CN102614789B - Nanofiltration separation membrane and preparation method thereof - Google Patents
Nanofiltration separation membrane and preparation method thereof Download PDFInfo
- Publication number
- CN102614789B CN102614789B CN2012100997641A CN201210099764A CN102614789B CN 102614789 B CN102614789 B CN 102614789B CN 2012100997641 A CN2012100997641 A CN 2012100997641A CN 201210099764 A CN201210099764 A CN 201210099764A CN 102614789 B CN102614789 B CN 102614789B
- Authority
- CN
- China
- Prior art keywords
- membrane
- dopa
- basement membrane
- solution
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a nanofiltration separation membrane which is prepared by dopa and/or dopamine through stem grafting and crosslinking after being stably auto-polymerized on the surface of a basement membrane. A poly-dopa or poly-dopamine composite layer which can be firmly combined with the basement membrane is obtained based on the principle of biological adhesion, and the composite layer is directly reacted with amino or sulfydryl in a long-chain molecule for crosslinking so as to prepare a series of nanofiltration separation membranes with different surface roughnesses, modified layer thicknesses, membrane pore diameters and hydrophilias. The nanofiltration separation membrane has the following advantages: (1) the composite strength between the composite layer and the basement membrane is large; (2) the seawater erosion resistant and hydrolytic resistance performances are strong so that the service life of the membrane is greatly prolonged; (3) the surface is smooth and uniform; (4) the surface hydrophilia is strong so that the permeability performance of the membrane can be improved; (5) the antibiosis is strong so that the pollution of the microbial membrane can be restrained; (6) the water flux is large and the separation efficiency of divalent ions is high; and (7) the process is simple, the condition is mild, and the realization is easy.
Description
Technical field
The invention belongs to and prepare the diffusion barrier field of compound material, be specifically related to a kind of nanofiltration separation membrane and preparation method thereof, namely under grafting and crosslinked condition, take DOPA and/or dopamine auto polymerization coating nanofiltration separation membrane and the preparation method as composite bed.
Background technology
NF membrane has nanoscale fenestra and special charge, with its uniqueness, efficient divalent ion (Ca
2+, Mg
2+, SO4
2-Deng) hold back characteristic, make take that its nanofiltration as core is softening at seawater, wastewater treatment and feed liquid is concentrated etc. that field is subject to extensive concern.For seawater desalination system, because nanofiltration has effectively been removed divalent ion, the desalting plant fouling is alleviated, vapo(u)rizing temperature and heat transfer coefficient and the water rate of recovery all significantly improve; The counter-infiltration system not only rate of recovery can bring up to 60%, and operating pressure decline, obvious energy conservation.Yet, expose in actual use some problems and restricted further developing of nanofiltration.This wherein, because film pollutes and film is deteriorated the NF membrane performance is significantly reduced be one of the most scabrous problem.
At present, commodity NF membrane both domestic and external, its functional material is the same with reverse osmosis membrane, is mainly aromatic polyamides class and cellulose acetate class.Polyamide has high flux and high selectivity, but resistance to oxidation not; Cellulose derivative easily is degraded by microorganisms, and the NF membrane of above-mentioned material directly applies in the various seawer system of algae, microorganism and organism kinds, and its stability and resistance tocrocking need to improve.The PA membrane NF membrane that China produces at present, though tentatively reach the commercial Application level, as the monomer of polyamide of major function material, still rely on import.Therefore, develop the nanofiltration diffusion barrier of a class for seawer system, have simultaneously lasting high score from performance and high antifouling property, the further application in and even other water source fields softening at seawater for development membrane science technology, have important theory significance and actual application value.
Summary of the invention
The object of the present invention is to provide a kind of nanofiltration separation membrane and preparation method thereof, namely based on nanofiltration separation membrane of DOPA/dopamine auto polymerization composite bed and preparation method thereof, on the basis that guarantees excellent separating property, strengthened combined strength bination between coating and basement membrane, diffusion barrier high anti-hydrolysis performance and antifouling property have been given, thereby extend the service life of diffusion barrier, also enlarged its range of application simultaneously.
Nanofiltration separation membrane of the present invention, be that DOPA and/or dopamine are stablized to auto polymerization in membrane surface, form poly-DOPA and/or poly-dopamine composite bed, then carry out grafting and crosslinked rear preparation.
Nanofiltration separation membrane of the present invention, its concrete preparation method is as follows:
1) basement membrane is alternately cleaned by ethanol and deionized water;
2) by step 1) basement membrane processed infiltrates in ethanol after, be placed in DOPA and/or dopamine solution, optionally add zinc powder, shake reaction; Then in ethanol and deionized water, alternately clean, obtain the basement membrane of surface with poly-DOPA or poly-dopamine composite bed;
3) by step 2) in the surface that obtains with basement membrane immersion treatment in the graft copolymer solution of 20～60 ℃ of poly-DOPA or poly-dopamine composite bed, obtain the basement membrane after grafting is processed;
4) by step 3) in the grafting that the obtains basement membrane after processing immerse in cross-linking agent solution and complete preparation after 4～24h.
Wherein, the described basement membrane of step (1) is organic basement membrane or the inorganic basement membranes such as aluminium oxide, titanium dioxide such as polyethylene, polypropylene, polyacrylonitrile, polysulfones, polyether sulfone; Described basement membrane can first carry out hydrolysis process, and the reagent of employing comprises sulfuric acid solution, hydrochloric acid solution, sodium hydroxide solution, liquor natrii hypochloritis or hydrogen peroxide solution.
Wherein, the solvent of the described DOPA of step (2) or dopamine solution is that seawater, deionized water, pH are that 6～10 Tris-hydrochloric acid buffer solution or ethanol mass fraction are 5～40% ethanol water; The addition of described zinc powder in DOPA and/or dopamine solution is 0～2%; Above-mentioned concussion reaction is to be that 100～200r/min, temperature are to carry out in the shaken cultivation case of 20～40 ℃ at rotating speed;
Wherein, the described graft copolymer solution of step (3) is the aqueous solution or the ethanolic solution that contains the long-chain molecule of amino or sulfydryl; The above-mentioned long-chain molecule that contains amino or sulfydryl comprises polymine, sulfhydrylation or amidized polyethylene glycol, shitosan, contains amino copper ion complex compound etc.
Wherein, the described crosslinking agent of step (4) is epoxychloropropane, glycerin triglycidyl ether or glutaraldehyde.
The present invention is based on the bioadhesive principle, obtain a kind of can with poly-DOPA or the poly-dopamine composite bed of basement membrane strong bonded, this composite bed directly and amino or sulfydryl in long-chain molecule react, and further process, thereby prepare the different nanofiltration diffusion barrier of a series of surface roughnesses, modified layer thickness, membrane aperture and hydrophily under crosslinked condition.Nanofiltration separation membrane involved in the present invention and preparation method's advantage are: (1) can not destroy the basement membrane body, and to basement membrane profile and not restriction of size; (2) prepared poly-DOPA or poly-dopamine composite bed, in film forming procedure, have special attachments (bonding) property, have greatly strengthened the combined strength bination between composite bed and basement membrane; (3) DOPA or dopamine have marine organisms secretion characteristic, and prepared poly-DOPA or seawater immersion erosion resisting and the hydrolytic resistance of poly-dopamine composite bed are strong, greatly extend the service life of diffusion barrier; (4) DOPA or dopamine auto polymerization degree are stablized controlled, prepared poly-DOPA or the smooth surface homogeneous of poly-dopamine composite bed; (5) surface hydrophilicity of prepared poly-DOPA or poly-dopamine composite bed is strong, can improve the film water permeability; (6) antibiosis of prepared poly-DOPA or poly-dopamine composite bed is strong, can suppress the film that the microorganism such as algae causes and pollute; (7) by grafting and crosslinked operation, give prepared poly-DOPA or poly-dopamine composite bed with the NF membrane characteristics, develop the high-performance nanofiltration separation membrane that is applicable to softening process, also enlarged its range of application simultaneously.
The accompanying drawing explanation
Fig. 1: DOPA is at membrane surface auto polymerization schematic diagram.
Fig. 2: the infrared spectrum of poly-DOPA composite bed.
Fig. 3: the infrared spectrum that adopts the poly-DOPA composite bed of polymine grafting.
The specific embodiment
The applicant finds in long-term research, the surface that poly-DOPA or poly-dopamine polymer is invested to inorganic or organic basement membrane can obtain the nanofiltration separation membrane with good nature, thereby has facilitated the present invention.Poly-DOPA or poly-dopamine polymer are by little molecule DOPA (left-handed-3, the 4-dihydroxyphenylalanine, L-DOPA) or the catechol derivatives-dopamine (3 of DOPA, 4-dihydroxy phenylpropyl alcohol ammonia, Dopamine) spontaneous polymerization forms under specific aqueous conditions, the present invention adopts original creation " be hydrolyzed-stablize autohemagglutination-grafting-crosslinked " filming technology, strengthen DOPA or dopamine auto polymerization stability, and give poly-DOPA or poly-dopamine coating surface nanofiltration characteristic and anti pollution property, thereby prepare the nanofiltration diffusion barrier that is applicable to multi-component complex feed liquid system.
The performance test methods of nanofiltration separation membrane of the present invention is as follows:
Preparation MgSO
4With NaCl mixed solution (concentration is 2000mg/L), under operating pressure 1.0MPa condition, adopt nanofiltration performance evaluation instrument to carry out the membrane filtration experiment, estimate the separating property of this series NF membrane, comprise water flux, divalent ion rejection and hold back the selection coefficient, computing formula is as follows:
J＝Q/A.t
In formula, J is water flux; Q is for seeing through the volume of liquid; A is the effective film area; T is filtration time.
In formula, R is rejection; C
FiConcentration for i ion in material liquid; C
PiFor seeing through the concentration of i ion in liquid.
r＝R
Mg/R
Na
In formula, r is for holding back the selection coefficient; R
MgAnd R
NaBe respectively Mg
2+And Na
+Rejection.
Using Seawater of Jiaozhou Bay as material liquid, adopt nanofiltration performance evaluation instrument to carry out the membrane filtration experiment, estimate separating property and the antifouling property of this series NF membrane.Wherein, the evaluation of separating property is referring to above computing formula.Antifouling property is estimated by pollution rate, i.e. the water flux attenuation rate of NF membrane longer-term (as 8h) operation, and pollution rate is less, and antifouling property is better.The computing formula of pollution rate is as follows:
AF＝1-J
0/J
E
In formula, AF is pollution rate; J
0For the NF membrane initial water flux in the filtering sea process; J
EWater flux during for the end of the NF membrane in the filtering sea process.
The antibiosis performance can characterize antifouling property to a certain extent.Adopt Escherichia coli to be the test bacterial classification, NF membrane and basement membrane are placed in respectively to cultured Escherichia coli nutrient solution, and (concentration is approximately 3 * 10
5Cells/ml), under 37 ℃ of constant temperature, cultivate 24h; After membrane sample is taken out, rinse and be diluted to certain multiple with the appropriate amount of fluid culture medium, be inoculated on solid medium and cultivate 24h under 37 ℃, count plate.The bacteriostasis rate computing formula is as follows:
T＝1-C/B
In formula: T is bacteriostasis rate; B and C are respectively the clump count of basement membrane sample and NF membrane sample.
Below in conjunction with specific embodiment, further illustrate the present invention.
Embodiment 1
After the polyacrylonitrile basement membrane is alternately shaken to cleaning by ethanol and deionized water, fully infiltrate in ethanol; DOPA is dissolved in deionized water, and configuration concentration is the DOPA solution of 2.0mg/L; Basement membrane is soaked in DOPA solution, is that 100r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; To in temperature is the polymine of 50 ℃, soak 3h with the basement membrane of poly-DOPA composite bed, concussion is cleaned in deionized water; Then crosslinked 6h in 0.5% glutaraldehyde solution that the diffusion barrier immersion obtained more than inciting somebody to action is 60 ℃; Rinsed with deionized water, make nanofiltration separation membrane.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 30L/m
2H, the magnesium ion rejection is 72%, and the sodium ion rejection is 25%, and the selective retention coefficient is 2.9; For former seawater, water flux is 26L/m
2H, the magnesium ion rejection is 64%, and the sodium ion rejection is 12%, and the selective retention coefficient is 7.1; Bacteriostasis rate is 30%.
Embodiment 2
After the polyacrylonitrile basement membrane is alternately shaken to cleaning by ethanol and deionized water, fully infiltrate in ethanol; It is that in 8.0 Tris-hydrochloric acid buffer solution, configuration concentration is the DOPA solution of 1.0mg/L that DOPA is dissolved in pH; Basement membrane is soaked in DOPA solution, is that 100r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; To in temperature is the polymine of 50 ℃, soak 3h with the basement membrane of poly-DOPA composite bed, concussion is cleaned in deionized water; Then crosslinked 6h in 0.5% glutaraldehyde solution that the diffusion barrier immersion obtained more than inciting somebody to action is 60 ℃; Rinsed with deionized water, make nanofiltration separation membrane.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 35L/m
2H, the magnesium ion rejection is 72%, and the sodium ion rejection is 19%, and the selective retention coefficient is 3.8; For former seawater, water flux is 26L/m
2H, the magnesium ion rejection is 70%, and the sodium ion rejection is 15%, and the selective retention coefficient is 4.7; Bacteriostasis rate is 37%.
Embodiment 3
The polyacrylonitrile basement membrane after static immersing 4h, after by ethanol and deionized water, alternately shaking cleaning, is fully infiltrated in ethanol in the 0.5%NaOH aqueous solution; It is that in 8.0 Tris-hydrochloric acid buffer solution, configuration concentration is the DOPA solution of 2.0mg/L that DOPA is dissolved in pH; Basement membrane being soaked in DOPA solution, adding the 0.2g zinc powder, is that 100r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; To in temperature is the polymine of 50 ℃, soak 6h with the basement membrane of poly-DOPA composite bed, concussion is cleaned in deionized water; Then crosslinked 12h in 1.0% glutaraldehyde solution that the diffusion barrier immersion obtained more than inciting somebody to action is 60 ℃; Rinsed with deionized water, make nanofiltration separation membrane.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 24L/m
2H, the magnesium ion rejection is 85%, and the sodium ion rejection is 20%, and the selective retention coefficient is 4.3; For former seawater, water flux is 18L/m
2H, the magnesium ion rejection is 82%, and the sodium ion rejection is 18%, and the selective retention coefficient is 4.6; Bacteriostasis rate is 42%.
Embodiment 4
The polyacrylonitrile basement membrane after static immersing 4h, after by ethanol and deionized water, alternately shaking cleaning, is fully infiltrated in ethanol in the 0.5%NaOH aqueous solution; It is in 20% ethanol-water solution that DOPA is dissolved in the ethanol mass fraction, and configuration concentration is the DOPA solution of 2.0mg/L; Basement membrane being soaked in DOPA solution, adding the 0.3g zinc powder, is that 100r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; To in temperature is the polymine of 50 ℃, soak 6h with the basement membrane of poly-DOPA composite bed, concussion is cleaned in deionized water; Then crosslinked 24h in 1.0% glutaraldehyde solution that the diffusion barrier immersion obtained more than inciting somebody to action is 60 ℃; Rinsed with deionized water, make nanofiltration separation membrane.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 27L/m
2H, the magnesium ion rejection is 83%, and the sodium ion rejection is 13%, and the selective retention coefficient is 6.4; For former seawater, water flux is 18L/m
2H, the magnesium ion rejection is 81%, and the sodium ion rejection is 14%, and the selective retention coefficient is 5.8; Bacteriostasis rate is 37%.
Embodiment 5
By the polyacrylonitrile basement membrane, be in 8.5 the 0.5%NaClO/NaOH aqueous solution after static immersing 4h at pH, after alternately concussion is cleaned by ethanol and deionized water, fully infiltrate in ethanol; DOPA is dissolved in actual Seawater of Jiaozhou Bay, and configuration concentration is the DOPA solution of 2.0mg/L; Basement membrane being soaked in DOPA solution, adding the 0.3g zinc powder, is that 180r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; To in temperature is the polymine of 50 ℃, soak 6h with the basement membrane of poly-DOPA composite bed, concussion is cleaned in deionized water; Then crosslinked 12h in 1.0% glutaraldehyde solution that the diffusion barrier immersion obtained more than inciting somebody to action is 60 ℃; Rinsed with deionized water, make nanofiltration separation membrane.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 28L/m
2H, the magnesium ion rejection is 91%, and the sodium ion rejection is 18%, and the selective retention coefficient is 5.1; For former seawater, water flux is 22L/m
2H, the magnesium ion rejection is 87%, and the sodium ion rejection is 19%, and the selective retention coefficient is 4.6; Bacteriostasis rate is 40%.
Embodiment 6
By the polyacrylonitrile basement membrane, be in 8.5 the 0.5%NaClO/NaOH aqueous solution after static immersing 4h at pH, after alternately concussion is cleaned by ethanol and deionized water, fully infiltrate in ethanol; DOPA is dissolved in actual Seawater of Jiaozhou Bay, and configuration concentration is the DOPA solution of 2.0mg/L; Basement membrane is soaked in DOPA solution, is that 180r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; To in temperature is the polymine of 30 ℃, soak 6h with the basement membrane of poly-DOPA composite bed, concussion is cleaned in deionized water; Then in glycerin triglycidyl ether/acetone (the mass fraction ratio is 0.5: 50) solution that the diffusion barrier immersion obtained more than inciting somebody to action is 60 ℃, and add HClO
4Regulating pH is 3, carries out crosslinked 12h; Rinsed with deionized water, make nanofiltration separation membrane.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 29L/m
2H, the magnesium ion rejection is 94%, and the sodium ion rejection is 24%, and the selective retention coefficient is 3.9; For former seawater, water flux is 23L/m
2H, the magnesium ion rejection is 90%, and the sodium ion rejection is 17%, and the selective retention coefficient is 5.3; Bacteriostasis rate is 43%.
Embodiment 7
By the polyacrylonitrile basement membrane, be in 8.5 the 0.5%NaClO/NaOH aqueous solution after static immersing 4h at pH, after alternately concussion is cleaned by ethanol and deionized water, fully infiltrate in ethanol; Dopamine is dissolved in actual Seawater of Jiaozhou Bay, and configuration concentration is the dopamine solution of 2.0mg/L; Basement membrane is soaked in dopamine solution, is that 180r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; To in temperature is the polymine of 50 ℃, soak 6h with the basement membrane of poly-dopamine composite bed, concussion is cleaned in deionized water; Then in glycerin triglycidyl ether/acetone (the mass fraction ratio is 1.0: 50) solution that the diffusion barrier immersion obtained more than inciting somebody to action is 60 ℃, and add HClO
4Regulating pH is 3, carries out crosslinked 12h; Rinsed with deionized water, make nanofiltration separation membrane.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 30L/m
2H, the magnesium ion rejection is 95%, and the sodium ion rejection is 20%, and the selective retention coefficient is 4.8; For former seawater, water flux is 25L/m
2H, the magnesium ion rejection is 89%, and the sodium ion rejection is 15%, and the selective retention coefficient is 5.9; Bacteriostasis rate is 38%.
Method of the present invention, carried out long-term optimization on grafting and crosslinked condition, select the better effects if of the product that condition of the present invention prepares.
Reference examples 1
After the polyacrylonitrile basement membrane is alternately shaken to cleaning by ethanol and deionized water, fully infiltrate in ethanol; DOPA is dissolved in deionized water, and configuration concentration is the DOPA solution of 2.0mg/L; Basement membrane is soaked in DOPA solution, is that 100r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean, obtain the diffusion barrier with a strata DOPA composite bed.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 40L/m
2H, the magnesium ion rejection is 0～1%, the sodium ion rejection is 0～1%; For former seawater, water flux is 32L/m
2H, the magnesium ion rejection is 0%, the sodium ion rejection is 0%; Bacteriostasis rate is 35%.
Reference examples 2
After the polyacrylonitrile basement membrane is alternately shaken to cleaning by ethanol and deionized water, fully infiltrate in ethanol; DOPA is dissolved in deionized water, and configuration concentration is the DOPA solution of 2.0mg/L; Basement membrane is soaked in DOPA solution, is that 100r/min, temperature are to shake 24h in the shaken cultivation case of 35 ℃ at rotating speed, then in ethanol and deionized water alternately concussion clean; Repeat above step and parameter, will be soaked in DOPA solution with the basement membrane of poly-DOPA composite bed for the second time; Then alternately concussion cleaning in ethanol and deionized water, obtain the diffusion barrier with two strata DOPA composite beds.
Measure this diffusion barrier performance, result is as follows.For MgSO
4With the NaCl mixed solution, water flux is 32L/m
2H, the magnesium ion rejection is 32%, the sodium ion rejection is 8～12%; For former seawater, water flux is 27L/m
2H, the magnesium ion rejection is 21～26%, the sodium ion rejection is 4%; Bacteriostasis rate is 40%.
Above result shows, if without grafting and the processing such as crosslinked, only carry out merely DOPA and/or dopamine coating (1 layer and 2 layers), with the present invention, compare through the prepared diffusion barrier of grafting and the processing such as crosslinked, the separating property of prepared diffusion barrier is poor, and the divalent ion rejection is below 30%.
Claims (9)
1. the preparation method of a nanofiltration separation membrane, is characterized in that, be by DOPA and/or dopamine auto polymerization in membrane surface, form poly-DOPA and/or poly-dopamine composite bed, then carry out grafting and crosslinked rear preparation; Include following step:
1) basement membrane is alternately cleaned by ethanol and deionized water;
2) basement membrane of step 1) being processed infiltrates in ethanol after, be placed in DOPA and/or dopamine solution, selectively add zinc powder, then shake reaction, then in ethanol and deionized water, alternately clean, obtain the basement membrane of surface with poly-DOPA or poly-dopamine composite bed;
3) by step 2) in the surface that obtains with basement membrane immersion treatment in the graft copolymer solution of 20～60 ℃ of poly-DOPA or poly-dopamine composite bed, obtain the basement membrane after grafting is processed;
4) basement membrane after the grafting processing obtained in step 3) is immersed in cross-linking agent solution and completes preparation after 4～24h.
Wherein, in step 3), graft copolymer solution is the aqueous solution or the ethanolic solution that contains the long-chain molecule of amino or sulfydryl; The above-mentioned long-chain molecule that contains amino or sulfydryl comprises polymine, sulfhydrylation or amidized polyethylene glycol, amidized shitosan or contains amino copper ion complex compound.
2. preparation method as claimed in claim 1, is characterized in that the basement membrane in described step 1) has carried out hydrolysis process, and the reagent of employing is sulfuric acid solution, hydrochloric acid solution, sodium hydroxide solution, liquor natrii hypochloritis or hydrogen peroxide solution.
3. preparation method as claimed in claim 1 or 2, is characterized in that the basement membrane in described step 1) is organic basement membrane or inorganic basement membrane.
4. preparation method as claimed in claim 3, is characterized in that described organic basement membrane is polyethylene, polypropylene, polyacrylonitrile, polysulfones or polyether sulfone.
5. preparation method as claimed in claim 3, is characterized in that described inorganic basement membrane is aluminium oxide or titanium dioxide.
6. preparation method as claimed in claim 1, is characterized in that described step 2) in DOPA and/or the solvent of dopamine solution be that seawater, deionized water, pH are that 6～10 Tris-hydrochloric acid buffer solution or ethanol mass fraction are 5～40% ethanol water.
7. preparation method as claimed in claim 1, is characterized in that described step 2) in the addition of zinc powder in DOPA and/or dopamine solution be 0～2%.
8. preparation method as claimed in claim 1, is characterized in that the crosslinking agent in described step 4) is epoxychloropropane, glycerin triglycidyl ether or glutaraldehyde.
9. a nanofiltration separation membrane, is characterized in that, by method claimed in claim 1, prepared by described nanofiltration separation membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100997641A CN102614789B (en) | 2012-04-06 | 2012-04-06 | Nanofiltration separation membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100997641A CN102614789B (en) | 2012-04-06 | 2012-04-06 | Nanofiltration separation membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102614789A CN102614789A (en) | 2012-08-01 |
| CN102614789B true CN102614789B (en) | 2013-11-27 |
Family
ID=46555205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100997641A Active CN102614789B (en) | 2012-04-06 | 2012-04-06 | Nanofiltration separation membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102614789B (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102961893B (en) * | 2012-11-07 | 2014-11-26 | 清华大学 | Super-hydrophobic and super-oleophylic oil-water separating mesh membrane and preparation method thereof |
| CN103272499A (en) * | 2013-05-10 | 2013-09-04 | 天津大学 | Dopamine-polyethersulfone composite membrane and preparation method thereof |
| CN103316600B (en) * | 2013-05-14 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Method for fixing heparin on polylactic acid hemodialysis membrane surface |
| CN104248913B (en) * | 2013-06-28 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method of polyolefin hollow fiber ultrafiltration membrane hydrophilic modification |
| CN103464013B (en) * | 2013-07-25 | 2014-11-05 | 烟台绿水赋膜材料有限公司 | High-performance hybrid separation membrane and preparation method thereof |
| CN103463997B (en) * | 2013-09-30 | 2015-05-20 | 中国海洋大学 | Manufacturing method for composite membrane containing aquaporin |
| KR102080283B1 (en) * | 2013-10-04 | 2020-02-21 | 주식회사 엘지화학 | Surface-modified membrane and method of modifyng the membrane surface |
| CN104548969A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing anti-pollution polysulfone porous membrane by self-assembling immobilization of metal ions |
| CN104785121B (en) * | 2015-03-30 | 2017-03-08 | 天津大学 | Sodium alginate/poly-dopamine polyethyleneimine/polyacrylonitrile sandwich diaphragm and preparation and application |
| CN104923082B (en) * | 2015-05-27 | 2017-07-18 | 清华大学 | A kind of hydrophilic antibiotic milipore filter and preparation method thereof |
| CN105214579A (en) * | 2015-11-04 | 2016-01-06 | 上海洁晟环保科技有限公司 | Realize the processing method of micron or nanoscale porous material functionalization |
| CN105289336A (en) * | 2015-11-20 | 2016-02-03 | 哈尔滨工业大学 | Method for preparing nanofiltration membrane by collectively coating pyrocatechol and polyethyleneimine |
| CN105601933A (en) * | 2016-01-30 | 2016-05-25 | 青岛科技大学 | Preparation method of silicone rubber surface hydrophilic coating |
| CN105688691A (en) * | 2016-03-07 | 2016-06-22 | 东南大学 | Preparation method and application of anti-pollution polyethersulfone membrane |
| CN105854638A (en) * | 2016-04-14 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Permanently hydrophilic PTFE hollow fiber membrane and preparation method thereof |
| CN106110910A (en) * | 2016-06-22 | 2016-11-16 | 江苏索普（集团）有限公司 | A kind of infiltration vaporization separation film and preparation method thereof |
| CN106039998B (en) * | 2016-07-18 | 2019-02-05 | 浙江大学 | Load the photocatalysis composite nanometer filtering film and preparation method thereof of β-FeOOH nanocrystal |
| CN106000125B (en) * | 2016-07-19 | 2021-02-26 | 重庆理工大学 | Bionic preparation method of inorganic composite nanofiltration membrane |
| CN106750462B (en) * | 2016-12-19 | 2019-11-08 | 大连理工大学 | A kind of surface modifying method of dopamine and its derivative polymerization and crosslinking curing |
| CN106621856A (en) * | 2017-01-22 | 2017-05-10 | 河北工业大学 | Stable-structure high-performance graphene oxide nanofiltration composite membrane and preparation method thereof |
| CN106861455B (en) * | 2017-04-14 | 2019-08-09 | 北京工业大学 | A kind of metal hydroxides for organic solvent nanofiltration/ceramic pipe type composite membrane and preparation method |
| CN106975371A (en) * | 2017-04-14 | 2017-07-25 | 浙江大学 | A kind of composite nanometer filtering film of polyolefin micropore substrate based on hydrophilic modifying and preparation method thereof |
| CN107927528B (en) * | 2017-07-24 | 2021-04-30 | 中国科学院过程工程研究所 | Bionic membrane for removing aflatoxin and preparation method and treatment method thereof |
| CN107715708B (en) * | 2017-09-26 | 2020-12-22 | 河海大学 | Preparation method and regeneration method of renewable polyelectrolyte membrane for forward osmosis technology |
| CN109865438A (en) * | 2017-12-01 | 2019-06-11 | 俞小峰 | A kind of preparation method of antibacterial stable type nanofiltration membrane material |
| CN108211826A (en) * | 2018-02-13 | 2018-06-29 | 温州莲华环保科技有限公司 | A kind of forward osmosis membrane and preparation method thereof |
| CN109568668B (en) * | 2018-11-29 | 2020-08-11 | 中山大学 | Preparation method of polypropylene/polydopamine composite patch, composite patch and application |
| CN109550408A (en) * | 2019-01-11 | 2019-04-02 | 重庆理工大学 | A kind of preparation method of anti-protein-contamination ceramic composite membrane |
| CN110756055B (en) * | 2019-05-15 | 2021-02-19 | 北京化工大学 | Bipolar membrane and preparation method thereof |
| CN110124537B (en) * | 2019-06-18 | 2021-08-10 | 浙江海洋大学 | Preparation method of composite polysulfone membrane and application of composite polysulfone membrane in mariculture wastewater treatment |
| CN110665373A (en) * | 2019-06-30 | 2020-01-10 | 浙江工业大学 | Preparation method of PDA- (HACC-CN & Ag) -PDA nanofiltration membrane with anti-pollution and antibacterial properties |
| CN111437741B (en) * | 2020-03-24 | 2021-08-31 | 中山大学 | Mussel bionic auxiliary polyelectrolyte layer-by-layer self-assembled nanofiltration membrane and application thereof |
| CN111974231B (en) * | 2020-08-31 | 2022-01-28 | 启成（江苏）净化科技有限公司 | Preparation method of surface-modified anti-pollution nanofiltration membrane |
| CN113293055A (en) * | 2021-01-15 | 2021-08-24 | 云南森博混凝土外加剂有限公司 | Concrete water-based release agent and preparation method thereof |
| CN114432847A (en) * | 2022-03-15 | 2022-05-06 | 辽宁石油化工大学 | Gas deep dehumidification film and preparation method thereof |
| CN115337790B (en) * | 2022-07-15 | 2023-10-20 | 上海工程技术大学 | Preparation method of super-hydrophilic polyethersulfone separation membrane and separation membrane prepared by same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745327A (en) * | 2009-12-29 | 2010-06-23 | 浙江大学 | Method for fixing biological molecules on polymer microporous membrane surface |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586542C (en) * | 2008-05-21 | 2010-02-03 | 天津大学 | Hollow fiber compound film with ultra-thin active layer, preparation method and application thereof |
-
2012
- 2012-04-06 CN CN2012100997641A patent/CN102614789B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745327A (en) * | 2009-12-29 | 2010-06-23 | 浙江大学 | Method for fixing biological molecules on polymer microporous membrane surface |
Non-Patent Citations (2)
| Title |
|---|
| 多巴胺的自聚-附着行为与膜表面功能化;徐又一等;《膜科学与技术》;20110630;第31卷(第3期);第32-38页 * |
| 徐又一等.多巴胺的自聚-附着行为与膜表面功能化.《膜科学与技术》.2011,第31卷(第3期),第32-38页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102614789A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102614789B (en) | Nanofiltration separation membrane and preparation method thereof | |
| Suwaileh et al. | Forward osmosis membranes and processes: A comprehensive review of research trends and future outlook | |
| Goh et al. | Membrane technology: A versatile tool for saline wastewater treatment and resource recovery | |
| Bar-Zeev et al. | Impaired performance of pressure-retarded osmosis due to irreversible biofouling | |
| Honarparvar et al. | Frontiers of membrane desalination processes for brackish water treatment: A review | |
| Goh et al. | The water–energy nexus: solutions towards energy‐efficient desalination | |
| CN103223302B (en) | Preparation method of self-assembly covalent cross-linked sodium filter membrane | |
| AU2009231909B2 (en) | Environmentally friendly hybrid microbiological control technologies for cooling towers | |
| US20100140162A1 (en) | Osmosis membrane with improved flux rate and uses thereof | |
| CN104474920B (en) | A kind of flat cellulose acetate/nanometer titanium dioxide blending forward osmosis membrane | |
| CN103691328A (en) | Method for preparing contamination-resistant composite reverse osmosis membrane | |
| Kim et al. | Modification strategies of membranes with enhanced Anti-biofouling properties for wastewater Treatment: A review | |
| CN109433023A (en) | The graphene oxide nanofiltration membrane and the preparation method and application thereof of one type graphitic nitralloy carbon intercalation | |
| CN111921388B (en) | Borate intercalation modified graphene oxide composite nanofiltration membrane and preparation method thereof | |
| Ahn et al. | Preparation and applications of poly vinyl alcohol (PVA) modified cellulose acetate (CA) membranes for forward osmosis (FO) processes | |
| Yang et al. | Biofilm formation and biofouling development on different ultrafiltration membranes by natural anaerobes from an anaerobic membrane bioreactor | |
| CN107617342B (en) | Bimetal hydroxide ceramic membrane for seawater desalination and preparation method thereof | |
| Wu et al. | Piperazine-based functional materials as draw solutes for desalination via forward osmosis | |
| CN110898687A (en) | Preparation method of hydrophilic antibacterial PVDF (polyvinylidene fluoride) membrane | |
| Bóna et al. | Progress towards stable and high-performance polyelectrolyte multilayer nanofiltration membranes for future wastewater treatment applications | |
| CN104445761A (en) | Energy-saving seawater purification equipment | |
| CN106139922B (en) | Ultrahigh flux nanofiltration membrane and preparation method thereof | |
| CN103752174A (en) | Antibacterial hydrophilic hollow fiber assembly for water treatment | |
| Osman et al. | Membrane technology for energy saving: principles, techniques, applications, challenges, and prospects | |
| CN111298651B (en) | Biological pollution resistant composite reverse osmosis membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |