CN109647224A - Chlorine-resistant polyamide composite reverse osmosis membrane and preparation method thereof - Google Patents
Chlorine-resistant polyamide composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN109647224A CN109647224A CN201811618515.2A CN201811618515A CN109647224A CN 109647224 A CN109647224 A CN 109647224A CN 201811618515 A CN201811618515 A CN 201811618515A CN 109647224 A CN109647224 A CN 109647224A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- 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
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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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- 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
Abstract
The invention discloses a kind of chlorine-resistant polyamide composite reverse osmosis membranes and preparation method thereof.The chlorine-resistant polyamide composite reverse osmosis membrane is by the way that polyamide reverse osmose membrane to be immersed in the active acyl chloride reactant solution that concentration is 1wt%~4wt%, oscillating reactions, secondary interface polymerization is carried out, formation is made completely with the polyamide separating layer structure of carboxy blocking.Chlorine-resistant polyamide composite reverse osmosis membrane of the invention overcomes the disadvantage of traditional commerce reverse osmosis membrane anti-chlorine performance difference, obtained complex reverse osmosis membrane has both good salt rejection rate and anti-chlorine performance, under the chlorization condition of 30000ppmh, still it is able to maintain the rejection for having 90% or more to NaCl, can long-play working condition existing for chlorine residue, have a extensive future.
Description
Technical field
The present invention relates to separation technical field of membrane, are related to a kind of reverse osmosis membrane and preparation method thereof, and in particular to Yi Zhongnai
Chlorine polyamide composite reverse osmosis membrane and preparation method thereof.
Background technique
With water resource worsening, shortage of water resources problem, which becomes, has become global problem.Reverse osmosis technology conduct
One of the economy of sea water desalination and bitter desalination, high efficiency technical have preferable market application prospect.Reverse osmosis membrane materials are made
For the core of the technology, long-term running stability is related to the normal operation of a set of membrane method water treatment system.
In the application of practical Seawater Desalination Project, seawater complicated composition, though the pretreatment such as ultrafiltration, seawater are carried out to water body
Desalination membrane component may still be polluted by existing suspended matter or difficulty soluble salt, microorganism (algae, mould, fungi) etc..For
The former, generallys use soda acid cleaning process；For the latter, sterilizing processing can be carried out to water inlet in advance.In engineer application, often
Fungicide has hydrogen peroxide, sodium hydrogensulfite and the fungicide (such as sodium hypochlorite) containing chlorine, every kind of fungicide Disinfection Effect
Difference, wherein the fungicide bactericidal effect containing chlorine is more significant.Though have by further pre-processing, fungicide in water inlet still
There may be certain residual, and most of reverse osmosis membrane resistance to oxidation and the ability of chlorine residue are poor at present.For example, business is reverse osmosis
Aromatic ring and amide nitrogen in UF membrane layer can be attacked by chlorine rapidly, cause film properties sharply decline (Desalination, 1994,
95,325-345).Furthermore reverse osmosis membrane surface is modified using glycylglycine, although it improves film to a certain extent
Anti-chlorine performance, but when chlorization condition is excessively harsh, film properties can still decline to obtain more obvious (ACS
Appl.Mater.Interfaces,2017,9,10214-10223).The oxidation of membrane material will result directly in film properties failure, sternly
Ghost image rings the service life of film.Although people achieve very in terms of the synthesis of novel oxidation-resistant membrane material and the modification of membrane material
Good achievement, but preferable industrialization product is actually rare, therefore develops chlorine-resistant reverse osmosis membrane and have a very important significance.
Summary of the invention
In order to overcome the defect of existing reverse osmosis membrane chlorine-resistant property difference, the present invention provides a kind of with excellent anti-chlorine
Performance and the chlorine-resistant polyamide composite reverse osmosis membrane of salt rejection rate and preparation method thereof.
Technical scheme is as follows:
Chlorine-resistant polyamide composite reverse osmosis membrane of the present invention, by active acyl chloride reactant to polyamide reverse osmose membrane
It carries out surface termination process to be prepared, the active acyl chloride reactant is the aromatic compound with acid chloride functional groups.
Polyamide reverse osmose membrane of the present invention is conventional use of polyamide reverse osmose membrane in water treatment field, including
The material of supporting layer and separating layer, the supporting layer is not particularly limited, usually can be by polyester, polyacrylonitrile, poly- inclined
At least one of the non-sulfonated polyether sulphone of vinyl fluoride, phenolphthalein type, polyether sulfone and polysulfones are made；The separating layer is not special
Ground limits, and is usually made by way of interfacial polymerization by m-phenylene diamine (MPD), p-phenylenediamine and pyromellitic trimethylsilyl chloride.
Supporting layer of the present invention with a thickness of conventional use of thickness, be specifically as follows 80~160 μm, more preferably
95~125 μm；
Separating layer of the present invention with a thickness of conventional use of thickness, be specifically as follows 0.05~0.3 μm, more preferably
It is 0.07~0.2 μm.
Polyamide reverse osmose membrane of the present invention is prepared by way of interfacial polymerization, specially first impregnates supporting layer
It in aqueous phase solution, is then immersed in organic phase solution again, last organic solvent cleaning, after solvent volatilization completely, washing
To reactionless residue, polyamide reverse osmose membrane is made.
Surface termination process of the present invention are as follows: it is 1wt%~4wt%'s that polyamide reverse osmose membrane, which is immersed in concentration,
In active acyl chloride reactant solution, oscillating reactions carries out secondary interface polymerization, is formed and is separated completely with the polyamide of carboxy blocking
Layer structure.
Surface end-capping reagent of the present invention is the aromatic compound with acid chloride functional groups, including but not limited to isophthalic
One of dimethyl chloride (IPC), chlorobenzoyl chloride (BC) and pyromellitic trimethylsilyl chloride (TMC) are a variety of.
Preferably, the solvent of the active acyl chloride reactant solution is one of n-hexane, normal heptane, Isopar G
Or it is a variety of.
Preferably, the secondary interface polymerization time is 1~60min；Secondary interface polymerization temperature is 20~50 DEG C.
Compared with prior art, the present invention having the advantage that
(1) aromatic compound of the invention to contain acid chloride functional groups is as surface end-capping reagent, by polyamide film surface
Remaining amino is completely reacted to carboxyl group, improves polyamide reverse osmose membrane anti-chlorine performance；
(2) separating property (permeability, choosing of polyamide composite reverse osmosis membrane of the invention and traditional reverse osmosis membrane materials
Selecting property) quite, and chlorine-resistant property is extremely excellent, under the chlorization condition of 30000ppmh, being still able to maintain has 90% to NaCl
Above rejection, therefore can long-play working condition existing for chlorine residue；
(3) synthesis technology of polyamide composite reverse osmosis membrane of the invention is simple, and raw material is cheap and easily-available, without using organic
Metallic catalyst or high-temperature and high-pressure conditions are suitable for industrial production and popularization, may be directly applied to the reverse osmosis membrane of commercialization
Surface greatlys improve the chlorine-resistant property of product film, extensive in water treatment field application prospect.
Detailed description of the invention
Fig. 1 is the basic property test and comparison figure of comparative example 1-2 and the reverse osmosis membrane in embodiment 1-9.
Fig. 2 is the performance degradation figure in comparative example 1-2 and embodiment 1-9 after reverse osmosis membrane chlorination.
The basic property and the performance map after chlorination that Fig. 3 is the reverse osmosis membrane of comparative example 3-4.
Specific embodiment
The invention will be further described with attached drawing with reference to embodiments.It should be understood that tool described herein
Body embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint and any value of the range illustrated herein are not limited to the accurate range or value, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The business SW30 reverse osmosis membrane used in following embodiment is purchased from auspicious anode membrane technology (Beijing) Co., Ltd, middle section.
The structural formula of each reagent used in the following embodiment is as follows:
M-phenylene diamine (MPD) (MPD), p-phenylenediamine (PPD), m-phthaloyl chloride (IPC), chlorobenzoyl chloride (BC) and equal benzene front three
Acyl chlorides (TMC),
The preparation of comparative example 1MPD/TMC reverse osmosis membrane
(1) preparation of aqueous phase solution A: m-phenylene diamine (MPD) 2g is dissolved in 100mL deionized water, after being completely dissolved, utilizes three second
Amine is adjusted after pH is 10 up to aqueous phase solution.
(2) preparation of organic phase solution B: pyromellitic trimethylsilyl chloride 0.15g is dissolved in 100mL n-hexane, after stirring and dissolving
Up to organic phase solution.
(3) aqueous phase solution prepared is poured over polyether sulfone support layer surface, it is molten to pour out extra water phase after immersion 10min
Liquid.Organic phase solution is poured into support layer surface again, contacts and pours out extra organic phase solution and clear with n-hexane after 60s
It washes, cleans its surface to reactionless residue with deionized water after solvent volatilization completely, aromatic polyamides reverse osmosis membrane is made
MPD/TMC is stored in spare in deionized water.
The preparation of 1 MPD/TMC/IPC chlorine-resistant reverse osmosis membrane of embodiment
The preparation process of IPC end-sealed type MPD/TMC film is similar with the preparation process of MPD/TMC reverse osmosis membrane in comparative example 1.
The difference is that the 100mL hexane solution for containing 2wt%IPC is poured on film again immediately after hexane solution cleaning treatment
Secondary interface polymerization reaction is carried out on surface.It stands dipping after five minutes, pours out solution again, rinse surface with fresh n-hexane
To remove unreacted acyl chlorides monomer.Finally, MPD/TMC/IPC chlorine-resistant reverse osmosis membrane is air-dried and store in deionized water to
It surveys.
The preparation of 2 MPD/TMC/BC chlorine-resistant reverse osmosis membrane of embodiment
The preparation process of BC end-sealed type MPD/TMC film is similar with the preparation process of MPD/TMC reverse osmosis membrane in comparative example 1.
The difference is that the hexane solution that 100mL contains 3wt%BC is poured on film table again immediately after hexane solution cleaning treatment
Secondary interface polymerization reaction is carried out on face.Stand dipping after ten minutes, pour out solution again, with fresh n-hexane rinse surface with
Remove unreacted acyl chlorides monomer.Finally, air-drying and storing to be measured in deionized water MPD/TMC/BC chlorine-resistant reverse osmosis membrane.
The preparation of 3 MPD/TMC/TMC chlorine-resistant reverse osmosis membrane of embodiment
The preparation process of TMC end-sealed type MPD/TMC film is similar with the preparation process of MPD/TMC reverse osmosis membrane in comparative example 1.
The difference is that the hexane solution that 100mL contains 1.5wt%TMC is poured on again immediately after hexane solution cleaning treatment
Secondary interface polymerization reaction is carried out in film surface.It stands dipping after ten minutes, pours out solution again, rinse table with fresh n-hexane
Face is to remove unreacted acyl chlorides monomer.Finally, MPD/TMC/TMC chlorine-resistant reverse osmosis membrane is air-dried and is stored in deionized water
It is to be measured.
The preparation of 2 PPD/TMC reverse osmosis membrane of comparative example
(1) preparation of aqueous phase solution A: p-phenylenediamine 3g is dissolved in 100mL deionized water, after being completely dissolved, utilizes three second
Amine is adjusted after pH is 11 up to aqueous phase solution.
(2) preparation of organic phase solution B: pyromellitic trimethylsilyl chloride 0.12g is dissolved in 100mL normal heptane, after stirring and dissolving
Up to organic phase solution.
(3) aqueous phase solution prepared is poured over polyether sulfone support layer surface, it is molten to pour out extra water phase after immersion 10min
Liquid.Organic phase solution is poured into support layer surface again, contacts and pours out extra organic phase solution and clear with normal heptane after 60s
It washes, cleans its surface to reactionless residue with deionized water after solvent volatilization completely, aromatic polyamides reverse osmosis membrane is made
PPD/TMC is stored in spare in deionized water.
The preparation of 4 PPD/TMC/IPC chlorine-resistant reverse osmosis membrane of embodiment
The preparation process of IPC end-sealed type PPD/TMC film is similar with the preparation process of PPD/TMC reverse osmosis membrane in comparative example 2.
The difference is that the n-heptane solution that 100mL contains 2.5wt%IPC is poured on again immediately after n-heptane solution cleaning treatment
Secondary interface polymerization reaction is carried out in film surface.Dipping is stood after 4 minutes, pours out solution again, rinses table with fresh normal heptane
Face is to remove unreacted acyl chlorides monomer.Finally, PPD/TMC/IPC chlorine-resistant reverse osmosis membrane is air-dried and is stored in deionized water
It is to be measured.
The preparation of 5 PPD/TMC/BC chlorine-resistant reverse osmosis membrane of embodiment
The preparation process of BC end-sealed type PPD/TMC film is similar with the preparation process of PPD/TMC reverse osmosis membrane in comparative example 2.
The difference is that the n-heptane solution that 100mL contains 4wt%BC is poured on film table again immediately after n-heptane solution cleaning treatment
Secondary interface polymerization reaction is carried out on face.Stand dipping 15 minutes after, pour out solution again, with fresh normal heptane rinse surface with
Remove unreacted acyl chlorides monomer.Finally, air-drying and storing to be measured in deionized water PPD/TMC/BC chlorine-resistant reverse osmosis membrane.
The preparation of 6 PPD/TMC/TMC chlorine-resistant reverse osmosis membrane of embodiment
The preparation process of TMC end-sealed type PPD/TMC film is similar with the preparation process of PPD/TMC reverse osmosis membrane in comparative example 2.
The difference is that the 100mL n-heptane solution for containing 1wt%TMC is poured on film again immediately after n-heptane solution cleaning treatment
Secondary interface polymerization reaction is carried out on surface.Dipping is stood after 6 minutes, pours out solution again, rinses surface with fresh normal heptane
To remove unreacted acyl chlorides monomer.Finally, PPD/TMC/TMC chlorine-resistant reverse osmosis membrane is air-dried and store in deionized water to
It surveys.
The preparation of 7 business SW30/IPC chlorine-resistant reverse osmosis membrane of embodiment
The Isopar G solution that 100mL contains 2.5wt%IPC is poured on quotient by the preparation process of IPC end-sealed type SW30 film
Secondary interface polymerization reaction is carried out in industry SW30 film surface.Dipping is stood after 4 minutes, solution is poured out again, with fresh Isopar
G rinses surface to remove unreacted acyl chlorides monomer.Finally, SW30/IPC chlorine-resistant reverse osmosis membrane is air-dried and is stored in deionization
It is to be measured in water.
The preparation of 8 business SW30/BC chlorine-resistant reverse osmosis membrane of embodiment
The Isopar G solution that 100mL contains 3wt%BC is poured on business by the preparation process of BC end-sealed type SW30 film
Secondary interface polymerization reaction is carried out in SW30 film surface.Dipping is stood after 18 minutes, solution is poured out again, with fresh Isopar G
Surface is rinsed to remove unreacted acyl chlorides monomer.Finally, SW30/BC chlorine-resistant reverse osmosis membrane is air-dried and is stored in deionized water
In it is to be measured.
The preparation of 9 business SW30/TMC chlorine-resistant reverse osmosis membrane of embodiment
The Isopar G solution that 100mL contains 1.3wt%TMC is poured on quotient by the preparation process of TMC end-sealed type SW30 film
Secondary interface polymerization reaction is carried out in industry SW30 film surface.Dipping is stood after 6 minutes, solution is poured out again, with fresh Isopar
G rinses surface to remove unreacted acyl chlorides monomer.Finally, SW30/TMC chlorine-resistant reverse osmosis membrane is air-dried and is stored in deionization
It is to be measured in water.
The preparation of 3 MPD/TMC/IPC chlorine-resistant reverse osmosis membrane of comparative example
The preparation process of IPC end-sealed type MPD/TMC film is similar with the preparation process of MPD/TMC reverse osmosis membrane in comparative example 1.
The difference is that the hexane solution that 100mL contains 0.5wt%IPC is poured on again immediately after hexane solution cleaning treatment
Secondary interface polymerization reaction is carried out in film surface.It stands dipping after five minutes, pours out solution again, rinse table with fresh n-hexane
Face is to remove unreacted acyl chlorides monomer.Finally, MPD/TMC/IPC chlorine-resistant reverse osmosis membrane is air-dried and is stored in deionized water
It is to be measured.
The preparation of 4 MPD/TMC/IPC chlorine-resistant reverse osmosis membrane of comparative example
The preparation process of IPC end-sealed type MPD/TMC film is similar with the preparation process of MPD/TMC reverse osmosis membrane in comparative example 1.
The difference is that the 100mL hexane solution for containing 5wt%IPC is poured on film again immediately after hexane solution cleaning treatment
Secondary interface polymerization reaction is carried out on surface.It stands dipping after five minutes, pours out solution again, rinse surface with fresh n-hexane
To remove unreacted acyl chlorides monomer.Finally, MPD/TMC/IPC chlorine-resistant reverse osmosis membrane is air-dried and store in deionized water to
It surveys.
The test of 10 reverse osmosis membrane performance of embodiment
The characterizing method of reverse osmosis membrane performance is that reverse osmosis membrane is put into the reverse osmosis testing mould of standard,
Under the conditions of 2000ppm NaCl, temperature are 25 DEG C, pH value 6.5-7.5, pressure are 1.2MPa, the flow of penetrating fluid is directly measured
P (unit L), and water flux J (L m is calculated according to formula J=P/ (S*T)-2h-1), wherein S is that (unit is effective membrane area
m2), T is the time (hour) of measurement；And according to formula R (%)=(1-CP/Cf) * 100 calculating salt rejection rates, wherein R is desalination hundred
Divide rate, CpIt is the solute concentration of penetrating fluid, CfIt is the solute concentration of test fluid.By the reverse osmosis membrane being prepared in above-mentioned standard
Film properties characterization under the conditions of test, test result is as shown in figs. 1 and 3.Reverse osmosis membrane in comparative example 1-3 and embodiment 1-9
To the rejection of sodium chloride 97% or more, and water flux is also at 14L m-2h-1Left and right.Unlike, comparative example 4 is made
Standby reverse osmosis membrane excessively leads to the smaller only 8.3L m of water flux due to sealing end agent content-2h-1.To sum up, the chlorine-resistant of end-sealed type
Reverse osmosis membrane is suitable with the common polyamide reverse osmosis membrane performance in comparative example.Therefore, the end blocking method that the present invention uses is not
Large effect can be generated to reverse osmosis basic film properties.
The test of 11 reverse osmosis membrane long-time chlorine-resistant property of embodiment
The characterizing method of reverse osmosis membrane performance is that reverse osmosis membrane is put into the reverse osmosis testing mould of standard,
Under the conditions of 2000ppmNaCl, temperature are 25 DEG C, pH value 6.5-7.5, pressure are 1.2MPa, the flow P of penetrating fluid is directly measured
(unit L), and water flux J (L m is calculated according to formula J=P/ (S*T)-2h-1), wherein S is that (unit is effective membrane area
m2), T is the time (hour) of measurement；And according to formula R (%)=(1-CP/Cf) * 100 calculating salt rejection rates, wherein R is desalination hundred
Divide rate, CpIt is the solute concentration of penetrating fluid, CfIt is the solute concentration of test fluid.This experiment is to comparative example 1-4 and embodiment 1-9 system
The reverse osmosis membrane obtained carries out dynamic chlorination experiment, is washed with deionized water, tests its separating property, test result such as Fig. 2 and 3 institute
Show.As can be seen from the results, the ordinary RO membrane in comparative example 1 and 2 is under the chlorization condition of 30000ppmh, to chlorine
The rejection for changing sodium can only be maintained at 70% or so, and comparative example 3 causes film in same chlorination item due to the deficiency of end-capping reagent concentration
Film properties under part can only also keep 80%, and the chlorine-resistant reverse osmosis membrane of comparative example 4 and the end-sealed type in embodiment 1-9 is same
Chlorization condition under be still able to maintain rejection to 90% or more sodium chloride.Therefore, illustrate that closed-end technology of the invention can have
The chlorine-resistant property of the promotion reverse osmosis membrane of effect.In conclusion closed-end technology of the invention is simple and easy to get, to the initial of reverse osmosis membrane
Performance has little effect, and chlorine-resistant property is excellent, there is wide prospects for commercial application.
Claims (10)
1. chlorine-resistant polyamide composite reverse osmosis membrane, which is characterized in that by active acyl chloride reactant to polyamide reverse osmose membrane into
Row surface termination process is prepared, and the active acyl chloride reactant is the aromatic compound with acid chloride functional groups.
2. chlorine-resistant polyamide composite reverse osmosis membrane according to claim 1, which is characterized in that the active acyl chloride reaction
Object is selected from one of m-phthaloyl chloride, chlorobenzoyl chloride and pyromellitic trimethylsilyl chloride or a variety of.
3. chlorine-resistant polyamide composite reverse osmosis membrane according to claim 1 or 2, which is characterized in that the polyamide is anti-
Permeable membrane, including supporting layer and separating layer, the supporting layer are non-sulfonated by polyester, polyacrylonitrile, Kynoar, phenolphthalein type
At least one of polyether sulphone, polyether sulfone and polysulfones are made；The separating layer is by m-phenylene diamine (MPD), p-phenylenediamine and equal benzene three
Formyl chloride is made by way of interfacial polymerization.
4. chlorine-resistant polyamide composite reverse osmosis membrane according to claim 3, which is characterized in that the thickness of the supporting layer
Be 80~160 μm, the separating layer with a thickness of 0.05~0.3 μm.
5. chlorine-resistant polyamide composite reverse osmosis membrane according to claim 3, which is characterized in that the thickness of the supporting layer
Be 95~125 μm, the separating layer with a thickness of 0.07~0.2 μm.
6. chlorine-resistant polyamide composite reverse osmosis membrane according to claim 3, which is characterized in that the polyamide reverse osmosis
Film is prepared by way of interfacial polymerization, and specially first supporting layer is immersed in aqueous phase solution, is then immersed in organic phase again
In solution, last organic solvent cleaning is washed to reactionless residue after solvent volatilization completely, and polyamide reverse osmosis is made
Film.
7. chlorine-resistant polyamide composite reverse osmosis membrane according to claim 1 or 2, which is characterized in that the surface sealing end
Processing are as follows: be immersed in polyamide reverse osmose membrane in the active acyl chloride reactant solution that concentration is 1wt%~4wt%, oscillation is anti-
It answers, carries out secondary interface polymerization, formed completely with the polyamide separating layer structure of carboxy blocking.
8. chlorine-resistant polyamide composite reverse osmosis membrane according to claim 7, which is characterized in that the active acyl chloride reaction
The solvent of object solution is one of n-hexane, normal heptane, Isopar G or a variety of, and the secondary interface polymerization time is 1
~60min；Secondary interface polymerization temperature is 20~50 DEG C.
9. the preparation method of chlorine-resistant polyamide composite reverse osmosis membrane according to claim 1 or 2, which is characterized in that will gather
Amide reverse osmosis membrane is immersed in the active acyl chloride reactant solution that concentration is 1wt%~4wt%, and oscillating reactions carries out secondary
Interfacial polymerization is formed completely with the polyamide separating layer structure of carboxy blocking.
10. application of -8 any chlorine-resistant polyamide composite reverse osmosis membranes in water process according to claim 1.
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| CN110141982A (en) * | 2019-04-26 | 2019-08-20 | 浙江工业大学 | A kind of high throughput equipment with high desalinization mixed-matrix reverse osmosis membrane and the preparation method and application thereof |
| CN112973448A (en) * | 2019-12-12 | 2021-06-18 | 南京理工大学 | Composite reverse osmosis membrane with chlorine resistance body, preparation method and application thereof |
| CN112973449A (en) * | 2019-12-12 | 2021-06-18 | 南京理工大学 | Polyester composite reverse osmosis membrane with chlorine resistance and preparation method and application thereof |
| CN113385047A (en) * | 2021-05-10 | 2021-09-14 | 清华大学 | Separation membrane for water treatment and preparation method and application thereof |
| CN113398784A (en) * | 2021-05-28 | 2021-09-17 | 北京碧水源分离膜科技有限公司 | Preparation method of novel nanofiltration membrane |
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| CN112973448B (en) * | 2019-12-12 | 2022-06-10 | 南京理工大学 | Composite reverse osmosis membrane with chlorine resistance body, preparation method and application thereof |
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