CN100484616C - PVC hollow fiber ultrafiltration membrane preparation method - Google Patents
PVC hollow fiber ultrafiltration membrane preparation method Download PDFInfo
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- CN100484616C CN100484616C CNB2005101014642A CN200510101464A CN100484616C CN 100484616 C CN100484616 C CN 100484616C CN B2005101014642 A CNB2005101014642 A CN B2005101014642A CN 200510101464 A CN200510101464 A CN 200510101464A CN 100484616 C CN100484616 C CN 100484616C
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Abstract
The invention relates to a method for using dry-wet weave method to prepare asymmetry polychloroethylene hollow fiber ultra-filter membrane, wherein the membrane prepare liquid comprises following components: polychloroethylene at 13-19%, hydrophilic agent at 0.8-8%, macromolecule holing agent at 8-20%, solvent at 40-80%. The test has proved that the factor of porosity of product is 80-90%, the water penetration is 900-1400L/m2h (0.1MPa), with high pollution resistance. And the invention has wide application.
Description
Technical field
The present invention relates to the hollow fiber ultrafiltration membrane method for making, particularly have the method for making of the polyvinyl chloride hollow fiber ultrafiltration membrane of unsymmetric structure.
Background technology
Membrane separation technique is because its good filtration effect, low, the no phase transformation of energy consumption, easy and simple to handle, obtains application more and more widely in fields such as food, biology, environmental protection, medicine, chemical industry.Hyperfiltration technique is very typical a kind of during film separates.Membrane material commonly used at present has cellulose acetate (CA), polysulfones (PS), polyether sulfone (PES), polypropylene nitrile (PAN), Kynoar (PVDF) etc., but the cost performance of these materials is generally lower, has restricted the application of film to a certain extent.Therefore, seek a kind of cheap, good filtration effect, membrane material that physico-chemical property is good is extremely important.
Polyvinyl chloride is a kind of synthetic resin material of extensive use, and it has following advantage: resistance to acids and bases is strong, under the room temperature, and long-term scope of application PH2-12; Organic solvent-resistant is as halogenated hydrocarbons, aliphatic hydrocarbon, aromatic hydrocarbons, alcohol, aldehyde etc.; And it is suitable for doing-wet spinning system film, and is easy to manufacture; Wide material sources, cost is low.Polyvinyl chloride was hydrophobic at that time, when doing membrane material and being used to filter, because hydrophobicity is easy to be blocked up by dirt, made troubles to filtration, and therefore, it is very important that polychloroethylene film is carried out hydrophilic modifying.The method of modification generally has modification by copolymerization, graft modification and blending and modifying, and wherein blending and modifying is the most simple and convenient, and the quality of blend effect depends on choosing of intermingling material and blending technology.In the various forms of film, doughnut is big owing to its specific surface, self-supporting, be convenient to advantage such as cleaning and gain great popularity.The performance of hollow fiber ultrafiltration membrane is closely related with filming technology with membrane material.
Summary of the invention
The invention provides a kind of directly by doing---wet method is produced the film-forming method and the product of high water flux, resistant to pollution polyvinyl chloride hollow fiber ultrafiltration membrane.
Technical scheme of the present invention is: doing---wet method spins in the preparation liquid of the polyvinyl chloride hollow fiber ultrafiltration membrane with unsymmetric structure, add following substances: polyvinyl chloride 14-15wt%, hydrophilizing agent 2-4wt%, macromolecule pore former polyethylene glycol 12-13wt%, solvent dimethylacetylamide 68-72wt%, this preparation liquid is behind abundant stirring and evenly mixing, by inserting tubular type doughnut spinning nozzle, after vertical aloft travel distance is 10-50cm, enter coagulating bath, coagulating bath China and foreign countries gel media is the water of steady temperature, and the groove coolant-temperature gage is controlled at 18-50 ℃.Inner gel medium during film forming is the mixed liquor of water or water and dimethylacetylamide, and temperature is controlled at 18-50 ℃.
The present invention compared with prior art, its beneficial effect is: the inventive method is by suitable content ratio, make full use of the dispersion of macromolecule pore former, thickening power, the hydrophilic modifying effect of hydrophilizing agent, and make each composition preparation liquid that suitable dispersiveness and stability be arranged, effectively control the interface wet ability of preparation liquid and solidification liquid, be easy to the directional diffusion infiltration of coagulating agent and solution at the interface, and influence the precipitating setting rate of polyvinyl chloride in coagulating agent, be controlled to the mass transfer dynamics of membrane process, thereby spin out stable performance, the polyvinyl chloride doughnut perforated membrane that flux is big.Technologies such as the hollow-fibre membrane silk process that spins out is preserved moisture, cast are preferably made membrane module.
The specific embodiment
Below by specific embodiment the present invention further is illustrated, but the present invention is not limited only to this:
Embodiment 1
With Corvic (1400) 14wt%, dimethylacetylamide 72wt%, polyethylene glycol 12%, polymethyl methacrylate 2wt% fully mixes, and stirs stirring frequency 50Hz 24 hours.In 60 ℃ of insulations down, vacuum defoamation 10 hours.Preparation liquid by the spinning head ejection, is extruded with interior solidification liquid after filtering simultaneously, through 30cm air walk distance, enters as in the outer solidification liquid.Be around on the wire wrapping wheel then.Resulting doughnut perforated membrane external diameter 1.6mm, internal diameter 0.9mm.After the doughnut perforated membrane handled with glycerine, the molecular cut off that records film was 100,000 dalton, under 25 ℃, and the porosity 80% of testing this doughnut perforated membrane, pure water permeation flux 1080L/m
2H (0.1Mpa).
Embodiment 2
With Corvic (1400) 15wt%, dimethylacetylamide 68wt%, polyethylene glycol 13%, trichloroactic acid ester 4wt% fully mixes, and following steps are with embodiment 1.The molecular cut off that records film is 100,000 dalton, under 25 ℃, and the porosity 90% of testing this doughnut perforated membrane, pure water permeation flux 1210L/m
2H (0.1Mpa).
Its degree of polymerization of Corvic among the present invention is 1000-3000, and preferable range is 1100-1900, and the degree of polymerization is on the low side to be that the film silk intensity that spins out can be on the low side, is difficult to dissolving when the degree of polymerization is higher in solvent.The weight percent content of Corvic in preparation liquid is 14-15wt%, extend as technology of the present invention, also the degree of Corvic can be extended to the scope of 13-19wt%, but the performance of polyvinyl chloride can be affected, when its content was lower than 13wt% again, preparation liquid viscosity was low excessively, and spinnability is poor, when its content was higher than 19wt% again, preparation liquid viscosity was too high.And generally speaking, resin content height in the liquid can make the additive addition reduce relatively, and membrane porosity reduces, and is difficult to obtain suitable aperture, high-throughout polyvinyl chloride hollow fiber ultrafiltration membrane.
Among the present invention,, also can adopt dimethyl formamide to replace as the dimethylacetylamide of preparation liquid solvent for use, or two kinds mixed solvent.When solvent surpasses when a kind of, total addition is constant, and total addition of solvent is 68-72wt%.
Macromolecule pore former polyethylene glycol among the present invention is a soluble high-molecular, should be dissolvable in water solidification liquid or aftertreatment fluid.It mainly act as dispersion, infiltration, emulsification, thickening power, also certain hydrophily should be arranged simultaneously.Polyethylene glycol (PEG) also can adopt polypropylene glycol (PPG) to replace or two kinds mixture.When the macromolecule pore former surpasses when a kind of, total addition is constant.Wherein any macromolecule pore former proportion is not then limited.Total addition of macromolecule pore former is 12-13wt%, and the stability that how much depends on preparation liquid of addition can not make it phase-splitting, and should be evenly, disperse, stable.
The hydrophilizing agent of using among the present invention is one or both in polyvinylacetate (PVAc) polymethyl methacrylate (PMMA), and when hydrophilizing agent surpasses when a kind of, total addition is constant.The usage ratio of hydrophilizing agent is 2-4wt%.Mainly utilize the strong hydrophilicity effect of this type of hydrophilic polymer, this type of material and Corvic have good compatibility simultaneously, and have better physical and chemical property.The adding of hydrophilizing agent has improved the resistance tocrocking of polychloroethylene film silk greatly, and the flux of keeping the film silk is played crucial effects.
Preparation liquid temperature of the present invention is controlled at 40-80 ℃, preferred 50-70 ℃.It is too big that temperature is crossed when low the film fluid viscosity, is not easy to spinning, and macromolecular material can decompose rotten when temperature was too high.
Spinning process of the present invention is for doing--and-wet spinning, preparation liquid are extruded through spinning head, behind one section air-gap, vertically enter coagulating bath.Preparation liquid air walk distance is 10-50cm, spinning speed 20-60m/min.By the composition of controlling inside and outside solidification liquid and the inside and outside cortex construction that temperature is controlled film forming speed and film.
Inside and outside solidification liquid among the present invention all with water as main solidification liquid, contain certain density dimethylacetylamide, adopt refractometer to measure the concentration of solvent, and control concentration in real time, the precipitating curing rate of Corvic when contacting with solidification liquid with the control preparation liquid is to influence polyvinyl chloride doughnut perforated membrane cortex construction.
The film silk that the present invention spins out had the operation of soaking glycerine water solution before using, purpose is the microcellular structure that soaks into film, to keep the flux of film.The working concentration of glycerine is 10-70%, preferred 20-60%.The polyvinyl chloride hollow fiber ultrafiltration membrane that obtains by film-forming method of the present invention, can be used for better: 1, biofermentation separates with refining, 2, water-oil separating, 3, the turbidity removal of Chinese medicine extract is refining, 4, medical artificial kidney, artificial lung, 5, purification of water quality, 6, electrophoretic paint reclaims, 7, aspect such as the turbidity removal of liquid such as beer, soy sauce, yellow rice wine, low alcohol white spirit is refining.
Claims (3)
1, a kind of doing--the film-forming method that-wet method spinning has the polyvinyl chloride hollow fiber ultrafiltration membrane of unsymmetric structure is characterized in that preparation liquid comprises following substances:
Polyvinyl chloride 14-15% (weight),
Hydrophilizing agent 2-4% (weight),
Macromolecule pore former polyethylene glycol 12-13% (weight),
Solvent dimethylacetylamide 68-72% (weight).
2, film-forming method according to claim 1 is characterized in that described hydrophilizing agent is one or both in trichloroactic acid ester (PVAc), the polymethyl methacrylate (PMMA), and when hydrophilizing agent surpasses when a kind of, total addition is constant.
3, the polyvinyl chloride doughnut perforated membrane produced of film-forming method according to claim 1 and 2, the porosity that it is characterized in that described perforated membrane is 80-90%, the pure water permeation flux is 1080-1210L/m
2H (0.1MPa), and have good antifouling property.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101014642A CN100484616C (en) | 2005-11-15 | 2005-11-15 | PVC hollow fiber ultrafiltration membrane preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101014642A CN100484616C (en) | 2005-11-15 | 2005-11-15 | PVC hollow fiber ultrafiltration membrane preparation method |
Publications (2)
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| CN1966132A CN1966132A (en) | 2007-05-23 |
| CN100484616C true CN100484616C (en) | 2009-05-06 |
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| CNB2005101014642A Expired - Fee Related CN100484616C (en) | 2005-11-15 | 2005-11-15 | PVC hollow fiber ultrafiltration membrane preparation method |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254422B (en) * | 2007-12-12 | 2011-06-29 | 深圳市诚德来实业有限公司 | High intensity PVC hollow fiber hyperfiltration membrane and method of preparing the same |
| CN101513593B (en) * | 2009-03-04 | 2011-03-16 | 哈尔滨工程大学 | Hydrophilic polyvinyl chloride membrane and preparation method thereof |
| CN101920171A (en) * | 2010-08-25 | 2010-12-22 | 茅忠海 | Polrvinyl chloride hollow fibre ultrafiltration membrane preparation method |
| CN102068920A (en) * | 2010-11-29 | 2011-05-25 | 天津市宝钜净化设备工程有限公司 | Asymmetrical polyvinyl chloride dry-wet reversible ultrafiltration/microfiltration membrane, preparation method and application thereof |
| CN102784563B (en) * | 2011-05-18 | 2014-12-24 | 杭州永腾膜科技有限公司 | High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method |
| CN102151491B (en) * | 2011-05-23 | 2014-04-09 | 刘镇江 | Modified polyvinyl chloride alloy ultra-filtration membrane and preparation method of hollow fiber ultra-filtration membrane |
| CN102861519B (en) * | 2011-07-05 | 2016-06-01 | 北京金通量科技有限公司 | The preparation method of long-acting hydrophilic polyvinyl chloride hollow fiber ultrafiltration membrane |
| CN102861518B (en) * | 2011-07-05 | 2014-11-26 | 北京金通量科技有限公司 | Preparation method of high polymerization degree polyvinyl chloride hollow fiber ultrafiltration membrane |
| CN102343220A (en) * | 2011-09-29 | 2012-02-08 | 浙江开创环保科技有限公司 | Polyvinyl chloride membrane with supporting materials and preparation method thereof |
| CN102512987B (en) * | 2011-12-09 | 2014-03-26 | 苏州中色德源环保科技有限公司 | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane |
| CN103031612B (en) * | 2013-01-21 | 2015-11-25 | 深圳市诚德来实业有限公司 | A kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane and a kind of spinning head |
| CN103495348B (en) * | 2013-09-30 | 2015-12-23 | 广州超禹膜分离技术有限公司 | A kind of PVC hollow fiber ultrafiltration membrane and preparation method thereof |
| CN104923093A (en) * | 2015-07-01 | 2015-09-23 | 芜湖市晨曦新型建材科技有限公司 | Hollow fiber ultrafiltration membrane of water purifier and preparation method for hollow fiber ultrafiltration membrane |
| CN106378011B (en) * | 2016-11-02 | 2020-01-03 | 湖北工业大学 | Adsorption ultrafiltration membrane containing sodium polystyrene sulfonate and preparation method thereof |
| CN107362696B (en) * | 2017-07-12 | 2020-06-09 | 平顶山学院 | Preparation method and application of super-hydrophilic underwater super-oleophobic and super-oleophilic oil-water separation cork filter membrane |
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Address after: Longgang District of Shenzhen City, Guangdong Province, about 518116 students a Baolong Lu Hua Feng Industry Park 3 Building 2 floor Patentee after: Chengdelai Industry Co., Ltd., Shenzhen Address before: 518122, No. two, No. 5, Jinsha Jinsha Industrial Road, Longgang District, Guangdong, Shenzhen Patentee before: Chengdelai Industry Co., Ltd., Shenzhen |
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