CN103846011B - A kind of conducting polymer perforated membrane - Google Patents
A kind of conducting polymer perforated membrane Download PDFInfo
- Publication number
- CN103846011B CN103846011B CN201210516832.XA CN201210516832A CN103846011B CN 103846011 B CN103846011 B CN 103846011B CN 201210516832 A CN201210516832 A CN 201210516832A CN 103846011 B CN103846011 B CN 103846011B
- Authority
- CN
- China
- Prior art keywords
- conducting polymer
- membrane
- dynamic
- perforated membrane
- casting solution
- 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.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention is a kind of conducting polymer perforated membrane.Surface specific resistance is 160 more than Ω m, is prepared by following methods: carbon black is carried out ultrasonic disperse 1 ~ 3h in 25 DEG C of water, and ultrasonic power is 0 ~ 300w, then stirs, and is added wherein by binding agent, and fully stirs, and obtains uniform Dynamic Membrane casting solution; Polymer-based film water is rinsed; The Dynamic Membrane casting solution obtained with step (1) is for liquid to be filtered, the polymer-based film obtained with step (1) for filtering material, under the operating pressure of 0.1 ~ 0.3MPa, at 25 ~ 90 DEG C of temperature, adopt depositional model to run continuously, obtain dynamic complex film; Natural air drying obtains described conducting polymer perforated membrane.Preparation method's technique of the present invention is simple, and do not produce environmental pollution, to appointed condition without particular/special requirement, cost is lower, is convenient to industrial applications.
Description
Technical field
The present invention relates to polymer separation film technology of preparing, be specially a kind of conducting polymer perforated membrane.
Background technology
UF membrane, as a kind of emerging efficient, energy-conservation, eco-friendly isolation technics, has become the effective means solving crisis of resource and environment deterioration problem, and it is also a key technology for the treatment of of Organic Wastewater simultaneously.But use membrane technology deep-treating organic waste water, there is problem (the Liu C X such as low, the easy pollution of separation accuracy of film, service life is short, Zhang D R, He Y, ZhaoX S, Bai R B.Modification of membrane surface for anti-biofouling performance:Effectof anti-adhesion and anti-bacteria approaches.J Membrane Sci, 2010,346 (1): 121-130).
Photocatalysis technology and membrane separation technique coupling are the effective ways realizing the anti-Organic Pollution of film.(Mozia S, Toyada M, Inagaki M, Tryba B, the Morawski AW.Application of carbon-coated TiO such as Mozia
2fordecompositi on of methylene blue in a photocatalytic membrane reactor, J HazardousMater, 2007,140 (1-2): 369-375) by TiO
2charcoal modification TiO has been prepared with polyvinyl alcohol mixing high temperature carbonization
2photochemical catalyst, and by photocatalytic process and Membrane Materials process integration process methylene blue waste water, successfully realizes being separated of catalyst and byproduct in treatment fluid.But the research of membrane material in antifouling property fails to make a breakthrough all the time, this is mainly because at TiO
2in photocatalytic process, the recombination rate of carrier is very high, causes quantum efficiency too low, lacks organic coupling between basement membrane and photochemical catalyst.For addressing this problem, additional low voltage electric field can be adopted to combine with illumination, the effect of external electrical field effectively can stop the compound of carrier, increases the formation efficiency of OH, eliminates and add electron capture agent (O in system
2) (He C, Li X Z, Xiong Y, Zhu X, Liu S.The enhanced PC and PEC oxidarion of formic acid in aqueous solutionusing a Cu-TIO
2/ ITO film, Chemosphere, 2005,58 (4): 381-389).Li Jianxin etc. with tubular type carbon membrane for basement membrane, in conjunction with electro-catalysis principle, surface modification technology and sol-gel technique, by nano-TiO
2be equipped on carbon membrane matrix and prepare electro-catalysis membrane material.With its process 200mg/L oily waste water, within the operating time of 200min, flux remains on more than 90%, chemical oxygen consumption (COC) clearance reaches 94.4% and is all better than conventional film separation process (see Li Jianxin etc., a kind of antipollution electro-catalysis membrane and reactor, international patent of invention, PCT/CN2009/074542).At present, about the research of electric field-photocatalysis-UF membrane coupling all uses the inorganic carbon membrane with electric conductivity as basement membrane, its preparation cost is high, and fragility is large.Polymer film is as the important component part of membrane material, and its raw material is extensive, preparation technology is simple, pliability is good, and the correlative study of the conductive porous film of covering polymer still rarely has report.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is: propose a kind of conducting polymer perforated membrane, with polymer microporous film or milipore filter for basement membrane, take conductive black as Dynamic Membrane material, by the method for surface deposition Dynamic Membrane, prepare conducting polymer perforated membrane.It is simple that the method has technique, and to appointed condition without particular/special requirement, cost is lower, is convenient to the feature of industrial applications, and made conducting polymer perforated membrane not only has good electric conductivity, also has good permeance property simultaneously.
Described kind of conducting polymer perforated membrane is prepared by following methods:
(1) carbon black particle is carried out ultrasonic disperse 1 ~ 3h in 25 DEG C of water, ultrasonic power is 0 ~ 300w, then high-speed stirred 1 ~ 3h, mixing speed is 800 ~ 1000r/min, binding agent is added wherein, and fully 1 ~ 3h is stirred at 70 ~ 95 DEG C, mixing speed is 300 ~ 500r/min, obtains uniform Dynamic Membrane casting solution;
Described carbon black particle is nanoscale, and average grain diameter is 1 ~ 9nm;
Described carbon black particle accounts for 0.01 ~ 10wt% of Dynamic Membrane casting solution;
Described binding agent is that polyvinyl alcohol, polyoxyethylene etc. are insoluble in normal-temperature water, are soluble in the water-soluble polymer of high-temperature water;
Described binding agent accounts for 1 ~ 5wt% of Dynamic Membrane casting solution;
(2) polymer-based film water is rinsed 10min;
Described polymer-based film is microfiltration membranes or milipore filter, its material comprises all polymeric film material such as TPO (polypropylene, polyethylene, polyvinyl chloride), polysulfones and polyether sulfone, cellulose family, Kynoar, and film shape comprises hollow-fibre membrane, Flat Membrane, tubular membrane etc.;
(3) the Dynamic Membrane casting solution obtained with step (1) is for liquid to be filtered, the polymer-based film obtained with step (2) is for filtering material, be 0.1 ~ 0.3MPa at operating pressure, temperature is under 25 ~ 90 DEG C of conditions, adopt depositional model to run 3 ~ 60min continuously, obtain dynamic complex film;
Described depositional model comprises dead end pressurization deposition and cross-flow pressurization deposition two kinds of patterns;
(4), after dynamic complex film natural air drying step (3) obtained, described conducting polymer perforated membrane is namely obtained.
Beneficial effect
Compared with prior art, Dynamic Membrane casting solution of the present invention not only adds conducting particles carbon black, makes Dynamic Membrane have electric conductivity, also adds binding agent, and Dynamic Membrane holding structure in filter process is stablized.Binding agent is indissoluble in normal-temperature water, when mainly avoiding normal temperature to filter, and the Dynamic Membrane structural deterioration that binding agent dissolves and causes.Easily molten in high-temperature water, making preparation process environmental protection more, and when fouling membrane is serious, cleaned by hot water, namely rebuilding Dynamic Membrane by repeating step (1) to step (4).Traditional Dynamic Membrane casting solution composition is single, and not only functional characteristic is not given prominence to, and structural stability is poor, and easily in filter process, recurring structure destroys; This invention takes the method for two step mixing simultaneously, obtain the Dynamic Membrane casting solution mixed.The Dynamic Membrane casting solution obtained is more even, and carbon black nano particle is not easily reunited; And preparation method of the present invention devises two kinds of different Dynamic Membrane depositional models, comprise dead end pressurization deposition and cross-flow pressurization deposition, these two kinds of depositional models all can ensure the uniform deposition of Dynamic Membrane, also by parameters such as adjustment pressure, temperature, times, effectively can control the thickness of Dynamic Membrane.The conducting polymer perforated membrane that preparation method of the present invention obtains has good permeance property, electric conductivity and antifouling property: described conducting polymer perforated membrane bubble point aperture is 0.25 ~ 0.3 μm, resistivity is 160 ~ 1000 Ω m, can be applicable to micro-filtration and ultrafiltration field, also may be used for electric assisted photo-catalysis membrane reactor.
The present invention has the Dynamic Membrane of electric conductivity at polymer-based film surface deposition in sum, not give only the electric conductivity that polymer film is good, and also effective preventing pollution thing is to membrane surface and diffusion inside, significantly slows down the pollution speed of film; Meanwhile, Dynamic Membrane reduces the effective aperture of film, improves the separation accuracy of film; In addition, when pollutant is difficult to remove, also can utilizes the unstable structure of gained Dynamic Membrane of the present invention, rebuild Dynamic Membrane.Preparation method's technique of the present invention is simple, and free from environmental pollution, to equipment without particular/special requirement, cost is lower, is convenient to suitability for industrialized production and application.
Detailed description of the invention
The preparation method of a kind of conducting polymer perforated membrane in the present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, but not limits the scope of the invention, and the spirit and scope of the invention only limited by claims.To those skilled in the art, under the prerequisite not deviating from essence of the present invention and scope, the various change carry out the material component in these embodiments and consumption or change also belong to protection scope of the present invention.
Embodiment 1:
By nano carbon black particle 6g in 188g water 25 DEG C carry out ultrasonic disperse 1h, ultrasonic power is 100w, then high-speed stirred 1h, mixing speed is 800r/min, polyvinyl alcohol 6g is added wherein, and fully 2h is stirred under 90 DEG C of conditions, mixing speed is 300r/min, obtains uniform Dynamic Membrane casting solution; Ultra-high molecular weight polyethylene hollow-fibre membrane water is rinsed 10min; With Dynamic Membrane casting solution for liquid to be filtered, with ultra-high molecular weight polyethylene hollow-fibre membrane for filtering material, under the operating pressure of 0.1MPa, at 70 DEG C of temperature, adopt dead end external pressurized depositional model, continuous operation 15min, after obtaining dynamic complex film natural air drying, namely obtains described conducting polymer perforated membrane.
Detect through contrast, the ultra high molecular weight polyethylene films of uncoated Dynamic Membrane, its water flux is 150.1L/ (m
2.h), bubble point aperture is 0.31 μm, and resistivity is greater than 1.0 × 10
10Ω m; The High molecular weight polyethylene film of coating Dynamic Membrane, its water flux 110.4L/ (m
2.h), bubble point aperture is 0.29 μm, and resistivity is 202 Ω m.
Embodiment 2:
By nano carbon black particle 8g in 184g water 25 DEG C carry out ultrasonic disperse 1h, ultrasonic power is 150w, then high-speed stirred 1h, mixing speed is 1000r/min, polyvinyl alcohol 8g is added wherein, and fully 2h is stirred under 90 DEG C of conditions, mixing speed is 400r/min, obtains uniform Dynamic Membrane casting solution; Ultra-high molecular weight polyethylene hollow-fibre membrane water is rinsed 10min; With Dynamic Membrane casting solution for liquid to be filtered, with ultra-high molecular weight polyethylene hollow-fibre membrane for filtering material, under the operating pressure of 0.2MPa, at 60 DEG C of temperature, adopt cross-flow external pressurized depositional model, continuous operation 45min, after obtaining dynamic complex film natural air drying, namely obtains described conducting polymer perforated membrane.
After testing, the water flux 98.3L/ (m of gained film
2.h), bubble point aperture is 0.27 μm, and resistivity is 170 Ω m.
Embodiment 3:
By nano carbon black particle 14g in 180g water 25 DEG C carry out ultrasonic disperse 2h, ultrasonic power is 100w, then high-speed stirred 2h, mixing speed is 1000r/min, polyoxyethylene 6g is added wherein, and fully 2h is stirred under 80 DEG C of conditions, mixing speed is 500r/min, obtains uniform Dynamic Membrane casting solution; Polyvinylidene fluoride flat film water is rinsed 10min; With Dynamic Membrane casting solution for liquid to be filtered, with polyvinylidene fluoride flat film for filtering material, under the operating pressure of 0.1MPa, at 80 DEG C of temperature, adopt cross-flow pressurization depositional model, run 30min continuously, after obtaining dynamic complex film natural air drying, namely obtain described conducting polymer perforated membrane.
Detect through contrast, the polyvinylidene fluoride flat film of uncoated Dynamic Membrane, its water flux is 350.1L/ (m
2.h), bubble point aperture is 0.31 μm, and resistivity is greater than 1.0 × 10
5Ω m; The polyvinylidene fluoride flat film of coating Dynamic Membrane, its water flux 243.9L/ (m
2.h), bubble point aperture is 0.27 μm, and resistivity is 165 Ω m.
Claims (3)
1. a conducting polymer perforated membrane product, described conducting polymer porous film surface ratio resistance is 160 more than Ω m, and described conducting polymer perforated membrane can be prepared by following methods:
(1) carbon black particle is carried out ultrasonic disperse 1 ~ 3h in 25 DEG C of water, ultrasonic power is 0 ~ 300w, then high-speed stirred 1 ~ 3h, mixing speed is 800 ~ 1000r/min, binding agent is added wherein, and fully 1 ~ 3h is stirred at 70 ~ 95 DEG C, mixing speed is 300 ~ 500r/min, obtains uniform Dynamic Membrane casting solution;
Described carbon black particle is nanoscale, and average grain diameter is 1 ~ 9nm;
Described carbon black particle accounts for 0.01 ~ 10wt% of Dynamic Membrane casting solution;
Described binding agent is polyvinyl alcohol or polyoxyethylene;
Described binding agent accounts for 1 ~ 5wt% of Dynamic Membrane casting solution;
(2) polymer-based film water is rinsed 10min;
Described polymer-based film is microfiltration membranes or milipore filter;
(3) the Dynamic Membrane casting solution obtained with step (1) is for liquid to be filtered, the polymer-based film obtained with step (2) is for filtering material, be 0.1 ~ 0.3MPa at operating pressure, temperature is under 25 ~ 90 DEG C of conditions, adopt depositional model to run 3 ~ 60min continuously, obtain dynamic complex film;
(4), after dynamic complex film natural air drying step (3) obtained, described conducting polymer perforated membrane is namely obtained.
2. conducting polymer perforated membrane product according to claim 1, in described step (3), treatment temperature is 80-90 DEG C.
3. conducting polymer perforated membrane product according to claim 1, described conducting polymer perforated membrane can be prepared by following methods: nano carbon black particle 14g in 180g water 25 DEG C carry out ultrasonic disperse 2h, ultrasonic power is 100w, then high-speed stirred 2h, polyoxyethylene 6g is added wherein, and fully 2h is stirred under 80 DEG C of conditions, mixing speed is 800 ~ 1200r/min, obtains uniform Dynamic Membrane casting solution; Polyvinylidene fluoride flat film water is rinsed 10min; With Dynamic Membrane casting solution for liquid to be filtered, with polyvinylidene fluoride flat film for filtering material, under the operating pressure of 0.1MPa, at 80 DEG C of temperature, adopt cross-flow pressurization depositional model, run 30min continuously, after obtaining dynamic complex film natural air drying, namely obtain described conducting polymer perforated membrane; Described conducting polymer perforated membrane water flux 243.9L/ (m
2.h), bubble point aperture is 0.27 μm, and surface specific resistance is 165 Ω m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210516832.XA CN103846011B (en) | 2012-12-05 | 2012-12-05 | A kind of conducting polymer perforated membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210516832.XA CN103846011B (en) | 2012-12-05 | 2012-12-05 | A kind of conducting polymer perforated membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103846011A CN103846011A (en) | 2014-06-11 |
| CN103846011B true CN103846011B (en) | 2015-09-09 |
Family
ID=50854405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210516832.XA Active CN103846011B (en) | 2012-12-05 | 2012-12-05 | A kind of conducting polymer perforated membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103846011B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL412800A1 (en) | 2015-06-22 | 2017-01-02 | Secura B. C. Spółka Z Ograniczoną Odpowiedzialnością | Manufacturing of conductive polymer filters |
| CN105268330A (en) * | 2015-11-14 | 2016-01-27 | 华文蔚 | Polymer electric-conduction porous membrane |
| CN110354695A (en) * | 2019-06-26 | 2019-10-22 | 中国科学院生态环境研究中心 | Conductive hydrophobic membrane, preparation method and the electric heating membrane component comprising it |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276262A (en) * | 1999-06-08 | 2000-12-13 | 中国科学院生态环境研究中心 | Process and special equipment for preparing anti-pollution compound plyvinyl alcohol film |
| CN101700473A (en) * | 2009-10-30 | 2010-05-05 | 北京工业大学 | Self-assembly method of inorganic nano particle hybridization organic membrane |
| CN102139188A (en) * | 2011-01-05 | 2011-08-03 | 常州大学 | Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane |
| CN102671551A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN102688701A (en) * | 2012-06-18 | 2012-09-26 | 中国海洋大学 | Preparation method of polyelectrolyte self-assembled composite nonafiltration membrane based on coordination |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2572015B2 (en) * | 1985-01-11 | 1997-01-16 | 日東電工株式会社 | Method for producing aromatic polysulfone composite semipermeable membrane |
-
2012
- 2012-12-05 CN CN201210516832.XA patent/CN103846011B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276262A (en) * | 1999-06-08 | 2000-12-13 | 中国科学院生态环境研究中心 | Process and special equipment for preparing anti-pollution compound plyvinyl alcohol film |
| CN101700473A (en) * | 2009-10-30 | 2010-05-05 | 北京工业大学 | Self-assembly method of inorganic nano particle hybridization organic membrane |
| CN102139188A (en) * | 2011-01-05 | 2011-08-03 | 常州大学 | Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane |
| CN102671551A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN102688701A (en) * | 2012-06-18 | 2012-09-26 | 中国海洋大学 | Preparation method of polyelectrolyte self-assembled composite nonafiltration membrane based on coordination |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103846011A (en) | 2014-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dou et al. | Electrospinning of metal–organic frameworks for energy and environmental applications | |
| Zhao et al. | Metal-organic framework based membranes for selective separation of target ions | |
| Chen et al. | Fabrication of a superhydrophilic PVDF-g-PAA@ FeOOH ultrafiltration membrane with visible light photo-fenton self-cleaning performance | |
| CN102614783B (en) | Method for preparing high-flux composite membrane from dopamine-modified nanometer material | |
| CN103861472B (en) | A kind of preparation method of amino modified graphene oxide compound forward osmosis membrane | |
| CN102580560B (en) | Method for preparing nano-material-doped polymer film | |
| CN104772048A (en) | Inorganic filler and dopamine compound inorganic and organic hybrid membrane as well as preparation method and application of membrane | |
| CN102210979B (en) | Positively charged polyvinyl chloride hollow fiber nanofiltration membrane and preparation method thereof | |
| CN103240005B (en) | Tubular composite nanofiltration membrane and preparation method thereof | |
| Mahdavi et al. | Preparation of high-performance PVDF mixed matrix membranes incorporated with PVDF-g-PMMA copolymer and GO@ SiO2 nanoparticles for dye rejection applications | |
| CN106621831B (en) | A method of it is quickly nanofiltration membrane by micro-filtration or ultrafiltration membrane converted in-situ | |
| CN102500250A (en) | Macromolecular-inorganic hybrid membrane, and preparation method and application thereof | |
| CN104923092A (en) | Hydrophilic/hydrophobic transition polyelectrolyte/titanium dioxide composite nanofiltration membrane and preparation method thereof | |
| WO2022227838A1 (en) | Preparation method for hollow fiber inorganic membrane | |
| CN103846011B (en) | A kind of conducting polymer perforated membrane | |
| CN109304088A (en) | A kind of sea water desalination membrane of strong alkali-acid resistance and the preparation method and application thereof | |
| CN102389722A (en) | Method for preparing nano composite ultrafiltration membrane by using polyaniline nano material | |
| Ma et al. | Hydrophilic PAA-g-MWCNT/TiO2@ PES nano-matrix composite membranes: Anti-fouling, antibacterial and photocatalytic | |
| CN106178975A (en) | A kind of Kynoar/polyacrylonitrile blended hollow-fibre membrane | |
| Mo et al. | A critical review on classifications, characteristics, and applications of electrically conductive membranes for toxic pollutant removal from water: Comparison between composite and inorganic electrically conductive membranes | |
| CN102974227B (en) | Method for preparing polymer conductive porous membrane | |
| CN108499361B (en) | Preparation method of nano-porous polymer film with adjustable pore size | |
| CN105498552B (en) | A kind of conductive filter membrane and its preparation method and application that conductor oxidate is modified | |
| CN102974233B (en) | There is conduction and photo-catalysis function polymer/inorganic thing particle hybrid separation membrane | |
| CN105664735A (en) | PTFE blend flat sheet membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |