CN101890310B - Porous membrane using acetic acid-2-ethoxyl ethyl ester and polyethylene glycol as diluents and preparation method - Google Patents
Porous membrane using acetic acid-2-ethoxyl ethyl ester and polyethylene glycol as diluents and preparation method Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003085 diluting agent Substances 0.000 title claims abstract description 23
- 125000004494 ethyl ester group Chemical group 0.000 title abstract 2
- 239000002202 Polyethylene glycol Substances 0.000 title description 3
- 229920001223 polyethylene glycol Polymers 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012809 cooling fluid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 10
- 235000012489 doughnuts Nutrition 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229960003511 macrogol Drugs 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000000873 masking effect Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims description 2
- 239000000110 cooling liquid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 238000001471 micro-filtration Methods 0.000 abstract description 8
- 239000012510 hollow fiber Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002033 PVDF binder Substances 0.000 abstract 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 abstract 1
- 238000000108 ultra-filtration Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000002210 biocatalytic effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- 239000010802 sludge Substances 0.000 description 1
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- 229920001897 terpolymer Polymers 0.000 description 1
Images
Abstract
The invention relates to a polyvinylidene fluoride porous hollow fiber membrane and a preparation method thereof. According to a formula, the membrane comprises the following components in percentage by mass: 25 to 45 percent of first polymer P1 polyvinylidene fluoride (PVDF), 0 to 3 percent of second polymer P2 polymethylmethacrylate (PMMA), 0.9 to 2 percent of third polymer P3 polyvinylpyrrolidone (PVP), 29 to 50 percent of first diluent D1 acetic acid-2-ethoxyl ethyl ester, and 19 to 27 percent of second diluent D2 polyethylene glycol 600. The PVDF hollow fiber ultrafiltration/microfiltration membrane prepared by the method has the advantages of high chemical stability, pollution resistance and high strength, and can provide high-performance membrane products for an MBR process.
Description
Technical field
The present invention relates to a kind of Kynoar (PVDF) porous hollow fiber membrane and method for making thereof, especially relate to a kind of diluent and be acetic acid-2-ethoxy-ethyl ester and polyethylene glycol Kynoar (PVDF) porous hollow fiber membrane and method for making thereof.
Background technology
Membrane biological reactor process (MBR) is a kind of novel, efficient sewage disposal technology, and it can realize separating of biocatalytic reaction and water and degradation material simultaneously, and water resource is regenerated, and realizes the reuse water standard.Waste water advanced processing and the regeneration new technology of advanced, efficient and low energy consumption in the present age.Prepare wherein that intensity is high, antifouling property good, milipore filter and microfiltration membranes cheaply, be the core technology of membrane biological reactor process.But most commercial super, the microfiltration membranes effect is all undesirable, can't satisfy industrial requirement.On the other hand, at present super, the most employing phase separation of microfiltration membranes legal system is standby, the film of making comprises the large cavity structure of finger-like mostly, membrane aperture skewness, intensity difference, use easy fracture of wire in sewage, membrane lifetime is short, is unsuitable for using in membrane biological reactor process.
Summary of the invention
The objective of the invention is to propose a kind of Kynoar porous hollow fiber membrane and method for making thereof that is suitable for using in membrane biological reactor process.
Kynoar porous hollow fiber membrane provided by the invention, the formula composition of its masking and content thereof be by percentage to the quality:
The first polymer P
1: Kynoar (PVDF) 25～45%
The second polymer P
2: polymethyl methacrylate (PMMA) 0～3%
Terpolymer P
3: polyvinylpyrrolidone (PVP) 0.9～2%
The first diluent D
1: acetic acid-2-ethoxy-ethyl ester 29～50%
The second diluent D
2: Macrogol 600 19～27%.
Preferably, wherein the mass ratio of each composition is:
P
2/P
1＝0～0.12，
P
3/P
1＝0.02～0.08，
D
1/D
2＝1.2/1～2.5/1，
P/ (P+D)=(25～45) %, wherein: P=P
1+ P
2+ P
3, D=D
1+ D
2
Wherein P+D is absolutely.
Preferred, wherein the mass ratio of each composition is:
Wherein said P
2/ P
1=0～0.04,
Wherein said P
3/ P
1=0.03～0.05,
Wherein said D
1/ D
2=1.4/1～2/1,
Wherein said P/ (P+D)=(30～40) %.
Preferably, add nucleant agent N in described first, second mixing diluents solvent: methyl hydroxybenzoate, and the addition of nucleator (mass ratio) is N/P
1=4 ‰.
Preferably, wherein said Kynoar (PVDF) weight average molecular weight is 300000, and described polymethyl methacrylate (PMMA) weight average molecular weight is 70000, and described polyvinylpyrrolidone (PVP) viscosity average molecular weigh is 130000.
On the other hand, the present invention also provides a kind of preparation method of described hollow-fibre membrane, comprises the following steps:
(1) pretreatment of polymeric material
Kynoar, polymethyl methacrylate, polyvinylpyrrolidone are carried out drying in dryer, bake out temperature is 50～80 ℃;
(2) preparation of masking blend raw material
With Kynoar P
1, polymethyl methacrylate P
2With polyvinylpyrrolidone P
3, acetic acid-2-ethoxy-ethyl ester D
1With Macrogol 600 D
2After weighing, first be placed in stirred tank in proportion, carry out stirring and dissolving at the temperature of 130～160 ℃, mixing time is 15～25 hours, speed of agitator is 80～120 rev/mins, and the masking Polymer Solution cooling granulation in air with being uniformly dissolved obtains the blend raw material;
(3) hollow-fibre membrane extrudes, is shaped
(4) diluent leaching
The doughnut intermediate of making is immersed in reverse osmosis water, remove the diluent mixture in film, water temperature is 50～80 ℃, and leaching time is 8～12 hours;
(5) dry
The hollow-fibre membrane of making is at room temperature dried namely get the doughnut membrane product.
Preferably, wherein the temperature in step (1) is 60～70 ℃.
Preferably, wherein the mixing time described in step (2) is 22～24 hours, and described speed of agitator is 90～100 rev/mins.
Preferably, wherein step (3) comprises the following steps:
(3-1) above-mentioned blend raw material is added in double screw extruder melt extrude;
The melt blended material of (3-2) extruding is extruded from the doughnut annular die through filter and spinning pump, forms the as-spun fibre of hollow;
(3-3) above-mentioned as-spun fibre is lowered the temperature in air, then cooling curing in cooling fluid, through the winder rolling, make the doughnut intermediate.
Preferred, wherein the charging rate of step (3-1) Raw is 8kg/h, and extruder is divided into 8 sections along the spiro rod length direction and heats, and the temperature range of 8 sections is 110～160 ℃, and screw speed is 120 rev/mins.
Preferred, wherein in step (3-2), the external diameter of annular die single hole is 5.5 millimeters (mm), and internal diameter is 5.0 millimeters, and temperature is 140～150 ℃, and the annular die centre bore passes into nitrogen, and the pressure of nitrogen is 20～40 millimeter of water (mmH
2O), preferred nitrogen pressure is 25～30 millimeter of water (mmH
2O).
Preferred, wherein in step (3-3), above-mentioned as-spun fibre in being the air of 5～25 ℃, temperature is lowered the temperature, and preferred air themperature is 10～20 ℃, and the winder rolling speed is 10～15m/min, and cooling fluid is acetic acid-2-ethoxy-ethyl ester C
1, Macrogol 600 C
2, and water C
3Three's mixed liquor, coolant temperature are 5～40 ℃, and the temperature of preferred described cooling fluid is 10～30 ℃.
Preferred, wherein remain 10～30 centimetres from the air gap that the mouth mould exports to cooling liquid level, preferred the air gap is 15～20 centimetres.
Preferably, wherein the ratio of three's mixing is (mass ratio): (C
1+ C
2)/C
3=1/1～2/1, C
1/ C
2=1.2/1～2.5/1.
Preferred, wherein said (C
1+ C
2)/C
3=1.2/1～1.5/1, C
1/ C
2=1.4/1～2/1.
Preferably, wherein the water temperature described in step (4) is 60～70 ℃, and the time is 9～10 hours.
The Kynoar (PVDF) that the present invention adopts has outstanding anti-solvent, acid and alkali-resistance, resistance to oxidation, the characteristic such as weather-proof, excellent heat resistance and toughness are arranged, particularly the fluorine element in material has stronger negative polarity, makes PVDF be difficult for the absorption organic pollution, show good anti pollution property, is the preferred material of MBR technique.
Yet because PVDF material hydrophobicity is strong, the surface can be low, and hydrone is had repulsive interaction, and the present invention adopts the blend with it of at least a hydrophilic high molecular material, thereby effectively improves the hydrophily of pvdf membrane.
On this basis, the present invention also proposes a kind of new mixed diluent system, this system is comprised of two component mixed solvents, one of them component is solvent or the cosolvent of polymer, another component is the non-solvent of polymer, by the different proportion between adjusting in mixed diluent both, come the power of telomerized polymer and diluent interaction, and then the phase-separated state of change polymer/diluent system, reach the purpose of regulation and control membrane pore structure, the film of the required three-dimensional net structure of preparation.
On this basis, the present invention adopts the mixed liquor of diluent and water as cooling fluid, by changing composition and the temperature of cooling fluid, regulate the aperture on film surface and the size of percent opening, the PVDF that preparation has the hole density gradient is super, microfiltration membranes, improves film pollutant held back characteristic and the stifled ability of anti-soil.
On the other hand, preparation method provided by the invention, utilized the principle of " high-temperature digestion, low temperature phase-splitting ", with polymer and diluent at high temperature mixed dissolution become uniform Casting solution, then after solution is made tabular, tubulose and hollow fiber, through cooling, cooling, casting solution system generation liquid-liquid or solid-liquid phase are separated, after polymeric system solidifies, then the diluent extraction is removed, namely obtain porous diffusion barrier.The method is extensive to the adaptability of high polymer material, not only is suitable for conventional high polymer, also be suitable for dissolved solution poor, even due to highly crystalline, undissolvable polymer under common normal temperature.Because film-forming temperature is relatively high, the concentration of corresponding filming polymer is also relatively high, can avoid occurring the large cavity structure of the sort of finger-like that the phase separation method is made, make pore structure even, the three-dimensional net structure that highly connects, therefore film strength is high, can adapt to the requirement of MBR technique.The PVDF doughnut that adopts the present invention to prepare is super, microfiltration membranes, has good chemical stability, and antipollution, the hollow-fibre membrane that intensity is high can provide high performance film product for MBR technique.
In addition, in traditional filming technology, diluent is non-water-soluble, needs to adopt alcohol, ketone, ester class organic solvent as extractant after film is shaped, and this technique is except own expense height with an organic solvent, also to add the cost that reclaims extractant, can't avoid the discharging of organic pollution.In the present invention because two components in mixed diluent system are water miscible, so just can adopt water to extract diluent (cosolvent) in membrane as extractant, can avoid the trouble that adopts organic solvent to bring as extractant, also can reduce the manufacturing cost of film.
Hollow-fibre membrane external diameter of the present invention is 1.2～1.3 millimeters, wall thickness is 290～310 nanometers, membrane pore structure is three-dimensional interpenetrating polymer network structure (seeing accompanying drawing 1), the film section is asymmetric, and film outmost surface aperture is minimum, and the outer wall edge hole is fine and close, the aperture is less, the aperture increases gradually from outside to inside, and the inner surface aperture is maximum, is a kind of super, microfiltration membranes with density gradient pores section structure.Super, microfiltration membranes of the present invention has good chemically-resistant cleaning and hydrophily, and intensity is high, flux is large, good toughness, and good contamination resistance is arranged, and is adapted at most using in MBR.City domestic sewage, industrial wastewater can be carried out advanced treating, reach middle water reuse water standard.Compare with traditional Wastewater Treated by Activated Sludge Process waste water, treatment effeciency improves more than 3 times, and effluent quality is good, and Chemical Oxygen Demand in Wastwater (COD) clearance is greater than 98%, ammonia-nitrogen removal efficiency is high, and treatment facility is compact, take up an area less, automaticity is high, convenient operation and management.
Description of drawings
The electron scanning micrograph figure of Fig. 1 film section.
The specific embodiment
For a more detailed description to the present invention below in conjunction with embodiment, but described embodiment is not construed as limiting the invention.
Embodiment 1
The quality percentage is that 35% PVDF, mass percent are that 1.4% polymethyl methacrylate and mass percent are the polymer blend that the oven dry resin of 1.05% polyvinylpyrrolidone forms, and 0.14% methyl hydroxybenzoate join in the mixed solvent that acetic acid-2-ethoxy-ethyl ester and Macrogol 600 form, wherein the quality percentage of acetic acid-2-ethoxy-ethyl ester is 36.07%, and the quality percentage of Macrogol 600 is 26.48%.Said mixture is joined in stirred tank, is to carry out stirring and dissolving after 24 hours under 120 rev/mins of kind conditions at the temperature of 160 ℃, rotating speed, and cooling granulation in air obtains blended material.Charging rate with 8kg/h joins preprepared blend composition in double screw extruder.The temperature in extruder 1-8 district is respectively 110 ℃, 120 ℃, 135 ℃, 150 ℃, 160 ℃, 160 ℃, 160 ℃, 150 ℃, and screw speed is 120 rev/mins.After mixed material melt extrudes, enter four orifice ring shape die extrusions by filter and spinning pump in dual-screw-stem machine, make the hollow as-spun fibre, a mouthful mould single hole external diameter is 5.5mm, and internal diameter is 5mm, and temperature is 150 ℃, and it is 30mmH that a mouthful mould centre bore passes into pressure
2The N of O
2Gas.As-spun fibre is in temperature is the air of 10 ℃, and idling stopping distance (the air gap) is 15cm, enters into the cooling fluid cooling curing, with the speed rolling of 15m/min.Wherein contain 40% water in cooling fluid, 25% Macrogol 600,35% acetic acid-2-ethoxy-ethyl ester, the temperature of cooling fluid is 30 ℃.Preformed hollow-fibre membrane leaches and at room temperature dries after 10 hours in the reverse osmosis water of 70 ℃, makes doughnut membrane product of the present invention.By scanning electronic microscope observation, the inierpeneirating network structure of the section of film, asymmetric milipore filter, the surperficial average pore size of film is 54 nanometers (nm), and the fiber external diameter is 1.3 millimeters (mm), and wall thickness is 305 microns (μ m).Under temperature was 25 ℃, 0.1MPa pressure, pure water flux was 720L/m
2H, tensile strength of fiber are 7.5MPa, elongation at break 110%.
Provide main preparation process condition and the film properties of embodiment of the present invention 2-5 below in conjunction with table 1, but the content of each composition of the present invention is not limited to listed numerical value in this table, for a person skilled in the art, fully can be in table rationally summarize and reasoning on the basis of listed number range, and of particular note, although listed file names with some other parameter in table 1, this this Parameter Conditions is described as necessary condition.For the present invention, the content of core is to improve the film formula of liquid, and therefore, other parameters that list file names with in table 1 are just in order to provide in more detail about technical information of the present invention, be all preferred condition, described as necessary condition of the present invention.
The formulation ratio of table 1. embodiment 2-5, main preparation process condition and film properties
Wherein, in table 1, relevant film properties data are after cooling brittle failure, to use stereomicroscope that the section of described film is taken a picture and measured in liquid nitrogen hollow-fibre membrane, and method is as follows:
(1) Micro-Structure Analysis of film
Sample is made in film brittle failure in liquid nitrogen, sample is fixed on sample stage, under the voltage of 30KV, adopt SEM (QuanTa 200FEG) observation film section and surface texture.
(2) film-strength test
Film is made the sample silk, and two ends reinforce with medical proof fabric.Stretch on universal testing machine in (GT-TS-2000, GOTECHCO, Taiwan), the hot strength of test membrane silk and elongation at break.
(3) pure water flux of film test
Testing arrangement is by external-compression type ultrafilter, N
2Gas cylinder, vacuum tank form, and hollow-fibre membrane is packaged into specimen with epoxide-resin glue, and the employing temperature is the deionized water of 25 ℃, tests under the pressure of 0.1MPa.
Pure water flux is defined as the pure water quality that unit interval, elementary membrane area see through under above-mentioned test condition.
That is: J=W/AT
Wherein, J is pure water flux (kg/m
2H), A is the external surface area (m of film
2), W is the permeable amount (kg) of film, T is testing time (h).
(4) mensuration of the external diameter of hollow-fibre membrane, internal diameter and wall thickness
Any corresponding improvement of carrying out on basis of the present invention does not all break away from thought of the present invention, all falls into the scope of protection of the invention.
Claims (17)
1. hollow-fibre membrane, the formula of its masking and content thereof be by percentage to the quality:
Add nucleant agent N in described the first and second mixing diluents solvents: methyl hydroxybenzoate, and the addition of nucleator (mass ratio) is N/P
1=4 ‰
Wherein said Kynoar weight average molecular weight is 300000, and described polymethyl methacrylate weight average molecular weight is 70000, and described polyvinylpyrrolidone viscosity average molecular weigh is 130000.
2. hollow-fibre membrane according to claim 1, wherein the mass ratio of each composition is:
P
2/P
1＝0～0.12，
P
3/P
1＝0.02～0.08，
D
1/D
2＝1.2/1～2.5/1，
P/ (P+D)=(25～45) %, wherein: P=P
1+ P
2+ P
3, D=D
1+ D
2
Wherein P+D is absolutely
N/P
1＝4‰。
3. hollow-fibre membrane according to claim 2, wherein the mass ratio of each composition is:
Wherein said P
2/ P
1=0～0.04,
Wherein said P
3/ P
1=0.03～0.05,
Wherein said D
1/ D
2=1.4/1～2/1,
Wherein said P/ (P+D)=(30～40) %
N/P
1＝4‰。
4. the preparation method of the described hollow-fibre membrane of claim 1-3 any one, comprise the following steps:
(1) pretreatment of polymeric material
Kynoar, polymethyl methacrylate, polyvinylpyrrolidone are carried out drying in dryer, bake out temperature is 50～80 ℃;
(2) preparation of masking blend raw material
With Kynoar P
1, polymethyl methacrylate P
2With polyvinylpyrrolidone P
3, acetic acid-2-ethoxy-ethyl ester D
1With Macrogol 600 D
2After weighing, first be placed in stirred tank in proportion, carry out stirring and dissolving at the temperature of 130～160 ℃, mixing time is 15～25 hours, speed of agitator is 80～120 rev/mins, and the masking Polymer Solution cooling granulation in air with being uniformly dissolved obtains the blend raw material;
(3) hollow-fibre membrane extrudes, is shaped
(4) diluent leaching
The doughnut intermediate of making is immersed in reverse osmosis water, remove the diluent mixture in film, water temperature is 50～80 ℃, and leaching time is 8～12 hours;
(5) dry
The hollow-fibre membrane of making is at room temperature dried namely get the doughnut membrane product.
5. preparation method claimed in claim 4, wherein the temperature in step (1) is 60～70 ℃.
6. preparation method claimed in claim 4, wherein the mixing time described in step (2) is 22～24 hours, described speed of agitator is 90～100 rev/mins.
7. preparation method claimed in claim 4, wherein step (3) comprises the following steps:
(3-1) above-mentioned blend raw material is added in double screw extruder melt extrude;
The melt blended material of (3-2) extruding is extruded from the doughnut annular die through filter and spinning pump, forms the as-spun fibre of hollow;
(3-3) above-mentioned as-spun fibre is lowered the temperature in air, then cooling curing in cooling fluid, through the winder rolling, make the doughnut intermediate.
8. preparation method claimed in claim 7, wherein the charging rate of step (3-1) Raw is 8kg/h, and extruder is divided into 8 sections along the spiro rod length direction and heats, and the temperature range of 8 sections is 110～160 ℃, and screw speed is 120 rev/mins.
9. preparation method claimed in claim 7, wherein in step (3-2), the external diameter of annular die single hole is 5.5 millimeters (mm), and internal diameter is 5.0 millimeters, and temperature is 140～150 ℃, the annular die centre bore passes into nitrogen, and the pressure of nitrogen is 20～40 millimeter of water (mmH
2O).
10. preparation method claimed in claim 9, wherein nitrogen pressure is 25～30 millimeter of water (mmH
2O).
11. preparation method claimed in claim 7 wherein lowers the temperature above-mentioned as-spun fibre in step (3-3) in temperature is the air of 5～25 ℃, the winder rolling speed is 10～15m/min, and cooling fluid is acetic acid-2-ethoxy-ethyl ester C
1, Macrogol 600 C
2, and water C
3Three's mixed liquor, coolant temperature are 5～40 ℃.
12. the described preparation method of claim 11, the temperature of wherein said cooling fluid are 10～30 ℃.
13. preparation method claimed in claim 7 wherein remains 10～30 centimetres from the air gap that the mouth mould exports to cooling liquid level.
14. the described preparation method of claim 13, wherein the air gap is 15～20 centimetres.
15. the described preparation method of claim 11, wherein the ratio of three's mixing is (mass ratio):
(C
1+C
2)/C
3＝1/1～2/1，C
1/C
2＝1.2/1～2.5/1。
16. the described preparation method of claim 12, wherein the ratio of three's mixing is (mass ratio):
(C
1+C
2)/C
3＝1.2/1～1.5/1，C
1/C
2＝1.4/1～2/1。
17. preparation method claimed in claim 4, wherein the water temperature described in step (4) is 60～70 ℃, and the time is 9～10 hours.
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| CN103657447A (en) * | 2013-12-17 | 2014-03-26 | 常熟丽源膜科技有限公司 | Polyvinylidene fluoride porous hollow-fiber membrane |
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