CN107138060B - A kind of reverse osmosis membrane and preparation method thereof - Google Patents
A kind of reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN107138060B CN107138060B CN201710322649.9A CN201710322649A CN107138060B CN 107138060 B CN107138060 B CN 107138060B CN 201710322649 A CN201710322649 A CN 201710322649A CN 107138060 B CN107138060 B CN 107138060B
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- reverse osmosis
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- 239000012528 membrane Substances 0.000 title claims abstract description 96
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000012071 phase Substances 0.000 claims abstract description 51
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims abstract description 30
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 27
- 239000008346 aqueous phase Substances 0.000 claims abstract description 22
- 239000004952 Polyamide Substances 0.000 claims abstract description 11
- 229920002647 polyamide Polymers 0.000 claims abstract description 11
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 10
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000010410 layer Substances 0.000 claims description 18
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 14
- 239000012498 ultrapure water Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- -1 aroyl chloride Chemical compound 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002346 layers by function Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims 1
- YFZOUMNUDGGHIW-UHFFFAOYSA-M p-chloromercuribenzoic acid Chemical compound OC(=O)C1=CC=C([Hg]Cl)C=C1 YFZOUMNUDGGHIW-UHFFFAOYSA-M 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GGBJHURWWWLEQH-UHFFFAOYSA-N butylcyclohexane Chemical compound CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/021—Pore shapes
Abstract
The present invention relates to a kind of reverse osmosis membranes, including reverse osmosis membrane and the fullerene derivate being dispersed in the reverse osmosis membrane, preferably described fullerene derivate PCBM.The present invention also provides the preparation methods of the reverse osmosis membrane, including preparing the aqueous phase solution dissolved with m-phenylene diamine (MPD) and the oil-phase solution dissolved with pyromellitic trimethylsilyl chloride, then PCBM are dissolved in the oil-phase solution, the reverse osmosis membrane is obtained by interfacial polymerization.Compared with prior art, PCMB is introduced into polyamide film layer, and selective removal by the present invention, and the film layer of acquisition has the spherical pore structure of unique nanometer, can greatly improve the water-flowing amount of film.
Description
Technical field
The present invention relates to a kind of reverse osmosis membrane and preparation method thereof, especially a kind of fullerene derivate adulterates reverse osmosis
Film and preparation method thereof belongs to membrane for water treatment separation technology field.
Background technology
With the high speed development of the industrialization of the country, pollution of waterhead becomes the big problem that country is urgently to be resolved hurrily at present.People couple
The pursuit of healthy living forms sharp contradiction with worsening Drinking Water.To solve Industrial Wastewater Treatment and the people day
The problem of common water, various water technologies come into being, and wherein nanofiltration and reverse osmosis membrane is because to organic molecule and inorganic salts
The remarkable separating property and safety of ion, it is environmental-friendly, it is easy to operate the advantages that and as water process key technology it
One.Especially reverse osmosis technology can even more carry out water body selectively purifying and detaching, and application is very extensive, including
The wide range of areas such as seawater and the bitter degree of saltiness, water softening, middle water recycling, Industrial Wastewater Treatment, ultra-pure water preparation.
Current reverse osmosis technology mostly using composite membrane, can stablize the rejection of film, water flux because of it by composite membrane
Property etc. performances optimization and as current development it is most fast, using most film kinds, the reverse osmosis membrane more than 90% currently on the market
It is composite membrane.Composite membrane refer on porous support counterdie it is compound one layer very thin, fine and close, have special separation function not
Same material.Compared with integrated film, the surface dense layer of composite membrane is thinner, so as to which film be made to have high solute separation simultaneously
The transmission rates and optimizable physicalchemical structure of rate and water, can meet a variety of different Selective Separation demands.It is current wide
The general composite membrane in water treatment field mainly takes the mode of interfacial polymerization, and polyamide film is combined to micropore support bottom
Film surface.Common technical process, such as Chinese patent CN1817433A, CN101462025A, CN105664742A Deng Duopian state
Interior patent has disclosure.
Although reverse osmosis technology large-scale use, there are still many problems, reverse osmosis membrane as filter membrane one
Kind, service life and water flowing performance are always one of people's focus, the structure of a lot of complex reverse osmosis membranes due to being multilayer,
Although desalting performance increases, since accumulation dirt causes water flux to become smaller after long-time use so that reverse osmosis effect
Rate reduces, and doping increase hydroaropic substance can improve the water-flowing amount of reverse osmosis membrane in membrane material, such as pass through hydrophilic radical
It is modified.And it is more and more to improve the method for water-flowing amount by adding modifying agent in reverse osmosis membrane in recent years, but this mode
Also the problem of many additional is brought, for example manufacturing cost increases, complex process, membrane stability is deteriorated etc..
The problems occurred in terms of for current reverse osmosis membrane and preparation process, the present inventor attempts will be macro
The various modes for increasing air quantity in the air filtration of sight are applied in reverse osmosis membrane, it is found by the applicant that being passed through in air filtration media
It is often using three-dimensional porous structure, especially three-dimensional gap structure is not only able to play filter effect, moreover it is possible to ensure ventilation rate,
Based on this, inventor attempts to adulterate the material of macromolecular structure and the good good hydrophilic property of stability in membrane body, passes through length
Phase experimental studies have found that the very good hydrophilicity of fullerene and macromolecular structure, are doped in reverse osmosis membrane
Unexpectedly there is the effect of unexpected enhancing water flux, but fullerene structure is excessively stablized, and whole spherical in shape, leads to it
Molecule rank and the binding performance of polymer film are bad, easily come off, and the present inventor further improves, and find to adopt by attempting
It is doped in polyurethane film with the derivative of fullerene, is not only able to its molecule being attached in film layer, additionally it is possible in film layer
Play the role of pore-foaming agent, the firm fullerene derivate in engaging portion can come off, and then leave nanosphere under ultrasonication
The hole of shape, this hole and the relatively good fullerene derivate of combination act on the bumps inside film layer, strengthen film layer
Three-dimensional gap structure improves the water flowing of film layer, and there has been no fullerene derivate is applied to polyurethane reverse osmosis membrane so far
In report.
The present invention specifically addresses reverse osmosis membrane in the prior art water-flowing amount it is low the problem of, with provide can improve water flowing
Complex reverse osmosis membrane of amount and preparation method thereof.
Invention content
The object of the present invention is to provide a kind of reverse osmosis membranes and preparation method thereof, to improve water-flowing amount, solve big portion at present
The defects of dividing reverse osmosis membrane water-flowing amount low.
A kind of reverse osmosis membrane, including reverse osmosis membrane and the fullerene derivate being dispersed in the reverse osmosis membrane.
Further, wherein reverse osmosis membrane includes porous supporting body layer and polyamide functional layer, fullerene derivate dispersion
In aramid layer.
Further, there is the nanometer spherical micropore knot that fullerene derivate leaves after washing off in the polyamide functional layer
Structure.
Further, porous supporting body layer choosing is more from polysulfone porous support membrane, polyether sulfone porous support membrane or polyacrylonitrile
Hole support membrane, preferably polysulfone porous support membrane.
Further, the derivative of the fullerene is selected from the derivative of C60, C72 or C82, and preferably described fullerene spreads out
Biology is PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester, [6,6]-Phenyl-C73-
Butyric Acid Methyl Ester、[6,6]-Phenyl-C83-Butyric Acid Methyl Ester)。
In addition, the application also provides a kind of preparation method of above-mentioned reverse osmosis membrane, include the following steps：
1) preparation of aqueous phase solution：Aromatic amine is dissolved in water, it is molten to be configured to the water phase that mass fraction is 0.1-5%
Liquid, preferred mass score 1-2%；
2) preparation of oil-phase solution：By aroyl chloride dissolving in organic solvent, it is 0.1-3%'s to be configured to mass fraction
Oil-phase solution, preferred mass score 1-2%；
3) fullerene derivate is dissolved in the oil-phase solution, matter of the fullerene derivate in oil-phase solution
Amount score is 0.001-0.2%, preferably 0.01-0.1%, more preferable 0.01-0.05%；
4) interfacial polymerization：Porous support membrane is immersed in aqueous phase solution, open support film surface remaining is removed after taking-up
Aqueous phase solution, then interface polymerization reaction 30-80s is carried out after the open support film surface is contacted with oil-phase solution, obtained
Reverse osmosis membrane takes out the reverse osmosis membrane from oil-phase solution, and the reverse osmosis membrane is obtained after dry.
Further, the aromatic amine described in the step 1) be p-phenylenediamine, m-phenylene diamine (MPD), in equal benzene triamine at least
It is a kind of；
Further, the aroyl chloride described in the step 2) is paraphthaloyl chloride, m-phthaloyl chloride, adjacent benzene two
At least one of formyl chloride, biphenyl dimethyl chloride, pyromellitic trimethylsilyl chloride；
Further, the water described in step 1) is ultra-pure water；
Further, the organic solvent in step 2) is selected from n-hexane, petroleum ether, hexamethylene, isopar range of solvents, first
Butylcyclohexane, ethyl cyclohexane；
Further, after reverse osmosis membrane takes out from oil-phase solution described in the step 4), the vacuum at 30~80 DEG C
Dry 5~30min, it is subsequently placed in ultra-pure water after being cleaned by ultrasonic removal PCBM and preserves.
Further, the cleaning temperature is 30~40 DEG C, time 10-60min, ultrasonic frequency 20-
40kHz。
Further, fullerene derivate is bought by buying in the market, such as by lark prestige, Wuhan Zhuo Xin producers.
The reverse osmosis membrane of the present invention has preferable water flowing through testing application attestation, is mixed in polyamide functional film layer
Heterofullerene derivative, and fullerene derivate has stronger hydrophilicity, in addition its unique spherical structure, can make original
This single plane PA membrane forms rough fractal, conducive to passing through for hydrone.
In addition, polyamide film layer in forming process, has some fullerene derivate molecules, it is by derivative branch
Hydrogen bond intersect combination with polyamide molecule reticular structure, with reference to ratio it is stronger, other fullerene derivate molecule with
Polyamide network structure fails to form hydrogen bond, and only intermolecular force or physics are mixed between film layer, with reference to and loosely
Gu for combining these unstable fullerene derivate molecules, the hydrophilic property of fullerene derivate molecule can be utilized,
Disengaging is cleaned by the way of high-energy ultrasound, after treating that these fullerene derivate molecules come off, in polyamide film layer
In just form the spherical holes of much similar Graphene derivative molecular sizes, the firm graphene in these engaging portions can serve as
The effect of pore-foaming agent, the spherical hole formed after coming off further can allow hydrone to pass through, and the water for strengthening reverse osmosis film layer leads to
Amount, and then improve the service life of reverse osmosis membrane.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1,
Prepare the reverse osmosis membrane of doping PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester), tool
Body step is as follows：
1) preparation of aqueous phase solution：M-phenylene diamine (MPD) is dissolved in ultra-pure water, it is molten to be configured to the water phase that mass fraction is 1%
Liquid；
2) preparation of oil-phase solution：Pyromellitic trimethylsilyl chloride is dissolved in n-hexane, it is 1.5% to be configured to mass fraction
Oil-phase solution；
3) that PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester) is dissolved in the oil phase is molten
In liquid, mass fractions of the PCBM in oil-phase solution is 0.002%；
4) interfacial polymerization：Polysulfone porous support membrane is immersed in above-mentioned aqueous phase solution, porous support membrane is removed after taking-up
The aqueous phase solution of surface remaining, then interface polymerization reaction 40s is carried out after the open support film surface is contacted with oil-phase solution,
Reverse osmosis membrane is obtained, the reverse osmosis membrane is taken out from oil-phase solution, 60 DEG C of dry 10min, are subsequently placed in 30 in an oven
It is cleaned by ultrasonic removal PCBM15min, ultrasonic frequency 25kHz in DEG C ultra-pure water to get to the reverse osmosis membrane of doping PCBM.
Embodiment 2,
Prepare the reverse osmosis membrane of doping PCBM ([6,6]-Phenyl-C73-Butyric Acid Methyl Ester), tool
Body step is as follows：
1) preparation of aqueous phase solution：P-phenylenediamine is dissolved in ultra-pure water, it is molten to be configured to the water phase that mass fraction is 1%
Liquid；
2) preparation of oil-phase solution：Adjacent three formyl chloride of benzene is dissolved in hexamethylene, it is 1.5% to be configured to mass fraction
Oil-phase solution；
3) that PCBM ([6,6]-Phenyl-C73-Butyric Acid Methyl Ester) is dissolved in the oil phase is molten
In liquid, mass fractions of the PCBM in oil-phase solution is 0.005%；
4) interfacial polymerization：Polysulfone porous support membrane is immersed in above-mentioned aqueous phase solution, porous support membrane is removed after taking-up
The aqueous phase solution of surface remaining, then interface polymerization reaction 45s is carried out after the open support film surface is contacted with oil-phase solution,
Reverse osmosis membrane is obtained, the reverse osmosis membrane is taken out from oil-phase solution, 60 DEG C of dry 8min, are subsequently placed in 30 DEG C in an oven
In ultra-pure water be cleaned by ultrasonic removal PCBM15min, ultrasonic frequency 30kHz to get to doping PCBM reverse osmosis membrane.
Embodiment 3,
Prepare the reverse osmosis membrane of doping PCBM ([6,6]-Phenyl-C83-Butyric Acid Methyl Ester), tool
Body step is as follows：
1) preparation of aqueous phase solution：O-phenylenediamine is dissolved in ultra-pure water, it is molten to be configured to the water phase that mass fraction is 1%
Liquid；
2) preparation of oil-phase solution：Pyromellitic trimethylsilyl chloride is dissolved in petroleum ether, it is 1.5% to be configured to mass fraction
Oil-phase solution；
3) that PCBM ([6,6]-Phenyl-C83-Butyric Acid Methyl Ester) is dissolved in the oil phase is molten
In liquid, mass fractions of the PCBM in oil-phase solution is 0.008%；
4) interfacial polymerization：Polysulfone porous support membrane is immersed in above-mentioned aqueous phase solution, porous support membrane is removed after taking-up
The aqueous phase solution of surface remaining, then interface polymerization reaction 45s is carried out after the open support film surface is contacted with oil-phase solution,
Reverse osmosis membrane is obtained, the reverse osmosis membrane is taken out from oil-phase solution, 60 DEG C of dry 8min, are subsequently placed in 35 DEG C in an oven
In ultra-pure water be cleaned by ultrasonic removal PCBM15min, ultrasonic frequency 35kHz to get to doping PCBM reverse osmosis membrane.
Embodiment 4,
Prepare the reverse osmosis membrane of doping PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester), tool
Body step is as follows：
1) preparation of aqueous phase solution：Equal benzene triamine is dissolved in ultra-pure water, is configured to the water phase that mass fraction is 1.5%
Solution；
2) preparation of oil-phase solution：Biphenyl dimethyl chloride is dissolved in petroleum ether, it is 1.0% to be configured to mass fraction
Oil-phase solution；
3) that PCBM ([6,6]-Phenyl-C83-Butyric Acid Methyl Ester) is dissolved in the oil phase is molten
In liquid, mass fractions of the PCBM in oil-phase solution is 0.005%；
4) interfacial polymerization：Polysulfone porous support membrane is immersed in above-mentioned aqueous phase solution, porous support membrane is removed after taking-up
The aqueous phase solution of surface remaining, then interface polymerization reaction 50s is carried out after the open support film surface is contacted with oil-phase solution,
Reverse osmosis membrane is obtained, the reverse osmosis membrane is taken out from oil-phase solution, 80 DEG C of dry 5min, are subsequently placed in 40 DEG C in an oven
In ultra-pure water be cleaned by ultrasonic removal PCBM10min, ultrasonic frequency 40kHz to get to doping PCBM reverse osmosis membrane.
Reference examples,
The reverse osmosis membrane without adulterating PCBM is prepared, is as follows：
1) preparation of aqueous phase solution：M-phenylene diamine (MPD) is dissolved in ultra-pure water, it is molten to be configured to the water phase that mass fraction is 1%
Liquid；
2) preparation of oil-phase solution：Pyromellitic trimethylsilyl chloride is dissolved in petroleum ether, it is 1.5% to be configured to mass fraction
Oil-phase solution；
3) interfacial polymerization：Polysulfone porous support membrane is immersed in above-mentioned aqueous phase solution, porous support membrane is removed after taking-up
The aqueous phase solution of surface remaining, then interface polymerization reaction 40s is carried out after the open support film surface is contacted with oil-phase solution,
Reverse osmosis membrane is obtained, the reverse osmosis membrane is taken out from oil-phase solution, 70 DEG C of dry 8min are not to get to mixing in an oven
The reverse osmosis membrane of miscellaneous PCBM.
Embodiment 5：Test experiments
Complex reverse osmosis membrane obtained by embodiment 1-3 and comparative example is subjected to reverse osmosis operation experiments, test is corresponding
Salt rejection rate (REJ) and water flux.
Test primary condition：Raw water salt content (NaCL) 1500PPM, operating pressure 150PSI
The water flux of 1 diaphragm of table and salt rejection rate (REJ)
Wherein, water flux (F, L/m2H) it is defined as at certain temperature and operating pressure, in the unit interval (t) thoroughly
The water volume (V) of per membrane area (S) is crossed, calculation formula is：F=V/ (St).Salt rejection rate (R) is defined as in certain temperature
Under operating pressure, feeding liquid salinity (cf) with permeate in salinity (cp) difference, then divided by feeding liquid salinity (cf).
Calculation formula is：R (%)=(1-cp/cf) × 100%.
By above-mentioned test result, it is apparent that the reverse osmosis membrane doped with PCBM of 1-4 of the embodiment of the present invention has
Higher water-flowing amount and metastable salt rejection rate can have obviously high water flowing in the case where ensureing salt rejection rate
Amount, and as the increase of PCBM dopings, water-flowing amount are consequently increased, illustrate water flowing of the PCBM doping to improvement reverse osmosis membrane
Amount is very effective, while can ensure comparable salt rejection rate, this increases water-flowing amount with the prior art and sacrifices salt rejection rate
Method is compared, and has incomparable effect.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to before
Embodiment is stated the present invention is described in detail, it will be understood by those of ordinary skill in the art that：It still can be to preceding
The technical solution recorded in each embodiment is stated to modify or carry out equivalent replacement to which part technical characteristic；And these
Modification is replaced, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (6)
1. a kind of reverse osmosis membrane, which is characterized in that its fullerene for including reverse osmosis membrane and being dispersed in the reverse osmosis membrane spreads out
Biology, wherein reverse osmosis membrane include porous supporting body layer and polyamide functional layer, fullerene derivate are dispersed in aramid layer,
There is the nanometer spherical microcellular structure that fullerene derivate leaves after washing off, the fullerene derives in the polyamide functional layer
Object is PCBM.
2. reverse osmosis membrane according to claim 1, which is characterized in that porous supporting body layer choosing from polysulfone porous support membrane,
Polyether sulfone porous support membrane or polyacrylonitrile porous support membrane.
3. the preparation method of reverse osmosis membrane according to claim 1 or 2, which is characterized in that include the following steps：
1) preparation of aqueous phase solution：Aromatic amine is dissolved in water, is configured to the aqueous phase solution that mass fraction is 0.1-5%；
2) preparation of oil-phase solution：By aroyl chloride dissolving in organic solvent, it is configured to the oil phase that mass fraction is 0.1-3%
Solution；
3) fullerene derivate is dissolved in the oil-phase solution, the fullerene derivate quality in oil-phase solution point
Number is 0.001-0.2%：
4) interfacial polymerization：Porous support membrane is immersed in aqueous phase solution, the water of open support film surface remaining is removed after taking-up
Phase solution, then interface polymerization reaction is carried out after the open support film surface is contacted with oil-phase solution, reverse osmosis membrane is obtained, it will
The reverse osmosis membrane takes out from oil-phase solution, and 5~30min is dried in vacuo at 30~80 DEG C, is subsequently placed in ultra-pure water and surpasses
It is preserved after sound cleaning.
4. according to the method described in claim 3, it is characterized in that, aromatic amine described in the step 1) be p-phenylenediamine,
At least one of m-phenylene diamine (MPD), equal benzene triamine；Aroyl chloride described in the step 2) is paraphthaloyl chloride, isophthalic two
At least one of formyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride and pyromellitic trimethylsilyl chloride.
5. according to the method described in claim 3, the water described in step 1) is ultra-pure water；Organic solvent in step 2) is selected from
N-hexane, petroleum ether, hexamethylene, isopar range of solvents, hexahydrotoluene, ethyl cyclohexane.
6. according to the method described in claim 3, it is characterized in that, the cleaning temperature be 30~40 DEG C, time 10-
60min, ultrasonic frequency 20-40kHz.
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