CN103031612B - A kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane and a kind of spinning head - Google Patents
A kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane and a kind of spinning head Download PDFInfo
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Abstract
The invention provides a kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane, the method add after fiber filament being put into the cutting of fiber filament fixed head (2) cover plate (1) fixing after, by thread passage introduce in casting solution passage (7) with casting solution compound, through spinning solution outlet (11) coextrusion, after sizing, obtain hollow fiber ultrafiltration membrane.Compared with prior art, first, the present invention, by by fiber filament and casting solution compound in advance, can make casting solution all have distribution inside and outside fiber filament, make casting solution and fiber filament difficult drop-off; Secondly, better, fiber filament runs through hollow fiber ultrafiltration membrane, makes the stretching stress point of milipore filter mainly concentrate on fiber filament, and then improves the TENSILE STRENGTH of hollow fiber ultrafiltration membrane for casting solution and fiber filament compound; Again, the present invention adopts special spinning head, and fiber filament is fixed location by the cutting of fiber filament fixed head and cover plate, simple to operation, is convenient to suitability for industrialized production.
Description
Technical field
The invention belongs to technical field of membrane separation, particularly relate to a kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane and a kind of spinning head.
Background technology
Membrane separation technique occurs in 20th century, a kind of separation technology developed rapidly nearly decades.UF membrane has separation, concentrated, purifying and refining function, has again that separative efficiency is high, energy consumption is low, is easy to recovery, automaticity advantages of higher without phase transformation, simple to operate, non-secondary pollution, separator.Wherein, comparatively typically hyperfiltration technique, especially hollow fiber ultrafiltration membrane.
Hollow-fibre membrane is a kind of threadiness, has the film of 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, be widely used in water treatment, pharmacy, brewage, food and drink, food, the field such as chemical industry separation process.
Prior art discloses and be multiplely applied to the macromolecular material that can make hollow-fibre membrane, comprise polyvinyl chloride (PVC), polysulfones (PS), polyether sulfone (PES), polyacrylonitrile (PAN), Kynoar (PVDF) etc.Hollow-fibre membrane is self supporting structure, higher to the requirement of strength of film silk, but the mechanical strength of the hollow-fibre membrane adopting above-mentioned material to prepare is lower, in application process, easily there is the situation of fracture of wire, cause that doughnut membrane lifetime is short, regular maintenance often, the problem such as cost of water treatment is high.
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 thermally induced phase separation film-forming process, and be that high score runs, while cost is high also easy in membrane body residual plasticiser.Therefore, need to research and develop new enhancement mode hollow fiber ultrafiltration membrane.
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 by polyvinylidene fluoride resin, and mix with additive and be made into casting solution, casting solution is coated on hollow support material, by the effect due to additive during coagulating bath, casting film material is delayed in a solvent be separated, a large amount of glue bundle body spreads to the contact surface of casting solution and coagulating bath, therefore produce the key-course of one deck densification, the hollow fiber ultrafiltration film with granule surface contral layer after solidifying, can be obtained.The TENSILE STRENGTH of this hollow fiber ultrafiltration membrane obtains larger raising, but casting solution is mainly distributed in skin, and internal layer distribution is less, causes cohesive force between casting solution and backing material not enough, 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 of enhancement mode hollow fiber ultrafiltration membrane and a kind of spinning head, and the enhancement mode hollow fiber ultrafiltration membrane compound that the method obtains is better and TENSILE STRENGTH is higher.
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 the cutting for holding fiber filament, and described thread passage communicates with described cutting;
Be installed on the cover plate (1) on described fiber filament fixed head (2), described cover plate (1) offer casting solution charging hole (12);
Be positioned at the base (3) below described fiber filament fixed head, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution and exports (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) exports (11) with core liquid passage (8) with described spinning solution and is communicated with.
Present invention also offers a kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane, comprise the following steps:
A) provide a kind of spinning head, comprising:
Fiber filament fixed head (2), described fiber filament fixed head (2) is provided with thread passage and the cutting for holding fiber filament, and described casting solution backflow preventing structure (14) offers thread passage, and described thread passage communicates with described cutting;
Be installed on the cover plate (1) on described fiber filament fixed head (2), described cover plate (1) offer casting solution charging hole (12);
Be positioned at the base (3) below described fiber filament fixed head, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution and exports (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) exports (11) with core liquid passage (8) with described spinning solution and is communicated with;
B) add after fiber filament being put into the cutting of described fiber filament fixed head (2) described cover plate (1) fixing after, by described thread passage introduce in described casting solution passage (7) with casting solution compound, through described spinning solution outlet (11) coextrusion, after sizing, obtain hollow fiber ultrafiltration membrane;
Described casting solution comprises:
Preferably, described fiber filament is selected from the one in terylene, nylon, cotton fiber and polyamide fibre.
Preferably, the quantity of described fiber filament is 1 ~ 10.
Preferably, described hydrophilizing agent is selected from one or more in the bipolymer of vinyl chloride and carboxyl compound, vinyl chloride and the terpolymer of carboxyl compound and the terpolymer of 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 tetramethylurea.
Preferably, described fiber filament puts into the cutting of fiber filament fixed head (6) after soak preliminary treatment.
Preferably, described soak is solvent or acid-base solution, described acid-base solution to be pH value be 3 ~ 12 acid-base solution.
The invention provides a kind of preparation method of enhancement mode hollow fiber ultrafiltration membrane, the method add after fiber filament being put into the cutting of fiber filament fixed head (2) cover plate (1) fixing after, by thread passage introduce in casting solution passage (7) with casting solution compound, through spinning solution outlet (11) coextrusion, after sizing, obtain hollow fiber ultrafiltration membrane; 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.Casting solution being coated in hollow support material with prior art prepares compared with hollow fiber ultrafiltration membrane, and long fiber, by by fiber filament and casting solution compound in advance, is positioned among casting solution and then obtains hollow fiber ultrafiltration membrane by the present invention.First, the present invention, by by fiber filament and casting solution compound in advance, can make casting solution all have distribution inside and outside fiber filament, make casting solution and fiber filament difficult drop-off; Secondly, better, fiber filament runs through hollow fiber ultrafiltration membrane, makes the stretching stress point of milipore filter mainly concentrate on fiber filament, and then improves the TENSILE STRENGTH of hollow fiber ultrafiltration membrane for casting solution and fiber filament compound; Again, the present invention adopts special spinning head, and fiber filament is fixed location by the cutting of fiber filament fixed head and cover plate, 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%.
Accompanying drawing explanation
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.
Detailed description of the invention
Refer to Fig. 1, in Fig. 1,1 is cover plate, and 2 is fiber filament fixed head, 3 is base, and 4 is bottom spinning head, and 5 is spinning head stage casing, 6 is fiber filament, and 7 is casting solution passage, and 8 is core liquid passage, 9 is second channel, 10 is core liquid pipe, and 11 is spinning solution outlet, and 12 is 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 the cutting for holding fiber filament, and as shown in Figure 2, in Fig. 2, a is the cutting for holding fiber filament, b is thread passage, and c is that screw hole is for being fixed with miscellaneous part.Described thread passage communicates with described cutting, and the quantity of wherein said cutting is also unrestricted, and be preferably 1 ~ 6 in the present invention, be more preferably 2 ~ 4, cutting can be evenly distributed on fiber filament fixed head (2), also can uneven distribution, there is no special restriction.
Be installed on the cover plate (1) on described fiber filament fixed head (2), described cover plate (1) offer casting solution charging hole (12);
Be positioned at the base (3) below described fiber filament fixed head, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution and exports (11).
Described casting solution passage (7) is communicated with described casting solution charging hole (12) by described thread passage, thread passage communicates with cutting, thus described casting solution passage (7) is communicated with described cutting by described thread passage, the width of described cutting is thinner, slightly larger than filament size, thus casting solution is not easily outflowed.
Fiber filament is through cutting and thread passage, and introduce in casting solution passage (7), herein, casting solution and fiber filament carry out compound.
The bottom of described casting solution passage (7) is pyramidal structure; Pyramidal structure outlet is comparatively thin, and controllable flow goes out the diameter of spinning solution, the casting solution rate of outflow also can be made comparatively slow, thus can make casting solution and fiber filament abundant 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) exports (11) with core liquid passage (8) with described spinning solution and is communicated with.
For convenience of cleaning and installation, described base (3) is preferably divided into bottom spinning head stage casing (5) and spinning head (4).Described first passage is preferably located at spinning head stage casing, and the second channel (9) of described pyramidal structure is preferably located at bottom spinning head.Described second channel (9) exports (11) and is communicated with described spinning solution.Described core liquid passage (8) exports (11) preferably by core liquid pipe (10) with spinning solution and is connected.
In order to optimize technique scheme, described core liquid passage (8) and described core liquid charging hole (13) can be located at and spinning head stage casing (5) also can be located at bottom spinning head on (4), there is no special restriction.In the present invention, preferred spinning head stage casing (5) is provided with core liquid charging hole (13) and described core liquid passage (8), and described core liquid passage (8) is arranged in parallel with the first passage of described casting solution passage (7).
Described cover plate (1), between fiber filament fixed head (2) with base (3), described spinning head stage casing (5) is all connected by attaching parts (14) between (4) with bottom spinning head.Described attaching parts (14) are preferably screw.
Present invention also offers 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, comprise the following steps: add after fiber filament being put into the cutting of fiber filament fixed head (2) described cover plate (1) fixing after, with casting solution compound in described thread passage introducing casting solution passage (7), through spinning solution outlet (11) coextrusion, after sizing, obtain hollow fiber ultrafiltration membrane.
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 make fiber filament better with casting film liquid phase compound, the present invention carried out preliminary treatment preferably put into the cutting of fiber filament fixed head (2) at fiber filament before.Described pretreated method is method well known to those skilled in the art, there is no special restriction.Preliminary treatment described in the present invention is preferably soaks.Described soak can be the solvent in casting solution, also can be acid-base solution, there is no special restriction.Described solvent be preferably in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, trimethyl phosphate, triethyl phosphate and tetramethylurea one or both.Described acid-base solution to be pH value be 3 ~ 12 acid-base solution, pH value is preferably 5 ~ 10.
Through the preliminary treatment of soak, the grease on fiber filament surface can be removed, also can the caking property of high molecular polymer in fortifying fibre long filament and casting solution.
The present invention also preferred by fiber filament through fiber filament dispensing rack, enter fiber filament fixed head (2).Described fiber filament dispensing rack is fiber filament dispensing rack well known to those skilled in the art, there is no special restriction.Fiber filament described in the present invention is first through the guide wheel of fiber filament dispensing rack, and by fiber filament coil stripping, be then directed on locating wheel, vertically imported in spinning head by fiber filament by locating wheel, it can reduce frictional force.
The material of fiber filament has higher intensity, it can be used as the backing material of 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 hydrophilizing agent well known to those skilled in the art, there is no special restriction.Hydrophilizing agent described in the present invention be preferably selected from the bipolymer of vinyl chloride and carboxyl compound, vinyl chloride and the terpolymer of carboxyl compound and the terpolymer of vinyl chloride and hydroxy compounds one or more,, be 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 pore-foaming agent well known to those skilled in the art, 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 organic solvent well known to those skilled in the art, there is no special restriction.Solvent described in the present invention be preferably in dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, trimethyl phosphate, triethyl phosphate and tetramethylurea one or both.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), described casting solution and fiber filament compound in casting solution passage (7).
The present invention, by by fiber filament and casting solution compound in advance, can make casting solution all have distribution inside and outside fiber filament, make casting solution and fiber filament difficult drop-off; Meanwhile, better, fiber filament runs through hollow fiber ultrafiltration membrane, makes the stretching stress point of milipore filter mainly concentrate on fiber filament, and then improves the TENSILE STRENGTH of hollow fiber ultrafiltration membrane for casting solution and fiber filament compound.
According to the present invention, described casting solution preferably stirs 10 ~ 30h under 50 DEG C ~ 80 DEG C conditions, and then inject casting solution charging hole after standing and defoaming, more preferably stir under 60 DEG C ~ 70 DEG C conditions, described mixing time is preferably 15 ~ 25h.Described time of repose is preferably 6 ~ 15h, is more preferably 7 ~ 10h.Adding thermal agitation can make each component of casting solution fully dissolve mixing.Fiber filament after abundant compound and casting solution are through spinning solution outlet (11) coextrusion, during described coextrusion, the present invention preferably adopts dry-wet spinning, spinning solution exports the fiber filament extruded and contacts with core liquid, first through one section of air layer before entering coagulating bath through spinning solution outlet (11) with casting solution.The spinning external diameter of described dry-wet spinning is preferably 1.0mm ~ 3.0mm, be more preferably 1.5mm ~ 2.0mm, the spinning internal diameter of described dry-wet spinning is preferably 0.5mm ~ 1.5mm, is more preferably 0.6mm ~ 1.2mm, described air gap height is preferably 10cm ~ 25cm, is more preferably 14cm ~ 20cm.
The method of described sizing is method well known to those skilled in the art, there is no special restriction.Solution phase disengagement method is preferably adopted to shape in the present invention: the fiber filament fully after 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, 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 organic solvent well known to those skilled in the art, there is no special restriction, and described organic solvent can be identical with the solvent in casting solution, also can be different, and unrestrictedly.In the mixture of described water and organic solvent, the ratio of water and organic solvent is also unrestricted, ensures that it contains moisture.Described core liquid can be identical with the composition of coagulating bath, 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 illustrate the present invention, below in conjunction with embodiment, the preparation method of a kind of enhancement mode hollow fiber ultrafiltration membrane provided by the invention and a kind of spinning head are described in detail.
Reagent used in following examples is commercially available.
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 the cutting for holding fiber filament, and described cutting is evenly distributed on that fiber filament fixed head (2) is upper and quantity is 4; Be installed on the cover plate (1) on described fiber filament fixed head (2), described cover plate (1) offer casting solution charging hole (12); Be positioned at the spinning head stage casing (5) below fiber filament fixed head, be provided with the first passage of casting solution passage, core liquid charging hole (13) and core liquid passage (8), the first passage of core liquid passage and casting solution passage is arranged in parallel; Be positioned at bottom the spinning head below spinning head stage casing (5) (4), 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) and core liquid pipe (10) all export (11) and are communicated with spinning solution; Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) exports (11) with core liquid pipe (10) with described spinning solution and is communicated with.
1.2 by following proportions 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 DEG C, stirs 16h, standing and defoaming 8h.
1.3 by 3 polyster fibre filaments after dimethylacetylamide dipping pretreatment, put into the cutting of spinning head fiber filament fixed head (2) and pass thread passage, introduce casting solution passage (7), the casting solution obtained in 1.1 is injected by casting solution charging hole (12), enter in casting solution passage (7) through thread passage, polyster fibre filament and casting solution are after the middle compound of casting solution passage (7), adopt dry-wet spinning, spinning external diameter 1.7mm, internal diameter 0.9mm, contact with core liquid after spinning solution outlet (11) coextrusion, through the air gap of height 17cm, spinning speed 35m/min, then enter coagulating bath sizing and obtain middle fiber ultrafiltration membrane.Core liquid and coagulating bath are water, and temperature is 30 DEG C.
After rinsing and 40% glycerine are soaked, performance test is carried out by obtaining hollow fiber ultrafiltration membrane in 1.3, 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 DEG C 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 the cutting for holding fiber filament, and described cutting is evenly distributed on that fiber filament fixed head (2) is upper and quantity is 4; Be installed on the cover plate (1) on described fiber filament fixed head (2), described cover plate (1) offer casting solution charging hole (12); Be positioned at the spinning head stage casing (5) below fiber filament fixed head, be provided with the first passage of casting solution passage, core liquid charging hole (13) and core liquid passage (8), the first passage of core liquid passage and casting solution passage is arranged in parallel; Be positioned at bottom the spinning head below spinning head stage casing (5) (4), 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) and core liquid pipe (10) all export (11) and are communicated with spinning solution; Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) exports (11) with core liquid pipe (10) with described spinning solution and is communicated with.
2.2 by following proportions 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 DEG C, stirs 16h, standing and defoaming 8h.
2.3 by 4 polyster fibre filaments after dimethylacetylamide dipping pretreatment, put into the cutting of spinning head fiber filament fixed head (2) and pass thread passage, introduce casting solution passage (7), the casting solution obtained in 2.1 is injected by casting solution charging hole (12), enter in casting solution passage (7) through thread passage, polyster fibre filament and casting solution are after the middle compound of casting solution passage (7), adopt dry-wet spinning, spinning external diameter 1.7mm, internal diameter 0.9mm, contact with core liquid after spinning solution outlet (11) coextrusion, through the air gap of height 17cm, spinning speed 35m/min, then enter coagulating bath sizing and obtain middle fiber ultrafiltration membrane.Core liquid and coagulating bath are water, and temperature is 30 DEG C.
After rinsing and 40% glycerine are soaked, performance test is carried out by obtaining hollow fiber ultrafiltration membrane in 2.3, 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 DEG C 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 the cutting for holding fiber filament, and described cutting is evenly distributed on that fiber filament fixed head (2) is upper and quantity is 4; Be installed on the cover plate (1) on described fiber filament fixed head (2), described cover plate (1) offer casting solution charging hole (12); Be positioned at the spinning head stage casing (5) below fiber filament fixed head, be provided with the first passage of casting solution passage, core liquid charging hole (13) and core liquid passage (8), the first passage of core liquid passage and casting solution passage is arranged in parallel; Be positioned at bottom the spinning head below spinning head stage casing (5) (4), 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) and core liquid pipe (10) all export (11) and are communicated with spinning solution; Described core liquid passage (8) is communicated with core liquid charging hole (13); The bottom of described casting solution passage (7) exports (11) with core liquid pipe (10) with described spinning solution and is communicated with.
3.2 by following proportions 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 DEG C, stirs 16h, standing and defoaming 8h.
3.3 by 6 polyster fibre filaments after dimethylacetylamide dipping pretreatment, put into the cutting of spinning head fiber filament fixed head (2) and pass thread passage, introduce casting solution passage (7), the casting solution obtained in 3.1 is injected by casting solution charging hole (12), enter in casting solution passage (7) through thread passage, polyster fibre filament and casting solution are after the middle compound of casting solution passage (7), adopt dry-wet spinning, spinning external diameter 1.7mm, internal diameter 0.9mm, contact with core liquid after spinning solution outlet (11) coextrusion, through the air gap height of height 17cm, spinning speed 35m/min, then enter coagulating bath sizing and obtain middle fiber ultrafiltration membrane.Core liquid and coagulating bath are water, and temperature is 30 DEG C.
After rinsing and 40% glycerine are soaked, performance test is carried out by obtaining hollow fiber ultrafiltration membrane in 3.3, 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 DEG C of water temperatures).
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 (8)
1. a preparation method for enhancement mode hollow fiber ultrafiltration membrane, is characterized in that, comprises the following steps:
A) provide a kind of spinning head, comprising:
Fiber filament fixed head (2), described fiber filament fixed head (2) is provided with thread passage and the cutting for holding fiber filament, and described thread passage communicates with described cutting;
Be installed on the cover plate (1) on described fiber filament fixed head (2), described cover plate (1) offer casting solution charging hole (12);
Be positioned at the base (3) below described fiber filament fixed head, described base (3) is provided with casting solution passage (7), core liquid charging hole (13), core liquid passage (8) and spinning solution and exports (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) exports (11) with core liquid passage (8) with described spinning solution and is communicated with;
B) add after fiber filament being put into the cutting of described fiber filament fixed head (2) described cover plate (1) fixing after, by described thread passage introduce in described casting solution passage (7) with casting solution compound, through described spinning solution outlet (11) coextrusion, after sizing, obtain hollow fiber ultrafiltration membrane;
Described casting solution comprises:
Described fiber filament is terylene.
2. preparation method according to claim 1, is characterized in that, the quantity of described fiber filament is 1 ~ 10.
3. preparation method according to claim 1, it is characterized in that, described hydrophilizing agent be selected from the bipolymer of vinyl chloride and carboxyl compound, vinyl chloride and the terpolymer of carboxyl compound and the terpolymer of vinyl chloride and hydroxy compounds one or more.
4. preparation method according to claim 1, is characterized in that, described hydrophilizing agent is vinyl chloride-vinyl acetate bipolymer and/or chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer.
5. preparation method according to claim 1, is characterized in that, described pore-foaming agent is selected from polyvinylpyrrolidone and/or polyethylene glycol.
6. preparation method according to claim 1, is characterized in that, described solvent be selected from dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, trimethyl phosphate, triethyl phosphate and tetramethylurea one or both.
7. preparation method according to claim 1, is characterized in that, described fiber filament puts into the cutting of fiber filament fixed head (2) after soak preliminary treatment.
8. preparation method according to claim 7, is characterized in that, described soak is solvent or acid-base solution, and described solvent is the solvent in described casting solution, described acid-base solution to be pH value be 3 ~ 12 acid-base solution.
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| 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 |
| CN108034999B (en) * | 2018-01-19 | 2023-09-01 | 山东招金膜天股份有限公司 | Spinneret plate for producing long fiber reinforced hollow fiber membrane |
| CN108677261B (en) * | 2018-06-15 | 2020-08-18 | 天津碧水源膜材料有限公司 | Integrated fiber tube pretreatment enhanced hollow fiber membrane spinneret plate and use method thereof |
| CN111020715B (en) * | 2019-11-26 | 2021-03-23 | 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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