CN103611430A - Production method for high-ion selectivity hollow fibrous nanofiltration membrane - Google Patents
Production method for high-ion selectivity hollow fibrous nanofiltration membrane Download PDFInfo
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- CN103611430A CN103611430A CN201310653021.9A CN201310653021A CN103611430A CN 103611430 A CN103611430 A CN 103611430A CN 201310653021 A CN201310653021 A CN 201310653021A CN 103611430 A CN103611430 A CN 103611430A
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- membrane
- nanofiltration membrane
- hollow fibrous
- etching
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Abstract
The invention discloses a production method for a high-ion selectivity hollow fibrous nanofiltration membrane. The method comprises the following steps of performing etching reaction on a polysulfone hollow fibrous nanofiltration membrane in a low-temperature air plasma to improve the hydrophilicity of the surface of a basement membrane, impregnating the hollow fibrous nanofiltration membrane in a 2-acrylamide-2-methylpropane sulfonic acid monomer solution for a certain time, taking out and drying the hollow fibrous nanofiltration membrane, carrying out irradiation grafting reaction on the hollow fibrous nanofiltration membrane in the low-temperature air plasma, and performing ultrasonic cleaning to obtain the hollow fibrous nanofiltration membrane. The production method has the advantages that the low-temperature air plasma is used for etching, so that difficult-to-graft 2-acrylamide-2-methylpropane sulfonic acid monomers can be grafted onto the surface of a hydrophobic polysulfone membrane; the prepared nanofiltration membrane is high in ion selectivity, and can be applied to the fields of water softening, drinking water purification, dyeing wastewater treatment, medicament purification and the like, required operation pressure is low, and the energy consumption is reduced.
Description
Technical field
The present invention relates to the technology of preparing of hollow fiber nanofiltration membrane, relate in particular to the modification technology of polysulfone hollow fibre milipore filter, be specially plasma etching-irradiation grafting two step plasma modification methods of polysulfone hollow fibre milipore filter.
Background technology
NF membrane aperture is in 1nm left and right, molecular cut off is generally between 200～1000Da, and because NF membrane often carries charged group, thereby it has filled up the blank between reverse osmosis membrane and milipore filter, it can see through the inorganic salts of being held back by reverse osmosis membrane, holds back the little molecular weight organic matter through milipore filter.The fields such as the concentrated and resource recovery of water correction, drink water purifying, wastewater treatment, medicine purifying have been widely used in recent years.
Hollow fiber nanofiltration membrane is a kind of superfine hollow film pipe, compares with the film of other form, and hollow-fibre membrane has the following advantages: (1) unit volume effective film surface area is high.Because doughnut diameter is little, can close-packed arrays in membrane module, so hollow fiber film assembly loading density is high, unit volume aquifer yield is large; (2) hollow-fibre membrane itself does not need backing material can tolerate very high pressure, has saved backing material, makes manufacture simplification, and expense reduces; (3) assembly is easy to leak detection and is repaired by the method for air-blowing, and Flat Membrane and rolled film are difficult for leak detection.
Interfacial polymerization be preparation NF membrane most widely used be also effective method, the method is the ultra-thin top layer that compound one deck has nanoscale aperture on micropore basal membrane, but this kind of method is applied in to prepare and on hollow fiber nanofiltration membrane, has some drawbacks, as restricted at doughnut basement membrane internal layer compound tense coating process, outer compound tense is because surface tension or the higher solution viscosity on film surface cause easily boning between film silk, reunite, not only affect membrane area, and make film surface produce more defect, in addition in assembling and use procedure, due to the friction between film silk, easily cause the breakage of functional layer, affect the normal separation function of film.Therefore, the main successful Application of interfacial polymerization is in the dull and stereotyped NF membrane of preparation at present, and the research of hollow fiber nanofiltration membrane is also in laboratory stage.
Irradiation grafting method is mainly by various radiation sources, as ultraviolet light, plasma, electron beam, gamma-rays etc., base material is carried out to irradiation, makes material surface produce reactivity point, causes the function monomer that contains unsaturated double-bond and carries out glycerol polymerization.Adopt irradiation grafting method that functional layer is received to hollow-fibre membrane surface by chemical bond-linking, good stability not only, having solved interfacial polymerization functional layer easily comes off, the problem that film properties declines in During Process of Long-term Operation, and can control fenestra and film surface effective charge density by controlling length, density and the distribution of grafted chain, thereby control the separating property of NF membrane.Low temperature plasma to handled material without strict demand, can process complex-shaped material, the good uniformity that material surface is processed, only relates to several to hundreds of nanometer to the effect of material surface, when improving material surface performance, do not affect the bulk properties of material.The Li Ji of Tsing-Hua University determines seminar take polyacrylonitrile flat plate ultrafiltration membrane as matrix, by low temperature Ar plasma radiation, cause graft acrylic acid and styrene respectively and prepare hydrophily and hydrophobicity NF membrane [Journal of Membrane Science, 2004,232 (1-2): 1-8; Journal ofMembrane Science, 2005,251 (1-2): 239-245].But yet there are no so far the research that plasma etching-irradiation grafting two step plasma methods are prepared hollow fiber nanofiltration membrane.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to propose a kind of manufacture method of reacting controlled hollow fiber nanofiltration membrane, prepared hollow fiber nanofiltration membrane has high ion selectivity feature.
The technical scheme that the present invention solves described NF membrane manufacture method technical problem is to design a kind of method of low temperature atomsphere plasma etching-irradiation grafting.It is characterized in that comprising the following steps:
1, in the low temperature atomsphere plasma that doughnut basement membrane is 20kPa～80kPa in vacuum, carry out irradiation etching reaction, irradiation time is 10s～300s, and power is 20W～80W.It is 6,000～20,000 polysulfone hollow fibre milipore filter that described basement membrane is specially molecular cut off.
2, it is 5min～30min in 3%～50% ethanol/water mixed solution that the basement membrane of the 1st step etching being crossed is immersed in monomer concentration, and described monomer is specially 2-acrylamide-2-methylpro panesulfonic acid, and the volume ratio of ethanol and water is specially 1/9～1/1.
3, the impregnated membranes that the 2nd step obtained is taken out, and to be placed in temperature be the dry 0.5h～4h of baking oven of 15 ℃～50 ℃.
4, the desciccator diaphragm the 3rd step being obtained is placed in low temperature atomsphere plasma and again carries out irradiation grafting reaction, and vacuum is 20kPa～80kPa, and power is 20W～80W, and the grafting time is 10s～300s.
5, the graft copolymer membrane the 4th step being obtained is removed unreacted monomer and homopolymers at ultrasonic cleaner ultrasonic cleaning 10s～120s, obtains the described selective hollow fiber nanofiltration membrane of macroion.
The invention has the advantages that:
1, hollow fiber ultrafiltration membrane is by low temperature atomsphere plasma etching, improve the hydrophily of membrane surface, make the monomer 2-acrylamide-2-methylpro panesulfonic acid uniform fold that carries strong acid functional group in membrane surface, finally realized difficult grafted monomers 2-acrylamide-2-methylpro panesulfonic acid in the grafting on hydrophobic PS membrane surface.
2, the hollow fiber nanofiltration membrane of preparation has the performance of low pressure nanofiltration, has high ion selectivity, under 0.4MPa operating pressure, to NaCl/Na simultaneously
2sO
4the permeation flux of mixed solution is 13Lm
-2h
-1～25Lm
-2h
-1, SO
4 2-rejection at 70%～94%, Cl
-rejection 5%～20%, and SO
4 2-rejection be subject to hardly the impact of two kinds of salt ratios of feed liquid.
The specific embodiment
Introduce specific embodiments of the invention below, but the present invention is not subject to the restriction of embodiment.
Embodiment 1.
By molecular cut off, be 20, it is 40kPa that the polysulfone hollow fibre milipore filter of 000Da is placed in vacuum, power is to carry out etching reaction in the low temperature atomsphere plasma of 40W, irradiation time is 20s, after reaction finishes, etching film is immersed in to 10min in the ethanol/water mixed solution that 2-acrylamide-2-methylpro panesulfonic acid concentration is 5%, ethanol/water=1/4 wherein, after taking-up, in temperature, be dry 3h in the baking oven of 20 ℃, being placed on vacuum is 40kPa again, power is to carry out graft reaction in the low temperature atomsphere plasma of 40W, the grafting time is 60s, after irradiation finishes, graft copolymer membrane is cleaned to 30s with ultrasonic cleaner and remove unreacted monomer and homopolymers, obtain hollow fiber nanofiltration membrane.This NF membrane is at 25 ℃, under 0.4MPa, to NaCl/Na
2sO
4sO in mixed solution
4 2-rejection at 70%, Cl
-rejection 5%, permeation flux is 25Lm
-2h
-1, wherein in feed liquid, NaCl concentration is 6mM, Na
2sO
4concentration is 6mM.
Embodiment 2.
By molecular cut off, be 20, it is 40kPa that the polysulfone hollow fibre milipore filter of 000Da is placed in vacuum, power is to carry out etching reaction in the low temperature atomsphere plasma of 40W, irradiation time is 30s, after reaction finishes, etching film is immersed in to 10min in the ethanol/water mixed solution that 2-acrylamide-2-methylpro panesulfonic acid concentration is 5%, ethanol/water=1/4 wherein, after taking-up, in temperature, be dry 3h in the baking oven of 20 ℃, being placed on vacuum is 40kPa again, power is to carry out graft reaction in the low temperature atomsphere plasma of 40W, the grafting time is 60s, after irradiation finishes, graft copolymer membrane is cleaned to 30s with ultrasonic cleaner and remove unreacted monomer and homopolymers, obtain hollow fiber nanofiltration membrane.This NF membrane is at 25 ℃, under 0.4MPa, to NaCl/Na
2sO
4sO in mixed solution
4 2-rejection at 77%, Cl
-rejection 10%, permeation flux is 20Lm
-2h
-1, wherein in feed liquid, NaCl concentration is 6mM, Na
2sO
4concentration is 6mM.
Embodiment 3.
By molecular cut off, be 20, it is 40kPa that the polysulfone hollow fibre milipore filter of 000Da is placed in vacuum, power is to carry out etching reaction in the low temperature atomsphere plasma of 40W, irradiation time is 30s, after reaction finishes, etching film is immersed in to 10min in the ethanol/water mixed solution that 2-acrylamide-2-methylpro panesulfonic acid concentration is 5%, ethanol/water=1/4 wherein, after taking-up, in temperature, be dry 3h in the baking oven of 20 ℃, being placed on vacuum is 40kPa again, power is to carry out graft reaction in the low temperature atomsphere plasma of 40W, the grafting time is 80s, after irradiation finishes, graft copolymer membrane is cleaned to 30s with ultrasonic cleaner and remove unreacted monomer and homopolymers, obtain hollow fiber nanofiltration membrane.This NF membrane is at 25 ℃, under 0.4MPa, to NaCl/Na
2sO
4sO in mixed solution
4 2-rejection at 87%, Cl
-rejection 15%, permeation flux is 16Lm
-2h
-1, wherein in feed liquid, NaCl concentration is 6mM, Na
2sO
4concentration is 6mM.
Embodiment 4.
By molecular cut off, be 20, it is 40kPa that the polysulfone hollow fibre milipore filter of 000Da is placed in vacuum, power is to carry out etching reaction in the low temperature atomsphere plasma of 40W, irradiation time is 30s, after reaction finishes, etching film is immersed in to 10min in the ethanol/water mixed solution that 2-acrylamide-2-methylpro panesulfonic acid concentration is 10%, ethanol/water=1/4 wherein, after taking-up, in temperature, be dry 3h in the baking oven of 20 ℃, being placed on vacuum is 40kPa again, power is to carry out graft reaction in the low temperature atomsphere plasma of 40W, the grafting time is 80s, after irradiation finishes, graft copolymer membrane is cleaned to 30s with ultrasonic cleaner and remove unreacted monomer and homopolymers, obtain hollow fiber nanofiltration membrane.This NF membrane is at 25 ℃, under 0.4MPa, to NaCl/Na
2sO
4sO in mixed solution
4 2-rejection at 81%, Cl
-rejection 12%, permeation flux is 13Lm
-2h
-1, wherein in feed liquid, NaCl concentration is 6mM, Na
2sO
4concentration is 6mM.
Embodiment 5.
By molecular cut off, be 20, it is 40kPa that the polysulfone hollow fibre milipore filter of 000Da is placed in vacuum, power is to carry out etching reaction in the low temperature atomsphere plasma of 40W, irradiation time is 30s, after reaction finishes, etching film is immersed in to 10min in the ethanol/water mixed solution that 2-acrylamide-2-methylpro panesulfonic acid concentration is 5%, ethanol/water=1/4 wherein, after taking-up, in temperature, be dry 3h in the baking oven of 20 ℃, being placed on vacuum is 40kPa again, power is to carry out graft reaction in the low temperature atomsphere plasma of 40W, the grafting time is 80s, after irradiation finishes, graft copolymer membrane is cleaned to 30s with ultrasonic cleaner and remove unreacted monomer and homopolymers, obtain hollow fiber nanofiltration membrane.This NF membrane is at 25 ℃, under 0.4MPa, to NaCl/Na
2sO
4sO in mixed solution
4 2-rejection at 94%, Cl
-rejection 17%, permeation flux is 18Lm
-2h
-1, wherein in feed liquid, NaCl concentration is 1mM, Na
2sO
4concentration is 1mM.
Claims (1)
1. a manufacture method for the selective hollow fiber nanofiltration membrane of macroion, is characterized in that comprising following steps:
A) in the low temperature atomsphere plasma that doughnut basement membrane is 20kPa～80kPa in vacuum, carry out irradiation etching reaction, irradiation time is 10s～300s, and power is 20W～80W;
B) by step a) basement membrane that etching is crossed be immersed in 5min～30min in the ethanol/water mixed solution that 2-acrylamide-2-methylpro panesulfonic acid monomer concentration is 3%～50%, wherein the volume ratio of ethanol and water is 1/9～1/1;
C) by step b) in impregnated membranes take out, be placed in temperature and be the dry 0.5h～4h of baking oven of 15 ℃～50 ℃;
D) by step c) in desciccator diaphragm to be placed in vacuum be that the low temperature atomsphere plasma of 20kPa～80kPa carries out irradiation grafting reaction, the grafting time is 10s～300s, power is 20W～80W;
E) by steps d) in graft copolymer membrane ultrasonic cleaning 10s～120s in ultrasonic cleaner remove unreacted monomer and homopolymers, obtain the described selective hollow fiber nanofiltration membrane of macroion.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437105A (en) * | 2014-11-14 | 2015-03-25 | 宁波摩尔森膜环保科技有限公司 | Low-pressure hollow fiber nanofiltration membrane |
| CN106731867A (en) * | 2016-12-08 | 2017-05-31 | 厦门建霖工业有限公司 | The preparation method and preparation facilities of a kind of efficient anti-pollution reverse osmosis membrane |
| CN107847873A (en) * | 2015-06-26 | 2018-03-27 | 恩特格里斯公司 | It is grafted PS membrane |
| CN114917756A (en) * | 2022-05-23 | 2022-08-19 | 河北钢铁集团矿业有限公司 | High-flux nanofiltration membrane for mine wastewater recovery and preparation method thereof |
-
2013
- 2013-12-04 CN CN201310653021.9A patent/CN103611430A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437105A (en) * | 2014-11-14 | 2015-03-25 | 宁波摩尔森膜环保科技有限公司 | Low-pressure hollow fiber nanofiltration membrane |
| CN107847873A (en) * | 2015-06-26 | 2018-03-27 | 恩特格里斯公司 | It is grafted PS membrane |
| CN107847873B (en) * | 2015-06-26 | 2021-11-26 | 恩特格里斯公司 | Grafted polysulfone membranes |
| CN106731867A (en) * | 2016-12-08 | 2017-05-31 | 厦门建霖工业有限公司 | The preparation method and preparation facilities of a kind of efficient anti-pollution reverse osmosis membrane |
| CN114917756A (en) * | 2022-05-23 | 2022-08-19 | 河北钢铁集团矿业有限公司 | High-flux nanofiltration membrane for mine wastewater recovery and preparation method thereof |
| CN114917756B (en) * | 2022-05-23 | 2024-01-23 | 河北钢铁集团矿业有限公司 | High-flux nanofiltration membrane for mine wastewater recovery and preparation method thereof |
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Application publication date: 20140305 |