CN102974232A - Method for producing anti-pollution modified polyvinylidene fluoride hollow fiber membrane - Google Patents
Method for producing anti-pollution modified polyvinylidene fluoride hollow fiber membrane Download PDFInfo
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- CN102974232A CN102974232A CN2012104884587A CN201210488458A CN102974232A CN 102974232 A CN102974232 A CN 102974232A CN 2012104884587 A CN2012104884587 A CN 2012104884587A CN 201210488458 A CN201210488458 A CN 201210488458A CN 102974232 A CN102974232 A CN 102974232A
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- cellulose acetate
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- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002033 PVDF binder Substances 0.000 title abstract description 21
- 229920002981 polyvinylidene fluoride Polymers 0.000 title abstract description 21
- 239000012510 hollow fiber Substances 0.000 title abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 31
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 29
- 238000009987 spinning Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 55
- 239000000835 fiber Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 11
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 11
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 17
- 239000000243 solution Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract 1
- 230000000295 complement effect Effects 0.000 abstract 1
- 229940113088 dimethylacetamide Drugs 0.000 abstract 1
- 230000003381 solubilizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 230000003373 anti-fouling effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010865 sewage Substances 0.000 description 6
- 230000010148 water-pollination Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 235000012489 doughnuts Nutrition 0.000 description 4
- 238000000578 dry spinning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000010618 wire wrap Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000131 polyvinylidene Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Abstract
The invention discloses a method for producing an anti-pollution modified polyvinylidene fluoride hollow fiber membrane, comprising the following steps of: mixing and stirring polyvinylidene fluoride, polyacrylonitrile and cellulose acetate at the mass ratio of (6-10):(0.5-2):(0.5-2), dissolving the mixture by using dimethyl acetamide or N-methylpyrrolidone as a solvent to obtain a 10-20% mixed solution, adding a solubilizing additive into the mixed solution to promote the mixed solution to be dissolved completely to obtain a membrane-making solution, defoaming the membrane-making solution, and spinning to make a membrane. Because the polyvinylidene fluoride, the polyacrylonitrile and the cellulose acetate are mixed together, and the three materials are complementary, the hydrophilicity and the anti-pollution properties of the polyvinylidene fluoride are improved. In addition, the hollow fiber membrane produced by mixing has high water flux, good anti-pollution performance, low cost and excellent membrane forming properties, and the technical support is provided for the wide range of application of the membrane technology to wastewater treatment.
Description
Technical field
The present invention relates to membrane material manufacturing technology field, refer to particularly a kind of manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane.
Background technology
Membrane bioreactor, Membrane Bio-Reactor is abbreviated as MBR, as a kind of new and effective sewage disposal technology, day by day receives various countries researcher's concern.The MBR film is the core component of membrane bioreactor system, and its effect is to realize accurate, efficient Separation of Solid and Liquid, and film pollutes, film cost height is the main cause that restriction MBR membrane bioreactor is applied.Therefore, be more widely used in water treatment field in order to make the MBR technology, just need further exploitation and development low cost, high performance anti-pollution, high-throughout MBR film.
The membrane material that is used at present the better performances of submerged membrane bioreactor mainly is Kynoar.Kynoar is a kind of fluorinated polymer, and stronger physical strength and chemical stability are arranged.But in use still there are some problems in the polyvinylidene fluoride (PVDF) ultrafiltration membrane assembly, as: stronger hydrophobicity easily makes fenestra block, film body is polluted, and film cleans difficulty.Therefore improve the hydrophilicity of polyvinylidene fluoride film, prevent that the further propagation and employment that film pollutes for polyvinylidene fluoride film from seeming particularly important.In the preparation of film, film is carried out study on the modification, introduce hydrophilic radical on film surface by adding multiple auxiliary material, or can effectively improve the film pollution situation with the compound one deck hydrophily of composite membrane means separating layer etc.
A kind of ideal selection by developing new MBR membrane material from the blend between existing membrane material.Blending and modifying is method commonly used in the polyvinylidene fluoride (PVDF) ultrafiltration membrane modification technology.Modified material mainly contains inorganic matter and organic matter two classes.Polyvinylidene fluoride blending film after the modification is compared with the pure film of Kynoar, and significant change has all occured the performance of membrane pore structure and film.As by the material blend, can improve the chemical stability of film, can improve the mechanical strength of film.
Common polyvinylidene fluoride material toughness is high, impact and anti-wear performance are also all better, also have simultaneously fabulous gasproof and chemical stability, the at room temperature corrosion such as the strong oxidizer such as acid and alkali, alkali element, be easy to casting film-forming during masking, thereby make it become outstanding person in the organic polymer membrane material, thereby be subject to numerous researchers' favor.But it is strong that its shortcoming is hydrophobicity, easily causes film to pollute, and therefore needs it is carried out hydrophilic modifying, to improve its resistance tocrocking.In contrast, the widely not strong oxidizer corrosion such as acid and alkali-resistance of the film made of acetate fiber cellulosic material of Another Application is easily degraded by many moulds and bacterium, but this film has the advantages such as good hydrophilic property, antifouling property are strong.Practice shows, can eliminate the weakness on the performance each other when with cellulose acetate and polyvinylidene blending, reaches the purpose of balanced each polymers compositions performance of learning from other's strong points to offset one's weaknesses, thereby finally can improve the hydrophily of polyvinylidene fluoride film.Therefore, select suitable polymeric system and to adopt physical blending be easy, effective a kind of method of improving the Kynoar film properties.
Kynoar and cellulose acetate carry out the blend film that blend makes, really many performances of polyvinylidene fluoride film have been improved largely, but also introduced simultaneously some problems, the purer polyvinylidene fluoride films of performance such as the acid resistance of film, non-oxidizability, toughness all descend to some extent.Therefore, for the impact of the chemical stability that reduces the blend caudacoria as far as possible, need the addition of strict control cellulose acetate, if but the addition of cellulose acetate is too small, then can affect the hydrophilic improvement of blend film.Therefore, in blend film, introduce another kind of material of preparing, polyacrylonitrile.The polyacrylonitrile masking is easy, cheap, have preferably chemical stability, and heat endurance, but its film forming is more crisp is restricted using.Hydrophilicity circle of polyacrylonitrile is between Kynoar and cellulose acetate, being added in when guaranteeing the blend film hydrophilicity of Kynoar, reduce the addition of cellulose acetate, also reduced simultaneously since the adding of cellulose acetate on the impact of blend film chemical stability.In addition, polyacrylonitrile is cheap, can reduce the cost of blend film, makes it have more advantage in the application of water treatment.
Therefore, the advantage such as Kynoar/polyacrylonitrile/cellulose acetate blend film has good antifouling property, good chemical stability, and is cheap, for applying of the large specification of membrane technology provide technical may.
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of antipollution modified polyvinilidene fluoride hollow-fibre membrane prepares hydrophily and the antifouling property that Kynoar/polyacrylonitrile/cellulose acetate blend hollow fiber membrane improves Kynoar by the cellulose acetate that hydrophily is strong, polyacrylonitrile and polyvinylidene blending.
Technical scheme of the present invention: the manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane, may further comprise the steps: be Kynoar, polyacrylonitrile, the cellulose acetate mix and blend of 6～10:0.5～2:0.5～2 with mass ratio, obtaining mass concentration with dimethylacetylamide or 1-METHYLPYRROLIDONE as dissolution with solvents is 10～20% mixed solution, then adding the solubilising additive in the mixed solution impels its dissolving to obtain preparation liquid, again preparation liquid is carried out deaeration and process spinning membrane system.
As preferred version, the mass ratio of Kynoar, polyacrylonitrile, cellulose acetate is 8:1:1.
As preferred version, the mass concentration of described mixed solution is 12%.
As preferred version, described solvent is dimethylacetylamide.Judge polymer-compatible according to the solubility parameter method, if two kinds of structure adaptability degree parameters are respectively δ
1And δ
2, make ︱ δ
1-δ
2︱＜0.5, then two kinds of polymer homogeneous phases are compatible; If ︱ is δ
1-δ
2︱＞0.5 then is that part is compatible, and structure adaptability degree parameter is more approaching, and compatibility is better, δ
PVDF=15.10, δ
PAN=14.39, δ
CA=19.56, three kinds of mutual solubility of material differs all greater than 0.5, so Kynoar/polyacrylonitrile/cellulose acetate belongs to the compatible system of part.1-METHYLPYRROLIDONE and dimethylacetylamide are during as solvent, and intermiscibility is all better, considers the economy of actual production, selects dimethylacetylamide more economical and practical as solvent.
As preferred version, described solubilising additive is LiCl.After adding LiCl, solution becomes gets clear, and viscosity is maximum, and film properties is good, be LiCl with the polar solvent with amide groups and with macromolecular material acting in conjunction result.LiCl can mix and cause viscosity rise with dimethylacetylamide, by X-ray diffraction analysis, can also find that they can form crystallization complex compound, wherein Li
+Ion and carbonyl on every side form coordinate bond, and Cl
-Form hydrogen bond with on every side amido, thus can think and formed complex compound with-CONH-group, thus break the formed intermolecular hydrogen bonding of similar group on this group and the adjacent chain, so just be equivalent to increase the solvability of solvent.
Further, the addition of described solubilising additive be Kynoar, polyacrylonitrile, cellulose acetate gross mass 2%～5%.
Further, described deaeration is processed and is comprised stirring at low speed 3～5h, more static 3～5h with preparation liquid elder generation.
The present invention is technical scheme more specifically:
(1) with mass ratio is Kynoar, polyacrylonitrile, the cellulose acetate adding stirred tank mix and blend of 6～10:0.5～2:0.5～2, regulating the temp controlled meter temperature is 80 ℃, obtaining mass concentration with dimethylacetylamide or 1-METHYLPYRROLIDONE as dissolution with solvents is 10～20% mixed solution, then adds the solubilising additive in the mixed solution and impels it to dissolve fully to obtain preparation liquid;
(2) squeeze into the spinning still with being stirred to consoluet preparation liquid in the stirred tank with the nitrogen pressurization, the preparation liquid stirring at low speed was left standstill after 3～5 hours carried out again deaeration in 3～5 hours first, can prepare spinning membrane system to discharging feed liquid without the even clear of bubble;
(3) the gel groove has been added deionized water as coagulant liquid, regulating the temp controlled meter design temperature is 20～25 ℃, slowly regulates the nitrogen pressure-reducing valve, and spinneret is installed on the spinning pipeline, after opening the spinning valve and observing spinneret and have continuous uniform film liquid to flow out, core liquid pipe is installed on the spinneret.Porose flowing for core liquid in the middle of the spinneret, core liquid mainly for generation of with control hollow-fibre membrane pore structure, core liquid is the deionized water under the room temperature, flow through spinneret hole through spinner flowmeter by Action of Gravity Field, when the spinning hollow-fibre membrane, the pressure of 0.2～0.3Mpa is provided as pressure source with high pressure nitrogen, to extrude from spinneret through the casting solution of metering, simultaneously under head tank pressure, enter the cavity of doughnut as supporter and interior setting medium by spinner flowmeter from the hole, center of spinneret, regulating core fluid valve flow is 2.7 ~ 3.1L/h, preparation liquid and core liquid are together discharged, after evaporating rapidly, dry-spinning path is 3 ~ 5 hoes, enters coagulation forming in the coagulation bath;
(4) hollow fiber film thread of moulding is put into collection makes hollow-fibre membrane on row's silk wheel/wire wrapping wheel, the hollow-fibre membrane of gained soaked 24 hours first in deionized water after, put into again mass percent and be 50% glycerine water solution and soaked 24 hours, make membrane module after naturally drying.
The invention has the advantages that: prepare Kynoar/polyacrylonitrile/cellulose acetate blend hollow fiber membrane by the cellulose acetate that hydrophily is strong, polyacrylonitrile and polyvinylidene blending, three kinds of material complementations, hydrophily and the antifouling property of Kynoar have been improved, blend hollow fiber membrane has higher water flux and good antifouling property in addition, while is with low cost, filming performance is good, for membrane technology provides technical support in the extensive use aspect the sewage disposal.The purer polyvinylidene fluoride film of the antifouling property of Kynoar/polyacrylonitrile/cellulose acetate is significantly increased.Can improve about 3 times before the purer Kynoar of the pure water flux of blend film, the clear frequency of film reduces, and operating cost is lower.The purer polyvinylidene fluoride film of material cost of Kynoar/polyacrylonitrile/cellulose acetate blend film low about 15%; Because the purer Kynoar of membrane flux is high, the purer Kynoar of membrane module number that same class sewage is selected is few, and the engineering construction cost is lower.Kynoar/polyacrylonitrile/cellulose acetate membrane component application in the MBR system, be can be used for the aspects such as municipal sewage treatment, Industrial Wastewater Treatment and middle water reuse.
The specific embodiment:
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1:
(1) with mass ratio is Kynoar, polyacrylonitrile, the cellulose acetate adding stirred tank mix and blend of 10:2:1, regulating the temp controlled meter temperature is 80 ℃, obtaining mass concentration with dimethylacetylamide or 1-METHYLPYRROLIDONE as dissolution with solvents is 20% mixed solution, then adds the solubilising additive in the mixed solution and impels it to dissolve fully to obtain preparation liquid;
(2) squeeze into the spinning still with being stirred to consoluet preparation liquid in the stirred tank with the nitrogen pressurization, the preparation liquid stirring at low speed was left standstill after 5 hours carried out again deaeration in 5 hours first, can prepare spinning membrane system to discharging feed liquid without the even clear of bubble;
(3) the gel groove has been added deionized water as coagulant liquid, regulating the temp controlled meter design temperature is 25 ℃, slowly regulates the nitrogen pressure-reducing valve, and spinneret is installed on the spinning pipeline, after opening the spinning valve and observing spinneret and have continuous uniform film liquid to flow out, core liquid pipe is installed on the spinneret.Porose flowing for core liquid in the middle of the spinneret, core liquid mainly for generation of with control hollow-fibre membrane pore structure, core liquid is the deionized water under the room temperature, flow through spinneret hole through spinner flowmeter by Action of Gravity Field, when the spinning hollow-fibre membrane, the pressure of 0.2Mpa is provided as pressure source with high pressure nitrogen, to extrude from spinneret through the casting solution of metering, simultaneously under head tank pressure, enter the cavity of doughnut as supporter and interior setting medium by spinner flowmeter from the hole, center of spinneret, regulating core fluid valve flow is 3.1L/h, preparation liquid and core liquid are together discharged, after evaporating rapidly, dry-spinning path is 3 hoes, enters coagulation forming in the coagulation bath;
(4) hollow fiber film thread of moulding is put into collection makes hollow-fibre membrane on row's silk wheel/wire wrapping wheel, the hollow-fibre membrane of gained soaked 24 hours first in deionized water after, put into again mass percent and be 50% glycerine water solution and soaked 24 hours, make membrane module after naturally drying.
Embodiment 2:
(1) with mass ratio is Kynoar, polyacrylonitrile, the cellulose acetate adding stirred tank mix and blend of 8:1:1, regulating the temp controlled meter temperature is 80 ℃, obtaining mass concentration with dimethylacetylamide or 1-METHYLPYRROLIDONE as dissolution with solvents is 12% mixed solution, then adds the solubilising additive in the mixed solution and impels it to dissolve fully to obtain preparation liquid;
(2) squeeze into the spinning still with being stirred to consoluet preparation liquid in the stirred tank with the nitrogen pressurization, the preparation liquid stirring at low speed was left standstill after 3 hours carried out again deaeration in 3 hours first, can prepare spinning membrane system to discharging feed liquid without the even clear of bubble;
(3) the gel groove has been added deionized water as coagulant liquid, regulating the temp controlled meter design temperature is 25 ℃, slowly regulates the nitrogen pressure-reducing valve, and spinneret is installed on the spinning pipeline, after opening the spinning valve and observing spinneret and have continuous uniform film liquid to flow out, core liquid pipe is installed on the spinneret.Porose flowing for core liquid in the middle of the spinneret, core liquid mainly for generation of with control hollow-fibre membrane pore structure, core liquid is the deionized water under the room temperature, flow through spinneret hole through spinner flowmeter by Action of Gravity Field, when the spinning hollow-fibre membrane, the pressure of 0.3Mpa is provided as pressure source with high pressure nitrogen, to extrude from spinneret through the casting solution of metering, simultaneously under head tank pressure, enter the cavity of doughnut as supporter and interior setting medium by spinner flowmeter from the hole, center of spinneret, regulating core fluid valve flow is 3L/h, preparation liquid and core liquid are together discharged, after evaporating rapidly, dry-spinning path is 5 hoes, enters coagulation forming in the coagulation bath;
(4) hollow fiber film thread of moulding is put into collection makes hollow-fibre membrane on row's silk wheel/wire wrapping wheel, the hollow-fibre membrane of gained soaked 24 hours first in deionized water after, put into again mass percent and be 50% glycerine water solution and soaked 24 hours, make membrane module after naturally drying.
Embodiment 3:
(1) with mass ratio is Kynoar, polyacrylonitrile, the cellulose acetate adding stirred tank mix and blend of 6:1:2, regulating the temp controlled meter temperature is 80 ℃, obtaining mass concentration with dimethylacetylamide or 1-METHYLPYRROLIDONE as dissolution with solvents is 10% mixed solution, then adds the solubilising additive in the mixed solution and impels it to dissolve fully to obtain preparation liquid;
(2) squeeze into the spinning still with being stirred to consoluet preparation liquid in the stirred tank with the nitrogen pressurization, the preparation liquid stirring at low speed was left standstill after 3 hours carried out again deaeration in 5 hours first, can prepare spinning membrane system to discharging feed liquid without the even clear of bubble;
(3) the gel groove has been added deionized water as coagulant liquid, regulating the temp controlled meter design temperature is 20 ℃, slowly regulates the nitrogen pressure-reducing valve, and spinneret is installed on the spinning pipeline, after opening the spinning valve and observing spinneret and have continuous uniform film liquid to flow out, core liquid pipe is installed on the spinneret.Porose flowing for core liquid in the middle of the spinneret, core liquid mainly for generation of with control hollow-fibre membrane pore structure, core liquid is the deionized water under the room temperature, flow through spinneret hole through spinner flowmeter by Action of Gravity Field, when the spinning hollow-fibre membrane, the pressure of 0.3Mpa is provided as pressure source with high pressure nitrogen, to extrude from spinneret through the casting solution of metering, simultaneously under head tank pressure, enter the cavity of doughnut as supporter and interior setting medium by spinner flowmeter from the hole, center of spinneret, regulating core fluid valve flow is 2.7L/h, preparation liquid and core liquid are together discharged, after evaporating rapidly, dry-spinning path is 5 hoes, enters coagulation forming in the coagulation bath;
(4) hollow fiber film thread of moulding is put into collection makes hollow-fibre membrane on row's silk wheel/wire wrapping wheel, the hollow-fibre membrane of gained soaked 24 hours first in deionized water after, put into again mass percent and be 50% glycerine water solution and soaked 24 hours, make membrane module after naturally drying.
The result shows:
The purer polyvinylidene fluoride film of the antifouling property of Kynoar/polyacrylonitrile/cellulose acetate is significantly increased.Can improve about 3 times before the purer Kynoar of the pure water flux of blend film, the clear frequency of film reduces, and operating cost is lower.
The purer polyvinylidene fluoride film of material cost of Kynoar/polyacrylonitrile/cellulose acetate blend film low about 15%; Because the purer Kynoar of membrane flux is high, the purer Kynoar of membrane module number that same class sewage is selected is few, and the engineering construction cost is lower.
Kynoar/polyacrylonitrile/cellulose acetate membrane component application in membrane bioreactor system, be can be used for the aspects such as municipal sewage treatment, Industrial Wastewater Treatment and middle water reuse.
Claims (7)
1. the manufacture method of an antipollution modified polyvinilidene fluoride hollow-fibre membrane, may further comprise the steps: be Kynoar, polyacrylonitrile, the cellulose acetate mix and blend of 6～10:0.5～2:0.5～2 with mass ratio, obtaining mass concentration with dimethylacetylamide or 1-METHYLPYRROLIDONE as dissolution with solvents is 10～20% mixed solution, then adding the solubilising additive in the mixed solution impels it to dissolve fully to obtain preparation liquid, again preparation liquid is carried out deaeration and process spinning membrane system.
2. the manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane according to claim 1, it is characterized in that: the mass ratio of Kynoar, polyacrylonitrile, cellulose acetate is 8:1:1.
3. the manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane according to claim 2, it is characterized in that: the mass concentration of described mixed solution is 12%.
4. the manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane according to claim 1, it is characterized in that: described solvent is dimethylacetylamide.
5. the manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane according to claim 1, it is characterized in that: described solubilising additive is LiCl.
6. the manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane according to claim 1 is characterized in that: the addition of described solubilising additive be Kynoar, polyacrylonitrile, cellulose acetate gross mass 2%～5%.
7. the manufacture method of antipollution modified polyvinilidene fluoride hollow-fibre membrane according to claim 1 is characterized in that: described deaeration is processed and is comprised stirring at low speed 3～5h, more static 3～5h with preparation liquid elder generation.
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| CN103551057A (en) * | 2013-11-12 | 2014-02-05 | 陈亭汝 | Heavy metal ion adsorption-type hybrid separation membrane |
| CN103816819A (en) * | 2014-03-10 | 2014-05-28 | 上海珺领生化科技有限公司 | Hollow fiber blend nanofiltration membrane and preparation process |
| 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 |
| CN115920658A (en) * | 2023-01-15 | 2023-04-07 | 安徽科博瑞环境科技有限公司 | Low-surface-energy anti-pollution hollow fiber membrane and preparation method thereof |
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| CN115920658A (en) * | 2023-01-15 | 2023-04-07 | 安徽科博瑞环境科技有限公司 | Low-surface-energy anti-pollution hollow fiber membrane and preparation method thereof |
| CN115920658B (en) * | 2023-01-15 | 2023-10-20 | 安徽科博瑞环境科技有限公司 | Low-surface-energy anti-pollution hollow fiber membrane and preparation method thereof |
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