CN105169962B - 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
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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 increasingly paid attention to.Wherein membrane separation technique is especially
New membrane separation technique is just by the extensive concern of scientists.
Nanofiltration starts from the middle and later periods eighties, is a kind of new pressure-actuated process without phase transformation physical separation.Nanofiltration
Aperture, aperture more than reverse osmosis membrane of the aperture of film less than milipore filter.The characteristics of NF membrane be it to divalence and multivalence from
The rejection higher of son, and it is then relatively low to monovalention rejection, and its molecular cut off is between 200-1000gmol-1.Thus, nanofiltration process is widely used in the desalination of dyestuff isoreactivity material different with concentration, water softening, molecular weight has
The feed separation of machine thing and the industrial circle such as removal of a small amount of organic matter in purifying, water.The subject matter of existing NF membrane research
When being excellent cutoff performance, the water flux of the unit pressure of NF membrane is but than relatively low.
The content of the invention
The NF membrane prepared the present invention is to solve existing method can not simultaneously have good cutoff performance and compared with Gao Shui
The problem of flux, there is provided a kind of method that LBL self-assembly method prepares NF membrane.
The method that a kind of LBL self-assembly method of the present invention prepares NF membrane, comprises the following steps：
First, solvent, pore former and polyacrylonitrile are mixed, polyacrylonitrile solution is obtained；
2nd, polyacrylonitrile solution is made ultrafiltration membranes, deionized water washing 3~5 using submergence-precipitation phase inversion
It is secondary, obtain polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in sodium hydroxide solution, 20min~60min is reacted at 20 DEG C~50 DEG C, instead
After should terminating, polyacrylonitrile basement membrane is taken out, be put into 0.5~2h of soaking and washing in deionized water, then be placed in leaching in hydrochloric acid solution
1~5h of bubble, the polyacrylonitrile basement membrane after being processed；
4th, 10~90min in the polyacrylonitrile basement membrane immersion polyethylenimine solution after step 3 is processed, puts after taking-up
Enter deionized water and soak 2~10min, obtain the polyacrylonitrile basement membrane containing polyethyleneimine amine layer；
5th, the polyacrylonitrile basement membrane containing polyethyleneimine amine layer is placed in graphene oxide solution, immersion 10~
90min, is put into deionized water and soaks 2~10min after taking-up, obtain the nanofiltration containing polyethyleneimine amine layer and graphene oxide layer
Film；
6th, the operation of repeat step four and step 5 0~7 time, that is, complete.
The present invention utilizes layer-by-layer, makes polyethyleneimine and the modified PAN films of graphene oxide, makes its hydrophily
Pore size with film surface is effectively regulated and controled, and film can be obtained than larger flux than relatively thin, while obtain
NF membrane has good cutoff performance, it is adaptable to the separation of various dyestuffs, desalinization etc., reduces energy consumption and purifies simultaneously
Water quality, has desalinated seawater, there is great application prospect.
Specific embodiment
Specific embodiment one：The method that a kind of LBL self-assembly method of present embodiment prepares NF membrane, including following step
Suddenly：
First, solvent, pore former and polyacrylonitrile are mixed, polyacrylonitrile solution is obtained；
2nd, polyacrylonitrile solution is made ultrafiltration membranes, deionized water washing 3~5 using submergence-precipitation phase inversion
It is secondary, obtain polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in sodium hydroxide solution, 20min~60min is reacted at 20 DEG C~50 DEG C, instead
After should terminating, polyacrylonitrile basement membrane is taken out, be put into 0.5~2h of soaking and washing in deionized water, then be placed in leaching in hydrochloric acid solution
1~5h of bubble, the polyacrylonitrile basement membrane after being processed；
4th, 10~90min in the polyacrylonitrile basement membrane immersion polyethylenimine solution after step 3 is processed, puts after taking-up
Enter deionized water and soak 2~10min, obtain the polyacrylonitrile basement membrane containing polyethyleneimine amine layer；
5th, the polyacrylonitrile basement membrane containing polyethyleneimine amine layer is placed in graphene oxide solution, immersion 10~
90min, is put into deionized water and soaks 2~10min after taking-up, obtain the nanofiltration containing polyethyleneimine amine layer and graphene oxide layer
Film；
6th, the operation of repeat step four and step 5 0~7 time, that is, complete.
Present embodiment utilizes layer-by-layer, makes polyethyleneimine and the modified PAN films of graphene oxide, makes its parent
Aqueous and film surface pore size is effectively regulated and controled, and film can be obtained than larger flux than relatively thin, while
To NF membrane there is good cutoff performance, it is adaptable to the separation of various dyestuffs, desalinization etc., reduce energy consumption simultaneously net
Change water quality, desalinated seawater, there is great application prospect.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Solvent described in step one is
1-METHYLPYRROLIDONE.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment and the pore-forming described in step one unlike specific embodiment one or two
Agent is polyethylene glycol or polyvinylpyrrolidone.Other are identical with specific embodiment one or two.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Gather in step one
The mass ratio of acrylonitrile, pore former and solvent is (15~25):1:(74~84).Other are one of with specific embodiment one to three
It is identical.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Described in step 3
Sodium hydroxide solution mass concentration be 5%~20%.Other are identical with one of specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Described in step 3
Hydrochloric acid solution concentration be 0.05mol/L~0.5mol/L.Other are identical with one of specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Described in step 4
Polyethylenimine solution concentration be 0.5~3g/L.Other are identical with one of specific embodiment one to six.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Soaked in step 4
Enter 30min in polyethylenimine solution, deionized water immersion 5min is put into after taking-up.Other and specific embodiment one to seven it
One is identical.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：Described in step 5
Graphene oxide solution concentration be 0.05~0.5g/L.Other are identical with one of specific embodiment one to eight.
Specific embodiment ten：Unlike one of present embodiment and specific embodiment one to nine：Put in step 5
In graphene oxide solution, 30min is soaked, deionized water immersion 5min is put into after taking-up.Other and specific embodiment one
It is identical to one of nine.
The following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1：The method that the present embodiment LBL self-assembly method prepares NF membrane, comprises the following steps：
First, by 79g N-methyls pyrrolidones and 1g polyethylene glycol, add in 20g polyacrylonitrile, polyacrylonitrile is obtained molten
Liquid；
2nd, polyacrylonitrile solution is made ultrafiltration membranes using submergence-precipitation phase inversion, deionized water is washed 5 times, obtained
To polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, is reacted at 40 DEG C
30min, after reaction terminates, polyacrylonitrile basement membrane is taken out, and is put into soaking and washing 0.5h in deionized water, then be placed in 0.1mol/L
3h is soaked in hydrochloric acid solution, the polyacrylonitrile basement membrane after being processed；
4th, 30min in the polyacrylonitrile basement membrane immersion 1g/L polyethylenimine solutions after step 3 is processed, puts after taking-up
Enter deionized water immersion 5min, obtain the polyacrylonitrile basement membrane containing polyethyleneimine amine layer；
5th, the polyacrylonitrile basement membrane containing polyethyleneimine amine layer is placed in 0.1g/L graphene oxide solutions, is soaked
30min, is put into deionized water immersion 5min after taking-up, obtain the NF membrane containing polyethyleneimine amine layer and graphene oxide layer；
6th, the operation of repeat step four and step 50 time, that is, complete.
Possess big permeation flux while having the index that rejection higher is preferable NF membrane film concurrently.
The measure of flux：The nanofiltration membrane sample of certain area is taken in nanofiltration test device, in room temperature and 0.5MPa (N2)
NF membrane is compacted 45min by lower solvent, methyl alcohol, ethanol, the quality m of isopropanol by film is tested, by calculating body
Product V.Treat tested after solvent flux is substantially constant before test every time.Under conditions of ensureing that certain pressure is constant,
Solvent volume Vs of the test certain hour t through NF membrane.
The measure of rejection：Nanofiltration is characterized to the rejection of RB Rose Bengal (RB) with NF membrane
The rejection of film.
The pure water flux of the polyacrylonitrile basement membrane after step 3 treatment is 129.45L/m2H bar, the rejection to RB is
24.21%, the flux of ethanol is 120.56L/m2The rejection of h bar, RB 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/m2H bar, to RB's
Rejection is 77.26%, and the flux of ethanol is 34.22L/m2The rejection of h bar, RB in the middle of ethanol is 49.19%.
The surface-assembled number of plies of the NF membrane that this example is obtained is 2 layers, and its pure water flux is 22.96L/m2H bar, to RB
Rejection be 80.46%, the flux of ethanol is 35.46L/m2The rejection of h bar, RB in the middle of ethanol is 51.26%.
Knowable to the experimental data of the present embodiment, NF membrane and step containing polyethyleneimine amine layer and graphene oxide layer
The polyacrylonitrile basement membrane that polyacrylonitrile basement membrane, step 4 after three treatment contain polyethyleneimine amine layer is compared, and can be compared
Big flux has good cutoff performance simultaneously.
Embodiment 2：The method that the present embodiment LBL self-assembly method prepares NF membrane, comprises the following steps：
First, by 79g N-methyls pyrrolidones and 1g polyethylene glycol, add in 20g polyacrylonitrile, polyacrylonitrile is obtained molten
Liquid；
2nd, polyacrylonitrile solution is made ultrafiltration membranes using submergence-precipitation phase inversion, deionized water is washed 5 times, obtained
To polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, is reacted at 40 DEG C
30min, after reaction terminates, polyacrylonitrile basement membrane is taken out, and is put into soaking and washing 0.5h in deionized water, then be placed in 0.1mol/L
3h is soaked in hydrochloric acid solution, the polyacrylonitrile basement membrane after being processed；
4th, 30min in the polyacrylonitrile basement membrane immersion 1g/L polyethylenimine solutions after step 3 is processed, puts after taking-up
Enter deionized water immersion 5min, obtain the ultrafiltration membranes containing polyethyleneimine amine layer；
5th, the ultrafiltration membranes containing polyethyleneimine amine layer are placed in 0.1g/L graphene oxide solutions, soak 30min,
Deionized water immersion 5min is put into after taking-up, the ultrafiltration membranes containing polyethyleneimine amine layer and graphene oxide layer are obtained；
6th, the operation of repeat step four and step 51 time, that is, complete.
Possess big permeation flux while having the index that rejection higher is preferable NF membrane film concurrently.
The surface-assembled number of plies of the NF membrane that this example is obtained is 4 layers, and its pure water flux is 16.45L/m2H bar, to RB
Rejection be 90.47%, the flux of ethanol is 34.34L/m2The rejection of h bar, RB in the middle of ethanol is 54.21%.
Embodiment 3：The method that the present embodiment LBL self-assembly method prepares NF membrane, comprises the following steps：
First, by 79g N-methyls pyrrolidones and 1g polyethylene glycol, add in 20g polyacrylonitrile, polyacrylonitrile is obtained molten
Liquid；
2nd, polyacrylonitrile solution is made ultrafiltration membranes using submergence-precipitation phase inversion, deionized water is washed 5 times, obtained
To polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, is reacted at 40 DEG C
30min, after reaction terminates, polyacrylonitrile basement membrane is taken out, and is put into soaking and washing 0.5h in deionized water, then be placed in 0.1mol/L
3h is soaked in hydrochloric acid solution, the polyacrylonitrile basement membrane after being processed；
4th, 30min in the polyacrylonitrile basement membrane immersion 1g/L polyethylenimine solutions after step 3 is processed, puts after taking-up
Enter deionized water immersion 5min, obtain the ultrafiltration membranes containing polyethyleneimine amine layer；
5th, the ultrafiltration membranes containing polyethyleneimine amine layer are placed in 0.1g/L graphene oxide solutions, soak 30min,
Deionized water immersion 5min is put into after taking-up, the ultrafiltration membranes containing polyethyleneimine amine layer and graphene oxide layer are obtained；
6th, the operation of repeat step four and step 52 times, that is, complete.
Possess big permeation flux while having the index that rejection higher is preferable NF membrane film concurrently.
The surface-assembled number of plies of the NF membrane that this example is obtained is 6 layers, and its pure water flux is 14.56L/m2H bar, to RB
Rejection be 94.27%, the flux of ethanol is 29.41L/m2The rejection of h bar, RB in the middle of ethanol is 65.26%.
Embodiment 4：The method that the present embodiment LBL self-assembly method prepares NF membrane, comprises the following steps：
First, by 79g N-methyls pyrrolidones and 1g polyethylene glycol, add in 20g polyacrylonitrile, polyacrylonitrile is obtained molten
Liquid；
2nd, polyacrylonitrile solution is made ultrafiltration membranes using submergence-precipitation phase inversion, deionized water is washed 5 times, obtained
To polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, is reacted at 40 DEG C
30min, after reaction terminates, polyacrylonitrile basement membrane is taken out, and is put into soaking and washing 0.5h in deionized water, then be placed in 0.1mol/L
3h is soaked in hydrochloric acid solution, the polyacrylonitrile basement membrane after being processed；
4th, 30min in the polyacrylonitrile basement membrane immersion 1g/L polyethylenimine solutions after step 3 is processed, puts after taking-up
Enter deionized water immersion 5min, obtain the ultrafiltration membranes containing polyethyleneimine amine layer；
5th, the ultrafiltration membranes containing polyethyleneimine amine layer are placed in 0.1g/L graphene oxide solutions, soak 30min,
Deionized water immersion 5min is put into after taking-up, the ultrafiltration membranes containing polyethyleneimine amine layer and graphene oxide layer are obtained；
6th, the operation of repeat step four and step 53 times, that is, complete.
Possess big permeation flux while having the index that rejection higher is preferable NF membrane film concurrently.
The surface-assembled number of plies of the NF membrane that this example is obtained is 8 layers, and its pure water flux is 12.78L/m2H bar, to RB
Rejection be 97.65%, the flux of ethanol is 25.16L/m2The rejection of h bar, RB in the middle of ethanol is 71.06%.
Embodiment 4：The method that the present embodiment LBL self-assembly method prepares NF membrane, comprises the following steps：
First, by 79g N-methyls pyrrolidones and 1g polyethylene glycol, add in 20g polyacrylonitrile, polyacrylonitrile is obtained molten
Liquid；
2nd, polyacrylonitrile solution is made ultrafiltration membranes using submergence-precipitation phase inversion, deionized water is washed 5 times, obtained
To polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in the sodium hydroxide solution that mass concentration is 10%, is reacted at 40 DEG C
30min, after reaction terminates, polyacrylonitrile basement membrane is taken out, and is put into soaking and washing 0.5h in deionized water, then be placed in 0.1mol/L
3h is soaked in hydrochloric acid solution, the polyacrylonitrile basement membrane after being processed；
4th, 30min in the polyacrylonitrile basement membrane immersion 1g/L polyethylenimine solutions after step 3 is processed, puts after taking-up
Enter deionized water immersion 5min, obtain the ultrafiltration membranes containing polyethyleneimine amine layer；
5th, the ultrafiltration membranes containing polyethyleneimine amine layer are placed in 0.1g/L graphene oxide solutions, soak 30min,
Deionized water immersion 5min is put into after taking-up, the ultrafiltration membranes containing polyethyleneimine amine layer and graphene oxide layer are obtained；
6th, the operation of repeat step four and step 54 times, that is, complete.
Possess big permeation flux while having the index that rejection higher is preferable NF membrane film concurrently.
The surface-assembled number of plies of the NF membrane that this example is obtained is 10 layers, and its pure water flux is 6.97L/m2H bar, to RB
Rejection be 99.99%, the flux of ethanol is 22.98L/m2The rejection of h bar, RB in the middle of ethanol is 81.26%.
Embodiment 1~4 utilizes layer-by-layer, makes polyethyleneimine and the modified PAN films of graphene oxide, makes its parent
Aqueous and film surface pore size is effectively regulated and controled, and film can be obtained than larger flux than relatively thin, while
To NF membrane there is good cutoff performance, it is adaptable to the separation of various dyestuffs, desalinization etc., reduce energy consumption simultaneously net
Change water quality, desalinated seawater, there is great application prospect.
Claims (3)
1. a kind of method that LBL self-assembly method prepares NF membrane, it is characterised in that the method is comprised the following steps：
First, solvent, pore former and polyacrylonitrile are mixed, polyacrylonitrile solution is obtained；
Solvent described in step one is 1-METHYLPYRROLIDONE；
Pore former described in step one is polyethylene glycol or polyvinylpyrrolidone；
The mass ratio of polyacrylonitrile, pore former and solvent is (15~25) in step one:1:(74~84)；
2nd, polyacrylonitrile solution is made ultrafiltration membranes using submergence-precipitation phase inversion, deionized water is washed 3~5 times, obtained
To polyacrylonitrile basement membrane；
3rd, polyacrylonitrile basement membrane is placed in sodium hydroxide solution, 20min~60min, reaction knot is reacted at 20 DEG C~50 DEG C
Shu Hou, polyacrylonitrile basement membrane is taken out, and is put into 0.5~2h of soaking and washing in deionized water, then be placed in immersion 1 in hydrochloric acid solution~
5h, the polyacrylonitrile basement membrane after being processed；
The mass concentration of the sodium hydroxide solution described in step 3 is 5%~20%；
The concentration of the hydrochloric acid solution described in step 3 is 0.05mol/L~0.5mol/L；
4th, 10~90min in the polyacrylonitrile basement membrane immersion polyethylenimine solution after step 3 is processed, is put into after taking-up
Ionized water soaks 2~10min, obtains the polyacrylonitrile basement membrane containing polyethyleneimine amine layer；
The concentration of the polyethylenimine solution described in step 4 is 0.5~3g/L；
5th, the polyacrylonitrile basement membrane containing polyethyleneimine amine layer is placed in graphene oxide solution, soaks 10~90min, taken
Deionized water is put into after going out and soaks 2~10min, obtain the NF membrane containing polyethyleneimine amine layer and graphene oxide layer；
The concentration of the graphene oxide solution described in step 5 is 0.05~0.5g/L；
6th, the operation of repeat step four and step 54 times, that is, complete, and obtains NF membrane；
The pure water flux of the NF membrane described in step 6 is 6.97L/m2H bar, the rejection to RB is
99.99%, the flux of ethanol is 22.98L/m2H bar, rejection of the RB in the middle of ethanol is 81.26%.
2. the method that a kind of LBL self-assembly method according to claim 1 prepares NF membrane, it is characterised in that in step 4
30min in immersion polyethylenimine solution, is put into deionized water immersion 5min after taking-up.
3. the method that a kind of LBL self-assembly method according to claim 1 prepares NF membrane, it is characterised in that in step 5
It is placed in graphene oxide solution, soaks 30min, deionized water immersion 5min is put into after taking-up.
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| 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 |
| 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 |
| 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 |
| 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 |
| CN110280143B (en) * | 2019-06-27 | 2022-04-19 | 三达膜科技（厦门）有限公司 | Preparation method of dopamine/graphene oxide/polyvinyl alcohol composite nanofiltration membrane |
| 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 |
| 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 |
| 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 |
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| US20130284338A1 (en) * | 2012-04-26 | 2013-10-31 | Gm Global Technology Operations Llc. | Self assembly of graphene materials |
| CN102824856B (en) * | 2012-08-31 | 2015-07-08 | 北京工业大学 | Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology |
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