CN107456880A - A kind of preparation method of hollow fiber nanofiltration membrane - Google Patents
A kind of preparation method of hollow fiber nanofiltration membrane Download PDFInfo
- Publication number
- CN107456880A CN107456880A CN201610383454.0A CN201610383454A CN107456880A CN 107456880 A CN107456880 A CN 107456880A CN 201610383454 A CN201610383454 A CN 201610383454A CN 107456880 A CN107456880 A CN 107456880A
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- Prior art keywords
- spinning
- fibre
- hollow
- hollow fiber
- beading
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—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
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Abstract
The present invention relates to the preparation method of a kind of antipollution, the hollow fiber nanofiltration membrane of high intensity.Technical solutions according to the invention are to design a kind of novel spinning technique（See Fig. 1, Fig. 2）, the technique is with polyether sulfone（PES）, sulfonated polyether sulfone（SPES）Or both blend be bulk material, electrostatic spinning technique is combined with traditional non-solvent inversion of phases spinning technique, when doughnut casting solution is extruded from spinneret, the solution that Static Spinning syringe needle sprays just enters in doughnut membranous wall, the two falls into coagulating bath and inversion of phases occurs together, and by processes such as rinsing, windings, obtain the hollow fiber nanofiltration membrane using the beading fiber of functionalization or superfine fibre beam as reinforcement.More beading fibers or superfine fibre Shu Zucheng reinforcements are firmly embedded in hollow fiber nanofiltration membrane（See Fig. 3, Fig. 4）, it is difficult to peel off, reinforcement is high-intensity resin mixed inorganic particle, assigns the higher intensity of hollow fiber nanofiltration membrane and stain resistance.Technique of the present invention is simply advanced, is suitable for the large-scale production of hollow-fibre membrane factory.
Description
Technical field
It is specially a kind of using beading fiber or superfine fibre beam as reinforcement the present invention relates to a kind of preparation method of NF membrane
The preparation method of the hollow fiber nanofiltration membrane of muscle, belong to seperation film manufacturing field.
Background technology
NF membrane（Nanofiltration, NF）It is a kind of new separation of the cutoff performance between ultrafiltration and counter-infiltration
Film.NF membrane is less than 50% to the rejection of monovalent salt, to divalence and the rejection of multivalent salts more than 80%；And can retention phase
To dissolved constituent of the molecular mass more than 200.In addition, the transmembrane pressure that nanofiltration process needs is generally 0.5~2.0 MPa,
It is lower 0.5~3.0 MPa than reaching the pressure difference applied needed for same permeation flux with counter-infiltration.Due to its selective retention feature and
Low pressure operability, nanofiltration start to be used widely in fields such as water resource, food, medicine, environmental protection, chemical industry.
Commodity NF membrane is mostly spiral membrane module, complex manufacturing, and use condition is harsh, cleaning and safeguard all compared with
For difficulty.
Hollow-fibre membrane has that unit volume inner ratio surface area is big, film and component simple production process, easy cleaning easy care
The advantages that.But homogeneous doughnut film-strength is lower slightly, easily deformed under nanofiltration operating pressure；Have at present using mesh grid and
Fiber does the hollow-fibre membrane strengthened, but reinforcing mat or reinforcing fibre easily occur in use and easily shows with what film body was peeled off
As bringing hollow fiber film structure damage and penalty.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of antipollution, the doughnut nanofiltration of high intensity
Film.Technical solutions according to the invention are to design a kind of novel spinning technique, and the technique is with polyether sulfone（PES）, sulfonated polyether sulfone
（SPES）Or both blend be bulk material, electrostatic spinning technique and traditional non-solvent inversion of phases spinning technique are mutually tied
Close, when doughnut casting solution is extruded from spinneret, the solution that Static Spinning syringe needle sprays just enters in doughnut membranous wall,
The two falls into coagulating bath and inversion of phases occurs together, and by processes such as rinsing, windings, obtains with the beading fiber of functionalization or super
Fine fibre beam is the hollow fiber nanofiltration membrane of reinforcement.
Compared with prior art, the inventive method has the following advantages that：
1. the reinforcement of doughnut is beading fiber, because beading fiber has continuous pearl expander, therefore and fiber
Contact surface it is big, pearl expander firmly be embedded in hollow-fibre membrane in, both compound fastness are very big.In addition, change Static Spinning
Pressure, the solution ejected can be divided into more superfine fibres, form fibre bundle, and superfine fibre can be bonded into section during decline
Point, it will also play reinforcing and strengthen supporting role.
2. beading fiber or superfine fibre beam are nanofiber, it is very thin, therefore will not be as conventional reinforcing fibre and fibre
Dimension net occupies larger volume like that, influences the separating property of hollow-fibre membrane.
3. beading fiber or superfine fibre beam material are high-intensity resin mixed inorganic particle, there is enhancing and toughness reinforcing to make
With.
4. often temperature is higher for electrostatic spinning solution, therefore is easy to dissolve high-intensity resin, blending inorganic nano-particle, fine
Although dimension is thin but intensity is higher.
5. the syringe needle of electrostatic spinning is superfine, therefore can be distributed multiple syringe needles along the circumferencial direction of doughnut, spray simultaneously
Go out beading fiber, more ultra-fine muscle of formation are uniformly distributed and enhancement mode, add the impact resistance ability of doughnut.
6. realizing the dynamic water-bath resultant yarn of electrostatic spinning fiber using hollow fiber spinning coagulating bath, casting solution and Static Spinning are molten
Inversion of phases together occurs for liquid, and both combinations are closer.
7. inorganic particulate selected by assigns doughnut higher intensity, contamination resistance and biocidal property.
8. patent simple production process of the present invention is advanced.
Brief description of the drawings
Fig. 1 is the spinning equipment and process schematic representation that beading fiber of the present invention or fibre bundle strengthen hollow-fibre membrane.
In Fig. 1：1. molten material kettle stirring system；2. molten material kettle；3. valve；4. measuring pump；5. spinneret；6. core liquid kettle stirring system；7.
Core liquid kettle；8. valve；9. measuring pump；10. coagulating bath；11. rinsing bath；12. take-up roll；13. electrostatic spinning device；14. Static Spinning
Discharge syringe needle
Fig. 2 is the arrangement position view of Static Spinning discharging syringe needle, and syringe needle quantity is 2-100.In Fig. 2：1. doughnut goes out
Discharge position；2. syringe needle.
Fig. 3 beading fiber strengthens the schematic diagram of hollow-fibre membrane.In Fig. 3：1. doughnut；2. beading fiber.
Fig. 4 fibre bundles strengthen the schematic diagram of hollow-fibre membrane.In Fig. 4：1. doughnut；2. fibre bundle.
Embodiment
With reference to embodiment and its accompanying drawing, the present invention will be further described：
The present invention designs a kind of novel spinning technique, and the technique is with polyether sulfone（PES）And sulfonated polyether sulfone（SPES）Blend is
Bulk material, electrostatic spinning technique is combined with traditional non-solvent inversion of phases spinning technique, exploitation reinforcing fibre and hollow fibre
The same spinning technique of film is tieed up, prepares beading fiber or fibre bundle using functionalization as reinforcement（Reinforcing fibre）Doughnut nanofiltration
Film.Concrete technology includes：
1. install electrostatic spinning apparatus additional on conventional wet spinning-drawing machine（See Fig. 1）, discharging syringe needle the going out in spinneret of Static Spinning
Below material mouth, the centre of following doughnut membranous wall；
2. prepare the casting solution of polyether sulfone and sulfonated polyether sulfone, standing and defoaming；
3. inorganic particulate, auxiliary agent, polymer etc. are configured to electrostatic spinning solution with solvent；
4. electrospinning conditions are set, including：Electrostatic pressure, spinning speed etc., electrostatic spinning equipment is opened, using air spinning and liquid stream
Control technology, spin beading fiber or fibre bundle（See Fig. 2）；
5. open hollow fiber spinning machine, under certain temperature and pressure, make casting solution by spinneret and with electrostatic spinning pin
Point, the polymer solution sprayed with Static Spinning is simultaneously into generation inversion of phases film forming in coagulating bath.The beading fiber of electrostatic spinning
Or fibre bundle is embedded in the fibre, the hollow fiber nanofiltration membrane that beading fiber or fibre bundle are strengthened is obtained.
Used hollow-fibre membrane spinning process is conventional wet spinning technology.Coagulating bath used in spinning technique is
Water.
The material pin mouth that goes out of Static Spinning is evenly distributed on hollow fibre spinneret discharging opening according to the direction of doughnut circumference
Lower section, quantity is is 2-100.
During electrostatic spinning the polymer refer to polycaprolactone, Kynoar, Triafol T, polyacrylonitrile,
One or several kinds in polystyrene, polyimides, polyether sulfone, polysulfones and polyamide etc..
The inorganic particulate refers to titanium dioxide, silica, carborundum, graphene, carbon nanometer during electrostatic spinning
One or several kinds in pipe etc..
During electrostatic spinning, electrostatic pressure 1-50kV, spinning speed 5-100m/s.
, need to be according to this if electrostatic spinning device sheet is as prior art, or only with the matching used equipment of the inventive method
Adaptability repacking is done in inventive method requirement, and those of ordinary skill in the art can be easily accomplished without creative work.
The inventive method is available for hollow-fibre membrane factory to carry out large-scale production use.
The present invention does not address part and is applied to prior art.
The specific embodiment of the inventive method is given below, but the inventive method claim is not limited by specific embodiment
System：
Embodiment 1
2 beading fibers strengthen polyether sulfone hollow fiber nanofiltration membrane：
1. prepare polyether sulfone casting solution, standing and defoaming；
2. silica, auxiliary agent, polyamide etc. are configured to electrostatic spinning solution with solvent；
3. electrospinning conditions are set, including：Electrostatic pressure is 1kV, spinning speed is 5m/s etc., opens electrostatic spinning equipment, is used
Air spinning technique, spin beading fiber；The discharging syringe needle of electrostatic spinning device is 2；
4. open hollow fiber spinning machine, under certain temperature and pressure, make casting solution by spinneret and with electrostatic spinning pin
Point, the polymer solution sprayed with Static Spinning is simultaneously into generation inversion of phases film forming in coagulating bath.The beading fiber of electrostatic spinning
It is embedded in the fibre, obtains the hollow fiber nanofiltration membrane that 2 beading fibers are strengthened.
Embodiment 2
100 beading fibers strengthen polyether sulfone hollow fiber nanofiltration membrane：
5. prepare polysulfones and polyethersulfone blended casting solution, standing and defoaming；
6. graphene, auxiliary agent, Kynoar etc. are configured to electrostatic spinning solution with solvent；
7. electrospinning conditions are set, including：Electrostatic pressure is 50kV, spinning speed is 50m/s etc., opens electrostatic spinning equipment, adopts
With air spinning technique, beading fiber is spinned；The discharging syringe needle of electrostatic spinning device is 100；
8. open hollow fiber spinning machine, under certain temperature and pressure, make casting solution by spinneret and with electrostatic spinning pin
Point, the polymer solution sprayed with Static Spinning is simultaneously into generation inversion of phases film forming in coagulating bath.The beading fiber of electrostatic spinning
It is embedded in the fibre, obtains the hollow fiber nanofiltration membrane that 100 beading fibers are strengthened.
Embodiment 3
6 fibre bundles strengthen polyether sulfone hollow fiber nanofiltration membrane：
9. prepare polysulfones and polyethersulfone blended casting solution, standing and defoaming；
10. titanium dioxide, auxiliary agent, polyamide etc. are configured to electrostatic spinning solution with solvent；
11. electrospinning conditions are set, including：Electrostatic pressure is 20kV, spinning speed is 100m/s etc., opens electrostatic spinning equipment,
Using quantitative control technology, spinning fibre Shu Jiaqiang hollow fiber nanofiltration membranes；The discharging syringe needle of electrostatic spinning device is 6；
12. open hollow fiber spinning machine, under certain temperature and pressure, make casting solution by spinneret and with electrostatic spinning pin
Point, the polymer solution sprayed with Static Spinning is simultaneously into generation inversion of phases film forming in coagulating bath.The beading fiber of electrostatic spinning
It is embedded in the fibre, obtains the hollow fiber nanofiltration membrane that 6 fibre bundles are strengthened.
Above-mentioned each embodiment is only one of possibility of the present invention, does not represent the whole of the present invention, doughnut casting film
The composition of liquid and electrostatic spinning solution, ratio can change in suitable scope.Hollow fiber spinning machine and electrostatic spinning device
Technological parameter can also be adjusted according to being actually needed, be not limited to described in example.
Claims (10)
1. the present invention is a kind of preparation method of the hollow fiber nanofiltration membrane of beading fiber or superfine fibre Shu Jiaqiang, this is reinforced
Hollow-fibre membrane is with polyether sulfone（PES）And sulfonated polyether sulfone（SPES）Blend is bulk material, fine with a beading for functionalization
Dimension or fibre bundle are reinforcement（Reinforcing fibre）.
2. according to claim 1, the present invention is to be combined electrostatic spinning technique with traditional non-solvent inversion of phases spinning technique, is adopted
Prepared with reinforcing fibre and hollow-fibre membrane with spinning technique.
3. concrete technology includes：
Electrostatic spinning apparatus is installed additional on conventional wet spinning-drawing machine（See Fig. 1）, discharging of the syringe needle in spinneret that discharge of Static Spinning
Below mouthful, the centre of following doughnut membranous wall；
Prepare the casting solution of polyether sulfone and sulfonated polyether sulfone, standing and defoaming；
Inorganic particulate, auxiliary agent, polymer etc. are configured to electrostatic spinning solution with solvent；
Electrospinning conditions are set, including：Electrostatic pressure, spinning speed etc., electrostatic spinning equipment is opened, spun and liquid stream control using air
Technology processed, spin beading fiber or fibre bundle（See Fig. 2）；
Open hollow fiber spinning machine, under certain temperature and pressure, make casting solution by spinneret and with electrostatic spinning needle point,
The polymer solution sprayed with Static Spinning is simultaneously into generation inversion of phases film forming in coagulating bath.
4. the beading fiber or fibre bundle of electrostatic spinning are embedded in the fibre, obtain beading fiber or fibre bundle strengthen it is hollow
Fiber nano filtering film.
5. according to claim 1 and 2, used hollow-fibre membrane spinning process is conventional wet spinning technology.
6. the coagulating bath used in spinning technique is water.
7. according to claim 1 and 2, the material pin mouth that goes out of Static Spinning is evenly distributed on hollow fibre according to the direction of doughnut circumference
The lower section of spinneret discharging opening is tieed up, it is 2-100 that quantity, which is,.
8. according to claim 1 and 2, it is fine to refer to polycaprolactone, Kynoar, three acetic acid for the polymer during electrostatic spinning
Tie up the one or several kinds in element, polyacrylonitrile, polystyrene, polyimides, polyether sulfone, polysulfones and polyamide etc..
9. according to claim 1 and 2, the inorganic ions refers to titanium dioxide, silica, carbonization during electrostatic spinning
One or several kinds in silicon, graphene, CNT etc..
10. according to claim 1 and 2, during electrostatic spinning, electrostatic pressure 1-50kV, spinning speed 5-100m/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610383454.0A CN107456880A (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of hollow fiber nanofiltration membrane |
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| CN201610383454.0A CN107456880A (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of hollow fiber nanofiltration membrane |
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|---|---|---|---|---|
| CN108607373A (en) * | 2018-04-19 | 2018-10-02 | 东华大学 | A kind of TiO2Compound forward osmosis membranes of/CNTs/PES and its preparation method and application |
| CN109758924A (en) * | 2019-03-16 | 2019-05-17 | 浙江清创环保新材料有限公司 | A kind of preparation method of supermolecule hollow-fibre membrane |
| CN112791647A (en) * | 2020-12-17 | 2021-05-14 | 安徽工程大学 | System for producing electromagnetic shielding composite fiber membrane |
| CN114369905A (en) * | 2021-12-28 | 2022-04-19 | 武汉理工大学 | Polymer blend film with gradient structure and preparation method thereof |
| CN115400616A (en) * | 2022-11-01 | 2022-11-29 | 富海(东营)新材料科技有限公司 | Preparation process and system of continuous integrated polysulfone hollow fiber membrane |
-
2016
- 2016-06-02 CN CN201610383454.0A patent/CN107456880A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607373A (en) * | 2018-04-19 | 2018-10-02 | 东华大学 | A kind of TiO2Compound forward osmosis membranes of/CNTs/PES and its preparation method and application |
| CN109758924A (en) * | 2019-03-16 | 2019-05-17 | 浙江清创环保新材料有限公司 | A kind of preparation method of supermolecule hollow-fibre membrane |
| CN112791647A (en) * | 2020-12-17 | 2021-05-14 | 安徽工程大学 | System for producing electromagnetic shielding composite fiber membrane |
| CN114369905A (en) * | 2021-12-28 | 2022-04-19 | 武汉理工大学 | Polymer blend film with gradient structure and preparation method thereof |
| CN114369905B (en) * | 2021-12-28 | 2023-11-07 | 武汉理工大学 | Polymer blend film with gradient structure and preparation method thereof |
| CN115400616A (en) * | 2022-11-01 | 2022-11-29 | 富海(东营)新材料科技有限公司 | Preparation process and system of continuous integrated polysulfone hollow fiber membrane |
| CN115400616B (en) * | 2022-11-01 | 2023-02-03 | 富海(东营)新材料科技有限公司 | Preparation process and system of continuous integrated polysulfone hollow fiber membrane |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171212 |
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| WD01 | Invention patent application deemed withdrawn after publication |