CN109999662A - A kind of amphoteric ion nanofiltration membrane and preparation method thereof - Google Patents
A kind of amphoteric ion nanofiltration membrane and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
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Abstract
The present invention relates to a kind of amphoteric ion nanofiltration membrane, including support layer and cortex, the support layer is the copolymer of ultrafiltration membrane, graphene oxide, super branched molecule, and the cortex is the compound aramid layer containing amphoteric ion polymer on supporting layer.The invention further relates to the preparation methods of above-mentioned amphoteric ion nanofiltration membrane.The present invention introduces graphene oxide on supporting layer, by the surface of its vacuum filter to ultrafiltration membrane, effectively raises the hydrophilicity of ultrafiltration membrane；The support that the copolymer of ultrafiltration membrane, graphene oxide, super branched molecule forms is placed in the oil-phase solution of the small-molecule substance containing acyl chlorides, the effectively catching to solute is realized；When nanofiltration film activity cortex and amphoteric ion solution further contact, generates and contain zwitterionic nanofiltration membrane, it is easier to Free water is adsorbed, to improve membrane flux；Repulsive interaction is all had to positive and negative charge containing anions and canons simultaneously in amphoteric ion film, therefore fouling membrane can be reduced greatly.
Description
Technical field
The invention belongs to UF membrane field, in particular to a kind of amphoteric ion nanofiltration membrane and preparation method thereof.
Background technique
Nanofiltration is the novel pressure-driven membrane separating process of one kind that developed recently gets up, be between reverse osmosis with ultrafiltration it
Between most promising one of the new and high technology of a kind of membrane separation technique and 21st century.Nanofiltration membrane has nanoscale
Aperture, operating pressure is low, can simplify conventional process, has to divalent, multivalent ion and relative molecular mass 200 or more
Machine object and big anion radical have a higher removal efficiency, and cost of investment and operation, maintenance cost are relatively low, are the current country
One of the hot spot of outer membrane separation field research.
Nanofiltration membrane currently on the market, supporting layer are usually fine and close ultrafiltration membrane, and therefore, the flux of nanofiltration membrane is generally not
It is high.In general, amphoteric membrane is mostly negatively charged film, this is because due to the water of acid chloride groups in traditional nanofiltration membrane preparation process
Solution, caused by so that film surface is generated carboxylic acid group, when in the solution of processing containing much ions containing positive electricity, nanofiltration membrane pollution is asked
Topic will be very serious, in terms of the preparation of antipollution nanofiltration membrane, be used for frequently with some hydrophilic, low pollution polymer materials
Prepare nanofiltration membrane.In recent years, amphoteric ion polymer due to having cation and anion, Yi Qite simultaneously on same monomer
Some contamination resistances and be concerned.Currently, most bio-compatibles for concentrating on improving material about zwitterionic research
Property aspect, in terms of film preparation, amphoteric ion is used to improve the performance of micro-filtration and ultrafiltration membrane by only a small amount of research, and by both sexes
The aspect of performance that ion is used to improve nanofiltration membrane is also rarely reported.
Summary of the invention
The first object of the present invention is to provide a kind of amphoteric ion nanofiltration membrane, including by ultrafiltration membrane, graphene oxide, over-expense
The compound aramid layer containing amphoteric ion polymer on the supporting layer and supporting layer of the copolymer composition of chemoattractant molecule, effectively mentions
The high hydrophilicity of ultrafiltration membrane, reduces the pollution of film.
The second object of the present invention is to provide the preparation method of above-mentioned amphoteric ion nanofiltration membrane.
The present invention is achieved through the following technical solutions:
One, a kind of amphoteric ion nanofiltration membrane, including support layer and cortex, the support layer are ultrafiltration membrane, graphene oxide, over-expense
The copolymer of chemoattractant molecule, the cortex are the compound aramid layer containing amphoteric ion polymer on supporting layer.Oxidation is added
After graphene, since graphene oxide is a kind of hydrophilic nano particle, pass through vacuum filter to ultrafiltration in graphene oxide
When on film, since graphene oxide contains a large amount of hydrophilic functional group, while its specific surface area is also very big, this is very beneficial for
The flowing of hydrone, thus the membrane flux of amphoteric ion film is caused to dramatically increase, hydrophilicity improves.
Specifically, the aperture of the ultrafiltration membrane be 0.01 μm -0.05 μm, by polysulfones, polyether sulfone, polyethylene, polypropylene,
One of PVDF or polyacrylonitrile polymer material are made, and have good thermal stability, chemical stability, excellent machinery
Performance and creep-resistant property outstanding.
Specifically, containing a large amount of primary amine group in super branched molecule, mentioned to be reacted with the group at graphene oxide edge
For possible.
Specifically, the super branched molecule is triethylene tetramine, in diethylenetriamine, 0-5 polyamide-amine dendrimer
One kind.
Two, the preparation method of above-mentioned amphoteric ion nanofiltration membrane, the specific steps are as follows:
Step 1: ultrafiltration membrane is immersed in positively charged solution, and shake it, make inside ultrafiltration membrane with positive electricity
Lotus；
Step 2: obtaining the graphite oxide that concentration is 0.1g/L-10g/L by graphene oxide ultrasonic disperse in deionized water
Aqueous solution；The graphene oxide thin slice is product of the graphene after chemical oxidation and removing, and graphene oxide is single
Atomic layer, can expand to some tens of pm on lateral dimension at any time, therefore, the general chemistry of construct trans and material supply section
Typical size, graphene oxide can be considered a kind of flexible material of non-traditional kenel, have polymer, colloid, film, with
And the characteristic of amphiphatic molecule, graphene oxide are considered as hydroaropic substance for a long time, because it has superior point in water
Dissipate property, but graphene oxide be of virtually it is amphipathic；
Step 3: the super branched molecule solution that concentration is 0.1-10mg/L is pressed with graphene oxide water solution made from step 2
Volume ratio 1:1-10 mixing, is made mixed liquor；
Step 4: by mixed liquor made from step 3 through ultrafiltration membrane vacuum filter, filtered ultrafiltration support membrane is spare；
Step 5: ultrafiltration support membrane filtered in step 4 is placed in oil-phase solution, time 10-720s, the oil phase
The solute of solution is the small-molecule substance containing acyl chlorides；In the carboxyl of surface of graphene oxide and super branched molecule molecule not at this time
With acid chloride groups interface polymerization reaction will occur for the remaining amido for participating in cross-linking reaction, generate ultra-thin polyamide cortex, the work
Property cortex for maintaining the interlamellar spacing of graphene oxide, realize to the effectively catching of solute, play important function；
Step 6: being placed in ultrafiltration support membrane obtained in step 5 containing in zwitterionic solution, 1-180min is reacted, is propped up
The acid chloride groups that reaction is had neither part nor lot in support layer will be chemically reacted with amphoteric ion, so that amphoteric ion is introduced into nanofiltration membrane
Surface；
Step 7: the film prepared in step 6 is placed in baking oven after heat treatment, cleaned with deionized water, obtained amphoteric ion is received
Filter membrane, film are placed in baking oven the further completion for promoting interface polymerization reaction.
Specifically, solution positively charged in step 1 is polyetherimide solution, polyallylamine hydrochloride solution, ten
One of dialkyl dimethyl ammonium chloride solution, dimethyl diallyl ammonium chloride solution.
Specifically, needing to increase catalyst Step between step 3 and step 4, the catalyst is ethanol solution, propyl alcohol
One of solution, phenol, ethoxy pyridine solution can be catalyzed reacting for super branched molecule and graphene oxide.
Specifically, mixed liquor made from step 3 is uniformly laid on ultrafiltration membrane using the method for vacuum filter in step 4
Surface.
Specifically, vacuum degree when vacuum filter is 0.2-1bar.
Specifically, the solvent of oil-phase solution is n-hexane or Isopars in the step 5, it can be preferable molten
Small-molecule substance of the solution containing acyl chlorides.
Specifically, the small-molecule substance containing acyl chlorides is m-phthaloyl chloride, paraphthaloyl chloride, three formyl of isophthalic
Ultra-thin polyamide activity cortex can be made in one or more of chlorine, four formyl chloride of isophthalic.
Specifically, amphoteric ion substance is polycarboxyl betaine, polysulfones base sweet tea in the zwitterionic solution of step 6
One of dish alkali, polyphosphoric acid glycine betaine, quaternary amine, N- amine ethyl piperazidine propane sultone (AEPPS).
Specifically, the concentration of amphoteric ion solution is 0.1-5.0%
Specifically, the temperature that baking oven is heat-treated in the step 7 is 10-150 DEG C, time 2-220min.
Specifically, final amphoteric ion film obtained is protected from light storage 1-96h.
To alleviate internal concentration polarization, the graphene oxide with two-dimensional layered structure is introduced in ultrafiltration membrane surface first,
Be conducive to construct unique aquaporin, and a large amount of hydrophilic radical is contained on its surface, and by the method for vacuum filter, makes to aoxidize
Graphene is laid in ultrafiltration membrane surface stratiform, is carried out by more amine monomers i.e. super branched molecule to graphene oxide interlayer
Crosslinking is fixed, and is finally contacted above-mentioned film with the small-molecule substance containing acyl chlorides to prepare the active cortex of ultrafiltration membrane.Therefore, it supports
The introducing of graphene oxide layer on film, so that the aperture above the support membrane contacted with active layer is no longer open state, therefore
From the design of membrane structure, it can suitably relax the aperture of supporting layer and carry out aperture optimization, improve permeation flux.
Since the highly-hydrophilic performance of graphene oxide makes it have and is highly susceptible to occurring interlayer disengaging or even is detached from super
The trend of basement membrane is filtered, therefore after introducing graphene oxide above ultrafiltration membrane, it is also necessary to by having neither part nor lot in instead in graphene oxide
The hydrophilic radical answered protects, it is prevented further to be swollen.Therefore the support membrane of above-mentioned load graphene oxide is further
It is mutually in contact with the oil of the small-molecule substance containing acyl chlorides, at this time in the carboxyl of surface of graphene oxide and super branched molecule molecule
With acid chloride groups interface polymerization reaction will occur for the remaining amido for having neither part nor lot in cross-linking reaction, generate ultra-thin polyamide activity skin
Layer, the activity cortex are realized to the effectively catching of solute for the interlamellar spacing of maintenance graphene oxide, play important function.
After introducing amphoteric ion in membrane structure, permeability of the membrane energy and antifouling property are significantly improved, modified
Film ZETA potential value in surface compared with former film increases, and shows to electronegative bacterium, Escherichia coli and positively charged epidermis
Staphylococcic anti-absorption pollution capacity enhances.Meanwhile the variation of film surface charge is to the rejection of its penetrating power and salt
Only slight change.Amphoteric ion film surface is capable of forming Free water hydration layer and makes it have good biocompatibility and resist
Pollutant performance.
The separation of ultrafiltration membrane depends on the size of membrane aperture, and fine and close support membrane can bring serious plug-hole problem,
To reduce plug-hole, it is preferably selected thin and big porosity supporting layer.
Good effect by adopting the above technical scheme: 1, introducing graphene oxide on supporting layer, by its vacuum filter to super
The surface of filter membrane effectively raises the parent of ultrafiltration membrane since surface of graphene oxide and edge contain a large amount of hydrophilic radical
Aqueous energy；2, the support that the copolymer of ultrafiltration membrane, graphene oxide, super branched molecule forms is placed on the small molecule containing acyl chlorides
In the oil-phase solution of substance, cross-linking reaction is had neither part nor lot in the carboxyl of surface of graphene oxide and super branched molecule molecule at this time
With acid chloride groups interface polymerization reaction will occur for remaining amido, generate ultra-thin polyamide cortex, for maintaining graphene oxide
Interlamellar spacing, realize to the effectively catching of solute, play important function；3, when above-mentioned nanofiltration film activity cortex and amphoteric ion
When solution further contacts, interface polymerization reaction is occurred into for the acyl chlorides with support membrane again, generates and contains zwitterionic nanofiltration
Film, simultaneously containing cation and anion in the zwitterionic same segment, therefore the amphoteric ion nanofiltration membrane prepared is more held
Easily absorption Free water, to improve membrane flux；4, contain anions and canons in amphoteric ion film simultaneously, therefore for handling material
In positive and negative charge all have repulsive interaction, therefore fouling membrane can be reduced greatly.
Specific embodiment
Technical method of the invention is described in further detail with test example combined with specific embodiments below, but not
Constitute any limitation of the invention, the modification of anyone limited times made within the scope of the invention as claimed, still at this
Within the scope of the claims of invention.
Embodiment 1
(1) polysulfone ultrafiltration membrane that aperture is 0.02 μm is immersed in polyetherimide solution, and it is shaken, make polysulfones
Positive charge is had inside ultrafiltration membrane；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 0.1g/L graphene oxide water solution；
(3) by graphene oxide water solution by volume 1 made from triethylene tetramine solution that concentration is 1mg/L and step (2):
1 mixing is added phenol solution as catalyst, mixed liquor is made；
(4) by the mixed liquor in step (3) through polysulfone ultrafiltration membrane vacuum filter, pressure is 0.4bar when vacuum filter, after filtering
Polysulfones ultrafiltration support membrane it is spare；
(5) polysulfones ultrafiltration support membrane obtained in step (4) is placed in oil-phase solution 60 seconds, the solvent of the oil-phase solution
Be positive hexane solvent, and solute is m-phthaloyl chloride；
(6) the polycarboxyl betaine solution phase for being further 3.0% with concentration by polysulfones ultrafiltration support membrane obtained in step (5)
Extra polycarboxyl betaine solution is poured out after reacting 180min, prepares amphoteric ion film by contact；
(7) the amphoteric ion film in step (6) is placed in baking oven after being heat-treated, temperature is 10 DEG C when heat treatment, and the time is
220min is cleaned with deionized water, and amphoteric ion nanofiltration membrane is made and is protected from light storage 1h.
Embodiment 2
(1) poly (ether-sulfone) ultrafiltration membrane that aperture is 0.01 μm is immersed in dimethyl diallyl ammonium chloride, and it is shaken
It swings, makes inside poly (ether-sulfone) ultrafiltration membrane with positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 1g/L graphene oxide water solution；
(3) by graphene oxide water solution by volume 1 made from diethylenetriamine solution that concentration is 5mg/L and step (2):
10 mixing are added ethanol solution as catalyst, mixed liquor are made；
(4) by the mixed liquor in step (3) through poly (ether-sulfone) ultrafiltration membrane vacuum filter, pressure is 0.6bar, filtering when vacuum filter
Polyether sulfone ultrafiltration support membrane afterwards is spare；
(5) polyether sulfone ultrafiltration support membrane obtained in step (4) is placed in oil-phase solution 10 seconds, the oil-phase solution it is molten
Agent is positive hexane solvent, and solute is paraphthaloyl chloride；
(6) the polysulfones base alkali solution of beet for being further 2.0% with concentration by polyether sulfone ultrafiltration support membrane obtained in step (5)
It is in contact, extra polysulfones base alkali solution of beet is poured out after reacting 10min, prepares amphoteric ion film；
(7) the amphoteric ion film in step (6) is placed in baking oven after being heat-treated, temperature is 60 DEG C when heat treatment, and the time is
180min is cleaned with deionized water, and amphoteric ion nanofiltration membrane is made and is protected from light storage 12h.
Embodiment 3
(1) polyacrylonitrile ultrafiltration film that aperture is 0.03 μm is immersed in dimethyl diallyl ammonium chloride solution, and to it
It is shaken, is made inside polyacrylonitrile ultrafiltration film with positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 5g/L graphene oxide water solution；
(3) by graphene oxide water solution by volume 1 made from triethylene tetramine solution that concentration is 8mg/L and step (2):
3 mixing are added propanol solution as catalyst, mixed liquor are made；
(4) by the mixed liquor in step (3) through polyacrylonitrile ultrafiltration film vacuum filter, pressure is 0.8bar, mistake when vacuum filter
Polyacrylonitrile ultrafiltration support membrane after filter is spare；
(5) polyacrylonitrile ultrafiltration support membrane obtained in step (4) is placed in oil-phase solution 180 seconds, the oil-phase solution
Solvent be positive hexane solvent, solute is three formyl chloride of isophthalic；
(6) the N- amine ethyl piperazidine third for being further 1.0% with concentration by polyacrylonitrile ultrafiltration support membrane obtained in step (5)
Sultones (AEPPS) solution is in contact, and falls extra N- amine ethyl piperazidine propane sultone (AEPPS) solution after reacting 1min
Out, amphoteric ion film is prepared；
(7) the amphoteric ion film in step (6) is placed in baking oven after being heat-treated, temperature is 100 DEG C when heat treatment, and the time is
120min is cleaned with deionized water, and amphoteric ion nanofiltration membrane is made and is protected from light storage for 24 hours.
Embodiment 4
(1) the polyethylene ultrafiltration membrane that aperture is 0.05 μm is immersed in polyallylamine hydrochloride solution, and it is shaken
It swings, makes inside polyethylene ultrafiltration membrane with positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 10g/L graphene oxide water solution；
It (3) is graphene oxide made from the 0-5 polyamide-amine tree dendrimer solutions of 0.1mg/L and step (2) by concentration
1:7 is mixed aqueous solution by volume, and ethoxy pyridine solution is added as catalyst, mixed liquor is made；
(4) by the mixed liquor in step (3) through polyethylene ultrafiltration membrane vacuum filter, pressure is 0.2bar, filtering when vacuum filter
Polyethylene ultrafiltration support membrane afterwards is spare；
(5) polyethylene ultrafiltration support membrane obtained in step (4) is placed in oil-phase solution 360 seconds, the oil-phase solution it is molten
Agent is positive hexane solvent, and solute is four formyl chloride of isophthalic；
(6) the quaternary amine salting liquid that polyethylene ultrafiltration support membrane obtained in step (5) is further 5.0% with concentration is in contact,
Extra quaternary amine salting liquid is poured out after reaction 80min, prepares amphoteric ion film；
(7) the amphoteric ion film in step (6) is placed in baking oven after being heat-treated, temperature is 130 DEG C when heat treatment, and the time is
60min is cleaned with deionized water, and amphoteric ion nanofiltration membrane is made and is protected from light storage 48h.
Embodiment 5
(1) the polypropylene ultrafiltration membrane that aperture is 0.04 μm is immersed in dodecyl dimethyl ammonium chloride solution solution, and right
It is shaken, and is made inside polypropylene ultrafiltration membrane with positive charge；
(2) by graphene oxide ultrasonic disperse in deionized water, obtaining concentration is 8g/L graphene oxide water solution；
(3) by concentration be 10mg/L diethylenetriamine solution and step (2) made from graphene oxide water solution by volume
1:5 mixing is added phenol solution as catalyst, mixed liquor is made；
(4) by the mixed liquor in step (3) through polypropylene ultrafiltration membrane vacuum filter, pressure is 1bar when vacuum filter, after filtering
Polypropylene ultrafiltration support membrane it is spare；
(5) polypropylene ultrafiltration support membrane obtained in step (4) is placed in oil-phase solution 720 seconds, the oil-phase solution it is molten
Agent is Isopars, and solute is paraphthaloyl chloride；
(6) the polyphosphoric acid alkali solution of beet for being further 0.1% with concentration by polypropylene ultrafiltration support membrane obtained in step (5)
It is in contact, extra polyphosphoric acid alkali solution of beet is poured out after reacting 120min, prepares amphoteric ion film；
(7) the amphoteric ion film in step (6) is placed in baking oven after being heat-treated, temperature is 150 DEG C when heat treatment, and the time is
2min is cleaned with deionized water, and amphoteric ion nanofiltration membrane is made and is protected from light storage 96h.
Test example 1
Control group: the commercialization nanofiltration membrane NF270 of DOW company.
Separation to further illustrate technical effect of the invention, to the amphoteric ion film in embodiment 1-5 and control group
Performance is tested, and is respectively the sodium sulphate, magnesium sulfate, sodium chloride solution and 0.1% of 1000mg/L with pure water and concentration
(wt.) BSA solution is shown in Table 1 as processing solution, test result:
1 amphoteric ion film properties test result of table
Seen from table 1, the water flux of amphoteric ion film is far longer than the water flux of NF270 nanofiltration membrane, in the retention to salt ion
See, since its surface is simultaneous with positive and negative two kinds of charges, there is good retention to divalent anions and canons in effect, it is special
It is not higher for monovalent ion and divalent ion separation selectivity.Amphoteric ion film for BSA permeation flux substantially 20
L/m2H or so, and the permeation flux of NF270 is 9.1 L/m2H, and amphoteric ion film initial flux and the ratio of stabilized flux are
Attenuation ratio is 1.06, and the flux decline of NF270 ratio is 1.25, i.e. the flux decline speed of amphoteric ion film is slower, antipollution
Effect is good.
Claims (10)
1. a kind of amphoteric ion nanofiltration membrane, it is characterised in that: including support layer and cortex, the support layer is ultrafiltration membrane, oxidation
The copolymer of graphene, super branched molecule, the cortex are the compound polyamide containing amphoteric ion polymer on supporting layer
Layer.
2. a kind of amphoteric ion nanofiltration membrane according to claim 1, it is characterised in that: the aperture of the ultrafiltration membrane is 0.01
It μm -0.05 μm, is made of one of polysulfones, polyether sulfone, polyethylene, polypropylene, PVDF or polyacrylonitrile polymer material.
3. a kind of amphoteric ion nanofiltration membrane according to claim 1, it is characterised in that: the super branched molecule is triethylene
One of tetramine, diethylenetriamine, 0-5 polyamide-amine dendrimer.
4. a kind of preparation method of amphoteric ion nanofiltration membrane according to claim 1, it is characterised in that: specific steps are such as
Under:
Step 1: ultrafiltration membrane is immersed in positively charged solution, and shake it, make inside ultrafiltration membrane with positive electricity
Lotus；
Step 2: obtaining the graphite oxide that concentration is 0.1g/L-10g/L by graphene oxide ultrasonic disperse in deionized water
Aqueous solution；
Step 3: the super branched molecule solution that concentration is 0.1-10mg/L is pressed with graphene oxide water solution made from step 2
Volume ratio 1:1-10 mixing, is made mixed liquor；
Step 4: by mixed liquor made from step 3 through ultrafiltration membrane vacuum filter, filtered ultrafiltration support membrane is spare；
Step 5: ultrafiltration support membrane filtered in step 4 is placed in oil-phase solution, time 10-720s, the oil phase
The solute of solution is the small-molecule substance containing acyl chlorides；
Step 6: being placed in ultrafiltration support membrane obtained in step 5 containing in zwitterionic solution, 1-180min is reacted；
Step 7: the film prepared in step 6 is placed in baking oven after heat treatment, cleaned with deionized water, obtained amphoteric ion is received
Filter membrane.
5. the preparation method of amphoteric ion nanofiltration membrane according to claim 4, it is characterised in that: positively charged in step 1
Solution be polyetherimide solution, polyallylamine hydrochloride solution, dodecyl dimethyl ammonium chloride solution, dimethyl
One of diallyl ammonium chloride solution.
6. the preparation method of amphoteric ion nanofiltration membrane according to claim 4, it is characterised in that: step 3 and step 4 it
Between need to increase catalyst Step, the catalyst is ethanol solution, propanol solution, phenol, one in ethoxy pyridine solution
Kind.
7. the preparation method of amphoteric ion nanofiltration membrane according to claim 4, it is characterised in that: when step 4 vacuum filter
Vacuum degree be 0.2-1bar.
8. the preparation method of amphoteric ion nanofiltration membrane according to claim 4, it is characterised in that: oily phase in the step 5
The solvent of solution is n-hexane or Isopars, and the small-molecule substance containing acyl chlorides is m-phthaloyl chloride, to benzene two
One or more of formyl chloride, three formyl chloride of isophthalic, four formyl chloride of isophthalic.
9. the preparation method of amphoteric ion nanofiltration membrane according to claim 4, it is characterised in that: the step 6 both sexes from
Amphoteric ion substance is polycarboxyl betaine, polysulfones base glycine betaine, polyphosphoric acid glycine betaine, quaternary amine, N- amine second in the solution of son
One of base piperazine propane sultone, the concentration of amphoteric ion solution are 0.1-5.0%.
10. the preparation method of amphoteric ion nanofiltration membrane according to claim 4, it is characterised in that: dried in the step 7
The temperature of case heat treatment is 10-150 DEG C, time 2-220min.
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| CN111517981B (en) * | 2020-04-23 | 2021-03-23 | 青海大学 | Zwitterion functionalized carbon nitride nanosheet and positively charged nanofiltration membrane |
| CN114452833A (en) * | 2021-12-28 | 2022-05-10 | 浙江大学 | Double-face nanofiltration membrane with positive and negative electricity heterogeneous structure and application thereof |
| CN114761110A (en) * | 2019-12-11 | 2022-07-15 | 日东电工株式会社 | Composite semipermeable membrane |
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| CN111517981B (en) * | 2020-04-23 | 2021-03-23 | 青海大学 | Zwitterion functionalized carbon nitride nanosheet and positively charged nanofiltration membrane |
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Application publication date: 20190712 |