CN103657437A - Preparation method of hollow-fiber asymmetric composite membrane - Google Patents
Preparation method of hollow-fiber asymmetric composite membrane Download PDFInfo
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- CN103657437A CN103657437A CN201210346742.0A CN201210346742A CN103657437A CN 103657437 A CN103657437 A CN 103657437A CN 201210346742 A CN201210346742 A CN 201210346742A CN 103657437 A CN103657437 A CN 103657437A
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Abstract
The invention discloses a preparation method of a hollow-fiber asymmetric composite membrane. The preparation method comprises the following steps: (a) uniformly mixing a high-molecular polymer or a high-molecular polymer/inorganic filler mixed matrix material and the mixture, copolymer, derivatives of the high-molecular polymer and the high-molecular polymer/inorganic filler mixed matrix material with a solvent or a nonsolvent to prepare film casting liquids, wherein the mass concentrations of the high-molecular polymer is 5-50%; (b) respectively conveying first film casting liquid and second film casting liquid through an outer circular passage and middle circular passage of a three-passage spinning nozzle, conveying a core liquid through a central pipeline of the three-passage spinning nozzle, wherein the flow ratio of the first film casting liquid to the second film casting liquid is 0.1-2 and the temperature of the spinning nozzle is 25-90 DEG C; and enabling a nascent-state hollow fiber membrane to pass through a coagulation bath, wherein the temperature of the coagulation bath is between 20 DEG C below zero and 60 DEG C. According to the preparation method disclosed, by a simple process, the prepared hollow-fiber asymmetric composite membrane can have enough heat stability and mechanical stability, and the total flux of the hollow-fiber asymmetric composite membrane reaches 6000g/m<2>.hr.
Description
Technical field
The present invention relates to a kind of preparation method of doughnut asymmetric compound film, be particularly applicable to the preparation method of the alcohols dehydration a kind of doughnut asymmetric compound film separated with bio-fuel.
Background of invention
Infiltration evaporation separation is a kind of membrane separation technique, and this technology realizes the separation of liquid mixture by the recognition effect based on active function film.In the per-meate side of film, the dividing potential drop that sees through each component of film purges and is maintained at the level far below feed side by vacuum draw or gas (as air or nitrogen), by the pressure differential generation mass transfer driving force of both sides.Fluid molecule progressively becomes vapour phase from liquid phase when carrying out mass transfer through film, after infiltration side form surface desorption, with vacuum or air-flow, moves in cold trap and condenses.
Due to its special separating mechanism, distillation more energy-conserving and environment-protective aspect Separation of Mixtures with Same Boiling Point, nearly boiling point and/or thermal sensitivity mixture that infiltration evaporation isolation technics is more traditional, have good utilization prospect.At present, infiltration evaporation isolation technics has been applied to ethanol-water mixture dehydration, the removal of organic pollution in low concentration organic liquid waste, and nearly boiling point mixture and the close mixture of character is separated.
In order to obtain higher separative efficiency, need the membrane module that flux is high, separation factor is high, unit transmission area is large.Osmotic, evaporating and dewatering commercial membranes used is all flat composite membrane at present, and wherein hydrophilic membrane is mainly to take cross-linking polyvinyl alcohol (PVA) as separating layer material, and oil-wet film mainly be take silicon rubber as parting material.Consider that the waste liquid that need process is of a great variety, and charging composition constantly changes, limited material is selected and the configuration of film can not meet the requirement of practice completely, and the research that various materials, microstructure and macroscopical configuration film are launched will contribute to search out more effective film and membrane module.
Scholars are studied the utilization of multiple material in infiltration evaporation field such as perfluorinated sulfonic acid, cellulose acetate, polyacrylic acid, graft polypropylene, grafting anion exchange polyethylene, cellulose acetate/shitosan, Triafol T, polyimides, pottery and polymer blends.At the studied all kinds of film configurations for osmotic, evaporating and dewatering, because hollow-fibre membrane is because have high-bulk-density, good pliability and the mechanical back-up system that has a style of one's own and have huge advantage, its correlative study is more.
No matter which kind of material and configuration, membrane structure generally includes integrated anisotropic membrane and the large class of MULTILAYER COMPOSITE anisotropic membrane two.Integrated anisotropic membrane has fine and close separating layer and porous support layer, the non-solvent inversion of phases forming technique preparation of the homogeneous phase solution (being conventionally referred to as casting solution) by high polymer and organic solvent/non-solvent.Composite membrane is also to consist of porous support layer and fine and close separating layer.Different from integrated anisotropic membrane is, and its double-layer structure is formed by different casting solutions, thereby can use different materials.Composite membrane is prepared by multistep operation conventionally: one of method is first to form anisotropic porous support layer, then this structure contacts with casting solution, or the preformed ultra-thin fine and close separating layer of one deck that superposes in its surface, obtain composite construction again or by interfacial polymerization (filling monomer in the hole of supporting layer, monomer polymerization in hole subsequently).
At present, double-layer coextrusion goes out the preparation that technology has been applied to multilayer complex films.Adopting the main cause of the method is that it can reduce material cost, and can carry out respectively modification to difference in functionality layer.
Below the existing hollow fiber composite membrane technology of preparing for osmotic, evaporating and dewatering is illustrated.
H.Yanagishita has developed the polyimides pervaporation membrane for separating of ethanol water
[4].By phase inversion by containing aromatic polyimide (PI-2080), N, the Casting solution of the preparation of N '-dimethyl formamide (DMF) and Isosorbide-5-Nitrae dioxane is prepared anisotropic membrane.In vacuum drying chamber, film is carried out to 300 ° of C annealing in process, and at 25 ° of C temperature, measure it and 95vol.% ethanol water is carried out to the performance of infiltration evaporation.The molecular cut off of the film of making containing the Casting solution of 25wt.% polyimides, 37.5wt.% dimethyl formamide and 37.5wt.% dioxane is 600.The separation Y at 60 ℃, 95vol.% ethanol water being dewatered through 300 ° of C heat treatment film of 3 hours
(H2O/EtOH)=900, flux is 1.0kg/m
2.h.
Prepared by Y.Q.Dong take the hollow fiber composite membrane that polysulfones (PSF) hollow fiber ultrafiltration membrane is separating layer as supporting layer, polyvinyl alcohol (PVA) and sodium alginate (SA) blended layer, for osmotic, evaporating and dewatering.Result of the test demonstration blend film component ratio is 4: 1, and obtains high selectivity and good permeability through the 1.5wt.% maleic acid solution film of crosslinked 8 hours.Under 45 ° of C, blend film is respectively 1727,414g/m to the separation of the aqueous solution of four kinds of alcohol and permeation flux
2h, 606,585g/m
2h, 725,370g/m
2h and 384,384g/m
2h.
The people such as A.Parthasarathy studied two kinds by selective polymerisation thing Film synthesis the method on microporous hollow fiber film surface.First method relates to interface oxidation reductive polymerization, at doughnut film outer surface, prepares electrolytic polymer (as polypyrrole, polyethylene (N methylpyrrole), polyaniline etc.) film; Second method is the styrene monomer interfacial polymerization on hollow-fibre membrane surface.
R.Liu etc. have prepared BTDA-TDI/MDI (P84)/polyethers (PES) double-layer hollow fiber that isopropyl alcohol (IPA) is had to good osmotic, evaporating and dewatering performance by coextrusion formation technology.At 200 ℃, this film is heat-treated and can be increased its separation but can reduce flux.Different from individual layer P84 doughnut, further improve heat treatment temperature and do not cause passive PES layer densified and strengthen its resistance, thereby the stalling characteristic of P84/PES double-layer hollow fiber is able to further reinforcement.Because P-benzene dimethylamine can only just can bring out cross-linking reaction at P84 skin, so duplicature is cross-linking modified very meaningful with P-benzene dimethylamine, in separating property and reduction material cost, realize " doulbe-sides' victory ".2 hours crosslinked optimized separations/selective of obtaining are found in research.
Y.Cohen etc. are for to facilitate the formation of polymer/ceramic composite hollow fibre to do a lot of work.On the top layer of doughnut ceramic support, be coated with hydrophilic selections layer of crosslinked poly-(ethene) alcohol of ultra-thin, high flux, high selectivity.This supporting layer is by γ-Al
2o
3layer and γ-Al
2o
3intermediate layer forms, for the coating of ultra-thin polyvinyl alcohol (PVA) layer provides smooth enough surface.At γ-Al
2o
3the PVA layer thickness that central exterior surface forms is about 0.3-0.8 micron, and has not observed obvious PVA to γ-Al
2o
3the infiltration in intermediate layer.In n-butyl alcohol (80 ℃, 5wt.% water) dehydration, this film shows very high water flux (0.8-2.6kg/m2.h) and higher separation factor (500-10000).This flux has surpassed the crosslinked corresponding parameter area of PVA film of individual layer with separated numerical value.In 2-propyl alcohol and n-butyl alcohol dehydration, can observe along with feeding liquid temperature or the wherein continuous rising of the content of water, water flux and separation increase simultaneously.The variation tendency of this trend and common viewed polymer membrane, i.e. the reduction of separation is followed in flux increase conventionally, forms sharp contrast.We can explain this phenomenon like this: due to γ-Al
2o
3the fixation of rigid structure to interface PVA, make it present the swelling compared with low degree.
Zeolite also can be used as liquefied mixture separation membrane material because of its molecular sieve effect.There are several patents to report the infiltrating and vaporizing membrane being formed by inorganic material completely.Wherein a class inoranic membrane is formed scribbling in advance the support layer surface deposition growing of crystal seed by A type molecular sieve.Seed particles is distributed at carrier surface by the spraying with decentralized medium (preferably water), also can be by being sneaked in raw material and be fixed when preparing porous support layer.A type molecular sieve selects layer to using sodium metasilicate, silicon gel or colloidal sol or Cab-O-sil (as silicon source) and sodium aluminium or aluminium hydroxide (as alumina source) etc. as raw material, by hydro-thermal method or vapor-phase process, forms.
The permeability of the main separation of concerns film of correlative study of prior art, the balance selectively and between the stability of film macrostructure.Yet in realizing the process of these requirements, prior art exists some problems.First, for making ultra-thin unsymmetric structure possess the separating property of expection, conventionally must take as the intensive treatment of high temperature thermal quenching and so on the film of synthesized; The improvement of selecting the chemical crosslinking of layer can reach mechanical stability and separation to polymer under temperate condition, but must take expendable film flux as cost.Secondly, the preparation section of some film (while particularly adopting inorganic supporting layer) is too complicated, causes production cost too high and impracticable.In addition, compare with business-like flat sheet membrane, the flux of hollow-fibre membrane is also lower, and this likely weakens its market competitiveness.Therefore, be necessary to design a kind of membrane structure and develop easy preparation method.
Summary of the invention
The object of this invention is to provide a kind of preparation method who is applicable to the alcohols dehydration doughnut asymmetric compound film separated with bio-fuel.
In order to achieve the above object, the present invention includes following steps:
A. prepare casting solution: by high molecular polymer or high molecular polymer/inorganic filler mixed-matrix material and composition thereof, copolymer, derivative mixes with solvent or non-solvent the casting solution being mixed with, the mass concentration of high molecular polymer in casting solution is 5～50%, wherein high molecular polymer is polyamide, polyimides, Merlon, polyethers, polyether sulfone, polysulfones, polyamidoimide, polyester, polyurethane, cellulose acetate, polyether-ketone, polyphenylene oxide, bromination polyimides, fluorine polyamide, rubber polymer, ethene polymers, solvent is water, alcohol, acetic acid, acetone, formamide, oxolane (THF), methyl ethyl ketone, ethyl acetate, acetonitrile, N, N dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), n-hexane, benzene, ether, diethylene glycol dimethyl ether (DGDE), carrene, carbon tetrachloride, trichloro-ethylene, 1-METHYLPYRROLIDONE (NMP), non-solvent is NaCl, LiCl, LiNO
3, LiClO
4, CaCl
2, CaBr
2, MgCl
2, ZnCl
2or be methyl alcohol, ethanol, 2-propyl alcohol, n-butyl alcohol, 1-amylalcohol, 1 octanol, cyclohexanol, glycerine, Isosorbide-5-Nitrae butanediol, ethylene glycol and composition thereof,
B. the preparation of double-layer hollow fiber film: outer ring passage and intermediate annular passage by triple channel spinning head are carried respectively the first casting solution and the second casting solution, central tube by triple channel spinning head is carried core liquid, the first casting solution is identical with the second casting solution or different, the flow-rate ratio of the first casting solution and the second casting solution is 0.1～2, spinning head temperature is 25～90 ℃, then make nascent state hollow-fibre membrane pass through coagulation bath, wherein coagulation bath is water, alcohol, acetic acid, acetone, formamide, oxolane (THF), methyl ethyl ketone, ethyl acetate, acetonitrile, N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), n-hexane, benzene, ether, diethylene glycol dimethyl ether (DGDE), carrene, carbon tetrachloride, trichloro-ethylene, 1-METHYLPYRROLIDONE (NMP), NaCl, LiCl, LiNO
3, LiClO
4, CaCl
2, CaBr
2, MgCl
2, ZnCl
2or be methyl alcohol, ethanol, 2-propyl alcohol, n-butyl alcohol, 1-amylalcohol, 1-octanol, cyclohexanol, glycerine, BDO, ethylene glycol and composition thereof, coagulation bath temperature is-20～60 ℃.
Preferably, the mass concentration of described high molecular polymer in casting solution is 10-35wt%.
Preferably, the flow-rate ratio of described the first casting solution and the second casting solution is 0.1～2.
Preferably, described spinning head temperature is 25～60 ℃.
Preferably, described coagulation bath temperature is 0～60 ℃.
As a further improvement on the present invention, after by coagulation bath, also heat-treat, heat treatment temperature is 40～300 ° of C.
Adopt preparation method of the present invention, can overcome the defect of prior art, and only need simple operation just can make the doughnut asymmetric compound film of preparation there is enough heat endurances and mechanical stability, the film that the composite membrane of producing thus produces compared with prior art processes has higher flux, and total flux reaches 6000g/m
2.hr, water/tert-butyl alcohol separation (selectively) scope reaches 1000 to 3000.In addition this preparation method also has wider material range of choice, and requires lower to the formation of film and treatment conditions.
The specific embodiment
This example is intended to illustrate process of the present invention.The flux of the infiltration product by hollow-fibre membrane is with g/m
2.hr unit calculates.
Comparative example 1-3
Draw materials the individual layer hollow-fibre membrane of Matrimid 5218 by individual layer spining technology manufacture success.Wherein additive and spinning condition are listed in table 1.
By the casting film making shown in table 1, by conventional monolayers spinning head, extrude, consequent nascent state hollow-fibre membrane enters coagulation bath or immediately first by entering coagulation bath behind special air gap.The curing tunica fibrosa of institute's phase transformation is concentrated and is placed in clean running water foam washing after mobile phone at least three days, and then successively uses methyl alcohol and hexane to process, to remove moisture residual in film.
Table 1 individual layer Matrimid hollow fiber spinning parameter:
According to the described program of the 4th joint, the flux in osmotic, evaporating and dewatering and the separation of above-mentioned hollow-fibre membrane are tested.Charging is the 85wt.%t-butanols aqueous solution, and probe temperature is 80 ℃.Test result is summarised in table 2.
The routine 1-3 individual layer of table 2 Matrimid doughnut infiltration evaporation performance:
[0040] comparative example 3-5
Utilized double-deck spining technology to produce with ectonexine and all take the double-layer hollow fiber film that Udel polysulfones is membrane material, the constituent of its skin, internal layer and core liquor is as follows:
Table 3 adopts each layer of material liquid component of polysulfone hollow fibre of double-deck spining technology
This hollow-fibre membrane is prepared by listed spinning condition in table 4, and test is carried out according to method described in comparative example 1-3 completely.Its infiltration evaporation performance is in Table 5.
The double-deck polysulfone hollow fibre spinning condition of table 4
Flux and the separation of the routine 4-6 ps hollow fiber uf membrane of table 5
[0041] comparative example 7-9
Composition (table 6) based on following casting solution and core liquid and spinning condition (table 7) also adopt double-layer coextrusion technology, and preparation makes with polysulfones the hollow-fibre membrane that cladding material and Matrimid make inner layer material:
The casting solution of table 6 polysulfones/Matrimid double-layer hollow fiber film and core liquid form:
The spinning condition of table 7 polysulfones/Matrimid double-layer hollow fiber film:
Under 80 ℃ of temperature conditions of PSF/Matrimid double-layer hollow fiber film, the 85wt.%t-butanols aqueous solution is carried out to the performance of osmotic, evaporating and dewatering as shown in table 8.
Flux and the separation of table 8PSF/Matrimid double-layer hollow fiber film:
Claims (6)
1. a preparation method for doughnut asymmetric compound film, is characterized in that, comprises the following steps:
A. prepare casting solution: by high molecular polymer or high molecular polymer/inorganic filler mixed-matrix material and composition thereof, copolymer, derivative mixes with solvent or non-solvent the casting solution being mixed with, the mass concentration of high molecular polymer in casting solution is 5～50%, wherein high molecular polymer is polyamide, polyimides, Merlon, polyethers, polyether sulfone, polysulfones, polyamidoimide, polyester, polyurethane, cellulose acetate, polyether-ketone, polyphenylene oxide, bromination polyimides, fluorine polyamide, rubber polymer, ethene polymers, solvent is water, alcohol, acetic acid, acetone, formamide, oxolane (THF), methyl ethyl ketone, ethyl acetate, acetonitrile, N, N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), n-hexane, benzene, ether, diethylene glycol dimethyl ether (DGDE), carrene, carbon tetrachloride, trichloro-ethylene, N-methyl pyrrolidone (NMP), non-solvent is NaCl, LiCl, LiNO
3, LiClO
4, CaCl
2, CaBr
2, MgCl
2, ZnCl
2or be methyl alcohol, ethanol, 2-propyl alcohol, n-butyl alcohol, 1-amylalcohol, 1-octanol, cyclohexanol, glycerine, BDO, ethylene glycol and composition thereof,
B. the preparation of double-layer hollow fiber film: outer ring passage and intermediate annular passage by triple channel spinning head are carried respectively the first casting solution and the second casting solution, central tube by triple channel spinning head is carried core liquid, the first casting solution is identical with the second casting solution or different, the flow-rate ratio of the first casting solution and the second casting solution is 0.1～2, spinning head temperature is 25～90 ℃, then make nascent state hollow-fibre membrane pass through coagulation bath, wherein coagulation bath is water, alcohol, acetic acid, acetone, formamide, oxolane (THF), methyl ethyl ketone, ethyl acetate, acetonitrile, N, N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), n-hexane, benzene, ether, diethylene glycol dimethyl ether (DGDE), carrene, carbon tetrachloride, trichloro-ethylene, N-methyl pyrrolidone (NMP), NaCl, LiCl, LiNO
3, LiClO
4, CaCl
2, CaBr
2, MgCl
2, ZnCl
2or be methyl alcohol, ethanol, 2-propyl alcohol, n-butyl alcohol, 1-amylalcohol, 1-octanol, cyclohexanol, glycerine, BDO, ethylene glycol and composition thereof, coagulation bath temperature is-20～60 ℃.
2. according to the preparation method of a kind of doughnut asymmetric compound film of claim 1, it is characterized in that, the mass concentration of described high molecular polymer in casting solution is 10-35 wt%.
3. according to the preparation method of a kind of doughnut asymmetric compound film of claim 1, it is characterized in that, the flow-rate ratio of described the first casting solution and the second casting solution is 0.1～2.
4. according to the preparation method of a kind of doughnut asymmetric compound film of claim 1, it is characterized in that, described spinning head temperature is 25～60 ℃.
5. according to the preparation method of a kind of doughnut asymmetric compound film of claim 1, it is characterized in that, described coagulation bath temperature is 0～60 ℃.
6. according to the preparation method of a kind of doughnut asymmetric compound film of claim 1, it is characterized in that, after by coagulation bath, also heat-treat, heat treatment temperature is 40～300
oc.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807247A (en) * | 2016-12-26 | 2017-06-09 | 中南大学 | A kind of polyamidoimide or/sulfonated polyether-ether-ketone and polyamidoimide NF membrane and its preparation technology |
| CN109679055A (en) * | 2018-12-12 | 2019-04-26 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of degradable microencapsulation material and the preparation method and application thereof that uvioresistant is modified |
| CN110732246A (en) * | 2019-09-10 | 2020-01-31 | 梧州中科鼎新工业技术研究院(有限合伙) | acid-resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN112535956A (en) * | 2020-11-17 | 2021-03-23 | 上海翊科聚合物科技有限公司 | Super-hydrophobic polyolefin hollow fiber membrane for oxygen-containing membrane and preparation method thereof |
| CN113244790A (en) * | 2021-04-27 | 2021-08-13 | 陕西禹慧智通环保科技有限公司 | Self-reinforced hollow fiber ultrafiltration membrane and preparation method and application thereof |
| CN113398774A (en) * | 2021-06-16 | 2021-09-17 | 四川凯歌微纳科技有限公司 | Hollow fiber ceramic membrane and preparation method thereof |
| CN114733373A (en) * | 2022-04-18 | 2022-07-12 | 江苏艾乐膜科技有限公司 | Preparation method for preparing composite hollow fiber ultrafiltration membrane by NIPS method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451465A (en) * | 2002-04-12 | 2003-10-29 | 四川大学 | Method for making composite membrane for separation of polymer fluid |
| US6663805B1 (en) * | 2002-09-20 | 2003-12-16 | L'air Liquide Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process for making hollow fiber mixed matrix membranes |
| CN101036861A (en) * | 2006-12-29 | 2007-09-19 | 浙江大学 | Hydrophilicity polyethylene hollow fiber micro-hole film and the preparation method |
| CN102228803A (en) * | 2011-04-19 | 2011-11-02 | 蒋兰英 | Method for preparing hollow fiber composite membrane |
-
2012
- 2012-09-18 CN CN201210346742.0A patent/CN103657437A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451465A (en) * | 2002-04-12 | 2003-10-29 | 四川大学 | Method for making composite membrane for separation of polymer fluid |
| US6663805B1 (en) * | 2002-09-20 | 2003-12-16 | L'air Liquide Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process for making hollow fiber mixed matrix membranes |
| CN101036861A (en) * | 2006-12-29 | 2007-09-19 | 浙江大学 | Hydrophilicity polyethylene hollow fiber micro-hole film and the preparation method |
| CN102228803A (en) * | 2011-04-19 | 2011-11-02 | 蒋兰英 | Method for preparing hollow fiber composite membrane |
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| CN106807247A (en) * | 2016-12-26 | 2017-06-09 | 中南大学 | A kind of polyamidoimide or/sulfonated polyether-ether-ketone and polyamidoimide NF membrane and its preparation technology |
| CN109679055A (en) * | 2018-12-12 | 2019-04-26 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of degradable microencapsulation material and the preparation method and application thereof that uvioresistant is modified |
| CN109679055B (en) * | 2018-12-12 | 2020-12-08 | 中国农业科学院农业质量标准与检测技术研究所 | Anti-ultraviolet modified degradable microcapsule material and preparation method and application thereof |
| CN110732246A (en) * | 2019-09-10 | 2020-01-31 | 梧州中科鼎新工业技术研究院(有限合伙) | acid-resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN112535956A (en) * | 2020-11-17 | 2021-03-23 | 上海翊科聚合物科技有限公司 | Super-hydrophobic polyolefin hollow fiber membrane for oxygen-containing membrane and preparation method thereof |
| CN112535956B (en) * | 2020-11-17 | 2022-09-23 | 上海翊科聚合物科技有限公司 | Super-hydrophobic polyolefin hollow fiber membrane for oxygen-containing membrane and preparation method thereof |
| CN113244790A (en) * | 2021-04-27 | 2021-08-13 | 陕西禹慧智通环保科技有限公司 | Self-reinforced hollow fiber ultrafiltration membrane and preparation method and application thereof |
| CN113398774A (en) * | 2021-06-16 | 2021-09-17 | 四川凯歌微纳科技有限公司 | Hollow fiber ceramic membrane and preparation method thereof |
| CN114733373A (en) * | 2022-04-18 | 2022-07-12 | 江苏艾乐膜科技有限公司 | Preparation method for preparing composite hollow fiber ultrafiltration membrane by NIPS method |
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