CN1683059A - Reinforced hollow fiber super filter film and its preparing method - Google Patents
Reinforced hollow fiber super filter film and its preparing method Download PDFInfo
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- CN1683059A CN1683059A CN 200510024195 CN200510024195A CN1683059A CN 1683059 A CN1683059 A CN 1683059A CN 200510024195 CN200510024195 CN 200510024195 CN 200510024195 A CN200510024195 A CN 200510024195A CN 1683059 A CN1683059 A CN 1683059A
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- hollow fiber
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- fiber ultrafiltration
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Abstract
The present invention discloses a kind of reinforced hollow fiber superfiltering film and its preparation process. Polyvinylidene fluoride resin is first dissolved in organic solvent and additive is added to compound filming liquid. The filming liquid is then painted onto hollow support material and made to pass through solidifying bath, so that the filming material producing delayed phase separation inside the solvent owing to the action of the additive and great amount of micelle diffuse to the contact interface between the filming liquid and the solidifying bath to form one compact layer, which is finally solidified to form the hollow superfiltering film with surface control layer. The hollow superfiltering film has the advantages of both the polyvinylidene fluoride material and the high strength support material, including excellent filtering performance, low resistance, high mechanical strength and high chemical stability.
Description
Technical field
The present invention relates to a kind of is matrix with the macromolecular material, and relating to a kind of specifically is the enhancement mode hollow fiber ultrafiltration membrane and preparation method thereof of matrix with the polyvinylidene fluoride.
Background technology
The hollow fiber ultrafiltration film is a kind of widely used filter medium, and the material that it can be removed comprises sugar, biomolecule, high molecular polymer, colloidal substance, can realize reclaiming, concentrates, technical process such as extraction.Hollow fiber ultrafiltration membrane is loaded advantages such as density is big, device volume is little, energy consumption is low, use is easy to operate, is widely used in industry fields such as biology, pharmacy, food, chemical industry, metallurgy and waste water control.
Polyvinylidene fluoride is a kind of engineering plastics with premium properties, over the past two years, existing business-like is the hollow fiber ultrafiltration membrane of membrane material with the polyvinylidene fluoride, and this product has good chemical stability, heat endurance and contamination resistance, and it is widely used in waste water control.But, present widely used polyvinylidene fluoride hollow fiber ultrafiltration film all has obvious defects, low, the poor rigidity of the most intensity of this milipore filter, under very low pressure reduction, promptly can produce deformation, influence filtering accuracy and flux, serious also can produce phenomenons such as holes, fracture of wire, and the probability that causes quality accident is big.Therefore research and develop a kind of new enhancement mode hollow fiber ultrafiltration membrane and preparation method thereof, will have crucial value.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of enhancement mode hollow fiber ultrafiltration membrane and preparation method thereof, to overcome the above-mentioned defective of prior art operation.
Design of the present invention is such:
The present invention's imagination, adopt polyester, glass or nylon as backing material, under the situation that does not reduce flux and filter efficiency, to strengthen the mechanical performance of milipore filter, the great raising that the withstand voltage difference of radial drawing intensity and forward all obtains, thereby improved the effect that recoil is cleaned, prolonged the service life of product.Simultaneously, macromolecule member material is dissolved in the organic solvent, and in mixture, adds additive, be made into casting solution.Casting solution is coated on the hollow support material, during by coagulating bath because the effect of additive, the casting film material is produced in solvent postpone to be separated, a large amount of glue bundle bodies are to the contact-making surface diffusion of casting solution and coagulating bath, therefore produce the key-course of one deck densification, after solidifying, can obtain a kind of hollow fiber ultrafiltration film with surperficial key-course.This milipore filter combines the advantage of polyvinylidene fluoride material and high strength backing material, not only has the good strainability and the low use resistance of common milipore filter, and has splendid mechanical strength and chemical stability.
According to above conception, the inventor has proposed following technical scheme:
A kind of enhancement mode hollow fiber ultrafiltration membrane, comprise supporting layer with large aperture passage, attached to supporting layer outer solidify by casting solution after the key-course that constitutes and the macroporous layer that fuses with key-course;
Key-course filtering holes aperture is significantly smaller than supporting layer access opening aperture, and filtering accuracy depends primarily on key-course.
Key-course thickness is 1.0～500 μ m, and supporting layer thickness is 10～1000 μ m;
Key-course filtering holes aperture is 0.01～0.1 μ m, and the access opening aperture is 0.5～50 μ m;
The thickness of macroporous layer is 100～500 μ m;
The component of said key-course comprises high molecular polymer and additive;
Said high molecular polymer is selected from one or more in polysulfones, polyamide-based, poly-fluorine class or the polyacrylonitrile;
Said polysulfones is selected from polysulfones, SPSF, polyether sulfone, sulfonated polyether sulfone or polysulfonamides;
Said polyamide-based nylon 6, nylon 66, the aromatic polyamides of being selected from;
Said poly-fluorine class is selected from polyvinyl fluoride, polyvinylidene fluoride or poly-trifluoro-ethylene, preferentially selects polyvinylidene fluoride;
Said additive is selected from a kind of or its mixture in polyethylene glycol, polyvinylpyrrolidone, glycerine, acetone, lithium nitrate, calcium chloride, calcium nitrate or the hydrochloric acid;
The weight of additive is 0.01～1 times of high molecular polymerization amount;
The material of said supporting layer is selected from porous glass hollow spinnerule, porous polyester hollow spinnerule or porous nylon hollow spinnerule, can adopt the commercially available prod;
The preparation of enhancement mode hollow fiber ultrafiltration membrane of the present invention comprises the steps:
(1) preparation of casting solution: at first high molecular polymer and additive are dissolved in the solvent, form macromolecule casting film material/solvent/additive ternary casting solution, airtight standing and defoaming;
High molecular polymer polymer quality concentration is 5.0～20.0% in the casting solution, and preferential is 8.0～18.0%;
Said solvent is selected from a kind of in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), N methyl pyrrolidone or the acetone;
The mass concentration of additive is 0.5～80.0% in the said casting solution, and preferential is 3.0～60.0%;
(2) film: in the casting film chamber, support layer material soaked in casting solution 0.1～1 hour, and then backing material was pulled out from scrape fenestra, thereby be that the casting solution of 100～1000 μ m evenly is coated on the backing material thickness; Casting film chamber relative humidity is 10%～80%, and the casting film room temperature is 0～60 ℃;
(3) forming film with phase transformation method: coated membrane material places 10～60 ℃ environment in the step 2, the evaporative removal solvent immerses gel film forming in the coagulating bath again, and the coagulation bath temperature is 0～60 ℃, time is 1～300 minute, promptly obtains enhancement mode hollow fiber ultrafiltration film of the present invention;
Said coagulation bath is a kind of solution, is made up of in water, ethanol, isopropyl alcohol, formic acid, ethyl acetate, hexamethyl phosphoramide or the calcium chloride inorganic salts one or more, and mass concentration is 0.5%～100%.
Because polyvinylidene fluoride is a kind of macromolecular material with good chemical stability, resistance to ag(e)ing, strong mechanical strength, characteristics such as adopt the milipore filter of this material preparation to be rich in long service life, antipollution, adaptability is strong, strainability is stable.Therefore the present invention is the casting film material with it preferentially.Common hollow fiber ultrafiltration membrane hot strength is low, the shortcoming of easy fracture of wire in order to improve simultaneously, it is backing material that the present invention preferentially adopts the weaving hollow glass fibre, because this kind mechanical strength height, stretch-proof, extruding, have good chemical stability simultaneously, the adhesive ability of casting solution on this kind material is strong, difficult drop-off, the cost of material is low, is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the cross section electromicroscopic photograph of enhancement mode hollow fiber ultrafiltration film of the present invention.
Fig. 2 is a structural representation.
Specific implementation method
Embodiment 1
The 500g polyvinylidene fluoride resin is placed wide-mouth bottle, add the 120g polyvinylpyrrolidone, the 2000ml dimethylacetylamide is heated to 70 ℃, stirs airtight standing and defoaming.
Casting film chamber humidity is controlled at relative humidity 45%, the casting film room temperature is controlled at 20 ℃, clean hollow glass was soaked in casting solution 8 seconds, glass after soaking into is pulled out from scraping the fenestra of diameter 2mm, after evaporating 10 seconds under 30 ℃ the condition, immerse film forming in 20 ℃ of water-baths, it is dry to treat that gel took out after 1 hour, promptly obtains the said milipore filter of the present invention.
According to the performance evaluation method of routine, this film is 95% to the bovine serum albumin rejection, pure water flux 1.8m under 20 ℃, 0.1Mpa pressure reduction condition
3/ hr m
2
Its electromicroscopic photograph such as Fig. 1, structural representation such as Fig. 2.As seen from the figure, this enhancement mode hollow fiber ultrafiltration film outermost layer is a macroporous layer 2, thickness 110 μ m, be key-course 3 inward, thickness 70 μ m, key-course filtering holes aperture is 0.01 μ m, internal layer then is the channel layer 1 that backing material forms, thickness 300 μ m, and the access opening aperture is 0.5 μ m.
Embodiment 2
The 500g polyvinylidene fluoride resin is placed wide-mouth bottle, add the 115g polyvinylpyrrolidone, the 15g lithium nitrate, the 2250ml dimethylacetylamide is heated to 40 ℃, stirs airtight standing and defoaming.
Casting film chamber humidity is controlled at relative humidity 45%, the casting film room temperature is controlled at 20 ℃, clean hollow glass was soaked in casting solution 5 seconds, glass after soaking into is pulled out from scraping the fenestra of diameter 1.8mm, evaporate after 5 seconds, immerse 20 ℃, weight concentration and be film forming in 10% the ethanol water, it is dry to treat that gel took out after 1.5 hours, promptly obtains the said milipore filter of the present invention.
Other conditions are identical with embodiment 1.
According to the traditional performance evaluation assessment, this film is 91% to the bovine serum albumin rejection, and pure water flux is 2.2m3/hr m2 under 20 ℃, 0.1MPa pressure reduction condition.
This enhancement mode hollow fiber ultrafiltration film outermost layer is a macroporous layer 2, and thickness 160 μ m are key-course 3 inward, and thickness 50 μ m, internal layer then are the channel layers 1 that backing material forms, thickness 250 μ m.Key-course filtering holes aperture is 0.01 μ m, and the access opening aperture is 50 μ m.
Claims (8)
1. enhancement mode hollow fiber ultrafiltration membrane, it is characterized in that, comprise supporting layer with large aperture passage, attached to supporting layer outer solidify by casting solution after the key-course that constitutes and the macroporous layer that fuses with key-course, key-course filtering holes aperture is significantly smaller than supporting layer access opening aperture;
The component of said key-course comprises high molecular polymer and additive;
Said high molecular polymer is selected from polysulfones, SPSF, polyether sulfone, sulfonated polyether sulfone, polysulfonamides, nylon 6, nylon 66, aromatic polyamides, polyvinyl fluoride, polyvinylidene fluoride or poly-trifluoro-ethylene;
Said additive is selected from a kind of or its mixture in polyethylene glycol, polyvinylpyrrolidone, glycerine, acetone, lithium nitrate, calcium chloride, calcium nitrate or the hydrochloric acid.
2. enhancement mode hollow fiber ultrafiltration membrane according to claim 1 is characterized in that high molecular polymer is selected from polyvinylidene fluoride.
3. enhancement mode hollow fiber ultrafiltration membrane according to claim 1 is characterized in that, the quality of additive is 0.01～1 times of high molecular polymerization amount.
4. enhancement mode hollow fiber ultrafiltration membrane according to claim 1 is characterized in that, the material of said supporting layer is selected from porous glass hollow spinnerule, porous polyester hollow spinnerule or porous nylon hollow spinnerule.
5. according to each described enhancement mode hollow fiber ultrafiltration membrane of claim 1～4, it is characterized in that key-course thickness is 1.0～500 μ m, supporting layer thickness is 10～1000 μ m;
Key-course filtering holes aperture is 0.01～0.1 μ m, and the access opening aperture is 0.5～50 μ m;
The thickness of macroporous layer is 100～500 μ m.
6. according to the preparation method of each described enhancement mode hollow fiber ultrafiltration membrane of claim 1～5, it is characterized in that, comprise the steps:
(1) high molecular polymer and additive are dissolved in the solvent, form macromolecule casting film material/solvent/additive ternary casting solution, airtight standing and defoaming;
The mass concentration of high molecular polymer is 5.0～20.0% in the casting solution;
Said solvent is selected from a kind of in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), N methyl pyrrolidone or the acetone;
The mass concentration of additive is 0.5～80.0% in the casting solution;
(2) in the casting film chamber, support layer material is soaked in casting solution, then backing material is pulled out from scrape fenestra, thereby evenly be coated in casting solution on the backing material;
(3) coated membrane material evaporative removal solvent in the step (2) immerses gel film forming in the coagulating bath again, and the coagulation bath temperature is 0～60 ℃, and the time is 1～300 minute, promptly obtains enhancement mode hollow fiber ultrafiltration film.
7. method according to claim 6 is characterized in that, said coagulation bath is made up of in water, ethanol, isopropyl alcohol, formic acid, ethyl acetate, hexamethyl phosphoramide or the calcium chloride inorganic salts one or more, and mass concentration is 0.5%～100%.
8. method according to claim 6 is characterized in that, casting film chamber relative humidity is 10%～80%, and the casting film room temperature is 0～60 ℃.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500271C (en) * | 2007-06-05 | 2009-06-17 | 天津膜天膜工程技术有限公司 | Making method and device for reinforced composite material hollow membrane |
| CN101205308B (en) * | 2006-12-22 | 2010-05-12 | 中国科学院兰州化学物理研究所 | Sulfonated polysulfonamide proton exchange membrane and preparation thereof |
| CN101810892A (en) * | 2010-04-21 | 2010-08-25 | 中国科学院长春应用化学研究所 | Method for filtering liquid medicine and application of composite membrane in filtering liquid medicine |
| CN1843600B (en) * | 2006-03-28 | 2010-11-24 | 上海一鸣过滤技术有限公司 | Intensified microporous membrane of polyethersulfone and method for preparing the same |
| CN101209396B (en) * | 2006-12-31 | 2011-07-06 | 山西金泉合成纤维制造有限公司 | Blended polysulfone hollow fiber film and preparation method |
| CN102172481A (en) * | 2011-03-09 | 2011-09-07 | 青岛科技大学 | Method for preparing separation membrane with composite structure |
| CN102489170A (en) * | 2011-12-23 | 2012-06-13 | 重庆绿色智能技术研究院 | Hollow fiber ultrafilter membrane and its preparation method |
| CN101421021B (en) * | 2006-04-10 | 2012-06-27 | 佛兰芒技术研究所 | Knitted support for tubular membranes |
| CN101632904B (en) * | 2009-08-19 | 2012-08-01 | 北京碧水源膜科技有限公司 | Polyvinylidene fluoride (PVDF) hollow-fiber membrane with base material and production method thereof |
| CN102698611A (en) * | 2012-06-27 | 2012-10-03 | 上海大学 | Method for preparing polysulfone amide hollow fiber separation membrane by wet spinning |
| CN101790413B (en) * | 2007-10-19 | 2013-05-08 | 川崎重工业株式会社 | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| CN102036741B (en) * | 2008-05-21 | 2013-08-14 | 三菱丽阳株式会社 | Hollow porous membrane and process for producing the same |
| CN103861474A (en) * | 2012-12-17 | 2014-06-18 | 厦门大学 | High-molecular ultrafiltration membrane and preparation method thereof |
| CN105344246A (en) * | 2015-10-23 | 2016-02-24 | 蓝星（成都）新材料有限公司 | Ultrafilter membrane and production method thereof |
| US20160268571A1 (en) * | 2013-12-26 | 2016-09-15 | Teijin Limited | Non-aqeous secondary cell separator and non-aqueous secondary cell |
| CN107715701A (en) * | 2017-10-20 | 2018-02-23 | 浙江帕尔环境科技有限公司 | Back-washable milipore filter of a kind of high flux antipollution and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1843600B (en) * | 2006-03-28 | 2010-11-24 | 上海一鸣过滤技术有限公司 | Intensified microporous membrane of polyethersulfone and method for preparing the same |
| CN101421021B (en) * | 2006-04-10 | 2012-06-27 | 佛兰芒技术研究所 | Knitted support for tubular membranes |
| CN101205308B (en) * | 2006-12-22 | 2010-05-12 | 中国科学院兰州化学物理研究所 | Sulfonated polysulfonamide proton exchange membrane and preparation thereof |
| CN101209396B (en) * | 2006-12-31 | 2011-07-06 | 山西金泉合成纤维制造有限公司 | Blended polysulfone hollow fiber film and preparation method |
| CN100500271C (en) * | 2007-06-05 | 2009-06-17 | 天津膜天膜工程技术有限公司 | Making method and device for reinforced composite material hollow membrane |
| CN101790413B (en) * | 2007-10-19 | 2013-05-08 | 川崎重工业株式会社 | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| US8752713B2 (en) | 2008-05-21 | 2014-06-17 | Mitsubishi Rayon Co., Ltd. | Hollow porous membrane and process for producing the same |
| CN102036741B (en) * | 2008-05-21 | 2013-08-14 | 三菱丽阳株式会社 | Hollow porous membrane and process for producing the same |
| CN101632904B (en) * | 2009-08-19 | 2012-08-01 | 北京碧水源膜科技有限公司 | Polyvinylidene fluoride (PVDF) hollow-fiber membrane with base material and production method thereof |
| CN101810892A (en) * | 2010-04-21 | 2010-08-25 | 中国科学院长春应用化学研究所 | Method for filtering liquid medicine and application of composite membrane in filtering liquid medicine |
| CN101810892B (en) * | 2010-04-21 | 2013-01-02 | 中国科学院长春应用化学研究所 | Method for filtering liquid medicine and application of composite membrane in filtering liquid medicine |
| CN102172481A (en) * | 2011-03-09 | 2011-09-07 | 青岛科技大学 | Method for preparing separation membrane with composite structure |
| CN102172481B (en) * | 2011-03-09 | 2013-01-09 | 青岛科技大学 | Method for preparing separation membrane with composite structure |
| CN102489170A (en) * | 2011-12-23 | 2012-06-13 | 重庆绿色智能技术研究院 | Hollow fiber ultrafilter membrane and its preparation method |
| CN102698611A (en) * | 2012-06-27 | 2012-10-03 | 上海大学 | Method for preparing polysulfone amide hollow fiber separation membrane by wet spinning |
| CN103861474A (en) * | 2012-12-17 | 2014-06-18 | 厦门大学 | High-molecular ultrafiltration membrane and preparation method thereof |
| CN103861474B (en) * | 2012-12-17 | 2015-11-11 | 厦门大学 | Polymer ultrafiltration membrane and preparation method thereof |
| US20160268571A1 (en) * | 2013-12-26 | 2016-09-15 | Teijin Limited | Non-aqeous secondary cell separator and non-aqueous secondary cell |
| CN105344246A (en) * | 2015-10-23 | 2016-02-24 | 蓝星（成都）新材料有限公司 | Ultrafilter membrane and production method thereof |
| CN107715701A (en) * | 2017-10-20 | 2018-02-23 | 浙江帕尔环境科技有限公司 | Back-washable milipore filter of a kind of high flux antipollution and preparation method thereof |
| CN107715701B (en) * | 2017-10-20 | 2024-04-05 | 浙江帕尔环境科技有限公司 | High-flux anti-pollution backwashing ultrafiltration membrane and preparation method thereof |
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