CN101185848A - 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
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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
Accompanying drawing 1 is an endodermis SEM photo.
Accompanying drawing 2 is an exodermis SEM photo.
Accompanying drawing 3 is transition supporting layer SEM photo.
Accompanying drawing 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.Composition and the composition of coagulating bath and regulate of method of the present invention by changing core liquid done a wet spinning technology parameter such as temperature, flow, spinning speed etc., can change the position of separating layer, forms 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 (9)
1. dissymmetric network shape pore structure hollow-fibre membrane, comprise endodermis and exodermis and be positioned at endodermis and exodermis between supporting layer, 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.
2. as claims 1 described dissymmetric network shape pore structure hollow-fibre membrane, 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.
3. as the preparation method of dissymmetric network shape pore structure hollow-fibre membrane as described in claims 1, 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.
4. as the preparation method of dissymmetric network shape pore structure hollow-fibre membrane as described in claims 3, it is characterized in that: high molecular polymer comprises one or more in polyether sulfone, polysulfones, Kynoar, polyacrylonitrile, the polyvinyl chloride.
5. as the preparation method of dissymmetric network shape pore structure hollow-fibre membrane as described in claims 3, it is characterized in that: spin solvent comprises N-N dimethyl pyrrolidone, N-N dimethylacetylamide, N-N dimethyl formamide.
6. as the preparation method of dissymmetric network shape pore structure hollow-fibre membrane as described in claims 3, it is characterized in that: the 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, acid, polyoxyethylene, polyoxyethylene and polyoxy third are rare.
7. as the preparation method of dissymmetric network shape pore structure hollow-fibre membrane as described in claims 3, it is characterized in that: additive comprises one or more in polyvinylpyrrolidone, silica, lithium chloride, sodium chloride, calcium chloride, the lithium nitrate.
8. as the preparation method of dissymmetric network shape layer pore structure hollow-fibre membrane as described in claims 3, it is characterized in that: spinning coagulation bath consist of in water, spin solvent, the hydrophily non-solvent one or more.
9. as the preparation method of dissymmetric network shape pore structure hollow-fibre membrane as described in claims 3, it is characterized in that: the composition of core liquid comprises one or more mixed liquors in water, spin solvent, the hydrophily non-solvent.
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