CN107469644A - A kind of nanofiltration membrane and preparation method thereof - Google Patents
A kind of nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN107469644A CN107469644A CN201710804418.1A CN201710804418A CN107469644A CN 107469644 A CN107469644 A CN 107469644A CN 201710804418 A CN201710804418 A CN 201710804418A CN 107469644 A CN107469644 A CN 107469644A
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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
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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
- B01D67/0002—Organic membrane manufacture
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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
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
The invention provides a kind of nanofiltration membrane, including：Basement membrane, is arranged on the separating layer of membrane surface, and the separating layer is prepared by aminated compounds and acyl chloride compound.Compared with prior art, nanofiltration membrane provided by the invention can realize the Selective Separation of single multi- valency ion in electrodialytic process, ion transport resistance in film is smaller, flux is high, the molecule cross-link structure of separating layer can be adjusted using the aminated compounds of different structure, obtain the consistency surface separation layer different with surface charge amount.The preparation method of nanofiltration membrane provided by the invention is simple and convenient, and obtained nanofiltration membrane limiting current density is high, has higher selectivity to single multi- valency cation and single multi- valency anion in electrodialytic process.Present invention also offers a kind of preparation method of nanofiltration membrane and electrodialysis plant.
Description
Technical field
The present invention relates to single multivalence Selective Separation technical field of membrane, more particularly to a kind of nanofiltration membrane and its preparation side
Method.
Background technology
Electrodialysis is a kind of isolation technics based on film, and ion is reached under electric field action by cationic membrane and anionic membrane
To different compartments, so as to for separating electrically charged in solution and neutral composition.Electrodialysis desalinization, wastewater treatment and
There is important application, electrodialysis has good compatibility, ease for operation, flexibility, without locating before progress in chemicals production
Manage and fouling membrane is relatively low.With the continuous development of electrodialytic technique, the transmission of specific ion is by original in electrodialytic process
Carry out more attention, the separation of single multi- valency ion turns into the focus of the development of electrodialysis in recent years because being with a wide range of applications.
As the central factor in electrodialytic process, the performance of ionic membrane is directly connected to separative efficiency and energy consumption.
Traditional ionic membrane has preferable separating effect to different electrical charge ions, for electrical different price of the same race
The ion selectivity of state is poor.The separation principle of single multi- valency ion selectivity seperation film of the prior art is concentrated mainly on size
Screening, Coulomb repulsion and hydrophobe difference etc., preparation method is generally surface coating, electrostatic precipitation, LBL self-assembly, thing
Reason or chemical method carry out surface grafting etc..LBL self-assembly is such as carried out and shape on commercial cationic film surface by Electrostatic Absorption
Into single polyvalent cation seperation film, concrete mode is that the films of Nafion 115 are immersed in poly- (the propylene amine salt of lotus positive electricity successively
Hydrochlorate) with bear electricity poly- (4- SSSs) solution in.In electrodialytic process, cation passes through under electric field action
Multiple Coulomb repulsion and reach high selectivity.But the film has the characteristic of facile hydrolysis, institute can be steady in electrodialytic process
Surely the working current density to work is very low, and flux is also extremely low, poor for the selection separation property of single multi- valency ion.
A kind of Chinese patent " electric nanofiltration device for being used for one/multivalent ion Selective Separation " (application number：
2015100301963) it first reported and carry out single polyvalent cation separation using electric nanofiltration device.But patent is not filtered to susceptance and filled
The middle nanofiltration membrane used is put to be defined.Nanofiltration membrane belongs to one kind of single multivalence selective diffusion barrier, it is characterised in that should
Film is made up of perforated substrate and separating layer, and separating layer is not charged or the minimal amount of electric charge of lotus.In electrodialytic process, separating layer
Sieved by size, Coulomb repulsion and hydrophobe difference are sieved to single multivalent ion, perforated substrate then reduces ion
Transport resistance, increase flux.
The content of the invention
In view of this, it is an object of the invention to provide a kind of nanofiltration membrane and preparation method thereof, electricity provided by the invention
NF membrane has preferable single multi- valency ion selectivity.
The invention provides a kind of nanofiltration membrane, including：
Basement membrane；
The separating layer of membrane surface is arranged on, the separating layer is prepared by aminated compounds and acyl chloride compound.
Preferably, the aminated compounds is selected from one kind in the aminated compounds with polyamino group or several
Kind, one kind for being more preferably selected from ethylenediamine, diethylenetriamine, TEPA, polyethyleneimine, propane diamine and hexamethylene diamine or
It is several.
Preferably, the one kind or several of the acyl chloride compound in the acyl chloride compound with more acid chloride groups
Kind, the one or more being more preferably selected from the formyl chloride of 1,3,5- benzene three, sebacoyl chloride and paraphthaloyl chloride.
Preferably, the basement membrane is porous charged membrane.
The invention provides a kind of preparation method of the nanofiltration membrane described in above-mentioned technical proposal, including：
Using inversion of phases, electrostatic spinning, pulling method, Thermal inactive, additive pore-creating, exchange of solvent pore-creating or electric wire
Basement membrane is prepared in radiation etching method；
The basement membrane is immersed in the aminated compounds aqueous solution and then dried, then immerses the organic solution of acyl chloride compound
In reacted, obtain nanofiltration membrane.
Preferably, the mass concentration of the aminated compounds aqueous solution is 0.5~5%.
Preferably, the mass concentration of the organic solution of the acyl chloride compound is 0.1~5%.
Preferably, the organic solvent in the organic solution of the acyl chloride compound is and water is immiscible volatile has
Solvent, it is more preferably selected from n-hexane, toluene or tetrachloromethane.
Preferably, the time that the basement membrane is immersed in the aminated compounds aqueous solution is 3~180 minutes；
The time for immersing the organic solution of acyl chloride compound is 30~3600 seconds.
Preferably, the temperature of the reaction is 10~50 DEG C.
Compared with prior art, the electrodialysis plant that nanofiltration membrane provided by the invention is prepared can both carry out it is single/
The separation of polyvalent cation, can also carry out the separation of single multi- valency anion, and the separation selectivity to sodium ion and magnesium ion is
3.1, higher than commercially available business single multi- valency cation selective seperation film CSO (selectivity 1.6), to chlorion and sulfate radical
Separation selectivity is 27, (is selectively far above commercially available business single multi- anion selectivity seperation film Neosepta ACS
7.56)。
Moreover, the preparation method of nanofiltration membrane provided by the invention can be by using the aminated compounds pair of different structure
The molecule cross-link structure of separating layer is adjusted, and obtains the consistency surface separation layer different with surface charge amount, regulative mode
It is simple and convenient, and the physicochemical characteristic metering system of nanofiltration membrane is reliably easy.
In addition, handed over present invention preferably employs charged perforated membrane as basement membrane, ion of the basement membrane with lotus positive electricity or bear electricity
Transport resistance of the ion in film can be reduced by changing group, improve flux.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is separation Na provided in an embodiment of the present invention+/Mg2+Electrodialysis plant structural representation；
Fig. 2 is separation Cl provided in an embodiment of the present invention-/SO4 2-Electrodialysis plant structural representation；
Fig. 3 is the profile scanning electron microscopic picture for the nanofiltration membrane that the embodiment of the present invention 1 is prepared；
Fig. 4 is the profile scanning electron microscopic picture for the nanofiltration membrane that the embodiment of the present invention 1 is prepared；
Fig. 5 is the profile scanning electron microscopic picture for the nanofiltration membrane that the embodiment of the present invention 7 is prepared；
Fig. 6 is the nanofiltration membrane atomic force microscope images that the embodiment of the present invention 1 is prepared；
Fig. 7 is the nanofiltration membrane that the embodiment of the present invention 1, embodiment 6 and embodiment 7 are prepared and polyacrylonitrile basement membrane
Zeta potential figure；
Fig. 8 is the current -voltage curve for the nanofiltration membrane that the embodiment of the present invention 1, embodiment 6 and embodiment 7 are prepared.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
The invention provides a kind of nanofiltration membrane, including：
Basement membrane；
The separating layer of membrane surface is arranged on, the separating layer is prepared by aminated compounds and acyl chloride compound.
In the present invention, the thickness of the basement membrane is preferably 20 μm~500 μm, more preferably 50~400 μm, is more preferably
100~300 μm, most preferably 150~250 μm.In the present invention, the basement membrane is preferably porous charged membrane, such as lotus positive electricity or
The perforated membrane of bear electricity.The present invention both directly can prepare basement membrane using charged polymer makes basement membrane charged, it is possible to use non-lotus
The polymer of electricity prepares basement membrane, is then modified by physics or chemical method, makes basement membrane charged.In the present invention, institute
It can be hydrolysis, grafting or crosslinking to state modified method.
The invention provides a kind of preparation method of the nanofiltration membrane described in above-mentioned technical proposal, including：
Using inversion of phases, electrostatic spinning, pulling method, Thermal inactive, additive pore-creating, exchange of solvent pore-creating or electric wire
Basement membrane is prepared in radiation etching method；
The basement membrane is immersed in the aminated compounds aqueous solution and then dried, then immerses the organic solution of acyl chloride compound
In reacted, obtain nanofiltration membrane.
In the present invention, the basement membrane can be made by inversion of phases, electrostatic spinning, pulling method, Thermal inactive, additive
A variety of methods such as hole, exchange of solvent pore-creating or electronics beta radiation etching method are prepared, and preferably pass through inversion of phases or electrostatic spinning
Method be prepared.In the present invention, preparing basement membrane by the method for inversion of phases is preferably：
First polymer is dissolved in the first solvent and obtains coating liquid；
It is immersed in again in water after during coating liquid immersion precipitation is bathed, obtains basement membrane.
In the present invention, the mass concentration of first polymer is preferably 15~30% in the coating liquid, and more preferably 20
~25%.In the present invention, the first polymer is preferably selected from one in polyacrylonitrile, Kynoar and sulfonated polyether sulfone
Kind is several.In the present invention, first solvent is preferably selected from N, N- dimethylformamides, dimethyl sulfoxide (DMSO) and N, N- dimethyl
One or more in acetamide.In the present invention, the coagulation bath is the poor solvent of first polymer, by Polymer Solution
Into after coagulation bath, high molecular polymer quickly separates out at interface, forms very thin compacted zone, and is formed below in compacted zone more
Aperture layer.In the present invention, the coagulation bath is preferably selected from deionized water, isopropanol, normal propyl alcohol, ethanol etc..
In the present invention, preparing basement membrane by method of electrostatic spinning is preferably：
Second polymer is dissolved in the second solvent, obtains polymer solution；
Polymer solution is sprayed by electrostatic spinning and cleaved, basement membrane is formed by fiber alignment.
In the present invention, the mass concentration of second polymer is preferably 10~40% in the polymer solution, more preferably
For 15~35%, most preferably 20~30%.In the present invention, the second polymer be preferably selected from nylon (such as nylon66 fiber),
One or more in sulfonated poly (phenylene oxide), quaternary ammoniated polyphenylene oxide and brominated polyphenylether.In the present invention, second solvent is preferred
Selected from N,N-dimethylformamide, dimethyl sulfoxide (DMSO) or DMAC N,N' dimethyl acetamide etc..
In the present invention, the electrostatic spinning preferably uses electrospinning device, in the injection apparatus of electrospinning device
Ten thousand volts of electrostatic field is applied between reception device, jet is formed from the cone end of spinning solution, and is stretched in the electric field, most
Form the nanofiber of nonwoven state on the reception device eventually.
In the present invention, the first polymer and second polymer both can be charged polymer, as sulfonated poly (phenylene oxide),
Quaternary ammoniated polyphenylene oxide, sulfonated polyether sulfone or polyacrylic acid, or uncharged polymer, as nylon (nylon66 fiber), polyamides are sub-
Amine, polyacrylonitrile or Kynoar.
In the present invention, the water that the aminated compounds aqueous solution uses is preferably deionized water, the aminated compounds
The mass concentration of the aqueous solution is preferably 0.5~5%, more preferably 1~4%, most preferably 2~3%.In the present invention, it is described
The organic solvent used in the organic solution of acyl chloride compound be preferably selected from one kind in n-hexane, toluene and tetrachloromethane or
It is several；The mass concentration of the organic solution of the acyl chloride compound is preferably 0.1~5%, and more preferably 0.5~4%, it is optimal
Elect 1~3% as.
In the present invention, the aminated compounds be preferably selected from one kind in the aminated compounds with polyamino group or
One kind that are several, being more preferably selected from ethylenediamine, diethylenetriamine, TEPA, polyethyleneimine, propane diamine and hexamethylene diamine
It is or several.In the present invention, the acyl chloride compound is preferably selected from one in the acyl chloride compound with more acid chloride groups
Kind or several, the one or more being more preferably selected from the formyl chloride of 1,3,5- benzene three, sebacoyl chloride and paraphthaloyl chloride.
In the present invention, the time that the basement membrane immerses the aminated compounds aqueous solution is preferably 3~180 minutes, more preferably
For 10~100 minutes, most preferably 30~60 minutes.In the present invention, the organic solution for immersing acyl chloride compound
Time is preferably 30~3600 seconds, more preferably 100~3000 seconds, most preferably 1000~2000 seconds.
In the present invention, the reaction is interface polymerization reaction, and reaction raw materials are acyl chloride compound and aminated compounds,
Reaction occurs on the surface of the interface of organic solvent and the aqueous solution, that is, basement membrane, and the reaction time is shorter, has from suppression effect
Fruit, form cross-linked structure.In the present invention, the temperature of the reaction is preferably 10~50 DEG C, more preferably 20~40 DEG C, optimal
Elect 30 DEG C as.In the present invention, after the completion of the reaction, preferably obtained reaction product is dried, obtains nanofiltration membrane.
Present invention also offers a kind of electrodialysis plant, including the nanofiltration membrane described in above-mentioned technical proposal.
In the present invention, the electrodialysis plant is preferably the compartment systems of electrodialysis four, as shown in figure 1, Fig. 1 is the present invention
The structural representation for the electrodialysis plant that embodiment provides, anode is followed successively by from the compartment where the compartment to negative pole where positive pole
Room (compartment 1), diluting compartment (compartment 2), enriched chamber (compartment 3) and cathode chamber (compartment 4), set between the anode chamber and diluting compartment
Anionic membrane is equipped with, the nanofiltration membrane described in above-mentioned technical proposal, the concentration are provided between the diluting compartment and enriched chamber
Anionic membrane is provided between room and cathode chamber.In the present invention, can be to Na using this electrodialysis plant+And Mg2+Carry out
Selectivity test, effective membrane area of the anionic membrane and nanofiltration membrane is preferably 7~7.5cm2, compacted zone towards positive pole,
The current density used is preferably 13~15mA cm-2, 0.1mol/L NaCl and 0.1mol/L are provided with diluting compartment
MgCl2Mixed solution, the enriched chamber is provided with 0.01mol/L KCl solution, and the anode chamber and cathode chamber are provided with
0.3mol/L Na2SO4Solution.
In the present invention, the electrodialysis plant is preferably the compartment systems of electrodialysis four, as shown in Fig. 2 Fig. 2 is the present invention
The structural representation for the electrodialysis plant that embodiment provides, anode is followed successively by from the compartment where the compartment to negative pole where positive pole
Room (compartment 1), enriched chamber (compartment 2), diluting compartment (compartment 3) and cathode chamber (compartment 4), set between the anode chamber and enriched chamber
Cationic membrane is equipped with, the nanofiltration membrane described in above-mentioned technical proposal, the desalination are provided between the enriched chamber and diluting compartment
Cationic membrane is provided between room and cathode chamber.In the present invention, can be to Cl using this electrodialysis plant-And SO4 2-Carry out
Selectivity test, effective membrane area of the nanofiltration membrane and cationic membrane is preferably 7~7.5cm2, compacted zone towards positive pole,
The current density used is preferably 13~15mA cm-2, 0.1mol/L NaCl and 0.1mol/L are provided with diluting compartment
Na2SO4Mixed solution, the enriched chamber is provided with 0.01mol/L KCl solution, and the anode chamber and cathode chamber are provided with
0.3mol/L Na2SO4Solution.
Ionic flux and selectivity are to evaluate two important parameters of nanofiltration membrane, the ionic flux of nanofiltration membrane and selection
The size of property directly determines the efficiency of true electrodialytic process.Ionic flux (J) refers under certain operating conditions, the unit interval
The ionic weight that unit area passes through.Selectivity (P) refers under certain operating conditions, it is contemplated that two kinds of ion concentration difference it
Afterwards, certain ionic flux and the ratio of another ionic flux are passed through in electrodialytic process.The bigger expression of selectivity is to certain ion
Selective transmitting effect it is stronger.
Raw material used in following examples of the present invention is commercial goods.
Embodiment 1
The polyacrylonitrile solution that mass concentration is 17% is prepared, using DMF as solvent：
17g polyacrylonitrile samples are weighed, 83g DMF is weighed, polyacrylonitrile is added to N by amount,
In dinethylformamide, it is standby that well mixed solution is put into removing bubble in ultrasonic instrument., will be certain using film applicator
The polyacrylonitrile solution of amount is poured on clean glass plate, and adjustment knifing speed is arranged to 120mm/s, and adjustment scraper is highly made
It is standby to obtain the porous basement membrane of polyacrylonitrile that thickness is 60 μm.
The sodium hydroxide that the above-mentioned porous basement membrane of the polyacrylonitrile being prepared is put into 1.5mol/L of the constant temperature to 60 DEG C is molten
The hydrolysis of 2 hours is carried out in liquid, after hydrolysis, polyacrylonitrile porous membrane is taken out from alkali lye, surface is washed away with pure water
Alkali lye；Then film is immersed in 1mol/L hydrochloric acid solution, finally by perforated membrane taking-up with pure water three times, remove surface
Unnecessary hydrochloric acid, obtain being acidified polyacrylonitrile porous membrane.
5cm × 5cm above-mentioned acidifying polyacrylonitrile porous membrane is taken to be immersed in the ethylenediamine solution that mass fraction is 2%
1 hour, perforated membrane is taken out and is put on the glass plate of cleaning, is disposed vertically to the water of excess surface and is dried.Prepare quality
Fraction is the hexane solution of 0.1% paraphthaloyl chloride, and the above-mentioned perforated membrane dried is put in into the wherein 180s times, is occurred
Interface polymerization reaction, then by its (reaction product do synthesize it is more) dried in fume hood after in 60 DEG C of baking oven do
It is dry, nanofiltration membrane is prepared.
The nanofiltration membrane that the embodiment of the present invention 1 is prepared is scanned Electronic Speculum test and AFM test,
Test result is as shown in Fig. 3, Fig. 4 and Fig. 6, it can be seen that the nanofiltration membrane basement membrane that the embodiment of the present invention 1 is prepared
For finger-like pore, surface dense layer thickness is 181nm, and carrying out AFM to compacted zone characterizes roughness, can obtain electricity
The common average roughness of NF membrane is 45.8nm, r.m.s. roughness 35.1nm, and carried out surface Zeta potential and
Electrical testing, as shown in Figure 7 and Figure 8, when pH is 7, current potential is -0.01V.
Embodiment 2
Na+/Mg2+The electrodialysis plant of selectivity test, as shown in Figure 1：
Using the conventional compartment systems of electrodialysis four, compartment is followed successively by anode to compartment where negative pole where from positive pole
Room (compartment 1), diluting compartment (compartment 2), enriched chamber (compartment 3), cathode chamber (compartment 4).Where compartment to negative pole where from positive pole
Film used in compartment is that the AMX types anion-exchange membrane, nanofiltration membrane, ASTOM companies of the offer of ASTOM companies provide successively
AMX type anion-exchange membranes.Effective membrane area of film is 7.07cm2, for compacted zone towards positive pole, the current density used is 14mA
cm-2.Diluting compartment is 0.1mol/L NaCl and 0.1mol/L MgCl2The mixed solution of solution, enriched chamber are 0.01mol/L's
KCl solution, anode chamber and cathode chamber are 0.3mol/L Na2SO4Solution.
Embodiment 3
Cl-/SO4 2-The electrodialysis system of selectivity test, as shown in Figure 2：
Using the conventional compartment systems of electrodialysis four, compartment is followed successively by anode to compartment where negative pole where from positive pole
Room (compartment 1), enriched chamber (compartment 2), diluting compartment (compartment 3), cathode chamber (compartment 4).Where compartment to negative pole where from positive pole
Film used in compartment is that the CMX types anion-exchange membrane, nanofiltration membrane, ASTOM companies of the offer of ASTOM companies provide successively
CMX type anion-exchange membranes.Effective membrane area of film is 7.07cm2, for compacted zone towards negative pole, the current density used is 14mA
cm-2.Diluting compartment is 0.1mol/L NaCl and 0.1mol/L Na2SO4The mixed solution of solution, enriched chamber 0.01mol/L
KCl solution, anode chamber and cathode chamber are 0.3mol/L Na2SO4Solution.
Embodiment 4
The nanofiltration membrane that the embodiment of the present invention 1 is prepared using the electrodialysis plant described in embodiment 2 and embodiment 3
Carry out ionic flux and selectivity test, test result are：The Na for the nanofiltration membrane that the embodiment of the present invention 1 is prepared+Flux
For 4.27 × 10-8mol·cm-2·s-1, Mg2+Flux is 3.82 × 10-8mol·cm-2·s-1；Na+Relative to Mg2+Selectivity
For 3.3.Cl-Flux be 8.12 × 10-8mol·cm-2·s-1, SO4 2-Flux be 5.10 × 10-9mol·cm-2·s-1；Cl-
Relative to SO4 2-Selectivity be 16.
Nanofiltration membrane that the embodiment of the present invention 1 is prepared while there is good cation selective and anion selection
Property.
Embodiment 5
The polyacrylonitrile solution that mass concentration is 22% is prepared, using DMF as solvent：
22g polyacrylonitrile samples are weighed, 88g DMF is weighed, polyacrylonitrile is added to N by amount,
In dinethylformamide, it is standby that well mixed solution is put into removing bubble in ultrasonic instrument., will be certain using film applicator
The polyacrylonitrile solution of amount is poured on clean glass plate, and adjustment knifing speed is arranged to 120mm/s, and adjustment scraper is highly made
It is standby to obtain the porous basement membrane of polyacrylonitrile that thickness is 80 μm.
The sodium hydroxide that the above-mentioned porous basement membrane of the polyacrylonitrile being prepared is put into 1.5mol/L of the constant temperature to 60 DEG C is molten
The hydrolysis of 2 hours is carried out in liquid, after hydrolysis, polyacrylonitrile porous membrane is taken out from alkali lye, surface is washed away with pure water
Alkali lye；Then film is immersed in 1mol/L hydrochloric acid solution, finally by perforated membrane taking-up with pure water three times, remove surface
Unnecessary hydrochloric acid, obtain being acidified polyacrylonitrile porous membrane.
Take 5cm × 5cm above-mentioned acidifying polyacrylonitrile porous membrane be immersed in mass fraction be 1% diethylenetriamine it is water-soluble
1 hour in liquid, perforated membrane is taken out and is put on the glass plate of cleaning, is disposed vertically to the water of excess surface and is dried.Prepare
Mass fraction is the hexane solution of 1.0% formyl chloride of 1,3,5- benzene three, when the above-mentioned perforated membrane dried is put in into wherein 60s
Between, interface polymerization reaction occurs, then dried after it is dried in fume hood in 60 DEG C of baking oven, susceptance filter is prepared
Film.
The nanofiltration membrane that the embodiment of the present invention 5 is prepared according to the method described in embodiment 1 is tested, test knot
Fruit is that the nanofiltration membrane basement membrane that the embodiment of the present invention 5 is prepared is finger-like pore, and surface dense layer thickness is 86nm, to densification
Layer carries out AFM and characterizes roughness, and the common average roughness that can obtain nanofiltration membrane is 40.7nm, root mean square
Roughness is 32.9nm, and has carried out the Zeta potential test on surface, and when pH is 7, current potential is -0.01V.
The nanofiltration membrane that the embodiment of the present invention 5 is prepared method according to embodiment 4 carries out ionic flux and selection
Property test, test result is：The Na for the nanofiltration membrane that the embodiment of the present invention 5 is prepared+Flux is 3.87 × 10-8mol·cm-2·s-1, Mg2+Flux is 1.35 × 10-8mol·cm-2·s-1；Na+Relative to Mg2+Selectivity be 2.9.Cl-Flux be
7.6×10-8mol·cm-2·s-1, SO4 2-Flux be 2.8 × 10-9mol·cm-2·s-1；Cl-Relative to SO4 2-Selectivity
For 27.
Nanofiltration membrane that the embodiment of the present invention 5 is prepared while there is good cation selective and anion selection
Property.
Embodiment 6
The quaternary ammoniated polyphenyl ethereal solution that mass concentration is 17% is prepared, using dimethyl sulfoxide (DMSO) as solvent：
The quaternary ammoniated polyphenylene oxide samples of 17g are weighed, 83g dimethyl sulfoxide (DMSO) is weighed, quaternary ammoniated polyphenylene oxide is added to by amount
In dimethyl sulfoxide (DMSO), it is standby that well mixed solution is put into removing bubble in ultrasonic instrument., will be a certain amount of using film applicator
Polyacrylonitrile solution is poured on clean glass plate, and adjustment knifing speed is arranged to 120mm/s, and adjustment scraper is highly prepared into
To the porous basement membrane of quaternary ammoniated polyphenylene oxide that thickness is 120 μm.
Take 5cm × 5cm above-mentioned quaternary ammoniated polyphenylene oxide perforated membrane be immersed in mass fraction be 2% TEPA it is water-soluble
2 hours in liquid, perforated membrane is taken out and is put on the glass plate of cleaning, is disposed vertically to the water of excess surface and is dried.Prepare
Mass fraction is the toluene solution of 0.1% formyl chloride of 1,3,5- benzene three, when the above-mentioned perforated membrane dried is put in into wherein 120s
Between, interface polymerization reaction occurs, then dried 2 hours in 40 DEG C of baking oven after it is dried in fume hood, electricity is prepared
NF membrane.
The performance for the nanofiltration membrane being prepared according to the method test embodiment of the present invention 6 described in embodiment 1, test knot
Fruit is that the nanofiltration membrane basement membrane that the embodiment of the present invention 6 is prepared is finger-like pore, and surface dense layer thickness is 73.5nm, to causing
Close layer carries out AFM and characterizes roughness, and the common average roughness that can obtain nanofiltration membrane is 28.1nm, just
Root roughness is 22.4nm, and has carried out the Zeta potential test on surface, and when pH is 7, current potential is -0.01V.
The nanofiltration membrane embodiment of the present invention 6 being prepared according to the method described in embodiment 4 carry out ionic flux and
Selectivity test, test result are：The Na for the nanofiltration membrane that the embodiment of the present invention 6 is prepared+Flux is 4.18 × 10- 8mol·cm-2·s-1, Mg2+Flux is 1.48 × 10-8mol·cm-2·s-1；Na+Relative to Mg2+Selectivity be 2.9.Cl-'s
Flux is 8.85 × 10-8mol·cm-2·s-1, SO4 2-Flux be 1.11 × 10-9mol·cm-2·s-1；Cl-Relative to SO4 2-
Selectivity be 8.
Nanofiltration membrane that the embodiment of the present invention 6 is prepared while there is good cation selective and anion selection
Property.
Embodiment 7
The sulfonated polyphenyl ethereal solution that mass concentration is 30% is prepared, using dimethyl sulfoxide (DMSO) as solvent：
30g sulfonated poly (phenylene oxide) samples are weighed, 70g dimethyl sulfoxide solvents is weighed, sulfonated poly (phenylene oxide) is added to two by amount
In methyl sulfoxide, it is standby that obtained mixed liquor is put into removing bubble in ultrasonic instrument.Using electrostatic spinning machine by above-mentioned sulfonation
Polyphenyl ethereal solution is carried out in electrospinning electro-spinning process, and temperature control is at 30 DEG C, humidity 30%, and the positive high voltage at syringe needle is 21KV,
The negative high voltage of receiver is -2KV, and rotating speed is 30 revs/min, fltting speed 0.07mLmin-1, between syringe needle and receiver
Distance is set as 20cm, after consuming 15mL sulfonated polyphenyl ethereal solutions, obtains the preferable sulfonated poly (phenylene oxide) electrospinning fibre of mechanical strength
Felt.The electrospinning fibre felt used from receiver obtains thickness as 90 μm of porous basement membrane by vacuum drying and hot pressing.
5cm × 5cm above-mentioned electrospinning perforated membrane is taken to be immersed in the polyethyleneimine (molecular weight 1000) that mass fraction is 2%
1 hour in the aqueous solution, perforated membrane is taken out and is put on the glass plate of cleaning, is disposed vertically to the water of excess surface and is dried.
The hexane solution for the formyl chloride of 1,3,5- benzene three that mass fraction is 0.1% is prepared, the above-mentioned perforated membrane dried is put in wherein
The 360s times, interface polymerization reaction occurs, then dried after it is dried in fume hood in 60 DEG C of baking oven, electricity is prepared
NF membrane.
The nanofiltration membrane that the embodiment of the present invention 7 is prepared method according to embodiment 1 is tested, and test result is such as
Shown in Fig. 4, the nanofiltration membrane basement membrane that the embodiment of the present invention 7 is prepared is superimposed what is formed for superfine Electrospun, has pole
Bigger serface, high porosity and interconnected network structure, surface dense layer thickness are 49nm, and atom is carried out to compacted zone
Force microscope characterizes roughness, and the common average roughness that can obtain nanofiltration membrane is 13.1nm, and r.m.s. roughness is
10.1nm, and the Zeta potential test on surface has been carried out, when pH is 7, current potential is -0.03V.
The nanofiltration membrane embodiment of the present invention 7 being prepared according to the method described in embodiment 4 carry out ionic flux and
Selectivity test, test result are：The Na for the nanofiltration membrane that the embodiment of the present invention 7 is prepared+Flux is 4.00 × 10- 8mol·cm-2·s-1, Mg2+Flux is 2.41 × 10-8mol·cm-2·s-1；Na+Relative to Mg2+Selectivity be 1.8.Cl-'s
Flux is 7.47 × 10-8mol·cm-2·s-1, SO4 2-Flux be 3.31 × 10-9mol·cm-2·s-1；Cl-Relative to SO4 2-
Selectivity be 2.
Nanofiltration membrane that the embodiment of the present invention 7 is prepared while there is good cation selective and anion selection
Property.
As seen from the above embodiment, the invention provides a kind of nanofiltration membrane, including：Basement membrane, it is arranged on membrane surface
Separating layer, the separating layer are prepared by aminated compounds and acyl chloride compound.Compared with prior art, the present invention provides
Nanofiltration membrane can realize the Selective Separation of single multi- valency ion, ion transport resistance in film is smaller, and flux is high, uses
The aminated compounds of different structure can be adjusted to the molecule cross-link structure of separating layer, obtain consistency and surface charge amount
Different surface separation layers.The preparation method of nanofiltration membrane provided by the invention is simple and convenient, obtained nanofiltration membrane pole
Current density of rationing the power supply is high, has higher selectivity to single multi- valency cation and single multi- valency anion in electrodialytic process.
Claims (10)
1. a kind of nanofiltration membrane, including：
Basement membrane；
The separating layer of membrane surface is arranged on, the separating layer is prepared by aminated compounds and acyl chloride compound.
2. nanofiltration membrane according to claim 1, it is characterised in that the aminated compounds is selected from and carries polyamino group
Aminated compounds in one or more.
3. nanofiltration membrane according to claim 1, it is characterised in that the acyl chloride compound is selected from and carries more acid chloride groups
One or more in the acyl chloride compound of group.
4. nanofiltration membrane according to claim 1, it is characterised in that the basement membrane is porous charged membrane.
5. a kind of preparation method of the nanofiltration membrane described in claim 1, including：
Using inversion of phases, electrostatic spinning, pulling method, Thermal inactive, additive pore-creating, exchange of solvent pore-creating or electronics beta radiation
Basement membrane is prepared in etching method；
The basement membrane is immersed in the aminated compounds aqueous solution and then dried, then immerses in the organic solution of acyl chloride compound
Row reaction, obtains nanofiltration membrane.
6. according to the method for claim 5, it is characterised in that the mass concentration of the aminated compounds aqueous solution is 0.5
~5%.
7. according to the method for claim 5, it is characterised in that the mass concentration of the organic solution of the acyl chloride compound
For 0.1~5%.
8. according to the method for claim 5, it is characterised in that organic molten in the organic solution of the acyl chloride compound
Agent be and the immiscible volatile organic solvent of water.
9. according to the method for claim 5, it is characterised in that the time that the basement membrane is immersed in the aminated compounds aqueous solution
For 3~180 minutes；
The time for immersing the organic solution of acyl chloride compound is 30~3600 seconds.
10. according to the method for claim 5, it is characterised in that the temperature of the reaction is 10~50 DEG C.
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Application publication date: 20171215 |