CN104069744A - Reinforced hollow fiber membrane with hydrophilic cellular structure, as well as preparation method and production device of reinforced hollow fiber membrane - Google Patents
Reinforced hollow fiber membrane with hydrophilic cellular structure, as well as preparation method and production device of reinforced hollow fiber membrane Download PDFInfo
- Publication number
- CN104069744A CN104069744A CN201410347527.1A CN201410347527A CN104069744A CN 104069744 A CN104069744 A CN 104069744A CN 201410347527 A CN201410347527 A CN 201410347527A CN 104069744 A CN104069744 A CN 104069744A
- Authority
- CN
- China
- Prior art keywords
- preparation
- hollow
- hydrophily
- stay pipe
- hollow fiber
- 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.)
- Granted
Links
Abstract
The invention provides a reinforced hollow fiber membrane with a hydrophilic cellular structure. The reinforced hollow fiber membrane is provided with a support tube and an outer skin layer, wherein cavities are formed in the contact surface of the support tube and the outer skin layer; the inner surface is hydrophilic; the average inner diameter of the cavities is 1.0-3.0 mm; the average depth is 0.2-0.5 mm. The invention further provides a preparation method of the reinforced hollow fiber membrane and equipment for realizing the method. According to the invention, the hollow fiber membrane with inner hydrophilic large cavities is obtained; on one hand, the hydrophilic and hydrophobic condition of the outer layer of the membrane is not affected, so that membrane fiber can be free from blockage of hydrophilic contaminant due to excess hydrophilicity, on the other hand, dense cavities are distributed inside the membrane, the liquid consumption is reduced, the material layer thickness of the membrane is not reduced, and the appropriate strength of the membrane fiber is guaranteed.
Description
[technical field]
The present invention relates to hollow-fibre membrane and preparation method thereof, particularly a kind of enhancement type hollow fiber film through modification with hydrophily honeycomb, also relates to its preparation method and the production equipment of realizing described preparation method.
[background technology]
With industrial development, the generation of sewage and complexity also increase thereupon, MBR (membrane bioreactor) is approved by more people for replacing traditional handicraft to solve effluent problem, but in complicated Sewage Environment, only have the film silk that high strength, resistance tocrocking are strong could operation steady in a long-term.
For this reason, to bring higher intensity also to improve production cost high simultaneously for enhanced fiber film.People attempt by optimizing thicknesses of layers to reduce cost of material, but thin thicknesses of layers can add Risks, and thicker rete cost is higher and filterability is poorer.
On the other hand, resistance tocrocking and filter efficiency are also the major issues of film, research thinks that improving hydrophily can make water more easily see through rete, can promote resistance tocrocking and improve filter efficiency, therefore in prior art, adopt the means such as surface graft modifications, blending and modifying to improve film surface or overall hydrophily more, but cannot make modification to film inside.The problem that it exists is to pollute complicated today for water, has a large amount of hydrophilic pollutants in water, and film surface hydrophilic is crossed the quick pollution that can cause by force film, shortens the life-span of film.
[summary of the invention]
The object of the invention is to obtain the enhancement type hollow fiber film of a kind of film inner hydrophilic modification, to avoid the excessively hydrophilic hydrophilic enriching pollutants causing in film outside, there is good film inner hydrophilic simultaneously, have compared with filtration efficiency, there is on the other hand lower production cost.
Object of the present invention also comprises the preparation method who obtains above-mentioned hollow-fibre membrane, and realizes described preparation method's production equipment.
To achieve these goals, the invention provides a kind of enhancement type hollow fiber film with hydrophily honeycomb, described hollow-fibre membrane has stay pipe and exodermis, wherein, on the contact-making surface of described stay pipe and exodermis, there is uniform macroscopic cavitation, the inner surface of described macroscopic cavitation has hydrophily, and the mean inside diameter of described macroscopic cavitation is 1.0-3.0mm, and mean depth is 0.2-0.5mm.
In the present invention, the exodermis that has an enhancement type hollow fiber film of hydrophily honeycomb is selected from one or more in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone and/or polyacrylonitrile.
The present invention also provides a kind of wet preparation method of the enhancement type hollow fiber film with hydrophily honeycomb, comprise by after wire-feed motor output stay pipe, stay pipe is carried out to hydrophily pretreatment, then to applying preparation liquid through the pretreated stay pipe of hydrophily, then the stay pipe that has applied preparation liquid is sent into coagulation bath, after dry, receive the silk type hollow-fibre membrane that is enhanced, wherein, while carrying out hydrophily pretreatment, making stay pipe pass into one has in the hollow pipe of through hole, by injection apparatus from the hydrophilically modified liquid of described hollow pipe lateral hollow spray tube, described modified liquid is distributed on stay pipe by described through hole, form equally distributed modified liquid drop, described hydrophilically modified liquid is selected from the aqueous solution of the nano silicon aqueous solution, the nano titanium oxide aqueous solution or hydrophilic PVA.
In the present invention, preferably, described hollow pipe has equally distributed through hole, and described through hole average pore size is 0.8-3.0mm, and pitch of holes is 2.0-4.0mm.
According to a kind of preferred embodiment of above-mentioned preparation method, the average diameter of described modified liquid drop is 1.0-3.0mm.
In the present invention, preferably, in described hydrophilically modified liquid, also contain solvent, described solvent is selected from 1-METHYLPYRROLIDONE, N, one or more in N-dimethyl pyrrolidone, dimethyl formamide, dimethylacetylamide or triethyl phosphate.
More preferably, in 100 parts of gross weights, described hydrophilically modified liquid contains 1-2 part nano silicon or nano titanium oxide or hydrophilic PVA, 8-20 part pure water, and surplus is solvent.
In the present invention, described preparation liquid is selected from one or more in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone and/or polyacrylonitrile.
The purposes of the hollow-fibre membrane that the invention still further relates to above-mentioned hollow-fibre membrane or obtain according to above-mentioned preparation method in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment.
The present invention also provides a kind of production equipment of the enhancement type hollow fiber film with hydrophily honeycomb, comprise the wire feeder setting gradually, hydrophilically modified liquid injection apparatus, coating device, coagulation bath device and receive silk device, wherein, hydrophilically modified liquid injection apparatus comprises the hollow pipe therefrom passing through for stay pipe, on described hollow pipe, be distributed with through hole, be provided with vaporizing liquid injection apparatus in described hollow pipe outside, described vaporizing liquid injection apparatus has connected fluid reservoir.
Below will describe in more detail technical scheme of the present invention.
A kind of enhancement type hollow fiber film with hydrophily honeycomb, described hollow-fibre membrane has stay pipe and exodermis, on the contact-making surface of described stay pipe and exodermis, there is uniform macroscopic cavitation, the inner surface of described macroscopic cavitation has hydrophily, the mean inside diameter of described macroscopic cavitation is 1.0-3.0mm, and mean depth is 0.2-0.5mm.
Described hollow-fibre membrane is prepared by wet method, step comprises by after wire-feed motor output stay pipe, stay pipe is carried out to hydrophily pretreatment, then to applying preparation liquid through the pretreated stay pipe of hydrophily, then the stay pipe that has applied preparation liquid is sent into coagulation bath, after dry, receive the silk type hollow-fibre membrane that is enhanced, wherein, while carrying out hydrophily pretreatment, making stay pipe pass into one has in the hollow pipe of through hole, by injection apparatus from the hydrophilically modified liquid of described hollow pipe lateral hollow spray tube, described modified liquid is distributed on stay pipe by described through hole, described hydrophilically modified liquid is selected from the aqueous solution of the nano silicon aqueous solution, the nano titanium oxide aqueous solution or hydrophilic PVA microgel.
According to one preferred embodiment, described hollow pipe has equally distributed through hole, and described through hole average pore size is 0.8-3.0mm, and pitch of holes is 2.0-4.0mm, and the average diameter of described modified liquid drop is 1.0-3.0mm.
In the present invention, " uniformly macroscopic cavitation " to should be understood to macroscopic cavitation be totally equally distributed on the contact-making surface of stay pipe and exodermis.Because the formation mechanism in hole is by spray hydrophilically modified liquid on stay pipe, hydrophilically modified liquid forms equally distributed drop on stay pipe, therefore applying after preparation liquid, hydrophilically modified drop first contacts with preparation liquid, form hole in contact-making surface phase-splitting, send into subsequently after coagulation bath, coagulation bath contacts with preparation liquid again.
Therefore, for macroscopic cavitation or hydrophilically modified liquid drop, they should be all relatively equally distributed, have the average grain diameter of particular range, but can not make excessive demands under microscopic state each hole or each drop has identical diameter.
A preferred embodiment of the invention, in 100 parts of gross weights, described hydrophilically modified liquid contains 1-2 part nano silicon or nano titanium oxide or hydrophilic PVA, 8-20 part pure water, and surplus is solvent.
Nano silicon should be understood to the nanoscale product of silica, the LF33 type hydrophilic nano silica that for example Xiushan Mountain Long Fei new material Co., Ltd sells.
Nano titanium oxide should be understood to the nanoscale product of titanium dioxide, the nanometer titanium dioxide titanium products that Henan Huarong Environmental Protection Technology Co., Ltd produces.
In the present invention, described preparation liquid is selected from one or more in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone and/or polyacrylonitrile.In fact the preparation liquid material that, prepared by other wet methods that are applicable to hollow-fibre membrane is also applicable to the present invention.Mixing between preparation liquid not of the same race belongs to prior art, and those skilled in the art can repeat to implement, and does not repeat at this.
Similarly, the component of coagulation bath and consumption also belong to the knowledge that those skilled in the art have grasped, and for example water, DMAC or their mixture are all conventional coagulation baths.
In the present invention, described stay pipe is selected from PA nylon fiber rope, PAN cyclization rope or PET dacron fibre rope.
The invention still further relates to hollow-fibre membrane that above-mentioned hollow-fibre membrane or above-mentioned preparation method the obtain purposes in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment.
The present invention also provides a kind of production equipment of the enhancement type hollow fiber film with hydrophily honeycomb, comprise the wire feeder setting gradually, hydrophilically modified liquid injection apparatus, coating device, coagulation bath device and receive silk device, wherein, hydrophilically modified liquid injection apparatus comprises the hollow pipe therefrom passing through for stay pipe, on described hollow pipe, be distributed with through hole, be provided with vaporizing liquid injection apparatus in described hollow pipe outside, described vaporizing liquid injection apparatus has connected fluid reservoir.
For injection apparatus, the internal diameter of hollow pipe should be slightly larger than the external diameter of stay pipe, for example stay pipe external diameter 2.0mm, and hollow pipe internal diameter is 2.2mm.In length, in order to ensure drop that can the hydrophilically modified liquid of reasonable layout on stay pipe, the shower nozzle of injection apparatus should not be too far away apart from hollow pipe distance, for example 1-10cm.Those skilled in the art can be according to wet spinning speed, adjusts the emitted dose of injection apparatus, guarantee to spray on rear supporting tube, to be uniformly distributed modified liquid liquid, and drop is inexcessive, it is overlapping can not cause.Generally speaking, different different with spinning speed according to projected area, emitted dose 0.1 milliliters/second-10 milliliters/second all can realize technical scheme of the present invention.
Preferably, by programme-control, discontinuity is sprayed water seeking liquid to stay pipe, and ensureing has and only have one deck water seeking liquid on every section of stay pipe, and the proportional relation of jet velocity and wire feed rate, is inverse relation with injection interval.
In the present invention, wire feeder, coating device, coagulation bath device and the receipts silk device of hollow-fibre membrane process units can adopt conventional wet-spinning frame, this equipment is the product that can buy acquisition on market, for example the spinning-drawing machine of Jiangsu Jing Kai Environmental Protection Technology Co., Ltd production and sales.
In the present invention, make stay pipe by thering is the hollow pipe of through hole, vaporizing liquid injection apparatus sprays hydrophilically modified liquid from hollow pipe outside at interval of a period of time, the drop of hydrophilically modified liquid that made stay pipe surface distributed, drop density and drop area can be controlled by adjusting injection apparatus and the distance of hollow pipe and the injecting time interval of injection apparatus.
Spray after hydrophilically modified liquid to stay pipe, by conventional film forming apparatus, stay pipe is applied to preparation liquid, then enter in coagulation bath.
Preparation liquid first contacts with the hydrophilically modified liquid on stay pipe, steam in modified liquid makes the contact-making surface (being the inner surface of preparation liquid) of preparation liquid and stay pipe first start to occur phase-splitting, enter after coagulation bath, the outer surface of preparation liquid starts to occur phase-splitting, thereby solidifies.After conventional drying, between preparation liquid inner side and stay pipe, form hole, it is densely covered poroid that hole is.
Because modified liquid has hydrophily, when preparation liquid runs into modified liquid drop, have hydrophilic substance in a small amount of modified liquid drop and enter into the interior surface layers in hole in the time of gel, therefore the inner surface in hole also possesses hydrophily.
The present invention has carried out the mensuration of macroscopic cavitation average pore size, intensity and pure water flux to prepared hollow-fibre membrane.
After the macroscopic cavitation diameter of described hollow-fibre membrane adopts ESEM Multiple-Scan, calculating mean value characterizes.
Described doughnut film strength refers to the fracture strength of single film, is by electronic universal material testing machine, measures to break that the required power of single film (N of unit) obtains.
The pure water flux of described hollow-fibre membrane is tested under 0.1MPa pressure with flux analyzer.
Compared to existing technology, the skin of hollow-fibre membrane is carried out to modification, or film silk entirety hydrophilic modifying, method of the present invention has obtained the inner hollow-fibre membrane that is hydrophilic macroscopic cavitation, on the one hand can not affect the outer field close and distant water state of film, that guarantees film silk can be due to the too hydrophilic obstruction that is subject to hydrophily pollutant.
On the other hand, because film inside has densely covered hole, be therefore minimized feed liquid consumption, and can not reduce the thickness of feed layer of film, therefore there will not be the defect of cover light.And film silk water flux can also effectively be improved in the macroscopic cavitation of film inside.
[brief description of the drawings]
Fig. 1-1 is the sample photo of the hollow-fibre membrane of embodiment 1;
Fig. 1-2 is the sample photo of the hollow-fibre membrane of embodiment 3;
Fig. 1-3 are the sample photo of the hollow-fibre membrane of embodiment 5;
Fig. 2 is the structural representation of enhancement type hollow fiber film of the present invention;
Fig. 3 is the structural representation of production method of the present invention;
Wherein, 1, wire-feed motor; 2, stay pipe wheel; 3, stay pipe; 4, hydrophilically modified liquid injection apparatus; 4-1, vaporizing liquid injection apparatus; 4-2, hollow pipe; 5, fluid reservoir; 6, preparation liquid material liquid tank; 7, coating unit; 8, gel bath; 9, receive silk machine; 10, wire drawing wheel.
[detailed description of the invention]
Following examples are for explaining without limitation method of the present invention.Protection scope of the present invention should be determined by claims.
In the present invention, if no special instructions, " part " is all interpreted as weight portion, and the ratio of each component is all interpreted as weight ratio.
Embodiment 1
As shown in Figure 2,3, adopt conventional hollow-fibre membrane wet-spinning frame, hydrophilically modified liquid injection apparatus is set between wire-feed motor and coating unit, comprises the hollow pipe that can pass through for stay pipe, the vaporizing liquid injection apparatus that is arranged on hollow pipe outside, the fluid reservoir being connected with injection apparatus.
Hollow pipe range 10cm, pitch of holes 4mm, aperture 1mm, makes PA nylon fiber rope stay pipe pass through hollow pipe with 5 ms/min of speed, and injection apparatus injection interval is 1.2 seconds.
Hydrophilically modified liquid is the nano silicon of 1:9:90: pure water: 1-METHYLPYRROLIDONE.
Preparation liquid is PVDF/PVP/DMAC=15:5:80
Coagulation bath is DMAC/ water=50:50
Under magnifying glass as Figure 1-1, wherein, the dark position on every hollow-fibre membrane is the macroscopic cavitation that is positioned at film silk inside to gained hollow-fibre membrane product, can observe different from other site color under ordinary ray.
Embodiment 2 (comparative example)
Carry out identical with embodiment 1, difference is that stay pipe does not carry out hydrophily pretreatment, directly applies preparation liquid from wire-feed motor output.
Embodiment 3
Carry out identical with embodiment 1, difference is pitch of holes 3mm, aperture 2mm, the nano titanium oxide that hydrophilically modified liquid is 1:14:85: pure water: 1-METHYLPYRROLIDONE.
Under magnifying glass as shown in Figure 1-2, wherein, dark position is the macroscopic cavitation that is positioned at film silk inside to gained hollow-fibre membrane product.
Embodiment 4 (comparative example 2)
Carry out identical with embodiment 3, difference is that stay pipe does not carry out hydrophily pretreatment, directly applies preparation liquid from wire-feed motor output.
Embodiment 5
Carry out identical with embodiment 1, difference is pitch of holes 2mm, aperture 0.8mm, the nano silicon that hydrophilically modified liquid is 1:8:91: pure water: N, N-dimethyl pyrrolidone.
Under magnifying glass as shown in Figure 1-2, wherein, dark position is the macroscopic cavitation that is positioned at film silk inside to gained hollow-fibre membrane product.
Embodiment 6
Carry out identical with embodiment 1, difference is pitch of holes 4mm, aperture 1.8mm, the nano titanium oxide that hydrophilically modified liquid is 2:20:78: pure water: dimethyl formamide.
Embodiment 7
Carry out identical with embodiment 1, difference is pitch of holes 2mm, aperture 3mm, the nano titanium oxide that hydrophilically modified liquid is 2:8:90: pure water: triethyl phosphate.
Product to above-described embodiment is measured, and result is as follows
Therefore, can find out the honeycomb enhancement type hollow fiber film of making through interior hydrophilic modifying, its honeycomb can't reduce film silk intensity, but the internal structure with macroscopic cavitation can significantly improve film silk flux, effectively alleviate deadweight, and be conducive to reduce the feed liquid cost of film silk simultaneously.
Claims (10)
1. one kind has the enhancement type hollow fiber film of hydrophily honeycomb, described hollow-fibre membrane has stay pipe and exodermis, it is characterized in that thering is uniform macroscopic cavitation on the contact-making surface of described stay pipe and exodermis, the inner surface of described macroscopic cavitation has hydrophily, the mean inside diameter of described macroscopic cavitation is 1.0-3.0mm, and mean depth is 0.2-0.5mm.
2. the enhancement type hollow fiber film with hydrophily honeycomb according to claim 1, is characterized in that described exodermis is selected from one or more in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone and/or polyacrylonitrile.
3. one kind has the wet preparation method of the enhancement type hollow fiber film of hydrophily honeycomb, comprise by after wire-feed motor output stay pipe, stay pipe is carried out to hydrophily pretreatment, then to applying preparation liquid through the pretreated stay pipe of hydrophily, then the stay pipe that has applied preparation liquid is sent into coagulation bath, after dry, receive the silk type hollow-fibre membrane that is enhanced, while it is characterized in that carrying out hydrophily pretreatment, making stay pipe pass into one has in the hollow pipe of through hole, by injection apparatus from the hydrophilically modified liquid of described hollow pipe lateral hollow spray tube, described modified liquid is distributed on stay pipe by described through hole, form equally distributed modified liquid drop, described hydrophilically modified liquid is selected from the aqueous solution of the nano silicon aqueous solution, the nano titanium oxide aqueous solution or hydrophilic PVA microgel.
4. preparation method according to claim 3, is characterized in that described hollow pipe has equally distributed through hole, and described through hole average pore size is 0.8-3.0mm, and pitch of holes is 2.0-4.0mm.
5. preparation method according to claim 2, the average diameter that it is characterized in that described modified liquid drop is 1.0-3.0mm.
6. preparation method according to claim 2, it is characterized in that also containing solvent in described hydrophilically modified liquid, described solvent is selected from 1-METHYLPYRROLIDONE, N, one or more in N-dimethyl pyrrolidone, dimethyl formamide, dimethylacetylamide or triethyl phosphate.
7. preparation method according to claim 6, is characterized in that in 100 parts of gross weights, and described hydrophilically modified liquid contains 1-2 part nano silicon or nano titanium oxide or hydrophilic PVA, 8-20 part pure water, and surplus is solvent.
8. preparation method according to claim 3, is characterized in that described preparation liquid is selected from one or more in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone and/or polyacrylonitrile.
9. the hollow-fibre membrane of claim 1 or 2 or the hollow-fibre membrane that obtains according to the preparation method described in any one claim in the claim 2-8 purposes in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment.
10. one kind has the production equipment of the enhancement type hollow fiber film of hydrophily honeycomb, comprise the wire feeder setting gradually, hydrophilically modified liquid injection apparatus, coating device, coagulation bath device and receive silk device, it is characterized in that hydrophilically modified liquid injection apparatus comprises the hollow pipe therefrom passing through for stay pipe, on described hollow pipe, be distributed with through hole, be provided with vaporizing liquid injection apparatus in described hollow pipe outside, described vaporizing liquid injection apparatus has connected fluid reservoir.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410347527.1A CN104069744B (en) | 2014-07-21 | 2014-07-21 | There is the enhancement type hollow fiber film of hydrophily honeycomb, its preparation method and process units |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410347527.1A CN104069744B (en) | 2014-07-21 | 2014-07-21 | There is the enhancement type hollow fiber film of hydrophily honeycomb, its preparation method and process units |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104069744A true CN104069744A (en) | 2014-10-01 |
| CN104069744B CN104069744B (en) | 2016-01-27 |
Family
ID=51591588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410347527.1A Expired - Fee Related CN104069744B (en) | 2014-07-21 | 2014-07-21 | There is the enhancement type hollow fiber film of hydrophily honeycomb, its preparation method and process units |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104069744B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846369A (en) * | 2015-03-30 | 2015-08-19 | 陕西科技大学 | Method for preparing super-hydrophilic and hydrophobic composite nano array interface material |
| CN108430936A (en) * | 2015-09-30 | 2018-08-21 | 株式会社拜特奇 | Wastewater treatment carrier, wastewater treatment carrier module, wastewater treatment carrier element and wastewater treatment equipment |
| CN115253710A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Hollow fiber membrane and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745324A (en) * | 2009-12-10 | 2010-06-23 | 杭州洁弗膜技术有限公司 | Preparation method of dry high-hydrophilic polyvinylidene fluoride hollow fibrous membrane |
| US20100163488A1 (en) * | 2007-04-23 | 2010-07-01 | Rainer Fislage | Hollow fiber capillary membrane and method for the production thereof |
| CN201519554U (en) * | 2009-11-11 | 2010-07-07 | 景德镇陶瓷学院 | Honeycomb hydrophilic ceramic filter membrane |
| CN103071398A (en) * | 2013-02-22 | 2013-05-01 | 厦门大学 | Porous polymer membrane with perforated structure and preparation method and application thereof |
-
2014
- 2014-07-21 CN CN201410347527.1A patent/CN104069744B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100163488A1 (en) * | 2007-04-23 | 2010-07-01 | Rainer Fislage | Hollow fiber capillary membrane and method for the production thereof |
| CN201519554U (en) * | 2009-11-11 | 2010-07-07 | 景德镇陶瓷学院 | Honeycomb hydrophilic ceramic filter membrane |
| CN101745324A (en) * | 2009-12-10 | 2010-06-23 | 杭州洁弗膜技术有限公司 | Preparation method of dry high-hydrophilic polyvinylidene fluoride hollow fibrous membrane |
| CN103071398A (en) * | 2013-02-22 | 2013-05-01 | 厦门大学 | Porous polymer membrane with perforated structure and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846369A (en) * | 2015-03-30 | 2015-08-19 | 陕西科技大学 | Method for preparing super-hydrophilic and hydrophobic composite nano array interface material |
| CN104846369B (en) * | 2015-03-30 | 2017-08-25 | 陕西科技大学 | A kind of method for preparing super hydrophobe composite Nano array interface material |
| CN108430936A (en) * | 2015-09-30 | 2018-08-21 | 株式会社拜特奇 | Wastewater treatment carrier, wastewater treatment carrier module, wastewater treatment carrier element and wastewater treatment equipment |
| CN115253710A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Hollow fiber membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104069744B (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tijing et al. | Recent progress of membrane distillation using electrospun nanofibrous membrane | |
| CN102600734A (en) | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof | |
| CN101837248B (en) | Production method of cellosilk enhanced compound hollow fiber membrane | |
| CN102836644B (en) | Method for synchronously preparing hollow fiber compound nanofiltration membrane through immersion precipitation phase inversion/interface crosslinking | |
| CN104117289B (en) | One kind enhancing composite support hollow-fibre membrane and preparation method thereof | |
| CN110124517B (en) | Method for preparing nanofiber-based composite nanofiltration membrane by low-temperature reverse interfacial polymerization | |
| CN107913603B (en) | Braided tube reinforced hollow fiber membrane, and preparation device and production process thereof | |
| US20100108599A1 (en) | Filtration membrane with tubular support | |
| CN104069744B (en) | There is the enhancement type hollow fiber film of hydrophily honeycomb, its preparation method and process units | |
| CN108273392A (en) | The method of modifying of hollow woven tube and the preparation method of hollow-fibre membrane | |
| SE0203857L (en) | Perm-selective membrane and process for its manufacture | |
| CN104437138A (en) | Polysulfonate separation membrane and preparation method thereof | |
| CN102512990B (en) | Method for preparing internal support polyvinylidene fluoride hollow fiber membrane | |
| CN107789986A (en) | Enhanced hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN106731897A (en) | A kind of pollution-resistant polyvinylidene fluoride hollow fiber ultrafiltration membrane high, preparation method and device | |
| CN108355499A (en) | Double separating layer hollow fiber ultrafiltration membranes of the net containing tubular support and preparation method thereof | |
| CN206500037U (en) | A kind of preparation facilities of high pollution-resistant polyvinylidene fluoride hollow fiber ultrafiltration membrane | |
| CN103432915A (en) | Method for preparing polyvinylidene-fluoride bilayer hollow fiber membrane | |
| CN110327787A (en) | A kind of enhancement type hollow fiber film, preparation method and device | |
| CN105771678A (en) | Enhanced composite hydrophobic membrane and preparation method thereof | |
| CN106139912A (en) | A kind of preparation method of inner support reinforced type polyvinylidene fluoride hollow fiber film | |
| CN109847595A (en) | A kind of preparation method of the big compound polyvinylidene fluoride hollow fiber ultrafiltration membrane of flux inner support | |
| CN109453673A (en) | A kind of preparation method of inner support polyethersulfone hollow fiber ultrafiltration membrane | |
| CN113996189A (en) | Preparation method of hollow fiber separation membrane with compact selective layer | |
| CN106310968B (en) | A kind of big flux symmetrical structure polymer hollow fiber 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 | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 650101 Yunnan city of Kunming province M1-4 high tech Development Zone, Road No. 1088 and block Haiyuan international A building 6 floor Patentee after: Yunnan Yunshui Construction Engineering Co.,Ltd. Address before: 650106 Yunnan Province, Kunming City Haiyuan Road No. 1088 and international A 15 Floor Patentee before: YUNNAN ORIGIN WATER TECHNOLOGY CO. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160127 Termination date: 20210721 |