CN1415407A - Method for preparing ultra filtration membrane in hollow fiber made from PVC with high flux - Google Patents
Method for preparing ultra filtration membrane in hollow fiber made from PVC with high flux Download PDFInfo
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- CN1415407A CN1415407A CN 02145427 CN02145427A CN1415407A CN 1415407 A CN1415407 A CN 1415407A CN 02145427 CN02145427 CN 02145427 CN 02145427 A CN02145427 A CN 02145427A CN 1415407 A CN1415407 A CN 1415407A
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Abstract
A high-through put ultrafilter membrane of hollow polyvinyl chloride fibres is prepared through mixing polyvinyl chloride, solvent and additive, stirring, and spraying it along with internal gelatinizing medium in the gelatinizing bath using distilled water as gelatinizing medium to obtain target membrane. Its advantages are high porosity up to 90% or more and high throughput (400 L/h.sq.m for purified water).
Description
Technical field
The present invention relates to a kind of preparation method of polymer ultrafiltration membrane, relate in particular to a kind of preparation method of polyvinyl chloride hollow fiber ultrafiltration membrane.
Background technology
At present, along with developing rapidly of membrane separation technique, membrane technology is at bioengineering, and food engineering has obtained in environment-friendly engineering and the many chemical processes using widely.Because milipore filter and isolation technics thereof have can be at normal pressure, normal temperature or low temperature is operation down, no phase transformation, and energy consumption is low, does not change the physics and the chemical property of filtrate, can concentrate simultaneously and characteristics such as separates, and is replacing traditional separation process gradually.Be widely used in preliminary treatment, wastewater treatment, separating of enzyme preparation, vaccine, medicine, genetically engineered biological goods and food service industry concentrates and purification, also obtained considerable progress in the application aspect biological enzyme reactor and the sewage disposal membrane bioreactor.In recent years, hyperfiltration technique is owing to have separative efficiency height, low power consumption and other advantages and obtained using widely.Membrane material develops into polysulfones (PS), polyacrylonitrile (PAN) and the Kynoar (PVDF) etc. of today also by early stage cellulose acetate (CA).Though these membrane materials all have advantage separately, all there is certain limitation when using them.As CAM facile hydrolysis under alkaline environment, the pH scope of application only 4～7, and not anti-bacterium and microbial attack.Though the temperature tolerance and the chemical stability of polysulfones, aromatic polyamide membrane are improved largely than CAM, cost an arm and a leg, it is limited to originate, and has limited its extensive use.Therefore, people are seeking function admirable always, and cheap membrane material is to satisfy the needs of large-scale application.PVC is one of three big synthetic resin of output maximum, and is cheap because the source is abundant, can reduce the film cost significantly, simultaneously it also to have chemical stability good, acid and alkali-resistance, advantages such as anti-bacterium erosion have been subjected to people's attention.In commercial macromolecular material, PVC has excellent acid alkalescence.The PVC homopolymers is dissolved in coatings prepared in the appropriate solvent, can stands the aging of acid, alkali, salt solution, oils, food, corrosive gas and atmosphere.Utilize the micropore filtering film commercialization of PVC preparation, carried out the research of PVC film in recent years again in succession.But, the research of PVC milipore filter only is confined on the flat sheet membrane, and to the research of doughnut PVC milipore filter seldom.
What hollow fiber membrane ultrafiltration device adopted is a kind of diffusion barrier that self supports, so in the processing of assembly, need not consider the support problem of film.Its maximum characteristics are that loading density is big, thereby have obtained using widely.The development of hollow fiber ultrafiltration membrane is the key problem of hollow fiber ultrafiltration device.The general employing of hollow-fibre membrane immersed the gel method preparation, and it is that Polymer Solution (spinning solution) is immersed in the precipitating reagent (non-solvent), forms asymmetric hollow fiber membrane by inversion of phases.The moulding of hollow-fibre membrane is the viscosity oneself support by self, has therefore determined the lower limit of the viscosity of spinning solution, if viscosity is too low, hollow-fibre membrane can't moulding.In this external precipitation process, the exchange of solvent and precipitating reagent all takes place in the surfaces externally and internally of film, and interacts and influence the final structure of film, and wherein membrane structure mainly is subjected to the influence of two aspects: 1, the epuilibrium thermodynamics character of spinning solution and precipitation system; 2, solvent and precipitating reagent exchange rate are the film forming procedure mass transfer dynamics in the film forming process.Therefore select suitable preparation liquid system and proper technical conditions to become the key of preparation high-performance hollow fiber ultrafiltration membrane.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of preparation method of high flux polyvinyl chloride hollow fiber ultrafiltration membrane, to overcome the above-mentioned defective that prior art exists.
Technical solution of the present invention:
The preparation method of high flux polyvinyl chloride hollow fiber ultrafiltration membrane of the present invention in turn includes the following steps:
(1) preparation of film liquid
After polyvinyl chloride, solvent and additive mixed film liquid, wherein:
The degree of polymerization of said polyvinyl chloride is 600-3000, and mass percentage content is 8%-25%;
Said solvent comprises dimethyl formamide, dimethylacetylamide or N-methyl pyrrolidone, and mass percentage content is 75%-92%;
Said additive is polyethylene glycol or the polyvinylpyrrolidone of molecular weight 200-20000, and mass percentage content is 0%-15%;
(2) film forming
The film liquid and the inner gel medium that will be made by step (1) are outer inner gel medium coagulation bath film forming by the shower nozzle injection with distilled water by 5-98wt% simultaneously, promptly obtain high flux polyvinyl chloride hollow fiber ultrafiltration membrane of the present invention.Wherein:
Said inner gel medium is water, the dimethyl formamide aqueous solution, the dimethylacetylamide aqueous solution or the N-methyl pyrrolidone aqueous solution;
Said outer gel media is a water;
The temperature of inside and outside gel media is 0-50 ℃;
The concentration of the preferred dimethyl formamide aqueous solution, the dimethylacetylamide aqueous solution or the N-methyl pyrrolidone aqueous solution is 5～98wt%.
For the milipore filter for preparing can be preserved, also must protect processing to film under drying regime.The protection processing method that adopts among the present invention is to soak into hollow-fibre membrane 10～30 hours with the 10-80wt% glycerine water solution; through after such processing; the hollow fiber ultrafiltration membrane that makes can not shunk in the kept dry process; keep its high osmosis energy fully; and when the assembling hollow fiber membrane ultrafiltration device, guarantee that hollow-fibre membrane and epoxy resin glue bond are good.
Adopt the high flux polyvinyl chloride hollow fiber ultrafiltration membrane that said method obtained to have very excellent performance, voidage reaches more than 90%, and pure water flux reaches 400L/ (hm
2) more than, utilize to the invention provides system preparation liquid prescription institute's modulation polymer and filming technology technology, can prepare hollow-fibre membrane with PSPP, they have very high pure water permeability.Prepared polyvinyl chloride hollow fiber ultrafiltration membrane can be in wastewater treatment, and food, concentrates and sterilization and ultra-pure water production application have the wide range of industrial applications prospect separation of medicine and other biogenetic products.
Description of drawings
Fig. 1 is the nozzle structure schematic diagram.
Fig. 2 is embodiment 1 film outer surface.
Fig. 3 is embodiment 1 a film inner surface.
The specific embodiment
Referring to Fig. 1, said shower nozzle comprises outer tube 1 and interior pipe 2, and interior pipe 2 diameters are 0.3-0.8mm, and outer tube 1 internal diameter is 0.6-1.2mm.
The film liquid that will be made by step (1) is squeezed between the annulus of the outer tube 1 of shower nozzle and interior pipe 2 by Compressed Gas, and pipe 2 injects the inner gel media in shower nozzle simultaneously, makes film liquid and inner gel medium inject the coagulation bath freezing film simultaneously.Shower nozzle and coagulation bath distance are 0-20mm.Can make hollow fiber ultrafiltration membrane by above-mentioned condition,
Below by example the present invention is illustrated, but it does not limit protection scope of the present invention.
Embodiment 1
Press column weight amount percentage and take by weighing raw material, PVC (1300): 14%; DMAC:81% and PVP:5% are mixed with preparation liquid, and its process is: earlier 5%PVP is added stirring and dissolving among 81% the DMAC, treat that PVP all after the dissolving, adds 14% PVC stirring and dissolving again.Placed 72 hours, temperature is 25 ℃.The preparation liquid for preparing is poured in the batch can, leaves standstill deaeration in 24 hours.Pipe 2 diameters were 0.5mm in shower nozzle was of a size of, and outer tube 1 internal diameter is 0.8mm, and preparation liquid is from the ejection of shower nozzle annular space, and temperature is controlled at 25 ℃, injected outer coagulation bath then and solidified, and again through rinsing bowl, became silk with 7 meters/bundling speed coiling boundling.The inner gel medium is gone into nascent state doughnut center to form hollow with the metering infusion, and the inner gel medium is the 95%DMAC aqueous solution, and outer coagulation bath is a pure water, and inside and outside coagulation bath temperature all is 25 ℃, and the rinsing bowl temperature also is 25 ℃.The hollow-fibre membrane that spinning forms is assembled into hollow fiber membrane ultrafiltration device in the time of can be in dry state after protection is handled.
Press example 1 described preparation process and condition, PVC (1300): 14%; DMAC:81% and PVP:5% are mixed with preparation liquid.Press example 1 described preparation process.Except changing inner gel liquid into pure water, other process conditions and the example 1 identical hollow-fibre membrane that makes adopt same protection to handle and be assembled into ultrafilter.
Embodiment 3
Press example 1 described preparation process and condition, but preparation liquid adopts following percentage by weight, PVC (1300): 12%; DMAC:81% and PVP:5%, other is identical with example 1, repeats example 1 process and makes hollow-fibre membrane, and be assembled into ultrafilter.
Embodiment 4
Press column weight amount percentage and take by weighing raw material, PVC (1300): 14%; DMAC:86% is mixed with preparation liquid, and other is identical with example 1, repeats example 1 process and makes hollow-fibre membrane, and be assembled into ultrafilter.
Embodiment 5
Press column weight amount percentage and take by weighing raw material, PVC (1300): 14%; DMAC:81% and PEG (1000): 5% is mixed with preparation liquid, and other is identical with example 1, repeats example 1 process and makes hollow-fibre membrane, and be assembled into ultrafilter.
Embodiment 6
Press column weight amount percentage and take by weighing raw material, PVC (1300): 14%; DMF:81% and PVP:5% are mixed with preparation liquid, and other is identical with example 1, repeat example 1 process and make hollow-fibre membrane, and be assembled into ultrafilter.
Embodiment 7
Press column weight amount percentage and take by weighing raw material, PVC (1300): 14%; NMP:81% and PVP:5% are mixed with preparation liquid, and other is identical with example 1, repeat example 1 process and make hollow-fibre membrane, and be assembled into ultrafilter.
Embodiment 8
Press column weight amount percentage and take by weighing raw material, PVC (800): 14%; DMAC:81% and PVP:5% are mixed with preparation liquid, and other is identical with example 1, repeat example 1 process and make hollow-fibre membrane, and be assembled into ultrafilter.
Embodiment 9
Press column weight amount percentage and take by weighing raw material, PVC (2000): 14%; DMAC:81% and PVP:5% are mixed with preparation liquid, and other is identical with example 1, repeat example 1 process and make hollow-fibre membrane, and be assembled into ultrafilter.
Embodiment 9
With the hollow fiber ultrafiltration membrane 4-6 root that embodiment 1-8 makes, to pack in φ 6 * 230mm stainless steel tube, two ends seal with epoxide-resin glue, are assembled into small-sized ultrafilter respectively, measure its pure water flux and rejection.Its water flux performance such as table 1, rejection such as table 2.
By table 1 and table 2 result as can be seen, the prepared a series of polyvinyl chloride hollow fiber ultrafiltration membrane of the present invention have different characteristic and the very high pure water permeability energy held back.Utilize ESEM further to study the structure of hollow-fibre membrane, can find that section is finger-like pore structure or macropore sponge assembling structure, inside and outside all have a dense layer surface.Hot strength has mechanical strength preferably at 1.3-3.5Mpa.
Embodiment 10
The membrane flux test:
Ready-made membrane module is installed in the testing arrangement, and after 1 hour, adjustment pressure is 0.2Mpa through pre-compacted, records the pure water transit dose that passes through membrane module in the certain hour, calculates the pure water flux of every kind of film.
Embodiment 11
The test of film rejection:
The preparation mass fraction is the range protein solution of 0.05%-0.1%, carries out the rejection test in the device of example 10, and operating pressure is 0.2Mpa.Record the solution concentration that film separates front and back with spectrophotometer, calculate the rejection of every kind of film.
Can see from above-mentioned example, utilize to the invention provides system preparation liquid prescription institute's modulation polymer and filming technology technology that can prepare the hollow-fibre membrane with different rejection, they have very high pure water permeability.Prepared polyvinyl chloride hollow fiber ultrafiltration membrane can be in wastewater treatment, and food, concentrates and sterilization and ultra-pure water production application have the wide range of industrial applications prospect separation of medicine and other biogenetic products.
The voidage of the different hollow-fibre membranes of table 1 and pure water flux
| Embodiment | Voidage | Pure water flux L/ (hm 2) |
| ????1 | ????86.9％ | ????332 |
| ????2 | ????78.8％ | ????192 |
| ????3 | ????90.3％ | ????402 |
| ????4 | ????73.2％ | ????46 |
| ????5 | ????81.5％ | ????170 |
| ????6 | ????89.2％ | ????320 |
| ????7 | ????90.6％ | ????210 |
| ????8 | ????90.3％ | ????406 |
| ????9 | ????86.0％ | ????316 |
The rejection of the different hollow-fibre membranes of table 2
| Embodiment | Bovine serum albumin (67000) | Egg albumin (45000) | Lysozyme (14400) |
| ??1 | ??99％ | ??93％ | ??37％ |
| ??2 | ??99％ | ??79％ | ??13％ |
| ??3 | ??99％ | ??93％ | ??63％ |
| ??4 | ??99％ | ??91％ | ??59％ |
| ??5 | ??99％ | ??84％ | ??71％ |
| ??6 | ??99％ | ??76％ | ??9％ |
| ??7 | ??99％ | ??91％ | ??37％ |
| ??8 | ??99％ | ??91％ | ??45％ |
| ??9 | ??99％ | ??90％ | ??15％ |
Claims (6)
1. the preparation method of a high flux polyvinyl chloride hollow fiber ultrafiltration membrane in turn includes the following steps:
(1) preparation of film liquid:
After polyvinyl chloride, solvent and additive mixed film liquid, wherein:
The degree of polymerization of said polyvinyl chloride is 600-3000;
Said solvent comprises dimethyl formamide, dimethylacetylamide or N-methyl pyrrolidone;
Said additive is polyethylene glycol or the polyvinylpyrrolidone of molecular weight 200-20000;
(2) film forming:
The film liquid and the inner gel medium that will be made by step (1) are outer inner gel medium coagulation bath film forming by the shower nozzle injection with distilled water simultaneously, promptly obtain high flux polyvinyl chloride hollow fiber ultrafiltration membrane of the present invention, said inner gel medium is water, the dimethyl formamide aqueous solution, the dimethylacetylamide aqueous solution or the N-methyl pyrrolidone aqueous solution; Said outer gel media is a water.
2. method according to claim 1 is characterized in that, mass percentage content is 8%-25% in the film liquid, and the mass percentage content of solvent is 75%-92%, and the mass percentage content of additive is 0%-15%.
3. method according to claim 1 is characterized in that it is outer inner gel medium coagulation bath film forming that film liquid and inner gel medium inject with distilled water by shower nozzle simultaneously by 5-98wt%.
4. method according to claim 1, the temperature that it is characterized in that inside and outside gel media is 0-50 ℃.
5. method according to claim 1 is characterized in that shower nozzle and coagulation bath distance is 0-20mm.
6. according to each described method of claim 1～5, it is characterized in that soaking into hollow-fibre membrane 10～30 hours with the 10-80wt% glycerine water solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 02145427 CN1415407A (en) | 2002-11-19 | 2002-11-19 | Method for preparing ultra filtration membrane in hollow fiber made from PVC with high flux |
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| CN 02145427 CN1415407A (en) | 2002-11-19 | 2002-11-19 | Method for preparing ultra filtration membrane in hollow fiber made from PVC with high flux |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014150A1 (en) * | 2003-08-06 | 2005-02-17 | Shanghai Litree Purifying Equipment Co., Ltd. | Pvc hollow filtration membrane and the preparation method thereof |
| CN1332738C (en) * | 2004-09-01 | 2007-08-22 | 中国科学院化学研究所 | Method for preparing high-flux crystalline polymer microporous filtering film |
| CN100427191C (en) * | 2005-12-28 | 2008-10-22 | 上海应用技术学院 | Production of hollow fibrous air single external skin separating film with polyether sulphone |
| CN101195084B (en) * | 2007-06-14 | 2010-11-17 | 海南立昇净水科技实业有限公司 | Hydrophilic polyvinyl chloride alloy ultrafiltration membrane and production method thereof |
| 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 |
| CN102202772A (en) * | 2008-11-03 | 2011-09-28 | 泽农科技合股公司 | Filtration membrane with tubular support |
| CN102614785A (en) * | 2012-04-12 | 2012-08-01 | 东华大学 | Polrvinyl chloride and cellulose acetate blend membrane and preparation method thereof |
| CN103495348A (en) * | 2013-09-30 | 2014-01-08 | 广州超禹膜分离技术有限公司 | Polyvinyl chloride hollow fiber ultrafiltration membrane and preparation method thereof |
| CN111558367A (en) * | 2020-05-25 | 2020-08-21 | 广东维清环境工程有限公司 | Preparation method of hollow fiber composite filtering adsorption dephosphorization material |
-
2002
- 2002-11-19 CN CN 02145427 patent/CN1415407A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014150A1 (en) * | 2003-08-06 | 2005-02-17 | Shanghai Litree Purifying Equipment Co., Ltd. | Pvc hollow filtration membrane and the preparation method thereof |
| US7435348B2 (en) | 2003-08-06 | 2008-10-14 | Shanghai Litree Purifying Equipment Co., Ltd. | Pvc hollow filtration membrane and the preparation method thereof |
| CN1332738C (en) * | 2004-09-01 | 2007-08-22 | 中国科学院化学研究所 | Method for preparing high-flux crystalline polymer microporous filtering film |
| CN100427191C (en) * | 2005-12-28 | 2008-10-22 | 上海应用技术学院 | Production of hollow fibrous air single external skin separating film with polyether sulphone |
| CN101195084B (en) * | 2007-06-14 | 2010-11-17 | 海南立昇净水科技实业有限公司 | Hydrophilic polyvinyl chloride alloy ultrafiltration membrane and production method thereof |
| 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 |
| CN102202772A (en) * | 2008-11-03 | 2011-09-28 | 泽农科技合股公司 | Filtration membrane with tubular support |
| CN102614785A (en) * | 2012-04-12 | 2012-08-01 | 东华大学 | Polrvinyl chloride and cellulose acetate blend membrane and preparation method thereof |
| CN103495348A (en) * | 2013-09-30 | 2014-01-08 | 广州超禹膜分离技术有限公司 | Polyvinyl chloride hollow fiber ultrafiltration membrane and preparation method thereof |
| 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 |
| CN111558367A (en) * | 2020-05-25 | 2020-08-21 | 广东维清环境工程有限公司 | Preparation method of hollow fiber composite filtering adsorption dephosphorization material |
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