CN112337317A - Enhanced hollow fiber composite nanofiltration membrane and preparation method thereof - Google Patents

Enhanced hollow fiber composite nanofiltration membrane and preparation method thereof Download PDF

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Publication number
CN112337317A
CN112337317A CN201910727594.9A CN201910727594A CN112337317A CN 112337317 A CN112337317 A CN 112337317A CN 201910727594 A CN201910727594 A CN 201910727594A CN 112337317 A CN112337317 A CN 112337317A
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casting solution
additive
membrane
hollow fiber
mass fraction
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王蕾
徐愿坚
陈卫文
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Beijing Xinyuan Guoneng Technology Group Co ltd
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Beijing Xinyuan Guoneng Technology Group Co ltd
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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
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • 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
    • 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
    • B01D69/085—Details relating to the spinneret
    • 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
    • B01D69/087—Details relating to the spinning process
    • B01D69/088—Co-extrusion; Co-spinning
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/40—Fibre reinforced membranes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to the technical field of membranes, in particular to an enhanced hollow fiber composite nanofiltration membrane and a preparation method thereof. The preparation method comprises the following steps: (1) the method comprises the following steps of (1) carrying out corona pretreatment on a braided tube to eliminate burrs on the outer surface of the braided tube, penetrating the braided tube through the center of a double-hole spinneret, entering a coagulation bath at a certain traction speed and an air section distance, and winding the braided tube by a yarn collecting fiber; (2) adding the first casting solution into the first spinning kettle; (3) adding a second casting solution into a second spinning kettle; (4) and (2) spraying the casting solution I and the casting solution II through a double-hole spinning nozzle under the driving of pressure, uniformly coating the casting solution I and the casting solution II on the outer surface of the weaving tube, entering a coagulating bath for forming at the same traction speed and air section distance as those in the step (1), and rolling by a take-up pulley to obtain the enhanced hollow fiber composite nanofiltration membrane. According to the invention, a water phase monomer and an organic phase monomer are respectively added into the first membrane casting solution and the second membrane casting solution, so that the reaction of the two phase monomers occurs in the membrane forming process, and the enhanced composite nanofiltration membrane of woven tube-ultrafiltration-nanofiltration-ultrafiltration is formed, so that a nanofiltration functional layer is well protected, and the composite membrane is stable in performance after long-term operation and backwashing, and can be widely applied to the fields of industrial and domestic wastewater treatment and the like.

Description

Enhanced hollow fiber composite nanofiltration membrane and preparation method thereof
Technical Field
The invention relates to an enhanced hollow fiber composite nanofiltration membrane and a preparation method thereof, belonging to the technical field of membrane separation.
Background
The nanofiltration membrane technology is a novel membrane separation technology which is developed rapidly at home and abroad in recent years. The nanofiltration membrane is a pressure-driven membrane interposed between the ultrafiltration membrane and the reverse osmosis membrane. Due to the characteristics of low energy consumption, high efficiency and the like of the nanofiltration membrane technology, the nanofiltration membrane is widely applied to wastewater treatment, food industry, chemical and pharmaceutical industry, drinking water industry and the like. However, most of the current commercial nanofiltration membranes are roll-type nanofiltration membranes, which have weak anti-pollution capability, complex cleaning process, periodic replacement and high use cost.
Compared with a roll type membrane, the hollow fiber membrane has large water treatment amount and large specific surface area, can be scrubbed by air water and backwashed, and is easy to control membrane pollution. As the hollow fiber membrane continuously swings in the using process, the hollow fiber membrane is easy to break due to low strength, so that the effluent quality is influenced.
The preparation method of the nanofiltration membrane comprises an interface polymerization method, a phase inversion method, a charge method, a blending method and the like, wherein the interface polymerization method is the most widely adopted method at present, the method has rapid reaction and low required temperature, and the method is usually obtained by sequentially passing the conventional external pressure ultrafiltration membrane through an aqueous solution of polyamine and an organic solution of polybasic acyl chloride. For the hollow fiber membrane, the existence of the cylindrical surface is difficult to effectively keep the polyamine aqueous solution to be fully and uniformly distributed on the surface of the membrane, so that the functional layer obtained in the subsequent process of impregnating the polyacyl chloride organic solution has defects.
At present, almost no hollow fiber nanofiltration membrane product exists in the market.
Disclosure of Invention
Aiming at the defects in the prior art, the invention mainly aims to solve the defects in the prior art and provides a reinforced hollow fiber composite nanofiltration membrane and a preparation method thereof. The enhanced hollow fiber composite nanofiltration membrane has high strength, large flux and good selectivity, can be backwashed, has simple operation and continuous process, and can be widely applied to the fields of industry, domestic wastewater treatment and the like.
In order to solve the problems, the invention adopts the technical scheme that:
a preparation method of an enhanced hollow fiber composite nanofiltration membrane is characterized by comprising the following steps:
(1) the method comprises the following steps of (1) carrying out corona pretreatment on a braided tube to eliminate burrs on the outer surface of the braided tube, then passing through the center of a double-hole spinneret, entering a coagulation bath at a certain traction speed and an air section distance, and winding by a wire winding wheel;
(2) adding a first casting solution into a first spinning kettle, wherein the first casting solution is composed of a first polymer, a first additive, a first solvent and a second additive; the first polymer is one or more of polysulfone, polyether sulfone, polyacrylonitrile and polyvinylidene fluoride, and the mass fraction of the first polymer is 10% -25%; the first additive is one or more of lithium chloride, glycerol, polyvinylpyrrolidone, polyethylene glycol and water, and the mass fraction of the first additive is 0-10%; the first solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and acetone, and the mass fraction of the first solvent is 70-85%; the second additive is one or more of m-phenylenediamine, m-xylylenediamine, piperazine, 3-aminopropanol, amino-terminated polyethylene glycol, melamine, cyanuric acid and polyglutamic acid, and the mass fraction of the second additive is 0.001-10%;
(3) adding a second casting solution into the second spinning kettle, wherein the second casting solution consists of a second polymer, a third additive, a second solvent and a fourth additive; the first polymer is one or more of polysulfone, polyether sulfone, polyacrylonitrile and polyvinylidene fluoride, and the mass fraction of the first polymer is 10% -25%; the additive III is one or more of lithium chloride, glycerol, polyvinylpyrrolidone and polyethylene glycol, and the mass fraction of the additive III is 0-10%; the second solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and acetone, and the mass fraction of the second solvent is 70-85%; the additive IV is one or more of trimesoyl chloride, paraphthaloyl chloride and cyanuric chloride, and the mass fraction of the additive IV is 0.001% -10%;
(4) and (2) spraying the membrane casting solution I and the membrane casting solution II through a double-hole spinning nozzle under the driving of pressure, uniformly coating the membrane casting solution I and the membrane casting solution II on the outer surface of the weaving tube, entering a coagulating bath for forming at the same traction speed and air section distance as those in the step (1), and rolling by a wire winding wheel to obtain the enhanced hollow fiber composite nanofiltration membrane.
Preferably, the first membrane casting solution passes through the outer hole of the double-hole spinneret, and the second membrane casting solution passes through the inner hole of the double-hole spinneret.
The traction speed is determined by the rotating speed and the circumference of a yarn winding wheel, the rotating speed of the yarn winding wheel is 0.001-10 r/min, the circumference of the yarn winding wheel is 2 m, namely the traction speed is 0.002-20 m/min, and the air section distance is 10-35 cm.
The coagulating bath is one or more of water, ethanol, ethylene glycol, N-dimethylformamide, N-dimethylacetamide, triethylamine and glycerol, and the temperature of the coagulating bath is 15-70%oC。
The invention also provides an enhanced hollow fiber composite nanofiltration membrane which is characterized by being prepared by the preparation method, and the structure of the enhanced hollow fiber composite nanofiltration membrane comprises a braided tube supporting layer, an ultrafiltration layer, a nanofiltration layer and an ultrafiltration protective layer from inside to outside in sequence.
Compared with the prior art, the invention has the beneficial effects that:
(1) a double-hole spinning nozzle is used, a water phase monomer commonly used for interfacial polymerization is added into a membrane casting solution I, an organic phase monomer commonly used for interfacial polymerization is added into a membrane casting solution II, and the concentration of the two-phase monomer, the contact time and the reaction are controlled by the traction speed of a take-up pulley, the distance of an air section and the ratio of the membrane casting solution;
(2) the strength of the obtained composite membrane is improved by using the braided tube for supporting;
(3) the enhanced hollow fiber composite nanofiltration membrane prepared by the method has high flux, high strength and good selectivity, can be backwashed, and can be widely applied to the fields of industrial and domestic wastewater treatment and the like.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following embodiments are provided to further explain the present invention in detail.
Example 1
(1) Weaving the tube warpCorona pre-treating to remove burrs on its outer surface, passing through the center of a double-hole spinneret, and entering at a temperature of 30 deg.C at a drawing speed of 0.05 m/min and an air zone distance of 10 cmoC, in a deionized water coagulation bath, and winding by a wire winding wheel;
(2) adding a first casting solution into a first spinning kettle, wherein the first casting solution is composed of a first polymer, a first additive, a first solvent and a second additive; the first polymer is polysulfone, and the mass fraction of the first polymer is 13%; the first additive is polyethylene glycol, and the mass fraction of the first additive is 4%; the solvent is N, N-dimethylacetamide, and the mass fraction of the solvent is 82%; the second additive is m-xylylenediamine with the mass fraction of 1 percent;
(3) adding a second casting solution into the second filament kettle, wherein the second casting solution consists of a second polymer, a third additive, a second solvent and a fourth additive; the second polymer is polyether sulfone, and the mass fraction of the second polymer is 13%; the third additive is lithium chloride, and the mass fraction of the third additive is 1%; the second solvent is N, N-dimethylacetamide, and the mass fraction of the second solvent is 85%; the fourth additive is trimesoyl chloride, and the mass fraction of the fourth additive is 1%;
(4) the first membrane casting solution and the second membrane casting solution are sprayed out through a double-hole spinning nozzle under the driving of pressure, are uniformly coated on the outer surface of the weaving tube, and enter the weaving tube at the temperature of 30 ℃ at the traction speed of 0.05 m/min and the air section distance of 10 cmoAnd C, forming by using deionized water coagulation bath, and rolling by using a wire winding wheel to obtain the enhanced hollow fiber composite nanofiltration membrane.
The first membrane casting solution passes through the outer hole of the double-hole spinning nozzle, and the second membrane casting solution passes through the inner hole of the double-hole spinning nozzle.
Through testing, the breaking strength of the reinforced hollow fiber composite nanofiltration membrane obtained in the embodiment is 200N; the membrane was continuously filtered at 0.2 MPa for 2 g/L MgSO4Solution 7 h, flux 80 L.m-2.h-1The salt rejection can reach 88%; the salt rejection rate is unchanged after backwashing for 1 h under 0.3 MPa.
Example 2
(1) The braided tube is subjected to corona pretreatment to remove burrs on the outer surface of the braided tube, and then passes through the center of a double-hole spinneret at a drawing speed of 0.05 m/min and an air sectionThe entry temperature was 40 at a distance of 13 cmoC, in a deionized water coagulation bath, and winding by a wire winding wheel;
(2) adding a first casting solution into a first spinning kettle, wherein the first casting solution is composed of a first polymer, a first additive, a first solvent and a second additive; the first polymer is polysulfone, and the mass fraction of the first polymer is 14%; the first additive is polyethylene glycol, and the mass fraction of the first additive is 4%; the solvent is N, N-dimethylacetamide, and the mass fraction of the solvent is 80%; the second additive is m-xylylenediamine with the mass fraction of 2 percent;
(3) adding a second casting solution into the second filament kettle, wherein the second casting solution consists of a second polymer, a third additive, a second solvent and a fourth additive; the second polymer is polyether sulfone, and the mass fraction of the second polymer is 13%; the third additive is lithium chloride, and the mass fraction of the third additive is 1%; the second solvent is N, N-dimethylacetamide, and the mass fraction of the second solvent is 85%; the fourth additive is trimesoyl chloride, and the mass fraction of the fourth additive is 1%;
(4) the first membrane casting solution and the second membrane casting solution are sprayed out through a double-hole spinning nozzle under the drive of pressure, are uniformly coated on the outer surface of the weaving tube, and enter the weaving tube at the temperature of 40 ℃ at the traction speed of 0.05 m/min and the air section distance of 13 cmoAnd C, forming by using deionized water coagulation bath, and rolling by using a wire winding wheel to obtain the enhanced hollow fiber composite nanofiltration membrane.
The first membrane casting solution passes through the outer hole of the double-hole spinning nozzle, and the second membrane casting solution passes through the inner hole of the double-hole spinning nozzle.
Through testing, the breaking strength of the reinforced hollow fiber composite nanofiltration membrane obtained in the embodiment is 230N; the membrane was continuously filtered at 0.2 MPa for 2 g/L MgSO4Solution 7 h, at a flux of 65 L.m-2.h-1The salt rejection can reach 94%; the salt rejection rate is unchanged after backwashing for 1 h under 0.3 MPa.
Example 3
(1) Corona pre-treating the braided tube to remove burrs on its outer surface, passing through the center of a double-hole spinneret, and allowing the braided tube to enter at 50 deg.C at a drawing speed of 0.2 m/min and an air section distance of 20 cmoC, in a deionized water coagulation bath, and winding by a wire winding wheel;
(2) adding a first casting solution into a first spinning kettle, wherein the first casting solution is composed of a first polymer, a first additive, a first solvent and a second additive; the first polymer is polyvinylidene fluoride, and the mass fraction of the first polymer is 16%; the additive I is a mixture of glycerol and polyethylene glycol, the mass fraction of the additive I is 4%, and the mass ratio of the glycerol to the polyethylene glycol is 1: 7; the solvent is N, N-dimethylformamide, and the mass fraction of the N, N-dimethylformamide is 78%; the second additive is piperazine with the mass fraction of 2%;
(3) adding a second casting solution into the second filament kettle, wherein the second casting solution consists of a second polymer, a third additive, a second solvent and a fourth additive; the second polymer is polyvinylidene fluoride, and the mass fraction of the second polymer is 14%; the third additive is a mixture of glycerol and polyethylene glycol, the mass fraction of the third additive is 4%, and the mass ratio of the glycerol to the polyethylene glycol is 1: 3; the second solvent is N, N-dimethylformamide, and the mass fraction of the second solvent is 80%; the additive IV is cyanuric chloride, and the mass fraction of the additive IV is 2%;
(4) the first membrane casting solution and the second membrane casting solution are sprayed out through a double-hole spinning nozzle under the drive of pressure, are uniformly coated on the outer surface of the weaving tube, and enter at the temperature of 50 ℃ at the traction speed of 0.2 m/min and the air section distance of 20 cmoAnd C, forming by using deionized water coagulation bath, and rolling by using a wire winding wheel to obtain the enhanced hollow fiber composite nanofiltration membrane.
The first membrane casting solution passes through the outer hole of the double-hole spinning nozzle, and the second membrane casting solution passes through the inner hole of the double-hole spinning nozzle.
According to the test, the breaking strength of the reinforced hollow fiber composite nanofiltration membrane obtained in the embodiment is 300N; the membrane was continuously filtered at 0.2 MPa for 2 g/L MgSO4Solution 7 h, flux 55 L.m-2.h-1The salt rejection can reach 96 percent; the salt rejection rate is unchanged after backwashing for 1 h under 0.3 MPa.
Example 4
(1) Corona pre-treating the braided tube to remove burrs on its outer surface, passing through the center of a double-hole spinneret, and allowing the braided tube to enter at 50 deg.C at a drawing speed of 0.4 m/min and an air section distance of 20 cmoC, in a deionized water coagulation bath, and winding by a wire winding wheel;
(2) adding a first casting solution into a first spinning kettle, wherein the first casting solution is composed of a first polymer, a first additive, a first solvent and a second additive; the first polymer is polyvinylidene fluoride, and the mass fraction of the first polymer is 16%; the additive I is polyvinylpyrrolidone, and the mass fraction of the additive I is 3%; the solvent is N, N-dimethylformamide, and the mass fraction of the N, N-dimethylformamide is 78%; the second additive is piperazine with the mass fraction of 3%;
(3) adding a second casting solution into the second filament kettle, wherein the second casting solution consists of a second polymer, a third additive, a second solvent and a fourth additive; the second polymer is polyvinylidene fluoride, and the mass fraction of the second polymer is 18%; the third additive is polyvinylpyrrolidone, and the mass fraction of the third additive is 2.5%; the second solvent is N, N-dimethylformamide, and the mass fraction of the second solvent is 78%; the additive IV is terephthaloyl chloride, and the mass fraction of the additive IV is 1.5%;
(4) the first membrane casting solution and the second membrane casting solution are sprayed out through a double-hole spinning nozzle under the drive of pressure, are uniformly coated on the outer surface of the weaving tube, and enter at the temperature of 50 ℃ at the traction speed of 1 m/min and the air section distance of 20 cmoAnd C, forming by using deionized water coagulation bath, and rolling by using a wire winding wheel to obtain the enhanced hollow fiber composite nanofiltration membrane.
The first membrane casting solution passes through the outer hole of the double-hole spinning nozzle, and the second membrane casting solution passes through the inner hole of the double-hole spinning nozzle.
Through testing, the breaking strength of the reinforced hollow fiber composite nanofiltration membrane obtained in the embodiment is 320N; the membrane was continuously filtered at 0.2 MPa for 2 g/L MgSO4Solution 7 h, at a flux of 65 L.m-2.h-1The salt rejection can reach 90%; the salt rejection rate is unchanged after backwashing for 1 h under 0.3 MPa.
From the above examples it can be seen that: (1) the enhanced hollow fiber composite nanofiltration membrane provided by the invention has the advantages of high breaking strength, high flux and high MgSO4Desalting rate and backwashing; (2) the preparation method provided by the invention is simple, is easy for industrial amplification, and has wide application prospects in the fields of industry, domestic wastewater treatment and the like.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the spirit of the invention, and these modifications and decorations should be regarded as being within the protection scope of the invention.

Claims (5)

1. A preparation method of an enhanced hollow fiber composite nanofiltration membrane is characterized by comprising the following steps:
(1) the method comprises the following steps of (1) carrying out corona pretreatment on a braided tube to eliminate burrs on the outer surface of the braided tube, then passing through the center of a double-hole spinneret, entering a coagulation bath at a certain traction speed and an air section distance, and winding by a wire winding wheel;
(2) adding a first casting solution into a first spinning kettle, wherein the first casting solution is composed of a first polymer, a first additive, a first solvent and a second additive; the first polymer is one or more of polysulfone, polyether sulfone, polyacrylonitrile and polyvinylidene fluoride, and the mass fraction of the first polymer is 10% -25%; the first additive is one or more of lithium chloride, glycerol, polyvinylpyrrolidone, polyethylene glycol and water, and the mass fraction of the first additive is 0-10%; the first solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and acetone, and the mass fraction of the first solvent is 70-85%; the second additive is one or more of m-phenylenediamine, m-xylylenediamine, piperazine, 3-aminopropanol, amino-terminated polyethylene glycol, melamine, cyanuric acid and polyglutamic acid, and the mass fraction of the second additive is 0.001-10%;
(3) adding a second casting solution into the second spinning kettle, wherein the second casting solution consists of a second polymer, a third additive, a second solvent and a fourth additive; the second polymer is one or more of polysulfone, polyether sulfone, polyacrylonitrile and polyvinylidene fluoride, and the mass fraction of the second polymer is 10-25%; the additive III is one or more of lithium chloride, glycerol, polyvinylpyrrolidone and polyethylene glycol, and the mass fraction of the additive III is 0-10%; the second solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and acetone, and the mass fraction of the second solvent is 70-85%; the additive IV is one or more of trimesoyl chloride, paraphthaloyl chloride and cyanuric chloride, and the mass fraction of the additive IV is 0.001% -10%;
(4) and (2) spraying the membrane casting solution I and the membrane casting solution II through a double-hole spinning nozzle under the driving of pressure, uniformly coating the membrane casting solution I and the membrane casting solution II on the outer surface of the weaving tube, entering a coagulating bath for forming at the same traction speed and air section distance as those in the step (1), and rolling by a wire winding wheel to obtain the enhanced hollow fiber composite nanofiltration membrane.
2. The method for preparing the enhanced hollow fiber composite nanofiltration membrane according to claim 1, wherein the first membrane casting solution is provided with an outer hole of a double-hole spinneret, and the second membrane casting solution is provided with an inner hole of the double-hole spinneret.
3. The method for preparing an enhanced hollow fiber composite nanofiltration membrane according to claim 1, wherein the drawing speed is determined by the rotating speed and the circumference of a take-up pulley, the rotating speed of the take-up pulley is 0.001-10 r/min, the circumference of the take-up pulley is 2 m, that is, the drawing speed is 0.002-20 m/min, and the air space distance is 10-35 cm.
4. The method for preparing the enhanced hollow fiber composite nanofiltration membrane according to claim 1, wherein the coagulation bath is one or more of water, ethanol, ethylene glycol, N-dimethylformamide, N-dimethylacetamide, triethylamine and glycerol, and the temperature of the coagulation bath is 15-70%oC。
5. An enhanced hollow fiber composite nanofiltration membrane, which is characterized by being prepared by the preparation method of claims 1 to 4, and the structure of the enhanced hollow fiber composite nanofiltration membrane comprises a braided tube supporting layer, an ultrafiltration layer, a nanofiltration layer and an ultrafiltration protective layer from inside to outside in sequence.
CN201910727594.9A 2019-08-07 2019-08-07 Enhanced hollow fiber composite nanofiltration membrane and preparation method thereof Pending CN112337317A (en)

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CN105396470A (en) * 2015-12-10 2016-03-16 广州中国科学院先进技术研究所 Hollow fiber composite nanofiltration membrane and preparation method thereof
CN105797601A (en) * 2016-03-25 2016-07-27 北京碧水源膜科技有限公司 Reinforced hollow fiber composite membrane and preparation method thereof
CN108126528A (en) * 2017-08-30 2018-06-08 江苏向阳科技有限公司 A kind of preparation method of double-layer hollow fiber NF membrane
CN109847595A (en) * 2018-12-21 2019-06-07 三达膜科技（厦门）有限公司 A kind of preparation method of the big compound polyvinylidene fluoride hollow fiber ultrafiltration membrane of flux inner support

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