CN105597552B - The method that the high salt-stopping rate forward osmosis membrane of high water flux and one-step method prepare the forward osmosis membrane - Google Patents
The method that the high salt-stopping rate forward osmosis membrane of high water flux and one-step method prepare the forward osmosis membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses the methods that a kind of high salt-stopping rate forward osmosis membrane of high water flux and one-step method prepare the forward osmosis membrane, (1) sulfonated polyether sulfone, Kynoar, chitosan graphene oxide are dissolved in organic solvent according to the ratio, stirs evenly to obtain film making solution；(2) it will be scraped in polyester screen after film making solution deaeration and make nascent tablet liquid film, film-forming in coagulating bath is immersed after nascent tablet liquid film is stopped 30~50 seconds in air；(3) film after film-forming is impregnated in deionized water, until solvent all removes in film, obtains forward osmosis membrane；Sulfonated polyether sulfone, Kynoar, CS GO and organic solvent quality proportioning be：Kynoar 12 18%, sulfonated polysulfone 2 10%, 0.1 1%, organic solvent 71 86%.Preparation process of the present invention is simple, and manufacturing cost is low, and the forward osmosis membrane hydrophily being prepared by this method is strong, and antifouling property is good, all has good application value in drinking water, Industrial Wastewater Treatment etc..
Description
Technical field
The invention belongs to technical field of membrane, more particularly to a kind of preparation with high water flux, high salt-stopping rate forward osmosis membrane
Method and product
Background technology
Currently, with the high speed development of social economy, global environment problem is increasingly serious, especially the shortage of water resource
The normal life of the mankind has been seriously affected, while having constrained economic development.Current shortage of water resources and energy consumption it is excessively high at
For one of the three big hot spots of global concern.Forward osmosis membrane isolation technics is exactly to grow up under this background.
Positive infiltration (Forward osmosis, FO) is that one kind being not required to impressed pressure and does driving force, and only relies on osmotic pressure drive
Dynamic membrane separating process.Forward osmosis membrane isolation technics is exactly relative to the most significant feature of membrane separation technique that impressed pressure drives
It does not need impressed pressure or is run under very low impressed pressure, and fouling membrane situation is relatively light, it can be for a long time
Operation and need not clean.Forward osmosis membrane isolation technics at present the countries and regions such as such as U.S., Singapore, Europe
Obtain numerous studies and application.
Membrane material preparation, technology exploitation, fouling membrane are concentrated mainly on about the research just permeated and draw liquid at present
In terms of the researchs such as exploitation.The FO films of the overwhelming majority are prepared by acetate fiber or polyamide at present, and Liu Leilei etc. is with three acetic acid fibre
Dimension element is membrane material, and using Isosorbide-5-Nitrae-dioxane and acetone as solvent, lactic acid is additive, obtains preparation liquid after blending reaction, adopts
With phase inversion prepare Triafol T forward osmosis membrane (Liu Leilei, Wang Duo, Wang Meng, etc.；Triafol T forward osmosis membrane system
The research of influence factor during standby；Membrane science and technology；31(1)2011；77-83).
Wang Liguo etc. is in its patent document (Wang Liguo；Shi Xinlian；Li Yuan, etc.；A kind of high performance flat formula acetate fiber
Element/nanometer titanium dioxide blending forward osmosis membrane；Publication number CN104474920A；Publication date：One kind is disclosed in 2015-04-01)
High performance flat formula cellulose acetate/nanometer titanium dioxide blending forward osmosis membrane, preparation method are by cellulose acetate, addition
Agent, nano-titanium dioxide, graphene and dimethylformamide or dimethylacetylamide or N-Methyl pyrrolidone are mixed with acetone
Dissolving tank, stirring and dissolving to full and uniform, obtained blending forward osmosis membrane casting solution is added in solvent in certain sequence；In backing material
On with phase inversion prepare high performance flat formula cellulose acetate/nanometer titanium dioxide blending forward osmosis membrane.What it was prepared just oozes
Permeable membrane makees driving liquid with 1M NaCl, deionized water makees material liquid, and in the testing time of 1h, pure water flux reaches 17.5L/m2·h
More than, reversed flux salt is less than 3.0g/m2·h..Patent document of the Foshan Zhongrun Water Treatment Technology Co., Ltd. in its application
(Zhou Wenle, Zong Tongqiang；A kind of preparation method of compound forward osmosis membrane；Publication number CN103962015A；Publication date：
2014.08.06 a kind of preparation method of compound forward osmosis membrane is disclosed in), this method joins nanotube and Triafol T
It closes and uses, nanotube is good moisture subchannel, using its special cavity structure, improves hydrone in forward osmosis membrane
It transmits, greatly improves the water flux of positive process of osmosis, while there is the interception capacity increased to salt ion, make forward osmosis membrane
Salt-stopping rate also increase.In addition, Xue Li newly waits (Xue Lixin；Liu Fu；Ding Hui, etc.；A kind of compound acetic acid of Kynoar is fine
The preparation method of the plain forward osmosis membrane of dimension；Publication number CN102580562A；Publication date：2012-07-18) disclose a kind of poly- inclined fluorine
The preparation method of ethylene multiple cellulose acetate forward osmosis membrane, preparation method are to be configured to gather by Kynoar and additive
Vinylidene casting solution is configured to cellulose acetate casting solution with cellulose acetate, Triafol T and molecular sieve, then will
Kynoar casting solution is uniformly scraped on non-woven fabrics, and hydrophilicity kynoar micro-filtration counterdie, drying or naturally dry are obtained
Afterwards, hydrophilicity kynoar dry film is formed, then cellulose acetate casting solution is uniformly scraped in hydrophilicity kynoar dry film
On, obtain compound forward osmosis membrane.
Other than blending-phase inversion prepares forward osmosis membrane, one layer is prepared on the surface of ultrafiltration membrane using interfacial polymerization
Hydrophilic desalination layer is also a main preparation methods of forward osmosis membrane.(the He Xumin such as He Xumin；Ding Wen；Li Zhenfeng, etc.；It is a kind of
Compound forward osmosis membrane and preparation method thereof；Publication number CN103170257A；Publication date：It 2013-06-26) discloses a kind of compound
Forward osmosis membrane and preparation method thereof, the forward osmosis membrane are polysulfones-carboxylated polysulfones blending/polyamide composite film.Preparation method
It is prepared for carboxylated polysulfones for polysulfones is carried out carboxylated modification, itself and polysulfones and additive are then configured to polysulfones-carboxyl
Change polysulfones and casting solution is blended, then on a glass uniformly spread apart it, the polysulfones that hydrophilic modifying is obtained after coagulating bath is total
Mixed ultrafiltration membrane.Drying or after drying in the shade naturally, by interfacial polymerization, making m-phenylene diamine (MPD)-pyromellitic trimethylsilyl chloride polyamides on it
Amine selects layer, polyamide that can be combined with carboxylated polysulfones by ionic bond, obtains good hydrophilic property, interior concentration polarization is small, water flux
It is higher, satisfactory mechanical property, the high composite polyamide forward osmosis membrane of salt rejection rate.Xue Lixin (Xue Lixin；Sun Yuanna；Huang Yan,
Deng；A kind of preparation method of compound forward osmosis membrane；Publication number CN102728247A；Publication date：One is disclosed in 2012-10-07)
The preparation method of the compound forward osmosis membrane of kind.Preparation method is that stirring and dissolving in solvent is added in polysulfones and additive, is divided
Dissipate uniform polysulfones casting solution；It is molten for the cyclodextrin aqueous solution of 0.05~5 ﹪ and equal benzoyl chloride n-hexane to prepare mass percent
Liquid；Then finely dispersed polysulfones casting solution is scraped on non-woven fabrics with scraper, is then immersed in coagulating bath deionized water, obtains
Polysulfones ultrafiltration counterdie；Polysulfones ultrafiltration counterdie is successively immersed in cyclodextrin aqueous solution and equal benzoyl chloride hexane solution, is cured
After obtain compound forward osmosis membrane.Prepared forward osmosis membrane has very high mechanical properties, solvent resistance, higher water flux and height
Salt rejection rate.
Freeman seminars (Jason T.Arena, Seetha the S Manickama, Kevin of texas,U.S university
K.Reimund,Benny D.Freeman,Jeffrey R.McCutcheon.Solute and water transport in
forward osmosis using polydopaminemodified thin film composite
Membranes.Desalination, 343 (2014) 8-16.) it has studied poly-dopamine (PDA) modification utilized thin film composite membranes and grinds
Study carefully water and the positive permeability and separation behavior of solute, and thinks that current institute cannot be because reverse osmosis by reverse osmosis membrane for just permeating
The active layer of film is relatively hydrophobic, therefore they carry out Hydrophilic modification to reverse osmosis membrane surface layer with poly-dopamine, the results showed that with
Unmodified RO films are compared, and the positive osmotic water flux of Modified Membrane improves 4 to 6 times, achieve preferable membrane modifying effect.Lu etc.
PEG is grafted to the compound layer surface of polyamide ultrathin by people using acid chloride and PEGDE reactions, significantly improves just oozing for Modified Membrane
Water flux and contamination resistance [X.Lu, S.R.-V. Castrillon, D.L.Shaffer, J.Ma, M.Elimelech, In
situ surface chemical modification of thin-film composite forward osmosis
membranes for enhanced organic fouling resistance,Environmental Science&
Technology,47(2013) 12219-12228.].Although the positive permeation flux of composite membrane can be improved by being modified to TFC
And resistance tocrocking, but the hydrophily improved may cause the reduction of film selection selection performance.Then, many research passes through
Change TFC and supports duct hydrophily and the pore passage structure of porous counterdie to eliminate concentration polarization and improve the water flux of film.
Additionally someone uses electrostatic spinning nano fiber film made of Kynoar as FO film counterdie supporting layers
[M.Tian,C.Qiu,Y.Liao,S.Chou,R.Wang,Preparation of polyamide thin film
composite forwardosmosis membranes using electrospunpolyvinylidene fluoride
(PVDF)nanofibers as substrates, Separation and Purification Technology,118
(2013) 727-736.], hence it is evident that the influence of inner wall concentration polarization is reduced, but between nanofiber supporting layer and activity TFC
The compound performance that can significantly affect film.
Membrane material preparation, technology exploitation, fouling membrane are concentrated mainly on about the research just permeated and draw liquid at present
In terms of the researchs such as exploitation.The FO films of the overwhelming majority are by acetate fiber or polyamide FO films at present.But acetate fiber FO films
Rejection, flux and corrosion resistance etc. are all unsatisfactory, although and the rejection and stability of polyamide FO composite membranes satisfaction are wanted
It asks, but since the factors such as fouling membrane and interior concentration polarization cause flux that can not be researched and developed compared with pressure drive membrane
Forward osmosis membrane with excellent properties has great importance.
Invention content
The method that the present invention provides a kind of high salt-stopping rate forward osmosis membrane of high water flux and one-step method prepares the forward osmosis membrane, just
Permeable membrane good hydrophilic property, permeation flux are big, and all show good performance on antipollution and salt-stopping rate.
A kind of high salt-stopping rate forward osmosis membrane of high water flux, film making solution is coated in polyester screen and is made, with quality percentage
Than meter, the film making solution is made by following raw material：
Kynoar 12-18%
Sulfonated polysulfone 2-10%
Organic solvent 71-86%.
Preferably, the chitosan-graphene oxide for being also 0.1~1% containing mass percent in the film making solution is received
Rice modifying agent, i.e. film making solution are made by following raw material by percentage to the quality：
Kynoar (PVDF) is that a kind of heat resistance is high, chemical stability is good, engineering properties is stable and filming performance
Excellent special engineering plastics, there is vast potential for future development.Although however, PVDF have good physical and chemical performance, but still
Have the shortcomings that membrane material hydrophily is poor.By the way that PVDF to be blended with the polymer with hydrophile function, it can both retain PVDF
The original excellent performance of membrane material, and improve the hydrophily of film.
The present invention selects sulfonated polysulfone (SPS) as PVDF hydrophilic modifiers, and SPS is by being obtained after the sulfonated reaction of polysulfones
It arrives.PVDF is blended to the forward osmosis membrane prepared with SPS not only has good hydrophily, but also with the selection of more good proton
Permeability.Since SPS hydrophilies are too strong, when shared mass ratio is excessively high in casting film material for it, cause film forming is made to be deteriorated, because
This cannot be excessively added.Simultaneous selection of the present invention adds a small amount of chitosan-stannic oxide/graphene nano modifying agent as another function
Modifying agent makes the hydrophily of film further increase, and osmotic efficiency is improved again.The present invention uses sulfonated polysulfone and chitosan-oxygen
For graphite alkene nano modifier collectively as hydrophilic agent, sulfonated polysulfone plays main resistance salt, hydrophilic interaction, and CS-GO is further increased
The hydrophilic resistance salt action of film, two kinds of hydrophilic agent roles are mutually promoted, common resistance salt, the hydrophilic interaction for improving film.
Preferably, the sulfonation degree of the sulfonated polysulfone is 10%-40%, and molecular weight is 30,000-50 ten thousand.
It is further preferred that film making solution is made by following raw material by percentage to the quality：
The film pure water flux being prepared with the optimization formula is up to 20L/m2H or more, reversed flux salt are less than 5.0g/
m2·h。
The raw material components of film making solution are most preferably：
The pure water flux for the forward osmosis membrane being prepared by the film making solution of the preferred ingredient is up to 23L/m2H or more,
Reversed flux salt is less than 5.0g/m2·h。
It is above-mentioned be most preferably formulated under when the sulfonation degree of sulfonated polysulfone is preferably 40%, the forward osmosis membrane that is prepared
Pure water flux is up to 27L/m2H or more, reversed flux salt are less than 3.0g/m2·h。
Preferably, the number-average molecular weight of the Kynoar is 1 × 105-2×106。
The chitosan-stannic oxide/graphene nano modifying agent (CS-GO) can be prepared by existing known method, it is preferable that
The chitosan-stannic oxide/graphene nano modifying agent (CS-GO) by under alkaline condition, by graphene oxide carboxyl with
Amino in chitosan carries out condensation reaction and prepares.For the molecular weight of chitosan 50,000 or more, deacetylation is more than 90%.Instead
The mass values of chitosan and graphene oxide are 3 during answering:1.
The preparation method of chitosan-stannic oxide/graphene nano modifying agent is preferably：Commercialization graphene oxide (GO) is added
Enter into deionized water, ultrasonic disperse 2h, 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride is then added
(EDCHCl) and n-hydroxysuccinimide (NHS), 1h is continuously stirred, then by chitosan (CS) solution with 0.15ml/min
Speed be added in GO dispersion liquids, in 60 DEG C react 1h, centrifuged after being cooled to room temperature, the mass ratio between each reactive material
GO/EDCHCl/NHS/CS=1:2:1:3, then with the NaOH aqueous solutions and deionized water of 0.5mol/L wash for several times until
PH is about the graphene oxide modifying agent (GO-CS) that 7.0,40 DEG C of vacuum drying can be obtained the modification of chitosan macromolecular.It is preferred that
Ground, the organic solvent are dimethyl sulfoxide, N- methyl pyrrolidones, n,N-Dimethylformamide and n,N-dimethylacetamide
At least one of.Most preferably N- methyl pyrrolidones.
Preferably, the sulfonated polysulfone is commercial prod, and sulfonation degree 10%-40%, number-average molecular weight is 30,000-
500000.
The Kynoar is commercial prod, and number-average molecular weight is 1 × 105-2×106。
The present invention also provides a kind of preparation methods of the high high salt-stopping rate forward osmosis membrane of water flux, include the following steps：
(1) sulfonated polyether sulfone, Kynoar, CS-GO are dissolved in organic solvent according to the ratio, stirs evenly to obtain film
Solution；
(2) it will be scraped in polyester screen after gained film making solution deaeration and make nascent tablet liquid film, nascent tablet liquid film is existed
Film-forming in coagulating bath is immersed after being stopped 30~50 seconds in air；
(3) film after film-forming is impregnated in deionized water, until solvent all removes in film, obtains forward osmosis membrane.
Forward osmosis membrane of the present invention has polyester screen as inner supporting structure, makes it have good mechanical property
Can, forward osmosis membrane service life is increased significantly.Forward osmosis membrane preparation method forms a film for one-step method simultaneously, easy to operate, makes into
This reduction.Prepared forward osmosis membrane good hydrophilic property, permeation flux are big, and are all shown very well on antipollution and salt-stopping rate
Performance.The mesh number of the polyester screen is 150~220 mesh.
Mixing time is 6-12 in step (1), and whipping temp is 60~70 DEG C；Preferably, it is stirred 8 hours at 60 DEG C.
The mixing time is not less than 6 hours, and uniform molding solution was more difficult to get less than 6 hours, can influence the uniformity of film.Institute
The whipping temp stated is preferably 50 DEG C to 70 DEG C, and at such a temperature, sulfonated polysulfone, Kynoar and organic solvent can be very fast
Be uniformly mixed.
The deaeration is handled：Preparation liquid stands 12-24h under 40-60 DEG C of constant temperature；Preferably, in 60 DEG C of perseverances
12h is stood under the conditions of temperature；The composition that constant temperature is conducive to preparation liquid is selected to keep so that property.
It scrapes that make blade thickness used in nascent tablet liquid film be preferably 80um or less thickness in polyester screen, makes prepared
Forward osmosis membrane thickness is small, has preferable permeability.
Obtained nascent liquid film stops 30-50 seconds in air, and main purpose is the surface texture of the nascent liquid film of optimization, is subtracted
The striking trace on nascent tablet liquid film surface less, the operation carry out in 20-30 DEG C, the air that relative humidity is 40-80%；Institute
The residence time stated is unsuitable long, and the residence time organic solvent on long nascent liquid film surface is readily volatilized, influences nascent liquid film
Surface texture.
The coagulating bath is deionized water or organic solvent, and the temperature of coagulating bath is 20-50 DEG C；Preferably gone at 30 DEG C from
Film-forming in sub- water.Most of organic solvent, which is dissolved into coagulating bath, in solidification process, in film removes.
Coating thickness of the film making solution in polyester screen is as thin as possible, it is preferable that nascent tablet liquid film (i.e. liquid film+gather
Ester sieve) thickness be 80~100um, the thickness for the positive osmosis composite membrane of finished product being prepared is generally 75-95um.
Film after film-forming impregnates at least three days time in deionized water, ensures the solvent in film completely from film
Middle removal.Meanwhile remaining a small amount of organic solvent I can also be dissolved in deionization liquid and remove in the film after film-forming.
Preparation film is blended using sulfonated polysulfone and CS-GO as hydrophilic charged functional modifier in it by the present invention with PVDF
Liquid is support frame by solution phase inversion using polyester screen, and the film being prepared is plate compounding forward osmosis membrane.CS-GO
For nano-hydrophilic modifying agent as modifying agent, the amino, the hydroxyl that dissociate in chitosan in film-forming process can be with the sulphurs in sulfonated polysulfone
Acid groups are combined together in the form of chemical combination key, will not be detached from away from film after film forming.It is obtained in this way just to ooze
Saturating composite membrane has good water flux and higher salt-stopping rate.
The preparation method of the forward osmosis membrane of the high resistance tocrocking of the present invention, preparation process is simple, and manufacturing cost is low, by the party
The forward osmosis membrane hydrophily that method is prepared is strong, and antifouling property is good, all has very in drinking water, Industrial Wastewater Treatment etc.
Good application value.
Description of the drawings
Fig. 1 a~Fig. 1 d are the section and surface electromicroscopic photograph of forward osmosis membrane prepared in embodiment 6.
Specific implementation mode
The present invention is described in more detail below in conjunction with following examples, but the example is not constituted to the present invention's
Limitation.
The characterizing method used in following embodiments mainly has：
The surface topography of film：It is measured using scanning electron microscope (SEM, Holland, Phenom G2pro).
Film permeation flux measures：By the special forward osmosis membrane test device in laboratory to the water flux of forward osmosis membrane and reversely
Flux salt is measured, and using 0.5mol/L Na2SO4Aqueous solution is as driving liquid.The water flux of forward osmosis membrane is according to formula
(1) can calculate the unit interval, elementary membrane effective area by water flux.
In formula：JwFor positive osmotic water flux, L/m2h；Δ m is the value added for drawing liquid quality, kg；ρ is the density of pure water,
kg/m3；S is positive infiltration effective area, m2；T is time, h.
Reversed flux salt can calculate the unit interval according to formula (2) in film process of osmosis, and elementary membrane effective area is logical
The reverse phase flux salt crossed.
J in formulasFor reverse phase flux salt, g/m2h；C is to draw salinity in liquid, can be obtained by conductivity reckoning, mol/L, V are
Draw liquid accumulates after running the t times；MNaClFor the relative molecular mass of sodium chloride；S is positive infiltration effective area, m2；T is the time,
h。
Embodiment 1
Sulfonated polysulfone (SPS, sulfonation degree 10%) and Kynoar are dissolved in and have been put into solvent dimethyl sulfoxide (DMSO)
Three-necked flask in, then stirred 5 hours at 50 DEG C.In the step, the Material Percentage of input is calculated by mass percentage
For：PVDF/SPS/DMAc=12/10/80.By preparation liquid at 40 DEG C discontinuous degassing 12 hours, then used in polyester screen
The nascent tablet liquid film of scraper striking, and stop at room temperature 30 seconds, then nascent liquid film is immersed solid in 20 DEG C of deionized water
It is melted into film.Continue to impregnate in deionized water 2 days after film solidification, so that remaining solvent removes.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.
Embodiment 2
Sulfonated polyether sulfone (SPES, sulfonation degree 15%), CS-GO modifying agent and Kynoar are dissolved in and have been put into N- bis-
It in the three-necked flask of methylacetamide (DMAc), is then stirred 10 hours at 60 DEG C, in the step, by mass percentage
Calculating the Material Percentage put into is：PVDF/SPS/CS-GO/DMAc=18/5/0.1/82.5.Preparation liquid is static at 60 DEG C
Then deaeration 12 hours is used the nascent tablet liquid film of scraper striking in polyester screen, and is stopped at room temperature 50 seconds, then will
Film-forming in the deionized water of nascent 50 DEG C of liquid film immersion.It is small that film after solidification is soaked in 2% glutaraldehyde acidic aqueous solution 2
When, the film after crosslinking curing continues to impregnate 2 days in deionized water, so that remaining solvent removes.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.
Embodiment 3
Sulfonated polyether sulfone (SPES, sulfonation degree 18%), CS-GO modifying agent and Kynoar are dissolved in and have been put into N- bis-
In the three-necked flask of methylformamide (DMF) DMAc, then stirred in 12 hours steps at 60 DEG C, by mass percentage
Calculating the Material Percentage put into is：PVDF/SPS/CS-GO/DMAc=15/5/0.3/79.5.Preparation liquid is static at 60 DEG C
Then deaeration 24 hours is used the nascent tablet liquid film of scraper striking in polyester screen, and is stopped at room temperature 40 seconds, then will
Film-forming in the deionized water of nascent 30 DEG C of liquid film immersion.Continue to impregnate in deionized water 2 days after film solidification, so that residual
Solvent removal.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.
Embodiment 4
Sulfonated polyether sulfone (SPES, sulfonation degree 20%), CS-GO modifying agent and Kynoar are dissolved in and have been put into DMAc
Three-necked flask in, then stirred 8 hours at 60 DEG C.In the step, the Material Percentage of input is calculated by mass percentage
For：PVDF/SPS/CS-GO/DMAc=15/5/0.5/79.5.By preparation liquid at 60 DEG C discontinuous degassing 24 hours, then exist
The nascent tablet liquid film of scraper striking is used in polyester screen, and is stopped at room temperature 40 seconds, and nascent liquid film is then immersed 30 DEG C
Film-forming in deionized water.Film after solidification continues to impregnate 2 days in deionized water, so that remaining solvent removes.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.
Embodiment 5
Sulfonated polyether sulfone (SPES, sulfonation degree 30%), CS-GO modifying agent and Kynoar are dissolved in and have been put into DMAc
Three-necked flask in, then stirred 8 hours at 60 DEG C.In the step, the Material Percentage of input is calculated by mass percentage
For：PVDF/SPS/CS-GO/DMAc=15/8/0.5/76.5.By preparation liquid at 60 DEG C discontinuous degassing 12 hours, then exist
The nascent tablet liquid film of scraper striking is used in polyester screen, and is stopped at room temperature 40 seconds, and nascent liquid film is then immersed 30 DEG C
Film-forming in deionized water.Film after solidification continues to impregnate 2 days in deionized water, so that remaining solvent removes.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.
Embodiment 6
Sulfonated polyether sulfone (SPES, sulfonation degree 40%) CS-GO modifying agent and Kynoar are dissolved in and have been put into N- first
In the three-necked flask of base pyrrolidone (NMP), then stirred 8 hours at 60 DEG C.In the step, throwing is calculated by mass percentage
The Material Percentage entered is：PVDF/SPS/CS-GO/DMAc=15/5/0.5/79.5.By preparation liquid at 60 DEG C discontinuous degassing
12 hours, the nascent tablet liquid film of scraper striking is then used in polyester screen, and stop 40 seconds at room temperature, then will come into being
Film-forming in the deionized water of 30 DEG C of liquid film immersion.Film after solidification continues to impregnate 2 days in deionized water, so that remaining
Solvent removes.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.The forward osmosis membrane so obtained breaks
As illustrated in figs. 1A and ib, surface electromicroscopic photograph is as shown in Fig. 1 c and Fig. 1 d for face electromicroscopic photograph.
Embodiment 7
Sulfonated polyether sulfone (SPES, sulfonation degree 20%) and Kynoar are dissolved in the three-necked flask for being put into DMAc
In, then stirred 8 hours at 60 DEG C.In the step, the Material Percentage that input is calculated by mass percentage is：PVDF/
SPS/CS-GO/DMAc=15/5/0.8/79.2.By preparation liquid at 40 DEG C discontinuous degassing 24 hours, then in polyester screen
It is come into being tablet liquid film, and stopped at room temperature 40 seconds with scraper striking, then immersed nascent liquid film in 30 DEG C of deionized water
Film-forming.Film after solidification continues to impregnate 2 days in deionized water, so that remaining solvent removes.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.
Embodiment 8
Sulfonated polyether sulfone (SPES, sulfonation degree 20%), CS-GO modifying agent and Kynoar are dissolved in and have been put into DMAc
Three-necked flask in, then stirred 8 hours at 60 DEG C.In the step, the Material Percentage of input is calculated by mass percentage
For：PVDF/SPS/CS-GO/DMAc=15/2/1/82.By preparation liquid at 60 DEG C discontinuous degassing 12 hours, then in polyester
Come into being tablet liquid film with scraper striking on sieve, and stop 40 seconds at room temperature, then by nascent liquid film immerse 30 DEG C go from
Film-forming in sub- water.Film after solidification continues to impregnate 2 days in deionized water, so that remaining solvent removes.
The forward osmosis membrane permeation flux so obtained and section salt performance are shown in table 1.
Forward osmosis membrane preparation liquid ingredient and film properties in 1 embodiment of table
As shown in Table 1, positive osmosis composite membrane made from the application has good water flux and higher salt-stopping rate, leads to
Crossing formula can preferably make the film pure water flux being prepared reach 20L/m2H or more, reversed flux salt are less than 5.0g/m2·h。
The foregoing is merely the specific implementation cases of patent of the present invention, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of patent of the present invention, made by changes or modifications all cover in the present invention
Among the scope of the claims.
Claims (4)
1. a kind of high salt-stopping rate forward osmosis membrane of high water flux, which is characterized in that film making solution is coated in polyester screen and is made, with
Mass percent meter, the film making solution are made by following raw material：
The sulfonation degree of the sulfonated polysulfone is 10%-40%, and molecular weight is 30,000-50 ten thousand；
Preparation method is as follows：
(1) sulfonated polysulfone, Kynoar, chitosan-stannic oxide/graphene nano modifying agent are dissolved in organic solvent according to the ratio
In, 50~70 DEG C of stirring 6-12h obtain film making solution；
(2) it will be scraped in polyester screen after gained film making solution deaeration and make nascent tablet liquid film, the thickness of nascent tablet liquid film is
80~100um immerses film-forming in coagulating bath after stopping nascent tablet liquid film in air 30~50 seconds；The coagulating bath
Temperature for deionized water or organic solvent, coagulating bath is 20-50 DEG C；
(3) film after film-forming is impregnated in deionized water, until solvent all removes in film.
2. the high salt-stopping rate forward osmosis membrane of high water flux according to claim 1, which is characterized in that the number of the Kynoar
Average molecular weight is 1 × 105-2×106。
3. the high salt-stopping rate forward osmosis membrane of high water flux according to claim 1, which is characterized in that the chitosan-oxidation stone
Black alkene nano modifier preparation method is as follows：Under alkaline condition, by the amino in the carboxyl and chitosan in graphene oxide
It carries out condensation reaction and obtains.
4. the high salt-stopping rate forward osmosis membrane of high water flux according to claim 1, which is characterized in that the organic solvent is diformazan
At least one of sulfoxide, N- methyl pyrrolidones, n,N-Dimethylformamide and n,N-dimethylacetamide.
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| CN105903359A (en) * | 2016-06-06 | 2016-08-31 | 西北大学 | Chitosan functionalized graphene oxide/polyvinylidene fluoride hybrid ultrafiltration membrane and preparation method thereof |
| CN109304103B (en) * | 2017-07-28 | 2021-11-02 | 中国科学院宁波材料技术与工程研究所 | Loose type high-flux seawater desalination membrane and preparation method and application thereof |
| CN109603590A (en) * | 2019-01-04 | 2019-04-12 | 清大国华环境集团股份有限公司 | Nano modification film formulation and preparation method thereof is blended in a kind of high throughput pollution-resistant |
| CN110772993B (en) * | 2019-09-20 | 2023-12-05 | 浙江工业大学 | Method for preparing graphene oxide/modified titanium dioxide composite nanofiltration membrane through multi-effect coupling and application of graphene oxide/modified titanium dioxide composite nanofiltration membrane in dye desalination |
| CN110841494A (en) * | 2019-11-22 | 2020-02-28 | 吾净科技(深圳)有限公司 | Amphoteric composite forward osmosis membrane and preparation method and application thereof |
| CN111229059A (en) * | 2020-01-16 | 2020-06-05 | 郑州大学 | Cyclodextrin grafted anglerite nanotube organic solvent nanofiltration membrane and preparation method thereof |
| CN113318602B (en) * | 2021-05-17 | 2022-04-26 | 江苏大学 | Preparation method and application of three-dimensional macroporous PVDF (polyvinylidene fluoride) -based anti-fouling molecular imprinting membrane |
| CN113304628B (en) * | 2021-06-04 | 2022-11-01 | 徐州禹慧环境科技研究院有限公司 | Preparation method of anti-pollution nano composite hollow fiber membrane |
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