CN101185848B - Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof - Google Patents
Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof Download PDFInfo
- Publication number
- CN101185848B CN101185848B CN2007101317682A CN200710131768A CN101185848B CN 101185848 B CN101185848 B CN 101185848B CN 2007101317682 A CN2007101317682 A CN 2007101317682A CN 200710131768 A CN200710131768 A CN 200710131768A CN 101185848 B CN101185848 B CN 101185848B
- Authority
- CN
- China
- Prior art keywords
- hollow
- fibre membrane
- pore structure
- preparation
- exodermis
- 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.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a production method of a hollow fiber membrane, in particular to a hollow fiber membrane in an asymmetric network pore structure and the preparation method thereof. According to the technical proposal of the invention, the hollow fiber membrane of the asymmetric network pore structure comprises an endodermis, an exodermis and a support layer between the endodermis and the exodermis. The hollow fiber membrane is characterized in that: the hollow fiber membrane is the hollow fiber membrane of an inter compression type with the aperture of the exodermis being 0.5 to 20 times more than that of the endodermis; or the hollow fiber membrane is the hollow fiber membrane of an outside-in type with the aperture of the endodermis being 0.5 to 20 times more than that of the exodermis. The preparation method of the hollow fiber membrane in the asymmetric network pore structure employs a dry-wet spinning process. The hollow fiber membrane prepared by the method is characterized in the high working pressure bearing capacity, good membrane integrity, high membrane flux, high separation accuracy and so on.
Description
Technical field
The present invention relates to the production method of hollow-fibre membrane, the preparation method of the network-like pore structure hollow-fibre membrane of specifically a kind of asymmetry.
Background technology
Hollow-fibre membrane because have the packing density height, preparation cost is low, but advantages such as hydraulic reverse flushing obtain wide industrial and use.Existing preparation doughnut membrane technology is meant the shape pore structure, the asymmetry in its separating layer and another cortex aperture a little less than.The weakness of finger-like pore is that mechanical performance is relatively poor, is difficult to bear higher operating pressure.When impact load is big, the destruction of film appears easily, and separation accuracy is not very high, and membrane flux is also on the low side.
Adopt traditional doing-when the wet method conversion process prepares hollow-fibre membrane, usually the quantity of solvent that adds in spinning solution is bigger, the aqueous solution with hydrophily non-solvent and slaine is pore-foaming agent, and its consumption is less, and there is following defective in this method: 1, form finger-like pore in the inversion of phases process easily; 2, dense layer thickness is thicker; 3, when the bigger hollow-fibre membrane in preparation aperture, need low temperature, to keep its spinnability; 4, be difficult to accurately control inversion of phases process 5, film surface holes asymmetry a little less than.
Summary of the invention
The objective of the invention is to invent a kind of dissymmetric network shape pore structure hollow-fibre membrane and preparation method thereof, to have the operating pressure of bearing higher for Zhi Bei hollow-fibre membrane in this way, and film integrality is good, and membrane flux is big, characteristics such as separation accuracy height.
According to technical scheme provided by the invention, dissymmetric network shape pore structure hollow-fibre membrane comprises endodermis (being the inwall of hollow-fibre membrane) and exodermis (being the outer wall of hollow-fibre membrane) and is positioned at supporting layer between endodermis and exodermis, it is characterized in that: described hollow-fibre membrane is the inner pressed hollow-fibre membrane, and its exodermis aperture is bigger 0.5～20 times than endodermis aperture; Perhaps, described hollow-fibre membrane is the external-compression type hollow-fibre membrane, and its endodermis aperture is bigger 0.5～20 times than exodermis aperture.
Supporting layer between described endodermis and the exodermis is network-like pore structure, and the internal diameter of hollow-fibre membrane is 0.6～2.2mm, and the wall thickness of hollow-fibre membrane is 0.15～0.5mm.
The preparation method of described dissymmetric network shape layer pore structure hollow-fibre membrane adopts dried-wet spinning silk technology, it is characterized in that,
A, preparation spinning solution and core liquid: the high molecular polymer with 14～32%, 20～50% spin solvent, 20～70% hydrophily non-solvent, 0～25% additive adds dissolution kettle, stirs 8～24 hours down at 40～80 ℃, is configured to spinning solution; Core liquid consists of one or more the mixed liquor in water, spin solvent, non-solvent and the acid;
B, one-tenth silk: the interior pipe at spinning head feeds core liquid, and the annular space in spinning head between pipe and the outer tube is extruded through the spinning solution after the deaeration; The distance of spinning head and coagulation bath interdigit is 0.5～45cm, and the spinning solution extrusion temperature is 25～80 ℃, and the core liquid temp is 25～80 ℃, 25～80 ℃ of coagulation bath temperature; Core liquid and coagulation bath temperature difference are not more than 15 ℃; Form the hollow-fibre membrane silk;
C, film forming: the hollow fibre filament of formation is behind the coagulating bath solidified forming, and wrapping wire forms hollow-fibre membrane after 40～150 ℃ hot water thermal are handled on wire wrapping wheel.
Described high molecular polymer comprises one or more in polyether sulfone, polysulfones, Kynoar, polyacrylonitrile, the polyvinyl chloride.Described spin solvent comprises N-N dimethyl pyrrolidone (NMP), N-N dimethylacetylamide (DMAC), N-N dimethyl formamide (DMF).Described hydrophily non-solvent comprises one or more in the following substances: the block copolymer that ethanol, ethylene glycol, diethylene glycol, triethylene glycol, TEG, polyethylene glycol, polyvinyl alcohol, organic acid, polyoxyethylene, polyoxyethylene and polyoxy third are rare.
Described additive comprises one or more in polyvinylpyrrolidone, silica, lithium chloride, sodium chloride, calcium chloride, the lithium nitrate.Described spinning coagulation bath consist of in water, spin solvent, the hydrophily non-solvent one or more.The composition of described core liquid comprises one or more mixed liquors in water, spin solvent, the hydrophily non-solvent.
The present invention accurately controls phase transfer speed according to the thermodynamic instability characteristic of forming the spinning solution system, and it shows as: 1, the formation of the network-like pore structure of control; 2, the asymmetry in control surface aperture; 3, add an amount of auxiliary agent, the control hollow-fibre membrane becomes the stability of silk.Reduce the formation of macropore (Macrovaid), thereby make film forming even; 4, can control the size in aperture by the consumption of control hydrophily non-solvent, when consumption was big more, the aperture was big more; 5,, can control the size in endodermis aperture by one or more the composition in water, solvent, non-solvent and the acid of control core liquid.The consumption of solvent and/or non-solvent increases, and the aperture increases; 6, the composition of the aqueous solution of the aqueous solution of water, the solvent by the control coagulating bath and/or solvent and non-solvent can be controlled the size in exodermis aperture, and solvent and/or non-solvent consumption increase, the aperture increase.
Description of drawings
Fig. 1 is an endodermis SEM photo.
Fig. 2 is an exodermis SEM photo.
Fig. 3 is a transition supporting layer SEM photo.
Fig. 4 is a supporting layer SEM photo.
The specific embodiment
Dissymmetric network shape pore structure hollow-fibre membrane comprise endodermis and exodermis and be positioned at endodermis and exodermis between supporting layer, described hollow-fibre membrane is the inner pressed hollow-fibre membrane, its exodermis aperture is bigger 0.5～20 times than endodermis aperture; Perhaps, described hollow-fibre membrane is the external-compression type hollow-fibre membrane, and its endodermis aperture is bigger 0.5～20 times than exodermis aperture.
Supporting layer between described endodermis and the exodermis is network-like pore structure, and the internal diameter of hollow-fibre membrane is 0.6～2.2mm, and the wall thickness of hollow-fibre membrane is 0.15～0.5mm.
The preparation method of described dissymmetric network shape pore structure hollow-fibre membrane adopts dried-wet spinning silk technology:
A, preparation spinning solution and core liquid: the high molecular polymer with 14～32%, 20～50% spin solvent, 20～70% hydrophily non-solvent, 0～25% additive adds dissolution kettle, stirs 8～24 hours down at 40～80 ℃, is configured to spinning solution; Core liquid consists of one or more the mixed liquor in water, spin solvent, non-solvent and the acid;
B, one-tenth silk: the interior pipe at spinning head feeds core liquid, and the annular space in spinning head between pipe and the outer tube is extruded through the spinning solution after the deaeration; The distance of spinning head and coagulation bath interdigit is 0.5～45cm, and the spinning solution extrusion temperature is 25～80 ℃, and the core liquid temp is 25～80 ℃, 25～80 ℃ of coagulation bath temperature; Core liquid and coagulation bath temperature difference are not more than 15 ℃; Form the hollow-fibre membrane silk;
C, film forming: the hollow fibre filament of formation is behind the coagulating bath solidified forming, and wrapping wire forms hollow-fibre membrane after 40～150 ℃ hot water thermal are handled on wire wrapping wheel.
Described high molecular polymer comprises one or more in polyether sulfone, polysulfones, Kynoar, polyacrylonitrile, the polyvinyl chloride.Described spin solvent comprises N-N dimethyl pyrrolidone (NMP), N-N dimethylacetylamide (DMAC), N-N dimethyl formamide (DMF).
Described hydrophily non-solvent comprises one or more in the following substances: the block copolymer that ethanol, ethylene glycol, diethylene glycol, triethylene glycol, TEG, polyethylene glycol, polyvinyl alcohol, organic acid, polyoxyethylene, polyoxyethylene and polyoxy third are rare.Described additive comprises one or more in polyvinylpyrrolidone, silica, lithium chloride, sodium chloride, calcium chloride, the lithium nitrate.Described spinning coagulation bath consist of in water, spin solvent, the hydrophily non-solvent one or more.The composition of described core liquid comprises one or more mixed liquors in water, spin solvent, the hydrophily non-solvent.
High molecular polymer content is 14～30% in the spinning solution of the present invention, increases the consumption of high molecular polymer, can reduce the size in aperture; The content of solvent is 20～50%; Hydrophily non-solvent content is 20～70%, changes the consumption of spin solvent and/or hydrophily non-solvent, causes the variation of spinning solution thermodynamic parameter, can be to the membrane aperture size, and membrane pore structure generation effect.Additive can be polyvinylpyrrolidone, silica, lithium chloride, sodium chloride, calcium chloride, lithium nitrate, and consumption is the consumption of 0～25% adjusting additive, can regulate the characteristic of silk process, what and size of control macropore (Macrovoid).
The hollow-fibre membrane internal diameter 0.6～2.2mm of the inventive method preparation, the thickness 0.15～0.5mm of film.The internal diameter of hollow-fibre membrane is by spinning head core pipe physical dimension, core liquid addition and become the control of silk hauling speed.Increase core pipe diameter, increasing core liquid addition can both increase the doughnut internal diameter.Increase to a hauling speed and can reduce the film internal diameter.The thickness of hollow-fibre membrane is added speed and is become the silk hauling speed to regulate by spinning head physical dimension, spinning solution extruded velocity, core liquid.In physical dimension one regularly, strengthen the thickness that the spinning solution extruded velocity can increase film, increase the thickness that becomes a hauling speed can reduce film.
Use method of the present invention can prepare the network-like hollow-fibre membrane of asymmetry, its molecular cut off is 2000～300,000 daltonian milipore filters; Also can prepare the aperture is the micro-filtration membrane of 0.1 μ m～1 μ m.The internal diameter of hollow-fibre membrane is 0.6～2.2mm, and external diameter is 0.9～3mm.Method of the present invention by changing core liquid the composition and the composition of coagulating bath and regulate the dry-wet spinning technological parameter such as temperature, flow, spinning speed etc., can change the position of separating layer, form inner pressed hollow-fibre membrane or external-compression type hollow-fibre membrane.Inner pressed is that separating layer is positioned at the doughnut inboard, and the aperture in its outside is 0.5～20 times of a medial aperture.
Use method of the present invention, can prepare exodermis is the external-compression type hollow-fibre membrane of separating layer, and its internal membrane aperture is bigger than outer surface membrane aperture.And the hollow-fibre membrane of preparation has stronger surface apertures asymmetry, network-like supporting layer pore structure (seeing accompanying drawing 3).
The embodiment of the invention
Embodiment 1: polysulfones ether 21%, and diethylene glycol 45%, N-N dimethyl pyrrolidone (NMP) 34% mixes under 50 ℃, leaves standstill vacuum defoamation 24 hours under 50 ℃, and spinning solution is transported to A type spinning head, and coagulating bath is a water, and core liquid is water.Control spinning speed 15m/ minute, with clear water washing film silk, after heat treatment obtaining internal diameter is 0.8mm, and external diameter is 1.3mm, and ovalbumin solution testing rejection is 97.5%, and pure water flux is 400L/m
2.h (0.1MPa).The extexine average pore size of film is that 250 μ m (SEM method) supporting layer is network-like through hole.The endosexine average pore size is 25nm (an AFM method).
Embodiment 2: polysulfones ether (Amoco) 19%, diethylene glycol (MIT) 46%, N-N dimethyl pyrrolidone (NMP) 34%, under 50 ℃, mix, under 50 ℃, left standstill vacuum defoamation 24 hours, spinning solution is transported to the Type B spinning head, and coagulating bath is a water, and core liquid is the mixed solution of water and NMP.Control spinning speed 15m/ minute, also after heat treatment obtaining internal diameter with the clear water washing is 1.1mm, and external diameter is 1.6mm, and bovine serum albumen solution test rejection is 97.0%, and pure water flux is 550L/m
2.h (0.1MPa).The extexine average pore size of film is 250 μ m (SEM methods), and supporting layer is network-like through hole.
Embodiment 3: polysulfones ether 20%, and diethylene glycol 46%, N-N dimethyl pyrrolidone (NMP) 34% mixes under 50 ℃, leaves standstill vacuum defoamation 24 hours under 50 ℃, and spinning solution is transported to the Type B spinning head, and coagulating bath is a water, and core liquid is water.Control spinning speed 15m/ minute, with the clear water washing, after heat treatment obtaining internal diameter is 1.1mm, and external diameter is 1.6mm, and ovalbumin solution testing rejection is 96.5%, and pure water flux is 450L/m
2.h (0.1MPa).The extexine average pore size of film is 250 μ m (SEM methods), and supporting layer is network-like through hole.The endosexine average pore size is 25nm.
Embodiment 4: polyether sulfone 20%, and diethylene glycol 46%, N-N dimethyl pyrrolidone (NMP) 34% mixes under 50 ℃, leaves standstill vacuum defoamation 24 hours under 50 ℃, and spinning solution is transported to C type spinning head, and coagulating bath is a water, and core liquid is water.Control spinning speed 18m/ minute, with the clear water washing, obtaining internal diameter after the heat treatment is 2.0mm, and external diameter is 2.6mm, and ovalbumin solution testing rejection is 96.5%, and pure water flux is 450L/m
2.h (0.1MPa).The extexine average pore size of film is 200 μ m (SEM methods), and supporting layer is network-like through hole.
Embodiment 5: polyether sulfone 20%, polyvinylpyrrolidone K-30 3%, DEG44%, N-N dimethyl pyrrolidone (NMP) 33% mixes under 50 ℃, leaves standstill vacuum defoamation 24 hours under 50 ℃, spinning solution is transported to A type spinning head, and coagulating bath is a water, and core liquid is water.Control spinning speed 15m/ minute, also after heat treatment obtaining internal diameter with the clear water washing is 0.8mm, and external diameter is 1.3mm, and ovalbumin solution testing rejection is 98.5%, and pure water flux is 350L/m
2.h (0.1MPa).The extexine average pore size of film is 180 μ m (SEM methods), and supporting layer is network-like through hole.
Embodiment 6: polyether sulfone 20%, diethylene glycol 46%, N-N dimethyl pyrrolidone (NMP) 34%, under 50 ℃, mix, under 50 ℃, left standstill vacuum defoamation 24 hours, spinning solution is transported to A type spinning head, coagulating bath is a water, core liquid is the mixed liquor of water and propionic acid, controls spinning speed 13m/ minute, or washs with clear water, obtaining internal diameter after the heat treatment is 0.8mm, external diameter is 1.3mm, and ovalbumin solution testing rejection is 95.5%, and pure water flux is 500L/m
2.h (0.1MPa).The extexine average pore size of film is that 230 μ m (SEM method) supporting layer is network-like through hole.
Embodiment 7: polysulfones ether 19%, diethylene glycol 46%, N-N dimethyl pyrrolidone (NMP) 34%, under 50 ℃, mix, under 50 ℃, left standstill vacuum defoamation 24 hours, spinning solution is transported to the Type B spinning head, and coagulating bath is a water, and core liquid is the mixed solution of water and NMP, diethylene glycol and propionic acid.Control spinning speed 15m/ minute, also after heat treatment obtaining internal diameter with the clear water washing is 1.1mm, and external diameter is 1.6mm, and bovine serum albumen solution test rejection is 90.3%, and pure water flux is 750L/m
2.h (0.1MPa).The extexine average pore size of film is 250 μ m (SEM methods), and supporting layer is network-like through hole.
Claims (5)
1. the preparation method of a dissymmetric network shape pore structure hollow-fibre membrane is characterized in that,
A, preparation spinning solution and core liquid: the high molecular polymer with 14～32%, 20～50% spin solvent, 20～70% hydrophily non-solvent, 0～25% additive adds dissolution kettle, and the each component sum is absolutely; Stirred 8～24 hours down at 40～80 ℃, be configured to spinning solution; Core liquid consists of one or more the mixed liquor in water, spin solvent, the hydrophily non-solvent;
B, one-tenth silk: the interior pipe at spinning head feeds core liquid, and the annular space in spinning head between pipe and the outer tube is extruded through the spinning solution after the deaeration; The distance of spinning head and coagulation bath interdigit is 0.5～45cm, and the spinning solution extrusion temperature is 25～80 ℃, and the core liquid temp is 25～80 ℃, 25～80 ℃ of coagulation bath temperature; Core liquid and coagulation bath temperature difference are not more than 15 ℃; Form the hollow-fibre membrane silk;
C, film forming: the hollow fibre filament of formation is behind the coagulating bath solidified forming, and wrapping wire forms hollow-fibre membrane after 40～150 ℃ hot water thermal are handled on wire wrapping wheel;
Described dissymmetric network shape pore structure hollow-fibre membrane, comprise endodermis and exodermis and be positioned at endodermis and exodermis between supporting layer, described hollow-fibre membrane is the inner pressed hollow-fibre membrane, its exodermis aperture is bigger 0.5～20 times than endodermis aperture; Perhaps, described hollow-fibre membrane is the external-compression type hollow-fibre membrane, and its endodermis aperture is bigger 0.5～20 times than exodermis aperture;
Additive comprises one or more in polyvinylpyrrolidone, silica, lithium chloride, sodium chloride, calcium chloride, the lithium nitrate.
2. the preparation method of dissymmetric network shape pore structure hollow-fibre membrane according to claim 1, it is characterized in that: high molecular polymer comprises one or more in polysulfones, Kynoar, polyacrylonitrile, the polyvinyl chloride.
3. the preparation method of dissymmetric network shape pore structure hollow-fibre membrane according to claim 1, it is characterized in that: spin solvent is N-N dimethyl pyrrolidone, N-N dimethylacetylamide or N-N dimethyl formamide.
4. the preparation method of dissymmetric network shape pore structure hollow-fibre membrane according to claim 1 is characterized in that: spinning coagulation bath consist of in water, spin solvent, the hydrophily non-solvent one or more.
5. the preparation method of dissymmetric network shape pore structure hollow-fibre membrane according to claim 1, it is characterized in that: the supporting layer between endodermis and the exodermis is network-like pore structure, the internal diameter of hollow-fibre membrane is 0.6～2.2mm, and the wall thickness of hollow-fibre membrane is 0.15～0.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101317682A CN101185848B (en) | 2007-08-29 | 2007-08-29 | Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101317682A CN101185848B (en) | 2007-08-29 | 2007-08-29 | Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101185848A CN101185848A (en) | 2008-05-28 |
| CN101185848B true CN101185848B (en) | 2010-12-01 |
Family
ID=39478595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101317682A Active CN101185848B (en) | 2007-08-29 | 2007-08-29 | Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101185848B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102847445A (en) * | 2011-06-28 | 2013-01-02 | 苏州顶裕水务科技有限公司 | Multi-component membrane-casting solution formulation |
| CN102343221A (en) * | 2011-09-29 | 2012-02-08 | 浙江开创环保科技有限公司 | Polyethersulfone membrane with supporting materials and preparation method thereof |
| CN102500158B (en) * | 2011-11-29 | 2014-03-26 | 无锡格瑞普尔膜科技有限公司 | Preparation method for high-efficiency filter medium with adion exchanging function and membrane filtering function |
| CN103100310B (en) * | 2013-01-29 | 2015-03-18 | 浙江理工大学 | Preparation method of polytetrafluoroethylene hollow fibrous membrane for membrane absorption |
| CN103463994A (en) * | 2013-07-23 | 2013-12-25 | 天津工业大学 | Hollow polysulfone fiber film for water purifying cup and preparation method thereof |
| CN103464002B (en) * | 2013-09-17 | 2015-01-28 | 宁波江东科海运拓机械科技有限公司 | Preparation method of composite hollow fiber membrane |
| CN104368246A (en) * | 2014-11-10 | 2015-02-25 | 苏州蔻美新材料有限公司 | Polyacrylonitrile/cellulose acetate fiber composite hemodialysis membrane and preparation method thereof |
| CN104891638A (en) * | 2015-05-25 | 2015-09-09 | 江苏博大环保股份有限公司 | High-salinity high-sludge-concentration industrial wastewater treatment system |
| CN104860446A (en) * | 2015-06-02 | 2015-08-26 | 江苏博大环保股份有限公司 | High-hardness industrial water softening and separation method and system |
| CN105233711A (en) * | 2015-10-31 | 2016-01-13 | 宁波欧梵卫浴有限公司 | Preparation method for water-purifying polysulfone hollow fiber membrane |
| CN106731878A (en) * | 2016-12-09 | 2017-05-31 | 唐山学院 | The preparation method of gradient aperture structure Pvdf Microporous Hollow Fiber Membrane |
| CN107362696B (en) * | 2017-07-12 | 2020-06-09 | 平顶山学院 | Preparation method and application of super-hydrophilic underwater super-oleophobic and super-oleophilic oil-water separation cork filter membrane |
| CN107413205B (en) * | 2017-09-09 | 2020-07-14 | 威海威高血液净化制品有限公司 | Hollow fiber membrane for purifying dialysis waste liquid and processing method thereof |
| CN108579469B (en) * | 2018-04-28 | 2020-07-31 | 河北优玖环保科技有限公司 | Hollow polyvinyl chloride membrane and preparation method thereof |
| CN113019155A (en) * | 2018-07-20 | 2021-06-25 | 安徽原上草节能环保科技有限公司 | Composite microfiltration membrane |
| CN111530306A (en) * | 2020-04-27 | 2020-08-14 | 天津汉晴环保科技有限公司 | Polyether sulfone hollow fiber ultrafiltration membrane with symmetrical structure and preparation method thereof |
| CN113856485B (en) * | 2021-11-05 | 2024-01-26 | 无锡达魔材料科技有限公司 | Preparation method of hollow fiber nitrogen-rich membrane for gas separation with compact inner edge of membrane wall |
| CN114272773B (en) * | 2021-12-24 | 2023-04-28 | 中化(宁波)润沃膜科技有限公司 | High-strength high-flux porous nanofiltration membrane and preparation method thereof |
| CN115475536A (en) * | 2022-09-30 | 2022-12-16 | 浙江工业大学 | Preparation method of permanent hydrophilic polyether sulfone hollow fiber membrane with gradient structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228262B1 (en) * | 1997-12-30 | 2001-05-08 | Kolon Industries, Inc. | Polysulfone based hollow fiber membrane, and a process for preparing the same |
| CN1583232A (en) * | 2003-08-06 | 2005-02-23 | 浙江欧美环境工程有限公司 | Manufacture and products of hollow fiber membrane of outer pressured polyvinylidene fluoride by immersion gelation |
| CN1817426A (en) * | 2005-12-28 | 2006-08-16 | 上海应用技术学院 | Production of hollow fibrous air single external skin separating film with polyether sulphone |
| CN1850639A (en) * | 2006-05-19 | 2006-10-25 | 东华大学 | Poly vinylidene fluoride three-component blend hollow fiber membrane and its preparing method |
| CN1864828A (en) * | 2006-04-28 | 2006-11-22 | 天津大学 | Method for preparing reticular fiber reinforced hollow fiber membrane of polyvinylidene fluoride |
-
2007
- 2007-08-29 CN CN2007101317682A patent/CN101185848B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228262B1 (en) * | 1997-12-30 | 2001-05-08 | Kolon Industries, Inc. | Polysulfone based hollow fiber membrane, and a process for preparing the same |
| CN1583232A (en) * | 2003-08-06 | 2005-02-23 | 浙江欧美环境工程有限公司 | Manufacture and products of hollow fiber membrane of outer pressured polyvinylidene fluoride by immersion gelation |
| CN1817426A (en) * | 2005-12-28 | 2006-08-16 | 上海应用技术学院 | Production of hollow fibrous air single external skin separating film with polyether sulphone |
| CN1864828A (en) * | 2006-04-28 | 2006-11-22 | 天津大学 | Method for preparing reticular fiber reinforced hollow fiber membrane of polyvinylidene fluoride |
| CN1850639A (en) * | 2006-05-19 | 2006-10-25 | 东华大学 | Poly vinylidene fluoride three-component blend hollow fiber membrane and its preparing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101185848A (en) | 2008-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101185848B (en) | Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof | |
| Peng et al. | Evolution of polymeric hollow fibers as sustainable technologies: Past, present, and future | |
| Khan et al. | Status and improvement of dual-layer hollow fiber membranes via co-extrusion process for gas separation: A review | |
| Yang et al. | Preparation of iPP hollow-fiber microporous membranes via thermally induced phase separation with co-solvents of DBP and DOP | |
| JP5878288B2 (en) | Highly permeable polyamide hollow fiber membrane and method for producing the same | |
| JP5293959B2 (en) | Hollow fiber membrane and method for producing the same | |
| CN108079795A (en) | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method | |
| JP2006088148A (en) | Hollow fiber membrane having excellent water permeability | |
| CN105289319B (en) | A kind of preparation method of polymer hollow fiber membrane | |
| KR101179161B1 (en) | Novel polymer resin of Polyvinylidenefluoride type hollow fiber membrane, PVDF hollow fiber membrane with resistant membrane-pollution and Preparing method thereof | |
| JP2003210954A (en) | Method of manufacturing hollow fiber membrane and hollow fiber membrane | |
| CN109692578A (en) | The preparation method of hollow-fibre membrane | |
| KR101269574B1 (en) | Acetylated alkyl cellulose membrane using thermal induced phase separation and preparing method thereof | |
| JP6405177B2 (en) | Polyamide hollow fiber membrane | |
| JP2736992B2 (en) | Polysulfone hollow fiber membrane and method for producing the same | |
| WO2003089120A1 (en) | Hollow fibres | |
| JP2011050881A (en) | Method of spinning hollow fiber membrane | |
| JP3760838B2 (en) | Method for producing hollow fiber membrane and hollow fiber membrane | |
| KR101401163B1 (en) | PVDF asymmetric porous hollow fiber membrane | |
| KR100581206B1 (en) | Polyvinylidene fluoride Porous Hollow Fiber Membrane and the Manufacturing Process thereof | |
| CN109621747B (en) | Preparation method of hollow fiber micro/ultrafiltration membrane | |
| JP2010082509A (en) | Porous membrane | |
| CN108854581B (en) | Preparation method of high-strength composite tubular membrane | |
| KR101415040B1 (en) | Manufacturing method of PVDF asymmetric porous hollow fiber membrane | |
| JP5894687B2 (en) | Highly permeable polyamide hollow fiber membrane and method for producing the same |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20080528 Assignee: Jiangsu Boda Environmental Protection Co., Ltd. Assignor: Jiangnan University Contract record no.: 2013320000302 Denomination of invention: Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof Granted publication date: 20101201 License type: Exclusive License Record date: 20130407 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |