CN1108588A - Method for preparation of improved complex film with coating - Google Patents
Method for preparation of improved complex film with coating Download PDFInfo
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- CN1108588A CN1108588A CN 94110113 CN94110113A CN1108588A CN 1108588 A CN1108588 A CN 1108588A CN 94110113 CN94110113 CN 94110113 CN 94110113 A CN94110113 A CN 94110113A CN 1108588 A CN1108588 A CN 1108588A
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Abstract
An improved method for preparation of composite film is that hollow fiber film is soaked in coating liquid for not less than 0.5 h, then vacuumed and after the coating liquid is removed the outer-cavity of the hollow fiber film is continuously dried under vacuum. The penetrant separation property of said hollow fiber composite film is increased. It is suitable for use in gas separation.
Description
The present invention relates to membrane separation technique, specifically provide a kind of preparation method of hollow fiber composite membrane, adopt the prepared hollow-fibre membrane of this two skill to be suitable for use as divided gas flow, particularly air separation.
Membrane separation technique has obtained development at full speed since coming out, successfully be applied to technical fields such as micro-filtration, ultrafiltration, electrodialysis, counter-infiltration dehumidifying, gas separation, film distillation, pervaporation.Masking technique, method emerge in an endless stream, but still are key with the film of preparation high permeability and high selectivity.
Film can be divided three classes substantially: 1) homogeneous membrane; 2) composite membrane anisotropic membrane and 3).Homogeneous membrane and anisotropic membrane all are by making with a kind of membrane material, and composite membrane is generally made by two or more membrane material.Homogeneous membrane is owing to the restriction of filming technology and material itself, and permeability is low, general only do research use.Anisotropic membrane structurally exists two different zones: the thin and fine and close cortex of one deck that the zone is an optionally osmotic fluid component of mixture, another zone is a porous supporting course optionally not, and its effect is that the cortex that prevents to approach is by compression failure.The thickness of cortex is about 0.1～1 μ m because it is very thin, so the permeability of film be improved, again because its is fine and close, so the selectivity of film has also obtained certain assurance.Yet often exist various defectives on the thin separating layer of this anisotropic membrane, as crackle, hole etc., these defectives reduce the selectivity of film greatly, thereby are not suitable for effective gas separation.Composite membrane is that (this porous matrix even can be above the anisotropic membrane stated) covers the thin dense top layer (being separating layer) of one deck on porous matrix, and this is two-layer normally to be made of different membrane materials.The advantage of composite membrane is can be respectively supporting course or separating layer to be optimized and to improve, and tries to achieve best of breed by suitable means again.
The preparation method of composite membrane mainly contains: interfacial polymerization; Immerse coating; Plasma polymerization; Homogeneous membrane modification etc.What the present invention was correlated with is to immerse coating process, and this method is a kind of method for preparing composite membrane by the thin and fine and close top layer of coating one deck on the porous supporting mass.Its process is: anisotropic membrane (hollow-fibre membrane or flat sheet membrane) is immersed in the coating liquid that is dissolved with polymer or prepolymer or monomer, take out subsequently, just on anisotropic membrane, adhered to the thin coating solution of one deck this moment, place baking oven to make solvent evaporates the film after taking out and make crosslinked polymer, promptly form the thin compacted zone of one deck---be called for short coating.U.S. Pat 4,230 discloses six kinds of coating processes in 463, and be respectively: A. immerses porous hollow fiber membrane in the liquid coating material of not diluted, and allows excess liquid drip; B. porous hollow fiber is immersed in the coating material of not diluted and in the fibre pipe of doughnut, apply vacuum simultaneously, stop to vacuumize the relief residual body and drip; C. porous hollow fiber membrane is immersed in the liquid coating material of varsol dilution, takes out the relief solvent evaporates; D. porous hollow fiber membrane is immersed in the liquid coating material of varsol dilution and applies vacuum in the fibre pipe at doughnut simultaneously, stop to vacuumize the relief solvent evaporates; E. porous hollow fiber is immersed in the coating liquid, coating liquid is polymerizable prepolymers and an amount of curing agent to be dissolved in the varsol make, and takes out the relief solvent evaporates and also makes prepolymer cures; F. the same E of process is to applying vacuum in the doughnut tube chamber in the immersion process.U.S. Pat 4,2140,20 have also set forth similar coating process at intermittence to the doughnut boundling.Above-mentioned patented method can access the film of better performances, but still can't reach the intrinsic separation/permeance property of film.A kind of method of post processing composite membrane is disclosed in the U.S. Pat 4767422, mainly be: the film that had been coated with layer with the volatile solvent post processing that contains or do not contain a small amount of additive, to repair the defective in the separating layer, evaporation removes to desolvate and makes the film drying again, a spot of fixedness additive is still stayed in the defective of separating layer, and block this defective, to improve the separation/permeance property of composite membrane.But the enforcement of this method is subjected to solvent effect bigger, is difficult for accomplishing neither to damage or dissolve very much the coating of the composite membrane that has made, can improve the separation/permeance property of composite membrane again significantly.
The object of the present invention is to provide a kind of preparation method of composite membrane, this method cost is low, and easy operating, prepared composite membrane have the intrinsic separation/permeance property near film.
The preparation method of composite membrane of the present invention comprise film immersion, vacuum coating, drain and operations such as dry solidification, it is characterized in that soaking operation is the pre-soaking that hollow-fibre membrane was no less than in coating liquid 0.5 hour; Drain operation and carry out under vacuum condition, promptly film takes out fibre bundle behind vacuum coating from masking liquid, keeps draining under the vacuum condition.Composite membrane preparation method specifically of the present invention is: 1. the hollow-fibre membrane of boundling is soaked in coating liquid and be no less than 0.5 hour; 2. will immerse through the fibre bundle of immersion and give in the coating liquid that soaks identical or different concentration, tube chamber applies vacuum in hollow-fibre membrane simultaneously; 3. behind vacuum coating, fibre bundle takes out from coating, and keeps draining under the vacuum; At last, with fiber conventional method airing or oven dry.
Coating liquid is by coating material and solvent composition, coating material: POLYPROPYLENE GLYCOL, polyvinyl alcohol, SPSF, poly-trimethyl silicane propine, polyvinyl pyridine, ethyl cellulose, polysiloxanes etc.; Solvent: boiling point can dissolve coating material and not dissolve the asymmetric hollow fiber counterdie between 20 °～100 ℃, as gasoline, benzinum, pentane etc.
Coating liquid concentration is 0.1～5% (weight) when giving immersion, preferably in 0.4～2% (weight), gives soak time and is at least 0.5 hour, and the suitable time is 1～50 hour.Give also can apply when soaking low vacuum (vacuum for-0.02MPa).
When vacuum coating, coating liquid concentration is 0.1～10% weight, is preferably in 0.4～5% weight, and vacuum should reach-0.070MPa at least, 1～30 minute time, is preferably 5～10 minutes.
Continue to apply vacuum from coating liquid, drain after taking out, vacuum should reach-0.094MPa at least, 3～60 minutes time, is preferably in 5～15 minutes.
The time of dry solidification was at least 2 hours, can be at N
2Dry solidification is swept down in air-blowing, can also use warm air blowoff, even the air air dry all can.
Method of the present invention can easily be permeated/composite membrane that separating property has improved, and performance is near the intrinsic infiltration/separating power of film, and this film is suitable for gas to be separated.
Be described further below in conjunction with embodiment.
Embodiment 1
Monofilament is of a size of external diameter 537 μ m, the polysulfone hollow fibre anisotropic membrane boundling of internal diameter 347 μ m is also made epoxy tube sheet end socket, soaked 50 hours in silicon rubber/benzinum coating liquid with tow immersion 0.4% (weight) subsequently, then vacuumize coating in the coating liquid of same concentrations, vacuum reaches-0.096MPa, 1 minute time, continued to vacuumize 3 minutes after removing coating liquid, vacuum reaches-0.098MPa, and the air dry of taking-up was solidified 2 hours, and the permeability of its hydrogen is 1.07 * 10
-4Cm
3/ cm
2ScmHg, hydrogen nitrogen selectivity are 66.9, and this film is suitable for hydrogen nitrogen to be separated.
Embodiment 2
Counterdie is with embodiment 1, in the silicon rubber/benzinum coating liquid of 0.5% (weight), soaked 21 hours, then in identical coating liquid, vacuumize coating, vacuum is 0.096MPa, time is 1 minute, continue to take out 3 minutes vacuum after removing coating liquid, vacuum is 0.098MPa, takes out the back air dry and solidifies 5 hours.Obtaining oxygen permeability is 2.03 * 10
-5Cm
3/ cm
2ScmHg, the oxygen nitrogen selectivity is 5.8 hollow fiber composite membrane, being suitable for the separation of oxygen nitrogen is air separation.
Pass through the foregoing description, technology provided by the present invention since adopted film give the immersion operation, and technology such as keeping draining under the vacuum condition, make the composite membrane coating densification of preparing, evenly, and the coating material relative rich is combined in the hole and reach the purpose of plug-hole.Therefore make composite membrane have good selectivity and permeability, even composite membrane more approaches its intrinsic separation/penetrating power.This hollow-fibre membrane can be suitable for the separation of hydrogen nitrogen or oxygen nitrogen.
Claims (6)
- A preparation that improves the composite membrane of coating comprise film immersion, vacuum coating, drain and operations such as dry solidification, it is characterized in that soaking operation is the pre-soaking that hollow-fibre membrane was no less than in coating liquid 0.5 hour; Drain operation and carry out under vacuum condition, promptly film takes out fibre bundle behind vacuum coating from masking liquid, keeps draining under the vacuum condition.
- 2. preparation method according to claim 1, it is characterized in that coating liquid by coating material and solvent composition, coating material is: POLYPROPYLENE GLYCOL, polyvinyl alcohol, SPSF, poly-trimethyl silicane propine, polyvinyl pyridine, ethyl cellulose or polysiloxanes etc.; Solvent is: boiling point can dissolve coating material and not dissolve the asymmetric hollow fiber counterdie between 20 °～100 ℃, as gasoline, benzinum, pentane etc.
- 3. preparation method according to claim 1 is characterized in that giving that coating liquid concentration is 0.1～5% (weight) when soaking, and preferably in 0.4～2% (weight), gives soak time 〉=0.5 hour, is preferably 1～50 hour.
- 4. one kind as preparation method as described in the claim 3, it is characterized in that giving when soaking applying low vacuum at the fibre pipe inner chamber, and vacuum reaches-0～0.02MPa.
- 5. a preparation method according to claim 1 is characterized in that when vacuum coating coating liquid concentration is 0.1～10% weight, is preferably 0.4～5% weight, and vacuum should reach-0.070MPa at least, 1～30 minute time, is preferably 5～10 minutes.
- 6. a preparation method according to claim 1 is characterized in that when draining vacuum should reach-0.094MPa at least, 3～60 minutes time, is preferably in 5～15 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110113A CN1053387C (en) | 1994-03-15 | 1994-03-15 | Method for preparation of improved complex film with coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110113A CN1053387C (en) | 1994-03-15 | 1994-03-15 | Method for preparation of improved complex film with coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1108588A true CN1108588A (en) | 1995-09-20 |
| CN1053387C CN1053387C (en) | 2000-06-14 |
Family
ID=5034101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110113A Expired - Fee Related CN1053387C (en) | 1994-03-15 | 1994-03-15 | Method for preparation of improved complex film with coating |
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| Country | Link |
|---|---|
| CN (1) | CN1053387C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073877C (en) * | 1997-05-17 | 2001-10-31 | 中国科学院大连化学物理研究所 | Preparation of hollow-fibre composite film |
| CN100411721C (en) * | 2006-04-04 | 2008-08-20 | 天津工业大学 | Hollow fiber composite membrane applicator, method for producing said hollow fiber composite membrane and product |
| CN102565282A (en) * | 2011-12-14 | 2012-07-11 | 天邦膜技术国家工程研究中心有限责任公司 | Sample evaluation method for hollow fiber membrane silk |
| CN105126644A (en) * | 2015-08-20 | 2015-12-09 | 张哲夫 | Preparation method for polypropylene hollow fiber ultrafiltration membrane coated with high-molecular composite coating |
| CN107789988A (en) * | 2016-08-31 | 2018-03-13 | 山东东岳高分子材料有限公司 | Hollow fiber composite membrane of ultra-thin active layer and preparation method thereof |
| CN114618321A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Hollow fiber membrane, preparation and application in hydraulic oil degassing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029822C (en) * | 1987-07-10 | 1995-09-27 | 联合碳化公司 | Composite membranes and their manufacture and use |
| CN1029773C (en) * | 1991-01-09 | 1995-09-20 | 中国科学院大连化学物理研究所 | Preparation of hypertonic polysulfone hollow fibred ultrafiltering film |
-
1994
- 1994-03-15 CN CN94110113A patent/CN1053387C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073877C (en) * | 1997-05-17 | 2001-10-31 | 中国科学院大连化学物理研究所 | Preparation of hollow-fibre composite film |
| CN100411721C (en) * | 2006-04-04 | 2008-08-20 | 天津工业大学 | Hollow fiber composite membrane applicator, method for producing said hollow fiber composite membrane and product |
| CN102565282A (en) * | 2011-12-14 | 2012-07-11 | 天邦膜技术国家工程研究中心有限责任公司 | Sample evaluation method for hollow fiber membrane silk |
| CN102565282B (en) * | 2011-12-14 | 2015-07-22 | 天邦膜技术国家工程研究中心有限责任公司 | Sample evaluation method for hollow fiber membrane silk |
| CN105126644A (en) * | 2015-08-20 | 2015-12-09 | 张哲夫 | Preparation method for polypropylene hollow fiber ultrafiltration membrane coated with high-molecular composite coating |
| CN107789988A (en) * | 2016-08-31 | 2018-03-13 | 山东东岳高分子材料有限公司 | Hollow fiber composite membrane of ultra-thin active layer and preparation method thereof |
| CN114618321A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Hollow fiber membrane, preparation and application in hydraulic oil degassing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053387C (en) | 2000-06-14 |
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