CN1296124C - Method for preparing compound nanometer filtering membrane of chitosan sulfate-high molecule polymer - Google Patents
Method for preparing compound nanometer filtering membrane of chitosan sulfate-high molecule polymer Download PDFInfo
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- CN1296124C CN1296124C CNB2004100361951A CN200410036195A CN1296124C CN 1296124 C CN1296124 C CN 1296124C CN B2004100361951 A CNB2004100361951 A CN B2004100361951A CN 200410036195 A CN200410036195 A CN 200410036195A CN 1296124 C CN1296124 C CN 1296124C
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Abstract
The present invention relates to a method for preparing a compound nanofiltration membrane of chitosan sulfate and high molecule polymer. The present invention is characterized in that an ultrafiltration membrane made from high molecular polymer is used as a basal membrane, and the high molecular polymer can be polyvinyl cyanide, polysulfone, polyethersulfone, polypropylene, polyethylene, polyvinylidene fluoride, cellulose acetate, polyurethane, polyvinyl chloride, polycaprolactam or polyfuran alcohol. The basal membrane is uniformly coated with a layer of water solution of chitosan sulfate or water solution containing chitosan sulfate and NaOH, and the coated basal membrane is processed at 50 to 60 DEG C for 0.5 to 2h. The coated basal membrane is coated with a layer of water-soluble aldehyde cross-linking agent or oil-soluble cross-linking agent, such as ethanol solution of epoxy chloropropane, tetracyanofuran solution of diisocyanate and tetracyanofuran solution of propanetriol glycidyl ether. Cross-linking is carried out at 50 to 65 DEG C for 2 to 4h, and then the membrane is washed by deionized water. The surface of the membrane of the present invention has a small amount of uncrosslinked free amino groups, so that the membrane has the sterilization effect. Algae and microorganism are not easy to attach to the membrane. Consequently, the present invention improves the service efficiency of the membrane, prolongs the service life, and has favorable efficiency of the nanofiltration membrane.
Description
Technical field:
The present invention relates to a kind of preparation method who is used for the NF membrane of water treatment, particularly relate to the preparation method of a kind of sulfated chitosan-high molecular polymer composite nanometer filtering film.
Background technology:
NF membrane is the film product of a kind of membrane aperture between counter-infiltration and milipore filter, and it has Na
+And Cl
-Lower Deng the monovalention rejection, but to Ca
2+, SO
4 2-, Mg
2+Advantages such as the rejection Deng high price ion and organic matter small-molecular weight (200～1000) material is very high, and operating pressure is low.Since last century the mid-1970s to have developed some NF membrane, as the asymmetric NF membrane of two acetic acid-triacetate fiber, aromatic polyamide composite nanometer filtering film and sulfonated polyether sulfone coating composite nanometer filtering film etc.These high molecular compound film surfaces are microorganism such as periphtic algae and bacterium easily, influences the service efficiency and the life-span of film.The NF membrane development ground zero of China.
Summary of the invention:
The purpose of this invention is to provide a kind of method for preparing sulfated chitosan-high molecular polymer composite nanometer filtering film, to remedy the above-mentioned deficiency of this technology both at home and abroad.
The preparation method of a kind of sulfated chitosan-high molecular polymer composite nanometer filtering film, it is characterized in that to hold back relative molecular weight be 6000～10000 high molecular polymer polyacrylonitrile, polysulfones, polyether sulfone, polypropylene, polyethylene, Kynoar, the cellulose acetate class, Polyurethane, polyvinyl chloride, the milipore filter of polycaprolactam or poly-furans alcohol is a basement membrane, the even aqueous solution of the sulfated chitosan of dip-coating one deck 2.0%～4.0% or contain 2.0%～4.0% sulfated chitosan and the aqueous solution of 5.0%～10%NaOH on this basement membrane, handle 0.5～2h for 50～60 ℃, dip-coating one deck 0.5～2% formaldehyde again, acetaldehyde, the water soluble aldehyde crosslinking agent of glutaraldehyde or the ethanolic solution of 0.5～1.0% epoxychloropropane, four cyanogen furans solution of vulcabond, four cyanogen furans solution, the one class oil-soluble crosslinking agent of propanetriol-diglycidyl-ether, crosslinked 2～4h under 50～65 ℃ cleans with deionized water.
Sulfated chitosan of the present invention-high molecular polymer composite membrane surface is because of there being a small amount of uncrosslinked free amine group, so have bactericidal effect, be difficult for periphtic algae and microorganism, thereby improved the service efficiency of film and prolonged its service life, still have good NF membrane effect simultaneously.
The specific embodiment:
Embodiment 1.
Get and hold back the milipore filter that relative molecular weight is 6000～10000 polyacrylonitrile, with washed with de-ionized water film surface, be fixed on the glass plate of level and smooth cleaning with the adhesive tape of wide 1cm, room temperature is evaporated near dried.Getting sulfated chitosan then is dissolved in and is made into 2.0%～4.0% (weight percent concentration in the deionized water, solution down together), filter with 4 flint glass F sand core funnels, getting filtrate carefully is poured on the above-mentioned membrane surface, with the smooth solution of smooth glass bar, make its even dip-coating in the surface of basement membrane, excessive solution allows it overflow, dry the back and handle 0.5～2h at 50～60 ℃, on film, carefully pour 0.5%～2% glutaraldehyde water solution again into, same solution with the glass bar flat surface, excessive solution allows it overflow, then this lamina membranacea is taken off from glass plate behind 50～65 ℃ of heat cross-linking 2～4h, thoroughly clean the back with deionized water and in deionized water, soak 24h, stand-by after the precompressed.Carry out the desalination experiment with this film on desalter, in room temperature, flow is 40L/h, and operating pressure is 4.0Mpa, to the NaCl and the Na of 1000mg/L concentration
2SO
4Solution is handled, when two kinds of feed liquid flux are 10.7kg/m
2During h, the rejection that records two kinds of salt is respectively 40% and 50%; When two kinds of feed liquid flux are 7.1kg/m
2During h, the salt rejection that records two kinds of salt is respectively: 81% and 92%.Illustrate that this film has good NF membrane function.
When using the glutaraldehyde in the present embodiment instead formaldehyde, acetaldehyde water soluble aldehyde crosslinking agent or its mixture, the film that makes also has similar nanofiltration effect.
Embodiment 2.
Polypropylene cyanogen milipore filter among the embodiment 1 used instead hold back the milipore filter that relative molecular weight is 6000～10000 polysulfones, polyether sulfone, polypropylene, polyethylene, Kynoar, cellulose acetate class, Polyurethane, polyvinyl chloride, polycaprolactam or poly-furans alcohol, conditions such as operating pressure are identical with embodiment 1, record corresponding high molecular polymer-sulfated chitosan composite nanometer filtering film and have and the similar nanofiltration effect of embodiment 1 polyacrylonitrile sulfated chitosan composite nanometer filtering film.
Embodiment 3.
Evenly the chitosan sulfate aqueous solution of ester of dip-coating changes and is coated with one deck and contains 2.0%～4.0% the sulfated chitosan and the aqueous solution of 5.0%～10%NaOH on the basement membrane described in embodiment 1 and the embodiment 2, with the smooth solution of smooth glass bar, make its even dip-coating in the surface of basement membrane, excessive solution allows it overflow, dry the back and handle 0.5～2h at 50～60 ℃, dip-coating one deck 0.5～1.0% epoxychloropropane ethanolic solution again, handle 2～4h at 50～65 ℃, clean with deionized water, its nanofiltration effect is similar.
When using the epoxychloropropane ethanolic solution in the present embodiment four cyanogen furans solution of vulcabond, propanetriol-diglycidyl-ether one class oil-soluble crosslinking agent instead, crosslinker concentration, operating condition and step are constant, and the film that makes has similar nanofiltration effect.
Claims (1)
1, a kind of preparation method of sulfated chitosan one high molecular polymer composite nanometer filtering film, it is characterized in that to hold back relative molecular weight be 6000～10000 high molecular polymer polyacrylonitrile, polysulfones, polyether sulfone, polypropylene, polyethylene, Kynoar, the cellulose acetate class, Polyurethane, polyvinyl chloride, the milipore filter of polycaprolactam or poly-furans alcohol is a basement membrane, the even aqueous solution of the sulfated chitosan of dip-coating one deck 2.0%～4.0% or contain 2.0%～4.0% sulfated chitosan and the aqueous solution of 5.0%～10%NaOH on this basement membrane, handle 0.5～2h at 50～60 ℃, dip-coating one deck 0.5～2% formaldehyde again, acetaldehyde, the ethanolic solution of glutaraldehyde water soluble aldehyde crosslinking agent or 0.5～1.0% epoxychloropropane, four cyanogen furans solution of vulcabond, four cyanogen furans solution oil-soluble crosslinking agents of propanetriol-diglycidyl-ether, crosslinked 2～4h under 50～65 ℃ cleans with deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100361951A CN1296124C (en) | 2004-10-29 | 2004-10-29 | Method for preparing compound nanometer filtering membrane of chitosan sulfate-high molecule polymer |
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|---|---|---|---|
| CNB2004100361951A CN1296124C (en) | 2004-10-29 | 2004-10-29 | Method for preparing compound nanometer filtering membrane of chitosan sulfate-high molecule polymer |
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| CN1631498A CN1631498A (en) | 2005-06-29 |
| CN1296124C true CN1296124C (en) | 2007-01-24 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101673831B (en) * | 2008-09-11 | 2011-09-21 | 元智大学 | Composite proton exchange membrane of acidic nanofiber/alkaline high polymer and preparation method thereof |
| CN102266727B (en) * | 2010-06-02 | 2013-10-30 | 中国科学院化学研究所 | Antibacterial ultrafiltration membrane or microfiltration membrane |
| CN102228802A (en) * | 2011-06-27 | 2011-11-02 | 张会艳 | Food-grade antibacterial filter membrane and preparation method thereof |
| CN102653597B (en) * | 2012-05-09 | 2013-11-06 | 江苏维赛科技生物发展有限公司 | Preparation method of cellulose acetate membrane surface crosslinked chitosan hydrophilic membrane |
| CN102974232B (en) * | 2012-11-26 | 2015-06-17 | 武汉江扬环境科技股份有限公司 | Method for producing anti-pollution modified polyvinylidene fluoride hollow fiber membrane |
| CN104548951A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Antibacterial composite nanofiltration membrane with high salt rejection rate and preparation method of antibacterial composite nanofiltration membrane |
| CN103785365B (en) * | 2014-02-25 | 2016-03-30 | 南开大学 | A kind of preparation method of metalloform-selective composite membrane for separation |
| CN105435646B (en) * | 2014-07-22 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof |
| CN105289321B (en) * | 2014-07-22 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof |
| CN105727768B (en) * | 2016-05-13 | 2018-07-10 | 高学理 | A kind of preparation method of the self-supporting forward osmosis membrane based on chitosan |
| CN105854650A (en) * | 2016-06-17 | 2016-08-17 | 安庆市天虹新型材料科技有限公司 | Anti-fouling high-throughput polysulfone composite membrane |
| CN106436313B (en) * | 2016-09-23 | 2018-10-12 | 泉州亚林新材料科技有限公司 | Chitosan quaternary ammonium salt anti-bacterial fibre, fabric, amenities and its preparation process |
| CN109289551B (en) * | 2017-07-25 | 2021-12-21 | 中国石油化工股份有限公司 | Reverse osmosis membrane and preparation method and application thereof |
| CN108636140A (en) * | 2018-05-04 | 2018-10-12 | 烟台金正环保科技有限公司 | A kind of preparation method of the lotus positive electricity polyamide composite nanofiltration membrane based on Lactated chitosan |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS632304A (en) * | 1986-06-20 | 1988-01-07 | Mitsubishi Electric Corp | Manufacture of electromagnetic coil for electromagnetic coupler |
| JPS63256119A (en) * | 1987-04-10 | 1988-10-24 | Kuraray Co Ltd | Dehumidifying and humidifying method |
| JPH0332726A (en) * | 1989-03-14 | 1991-02-13 | Nakano Vinegar Co Ltd | Composite separating membrane and production thereof |
-
2004
- 2004-10-29 CN CNB2004100361951A patent/CN1296124C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS632304A (en) * | 1986-06-20 | 1988-01-07 | Mitsubishi Electric Corp | Manufacture of electromagnetic coil for electromagnetic coupler |
| JPS63256119A (en) * | 1987-04-10 | 1988-10-24 | Kuraray Co Ltd | Dehumidifying and humidifying method |
| JPH0332726A (en) * | 1989-03-14 | 1991-02-13 | Nakano Vinegar Co Ltd | Composite separating membrane and production thereof |
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| CN1631498A (en) | 2005-06-29 |
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