CN104998563A - Charged nanofiltration membrane preparing method - Google Patents
Charged nanofiltration membrane preparing method Download PDFInfo
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- CN104998563A CN104998563A CN201510484561.8A CN201510484561A CN104998563A CN 104998563 A CN104998563 A CN 104998563A CN 201510484561 A CN201510484561 A CN 201510484561A CN 104998563 A CN104998563 A CN 104998563A
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- nanofiltration membrane
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Abstract
The invention discloses a charged nanofiltration membrane preparing method. According to the method, a newly-prepared ultrafiltration membrane serves as a base membrane, base membrane polymer is photosensitive polymer with a main chain or a side chain provided with carbonyl or sulfonyl, the base membrane is soaked in a rigid airtight container containing a grafting monomer solution after being cleaned, vacuumizing is conducted on the rigid airtight container after the base membrane is soaked, and the intensity of pressure in the container is made to be negative pressure; the processed base membrane is taken out to be placed under an ultraviolet lamp to conduct stem grafting in an illumination mode, nitrogen is injected to protect the base membrane, then the base membrane is taken out to be cleaned with deionized water more than three times, and a charged nanofiltration membrane is obtained. According to the method, an interfacial polymerization mode is adopted, the positively-charged nanofiltration membrane is prepared on the base membrane, the prepared nanofiltration membrane is charged, high in stability, high in retention rate and capable of achieving industrial production on the basis of an existing composite film production line.
Description
Technical field
The invention belongs to preparation method's technical field of diffusion barrier, be specifically related to a kind of preparation method of charged nanofiltration membrane.
Background technology
NF membrane (NF) appears at the end of 20 century 70s the earliest, is development in recent years membrane separation technique rapidly.NF membrane is a kind of aperture is the diffusion barrier driven between reverse osmosis membrane and milipore filter, with pressure, start from the research of J.E.Cadotte to NS-300 film, obtain by the mode of interfacial polymerization the composite membrane that function separating layer and porous support layer optimize respectively, substantially increase the performance of NF membrane product.To the nineties, NF membrane obtains develop rapidly, in succession develops the NF membrane of a collection of separating property uniqueness, and realize commercialization for different applications.According to the difference of ultra-thin cortex, mainly can be divided into: aromatic polyamides class composite nanometer filtering film, polypiperazine-amide class composite nanometer filtering film, sulfonation poly-(ether) sulfone class composite nanometer filtering film, mixed type composite nanometer filtering film.NF membrane has the advantages such as operating pressure is low, permeation flux is large, and being therefore widely used in the separation of the less compound of the field relative molecular masses such as water treatment, food, pharmacy, dyestuff, chemical industry, is a kind of isolation technics with applications well prospect.
Major part NF membrane is charged membrane, mainly realizes by aperture sieving actoion and electrostatic repulsion, show as and have very high rejection to the salting liquid containing high valence ion the separation of material.At present, most of commodity NF membrane is all adopt the method for interfacial polymerization to prepare.Due to the restriction of polymerization, available monomeric species is less.Adopt and prepare charged nanofiltration membrane in the method for microfiltration membranes surface grafting polyelectrolyte monomer, the kind of NF membrane and performance are well expanded (as Chinese patent CN1586702 and CN1803265A); High chitosan quaternary ammonium salt etc. is then adopted to prepare and the NF membrane of positive electricity for material from Congjie etc.; Xu's copper literary composition etc., methylates and amination treatment through bromine (chlorine) for raw material with modification 2,6-dimethyl polyphenylene oxide (PPO), through the NF membrane of coating preparation lotus positive electricity; Tan Shao is early basement membrane with polyacrylonitrile film, and shitosan is modifier, a kind of NF membrane of lotus positive electricity that adopted ultra-violet radiation legal system standby; Zhang Haoqin etc. adopt polymine and pyromellitic trimethylsilyl chloride to obtain the NF membrane of lotus positive electricity by the mode of interfacial polymerization.These films to containing and the high valence ion salting liquid of central ion identical charges have good crown_interception.
In addition, phase inversion can also be adopted to prepare charged nanofiltration membrane.
Although these methods are used widely, also come with some shortcomings.The composition of method to monomer of such as interfacial polycondensation has strict requirement, and the technical difficulty of polymerisation is high, and product quality is wayward; And the NF membrane permeability prepared with phase transition method is often poor.And along with film is in extensive use that is biological and medicine and other fields, also propose requirements at the higher level to the hydrophily on film surface, new preparation method is subject to increasing attention.
Summary of the invention
The object of the invention is to the preparation method proposing a kind of charged nanofiltration membrane, on basement membrane, the NF membrane of lotus positive electricity is prepared by the mode of interfacial polymerization, NF membrane prepared by the method is electrically charged stable, and rejection is high, can realize the production of industrialization on existing composite membrane production line.
For reaching this object, the present invention by the following technical solutions:
A preparation method for charged nanofiltration membrane, comprises the following steps:
(1) with newly formed milipore filter for basement membrane, basement membrane polymer is main chain or side chain with the photosensitive polymers of carbonyl or sulfonyl, molecular cut off is 7000-9000, being soaked in after being cleaned by basement membrane and mass concentration is housed is in the rigidity closed container of the grafted monomers solution of 0.5-10%, soak 5-10min, afterwards described rigidity closed container is vacuumized, make pressure wherein be 0.5-0.8 large atmospheric pressure, keep 2-10min;
(2) the basement membrane taking-up after process in step (1) being placed in power is irradiate grafting under the uviol lamp of 400W; pour nitrogen protection; the distance of basement membrane and uviol lamp is 5-40cm; the time of irradiation grafting is 0.5-30min; take out with deionized water ultrasonic cleaning more than three times afterwards, obtain this charged nanofiltration membrane.
Preferably, described basement membrane polymer is polysulfones, polyether sulfone or polyether-ketone
Preferably, described grafted monomers is ALS, methacrylic acid-3-potassium sulfonate propyl ester, 2-acrylamide-2-methyl propane sulfonic, 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride or methacrylic acid-N, N-dimethylamino methyl esters.
The present invention has following beneficial effect: (1) selects molecular cut off to be the photosensitive polymers of 7000-9000, the structure of film can be made more homogeneous, stable, make NF membrane have stable high rejection; (2) soak in the process of grafting unit and adopt negative pressure, the gas in film inner duct is diffused out, and monomer can enter in milipore filter duct, completes graft reaction, improves carrying capacity; (3) grafting process adopts nitrogen protection, decrease oxygen and grafted monomers in grafting process or and basement membrane polymer between reaction, make film surface grafting more complete, more homogeneous.
Detailed description of the invention
Embodiment 1
(1) with newly formed polysulphone super-filter membrane for basement membrane, the molecular cut off of masking polysulfone polymer is 7000D, being soaked in after basement membrane deionized water repeatedly being rinsed and mass concentration is housed is in the rigidity closed container of the allyl sulphonic acid sodium solution of 0.5%, soak 10min, afterwards rigidity closed container is vacuumized, make pressure wherein reduce to 0.5 large atmospheric pressure, keep 2min, ALS is immersed in the duct of milipore filter fully;
(2) basement membrane after process in step (1) is taken out; being placed in power is irradiate grafting under the uviol lamp of 400W; be filled with nitrogen protection; the distance of basement membrane and uviol lamp is 5cm; the time of irradiation grafting is 0.5min; after grafting, take out and use deionized water ultrasonic cleaning more than three times, obtaining this charged nanofiltration membrane.After tested and calculate, this film is to MgCl
2rejection be 89.4%.
Embodiment 2
(1) with newly formed polysulphone super-filter membrane for basement membrane, the molecular cut off of masking polysulfone polymer is 8000D, being soaked in after basement membrane deionized water repeatedly being rinsed and mass concentration is housed is in the rigidity closed container of the allyl sulphonic acid sodium solution of 10%, soak 10min, afterwards rigidity closed container is vacuumized, make pressure wherein reduce to 0.8 large atmospheric pressure, keep 10min, ALS is immersed in the duct of milipore filter fully;
(2) basement membrane after process in step (1) is taken out; being placed in power is irradiate grafting under the uviol lamp of 400W; be filled with nitrogen protection; the distance of basement membrane and uviol lamp is 10cm; the time of irradiation grafting is 5min; after grafting, take out and use deionized water ultrasonic cleaning more than three times, obtaining this charged nanofiltration membrane.After tested and calculate, this film is to MgCl
2rejection be 90.5%.
Embodiment 3
(1) with newly formed polysulphone super-filter membrane for basement membrane, the molecular cut off of masking polysulfone polymer is 9000D, being soaked in after basement membrane deionized water repeatedly being rinsed and mass concentration is housed is in the rigidity closed container of the allyl sulphonic acid sodium solution of 5%, soak 8min, afterwards rigidity closed container is vacuumized, make pressure wherein reduce to 0.6 large atmospheric pressure, keep 8min, ALS is immersed in the duct of milipore filter fully;
(2) basement membrane after process in step (1) is taken out; being placed in power is irradiate grafting under the uviol lamp of 400W; be filled with nitrogen protection; the distance of basement membrane and uviol lamp is 10cm; the time of irradiation grafting is 10min; after grafting, take out and use deionized water ultrasonic cleaning more than three times, obtaining this charged nanofiltration membrane.After tested and calculate, this film is to MgCl
2rejection be 91.2%.
Embodiment 4
(1) with newly formed poly (ether-sulfone) ultrafiltration membrane for basement membrane, the molecular cut off of masking polysulfone polymer is 7000D, being soaked in after basement membrane deionized water repeatedly being rinsed and mass concentration is housed is in the rigidity closed container of methacrylic acid-3-potassium sulfonate propyl ester solution of 2%, soak 5min, afterwards rigidity closed container is vacuumized, make pressure wherein reduce to 0.6 large atmospheric pressure, keep 10min, methacrylic acid-3-potassium sulfonate propyl ester is immersed in the duct of milipore filter fully;
(2) basement membrane after process in step (1) is taken out; being placed in power is irradiate grafting under the uviol lamp of 400W; be filled with nitrogen protection; the distance of basement membrane and uviol lamp is 20cm; the time of irradiation grafting is 5min; after grafting, take out and use deionized water ultrasonic cleaning more than three times, obtaining this charged nanofiltration membrane.After tested and calculate, this film is to MgCl
2rejection be 92.4%.
Embodiment 5
(1) with newly formed poly (ether-sulfone) ultrafiltration membrane for basement membrane, the molecular cut off of masking polysulfone polymer is 8000D, being soaked in after basement membrane deionized water repeatedly being rinsed and mass concentration is housed is in the rigidity closed container of methacrylic acid-3-potassium sulfonate propyl ester solution of 4%, soak 5min, afterwards rigidity closed container is vacuumized, make pressure wherein reduce to 0.8 large atmospheric pressure, keep 5min, methacrylic acid-3-potassium sulfonate propyl ester is immersed in the duct of milipore filter fully;
(2) basement membrane after process in step (1) is taken out; being placed in power is irradiate grafting under the uviol lamp of 400W; be filled with nitrogen protection; the distance of basement membrane and uviol lamp is 30cm; the time of irradiation grafting is 20min; after grafting, take out and use deionized water ultrasonic cleaning more than three times, obtaining this charged nanofiltration membrane.After tested and calculate, this film is to MgCl
2rejection be 89.7%.
Embodiment 6
(1) with newly formed polyether-ketone milipore filter for basement membrane, the molecular cut off of masking polysulfone polymer is 7000D, being soaked in after basement membrane deionized water repeatedly being rinsed and mass concentration is housed is in the rigidity closed container of 2-acrylamide-2-methyl propane sulfonic solution of 8%, soak 10min, afterwards rigidity closed container is vacuumized, make pressure wherein reduce to 0.5 large atmospheric pressure, keep 10min, 2-acrylamide-2-methyl propane sulfonic is immersed in the duct of milipore filter fully;
(2) basement membrane after process in step (1) is taken out; being placed in power is irradiate grafting under the uviol lamp of 400W; be filled with nitrogen protection; the distance of basement membrane and uviol lamp is 10cm; the time of irradiation grafting is 10min; after grafting, take out and use deionized water ultrasonic cleaning more than three times, obtaining this charged nanofiltration membrane.After tested and calculate, this film is to MgCl
2rejection be 88.3%.
Embodiment 7
(1) with newly formed polyether-ketone milipore filter for basement membrane, the molecular cut off of masking polysulfone polymer is 9000D, be soaked in after basement membrane deionized water is rinsed repeatedly and the methacrylic acid-N that mass concentration is 10% is housed, in the rigidity closed container of N-dimethylamino methyl ester solution, soak 5min, afterwards rigidity closed container is vacuumized, pressure is wherein made to reduce to 0.6 large atmospheric pressure, keep 5min, make methacrylic acid-N, N-dimethylamino methyl esters immerses in the duct of milipore filter fully;
(2) basement membrane after process in step (1) is taken out; being placed in power is irradiate grafting under the uviol lamp of 400W; be filled with nitrogen protection; the distance of basement membrane and uviol lamp is 5cm; the time of irradiation grafting is 20min; after grafting, take out and use deionized water ultrasonic cleaning more than three times, obtaining this charged nanofiltration membrane.After tested and calculate, this film is to MgCl
2rejection be 90.6%.
Above are only specific embodiments of the invention, but design concept of the present invention is not limited thereto, all changes utilizing this design the present invention to be carried out to unsubstantiality, all should belong to the scope of protection of the invention.
Claims (3)
1. a preparation method for charged nanofiltration membrane, is characterized in that:
(1) with newly formed milipore filter for basement membrane, basement membrane polymer is main chain or side chain with the photosensitive polymers of carbonyl or sulfonyl, molecular cut off is 7000-9000, being soaked in after being cleaned by basement membrane and mass concentration is housed is in the rigidity closed container of the grafted monomers solution of 0.5-10%, soak 5-10min, afterwards described rigidity closed container is vacuumized, make pressure wherein be 0.5-0.8 large atmospheric pressure, keep 2-10min;
(2) the basement membrane taking-up after process in step (1) being placed in power is irradiate grafting under the uviol lamp of 400W; pour nitrogen protection; the distance of basement membrane and uviol lamp is 5-40cm; the time of irradiation grafting is 0.5-30min; take out with deionized water ultrasonic cleaning more than three times afterwards, obtain this charged nanofiltration membrane.
2. the preparation method of a kind of charged nanofiltration membrane as claimed in claim 1, is characterized in that: described basement membrane polymer is polysulfones, polyether sulfone or polyether-ketone.
3. the preparation method of a kind of charged nanofiltration membrane as claimed in claim 1, it is characterized in that: grafted monomers is ALS, methacrylic acid-3-potassium sulfonate propyl ester, 2-acrylamide-2-methyl propane sulfonic, 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride or methacrylic acid-N, N-dimethylamino methyl esters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697833A (en) * | 2019-10-09 | 2020-01-17 | 宁波泰意德过滤技术有限公司 | Nanofiltration membrane for heavy metal treatment and preparation method thereof |
| CN117654272A (en) * | 2024-02-01 | 2024-03-08 | 蓝星（杭州）膜工业有限公司 | Positively charged nanofiltration membrane and preparation method and application thereof |
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|---|---|---|---|---|
| CN1803265A (en) * | 2005-12-15 | 2006-07-19 | 复旦大学 | Method for preparing nanometer filter membrane using irradiating surface and copolymerized grafting technology |
| CN102151502A (en) * | 2010-02-11 | 2011-08-17 | 厦门大学 | Imidazole onium salt anion-exchange membrane and preparation method thereof |
| CN103071395A (en) * | 2013-02-01 | 2013-05-01 | 北京碧水源膜科技有限公司 | Dynamic preparation method of ultra-low pressure charge nanometer filtration membrane |
| CN104307391A (en) * | 2014-11-10 | 2015-01-28 | 华玉叶 | Preparation method of amphoteric charged nanofiltration membrane |
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2015
- 2015-08-07 CN CN201510484561.8A patent/CN104998563A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803265A (en) * | 2005-12-15 | 2006-07-19 | 复旦大学 | Method for preparing nanometer filter membrane using irradiating surface and copolymerized grafting technology |
| CN102151502A (en) * | 2010-02-11 | 2011-08-17 | 厦门大学 | Imidazole onium salt anion-exchange membrane and preparation method thereof |
| CN103071395A (en) * | 2013-02-01 | 2013-05-01 | 北京碧水源膜科技有限公司 | Dynamic preparation method of ultra-low pressure charge nanometer filtration membrane |
| CN104307391A (en) * | 2014-11-10 | 2015-01-28 | 华玉叶 | Preparation method of amphoteric charged nanofiltration membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697833A (en) * | 2019-10-09 | 2020-01-17 | 宁波泰意德过滤技术有限公司 | Nanofiltration membrane for heavy metal treatment and preparation method thereof |
| CN117654272A (en) * | 2024-02-01 | 2024-03-08 | 蓝星（杭州）膜工业有限公司 | Positively charged nanofiltration membrane and preparation method and application thereof |
| CN117654272B (en) * | 2024-02-01 | 2024-04-23 | 蓝星（杭州）膜工业有限公司 | Positively charged nanofiltration membrane and preparation method and application thereof |
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