CN103212312B - A kind of Asymmetric antioxidant permeable membrane and preparation method thereof - Google Patents
A kind of Asymmetric antioxidant permeable membrane and preparation method thereof Download PDFInfo
- Publication number
- CN103212312B CN103212312B CN201310158835.5A CN201310158835A CN103212312B CN 103212312 B CN103212312 B CN 103212312B CN 201310158835 A CN201310158835 A CN 201310158835A CN 103212312 B CN103212312 B CN 103212312B
- Authority
- CN
- China
- Prior art keywords
- film
- permeable membrane
- treated
- polyamide
- asymmetric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation method of asymmetric antioxidant polyamide permeable membrane.The method is used to the ammonium of benzene two (MPD) and pyromellitic trimethylsilyl chloride (TMC) monomer, the method closed by interfacial polycondensation is in the strata acid amides cortex of polysulfones (PES) support membrane surface recombination one, and coordinate dehydrating agent to post-process cortex using ethanedioic acid, prepare the polyamide composite permeable membrane of resistance to oxidation.The ethanedioic acid that the present invention uses coordinates the processing method of dehydrating agent to be effectively improved the oxidative resistance and hydrophily of polyamide cortex, and coordinate anisotropic membrane structure that influence of the concentration polarization to membrane separating property has been dramatically reduced, further improve the water flux of film and the rejection to salt ion.The preparation method category of the present invention is pioneering, is operated under the technique normal temperature and pressure, experiment condition is simple, short preparation period, the preparation particularly suitable for large quantities of quantity high performance permeability and separation films.
Description
Invention field
The present invention relates to a kind of asymmetric antioxidant polyamide permeable membrane and preparation method thereof.
Technical background
China is the big country of a serious water shortage, and water resource is only the 1/4 of world average per capita.Shortage of water resources is increasingly
Seriously, it is an important channel of solution water resources problems to the seawater and brackish water source of warding off, infiltration membrane separation technique will be played increasingly
Important function.The characteristics of polyamide permeable permeable membrane has good hydrophilic property, and flux is big, and ion rejection rate is high, and have well
Mechanical performance, heat endurance and hydrolytic stability.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 polyamides
There is the problems such as oxidation, concentration polarization in amine permeable membrane, and influence its stability and service life in application process.
Concentration polarization phenomenon produces pole to infiltration film properties in the oxidative resistance and hydrophily and membrane process of permeable membrane
Big influence, it is the three big factors for carrying out needing emphasis to consider during infiltration Design of Membrane Structure.At present, the preparation of high flux permeable membrane
Method mainly has phase inversion and interfacial polymerization.Wherein, phase inversion is most ripe and obtains the film of commercial applications earliest
Technology of preparing, phase transition method be made can self-supporting integrated anisotropic membrane：Cortex is same material with supporting layer, and film supports
Body is chimeric with Motor cortex, and the air remaining in membrane pores reduces porosity, hinder water by the way that the interior concentration polarization of film is inclined
It is high.And interfacial polymerization prepares asymmetric permeable membrane can optimize membrane structure, cortex is finer and close, hypodermic layer in gradient loose.
Different cortex and supporting layer can be selected respectively, so can both reduce skin thickness, can eliminate the transition zone for causing densification again,
So as to reduce concentration polarization, water flux is improved.But the amino of polyamide permeable permeable membrane surface is easily oxidized to nitro, hydroxylamino,
Surface hydrophilicity is reduced, concentration polarization phenomenon is obvious, reduces water flux.Therefore improve the oxidative resistance of film, make it in richness
Stable operation is urgent problem to be solved under the conditions of oxygen.
In recent years, people pass through new filming technology so that polyamide permeable permeable membrane is widely used, especially into
For the main product of RO films.Compared to RO technologies or other membrane separation techniques, FO technologies have the low innate advantage of energy consumption, in recent years
It is the optimal path for realizing low energy consumption seawater desalination to quickly grow and turn into study hotspot, can be used for penetration of sea water hair
Electrical domain.Therefore, a kind of preparation method of special high flux antioxidant polyamide permeable membrane is developed, for film permeability and separation technology
Using having great importance.
The content of the invention
It is an object of the invention to provide a kind of asymmetric antioxidant polyamide permeable membrane and preparation method thereof, the preparation side
Method process conditions are gentle, and equipment is simple, and energy consumption is low, and the cycle is short.
The preparation method of the asymmetric antioxidant polyamide permeable membrane of the present invention is to close technique using interfacial polycondensation.Room temperature
Under, monomer pyromellitic trimethylsilyl chloride (TMC) and m-phenylene diamine (MPD) (MPD) are polymerize a strata acid amides in the outer surface of ultrafiltration support membrane
Cortex；Recycle ethanedioic acid, dehydrating agent 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) and compounding ingredient
N-hydroxysuccinimide (NHS) post-processes under certain condition to cortex so that film superficial cortical layers are finer and close, oxytolerant
The property changed and hydrophily greatly improve, and effectively reduce influence of the interior concentration polarization to water flux, obtain high water flux and retention
The polyamide permeable antireflective film material of rate.
The preparation method of a kind of asymmetric antioxidant polyamide permeable membrane of the present invention, including at least following steps：
(1) doughnut support film layer is heat-treated, dried 60 minutes under the conditions of 90 DEG C, film is fully dried；
(2) film treated through step (1) is immersed to contain in the m-phenylene diamine (MPD) of mass fraction 2% (MPD) aqueous solution and carried out
Processing, MPD molecules are made to penetrate into the surface of film；
(3) film that will be treated through step (2), which immerses, contains the pyromellitic trimethylsilyl chloride of mass fraction 0.5% (TMC) n-hexane
Interfacial polycondensation conjunction is carried out in solution, makes MPD and TMC that first step initial reaction occur on film surface, reaction is taken out after 30~50 seconds,
Form one layer of initial film；
(4) film treated through step (3) is placed in 90 DEG C progress second step reaction in baking oven, makes two kinds of monomers abundant
Reaction, the compactness extent of polyamide cortex is improved, realize high rejection of the film to salt ion, taken out after reacting a period of time, two
Secondary water fully cleans, and removes unreacted participation monomer；
(5) the asymmetric polyamide permeable permeable membrane prepared through step (4) is placed in 10% aqueous oxalic acid after carrying out and located
Reason, and add in the solution a certain amount of dehydrating agent 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) and
Compounding ingredient n-hydroxysuccinimide (NHS) reacts certain time, ethanedioic acid is fully reacted with polyamide, taking-up secondary water
Clean repeatedly.
Wherein, the experimental procedure post-processed using the aqueous oxalic acid for adding dehydrating agent to film is to be divided into two ranks
Section：First configuration quality is 10% aqueous oxalic acid, will pass through the permeable membrane that step (1)~(4) treat and enter the solution
In, react 3 hours at room temperature, film surface amino groups is carried out initial reaction with ethanedioic acid；Adding mass fraction in the solution again is
3% dehydrating agent EDC and 0.5% compounding ingredient NHS, is completely dissolved, and magnetic stirring apparatus stirs, and lucifuge is anti-at room temperature
Answer 15~21 hours, film surface amino groups is further fully reacted with ethanedioic acid carboxyl, weaken the oxidation effect of amino, improve film
Resistance to oxidation stability, and film surface carboxyl groups number increase, make surface hydrophilic degree strengthen, reduce concentration polarization to water
The influence of flux；The film treated by step (1)~(5) is fully cleaned up with secondary water, removes remaining ethanedioic acid list
Body, preserved in secondary water.
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 processing time was at 18~24 hours.
Compared with prior art, this preparation method has the characteristics that：
(1) asymmetric polyamide permeable permeable membrane is prepared using interfacial polymerization, advantageously reduces concentration polarization to UF membrane
The influence of energy, and monomer reaction activity is big, and preparation condition is gentle, and cost is low；
(2) preparation method of Asymmetric antioxidant PA membrane of the invention, is post-processed using ethanedioic acid to film, is grasped
Make simply, to realize the target of high flux high oxidation resistance, and the hydrophiling degree on film surface is further improved, for a long time
Interior stable, this method is particularly suitable for preparing high-volume doughnut permeable membrane；
(3) the resistance to oxidation permeable membrane prepared using this method is easy to store, and will not occur in long-term storing process obvious
Oxidative phenomena.
Brief description of the drawings
Fig. 1 is the reaction mechanism schematic diagram that ethanedioic acid handles polyamide permeable permeable membrane；
Fig. 2 is section and the surface electromicroscopic photograph (S-4800) 1 of doughnut polyamide permeable permeable membrane：Blank film cross section
(10000 times)；2：PA membrane cross section (10000 times)；3：Blank film surface (10000 times)；4 polyamide film surfaces (10000
Times)；5 hollow-fibre membrane entirety cross sections (60 times).
Fig. 3 is the surface color change 1 of different post-processing approach films after 30 days：Not post-treated permeable membrane；2、3：Through
Cross the permeable membrane of monomer TMC post processings；4、5：The permeable membrane post-processed by ethanedioic acid.
Embodiment
Embodiment 1
The NaCl aqueous solution using concentration 2M is draws liquid, and using secondary water as material liquid, test sample is as forward osmosis membrane
Water flux and rejection.First the doughnut permeable membrane of preparation is placed in self-control detection means and carries out positive penetration testing, in room
Under temperature (23 DEG C), the certain flow velocity of adjustment control, water flow pressure is maintained at 0.1MPa, tested using AY220 types electronic balance
The quality consumed through the material liquid of forward osmosis membrane.One-shot measurement is carried out to mass change every 1min, calculates forward osmosis membrane list
The water transit dose of position area per time, maximum can reach 40L/ (m2h).Liquid is drawn using the test of DDS-307 type electric conductivities instrument
Front and rear change in concentration, calculate rejection of the permeable membrane to salt ion.The permeable membrane handled by ethanedioic acid is cut to NaCl ions
Rate is stayed to can reach 96%.
Embodiment 2
With concentration 2M MgCl2The aqueous solution is draws liquid, and using secondary water as material liquid, test sample is as forward osmosis membrane
Water flux and rejection.The doughnut forward osmosis membrane of preparation is placed in self-control detection means and carries out positive penetration testing, in room
Under temperature (23 DEG C), the certain flow velocity of adjustment control, water flow pressure is maintained at 0.1MPa, passed through using electronic balance test and just oozed
The consumption quality of the material liquid of permeable membrane.One-shot measurement is carried out to mass change every 1min, calculates forward osmosis membrane unit area list
The water transit dose of position time, maximum can reach 52L/ (m2h).Concentration before and after liquid is drawn using the test of DDS-307 type electric conductivities instrument
Change, calculate rejection of the permeable membrane to salt ion.The permeable membrane handled by ethanedioic acid is to MgCl2The rejection of ion can
Reach 98%.
Embodiment 3
With concentration 0.6M NaCl aqueous solution simulated seawaters, pressure damping infiltration (PRO) hair is built using river as liquid is penetrated into
Electric system, water flux and rejection of the test sample as forward osmosis membrane.The doughnut permeable membrane of preparation is first placed in PRO
In energy detection means, at room temperature (23 DEG C), control valve size controls certain flow velocity, using electronic balance test through just
The consumption quality of the material liquid of permeable membrane.One-shot measurement is carried out to mass change every 1min, calculates forward osmosis membrane unit area
The water transit dose of unit interval, maximum can reach 100L/ (m2h).Drawn using the test of DDS-307 type electric conductivities instrument dense before liquid
Degree change, calculate rejection of the permeable membrane to salt ion.The permeable membrane handled by ethanedioic acid can to the rejection of NaCl ions
Reach 99%.
Claims (6)
1. a kind of asymmetric antioxidant polyamide permeable membrane, it is characterised in that the preparation method of the film comprises at least following steps：
(1) doughnut supporting layer is heat-treated, 60min is dried under the conditions of 90 DEG C, film is fully dried；
(2) the film sealing two ends that will be treated through step (1), immersion contain the m-phenylene diamine (MPD) of mass percent 2% (MPD) aqueous solution
In handled, make MPD molecules penetrate into film surface；
(3) film that will be treated through step (2) immerses molten containing the pyromellitic trimethylsilyl chloride of mass percent 0.5% (TMC) n-hexane
Interfacial polycondensation conjunction is carried out in liquid, makes MPD and TMC that first step initial reaction occur on film surface, is taken out after reacting a period of time, shape
Into one layer of initial film；
(4) film treated through step (3) is placed in progress second step reaction in 90 DEG C of baking oven, makes two kinds of monomers fully anti-
Should, the compactness extent of polyamide cortex is improved, realizes high rejection of the permeable membrane to salt ion, is taken after reacting a period of time
Go out, secondary water is fully cleaned, and removes the monomer for having neither part nor lot in reaction；
(5) the asymmetric permeable membrane prepared through step (4) is placed in quality to be post-processed in 10% aqueous oxalic acid, and
A certain amount of dehydrating agent 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) are added in the solution and are coordinated
Agent n-hydroxysuccinimide (NHS), play a part of activated carboxyl and amino, reaction a period of time, make ethanedioic acid and polyamides
Amine is fully reacted, and taking-up is cleaned repeatedly with secondary water,
Described step (5) experimental procedure is divided into two stages：The aqueous oxalic acid that quality is 10% is first prepared, will be passed through
The treated film in step (1)~(4) is immersed in the solution, is reacted 3 hours at room temperature, film surface amino groups is carried out just with ethanedioic acid
Begin to react；Add the compounding ingredient NHS for the dehydrating agent EDC and 0.5% that mass fraction is 3% in the solution again, fully dissolving, use magnetic
Power agitator is stirred, and lucifuge is reacted 15~21 hours at room temperature, the carboxyl of film surface amino groups and ethanedioic acid is further filled
Divide reaction, weaken the oxidation effect of amino, improve the resistance to oxidation stability of permeable membrane, and the increase of film surface carboxyl groups number, make
Surface hydrophilicity strengthens, and reduces influence of the concentration polarization to water flux；The treated film in step (1)~(5) will be passed through with two
Secondary water fully cleans up, and removes remaining ethanedioic acid monomer, is preserved in secondary water.
2. a kind of asymmetric antioxidant polyamide permeable membrane according to claim 1, it is characterised in that described in step (2)
The immersion time be 5~10 minutes, overlong time solution passes through film layer, can not prepare anisotropic membrane structure.
3. a kind of asymmetric antioxidant polyamide permeable membrane according to claim 1, it is characterised in that described in step (3)
Reaction time starting stage be 30~50 seconds.
4. a kind of asymmetric antioxidant polyamide permeable membrane according to claim 1, it is characterised in that described in step (4)
Film second stage processing time control at 15~20 minutes.
5. a kind of asymmetric antioxidant polyamide permeable membrane according to claim 1, it is characterised in that described in step (5)
Ethanedioic acid to the post-processing stages of film, processing time is 18~24 hours.
6. a kind of preparation method of asymmetric antioxidant polyamide permeable membrane, it is characterised in that this method comprises at least following step
Suddenly：
(1) doughnut supporting layer is heat-treated, 60min is dried under the conditions of 90 DEG C, film is fully dried；
(2) the film sealing two ends that will be treated through step (1), immersion contain the m-phenylene diamine (MPD) of mass percent 2% (MPD) aqueous solution
In handled, make MPD molecules penetrate into film surface；
(3) film that will be treated through step (2) immerses molten containing the pyromellitic trimethylsilyl chloride of mass percent 0.5% (TMC) n-hexane
Interfacial polycondensation conjunction is carried out in liquid, makes MPD and TMC that first step initial reaction occur on film surface, is taken out after reacting a period of time, shape
Into one layer of initial film；
(4) film treated through step (3) is placed in progress second step reaction in 90 DEG C of baking oven, makes two kinds of monomers fully anti-
Should, the compactness extent of polyamide cortex is improved, realizes high rejection of the permeable membrane to salt ion, is taken after reacting a period of time
Go out, secondary water is fully cleaned, and removes the monomer for having neither part nor lot in reaction；
(5) the asymmetric permeable membrane prepared through step (4) is placed in quality to be post-processed in 10% aqueous oxalic acid, and
A certain amount of dehydrating agent 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) are added in the solution and are coordinated
Agent n-hydroxysuccinimide (NHS), play a part of activated carboxyl and amino, reaction a period of time, make ethanedioic acid and polyamides
Amine is fully reacted, and taking-up is cleaned repeatedly with secondary water,
Described step (5) experimental procedure is divided into two stages：The aqueous oxalic acid that quality is 10% is first prepared, will be passed through
The treated film in step (1)~(4) is immersed in the solution, is reacted 3 hours at room temperature, film surface amino groups is carried out just with ethanedioic acid
Begin to react；Add the compounding ingredient NHS for the dehydrating agent EDC and 0.5% that mass fraction is 3% in the solution again, fully dissolving, use magnetic
Power agitator is stirred, and lucifuge is reacted 15~21 hours at room temperature, the carboxyl of film surface amino groups and ethanedioic acid is further filled
Divide reaction, weaken the oxidation effect of amino, improve the resistance to oxidation stability of permeable membrane, and the increase of film surface carboxyl groups number, make
Surface hydrophilicity strengthens, and reduces influence of the concentration polarization to water flux；The treated film in step (1)~(5) will be passed through with two
Secondary water fully cleans up, and removes remaining ethanedioic acid monomer, is preserved in secondary water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310158835.5A CN103212312B (en) | 2013-04-28 | 2013-04-28 | A kind of Asymmetric antioxidant permeable membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310158835.5A CN103212312B (en) | 2013-04-28 | 2013-04-28 | A kind of Asymmetric antioxidant permeable membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103212312A CN103212312A (en) | 2013-07-24 |
| CN103212312B true CN103212312B (en) | 2018-03-02 |
Family
ID=48810667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310158835.5A Expired - Fee Related CN103212312B (en) | 2013-04-28 | 2013-04-28 | A kind of Asymmetric antioxidant permeable membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103212312B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214521B (en) * | 2014-06-25 | 2017-08-04 | 天津大学 | A kind of polyetherimide amine composite nanofiltration membrane and preparation method |
| 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 |
| CN111841343B (en) * | 2020-07-30 | 2022-04-15 | 河南师范大学 | Asymmetric polyamide nano-film and preparation method thereof |
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 |
-
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 |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103212312A (en) | 2013-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103212312B (en) | A kind of Asymmetric antioxidant permeable membrane and preparation method thereof | |
| CN102989331B (en) | Polymer/graphene hybridization nanofiltration composite membrane and preparation method thereof | |
| CN109589804A (en) | A kind of hydrophilic polyolefin substrate composite nanometer filtering film and preparation method thereof | |
| CN105214511A (en) | A kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof | |
| CN103394295B (en) | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof | |
| CN105854630B (en) | A kind of forward osmosis membrane and preparation method thereof | |
| CN102989330A (en) | Hybrid graphene/aromatic polyamide reverse osmosis membrane and preparation method thereof | |
| CN108435002A (en) | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified | |
| CN103537200B (en) | A kind of Cellulose acetate forward osmotic membrane and preparation method thereof | |
| Arthanareeswaran et al. | Development, characterization and separation performance of organic–inorganic membranes: part II. Effect of additives | |
| CN105396471A (en) | Preparation method of high water flux reverse osmosis membrane | |
| CN106890570A (en) | A kind of preparation method of the hollow fiber nanofiltration membrane of graphene oxide doped | |
| CN114100374B (en) | Monovalent ion selective cation exchange membrane and preparation method and application thereof | |
| CN106943902A (en) | Ester modified polyamide reverse osmosis composite film of a kind of silicic acid and preparation method thereof | |
| CN103785301B (en) | A kind of Cellulose acetate forward osmotic membrane material and preparation method thereof | |
| Zhang et al. | Fabrication of polyamide thin film nanocomposite reverse osmosis membrane incorporated with a novel graphite‐based carbon material for desalination | |
| CN104107638A (en) | Forward osmosis membrane and preparation method thereof | |
| CN104289116A (en) | Composite reverse osmosis membrane and preparation method thereof | |
| KR102375661B1 (en) | Polyaniline membranes formed by phase inversion for forward osmosis applications | |
| CN104437135A (en) | Hydrophilic polymer modified fiber composite forward osmosis membrane and preparation method and application thereof | |
| CN104107641A (en) | Forward osmosis organic-inorganic composite membrane and preparation method thereof | |
| CN103831026B (en) | A kind of production technology of high rejection composite hollow fiber nano | |
| CN111330460B (en) | Method for modifying polysulfone nanofiltration membrane by using DNA/ZIF-8 and obtained membrane | |
| CN109718667A (en) | A kind of multi-functional forward osmosis membrane and preparation method thereof | |
| CN104492274A (en) | Preparation method of reverse osmosis membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180302 |