CN102600736B - Preparation method of hollow fiber composite membrane - Google Patents
Preparation method of hollow fiber composite membrane Download PDFInfo
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- CN102600736B CN102600736B CN201210081941.3A CN201210081941A CN102600736B CN 102600736 B CN102600736 B CN 102600736B CN 201210081941 A CN201210081941 A CN 201210081941A CN 102600736 B CN102600736 B CN 102600736B
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Abstract
The invention discloses a preparation method of a hollow fiber composite membrane, aiming at providing a preparation method of the hollow fiber composite membrane, by which the influence on the stability of casting solutions of two kinds of membrane forming systems and the stability of the dimension of the hollow fiber composite fibers during the compositing process can be avoided. The preparation method comprises the following steps: preparing the casting solution of a solution spinning membrane forming system I by a polymer capable of being subjected to solution spinning, an organic solvent and a pore-forming agent; preparing the casting solution of a solution spinning membrane forming system II by a polymer capable of being subjected to solution spinning, an organic solvent and a pore-forming agent; spinning the casting solution of the solution spinning membrane forming system I by a solution spinning method, immersing into the casing solution of the solution spinning membrane forming system II under the conditions that spinning forming is carried out and a hollow inner cavity is filled with a core liquid, and then performing coating; and quickly immersing into coagulating bath for full solidification to obtain the hollow fiber composite membrane. The preparation method is suitable for preparing the hollow fiber composite membrane by utilizing the casing solutions with big difference of temperature or concentration in solution spinning membrane forming systems.
Description
Technical field
The invention belongs to hollow-fibre membrane preparing technical field, in particular, is a kind of preparation method of hollow fiber composite membrane.
Background technology
Hollow-fibre membrane is a kind of important form of diffusion barrier, has been widely used in film distillation and sewage recycling field, relates to a plurality of industries such as chemical industry, environmental protection, building, weaving, papermaking.With regard to its preparation method, mainly comprise solution spinning (also claiming solution phase conversion method, dipper precipitation method or phase separation method), thermally induced phase separation and melt spinning-pulling method etc.Wherein, solution spinning is the particularly main flow technology of preparing of surpass/microfiltration membranes of doughnut of current hollow-fibre membrane, gained hollow-fibre membrane has the advantages that separation accuracy is high, resistance tocrocking is good, the method both can be for the preparation of the hydrophilic hollow-fibre membrane of sewage recycling, also can be for the preparation of the hydrophobic type hollow-fibre membrane in the fields such as film distillation.
The material of preparing that is applicable to solution spinning mainly comprises polysulfones (PS), polyether sulfone (PES), sulfonated polyether sulfone (SPES), polyacrylonitrile (PAN), Kynoar (PVDF) and polyvinyl chloride (PVC) etc., physical property and the chemical property of various material of preparing differ from one another, and the cost of different material of preparing also just differs.Even same material, as PVDF, the tandem product that also exists different molecular weight to distribute.Therefore the hollow-fibre membrane that, the feature of performance different materials is prepared excellent combination property is the focus of membrane preparation technology area research.
The patent No. is 200610035536.2, patent name is the preparation method that the patent documentation of the preparation method > > of a < < composite hollow fiber membrane discloses a kind of PVDF/PS (or PES) composite hollow fiber membrane, to adopt solution spinning membrane system technology, by PS or PES, pore formers etc. are uniform dissolution in organic solvent, as basement membrane film forming system, by PVDF, pore formers etc. are uniform dissolution in organic solvent, as composite bed film forming system, through composite spinning spinning pack and coagulating bath etc., obtaining separating layer is PVDF, basement membrane is the composite hollow fiber membrane of PS or PES.Number of patent application is 200910112298.4, patent name is the preparation method that the patent documentation of the preparation method > > of a < < composite hollow fiber membrane discloses a kind of PVDF/PVC composite hollow fiber membrane, its main technical schemes and the patent No. are that 200610035536.2 patent is basic identical, and difference is mainly that basal lamina material is replaced by the relatively low PVC material of cost.
The common feature of above-mentioned two kinds of methods is all to adopt composite spinneret pack, and cortex film forming system casting solution and sandwich layer film forming system casting solution are extruded through internal layer and the skin of composite spinneret pack simultaneously, then immerse in coagulating bath solidified forming under the acting in conjunction of core liquid and coagulating bath simultaneously.Obviously, it is identical or approach identical and casting solution mobile performance is identical or approach identical solution is spun to film system that the subject matter that this method exists is to be only applicable to casting solution temperature.Otherwise, for two kinds of film forming system casting solution temperature, differ larger system, at two kinds of film forming system casting solutions, pass through in the process of composite spinneret pack simultaneously, will inevitably there is the composite spinneret pack temperature that causes because of two kinds of film forming system casting solution temperature contrasts unstable, and the influence each other process of phase-splitting of two kinds of film forming system casting solutions, then cause the inhomogeneous or phenomenon such as wall unevenness is even along its length of gained hollow fiber composite membrane pore structure; For two kinds of film forming system casting solution mobile performances, differ larger system, as two kinds of film forming system casting solution concentration differ larger, can be higher than the low film forming system casting solution of concentration thereby the film forming system casting solution that concentration is high flows viscosity, at two kinds of film forming system casting solutions, pass through in the process of composite spinneret pack simultaneously, will inevitably there is the spin fluid integral body that causes due to difference of flowability unstable, then cause the even problem of gained hollow fiber composite membrane wall unevenness.
Summary of the invention
The present invention is in order to overcome weak point of the prior art, and a kind of hollow fiber composite membrane preparation method that can avoid recombination process to exert an influence to two kinds of film forming system casting solution stability and hollow-fibre membrane dimensional stability is provided.
The present invention is achieved through the following technical solutions:
A preparation method for hollow fiber composite membrane, is characterized in that, comprises the steps:
(1) polymer, organic solvent and pore former that can solution spinning be configured to the casting solution that solution is spun to film system I;
(2) polymer, organic solvent and pore former that can solution spinning be configured to the casting solution that solution is spun to film system II;
(3) casting solution that solution is spun to film system I is through solution spinning spinning, under spinning technique and hollow cavity are full of the state of core liquid, immerse in the casting solution that solution is spun to film system II and apply, the membrane surface coating solution that the casting solution that makes solution be spun to film system I obtains through solution spinning is spun to the casting solution of film system II; Be immersed in fast afterwards in coagulating bath fully curingly, obtain being spun to sandwich layer that film system I forms and solution by solution and be spun to the hollow fiber composite membrane that cortex that film system II forms forms; Described core liquid is the mixed liquor of water or organic solvent and water, and wherein, in the mixed liquor of organic solvent and water, water content is not less than 50% of core liquid gross mass.
Solution be spun in the casting solution of film system I can solution spinning polymer be any in PS, PES, SPES, PAN, PVC, PVDF.
Described solution is spun in the casting solution of film system I by mass percentage: polymer poly compound that can solution spinning is 10-30%, and organic solvent is 50-80%, and pore former is 10-30%.
Solution be spun in the casting solution of film system II can solution spinning polymer be any in PS, PES, SPES, PAN, PVC, PVDF.
Solution is spun in the casting solution of film system II by mass percentage: polymer that can solution spinning is 10-30%, and organic solvent is 50-80%, and pore former is 10-30%.
Described solution is spun to that the casting solution of film system I and casting solution that solution is spun to film system II form can be identical, can be not identical yet, can be spun to film system for the solution of different film forming polymers, also can be spun to film system for the solution of film forming polymer variable concentrations of the same race.
Wherein, to be spun to film system I all identical with existing solution spinning membrane system technology with pore former with the organic solvent that solution is spun in film system II for solution.Organic solvent can be selected the various good solvents of polymer (PS, PES, SPES, PAN, PVC, PVDF), as N, dinethylformamide, N, N-dimethylacetylamide, N-hydroxymethyl pyrrolidine ketone etc., pore former can be selected various water-soluble components, as organic matter and inorganic matters such as polyethylene glycol, PVP, lithium chloride, Tween 80s.
The present invention has following technique effect:
1, preparation method of the present invention selects identical or different filmogen, configure respectively two kinds of solution and be spun to film system, the casting solution of a kind of film forming system is wherein prepared into hollow-fibre membrane as basement membrane through solution spinning (interior logical core liquid, soak outward coagulating bath), after basement membrane is shaped, the casting solution of another film forming system is evenly coated on to gained membrane surface, be immersed in fast afterwards in coagulating bath fully curingly, obtain the different hollow fiber composite membrane of skin-core structure difference or material.It is identical or approach identical and casting solution mobile performance is identical or approach identical solution is spun to film system that method of the present invention both can equally be applicable to casting solution temperature with conventional composite spinning method, also go for that conventional composite spinning method is restricted, utilize two kinds of different temperatures, the solution that particularly temperature contrast is larger is spun to film system casting solution and prepares hollow fiber composite membrane, and the solution that utilizes two kinds of concentration to differ larger is spun to film system casting solution and prepares hollow fiber composite membrane.Can effectively avoid following situation:
1. the composite spinneret pack temperature causing because of two kinds of film forming system casting solution temperature contrasts is unstable, thereby causes spin fluid flowing instability and the even phenomenon of gained hollow fiber composite membrane wall unevenness;
2. film formation at low temp system casting solution can make high temperature film forming system casting solution Yin Wendu decline and the too early microphase-separated occurring, and then makes the poor problem of gained hollow fiber composite membrane aperture uniformity;
3. high temperature film forming system casting solution makes film formation at low temp system casting solution cause the unstable disturbances such as part component undergoes phase transition because local temperature raises, thereby causes the even phenomenon of gained hollow fiber composite membrane wall unevenness.
4. efficiently solve two kinds of film forming system casting solutions from spinning head is extruded simultaneously because the two concentration differs compared with the mobile performance difference problem causing greatly, ensured the homogeneity of hollow fiber composite membrane wall thickness.
2, particularly support performance is relatively poor for the common mechanical property of hollow-fibre membrane of preparing due to solution spinning, preparation method of the present invention be solution be spun to the casting solution spinning technique of film system I and therein empty inner chamber be full of under the state of core liquid and apply, by the supporting role of core liquid, guarantee the hollow rounding property of gained hollow-fibre membrane.And, the basement membrane outer surface that both can be spun to film system I formation to solution by core liquid permeates, also be conducive to the solidification process that solution is spun to film system II casting solution, thereby avoid occurring the casting solution that solution is spun to film system II solution is spun to the problem that the established duct of film system I is stopped up, be then conducive to the raising of gained hollow fiber composite membrane porosity.
3, the designed solution spinning membrane system method of hollow fiber composite membrane preparation method of the present invention has realized serialization and scale in industrial circle, and agent technology is comparatively ripe, is conducive to the Rapid Implementation of industrialization.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but embodiment does not limit the scope that the present invention protects.
Embodiment 1
(1) according to mass ratio PS, be 30%, organic solvent DMA is 60%, and pore former polyethylene glycol is 10%, and deaeration after temperature is 65 ℃ of blend, is configured to the casting solution that solution is spun to film system I.
(2) according to mass ratio PVDF, be 15%, organic solvent DMF is 65%, and pore former polyethylene glycol is 20%, and deaeration after temperature is 85 ℃ of blend, is configured to the casting solution that solution is spun to film system II;
(3) casting solution that solution is spun to film system I is through solution spinning spinning, in logical core liquid be water, have a coagulating bath outward, under spinning technique and hollow cavity are full of the state of core liquid, immerse in the casting solution that solution is spun to film system II and apply, make solution be spun to the casting solution that membrane surface coating solution that film system I obtains through solution spinning is spun to film system II; Be immersed in fast afterwards in coagulating bath fully curingly, obtaining inner surface is the hollow fiber composite membrane that PS, outer surface are PVDF.In whole spinning membrane system process, the casting solution of two kinds of film forming systems flows and stablizes, the wall thickness homogeneous of the hollow fiber composite membrane obtaining (for 0.25mm), and pore-size distribution homogeneous, average pore size is 0.02 μ m.
Embodiment 2
(1) according to mass ratio SPES, be 15%, organic solvent DMA is 65%, and pore former polyethylene glycol is 20%, and deaeration after temperature is 75 ℃ of blend, is configured to the casting solution that solution is spun to film system I;
(2) according to mass ratio PES, be 20%, organic solvent DMA is 70%, and pore former polyethylene glycol is 10%, and deaeration after temperature is 75 ℃ of blend, is configured to the casting solution that solution is spun to film system II;
(3) casting solution that solution is spun to film system I is through solution spinning spinning, in logical core liquid be the 50% dimethylacetylamide aqueous solution, have a coagulating bath outward, under spinning technique and hollow cavity are full of the state of core liquid, immerse in the casting solution that solution is spun to film system II and apply, make solution be spun to the casting solution that membrane surface coating solution that film system I obtains through solution spinning is spun to film system II; Be immersed in fast afterwards in coagulating bath and fully solidify that to obtain inner surface be the hollow fiber composite membrane that SPES, outer surface are PES.In whole spinning membrane system process, the casting solution of two kinds of film forming systems flows and stablizes, the wall thickness homogeneous of the hollow fiber composite membrane obtaining (for 0.30mm), and pore-size distribution homogeneous, average pore size is 0.05 μ m.
Embodiment 3
(1) according to mass ratio PAN, be 10%, organic solvent N-hydroxymethyl pyrrolidine ketone is 80%, and pore former lithium chloride is 10%, and deaeration after temperature is 70 ℃ of blend, is configured to the casting solution that solution is spun to film system I;
(2) according to mass ratio PVC, be 10%, organic solvent DMA is 75%, and pore former polyethylene glycol is 15%, and deaeration after temperature is 65 ℃ of blend, is configured to the casting solution that solution is spun to film system II;
(3) casting solution that solution is spun to film system I is through solution spinning spinning, in logical core liquid be the aqueous solution of 40% dimethyl formamide, have a coagulating bath outward, under spinning technique and hollow cavity are full of the state of core liquid, immerse in the casting solution that solution is spun to film system II and apply, make solution be spun to the casting solution that membrane surface coating solution that film system I obtains through solution spinning is spun to film system II; Be immersed in fast afterwards in coagulating bath and fully solidify that to obtain inner surface be the hollow fiber composite membrane that PAN, outer surface are PVC.In whole spinning membrane system process, the casting solution of two kinds of film forming systems flows and stablizes, the hollow fiber composite membrane wall thickness homogeneous obtaining (for 0.25mm), pore-size distribution homogeneous, average pore size is 0.12 μ m.
Embodiment 4
(1) according to mass ratio PVDF, be 25%, organic solvent DMA is 50%, and pore former polyethylene glycol is 25%, and deaeration after temperature is 80 ℃ of blend, is configured to the casting solution that solution is spun to film system I;
(2) according to mass ratio PVDF, be 15%, organic solvent DMA is 70%, and pore former polyethylene glycol is 15%, and deaeration after temperature is 80 ℃ of blend, is configured to the casting solution that solution is spun to film system II;
(3) casting solution that solution is spun to film system I is through solution spinning spinning, in logical core liquid be water, have a coagulating bath outward, under spinning technique and hollow cavity are full of the state of core liquid, immerse in the casting solution that solution is spun to film system II and apply, make solution be spun to the casting solution that membrane surface coating solution that film system I obtains through solution spinning is spun to film system II; Be immersed in fast afterwards in coagulating bath and fully solidify and obtain the hollow fiber composite membrane that surfaces externally and internally is PVDF.In whole spinning membrane system process, the casting solution of two kinds of film forming systems flows and stablizes, the hollow fiber composite membrane wall thickness homogeneous obtaining (for 0.25mm), and pore-size distribution homogeneous, average pore size is 0.04 μ m.
Embodiment 5
(1) according to mass ratio PAN, be 30%, organic solvent DMA is 50%, and pore former polyethylene glycol is 20%, and deaeration after temperature is 70 ℃ of blend, is configured to the casting solution that solution is spun to film system I;
(2) according to mass ratio PVDF, be 25%, organic solvent DMA is 60%, and pore former Tween 80 is 15%, and deaeration after temperature is 80 ℃ of blend, is configured to the casting solution that solution is spun to film system II;
(3) casting solution that solution is spun to film system I is through solution spinning spinning, in logical core liquid be water, have a coagulating bath outward, under spinning technique and hollow cavity are full of the state of core liquid, immerse in the casting solution that solution is spun to film system II and apply, make solution be spun to the casting solution that membrane surface coating solution that film system I obtains through solution spinning is spun to film system II; Be immersed in fast afterwards in coagulating bath and fully solidify that to obtain inner surface be the hollow fiber composite membrane that PAN, outer surface are PVDF.In whole spinning membrane system process, the casting solution of two kinds of film forming systems flows and stablizes, the hollow fiber composite membrane wall thickness homogeneous obtaining (for 0.20mm), and pore-size distribution homogeneous, average pore size is 0.06 μ m.
Claims (5)
1. a preparation method for hollow fiber composite membrane, is characterized in that, comprises the steps:
(1) polymer, organic solvent and pore former that can solution spinning be configured to the casting solution that solution is spun to film system I;
(2) polymer, organic solvent and pore former that can solution spinning be configured to the casting solution that solution is spun to film system II;
(3) casting solution that solution is spun to film system I is through solution spinning spinning, under spinning technique and hollow cavity are full of the state of core liquid, immerse in the casting solution that solution is spun to film system II and apply, the membrane surface coating solution that the casting solution that makes solution be spun to film system I obtains through solution spinning is spun to the casting solution of film system II; Be immersed in fast afterwards in coagulating bath fully curingly, obtain being spun to sandwich layer that film system I forms and solution by solution and be spun to the hollow fiber composite membrane that cortex that film system II forms forms; Described core liquid is the mixed liquor of water or organic solvent and water, and wherein, in the mixed liquor of organic solvent and water, water content is not less than 50% of core liquid gross mass.
2. the preparation method of hollow fiber composite membrane according to claim 1, is characterized in that, solution be spun in the casting solution of film system I can solution spinning polymer be any in PS, PES, SPES, PAN, PVC, PVDF.
3. the preparation method of hollow fiber composite membrane according to claim 1 and 2, it is characterized in that, described solution is spun in the casting solution of film system I by mass percentage: polymer poly compound that can solution spinning is 10-30%, and organic solvent is 50-80%, and pore former is 10-30%.
4. the preparation method of hollow fiber composite membrane according to claim 1, is characterized in that, solution be spun in the casting solution of film system II can solution spinning polymer be any in PS, PES, SPES, PAN, PVC, PVDF.
5. according to the preparation method of the hollow fiber composite membrane described in claim 1 or 4, it is characterized in that, solution is spun in the casting solution of film system II by mass percentage: polymer that can solution spinning is 10-30%, and organic solvent is 50-80%, and pore former is 10-30%.
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| CN112206660A (en) * | 2020-09-16 | 2021-01-12 | 北创清源(北京)科技有限公司 | Enhanced anti-pollution low-cost ultrafiltration membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040328A (en) * | 1987-07-10 | 1990-03-14 | 联合碳化公司 | Composite membrane and manufacturing thereof and application |
| CN1883779A (en) * | 2006-05-19 | 2006-12-27 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN101837249A (en) * | 2010-06-13 | 2010-09-22 | 苏州绿膜科技有限公司 | Composite polrvinyl chloride hollow fiber ultrafiltration membrane and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040328A (en) * | 1987-07-10 | 1990-03-14 | 联合碳化公司 | Composite membrane and manufacturing thereof and application |
| CN1883779A (en) * | 2006-05-19 | 2006-12-27 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN101837249A (en) * | 2010-06-13 | 2010-09-22 | 苏州绿膜科技有限公司 | Composite polrvinyl chloride hollow fiber ultrafiltration membrane and preparation method thereof |
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