CN104043346A - Enhanced polyvinylidene fluoride hollow fiber film with highly-asymmetric spongy structure - Google Patents
Enhanced polyvinylidene fluoride hollow fiber film with highly-asymmetric spongy structure Download PDFInfo
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- CN104043346A CN104043346A CN201410214215.3A CN201410214215A CN104043346A CN 104043346 A CN104043346 A CN 104043346A CN 201410214215 A CN201410214215 A CN 201410214215A CN 104043346 A CN104043346 A CN 104043346A
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Abstract
The invention provides an enhanced polyvinylidene fluoride hollow fiber film with a highly-asymmetric spongy structure. The enhanced polyvinylidene fluoride hollow fiber film is prepared by coating the outer surface of a hollow enhancing pipe with a polyvinylidene fluoride film casting liquid. A preparation method for the enhanced polyvinylidene fluoride hollow fiber film comprises the following steps: preparing the transparent, uniform and stable film casting liquid from polyvinylidene fluoride, an organic polar solvent, a hydrophilic second polymer and an organic micromolecular additive; uniformly coating the outer surface of the hollow enhancing pipe with the film casting liquid via a molding spinning device so as to prepare a polyvinylidene fluoride hollow fiber with an enhanced layer; carrying out water-bath consolidation forming so as to prepare the enhanced polyvinylidene fluoride hollow fiber film; and fully extracting the polyvinylidene fluoride hollow fiber film in hot water with a temperature of 20 to 80 DEG C and carrying out drying so as to obtain the enhanced polyvinylidene fluoride hollow fiber film with the highly-asymmetric spongy structure. Compared with the prior art, the invention has the following advantages: the preparation method is simplified; starting with preparation of the film casting liquid, the polyvinylidene fluoride film which can be bonded with the hollow enhancing tube and has the highly-asymmetric spongy structure is prepared, and permeation flux, interception capability and bursting strength of the hollow fiber film are substantially improved.
Description
Technical field
The invention belongs to membrane separation technique field, 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 processing of feedwater etc.
Background technology
Membrane biological reactor process (MBR) is a kind of novel, efficient sewage disposal technology, it can realize the separated of biocatalytic reaction and water and degradation material simultaneously, water resource is regenerated, reach recycling water standard, that the present age is advanced, waste water advanced processing and the regeneration new technology of efficient and low energy consumption, it has effluent quality excellence, stable, compact conformation, simple to operate, the film silk that swings friction has advantages of that certain automatic cleaning action etc. is many outstanding, be widely used in the recycling of water and the fields such as advanced treating of industrial wastewater in municipal works, but these films need to carry out the steps such as aeration and backwash in application process, high-velocity flow or air-flow all can produce larger infringement to film silk, the normal fracture of wire phenomenon that occurs, water quality treatment is produced to greatly impact, cause service life of equipment to shorten, bring problems such as increasing replacement cost.As can be seen here, preparing a kind of hollow-fibre membrane tool with high mechanical properties, applicable different operating environment is of great significance, in many membrane materials, because having excellent mechanical properties, enhancement type hollow fiber film is used widely, become a kind of membrane material that has competitiveness.
At present, business-like reinforced type polyvinylidene fluoride hollow fiber membrane material still 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 etc.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, how those skilled in the art both domestic and external improve the adhesive property of reinforced pipe itself and change on cortex casting solution coating method has been done a large amount of research work, as patent US7306105B2, US7165682B1, CN101632904A, CN101254420A etc., what adopt is first at hollow reinforced pipe outer surface, to apply one deck adhering resin, apply again casting solution, or adopt first heat treatment hollow reinforced pipe to be coated with again the methods such as one deck casting solution to improve the adhesive property between hollow reinforced pipe and membrane material, but the bad operation of these techniques, also easily stop up the hole of hollow reinforced pipe, reduce the flux of enhancement type hollow fiber film, patent CN102512990A has announced a kind of method that reinforced pipe is first soaked and then processed with atmospheric plasma with sodium hydrate aqueous solution, the numerous and diverse and effective property restriction of Cement Composite Treated by Plasma of technique, patent CN102784566A has announced a kind of Kynoar hollow membrane of reinforced pipe reinforcement of high burst strength, the reinforced pipe of this film is first used the mixed liquor heat treatment rinsing oven dry again of NaOH and surfactant, precoating one deck Kynoar weak solution again, after centrifugal oven dry, apply again Kynoar solution, processing step is various, the high and difficult control of production cost, the defects such as patent 201110297245.1 discloses monofilament enhancing and prepared the method that strengthens composite membrane, although the mode strengthening by monofilament has solved subproblem, still exists burst pressure lower, and tensile strength is poor, patent CN102500246A provides a kind of low temperature thermic to be separated to prepare the method for 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 flux requirement, patent 201110280830.0 discloses by body porous substrate and has applied the method that makes porous composite film, though can produce the withstand voltage and excellent enhancing composite membrane of bursting property, but its inner core supporting layer is high price material, and do not have the characteristics such as good bend resistance, stretch-proof, anti-jitter, patent 200910115557.9 discloses by the organic casting solution of inorganic reinforced pipe dip-coating and has made enhancing composite membrane, but due to inorganic reinforced pipe material and organic film material performance difference larger, the shortcomings such as inorganic/organic material compatibility is poor, easily causes coating heterogeneity, and adhesion is poor, in patent CN102512989A, announced the preparation method of the composite thermotropic phase of the polyvinylidene fluoride porous film that a kind of reinforced pipe strengthens, but this film needs the aqueous solution of alcohols to extract and thermal finalization, has increased the complexity of technique, unfavorable to producing, in patent 200710056916.9, announced a kind of reinforced pipe of gradient establishment, 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 solves the existing technical problem of prior art, and the reinforced type polyvinylidene fluoride hollow fiber film of the asymmetric cavernous structure of a kind of height is provided.
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, by Kynoar casting solution, be coated on the hollow reinforced pipe outer surface that polyester fiber is woven into and form, its preparation method comprises the following steps: that (1) is dissolved in solid-state polymer material Kynoar in organic polar solvent, and add can be compatible with this macromolecular material hydrophily the 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 the 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 the 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 water, ethanol, ethylene glycol, glycerine, diglycol, triethylene-glycol, tetraethylene-glycol, polyethylene glycol, 1,2-PD, 1,3-PD, gamma-butyrolacton, sulfolane, tween, inorganic salts, polyoxyethylene, polyvinyl alcohol, the mixture of one or more of lauryl sodium sulfate, described organic polar solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, 1-METHYLPYRROLIDONE, triethyl phosphate, the mixture of one or more of trimethyl phosphate, (2) keeping being delivered to recombination region under the state that hollow reinforced pipe is hollow pipe, and the casting solution without bubble and impurity that is 30-150 ℃ by temperature in step (1) is evenly coated on the outer surface of described hollow reinforced pipe by moulding spinning appts, make the polyvinylidene fluoride hollow fiber with enhancement layer, (3) the described polyvinylidene fluoride hollow fiber with enhancement layer is immersed behind the airspace of 0-20cm length to coagulation forming in the water-bath of 0-80 ℃, make reinforced type polyvinylidene fluoride hollow fiber film, (4) product is processed afterwards and is drying to obtain in the abundant lixiviate in the hot water of 20-80 ℃ of above-mentioned reinforced type polyvinylidene fluoride hollow fiber film.
A kind of reinforced type polyvinylidene fluoride hollow fiber film of being prepared by said method, the film that described Kynoar casting solution forms 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 comprised of same material and form in the preparation process of film simultaneously, two-layerly be connected to each other on the whole, transition from from separating layer to micropore internal layer, only there is membrane structure to change, be that the whole section that film extends to inner face by outer face is highly asymmetrical cavernous structure, and not containing finger-like pore, wherein the separating layer of outer face has the separated aperture of 0.002～0.1 μ m, hole dimension in film is started to increase until inner face by outer face, the wall thickness of film is 20～300 μ m, under 0.1MPa pressure, the pure water permeation flux of film is at least 1000L/ (m
2h), the burst strength that film is peeled off hollow reinforced pipe in normal temperature pure water is at least 0.2Mpa.
As preferably, the average pore size ratio of the average pore size of described spongy membrane inner face and outer face is at least 20.
As preferably, described spongy membrane has at least volumetric porosity of 50vol.%.
Compared with prior art, feature of the present invention is: simplified preparation technology, preparation from casting solution, prepared can be better in conjunction with hollow reinforced pipe and there is the polyvinylidene fluoride film of highly asymmetric cavernous structure, significantly improved permeation flux, interception capacity and the burst strength of hollow-fibre membrane.
Accompanying drawing explanation
Fig. 1 is outer surface ESEM (SEM) image that amplifies hollow-fibre membrane described in 50000 times of lower embodiment 1.
Fig. 2 is profile scanning Electronic Speculum (SEM) image that amplifies hollow-fibre membrane described in 150 times of lower embodiment 1.
Fig. 3 amplifies described in 2000 times of lower embodiment 1 hollow-fibre membrane near profile scanning Electronic Speculum (SEM) image of outer surface.
Fig. 4 is outer surface ESEM (SEM) image that amplifies hollow-fibre membrane described in 50000 times of lower embodiment 2.
Fig. 5 is profile scanning Electronic Speculum (SEM) image that amplifies hollow-fibre membrane described in 180 times of lower embodiment 2.
Fig. 6 amplifies described in 2000 times of lower embodiment 2 hollow-fibre membrane near profile scanning Electronic Speculum (SEM) image of outer surface.
The specific embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: in heatable still, pour the gamma-butyrolacton of 500g of 70 ℃ and the mixture of the 1-METHYLPYRROLIDONE of 3450g into, under agitation in 5 hours, dissolve the Kynoar of 800g and the polyvinylpyrrolidone (PVP of 250g, K90), make the casting solution of transparent stable homogeneous, after standing and defoaming, deliver on moulding spinning appts, keeping being delivered to recombination region under the state that hollow reinforced pipe is hollow pipe, the casting solution of 10g/min being extruded by moulding 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 ℃, form reinforced type polyvinylidene fluoride hollow fiber film, with the hauling speed of 10m/min, reel after this film, again hollow-fibre membrane is put into the abundant lixiviate of hot water of 60 ℃ and processed afterwards and be drying to obtain product.
The external diameter of gained hollow-fibre membrane is about 2.0mm, and wall thickness is about 150 μ m, and referring to Fig. 1-3, its outer surface, section show that this film has highly asymmetric cavernous structure respectively 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 is peeled 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 ℃ and the 1-METHYLPYRROLIDONE of 3700g into, under agitation in 5 hours, dissolve the Kynoar of 800g and the polyvinylpyrrolidone (PVP of 250g, K17), make the casting solution of transparent stable homogeneous, after standing and defoaming, deliver on moulding spinning appts, keeping being delivered to recombination region under the state that hollow reinforced pipe is hollow pipe, the casting solution of 15g/min being extruded by moulding 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 ℃, form reinforced type polyvinylidene fluoride hollow fiber film, with the hauling speed of 12m/min, reel after this film, again hollow-fibre membrane is put into the abundant lixiviate of hot water of 60 ℃ and processed afterwards and be drying to obtain product.
The external diameter of the hollow-fibre membrane of gained is about 1.95mm, the thick 120 μ m that are about, and referring to Fig. 4-6, its outer surface, section show under the multiplication factor of 50000 times, 180 times and 2000 times that respectively this film has 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 is peeled 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 or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. the reinforced type polyvinylidene fluoride hollow fiber film of highly asymmetric cavernous structure, by Kynoar casting solution, be coated on the hollow reinforced pipe outer surface that polyester fiber is woven into and form, the preparation method who it is characterized in that described reinforced type polyvinylidene fluoride hollow fiber film comprises the following steps: that (1) is dissolved in solid-state polymer material Kynoar in organic polar solvent, and add can be compatible with this macromolecular material hydrophily the 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 the 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 the 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 water, ethanol, ethylene glycol, glycerine, diglycol, triethylene-glycol, tetraethylene-glycol, polyethylene glycol, 1,2-PD, 1,3-PD, gamma-butyrolacton, sulfolane, tween, inorganic salts, polyoxyethylene, polyvinyl alcohol, the mixture of one or more of lauryl sodium sulfate, described organic polar solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, 1-METHYLPYRROLIDONE, triethyl phosphate, the mixture of one or more of trimethyl phosphate, (2) keeping being delivered to recombination region under the state that hollow reinforced pipe is hollow pipe, and the casting solution without bubble and impurity that is 30-150 ℃ by temperature in step (1) is evenly coated on the outer surface of described hollow reinforced pipe by moulding spinning appts, make the polyvinylidene fluoride hollow fiber with enhancement layer, (3) the described polyvinylidene fluoride hollow fiber with enhancement layer is immersed behind the airspace of 0-20cm length to coagulation forming in the water-bath of 0-80 ℃, make reinforced type polyvinylidene fluoride hollow fiber film, (4) product is processed afterwards and is drying to obtain in the abundant lixiviate in the hot water of 20-80 ℃ of above-mentioned reinforced type polyvinylidene fluoride hollow fiber film.
2. a reinforced type polyvinylidene fluoride hollow fiber film of being prepared by method described in claim 1, it is characterized in that the film that described Kynoar casting solution forms has micropore internal layer and the separating layer that covers micropore internal layer outer face, separating layer has the structure finer and close than micropore internal layer, separating layer and micropore internal layer are comprised of same material and form in the preparation process of film simultaneously, two-layerly be connected to each other on the whole, transition from from separating layer to micropore internal layer, only there is membrane structure to change, be that the whole section that film extends to inner face by outer face is highly asymmetrical cavernous structure, and not containing finger-like pore, wherein the separating layer of outer face has the separated aperture of 0.002～0.1 μ m, hole dimension in film is started to increase until inner face by outer face, the wall thickness of film is 20～300 μ m, under 0.1MPa pressure, the pure water permeation flux of film is at least 1000L/ (m
2h), the burst strength that film is peeled 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. according to a kind of reinforced type polyvinylidene fluoride hollow fiber film described in claim 2 or 3, it is characterized in that described film has at least volumetric porosity of 50vol.%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110652888A (en) * | 2019-11-13 | 2020-01-07 | 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 |
| US11667782B2 (en) | 2020-09-09 | 2023-06-06 | Industrial Technology Research Institute | Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film |
Citations (3)
| 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 |
| US20070262017A1 (en) * | 2002-11-12 | 2007-11-15 | Mitsubishi Rayon Co., Ltd. | Composite porous membrane and method for producing the same |
| 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 |
-
2014
- 2014-05-20 CN CN201410214215.3A patent/CN104043346B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070262017A1 (en) * | 2002-11-12 | 2007-11-15 | Mitsubishi Rayon Co., Ltd. | Composite porous membrane and method for producing the same |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110652888A (en) * | 2019-11-13 | 2020-01-07 | 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 |
| 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 |
| US11667782B2 (en) | 2020-09-09 | 2023-06-06 | Industrial Technology Research Institute | Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film |
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