CN103721573A - High-strength hollow fiber film and preparation method thereof - Google Patents
High-strength hollow fiber film and preparation method thereof Download PDFInfo
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- CN103721573A CN103721573A CN201410007868.4A CN201410007868A CN103721573A CN 103721573 A CN103721573 A CN 103721573A CN 201410007868 A CN201410007868 A CN 201410007868A CN 103721573 A CN103721573 A CN 103721573A
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Abstract
The invention provides a high-strength hollow fiber film and a preparation method thereof, belongs to the technical field of composite materials, and the high-strength hollow fiber film can be used for solving the problems of poor hollow fiber film intensity, high silk breakage and deformation and the like in the prior art. The high-strength hollow fiber film comprises a hollow fiber film wall and four reinforcing ribs symmetrically arranged in the wall, wherein the reinforcing ribs are composed of 25-150 reinforcing fiber silks in a twisting manner, the diameter lengths of the reinforcing ribs are 0.03-0.05mm, and the reinforcing fiber silks are one of polyester fibers, glass fibers, carbon fibers and nylons. The invention provides the preparation method of the high-strength hollow fiber film, the high-strength hollow fiber film has the good property and particularly has the strong compression resistance, rupturing tensile strength and water passing volume, the tensile strength can achieve 20N and is more than 5 times of that of the hollow fiber film without the reinforcing ribs, the high-strength hollow fiber film is not deformed under the pressure of 1.8-3MPa, and the service life of the hollow fiber film is greatly prolonged.
Description
Technical field
The present invention relates to a kind of hollow-fibre membrane, be specifically related to a kind of high-intensity hollow tunica fibrosa and preparation method thereof, belong to technical field of composite materials.
Background technology
Along with China's rapid development of economy, water resource more and more becomes the restraining factors of economic development, therefore reduces sewage discharge, and the regeneration of carrying out water has become a kind of inexorable trend.Traditional wastewater regeneration treatment technology exists the shortcomings such as effluent characteristics is not high, occupation of land is large, poor stability, cannot meet new requirement, new technique-embrane method water treatment is arisen at the historic moment, and this technique is applied to the regeneration of water purification and sewage more and more.Membrane separation technique has the advantages such as energy consumption is low, process is simple, separative efficiency is high, non-environmental-pollution, it is the important new and high technology that solves the contemporary energy, resources and environment problem, that other any chemical separation technologies are irreplaceable, its application has related to the fields such as chemical industry, food, medicine, biochemistry, environmental protection, to saving the energy, raise the efficiency, environment purification etc. made significant contribution, is called one of ten the most rising large new and high technologies of 21st century abroad.The conventional membrane material for water treatment has polysulfones, polyacrylonitrile, polyvinyl chloride, polypropylene, Kynoar etc.Wherein Kynoar suitable especially sewage disposal due to its excellent performance.
In sewage disposal, because applied environment is very poor, to having relatively high expectations of film-strength.What hollow-fibre membrane was in the market common is all without supporter in membrane body layer, as Chinese invention patent (publication number: CN103041712A) exists physics hot strength deficiency for hollow-fibre membrane, the problem of the easily broken deformation of filament of film silk discloses a kind of hollow-fibre membrane that comprises the some short fibers of blending in membrane body layer and membrane body layer.Although this hollow-fibre membrane bulk strength is significantly improved, be the twice that does not add the doughnut of short fiber service life, but because short fiber is to sneak in casting solution, when spray silk obtains hollow-fibre membrane, the arrangement of short fiber is irregular, make the physics hot strength of hollow-fibre membrane inhomogeneous, intensity is inhomogeneous, still Shortcomings, and film silk is easily broken deformation of filament still.
Summary of the invention
The object of the invention is to the deficiency for above-mentioned existence, provide a kind of intensity high, the high-intensity hollow tunica fibrosa that water flux is high.
For realizing the object of foregoing invention, the present invention adopts following technical scheme: a kind of high-intensity hollow tunica fibrosa, this high-intensity hollow tunica fibrosa comprises doughnut membranous wall and four reinforcements of symmetric arrays in wall, wherein said reinforcement is closed and is formed by 25-150 reinforcing fibre skein silks respectively, the path length of described reinforcement is 0.03mm-0.05mm, and reinforcing fibre silk is the one in polyster fibre, glass fibre, carbon fiber, nylon.
The present invention has added four reinforcements of symmetric arrays on the basis of existing hollow-fibre membrane, due to the booster action of reinforcement, the hot strength of hollow-fibre membrane is improved significantly, the hot strength of common hollow-fibre membrane is generally at 3-5.5N, and the present invention synthesizes reinforcement according to the demand of different tunica fibrosas by 25-150 reinforcing fibre skein silks, again reinforcement symmetry is added in doughnut membranous wall, making the hot strength of every hollow-fibre membrane be increased to 20N left and right, is the more than 5 times of hollow-fibre membrane that do not add reinforcement.Because reinforcement is in doughnut membranous wall, reinforcement and fiber membranous wall have certain compatibility, and reinforcement is completely in doughnut membranous wall, can not occur to separate and peel off, and lose filtering function.The enhancing successful of the reinforcement that this employing physical method forms is better than the methods such as other chemical modifications, has also overcome and has adopted the film of fortifying fibre method and the shortcoming that fiber easily departs from simultaneously.
In above-mentioned high-intensity hollow tunica fibrosa, the external diameter of described high-intensity hollow tunica fibrosa is 1.5mm-1.6mm, and internal diameter is 0.7mm-0.9mm.The hollow-fibre membrane of above-mentioned specification can reach the intensity needing does not affect again the water flux of hollow-fibre membrane.
In above-mentioned high-intensity hollow tunica fibrosa, described doughnut membranous wall is the one in the polymeric materials such as Kynoar, polytetrafluoroethylene (PTFE), polyvinyl chloride, polysulfones, polyether sulfone, hollow-fibre membrane wall thickness 0.2mm-0.8mm.The footpath ratio different according to different product scale selection.In the present invention, reinforcement selects these materials to have good compatibility by modification and hollow-fibre membrane wall material.
As preferably, described doughnut membranous wall is Kynoar.
Another object of the present invention is to provide a kind of preparation method of above-mentioned high-intensity hollow tunica fibrosa, and this preparation method comprises the steps:
A, the inorganic additive (percentage by weight) of the organic additive (percentage by weight) of the polymer of 15-23% (percentage by weight), 20-25%, 2-6% and 46-63% solvent (percentage by weight) are mixed and made into mixed liquor, each component sum is absolutely, described mixed liquor fully stirs at 50-80 ℃, after deaeration, obtain casting solution; Wherein polymeric material is the one in Kynoar, polytetrafluoroethylene (PTFE), polyvinyl chloride, polysulfones, polyether sulfone;
B, by synthetic 25-150 reinforcing fibre skein silks reinforcement, getting four reinforcements is embedded in mould, preparation liquid in step a is passed through to two sleeve pipe spinning heads, together spray with the reinforcement being embedded in mould, then enter coagulation bath and solidify, film silk outside is by coagulation bath moulding, inner by the moulding of core lyogel, be used to form hollow-fibre membrane internal cavities, thereby form nascent hollow-fibre membrane;
C, the nascent hollow-fibre membrane obtaining in step b is put into clear water rinsing 10-12 hour, then soak after 10-12 hour and dry with 40-50% glycerine water solution, obtain high-intensity hollow tunica fibrosa.
Mixed liquor of the present invention carries out deaeration after stirring, and through spinning head basis, this feed mode can effectively guarantee mixing of mixed liquor, makes the stable performance of hollow-fibre membrane.And after film forming, also need through overpickling or alkali cleaning, removing after the mixed liquor of interior surface, effectively formed the high-intensity hollow-fibre membrane of high flux, its pure water flux is improved.The technology that the present invention prepares hollow-fibre membrane is simple and ripe, excellent product performance, and cost is low.
In the preparation method of above-mentioned high-intensity hollow tunica fibrosa, described organic additive is two or more in polyvinylpyrrolidone class, polyethylene glycols, polyvinyl alcohol, polyoxyethylene, methylcellulose, triton class emulsifying agent.When organic additive exceedes two kinds, total amount addition is constant.
In the preparation method of above-mentioned high-intensity hollow tunica fibrosa, described inorganic additive is one or more in lithium chloride, lithium nitrate, sodium chloride, calcium chloride, sodium acetate, sodium nitrate, calcium nitrate solution.When organic additive exceedes two kinds, total amount addition is constant.
In the preparation method of above-mentioned high-intensity hollow tunica fibrosa, described solvent is one or both in dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, triethyl phosphate, dimethyl sulfoxide (DMSO), water, methyl alcohol, ethanol, ethylene glycol, acetone, oxolane, propane diols, dioxane, when organic additive exceedes two kinds, total amount addition is constant.
In the preparation method of above-mentioned high-intensity hollow tunica fibrosa, mixed liquor described in step a fully stirs 10-25 hour, and after stirring, under the pressure of 0.1-0.4MPa, used 200-400 order filter to be pressed into holder and bullied, after filtration, standing or vacuum defoamation 20-30 hour.
High-intensity hollow tunica fibrosa tool of the present invention has the following advantages:
1, hollow-fibre membrane of the present invention has added four reinforcements of symmetric arrays, resistance to compression, fracture tensile strength and the water-flowing amount of hollow-fibre membrane have been improved significantly, its hot strength can reach 20N, is the more than 5 times of hollow-fibre membrane that do not add reinforcement, is subject to 1.8-3MPa pressure indeformable.
2, the present invention adopts the reinforcement that physical method forms, and reinforcement and bulk material have certain compatibility, and complete tunicle bulk material parcel, separation can not occur and peel off, thereby greatly increase service life of hollow-fibre membrane.
3, it is simple that the present invention prepares the method for high-intensity hollow tunica fibrosa, and cost is low.
Accompanying drawing explanation
Fig. 1 is the structural representation of high-intensity hollow tunica fibrosa of the present invention.
As shown in the figure: 1, doughnut membranous wall; 2, reinforcement.
Fig. 2 is the top view of high-intensity hollow tunica fibrosa of the present invention.
As shown in the figure: 1, doughnut membranous wall; 2, reinforcement.
The specific embodiment
Be below specific embodiments of the invention by reference to the accompanying drawings, technical scheme of the present invention is further described, but the present invention is not limited to these embodiment.
Please refer to Fig. 1,2, Fig. 1 is the structural representation of high-intensity hollow tunica fibrosa of the present invention, and Fig. 2 is the top view of high-intensity hollow tunica fibrosa of the present invention.In Fig. 1,2, high-intensity hollow tunica fibrosa of the present invention comprises doughnut membranous wall 1 and four reinforcements 2 of symmetric arrays in wall.
The external diameter of the high-intensity hollow tunica fibrosa making is 1.5mm-1.6mm, and internal diameter is 0.7mm-0.9mm.
20% Kynoar (percentage by weight), 10% polyvinylpyrrolidone and 12% polyoxyethylene (percentage by weight), 4% lithium chloride (percentage by weight) and 54% dimethyl formamide (percentage by weight) are mixed and made into mixed liquor, each component sum is absolutely, described mixed liquor fully stirs 10 hours at 70 ℃, after stirring, under the pressure of 0.2MPa, used 200 order filters to be pressed into degassed still, after filtration, standing or vacuum defoamation 20 hours, obtain casting solution;
50 polyster fibres are twisted into the reinforcement that path length is 0.04mm, getting four reinforcements is embedded in mould, above-mentioned preparation liquid is passed through to two sleeve pipe spinning heads, together spray with the reinforcement being embedded in mould, then enter coagulation bath and solidify, film silk outside is by coagulation bath moulding, inner by the moulding of core lyogel, be used to form hollow-fibre membrane internal cavities, thereby form nascent hollow-fibre membrane;
The nascent hollow-fibre membrane of above-mentioned acquisition is put into clear water rinsing 11 hours, then dry after 11 hours with 45% glycerine water solution immersion, obtain high-intensity hollow tunica fibrosa.
15% polytetrafluoroethylene (PTFE) (percentage by weight), 18% polyethylene glycol and 7% methylcellulose (percentage by weight), 2% lithium nitrate (percentage by weight) and 48% dimethylacetylamide (percentage by weight) are mixed and made into mixed liquor, each component sum is absolutely, described mixed liquor fully stirs 15 hours at 50 ℃, after stirring, under the pressure of 0.1MPa, used 300 order filters to be pressed into degassed still, after filtration, standing or vacuum defoamation 25 hours, obtain casting solution;
30 glass fibers are twisted into the reinforcement that path length is 0.03mm, getting four reinforcements is embedded in mould, above-mentioned preparation liquid is passed through to two sleeve pipe spinning heads, together spray with the reinforcement being embedded in mould, then enter coagulation bath and solidify, film silk outside is by coagulation bath moulding, inner by the moulding of core lyogel, be used to form hollow-fibre membrane internal cavities, thereby form nascent hollow-fibre membrane;
The nascent hollow-fibre membrane of above-mentioned acquisition is put into clear water rinsing 10 hours, then dry after 12 hours with 40% glycerine water solution immersion, obtain high-intensity hollow tunica fibrosa.
Embodiment 3
23% polyvinyl chloride (percentage by weight), 18% polyvinyl alcohol and 2% polyoxyethylene (percentage by weight), 6% sodium acetate (percentage by weight) and 51% dimethyl sulfoxide (DMSO) (percentage by weight) are mixed and made into mixed liquor, each component sum is absolutely, described mixed liquor fully stirs 210 hours at 80 ℃, after stirring, under the pressure of 0.4MPa, used 400 order filters to be pressed into degassed still, after filtration, standing or vacuum defoamation 30 hours, obtain casting solution;
100 carbon fibers are twisted into the reinforcement that path length is 0.05mm, getting four reinforcements is embedded in mould, above-mentioned preparation liquid is passed through to two sleeve pipe spinning heads, together spray with the reinforcement being embedded in mould, then enter coagulation bath and solidify, film silk outside is by coagulation bath moulding, inner by the moulding of core lyogel, be used to form hollow-fibre membrane internal cavities, thereby form nascent hollow-fibre membrane;
The dilute sulfuric acid that is 1% by concentration by the nascent hollow-fibre membrane of above-mentioned acquisition soaks 15 minutes, then puts into clear water rinsing 3 hours, then dries after 1 hour with glycerine immersion, obtains high-intensity hollow tunica fibrosa.
The nascent hollow-fibre membrane of above-mentioned acquisition is put into clear water rinsing 12 hours, then dry after 10 hours with 50% glycerine water solution immersion, obtain high-intensity hollow tunica fibrosa.
Comparative example
The hollow-fibre membrane that does not add reinforcement that adopts common preparation method to prepare
Hollow-fibre membrane in high-intensity hollow tunica fibrosa in the embodiment of the present invention and comparative example is carried out to Performance Ratio, the results are shown in Table 1
Table 1: the Performance Ratio of the hollow-fibre membrane of embodiment 1-3 and comparative example
In sum, hollow-fibre membrane of the present invention has added four reinforcements of symmetric arrays, resistance to compression, the fracture tensile strength of hollow-fibre membrane have been improved significantly, its fracture tensile strength can reach 20N, be do not add reinforcement hollow-fibre membrane 5-7 doubly, be subject to 2MPa pressure indeformable, water-flowing amount obtains certain raising.And the reinforcement that the present invention adds and bulk material have certain compatibility, and complete tunicle bulk material parcel, can not occur discrete from peeling off, thereby greatly increased service life of hollow-fibre membrane.In addition it is simple that the present invention prepares the method for high-intensity hollow tunica fibrosa, and cost is low.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or supplement or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Claims (8)
1. a high-intensity hollow tunica fibrosa, this high-intensity hollow tunica fibrosa comprises doughnut membranous wall and four reinforcements of symmetric arrays in wall, wherein said reinforcement is closed and is formed by 25-150 reinforcing fibre skein silks respectively, the path length of described reinforcement is 0.03mm-0.05mm, and reinforcing fibre silk is the one in polyster fibre, glass fibre, carbon fiber, nylon.
2. high-intensity hollow tunica fibrosa according to claim 1, is characterized in that, the external diameter of described high-intensity hollow tunica fibrosa is 1.5mm-1.6mm, and internal diameter is 0.7mm-0.9mm.
3. high-intensity hollow tunica fibrosa according to claim 1, it is characterized in that, described doughnut membranous wall is the one in the polymeric materials such as Kynoar ethene, polytetrafluoroethylene (PTFE), polyvinyl chloride, polysulfones, polyether sulfone, hollow-fibre membrane wall thickness 0.2mm-0.8mm.
4. a preparation method for the high-intensity hollow tunica fibrosa described in claim 1-3, is characterized in that, this preparation method comprises the steps:
A, the inorganic additive (percentage by weight) of the organic additive (percentage by weight) of the polymer of 15-23% (percentage by weight), 20-25%, 2-6% and 46-63% solvent (percentage by weight) are mixed and made into mixed liquor, each component sum is absolutely, described mixed liquor fully stirs at 50-80 ℃, after deaeration, obtain casting solution; Wherein polymeric material is the one in Kynoar, polytetrafluoroethylene (PTFE), polyvinyl chloride, polysulfones, polyether sulfone;
B, by synthetic 25-150 reinforcing fibre skein silks reinforcement, getting four reinforcements is embedded in mould, preparation liquid in step a is passed through to two sleeve pipe spinning heads, together spray with the reinforcement being embedded in mould, then enter coagulation bath and solidify, film silk outside is by coagulation bath moulding, inner by the moulding of core lyogel, be used to form hollow-fibre membrane internal cavities, thereby form nascent hollow-fibre membrane;
C, the nascent hollow-fibre membrane obtaining in step b is put into clear water rinsing 10-12 hour, then soak after 10-12 hour and dry with 40-50% glycerine water solution, obtain high-intensity hollow tunica fibrosa.
5. the preparation method of high-intensity hollow tunica fibrosa according to claim 4, it is characterized in that, described organic additive is two or more in polyvinylpyrrolidone class, polyethylene glycols, polyvinyl alcohol, polyoxyethylene, methylcellulose, triton class emulsifying agent, when organic additive exceedes two kinds, total amount addition is constant.
6. the preparation method of high-intensity hollow tunica fibrosa according to claim 4, it is characterized in that, described inorganic additive is one or more in lithium chloride, lithium nitrate, sodium chloride, calcium chloride, sodium acetate, sodium nitrate, calcium nitrate solution, when organic additive exceedes two kinds, total amount addition is constant.
7. the preparation method of high-intensity hollow tunica fibrosa according to claim 4, it is characterized in that, described solvent is one or both in dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, triethyl phosphate, dimethyl sulfoxide (DMSO), water, methyl alcohol, ethanol, ethylene glycol, acetone, oxolane, propane diols, dioxane, when organic additive exceedes two kinds, total amount addition is constant.
8. the preparation method of high-intensity hollow tunica fibrosa according to claim 4, it is characterized in that, mixed liquor described in step a fully stirs 10-25 hour, and after stirring, under the pressure of 0.1-0.4MPa, used 200-400 order filter to be pressed into degassed still, after filtration, standing or vacuum defoamation 20-30 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607060A (en) * | 2014-12-16 | 2015-05-13 | 广州中国科学院先进技术研究所 | High-oil pollution resistant oil/water separation membrane and preparation method thereof |
| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
| CN109758923A (en) * | 2019-01-22 | 2019-05-17 | 山东奥美环境股份有限公司 | A kind of high pressure resistant hollow fiber nanofiltration membrane and preparation method thereof |
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| CN102343219A (en) * | 2011-09-29 | 2012-02-08 | 浙江开创环保科技有限公司 | Polysulfone membrane with supporting materials and preparation method thereof |
| CN202638297U (en) * | 2012-05-15 | 2013-01-02 | 北京碧水源膜科技有限公司 | Composite reinforced hollow fiber membrane |
| CN103041712A (en) * | 2013-01-10 | 2013-04-17 | 浙江开创环保科技有限公司 | High-strength hollow fiber membrane |
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- 2014-01-08 CN CN201410007868.4A patent/CN103721573B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102343219A (en) * | 2011-09-29 | 2012-02-08 | 浙江开创环保科技有限公司 | Polysulfone membrane with supporting materials and preparation method thereof |
| CN202638297U (en) * | 2012-05-15 | 2013-01-02 | 北京碧水源膜科技有限公司 | Composite reinforced hollow fiber membrane |
| CN103041712A (en) * | 2013-01-10 | 2013-04-17 | 浙江开创环保科技有限公司 | High-strength hollow fiber membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607060A (en) * | 2014-12-16 | 2015-05-13 | 广州中国科学院先进技术研究所 | High-oil pollution resistant oil/water separation membrane and preparation method thereof |
| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
| CN109758923A (en) * | 2019-01-22 | 2019-05-17 | 山东奥美环境股份有限公司 | A kind of high pressure resistant hollow fiber nanofiltration membrane and preparation method thereof |
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