CN106178975A - A kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane - Google Patents
A kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane Download PDFInfo
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- CN106178975A CN106178975A CN201610730579.6A CN201610730579A CN106178975A CN 106178975 A CN106178975 A CN 106178975A CN 201610730579 A CN201610730579 A CN 201610730579A CN 106178975 A CN106178975 A CN 106178975A
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- kynoar
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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
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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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Abstract
The present invention provides a kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane, using Kynoar as main membrane material, add polyacrylonitrile to be blended, and add macromolecular pore generators, inorganic additive, surfactant and solvent etc. and make casting solution, use wet-dry change i.e. phase separation method spinning technique to prepare Kynoar/polyacrylonitrile blended hollow-fibre membrane.The present invention with the addition of the Pvdf Microporous Hollow Fiber Membrane of polyacrylonitrile blended modification and has good hydrophilic, resistance tocrocking, flux is high, pure water flux is 300 ~ 3500L/M2 H(0.1MPa, 25 DEG C), the hollow-fibre membrane of preparation has higher intensity and good flexibility.
Description
Technical field
The present invention relates to hollow-fibre membrane, particularly a kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane.
Background technology
Membrane separating method includes microfiltration, ultrafiltration, nanofiltration and reverse osmosis, compared with traditional separation method, and membrane separating method
There is efficiency low, without advantages such as phase transformation, simple, the environmentally safes of technique.Membrane separation technique is widely used to chemical industry, food
The Industrial Wastewater Treatment such as product, medicine, electronics, electric power, iron and steel, along with socioeconomic development, large-scale Industrial Wastewater Treatment
Engineering will be more and more.Water pollution is increasingly becoming the biggest obstacle that China's urban safety supplies water, city tap-water, life at present
Sewage disposal alive and Treated sewage reusing become one of effective way solving future city water resources crisis.Along with people are increasingly closed
Note human settlement and safe drinking water, membrane separation technique, particularly Ultrafiltration Membrane process and drinking water treatment city at municipal administration water
Field will obtain large-scale application.
There are cellulose acetate, polyethylene, polypropylene, polrvinyl chloride, polyacrylonitrile for manufacturing the material separating film, gather
Sulfone, polyether sulfone, Kynoar etc..Kynoar has good mechanical mechanics property, and good has flexibility, shock resistance
Intensity is high；There is higher thermostability and tolerance to cold；Having excellent non-oxidizability, weatherability, service life is long；Poly-
Vinylidene has excellent chemical stability, is not corroded by acid, alkali, strong oxidizer and halogen under room temperature, general organic molten
Agent on it also without impact.Kynoar, as a kind of excellent membrane material, has been widely used for separating the manufacture of film.
Kynoar has good non-oxidizability, and resistance tocrocking is good, but Kynoar itself is a kind of hydrophobic material
Material, hydrophilic is poor, during so making hollow-fibre membrane, it is necessary to improve its hydrophilic, and method currently mainly is poly-in preparation
Hydrophilic modifying agent is added during vinylidene hollow-fibre membrane.China Patent Publication No. CN1579602 A introduces a kind of unsymmetrical knot
The preparation method of the sintering-aluminium oxide/polyvinylidene blending hollow-fibre membrane of structure, this hollow-fibre membrane is with polyvinyl alcohol, poly-
Vinylpyrrolidone or Polyethylene Glycol improve the hydrophilic of Pvdf Microporous Hollow Fiber Membrane as hydrophilic modifying agent.Chinese patent
Publication number CN101703895 A describes a kind of method preparing high-strength anti-pollution polyvinylidene fluoride ultrafiltration membrane filaments, the method
With the addition of alumina in Nano level and zinc oxide hybrid particles, make the hydrophilicity of film silk be greatly improved, and make prepare to gather
The intensity of vinylidene ultrafiltration membrane filaments is improved.
Polyethylene Glycol, polyvinylpyrrolidone class organic polymer hydrophilic modifying agent meeting during hollow-fibre membrane uses
Along with water slowly runs off, the hydrophilic of hollow-fibre membrane can slowly decline；Aluminium oxide, oxidisability class inorganic hydrophilic modifying agent are with poly-
The poor compatibility of vinylidene, inorganic hydrophilic modifying agent improves the hydrophilic effect of Pvdf Microporous Hollow Fiber Membrane and also fails to understand
Aobvious.
Be blended with hydrophilic polymer is also to improve a kind of hydrophilic method of Kynoar.China Patent Publication No.
CN101703897 A introduces the preparation method of a kind of polyvinylidene fluoride (PVDF) ultrafiltration membrane improving permeability, and this ultrafilter membrane adds polyethers
Sulfone and polyvinylidene blending, compared with Kynoar, polyether sulfone has preferable hydrophilic, makes the logical of polyvinylidene fluoride film
The water yield is greatly improved.China Patent Publication No. CN101422706 A introduces one and has the hydrophilic blend polyvinylidene fluorine second of improvement
The preparation method of alkene hollow-fibre membrane, adds polyether sulfone, cellulose diacetate, Triafol T or hydroxymethyl cellulose and prepares
Go out polyvinylidene fluoride/polyethersulfone sulfone/cellulose derivative blended membrane, improve hydrophilic and the dimensionally stable of polyvinylidene fluoride film
Property.China Patent Publication No. CN 102600733 A describes the preparation of a kind of homogeneity reinforced type polyvinylidene fluoride hollow fiber film
Method, this hollow-fibre membrane adds hydrophilic polymer polyacrylonitrile or polyvinyl alcohol, or hydrophilic inorganic particles hydrophilic two
Silicon oxide, as hydrophilic component, significantly improves the hydrophilic of Pvdf Microporous Hollow Fiber Membrane.
Polyacrylonitrile has good chemical stability, with membrane material phases such as Kynoar, polyether sulfone, polrvinyl chloride
Ratio, polyacrylonitrile has good hydrophilic, and the present invention uses Kynoar to be blended with two kinds of membrane materials of polyacrylonitrile, and adds
Adding the inorganic additive of modification, modified inorganic additive is good with organic polymer Kynoar and the polyacrylonitrile compatibility, system
Standby Kynoar/polyacrylonitrile blended hollow-fibre membrane good hydrophilic property, flux are high, and have higher intensity.
Summary of the invention
In order to overcome the disadvantages mentioned above of prior art, it is an object of the invention to provide and there is higher-strength, high flux, and tool
There is a kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane of improved flexibility.
The technical solution adopted for the present invention to solve the technical problems is: in a kind of Kynoar/polyacrylonitrile blended
Hollow fiber film, including the component of following percetage by weight:
Kynoar: 75～95%；
Polyacrylonitrile: 5～15%；
Inorganic additive: 0～10%；
Surfactant: 0～10%.
The preparation method of a kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane, prepares raw material and includes following weight
The component of percent:
Kynoar: 10～20%；
Polyacrylonitrile: 2～10%；
Macromolecular pore generators: 10～22%；
Inorganic additive: 0～8%；
Surfactant: 0～5%；
Water: 0～2%；
Solvent: 50～80%.
Preferably, the molecular weight of described Kynoar is 150,000 ~ 1,000,000, and the molecular weight of polyacrylonitrile is
30,000~100,000。
Preferably, described macromolecular pore generators is selected from Polyethylene Glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyoxy second
One or more in alkene, methylcellulose.
Preferably, described inorganic additive selected from nano-calcium carbonate, nano silicon one or both.The present invention selects
Inorganic additive calcium carbonate be nanoscale, mean diameter is 25～100nm, and through couple activation process；The present invention is also
Can be selected for mean diameter is 10～60nm, and through the silicon dioxide of organochlorosilane modification, treated nano-sized carbon
Acid calcium and silicon dioxide and Kynoar, polyacrylonitrile have a good compatibility, and good dispersion, do not reunite.
Preferably, described surfactant is selected from sodium lauryl sulphate, dodecylbenzene sodium sulfonate, dodecyl ammonia
One or more in base sodium propionate, cetyl trimethylammonium bromide, tween 20, Tween-60, tween 80.
Preferably, described water is deionized water.
Preferably, described solvent is selected from dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide, N-methylpyrrole
One or more in alkanone, tricresyl phosphate methyl, tricresyl phosphate ethyl.
Another object of the present invention is to provide the preparation side of a kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane
Method, uses dry-i.e. phase separation method of wet method to prepare, and its preparation process is as follows:
Step (1): first, by Kynoar, polyacrylonitrile, macromolecular pore generators, inorganic additive, surfactant, water
Put into by a certain percentage in reactor with solvent, at a temperature of 60～90 DEG C, stir the full and uniform dissolving of more than 20h；
Step (2): then, stop stirring, carry out filtering, vacuumizing and defoaming lowering the temperature, it is thus achieved that the casting film of 40～80 DEG C
Liquid；
Step (3): then, is transported to the bushing type spinning head that temperature is 50～90 DEG C by described casting solution, and spinning head endoporus leads to
Enter interior solidification liquid, form endoporus, be extruded into doughnut；
Step (4): last, by described doughnut through the air distance of 10～150mm, enters the outer solidification liquid of 20～60 DEG C
In carry out being separated and coagulation forming, and solidification liquid carries out to hollow-fibre membrane the stretching of 0～100% the most outside at once, obtains institute
State Kynoar/polyacrylonitrile blended hollow-fibre membrane.
In a preferred embodiment of the invention, it is also possible to farther include step (5): select extractant polyvinylidene fluoride
Inorganic additive inside alkene/polyacrylonitrile blended hollow-fibre membrane extracts.
Preferably, before step (1), polyacrylonitrile is put into the drying baker of 40 ~ 80 DEG C is dried more than 4h.
Preferably, the described mixed solution that interior solidification liquid is water and solvent, the concentration of solvent is 0～90%, outer solidification
Liquid is the mixed solution of water and solvent, and the concentration of solvent is 0～60%.
Preferably, one or more in hydrochloric acid, sulphuric acid, sodium hydroxide, potassium hydroxide of described extractant.
The present invention uses polyacrylonitrile and polyvinylidene blending, and polyacrylonitrile has preferable hydrophilic, improves poly-
The hydrophilic of vinylidene hollow-fibre membrane；The price of polyacrylonitrile is more much lower than Kynoar, is blended and reduces poly-inclined fluorine
The cost of ethylene hollow-fibre membrane.
The inorganic additive that the present invention adds plays the effect of pore former, improves the porosity of film.Inorganic additive from
Kynoar/polyacrylonitrile blended hollow-fibre membrane extracts, the hole size of formation and be evenly distributed, improve film
Porosity, and the pore size of film can be regulated by selecting the inorganic additive of different-grain diameter, prepare Kynoar/poly-third
The pure water flux of alkene nitrile blend hollow fiber membrane be 300～3500L/M2 H(0.1MPa, 25 DEG C), average pore size be 0.01～
0.4 μm,.
The calcium carbonate of present invention interpolation and silicon dioxide are all through modification, with Kynoar, the phase of polyacrylonitrile
Capacitive is good, can play the effect of reinforcing agent, improves tension and the resistance to compression of Kynoar/polyacrylonitrile blended hollow-fibre membrane
Intensity, makes the Kynoar/polyacrylonitrile blended hollow-fibre membrane of preparation have good mechanical mechanics property, polyvinylidene fluoride
The tensile break strength of alkene/polyacrylonitrile blended hollow-fibre membrane is 3.0～6.0MPa, elongation at break is 90～200%.
The present invention is when preparing Kynoar/polypropene blended nitrile hollow-fibre membrane, by adjusting in outer solidification liquid
Godet roller and the speed of wire wrapping wheel carry out the stretching of 0～100%, doughnut in drawing process to the hollow-fibre membrane of firm solidification
Film is immersed in outer solidification liquid, is improve the porosity of hollow-fibre membrane by stretching.
The Kynoar of the present invention/polyacrylonitrile blended hollow-fibre membrane has good hydrophilic, resistance tocrocking, tool
Having higher flux, good pliability, can be applicable to Drinking Water Filtration and process, municipal tap water and sewage disposal, industry is dirty
The aspects such as water processes, the pre-treatment of desalinization.
Detailed description of the invention
In conjunction with embodiment, the present invention is further described:
A kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane, it includes the component of following percetage by weight:
Kynoar: 75～95%
Polyacrylonitrile: 5～15%
Inorganic additive: 0 ~ 10%
Surfactant: 0～10%.
Kynoar/polyacrylonitrile blended doughnut film preparation raw material includes following components in percentage by weight:
Kynoar: 10～20%
Polyacrylonitrile: 2 ~ 10%
Macromolecular pore generators: 10～22%
Inorganic additive: 0 ~ 8%
Surfactant: 0 ~ 5%
Water: 0～2%
Solvent: 50 ~ 80%.
In the present invention, the molecular weight of described Kynoar is 150,000 ~ 1,000,000, and the molecule of polyacrylonitrile
Amount is 30,000 ~ 100,000；Described macromolecular pore generators is selected from Polyethylene Glycol, polyvinylpyrrolidone, polyvinyl alcohol, gathers
One or more in oxygen ethylene, methylcellulose；Described surfactant is selected from sodium lauryl sulphate, detergent alkylate
In sodium sulfonate, sodium dodecyl aminopropionitrile, cetyl trimethylammonium bromide, tween 20, Tween-60, tween 80 one
Plant or several；Described water is deionized water；Described solvent selected from dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide,
One or more in N-Methyl pyrrolidone, tricresyl phosphate methyl, tricresyl phosphate ethyl.
In the present invention, described inorganic additive one in calcium carbonate, the silicon dioxide or two several.Preferably nanometer
Level calcium carbonate and nanometer grade silica, wherein, nano-calcium carbonate mean diameter is 25～100nm, and it is pre-first passes through coupling and live
Change processes；Nano silicon mean diameter is 10～60nm, and it is pre-first passes through organochlorosilane modification.
The internal diameter of described hollow-fibre membrane is 0.5～1.0mm, external diameter is 0.8～1.6mm, tensile break strength be 3.0～
6.0MPa, elongation at break is 90～200%, pure water flux be 300～3500L/M2 H(0.1MPa, 25 DEG C), average pore size
It it is 0.01～0.4 μm.
Present invention also offers the preparation method of a kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane, described in it
Hollow-fibre membrane prepared by dry-i.e. phase separation method of wet method, its preparation process is as follows:
Step (1): first, by Kynoar, polyacrylonitrile, macromolecular pore generators, inorganic additive, surfactant, water
Put into by a certain percentage in reactor with solvent, at a temperature of 50～90 DEG C, stir the full and uniform dissolving of more than 20h；
Step (2): then, stop stirring, carry out filtering, vacuumizing and defoaming lowering the temperature, it is thus achieved that the casting film of 40～80 DEG C
Liquid；
Step (3): then, is transported to the bushing type spinning head that temperature is 50～90 DEG C by described casting solution, and spinning head endoporus leads to
Enter interior solidification liquid, form endoporus, be extruded into doughnut；
Step (4): last, by described doughnut through the air distance of 10～150mm, enters the outer solidification liquid of 20～60 DEG C
In carry out being separated and coagulation forming, and solidification liquid carries out to hollow-fibre membrane the stretching of 0～100% the most outside at once, obtains institute
State Kynoar/polyacrylonitrile blended hollow-fibre membrane.
In a preferred embodiment of the invention, it is also possible to farther include step (5): select extractant polyvinylidene fluoride
Inorganic additive inside alkene/polyacrylonitrile blended hollow-fibre membrane extracts.
Polyacrylonitrile, before step (1), is put into and is dried more than 4h in the drying baker of 40 ~ 80 DEG C by the present invention.
The described mixed solution that interior solidification liquid is water and solvent, the concentration of solvent is 0～90%；Outer solidification liquid be water and
The mixed solution of solvent, the concentration of solvent is 0～60%；Described extractant is selected from hydrochloric acid, sulphuric acid, sodium hydroxide, hydroxide
One or more in potassium.
Below by way of specific embodiment, the present invention is described in detail.
Embodiment 1: weigh that Kynoar 14.5%, polyacrylonitrile be poly-3%, Polyethylene Glycol 10%, poly-second by weight percentage
Alkene pyrrolidone 3%, nano silicon 1.5%, tween 2%, water 1%, dimethyl acetylamide 65% are put in reactor, 90
Stir more than 20h at a temperature of DEG C, then stop stirring, filter, vacuumizing and defoaming carrying out is lowered the temperature and is obtained the casting solution of 75 DEG C, casting
Film liquid is transported to the bushing type spinning head of 75 DEG C under nitrogen pressure effect, is passed through 50 DEG C, 50% dimethyl acetylamide in sleeve pipe
The interior solidification liquid of aqueous solution, is extruded into doughnut, is then passed through the air distance of 50mm, enters 40 DEG C, 5% dimethylacetamide
The outer solidification liquid of amine aqueous solution solidifies, and hollow-fibre membrane is stretched 50% by horse back solidification liquid the most outside, then film silk is received
Collection, obtains Kynoar/polyacrylonitrile blended hollow-fibre membrane.The Kynoar of preparation/polyacrylonitrile blended hollow is fine
Dimension film internal diameter be 0.52mm, external diameter 1.02mm, pure water flux be 1250L/M2 H(0.1MPa, 25 DEG C), average pore size is
0.07 μm, tensile break strength is 3.4MPa, elongation at break is 120%.
Comparing embodiment 1: weigh Kynoar 17.5%, Polyethylene Glycol 10%, polyvinylpyrrolidine by weight percentage
Ketone 3%, nano silicon 1.5%, tween 2%, water 1%, dimethyl acetylamide 65% are put in reactor, use embodiment 1
Spinning technique, prepare Pvdf Microporous Hollow Fiber Membrane, the internal diameter of this hollow-fibre membrane is 0.51mm, external diameter is
1.00mm, pure water flux be 1030L/M2 H(0.1MPa, 25 DEG C), average pore size be 0.07 μm, tensile break strength is
3.3MPa, elongation at break are 130%.
Finding out from comparing embodiment 1, without polyacrylonitrile, the pure water flux of Pvdf Microporous Hollow Fiber Membrane declines
220L/M2 H(0.1MPa, 25 DEG C), polyacrylonitrile is to the hydrophilic modifying of Pvdf Microporous Hollow Fiber Membrane clearly.
Embodiment 2: weigh that Kynoar 14%, polyacrylonitrile be poly-2.5%, Polyethylene Glycol 15%, tween by weight percentage
2%, water 0.5%, nano-calcium carbonate 3%, dimethyl acetylamide 63% are put in reactor, at a temperature of 90 DEG C stir 20h with
On, then stop stirring, filter, vacuumizing and defoaming carrying out is lowered the temperature and is obtained the casting solution of 80 DEG C, casting solution is at nitrogen pressure masterpiece
It is transported to the bushing type spinning head of 70 DEG C under with, in sleeve pipe, is passed through 50 DEG C, the interior solidification liquid of 50% dimethylacetamide amine aqueous solution,
It is extruded into doughnut, is then passed through the air distance of 50mm, enter 40 DEG C, the outer solidification liquid of 5% dimethylacetamide amine aqueous solution
Middle solidification, and solidification liquid stretches 100% outside, then film silk is collected, with hydrochloric acid the calcium carbonate inside hollow-fibre membrane
Extract, obtain Kynoar/polyacrylonitrile blended hollow-fibre membrane.The Kynoar of preparation/polyacrylonitrile blended
The internal diameter of hollow-fibre membrane is 0.52mm, external diameter 1.04mm, pure water flux be 3080L/M2 H(0.1MPa, 25 DEG C), average hole
Footpath is 0.20 μm, and tensile break strength is 3.1MPa, elongation at break is 100%.
Comparing embodiment 2: dissolve by percentage by weight material identical in embodiment 2, in spinning technique after solidification
Hollow-fibre membrane do not stretch, other technique and extraction process are same as in Example 2.Kynoar/poly-third of preparation
The internal diameter of alkene nitrile blend hollow fiber membrane is 0.50mm, for 1.01mm, pure water flux be 2500L/M2 H(0.1MPa, 25 DEG C),
Average pore size is 0.17 μm, and tensile break strength is 3.1MPa, elongation at break is 150%.Kynoar/polyacrylonitrile is common
After mixed hollow-fibre membrane is stretched, aperture can become greatly, flux becomes big.
Embodiment 3: weigh Kynoar 17%, polyacrylonitrile 4%, Polyethylene Glycol 10%, polyethylene pyrrole by weight percentage
Pyrrolidone 3%, tween 2%, water 1%, nano silicon 2%, dimethyl acetylamide 61% are put in reactor, 90 DEG C of temperature
Lower stirring more than 20h, then stop stirring, filter, vacuumizing and defoaming carrying out is lowered the temperature and is obtained the casting solution of 80 DEG C, casting solution exists
Nitrogen pressure effect is transported to the bushing type spinning head of 80 DEG C, be passed through in sleeve pipe 50 DEG C, 50% dimethylacetamide amine aqueous solution interior
Solidification liquid, is extruded into doughnut, be then passed through the air distance of 50mm, enters 40 DEG C, 5% dimethylacetamide amine aqueous solution
Outer solidification liquid solidifies, and solidification liquid stretches 80% outside, then film silk is collected, with sodium hydroxide in hollow-fibre membrane
The silicon dioxide in face extracts, and obtains Kynoar/polyacrylonitrile blended hollow-fibre membrane.The Kynoar of preparation/
The internal diameter of polyacrylonitrile blended hollow-fibre membrane is 0.52mm, external diameter 1.03mm, pure water flux be 700L/M2 H(0.1MPa,
25 DEG C), average pore size is 0.02 μm, and tensile break strength is 4.8MPa, elongation at break is 160%.
Embodiment 4: weigh Kynoar 17%, polyacrylonitrile 2%, Polyethylene Glycol 12%, polyethylene pyrrole by weight percentage
Pyrrolidone 2%, tween 2%, water 1%, nano-calcium carbonate 3%, dimethyl acetylamide 61% are put in reactor, at a temperature of 90 DEG C
Stirring more than 20h, then stop stirring, filter, vacuumizing and defoaming carrying out is lowered the temperature and is obtained the casting solution of 80 DEG C, casting solution is at nitrogen
Be transported to the bushing type spinning head of 80 DEG C under atmospheric pressure effect, be passed through in sleeve pipe 50 DEG C, 50% dimethylacetamide amine aqueous solution interior
Solidification liquid, is extruded into doughnut, be then passed through the air distance of 50mm, enters 40 DEG C, 5% dimethylacetamide amine aqueous solution
Outer solidification liquid solidifies, and solidification liquid stretches 100% outside, then film silk is collected, obtain Kynoar/polyacrylonitrile
Blend hollow fiber membrane.The internal diameter of the Kynoar/polyacrylonitrile blended hollow-fibre membrane of preparation is 0.53mm, external diameter
1.02mm, pure water flux be 960L/M2 H(0.1MPa, 25 DEG C), average pore size is 0.04 μm, and tensile break strength is
4.3MPa, elongation at break are 110%.
Comparing embodiment 4: film silk hydrochloric acid embodiment 4 collected extracts the calcium carbonate inside hollow-fibre membrane
Come, obtain Kynoar/polyacrylonitrile blended hollow-fibre membrane.The Kynoar of preparation/polyacrylonitrile blended hollow is fine
Dimension film internal diameter be 0.52mm, external diameter be 1.01mm, pure water flux be 1550L/M2 H(0.1MPa, 25 DEG C), average pore size is
0.06 μm, tensile break strength is 4.2MPa, elongation at break is 110%.After inorganic additive nano-calcium carbonate extracts,
The average pore size of film increases, and porosity increases, and pure water flux is greatly improved.
In sum, after those of ordinary skill in the art reads file of the present invention, according to technical scheme and
Technology design makes other various corresponding conversion scheme without creative mental work, belongs to the model that the present invention is protected
Enclose.
Claims (10)
1. Kynoar/polyacrylonitrile blended hollow-fibre membrane, it is characterised in that include following percetage by weight
Component:
Kynoar: 75～95%；
Polyacrylonitrile: 5～15%；
Inorganic additive: 0～10%；
Surfactant: 0～10%.
Kynoar the most according to claim 1/polyacrylonitrile blended hollow-fibre membrane, it is characterised in that described hollow
The internal diameter of fibrous membrane is 0.5～1.0mm, external diameter is 0.8～1.6mm, and tensile break strength is 3.0～6.0MPa, extension at break
Rate is 90～200%, pure water flux be 300～3500L/M2 H(0.1MPa, 25 DEG C), average pore size is 0.01～0.4 μm.
Kynoar the most according to claim 1/polyacrylonitrile blended hollow-fibre membrane, it is characterised in that prepare raw material
Component including following percentage by weight:
Kynoar: 10～20%；
Polyacrylonitrile: 2～10%；
Macromolecular pore generators: 10～22%；
Inorganic additive: 0 ~ 8%；
Surfactant: 0～5%；
Water: 0～2%；
Solvent: 50～80%.
Kynoar the most according to claim 3/polyacrylonitrile blended doughnut film preparation raw material, it is characterised in that
Kynoar is 6 ~ 10:0 ~ 4 with the adding proportion of polyacrylonitrile.
Kynoar the most according to claim 3/polyacrylonitrile blended doughnut film preparation raw material, it is characterised in that
The molecular weight of described Kynoar is 150,000 ~ 1,000,000, and the molecular weight of polyacrylonitrile is 30,000 ~ 100,000.
Kynoar the most according to claim 3/polyacrylonitrile blended doughnut film preparation raw material, it is characterised in that
Described macromolecular pore generators is in Polyethylene Glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene, methylcellulose
One or more；Described inorganic additive selected from nano-calcium carbonate, nano silicon one or both, nano-calcium carbonate
Mean diameter is 25～100nm, and its pre-couple activation that first passes through processes, and nano silicon mean diameter is 10～60nm, its
First pass through organochlorosilane modification in advance；Described surfactant is selected from sodium lauryl sulphate, DBSA
One in sodium, sodium dodecyl aminopropionitrile, cetyl trimethylammonium bromide, tween 20, Tween-60, tween 80 or
Several；Described water is deionized water；Described solvent is selected from dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide, N-
One or more in methyl pyrrolidone, tricresyl phosphate methyl, tricresyl phosphate ethyl.
7. the preparation method of Kynoar/polyacrylonitrile blended hollow-fibre membrane, it is characterised in that described hollow is fine
Dimension film is prepared by dry-i.e. phase separation method of wet method, and its preparation process is as follows:
Step (1): by Kynoar, polyacrylonitrile, macromolecular pore generators, inorganic additive, surfactant, water and solvent
Put into by a certain percentage in reactor, at a temperature of 60～90 DEG C, stir the full and uniform dissolving of more than 20h；
Step (2): stop stirring, carry out filtering, vacuumizing and defoaming lowering the temperature, it is thus achieved that the casting solution of 40～80 DEG C；
Step (3): described casting solution is transported to the bushing type spinning head that temperature is 50～90 DEG C, spinning head endoporus is passed through interior solidifying
Solid-liquid, forms endoporus, is extruded into doughnut；
Step (4): by described doughnut through the air distance of 10～150mm, enter in the outer solidification liquid of 20～60 DEG C
Row is separated and coagulation forming, and hollow-fibre membrane carries out in horse back solidification liquid the most outside the stretching of 0～100%, obtains described poly-
Vinylidene/polyacrylonitrile blended hollow-fibre membrane.
Kynoar the most according to claim 7/polyacrylonitrile blended doughnut membrane preparation method, its feature exists
In: farther include step (5): select extractant that the Kynoar obtained in step (4)/polyacrylonitrile blended hollow is fine
Inorganic additive inside dimension film extracts.
Kynoar the most according to claim 7/polyacrylonitrile blended doughnut membrane preparation method, it is characterised in that
Before step (1), polyacrylonitrile is put into the drying baker of 40 ~ 80 DEG C is dried more than 4h.
Kynoar the most according to claim 7/polyacrylonitrile blended doughnut membrane preparation method, its feature exists
In the described mixed solution that interior solidification liquid is water and solvent, the concentration of solvent is 0～90%；Outer solidification liquid is water and solvent
Mixed solution, the concentration of solvent is 0～60%；Described extractant is in hydrochloric acid, sulphuric acid, sodium hydroxide, potassium hydroxide
One or more.
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| CN110983631A (en) * | 2019-12-19 | 2020-04-10 | 北京科技大学 | Composite nanofiber membrane and preparation method thereof |
| CN111013407A (en) * | 2019-12-31 | 2020-04-17 | 杭州帝凡过滤技术有限公司 | Multi-stage filtration hydrophilic nanofiber membrane and manufacturing method thereof |
| CN111530286A (en) * | 2020-04-28 | 2020-08-14 | 南京工业大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
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| CN112813522A (en) * | 2020-12-28 | 2021-05-18 | 乐昌市宝创环保新材料制品有限公司 | Antibacterial and bacteriostatic non-woven fabric fiber material and production process and application thereof |
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Application publication date: 20161207 |