CN1108583A - Method for preparation of complex film - Google Patents
Method for preparation of complex film Download PDFInfo
- Publication number
- CN1108583A CN1108583A CN 94110114 CN94110114A CN1108583A CN 1108583 A CN1108583 A CN 1108583A CN 94110114 CN94110114 CN 94110114 CN 94110114 A CN94110114 A CN 94110114A CN 1108583 A CN1108583 A CN 1108583A
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- CN
- China
- Prior art keywords
- coating
- vacuum
- coating liquid
- membrane
- preparation
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000012510 hollow fiber Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims description 59
- 239000011248 coating agent Substances 0.000 claims description 55
- 239000012528 membrane Substances 0.000 claims description 51
- 239000000835 fiber Substances 0.000 claims description 22
- 235000012489 doughnuts Nutrition 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- -1 SPSF Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The method for preparation of composite film is of applicating coating-material to the internal surface of hollow fiber-film. It is characterized by that the coating-liquid is immersed in the internal cavity of hollow fiber-film and at the same time the outer-cavity of hollow fiber-film is vacuumed for a certain time and after the coating-liquid is removed out the outer-cavity of hollow fiber-film is continuously vacuumed for a certain time. The hollow fiber composite film is specially suitable for use in air separation.
Description
The present invention relates to membrane separation technique, specifically provide a kind of system method of hollow fiber composite membrane, adopt the prepared composite membrane of this technology to be suitable for use as divided gas flow, particularly air separation.
Till settled the present, membrane separation technique has been successfully used to fields such as micro-filtration, ultrafiltration, counter-infiltration, dialysis, gas separation, dehumidifying, pervaporation.Gas separates, and the technology of two industryizatioies has: H
2/ N
2Separation is reclaimed H from synthetic ammonia relief gas
2, H
2/ CO separates and is used for synthetic controlled atmosphere ratio, and oxygen nitrogen separates and is used to make rich nitrogen and oxygen rich gas etc.The core that film separates is that preparation has certain saturating amount and film optionally, and we are referred to as to ooze and sow film.
Permeable membrane divides three types: 1) homogeneous membrane; 2) anisotropic membrane; 3) composite membrane.Homogeneous membrane and anisotropic membrane are to be formed by a kind of membrane material, and composite membrane is then formed by two or more membrane material.After homogeneous membrane forms, have identical density on the film thickness of trimming, because the restriction of filming technology and the restriction of material itself, infiltration rate is low.Anisotropic membrane exists two different zones on the structure of film, one deck that zone is an optionally osmotic fluid component of mixture as thin as a wafer and fine and close cortex, another zone is the porous supporting course.Composite membrane is stack thin layer of one or more permeable membrane materials or coating and form on porous matrix normally, described in US3616607, porous matrix does not have separating power basically, play supporting role, coating or thin layer must approach and densification, and centrifugation is arranged.Disclose principle and method that a kind of preparation has the anisotropic membrane of thin epidermal area among the US3133132, but the epidermal area of the anisotropic membrane that this method makes often exists various defectives, as crackle, hole etc., this kind film also is not suitable for the gas separation.A kind of resistance composite membrane is disclosed among the US4230463, this composite membrane is to apply the another kind of parting material of one deck on anisotropic membrane, the intrinsic separation selectivity of this parting material is lower than the intrinsic separation selectivity of asymmetric counterdie, but the separation selectivity of the composite membrane after the coating is significantly higher than the coating material and the separation selectivity of the anisotropic membrane of coating not, therefore Henis etc. has proposed famous Henis model, is instructing further developing of coating and composite membrane preparation.Coating technology to doughnut has two kinds of typical operation modes: intermittently operated and continued operation, relevant with the present invention is andnon-continuous operation manner.Disclose six kinds of coating processes among the US4230463, 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.A kind of method that coating material is overlayed on the inner surface of doughnut is disclosed in the embodiment, its process is to be that presulfurization Sylgand 184 silicon rubber/pentane coating liquid of 3% is squeezed into the inner chamber of ps hollow fiber uf membrane with pump with concentration, make solution pass the inner chamber of fibre pipe lentamente, then with doughnut air drying.But this method can not guarantee coating material and be distributed in equably on the inner surface of fibre pipe.US4214020 discloses a kind of coating process at intermittence to the doughnut boundling.Its method is: the doughnut boundling is immersed in by in the prepared coating liquid of suitable solvent dissolving suitable coating material, simultaneously by applying a pressure reduction in the export-oriented fibre bundle of fibre bundle, vacuumize as shell pressurization or tube chamber, coating material is deposited on the outer surface of hollow fiber bundle.Because coating is at the outer surface of doughnut, thus bonding just being difficult between the fiber avoid.A kind of method for preparing amberplex is disclosed among the US4014798.Be that hollow-fibre membrane with porous is immersed in the crosslinkable polymer solution that contains the tetravalence amido and prepares amberplex.Described a kind of implementation method in embodiment: polymerisable monomeric compound solution is beaten to the other end by pump from an end of doughnut boundling, solution mixture will pass permeable doughnut tube wall and be extruded, after the polymer monomer polymerization, residuals in the fiber core is driven out of by forced flow, but this method still can not guarantee the uniformity of coating.
The object of the present invention is to provide a kind of preparation method of internally coated hollow-fibre membrane, this technology is suitable for the hollow-fibre membrane of boundling is carried out the coating at intermittence.Adopt the prepared composite membrane of this technology evenly fine and close, have good selectivity and permeability, be applicable to that gas separates, particularly air separation.
The preparation method of composite membrane of the present invention is: counterdie is the hollow-fibre membrane with internal dense lamella, when it is characterized in that coating coating liquid is immersed in the hollow-fibre membrane inner chamber, applies vacuum at outer surface simultaneously, shifts out coating liquid, needs to keep vacuum a period of time.
White coating material of coating liquid and solvent composition, coating material is: POLYPROPYLENE GLYCOL, SPSF, polyvinyl pyridine, ethyl cellulose, polysiloxanes are preferably polysiloxanes.Solvent is to dissolve coating material and don't dissolving asymmetric hollow fiber counterdie, boiling point is between 20 °～100 ℃, be preferably gasoline, pentane, benzinum etc., coating liquid concentration is in 0.1～15%(weight) between, best 0.5～7%(weight) between.
Coating liquid applies vacuum when immersing the doughnut tube cavity outside fibre pipe, vacuum should reach-0.080MPa at least, and the time is 3～30 minutes, is preferably 5～10 minutes.
Remove the back at coating liquid and continue to apply vacuum outside the fiber tube chamber, vacuum should reach-0.094MPa at least, and the time is 3～60 minutes, preferably 5～15 minutes.
After stopping to apply very, can adopt usual manner to solidify, as N
2Air-blowing is swept, methods such as hot-air solidifies, air curing, and hardening time was more preferably greater than 2 hours.
The composite membrane that preparation method of the present invention prepares is suitable for gas and separates, especially air separation, the i.e. process of preparation nitrogen-rich gas or oxygen rich gas from air.
Preparation has the doughnut anisotropic membrane of internal dense lamella only need regulate suitable condition, adopts a conventional wet spinning or a dried wet spinning process to copy and gets final product.The existence of dense layer surface makes inner coating process become feasible and practical in this.
In deep layer and the after-applied vacuum of coating, its purpose be to doughnut tube bank apply homogeneous by the outer power of interior sensing, make coating material can enter defective on the asymmetric counterdie, hole and reach the purpose of plug-hole, also make simultaneously coating material equably tight adhesion the doughnut anisotropic membrane on the surface.
Adopt process of the present invention can solve sticking problem between the doughnut, and greatly saved coating liquid, as to long 1.2 meters, diameter is that the hollow fiber bundle of 20mm carries out coating, need about 1200ml coating liquid with common coating process, and this method only needs 500ml.
Find that in the research of air separation when preparation nitrogen-rich gas or oxygen rich gas, the feeding gas hollow fiber cavity is better than walking exocoel, especially prepares the high concentration nitrogen-rich gas.Coating is made on the inner surface of hollow-fibre membrane, helps the technical process of unstripped gas in silk; And coating is coated on the outer surface of doughnut, if in the unstripped gas wire, then will be easy to cause coating shedding or the arch formation that the people retouched such as Henis occur, thus the life-span of reducing membrane separating property and membrane separator.
The hollow fiber composite membrane of the inventive method preparation simultaneously also has unique advantage in assembling aspect growing up to be a useful person, when film is loaded into shell separator, can damage the outer surface of hollow-fibre membrane because of some factor, if external coating, then damaged coating and the separating property of whole membrane separator is decreased, and the present invention is a undercoating, even outer surface damages to some extent, also can not have influence on the separating property of separator.
Below in conjunction with embodiment the present invention is described further:
Embodiment 1
Selecting the asymmetric hollow fiber membrane that interior dense layer surface is arranged of polysulfone material preparation for use is counterdie, at the two ends casting epoxy resin, make the epoxy tube sheet bundle of both ends open, place sealable container, use 4%(weight) the benzinum coating solution of silicon rubber immerse the hollow fiber bundle inner chamber, exocoel (being container intracavity) at fibre bundle applied vacuum 5 minutes simultaneously, and vacuum is-0.098MPa; Continued to apply vacuum 5 minutes after removing coating liquid, vacuum is-0.0995MPa; After stopping to vacuumize assembly is placed N
2Purge in the air-flow and solidified 2 hours.The oxygen permeability that obtains hollow fiber composite membrane is 1.62 * 10
-5Cm
3/ cm
2ScmHg, oxygen nitrogen selectivity are 4.5.
Claims (5)
1, a kind of preparation method of composite membrane, counterdie is the hollow-fibre membrane with internal dense lamella, when it is characterized in that coating coating liquid is immersed in the hollow-fibre membrane inner chamber, applies vacuum at outer surface simultaneously, shifts out coating liquid, needs to keep vacuum a period of time.
2, according to the described preparation method of claim 1, it is characterized in that coating liquid by coating material and solvent composition, coating material is: POLYPROPYLENE GLYCOL, SPSF, polyvinyl pyridine, ethyl cellulose, polysiloxanes are preferably polysiloxanes; Solvent be boiling point between 20 °～100 ℃, can dissolve coating material and don't dissolving asymmetric hollow fiber counterdie, as gasoline, pentane, benzinum etc., coating liquid concentration is in 0.1～15%(weight) between, best 0.5～7%(weight) between.
3, according to the described preparation method of claim 1, when immersing the doughnut tube cavity, coating liquid outside fibre pipe, applies vacuum, it is characterized in that vacuum should reach-0.080MPa at least, the time is 3～30 minutes, is preferably 5～10 minutes.
4, according to the described preparation method of claim 1, remove the back at coating liquid and continue outside the fiber tube chamber, to apply vacuum, it is characterized in that vacuum should reach-0.094MPa at least, the time is 3～60 minutes, preferably 5～15 minutes.
5, a kind of composite membrane according to the described preparation method's preparation of claim 1 is used for the divided gas flow separation, it is characterized in that this film is suitable for air separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110114 CN1108583A (en) | 1994-03-15 | 1994-03-15 | Method for preparation of complex film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110114 CN1108583A (en) | 1994-03-15 | 1994-03-15 | Method for preparation of complex film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1108583A true CN1108583A (en) | 1995-09-20 |
Family
ID=5034102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94110114 Pending CN1108583A (en) | 1994-03-15 | 1994-03-15 | Method for preparation of complex film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1108583A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7556761B2 (en) | 2002-12-27 | 2009-07-07 | Shenzhen Yang Qian Material Application Technology Co., Ltd. | Process of manufacturing core-sheath composite fiber |
| CN103028536A (en) * | 2012-12-20 | 2013-04-10 | 天邦膜技术国家工程研究中心有限责任公司 | Vacuum Coating Process of Hollow Fiber Nitrogen-Hydrogen Membrane Module |
| US8528883B2 (en) | 2007-08-01 | 2013-09-10 | Kolon Industries, Inc. | Hollow fiber membrane for humidifier and method for manufacturing the same |
| 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 |
| CN105344314A (en) * | 2015-12-07 | 2016-02-24 | 上海绿强新材料有限公司 | Porous hollow tubular composite membrane and preparation method and application thereof |
| CN107438518A (en) * | 2016-04-14 | 2017-12-05 | 塞法尔股份公司 | Composite membrane and method for preparing composite membrane |
-
1994
- 1994-03-15 CN CN 94110114 patent/CN1108583A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7556761B2 (en) | 2002-12-27 | 2009-07-07 | Shenzhen Yang Qian Material Application Technology Co., Ltd. | Process of manufacturing core-sheath composite fiber |
| US8528883B2 (en) | 2007-08-01 | 2013-09-10 | Kolon Industries, Inc. | Hollow fiber membrane for humidifier and method for manufacturing the same |
| CN103028536A (en) * | 2012-12-20 | 2013-04-10 | 天邦膜技术国家工程研究中心有限责任公司 | Vacuum Coating Process of Hollow Fiber Nitrogen-Hydrogen Membrane Module |
| 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 |
| CN105344314A (en) * | 2015-12-07 | 2016-02-24 | 上海绿强新材料有限公司 | Porous hollow tubular composite membrane and preparation method and application thereof |
| CN105344314B (en) * | 2015-12-07 | 2017-10-27 | 上海绿强新材料有限公司 | A kind of porous hollow tubular composite membrane and preparation method and application |
| CN107438518A (en) * | 2016-04-14 | 2017-12-05 | 塞法尔股份公司 | Composite membrane and method for preparing composite membrane |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |