CN101579604A - Method for preparing pipe-type composite hollow fiber membrane - Google Patents
Method for preparing pipe-type composite hollow fiber membrane Download PDFInfo
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- CN101579604A CN101579604A CNA2009101155579A CN200910115557A CN101579604A CN 101579604 A CN101579604 A CN 101579604A CN A2009101155579 A CNA2009101155579 A CN A2009101155579A CN 200910115557 A CN200910115557 A CN 200910115557A CN 101579604 A CN101579604 A CN 101579604A
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Abstract
A method for preparing a pipe-type composite hollow fiber membrane is characterized in that the preparation method comprises the following steps of: (1) mixing a high polymer organic membrane material, a solvent and an additive by the mass ratio of 10-30:50-90:1-20; stirring and dissolving the mixture uniformly to prepare the composite layer casting solution of a pipe-type composite hollow fiber membrane; and (2) drawing an inorganic material weaving pipe with the outside wrapped by the high polymer organic membrane material at the temperature of 20-90 DEG C, the pressure of 0-0.5MPa and speed of 0.2-5m/min to pass by a solidification liquid at the temperature of 20-50 DEG C, thus preparing the pipe-type composite hollow fiber membrane. The method has the technical effects that the combination is compact; and by controlling the preparation conditions of the pipe-type composite hollow fiber membrane, the prepared pipe-type composite hollow fiber membrane has the following parameters that the external diameter is 0.5-4mm, the wall thickness is 0.1-1mm, the porosity is 40-80 percent and the membrane separation aperture is 0.01-1 microns.
Description
Technical field
The present invention relates to a kind of preparation method of composite hollow fiber membrane, relate in particular to a kind of.
Background technology
Hollow-fibre membrane is a kind of important form of diffusion barrier, its product mainly comprises the little worry film of doughnut, hollow fiber ultrafiltration membrane, doughnut curtain type membrane etc., as membrane bioreactor vouching unit application industry is preferably being arranged aspect wastewater treatment, the sewage reuse.The doughnut membrane material of scale and city's productization application adopts organic film mostly at present, and its membrane material mainly comprises cellulose acetate, polysulfones, Kynoar, polyethylene, polypropylene, polyacrylonitrile etc.But organic film-strength is poor, and service life is short, is a critical limitation sexual factor and the great technical barrier that hinders the extensive and popularization and application of membrane bioreactor.Organic film exists film-strength not high, and membrane material regular meeting breaks, and particularly the fracture of film silk appears in hollow-fibre membrane easily.The hollow-fibre membrane of conventional method preparation, film-strength is provided by separation membrane material self fully, the practicality of diffusion barrier is not only relevant with separation function, and it is closely related with film-strength, particularly the own character of some membrane materials (as Kynoar) makes that also the intensity of preparation doughnut is lower, is difficult to meet the demands.Because hollow-fibre membrane has the density of filling height, but advantages such as backwash are introduced the composite membrane technology of preparing, make the doughnut film strength higher, have important practicality meaning.And be that backing material joins in the doughnut with the inorganic material braided tube, utilize inorganic material braided tube high-intensity performance to bear stressed effect, be a kind of effective ways that improve the doughnut film-strength.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of tubular type composite hollow fiber membrane, adopting the inorganic material braided tube is supporting layer, at the organic film of its compound one deck in outside, prepares the tubular type composite hollow fiber membrane by phase transfer.This method preparation process is simple, and prepared doughnut film-strength height, flux are big.
The present invention is achieved like this, and it is characterized in that the preparation method is:
(1) being composite material with the macromolecule organic material membrane material, is 10～30: 50～90 with macromolecule organic film material, solvent, additive by mass ratio: 1～20 mixes, and stirring and dissolving is even, makes the composite bed casting solution of tubular type composite hollow fiber membrane;
(2) be support layer material with the inorganic material braided tube, the inorganic material braided tube is immersed in the casting solution of step (1) gained, 20～90 ℃ of temperature, pressure 0～0.5Mpa, with the outside inorganic material braided tube that includes the macromolecule organic film material of speed 0.2～5m/min traction, through excess temperature is 20～50 ℃ solidification liquid, makes the tubular type composite hollow fiber membrane.
Described macromolecule organic film material can be the mixture of one or more following high-molecular organic materials: Kynoar, cellulose acetate, polysulfones, polyethylene, polypropylene, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate.
Described support layer material is selected inorganic glass fiber braided tube or stainless steel braided tube for use, is preferably the inorganic glass fiber braided tube.
Described solvent can be the mixture of one or more following solvents: dimethyl formamide, dimethylacetylamide, N～methyl pyrrolidone, dimethyl sulfoxide (DMSO), trimethyl phosphate, triethyl phosphate, sulfolane, tetramethylurea, hexamethyl phosphoric acid ammonium.
Described additive is one or more following mixtures: polyvinylpyrrolidone, polyethylene glycol, lithium chloride, sodium nitrate, polyoxyethylene, ethanol, glycerine.
Technique effect of the present invention is: preparation process is simple, many with contact point between inorganic material braided tube supporting layer and the diffusion barrier composite bed, in conjunction with closely, by the control of tubular type composite hollow fiber membrane preparation condition, prepared tubular type composite hollow fiber membrane, its external diameter is 0.5～4mm, and wall thickness is 0.1～1mm, and porosity is 40～80%, it is 0.01～1 micron that film separates the aperture, hot strength reaches 12.5～50MPa, and anti-burst intensity reaches 0.25～1.5MPa, and pure water flux is 500～10000L/m
2H.
The specific embodiment
Embodiment one
1. get Kynoar 78g, dimethylacetylamide 312g, polyvinylpyrrolidone 24g adds in the molten batch can, and is even 50 ℃ of following stirring and dissolving, and standing and defoaming is made doughnut composite bed casting solution.
2. be the casting solution of the fiberglass braided tube of 1mm by step 1 with diameter, 50 ℃ of temperature, hauling speed 0.8m/min applies, and through entering the solidification liquid pure water after the dried journey of 0.2m, 20 ℃ of solidification liquid temperature make the tubular type composite hollow fiber membrane.
3, obtained tubular type composite hollow fiber membrane was soaked in water 8 hours, glycerine soaked after 4 hours to be tested.The tubular type composite hollow fiber membrane aperture that makes is its external diameter 1.2mm, wall thickness 0.2mm, porosity 65.4%, aperture 1.0 μ m, hot strength 15.2MPa, anti-burst intensity 0.7MPa, pure water flux 1500L/m
2H.
Embodiment two
1. get polyacrylonitrile 78g, dimethylacetylamide 312g, polyethylene glycol 24g adds in the molten batch can, and is even 50 ℃ of following stirring and dissolving, and standing and defoaming is made doughnut composite bed casting solution.
2. prepare the tubular type composite hollow fiber membrane with embodiment one step 2 identical materials and operating condition.
3, obtained tubular type composite hollow fiber membrane was soaked in water 8 hours, soaked in absolute ethyl alcohol was tested after 2 hours.The tubular type composite hollow fiber membrane aperture that makes is its external diameter 1.2mm, wall thickness 0.2mm, porosity 56.2%, aperture 0.5 μ m, hot strength 12.2MPa, anti-burst intensity 0.6MPa, pure water flux 1020L/m
2H.
Embodiment three
1. prepare hollow-fibre membrane composite bed casting solution with embodiment one step 1 identical materials and operating condition.
2. be the casting solution of the fiberglass braided tube of 2mm by step 1 with diameter, 60 ℃ of temperature, hauling speed 0.6m/min applies, and through entering the solidification liquid pure water after the dried journey of 0.2m, 20 ℃ of solidification liquid temperature make the tubular type composite hollow fiber membrane.
3, obtained tubular type composite hollow fiber membrane was soaked in water 8 hours, glycerine soaked after 4 hours to be tested.The tubular type composite hollow fiber membrane aperture that makes is its external diameter 2.3mm, wall thickness 0.3mm, porosity 75.2%, aperture 2 μ m, hot strength 10.3MPa, anti-burst intensity 0.5MPa, pure water flux 1500L/m
2H.
Claims (5)
1, a kind of preparation method of tubular type composite hollow fiber membrane is characterized in that the preparation method is:
(1) being composite material with the macromolecule organic material membrane material, is 10～30: 50～90 with macromolecule organic film material, solvent, additive by mass ratio: 1～20 mixes, and stirring and dissolving is even, makes the composite bed casting solution of tubular type composite hollow fiber membrane;
(2) be support layer material with the inorganic material braided tube, the inorganic material braided tube is immersed in the casting solution of step (1) gained, 20～90 ℃ of temperature, pressure 0～0.5Mpa, with the outside inorganic material braided tube that includes the macromolecule organic film material of speed 0.2～5m/min traction, through excess temperature is 20～50 ℃ solidification liquid, makes the tubular type composite hollow fiber membrane.
2, the preparation method of a kind of tubular type composite hollow fiber membrane according to claim 1 is characterized in that described macromolecule organic film material is the mixture of following one or more high-molecular organic materials: Kynoar, cellulose acetate, polysulfones, polyethylene, polypropylene, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate.
3, the preparation method of a kind of tubular type composite hollow fiber membrane according to claim 1 is characterized in that described support layer material selects inorganic glass fiber braided tube or stainless steel braided tube for use, is preferably the inorganic glass fiber braided tube.
4, the preparation method of a kind of tubular type composite hollow fiber membrane according to claim 1 is characterized in that described solvent is the mixture of following one or more solvents: dimethyl formamide, dimethylacetylamide, N～methyl pyrrolidone, dimethyl sulfoxide (DMSO), trimethyl phosphate, triethyl phosphate, sulfolane, tetramethylurea, hexamethyl phosphoric acid ammonium.
5, the preparation method of a kind of tubular type composite hollow fiber membrane according to claim 1 is characterized in that described additive is one or more following mixtures: polyvinylpyrrolidone, polyethylene glycol, lithium chloride, sodium nitrate, polyoxyethylene, ethanol, glycerine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101155579A CN101579604A (en) | 2009-06-19 | 2009-06-19 | Method for preparing pipe-type composite hollow fiber membrane |
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| CNA2009101155579A CN101579604A (en) | 2009-06-19 | 2009-06-19 | Method for preparing pipe-type composite hollow fiber membrane |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851361A (en) * | 2010-05-25 | 2010-10-06 | 南昌航空大学 | Hollow fiber damping material of nitrile butadiene rubber and preparation method thereof |
| CN102068913A (en) * | 2009-11-25 | 2011-05-25 | 顾文锦 | Expanded polytetrafluoroethylene hollow membrane and preparation method thereof |
| CN102091535A (en) * | 2010-12-21 | 2011-06-15 | 北京碧水源膜科技有限公司 | Light membrane for treating wastewater |
| CN102240509A (en) * | 2010-05-10 | 2011-11-16 | 武汉美克安波科技有限公司 | Composite hollow fiber film preparation method based on on-line braiding-phase transfer moulding |
| CN102389718A (en) * | 2011-09-29 | 2012-03-28 | 浙江理工大学 | Preparation method of acetyl cellulose hollow fiber nano filter membrane |
| CN102580577A (en) * | 2012-03-02 | 2012-07-18 | 天津工业大学 | Preparation method of enhanced polyacrylonitrile hollow fiber membrane |
| CN102781559A (en) * | 2010-03-23 | 2012-11-14 | 东丽株式会社 | Separation membrane and method for producing same |
| CN102921306A (en) * | 2012-11-16 | 2013-02-13 | 北京碧水源膜科技有限公司 | Recovery method of separating film gelling bath solution and separating film prepared by recovered material |
| CN105289328A (en) * | 2015-10-21 | 2016-02-03 | 常州市美纤膜技术有限公司 | Reuse type PVDF filter membrane and preparation technology thereof |
| CN106799170A (en) * | 2017-01-03 | 2017-06-06 | 王玲燕 | A kind of doughnut membrane preparation method |
| CN107376668A (en) * | 2017-09-06 | 2017-11-24 | 天津工业大学 | A kind of pressure resistant type doughnut reverse osmosis membrane and preparation method thereof |
| CN108977927A (en) * | 2018-05-30 | 2018-12-11 | 南昌航空大学 | A kind of nano-tailings sand hollow fiber damping material and preparation method thereof |
| CN110710408A (en) * | 2019-09-30 | 2020-01-21 | 黄鲁鑫 | Preparation method and application of low-temperature-resistant and anti-aging efficient insulation cover cloth for grape vine winter protection |
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2009
- 2009-06-19 CN CNA2009101155579A patent/CN101579604A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068913A (en) * | 2009-11-25 | 2011-05-25 | 顾文锦 | Expanded polytetrafluoroethylene hollow membrane and preparation method thereof |
| CN102781559B (en) * | 2010-03-23 | 2014-12-17 | 东丽株式会社 | Separation membrane and method for producing same |
| CN102781559A (en) * | 2010-03-23 | 2012-11-14 | 东丽株式会社 | Separation membrane and method for producing same |
| CN102240509A (en) * | 2010-05-10 | 2011-11-16 | 武汉美克安波科技有限公司 | Composite hollow fiber film preparation method based on on-line braiding-phase transfer moulding |
| CN101851361A (en) * | 2010-05-25 | 2010-10-06 | 南昌航空大学 | Hollow fiber damping material of nitrile butadiene rubber and preparation method thereof |
| CN102091535A (en) * | 2010-12-21 | 2011-06-15 | 北京碧水源膜科技有限公司 | Light membrane for treating wastewater |
| CN102389718A (en) * | 2011-09-29 | 2012-03-28 | 浙江理工大学 | Preparation method of acetyl cellulose hollow fiber nano filter membrane |
| CN102580577B (en) * | 2012-03-02 | 2014-04-16 | 天津工业大学 | Preparation method of enhanced polyacrylonitrile hollow fiber membrane |
| CN102580577A (en) * | 2012-03-02 | 2012-07-18 | 天津工业大学 | Preparation method of enhanced polyacrylonitrile hollow fiber membrane |
| CN102921306A (en) * | 2012-11-16 | 2013-02-13 | 北京碧水源膜科技有限公司 | Recovery method of separating film gelling bath solution and separating film prepared by recovered material |
| CN102921306B (en) * | 2012-11-16 | 2015-05-20 | 北京碧水源膜科技有限公司 | Recovery method of separating film gelling bath solution and separating film prepared by recovered material |
| CN105289328A (en) * | 2015-10-21 | 2016-02-03 | 常州市美纤膜技术有限公司 | Reuse type PVDF filter membrane and preparation technology thereof |
| CN105289328B (en) * | 2015-10-21 | 2018-01-23 | 常州市美纤膜技术有限公司 | Multiplexing type PVDF filter membranes and its preparation technology |
| CN106799170A (en) * | 2017-01-03 | 2017-06-06 | 王玲燕 | A kind of doughnut membrane preparation method |
| CN107376668A (en) * | 2017-09-06 | 2017-11-24 | 天津工业大学 | A kind of pressure resistant type doughnut reverse osmosis membrane and preparation method thereof |
| CN108977927A (en) * | 2018-05-30 | 2018-12-11 | 南昌航空大学 | A kind of nano-tailings sand hollow fiber damping material and preparation method thereof |
| CN108977927B (en) * | 2018-05-30 | 2021-04-09 | 南昌航空大学 | Nano tailing sand hollow fiber damping material and preparation method thereof |
| CN110710408A (en) * | 2019-09-30 | 2020-01-21 | 黄鲁鑫 | Preparation method and application of low-temperature-resistant and anti-aging efficient insulation cover cloth for grape vine winter protection |
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Open date: 20091118 |