CN103521099A - Preparation method of cationic polyacrylamide polyvinyl alcohol nanofiltration membrane - Google Patents
Preparation method of cationic polyacrylamide polyvinyl alcohol nanofiltration membrane Download PDFInfo
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- CN103521099A CN103521099A CN201310482403.XA CN201310482403A CN103521099A CN 103521099 A CN103521099 A CN 103521099A CN 201310482403 A CN201310482403 A CN 201310482403A CN 103521099 A CN103521099 A CN 103521099A
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- polyvinyl alcohol
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Abstract
The invention discloses a preparation method of a high polymer material membrane and specifically discloses a preparation method of a cationic polyacrylamide polyvinyl alcohol nanofiltration membrane. The preparation method comprises the following steps of firstly, preparing glutaraldehyde aqueous liquor, and mixed aqueous liquor of polyvinyl alcohol and cationic polyacrylamide; then, pre-treating a polysulfone bottom membrane by the glutaraldehyde aqueous liquor for 2-4 minutes, drying in the shade, and coating the pre-treated polysulfone bottom membrane with the mixed aqueous liquor of the polyvinyl alcohol and the cationic polyacrylamide for 1-3 minutes; and finally, treating the obtained composite membrane for 1-4 hours at 90 DEG C to obtain the cationic polyacrylamide polyvinyl alcohol nanofiltration membrane. The preparation method disclosed by the invention has the advantage that the preparation method is simple and novel, the nanofiltration membrane has very high water flux and high retention rate, especially has high retention rate for PEG (Polyethylene Gycol) 600 and has good selectivity.
Description
Technical field
The present invention relates to a kind of preparation method of polymer material film, specifically refer to that a kind of hydrophily is good, the preparation method of the NF membrane that water flux is higher.
Background technology
NF membrane, belongs to a kind of of pressure-driven diffusion barrier, and stalling characteristic and reverse osmosis membrane are similar, but operating pressure is much lower compared with counter-infiltration.Composite membrane is first with a kind of polymer, to make porous support membrane, the film of then 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 who prepares at present NF membrane.Polyvinyl alcohol (being called for short PVA) outward appearance is 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, be therefore a kind of desirable membrane material.Polyvinyl alcohol be take water as solvent, very little to the pollution of environment, and can be cost-saving.PAMC (CPAM) is chain macromolecule compound, because it has multiple active group, and can, absorption formation hydrogen bond affine with many materials.Be mainly the electronegative colloid of flocculation, there is turbidity removal, decolouring, absorption, the function such as bonding, be applicable to dyeing, papermaking, food etc.
Polyvinyl alcohol glutaraldehyde be take strong acid as catalyst in the aqueous solution, and the large molecule of polyvinyl alcohol contracting glutaraldehyde that can be synthesizing cross-linked can prevent polyvinyl alcohol swelling on the one hand, is cross-linked and also can makes face finer and close on the other hand, improves rejection.In the process of polyvinyl alcohol and glutaraldehyde cross-linking, PAMC is mixed in polyvinyl alcohol uniformly, can there is physical crosslinking in PAMC and polyvinyl lactam, polyvinyl alcohol is in crosslinked like this, PAMC and polyvinyl lactam are present between polyvinyl alcohol, crosslink density is with regard to slight reduction like this, water flux increases, in addition, also can there is physical entanglement in the PAMC self being present between polyvinyl alcohol, be equivalent to form one by one little " tank " between cross-linking polyvinyl alcohol, water flux increases.At present, a lot of scholars also endeavour the exploitation with this two series products.
Bian Xiaokai etc. are by the variation to film liquid composition and preparation condition, adopt coating process to prepare composite membrane, be about to the coating solution of certain polyvinyl alcohol and glutaraldehyde proportioning, with Mei Er pole (Mayor rod), be coated in equably on basement membrane, prepared PVA composite nanometer filtering film.Wu Hong etc. are poured on knifing on glass plate by 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) with the polyvinyl alcohol water solution of variable concentrations, prepare with mechanical cladding process from glutaraldehyde water solution there are different water imbibitions, alcohol is selective and the cross linking membrane of the interpenetrating networks of electric conductivity.
Paul D.Drumheller etc. (US Patent:5914182B1,1999) react to prepare with polyvinyl alcohol water solution and the glutaraldehyde of variable concentrations is water-soluble the matrix of bioactive materials of fixing.
Summary of the invention
The present invention proposes a kind of preparation method of PAMC polyvinyl alcohol nanofiltration membrane of high water flux.Polysulfones counterdie is processed to 2-4min with the glutaraldehyde water solution of 1%-5%, dry in the shade, then the polyvinyl alcohol water solution that is 1%-5% by mass fraction is coated in 1-3min on the film that pretreatment is good, and the composite membrane of gained processes through 90 ℃ the PAMC polyvinyl alcohol nanofiltration membrane that 1-4h prepares high water flux.
The present invention is achieved by the following technical programs
A preparation method for PAMC polyvinyl alcohol nanofiltration membrane, is characterized in that comprising the following steps:
(1) preparation of casting solution
Preparation quality mark is the glutaraldehyde water solution of 1%-5%, stand-by; The mixed aqueous solution of preparing polyvinyl alcohol and PAMC, wherein the mass fraction of polyvinyl alcohol is 1%-5%, and the mass fraction of PAMC is 0.01%-0.03%, and deaeration is stand-by;
(2) preparation of PAMC polyvinyl alcohol nanofiltration membrane
Glutaraldehyde water solution pretreatment 2-4min by polysulfones counterdie with 1%-5%, dries in the shade, and then the mixed aqueous solution of polyvinyl alcohol and PAMC is coated in to 1-3min on the polysulfones counterdie that pretreatment is good; The molecular cut off of wherein said polysulfones counterdie is 2-3 ten thousand;
(3) composite membrane of gained, through 90 ℃ of processing 1-4h, makes glutaraldehyde occur to react fully with polyethylene glycol and PAMC.
As preferably, the degree of hydrolysis of the polyvinyl alcohol described in above-mentioned preparation method is 86-89%.
The preparation process of NF membrane seems similar, but wherein far from each other for the separating effect of different material, so in order there to be good separating effect for predetermined substance, need to be in the preparation process of NF membrane, the selection material that has certain requirements, then carries out the heat treatment of specialization, and the difference of the reactant that adopts of film surface, selection effect to film plays crucial effect, and this selection is to draw on the basis of inventor by great many of experiments.Certainly, these selections are for basic according to certain theory.Selective for PEG600 in the present invention, inventor has adopted the preparation-obtained film of aforesaid way to have good effect.
Effective effect: the preparation method in the present invention is simple, novel, NF membrane has very high water flux and good rejection, higher for the rejection of PEG600, selectively good.
The specific embodiment
Below in conjunction with example, the present invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
First be the preparation of casting solution
Preparation quality mark is 2% glutaraldehyde water solution, stand-by; The mixed aqueous solution of preparing polyvinyl alcohol and PAMC, wherein the mass fraction of polyvinyl alcohol is 1%, and the mass fraction of PAMC is 0.01%, and deaeration is stand-by;
(2) preparation of PAMC polyvinyl alcohol nanofiltration membrane
By 2% glutaraldehyde water solution pretreatment 2min for polysulfones counterdie, dry in the shade, then the mixed aqueous solution of polyvinyl alcohol and PAMC is coated in to 1min on the polysulfones counterdie that pretreatment is good; The molecular cut off of wherein said polysulfones counterdie is 2-3 ten thousand;
(3) composite membrane of gained is processed 2h through 90 ℃.
To above-mentioned preparation-obtained film, under the condition that is 1MPa at operating pressure, the Na of prepared composite membrane to 2000ppm
2sO
4rejection be 50%, water flux is 130L/ (m
2h), to the rejection of the NaCl of 2000ppm, be 17%, water flux is 135L/ (m
2h), to the rejection of the PEG600 of 2000ppm, be 53%, water flux is 131L/ (m
2h).
Embodiment 2
The method of preparing film identical with embodiment 1, then polysulfones counterdie is processed to 2min with 2% glutaraldehyde water solution, dry in the shade, then by polyvinyl alcohol mass fraction, be 2% to be 0.01% with PAMC mass fraction mixed solution is coated in 1.5min on the film that pretreatment is good, the composite membrane of gained is through 90 ℃ of processing 2h, and wherein the degree of hydrolysis of polyvinyl alcohol is 86%.Under the condition that is 1MPa at operating pressure, prepared polyvinyl alcohol nanofiltration membrane to holding back of 2000ppm sodium sulphate, be 58%, water flux is 120L/ (m
2h).To holding back of 2000ppm sodium chloride, be 23%, water flux is 125L/ (m
2h).To holding back of 2000ppm Macrogol 600, be 61%, water flux is 128L/ (m
2h).
Embodiment 3
The method of preparing film identical with embodiment 1, then polysulfones counterdie is processed to 2min with 2% glutaraldehyde water solution, dry in the shade, then by polyvinyl alcohol mass fraction, be 3% to be 0.01% with PAMC mass fraction mixed solution is coated in 1.5min on the film that pretreatment is good, the composite membrane of gained is processed 2h through 90 ℃.Under the condition that is 1MPa at operating pressure, prepared polyvinyl alcohol nanofiltration membrane to holding back of 2000ppm sodium sulphate, be 63%, water flux is 115/ (m
2h).To holding back of 2000ppm sodium chloride, be 31%, water flux is 118L/ (m
2h).To holding back of 2000ppm Macrogol 600, be 65%, water flux is 118L/ (m
2h).
Embodiment 4
The method of preparing film identical with embodiment 1, then polysulfones counterdie is processed to 2min with 3% glutaraldehyde water solution, dry in the shade, then by polyvinyl alcohol mass fraction, be 4% to be 0.02% with PAMC mass fraction mixed solution is coated in 2min on the film that pretreatment is good, the composite membrane of gained is through 90 ℃ of processing 2h, and wherein the degree of hydrolysis of polyvinyl alcohol is 88%.Under the condition that is 1MPa at operating pressure, prepared polyvinyl alcohol nanofiltration membrane to holding back of 2000ppm sodium sulphate, be 25%, water flux is 135L/ (m
2h).To holding back of 2000ppm sodium chloride, be 11%, water flux is 138L/ (m
2h).To holding back of 2000ppm Macrogol 600, be 28%, water flux is 138L/ (m
2h).
Embodiment 5
The method of preparing film identical with embodiment 1, then polysulfones counterdie is processed to 2min with 4% glutaraldehyde water solution, dry in the shade, then by polyvinyl alcohol mass fraction, be 5% to be 0.03% with PAMC mass fraction mixed solution is coated in 2min on the film that pretreatment is good, the composite membrane of gained is processed 2h through 90 ℃.Under the condition that is 1MPa at operating pressure, prepared polyvinyl alcohol nanofiltration membrane to holding back of 2000ppm sodium sulphate, be 9%, water flux is 148L/ (m
2h).To holding back of 2000ppm sodium chloride, be 5%, water flux is 150L/ (m
2h), to holding back of 2000ppm Macrogol 600, be 11%, water flux is 147L/ (m
2h).
Embodiment 6
The method of preparing film identical with embodiment 1, then polysulfones counterdie is processed to 2min with 5% glutaraldehyde water solution, dry in the shade, then by polyvinyl alcohol mass fraction, be 4% to be 0.01% with PAMC mass fraction mixed solution is coated in 2min on the film that pretreatment is good, under the condition that is 1MPa at operating pressure, the Na of the prepared composite membrane of gained to 2000ppm
2sO
4rejection be 71%, water flux is 110L/ (m
2h), to the rejection of the NaCl of 2000ppm, be 23%, water flux is 125L/ (m
2h), to the rejection of the PEG600 of 2000ppm, be 75%, water flux is 107L/ (m
2h).
Claims (2)
1. a preparation method for PAMC polyvinyl alcohol nanofiltration membrane, is characterized in that comprising the following steps:
(1) preparation of casting solution
Preparation quality mark is the glutaraldehyde water solution of 1%-5%, stand-by; The mixed aqueous solution of preparing polyvinyl alcohol and PAMC, wherein the mass fraction of polyvinyl alcohol is 1%-5%, and the mass fraction of PAMC is 0.01%-0.03%, and deaeration is stand-by;
(2) preparation of PAMC polyvinyl alcohol nanofiltration membrane
Glutaraldehyde water solution pretreatment 2-4min by polysulfones counterdie with 1%-5%, dries in the shade, and then the mixed aqueous solution of polyvinyl alcohol and PAMC is coated in to 1-3min on the polysulfones counterdie that pretreatment is good; The molecular cut off of wherein said polysulfones counterdie is 2-3 ten thousand;
(3) composite membrane of gained is processed 1-4h through 90 ℃.
2. preparation method according to claim 1, is characterized in that the degree of hydrolysis of described polyvinyl alcohol is 86-89%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437143A (en) * | 2014-12-18 | 2015-03-25 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyvinyl alcohol-ammonium alcohol polyvinyl phosphate nanofiltration membrane |
| CN104474924A (en) * | 2014-12-18 | 2015-04-01 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyvinyl alcohol ultra-filtration membrane |
| 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 |
| 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 |
| CN107754619A (en) * | 2017-11-12 | 2018-03-06 | 韦韬 | A kind of preparation method of natural polyelectrolyte NF membrane |
| CN108126530A (en) * | 2017-12-22 | 2018-06-08 | 南京湶膜科技有限公司 | A kind of preparation method and reverse osmosis composite membrane of anti-pollution reverse-osmosis composite membrane |
| CN112755810A (en) * | 2020-12-18 | 2021-05-07 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437143A (en) * | 2014-12-18 | 2015-03-25 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyvinyl alcohol-ammonium alcohol polyvinyl phosphate nanofiltration membrane |
| CN104474924A (en) * | 2014-12-18 | 2015-04-01 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyvinyl alcohol ultra-filtration membrane |
| CN104474924B (en) * | 2014-12-18 | 2016-05-25 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of polyvinyl alcohol milipore filter |
| CN104437143B (en) * | 2014-12-18 | 2016-06-08 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of polyvinyl alcohol-ammonium alcohol polyvinyl phosphate NF membrane |
| 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 |
| 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 |
| 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 |
| CN107754619A (en) * | 2017-11-12 | 2018-03-06 | 韦韬 | A kind of preparation method of natural polyelectrolyte NF membrane |
| CN107754619B (en) * | 2017-11-12 | 2020-05-19 | 韦韬 | Preparation method of natural polyelectrolyte nanofiltration membrane |
| CN108126530A (en) * | 2017-12-22 | 2018-06-08 | 南京湶膜科技有限公司 | A kind of preparation method and reverse osmosis composite membrane of anti-pollution reverse-osmosis composite membrane |
| CN112755810A (en) * | 2020-12-18 | 2021-05-07 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
| CN112755810B (en) * | 2020-12-18 | 2023-05-12 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
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Application publication date: 20140122 |