CN104028110B - A kind of thin layer composite forward osmosis membrane and preparation method thereof - Google Patents
A kind of thin layer composite forward osmosis membrane and preparation method thereof Download PDFInfo
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- CN104028110B CN104028110B CN201410261478.XA CN201410261478A CN104028110B CN 104028110 B CN104028110 B CN 104028110B CN 201410261478 A CN201410261478 A CN 201410261478A CN 104028110 B CN104028110 B CN 104028110B
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Abstract
The invention provides the preparation of a kind of thin layer composite forward osmosis membrane, the forward osmosis membrane of preparation, on the basis keeping original advantage, can effectively reduce interior concentration polarization, thus reach the target significantly improving water flux, and greatly can strengthen the combined strength bination of screen cloth supporting layer and interfacial polymerization cortex, thus improve the endurance quality of forward osmosis membrane and extend its service life, solve positive infiltration applications bottleneck problem.Adopt DOPA and/or dopamine to carry out chemical modification and modification to screen cloth, both maintained the supporting layer structure of the original excellence of screen cloth, screen cloth hydrophily and reactive thus improve matching between screen cloth and cortex can be strengthened again.In addition, add in polyamine aqueous phase solution containing amino long-chain/hyperbranched macromolecular and surfactant, active group quantity can be improved, spatial configuration of molecules can be expanded again, be conducive to aqueous phase solution to sprawl at the complete of screen surface, thus improve the object of cortex integrality and adjustment cortex cross-linked structure.
Description
Technical field
The invention belongs to preparative separation film composite material field, be specifically related to a kind of thin layer composite forward osmosis membrane and preparation method thereof, namely directly carry out thin layer composite forward osmosis membrane that interfacial polymerization obtains and preparation method in the screen surface of chemical modification.
Background technology
Water resources shortage and water quality deterioration have badly influenced life and the health of the mankind, and following peace and sustainable development are also by closely bound up with the acquisition of water purification and fresh water.How low cost realizes Water warfare and desalination becomes the Scientific And Technical Problems paid close attention to countries in the world.Positive infiltration technology arises at the historic moment just in this context.This technology relies on film both sides permeable pressure head to be the spontaneous low-pressure membrane separation process realizing Water transport of driving force at ambient pressure.Compared with counter-infiltration, positive process of osmosis has advantageous advantage: low pressure even without press operation, low energy consumption; Excellent desalting performance, low fouling membrane feature; High-recovery, zero-emission, pollution-free etc.
Forward osmosis membrane is one of core of positive infiltration technology.Mainly be divided into two classes at present, i.e. polyamide-based thin layer composite (TFC) film prepared of the cellulose acetate class forward osmosis membrane prepared of phase inversion and interfacial polymerization.The latter has unique advantage, as ultra-thin cortex, extensive chemical/heat endurance, not easily biological-degradable, can optimum organization etc. separately to supporting layer and cortex, be just day by day subject to the extensive concern of scholar.Form similar to reverse osmosis membrane, TFC forward osmosis membrane is formed in porous support layer surface recombination by ultra-thin cortex.But due to exist in porous support layer serious in concentration polarization (ICP), current commercialization and to grind forward osmosis membrane water flux general lower.Therefore, desirable forward osmosis membrane does not preferably have porous support layer to eliminate ICP phenomenon, but such film-strength is too poor, and this just needs reasonable consideration membrane structure and character, is particularly optimized supporting layer, ensures high-performance and the high strength of film simultaneously.In recent years, the supporting layer of TFC forward osmosis membrane mainly concentrates on porous milipore filter, self-supporting hollow-fibre membrane and nano fibrous membrane, improves supporting layer structure and surface nature (as hydrophily) by regulating casting solution composition, optimization film forming condition etc.But it should be noted that these improvement still do not change the present situation of " positive osmotic water flux is far below desired value ", the editor's Parker as the U.S. " desalinization Leader " draws thatch to think " main bugbear that positive infiltration technology faces finds suitable film ".
Develop a kind of TFC forward osmosis membrane containing support layer, its supporting layer had both had suitable design feature (thickness is thin, flexibility is low and porosity high), have again good chemical property (hydrophily, intensity, chemical stability and with cortex matching), significantly will certainly improve TFC forward osmosis membrane water flux, this in the further application of water treatment and even electric power, space industry, has important theory significance and actual application value for the energy-saving positive infiltration technology of development.
Summary of the invention
The invention provides a kind of net surface at chemical modification sieve and directly carry out the thin layer composite forward osmosis membrane preparation method that interfacial polymerization obtains, forward osmosis membrane prepared by the method, on the basis keeping original advantage, can effectively reduce interior concentration polarization, thus reach the target significantly improving water flux, and greatly can strengthen the combined strength bination of screen cloth supporting layer and interfacial polymerization cortex, thus improve the endurance quality of forward osmosis membrane and extend its service life, solve positive infiltration applications bottleneck problem.
Forward osmosis membrane of the present invention, its preparation method is as follows:
1) by screen cloth ethanol and deionized water alternately cleaning, low temperature drying;
Wherein, screen cloth is inorganic screen cloth and the wire mesh screens such as nickel foam and copper mesh such as organic screen cloth such as mulberry silk, polyester material, aluminium oxide and zirconia;
2) by step 1) screen cloth that processes is placed in the solution being dissolved with DOPA and/or dopamine and carries out oscillating reactions; Then alternately cleaning in ethanol and deionized water, obtains surface with the screen cloth gathering DOPA or poly-dopamine composite bed;
Wherein, the solution being dissolved with DOPA and/or dopamine described in step (2), solvent is wherein seawater, deionized water, pH be 6 ~ 10 Tris-hydrochloric acid buffer solution or ethanol mass fraction be the ethanol water of 5 ~ 40%; Described DOPA and/or dopamine solution concentration are 0.1 ~ 4.0g/L; Described concussion reaction be rotating speed be 100 ~ 200r/min, temperature is carry out 1 ~ 24h in the shaken cultivation case of 20 ~ 40 DEG C;
3) by step 2) in the surface that obtains be placed in the screen cloth of poly-DOPA or poly-dopamine composite bed and be dissolved with on polyamine aqueous phase solution, make screen cloth be positioned at aqueous phase solution surface; Then the oil-phase solution being dissolved with pyromellitic trimethylsilyl chloride is evenly introduced screen surface, after reaction, complete preparation.
Wherein, the polyamine aqueous phase solution described in step (3) is the mixed aqueous solution containing amino long-chain/hyperbranched macromolecular, m-phenylene diamine (MPD), triethylamine and surfactant;
Above-mentioned containing amino long-chain/hyperbranched macromolecular comprise polymine, amination polyethylene glycol, shitosan etc. one or more;
Above-mentioned surfactant be neopelex, dodecyl sodium sulfate, cetyl ammonium bromide etc. one or more;
Above-mentioned m-phenylene diamine (MPD) and the concentration of triethylamine in polyamine aqueous phase solution are respectively 5 ~ 30g/L and 0 ~ 30g/L;
Pyromellitic trimethylsilyl chloride oil-phase solution concentration described in step (3) is 0.5 ~ 10g/L.
The present invention adopts DOPA and/or dopamine to carry out chemical modification and modification to screen cloth, has both maintained the supporting layer structure of the original excellence of screen cloth, can strengthen again screen cloth hydrophily and reactive thus improve matching between screen cloth and cortex.In addition, add in polyamine aqueous phase solution containing amino long-chain/hyperbranched macromolecular and surfactant, active group quantity can be improved, spatial configuration of molecules can be expanded again, be conducive to aqueous phase solution to sprawl at the complete of screen surface, thus improve the object of cortex integrality and adjustment cortex cross-linked structure.The present invention has given full play to the advantage of response type screen cloth and ultra-thin cortex, obtains high flux forward osmosis membrane of new generation.
Detailed description of the invention
Preparedly in following embodiment use the NaCl of 1M as drawing liquid with during the thin layer composite forward osmosis membrane test that is supporting layer of response type screen cloth, deionized water is as material liquid.
Forward osmosis membrane of the present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
1), after 300 order polyester screen ethanol and deionized water alternately being shaken cleaning, fully infiltrate in ethanol;
2) DOPA is dissolved in 0.1g/LTris solution (pH8), and configuration concentration is the DOPA solution of 0.1g/L; Screen cloth is soaked in DOPA solution, rotating speed be 100r/min, temperature is shake 5h in the shaken cultivation case of 35 DEG C, then in ethanol and deionized water, alternately shakes cleaning;
3) carry out interfacial polymerization in poly-DOPA modification screen surface, interfacial polymerization conditions is: in polyamine aqueous phase solution, m-phenylene diamine (MPD), triethylamine concentration are 20g/L, and pyromellitic trimethylsilyl chloride oil-phase solution concentration is 1g/L, reaction 30min; Rinsed with deionized water, obtained nanofiltration separation membrane.Measure its positive permeance property, result is as follows: water flux is 12L/m
2h, salt-stopping rate is 99.1%.
The performance for stability of test membrane.Respectively film to be immersed in the HCl aqueous solution (pH=2), the NaOH aqueous solution (pH=12), NH4HCO3 solution 7 days, take out also clean with deionized water rinsing, then test its positive permeance property.Result shows, water flux respectively about 12.2,11.9 and 12L/m
2h, rejection respectively about 99.2%, 99.3% and 99.1%.As can be seen here, this film shows good resistance to acids and bases and chemical stability.
Embodiment 2
After 300 order polyester screen ethanol and deionized water are alternately shaken cleaning, fully infiltrate in ethanol; DOPA is dissolved in 0.1g/LTris solution (pH8), and configuration concentration is the DOPA solution of 0.1g/L; Screen cloth is soaked in DOPA solution, rotating speed be 100r/min, temperature is shake 5h in the shaken cultivation case of 35 DEG C, then in ethanol and deionized water, alternately shakes cleaning; Interfacial polymerization is carried out in poly-DOPA modification screen surface, interfacial polymerization conditions is: in polyamine aqueous phase solution, the concentration of m-phenylene diamine (MPD), triethylamine and polymine is respectively 20g/L, 20g/L and 1g/L, pyromellitic trimethylsilyl chloride oil-phase solution concentration is 1g/L, reaction 30min; Rinsed with deionized water, obtained nanofiltration separation membrane.Measure its positive permeance property, result is as follows: water flux is 17L/m
2h, salt-stopping rate is 99.6%.The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Embodiment 3
After 500 order polyester screen ethanol and deionized water are alternately shaken cleaning, fully infiltrate in ethanol; DOPA is dissolved in 0.1g/LTris solution (pH8), and configuration concentration is the DOPA solution of 0.1g/L; Screen cloth is soaked in DOPA solution, rotating speed be 100r/min, temperature is shake 12h in the shaken cultivation case of 35 DEG C, then in ethanol and deionized water, alternately shakes cleaning; Interfacial polymerization is carried out in poly-DOPA modification screen surface, interfacial polymerization conditions is: in polyamine aqueous phase solution, the concentration of m-phenylene diamine (MPD), triethylamine and polymine is respectively 20g/L, 20g/L and 1g/L, pyromellitic trimethylsilyl chloride oil-phase solution concentration is 1g/L, reaction 60min; Rinsed with deionized water, obtained nanofiltration separation membrane.Measure its positive permeance property, result is as follows: water flux is 20L/m
2h, salt-stopping rate is 99.4%.The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Embodiment 4
After 500 order polyester screen ethanol and deionized water are alternately shaken cleaning, fully infiltrate in ethanol; DOPA is dissolved in 0.1g/LTris solution (pH8), and configuration concentration is the DOPA solution of 0.1g/L; Nickel foam is soaked in DOPA solution, rotating speed be 100r/min, temperature is shake 5h in the shaken cultivation case of 35 DEG C, then in ethanol and deionized water, alternately shakes cleaning; Interfacial polymerization is carried out in poly-DOPA modification screen surface, interfacial polymerization conditions is: in polyamine aqueous phase solution, the concentration of m-phenylene diamine (MPD), triethylamine and polymine is respectively 20g/L, 20g/L and 5g/L, pyromellitic trimethylsilyl chloride oil-phase solution concentration is 1g/L, reaction 30min; Rinsed with deionized water, obtained nanofiltration separation membrane.Measure its positive permeance property, result is as follows: water flux is 26L/m
2h, salt-stopping rate is 99.7%.The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Embodiment 5
Be nickel foam ethanol and the deionized water alternately after concussion cleaning of 95% by porosity, fully infiltrate in ethanol; DOPA is dissolved in 0.1g/LTris solution (pH8), and configuration concentration is the DOPA solution of 0.1g/L; Nickel foam is soaked in DOPA solution, rotating speed be 100r/min, temperature is shake 5h in the shaken cultivation case of 35 DEG C, then in ethanol and deionized water, alternately shakes cleaning; Interfacial polymerization is carried out in poly-DOPA modification screen surface, interfacial polymerization conditions is: in polyamine aqueous phase solution, the concentration of m-phenylene diamine (MPD), triethylamine and polymine is respectively 20g/L, 20g/L and 1g/L, pyromellitic trimethylsilyl chloride oil-phase solution concentration is 1g/L, reaction 30min; Rinsed with deionized water, obtained nanofiltration separation membrane.Measure its positive permeance property, result is as follows: water flux is 24L/
2h, salt-stopping rate is 99.7%.The result of membrane stability test shows, water flux and rejection have no significant change, and this film shows good resistance to acids and bases and chemical stability as seen.
Reference examples 1
The positive permeance property of the commercialization thin layer composite forward osmosis membrane of test HTI company, with 1MNaCl as drawing liquid, deionized water is as material liquid.Test result is as follows: water flux is 3L/
2h, salt-stopping rate is 99.8%.
Result shows, the present invention obtain with the response type screen cloth thin layer composite forward osmosis membrane performance that is supporting layer far away higher than commercialization forward osmosis membrane performance.Such as, under same test condition, the forward osmosis membrane that the present invention obtains is under the prerequisite ensureing high salt-stopping rate (being greater than 99%), and water flux is 5 ~ 9 times of commercialization forward osmosis membrane water flux.
Reference examples 2
Screen cloth is not carried out to chemical modification and the modification of DOPA and/or dopamine.The forward osmosis membrane preparation process being supporting layer with unmodified screen cloth is as follows: after 500 order polyester screen ethanol and deionized water are alternately shaken cleaning, float on polyamine aqueous phase solution and carry out interfacial polymerization, interfacial polymerization conditions is: in polyamine aqueous phase solution, the concentration of m-phenylene diamine (MPD), triethylamine and polymine is respectively 20g/L, 20g/L and 5g/L, pyromellitic trimethylsilyl chloride oil-phase solution concentration is 1g/L, reaction 30min; Rinsed with deionized water, obtained nanofiltration separation membrane.Measure its positive permeance property, result is as follows: water flux is 13L/m
2h, salt-stopping rate is 99.5%.
Result shows, carries out chemical modification and modify the water flux that significantly can improve forward osmosis membrane to screen cloth.Comparative example 4, adopt the screen cloth of the chemical modification of DOPA and/or dopamine to be that the water flux ratio supporting the forward osmosis membrane prepared adopts unmodified screen cloth to be that the forward osmosis membrane supporting preparation exceeds more than 50%.
Claims (8)
1. a thin layer composite forward osmosis membrane, is characterized in that, the preparation method of described thin layer composite forward osmosis membrane is as follows:
1) by screen cloth ethanol and deionized water alternately cleaning, low temperature drying;
2) by step 1) screen cloth that processes is placed in the solution being dissolved with DOPA and/or dopamine and carries out oscillating reactions; Then alternately cleaning in ethanol and deionized water, obtains surface with the screen cloth gathering DOPA and/or poly-dopamine composite bed;
3) by step 2) in the surface that obtains be placed in the screen cloth of poly-DOPA and/or poly-dopamine composite bed and be dissolved with on polyamine aqueous phase solution, make screen cloth be positioned at aqueous phase solution surface; Then the oil-phase solution being dissolved with pyromellitic trimethylsilyl chloride is evenly introduced screen surface, after reaction, complete preparation;
Be dissolved with the solution of DOPA and/or dopamine in described step (2), solvent be wherein seawater, deionized water, pH be 6 ~ 10 Tris-hydrochloric acid buffer solution or ethanol mass fraction be the ethanol water of 5 ~ 40%;
In described step (3), polyamine aqueous phase solution is the mixed aqueous solution containing amino long-chain/hyperbranched macromolecular, m-phenylene diamine (MPD), triethylamine and surfactant.
2. thin layer composite forward osmosis membrane as claimed in claim 1, it is characterized in that, described screen cloth is organic screen cloth, inorganic screen cloth or wire mesh screen.
3. thin layer composite forward osmosis membrane as claimed in claim 1, it is characterized in that, described DOPA and/or the concentration of dopamine solution are 0.1 ~ 4.0g/L.
4. thin layer composite forward osmosis membrane as claimed in claim 1, is characterized in that, described step (2) concussion reaction be rotating speed be 100 ~ 200r/min, temperature is carry out 1 ~ 24h in 20 ~ 40 DEG C of shaken cultivation casees.
5. thin layer composite forward osmosis membrane as claimed in claim 1, is characterized in that, the described long-chain/hyperbranched macromolecular containing amino comprises one or more in polymine, amination polyethylene glycol, shitosan.
6. thin layer composite forward osmosis membrane as claimed in claim 1, it is characterized in that, described surfactant is one or more in neopelex, dodecyl sodium sulfate, cetyl ammonium bromide.
7. thin layer composite forward osmosis membrane as claimed in claim 1, it is characterized in that, described m-phenylene diamine (MPD) and the concentration of triethylamine in polyamine aqueous phase solution are respectively 20g/L and 20g/L.
8. thin layer composite forward osmosis membrane as claimed in claim 1, is characterized in that, in described step (3), pyromellitic trimethylsilyl chloride oil-phase solution concentration is 0.5 ~ 10g/L.
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| CN104368244B (en) * | 2014-09-24 | 2017-01-25 | 浙江大学 | Making method of catechol compound nanoparticle modified polymeric composite membrane |
| CN105032214B (en) * | 2015-09-15 | 2017-04-12 | 哈尔滨工业大学 | Forward osmotic membrane preparation method |
| CN105727768B (en) * | 2016-05-13 | 2018-07-10 | 高学理 | A kind of preparation method of the self-supporting forward osmosis membrane based on chitosan |
| CN106807249A (en) * | 2016-12-26 | 2017-06-09 | 中南大学 | A kind of interfacial polymerization forward osmosis membrane with double-deck PEEK WC as basement membrane and preparation method thereof |
| CN108854991A (en) * | 2018-04-17 | 2018-11-23 | 中国地质大学（武汉） | A kind of poly-dopamine cladding polyethylene sieve plate and its application |
| CN108771985A (en) * | 2018-06-12 | 2018-11-09 | 上海凯矜新材料科技有限公司 | A kind of complex reverse osmosis membrane and preparation method thereof |
| CN109012186A (en) * | 2018-08-24 | 2018-12-18 | 天津碧水源膜材料有限公司 | Modified reverse osmosis membrane of antipollution and preparation method thereof |
| CN110548423B (en) * | 2019-08-28 | 2022-04-01 | 陈泉学 | Modified ultrafiltration membrane and modification method thereof |
| CN110813104B (en) * | 2019-10-31 | 2021-06-08 | 北京化工大学 | Super-hydrophilic alkyne-carbon composite nanofiltration membrane and preparation method thereof |
| CN111644078A (en) * | 2020-06-03 | 2020-09-11 | 武汉纺织大学 | Polydopamine modified nanofiber coating nanofiltration membrane and preparation method thereof |
| CN113019157B (en) * | 2021-05-25 | 2021-08-06 | 中国科学院宁波材料技术与工程研究所 | Multifunctional supported nano multilayer composite film and preparation method and application thereof |
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