CN109260968A - A kind of preparation method of amphoteric ion Nano capsule modified polyamide nanofiltration membrane - Google Patents
A kind of preparation method of amphoteric ion Nano capsule modified polyamide nanofiltration membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
A kind of preparation method of amphoteric ion Nano capsule modified polyamide nanofiltration membrane includes: the preparation of (one) amphoteric ion Nano capsule: Tween 80 and Span 80 being dissolved in n-hexane and obtain oily phase；By ammonium persulfate, amphiphilic poly (MAA16‑Co‑MMA9) RAFT reagent, methacryloylethyl sulfobetaines and N, N- methylene-bisacrylamide be dissolved in the phosphate buffered saline solution of pH value 6-9, obtain water phase；Water phase is slowly dropped into oily phase in stirring, stirring pre-emulsification forms thick lotion in ice-water bath；Thick lotion is through the obtained miniemulsion of ultrasound；Tetramethylethylenediamine is added in miniemulsion, reaction obtains amphoteric ion Nano capsule；(2) preparation of nanofiltration membrane: being that using pyromellitic trimethylsilyl chloride and piperazine as principal monomer, using amphoteric ion Nano capsule as additive, nanofiltration membrane is prepared by interfacial polymerization in support counterdie with polysulfones basement membrane.The present invention substantially increases the antifouling property of former film, in the case where rejection variation is little, improves its water flux.
Description
Technical field
The invention belongs to nanofiltration membrane separation fields, are related specifically to a kind of amphoteric ion Nano capsule modified polyamide nanofiltration
The preparation method of film.
Background technique
Nanofiltration (Nanofiltration, abbreviation NF) is usually used in separating because of the features such as its operating pressure is low, selectivity is good
Small organic molecule and salt ion.But with the continuous development of nanofiltration, the pollution problem of nanofiltration membrane is sent out as membrane technology
The important bottleneck of exhibition.Amphoteric ion hollow nano capsule has good hydrophily, and being entrained on film can not only improve
The antifouling property of film, and its water flux can be improved.
With specific surface area sharply increases, surface atom number increases, surface free energy increases when nanoparticle reaches nanoscale
By force, the advantages that surface-active enhances makes nanoparticle have some characteristics different from general material.And its big specific surface
Product, strong―binding interface effect and objective quantum tunneling effect make nano material have excellent properties not available for general material,
So nanoparticle to be blended to the many-sided performance that can effectively improve original membrane with some filmogens.
Sulphonic acid betaine type polymer is a kind of with azochlorosulfonate acid anion and quaternary ammonium salt cationic group and the two position
Substance on the same monomeric unit of macromolecular chain has been increasingly becoming a kind of new because of its good hydrophily and stain resistance
The membrane modifying material of type.Sulphonic acid betaine type polymer is acted on by molecule interchain electrostatic attraction effect and hydrophobe, can be formed
Aggregation containing certain amount macromolecular chain, i.e. colloidal nanoparticles.If sulfoacid betaine type colloid nanometer particle is introduced
Into PA membrane, good hydrophily and strong stain resistance not only can use, can also rely on its unique nano aperture knot
Structure improves the water permeability and stain resistance of film, can preferably meet the needs of daily life.Amphoteric ion nanometre glue
The appearance of capsule has amphoteric polymer and nanoparticle, and respectively unique feature is greatly improved due to its good hydrophily
The antifouling property of former film, rejection variation less in the case where, water flux significantly improves.
Summary of the invention
The present invention is heavily polluted problem for nanofiltration membrane in water process, and it is modified to propose a kind of amphoteric ion Nano capsule
The preparation method of polyamide nanofiltration membrane, in the case where rejection variation is little, is mentioned with greatly improving the antifouling property of former film
Its high water flux.
The present invention is achieved through the following technical solutions:
A kind of preparation method of amphoteric ion Nano capsule modified polyamide nanofiltration membrane comprising the steps of:
(1) preparation step of amphoteric ion Nano capsule is as follows:
(1-1) configures oily phase: Tween 80 (tween80) and Span 80 (span80) being added in n-hexane, magnetic force stirs
Mixing makes its uniform dissolution, obtains oily phase, wherein the mass percent concentration of Tween 80 and Span 80 be respectively 0.3-1.5% and
0.9-4.5%；
(1-2) configures water phase: successively adding after adjusting phosphate buffered saline solution (PBS) pH value to 6-9 with sodium hydroxide solution
Enter ammonium persulfate (APS), amphiphilic poly (MAA16-Co-MMA9) RAFT reagent, methacryloylethyl sulfobetaines
(SBMA) it is made it dissolve uniformly with N, N- methylene-bisacrylamide (MBAA), magnetic agitation, obtains water phase, wherein persulfuric acid
Ammonium, amphiphilic poly (MAA16-Co-MMA9) RAFT reagent, methacryloylethyl sulfobetaines and N, N- di-2-ethylhexylphosphine oxide third
The mass percent concentration of acrylamide is respectively 0.2-0.5%, 0.1-0.7%, 1-3% and 2-5%；
(1-3) oil is mutually vigorously stirred, and water phase is slowly dropped into oily phase, makes the volume ratio 1:10-20 of water phase with oily phase,
After 15-30min clock, the lotion stirred to get is placed in ice-water bath, continues to be vigorously stirred pre-emulsification 15-40min, forms thick cream
Liquid；
Thick lotion in ice-water bath is carried out ultrasound, ultrasound procedure are as follows: ultrasonic 2- by (1-4) under 350-600W operation power
5s stops 1-2s, and total ultrasonic time is 6-20min, and miniemulsion is made, and (fine crankshaft process is side reaction in order to prevent in ice-water bath
Generation)；
(1-5) pours into miniemulsion in reaction vessel, and tetramethylethylenediamine (TEMED) is added, tetramethylethylenediamine
Additional amount is calculated as 60-80 μ L/10-20g with the quality of miniemulsion, is condensed back, and leads to magnetic agitation after nitrogen deoxygenation, at 25-35 DEG C
It in water-bath, reacts 6-8 hour, and washing and drying treatment product is to get to amphoteric ion Nano capsule；
(2) preparation step of nanofiltration membrane is as follows:
Pyromellitic trimethylsilyl chloride is added in n-hexane by (2-1), and heating stirring dissolution is as oily phase, wherein three formyl of equal benzene
The concentration of chlorine is 0.05-0.25g/100mL；Amphoteric ion Nano capsule is added in oily phase, amphoteric ion Nano capsule is made
Concentration be 0.02-0.1g/100mL, stirring forms a white milky liquid, and sealing and standing obtains nanometre glue containing amphoteric ion
The oily phase of capsule；
(2-2) regard piperazine dissolved as water phase into deionized water, makes piperazine concentration 0.1-0.3g/100mL, adjusts molten
Liquid pH value 9-11；
Water phase is first poured on polysulfones basement membrane by (2-3), stand 5-10 minutes, then outwell extra aqueous phase solution, drain to
Surface water stain-free, then the oily phase of the Nano capsule containing amphoteric ion is poured on surface, after reacting 30-50s, amphoteric ion is made in drying
Nano capsule modified polyamide nanofiltration membrane.
Amphoteric ion Nano capsule described in step (1) is sulfonic acid beet type Nano capsule, and conversion ratio is in 50%-65%
Between.The amphoteric ion Nano capsule can be hollow capsules, be also possible to solid capsule, and those skilled in the art can be with
In rate-determining steps (1-1) in oily phase the concentration of Tween 80 and Span 80 come to control capsule be hollow or solid.The present invention is preferred
The amphoteric ion Nano capsule is amphoteric ion hollow nano capsule, and Tween 80 and the mass percent of Span 80 are dense in oily phase
Degree is respectively 0.3-0.9% and 0.9-2.7%.
In step (1-2), ammonium persulfate, amphiphilic poly (MAA in water phase16-Co-MMA9) RAFT reagent, metering system
The mass percent concentration of acyl ethyl sulfobetaines and N,N methylene bis acrylamide is respectively preferably 0.5%, 0.7%,
3% and 5%.
In step (1-5), the volumetric usage of tetramethylethylenediamine is preferably 60-80 μ L/ with meter with the quality of miniemulsion
15.5-16.5g。
In step (2-2), the pH value of water phase is preferably adjusted with tertiary sodium phosphate and hydrochloric acid, more preferably by 0.15mol/L's
The hydrochloric acid solution of trisodium phosphate solution and 0.6mol/L are by the pH value for being used to adjust aqueous phase solution after the volume ratio mixing of 4:1.
In step (2-3), drying temperature is 60-70 DEG C, preferably 65 DEG C；Drying time is 5-15min, preferably 10min.
Compared with prior art, the beneficial effects of the present invention are: on ultrafiltration support membrane interfacial polymerization occurs for the present invention
While reaction, amphoteric ion Nano capsule is entrained in aramid layer, so that novel Nano filtering composite membrane is prepared, because of both sexes
Ion Nano capsule has good hydrophily, and the antifouling property of film can not only be improved by being entrained in nanofiltration membrane, and
And in the case where rejection variation is little, its water flux can be improved.
Detailed description of the invention
Fig. 1 is the schematic diagram for the film properties evaluating apparatus instrument that the present invention uses, wherein 1- controlling value；2- pressure gauge；3- film
Component；4- permeates liquid pool；5- permeates liquid pool；6- membrane module；7- pressure gauge；8- controlling value；9- feed liquid pond.
Specific embodiment
The present invention is further described in conjunction with following Examples, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:
0.04g Tween 80 (tween80) and 0.12g Span 80 (span80) are added in 20mL n-hexane, magnetic force stirs
Mixing makes its uniform dissolution, obtains 13.36g oil phase；
Phosphate buffered saline solution (PBS) pH value is adjusted to 6 with sodium hydroxide solution, is sequentially added into 1.6g buffer solution
Amphiphilic poly (the MAA of 0.02g ammonium persulfate (APS), 0.02g16-Co-MMA9) RAFT reagent, 0.84g methacryloylethyl
Sulfobetaines (SBMA) and 0.03gN, N- methylene-bisacrylamide (MBAA), so that ammonium persulfate (APS), amphiphilic
poly(MAA16-Co-MMA9) RAFT reagent, methacryloylethyl sulfobetaines (SBMA) and N, N- methylene bisacrylamide acyl
The mass percent concentration of amine (MBAA) is respectively 0.5%, 0.7%, 3%, 5%, and magnetic agitation makes it dissolve uniformly, is obtained
2.50g water phase.
Under stirring conditions, 2.50g water phase is slowly dropped into 13.36g oil phase, the volume ratio of water phase and oily phase is 1:
After 10,15min clocks, the lotion stirred to get is placed in ice-water bath, continues to be vigorously stirred pre-emulsification 40min, forms thick lotion；
By the thick lotion in ice-water bath in 390W operation power, ultrasonic 2s/ stops ultrasound 6min under the spaced apart condition of 1s, and obtained partial size is
The miniemulsion of 100~150nm；And pour into miniemulsion in reaction vessel, and the tetramethylethylenediamine (TEMED) of 60 μ L is added,
It is condensed back, leads to magnetic agitation after nitrogen deoxygenation, in 35 DEG C of water-baths, react 6 hours, collect last product and wash dry place
Reason, can be obtained amphoteric ion hollow nano capsule.
Embodiment 2:
0.198 Tween 80 (tween80) and 0.594 Span 80 (span80) are added in 20mL n-hexane, magnetic force stirs
Mixing makes its uniform dissolution, obtains 13.992g oil phase；
Phosphate buffered saline solution (PBS) pH value is adjusted to 6 with sodium hydroxide solution, is sequentially added into 1.6g buffer solution
Amphiphilic poly (the MAA of 0.02g ammonium persulfate (APS), 0.02g16-Co-MMA9) RAFT reagent, 0.84g methacryloylethyl
Sulfobetaines (SBMA) and 0.03gN, N- methylene-bisacrylamide (MBAA), so that ammonium persulfate (APS), amphiphilic
poly(MAA16-Co-MMA9) RAFT reagent, methacryloylethyl sulfobetaines (SBMA) and N, N- methylene bisacrylamide acyl
The mass percent concentration of amine (MBAA) is respectively 0.5%, 0.7%, 3%, 5%, and magnetic agitation makes it dissolve uniformly, is obtained
2.50g water phase.
Under stirring conditions, 2.50g water phase is slowly dropped into 13.992g oil phase, the volume ratio of water phase and oily phase is
After 1:10,15min clock, the lotion stirred to get is placed in ice-water bath, continues to be vigorously stirred pre-emulsification 40min, forms thick cream
Liquid；
By the thick lotion in ice-water bath in 390W operation power, ultrasonic 2s/ stops ultrasound 6min under the spaced apart condition of 1s, is made
Partial size is the miniemulsion of 100~150nm；And miniemulsion is poured into reaction vessel, and the tetramethylethylenediamine of 60 μ L is added
(TEMED), it is condensed back, leads to magnetic agitation after nitrogen deoxygenation, in 35 DEG C of water-baths, react 6 hours, collect last product and wash
Drying process is washed, the solid capsule of amphoteric ion nanometer can be obtained.
Embodiment 3:
0.12g Tween 80 (tween80) and 0.36g Span 80 (span80) are added in 20mL n-hexane, tween is made
80 and the mass percent concentration of Span 80 be respectively 0.9% and 2.7%, magnetic agitation makes its uniform dissolution, obtains 13.68g
Oily phase；
Mixed phosphate buffer salt (PBS) pH value is adjusted to 9 with sodium hydroxide solution, is sequentially added into 1.6g buffer solution
Amphiphilic poly (the MAA of 0.02g ammonium persulfate (APS), 0.02g16-Co-MMA9) RAFT reagent, 0.84g methacryloylethyl
Sulfobetaines (SBMA) and 0.03g N, N- methylene-bisacrylamide (MBAA), so that ammonium persulfate (APS), amphiphilic
poly(MAA16-Co-MMA9) RAFT reagent, methacryloylethyl sulfobetaines (SBMA) and N, N- methylene bisacrylamide acyl
The mass percent concentration of amine (MBAA) is respectively 0.5%, 0.7%, 3%, 5%, and magnetic agitation makes it dissolve uniformly, is obtained
2.50g water phase.
Under stirring conditions, 2.50g water phase is slowly dropped into 13.36g oil phase, the volume ratio of water phase and oily phase is 1:
After 20,30min clocks, the lotion after stirring is placed in ice-water bath, continues to be vigorously stirred pre-emulsification 15min, forms thick lotion；
By the thick lotion in ice-water bath in 585W operation power, ultrasonic 5s/ stops ultrasound 20min under the spaced apart condition of 1s, system
Obtain miniemulsion；And pour into miniemulsion in reaction vessel, and the tetramethylethylenediamine (TEMED) of 80 μ L is added, it is condensed back, leads to
Magnetic agitation after nitrogen deoxygenation is reacted 8 hours in 25 DEG C of water-baths, is collected last product and washing and drying treatment, be can be obtained
Amphoteric ion hollow nano capsule.
Embodiment 4
0.1g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.06g embodiment 1 is added in oily phase, amphoteric ion is made to receive by 0.1% (m/v)
The quality volume fraction of rice hollow capsules is 0.06%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
Film properties test method is as follows:
The performance of Nano filtering composite membrane is the dynamic filtration experiment test by film, and the performance evaluation instrument of the film is cross-current type
Device is shown in attached drawing 1.At normal temperature, it is surveyed under 0.6MPa using flux and cutoff performance of the evaluation instrument device to film to be measured
Examination.The effective diameter of this experiment experiment film to be measured used is 5cm, when device starts, by film elder generation precompressed 45min clock to be measured.Respectively
NaCl, the Na for the use of salt additive amount being 2g/L2SO4Solution carries out film properties test.The flux of film can be expressed as the unit plane of film
Product, the liquid volume of unit time outflow, basic calculating formula can indicate are as follows:
Δ ν-penetrating fluid volume
Δ t-testing time
S-film validity test area
The rejection of film can indicate with the variation by film two sides inorganic salts additive amount to be measured, and basic calculating formula can be with
It indicates are as follows:
cs,pThe additive amount of salt in-penetrating fluid
cs,fThe additive amount of salt in-stoste
In addition, the bovine serum albumin (BSA) with additive amount for 2000mg/L is that simulated solution replaces salting liquid, using above-mentioned same
The test method of sample tests the antifouling property (flux recovery rate) of film.The basic relational expression specifically used is as follows:
J-film permeation flux (L/m2h)
Δ V-water transit dose (L)
A-film effective area (m2)
Δ t-time variation amount (h)
FRR-film flux recovery rate (%)
JtThe flux of-the film containing protein filtered fluid
J0The pure water flux of-film
The result shows that: it is tested under 0.6MPa pressure, diaphragm permeation flux Na2SO4For 73.8L/m2H, NaCl is
98.6L/m2H, salt rejection rate are 93.1% and 36.9% respectively, and flux recovery rate is 94.6%.
Comparative example 3
Referring to 4 step of embodiment, it is a difference in that and does not add amphoteric ion hollow nano capsule in oily phase.
The performance test methods of film are the same as embodiment 3, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 43.2L/m2.h, NaCl 63.6L/m2.h, salt rejection rate is 92.1% and 33.2% respectively, and flux recovery rate is
51.2%.
Comparative example 4
Referring to 4 step of embodiment, it is a difference in that the solid capsule of amphoteric ion nanometer that embodiment 2 is added in oily phase.
The performance test methods of film are the same as embodiment 3, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 30.2L/m2.h, NaCl 53.1L/m2.h, salt rejection rate is 91.7% and 30.4% respectively, and flux recovery rate is
49.9%.
Embodiment 5
0.05g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.06g embodiment 1 is added in oily phase, amphoteric ion is made to receive by 0.05% (m/v)
The quality volume fraction of rice hollow capsules is 0.06%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 87.2L/m2.h, NaCl 110.2L/m2.h, salt rejection rate is 85.1% and 24.7%, flux response rate respectively
91.8%.
Embodiment 6
0.15g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.06g embodiment 1 is added in oily phase, amphoteric ion is made to receive by 0.15% (m/v)
The quality volume fraction of rice hollow capsules is 0.06%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 72.7L/m2.h, NaCl 94.2L/m2.h, salt rejection rate is 93.8% and 38.1%, flux response rate respectively
92.7%.
Embodiment 7
0.2g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.06g embodiment 1 is added in oily phase, amphoteric ion is made to receive by 0.2% (m/v)
The quality volume fraction of rice hollow capsules is 0.06%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 71.8L/m2.h, NaCl 93.1L/m2.h, salt rejection rate is 93.4% and 37.5%, flux response rate respectively
92.1%.
Embodiment 8
0.25g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.06g embodiment 1 is added in oily phase, amphoteric ion is made to receive by 0.25% (m/v)
The quality volume fraction of rice hollow capsules is 0.06%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 70.9L/m2.h, NaCl 91.5L/m2.h, salt rejection rate is 92.7% and 37.8%, flux response rate respectively
91.3%.
Embodiment 9
0.1g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.02g embodiment 3 is added in oily phase, amphoteric ion is made to receive by 0.1% (m/v)
The quality volume fraction of rice hollow capsules is 0.02%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 51.3L/m2.h, NaCl 65.7L/m2.h, salt rejection rate is 93.1% and 34.7%, flux response rate respectively
81.9%.
Embodiment 10
0.1g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.04g embodiment 3 is added in oily phase, amphoteric ion is made to receive by 0.1% (m/v)
The quality volume fraction of rice hollow capsules is 0.04%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 55.9L/m2.h, NaCl 74.9L/m2.h, salt rejection rate is 93.4% and 36.1%, flux response rate respectively
89.8%.
Embodiment 11
0.1g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.08g embodiment 3 is added in oily phase, amphoteric ion is made to receive by 0.1% (m/v)
The quality volume fraction of rice hollow capsules is 0.08%, and heating stirring forms white milky solution after twenty minutes.By 0.2g piperazine
It is added in 100mL deionized water as water phase, makes the mass fraction 0.2% of piperazine, it is molten with the tertiary sodium phosphate of 0.15mol/L
The mixed liquor that the hydrochloric acid solution of liquid and 0.6mol/L are mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is fallen
On polysulfones counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface,
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after reaction 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 70.6L/m2.h, NaCl 94.3L/m2.h, salt rejection rate is 93.1% and 36.9%, flux response rate respectively
91.4%.
Embodiment 12
0.1g pyromellitic trimethylsilyl chloride is added in 100mL n-hexane, the quality volume fraction of pyromellitic trimethylsilyl chloride is made
Amphoteric ion hollow nano capsule prepared by 0.1g embodiment 3 is added in oily phase, makes amphoteric ion nanometer by 0.1% (m/v)
The quality volume fraction of hollow capsules is 0.1%, and heating stirring forms white milky solution after twenty minutes.0.2g piperazine is added
Be used as water phase into 100mL deionized water, make the mass fraction 0.2% of piperazine, with the trisodium phosphate solution of 0.15mol/L with
The mixed liquor that the hydrochloric acid solution of 0.6mol/L is mixed to get by the volume ratio of 4:1 adjusts water phase pH and is adjusted to 11.Water phase is poured on poly-
On sulfone counterdie, 5 minutes are stood, extra water phase is then removed, drains to surface water stain-free.Oily phase finally is poured on surface, is reacted
Baking oven drying film forming (65 DEG C of heat treatment temperature, heat treatment time 10min) is put into after 30s.
The performance test methods of film are the same as embodiment 4, the results showed that test under 0.6MPa pressure, diaphragm permeation flux
Na2SO4For 68.9L/m2.h, NaCl 91.8L/m2.h, salt rejection rate is 94.4% and 35.1%, flux response rate respectively
89.5%.
1 difference TMC monomer concentration of table corresponds to the performance of Nano filtering composite membrane
The ZNP of 2 Different adding amount of table corresponds to the performance of Nano filtering composite membrane
Claims (7)
1. a kind of preparation method of amphoteric ion Nano capsule modified polyamide nanofiltration membrane comprising the steps of:
(1) preparation step of amphoteric ion Nano capsule is as follows:
(1-1) configures oily phase: Tween 80 and Span 80 being added in n-hexane, magnetic agitation makes its uniform dissolution, obtains oil
Phase, wherein Tween 80 and the mass percent concentration of Span 80 are respectively 0.3-1.5% and 0.9-4.5%；
(1-2) configures water phase: sequentially adding persulfuric acid after adjusting phosphate buffered saline solution pH value to 6-9 with sodium hydroxide solution
Ammonium, amphiphilic poly (MAA16-Co-MMA9) RAFT reagent, methacryloylethyl sulfobetaines and N, N- di-2-ethylhexylphosphine oxide third
Acrylamide, magnetic agitation make it dissolve uniformly, obtain water phase, wherein ammonium persulfate, amphiphilic poly (MAA16-Co-MMA9)
The mass percent concentration of RAFT reagent, methacryloylethyl sulfobetaines and N,N methylene bis acrylamide is respectively
0.2-0.5%, 0.1-0.7%, 1-3% and 2-5%；
(1-3) oil is mutually vigorously stirred, and water phase is slowly dropped into oily phase, makes the volume ratio 1:10-20,15- of water phase with oily phase
After 30min clock, the lotion stirred to get is placed in ice-water bath, continues to be vigorously stirred pre-emulsification 15-40min, forms thick lotion；
Thick lotion in ice-water bath is carried out ultrasound, ultrasound procedure by (1-4) under 350-600W operation power are as follows: ultrasonic 2-5s,
Stop 1-2s, total ultrasonic time is 6-20min, and miniemulsion is made；
(1-5) pours into miniemulsion in reaction vessel, and tetramethylethylenediamine is added, and the additional amount of tetramethylethylenediamine is with thin cream
The quality of liquid is calculated as 60-80 μ L/10-20g, is condensed back, and leads to magnetic agitation after nitrogen deoxygenation, in 25-35 DEG C of water-bath, reacts 6-
8 hours, and washing and drying treatment product to get arrive amphoteric ion Nano capsule；
(2) preparation step of nanofiltration membrane is as follows:
Pyromellitic trimethylsilyl chloride is added in n-hexane by (2-1), and heating stirring dissolution is as oily phase, wherein pyromellitic trimethylsilyl chloride
Concentration is 0.05-0.25g/100mL；Amphoteric ion Nano capsule is added in oily phase, the dense of amphoteric ion Nano capsule is made
Degree is 0.02-0.1g/100mL, and stirring forms a white milky liquid, and sealing and standing obtains the Nano capsule containing amphoteric ion
Oily phase；
(2-2) regard piperazine dissolved as water phase into deionized water, makes piperazine concentration 0.1-0.3g/100mL, adjusts pH value of solution
Value 9-11；
Water phase is first poured on polysulfones basement membrane by (2-3), is stood 5-10 minutes, is then outwelled extra aqueous phase solution, drain to surface
Water stain-free, then the oily phase of the Nano capsule containing amphoteric ion is poured on surface, after reacting 30-50s, amphoteric ion nanometer is made in drying
Encapsulation modification polyamide nanofiltration membrane.
2. preparation method as described in claim 1, it is characterised in that: in step (1-1), the amphoteric ion Nano capsule
For amphoteric ion hollow nano capsule, controlling Tween 80 and the mass percent concentration of Span 80 in oily phase is respectively 0.3-
0.9% and 0.9-2.7%.
3. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (1-2), ammonium persulfate, parents in water phase
Property poly (MAA16-Co-MMA9) RAFT reagent, methacryloylethyl sulfobetaines and N,N methylene bis acrylamide
Mass percent concentration is respectively 0.5%, 0.7%, 3% and 5%.
4. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (1-5), the volume of tetramethylethylenediamine
Dosage is calculated as 60-80 μ L/15.5-16.5g with the quality dosage of miniemulsion.
5. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (2-2), with tertiary sodium phosphate and hydrochloric acid come
Adjust the pH value of water phase.
6. preparation method as claimed in claim 5, it is characterised in that: in step (2-2), by the tertiary sodium phosphate of 0.15mol/L
The hydrochloric acid solution of solution and 0.6mol/L are by the pH value for being used to adjust aqueous phase solution after the volume ratio mixing of 4:1.
7. preparation method as claimed in claim 1 or 2, it is characterised in that: in step (2-3), drying temperature is 60-70 DEG C,
Drying time is 5-15min.
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