CN103031612A - Preparation method of enhanced hollow fiber ultrafiltration membrane and spinning nozzle - Google Patents
Preparation method of enhanced hollow fiber ultrafiltration membrane and spinning nozzle Download PDFInfo
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- CN103031612A CN103031612A CN2013100215225A CN201310021522A CN103031612A CN 103031612 A CN103031612 A CN 103031612A CN 2013100215225 A CN2013100215225 A CN 2013100215225A CN 201310021522 A CN201310021522 A CN 201310021522A CN 103031612 A CN103031612 A CN 103031612A
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Abstract
The invention provides a preparation method of an enhanced hollow fiber ultrafiltration membrane. The method comprises the steps as follows: placing a fiber filament in a notch groove of a fiber filament fixing plate (2) and fixing with a cover plate (1); introducing the fiber filament from a fiber filament channel to a casting film liquid channel (7) to be composited with a casting film liquid; co-extruding through a spinning solution outlet (11); and sizing to obtain the hollow fiber ultrafiltration membrane. Compared with the prior art, firstly, the fiber filament is pre-composited with the casting film liquid, so that the casting film liquid is distributed inside and outside the fiber filament and the casting film liquid and the fiber filament are not easy to fall off; secondly, the casting film liquid is composited with the fiber filament well, and the fiber filament passes through the hollow fiber ultrafiltration membrane, so that the stretch force bearing point of the hollow fiber ultrafiltration membrane is mainly centralized on the fiber filament, therefore, the stretch strength of the hollow fiber ultrafiltration membrane is further improved; and thirdly, a special spinning nozzle is adopted to fix and position the fiber filament through the notch groove of the fiber filament fixing plate and the cover plate, so that the method is simple and convenient to operate and is convenient for industrialized production.
Description
Technical field
The invention belongs to the membrane separation technique field, relate in particular to a kind of preparation method and a kind of spinning head of enhancement mode hollow fiber ultrafiltration membrane.
Background technology
Membrane separation technique is to occur in 20th century, a kind of separation technology that develop rapidly nearly decades.Film separate have separations, concentrated, purifying and refining function, have again that separative efficiency is high, energy consumption is low, be easy to recovery, automaticity advantages of higher without phase transformation, simple to operate, non-secondary pollution, separator.Wherein, comparatively be typically hyperfiltration technique, especially hollow fiber ultrafiltration membrane.
Hollow-fibre membrane is a kind of fibrous, film with self-supporting effect.Hollow-fibre membrane has that packed density is high, floor space is little, flux is large, low power consumption and other advantages, is widely used in water treatment, pharmacy, brewages, the separation process in the field such as food and drink, food, chemical industry.
Prior art discloses the multiple macromolecular material that is applied to make hollow-fibre membrane, comprises polyvinyl chloride (PVC), polysulfones (PS), polyether sulfone (PES), polyacrylonitrile (PAN), Kynoar (PVDF) etc.Hollow-fibre membrane is self supporting structure, requirement of strength to the film silk is higher, but the mechanical strength of the hollow-fibre membrane that the employing above-mentioned material prepares is lower, the situation of fracture of wire easily occurs in application process, cause that the doughnut membrane lifetime is short, regular maintenance often, the problem such as cost of water treatment height.
At present, the enhancement method of hollow fiber ultrafiltration membrane mainly comprises: braided tube strengthens and thermally induced phase separation.But it is higher that braided tube strengthens technical costs, and production efficiency is low; And need to add diluent in the thermally induced phase separation film-forming process, and and be the high score operation, also easy residual plasticiser in membrane body when cost is high.Therefore, need the new enhancement mode hollow fiber ultrafiltration membrane of research and development.
Publication number is that the Chinese patent of CN1683059A discloses a kind of enhancement mode hollow fiber ultrafiltration membrane and preparation method thereof, the method is by being dissolved in organic solvent with polyvinylidene fluoride resin, and mix with additive and to be made into casting solution, casting solution is coated on the hollow support material, during by coagulating bath because the effect of additive, the casting film material is produced in solvent postpone to be separated, a large amount of glue bundle bodies are to the contact-making surface diffusion of casting solution and coagulating bath, therefore produce the key-course of one deck densification, can obtain to have the hollow fiber ultrafiltration film of surperficial key-course after solidifying.The TENSILE STRENGTH of this hollow fiber ultrafiltration membrane obtains larger raising, but casting solution mainly is distributed in skin, and the internal layer distribution is less, causes cohesive force deficiency between casting solution and the backing material, easily comes off in backwash process; And this hollow fiber ultrafiltration membrane is not suitable for interior pressure.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method and a kind of spinning head of enhancement mode hollow fiber ultrafiltration membrane, the enhancement mode hollow fiber ultrafiltration membrane that the method obtains compound better and TENSILE STRENGTH higher.
The invention provides a kind of spinning head, comprising:
Fiber filament fixed head (2), described fiber filament fixed head (2) are provided with thread passage and are used for holding the cutting of fiber filament, and described thread passage communicates with described cutting;
Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1);
Be positioned at the base (3) of described fiber filament fixed head below, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution outlet (11); Described casting solution passage (7) is communicated with described casting solution charging hole (12) by described thread passage, and the bottom of described casting solution passage (7) is pyramidal structure; Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid passage (8) export (11) with described spinning solution and are communicated with.
The present invention also provides a kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane, may further comprise the steps:
A) provide a kind of spinning head, comprising:
Fiber filament fixed head (2), described fiber filament fixed head (2) are provided with thread passage and are used for holding the cutting of fiber filament, offer thread passage on the described casting solution backflow preventing structure (14), and described thread passage communicates with described cutting;
Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1);
Be positioned at the base (3) of described fiber filament fixed head below, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution outlet (11); Described casting solution passage (7) is communicated with described casting solution charging hole (12) by described thread passage, and the bottom of described casting solution passage (7) is pyramidal structure; Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid passage (8) export (11) with described spinning solution and are communicated with;
B) fiber filament is put into add after the cutting of described fiber filament fixed head (2) described cover plate (1) fixing after, introduce in the described casting solution passage (7) compound with casting solution by described thread passage, through described spinning solution outlet (11) coextrusion, obtain hollow fiber ultrafiltration membrane after the typing;
Described casting solution comprises:
Preferably, described fiber filament is selected from a kind of in terylene, nylon, cotton fiber and the polyamide fibre.
Preferably, the quantity of described fiber filament is 1 ~ 10.
Preferably, described hydrophilizing agent is selected from one or more in the terpolymer of the terpolymer of bipolymer, vinyl chloride and carboxyl compound of vinyl chloride and carboxyl compound and vinyl chloride and hydroxy compounds.
Preferably, described hydrophilizing agent is vinyl chloride-vinyl acetate bipolymer and/or chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer.
Preferably, described pore-foaming agent is selected from polyvinylpyrrolidone and/or polyethylene glycol.
Preferably, described solvent is selected from one or both in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, trimethyl phosphate, triethyl phosphate and the tetramethylurea.
Preferably, described fiber filament is put into the cutting of fiber filament fixed head (6) after the soak preliminary treatment.
Preferably, described soak is solvent or acid-base solution, and described acid-base solution is that the pH value is 3 ~ 12 acid-base solution.
The invention provides a kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane, the method fiber filament is put into add after the cutting of fiber filament fixed head (2) cover plate (1) fixing after, introduce in the casting solution passage (7) compound with casting solution by thread passage, through spinning solution outlet (11) coextrusion, obtain hollow fiber ultrafiltration membrane after the typing; Described casting solution comprises: the polyvinyl chloride of 9 ~ 16wt%, 4 ~ 11wt% hydrophilizing agent, the pore-foaming agent of 3 ~ 12wt% and 62 ~ 83wt% solvent.With prior art casting solution is coated in the hollow support material and prepares hollow fiber ultrafiltration membrane and compare, the present invention is by compound in advance with fiber filament and casting solution, is positioned at long fiber among the casting solution and then obtains hollow fiber ultrafiltration membrane.At first, the present invention is by compound in advance with fiber filament and casting solution, can make casting solution at fiber filament inside and outside distribution be arranged all, makes casting solution and fiber filament difficult drop-off; Secondly, casting solution and fiber filament are compound better, and fiber filament runs through hollow fiber ultrafiltration membrane, makes the stretching stress point of milipore filter mainly concentrate on fiber filament, and then has improved the TENSILE STRENGTH of hollow fiber ultrafiltration membrane; Again, the present invention adopts special spinning head, and cutting and the cover plate of fiber filament by the fiber filament fixed head is fixed the location, and is simple to operation, is convenient to suitability for industrialized production.
Experimental result shows, the enhancement mode hollow fiber ultrafiltration membrane film silk tensile break strength that the present invention prepares is 20 ~ 30N, and elongation at break is 10% ~ 14%.
Description of drawings
Fig. 1 is the structural representation of spinning head of the present invention;
Fig. 2 is the top view of fiber filament fixed head of the present invention.
The specific embodiment
See also Fig. 1,1 is cover plate among Fig. 1, and 2 is the fiber filament fixed head, 3 is base, and 4 is the spinning head bottom, and 5 is the spinning head stage casing, 6 is fiber filament, and 7 is the casting solution passage, and 8 is core liquid passage, 9 is second channel, 10 is core liquid pipe, and 11 are the spinning solution outlet, and 12 is the casting solution charging hole, 13 is core liquid charging hole, and 14 is attaching parts.
The invention provides a kind of spinning head, comprising:
Fiber filament fixed head (2), described fiber filament fixed head (2) is provided with thread passage and is used for holding the cutting of fiber filament, and as shown in Figure 2, a is for being used for holding the cutting of fiber filament among Fig. 2, b is thread passage, and c is that screw hole is used for being fixed with miscellaneous part.Described thread passage communicates with described cutting, and the quantity of wherein said cutting and unrestricted is preferably 1 ~ 6 among the present invention, and more preferably 2 ~ 4, cutting can be evenly distributed on the fiber filament fixed head (2), but also uneven distribution there is no special restriction.
Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1);
Be positioned at the base (3) of described fiber filament fixed head below, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution outlet (11).
Described casting solution passage (7) is communicated with described casting solution charging hole (12) by described thread passage, thread passage communicates with cutting, thereby described casting solution passage (7) is communicated with described cutting by described thread passage, the width of described cutting is thinner, be slightly larger than the long filament size, thereby make casting solution be difficult for outflow.
Fiber filament is introduced in the casting solution passage (7) through cutting and thread passage, and herein, casting solution and fiber filament carry out compound.
The bottom of described casting solution passage (7) is pyramidal structure; Pyramidal structure outlet is thinner, and controllable flow goes out the diameter of spinning solution, also can make the casting solution rate of outflow slower, thereby can make casting solution and fiber filament fully compound in casting solution passage (7).In order to optimize technique scheme, described casting solution passage (7) preferably includes first passage and second channel (9), and described second channel is pyramidal structure.
Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid passage (8) export (11) with described spinning solution and are communicated with.
Clean and install for convenient, described base (3) preferably is divided into spinning head stage casing (5) and spinning head bottom (4).Described first passage preferably is located at the spinning head stage casing, and the second channel of described pyramidal structure (9) preferably is located at the spinning head bottom.Described second channel (9) exports (11) with described spinning solution and is communicated with.Described core liquid passage (8) preferably is connected with spinning solution outlet (11) by core liquid pipe (10).
In order to optimize technique scheme, described core liquid passage (8) can be located at described core liquid charging hole (13) and also can be located on the spinning head stage casing (5) on the spinning head bottom (4), there is no special restriction.Preferred spinning head stage casing (5) is provided with core liquid charging hole (13) and described core liquid passage (8) among the present invention, and described core liquid passage (8) is arranged in parallel with the first passage of described casting solution passage (7).
Between described cover plate (1), fiber filament fixed head (2) and the base (3), all link to each other by attaching parts (14) between described spinning head stage casing (5) and the spinning head bottom (4).Described attaching parts (14) are preferably screw.
The present invention also provides a kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane, described hollow fiber ultrafiltration membrane adopts above-mentioned spinning head to be prepared, may further comprise the steps: fiber filament is put into add after the cutting of fiber filament fixed head (2) described cover plate (1) fixing after, introduce in the casting solution passage (7) compound with casting solution through described thread passage, through spinning solution outlet (11) coextrusion, obtain hollow fiber ultrafiltration membrane after the typing.
Wherein, described fiber filament is terylene, nylon, cotton fiber or polyamide fibre, is preferably terylene, nylon or polyamide fibre.The quantity of described fiber filament is 1 ~ 10, is preferably 3 ~ 7.
For making fiber filament compound with the casting film liquid phase better, the present invention preferably carried out preliminary treatment before fiber filament is put into the cutting of fiber filament fixed head (2).Described pretreated method is that method well known to those skilled in the art gets final product, and there is no special restriction.Preliminary treatment described in the present invention is preferably immersion.Described soak can be the solvent in the casting solution, also can be acid-base solution, there is no special restriction.Described solvent is preferably one or both in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, trimethyl phosphate, triethyl phosphate and the tetramethylurea.Described acid-base solution is that the pH value is that 3 ~ 12 acid-base solution gets final product, and the pH value is preferably 5 ~ 10.
Through the preliminary treatment of soak, can remove the grease on fiber filament surface, but the also caking property of high molecular polymer in fortifying fibre long filament and the casting solution.
The present invention also preferably distributes frame with fiber filament through fiber filament, enters fiber filament fixed head (2).It is that fiber filament well known to those skilled in the art distributes frame to get final product that described fiber filament distributes frame, there is no special restriction.Fiber filament described in the present invention at first distributes the guide wheel of frame through fiber filament, with the fiber filament coil stripping, then be directed on the locating wheel, fiber filament is vertically imported in the spinning head its power of can reducing friction by locating wheel.
The material of fiber filament has higher intensity, with its backing material as hollow fiber ultrafiltration membrane, can improve the bulk strength of tunica fibrosa.
According to the present invention, described casting solution comprises: the polyvinyl chloride of 9 ~ 16wt%, the hydrophilizing agent of 4 ~ 11wt%, the pore-foaming agent of 3 ~ 12wt%, the solvent of 62 ~ 83wt%.
The content of described polyvinyl chloride is preferably 10 ~ 16wt%.
Described hydrophilizing agent is that hydrophilizing agent well known to those skilled in the art gets final product, and there is no special restriction.Hydrophilizing agent described in the present invention is preferably selected from one or more in the terpolymer of the terpolymer of bipolymer, vinyl chloride and carboxyl compound of vinyl chloride and carboxyl compound and vinyl chloride and hydroxy compounds,, more preferably vinyl chloride-vinyl acetate and/or chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer.The content of described hydrophilizing agent is preferably 5 ~ 10%.
Described pore-foaming agent is that pore-foaming agent well known to those skilled in the art gets final product, and there is no special restriction.Pore-foaming agent described in the present invention is preferably polyvinylpyrrolidone and/or polyethylene glycol.The content of described pore-foaming agent is preferably 5 ~ 10%.
Described solvent is that organic solvent well known to those skilled in the art gets final product, and there is no special restriction.Solvent described in the present invention is preferably one or both in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, trimethyl phosphate, triethyl phosphate and the tetramethylurea.The content of described solvent is preferably 65 ~ 80%.
The casting solution charging hole of described casting solution on cover plate (1) injects, and enters casting solution passage (7), and described casting solution and fiber filament are compound in casting solution passage (7).
The present invention is by compound in advance with fiber filament and casting solution, can make casting solution at fiber filament inside and outside distribution be arranged all, makes casting solution and fiber filament difficult drop-off; Simultaneously, casting solution and fiber filament are compound better, and fiber filament runs through hollow fiber ultrafiltration membrane, makes the stretching stress point of milipore filter mainly concentrate on fiber filament, and then has improved the TENSILE STRENGTH of hollow fiber ultrafiltration membrane.
According to the present invention, described casting solution preferably stirs 10 ~ 30h under 50 ℃ ~ 80 ℃ conditions, then injects the casting solution charging hole after the standing and defoaming, more preferably stirs under 60 ℃ ~ 70 ℃ conditions, and described mixing time is preferably 15 ~ 25h.Described time of repose is preferably 6 ~ 15h, more preferably 7 ~ 10h.Adding thermal agitation can make each component of casting solution fully dissolve mixing.Fiber filament after fully compound and casting solution are through spinning solution outlet (11) coextrusion, the present invention preferably adopts dry-wet spinning during described coextrusion, the fiber filament that spinning solution outlet is extruded contacts with core liquid through spinning solution outlet (11) with casting solution, before entering coagulating bath first through one section air layer.The spinning external diameter of described dry-wet spinning is preferably 1.0mm ~ 3.0mm, 1.5mm ~ 2.0mm more preferably, the spinning internal diameter of described dry-wet spinning is preferably 0.5mm ~ 1.5mm, more preferably 0.6mm ~ 1.2mm, described air gap height is preferably 10cm ~ 25cm, more preferably 14cm ~ 20cm.
The method of described typing is that method well known to those skilled in the art gets final product, and there is no special restriction.The preferred solution phase separation method that adopts is finalized the design among the present invention: the fiber filament after fully compound and casting solution are through spinning solution outlet (11) coextrusion, simultaneously, core liquid is incorporated into core liquid passage from core liquid charging hole (13), and the fiber filament of coextrusion and casting solution be film forming under the effect of core liquid and outer coagulating bath.
Described core liquid and coagulating bath are core liquid well known to those skilled in the art and coagulating bath gets final product, and there is no special restriction.The liquid of core described in the present invention and coagulating bath are mixture or the water of water and organic solvent, described organic solvent is that organic solvent well known to those skilled in the art gets final product, and there is no special restriction, described organic solvent can with casting solution in solvent phase with, also can be different, and unrestricted.The ratio of water and organic solvent and unrestricted guarantees that it contains moisture and gets final product in the mixture of described water and organic solvent.The composition of described core liquid and coagulating bath can be identical, also can be different, there is no special restriction.
Experimental result shows, the hollow fiber ultrafiltration membrane film silk tensile break strength that the present invention prepares is 20 ~ 30N, and elongation at break is 10% ~ 14%.
In order to further specify the present invention, below in conjunction with embodiment preparation method and a kind of spinning head of a kind of enhancement mode hollow fiber ultrafiltration membrane provided by the invention are described in detail.
Used reagent is commercially available in following examples.
Embodiment 1
1.1 use spinning head as shown in Figure 1, comprise: fiber filament fixed head (2), described fiber filament fixed head (2) is provided with thread passage and is used for holding the cutting of fiber filament, and described cutting is evenly distributed on fiber filament fixed head (2) upward and quantity is 4; Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1); Be positioned at the spinning head stage casing (5) of fiber filament fixed head below, be provided with first passage, the core liquid charging hole (13) and core liquid passage (8) of casting solution passage, the first passage of core liquid passage and casting solution passage is arranged in parallel; Be positioned at the spinning head bottom (4) of below, spinning head stage casing (5), be provided with second channel (9) and the core liquid pipe (10) of casting solution passageway cone structure, core liquid pipe (10) is communicated with core liquid passage (8); Described second channel (9) all is communicated with spinning solution outlet (11) with core liquid pipe (10); Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid pipe (10) export (11) with described spinning solution and are communicated with.
1.2 in following ratio preparation casting solution: polyvinyl chloride resin powder 14wt%, polyethylene glycol 7wt%, dimethylacetylamide 50wt%, 1-METHYLPYRROLIDONE 25wt% and vinyl chloride-vinyl acetate 4wt%.Casting solution is heated to 65 ℃, stirs 16h, standing and defoaming 8h.
1.3 with 3 polyster fibre filaments behind the dimethylacetylamide dipping pretreatment, put into the cutting of spinning head fiber filament fixed head (2) and pass thread passage, introduce casting solution passage (7), 1.1 in the casting solution that obtains injected by casting solution charging hole (12), enter in the casting solution passage (7) through thread passage, after polyster fibre filament and casting solution are compound in casting solution passage (7), adopt dry-wet spinning, spinning external diameter 1.7mm, internal diameter 0.9mm contacts with core liquid after spinning solution outlet (11) coextrusion, through the air gap of height 17cm, then spinning speed 35m/min enters the coagulating bath typing and obtains middle fiber ultrafiltration membrane.Core liquid and coagulating bath are water, and temperature is 30 ℃.
In 1.3, obtain hollow fiber ultrafiltration membrane through carrying out performance test after rinsing and the immersion of 40% glycerine, the result shows, the fracture tensile strength of described hollow fiber ultrafiltration membrane is 20N, elongation at break is 12%, airblasting pressure is 1.2MPa, molecular cut off 80,000 dalton, pure water flux 700L/m
2H(0.15MPa, 25 ℃ of water temperatures).
Embodiment 2
2.1 use spinning head as shown in Figure 1, comprise: fiber filament fixed head (2), described fiber filament fixed head (2) is provided with thread passage and is used for holding the cutting of fiber filament, and described cutting is evenly distributed on fiber filament fixed head (2) upward and quantity is 4; Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1); Be positioned at the spinning head stage casing (5) of fiber filament fixed head below, be provided with first passage, the core liquid charging hole (13) and core liquid passage (8) of casting solution passage, the first passage of core liquid passage and casting solution passage is arranged in parallel; Be positioned at the spinning head bottom (4) of below, spinning head stage casing (5), be provided with second channel (9) and the core liquid pipe (10) of casting solution passageway cone structure, core liquid pipe (10) is communicated with core liquid passage (8); Described second channel (9) all is communicated with spinning solution outlet (11) with core liquid pipe (10); Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid pipe (10) export (11) with described spinning solution and are communicated with.
2.2 in following ratio preparation casting solution: polyvinyl chloride resin powder 15wt%, polyethylene glycol 4wt%, polyvinylpyrrolidone 6wt%, dimethylacetylamide 37wt%, 1-METHYLPYRROLIDONE 33wt%, vinyl chloride-vinyl acetate 2wt% and chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer 3wt%.Casting solution is heated to 60 ℃, stirs 16h, standing and defoaming 8h.
2.3 with 4 polyster fibre filaments behind the dimethylacetylamide dipping pretreatment, put into the cutting of spinning head fiber filament fixed head (2) and pass thread passage, introduce casting solution passage (7), 2.1 in the casting solution that obtains injected by casting solution charging hole (12), enter in the casting solution passage (7) through thread passage, after polyster fibre filament and casting solution are compound in casting solution passage (7), adopt dry-wet spinning, spinning external diameter 1.7mm, internal diameter 0.9mm contacts with core liquid after spinning solution outlet (11) coextrusion, through the air gap of height 17cm, then spinning speed 35m/min enters the coagulating bath typing and obtains middle fiber ultrafiltration membrane.Core liquid and coagulating bath are water, and temperature is 30 ℃.
In 2.3, obtain hollow fiber ultrafiltration membrane through carrying out performance test after rinsing and the immersion of 40% glycerine, the result shows, the fracture tensile strength of described hollow fiber ultrafiltration membrane is 25N, elongation at break is 10%, airblasting pressure is 1.2MPa, molecular cut off 80,000 dalton, pure water flux 600L/m
2H(0.15MPa, 25 ℃ of water temperatures).
Embodiment 3
3.1 use spinning head as shown in Figure 1, comprise: fiber filament fixed head (2), described fiber filament fixed head (2) is provided with thread passage and is used for holding the cutting of fiber filament, and described cutting is evenly distributed on fiber filament fixed head (2) upward and quantity is 4; Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1); Be positioned at the spinning head stage casing (5) of fiber filament fixed head below, be provided with first passage, the core liquid charging hole (13) and core liquid passage (8) of casting solution passage, the first passage of core liquid passage and casting solution passage is arranged in parallel; Be positioned at the spinning head bottom (4) of below, spinning head stage casing (5), be provided with second channel (9) and the core liquid pipe (10) of casting solution passageway cone structure, core liquid pipe (10) is communicated with core liquid passage (8); Described second channel (9) all is communicated with spinning solution outlet (11) with core liquid pipe (10); Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid pipe (10) export (11) with described spinning solution and are communicated with.
3.2 in following ratio preparation casting solution: polyvinyl chloride resin powder 15wt%, polyethylene glycol 1wt%, polyvinylpyrrolidone 6wt%, dimethylacetylamide 42wt%, 1-METHYLPYRROLIDONE 33wt% and chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer 3wt%.Casting solution is heated to 70 ℃, stirs 16h, standing and defoaming 8h.
3.3 with 6 polyster fibre filaments behind the dimethylacetylamide dipping pretreatment, put into the cutting of spinning head fiber filament fixed head (2) and pass thread passage, introduce casting solution passage (7), 3.1 in the casting solution that obtains injected by casting solution charging hole (12), enter in the casting solution passage (7) through thread passage, after polyster fibre filament and casting solution are compound in casting solution passage (7), adopt dry-wet spinning, spinning external diameter 1.7mm, internal diameter 0.9mm contacts with core liquid after spinning solution outlet (11) coextrusion, through the air gap height of height 17cm, then spinning speed 35m/min enters the coagulating bath typing and obtains middle fiber ultrafiltration membrane.Core liquid and coagulating bath are water, and temperature is 30 ℃.
In 3.3, obtain hollow fiber ultrafiltration membrane through carrying out performance test after rinsing and the immersion of 40% glycerine, the result shows, the fracture tensile strength of described hollow fiber ultrafiltration membrane is 30N, elongation at break is 14%, airblasting pressure is 1.2MPa, molecular cut off 80,000 dalton, pure water flux 800L/m
2H(0.15MPa, 25 ℃ of water temperatures).
The above only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a spinning head is characterized in that, comprising:
Fiber filament fixed head (2), described fiber filament fixed head (2) are provided with thread passage and are used for holding the cutting of fiber filament, and described thread passage communicates with described cutting;
Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1);
Be positioned at the base (3) of described fiber filament fixed head below, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution outlet (11); Described casting solution passage (7) is communicated with described casting solution charging hole (12) by described thread passage, and the bottom of described casting solution passage (7) is pyramidal structure; Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid passage (8) export (11) with described spinning solution and are communicated with.
2. the preparation method of an enhancement mode hollow fiber ultrafiltration membrane is characterized in that, may further comprise the steps:
A) provide a kind of spinning head, comprising:
Fiber filament fixed head (2), described fiber filament fixed head (2) are provided with thread passage and are used for holding the cutting of fiber filament, and described thread passage communicates with described cutting;
Be installed on the cover plate (1) on the described fiber filament fixed head (2), offer casting solution charging hole (12) on the described cover plate (1);
Be positioned at the base (3) of described fiber filament fixed head below, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution outlet (11); Described casting solution passage (7) is communicated with described casting solution charging hole (12) by described thread passage, and the bottom of described casting solution passage (7) is pyramidal structure; Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) and core liquid passage (8) export (11) with described spinning solution and are communicated with;
B) fiber filament is put into add after the cutting of described fiber filament fixed head (2) described cover plate (1) fixing after, introduce in the described casting solution passage (7) compound with casting solution by described thread passage, through described spinning solution outlet (11) coextrusion, obtain hollow fiber ultrafiltration membrane after the typing;
Described casting solution comprises:
3. preparation method according to claim 2 is characterized in that, described fiber filament is selected from a kind of in terylene, nylon, cotton fiber and the polyamide fibre.
4. preparation method according to claim 2 is characterized in that, the quantity of described fiber filament is 1 ~ 10.
5. preparation method according to claim 2, it is characterized in that, described hydrophilizing agent is selected from one or more in the terpolymer of the terpolymer of bipolymer, vinyl chloride and carboxyl compound of vinyl chloride and carboxyl compound and vinyl chloride and hydroxy compounds.
6. preparation method according to claim 2 is characterized in that, described hydrophilizing agent is vinyl chloride-vinyl acetate bipolymer and/or chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer.
7. hollow fiber ultrafiltration membrane according to claim 2 is characterized in that, described pore-foaming agent is selected from polyvinylpyrrolidone and/or polyethylene glycol.
8. hollow fiber ultrafiltration membrane according to claim 2, it is characterized in that, described solvent is selected from one or both in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, trimethyl phosphate, triethyl phosphate and the tetramethylurea.
9. preparation method according to claim 2 is characterized in that, described fiber filament is put into the cutting of fiber filament fixed head (6) after the soak preliminary treatment.
10. preparation method according to claim 2 is characterized in that, described soak is solvent or acid-base solution, and described acid-base solution is that the pH value is 3 ~ 12 acid-base solution.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498206A (en) * | 2013-10-18 | 2014-01-08 | 天津膜天膜科技股份有限公司 | Hollow fiber membrane spinning pack |
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| CN104587849A (en) * | 2014-12-10 | 2015-05-06 | 广州海科滤膜科技有限公司 | Enhanced polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6454943B1 (en) * | 1998-11-03 | 2002-09-24 | S. Search B.V. | Longitudinal reinforced self-supporting capillary membranes and their use |
| CN1966132A (en) * | 2005-11-15 | 2007-05-23 | 深圳市诚德来实业有限公司 | PVC hollow fiber ultrafiltration membrane preparation method |
| CN101254422A (en) * | 2007-12-12 | 2008-09-03 | 深圳市诚德来实业有限公司 | High intensity PVC hollow fiber hyperfiltration membrane and method of preparing the same |
| CN102266726A (en) * | 2011-08-23 | 2011-12-07 | 浙江大学 | Method for preparing long fiber reinforced hollow fibrous membrane |
| WO2012148068A1 (en) * | 2011-04-26 | 2012-11-01 | 제일모직 주식회사 | Hollow fiber membrane having a reinforced monofilament |
| CN203080126U (en) * | 2013-01-21 | 2013-07-24 | 深圳市诚德来实业有限公司 | Spinning nozzle |
-
2013
- 2013-01-21 CN CN201310021522.5A patent/CN103031612B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6454943B1 (en) * | 1998-11-03 | 2002-09-24 | S. Search B.V. | Longitudinal reinforced self-supporting capillary membranes and their use |
| CN1966132A (en) * | 2005-11-15 | 2007-05-23 | 深圳市诚德来实业有限公司 | PVC hollow fiber ultrafiltration membrane preparation method |
| CN101254422A (en) * | 2007-12-12 | 2008-09-03 | 深圳市诚德来实业有限公司 | High intensity PVC hollow fiber hyperfiltration membrane and method of preparing the same |
| WO2012148068A1 (en) * | 2011-04-26 | 2012-11-01 | 제일모직 주식회사 | Hollow fiber membrane having a reinforced monofilament |
| CN102266726A (en) * | 2011-08-23 | 2011-12-07 | 浙江大学 | Method for preparing long fiber reinforced hollow fibrous membrane |
| CN203080126U (en) * | 2013-01-21 | 2013-07-24 | 深圳市诚德来实业有限公司 | Spinning nozzle |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498206A (en) * | 2013-10-18 | 2014-01-08 | 天津膜天膜科技股份有限公司 | Hollow fiber membrane spinning pack |
| CN103541029A (en) * | 2013-10-18 | 2014-01-29 | 北京碧水源膜科技有限公司 | Novel spinneret plate for producing long-fiber enhanced hollow fiber membrane |
| CN103498206B (en) * | 2013-10-18 | 2015-10-28 | 天津膜天膜科技股份有限公司 | A kind of hollow-fibre membrane spinning pack |
| CN103541029B (en) * | 2013-10-18 | 2015-12-23 | 北京碧水源膜科技有限公司 | The spinnerets of novel production long fiber reinforcement type hollow-fibre membrane |
| CN104587849A (en) * | 2014-12-10 | 2015-05-06 | 广州海科滤膜科技有限公司 | Enhanced polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
| CN106139921A (en) * | 2016-08-23 | 2016-11-23 | 北京中环膜材料科技有限公司 | The preparation method of TPVC hollow fiber ultrafiltration membrane and the milipore filter of preparation thereof |
| CN107486035A (en) * | 2017-09-23 | 2017-12-19 | 李日升 | A kind of PVC hollow fiber ultrafiltration membrane and preparation method thereof |
| CN108034999A (en) * | 2018-01-19 | 2018-05-15 | 山东招金膜天股份有限公司 | A kind of spinneret for producing long fiber reinforced type hollow-fibre membrane |
| CN108677261A (en) * | 2018-06-15 | 2018-10-19 | 天津碧水源膜材料有限公司 | Integrated fiber pipe pre-processes enhancement type hollow fiber film spinneret and its application method |
| CN111020715A (en) * | 2019-11-26 | 2020-04-17 | 江苏凯米膜科技股份有限公司 | Spinneret for preparing enhanced hollow fiber membrane, membrane preparation method and hollow fiber membrane |
| CN111111462A (en) * | 2020-01-06 | 2020-05-08 | 浙江长兴求是膜技术有限公司 | Fiber-reinforced hollow fiber multi-core membrane and preparation method thereof |
| CN112604509A (en) * | 2020-11-24 | 2021-04-06 | 上海工程技术大学 | Preparation facilities of many monofilament reinforcing hollow fiber membrane |
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