CN103212312A - Asymmetric antioxidant permeable membrane and preparation method thereof - Google Patents
Asymmetric antioxidant permeable membrane and preparation method thereof Download PDFInfo
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- CN103212312A CN103212312A CN2013101588355A CN201310158835A CN103212312A CN 103212312 A CN103212312 A CN 103212312A CN 2013101588355 A CN2013101588355 A CN 2013101588355A CN 201310158835 A CN201310158835 A CN 201310158835A CN 103212312 A CN103212312 A CN 103212312A
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 title 1
- 230000003078 antioxidant effect Effects 0.000 title 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004952 Polyamide Substances 0.000 claims abstract description 29
- 229920002647 polyamide Polymers 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000004907 flux Effects 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 230000010287 polarization Effects 0.000 claims abstract description 10
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract 10
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 15
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 12
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 238000012696 Interfacial polycondensation Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims 3
- 230000003213 activating effect Effects 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 claims 1
- 239000012510 hollow fiber Substances 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 239000012466 permeate Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 3
- -1 salt ions Chemical class 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000005371 permeation separation Methods 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 14
- 238000001764 infiltration Methods 0.000 description 14
- 230000008595 infiltration Effects 0.000 description 14
- 238000009292 forward osmosis Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 238000012805 post-processing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 235000012489 doughnuts Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- HOGDNTQCSIKEEV-UHFFFAOYSA-N n'-hydroxybutanediamide Chemical compound NC(=O)CCC(=O)NO HOGDNTQCSIKEEV-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开了一种非对称耐氧化聚酰胺渗透膜的制备方法。此方法采用对苯二铵(MPD)和均苯三甲酰氯(TMC)单体，通过界面缩聚合的方法在聚砜(PES)支撑膜表面复合一层聚酰胺皮层，并采用乙二酸配合脱水剂对皮层进行后处理，制备出耐氧化的聚酰胺复合渗透膜。本发明使用的乙二酸配合脱水剂的处理方法可以有效改善聚酰胺皮层的耐氧化性和亲水性，并且配合非对称膜结构大幅度地减小了浓差极化对膜分离性能的影响，进一步提高膜的水通量和对盐离子的截留率。本发明的制备方法属首创，该工艺常温常压下操作，实验条件简单，制备周期短，特别适合于大批量高性能渗透分离膜的制备。The invention discloses a preparation method of an asymmetric oxidation-resistant polyamide permeable membrane. This method uses terephthalic diammonium (MPD) and trimesoyl chloride (TMC) monomers to compound a layer of polyamide skin on the surface of polysulfone (PES) support membrane through interfacial condensation polymerization, and uses oxalic acid to coordinate dehydration. The post-treatment of the cortex was carried out with the agent, and the oxidation-resistant polyamide composite permeable membrane was prepared. The treatment method of oxalic acid combined with dehydrating agent used in the present invention can effectively improve the oxidation resistance and hydrophilicity of the polyamide skin layer, and cooperate with the asymmetric membrane structure to greatly reduce the influence of concentration polarization on membrane separation performance , to further improve the water flux and the rejection rate of salt ions of the membrane. The preparation method of the present invention is original, and the process is operated under normal temperature and pressure, the experimental conditions are simple, the preparation period is short, and it is especially suitable for the preparation of large batches of high-performance permeation separation membranes.
Description
Invention field
The present invention relates to a kind of asymmetric resistance to oxidation polyamide infiltration film and preparation method thereof.
Technical background
China is the big country of a serious water shortage, and water resource only is 1/4 of a world average per capita.Shortage of water resources is serious day by day, is an important channel that solves water resources problems to seawater, the bitter source of warding off, and the permeable membrane isolation technics will day by day play a significant role.Polyamide infiltration film possess hydrophilic property is good, and flux is big, and the high characteristics of ion rejection, and good mechanical performance, heat endurance and hydrolytic stability are arranged.The main application of PA membrane at present have NF membrane (Nanofiltration, NF), reverse osmosis membrane (Reverse Osmosis, RO) and forward osmosis membrane (Forward Osmosis, FO) etc.But there are problems such as oxidation, concentration polarization in polyamide infiltration film in application process, and influences its stability and service life.
The concentration polarization phenomenon all produces influence greatly to the permeable membrane performance in the oxidative resistance of permeable membrane and hydrophily and the membrane process, is the three big factors that need emphasis to consider when carrying out the permeable membrane structural design.At present, the preparation method of high flux permeable membrane mainly contains phase inversion and interfacial polymerization.Wherein, phase inversion is the most ripe and obtains the membrane preparation technology of commercial applications the earliest, but phase transition method makes the integrated anisotropic membrane of self-supporting: cortex and supporting layer are commaterial, film support and function cortex are chimeric, the remaining porosity that reduced of air in the membrane pores, hinder passing through of water, the interior concentration polarization of film is higher.And interfacial polymerization prepares asymmetric permeable membrane and can optimize membrane structure, and cortex is fine and close more, in gradient loose of hypodermic layer.Can select different cortexes and supporting layer respectively, so both can reduce skin thickness, can eliminate the transition zone that causes densification again, thereby reduce concentration polarization, improve water flux.But the amino on polyamide infiltration film surface easily is oxidized to nitro, and hydroxylamino has reduced surface hydrophilicity, and the concentration polarization phenomenon is obvious, and water flux is reduced.Therefore improve the oxidative resistance of film, making its stable operation under excess oxygen is problem demanding prompt solution.
In recent years, people make polyamide infiltration film obtain using widely by new filming technology, especially become the main product of RO film.Compared to RO technology or other membrane separation technique, the FO technology has the low innate advantage of energy consumption, and development in recent years is rapid and become the research focus, is the optimal path of realizing the low energy consumption seawater desalination, also can be used for the penetration of sea water power field.Therefore, develop a kind of preparation method of special-purpose high flux resistance to oxidation polyamide infiltration film, utilization has great importance for film permeability and separation technology.
Summary of the invention
The object of the present invention is to provide a kind of asymmetric resistance to oxidation polyamide infiltration film and preparation method thereof, this preparation method's process conditions gentleness, equipment is simple, and energy consumption is low, and the cycle is short.
The preparation method of asymmetric resistance to oxidation polyamide infiltration film of the present invention utilizes interfacial polycondensation to close technology.Under the room temperature, with monomer pyromellitic trimethylsilyl chloride (TMC) and m-phenylene diamine (MPD) (MPD) outer surface polymerization one deck polyamide cortex at the ultrafiltration support membrane; Utilize ethanedioic acid, dehydrating agent 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) and compounding ingredient N-hydroxy-succinamide (NHS) that cortex is carried out post processing under certain condition again, make that film surface cortex is fine and close more, oxidative resistance and hydrophily significantly improve, effectively reduced the influence of interior concentration polarization, obtained the polyamide permeable antireflective film material of high water flux and rejection water flux.
The preparation method of a kind of asymmetric resistance to oxidation polyamide infiltration film of the present invention may further comprise the steps at least:
(1) doughnut is supported rete and heat-treat, drying is 60 minutes under 90 ℃ of conditions, makes film fully dry;
(2) film that will handle through step (1) immerses contain in mass fraction 2% m-phenylene diamine (MPD) (MPD) aqueous solution and handles, and makes the MPD molecule infiltrate the surface of film;
(3) film that will handle through step (2) immerses contain and carries out interfacial polycondensation in mass fraction 0.5% pyromellitic trimethylsilyl chloride (TMC) hexane solution and close, make MPD and TMC first step initial reaction take place on the film surface, react after 30～50 seconds and take out, form one deck initial film;
(4) will place 90 ℃ of baking ovens to carry out the reaction of second step through the film that handled step (3), two kinds of monomers are fully reacted, improve the compactness extent of polyamide cortex, realize the high rejection of film to salt ion, take out after reaction a period of time, secondary water fully cleans, and removes unreacted participation monomer;
(5) will place the 10% ethanedioic acid aqueous solution to carry out post processing through the asymmetric polyamide infiltration film of step (4) preparation, and in solution, add a certain amount of dehydrating agent 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) and compounding ingredient N-hydroxy-succinamide (NHS) reacts certain hour, ethanedioic acid and polyamide are fully reacted, take out and clean repeatedly with secondary water.
Wherein, the experimental procedure that the ethanedioic acid aqueous solution that utilize to add dehydrating agent carries out post processing to film is for to be divided into two stages: first configuration quality is 10% the ethanedioic acid aqueous solution, to enter through the permeable membrane that step (1)～handled (4) in this solution, reaction is 3 hours under the room temperature, makes film surface amino groups and ethanedioic acid carry out initial reaction; In solution, add mass fraction again and be 3% dehydrating agent EDC and 0.5% compounding ingredient NHS, dissolving fully, magnetic stirring apparatus stirs, the lucifuge reaction is 15～21 hours under the room temperature, makes the further fully reaction of film surface amino groups and ethanedioic acid carboxyl, weakens amino oxidation effect, improve the resistance to oxidation stability of film, and film surface carboxyl number increases, and the surface hydrophilic degree is strengthened, and has reduced the influence of concentration polarization to water flux; To fully clean up with secondary water through the film that step (1)～handled (5), remove remaining ethanedioic acid monomer, in secondary water, preserve.
The second stage processing time of described film was controlled at 15～20 minutes.
Described ethanedioic acid is to the post-processing stages of film, and the processing time was at 18～24 hours.
Compared with prior art, this preparation method has following characteristics:
(1) adopt interfacial polymerization to prepare asymmetric polyamide infiltration film, help reducing the influence of concentration polarization, and monomer reaction is active big membrane separating property, the preparation condition gentleness, cost is low;
(2) preparation method of asymmetric resistance to oxidation PA membrane of the present invention, utilize ethanedioic acid that film is carried out post processing, simple to operate, realized the target of high flux high oxidation resistance voltinism, and the hydrophiling degree on film surface is further improved, stable in long-time, this method is particularly suitable for preparing doughnut permeable membrane in enormous quantities;
(3) utilize the resistance to oxidation permeable membrane of this method preparation to be easy to storage, in the longer-term storage process, obvious oxidative phenomena can not take place.
Description of drawings
Fig. 1 handles the reaction mechanism schematic diagram of polyamide infiltration film for ethanedioic acid;
Fig. 2 is the cross section and the surperficial electromicroscopic photograph (S-4800) 1 of doughnut polyamide infiltration film: blank film cross section (10000 times); 2: PA membrane cross section (10000 times); 3: blank film surface (10000 times); 4 PA membrane surfaces (10000 times); The whole cross section (60 times) of 5 hollow-fibre membranes.
Fig. 3 is that the surface color of different post-processing approach films after 30 days changes 1: without the permeable membrane of post processing; 2,3: through the permeable membrane of monomer TMC post processing; 4,5: through the permeable membrane of ethanedioic acid post processing.
The specific embodiment
For drawing liquid, is material liquid with secondary water with the NaCl aqueous solution of concentration 2M, and specimen is as the water flux and the rejection of forward osmosis membrane.Doughnut permeable membrane with preparation places the self-control checkout gear to carry out positive penetration testing earlier, at room temperature (23 ℃), regulate the certain flow velocity of control, make water flow pressure remain on 0.1MPa, the quality that the material liquid that utilizes the test of AY220 type electronic balance to see through forward osmosis membrane consumes.Every 1min mass change is carried out one-shot measurement, calculate the water transit dose of forward osmosis membrane unit are unit interval, maximum can reach 40L/ (m
2H).Utilize the test of DDS-307 type electric conductivity instrument to draw liquid front and back change in concentration, calculate the rejection of permeable membrane salt ion.The permeable membrane that the process ethanedioic acid is handled can reach 96% to the rejection of NaCl ion.
MgCl with concentration 2M
2The aqueous solution is material liquid for drawing liquid with secondary water, and specimen is as the water flux and the rejection of forward osmosis membrane.Place the self-control checkout gear to carry out positive penetration testing the doughnut forward osmosis membrane of preparation, at room temperature (23 ℃), regulate the certain flow velocity of control, make water flow pressure remain on 0.1MPa, utilize the electronic balance test to see through the consumption quality of the material liquid of forward osmosis membrane.Every 1min mass change is carried out one-shot measurement, calculate the water transit dose of forward osmosis membrane unit are unit interval, maximum can reach 52L/ (m
2H).Utilize the test of DDS-307 type electric conductivity instrument to draw liquid front and back change in concentration, calculate the rejection of permeable membrane salt ion.The permeable membrane that the process ethanedioic acid is handled is to MgCl
2The rejection of ion can reach 98%.
With the NaCl aqueous solution simulated seawater of concentration 0.6M, be that infiltrate makes up pressure damping infiltration (PRO) electricity generation system with the river, specimen is as the water flux and the rejection of forward osmosis membrane.Doughnut permeable membrane with preparation places the PRO device for detecting performance earlier, and at room temperature (23 ℃), the certain flow velocity of control valve size control utilizes the electronic balance test to see through the consumption quality of the material liquid of forward osmosis membrane.Every 1min mass change is carried out one-shot measurement, calculate the water transit dose of forward osmosis membrane unit are unit interval, maximum can reach 100L/ (m
2H).Utilize the test of DDS-307 type electric conductivity instrument to draw liquid front change in concentration, calculate the rejection of permeable membrane salt ion.The permeable membrane that the process ethanedioic acid is handled can reach 99% to the rejection of NaCl ion.
Claims (6)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015196753A1 (en) * | 2014-06-25 | 2015-12-30 | 天津大学 | Polyetherimide composite nanofiltration membrane and preparation method thereof |
| CN106853343A (en) * | 2016-11-29 | 2017-06-16 | 攀枝花市九鼎智远知识产权运营有限公司 | The treatment Application way and equipment of a kind of sand slurry |
| CN109647224A (en) * | 2018-12-28 | 2019-04-19 | 南京理工大学 | Chlorine-resistant polyamide composite reverse osmosis membrane and preparation method thereof |
| CN111841343A (en) * | 2020-07-30 | 2020-10-30 | 河南师范大学 | A kind of asymmetric polyamide nano-film and preparation method thereof |
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| CN101439271A (en) * | 2008-12-04 | 2009-05-27 | 宁波灏钻科技有限公司 | Method for preparing hydrophilic anti-pollution reverse osmosis membrane |
| CN102641667A (en) * | 2012-05-03 | 2012-08-22 | 天津大学 | Preparation method of polyamide composite nanofiltration membrane |
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2013
- 2013-04-28 CN CN201310158835.5A patent/CN103212312B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1054200A (en) * | 1989-12-14 | 1991-09-04 | 联合信号股份有限公司 | Dry high flux semipermeable membranes |
| CN101439271A (en) * | 2008-12-04 | 2009-05-27 | 宁波灏钻科技有限公司 | Method for preparing hydrophilic anti-pollution reverse osmosis membrane |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015196753A1 (en) * | 2014-06-25 | 2015-12-30 | 天津大学 | Polyetherimide composite nanofiltration membrane and preparation method thereof |
| US9889413B2 (en) | 2014-06-25 | 2018-02-13 | Tianjin University | Polyetherimide composite nanofiltration membrane and preparation method thereof |
| CN106853343A (en) * | 2016-11-29 | 2017-06-16 | 攀枝花市九鼎智远知识产权运营有限公司 | The treatment Application way and equipment of a kind of sand slurry |
| CN106853343B (en) * | 2016-11-29 | 2019-11-12 | 江苏银服智能装备有限公司 | A method and equipment for processing and utilizing sand slurry |
| CN109647224A (en) * | 2018-12-28 | 2019-04-19 | 南京理工大学 | Chlorine-resistant polyamide composite reverse osmosis membrane and preparation method thereof |
| CN111841343A (en) * | 2020-07-30 | 2020-10-30 | 河南师范大学 | A kind of asymmetric polyamide nano-film and preparation method thereof |
| CN111841343B (en) * | 2020-07-30 | 2022-04-15 | 河南师范大学 | Asymmetric polyamide nano-film and preparation method thereof |
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