CN106345309A - PVDF organic membrane modifying method - Google Patents
PVDF organic membrane modifying method Download PDFInfo
- Publication number
- CN106345309A CN106345309A CN201610916070.0A CN201610916070A CN106345309A CN 106345309 A CN106345309 A CN 106345309A CN 201610916070 A CN201610916070 A CN 201610916070A CN 106345309 A CN106345309 A CN 106345309A
- Authority
- CN
- China
- Prior art keywords
- dispersion liquid
- pvdf
- membrane
- organic membrane
- modifying
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a PVDF organic membrane modifying method which comprises the following steps: adding a carbon nanotube and graphene into N,N-dimethyl acetamide to form dispersion liquid A; mixing PVDF and a solvent polyvinyl pyrrolidone to form dispersion liquid B; adding the dispersion liquid B into the dispersion liquid A, stirring to obtain membrane casting liquid, and standing and defoaming in a vacuum drying oven for 2-3h; and casting, scraping and cleaning to obtain an ultrafiltration membrane. In the invention, the PVDF is modified by a carbon composite material carbon nanotube and graphene, the dispersity of nanoparticles in the membrane casting liquid is improved, so that the performance of the PVDF ultrafiltration membrane is enhanced, and the problems that the nanoparticles are easily gathered and have low dispersity in the membrane casting liquid, the prepared ultrafiltration membrane has low hydrophility, the nanoparticles easily block the membrane holes to reduce the water flux and pollution frequently occurs are solved; and the hydrophility of the modified PVDF organic membrane is improved, the water flux is increased, the mechanical performance is enhanced, the anti-pollution property is improved, and the service life of the membrane is prolonged.
Description
Technical field
The present invention relates to field of material technology, specifically a kind of pvdf organic membrane method of modifying.
Background technology
Membrane separation technique, as new, the efficient fluid separation techniques of one kind, quickly grows, acquirement attracts people's attention in recent years
Achievement in research, play an important role in energy-saving and emission-reduction, clean manufacturing and recycling economy, especially water resource using and ring
The effect of border protection aspect is even more very important.Membrane separation technique is used in mbr, and available membrane material is more, has poly- carbonic acid
Ester, cellulose esters, Kynoar, polysulfones, politef, polrvinyl chloride, Polyetherimide, polyethylene, polypropylene, polyethers
Ether ketone, polyamide etc..But the larger only Kynoar (pvdf) of usage amount in current mbr membrane module, polyethylene (pe) and
Polypropylene (pp).Wherein Kynoar (pvdf) is due to its excellent process based prediction model (intensity and corrosion resistance), state
Interior and external consumption is all larger.Feature according to handled dissimilar water it is desirable to macromolecule member material used have good
Heat stability well, the erosion of chemical stability, acid and alkali-resistance and microorganism and oxidative resistance；In addition, having to different types of film
Different requirements.Reverse osmosiss, ultrafiltration and microfiltration film are preferably hydrophilic film, to obtain high water flux and contamination resistance；
Resistance to acids and bases and the heat stability of film is especially emphasized in electrodialysis.Therefore, it is necessary to be modified to pvdf organic membrane, make prepared
Membrane material there is excellent performance.
Content of the invention
It is an object of the invention to provide a kind of pvdf organic membrane method of modifying.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of method of modifying of pvdf organic membrane is it is characterised in that comprise the following steps:
(1) CNT is added to solvent n with Graphene by weight 1:1-2, in n- dimethyl acetylamide, in 45-
Ultrasonic disperse 1-3h at a temperature of 60 DEG C, forms dispersion liquid a；
(2) pvdf and solvent polyvinyl pyrrolidone are mixed by weight 1:8-10, form dispersion liquid b, will disperse
Liquid b is added in dispersion liquid a, controls the stirring of certain bath temperature agitated device to obtain casting solution, is placed in quiet in vacuum drying oven
Put deaeration 2-3h；
(3) by casting solution cast in cleaning glass substrate on, in casting cycle using knifing machine glass after pouring
Knifing is carried out on substrate, obtains the glass substrate of the casting solution for 0.2-0.3mm containing thickness；To be 0.2- containing thickness
The glass substrate of the casting solution of 0.3mm volatilizees 50s in atmosphere, then is immersed in immersion 8-16h in coagulating bath, after being come off
Ultrafilter membrane；
(4) using distilled water, the ultrafilter membrane after coming off is carried out 2-4 time, is saved in distilled water, obtain carbon and be combined
Material modification pvdf organic membrane.
Preferably, in described step (1) dispersion liquid a, CNT with the gross mass of Graphene with the volume ratio of solvent is
(12-15mg): 1ml.
Preferably, described step (1) ultrasonic power 300-500w.
Preferably, described step (2) bath temperature is 75-83 DEG C；Described mixing speed is 500-600r/min, during stirring
Between 3-5h；Vacuum drying oven temperature is 20-30 DEG C.
Preferably, the weight of described step (2) dispersion liquid a and dispersion liquid b is than for 1:2.
Beneficial effects of the present invention: the present invention carrys out modified pvdf with carbon composite CNT and Graphene, improves
Dispersibility in casting solution for the nano-particle, thus improve the performance of pvdf ultrafilter membrane, solving nano-particle and being susceptible to
Reunite, bad dispersibility in casting solution, prepared ultrafilter membrane hydrophilic is poor, and nano-particle easily blocks fenestra, and to reduce water logical
Amount, the easily problem of pollution；Present invention modification pvdf organic membrane hydrophilic increases, and so that water flux is increased, improves mechanical performance, change
It has been apt to resistance tocrocking, increased the service life of film.
Specific embodiment
Below in conjunction with embodiment, technical scheme is clearly and completely described with the reality it is clear that described
Applying example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is general
All other embodiment that logical technical staff is obtained under the premise of not making creative work, broadly falls into present invention protection
Scope.
In the description of this specification, the description of reference term " embodiment ", " example ", " specific example " etc. means
It is contained at least one enforcement of the present invention in conjunction with the specific features of this embodiment or example description, structure, material or feature
In example or example.In this manual, identical embodiment or example are not necessarily referring to the schematic representation of above-mentioned term.
And, the specific features of description, structure, material or feature can be to close in any one or more embodiments or example
Suitable mode combines.
Embodiment 1
A kind of method of modifying of pvdf organic membrane, comprises the following steps:
(1) CNT is added to solvent n with Graphene by weight 1:1, in n- dimethyl acetylamide, in 45 DEG C of temperature
Degree lower ultrasonic disperse 1h, ultrasonic power 300w, form dispersion liquid a, the gross mass of CNT and Graphene and the volume of solvent
Than for 12mg:1ml；
(2) pvdf and solvent polyvinyl pyrrolidone are mixed by weight 1:10, form dispersion liquid b, by dispersion liquid b
It is added in dispersion liquid a, the weight of dispersion liquid a and dispersion liquid b ratio for 1:2, controls bath temperature to be 83 DEG C of agitated devices stirrings
Obtain casting solution, mixing speed is 600r/min, mixing time 3h is placed in standing and defoaming 3h in 20 DEG C of vacuum drying oven；
(3) by casting solution cast in cleaning glass substrate on, in casting cycle using knifing machine glass after pouring
Knifing is carried out on substrate, obtains the glass substrate of the casting solution for 0.2-0.3mm containing thickness；To be 0.2- containing thickness
The glass substrate of the casting solution of 0.3mm volatilizees 50s in atmosphere, then is immersed in immersion 8h in coagulating bath, super after being come off
Filter membrane；
(4) using distilled water, the ultrafilter membrane after coming off is carried out 2 times, is saved in distilled water, obtain carbon composite wood
The modified pvdf organic membrane of material.
Embodiment 2
A kind of method of modifying of pvdf organic membrane, comprises the following steps:
(1) CNT is added to solvent n with Graphene by weight 1:2, in n- dimethyl acetylamide, in 60 DEG C of temperature
Degree lower ultrasonic disperse 3h, ultrasonic power 500w, form dispersion liquid a, the gross mass of CNT and Graphene and the volume of solvent
Than for 15mg:1ml；
(2) pvdf and solvent polyvinyl pyrrolidone are mixed by weight 1:8, form dispersion liquid b, by dispersion liquid b
It is added in dispersion liquid a, the weight of dispersion liquid a and dispersion liquid b ratio for 1:2, controls bath temperature to be 75 DEG C of agitated devices stirrings
Obtain casting solution, mixing speed is 500r/min, mixing time 5h is placed in standing and defoaming 2h in 30 DEG C of vacuum drying oven；
(3) by casting solution cast in cleaning glass substrate on, in casting cycle using knifing machine glass after pouring
Knifing is carried out on substrate, obtains the glass substrate of the casting solution for 0.2-0.3mm containing thickness；To be 0.2- containing thickness
The glass substrate of the casting solution of 0.3mm volatilizees 50s in atmosphere, then is immersed in immersion 16h in coagulating bath, super after being come off
Filter membrane；
(4) using distilled water, the ultrafilter membrane after coming off is carried out 4 times, is saved in distilled water, obtain carbon composite wood
The modified pvdf organic membrane of material.
Embodiment 3
A kind of method of modifying of pvdf organic membrane, comprises the following steps:
(1) CNT is added to solvent n with Graphene by weight 1:1.5, in n- dimethyl acetylamide, at 53 DEG C
At a temperature of ultrasonic disperse 2h, ultrasonic power 400w, form dispersion liquid a, the gross mass of CNT and Graphene and the body of solvent
Long-pending ratio is 13mg:1ml；
(2) pvdf and solvent polyvinyl pyrrolidone are mixed by weight 1:9, form dispersion liquid b, by dispersion liquid b
It is added in dispersion liquid a, the weight of dispersion liquid a and dispersion liquid b ratio for 1:2, controls bath temperature to be 78 DEG C of agitated devices stirrings
Obtain casting solution, mixing speed is 550r/min, mixing time 4h is placed in standing and defoaming 2.5h in 25 DEG C of vacuum drying oven；
(3) by casting solution cast in cleaning glass substrate on, in casting cycle using knifing machine glass after pouring
Knifing is carried out on substrate, obtains the glass substrate of the casting solution for 0.2-0.3mm containing thickness；To be 0.2- containing thickness
The glass substrate of the casting solution of 0.3mm volatilizees 50s in atmosphere, then is immersed in immersion 12h in coagulating bath, super after being come off
Filter membrane；
(4) using distilled water, the ultrafilter membrane after coming off is carried out 3 times, is saved in distilled water, obtain carbon composite wood
The modified pvdf organic membrane of material.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply this
Bright.Person skilled in the art obviously easily can make various modifications to case study on implementation, and described herein one
As principle be applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to enforcement case here
Example, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be for those skilled in the art
Within protection scope of the present invention.
Claims (5)
1. a kind of method of modifying of pvdf organic membrane is it is characterised in that comprise the following steps:
(1) CNT is added to solvent n with Graphene by weight 1:1-2, in n- dimethyl acetylamide, at 45-60 DEG C
At a temperature of ultrasonic disperse 1-3h, formed dispersion liquid a；
(2) pvdf and solvent polyvinyl pyrrolidone are mixed by weight 1:8-10, form dispersion liquid b, dispersion liquid b is added
Enter in dispersion liquid a, control the stirring of certain bath temperature agitated device to obtain casting solution, be placed in standing and defoaming in vacuum drying oven
2-3h；
(3) by casting solution cast in cleaning glass substrate on, in casting cycle using knifing machine glass substrate after pouring
On carry out knifing, obtain the glass substrate of the casting solution for 0.2-0.3mm containing thickness；By containing thickness for 0.2-0.3mm's
The glass substrate of casting solution volatilizees 50s in atmosphere, then is immersed in immersion 8-16h, the ultrafilter membrane after being come off in coagulating bath；
(4) using distilled water, the ultrafilter membrane after coming off is carried out 2-4 time, is saved in distilled water, obtains carbon composite
Modified pvdf organic membrane.
2. the method for modifying of pvdf organic membrane according to claim 1 is it is characterised in that in described step (1) dispersion liquid a
CNT and the gross mass of Graphene are (12-15mg): 1ml with the volume ratio of solvent.
3. the method for modifying of pvdf organic membrane according to claim 1 is it is characterised in that described step (1) ultrasonic power
300-500w.
4. the method for modifying of pvdf organic membrane according to claim 1 is it is characterised in that described step (2) bath temperature
For 75-83 DEG C；Described mixing speed is 500-600r/min, mixing time 3-5h；Vacuum drying oven temperature is 20-30 DEG C.
5. pvdf organic membrane according to claim 1 method of modifying it is characterised in that described step (2) dispersion liquid a with
The weight of dispersion liquid b is than for 1:2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610916070.0A CN106345309A (en) | 2016-10-20 | 2016-10-20 | PVDF organic membrane modifying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610916070.0A CN106345309A (en) | 2016-10-20 | 2016-10-20 | PVDF organic membrane modifying method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106345309A true CN106345309A (en) | 2017-01-25 |
Family
ID=57863407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610916070.0A Pending CN106345309A (en) | 2016-10-20 | 2016-10-20 | PVDF organic membrane modifying method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106345309A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107433141A (en) * | 2017-06-27 | 2017-12-05 | 上海师范大学 | A kind of multi-walled carbon nanotube hybrid membranes for possessing antipollution automatically cleaning, anti-microbial property |
| CN108031313A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of strong antipollution ultrafiltration membrane of hydrophily |
| CN108854595A (en) * | 2018-06-28 | 2018-11-23 | 华南师范大学 | Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof |
| CN114016285A (en) * | 2021-12-14 | 2022-02-08 | 盐城工业职业技术学院 | Preparation method of functional nanofiber membrane for seawater desalination |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110624A3 (en) * | 2009-03-27 | 2011-01-06 | Bioneer Corporation | Nanoporous films and method for manufacturing the same |
| CN103084074A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Hydrophilic polyvinylidene fluoride modified separation membrane and preparation method thereof |
| CN103252174A (en) * | 2013-06-06 | 2013-08-21 | 东华理工大学 | Piezoelectric polyvinylidene fluoride porous membrane and preparation method thereof |
| CN103585891A (en) * | 2013-11-13 | 2014-02-19 | 济南泰易膜科技有限公司 | Compression-resistant microporous membrane and preparation method thereof |
-
2016
- 2016-10-20 CN CN201610916070.0A patent/CN106345309A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110624A3 (en) * | 2009-03-27 | 2011-01-06 | Bioneer Corporation | Nanoporous films and method for manufacturing the same |
| CN103084074A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Hydrophilic polyvinylidene fluoride modified separation membrane and preparation method thereof |
| CN103252174A (en) * | 2013-06-06 | 2013-08-21 | 东华理工大学 | Piezoelectric polyvinylidene fluoride porous membrane and preparation method thereof |
| CN103585891A (en) * | 2013-11-13 | 2014-02-19 | 济南泰易膜科技有限公司 | Compression-resistant microporous membrane and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107433141A (en) * | 2017-06-27 | 2017-12-05 | 上海师范大学 | A kind of multi-walled carbon nanotube hybrid membranes for possessing antipollution automatically cleaning, anti-microbial property |
| CN108031313A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of strong antipollution ultrafiltration membrane of hydrophily |
| CN108854595A (en) * | 2018-06-28 | 2018-11-23 | 华南师范大学 | Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof |
| CN114016285A (en) * | 2021-12-14 | 2022-02-08 | 盐城工业职业技术学院 | Preparation method of functional nanofiber membrane for seawater desalination |
| CN114016285B (en) * | 2021-12-14 | 2024-01-30 | 盐城工业职业技术学院 | Preparation method of functional nanofiber membrane for sea water desalination |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bet-Moushoul et al. | TiO2 nanocomposite based polymeric membranes: a review on performance improvement for various applications in chemical engineering processes | |
| CN102580560B (en) | Method for preparing nano-material-doped polymer film | |
| CN106345309A (en) | PVDF organic membrane modifying method | |
| CN102974238B (en) | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation | |
| CN105749766B (en) | A kind of Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane | |
| CN108159888A (en) | A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance | |
| CN104096488B (en) | The preparation method of a kind of polymer/graphene oxide composite separating film | |
| CN103170257B (en) | Compound forward osmosis membrane and preparation method thereof | |
| CN105642129A (en) | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof | |
| CN108554206A (en) | A kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube | |
| CN106823830A (en) | A kind of preparation method of the self-supporting graphene oxide film with water phase stability high | |
| CN105126647B (en) | A kind of high efficiency oil-water separates the preparation method of composite hyperfiltration membrane | |
| CN109499397A (en) | A kind of modified Nano composite membrane and its preparation method and application | |
| CN104941466B (en) | A kind of preparation method for being used to remove the hepatotoxic mesoporous carbon organic hybrid films of macromolecular in water removal | |
| CN112755805B (en) | Underwater super-oleophobic two-dimensional nanoscale mica sheet oil-water separation membrane and preparation method and application thereof | |
| CN106914154A (en) | PEG‑TiO2The preparation method of the hydrophilic milipore filters of/PES/PVA and application | |
| CN109289548A (en) | A kind of preparation method of forward osmosis membrane | |
| CN106040014B (en) | A kind of antioxidant nanofiltration membrane and preparation method thereof that nanocrystalline cellulose is compound | |
| CN107837690A (en) | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework ZIF 8 | |
| CN105854625B (en) | A kind of preparation method of unpowered PVDF hollow-fibre membranes | |
| Zhong et al. | Recent advances in membrane distillation using electrospun membranes: advantages, challenges, and outlook | |
| CN109647221A (en) | Preparation method of forward osmosis membrane based on 3D printing technology | |
| Liu et al. | Strategies for the construction of special wettability metal organic framework membranes: A review | |
| CN105921034A (en) | Preparation and application of graphene oxide-modified cellulose acetate forward osmosis membrane | |
| CN106139912A (en) | A kind of preparation method of inner support reinforced type polyvinylidene fluoride hollow fiber film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170125 |
|
| RJ01 | Rejection of invention patent application after publication |