CN109821418A - It is a kind of with aligned carbon nanotube basement membrane, utilize its interfacial polymerization nanofiltration membrane and preparation method thereof - Google Patents
It is a kind of with aligned carbon nanotube basement membrane, utilize its interfacial polymerization nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN109821418A CN109821418A CN201910252198.5A CN201910252198A CN109821418A CN 109821418 A CN109821418 A CN 109821418A CN 201910252198 A CN201910252198 A CN 201910252198A CN 109821418 A CN109821418 A CN 109821418A
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Abstract
The present embodiments relate to Material Fields, and in particular to it is a kind of with aligned carbon nanotube basement membrane, utilize its interfacial polymerization nanofiltration membrane and preparation method thereof.Preparation method provided in an embodiment of the present invention with high voltage electric field aligned carbon nanotube basement membrane, it include: that the casting solution containing carbon nanotube is coated on insulation smooth base plate, it is put into high voltage electric field device and acts on, insulation smooth base plate is put into water coagulating bath and removes organic solvent, is obtained with aligned carbon nanotube basement membrane.The preparation method of interfacial polymerization nanofiltration membrane provided in an embodiment of the present invention, comprising: using above-mentioned there is aligned carbon nanotube basement membrane to prepare interfacial polymerization nanofiltration membrane.Have certain orientation and water flux big with high voltage electric field aligned carbon nanotube basement membrane；Interfacial polymerization nanofiltration membrane is prepared using it, is greatly improved efficiency of the hydrone by basement membrane, and is infiltrative while ensure that selectivity improving interfacial polymerization nanofiltration membrane.
Description
Technical field
The present invention relates to Material Fields, and in particular to it is a kind of with aligned carbon nanotube basement membrane, utilize its interfacial polymerization
Nanofiltration membrane and preparation method thereof.
Background technique
Since increasing environmental pollution and population constantly increase, shortage of fresh water is causing global concern.Film point
From technology as a kind of method for treating water, with low energy consumption, operating condition is moderate, advantages of environment protection.Ultrafiltration membrane, nanofiltration membrane
It is developed for use in the various sizes of substance of retention with reverse osmosis membrane, wherein nanofiltration is a kind of emerging pressure drive membrane work
Skill has excellent separating capacity to divalent ion and low-molecular-weight organic matter.
Interfacial polymerization nanofiltration membrane based on aromatic polyamide, due to its cost effective and it is fairly simple operation and by
It is widely used in water body purification and removing divalent salts, for the stabilization for further increasing its separating property and permeance property and having kept
Property, it needs to be modified film further to explore the potentiality of nanofiltration membrane.For the method for modifying master of interfacial polymerization nanofiltration membrane
There is the boundary layer of film modified two kinds modified with basement membrane.And the appearance of nano material, such as carbon nanotube, silica, titanium dioxide
Titanium and graphene oxide etc. can be used as a kind of better choice of modified filler in basement membrane.
Carbon nanotube from the mechanical strength of height and excellent chemical stability be extremely advantageous to the durability of film.And
And its smooth unresisted inner wall can be used as a kind of express passway of hydrone, so that hydrone is passed through film faster, is conducive to
Permeability of the membrane energy.However, carbon nanotube forms the trend of entanglement agglomerate and its weak interface phase interaction with polymer substrate
With being difficult to it evenly dispersed in casting solution.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
In order to solve the above technical problems, people start to be modified carbon nanotube using physical method or chemical method, with
Just it forms homogeneous dispersion in a solvent, to improve the performance of film.The purpose of the present invention is to provide one kind to have orientation
Carbon nanotube basement membrane utilizes its interfacial polymerization nanofiltration membrane and preparation method thereof.In the preparation with aligned carbon nanotube basement membrane
In method, by applying external high pressure electric field to the casting solution containing carbon nanotube, make carbon nanotube in the effect of high voltage electric field
It is lower to polarize, so that tangling phenomenon mitigates；And carbon nanotube both ends induce the conduction up and down with high voltage electric field device
The opposite charge of pole plate is orientated carbon nanotube along direction of an electric field to generate torque；Therefore as made from the preparation method
Have certain orientation and water flux big with high voltage electric field aligned carbon nanotube basement membrane.There is aligned carbon nanotube using above-mentioned
Basement membrane prepares interfacial polymerization nanofiltration membrane, substantially increases efficiency of the hydrone by basement membrane, and improving interfacial polymerization nanofiltration membrane
It is infiltrative while ensure that selectivity.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of with high voltage electric field aligned carbon nanotube basement membrane
Preparation method includes the following steps: for the casting solution containing carbon nanotube to be coated on insulation smooth base plate, is put into high voltage electric field
It is acted in device, insulation smooth base plate is put into water coagulating bath, is obtained with aligned carbon nanotube basement membrane.Wherein, insulate light
Sliding substrate includes glass plate etc..
The embodiment of the invention also provides a kind of preparation method of interfacial polymerization nanofiltration membrane, include the following steps: using upper
It states and prepares interfacial polymerization nanofiltration membrane with aligned carbon nanotube basement membrane.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, contains
The casting solution of carbon nanotube is made by following step:
Carbon nanotube, film additive and membrane material are added in organic solvent, ultrasonic disperse, then added at 50-70 DEG C
Thermal agitation 4-8h forms uniform casting solution, and casting solution is carried out vacuum defoamation, obtains the casting solution containing carbon nanotube；It can
Selection of land, the heating stirring 6h at 60 DEG C.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, casting film
In liquid, the quality of carbon nanotube account for carbon nanotube, film additive, membrane material and organic solvent gross mass 0.2-2%；Optionally
For 0.5-1.5%, 0.5-1% or 1-1.5%.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, casting film
The mass ratio of carbon nanotube in liquid, film additive and membrane material are as follows: (0.5-1.5): (0-2): (10-30).
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, high pressure
Electric field arrangement includes power supply unit, conductive top crown, conductive bottom crown, the insulation between conductive top crown and conductive bottom crown
Support column, and it is used to support the insulation rack of the insulation smooth base plate coated with casting solution；The insulating supporting column is for branch
Conductive top crown and conductive bottom crown are supportted, and forms the chamber that can accommodate the smooth base plate of the insulation coated with casting solution between
Body, the height of cavity are 10-30cm；Insulation rack is set in cavity；Conductive top crown and conductive bottom crown pass through conductive electricity
Pole is connected with power supply unit.Wherein, insulation rack size is slightly larger than insulation smooth base plate.When energized, conductive top crown
High voltage electric field can be generated between conductive bottom crown.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, power supply
Portion is DC constant voltage power supply, operating supply voltage≤30000V of high voltage electric field device；Optionally, operating voltage≤20000V,
Operating current≤0.02mA；Still optionally further, operating voltage 20000V, operating current 0.01mA, electric field strength range
It is 2000-2800V/cm.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, high pressure
Electric field arrangement action time is 0.5-5min.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, receive by carbon
Mitron is multi-walled carbon nanotube or single-walled carbon nanotube, and outer tube diameter 10-20nm, length is 10-30 μm, purity >=
98wt%.
In one possible implementation, film adds the above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane
Adding agent includes at least one of polyvinylpyrrolidone, methyl pyrrolidone, ethyl alcohol, lithium chloride, polyethylene glycol.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane in one possible implementation, membrane material
Material includes at least one of polysulfones, polyether sulfone, Kynoar, polyacrylonitrile.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane is in one possible implementation, organic
Solvent includes N-N- dimethylformamide, N-N- dimethyl acetamide, methyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide
At least one of.
The above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane is in one possible implementation, ultrasonic
Dispersion machine ultrasonic disperse 1-2h, ultrasonic power 100-200W.
The preparation method of above-mentioned interfacial polymerization nanofiltration membrane is orientated carbon nanometer in one possible implementation, using having
The method that pipe basement membrane prepares interfacial polymerization nanofiltration membrane includes: interfacial polymerization.Interfacial polymerization is common preparation interfacial polymerization
The method of nanofiltration membrane.
The preparation method of above-mentioned interfacial polymerization nanofiltration membrane in one possible implementation, interfacial polymerization step packet
It includes:
Aqueous phase solution and oil-phase solution are prepared respectively, and the aqueous phase solution prepared will be immersed in aligned carbon nanotube basement membrane
In, it obtains to surface and covers the basement membrane of aqueous phase solution；Sealing reaction tank is placed in the film upper surface, the oil-phase solution prepared is fallen
Enter in reaction tank, reacts, basement membrane is taken out, interfacial polymerization nanofiltration membrane is obtained.Wherein, during being somebody's turn to do, interface polymerization reaction is only sent out
Life is in the upper surface of basement membrane.
The preparation method of above-mentioned interfacial polymerization nanofiltration membrane is orientated carbon nanometer in one possible implementation, using having
Pipe basement membrane prepares the step of interfacial polymerization nanofiltration membrane further include: it is remaining molten that interfacial polymerization nanofiltration membrane is put into removing in n-hexane
Liquid, the then heat cure in vacuum drying oven, is put into deionized water and stores；Heat curing temperature is 60-80 DEG C, is optionally 70
℃。
In one possible implementation, the solute of aqueous phase solution includes the preparation method of above-mentioned interfacial polymerization nanofiltration membrane
M-phenylene diamine (MPD), piperazine, diethylenetriamine, at least one of triethylene tetramine, solvent are water；Solute concentration is 0.2-2wt%.
The preparation method of above-mentioned interfacial polymerization nanofiltration membrane in one possible implementation, impregnates 1- in aqueous phase solution
10min。
In one possible implementation, the solute of oil-phase solution includes the preparation method of above-mentioned interfacial polymerization nanofiltration membrane
Benzene diacid chloride, at least one of pyromellitic trimethylsilyl chloride, solvent are n-hexane；Solute concentration is 0.02-0.2wt%.
In one possible implementation, the oil-phase solution prepared is fallen for the preparation method of above-mentioned interfacial polymerization nanofiltration membrane
After entering in reaction tank, 0.5-2min is reacted.
The preparation method of above-mentioned interfacial polymerization nanofiltration membrane in one possible implementation, in vacuum drying oven when heat cure
Between be 10-30min.
In one possible implementation, sealing reaction tank material includes the preparation method of above-mentioned interfacial polymerization nanofiltration membrane
At least one of nylon66 fiber, organic glass, polyether-ether-ketone or polycarbonate.
The embodiment of the invention also provides made from the above-mentioned preparation method with high voltage electric field aligned carbon nanotube basement membrane
With high voltage electric field aligned carbon nanotube basement membrane.
The embodiment of the invention also provides interfacial polymerization nanofiltration membranes made from the preparation method of above-mentioned interfacial polymerization nanofiltration membrane.
There is application of the high voltage electric field aligned carbon nanotube basement membrane in water process the embodiment of the invention also provides above-mentioned.
The embodiment of the invention also provides application of the above-mentioned interfacial polymerization nanofiltration membrane in water process.
Beneficial effect
(1) preparation method provided in an embodiment of the present invention with high voltage electric field aligned carbon nanotube basement membrane, by containing
There is carbon nanotube casting solution to apply external high pressure electric field, carbon nanotube polarizes under the action of high voltage electric field, so that tangling
Phenomenon mitigates；And carbon nanotube both ends induce the charge opposite with upper bottom crown, make carbon nanotube along electricity to generate torque
Field direction orientation；So that obtained have high-voltage electricity aligned carbon nanotube basement membrane water flux big.
(2) preparation method provided in an embodiment of the present invention with high voltage electric field aligned carbon nanotube basement membrane, the height used
The insulation rack for the insulation smooth base plate for being coated with casting solution that can be supported is provided in piezoelectricity field device, so that casting solution exists
In the position close to top crown in electric field, be conducive to carbon nanotube under electric field force effect to the movement of top crown direction, so that
The probability that carbon nanotube appears in film upper surface after basement membrane molding increases, and when carbon nanotube appears in film upper surface, exists
Increase in the probability of separating layer, directly acts on the carbon nanotube of separating layer, spy of the smooth inner wall as transport aquaporin
Property can be developed and used preferably.
(3) preparation method of interfacial polymerization nanofiltration membrane provided in an embodiment of the present invention has orientation carbon nanometer using above-mentioned
Pipe basement membrane prepares interfacial polymerization nanofiltration membrane, substantially increases efficiency of the hydrone by basement membrane, and improving interfacial polymerization nanofiltration
It ensure that selectivity while membrane permeability.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 is the preparation flow schematic diagram of the embodiment of the present invention.
Fig. 2 is the cross section structure figure obtained with aligned carbon nanotube basement membrane M-1-DC of the embodiment of the present invention 1.
Fig. 3 is the cross section structure figure of No yield point basement membrane M-1 made from comparative example 1 of the present invention.
Fig. 4 be test example of the present invention to made from embodiment 1 and comparative example 1 without/there is aligned carbon nanotube basement membrane to carry out
Water flux test result.
Fig. 5 is that test example of the present invention carries out water flux and Na to interfacial polymerization nanofiltration membrane made from embodiment 22SO4Retention
Rate test result.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Multi-walled carbon nanotube used in following embodiment, outer tube diameter 20nm, length are 20 μm, purity 98wt%；
Polyether sulfone model Ultrason E6020P, molecular weight 58000Da；
Polyvinylpyrrolidone model K-30, molecular weight 58000Da.
High voltage electric field device used in following embodiment:
Including power supply unit, conductive top crown, conductive bottom crown, and between conductive top crown and conductive bottom crown
Insulating supporting column；The cavity that can accommodate the glass plate coated with casting solution, institute are formed between conductive top crown and conductive bottom crown
The height for stating cavity is 10cm；
High voltage electric field device further includes a pair of conductive electrode being connected with power supply unit；Conductive electrode respectively with pole in conduction
Plate is connected with conductive bottom crown, when energized, can generate high voltage electric field between conductive top crown and conductive bottom crown；
High voltage electric field device is additionally provided with the insulation rack that can support the glass plate coated with casting solution, and insulation rack is bigger
In glass plate；
Power supply unit is DC constant voltage power supply, operating voltage 20000V, operating current 0.01mA, and electric field strength range is
2000-2100V/cm；
The high voltage electric field device action time is 1min.
Preparation flow schematic diagram of the invention incorporated by reference to following specific embodiments as shown in Figure 1, and understood.
Embodiment 1
No yield point basement membrane M-0-DC is prepared respectively and there is aligned carbon nanotube basement membrane M-0.5-DC, M-1-DC and M-1.5-
DC, the difference is that multi-walled carbon nanotube content is different:
(1) preparation method of No yield point basement membrane M-0-DC includes the following steps:
It disperses 0.5g polyvinylpyrrolidone in 41.5g N-N dimethyl acetamide, it is molten to this under stirring
8g polyether sulfone is added in liquid and forms uniform casting solution at 60 DEG C after heating stirring 6h.Casting solution is removed under vacuum conditions
Bubble on a glass by casting solution, is uniformly scraped film on a glass, in height using 150 μm of hymenotome of scraping at room temperature
In piezoelectricity field device place 1min after, move in water coagulating tank (15 DEG C, solvent-free volatilization), after 0~1min visible film from
It is dynamic to be detached from glass plate, it impregnates in deionized water for 24 hours, it is ensured that mutually separate completely, obtain No yield point basement membrane M-0-DC.
(2) with the preparation method of aligned carbon nanotube basement membrane M-0.5-DC: with the preparation method of M-0-DC film, difference is only
It is: disperses 41.25g N-N diformazan under ultrasound condition for 0.25g multi-walled carbon nanotube and 0.5g polyvinylpyrrolidone
In yl acetamide；Ultrasonic power is 100W, ultrasonic time 30min." 0.5 " in M-0.5-DC indicates carbon nanotube additive amount
(carbon nanotube additive amount refers to that the quality of carbon nanotube accounts for the ratio of carbon nanotube, film additive, membrane material and organic solvent gross mass
Example) it is 0.5%, remaining and so on.
(3) with the preparation method of aligned carbon nanotube basement membrane M-1-DC: with the preparation method of M-0.5-DC film, difference is only
It is: disperses 41g N-N dimethyl second under ultrasound condition for 0.5g multi-walled carbon nanotube and 0.5g polyvinylpyrrolidone
In amide.Cross section structure figure obtained with aligned carbon nanotube basement membrane M-1-DC is shown in Fig. 2.
(4) with the preparation method of aligned carbon nanotube basement membrane M-1.5-DC basement membrane: poor with the preparation method of M-0-DC film
It is not only that: dispersing 40.75gN-N bis- under ultrasound condition for 0.75g multi-walled carbon nanotube and 0.5g polyvinylpyrrolidone
In methylacetamide.
Comparative example 1
Prepare respectively multi-walled carbon nanotube content it is different without high voltage electric field handle No yield point basement membrane M-0, M-0.5,
M-1 and M-1.5；
(1) preparation method of M-0 film includes the following steps:
It disperses 0.5g polyvinylpyrrolidone in 41.5g N-N dimethyl acetamide, it is molten to this under stirring
8g polyether sulfone is added in liquid, at 60 DEG C after heating stirring 6 hours, forms uniform casting solution.Under vacuum conditions by casting solution
Bubble removing is removed, at room temperature, on a glass by casting solution, is uniformly scraped film on a glass using 150 μm of hymenotome of scraping,
After placing 1min in air, (15 DEG C, solvent-free volatilization) are moved in water coagulating tank, visible film automatically disengages after 0-1min
Glass plate impregnates 24 hours in deionized water, it is ensured that mutually separates completely, obtains M-0 film.
(2) preparation method of M-0.5 film: with the preparation method of M-0 film, difference is only that: by 0.25g multi-walled carbon nanotube
It is scattered under ultrasound condition in 41.25g N-N dimethyl acetamide with 0.5g polyvinylpyrrolidone.
(3) preparation method of M-1 film: with the preparation method of M-0 film, difference is only that: by 0.5g multi-walled carbon nanotube and
0.5g polyvinylpyrrolidone is scattered in 41g N-N dimethyl acetamide under ultrasound condition.It ties in the section of M-1 film obtained
Composition is shown in Fig. 3.
(4) preparation method of M-1.5 film: with the preparation method of M-0 film, difference is only that: by 0.75g multi-walled carbon nanotube
It is scattered under ultrasound condition in 40.75g N-N dimethyl acetamide with 0.5g polyvinylpyrrolidone.
Embodiment 2
1. the nothing being prepared using embodiment 1/there is aligned carbon nanotube basement membrane to prepare interfacial polymerization nanofiltration membrane respectively
M-0-DC/PA, M-0.5-DC/PA, M-1-DC/PA and M-1.5-DC/PA:
(1) preparation method of M-0-DC/PA interfacial polymerization nanofiltration membrane includes the following steps:
0.4g piperazine is dissolved in 20mL water, ultrasonic disperse 10min, aqueous phase solution is made；By 0.04g pyromellitic trimethylsilyl chloride
It is dissolved in 20mL n-hexane, ultrasonic disperse 10min, oil-phase solution is made；
M-0-DC obtained in embodiment 1 is immersed in 5min in the aqueous phase solution prepared, obtains to surface and covers water phase
The composite membrane of solution places a sealing reaction tank in the film upper surface, the oil-phase solution 2mL prepared is taken to instill reaction later
Chi Zhong only occurs in interface polymerization reaction on the upper surface of basement membrane, after reacting 1min, basement membrane is taken out, interfacial polymerization is obtained
Nanofiltration membrane；Interfacial polymerization nanofiltration membrane is put into n-hexane and removes residual solution, then 70 DEG C of heat cures in vacuum drying oven
30min obtains M-0-DC/PA interfacial polymerization nanofiltration membrane, is finally putting into deionized water and stores.
(2) preparation method of M-0.5-DC/PA interfacial polymerization nanofiltration membrane: with the system of M-0-DC/PA interfacial polymerization nanofiltration membrane
Preparation Method, difference are only that: changing M-0-DC into M-0.5-DC.
(3) preparation method of M-1-DC/PA interfacial polymerization nanofiltration membrane: with the preparation of M-0-DC/PA interfacial polymerization nanofiltration membrane
Method, difference are only that: changing M-0-DC into M-1-DC.
(4) preparation method of M-1.5-DC/PA interfacial polymerization nanofiltration membrane: with the system of M-0-DC/PA interfacial polymerization nanofiltration membrane
Preparation Method, difference are only that: changing M-0-DC into M-1.5-DC.
Preparation flow figure of the invention is as shown in Figure 1.
2. the No yield point basement membrane being prepared using comparative example 1 prepares interfacial polymerization nanofiltration membrane M-0/PA, M-0.5/ respectively
PA, M-1/PA, M-1.5/PA:
(1) M-0/PA interfacial polymerization nanofiltration membrane prepares Fang Shu: with the preparation side of M-0-DC/PA interfacial polymerization nanofiltration membrane
Method, difference are only that: changing M-0-DC into M-0 that comparative example 1 is prepared.
(2) preparation method of M-0.5/PA interfacial polymerization nanofiltration membrane: with the preparation side of M-0-DC/PA interfacial polymerization nanofiltration membrane
Method, difference are only that: changing M-0-DC into M-0.5 that comparative example 1 is prepared.
(3) preparation method of M-1/PA interfacial polymerization nanofiltration membrane: with the preparation side of M-0-DC/PA interfacial polymerization nanofiltration membrane
Method, difference are only that: changing M-0-DC into M-1 that comparative example 1 is prepared.
(4) preparation method of M-1.5/PA interfacial polymerization nanofiltration membrane: with the preparation side of M-0-DC/PA interfacial polymerization nanofiltration membrane
Method, difference are only that: changing M-0-DC into M-1.5 that comparative example 1 is prepared.
Test example
1. nothing made from pair embodiment 1 and comparative example 1/there is aligned carbon nanotube basement membrane to carry out water flux test:
Experimental result is shown in Fig. 4, as shown in Figure 4: it is compared with the corresponding No yield point basement membrane of aligned carbon nanotube basement membrane,
With higher water flux.Wherein, the water flux with aligned carbon nanotube basement membrane becomes with the additive amount difference of carbon nanotube
Change, when carbon nanotube additive amount is 1%, the water flux with aligned carbon nanotube basement membrane (M-1-DC) is maximum, and it is significant
Better than the water flux of corresponding No yield point basement membrane (M-1)；When carbon nanotube additive amount increases to 1.5%, there is orientation carbon
The water flux of nanotube basement membrane (M-1.5-DC) is slightly better than corresponding No yield point basement membrane (M-1.5).
2. interfacial polymerization nanofiltration membrane made from pair embodiment 2 carries out water flux and Na2SO4Rejection test:
As a result see Fig. 5, it is as shown in Figure 5, obtained with the increase for having content of carbon nanotubes in aligned carbon nanotube basement membrane
The water flux of interfacial polymerization nanofiltration membrane is in rising trend；And it is generally than interfacial polymerization nanofiltration made from corresponding No yield point basement membrane
The water flux of film is high, and the trend risen is presented with the increase of content of carbon nanotubes in this species diversity, and in content of carbon nanotubes
When lower, this species diversity is unobvious.
Meanwhile the Na with interfacial polymerization nanofiltration membrane made from aligned carbon nanotube basement membrane2SO4Rejection generally compare
Interfacial polymerization nanofiltration membrane made from the No yield point basement membrane answered is high, and Na2SO4Rejection be maintained at 94% or more.
In addition, in general, the basement membrane for having added electric field treatment to obtain, the water of further interfacial polymerization nanofiltration membrane obtained
Flux and Na2SO4Rejection be above its and corresponding basement membrane that electric field treatment obtains be not added further interfacial polymerization obtained is received
Filter membrane.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (11)
1. a kind of preparation method with high voltage electric field aligned carbon nanotube basement membrane includes the following steps: that carbon nanotube will be contained
Casting solution be coated on insulation smooth base plate, be put into high voltage electric field device and act on, insulation smooth base plate is put into water-setting and consolidates
In bath, obtain with aligned carbon nanotube basement membrane.
2. a kind of preparation method of interfacial polymerization nanofiltration membrane includes the following steps: there is orientation carbon using described in claim 1
Nanotube basement membrane prepares interfacial polymerization nanofiltration membrane.
3. preparation method according to claim 1 or 2, it is characterised in that: the casting solution containing carbon nanotube is by following steps
It is rapid to be made:
Carbon nanotube, film additive and membrane material are added in organic solvent, ultrasonic disperse, then heat and stir at 50-70 DEG C
4-8h is mixed, uniform casting solution is formed, casting solution is subjected to vacuum defoamation, obtains the casting solution containing carbon nanotube；Optionally,
The heating stirring 6h at 60 DEG C.
4. preparation method according to claim 3, it is characterised in that: in casting solution, the quality of carbon nanotube accounts for carbon nanometer
Pipe, film additive, membrane material and organic solvent gross mass 0.2-2%；It is optionally 0.5-1.5%, 0.5-1% or 1-
1.5%；
And/or in casting solution, the mass ratio of carbon nanotube, film additive and membrane material are as follows: (0.5-1.5): (0-2): (10-
30)。
5. preparation method according to claim 1 or 2, it is characterised in that: above-mentioned that there is high voltage electric field aligned carbon nanotube
In one possible implementation, high voltage electric field device action time is 0.5-5min to the preparation method of basement membrane.
6. preparation method according to claim 1 or 2, it is characterised in that: high voltage electric field device includes power supply unit, in conduction
Pole plate, conductive bottom crown, the insulating supporting column between conductive top crown and conductive bottom crown, and be used to support and be coated with
The insulation rack of the insulation smooth base plate of casting solution；The insulating supporting column is used to support conductive top crown and conductive bottom crown,
And the cavity that can accommodate the smooth base plate of the insulation coated with casting solution is formed between, the height of cavity is 10-30cm；Absolutely
Hoddy erection is placed in cavity；Conductive top crown and conductive bottom crown are connected by conductive electrode with power supply unit；Optionally, electric
Source portion is DC constant voltage power supply, operating voltage≤30000V of high voltage electric field device；Optionally, operating voltage≤20000V, work
Make electric current≤0.02mA；Still optionally further, operating voltage 20000V, operating current 0.01mA, electric field strength range are
2000-2800V/cm。
7. preparation method according to claim 3, it is characterised in that: carbon nanotube is that multi-walled carbon nanotube or single wall carbon are received
Mitron, outer tube diameter 10-20nm, length are 10-30 μm, purity > 98wt%；
And/or film additive include polyvinylpyrrolidone, methyl pyrrolidone, ethyl alcohol, lithium chloride, in polyethylene glycol extremely
Few one kind；
And/or membrane material includes at least one of polysulfones, polyether sulfone, Kynoar, polyacrylonitrile；
And/or organic solvent includes N-N- dimethylformamide, N-N- dimethyl acetamide, methyl pyrrolidone, diformazan Asia
At least one of sulfone, hexamethyl phosphoramide；
And/or ultrasonic disperse machine ultrasonic disperse 1-2h, ultrasonic power 100-200W.
8. preparation method according to claim 2 prepares interfacial polymerization nanofiltration membrane using with aligned carbon nanotube basement membrane
Method include: interfacial polymerization；
Optionally, interfacial polymerization step includes: to prepare aqueous phase solution and oil-phase solution respectively, will have aligned carbon nanotube base
Film is immersed in the aqueous phase solution prepared, is obtained to surface and is covered the basement membrane of aqueous phase solution；It is anti-that sealing is placed in the film upper surface
Ying Chi pours into the oil-phase solution prepared in reaction tank, and basement membrane is taken out, obtains interfacial polymerization nanofiltration membrane by reaction.
9. preparation method described in claim 1 is obtained to have high voltage electric field aligned carbon nanotube basement membrane.
10. interfacial polymerization nanofiltration membrane made from preparation method as claimed in claim 2.
11. as claimed in claim 9 have high voltage electric field aligned carbon nanotube basement membrane or interfacial polymerization described in any one of claim 10
Application of the nanofiltration membrane in water process.
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