CN105169962A - Method for preparing nanofiltration membrane by adopting layer-by-layer self-assembly method - Google Patents
Method for preparing nanofiltration membrane by adopting layer-by-layer self-assembly method Download PDFInfo
- Publication number
- CN105169962A CN105169962A CN201510586136.XA CN201510586136A CN105169962A CN 105169962 A CN105169962 A CN 105169962A CN 201510586136 A CN201510586136 A CN 201510586136A CN 105169962 A CN105169962 A CN 105169962A
- Authority
- CN
- China
- Prior art keywords
- membrane
- polyacrylonitrile
- layer
- solution
- legal system
- 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.)
- Granted
Links
Abstract
The invention discloses a method for preparing a nanofiltration membrane by adopting a layer-by-layer self-assembly method, and relates to a preparation method of a nanofiltration membrane, aiming at solving the problems that a nanofiltration membrane prepared by adopting an existing method cannot have both good interception performance and high water flux. The method comprises the following steps: preparing a polyacrylonitrile solution, preparing a polyacrylonitrile basilar membrane, preparing a treated polyacrylonitrile basilar membrane, assembling a layer of polyethlenimine, assembling a layer of graphene oxide, and reassembling polyethlenimine and graphene oxide, thus obtaining the nanofiltration membrane. According to the method disclosed by the invention, a layer-by-layer self-assembly method is adopted, polyethlenimine and graphene oxide are adopted for modifying a PAN membrane, so that the hydrophilia and the pore size of the surface of the membrane are effectively adjusted; because the membrane is relatively thin, relatively large flux can be obtained, and the obtained nanofiltration membrane has good interception performance. The method can be applied to the fields of antibiotics separating, fruit juice concentrating and seawater desalting.
Description
Technical field
The present invention relates to a kind of preparation method of NF membrane.
Background technology
Because freshwater resources day is exhausted, desalination technology is just more and more paid attention to.Wherein membrane separation technique especially new membrane isolation technics be just subject to the extensive concern of scientists.
Nanofiltration starts from the middle and later periods eighties, is a kind of novel pressure-actuated process without phase transformation physical separation.The aperture of NF membrane is less than the aperture of milipore filter, is greater than the aperture of reverse osmosis membrane.The feature of NF membrane is its higher rejection to divalence and multivalent ion, and then relatively low to monovalention rejection, its molecular cut off is between 200-1000gmol
-1.Thus, the industrial circle such as a small amount of organic removal in the organic feed separation that the nanofiltration process desalination that is widely used in dyestuff isoreactivity material and concentrated, water softening, molecular weight are different and purifying, water.The subject matter of existing NF membrane research be cutoff performance excellent time, the water flux of the unit pressure of NF membrane is lower.
Summary of the invention
The present invention will solve the problem that NF membrane prepared by existing method can not have good cutoff performance and higher water flux simultaneously, provides a kind of LBL self-assembly legal system for the method for NF membrane.
A kind of LBL self-assembly legal system of the present invention, for the method for NF membrane, comprises the following steps:
One, solvent, pore former and polyacrylonitrile are mixed, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washing 3 ~ 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in sodium hydroxide solution, 20min ~ 60min is reacted at 20 DEG C ~ 50 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5 ~ 2h, be placed in hydrochloric acid solution again and soak 1 ~ 5h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 10 ~ 90min in polyethylenimine solution, put into deionized water after taking-up and soak 2 ~ 10min, obtain the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer;
Five, the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer is placed in graphene oxide solution, soaks 10 ~ 90min, put into deionized water after taking-up and soak 2 ~ 10min, obtain the NF membrane containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 0 ~ 7 time of step 4 and step 5, namely complete.
The present invention utilizes layer-by-layer, make polymine and graphene oxide modification PAN film, the pore size on its hydrophily and film surface is is effectively regulated and controled, and film is thinner, larger flux can be obtained, the NF membrane simultaneously obtained has good cutoff performance, be applicable to the separation of various dyestuff, desalinization etc., reduce energy consumption and purified water quality simultaneously, desalinate seawater, have great application prospect.
Detailed description of the invention
Detailed description of the invention one: a kind of LBL self-assembly legal system of present embodiment, for the method for NF membrane, comprises the following steps:
One, solvent, pore former and polyacrylonitrile are mixed, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washing 3 ~ 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in sodium hydroxide solution, 20min ~ 60min is reacted at 20 DEG C ~ 50 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5 ~ 2h, be placed in hydrochloric acid solution again and soak 1 ~ 5h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 10 ~ 90min in polyethylenimine solution, put into deionized water after taking-up and soak 2 ~ 10min, obtain the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer;
Five, the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer is placed in graphene oxide solution, soaks 10 ~ 90min, put into deionized water after taking-up and soak 2 ~ 10min, obtain the NF membrane containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 0 ~ 7 time of step 4 and step 5, namely complete.
Present embodiment utilizes layer-by-layer, make polymine and graphene oxide modification PAN film, the pore size on its hydrophily and film surface is is effectively regulated and controled, and film is thinner, larger flux can be obtained, the NF membrane simultaneously obtained has good cutoff performance, be applicable to the separation of various dyestuff, desalinization etc., reduce energy consumption and purified water quality simultaneously, desalinate seawater, have great application prospect.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: the solvent described in step one is 1-METHYLPYRROLIDONE.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two are polyethylene glycol or polyvinylpyrrolidone unlike the pore former described in step one.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: in step one, the mass ratio of polyacrylonitrile, pore former and solvent is (15 ~ 25): 1:(74 ~ 84).Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: the mass concentration of the sodium hydroxide solution described in step 3 is 5% ~ 20%.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: the concentration of the hydrochloric acid solution described in step 3 is 0.05mol/L ~ 0.5mol/L.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six unlike: the concentration of the polyethylenimine solution described in step 4 is 0.5 ~ 3g/L.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven unlike: immerse 30min in polyethylenimine solution in step 4, put into after taking-up deionized water soak 5min.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight unlike: the concentration of the graphene oxide solution described in step 5 is 0.05 ~ 0.5g/L.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine unlike: be placed in graphene oxide solution in step 5, soak 30min, put into after taking-up deionized water soak 5min.Other is identical with one of detailed description of the invention one to nine.
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1: the present embodiment LBL self-assembly legal system, for the method for NF membrane, comprises the following steps:
One, by 79g nitrogen methyl pyrrolidone and 1g polyethylene glycol, add in 20g polyacrylonitrile, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washs 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, 30min is reacted at 40 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5h, be placed in 0.1mol/L hydrochloric acid solution again and soak 3h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 30min in 1g/L polyethylenimine solution, put into deionized water after taking-up and soak 5min, obtain the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer;
Five, the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer is placed in 0.1g/L graphene oxide solution, soaks 30min, put into deionized water after taking-up and soak 5min, obtain the NF membrane containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 0 time of step 4 and step 5, namely complete.
Have large permeation flux and have the index that higher rejection is desirable NF membrane film simultaneously concurrently.
The mensuration of flux: get the NF membrane sample of certain area in nanofiltration testing arrangement, under room temperature and 0.5MPa (N2) with solvent by NF membrane compacting 45min, test the quality m by the methyl alcohol of film, ethanol, isopropyl alcohol, by calculating volume V.Treat before each test that solvent flux is being tested after roughly stable.Namely, under will ensureing the condition that certain pressure is constant, test certain hour t is through the solvent volume V of NF membrane.
The mensuration of rejection: the rejection characterizing NF membrane with the rejection of NF membrane to RB RoseBengal (RB).
The pure water flux of the polyacrylonitrile basement membrane after step 3 process is 129.45L/m
2hbar is 24.21% to the rejection of RB, and the flux of ethanol is 120.56L/m
2hbar, the RB rejection in the middle of ethanol is 19.87%.
The pure water flux that step 4 contains the polyacrylonitrile basement membrane of polyethyleneimine: amine layer is 20.49L/m
2hbar is 77.26% to the rejection of RB, and the flux of ethanol is 34.22L/m
2hbar, the RB rejection in the middle of ethanol is 49.19%.
The surface-assembled number of plies of the NF membrane that this example obtains is 2 layers, and its pure water flux is 22.96L/m
2hbar is 80.46% to the rejection of RB, and the flux of ethanol is 35.46L/m
2hbar, the RB rejection in the middle of ethanol is 51.26%.
From the experimental data of the present embodiment, compared with the polyacrylonitrile basement membrane that NF membrane containing polyethyleneimine: amine layer and graphene oxide layer and the polyacrylonitrile basement membrane after step 3 process, step 4 contain polyethyleneimine: amine layer, larger flux can be obtained there is good cutoff performance simultaneously.
Embodiment 2: the present embodiment LBL self-assembly legal system, for the method for NF membrane, comprises the following steps:
One, by 79g nitrogen methyl pyrrolidone and 1g polyethylene glycol, add in 20g polyacrylonitrile, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washs 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, 30min is reacted at 40 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5h, be placed in 0.1mol/L hydrochloric acid solution again and soak 3h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 30min in 1g/L polyethylenimine solution, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer;
Five, the ultrafiltration membranes containing polyethyleneimine: amine layer is placed in 0.1g/L graphene oxide solution, soaks 30min, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 1 time of step 4 and step 5, namely complete.
Have large permeation flux and have the index that higher rejection is desirable NF membrane film simultaneously concurrently.
The surface-assembled number of plies of the NF membrane that this example obtains is 4 layers, and its pure water flux is 16.45L/m
2hbar is 90.47% to the rejection of RB, and the flux of ethanol is 34.34L/m
2hbar, the RB rejection in the middle of ethanol is 54.21%.
Embodiment 3: the present embodiment LBL self-assembly legal system, for the method for NF membrane, comprises the following steps:
One, by 79g nitrogen methyl pyrrolidone and 1g polyethylene glycol, add in 20g polyacrylonitrile, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washs 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, 30min is reacted at 40 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5h, be placed in 0.1mol/L hydrochloric acid solution again and soak 3h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 30min in 1g/L polyethylenimine solution, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer;
Five, the ultrafiltration membranes containing polyethyleneimine: amine layer is placed in 0.1g/L graphene oxide solution, soaks 30min, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 2 times of step 4 and step 5, namely complete.
Have large permeation flux and have the index that higher rejection is desirable NF membrane film simultaneously concurrently.
The surface-assembled number of plies of the NF membrane that this example obtains is 6 layers, and its pure water flux is 14.56L/m
2hbar is 94.27% to the rejection of RB, and the flux of ethanol is 29.41L/m
2hbar, the RB rejection in the middle of ethanol is 65.26%.
Embodiment 4: the present embodiment LBL self-assembly legal system, for the method for NF membrane, comprises the following steps:
One, by 79g nitrogen methyl pyrrolidone and 1g polyethylene glycol, add in 20g polyacrylonitrile, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washs 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, 30min is reacted at 40 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5h, be placed in 0.1mol/L hydrochloric acid solution again and soak 3h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 30min in 1g/L polyethylenimine solution, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer;
Five, the ultrafiltration membranes containing polyethyleneimine: amine layer is placed in 0.1g/L graphene oxide solution, soaks 30min, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 3 times of step 4 and step 5, namely complete.
Have large permeation flux and have the index that higher rejection is desirable NF membrane film simultaneously concurrently.
The surface-assembled number of plies of the NF membrane that this example obtains is 8 layers, and its pure water flux is 12.78L/m
2hbar is 97.65% to the rejection of RB, and the flux of ethanol is 25.16L/m
2hbar, the RB rejection in the middle of ethanol is 71.06%.
Embodiment 4: the present embodiment LBL self-assembly legal system, for the method for NF membrane, comprises the following steps:
One, by 79g nitrogen methyl pyrrolidone and 1g polyethylene glycol, add in 20g polyacrylonitrile, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washs 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, 30min is reacted at 40 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5h, be placed in 0.1mol/L hydrochloric acid solution again and soak 3h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 30min in 1g/L polyethylenimine solution, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer;
Five, the ultrafiltration membranes containing polyethyleneimine: amine layer is placed in 0.1g/L graphene oxide solution, soaks 30min, put into deionized water after taking-up and soak 5min, obtain the ultrafiltration membranes containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 4 times of step 4 and step 5, namely complete.
Have large permeation flux and have the index that higher rejection is desirable NF membrane film simultaneously concurrently.
The surface-assembled number of plies of the NF membrane that this example obtains is 10 layers, and its pure water flux is 6.97L/m
2hbar is 99.99% to the rejection of RB, and the flux of ethanol is 22.98L/m
2hbar, the RB rejection in the middle of ethanol is 81.26%.
Embodiment 1 ~ 4 utilizes layer-by-layer, make polymine and graphene oxide modification PAN film, the pore size on its hydrophily and film surface is is effectively regulated and controled, and film is thinner, larger flux can be obtained, the NF membrane simultaneously obtained has good cutoff performance, be applicable to the separation of various dyestuff, desalinization etc., reduce energy consumption and purified water quality simultaneously, desalinate seawater, have great application prospect.
Claims (10)
1. LBL self-assembly legal system is for a method for NF membrane, it is characterized in that the method comprises the following steps:
One, solvent, pore former and polyacrylonitrile are mixed, obtained polyacrylonitrile solution;
Two, utilize submergence-precipitated phase conversion method that polyacrylonitrile solution is made ultrafiltration membranes, deionized water washing 3 ~ 5 times, obtains polyacrylonitrile basement membrane;
Three, polyacrylonitrile basement membrane is placed in sodium hydroxide solution, 20min ~ 60min is reacted at 20 DEG C ~ 50 DEG C, after reaction terminates, polyacrylonitrile basement membrane is taken out, put into deionized water soaking and washing 0.5 ~ 2h, be placed in hydrochloric acid solution again and soak 1 ~ 5h, obtain the polyacrylonitrile basement membrane after processing;
Four, the polyacrylonitrile basement membrane after step 3 process is immersed 10 ~ 90min in polyethylenimine solution, put into deionized water after taking-up and soak 2 ~ 10min, obtain the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer;
Five, the polyacrylonitrile basement membrane containing polyethyleneimine: amine layer is placed in graphene oxide solution, soaks 10 ~ 90min, put into deionized water after taking-up and soak 2 ~ 10min, obtain the NF membrane containing polyethyleneimine: amine layer and graphene oxide layer;
Six, repeat the operation 0 ~ 7 time of step 4 and step 5, namely complete.
2. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that the solvent described in step one is 1-METHYLPYRROLIDONE.
3. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that the pore former described in step one is polyethylene glycol or polyvinylpyrrolidone.
4. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that the mass ratio of polyacrylonitrile in step one, pore former and solvent is for (15 ~ 25): 1:(74 ~ 84).
5. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that the mass concentration of the sodium hydroxide solution described in step 3 is 5% ~ 20%.
6. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that the concentration of the hydrochloric acid solution described in step 3 is 0.05mol/L ~ 0.5mol/L.
7. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that the concentration of the polyethylenimine solution described in step 4 is 0.5 ~ 3g/L.
8. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that immersing 30min in polyethylenimine solution in step 4, puts into deionized water and soak 5min after taking-up.
9. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that the concentration of the graphene oxide solution described in step 5 is 0.05 ~ 0.5g/L.
10. a kind of LBL self-assembly legal system according to claim 1 is for the method for NF membrane, it is characterized in that being placed in graphene oxide solution in step 5, soaks 30min, puts into deionized water and soak 5min after taking-up.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510586136.XA CN105169962B (en) | 2015-09-15 | 2015-09-15 | Method for preparing nanofiltration membrane by adopting layer-by-layer self-assembly method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510586136.XA CN105169962B (en) | 2015-09-15 | 2015-09-15 | Method for preparing nanofiltration membrane by adopting layer-by-layer self-assembly method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105169962A true CN105169962A (en) | 2015-12-23 |
| CN105169962B CN105169962B (en) | 2017-05-24 |
Family
ID=54892676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510586136.XA Active CN105169962B (en) | 2015-09-15 | 2015-09-15 | Method for preparing nanofiltration membrane by adopting layer-by-layer self-assembly method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105169962B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107441956A (en) * | 2017-09-05 | 2017-12-08 | 景德镇陶瓷大学 | A kind of preparation method of adjustable asymmetric graphene oxide composite membrane of passage and its obtained product |
| CN107803119A (en) * | 2017-11-03 | 2018-03-16 | 宁夏大学 | A kind of preparation method of composite film and the method using residual tetracycline in its removal pharmacy waste water |
| CN107829084A (en) * | 2017-11-07 | 2018-03-23 | 上海电力学院 | A kind of modification processing method that PEI GO chitosan composite membranes are prepared in aluminum alloy surface |
| CN108103771A (en) * | 2017-11-28 | 2018-06-01 | 东华大学 | A kind of redox graphene assembling polyacrylonitrile fibre and preparation method thereof |
| CN109758928A (en) * | 2018-12-10 | 2019-05-17 | 天津城建大学 | A kind of preparation method and application of graphene oxide composite membrane |
| CN109794175A (en) * | 2018-12-26 | 2019-05-24 | 浙江大学 | Graphene oxide composite membrane and its preparation method and application with pH responsiveness |
| CN110038436A (en) * | 2019-04-04 | 2019-07-23 | 三达膜科技（厦门）有限公司 | A kind of preparation method of titanium dioxide graphene oxide polyethylene glycol composite ceramics nanofiltration membrane |
| CN110280144A (en) * | 2019-06-27 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of preparation method of aluminium oxide/graphene oxide/polyvinyl alcohol composite nanometer filtering film |
| CN110280143A (en) * | 2019-06-27 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of preparation method of dopamine/graphene oxide/polyvinyl alcohol composite nanometer filtering film |
| CN110559891A (en) * | 2019-09-19 | 2019-12-13 | 河海大学 | Preparation method of borate crosslinking-based high-strength graphene oxide film |
| CN110882631A (en) * | 2019-12-17 | 2020-03-17 | 西安工业大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
| CN111437739A (en) * | 2020-04-23 | 2020-07-24 | 北京工业大学 | Preparation method of polyacrylonitrile-based composite loose nanofiltration membrane |
| CN113797773A (en) * | 2020-06-12 | 2021-12-17 | 三达膜科技（厦门）有限公司 | Molybdenum disulfide oxide-graphene oxide-PEI composite ceramic nanofiltration membrane and preparation method thereof |
| CN114950148A (en) * | 2022-05-23 | 2022-08-30 | 厦门大学 | Layer-by-layer self-assembly preparation method of graphene oxide nanofiltration membrane |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474897A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Grapheme-organic material layered assembling film and preparation method thereof |
| CN102824856A (en) * | 2012-08-31 | 2012-12-19 | 北京工业大学 | Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology |
| CN103285741A (en) * | 2013-05-20 | 2013-09-11 | 哈尔滨工业大学 | Preparation method of solvent-resistant compound nanofiltration membrane |
| CN103373727A (en) * | 2012-04-26 | 2013-10-30 | 通用汽车环球科技运作有限责任公司 | Self assembly of graphene materials |
| CN103706264A (en) * | 2014-01-14 | 2014-04-09 | 中国海洋大学 | Layer-by-layer self-assembling oxidized graphene nano-filtration membrane and preparation method thereof |
| CN103877940A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | 4-mercaptophenylboronic acid immobilized graphene oxide composite nanometer material, preparation and application thereof |
| WO2015060782A1 (en) * | 2013-10-21 | 2015-04-30 | Hwv Technologies Pte. Ltd. | Graphene oxide/polymer composite membranes and methods of forming thereof |
-
2015
- 2015-09-15 CN CN201510586136.XA patent/CN105169962B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474897A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Grapheme-organic material layered assembling film and preparation method thereof |
| CN103373727A (en) * | 2012-04-26 | 2013-10-30 | 通用汽车环球科技运作有限责任公司 | Self assembly of graphene materials |
| CN102824856A (en) * | 2012-08-31 | 2012-12-19 | 北京工业大学 | Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology |
| CN103877940A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | 4-mercaptophenylboronic acid immobilized graphene oxide composite nanometer material, preparation and application thereof |
| CN103285741A (en) * | 2013-05-20 | 2013-09-11 | 哈尔滨工业大学 | Preparation method of solvent-resistant compound nanofiltration membrane |
| WO2015060782A1 (en) * | 2013-10-21 | 2015-04-30 | Hwv Technologies Pte. Ltd. | Graphene oxide/polymer composite membranes and methods of forming thereof |
| CN103706264A (en) * | 2014-01-14 | 2014-04-09 | 中国海洋大学 | Layer-by-layer self-assembling oxidized graphene nano-filtration membrane and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| NAIXIN WANG ET AL.: "Self-assembly of graphene oxide and polyelectrolyte complex nanohybrid membranes for nanofiltration and pervaporation", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 刘杰等: "用静电自组装法制备的石墨烯薄膜特性研究", 《光散射学报》 * |
| 王乃鑫: "动态自组装聚电解质及纳米杂化复合分离膜研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107441956A (en) * | 2017-09-05 | 2017-12-08 | 景德镇陶瓷大学 | A kind of preparation method of adjustable asymmetric graphene oxide composite membrane of passage and its obtained product |
| CN107441956B (en) * | 2017-09-05 | 2019-07-16 | 景德镇陶瓷大学 | A kind of preparation method of the adjustable asymmetric graphene oxide composite membrane in channel and its product obtained |
| CN107803119A (en) * | 2017-11-03 | 2018-03-16 | 宁夏大学 | A kind of preparation method of composite film and the method using residual tetracycline in its removal pharmacy waste water |
| CN107803119B (en) * | 2017-11-03 | 2021-01-05 | 宁夏大学 | Preparation method of composite film and method for removing residual tetracycline in pharmaceutical wastewater by using composite film |
| CN107829084B (en) * | 2017-11-07 | 2019-12-27 | 上海电力学院 | Modification treatment method for preparing PEI-GO-chitosan composite membrane on surface of aluminum alloy |
| CN107829084A (en) * | 2017-11-07 | 2018-03-23 | 上海电力学院 | A kind of modification processing method that PEI GO chitosan composite membranes are prepared in aluminum alloy surface |
| CN108103771A (en) * | 2017-11-28 | 2018-06-01 | 东华大学 | A kind of redox graphene assembling polyacrylonitrile fibre and preparation method thereof |
| CN108103771B (en) * | 2017-11-28 | 2020-10-30 | 东华大学 | Reduced graphene oxide assembled polyacrylonitrile fiber and preparation method thereof |
| CN109758928A (en) * | 2018-12-10 | 2019-05-17 | 天津城建大学 | A kind of preparation method and application of graphene oxide composite membrane |
| CN109794175A (en) * | 2018-12-26 | 2019-05-24 | 浙江大学 | Graphene oxide composite membrane and its preparation method and application with pH responsiveness |
| CN110038436A (en) * | 2019-04-04 | 2019-07-23 | 三达膜科技（厦门）有限公司 | A kind of preparation method of titanium dioxide graphene oxide polyethylene glycol composite ceramics nanofiltration membrane |
| CN110038436B (en) * | 2019-04-04 | 2022-01-04 | 三达膜科技（厦门）有限公司 | Preparation method of titanium dioxide/graphene oxide/polyethylene glycol composite ceramic nanofiltration membrane |
| CN110280143A (en) * | 2019-06-27 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of preparation method of dopamine/graphene oxide/polyvinyl alcohol composite nanometer filtering film |
| CN110280144A (en) * | 2019-06-27 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of preparation method of aluminium oxide/graphene oxide/polyvinyl alcohol composite nanometer filtering film |
| CN110280144B (en) * | 2019-06-27 | 2022-01-04 | 三达膜科技（厦门）有限公司 | Preparation method of aluminum oxide/graphene oxide/polyvinyl alcohol composite nanofiltration membrane |
| CN110559891A (en) * | 2019-09-19 | 2019-12-13 | 河海大学 | Preparation method of borate crosslinking-based high-strength graphene oxide film |
| CN110882631A (en) * | 2019-12-17 | 2020-03-17 | 西安工业大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
| CN110882631B (en) * | 2019-12-17 | 2022-03-15 | 西安工业大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
| CN111437739A (en) * | 2020-04-23 | 2020-07-24 | 北京工业大学 | Preparation method of polyacrylonitrile-based composite loose nanofiltration membrane |
| CN113797773A (en) * | 2020-06-12 | 2021-12-17 | 三达膜科技（厦门）有限公司 | Molybdenum disulfide oxide-graphene oxide-PEI composite ceramic nanofiltration membrane and preparation method thereof |
| CN113797773B (en) * | 2020-06-12 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Molybdenum disulfide oxide-graphene oxide-PEI composite ceramic nanofiltration membrane and preparation method thereof |
| CN114950148A (en) * | 2022-05-23 | 2022-08-30 | 厦门大学 | Layer-by-layer self-assembly preparation method of graphene oxide nanofiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105169962B (en) | 2017-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105169962A (en) | Method for preparing nanofiltration membrane by adopting layer-by-layer self-assembly method | |
| CN103223302B (en) | Preparation method of self-assembly covalent cross-linked sodium filter membrane | |
| CN102773024B (en) | Method for preparing hollow fiber type forward osmotic membrane | |
| CN104984666B (en) | Metal polyphenol film and preparation method and application | |
| CN105169970A (en) | Preparation method for polydopamine-modified polyamide composite forward osmosis membrane | |
| CN103394295B (en) | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof | |
| CN106512729B (en) | A kind of equipment with high desalinization reverse osmosis composite membrane and preparation method thereof | |
| CN107433143B (en) | Polyelectrolyte-loaded antibacterial cellulose nanofiltration membrane and preparation method thereof | |
| He et al. | Polyelectrolyte-based nanofiltration membranes with exceptional performance in Mg2+/Li+ separation in a wide range of solution conditions | |
| CN105396471A (en) | Preparation method of high water flux reverse osmosis membrane | |
| CN105617882A (en) | Chitosan modified graphene oxide nano composite positive osmotic membrane and preparation method thereof | |
| CN105107393A (en) | Preparation method of monovalent ion selective composite film based on template method | |
| CN102824859B (en) | Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method | |
| CN108187511A (en) | High flux and high retention ratio polyamide composite reverse osmosis membrane and preparation method thereof | |
| CN103768963A (en) | Preparation method for polyamide composite nanofiltration membrane | |
| CN103212309A (en) | Preparation method of supportless forward osmosis membrane | |
| CN112535955B (en) | Decolorizing membrane and preparation method and application thereof | |
| CN108722203B (en) | Preparation method of high-flux polyaniline composite nanofiltration membrane | |
| CN102814126A (en) | Preparation method of high-flux antioxidant nanofiltration membrane | |
| CN107837685A (en) | A kind of renovation process of waste water hyperfiltration film | |
| CN113578061B (en) | Method for preparing composite nanofiltration membrane by using polluted polyethersulfone ultrafiltration membrane and composite nanofiltration membrane | |
| CN105032204A (en) | Method for preparing titanium dioxide modified polypyrole composite nanofiltration membrane | |
| CN110787654B (en) | Method for preparing reverse osmosis membrane by using 1-methylimidazole as water phase additive | |
| CN110394066B (en) | Composite nanofiltration membrane and preparation method and application thereof | |
| CN104548951A (en) | Antibacterial composite nanofiltration membrane with high salt rejection rate and preparation method of antibacterial composite nanofiltration membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |