CN104043346B - The reinforced type polyvinylidene fluoride hollow fiber film of highly asymmetric cavernous structure - Google Patents
The reinforced type polyvinylidene fluoride hollow fiber film of highly asymmetric cavernous structure Download PDFInfo
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Abstract
The reinforced type polyvinylidene fluoride hollow fiber film of the asymmetric cavernous structure of a kind of height, form by the outer surface that Kynoar casting solution is coated in hollow reinforced pipe, first use Kynoar, organic polar solvent, hydrophily second polymer and organic molecule additive make the casting solution of transparent stable homogeneous, the outer surface by shaping spinning appts casting solution being evenly coated in hollow reinforced pipe makes the polyvinylidene fluoride hollow fiber with enhancement layer, reinforced type polyvinylidene fluoride hollow fiber film is made after water-bath coagulation forming, hollow-fibre membrane is drying to obtain product after abundant lixiviate process in the hot water of 20-80 DEG C.Compared with prior art, this invention simplifies preparation technology, from the preparation of casting solution, prepare and better can have a polyvinylidene fluoride film of highly asymmetric cavernous structure in conjunction with hollow reinforced pipe, significantly improve the permeation flux of hollow-fibre membrane, interception capacity and burst strength.
Description
Technical field
The invention belongs to technical field of membrane separation, specifically relate to the reinforced type polyvinylidene fluoride hollow fiber film of the asymmetric cavernous structure of a kind of height, be applicable to the recycling of advanced treatment of wastewater and the deep purifying process etc. of feedwater.
Background technology
Membrane biological reactor process (MBR) is a kind of novel, efficient sewage disposal technology, it can realize being separated of biocatalytic reaction and water and degradation material simultaneously, water resource is regenerated, reach recycling water standard, that the present age is advanced, the Sewage advanced treatment of efficient and low energy consumption and regeneration new technology, it has effluent quality excellence, stable, compact conformation, simple to operate, the film silk swinging friction has many outstanding advantages such as certain automatic cleaning action, be widely used in the field such as the recycling of water and the advanced treating of industrial wastewater in municipal works, but these films need to carry out the step such as aeration and backwash in application process, high-velocity flow or air-flow all can produce larger infringement to film silk, normal generation fracture of wire phenomenon, extreme influence is produced to water quality treatment, service life of equipment is caused to shorten, bring problems such as increasing replacement cost.As can be seen here, prepare a kind of there is high mechanical properties, the hollow-fibre membrane tool of applicable different operating environment is of great significance, in many membrane materials, be used widely because enhancement type hollow fiber film has excellent mechanical properties, become a kind of membrane material having competitiveness.
At present, business-like reinforced type polyvinylidene fluoride hollow fiber membrane material still also exists many deficiencies, is mainly manifested in the adhesion defective tightness between film and reinforced pipe, is easy to come off, burst strength is poor.The key technology of reinforced pipe support hollow tunica fibrosa is how to improve the bonding force between reinforced pipe and coat membrane material, makes to strengthen the problem that laminating film in use there will not be cortex to come off.Round this key technology, those skilled in the art both domestic and external have done a large amount of research work on the adhesive property how improving reinforced pipe itself and change cortex casting solution coating method, as patent US7306105B2, US7165682B1, CN101632904A, CN101254420A etc., what adopt is first at hollow reinforced pipe outer surface one deck adhering resin, apply casting solution again, or adopt first heat treatment hollow reinforced pipe to be coated with the methods such as one deck casting solution again to improve the adhesive property between hollow reinforced pipe and membrane material, but the bad operation of these techniques, also easily block the hole of hollow reinforced pipe, reduce the flux of enhancement type hollow fiber film, patent CN102512990A discloses a kind of first to soak with sodium hydrate aqueous solution reinforced pipe and then by the method for atmospheric pressure plasma jet treatment, and cumbersome and plasma treatment sometimes validity limit, the Kynoar hollow membrane that the reinforced pipe that patent CN102784566A discloses a kind of high burst strength is strengthened, the reinforced pipe of this film first uses the mixed liquor heat treatment rinsing oven dry again of NaOH and surfactant, precoating one deck Kynoar weak solution again, Kynoar solution is applied again after centrifugal oven dry, processing step is various, the high and difficult control of production cost, patent 201110297245.1 discloses monofilament and strengthens method prepare enhancing composite membrane, although the mode strengthened by monofilament solves subproblem, still there is burst pressure lower, the defects such as tensile strength is poor, patent CN102500246A provides a kind of method that low temperature Thermal inactive prepares the Pvdf Microporous Hollow Fiber Membrane that reinforced pipe strengthens, but the flux of this film is lower, is not suitable in the wastewater treatment of large throughput requirements, patent 201110280830.0 discloses the method by the obtained porous composite film of body porous substrate coating, though the withstand voltage and excellent enhancing composite membrane of bursting property can be produced, but its Core support layer is high price material, and does not have the characteristics such as good bend resistance, stretch-proof, anti-jitter, patent 200910115557.9 discloses and strengthens composite membrane by the organic casting solution of inorganic reinforced pipe dip-coating is obtained, but due to inorganic reinforced pipe material and organic film material performance difference larger, inorganic/organic material compatibility is poor, easily causes coating heterogeneity, the shortcomings such as adhesion is poor, disclose the preparation method of the composite thermotropic phase of the polyvinylidene fluoride porous film that a kind of reinforced pipe is strengthened in patent CN102512989A, but this film needs the aqueous solution of alcohols to carry out extracting and thermal finalization, adds the complexity of technique, unfavorable to production, the reinforced pipe of a kind of gradient establishment is disclosed in patent 200710056916.9, the density of this reinforced pipe changes in gradient, density reduces from the inside to surface, density gradient ratio is 2 ~ 6, but this kind of gradient has little significance to the permeation flux of film and interception capacity raising, because on the permeation flux of film and interception capacity major embodiment polyvinylidene fluoride film, but not on reinforced pipe.
Summary of the invention
The present invention mainly solves the technical problem existing for prior art, provides the reinforced type polyvinylidene fluoride hollow fiber film of the asymmetric cavernous structure of a kind of height.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals: the reinforced type polyvinylidene fluoride hollow fiber film of highly asymmetric cavernous structure, be coated on hollow reinforced pipe outer surface that polyester fiber is woven into by Kynoar casting solution and form, its preparation method comprises the following steps: (1) is dissolved in organic polar solvent by solid-state polymer material Kynoar, and add can be compatible with this macromolecular material hydrophily second polymer and organic molecule additive, make the casting solution of transparent stable homogeneous, in casting solution, the mass concentration of Kynoar is 8%-40%, the mass concentration of hydrophily second polymer is 1%-20%, the mass concentration of organic molecule additive is 1%-30%, the mass concentration of organic polar solvent is 20%-80%, wherein said hydrophily second polymer is polyacrylic acid, polyacrylate, carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, propylene glycol block polyether, the modifier of polysorbate or these polymer or copolymer, described organic molecule additive is ethanol, ethylene glycol, glycerine, diglycol, triethylene-glycol, tetraethylene-glycol, polyethylene glycol, 1,2-PD, 1,3-PD, gamma-butyrolacton, sulfolane, tween, polyoxyethylene, polyvinyl alcohol, one or more mixture of lauryl sodium sulfate, described organic polar solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, 1-METHYLPYRROLIDONE, triethyl phosphate, one or more mixture of trimethyl phosphate, (2) under the state keeping hollow reinforced pipe to be hollow pipe, recombination region is delivered to, and be that the bubble-free of 30-150 DEG C and the casting solution of impurity are evenly coated on the outer surface of described hollow reinforced pipe by shaping spinning appts by temperature in step (1), make the polyvinylidene fluoride hollow fiber with enhancement layer, (3) the described polyvinylidene fluoride hollow fiber with enhancement layer is immersed coagulation forming in the water-bath of 0-80 DEG C behind the airspace of 0-20cm length, make reinforced type polyvinylidene fluoride hollow fiber film, (4) above-mentioned reinforced type polyvinylidene fluoride hollow fiber film is drying to obtain product after abundant lixiviate process in the hot water of 20-80 DEG C.
A kind of reinforced type polyvinylidene fluoride hollow fiber film prepared by said method, the film that described Kynoar casting solution is formed has micropore internal layer and covers the separating layer of micropore internal layer outer face, separating layer has the structure finer and close than micropore internal layer, separating layer and micropore internal layer are made up of same material and are formed in the preparation process of film simultaneously, two-layerly to be connected to each other on the whole, to the transition of micropore internal layer, only membrane structure is had to change from separating layer, namely film is extended to the whole section of inner face in highly asymmetrical cavernous structure by outer face, and not containing finger-like pore, wherein the separating layer of outer face has the separation aperture of 0.002 ~ 0.1 μm, hole dimension in film increases until inner face by outer face, the wall thickness of film is 20 ~ 300 μm, under 0.1MPa pressure, the pure water permeation flux of film is at least 1000L/ (m
2h), the burst strength that film peels off hollow reinforced pipe in normal temperature pure water is at least 0.2MPa.
As preferably, the average pore size of described spongy membrane inner face and the average pore size ratio of outer face are at least 20.
As preferably, described spongy membrane has the volumetric porosity of at least 50vol.%.
Compared with prior art, feature of the present invention is: simplify preparation technology, from the preparation of casting solution, prepare and better can have a polyvinylidene fluoride film of highly asymmetric cavernous structure in conjunction with hollow reinforced pipe, significantly improve the permeation flux of hollow-fibre membrane, interception capacity and burst strength.
Accompanying drawing explanation
Fig. 1 is outer surface ESEM (SEM) image of hollow-fibre membrane described in the lower embodiment 1 of amplification 50000 times.
Fig. 2 is profile scanning Electronic Speculum (SEM) image of hollow-fibre membrane described in the lower embodiment 1 of amplification 150 times.
Fig. 3 is that hollow-fibre membrane described in the lower embodiment 1 of amplification 2000 times is near profile scanning Electronic Speculum (SEM) image of outer surface.
Fig. 4 is outer surface ESEM (SEM) image of hollow-fibre membrane described in the lower embodiment 2 of amplification 50000 times.
Fig. 5 is profile scanning Electronic Speculum (SEM) image of hollow-fibre membrane described in the lower embodiment 2 of amplification 180 times.
Fig. 6 is that hollow-fibre membrane described in the lower embodiment 2 of amplification 2000 times is near profile scanning Electronic Speculum (SEM) image of outer surface.
Detailed description of the invention
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: in heatable still, pour the mixture of the gamma-butyrolacton of the 500g of 70 DEG C and the 1-METHYLPYRROLIDONE of 3450g into, in 5 hours, under agitation dissolve the Kynoar of 800g and the polyvinylpyrrolidone (PVP of 250g, K90), make the casting solution of transparent stable homogeneous, deliver on shaping spinning appts after standing and defoaming, recombination region is delivered under the state keeping hollow reinforced pipe to be hollow pipe, the casting solution extruded by 10g/min by shaping spinning appts is evenly coated on the outer surface of hollow reinforced pipe, behind the airspace of 8cm length, enter coagulation forming in the water-bath of 50 DEG C, form reinforced type polyvinylidene fluoride hollow fiber film, reel after this film with the hauling speed of 10m/min, the hot water again hollow-fibre membrane being put into 60 DEG C is fully drying to obtain product after lixiviate process.
The external diameter of gained hollow-fibre membrane is about 2.0mm, and wall thickness is about 150 μm, and referring to Fig. 1-3, its outer surface, section show this film respectively and have highly asymmetric cavernous structure under the multiplication factor of 50000 times, 150 times and 2000 times.For this film, porosity is 70vol.%, and under 0.1MPa pressure, the pure water permeation flux of film is 1200L/ (m
2h), the burst strength that this film peels off hollow reinforced pipe in normal temperature pure water is greater than 0.4MPa.
Embodiment 2: in heatable still, pour the mixture of the polyethylene glycol (PEG600) of the 250g of 70 DEG C and the 1-METHYLPYRROLIDONE of 3700g into, in 5 hours, under agitation dissolve the Kynoar of 800g and the polyvinylpyrrolidone (PVP of 250g, K17), make the casting solution of transparent stable homogeneous, deliver on shaping spinning appts after standing and defoaming, recombination region is delivered under the state keeping hollow reinforced pipe to be hollow pipe, the casting solution extruded by 15g/min by shaping spinning appts is evenly coated on the outer surface of hollow reinforced pipe, behind the airspace of 8cm length, enter coagulation forming in the water-bath of 50 DEG C, form reinforced type polyvinylidene fluoride hollow fiber film, reel after this film with the hauling speed of 12m/min, the hot water again hollow-fibre membrane being put into 60 DEG C is fully drying to obtain product after lixiviate process.
The external diameter of the hollow-fibre membrane of gained is about 1.95mm, is thickly about 120 μm, referring to Fig. 4-6, its outer surface, section respectively under the multiplication factor of 50000 times, 180 times and 2000 times this film of display there is highly asymmetric cavernous structure.For this film, porosity is 75vol.%, and under 0.1MPa pressure, the pure water permeation flux of film is 1350L/ (m
2h), the burst strength that this film peels off hollow reinforced pipe in normal temperature pure water is greater than 0.4MPa.
Finally, it should be pointed out that above embodiment is only the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to above-described embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1. the reinforced type polyvinylidene fluoride hollow fiber film of a highly asymmetric cavernous structure, be coated on hollow reinforced pipe outer surface that polyester fiber is woven into by Kynoar casting solution and form, it is characterized in that the preparation method of described reinforced type polyvinylidene fluoride hollow fiber film comprises the following steps: that solid-state polymer material Kynoar is dissolved in organic polar solvent by (1), and add can be compatible with this macromolecular material hydrophily second polymer and organic molecule additive, make the casting solution of transparent stable homogeneous, in casting solution, the mass concentration of Kynoar is 8%-40%, the mass concentration of hydrophily second polymer is 1%-20%, the mass concentration of organic molecule additive is 1%-30%, the mass concentration of organic polar solvent is 20%-80%, wherein said hydrophily second polymer is polyacrylic acid, polyacrylate, carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, propylene glycol block polyether, the modifier of polysorbate or these polymer or copolymer, described organic molecule additive is ethanol, ethylene glycol, glycerine, diglycol, triethylene-glycol, tetraethylene-glycol, polyethylene glycol, 1,2-PD, 1,3-PD, gamma-butyrolacton, sulfolane, tween, polyoxyethylene, polyvinyl alcohol, one or more mixture of lauryl sodium sulfate, described organic polar solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, 1-METHYLPYRROLIDONE, triethyl phosphate, one or more mixture of trimethyl phosphate, (2) under the state keeping hollow reinforced pipe to be hollow pipe, recombination region is delivered to, and be that the bubble-free of 30-150 DEG C and the casting solution of impurity are evenly coated on the outer surface of described hollow reinforced pipe by shaping spinning appts by temperature in step (1), make the polyvinylidene fluoride hollow fiber with enhancement layer, (3) the described polyvinylidene fluoride hollow fiber with enhancement layer is immersed coagulation forming in the water-bath of 0-80 DEG C behind the airspace of 0-20cm length, make reinforced type polyvinylidene fluoride hollow fiber film, (4) above-mentioned reinforced type polyvinylidene fluoride hollow fiber film is drying to obtain product after abundant lixiviate process in the hot water of 20-80 DEG C.
2. the reinforced type polyvinylidene fluoride hollow fiber film prepared by method described in claim 1, it is characterized in that the film that described Kynoar casting solution is formed has micropore internal layer and covers the separating layer of micropore internal layer outer face, separating layer has the structure finer and close than micropore internal layer, separating layer and micropore internal layer are made up of same material and are formed in the preparation process of film simultaneously, two-layerly to be connected to each other on the whole, to the transition of micropore internal layer, only membrane structure is had to change from separating layer, namely film is extended to the whole section of inner face in highly asymmetrical cavernous structure by outer face, and not containing finger-like pore, wherein the separating layer of outer face has the separation aperture of 0.002 ~ 0.1 μm, hole dimension in film increases until inner face by outer face, the wall thickness of film is 20 ~ 300 μm, under 0.1MPa pressure, the pure water permeation flux of film is at least 1000L/ (m
2h), the burst strength that film peels off hollow reinforced pipe in normal temperature pure water is at least 0.2MPa.
3. a kind of reinforced type polyvinylidene fluoride hollow fiber film according to claim 2, is characterized in that the average pore size of described film inner face and the average pore size ratio of outer face are at least 20.
4. a kind of reinforced type polyvinylidene fluoride hollow fiber film according to Claims 2 or 3, is characterized in that described film has the volumetric porosity of at least 50vol.%.
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| CN107441945A (en) * | 2017-07-07 | 2017-12-08 | 翟锦树 | A kind of method for preparing water process filter membrane |
| 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 |
| CN110652888B (en) * | 2019-11-13 | 2021-09-17 | 湖北瑞滤膜科技有限公司 | Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof |
| TWI740635B (en) | 2020-09-09 | 2021-09-21 | 財團法人工業技術研究院 | Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069818A (en) * | 2007-03-14 | 2007-11-14 | 天津森诺过滤技术有限公司 | Reinforced capillary-pipe film and preparing method |
| CN102512989A (en) * | 2011-12-31 | 2012-06-27 | 北京坎普尔环保技术有限公司 | Method for preparing braided tube reinforced polyvinylidene fluoride porous membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7306105B2 (en) * | 2002-11-12 | 2007-12-11 | Mitsubishi Rayon Co., Ltd. | Composite porous membrane and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069818A (en) * | 2007-03-14 | 2007-11-14 | 天津森诺过滤技术有限公司 | Reinforced capillary-pipe film and preparing method |
| CN102512989A (en) * | 2011-12-31 | 2012-06-27 | 北京坎普尔环保技术有限公司 | Method for preparing braided tube reinforced polyvinylidene fluoride porous membrane |
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