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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Abstract
The invention discloses a preparation method of an asymmetric antioxidant polyamide permeable membrane. The method comprises the steps of: adopting p-phenylenediamine (MPD) and trimesoyl chloride (TMC) monomers, combining a polyamide surface layer on the surface of a polysulfone (PES) support membrane through an interfacial polycondensation way, and implementing posttreatment on the surface layer through oxalic acid cooperating with a dehydrating agent, thus preparing an antioxidant polyamide composite permeable membrane. The treatment method, which adopts the oxalic acid cooperating with the dehydrating agent, can effectively improve the oxidative resistance and the hydrophilicity of the polyamide surface layer, and the method, cooperating with an asymmetric membrane structure, can greatly reduce the influence of concentration polarization on membrane separating property, so as to further enhance the water flux of the membrane as well as the reject rate to salt ions. The initiative preparation method, which operates at normal temperature and under normal pressure, is simple in experimental condition and short in preparation cycle, and the method is specifically applicable to mass preparation of high-performance permeable separating 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)
1. an asymmetric resistance to oxidation polyamide permeates film and preparation method thereof, it is characterized in that this method may further comprise the steps at least:
(1) polysulfones (PES) doughnut supporting layer is heat-treated, drying is 60 minutes under 90 ℃ of conditions, makes film fully dry;
(2) the film sealing two ends that will handle through step (1) immerses to contain in mass percent 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 percent 0.5% pyromellitic trimethylsilyl chloride (TMC) hexane solution and close, make MPD and TMC first step initial reaction take place on the film surface, take out after reaction a period of time, 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 permeable membrane to salt ion.Take out after reaction a period of time, secondary water fully cleans, and removes the monomer that has neither part nor lot in reaction;
(5) will place the 10% ethanedioic acid aqueous solution to carry out post processing through the asymmetric permeable membrane 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), play activated carboxyl and amino effect, reaction a period of time, ethanedioic acid and polyamide are fully reacted, take out and clean repeatedly with secondary water.
2. a kind of asymmetric resistance to oxidation polyamide infiltration film according to claim 1 and preparation method thereof is characterized in that the immersion time described in the step (2) is 5～10 minutes, and overlong time solution sees through rete, can't prepare the anisotropic membrane structure.
3. the preparation method of a kind of asymmetric resistance to oxidation polyamide infiltration film according to claim 1 is characterized in that reaction time starting stage described in the step (3) is 30～50 seconds.
4. the preparation method of a kind of asymmetric resistance to oxidation polyamide infiltration film according to claim 1 is characterized in that the second stage processing rank time of the film described in the step (4) was controlled at 15～20 minutes.
5. the preparation method of a kind of asymmetric resistance to oxidation polyamide infiltration film according to claim 1 is characterized in that the post-processing stages of the ethanedioic acid described in the step (5) to film, and the processing time was at 18～24 hours.
6. the preparation method of a kind of asymmetric resistance to oxidation polyamide infiltration film according to claim 1, it is characterized in that experimental procedure that the ethanedioic acid aqueous solution that the utilization described in the step (5) adds 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 film 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, fully dissolving, stir with magnetic stirring apparatus, the lucifuge reaction is 15～21 hours under the room temperature, makes the further fully reaction of carboxyl of film surface amino groups and ethanedioic acid, weakens amino oxidation effect, improve the resistance to oxidation stability of permeable membrane, and film surface carboxyl number increases, and surface hydrophilicity 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.
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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 | Asymmetric polyamide nano-film and preparation method thereof |
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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 |
| CN102641667A (en) * | 2012-05-03 | 2012-08-22 | 天津大学 | Preparation method of polyamide composite nanofiltration membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102641667A (en) * | 2012-05-03 | 2012-08-22 | 天津大学 | Preparation method of polyamide composite nanofiltration membrane |
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 kind of processing of sand slurry utilizes method and equipment |
| 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 | 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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