CN106000115A - Hollow fiber membrane with efficient filtering defect-free structure and preparation method of hollow fiber membrane - Google Patents
Hollow fiber membrane with efficient filtering defect-free structure and preparation method of hollow fiber membrane Download PDFInfo
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- CN106000115A CN106000115A CN201610415030.8A CN201610415030A CN106000115A CN 106000115 A CN106000115 A CN 106000115A CN 201610415030 A CN201610415030 A CN 201610415030A CN 106000115 A CN106000115 A CN 106000115A
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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
- 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
-
- 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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a hollow fiber membrane with an efficient filtering defect-free structure and a preparation method of the hollow fiber membrane, and relates to a hollow fiber membrane and the preparation method thereof. According to the technical scheme, the preparation method comprises the steps that macromolecular resin, an organic solvent and an additive are prepared into a spinning solution; internal solidification liquid is prepared from dihydroxy alcohol compounds or an aqueous solution containing the dihydroxy alcohol compounds or an aqueous solution containing an organic solvent; the spinning solution and the internal solidification liquid achieve spinning towards air through two layers of tubular nozzles; a product enters a solidification tank to make contact with external solidification liquid, and then washing is conducted; after rolling is conducted, the hollow fiber membrane is prepared. According to the hollow fiber membrane and the preparation method thereof, a thin and uniform defect-free external surface layer can be formed, the target solute clearing property is high, pores can be mutually connected by controlling the certain phase separation speed to form the fishing-net-shaped porous structure, therefore, the fluid resistance is decreased to the minimum, the clearing property is high, the filtering property is very excellent, and a treatment result is efficient and credible.
Description
Technical field
The present invention relates to a kind of hollow-fibre membrane and manufacture method thereof, be specifically related to one and there is high efficiency filter
The hollow-fibre membrane of zero defect structure and manufacture method thereof.
Background technology
Recently, the lock out operation technology of the polymeric membrane for separation with selective filter is used particularly to develop.
For example, this technology is becoming widely adopted in extensive clean water treatment and Xia Shui, waste water process, quilt
It is used in the ultra-pure water manufacturing process of every field, pharmaceuticals manufacturing process and bio-fabrication process etc. and there is generation
The field of table.From form, polymeric membrane for separation can be divided into flat film and hollow-fibre membrane.With
Flat film is compared, and the surface area of the internal hollow-fibre membrane with center cavity (Lumen) is bigger, therefore, and hollow
The treatment effeciency of fibrous membrane is apparently higher than flat film.It is being similar to the field of blood purification of hemodialysis, various
Separation in medium-sized, small-sized and extensive clean water treatment field, biological medicine manufacturing process, refined, under
The fields such as water, waste water process, the use of hollow-fibre membrane is significantly more than flat film.Current hollow-fibre membrane
Material be commonly cellulose acetate (Cellulose acetate, CA), polyacrylonitrile (Polyacrylonitrile,
PAN), polrvinyl chloride (Polyvinylchroride, PVC), polymethyl methacrylate
(Polymethylmethaacrylate, PMMA), polyethylene (polyethylene, PE), polypropylene
(Polypropylene, PP), polysulfones (polysulfone, PS), polyether sulfone (Polyethersulfone,
PES), polyamide (Polyamide, PA), polyimides (Polyimide, PI) and polyvinylidene fluoride
(Polyvinylidene fluoride, PVDF) etc., wherein, polysulfones, polyether sulfone and poly-inclined difluoro second
The polymeric membrane for separation of alkene material has significant thermostability, chemical resistance and resistance to pressure, its scope of application
Expand to every field.Additionally, polysulfones, polyether sulfone and the hollow-fibre membrane of polyvinylidene fluoride material
The spinning liquid being made up of macromolecule resin, organic solvent and additive and solidified inside liquid are passed through bimetallic tube
The spinning in air of shape nozzle, subsequently into coagulating basin, contact with outside solidification liquid, main by washing,
Dry, batch this dry-and wet-type spinning technique (Dry-wet spinning) and manufacture.Through this mistake
Cheng Hou, the aperture form of the hollow-fibre membrane made is the most rounded or oval, and its size and distribution are right
Separation property and permeability play main decisive action.
In order to make filterability the most outstanding, needing two kinds of performances most basic, most important, one is to determine
Can effectively remove the separating property of how many target substances, namely repel (Rejection) performance, another
Plant the through performance being to determine to process while keeping effective separating property quantity, but, this
Two kinds of performances are difficult to and deposit.
When manufacturing hollow-fibre membrane according to existing dry-and wet-type spinning method, in order to strengthen through performance, improve
The rate of filtration, it should the aperture in increased fiber film, but after hole diameter enlargement, just cannot meet repulsion performance
Requirement level, therefore, it is difficult to obtain satisfied result when actually used.It addition, its compressive resistance is relatively
Low, cause the process flow in processing procedure to reduce rapidly.In general, in order to strengthen porous, should
Reduce the macromolecule content in spinning liquid, but so, the viscosity of spinning liquid will reduce, according to dry
When wet-spinning manufactures hollow-fibre membrane, spinnability will be deteriorated, and then causes production efficiency to be difficult to carry
High.Meanwhile, can produce separated during dry-and wet-type spinning, the machine of the hollow-fibre membrane made
Tool intensity is relatively low, in order to make this problem be improved, currently studies multiple method.But,
Reduce the macromolecule content in hollow-fibre membrane in order to improve mechanical strength, hollow-fibre membrane will be reduced
Permeability, the main performance causing hollow-fibre membrane is low.
In order to solve this problem, research worker once attempted improving while keeping macromolecule content passing through
Property.Method in Japanese Laid-Open Patent 1995-163847 is, in the process manufacturing ps hollow fiber uf membrane
Its phase separation temperature of middle regulation, increases the permeability of water while improving intensity with this.But its shortcoming
It is first to manufacture at a temperature of stable, take care of spinning liquid, in nozzle, then change rapidly temperature, meeting
Spinning liquid is made to become unstable.Along with the change of temperature, also there is serious change in the stability of spinning liquid,
It is difficult to control at a temperature of equilibrium again the steady statue of spinning liquid, accordingly, because spinning liquid is when spinning
Instability, causes shredding phenomenon during spinning serious, it is impossible to apply in the middle of production technology.
Japanese Laid-Open Patent 1995-163849 and Japanese Laid-Open Patent 2002-79066 also describe a kind of system
Make method, during manufacturing film, first add inorganic particulate, make after film again by inorganic particulate dissolution,
Purpose is to increase water permeability.But the shortcoming of this method is, if adding base polymer (Base
Polymer) with there is no the inorganic particulate of the compatibility, the stability of masking stock solution will decline to a great extent, not only difficult
For production, after masking, also to increase a dissolution operation, the most loaded down with trivial details.
Meanwhile, research worker has also carried out various trial, such as by reducing surface tension
Improve through performance etc..United States Patent (USP) 4,340,482 describes at separation membrane surface grafting hydrophilic monomer
Method；The method that Japanese Unexamined Patent Publication the 60-246812nd and Japanese Unexamined Patent Publication the 62-011503rd are introduced is,
First with hydrophobic resin manufacture separation film, then this separation film is immersed in and is lived by hydroaropic substance or surface
Property agent composition wetting agent solution in, be dried subsequently, allow be made up of hydrophobic resin separation film tool
There is hydrophilic.
It addition, United States Patent (USP) 5,340,480 describes and makes polyvinylpyrrolidone (polyvinyl
Pyrrolidone, PVP) etc. hydrophilic macromolecule be aggregated in separation membrane surface, thus it is hydrophilic to give separation film
The method of property.Japanese Unexamined Patent Publication the 59-186604th is described to be processed by plasma discharge and allows separation film
Surface has hydrophilic method.
As can be seen here, in conventional method, the hydrophilicity-imparting treatment work of hydrophobicity polysulfones system polymeric membrane for separation
Sequence is extremely complex, and the hydrophilic effect after processing is unsatisfactory, the hollow-fibre membrane made
Mechanical strength is the most barely satisfactory.
Summary of the invention
Present invention aims to defect and the deficiency of prior art, it is provided that one has high efficiency filter
The hollow-fibre membrane of zero defect structure and manufacture method thereof, it can be formed the thinnest but also the most flawless
External surface layer is strong to the scavenging of target solute, it is possible to make pore by controlling certain phase separation speed
Being connected with each other, form the cellular structure of fishing net shaped, make fluid resistance be down to minimum, not only scavenging is strong,
Strainability is the most outstanding, and result is efficient, credible.
For achieving the above object, the technical solution used in the present invention is: 1, use macromolecule resin, organic
Solvent and additive make spinning liquid；2, dihydroxy alcohol compounds is used, containing dihydroxy alcohol compounds
Aqueous solution or configure solidified inside liquid containing the aqueous solution of organic solvent；3, spinning liquid and solidified inside liquid
By double-deck shaped nozzles spinning in air；4, subsequently into coagulating basin, contact with outside solidification liquid,
Clean；5, hollow-fibre membrane is made after batching.
Described spinning liquid at least will be by macromolecule resin, fine pores forming agent, non-solvent, solvent etc. four
Plant into and be grouped into.Use macromolecule resin time, can use cellulose acetate, polyacrylonitrile, polrvinyl chloride,
The various macromolecule resins such as polyamide, polyimides, polysulfones, polyether sulfone and polyvinylidene fluoride.
Described solvent can be selected for N-N-dimethyl acetylamide (DMAc), N,N-dimethylformamide (DMF), N-
N-methyl-2-2-pyrrolidone N (NMP), dimethyl sulfoxide (DMSO) etc..
Described solvent is 45～85%.
The additive of described composition spinning liquid at least uses two or more hydrophilic compounds；Hydrophilic
Compound uses macromolecular compound and low molecular compound simultaneously, and usage rate is macromolecular compound:
Low molecular compound 1:1～5:1.
The additive of described composition spinning liquid accounts for 5～25%.
The temperature of described spinning liquid is maintained in the range of 15 DEG C～60 DEG C.
Polymer content in described spinning liquid is 10～30%.
Described spinning liquid at least should use two or more fine pores forming agent, and described fine pores is formed
Agent is the poly alkylene glycol with Polyethylene Glycol, polypropylene glycol as representative, polyvinylpyrrolidone etc.
Hydrophilic macromolecule is low with hydrophilic such as low molecule dihydroxy alcohols, ethanol class, inorganic salts, water
The compound of molecule；
Described solidified inside liquid can use dihydroxy alcohol compounds, water containing dihydroxy alcohol compounds
Solution or the aqueous solution containing organic solvent.During preparation solidified inside liquid, dihydroxy alcohol compounds uses
Diethylene glycol and the mixed solution of water.Solidified inside liquid should be regulated according to the position on top layer and compactness
Mixed proportion.In order to make the external pressure filtering type hollow-fibre membrane with top layer, solidified inside in outside
Water content in liquid should control within 20% weight.
The speed batched in described step 5 is 10～70m/min.
The outer skin structure of the hollow-fibre membrane that the present invention makes solidifies by postponing phase separation,
Top layer is uniform, there's almost no defect；Lower floor is the fishing net shaped cellular structure of perforate；Interior skin
It is made up of more than the major diameter pore of 10 μm diameter.
The hollow-fibre membrane that the present invention makes there is external surface layer and porous lower layer, in unsymmetric structure,
The hole diameter of external surface layer is 0.1～0.5 μm, and water penetration is 5～30ml/c min kg/
cm2；The Solute removal rate of microballon is more than 5log (99.999%)；Compress index and be less than solute 0.2, resistance to
Pressure property is strong.
The present invention, after making spinning liquid and solidified inside liquid according to above-mentioned condition, uses and allows liquid from spinning
The dry-and wet-type spin processes of ejection in silk nozzle.Through air-gap before solidification in coagulating basin, by regulation
The temperature of air-gap, humidity and the structure of distance regulation external surface layer.
When the present invention manufactures hollow-fibre membrane, the environment of setting air gap according to dry-and wet-type spin processes, temperature
Degree is set between 20～40 DEG C, and humidity is set to more than 50%, and distance is set to 5～30cm.The distance of air-gap
The longest, separated (Delay demixing) process of delay in air-gap (Air Gap) is the longest, has
It is beneficial to formation and does not has top layer, defective uniform outer, but result is likely according to the thermodynamics shape of spinning liquid
State and viscosity etc. produce change.
The invention have the benefit that and can form thin and uniform zero defect external surface layer, formed all
Behind even top layer, the speed of the phase separation being carried out continuously is the most consistent, and lower floor no longer exists inequality
Even huge hole, meanwhile, pore is connected with each other, and forms the cellular structure of fishing net form,
The most outstanding to the separation selectivity of target substance, make hydrodynamics resistance be down to minimum, not only remove
Property strong, strainability is the most outstanding, and result is efficient, credible.
Accompanying drawing explanation
Fig. 1 is the physical property structural representation of specific embodiment of the invention hollow-fibre membrane
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out
Clearly and completely describe, it is clear that described embodiment is only a part of embodiment of the present invention, and
It is not all, of embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are not doing
Go out the every other embodiment obtained under creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1:
By the polysulfone resin of 17% weight, the polyvinylpyrrolidone of 10% weight, the ethylene glycol of 10% weight
Put into the dimethyl acetylamide stirring and dissolving of 63% weight, make transparent spinning liquid.This spinning liquid is allowed to protect
Holding at 50 DEG C, the ratio divided with 11.0g/ from bimetallic tube spues, simultaneously from internal discharge opening with 5.0g/
The speed divided injects 85% dimethylacetamide amine aqueous solution, uses as solidified inside liquid.Then its warp is allowed
Cross the air-gap of 20cm, spin doughnut by the outside coagulating basins (water) of 45 DEG C, after solidification washing
It is cleaned continuously, batches with the coiling speed that 50m/ divides, produce hollow-fibre membrane.Hollow is fine
Shown in structure figure below of dimension film:
Embodiment 2:
By the polysulfone resin of 15% weight, the Polyethylene Glycol of 13% weight, the polyvinylpyrrolidone of 5% weight,
The calcium chloride of 4% weight puts into the dimethyl acetylamide stirring and dissolving of 63% weight, makes transparent spinning liquid.
Allowing this spinning liquid be maintained at 40 DEG C, the ratio divided with 14.0g/ from bimetallic tube spues, simultaneously from inside
Discharge opening injects 85% dimethylformamide in water with the speed that 6.0g/ divides, and makes as solidified inside liquid
With.Then allow it through the air-gap of 30cm, spin hollow by the outside coagulating basins (water) of 55 DEG C fine
Dimension, cleans it continuously after solidification washing, batches with the coiling speed that 60m/ divides, produce hollow
Fibrous membrane.Shown in structure figure below of hollow-fibre membrane:
Embodiment 3
By the polysulfone resin of 14% weight, the polyvinylpyrrolidone of 10% weight, poly-the third the two of 5% weight
Alcohol, the calcium chloride of 3% weight, the water of 2% weight put into the METHYLPYRROLIDONE stirring of 64% weight
Dissolve, make transparent spinning liquid.Allow this spinning liquid be maintained at 60 DEG C, divide with 8.0g/ from bimetallic tube
Ratio spue, the speed simultaneously divided with 4.0g/ from internal discharge opening injects 85%N-methyl-2-pyrrolidine
Ketone aqueous solution, uses as solidified inside liquid.Then allow its through the air-gap of 25cm, by 40 DEG C
Outside coagulating basin (water) spinning doughnut, solidification washing after it is cleaned continuously, the volume divided with 40m/
Take speed to batch, produce hollow-fibre membrane.The structure of hollow-fibre membrane is as shown below:
Embodiment 4:
By the polyvinylidene fluoride resin of 16% weight, the polyvinylpyrrolidone of 10% weight, 5% weight
Propylene glycol, the calcium chloride of 2% weight, the water of 1% weight put into the METHYLPYRROLIDONE of 66% weight
Stirring and dissolving, makes transparent spinning liquid.This spinning liquid is allowed to be maintained at 60 DEG C, with 7.0g/ from bimetallic tube
The ratio divided spues, and the speed simultaneously divided with 3.0g/ from internal discharge opening injects 90%N-methyl-2-pyrroles
Alkanone aqueous solution, uses as solidified inside liquid.Then allow its through the air-gap of 40cm, by 45 DEG C
Outside coagulating basin (water) spinning doughnut, solidification washing after it is cleaned continuously, the volume divided with 30m/
Take speed to batch, produce hollow-fibre membrane.The structure of hollow-fibre membrane is as shown below:
Comparative example 1:
The polysulfone resin of 17% weight, the polyvinylpyrrolidone of 15% weight, the ethylene glycol of 2% weight are put
Enter the dimethyl acetylamide stirring and dissolving of 66% weight, make transparent spinning liquid.This spinning liquid is allowed to keep
At 50 DEG C, the ratio divided with 11.0g/ from bimetallic tube spues, simultaneously from internal discharge opening with 5.0g/
The speed divided injects 85% dimethylacetamide amine aqueous solution, uses as solidified inside liquid.Then its warp is allowed
Cross the air-gap of 20cm, spin doughnut by the outside coagulating basins (water) of 45 DEG C, after solidification washing
It is cleaned continuously, batches with the coiling speed that 50m/ divides, produce hollow-fibre membrane.Hollow is fine
The structure of dimension film is as shown below:
Comparative example 2:
The polysulfone resin of 14% weight, the polyvinylpyrrolidone of 22% weight are put into the N-of 64% weight
N-methyl-2-2-pyrrolidone N stirring and dissolving, makes transparent spinning liquid.This spinning liquid is allowed to be maintained at 60 DEG C,
The ratio divided with 8.0g/ from bimetallic tube spues, the speed note simultaneously divided with 4.0g/ from internal discharge opening
Enter 85%N-N-methyl-2-2-pyrrolidone N aqueous solution, use as solidified inside liquid.Then allow it through 25cm
Air-gap, spin doughnut by the outside coagulating basins (water) of 40 DEG C, after solidification washing, it is continuous
Clean, batch with the coiling speed that 40m/ divides, produce hollow-fibre membrane.The knot of hollow-fibre membrane
Structure is as shown below:
Understand referring to Fig. 1:
Pure water transmission coefficient: averaging after measuring 5 times under the same conditions, numerical value is the biggest, filterability
The strongest.
Elimination factor: average after measuring 5 times under the same conditions, be as the criterion with same microballon, numerical value is more
Greatly, removing property is the strongest.
Compress index: averaging after measuring 5 times under the same conditions, numerical value is the least, and resistance to pressure is the strongest.
This detailed description of the invention can form thin and uniform zero defect external surface layer, forms uniform table
After Ceng, the speed of the phase separation being carried out continuously is the most consistent, and lower floor no longer exists uneven huge
Macrovoid, meanwhile, pore is connected with each other, and forms the cellular structure of fishing net form, to target
The separation selectivity of material is the most outstanding, makes hydrodynamics resistance be down to minimum, and not only scavenging is strong,
Strainability is the most outstanding, and result is efficient, credible.
Although an embodiment of the present invention has been shown and described, for those of ordinary skill in the art
Speech, it is possible to understand that these embodiments can be carried out without departing from the principles and spirit of the present invention
Multiple change, revising, replace and modification, the scope of the present invention is limited by claims and equivalent thereof
Fixed.
Claims (10)
1. there is hollow-fibre membrane and the manufacture method thereof of high efficiency filter zero defect structure, its feature
The manufacture method being it is: 1, use macromolecule resin, organic solvent and additive to make spinning liquid；
2, dihydroxy alcohol compounds, the aqueous solution containing dihydroxy alcohol compounds or the water containing organic solvent are used
Solution configures solidified inside liquid；3, spinning liquid and solidified inside liquid pass through double-deck shaped nozzles in air
Spinning；4, subsequently into coagulating basin, contact with outside solidification liquid, clean；5, hollow is made after batching
Fibrous membrane.
A kind of hollow-fibre membrane with high efficiency filter zero defect structure the most according to claim 1 and
Its manufacture method, it is characterised in that described spinning liquid at least will by macromolecule resin, fine pores forming agent,
Four kinds of one-tenth such as non-solvent, solvent are grouped into；When using macromolecule resin, cellulose acetate can be used, gather
Acrylonitrile, polrvinyl chloride, polyamide, polyimides, polysulfones, polyether sulfone and polyvinylidene fluoride etc. are each
Plant macromolecule resin.
A kind of hollow-fibre membrane with high efficiency filter zero defect structure the most according to claim 1 and
Its manufacture method, it is characterised in that described solvent can be selected for N-N-dimethyl acetylamide (DMAc), N, N-bis-
Methylformamide (DMF), METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO) etc.；Solvent
Content is 45～85%.
A kind of doughnut with high efficiency filter zero defect structure the most according to claim 1
Film and manufacture method thereof, it is characterised in that the additive of described composition spinning liquid at least uses two or more
Hydrophilic compounds；Hydrophilic compounds uses macromolecular compound and low molecular compound simultaneously, makes
It is macromolecular compound with ratio: low molecular compound 1:1～5:1；Adding of described spinning liquid
Add agent and account for 5～25%；The temperature of described spinning liquid is maintained in the range of 15 DEG C～60 DEG C；Described spinning liquid
In polymer content be 10～30%.
A kind of doughnut with high efficiency filter zero defect structure the most according to claim 1
Film and manufacture method thereof, it is characterised in that described spinning liquid at least should use two or more fine pores shape
Becoming agent, described fine pores forming agent is the polyalkylene two with Polyethylene Glycol, polypropylene glycol as representative
The hydrophilic macromolecule of alcohol, polyvinylpyrrolidone etc., with low molecule dihydroxy alcohols, ethanol class,
The low molecular compound of the hydrophilic such as inorganic salts, water.
A kind of hollow-fibre membrane with high efficiency filter zero defect structure the most according to claim 1
And manufacture method, it is characterised in that described solidified inside liquid can use dihydroxy alcohol compounds, contain
The aqueous solution of dihydroxy alcohol compounds or the aqueous solution containing organic solvent.
A kind of hollow-fibre membrane with high efficiency filter zero defect structure the most according to claim 1
And manufacture method, it is characterised in that during preparation solidified inside liquid, dihydroxy alcohol compounds uses two
Glycol and the mixed solution of water.
A kind of hollow-fibre membrane with high efficiency filter zero defect structure the most according to claim 1
And manufacture method, it is characterised in that the speed batched in described step 5 is 10～70m/min.
A kind of hollow-fibre membrane with high efficiency filter zero defect structure the most according to claim 1
And manufacture method, it is characterised in that the outer skin structure of the hollow-fibre membrane that the present invention makes passes through
Postponing phase separation solidification, top layer is uniform；Lower floor is the fishing net shaped cellular structure of perforate；Internal
Top layer is made up of more than the major diameter pore of 10 μm diameter.
A kind of doughnut with high efficiency filter zero defect structure the most according to claim 1
Film and manufacture method thereof, it is characterised in that the hollow-fibre membrane that the present invention makes have external surface layer and
Porous lower layer, in unsymmetric structure, the hole diameter of external surface layer is 0.1～0.5 μm, water penetration
It is 5～30ml/c min kg/cm2；The Solute removal rate of microballon is more than 5log；Compress index
Less than solute 0.2.
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| CN201610415030.8A CN106000115A (en) | 2016-06-14 | 2016-06-14 | Hollow fiber membrane with efficient filtering defect-free structure and preparation method of hollow fiber membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110799261A (en) * | 2017-06-28 | 2020-02-14 | 3M创新有限公司 | Polyamide flat sheet membrane with microporous surface structure for trapping nanoparticles |
| CN113457476A (en) * | 2021-07-08 | 2021-10-01 | 山东招金膜天股份有限公司 | Polysulfone hollow fiber membrane and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143304A (en) * | 2007-07-17 | 2008-03-19 | 天津工业大学 | Hollow fiber membrane and its preparing process |
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| CN110799261A (en) * | 2017-06-28 | 2020-02-14 | 3M创新有限公司 | Polyamide flat sheet membrane with microporous surface structure for trapping nanoparticles |
| CN113457476A (en) * | 2021-07-08 | 2021-10-01 | 山东招金膜天股份有限公司 | Polysulfone hollow fiber membrane and preparation method thereof |
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