CN106521654A - Hollow fiber membrane spinning nozzle and method for preparing hollow fiber membrane - Google Patents
Hollow fiber membrane spinning nozzle and method for preparing hollow fiber membrane Download PDFInfo
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- CN106521654A CN106521654A CN201610918150.XA CN201610918150A CN106521654A CN 106521654 A CN106521654 A CN 106521654A CN 201610918150 A CN201610918150 A CN 201610918150A CN 106521654 A CN106521654 A CN 106521654A
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- spinning
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- passage
- liquid
- collector tube
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
Abstract
Disclosed are a hollow fiber membrane spinning nozzle and a method for preparing a hollow fiber membrane. The hollow fiber membrane spinning nozzle comprises a nozzle body with a solution channel, wherein a channel I, a channel II, a central liquid pipe, a liquid collection pipe and a spinning shaping area are arranged in the nozzle body, tail ends of the channel I and the channel II are both connected with the liquid collection pipe, the central liquid pipe is arranged at the center of the nozzle body, and the lower half portion of the central liquid pipe passes through the liquid collection pipe and extends to the spinning shaping area. A spinning solution for preparing the hollow fiber membrane is injected into the hollow fiber membrane spinning nozzle respectively through the channel I and the channel II, converges in the liquid collection pipe, and then is contacted with core liquid for solvent exchange, and finally forms the membrane through spinning. According to the hollow fiber membrane spinning nozzle and the method for preparing the hollow fiber membrane, the spinning solution converges well, and a stratification phenomenon of membrane filaments is avoided. A separating layer and a support layer of the hollow fiber membrane prepared by the hollow fiber membrane spinning nozzle are tightly combined, and can not be separated or layered, and the hollow fiber membrane has good selective permeability.
Description
Technical field
The present invention relates to a kind of spinning nozzle for preparing hollow-fibre membrane and the method for carrying out film preparation using which.
Background technology
Hollow-fibre membrane is one kind of anisotropic membrane, big with unit volume loading density, is acted on self-supporting, pressure
Performance is high, and life-span length, the equipment investment expense of film device are low, the advantages of miniaturized structure is simplified, therefore high-performance (Thief zone is logical
Amount P, high selectivity α) preparation of hollow fiber composite membrane is always one of emphasis of membrane technology development.For polymeric film material
For, generally there is trade-off relations between its permeation flux and selectivity, permeation flux is high, selective just low, otherwise also
So.The performance of hollow-fibre membrane is except having outside the Pass with raw material etc., also closely related with the material of spinning head, structure, the accuracy of manufacture.
Used as the core component spinning head of Ho llow fiber membrane for gas separation, it directly affects the production process of spinning, product quality, former material
Material consumption and the labour intensity of workman, therefore, generally there is certain particular/special requirement to spinning head.If spinning head structure design
Unreasonable, easily there is the situation of unbalance stress in shower nozzle internal flow in silk liquid, makes a liquid in Turbulent Flow, causes in spinning out
Hollow fiber membranous wall thickness ununiformity, occur hole it is eccentric the problems such as.
The core component of spinning hollow-fibre membrane is hollow spinning head, and shower nozzle mainly has two classes, and a class is equipped with needle tubing
Looping pit shower nozzle, the film supporting layer of preparation is identical with separation layer materials, and this shower nozzle is widely used in milipore filter and microfiltration membranes
Preparation.Another kind of is Crossed Circle hole spinning head, has inside and outside bilayer looping pit, injects in porch respectively and be polymerized by variety classes
The spinning solution of thing composition, supporting layer and separating layer can adopt different membrane materials, the film for preparing by this method mainly to use
Separate in gas.Two kinds of spinning solutions carry out exchange of solvent with core liquid simultaneously from spinneret exits, after coagulation bath, make by
The composite hollow fiber membrane of separating layer and supporting layer composition.Using this spinning head during spinning composite hollow fiber membrane
It is easy to the problem that separating layer and supporting layer depart from occur.
Composite membrane be by interfacial polymerization in one functional layer of support membrane surface recombination, the performance of composite membrane not only with functional layer
Property it is closely related, be also supported the impact of aperture, pore size distribution and the hole density of layer.Prepare the side of hollow fiber composite membrane
Method is usually first to make doughnut basement membrane, then applies the separating layer of layer on basement membrane, is generally separated layer and support
The material of tunic is different.With film made by the membrane material with larger flux, but intensity is often relatively low, it is difficult in being individually spun into
Hollow fiber film, can be using it as basic unit's supporting layer, and higher with another intensity, the higher polymer of separation value is used as separation
Layer, and using the excellent hollow fiber film thread of suitable shower nozzle processability.
The content of the invention
The spinning nozzle of the hollow-fibre membrane of the present invention makes the two kinds of polymer solution for preparing tunica fibrosa carry out solvent friendship
Alternatively before converge, Jing shower nozzles are once spun into composite hollow fiber membrane, its separating layer is not easily disconnected from supporting layer, it is ensured that product
Quality simultaneously improves production efficiency.
For realizing above technical purpose, first aspect present invention provides a kind of hollow-fibre membrane spinning nozzle, including one
Passage I, passage II, center liquid pipe, collector tube and spinning moulding are set in the individual sprayer body with solution channel, the shower nozzle body
Area, the passage I are " L " type, and its entrance is arranged on the upper surface of sprayer body, its end be arranged in sprayer body lower half
The collector tube upper end of the heart communicates；The entrance of the passage II is arranged on the side wall of sprayer body, extends horizontally to liquid collecting tube side wall
And communicate therewith；The center liquid pipe is the hollow liquid pipe for being arranged at sprayer body center, and its latter half passes through collector tube and prolongs
Extend spinning moulding area；The collector tube is arranged at the center of sprayer body, and its upper end starts from the outlet of passage I, and lower end terminates in spinning
Silk shaping area；The spinning moulding area is arranged at below the liquid pipe of center.
The technical purpose of second aspect present invention is to provide the method for preparing hollow-fibre membrane using above-mentioned shower nozzle, step
For：Core liquid is injected in the liquid pipe of center, will prepare the supporting layer spinning solution and separating layer spinning solution of hollow-fibre membrane respectively from logical
Road I and passage II inject, and separating layer spinning solution and supporting layer spinning solution enter collector tube, and passing through in passage II and collector tube
The place of wearing crosses, and the two is contacted with core liquid at the shower nozzle of center liquid pipe, forms an exchange area, carries out exchange of solvent film forming,
Hollow-fibre membrane is formed via shower nozzle.
Compared with prior art, the present invention has the advantage that：
Prepare hollow-fibre membrane using spinning solution be viscoelastic fluid, while spinning head aperture does VISCOUS FLOW send out
Raw elastic deformation, and the presence of elastic deformation, are one of unstable key factors of spinning；Reduce elastic deformation mainly to pass through
Reduce flowing velocity of the spinning solution in spinning head and improve spinning temperature, so as to reduce viscosity, the reduction of spinning solution
The purpose of elastic deformation；But spinning speed is too low to cause production efficiency too low, and improve spinning temperature, although bullet can be reduced
Property deformation, but with the rising of temperature, the film silk tensile strength produced substantially is reduced；The integrated design of shower nozzle of the present invention can
Make two kinds of polymer solution respectively by II injection of passage I and passage, first converge before the core liquid contact in the liquid pipe of Bing Yu centers,
The length of spinning solution material guide hole is increased, can make that spinning solution converges is more preferable, so as to avoid the lamination of film silk；Spinning
Liquid carries out exchange of solvent at shower nozzle again with core liquid, and can once spin shaping, the Middle hollow fiber membrane layer of preparation and support
Layer is not easily disconnected from, with preferable selective penetrated property, it is ensured that product quality simultaneously improves production efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the front view of the shower nozzle of embodiment 1；
Fig. 2 is the top view of the shower nozzle of embodiment 1；
Fig. 3 is the tangent plane schematic diagram in A-A directions in Fig. 2；
Fig. 4 is the tangent plane schematic diagram in B-B directions in Fig. 2；
Fig. 5 is the tangent plane schematic diagram in D-D directions in Fig. 4；
Wherein, 11. passage I, 12. passages II, 121. first liquid input sections, 122. solution buffering areas, 123. second liquid input sections,
13. center liquid pipes；14. collector tubes, 2. spinning moulding area, 21. through holes.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The technical purpose of first aspect present invention is to provide a kind of hollow-fibre membrane spinning nozzle, leads to including a band solution
Passage I, passage II, center liquid pipe, collector tube and spinning moulding area, the passage I are set in the sprayer body in road, the shower nozzle body
For " L " type, its entrance is arranged on the upper surface of sprayer body, its end be arranged on the collector tube at sprayer body lower half center
End communicates；The entrance of the passage II is arranged on the side wall of sprayer body, is extended horizontally to liquid collecting tube side wall and is communicated therewith；Institute
The center liquid pipe of stating is the hollow liquid pipe for being arranged at sprayer body center, and its latter half passes through collector tube and extends to spinning moulding
Area；The collector tube is arranged at the center of sprayer body, and its upper end starts from the outlet of passage I, and lower end terminates in spinning moulding area；It is described
Spinning moulding area is arranged at below the liquid pipe of center.
Hollow-fibre membrane spinning nozzle of the present invention, II point of the passage are three sections：First liquid input section, solution buffering area
With the second liquid input section, first liquid input section be a horizontal channel, the solution buffering area be one with collector tube as axle center,
Deep trouth shape annular region of the depth more than the first liquid input section, second liquid input section are connect solution buffering area and collector tube logical
Road, which is an annular region, or is 2N bars axisymmetric passage, wherein N >=1 centered on collector tube.First feed liquor
The depth of section is 0.3～0.8mm, and the depth of the solution buffering area is 0.7～1.3mm, and the depth of second liquid input section is
0.3～0.8mm, the depth of the solution buffering area is always greater than the first liquid input section and the depth of the second liquid input section.
Hollow-fibre membrane spinning nozzle of the present invention, in the horizontal direction, the width of the solution buffering area is 0.2～
0.5mm, the length of the second liquid input section (123) is 1.5～6mm.
Design based on more than, it will be apparent to a skilled person that in the preparation process of hollow-fibre membrane, due to
The feeding manner of spinning solution and the time of staying in the runner are to spinning solution viscoplasticity and flow to the change of force direction and have very big
Affect, when the solution buffering area increased on the passage II of the present invention can increase stop of the spinning solution in runner as storage area
Between, change spinning solution viscoplasticity, so that the quality of film silk is more stable.
Hollow-fibre membrane spinning nozzle of the present invention, the passage I are provided with 2N, N >=1, preferably 4,6 or 8,
The entrance of passage I is symmetrically distributed on the upper surface of sprayer body.The porch of passage I arranges sealing ring sealing.Passage I it is symmetrical
It is uniform in all directions when into collector tube that distribution causes solution, is conducive to which equal with the mixing of solution in passage II
It is even.
Hollow-fibre membrane spinning nozzle of the present invention, hollow-fibre membrane spinning nozzle of the present invention, the central liquid
Pipe and shower nozzle body by integral forming, its lower end are chamfering, form showerhead, and its chamfering radian is 75～87 degree.The chamfering is referred to
Center liquid pipe lower end termination face and the angle of horizontal plane.The entrance of center liquid pipe and the upper surface of sprayer body flush or above
Upper surface, its wall thickness are 0.03～0.10mm, and its center bore is 0.05～0.15mm.The structure of integration makes the center liquid pipe can
Only chamfering is carried out in port, and the thickness of tube wall can keep larger, so as to ensure also to protect while whole center liquid pipe intensity
The precision in aperture is demonstrate,proved, and integrally formed design can make hollow-fibre membrane not produce bias under spinning pressure, it is to avoid film silk
The generation of phenomenon in uneven thickness, it is ensured that precision and draw ratio, serves important function to film silk performance.
Hollow-fibre membrane spinning nozzle of the present invention, the distance of the central liquid tube wall to liquid collecting tube wall is 0.2
～0.5mm.
Hollow-fibre membrane spinning nozzle of the present invention, the length of the collector tube is 6～15mm, the passage II and collection
The through part of liquid pipe is 2～8mm with the distance of collector tube bottom.The present invention is from passage II and the through part and collector tube of collector tube
Bottom provides merged inside space for spinning solution, and the optimal shear rate that spinning solution flows through shower nozzle is obtained.
Hollow-fibre membrane spinning nozzle of the present invention, is provided with a through hole on the side wall in the spinning moulding area, described
Through hole is arranged at 30～60 degree in the polarization of side of position, does not directly blow silk.By through hole be capable of achieving control gas flow and
Temperature, and further control the thickness of exchange of solvent speed and spinning cortex.
Hollow-fibre membrane spinning nozzle of the present invention, the material of the sprayer body are selected from high temperature resistant, corrosion resistant material
Material, preferably stainless steel, as more specifically embodiment, are stainless steel sus630.
The technical purpose of second aspect present invention is to provide the method for preparing hollow-fibre membrane using above-mentioned shower nozzle, step
For：Core liquid is injected in the liquid pipe of center, will prepare the supporting layer spinning solution and separating layer spinning solution of hollow-fibre membrane respectively from logical
Road I and passage II inject, and separating layer spinning solution and supporting layer spinning solution enter collector tube, and passing through in passage II and collector tube
The place of wearing crosses, and the two is contacted with core liquid at the shower nozzle of center liquid pipe, forms an exchange area, carries out exchange of solvent film forming,
Hollow-fibre membrane is formed via shower nozzle.
In above-mentioned preparation method, the injection flow velocity of the core liquid is 0.5～2mL/min, the injection of supporting layer spinning solution
Flow velocity is 1～3mL/min, and the injection flow velocity of separating layer spinning solution is 0.05～2mL/min, and the temperature control in preparation process exists
50～80 DEG C；It is 300～500mL/min by the gas flow that through hole is passed through.
In above-mentioned preparation method, as it will be apparent to a skilled person that the core liquid, separating layer spinning solution
With being chosen for known in doughnut field of membrane preparation for supporting layer spinning solution, inventor's here include specific embodiment it
One：The core liquid is water, and the separating layer spinning solution is polyimide solution, and the supporting layer spinning solution is polysulfones solution, its
Described in separating layer spinning solution and supporting layer spinning solution viscosity be ten thousand centipoises of 8-10.
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
A kind of hollow-fibre membrane spinning nozzle, as shown in figure 1, for a sprayer body with solution channel, arrange in which logical
Road I 11, passage II 12, center liquid pipe 13, collector tube 14 and spinning moulding area 2, as shown in Fig. 2, Fig. 3, Fig. 4 and Fig. 5, passage I
11 be " L " type, be provided with 4, its entrance is symmetrically distributed on the upper surface of sprayer body, its end be arranged at sprayer body lower half
14 upper end of collector tube at portion center communicates；The entrance of passage II 12 is arranged on the side wall of sprayer body, and II 12 points of passage is three sections：
First liquid input section 121, solution buffering area 122 and the second liquid input section 123, the first liquid input section 121 is a horizontal channel, and solution delays
Rush area 122 for one with collector tube 14 as axle center, depth more than the first liquid input section 121 deep trouth shape annular region, the second feed liquor
Section 123 is connection solution buffering area 122 and the annular region of collector tube 14, and its depth is less than solution buffering area 122；The center
Liquid pipe 13 is the hollow liquid pipe for being arranged at sprayer body center, and its latter half is through collector tube 14 and extends to spinning moulding area 2,
The collector tube 14 is arranged at the center of sprayer body, and its upper end starts from the outlet of passage I 11, and lower end terminates in spinning moulding area 2；Institute
State spinning moulding area 2 to be arranged at below center liquid pipe 13, on its side wall, be provided with a through hole 21.
In the hollow-fibre membrane spinning nozzle, center liquid pipe 13 and shower nozzle body by integral forming, its lower end is chamfering, is formed
Showerhead, its chamfering radian are 85 degree, and the entrance of center liquid pipe 13 is higher than sprayer body upper surface 10mm, and its wall thickness is 0.05mm,
Its center bore is 0.09mm.The perforate depth of the first liquid input section 121 of passage II 12 be 0.5mm, the depth of solution buffering area 122
Spend for 1.0mm, width is 0.35mm, and the length of the second liquid input section 123 is 0.3mm, and depth is 0.5mm.The collector tube 14
Length is 11mm, and the second liquid input section 123 and the connectivity part of collector tube 14 and the distance of 14 bottom of collector tube are 4mm, collector tube 14
The distance of tube wall of tube wall and center liquid pipe 13 be 0.4mm.The through hole 21 is arranged at 45 degree in the polarization of side, is not directly blown
Silk.
Embodiment 2
The method that doughnut film preparation is carried out using the shower nozzle of embodiment 1, comprises the following steps：
Respectively from passage I 11, passage II 12 and center liquid pipe 13 injection supporting layer spinning solution, separating layer spinning solution and core
Liquid, injection rate are respectively 2mL/min, 0.2mL/min and 1mL/min, and keep each solution temperature to be 65 DEG C, separating layer spinning
Liquid, supporting layer spinning solution are converged with the connectivity part of the second liquid input section 123 in collector tube 14, and flow to 14 bottom of collector tube,
Contact with core liquid at the shower nozzle of center liquid pipe 13, carry out exchange of solvent, then Jing shower nozzles form doughnut in spinning moulding area 2
Film, is passed through 65 DEG C of air by through hole during spinneret, intake is 400mL/min.
The core liquid be water, the separating layer spinning solution be polyimide solution, its viscosity be 90,000 centipoises, the support
Layer spinning solution is polysulfones solution, and its viscosity is 90,000 centipoises.
Hollow-fibre membrane prepared by the embodiment of the present invention 2, two kinds of polymer solution converged before exchange of solvent is carried out, Jing
Shower nozzle is once spun into the supply that the more general single layer hollow tunica fibrosa of composite hollow fiber membrane saves separating layer spinning solution, and
The price of separating layer spinning solution is significantly larger than supporting layer solution, therefore with suitable economy.And its separating layer and support
Layer is not easily disconnected from, it is ensured that product quality simultaneously improves production efficiency.
Claims (14)
1. hollow-fibre membrane spinning nozzle, including a sprayer body with solution channel, it is characterised in that set in the shower nozzle body
Passage I (11), passage II (12), center liquid pipe (13), collector tube (14) and spinning moulding area (2) are put, the passage I (11) is
" L " type, its entrance are arranged on the upper surface of sprayer body, its end and the collector tube (14) for being arranged at sprayer body lower half center
Upper end communicates；The entrance of the passage II (12) is arranged on the side wall of sprayer body, extends horizontally to collector tube (14) side wall simultaneously
Communicate therewith；Center liquid pipe (13) are the hollow liquid pipe for being arranged at sprayer body center, and its latter half passes through collector tube
(14) and extend to spinning moulding area (2)；Collector tube (14) are arranged at the center of sprayer body, and its upper end starts from passage I
(11) outlet, lower end terminate in spinning moulding area (2)；Spinning moulding area (2) are arranged at below center liquid pipe (13).
2. hollow-fibre membrane spinning nozzle according to claim 1, it is characterised in that center liquid pipe (13) and shower nozzle
Body by integral forming, its lower end are chamfering, form showerhead, and its chamfering radian is 75～87 degree.
3. hollow-fibre membrane spinning nozzle according to claim 1, it is characterised in that the passage II (12) is divided into three
Section：First liquid input section (121), solution buffering area (122) and the second liquid input section (123), described first liquid input section (121) are one
Horizontal channel, described solution buffering area (122) be one with collector tube (14) as axle center, depth is more than the first liquid input section (121)
Deep trouth shape annular region, described second liquid input section (123) for connection solution buffering area (122) and collector tube (14) passage,
Which is an annular region, or is 2N bars axisymmetric passage, wherein N >=1 centered on collector tube (14).
4. hollow-fibre membrane spinning nozzle according to claim 3, it is characterised in that the first liquid input section (121)
Depth is 0.3～0.8mm, and the depth of solution buffering area (122) is 0.7～1.3mm, the second liquid input section (123)
Depth is 0.3～0.8mm, and the depth of solution buffering area (122) is always greater than the first liquid input section (121) and the second liquid input section
(123) depth.
5. the hollow-fibre membrane spinning nozzle according to claim 3 or 4, it is characterised in that in the horizontal direction, described molten
The width of liquid buffering area (122) is 0.2～0.5mm, and the length of the second liquid input section (123) is 1.5～6mm.
6. hollow-fibre membrane spinning nozzle according to claim 1, it is characterised in that the passage I (11) is provided with 2N
It is individual, N >=1, preferably 4,6 or 8, the entrance of passage I (11) is symmetrically distributed on the upper surface of sprayer body.
7. hollow-fibre membrane spinning nozzle according to claim 1, it is characterised in that the entrance of center liquid pipe (13)
With the upper surface of sprayer body flush or above upper surface, its wall thickness is 0.03～0.10mm, its center bore is 0.05～
0.15mm。
8. hollow-fibre membrane spinning nozzle according to claim 1, it is characterised in that center liquid pipe (13) tube wall is arrived
The distance of collector tube (14) tube wall is 0.2～0.5mm.
9. hollow-fibre membrane spinning nozzle according to claim 1, it is characterised in that the length of collector tube (14) is
6～15mm, the passage II (12) are 2～8mm with the through part of collector tube (14) and the distance of collector tube (14) bottom.
10. hollow-fibre membrane spinning nozzle according to claim 1, it is characterised in that the side of spinning moulding area (2)
A through hole (21) is provided with wall, and through hole (21) are arranged at 30～60 degree in the polarization of side of position, directly do not blow silk.
11. methods for preparing hollow-fibre membrane using the shower nozzle described in claim 1～10 any one, step is：At center
In liquid pipe (13), injection core liquid, will prepare the supporting layer spinning solution and separating layer spinning solution of hollow-fibre membrane respectively from passage I
(11) inject with passage II (12), separating layer spinning solution and supporting layer spinning solution enter collector tube (14), and in passage II
(12) cross with the through part of collector tube (14), the two is contacted with core liquid at the shower nozzle of center liquid pipe (13), form a friendship
Area is changed, exchange of solvent film forming is carried out, and hollow-fibre membrane is formed via shower nozzle.
12. methods according to claim 11, it is characterised in that the injection flow velocity of the core liquid is 0.5～2mL/min,
The injection flow velocity of the supporting layer spinning solution is 1～3mL/min, and the injection flow velocity of separating layer spinning solution is 0.05～2mL/min.
13. methods according to claim 11, it is characterised in that the temperature control in preparation process is at 50～80 DEG C.
14. methods according to claim 11, it is characterised in that the gas flow being passed through by through hole (21) is 300～
500mL/min。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517574A (en) * | 2018-06-04 | 2018-09-11 | 宁波建嵘科技有限公司 | A kind of spliced hollow tunica fibrosa spinneret |
| CN108914229A (en) * | 2018-07-12 | 2018-11-30 | 武汉中智德远科技开发有限公司 | A kind of hollow-fibre membrane spinning coating unit avoiding blocking |
| CN110621815A (en) * | 2017-05-11 | 2019-12-27 | 费森尤斯医疗护理德国有限责任公司 | Spinning nozzle, device having a spinning nozzle, method for producing hollow fibers or hollow fiber membranes by means of a spinning nozzle, and filter |
| CN113996189A (en) * | 2021-11-30 | 2022-02-01 | 3E膜科技有限责任公司 | Preparation method of hollow fiber separation membrane with compact selective layer |
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