably, the pore diameter of the porous framework layer is 15 nm-50 nm.
Preferably, the porous architecture layer is formed inside the reinforcement layer by means of interfacial polymerization.
Preferably, the first solution containing anhydrous piperazine is adsorbed on the inner wall of the reinforcement layer, and then interfacial polymerization is performed in the second solution containing trimesoyl chloride.
Preferably, the second solution further comprises a diffusion retarder.
Preferably, the interfacial polymerization reaction time for forming the porous structure layer is 20 s-60 s.
Preferably, the reaction temperature for forming the porous framework layer is 0 ℃ to 10 ℃.
Preferably, the reinforcing layer is a hollow tube, preferably a woven tube made of polyester fiber or terylene.
Preferably, the mesh number of the tube wall of the hollow tube is 30-40 meshes.
Preferably, the porous support layer comprises polysulphone and/or polyethersulphone.
Preferably, the polysulfone and polyethersulfone are independently modified with a hydrophilic polymer.
Preferably, the hydrophilic polymer is one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone, and more preferably polyvinylpyrrolidone.
Preferably, the thickness of the porous supporting layer is 30-100 μm.
Preferably, the pore diameter of the porous supporting layer is 3-25 nm.
Preferably, the active layer is a polyamide active layer, preferably a polyamide active layer having a surface with a regular stripe structure.
Preferably, the thickness of the active layer is 3-10 μm.
Preferably, the aperture of the active layer is 3-25 nm.
The second object of the present invention is to provide a method for producing a hollow fiber forward osmosis membrane, comprising: firstly, forming a porous supporting layer on the outer wall of the reinforcing layer, then forming an active layer on the porous supporting layer, and finally forming a porous framework layer on the inner wall of the reinforcing layer.
Preferably, the formation of the framework layer on the inner wall of the reinforcing layer is performed at 0-10 ℃.
Preferably, the method of forming an architecture layer inside the reinforcement layer comprises: placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath, firstly introducing a first solution into the membrane wire, adsorbing the first solution on the inner wall of the membrane wire, then discharging the first solution, drying the surface of the inner wall of the membrane wire, introducing a second solution, discharging the second solution after the reaction, and drying the membrane wire.
Preferably, the residence time of the first solution and the second solution in the membrane filament is 20-60 s independently.
Preferably, the first solution comprises an aqueous phase high activity monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of water, 1.5-2.5 parts of anhydrous piperazine and 0-7.5 parts of diffusion retarder.
Preferably, the second solution comprises an organic phase highly reactive monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of normal hexane and 0.08-0.15 part of trimesic acid chloride.
Preferably, the diffusion retarder comprises one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone, preferably polyvinylpyrrolidone.
Preferably, the method of forming the porous support layer on the outer wall of the reinforcing layer includes: and uniformly coating the casting solution on the outer wall of the reinforcing layer, and then soaking the reinforcing layer in a coagulating bath.
Preferably, after the membrane casting solution is defoamed, the membrane casting solution is uniformly coated on the outer wall of the reinforcing layer.
Preferably, the casting film liquid comprises the following raw materials in parts by weight: 10-20 parts of polysulfone and/or polyethersulfone, 0-5 parts of hydrophilic polymer and 80-90 parts of N-methylpyrrolidone.
Preferably, the formation of the active layer on the porous support layer is performed at 20 ℃ to 45 ℃.
Preferably, the method of forming an active layer on a porous support layer includes: firstly, adding water into the membrane wire after the porous supporting layer is formed, immersing the outer wall of the membrane wire into the third solution, then taking out the membrane wire, drying the outer wall surface of the membrane wire, immersing the membrane wire into the fourth solution, and taking out and drying the membrane wire after the reaction.
Preferably, the soaking time of the membrane filaments in the third solution is 1-3 min.
Preferably, the soaking time of the membrane filaments in the fourth solution is 0.5-1.5 min.
Preferably, the third solution comprises an aqueous phase high activity monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of water, 1.5-2.5 parts of anhydrous piperazine and 0-7.5 parts of diffusion retarder.
Preferably, the fourth solution comprises an organic phase high activity monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of normal hexane and 0.08-0.15 part of trimesic acid chloride.
Preferably, the diffusion retarder comprises one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone, preferably polyvinylpyrrolidone.
It is a further object of the present invention to provide the use of a hollow fiber forward osmosis membrane for water treatment applications.
Preferably, the water flux of the hollow fiber forward osmosis membrane is reduced to 6L.m -2 ·h -1 ~12L·m -2 ·h -1 After cleaning the contaminated porous architecture layer, the architecture layer is formed again inside the reinforcement layer.
The beneficial effects of the invention include:
in the invention, the polyamide porous framework layer is directly formed on the inner wall of the reinforcing layer, and is not peeled off or shed in the use process, and when the membrane wire is washed, the polyamide porous framework layer can be shed from the reinforcing layer easily due to lower strength of direct compounding of the polyamide and the reinforcing layer, so that carrying pollutants shed from the reinforcing layer and then flow out along with the washing liquid, thereby removing membrane pollution. Then the porous framework layer can be formed again through simple chemical treatment, the water flux of the forward osmosis membrane is recovered, and the service life of the membrane is prolonged.
Detailed Description
In the following description, certain specific details are included to provide a thorough understanding of various disclosed embodiments. One skilled in the relevant art will recognize, however, that the embodiments may be practiced without one or more of the specific details, or with other methods, components, materials, etc.
Throughout this specification, unless the context requires otherwise, the words "comprise" and "comprising" are to be interpreted in an open, inclusive sense, i.e. "including but not limited to.
Reference throughout this specification to "one embodiment" or "an embodiment" or "one preferred embodiment" or "certain embodiments" means that a particular reference element, structure, or feature described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrase "in one embodiment" or "in an embodiment" or "in a preferred embodiment" or "in certain embodiments" appearing in various places throughout the specification are not necessarily all referring to the same embodiment. Furthermore, the particular elements, structures, or features may be combined in any suitable manner in one or more embodiments.
According to a first aspect of the present invention, there is provided a hollow fiber forward osmosis membrane comprising, in order from the outside to the inside, an active layer, a porous support layer, a reinforcing layer and a porous architecture layer.
The porous framework layer is a polyamide porous framework layer, and the thickness of the porous framework layer is 0.5-1.2 mu m.
In the invention, the active layer plays a role in filtration, the porous supporting layer is used for supporting the active layer, the reinforcing layer is used for supporting the whole hollow fiber forward osmosis membrane wire, and the porous framework layer is used for gathering pollutants and can carry the pollutants to fall off from the reinforcing layer.
In the invention, when the thickness of the porous architecture layer exceeds 1.2 mu m, on one hand, after the thickness exceeds 1.2 mu m, the strength of the architecture layer is obviously enhanced, and the architecture layer is difficult to break and peel; on the other hand, the water flux of the hollow fiber forward osmosis membrane is greatly influenced, so that the water flux of the hollow fiber forward osmosis membrane is obviously reduced, and the water treatment efficiency is influenced. When the thickness of the porous framework layer is smaller than 0.5 mu m, on one hand, the porous framework layer is not easy to form, and the effect of trapping pollutants to form a pollutant layer is not achieved; on the other hand, the strength of the porous framework layer is smaller, and the porous framework layer is easy to break in the use process. Thus, the thickness of the porous structure layer is 0.5 to 1.2 μm, for example, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm or 1.2 μm.
In the invention, the polyamide porous framework layer is directly formed on the inner wall of the reinforcing layer, and is not peeled off or fallen off in the use process, and when the membrane wire is washed, the polyamide porous framework layer can fall off from the reinforcing layer easily due to low composite strength of the polyamide and the reinforcing layer and then flows out along with the washing liquid, so that membrane pollution is removed. And then carrying out interfacial polymerization on the inner wall of the enhancement layer in the membrane wire, thus forming the polyamide porous framework layer again.
Membrane fouling in the general sense is that the pores inside the porous support layer are occupied by the draw solution, raw material solutes and contaminants and form a bridge effect such that the pores inside the support layer are filled with solute accumulation and compaction, the water flux is greatly reduced and cannot be recovered. In the invention, a porous framework layer is formed on the inner wall of the reinforcing layer, so that pollutants are blocked by the framework layer and the pollutant layer of the surface bridge frame of the framework layer in the use process, and are accumulated on the porous framework layer to form a pollution layer, and the pollution layer can be cleaned by using pure water in the daily use process. When the pure water flowing cleaning effect is poor, the porous framework layer can be peeled off by the cleaning means such as pressurization, pulse, vibration, medicament soaking and the like, so that the carried pollutants fall off from the enhancement layer, and the membrane pollution is removed. Then the porous framework layer can be formed again through simple chemical treatment, the water flux of the membrane wires is recovered, and the service life of the membrane is prolonged.
In a preferred embodiment of the invention, the porous architecture layer is a polyamide porous architecture layer having a regular striped structure.
In the invention, the regular stripe structure of the porous framework layer is a natural pattern with periodic regular variation formed by interaction of two monomers for generating polyamide, and the structure can provide the porous framework layer with interception performance enough for forming a pollutant layer, and has excellent destructibility due to ultra-thin thickness.
Preferably, the pore diameter of the porous framework layer is 15 nm-50 nm.
In the present invention, the pore size of the porous architecture layer exceeds 50 a nm a, and the interception rate of contaminants by the porous architecture layer is reduced. The pore diameter of the porous framework layer is smaller than 15nm, the water flux of the forward osmosis membrane is rapidly reduced in the use process, and the cleaning frequency is increased. Thus, the pore size of the porous structure layer is 15nm to 50nm, for example, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm.
In a preferred embodiment of the invention, the porous architecture layer is formed inside the reinforcement layer by means of interfacial polymerization.
Preferably, the first solution containing anhydrous piperazine is adsorbed on the inner wall of the reinforcement layer, and then interfacial polymerization is performed in the second solution containing trimesoyl chloride.
Preferably, the first solution further comprises a diffusion retarder.
The interfacial polymerization is to adopt two high-activity monomers, namely anhydrous piperazine and trimesoyl chloride, to be respectively dissolved in water and organic solution to prepare mutually-insoluble solution, and the polymerization is carried out at the interface.
In the invention, the porous framework layer is formed in an interfacial polymerization mode, so that the method for using the interfacial polymerization is easier to operate because the medium fiber membrane filaments are very thin; in a second aspect, the interfacial polymerization method facilitates control of the thickness of the polymer film formed; in the third aspect, the interfacial polymerization method is more advantageous for controlling the diffusion rate of two monomers involved in the reaction, thereby more advantageous for controlling the formation of a regular striped structure.
Preferably, the interfacial polymerization reaction time for forming the porous structure layer is 20s to 60s, for example, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s or 60s.
Preferably, the reaction temperature for forming the porous structure layer is 0 ℃ to 10 ℃, for example, 0 ℃, 1 ℃, 2 ℃, 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃, or 10 DEG C
In the invention, in the process of interfacial polymerization, the thickness of the porous framework layer is gradually increased along with the progress of interfacial polymerization, the roughness of the surface of the porous framework layer is firstly reduced and then increased, when the surface roughness is reduced to the lowest point and begins to be increased, the strength of the porous framework layer begins to be obviously increased, and the porous framework layer is not easily damaged, so that the porous framework layer is difficult to peel from the reinforcing layer. The thickness and surface roughness of the porous architecture layer can be controlled by controlling the reaction time or reaction temperature using interfacial polymerization, thereby allowing the porous architecture layer to be easily peeled from the reinforcing layer.
In a preferred embodiment of the invention, the reinforcing layer is a hollow tube, preferably a woven tube of polyester fibers and/or polyester. The reinforced layer is a woven tube made of polyester fiber and polyester material, so that on one hand, the composite strength of the porous supporting layer and the reinforced layer is improved, and the service life is prolonged; on the other hand, when the polyamide porous structure layer is directly compounded with the polyester fiber and polyester material reinforcing layer, the composite strength is low, and the polyamide porous structure layer is beneficial to stripping from the reinforcing layer during flushing.
Preferably, the mesh number of the tube wall of the hollow tube is 30-40 meshes.
In a preferred embodiment of the present invention, the porous support layer comprises polysulfone or polyethersulfone in order to provide good stability, selectivity and permeability to the porous support layer.
In the present invention, the porous support layer is, for example, a polysulfone porous support layer, a polyethersulfone porous support layer, or a porous support layer prepared by mixing polysulfone and polyethersulfone.
Preferably, the polysulfone and polyethersulfone are independently modified with a hydrophilic polymer, preferably one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone, more preferably polyvinylpyrrolidone.
Hydrophilic modification of the support layer can increase the hydrophilicity of the surface of the support layer, optimize the pore size distribution state and the porosity of the internal structure, and promote the transportation of water molecules, thereby increasing the water flux. The surface of the hydrophilically modified supporting layer is of a uniform pore structure, the section of the supporting layer is of a uniform and compact spongy structure, a substrate with uniform pore structure distribution can provide favorable attachment sites for the load of the active layer, and an active layer with lower roughness is generated on the surface of the porous supporting layer.
Preferably, the thickness of the porous supporting layer is 30-100 μm.
The smaller the thickness of the porous supporting layer is, the shorter the water molecule transmembrane transport path is, the smaller the mass transfer resistance is, and the water flux is improved. In the present invention, when the thickness of the porous support layer is more than 100 μm, the water flux of the membrane is greatly reduced; when the thickness of the porous support layer is less than 30 μm, the support strength for the active layer is significantly reduced. Therefore, the thickness of the porous support layer is preferably 30 to 100 μm, for example, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm.
Preferably, the pore diameter of the porous supporting layer is 3-25 nm.
In the present invention, the pore diameter of the porous support layer is, for example, 3nm, 5nm, 8nm, 10nm, 12nm, 15nm, 17nm, 20nm, 22nm or 25nm.
Preferably, the porosity of the porous supporting layer is 70% -90%.
In the present invention, the porous support layer has a porosity of, for example, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 88%, or 90%.
In a preferred embodiment of the invention, the active layer is a polyamide active layer, preferably a polyamide active layer having a regular stripe structure.
The polyamide as the active layer has the advantages of good hydrophilicity, high interception rate, excellent biodegradability and the like, and the polyamide active layer with a regular stripe structure can further increase the water flux and interception performance of the membrane.
Preferably, the thickness of the active layer is 3-10 μm.
In the present invention, the thickness of the active layer is, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
Preferably, the aperture of the active layer is 3-25 nm.
In the present invention, the pore diameter of the active layer is, for example, 3nm, 5nm, 8nm, 10nm, 12nm, 15nm, 17nm, 20nm, 22nm or 25nm.
Preferably, the porosity of the active layer is 70% -90%.
In the present invention, the active layer has a porosity of, for example, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 88%, or 90%.
According to a second aspect of the present invention, there is provided a method for producing a hollow fiber forward osmosis membrane, the method comprising: firstly, forming a porous supporting layer on the outer wall of the reinforcing layer, then forming an active layer on the porous supporting layer, and finally forming a porous framework layer on the inner wall of the reinforcing layer.
Specifically, a porous support layer is formed on the outer wall of the reinforcing layer by using a phase inversion method, then an active layer is formed on the porous support layer by using an interfacial polymerization method, and a porous framework layer is formed on the inner wall of the reinforcing layer by using an interfacial polymerization method.
In a preferred embodiment of the present invention, the formation of the structural layer on the inner wall of the reinforcement layer is performed at 0 to 10 ℃.
In the invention, a porous framework layer is formed on the inner wall of the reinforced layer, and a thin-layer composite film is prepared by adopting an interfacial polymerization method. Controlling the diffusion rate helps to regulate the film structure and film thickness, and helps to control the formation of regular stripe structures. The polymerization reaction is carried out at the temperature of 0-10 ℃, so that the diffusion rate of two high-activity monomers from aqueous solution to organic solution can be slowed down, the formation of a regular stripe structure is facilitated, and the thickness of the porous framework layer is controlled. The temperature at which the framework layer is formed on the inner wall of the reinforcement layer is, for example, 0 ℃, 1 ℃, 2 ℃, 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃, or 10 ℃.
Preferably, the method of forming an architecture layer inside the reinforcement layer comprises: placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath, firstly introducing a first solution into the membrane wire, soaking the inner wall of the membrane wire, then discharging the first solution, drying the surface of the inner wall of the membrane wire, introducing a second solution, discharging the second solution after reaction, and drying the membrane wire.
Specifically, the outer wall of a membrane wire after a porous supporting layer and an active layer are formed is placed in a water bath at 0-10 ℃, after a first solution is introduced into the membrane wire, the first solution is adsorbed in a reinforcing layer, the membrane wire is taken out from the water bath, the first solution is discharged, then the surface of the inner wall of the reinforcing layer is air-dried for 1min, a second solution is introduced into the membrane wire, and the first solution and the second solution adsorbed in the reinforcing layer undergo interfacial polymerization reaction in the inner wall of the reinforcing layer; after the second solution was drained, the filaments were removed from the water bath and dried.
Preferably, the residence time of the first solution and the second solution in the membrane filament is 20 s-60 s independently.
In the present invention, after the first solution is introduced into the membrane filament, the residence time of the first solution in the membrane filament is, for example, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s or 60s.
In the present invention, after the second solution is introduced into the membrane filament, the residence time of the second solution in the membrane filament is, for example, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s or 60s.
Preferably, the first solution comprises an aqueous phase high activity monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of water, 1.5-2.5 parts of anhydrous piperazine and 0-7.5 parts of diffusion retarder.
According to the invention, the diffusion retarder is added into the aqueous phase high-activity monomer solution, so that on one hand, the concentration of the solution can be increased, and on the other hand, the diffusion rate of the anhydrous piperazine in the aqueous solution can be weakened through interaction with the anhydrous piperazine in a hydrogen bond mode, thereby increasing the difference of the diffusion rates of the monomer in the first solution and the monomer in the second solution, and forming the polyamide framework layer with a uniform and regular stripe structure on the surface.
In the present invention, the anhydrous piperazine in the first solution is, for example, 2 parts, 2.2 parts, 2.4 parts, or 2.5 parts.
The diffusion retarder in the first solution is, for example, 4.5 parts, 5.0 parts, 5.5 parts, 6 parts, 6.5 parts or 7 parts.
Preferably, the second solution comprises an organic phase highly reactive monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of normal hexane and 0.08-0.15 part of trimesic acid chloride.
In the present invention, trimesoyl chloride in the second solution is, for example, 0.08 part, 0.09 part, 0.1 part, or 0.12 part.
Preferably, the diffusion retarder comprises one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone, preferably polyvinylpyrrolidone.
In the invention, the hydrogen bond formed by polyvinylpyrrolidone and anhydrous piperazine has stronger interaction force, can weaken the diffusion rate of the anhydrous piperazine in aqueous solution, and is favorable for forming a polyamide active layer with relatively more uniform and regular surface.
In a preferred embodiment of the present invention, a method of forming a porous support layer on the outer wall of a reinforcing layer comprises: and uniformly coating the casting solution on the outer wall of the reinforcing layer, and then soaking the reinforcing layer in a coagulating bath.
Preferably, after the membrane casting solution is defoamed, the membrane casting solution is uniformly coated on the outer wall of the reinforcing layer.
Preferably, the coagulation bath is water.
Preferably, the casting film liquid comprises the following raw materials in parts by weight: 10-20 parts of polysulfone and/or polyether sulfone, 0-5 parts of hydrophilic polymer and 100 parts of N-methylpyrrolidone.
In the present invention, when polysulfone is used for the porous support layer, the polysulfone is, for example, 10 parts, 12 parts, 14 parts or 16 parts.
When polyethersulfone is used for the porous support layer, the polyethersulfone is, for example, 14 parts, 16 parts, 18 parts, or 20 parts.
When a mixture of polysulfone and polyethersulfone is used for the porous support layer, the polysulfone and polyethersulfone is, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts.
The hydrophilic polymer is, for example, 2 parts, 3 parts, 4 parts or 5 parts.
Preferably, the preparation method of the casting film liquid comprises the following steps: and adding N-methyl pyrrolidone, heating to 50-60 ℃, adding polysulfone and/or polyether sulfone and a hydrophilic polymer, and dissolving.
In the present invention, the temperature at which polysulfone and/or polyethersulfone, and hydrophilic polymer are dissolved in N-methylpyrrolidone is, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, or 60 ℃.
Specifically, after heating N-methyl pyrrolidone to 50-60 ℃, adding polysulfone and/or polyether sulfone and a hydrophilic polymer, stirring for 5-10 hours to obtain pale yellow uniform transparent casting solution, defoaming the casting solution, uniformly coating the casting solution on the outer wall of the reinforcing layer, and then soaking in water to obtain the porous supporting layer with the thickness of 30-100 mu m.
In a preferred embodiment of the present invention, the formation of the active layer on the porous support layer is performed at 20 ℃ to 45 ℃.
The temperature at which the active layer is formed on the porous support layer is, for example, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, or 45 ℃.
In the invention, the active layer is formed on the porous supporting layer by adopting an interfacial polymerization method, and the thickness of the active layer can be influenced by adjusting the temperature for forming the active layer.
Preferably, the method of forming an active layer on a porous support layer includes: adding water into the membrane wire after the porous supporting layer is formed, immersing the outer wall of the membrane wire into the third solution, taking out the membrane wire, drying the outer wall surface of the membrane wire, immersing the membrane wire into the fourth solution, reacting, taking out the membrane wire and drying.
Preferably, the residence time of the membrane filaments in the third solution is 1-3 min.
In the present invention, the residence time of the membrane filaments in the third solution is, for example, 2min, 2.5min or 3min.
Preferably, the residence time of the membrane filaments in the fourth solution is 0.5-1.5 min.
In the present invention, the residence time of the filaments in the fourth solution is, for example, 0.8min, 0.9min, 1min or 1.2min.
Specifically, water is added into the membrane wire after the porous supporting layer is formed, the outer wall of the membrane wire is immersed in the third solution, the retention time is 1-3 min, then the membrane wire is taken out, the surface of the outer wall of the membrane wire is air-dried, then the membrane wire is immersed in the fourth solution at 20-45 ℃, the retention time is 0.5-1.5 min, then the membrane wire is taken out, the water in the membrane wire is discharged, and the membrane wire is dried.
Preferably, the third solution comprises an aqueous phase high activity monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of water, 1.5-2.5 parts of anhydrous piperazine and 0-7.5 parts of diffusion retarder.
In the invention, the diffusion retarder is added into the third solution, so that on one hand, the concentration of the solution can be increased, and on the other hand, the diffusion retarder interacts with the anhydrous piperazine in a hydrogen bond mode, and the diffusion rate of the anhydrous piperazine in the aqueous solution can be weakened, so that the difference between the diffusion rates of the monomer in the second solution and the monomer in the third solution is increased, and a polyamide framework layer with a uniform and regular surface is formed.
In the present invention, the anhydrous piperazine in the third solution is, for example, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, or 2.5 parts.
The diffusion retarder in the third solution is, for example, 0 part, 4.5 parts, 4.7 parts, 4.9 parts, 5.0 parts, 5.2 parts, 5.5 parts, 5.7 parts, 6 parts, 6.3 parts, 6.5 parts, 6.8 parts, 7 parts, 7.3 parts, or 7.5 parts.
Preferably, the fourth solution comprises an organic phase highly reactive monomer solution, preferably comprising the following raw materials in parts by weight: 100 parts of normal hexane and 0.08-0.15 part of trimesic acid chloride.
In the present invention, the trimesic acid chloride in the fourth solution is, for example, 0.08 part, 0.09 part, 0.1 part, 0.11 part, 0.12 part, 0.13 part, 0.14 part or 0.15 part.
Preferably, the diffusion retarder comprises one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone, preferably polyvinylpyrrolidone.
In the invention, the hydrogen bond formed by polyvinylpyrrolidone and anhydrous piperazine has stronger interaction force, can weaken the diffusion rate of the anhydrous piperazine in aqueous solution, and is favorable for forming a polyamide active layer with a Turing structure with relatively more uniform and regular surface.
According to a third aspect of the present invention there is provided the use of a hollow fibre forward osmosis membrane for use in water treatment.
Preferably, when the water flux of the hollow fiber forward osmosis membrane is reduced to 6L.m -2 ·h -1 -12L·m -2 ·h -1 When the polluted porous framework layer is cleaned, the porous framework layer is formed on the inner wall of the reinforced layer again.
Specifically, the method of cleaning away the contaminated porous architecture layer includes: pressurizing, pulsing, vibrating, soaking in medicine, etc
After the polluted porous structure layer is washed away, the method for forming the structure layer on the inner wall of the reinforcing layer is the same as the method for forming the structure layer on the inner wall of the reinforcing layer in the preparation method of the hollow fiber forward osmosis membrane.
Examples
The present application is described in further detail below with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
In the following examples, each raw material component was a commercially available product unless otherwise specified.
Example 1
The reinforcing layer is a polyester fiber woven tube with 40 meshes of tube wall holes, the outer diameter of 1.80-1.85 mm and the inner diameter of 1.05 mm.
S1, forming a porous supporting layer on the outer wall of the reinforcing layer
100 parts of N-methylpyrrolidone, 16 parts of polysulfone and 3 parts of polyvinylpyrrolidone are added, stirring is carried out for 8 h, after the temperature is raised to 60 ℃, light yellow uniform transparent casting solution is obtained, after the casting solution is defoamed, the casting solution is uniformly coated on the outer wall of the reinforcing layer, the coating thickness of the casting solution is controlled to be 50 mu m, and then the membrane filaments forming the porous supporting layer are obtained after soaking in water.
The average pore diameter of the porous supporting layer was 18nm, the porosity was 80%, and the pure water flux was 65L. Mu.m -2 ·h -1 。
S2 forming an active layer on the porous support layer
The third solution was a mixed solution of 100 parts of water, 2 parts of anhydrous piperazine and 6 parts of polyvinylpyrrolidone.
The fourth solution was a mixed solution of 100 parts of n-hexane and 0.1 part of trimesic acid chloride.
Adding water into the membrane wire after the porous supporting layer is formed, immersing the outer wall of the membrane wire into the third solution, staying for 2min, taking out the membrane wire, air-drying the outer wall surface of the membrane wire, immersing into the fourth solution, staying for 1min, taking out the membrane wire, discharging the water in the membrane wire, and drying the membrane wire.
The thickness of the active layer was 7. Mu.m, the average pore diameter was 12nm, the porosity of the membrane filaments after forming the porous support layer and the active layer was 90%, and the pure water flux was 62L. Mu.m -2 ·h -1 。
S3 forming a porous framework layer on the inner wall of the reinforcing layer
The first solution was a mixed solution of 100 parts of water, 2 parts of anhydrous piperazine and 6 parts of polyvinylpyrrolidone.
The second solution was a mixed solution of 100 parts of n-hexane and 0.1 part of trimesic acid chloride.
Placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath at the temperature of 6 ℃, after the first solution is introduced into the membrane wire, staying for 30s, taking the membrane wire out of the water bath, discharging the first solution, then airing the inner wall of the reinforcing layer for 1min, then placing the outer wall of the membrane wire in the water bath at the temperature of 6 ℃, introducing the second solution into the membrane wire, staying for 30s, taking the membrane wire out of the water bath, discharging the second solution, and drying the membrane wire.
The thickness of the porous framework layer is 0.7 μm, and the average pore diameter is 25nm; pure waterFlux 62 L.m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer can be peeled off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
After use, the water is cleaned every day, when the flux is reduced to 10 L.m -2 ·h -1 At this time, the water flux was restored to 97% of the original water flux by the drug infusion.
Example 2
Otherwise, the same as in example 1 was conducted.
The difference is that:
the formation of the porous structure layer on the inner wall of the reinforcing layer is carried out at 8 ℃, namely: and (3) placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath at 8 ℃, discharging the first solution, and after air-drying, continuously placing the outer wall of the membrane wire in the water bath at 5 ℃.
The thickness of the porous architecture layer was measured to be 0.8 μm and the average pore diameter was 30nm; the pure water flux is 64L m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer can be peeled off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
Example 3
Otherwise, the same as in example 1 was conducted.
The difference is that:
the formation of the porous structure layer on the inner wall of the reinforcing layer is carried out at 10 ℃, namely: and (3) placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath at 10 ℃, discharging the first solution, and after air-drying, continuously placing the outer wall of the membrane wire in the water bath at 10 ℃.
The thickness of the porous architecture layer was measured to be 1 μm and the average pore diameter was measured to be 50nm; pure water flux 65L m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer can be peeled off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
Example 4
Otherwise, the same as in example 2 is carried out.
The difference is that:
the first solution was a mixed solution of 100 parts of water, 1.5 parts of anhydrous piperazine and 5 parts of polyvinylpyrrolidone.
The second solution was a mixed solution of 100 parts of n-hexane and 0.1 part of trimesic acid chloride.
The residence time of the first solution in the membrane filaments was 40s and the residence time of the second solution in the membrane filaments was 50s.
The thickness of the porous architecture layer was measured to be 1.1 μm and the average pore diameter was 30nm; pure water flux 63L m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer can be peeled off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
Example 5
Otherwise, the same as in example 2 is carried out.
The difference is that:
the first solution was a mixed solution of 100 parts water, 2.5 parts anhydrous piperazine and 7.5 parts polyvinylpyrrolidone.
The second solution was a mixed solution of 100 parts of n-hexane and 0.15 part of trimesic acid chloride.
The residence time of the first solution in the membrane filaments was 60s and the residence time of the second solution in the membrane filaments was 60s.
The thickness of the porous architecture layer was measured to be 1 μm, and the average pore diameter was 35 nm; the pure water flux is 64 L.m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer can be peeled off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
Example 6
Otherwise, the same as in example 1 was conducted.
The difference is that:
the first solution was a mixed solution of 100 parts of water, 1.5 parts of anhydrous piperazine and 1 part of polyvinylpyrrolidone.
The second solution was a mixed solution of 100 parts of n-hexane and 0.1 part of trimesic acid chloride.
The thickness of the porous framework layer is 0.8 μm, and the average pore diameter is 30nm; pure water flux 60 L.m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer can be peeled off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
Example 7
Otherwise, the same as in example 1 was conducted.
The difference is that:
the formation of the porous structure layer on the inner wall of the reinforcing layer is carried out at 0 ℃, namely: and (3) placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath at 0 ℃, discharging the first solution, and after air-drying, continuously placing the outer wall of the membrane wire in the water bath at 0 ℃. The residence time of the first solution in the membrane filaments was 20s and the residence time of the second solution in the membrane filaments was 20s.
The thickness of the porous architecture layer was measured to be 0.5 μm and the average pore diameter was 15nm; pure water flux 62L.m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer can be peeled off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
Comparative example 1
Otherwise, the same as in example 1 was conducted.
Except that the porous architecture layer is no longer formed on the inner wall of the reinforcement layer.
After use, the flux is reduced to 10 L.m after daily pure water flushing and pulse flushing -2 ·h -1 At this time, the water flux was restored to 80% of the original water flux by the drug infusion.
Comparative example 2
Otherwise, the same as in example 1 was conducted.
The difference is that:
forming a porous architecture layer on the inner wall of the reinforcement layer
The first solution was a mixed solution of 100 parts of water, 2 parts of anhydrous piperazine and 6 parts of polyvinylpyrrolidone.
The second solution was a mixed solution of 100 parts of n-hexane and 0.1 part of trimesic acid chloride.
Placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath at the temperature of 0 ℃, after introducing the first solution into the membrane wire, staying for 15s, taking the membrane wire out of the water bath, discharging the first solution, then airing the inner wall of the reinforcing layer for 1min, then placing the outer wall of the membrane wire in the water bath at the temperature of 0 ℃, introducing the second solution into the membrane wire, staying for 15s, taking the membrane wire out of the water bath, discharging the second solution, and drying the membrane wire.
The thickness of the porous architecture layer was measured to be 0.3 μm and the average pore diameter was 14nm.
In normal use, the architecture layer is vulnerable.
Comparative example 3
Otherwise, the same as in example 1 was conducted.
The difference is that:
forming a porous architecture layer on the inner wall of the reinforcement layer
The first solution was a mixed solution of 100 parts of water, 2 parts of anhydrous piperazine and 6 parts of polyvinylpyrrolidone.
The second solution was a mixed solution of 100 parts of n-hexane and 0.1 part of trimesic acid chloride.
Placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath at 15 ℃, after the first solution is introduced into the membrane wire, staying for 1min, taking the membrane wire out of the water bath, discharging the first solution, then airing the inner wall of the reinforcing layer for 1min, then placing the outer wall of the membrane wire in the water bath at 15 ℃, introducing the second solution into the membrane wire, staying for 1min, taking the membrane wire out of the water bath, discharging the second solution, and drying the membrane wire.
The thickness of the porous structure layer was measured to be 1.5 μm, the average pore diameter was measured to be 55nm, and the water flux of the membrane filaments was measured to be 50 L.m -2 ·h -1 。
The membrane wires are not damaged in normal use and pure water cleaning processes, and the porous framework layer is difficult to peel off by using cleaning means such as pressurization, pulse, vibration or medicament soaking.
Claims (10)
1. The hollow fiber forward osmosis membrane is characterized by comprising an active layer, a porous supporting layer, a reinforcing layer and a porous framework layer from outside to inside in sequence;
the reinforcing layer is a woven tube made of polyester fiber;
the porous framework layer is a polyamide porous framework layer, and the thickness of the porous framework layer is 0.5-1.2 mu m;
the porous architecture layer is used for gathering pollutants and can carry the pollutants to fall off from the enhancement layer.
2. The hollow fiber forward osmosis membrane of claim 1, wherein the porous architecture layer is a polyamide porous architecture layer having a regular stripe structure;
the pore diameter of the porous framework layer is 15 nm-50 nm.
3. The hollow fiber forward osmosis membrane according to claim 1, wherein the porous architecture layer is formed on the inner wall of the reinforcement layer by interfacial polymerization;
adsorbing a first solution containing anhydrous piperazine on the inner wall of the enhancement layer, and performing interfacial polymerization in a second solution containing trimesoyl chloride;
the second solution further comprises a diffusion retarder;
the interfacial polymerization reaction time for forming the porous framework layer is 20 s-60 s;
the reaction temperature for forming the porous framework layer is 0-10 ℃.
4. The hollow fiber forward osmosis membrane according to claim 1, wherein the mesh number of the woven tube wall is 30-40 mesh.
5. The hollow fiber forward osmosis membrane of claim 1, wherein the porous support layer comprises polysulfone and/or polyethersulfone;
the polysulfone and polyethersulfone are independently modified with hydrophilic polymers;
the hydrophilic polymer is one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone;
the thickness of the porous supporting layer is 30-100 mu m;
the pore diameter of the porous supporting layer is 3-25 nm.
6. The hollow fiber forward osmosis membrane of claim 1, wherein the active layer is a polyamide active layer;
the thickness of the active layer is 3-10 mu m;
the aperture of the active layer is 3-25 nm.
7. The method for preparing a hollow fiber forward osmosis membrane according to any one of claims 1 to 6, comprising: firstly, forming a porous supporting layer on the outer wall of the reinforcing layer, then forming an active layer on the porous supporting layer, and finally forming a porous framework layer on the inner wall of the reinforcing layer;
forming a framework layer on the inner wall of the reinforced layer at 0-10 ℃;
a method of forming a structural layer within an inner wall of a reinforcement layer, comprising: placing the outer wall of the membrane wire after the porous supporting layer and the active layer are formed in a water bath, firstly introducing a first solution into the membrane wire, adsorbing the first solution on the inner wall of the membrane wire, then discharging the first solution, drying the surface of the inner wall of the membrane wire, introducing a second solution, discharging the second solution after the reaction, and drying the membrane wire;
the residence time of the first solution and the second solution in the membrane filament is respectively and independently 20-60 s;
the first solution comprises the following raw materials in parts by weight: 100 parts of water, 1.5-2.5 parts of anhydrous piperazine and 0-7.5 parts of diffusion retarder;
the second solution comprises the following raw materials in parts by weight: 100 parts of normal hexane and 0.08-0.15 part of trimesic acid chloride;
the diffusion retarder comprises one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone.
8. The method for preparing a hollow fiber forward osmosis membrane according to claim 7, wherein the method for forming the porous support layer on the outer wall of the reinforcing layer comprises: uniformly coating the casting solution on the outer wall of the reinforced layer, and then soaking the reinforced layer in a coagulating bath;
after defoaming the casting solution, uniformly coating the casting solution on the outer wall of the enhancement layer;
the casting film liquid comprises the following raw materials in parts by weight: 10-20 parts of polysulfone and/or polyether sulfone, 0-5 parts of hydrophilic polymer and 100 parts of N-methylpyrrolidone.
9. The method for producing a hollow fiber forward osmosis membrane according to claim 7, wherein the formation of the active layer on the porous support layer is performed at 20 ℃ to 45 ℃;
a method of forming an active layer on a porous support layer, comprising: firstly, adding water into the membrane wire after the porous supporting layer is formed, immersing the outer wall of the membrane wire into a third solution, then taking out the membrane wire, drying the outer wall surface of the membrane wire, immersing the membrane wire into a fourth solution, and taking out and drying the membrane wire after the reaction;
the soaking time of the membrane filaments in the third solution is 1-3 min;
the soaking time of the membrane filaments in the fourth solution is 0.5-1.5 min;
the third solution comprises the following raw materials in parts by weight: 100 parts of water, 1.5-2.5 parts of anhydrous piperazine and 0-7.5 parts of diffusion retarder;
the fourth solution comprises the following raw materials in parts by weight: 100 parts of normal hexane and 0.08-0.15 part of trimesic acid chloride;
the diffusion retarder comprises one or more of polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone.
10. Use of the hollow fiber forward osmosis membrane according to any one of claims 1 to 6 for water treatment;
the water flux of the hollow fiber forward osmosis membrane is reduced to 6L m -2 ·h -1 ~12 L·m -2 ·h -1 After cleaning the contaminated porous architecture layer, an architecture layer is formed on the inner wall of the reinforcement layer.
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| WO2022124554A1 (en) * | 2020-12-10 | 2022-06-16 | 도레이첨단소재 주식회사 | Polyamide reverse osmosis membrane having excellent durability and antifouling properties, and method for manufacturing same |
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| JP6103794B1 (en) * | 2015-08-27 | 2017-03-29 | 三菱電機株式会社 | Water treatment method and water treatment apparatus |
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| CN2520935Y (en) * | 2001-08-22 | 2002-11-20 | 盘锦市华意环境工程有限公司 | Diatomite dynamic film ultra filtering machne |
| CN204469560U (en) * | 2015-02-13 | 2015-07-15 | 湖南澳维环保科技有限公司 | A kind of coiled reverse osmosis membrane element |
| CN106693715A (en) * | 2016-11-22 | 2017-05-24 | 扬州大学 | Electric field coating process of ultrafiltration membrane |
| CN206631445U (en) * | 2017-04-05 | 2017-11-14 | 卢静琼 | A kind of anti-bacterial and anti-fouling contaminates filter membrane |
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