CN103611429A - Preparation method of composite phase separated flat plate micro-filtration membrane - Google Patents
Preparation method of composite phase separated flat plate micro-filtration membrane Download PDFInfo
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- CN103611429A CN103611429A CN201310594642.4A CN201310594642A CN103611429A CN 103611429 A CN103611429 A CN 103611429A CN 201310594642 A CN201310594642 A CN 201310594642A CN 103611429 A CN103611429 A CN 103611429A
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Abstract
The invention provides a preparation method of a composite phase separated flat plate micro-filtration membrane, which belongs to the technical field of membrane separation. The preparation method comprises the following steps: respectively weighing out 12%-22% of polyacrylonitrile (PAN), 7%-12% of organic acid and 66%-81% of N, N-dimethyl formamide by mass percentage; mixing the polyacrylonitrile (PAN), the organic acid and the N, N-dimethyl formamide evenly to obtain a mixture; heating the mixture to 40-60 DEG C to obtain a film-casting liquid; then casting the film-casting liquid on a glass plate with the temperature of 20-80 DEG C to prepare a flat plate membrane intermediate; immersing the flat plate membrane intermediate in a 2% aqueous solution of carbonate or bicarbonate with the temperature of 5-35 DEG C to remove the N, N-dimethyl formamide; and carrying out a chemical reaction to obtain the polyacrylonitrile flat plate micro-filtration membrane. The cross section of the obtained flat plate micro-filtration membrane is asymmetric and anisotropic, and the flat plate micro-filtration membrane has relatively excellent anti-pollution performance.
Description
Technical field
The present invention relates to a kind of preparation method of compound phase separating plate micro-filtration membrane, disclose a kind of use compound phase partition method and prepare dull and stereotyped microfiltration membrane process, the perforated membrane making can be used in the fields such as environmental protection, water treatment, belongs to membrane separation technique field.
Technical background
The multidisciplinary contents such as polymer material science, physical chemistry, organic synthesis, separation engineering, plant equipment that membrane separation technique is integrated.The development of membrane technology has obtained countries in the world government and scientist's great attention.U.S.'s official document says when mentioning the importance of membrane separation technique: 18th century electrical equipment changed whole industrial process, and 21 century membrane technology changed All Around The World ".International academic community is unanimously thought: " who has grasped membrane technology, and who has just grasped the future of chemical industry ".Appropriate authority is also pointed out: membrane technology will become to take as the leading factor one of six large new and high technologies of futurity industry with technology such as optical fiber, superconductions, will be also 21 centurys ten one of large high-tech industries.Visible, development membrane separation technique has important and far-reaching meaning for economic development and Scientific Construction.Film separation process as a novel high score from, concentrated, purification and purification techniques; there is the plurality of advantages such as energy consumption is low, effluent quality good, floor space is little, treatment effeciency is high, sludge yield is low; compare with other traditional isolation technics; membrane separation technique has unrivaled advantage; particularly its outstanding behaviours aspect the regeneration of energy-conservation, environmental protection and water resource, makes people regard with special esteem to the development prospect of membrane separation technique.Membrane separation technique is widely applied at industry fields such as desalinization, sewage disposal, petrochemical industry, power-saving technology, clean technologies, biochemistry, medicine, light industry, food, health care, environmental protection, electronics, weaving, metallurgy, the energy, space flight, heavy industrys.
The preparation method of polymer porous film has a variety of, mainly contains phase inversion, inorganic particulate as filler or additive, sintering and nuclear track.Because the feature that phase inversion has simply, production scale is flexible and cost is low, industrial main employing phase inversion is prepared film at present.Phase inversion mainly comprises that phase separation and thermic are separated.Phase separation method (NIPS), is also dipper precipitation method (L-S method), is during casting solution immersion precipitation is bathed time, and solvent and non-solvent exchange, and finally cause Gelation.Thermally induced phase separation (TIPS) refers at high temperature makes homogeneous phase solution by polymer dissolution in the little diluent of boiling point HMW, then the polymer solution of this homogeneous phase be prefabricated into needed shape and coolingly allow it be separated, thereby making perforated membrane.Thermally induced phase separation (TIPS) is that with the difference of phase separation method (NIPS) maximum the former needs exchange heat to convert homogeneous membrane liquid to two-phase, and the latter relies on the mass exchange of solvent and non-solvent to carry out film forming.When thermally induced phase separation (TIPS) is prepared perforated membrane, easily form intensity difference, spherocrystal packed structures that flux is low, and be difficult for forming the inierpeneirating network structure of high and the asymmetric and incorgruous type that flux is high of intensity.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of compound phase separating plate micro-filtration membrane.
Many researchers is prepared perforated membrane to thermally induced phase separation (TIPS) and phase separation method (NIPS) and has been done a large amount of research, but the film-forming method that both are combined, and the correlative study of compound phase partition method is rarer.Therefore the non-solvent that the present invention induces chemical reaction causes mutually and thermic is combined together the dull and stereotyped micro-filtration membrane of preparation, the film section of resulting dull and stereotyped micro-filtration membrane is asymmetric and incorgruous type, film surface apertures is 0.085～0.1 micron (μ m), has good antifouling property.
Concrete technical scheme of the present invention is as follows:
A preparation method for compound phase separating plate micro-filtration membrane, is characterized in that, comprises the following steps:
(1) preparation of casting solution
Successively dimethyl formamide, organic acid are placed in to container, stir to dissolving completely, then add polyacrylonitrile (PAN), stir to dissolving completely, obtain casting solution and be heated to 40～60 ℃; Wherein the mass percent of polyacrylonitrile (PAN), organic acid, DMF is respectively 12%～22%, 7%～12%, 66%～81%;
(2) preparation of Flat Membrane intermediate
By the casting solution curtain coating of 40～60 ℃ of step (1), to temperature, be 20～80 ℃ of glass plate one end, make it be in one line, then with glass slicker, the casting solution arranging is pushed into the glass plate other end, obtain Flat Membrane intermediate;
(3) preparation of the dull and stereotyped micro-filtration membrane of polyacrylonitrile (PAN)
It is in the aqueous solution of carbonate (sodium carbonate, sodium acid carbonate, potash or saleratus) of 5～35 ℃ that the Flat Membrane intermediate that step (2) is made is immersed in temperature, preferred carbonate solution concentration 2wt%, remove the N in film, dinethylformamide, concurrent biochemical reaction, soak after 2 hours to take out and put into pure water and soak, obtain the dull and stereotyped micro-filtration membrane of PAN.
Organic acid in step (1) can be sulfamic acid, fumaric acid, maleic acid, malic acid or glacial acetic acid, preferably fumaric acid, malic acid.
In preferred steps (1), the mass fraction of polyacrylonitrile is 18%.
Advantage of the present invention:
The present invention mainly adopts the method that the non-solvent of chemical reaction induction causes mutually and thermic is separated and combines, and compound phase separation method is prepared the dull and stereotyped micro-filtration membrane of polyacrylonitrile.The dull and stereotyped micro-filtration membrane of polyacrylonitrile of the present invention has reached 95.6% to the rejection of protein molecule.
Accompanying drawing explanation
Fig. 1 is the electron scanning Electronic Speculum figure of the dull and stereotyped micro-filtration membrane of polyacrylonitrile of the present invention;
Fig. 2 is the graph of pore diameter distribution of embodiment 3.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.But the present invention is not limited to following examples, the thickness of following examples gained is 0.15 millimeter (mm) left and right.
Embodiment 1
The first step, is placed in container by DMF, organic acid successively, stirs to dissolving completely, then adds polyacrylonitrile (PAN), stirs to dissolving completely, and the casting solution obtaining is also heated to 50 ℃; Polyacrylonitrile (PAN) wherein: malic acid: the mass ratio=16%:9%:75% of DMF;
Second step, is 50 ℃ of glass plate one end by the casting solution curtain coating of 50 ℃ of step (1) to temperature, makes it be in one line, then with glass slicker, the casting solution arranging is pushed into the glass plate other end, obtains Flat Membrane intermediate;
The 3rd step, it is, in the aqueous solution of 2% sodium acid carbonate of 15 ℃, to remove the solvent in film that the Flat Membrane intermediate that step (2) is made is immersed in temperature, concurrent biochemical reaction is soaked to take out after 2 hours and is put into pure water and soak, and obtains the dull and stereotyped micro-filtration membrane of PAN.
Micro-filtration membrane prepared by the present embodiment, at 25 ℃, the water flux under 0.1MPa is 134.7mlcm
-2h
-1, the rejection of protein is 88.5%.
Embodiment 2
The first step, is placed in container by DMF, organic acid successively, stirs to dissolving completely, then adds polyacrylonitrile (PAN), stirs to dissolving completely, obtains casting solution and is heated to 50 ℃; Polyacrylonitrile (PAN) wherein: fumaric acid: the mass ratio=18%:10%:72% of DMF;
Second step, is 80 ℃ of glass plate one end by the casting solution curtain coating of 50 ℃ of step (1) to temperature, makes it be in one line, then with glass slicker, the casting solution arranging is pushed into the glass plate other end, obtains Flat Membrane intermediate;
The 3rd step, it is, in the aqueous solution of 2% salt sodium carbonate of 25 ℃, to remove the solvent in film that the Flat Membrane intermediate that step (2) is made is immersed in temperature, concurrent biochemical reaction is soaked to take out after 2 hours and is put into pure water and soak, and obtains the dull and stereotyped micro-filtration membrane of PAN.
Micro-filtration membrane prepared by the present embodiment, at 25 ℃, the water flux under 0.1MPa is 100mlcm
-2h
-1, the rejection of protein is 83.4%.
Embodiment 3
The first step, is placed in container by DMF, organic acid successively, stirs to dissolving completely, then adds polyacrylonitrile (PAN), stirs to dissolving completely, obtains casting solution and is heated to 60 ℃; Polyacrylonitrile (PAN) wherein: glacial acetic acid: the mass ratio=18%:9%:73% of DMF;
Second step, is 50 ℃ of glass plate one end by the casting solution curtain coating of 60 ℃ of step (1) to temperature, makes it be in one line, then with glass slicker, the casting solution arranging is pushed into the glass plate other end, obtains Flat Membrane intermediate;
The 3rd step, it is, in the aqueous solution of 2% sodium acid carbonate of 35 ℃, to remove the solvent in film that the Flat Membrane intermediate that step (2) is made is immersed in temperature, concurrent biochemical reaction is soaked to take out after 2 hours and is put into pure water and soak, and obtains the dull and stereotyped micro-filtration membrane of PAN.
Micro-filtration membrane prepared by the present embodiment, at 25 ℃, the water flux under 0.1MPa is 82mlcm
-2h
-1, the rejection of protein is 95.6%.
Pure water flux is defined as the pure water volume that unit interval, unit are pass through, i.e. mistake! Do not find Reference source., wherein J is pure water flux, the area that A is film, and the permeable amount that V is film, t is the testing time.
Bovine serum albumin(BSA) (BSA) filters: a certain amount of bovine serum albumin(BSA) is dissolved in 0.3g/L NaOH solution, is mixed with the BSA solution of 0.1g/L.
Electron scanning Electronic Speculum map Fig. 1 of the dull and stereotyped micro-filtration membrane section of polyacrylonitrile that compound phase partition method of the present invention makes, pore-size distribution map Fig. 2 of embodiment 3, pass through scanning electronic microscope observation, the film that embodiment 3 obtains is the incorgruous type structure of typical asymmetric membrane, and film surface apertures major part is distributed in 0.1 micron (μ m).
Claims (6)
1. a preparation method for compound phase separating plate micro-filtration membrane, is characterized in that, comprises the following steps:
(1) preparation of casting solution
Successively dimethyl formamide, organic acid are placed in to container, stir to dissolving completely, then add polyacrylonitrile (PAN), stir to dissolving completely, obtain casting solution and be heated to 40～60 ℃; Wherein the mass percent of polyacrylonitrile (PAN), organic acid, DMF is respectively 12%～22%, 7%～12%, 66%～81%;
(2) preparation of Flat Membrane intermediate
By the casting solution curtain coating of 40～60 ℃ of step (1), to temperature, be 20～80 ℃ of glass plate one end, make it be in one line, then with glass slicker, the casting solution arranging is pushed into the glass plate other end, obtain Flat Membrane intermediate;
(3) preparation of the dull and stereotyped micro-filtration membrane of polyacrylonitrile (PAN)
It is in the aqueous solution of carbonate of 5～35 ℃ that the Flat Membrane intermediate that step (2) is made is immersed in temperature, remove the DMF in film, concurrent biochemical reaction, soak after 2 hours to take out and put into pure water and soak, obtain the dull and stereotyped micro-filtration membrane of PAN.
2. according to the preparation method of a kind of compound phase separating plate micro-filtration membrane of claim 1, it is characterized in that, in step (1), related organic acid is sulfamic acid, fumaric acid, maleic acid, malic acid or glacial acetic acid.
3. according to the preparation method of a kind of compound phase separating plate micro-filtration membrane of claim 1, it is characterized in that, in step (3), related carbonate is sodium carbonate, sodium acid carbonate, potash or saleratus.
4. according to the preparation method of a kind of compound phase separating plate micro-filtration membrane of claim 1, it is characterized in that, the organic acid in step (1) is fumaric acid and malic acid.
5. according to the preparation method of a kind of compound phase separating plate micro-filtration membrane of claim 1, it is characterized in that, in step (1), the mass fraction of polyacrylonitrile is 18%.
6. according to the preparation method of a kind of compound phase separating plate micro-filtration membrane of claim 1, it is characterized in that, carbonate aqueous solution concentration is 2wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107803118A (en) * | 2017-11-03 | 2018-03-16 | 宁波大学 | A kind of Triafol T/polyamide composite film and application thereof |
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| CN1817419A (en) * | 2005-11-28 | 2006-08-16 | 国家海洋局杭州水处理技术研究开发中心 | Production of liquid separating film |
| CN101053782A (en) * | 2007-05-16 | 2007-10-17 | 河北科技大学 | Antibiotic cellulose acetate nanofiltration membrane and its preparation method |
| CN101733025A (en) * | 2010-01-21 | 2010-06-16 | 天津大学 | Polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution and preparation method thereof |
| CN103120901A (en) * | 2013-03-01 | 2013-05-29 | 北京工业大学 | Preparation method of polyacrylonitrile flat micro-filtration membrane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817419A (en) * | 2005-11-28 | 2006-08-16 | 国家海洋局杭州水处理技术研究开发中心 | Production of liquid separating film |
| CN101053782A (en) * | 2007-05-16 | 2007-10-17 | 河北科技大学 | Antibiotic cellulose acetate nanofiltration membrane and its preparation method |
| CN101733025A (en) * | 2010-01-21 | 2010-06-16 | 天津大学 | Polyacrylonitrile hydrolyzed modified ultrafiltration membrane resisting protein pollution and preparation method thereof |
| CN103120901A (en) * | 2013-03-01 | 2013-05-29 | 北京工业大学 | Preparation method of polyacrylonitrile flat micro-filtration membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107803118A (en) * | 2017-11-03 | 2018-03-16 | 宁波大学 | A kind of Triafol T/polyamide composite film and application thereof |
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Application publication date: 20140305 |