CN102091538A - Method for preparing polyvinyl alcohol nanofiltration membrane with high rejection coefficient - Google Patents
Method for preparing polyvinyl alcohol nanofiltration membrane with high rejection coefficient Download PDFInfo
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- CN102091538A CN102091538A CN2011100043291A CN201110004329A CN102091538A CN 102091538 A CN102091538 A CN 102091538A CN 2011100043291 A CN2011100043291 A CN 2011100043291A CN 201110004329 A CN201110004329 A CN 201110004329A CN 102091538 A CN102091538 A CN 102091538A
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- polyvinyl alcohol
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Abstract
The invention relates to a method for preparing a polyvinyl alcohol nanofiltration membrane with high rejection coefficient by using interface control. The method comprises the following steps: processing a polysulfone base membrane with 2%-8% glutaraldehyde aqueous solution for 2-4 minutes; drying the base membrane in a shade place; coating the polyvinyl alcohol aqueous solution with a mass fraction of 1%-5% onto the preprocessed membrane for 1-3 minutes; and processing the acquired compound membrane for 2-4 hours at 90 DEG C, so as to have full cross-linking reaction between the glutaraldehyde and the polyvinyl alcohol. The prepared polyvinyl alcohol nanofiltration membrane has a rejection coefficient of 98.5% to 2000ppm sodium sulfate, a rejection coefficient of 80.1% to 2000ppm sodium chloride and a rejection coefficient of 98.7% to 2000ppm polyethylene glycol 600. The method provided by the invention is novel and simple and the repeatability of membrane property test is good.
Description
Technical field
The present invention relates to a kind of preparation method of polymer material film, be meant that specifically a kind of hydrophily is good, the preparation method of the NF membrane that rejection is high.
Background technology
Nanofiltration is a kind of novel membrane separation technique, and the scope of holding back of NF membrane is between 200-2000, and operating pressure is low than counter-infiltration, will hold back far below bivalent ions the rejection of monovalention.And organic pollution there is separating effect preferably.
Composite membrane is to make porous support membrane with a kind of polymer earlier, then the film of making in the method for support membrane surface formation one deck fine and close separating layer as thin as a wafer with another kind of polymer.Its preparation method is divided into four classes and comprises laminating, dip coating, plasma vapor deposition processes and interfacial polymerization.In the whole bag of tricks, interfacial polymerization is the maximum preparation method of use that preparation at present meets NF membrane.This method is to make reactant immiscible two polymerization film formation take place at the interface, and compound one deck plays the superthin layer of desalination on film.The effective area that filters has also been improved on rough film blank surface, and flux is increased.But this method also has shortcoming, such as the selection to basement membrane higher requirement is arranged, and film forming procedure was finished in moment, is difficult to the structure and the performance of superthin layer are effectively controlled.
Polyvinyl alcohol (being called for short PVA) outward appearance is a white powder, it is a kind of purposes high molecular weight water soluble polymer quite widely, because PVA has unique powerful cementability, film pliability, flatness, oil resistivity, solvent resistance and wearability, and hydrophily is good, is a kind of desirable membrane material therefore.Polyvinyl alcohol with water is solvent, and is very little to the pollution of environment, and can save cost.
The NF membrane that directly applies preparation with polyvinyl alcohol is held back DeGrain, and meets water-soluble expanding in the process of using easily, and the polyvinyl alcohol that swelling is enough comes off from face easily and causes scrapping of film.In order to control its swellbility in water, can adopt the method for chemical crosslinking, crosslinking agents such as adding glutaraldehyde make it form a kind of network-like cross-linked structure.
The polyvinyl alcohol glutaraldehyde is a catalyst with strong acid in the aqueous solution, and the big molecule of glutaraldehyde that can synthesizing cross-linked polyvinyl alcohol contracts can prevent the polyvinyl alcohol swelling on the one hand, and the crosslinked on the other hand face that also can make is fine and close more, improves rejection.
Bian Xiaokai etc. adopt coating process to prepare composite membrane by the variation to film liquid composition and preparation condition, are about to the coating solution of certain polyvinyl alcohol and glutaraldehyde proportioning, and (Mayor rod) is coated on the basement membrane equably with the Mei Er pole, prepared the PVA composite nanometer filtering film.Wu Hong etc. are poured on knifing on the glass plate with the polyvinyl alcohol glutaraldehyde water solution of certain proportioning, have prepared conductive polyvinyl alcohol glutaraldehyde cross-linking film.Charles.W.Walker etc. (US Patent:7176247B1,2007) use mechanical cladding process to prepare the cross linking membrane of the interpenetrating networks with different water imbibitions, pure selectivity and electric conductivity with the polyvinyl alcohol water solution and the glutaraldehyde water solution of variable concentrations.(US Patent:6214331B1,2001) such as John W.Vanderhoff use the PVA aqueous solution and glutaraldehyde cross-linking at normal temperatures, and are the particulate that catalyst prepares swellable with the p-methyl benzenesulfonic acid.The matrix that (US Patent:5914182B1,1999) such as Paul D.Drumheller prepare the bioactive materials that fixes with the polyvinyl alcohol water solution and the water-soluble reaction of glutaraldehyde of variable concentrations.
Summary of the invention
The present invention proposes a kind of new preparation method of the high polyvinyl alcohol NF membrane of holding back.The polysulfones counterdie is handled 2-4min with the glutaraldehyde water solution of 2%-5%, dry in the shade, the polyvinyl alcohol water solution that with mass fraction is 1%-5% then is coated in 1-3min on the good film of preliminary treatment, the composite membrane of gained is handled 2-4h through 90 ℃, makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place and then makes the polyvinyl alcohol NF membrane that height is held back.
The present invention is achieved by the following technical programs:
The preparation of A, casting solution
The preparation quality mark is the glutaraldehyde water solution of 2%-5%, drips acid solution and regulates its pH value to the 3-6, and is stand-by.The preparation quality mark is the polyvinyl alcohol water solution of 1%-5%, and deaeration is stand-by.
The preparation of B, polyvinyl alcohol NF membrane
The polysulfones counterdie being handled 2-4min with the glutaraldehyde water solution of 2%-5%, dry in the shade, is that the polyvinyl alcohol water solution of 1%-5% is coated in 1-3min on the good film of preliminary treatment then with mass fraction.The composite membrane of gained makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place through 90 ℃ of processing 2-4h.
As preferably, the pH conditioning agent in the above-mentioned preparation process is watery hydrochloric acid or dilute sulfuric acid, wherein uses hydrochloric acid to be the best.
As preferably, the molecular cut off of the polysulfones counterdie in the above-mentioned preparation process is that 2-3 ten thousand is for best.
As preferably, the molecular weight of the polyvinyl alcohol in the above-mentioned preparation process is 50000～100000 moderate molecular weight.
Effective effect: the preparation method among the present invention is simply novel, and NF membrane has very high rejection and good hydrophily, and higher for the rejection of PE6600, selectivity is good.
The specific embodiment
The present invention will be further described below in conjunction with example, but protection scope of the present invention is not limited to this.
Embodiment 1
The preparation quality mark is 2% glutaraldehyde water solution, dripping hydrochloric acid solution is regulated about its pH value to 4, the polysulfones counterdie is handled 2min with 2% glutaraldehyde water solution, dry in the shade, be that 1% polyvinyl alcohol water solution is coated in 1min on the good film of preliminary treatment then with mass fraction, the composite membrane of gained makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place through 90 ℃ of processing 2h.Prepared polyvinyl alcohol NF membrane be 70.1% to holding back of 2000ppm sodium sulphate, be 58.2% to holding back of 2000ppm sodium chloride, be 73.2% to holding back of 2000ppm Macrogol 600.
Embodiment 2
The preparation quality mark is 2% glutaraldehyde water solution, dripping hydrochloric acid solution is regulated about its pH value to 5, the polysulfones counterdie is handled 2min with 2% glutaraldehyde water solution, dry in the shade, be that 2% polyvinyl alcohol water solution is coated in 1.5min on the good film of preliminary treatment then with mass fraction, the composite membrane of gained makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place through 90 ℃ of processing 2h.Prepared polyvinyl alcohol NF membrane be 78.7% to holding back of 2000ppm sodium sulphate, be 59.5% to holding back of 2000ppm sodium chloride, be 80.1% to holding back of 2000ppm Macrogol 600.
Embodiment 3
The preparation quality mark is 3% glutaraldehyde water solution, dripping sulfuric acid solution liquid regulates about its pH value to 5, the polysulfones counterdie is handled 2min with 2% glutaraldehyde water solution, dry in the shade, be that 3% polyvinyl alcohol water solution is coated in 1.5min on the good film of preliminary treatment then with mass fraction, the composite membrane of gained makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place through 90 ℃ of processing 2h.Prepared polyvinyl alcohol NF membrane be 83.2% to holding back of 2000ppm sodium sulphate, be 65.3% to holding back of 2000ppm sodium chloride, be 85.7% to holding back of 2000ppm Macrogol 600.
Embodiment 4
The preparation quality mark is 3% glutaraldehyde water solution, dripping hydrochloric acid solution is regulated about its pH value to 5, the polysulfones counterdie is handled 2min with 3% glutaraldehyde water solution, dry in the shade, be that 3% polyvinyl alcohol water solution is coated in 2min on the good film of preliminary treatment then with mass fraction, the composite membrane of gained makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place through 90 ℃ of processing 2h.Prepared polyvinyl alcohol NF membrane be 85.8% to holding back of 2000ppm sodium sulphate, be 70.3% to holding back of 2000ppm sodium chloride, be 88.3% to holding back of 2000ppm Macrogol 600.
Embodiment 5
The preparation quality mark is 3% glutaraldehyde water solution, dripping sulfuric acid solution regulates about its pH value to 5.5, the polysulfones counterdie is handled 2min with 3% glutaraldehyde water solution, dry in the shade, be that 4% polyvinyl alcohol water solution is coated in 2min on the good film of preliminary treatment then with mass fraction, the composite membrane of gained makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place through 90 ℃ of processing 2h.Prepared polyvinyl alcohol NF membrane be 90.6% to holding back of 2000ppm sodium sulphate, be 77.2% to holding back of 2000ppm sodium chloride, be 91.8% to holding back of 2000ppm Macrogol 600.
Embodiment 6
The preparation quality mark is 4% glutaraldehyde water solution, dripping hydrochloric acid solution is regulated about its pH value to 5.8, the polysulfones counterdie is handled 2min with 4% glutaraldehyde water solution, dry in the shade, be that 4% polyvinyl alcohol water solution is coated in 2min on the good film of preliminary treatment then with mass fraction, the composite membrane of gained makes glutaraldehyde and polyethylene glycol that sufficient cross-linking reaction take place through 90 ℃ of processing 2h.Prepared polyvinyl alcohol NF membrane be 98.1% to holding back of 2000ppm sodium sulphate, be 79.3% to holding back of 2000ppm sodium chloride, be 98.3% to holding back of 2000ppm Macrogol 600.
Claims (5)
1. the preparation method of one kind high rejection polyvinyl alcohol NF membrane, its feature mainly comprises step:
The preparation of A, casting solution
The preparation quality mark is the glutaraldehyde water solution of 2%-8%, drips acid solution and regulates its pH value to the 3-6, and is stand-by;
The preparation quality mark is the polyvinyl alcohol water solution of 1%-5%, and deaeration is stand-by;
The preparation of B, polyvinyl alcohol NF membrane
The polysulfones counterdie being handled 2-4min with the glutaraldehyde water solution of 2%-8%, dry in the shade, is that the polyvinyl alcohol water solution of 1%-5% is coated in 1-3min on the good film of preliminary treatment then with mass fraction; The composite membrane of gained is handled 2-4h through 90 ℃, makes glutaraldehyde and polyethylene glycol generation cross-linking reaction; Wherein said polysulfones counterdie molecular cut off is 2-3 ten thousand.
2. preparation method according to claim 1 is characterized in that described pH conditioning agent is watery hydrochloric acid or dilute sulfuric acid.
3. preparation method according to claim 2 is characterized in that described pH conditioning agent is a watery hydrochloric acid.
4. preparation method according to claim 1 is characterized in that described polyvinyl alcohol is an alcoholysis degree 98～99%, and molecular weight is 50000～100000 moderate molecular weight.
5. preparation method according to claim 1 is characterized in that described poly-vinyl alcohol solution is for to handle through the vavuum pump deaeration.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521099A (en) * | 2013-10-15 | 2014-01-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of cationic polyacrylamide polyvinyl alcohol nanofiltration membrane |
| CN104587851A (en) * | 2014-11-28 | 2015-05-06 | 北京碧水源膜科技有限公司 | Preparation method of composite nanofiltration membrane |
| CN104607056A (en) * | 2015-02-03 | 2015-05-13 | 贺攀 | Hollow fiber compound nanofiltration membrane and preparation method thereof |
| CN104801200A (en) * | 2015-04-02 | 2015-07-29 | 江苏大孚膜科技有限公司 | Preparation method for composite nano-filtration membrane |
| CN106268362A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | The preparation method of a kind of antimicrobial compound film and the antimicrobial compound film prepared by the method thereof and its application in water treatment field |
| CN106621841A (en) * | 2016-12-30 | 2017-05-10 | 北京碧水源膜科技有限公司 | Preparation method of positively charged nanofiltration membrane |
| CN106914156A (en) * | 2017-04-10 | 2017-07-04 | 浙江工业大学 | A kind of preparation method of Novel polyvinyl alcohol NF membrane |
| CN109126489A (en) * | 2018-09-30 | 2019-01-04 | 浙江工业大学 | A kind of preparation method of small molecular cut off polysulfone ultrafiltration membrane |
| CN110280143A (en) * | 2019-06-27 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of preparation method of dopamine/graphene oxide/polyvinyl alcohol composite nanometer filtering film |
| CN112397848A (en) * | 2020-12-11 | 2021-02-23 | 宁波启新精合新能源研究院有限公司 | High-performance lithium ion battery diaphragm and preparation thereof |
| CN113230889A (en) * | 2021-05-25 | 2021-08-10 | 浙江工业大学 | Preparation method of novel nanofiltration membrane based on copper hydroxide nanowires |
-
2011
- 2011-01-10 CN CN2011100043291A patent/CN102091538A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| 卞晓锴等: "聚乙烯醇复合膜的制备研究初探", 《化学世界增刊》 * |
| 康芳萍: "聚乙烯醇复合纳滤膜的制备", 《中国优秀硕士论文学位论文全文数据库(电子期刊)工程科技I辑》 * |
| 李兆魁等: "纳滤膜功能材料研究进展", 《水处理技术》 * |
| 肖凯军等: "新型聚乙烯醇超滤膜的制备、表观特性及应用", 《工程塑料应用》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521099A (en) * | 2013-10-15 | 2014-01-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of cationic polyacrylamide polyvinyl alcohol nanofiltration membrane |
| CN104587851A (en) * | 2014-11-28 | 2015-05-06 | 北京碧水源膜科技有限公司 | Preparation method of composite nanofiltration membrane |
| CN104587851B (en) * | 2014-11-28 | 2017-04-05 | 北京碧水源膜科技有限公司 | A kind of preparation method of composite nanometer filtering film |
| CN104607056A (en) * | 2015-02-03 | 2015-05-13 | 贺攀 | Hollow fiber compound nanofiltration membrane and preparation method thereof |
| CN104607056B (en) * | 2015-02-03 | 2016-09-28 | 贺攀 | A kind of hollow fiber compound nanofiltration membrane and preparation method thereof |
| CN104801200A (en) * | 2015-04-02 | 2015-07-29 | 江苏大孚膜科技有限公司 | Preparation method for composite nano-filtration membrane |
| CN106268362A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | The preparation method of a kind of antimicrobial compound film and the antimicrobial compound film prepared by the method thereof and its application in water treatment field |
| CN106268362B (en) * | 2015-06-12 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of preparation method of antimicrobial compound film and its antimicrobial compound film and its application in water treatment field by this method preparation |
| CN106621841B (en) * | 2016-12-30 | 2020-09-18 | 北京碧水源膜科技有限公司 | Preparation method of positively charged nanofiltration membrane |
| CN106621841A (en) * | 2016-12-30 | 2017-05-10 | 北京碧水源膜科技有限公司 | Preparation method of positively charged nanofiltration membrane |
| CN106914156A (en) * | 2017-04-10 | 2017-07-04 | 浙江工业大学 | A kind of preparation method of Novel polyvinyl alcohol NF membrane |
| CN106914156B (en) * | 2017-04-10 | 2019-09-17 | 浙江工业大学 | A kind of preparation method of polyvinyl alcohol nanofiltration membrane |
| CN109126489A (en) * | 2018-09-30 | 2019-01-04 | 浙江工业大学 | A kind of preparation method of small molecular cut off polysulfone ultrafiltration membrane |
| CN109126489B (en) * | 2018-09-30 | 2020-10-02 | 浙江工业大学 | Preparation method of small-interception-molecular-weight polysulfone ultrafiltration membrane |
| CN110280143A (en) * | 2019-06-27 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of preparation method of dopamine/graphene oxide/polyvinyl alcohol composite nanometer filtering film |
| CN112397848A (en) * | 2020-12-11 | 2021-02-23 | 宁波启新精合新能源研究院有限公司 | High-performance lithium ion battery diaphragm and preparation thereof |
| CN112397848B (en) * | 2020-12-11 | 2023-03-24 | 宁波启新精合新能源研究院有限公司 | High-performance lithium ion battery diaphragm and preparation thereof |
| CN113230889A (en) * | 2021-05-25 | 2021-08-10 | 浙江工业大学 | Preparation method of novel nanofiltration membrane based on copper hydroxide nanowires |
| CN113230889B (en) * | 2021-05-25 | 2022-04-19 | 浙江工业大学 | Preparation method of novel nanofiltration membrane based on copper hydroxide nanowires |
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Application publication date: 20110615 |