CN101874991A - PVDF ultra-filtration membrane taking ethyl orthosilicate as additive and preparation method - Google Patents
PVDF ultra-filtration membrane taking ethyl orthosilicate as additive and preparation method Download PDFInfo
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- CN101874991A CN101874991A CN 201010153223 CN201010153223A CN101874991A CN 101874991 A CN101874991 A CN 101874991A CN 201010153223 CN201010153223 CN 201010153223 CN 201010153223 A CN201010153223 A CN 201010153223A CN 101874991 A CN101874991 A CN 101874991A
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- 239000012528 membrane Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 8
- 239000002033 PVDF binder Substances 0.000 title claims abstract 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 title claims description 6
- 238000000108 ultra-filtration Methods 0.000 title abstract 2
- 239000000654 additive Substances 0.000 title description 3
- 230000000996 additive effect Effects 0.000 title description 3
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 15
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 polyoxyethylene Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012809 cooling fluid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 235000012489 doughnuts Nutrition 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 9
- 229960003511 macrogol Drugs 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 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
- 239000002826 coolant Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 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
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 238000001471 micro-filtration Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000004907 flux Effects 0.000 description 5
- 239000012510 hollow fiber Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- 239000010865 sewage 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
- 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
- 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
- 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
- 238000000280 densification Methods 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
- 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
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 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
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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Abstract
The invention relates to a polyvinylidene fluoride porous hollow fibrous membrane and a preparation method thereof. A formula for preparing the membrane comprises the following components in percentage by mass: 25 to 45 percent of polyvinylidene fluoride (PVDF) serving as a first polymer P1, 0 to 4.5 percent of polymethylmethacrylate (PMMA) serving as a second polymer P2, 0.9 to 3 percent of polyoxyethylene (PEO) serving as a third polymer P3, 27 to 40 percent of dimethyl sulfoxide serving as a first diluent D1 and 27 to 36 percent of polyethylene glycol 600 serving as a second diluent D2. The PVDF hollow fibrous ultra and micro-filtration membrane prepared by adopting the method has excellent chemical stability, is a pollution-resistant and high-strength hollow fibrous membrane, and can provide a high-performance membrane product 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 relating to a kind of is Kynoar (PVDF) porous hollow fiber membrane and the method for making thereof of additive with the ethyl orthosilicate.
Background technology
Membrane biological reactor process (MBR) is a kind of novel, sewage disposal technology efficiently, 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.Be the waste water advanced processing and the regeneration new technology of advanced, efficient and low energy consumption in the present age.Wherein preparing intensity height, antifouling property good, milipore filter and micro-filtration membrane cheaply, is the core technology of membrane biological reactor process.But at present most ofs commercially surpass, the micro-filtration membrane effect is all undesirable, can't satisfy industrial requirement.On the other hand, super at present, the most employing non-solvents of micro-filtration membrane cause the phase separation method preparation, and the film of being made comprises the big 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 in membrane biological reactor process, using.
Kynoar porous hollow fiber membrane provided by the invention, its system prescription composition of film and content thereof be by percentage to the quality:
First polymer P
1: Kynoar (PVDF) 25～45%
Second polymer P
2: polymethyl methacrylate (PMMA) 0～4.5%
Terpolymer P
3: polyoxyethylene (PEO) 0.9～3%
The first diluent D
1: methyl-sulfoxide 27～40%
The second diluent D
2: Macrogol 600 27～36%.
Preferably, wherein the mass ratio of each composition is:
P
2/P
1＝0～0.18，
P
3/P
1＝0.02～0.12，
D
1/D
2＝4/5～7/5，
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=0.02～0.06,
Wherein said P
3/ P
1=0.04～0.08,
Wherein said D
1/ D
2=1/1～6/5,
Wherein said P/ (P+D)=(30～38) %.
Preferably, add nucleator N in described first, second mixing diluents solvent: ethyl orthosilicate, and the addition of nucleator (mass ratio) is N/P
1=2 ‰.
Preferably, wherein said Kynoar (PVDF) weight average molecular weight is 300000, and described polymethyl methacrylate (PMMA) weight average molecular weight is 70000, and polyoxyethylene (PEO) weight average molecular weight is 20000.
On the other hand, the present invention also provides a kind of preparation method of described hollow-fibre membrane, comprises the following steps: the preliminary treatment of (1) polymeric material
Kynoar, polymethyl methacrylate, polyoxyethylene are carried out drying in dryer, bake out temperature is 50～80 ℃;
(2) preparation of system film blend raw material
With Kynoar P
1, polymethyl methacrylate P
2With polyoxyethylene P
3, methyl-sulfoxide D
1With Macrogol 600 D
2After the weighing, be placed on earlier in the stirred tank in proportion, under 130～160 ℃ temperature, carry out stirring and dissolving, mixing time is 15～25 hours, speed of agitator is 80～120 rev/mins, will dissolve system film Polymer Solution cooling granulation in air uniformly, obtains the blend raw material;
(3) hollow-fibre membrane extrudes, is shaped
(4) diluent leaching
The doughnut intermediate of making is immersed in the reverse osmosis water, remove the diluent mixture in the film, water temperature is 20～35 ℃, and leaching time is 3～6 hours;
(5) dry
The hollow-fibre membrane of making at room temperature dried promptly get the doughnut membrane product.
Preferably, wherein the temperature in the step (1) is 60～70 ℃.
Preferably, wherein the mixing time described in the step (2) is 22～24 hours, and described speed of agitator is 90～100 rev/mins.
Preferably, wherein step (3) may further comprise the steps:
(3-1) will melt extrude in the above-mentioned blend raw material adding double screw extruder;
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, cooling curing in cooling fluid through the winder rolling, is made the doughnut intermediate then.
Preferred, wherein the charging rate of raw material is 8kg/h in the step (3-1), and extruder is divided into 8 sections along the spiro rod length direction and heats, and the temperature range of 8 sections is 120～160 ℃, and screw speed is 120 rev/mins.
Preferred, wherein the external diameter of annular die single hole is 5.5 millimeters (mm) in the step (3-2), and internal diameter is 5.0 millimeters, and temperature is 140～150 ℃, and the annular die centre bore feeds nitrogen, and nitrogen gas pressure is 10～30 millimeter of water (mmH
2O), preferred nitrogen pressure is 15～25 millimeter of water (mmH
2O).
Preferred, wherein in the step (3-3) above-mentioned as-spun fibre in being 5～20 ℃ air, temperature is lowered the temperature, 10～15 ℃ of preferred air themperatures, winder rolling speed is 10～15m/min, cooling fluid is methyl-sulfoxide C
1, Macrogol 600 C
2, and water C
3Three's mixed liquor, coolant temperature are 10～30 ℃, and the temperature of preferred described cooling fluid is 15～25 ℃.
Preferred, wherein export to the air gap of cooling off liquid level and remain 5～30 centimetres from the mouth mould, preferred the air gap is 10～20 centimetres.
Preferably, wherein the ratio of three's mixing is (mass ratio): (C
1+ C
2)/C
3=1.4/1～2.5/1, C
1/ C
2=4/5～7/5.
Preferred, (C
1+ C
2)/C
3=1.5/1～2/1, C
1/ C
2=1/1～6/5.
Preferably, wherein the water temperature described in the step (4) is 20～30 ℃, and the time is 4～5 hours.
The Kynoar (PVDF) that the present invention adopts has outstanding anti-solvent, acid and alkali-resistance, resistance to oxidation, characteristic such as weather-proof, excellent hear resistance and toughness are arranged, particularly the fluorine element in the material has stronger negative polarity, makes PVDF be difficult for being adsorbed with organic pollutants, show good anti pollution property, is the preferred material of MBR technology.
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 improves the hydrophily of pvdf membrane effectively.
On this basis, the present invention also proposes a kind of new mixed diluent system, this system is made up of two component mixed solvents, one of them component is the solvent or the cosolvent of polymer, another component is the non-solvent of polymer, by adjusting the different proportion between the two in the mixed diluent, come interactional power between telomerized polymer and the diluent, and then the phase-separated state of change polymer/diluent system, reach the purpose of regulation and control membrane pore structure, prepare the film of required three-dimensional net structure.
On this basis, the present invention adopts the mixed liquor of diluent and water as cooling fluid, by changing the composition and the temperature of cooling fluid, regulate the aperture on film surface and the size of percent opening, super, the micro-filtration membrane of the PVDF that preparation has the hole density gradient improves film pollutant is 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 film solution, again solution is made tabular, tubulose and hollow fiber after, through cooling, cooling, casting solution system generation liquid-liquid or solid-liquid are separated, after polymeric system solidifies, again the diluent extraction is removed, promptly obtain porous diffusion barrier.This method is extensive to the adaptability of high polymer material, not only is suitable for conventional high polymer, and it is poor even because highly crystalline also to be suitable for dissolved separating property, undissolvable polymer under common normal temperature.Because film-forming temperature is higher relatively, the concentration of corresponding filming polymer is also higher relatively, can avoid occurring non-solvent and cause the big cavity structure of the sort of finger-like that phase separation method is made, it is even to make pore structure, the three-dimensional net structure of Guan Tonging highly, therefore the film strength height can adapt to the requirement of MBR technology.Super, the micro-filtration membrane of the PVDF doughnut that adopts the present invention to prepare has excellent chemical stability, and antipollution, the hollow-fibre membrane that intensity is high can provide high performance film product for MBR technology.
In addition, diluent is non-water-soluble in traditional filming technology, needs to adopt alcohol, ketone, ester class organic solvent as extractant after film is shaped, and this technology 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.Among the present invention since mixed diluent system in two components be water miscible, so just can adopt water as come together diluent (cosolvent) in the membrane of extractant, can avoid the trouble that adopts organic solvent to bring, also can reduce the manufacturing cost of film as extractant.
Hollow-fibre membrane external diameter of the present invention is 1.1～1.3 millimeters, wall thickness is 275～315 nanometers, membrane pore structure is three-dimensional interpenetrating polymer network structure (seeing accompanying drawing 1), the film section is asymmetric, film outmost surface aperture minimum, the densification of outer wall edge hole, the aperture is less, the aperture increases gradually from outside to inside, and inner surface aperture maximum is a kind of super, micro-filtration membrane with density gradient pores section structure.Super, micro-filtration membrane of the present invention has good chemically-resistant cleaning and hydrophily, and intensity height, big, the good toughness of flux have good contamination resistance, are adapted at most using among the MBR.City domestic sewage, industrial wastewater can be carried out advanced treating, water reuse water standard in reaching.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 consumption (COC) in the waste water (COD) clearance is greater than 98%, ammonia-nitrogen removal efficiency height, the treatment facility compactness, take up an area of less, automaticity height, 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 below in conjunction with embodiment to the present invention, but described embodiment is not construed as limiting the invention.
Embodiment 1
The quality percentage is that 38% PVDF, mass percent are that 2.3% polymethyl methacrylate and mass percent are the polymer blend that 3.0% polyoxyethylated oven dry resin is formed, and 0.08% ethyl orthosilicate join in the mixed solvent that methyl-sulfoxide and Macrogol 600 form, wherein the quality percentage of methyl-sulfoxide is 28.35%, and the quality percentage of Macrogol 600 is 28.35%.Said mixture is joined in the stirred tank, is to carry out stirring and dissolving after 24 hours under 120 rev/mins of kind conditions at 160 ℃ temperature, rotating speed, and cooling granulation in air obtains blended material.Charging rate with 8kg/h joins preprepared blend composition in the double screw extruder.The temperature in extruder 1-8 district is respectively 120 ℃, 125 ℃, 130 ℃, 140 ℃, 160 ℃, 160 ℃, 160 ℃, 150 ℃, and screw speed is 120 rev/mins.After mixed material melt extrudes in dual-screw-stem machine, enter four hole annular dies by filter and spinning pump and extrude, 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 25mmH that a mouthful mould centre bore feeds pressure
2The N of O
2Gas.As-spun fibre is in temperature is 15 ℃ air, and idling stopping distance (the air gap) is 20cm, enters into the cooling fluid cooling curing, with the speed rolling of 15m/min.Wherein contain 33.3% water in the cooling fluid, 33.4% Macrogol 600,33.3% methyl-sulfoxide, the temperature of cooling fluid is 20 ℃.Preformed hollow-fibre membrane leaches and at room temperature dries after 4 hours in 30 ℃ reverse osmosis water, 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, film surface average pore size is 40 nanometers (nm), and the fiber external diameter is 1.3 millimeters (mm), and wall thickness is 310 microns (μ m).Under temperature was 25 ℃, 0.1MPa pressure, pure water flux was 550L/m
2H, tensile strength of fiber are 6.5MPa, elongation at break 50%.
Provide main preparation process condition and the film properties of embodiment of the 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 the table 1, this this parameter condition 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 the table 1 are just in order to provide in more detail about technical information of the present invention, all be preferred condition, described as necessary condition of the present invention.
Table 1: the formulation ratio of embodiment 2-5, main preparation process condition and film properties
Wherein, film properties data relevant in the table 1 are hollow-fibre membrane is cooled off brittle failure in liquid nitrogen after, and the use stereomicroscope is taken a picture to the section of described film and measured, 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 the sample platform, 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.On universal testing machine, stretch in (GT-TS-2000, GOTECHCO, Taiwan) 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 are formed, and hollow-fibre membrane is packaged into test x sample with epoxide-resin glue, and the employing temperature is 25 ℃ a deionized water, tests under the pressure of 0.1MPa.
Pure water flux is defined as the pure water quality that sees through at following unit interval of above-mentioned test condition, elementary membrane area.
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 (16)
1. hollow-fibre membrane, the prescription of its system film and content thereof be by percentage to the quality:
First polymer P
1: Kynoar (PVDF) 25～45%
Second polymer P
2: polymethyl methacrylate (PMMA) 0～4.5%
Terpolymer P
3: polyoxyethylene (PEO) 0.9～3%
The first diluent D
1: methyl-sulfoxide 27～40%
The second diluent D
2: Macrogol 600 27～36%.
2. hollow-fibre membrane according to claim 1, wherein the mass ratio of each composition is:
P
2/P
1＝0～0.18，
P
3/P
1＝0.02～0.12，
D
1/D
2＝4/5～7/5，
P/ (P+D)=(25～45) %, wherein: P=P
1+ P
2+ P
3, D=D
1+ D
2
Wherein P+D is absolutely.
3. hollow-fibre membrane according to claim 2, wherein the mass ratio of each composition is:
Wherein said P
2/ P
1=0.02～0.06,
Wherein said P
3/ P
1=0.04～0.08,
Wherein said D
1/ D
2=1/1～6/5,
Wherein said P/ (P+D)=(30～38) %.
4. according to each described hollow-fibre membrane of claim 1-3, add nucleator N in described first, second mixing diluents solvent: ethyl orthosilicate, and the addition of nucleator (mass ratio) is N/P
1=2 ‰.
5. hollow-fibre membrane according to claim 1, wherein said Kynoar (PVDF) weight average molecular weight is 300000, and described polymethyl methacrylate (PMMA) weight average molecular weight is 70000, and polyoxyethylene (PEO) weight average molecular weight is 20000.
6. the preparation method of each described hollow-fibre membrane of claim 1-5 comprises the following steps:
(1) preliminary treatment of polymeric material
Kynoar, polymethyl methacrylate, polyoxyethylene are carried out drying in dryer, bake out temperature is 50～80 ℃;
(2) preparation of system film blend raw material
With Kynoar P
1, polymethyl methacrylate P
2With polyoxyethylene P
3, methyl-sulfoxide D
1With Macrogol 600 D
2After the weighing, be placed on earlier in the stirred tank in proportion, under 130～160 ℃ temperature, carry out stirring and dissolving, mixing time is 15～25 hours, speed of agitator is 80～120 rev/mins, will dissolve system film Polymer Solution cooling granulation in air uniformly, obtains the blend raw material;
(3) hollow-fibre membrane extrudes, is shaped
(4) diluent leaching
The doughnut intermediate of making is immersed in the reverse osmosis water, remove the diluent mixture in the film, water temperature is 20～35 ℃, and leaching time is 3～6 hours;
(5) dry
The hollow-fibre membrane of making at room temperature dried promptly get the doughnut membrane product.
7. the described preparation method of claim 6, wherein the temperature in the step (1) is 60～70 ℃.
8. the described preparation method of claim 6, wherein the mixing time described in the step (2) is 22～24 hours, described speed of agitator is 90～100 rev/mins.
9. the described preparation method of claim 6, wherein step (3) may further comprise the steps:
(3-1) will melt extrude in the above-mentioned blend raw material adding double screw extruder;
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, cooling curing in cooling fluid through the winder rolling, is made the doughnut intermediate then.
10. the described preparation method of claim 9, wherein the charging rate of raw material is 8kg/h in the step (3-1), and extruder is divided into 8 sections along the spiro rod length direction and heats, and the temperature range of 8 sections is 120～160 ℃, and screw speed is 120 rev/mins.
11. the described preparation method of claim 9, wherein the external diameter of annular die single hole is 5.5 millimeters (mm) in the step (3-2), and internal diameter is 5.0 millimeters, and temperature is 140～150 ℃, the annular die centre bore feeds nitrogen, and nitrogen gas pressure is 10～30 millimeter of water (mmH
2O), preferred nitrogen pressure is 15～25 millimeter of water (mmH
2O).
12. the described preparation method of claim 9 wherein lowers the temperature above-mentioned as-spun fibre in the step (3-3) in temperature is 5～20 ℃ air, 10～15 ℃ of preferred air themperatures, and winder rolling speed is 10～15m/min, cooling fluid is methyl-sulfoxide C
1, Macrogol 600 C
2, and water C
3Three's mixed liquor, coolant temperature are 10～30 ℃, and the temperature of preferred described cooling fluid is 15～25 ℃.
13. the described preparation method of claim 9 wherein exports to the air gap of cooling off liquid level from the mouth mould and remains 5～30 centimetres, preferred the air gap is 10～20 centimetres.
14. the described preparation method of claim 12, wherein the ratio of three's mixing is (mass ratio):
(C
1+C
2)/C
3＝1.4/1～2.5/1，C
1/C
2＝4/5～7/5。
15. the described preparation method of claim 14, wherein the ratio of three's mixing is (mass ratio):
(C
1+C
2)/C
3＝1.5/1～2/1，C
1/C
2＝1/1～6/5。
16. the described preparation method of claim 6, wherein the water temperature described in the step (4) is 20～30 ℃, and the time is 4～5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877869A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Porous membrane made of polytetrafluoroethylene hollow fibers, preparation method and application thereof in membrane contactor |
| CN105879714A (en) * | 2014-11-17 | 2016-08-24 | 天津工业大学 | Anti-pollution hollow fiber ultrafiltration membrane and preparation process thereof |
| CN112397600A (en) * | 2019-08-16 | 2021-02-23 | 福建金石能源有限公司 | High-waterproof flexible solar cell packaging material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN101507902A (en) * | 2009-02-19 | 2009-08-19 | 苏州膜华材料科技有限公司 | Preparation method of porous polyvinylidene fluoride alloy membrane for wastewater treatment and recycling |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN101507902A (en) * | 2009-02-19 | 2009-08-19 | 苏州膜华材料科技有限公司 | Preparation method of porous polyvinylidene fluoride alloy membrane for wastewater treatment and recycling |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877869A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Porous membrane made of polytetrafluoroethylene hollow fibers, preparation method and application thereof in membrane contactor |
| CN105879714A (en) * | 2014-11-17 | 2016-08-24 | 天津工业大学 | Anti-pollution hollow fiber ultrafiltration membrane and preparation process thereof |
| CN112397600A (en) * | 2019-08-16 | 2021-02-23 | 福建金石能源有限公司 | High-waterproof flexible solar cell packaging material and preparation method thereof |
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